PB85-245280
Industrial Process Profiles for
Environmental Use. Chapter 10
The Plastics and Resins Production Industry
Radian Corp., McLean, VA
Prepared for
Environmental Protection Agency, Cincinnati, OH
Jul 85
U.S. Dipntaart tf
urns
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EPA/600/2-85/085
July 1985
INDUSTRIAL PROCESS PROFILES POR ENVIRONMENTAL USE
Chapter 10, The Plastics and Resins Production Industry,
Radian Corporation
McLean, Virginia 22102
EPA Contract No. '8-02-3994
Project Officer
Mark J. Stutsaan
Industrial Wastes and Toxics Technology Division
Vater Engineering Research Laboratory
Cincinnati, Ohio 4)268
WATER ENGINEERING RESEARCH LABORATORY
OP7ICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 4)268
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*
i MI PORT wo.
EPA/600/2-8S/C8S
•. TITLI AND SU9TITLI
Industrial Process Profiles
^^ TECHNICAL REPORT DATA
3
for Environmental Use
Chapter 10: The Plastics and Resins Production Industry
Radian Corporation
Radian Corporation
7655 Old Sprlnghouse Road
McLean, VA 22102
Hater Engineering Research
Office of Research and Deve
U.S. Environmental Protect!
Cincinnati, Ohio 45268
NIW
Laboratory
lopment
on Agencv
1 MClFlCNTI ACCISSION NO.
PBS 5 2 4 5 2 8 0 /IS
July 1985
I Pt WONMINO OHOANIZATION COOI
1 PINPOMMINa OMQANIZATION fttPOIT KO
..rM00MAM|L|M.NTPIB.
11 CCNTRACT/BNANT NO
68-02-3994
68-02-3171
i* Tvra o» mtfomt ANO^IHIOO covimo
Final Bannrr (7/A1 . A/HS)
14. W*ONtONlNa AOINCY COOI
EPA/600/14
Contact Clyde R. Dempsey, (513)684-7502
This report presents a detailed analysis of the plastics and resins production
Industry, which Includes operations that convert industrial organic chemicals into
solid or liquid polymers. Elements of the analysis include an industry definition,
raw materials, products and manufacturers, environmental Impacts, and occupational
health concerns.
The following polymers are discussed: acrylic resins, actylonitrile-rbutadiene
•• tVT&nm ( ARC \ m\ lr«f«4 MM! A Ann ••AM^M^ m^t^.** «^^ 4 «* _.,_,_ j _..__._ *_— *.«_ . « » » _
epoxies, fluoropolymers, phenolic resins, polyacetal, polyamides, pollmldes, poly-
oleflns (polybutylene, polyethylenes, polypropylene), polycarbonate, polyesters,
polystyrenes, polyurethane, polyvlnyl acetate and alcohol, polyvinyl chloride,
polyvlnylidene chloride, and styrene-acrylonierile (SAN). Fabrication of these reaina
is discussed in IPPEU Chapter lOa m.e Plastics and Resins Processing Industry). Major
additives used in resin production are discussed in IPPtU Chapter lOb (Plastics
Additives).
The IPPEU Chapter 10, lOa and lOb series is1 an update and expansion of
naterlsl published in the 1977 report, IPPEU Chapter 10, the Plastics and Resins
Industry. KPA-600/2-77-023L
M V WOftOS AND OOCWMtNT ANALV»l«
lOINtl»ltNt/Of N tftlMO TIMMt
• IPIVI HIVVTION •TATIMIWT
Release to Public
j« u ai uaii
7*!
1
9um fae.i (e«« 4-m
it
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DSCLAI) R
The Lnforiiattón In thu docu.ent has been funded ‘sholly or in part b
he United States Environmental Protection Agency under Contract No.
68-02—3994 to Radian CrporatLon. It has been subject to the Agency’s peer
and administrative review, and it ha. been approved for publicationas an
EPA document. Mention of trade naacp or conmercial products does not con-
stittste endorsement or rocoáendation for use.
Ii
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FOREWORD
Th’. U.S. Environmental Protection Age cy is charged by Congress with
protec’.ing the Nation’s land, air, and water systems. Under a mandate of
ratloral environmental laws, the Agency strives to formulate and impl’.ment
acO3is leading to a compatible balance betveen human activities and the
abiLity of natural systems to support and nurture life. The Clean Water
Act, the Safe Drinking Water Act, and the Toxic Substances Control Act are
three of the major congressional laws that provide the framework for restor-
ing and maintaining the integrity of our Nation’’. wutet, for preserving and
enhancing the water we drink, and for protecting the environment from toxic
substances. These laws direct the EPA to perform research to define our
environmental problems, measure the impa’ ts, and search for solutions.
The Water Engineering Research Laboratory is that c’.ponent of EPA’S
Reqegrch and Development program concerned with preventing, treating, and
managing municipal and industrial wastewater discharges; establishing prac-
tices to control and remove contaminants from drinking water and to prevent
its deterioration during storage and distribution; and assessing the nature
and controllability of releases of toxic substances to the air, water, and
land from manufacturing processes and subsequent product uses. This publi-
cation is one of the products of that research anti provides a vital comsuni•
cation link between the researcher and the user community.
Thi. report covers the release of toxic materials to the environment
and to the workplace during the manufacture of plastic reiins. This report
wilt be used in EPAs re iev of premanufacturing notices (PP J’s).
Francis T. Nayo, Dirictor
Water Engineering Research Laboratory
iii
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ABSTRACT
This docement presents a detailed anaysis of the plastics and resins
production industry, which includes operations that convert industrial
crganic chemicals into solid or liqutd polymers. Kleaen s of the analysis
Inelude, an industry definition,rav materials, products and manufacturers,
environmental impacts, and occupational health concerns.
The following polymers are discussed: acrylic resins, acrylonitrile-
butadiene—styrene (ASS), alkyd molding resins, amino resins, engineering
thermoplastics, epoxies, fluccopolymers, ph.nolic resins, polyscetal, poly—
smtdes, polyimides, polyolef ins (polybutylene, polyethylene., polypropy-
lene), polycarbonete, polyestirs,polystyrenes, polyurethane, polyvinyl
acetate and a cohel, polyvinyl’ chlorid , ’ polyvinylidene chloride, and
styrene—acrylonitrile (5*11).. Vabrication of these resin, is discussed is
IPPRU hspcer 10. ( The Plastics and Resine Processin Ind’ist ). ) jor
additives used in resin production’ are iscus e n IUE pter lOb
( PlasticsAddftjves) .
Ppm materials for plastics and resins are industrial org,nie chemicals
used as monomers or plasticizers and specialty chemicals used as additives
to modify resin properties.
Polyethylenes, polyvinyl chloride, polypropylene, and polystyrene
accounted for almot 80 percent ( y weight) of the plastics produced in the
United States in 1980. The types of companies involved in plastics produc-
tion vary, but the principal produe.rs are major oil and chemical, paint,
‘tire and rubber, steel, and electrical asnufacturing companies.
Plastic and resin production ;roceeus generate air emissions, west.—
mater, and solid waste. Volatile emission, are generally highest in procee-
sing steps upstream of th. reactor and is mass and solution polymerization
monomer and solvent recovery stepe. Suspension and emulsion polyuer iaatine
processes typically generate more particulate ons 1
The most significant source of vastivater in plastics prodvcrin is the;
water used for emulsion and suapension polymeriaatinn, Vastevater soy con-
tain monomer , comonoser, sdditives, and fillers.’
Solid waste is generated from plastics production in one of two ways:
polymer lost from th. process (I.e. spills, routine cleaning, particulate
collection) and byprtduct formation (i.e. lod— lecular-weight polymers).
Spent catalyst or additive, also may constitute solid meets from s
processes.
iv
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Some of the chemicals used as raw materials in plastics production are
highly toxic and may pr,duce serious adverse health effects in overexposed
employees. However, effective engineering ccntrols and personal protective
equipment and clothing exist that greatly reduce worker exposure potential.
Successful application of these controls depends on plant—specific factors
such as plant design, materials handled, process configuration, and
management and employee dedication to maintaining a good occupational health
program.
This report was submitted in fulfillment of Contract No. 68—02—3994 by
Radian Corporation under the sponsorship of the U.S. Env ronmental Protec
tion Agency. This assignment covers the period October 1984 to April 1985.
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CONTENTS
I • I • I • I I
Foreword .
Abstract
Figures
Tables
Section 1.
Section 2.
Section 3.
Section 4.
Section 5.
Section 6.
Section 7.
Section 8.
Section 9.
Section 10.
Section ii.
Section 12.
Section 13.
Section 14.
Section 15.
Sect Ofl if,.
Section 17.
Section 18.
Section 19.
Sect i03 20.
SectIon 21.
Sect’Loi 22.
SectSofl 23.
Section 24.
Section 25.
Section 26.
SectIon 27.
Section 28.
S lbllogra’phl
Appendices
I I I I I I I • • I I a I • I I • • • I I I I I S I •
• I I I • I I I I I I I I I I I • • I I I I I • • S S I I •
• • • I I I I • I • S I I I I • I S I I • I I • I • S •
• I I I • I I I • I • I • • I • S I I I • • • • • • • • I •
Industry Analysis. • . . . . . . .
Acrylic Resins . . . . . . . . . . . . .
Acry1o.itrile_8utadieflStY!e1 e (AES). .
Alkyd Molding Resins . . . • . . . . . .
Am lao Resins . • . . . . • . . • . . . .
Modified P,lyphenylene Oxide and Polyphenylefle
E p3zy Resins . • . • . . . . . . . . . . a •
F luotopolymets . . . . . . . • . . . . . . .
rienolic Resins. • . . . . . . . . . . . . .
Polyacetal . . . . • . . a • a • a • a • •
Polyamide Resins • . . . . . . . . . . . a
Potybutylefle . . • . . • . . . . . a • • •
PolycarbOnate. . . . . . . . . . . . . . .
Poly(Esterlmide) and Poly(EPhSDImide) Resins
P,lyester Resins (Saturated) . . . . . . . a •
Polyester Resins (Unsaturated) . . a • • a
Polyethylene — High Density (ND?!) . . . .
Polyethylene — Linear Low Density (LLDPE)
Polyethylene — Low Density (LOPE). . • a . •
Po1yptop lSflS . . . . . . . . . a • • • • •
Polystyrene (General Purpoa ) . . . . . . .
Polystyrene (Impact) . . . . . . . . . . . .
Polyurethane Foam . a • • • • • • . . . a a
Polyvinyl Acetate . a . a a • a • • • • •
Polyvinyl Alcohol a • • • a • a • • a a a •
Polyvinyl Chinride . a • • • a a a . • • a
Po1yv1ny1ide Chloride (PVDC) a • • • • • •
StyreneActylOflit rile (SAN). . . . . . . . . a
. . I S • • • a a I a a a • . a a a a I I I I
iii
iv
vii
z
I
41
74
95
1,
S —
154
169
201
223
249
267
293
303
316
333
3”
377
401
416
443
465
493
519
542
570
589
623
641
• I I • I
• . . . .
a I I I I
. a I I I
Sulfide
a a a I
I I I I I
I I I I a
a a •. I I
a I I a I
• I I I I
I I I a a
. a ala
• • a I
• a a a a
a a a . a
. a • a .
• ala a
. a. •a
• I I I I
I I I I I
a I I •I
• a I I I
a a • I I
11111
a...’
a a a . I
A. Typical physical and chemical properties of
B. Input nonoiners. . . . . . . . . . . .
( . Coepanies that produce plastics • . . •
• 659
• . . • 681
• • a a 726
I a a • 733
polymers .
• . • a a a a
• I I I I I S
vi
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FIGURES
Mumber
1 Mass polymerization process • • • •
2 Solution polymerization process . . . . . . . . . . . . . . . 61
3 Suspension polymeriz.tjon process . . . . . . . . . . . . . . 62
4 Emulsion polymerization process . . . . . . . . . . . . . . . 64
5 EmullionA3 sprocess ..,...... 83
6 Mass suspension AIS process . . . . . . . . . . . . . . . . . 05
1 Mass ABS process . . . . . . . . . . . . . . . . . . . . . . . 87
8 Alkyd resin production using the alcoholysi. method . . . . a 113
9 Alkyd resin production using th. fatty acid method . . . . . . 115
10 Amino adhesive resin production process . . . . . . . . . . . 142
ii Amino coating resin production procuss . . . . a . • • • . . . 143
12 Amino laninating resin producLion process . . . . . . . . . . 145
13 Amino molding resin production process . . . . . . . . . . . . 147
14 MPO production pr’icess . . . . . . . . . . . . . . . . . . . . 161
15 PPS production process . . . . . . . . . . . . . . . . • . . . 162
16 Low molecular weight liquid epoxy resin production process . . 188
17 Medium molecular weight epoxy resin production using the
taffy process . . . . . . . . . . . . . . . . . . . . a . a • 190
18 High molecular weight epoxy resin using the advancement
process . . . . . . . . a . • • • . • . . . . . . . . a . . a 191
19 Aqueous PTFE dispersion produced batchvi.. . . . . . . . . . . 209
20 Bat’ h fine PilE powder production a • • . • • • . . . . . . . 210
21 Batch granular PTVE production . . . . . . . . . . • . . . 212
22 Mass polymerization of PCTFE . . . . . . . . . a . . . a • a . 213
23 Suspension polymerization of PCTFE . . a . . a • • • a • a a • 215
24 Emulsion polymerization of PCTPE. . . . . . . . . . . . . . . 216
25 Reso production process . . . . a . . . • • • . . . . . . . . 239
26 Movolak production process . . . . . . . . . . . . . . . . . . 241
21 Acetal homopolymer production process . a • • . • • . . . . . 258
28 Acetil copolymer production . . . . . . . . . . . . . . . . . 260
29 Polyamide production using the polysdditfon process . . . . . 203
30 Polya.ide resin production using the poiyccidensaijon
proc!.s . . . . . . . . . . . . . . . • . . . . . a . . . . . 284
31 Mass polymoriz i.1on of polybutylene . . . . . . . . . . . . . 291
32 Block diagra. for polycarbonat. production (Loterfacial
0 lymertzation . . . . . . . . . . a a • • a . . • • . . . . a 310
33 PoIy(ester—tml de) redin manufacturing process. a a . a a . • . 323
34 Poly(ether—fmlde) resin manufacturing process. . . . . . . . . 325
35 PET production process using OFf? a a . . • • • • . a a . . • • 344
36 PET pr.iducttn, process ising l.A . . a a a • a . • • a a a a . 343
31 PBT production proc.ss . . . . . . . . . . a • a a a a a a . a 347
vii
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FiGURES (Continued)
Number
38 Unsaturated polyester resin production process . . . . . . . . 310
39 Particle form polymerization process . . . . . . . . . . . a . 389
40 Solution polymertzatl ,n process . . . . . . . . . . . . . . . 391
41 Low pressure gas phasepolymerization . . . . . . . . . . . 392
42 Particle form po1ym ’rtzation process . . . . . . . • • • • • • 408
43 Solution polymerization process . . . . . . a • • • • . . . . 409
44 Low pressure gas phase polymerization . . . . . . . . . . . . 411
43 High pressure mass polymerization . . . . . . . . . . . . . . 431
46 Solution polymerizatin . . a • . • • . . . a . • • • . . . . . 432
4! Low pressure gsa phase polya.rization . . . . . . . . . . . . 434
48 Solution po1ymertz tiàn of PP using a conventional
catalyst . . . . . . a • • • • . . . . . . . . a • • • • • . . 452
49 Solution polymerization of PP using a high, yield cata’ it . . 453
30 Mass polymerization of polypropylene u.ing a conventto. 1
catalyst . . . a a • • • • . . . . a • • • • . . . . . . . . 456
Si Gas phase polymerization . a • • a . . . . . a • • • • • a • 457
52 P ,1ygtyrene production using the suspension polymerization
process . . . . . . . . . . . . . . . . . . . . . . . . . . 478
53 Expandable bead pólyatyrèn. production using the suspension
polymerization process . . . . . a a . • a . . . . . . . . . . 480
54 Polystyrene production via mass polymerization . . . . . . . . 481
55 Polystyrene production via solution polymerization . . . a . a 483
56 Polystyrene prodãction using the suspension polymerization
process • a . . a . a •. • . • . • . . . . . . • • • • • .507
51 Polyityrene production vt a mass polymerization a . • • . . . . 309
58 Polysfyrene production via solution polymerization . . . . . . 511
59 ‘Polyurethane foam pro’duction using the one—shot process a • . 536
60 Polyvinyl acetate production using emulsion polymerization . . 555
61 Polyvinyl acetate usinl continuous emulsion polymerization . . 556
62 Polyvinyl acetate using auspenCion polymerization . . . . . .
63 Polyvinyl acetate producUon via centimaou solution
polymerization . . . . . . . . . . . . . a . • a • . . • . . . 5131
64 Polyvinyl acetate production via continuous mass
polymerization. . . . . • .. . . . . . . . . . . . . . . . .562
65 Continuous polyvinyl alcohol production using the suspension
polymerization process • -. . • . • . . . . . . . . . . . a • a 579
Continuous polyvinyl alcohol production using the solution
polymerization process . . . . .. . • . . • . •. . . . . . . 980
61 PVC production usinl the suspension polymerization process . . 606
68 PVC production using the emulsion polymerization process . . . 608
69 PVC production using the ease polymerization process . . . . .610
70 PVC production using th. solution polymerizstlon process . a 612
71 PVC production using the pr.eipttation polymerization
process . . . . . • . . . . . . . • . . . . . . . . . . . • 613
7? P lyviny1idene chloride production using emulsion
polymerization . . • • • • • • • • a • • • • • . . . . . . . • 832
viii
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Number
FIGURES (Continued)
73 Polyvinyitdene chloride production
polymerization
74 SAN emulsion procees . . . .
75 SAN suspension process . . .
76 SAN mass polymerization
using suspension
• • • • . . 634
• • • • . . . . • • • • . 649
• • • . • • • 651
• • • • 652
i x
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TABLES
Number
1 Value of Product Shipped by Major Chemical Industries . . . . 2
2 Industry Sector Descriptions . . . . . . . . . . . . . . . . . 4
3 Principal Raw Materials Used in the Plastics Industry . . . . 9
4 Major Additive Classed Used in the Plastics Industry . . . . . 11
5 Plastics and Resins Production— 1980 . . . . . . . . . . . . 16
6 Specialty Plastics . . . . . . . . . . . . . . . . . . . . . . 17
7 U.S. Markets for Plastics — 1980 . . . . . . . . . . . . . . . 18
8 Diversified Plastic and Resins Producers . . . . . . . . . . . 22
9 Plastic Production Emissions Suesary . . . . . . . . . . . . . 23
10 Regulations and Recommendations for Airborne Emissions of
Chemicals of Concern. . . . . . . . . . . . . . •1 •s••• 28
11 U.S. Acrylic Resin Producers . . . . . . . . . . . . . . . . . 43
12 l98lConsumptlonofAcryltcResins. ....•... •1S ... 50
13 Typical Input Materials to PPQ(A Production Proceoses in
Addition to Monomer and Initiator . . . . . . . . . . . . . . 54
14 Typical Operating Parameters for PPQIA Production Processes . . 54
15 Input Materials and Specialty Chemicals Used in PMM&
,Ianufacture in AdditIon to Monimer . . . . . . . . . . . . . . 55
16 Worker Distribution Estimates for Acrylic Resin Production . . 66
17 Sources of Pugitive Emissions from PPIMA Manufacture . . . . . 61
18 Sources of Wastewater from I (M& Manufacture . . . . . . . . . 61
19 11.5. Produce:s of ABS . . . . . . . . . . . . . . . . . . . . 76
20 ASS ConeutsptionAcccrding to Resin Use. . . . . . . . . . . . 78
21 AP.S Consumption by End Use Market . . . . . . . . . . . . . . 78
22 Typical Input Materials to ASS Production Processem in
Addition to Styrene, Acrylonitrtle, Polybutadisne, and
Initiator . . . . . . . . . . . . . . . . . . . . . . . . . . 81
23 Typical Operating Parameters for ABS Production Processes . . 81
24 Input Mat. ria1s and Specialty Chemicals Used in ABS
Manufacture (In Addition to Monomer and Polybutadiane) . . . . 82
25 Worker Distribution Esttmataa (or ABS Resin Production . . . . 89
26 Sources of Fugitive Emissions from ABS Manufacture . . . . . . 91
27 Sources of Vastevater from ABS Manufacture . . . . . . . . . . 93
28 Typical Fihers for Alkyd Molding Resins and the Properties
they Provide . . . . . . . . . . . . . . . . . . . . . . . . . 96
29 U S. Alkyd Resin Producers . . . . . . . . . . . . . . . . . . 98
30 T rpical Operating Parameters for Alkyd Resin Production
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . 105
31 Tyh,ical Input Naqerials for Alkyd Resin Production
Processes . . . . . . . . . . . . . . . . . 106
32 Ef?øct of Modifiers on Alkyd Resins . . . . . . . . . . . . . 109
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TABLES (Continued)
Number
33 Coating Properties of Blended Alkyds . 111
34 Worker Distribution Estimates for Alkyd Restn Production . . . 117
35 Sources of Fugitive Emissions from Alkyd Resin Manufacture . . 118
36 J.S. Amino Resin Producers . . . . . . . . . . . 122
37 1981 Pattern of Consumption for Amino Resins . . . . . . . . . 132
38 1981 Molding Powder Markets for Urea—Formaldehyde Resins . . . 133
39 1981 Molding Powder Markets for Melamine— Formaldehyde
Resins . • • • • • 133
40 Typical Input Materials to Amino Resin Production in
Addition to “tea, Melamine, and Formaldehyde . . . . . . . . . 137
41 Typical Operating Parameters for Amino Resin Production . . . 137
42 tnput Materials and Specialty Chemicals Used in Amino Resin
Manufacture (In Addition to Urea, Melamine, and
Formaldehyde) • • • • • 138
43. Worker Distribution Estimates for Amino Resin Production . . . 148
44 Sources of Fugitive Emissions from AmLno Resin Manufacture . . 149
45 Sources of Wastevater from Amino Resin Manufacture . . . . . . 152
46 U.S. Consumption of Modified Polyphenylene Oxide and
Polyphenylene Sulfide . . . . . . . . . . . . . . . . . . . . 157
47 Typ±cal Input Materials for MPO Production . . . . . . . . . . 159
48 Worker Distribution Estimates for Engineering
Thermoplastics Prcfuction . lea
49 Sources of Air Emissions from MPO and PPS Processing 165
50 Sources of Wastewater MPO an4 PPS Processing . . . . . . 167
51 U.S. Epo ’-” Resin Producers . . . . . . . . . . . . . . . . . . 170
52 U.S. Mar ets for Epoxy Resin. . . . . . . . . . . . . . . . . 173
53 Other Commercial Epoxy Resins . . . . . . . . . . . . . . . . 175
54 T ,,’pical Input Materials to Epoxy Resin Production
Processes . . . . . . . . . . . . . . . . . . . . . . , . . . 179
55 Typical Operating Parameters for Epoxy Resin Production
Processes . . . . 179
56 Input Materials Used in Epoxy Resin Manufacture (In Addition
to Bisphenol-A and Epichlorohydrin) . . . . . . . . . . . . . 180
57 Worker Distribution Estimate, for Epoxy Resin Production . . . 193
58 Sources of Fugitive Emissions from Epoxy Resin Manufacture . . 194
59 Sources of Wastevater from Epoxy Resin Manufacture . . . . . . 199
60 U.S. Producers of PTPE Resins . . . . . . . . . . . . . . . . 202
61 U.S. Producers of Miscellaneous Fluoropolymers . . . . . . . . 203
62 Typical Input Materials to PTFE and PCTFE Production
Processes • 207
63 Typical Operating Parameters for PTFE and ‘CTFE Production
Processes . . . • . . . • . . . . . . . . . . • • . . . . • . 207
64 Input Materials and Specialty Chemicals Used in PTFE and
PCTFE Manufacture . . . . • . . . . • • . . • • • ‘08
65 Worker Distribution Estimates for Fluoropolymer Production • . 218
66 Sources of Fugitive Emissions from PTFE and PCTFE
Production . .......2&9
xi
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TABLES (Continued)
Number
67 Sources of Vastevater from PTPE and PCI’PE Production . . . . . 221
68 U.S. !henolic Resin Producers . . . . . . . . . . . . . . . . 225
69 1981 Consumption of Phenolic Resii , . . . . . . . . . . . . .231,
70 1981 1 henolic Resin Holding Compound Markets . . . . . . . . . 232
11. T’pical Input Materials to Phenolic Resin Production in
Addition to Formaldehyde and Phenol . . . . . . . . . . . . . 237
72 Typical Operating Parameters for Phenolic Resin Production . . 237
73 Typical Input Materials and Specialty Chemicals Used in
Phenolic Resin Production in Addition to Ph.nol and
Fo 1 ehyde . . . . . . . . . . . . . . . . . . . . . . . . . 238
74 Worker bistribution Estimates for Phenolic Resin
Production . . . . . . . . . . . . . . . . . . . . . . . . . . 243
75 Sources of Fugitive Emission, from Phenolic Resin
Manufacture . . .. . . . . . . . . . . . . . . . . . . . . .244
76 Sources. of Uastevat.r from Phenoli.c Resin Manufacture . . . . 247
77 U S.Producers of Po1yacetals . . . . . . . . . . . . . . . . 250
18 Major U.S. Markets for Polyacetal Resins . . . . .‘. . . . . . 232
79 Typical Input Materials toPolyaeetal Production Process.. . . 253
80 Typical Operating Parameters for Polyacetal Production
Processes . . . . . . . , . , , . . . . . . . . . 255
81 Input Materials and Specialty Chemicals Used in P lyacetal
Manufacture . . . . . . . . . . . . . . . . . . . . ,. . . . . 236
82 Worker Distribution Estimates for Polyacetal Producçion . . . 262
83 Sources of Fugitive Emissions from Polyacetal Manufacture . . 263
84 Sources of Wastewater from Polj’acetal Manufacture . . . . . . 266
85 U.S. Nylon Resin Producers . . . . . . . . . . . . . . . . . . 269
86 U.S. Producers. of Diner Mid Based Non—Nylon Polyamide
Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
87 U.S. Producers of Eptchlorohydrin Based Polyanid. Resins . . . 272
88 Major U.S. Nylon Markets . . . . . . . . . . . . . . . . . . . 274
89 Typical Input Materials to Polyamide Prod.iction Processes . . 279
90 Typical Operating Parameters for Polyemid. Production
Processes .‘ . ,. . . . . . . . . . . . . . . . . . . . . . . . 279
91 Input Materials and Specialty Chemicals Used in Pol,a.ide
Re sin M.nufacture . . . . . . . . . . . . . . . . . . . . . . 280
92 Worker Distribution Estimates for Polyamide Production . . . . 287
93 Sources of Fugitive Emissions from Polyamide Manufacture . . . 288
94 Sources of Vastevater from Polyamide Production . . . . . . . 291
95 Typical Input Material, to Polybutylene Polymerization . . . . 296
96 Typical operating Parameters for Polybutylene
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . 296
97 Worker Distribution Estimates for Polybutyl.ne Production . . 299
98 Sources of Fugitive Emission, from Polybutylene
Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . 301
99 U.S. Polycsrbonate Producers . . . . . . . . . . . . . . . . . 30%
100 MajorPolycarbonateMa t, ............ ...•,
101 Typical Input Materials for Polycarbonate Processing . . . . . 3119
xii
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TABLES (Continued)
Number
102 Worker Distribution Estimates for Polycarbonate
Production 312
103 Probable Sources of Air Emission. from Polycarbonate
Processing . . . . . . . . . . . . . . . . . . . . . . . . . . 313
104 U.S. Poly(Ester—Imide) and Poly(Ether—lmide) Resin Products. . 318
105 Typical Input flateriais for Poly(Ester—I.ide) and
Poly(Ether—Imide) Resins . . . . . . . . . . . . . . . . . . . 319
106 Worker Distribution Estimates for Poly(Ester—I.ide) and
Poly(Ether—lmtde) Production . . . . . . . . . . . . . . . . . 321
107 Sources of Fugitive Emissions from Poly(Ester—Imids) and
Poly(Ether—Imide) Manufacture. . . . . . . . . . . . . . . . . 328
108 Toxic Compounds Used in Poly(L ter—Imide) and Poly(Ether—
Imide) Manufacture . . . . . . . . . . . . . . . . . . . . . . 329
109 Sources of Wastevat.r from Poly(Ester-Imide) and
Poly(Ether—Imtde) Production . . . . . . . . . . . . . . . . . 332
110 U.S. Polyethylene Terephthalate Resin Producers . . . . . . . 335
111 U.S. Polybutylene Terephthalate Resin Producers . . . . . . . 33/
112 1981 Con .umptton of PET . . . . . . . . . . . . . . . . . . . 338
113 Typical Input Materiais to Polyethylene Terephthalate and
Polybutylene Terephthalate Processing . . . . . . . . . . . . 342
11 TypLal Operating Parameter; for Polyethylene Terephthalare
and Polybutylene Terephthal.te Processing . . . . . . . . . . 342
115 Specialty Cheeieals Used in Polyethylene Terephthalate
and Polybutylene Tcrephthalate Production . . . . . . . . . . 343
11’, Worker Distribution Estisate for Saturated Polyester Resin
Production . . . . . . . . . . . . . . . . . 349
117 Characteristics of Vent Streams from the Poly(Ethylens
Terephthalate) TPA Proces. . . . . . . . . . . . . . . . . . . 350
118 Characteristics of Vent Streams from the Poly(Ethylene
Terephthalete) DMT Process . . . . . . . . . . . . . . . . . . 351
119 Scurces of Fugitive Emisston.a from Polybutylen. ?.rephthalate
and Polybutylene Terephthalate Manufacture . . . . . . . . . . 352
120 U.S. Producers of Unsaturated Polyester Resins . . . . . . . . 356
121 1981 Co’sumption of Unsaturated Polyester Resins . . . . . . . 361
122 1981 Consumption of Reinforced bnsaturated Polyester
Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
123 Input ‘(eterials and Specialty Chemicals Used in Unsaturated
Polyester Resin Production . . . 364
124 Typical Operating Parame ere for Unsaturatel Polyester Resin
Production . . . . . . . . . . . . . . . . . . . . . . . . . 368
125 Worker Distribution Estimates for Unsaturated Polyester
Resin Production . . . . . . . . . . . . . . . . . . . . . . 371
l2 , Sources of Pigitive nisstons from Unsaturated Polyeste
Resin Pisnufactire . . . . . . . . . . . . . . . . . . . . . . 373
127 Suitable Solvents for MDPE . . . . . . . . . . . . . . . . . . 379
128 U.S. Producers of HDPE Resins . . . . . . . . . . . . . . . . 380
129 HDP! Consumption for 1982 . . . . . . . . . . . . . 384
xiii
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TABLES (Continued)
Number
130 Typical Input Materials to ROPE Processes . . . . . . . . . . 387
131 Typical Operating Parameters for HDPE Processes . . . . . . . 387
132 Input Materials and Specialty Chemicals for HOPE Processes
in Addition to Monomer . . . . . . . . . . . . . . . . . . . . 388
133 Worker Distribution Estimates for ROPE Production . . . . . . 394
134 Source of Fugitive Emissions from HOPE Manufacture , . . . . 393
135 Characteristics of Vent Streams from the Nigh Density
Polyethylene Liquid Phase Particle Form Process. . . . . . . 397
136 Characteristics of Vent Streams from the High Density
Polyethylene Liquid Phase Solution Process . . . . . . . . . . 398
137 Char cteristics of Vent Streams from the Nigh Density
Polyethylene Gas Phase Process . . . . . . . . . . . . . . . . 399
138 LLDPE Consumption by End—Use for 1981 . . . . . . . . . . . 403
139 Typical Input Materials toi .LDpg Processes . . . . . . . . . . 403
140 Typical Operating Parameters for LLDPE Processes . . . . . . . 403
l’e l Input Materials and Specialty chemicals for (LOPE Processes
in Addition to Monomer . . . . . . . . . . . . . . . . . . . 406
142 Worker Distribution Estimates for LLDPE Production . . . . . . 412
143 Sources of Fugitive Emission. from LLDPR Manufacture . . . . . 414
144 U.S. Producer, of LOPE Resins . . . . . . . . . . . . . . . . 418
145 LOPE Plant Capacities Which are More than 15 Year. Old . . . . 421
146 1981 LOPE Concentration of Major Grades by Producer . . . . 422
147 LOPE Consumption by End—Use for 1981 . . . . . . . . . . . . . 424
148 LOPE Pu. Market Consumption or L’ 81 . . . . . . . . . . . . 423
149 Typical Input Materials to LOPE Process., . . . . . . . . . . 428
150 Typical Operating Parameters for LOPE Processes . . . . . . . 428
151 Input Materials and Specialty Chemicals Lor LOPE Processes
in Addition to Monomer . . . . . . . . . . . . . . . . . . . . 429
152 Worker Distribution Estimates for LOPE Production . . . . . . 436
153 Sources of Fugitive Emissions from LOPE Manufacturing
Processes . . . . . . . . . . . . . . . . . . . . . . . . . 438
1!,4 Characteristics of Vent Streams from the Low Density
Polyethylene Nigh—Pressure Process . . . . . . . . . . . . . . 439
155 Characteristics of Vent Streams from the Low Density
Polyethylene Low—Pressure Process. . . . . . . . . . . . . . 440
1 6 U.S. PolypropylenerProduc.rs . . . . . . . . . . . . . . . . .443
157 MaJor Polypropylene Markets . . . . . . . . . . . . . . . . . 448
158 Typical Input Materials to PP Production Processes In
Addition to Monomer . . . . . . . . . . . . . . . . . . . . . 430
159 Typical Operating Parameters for PP Production Processes . . . 430
16 ’) Input Materials and Specialty Chemicals Used In Polypropylene
Production (in Addition to Monomer. . . . . . . . . . . . . .451
161 Worker Distribution Estimates for Polypropylene Production . . 439
1F.Z Sources of Fugitive Emissions from Polypropylene
Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . 460
1!.3 Characteristics of Vent Streams from the Polypropylene
Solution Process . . . . . . . . . . . . . . . . . . . . . . .461
xiv
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TABLES (Continued)
Number
164 Characteristics of Vent Streams from the Polypropylene
Gas Phase Process. . . . . , . . . . . . . . . . . . . . . . .462
165 Major U.S. Producers of Polystyrene . . . . . . . . . . . . . 467
166 Polystyrene Producers Which are Also Major Styr.ne
ButadienetatexPrOdUcer s . . . . . . . . . . . • • • • • • . 471
167 Ccnsuaption of Polystyrene for 1980 . . . . . . . . . . . . . 472
168 Typical Input Materials to General Purpose Polystyrene
Production Processes in Addition tO Monomer and Initiator . . 474
169 Typical Operating Parameters for General Purpose Polystyrene
Production Processes . . . . . . . . . . . .474
170 Input Materials Used in General Purpose Polystyrene
Manufacture (in Addition tO Styrene Monomer) . . . . . . . . . 475
111 Worker Distribution Estimates for General Purpose
Polystyrene Production . . . . . . . . . . ,. . . . . . . . . . 485
172 Sources of Fugitive Emissions from Polystyrene Mai ufacture . . 486
173 Characteristics of Vent Streams from Expandable Polystyrene
les d Production via Suspension PolymerizatiOn. . . . . . . . . 488
174 Chsractetisties of Vent Streams from the Polystyrene Mass
or Solution Polymerization Processes . . . . . . . . . . . . . 489
115 Sources of Wastevster from Polystyrene Manufacture . . . . . . 491
176 Major U.S. Producers of Polystyrene . . . . . . . . . . . . . 495
177 Polystyrene Producers Which are Also Major Styrene—
lutadiend Latex Producers . . . . . . . . . . . . . . . . . . 499
173 Consumption of Polystyrene for 1980 . . . . . . . . . . . . . 500
179 Typical Input Material. to Impact Polystyrene Productiun
Processes in Addition to Styrene Monomer and Rubber . . a • . 502
8O Typical Operating Parameters for Impact Polystyrene
Production Processes . . . . . . . . . . . . . . . . . . . . . 502
18 1 Input Materials Used in Impact Polystyrene Manufacture
(in Addition to Styrene Monomer and Rubber) . . . . . . . . . 503
182 Worker Distribution Estimates for Impact Polystyrene
Production. . . . . . . . . . . . . . . . . . . . . . . . . . 513
183 Sources of Fugitive Emissions from Polystyrene Manufacture . . 315
184 Sources of Wastewater from Polystyrene Manufacture . . . . . . 517
185 U.S. Polyurethane Foam Producers . . . . . . . . . . . . . . . 521
186 U.S. Consumption of Polyurethane Foams . . . . . . . . . . . . 524
187 Typical Input Materials to Polyurethane Poem Production . . . 528
188 Typical Operating Parameters for Polyurethane loam
Pr duction . . . . . . . . . . . . . . . . . . . . • . . . . . 335
189 Major rolyvinyl Acetate Manufacturers . . . . . . . . . . . . 344
1 ) 1980 Sales and Captive Use of Polyvinyl Acetate . . . . . . . 350
191 Typical Input Materials to Polyvinyl Acetate
Production Processes in Addition to Monomer . . . . . . . . 551
192 Typical Operating Parameters for Polyvinyl
Acetate Production Processes . . . . . . . . . . . . . . . . . 551
193 Input Materials Used in Polyvinyl Acetate Manufacture . . . . 532
194 Worker Distribution Estimates for Polyvinyl Acetate
Production . . . . . . . . . . . . . . . . . . . . . . . . . .564
xv
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TABLES (Continued)
Number
195 Sources of Fugitive Emissions f;om Polyvinyl
AcetateManufacture .............•.••••••3
196 Sources of Wastevater from Polyvinyl Acetate Manufacture . . . 568
197 1978 Consumption of Polyvinyl Alcohol . . . a . a . a a . . . 572
198 Polyvinyl Alcohol Producers and Nameplate Capacity . . a . . • 573
199 Typical Input Materials to Polyvinyl AcetaLe
(Polyvinyl lcohol) Production Processes
in Addition to Monomer and Initiator . . . . . a . • . • . . . 376
200 Typical Input Matirials and Operating Parameters
for Po1yvi yl Alcohol Production Processes . . . . . . . . . . 576
201 Input Materials and Specialty Chemicals Used in Polyvinyl
Alcohol Manufacture in Addicton to Polyvinyl Acetate . . . . . 577
202 Worker Dist:ibution Estimates for Polyviiyl Alcohol
Production . . . . . . . . . . . . . . . . . . . . . . . . . . 583
203 Sources of Fugitive Emisoions f roe ‘A Manufacture . a . . • . 584
204 Sources of Vastevater from Polyvinyl Alcohol Manufacture . . . 587
205 Major Polyvinyl Chloride Man if.cturers . . . . . . . . . . . . 390
206 MaJor Mark.ts for Polyvinyl Chloride . . . . . . . . . . . . . 393
207 Typical Input Materials to PVC Prod’actlan
Processes in Addition to Monomer end initiator . . . . . a a . 600
208 Typical Cper.ting Perimeters for PVC Production Processes . . 600
209 Input Materials for PVC Manufa’eture . . . . . . . . . . . . . 601
210 Recipe for PVC Product ton Using Suspension Polymeetgation . .
211 Vork,.r DistrjbgtTióngstt .teq for PVC Production . a a a . a .. 613
212 Sources of Air Emissions from PVC Manufacture . . . . . . . . 616
213 Sources of Fugitive Emissions from PVC Manufacture • • • • • a 617
214 Sources of Vaseevat.r from PVC Manufacture • • a a a • • a . a 620
215 US. Polyvinylidene Chloride Producers a . • . • a a • • • . a 625
216 Typical Input Materialó to Polyvinylid.ns Chloride
Processing • . • a . . • . • a a • . a a • . • a a a a . e • a 628
217 Typical Operating Parameters fer Polyvtnylidene
ChiorideProcessing a aa •. a • • a a...... • • • .628
218 Input Materials and Specialty Chemicals Used is
Polyvisylidene Chloride Manufacture . a • • a • . . , 679
219 Worker Distribution Estimates for PVDC Production . . . . . a 636
220 Sources of Fugitive Emislions from P70C Manufacture . . . . a 637
22t Sources of Vastevater from PVDC N.nu acgure . . . . . . . . . 631
222 U.S. Producers of SAN . . . . . . . . . . . . .. . . . . . .642
223 SA l Major Market. and the 1981 Market 5hsre . . . . . a a 644
224 Typical Input Materials to SAN Pvoducti,n Processes in
Mditioe toStyrene, Mry1on itri1e and Littator . . . a • . 647
225 Typical Operating Parameters for SAN Pro ict1on Processes . . 647
226 Iiput Mat,rials end Specialty Chemicals Used in SAN
PI nufacture (in Addition to Styr.ne and Acrylonitrile) . . . . 648
227 Worker Distributjo Estimates for SAN Production a a . a a a . 654
228 Sources of Fugitive Emissions from SAN Manufacture . . . . . a 653
229 Sources of Vastevater from SAIl Manufacture . . . . . . a • . . 657
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SECTION 1
INDUSI’RT ANALYSIS
INTRODUCTIOI
Sit’ce their discovery and early use nearly 60 years ago, plastic prod
uctq have evolvsd f roe a few materials that were typically consiJered to be
cheap subct tutes to a group of about 100 products that can be processed to
produce goods aiioerior to those made f roe wood, metal, and leather. In some
cases, plastic substitutes have virtually replaced the original products.
The economic importance of plastics can be illustrated by considering indus-
try statistics. Nearly 250 companies are listed as plastics and resins
manufacturers in the 1982 Directory of Chemical Producers . The U.S. pro
ducers of plastics and resins employ approximately 54,000 people; in 1981,
shipments of plastic and resin products were valued by the Sureau of Census
at $20.7 billion for a total of 18 x i06 metric tons (40 * pounds).
The processing of resins to genera’s plastic end products resulted in an
addItional value of slq.n billion in 1981, so that the value f all end
prod ts was about $39 billion. , estns are processed in more that 10,000
establistuae’its with 468,000 employee.. The relative importance of plastics
compared with other chemical products, is illustrated by considering
statistics for other industries in Table 1.
The pri,duction of plastic products, in addition to being the larg-
est. is the most complex industrial activity involving chemicals. This
industry uses a wide variety of onomer and additive combinations nd Is
dynamic in nature. Changie in processes, products offered, and production
technology ace constant.
INDUSTRY DEFINITION
fr. suggested by the data above, the production of plastic consumer
products Involves processing in t’.o distinctly different industries. The
first comprises coepaiies that employ conventional chemical processing to
onvert induetrLa organic chemicals, using polymerisation, into plastic and
resin products. The plastic prodwto from this industry are fabricated into
what is essentially their final form——for example, polyester files. These
may be further processed, as polyester films are processed to manufacture
photogrophic film, but the processing does not alter the film itself. The
resins are in the form of solids (pellets, powders, or granulA!) or lt uids
that are further processed to produce the wide variety of plastic products
that are so pervasive in our present society.
1
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TABLE 1. VALUE OF PRODUCT SiIIPPED BY MAJOR QIEMICAL INDUSTRIES
(198 1)
Value of
Industry Product Employees
($10 ) (103)
Plasttcs and Plastic Products 38.7 52
Paints and Allied Products 8.1 51
9edlcinal Chemicals 5.8 35
Pharmaceuticals 14.9 145
Cosmetica 10.0 55
Synthetic Rubbers 3.9 9
Rubber Products (tires, inner 116 126
tubes, belting, etc.)
Pesticides 4.8 17
Source: Iureaii of the Cemsus.
2
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For purposes of incorporatiofl in the Industrial. Process Profile., the
‘wo industries involved have bee., assigned Individual chapters. The plas-
tics and resins industry is discussed here in Chapter 10, and the plastics
products industry is described in Chapter lOa. For purposes of analysis,
both industries were considered simultaneously, and the two chapters are
cross—referenced. To addition, though th end products of the plastics and
resins industry ar the solids or liquids that are shipped to processors,
th usage discussion to thts chapter has been expanded to include end
p:oducts where it secised appropriate.
Other industries involving polymer products are onsidered in other
IPPEU chapters. These Include: Chapter 9 ( The Synthztic Rubber Industry )
and Chapter 11 ( The Synthet1’ Fiber Industry) .
Thd plastics industry Lr the United States is expected to continue to
grow, with a compound annual rate of 6 percent predicted into the late
19 1 30’s . Although this growth is forecast st a constant rate, there will
Inevitably be years during which it will exceed or drop below this level.
As seen in 1979, production tends to peak, then frop according to the over-
all state of t) ie U.S. economy. The 1986 production is forecast to exceed 24
* [ 1)6 metric tons (54., oundg) in spite of competition from foreign
companies. 1nexpens e feedetocks ii the Middle East have led to new plas-
tics facilities in that region. However, the proximity of U.S. prodtcers to
established markets and effective marketing system. will take advantage of
th. growth In majur applications such as pipe, plumbing systems, and films,
resilting In an increased advantage over Middle Pastern products.
As the plastics industry grows, interest on the parL of Federal regula-
tory agencies increases in this industry. A number of raw materials and
products ar• either known or suspected carcinogens or are potentially
hazardous if handled Improperly. The U.S. Environmental Protection Agency,
the Occupational Safety and Health Administration, and the Consumer Product
afety Commission are all considering me form cf regulation that could
potentially affect the industry.
The balance of this section deals with (1) raw material, that are con-
sumed, (2) the rieture of the products. and markets to which they are sup—
plied, (3) companies that make up the industry, (4) environmental iwpacts
associated with air pollution, water pollution, end solid waste, and (5)
health effects information for t).e Industry. After the induitry analysis,
details pertaining to the technology are presented in 21 sections that ueal
with the categories of polymers shown in Table 2.
Paw Materials
The principal raw material. for plastic. and restis are industrial
organic chemicals that are used as monomers or plasticizers and speciality
cheelcala that are used a; additives to modify the properties of the resins
or plastic products.
More that 200 1n IustrIal organic chemicals used as moiiomere are listed
In Appendix 8. The 12 with the greatest percent of use in the plastic.
3
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TABLE 2 • INDUSTRY SECTOR DESCRIPTIONS
Acrylic Resins — Acrylic resina are water—clear polymers that are light-
weight, durable, and exhibit excellent stability. Methyl aethacrylate is
the starting block for nearly all acrylics. Polymethyl methàcrylate is the
most common polymer, but many other comonomers may be employed -to produce
polymers that range from tacky adhesives o the more common hard plastics
that are used in cciismercial aircraft windows.
Acrylonitrile—Butadiene—Styrene (ABfl — Variations in the manufacturing
process for ABS polymers can be made. to produce a wide range of physical
properties. Typically, ABS is a tough, rigid, heat and chemical resistant
polymer with high impact strei gth and low temperature property retention
that make. it useful in pipe, tusinees sachine housings, automotive parts,
toys, and packaging.
Alkyd Molding Resins — Alkyd resins are typically made from a poiynyaric
alcohol (such as ethylene glycol) and a polybasic acid (such as phthalic
anhidride) reacted in the presence of a drying oil such as tung or linseed
oil. Such resins are widely used in surface coatings such as printing inks
a d lacquer.. Alkyd molding resiis are manufactured as solid molding
compounds used in automobile parts, furniture, electrical equipment and
cables, and construction components for buildings.
Amino Resins — Two major types of amino resins are produced: melamine—
formald P,yde and uree-formaldehyde resins. Although they say be produced in
a variety of forms, amino resins exhibit excellect resistance-to-heat,
solvents, and chemicals which makàs them useful in adhesives, lamination,
dinnerware, and molding compounds. Adhesives represent the largest single
market for amino resins.
Modified Polyphenylene Oxide and Polyphenylene Sulfide — Since this category
typically include, fluorocarbons, nylons, polycarbonates,, and othàr polymers
which are presented as se, arate segments, only modified polyphenylene oxide
and polyphenylene sulfide are included in this segment. These two polymer.
exhibit highteeperature performance, and easy processabiiity. Most engi-
neering th rmopla tic uses center around appliances, business machines, and
‘electrical or electronic uses.
Epoxy Re tns - . kpoxy resins are tough, hard, thers setting solids which cure
qutckl over a wide temperature ringe. Epoxy resins may be fill.d and come
in ltqutd ea solid form for use as coatings. paints, mortar, a.ltesives,
laminates, and high—performance casc parts. The liquid resins a;e produced
by a two steç reaction between bisphenol-A and epichiorohydrin while the
sot ii resins are manufactured from these riw materials by the Taff i or
advancement processes.
(continued)
4
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TABLE 2 (continued)
Fluoropolyiiers — Fluoropolymers, named for the inciusion of fluorine in the
polymer chain, are hlgh’y corrosiye resistant. In addition, they exhibit
outstanding eLectrical properties and maintain self—lubricating surface
qualitlen. These polymers are used in chemical processing equipment,
insulation ard jacketing For wire and cable, nonstick cookware, and
industrial equipment parto.
Phenolic Resins — Heat rejistance, chemical resistance, stability, and low
cost characterize phenolic resins. They are easily molded, exhiott good
electrical properties, and retain surface hardness. Phenolic resins are
used in the electrical, automotive, appliance, and consumer industries. One
of the spectal uses for phenolic ‘csins is in the sands used to make foundry
shell molds and cores.
Polyace al — Polyacetals, o acetal resins, are produced from the
polymerization of formaldehyde. These plastics are the first with strength
properties approaching those of nonferrous metals. Polyacetals are rigid,
tough, and resilient and retain these properties over an extended time.
They are used primarily as metal replacements in the automotive, plumbing.
machinery, and consumer products markets.
Polyamide Resins — Two distinct types of polyamide resins exist: linear
nylon •p lymers and non linear non—.iylon polymers. Nylons contribute
approximately 90 percent to the total polyamide market, which is comprised
of electrl’al parts, gears and fasteners, tubing, pipe, fibers, and fiJi.
The fLame resistance, chemical resistance, toughness, low coefficient of
friction, stiffness, outstanding wear resistance, good electrical proper-
ties, and high temperature resistance of polyamides enables their use in
these varied applications.
Polybutylene — Commercial polybutylene resins are polymers of 1—butene. The
major uses of these resins, pipe and film, utilize th. high temperature
stability, chemical resistance, tear strength, punctur, resistance, and
moisture impermeability of the polymer. Polybutylene is still in the
developmental stage of commercialization.
Polycarbot te — Poiycarbonatea are a special class of linear polyesters.
Although polycarbonates result from many ditf’r.it carbonic acid derivatives
and diols, the polycarbonate of blaphenol ’A is the only product f major
commercial Imporfance. The properties exhibited by polycarbonates, includ
Jn •mpsct strength, complete transparency, good weathering properties, and
self—extinguuthing properties, make these polymers suitable replacements for
metals, glass, w ,od, and other thermoplt stics. Some uses Include electrical
a ,ll stions, appliances, instrumentation, marine, aerospace, photography,
end food packaging.
(continued)
5
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TABLE 2 (continued)
Poly(Ester—lmide) and Poly(Ether—lmide) Resins — Poly(estir—imide) and
poly(ether—imide) resins are condensation polymers which have a repeating
inide group as an integral part of the chain structure. High temperature
resistance, good electrical properties, good wear and friction properties,
chemical !nertnesg, radiation and cryogenic temperature stability, and
inherent nonflanmability are properties of polythides which allow their use
in a variety of applications. Poly(ester—imidas) are used primarily for
wire insulation. Poly(ether—i.ides) are used for injection molding,
extrusion, blow molding, and structural foam molding.
Pc.lyester Resins (Saturated ) — The saturated polyester resin market is
dominated by two products: polyethylene terephthalate (PET) and
polybutylene terephthalate (PIT). PET is a stiff resin which is a good
CO 2 barrier, making one of the major uses of this polymer bottles for
carbonated beverages. PIT is chemically resistant and is not affected by
soldering, acids, freon, or cleaning solutions. This polymer is used in
electrical, automotive, and industrial ap lieations.
Polyester Resins (Unsaturated ) — Ur.saturated polyester resins are produced
from the .:ondensat ion reaction of glycols and dibasic acids, one component
of which is unaa urated. These resins exhibit varying degrees of hardness,
flexibility, and flexural strength depending on the input materials used.
Due t thin wide range “f properties, unm torated polyester resins-are used
in marine products, automobile patti, bathroom fixtures, electrical
components, furniture, auto coatings, and appliances.
Polyethylene——High Density (MDPE ) — Nigh density polyethylene is a highly
ordered structure which is essentially linear. ft exhibits increased
stiffness, tensile strength, hardness, and barrier properties when compared
to low density polyethylene. Polyethylene is a lightweight, flexible
polymer which exhibits outstanding electrical insulation properties. HOPE
has the third largest volume of polymers produced in the United States.
Polyethylene——Linear Low Density ( [ LOPE. ) — LLDPE is a newcomer to the
polyethyienes. it has the liflear structure of NOPE combined with lover
densities, giving the polymer better elongation and environmental stress
eracb resistance when compared to LOPE. LLDPE also possesse. the high
tensLie strength and rhemical resistance of other polyethylene.. Its uses
include housewares, toys, pipe, packaging, and bags for a variety of uses.
PolLethy!ene—Lov Density (LOPE ) — LOPE has been produced the longest of the
three polye ’I ylene .: HOPE, LLDPE, and LOPE. ft is a tough, chemical
resistant, low cost polymer. The partially crystalline nature of LOPE
distinguishes it f toe LLDPE and HOPE. LDPZ is the largest volume plastic in
the United States. its uses Include files, coating, pipes, and housevar. .
(gontlmaed)
6
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TABLE 2 (continued)
Polypropylene — Commercial polypropylene is a highly crystalline polymer
which is resi ant to chemicals and moisture as well as exhibiting high
tensile strength. Ethylene is commonly added as a coinonomer to improvt the
low temperature performance of the polymer. The Largest markets for
polypropylene are consumer oriented, including packaging, squeeze bottles,
automobile parts, carpet backing, and piping.
? olystyrene (General Purpose and Impact ) — Polystyrene is a clear, odor—free
polymer with low specific gravity and good thermal stability. Impact, or
rubber modified, polystyrene has rubber incorporated into the polymer chain
to increase impact strength. Both the modified and unmodified polymer are
easily fabricated and exhibit excellent thermal and electrical properties.
Uses include doors, air conditioner housings, (lover pots, caps, closures,
toys, disposable cutlery and drinking cups, and food packaging.
Polyurethane Foam — Polyurethane foams are cellular plastics v ich are
produced by the reaction of a polyol and a polyisocyanate in the presence of
a blowing agent. Both rigi4 and flexible foams are used in the furniture,
bedding, seating, refrigerati.,n, rinstruction, and automotive parts indus-
tries. Flexible foam must have good ecov ry from compression vhile rigid
foam Is ubcd for insulation or sound deadeniii .
Polyvinyl Acetate — PolyVInyl acetate 1 5 a tasteless, transparent polymer.
It resists oxidation and Is inert to the effects of both ultraviolet and
visible light. These properties make polyvinyl acetate useful in latex
paints, adhesives, surface coatings, and textile finishings. It. most
familiar use is the white glue used in many homes and schools. Polyvinyl
acetate also s.rve as au intermediate for polyvinyl alcohol production.
Polyvinyl Alcohol — Polyvinyl alcohol s a water sensitive polymer which is
derived from polyvinyl acetate since the theoretical monomer (vinyl alcohol)
rearranges to acetaldehyde. Many of the properties of polyvinyl alcohol
depend on the parent polyvinyl acetate. Major uses for polyvinyl alcohol
include textile warp sizing, adhesives, suspension aids, paints, and
membranes. Polyvinyl alcohoi is also an intermediate in the production of
polyvlr.yl butyral.
Po yvIny1 Chloride (PVC ) — PVC Is the 5e. nd largest volume plastic produced
In the United States. It Is a strong, mo’a tely rigid, lightweight
replacement for metals. PVC is used mainly In building and construction.
‘)ther usea include transporatlon, upholstery, packaging, electrical tapes,
and consumer goods. PVC exhibits guOd lnepact resistance when modified.
(continued)
7
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TABLE 2 (continued)
Po lyvinylidene Chloride — Polyvinylidene chloride is a thermally stable,
chemical resistant, highly imperme& le polymer. Only copolymers are commer-
cially produced since the honopolymer is difficult to process due to high
crystallinity. Saran vae the original trademark for this polymer, but has
now become a generic term in the United States. Polyvinylidene chloride is
prinarly used as a film or coating on flexible surfaces for food packaging.
Styrene—Acrylonjtrjle (SAN ) ,— Styrene—acrylonitrile combines the high
clarity and gloss of atyrene with the added chemical resistance and tough-
ness of acrylonitrjle. This transparent resin is easily processed and
retains good dimensional stability. Polymer properties are partially
determine d by the molecular weight and acrylonitrile content. SAN is used
for vegetable compartments, appliances, dash components, medical products,
packaging, and specialty items.
8
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TABLE 3. PRINCIPAL RAW MATERIALS USED IN THE PLASTICS INDUSTRY
1980 Percent
Production Used In
Thousand Plastics
Raw Material Metric Tons Industry Polymers
Ethylene 12,618 61 LDPE, IIDPE, LLDPE
Propylene 5,573 44 Polypropylene
Styrene 3,136 72 ABS, SAN, IPS, GPPS
Vinyl Chloride 2,941 100 PVC
Formaldehyde 2,586 76 Aiilno Resins,
Phenolic Resins
Dimethyl Terephthalate 1,529 100 PBT, PET
Butadiene 1,334 15 ABS
Phenol 1,118 73 Phenolic Resins
Vinyl Acetate 873 100 PVA, PVAc
Acrylonitrile 832 12 ABS, SAN
Phthalic Anhydride 389 57 Alkyd Resine,
Unsaturated
Polyester Resins
Bispheno l—A 239 82 Epoxy Resing
9
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industry are shown in Table 3. The data show order—of-magnitude differences
in the volume used for these top 12 monomers. Moat of the other monomers
identified show even greater variation in the amounts used, since these
monomers are consumed in low volumes.
Plasticizers are uset 1 principally with vinyl chloridà polymers and
copolymers. About 75 percent of the U.S. plasticizer consumption is used to
make PVC, which is otherwise brittle but workable. The largest volume plas-
ticizers are phthalic acid esters. The 1982, consumption of phthalates was
400,000 metric tons, which amounted to 64 percent of the U.S. plasticizer
consumption. Most of these chemicals are used to impart flexibility to
resins; however, other applications include uses as insect repellents,
solvents, and lubricants. Many additives other than plasticizers are used
to modify the properties of polymers and plastic products. Table 4 pre-
sents major additive categories that inciáde more than 1,000 specific chemi-
cals. Chapter lOb of Indubtrial Process Profiles describes these major
additives in detail.
Products
Table 5 displays the polymer categories and the 1980 production for
each. Polyethylene (combining LDPE, LLDPE, and HDPE — 33.7 percent) and
polyvinyl chloride (15.4 percent) account for approximately 50 percent by
weight of the total plastic resin production. Together with polypropylene
and polystyrene, these four major prodwt. ae.counr for approximately 70 per-
cent by weight of the plastic resins produced in 1980.
A separate category called specialty plastics is listed in Table 5.
These products are polymers which have highly selective uses and are
generally produced in very low volumes. Table 6 gives a listing of the
products considered to be specialty plastic.. The combined production
volume of all the polymers listed i approximately 23,000 metric ton..(143J
Since these 40 plastics have such small, production volumes and widely vary-
ing technologies associated with their production, they have been excluded
from this analysis.
Table 7 shows the general markets for plastics and gives an indication
of their role in the economy. Although the demand for plastics products is
expected to grow into the late 1980’s, it is tied to the vitality of the
economy and is sensitive to demands in the basic industrt.s (automobiles,
houst. g, construction) and to consumer buying patterns. PVoduction of most
plastics has increased since 1976, peaking in 1979. Since 1979, production
has generally declined with the tightening economy. Available capacities
should be adequate to accomodate any foreseeable growth.
High volume plastics such as low density polyethylene, high density
polyethylene, polyvinyl chloride, polypropyle a, and polystyrene are
expected to continue downward trends into 1983. Plastics each as PVC, which
are closely associated with the automobili and conatructiut, industries, have
suffered in particular and should lag any economic upturn.
Sarring any major moves by the e:clnomy, increases in production of
specific plastics will be related to two functions:
10
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TABLE 4. PVIJOR ADDITIVE CLASSES USED IN THE PLASTICS INDUSTRY
Activators — See Blowing Agents and Initiators.
Accelerators — See Catalysts and Curing Agents.
Antiblocking Agents — Also known as adP arenrs, prevent adhesion of films to
themselves. This term is specifically used for PVC, while the term slip
agent is generally used for polyoleflnn. Silicate minerals and high melting
waxes which migrate to the surface of the plastic are commonly used.
Antioxidants — Retard oxidative degradation of the plastic at processing
tenperatures and for extended life uses. The most commonly used antioxi-
dant. include alkylated phenols, amine., phosphates, and thi,, compound. for
polyolef ins, polystyrene, and ABS.
Antistatic Agents — Reduce the accumulation of electronic charge on the sur-
face of polymers. These additives function either as lubricants to reduce
friction and therefore reduce charge buildup or by providing a conductive
path for dissipation of accumulated charge.
Blowing (Foaming) Agents — Produce large quantities of gases upon heating
which form cellular plastics. The.. additives can be gasee solvents which
volatize upon heating, or chemical agents which decompose to form gases.
Activators may be used to promote gas formation. They are used for a wide
variety of polymers. Cell stahilize u and nucleating agents control cell
size and distribution in foamed plastics.
Buffers — Compounds concainir.g both weak acids and weak bases. The pH of
solutions containing buffers changes only slightly upon addition of acid or
alkali.
Catalysts — Affect the rate of i hemical reactions without themselves being
consumed or undergoing chemical change. The catalyst can be either an
inorganic or organic compound or an element. The c.e.ignation of catalyst is
used rather loosely in plastics processing, since some c mpounds designated
as catalysts are consumed by the reaction, for example peroxides. 01sf in
polymerizations, for example, use orgaaotransition metal compounds and
Ziegler—Natta catalyst.. Because the catalyst is not consumed in the
reaction, catalyst neutralizer, are sometimes added to deactivate or limit
the catalyst’s activity during product use.
Catalyst Neutralizers — See Catalysts.
Cell Stabilizers — See Blowing Agents.
Chain Trati fe 1 Agents — React with a growing polymer molecule to remove its
free radical aite and terminate polymer growth. The chain transfer agent is
then a free radical capabld of initiating the growth of another polymer
chain.
11 (contInued)
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TABLE 4 (continued)
Coalescij ! — Are used primarily in suspension polymerization to
promote the formation of large droplets (beads) vhtch viii readily settle
out of the aqueous phase.
Colorants — Impart hue (shade), value ( rtghtness), and chroia ( trength of
color) to plastics. They increase the isthetic appeal of a product, and ma,
enh&nce other properties including strength and UV stability. This broad
classification includes dyes, organic aid inorganic pigments, deiusturants,
pearlescents, and metailics. Titanium ftozlde and carbon black constitute
almost 90 percent of the consumption of colorants in plastics.
Coupling Agents — Znhance polymer—mineral surface bonds and the ability of a
composite to retain its original properties after prolonged exposure to
moisture. Silane and tttanate compounds are high volume chemicals in this
clasa.
Craze Resistant Agents — Reduce the tendency of a polymer to crack. Theze
are commonly used in amino resins.
Cros 1inking Agents — Form a bridge between indi’ idual polymer chains,
changing a thermoplastic to a thermosetting resin.
Cure Retardants — Reduce the cure rate for thermosetting resine.....They are
Most commonly amine. used in amino resins.
Aen — Improve the curing of thermosetting resins upon exposure to
heat. The largest class Is the amine compounds for curing of epoxy, amino,
and phenolie resins. Organotin and amine compounds are commonly used for
polyurethane foams.
Defoai.ern — Redu:e th. tendency of solutions to emulsify.
Diluents — See Solvents.
Dispersing Aid . — See Emulaifi.rg.
Elastomers and Flextbtiigers — Increase the pliability of polymere, and
reduce their tendency to break.
Emulsifier . — Reduce the surface tension of water or the .nt.rfacja1 tension
between two liquids or a liquid and a solid. They are commonly used in
emulsion polymerization, and include various soaps and detergent..
Fillers and Extender . — Increase the bulkiness and decrease the total cost
of plastic formulations. These compounds generally end to reduce the
desirable properties of the plastic, although some fillers are added to also
reinforce, harden, insulete, and improve the appearance of the plastics they
fill.
(continued)
-------
TABLE 4 (continued)
name Retardants — Act chemically or physically as insulators; by creating
endothernic cooling reactions, by coating the plastic to exclude oxygen, or
by influencing combustion through reaction with materials that have differ-
ent physical properties. Antimony, halogen, boron, nitrogen, and phosphorus
based compounds are most common. Smoke suppressants and self—extinguishing
agents are also used to reduce the fire hazard of polymers.
Flow Control Agents — Either promote or inhibit the flow properties of
thermosettiflg resins.
— See Preservatives.
Hardeners — Can be either internal or e 4 cternal. These compounds improve the
firmness and set of resins. Also see Curing Agents.
Heat Stabilizers — Are primarily uaed in PVC and other vinyl formulations.
These additives prevent the degradation of the plastic duricg process
heating and for extended life uses. A variety of organic and organometallic
compounds are used to react with chlorine radicals formed during heating and
thus limit further degradation of the polymer.
j p ct Modifiers — Decrease the plastic’s tendency to break or crack upon
impact. These additijes include polymers such as acrylics and chlorinated
polyethylene, and are primarily used in PVC formulations.
Initiators — Form free radicals upon heating or activation to begin polymer-
ization. They are used in the production of thermoplastic resins, unsatu-
rated polyester thermosetting resins and in crosslinking. Peroxy compounds
such as bencoyl peroxide and methyl ethyl ketone peroxides are the highest
volume initiators. Other peroxides, azo compounds and so .. inorganic. are
also used. Activators (also called promotors) may be used to lower the
temperature at which the free radical forms.
Inhibitors — Prevent the polymerization of resins during storage and
blending.
Lubricants — Enhance resin proees. ibility and appearance of the end product.
Desirable properties for lubricants include compatibility with the resin.
ease of mixing, and FDA approval (where applicable). The lubricant should
not adversely affect the end product. ‘ommon lubricants include fatty acid
esters, P ydrocarbon oils and paraffin wax, and amides.
Mold Release ents — Coat the mold to prevent sticking of newly formed
p&rts and to reduce static buildup. These additives can be sprays, powders,
or pai t—on liquidr- Silicone, fluorocarbons, mineral oil, waxes, f tty
acids, mica, and talc are used as mold release agents.
N utralizerB — Are either acida or bases used to bring aqueous solutions to
a neutral pH.
13 (continued)
-------
IAILE 4 (continued)
Peroxide Decomposers — See Initiators.
Plasticizers — Impart flexibility, resiliency, and melt flow to polymers.
These additives act by reducing the intramolecular forces between polymer
chains. Seventy to 80 percent of plasticizers a’e used in PVC formulation.
The major chemical classes include phthalates, adipates, trimellitates,
glycolater epoxies, polyesters, fatty acid esters and organic phosphates.
Preservatives and liocides — Inhibit biological degradaLion of polymers.
This class of additives includes fungic 4 den &nd bacteriostats.
Promoters — See Initiators.
Protective Colinids — Are special surface active substances which prevent
the dispersed phase from coalescing. These are commonly need in emulsion
polymerization, and include polyvinyl alcohol and various cellulose
derivatives.
Reinforcing Agents — Impart tensile, flezural, and compressive strength to
plititics. These reinforcers can be synthetic fibers, carbon fibers, glass
fibers, asbestos or silica or other combination. of materials. The most
common reinforcera are glass fibers which ar available in chemical and
electrical grades to provide increased chemical resistance and electrical
insulating properties, respectively, to the plastic.
Reodorants — Improve the olefactory appeal of polymers by masking their
odor.
Siz L. ts — Coatings which protect the polymer surface. Waxes are
commonly used.
Slip Promoters — Provide surface lubrication during processing and use.
They have minimal compatibility with the polymer, are added internally, and
flow to the surface immediately following processing. since campatiblity is
minimal, slip promoters may exude from the product Jong before the end of
Its useful life. This term is commonly applied to abberenta for
polyolcf ins.
Solution Modifiers — Include a wide variety of chemicals used for
plastisols, coatings, and latexes. These additives have a wide variety of
uses, but are mainly incorporated for ease of handling and for oplcation to
the selected processing gtep.
Solvents — Are liquids capable of dissolving various substances. They are
Irequently used in polymerization end include water, hydrocarbons, and
a icohols.
(continued)
14
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TABLE 4 (continued)
Stabilizer ! — Include a wide variety of compounds which improve the
stability of plastic. during processing and use. See also, Antioxidant.,
Heat Stabilizers, and LIV Stabilizers.
Surf.4ctants — See Emulsifier..
Suspen&ion Aids — See Emulsifters and Protective Collolds.
Thixotropic Agents — Used for thermosetting resins to promote gellisg upon
standing, and liquefaction upon shaking.
UV Stabilizers — Function either to absorb ultraviolet radiation and
reradiate it at a harmless waveLength or as quencher. which consume the free
radicals generated by LIV light. Benzotriazoles and beozophenones constitute
the major compounds used as UV absorbers. Nickel compounds are commonly
used as quencher..
Viscosity Aids — Reduce or increase the viscosity of plastisols
(PVC—plasticizer—solvent mixtures) eith.r during normal processing or for
olastisols which have been subjected to prolonged storage.
Source: IPPEU Chapter lOs.
15
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TA3LE 5. PLASTiCS MID RZSINS PRODUCTION — 1980
U.S. Production Percent
Thousand.Netric Tons of Total
Acrylic Resins 241 1.5
Acryloni trile—Butadiene—Styrene 416 2.6
Alkyd Resins 210 1.3
Amino Resins 589 3.7
Engineering Thermoplastic. 56 0.4
Epoxy Resins 145 0.9
Fluoropolymer. 6 (0.1
Phenolic Resins 686 43
Polyacetal. 40 0.3
Polyamide Resins l58 1.0
Polybuty leau 7 0.1
Po lycarbonate 106 0.7
Poly(ester—imide) and Poly(eth.r— 5 0.1
intO) Resins
Polyester Lesion (Saturated) 480 3.0
Polyester Resins (Unsaturated) 438 2.7
Polyethylene--High Density 1,991 12.
Polyethylene——Linear Low Density 336 2.1
Polyethylene—Low Density 3,058 19.1
Polypropylene 1.689 10.6
Polystyrene (General Purpose 1,599 10.0
a 1 J Impact)
Polyurethane Foam 762 4.8
Polyvinyl Acetate 304 1.9
Polyvinyl Alcohol 64 0.4
Polyvinyl chloride 2,458 15.4
Polyvinylidena chloride 78 0.5
Seyrene—Acrylonitrile 47 0.3
Specialty Plastics N/A N/A
15,981 100.0
•The most recent polyamide production figures available are for 1919.
N/A — Not aesilable.
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TABLE 6. SPECIALTY PLASTICS
Acrylamide—Acrylic Acid Copolymer
Acrylaitide Resins
Aikyiphenol—Acetylene Resins
Cellophane
Cellulose Acetate
Cellulose Acetate Butyrat.
Cellulose Acetate Phthalate
Cellulose Acetate Propionate
Couiurone—Indene and Hydrocarbon Resins
Cresol—Formaldehyde Resins
Cyclohexanone Formaldehyde Resins
Dicyandiamide Resins
Dteethylhydantoln—Foraaldehyde Res!ns
Puran Resins
Clyozal—Formaldehyde Resins
Hydrocarbon Resins
lonomer Resins
Ketone—Aldehyde Resins
Maleic Resins
riethyl Vinyl Ether—Maleic Anhydride Copelyner
Reqi ns
Methyl Vinyl Ether—Monobutyl Malecte Cop3lyuer
Resins
Methyl Vinyl Ether—Plonoethyl Haleate Copo r r
Resins
Ni trocellulose
Nonyl Phenol—Formaldehyde Resin
Phenoxy Resins
Polyeulfode Resins
Polyterpene Resins
Miscellaneous Polyurethane Resins
Polyvinyl Butyral Resins
Polyvinyl Formal Resins
Resorcinol Formaldehyde Resins
Rosin and Rosin Ester Resins
Silicone Resins
Styrene—Allyl Alcohol Resins
S tyrene—Div4nylbengene Copoly.er Resins
Styrene—Maleic Anhydride Copolymer Resins
Triazone Resins
Vinyl Polybutadlene Resins
1—Vlnyl—2—Pyrrolidtnone—Styrene Copolyner
Renins
Vinyl Toluene Copolymer Resins
17
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TABLE 7. U.s MARKETS FOR PLASTICS - 1980
Thousand 2 of
Metric P1 sttcs
Market Tons Market Plastics Used 2
Trinsporation 729.5 4.6 ABS/3M 11.5
Nylon 5.0
Phenolic 8.4
Polyester 16.3
Polyethylene——High
Density 5,3
Polypropylene 14.3
Polyvinyl Chloride 12.2
Other Thereoplast cs 15.2
Other Thermosats 11.8
Packaging 4,546.8 28.4 Polyester (Thermo—
pIa tie) 4.1
Polyethylene——High
Density 20.5
Polyethylene——Low
Density 45.8
Polypropylene 7.2
Polystyrene 133
Polyvinyl Chloride 4.1
Other Theu p1astice 4.4
Theruosets 0.4
Building and 2,920.0 18.3 ABS/SAN 3.6
Construction Aelno 13.0
Phenolic 13.4
Polyester b.0
Polyethylene——Low
Density 2.9
Polyethylene——High
Density
Polystyrene 4.3
Polyvinyl ChlorIde 41.9
Other ThermoplastIc. 7.6
Other Ther.oset. 0.6
Electrical and 1,115.0 7.0 ABS/SAN 10.8
Electronic Epoxy 2.2
Phenolic 7.4
Polypropylene 8.0
Polyethylene—High
Density 6.8
(cent inued)
18
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TA1!LE 7 (continued)
Thousand Z of
Metric Plastics
Market Tons Market Plastics Used 2
Electrical and Polyethylene——Lov
Electronic Density 17.0
(Continued) Polystyrene 12.3
Polyvinyl Chloride 22.0
Other Thermoplastic. 12.0
Other Thermoset 1.5
Furfliture and 748.2 4.7 Amino 10.2
Furnishings Polypropylene 44.2
Polystyrene 4.5
Other Styrena Poly aers 18.8
Polyvinyl Chloride 13.1
Other Thermoplastic. 6.9
Other Thermosets 2.3
Consumer and 1,615.0 10.1 ABS/SAN 2.6
Institutional Polyester 2.8
Polyethylene-—High
Density 13.9
Polyethylene——Lov
Density 16.0
Polypropylene 14.2
Polystyr. ’ e 21.9
Po’,vinyl Chloride 12.0
Other Thermoplastic. 14.2
Other marmosets 2.4
Industrial and 171.1 1.0 ABS/ftN 3.3
Machinery Nylon 5.1
Pheuo ltc 5.4
Polypropylene 13.3
Polyvinyl Chloride 4.1
Other Thermoplastic. 53.0
Other Thermosets 13.8
(continued)
19
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TABLE 7 (continued)
Thousand 2 of
Metric Plastics
Market Ton. — Market Plastics Used 2
Adhesives, 1,085.0 618 Aaino 4.1
Ink., and Epoxy 6.3
Coatings Phenolic 7.8
Polyvinyl Chloride 3.3
Other Vinyl Poly..rs 27.2
Other Ther.oplaatics 34.7
Other Thereosets 16.6
Other 1,388.2 8.7
Export 1,668.2 10.4
TOTAL 15,993.6 100.0
Source: Pacts and Figures of the Plastics Industry , 1981.
20
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• Improved technologies which make products of a specific plastic or
specific manufacturing route more desirable or cost effective than
alternative production or process procedures; or
• An increased demand resulting from a basic switch in consumer buying
patterns, a new product, or the displacement of a non—plastic
matftrial used in the manufacture of nn item. (In either case a new
market is created.)
The anticipated growth of linear low density polyethylene is an example of
the farmer function. The increase in production of PET and PBT through the
1980 to 1981 time frame and the anticipated continued growth of engineering
thermoplastics are e’amplen of the latter phenomena.
Companies
The companies involved in the production of plastics and resins re
varied, being comprised of major oil and chemical, paint, tire and rubber,
steel, electrical manufacturing, and miscellaneous manufacturing companies.
This diversity IS a result of both horizontal and vertical integration
within t. e economy and the general economic attractiveness that has marked
plastic and retrin production during the 1970’s. The horizontal and vertical
integration of plastics production involves a large number of extremely
differen’. , roducts, thus requiring the pa tlcipation of a range of companies
from large to small. For example, paint manufacturers produce the emulsions
aed for their products.
Companies that produce six or more types of plastic and resin are shovn
in Table 8. Another 211 compar’ies produce five or fever products and 2O of
these have a single product. A complete listing of producers and their
products are shown in Appendix C. From Table 8 it can be seen that the
diversified producers are major chemical companies and oil companies vith
chemical production operations. The firms that produce only one or two
products are generally small companies competing for a very limited share of
the lover volume plastics market such as amino, acrylic, alkyd, phenolic,
and polyvinyl acetate. They are not involved with the high volume plastics,
such as polyvinyl chloride and low density polyethylene, which have experi-
enced not only a change in technology but also a shakedown in prices due to
a strongly competitive market. Smaller volume plastics, such as amino
resins and phenolic resins, are not experiencing the flux associated vith an
emerging technology, and are also not ersperiencing the competition from
other plastics which can provide the aamn, or similar, properties. “VC and
polyethylene. have started to experiei ce coinpetitLon from other thermo—
plast lea, such as polybutylene and polypropylene, which has forced these
resins Into a very competitive croas—product market.
E vironmenta1 and Occupational Health Impacts
Pla8tic production processes generate air emissions, vastevater, and
solid waste. Although every process does not generate all three waste
streams, most processes have air emission., eolid wastes, nd vaste’saters
other than routine cleaning water. Table 9 presents a sumeary of the
21
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TABLE 8. DiVERSIFIED PLASTIC AND RESINS PRODUCERS
Number of Number of
Products Plants
E. I. du Pont de Nemours 10 16
Dow Chemical 9 9
Monsanto Co. 9 9
Celanege 8 4
Gulf Oil 8 11
Reichhold ChemIcals 8 20
Borden Inc. 7 14
General Electric 7 6
Mobil Corporation 7 9
Uni. n Carbide 7 12
American Hoescht 6 7
Occidental Petroleum 6 6
22
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TABLE 9. PLASTIC PRODUCTION EMISSIONS SUMMARY
Air Emissions Waste— Solid
Plastic Volatjles Partjculates water Waste
Acrylic Resin X X X X
Acrylont irile—Butadjene—
Styrene X X X X
Alkyd Resins X X X
Amine Resins X X X X
Engineering Thermoplastics X X X X
Epoxy Resins X X X
Fluoropolymerg X X X X
Phenolic Resins x X X X
Polyacetal 1 X X X
Polyamide Resins X X X X
Polybutylene X X X X
Polycarbonate X X x x
Pcly(Eter—Imjde) and Poly(Ether—
Inide) Resins x X x
Polyester (Saturated) x X X X
Polyester (Unsaturated) x x x x
Polyethylene——high Density X * X
Polyethylene——Linear Low
Density X X * X
Polyethylene——Low Density X X * X
Polypropylene X X X X
Polystyrene X X X x
Polyurethane Foiui X X X
Polyvinyl Acetate X X X X
Polyvinyl AlcoPrnl X Xa x x
Polyvinyl Chloride X X X x
Polyvinylidene Chloride X X X X
Styrene—Acry lonjtrj le X X x x
aonly if product is dried for shipment.
*Routine cleaning water only.
23
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related emissions and waste streams generated by the production of the plas-
tics listed in Table 2. £ detailed description of the emissions from each
polymerization process can be found in the section describing the plastic of
interest.
Occupational health concerns in plastics and resins manufacturing vary
widely with the type of plastic being produced. Production processes for
polyethylene and polypropylene, for example, use input materials of subétan—
tially lower toxicity than polyurethane, polyvinyl chloride or epoxy resins.
orresponding1y, the most rigid control measures are typically applied in
the latter processes. Chemical substances and physical agents of particular
oncern in each process are discussed in the section describing that
process.
Ur Emissions,
The air emissions from plastics produetion are of two types: volatile
and particulates. Volatile emissions for most processes are greatest in the
rocessing steps upstream of the reactor. While this is generally true,
aass (bulk) polymerization and solution polymerization processes experience
dgnificant volatile emissions during the monomer recovery and solvent
recovery steps which are downstream of the reactor. Lover conversion for
aass polymerization make monomer recovery necessary. Solvents added during
oluUon polymerization are typically volatile organics, which increase the
rolatile emissions for this process. Typical volatile emissions contain
iostly monomeLs, comonoaers, and solvents with small quantities of plasti—
izers,- initiators, emulsifiers, and suspension stabilizet. (protective
olloids).
Though they g.ner lly exhibit fever volatile emissions than mass or
olutioa processes, suspension and emulsion polymerization processes typi—
ally generate more particulates. Since these processes, use water as a heat
ransfer medium, the pol -mer produced must be separated and dri?d. The
iltration and drying steps generate particulate. which may be ontrolled by
sing cyclones or filters. Some particulate. a e generated during pellet—
zing the product of mass polymerization and drying the solution polymeriza—
f eq product; however, the bulk of the emissions from these processes will
e volatile, The particulate. from plaetic production are mainly polymer
articles, but they may includ. any non—reactive fillers or additives
ocorporated during the polymerization process or reactive additives prior
o pelletization for mass polymerization.
Venting emissions outside the polymerization area, providing adequate
entilation, operating the polymerization area at a slightly negative pree—
ire, and collecting particulates are examples of lew3d engineering practices
ich aid in the control of air emissions. Instituting a routine system for
eapection and detection of leaks also helps reduce the air emissions from
ese processes.
Variability in the nature of materials handled, the involvement of many
rpes of large and small companies, and the large number of establishments
avolved all combine to make it difficult to generalize regarding the
24
-------
overall adequacy of air pollution control in the plastics and resins
induscry. Where known potenti il problems exist (e.g., exposure to vinyl
chloride) highly effective measures are taken to control emissions. Other
considerations such as process economics contribute to the use of control
equipment in some instances. However, in the absence of more information on
toxicity and other potential hazards of many of the materials that may be
dis .harged and background on processes and practices in the industry, poten-
tial for discharge of significant amounts of air pollution must be con-
sidered a possibility even though specific problems have not been identi-
fied.
Wastewater
The most significant source of vastevatet generated from plastic
production is the vater used for emulsion and suspension polymerization.
The water used in these processes as a heat transfer medium allows the mono-
mer to be polymerized without the difficulties associated with the increas-
ing viscosity of the polyiserizing mass (mass polymerization) or the added
emissions and hazards of an organic solvedt (solution polymerization).
Another wastevater source arises from the polymerization reaction itself
when the polymer in produced by a condensation reaction. Water used to wash
the polymer, collected condensate from steam stripping for solvent recovery,
and routine cleaning water are other sources of waste ater associated with
plastics production.
These vastewaters may contain monomer, comonomer, ftller, and addi-
tives. Enulsifiers, suspension stabilizers (protective colloids), and
initiators are present if water s,luble, but found in very small amounts.
Polymer particles are present in polymer wash waters and routine cleaning
water. Some of the plastics have been selected by the Environmental Protec-
tion Agency for Effluent Limitations Guidelines. Specific regulations may
be found in the section concerning the plastic of interest.
The treatment of wastewaters generated by these processes is highly
specific. The different variables which effect the treatment include
plastics produced, ac ditives used, and process operating parameters. There-
fore, no general form of va qtevater control is applicable to this industry.
Solid Waste
Solid waste occurs from plastics production in one of two ways:
polymer is lost or by—products are formed. The largest portion of solid
waste for plastics production may be attributed to lost polymer. Spillage,
routine cleaning, and collected particulates are classified as polymer lost
during the production process. Substandard polymer which cannot be blended
is also defined as lost polymer.
Sy—producta formed during tt”e production process are anot ar source of
solid waste. They are found in fewer processes and conati ute a smaller
portion of the solid waste than polymer losses. Finally, spent catalyst,
spent filter material, and low molecular weight polymers are included as
solid wastes. However, their small volume and applicability to only
25
-------
select processes make them less important than the lost polymer portion. As
with vastevater, solid waste disposal and generation is highly process
specific.
Health Effects
As indicated ii the prec.ding discussion, the macufacture of plastics
and resins involves the use of a large number of organic and inorganic
chemicals for process raw materials, processing aids, property enhancers,
and other specialty uses. Worker exposure to these chemicals, some of which
are potentially dangerous, can occur through accidental ingestion, inhala-
tion of volatile or particulate emissions, and skin contact.
To delineate better the potential for adverse health effects or harm to
the environment from the use of chemicals in the plastics and .resins indus-
try, a chemical hazardous screening task was undertaken to idjntify chemi-
cals that had a history of health effects investigations. This involved
conducting a comprehensive literature search and screening of information
for 476 chemical raw materials in three on—line data banks operated by the
National Library of ‘!edicine—the Registry of Toxic Effects of Chemical
Substances (RTECS), Toxicology Data Bank (TDB), and Toxline. The chemi-
cals were screended for toxic, carcinogenic, autageaic, and teratogenic
effects and classified accordiflg to hazard potential.
The chemicals screened included specialty chemicals used as additive.
as veil as major industrial organic chemicals input to the industry. Almost
200 of the 476 chemicals screened had little or no history of investigation.
As a result, the hazard potential of these chemicals could not be deter-
mined.
Slightly more than 200 chemicals were considered to hav, either very
low or slight to moderate hazard potential. The balance of 71 chemicals was
found to have some recurd of study to suggest they could be considered
chemicals of concern with regard to hazard potential.
It should be noted that the results of this screening cannot be con-
sidered comprehensive because they are limited in terms of nth etry cov-
erage. Chemicals which were not screened include: (1) chemicals which were
not identified as input materials to the plastics industry due to the pro-
prietary nature of some processes; (2) several hundred input chemicals (most
believed to be of minor importance) which have not yet been as igned a CAS
identification number, e.g., dihydroxy diphenyl sulfone, a croàslinking
agent in the ma.aufartur. of polyvinyl alcohol; and (3) an additional several
hundred input materials which were identified only as classes of compoinds,
e.g., aldehydes or alkyl acrylates. Despite these limitations, the results
of the screening do represent a useful step in putting into perspective the
potential hazards of • oonure to chemicals used in the industry.
searches were keyed to the Chemical Abstrects Service idenLification
number (CAS number).
26
-------
Table 10 provides details on the reported health effects associated
with the 71 chemicals of concern a well as pertinent information on OSHA,
NIOSH, and ACGIH regulations. Recommendations have b.en made for 12 of these
chemicals for which no OSHA standard has been set as yet. They are:
acrylic acid, antimony oxide, cadmium sulfide, ferrous sulfate, mercuric
Dromide, mercuric chloride, methyl ethyl ketone peroxide, pyrocatechol,
resorcino]., thiophenol, vinylcyclohexene dioxide, and vinylidene chloride.
Neither a standard nor a reconmendatjon has been made for 18 chemicals of
interest, moat of which pose a possible hazard due to carcinogenic potential
rather than acute toxicity. In many cases, sufficient health effects and
exposure data do n. •xist on which to base a standard or recommendation.
There is considerable variation among the 71 chemicals of cnnceril in
factors such as number and types of application. About one third are
industrial organic chemicals used in relatively large volumes. The balance
are specialty chemicals used in smaller amounts as additivies. More than
one—half of these chemicals are used by one industry segment only. Others
are used by several indiatry segments, sometimes for varied purposes.
Styrene, for example, is a monomer in the production of ABS, SAN, and poly-
styrene; a comonomer in the producticn of acrylic resins and polyvinylidene
chloride; a crosslinking agent in the production of unsaturated polyester
resins; a modifier in the production of alkyd resins; a diluent in the pro-
duction of epoxy resins; and a polymer for blending in the production of
engineering thermoplastics. The acrylic resins segment of the, industry uses
the largest number of chemicals of concern (21), followed by epoxy resins
(15) and polyurethane foam (12). However, more than half of the plavti .e
ard resins industry segments use four or fewer of these chemicals.
Employee Exposure Controls
Good industrial hygiene practice and OSHA policy dictate that personnel
exposures to workplace hazards should first be controlled by engineering and
administrative means, and then by personal protectIve equipment where neces-
sary. The full use of both control types in plastics manufacturing is beat
demonstrated in polyvinyl chloride production. For this reason, that indus-
try will be used as a model in the discussion which follows.
Polymerization processea are such that a control system for one process
may be applicable to an entirely different process. Thus, with minor modi-
fication (e.g. for low volatility monomers such as acrylonitrile), exposure
controls for polyvinyl chloride production may be applied to most of the
plastics and resins industry. Similarly, administrative measures such as
real—time and personnel monitoring programs, fugitive emissions reduction
measures, and personal protective equipment and clothing programs developed
for one industry segment very likely can be successfully used throughout the
industry.
Controls, monitoring programs and protective measures must be ttilored
to meet, the needs of individual plants. With sufficient time, resources and
technical expertise, however, worker exposure to hazardous materials can be
successfully controlled.
27
-------
TABLE 10. REGULATIONS AND RECOPO(ENDATIONS FOR AIRBORNE EMISSIONS OF CHEMICALS OF - CONCERN
________ 51055 (°) or A II (+)
Chocic .I Po ly o sr . Chatical mod ion Ibjor Conc.ru 0511A Air latolution Pocoocund. ; ion .
Aer yI ..id. .ln . IsaAc. hut rsalsiauc :mir o.ln; po l.nei.l n.ta sn liii si . 3 TLV—NA 300 - .5 (skin)
S tditlv. and I.rst ,o SilL IO U
lvi 0.3 . 8 l. .
Vus.tor. .d Foly .st.r Cro..1isbio ...I
P 1* _______
Acrylic Acid PVAc ; Acrylic S..iu. . — — Issbr. .11.. y. ond r..plr.— m St.sd.rd TLY—NA 10 pp.,
PolyvisyliAcu, tory irritant; i..lls. —,
Clilorid. pr.diic. ctrcviato,y coliaps,.
and in ..v,c, c.... doath ds
to shock; potonilsi I. ri$..
sri tsraio$s.
All US Sosp...io. .t.bilia,.
Acryto.ht,ti. AISSu, Suiap.ct.d ‘bjsn cari’.o$..t; l v i S TLV-IVI 2 pp. (ski.)
lal ‘áta .. d t.rat.- a. to pp. 1110 a. 4 pp.
flC; P1*; Acrylic C- _ r s; •o.ic; C. .... cy....i.
mobs; Potyolsyft. na aya. and eo.sl.is..; •y
doss l.rbd, .St r spir .iiry irritant
Alkpl mats
Uposy Ississ
AlIpi Clycidyl Sib., Spoap Isains bib.s. t Pataasia l t.asuri .a and osta- Q. 10 pp. Tl -l pp.’ (skis)
s ; ea . .ss ,sr. local rs.c- SIlL tO pp.’
Sins.; corr,selp Poius i..t.d a. *3 raj.Jll3Ip
tsr coddiasysusaia
tat imssp Onido li 5sst.,at.4 1.1,- msp.ctud onr.lssssh pst 105 0.1 u l.) (at lvi 0.1 ‘.I.3a
oct., Is.lu, loip.— 11.1 se .oc Sb)
foal... I —
Ill PUT catalyst
posp m.iu, -
d.si Pastoubist. t.lp.ppii PUs Cstalp.t lstr lp u s da b, ls ..da . 10* 0.1 n .J . 3 (a. T W A c al syI. 3 °
l l.ut .n; can as.,. •,— Sb)
beta d. . s . acs., sops- -
osra;, pia.âi 1.1 51s..
*ati.s . TrtcSI. ,(d, Pdp.s.e , , d.s.lyst Susrsn.l tonic; pr. .s p., l v i 0.3 as!.) (a. 10* 0.1 syI.)
uuspirat.ry tract lrritatin. Sb)
•bd..laal psl. to.. St
sypotil.
PUPU t.ociou. is..
cast iou.d)
-------
TABLE 10 (conUnued)
P ol . s rq . .lc.1 Piancilo. Major Cone., .
ls. Pastas ft...— P 11 1.1 tutu.. ha... carctiuo 5 ..
tic t. .t.. , tpo•y
tall.., PuLy..id,
15 111.1, Ia$lfl55f fl
Th .r .op l.. 1e., PTV I,
TV I
PVC LOIS, Acrylic Io l, s .c
P ast..
Cbsatc.1
Asb..to.
1 . 1 11 . 1W
p P . oqul so..
I-Pat p1 pdrop.roaIds
Ca t. Selild.
Cart.. Tslr.cblneld,
Churl.,
Ch1.rela.
CL ioropu..,
P1A llsl.u.l..l Is..
‘ 5
Us.aluar.t.d Poiy..t.,
I..’..
PS, LUIS
Polp..ids
a’.’..
P lC PSAc, PS,
Acrylic Islaa
Pluoropoly .,,,
PIuiopoIp., r.
Chiorid,
ISt.rds .t
Pulp .srl.at Is.
i s t lbll.r
tadLcM laIlI.lo
Calorant
Chain irs .. ? ,, asac
p..st.. .1 1th ha.r
lta lsr a .t
a — _
OtIt Air I Slu a l si 10.
IIIOSM (a) o A IM (0)
I .co ndatj .n.
T WA 0.5
lb/cc
TLV—TVA0.3 lb/c c
TWA 100,000 lbIp )*
3, 300,0 ,) b/ s
Suasp.ci.d aa care 1oo..?
NA 10
po l.,l s i .,ta.. and l.raeo—
pp.
CL 25
TLV—TWA 10 pp.
S. .. lode 1. lb. c..u.1 s.r—
vps
11 30 ppo/l0i’#Iit
STIL 25 pp.’
‘0 o •p.i. by I.poitIo.,
0. 10 pp./tOuts
1s 1a1. 11us, and t. •b.or.flo.
P.l..eiai l rl s. and W1 1-
TWA 0.1
ss, •slz.e.I, lode by hu.s—
pp.
I L , -TWA 0.1 pp.
1101., app.rs.tlp ha. a diract
5Th. 0.3 pp.0
•ll•ct a. a.du. I Ia s.d eap u.—
c•rryIs 5 capacity . 1 bio.d
1 trss.iy o.ic. produc.. •p.p-
Ms ila.dard
to.. of .,vtr. dspr...Io.
P. Iaco..dat is.
as. rsaptialsrp
arr.,t; ss,.r. loc.1 Irrita.t
5 ._a .al.al cqrcl.o..p
pot,.lhaL s.1a 55., l uiy tOsic
TWA 0.2 sal. 3
0. 0.1 op/s 3
111* 0.05 sal . 3 (a. Cd)
by lo.gaatIo. and I1t . atlo.,
(a.
Cd)
TWA A0 1 / ,Sa
alf.ct. r•splralory tact s.d
0. 200 s/.)IIWsa
ktd..p.
lua .p.c l.d h_a. caechss..j;
TWA 10
•slIa.s ly lode by lst.i.ei..
pp.
0. 23
ILl-lilA S pp . (ski.)
or tap.sthoa , d..tro,. Its.,.
pp.
II 200 p -./1uIlAu
STIL 20 pp.’
a. 2 • l0ow .
east,....
Ni b1p site to lb. respiratory
CL I
tract by istalatto.; . lroa
pp.
ILl-lilA 1 pps 0
local hr,ilan , p.ts.ll.I
1101. 3 pp.0
0. 0.3 pp./13 1 1*
a.ca$s.
1e.p.cc.d t.a.. carct...t;
CL 30
pol..t 14 eatas.. and lerat.—
pp.
ILl-TWA 10 pp.
se— , a d,rat .ly bale; caaas.
1101. 30 pp.’
r..ph ..torp dspr.saio., 4h..t—
0. 2 p .I00Na
.. .a. ass..., tacracr..ia
pr ‘.acr., and Is hiI c_a..—
tr.tlc.a, ear4l, u,r..l
lu.p.ctad h.an.. care l.o ,.t,
polsaitsi ea11.. and t.ral.ps.
TWA 25 pp.
TLV-TIIA tO pp (ski.)
0. 1 pp./1311*
-------
? 1330 l.s$asl is..
TABLE 10 (continued)
Cbfssis. J .i u
00PI Urt. &L0N
$imtyst
C . U,drspsu .(
I .al.,.i.4 Psip. .,
ls•i. s
l .i psi cer. sisal
ion.
lailesi isilists.
£00
sysis. -
4.s isilis lis .
PU? P00
s ysi s .
Csr sp s.d srs.p
1 5 . 11.1
SlUSH (I) s .c £Cl.IH ( )
lscusu .dal is.s
‘ Cs.isi. 1 131 1 air Is sit.. .
.sis c.eris.is . iwa 0.1 .1.)
p 1 5 . 1 1. 1 s.is . s .d 1.1.1.- (C,$b)
$ 55. isdc u,s. chrss*c •.po-
s l I d. •1I.ci. L$vsg ssd e.sirst
•.rvuss SySls -
Icuis ip lesic by i..st Is.. $1s.di ci
isasiss Is. sad ski. sbs. . p-
Iiss p’sè.c. bsod.ch. sad
Ibrust irrIi.ti.. psl.s4i .
- •15s lsss
s.i..$ carcis.iss 1 0.3
kIy LMc by I.Mi.tl.. s .
• UI . 15 (brS I SipG15(s Cs.
1s. C l55t . 5 C5s .$b.
CSas.sis Sk.b 1 sad d..is
is. acisd carcI os..t; 1 l W
psls.. . s.e scuesly a. i o u pps
S..ie by I.issltss $sb.ia— 00 300 pps!3.1J30
I I .. . CSa stisci $ssl, SIM..i C-
.sI SIsct CSflIra* s.,,s.m
•P5 ss. - Li . . bldssy sad
.dr...1 sysi
Siply lust. by Isisslis. .d Q. 0
isksIst . j 5. rsl.Iy issic by
ski. •b c .tpe tss •U.ci. css—
lest s.r s puss. sad ussr
*csa.ly uRic by i s.e s. 5 i I ps
$ .ise Is. skis sbsscp—
I is. Cs. yrs cs s.Ibsuss*.—
bis.sI.; psl.aei.1 IsrI s
Ui lp Colic by i.gsse ls.• Na 0.1 Pr.
I.bsi.i$s. 5 s.d skis sbso p
I is cs. cs .
fOsitislory spsts. ilr.r ss
blood. k . s.i. c.rcis.-
r.sPt ps s.t tal s.i.•.a
luvor. ski. s.d sy. irrii..i; 11 iIsai.rd
losic, •a. cs..s s.sys. Iskibi-
lisa
DisipciiyI leh.r
I.UOi lh pI. .i ii
I .I—0Is.lb,3by u PS
0i.i . . I i.it.
WA 0.05 s/ . (CessJ
TIM 21 $l. (Cr )
0 •/.3/ ( ,54)
. Uc od .i to.
TLV-Na 0.2 pp.
TLV-Tws 10 pps
flu. 11 pp.
lVAipp . a
Q. 2 pç.ll’J.P
TLV—Tva 0.1 pp..
a. a
TLV-iV4 I pps• (ski.)
3111. 10 I’P’
‘ 1.3-Na 0.1 ppU (ski.)
SIlL 1 ppu
a. 0.11 ,41S3/3$*
No Is v —a—i I ..
s.sliskiui 1 .
(cons Isusi)
-------
TABLE 10 (continued)
Cbe.l.iI Furi iLori
Iposy Iaeiua• Poiya- lk)no..r
mid. last. ..
)..-Ipo .y-S-iS.iby l Iposy lest...
tic 1obssyi..tb L-3 b—
Epusrb—lirlbyl cyclo—
hens . .. Carbosplat.
PVAC. Acrylic le.ioa
PoIyeinpl i d.n.
Cb b srtd.
PVa 1yace ai
AU Pads. imuttacios
e yel
AmIno l..l..; Phone—
lIe last...
Poly.c.tal
iii 5 h ly lumic by ii estiun•
1uhaiaiiun and shin abeurp—
lion. acul. •.pu.ur. say i.e
respiratory pcraly.ie a d
hruni.. •npoaure La o cause
biJuluy injury, keown animal
car..lno 8 .nt , potential malag..
and sca t. .$ . .
Known animal carcinu .nt No Standard
Nl u.Lp tonic by Istestion
inhalation, and skin abasry—
thin upon acute eepoaur., pro-
duces hyp.rsoonia arid
Cunvui mlusa
Know., animal carcimo.n m , NA 0.3 pp.
severe ski., aye, and respira-
tory tract irril.nt , .atr..ety
bale by lri sstton
Tonic upon acut. •spo.ur.,
alluct. Saetroint.st tooaj tract
sod pul monary systs , poteniial
tuonri$.s. . .1a.. , and
I•ralo l an
Nighip tonic upon acute sap.— No Standard
Cur., climate ca.lr.l servo ..
system, t iigs. 55 1 moIs 5e.
Nigbiy issue by injection,
inhalation, and skin absorption
upon acute elposurs, suapsct.4
carets. 5 . ., potential motssea
arid lsratop.a
Acutely Ionic; •li.ct. r.apira— TWA ) pp.
bios and body leuperstur.,
pot sal asS lu..ri$.n and mat s$so
Highly ionic by iui$..tio. ,
irlialet ion, and shi, absorption
upon •cutu eaposur., produc..
cyano,is, w.coaacisusn... , and
convulsions
t u SC lal.ralnst is.
1 9 1 , -i l rohy4rin
Nijur Concern
TWA S ppm
Nil)iil () or AQ .iH (+)
U ItA Air kvgulaliu . , tecoesgndat i ns
‘VS
TWA 23 pp.
tchgi Acrylate
Ithyi.s.isin.
Itbyl... 0.1dm
Par . .... 5.1(51.
ror.sl lu Ld.
Puriurpi Alcebsi
lydrocyaalc Acid
TLV—TWA 2 pp. (shin)
STEL S pp . °
NA 2 m$/.3i
Ci. 19 .iI. 3 1I5N”
Mo lecos.endatio,
TLV—NA (skin)
iTSi. 23 pp.
TLV-TWA 0 3 py. (skin)
TLV-TVA I pp.°
•Ti.V-TWA I
STII. 2 /.3+ (as V.)
TIlL ) pp.
Ants, lasts. Crags resistance
sass ’
Polyus,tkssa Peso Sieckt.g ags.,
TWA 3 pps TLV—TiIA I pp.°
Q. S pp. STEL 2 pp. 0
P S 10 pp./10M/ i 0. 1.2 ag/.3 30N5
TWA 10 pp.
TtV—TVA 10 pp. (skin)
STIL IS pp.’
TWA 200 njI. 3
Ci. 10 pps,
0. 3 .a(cui)I. 3 Iioits
(continued)
-------
TABLE 10 (contInued)
Ns$s cosc.r .
sigbly es1c by lss ilus pos
unit. sayos,ir. p is .il.l
tusunli... sul..... m .d
l.f.io$.. -
S.p.cl.d
U.ltsslIal s . d isrmio$. .
I$hiy i. c by l* .iil . . or
lsk&.i$m. .1 1usd óala. ái.t 1
Pe s lls* iiortgs. mad usisgm.
llbly Sods by tisiStios m .d
l 1.slos; csuuus poluossny
ld . sidodusi pots mod
om. 1 1 1o 1 ; . srs skIa mud .ys
rile. ii; poSssii.l lum.rly. s
ilty Iy lids $s...ll.. Sisodsid
litholmit.. . s .d skis s1uorp-
Lisa; cm . . ,. sy.c.,d$.l
dm.sss , emidlm. .uci.l.,
dL.....s• mud mriuf SiOSCl., . .u.
t russ maid.
•l 1y Soil. by 1.i lse Ur SS.M.rd
ldus$jsio. od skis sksorpsl..
u mess. or ckromle sups. r.
c.II teal ‘or s .r. ih. kidusy
sd isessil . i._ Sf.ci
ll l, Soils by l.tt.. - IS $tmmdmr4
i .bs1att .. s .d skis abmorplim.
up.. mess. or ebrosic .uyos .,. ;
criltesi Ol$smo Ofs ibm k i d . . y
sud 1st. SIsal trust
Ulpb$y Susie b, ls suitss IVk £0 ppo
*sku1silsa mud sits mbsorpsl..
ursa scab •ursser.; say cm ...
luSbs d cm. I s I s . . ;
usv . . silu .,s, sad rssplr.—
tory iirti..s
Ui i$ toils by th .s ao - IS Slusdard
upsa scubo sspo . r.
.1 sets dssitoslouiiu.1 trust I
poiositsj irty. .
si LI, 1 . 5 . 1. 1
l vi z ie
lvi 0.01 ui, .) (ma
.‘•b)
lvi 200 •(Pb) u)
ivi o. s
5 . 1
p..)
Ipdre i.$ so . s
Ususis,.i.d Pulposi,, P.l, . .,ta.i Isk
last..
lsktblic
laud Muia 5s
Poipur.sb.mo P.m.
Polysula, U..t..
1. upsustos sisal ii..,
1u.i$sS SI...
.s4 Oddo
? ; P
Css .L yu s
11.1.5. Lskydrtdu
Ussoiralud P.Lp.sis,
Pob..s . asbydria.
i . .
Ipsip lasts.
IS,. .,.s
5-Il.rc.peo. sb.s.
Likyl lasts.
Aseptic rust..
,olpb . .ic .cid
1a se t . ,
lareiri. Ursula.
PoIplds
ISclu.st. .I.
I1.r.u ,ts ISl.,tdu
Niya.i i. .
ISsls.it%
laibji Asepimi.
PelyvIsyl loU
vseky l Ilbj i b.i..s
Pes.tur . .j Po*ps.is,
• II ( ) or LQ.th (•1
_ I.c ..dsi loam
TLV-lVa 2
11Th. 5 l 4I. °
P es/. 3 1l1 1 1 5
PLV—lVi 0.51 u !. 3 C..
Pb)
TWO 0.10 .$(Pb)I. 3 5
TLV—IIii I Oil m.j_) .,
Pb)
ThA 0.10 •s(PbiI. 3 5
U.S-TWA 0.21 pps
IS
TLV-TW* 0.1 e I .) (us
lvi 0.01 .0(14 )/ 3 .
1 1W-TWO 0.5 s/.) si
0.0 .s(Us) .
71W—IWO 10 pp. (ski.)
0. 0.2 ri’
HAlO ISisrulm.tto..
-------
TABLE 10 (conttnued)
Ui..i.al
N.ihyt.o. It.phei iyl
1.. y.uimt. Ii I)
U .s.t.r.t.d PoltiaI.r Pol ..rt ..t is.
i ib I ton
M..Jur_Concimin
ToiL by1a 5 ..tIu. inha1.tIu .
and ibm ab .orpt too ..y cam ...
•y.ee.1 da..g.. saver. lo.ai
I rr I limit
Acutely tunic Co luIl$a by TWA 200
i0hiIatIu . savor. irritant to
.ki i, vy.. and e.comm.
aia zJnaa. potential IueurI$.a.
sue i en. and 1.rato 5r .
Ac m . alp and chu..ntciy tonic by TWa pp.
iug.stIuo imiha1a1iuo and akin
aba mrptlo ..y can.. canal amid
he , .tI.. d..a e. potentIal
tuairi a.t• e.ta 5es. amid
Cal itog..
SIrnii local Irritant TWA 0.1 pç.
•mtr...iy tonic by inhalation—
• orI esposuares at low cuncea-
Iral Ion. c ia c i . .. d.a lh
‘intc...ip tonic by ln .stiun TWA 0.1 % 53
tnb.iiatlo. and .hI . coat.ct og
dsai .1 picnic acid or It.
salt.. e.y can.. sass.. 5a5
trosnirrIti.• ..phniti.. and
acne, hepatitis
Ui hiy tonic by iss .iIo. and N Standard
akin ab.orptio.. e.d.rat.iy
toil. by iahal.tioa . iay .iI.ct
cent .aL rvan. •y.t... put—
poo.nry spat . . ussr and
kid.,. , potential e.ta$.. and
l. i t5ea
Anomat •nj..i c..cisoa..t N. Standard
NIOSII () or *0.15 (+1
Reco..emidat tuna
TLV—TWA 0.01 pp.•
IIAIC OstsrsI.aeio..
Pu lye. r
Pol yimr.Ih.ne Pu..
Ch .aicai Fun.lion
l.ocy.nai.
Pluoropolp..r. S,nap.aaIon stahl hair
OSIIA Air tegul.t Ion
TWA 0 02 pp.
Phenotic hesins
Pulyvr.i baa. Pu..
Ipo .y S..i ..
Polycarboast.
Nsau..r
Sloching ag.at
Cure accelerator
N.l.cshar w.ilmt
rsgu lal
Picric ACId
Ptp.nidi..
Polypropyt. . .
Spa., N..ie. Cu. agasi
TLV-TWA 100 ppb
STCI. l0 ppb’
TLV—TWA S pp.’
STEL 10 pp. ’
TWA 20 si$J .3
TLV-TWA 0.1 p i.•
TWA 0 I pp. a
0. 0.2 pps/ 15 1 1
TLV-TWA 0 1 • , .3+
STEI. 300 g .3.
No Ieco .dat 10mm.
No t.co ndation
pp
Pol,b .sple ..
lia 5.51.5
Span, Neal..
l .0s .r
Tree.ior..t$o. eld
S5U estingui.hteg
a.s.t
Pill..
(cool Insad)
-------
UA20 Dste_si..t ion.
TA5L tO (continued)
Ch..I .i
Pulyont.
Sesical Pinclien
ajur Lvu ..ern
US’tA. ir le uIsI
PnLyl.ir.tiuuro—
eIIly .a.
Poiy..lde S..ls.
Sell eotlngu.sbln
1 5 51
ln. u. mnls.l car oo 55 5?
‘ kisudard
Pulperellian.
Polyasid. Pasta.
—-a..
iiiuwo ant..i carcmnoposi?
No Standard
Puip.slnyi Aicobol
PVC. PS ASS. Acrylic
Pasts. Polyvinyil—
l.n. chloride
Ua.ps..l.s stabill...
ouwa •nL_s2 c .ucinupe,t
N. Standard
ppM
P.oc.ctiu. coilold
Polyvinyl Chloride
Acrylic Peaks
5.1 1 •sllngvishia
• 5s 51
Ss..p.cI.d ku_sn cauclno ..t
No Standard
Ipsop Pastsa
NodUlar
Pylocascirl
Poiperethan. Poe.
Slockia q..l
Nightp tool. dspsndina Os root.
of aAa*nist ralloa af1.cts
sisiI to affects of pb.noi
No Standard
Uaaalsrat.4 Poly.at.r
lesion
Folyrla.t$q.
is hib ito r
Ni 5h*, tonic by ln .ssioe•
lnk.latIos and skin absorp-
tion. cans..
be_sIp,ie and r.nil injury.
potential t rlp.n ao l .stspon
N, Standa,d
teaurcisot
PPan.*lc Saab.
Polpu.r.ihas. Poe.
r
dee is *d.nS
Nighip lusIc by inge.tbo_s.
oral •.posi.re of 55 san
Ca ... da.lh . potential ti_sir 1—
gas sod
Ns Standard
4e.tna S
Acrylic Nosion
Color
kn,n.i aol_si •srcinog.nt;
potential ontagan
No Standard
on
Acrylic S..ina
5.lot.a e
Known sal_si care taag.nt
potential ontagas
No StasOard
St y . . .s
ASS. SAM; PS
Acrylic Sealsa; Paly—
vIny tide.. chloride
Ce.o r
Mig*,lp losic; affect, central
onr oo. cyst..; potential
tu.origas . enta es. sod tars-
togas
IVI Re. pp.
Ch 200 pp.
PP 6 )0 pp..’5013N
uis.atsrae.d Polyester
Seal..
Cr.saliskin agast
NIII ll ( ) or *Q.IN (+)
n S . s.useend.i loae
No t.co n4.t too
No Iecondetio.
No Iec. nd.t Ion
No leco_sendat Ion
TLV—?WA pps
No Secendat Ion
TLV-TIIA *0
ITS). 20 pp.
No S.co.dat Los
No Secoendat ion
1LV—1WA 50 pp.+
STUL 100 pp.’
(continec d)
-------
TABLE 10 (corLinued)
h. .i. .1
t ren. (t . ,%lInueJI
P.,l n .e r a
Alkyd begin.
Ep ty teeing
Engineeri,. 5 Theren—
plait i.i
Cheeic.i F u, t lv i
Ibid (tier
D I luent
Pvlye.r fur blendln
J _ Con,ern
OSIIA Air Negulatiun
NIOSIl ( ) yr AU.III
seyjal Ion . —
T uIu.n.-2 .4.
diisncyaaat.
Tr lchi i ro.th,1. a n
Tri(2-Cfllgr n etby I)
Ploaphat.
Ca. 0 n 0 .s r
Acrylic &aalna• Ipsay lolvent
Reams. lnjln..r
Tharsuplastic.. Pulp—
vi.pltd.ae ChIo,j4.
Pulyur.t’sane Poan Isucyanate
HiAh1 toil by iu .atirn. and
Ioh IalIun a(fe.ts central
erinva cyst.. 1Iver and
Id n e
Hl 1 hir tusic by Inisat ion
tithalat Ion, and akin absurp—
tiu . say Cay.. behsvto r. iI
•Y p(oua . puieon.ry •yate.
Co.. and death
Vnuwo anisgi carcino..nt ,
put.nl tat enteRs.. toiic, death
Li i o...urr.d when lb. bu a .
•spogure level ranched 141
al/kg
Potential tii rIg.u , sails 1 , ,,
and tecatoten. tonic caoa.s
paycbc.troplc and central
nervy.. spec. •t(.cts
Toil, by luigeeijou , t hat.tlu .
and skin abs rpiio, , sever.
skin and reeptr.tvry tract
Irritant, genera respiratory -
1aug11 liar.
C,u. .u anlagi carclno 8 ent ,
putentla l saatagen and Isralo-
jrn , to tic, agy Cauge death
I ro. rasplr.iory failure liver
and kidney leglong, reversibte
nerve da na 1 . , long biological
hall—lila
Suspected carctno 1 , 4 y
PIAIC Deter.lniI .n
A u rylic test.. Chain tcan.f.r dent
Thiophenat
Thlu re g PV C
Totuen.
1WA 200 pys TLV-TWA 200 pp.
STkL 230 pp.
No Standard TLV—flJA O.S pp.’
CL 0 S .lI. 3 /lSM
No Standard No . coanenda( on
TVA 200 pp. TLY-IVA 100 pp +
CL 300 pp. STIL 130 pp.’
Pt 300 pp./10 11 TWA 100 pp.
CL 2J0 pp./ 10115
CL 0.02 pp. TLV—Tha 0.005 pp .
STbL 0 02 pps
TWA 0.005 pp.
CL 0.02 pp.
TWA 100 pp. TLV-TWA 50 pp.
CL lOt) pp. STkI. I SO pp.
Pt 300 pp./5M/211 TWA 100 pp.a
CL lW) ppa/tON i
N e Standard N e lecuanendat ion
Pulyvi nyiid, n.
Qu in, ida
Pulpuirethan. Poe. ILaan retardant
(continued)
-------
TABLE 10 (continued)
Na r ....ncern
Ni hiy tonic by ine.iiun and
tuhaiatton moderately tori.. by
skin absorption atrwn ink—
t int to tissue potential
s u• Le n
leuvu animal carcInogen?
putential mola$.n arid tori’,-
,en tonic by ingesti... and
inh.lation• strong i ni:int to
silo and eyes
Suspected huaa caIclno .nt. No Standard
potential moiag.n and unto—
•en lr.ilant to ski.. and eyes;
moderately ionic by iri estion
known hum.. caictsu 5.nt . highly Na 1 pp.
tonIc may cauma death or per CL 1 pp.11511
.aneoe injury after inbalat in.
even if nape.ur. is short
Suspected carcinogens. pot..- No Standard
tiat .utagan. strong Irritant
to skin and tlasu. moderately
tonic by ingaat to. and skin
absorption
known animal carci.og.nt;
potential Notag.n and terato—
pen. higMy tonic. cans..
sy.teeic .llsct. of Low conc. .—
tral tuna
NIU H (•) or *a.lii (4)
Necoonend.t Lu. ..
TLV-TU4 LU pp.
aTEi. IS Pt..’
N.. lecoonendsi ion
TLV-Na S ppm
TWA 1 pp.S
U. S pp.11 5115
TLV-TWA 10 ppe
TLV-TV& S p, +
STEL 20 p ø+
lila 1 pp. 1
U. S pp. 1 1 5115
tISIC Dat.r.inat to..
51in nolatlo. indicate. ast.rt.l is highly .b..rb.aL. through the akin.
Sourc.i Na istry of Tonic hIatt. of CL.nical Sub.tanca . Na—Lion File U.S. Department of HeaRtS, and Shim.. Services, Public Health Service,
C.nt.r tot Sham Control. National Institute tar Oceupatloas l Satety and flealth , Cincinnatl Ohio, updated monthly. Data retrieved
September aM Octnb.r 1112.
Chastest Function
OSIIA Air Segulat on
TWA 25 pp.
No St.snd.rd
.h.si . .al Polymers _________________
Triethylami . .. Polyurethane Foam Catalyst
Tni.ethyi Phosphate anion I.sl ,,a O.r. agss$
Tni.(2.)—Dlbru. .- Polyurethane Pu.. P1.me retardant
propyl) Phoaphat.
Vinyl Cblontda C hansen
Vinylc, i .b.m. .. Ipony Seat.. Dtlu.nt
Dioulde
Vinyl ld .. Chloride louyvinylidsas
Chloride
acrylic .sins , flC - - r
.1
0’
it, Iecuanro4g ion
No Standard
-------
Engineering Controls
A recent NIOSH study documented engineering controls in use at several
polyvinyl chloride manufacturing operations employing each of the five
polym rization processes discussed in Section 26.(280J Most polymer produc-
tion operations are carried out in closed .iessels and reactors. The closed
process, in itself, is an effective engineering control. Additional effec-
tive engineering controls include:
Computerized pro ess control——by reducing the potential for operator
error during manual operations, the possibility of significant monomer
escape is reduced. Computer control reduces the number of operators needed
to run the plant and the amount of time operators actually spend in poten-
tial exposure areas.
Specialized equipment——use of certain types of valves, pumps, and
agitator, compressor and pump sea 1 s may reduce the occurrence of leaks and
thus reduce employee exposure potential. Reportedly successful equipment
pes include butterfly valves with a double blind and bleed system, pres-
surized, grease—packed agitator seals, nitrogen—pressurized compressor
seals, double aechanical seals for pumps and compressors and dual rupture
disks.
Enclosed ...ontrol room——locating process controls in an enclosed,
positive pressure control room, supplied with clean, filtered air is a most
effectivu? on rol measure. Employees minimize time spent in the plant and
maximize time spent in a clean environment.
Local exhaust ventilation——a local exhaust system flexible enough to
control multiple, periodic leaks may be an effective control for highly
toxic substances such ae vinyl chloride. Permanent exhaust hoods or flexi-
ble duct openings may be located near compressors, pumps, valves or other
equipment with a high leak potefltial. Alternatively, portable exhaust
systems may be used.
Administrative Controls
Rapid leak detection is an important administrative means of reducing
employee exposure to hazardous fugitive emissions. A portable hydrocarbon
detector may be used to r gularly inspect potential leak sources (e.g. valve
stems, pump and compressor seals, blind flanges) to facilitate early leak
detector and repair. Continuous, real—time leak detection may be accom-
plished via a process gas chromatograph monitoring system. Air samples era
taken periodically at several locations throughout a plant; individual
readings greater than a predetermined level activate an alarm in the control
room.
Another effective administrative control is the development and use of
standard operating prc.cedures. In performing any operation in the reaction
area, employees must follow a checklist step—by—step. Each step must be
signed off, with critical steps verified by at least two employees.
37
-------
Employee training is very important. workers should be knowledgeable
about the nature of the safety and health hazards in the plant and the
provisions that are available to them for protection against the hazards.
They must be educated in the proper use and reason for each protective
device or procedure required. Employee knowledge has particular signif 1—
cance for hazards involving skin contact with carcinogenic compounds, where
good personal hygiene is essential.
Actual contaminant levels in the plant can be determined only through
implementation of a comprehensive employee monitoring program. Employees
typically wear personal sampling pumps or monitoring badges throughout an
average work shift.
Personal sampling pumps can be used to collect samples for many dif-
ferent airborne contaminants. The sampling pump is worn by the ‘employee and
is connected to an appropriate sample collection medium which is positioned
in the employee’s breathing zone. NIOSH has developed sampling techniques
with recoemendations for collection medium, pump flow rate, and sample
volume • Additional sampling echniques can be found in the HygienL Guide
Series for individual substances, published by the American Industrial
Hygiene Association, and in SlOSH criteria documents for individual
subatances.
Monitoring badges (passive dosimeters) are available for measuring
employee exposure to organic vapors and some inorganic gases • These badges
are eney to. use and allow samples to be collected by non—technical person—
nel Subsequent analysis is dane by gas chromatography (organic vapors) or
colorimetric methods (inorganic gases).
Personal Protective Equipment and Clothing
Use of personal protective equipment 8nd clothing minimizes employee
exposure to hazardous materials in situations where engineering or adminis-
trative controls cannot reduce exposure to reported safe levels. The degree
of protect ion necessary depends on the types of hazardous materials in the
workplace environment and the conditions under which an employee may be
exposed.
Dermal protection minimizes or prevents contact of the skin with,
potentially hazardous materials which may be absorbed into the body, cause
contact burns chemical or physical), skin lesions, or carcinomas. Use of a
removable protective layer also provides a means for removing contaminants
from employees before they leave work, thus minimizing exposure to persons
Outside the plant. Coverall., gloves, aprons and other dermal protection
devices must be constructed of materials which will not allow hazardous
material penetration. Eye protection is necessary for employ... involved in
operations such as handling input chemicals, taking process samples, per-
forming maintenance and machining or grindi .g. ANSI Z87.l gives specifica-
tions for protective eyeveax used in a variety of situations.
Respiratory protection is important because the potential exists in
some plastics manufacturing plants for conditions resulting in imeediate
38
-------
respiratory failure or long term damage to internal organs. Use of respira-
tory protection is not recommended as a substitute for other control
methods, but should be used in emergency conditions or in nonroutine opera-
tions where protection can be afforded in no other way.
Selection of the proper type of respiratory protection may be a complex
task. This is due to multiple potential hazards encountered in particular
activities, as well as the large number and variety of respiratory protec-
tive devices available.
Resp ratori are of either the air—purifying type or atmospheric sup-
plying type. Air—purifying respirators are limited in they can only be used
in atmospheres with sufficient oxygen. Additionally, they are specific for
particular substances or classes of substances. In contrast, atmosphere
supplying respirators provide the breathing at.aosphere and are not dependent
on either of the two above factors. However, : tmosphere supplying respira-
tors are sometimes cumbersome because they must have an air supply attached.
Common air—purifying respirators draw air through cannisters or
cartridges to clean the contaminant from the air before it is taken inLo the
facepiece for breathing. Typical cartridges or cannisters are specific for
organic vapors, acid gases, or dusts, mists, and fumes. Air purifying
respirators with various facepiece styles (full facepiece, half fa epiece)
have upper limits of contaminant concentrations, established by NIOSH and
used in areas or operations where the expowire level is known to be below
the ceiling allowed for the respirator, and where no chance exists of
encountering an oxygen deficient atmosphere. Additionally, this type of
respirator should be used only in areas where no significant concentrationo
of toxic gases are present for which the respirator may be ineffective.
In oxygen—dericient atmospheres, employees should wear atmosphere sup-
plying respirators with full facepieces. Either a supplied air respiratc.r
or self contained breathing apparatus (SCLt) is an appropriate choice.
Supplied air (air line) respirators may be preferrable for this type of work
if an air supply connection is available and if the work is limited to a
single area without need f or .Iovement over great distances. A standard
supplied air respirator (preferrably positive pvessure or pressure demand),
ccrtified by NIOSH or MSHA for work in this type of atmosphere is recom-
mended for use in areas where exposure levels remain below those TM immedi—
ately dangerous to life or health.
A typical SCBA unit is bulky, heavy, and usually can supply air for a
maximum of 30—60 minutes. This type of respirator should be used for emer-
gency responses to unknown conditions, or entry and work sbere movement over
large areas is required.
Summa
The plastics and resins producers comprise a relatively large segment
of the Un. ted States chemical manufacturing capability. Although the
economic downturn of the late seventies and early eighties has reduced the
production of most polymers, the market is still strong for most plastic
39
-------
materials. Their ease of handling, energy efficient procassability, and
s iperior qualities have established a place for them in the market.
The plastics and resins industry generates air emissions, vastevaters,
and solid wastes. Air emissions are either perticulates or volatile..
Solution polymerization processes typically generate more volatile emissions
tha t n ass (bulk), suspension, or emulsion. Wastewatere are primarily from
sucpension and emulsion polymerization processes, both of which use large
quantities of water. Solid wastes are typically polymer lost, such as
particulate., or by—products formed during polymerization. Due to the
variability in the chemicals used in each of these processes and the wide
range of onerating parameters, no general form of environmental control for
any of these processes is applicable.
A wide range of chemicals is used in the manufacture of p lastics and
resins. The potential hazards to workers depends upon process type,
ongineering controls, practices, and, of course, the chemicals used. The
methods outlined in the prev 4 ous section list the types of control and
practices used to minimize amy worker health problems. -.
40
-------
SECTION 2
ACRYLIC RESINS
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Acrylic re3ins are water—clear polymers which exhibit excellent stabil-
ity upon aging. Acrylic monomers are very versatile, polymerjzj and
copolymerjzjng with a variety of other monomerm with relative ease. Poly—
methyl methacrylate is the major polymer produced from the acrylic family.
Methyl methacrylate is the starting block for almost all acrylic polymers.
13, 140, 286] Other acrylics include: methyl acrylate, ethyl acrylate,
butyl acry late, 2 —ethylhexyl acrylate, 2 —ethoxyethy l acrylate, acrylic acid,
ethyl Inethacrylate butyl methacrylate, 2 —hydroxypropy methacrylate, ethyl
2 —hydroxymethyl acrylate, t—butylamj nc.ethyl methacrylate, dimethylaminoethyl
methacrylate, glycidyl methacrylate, and methacrylic acid.
Polymethy l methacryl (PMM ) is a crystal clear, lightweight, durable
polymer. PT4JIA properties can be varied to form extremely tacky adhesives,
rubbers, tough plastics, or hard powders. When produced in thin sections,
PPfM& is flexible. The polymer may be cut, turned on a lathe, saved,
drillei, poltshed, or formed. [ 247J PMMA is the most resistant of all
transparent plastics to ultraviolet radiation, and moisture. PMMA polymers
with varying degrees of flexibility are achieved by incorporating various
copolymers into the resin.
The outstanding transparency, light piping qualjti , colorability, and
dimensional stability of PMMA coupled with the retention of these properties
in outdoor applications over long periods of time make this resin useful in
many industries. PMMA is used for aviation parts, including pilots’ cano-
pies and windows on commercial aircraft, because it is free from optical
distortion, resistant to light and weathering, resistant to shattering, and
able to withstand sharp pressure and temperature differentia1s.ii j Other
uses include safety glass interlaying, glazing, dentures, contact lenses,
and various coatings and finishes.
PMI(A properties are in part a function of the Processing step used to
produce the iinjshed plastic product. PPO(A in bulk form starts an auto—
acceleration reaction at about 50 Percent conversion. Therefore, complete
conversion is not attained until the polymer ib processed, for example cast
or mol4ed. Proper tea of cast and molded PMNA ae listed in Table A—i in
Appendix A.
41
-------
Modifiers are used in PMMA production to improve impact strength, give
higher service temperatures, increase toughness and add extinguishing
propert...es. Impact nodif Led resins exhibit lessened stiffness,
transparency, weather stability, and abrasion resistance when compared to
unmodified resins. However, in addition to improved impact strength, the
modified resins also have harder surfaces, lower water absorption, greater
resistance to staining, and better color stability. Table A-2 of Appendix A
lists properties of impact modified compounds.
PMMA is not affected by alkalis, oils, dilute acids, hydrochloric acid,
sulfuric acid, or dilute alcohols. This resin is soluble in polar solvents,
such as ketones, esters, ethers, and aromatic hydrocarbon/alcohol mixtures.
Thermosetting PMWi are used for bake coatings. The PMM& resin is
postreacted with formaldehyde and butanol. A cure agent, such as styrene,
is added to provide cr’ sslinking during curing. These resins vary from very
flexible coatings, vhich may be applied by rolicoating to tinplate or
aluminum stock used for cans or siding, to spraysbla, cheaicall,y resistant,
very hard enamels for household appliances. Uncured, these resins, are
hard, brittle, weak, and lack chemical and solvant ranistance. Upon curing,
they become tough, flexible, impact resistant, very hard, very insoluble,
and resistant to solvents, alkalis, acids, and detergents.
PIOlA is produced by mass, solution, suspenaioi, or emulsion
polymerization. Bulk polymerization is carried to less than 50 percent
conversion due to the autoacceleration that occurs between 20 and SO
percent. The res ’lting resL is usually cast. Solution resins are used in
the preparation of coatings, adhesives, impregnates, and laainotes.
Suspension resins are used as molding powders or ion exchange resins, while
emulsion resins are used in the paint, paper, textile, floor polish, and
leather industries for coatings and binders.
PMMA solid resins are molded, extruded, or cast sheet. Finishing
processes used include hot stamping, spray painting, and vacuum metalizing.
Higher molecular weight molding resins have a lower malt flow rate, greater
hot strength during processing, and improved resistiunce to cracking during
ejection. Lower .olwcglar weight molding resins have a higher melt flow
rate and are designed for complex parts with hard to fill molds.(3j When
heated, PlOlA is a tough, pliable polymer that is easily bent or formed into
complex shapes that can be molded or extruded.
INDUSTRY DESCRIPTION
Fifty-four producers with 104 sites in 27 states comprise the acrylic
resin industry; P 0(A is the major acrylic product. A preponderance of sites
(33) are located in the Great Lakes States (EPA Regio’ V). Over 10 percent
are located in each of the follo sing regions: New England (EPA Region I),
Mew York and New Jersey (EPA Region Ii), Mid—Eastern States (EPA Region
III), Southeastern States (EPA Region IV), and the Southwestern States (EPA
Region IX). Acrylic resin producers and locations are ilited in Table 11.
Plant capacities are considered to be proprietary.
42
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TABLE 11. U.S. ACRYLIC RESIN PRODUCERS
Producer Location
AD O Chemical Co., Inc. Newark, NJ
American Cyanamid Co.
Indu ,tria1 Chemicals Division Vallingford, CT
AZS Corp.
AZS Chemical Co. Division Atlanta, CA
Beatrice Foods Co.
Beatrice Chemical Divjsto
Farbroj l Co. Division Baltimore, MD
Polyvinyl Chemical Industry Division Wilmington, MA
Stahl Finish Division Peabody, MA
Borden Inc.
Borden Chemical Division
Thermoplastic s Products Compton, CA
Illiopolis, IL
Leomineter, MA
Celanese Corp.
Celanese Plastics and Specialties Co. Division
Celanege Specialty Resins Division Los An;eles, CA
Louisville, KY
Chemical Products Corp. Elawood Park, N.J
Cook Industrial Coatings Co. Detroit, M I
Cook Paint and Varnish Co. Milpitas, CA
North Kansas City, NO
Crown—Metro, Inc. Greenville, SC
The Derby Co., Inc. Ashland, P tA
DeSoto, Inc. Chicago Heights, IL
Garland, TX
The Dexter Corp.
Midland Division Cleveland, oa
Hayward, CA
Rocky Hill, CT
Vaukegan, IL
(continued)
43
-------
TABLE 11 (continued)
Producer Location
Dock Resin. Corp. Linden, NJ
H. I. DuPont do Nemours & Co., Inc.
Fabrics and Finish s Department Chicagt , IL
Flint, Pit
Fort ‘Madison, IA
Front Royal, VA
Parlin, NJ
Philadel hia, PA
S. San Francisco, C&
Tcledo OH
Polymer Product. Department Parkersburg, WV
(Lucite)
Dutch Boy, Inc.
Coiltings Group Baltimore, m
H. B. Fuller Co. Atlanta, GA
Blue Ash, OH
General Latex and Chemical Corp. Ashland, OH
Cnmbçidge, M
Charldtte, N
Dalton; CA
The IF Goodrich Co.
IF Goodlich Chemical Group Avon Lake, OR
V. ft. Grace & Co.
Industrial Chemicals Group neboro, KY
Orginic Chemicals Division South Acton, MA
Guardsman Chemicals, Inc. Grand Rapids, NI
Gulf Oil Corp.
Mullesister Onyx Group, subsidiary
Lyadal Chemical Division Lyndhurst,NJ
Banns Chemical Coatings Corp. Columbus, OH
Hart. Products Corp. Jersey City, NJ
Henkel of America, Inc.
Henkel Corp., subsidiary Kankakee, ‘L
(continued)
44
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TABLE 11 (continued)
Producer Location
Hercules Inc. Clairton, PA
Hugh 3.—Resins Co. Long Beach, CA
S. C. Johnson & Son, Inc. Racine, WI
Koinac Paint, Inc. Denver, Co
Minnesota Mining and Manufacturing Co.
Cheetcal Resources Division St. Pauj, t4
Mobay Chemical Corp.
Dyes and Pigments Division Bayonne, NJ
Mobil Corp.
Mircor Inc.
Montgomery Ward & Co., Inc., subsidiary
Standard T Chemical Co., Inc., subsidiary Chicago Heights, IL
Staten Island, N Y
Mobil Oil Corp.
Mobil Chemical Co. Division
Chemical Coatings Division Rochester, PA
Morton—Norwich Products, Inc.
Morton Chemical Division Ringvood, IL
National Starch and Chemfeal Corp. Meredosia, IL
Resins Division
Charles S. Tanner Division Enoree, SC
Norris Paint Co., Inc. Salem, OR
The O’Brien Corp.
The O’Brien Corp.—Central Region South Bend, IN
The O’Brien Corp.—Weetern Region S. San Francisco, CA
Phillip Morris, Inc.
Polymer I’idustrjea, Inc., subsidiary
Adhenives and Liquid Coatings Division Stamford, CT
Textile Chemicals Division Greenville, SC
(continued)
45
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TABLE 11 (continued)
Producer Location
PPG Industries, Inc.
Coatings and Resin. Division Circlevjlle, OH
Oak Creek 1 WI
Torrance, CA
Purex Corp. Carson, CA
K. J. Quinn & Co., Inc.
Polymer Division Maiden, MA
Seabrook, NH
Raffi and Swanson, Inc.
Polymeric Resins Division Wilmington, MA
Reichhold Chemicals, Inc. Detroit, 4 1
Elizabeth, NJ
S. San Francisco, CA
Emulsion Polymers Divi.ion Cheewold, DE
Retchho d Chemicals Del Caribe, Inc., subsidiary Rio Piedra., PR
H. U. Robertson Co.
Freeman Chemical Corp., subeidiary Chatham, VA
Saukville, WI
Robe & Haas Co. Bristol, PA
Croydon, PA
Rob. & Haas California Inc., subsidiary Hayward, CA
Rohm & Uaas Kentucky Inc., subsidiary Louisville, KY
Robe 6 Haas Tennessee Inc., subsidiary Knoxville, TN
S Q l Corp.
Glidden Coatings & Resins Division Huron, OH
Reading, PA
San Francisco, c&
The Shervin—Williama Co.
Coatings Group Chicago, IL
Sun Chemical Corp.
Chemicals Group
Chemical. Division Chester, SC
Sybron Corp.
Chemical Division
lonac Chemical Co. Division Birmingham, NJ
Jersey State Chemical Co. Divisio. Haledon, NJ
(continued)
46
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TABLE 11 (continued)
Producer Location
Textron Inc.
Spencer Kellogg Division Newark, NJ
Union Oil Co. of California
Union Chemicals Division Bridgeviev, IL
Charlotte, NC
Kearny, NJ
Lemont, IL
United Merchanto & Planufacturers, Inc.
Vaichem—Chemical Division Langley, SC
United Technologies Corp.
Inmont Corp., subsidiary Anaheim, CA
Cincinnati, OH
Detroit, MI
Greenville, OH
Valapar Corp.
McWhorter, Inc., subsidiary Baltimore, W
Carpenteraville, IL
Yenkin—tiajestic Paint Corp.
Ohio Polychemicals Co. Division Columbus, OH
Source: Directory of Chemical Producers , 1982.
47
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Acrylic resins are used in many consumer products. from 1975 to 1979,
acrylic resin production increased from 352,000 metric tone to 519,000
metric tons.(65J The production fell from this peak to 247,000 metric tone
in 1980;, with 1981 production increasing to 256,000 metric tons.f143j The
excess capacity exhibited by 1979 production figures of at least 263,000
metric tone is sufficient to accommodate any industry growth in the near
future.
Low level “additives, including surfactantn used in the manufacture of
P Q1& latexes, may be toxic. The following inputs to the PMM& process are
listed as hazardous: acetone, acrylic acid, acrylonitrile, beuzene, carbon
tetrachioride, chlorobenzene, chloroform, cumene, cyclohexane, ethyl
acetate, ethyl acrylate, isobutyl alcohol, methyl methacrylate, t luene,
!richloroethylene, vinyl chloride, an4, vinylidene chloride.
Ti’s comonomer vinyl chloride is a known human carcinogen. Suspected
human carcinogens used in this process include the comonomer acrylonitrile,
the self—extinguishing agent polyvinyl chloride, the solvent benzene, and
the chain transfer agents chloroform sac 1 carbon tetrechloride. Poçential
human carcinogens iwlude the suspending, agent polyvinyl alcohol, the chain
transfer agent triehlor’ethylene, the comononer vinyliden. chloride,, and the
colorants cadmium sulfide, Rhodamine 3, and Rhodamine 6GDN. Other input.
which pose a significant health risk are styrene, ethyl acrylate, acrylic
acid, N,N—diieethylanilir e, toluene, triethylamine, 2-mercaptoethanol, and
thiophenol.
Solution polymers, molding povders, and plastic sheet are consideredto
be flammable a iteriala; dispersion polymers are qot vh.n water in present.
Closed kettle reactors reduce both the exposure and flammability hazard
associated with the polymerization process. Dust control also reduces the
explosive potential in the handling of powders or the manufacture of plastic
sheet. Acrylic products require the same tire precautions as wood; they
must comply with building codes, meet applcable Underwriters Laboratory
(Ut) standards, and be installed while observing established principles of
fire safety.(3J Ligh’ing fixture lenses sod diffusers are freely mounted so
that they fall prtor to ignition in case of fire, preventing fire spread to
the ceiling.(3J
PRODUCTION AND END USE DATA
In 1981, acrylic resiu production totaled 256,000 metric tone.(l43J
These resins have many uses, including:(3, 120, 121, 140, 247J
• Airplane windows, cockpit elomures, aviation canopies, radar plot
boards, instrument panels, and landing light covers;
• Sighting devices, photographic equipment, wide—angle TV screens,
storm doors and windows, solar collector panel., safety glass
interlaying, complex reflex lenses, bank tellers’ windows,
panels around hockey rinks, bath and shower enclosures, show cases,
cast plastic eyeglass lenses, Fresnel lenses and Fresnel lens film,
windshields for small boats, safety guards for tools and machinery,
push buttons and panels for business and vending machines;
48
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• Automotive parts, including tail lights, dials, instrument panels,
and lenses;
• LLghtlng refractors for fluorescent and mercury—vapor lamp sources,
and indoor and outdoor lighting and signs;
• Thermosetting resins for upgrading polyester systems, impregnating
varnishes, electrical and electronic encapsulating and plotting
compounds, automotive glazes, and plazes for windows;
• Domes over stadiums, pools, and tennis courts, and glazed archways
between buildings;
• Cosmetic and food packaging, dentures and denture bases, tooth
filling materials, orthodontic sealants, dental and surgical
bindings and filling agents which adhere to bones and teeth, and
hard and soft contact lenses;
• Plastic sanitary fixtures, thermoformed bathtubs, toys, transparent
drawers for storage and display of goods, racks and holders,
countertop displays, buttons and bars on typewriters, business
machine parts, pump parts, and piano keys;
• Leather finishes for furniture, auto upholstery, garments, and
shoes;
• Coatings for stucco, cinder block, concrete, asbestos shingle, and
exterior v jd shingle, heat resistant enamels, aluminum paints,
fumeproof enamels, luminescent and phosphorescent finishes,
furniture lacquers, vinyl printing inks, vii yl film topcoats, and
military aircraft paint;
• Paper uses, including pigment binders, saturants, fiber binders,
coating for paperboard and letter—press, offset, and rotogravure
paint±ng papers (such as frozen—f ,,od containers, bread wrap, folding
boxboird, greaseproof paper, wallpaper, business a achine paper, and
reproductive paper), artificial leather, pressure sensitive tape,
window shades, and gaskets;
• Floor polishes, flooring products, ceramics, mortar cements,
protective and decorative overlay on wood, masonite, plywood, and
other surfaces, and wire coatings; and
• Cast furniture, skylights, and outdoor table tops.
Table 12 lists 1931 consumption of acrylic resins.
49
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TABLE 12. 1981 CONSUMPTION OF ACRYLIC RESINS
Market Thousand Metric Tone
Cast Sheet 82
Molding and Extrusion Compounds ii
Other rades 32
Coatings 46
Other (Emulsion Polymts, Transesterification 25
Resins, etc.)
TOTAL 256
Source: Modern Plastics , January 1982.
50
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PROCESS DESCRIPTIONS
P OfA is produced by mass, solution, suspension, or emulsion polym-
erization. The process used depends upon the desired end product. Mass
polymerization resins are used mainly for cast products; solution polym-
erization is used to manufacture coatings and binders. Suspension
polymerization resins are tiny beads which are used as molding compounds
while emulsion polymerization latexes produce ingredients for paints.
Acrylic monomers have the general formula CH2CIICOOR. Methyl meth—
acrylate resins are a specific type of acrylic resin which have a methyl
group substituted for the ci—hydrogen, CH 2 —CCH 3 OOR. This c*—methyl group
gives methacrylate polymers increased stability, hardness, and stiffness due
to the stereochemistry of the molecule.(121j
PMMA is produced by polymerization of the methyl methacrylate monomer
with a radical initiator (R.), commonly benzoyl peroxide. The initiator
combines with a methyl methacrylate monomer to produce a methyl methacrylate
radical. This new radical then combines with other monomer moJecules to
for’s the PMMA chain. The reaction is terminated either when two radical
groups combine or by disproportionation. This series of reactions is shown
below.
Initiation
CH3 C113
CH 2 —C +
COOCH 3 COOCH 3
Propagation
r 3 COOCH 3
R-CH 2 —C. + Q 2 t —0 R—C’d 2 —(!— CH2 — .
COOCH 3 C l ! 3 OOCR 3 cH 3
51
-------
Termination
Radical Combination
r 3
1-012 0121 + k -C 21 . .— —4
COOCH 3 3 C0 00H 3
r 3 r 013
R —CR 2 —C d3 2 -C
I I
000013 013 000013
Disproportionation
_ r 013 r 3
R-01 2 -C 012111 + ft-012C 0121.
COOCH 3 013 3 Q1
+ 013_ [ 01100
000cR 3 CR 3 \03
This series of reactions is inhibited by oxygen. Oxygen becomes a comonomer
in the polymerization process, decreasing the rate of reaàtios end’ the
molecular weight of the polymer. This copolymerization reaction is shown
below.
r 3 r 3
R—C1 12-4j. + 02+R012000s
COOCH 3 ãoooi 3
P)O(A production is performed in an inert gas atmosphere to minimize this
copolymerization.
52
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Tables 13 and 14 list typical input materials and operating parameterl
for the four P?O & production processes. Other input materials used i PPIMA
produer t euwh s buffers, lubricants, pigments, and comonomers are listed
in Table 15.
Mass Polymerization
Mass polymerization is the major process used for the production of
PMMA casting resin. Mass polymerized PMM& may be discharged directly from
the polymerization reactor to the casting process. In contrast to solution,
suspension, or emulsion polymerization, no solvent removal or dewatering ts
necessary prior to casting the resin.
Mass polymerization using a batch process is depicted in Figure 1.
Methyl methacrylate, any comonomer desired, UV absorbers, pigments or dyes,
additives, and an initiator are added to the reactor. Higher acrylatee are
often added to soften and improve the flexibility of the resin without
decreasing durability. An inert gas is sometimes introduced to prevent
oxygen from slowing the reaction while heat is added to increase the
reaction rate. When the monomer/polymer mixture has reached the desired
conversion, the mass is discharged from the reactor and processed to form
the desired product, such as cast sheets, rods, or tubes.
Methyl methacrylate starts an autoacceleration reaction when the PMMA
conversion reaches 20 to 50 percent. There is a sudden increase in molecu-
lar weight, increase in viscosity, and decrease in termination. Therefore,
conversions for this process are kept low. The monomer/polymer mixture is
then processed with the processing temperature completing the
polymerization.
A typical recipe for mass polymerization of PMMA is given below [ 733:
Material Parts by Weight
Methyl Methacrylate 2,703
Benzoyl Peroxide (initiator) 13.5
Dibutyl Phthalate (plasticizer) 81.1
UV Absorber 27
Pigment or Dyes
Lubricant
Ethylene Glycol Dimethacrylate (com000mer) 13.8
Solution Polymerization
Solution polymerization is used in the preparation of PMMA for
coatings, adhesives, impregnates, and laminates. The solvent, such as
beuzene or toiuene, is chosen on the basis of cost, toxicity, flammability,
volatility, and chain transfer. Thiols and chiorohydrocarbons exhibit high
chain transfer; therefore, they are rarely used as so1ve .s but are u’ed in
concentrations of 0.1 to 3 percent as chain transfer agents.
53
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E BLE 13. TYPICAL INPUT MATERIALS TO P?Q A PRODUCTION PROCESSES
IN ADDITION TO MONOMER AND INITIATOR
Chain Transfer Suspending
Process Agent Water Solvent Emulsifier
Mass I
Solution I I
Suspension I I I
Emulsion I I X
TABLE 14. TYPICAL OPERATING PARAMETERS FOR PMMA PRODUCTION PROCESSES
Process Temperature Reacr ion Time Conversion
Mass 30—90°C 8-24hours 20—502
Solution 136 — 143C 6 — 8 hours >952
Suspension 30 — 15°C 3 — 6 hours >952
Emulsion 25 — 90°C >2.5 hours >952
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Sci•nce and Technolog .
54
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TABLE 15. INPUT MATERIALS AND CeECIALTY CHEMICALS USED I i PPQI&
MANUFACTURE IN ADDIUON TO MONOIIER
Function Chemical
Buffer Sodium hydrogen phosphates
Chain Transfer Agents Chiorohydrocarbons
Chlorobenzene
Butyl chloride
Chloroform
Carbon tetrachlorjde
Carbon tetrabromide
Lauryl mercaptan
Mercapto acids
t—dodecyl mercaptan
Thto].a
Ethanethiol
2—propanethiol
1—butanethiol
2 —methyl—2—propanethjo l
2— mercaptoethanol
Ethyl mercaptoacetate
Thiophenol
2—naphthalenethjo l
Trichioroethylene
Colorants
Whtte Titanium dioxide (alone or with
barium sulfate, zinc oxide, or
pearl essence)
Black Channel black
Furnace black
Red, Orange Aminoanthraquinone dyes
Cadmium sulfoge]enjdes
Iron oxides
Rhodamine B
Rhodamine 6 GDN
Yellow Cadmium sulfide
Ransa yellov R
Quinoline yellow D
Green Phthalocyanide greens
Blue Alizarine sky blue B
Indanthrene blue GCD
Phthalocyanide blue (noncryatalljne)
Ultramarine blue
(continued)
55
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TABLE 15 (continued)
Punct ion Chemical
Comonomers Acrylic acid
Acrylic es:ers
Acrylonitrile
Allyl ester, of dicarbeixylic acids
Allyl ethers of dihydric alcohols
Allyl methacrylate
—nethy1 styrefle
Butadiene
t—butylaminoethyl mePhacrylate
1 ,4—butylene dimethacrylate
Dialkyl fuiiiarates
Dialkyl aleatis
Diallyl phthalate (DAP)
Dimethyla.inoethyl aethacrylate
Divinyl bennen.
Ethyl acrylate
Glycidyl ethacrylate
Glycol di.ethacrylates
2—hydroxyethyl acrylate
ti—hydroxymethyl acrylamid.
M—hydroxymethyl .ethacrylamide
Itaconic acid
Plethacrylate esters
Methacrylic acid
Styrene
Triallyl cyanurat.
Unsaturated polyesters
Vinyl acetate
Vinyl chloride
Vinylidene chloride
Vinyl toluene
Cure Agent Benzoyl peroxide and dimethyl aniline
Emulsifier.
Anionic Surfactants Alkyl sulfates
Alkylarene sulfates
Phosphate.
Nonionic Surfactants Alkyl polyozyethylenes
Aryl polyoicyethylenes
Filler Glass fiber
(continued)
56
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TABLE 15 (continued)
Function Chemical
Initiators Amisonium persulfate
Azo compounds
2,2’ -Azobisisobutyronjtrjje (AIBN)
Benzoyl peroxide
Butyl peroxide
Cumene hydroperoxide
Dicumyl peroxide
Di—t—butyl peroxide
Hydrogen peroxide
Lubricants Cetyl alcohol
Lauryl alcohol
Stearic acid
Redox System Initiators Peroxydisulfate and sodium bisulfite,
aodium thiosulfite, sodium hydrosul—
fite, or sodium formaldehydesuif—
oxylate
Self Extinguishing Agent Polyvinyl chloride (PVC)
Solvents Acetic acid
Acetone
Benzene
Butanol
2—butanone
t—buty lbenzene
Cumene
Cyclohexane
Ethyl acetate
Ethylbenzene
Isobutyric acid
Isobutyl alcohol
Methyl isobutyrata
3 —pentanone
2— ropanol
s—butyl alcohol
t—butyl alcohol
Toluene
Triethylamine
(continued)
57
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TABLE 15 (continued)
Function Chemical
Suspending Agents Cellulose derivatives
(Protective Colloids) Diaodiua phosphate
Gelatin
MOnosodium phosphate
Polyacrylate salts
Polyvinyl alcohol (PVA)
Sta’ch
Suspension or Emulsion Modifier Glycerol
Clycols
Inorganic salts
Polyglycols
UV Light Stabilizer o-nyurozybenzophenoue
Sources: Encyclopedia of Chemical Technolog 1 , 3rd Edition.
Encyclopedia of Polymer Science end Technolo .
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
58
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Vent
Monomer
Initiator
Inert Gas
Additives
Monomer/Polymer
Mixture to
Processing
Figure 1. Maus polymerization process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
59
-------
Solution polymerization is typically a batch process. As shown in
Figure 2, the solvent and an inert gas are charged to the reactor and heated
to the desired temperature. The monomer and initiator (typically 0.01 to 7
percent of the charga are added via a small continuous stream. When the
monomer addition is comp ete, the reaction temperature is maintained until
the resin reaches a high conversion (>95 percent). The solvent is ref luxed
to the reactor during this process to provide better heat tran .fer. [ 247J
When the reaction is complete, the solvent and resin are discharged from the
reactor and diluted, if necessary, to the desired resin concentration. Any
emissione from the resin will result during the production of the end prod-
uct, such as solvent emissions during solution casting of the resin.
A typical recipe for solution polymerization of an acrylic resin is
given below [ 731:
Material Parts by Weight
Ethyl Acrylate 7,265
Toluene (solvent) 10,897
Beuzoyl Peroxide (initiator) 91
2.4.3 Suspension Polymerization
Suspension polymerizatIon resins are produced as tiny beads which are
used as molding powders and ion exchange resins. Acrylate resins are often
added for reduced resin brittleness and improved processibility of moiding
compounds. Aeino functional monomers, acid functional monomers, divinyl
monomers, or trivinyl monomers are added for crosslinking in ion exchange
resins.
As shove in figure 3, the polymerization reactor is first charged with
water and an inert gas. The monomer and suspending agent (or protective
collotd) are then added. The monomer is staMlized as tiny droplets in the
water with the suspending agent. When the suspension is stabilized, a
monomer soluble initiator is added to start the reaction. The water acts as
both a dispersion medium and a heat transfer agent. When the beads have
reached a high conversion (greater than 95 percent), the suspension is
cooled, the beads are dewatered, washed, and dried.
A typical recipe for suspension polymerization of PMMA is shown below
(73j:
Material Parts by Weight
Methyl Methacrylate 2,876
Ethyl Acrylate 508
Water 11,032
Sodium Polyacrylate (protective colloid) 29.25
Anhydrou. Disodium Phosphate (suspending agent) 62.25
Stearie Acid (lubrica, t) 70
Ethyl Crotonate (chal, transfer agent) 7
Benzoyl Peroxide (initiator) 35
60
-------
Vent
Inert Gas
Solvent
Monomer
Initiator
Figure 2. Solution polymerization process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
Vent
PIOIA in Solution
Solvent for
Dilut ion
61
-------
Veni
Inert Ga.
Water
54a .p .ndlng Agent
Iknwm.r
Inittator
FIgure 3. Suspension polyRerisetion process.
Source: Encyclopedia of Chertcal Technology , 3rd Edition.
MI A Read.
Waler to V.t.r to
Wa.tewat.r Wa.tewat.r
Treatment Tr..tne.nt
-------
Emulsion PolymerIzation
Emulsion polymerization using batch processing is the most important
industrial method for the preparation of acrylic polymers.(120J This
process is used to produce coatings and binders for the paint, paper,
textile, floor polish, and leather industries. The safety hazards and the
expense associated with the flau mahle solvents used in solution
poly_terizatlo.. ere eliminated.
The emulsion polymerization process, illustrated in Figure 4, uses a
reactor charged f .rst with water and a inert gas. In a separate mixing
tank, water, an emulsifier (typically 1 to 5 percent of the monomer charge),
methyl methacrylate, and any comonoiner are mixed. The monomer emulsion is
then metered into the polymerization reactor where a water soluble initiator
has been added. When the monomer addition is complete, the reaction is
allowed to proceed to a high conversion (greater than 95 percent) before it
is cooled and filtered.
A typical recipe for emulsion polymerization of PMMA is shown below
(73]:
Material Parts by W gh
Ethyl Acrylate 1,460
Methyl Methacrylate 720
Methacrylic Arid (93%) (comonomer) 34
Potassium Persulfate (initiator) 5
Sodium Bisulfite (reducing agent) 5
Water 2,175
Sodium Lauryl Sulfate (30%) (emulsifier) 539
The resulting emulsion typically contains 30 to 60 percent solids and
contains particles with size ranging from 0.1 to 1.0 microns. Anionic
surfactants give finer particles while nonionic surfactants produce resins
with better shelf stability and resistance to salts and f. eeze—thaw. Blends
of surfactants are often used to obtain advantages of both types. Additives
such as thickeners, flow improving agents, freeze—thaw stabilizers, pigment
dispersants, and preservatives are typically added after polymerization of
the resin. (247J
Energy Requirements
No data listing the energy requirements for acrylic polymer production
were found in the literature, consulted.
ENVIRONMENTAL AND INDUSTRIAL hEALTH CONSIDERATIONS
Acrylic resins are considered to be nontoxic and are used in food
packaging, medEcine diapensing, and medical applications such as contact
lenses and dentures. The resin producers would be adversely impacted by any
toxic effect. Acrylic monomers are mild to moderate toxic chemicals, but
63
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Inert Gas
Water
Emulsifier
(Surfactant)
Vent
Additives
Vent
Figure 4. Emulsion polymerizatic. process.
Source: Encyclope dja of Chemical rechnology , 3rd Edition.
64
Monomer
Iflitiator
PNMA Emulsion
-------
they may be handled safely by trained personnel.(l401 The following com-
pounds are listed as hazardous under RCRA: acetone, acrylic acid, acrylo—
nitrile, benzene, carbon tetrachloride, chlorobenzene, chloroform, cumene,
cyclohexai’e, ethyl acetate, ethyl acrylate, isobutyl alcohol, methyl
methacrylate, toluene, trichloroethylene, vinyl chloride, and vinylidene
chlorid.2. In addition to the hazardous listing, vinyl chloride is a con—
firme 1 human carcinogen, and the suspected human carcinogens acrylonitrile,
polyvinyl chloride, benzene, chloroform, and carbon tetrachioride are inputs
to this process. Potential human carcinogens used include polyvinyl
alcohol, trichloroethylene, vinylidene chloride, and three colorants,
Rhodamine B, Rhodamine 6CDN, and cadmium sulfide. Several other chemicals
pose a significant health risk: cumene hydroperoxide, styrene, ethyl
acrylate, acrylic acid, N,N—dimethy]aniline, toluene, triethylamine,
2—mercaptoethanol, and thiophenol.
Solvent, suspension, and emulsion polymerization are carried to over 95
percent conversion. Due to this high conversion, the sources upstream of
and including the reactor contribute significantly more to the total VOC
emissions than downstream sources. This is not the case, however, with mass
polymerization. Since the conversion for this process is between 20 and 50
percent, a significant amount of VOC emissions result from polymer casting,
molding, or finishing.
Solution polymerization has added VOC emissions due to the solvent
used. Although monomer emissions are reduced because of high conversion,
solvent emissions are also present after the reactor.
Worker Distribution and Emissions Release Points
We have estimated ‘orker distribution for acrylic resin production by
correlating major equipment manhour requirements with the process flow
diagrams in Figures 1 through 4. Estimates for each polymerization process
are shown in Table 16.
The closed process conditions associated with acrylic restn production
minimize employee exposure potential to hazardous chemical eub tancea and
physical agents. Fugitive emissions from the sources listed in ti ble 17 and
from leaks in valves, pump and compressor seals, and drains are t e major
sources of workplace contamination.
As Table 17 shows, principal contaminants from acrylic resin manufac-
ture are methyl methacrylate, polymer particulatee (nuisance dust) and
solvent (probably toluene) from solution polymerization. Toxicity informa-
tion for these and other potential input materials to t’ process is
discussed in the “Health Effects” subsection which follt,ie.
Additionally, employees may be exposed to fugitive emissions of nitro-
gen gas n other inert gases used to blanket the reactor during polymeriza-
tion. Inert gases are classified as simple asphyxiants because their
presence limits the available oxygen in the atmosphere.
65
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TABLE 16, WORKER DISTRIBUTION ESTIMATES FOR ACRYLIC RESIN PRODUCTION
Process Unit Workera/Un .t/8—hour Shift
Mass Polymerization Batch Reactor 1.0
Solution Polymerization Batch Reactor 1.0
Ref lux Condenser 0.125
Cooling Tank 0.125
Suspension Polymerization Batch Reactor 1.0
Devatering 0.25
Polymer Wash 0.25
Dryer o.s
Fnulsion Polymerization Batch Reactor 1.0
Ref lux Condenser 0.125
Batch Mixer i.o
66
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TABLE 17. SOURCES OF FUGITIVE EMISSIONS FROM PMMA MAMJFACrURE
Process
Source Constituent Mass Solution Suspension Eiiaulsjoj
Polymerization Methyl Methacrylate X X
Vent
Condenser Vent Methyl Methacrylate X X
Solvent X
Cooling Tank Methyl Methacrylate X
Vent Solvent X
Dewatering Methyl Methacrylate X
Vent PMMA Particulates X
Dryer Vent Methyl Methacrylate X
PMMA Particulates X
Emulsification Methyl Methacrylate X
Tank Vent
Mixing Tank Methyl Methacrylate X
Vent
TABLE 18. SOURCES OF WASTEWATER FROM PMMA MANUFACTURE
Process
Source Mass Solution Suspension Emulsion
Polymer Devatering X
Polymer Bead Wash X
Routine Cleaning Water X X X X
67
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No data were located in the literature f roe which worker exposure
potential may be estimated.
Health Effects
More than 100 input materials and specialty chemicals are used in the
manufacture of acrylic polymers. The health effects of exposure to over
one—half of these chemicals cannot be evaluated because sufficient data do
not exist in the available literature. Input materials for which data have
been compiled include a.large number of tumorigenic, mutagenic, and
teratogenic agents and highly tâxic chemicals.
The comonomer vinyl chloride is a confirmed human carcinogen. Pive
other chemicals are suspected human carcinogens, including the c onoaer
acrylonitrije; polyvinyl chloride, a self eztinguiahing agentfthe solvent
benzene; and the chain transfer and terminating agents ehlorofo rm andcarbon
tetrachioride. Six additional chemicals have produced positive resizlts in
animal tests for careinogenesj 9 and hus are also potential carcinogens.
They are polyvinyl, alcohol, a suspending agent; trichloroethyl ne, a chain
transfer agent; the comonomer vinylidene chl ride; and three colorants,
Ehodamine B, Rhodamine 6GDN, and cadmium sulfide.
Several chemicals in addition to these potential carcinognn, pose a
significant health risk to workers in acrylic polymer manufacturing, plants
due to high toxicities or to mutagenic or’ teratogenic potential. They
include: cumene hydroperozide , an initiator in the proces8 the comonomere
styrene, ethyl acrylate, and acrylic acid; N,N—dimethylanhljne, a cure
agent; the solvents toluene and triethylamine; and the chain transfer and
tereinatiofl agents 2 -mercaptoethano l and thiophenol.
A brief-synopsis of the reported health effects resulting fro, exposure
to each ?fthese substances follows.
. Efd is a severe skin and respiratory irritant 11701 and causes
serious eye injury. [ 157j Ingestion may produce epigastric pain, nausea,
vomiting,., circulatory collapse, and in severe cases, death due to shock.(85J
Although tho data are not sufficient to make a carcinogenic determination,
the chem?cal has been associated with tumorigenic and teratogenic effects in
laboratory animals. (233]
Acrylonitrile , a suspected human carcinogen 11071, causes irritation of
the eyes-and nOSe, Weakness, labored breathing, dizziness, impaired judg-
ment, cyanosis, nausea, and convulsions in humans. Nutagenie, tiratogenic,
and tumorigenic effects have been reported in the literature.(233J The OSHA
air standard is 2 ppm (8 hour TWA) with a 10 pp. ceiling. [ 4J
Bennene is a suspected human carcinogen (101] which also exhibits
mutagenic and teratogenic properties. It poses a moderate toxic hazard for
acute exposures and a high hazard for chroniL exposures t!’rough injeetion,
inhalation, and skin adsorption. [ 242J Effects on the ceetral nervous system
have been observed in humans upon exposure to concentrations of 100 ppm.
(98] Intermittent exposure to 100 ppm over 10 years has been linked with
68
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the development of cancers in humans.(27lJ The OSHA standard in air is 10
ppm (8 hour TWA) with a ceiling of 25 ppm.(67]
Cadmium Sulfide appears to be a mutagenic agent and has produced
posilive results in animal tests for carcinogenicity. [ 993 It is also highly
toxic by ingestion or inhalation following acute or chronic exposures.(242]
Sulfides of heavy metals are generally insoluble and usually have little
toxic action except through liberation of hydrogen sulfide. [ 242J However,
inhalation of dust or fumes of cadmium compounds affects the respiratory
tract and may also involve kidney damage. [ 149J Even brief exposures to high
concentrations may result in pulmonary edema and death.(149]
Carbon Tetrachlorlde is a suspected human carcinogen (1083 which is
also extremoly toxic after inhalation or injection of small quantitiee.(241]
The toxic hazard posed by skin absorption is slight for acute exposures but
high for chronic exposures.(241J The toxicity of carbon tetrachioride
appears to be primarily due to its fat solvent action which destroys the
selective permeability of tissue membranes and allows escape of certain
essential substances such as pyridine nucleotides. (783 The OSHA air stand-
ard is 10 ppm (8 hour TWA) with a 25 ppm ceiling. [ 673
Chloroform produces tumorigenic, mutagenic, terotogenic, and carcino-
genic effects in laboratory animals.(233J It has been designated a sus-
pected human carcinogen by the International Agency for Research on Cancer.
[ 108J Chloroform is also moderately toxic and in high concentrations may
cause narcosis and death.(1573 Rapid death is attributable to cardiac
arrest, vhile delayed death has been associated with liver and kidney
dama e.(108J Symptoms of chloroform exposure at sublethal concentrations
include respiratory depression, dizziness, nausea, and intracranial
pressure; after—effects include fatigue and headache. [ 53 The OSHA air
standard is 50 ppm (8 hour TWA).(67J
Cumene Hydroperoxide is highly toxic after short exposures involving
ingestion, inhalation, or skin absorption of relatively small quantities.
(242] Animal test data indicate that the substance is also a tumorigenic
and a mutagenic agent. P?olonged inhalation of vapors results in headache
and throat irritation while prolonged skin contact with contaminated
clothing may cause irritation and blistering.(278J
Ethyl Acrylate is currently being tested by the National Toxicology
Program for carcinogenesio by standard bioassay protocol. Previous test
data led to indefinite results.(1073 It is very toxic by injestion,
inhalation, or skin absorption (242], producing symptoms of hypersomnia and
convulsions.(l49J The OSHA air standard is 25 ppm (8 hour TWA). [ 673
2—Mercaptoethanol is highly toxic by injestion, inhalation, and skin
contact according to animal test data.(233J The substance has induced
myocard’ l effects on isolated frog hearts, hamster lung cells (89, 2623 and
chromosome abberatio.s in laboratory animals. However, very little human
toxicity data exist A.n the available literature.
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! iN-Dimethylaniline is highly toxic by ingestion, inhalation., and skin
absorption following ácite ezpos’ re.(242J It can be absorbed through intact
skin to produce dangerous methem_oglobinomia [ 85), and has been lethal to
humans by ingestion at a dose of 50 mg/kg.(156J N,N—Dimetby1amjji has
exhibited tumorigenic potential ic animal testing and is currently being
tested for carcinogenisis by the National Toxicology Program. [ 233 ] OSHA has
set an air standard of 5 ppm (8 hour TWA).(67J
Polyvinyl Alcohol has produced positive results in animal testing for
carcinogenicity.(1O7J Its single dose toxicity, however, is presumably
lov.(85j Implantation of PVA sponge as a breast prosthesis has been asso-
ciated only with foreign body type of reaction (107]; neutral solutions of
PVA have also been used in eyedrops on human eyes without difficulty. [ 87J
Polyvinyl Chloride is a suspected human carcinogen. (lolJ Although the
finished foam resin may cause allergic dermatitis, it is generally free from
health hazard unless cosainuted or strongly heated.(3J It bums readily and
gives of f objectionable saoke.(285J Several cases of angiosarcoma of the
liver have been detected among long—time workers in plants that make poly-
vinyl chloride from monomeric vinyl chloride.Lg5 ]
Rhodamine B [ (9—( o—carboxyphenyl ) 6 —(Diethylamino)_3H_, nthefl_3..ylid.fl)
diethylámmoniumchlortdej has induced utagenic (233] and carcinogenic [ 106]
effects in laboratory animals. To date, no data exist in the available
literature on the human health effects of exposure to this colorant.
Rhodamjne 6CDN Io_( 6 _(ethYlamino)...3_(eth,1jmiflo)_2,7... imethyI_ 3 fl..
xanthen—9—YL)—ethylester, monohydrochlo i e ucnzoic acid] produced positive
result s for carcinogenicity in animal testing. [ l06j It is currently under-
going additional tests by the National Toxicology Program. (233J Some evi-
dence also exists for mutagenic potential.(l06J There is no human toxicity
data in the available literature with which to evaluate the toxic effects of
this colorant on humans.
Styrene has been linked with increased rates of chromosomal aberrations
in persons exposed in an occupational setting. (107] Animal test data
strongly support epidem.tological evidence of its mutagenic potential. [ 233J
Styrene also produces tumors and affects reproductive fertility in labora-
tory ani.als.(233J Toxic effects of exposure to styrene usually involve the
central nervous system. [ 233J The OSRA air standard is 100 ppm (8 hour TWA)
with a ceiling of 200 pp.. [ 67J
Thiophenol has produced toxic effects in laboratory animálè at very low
doses adminijtjred orally, by skin contact, and by inhalation.(233J
Observed effects include behavioral symptoms, pulmonary system effects
coma, and death. No human toxicity data exist in the available literature,
however, with which to confirm the effects on humans.(233J
Toluene exhibits tumorigenic, mutagenic, and teratogeni c potential in
laboratory teats.(233J Human exposure data indicate that toluene is also
very toxic. Exposures at 100 ppm have produced psychotropic effects and
70
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central nervous system effects have been observed at 200 ppm.(233J Symptoms
of exposure include headache, nausea, vomiting, fatigue, vertigo, paresthe—
sias, anorexia, mental confusion, drowsiness, and loss of consciousness.
The OSHA air standard is 200 ppm (8 hour TWA) with a 300 ppm ceiling.(67J
Trichioroethylene has produced positive results in animal testin3 for
carcinogenicity.(108j It has also produced mutagenic and teratogenic
effects in laboratory animals (233j and is classified as an acute narcotic
which causes death from respiratory failure if exposure is severe and
prolonged.(5J Since trichioroethylene has a rather long biologic half—life,
major consideration must be given to cumulative effects of this compound.
(31] Sublethal exposure may cause liver and kidney lesions, reversible
nerve damage, and psychic diaturbancea.f85j OSHA has set an air standard of
100 ppm (8 hour TWA) with a 200 ppm ceiling.(67J
Triethylamine is highly toxic by ingestion and inhalation and moder—
nrely toxic via dermal routes.(243j It is a strong irritant to tissue. At
least one animal study has shown that triethylamine produced mutagenic
effects in rats at the low dose of 1 mg/m 3 .f96J The OSHA air standard is
25 ppm (8 hour TWA).(67J
! inyl Chloride is a proven human carcinogen (106] which may cause per-
manent injury or death after inhalation, even if the exposure is relatively
short.(242J Human reproductive effects occur at concentrations as low as 30
mg/rn 3 (1261; both tumorigenic and mutagenic effects have been observed in
humans as well as test animals. The OSHA air standard for vinyl chloride is
I ppm (8 hour TWA) vfth a 5 ppm ceiling.(683
Vinylidene Chloride has produced mutagenic, teratogenic, and carcino-
genic effects in laboratory animals.(106J In addition, concentrations as
low as 25 ppm have been associated with systnmatic effects in humans.(37 ]
If ignited, the highly toxic hydrogen chloride will likely evolve.(157J
Air Emissions
There are no major air emission point sources associated with the PNM&
process. However, fugitive emission sources may pose a significant environ-
mental and/or worker health problem depending on stream constituents,
process operating parameters, engineering and administrative controls, and
uaintenance programs.
Sources of VOC process emissions from PMM& manufacture are summarized
in Table 17 by process and constituent type. All of these process sources
are vents of some type. Control technologtes used for the VOC emissions
from vents are: (285]
• Incineration of the hydrocarbons in the vented stream by use of a
fll3re; and/or
• Routing the vLnt stream to a blowdown.
71
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Nonprocess sources of YOC emissions include leaks from valves, flanges,
pumps, compressors, agitators, relief valves, drain., air cooling towers.
Although equi’pment modification (for example, closing the atmospheric side
of open—ended valves) may be used to reduce VOC emissions, a regular
inspection and maintenance program to detect and repair leaks is the most
effective control.
Sources of particulates from PMt& processing are also listed in Table
17. Particulate emissions may be controlled by:
o Venting the dryer and devatering vent streams to a baghouse or
electrostatic precipitator for collection of particulates.
According to EPA estimates, the population exposed to acrylic r sin emis-
sions in a 100 km 2 area around an acrylic resin plant is: 41 pErsons
exposed to hydrocarbons and two persona exposed to particulat.s. [ 286J
Wastewater Sources
There are several wastewater sources associated with the various PI01&
polymerization processes shown in Table 18. The major vastevater source
results f rom suspension polymerization which uses water in the polymeriza-
tion f the PTIMA resin. Emulsion polymerization, which also uses water to
carry the i onómer through the procesi, does not generate vastevater of this
magnitude since tha polymer is not dewatered.
Ranges of several vastewater parameters for vastewaters from acrylic
resin, production are shown below. Values for the wastevater from the
processes presented were not distinguished by process type by EPA for the
purpose of establishing effluent limitations for the acrylic resin
industry. (284 3
Acrylic Resin Unit/Metric
Vastevater Ton of
Characteristic
Production 2.50 — 50.87 m 3
B0D 10—40kg
COD 10—70kg
TSS 0.1 — 1.7 kg
Solid Wastes
The solid wastes generated by this process are mostly P)IM&. Solid
waste streams include substandard resin which cannot be blended and resin
lost during routine cleaning, product blending, and spillage. P)O(& shows a
high conversion of polymer to monomer at temperatures greater than 350°C;
therefore, most PPGI solid waste can be recovered and recycled to the
polymerization process. (1213
72
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Environmental Regulation
Effluei t ii. ittations guidelines have been set for the acrylic resin
industry. BPT, MT , and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New Source Performance Standards (NSPS) (proposed by EPA on January 5,
1981) for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds are listed as solid wastes (46 Federal Register
27476, May 20, 1981):
A:etone — U002
Acrylic acid — U008
Acrylonitrile — U009
Benzene — U019
Carbon Tetrachioride — U221
Chlorobenaene — U037
Chloroforui — 11044
Cuisene — U055
Cyclohexane — U056
Ethyl acetate — U112
Ethyl acrylate — U113
Isobutyl alcohol — U140
Methyl nethacrylate — Ul62
Toluene — U220
Trichloroethylene — U228
Vinyl chloride — U043
Vinylidene chloride — U078
All disposal of these materials or FNMA which contains any residuals of
these materials must comply with the provisions set forth in the Resource
Conservation and Recovery Act (RCRA).
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SECTION 3
ACRYLONITRILE—SUTADIENE _STT gNE (ABS)
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Acrylonitrile —butadiene..styrene (ASS) polymers can be manufactured to
provide a wide range of physical properties. Typically, ABS is tough,
rigid, heat and chemical resistant with high impact strength, low tempera-
ture property retention, and high gloss. Ta combination with these proper-
tIes, the ease of fabrication makes ASS well suited for the manufacture of
drain, waste, and vent pipes business machine housings, refrigerator cris-
per trays, automotive parts, television cabinets, telephones, electrical and
electronic equipment, and other uses (e.g., toys, luggage, and packaging).
ASS, which is not a random terpolymer, is manufactured by grafting
styrene and acrylonitrile monomers onto particles of polybutadiene. Varying
ASS physical properties are obtained by altering the degree of grafting,
molecular weight of the resin, and the ratio of acrylonitrilà to styrene.
Tabla A—3 in Appendix A presents typical ASS properties according to resin
grade. The rubber content of the resin determiaes:(153, 270J
• Resistance to abrasion and heat,
• Impact strength,
• Tensile strength,
• Tenaile modulus,
• Hardness,
• Deflection temperature,
• Elongation,
• Specific gravity, and
• Coefficient of expansion.
Generally, ASS exhibits good chemical resistance. ABS is very resis-
tant to water, inorganic salts, weak bases, strong bases, and weak acids
while possessing good resistance to strong acids and poor resistance to some
solvents (such as esters, ketones, aldehydes, and some chlorinated hydro—
carbons).(130, 270]
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ABS is produced by emulsion, suspension, or mass polymerization.
Although each process has advantages and disadvantages, emulsion polyweri—
zatf on offers the greatest flexibility and can produce ABS with a superior
balance of properties. [ 270J In general, emulsion polymerization is used to
manufacture ABS with higher impact strength while suspension and mass
polymerization are utilized to produce resins with iower impact strength.
11531 Heat resistant grades are produced by the addition of ct—methyl
styrene to the polymerization reactor.
INDUSTRY SCRIPTION
Four chemical manufacturers comprise the ABS industry. These four
producers have nine sites located in eight states: California, Connecticut,
Illinois, Iowa, Massachu ects, Michigan, Ohio, and Vest Virginia. Table 19
lists these ABS prod era and their locations.
ASS i3 used in consumer hard—goods markets and construction, which
reflect the general trends of the U.S. economy. In 1980, the use of ABS in
electrical md electronic applications, including television cabinets and
plp$ng, fell 23 percent.(35 74) U.S. automobile markets have also
declined, causing a decline in ABS automotive markets. Production of ABS
for the industry has ranged from 65 to 68 percent of the total capacity
available during the period from 1976 to 1979. Therefore, the existing
capacity, co!!,bined with the planned Borg—Warner expansion, will accomodate
any industry growth in the near future.
PRODUCTION AND END USE DATA
In 1980, total ABS production was 441,000 metric tons. (143] ABS has
zany uses, which include:(130, 153, 270]
• Power tool and appliance housing;
• Protective safety equipment;
• Functional and decorative automotive parts;
• Business machine components;
• Telephones;
• Toys;
• Electronic components such as computer terminals, business machine
housings, and consumer electronic goods;
• Electronic housings;
• Consumer items such as faucets, shov r heads, and refrigerator
crisper trays;
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TABLE 19. U.s. PRODUCERS OF ABS
January 1, 1982 Capacity
Producer Thousand Metric Tone
Borg Warner Corp.a
Borg Warner Chemicals USA
Plastes Divjsion
Ottawa, IL 136.4
WaShington, WV 159.1
COMPANY TOTAL 295.5
Dow Chemical USA
Gales Perry, C l ’ 29.5
Ironton, 00 29.3
Midland, MI 34.1
Torrance, CA 34.1
COMPANY TOTAL 127.2
Mobay. Chemical Corp.b 22.7
Monsanto Co.
Monsanto Plastics and Resins Co.
Addyston, 00 145.5
Muscatine, IA 63.6
Springfield, MA 18.2 .
COMPANY TOTAL 227.3
U.S. Steel Corp.
USS Chemicals Division
Scotts Bluff, LA 68.2
740.9C
aCempany plans to build a 68,200 metric ton per year ABS plant at Port
Bienville, MS to be completed by the-end of 1982.
bResin sold by Mobay is produced by B. F. Goodrich at Louisville, KY.
CCarl Cordon Industries has a 4,500 metric ton per year plant at
Vorchester, MS on standby.
Sources: Chemical Economics Handbook , updated annually, 1981 data.
Directory of Chemical Producers , 1982.
76
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• Drain, waste, and vent applications;
• Refrigerator tuner liners and door liners;
• Boats, canoes, camper tops, luggage, and construction products; and
• Specialty applications such as video display ‘iousing, public
transportation components, and the aircraft industry.
Table 20 lists ABS consumption by processing step and Table 21 presents the
ABS consumption by end use.
PROCESS DESCRIPTIONS
ABS is produced by emulsion, suspension, or mass rolymerization. Emul-
sion and suspension proceqses have historically dominated the ABS industry;
however, the mass polymerization process has recently gained commercial
importance.(l53 Mass polymerization generates a minimum amount of waste—
water and eliminates the need for dewatering and drying. These advantages
are offset by the lessened product flexibility, greater mechanical complex-
ity of the process, and lowered conversion of monomer to polymer which
requires devolatilizatioa, f r this process.
ABS is produced by grafting acrylonitrile and styrene ontc a polybuta—
diene chain. Although the exact mechanism is not known, the polybutadien
chain probably reacts with a free radical initiator (R.) to start the
polymerization reaction. The polym r radical then combines with either
acrylonitrile (CH 2 —CHCN) or styrene r CHaC*fl to propagate the
reaction. Polystyrene and acrylonitrile may be polymerizing simultaneously,
and the reaction is terminated by either two radical groups combining or the
introduction of a chain transfer agent (R’R). The polymerization reaction
is shown below:
Initiation
i”1 I -CR—CH—CH 2 ’rl + R • l.Cli—CN.CM_Cfl 2 s. + RN
polybutadiene
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tABLE 20. ABS CONSUMPTION ACCORDING TO RESIN USE
Resin Use 1981 Thousand Metric Tons
Extrusion 182
Molding 205
Export 20
Other 34
TOTAL 441
Source: Modern Plastics , January 1982.
TABLE 21. ABS CONSUMPTION BY END USE MaRKET
Market 1981 Thousand Metric Tons
App ltances 85
dusinese Machines, Telephones 35
Consumer Electronics 25
Furniture 6
Luggage 13
Modifiers 11
Packaging 4
Building and Construction 100
Recreation 25
Transportation 56
Export 20
Other 61
TOTAL 441
Source: Modern Plastics , January 1982.
78
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Propagation
b CHCHCH-CH + CU 2 aCUCN
acrylonjtrjle
—
CH2
‘CU-CM
I
CH-CH CH-CH I’j I-CH 2 __-.___ —
9 yrene
$4 CH—CH CH CH 2 lA
SI
f l -C l ! 2
Termination
Radical Combination
+ M H_CH_CH_CH 2 A..l. ......................
•CH-CN
“v- CH—CM—CH—CH 2 ft. .
CH—CN
N CH—CH-Clj—CH 2
Chain Transfer
N 1 H—CH’Cll—C} 1 2 #v’. + R’R ‘ H—CH.CII —CHr+ a’.
CH2
•Cll—CN R”-CH—CN
79
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Oxygen reacts with the free radical initiators used, thus making a peroxide
radical shown below:
R• +
which slows the reaction rate. Polymerization is performed in a nitrogen
atmosphere to minimize this reaction.
Tables 22 and 23 list typical input materials and operating parameters
for the three ABS produceion processes. Other input materials used in ABS
production such as free radical initiators, redox initiation systems, emul-
sifier., coagulant., chain transfer agents, suspension stabilizer., and
specialty chemicals (e.g. antioxidant.) are listed in Table 24. Styrene and
acrylonitrile monomers are typically used; however, some ASS procesees use
SAN as an input to the polymerization process (see the section on SAN).
Emulsion Polymerization
Emulsion polymerization of ABS resins can be broken into four basic
steps: polybutadiene polymerization, ASS polymerization, polymer coagula-
tion, and product separation. In the first step, shown in Figure 5, poly—
butadiene is produced in a batch reactor using emulsion polymerization. The
initiatoç, activators, and emulsifier. are fed to a reactor which has been
purged of oxygen. Water and butadiene are added and the temperature is
increased Lo initiate the reaction. The polybutadiene.produced may be
either a honopolymer or copolyler which includes up tc 35 percent etyrene
or acrylonitrile. The temperatures for this reaction range f.om 5 to 70’C.
Free radical initiators or a redox initiation system may be une I to promote
the polybutadiene po1ymerjzation. A typical recipe for polybutadiene
production uiing a redox initiation system follovs:(1S3J
tater a1 Parts by JeigIi
butadiene 175.00
cumeme ydroperozlde (initiator) 0.30
sodium pyrophoephate (activator) 2.50
dextrose (activator) 1.00
ferrous sulfate (avivator) 0.05
sodium oleate (emulsifier) 4.00
water 200.00
When the polybutadiene polymerization has reached the desired conver-
sion, the polymer latex i, fed into the ABS polymerization reactor where
acrylonitrile, styrene, emulsifier., and initiators are added. The ABS
produced in this second step has a polybutadiene content which range. from
10 to 60 percent. The graft polymerization reaction may be either batch or
semi—batch processes.
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TABLE 22. TYPICAL INPUT MATERIALS TO ABS PRODUCTION PROCESSES IN ADDITION
TO STYRENE, ACRYLONITRILE, POLYBUTADIENE, AND INITIATOR
C ain
Transfer Suspension
Process Water Stabilizer Emulsifier lant
Emulsion X X X X
Suspension X X X
Mass X
TABLE 23. TYPICAL OPERATING PARAIIE(’LRS FOR ABS PRODUCTION PROCESSES
Reaction
Process Temperature Pressure Time Conversion
Emulsion 55 — 75C atmospheric 1—6 hrs 99%
Suspension 100 — 170C 350 kPa 8-16 hrs 99%
Mass 120 — 180C atmospheric 1—5 bra 50 — 8OR
Source: Encyclopedia of Chemical Techno1og , 3rd Edition.
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TABLE 24 • INPUT MATERIAT.S AND SPECIALTY CHEMICALS USED IN ABS MMWPACTTIUE
(IN ADDITION TO MONOMER AI13POLYBUTADIENE)
Free Radical Initiators Azo compoucds
Di—tert—buty] peroxide
Other organic peroxides
Potassium peroxydisulfate (aqueous potassium
pereulfat )
ert—butyL peraeetate
Redox Initiacion Systems
Initiator Cumeme hydroperozide
Activators Dextrose
Ferrous sulfate
Sodium pirophosphate
Esulsifiers Sodium oleate
Ant toxidants Di—tert—butyl—p—cresol
Tris( nonyiphenyl) phosphite
Coagulants Cal’ium chloride
Hydrochloric acid
Soiium chloride
Sulfuric acid
Chain Transfer Agents Pfercaptans
Terpenes
Terpinolene
Suspension t b iiz.rs Acrylic acid—2—ethylhexyl acrylate copolymer
Carboxymethylcel lulose
Polyvinyl alcohol
Water melubi., acrylic polymers
Sources: Encyclopedia of Chemical TechnololZ , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
82
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buia itw e.
kauL It
IiiU i. tur .
e r
Mr)i.nhLriLe.
uiiift rS,
Figure S. Euaulsion AIS process.
V.DL
AIILI xtd.iiiI,
Stea.
Hut
V iit Air
Dry
Ke6 1u
L I I Luent
Wa8tewaLer
Source: Encyclopedia of Chemical Technolcgy . 3rd Edition.
-------
A typica’ recipe for A8S with a 40 pe cent polybutadiere content
follovs:- [ 153J
Material Parts by Weight
polybutadiene—acryloni true
(93:7) latex (50% solids) 900.0
water 1055.0
emulsifier 2.0
initiator (2% aqueous solution
of potassium persulfate) 240.0
styrene 455.0
acrylonitrij.e 235.0
terpinolene (chain transfer agent) 4.8
After the reaction reaches the desired conversion, the mixture is
cooled and sent to the coagulation system, which is the thLrd 3tep. AU is
recovered from the emulsion by coagulation with dilute salt or acid solu—
tLons. Those emulsions using a detergent as an emulsifying agent are
coagulated with salt while those using soaps may use either salts or acid
solutions.(153J Agglomeration of particles is aided by increasing the
temperature to the range from 80 to 100C.(153J
The resulting slurry is sent t a holding tank before devatering and
drying. Ii these last twa, processes which constitute the product separation
step the polymer is first aeparated from any remaining water. The ASS is
dried while the effluent is sent to wastevater treatment.
Reactors used to produce the polybutadiene latex are designed to with-
stand pressures up to 1.0 x i06 Pa, have capacities that range from 13 to
30 m 3 , and are constructed of stainless steel or glass—lined carbon steel.
ABS polymerization reactors are stainless bteel or glass—lined vessel, with
capacities of up to 20 m 3 .(153J
Mass Suspension Poly.e’ization
There are tw major differences between amulsion polymerization and
suspension p,lyiserization. First, the polybutadiene used for suspension
polymerization must be soluble in the organic phase (styrene and acrylo—
nitrile). Polybutadiene must have very little crosslinking in order to
attain this desired solubility. Sec3ndly, suspension polymerization doss
not requir, a nolybutadiene latex as input to the polymerization reactor.
Therefore, the polybutadiene need aoi. be suaiufactured on—site and may ho
added aa a dried resin.
Mass suspension polymerization consists of three basic steps: pre—
polymerization, polymerization, and product separation. As shown in Figure
6, polybutadiene is dissolved in styr.ne before entering the prepolymer lza—
tt-i reactor. The sty!ene/polybuaadiene mixture in the reactor is combinnd
vi h acrylonitrile and initiator, and heated. Temperatures ?nr the pie—
polymerization step range from 80 to 120’C and reaction times are typically
between two and eight hours.
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Figue 6. Mass suspension A S process.
Source: Encyclopedia of Chesical Technology , 3rd Edition.
1u I&&Lur.
V. nt
Hot Air
V i t
to
Wd t ewdiur
-------
When the conversion in the prepolymerization reactor reaches 25 to 35
percent, the reaction mass is transferred to a polymerization reactor filled
with water. In this step, a sus rAing agent. is added and the reactor is
heated. Th# reaction proceeds until the desired conversion is reached.
After polymerization, th polymer beads are separated from the suspen-
sion medium. The effluent Is sent to veatevater treatment while the beads,
which enter the dryer at 10 percent m,isture, are dried to a moisture
content of less than 1 percent.
Suspension polymerization ABS beads range f torn 0.4.to 1.2 me in diam-
eter. The rea tora used have capacities of up o 41 m 3 and are con-
structed of stainless steel, stainless—clad ceroon steel, or glass—coated
carbon steel. A typical suspension polymerization recipe follovs:(153j
Material Parts by Weight
soluble polybutadiene rubber 14.00
etyrene, 62. ’)O
acrylonitrile 26.00
tert—butyl peracetate (initiator) 0.07
di—tert—butyl peroxide (initiator) 0.05
terpinolene (chain transfer agent) 0.90
water 120.00
acrylic acid—2—ethylhexyl acrylate
copolymer (suspensior stabilizer) 0.30
Mass Polymerization
Mass polymerization of ABS differs frr’. the emulsion and suspension
polymerization processe. used since water is not used as the polymerization
medium. Therefore, the polybutadicne must be soljble in the •tyrene and
acrylonitrile monomers. In tt’!a ‘aspect, mass and suspension polymerization
use polybutadiene that has simili’ r solubility propert 6 ze.
Mass polymerization consists of fotar basic processing steps pro—
polymerization, polymerization, devolatilization, and extrusion. As shown
in FIgure 7, the polybutadiene Is disaol-sad in styrene before it enters the
prepolymerization reactor. In this first step acrylonltril. and initiators
are combined with the styrene/butadjen. mixture in the prepolymertzatjon
reactor and heated. When the polymerization reaches about 30 percent, the
reaction mass is fed to a bulk polymerization reactor.
The reaction continues during the second ,t.p In the polyrneriEaeioft
reactor until It reache, the desired conversion, typically 50 to 80 percent.
1153J The reoiilting monomer/polymer mixture In then fed to a devolattlizer.
Tn third step, unreacted s yrene and acrylon itriie are reoved In a
devolitiltzpr and recycled to the feed stream. Thene recycled monomers
covistitu’e between S and 30 percent o? the Input to the polymerization
reactor.
86
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Sly
PutybuclJLdnd
r v Cr t I
hilt Ljtur*
Figure 7. Mass A3S process.
Source: ! cyci pedia of Chemical Technology , 3rd Edition.
ir
A I H
-------
The devolatilized polymer is cooled in a water bath before it is
pelletized in an extruder. The resulting A3S pellets are then ready for
bagging and shipping.
A typical mass polymerization r cipe for ABS was not found in the
literature.
Energy Reguireme,.cg
There were no data giving the energy requirements for ABS production in
the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH CX)NSIDERATIONS
Although ABS is considered to be a nontoxjc compound, used as pipe for
rotable vat2r, sove input materials to ABS processing are consLdered to pose
a significant health risk. Styrene is considered to be a relatively safe
organic chemical 1171; however, prolonged or repeated contact with the skin
may cause skin irritation and over exposure to vapor may cause eyç and
nawal irritation. Styrene odors are detectable at 60 ppm andare quite
strong at 100 ppm. [ llJ
Emulsion and susnension polymerization processes for ABS carry the
polymerization reactl)n to 99 perceflt. Due to this high conversion, the
sources upstream of and including the reactor contribute significantly more
to the total VOC emissions than the sou ces downstream of the reactor.
‘The low convergion in the mass polym rtzat Ion process (50 to 80 per-
cent) necessitates recycling the unreacted monomers to the reactor. This
lEN eon, .rQtOfl iliu, c. .. Ph reartor vent suspect as a source of. acr.y-lo—
nitrile, styrene, and butadipne emissions. The lower levels of conversion
which are achieved by the mass polymerization process require a devolatili—
zat ion step. Although the mass polymerization process generates signifi-
cantLy less wastevater the added devoigtiljgatlon step adds additional
fugitive VOC emissions.
Worker Distribution and Emissions Release Points
Worker distribution estimate, have been made by correlating major
equipsent manhour requirement, with the proc.sa how diagrams shown in
FIgures 5 through 7. Estimates for iiach polymertiation process are shown in
Table 25.
No naj,r air emission point sources are associated with ABS polymeri-
zation proceaqeg. Fugitive emission sources, however, may significantly
impact environmental residuals and/or worker health. The degree to which
thege mpect the worker’s environment are determined ‘j the stream con—
stitijents, process operating paramet rg, engineering and administrative
controls, and maintenance programs.
88
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TABLE 2 ,. b RKER DISTRIBUTION ESTIMATES FOR ABS RESiN PRODUCTION
Process Unit Workers/Unit/8—hour Shift
Emulsion Polymerization Batch Reactor 1.0
Coagulator 1.0
Slurry Tank 0.125
Devatering 0.25
Dryer 0.5
Mass Suspension Polymerization Batch Miz r 1.0
Batch Reactor 1.0
Dewatering 0.25
Dryer 0.5
Mass Polymerization Patch Mixer 1.0
Batch Reactor 1.0
Devolattlizer 0.25
Water Bath 0.25
Extruder 1.0
89
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Sources of fugitive emissions are shown in Table 26. As the table
qhowg, prtncip.’l contaminants to which workers may be exposed include
butadiene, styrene, acrylonitrile, and polymer particulates (nuisance dust).
Additiondlly. employees may be exposed to a variety of product additives,
stabilizers, polymerization initiators and emulsifier. available. Toxicity
information for these contaminantz is discussed below in t e Health
effects” subsecticn of this section and in IPPEU Chapter lOb, ! lastics
Additives.
Health Effects
Ar mal test data indicate that several input materials and specialty
chemicals used in ABS manufacture are tumorigenic agents; however, only one,
the suspension stabilizer polyvinyl alcohol, tests positive for carcino—
genicity. Other substances that pose a significant health risk to plant
employees by virtue of high toxicities include cumene hydroperozide and
ferrous sulfate, which are .sed ii the redox initiation system; and the
suspenaion stabilizer, acrylic acid. The reported health effects of
exposure to these substances are summarized below.
Acrylic Acid is a severe skin and respiratory irritant (1701 and Is one
of the most serious eye injury chemicals. (157J Ingestion may produce epi
gantric pain, nausea, vomiting, circulat ,ry collapse, and in severe cases,
death due to shock.(EJ Although th data are not sufficient to make a
carcinogenic determination, the chemical has been associated with tumori—
genic and teratogenic effects in laboratory animals.
Acrylonitrile , a suspected human carcinogen (1061, causes irritation of
the eyes and nose, weakness, labored breathing, dizziness, impaired judg—
sent, cyanosis, nausea. and cont lsIonn in humans. Ilutagenie, terstogenic,
and tumorigenic effects have been reported ii the literature. The OShA air
standard is 2 ppm (8 hour TWA) with a 10 pp. coiling.(67J
Cumene Hydroperoxide is highly toxic after hort exposures involving
Ingestion, inhalation, or skin absorption of relatively small quantities.
f242J Animal test data indicate that the substance is also a tui.origenic
and a mitagenic agent. Prolonged inhalation of vapors results in headacha
and throat irritation, prolonged skin contact with contaminated clothi:ig may
cause Irritation and blistering.(278J
Ferrous Sulfate nan produced toxic effects involving th. central
nervous system in children at doeses as low as 20 sg/kg. (1llJ Death has
occurred in humane at exposures of 200 mglkg.(21J Although iron salts
differ considerably in astringency, lethal doses appear to be clearly
related to total iron conte t. (85J Animal test data suggest that ferrous
sulfate Is also a tumorigen and a mutagen.
P,1yvinyl Alcohol has produced positive results in animal testing for
carclnogenic lty.jlOlJ Its single dose toxicity, however, Is pressivably
Iow.f9 j Implantation of PVA sponge as a breast prosthesis has been
associated only with f re1gn body type of reaction (lOlJ; neutral solutions
of PVA have also ‘,een jq d in eyedrops on human eyes without di i f1culty.(87
90
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TABLE 26. SOURCES OF FUGITIVE EMISSIONS FROM ABS MANUFACTURE
Process
Source Constituent Emulsion Suspension Mass
Reactor Vents Butadiene X X X
Styrene X X X
Acrylonitrile X X X
Initiators X X
Emulsifiers X
Suspension Stabilizers X
Slurry Tank Styrene X
Acryionitrile X
Butadiene X
Dewatering ABS and Monomer
Emissions and
Particulates X X
Dryer Vent ABS and Moncmer
Emissions and
Particulates X X
Extruder ABS and Monomer
Emissions and
Particulates X
91
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Styrene has been linked with increased rates of chromosomal aberrations
in persons exposed in an occupational setting. l06J Animal test data
strongly support epideiniologi a]. evidence of its mutagenic potential.1233J
Styrene also produces tumors sad affects reproductive fertility in
laboratory animals.12333 Toxic effects of exposure to styrene usually
involve the central nervous system.(2333 The OSHA air standard is 100 ppm
(8 hour TWA) with a ceiling of 200 ppm. 1671
Air Emissions
VOC emission sources for ABS processing are summarized in Table 26.
Both the constituent and the process type are indicated for each source.
Most of these sources are vents, which use the following control
technologies: (2853
• Venting the stream co a flare where hydrocarbons are inc tnerated;
and/or
• Venting the stream to a blovdovn.
The VOC emissions from devatering may be controlled by:
• Enclosing any atmospheric dewateriug process; and/or
• Venting any centrtf ge streams to either a flare or a blQwdovn.
Similarly, VOC emissions from the wxtruder may be controlled by:
• Extrusion under reduced pressure followed by routing the of fgasee to
the reactor; and/or
• Venting the stream to a flare or blovdovn.
Sources f particulatea for the ABS process are al.o listed in Table
26. Particulate emissions from dewatering may be reduced by:
• Enclosing any atmospheric dewatering sources; and/or
• Venting any centrifugal streams to either an electrostatic
precipitator or a baghouse.
Particulate emissions from the extruder and the dryer vent may also be con-
trolled by venting the streams to either an electrostatic precipitator or a
baghouse.
Wastewater Sources
There ere several wastewater sources associated with the various ABS
polymerization processi shown in Tnble 27. The major wastevater sources
result from emulsion and suspension polymerization which use water to
polymerize the ABS resin. The water separated from the polymer in emulsion
92
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TABLE 27 • SOURCES OF WASTEWATER FROM ABS MANUFACTURE
Process
Source Emulsion Suspension Mass
Polymer Dewatering X X
Spent Water Bath X
Routine Cleaning Water x x x
93
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polymerization is reported to contain: 0.25 kg styrene; 0.5 kg acryloni—
true; 0.25 kg sulfuric acid; 2.5 kg emulsifier; 0.25 kg sodium bisulfite;
and 0.75 kg calcium chloride per ton of ABS produced.f93J
Ranges of several vastevater parameters for wastevaters from ABS
production are shown below. Values for the vastevater from the processes
presented were not distinguished by process type by EPA for the purpose of
establishing effluent limitations for the ABS industry: [ 284J
ABS Wastevater Unit/Metric
Characteristics Ton of ABS
Production 1.67 — 24.03 m 3
BOD 2 — 20.7 kg
COD 5—33.3kg
TSS O30kg
Solid Wastes
The solid wastes generated by this process are mostly ABS. Solid waste
streams originate from reactor cleaning, product blending, particulate
removal, and spillage.
Environmental Regulation
Ef fluent limitations guidelines have been set for the ABS industry.
BPT, BAT, and NSPS call for the ph of the effluent to fall between 6.0 and
9.0 (41 Federal RegisLer 32587, August 4, 1976).
New source performanc, standard. (proposed by EPA on January 5 1981)
for volatile organic carbon (VOC) fugitive emissions includeg
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure release., which should not
last more than fly, day.; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 13 days.
Acrylonitrjle is listed as a hazardous waste (46 Federal Register
27476, May 20, 1981) and dasignated as O9. All disposal of acrylonitrile
or ABS which contains any residual acrylonitrtle must comply with the
provisions set forth in the Resource Conservation and Recovery Act (ECRA).
94
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SECTION 4
ALKYD MOLDING RESINS
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Alkyd resins comprise a segment of the plastics industry whose major
use (90 percent) is in the manufacture of coatings. The other 10 percent
produced as molding comp’,unds viii be the subject of this section. Alkyd
molding resins exhibit high arc resistance, track resistance, good high
temperature dielectric properties, and dimensional stability up to 232C
(450F). Specialty grades offer self—heating arc resistance as well as
X—radiation barrier and flame retardant properties. ADyd molding resins
may be pigmented in a wide range of colors which exhibit relatively good
heat and ligit stability. Table A—4 in Appendix A lists typical properties
of alkyd resins.
Molding compounds are manufactured as solids, classified as granular,
putty, rope, or bulk.12471 Alkyd molding resins cure rapidly at low molding
temperatures and exhibit heat r.sistance, dimensional stability, and
electriral properties over a wide temperature range. Fillers are added t
i%lkyd resin molding compounds to control shrinkage as well as internal
stresses and strains, reduce coat, control flow properties, impart heat
resistance, provide an improved surface appearance, increase electrical
resistance, reduce moisture absorption, or provide other, more specific
properties. Typical fillers f or alkyd molding resins and the properties
they provide are listed in Table 28.
Alkyd resins may be classified in three different ways: by the alkyd
ratio (polyhydric alcohol to phthalate ratio); by the oil length or percent
oil; or by the percent phthaiic anhydrid . 128J The oil length, or type of
oil, describes a general classification of oils which are used for a
specific alkyd resin appitcdtion. The following table gives a list of
cta sifications with the fatty acid (or oil) content and the phthalic
anhydride coucev t.fl28, 154J
Classification Fatty Acid (Oil) Phihalic Anhydride
( Type of Oil) Content, Z Content, 2
short 30—45 35—46
medium 43 — 55 rn — 37
long 55-7fl 20—30
very long >71 <23
95
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TABLE 28. TYPICAL FILLERS FOR ALKYD MOLDING RESINS AND THE
PROPZRTIES THEY PROVIDE
Filler Properties
Antimony Oxide Used to impart flame resistance, usually
in conjunction with a chlorinated or
brominated resin
Asbestos Fibrous in nature, fnrl!g a strong bond
with the resin to impart toughness and
qtiffness, and is a good flow control
agent
Earl urn Sulfate High specific gravity and opaque to
X—rays
Calcium Carbonate Near white appearance, high filler load-
ing. possible with good flow, imparts
excellent high frequency electrical
properties
Clay towers moistur, absorption, raises hard—
ness andflexural strength, excellent in
high voltage applications
Iydrated tiumina Raises heat, arc—tracking, and flame
resistance
Mica Good flow control agent, imparts high
dielectric strength
Silica and Talc Inert, inexpensiv, fillers
Titanium Dioxid, Very white appearance, raises dielectric
constant
IJol lzgtonite Improves hardness
Source: Seymour S. Schwartz and Sidney N. Goodman, Plastics Mterials and
! rocesses , 1982.
96
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Alkyd resins are currently manufactured by one of two processes: the
alcoholysis method or t e fatty acid method. These two processes diffez in
that the fatty acid method uses dir2ct esterification while th.
method uses an alcoholizing tr1 l7cL•r1d . oL ad a polyol to form partial
esters before ne esterificatton is c.c pleted with the addition of dibasic
acic s. Alcoholysis is currently the most widely used process.(128J
INDUSTRY DESCRIPTION
The alkyd resin industry is co’sprised .if 61 producers with 117 sites in
24 ‘Jifferent states. Although these pla.’rs are distributed across the con-
tinent, a preponderance of sites (28 percent) are located in the Great Lakes
States, EPA Region V. New York and New Jersey (EPA Region Ii), the West
Coast (EPA Region IX), and the North Central States (EPA Rdgion III) contain
17, 17, and 14 percent of the aikyd resin sites, respectively. Alkyd resin
producerq and their locatLons are listed in Table 29. Plant capacities are
considered to be proprietary.
Alkyd resins are uóed primarily as coatings. Over 90 percent of all
alkyd resins produced are used to manufacture paint, varnish, or lacquer for
industrial and home consumption. bver half of the alkyd resins produced are
sold to formulators while the remaining resin is formulated by the alkyd
producer. Most alkyd resins used for coatings are pigmented. 154J
S 4 nce 1976, alkyd resin production has ir.creased from 30G,000 metric
tons to 320,000 metrtc tons, 342,000 metric tone, and 343,000 metric tons in
1971, 1978, and 1979, respectively, Unlike other polymers whih suffered
ir’,m declining markets In 1980, alkyd rcsin production remained at 341,000
metric tons.165J
Processing alkyd resins requires adherence to stringent safety prac-
tices; volatility and flash poinrs f the solvents and vinyl crosslinking
agents used pose pt ten ia1 fire and explosive hazards. ALkyd resin equip-
ment should bc separated from storage areas using firevalls and automatic
fire doors. Other safety precautions are listed below: 154j
• The use of explosion—proof electric motors, switches, and wirtng.
The electrical installation should conform to the Class 1, Grout D
outline in the N’tional Electrical Cod’.
• The removal of causes ef static electricity and grounding of all
equipment in acr,rdance with NFPA Pamphlet No. 77, Statlc
Electricity.”
• Adequate wpntilatlon to minimize buildup of an explosive or toxic
solven’ ‘.on entration as a result of pumping or thinning.
• The protection of kettles with rupture discs designed ‘o relieve
excess pressure. Thi. rupture disc should be vented to a safe
torqtton, so that the hot vapors will not he ignited.
97
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MILE 29. U.S. ALKYD RESIN PRODUCERS
Producer Location
AD Chemical Co., Inc. Remark, NJ
AZS Corporet ion
AZ Products, Inc. Division Eaton Park, FL
AZS Chumical Co. Division Atlanta, GA
Ball Chemical Co.
Electrical Insulation Resins Clenshav, PA
Beatrice Food. Co.
Beatrice Chemical Division
Parboil Co. Division Baltimore, MD
Bennett’s Salt Lake City, U?
Bisonite Co., Inc. Tonavanda, NT
P1’. A. Bruder & Sons, Inc. Philadelphia, PA
California Resin and Chemical Cu.,
Inc. Vallejo, CA
Cargill, Inc.
Chemical Products Division Carpenterevill., IL
Forest Park, GA
Lynvood, CA
Celanese Corporation
Celaneee Plastics & Specialties Co.
Division
Celanese Specialty Resins Division Los Angeles, CA
Louisville, KY
Chemical Products Corporation El.wood Park, NJ
Degan Oil & Chemical Co. Jersey City, NJ
DeSoto, Inc. Chicago (eights, II.
Garland, TX
The Dexter Corporation
Midland Di-iiston Cleveland, OH
Hayward, CA
nocky Hill, C T
Vaukegan, IL
(continued)
98
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TABLE 29 (continued)
Producer Location
Dock Resins Corpocation Linden, NJ
Enkay Chemical Co. Elizabeth, NJ
Foy—Johnsto , Inc. Cincinnati, OH
Ceneral Electric Co.
Engineired Materia Group
ElectLonlaterials Business Department Chelsea, MA
Schenectady, NY
The P. D. George Co. St. Louis, 4O
Guardsman Chemicals, Inc. Grand Rapids, MI
Hanrzschy Chemical Co.
Ferac Oil & Chemital Co. Division Riverdale, IL
Hugh J.—Resins Co. Long leach, CA
Insilco Corporal on
The Enterprise Companies Division Whei ltng, IL
Tovite Chemical;, Inc. Matt so’ , IL
Jones—Blair Co.
Texas Resins Corporation, su’,sidiary Dallas, TX
Lavter Interna.ional, Inc. South ICearny, i4J
Mobil Corpo tion
Marcor Inc.
Montgomery Ward & Co. Ic c.,
subsidiary
Standard T Chemical Co., Inc.
subsidiary Chicago Heights, IL
The O’Brien r,rporatlon
The O’Brien Corpor tion—Centrai
Region South l d, IN
The O’Brien Corporation—Eastern
Region Baltimore, MD
The O’Brien Ccrporation—Southwestern
Region Houston, TX
The O’Brien Corporation—Western
Region South Sat’ Francisco, CA
(continued)
99
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2ABLE 29 (continued)
Producer Location
C. .1. (Jeborn Cheiiicals, Inc. Pennsauk,n, NJ
Perry & Derrick Co. D4!?tOnIP KY
Phillips Petroleum Co.
Interplastjc Co’poratjon, subsidiary
Commercial Resins Division Mtnneapolis, MN
Polychrome Corporation
Cellomer Corporatic.n, sub.tdiary Newark 1 NJ
PPC Industries, Inc.
Cuatings and Resins Divisiv n Circievill., 00
East Point, CA
Houston, TX
Oak Creel, WI
Springdale, PA
Torrance, CA
Reichhold Chemicals, Inc. Asusa, CA
Detroit, MI
Eliaabeth, NJ
Ibust , IX
Jacksonville, FL
South San Francisco, CA
Tust.alooaa, AL
SPerling Division Savicirley, PA
0 . oberston Co.
ireu ean Chemical Corporation,
subsidiary Burlington, IA
Chathau., VA
Saukville, WI
Schenectady Chemicals, Inc. Schenectady, NY
SO! Cc rporat ion
Clidden Coatings & Resins Division leading, PA
San Francisco, CA
Sybron Corporation
Chemical Division
Jersey State Chemical Co. Division Haledon, NJ
Synray Corporation Kenilworth, NJ
(e ,nt aued)
100
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TABLE 29 ( ontinned)
Producer Location
Textron Inc.
Snencer Kellogg Division Baltimore MD
Newark, NJ
Pensacola, FL
San Canoe, CA
Valley Park, MO
Tyler Corporation
Reliance Ufliversal Inc., subsidiary
Specialty Chemicals and Resins
Division Louisville, KY
U.S. Polqmers, Inc. St. Louis, MO
U itad States Steel Corporation
U.S.S. Chemicals Division Colton, CA
United Technologies Corporation
Inisont Corporation, subsidiary Anaheim, CA
Cincinnati, OH
Detroit, MI
C:reenville, OH
Vaispar “.orporation
McUhorter, Inc., subsidiary Baltimore, MD
Carpentereville, IL
Rockford, IL
Westin ”ouse Electric Corporation
Insulating Materials Divisfon Manor, PA
Yenkin—Majegtic Paint Corporation
Ohio PolychemicaJg Co. Division Columbus, OH
Source: Directory of Chemical Producers , 1982.
101
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• When a chirge is removed f roe the kettle, the introduction of an
inert gas at a rate sufficient to relieve the displacement, in order
to avoid the entry of air through the vent on the condensing system
and thus the formation of a potentially explosive atmosphere.
PRODUCTION MiD END USE DATA
In 1980, alkyd resi i production totaled 343,000 metric tona46SJ Alkyd
molding resins constitute about 10 percent of the market. Finished products
include automobile parts, furniture, electrical equipment and cables,
packaging, and construction components for buildings. Other uses for alkyd
molding resins include:(128, 154, 247, 263)
• Automotive ignition parts vhere high track resistance and low
dielectric losses at higI temperatures are desired as well as brush
holders, coils, distributors, housings, solenoids and switches;
• Electrical and electronic parts where mechanical strength is needed,
including bobbins, capacitors, coils, relays, encapsulated compo-
nents, molded circuitry, resistor., and transformer.;
• Appliances and parts vuich require both color and high temperature
stability such as connectors, pump impellers, relays, switches,
thermostats, and timers;
• Circuit breakers, contactors, and overload protection for motors;
• Starters, interlock switches, and siitch covers;
• Television parts, includi:.g coils, corona caps, sockets,
transformers, terminal boards, and tuner strips; and
• Phonograph records.
PROCESS D€SCRIPTIONS
Alkyd resins are produced by either the alcoholysis method or the fatty
acid method. The alcoholysis method combines an alcoholising triglyceride
oil, such as soya or linseed, with a polyol, usually pontaerythritol or
glycerol. The’partial esters produced are then esterified using a dibasic
acid, such as phthaltc anhydride. The fatty acid method uses direct
esteriflcation of the. reactants to form the resin.
Alkyd resin product ton processes are batch due to th. difficulties
encountered with continuous processe3, including buildup of erosslinkad
monot er on the reactor walls. The procedure used for each process depend.
upon the properties desired In the alkyd resin. A solvent may be used to
carry the resin through the reaction process. Solvent is added directly to
the reactor for the fatty acid method and to the reactor after the dibasic
acid in the alcoholysis method. Using a solvent provides resins of better
color and uniformity, higher r stn yl Id due to lover phthalic anhydrida or
102
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polyol (polyhydric alcohol) losses through the condenser, lover ester.Liea—
tion t ’nperatures, fa3ter esterification cycles, and easier kettle cleaning.
If these parameters are not important for the processor, the fusion process,
which uses no qolvent, may be used. Currently, this process has a large
investment in existing plants, makes alk yds with isophthalic acids more
easily, represent ’ a lover investment cost for new plant’, and requires less
s rtrigent safety precautions. [ 154J
Alkyd resins produced by partial alcoholysis combine an oil with a
polyot to form a partial ester which in turn is esterified with a dibasic
acid. The alcoholysa reaction is shown below.
OH OH
c -0—c—a I
2 CE 2 A1UIIn. CE
I I Catalyst i 2 u 2 o
I P I I I I
ii (11—0—C-S + n HO—CE -C-CE -OH n (II - OH • , R—C—O—CH C—CE -0-C-S
212 A 2p 2
O I CH -uC-O C II
CM 2 p2
CH 2 .O—C—S i 2 5 OH
O i l
Trtglycerid. Panta.rythritol Partial Eater.
Polyhydr1 ALrohol)
C I I
0 2 0 2 o Alkalins
fl - -O-C 1 l 2 -C .C II 2 -O .R CII -CE C-C
H 2 -O-C-0 () A
Pirtlal E.t.ri Phth.llc Anliydrld. (dlb.1c acid)
r 1 0
HO CM — CH ______
CE Ol -ocii CEO I I
, i 21
(-0—C 1 1 2 CI I ‘ -I) H O
p 2
I—c—,
Alkyd R.s.i
‘I
41voho1yst is used in the preparation of alkyda which have an oil
suibqt1t, te.1 for the f’itty aci4. Monomers aral peroxide ratalyata are added
to cr(,sglink the pol,’mv. .f247J
103
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Using the fatty acid process, aikyd resine are produced from the
reaction of a polyol, a polyacid, and an u 1 isaturated fatty acid. This
reaction yields a c mplex branched structure or network which is an
infusible, insoluble compo’ind at 80 percent esterification. This overall
reaction is shown below.
0
0 C C0
2
na—c • aCt—OH ‘a
H-OH
‘n.aturat.d Glye.rol Phehalic Anh drLd
Pauy Acid
I—oN
a —t,_ T I: (Zn-i) 520
Mkyd 5.,ta
Table 30 lists typical operating parameters for the two alkyd resin
production processes. Aikyd resin propert.ae, however, are determined
primarily by the input materials used instead of the process performed. For
example, unmodified phthalate/giyeol resins eshi it poor solublltty charac-
tencctcs. Modification with oils and reaf-is as veil as vising more than one
alcohol or acid viii upgrade the resin proNrties to the desired l.v.l.(2633
Input materials for these processes are listed afl Table 31.
M,dtfier. and blending agents are added to alkyd resins to provide
desired properties, including better hariness, faster drying speed, tough-
ness, corrosion and chemical resistance, heat resistance, and improved color
ri•tentton. Modifiers are typically added during alkyd preparation. Ilend—
ing agents cannot withstand the high temperatures of th. preparation step,
usually over 200’C, md are added after the alkyd is produced. Table. 32
and 3) give the effects of various modifiers arid blending agents, ?.spec—
tlvely, on alkyd resin properties.
Aikyd resins which are fabrtiated into molding compounds are usually
combined with fillers. Asbestos, sisal fiberi, cellulose fibers, synthetic
fiber. (such es polyeste, nylon, or acrylic), or glass fibers are used.
Solvents, including toluene, xylene, and coal—tar naphthas,. may also be
combined vith the alkyd resin. Other additives used at. drying oils, pig—
merits, and thixotropes. Organic acid salts of cobalt, lead, and manganers
may be added to enhance resin drying.
104
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TABLE 30. TYPICAL OPERATING PARAMETERS FOR ALKYD RESIN
PRODUCTION PROCESSES
Process Temperature Reaction Time
Alcoholysis Method 210 — 260°Ca 5 — 16 hours
Fatty Acid Method 210 — 280°C 5 — 16 hours
awith catalyst. Without a catalyst, reaction temperatures must exceed
280 3 C.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
105
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TABLE 31. TYPICAL INPUT MATERIALS Fr)R ALKYD RESIN PRODUCTION PROCESSES
Function Compounds
Polybaeic Acids Adipic acid
Azelaic acid
Camphoric acid•
Chiorendic anhydride
Citric acid
Cyclopentadiene
Diallyl phthalic acids and
anhydrides
Dimerized fatty acid
Fumaric acid
Clutaric acid
Hexahydrophthalic anhydride
Isophthalic acid
Maleic acid
Maleic anhydride
Phthalic anhydride
Pimelic acid
Sebacic acid
Succinic acid
Tartartc acid
Terephthalic acid
Tetrachlorophthalic anhydrida
Tetrahydrophtnaljc anhydride
Trieelliti anhydride
Oils China wood
Coconut
Cottonseed
Dehydrated castor
Fish
Linseed
Oiticica
Safflower
Soya
Soybean
Sunflower
Tung
Walnut
(continued)
106
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TABLE 31 (continued)
Function Compounds
?lonobasic Acids Bem.oic acid
Fatty acids and fractionated fatty
acids obtained from oils
eleostearic
lauric
1 icanic
linoleic
lirvleic (conjugated)
linolenic
3 leic
ricinoleic
paliiiitic
stearic
p—tert—butylbenzoic acid
Synthetic saturated fatty acids
2-ethyl hezanoic
isodecanoic
isononanoic
isooctanoic
pelargonic
Tall oil fatty acids
Polyols (Polyhydric Diethylene 0 lycol
Alcohois) Dipentaerythrito l
Dipropylene glycol
Ethylene glycoi
Glycerol
Manni tol
Neopentylene glycol (2 ,2—di.ethyl—
1, 3—propanediol)
Pentaerythritol
Polyethylene glycol
Propylene glycol
Sorbi tol
Trimethylolethane (2—(hydroxy—
mathyl)—2—methyl—l ,3—propan diol)
Trimethyloipropane (2—ethyl—2—
(hydroxymethyl)—l ,3—propane—
diol)
(continued)
107
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TABLE 31 (continued)
Function Compounds
Modifiers Acid modifiers
Rosin
Benzoic Acid
Acrylonitrile
Amines
Amino resins
Epoxides
Formaldehyde.
Hydroxyl containing modifiers
Hydroxylabietyl alcohol
Isocyanates
Methyl aethacrylate
Phenolic resins
Polyamides
Resins and ester gums
Silicone.
Vinyl monomers
Styrene
Vinyl acetate
Vinyl toluene
31. n ing Agent. Amino resins
Calluluae nitrate
Chlorinated rubber
Catalysts Calcium acetate
Calcium hydroxide
Calcium naphthenate
Cerium naphthenate
Lanthanum naphihenate
Lime
Lithium salts
Lithium carbonate
Sodium bicarbonate
Sublimed litharge (PbO)
Free Radical Initiators Oxygen
Inert Gas Carbon dioxide
Mixture of 2 and N 2
Nitrogen
Sot rcea: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
108
-------
TABLE 32. EFFECT OF MODIFIERS ON ALKYD RESINS
Modifier ______________
Epoxides Improved adhesioq Poorer color reten—
Better alkali re istance tion
Better detergent Rapid chalking
resistance
Better solvent
resistance
Hydroabietul Better brushing Slightly more
Alcohol (Abitol, Reduces alkyd function— yellowing
trademark ality and acts as Slightly decreased
Hercules Powder gelation inhibitor durability when
Co.) Better solubility (in used, in excess
aliphatic solvent)
Better gloss
Better flow
Creater hardness
Isocyanates Better water resistance Greater ye luwing
Faster dry Toxicity problem
Better abrasion (in manufacture)
resistance
Phenolic Greater hardness More yellowing
Better water resistance Poorer stability
Better alkali
resistance
Better solvent
re3istance
p—tert—butylben— Reduces alkyd function— Pourer solubility
zoic acid 1 ality and acts as a Poorer flexibility
benzoic acid gidacton inhibitor
Greater hirdness
Higher viscosity
Faster dry
Improved color and gloss
Improved chemical
resistance
Rosin or Rosin Faster dry More yellowing
Ester Better brushing Decreased exterior
(reater hardness durability when
Better mar resistance used £n excess
Better adhesion
(continued)
109
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TA3LE 32 (continued)
Modifier taes vantaes
Silicones Inproved heat Higher cost
reP &stance Higher curing
Gr_ater hardness ter perature
More resistance to
thereal shock
Styrene, Vinyl— Faster dry Poorer •o1ven’
toluene, Methyl Improved color and resistance
Methacrylate, gloss
Acrylonitrite Improved color and
gloss retention
Improved chemical
resistance
Source: Encyclopedia of Polyme’ Science and Technology .
110
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TABLE 33. COATING PROPERTIES OF BLENDED ALKYDS
Blending Agent Ad antages aes
Cellulose Nitrate Faster dry Poorer ciurability
Better chemical Poorer flexibility
resistance Lover solids
Better soylent
resistance
Greater hardness
Chlorinated
Rubber Greater to :ghness and Poorer solvent
hardness rasistance
Better abraaio
resistance
Better chemical
resistance
Faster dry
Urea—formaldehyde
and Melamine—
fr,rma idehyde
7’. atns Better chemical Poorer flexibility
resistance Higher coat
Better color and Poorer adhesion
color retention
Greater hardness
Faster cure
Higher heat resistance
Source: Encyclopedia of Polymer Science and Technology .
111
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Inert gases nay be used in tbeae processes for several reasons. These
aparge. pro’iide more rapid reaction, more unifor, molecular weight distribu-
tion, fever side reav tLona, and better colors in alkyd resins in addition to
Increased safety.
Alcoholysis Method
The alcoholysis method is currently the most ommonly used process for
•tkyd resin production.(128j Alcoholizing triglyceride oils, such as soya
or linseed, are combined with either pentaerythritoi or glycol. When par-
tial esters are produced, the esterification is completed by the addition of
a dibasic. acid, such as phthalic anhydride. A typical recipe for production
of alkyd resins via alcoholysis includes’the folloving:(128, 154J
Material Parts by Wei ht
Glycerol (polyol, monomer) 533
Pbthalic Anhydride (polybasic acid, monomer) 296
Soybean Oil $43
Sublimed Litharge (catalyst) 376
The alcoholysis method, shown in Figure 8, nay be performed with or
without a catalyst. If a catalyst is nct ‘used, the reaction temperature
most be raised to 280°C or above.(154J Basic catalysts are used in snail
amounts (typically 0.902 moles catalyst pee kg of oil) o promote redistri-
bution of the fatty acid groups on the triglyceride oils. Alkali metal
hydroxides may be used, but they give the resin a dark color and render
alkyd films 5oTe water sensitive. Leadconpound, re the most efficient
catalysts. ‘Sublimed litharge (PbO) is used commercially since it gives a
faster esterfication rate, equivalent resin color, and higher resin viscos-
ity than calcium or lithium salts at a concentration of 0.01 to 0.03 per—
cent.(l7 i, 154) When a catalyst is used, the oil is heated first until the -
temperature reaches 225 to 250°C. The catalyst and polyol are then added to
the hot oil and this mixture is reheated to 230 to 250°C.
After the fatty acid groups have been redistributed, th. partial esters
prodãced coc.tain free hydroxyl groups. The dibasic acid is then added and’
the esterificatiom is completed at tenperat ires between 210 and 260 °C.
An azeotropic liquid (zylene), typically 3 to 10 percent of the batch,,,
nay be added to-the reactor to facilitate water removal. The ref luxed
vapore are then sent from the condenser to a decanter where the water is
removed and the solvent is recycled to the reactor. If no solvent is used,
the water vapor may be vented to the atmo.phere.(154j
Conversion ‘is determined by the acid number or the viscosity of the
mixture.(247J When the react ton is completed, any solvent desired is added
to a mixing tank where th. bottoms stream containing the alkyd resin is fed.
The resulting resin mixture is then filtered and stored.
112
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Alconoltzing
Figure 8. Alkyd res.r production using the alcoholygi, method.
Sources: clopedia of Chenica] Technology , 3rd Edition.
Encyclopedia of Poiymer Science and Techno1og .
113
V t
AlkTd
Rs in
-------
Fatty Acid Method
The faLty acid method Is the second of two processes used to manufac-
ture alkyd resins. This process allows greater freedGm of formulation than
does the alcoholyqis method since a wider range of fatty acids are available
for reactions of this type.(128J In th!s roceas, presented in Figure 9,
the entire charge of raw materials is fed into the reactor where an inert
gas is used to provide a safe atmosphere for the reacti’ n. T 1l oil, pelar—
gonic acid, or 2—ethyihexanoic acid are most commonly wed. If both an oil
and a fatty acid are used, the alkyd coating resin produced exhibits more
rapid top drying and slower through drying than resins made by the alcoholy—
sis method.(154j
The temperature is typically raised to between 210 and 260C, although
temperatures up to 280’C have been used. The water generated by the conden—
sa:ion reaction is removed overhead from the ref lux condenser. An asso—
tropic liquid, sucti as xylene, may b used to promote water removal. The
ref luxed vapors are sent to a decanter where the azeotropic solvent ii
recycled to the reactor while the water is removed and treated. If no sol-
vent is used, the water vapors may be “anted to the atmosphere. Information
regarding a typical recipe for alkyd resin production ila the fatty acid
method was not found in the literature.
After the reaction proceeds to the desired end point as indicated by
either the acid number or viscosity, the bottoms stream containing the resin
is quickly fed into a Jacketed kettle containing a dilution solvent before
It is filtered and stored.
Energy Requirements
Energy requiremenra for thI. process were not found in the literature
consulted.
ENIRONMENTAL AND WORKER HEALTH CONSIDERATIONS
There are seven compound. used in alkyd resin production proressing
which have been listed as hazardous under RCRA: acrylonitrile, formalde-
hyde, maleic anhydride, methyl methat.rylate, phthalic anhydride, toluene,
and xylene. The solvents used in alkyd resin production are very volatile;
therefore, solve’ t reflux washes are roused and recovered b7 distillation.
Caustic washes used in kettle cleaning are also reused until th. caustic is
spent. ( 128 j
Alkyd resins are typically carried to high conversions. Removal of the
water generated by’ the condensation reaction force. the resin to complete
polymerization, making the reactor vent most suspect for fatty acid, oil,
polyol, and polybasic acid emissions. Recycl ng the solvent and other
nonwater vapors to the reactor also serves to reduce emissions from the
downstream vents. Overall system losses for all streams is reported to be 3
to 10 pecent. [ 154J
114
-------
Figure 9. Alkyd resin production using the fatty acid method.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
V. t
AUYD
aEs1I
115
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4.5.1 Worker Distribution and Emissions Release Points
Worker distribution estimates have been made by correlating major
equipment manhour requirements with the process flow diagrams in F l gures 8
d. d 9. Estinateg for both the alcoho ysis process and the fatty acid method
are shown in Table 34.
The cicined process conditions associated with alkyd resin production
mtnlmi e employee exp)sure potential tohaz mrdous cheuical subatanc.s and
physical agents. However, fugitive eMissions from the sources listad in
Table 35 and from leaks in pump and compressor seals, valves, and drains may
result in idevated workplace levels of fatty acids, polyols, polybasie
acids, solvents and particulate matter (nuisance dust). Available toxicity
information for major cortaminants is given in the Health Effects discus-
sion below and summarized in Table 10 in Section 1 of this documeit.
The additives used in alkyd molding resin formulation vary with product
specifications. Asbestos, a known human carcinogen, is commonly used as a
-einforcing agent. Chromiun— and lead-based organic acid salts may be used
as drying agents. Toxicity irf ,’mation about these and other additives may
be found in IPPEU Chapter lOb.
Employees in alkyd resin production may be exposed to inert gases (i.e.
carbon dioxides or nitrogen) which are used to ennance reaction time and
color development. Such gases are simple asphyxiant. which are potentially
nazardous because they reduce the available oxygen in tse atmosphere.
Maintenance employees risk overexposure to sodium hydroxide, which is
used periadically to clean polymerization reactors. Sodium hydroxide is
extremely irritating to the skin and mucous membranes, and even shu:t
periods of overexposure can rasult in severe chemical burns.
Health Effects
Sufficient data do not exist in the available literature with which to
evaluate the health effects of exposur. to more than tvo—tliirde of the
typical input materials in the production of alkyd resin, excluding oils and
inert gases. The chemicals for uhich eutficient data do exist ‘include
several highly toxic substances and chemicals noted for mutagenic and/or
teratogenic potential. Although a number ‘of input material. ar. reported
t’iworlgentc agents, only two; the modifier acrylonitrile, and the catalyst
lead oxide, are suspected human carcinogens. Styrene, also a mo-lifter in
the process, and maleic anhydride, a polybseic acid, also may.pose a sir
nif leant health risk to plant employees due to high toxicities and other
properties. The reported health effects of exposure to these three sub-
stances are summarized below.
Acryloriitrile , a sus .ected human carcinogen 11071, causes irritation of
the eyes and nose, weakness, labored breathing, dizziness, impaired Judg-
ment, cyanosi , nausea, and convulsions In humans. Nutagentã, teratogenic,
and tumortgentc effects have been reported in the literature, The OSU air
staidard is 2 ppm (8 hour TWA) with a 10 ppm ce lling.(69J
116
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TABLE 34. WORKER DISTRIBUTION ESTIMATES FOR ALKYD RESIN PRODUCTION
Process Unit Workers/Unjt/8—hour Shift
A1coho1y is Batch Reactor 1.0
Reflux Condenser 0.125
Decanter 0.25
Batch M.xer 1.0
Fatty Acid Method Batch Rea:tnr 1.0
Ref lux Condenser 0.125
Decanter c.zs
Batch Mixer i.o
117
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TABLE 35. SOURCES OF FUGITIVE EMISSIONS ?ROM ALKYD RESLN MANUFACTURE
Process
Fatty
Source C)astjtuent Acid Alcoholyuj
Reactor Vent Fatty Acid (Oil) X X
Polyol X X
P01 7 b .ic Acid X X
Solvent Ra
Modifiers za Xe
Ref lux Condenser
Vept Polyol I I
Polybasic Acid X I
Solvent Xe
Modifiers x c
Mixing Tank Vent Dilution Medium I I
Blending Agents xc xc
Alcohol Pecovery
Column Vent Polyol X I
Solvent xc xc
Modt’L.rg xc
ajf used.
118
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Lead oxide is a suspected human carcinogen which cause severe c. ute and
chronic toxicological effects. Acute overexposure results in fatigue,
colic, anemia and neuritis. Chronic overexposure can produce anemia and
damage to the liver, kidneys, and nervous system. Instances of sterility,
fetal toxicity, and isutagenicity have been reported. [ 170J The OSHA air
standard is 0.05 mg/rn 3 (8 hour TWA) (as lead). [ 69J
Maleic Anhydrlde is highly toxic by ingestion and inhalation (242] and
is a powerful irritant to the skin and eyes.(149J Inhalation can cause
pulmonary edema (149]; other effects of exposure include conjunctivitis,
corneal damage, cough, bronchitis, headache, abdominal pain, nausea, and
vomiting. [ 238J Animal data also suggest that maleic anhydride is a tumori—
genie agerit.(233J The OSHA air standard is (.25 ppm (8 hour TWA).(67]
Styrene has been linked with increased rates of chromosoma]. aberrat..,ns
in persons exposed in an occupational setting. [ 107] Animal test data
strongly support epidemiological evidence of its mutagenic potential. [ 233]
Styrene also produces tumors and affects reproductive fertility in labora-
tory animals.(233J Toxic effects of exposure to styrene usually involve the
central nervous system. [ 233] The OSHA air standard is 100 ppm (8 hour TWA)
with a ceiling of 200 ppin.(67J
Air Emissions
Fugitive VOC emission sources for alkyd resin production are listed in
Table 35. These emission sources are all vents, including condenser vents,
reactor vents, and mixing tank vents. Control technologies available for
theBe vent streams include: [ 285]
• Venting the stream to a flare to incinerate noncondensible
hydrocarbons; and/or
• Venting the streae to blowdown.
Other sources include fugitive VOC emissions which result from flanges,
valves, pumps, compressors, relief valves, and agitarors. Althoguh equip-
ment mc.dification is helpful in reducing VOC emissions from these sources in
so,ne cases, a regular inspection and maintenance prograu is the best control
available.
There are no sources of particulate emissions from the alkyd resin
production process.
Wastewater Sources
There are only two sources f vas ewater associated with alkyd resin
production: water generated by tne condensation reaction used to manufac-
ture the resin and routine cleaning water. These wastewater streams may
contain trace amounts of alkyd resin, regardless of which process is used.
Wastewater from the alcohnlysis method may contain small amounts of catalyst
residues. The caustic cleaning water is reused until the caustic is spent
119
-------
efore being sent to wastewater treatment, flare are no data listing the
values for vastewater generation or characteristic. in the literature
consulted.
Solid Wastes
The solid wastes generated by this process are meetly alkyd resins.
Solid waste streams result from substandard product which cannot be blended
as well as product lost during reactor cleaning, product blending, and
spillage.
Eavironmental Regulation
Effluent limitations guidelines have been set for the alkyd resin
industry. EPT, RAT, ard NSPS call for the p8 of the effluent to fall
between (.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New sourc performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, ezcept in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The followi ig compounds are listed as hazardous wastes (46 Federal
Register 27476, 20 Nay 1981):
Acrylonitrile — U009
Pormeldehyde — U122
Maleic anhydride — Ul47
Methyl .ethacryla’e — U162
Phthalic anhydride — U190
Toluene — U220
Zylene — U239
All disposal of these compounds and alkyd resins which contain residuals of
these compounds must comply “ith the provisions set forth in the Resource
Conservation and Recovery Act (RCRAj.
120
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SECTION 5
AMINO RESINS
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Amino resins are produced by reacting formaldehyde and a compound con-
taining aq amino group (—NH2); melamine—formaldehyde and urea—formaldehyie
are the major amino resins produced. Amino resins may be manufactured in a
variety of forms: as liquids, spray dried solids, or filled molding com-
pounds. Although the end uses differ, there is essentially only one process
used for producing these compounds.
Amino resins are used in a wide variety of applications. Their ras. s—
tance to heat, solvents, chemicals, and discoloration is combined with
extreme surface hardness, making amino resins an excellent choice for use
in adhesives, lamination, paper coating, dinnerware, and molding compounds.
Table A—5 in Appendtx A presents typical pro?erttes of filled amino
resin molding compounds. Fillers impart strength and moldability, improve
dimengional stability, and reduce internal stresses. Coating, laminating,
and adhesive resins form hard, solvent resistant bonds or finishes.
Pt opertieg for these resins are formulation specific; that is, specific to
end use requirements.
There are four major amino resin products: molding resins, coating
resins, laminating resins, and adhesive resins. Adhesives represent the
largest single market for amino resins, for which the uses include plywood,
chipboard, and sawdust board manufacture.(279J Other amino resin applica-
tions include textile coati.igs, automobile tire adhesives, paper coatings,
molded dinnerware, automotive topcoats, and buttona. [ 279J
I NDUSTRY DESCRIPTION
In 1980, awno resin sal’s ac’ ounted for 3.7 percent of the total sales
for the plastics industry. [ 653 The aminu resin industry is comprised of 52
producers with 112 sites diatributed between 21 states. There is a prepon-
derance of plants in the southeast and great lakes areas (EPA Regioni IV and
V). Of the 112 sites, 73 sites produce melamine—formaldehyde recins, 105
sites produce urea—formaldehyde resins, and 66 sited produce both. Major
U.S. amino resin producers are listed in Table 36 as veil as the amino com-
pound used for resin manufacture and resin end uses for each producer. The
capacities of the amino resin plants listed are not available in the
literature.
121
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TABLE 36. U.S. AMINO RESIN PRODUCERS
Urea— Melamine—
Formal— Formal-
dehyde dehyde
Produc. r Resins Resire End Uses
American Cyanamid Co.
Formica Corp., subsidiary
Evendale, OH X Molding cc npounds,
Industrial Chemicals Division fibrous and granu—
Kalamaioo, MI X lated w iod, ply—
P’obile, AL X X vood, -aminites,
Uallingford, C? X X protec_ive coat—
Organic Chemicals Division in s, paper treat—
Charlotte, NC X X ing, textile
treating
American Hoechst’Corp.
Industrial Chemicals Division
Mow.t Holly, NC I X Laminates, textile
treating
Apex C. eaica1 Corp., Inc.
Elizabethport, NJ X Paper treating,
textile treating
Auralux Chemical Associate,. Inc.
Hope Valley, RI I I Textile tresting
The Bendix Corp.
Friction Materials Division
Green Island, NY I Paper treating,
oth.r
Borden Inc.
Borden Chemical Division
Adhesive, & Chemicals
Division East
Denopolib, AL I Fibrous and gran—
Diboll, TX X I ulated wood, ply—
Fayettevilla, NC X wood, laminate,,
Louisvtlle, KY I pap.r treating,
Sheboygan, Vt I I other markets
(continued)
122
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TABLE 36 (continued)
Urea— Melamine—
Formal— Formal-
dehyde dehyde
Producer Resins Resins End Uses
Borden Inc.
Border. Chemical Division
Adhesives and Chemicals
Division West
Freemont, CA X
Kent, WA X X
La Grande, OR X
Missoula, MT X
Springfield, OR X
Cargill Inc.
Chemical Products Division
Carpentersville, IL X X Prott ctive
Forest Park, GA X X coatings
Lynwood, CA X X
Celanese Corp.
Celanese P1a tics and Specialties
Co. Division
Celanese Speciality Resins
Division
Louisville, KY X X
Chagrin Valley Co. Ltd.
Nevamar Corp., subsidiary
Odenton, ?W X Laminates
Clark Oil & Refining Corp.
Clark Chemical Corp., subsidiary
Blue Island, IL X X
C.N.C. Chemical Corp.
Providence, RI X X Textile treating
Commercial Products Co., Inc.
Hawthorne, NJ X
Consolidate 1 Papers, Inc.
Consoveld Corp., subsidiary
Wisconsin Rapids, WI X Laisinates
(continued)
123
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TABLE 36 (continued)
Urea— Melanine—
Formal— Formal-
dehyde dehyde
Producer Resins Resins End Uses
Cook Paint and Varnish Co.
Detroit, MI I I Protective
Cock Industrial Coatings Co. coatings
Ncrth Kansas City, MO X I
Crown—Metro, Inc.
Greenville, SC I K
Dan River, Inc.
Chemical Products Division
Da vtlle, VA K I Textil, treating
DeSoto Inc.
Garland, TX I Protective
coatings
Dock Resins Corp.
Linden, NJ K K Protective coat-
ings, textile
treating
Eastern Color and Chemical Co.
Providence, RI I Textile treating
General Electric Co.
Engineered Materials Group
E1 ectromaterja1s Busineer
Department’
Coshocton, OH I Laminates
Schenectady, NY I
Georgia—Pacific Corp.
Chemical Disision
Albany, OR I I Fibrous and granu—
Columbus, OH K K laced wood, ply—
Conway, NC K I wood, paper
Coos Bay, OR I I treating
Crossett, AR K K
Eugene, OR K K
Louisville, P K X
(continued)
124
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TABLE 36 (continued)
Urea— Melamine—
Formal— Formal-
dehyde dehyde
Producer Resins Resins End Uses
Georgia—Pacific Corp. (Cont.)
Chemical Division
Lufkin, TX X X
Newark, OH X X
Peachtree City, CA X
Port Wentworth, GA X X
Richmond, CA X X
Russellville, SC X X
Tayloraville, MS X X
tlkiah, CA X X
Vienna, GA X X
Getty Oil Company
Chembond Corp., nubsidiary
Andalusia, AL X Fibrous and granu—
Springfield, OR X X lated wood,
Winnfield, LA X X plywood
Guardsman Chemicals Inc.
Grand Rapids, MI X X Protective
coatings
Gulf Oil Corporation
Gulf Oil Chemicals Co.
industrial Chemicals
Division
High Point, NC X
West Memphis, AR X
Milmaster—Oriy,c Group
Lyndhurst, NJ X
Manna ChemJcal Coatings Corp.
Columbus, OH X X Protective
coatings
Hetcules, Inc.
Chicopee, MA X
Hattiesburg, MS X
Milwaukee, WI X
Portland, OR X
Savannah, GA X
(continued)
125
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TABLE 36 (continued)
Urea— Melamine—
Formal— Formal-
dehyde dehyde
Producer Resins Pesine End Uses
H & N Chemical Co.
Totowa, NJ X
LibbY—Owens—Ford Co.
LOP Plastic Products,
subsidiary
Auburn, ME X X Laminates
Mobil Oil Corp.
Mobil Chemical Co. Division
Chemical Coatings Division
Kankakee, IL X X Protective
Aoatings
Monsanto Co.
Monsanto Plastics and Resins Co.
Addyston, OH K Molding compounds 1
Chocolate Bayou, TX K fibrous and granu—
Eugene, OR K lated wood, ply—
Santa Clara, C K K wood, laminates
Springfield, Pt K K protective coat-
ings, vapor treat-
ing, textile
treating
National Casein Co.
Chicago, IL K
Tyler, TX K
National Casein of CA
Affiliate of National Cagein Co.
Santi Anna, CA X
National Casein of NJ
Affiliate of National Casein Co.
Adhesives Division
Riverton, ki K
National Starch & Chemical Corp.
Proctor Chemical Co., Inc.,
subsidiary
Salisbury, NC X K Paper treating,
textile treating
(continued)
126
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TABLE 36 (continued)
Urea— Melamine—
Formal— Formal-
dehyde dehyde
Producer Resins Resins End Uses
Perstorp Inc.
Owned by Perstorp, AS Sweden
Florence, MA X X Molding compounds
Plaskon Products, Inc.
Toledo, OH X
Plastics Manufacturing Co.
Dallas, TX X X Molding compounds,
lasinates
PPG Industries Inc.
Coatings and Resin Division
Circleville, OH X Protective
Oak Creek, WI X X coatings
Reichhold C. emicals Inc.
Andover, PiA X X Fibrous and granu—
Azusa, CA X lated wood, ply—
Detroit, I X X v od, protective
Moncure, NC X coatings, paper
South San Francisco, CA X X treating, textile
Tacoinii, WA X X treating
Tuscaloosa, AL X
White City, OR X X
Vacuum Divi ton
Niagara Falls, NY X
Scott Paper Co.
Packaged Products Division
Chester, PA X X Paper treating
Everett, WA X
Fort Edward, NY X
Marinette, WI X
Mobile, AL X X
Southeastern Adhesives Co.
Lenoir, NC X
(continued)
127
-------
TABLE 36 (continued)
Urea— Melamine—
Formal— F’nmal—
dehyde dehyde
Producer Reiins Resins End Uses
The Stanth rd Oil Co. (Ghio)
Sohio Industrial Pro.3ucts
Co. Division
Dorr—Otiver, Inc. Unit
Niagra Falls, NY X
5un Chemical Corp.
Chemicals Group
Chemicals Division
Chester, SC X X Paper treating,
textile treating
Sybron Corp.
Chemical Division
Jersey State Chemical Co.
Division
Haledon, NJ X X Protective coat-
ings, textile
treating
Synthron, Inc.
Ashton, RI X I Textile treating
Mor.ganton, NC I I
Tyier Corporation
Reliance Universal Inc.,
subsidiary
Speéialty Chemicals and
Resins Division
Louisville, KY I I
United Merchants and Manufac-
turers, Inc.
Vaichem Chemical Division
Langley, SC X I Textile treating
U.S. Oil Company
East Provtder 1 ce, RI I I Textile treating
Southern U.S. Chemical Co.,
In’ ., subsidiary
Rock Hill, SC I I
(continued)
128
-------
TABLE 36 (continued)
Urea— Melamine—
lot sal— For ,ial-
dehyde tiehyde
Producer Resins Resins End Usei
Valapar Corporation
McWhorter, Inc., subsidiary
Baltimore, MD X X
Westinghouse Electric Corp.
Insulating Materials Division
Manor, PA X Laminates
West Point—Pepperell, Inc.
Grifftex Chemical Co., subsidiary
Opelika, AL X Textile treating
W.yerhaeuser Co.
:larshfield, WI X Fibrous and granu—
lated vood,
plywold
Sources: Chemical Economics Handbook , updated annually, 1980 data.
Directory of Chemical Producers , 1982.
129
-------
The amin3 resin industry is consumer oriented. Adhesive., coatings,
and laminates are used in the constructiGn, transportation, and consumer
goods industries. Urea—formaldehyde resin production peaked in 1979 at
L21,600 metric tons, then fell to 529,500 metric tons in 1980. This
production level, however, represents an 11 percent coupound growth rate
from 1975 to 1980.(65J Melamine—fórmaldehyde resins have not fared as
veil. After a 1978 production peak of 91,800 metric tons, 1980 production
fell to 75,900 metric tons which 1. 9,400 metric tons below the 1976 pro-
duction level. Compound growth for melamine—forma!dehyde ream production
from 1975 to 1980 was 7.7 percent.(65J Total amino resin production for
1981 was 645,000 metric tone.(143J
PRODUCTION AND END USE DATA
In 1981, U.S. production of amino resins totaled 645,000 metric tons.
Amino resins have many uses, including:(136, 279, 288J
• Adhesives for the manufacture of plywood, particle board, chip
board, and sawdust board, ann furniture assembly clues;
• Adhesives to bond rubber to tire cord an binders for metal
coatings;
• Protective surface coatings, durabl baked enamels f or applicance.,
wood furniture coatings, and automotive primer and topcoats;
• Textile treating;
• Coatings for floor finishes, metals, primer coats, and paper
coating;
• Decorative laminated plastic sheets for counter and table tops;
• Flexible backing on carpets iind Irapertes;
• Wiring devices, including circuit treakers, wall plates, end
receptacles;
• Molded products, including cutlery and telephon, handles, ceiling
panels, staircases, bottle and jar caps, dinnerware, buttons,
cosmetic caps, electric blanket control housings, toothpaste
tube inscrts, toilet seats, housings, knobs, handles, ashtri ys,
lavatory bowls, utensil handles, electric shaver housings, mixing
bowls, and appliance components;
• Automotive parts, including ignition plugs and connector plug
inserts;
• Foam for insulation in commercial buildings, private reiidences,
.hlp., air frames, and tunnels, and for supporting florel displays;
• Oil absorbers for ocean spills;
130
-------
• Dreesirg for wounds;
• Leather tanning;
• Cure of other resins; and
• Plant nutrients and conditioners.
Tabie 37 lists amino resin consumption by market, and Tables 38 and 39 pre-
sent consumpt’on of urea—formaldehyde and elamine—formaldehyde molding
resins, respectively.
PROCESS DESCRIPTIONS
Amino resins are produced by essentially one process. Variations in
the process enable the production of the variety of products which consti-
tute the aa .i o resin industry. vor example, coating resins are manufactured
by adding methanol or butanol to the reactor; these compounds then contrib-
ute to the condensation reaction to form the desired resin. Adhesives are
the largest single segment of the amIno resins market, and most of the adhe—
siveq produced are used for the manufacture of plywood, particle board, and
other wood products.
Amino resins are produced in a two step reaction. In the first step,
intermediate compounds are formed. Intermediate formation may be catalyzed
by either acidic or alkaline conditions. Reactions for the formation of
ureaforr aldehyde and melamine—formaldehyde i. termediates are shown below:
Urea—Formaldehyde
o 0 0
I I I
H 2 11-C—11H 2 i Il -C -H I f 2 1 C-NHCH 2 OH
?otmald.hydl MonomathyLOtursa
- 0 0
I I I
t 1 2 If-C-IMCH 2 OH • N-C-N WIOCH 2 NHCNHCH 2 OH
ionom.thyLoLurIa Focm.ld.iyds Dtm.thylOlUCeI
le1amine—Formaldehyde
II N HON,C1IN
2
C-N 0
I
N C- N M 2 • 311-C-N N C-NMCPI 2 OH
/ Forsa dshyd. ‘ /
C.,. C.,.
/ ,
HON 2 CNN
Metamin. ?rai..thytoL l.lai’etne
131
-------
TABLE 31. 1981 PATTERN OF NSUMPTION FUR AMINO RESINS
Market Thousand Metric Tons
Bonding and Adhesive Resins for:
Fibrous and Gra u1ated Wood 427
Laminating 16
Plyw,od 36
Molding Compounds 39
Paper Treatment and Coating Resins 37
Prote tive Coatings 36
Textile Treatment and Coating Rrnsine 39
Export 10
Other 5
TOTAL 645
Source: Modern Plastics , January 1982.
132
-------
TABLE 38. 1981 MOLDING POWDER MARKETS FOR UREA—PORMALDEHYDE RESINS
Market Thousand Metric Tons
Closures 6
Electrical 15
Oti r 1
TOTAL 22
Source: Modern Plastics , January 1982.
TABLE 39. 1981 MOLDING POWPER MARKETS FOR )IELAMINE-FORMALDEHYDE RESINS
Market Thousand Metric Tons
Buttons 1
Dinnerware 14
Sanitary Ware 1
Other 1
TOTAL 17
Source: Modern Plastics , January 1982.
133
-------
HON 2 CIIII (NOH 2 C) 2 N
C-N 0 C-N
S S S %
N C-NNCH ON + iH C —II N C—N(C)I..ON) 2
/ 2 FoceaLdehyde ‘ /
C -N C-N
I I
HON 2 CNN (KON 2 C) 2 N
?r aethy1o1 Nelaazn• Hexansehylol M.laaini
The second reaction step results in the formation of low molecular weight
polymers by several condensation reactions. These reactions form methylene
bridges (—CE 2 —) between a methylol and an amino group and either a methy—
lene bridge (— 2—) or an ether linkage (—C0 2 -O—cH 2 —) between two
methylol groups. Example condensation reactions are shown below:
(1) Methylol and amino group methylene bridge
General: RNdCN 2 OI I + flNNCH 2 NHR • 1120
1 10C 1 1 2
0 ___ \o
Urea: N 2 N-C-10C1 1 2 011 • H0CN 2 NN -( —NIIC,f 2 O,, 0 I—C-NNCJI 3 ON • 1120
Nononsehylotur.. Dtethy o1ugea 1 1 2 N-C-NHC I I 2
Melamine (Product) :
NI NNCHON
2 1 2
CN N-C
S I
N C-NNCII,IIH-C N
* S S 5
C-N N-C
112 11 NNCN 2 0II
134
-------
(2) Two methylol groups methylene bridge
General: + H 2 0 + HCI4O
0 0 0 0 0
I I I p
Urea: H 2 N—C NHCq 2 O + HOCH 2 NH-C -NNCH 2 OH - H 2 N-C-NHCH 2 MN_C_NHCH 2 OII + H 2 0 + H—C-fl
Monomethyjolurea OLmethylolurea
Melamin. (Product):
NOH C 4N NNCH ON
2 . , 2
C —N NC
I
N C-NNCN NH-C N
i 2 ,
C-N N-C
I
HOH CIf N NHCN OH
2
(3) Two methylol groups ether linkage
General: RMHCII 2 0N • HOCH 2 NHR’— RNHCH 2 OCHNNR. • K 2 0
O 0 0 0
I p
Urea: N 2 N-C—NH-CP1 2 0 1 1 • I0CN 2 NN C_NN.CN 2 OH * N 2 N C—NHCN 2 _0..CN 2 NH..CNHCH 2 0H • H 2 0
ionomsthylolur.a DLm•thytolur.a
M.l.m*n. (Product):
NON CHN NHCH 2 OH
2 ..
C.N NC
I I
N C-NHCH,-O..Cn 1 Nfl..c N
% I £ ,
C-N N-C
HON 2 CHN NNCHq ON
Ether
135
-------
? 20 l
N-C-N’
bIO-C 12’ CR2-Gil
+2 120
Urea—formaldehyde and melamine—fornaldehyde coating resins incorporate
an alkyl group to increase the realm’s solubility in o!gantc solvent. and
render it more stable for iacrea8ed shelf life. The hydrogen of the
isethylol group i replaced with n alkyl group (alkylation) from either
methanol or butanol. The reaction is catalyze4 by acids and carried out
with excess alcohol. The excess alcohol help. suppress condensation
reactions which compete with the alcohol reaction. Folloving are examples
of the alkylat ion:
Urea—Fnrma Idehyde
IIO-CB2 ? 1 CR2
+ aoii
U0-øI2 ‘CR2-CR
where 1 includes C R 3 and CR 3 CH 2 CH 2 Cg 2 .
+2 w 20
Urea—formaidehyde resin. are essentially monomeric with five or aim
units in a polymer. Melamine—formaldehyde resins have 20 to 30 units per
polymer., This difference is due to urea having two sites which react,
making it difuncctonal, while melanin. contains three active sites,
rendering it trifunctional.
Tablea 40 and 41 list typical input material. and operating parameters
for the four types of amino resins produced. Other input material, used such
as fillers, cure catalysts, stabilizers, and self—exriiguighing agent. for
foam, such as polypropylene, are Listed in Table 42.
Adl e ives
Adhesive resins ace produced using either elamine, urea, or both
compounds. Melamine is more costly but produces more durable glue which
Melamine—Formaldehyde
where N includes CR 3 and
136
-------
TABLE 40. TYPICAL INPUT MATERIALS TO AMINO RESIN PRODUCTION
IN ADDITION TO UREA, MELAMINE, AND FORMALDEHYDE
Modi— Mold
fying pH Curing Cata— Release
Product Alcohol Agent Filler Buffer Dyes lyst .! .
Adhesives x X X
Coatings xa x
Laminates X
Molding
Resins X X X X X
aFor production.
1 ’For dilution.
TABlE 41. TYPICAL OPERATING PARAMETERS FOR AMINO RESIN PRODUCTION
urea: Melamine:
Reaction Formaldehyde Formaldehyde
Product Temperature Time Ratio Ratio
Adhesives 20°C 7.5 8 hours 1:1.5—1:2.0 1:3
ga
Coatings 24_66°Cb 7_gb 4 hours 1:1—1:2 1:2—1:6
Laminates N/A 7—10 N/A Not used 1:2
Molding
Resins 24_66°Cb 7—8b 4 hours 1:1.3—1:1.5 1:2—1:3
50 —60°CC 6.0-
6.5C
N/A — Not available.
apo1 erjzatjon pH starts at 7.5—8.0, is reduced to 6.O then
raised to 8.0 when the reaction is completed.
bpolymar zation
CMLXIflB.
137
-------
TABLE 42 • INPUT I’tATERIALS AND SPECIALTY CHEMICALS USED IN AMINO RESIN
MANUFACTURE (IN ADDITION TO UREA, MELAMINE, AND FORMALDEHYDE)
Function Compound
Heat Resistance Additive Acrylamide
Hafnium chloride
Melamine
Zirconium chloride
Impact Resistance Addftive Ammonium polysulfide
Glycidyl methacrylate
Odor Reducing Additive Methylen. acetoacetate
Methylene phosphate
Crosslinking Agent bipropylene glycol
ternal hardener 2 —aiiino—2—ethyl—l,3—propane—
diol hydrochloride
Self—Extinguishing Agent Polypropylene
Catalyst Neutralizer Tricalcium phosphate
Triethanolanjee
External Hardeners Chlorides of organic amides
Formic acid
Phthalic acid
Pyrridine monochioroacetic
acid
p—toluene aulfonic acid
Sulfates of organic amides
Sulfites
Sodium disuif it.
Sodium sulfite
Sulfur dioxide
Weak organic acids
Cure Retardant Ammonia tetramine
Ilexamethyl tetramine
Buffer Sodium format.
(continued)
138
-------
TABLE 42 (continued)
Function Compound
Fillers Asbestos
a—cellulose
Bleached kraft cellulose
Bleached wood pulp
Cellulose filler
Cereals
Chopped cotton yarn
Chopped nylon
Coconut shell powder
Cotton linters
Diced cotton fabric
Dimethyl formnmide
Purfurylaldehyde
Class fiber
Ground silica
Maize
Mica
Potato, tapioca or wheat
starches
Powdered phenolic molding
waste
Retch (a weed in cereals)
Root flour
Rye
Rye flour
Sulfite cellulose
Walnut shell powder
Wood flour
Sizing Agent Wax
Modifying Agent Amide polymer
Carboxyl polymer
Rydroxyl polymer
Craze Resistance Agent Benzyl alcohol
Furfuryl alcohol
Mold Release Agent Calcium stearate
Dicresyl glyceryl ether
Glyceryl monostearate
Magnesium stearate
Oxidized paraffin vax
Su’.fonatel castor oil
Z, ’ stearate
(continued
139
-------
TAELE 42 (continued)
Function Compound
Flow Control Agent Melamine—formaldehy spray
dried resin
Urea—formaldehyde spray dried
resin
Water
Stabilizer Diethanolamine
Hexamethylenetetramina (HMIA)
Thiethanolamima
Curing Catalysts Ammonium chloride
Ammonium sulfate
Dichiorohydrin
Hexamine thiogyanate
Trimethyl phosphate
Zinc sulfate
Ziac sulfite
Plow Promoter, and Plasticizers Aromatte ,noethers of
glycerol
o — methyl—D —g lucos ide
Beniamida
ptoluenesulfonamjde
p—toluene ,ulfona j
formaldehyde
Pigments Azo pigments
Cadmium suif ides
Hansa yellow.
Iron oxides
Phtha ocyanine blues
Titanium dioxide
Ultramarine.
Zinc oxides
Comonomers 3enzoguana.ine
Dihydroxyethy1en r
Phenol ‘
Vinyl acetate
Sources: Joha P. Mats, Amino 1959.
Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology.
Beat Meyer, Urea—Formaldehyde Resins, 1979.
Modern Plastics Enc yclopedia , 1981—1982.
C. P. Vale and V. C. K. Taylor, Aminoplagtj s , 1964.
140
-------
is waterproof, rendering it useful for exterioc and sarine applications.
One alternative to lower the cost of using melamine is to combine melamine
and urea in the same formulation.
Adhesives are produced by reacting formaldehyde with urea or melamine
under carefully controlled conditions. Fillers are often added to the glue,
as are acid catalysts to harden the glue after application and furfuryl or
benzyl alcohol which renders the glue resistant to cracking and crazing.
Urea glues are sold as a liquid resin with a separate powdered hardener
which co nains a catalyst, a pH buffer, and a cure retardant.
As illustrated in Figure 10, adhesive manufacture begins with formalde-
hyde and the amino compound being fed into a stirred tank reRctor where the
pH is carefully controlled. Reactor inputs for the production of adhesive
amino resins typically include: (281J
Material Parts y jJht
Urea (amino monomer) 273.0
Formaldehyde (30Z) (monomer) 908.7
Boric Acid (catalyst) 45.4
Sodium Hydroxide (pH adJustment) small aI’lount
The water produced by the condensation reaction is removed in a separator
and the resulting resin mixture is filtered. Additives used in the apectfic
adhesive formulation desired are blended into the resin in a mixer before
the adhesive is subsequently sold in liquid form.
Amino adhesives have low shrinkage, are craze resistant, and form thick
glue lines. Urea adhesives are sold as a liquid resin with a separate
powdered hardener while aelamine resins are sold as a liquid resin with the
hardener suspended in the liquid. The solids content of these resins ii 50
to 60 percent.
ne
Coating resins are manufactured using an alcohol, such as n—butanol or
methanol, in an alkylation reaction. This a1kyla ion step renders the
liquid product soluble in the common orgcnic solvents used in most coating
processes. Both urea and melamine r.sin . are used. Urea resins have poor
water resistance but cure rapidly while melamine resins are more costly, yet
exhibit better overall performance. If methanol is used in the alkylation,
the resulting coating is water soluble and is used in textile treating.
Amino resins create a hard, solvent resistant coating upon heating with
‘ydroxyl, carboxyl, and a iide polymer..
A. illustrate i in Figure 11, the amino compound and formaldehyde are
fed to a polymerization reactor to start the production process. The water
is removed in a seperator beforc the polymer mixture is filtered and diluted
with either methanol or butanol. An azeotrope may be formed i adding
xylene to the reactor which aids tn removing any remaining water from the
resin. The xylc.ne is not removed f roe the coatir. resin. Modifying ageecs
141
-------
Additive.
Vaut Veut
__ Vent
1 s1 .aine or Urea LTMIRI. SKPARA
ATICtI TOE MIXER
Water
I Liquid Adhesive Resin
Plgure 10. kaino adhesive resin production process.
Sources: Incyclopedja of Chemical Technology , 3rd EdttLo .
Encyclopedia of Polymer Science and Technolo Z.
Nodern Plastic. Encyclopedia , 1981—1982.
-------
Alcohol
Figure 11. Aalno coating resin production process.
Sour ea: Encyclopedia of
Encyclopedia of
Modern Plaitice
Cheeical Technology , 3rd E Ltton.
oly.er Science and Technology.
Encyclopedia, 1981—1982.
Ne1a ine or Urea
Vent
Modifying Agents
Vents
.1
Water
Liquid
Resin
Spray Dried Coating Resin
Vent
-------
(e.g., hydroxyl, carboxyl, or aside polymers) are added to the dilution
kettle to enable a hard, solvent resistant coating upon application of the
resin. If the resin is desired in liquid form, no further processing is
necessary; the resin content of the liquid ranges from 50 to 60 percent.
Dried resins are produced via spray dryin,. Typical quantities of input
material for the production of amino resin coatings were not found in the
literature.
Laminates
Laminating resins are based on melamine—formaldehyde products; urea is
not used. Melamine—formáldehyde resin laminates exhibit excellent hardness,
clarity, stain resistance, slid fveedou eros yellowing.
Laminating resin manufacture is presented in Figure 12. A typical pro-
duct ion recipe is as follows:
Material Parts by Weight
Melamine (aminà monomer) 100
Formaldehyde (37Z) (monomer) 133
Catalyst 2—12
Sodium Hydroxide (p11 adjustment) small amount
Formic Acid (pH adjustment) small amount
Plelamine and formaldehyde are combined in a mactot arid polyxerixed. Water
produced by the cond neation reaction i. removed in a separator before the
polymer mixture fs filtered. Laminating resin may be sold as a viscous
liquid or aa a dried resin following pray dry ing. spray dried resins
exhibit a longer shelf life than the syrups which hav a resin content of 60
to 65 percent. Ethanol or isopropyl alcohol may be added after the syrup is
manufactured for specific laminating uses.
Molding Resins
Both melamine and urea are used to manufacture molding rains. Fillers
are added to impart strength and moldability, improve dimensional stability,
and reduce internal stresses. Asbestos is used as a filler for compounds
requiring high arc, heat, and flame resistance and high dielectric strength.
Class fiber is used to give high impact strength, heat and arc resistance,
and good electrical properties. A typical produetton recipe for molding
amino resins is as follovs (236, 257J
Material Parts by Weight
Melamine (amino monomer) 100
Formaldehyde (37Z) (monomer) 133
Alpha Cellulose (filler)
Dyes, Pigments
The amounts of filler or dyes and pigments used were not found in the
Literature.
144
-------
Vent
Figure 12. Amino laminating resin production pr cess.
Spray Dried
Laminating
Resin
Liquid Laminating Resin
Sources: Encyclopedia of Chemical Te”hziulogy 1 3rd Edition.
Encyclopedia of Polymer .cience ai d rechnology.
Modern Plastics Encyc pedia , 1981—1982.
Vent
U’
Vent
-------
Molding resin production is depicted in Figure 13. Formaldehyde and
the amino compound are added to a stirred reactor to start the pr,duction
process. Water from the condensation reaction is separated from the polymer
mixture before filtration. The resin may be diluted with alcohol prior to
mixing where the fillers appropriate for the desired resin end use are
added. After mixing, the resin is screened, dried, and compounded in a ball
mill. Mold release 3gents, cataly,ts, dyes, and curing agents are added
before the formulated polymer is extruded.
Energy Requirements
No data were found giving the energy requirements for amino resin pro-
duction in the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH NSIDERATIONS
Urea-formaldehyde and melamine—formaldehyde resins are considered to be
nontoxic in the cured state. Uncured resins, however, contain a small
amount of free formaldehyde; therefore, care should be taken in the handling
and storage of these resins. Since most recipes for amino resins call for a
limiting amount of formaldehyde, the majority of the formaldehyde emission.
viii occur in the reactor vent and other upstream operations. Four input
materials have been listed as hazardous under RCRA: asbestos, formaldehyde,
formic acid, and phenol. Input mat.riils which pose significant health
effects inc1ut e: asbestos, a known human carcinogen; polypropylene and tn—
methyl phosphate, potential human carcinogens; and acrylamide and furfuryl
alcohol.
Worker Distribution and Emissions Release Points
We have estimated worker distribution for amino resin production pro-
cesses by correlating major equipment manhour requirements with the process
flow diagrams in Figure. 10 through 13. Estimates for adhesive, coating,
laminate and moWing resin production are shown in Table 43.
No major air emission point sources are associated with amino resin
production. FugiUve emission sources, however, may significantly impact
environmental residuals md/or worker health. The degree to which these
Impact the worker’s environment are determined by the stream constituents,
process operating pananetere, engineering and administrative controls 1 and
maintenance programs.
Sourcer of fugitive emissions and the probable contaminants emitted are
listed in Table 44. In addition to these contaminants, numerous other minor
additives (see Table 42) may be emitted, especially around the batch mixer
(all processes), dryer (coating and laminate production), and ball mill and
extruder ients (molding resin production). Additive toxicity is discussed
in IPPEU Chapter lOb. Available toxicity data for principal input materials
and additives are discussed below and sunmartzed in Table 10 in Sect 4 . , £ of
this document.
146
-------
Vent
Alcohol
Figure 13.
Sources: Encyclopedia of
Encyclopedia of
Modern Plastics
Amino molding resin production process.
Chemical Techno gy, 3rd Edition.
Polymer Science and Technotogy.
Encyclopedia, 1981—1982.
Me]
Vent
-J
Amino
Vent
Water
Vent
Resin
Vent
Dyes, pigments, mold release agents,
catalysts, curing agents
-------
TABLE 43. WORKER DISTRIBUTION ESTIMATES FOR AMINO RESIN PRODUCTION
Process Unit Workers/Unit/B—hour Shift
Adhesive Manufacture Batch Reactor 1.0
Separator 0.25
Filter 0.25
Batch Mixer 1.0
Coating Manufacture Batch Reactor 1.0
Separator 0.25
Filter 0.25
Dilution Kettle 1.0
Spray Dryer 1.0
La.inate Manufacture Batch Reactor 1.0
Separator 0.25
Filter 0.25
Spray Dryer 1.0
Molding Resin Production Batch Reactor 1.0
Separator 0.25
Filter 0.25
Dilution Kettle 1.0
Batch Mixer 1.0
Screens 0.25
Dryer 0.5
Ball Mill 0.25
Extruder 1.0
148
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TABLE 44. SOURCES OF FUGITIVE EMISSIONS FROM AMINO RESIN MANUFACTURE
Product
Adhe— Coat— kmi— Molding
Source Constituent sives mates Resins
Reactor Vent Formaldehyde X X X X
Urea or Melamine X X X
Separator Vent Formaldehyde * * * *
Urea or Melamine X X X X
Mixer Vent Formaldehyde * *
Urea or Melamine X X
Dilution Kettle Formaldehyde * *
Vent
Urea or Melamine X X
Alcohol X X
Spray Dryer or Formaldehyde, Urea
Dryer Vent or Melamine, and
Resins Emissions
and Particulates X X X
Alcohol X X
Ball Mill Vent Formaldehyde, Urea
or Melamine, and
Resins Emissions
and Particulates X
Alcohol X
Extruder VeoL Formaldehyde, Urea
or Melamine, and
Resins Emissions
and Particulates X
Alcohol X
*Expected in trace amounts if present in this stream due to high conversion
and limiting amount of formaldehyde in the reactor.
149
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Little data are available fro. which employee exposure potential in
amino resin production processes may be estimated. However 1 one source
gives the following emission factors (286):
• Adhesives——25 g hydrocarbon/kg product
• Molding——iS g particulate matter/kg product
Health Effects
Formaldehyde, one of the major raw materials in amino resin manufac-
ture, is highly toxic and exhibits tumorigenic, autagenic, and teratogenic
potential. Three other input materials and specialty chemicals in this
industry are known or potential carcinogens. They are: the filler asbes-
tos, which is a Irnown human carcinogen; polypropylene, a self—extinguishing
agent, and trimethyl phosphate, a curing agent, both of which are known
animal carcinogens. Acrylamidi , used as a heat resistance additive, and
furfuryl alcohol, a craze resistance agent in the process, also pose a
significant risk to the health of plant employees if overexposure occurs.
The following paragraphs provide a brief synopsis of the reported health
effects of exposure to these substances.
Acrylaxide is a neurotoxin, causing symptoms of ataxia, hypereomnia,
and vertigo.(170j Although the polymer is nontoxic, absorption of acryl—
amid. through skin’ or dusts is associated with serious ne relogical conse—
quences. [ 88 Animal test data indicate that exposure to acylamide might
also cause .nutagentc and teratogenic effects. The OSHA air standaid is 30
ug/m 3 (8 hour TWA). [ 67j
Asbestos is classified as a human carcinogen by the International
Agency for Research on Cancer [ 104) and by the Americaa Conference of
Governmental Industrial Hygienists.(4J ft is currently undergoing addi-
tional tests by the National Toxicology Program. [ 233) Many deaths from
exposure to absestos are due to lung cancer.(104J Not only is the lung
cancer risk dose—related, but there is also an important enhancement of the
risk in chose exposed to asbestos who also smoke cigarettes.(104j The OSHA
emergency air standard is 0.5 fiber >5 un/cc (8 hour TWA).
Formaldehyde poses a high toxic hazard upon ingestion, inhalation, or
skin contact (2 !) with human effects reported at doses as low as 8 pp..
(127) This suspected carcinogen is a potent mutagen and teratogen. The
OSHA air standard is 3 ppm (8 hour TWA) with a 5 ppm ceiling. (67)
Furfuryl Alcohol exhibits tumorigenic and nutagenic potential in lab-
oratory testing.(233J Animal experiments also suggest high toxicLty. [ 242j
Human data indicate that small doses stimulate respiration, while large
doses depress respiration, reduce body temperature, and produce nausea,
salivation, diar€hea, dizziness, and diuresis.(5J The OSHA air staniard is
50 ppm (8 hour TWA).(671
Polypropylene has produced positive results in animal testing for
carcinogenicity.(107j It poses a very low toxic hazard, however. For
example, polyprop7lene medical devices have produced little or no irritant
150
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response when placed into connective or u iuscle tissues for short periods of
tiuze.(31J The propensity for diffusion of polypropylene from the material
is so small that biological response cannot be detected.(31J
Trimethyl phosphate recently produced positive results in a National
Cancer Institute carcinogenesis bioasaay.(233) Soltd evidence also exists
of its mutagenic and teratogenic potential.1233J The substance is also
toxic by ingestion and inhalation and is a strong irritant to skin and
eyes. [ 42
Air Emissions
Sources of VOC emissions from amino resin production are listed in
Table 44. The sole sources of process VOC emissions are vents. Emissions
from these vents may be contcolled by: [ 2851
• Routing the vented stream to a flare to incinerate the hydrocarbons;
and/or
• Routing the vented stream to blowdown.
Other VOC emissions rcsult from leaks or joints associated with flanges,
valves, relief valves, pumps, compressors, and drains. Enclosing the
atmospheric aide of open—ended valves and covering open drains are methods
which may be used to control the emissions. However, a routine maintenance
and inspection program can be a very effective means of control. Air emis-
sions for amino resin production are estimated as 35 kg of formaldehyde and
35 ‘ g of urea per aietric ton of urea—formaldehyde resin produced and 20 kg
formaldehyde and 20 kg of melamine per metric ton of melaraine—forinaldehyde
resin produced. [ 93)
Sources of particulates are also listed in Table 43. Particulates from
the dryer, ball mill, and extruder may be controlled by!
• Venting the stream to a baghouse or electrostatic precipitator for
particulate collection.
According to EPA estimates, the population exposed to amino resin emissions
in a 100 2 area surro rnding an amino resin plant is 40 persona exposed
to hydrocarbons and 8 persons exposed to partlculatea. [ 286 1
Wastewater Sources
There are several wastewater sources associated with the amino resins
produced, as shown in Table 45. The production of molding resins contains
the most sources of wastewater since these resins are available only in
dried form. All amino resin products generate wastewater from the conden-
sation reaction required to produce them.
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ThSLE 45. SOURCES OF WASTEWATER FROM AMINO RESIN M NUPACrURE
Product
Source Adhesives ns Laeinates - Molding Resins
Condensation
Reaction X X X X
Dilution Kettle I I
Screens X
Routine Cleaning
Water I X I I
152
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Wastewatec production from these processes are shown below. Values
presented were not distinguished by product type by EPA for the purpose of
establishing effluent limitations for the amino resin industry: [ 93, 284J
Urea— Melamine—
Formdldehyde Furmaldehyde
Resin Resin
Production,
m 3 /metric ton 0.9 — 1.8 0.6 — 1.3
Solid Wastes
The solid wastes generated by amino resin processing include
substandard resins which cannot be blended, collected particulates, end
resin lost due to spillage and reactor cleaning. These wastes are mostly
amino resins with very little contribution from other sources.
Environmental Regulation
Effluent limitations guidelines have been set for the amino resin
industry. EPT, UT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source performance stsndards (proposed by EPA on January 5, 1981)
for volatile organic carbon (!ICC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• teaks (whict. are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds are listed as hazardous wastes (46 Federal
Register 27476, May 20, 1981):
Asbestos — U013
Formaldehyde — U122
Formic Acid — U 123
Phenol — U188
All disposal of these compounds or amino resins which contain any residua]
amounts of these compounds (i.e., uncured resins) must comply with the
provisions set forth in the Resource Conservation and Recovery Act (RCRA).
153
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SECTION 6
MODIFIED POLYPNENYLENE OXIDE AND POLYPHENTLENE SULPIDE
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Resins considered to be engineering thermoplastic. possess high perfor-
mance characteristics. Polymers generally reported in this category are:
fluoropolyisers, thermoplastic polyesters, polycarbonetes, polyacetals, poly—
amides, A3S, SAN, modified polyph ny1ene oxide, polyphenylene sulfide, poly—
laid.., polyamide—imides, and polysulfones. The first áeven of these resins
are discussed in other sections of this document. Of the remaining resins
listed, only modified polyphenylene oxide and polyphenylene sulfide are
presented in this section because they represent a major portion of the
remainder of the engineering thermoplastic market.
Polyphenylene oxide is the product of oxidative coupling using phanolic
monomers, typically 2 , 6 —xylenol. The homopolymer is combined with polysty-
rene to give an unusually compatibl, polymer blend. High temperature prop-
erties of polyphenylene oxide are complimented by the easy processability of
polystyrene, making modified polyphenylene oxide (NPO) an excellent choice
for electrical and electronic applications.
Polyphenylene sulfide (PPS) is characterized by a repeating group con-
taining benzeue rings pars linked with sulfur atoms. This polymer is
remarkably stable, exhibiting outstaáding high—temperature performance,
inherent flame resistance, and chemical resistance second only to PTPE.
Typical properties of polyphenylene sulfide and modified polyphemylene oxide
are listed Lu Table A—6 in Appendix A.
These polymers are each produced by only one manufacturer. Therefore,
the polymerization processes used I or these resins are presented according
to the polymer produced.
NDUSTRI DESCRIPTION
General Electric Company is the sole producer of modified polyphenylene
oxide. No capacity information was available in the literature consulted
for the Selkirk, New York facility. Similarly, polyphenylen, sulfide is
produced by the Phillips Petroleum facility in lorger, Texas. In tJôl, the
capacity was expanded to 4,080 metric tons.(943
Engineering thermoplastics are experiencing an inc iase in demand.
Their high performance characteristics and strength hav,z made these polymers
154
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excellent replacements for more expensive metals in automotive and proces-
sing applications. The market for these resins is expected to grow
steadily into the 1990’s.(86J
PRODUCTION AND END USE DATA
MPO and PPS are used for appliances, business machines, and electrical
and electronic uses. In 1980, consutrption of PPS totaled 1,720 metric
tons. The most recent information for MPO consumption shows 58,000 metric
tons for 1981. The uses of these polym rs inckide:(14, 92, 94, 151, 247,
258, 295]
Modified Polyphenylene Oxide
• Electrical applications, including us in appliances, electrical
construction products, and business machine housings;
• Automobile applications, including d shboarda, electrical connec-
tors, filler panels, grilles, wheel covers, and exter.Lor body parts;
• Television market for tuner and deflection yoke components as veil
as cabinetry;
• Liquid handling uses, such as pump., underwater components, and
shower heads;
• Photographic film processing tanks and housings; and
• Small appliances and personal care products, especially those
involving exposure to heat and moisture such as food processors,
hair dryers, steam iron., and hot combs.
Polyphenylene Sulfide
• Telecommunications and computer components, such as connector, coil
forms, and bobbins;
• Electrical components for high—voltage applications and structural
components recuiring Underwriter’s Laboratory direct support
capability;
• Chemical processing equipment, including submersible, centrifugal,
vane, and gear—type pumps;
• Under the hood automotive applications;
• Hair dryers, other personal care appliances, swall cooking
appliances, and range components;
• Release coatings for cookware and metal tire—mold surfaces; and
155
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• Protective coatings for valves, pipes, pipe fittings, heat
exchangers, and electromotive coils.
-Table 46 lists major markets for MPO and PPS resins.
PROCESS DESCRIPTIONS
Modified polyphenylene oxide is formed by blending the polymer product
Of the oxidative coupling of 2,6—xylenol with polystyrene and impact mo4i—
fiers. Although low molecular weight polyphenylene oxides (used for heat
transfer fluids) and brominated polyphenylene oxides (used as f lane—
retardants for other polymers) are also produced, the production of MPO for
engineering uses is the only process of commercial importance.
Polyphenylene sulfide was first identifed in tte late 1800’s but com-
mercial production d1d not begin until 1973.(94J Dichlorobenzene is reacted
with sodium sulfide in a polar organic solvent, producing PPS and by—product
sodium chloride.
Modified Polyphenylene Oxide Reaction Chemistry
Polyphenylene oxide, blended with poty tyrsn. for IPO, is formed by
oxi att. c” i,’I& ig of Z,’ —vyh ol. (he verd1L r action is:
o HO-C\ + 0., st_tc::
The xylenol forms an aryloxy radical when combined with a copper—amine
complex, such as copper ti) chloride and pyrtdine. The resulting aryloxy
radi a1s couple to form cyclohexadienones, which then enolizeand redistrib-
ute the double bonds. Diners, trtners, and other oligomers combine until
phenolic groups are no longer available for oxidation. These reactions are
depicted bel i,.
OH
Catalyst
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TABLE 46. U.S. CONSUMPTION OF MODIFIED POLYPHENYLENE OXIDE
Market 1981 Thousand Metric Tons
Appliances 15
Business Machines 15
Electrical/Electronics ii
Plumbing and Hardware 3
Transpoiation 10
Other 4
TOTAL 58
Source: Modern Plastics , January 1982.
U.S. CONSUMPTION OF POLYPHENTLENE SULFIDE
Market 1980 thousand Metric Tons
Electrical/Electronics 1.45
Other 0.27
TOTAL 1.72
Source: Chemical Econ lca Handbook , updated annually, January 1982 Data.
157
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0
0.
C u 3
The resulting polymer is blended with polystyrene to
comp isite.
Polyphenylene Sulfide Reaetion Chemiatry
Although the overall reaction which produces PPS is known, the details
of the complex chemical mechanism are not fully understood.(94J Dichioro—
beizene and sodium sulfide react to form the PPS chain and by—product sodium
chlorIde. This overall reactton is shown below.
Table 47 lists typical input materials for NPO and PPS processing. perat—
ing parameters for these p ocesses are considered to be proprietry.
Therefore, any availabje information viii be presented in the appro late
processing sect ion.
Cl
+ 2nNaCl
C l 3
form a polymer
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TABLE 47. TYPICAL INPUT MATERIALS FOR KPO PRODUCTION
Function Compound
Monomer 2 ,6—xylenol (2,6—dimethylphenoi)
Comonomers 2 ,6—diphenyiphenol
2—methyl—6—pheny lpheno i
Polymer for Blending poljstyrene
Catalyst copper—amine complex
copper halide and aliphatic amines
copper halide av d pyridine
Fillers glass
m l nera is
Solvent methanol
methyl chloride
toluene
TYPICAL INPUT MATERIALS FOR PPS PRODUCTION
Monomer p—dichiorobenzene
sodium sulfide
Solvent polar organic solvent*
11cr asbestos
chopped glass
iron oxide
*Not specified.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
159
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Modified Polyphenylene Oxide Production Process
The oxidative coupling reaction used to produce polyphenylene oxide for
MPO is a one—step polymerization process. Xylenol is reacted with oxygen in
the presence of a cop?er—amine catalyst complex. The following is a typical
recipe for the preparation of polyphenylene oxide: [ 92J
Material Quant ct
Nitroberizene (solvent) 0.200 1
Pyridine (catalyst) 0.070 1
Copper (I) Chloride tcatalyst) O.OC1 kg
2,6—Xylenol (monomer) 0.015 kg
Chloroform (diluent solvent) 0.600 1
Methanol (solvent) 3.050 1
Concentrated Hydrochloric Acid (solvent) O.Ol 1
Oxygen
Reaction times of seven (1) minutes at 20 to 46°C are reported.(247J Other
processing det4ils were not available in the literature consulted. A
typical reaction train is pictured in Figure 14. The polyphenylene oxide,
once formed, is separated from the vaP, by—product and washed with solvent
to purify the polymer prior to blending with polystyrene and impact
modifiers to produce PfPO.
Polyphenylene Sulfide Production ProceoR
Polyphenylene sulfide production is represented by the process flow
diagram jr Figure 15. Although it 13 not shown in the figure, Phillipa
Petroleum Company produces sodium sulfide for input to this process. No
specific processing details or production recipes were available in the
literature consulted.
Sodiula sulfide, p—dichlorobenzene, and solvent are fed into a polymeri-
zation reactor. Once the polymerization is complete, the solvent La
stripped from the polymer—solvent mixture snd recycled to the reict r. The
p Lymer is then washed with water to remove the sodium chloride y—product
and dried. Molding resins diff r from virgin resins since they are cured
before pelletization and packaging.
Energy Reguirer. nts
No data concerning energy requirements for this process were found in
the literature consulted.
ENVIRONMENTAL ANT) !tV)USTRIAL HEALTH CONSIDERATIONS
MPO and PPS, whIch are considered to be nontoxic compounds, are used in
food contact as well as potable water applications. However, several inputs
to these processes have been tdentified ar hazardous under ECRA: asbestos,
a filler; methanol and toluene solvents; and 1,4—dichlorobenzene and. ,6—
,cylenol (2,4—dinethyiphenul) monomers. MPO processing uses asbestos,
160
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Vent
Figure 14. MPO productjc n process.
Sour.es; Encyclopedia of Chemical Te hno1o 7 , 3rd Edition.
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
Solvent
Polystyrene
Modifiers
Vent
(Desiccant)
Vent
Water
161
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Vent
Na $
p—Dichloro—
benzene
Solvent
Figure 15. PPS production process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
POLYMER—
IZAT ION
REACTOR
Water
Vent
SOLVENT POLYMER
STRIPPING WASHING
I . . )
.1
Condensed
Steam
Vent
1
NaC I
Solution
Vent
POLYMER Virgin i ;
DRY INC
1 _,Vent
I
4
PPS
Molding Resin
-------
methanol, toluene, and 2,6—xylenol while PPS processing involves only
1 ,à_di hlorobenzene.
Worker Distribution and Emissiona Release Points
Estimates of worker distribution for PPS and MPC production are ahovn
in Table 48. These estimates were derived by correl ing major equipment
manhour requirements with the process flow diagrams in Figures 14 and 15.
There are no major point source air emissions associated with either
MPO or PPS processing. The only air emissions are fugitive emissions from
such sources as reactor vents, dryer vents, and condenser ventq. The impact
of these emissions depends on the process operating parameters, engineering
and administrative controls, and input materials used.
Sources of fugitive emissions are shown in Table 49. Solvents typi-
cally used in both processes include methanol, methylene chloride or tolu—
ene. Particulates emitted from blending, washing, drying and curing vents
may result in overexposure to nuisance dust or to particular additives such
as asbestos. Available toxicity information for major process reactants and
additives is summarized under “Health Effects” below.
Health Effects
The production of PPS involves the use of asbestos as a filler. Asbes-
tos is a known human carcinogen whose reported health effects are summarized
below.
Asbestcs ir classifie’ as a human carcinogen hy the International
Agency for Research on Cancer [ 104J and by the American Conference of
‘ overnmenta]. Industrial Hygienists. [ 5J It is currently undergoing addi-
tional tests by the National Toxicology Program.(233J Most deaths from
exposure to asbestos aredue to lung cancer. [ 107J Not only is the lung
cancer risk dose—related, but there is also an important enhancement of the
risk in those exposed to asbestos who also smoke cigarettes.f107J The OSHA
emergency air standard is 0.5 fiber >5 urn/cc (8 hour TWA).
The production of MPO involves the use of an animal carcinogen, poly-
styrene, as 3 polymer for blending. Toluene, a highly toxic substance, is
used as a solvent. The reported health effects of exposure to these two
substances are brief l r summarized in the following paragraphs.
Polystyrene has produced positive results in animal tests for carcino—
genicity. [ 107J The available animal test data is quite limited, however,
and other potential adverse effects cannot be evaluated. [ 233J
Toluene exhibits tumorigenic, mutagenic, and teratogenic potential in
laboratory tests.(233J Human exposure data indicate that toluene is also
very toxic. Exposures at 100 prn have pro’tced psyc’ otropjc effects and
central nervous system effects have been oJ served at 200 ppm. 233J Symptoms
of exposure include headache, nausea, vomiting, fatigue, vertigo, paresthe—
alas, anorexia, mental confusion, drowsiness, and loss of consciousness.
The OSRA air standard is 200 ppm (8 hour TWA) with a 300 ppm ceiling.(67J
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tABLE 48. WORKER DISTRIBUTION ESTIMATES FOR ENGINEERING
THERMOPLASTI S PRODUCTION
Process Unit Workerg/Unit/$—hour Shift
Modified Polyphenylene Oxide Batch Reactor 1.0
Centrifuge 0.25
Solvent Bath 0.25
Batch Mixer 1.0
Solvent Stripping 0.25
Polyphenylene Sulfide Batch Reactor 1.0
Solvent Stripping 0.25
Washing 0 25
Drying 0.5
Curing 0.25
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TABLE 4 • SOURCES OF AIR EMISSIONS FROM MPO AND PPS PROCESSING
Process
Source Constituent MPO PPS
Reactor Vent Z,6—xylenol X
p—dichlorobenzene X
Solvent X
Water Removal
Vent 2 6—xy lenol *
Polymer Purifica- .
tion Vent 2 ,6—xyleno l *
Solvent X
Solvent Stripping
Vent Solvent * *
Polymer Blending
Vent 2 ,6—xyleno l *
Solvent *
Particulatea X
Polymer Washing Solvent *
Part iculates X
Polymer Drying Solvent *
Part iculateg X
Polymer Curing Solvent *
Particulateg *
*Trace amounts are expected due to removal upstream.
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Air Emissions
Sources of fugitive emissions VOC from these processes are sumuarized
in Table 49 by process and constituent type. These vented sources may be
controlled by routing the stream to a flare to incinerate any remaining
hydrocarbo or routing the stream to blowdovn.(285j Other sources of VOC
emissions include leaks from process equipment. Although equipment modif i—
cations are available, a regular maintenance and inspection program may be
the best control for these sources,
Particulate fugitive emissions are also listed in Table 49. These
sources may be controlled by venting to a baghu’ se or an electrostatic
precipitator.
Wastewater Sources
The sources of wastewater associated with NPO and PPS proc ssing are
listed in Table SO. No data concerning wastewater productt’. or character-
istics for these processes were found in th3 literatuie consulted,
Solid Waste
The solid wastes from MPO and PPS production include polymer loct due
to spillage and cleaning, collected particulates, and substandard polymer
which cannot be blended. The solid waste found only in NPO processing is
the spent catalyst and desiccant while PPS production generates the
by-product sodium chloride as a solid waste stream.
Environment _ al Regulation
Effluent limitations guidelines have not been set for the NPO or PPS
induntry.
Mew source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous wastes: (46
Federal Register 27476, May 20, 1981).
Asbestos — U013
l, 4 —Dichlorobenzene — U072
2 , 4 —Dimethylplenol ( 2 ,6—xylenol) — UlOl
Methanol — U154
Toluene — U220
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ZABLE 50. SOURCES OF WASTEWATER FROM MPO AND PPS PROCESSING
— Process —
source MPO PPS
Water Removal X
Solvent Stripping X X
Polymer Washing X
Routine Cleaning Water X X
167
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Dispoe 1 of these conpounda and any $PO or PPS resin containing res4ual
amounts of these compounds must comply with the provisions set forth in the
Resource Conservation and Recovery Act (RCRA).
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SECTION 7
EPOXY RESINS
EPA Source Classification Code — Polyprod. Ceneral 3-01-018—2
INTRODUCTION
Epoxy resins are tough, hard, thermosetting solids which quickly cure
at temperatures ranging from 5 to 150’C.(247J They are available in a
variety of forms which vary from low-viscosity clear liquids to highly
filled viscous pastes to free flowing molding powders. Epoxy resins rear—
range very little during reaction, in most cases produce no by—products, and
maintain surface adhesion and freedom from voids during cure. Their use in
metal replacement is enhanced by their moldability at low pressure, unlimi-
ted colorability, high gloss, and excellent chemical resistance.
Epoxy resins have a unique combination of properties. Their toughness,
adhesive strength, chemical resistance, and superior electrical properties
make them suitable for the manufacture of many different products. Resin
properties may be modified by blending resin types, by selecting applicable
cure events , end by ue ng ‘todifiern and fillers. The casting resins exhibit
excellent strength and low shrinkage during cure. Table A—i in Appendix A
lists some typical properties of epoxy resins.
Over 90 percent of the commercial epoxy resins produced are manufac-
tured from the reaction of epiehiorohydrin and bisphenol—A.(131J Other
epoxy resins include novolaks (i.e., two—step phenolic resins) epoxidised
with epichiorohydrin and unsaturated monomers epoxidiznd by reaction with
hydrogen peroxide or peracetic acid. Unsaturated monomers used include both
cyclic aliphatic monomers such as vinylcyclohexane and acyclic aliphatic
monomers such as butadiene.
Epoxy resins are manufactured either as low molecular weight liquid
resins or higher molecular weight solid resins. Liquid resins are produced
using a two step reaction vhil. higher molecular weight resins are produced
by either the Taffy process or the advancement process.(247J
INDUSTRY DESCRIPTION
Six chemical produc . rs comprise the epoxy resin industry. These
producers have 10 iites located in seven states: California, Kentucky,
Louisiana, ‘lassachujetts, Michigan, New Jersey, and Texas. Table 51 lists
the epoxy resin producers and their capacities.
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TABLE 51. U.S. EPOXY RESIN PRODUCERS
1982 Capacity
Producer and Location Thousand Metric Tone
Celanese Corporation
Celanese Plastics & Specialties Co.
Division
Celanese Specialty Resins Division
Louisv lle, KY 11
Ciba-Geigy Corporation
Plastics and Additives Division
Resins Departgaent
Toiis River, NJ 27
Dow Cheaical U.S.
Freeport, TX 104
Reichhold Cheisicals, Inc.
Andover, MA
Azusa, CA 15
Detroit, MI
Houston, TX
Shell Chemical Co.
Deer Perk, TX 122
Union Carbide Corporation
Coatings Materials Division
Bound Brook, N.J
Specialty chemicals and Plastics Division
Taft, LA 90
TOTAL 293
a lncludes vinyl ester resins.
bThenoxy resins.
CCyc1 1iphatic epoxy resins.
Sources: Chemical Economics Hand uok , updated annually, 1980 data.
Directory of Chemical Producere , 1982.
170
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Epoxy resins are used in coatings for many applications as well as
encapsulating electronic equipment. U.S. production of epoxy resins has
increased f con 111,000 mc.ric tons in 1976 to 143,000 metric tons in 1980.
A producti n peak occurred in 1979 with 164,000 metric tons of resin pro-
duced and only 151,000 metric tons sold. [ 65J Sales for 1981 remained the
same as the 1980 level, 145,000 metric tons. [ 143] The current unused epoxy
resin production capacity (293,000 metric tons) is sufficient to accommodate
growth in the near future.
PRODUCTION AND END USE DATA
In 1981, epoxy resin qales totaled 145,000 metric tons. [ 143] Epoxy
resins, 4 ue to their versatility, have many uses which include: [ 131, 219,
229, 247, 249, 289)
• Photocurable coatings and printing inks, concrete coatings, wire
coatings, marine coatings, coatings for steel pipes, chemically
resistant and electrical grade coatings, can and drum linings,
military aiccraft coatings, floor coatings, masonry coatings,
swimming pool paints, formulations for automotive primers, and
maintenance paints;
• FDA approved coatings for the interiors of beer and beverage cans;
• Stainless steel and anticorrogive paints, electrical resistor inks,
and textile and paper binders and finishes;
• Solution coatings used for maintenance and product fin ahe ,
laboratory furniture, lawn furniture, appliances, hardware, and
magnetic wire;
• Flowable mortar for traffic areas, chemically resistant mortars and
floor topping compounds, monolithic concrete topping applications,
decorative applications such as thin—coat terrasso, and highway
maintenance compounds;
• Solid coating coapound for small motor stackq, refrigerator liners,
oil filters, hospital equipment, primers, shelving, automobile
springs, fire extinguishers, and protection of metal window frames;
• Adhesives for aircraft hoieycomb structures and paint brush
bristles; adhesion and grouting in buildings, roads, and bridges;
adhesives to bond polyester and phenolic laminates to metal, attach
metal s uda to concrete, bond reflective markers to airport runways,
bond solar cells in satellites, bond chemically resistant films to
tanks and piping, bond copper sheet to laminates for printed circuit
boards, mount gems, restore museum pieces, and bond stained glass
windows to replace lead; metal bonding and sealing in the aerospace
industry; and highway paving materials, grouts, and adhesives for
segmentnl bridge construction;
171
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• Airframe laminates for wing fairing surfaces, fin tips, tail cones,
leading wing panels, double floor constructions, propeller cuff
cove’r , ’füel ducting, and radomes;
• Filament wound glass reinforced pipe for use in oil fields, mining,
chemical plants, water distribution, electrical conduits, pressure
bottles, and t’ocket motor casings;
• Body solders and caulking compounds for the cepair of plastics,
metal boats, and automobiles, and caulking and sealant compounds in
building, highway construction applications, and in applications
where high orders of chemical resistance are requir3d;
• Insulation in motors and generators, distribution svitchgear,
transformers, cable jointing, high— and low—voltage lines,
cross—atas for towers, and railway overhead lines and field coil
insulation, form coil tying, blocking, impregnation, and reinforce-
ment;
• Casting compounds for the fabrication of short—run prototype molds,
stampiñ dies, patterns, tooling, brushingá, and low-voltage cable
splices; encapsulation of high voltage coils for automobiles, power
saws, small components in the telephone industry, and random wound
motors; post insulators, bus bar aupprts, i’witchgear components,
instrument transformers, distribution transformers, high— and low—
voltage bushingi, outdo.r insulators, iitchgéar components,
instrument transformers, con ct andisatch molds, stretéh blocks,
vacuu forming tools, and foundry patterns; and thin sheet castings
between television tubes and their contoured safety plates; -
•. Encapsulation of solid state devices, such as diodes, transis ,rs,
and integrated circuits, and passive electrical components, such as
coils,’capacitors, transformers, and ignition coils, and to
mai ufacture pump housings, impellers, pipe fittings, and valves;
• Manufacture of golf clubs, arrow shafts, vaulting poles, fishing
rods, polo sticks, and racetrack railings; and
• Use in printing inks, fabric treating, dental, surgical, and
prosthótic applications, breaking petroleum emulsions, lightweight
chemic ally re Lstant foams, and additives for a variety, of plastics,
such as vinyl and acrylic resins as veil a. natural and synthetic
fibers.
Table 52 lists epoxy resins markets for 1981.
PROCESS DESCRIPTIONS
Epoxy resins are produced using a two stage reaction for liquid epoxy
resins and either the Taffy pron.ss or the advancement process for solid
resins. The process used depends upon the end product and properties
desired. Typically, liquid epoxy resins have lower molecular weights than
the solid resins.
172
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TABLE 52. U.S. MARXETS FOR EPOXY RESINS
Market Thousand Metric Tons in 1981
Bonding and Adhesives 8
Flooring, Paving, Aggregates 8
Protective Coatings
Appliance Finishes 3
Auto Primers 7
Can and Drum Coatings 18
Pipe Coatings 5
Plant Maintenance 13
Ott’er (thcluding trade sales) 16
Reinforced Uses
Electrical anlnates 11
Filament Witiding 10
Other 5
Tooling, Casting, Molding io
Export 18
Other 13
TOTAL 145
Source: M .dern Plastica , January 1982.
173
-------
Epoxy resins are primarily the diglycidyl ethers of bispheno’—A (over
90 percent). Therefore, only the reaction chemistry and proceesi g param-
eters used for these resins are discussed in this section. Other commercial
epoxy resins produced are listed in Table 53. Epoxy resins are manufactured
from eoichlorohydrin and bisphenol—A via a condensation reaction which is
usually carried to very low polymer molecular weights. A curing agent is
typically added to produce erosslinking during the curing reaction, forming
a tough, thermosetting solid. Epichlorohydrin and bisphenol—A first combine
to form a chlorohydrin intermediate which, in the presence of sodium h7drox—
ide, eiim:nates water sodium chloride. This series of reactions is
shown below:
!piChIoTOhydTtIl $iaphaaol—A
+
Chiorohydria I t.r diae.
um_4f ’ . p_. G ..o_caz cazci + UOH
110 Q. .ocii CL ii 2 + liCi + S 0
The epoxy intermediate adds additional epichierohydrin in a similar manner
to produce the diglycidyl ether of biephenol—A (DOEM), with water and salt
as by—products:
lID _(‘/‘ t.4( )O_C1I 2 Cll_C1 2 + C1CU 2 C 11 2
,
c 2dH 2 .0 _Q . .E .C)O_CI 2 C lI 2 + lad + l 0
174
-------
TABLE 53. OTHER COMMERCIAL EPOXY RESINS
Hydroxyl Compound Used
,4—isopropylidenebig(2 , 6—di—
bromophenol)(tetrabromo—
bisphenol A)
Resorcinol
Phenol—formaldehyde novc’1i k
o—cresol—formaldehyde novolak
p—aminopheno l
1,1,2 ,2—tetra(p—hydro ypheny1,
ethane
Epoxy Resin Obtained
Br
0
C5 2 —CNC,1 2 o _ cL 5 ,c
3r :1I3 Br
cacs o OLC 12 b 12
.0.
I 2 c1,- 2
0
c cz —
[ r cwc i 0
(continued)
175
-------
TABLE 53 (continued)
Hydroxyl Conpound Used
1 ,4-butanediol
Glycerol
Po ly(oxypropylene)glycol
Inoleic diner acid
(one structure shown)
1,1 3-tris(p—hydroxy—
phenyl ) propane
(continued)
Epoxy Resin Obtained
CE 2 CH C E 2 0 (CE 2 ) 4 OCH 2 CH—cH 2
I ’
0 OCHCH—CE
12 2,
CH 2 —CHCH 2 O_CH 2 ..CH_CH 2 ..OCH 2 CE...CH
[ 75 175
CH 2 _CHCH 2 _OIC.1I...C 1 1 2 _ICH_CE 2 .JJCE 2 CECE
[ Jn
o 0
I
(CE 2 ) 7 —C—0cH 2 ’CH—cH 2
2
) 7 —C—0CH 2 CE-CE 2
.—CH”CH(CH 2 ) 4 —CH 3
2
Epoxidized polybutadfene
TYPICAL COHMPRCIAL PRODUCTS OBTAINED BY EPOXIDATION
WITH PERACETIC ACID — __________
‘. 0
C
I .0
sic
J 76
-------
TABLE 53 (continued)
Vinylcyclohexene dioxide
3 , 4 —epoxycyclohex-ilmethyl—
3 , 4 —epoxycyc1oh xane
carboxylate
3—(3 , 4 —expoycyc lo’iexane)—8 ,9—
epoxy—2 1 4—dioxasplro(5,5J—
undecane
blg(2 ,3—,poxycyc lopentyl)ether
biq( 3 , 4 -epoxy—6—metPiylcyclo—
hexylmethyl)adlpate
C_CH2 —f”:::3 :::
/9 o-
Source: ! nç çjop d1a of Polymer Science and
0
0
171
-------
This reaction continues until the epoxy groups have coabirged with all of the
available bisphenol—A. A general structure used to represent both high and
low molecular veigl’t epoxy resins is shown below.
Tables 54 and 55 list typical input materials and operating parameters for
epoxy resin production processes. Other input materials, including
diluents, hardener., fillers, and accejerators, are listed in Table 56.
! 4quid Resin Production
The production of low molecular weight epoxy resine is accomplished by
a two stage reaction. Epich1oroh drjn and biepheno l—A are added to an
agitated reactor in a 10:1 ratio. The condensa i reaction .s then started
by adding a 40 percent aqueous sodium hydroxide solution to the reactor and
heated to the desired temperature. - The epichlorohydrin is separated from
the water by condensation and returned to the reactor whil, the vatet is
een’ to vastevater treatment. Afcer the sodium hydroxide addition is
collipieted, the excess epichlorohyijrtn is recovered using distillation at
reduced preasuree. The resulting epoxy resin Is cooled and a solvent is
added to dissolve the resin and carry the salt out of the reactor, * hot
water wash removes the brine and the. solvent is removed after the resin is
filtered and unshed. The resin may be dried using heating under vacuum or
thin film evaporation.f219J Figure 16 illustrate, this batch process. A
typical recipe for product ion of epoxy resin, via the two—stage liquid
process follow .:f116, 219J
Material Parts b! Vej nt
Epichiorohydrin 46,000
Bispheool—A 11,400
NeOll (402 aqueous Solution)
(dehydrochlorj tor) 9 50O
Methyl lanbutyl Ketone (solvent) 18,03%
Water (polymer wash agent) 57,165
Taffy Pr,ce.s
The Taffy races. Is typically used to produce medium molecular weight
epoxy teems. It 1. very s m1ler to the liquid epoxy resin pro:ess since
epichiorohydrin and bisphenol A ar reacted to produce the epoxy resins.
The noleculqr weight of the product Is determined by the ratio of epichloro—
hydrin to biephenol—A. A smaller excess of epieblorehydela then that weed
178
-------
TABLE 54. TYPICAL INPUT MATERIALS TO EPOXY RESIN PRODUCTION PROCESSES
Ltquii
Epichloro- Risphenol Epoxy Aqueous
Process hjdrin A Resin NaON S lvent
Liquid X X X 2
Taffy 2 X 7.
Advancement 2 2 2
TABLE 55. TYPICAL OPERATINC PARAMETERS FOR EPOXY RESIN
PRODUCTION PROCESSES
Process Temperature R. ct on Time Yield
Liquid 99 — 119C 3 1/2 hours 96.92
Taffy IOO’C O 2 3 hours >9OZ
Advancement lOO’C 5 2 — 3 hour s > z
aEstimete
Sources Fu yc1opedia of ‘hemics! Te InoIoJZ , )rd Edition.
Encyclopedia cf Polymer Sc1rnc.ir4Techno1 g 1 .
179
-------
TABLE 56. INPUT MATERIALS USED IN EPOXY RESIN MANUPAC URE
(IN ADDITION TO BISPHZNOL-A AND EPICIILOROflYDRI?’)
Vur.ction pound
Diluents o-methylnaphthalene
Nonreactive biaphenols
chlorinated phenol
dibutyl pPthalata
dichiorohydrin
4 ,4—dieethy l—5—hydroxyTaethy leetha
diozane
dimethyl phthalate
dioctyl phthalate
ethylene glycol ethers
glyéol ether—esters
hydrocarbon otle
indene
low molecular weight polystyrene
methyl methacrylate
monobasic aliphatic acids
phenols
3—(p.rtadecyl) phenol
pine oil
styrene
xy .iie
Epoxy—’ontairiing allyl glycidyl ether
Reactive —pinene oxide
Nonoepox? butyl glycidyl ether
cr.eyl glycidyl ether
cyclohexene vinyl monoxide
(C 12 _ 14 H 22 _ 26 03)glYtidYl
ester of tert—carbozylic acid
dip.nt ne mnoxtde
I ,2-evzy—4—vinyl cyclohexane
2,3—epoxyoctane (152 1,2—isomer)
1ycidyl methacrylate
è—.ethylphenyl glycidyl ether
octylene oxide
olef in oxides
p—butyl phenyl glycidyl ether
3—(pentadecyl)phenol glycidyl •th.’r
phenyl glycidyl •ther
styrene oxide
(continued)
180
-------
TANLE 56 (continued)
Functiot CO mp3und
Epoxy bia(2,3—epoxycyclopentyl) ether
butanediol diglycidyl ether
butadiene dioxide
diechylene 1ycol dlglycidyl ether
diglycidyl ether
diglycidyl ethar of resorcinol
2,6—diglycidyl phenyl g]ycidyl
ether
dimethylpentan. dioxide
divinylbenz.ne dioxide
3, 4—epoxy—6—meth 1cyclohexy —
m .thyl—3,4—epoxy—6—mothyY.cy.1n-
hexane carboxylat.
2—glycidvi ph.nyl glycidyl •thrar
li.onane dioxide
vinyli.yclohexens dioxide
Non—epoxy Containing acrylonitril.
Reactive Diluerti d-l l monemo
0 -caprolactam
lactonee
butyro lactone
phenol.
short chain poiyois
etyr.n.
tertiary aminae combin.d with fatty
polynmide.
unsaturated dines
Colorants
Whi .. antimony oxide
titanium 4ioiid.
Mack carbon black
hyth.rm black (Patent Chemicals)
Red cadmium red
National fast red (National
Anilin.)
toluidene red
Biown brown iron odd.
(continued)
‘Al
-------
TABLE 56 (continued)
Function Compo’ind
Yellow cadmalith golden (Chemical and
Pigment Co.)
Calco condensation yellow BTC
(American Cyanamid)
Mania yellow
Blue Calco condensation blue (American
Cyanamid)
Phthalocyarine blue
Green Calco condensat ion gree’i AT
(American Cy&namid)
Ththalocyanine green
Gray aluminum powder
Fillers aluminum
aluminum powder #44 (Metals
Disintegration Co.)
aluminum silicate
antimony oxide
asbestos
barium titanate
buytes
calcium carbonate
calcium sulfate
carbon
ceramic xir. on
colloidal silica
copper
dimethyl dioctadecyliimouium
bentonite
ferric oxide
fPnt powder
glass
graphite
hydrated alumina
I ton
kry l Ito
limestone
lithium aluminus silicate
magnesium aluminum silicates
magnesium silicate
(continued)
182
-------
TABLE 56 (continued)
Function Compound
Fillers (continued) marble
methane diamine
ml ca
molybdenum dtsulfide
polypropylene
Portland cement
quartz
silica
silicone carbide
silver
steel
tabular aluminum T—60 (ALCOA)
talc
volliistonjte
zinc o*lde
zirconium silicate
Solvent toluene
Flame ketardent cured, chlorinated polyester vith
antimony trioxide
Surface 1,ubrlcetlon graphite
molybdenum disulfide
Cure Accelerator carboxytermtnated pniyest.rs
dimerized and trinerized fatty
acids
morpholine salt of ptctluenesul—
fonic acid
organic acids
maleic acid
oxali acid
phthalic acid
phenol
phomphorlc acid
tertiary amlnea
bsnzyld1methyla 1 (BDMA)
trJs(d lmethylamjnomethy l)pheno l
(DMP -30)
zinc oitfde
(cont Inued)
183
-------
TABLE 56 (continued)
Function
Curing Agents amide derivative of 4—aminomethyl—
Anine Hardeners 1,8—diaminooctan.
amine adduct of o—hydrozylbenzotc
acid
aminoethylpiperaxine
amino resins
2—amino alkyl eaters of polyhydric
polyphenols
aromatic bis(amino—imjde) compounds
aromatic polyamines
benayl dimethylamine
bisanthrantlates of bis(hydroxy—
alkyl) ureas
bisanthrantlates of polyethylated
carboxylic acid
bisanthranilates of polyoxyothy—
lated urea
bis ( 4—ami no—3—aminomethyl—
piperidyl—(t )jalkanes
J,9bis(2—hydragidoethyl)—2 4,
8,1O—te’raoxaspiro(5. SJur.decane
carboxylic acid metal salt/amine
complexes
compounds derived from mennich
bases
cyctoaliphatic epox and isidagolei
diaminodi phenyisulfor
1 .4—diamino butanep
1, 3—dtaminopropan.s
dicyan i am lde
dicyandis,i de/imtdagolin.
derivative
di ethano lamE ne
diethy lamlnopropylaipjn.
diethytenet riamide
dtethy l .thano la.ine
2 ,3—dieethy l—2 ,5—hexanedisiej e
2 —ethyl-4— methylt.id.go l.
guan*mtnee
hydrogenated polynitril. mixture
imidazoles
Imidezole—tsocyanuric acid adducts
maclocyclic polyamtne.
(continued)
184
-------
TABLE 56 (continued)
Function Compound
Ci’ring Agent. mixed amine—phenol products
Am1n. Hardener. w—phenylenediamin .
(continued) n—alkyl .ubst1tute pol)a’llne
N—substituted piperazine adduct
cocuring agent
oligom rL poly(ethylene
piperazine)
phenolic aminee
phenol—polyamide—carbonyi compound.
phenylenediamine
phenvl’ndane diamine.
phenylurea
piperidine
polyalkylene polyether polvol
polyamine.
polyamide. from polymeriged fatty
acid.
polya&ne—aryl imide group.
polycyclic polyamine.
polyepoxl de
polyoxyalkylen. polyamine
pyridine
pyrrol tdone—5—carboxyUc neid/
metal/amine complex.
.terically hindered uireas
t riethylenetet ramine
trimethlyami,e
7 , 4 .6—trls(dim.thylamino thy1)
phenol
Anhydride and Acid aluminum chloride
Hardener, aromatic amlnocarboxyllc acid.
arylowydianhydr lde.
bisphenol ant ydrid.
carboxylte actiJ anhydrldeg
chiorendle anhydrid.
cyanoaceric acid 6erivatlv..
dl.erized fatty acid.
dodecylsuccinlc anhydride
fettle chloride
hezahydrophth lic anhydrtde
(continued)
185
-------
TABLE 56 (continued)
Function Compou d
Anhydrtde and Lcid hydrophthalic arhydride
Hardencra (i ,ntinued) imidyl phtllalic anhydride
latent Levis acid catalyst system
IF 3 adducts
5F3—munoethylasine
stannic chloride
ealeic acid
ealeic anhydride
nadic methyl anhydride
ozalte acid
phthalic acid
phthalic anhydridee
polyester polycirbozylic acid
salicylic acid and m8thyliminobis—
propy lamine
tetrahydrophthal Ic anhydride
trimellitic acid ester
trimeriged fatty acids
Sulfur Containing bis(fluoroaikylsulfonyl) methane
Compounds salt
dialkyl hydroxynryi sulfonju salts
and organic oxidant
fluoroaliphatic aulfonyl substi-
tuted ainylenes
methylol derivatives of polythiols
polyether thiourea compound.
polyrnercaptana
Other Catalysts chromium III ehelates
diarylIodonjui and copper chelate
diaryliodonium salt, copper salt,
and reducing agrnt
hydroxy functional organophnsphat.
eater
inorganic bases
Levis bases
oni urn salts and reducing agent.
stabtl’xed iodonium/copper salt
compositions
Reslnoue Pfodi(iera acrylic resins
amino resins
butadiene—icrylonitrite resins
(continued)
186
-------
TABLE 56 (continued)
Function Compound
Resinous Modifiers coal—tar pitch
(continued) furfural resins
isocyanates
nylons
petroleum—derived bitumens
pheno’ic resins
polyester resins
po]ysulfide polymers
polyurethane resins
polyvinyl chloride
silicone resins
vinyl resins
vinyl cyclohexane
Reinforcements aramide
boron
carbon
glass fibers
graphite
Kevlar
metal fibers
Thixotropic Filler colloidal silica
Internal Release Agent zinc stearate
Acidic Reactants hydrogen peroxide
eracetic acid
Sources: EncyclopedlE. of Chemical Technology , 3rd Edition.
Encyclopedia of Poiywer Science and echnol .
Epoxy Resin Technolo , Paul F. Bruins, editor, 196g.
Henry Lee and Kris Meville, Handbook ofEpox Resins , 1967.
Modern Plastics Encyclopedia , 1981—1982.
187
-------
Vent
Brine to
Vnstewat.r
Treatment
Ep lchloro%ydrin
Recycle
4
W er to
WastewaLer
Treatment
Figure 16.
Low molecular weight liqaid epoxy resin production process.
Ptchlorohydri n .
I phenol-A -
NaOH
a
SQlvenc
a
IZAT ION
REACTOR
I Vent
V
I
I
Vent
SOLVENT
Epoxy
Resin
Solvent
eccle
DISTIL—
LAT ION
Source: U. C. Potter, Epoxid. Resins , 1970.
-------
for liquid resin production enables . medium molecular weight product
(usually I to 4 repeatIng groups) to be formed. Production nf solid epoxy
resins via the taffy process typically have a recipe as follows:(244AJ
Material Parts by Weight
Bisphenol—A 228
Epfchiorohydrin 145
NaOH (102 aqueous solution) (dehydrochiorinstor) 750
The highly viscous product Is actually a mixture of an alkaline—brine
solution and a vater—!esin emulsion. The epoxy resin is recovered by
separation of these phases, washing the resin with water, and removing the
water under vacuum. This process is presented in Figure 17.
Advancement Proce3s
The advancement process, also referred to as the fusion method, uses
llqtid epoxy resin as a starting material and extends the chain by adding
bisphenol A. lii contrast to the liquid epoxy resin and Taffy processes,
thisi method uses a catalyst to accomplish the reaction. Catalysts are
considered to be proprietary, although a variety is available to provide
spettal requiremerta, such as resins free from resin branching.(249J The
molecular weight of the resulting resin is determined by the ratio of excess
1ltild enoxy resin ro bisphenol A. No by—products are generated by this
process, and it produces resins with only even numbers of repeating units.
(249J This process I . depicted in Figure 18. A typical production recipe
for solid epoxy resin via th. advancement process was not found in the
literature.
Energy Reguirennnts
lo data on the energy requirements for epoxy resin processing ,ere
fcuid in the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTh CONSIDERATiONS
Cured epoxy resins are toxicologically inert compounds which are FDA
approv .d for coattt g the interiors of beverage cans.(63J However, the use
of curing agents, many of which are skin sensitizers, does increase the
toxic effect ot uncurad epoxy resins. MethyL ieobutyl ketone, a by—product
from some epoxy resin processes, has been listed as hazardous, as well as
the following Input materials: acrylonitrile, asbestos, di—n—butyl
phthalate, ullmethyl phthalate, di—n—octyl phthaiate, maleic anhydride,
methyl methacrylate, phenol, phthalic anhydrid., pyridine, toluena, and
xylene.
Although the advancement process do.. not generate any wastes during
the chain extentlon reaction, the liquid epoxy resin used as aninput to
this process generates wastewater during it. production. Therefore, all of
189
-------
Veat
Pture 1?. N d1u 1ecu1ar vslght spozy resin product ton usiug th. taffy process.
Source: lncyclopedj. of Dienical Technology , 3rd gditton.
I - .
•0
0
Water
Water to
Tree tenat
Sr ins to Water to Epozy
Vastewater Wastewater Seem
Treatenat Treatsent
-------
Vent
Liquid
Pigure 18. HIgh molecular weight epoxy resin using the advancement process.
Source: j,c1opedia of Chemical Technology , 3rd Edition.
191
Resin
Epoxy
Resin
-------
these processes generate vastevater from polymer washing and brine removal
in eddition to routini cleaning water.
High coniersion. in these processes ( >90 percent) indicate, that
sources upstream of and including the polymerization reactor are suspect as
the major VOC emissions contributors. The liquid epoxy resin production
process has added VOC emissions due to the use and recovery of the solvent.
Worker Distribution and Emissions Release Points
We have es.tlmated worker distribution for epoxy resin production by
correlet ing major equipment ma ihour requirements with the process flow
diagrams in Figures 16 throu h 18. Estimates for the three major production
praceaseq are shown In Table 57.
There rare no lajor air emission point sources associated with epoxy
resin production. However, fugitive emi .sio s fro. process vent, and leak a
may pre .enP a significant environmental impact andfor worker health thres.t.
The magnitude of these problems is a function of the .tream constituents,
process c erating parameters, engineering and administrativ, controls, and
maintenance p’ograms.
Probable fugitive emission sources and contamJnants are identified in
Table 5 . Typically, Poluene ii the solvent used In th. liquid resin
process. Available toxtcity information for these chemicals i . sumeariged
under “Hcalth Effects.”
Numerous additives (see Table 56) m.y be incorporated Into epoxy
resin.. Available toxicity int rmatjon for additives is provided in IPPEU
Chapter lOb.
In addition to the fugitive process emission, listed in Table 58
e sployees may be exposed to sodium hydroxid. added as a reaction Initiator.
Sodium hydroxIde Is highly corrosive and even brief contact with skin or
mucous m .usbranes can produc. severe irritation and chemical burn..
Maintenance employees may be exposed to methyl isobutyl ketone (MIII)
used to periodically clean polymerization reactors. MIlE is irritating to
the eyes and respiratory tract and p.oducas headache, nausea and drowsiness
at high concentration,. Milk Is a defatting agent and prolonged akin con-
tact say produce dryness or dermatitis.
Little data are available from which employee exposure potential may be
esc.nated. However, one source estimates hydrocarbon emissions from epoxy
iudhpq j production at 25 glkg pr’iduct.(236J
Health effects
The manufacture of epoxy resin i.ivolves the ‘ ie of over 200 input
•mate 1als and specialty c’ emIcal,, Sufficient data do not exist with which
to evajiate potential health effects for over hell of these materials.
192
-------
TABLE 57. WORKER DISTRIBUTION ESIIMATES PO EPOXY RESIN PRODUCTION
Procea Unit Wo;kere/Unit/8—hour Shift
Li iid eqict Batch Rractor 1.0
C’ndenaer 0.125
Separator 0.25
Uaehing 0.25
fIlter 0.25
Solient Recovery 0.25
Diattllation 0.25
Taffy Batct Re. ctor 1.0
Condeneer 0.125
Separator 0.25
Phaee Separator U.25
Waehing 0.25
Evaporator 0.25
Advencem°nt Batch Reactor 1.0
193
-------
TAPiR 58. SOURrES OP FUCITIVE EMISSIONS PROM EPOXY RESIN MANUFACTURE
Process
Source Constituent Advancesent
Reactor Vent Epichiorohydrin X X
Bisphenol A X X X
Solvent x
Condenser Vent Epichiorohydrin I I
Eptehiorohydrin
Separator Vent Epichlorohydrin I I
Phase Separator
Vent Ep lchiorohydrin *
P ilyner Wash Tank Solvent x
- Epichiorohydrigi * C
Solvent Recovery Solvent
Vent
Distillation
Colu.n Vent Solvent x
Only trace asounts of eptehiorohydrin are upected in these streams due to
the ree ya1 upstream in the eplchlorohydrjgi separation step.
194
-------
Those that d c have a significant history of aniisiil test data and/or epidemi—
ological data include one known human carcinogen——the filler asbestos——and
two suspected human carcinogens._ acry1onI rj , a diluent; and p 1yvinyl
chloride, a resinous modifier. Four known animal .ccinogens are also used
by the industry: epichlorohydrjn, a major raw ‘ — . rial in the process; the
filler polypropylene; and two diluenta, vinyl cyclohexene dioxide and 3,4—
ePoxY_ 6 _methylcyclohexylmethyl_3,4_ePoxy_6_laethylcyclohe, ne carbozylate.
Other chemicals that may pose a significant risk to the health of plant
employees because of high toxicity, mutagenicity, and/or teratogenicity
include three diluents——allyl glycidyl ether, diglycidyl ether, and styrene;
two curing agents——piperidene and maleic anhydride; phenol, which is used as
a pure accelerator; the solvent toluene; and the colorant antimony oxide.
The reported health effects of exposure to these substances are suarized
belcw.
Acrylonitrile , a suspected human carcinogen (107J, causes irr tat1on of
tne e’es and nose, weakness, labored breathing, dizziness, impaired judg-
ment. cyanosis, nausea, and convulsions in humans. Hutagen4c, teratogenic,
and t umorigenjc effects have been reported in the literature. The OSHA air
st.iddarvj is 2 ppm (8 hour TWA) with a 10 ppm ceiling.(69J
Allyl Glycidyl Ether has exhibited tumorigenic and mutagenic potential
In animal tests, and is currently being tested for carcinogenesis by the
? 1 ’tional Toxicology Program. [ 233J It produces severe local reacLions fol-
lowing acute exposure, but systematic effects are considered moderate by
Inhalation an 1 slight by ingestion ard akin absorpfIon. [ 242J Symptoms of
•xpoqure irw)iide cei’tral nervous system depresson and pulmonary •dema.(242J
OSMA has set the ceiling for exposure at 10 ppm (8 hour TWA).(67J
Antimc,ny Oxide is a suspected carcinogen 15J which has also produced
positive results in teats for mutagenic effecs. [ 155J Animal testing of this
substance is limited, however, and no epHemiological data exist.
A begtog I classified as a human carcinogen by the international
Agency for Research on Cancer (104J and by the American conference of
Governmental Industrial Ifygienistg. 5J It is currently undergoing addi-
tional tests by thy National Toxicology Progrnm.f233J Most deat 1 s from
exposure to asbestos are due to lung eanger. lO4J Not only is the l ’ng
cancer risk dose—related, bit there is also an important enhancement of the
risk In those exposed to asbestos who also smoke clgarettes.(104J The 0 HA
emergency air standard is 0.5 fiber >5 urn/cc (8 hour NA).
Q j1yc1dy1 Ether is regarded as a hazardous compound and persons should
be pr tected from all contact with liquid or Its vapor.(5J It is highly
tr,xtc via oral and inhatatior. routes and moderately toxic via the dermal
roiite. 243J Effec q observed in man include akin burns that are slow to
h’.aJ and acute Irritation of eyes and respiraLory tract.fl70J In l&oratory
ailinats, central ervous system depression, liver damage, and mutagente
act ty have been reported.(233J OSHA has set * ceiling for exposure at
0.5 ppm.f67J
195
-------
Epichiorohydrin is highly toxic by ingestion, inhalation, and skin
absurption.f242J in acute poisoning, death nay be caused by respiratory
paralysis (242j chronic exposure can cause kidney injury.(l491 Symptoas of
chronic poisoning at concentrations lover than 20 ppm include fatigue,
gastrointestinal pains, and chronic conjunctivitis.(134J Enichiorohydrin
has also produced positive results in an aa1 tests for carcinogenicity (102J
and for iaitagentci.ty and teratogenicity.(233J The OSHA air standard is 5
ppm (8 ‘hour TWA).(67j
3 , 4—Epoiy—6—Methylc,clohexylmeta 7 1—3 , 4—Epoxy—6—Piethylcyclohezane Car—
boxylate produced positive results in animal tests for carcinogenicity. lO2J
Very little animal data and no human data exist, however, with which to
evaluate the toxicity or other adverse effects of exposure to this chemi—
cal.(233j
Maleic Anhydride is highly toxic by ingestion and inhalation t2421 and
is a power irritant to the skin md eyes.(149J Inha1ation can cause pulmo-
nary edema 11491; other effects of exposure include conjunctivitis, corneal
damage, cough, bronchitis, headache, abdominal pain, nausea, and vomiting.
(Z33J Animal data also suggest that maleic anhydrid. is a tumorigen! C
agent.f2333 The OSHA air standard is 0.25 pp. (8 hour TWA).(67J
Phenol is extremely toxic by ingestion, inhalation, and skin asorp-’
tion.(85j Approximately half of all reported cases of acute phenol poison-
ing has regulted in death.1278J Chronic po1soning may also occar from
industrial contact and has caused renal and hepatic dxmage.(149J Evidence
indicates that phenol is also a tumorigenic, eutagenic, and t ’eratogeaic
agent; however, a recent carcinogçncisls bic.aseay by the Nationa l C i èer
tnstitute prothieed negative results.(233J Ve OSHA air standard is S ppm
(8 hour TVA).(67J
Piperidine , accordin to animal test data, is highly toxic by ingestion
and skin absorption and moderately toxic by inhalaeion.(233J It also pro-
duces mutagneic and teratogenic effuct• in laboratory nimal.. 233,J How-
ever, there is no record in the available literature of the ef fecLi on
humans of exposure to piperidine. 233J
Polj 1 iropylene has produced positive results in animal testing for car—
cinogen1cttr .I!V)TJ It poses a very low toxic hazard, however. for enampi.,
polypropylene medical devices have produced little or no irritant response
when placed into connective or muscle tissues for-short periods of time.(31J
The propensity for diffusion of polupropylen, from the material is so mall
that b1 logic &1 reiponse cannot be d.tected. 1311
Pnl;v1r yl Chloride is a suspectel human earcinogen.(1O7 Although the
finished foam resin nay cause allergic dermatitis, it Is ‘generally free froá
health hazard unless comeinuted or strongly heatef.(3J ft burnsreadily and
gives off objectionable s.oke.f285J Several cases of angiosaiCom . of the
liver have been detecred among long—time yorkers in plact. thatmake poly—
vinyl chloride from monomeric vinyl :hl aride.t85J
196
-------
Styrene has been linked with increased rates of chromosomal aberrations
in persons exposed in an occupational setting.L107J Animal teat data
strongly support epideraiological evidence of its mutagenic potential. 233j
Styrene also produces t .mors and affects reproductive fertility in labora-
tory animalq.(233p Toxic effects of exposure to styrene usually involve the
central nervoun system. [ 233J The OSHA air standard is 100 ppm (8 hour TWA)
with a ceiling of 200 ppm. [ 67J
Toluene 2xhibits tumorlgenic,sutagenic, and teratogenic potential in
laboratory tests. [ 233J Human exposure data indicate that toluene is aiso
very toxic. Exposures at 100 ppm have produced psychotropic effects and
central nervous system effects have been observed at 200 ppm. 233J Symptoms
of !xpo5 re include headache, nausea, vomiting, fatigue, vertigo, paresthe—
alas, anorexia, mental confusion, drowainess, and 1 ,g of consciousness.
The OSHA air standard is 200 ppm (8 hour TWA) with a 300 ppm ceiling.(67J
Vinylcyctohexene Dioxide , a suspected carcinogen (104J, is currently
undergoing additional tests for carcinogenesis by the National Toxicology
Program.f233J It is a strong Irritant to skin and tissue, but only moder-
ately toxic by ingestion and skIn absorption.(421 Risk by inhalation is
considered to be alight.(4J Tests with microorganisms and mammals demon-
strate the mutagenic potential of this sub .tance. [ 233J
Air Enissiong
VOC emission sources for epoxy resin processing are summarized in Table
by process and constituent type. All of the process sources hated are
vents, and may be controlled by: 285J
• Routing the vented stream to a flare to incinerate any remaining
hydrocarbons; ant/or
• Routing the vented stream to blowdown.
Other sources of ‘/UC emissions incljde leaks from valve., flanges, cooling
towers, drains, p nps, and compressors. Although some equipment modifica-
tions may be performed to reduce these emissions, such as enclosing the
atri,ospher’.c side of open—ended v lvea or covering open drains where explo—
give limits are not a pr ,blem, the best control may be achieved by inettiut—
i ug a regular inspection and maintenance program.
o particulate emissions are expected from the polymerization process.
However, some particulate emissions say result from storage and handling of
the raw materials or end products. According to EPA estimates, the popula—
tton exposed to epoxy resin emissions In a 100 km 2 area around an epoxy
reqin plant is: 64 persons exposed to hydrocarbi,nm aiif 2 per.’in. exposed to
part tcu1 ate s.I2 6J
197
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Wastewater Sources
There are several wastewater sources associated with the various enoxy
resin production processes, as shown in Table 59. The advancement process
appears to generate less vastevater than the other tw3 processes since this
process advances the molerular, weight of an existing liquid epoxy resin.
Ranges of several vas evater parameters for wastevaters from epoxy
resin production are shown below. Values tor the wastewaters from various
Droce9 es presented were not distinguished by process type by EPA for the
(.r oqp of establishing effl.ent limitations for the epoxy resin industry.
1284J
Epoxy Resin
Wastewater Unit/Metric Ton
Characteristic of Epoxy Resin
Production 2.5 — 5.1 is 3
SOD 5 57— 82kg
C ’D 30 — 121 kg
TSS 5—24kg
Solid Wasteg
The solid wastes generated by this process may be: sodium chloride,
other by—productg, unrecov’ red eptchlorohydrin, substandard epoxy resin
)utch cannot be biend d ar.d epo resin 1 as due to aptilage and reactor
cleaning. Valu’ s for some of the solid wastes generated by some epoxy resin
processes are l1at d below.1931
Mount, kg/Metric
solId Waste fun of Epoxy
Source Constituents Resin Produced
Brine Sodium ChlorIde 344
Reactor Clenning Methyl lsobutyl
Retone 45
Reactor Cleaning Sodium Monohydrogen
(continued) Phosphate 16.7
Ep lchlnrohydr ln—
Methanrrl :—
Product 14.8
P.pich lornhydr ln
Separator Epiehlornhydrfn 0.9
198
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TABLE 59. SOURCES OF tJASTEWArER FROM EPOXY RESIN MANUFACTURE
Proce9s
Source Liquid Taffy Advancement
Conder’sation Reaction X X
Reqiri Wash X X
RoutirmeCleanirig Water X X X
19’)
-------
Environmental Regulation
Effluent limitations guidelines have been set for the epoxy resin
industry. BPT, BAT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repai ed vithin 15 days.
The following compounds have been listed as hazardous wastes (46
Federal Register 27476, May 20, 1981):
Acrylonitrile — U009
Asbestos — U013
Di—n—butyl phthalate — 1 1069
Dimethyl phthalate — 11102
Di—n—octv1 phthalate — 11107
Maleic anhydride — U147
Methyl i buty1 ketone — U161
Phenol — U188
Phthaltc anhydride — UIQO
Pyridine — U196 -
Toluene — 13220
Xy lene — U239
Di9posal of these compounds or epoxy resins containing residual amounts of
these compounds must comply with the provisions set forth in the Resource
Conservation and Recovery Act (RCRA).
200
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SECTION 8
FLUOROPOLYMERS
EPA Source Classification Code Polyprod. General 3-01-018-02
INTRODUCTION
Fluoropolymers, named for the inclusion of fluoriae in the monomer,
offer unique performance characteristics. These polymers survive even the
most corrosive conditions. Although they are higher in price than other
thermoplastics, fluoropolymers exhibit outstanding electrical properties,
possess a low coefficient of friction, and maintain nonabrasive and self—
lubricating surface qualities. These properties make fluoropolymers useful
in chemical processing equipment, as insulation and jacketing for wire and
cable, in nonstick home cookware, and as parts for industrial equipment.
There are two major commercial fluoropolymers: polytetrafluoroethy—
lene (PTFE) and polychiorotrifluoroethylene (PCTFE). [ 35J Table A—8 in
Appendix A lists typical properties for PTFE and PCTFE. Other fluoropolymers
used ‘n specialty applications Include fluorinated ethylene—propylene (PEP),
polyvinylidene fluoride (PVDF), poly(ethylene—tetrafluoroethylene) (PETFE),
poly (ethyene—chlorotrifluoroethylene) (PECTFE), perfluoroalkoxy resin
(PPA), and polyvinyl fluoride (PVF). Table A—9 in Appendix A compares
density and e1or. ation for these polymers.
PTFE and PCTPE production processes are presented for this analysis
since they dominate the fluoropolymer inarket.(35J PTFE, produced by sus-
pension or emulsion polymerization, is available in three forms: granular
(guspension), fine powder (emulsion), and aqueous dispersion (emulsion).
PCTPE is produced by bulk, suspension, and emulsion polymerization pro—
esses. In order to discuss the differences in polymer properties as they
relate to the production method used, these processes will be presented as
PTYE production processes and PCTFE production processes.
INDUSTRY DESCRIPTION
The fluoropolym rs are typically divided into two categories: PTFE and
PCTFE resins; and other resins. PTFE and PCTFE producers are listed in
Table 60 whiie miscellaneous resin producers and theu products are pre-
sented in Table 61. Allied Corporation and Minnesota Mining and Manufactur—
big are the PCTPE producers and they consider the plant capacity data to be
proprietary. The fluoropolymer dustry is c ’mprised of six producers with
eight plants located in seven states: Alabama, Kentucky, New Jersey (2
sites), New York, Pennsylvania, Virginia, an West Virigina. Although total
capacity for the industry is not published in the literature, the capacity
of the PTPE segment is 11,400 metric tons.(56J
201
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TABLE 60. U.S. P 0DUCERS OF PTYE RESINS
1982 Capacity
Thousand
Producer Location Metric Tone
Allied Corporation
Allied Fibers &
Plastics Co. Elisabeth, NJ 1.4
E. I. du Pont de Nemours
& Co., Inc.
Polymer Products Dept. Buffalo, NT
Park raburg, WV 7.7
IC! Americas Inc.
Perforiiiance Resins
Division Bayonne, NJ
11.4
U.S. PRODUCER OP PCTPE RESINS
Producer Location
Allied Corporation
Allied Fibers &
Plastics, Co.
Nypel, Inc., subsidiary Chesterfield, VA N.A.
Minnesota P 1mb 8 and
Manufacturing Co.
Comeercial Chemicals
Division Decatur, AL N.A.
N A. — Not Available.
Source: Directory of Chemical Producers , 1982.
202
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TABLE 61. U.S. PRODUCERS OF MISCELLANEOUS FLUOROPOLYMERS
Producer Location Resin Type
Allied Corporation
AlIie’ Fibers &
Plastics Co. Elizabeth, NJ Poly(chlorotrifluoro—
ethylene—vihylidene
fluoride)
Poly( ethylene—chioro—
tn f luoroethylene)
E. I. du Pont de Nemours
& Co., Inc.
Polymer Products
Department Buffalo, NY Polyvinyl fluoride
Parkeraburg, WV Fluorinated ethylene—
propylene
Poly(ethylene—tetra—
fluoroethylene)
Polyfluoroalkozy
Minnesota Mining and
Manufacturing Co.
Commercial Chemicals
Division Decatur, AL Polychlorotrifluoro—
ethylene and poly
(chiorotrifluoro—
ethylene—vinylidene
fluoride)
Occidental Petroleum
Corporation
Hooker Chemical
Corporation, subsidiary
Plastics & Chemicals
Specialties Group
PVC Raging Diviaion Pottgtovn, PA Poly(chlorotrifluoro—
ethylene—vinyl
chloride)
Pennvalt Corporation
Chemicals Group
Inorganic Chemical
Division Caivert City, RY Polyvinylidene
fluoride
Source: Directory of Chemical Producers , 1982.
20J
-------
Pluoropolymer production follows the trends of the U.S. economy.
Nonatick cookware, chemical processing equipment, and insulation needs ter.d
to exhibit the same upswings and downturns as the U.S. economy. Sales of
granular PTFE have increased from 5,000 to 6,140 metric tons during the 1976
to 1980 tine period with a peak In 1979 at 6,550 metric tons.t65J Current
capacity for this industry is sufficient to accommodate any near term
growth.
PRODUCTION AND ND USE DATA
In 1980, granular PT Z sales were 6,140 metric tons.165J Uses for
fluoropolyners include: [ 19, 23, 72, 77, 145, 245, 2 94J
• Electrjc applicatio , such as hookup and hookup—typ, wire for the
military and aerospace industries, coaxial cable tapes, intercon-
necting wires for airframes, computer wire, electrical tape, elec-
trical components, spaghetti” tubing, and insulation and jacketing
for high performance wire and cable;
• Mechanical applications, such as seats and piston rings, bearings,
mechanical tapes, coated glass fabrics, and basic shapes for
industrial equipment, farm machinery, and passenger vehicles;
• Chemical applications, such as hard and soft packing, overbrajded
hose liners, thread—sealant tapes, gaskets, fiber and filament,
membranes, and instrument part, for chemical equipment;
• Cryogenic seals, gaskets, valve seats, and liners;
• Medical packaging and i otru.snt parts for medical equipment;
• Low molecular wei ht inert sealant. and lubricaft!,. for handling
oxygen or other corrosive meterLal., gyroscope flotation fluids,
plasticizers for thermoplastic., and greases for specialty
lubrication;
• Coatings and linings for valves, pumps, pipe and fittings; and large
tanks and process vessela;
• Molded filter housing., pmmp casings, impellers, and other fluid
handling equipment; and
• General ap’lieations such as sockets; pir.i and connectors; coatings
for home cookware, tools, and food processing eq•iipuent; flame—
retardant laminates for aircraft interiors; bearing pads for
bridges, pipe lines, and high—rise bufld lngs; and packaging and
production line conveyor equipment parts that most be self—lubri-
cating nnd noncontaminatjng.
204
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PROCESS DESCRIPTIONS
Fluoropolymers are produced by mass (bulk), suspension, or emuls!on
polymerization. Suspension and emulsion processes are used to make both
PTFE and PCTFE; mass polymerization produces PCTFE. Eac t i of these processes
h s various advantages and disadvantages when related to the properties of
the polymer obtained.
PTFE Reaction Chemistry
PTFE is polymerized using a free—radical initiator (R.) in the presence
of small amounts of oxygen. The initiator reacLs with a tetrafluoroethylene
(TFE) monomer to form a TVE radical, which in turn reacts with other TTE
monomers to produce the PTFE chain. Termination is predominantly by radical
combination. This series of reactions is shown below.
Initiation
F F P
\ / . - -
C.C + —
/ ‘ I
F F F
Propagation
__ r1 rr
R— —• + nCP 2 —CF 2
Termination by Radical Combination
ft
Tn close packing of the fluorine atoms around the carbon backbone provides
a protective shield; thus, the polymer is resistant to many corrosive
env ronments.
PCTFE Reaction Chemistry
YCTFE, production similar to that for P17K, uses a free—radical initi-
ator (RI) and the chiorotrifluoroethylene (CTPE) wonomer. The initator
combines with the monomer to produce a CTFE rcdical which then reacts with
other monomers to form the PCTPE chain. Termi ation occure primarily by
radical combination. This sequence of events is shown below.
205
-------
Initiation
Cl
+ — ,
Cl
C—
Propagation
+ nCC1P-C7 2 - 1} F-f
ft
Table. 62 and 63 list typical input materials and operati*tg parameter. for
PTPE and PCTFE production. Other input materials, such as eulsifiers md
protective colloids, are listed in Table 64.
PTFE Production Proceu3 ,
P V is produced by emulsion and suspension,po lymerigatioe Proc......
Emulsion ;olymerizatjon produces two resin type.: an aqueous dispersion an
a fine powder. Granular PT?! is manufactured using the suspension
polvnerizatjon process. A brief description of each process follows.
Emulsion !olyerization
The process used to form aqueous dispersions of FTP! is not a typical
emulsion process. The TIE gas is introduced to a water—filled reactor vher
initiator, emulsifier, and any comonomer, if desired, are added. The
dispersion formed must be stable enoug!l to prevent premature coagulation;
however, coagulation when the poly meri zat i is Completed is desired for thi
fine powder resin.
As shown in Figure 19, the polymer emulsion produced is typically
stabilized and concentrated by evaporation if a dispersion is the denired
end product. Figure 20 illustrates the steps taken to produce the TE fine
powder. Roth of these processes are performed batchvis.. A typical produc-
tion recipe was not found in the literature consulted.
Very little detail is available on the drying of the agglomerated FTP!
resin. However, care must be taken to ensure the abesoce of sheartng.(173
206
-------
TABLE 62 • TYPICAL INPUT MATERALS TO PTPE M D PCTFE PRODUCTION PROCESSES
Product Process Water Initiator Monomer Emulsifier
PTFE Emulsion X X X X
Suspension X X X
PCTFE Emulsion X X X
Suspension X X X
Mass X X
TALBE 63. TYPICAL OPERATING PARAJIETEaS FOR PTPE AND PCTFE
PRODUCTION PROCESSES
Product Process Temperature
PTYE
Fine Powder 1,000 psi 55 — 240C
Aqueous Dispersion 15 — 500 psi 0 — 95C
PCTFE SO—iSOpsi 21—52c
Sources: yclopedia of Chemical Technol , 3rd Edition.
Encyclopedia uf Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Guodman, Plastics Materials and
Processes , 1982.
207
-------
TABLE 64. INPUT MATERIALS AND SPECIALTY EMICALS
USED IN PTPE AND PCTPE NANUFACTUNg
Punc? ion
i onomer chiorot rifluoroe hylene (dPI)
tetrafluoroethy lene (TiE)
Comonomer ethylene
hexafluoropro y1ena
Leobutylena
methyl methacrylat.
rinylidene fluoride
Initiator disu e$ j acid peroxide
organic peroxide.
peroxydj,ulfates of aemonium,
potassium, and sodium
Filler asbestos
bronze powder
carbon
graphite
molybdenum disulfide
polyimide powders
poly( p—oxybenzoat.)
Promoter chloroform
silver salt.
Stabilization Aid Carboxylic acids
c lorLne
cobalt trifluorjde
ozone
Emo lsift.r C 5 .. 20 psrfluoroearboxyljc acid
Source,: Enc7cj9pedia of Chemical Teehnolo . , 3rd !dition.
Ene7clopedia of Polymer $cn. and T.chno1o .
Flioropolymers , Leo A. Wall, elitor, 1972.
Seymour S. Schwartz and Sidney 4. Coodman, Plastiës Ilaterial , and
Process., , 1982.
208
-------
Emergency
fi Vent
Monomer
Water__
P POLY’IER-
Emulqifier 1 IZATION
Initiator REACTOR
I
Comonome r
Stabilizer Vent
TF NSEer
0 Waetewat
EVAPORATION
Treatment
AddLtives
Concentrated
PTFE Dieperelon
FIgure 19. Aqueoua PTFE dinperelon produced batchviee.
Sourceq: Encyt lopedia f Chemical Technology , 3rd Edition.
Seymour !. Schvartz and Sidney H. C odman , Plaatice Materiale and
Proce see , 1982.
209
-------
EmergenCy
% Vent
Monomer
Emisaion
Water POLYMER— ___________
E miisifjer IZATION Fine
P IZACTOR l DRYING I PTFE
Initiator i i Powder
Comovtomer
To Was tevater
Treatment
Figure 20. Batch fine PTFE powder production.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Seymour S. Sc;wartz and Sidney H. Goodman, Plastics Materials and
Processes , 1 )82.
210
-------
Suspension Pol erization
Granular resins are manufactured using a batch suspension polymeriza-
tion process. The TFE monomer and any comonorner are polymerized in an
aqueous medium using an initiator. A dispersing agent may or may not be
used. Vigorous agitation is used to keep the forming polymer in a partially
Coa u1ated state. When the batch reaches the desired conversion, the polymer
is separated from the medium, shown in Figure 21, dried, and ground to the
desired size. The resulting polymer has a higher void co’ltent than the fine
powder. A typical production recipe was not found in the literatire
consulted.
PCTFE ?roductjon Processes
PCTFE is produced by mass, suspension, or emulsion polynerization. Each
process exhibits advantages and disadvantages when compared to the other
prccesses. ?tass polymerization gives very pure resins sinc no suspension
stabilizers or enulsifiers are useti. However, the, disadvantages include
poor temperature control and low conversion. Suspension polynerizatio
remedies the problems of temperature control and conversion, but produces a
polymer of high melt viscosity for a given molecular weight which compli-
cates resin fabrication. Overcoming the problems of both 01 these processes
Is emulsion polymerization. The major disadvantage of this final process is
the presence of increased impurities in the resin produced. Ultim. t.ely, the
end use of the product determines the process used.
Mass
Mass polymerization of PCTFE uses only CTFE monomer, a comonolner (if
desired), and an initiator. Mass polymerization gives products of high
purity but suffers from poor temperature control, poor reproducibility, low
conversion (35 to 40 percent), and long reaction times (seven day ) at los,
temperatures (—49°c).
Monomer, initiator, and comonoiser, if desired, are combined in a polym-.
ertzatioi reactor. Shown in Figure 22, the ‘:iction mass is discharged when
the conversion reaches 35 to 40 percent. dnreacted monomer is removed and
recycled while the polymer mass is extruded in a vacuum extrudet, A typical
production recipe was not found in the literature consulted.
Suspension Polymeriza j
Suspension polymertza ion of PCTPE overcomes some of the disadvantages
of ales polymerization since the water used to uspend the polymer aids Ln
teeperature control and reproducibility, increases conversion, and reduces
the reaction rime. However, unless a comonomer (vinylidene fluoride) is
included, it exhibits an unfavorable molecular veight—me t viscosity rela-
tionship. That is, the melt viscosity is higher at a given molecular weight
than nags or enrjlsLon polymerization resins, complicating resin
p:ocessing. (19J
211
-------
FIgure 21. Batch granular PTFE production.
Sovceg Encyc1 p!dia of Chem1ca1Te 0 3rd Zdition.
Seyno r S. Schwartz and Sidney H. Goodman, Pligtic , Material, and
Ptc ea ,e. , 1982.
ion’
To Wastevater
Treatiiient
a ion,
212
-------
Recycled Monomer
onome r
Vent
rnitiator
POLY R—
Comonomer
17.ATION
L r
VACUUM
EXTRUDER
1
PC TV!
Resin
Vent
F1c ure 22. Mass polymerization of PCTFE.
Source: Encyctopedia of Polyi ,er Science and TechncAogy .
213
-------
The suspension polymerization process is very similar to that used in
PTFE production. Shown in Figure 23, monomer, comonomer, initiator, and
dispersing agent are fed to a water filled reactor. When the reaction is
completed, the polymer is separated from the water and dried. A typical
production recipe was not found in the literature consulted.
Emulsion Polymerization
Emulsion polymerization exhibits the same advantages as suspension
polymerization as well as overcoming the unfavorable molecular weight—melt
viscosity relationchip. However, this produces a polymer with more impuri-
ties than either of the other two PCTFE types. Offsetting this problem is
the best reproducibility of the three processes and the most thermally
stable resi i.
Emulsion polymeri’ation of PCTFE is similar to the process used for
PTFE. As s ovn in Figure 24, CTPE monomer, any desired comonomer, emulsi-
fier, a’td initiator are added to a water filled polymerization reactor. A
typical recipe for producing PCTFE by emulsion polymerization is nhowr.
below:(72J
Material Parts by Weight
Chlorotrifluoroethylene (monomer)
Deionized Water 200
Perfluotooctanoic Acid (emulsifier) 1
Potassium Persulfate (initiator component) 1
Fcrrou Sulfate—Heptzhydrate (inItiator
componP t) 0.1
Sodium Sulfate (initiator component) 0.4
The details of polymer separation were ot available in the literature
sources consulted; however, the polymer particles are probably coagulated
and dried.
Energy Requirements
So data on the energy requirements for fluoropolymer processing were
found in the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH (X)NSIDERATION$
PTPE and PCTFE are nontoxic compounds used in coatings for food pro—
essing equipment. Although the polymer La not considered to be toxic, the
TPE monomer must be inhibited to prevent the hazards associated with violent
polymerization. Tfl is also flammable in air, with limits of 11 and 60
percent. The monomer forms explosive mixtures in air and oxygen, and can
disproportionate in the absence of air with the violence of black—powder
ezplosiong.177j Proper precautions and ventilation can control these
hazards.
Heated polymers are suspected as possible health hazards. [ 77J
214
-------
Vent
Monosier a -
Water
Initiato POLYMER-
IZATION
Dispersing REACTOR
rnonos e r
Emissions Emt sio
[ _ SEPARATION f— a’ 1 RyIgG “ ‘F - PCTFE Beads
To Was tevater
Treat gant
Figure 23. Suspension polymerization of PCTFE.
Source: Encyclopedia of Polymer Science and Technology .
215
-------
Figure 24. Emulsion iolymerizati’ n of PCTFE.
Source: Encyclopedia of Polymer Science and Technology .
216
PCTTE Resin
POLYMER—
IZATION
REACTOR
Emissions
To Was tevater
Treatment
-------
Above 400’C, perfluoroisobutylene and hydrogen fluoride, toxic com-
pounds, are released from PTFE in small amounts, though normal use does not
involve these high temperatures. There have been reports of polymer fume
fever in huna.is exposed to the unfinished product and thermodegration prod—
ucts.(107, 149J Exposure produces influenza—like symptoms, including
chills, headaches, rigor—like shaking of limbs, mild respiratory discomfort
and high fever. [ 107j
Only two compounds used in fluoropolymer production have been listed as
hazardous under RCRA: aSbestos, a filler, and chloroform, a polymerization
promoter.
Mass polymerization of PCTPE is carried to 35 or 40 percent conversion.
Therefore, it is expected that this process will have more VOC emissions
downstream of the reactor than the other processes.
Worker Distribution and Emissions Release Po 1 nts
Worker distribution estimates have been made by correlating major
equipment manhour requirements with the process flow diagrams in Figures 19
through 24. Estimates for PTFE and PCTFE production processes are shown in
Table 65.
No major point source air emissions are associated vith fluoropolymer
processing. The only air emissions are fugitive emissions from such sources
as reactor vents, bead dryers, and extrudera. The magnitude of the impact
of these emissions on the environment and/or worker health depends upon pro-
cess operating parameters, input materials, and engineering and administra-
tive controls.
Table 66 shows sources of fugitive emissions from fluoropolymer manu-
facture. Employees may be exposed to vapor—phase monomer and comonomer (see
Table 64) and polymer particulates which may contain residual fillers,
stabilizers, and other additives. Avai1abl toxicity information for major
contaminants is given below. More complete health effecta information is
summarized iti Table 10 and in IPPELI Chapter lOb.
Health Effects
The manufacture of fluoropolyisers involves the use of a confirmed human
carcinogen, asbestos, and a suspect!d human carcinogen, chloroform. Asbes-
tos is used as a filler and chloroform as promoter in the process.
Chlorine ar.d ozone, both highly tf zic substances, are used as stabilization
aids. The reported health effects f exposure to these substances are
summarized in the following paragraphs.
Asbestos is classified as a human carcinogen by the International
Agency for Research on Cancer 11041 and by the American Conference of
Governmental Industrtaj Rygienista.(5J It is c.urrently undergoing addi-
tional tests by the National Toxicology Program.(233J Many deaths from
exposure to asbestos are due to lung cancer.(104J Not oiily is the lung
cancer risk dose—related, but there is also an important enhancement of the
217
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TABLE 65. RKER DISTRIBUTION ESTIMATES FOR PLUOROPOLYNER PRODUCTION
Process Uait Votkerg/Ijnjt/8—hour Shift
flfl :
Aqueous Emulsion Batch Reactor 1.0
Polymerization Condenser 0.125
Evapor tor 0.25
Fine Powder Emulsion Batch Reactor 1.0
Polymerization Dryer o.s
Suspension Polymerization Batch Reactor 1.0
Polymer Separator 0.25
Dryer 0.5
Grinding 0.25
PCTFE :
Mass Pnly.erigation Batch Reactor 1.0
Extruder 1.0
Suspension Polymerization Batch Reactor 1.0
Polymer Separation 0.25
Dryer
Emulsion Polymerization Batch Reactor 1.0
Dryer o.s
218
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TABLE 66. SOURCES OF FUGITIVE EMISSIONS FROM PTFE AND PCTFE PRODUCTION
PTFE Processes PCTFE Processes
Emul— Sue— Sue— Emul—
Source Constituent sion pension Mass pension- slot ?
Reactor Vent Monomer X X X X X
Comonomer X X X X X
Evaporator
Condenser Vent Monomer
Co ’”io mer
Polymer Dryer
Vent Monomer * * *
Comonomer * * *
Particulates 7 b x x x
Polymer
Separation Monomer * *
Couuoi’mer * *
Polymer
Grinding Monomer *
Comonomer *
Particulates X
Vacuum
Extruder Monomer X
Comonomer x
&Aqueous dispersion resin only.
bpine powder resin only.
*Trace amounts of monomer end comonomer are expected due to high conversion
levels and removal of unreacted compounds.
219
-------
risk in those exposed to asbestos who also smoke cigarettes.(104j The 058*
emergency air standard is 0.5 fiber >5 tim/cc (8 hour TUA).
Chlorine is highly toxic by inhalation and a strong local irritant.
(2421 Exposures to 3—6 ppm causes a stinging or burning sensation in the
eyes, nose, and throat, headache, sneezing and coughing, loss of voice, and
nose bleeding.(173j Chronic exposures to concentrations on th. order of S
ppm have led to premature aging, bronchial disease, and predisposition to
tuberculosi 9. (1701 It has also caused matat ions in human lymphocyte somatic
cells at 20 Pp..(363 The OSHA air standard has been set ati ceiling for
exposure of 1 pps.(693
Chloroform produces tumorigenic, nutagenic, teratogenic, and careino—
genie effects in laboratory animals. (233] It has been designated a sus-
pected human carcinogen by the International Agency for Research on Cancer.
(1083 Chloroform is also moderately toxic and in high concentrations may
cause narcosis and death. [ 1573 Rapid death is attributable to cardiac
arrest, while delayed death haa been associated with liver and kidney
damage. (108] Syiptoms of chloroform exposure at sublethal concentrations
include respiratory depression, dizziness, nausea, and intracranial pres-
sure; after—effects include fatigue and h.adache.(53 The OSUA air standard
is 5.0 ppm (8 hour TWA).(67j
Ozone produces tumorigenic, .tagenic, and teratogenic effects in
laboratory anlmals.(2333 It ii .also highly irritating to the relpiratory
tract, skin, eyes, and mucous membranes.(243J The primary site of acute
injury is the lung, which is characterized by pulmonary congeetionand
hemorrhage, but there are IndIcations in man that there are aeëondary sites
of reaction.(4j When inhaled at concentrations not acutely injurious per
se, ozone may initiate, accelerate, or. exacerbate respiratory tract disease
of bacterial r viral origin.(4J The 058* standard in air is 0.1 ppm (8
hour TV*).(67!
Air Emissions
Sources of fugitive emissions are summarized in Table ó6 by process and
eon;titue t type. These sources are priestly process vents and may be con—
trc’ “led by routing the veotedetrea. to a flare or blowdown.(285J Other
process VOC emissions result from leaks in valves, flanges, pumps and cóâ—
preesors. *lth iugh some equipment modifications are available to, reduce
elissions, a regular inspection and maintenance program may be ‘the best
control.
Sourcem of fugitive particulate. at. also listed In Table 66. These
emissions may be controlled by venting the stream to a baghouse or electro-
static precipitator for particulate removal.
Vaatevater Sources
There are several sources of va cevater asse.iated with fluoropoly.er
processing, shown in Table 67. The major wastewater sources result from
emulsion ar 1 suspension polymerization which use water as a medium to aid in
220
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TABlE 67. SOURCES OF WASTEWATER FROM FrYE AND PCT?E PRODUCTION
FrYE Processes PCTPE Processes
Source E uleion Suspension Mass Suspension E u1si n
Polymer Concentration Xa
Polymer Isolation Xb x
Polymer Separation X x
Routine Cleaning Water X X X X X
aaqueoui dispersion resin only.
bfjne powder resin only.
221
-------
heat transfer. No data concerning wastevater production or characteristics
ver found in the literature consulted.
Solid Wastes
The solid wastes generated by this process are mostly fluoropo’mers.
Solid vOste streams include: resin lost during spil1a e and cleaning,
collected particulate., and substandard resin which cannot be blended.
Environmental Regulation
Effluent limitations guideline. have been set for only the PTPE resins
portion of the fluoropolymerindustry. IPT, UT, and NSPS call for the p0
of the effluent to fall between 6.0 and 9.0 (41 Pederal Register 32587,
August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release mote than 200 ppm above
backgrc und, except in emergency pressure releases, which should not
last more than five days; .ind
• Leaks (which are defined as VOC emissions r.ater than 10,000 ppm)
must be repaired with 15 days.
Asbestos (a filler) and chloroform (a promoter), designated as uD13 and
U044 , reapectively, are lLsted as haaardous wastes (#6 7e cral Register
27476, May 20, 1981). All disposal of these compound. or fluoropolymers
containing these compounds must L3sp17 with th. provisions set forth in the
Resource Conservation and Recovery Act (RCRA).
222
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SECTION 9
PHENOLIC RESINS
EPA Source Classification Code — Polyprod. General 3-01-018-02
Bakelite — General 3—01-018-05
INTRODUCTION
Phenolic resins are heat resistant, chemical resistant, dimensionally
and thermally stable, low Cost resins. Their easy moldability, good elec-
trical properties, and surface hardnes, make phenolic resins desirable in
many applications, including use in the electrical, automotive, appliance,
ano conswner industry. Phenolic resins also have several industrial appli-
cations which include use in the sands used to make foundry shell molds and
cores.
Phenolic resins are the condensation product of phenol and formalde-
hyde. There are two types of resins produced: single—stage and two—stage.
Single—stage resins, which are more commonly called resole, are inherently
thermosetting. Once the reaction is completed, the resin will crosslink
without a catalyst at room temperature. Therefore, resols are stored at
cool tei iper ture , arid exhibit a snorter shelf life than two—stage resins.
Alkaline catalysis and a stoichiometric amount of formaldehyde and phenol
characterize resol production.
Two-stage resins, called novolaka, are manufactured using acid cataly-
sis and less than a stoichiorietric amount of formaldehyde to react with the
phenol present. The result is a brittle, thermoplastic solid which requires
a catalyst, or curing agent, for cross—linking to occur.
Table A—b in Appendix A presents typical properties of phenolic resia
compounds aecordiiig to specification. Molding compounds, as well as other
phenolic resins, are formulated according to the specific end use. The
propertie, of the resulting resins also depend upon the formulation used to
manufacture them.
The two major phenolic resins are used in six different product areas:
molding compounds, laminates, bonding resins for plywood, other bonding
resins, foundry use, and coatings. Bonding and adhesive resins for plywood
is the largest single market for phenolic resins, which captured over 29
percent of the sale . for l980.(65J Other phenolic resin uses include:
coated and bonded abrasive production, fiber bonding for insulation, fric—
ion materials (including brake linings, clutch facings, and transmission
i...nds), and ‘ded parts for automotive and electrical uses.
223
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INDUSTRY DESCRIPTION
In 1980, phenolic resins contributed 4.3 percent of the total sales for
the plastics industry.(65J The phenolic resins industry consists of 50
producers which have 108 sites in 29 different states. One—fourth of the
sites are located in the Great Lakes Region (EPA Region V); the remaining
sites are distributed throughout the remaining states with New York and New
Jersey, the southeast, the south—central, and the northwest regions each
containing at least 10 percent of the sites., Major U.S. phenolic resin
producers and their locations are listed in Table 68. The capacities of the
plants listed are not available in the literature.
Phenolic resins are used in s wide variety of goods for consumers and
industry. Adhesives, coatings, an laminates are used not only in the con-
struction industry, but also in furniture and furnishings, appliances, and
electrical products, The phenolic resin industry is affected by consumer
siending and the automobile and.,housjng industries. After growth to a pro-
duction peak of 830,500 metric tons in 1978 from 609,100 metric tons in
1976, the 1981 level fell to 667,000 metric tons.f 65, 1433 Th compound
growth rate of phenolic resin production for 1975 to 1980 was 7.4 percent.
(651
PRODUCTION AND END USE DATA
In 1981, U.S. sale. of phenolic resins totaled 667,000 metric tons.
Phenolic resins are used in many products, which include: [ 22, 118, 2643
• Adheajve ‘for plywood, particle board, fiberboard, wafer board,
beams, an d arche, where durability in high humidity is required;
• Bonding for glass and rock wool fibeis used in insulation,
acoustical insulation, and carpet underlay;
• Decorative and industrial laminates ‘for paper, cotton, or glass,
including electronic circuit boards, gears, rods, bearings, tube,,
furniture, wall paueling, and home and office furnishings;
• Foundry resins for synthetic, resin—bonded sand mold, used to
produce machine housings, automotive transmissions, cylinder heads,
large metal part., and intricate meta, objects;
• Resins for bonding abrasive., including grinding wheels and snagging
wheels’, and for coated abrasive., including sandpaper, discs, and
belts;
• Resins for friction materials used in automotive applications
(including brake linings, clutch facings, and transmission bends) as
well as for aircraft, train, and drilling rig parts;
• Molding compounds used for electrical sockets, sUch gear, circuit
breakers, automotive distributor caps, relays, brake pistons, coffee
makers, utensil handles, and general appliance parts;
224
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TABLE 6C. U.S. PHENOLIC RESIN PRODUCERS
°roducer Location
American Cvanaisid Co.
Formica Corporation, subsidiary Evendale, OH
American Hoecl st Corporation
Industrial Chemicals Piv sion Mount Holly, NC
AMETEK, Inc.
Have , Divic ion Wilmington, DE
Ashland Oil, Inc.
Ashland Chemical Co., subsidiary
Chemical Systems Division Columbus, OH
Four Jry Products Division Calumet City, IL
Cleveland, OH
Baker International Corporation
Magna Corporation, subsidiary Houston, TX
The Bendix Corporation
Friction Materials Division Green Island, NY
Borden Inc.
Borden Chemical Division
Adhesives and Chemical i Division Demopolis, AL
Diboll, TX
Fayetteville, NC
Premont, CA
Rent, W A
La Crande, OR
Louisville, KY
Miseoula, PIT
Sheboygan, WI
Springfield, OR
Brand—S Corporation
Cascade Resins Division Eugene, OR
Chargiri Villey Co. Ltd.
Nevamar Corporation, subsidiary OdenP,n, MD
Clark Oil & Refinery Corporation
Clark Chemical Corporation,
subsidiary Blue Island, IL
Core—Lube, Inc. Danville, IL
(continued)
225
-------
TABLE 68 (continued)
Producer ocation
CPC International Inc.
CPC North American Division
Industrial Diversified Unit
Acme Resin Group Forest Park, IL
The Dexter Corporation
Midland DiVib on Vaukegan, IL
General Electric Co.
Engineered Materials Group
Electromaterjals Business Department Coshocton, OH
Schenectady, NT
Plastics Business Operations Pittsfield, MA
The P. D. George Company St. Louis, MO
Georgia—Pacific Corporation
Chemical Division Albany, NT
Columbus, OH
Conway, NC
Coos lay, OK
C osett, AR
E g ne, OR
Louisi4lle, MS
Lufkin, F
Newark, OH
Peachtree City, GA
Port Ventvorth, GA
Richmond, C?
Russeilville, SC
Taylorsville, MS
Iflciah, CA
Vienna, GA
Getty Oil Co.
Chembond Corporation, subsidiary Andalu.ia, AL
Spokane, VA
Springfield, O k
Vinnfield, LA
Gulf Oil Corporation
Gulf Oil Chemicals Co.
Industrial Chesicals Division Alexandçja, LA
Heresite—Saekaphen, Inc. Manitovoc, VI
(continued)
226
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TABLE 68 (continued)
Producer Location
Hugh J.—Resins Co. Long Beach, CA
Inland Steel Co.
Inland Steel Container Co. Division Alsip, IL
The Ironsidea Co. Columbus, OR
hoppers Co., Inc.
Organic Materials Group Bridgeville, PA
Lavter International, Inc. Moundsville, AL
Libbey-Owens—Pord Co.
LOP Pinstic Products, subsidiary Auburn, P
MasonJte Corporation
Alpine Division Culfport, MS
Minnesota Mining and Manufacturing Co.
Chemical Resources Division Cordova, IL
Cottage Grove, PQ4
Mobil Corporatton
Mobil Oil Corporation
Mobil Chemical Co. Division
Chemical Coatings Division Kankakee, IL
Rochester, PA
Monogram Industries Inc.
Spaulding Fibre Co., Inc. subsidiary DeKalb, IL
Tonawanda, PlY
Monsanto Co.
Monsanto Plastics and Resins Co. Addyston, OH
Chocolate Bayou, TX
Eugene, OR
Santa Clara, CA
Springfield, MA
Pities Chemical Paint Co.
Kordell Industries Division Mishavaka, IN
The O’Brien Corporation
The O’Brien Corporation—Southwestern
Region Houston, TX
(continued)
227
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TABLE 68 (continued)
Producer Location
Occidental Petroleum Corporation
Hooker Chemical Corporation, subsidary
Plastics and Chemical Specialties
Group
Durez Division Kenton, OH
North Tonavanda, NY
Owens—Corning Fiberglass Corporation
Resins and Coatings Division Barrington, NJ
Kansas City, KS
Newark, OH
Wazahachie, TX
Plastics Engineering Co. Sheboygan, WI
Polymer Applications, Inc. Tonavanda, NY
Polyrez Co., Inc. Woodbury, NJ
Raybestos—Manhat tan, Inc.
Adhesivies Department Stratford, CT
Relchhold Chemicals Inc. Andover, MA
Carteret, NJ
Detroit, Mt
Kansas City, KS
Moneure, NC
South San Francisco, CA
Tacoma, WA
Tuscaloosa, AL
White City, OR
Vacuum Division Niagara Falls, NY
Rogers Corporation Manchester, Cr
Schenectady Chemicals Inc. Oyster Creek, TX
Rottardam Junction, NY
Schenectady, NY
The Sherwin—Williams Co.
Chemicals Division Fords, NJ
Simpson Timber Co.
Oregon Overlay Division Portland, OR
(continued)
228
-------
TABLE 68 (continued)
Producer Location
The Standard Oil Co. (Ohio)
Sohio Industrial Products Co.,
Division
Don—Oliver Inc. Unit Niagara FalLs, NY
Union C irbide Corporation
Coatings Materials Division Bound Brook, NJ
Elk Grove, CA
United Technologies Corporation
Inmont Corporation, subsidiary Anaheim, CA
Cincinnati, OH
Detroit, MI
Valentine Sugars Inc.
Valite Division Lockport, LA
West Coast Adhesives Co. Portland, OR
Westinghouse Electric Corporation
Insulating Materials Division Manor, PA
Micarta Division Hampton, SC
Weyerhauser Co. Longview, WA
Marshfield, WI
Sources: Chemical Economics Handbook , updated annually, 1981 data.
Directory of Chemical Producers , 1982.
229
-------
• Resins for coatings and adhesives which include automotive primer.,
can coatings, dnu linings, anticorrosion paints, printing inks,
wire enamels, and varnishes; and
• Foam for flower arrangement bases and decorative arts.
Table 69 lists phenolic resin consumption by market, while Table 70 presents
major markets for phenolic resin molding compounds.
Novolaks exhibit greater molding latitude, better dimensional stabil-
ity, and better long—term storage capabilities than resol resins. The addi-
tion of nexa ma a curing agent,,however, adds the possibility of ammonia
emissions after the resin has been :ure4.
Resols are used in electrical, electronic, and appliance applications
where ammonia outgassing, a problem with hexa addition in novolaks, might
corrode metal or where odor may be objectionable. Resols offer batter
resistance to cracking where one side is wet and the other side is dry, asi
in steam iron handles, percolator bases, and dishvasher part.. I
PROCESS DESCRIPTIONS
There are two types of phenolic resins produced: single—stage resins,
called resols, and two—stage resins, called novolaks. Resols are produced
using stoichiometric amounts of formaldehyde and phenol. The polymerization
produces thermosetting chains wI tch are not cross—linked. In fabrication of
the desired end product, heat causes the resin to form an infusible cross—
linked material. Novolaks are produced with only part of the formaldehyde
stoichlometrtcally necessary for reaction with the phenol. The thermopla.—
tic produced is a brittle solid at room temperature. Hememethylenetetra—
mine, called hexa, is added to provide the necessary crosslinking when heat
is applied during product fabrication.
Resol Chemistry
Resol production uses an alkaline catalyst, such as sodium hydroxide,
to initiate the reaction., A phenol anion is formed which then reacts with a
formaldehyde molecule to yield a methylolphenol anion. ThLs methylolphenol
anion, in turn, reacts with a phenol molecule to produce a methylolphenoj.
molecule and a phenol anion. O. ce the methylolphenol molecule is formed, it
will react with other formaldehyde molecule. until all the reactive sites
are occupied. Once there is no free formaldehyde, the methylol groups on
the phenol molecule combine with other ‘ t hylol groups in a condensation
reaction. These condensation reactions tovide the structure necessary for
crosslinliing. Upon heating during the processing steps, the polymerization
is completed when the infusible, cross—linked state is reached. This
sequence of steps is shown below.
230
-------
tABLE 69. 1981 cONSUMPTION OF PIjENOLIC RESINS
Market Thousand Metric Tons
Bonding and Adhesive Resins for:
Coated and Bonded Abrasives 16
Fibrous and Granulated Wood 42
Friction Materials 15
Foundry and Shell Moldings 33
Insulation Materj3ls 135
Laminating
Building 15
Electrical/Electronics 10
FurnIture 8
Other 5
Plywood 200
Molding Compounds 116
Export 12
Other 60
TOTAL 667
Source: Modern Plastics , January 1982.
231
-------
tABLE 70 • 1981 PHENOLIC RESIN MOLDING MPOUND MARKETS
Market Thousand Metric Tons
Appliances ii
Closures
Electrical/Electronics 55
Housewares 17
Industrial 4
Transporation 12
Other 3
TOTAL 116
Source: Modern Plastics 1 January 1982.
232
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tnt t tat ion
OH 0 0
0H _____
O Y
Intermediate Formation
O_ O_
+ ______ CH 2 OH
CH 2 O
O OH OH
( rCH 9 OH + . + (‘ .-CH 2 OH
OH
CH 2 OH
OH
OH
( CH 2 OH — -v + CH 2 O
+ CH 2 O * OH
c CH20} + 20 CH 2 OII
233
-------
Condensation
OH
2 OH
I 20
Cured State
OH
o -
OH OH OH
CH 2 OH cHrf/ f.cH 2 OH
¼ ) 120
Movolaks are prodvced using an acid catalyst. This reaction is initi-
ated vhen formaldehyde reacts with a hydrogen ion in solution to for. a
protonated formaldehyde molecule. This reactive group then combine. vi th
the phenol molecule at a po.itiofl para to the OH group. Thi, reaction also
regenerates a hydrog.n ion. The hydrated carbonium ion and the alcohol (OH)
grour on the cyclic ring may eliminate a molecule of vater to form a rcac—
tive group. This zroup may then react with a phenol molecule to produce a
hydrogefl ion and a dihydroxydiphenylmethane molecule. Hexamethylenetetra—
mine (hexa) 1. added to the product before shipping. Upon the addition of
heat during product processing, the novolak structure will crosslink to form
an infusible solid with hex.e providing the additional formaldehyde for the
linkages. This series of reactions is shown below.
1
Novolak Chemistry
234
-------
Initiation
20 + W —ø 20
Intermediate Formation
OH OH
—
CH 2 04 CH 2 OH
Condensation
+ CH 2 OH
OH
CH 2 OH 2
CH 2
OH
A
+
OH
+ Il
+
OH
V
+
235
-------
Curing Reaction
+
OH
OH heat
+ H 4 — -
+ NH 3
Table. 71 and 72 list typical input materials and operating parameters
for the two types of phenolic resin, produced. Other input material,, such
as cononomers, fillers, and c ta1ysts, are listed in Table 73.
esols
Resol production, as presented In PiBure 25, starts when phenol and
formaldehyde are charged to a stirred reactor. An alkaline catalyst is
added to adjust the p11 of the solution to the reaction condition, desired,
Vacuum removal of the water formed by the condensation reaction is performed
at temperatures below 100C to prevent over—reaction or gslatjon.
A typical recipe for resol production is shown belov:11233
Matecial Parts by Weight
Phenol 94
Formaldehyde (372) 123
Barium Hydroxide Hydrate (rsitalyst) 4.7
2
‘2
OH
236
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TABLE 71,. TYPICAL INPUT M&TERIALS TO PHENOLIC RESIN PRODUCTICN
IN ADDITION TO FORMALDEHYDE AND PHENOL
Phenolic Alkaline Acid Cure
Resin Type Catalyst Catalyst Fillers Catalyst
Resol X X
Novolak X X
TABLE 72. TYPICAl. OPERATING PARAMETERS FOR PRENOLIC RESIN PRODUCTION
Phenoljc Formaldehyde—
Resin Type Temperature Phenol Ratio Reaction Time
Resol 80 to 100°C 1:1 to 1.5:1 1 to 3 hours
Novolak 85 to 90°C 0.75:1 to 0.93:1 3 to 6 hours
Source: Encyclopedia of Chemical Technology , 3rd Edition.
237
-------
TABLE 73. TYPICAL IPWUT MATERIALS AND SPECIALTY QIEMICALS USED IN
PHENOLIC RESIN PRODUCTION IN ADDITION TO PHENOL AND
FORMALDEHYDE
Function
Curing Agent Hexamethylenecetranine (hexa)
cid Catalyst. Hydrochloric acid
Ozalic acid
Phosphoric acid
p—toluenesulfontc acid
Sulfuric acid
Alkaline Catalysts Bartu. hydroxide
Calciun hydroxide
Organic amines
Sodiun carbonate
Sodiun hydroxide
Conononers Acetaldehyde
Siephesol—A
Cresols
Furfuraldehyde
Nonylphenol
Octylpheool
p—phenylphenol
p—tert—butylphenol
Easorcinol
t—butylphenol
Xy lenole
Fillers Asbestos
Cellulose
Clay
Cotton flock
Glass
Nydratid alunina
Mica
Organic fibers
Wood flour
Sources: Eucyclopedia of Chenical Teehuology , 3rd Edition.
Encyclopedia of Polyner Science and Technology.
Modern Plastics Encyclopedia 1 1981—1982.
238
-------
25.
Resol production proceee.
Snurce.: Encyclopedia of Chemical Technology , 3rd !dition.
Encyclopedia of Iolvmer Science and Technology .
I )
‘0
Liquid
aesin
Lu.p.
Organic
Solveiat
It
-------
When the reaction has reached the desired end—point, usually over 95
percent conversion based on phenol, the contents are cooled by a rapid
discharge to either a cooled stainless steel floor or a resin cooler. [ 22J
Resin coolers are aseemblies of water—cooled, baffle plates spaced approxi-
mately 4 cm apart. [ 22J The resin is cooled quickly in layers between the
plates.
Resols may be produced as liquid resins (resins in solution or casting
resins) or as solid resin lumps, solid resin flakes, or coarsely—crushed
solid resin. Liquid resins require no di ,hydratjon step. They are fed from
the reactor into drums or tank cars for shipping. The dried resin may be
dissolved in an organic solvent, such as alcohol, and used as a varnish,
coating, ur prelamination treatment. Casting resins are transferred from
the reactor to molds. Solid resins maybe combined with fillers and are
shipped in fiber drums, plastic bags, or molti—wall paper begs.
Resols have recently been p’oduced in a dispersion, The addition of a
protective colloid to the reactor allows the production of an in—sit :: dis-
persion. If a solid resin is desired, the ophecial particles may be
recovered from the liquid resin and dried via rapid sedimentation at the end
of the reaction.(7J Protective colloids used include polyvinyl alcohol,
natural gums, and cellulose derivatives.
Novolaka
La illustrated in Figure 26, n’ volaka are produced using phenol, for-
maldehyde, and an acid cataly t. A limiting amount of formaldehyde is used
to prevent croeslinking when the phenol and formaldehyde are charged to a
stirred eactor, T-e catalyst is added until the solution reaches the
desired p11, the temperature of the solution is adjusted, and the water is
ref luxed to the reactor for the duration of the reaction period.
A typical recipe for novolak production is shown below: (251J
Material Parts by Vei ht
Phenol 42
Formaldehyde 27
Wood Flour (filler) 52
(curing agent) 3.7
Sulfuric Acid (catalyst) 0.1
Nigrosj (black dye) 1.3
Calcium Stearate (mold release agent) 0.7
When the reaction has proceeded to the desired end point, usually to a
conversion greater than 95 percent, the water is no longer recycled to the
reactor. Any remaining moisture is removed under a vacuum. When the water
removal is complete, the resin is dischar&ed to resin coolers, which may be
shallow pans or cleaned floor areaa.f22J If a flaked resin is desired, th
molten resin Is sent directly to a resin flaker. Resins used in solutIc
are produced by the addition of solvent to the reactor, eliminating t ie
dehydration step. is added after all processing is
completed to provide erosslinking upon heating.
240
-------
dnd
Figure 26.
Novolak production process.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Reein
IJquld
Rss In
Veu
Rea in
-------
Energy Regujremen
No data on the energy requirements for phenolic resin proce sing were
found in the literature consulted.
ENVIKOrjpi r j AND INDUSTRt L HEALTh CONSIDERATIONS
Phenolic resins are considered to be nontoxic in the cured state.
Uncured resins, however, contain small amounts of free phenol and formalde-
hyde. Therefore, care should be taken in the handling and storage of these
resins. The manufacture of novolaks calls for a limiting amount of formal-
dehyde, and all phenolic resins are carried to over 95 percent conversion
based on phenol. Most emissions of phenol and formaldehyde will occur in
the reactor vent and ref lt’ condenser vent; little emission of these sub-
stances is expc ted from downstream operations.
Worker Distribution and Emissions Release Points
Worker distribution estimates have been made by correlating major
equipment manhour requirements with the process flow diagrams in Figures 25
and 26. Table 74 shows estimate, for both resol and novolak production.
There are no major air emission point source, associated with the
phenolic resin proceases. Fugitive emissions from process sources as vents
and leaks, however, nay nose a signific environmental and/or worker
health problem dependiag on stream constituents, process operating param-
eters, engineering and administrative controls, and maintenance programs.
Sources of fugitive emissions are listed in Table 75. Principal
gaseous emissions of concern are phenol and formaldehyde. Cresols, bis—
phenol A, furfuraldehyde and acetaldehyde may be uied as cnmonon era.
Phenol an’s formaldehyde handling is highly automated in moat plants,
thus minimiziag employee exposure potential.I118J
The of huamethyleaetetramjne as a curing agent in novolak produc-
tion presents the possibility of employee exposure to ammonia, a by—product
of the curirg reaction. Acid catalysts (sulfuric, hydrochloric or phos—
horic acics) us d in novolak production also may present a hazard.
Employees assigned to crushing, grinding and flaking operations may be
Overexposed to nuisance dust from polymer particulate emission, or to such
additives as asbestos. Available toxicity information for contaminants
associated with phenolic resin production is sumaarjzed in the following
paragt-aphs, in Table 10 and in IPPEU Chapter lOb.
Little data are available in the literature from which employee expo-
sure potential may be estimated. However, one source gives the following
emission factors for phenolic resin processing: f286J
• CriMing——16 g p ’rticula e matter/kg product
• Adhesives produetion——25 g hydrocarbon/kg product
• Molding——7— g hydrocarbon/kg product
242
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TABLE 74. RXER DISTRIBUTION ESTIMATES FOR PRENOLIC RESIN PRODUCTION
Process Unit Workers/Unjt/8—hour Shift
Resol Production Batch Reactor i.o
Ref lux Condenser 0.125
Resin Cooler 0.25
Crusher 0.25
Haunneruilil 0.25
Batch Mixer 0.5
Novolak Production Batch Reactor i.o
Reflux Condenser 0.125
Resin Cooler 0.25
Crusher 0.25
Haininerinji ]. 0.25
Flaker 0.25
Batch Mixer 0.5
243
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TABLE 75. SOURCES OF FUGITIVE EMISSIONS FROM PHENOLIC RESIN M&NUPACTURE
Phenoije Resin
Source Constituent Resol Novolak
Reactor Vent Phenol X X
Formaldehyde x X
Ref lux Condenser
Vent Phenol X X
Formaldehyde x x
Resin Cooler Vent Phenol * *
Formaldehyde * *
Resin Crusher Vent Resin Particulate. X X
Resin Flaker Vent Resin Particulates X
Hammermill Vent Resin Particulate. X X
Mixer Vent Solvent K
Resin Particulate. K
*Near complete reaction, combined with recycle of unreacted monomers to the
reactor, reduces the phenol and formaldehyde emissions downstream to trace
amounts.
244
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Health Effects
Phenol and formaldehyde, two of the major raw materials in phenolie
resin production, pose a significant health risk if exposure occurs. The
comonomer resorcinol, and asbestos, which is used as a filler, also are
significant due to carcinogenic, mutagenic, teratogenic, or toxic proper-
ties. The reported health effects of exposure to these four substances
follow.
Asbestos is classified as a human carcinogen by the International
Agency for Research on Cancer (104) and by the American Conference of
Governmental Industrial Hygieniats. [ 5J It is currently undergoing addi-
tional tests by the National Toxicology Program. [ 233J Many deaths from
exposure to asbestos are due to lung canger. (104J Not only is the lung
cancer risk dose—related, but there is also an important enhancement of the
risk in those exposed to asbestos who also smoke cigarettes. [ 104J The OSHA
emergency air standard is 0.5 fiber >5 urn/cc (8 hour TWA).
Formaldehyde poses a high toxic hazard upon ingestion, inhalation, or
skin contact [ 242) with human effects reported at doses as low as 8 ppm.
[ 127) This suspected carcinogen is a potent mutagen and teratogen. The
OSHA air standard is 3 ppm (8 hour TWA) with a 5 ppm ceiling. [ 67]
Phenol is extremely toxic by ingestion, inhalation, and skin absorp—
tton.18S1 Approximately half of all reported cases of acute phenol poison-
ing has resulted in death.(278J Chronic poisoning may also occur from
industrial contact and has caused renal and hepatic darnage. (149J Evidence
indicates that phenol is also a tumorigenic, mutagenic, and teratogenic
agent; however, a recent carcinogenesis bioassay by the National Cancer
Institute produced negative results.(233) The OSFIA air standard is 5 ppm (8
hour TWA).f67J
Resorcinol is a turnorigen and a mutagen according to animal test data
(233]; however, carcinogenic testing has produced indefinite results. [ 105J
The chemical is currently being tested for carcinogeneais under the National
Toxicology Program. Resorcinol is also highly toxic by ingestion. An oral
exposure of 29 mg/kg has caused death in humana. [ 52J
Air Emissions
Pugitive VOC emission sources are listed in Table 75 by resin type and
constituent. All of these sources are vents and may be controlled by: [ 285J
• Venting the stream to a flare to incinerate the hydrocarbons;
and/or
• Venting the stream to blovdown.
Other VOC emisqions may result from valves, relief valves, flanges, drains,
pumps, compressors, md cooling towers. Equipment modification may be used
to control these emissions, but a regular inspection and maintenance program
may effectively reduce most of the VOC emissions from these sources.
245
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Fugitive particulate emissions are also summarized in Table 75. These
also result from vents and say be controlled by:
• Venting the stream to a baghouse or electrostatic precipitator to
remove particulates.
According to EPA estimates, the population exposed to pheuolic resin emis-
sions in a 100 km 2 area surrou . d1ng a phenolic resin plant is: 40 persons
exposed to hydrocarbons and 22 persons exposed to pa.ticulates. [ 286J
Vastewater Sources
There are only two sources of vastewater associated with phenolic resin
production, as shown in “able 76. The water generated from the condensation
reaction used to produce the resin is the major vastevater stream. Routine
cleaning water contribut , s a smaller amount to the wastevater produced.
Ranges of several parameters for vastevaters from phenolic resin
Processing are shown below. Values for the vastevater from the processes
described were not distinguished by process type by EPA for the purpose of
establishing effluent limitations for the phenolic resin industry.(284J
Phenoljc Resin Unit/Metric
Wastewater Ton of Phenojic
Charactexjsti . , Resin —
Pr3dUCtio 1.67 — 24.03 3
80D 3 2 — 20.7 kg
COD 5 — 33.5 kg
TSS O30kg
Solid Waste ,
The solid wastes generated by this procee , include eubstanda,’d product
which cannot be blended, collected particulate., and resin lost during
routine cleaning and spillage. These wastes are comprised mainly of
phenolic resins.
Environmental Regulation
Effluent limitations guidelines have been set for the phenolic resin
industry. BPT, BAT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source p’rformance standard, proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safet,/-.lea ,e valves must not release more than 200 ppm above
background, except in emergenc r pressure release., which should not
last more than five days; and
246
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TAL 7 . Sou CZs ‘ ‘ ‘J STEWATER FROM PHENOLIC RESIN M&NUFAC URE
Phenolic Resin
Source Resol Novolak
Condensation Reaction Water X X
Routine Cleaning Water X X
247
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• Leaks (which are defined as VOC emissiona greater than 10,000 ppa)
must be repaired within 15 days.
The following compounds are listed as hazardous wastes (46 Federal
Register 27476, May 20, 1981):
Acetaldehyde — U001
Asbestos — U013
Cresole — U052
Formaldehyde — U122
Phenol. — U188
Resorcinôl — U201
All disposal of either of these compounds or phenolic resins which contain
restdual amounds of these compounds (i.e., uncured resins) must comply with
the provisions set forth in the Rec *rce Conservation and Recovery Act
(RcR ,).
248
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SPCTION 10
P0LYA ETAL
EPA Source Classification Code — Polyprod. General 3-Oi-018-02
INTRODUCTION
Polyacetals, or acetal resins, are strong, hard, highly crystalline
thermoplastics. First commercially produced in the 1960’s, these versatile
polymers possess a good balance of short— and lcng—term mechanical proper-
ties. Their high melt temperature, stiffness, and good processibility
(short—term properties) are combined with low friction, fatigue resistance,
corrosion resistance, and dimensional stability (long—term properties),
making them an ideal replacement for nonferrous metals in many applications.
Polyacetals are produced from the polymerization of formaldehyde. The
repeating oxymethylene structure, —OC R2—, gives these resins a chemistry
similar to that of simple acetals. Metal homo olymera consist of only this
repeating oxyniethylene structure while acetal copolymers have an occasional
interruption in the oxymethylene chain for a comonomer unit, such as an
ethylene linkage. Trioxane, an oligomer of formaldehyde consisting of three
units in a cyclic structure, is used along with a cyclic comonomer to manu—
factt.re the acetal copolymer. Copolymers are more stable to thermal degra-
dation, oxidation, and chemical attack due to the stabilizing nature of the
comonomer unit. Table A—il in Appendix A lists some typical properties for
acetal homopoly’mers and copolymers.
Polyacetals are the first plastics with strength properties approaching
those of nonferrous metals. [ 247J These resins are rigid, tough, and resili-
ent but not brittle. Properties are retained over an extended time, even
during adverse temperature and humidity condit ona or while being exposed to
most solvents. Polyacetals are denser than most plastics, yet they are
lighter than any of the die—casting metal alloys: 85 percent lighter than
brass, 80 percent lighter t 1 lan zinc and iron, 45 percent lighter than
aluminum, and over 20 percent lighter than magnesium.(247j
INDUSTRY DESCRIPTION
Two producers make up the polyscetal industry. Celanese manufactures
various grades of acetal copolymers at their Bishop, rexas site while du
Pont produces acetal homopo lymers at their Parkersburg, West Virginia plant.
These producers and their capacities are presented in Table 77.
Polyacetals are used primarily as metal replacements. Automotive,
pii mbing, and machinery parts and consumer products are the largest markets.
249
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TA8LE 77. U.S. PRODUCERS OF POLYACETALS
1982 Capacity
Thousand
Producer Location Metric Tons
Celanese Corp.
Celanese Plastics and
Specialties Co. Division
Celanese Engineering
Resins Div. lishop, TX 56.8
E.I. du Pont de Nemouts
& Co., Inc.
Po1y er Products Dept. Parkereburg, W V 34.1
TOTAL 90.9
Source: Directory of Chemical Producers , 1982.
250
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Polyacetal sales reached 48,000 metric tons in 1979, with a subsequent
decline in 1980 to 40,000 metric toni. A small increase in sales occurred
in 1981 (42,000 metric tons). [ 143J The polyacetal market is effected by the
general trend of the U.S. economy. However, this new plastic is also
experiencing growth in the number of applications for which it is used. The
current capacity (90.9 thousand metric tons) for polyacetal production is
sufficient for any growth in the near future.
PRODUCTION AND END USE DATA
In 1981, sales for polyacetaig totaled 42,000 metric tons. [ l43J Uses
for acetal polymers incluc’a: [ l2, 173, 174, 247, 297J
• Transportation: automotive electrical switches, body hardware,
safety—belt hardware, collapsible steering column hardware, fuel
system co ’ponents, and window handles;
• Machinery: specL lized equipment for con Ieying and handling food,
general purpose tabletop conveyor chain, mechanical couplings, small
engine starter pulleys, pump impellers, and a variety of textile
and agricultural machinery compc ents;
• Plumbing and hardware: ball cocks, shover heads, faucets, pumps,
sinks, wa r ofteners, lawn sprinklers, irrigation systems, piping,
and storage tanks;
• Appliances: gears, cams, springs, and bearings;
• Mill shapes: rods, slab, tubing, and sheet for the machining and
stamping of commercial quantities of gears, bearings, vearstrips,
thrust washers, and bushings;
• Packaging: aerosol bottle,, valves, and containers; and
o Consumer products: pens, pencils, cigarette lighters, electric and
hand razors, zippers, toys, and tape cartridge components, telephone
parts, handles and other hardware items, meat hooks, milk pumps, and
coffee spigots.
Table 78 lists major U.S. markets for polyacetal resins.
PROCESS DESCRIPTIONS
Polyacetals are produced according to the end product desired. Acetal
homopolymers are manufactured by the polymerization of formaldehyde while
acetal copolymers use trioxane to produce the desired resin. Copolymers are
more resistant to degradation caused by hedt, oxidation, or solvent attack.
This resistance is gained, however, at the expense of impact strength.
251
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TABLE 78. MAJOR U.S. MARKETS FOR POLY4CETAL RESINS
1981 Consumption
Market Thousand Metric Tons
Appliances 3
Consumer Products 11
Electrica l/E lectrongcs 2
Industrial 8
Plumbing and Hardware 9
Sheet, Rod, and Tube 2
Transportation 6
Other 1
TOTAL 42
source: Modern Plastics , January 1982.
252
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Acetal Homopolymer Reaction Chemistry
The polymerization of formaldehyde is accomplished using an ionic
initiator, A (either anionic or cationic) to start the reaction. Chain
transfer agents such as water, serve to terminate the growth of the poly—
acetal chain. Chain transfer and reinitiatjon lead to more polymer chains
than can be accounted for by the initiator concentration.(173J The polym-
erization reactions are shown below for the anionic case.
Initiation
A + 20 - ACH 2 O
Propagation
AC}1 2 0 + nCH 2 O.—.* A(C1120)nCH 2 O
Chain Transfer
A(CH 2 O)nCR 2 O + H 2 0 A(CH O) 1 H + 0H
Reini t iation
0H + CH 2 O HOCH2O
A polyacetal chain—terminated with a hydroxy] end group tends to
depolymerize due to the highly unstable hydroxyl group. The chain is
stabilized by chemical modification, called end-capping. The hydroxyl group
is replaced by a more stable group, commonly done by esterificatfon with
acetic anhydride.
Acetal Copolymer Reaction Chemistry
Like the reaction which produces ace’tal homopolymers, the acetal
copolymer polymerization uses an ionic inttiator (typically a cation, such
as boron trifluoride). The initiator first reacts with any trioxane to open
the rings, and no polymerization occurs until equilibrium with formaldehyde
is reached. The chain then grows in a manner similar to the homopolymer,
except several comonomer units are incorporated into the chain. The series
of polymerizatLon steps is s)own below for the boron trifluoride initiator
case.
Initiation
0—c l ’
BF 4 Cl’ 2 0 —- CH 1 O + F 3 3—O—C11 2 -O—CH 2
Pr p at. Ion
0
F 3 5-0—CH 2 -o—ci, + (n+I)CN 2 0 + mCH 2 -CH 2 — • 3 B-OCH 2 0CH 2 0I(CH 2 ) 2 OJ(Cfl 2 O)CH 2
25
-------
Chain Transfer
r 3 s—oca 2 -ocH-o( ( 2)2OIm( 2O)aOL2 + H 2 0 ø ? 3 1 O C X 2 OCIt -O( (C11 2 ) 2 01a(CX 2 O)nCII 2 OH + 11•
Polyacetal copolyiners do not tend to depolymerize with hydioxyl end
groups due to the oxyethylene groups randomly dispersed throughout the
polymer.
Tables 79 and 80 list typical input materials and operating paremeters
for the two polyacetal production processes. Other input materials such as
fillers and initiators are listed in Table 81.
Acetal Homopolymer Production
The polyiserizat ion of formaldehyde for acetal homopolymers consists of
four basic steps: purification, polymerization, end—capping, and finishing.
Each of these steps, shown in Figure 27, performs an essential function
necessary.in order to produce a useful commercial product.
Formaldehyde is typically supplied in a stable aqueous solution, about
40 percent of which is water, called formalin. Impurities present include
methanol, formic acid, methyl formate, and carbon dioxide. Water, methanol,
and formic actd retard polymerization and, therefore, must be removed. In
order to accomplish the removal of impurities, partial polymerization is
performed and the low molecular weight polymer is first precipitated vith
alkali, then washed with distilled water and v cuum dried. The dried for-
maldehyde polymer is pyrolyzed at 150 to 160°C; the formaldehyde which
results is passed through a series of low temperature traps (—15°C) to
remove any remaining impurities. This purified formaldehyde is necessary to
produce the acetal homopolymer.
The purified fornaldehy e is fed to a reactor which contains a dried
inert solvent, such as heptane. A polymerization initiator, a chain trans-
fer agent, and any stabilizers desired are then added. The polymerization
reaction is complete when a 20 percent solids content is reached.(247J The
polymer is filtered out of the solution, washed with solvent, and vacuum
dried.
The resulting polymer now has predominantly hydroxyl end groups. The
stability of the r lecule s improved by end—capping the polymer chain by
reacting the polyser with acetic arhydride, giving the chain acetate ester
end groups which are more stable it elevated temperatures. This end—capping
is achieved by reacting the polymer with an excess of acetic anhydride
followed by filtration and washing.
25’.
-------
TABLE 79. TYPICAL INPUT MATERIALS TO POLYA( TAL PRODUCTION PROCESSES
Formal .c—
Process Solvent hyde Initiator Comonomer
Homopolymer X X X
Copolymer X X X X
TA8LE 80. TYPICAL OPERATING PARAMETERS FOR POLYACETAL PRODUCTION PROCESSES
Process Temperature Reaction Time
Homopolymer up to 119°C a
Copolyrner
Polymerization 65—80°C *
Stabilization 100—250°C 1—2 mm.
aThese processes are considered to be proprietary.
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
255
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TABLE 81 • INPUT MATERIALS MD SPECIALTY CHEMICALS USED IN
POLYACETAJ, MANUFACTURE
Process Compound
Monomer formaldehyde
trioxane
Comonomer 1 ,3—dioxolane
ethylene oxide
Initiator acetal perchiorate
amides
amid ines
amines
ammcnium salts
arsines
diazonjum salts
p—chloro henyldiazonium
hexafluoroargenate
p chloropheny1djazonju m I
hexafluocophoephate
Levis acids
boron trifluoride dibutyl etherate
stannic chloride
Lewie bases
%.rganomE a j compounds
phosphi nes
phosphoric acid
stibineg
sulfonium salts
sulfuric acid
Chain rrangfer Agent acids
alcohols
vater
Stabilizer diphenylamine
polyamides
polyurethanes
substituted ureag
Egrerjfjcat ion acetic anhydride
Compounds aminee
soluble alkali metal salts
sodium acetate
(continued)
256
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TABLE 81 (continued)
Process Compound
Antioxidant a—coriidendro l
di naphthyl_p_pheflylenediamine
Properiy Enhancers glass fibers
molybdenum disulfide
Teflon® fibers
UV Stabilizer carbon black
Acid Acceptors basic salts
epoxides
nitrogen compounds
Hydrolysis Solvents water soluble alkanols
isopropyl alcohol
Hydrolysis Initiator ammonia
basic hydroxides
Solvent cyclohexane
heptane
hexane
methylene chloride
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
257
-------
V t
Figure 27. Acetal homopolyiiier production process.
Sources: Encyclopedia of Chenical Technology , 3rd Edition.
Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials aud
Processes , 1982.
TTSUenIIt
Metal
NO nopo1y r
Psll.ts
258
-------
The end—capped polymer is then finished by adding the desired anti—
oxidants and stabilizers. The formulated polymer is extruded into pellets
before shipping.
A typical recipe for the production of polyacetal via homopolymer
polymerization 13 as follows: [ 253J
Material Parts by Weight
Formaldehyde (nonomer) 1,000
Boron Trifluoride (catalyst) i
Heptane (solvent) 500
Acetic Anhydride (esterification chain end
compound) 800
Acetal Copolymer Production
Acetal copolymers are produced by the reaction of trioxane and a
comonomer, usually ethylene oxide. This process, shown in Figure 28, con—
ai ts of four major steps: preparation and purification of trioxane,
copolymerization, stabilization, and finishing.
Trioxane is produced from formalin by introducing a strong mineral
acid, such aa sulfuric acid, to the solution. Pure trioxane is subsequently
recovered by removing the water frcm the aolution, typically by adding an
azeotropic solvent.
The copolymerlzation of the pure trioxane is typically performed in a
solvent, such as cyclohexane, hexane, or methylene chloride. The trioxane,
solvent, and small amounts of comonomer (0.01 to 15 percent is incorporated
to improve the thermal, oxidative, and solvent r!sistance of the polymer)
are combined in a reactor. As with formaldehyde polymerization, an initia-
tor and chain transfer agent are also used. When the polymerization is
completed, the polymer is filtered and wished with solvent.
Acetal copolymers are stabilized by alkaline hydrolysis of the oxy—
methylene end groups of the polymer chain. More stable carbon—carbon link-
ages are unaffected. A water miscible organic solvent, such as isopropyl
alcohol, is used to hydrolyze the acetal copolymer with ammonia. After a
short contact time (one to two minutes), excess water is added to precipi-
tate the polymer. The precipitated polymer is then washed and dried.
Further stabilization is achieved in the finishing step by the addition
of antioxidants and stabilizers. The formulated polymer is then extruded
into pellets before shtpping.
A typical recipe for acetal copolymer production includes:(253J
259
-------
Copo1y t
P.11.t.
Figure 28. Acetal copo1y er production.
Sources: EncycIo edfaof Chemical Technology , 3rd Edition.
Encyclopedja-of Polymer Science and Technology .
Seymour S. Schwartz and Sidney H. Goodman, Pleetics Materials and
ProcesiTes , 1982.
To Vaat.va sr
260
-------
Ma:ertal Parts by Weight
Trioxane (monomer) 900
Ethylene C ide (comonomer) 0.44—77
‘Boron Fluoride Etherate Catalyst 0.03—0.90
Solvent
The amount of solvent and othei additives were not found in the literature.
Energy Requirements
The following energy requirements are listed for an unspecified poly—
acetal production process:(180J
Energy Required Unit/Metric Ton of Product
Electricity 3.39 x 106 Joules
Steam 14.3 metric tons
EnVIRONMENTAL AND INDUSTRIAL HEALTH a)NSIDERATIONS
Polyacetals are no. toxic resins used as pipe for potable water and con—
veyors for food. However, care must be used in handling both ethylene oxide
and formaldehyde since both can be toxic and improper handling may result in
in explosive mixtures with air. [ 173J Cyclohexane, ethylene oxide, and
formaldehyde are listed Sd hazardous materials.
Worker Distribution and Emissions Release Points
We have estimated worker distribution in polyacetal production pro-
cesses by correlating major equipment manhour requirements with the process
flow diagrams in Figures 27 and 28. Estimates for homopolymer and copolymer
production are shown in Table 82.
No major air emission point sources are associated with polyacetal pro-
cessing. However, fugitive emissions resulting from process sources and
leaks may pose significant environmental and worker health problems depend-
ing on stream constituents, process operating parameters, engineering and
administrative controls, and maintenance programs.
Sources of process fugitive emissions are shown in Table 83. Vapor—
phase emissions of concern include formaldehyde, ethylene oxide and such
solvents as cyclohexane, heptane, haxane and methylene ehlori e. Particu-
late emissions from pelletizing operations may result in elevated workplace
levels of nuisance dust.
Employees assigned to formaldehyde purification operations may be
exposed to formic acid, methyl alcohol, ant methyl formite, all of which are
impurities removed from the formation feedstock. Workers in acetal copoly—
mer production operatli ns may contact sulfuric or othei strong mineral ac 4 ds
used in the trioxane formation reaction.
261
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TABLE 82. WORKER DISTRIBUTION ESTIM&TES FOR POLYACETAL PRODUCTION
Process Unit Workers/Unit/B—hour Shift
Homopolyner Production Batch Reactor i.o
Vacuum Filter 0.25
Vacuum Dryer 0.25
Pyrolyzer 1.0
Traps 0.125
Extruder 1.0
Copolymer Production Batch Reactor i.o
Vacuum Filter 0.25
Extruder 0.5
Azeotrope/ Water
Separation 0.25
Solvent Recovery 0.25
262
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TABLE 83. SOURCES OF FUGITIVE EMISSIONS FROM POLYACETAL MANUFACTURE
Process
Source Constituent Homopolymer Copolymer
Prepolynerizat ion Formaldehyde x
Reactor Vent
Polymerization Formaldehyde x X
Reactor Vent Solvent x X
Trioxane X
Comonos.er x
Filters Formaldehyde * *
Particulates X X
Solvent * *
Trioxane
Comonomer *
End—Capping Formaldehyde *
Reactor Vent Solvent *
Pelletizing Formaldehyde * *
Extruder Vent Solvent * *
Particulates X X
Trioxane Reactor Formaldehyde X
Vent Trioxane X
Hydrolysis Reactor Formaldehyde *
Vent Solvent *
Ammonia X
*Trace ar.ounts of these compounds, if they are present in these streams, are
expected due to high conversion and efficient removal steps upstream of
these sources.
263
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Available toxicity information regarding the above contaminants is
given under NHealth Effects below, in Table 10 and in IPPEU Chapter lOb.
Little data are available from which employee exposure potential, may be
estimated. However, one source estimates hydrocarbon emissions from poly—
acetal molding at 1.5 g/kg product.f286J
Health Effects
The list of input materials and specialty chemicals used in the manu-
facture of polyaceta]. include many generic, non—specific compounds which
cannot be evaluated for potential health risk. The industry does use at
least two highly toxic materials: the monomer formaldehyde and the comoromer
ethylene oxide. The reported health effects associated with exposure to
these two substances are summarized below.
Ethylene Oxide exposure of 500 ppm has been associated with convul
sions, gastrointe tjna tract effects, .nd pulmonary system effects in
humans.(58J Although testing for carcniogenic effects is inconclusive,
ethylene oxide causes tumorigenic, metagenic, and teratogenic effects. The
current OSHA air standard is 50 ppm (8 hour TWA).f67j
!!E dehde poses a high toxic hazard upon ingestion, inhalation, or
skin contact f242J with human effects leported at doses as low as $ pp..
f127j This suspected carcinogen is a potent mutagea and teratogen. The
OSHA air standard is 3 pp. (8 hour TWA) with a 5 ppm ceiling.(67J
Air Emissions
Sources of fugitive VOC emissions from polyac.tal processing are sum-
marized In Table 83 by process and constituent type. Most of these sources
are vents, and controls which are applicable include:(285J
• Routing vent streama to a flare to incinerate the remaining
hydrocarbons; and/or
• Routing vent stre8.s to blowdown.
Other VOC emissions result from open sources such as filters, drains, and
valves. Enclosing the atmospheric side of these sources is not feasible in
this case due to the explosive limit of ethylen. oxide. Leaks fro. flanges,
relief valves, valves, pumps, and compressors also contribute, to the VOC
emissions for this process.
The one process source of fugitive part iculates is also listed in Table
83. Again, due to the explosive limit of ethylene oxide, enclosing the
filter is not an available control option. According toEPA estimates, the
population exposed to air emissions in a 100 k. 2 area surrounding a poly—
acetal production facility are: 11 persons exposed to hydr.,carbons and 2
persons exposed to particulates.f286J
264
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Wastewater Sources
There are four sources of vastewater for polyacetal processing: for—
maldehvde purification, trioxane water removal, filtration) and routine
cleaning water. If steam stripping is used for solvent recovcry, an addi—
ttonal wastewater stream will be generated. These sources are listed in
Table 84 by process. No d ta are available in the literature concerning
vast ewater’ parameters.
Solid Wastes
The solid wastes generated by this process are: polyacetal resin lost
due to reactor cleaning and spillage; collected particulates; and substand-
ard resin which cannot be blended.
Environmental Regulation
Efflueu limitations guidelines have not been set for the polyacetal
industry.
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organi: carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous wastes (46
Federal Register 27476, May 20, 1981):
Cyclohezane — U056
Ethylene oxide — U115
Formaldehyde — U122
All disposal of these compounds or polyacetal resins containing residual
amounts of these compounds must comply with the provisions set forth in the
Resource Conservation and Recovery Act (RCRA).
265
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TABLE 84 • SO TRCES OP WASTEWATER FROM POLYACETAL MANUFACTURE
Source Romopolymer
Formaldehyde Purification
(Prepolym*rir it toe) X
Filtration X X
Trioxane Water Removal X
(Solvent Recovery)
Routine Cleaning Water X X
266
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SECTION 11
POLYAMIDE RESINS
EPA Source Cldssificatjon Code — Polyprod. General 3-01-018—02
INTRODUCTION
Polyas ide resins are condensation polymers which have a repeating amide
group as an incegral part of the linear chain structure, flame resistance,
chemical resistance, toughness, low coeificient of friction, stiffness, out-
standing wear resistance, good electrical properties, and high temperature
resistance are properties of polyamide, which allow their use in a variety
of applications [ 246j The raw materia.s used in the manufacture of polya—
mide resins determine the physical and chemical properties of the product.
However, additives may be used to provide heat and light stability, lover
molecular weight, and increased mold release. Table a.—12 in Appendix A
lists typical properties of polyamide resins, nylon 6 and nylon 66.
Although polyamides are typically referred to as nylor.a, two distinct
polyaunide resins exist: linearnylon polymers and nonlinear non—nylon
polymers. Non—nylon resins are classified as either reactive or nonreac-
tive. Reactive resins are combined with epichlorohydrin to produce one type
of nonreactive non—nylon resin. Approximately 75 percent of the nylon poly—
amide resins produced is made up of nylon 6 and nylon 6b. Non—nylon polya—
aides contributed approximately 10 percent to the total polyamide market in
1981. [ 65)
Polyamide resins are used to produce extruded, injection molded, and
cast parts as well as fibers. End products made from these resins include
electrical groamets, bearings, gears, fastenera, valve components, rollers,
tubing, pipe, film, monofilaments, wire straps, wire covering, electrical
connectors, and sports equipment.
Two methods are used to produce polyamides: polyaddition and polycon—
densation. Nylon 6 is produced by initiating a ring opening reaction using
E—caprolactam and subsequent polyaddttton. This reaction proceeds to a
polymer/monomer equilibrium; therefore, careful control of the stoichiometry
is not needed. Nylon 66 and non—nylon polyamides are manufactured using the
polycondensation process. A carefully controlled reactor is necessary in
ocder to provide the stoichiometric amount of the reactants used.
I HDUSTRY DESCRIPTION
Thirty—two manufacturers comprise the polyamide industry, supporting 44
plants in 21 states. The largest concentration of plants is in the south-
east (EPA Region IV), which contains 36 percent of the production locations.
267
-------
The mideast (EPA Region III), New England states (EPA Region I), and Great
Lakes states (EPA Region V) contain 16, 14, and 14 percent of the production
sites, respectively. lable 85 lists nylon producers while Tables 86 and 87
list diner—acid based and epichlorohydrjn based non—nylon resins,
respectively.
Nylon resins are used in two forms: fibers and nonfibers. Fibers are
used to make tire cord, carpet filarn nt , and textiles for garments and
furniture. Nonf,ibers are used in a variety of applIcations which require
high strength and high performance. Nylon sales increased 7 percent from
1980 to 1981, reaching 132,000 metric tons.(143J From 1976 to 1979, nylon
sales increased from 100,500 metric tons to a peak of 143,200 metric tone.
During the same period, production also increased from 112,300 metric tons
in 197 to 148,600 metric tons in 1979. A decline in the 1980 production
brought the level back to 124,500 metric tona.(65 ’J
Non—nylon resins are used in adhesives, coatings, and copolyiner . for
engineering applications. These resins reached a’ sales peak of 18,200
metric tons 1977 when production also peaked at 18,600 metric tons. The
sales level increased fron- ’1978 to 1979, however, to result in sales of
15,500 metric tons and production of 15,900 metric tons.(65J
Nylon resins are projected to exhibit the fastest growth, along with
thermoplastic polyesters, of the engineering plastics between now and 1990.
A, 16 percent annual increase in nylon outnut for-engineering applications is
forecast for this same-period. The largest increase is expected for
reaction—injected—molded (RIM) and extrulion grades. 1861
PRODUCTION AND END USE DATA
In .1981, nylon sales tataled 132,000 metric tons. ( 143J Nylon has many
uses, which include: (159, 246, 247, 250, 267, 2911
• Production of synthetic fibers used in tires, carpets, stockings,
and upholstery;
• Molding powders for valve seats, bearings, gears, came, and mechine
pert 5;
• Automotive applications, including stone shields, emissions canis-
ters, windshield wiper and speedometer gears, trim clips, -wire
jacketing, electrical connectors, ddiue light lenses, engine fan
blad es, radiator headers, brake fluid and power steering fluid
reservoirs, valve covers, steering column housing., emission control
val vee, mirror housings, fender extensions, and license plate
pockets;
• Electrical and electronic applications, including plugs, connectors,
wiring devices, terminals, coil forms, cable ties, wire jacketing,
. ntenna mounting devices, and mechanical components for use in corn—
putars, televfsion sets, and other consumer—oriented products;
268
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TABLE 85. U.S. NYLON RESIN PRODUCERS
I J82
Capacity
rbouund
Prnducer Location Product Types Metric Tons
dell Lasttcs• Inc. SaIti.ors ‘W Nylon 6 and 66 9.1k
Allied Corp.
Allied Fibers and Plastics Co. Che.c.rtteid. VA iylon 6 5.0
4ypeL. lnc. subsidiary Ch.sterfisld, VA Iylon 6 and 66 6.8*
nsrican Crilon tt c. Suntsr. SC lyLon 6 and 12 5.0
4 rican Hoechst rorp
Pigatics ivtsion ianchest.r. N M Nylon 6 8.2
Sadischs Corp. Pr..port. TX Nylon 6 6.8
Balding lelinvay Co.. Inc.
gelding Cb..ical Industries, Groevonordal.. CT Nylon 69 1.8
subsiitary
Sent. Co.. Inc.
Custo. Resins Division Hend.rson iT ‘lylon 6 9.1
Celaiiese Corp.
Celansse Plastics I Spscialti.s
Co. Division
C.lanss. Engin..ring issins Bishop. TX Nylon 66 18.2
Division
!. I. di Pont di lenours 6 Co.
Inc.
Polyner Products Depart..nt Psrk.rsburg. WV Nylon 66 and 612 73.0
he Firestone tire and Rubber
Co.
Firestone Synthetic Pibers Co. Hopewell, VA Nylon 6 5.3
tvtston
t ionsanco Co.
Monsanto Plastics & ResIns Co. Pensacola. P1. Nylon 66 and 69 31.8
Rilsan Corp.
Rilsan industries Inc., Birdsboro, PA Nylon IL and 12 3.0
subsidiary
Shake.ipeare Co.
Monoftls snt Division Colusbis. SC Nylon 6 1.8
Tezapol Corp. B .thl.h.a. PA Nylon 6 and 66 . ..b
Welinan, Inc.
‘4allnan Industries, Inc.,
subsidiary
Man-Made Fiber Divilion .Iohnsonvill.. SC Nylon 6 and 66 3.61
TOTAL. 212.7
‘These producers eanufectur. regenerated nylon resins fron fiber vast..
bconpany produces lees then 2.215 kg/year of nylon resins.
SourceS Directory of Chenical Producers , 1982.
269
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tABLE 86. U.S. PRODUCERS OF DIMER ACID BASED NON—N?T.ON POLYAMIDE RESINS
1982 Capacity
Thousand
Producer Location Metric Tons
AZS C.rp.
AZ Products, Inc. Div. Eaton Park, FL 5.9
Celanese Corp.
Celanese Plastics &
Spe ia1ttes Co. Div.
Celanese Specialty
Resins Div. Louisville, KY 0.9
Cooper Polymers, Inc. Wilmington, MA 2.3
Crosby Chemicals, Inc. Picayune, MS 1.8
Emhart Corp.
USM Corp., sub.
Bostit Div. Eastern
Region Middle on, HA 0.9
Henkel of America, Inc.
HenkrL Corp., sub. Kankakee, IL 11.4
L.awter Int’l., Inc. Moundsville, AL 1.4
Mobil Corp.
Mobil Oil Corp.
Mobil Chemical Co. Div.
Chemical Coatings Div. Edison, NJ 1.4
National Distillers and
Chemical Corp.
Emery Industries, Inc.,
sub. Cincinnati, OH 4.5
The O’Brien Corp.
The O’Brien Corp.—
Southwestern Region Houston, IX 0.5
Pacific Anchor Chem.
Corp. Los Angeles, CA 0.9
(continued)
270
-------
TABtE 86 (continued)
1982 Capacity
Thousand
Producer Location Metric Tons
Reichho].d Chemical,, Inc. Andover, MA 2.3
Sun Chemical Corp.
Chemicals Group
Chemicals Div. Chester, SC 1.8
Union Camp Corp.
Chemicals Products Div. Dover, OH 4.5
TOTAL 40.5
Source. Directory of chemical Producers , 1982.
271
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TABLE 87. U.s. PRODUC j OF EPICHLORONYDRIN BASED POLYAJIIDE RESINS
Producer Location
Borden, Inc.
Borden Chemical Div.
Adhesives and Chemicals Div. Demopolis, AL
Dibull, TX
Payettevj l NC
Sheboygan, VI
Diamond Shamrock Corp.
Int’l. Technology Unit
Process Chemicals Div. Charlotte, NC
GeorgLa—pa jfj Corp.
Chemical Div. Eugene, OR
Newark, OH
Peachtree City, CA
Richmond, C&
Hercules, Inc. Chicope., M&
Hattieeburg, MS
Milwaukee, VI
Portland, OR
Savannah, GA
Source: Director 7 of Chemical Producer . , 1982.
272
-------
• Consumer goods, including roller ska e sole plates, ski bootd, and
ice skate supports as well as bicycle wheels and racquetball
racquets;
• Films for oven cooking bags and packaging for surgical instruments;
and
• Other uses, including gun stocks, lighter fluid cases, printing
plates, air conditioner hose, power tool housings and hardles, brush
bristles, fishing line, mallet heads, combs, self—sealing fuel tanks
for military aircraft, medical devices, storm window and furniture
parts, and beverage dispensing valves.
Table 88 presents major nylon markets for 1981.
Non—nylon polyamide resins are used in heat-seal adhesives, overprint
varnishes, can eid’—geam cements, inks, thixotro?ic paints, thermosetting
adhesives, potting •:ompour dg, casting compounds, solvent—based t)ermosettlng
coatings, solventless r3atings, and plastic terrazo . [ 171J
PROCESS DESCRIPTIONS
Polyamide resins are produced by two basic processes: polyadditjo and
polycondensatlon. Monomeric ring structures, such as caprolactam. are
polyinerized by first opening the ring and then propagating the resulting
polymer chaIn usIng the polyadditfon process. The polycondengatlon process
uses an acid and an amine to form the polyamide and by—product water.
Nylon 6 is the major product manufactured by the polyaddition process.
Nylon 6 and non—nylon diser acid based and eptchlorohydrjn based resins are
produced via the polycondensation process.
Polyaddition Reaction Chemistry
Nylon 6, so named for the six carbon atoms in the caprolactatn molecule,
is produced by hydrolysis and polymerization of caprolactam. Vater and 66
salts are used to open the ring structure. Once the ring is opened, the
resulting chain may react with other opened ring chains or caprolactam rings
to produce the polymer. This sequence of reactions is depicted below: [ 247J
ydrolysts of the Caprolactam?qolgcule (Ring Opening )
I 1
+
273
-------
TABLE 88. MAJOR U.S. NYLON MARKETS
Market 1981 Thousand Metric T ..ns
Extrusion
Filaments 11
Film 11
Sheet, Rod, Tube 5
W±re and Cable 4
I ecrion Mo Jing
Apu Jances 7
Consumer Products 20
lectrical/Electronjc 14
Industrial 14
Transportation 28
Export 9
Other 9
TOTAL 132
Surce: Modern Plastics , January 1982.
274
-------
Propagation of the Polymer Chain
0 0
R2N(CM2)S OH 4 H 2 P4(CH 2 )JOH
H (CH 2 ) 5 OH + H 2 0
w [ H(cH 2 ) 5 0H
Polycondensa
NylOl 66
ion Reaction Chemistry
Nylon 66 s produced by the reaction of adipic acid and hexamethylene—
diamine. Each of these reactants co’tains aiX carbon atoms, hence the 66
nomenclature. The dibesic acid groups on the adipic acid molecule combine
with the anine groups of the hexamethylenediamina molecule, resulting in the
elimination of a molecule of water after the formation of an intermediate
salt. An exact 1:1 molar ratio of reactants is necessary In order to form
the repeating group which characterizes nylon 66. The condensation reaction
Is shown below.
HO (CH 2 ) 4 H ‘ H 2 N(C:1 2 ) 6 NH 2 —
1+H 3 N(CH 2 )&NH 3 +J(-O (Cu 2 ) 4 J
HO (CH 2 ) 4 C (CH 2 ) 6 NH 2 + H 2 0
H
275
-------
o 0 0 0
ROC(Cfl 2 ) 4 (CH 2 ) 6 NR 2 + HOC(CH 2 ) 4 &H
o 0 0 0
U I, U
HOC(CH2)4CN(CHZ) 6 NC(C1j 2 ) 4 ft + 1120
I I H
0 0 0 0
H0L(C11 2 ) 49 Cii 2 ) 6 ’C(CR 2 ) 4 OH + H 2 N(CH 2 ) gH 2
1? 1
HOtC (CH2)49(cH 26 Ic(cH 2 ) 4 c 7 (cH 2 ) 6 J .H + 1420
Nnn—4yJon Diner 3ased
Dimer acid based non—nylon polyamide resins use high molerular weight
acids, such as the polytlerizatjon product of linolej acid ( 9 1 1 l —octadecadj—
enoic acid), and an amine, such as etbylenediamine, to produce th. polymer
chain. Tho condenlatjon reaction is similar to the one Ear ‘vlon 66 end is
shown below.
0
N
(E2
c ’ + H 2 NCH 2 Cff 2 g 2
412 ’ ,
aN 3
276
-------
0
Epichiorohydrin Rased
0
(CH 2 ) 1 4 NCH 2 CH 2 NH 2
II
—CH”Cl4—(Cli 2 ) 4 —CH 3
Epichlorohydrin based polyamide re ii . are produced by the reaction of
epichlc .rohydrin and a reactive polyamide resin. Adipic acid and diethylene—
amine are oinmonly L.sed as the raw materials for the reactive polyamide.
This reaction is shown ,elow.
Reactive P’iljamide Production
0 0
I II
HOC(CH 2 ) 4 COH + l1 2 l(CH 2 ) 2 MH 2 (CH2)ZNH 2 —
0 0
HOC(CH 2 ) 4 CN(CH 2 ) 2 NHZ(CH 2 )2MH
H0iC(CHZ) (
0
‘I
I ’
nC ICH 2 CHCH 2
+ flH2O
+ H 2 0
H3
Reaction with Epichiorohydrin
0
It
H
*
0
II
HO C(CH 2 ) 4 CM((}1 2 ) 2 N(’U 2 ) 2 N
H 11
277
-------
Typical input materials and operating parameters for the polyaddition
and polycondensation processes are presented in Tables 89 and 90, respec-
tively. Table 91 lists input materials, including lubricants, filler., UY
light stabilizers, and colorants.
Polyaddit i ,n Process
The polyadditi on process is based on the use of a compound which con-
tains both an acid and an amine functional group. Nylon 6 is the major
polymer produced using this method, depicted in Figure 29. Roth batch and
continuous processes are used for the polyadditlon process. A typical
production recipe for polyamldes via the po1yad.j jon process is given
below: 1125J
Material Parts by Weight
Caprolactam (monomer)
Water (catalyst) 10
Acetic Acid (chain terminating agent)
Caprolactaip is ed to a polymerization reactor along with water, or another
suitable catalyst, and a chain terminating agent (acetic acid). The temper-
ature 15 raised to 250’C and the reaction starts by opening the caprolactam
ring. The polymerization does not go to completion; instead, a monomer/
polymer equilibrium is reached at around 85 to 90 percent conversion.(246J
When the reaction reaches the desired conversion, the reaction mixture
is discharged from the reactor through a die to form a polymer rod. These
rods are subsequently cut into pellets and 4 ried. If the unreacted capro—
lectam monomer is not removed, it acts as a plasticizer. Caprolacta.
removal may be accomplished by feeding the polymer mixture from the reactor
into a vacuum chamber vhere the monomer is flashed and recycled. Pelletiga—
tion is then performed and the pellet. dried to the desired moisture
content.
Polycor.densat ion Reaction
Polyamides made by the pnlycondensatjoii reaction utilize a stoichie—
meeric ratio of maine to acid of l:1.(125J Therefore, iareful control of
losses from the reactor is necessary to maintain the correct reaction com-
position. Due to this onstraint, batch processing is used for these
reactions.
The olycondensat ion process used to manufacture nylon 66, shown in
Figure 30 is actually a two—stage reaction. In th. first stage, stoichio—
metric portions of hexamethylpnediamf ma and alipic acid are mixed in water.
The resulttn 9 intermediate .at, soluble in water, is decolorod with acti-
vated c4rbem and concentrated to a 60 percent solution by evaporstion.(246j
U a chain terminating a’ert (acetic acid) Is desired, it is added to the
coicentreted solution. A typt a1 production recipe for this process ae not
round In the lfterat ,e.
278
-------
TABLE 89. TYPICAL INPUT MATERIALS TO POLYAMID! PRODUCTION PROCESSES
Reactive
Poly— Epi—
Cy : lic Cata— Dibasic ainide chioro-
Process Monomer lyst Acid Amine Resin hydrin
Polyadditton X X
‘olycondensation
Nylon 66 X X
Non—Nylon Diner Eased X 5 X
Epichiorohydrin Based X X
aHigher molecular weight than those used for nylon 66
production.
TABLE 90. TYPICAL OPERATING PARAMETERS FOR POLYAMIDE PRODUCTION PROCESSES
Process Pressure Conversion
Polyaddttion 240 — 280°C 1.8 MPa 85 — 902
Polycondensation 250 — 300°C 1.8 a >992
RApproximgt.e.
Sourcea: Entyç pedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
279
-------
TABLE 91. INPUT MATERIALS AND SPECIALTY CHEMICALS USED IN
PI)LYAMIDE RESIN MANUFACTURE
Function Compound
Monomers adtpic acid
diethylenetriamine
E—caprolactam
epichiorohydrin
ethylened Lamine
hexamethylenediamine
high molecular weight fatty acid
triethylenetetramine
Catalysts phosphoric acid
water
Molecular Weight Regulator acetic acid
Fillers asbestos
glass fiber
mica
talc
Plasticizers amide
couma cone— I radene resima
resorclnvil. esters
toluene sulfonamide.
Comonomers amino resins
phenolic resins
polyurethane
polyvinyl acetate
Heat StabLl!zerg combination i of eupric salt.
and halides of alkali metals
!JV Light Stabilizer carbon biack
copper cciapounds
manganese compounds
Slip Enhancers graphite
metal stearates
zinc Atearat
molybdenum disulfid.
polytet rat luoroethylen.
silicone,
Delusterant titanium dioxide
(continued)
280
-------
TABLE 91 (continued)
Function Comp nd
Antloxidants aromatic amine.
organic phosphites
phenolics
phosphinates
Colorants aluminum
anthraquirione
bronze
cadmium mercury
cadmium sulfide
cadmi.’m sulfoselenjde
carbon black
ceramic black
chrome cobalt aluminate
chrome in
cobalt aluminate
lit io one
metallic oxides
phthalocyanjne blue
phthalocyanine green
titanium dioxide
ultramarine b1.
ultramarine green -
ultramarine pink
ultramarine red
ultramarine violtt
zinc sulfide
Mold Release Agents aliphatic monoalcohol,
aliphatic monoamineg
belenic acid
esters of aliphatic monoalcohol,
ucIeat1ng Agents alumina,
q4n,fum acetate
lead acetate
m gnegium oxide
mercuric bromide
mercuric chloride
phenol phthalein
si licas
sflver halide,
sodium isobuitylphoa 1 ihlnate
qodium phenyphogphirate
(continued)
281
-------
Table 91 (continued)
Functioi Compound
Fire {e ardant organic halide and a metallic
oxide or halide
Sourceg: Encyclopedia of Chei,ical Technology , 3rd Flitlon.
Encyclopedia of Polymer Science and TechnolcM .
Melvin I. Kohan, 7lon P1aotieg 1973.
Modern Plaat ice Enc 1 1opedLa, 1981-1982.
-------
Capi
?tgure 29. Polyamide production using the polyadditton process.
Source: Encyclopedia of Polymer Science and Technology .
283
Chain
tenilnacing
% ent
Plasticized
‘ vLon 6
6
-------
Vent
to
?rsotoent
Figure 30. Polyamide resin production using the polycondansatton process.
Source: Encyclopedia of Poly.er Science and Technology .
Vent
Condensate to
Wsaiswetst frutasL.
Treatasat
Metie Mid _________
Ribbon
Vent
284
-------
The Concentrated salt solutior. is then fed to the polymerization reac-
tor where the second—stage of the reactIon begtns. Increased temperature and
pressure are used to initiate the polymerizatIon reaction. Water vapor is
bled from the reactor to keep it at Constant pressure. Diamine losses,
which may be substantial due to low vapor pressure, are prevented by
partially polymerizing the reactants to nylon 66 orepolymer. When the
temperature of the batch reaches 275°C, the pressure is allowed to fall to
atmospheric. The batch is held at 2 O°’ and atmospheric pressure or half
an hour to allow removal of the water vapor. If an extremely high conver-
sion is desired, the batch is held under partial vacuum at the end of the
polymerization. [ 2461
The polymer is extruded through the bottom of the reactor to form a
ribbon which is flaked. 5sLches of flaked polymer are blended to minimize
any variation, from batch to batch.
Polyc.ndensatjofl reactions fo non—nylon polyamideg are much simpler
than the nylon 66 process. The input maperlal; aL adeed to the polymeriza-
tion reactor where the temperature and pressure is increased to the reaction
conditions. Water evolved during the co densatjon reaction is vented as
water vapor. Dimer acid based non—nylon resins are occasionally used in
solution; the solvent is added to the reactor after the polymerization is
completed. Epichiorohydrin resins are diluted tc a 12.5 percent solids
solution for use in the paper industry as coatings.
Energy Requirements
Data concerning the energy requirements for this process were not found
in the literature consulted.
ENVIRONMENTAL AND IMDUSTRIAL HEALTH Q)NSIDERATIONS
P’lyamideg are biologically inert compounds which have been approved by
the FDA for use in food wrap. However, hexamethylenedjamine and caprolactam
are skin and tissue irritants. Care must be used in handling not only these
materials but also nylon 6 plasticized with caprolaetam. Two of the input
materials to polyamide production, asbestos and lead acetate, are listed as
hazar,us wastes under RCRA.
Conversions of 90 percent or greater indicate that most f the emis-
sions for these processes occur in or of the reactor. Care Is
taken in the polycondengatlon process to reduce monomer loss since a stoi—
chiometric amount of reactant is required to ensure the desired product. The
polyaddition process removes and recycles caprolactam if an uplagtie ized
product is desired. Therefore, although sources upstream of the reictor
have relatively more emiasiong the magnitude of these emissions I still
gm 11.
285
-------
Worker Distribution and Emissions Release Points
Estimates of worker distribution have been made by correlating major
equipment manhour requirements with the process flow diagrams in Figures 29
and 30. Table fl shows estimates for both the polyaddition and polyconden—
sation processes.
Only fugitive emissions from process sou’ces and ‘eaks are associated
with polyamide production. Although there are no major point source air
emissions, fugitive emissions may be a significant environmental and/or
worker health problem. The magnitude of these emissions’ impact is a func-
tion of stream constituents, process operating parameters, engineering and
administrative controls, and maintenance programs.
Fugttiva emissions and their principal sources are shown in Table 93.
AdditLonally, employees may be •xpogad to monomar;, couonoaara, catalysts
ana, other additives (see Table 91) during raw materials and final product
handling and packaging.
Available toxicity information for contaminants of concern is discussed
under health Effects below and e’jmuiariged in Table 10. Information about
the many specialty chemicals potentially used in polyamide production may be
found in IPPEU Chapter lOb.
Little data are available from which employee exposure potential may be
estimated. However, one source gives a hydrocarbon release rate of 13 g kg
product from nylon molding operations (286j .
Health Effects
The manufacture of polyamide resin involves the use of one known human
carcinogen and five suspected carcinogens. They ares the filler asbestos;
lead acetate, a inicleating agent; polytetraf luoroethy lene, which is used as
a s 1 ip enhancer; polyurethane, a comonomer in the procesi; the monomer
epichiorohydrin; and the colorant cadmium sulfide. Two nucleating agents,
mercuric chl ride and mercuric bromide, are considered extremely toxic and
may also adversely affect the health of plant employees if exposure occurs.
The following paragraphs summarise the reported health effects associated
with exposure to these substances.
Asbestos is classified as a human carcinogen by the International
Agency for Research on Cancer 11041 and by the American Conference of
Covârnmenta l Industrial Hygienists.f3J ft is currently undergoing addi-
tional tests by the National Toxicology Program. 233J Most deaths from
exposure to asbestos are due to lung cancer.(104j Not only is the lung
cancer risk dose—related, but there is also an important enhancement of the
risk in those exposed to asbestos who also smoke cigarettes.flo4J The 05 11*
emergency air standard is 0.5 fiber >3 ua/cc (8 hour TWA).
Cadmium Sulfide appears to be a ‘vutagenic agent and has produced posi-
tive results in animal tests for careinogentcity.(98J It is also highly
286
-------
TABLE 92. WORICER DISTRIBUTION ESTIMATES ?U POLYAMIDE PRODUCTION
Process Unit Workers/Unit/B—hour Shift
Polyaddition Batch or Contin oua P.es tor 1.0 or 0.5
Flash Tank 0.115
Pelletirer 0.5
Dryer 0.5
Polycondensation Batch Reactor 1.0
Filter 0.25
Evaporator 0.25
Condenser 0.125
Fiaker 0.25
287
-------
1A3LE 93. SOURCES OF FUGITIVE EMISSIONS FROM POLTAIIIDE MANIJPAC?URE
Process
Source Constituent Polyaddition Polycondeneation
Polymerization Caprolacta *
Reactor Vent Amine Compound *
Acid Compound *
Epichiorohydrin *
Water X X
Mixing Tank Vent Hexamethylenediamine *
Adipic Acid *
Water X
Evaporator Vent Hexamethylenediami ne *
Adipic Acid a
Water X
Pelletizer Vent Caprolactam *
Particulatea X
Flaker Vent Part iculate. X
Dryer Vent Part iculates
*Trace amounts of these compounds are expected, if they are present, due
tc. the high conversion of the polyamide polymerization process...
286
-------
toxic by ingestion or inhalation following acute or chronic exposures.(242J
Sulfides of heavy metais are generally innoluble and usually have little
toxic action except through liberation of hydrogen sulfide. [ 242J However,
inhalation of dust or fumes, of L. d ’1um compounds affects the respiratory
tract and may also involve k4dney damage.(148J Even brief exposures to high
concentrations may result in pulioonar edema and death. (148J The OSHA air
standard for cadmium dust is 0.2 mg/mi (8 hour TWA) with a 0.6 mg/rn 3
ceiling.
Epichiorohydrin is highly toxic by Iagestion, inhalation, and skin
absorptlon. [ 242J In acute poi oning, death may be caused by respiratory
para l}sig (2421; chronic exposure can cause kidney injury.(149J Symptoms of
chronic poisoning at concentrations lower than 20 ppm include fatigue,
gastrointestinal patio, and chronic conjuncttvitis.(134J Epichiorohydrin
has also produced positive results in animal tests for carcinogeniclty [ 101]
and for mutagenicity and teratogenicity.(233J The OSHA air standard is 5
ppm (8 hour TWA).(67J
Lead Acetate , a suspected human carcinogen (109], is also associated
with mutagenic and teratogenic effects in laboratory anioals. (233J The OSHA
air standard ii 50 ug (Pb)/m 3 (8 hour TWA).(67J
Mercuric Bror ide , as is the case for all forms of mercury, is highly
toxic if absorbed.(85J It is capable of causing death or permanent injury
due to exposures of normal use [ 243] by inhalation, ingestion, and skin
absorption.142J The bromide ion is also toxic; the systematic effects of
thc bromide ion are chIefLy mantal: drowsiness, irritability, ata Ia,
vertigo, confusion, mania, hallucination, and coma.(851 NIOShI has recom-
mended an air standard in the work place for inorganic mercury of 0.05
mg(Hg)/m 3 (8 hour TWA). [ 158J OSHA has set a ceiling air standard of 1
mg/b 3 ,
Mercuric Chloride is one of the most toxic forms of mercury.(85J
P ta1ities have resulted from as littte as U.S grams by mouth, .ithough the
mean lethal dose In adults probably lies between 1 and 4 grams. [ 85J Occu-
pational poisoning due to mercury or its inorganic compounds Is usually
associated with chronic exposure.(278] Mercuric chloride is currently being
tested for carcinogenesis by the National Toxicology Prograa. [ 233J NIOSH
has recommended an air standard in the work place for in3rganic mercury of
0.05 mg(H )/n 3 (3 hour TWA). [ 158J OSHA has set a ceiling air standard of
1 mg/10 m .
Po1ytetrafluoroe !yr1ene has produced positive results In animal tests
for carcinogenicity, although the data provide insufficient evidente to
issess the carcinogenic risk In humans. (l07J The finished compound is inert
und€r ordinary conditions, but there have been reports of polymer fume fever
in humans exposed to the unfIs tshed product and thermodegration products.
[ 107, 149] Exposure produces influenza like symptoms, including chills,
headac -.e., rlgor—P’ce shaking of limbs, mild respiratory discomfort and high
fever. (107]
289
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Polyurethane in the form of foam, has produced positive results in
animal tests forcarcinogefljcjty.(i o7J However, very little animal data and
ru, human data exist in the available literature with which to evaluate the
potential for other adverse effects in humans following exposure to this
substance.
Air Emission ,
Sourceg of fugitive VCC emissions are listed in Table 93. All the
process sources are vents which may be controlled by: [ 285j
• Ruting the stream to a flare to incinerat, the hydrocarbons
present; and/or
• Routing the at-earn to blowdown.
One e,timete of emissions from the mixing tank in nylon 66 production is 1.3
kg hexamethy lenedi,m.ne per metric ton of product.f93J Other sources of
fugitive emission; Include valve., relief valve., flanges, pumps, compres-
sors, and drotna. Equipment modification (covering open drains or closing
the ar.ao ;phertc aide of open—ended valves) may reduce these emission.; how-
ever, a regular inspect br. and maintenance program may be the most effective
control.
Sources of fugitive particulate, are also listed in Table 93. These
emiasior.q may be rediw..4 by ventbig the evaporator, pelletiger, flaker, and
dryer vents to either a baghouse or e.ectrostatjc precipitator to collect
the particulate,. According to EPA estimates, the population exposed to
nylon resin emissions in a 100 km 2 area surroundin 3 a nylon resin plant
is: 27 persona exposed to hydrv,carbon. and two pera,ns exposed to
particulate,. 12861
Wastev ter Source .
The vastevatpr sources Issociated with polyarnide production are listed
In Table 94. Nylon 6 has only one source: routine cleaning water. Water
vapor from the evaporator arid reactor in rtyl ’rn 66 production may be con-
densed although these streams contain very little amine or acid co onent ,.
Ra-tges of several vastewater paramete: , for wastevater, from nylon pro—
dnct Ion are shown below. Value, for the wastevae r from the processes
presented were not diatilgujshed by process type by EPA for the purpose of
eatabl ls ’ing effluent limitations for the nylon segment of the polyamide
Industry. (284J
Nylon Vastewater Unit/pletric Ton
Characteristic _ of Nylon —
ProductIon 0 — 152.3
B0D 0.1 — 70
CC D 0.2 — 300
TSS 0 —8
290
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TABLE 94. SOURCES OF bLASTEWI.TER FROM P )LYAMIDE PRODUCTION
Process
Sour’:e Polyaddition Polycondensatlon
Activated Carbon Filter Backwash X
Evaporator Condensate x
Reactor Condensate
Rout tne C1eanir g Water X X
291
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Solid Wastes
One solid waste may result from the polyaddition process: low molecu—
, .ar weight polymer from the f].ach tank. The magnitude of this waste is
eecima’ed to be 19 kg per metric ton of product.(93J
One solid vas e also results from the polycondrnsatin of nylon 66. The
activated carbon tilter used to purify the intermediate salt reaults in a
so d vas’e contain ng 15 kg activated carbon and 3.7 kg trapped intermedi-
ate salt per laeLric ton of product.(93J
Reactor cleaning, product blendinC, particulate removal, and spillage
co trib’ite to the solid waste load. Substandard product which cannot be
blended is also a solid vdste for these processes.
Envirc,nmenrnl ulation
Effluent limitations guidelines have been set for the nylon 6, nylon
66, and i ylon 61’. segments of the polyamide industry. EPT, BAT, and NSPS
call for the p11 of the effluent to fal between 6.0 and 9.0 (41 Federal
Register 32587, August, 4, 1976).
New source performaoca standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release alves must not release more than 200 ppm above
background, except in emergency pressure release., which should not
list more than five days; snd
• Leaks (which are defined as VOC emissions greatir than 10,000 pp.)
must be repaired within 15 days.
The following compounds have been listed as hazardous:
Asbestos — U0 13
Lead acetate - U144
All disposal of these compounds and polyamide resins which contain residual
amounts of these compounds must comply with the provisions set forth in the
Resource Conservat1o’ and Recovery Act (ECU).
292
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SECTION 12
POLY BUTYLENE
EP!t Source Classification Code — Polyprod. General 3-01-018—02
I NTRODUCT I ON
Polybutylene refers to a group of polymers comprised primarily of
poiy—1—butene. Commercial polybutylene resins are used for pipe and film.
These appitcations utilize the high temperatvre stability, chenical resis-
tance, tear strength, puncture resistance, high impact strength, and mois-
ture impermeability of the polymer. Polybutylene pipe is used for cold
water distribution and service; veil piping; hot water service, which
Lr%cludeg resld nt al and solar plumbing as veil as underfloor and hot water
‘ eating; Industrial high—temperature and abrasive slurry lines; high—
te. perature acid efflueat lines; ind rhemical process lines. Polybutylene
film finds uses in heavy—duty shipping containers, food a d meat packaging,
compression wraps, hot—fiji containers, agricultural packaging, and indus-
trial sheet [ ng. [ 32
Polybutylene is produced by the polymerization of 1—butene using a
Ziegler—Platta cataljst. Polybutylene hai’ been identif ted an poseesning four
aeparatc &oUd forms; forms I, II, III, and 1’ The str’cture for poly—
butylene is shown below.
fCH2_CH —
CH 2 —Ce 13
The commercial resin (form I) is one of four identified crystalline forms of
poiy—l—butene. °oly—l—butene crystallizes into form TI when the polymer is
hdated above the melting point and resoltdified. Form II transforms to form
I (via a goltd-gol [ d ransformstion) after abo it one week at ambient condi—
tiong. Poly—1-buc. :e man’ifactured by solution poi7mert ation of the monomer
and subuequent precipttation cry taliizes into form Ill, g s—pIase polym—
rizatIon or low temperature solution polymerization of 1—butene results in
form I’. Both forms III and I’ transform to form I upon heating.112 11
These soI d—solid trarqforinationq cause shrinkage and warptig In molded
parts slice the c’lei tee mnld.ng temp ratures cause Lhe polybuty ene to
crysialilze as form 11, Lhcn transform to form I. Th a44fth n of propylene
as a comonom ’r prevents the formation of form TI c iring moliing, tbus
eliminating the poblem u( shrinkage ‘nd varping.1L24J
293
-------
Polybutylene has a crystalline structure which is also spherical, giv-
ing the polymer excellent environmental stress crack r . aJstance and recovery
from elongation. Polybutylene samples demonstrate fast and coriplate recov-
ery after SO percent elongation, and 80 to 85 percent recovery after 100
percent elongation.(l24j Table A—13 in Appendix A lists some typical prop-
erties of polybutylene.
INDUSTRY DESCRIPTION
At the present time, Shell Chemical Company is the only U.S. producer
of polybutylene.(56, 1241 The production facility, located in Taft,
Louisiana, has a capacity of 22,300 metric tpns. The total demand for poly—
butylene in 1980 was 7,300 metric tons. Therefore, sufficient capacity is
available for growth in the polybutylene market in the near future.(53J
Polybutylene is a nontoxic compound which is used in packaging meat and
other food items, transporting water, including potable water, and other
piping and packaging applications. None of the chemicals which have been
identified as inputs to polyburylene processing are knovn carcinogens. How-
ever 1 two substances used in polybutylene manufacture (1,1—dimethylhydra—
tine, a catalyst, and teotactic polypropylene, a transformation aid) have
been identified as animal carcinogens and are therefore potential human
carcinogens. One compound, 1,1—dimethyihydrasine, has been listed as
hazardous under RCRA.
PRODUCTION AND END USE DATA
Pol’ybutylene is still In the developmental ; age of commerciali;azion,
with 1980 produ:tion sligitly under 7,300 metric tons.(53J Polybutylene
markets include:(32J
• Pipe for cold water service; veils; hot water service, including
residential, solar, underfloor and hydronit heating plumbing;
high—temperature and abrasive slurry lines; high—temperature acid
effluent lines; and chemical procesa lines; and
• Film for heavy—duty shipping containers, food and meat packaging,
compression wraps, hot—fill containers, agricultural packaging, and
industrial sheeting.
PROCESS DESCRIPTION
Polybutylene is presently manufactured via mass polymerization using a
Ziegler—Platta catalyst. The pelymerization is initiated when 1—butane
reacts with an active site on the catalyst to form a radical group. As other
1—butene molecules react with the 1—butene/catalyst radical, the polybuty—
lene chain is propagited. The polyinertzatlor. terminates when either the
carbon—catalyst bor.d becomes weak In relation to the carbon-carbon bonds in
the chain or a mn1e ular weight regulating agent, such as hydrogen, reacts
with the polymer chain. The polymerization reaction is depicted below.
2 Q4
-------
Initiation
Ca t l y St
CH 2 —CIICH 2 CH 3 —-- ‘ —CH —CHI
Propagation
—CH 2 —CH• + n H 2 —CHCH 2 CH3 ’
CH 2 —CI( 3
CH 2 -C}i
H 2 —CHi n 2 H3
Termination by Elimination
—f CH 2 -C I I 1 2
[ CH —CH 3 Jn C1 1 2 —CH 3
CH 2 ( CH 2 —CH CH 2 H 2
CH 2 —CH 3 2 CH 3 n—i H2-CH3
Termination by Hydroge.iatton
CH?-’H— + H 2 —— ‘
Cf1 2 —CH 3 n CH 2 -CH 3
H 1 cH2_r_ J
CH 2 —CH 3 fl CH 2 -CH 3
Tah1 95 and 96 lIst typical input materials and operating parametv re
for mass polymcrizatlon of pnlybutylene, respectively. The mass o1ymerixa—
tion proce a, qh i,, In FIgure 31, iis a high pressure to liquefy the 1—butene
.i, nomer. A conionomer, if leqired, a molecular weight regulator (e.g.,
hydrogen), and the catalyst are added to the reactor. When th reaction has
reached the desired ronverston, the monomer-polymer mixture is fed t a wash
tank.
295
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TABLE 95. TYPICAL IMPUT MATERIALS TO POLYBUTYLENE POLYMERIZATION
Function Compound
Monomer 1—butene
Counonomer 1—pentene
Propylene
Ethylene
CatalysP Titanium chloride
Diethyl •luminum chloride
Diethyl aluminum iodide
1 ,l—dimethylhydrazine
Magnesium chloride
Ethyl bennoate
Triethyl aluminum
Molecular Weight Regulator Hydrgen
Transformation Aids Stearic acid
Isotactic polypropylene
Sources: Encyclopedia of Chemical Technology , 3rd EditIon.
Modern Plastics Encyclopedia , 1981—1982.
TABLE 96. TYPICAL OPERATING PARAMETERS FOR POLYBUTTLENE POLYMERIZATION
Parameters Value
Temperature, °C 65
Pressure, Pa 800,000
No other information on this process is available in the
literature.
Sources: ncyc1opedia of Chemical Techno4oV , 3rd Edition.
Carl L. Yaws, Physical Properties , 1977.
296
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Figure 31. Mass polymerization of polybutylene.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
- Vent
Polybutylene
Pellets
Other C Compounds
to I—bu ene Makeup
Spent
Catalyst
Effluent to
Was tewat e r
Treatment
-------
Deoxygenated water is added to the wash tank to remnve any catalyst
residues which are then either recycled and regenerated or sent to disposal.
The polymer q elt is then fed to a flash tank and heated to facilitate
monomer removal. The separated monomers are purified while the devolatilzed
polymer is pelletized in an extruder.
The molecular weight of the polybutylene manufactured by this process
ranges from 250,000 to 650000. [ 32J Polybutylene resins whhh are usud for
film have antiblock and slip agents added to the polymer .ihile it is in the
extruder.
A recipe for producing polybutylene by mass polymerization was not
found in the literature. However, a recip for pLoducing polybutyler e by
solution poly’nerjzation, based on an Imperial Chemical Lndustrieo patent, is
shown below: (25J
Material antity
1—Butene (monomer) 40 1
Titanium Tetrachioride (catalyst) 0.00931 k 5
Triethyl fluminum (catalyst) 0.0056 kg
Hexane (solvent) 0.13 1
Ethyl Alcohol (molecular weignt regulator)
Energy Requirements
No data giving energy requirements for polybutylene production were
found in the literature consulted.
FNYIRONMrrM. AND INDUSTRIAL HEALTh CONSIDERATIONS
P ..lybutylene is a nontoicic compound which is used in packaging meat. and
other food items, transporting ‘.ater, including potable water, and or’ er
piping and packaging applications.(32j None of the chemicals which have
been identified as inputs to polybutylene processing are known carcinog.na.
P.owever, two substances used in polybutylene manufacture (1,1—dimethyihydra—
zine, catalyst, and Lsotacttc polypropylene, a transformation aid) have
been identified as av i’ual carcinogens and are therefore potential human cir—
cinogens. One compound, I,l—dimeehylhydrazine, has been listed as hazardous
under RCRA.
Worker Distribution and Emissions Release Points
Estimates of worker distribution have been made by correlating major
equipment uanhour requirements with the process flow diagram in Figure 31.
Estimates are shown In Table 97.
Only fugitive emissions from process vents and leaks are present in
polybutylene processing. These fugitive emissions, however, may pose a
significant environmental and/or worker health problem based on the stream
constituents, process operating parameters, engineering and administrative
controls, and maintenance programs.
298
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TABLE 97. WORKER DISTRIBUTION ESTIMATES FOR POLYBUTYLENE PRODUCTION
Unit Workers/Unit/8—hovr Shift
Batch Reactor 1.0
Monomer Purification Column 0.25
Washing 0.25
Flash Tank 0.125
Extrusion 0.5
299
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Process sources of fugitive emissions are shown in Table 98. Neither
OSHA nor the American Conference of Covernmeatal Industrial Hygienists
(AcGIH) have set standards or recommended exposure levels for 1-butene and
the other gaseous hydrocarbons p3tentially emitted from polybutylene produc-
tion. However, polymer particulates from pelletizing may produce aaiaance
dust levels which exceed the OSHA standard.
Propylene, ethylene and hydrogen are simple asphyxiants whose presence
in workplace air reduces the amount of available oxygen.
Available health effects information for substances which have yielded
positive animal carcinogenicity tests is given in the following paragraphs.
Other toxicity information is summarized in Table 10 and in IPPEU Chapter
lOb.
Health Effects
Relatively little health effects data exist for the input materials to
polybutyleue polymerization. Two substances, however, have tested positive
in animal tests for carcinogenicity and are therefore pctóntial human car-
cinogens. They are ll—dieethylhydraztne, a catalyst, and the transforma-
tion aid, isotactic polypropylene. The reported health effects of exposure
to these substances are summarized below.
l,l—Dimethylhydrazine poses a high toxic hazard through ingestion,
inhalaticn, and skin absorption.1242J Although no epidemiological data dre
available, it has produced positive results in animal testing frr carcino-
genic át d mutagentc effects.(lOOJ OSM has set an air standard of 0.5 ppm
(8 hour NA).1671
Polypropylene has produced positive results in animal testing for
carcinogenicity.(1O7j ft poses a very low toxic hazard, however. For
example, polypropylene medical devices have produced little or no irritant
respon eu ‘hen placed into connective or moscle tissues for short periods of
time.(31J lie propensity fo’ diffuson ot polypropylene from the material
is so smak that biological response cannot be detected.(3lJ
Air Emissions
Table 98 lists the sources of fugitive VOC emissions associated with
this process. These three sources are vents and may be controlled byif 2851
• kouting the stream to an incinerator to remove any remaining
t ydrocarbona; and/or
• Routing th. stream to a blowdown.
Other sources of fugitiv. VOC emissions, such as flanges, valves, pumps,
compressors, and cooling towers, may be controlled by equipment modifica-
tion. However, a regular inspection and maintenance program may be the best
method for reducing these emissions.
300
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TABLE 98. SOURCES OF FUGITIVE Ei1ISSIONS FROM POLYBUTYLENE M&NUFACTURE
Source Constituent
Reactor Vent 1—butene
Polybutylene
Other C4 mcnomers
Wash Tank Vent 1—butene
Polybutylene
Other C 4 ono _ers
Pellerizing Extruder Vent 1—butene and Polybut:’lene
Particulates and Emissions
301
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The particulate emissions associated with this process are also listed
in Table 98. The extruder vent may be routed to a baghouse or electrostatic
precipitator to collect particulates.
Wastewater Sources
Polybutylene .anufac .ure generates two vastewater streams: the efflu-
ent from the wash tank and routine cleaning water. The effluent from the
wash tank may contain a small amount of catalyst which is carried from the
reactor to the wash tank with the polymer—monomer mixture. Polybutylene and
1—butene are virtually insoluble in water, and therefore. are not band In
the vastevater. There are no data in the literature which give wastewater
characteristics for this process.
Solid Waste
The solid wastes geneTated during polybutylene production include
substandai d polymer which cannot be salvaged by blending and collected
part iculates. These wastes are not hazardous; therefore, their disposal
should not pose an environmental problem.
Environmental Regulation
Effluent limitations guidelines for polybutylene have not been
established.
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Sa . .y/release valves must not release more than 200 ppm above
background, except in emergency pressure releaseia, which should not
last more than five days; and
• Leaks (which are defined by VOC emissions greater than 10,000 pp .)
must be repaired within 13 days.
One input to polybutylene product has been listed as hazardous (45
Federal Register 3312, May 19, 1980):
1,l—dimethylhydraztae — U098
All disposal o’ this material or polybutylene containing residual amounts of
this must comply with the provisions of the Resource Conservation and
Recovery Act (ECRA).
302
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SECTIOr. 13
POLTCAR3ONATE
EPA Source Classification Code — Polyprod. General 3-01-081-02
INTRODUCTION
Palycarbonates, a special class of linear polyesters, result from the
reaction of carbonic acid derivatives with aromatic, aliphatic, or mixed
diol . Although many diffecent polycarbonates exist, the pol carbonate of
bisphenol—A ( 4 , 4 ’dihydroxy—2,2’—diphenyl —propane) is the only resin of
major commercial importance. Polycarbonaces combine desirable product
properties, high heat stability, toughness, and transparency with easy
processability and low cost. specialty resins contain small amounts of
other polyhydric phenols in additior. to bispl’enol—A. Tetrabromobisphenol—A,
tetramethylbisphenol—A, and 2 , 2 —bis(4—hydroxyphenyl)—l,l —dichlorethy lene
constitute the major comonomer. used.1751
The most valuable properties of polycarbonate. include: good mechanical
properties, especially i p ct strength, over a wile temperature range; good
resistance to high temperatures, even on lo.ig—term exposure; low water
absorption; od dimensi3nal stability; complete transparency; good weather—
in properties; physiological inertness; good resistance toward aqueous
agents, oils, fats, aliphatic hydrocarbons, and alcohols; and self—extin-
guishing properties.f16J These properties make polycarbonates suitable as
replacements for metals, glass, wood, and other thermoplastic.. Table A—14
in Appendix A lists some typical polycarbonate properties.
The many differing uses of polycarbonates inc1 de electrical applica-
tions, appliance., instrumeutation, communication and electronics, automo-
tive, marine, aerospace, photography •.ad films, light and optical technol-
ogy, of f ice equipment, various induitrial equipment, food packaging, sport-
ing good., toys, medical appliances, household goods, and appiiances.(16J
Although most commercial polycarbonates are biephenol—A based, pertinent
detailc concerning the production proe sses are scRrce. Direct reaction,
transesterification, and interfactal polymerization reportedly work.
Polymers çroduced ny the transesterification process, first favored over
direct reaction for its iow cost, exhibit a narrow range of properties;
therefore, use of this process ha. declined. Present production is probably
performed by the interfacial polymerization process.(75J
I NDUSTRY DESCRIPTION
Two producers comprise the polycarbon&te industry: General Electric
Company and Mobay Chemical Corporation. Production facilities are located
303
-------
in three states: Indiana, Texas, and Vest Virginia. Table 99 lists these
producers, their locationb, and their 1982 capacities.
Polycarbonates, usd4 as metal and glass replacements, have experienced
stable &alee from 1979 to 1981. The small growth experienced during this
tine frame (from lO7, OO to 111,000 metric tons) concurs witis the
optic fiber usage. Current existing capacity oZ 193,200 metric tons is
suffi ient to accomodate any industry growth in the near future.
PROD(JCTION AND END USE DATA
In 1981, polycarbonate production totaled 111,000 metric tons.t 1431
Polycarbo .iate applications inclbde:(16, 30, 75, 247j
• Beer pitchers, mugs, and other high—volume non—electric hoUsewares,
such as tableware, flatware, coffee filters, trays, and baby
bottles;
• Returnable bottles, particu1arly large milk and water bottles;
• Iledical equipment, including bjochemical laboratory, apparatus,
syringes, dental prosths es, and cages for rats and’other small
animals;
• Automotive markets, including lenses and bright trim extrusions,
lamp housings, electrical components, decorative pieces, thin-wall
mechanical parts, large exterior parts, instrument panels, and
bumpers;
• Construction applicat..ons, including door and window com#onene.,
drapery fixtures, furniture, and plumbing;
• Electrical and electronic product., including printers, copier.,
other business machines, telephon, connectors, circuit boards,
wiring blocks, and other industrial components;
• Lighting applications, including diffusers and globes, housings, and
other compcnent parts;
• Mirro izi d sheet for schools, off—highway equipment, and security
facilitias;
I Protective eyewar. and helmets;
• Sheet for appliances, business machines, sound attenuation, aircraft
interiors, transparent canopies for high speed military aircraft,
solar collectors, and bulJet—reststant parts;
a- Electrical insulation for radios, television sets, X—ray equipment,
and insulation of coils and wires;
-------
TABLE 99. U.S. POLYCARBONATE PRODUCERS
1982 Capacity
Producer Location Thousand Metric Tons
Ger eral Electric Co.
Engineered Materials
Group
Plastics Business
Operations Mount Vernon, IN 120.5
Mobay Chemical Corp.
Plastics & Coatings
Division Cedar Bayou, TX 59.1
New Martinaville, WV 13.6
TOTAL 193.2
Source: Direct3ry of Chemical Producers , 1982.
305
-------
• Transparent covers for meter housings and transformers, street and
industrial lamps, signal lamps, and housings for traffic signals;
• Implosion shields for tálevision sets and housings for radio
receivers and transmitters, hair dryers, electric shavers, and
kitchen utensils;
a Cabin coverings, cable casings, and battery cases;
• Engineering applications including frames I or various neterin and
regulating apparatus, covers of various kinds where transpai’ncy is
important, filter vessels, parts for pumps (such as rotors), and
various other housing and ppe; I
• Parts for fire extinguishers, protective masks, ski mobiles, hockey
gear, and motorcycle shields;
• Photographic equipment including movie cameras and projectors as
veil as housings, cassettes, and reels;
• Drafting films, drafting tools, and ball point and fountain pens;
and
• Break—resistant windows for buildings (gymuasiums, schools), buses,
and trains.
Table 100 lists”poiycarbonate markets for 1981.
PROCESS DESCRIPTIONS
Most polycarbonates are produced by interfacial polymerization.
Although other processes are reported in the literature, the most recent
information indicates the predominance of the interfacial polymerization
process. Transesterification processing gives polymers which exhibit a
narrow range of properties; therefcre, use of this process has declinea in
spite of the lover production cost.(73J
Polycarbonates of bisphenol—A produced by interiacial polymerization
utilize an inert organic medium (aethylaus chloride) and an aqueous alkaline
solution (sodium hydroxide) for the tvu—phase polymerization medium. The
polymerization occurs in an emulsion at the interface of the two immiscible
solvents. Phosgone is soluble in the chlorinated hydrocarbon, and bie—
phenol—A is soluble in the aqueous caustic aulution. The two solvents are
intimately mixed to form an emulsion. Crude polymer solubilizes into the
hydrocarbon phase.!247J
Durtng polymerization, bisphenol—A acts as a nui leophile and attacks
the carbon atom of the phosgene. ‘the chloride ion is displaced, and
di eqolves into the aqueous phase, as shown belays
306
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TABLE 100. MAJOR POLYCARBONATE MARKETS
1981
Market Thousand Metric Tons
ApplianCes 14
Com uni:at ions and Electronics 22
Glazing 32
Lighting 4
Signs 3
Sports and Recreation 8
Transportation 13
Other 15
TOTAL 111
Source: Modern Plastics , January 1982.
301
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Ott + Cl-C-Cl + NaOH — H0_i() - _(). 0 C Cl + 1120 + Ned
C it 3 CH 3
In the presence of a catalyst or accelerator, these low molecular weight.
Doly’arbonate building blocks react to form higher molecular weight poly—
carbonatee. Accelerators enable the reaction to be carried out at room
temperatute in a continuous process.
ii tto_f - . _c ..ci • (n—I)N 0N Catalyst , + (st_I)Rlo + (n-l)N.Cl
Molecular weight is rc!gulated by adding a chain terminator such as a
nonofunctional phenol to tte monomer charge.
Table 101 lists typical Input materials for this ?rocess. Adlitives are
used to give greater flame retardai ce , thermal atablflty, WI light stabil-
ity, color stability, and eisler mold release.(30j Operating parameters for
thL’ process are considered to be proprietary.
inte facial Polymerization
The interfacial polymerization pro eas in Figure 32 presents a block
dtagr.w which traces the flow of matezials through the manufacture. Bia—
phenol—A and a small amount (1 to 3 percent) of monofunctional phenol are
dissolved or slutried in an aqueous sodium hydroxide solution. Methylene
chloride, a polymer solvent, is added along with a catalytic amount of
tertiary amine, an accelerator. Phosgene gas is dispersed in the stirred
mixture. The polycarbonate formed dissolves in the solvent while the sodium
“hloride by—product remains dissolved in the aqueous phase. Polymerization
is complete when the concentration of phenol in the aqueous phase falls to
zero.
The two—phase reaction system is then separated and the organic phase,
cont itning the polymer, is voahed with water and acid to remove any alkaline
residues. Recovery processes for isolating the polymer from the reaction
solvent are closely gaard.d trade secrets.(15J One proposed process uses
solvent str pptng followed by drying and vacuum—vented extrusion. The
pellets prod ed are then ready for bag fng and shipm.nt.
3O
-------
TABLE 101. TYPICAL INPUT MATERIALS FOR POLYCARBONAIE PROCESSING
Function Compound
Monomer bisphenol—A
phosgene
Comonomer 2 ,2—bis(4—hydroxyphenyl)—l , 1—
dichioroethylene
tet rabromobtsp’ienol—A
t2tramethylbispheno l—A
Initiator potassium hyd:o .ide
sodium hydroxide
water
Molecular Weight Regulator monofunctional phenol
Color Enhancer sodium dithicnite
Solvent methylene chloride
Accelerators quarternary ammonium salts
triethylbenzyl ammonium chloride
tertiary anines
N ,N—dierhylcyclohexy lamjna
- trtethylamine
Acid Wash hydrochloric acid
phosphoric acid
Sources: En yelopedia of Chemic i Technology , 3rd Edition.
Encyclopedia of Polymer Scicn e and Technology .
309
-------
Figure 32. Block diagram for polycarbon e production (interfacjai polymerization).
Source: Bn clopedja cf Polymer Science and Technology .
Wd
A. U
Li,
I —
0
a*ijflzuI
kmL iini
Condenaed
Stem.
5u1v n t
-------
A typical recipe for producing 100 parts of polycarbonate by the
interfacial phosgenatf,n process is shown below: (260J
Material Parts by Weight
Bisphenol—A 92
Phosgene 42
P—tert—butyl Phenol (chain terminator) 1
Sodium Hydroxide Sufficient to produce
a 5—10% aqueous caustic
solution
Methylene Chloride (solvent)
Water
Energy Requirements
The energy required for a polycarbonate process has been specified
as: ( 1811
Energy Required Unit/Metric Ton of Product
Steam 600 kg
Electricity 2.34 x IO Joules
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Polycarbonate resins are non—toxic compounds, approved by the FDA for
food contact applications, which impart no odors or taste to foods. How-
ever, one of the input materials to the polycarbonate production process
(phosgene) has been listed as a hazardous waste under RCRA.
Worker Distribution and Emissions Release Points
Worker distribution estimates for polycarbonate production are shown in
Table 102. Estimites were made for the interfacial polymerization process
outlined in Figure 32.
Probable air emission sources are listed in Table 103. No major air
emission point sources are expected from this process. The only air emis-
sions are fugitive emissions from such sources as reactor vents, dryer
vents, and extrudera. These may pose a significant environmental ‘iorker
health impact depending on process operating conditions, input materials and
degree of process contrcl.
HealPh effects of three contaminants of concern are summarized below.
Additional toxicity data for the substances in Table 101 are provided in
Table 10 and IPPEU Chapter lOb.
Potassium and sodium hydroxides, hydrochloric acid and phosphoric acid
are highly irritating to the skin and mucous membranes. Brief contact to
concentrated amounts of these substances can cause severe chemical burns.
311
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TABLE 102 • WORKER DISTRIBUTION ESTIMATES FOR POLYCARBONATE PRODUCTION
Unit WorkerslUnit/8—hour Shift
Batch Reactor 1.0
Phase Separator 0.25
Washing 0.25
Solvent Stripping 0.25
Dryer 0.5
Extrusion 0.5
312
-------
TABLE 103. PROBABLE SOURCES OP AIR EMISSIONS FROM POLYCARBONATE PROCESSING
Reaction Step Probable Source Constituent
Interfacial Poly eri— Reactor Vent Phosgene
zat ion Bisphenol—A
Methylene Chloride
Phase Separation separation Tank Methylene Chloride
Vent
Washing Wash Tank Vent Methylene Chloride
Solvent Stripping Condenser Vent Methylene Chloride
Drying Dryer Vent Methylene Chloride
Particulates
Vacuum—Vented Extruder Extruder Vent Methylene Chloride
Particulatee
313
-------
Little data are available from which employee exposure potential may be
estimated. However, one source estimates hydrocarbon emisaione from poly—
carbonate molding operations at 32 g/kg product.(286J
Health Effects
Polycarbonate processing typically involves the use of less than 20
input materials and specialty chemicals. Most of these are only slightly to
moderately toxic. Three substan es used by the industry are highly toxic,
however. They are: phosgene, ne of the monomers; the accelerator tn—
ethylamine; and phenol, a molecular weight regulator. The paragraph, below
summarize the reported health effects of exposure to these three substances.
Phenol is extremely toxic by ingestion, inhalation, and skin absorp—
tion.fl5rApproximateiy half of all reported cases of acute phenol poison-
ing has resutled in death.12781 Chronic poisoning may also occur from
industrial contact and has caused renal and hepatie damange.(149J Evidence
indicates that phenol is also a tumorigenic, mutagenic, and teratogenie
agent; however, a recent carcinogenesis bioassay by the National Cancer
Institute produced negative resules.(233J The OSHA air standard is 5 pp. (8
hour TVA).(67J
a strong local irritant, is also extremely toxic by inhala—
tion.(2423 Concentrations greater than 0.25 ag/i of air (62 pp.) may be
fatal when breathed for one—half hour or aore.1273J Three to 5 ag/i causes
death within a few mtnutes.(273J Any exposure is extremely dangerous
because there is no protective respiratory reflex to prevent deep inspira-
tion of phosgene.(88J ft has been reported to have the ability to condition
the olfactory senses so that the characteristic odor may be dei.ected only
briefly at the time of initial exposure.1238J The OSHA air standard is 0.1
pp. (8 hour TWA).f67j
Triethylamine is highly toxic by ingestion and inhalation and moder-
ately toxic via dermal route..(2433 It is a strong irritant to tissue. At
least one animal study has shown that tniethylamine produced aitagenic
effects in rats at the low dose of 1 mg/m 3 .(96J The 0311* air standard is
25 ppm (8 hour TVA).(67J
Air Emissions
According to EPA estimates, the population e.posed to air emissions in
a 100 km 2 inca surrounding a polycarbonate production.plaiit is: 41 per-
sons exposed o hydrocarbons and 2 parsons exposed to particulates.(286J
These sources may be controlled by venting VOC emission streams to a flare
or blovdovn f285J and streams containing particulate. to either an electro-
static precipitator or a baghouse.
Vastevater Sources
The major wastewater sources associated with tt.i. process include the
alkaline salt solution generated during phase separation, the ult solution
314
-------
generated during washing, condensed steam from the solvent stripping pro-
cess, and routine cleaning water. No data concerning either vastewater
production or wastewater characteristics were found in the literature
consulted.
Sojid Waste
The major solid waste generated by this process is the by—product
sodium chloride, estimated at 760 kg of salt per metric ton of polycarbonate
produced. 93J Other solid wastes include polymer lost due to reactor clean-
ing and spillage, collected particulates, and substandard product which
cannot be blended.
Environmental Regulation
Effluent limitations guidelines have not been set for the polycarbonate
industry.
New source performancestandards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which re defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
Phosgene has been listed as a hazardous waste and designated as U095
(46 Federal Register ?7476, May 20, 1981). Disposal of any polycarbonate
resin containing residual amounts of phosgene or any containerized phosgene
gas must comply with the provisions set forth in the Resource Conservation
and Recovery Act (RCR ).
315
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SECTION 14
POLY(ESTER—IMIDE) AND POLY( THER—IMIDE) RESINS
EPA Source Classification Code — Polyprod. General 3-0101802
INTRODUCTION
Poly(ester—imide) and poly(ether—imide) resins are condensation
polymers which have a repeating imide group as an integral part of the chain
structure. An inide group is shown below;
0
I
>
I
0
PoIy(ester—imides) are characteriged by repeating ester and imide linkages,
while poly,(ether—imides) contain sther and imide linkages. -
High temperature resistance, good electrical properties, good wear and
friction properties, chemical ine ,rtness, radiation and cryogenic temperature
stability, and inherent nor.flammability are properties of polyinides which
allow their use in a variety of applications.1441 Modified polyimides have
poorer thermal stabiity than the compaiable arcaatic polyimides; however,
they offer greater versatility in procissii.g. Typical properties of polr
(ether—imide) resins are presented in Tab ie A—iS in Appendix A.
Poly(ester—imjdes) are used primarily for wire insulation.(248J Poly
(ether—imides) are used for inJectio molding, extrusion, blow molding, and
structural foam molding. Commercial use of poly(ether—i.ide) resins include
circuit—breaker housings, under—the—hood automotive applications, microwave
oven stirrer shafts, and integrated—circuit chip carriers. [ l50J
The polycondensat ion processes used to produce poly(ester—imide) and
poly(ether—imide) resins involves the reaction, in solution, of an aromatic
anhydride, a diamine, and a dianion, such as glycol or an alkali metal salt.
Poly(ester—imide) resins can be produced by two processes, both af which
start with trimellitic ar.hydride. The difference between the two processes
is the reactanr addition sequence. These prr- esses, as well as the poly
(ether—imide) resin production process, are described in . ore detail later
in this section.
316
-------
INDUSTRY DESCRIPTION
The producers of poly(ester—imide) and poly(ether—imide) resins are
listed In Table 104.
Poly(ester—imide) resins are manufactured by three firms, representing
three facilities In two states. Two tacilities are located in New York
State, and one facility is in Missouri. No production data were reported in
the literature for these f3cilittes.
Poly(ether—Imlde) resins are manufactured by two firms. General
Electric began commercial production of poly(ether—imide) at their Mount
Vernon, Indiar.a facility in 1982. C.E.’s production is reportedly t tween
2.3 and 4.5 thousand metric tons per year. G.E. is planning to expand
prod.. tion capacity at this faciljty.(150J LNP Corporation reports the
availability of small quantities of poly(ether—imide) risins; however, the
manufacturing location Is not listed in the literature.(33J
PRODUCTION AND END USE DATA
The 1982 U.s. market for all types of polyleide resins is estimated to
have been 2.5 thousand metric tune, valued at about $120 million. 4odified
polyimides, including poly(amide—imldes), poly(ester—imjdes), and poly
(ether—imides), comprised about 45 percent of the polyimide market. Modi-
fied polyiinides have many uses, including:(44J
• Wirp n ’m is and other coatlng applicitions, and
• Molded parts for the aerospace and hydraulic equipment industries.
Poly(ether—imlde) is reported to be more competitive witb engineering
materials such as polyphenylene sulfide and polyaulfone than with other
aromatic polyimideg. End uses for poly(ether—imide) resins being developed
include fibers, film, sheet, and wire inaulation.t71J
PROCESS DESCRIPTIONS
The Dolycondensation process used to produce poly(eeter—imide) and
poly(ether—jmjde) resins Involves the reaction, in solution, of an aromatic
anhydride, a dianiine, and a dia ion, suc a as glycol or an alkali metal salt.
Not mui h information is availabla in the literature on the industrial
processes used to manufacture either poiy(ester—Imide) or poly(ether—Lmide)
regjrie. Little information is available on reaction mechanisms. Reaction
chemistry, mainly available from patent literature, is discuseed below for
each resin.
Table 105 listg typical input materials for these r”sins.
Poly(ester—im(de) Resins
Poly(egter—jmjde) resins can be produced by two processes. Both pro-
cesses start witi trimellitic anhydride (ThA). In one process, TMA is first
reacted, In solution, with a diamir.e. The intermediate product is then
317
-------
TABLE 104. U.S. POLY(ESTER—IMIDE) MD PbLY(ETHER—IMIDE) RESIN PRODUCERS
1982
Capacity
Thousand
Product Mecric
Producer Location Type Tons
General Electric Company
Engineered Materials Group Schenectady, NT Poly(ester— N.E.
Electromaterials Business imide)
Department
Plastics Business Opera— Mount Vernon, IN Poly(ether- a
tions teide)
The P.D. George Company St. Louis, NO Poly(ester— N.E.
imide)
Schenectady Chemicals, Inc. Schenectady, NY Poly(ester— N.E.
im tde)
LNP Corporation Malvern, PAb Poly(ether— N.E.
imide)
N.E. — Not reported.
aModern Plastics reports a production range c 2.3 to 4.5 thoasand metric
tons per year.
bplant location not rep rte : corpcrate headquarter location listed.
Sources: Diri ctory of Chemical Producers , 1984.
Chemcyclopedla , 1985.
318
-------
TABLE 105. TYPICAL INPUT MATERIALS FOR POLY(ESTER—IMIDE)
AND POLY(ETHER—IM1DE) RESINS
Anhydrides Trlinellitic Anhydri!Je (TMA)
3—Nitrophrhalic Anhydride
4—Nitrophthalic Anhydride
Arylenes 2,4 ‘—d hydroxy diphenylmethane
bis(2—hydroxyphenyl) nethane
2,2—bis(4—hydroxyphenyl) propane (Bisphenol A)
1 ,2b1s(4—hydroxyphenyl) ethane
4,4 ‘—dihydroxydiphenyl ether
4,4’ —dihydroxybiphenyl
Hydroqui none
Phenylene
Glycols 1,2—ethylene glycol
l,3—trimethylene glycol
1 , 4 —tetraisethylene glycol
1, 5—pentamethylene glycol
1 ,6—hexaaethylene glycol
3—inethylpentane-l ,5—diol
I , lO—decamethylene glycol
Solvents Methanol
Ethanol
Isopropyl Alcohol
Benzene
Toluene
Pen ta ne
He xa ne
Octane
Cyc lohexane
Hep ane
Dimet hyl foriiiamide
N—inethyl—2—pyrrol idone
N ,N—dimethylacetamjde
diaieihyl sulfoxide
H—creso l
N—inethylpyrrol Idone
Hexamethy Lphosphoramide
Aroclor
(continued)
319
-------
TABLE 105 (continued)
Diamines Hexamithyler.e diamine
Pheny]enediamine
Benzidene
4,4 ‘—Dialninodiphenyl ether
3,3, —Dimethoxy—4, 4’ —dia i ne diphenyl
4,4 ‘—Diaminodiphenyl methane
4 ,4’—Diaminodiphenyl sulcun
3, 5—Diaminobenzojc acid
Durenedjainine
Additives Thionyl Chloride
Tetrabutyl Titanate
Zinc Acetate (catalyst)
Antimony Triozide (catalyst)
Sod um Hydroxide
Acetic Acid
Sources: Loncrini, “Aromatic Polyesterimides,” Journal of Polymer Science:
Part A—I , Vol. 4, pp. 1531—1541, 1966.
Wirth, Joseph G., and Darrell B. Heath, U.S. Patent No. 3,838,097,
September 24, 1974, assigned to General Zlectric Company.
Ranney, Polyimide Manufacture 1971 , Moves Data Corporation,
Park Ridge, NJ.
320
-------
reacted with a glycol to produce the poly(eater—imide) resins. This
sequence of reactions is shown below: [ 230]
0
HOOC j( C C I I OH
+ H 2 N(CH 2 ) 6 NH I. .
Sol n.
0
TPqA He ia.ethyIene
Diawine
o 0
• I
r /
2 +
N—(CH )
I • COOCH 3 1 120
o
Bie—trimel lit imidate
Intermediate
0
I
Bie-crimellitimidate + I4o_(CN2)4_oH_..__a [ ,L L N—(cH 2 ) 6 —N
—
I
0
Tat rameth I.n.
Glycol
In the second process, TMA is first reacted with an aromatic diacetozy
compound to prcduce an aromatic bisesteranhydrtde intermediate. The inter-
mediate is then reacted with an aromatic diamine in a polar solvent to give
a polyamic acid precursor. The precursor is then Phermally converted to the
poiy(ester—lmide) re3in. Thi; aequance of reactiuna is shown below: [ 139J
HOOC11I (Ci . — •
C-O-A,• 0-c
ma
$IIIIIersnIiyd,jd. r.eardlat.
Pu I .r
IIIIIerdflhIyd,id.
Iflt.r.,dlat, • II/I I NIIz
P.1 ..I A. Id
Pm .r ,,r
w) cx: c-NI’.
C-OH
o 8
Pnlpa.h Atid Pre u,.,u
0 0
I
- Il_i. • N 1 0
‘-0-Ar 0-C ( J
I ,
,
321
-------
The dixference between these two processes is the order of adding reac-
tants to TMA. In the first process, a diamine is added to the TMIt—methanol
solution before adding glycol. In this process, methanol is removed by
distillation, and diimide diacid is recrystallized from dimethyl forinamide.
Bis—trlmellitimidate inteL-mediate is produced by reacting the diimide diacid
with thionyl chloride in a methanol—toluene solution. Bia—trimellitim±date
is converted to poly(ester—imide) by reacting with glycol and tetrabutyl
titanate. A typical recipe for the production of poly(ester—imide) resin by
this çrocess is given below:(230J
Step Material Quantity
1 rrimellittc anhydride (TMA) 0.096 kg
Methanol (solvent) 0.5 1
hexamethylene diamine 0.029 kg
2 N,N’ —hexa .ethy1e : e—bjs— 0.047 kg
trimellitimide (ditmide
diacid)
Toluene (solvent) 0.2 1
Methanol (solvent) 0.05 1
Tnionyl chloride 0.098 1
Parts by Weight
3 Bis—trilellitim ldate S
1, 4 —tetramethylene glycol 2
Tetrabutyl tttanate 0.5
in the second process, the diacetozy or glycol is reacted with the TMA
solution to produce an intermediate before the diamine is introduced. A
typical rect’ie for producing a bisesteranhydrid, intermediate is given
below: 11391
Material Quantity
Trimellitic anhydride (TMA) 0.192 kg
p—Phenylene diacetate 0.097 kg
Aroclor #1242 (solvent) 0.5 1
n—Heptane (solvent) z 1
Diethylether Washing
A recipe was not found for producing a poly(ester—imide) resin from
this internediate.
Although information was not found in the literature on industrial
manufacturing processes for poly(ester—i.jde) resins, a process, based on
engineering Judgement, is shown in Figure 33.
322
-------
t—I It II I.
.h drIJ .
M th .u. ‘I
I . . )
I.
at...
VL III
1.4 I. trdm.thyIel..
(Iv. ..I
Dl.. II .vI thiunyl
F..ta..I L u (I,...rI,’e
I
IIiI , .nyl
I hk,r IJe
I.Id.) ReaIft
Jut r .b..IyI
III aliat.
Figur. 33. Po1y(ester—i ide) resin anufacturtng process.
-------
Poly(ether—imide) Resins
Poly(ether—imide) resins are produced by reacting a bis(nitrophthali—
mide) with an alkali metal salt in a solvent. Bis(nitrophthalimide) is an
intermediate produced by reacting a dianine with a nitro—substituted
aromatic anhydride. This sequence of reactions is shown below [ 298J
0 0
Bha(Nitrnphthaljmide) • SuIv.nt [
Alkali ecal
Salt
A typical kecipe for the production of poly(ether—iniide) 1. shown
heiow:f298J -
Material
Bisphenol A
Sodium hydroxide (50.32 solution)
Dimethylsulfoxjde (solvent)
Benzene (solvent)
4 , 4 ’ —Bis(3—nitrophthaLjmjdo)
diphenylmethane
Claclal acetic acid (quench
reaction)
Methanol (precipitate product)
Quantity
2.2828 x to kg
1.5904 x kg
0.05 1
0.006 1
5.845 x i 3 kg
2 * i0 4 1
0.6 1
Although information was not found in the literature on industrial
maiufacturing processes for poly(ether—lmide) resins, a process, based on
en neering judgment, is shown in Figure 34.
Cnergy Requirements
Data concerning the energy requirements for this proceis were not found
in the literature consulted.
+
0
I
C.’.-
0
C
3 I
0
0 0
I I
•_Ø•
JJ N—R ii
N0 3 ’”.C” I C 3
I I
0 0
Djam ne
Nit ro—Subgt itutt’d
Aromatic
Bi’(NitrophchalI.jd.)
+
324
-------
tool ipo
1 r
Rliph.ni l
Ben ne
Dimyl by I -
Stilt OX i d e
B. then..
& 1I, inol
W.i.tli Wati.
NIL rogen
4.4Bis(3—’Iiirc,—
phihil I l o)
Dipheryl tIet bane
Atet It
At d
Fill F
Poly( Et her-
linide) Brain
Heihy len —
Chloride.
Methanol
Figure 34. Poly(ether—imide) resin manufacturing process.
-------
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Polyimide resins do not pose a significant health concern.(71J How-
ever, trimellitic anhydride and phthalic anhydride are reported as toxic
(91], and care must be used in handling these materials. In addition, sev-
eral of the solvents and diamines used in poly(ester—imide) and poly(ether—
imide) resin manufacture are also regarded as toxic.
Vorker Distribution and Emissions Release Points
Estimates of worker dietribution have been made by correlating major
equipment manhour requirements with the process flow diagrams in Figures 33
and 34. Table 106 shows estimates for both poly(ester—imide) and poly—
(ether—imide) resin manufacturing processes.
There are no major point source air emissions associated with either
poly(ester—imjde) or poly(ether—jmide) processing. The only air emissions
are fugitive emissions from such sources as reactor vents, dryer vents, and
condenser vents. The impact of these emissions depends on the process
operating parameters, engineering and administrative controls, and input
materials used.
Sources of fugitive emissions are shown in Table 107, based on engi-
neering judgement. Solver ts typically used in both processes include
methanol, dimethyl formamide, dimethyl sulfoxjda, bensene, and toluene.
Available toxicity information for major process reactants and additives is
summarized under “Health Effects” beJow.
No data were located in the literature from which worker exposure
potential may ‘e estimated.
Health Effects
The mai’ufacture of poly(ester—jmtde) and poly(ether—imide) resins
involves the use of several toxic materials. As discussed earlier, both
trimellitic anhydride and phthalic anhydride are reported as toxic. In
addition, several of the solvents, including methanol, benzene, toluene,
dimethylformamide, and dimethylsulfoxide, and several of the diamines,
including hexamethylene diamine, phenylenedjamjne, diamiriodiphenyl methane,
and diaminodiphenyl sulfone are reported as toxic compounds. Table 108
presents some additional information on these toxic compounds, based on data
in IPPEU Chapter lob.
Air Emissions
Sources of fugitive VOC emissions are listed in Table 107. All the
process sources are vents which may be controlled by: 12851
• Routing the stream to a flare to incinerate the hydrocarbons
present; and/or
• Routing the stream to blowdown.
326
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TABLE 106. WORKER DISTRIBUTION ESTIMATES FOR POLY(ESTER—IMIDE) AND
POLY(ETHER—IMIDE) PRODUCTION
Process Unit Workers/Unit/S—Hour Shift
Poly(ester—imide) Reactor 1.0
Crystallizer 0.5
Polymerization Reactor 1.0
Poly(ether—jmjde) Reactor i.o
Heat Exchanger 0.25
Filter 0.75
Dryer 0.25
Dissolver 0.75
327
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TABLE 107. SOURCES OF FUGITIVE EMISSIONS FROM POLY(ESTER—IMIDE) AND
POLY(ETHER—IMIDE) MANUFACTURE
Process
Poly(ester— Poly(ether—
Source Constituent iinide) ixide )
Precursor Reactor Trimellitic Anhydride
Vent Methanol X
Hezaxethy Lane Diaxine *
Diaethyl Foreaaide *
Thionyl Chloride
Toluene *
Bisphenol A
SodiuR Hydroxide
Dixethyl Suif oxide *
Benzene X
Water X X
Crystallizer Vent Bis—triaellitimidate *
Water X
Precipitation, Alkali Metal Salt
Filtration, Drying Diaethyl Sulfoxide *
Vents 4,4 ‘-Bis(3—Nitropnthalieido)
Diphenyl Methane
Acetic Acid
Methanol X
Water X
Part icula tes X
Polyxerization Glycol *
Reactor Vent Tetrabutyl Titanate *
Zaidate a
Poly.er *
Dissolver and Methylene Chloride *
Crystallizer Vents Methanol *
Intaruiediata *
Polyeer a
*Trace asounts of these coapound. are expected, if they are present at all.
328
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tOXIC M1P0UNDS USED IN POLY(ESTER—IMIDE) AND
Y(ETHER-INIDE) MANUFACTURE
rt y —
ion, Humans
100 ppm/1OY—l
Concern
Mutagen
Teratogen
Primary Irritant
Dangerous Fire
Risk
Ingestion
Inhalation
Skin Absorption
Mutagen
Teratogen
Carcinogen
Primary Irritant
Primary Irritant
Ingestion
Inhalation
Skin Absorption
Dangerous Fire
Risk
Tumorigen
Mutagen
Teratogen
Tumorigen
Teratogen
Strong Tissue
Irritant
Ingest ion
Mutagen
Corrosive
Ingestion
Irritant
OSHA Regulation
200 ppm TWA
10 ppm TWA
200 ppm TWA
300 ppm Ceiling
10 ppm TWA
(skin)
(continued)
329
-------
Table 108 (continued)
Input Kateria . Toxicity Concern OSHA Regulation
Phenylenediauiine ,Toxic Inhalation
Oral, Rat Irritant to Skin
LD5O: 650 mg/kg Tumorigen
Ilutagen
Diaminodipher 1 yl Subcutaneous, Rat Causes Toxic
thane LD5O: 3300 mg/kg Hepatitis
Diaminodiphenyl Toxic Positive Carciii—
Su]fone Oral, Humans ogen (Animal)
LDLO: 18 gm/kg/15 Ingestion
years Tumoitgeo
Effect: Systemic Mutagen
Oral, Rat
1000 mg/kg
330
-------
No data were found in the literature on the quantity of air emissions
from the polyitnide uian•ifacturing process.
Wastewater Sources
The wastewater so.irceg associated with poly(ester—imide) and poly
(ether—imtde) ream production are listed in Table 109. Poly(ester—imide)
has two 3curces of wastevater: routine cleaning water, and condensate from
the reactor in which TMA is reacted with diamine. Poly(ether—jmjde) has
three sources of wastewater: routine cleaning water, condensate from the
reactor in which Bisphenol A is reacted with sodium hydroxide, and filtrate
and wash water froa the polymer recovery filter.
Data were not found on the quantity of vastewater generated by poly—
imide manufacturing.
S1id Wastes
Only routine solid wastes are generated by the manufacture of poly
(ester—imide) and poly(ether—iimide) resins. These wastes include those from
reactor cleaning, product blending, particulate removal, and spfllage.
Enviroflmental Regulation
Effluent limitations guidelines have not been set for the poly(ester—
imide) and poly(ether—imide) resin manufacturing industry.
New source performance standard, (proposed by CPA on January 3, 1981)
for volatile organic carbon (JOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should
not last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous (46 Federal
May 20, 1981):
Benzene — U 019
Methanol — U154
Phthalic Annydride — U 190
Toluene — U220
All disposal of the compounds and resins which contain residual amounts of
these compounds must comply with the proviaicns set forth in the Resource
Conservation and Recovery Act (RCM).
.‘ 31
-------
TABLE 109. SOURCES OF WASTEWATER FROM POLT(ESTER—IMIDE) AND
POLY(ETHER—fl4IDE) PRODUCTION
Process
Source Poly(Ester—Imjde) Poly(Ether—Jmide )
Precursor Reactor Condensate X X
Filtration Effluent and Wash X
Routine Cleaning Water X X
332
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SECTION 15
POLYESTER RESINS (SATURATED)
F.PA Source Classification Code — Polyprod. General 3—01-018-02
INTRODUCTION
Two pro ucts dominate the saturated polyester market: polyethylene
terephthalate (PET) and polybutylene terephthalate (PET). ‘PET is a stiff
resin which exhibits higher impact and tensile strength when compared to
?BT. PET is a relatively short chain polymer which crystallizes more slowly
than PET but exhibits greater diseneional stability at high temperatures.
Good carbon dioxide barrier properties and the ability of PET bottles to
withstand high internal pressures (100 psi) make these resins excellent
containers for carbonated bev,rageg. Thm PET containers used are also
shatter resistant and light weight. Table A—16 in Appendix A presents some
typical PET properties.
PET is a crystalline thermoplastic whose rapid crystallization rate
combinEd with its good mold flow results in very short molding cycles. PET
is a high—strength, rigid, dimensionally stable, creep—resistant material
when filled. Mineral and mineral/glass fillers increase the strength and
stiffness of PET, as well as reducing the warpage which is experienced j
glass reinforced resins. Unfilled resins are chemically resistant, and
exhibit good tensile strength, toughness, and dimensional utability. Table
A—17 in Appendix A lists some typical properties of PET reqins.
PET is inherently resistant to most chemicals partly due to its
crystalline nature. At moderate temptratures, the following organic sol-
vents have little effect on PET: hydrocarbons, chlorinated hydrocarbons,
alcohols, ketones, esters, gasoline, and oils. Dilute bases and weak acids
have little effect at room temperature. PET parts are not harmed by solder-
ing flux, acid, freon, cleaning Solutions, and other substances used during
cleaning, testing, and aoldering.f9J
PET and PET may be produced by either a batch or COntinuous process.
The processes used to produce these two polymers are similar, with the major
difference being the input materials.
INDUSTRY DESCRIPTION
The PET industry Is made up of 12 producers with 19 sites located in
six states: Virginia, West Virginia, Tennessee, North Carolina, South
Carolina, and Alabama. Four producers constitute over 80 percent of the T
industry’s capacity. DuPont commands 30 percent with Fiber Industry,
333
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Eastman Kodak, and American Hoechst contributing 25, in, nd 10 percent.
respectively. Table 110 lists PET resin producern and their 1982
capacities.
The PIT industry is much smaller with only three producers located in
three different states. Table 111 presents these producers and their 1982
capacity.
PET and PIT resin usage is growing. In 1981, total sales of both PET
and PIT resins grew from 480,000 metric tons in 1980 to 561,000 metric tons.
PET resin production increased to 537,000 metric tons from 458,000 metric
tons while PIT resin production grew by 2,000 metric tons to 24,000 metric
tons.(14ZJ PET fiber production increased from 1,809,000 metric tons in
1980 to 1,869,000 metric tons in 1981.1351 The current excess capacity in
both the PET and PB industries is sufficient to accommodate any industry
growth In the near future.
PRODUCTION AND END USE DATA
In 1981, total PET production was 537,000 metric tons.(l43j PET’s many
uses include:(80, 82j
• Carbonated soft drink containers;
• Noncarbonated beverage containers for fruit drinks, lemonade,
and mineral water;
• Containers for mouthwash, edible oil, and chocolate jrup;
• Containers for foods, medicines, toiletries, cosmetics, and
household chemicals;
• Strapping materials used for industrial banding applications,
conveyor belting, filter fabrics, laundry bags, webbing, tire
cords, sewing threads, and ropes;
• Upholstery fabrics and curtains as well as light weight,
easy—care,” permanently pleatable articles of clothing;
• Ovenabie paperboard that is used for cooking
utensils in conventional and microwave ovens;
• Coatings for milk carton stock;
• Films, including magnetic tape, x—ray and photographic f ii.,
typewriter ribbons, and electrical insulation; and
• lackaging for boil—in—bags, retort pouches, packages for
processed meats and cheeses, shrink films, and blister packs.
Table 112 lists 1981 PET consumption by market.
334
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TABLE 110. U.S. POLYETHYLENE TEREPHTHALATE RESIN PRODUCERS
1982 Capacity
Producer and Location Thousand Metric Tons
Akzona, Inc.
American Enka Co. Division
Central, SC 25.0
Lowland, TN 48.2
Allied Corp.
Allied Fibers and Plastics Co.
Moncure, NC 38.6
American Hoechst Corp.
Hoechst Fibers Industrial Division
Spartanburg, SC 261.4
E. I. duPont de Nemours & Co., Inc.
Textile Fibers Department
Old Hickory, TN 250.0
Wilmington, NC 568.2
Eastman Kodak Co.
Eastman Chemical Products, Inc.,
subsidiary
Carolina Eastman Co.
Columbia, SC 204.6
T .nnessee Eastman Co.
Kingsport, TN 238.6
Fiber Induatry, Inc.
Florence, SC
Greenville, SC 681.8
Salisbury, NC
Shelby, NC
The Firestone Tire & Rubber Co.
Firestone Synthetic Fibers Co.
Division
Hopewell, Vh 22.7
ihe Goodyear Tire & Rubber Co.
Chemical Division
Point Pleasant, WV 122.7
(continued)
335
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TASLE 110 (continued)
1982 Capacity
Producer and Location Thousand Metric Tons
IC ! &mertcas Inc.
‘lies Div.sion
Hopevell, VA 36.4
Minnesota Mining and Sanufacturing Co.
Fun and Allied Products DiViSaOfl
De’ atur, AL 25.0
Greenville, SC 10.0
Monsanto Co.
Monsanto Textiles Co.
Decatur, AL 90.9
Rohm and Haas Co.
Carodel Corp., subsidiary
Fayetteville, NC 90.9
TOTAL 2,715.0
Source: Directory of Chemical Producers , 1982.
336
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TAB..E 111. U.S. POLThUTYLENE TEREPHTIIALATE RESIN PRODUCERS
1982 Capacity
Producer and Location Thousand Metric Tons
Celanese Corp.
Celanese Plastics & Specialties Co.
Division
Celanese Engineering Resins Division
Bishop, TX 31.8
GAF Corp.
Chen.cal Product,
Calvert City, KY 4.5
General Electric Co.
Engineered Materials Group
Plastics Business Operat tong
Mount Vernon, IN 59.1
TOTAL 95.4
Source: Directory of Chemical Producers , 1982.
337
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TABLE 112. 1981 CONSUMPTION OF PET
Market Thousaid Metric Tons
Blmv Nolding
Soft drink bottlis 250
Other bottles (ir.cludes cosmetics,
toiletries, pharmaceuticals, foods) 7
Extrusion
Merchant film 13)
Captive film 95
Coating for ovenable board 32
Sheeting for blister pack. 11
Strapping 6
Injection Molding 6
Fibers
Yarn artd Monofilament
Textiles 576
Industrial uses 159
Staple and tow 1,134
TOTAL 2,406
Sources: Chemical Economics Handbook , updated annually, 1981 data.
Modern Plastics , January 1982.
38
-------
In 1981, PBT prnduction totaled 24,000 metric tons. [ 143J PBT has many
uses, including: [ 9J
• Electrical/electronic applications, including connectors,
switches, potentiometers, relays, TV tuner components, high
voltage components, terminal boards, integrated circuit
carriers, motor brush holders, end bells, and housings;
• Automotive applications from large exterior body components to
windshield wiper structures, high—energy ignition caps and
rotors, ignition coil caps, coil bobbins, fuel tnjection
controls, s . nsors, Connectors, window and door hardware,
speedometer frames, and gears;
• Housewares, such as appliance housings for irons and toasters,
handles, gasoline—powered tool housings, food processor
blades, and hair dryer nozzles; and
• Industrial applications, including pump impellors, housings
and support brackets, showerhead and faucet components, paint
brush filaments, nonwoven fabric, irrigation valves and
bodies, and water meter chambers and components.
PROCESS DESCRIPTIONS
In PET resin production, two routes may be used. Dimethyl terephthal—
ate (DMT) and ethylene glycol may be reacted to yield a PET chain and
methdnol, or pure terephthalic acid (TPA) and ethylene glycol may be corn—
bined to form the PET resin and water. Both routes use a two—step esteri—
fication process. In the first step, the prepolymer bis(2—hydroxyethyl)
terepht ialate (BHET) is formed. In the second step, which is the same for
both routes, the BHET monomer is polymerized by polycondensation to produce
PET and ethylene glycol. These ester interchange reactions are shown below.
From DMT — Step 1
c 3 oOC— —COOCH 3 + 2nKOCH 2 C)1 2 0H ta1 t nHOC)i 2 CIt 2 OC _COC14 2 CH 2 0H + 2nCB 3 OH
BRET Methanol
339
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Prom TPA — Step 1
0 0
fl1*O0C—c: 9 -C0OII 4 nH0CH 2 CH OH Catalyst nI1OC1I 2 CH 2 O _ 3_ _OCH 2 CH 2 0H + 251 (20
SHE? Water
Step 2
n1lOCli 2 CH 2 OC_ -C0C1I 2 C1I 2 OH IIO [ CH 2 CH 2 0C_ I_CO}C1I 2 cH 2 0H + ( -L)HOCH 2 CH 2 OH
EG
SHE?
PET Chenistry
In PET resin production, 1,4—butanedjol and DW react to fort, the PBT
chain and methanol. As with PET resin production, PET esterificatton is
also a two—step process, with bis(4-hydroxybutyl) terephthalate as the
precursor. This ester exchange reaction is shown below.
ncH 3 00c_Q...cooc 1( + ZSIIOCH 2 CH 2 CH 2 C1(OH Catalyst 2 ) 4 _OC_(O_ O(CHZ) 4 ..OH + 2ncH 3 oH
—*nHO(CH
Bis(4—hydroxybutyl) terSphtIIA t e Methanol
340
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The condensation of the intermediate yields the polymer and 1,4—butanediol,
as shown below.
HO_(CH 2 ) 4 .(.OOC_. 3_COO(CH 2 ) 4 ). OH + (n—1)HO—(CH 2 ) 4 -OH
PIT 1 .4—butanediol
Tables 113 and 114 list typical input materials and operating parameters for
the PET/PBT process. Other input materials used in this process, including
catalysts, fillers, and stabilizers or color improvers, are listed in Table
115.
PET Production
PET may be produced by either batch or continuous p!oceeses. As illus-
trated in Figure 35, ethylene glycol and a catalyst are mixed prior to being
fed to an ester interchange reactor with either DMTor TPA. Typical process
feeds using either DMT or TPA as monomer are as follows: [ 81J
Material Parts by Weight
Dimethyl Terephthalate (DMT) (monomer) 1,460
Ethylene Glycol (monomer) 1,240
Catalyst 1
Additives 0.3—3
Terephthalic Acid (TPA) (monomer) 1,660
Ethylene Glycol (monomer) 1,240
Catalyst 1
Additives 0.3—3
The most frequently used ester—exchange catalyst is zinc acetate; however,
numerous other catalysts for this polymerization process exist. Stabilizers
and color iinprovers such as triaryl phosphites or phosphates are examples of
additives used in the production of PET.
If DMT is used, methanol is separated overhead from the ref lux stream
in a distillation column. The bottoms stream, containing the partially
reacted DMT/ethylene glycol mixture, is filtered before being fed to the
polycondensation reactors. The excess ethylene glycol, added to facilitate
methanol separation, is removed overhead and recycled to the mixing tank as
the po1 erization reaction proceeds under reduced pressures.
If pure TPA is used, water is separated overhead from the rellux stream
in a dIstillation column. As depicted in Figure 36, the bottoms stream,
which ‘ ontains the partially esteriried ‘PA/ethylene glycol mixture, is
filtered before entering the polycondensation reactors. The excess ethylene
341
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TABLE 113. TYPICAL INPUT !4&TERIALS TO POLYETHYLENE TEREPHTHAI.ATE
AND POLYBUTYLENE TEREPHTHALATE PROCESSING
Ethylene
Resin DMT TPA Glycol 1,4—Butanediol Catalyst
PET X X X X
PBT X X
TABLE 114. TYPICAL OPERATING PARAMETERS FOR POLYETHYLENE TEREPUTHALATE
AND POLYBUTYLENE TEREPHTHALATE PROCESSING
Ester— Poly—
!‘ ter change condensation Polycondensation
Resin Reactor Temp. Reactor Temp. Reaction Pressure
PET or PBT 150 — 210°C 270 — 280°C 67.5 — 135.1
Batchvise Pascals
Continuous 245°C 27 0°Ca 2,030 — 3,380
PET Pascalsa
280 — 285°Cb 67.5 — 135.1
pascalab
apirat stage.
bSecond stage.
Source: Encyclopedia of Polymer Science and Technology .
342
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TABLE L15.
SPECIALTY CHEMICALS USED IN POLYETHYLENE TEREPHTHALATE
AND POLYBUTYLENE TEREPETHALATE PRODUCTION
Function
Catalyst
Stabilizer or Color Improver
Deluster Agent
Thermal and Photoatabilizer
Carboxyl End Group Control
Compour d
antimony complexes
antimony trioxide
bensil
benzophenone
biacetyl
calciu. acetate
:calcium carbonate
calcium oxide
gallium compounds
•.germanium compounds
indium compo’ nds
lead oxide
magnesium acetate
magnesium carbonate
magnesium oxide
manganese acetate
manganese carbonate
manganese oxide
tetramethylguanidine
thallium compounds
titanium complexes
zInc acetate
zinc carbonate
zinc oxide
‘i
tz iary1 phosphates
phoaphites
•pzides
Pyrocarbonatea
Source: Encyclopedia of Polymer Science and Technology .
diazomethane
343
-------
Ethylene
Clycol,
Catalyst
To Pli thanol
Recovery
Glycol
Figure 35. PET production process using DMT.
Sources: Encyclopedia of Polymer Science and Technology.
Uydroc.arboo Processing , November 1979 and 1981.
,PET
Fiber
-------
Figure 36.
Sources: Encyclopedia of Polymer Science and Technology.
Hydrocarbon .roce!sin, November 1979 ar d 1981.
Water i ,
Wastew ter
Trejtmeiit
4 - )
4-,
TM
Ethylene Clycol
PET
Chipi
PET production process using TPA.
-------
glycol used to promote water separation is removed overhead and recycled to
the mixing tank. The polymerization reaction takes place under reduced
pressures to a .d in ethylene glycol removal and to shift the reaction
equilibrium to the polymer side.
The PET resin is then either extruded or fed directly to fiber spinner—
ettes when the reaction is completed. The excess ethylene glycol used
speeds up the reaction rate. Residual-acetaldehyde levels of less than 2.5
porn are desired in bottle resins since acetaldehyde adversely effects
beverage taste and resifl color. [ 122J
PIT Production
PIT production is very similar to the process used to manufacture PET.
As illustrated in Figure 37, 1,4—butanedjol and a catalyst are combined in a
mixing tank prior to entering the ester interchange reactor. DMT is then
fed to the reactor to start the esterification. Methanol La separated from
the overhead stream in a distillation column while the bottoms stream,
containing the partially esterifiej DMT/1,4—butanedjo l mixture, is fed to
the polycondensatjop reactors. Excess 1,4—butanedjol, used to facilitate
methanol separation, is removed and recycled to the mixing tank. The PIT
mass is then extruded into PIT chips. The excess l,4—butanedio l used makes
very high conversions possible for this process. £ shown below, the recipe
for PIT is very similar to that for PET (81]:
Material Parts by Veight
Dimethyl Terephthalate (DMT) (monomer) 1,460
1,4—Butanedjol (monomer) 1,800
Catalyst 1
Additives 0.3—3
Energy Requirements
No data listing the energy required for these processes were found in
the literatur, consulted.
IRONMENTAL AND INDUSTRIAL HEALTh CONSIDERATIONS
PET and PIT are considered to be nontozic compounds. PET has bee’i used
as a food film wrap for over 20 years; therefore, any toxic affect would
impact the use of this resin in th. food and housewares industries. Simi-
larly, FIT is used in many appliances and a toxic effect would alto alter
its usage.
Both PET and PIT processes achieve high conversion of rev materials due
t, the excess polyhydric alcohol used. This high conversion indicates that
sour..ee upstream of and including the ester interchange reactor contribute
significantly more to the total VOC emissions than the sources downstrea, of
the reactor. The polycondensatjon reactors are operated at reduced
pressures, making them unlikely sources of VOC emisskns.
346
-------
Figure 37. PBT production process.
Source: cyc1opedia of Po1y er Science and Technology .
I - )
.1
— PIT
C l i Ipi’
-------
Worker Distribution and Emissions Release Points
Worker distribution estimates for PET and PET ?rOduction viii vary
because each can be made via either a continuous or batch process. We have
estimated worker distributiun by correlating major equipment manhour
requirements with the process flow diagrams shown in Figures 35 through 37.
An estimate of 1.0 vorker/unjt/8—hour shift has been used for batch reactors
and mixers; a factor of 0.5 vorker/unjt/8—hour shift has been used for con—
tinuouø reactors and mixers. Estimates are shown in Table 116.
Principal sources of employee exposure are the fugitive emission
sources listed in Table 119 and ether fugitive emissions from leaks in pump
and compressor seals, valves and drains. Health effects information for
process additives of particular concern due to their potential carcinogenic—
ity or mutagenicity are discussed below. Available toxicity data for other
major input materials is summarized in Table 10 md discussed in IPPEU
Chapter lOb.
Emission ranges from which potential for employee exposure to volatile
organic compounds estimated are shown in Tables 117 and 1J8 for PET produc-
tion from TPA and DIfT, respectively.
Health Effects
Relatively little health effects data exist for the input matertale to
polyethylene terephthalate and polybutylene terephthalate production. Two
subetanceB, however, have tested posltive in animal tests for carcinogenic—
ity and are therefore potential human carcinogens. They are antimony oxide,
a catalyst, an diazomethane, which is uled for carboxy end group control.
The catalyst lead oxide is also a potential health risk due to its high
toxicity and tumorigenic and motagenic potential. The reported health
effects of exposure to these three substances are summarized below.
Antimony Oxiie is a suspected carcinogen (5J which has al*o produced
positive results in tests for mutagenic effects. [ 155J Animal testing of
this substance is limited, however, and no epidemiological data exist.
Diazomethane has produced positive results in animal tests for carcino—
genicity.(1oLJ It is also highly toxic by inhalation following acute or
chronic exposure. [ 242J Inhalation of diazoisethane by man, depending on
degree of exposure, has caused chest pains, asthmatic symptoms, cough and
fevu, fulminating pneumonia, moderate cyanosis, shock, and death.(lOlJ The
OSRA air standard is 0.2 ppm (8 hour TWA).(67J
Lead Oxide exhibits tumorigenic and mutagenic potential in animal
tests, but carcinogenesig tcst have produced indefinite results.(99j In
addition, lead poisoning can occur through ingestion or inhalation of lead
oxide dust. The monoxide of lead is more toxic even than metallic lead or
other less soluble compounds.(88J The OSHA air standard is 50 ug (Pb)/m 3
(8 hour TWA).
348
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TABLE 116. WORKER DISTRIBUTION ESTIMATES FOR SATURATED POLYESTER
RESIN PRODUCTION
Process Unit Workers/Unit/8—hour Shift
Polyethylene 3atch or Continuous Reactor 1.0 or 0.5
Terephthalate Batch or Continuous Mixer 1.0 or 0.5
(DMT and TPA) Distillation Column 0.25
Vacuum Filter 0.25
Extruder 1.0
Spinerette 0.5
Polybutylene Batch or Continuous Reactor 1.0 r 0.5
Terephtha late Batch or Continuous Mixer 1.0 or 0.5
Distillation Column 0.25
Vacuum Filter 0.25
Extruder 1.0
349
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TABLE 117. cHARACTERISTICS 01, VENT STREAJIS FROM ThE FOLY(ETHYLENE TEREPHTUALATE) TPA PROCESSa
_____ kg VOC/I4g Temperature Pre. ,,jre Cuepu o,
Strusa Name Nature _ pruJui.t — _______ Wt.2
IMP Mathanul FV overy Estetlfj f Ve 0 IC Ctjo, a 0.04 38 * i m. VOC
H 2 0
P 1 IthyLeo glycol Polymurlier Se...tors Coot nuu. ,e 0.2 VOC
ro, o v Cooling Water Tower Air
— with spent
•thyleii, glycul
spray C0fld5flg
- Without spe.u 9 . 5e
ethylene glycol
spray coUdene.,
Total Imitijon fts .
— with IC spray 0.3
0 Onds nmer
— without ic 9. 5
condenser
lourc. of tntormu o, Industry correapo 0 g , , 5
biMp — raw material preparetlon; Pt — polymerj.a jo, reaction.
CTh. potential e.l,.Loa. fm. this utrea. ar, sent to reactor cooling dat.r tower when the spray conden .e Is not
used.
upon 0.02 kg VOC/Ng proáici fro, recovery equIpasn and 0.295 kg VOC/Ng product fro, cooling water tower.
•EnC nde. potential emissions from Stre . , A. The actual emission rat, will VCC7 depending upon the number of
polymurilatlon reactor, per line at a plant.
Sourc. Polymer Manufacturing Industry - eckirouo lnior ,a:Ion Per Proposed Standards , September 1983.
-------
TABLE ItS. QIARACTERISTICS OF VENT STREAZIS FROM THE POLY(ETMYLENE TEREPiITHALATE) DMT pROCESSa
Proc ...
3 .ctio 1 b Sue. .
4 5 IWihanol recovecy
Eat.. Ion
rat.
kg VOC/Ng
Na .. Nature product
E.i.ilft.r Vent Conti iluOu 0.15
(Neihanol recovery
vent)
Ithyl.o. gIy o) .. - Isly . .rt.er leactors -
Cooling Water Tower ContInuous
• without IC .pray
condenser
Teaperature Pressure Goaposicion.
•c p. 15 ___________
35 0 49 I4.Lhanol
51 NItrogen
2$
0.2 VOC
Air
5 Sovrce of tot or..iton. Industry corr..pond.nce.
— eatartal recovery PR — po ly .erizat ion react ton.
CAa.u . .d aa a (or the total TPA ..t..Ion rate with KG epray condenser.
dEacI tnd to ha the a ... a. lot the TPA proc.... £11 a.ts .ton. (to. cooling water tower. The actual e.is.ion
rate will vary d.p.n iug . poo iii. nuab.r of poly.arizutlon reactor. per line at a plant.
with SC spray:
c. ndenaer
S urc.. Poly..r tianutacturlog Induatry Iackgr und Lnfor.atioii for Propoaed Standard. . SepLeab r 1983.
-------
TABLE 119. SOURCES OF FUGITIVE EMISSIONS FROM POLYETHYLENE TEREPHTHALATE
AND POLYBUTYt.ENE TEREPHTIIAL.ATE MANUFACTURE
Process
Source Constituent PET w/DMT PET w/TPA PBT
Mixing Tank Ethylene Glycol X X
Vent
1,4—Sutanediol X
Reactor Vent Ethylene Clycol X X
k,4—Butanediol X
DMI X X
TPA X
Methanol X X
Water X
Distillation Methanol X X
Colunn Vent
Water X
Ethylene GJyco * *
1,4—Butanedtol *
Extruder Vent PET Em1ssLo is X X X
and Perticu—
lates
*Trace amounts of these compounds are expected due to the high conversion
achieved in the ester interchange reactor.
352
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Air Emissions
The sources of VOC fugitive emissions from these processes are listed
in Table .19 according to process and constituent type. Controls for the
process emissions, which are all vents, include routing the vented stream to
a flare to incinerate the remaining hydrocarbons and routing the vented
stream to blowdown.12851 Fugitive VOC emissions from leaks resL.lting from
vents, flanges, open drains, pumps, and compressors may be controlled by
equipment modification. However, the most effective control may be a
regular inspection and maintenance program.
Sources of fugitive particulates are also listed in Table 119. These
particulates may be collected by venting the stream to a baghouse or
electrostatic precipitator.
Wastewater Sources
The.e are nly two wastewater sources associated with PET production:
water generated during the condensation reaction between TPA and eth:7lene
glycol; and routine cleaning water. The TPA/ethylene glycol route generates
water during reaction which, in turn, contributes to the wastewater load.
How ver, this process also has reduced VOC emissions since the condensation
by—product is water, not methanol.
PB? production has only one wastewater stream: routine cleaning water.
No quantitative data are available on the wastewater streams generated by
these proces ;es.
Solid Wastes I
The solid wastes generated by these processes are mostly PET and PB?.
Solid waste streams include substandard resin which cannot be blended, resin
removed during reactor cleaning, and resin lost during product blending or
due to spillage. If the ethylene glycol is purified before recycle to the
mixing tank, a solid waste stream consisting of solid ethylene glycol and
polyethylene glycol is generated. [ 93J
Environmental Regulation
Effluent limitations guidelines have been set for the PET/PBT industry.
BPT, BAT, and NSPS call for the pH of the effluent to fall between 6.0 and
9.0 (41 Fe”eral Register 32587, 4 August 1976).
New source performance standards (proposed by EPA on 5 January 1981)
for volatile orgauLc carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emer ncy pressure releases, which
should not last more than five days; ar.j
• Leaks (which are defined as VOC emissions greater than 10,000
ppm) must be repaired within 15 days.
353
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The following compounds have been listed as hazardous (46 Pederal
Register 27476, 20 May 1981):
lead acetate — U144
methanol — U154
All disposal of these compounds or PET and PET which contain any residual
amounts of these compounds must comply with the provisions set forth in the
Resource Conservation and Recowery Act (RCRa).
354
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SECTION 16
POLYESTER RESINS (UNSATURATED)
EPA Source Classification Code — Polyprod. General 3 -01-018-02
INTRODUCTION
Unsaturated polyester resins are produced from the condensation reac-
tion of glycols and dibasic acids, one component of which is unsaturated.
These resins exhibit varying degrees of hardness, flexibility, and flexura]
strength based on the ratio of unsaturated to saturated acid, the glycol
used, the crosslinking agent employed, and the concentration and type of
acid used.
Unsaturated polyesters are used in a wide variety of applications
including: marine products; automobile, truck, and bus parts; bathroom com-
ponents and fixtures, general purpose tanks and pipes and corrosion resis-
tant tanks and pipes; electrical generation, transmission, and distribution
pdrts; consuner goods, such as major appliances and parts, recreational
goods, and toys; gel coats; furniture and cultured marble castings; auto
body coatings; and bonding and adhesive resins.(65J
The physical and chemical properties of unsaturated polyester resins
are partially dependent. upon the crosslinking agent used. Table A—18 in
Appendix A lists typical crosslinking agents and the characteristics
imparted. Table A—19 in Appendix A presents typical properties for
unsaturated polyester resins.
One process is used to produce unsaturated polyester resins. The
sequence used for the addition of the raw materials to the reactor deter-
mines the molecular structure of the resin. Unsaturation nay be either
randomly distrtbuted along the polymer chain or concentrated in one area,
for example at either the middle or the ends of the chain.(1641
INDUSTRY DESCRIPTION
The unsaturated polyester resin industry is comprised of 26 producers.
These producers operate at 63 sites in 27 states. Over 20 pecent of the
sites are located In California. The sites located in Ohio, Illinois,
Indiana, and Pennsylvania contribute almost 30 percent of the total. The
remaining plants are distributed through the ‘eat of the states. Table 120
lists the producers of unsaturated polyester resins and piant capacities.
I
Unsaturated polyester resins are used in appliances, business
equipment, construction, consumer goods, corrosion—resistant products,
355
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TABLE 120. U.S. PRODUCERS OF UNSATURATED POLYESTER RESINS
Capacity as of
July 1, 1980
in Thousand
Producer Location Metric Tons
The Alpha Corporation 45
Alpha Resins Division Collierville, TN
Kathleen, FL
Penis, CA
American Cyanamid Co. *
Industrial Chemicals Division Wallingford, Cr
Ashland Oil, Inc. 64
Ashland Chemical Co., subsidiary
Polyester Division Aahtabula, 00
Caluinet City, IL
Los Angeles, CA
Philadelphia, PA
AZS, Corporation 5
AZ Products, Inc. Division Eaton Park, FL
Lancaiter Chemical Corporation Nevark, NJ
Division
Barton Chemical Corporation Chicago, IL *
Beatrice Foods Co. *
Beatrice Chemical Division
Parboil Co. Division Baltimore, ND
Cargill, Inc. 23
Chemical Products Division Carpentersville, IL
Forest Park, CA
Lynwood, CA
Cook Industrial Coatings Co. Detroit, MI 14
Cook Paint and Varnish Co. Atlanta, GA
Bethlehem, PA
Miami, FL
Milpitas, CA
North Kansas City, NO
*A1l of these sources total 9,000 metric tons per year.
(continued)
356
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TABLE 120 (continued)
Capacity as of
July 1, 1980
in Thousand
Producer Location Metric Tons
Eahart Corporation *
USM Corporation, subsidiary
Bostik Division
Eastern aegion Middleton, MA
The P. D. George Co. St. Louis, MO *
Hugh J.—Resins Co. tong Beach, CA *
ICI Americas Inc. 11
Specialty Chemicals Division New Castle, DE
Koppers Co., Inc. 59
Organic Materials Group Bridgeville, PA
Cicero, IL
Redwood City, CA
Richmond, CA
Mob 1 Corporation *
Mobil Oil Corporation
Mobil Chemical Co. Division
Chemical Coatings Division Rochester, PA
The O’Brien Corporation *
The O’BrIen Corporation —
Central Region South Bend, IN
Owens—Corning Fiberglas 54
Corporation
Resins and Coatings Division Anderson, SC
Valparaiso, IN
Phillips Petroleum Co. 45
Interplastic Corporation,
subsidiary
Commercial Resins Division Jackson, MS
Minneapolis, MN
Pryor, 0IC
*A]1 of these sources total 9,000 metric tons per year.
(continued)
357
-------
TABLE 120 (continued)
Capacity as of
July 1, 1980
in Thousand
Producer Location Metric Tons
PPG Industries, Inc. 27
Co - .ings and Resins Division Cir1cvil1 , OH
Sprtngdale, PA
Totrance, CA
Rei:hhold Chemicals, Inc. Azusa, CA 159
Detroit, MI
Elizabeth, NJ
Houston, TX
Jaciis. uville, FL
Morris, IL
South San Francisco, CA
Tacoma, WA
H. H. Robertson Co. 45
Freeman Chemical Corporation,
subsidiary Chatham, VA
Marshall, TX
Saukville, WI
Schenectady Chemicals Inc. Schenectady, NT *
sat Corporation 9
Glidden Coatings & Resins
Division Huron, OH
Reading, PA
San Francisco, CA
The Sherwin—Williams Co. 9
Coatings Group Onklnnd, CA
The Standard Oil Co. (Ohio) 34
Vistron Corporation, subsidiary
Chemicals Department
Filon/Silinar Department Covington, KY
Hawthorne, CA
*Al] of these sources total 9,000 metric tons per year.
(continued)
358
-------
TABLE 120 (continued)
Capacity as of
July 1, 1980
in Thousand
Producer Location Metric Tons
United States Steel Corporation 136
U.S.S. Chemicals Division Bartow, FL
Colton, CA
Jacksonville, A
Linden, NJ
Neville Island, PA
Swanton, Oil
TOTAL 748
*All of these sources total 9,000 metric tons per year.
Sources: Chemical Economics Handbook , updated annually, September 1980
Data.
Directory of Chemical Producers , 1982.
359
-------
electrical equipment, marine products, and the transportation industry,
which is the largest single category.(43J In 1981, unsaturated polyester
resin production totaled 452,000 metric tons. [ 143) Since 1976, the sales of
unsaturated polyester resins have risen from 436,000 metric tons to a peak
of 545,000 metric tons in 1978. Sales declined in 1979 and 1980, but the
1981 production level was 21,000 metric tons above that of 1980. Present
excess production capacity of 296,000 metric tons is suffic Lent to sustain
growth in the near future.
PRODUCTION AND END USE DATA
In 1981, unsaturated polyester resin production totaled 452,000 metric.
tons.(143) These resins have many uses, including:(13, 143, 164)
• Coatings for wire insulation, cast products, and nonshiny furniture
finishes;
• Coatings used to precoat molds or cured moldings;
• Parts for comeercial and pleasu€e boats;
• Construction industry uses, including tub and shower stalls,
sanitary ware, and cultured marble lavatories;
• Corrosion—resistant materials, such as pipe and filler elements for
cooling towers;
• Molded electrical appliances, hand tools, and motor housings;
• Filament wound railway tank cars with a capacity of over 22,000
gallons, gasoline storag. tanks, pipes for the oil industry, and
rocket casings for military use;
• Fishing poles, golf clubs, and I—beams and channels for
construction; and
• Automobile bodies, truck cabs, headlamp mountings, fender exten-
sions, window frames, and hood scoops as well as recreational
vehicle, airplane, camper, and trailer parts.
Table 121 lists unsaturated polyester resin uses while Table 122 presents
markets for ieinforced polyester resins.
PROCESS DESCRIPTION
Unsaturated polyester resins are manufactured from glycols and dibasic
acids or anhydrides, with agents added to provide crosslinking. These
resins are used either with or without reinforcing fillers in the areas of
transportation, marine applications, construction, and electrical equip-
ment. Only one process is used to manufacture unsaturated polyester resins.
Va ious resin properties are achieved by changing the input materials to
this process.
360
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TABLE 121. 1981 CONSUMPTION OF UNSATURATED POLYESTER RESINS
Market Thousand Metric Tons
Reinforced Polyestera
Sheet, Flat and Corrugated 60
AllOther 285
Surface Coatings 7
Export 5
Other (including cultured marble, body
putty, furniture applications, buttons,
etc.) 95
TOTAL 452
ageqin only.
Source: Modern Plastics , January 1982.
361
-------
TABLE 122. 1981 CONSUMPTION OF REINFORCED UNSATURATED POLYESTER RES1N$
Market Thousand Metric Tons
Aircraft/Aerospace (includes all
military, commercial, and private
aircraft) 12
Appliance/Business Equipment 38
Corstruction 138
Consumer (includes motor homes and
recreational vehicles)
Corrosion—Resistant Products 120
Electrical 74
Marine 132
Transportation (includes passenger
cars, trucks, buses, mass transit,
etc.) 139
Other 37
TOTAL 140
aTone include all reinforcements, fillers, etc.
Source: Modern Plastics , January 1982.
362
-------
A typical recipe for unsaturated polyester production follows:(119J
Material Parts by Weight
Phthalic Anhydride (monomer) 43
Maleic Anhydride (monomer) 19
Propylene Clycol (monomer) 38
Styrene (cross—linking agent) io
Unsaturated polyester resins are produced by first opening the dibasic
acid in the presence of a catalyst. The newly generated polyester radical
then reacts with other dibasic acid and gl,col molecules to form the
polyester chain. The crosslinking agent (M) is added to crosalirik the
chains. This series of reactions is shown below:
Initiation
CR—CM Catalyst 0 0
II I I
C C -O—C—CH—C}j—C
000
Propagation
0 0
II a
- H0-CH 2 -CH 2 -OH + -O—C-CH-C}I-C
0 0
I It
—0—C-CH —CH—C-O—CH 2 —CM 2 — + H 2 0
linkin
ORMO
___ iii Iii
—C-C-C-C-o —
U
o 0 011 0
II I I
—R -O—C-R’ -C-O—R-O—C—C-C-C-o—
Tables 123 and 124 list typical input materials and operating parameters for
unsaturated polyester resins.
363
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TABLE 123. INPUT MATERIALS AND SPECIALTY CHEMICALS USED IN
UNSATURATED POLYESTER RESIN PRODUCTION
Function Chemical
Dibasic Acids or Anhydrides adipic acid
azelaic acid
fumaric ecid
glutaric acid
isophthalic acid
teosebacic acid
maleic anhydride
-methyl adipic acid
phthalic anhydride
piselic acid
sebacic acid
succinic acid
terephthalit. acid
Glycols Blsphenol—A
1 , 4 —buLylene glycol
2 3—butylene glycol
cyclohexanedjol
diethylene glycol
dipropylene glycol
ethylene glycol
propylene glycol
triethylene glycol
Croeslinking Agents acrylauuide
t—butyl styrene
chiorostyrene
diallyl fumarate
diallyl phthalate
divinyl bennene
eethyl acrylate
methyl methacrylate
s—methyl styrene
styrene
n—tert butyl acrylamide
1. S—triacrylyl—hexahydro —
s—triazine
triallyl cyanurate
triallyl( isojcyanurate
Vt fly lioluene
(continued)
364
-------
TABLE 123 (continued)
Function Chemical
Viscosity Aids pyrogenic silica
2—vinyl. pyridtne
Polymerization Inhibitors benzaldehyde
p—benzoquinone
choranil
copper
dihydroxydiphenyl naphth’iquinone
2 ,S—diphenyl—p—benzoqu none
ethylenebis(pyridinjum chlorIde)
hydroquinone
hydroquinone monomethyl ether
mono—t—butyl—hydroquinone
nitrites
oxygen
phenyl trimethyl ammonium acetate
phenyl trimethyl ammonium phosphate
picric acid
primary and secondary amines
pvrogallol
sulfur
p—tert—butylcatechol
toluhydroqutnon.
toluquinone
trimethylbenzyl a monium acetate
trimethylbenzyl ammonium bromide
trimethylbenzyl ammonium chloride
Cure Agents 2—2 ‘—azobisiaobutyronitrile
2—t—butylazo 2—cyeno—4-methyl—
pentane
2—t—butylazo—2 ,4—dimethoxy—4—
methylpentarie
2 —(t—butylazo)taobutyronj true
1—cyano—1 (t—butylazo)cyc lohexane
(continued)
365
-------
TABLE 123 (continued)
Function Chemical
Accelerators and Activators aluminum compounds
t—butyl peroxyacetate
cobalt naphthenate
cobalt octoate
cobalt salts
copper compounds
cyclohexano e peroxide
N ,N—dimethylaniline
2 ,5—dimethylhexyl—2 , 5—diperoxyocto—
ate
N, N—dtmethyl—p—toluidine
2 ,5—diperoxybenzoate
iron compounds
lauryl mercaptan
manganese compounds
sulfur compounds
vanadyl acetyla:etone with ketone
peroxides or t—butyl hydroperozide
Catalysts acetal peroxide
benzoyl peroxide
bis(p—bromobenaoyl)peroxid
t—butyl peroxybenzoate
cumene hydroperoxide
cyc lohexanone peroxide
2 ,4—dichiorobenzoyi peroxide
diisobutylene osonide
diisopropylene ozonide
2 ,5—diisethylhexane
2 ,5—dlperoxyoctoate
lauryl(dodecyl )n.ercaptan
lauroyl peroxide
methyl ethyl ketone peroxide
atannous oxalate in conjunction
with eod um acetate or stnc
acetate
eulfuric acid
tetrabutyl titanate
tetrabutyl zirconate
tei.raoctyl titanate
teLraoctyl zircona:e
p—toluenesulfonic acid
(continued)
366
-------
TABLE 123 (continued)
Function Chemical
Cata1ys g (continued) t—butyl benzoyl peroxide
t—butyl perbenzoate
cetyl peroxide
peroxycarbonateg
Color Improvers titanium dioxide
triaryl phosphates
triaryl phosphites
Flame Retardants alkyl phosphates
iJkyl phosphites
antimony oxide
Chioran Th
(2 ,3—dicarboxy—5,8—endomethylene—
S,6,7,8,9,9—hexaehloro—1,2 ,3,4,
4a, S, 8 ,8a—octahydronaphthaiene
anhydride)
chiorendic anhydride (2,3—dicarboxy—
1,4,5,6,7 ,7-hexachlorobicyclo
12.2.LJ—5-heptene anhydrtde)
dibromoneopentylene glycol
d hrom- styr ne
d lchlorostyene
halogen containing compounds
chlorinated paraffin
hydrated aluminum oxide
monocklorostyrene
tetrabromophthalic anhydri’Je
tetrachlorophthaltc anhydride
trichioroethyl phosphate
triethyl phosphate
vinyl phosphorus compound.
zinc borate
Soujrce : jot, 2nd EditIon.
nry p d1a of P’ 1 ’rn r3c,ence and TDchnoiogy .
Modern Plaqtlcs Encyciopedia, 19 —1982.
if, 7
-------
TADLE 124. TYPICAL OPERATING PARAMETERS FOR UNSATURATED POLYESTER
RESIN PRODUCTION
Temperature ! eaction Time
Polymerization 180—220’C 6—20 houra
Crosalinking Agent
Addition 100—150°C
Polymerization of Anhydridea
and Epoxides 95—125°c 38 hours
Post—Polymerization Heating
for Resins from Epoxides 190—230°C 2—5 hour.
Source: Encyclopedia of Chemical Technology , 2nd EdItion.
368
-------
As illustrated in Figure 38, the first step in the production of
unsaturated polyester resins is polymerjzatjon. A catalyst, glycol, and
dibasic acid or anhydride are fed to the reactor along with an Inert gas.
The inert gas provides an oxygen free atmosphere for the reaction since
oxygen is an Inhibitor. During polymerization, the water produced is
removed overhead using a packed distillation column. [ 50J The unreacted
glycol (the b ott o mg stream) is recycled to the reactor. When the reaction
reaches the desired end point, the resin mixture is sent to a mixing tank
where the polymer Is dissolved in the crosalinking agerit.(45J Other
additives, including polys.erizat lon inhibitors, flame retardants, and
pigments, may be added to the mixing tank. The formulated resin Is then
ready for shipping or storage. Cure catalysts are added just prior to the
final use.
One method used to eliminate removing the water generated by the con-
densation of a glycol with a dibasic acid is to substitute an epoxide for
the glycol. In addition to eliminating water removal, this combination of
raw .zaterialg requires shorter reaction times and lower reaction tempera-
tures than other unsaturated polyester resins; however, post—polymer lgatjon
heating is required for this process to achieve sufficient crosslinking.
11641
Energy Regu1remen
No data listing the required energy for unsaturated polyester resin
production were found in the literature consulted.
ENVIRnNMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Unsaturated polyester resins are nontoxic compounds used in the
construction, transportation, and consumer goods Industries. Several of the
chemicals which have been identified as inputs to unsaturated polyester
resin processing have been listed as hazardous under RCRA: acrylamtde,
maleic anhydride, methyl ethyl ketone, methyl ethyl ketone peroxide, methyl
methacryjate, and phth 11c anhydride. Therefore, special haniling of
unsaturated polyPster wastes which contain these compound, is necessary.
Worker Diqtrjbutlon and Emission, Release Points
Worker distribution e ?ima’pg, made by correlating major equipment
manhour reliair,ment, with the process flow diagram In Figure 38, are shown
In Table 12’5 .
No major suit piiint source em1 ,lons are associated with unsaturated
poJye trr resin produjctfon. However, fugitive and process emiqsjon say
contrJhut slgntfirantjy to env’ronmental and/or worker health problems.
The magnitude of the impact is a function of Stream constituents, process
operating parameters, engineering and adminlstrgtiv cr’ntrol,, and
maintenance Drogr ins.
369
-------
Ste,.m
WAlER
FLASH
DIStIL-
LATION
— COLUIO
Inert Cas
p
Cly ol Liquid Crosslinking
POLYMER Agent
Diba.s tc
REACtOR
Catilyst — . l rIoN Other Additives
Inhibitor and
A tJ or
Aithvdrtde
pVen
C MIXING
TANK
Y
Unsaturated
Polyester
Resin
Figure 38. insaturated polyester resin production process.
Sources; Encyclo,.dja of Chesical Technology 2nd Edition.
sUe Research Center, cystic Monograph No. 2, Polyester Handbook , 1977.
-------
TABLE 125. WORICZR DISTRIBUTION ESTIMATES FOR UNSATURATED POLYESTER
RESIN PRODUCTiON
Unit Workers/Unjt/8—hour Shift
Batch Reactor 1.0
Batch Mixer 1.0
Distillation Column 0.25
71
-------
Table 126 shows process sources of fugitive emissions from unsaturated
polyester resin manufacture. Employees also may be exposed to contaminants,
fugitive emissions f roe pump and compressor ceals, valves and drains.
The diversity of input r.aterials used in unsaturated polyester produc-
tion makes a complete discussion of exposure effects beyond the scope of
this document. However, health effects of several compounds of concern are
discussed in the paragraphs which follow. Additinal toxicity data for major
input materials are given in Table 10. Toxicity information for many of the
specialty chemicals used as additives is provided in IPPEU Chapter lOb.
Little data are available in the literature from which employee expo—
s :n potential may be estimated. However, one source gives an emission fac-
tor of 20 g/kg product f r hydrocarbons generated in molding operations.
1286 J
Health Effects
Health effects data have not been published in the available literature
for almost half of the input materials and specialty chemical’. used in
unsaturated polyester production processing. Although the industry uses
many chemicals that hays exhibited tumorigenic potential, only one, the
flame retardant antimony oxide, has been classified as a suspecred carcino-
gen. Several input materials are currently being tested for cercinogenesis
by the National Toxi..ology Program.
Other chemjcalq are considered significant health risks due to high
toxicity, mutagenic potenttal, and/or teratogenic potential. These Include:
maletc anhydride, a dibasic anhydride; tiree crosslinking agente——styrene,
methyl acrylate, and acrylamide; four polymerization inhibitors-—hydro—
quinone, benzoquinone 1 pyrogallol, and ptcric acid; methyl ethyl ketone
peroxide and cumene hydroseroxide, which are used both as cure agents and
catalysts; and N,N—dimethylaniline, an accelerator and activator,
The per graph. which follow provide a brief synopsis of the reported
health effects of exposur’ to these substances.
Acrylamide is a neur tox1n, causing symptoms of ataxia, hypiersoumia,
and vertigo.(1TOj Although the polymer is nontoxie, absorption of
L..rylamtde throug’i skin or dusts is associated with serious neuorologieal
consep en.e ..l87J Animal test data indicate that exposure to acylamide
iibht also cause sutagenic and teratogenic effects. The 0 M air standard
1. 30 ug/m 3 (8 ho’ir NA).(67j
Antimony Oxide is a suspected carcinogen (5J which has also produced
positive rrsults in tests for nutagenie effects.(1SSJ Animal testing of
this ubstgnce is limited, hov ver, and no epldei.iological data exist.
Cunene Hydroperoxfde Is highly toxic after short exposures involving
Ingestion, Inhalatico, or skin absorption of relatively small quantities.
1242J Animal test data indicate that the substance is also a tumorigenc and
372
-------
TABLE 126. SOURCES OF FUGI I’/E EMISSIONS FROM UNSATURATED
POLYFSIEP. RESIN MANUFACTURE
Source Constituent
Conoenser Veit Clycol
Dibasic acid or anhydride
Mixing Tank Vent Croaslinking agent
Ciycol
Dibasic acid or anhydride
p3
-------
a mutagenic agent. Prolonged inhalation of vapors results in headache and
throat irritation, prolonged skin contact with contaminated clothing may
cause irritation and blistering. [ 278J
Hydroguinone nan exhibited potential as a tumorigenic, m-.atagenic, and
teratogenic agent in animal tests.(2333 Carcinogenesja tests have produced
indefinite results, but the substance l currently being tested by the
National Toxicology Program for carcinogenicity. [ 233J Hydroqutnone is also
highly toxic. Fatal human doses have ranged from 5 to 12 grams, although
300 to 500 milligrams have been ingested da1l for 3 to 5 months without ill
effects.I$5j The OSHA air standard is 2 mg/& (8 hour TVA).1671
Maleic Anhydride i highly toxic by ingestion and inhalation (242J and
is a powerful irritant to the skin and e,es.(149J Inhalation can cause
pulr ’onary edema (149J; other effects of exposure include conjuncetvitts,
corneal damage, cough, bronchitis, headache, abdominal pain, nausea, and
vomiting.(2381 Animal data also suggest that nude anhydride is a tumari—
genie agent.(233J The OSIIA air standard ii 0.25 ppm (8 hour TVA).(673
Methyl Acrylate in highly toxic by ingestion, inhalation, and skin
absorption upon a 0 ite exposure to relatively low dosea.(242J The monomer is
very irritating to eyes, skin, and mucous membranes; lethargy and convul-
sions may occur if the vapor is inhaled in high concsetration.( 149J toxic
effects have been observed in humans at a concentration of 75 ppm.152J
Methyl acrylate also produces tumorg in laboratory animals, but sufficient
data do not exist to make a carcinogenic deterisinatjon.1 107; The OSIIA air
st ’ndar 1. 10 ppm (8 hour TWA).167J
Methyl Ethyl Ketone Psroxlde has produced toxic effects iii labora!ory
animals by ingestion and inhalation of relatively low do.es.(233J An oral
dose of 480 mg/kg has affected the gastrolnteatjonu l tract is humans.(I56J
There is some evidence of tumorlgentc potential in the available lLt.ratur.
and the substance is currently being ‘ested tot carcinog.n..i, tPe
National Toxicology Program.(2 3
N,N —D lmethylanhine is highly toxic by ingeotjoi, inhalation, and skin
absorpt!in followiig acute ewposure.1242J It can be absorbed through intact
akin to produce dangerous sethenogiobinenla I8 J, and has been lethal to
humans by Ingestion at a dose of 50 mglkg.(l5oJ N,NDissthylaattjne has
exhibited tunorlger .ic potential in animal testing and i currently being
te.t d or carctiogenste by the National Toxicology Progras4Z33J 08114 ha.
set an air standard of 5 ppm (8 hour NA).( 7J
p—Benzogulnone I. a tumorigenic and a mutageaL agent, but testing ham
produced Indefi Ite results for caaLtnolentciey.(1o5J The mibstance is
currently ‘mndergotig additional tests for carcinogeneqi. by standard
bioassay protocol under the mpons irsh1p of the National tOxicology- Program.
Beneoqulnone Is very toxic; the pr’bable lethal oral dose for hweang is 50
to 500 uig/kg.f85j The )SIIA air standard i. 0.01 ppm (8 hour NA).(67)
314
-------
Picric Acid is extremely toxic; the lethal dose for humans is less than
5 mg/kg.(85J Toxic effects, including headache, vertigo, nausea, vomiting
and diarrhea, yellov coloration of the skin and c njunctiva, gastroenteri—
tie, hemorrhagic nephritis, and acute hepatitis (5J, may result from skin
contact inhalation, or ingestion of the dust of picric acid or its salts.
(278J Bacteria test data also provide evidence of mutagenic potential.(233J
The OSHA standard in air is 100 ug/m 3 (8 hour TWA). [ 67J
Pyrogallol is highly toxic ingestion, inhalation, and skin absorp-
tion upon either acute or chronic exposure.(242J Because of its marked
reducing action, pyrogallol has tremendous affinity for the oxygen in the
blood; most of its toxic effects can be traced directly to its potent reduc-
ing acrion.Il70j Toxic action lnvovles methemolobinemia, hemolysis, and
renal injury. 85J Delayed deaths from uremia have been reported.(85J
Pyrogallol has alsn produced tunorigenic and nsatagenic effects in laboratory
animals. [ 233J
Styrene has been linked with increased rates of chromosomal aberrations
in persons *‘xpoaed in an occupational setting. l07J Animal test data
strongly support epidemiological evidence of its sutagenic potentiaJ. 233J
Styrene also produces tumors and affects reproductive fertility in labora-
tory animals.f233J Toxic effects of exposure to styrene usually involve the
certral nervous system.1233J The OSHA air standard is 100 ppm (8 hour NA)
with a ceiling of 200 ppm.f67J
Air misgio’is
So, vces of fugitive VOC emissions are listed In Table 126. These two
m , b ontroLL d by venting to a flare or biowduvn fur hydrocarbon
removal.I2P’ I Leaks from process equipment and other fugitive emission;
enurces may e best controlled by a routine inspection and maintenance
program.
Wastewater Sources
There are only two sources of vastevater associated with unsaturated
p&,lyester resin production: water from the condensation reaction and rou-
tine cleaning water. The water generated from the condensation reaction Is
the major va;tevater stream. Routine cleaning water contributes a smaller
ano’jnt to the wastewater prod’iced. If the glycol is replaced by an epoxide,
only routine cieanlng water ii generated.
Range. of several parae.eterg f r wactevaters from unsaturated polyester
reelo processing are shown below. Valaes ‘or the vastevater from the pro-
cess described were not dletingulsned by polyester type by EPA for the pur-
pos. of establishing effiupnt limitations for the polyester resin industry.
[ 2 J
375
-------
Polyester Resin Unit/Metric
Wastevater Ton of Unsaturated
Characteristics Polyester Resin
Production 4.5 is 3
BOD 5 3—20kg
COD 6—45kg
TSS 0—12kg
Solid Wastes
The solid wastes generated by this process include substandard product
which cannot be blended and resin lost during routine cleaning and spillage.
These wastes are comprised mainly of polyester resins.
Environmental Regulation
Effluent limitation, guidelines have been set for the polyester resin
Industry. BPT, BAT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, 4 August 1976).
PJev source performance standards (proposed by EPA on 5 January 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressu,e releases, which should not
last more than five days and
• Leaks which are defined as V C emissions (greater than 10,000 ppm)
must be re,ajred within l days.
The following compounds have been listed as hazardous wastes (46
Federal Register 27416, 20 May 1981):
Acrylamide — U007
Maleic anh dride — 11147
Methyl ethyl ketone — 11159
Methyl ethyl ketone peroxide — 11160
Methyl methacrylate — 11162
Phthalic anhydrlde — 11191)
AlL disposal of these eompounds and unsaturated polyester resins which
contain residual, of these compounds (i.e., incured resins) must comply with
the provisions set forth in rho Resource Conservation and Recovery Act
(RCRA).
-------
SECTION 17
POLYETHYLENE — HIGH DENSITY (HDPE)
EPA Source Classification Code — Polyprod General 3—01-018-02
I NTRODUCTI ON
Polyethylene Is a lightweight, flexible, tough, chemical resistant
polymer whic)- exhibits outstanding electrical i.sulatlon properties. These
characteristics ‘omblned with ease of fabrication and low production cost
make polyetnylene suitable for a wide variety of end products used in the
packaging, housewares, construction, communications, and medical
indija tries.
The empirical formula for polyethylene [ —(CH 2 CH 2 ).-J illustrates
the repeating ethylene unit of the polymer. The molecul’r structure of
polyethylene may be highly branche,. o& basically linear depending upon the
polymerization reaction c3ndltiong.
High density polyethylene (HDPF) Is a very ordered linear ntr.u-ture
with little branching. ThIq structure flakes the polymer highly crystalline,
giving HOP?, the following advantages over low aeriatty polyethylene (LOPE):
increased stiffness, tensile strength, hardness, heat and chemical resis-
tance, opacity, and barrier properties. However, the more crystalline
nature of HOPE red icea Impact strength and envtronmen .a1 stress—crack
ree I stance.
This section presents the polymerization processes used to produce
HOPE. Low density polyethylene (LOPE) and linear low ienatty polyethylene
(r.IMPE) are dlqc’,q,ed separately.
T..hle A—20 in Appendix A lists typical properties of hfgh density
polyethylene. HOPE is characterized by a density greater than 0.940
gfem 3 , with the usual density range from O.95 to 0.970 g/cm 3 . Some
HOPE phyqi al propl!rtJPa are determined by the density and the molecular
weight of the polymer. Tables A—21 and A—22 In Appendix A rreqent density
and molecular v. ght dependent properties, respectively, for a range of HOPE
resins. The en use of HOPE also requires some variation in pnysical prop-
erties. Table A-23 in Appendix A lists HOPE properties according to resin
graeia.
Two specialty gr døs of HOPE are produced: high molecular weight HDP!
(uMw—Hrw ) and ultra—high rnnlocujlar weight IIDP (IJHMWPE). HMV—)lDF is con-
sIdered to he oiythu ’iene with a moiecular weight in the range of 200,000
to 7)O,00(); rJIi çijp Is defined by a molecular weight ot greater than 3
377
-------
million. These oolymers have chemical, physical, and electrical properties
very similar to those of HDPE. The differences lie in the unique abrasion
resistance impact strength, and special processing characteristics due to
the higher melt viscosity of these polymern 226J Typical properties of
U}IMWPE are presented in Table A—24 in Appendix A for rcsins made using tvo
different catalysts and for one copolymer resin.
IDPE, due to its crystalline structure, is virtually insoluble in any
solvent at ambient temperature.(l68J Chlorinated hydrocarbons cause smell-
ing of the polymer below 100C; at temperatures above lOOC, HDPE will
dissolve in these solvents. Polar compounds such as water, alcohels, ec Js,
esters, Ice ones, and nitriles have no effect on HDPE. Suitable IIDPE soy—
vents are listed in Table 127.
HDPE copolymers are formed by adding an a—olef in, such u 1—butene,
1—hexene, and propylene to the polymerization reactor. These cmpounds
Increase branching along the HDPE chain and reduce the erystallinity of the
resin.
HOPE can be produced by particle form (slurry) polymerization, sol ition
polymerization, or low pressure ga phase polymerization. Fifty—might
percent of the total United States installed capacity for HOPE uses the
particle form polymerizatton process with a Phillips catalyst. Thirty—two
percent of the capacity ‘s comprised of either solution or particle form
polymerization with a Ziegler catalyst, while the remaining 10 percent
utilizes other processes, including gas phase polymerization.(169J Process
pressures are much lover than those for LOPE and are typcially less than
1.03 x IO Pascals.
UDUSTRY DESCRIPTION
The HOPE industry is made of the 14 major chemical and petrochemical
producers listed In Table 128. These producers have 16 sites; 12 inTezas,
3 In Louisiana, and I in Iowa. The rocess technology used by these plants
Is noted in Table 128. When available, the polymerization techr.oiogy
(particle form or slurry, solution, and gas phase) is also listed.
HOPE is used primarily in consumer related industries including con—
strucilon, packaging, and housevares. Due to the large number of products
manufactured from HOPE, the general trend of the economy and consumer spend-
ing affects the production and sales of HOPE resins. After a production
peak in 1979 of 2,277,000 metrIc tons, 1981 production (2,177,000 metric
tons) remains below the 1919 level bu is still well above the production
level of 1,420,000 metric tons for 1976.165, 143J
The emergence of high efficiency catalysts has resulted in a reduction
of processing steps fcr the three HOPE processes presented. These catalysts
provide luW catalyst concentration. in the recycle stream and the resulting
polymer. Therefore, catal”st deactivation using methanol and catalyst
removal from the polymer (polymer deashing) are eliminated. Simplifying the
process in this manner significantly reduces the amount of VOC emissions due
to methanol addition and catalyst removal.
378
-------
TABLE 127. SUITABLE SOLVENTS FOR HDPE
chiorocyclohezane
chloronaphthalene
decahydronaphthalene
di nethylcycloh xane
dimethylhe taie
methylnaphtha lene
n—hexyl chloride
octane
trich lorobenzene
xylene
Source: Encyclopedia of Chemical Technology , 3rd Edition.
379
-------
TABLE 128. U.S. PR0DU ERS OF HDPE RESINS
January 1, 1982
Capacity 8
houaand
Company Metric Tons Process
Allied Corporation
Fibers and Plastics Co.
Baton Rouge, LA 300 Phillips
American Hoechst Corp.
Plastics Division
Bayport, TX 136 Hoechst
Atlantic Richfield Co.
ARcO Polymers, Inc., subsidiary
Port Arthur, TX 159 Solvay, US!
Chemplex (jointly owned by
American Can Company and Cetty
OiL ,Co.)
Clinton, IA 123 Phillips
Cities Service Co.b
Chemicals and Minerals Group
Petrochemicals Division
Texas City, TX 86 Monsanto
Dow Chemical USAC
Freeport, TX 54 Dc v solution
Plaquemine, LA 150 Dow slurry
E. I. duPont de Ne.ours and Co., Inc.
Polymer Products Department
Orange, TX 105
Victoria, TX 102 DuPont
Gulf Oil Corporationd
Gulf Oil Chemicals Co.
Plastics Division
Orange, TX 191 Phillips,
Union Carbide
Hercules Inc.
Lake Charles, LA 1 N/Ae
N/A — No Available.
(continued)
380
-------
TABLE 128 (continued)
January 1, 1982
Capacitya
Thousand
Company Metric Tons Process
National Petrochenicals Corp.
(jointly owned by National Distillers
and Chemical Corporation and Owens
Illinois, Inc.)
La Porte, TX 284 PhillIps,
Solvay, USI
Phillips Petroleum Co.
Plastics Division
Pasadena, TX 682 Phillips
Sciltex Polymer Corp.
Deer Park, TX 341 Phillips,
Solvay
Standard Oil Co. of Indiana
AMOCO Chemicals Corp., subsidiary
Chocolate Bayou, TX 173 AMOCO Gas
Phase, Solvay,
us!
Union Carbide Corporsttf-n 1
Plastics and Chemicals Division
Seadrift, TX 91 Union Carbide
Gas Phase
TOTAL 2,984
auss Chemicals and Texaco, Inc. have announced plans of a Joint venture to
conStruct an HDPI plant expected to have a capacity of approximately
272,000 metrIc tons per year at La Porte, TX by 1983. Conoco Inc. has
announced plans to build a 19 ,OOO metric tone per year plant by 1983 at
Montagora County near Bay City, Texas. Exxon Corporation is also known to
be Interested in HDPE production although no plant construction is
pending.
bTexas City plant is leased from Monsanto and will be operating until
Cities Service completes the construction of a 204,000 metrIc t i HDPE
plant at Bay City, TX by 1984.
(continued)
381
-------
TABLE 128 (continued)
C additional HDPE plant capacity of 68,000 metric tons per year is being
used for the pruduction of LL.DPE at Freeport.
dCompany has announced debottleneeking plans that viii bring total
capacity to 261,000 metric tons per year by 1982.
eHercules produces Ultra—High Molecular Weight HDPE.
Seadrift capacity is convertable between HDPE and LLDPE and additional
capacity of 181,000 metric tons per year !B being used to produce LLDPE in
1981.
Sources: Chemical.Econoajcg Handbook , updated annually, 1981 Data.
Directory of Chemical Producers , 1982.
382
-------
PRODUCTION AND END USE DATA
HDPE production is one of the largest in the plastic. industry, follov—
ing LDPE and polyvinyl chloride (PVC) in tons produced. In 1981, U.S. RDPE
production totaled 2,111,000 metric tons. The largest HDPE markets include:
11681
• Wire and cable insulation;
• Bottles for liquid detergents, household bleach, and milk;
• Large drums and gas tanks;
• Cogmetic, medicine, and other consumer products bottles;
• Containers including freezer boxes, fish crates, garbage barrels,
fuel tanks, and water storage tanks;
• Pipe for transporting potable water, gas, acids, liquid hydro-
carbons, oils, salt water, and other chemicals and solvents;
• Housewares;
• Toys;
• Institutional seating;
• P!lament for cord, rope, ribbon, yarn, and gauze for surgical tissue
reinforcement; and
• Pijm for boil—in—beg food packaging, hospital begs, heavy—duty
bagging, drum liner., and merchant bags.
Table 129 presents HDPE consumption hy end—use and major markets.
PROCESS DESCRIPTIONS
HDPE resins are manufactured by particle form (slurry), solution, or
gas phase polymerization processes. Particle form polymerization processes
using a Phillips catalyst contribute over half of the HDPE produced. One
third of the U.S. production is manufactured using either particle form or
solution polymerization processes end a Ziegler catalyst. The remaining
HDPE t produced from other methods, including gas phase polymerization.
The’ emergence of high yield catalysts has eliminated the need for
catalyst deactivation and catalyst removal from the polymer, called polymer
de ishIng. The simplification of the HDPE process by removing these steps
also reduces the amount of VOC emissions generated by this process.
HDPE is produced from ethylene using coordination polymerization.
During initiation, ethylene coordinates at the surface of the catalyst.
Propagation occurs by adding monomer in a similar manner. The p, lymeriza—
tion terminates either by monomer transfer or by hydrogenation.
383
-------
TABLE 129. KDPE CONSUMPTION FOR 1982
Market Thouaand Metric Tone
3l Molding
Bottles
Milk 239
Other Food 70
Household Chemical. 272
Pharaiiaceut ical;fCoeaet ice 66
Drums (15 gallon and larger) 27
Fuel tank. (all type.) 9
Tight—Head Pail. 26
Toys 12
Housewares 5
Other Blow Molding 41
TOTAL BLOW MOLDING 761
Extrusion
Coating 17
Film (12 nil and under)
Merchandise Bags 65
Tee—Shirt Sacks 1
Trash Bag. 4
Food Packaging (bage and bo liner.) 22
Dell Paper
Other 32
Pipe
Corrugated 151
Water 28
Gas 24
Other 40
Sheet (over 12 nil) 29
Wire and Cable 41
Other Extrusion 13
TOTAL EXTRUSLON 47$
Injection Molding
Industrial Containers
Dairy Crate. 18
Other Crates, Cases, PaIlets 35
pails 81
(continued)
384
-------
TABLE 129 (continued)
Market Thousand Metric Tons
Injection Molding (Continued)
Consuner Packaging
Milk Bottle Caps 9
Other Caps 16
Dairy Tube 34
Ice—Cream Containers 20
Beverage—Bottle Bases 45
Other F ,od Containers 5
Paint Cans 10
Housewares 68
Toys 29
Other Injection Molding 93
TOTAL INJECTI(,N MOLDING 469
Rotomolding 30
Export 200
Other (Chiefly resoH resin and resin used
for blending and compo’.nding) 233
TOTAL 2,177
Source: Modern Plastics , January 1982.
J8 ,
-------
Initiation
+ Cat alyst — &+Cstalyst—C14 2 —C 2 —g
tion
Catal,st—cH 2 —cH 2 —g + (n—1)CH 2 .cH 2 —
Catalyst_4C0 2 Q1 2 )H_.g
Termination by Monomer Transfer
Catalyst.4cH 2 ajz½a + 2 1Z —
Cataly.t— lI 2 — g 3 + .‘ .( 4cH2—QI2)lJa
Termination by Hydrogenat ion
Catalyst.4CH 2 cg 21 .....g + H2-’Catalyst — H +
C I 34CM 2 I2+I
Tables 1 and 131 list typical input materials and operating parse—
leers for HOPE proc.sses, respectively. Other input materials used in lID?!
production such as catalyst., comonomers, molecular uelght regulating
agents, solvent., diluents, and specialty chemicals (e.g., anti uidsnts, UV
light stabilizers, and crosslinking agents) are li.t.d in Table 132.
Particle Form Polymerigar ion
The particle form (or slurry) polymerigation process is aced to produce
over half of the NOPE in the United Stat.s.(169J This process, depicted in
Figure 39, consists of three major stepss polymerization, polymer separa-
tion, and pelletigation. A typical recipe for HOP! production via particle
form poljuerisation follovs;(8lj
Material Parts byVeight
Ethylene (monomer) i,u23
Hydrogen (molecular weight regulator) is
Macan. (diluent) 1
Chrom um—Ia.e4 Catalyst (1
A 4iluent, typically hecane, is used to feed the chromium owide cata-
lyst suspended on sll’Les gel to the reactor. The ethylene and comonomers
are then continuously fed into the liquId-filled reactor, which may be
either an auto’tav, or a ioop reactor. Agitation is used to facilitate heat
removal, prevent agglomeration of the polymer particles, and circulate the
liquid dil’aent ehrough the loop reactor.
The monomer—polymer slut sy is continuously discharged from the reactor
settling zone and fed Into a flash tank. The diiuent, unreacted ethylene,
386
-------
TABLE 130. TYPICAL INPUT MATERIALS TO HDFE PROCESSES
Solvent or
Process Monomer Catalyst Diluent Comonomer
larticle Foris X X X X
Solution x X X X
Gas—Phase x X
TABLE 131. TYPICAL OPERAT1.C PARAMEER$ FOR HDPE PROCESSES
? rocegs Tewpera:.ure Pressure Reaction Time
Particle Form 7 0-l [ O .C 0.5—3 x 106 Pa 1 — 4 hours
Solution 150—250c 2—4 106 Pa eeveral minutes
Ga Phase 70-110C 2—3 106 Pa
N 0 reaction ti ies were given in the 11ter ture; however, several passes
are necessary to actieve the desired conversion.
Sources: Eneyelopedia of Chemical Techn , , 3rd Edition.
Eicyclopedla of Polymer Science and Technology.
Modern Plastics Encyclopedia , l 81—l982.
387
-------
TABLE 132. INPUT ?tA ERIALS AND SPECIA .TY CHEMLCAL5 FOR
HDPE PROCFSSE$ IN ADDITION TO MONOMER
Function Compo nd Process
Solvent cyclohexar.e solution
Diluent butane oarticle tons
hexane
I sobutane
iaopentane
Cata yst
Phillips chromium (VI) oxide particle form
supported on silica solution
or si1I. a—alunjna gel gas phase
Ziegler transition metal particle form
coupled vith an alkvl solution
metal compound gas phase
Stan ard Oil of moly idena (MoO 3 ) particle for.
Indiana (MO’ O supported on an solution
alumina gel
Motetular Weight
Regulator hydro en particle form
Cononotnera 1—hutene particle form
1—hexene solution
1—octene gas phase
propylene
Ant loxidants hindered phenols particle for.
phosphates solution
stearat g gas phase
UV Light benzophenone s particle fcrm
Stabilizers carbon black solution
gas phase
Cro slinking benzoyl peroxide particle form
Agents dicumyl peroxide solution
gas phase
Sources: ! nr.yclopedla of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and
Modern Plaatics Encyclopedtu , 1981—198
388
-------
Figure 39. Particle form polymerization process.
Source: Encyclopedia of Cheelc l Technology , 3rd Edition.
‘0
anJ
Comenume t
Vent
S I I REEl)
A’!TUCLAVE
O h
LOOP
REACTOR
Pellets
-------
and comononer are returned to the reactor white the. polyethylene particles
are dried and pelletized before bagging.
HMW—HDPE and UHM’4PE are manufactured using this process when a molec-
ular weight inhibitor is not ii’troduced. The average molecular weight of
polyethylene from this process ranges from 250,000 to greater than
Solution Polymerization
Solution polymerization is used for the pr9ducLion of homogeneous
polym.rs of comparitively low molecular weight for injection molding and
film extrusion. These polymers are more readily 4issalved in hydrocarbons;
in c ntra t to particle form polymerization, the HDPE produced by the
qolu..ion process does not precipitate out of solution.
As depicted in Figure 40, ethylene and a comonomer (such as 1—hexene)
are dissolved in the solvent and fed to the polymerization reactor. A high
e.flcieney Latalyst is fed separatel, into the reactor and the polymeriza-
tion reaction is completed in several minutes. Information on a typical
recipe for producing HOPE via solution polymerizetion was not found in the
literature. The maximum polymer conversion is 35 to 40 percent; conversion
Is typIcally 18 to 25 percent in order to retain the polymer in solution.
The high polymer pro.uction per kilogram of catalyst eliminates the need for
the catalyst removal. The unreacted ethylene and solvent are removed in a
flash tar.k and recyrled to the reactor while the resulting polymer is dried
a d extruded Into pellet,.
Gas Phase Polymerizat ion
A low pressure gas phase polymerization process is used to produce both
LLDPE and HOPE. The density of the HDPE product from this process ranges
from 0.940 to0.970 *1cm 3 , and the process ii capable of producing
polymers with densities In the range of 0.915 to 0.970 g/cm 3 .f168J
As departed in Figure 61, ethylene, comonom.r, and a catalyst are fed
to a fluidtzed bed reactor. Typical input to the reactor is as follove
118’,, 181J
Material Parts by Weight
Ethylene (monomer) 1,010
Hydrogen (molecular weight regulator) 4
Comonomer 20
Chromium—Based Catalyst <1
Unreacted gasen are recycled using a single—stage centrifugal compressor and
are cooled in a heit exchanger before reentering the reactor. The granular
polymer Is discharged from the r actor Intermittently. Nigh catalyst conver-
sion in the reactor eliminates the need for catalyst removal. Unreactid
gases are separated and returned to the reacior and a nitrogen purge Is used
to remove any remni.iing hydrocarbons. This process, which requires no
390
-------
Vent
Figure 40. Solution polymertiation roceas.
Source: Ency lopedta of Chemical Technology , 3rd Edition.
Vent
ST IKRED
AUrOCl.AVE
Og
LOOP
REACIOR
Vent
Pellets
-------
Figure 41. Low pressure gas phase polymerization.
Source: Hydrocarbon Processing , November1979.
I . . )
YLULDIZgi
BED
N 2 Puige
Vent
TANK
Granular
NDPE
Product
-------
solvent stripping or pelletizing, results in lover capital and operating
costs when compared to particle form and solution polymerization.
Energy Requirements
The following data were !ound in the literature and listed according to
the technologies designed below: [ 185, 186, 187J
Unit/Metric Ton
Technolo 1 Energy R qu red of Product
Chemiache Werke
Huels AG Electricity 1.58 x j 9 Joules
Hoechst AG Electrf:ity 3.46 x i 9 Joules
Naphthachimje Electricity 7.56 x 108 Joules
Steam 0.3 metric tons
ENVIR0NMENT AND INDUSTRIAL HEALTh CONSIDERATIONS
HDPE, considered to be a non oxic compound, is used in the packaging
and nedicsl industries as well as for pipe which transports potable water.
These products affect a large percentage of the population and any toxic
effect would have a significant impact on this industry.
High efficiency catalysts have eliminated the need for catalyst
deactivation using methanol and polymer deashing. This simplification in
processing also eliminates fugitive VOC emissions which are the result of
methanol addition and the deashing step.
Worker Distribution and Emissions Release Points
Worker distribution estimates have been made for HDPE production via
the three processes discussed previously. The estimates, shown in Table
133, were developed by correlating major equipment manhour requirements with
the process flow diagrams in Figures 39 through 41.
No major air emission point sources are associated with the HDPE
processes. However, fugitive emissions from such sources as reactor vents,
storage tanks, polymer driers, and pelletizing extruder vents may pose
significant environmental and/or worker health problems based on the
constituents present in the stream, operating parameters for the process,
engineering and administrative controls used, and maintenance programs.
Table 134 shows the principal process sources of fugitive emissions
from HDPE manufacture. Ethylene, ethane, and several other possible input
materials listed in Table 132 (hydrogen, butane, propylene), are simple
asphyxiants, whici pose a potential hazard because their presence limits the
amount of oxygen available in the atmosphere. The nitrogen used to purge
granular HDPE of residual hydrocarbon is also a simple asphyxiant.
393
-------
TABLE 133. WORKER DISTRIBUTION ESTIMATES FOR HDPE PRODUCTION
Process Unit Workerg/Unjt/8—hour Shift
Particle Form Polymerization Storage 0.5
Reactor 0.5
Flash Tank 0.125
Dryer 0.5
Extruder 1.0
Solution Polymerization Storage 0.5
Conti ou ReActor 0.5
Flash Tank 0.125
Dryer 0.5
Extruder 1.0
Gas Phase Polymerization Heat Exchanger 0.125
Compressor 045
Continuous Reactor o.s
Storage Tank 0.125
394
-------
TABLE 134. SOURCES OF FUGITIVE EMISSIONS FROM HDPE MANUFACTURE
Process
Particle Gas
Source Constituent Form Solution Phase
Reactor Vents Ethylene X x x
Ethane X X X
Solvent X X
Flash Tank Vent Ethylene X X X
Ethane X X
Solvent X X
Mixing Tank Vent Ethylene X
Solvent X
Polymer Drying Ethylene and Poly—
Vent ethylene Particu—
latea and Emissions x x
Pelletizing Ethylene and Poly—
Extruder Vent ethylene Particu—
latee and Emissions X
Compressor Vent Ethylene X
Ethane X
Discharge Tank Ethylene X
Ethane
3 9 ,
-------
Solvents and diluents used in HDPE productjor are central nervous aye—
ten depressants. Overexposure may result in dizziness, headache, nausea,
and narcosis.
Particulate emissions from drying and pelletizing 3perations may con—
si t of polymer fines (nuisance dust) and specific additives which may be
hazardoun in themselves.
Available toxicity and standards tnformation about contaminants poten—
tiallv associated with HDPE production is summarized in Table 10. IPPEU
Chapter lOb contains more detailed information regarding additives to the
process.
Emission ranges from which potential for employee exposures to volatile
organic compounds may be estimace are shown in Tables 135 through 137 for
the particle form, solution, and gas phase processes, respectively.
Health Effects
Animal test data indicate that several input materials and specialty
chemicals for HDPE processes are tumortgenic agents; however, only one, the
catalyst chromium (VI) oxide, presents solid evidence of careinogenicity.
Others, including benzoyl peroxide, a croaslinking agent, and hexane, a
diluent, exhibit teratogenle properties. In addition, the solvent cyclo—
hexane has produced imitations in laboratory animals.
Chromium (VI) Oxide has produced positive results in animal tests for
carcinogenicity (l 9J and there is e tenelve evidence of its mutagenic
properties. Teratogenic effects have also been observed in laboratory
animals. Chr ntc industrial exposures hiv led to severe liver damage and
central nervous system involvement in humans; allergic reactions are com—
mon.L85j The American Conference of Governmental Industrial Hygienists
(ACGIH) as recunmended a Threshold Limit Value (TLV) of 0.05 mg/ti 3 (S
hour TWA). The OSHA air standard 1. 0.3 mg/u 3 (8 hour NA).
Air Emissions
Sources of fugitive VOC emissions from HDPE processing are summarized
in Table 136 by process and constituent type. The major portion of the
fugttive VOC emlssione from HDPE processing originates in the polymerization
section, which includes ethylene recycle and recospression. Polymerization
bl CtlOn VOC emission, fro, vents are reported to contain 20 kg ethylene, I
kg ethane, anJ 22 kg solvent, if used, per ton of HDPEprodueed.1931 VOC
leak rates from .alves and flanges are reported as 0.018 and 0.021 kg per
hour per source, respectively, for liquids and 0.0059 and 0.0022 kg per hour
per source, respectively, for gas serviee. [ 287J Control technologies for
vents Include venting the stream to a flare to incinerate any hydrocarbons
and/or venting to blovdovn.(285j Controls for valves, £ 1. iges, and other
leak include equipment modification and a routine maintenance and inspection
program.
396
-------
TABLE 135. CHARACTERISTICS OF VENT STREAMS FROM THE HIGH DENSITY
POLYETHYLENE LIQUID PHASE PARTICLE FORM PROCESS
Emission
rate,
Stream kg VOC/Mg Composition,
Nam Nature product Wt.Z
Feed preparation Intermittent 0.2 100.0 Ethylene
Dryer nitrogen blower Continuous 0.06—0.4 0.3 Isobutane
99.7 Nitrogen
Contir.uous mixer Continuous 0.006 0.6 Isobutane
99.4 Nitrogen
Recycle treaters Continuous 12.7 61.0 Ethylene
18.0 Isobutane
20.0 Ethane
1.0 Hydrogen
Total Emission Rate 13.0—13.3
Source: Polymer Manufacturing Industry Background Information for Proposed
Standards , September 1983.
397
-------
TABLE 136. QIARACTERISTICS OF VENT STREAMS FROM THE HIGH DENSITY
POLTETHYI2HE LIQUID PEASE SOLUTION PROCESS
E mi sio
rate,
Stream kg VOC/Mg Composfti ,
Nams Nature
Tank vents Continuous; 0024
C7 Cl. i
Cy loh i e treatet vents Intermittent (to flare) —
Catalyst preparation YSflt Generally (to flare)
continuous
Continuous and (to flare)
intermittent
Reactor vents Generally (to flare)
intermit tent
Separation v n s So.. coatinnous (to flare)
and intermittent
Recycl, ethylene treaters Continuous 1217 61.0 .t:,l.ou
1.0 hydrogen
18.0 isobutal
20.0 ethane
Recovery dtsti l l ,tio. Continuous and (to flare)
intermittent
Extruder vents Continuous 0.63 VOCI — 0.03
steon and air —
9, • 93
Stripper vents Continuous o.ss voca — o.oi
air — 99.99
All indicated strea 14.8 V Cb
to flare air
Total Emission Rate 2 .o
‘CycIohp g ,.
bincludes ethylene, cycloh.,in ,, end other voc com000mers. IthyleLS is
emitted at about 4.33 kg VOC/Pig product; cyc1ohe at about 8.7 kg VOC/pqg
product; end other voc at about 1.74 kg VOC/Pig product.
Source: y er Manufacturing Industryplckgroufld Information for Proposed
Standards, September 1981 . —___________________________________
398
-------
TABLE 137. QIARACTERISTICS OF VENT STREAIIS FROM THE HIGH DENSITY
POLYETHYLENE GAS PHASE PROCESS
Emission
rate,
Stream kg VOC/Mg Composition,
Name Nature product Wt.Z
Raw materials Interaijttent 0.04 0.5 VOC
purification vent 99.5 112
Catalyst additive vent Intermittent 0.01 35 VOC
65 112
Comonomer purification Continuous 0.10 92 VOC
vent 8 112
Catalyst dehydrator Intermittent 0.004 2 VOC
handling vent 98 Air
Vacuum pump vent Intermittent 0.03 41 VOC
59 112
Recovery vessel vent Intermittent 0.06 46 VOC
54 Air
Emergency reactor Intermittent 0.05 83 VOC
blowdovn vent 17 N 2
Reactor purge vent Intermittent o.ii 1-83 VOC
99—17 112
Product discharge vent Continuous - 22.3 35 VOC
65 112
Bin vent Continuous 0.05 0.02 VOC
99.98 Air
Coiipres,or seal (oil) Continuous 0.01 50 VOC
vent 50 112
ia1yzer vents Continuous o.oi 100 voc
Total Emission Rate 23.37
3o-irce: Polymer Manufacturing Industry ackground Information for Propo .d
Standards , September 1983.
399
-------
Sources of fugitive particulates ar also lidted in Table 134. Fugi-
tive par:L l , may be collected by venting these streams to a baghouse or
an electrostatic precipitator. According iv EPA e t1 a ea, the population
exposed to HDPE emissions in a 100 lie 2 area surrounding an HDPE plant is:
21 persons exposed to hydrocarbon, and 2 persona exposed to particulates.
(286J
hastewater Sources
PC roce eeg gonar.P, only roueine cleaning water. Several waste—
water parameters from HDPE pocesses, shown below, are reported by EPA.
These parameters were not separated according to process type for the
purpose of establishing effluent limitations for the HDP! iodustry.(284J
Wastewater Unit/Metric
- Characteristic Ton of NDPE
Production 0 — 30.87 i 3
SOD 5 0—1kg
COD 0—2.4kg
TSS 0—3.4kg
The control treatment technologies common to HDPE facilities are: screening,
chem t cal treatment, and aeration. This. vastevater treatment system ha. been
shown to effectively treat HDPE wastevatere.12 541
Solid Waste
The solid wastes generated during IIDPE production include substandard
polymer which cannot be salvaged by blending and low—molecular weight poly-
ethylene waxes. The high efficiency catalysts hav, all but eliminated wax
próduction.(l683 Thise wastes are not hazardous; therefore, their disposal
should’ aot pose an environmental problem.
Environmentai Regulation
Effluent limitations guidelines have been set for the polyethylene
industry. Bfl, BAT, and NSPS call for the p 11 of the •?flusnt to fell
between 6.0 and 9.0 (41 Fe ’eral Register 32587, August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions includsi
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which sho ld not
last more than five days; and
• Leaks (which are defined as VOC emissions greeter than 10,000 ppm)
muSt be repaired with 15 days.
None of the input materials used in this process have been listed as
hazardous (45 Federal Register 3312, Play 19, 1980).
400
-------
S! CTTON 18
POLYETHYLENE - LINEAR LOW DENSITY (LLDPE)
EPA Source Classification Code — Polyprod. Ceneral 3-01-018-02
INTRODUCTION
Polyethylene is a lightweight, flexible, tough, chemical resistant
polymer which exhibits outstanding electrical insulation properties. These
rharacteristics combined with ease of fabrication and low production cost
makes polyethylene suitable f r a wide variety of end products used in the
packaging, housewares, construction, communications, and medical
industries.
The empirical formula for polyethylene F-4CH2CH2 -—J illustrates the
repeating ethylene unit for the polymer. The molecular structu..’e of poly-
ethylene may be highly branched or basically linear depending upon the
polymerization reaction conditioi s.
Linear low density polyethylene (LL1 PE) has a linear structure with
short side chains. These short side chains keep the polymer chain from
forming a highly crystalline Structure like high density polyethylene
(HOPE). Short chain branching gives LLDPE the ol1owing advantage, over low
,den ity polyethylene (LDPE): higher melting point, higher tensile strength,
higher flexural modulus, better elongation, and better environmental stress
crack resistance. This section presents the polymerization processes used
to produce LLDPE. Low density polyethylene (LDPE) and high density poly-
ethylene (HDPE) are discussed separately.
Table A—25 in Appendix A compares typical properties of LLDPE and LDPE
resin;. The LLDPE resins display higher viscositie, at the same density due
to increased crystallinity and the absence of long chain branching;1168J
therefore, in order to use the same processing equipment as was used for
LDPE, an LLDPE resin “ith a sufficiently high melt index must be selected.
Comonomera are added to the ethylene to control chain branching. Typi-
cally. 1—butene is used; however, 4 —methyl—1—pentene, 1—hexene, and l—octene
are also used. The type of catalyst used determines which comonomer is
selectel since various catalysts d!.play differing copolymerization activi—
ties.(147J
LLDPE Is produced by particle form (slurry) po’ymerizatton, aolution
polynerization, or 1ev pressure gas phase polymerization. Process pressure,
are much lower than those used f’r LDPE production, typically less than 1.03
x Pascaig. Low preLsure gas pha’ polyae izatjon require. iio solvent
401
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strippii g which results in lower capital and operating costs than slurry Ot
solution polymerization.
INDUSTRY DESCRIPTION
The LLDPE industry is presently ‘sade up of two commercial resin pro-
ducers: Dow Chemical, Preeport, Texas and Union Carbide, Seadrift, Texas.
(35J Although the present LLDI’E production of 451,000 metric tons is
relatively small when compared to LDPE production, LLDPE is expected to
replace 70 percent of the LDPE resin and 20 percent of the HDPE resin
markets in the next LC years.(35, 38J
PRODUCTION AND END USE DATA
L.LDPE production is relatively small whet. competed to LDPE product ion.
As shown below, 363,700 metric tons were produced by Dow and Unicn Carbide
in 1980.1351
1980 Product Ion
Producer Thousand Metric Ton .
D c v 136,400
Union Carbide 227 300
Total 363,700
LLDPE markets and uses include; (41J
• Injection molded parts, including housewares, closure., and lids;
• 3low molded part., including toys, bottle•, and drum liner.;
• Extruded vire and cable insulation;
• Extruded pipe and tubing;
• Extruded film used in fond packaging applications, including ice
bags, retail merchandise bags, and produce bags; and
• Extruded film used in nonfood application., including tras1 bags,
industrial liner., and garment begs.
Table 138 list, end—use. for LLDPE resins in 1981.
PROCESS DESCRIPTIONS
LLDPE resins are manufactured by particle form (slurry), solution, or
gas p iase polymerization processes. There is no definitive information on
the pro es. used by Dow. Union Ca& bide uses a low pre s irq gas phase
process to manufacture .DPE. El Paso Polyolefins has built a demonstration
unit in Odessa, Texas whli uses the particle form process to manufacture
LLDPE. 38J
402
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TABLE 138. LLDPE CONSUMPTION BY END—USE FOR l981
End—Use Thousand Metric Tons
Blow Molding 1
Ext rus ion
FUn (12 mu and under) 266
Pipe and Conduit
Sheet and Profile 2
WIre and CAble 42
In eL 1on MoldIng 40
Rotomolding 20
Export 23
Other (blaisdin resin and resold resIn) 27
TOTAL 451
aTonnage in this table is broken out from tonnige in the LD E section,
Table 147.
bNote discrepancy with pipe figures in LDPE Table 141.
Source: Mooern Plastics , Janu iry 1982.
403
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The emergence of high yield catalysts for the three LLDPE processes
presented has eliminated tie need for catalyst deactivation and catalyst
removal from the polymer, called polymer deashing. The simplification of
the LLDPE process by r. moving these step. also reduces the amount of
fugitive VOC erniastonp generated by this process.
LLDPE is,polym rized f roe ethylene using a catalyst vith what can be
desccj bed as an anionic polymerization mechanism. During initiation,
cthylene ia added to ‘an organometal ljc active center, depicted as ,f’R.
Propagation occurs by adding other ethylene molecules at the active organo-
metallic center.
Initiation
2 2f 4 CH 2 —CH 2 --R
Propa&. a
+ 22øPf 2-Q 2 Cg 2 3,,R
The polymerization c n be terminated by several mechanisms. Monomer trans-
fer produces a polymer molecule conraiming an unsaturated bond, and an alkyl
group on the 5 face of the catalyst. A hyd?tdc ion may be transferred,
coupled vith reàikylation of the catalyst. Finally, a transfer reaction may
occur bet been an active polymer chain and a metal alkyl.
Termination by Monomer transf
W’.CRZH 2 H 2 _CH 2 P, R + _________
?f 4 -CH 2 —Cq 3 +
Termination by Rydride Ion Transfer
M -CH 2 CH 2 +Cff 2 4’ M’ -H+CH 2 —CH—4C0 2 C1lz½1
+
Termination by Transfer Reaction
f’—CH 2 —Ca 2 —4cH 2 —Qi 2 $ R + 2 nR ‘2 —
+ R’ ?flCH 2 -CH 2 ..+CH 2 -CH 2 3II, R
Tables 139 and 140 list typical input materials and operating paran—
e erg for LLDPE processes, respectively. Other input materials used in
LLDPE produ’ t ion such as catalysts, comonomers, molecular weight regulatlvg
agents, solvents, diluents, and specialty enemical, (e.g., antioxidant,, UV
light s abl1Lzerg, and crosslinking agents) are listed in Table 141.
404
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TABLE 139. TYPICAL INPUT MATERIALS TO LLDPE PROCESSES
Solvent or
Process Monomer Catalyst Diluent Comon’)mer
Particle Form X X X x
Solution x x X x
Cas—Phage X X X
TABLE 140. TYPICAL OPERATING PARAMETERS FOR LLDPE PROCESSES
Process Temperature Pressure Reaction Time
Particle Form 55—70 °C 1.5—2.9 x 106 Pa 1 — 2 hours
Solution 250°C 8 x 106 Pa several minutes
G P iage 85—95°C 2 x 106 Pa
N 0 reaction t 1 mes were given in the literature; however, conversion ii
appro imate1y 2Z per pass, and several passes are necessary to achieve the
desired conversion.
Sources: Chemlcal ineerin, May 17, 1982.
Encyclopedia of Chemical Technology , 3rd Edition.
EnçycloDedia ot Polymer Science and Technology.
Modern Plastirs Encyclopedia , 1981—1982.
‘.05
-------
TABLE 141. INPUT MATERIALS AND SPECIALTY CHEMICALS FOR
LLDPE PROCESSES IN ADDITION TO MONOMER
Function Compound Process
Solvent cyclohexan , solution
Diluent butane particle form
hexane
I sobutane
isopentane
propaae
Catalyst
Phillips chromium (VI) oxide particle form
supported on silica solution
or silica—a1u j gel gas phase
Ziegler transition metal particle form
coupled with an alkyl solution
metal compound gas phase
Standard 011 of ‘nolybdena (MoO 3 ) particle form
Indiana (AMOCO) supported on an solution
alumina gel
Molecular Weight
Regulator, hydrogen particle form
Cononomerg 1—bLtene particle form
1—hexene solution
1—octene gas phase
propylene
Ant loxidants hindered phenols particle form
phosphates solution
stearates gas phase
UV Light benzophenones particle form
Stabilizers carbon black solution
gas phase
Crogglinking benzoyl peroxide particle form
Agent, dicumyl peroxide solution
gas phase
Sources: Chemical ng1neering , May 17, 1982.
Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopejj!a df Polymer Science and Technology.
Modern Plastics Encyclopedia , 1981—1982.
406
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Particle Form Polymerization
The particle form (or slurry) polymerization process, depicted in
Figure 42, consists of three major steps: polymerization, polymer separa-
tion, and pelletization. A diluent, typically hexane, is used to feed the
chromium oxide catalyst suspended on silica gel to the reactor. The ethy-
lene and comonomers are then continuously fed into the liquid—filled
reactor, which may be either an autoclave or a loop reactor. Agitation is
used u fac 1itate heat removal, prevent agglomeration of the polymer
particles, and circulate the liquid diluent through the loop reactor.
The following is a typical recipe for the production of LLDPE via
particle form polymerizatjon: [ 198 1
Material Parts by Weight
Ethylene and l—Butene (monomer and comonomer) 18,680
Catalyst 1
Hydro ;en (molecular weight regulator)
Butane/Propane (diluent)
The amounts of hydrogen and diluent were not found in the literature;
however, tIley are expected to be on the order of 1 and 2 parts by weight,
respectively.
The monomer—polymer slurry is continuously discharged from the reactor
settling zone and fed into a flash tank. The diluent, unreacted ethylene,
and comonomer are returned to the reactor while the polyethylene particles
are dried and pelletized before bagging.
Solution Polymerization
Solution polymerization is used for the production of homogeneous
polymers of comparitively low molecular weight for injection molding and
film extrusion. These polymers are more readily dissolved in hydrocarbons;
in contrast to particle form polymerization, the LLDPE produced by the solu-
tion process does not precipitate out of solution. Information regarding a
typical production recipe for LLDPE by the solution polymerization process
was not found in the literature.
As depicted in Figure 43, ethylene and a comonomer are dissolved in the
solvent, typically cyclohexane, and fed to the polymerization reactor. A
high efficiency catalyst is fed separately into the rea’tor and the polymer-
ization reaction L completed in several minutes. The maximum polymer
conversion is 35 to 40 percent; conversion is typically 18 to 25 percent in
order to retain the polymer in solution. The high catalyst conversion
eliminates the need for the catalyst removal. The polymer is either used in
solution r the unreacted ethylene and solvent may be removec in a flash
taik and rccycled to the reactor while the resulting polymer is dried and
extruded into pellets.
407
-------
Figure 42. Perticle fore poly.erizatjon procees.
Source: Encyclopedia of Chemical lechnology , 3rd Edition.
0
-------
Figure 43. Solution polymerization process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
0
0
V n
im z t, Sojuit
Pe 1 1.1.
-------
Cas Phase Polymerization
A low pressure gas ph. se polymerization process is used to produce both
LLDPE and HDPE. The density of the LLDPE product from this pro,. ess ranges
from 0.915 to 0.940 g/cm 3 , and the process is capable of producing poly—
mere with densities in the range of 0.915 to 0.970 g/cm 3 • 168J
As depicted in Figure 44, ethylene, comonomer, and a catalyst are fed
to a fluidized bed reactor. Typical input materials and quantities are
given below:1197J
Material Parts by Weight
Ethylene and l-Butene (monomer and com000mer) 1,020
Zieglet Catalyst 1
Hydrogen (molecular weight regulator)
The amount of hydrogen was ‘tot reported, but is expected to approximately
equal that of the catalyst. Unreacted gases are recycled using a single—
stage centrifugal co pressor and are cooled in a heat exchanger before
reentering the reactcl’. The granular polymer is discharged from the reactor
intermittently. High catalyst conversion in the reactc’r eliminates the need
for catalyst removal. Unreacted gases are separated and returned to the
reactor and a nitrogen purge is used to remove any remaining hydrocarbons.
This p aces., which requires no solvent stripping or pelletizing, results in
lower capital and operating costs when compared to particle form and solu-
tion polymerizatj,n.
Energy Requirements
No specific data for the energy required by LLDPE production were fcund
in the literature consulted.
EL/IR0pIflgNT AND INDUSTRjA ,, HEALTh CONSIDERATIONS
Like other polyethylene,, LLDPE is a nontoicic compound used in the
packaging and consumer goods industries as yell as for pipe which transportj
potable water. These products have the potential to affect a large percent-
age of the populatiun and any toxic effect would have a significant impact
on this industry.
High efficiency catalysts for the three LLDPE processes presented have
eliminated the need for catalyst deactivation using methanol a well as
polymer deashing. This simplificatio n in processing also eliminate, fugitive
V’jC emissions which are th. result of methanol addition and the deashing
step.
Worker Distribution and Emissions Release Points
MrIcer distribut ion estimates have been mad for RDPE production via
the thiee processes discussed previously. The estimates, shown in Table
142, were developed by correlating major equipment manhour requirements with
the process flow diagrams in Figures 42 through 44.
410
-------
Figure 44. Low pressure gas phase po1y ertzation.
Source: Hydrocarbon Processing , Noveisber 1979.
Ci anuj
- LLDP!
Product
-------
TABLE 142. RICER DISTRIBUTION ESTIMATES FOR LLDPE PRODUCTION
Process Unit Workers/Unjt/8—hour Shift
Particle Form Polymerization Storage
Continuous Reactor 0.5
Flash Tank 0.125
Dryer 0.5
Extruder 1.0
Solution Polymerization Storage 0.5
Continuous Reactor o.s
Flash Tank 0.125
Dryer 0.3
Extrude 1.0
Gas Phase Polymerization Heat Exchanger 0.125
Compressor 0.25
Continuous Reactor 0.5
Storage Tank 0.123
412
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No major air emission point sourcea are associated with the LLDPE
processes. However, fugitive emissions from such sources as reactor venca,
storage tanks, polymer dryers 1 and pelletizing extruder vents may pose
significant environmental and/or worker health problems based on the
constituents present In the stream, operating parameters for the process,
engineering and administrative controls used, and maintenance .rograrns.
Table 143 shows the principal process sources of fugitive emissions
from LLDPE manufacture. Ethylene, ethane, and several other possible input
materials listed in Table 141 (hydrogen, butane, propylene), are simple
asphyxiants, which pose a potential hazard because their presence limits the
amount of oxygen available in the atmosphere. The nitrogen used to purge
granular LLDPE of residual hydrocarbon is also a simple asphyxiant.
Solvents and diluents used tn LLDPE production are central nervous
system depreSsants . Overexposure may result in dizziness, headache, nausea,
and narcosis.
Particulece emissions from drying and pelletizing operations may con-
sist of polymer fines (nuisance dust) dnd specific additives vhich may be
hazardous in themselves.
Available toxicity and standards information about contaminants poten-
tially associated with LLDPE production is summarized in Table 10. IPPEU
Chapter lOb contains more detailed inforrnatjonregarding additives to the
process.
Health Effects
Animal test data indicate that several input materials and specialty
cnemtcals for LLDPE processes are tumorigenic agents; however, only one, the
catalyst cI romium (Vt) oxide, presents solid evidence of carcinogenicity.
Others, including benzoyl peroxide, a crosalinking agent, and hexane, a
d!luent, exhibit teratogenic properties. In addition, the solvent cyclo—
hexane has produced mutations in laboratory animals.
Chromium (V I) Oxide has produced positive results in animal tests for
carcinogenicity (109J and there is extensive evidence of It. mutagenic
properties. Teratogenic effects have also been observed In laboratory
animals. Chronic indjstrial exposures hive led to severe liver damage and
central nervous system involvement in humans; allergic reactions are
co on. [ 85J The American Conference of Governmental Industrial Hygienists
(ACCIII) has recommended Threshold Limit Value (TLV) of 0.05 mg/mi (8
hour TWA). The OSflA air standard Is 0.5 mg/rn 3 (8 hour TWA).
Air Emissions
Sources of VOC emissions are listed in Thble 143 by process and
constituent type. The major portion of the fugitive voc emissions from
ILOPE processing originates in the polymerization section, which ineludeg
ethylene recycle and recompression. These sources, all vents, may be
Controlled by routing the vented stream to a flare for the incineration of
413
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TASLE 143. SOURCES OF IUGITIVE EMISSIONS FROM LLOPE MANUFACTURE
Process
Particle ae
Source Constituent Form Solution Phase
. .. _________ _________ ______
Reactor Vents Ethylene X X X
Ethane X X X
Solvent X X
Flash Tank Ethylene X X X
Ethane X X
Solvent X X
Mixing Tank Ethylene X
Solvent X
Polymer Drying Ethylene and Poly—
Vent ethylene Particu-
late. and Emissions X X
Pelletizing Ethylene end Poly
Extruder Vent ethylene Particu-
late. and Emissions X X
Compressor Vent Ethylene X
Ethane X
Discharge Tank Ethylene X
Ethane X
414
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hydrocarbons and/or routing the vented stream to blovdown. [ 285J Other VOC
emissions may result from leaks associated with valves, flanges, pumps,
compressors, and drains. Equipment modification as dell as a routine
inspection and maintenance program are the available controls for these
sources.
Fugitive particulate sources are also listed in Table 143. These
sources, also vents, may be controlled by venting the stream to a baghouse
or electrostatic precipitator for particulate collection.
Wastewater Sources
LLDPE processes generate only routine cleaning water. No data
concerning LLDPE wastewater were found in the sources consulted.
Solid Waste
The solid vastes generated during LLDPE production include substandard
polymer which cannot be salvaged by blending and low—molecular weight
polyethylene waxes. The high efficiency catalysts have all but eliminated
wax productton. [ 38, 235] These wastes are not hazardous; therefore, their
discosal should not pose an environmental problem.
Environmental Regulation
Effluent limitations guidelines have been set for the polyethylene
industry. 3PT, 8AT, and NSPS call for the pH of the effluent t3 fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4,1976).
New source performance sLa darda (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five day.; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired with 15 days.
None of the input materials used in LLDPE processing have been listed
as hazardous (45 Federal Registec 3312, Play 19, 1980).
415
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SECTION 19
POLYETHYLENE — LOW DENSITY (LOPE)
EPA Source Classif (cat ion Code — Polyprod. General 3-01-018-02
INTRODUCTION
Polyethylefle is a lightweight, flexible, tough, chemical resistant
polymer which exhibfts outstanding electrical properties. These character-
istics combined with ease of fabrication and low production cost make p° 1 r
ethylene suitable for a wide variety of end products used in the packagi . g,
housewares, constructjon, communications, and medical industries.
The empirical formula for polyethylene f—4CH 2 Ca 2 . ...j illustrates the
repeating ethyleme unit of the polymer. The molecular structure of poly-
ethylene may be highly branched or basically linear depending upon the
polymeriza j reaction condition 1 .
Low density polyethylene (LOPE) is a polymer with a branched chain
structure. The partially crystalline nature of the solid is-due to the
structural synmetry caf tne molecules, which enables close packing ofthe
ordered regions of the chai:.s knows as crystalli , Complete crystalliga...
tion is prevented since the highly branched regions of the polymer chain
will not pack closely, leaving unordered regions in the molecule. Linear
LDPE (LLDPE), o’ the other hand, has a very ordered structure with little
branching which resembles the structure of high density polyethylene (HDPE).
This Section presents the processes used to produce
LOPE. Linear sow density Polyethylene (LLDPE) and high density polyethylene
(Nr1PE) are discussed separately.
Table A—26 in Appendix A lists typical properties of low density poly-
ethylene. LDPE and LLDPE are characterized by a density of less than 0.94
g/cm 3 , with the usual density ranging from 0.915 to 0.935 glen 3 . LOP!
with densities between 0.926 and 0.940 g/cm 3 may be referred to as medium
density polyethylene. The properties for these polymers are also listed in
Table A—26 in Appendix A. LOPE is only slightly soluble in most organic and
inorganic solvents at temperatures below 40’C. Above 50C, the solubility
Increases in hydrocarbons and halogena e hydrocarbons; however, LOP?. is
only slightly soluble in polar liqu...da such as alcohols, esters, mines, and
phenols. Animal, vegetable, and mineral oils are absorbed by LOPE.
LOPE is pr0d ,c d using high pressure mass polymerigatio , medium pres-
sure Solution polymerization ani low pressure gas phase polymerization.
Low pressure proceqqe 5 allow the production of LOPE or LLDPE at substantial
416
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energy savings; however, most of the LDPE produced is manufactured by the
high pressure processes since the low press ire technology is relatively new.
LDPE copolymers are produced by adding but.’ne, octene, hex2ne, or vinyl ace-
tate to the polymerization reactor. These comonomers increase tle branching
of the LOPE structure.
INnUSTRY DESCRIPTION
The LOPE industry is composed of the 14 maJor chemical and petrochemi-
cal producers listed in Table 144. These producers have 20 sites in the
United States: 13 in Texas, 3 in Loutsiard, 2 in Illinois, and one each in
Iowa and Califor ija; and one site in Puerto Rico. The type of reactor used
is also listed in Table 144. High press’tre processes are denoted by “tubu-
lar” or “autoclave” reactors while low pressure processes are designated as
such.
LDPE is used primarily for consumer related goods includ ng packaging,
institutional products, and the electronic industry. Due to the large
number of products manufactured from LDPE, the general trend of the economy
and consumer spending affects the production and sales ot LDPE resins.
After a production peak in 1979 of 3,542,000 metric tons, 1981 production
(3,417,000 metric tcins) remains below the 1979 level, but is still veil
above the 1976 production level of 2,642,000 metric tona.165, 143J table
145 presents the LOPE capacities for plants more than 15 years old. These
plant capacities may be permanenely shut down or replaced by the new low
rressure technology. [ 35J In the even’ that the entire 904,500 metric tons
are permanently shut down, which represents 21 percent of the total LDPE
capacity, additional LDPE plants would be needed iii the ne,.r future.
PROOUCTION AND END USE DATA
LOPE production is the largest in the plastics Industry. In 1981, U.s.
LOPE production totaled 3,417,000 metric tons. The LDPE resi— grades pro-
duced include: film, extrusion coating, injection molding, wire and cable
coating, and specialty resins. Resin production is presented by LDPE
producer in Table 146. The laigest LDPE uses ir.ciude:11681
• High c1ari y extruded film;
• Coating for paper, metal foil, and other plastic films;
• Barrier coating;
• Pipe;
• Wire and cable coating;
• Injection molded items vhicn require flexibility and toughness, such
as housewares, pails, lit o, packaging materials, furniture,
automotive Parts, crates, and toys;
• Blow nnlded items which require flexibility, such as squeeze
bottles;
417
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TABLE 144. U.S. PRODU EftS OF LDPE RESINS
March 1, 1982
Capacity 4u
Thousand Type of
Company Metric Tons Reactor
At’antic Richfield Company
ARcO Polymers, Inc. subsidiary
Port Arthur, TX 182 Tubular
Chemplex Co. (jointly owned by
American Can Co. and Cetty 011 Co.)
Clinton IA 189 Autoclave
Cities Service Co.
Chemicals and Minerals Group
Petrochemicals Division
Lake Charles, LA 330 Autoclavea
Dow Chemical USA
Freeport, TX 448 Tubular, auto—
Plaquemine, LA 254 dave, and low
pressura
processb
E. I. duPont de Ipmours & Co., Inc.
Polymer Products Depirtment
Orange, TX 211 Tubular and
Victoria, TX 109 autoclave
Eastman Kodak Co.
Eastman Chemical Products, Inc.,
subsidiary
Texas Eastman Co.
Longview, TX 166 Autoclav.C
El Paso Natural Gas Co.
El Paso Products Co., subsidiary
El Paso Polyolef ins Co.
Rexene Co.
Pasadena, TX 182 Tubula-
Odessa, TX 68
Exxon Corp.
Exxon Chemical Co. Division
Exxon Chemical Americas
Baton Rouge, LA Tubular and
autoc laved
(continued)
418
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TABLE 144 (continued)
March 1, 1982
Capacity in
Thousand Type of
Comp Metric Tons Reactor
Gulf Oil Corporation
Gulf Oil Chemical Co.
Plaaticg Division
Cedar Bayou, Ixe 259 Autoclave
Orange, TX 130 special process
InterNorth , Inc.
Northern Petrochemical Co.,
subsidiary
Polymers Division
Morris, TL 295 Tubular
Mobil Corp.
Mobil Oil Corp.
Mobil Chemical Co. Division
Petrochemicals Division
Beaumont, TX 136 Tubularf
National Distillers and Chemical
Corp.
Chemicals Division
U.S. Industrical Chemicals Co.
Division
Deerpark, TX 250 Tubular and
Tuacola, IL /5 autoclave
Phillips Petroleum Co.
Plastics Division
Pasadena, TX Low pressure
process
Union Carbide Corp.
Chetricals and Plastics Division
Seadrift, TXh 545 Tubular and
low pressure
process
Taft, LA 273 i Low pressure
Union Carbide, Inc., subsidtary
Penuelas, PR 141 Tubular
TOTAL 1 4,543
(continued)
419
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TABLE 144 (continued)
aA 90,900 metric tone per year e pangion came onetream in 1981.
bCompany plans to add 90,900 metric tone of capacity for low pressure LDPE
at Plaquemine in 1982.
Ccompany plans to debottleneck and add new capacity for conventional LDPE
to give a total of 272,700 metric torts capacity at this location by 1983.
dCompan, is planning to add 18,200 metric tons of capacity at Baton Rouge
by 1983 and plans to build a new facility of 272,700 metric tons annual
capacity for low pressure LDPE at Mont Béliview, TX in 1982 or 1983.
eCoiipany plans to add 227.300 metric tons capacity at Cedar Bayou.
Coapany plane to expand its high preeeue LDPE capacity to 227,300 metric
tons per year and conetruced 136,400 metric tons unit to produce low
pressure linear resin by 1983.
BThe bulk of the plant’s actual production is UDPE, but some LDPE resin (a
medium density pipe resin) is produced.
hgeadrjft capacity includes 181,800 metric tons convertible HDPE/LLDPE
capacity which was used to make LLDPE in 1981. A portion of the capartity
at Taft. LA is also used for ROPE production.
1981 produ on1s reported as 3,417 metric tons, which includes 451,000
metric tons of LLDPE resins aLd 290,000 metric tons of ethylene—vjny
acetate copolymer resins.
Sources: Chemical Econoai’s Handbook , updated annually, 1982 data.
Directory of Chemical Producers , 1982.
Modern Plastics , January 1982.
420
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TABLE 145. LDPE PLAJT CAPACITIES WHICH ARE MORE THAN 15 YEARS OLD
Thousand Metric Tons/Year
ARGO Port Arthur, TX 31.8
Dow Freeport, TX 63.6
Plaquemine, LA 36.4
DuPont Orange, TX 136.4
Victoria, TX 45.5
Eastman Longview, TX 90.9
El Paso, Inc. Odessa, TX 136.4
Gulf Cedar Bayou, TX 90.9
Orange, TX 90.9
National
Distillers
(USI) Tuscola, IL 54.9
Union Carbide Seadrift, TX - 90.9
Torrance, CA 3 _ 4 __
904.5
Source: Chemical Economics Handbook , updated annually, 1 81 data.
421
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TABLE 146. 981 LDPE NcENTRATION OF M J0R CRA)E BY PRODUCER
Company Production in Thousand Metric Tons
ARGO 181
Chemplex 188
Cities Service 329
475
DuPont 320
Eastman 166
Exxon 299
Cuif 388
Mobil 136
Northern Petrochemical 296
El Paso 249
Union Carbide 573
US! 324
Source: Chemical Economics Handbook , updated annually, 1981 data.
422
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• Powder coating used for textile, paper, flexible substrates, pipe,
and metal drums, as well as automotive carpet backs;
• Rotational molded articles such as toys, storage tanks, and
recreational vehicle tanks; and
• Extruded foam sheets and planks, which include the envelopes and
bags used to protect delicate articles during shipping.
Tables 147 and 148 present LDPE consuapt ion by end use and major markets for
LOPE film, respectively.
PROCESS DESCRIPTIONS
LOPE resins are manufactured by high pressure mass polymerization,
solution polymerization, or low pressure gas phase polymerization. Most of
the LDPE produced is manufactured using the high pressure procesee .
The emergence of high yield catalysts for solution and low pressure gas
phase polymerization has eliminated the need for catalyst deactivation and
catalyst removal from the polymer, called polymer deashing. Th! production
of low molecular weight polyethylene wax is also reduced. The simplifica-
tion of the LOPE process by removing or minimizing these steps reduces the
amount of VOC emissions generated.(168, 184, 190, 193, 195, 240, 274J
LDPE is polymeri ed from ethylene using either a radical initiator in a
high pressure masa p’lymerization procear or a catalyst in a low pressure
fluidized bed reactor. Solution polymerization processes may use either a
catalyst or an initiator.
For the LOPE processes using a radical initiator, the ethylene reacts
with the radical initiator (R ) to form a radical group. As other ethylene
molecules react with the ethylene rad’cal, the polyethylene chain is
propagated. The polymerization terminates when either two radical groups
combine (radical combination), by disproportionation, or when the raJicLl
reacts with a molecular weight regulating agent, such as hydrogen. The
polymerization reaction is depicted below:
I nit I at ion
+ R-. & 2 CH 2 R
Propagation
• S
2 CH 2 R + n(CR 2 CH 2 )—*cH 2 cn 2 — cH 2 c 2 g
Termination by Radical Combination
• •
CH 2 CH 2 R 2 2fCH2CH2tirR
RCH 2 CH 2 CH 2 CH 2 — C,I 2 CH 2 - ft
423
-------
TABLE 147. LDPE C NSUMPTION BY END—USE FOR 1981
End—Use Thousand Metric Tons
Blow Molding 26
Extrusion
Coating 251
Film ( 2 il and under) 1,875
Pipe and Conduit 12
Sheet (oyer 12 mil) 6
Vice and Cable 155
Other Exttu jo 0 29
Injection Molding 234
Rotomolding 25
Export 409
Other (chiefly resold resins and resin
used for blending and compounding) 395
TOTAL. 3,417
Source: Modern Plastics , January 1982.
424
-------
TABLE 148. LOPE FILM MARKET CONSUMPTION FOR 1981
Market Thousand Metric Tons
Packaging, Food
Baked Goods 118
Candy 15
Dairy 22
Frozen Food 42
Meat/Poultry/Seafood 61
Produce 59
Packaging, Retail Carryout Bags
Tee—Shirt Sacks (both grocery and
non—grocery applications) 18
Other Merchandise Bags (handle,
drawstring, and other types) 30
Grocery Wetpack 15
Self—Service Bags (includes perforated
rolistock — e.g. for produce) 22
Garment Bags (new—clothes bags and
bags used by 1 aundries or dry cleaners) 47
Pa:kaging, Other
Heavy—Duty Sacks (all—plastic sacks) 47
Industrial Liners (drum, bin, and box
liners) 74
ack and Counter Bags 79
Mdltiwall Sack Liners 15
Shcink Wrap, Pallet 30
Shrir Jc Wrap, Other (fnr overwrappjng
or bundling) 82
Stretch Wrap 35
Textile 82
Packaging, Miscellaneous Food, Nonfood 210
TOTAL PACKAGING 1,103
NonpackaRing
Agriculture 60
Diaper 8a king 60
Household (food and storage bags and
wraps) 49
Industrial Sheeting (construction and
Industrial rollstock) 93
Non , yen Disposables 11
Trash Bags (for home, Listitutional,
or industrial use) 529
Miscellaneous — 49
TOTAL NONPACKAGING 8 SF
TOTAL 1,954
(continued)
425
-------
TABLE 148 (continued)
Market Thousand Metric Tons
Less Tonnage From Resold Resin —56
Less Tonnage rua ‘. ovngagtng’ — 23
ADJUSTED TOTEd. 1,875
aAse es 152 dovugaging factor vith use of LLDPE.
Source: Modern Plastics , January 1982.
426
-------
Termination by Disproportjcnatjo
R—CH 2 -CH 2 3 Q 2 - 2 + R’—fCfl2-CH 2 cH 2 -&j 2
+ R’—fCH2Cfl 2 CH 2 -aj 3
Termination by Chain Transfer
R—CH 2 CH 2 ) -cH 2 & 2 + R’R -
R —1I2CH 2 _CH 2 2 _ft + R.
The LDPE process may also be initiated by a Ziegler type catalyst. If a
catalyst is used, the ethylene reacts with an active site on the catalyst to
form a radical group. As other ethylene molecules react with the ethylene—
catalyst radical, the polyethylene chain is propagated. The polymerization
terminates when either the carbon—catalyst bond becomes weak in relation to
the carbon—carbon bond3 in the chain or a molecular weight regulating agent,
such aa hydrogen, reacts with the polymer chain. The polymerization reac-
tion is depicted below:
Initiation
2 —cH 2 + Catalyst- .Catalygt —dH 2 ...
Propagation
Cata1yst—CH 2 — H 2 + nCH 2 —CH 2
Ca talys t—4CH 2 2+,rcH2 —CH 2
Termination by Elimination
Catalyst-CH 2 —cHfcH 2 2 _ 2 _ 2 -
Cataiy.t +
Termination by Hydrogenation
I I
Catalyet—fCH 2 QI 2 $. . .Qj 2 _ 2 + H2 —
Catalyct + 1 1+
Tables 149 and ISO list typical input materials and operating param—
e..er3 for the L)PE processes, respectlve3y. Other input materials used in
LDPE production such as radical initiators, comonomers, molecular weight
regulating agents, e’Lvents, and specialty chemicals (e.g. antiozidanta) are
lIsted in Table 151.
427
-------
TABLE 149. TYPICAL INPUT M&TERIALS TO LDPE PROCESSES
Radical
Initiator or
Process Catalyst Solvent Comonomer
Mass 2 X 2
Solution 2 2 2 2
Gas—Phase 2 2 2
TABLE 150. TYPICAL OPERATIPIC PARAIWTE POE LDPE PROCESSES
Process Pressure Reaction Time Conversion
Mass 150—350° c 6.9x1 0 6 — 20 sec—2 at m 15—26Z
3.4 1O 8 Pa
Solution 150 —200 ° C 2.8 — N/A >972
4.1x10 6 Pa
Gas Phase 100C 6.9x10 5 —
2.lxlOé Pa
aAutocla7e — 8—202.
Tubular — 20—30%.
bpjo reaction times were given in the literature; hovev.&, several passes
are necessary to achieve the desired conversion.
N/A — Not Available.
Sources. Encyclopedia of Chemical Techno1o , 3rd Edition.
Encyclopedia of Polymer Science and Techno1oj .
ydrocarbon Procegs , November 1979 4nd November 1981.
Modern Plastics Eruyclopedja , 1981—1982.
428
-------
ThBLE 151. INPUT MATERIALS AND SPECIALTY CHEMICALS FOR
LOPE PROCESSES IN ADDITION TO MONOMER
Compound Process
Comonomer Rutene Mass
Hexene Solution
Octene Gas Phase
Vinyl Acetate
Radical Initiator Caprylyl peroxide Mane
Cuinene hydroperoxide Solution
Decanoyl peroxide
Lauroyl peroxide
Oxygen
t—butyl hydroperoxide
t—butyl perbenzoate
t—butyl peroctoate
tbutyl peroxyacetate
t—butyl peroxyneodecanoate
t—butyl peroxypivalate
Catalyst Powdered chromium oxide Solution
Proprietary composition Gas Phase
Solvent 3eri ene Solution
Chlorobenzene
Ant Loxidants Dilauryl Thiodiproptonate Mass
(DLTDP) Solution
Hindered phenols Gas Phase
Phosphates
SteL rates
Sources: Encyclopedia c,f Chemical Technolo , 3rd Edition.
Encyclopedia of Polymer Science and Technology.
t 4 odern Plastics Encyclopedia, 1981—1982 .
429
-------
High Pressure Mass Polymerization
aigh pressure mass polymerization has been used for !.DPE production
since 1933.(168J As shown in Figure 45, the ethylene feed is first mixed
with ethylene from the low pressure recycle, compressed in a multistage
compressor, and mixed with the medium pressure recycle gas. The nixed
ethylene stream is then compressed in a second compressor to achieve the
desired pressure. The ethylene feed stream is mixed with the radical
initiator either before or after the second compression step and sent to the
reactor.’ A typical recipe for LDPE production via high—pressure mass
polymerization is as follovs:(l, 192, 195J
Material Parts by Veight
Ethylene 1,025
Initiator 2
Antioxidant <1
The polymerization is performed in either a stirred autoclave or a
tubular reactor. Stirred autoclave reactors typically have length to
diameter ratios which start at 2:1 and may reach 20:1. Baffles divide the
autoclave reactor into separate reaction zones while tubular reactors have
three reaction zones: preheating, reaction, and cooling. Temperatures
increase from 1500 to 250 ’C La the preheating zone to 300’ to 350C in the
reaction zone and fall back to 180’ to 230 ’C in the cooling zone. Tube
diameters range from 7.6 x to 7.6 z 10—2 meters and the reactors
typically have a length to diameter ratio which starts at 250:1 and may
re4ch 10,000:1.
Following polymerization, the ethylene/polyethylene gas stream is
separated in two steps. The first step separates unreacted gacee, cools
them, and returns them to the secondary compressor. In the second step, the
low pressure separator removes thø unreacted ethylene and routes it to a
cooler before returning it to the feed stream. The molten LDPE is fed to a
pelletizing extruder where antioxidants are added as veil as slip, block,
and anti—block agents. The resulting LDPE pellets are them ready for
bagging,
Solution Polymerization
Solution polymerization can be used to produce polyethylen, in a
density range from 0.92 to 0.96 glen 3 . To manufacture LDPE, moderati
pressures and careful selection of the catalyst or radical initiator are
required. The polymerization, as depicted in Figure 46, occurs when
ethylene,solvent, and the initiator (either a catalyst or a free radical
initiator) are fed to the reactor. After the polymei Lzation reaction
attains the desired conversion, the unreacted ethylene and the solvent are
removed from the polymer and recycled to the reactor while the LDPE polymer
is pellet zed in an extruder. [ 184j
430
-------
Figure 45. High pressure mass polymerjzatj,n.
Source: y roearbon Proceesj , 1981.
LDP
let.
-------
Figure 46. Solution polymerization.
Source: Rydrocarbon ProcessIng , 1981.
‘ -I
I. . )
LDPk
ta
-------
Typical input materials and quantities for solution polyiserizatioi 1 are given
below: t193J
Material Quantit 1
Ethylene (monomer) 918 kg
Organic Peroxide (initiator) 1.8 kg
Antioxidant 1.4 kg
Hydrocarbon Solvent 3.8 1
The major advantage of the solution polymerization process over high
pressure mass polymerization is the lower equipment cost. Lover pressures
also make the operating costc lover for solution polymerization when com-
pared to mass polymerization. The elimination of the monomer stripping step
also helps reduce the capital and operating costs for this process.
Low Pressure Gas Phase Polymerization
Low pressure gas phase polymerization of LDPE is a relatively nev tech-
nology. As depicted in Figure 47, ethylene, a comonomer, and catalyst are
fed to a fluidized bed reactor. The unreacted gases are rerouted to the
reactor through a single—gta2e centrifugal compresso,r followed by a heat
exchanger which cools the gases. The LDPE granular polymer leaves the reac-
tor and eaters a discharge tank. Nitrogen or another inert gas is used as a
purge to remove any remaining hydrocarbons since ethylene is explosive at
very low concentrations. The production recipe is thesame as for LLDPE, as
follows: (197]
Material Parts by Weight
Ethylene and 1—Butene (monomer and comonomer) 1,020
Catalyst 1
Hydrogen (molecular weight regulator)
Low pressure gas phase polymerization manufactures LDPE with only half
the capital cost and one—fourth of the energy required for a traditional
high—pressure mass polymerization process.134, 129] The process is simpli-
fied since no monomer stripping or pelletizing is required. Lower pressures
reduce the operating costs associated with the compressors.
Energy Requirements
The following energy requirements were classified by technology in the
literature consulted: (191, 192, 193, 194, 195, 1961
Unit/Metric
Technology Energy Required Ton of Product
ANIC Electricity 2.88—3.06 x IO Joules
Steam (24 atm.) 0.15 mE nc tons
AR 0 Technol— Electricity 4.16—5.03 x LO Jouies
ogy, Inc. Steam (35 atm.) 3.6—1.0 metric tons
433
-------
Figure 47 • -Low pree sure gee phase polyaerization.
Source: Hydrocarbon Processing , November 1979.
-------
Unit/Metric
Technology Energy Required Ton of Product
ATO Chimie Electricity 3.78 x i0 9 Joules
Steam 0.2 metric tons
El Pa8o Poly— Electricity 3.46 x iø Joules
olefins Co. Steam 0.5 metric tons
Gulf Oil Electricity 5.40 x i0 9 Joules
Chemicals Co. Steam, low pres— 0.5 mettic tons
sure (4 atm.)
Steam, high pres— 0.125 metric tons
sure (28 atm.)
Fuel for oil 5.28 x 108 Joules
heater
Imhausen Inter— Electricity 2.83—3.89 x Joules
national Co. Steam (28 atm.) 0.12—0.20 metric tons
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Polyethylene is a nontoxic compound used in the packaging and medical
industries. Some evidence of tumorigenic activity in test animals has been
observed; however, these results have not conclusively indicated the toxic-
ity of polyethylene.(224J Benzene, a suspected carcinogen, and chromium
oxide, a known animal carcinogen, are used in this process, as are the
radical i 1tiatorg cumene hydroperoxide and tert—butyl hydroperoxide.
The emergence of high efficiency catalysts and the use of radical
initiators has resulted in a reduction of processing steps for the solution
and low pressure gas phase polymerization processes. These catalysts
provide low catalyst concentration in the recycle stream and the resulting
polymer. Therefore, catalyst deactivation using methanol and catalyst
removal from the polymer (polymer deashing) are eliminated. Simplifying the
process in this manner significantly reduces the amount of VOC emissions due
to methanol addition and catalyst removal.(168, 184, 190, 193, 195, 240,
274J.
Worker Distribution and Emissions Pelease Points
Worker distribution estimates have been made by correlating major
equipment manhour requirements with the process flow diagrams in Figures 45
through 47. Estimates for each polymerization process are given in Table
152.
No major air emission points are ansociated with LDPE production.
Although there are no point source air emissions, fugitive and process
sources may pose a significant environmental and/or wor er health problem.
T1e impact of these emissions depends on the stream constituents, pt cess
c perating parameters, engineering and administrative controls, and r..ainte—
nance program.
435
-------
TABLE 152. W)RKER DI5TRIBLrl’ pj ESTIM&TES FOR LDPE PRODUCTION
Process Unit ! orkera/Unit/8 _ hour Shift
Mass Polymerization Compressor 0.25
(High Pressure) Continuous Reactor 0.5
High/Low Pressure Separator 0.25
Gas Cooler 0.25
ExIruder 1.0
Solution Polymer— Continuous Reactor 0.5
ization Polymer Recovery 0.25
Extruder 1.0
Gas Phase Polymer- Heat Exchanger 0.125
izat to Continuous Reactor 0.5
(Low Pressure) Storage Tank 0.125
Compressor 0.25
436
-------
Process sources of fugitive emissions are listed in Table 153. Con-
taminants of major concern are ethylene and nitrogen, which are simple
asphyxiants, chromluni (VI) oxide, a human carcinogen, and benzene, a sus-
pected human carcinogen. Particulate emissions from extruding operations
may produce potentially hazardous airborne nuisance dust concentrations.
Polymer additives (see Table 151) in elevated concentrations also may pose a
hazard.
Health effects information for the contaminants associated with LDPE
production are summarized below and in Table 10. Additive information is
given in IPPEU Chapter lOb’.
Emission ranges from which potential for employee exposure to volatile
organic compounds may be estimated are given in Tables 154 and 155.
Health Effects
The input materials and specialty chemicals for LDPE processes include
the suspected human carcinogen, benzene, and the known animal carcirogen,
chromium oxide. In addition, the highly toxic cumene hydroperoxide and
tert—butyl hydroperoxide, both radical initiators in the process, pose a
significant risk to plant employees if exposure by ingestion, inhalation or
skin absorption occurs. The following paragraphs provide a brief synopsis
of the reported health effects of exposure to these substances.
Benzene jq suspected human carcinogen [ 1OlJ which also exh bita
mutagenic and teratogenic propeties. It poses a moderate toxic hazard for
acute exposures and a high hazard for chronic exposures through ingestion,
inhalation, and skin absorption. [ 2’.2J Effects on the centcal nervous system
have been observed in humans upon exposure to concentrations of 100 ppm.
(98J Intermittent exposure to 100 ppm over 10 years has been linked vith
the development of cancers in huaans.(271J The OSHA standard in air is 10
ppm vith a ceiling of 25 ppa. [ 67J
Chromium (VI) Oxide has produced positive results in animal tests for
earcinogenicity [ 109J and there is extensive evidence of its mutagenic
properties. Teratogenic effects have also been observed in laboratory
animals. Chronic industrial exposures have led to severe liver damage and
central nervous system involvement in humans; allergic reactions are
common. [ 85J The American Conference of Governmental Industrial Hygienists
(ACCIH) has recommended a Threshold Limit Value (TLV) of 0.05 mg/m 3 (8
hour TWA) for chromium VI compounds. The OSHA air standard ii 0.5 r4g/m 3
(8 hour TWA).
Cumene Hydroperoxide is highly toxic after short exposures involving
ingestion, inhalation, or skin absorption of relatively small quantities.
(242J Animal test data indicate that the substance is also a tumorigenic
and a mutagenic agent. Prolonged inhalation of vapors results ii. headache
and throat irritation, prolonged skin contact with contaminated clothing may
cause irritation and blistering. [ 278J
437
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TABLE 153. SOURCES OF FUGITIVE EMISSIONS FROM LDPE MANUFACTURING PROCESSES
High Low
Pressure Pressure
Source Constituent Mass’ Solution G a—?hase
Discharge
Tank Vent Ethylere X
Comono ei x
Compressoc
Vent Ethylene x X
Coeonomer X X
Extruder Vent Ethylene and Poly—
ethylene Part icu—
lates and Emissions X X
438
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TABLE 154. QIARAcTERISTICS OF VENT STRYAJIS JM TME LOW DENSITY
POLYETHyLENE HICH—PREsSu g PROCESS
Emission
rate,
Stream kg VOC/Mg Composition,
Name Nature _ product Wt. ’ —
Emergency reactor vent Intermittent 0.08—4.65 95.3 Ethylene
1.0 Ethsne
1.5 Propylene
2.2 Isopropanol
Combined dryer and Continuous 0.71—6.01 0.2 Ethylene
storage bin venrs 99.8 Air
Emergency vent excluding Intermittent 0.2—7.65 100 Ethylene
reactor
Total Emission Rate 0.99—18.31
Source: Polymer Manufacturing Industry Background Information for Proposed
Standards , September 1983.
439
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TRBLE 155. QIARACTERISTICS OF VENT STREAMS FROM THE
LOW DENSITY POLYETHYLENE LOW—PRESSURE PROCESS
Emission
rate,
Streaiit kg VOc/Hg Composition,
Name Nature product Wt.Z
Raw materials Intermittent 0.04 0.5 VOC
purification vent 99.5 R 2
Catalyst additive vent Intermittunt 0.01 35 VOC
65N2
Comonomer purification Continuous 0.10 92 VOC
vent 8 N 2
Catalyst dehydrator Intermittent 0.004 2 VOC
handling vent 98 Air
Vacuum pump vent Intermittent 0.03 41 VOC
59 N 2
Recovery vessel vent Intermittent 0.06 46 VOC
54 Air
Eiae:gency reactor Intermittent 0.05 83 VOC
blovdoi,n vent 17 N 2
Reactor purge vent Intermittent o.7i 1—83 VOC
99—17 N2
Product discharge vent Continuous 22.3 35 VOC
65 12
Bin vent Continuous 0.05 0.02 VOC
99.98 Air
Compressor seal (oil) Continuous 0.01 50 VOC
vent 50 12
Analyzer vents Continuous o.oi 100 VOC
Total Emission Rate 23.37
Source: Polymer Manufacturing Industry Background Information for Proposed
StLndards , September 1983.
440
-------
Tert—Butyl Hydroperoxide has produced symptoms of severe depression,
incoordjnation, cyanosis, and respiratory arrest in laboratory animals. [ 243J
Skin contact is associated with severe local reactions. Limited animal test
data also i dieate mutagenic ef fees. No epidemiological data are available,
however, to evaluate the toxic hazard to humans.
Air Emissions
Sources of fugitive VOC emissions from LDPE processing are summarized
in Table 153 by process and constituent type. Fugitive emissions of ethy-
lene and comonomers are kept at very low levels for polyethylene production.
Since ethylene is explosive in low concentrations, management practices pre—
compressors and other pieces of equipment from developing significant
leaks. Safety conqidera ion dictate venting any air emissions outsine the
process area, as well as the use of Class 1, Group D electrical equipment
and non—sparking maintenance tools. The major portion of the fugitive VOC
emissions from LDPE processing originates in the polymerization section,
which includes ethylene recycle and recompression. Polymerization section
emissions from vents are typically flared and reported to contain 30 to 40
kg ethylene and 1 kg ethane per ton of LDPE produced. [ 93J
Sources of fugitive particulates are also listed in Table 153. The
particulates may be collected by venting the stream to either a baghouse or
electrostatic precipitator. According to EPA esti ateg the population
exposed to LDPE emissions in a 100 Ius 2 area surroLndjng an LDPE plant is:
30 persona exposed to hydrocarbona and 2 persons exposed to
partlculates. [ 286]
Wastewater Sources
LOPE processes generate only routine cleaning water. Several waste—
water parameters from LDPE processes, shown below, are reported by EPA.
These parameters were not separated accorJing to process type for the pur-
pose of establishing effluent limitations for the LDPE industry.(284 1
Wastevater Unit/Metric
Characteristic Ton of LDPE
Production 0 — 41.72 m 3
10D 5 0.2 — 4.4 kg
COD O. 2 54kg
TSS O—4. lkg
The control treatment technologies common to LDPE facilities are: oil and
water separator, equalization, aer ted lagoon, clarification, and polishing.
This wastewater treatment system has been shown to effectively treat LDPE
was tevaters. (284J
441
-------
Solid Waste
The solid wastes generated during LDPE production include substandard
polymer which cannot be salvaged by blending and low—molecular weight
polyethylene waxes. The high efficiency catalysts have reduced wax produc-
tion, which is reported as 2.6 kg per metric ton LDPE.(93 168J These
wastes are not hazardous; therefore their disposal should not pose an
environmental problem.
Environmental fl!at ion
Effluent limitations guidelines hav’e been set for the polyethylene
industry. BPT, BAT, and NSPS call for the pa of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired with 15 days.
Two input materials have been listed as izardoup (45 Federal Register
3312, May 19, 1980):
Beozene — Ufl19
Ch lorobenzene — U037
Disposal of these materials and all LDPE resins containing residual amounts
of these materials should comply with the provisjor.s set forth in the
Resodrce Conservation and Recovery Act (RCRA).
442
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SECTION 20
POLYPROPYLENE
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Polypropylene (PP) is a stiff, heat resistant polymer. Its low spe-
cific gravity pr .duces more finished parts per pound of polymer when com-
pared to other thermuplastic resins. The moisture and chemical resistance
of PP coupled with high teu ile strength make the polymer an excellent
choice for pipes and packaging. Although polypropylene homopolymers have
poor impact strength at low temperatures, the addition of ethylene as a
comonomer greatly improves the low temperature performance. Polypropylene
production in 1981 totaled 1,774,000 metric tons.(143J
Polypropylene is produced by the polymerization of propylene using a
catalyst to form the repeating structure shown below:
CL.
+211
A highly crystalline form of polypropylene, called isotactic, is produced
for commercial applicationa while the amorphous form, called atactic poly-
propylene, is an unwanted byproduct. The introduction of new catalysts has
minimized the production of atactic PP thereby eliminating the need for
atactic polymer removal and deashing.
Table A—27 in Appendix A presents typical proparties of polypropylene
homopolymer, random copolymer (where the comonomer is copolymerized randomly
with propylene), and block copolymer (where the comonomer is copolymerized
with regular segments of PP). Random copolymers are formed by adding ethy-
lene to the propylene monomer feed prior to polymerization reactor; block
copolymers are manufactured by adding ethylene and propylene to a post——
polymerization reactor which contains poiypropyjene.
Polypropylene may be manufactured to provide resins for a variety of
applications. Table A—28 in Appendix A presents typical properties of
various polypropylene grades.
443
-------
INDUSTRY DESCRIPTION
Twelve chemical and petrocheaic&l companies constitute the polypropy-
lene industry. These producers have 16 sites; 1] are located in Texas while
the other 5 sites are in Louisiana, Hey Jersey, Illinois, and West Virginia.
Total annual polypropylene capacity for 1981 was 2,359,100 metric tons.t35,
56, 90, 142J Major U.S. PP producers are listed in Table 156 as well as
their capacity, process type, and merchant source. Captive u’e constitutes
52 percent of the available capacity; the remaining 48 percent 4 s available
for production of PP for merchan use (eicternal sales).
Polypropylene may be produced by solution, mass, or gas phase polymeri-
zation. New high yield catalysts used in any of these, processes contribute
significart energy savings and result in a reduction of the atactic PP con-
centration in the product.
Polypropylene is used in many segments of the U.S. economy. Therefore,
general trends in consumer buyia and the automotive industry are reflected
in PP production. Polypropylene production in 1979, 1980, and 1981 was
1,746,000 metric tons, 1658,OOo i t ic tons, and 1,774,000 metric tons,
respectively. The current ezcese PP capacity (33 percent) will accomodate
any industry growth in the near future.
PRODUCTION AND END USE DaTA
The polypropylene segment of the plastics and :esina indus .r ’ comprised
10 pe..cent of the total industry production in 1980.(65J The larbest mar-s
kees for polypropylene are consumer oriented, with over half of the PP pro-
duced used for packaging, consumer and institutional goods, md furniture
and furnishings. Polypropylene is used to manufacture: [ 46, 90J
• Syrup bottles;
• Packaging for detergents, shampoo., mediciaes, medical irrigation
solutions, and a wide variety of over—the—counter drugs;
• Fenders, splash shields, automotive fan shrouds and heater ducts,
replacement battery housings, and replacement for hard rubber
original equipment;
• Primary and secondary carpet backing;
• Woven mats which separate the road surf a e fro. the road bed;
• Shipping sacks for potatoes, cebbage, and industrial products;
• Sandbags;
• Rags an overwrap film for soft goods;
• Electrical capacitors;
444
-------
TABLE 156. U.S. POLYPROPYLENE PRODUCERS
January 1982
Capacity Merchant
Producer ( Metric Tons) Process Sourcc _
Atlantic Richfield Co.
ARCO Polymers, Inc.,
subsialary
ARCO Chemical Company
Division
La Porte, TX 181,800 Mass Captive
Eastman Kodak Co.
Fastman Chemical Products,
I.c., subsidiary
Texas Eastman Co.
Longvlew, TX 63,600 Solution Captive
El Paso Natural Gas Co.
El Paso Products, Co.,
subsidiary
El Paso Polyolefins Co.
Rexene Co.
Pasadena, TX 68,200 Mass, Gas Merchant
Odessa, TX 68,200 Phase Captive
Exxon Corp.
Exxon Chemical Co. Division
Exxon Chemical Co. USA
Baytown, TX 181,800 Solution Captive
Gulf Oil Corporation
Gulf Oil Chemicals Co.
Olef ins & Derivatives
Division
Cedar Bayou, TX 181,800 Solution Captive
Hercules Inc.
Polymers Dept.
Bayport, TX 204,500 Solution Merchant
Lake Charles, LA 395,500 Merchant
InterNorth, Inc.
Northern Petrochemical
Co., subsidiary
Polymers Division
Morris, IL 90,900 Gas Phase Captive
(continued)
445
-------
TABLE 156 (continued)
January 1982
Capacity Merchant
Producer ( trjc Tons) PTocess Source
Phillips Petroleum Co.
Phillips Chemical Co.,
Subsidiary
Plastics Division
Pasadena, TX Mass Captive
Shell Chemical Co.
Norco, LA 136,400 Mass, Gas Captive
Woodbury, NJ 136,400 P iase Merchant
Soltex Polymer Corp.
Deer Park, TX 90,900 Solution Merchant
Standard Oil Co. (IN)
AMO Chemicals Corp.,
subsidiary
Chocolate Bayou, TX 234,100 Gas Phase, Captive
Solution
U.S. Steel Corp.
IJSS Chemicals Dijjs.ton
.USS Novamont, Irt .,
subsidiary
Kenova, WV 75,000 Solution Merchant
La Porte, TX 159,100 Merchant
TOTAL 2,359,100
Sources: Chemical Economics Handbook , updated annually, 1981 Data.
Directory of Chemical Producers , 1982.
EncyL1’ edja of Chemical Tech lo 1 , 3rd Edition.
Moderp Plastic: , May 1982.
446
-------
• Aerosol covers and valves, tote boxes, beveragE cases, fresh produce
• shipping containers, and thin sheet for food containers;
• Car bumpers;
• Large boxes and tanks for shipping products;
• Decorative ribbons, straps for automotive and nonautomotive packing,
monofilanents for brushes, and yarns for textiles and cords; and
• Pipes for industrial waste systems, irrigation systems, and floor
heating systems.
Table 157 lists polypropylene consumption according to major markets.
PROCESS DESCRIPTIONS
Polypropylene may be produced using solution, mass, or gas phase, or a
combtnation of these polymerization processes. Of the twelve polypropylene
producets listed in Table 156, six use solution polymerization. The remain-
ing six producers utilize: mass polymerization (two producers), mass and
gas phase polymerization (two producers), gas phase polymerization (one
producer), and solution and gas phase polymerization (one producer). Solu-
tion polymerization contributes 57 percent of the tc al PP capacity, with
mass, gas phase, mass/gas phase, and solution/gas phase adding the remaining
12, 4, 17, and 10 percent, respectively.
In polypropylene production, propylene monomer is polymerized to make
the homopolymer. Random copolymers are manufactured when ethylene is fed
along with propylene to the polymerization reactor; block copolyviera are
formed when ethylene and propylene are fed to a post—polymerization reactor
which contains polypropylene. The reaction is initiated when a propylene
mo ecule is added to an organometallic active center, depicted as
Propagation occurs by adding monomer at the acti’.e organometallic’ center.
The reat tion terminates either by mono’uer transfer, metal alkyl transfer, or
by hydride ion transfer, along with realkylation of the cataljst.
Initiation
M -R + CE 2 CH I 3 -*M -CH2CH-R
H3
ion
W’-CH 2 -CH-R + ncH 2 .cH-cH 3 —ØH+-dH 2 -ca_fcu 2 —cw _ .a
C R 3 CH 3 L CH3Jn
447
-------
TABLE 157. MAJOR POLyP80 y1 g MARKETS
rket 1981 Metric Tone
Blow Molding
Medical Containers 5,000
Consumer Packaging 28,000
TOTAL BLOW MOLDING J 3 , 000
Eztrusi 00
Coating 5,000
Fibers andd Filaments 473,000
Film (up to 10 nil)
Oriented 107,000
Unorented 38,000
Pipe and Conduit 9,000
Sheet (over 10 nil) 17,000
Straws 15.000
Wire and Cable 5,000
Other E tt’i i _ 1l,00 0
TOrAI. EXTRUSION 680,000-
Injection Molding
Appliances 43,000
Furniture 16,000
Housewares 86,000
Luggage and Cases 5,000
Medical 47,000
Dackaging
Closures 72,000
Containers and Lids 49,000
Toys and Novelties 41,000
Transportation
Battery Cases 63,000
Other 63,000
Other Injection Molding 92 ,ooo
TOTAL INJECTION MOLDING 577,00 0
Export 282,000
Other (Chiefly resold material and material
used for blending) — 202,000
TOTAL 1,774,000
Source: Modern Plastics , January 1982.
448
-------
Termination by Monomer Transfer
M+_CH 2 _ H..fcH 2 _dHR1+ 2 1 H — .
CH 3 [ CH3Jn CH 3
2 -CH 2 + cH2UICfH?_CH.j.R
H3 CHt C113Jn
Termination by Metal Alkyl Transfer
M+_CH 2 _?H_f H 2 _rH fR + A1R’ 3
3Jn
+ R’2A1CH 2 _CH_fCH 2 _ . .R
cH 3 L c 3 j
Termination by Hydrtde Ion Transfer
M -CH2 1 R—fH 2 H.j.R_M+_-11 + CH 2 -C —f H 2 cH 1 R
CH 31 H3Jn CH 3 [ 3Jn
M -H + 2 CR 3 -
The tertiary hydrogen atoms in the polypropylene chain are susceptible to
attack by oxygen and UV radlition; therefore, antioxidants and light
stabilizers are added to .‘ie pelletization step to ensure a stable polymer
during storage and shipping.
Tables 158 and 159 present typical input materials and operation param-
eters for polypropylene production processes. Input materials, including
specialty chemicals, used in polypropylene production are listed in Table
160.
‘ olution Poly’,ierjzatjon
Solution polymerization processes constitute 63 percent of the U.S.
polypropylene capacity. This process, as illustrated in Figures 48 and 49,
uses a solvent, typically heptane, as the polymerization medium. Propylene,
catalyst, and solvent are charged to the polymerization reactor. The
resulting polymer slurry is fed to a flash tank where the unreacted propy-
lene is removed and recycled to the reactor.
449
-------
TABLE 158. TYPICAL INPUT MTERIALS TO PP PRODUCTION
PROCESSES IN ADDITION TO MONOMER
Input
Organic Molecular Weight
Process Catalyst Solvent Regulating Agent
Solutton X X X
Mass X X
Gas Phase X X
TABLE 159. TYPICAL OPERATINC PARAMETERS FOR PP PRODUCTION PROCESSES
Process perature Pressure
Solution 50 — 90°C 500,000 — 1,500,000 Pa
Mass 55 — 80°C 2,700,000 — 4,100,000 Pa
Gas Phase Proprietary Proprietary
Sources: Chevical Engineering , April 20, 1981.
EncjclOpedia of Chemical Technology , 3rd Edition.
Nyirôcarhon Processing , Noveaber 1979, 1980, 1981.
450
-------
TABLE 160. INPUT MATERIALS AND SPECIALTY QIEMICALS USED IN
POLYPROPYLENE PRODUCTION (IN ADDITION TO MONOMER)
Function Compound
Comonomer Ethy ler .e
Catalyst
Ziegler Titanium trichioride and aluminum
diethy lmonochlor idea
Supported Titanium tetrachioride supported on:
Alumina
Magnesium chloride
Magnesium hydroxide
Magnesium hydroxychloride
Silica
Solvent Heptane
Catalyst Removal Isopropyl alcohol
Methanol
Molecular Weight
Regulating Agent Hydrogen
Ant [ oxidants Dilauryl thiodipropionate
Distearyl pentaerythitol diphosphite
Distearyl thiodipropionate
2 , 6 —di—tert—butyl—4—methy lphenol
Octadecyl 3 ,5—di C tert—butyl—4—hydro,cy)
hydroci nnama t e
Sterically hindered phenols
Tris (nonylphenyl )phospite
Quenchers (absorb excitation
energy caused by UV
radiation) Nickel dibutyl dithiocarbamate
Sterically Hindered Amine Light
Stabilizers (HALS) (capture
radicals, ‘ecompoee peroxides,
act as quenchers) Sterically hindered amines
aSecond generation catalysts include Lewis bases (e.g., esters, ethers,
amines, chlorides, and oxychlorideè of phosphorus and phosphites).
Sources: En -yclopedia of Chemical Technology , 3xd Edition.
ydrocarbon Processing , November 1977 and 1979.
Modern Plastics , November 1979.
451
-------
Figure 48. Solution polymerjzatjo of PP u8iug a conventjo 1 catalyst.
Source: EncyC1Op dj 8 of Chemical Techno1c 3rd Edition.
NOt bano I
Dominal Ited
‘I ,
Solvent
Vent
pp P01lOtb
to Va.ten t.r Tr.at , t
-------
Propylene Recycle
_____ Vent ____
Propylene
POLYMER-
FLASH
Solvent IZATION
REACTOR TANK
Catalyst
4 R1UGE_
- Nit rogen DR ER Vent
“I
ATACTIC I
Vent
Solvent Recycle POLYMER —
REMOVAL PELLETIZING
EXTRUDER
Mactic PP PP Pellets
Figure 49. Solution polymerization of PP using a high yield catalyBt.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
-------
Convent one iCataist
A typical recipe fur the production of polypropylene via solution
polymerization using a conventional catalyst is as follovs:!202J
Matertal Parts by Weight
Propylene (mon s r) 1,045
Titanium Catalyst 0.4
Alcohol 0.5
Hydrocarbon Solvent 8
In the conventional PP solution polymerization process, the polymer—
solvent mixture is washed first with methanol (or isopropyl alcohol) to
deactivate the catalyst, then with water to remove any remaining catalyst
solids. The spent catalyst is either regenerated or sent to disposal. The
washed slurry is decanted; the solids are centrifuged, dried in a nitrogen
atmosphere, and pelletized in an extruder. The liquid mixture from the
decanter is distilled so that the remaining solvent may be recycled to the
reactor while the water is sent to vastevater treatment. The effluent from
the centrifuge is heated to facilitate atactic polymer remOval before the
affluent is distilled.
High Yield Catalyst
The hig’ yield catalysts reduce the complexity and energy consumption
of the s’4utio polymerization process. After any unreacted propylene is
recycled to the reactor, the polymer—solvent mixture is centrifuged. The
polymer is dried in a nitrogen atmosphere and pellet ized while the effluent
is heated to facilitate atactic polymer removal. The purified solvent is
then recycled to the reactor. High polymer yield per pound of catalyst
(typically 3,000 g/g for conventional catalysts and over 250,000 g/g for
high yield catalysts) reduces the amount of catalyst in the polymer,
eliminating the need for methanol addition for deactivation and subsequent
washing. Since catalyst levels in the polymer are so small (ppb or less),
the catalyst residues are not removed. Since methanol and water are not
needed for catalyst removal, distillation of the centrifugate is also
eliminated. This process simplification results in a reduction of process
steam and electrical energy usage by 85 and 12 percent, respectively. [ 39j
Following are typical reactor inputs for polymerization of propylene
using a high—yield catalyst: 202, 225j
Material Parts by Weight
Propylene (lononer) 1,045
High—Yield Catalyst 0.004
Hydrocarbon Solvent 8
454
-------
Mass Polymeriz ition
35 polymerization of polypropylene uses liquid propylene as the
reaction medium. Propylene and a catalyst are fed into a loop or liquid
pool reactor where the polymerization takes place. A typical production
recipe for polypropylene via mass polymerization is shown below: [ 201]
Material Parts by Veight
Propylene 1,010
Ziegler—Natta Supported Catalyst 0.14—0.20
Hydrocarbon (diluent)
The anount of solvent was not found in the literature, but is expected to be
less than 30 parts by weight.
As depicted in Figure 50, after the monomer—polymer mixture is removed
from the reactor, methanol is added to facilitate catalyst removal. Spent
catblyst residues are either recycled for regeneration or sent to disposal.
Following catalyst removal, the mixture is washed with propylene and fed to
a flash tank. The unreacted monomer is separated and recycled to the
reactor while the polymer is dried in a nitrogen atmosphere and pelletized.
If a high yield catalyst is used, the catalyst removal step is eliminated
since the catalyst residues are left in the polymer and advantages similar
to those presented earlier in this section are realized.
Gas Phase Polymerization
In gas phase polymerization, a highly active, highly stereospecific
catalyst is used in order to minimize catalyst reaidues and atactic polymer
in the product. As shown in Figure 51, polymerization occurs in an agitated
reactor.
Propylene and the catalyst are fed to the polymerization reactor where
the reaction proceeds to the desired conversion. The resulting gaseous
polymer—monomer mixture is then fed to a flash tank where unreacted propy-
lene is separated and recycled to the reactor. Catalyst residues are a very
small part of the polymer mLxture (ppb or less); therefore, they are not
removed. The polymer is then dried In a nitrogen atmosphere and pelletized
in rn extruder; the dryer exhaust gases are recycled to the reactor to
recover any unreacted propylene. A typical gas phase reactor production
recipe for polypropylene was not found in the literature.
Energy Requirements
The following energy requirements are given for the various technolo-
gies listed belov: [ 199, 203, 205]
455
-------
Propylene Recycle
Prop lene
_____ Vent _L,_Vent j..
Propylene —
LOOP OR
LIQUID CATALYST POLYMER FLASH
Catalyst —
POOL ________
RECOVERY - TANK
T J T JTT _
Vent
1I
catalyst ._IPI DRYEIII
0 ’ Spent Nitrogen
Vent
P LETIZING
EXTRUD 1
Eets
Figure 50. Maes polymerization of polypropylene using a conventional catalyst.
Source: Encyclopedia of Chenical Technology , 3rd Edition.
-------
Catalyst
Figure 51. Gas phase polymerization.
Source: Encyclopedia of Chemical Technology 1 3rd Edition.
U I
-.1
N 2
Vent
Vent
PP Pellets
-------
Technology Energy Required Unit/Metric Ton Produced
El Pa. Poly— Electricity 1.69—1.98 x iø6 Joule.
olef ins Co. Steam 0.5 netric ton
Mitsui oatsu Electricity 1.87 x iO Joule.
Chemicals, Inc. Steam 2.6 metric tons
Sumitomo Chemi— Electricity 2.16 x IO Joule.
Cal Co., Ltd. Steam i.a metric tons
ENIROt AL AND INDUSTIUAj. HEALTH CONSIDERATIONS
Worker Distribution and Emissions Release Points
Worker distribution estimates have been made by correlating major
equipment manhour requirements with the process flow diagrams shown in
Figures 48 through 51. Estimates, shown in Table 161, have been made for
solution polymerization usin; two catalyst types and for mass and gas phase
polymerization.
Air emissions from process and fugitive sources comprise the emissions
from PP production. Although there a e no major point source air emissions,
fugitive and process emissions way impose a significant environmental and/or
worker health ‘problem. The magnitude ot this problem depends upon the
stream components, process operating controls, and maintenance program.
T: ble 162 lists major sources of fugitive emissions from polypropylene
production. Propylene, ethylene, and hydrogsn are simple asphydants whose
presence may reduce the available oxygen in the atmosphere. Reptane, iso—
propanol and methanol, while not highly toxic, may be irritating to the skin
and, in h1 h concentrations, may cause central nervous system depression.
Polymer and additive particulates may produce localized elevated nuisance
dust concentratjou 4 .
Emission ranges from whIch potential employee exposure to volatile
organic compounds may be estimated are given in Tables 163 and 164.
Health Effects
Several of the input materials and specialty chemicals used in poly-
propylene production have exhibited tumorigenic, mutagenic, or teraogenic
potential in animal tests. These include ethylene; methanol; isopropyl
alcohol; 2 6 di —tert —butyl...4....asthyl phenol; and nickel dibutyl dithiocarha—
mate. Available data indicate, however, that these substances, except
nickel dibutyl dithiocarbamate, are not highly toxic to humans upon expo-
sure, of short duration. Nickel dib’ityl dithiocarb te is considered very
toxic by ingestion.(85J
Although polypropylene has produced positive results in animal testing
for carcinogenicjty [ 107J, it poses a very low toxic hazard. For example,
458
-------
TABLE 161. WORXER DISrRIBUTI0N ESTIMATES FOR POLYPROPYLENE PRODUCTION
Process Unit Workers/Unit/8—hour Shift
Solution Polymerization Batch Reactor 1.0
(Conventional Catalyst) Flash Tank 0.125
Catalyst Removal 0.25
Washing 0.25
Decanter 0.25
Centrifuge 0.25
Dryer 0.5
Extruder 1.0
Distillation 0.25
Atactic Polymer
Removal 0.25
Solution Polymerizatiàn Batch Reactor 1.0
(High Yield Catalyst) Flash Tank 0.125
Centrifuge 0.25
Dryer 0.5
Extruder 1.0
Atactic Polymer
Removal 0.25
Mass Polymerization Batch Reactor 1.0
Catalyst Removal 0.25
Polymer Recovery 0.25
P ash Tank 0.125
Dryer 0.5
Extruder 1.0
Gas Phase Polymerization Batch Reactor 1.0
Flash Tank 0.125
Dryer 0.5
Extrud .’r 1.0
459
-------
TABLE 162 • SOURCES OF FUGITIVE EMISSIONS FROM POLTPROPTLENE MANUFACTURE
Process
Gas
Source Constitutent Solution Mass Phase
Reactor Vent Propylene X X X
Solvent X
Catalyst Removala Propylene x
Alcohol X X
Wash Tank Yenta Propylene
Alcohol x
Polymer Recovery Propylene
Dryer Vent Propylene and Poly-
propylene Emissions
and Particulates X X X
Solvent X
Pellet tzing Propylene and Poly—
Extruder Vent propylene Eeissions
and Particulates X X X
Solver Z
Distillation Vent Propylene
Methanol x
Solvent x
aNot present in high yield catalyst processes.
460
-------
TABLE 163. CHARACTERISTICS OF VENT STREAMS FROM THE POLXPROPYLENE SOLUTION
PROCESS
Emission
rate,
Stream kg VOC/Mg
Name Nature _ p 1 roduct Compositiona , b
Catalyst preparation Continuoug 0.07 C 10 HC, isopropyi
alcohol
Reactor vents COntinuous 4.07 C 3 HC, C 10 UC
Decanter vents Continuous 11.49 C 3 HC, C 10 RC,
isopropyl alcohol
Neutralizer vents Continuous 1.82 C3HC, C4HC,
C 10 HC,
isopropyl alcohol
Slurry vacuum/filter Continuous 7.93 C 1 OHC, isopropy],
system vent alcohol
Diluent separation Continuous 8.72 Ci HC, isopropyl
and recovery alcohol
Dryer vents Continuous 0 to 0.6 Air and 8m l1
amount of VOC
Extrusion/pelletizing Cønti uo ug 2.0 252 HC
vent
Total Emission Rate 36.79
astreamg are diluted in 10 to 30 percent nitrogen.
bC 3 HC — Propylene or any other hydrocarbon compound with three carbon
atoms such as propane.
C 4 HC — Butylene or any other hydrocarbon compound with four carbon atoms.
C 10 RC — Amixtiire of aliphatic hydrocarbons with 10—i2 carbon atoms.
Source: Polymer Manufacturing Industry Backgrc,und Information for Proposed
Stanciards , September 1983.
461
-------
TABLE 164. cHARACTI RISTICS OF VENT STREAMS FROM THE POLYPROpyLg
GAS PHASE PROCESS
Emission
rate,
kg VOC/Mg
Name Nature product Composition
Scrubber vent 25 Propylene, Propane,
Hexane
Reactor blow—down vent Intermittent 11.5 Hydrogen, Propylene,
Propane, Hezane
Total Emission Rate 36.5
Source: Polymer Manufacturing Industry Background Information for Proposed
Standards , September 1983.
462
-------
potypropylene medical devices have produced little or no irritant response
when placed into connective or muscle tissues for short periods of time.(31J
The propensity for diffusion of polypropylene from the material is so smnll
that biological resp. nse cannot be detected. [ 31J
No data exjs . in the available literati re with which to evaluate the
potential health effects associated with the catalysts and most of the anti—
oxidants used in the production of polypropylene.
Air Emissions
VOC fugitive emission sources for PP production are listed in Table
162. Emissions from the distillation column in solution polymerization are
reported to be: ethane, 0.8 kg; propylene, 20 kg; propane, 0.2 kg; and
alcohol and solvent, 10 kg per metric ton of polypropylene produced. Emis-
sions from the d’yers are reportea to be 9 kg per metric ton o product.(93J
The use of high yield catalysts reduces the number of processing steps,
which in turn reduces Lhe fugithe VOC emissions for the process. Other ‘)OC
emissiois may result from leaks in process equipment including flanges,
valves, pumps, compressors, and cooling towers. Although equipment modlfic a—
tion may reduce these emissions, a routine inspection and maintenance pro-
gram may be the most effective control.
Fugitive particulate sources are also listed in Table 162. These emis-
sions may be controlled by venting these streams to baghouse or electro-
static precipitator to collect particulateg. According to EPA estimates,
the oopilation exposed to PP em1qq on 9 In a 101) k ’n 2 area surrounding a PP
. .1ant is: 43 persons exposed to hydrocarbons and 2 persons exposed to
part tculates.(286J
IJastewater Sources
There are only two sources of vastevater associated with polypropylene
processing: routine cleaning water and wash water from solution polymeriza-
tiori. Rang•s of several wastewater parameters for vastewaters from polypro-
pylene production are shown below. Values for the vastevater from the pru—
ceases presented were not distinguished by process or resin type by EPA for
the purpose of establishing effluent limitations for the polypropylene
iridustry. 284J
Polypropylene Uastewat,r Unit/Metric Ton
Characteristics — Polypropylene
Production 2.50 — 66.75 m 3
POD 5 0—10kg
COD 0—20kg
The control treatment technologies common to polypropylene facilities are:
screening, equalizatl i, chemical trerPrs.rit, activated sludge, and polishing
pond. This wastewater treatment system has been shown to effectively treat
PP wastewaters. [ 284J
463
-------
Solid Waste
The solid wastes generated during polypropyleiau pr d t!’ n Include
substandard resins which cannot be blended, collected particulates, atactic
polymer, and catalyst residues. These wastes are not hazardous.
Environmental Regulation
Effluent limitations guidelines have been set for the polypropylene
industry. EPT, EAT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
backgroând, except in emergency pressure releases, which should not
last lore than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired with 15 days.
The only input to PP production which has been listed as hazardous is
methanol, designated U154 (45 Federal Register 3312, May 19, 1980).
Disposal of methanol and PP wastes containing residual amounts of methanol
must comply with the criteria set forth in the Resource Conservation and
Recovery Act (RCRA).
464
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SECTION 21
POLYSTYRENE (GENERAL PURPOSE)
EPA Source Classification Code—Pojyprod. General 3-01-018-02
INTRODUCTION
Polystyrene is a brittle thermoplastic which is clear, rigid, odor—
free, and tasteless. Its physical properties include low specific gravity
and good thermal stability. The ease with which polystyrene can be fabri-
cated using heat contribute, to the low cost of polystyrene products.
Polystyrene has excellent thermal and electrical properties which render the
polymer useful for manufacturing interior doors, lighting covers, air condi-
tioner housings, and shutters. Other applications include flower pots,
margarine tuba, cap ,, closures, disposable cutlery, toys, drinking cups, and
egg cartons.
Polystyrene is produced by the polymerization of styrene by means of a
free radical initiator. The formula
represents the repeating styrene group which provides the backbone for the
polymer chain. Table A—29 in Appendix A presents typical physical proper-
ties of general purpose polystyrene.
General purpose pcly;tyr.ne (GPPS) differs from impact (or rubber modi-
fied) polystyre,, In that, the general purpose resin is a pure homopolymer.
The absence of comoyrnmer. or modifiers, such as rubber, make the polymer
brittle. This section describes the manufacture of general purpose poly—
styren ; the section on impact (rubb.’r modified) polystyrene presents the
types of processes used in the manutar.ture of the copolymer. In 1980,
general purpose polystyrene accounted for 49 percent of the polystyrene
produced. Impact, or rubber modified, polystyrene accounted for the other
51 percent.(35J
General purpose polystyre’te is produced by suspension polymerization,
mass (or bulk) polytneri ntjo , or solution polymerization (also called
n
4 b5
-------
conrinuous mass polymerization with solvents). Over half of the general
purpoac nolystyrene produced is manufactured by the suspension polymeriza-
tion proceb:. Expandable bead polystyrene 1 used for cups and containers, is
also produced by this method. Emulsion polymerizatio’ is not used for the
production of generaj. purpose polystyrene due to the detrimental effect
large quantities of soap have on the clarity and electrical—insulation
characteristics of the product. However, emulsion polymeriz.ition is used in
the production of styre a copoly ’s (see the sections on acrylonitrile—
butadiene—styrene pu yuiers (ABS) and bLyrene—acrylonitrile polymers (SAN)).
INDUSTRY DESCRIPTION
The polystyrene indu.try is coisprised of 18 producers of general pur-
pose and/or impact polystyrene, three of which also produce styrene—buta—
diene latexes in addition to the polystyrene. These 18 producers have 44
3ites, Li of which are in Ohio, Michigan, Illinois, and Pennysivania, and
another 8 in California. The remaining plants are located in the east and
southeast. Polystyrene producers are listed in Table 165 and atyrene—buta—
diene latex producers are presented in Table 166.
Polystyrene is used in consumer related industries, such as construc—
tiot , appliances, and packaging. Therefore, polystyrene consumption followc
the trend set by housing starts and consumer spending. After a production
peak of 1,820,000 metric tone in 1979, a drop to 1,490,900 metric tons
occurred in 1980.(35, 64, 65J Most of the expansion planned is for expand-
able polystyrene. Excess capacity for impact polystyrene is sufficient to
support industry growth for the near future. Therefore, no new plants for
impact polystyrene are expected to be built.
PRODUCTION AND END USE DATA
In 1980, total polystyrene sales were 1,490,900 metric tons.(353
Polystyrene is used for packaging, toys, foam insulation, electrical and
electronic uses, and serviceware, which includes the familiar cup.. Table
167 presents the 1980 consumption of polystyrene. These product. can be
classified as either molding resins, extrusion resins, or expandable beads.
General purpose polystyrene contributes 64 and 51 percent of the total
polystyrene produced for molding and extrusion resins, respectively.(35J
PROCESS DESCIIIPTION5
General purpose polystyrene is produced by suspension, mass, or solu-
tion polymerization. According to one estimate, over half of the general
purpose resin is manufactured using suspension polymerization,(l7J ac is the
majority of the expandable bead polystyrene since the polymer is produced in
a for’n which is readily used.(2j The remainder of the general purpose poly-
styrene oroduction is performed by mass an solution polymerization. Sus—
ension polymerization of general purpose polystyrene has excellent versa-
tility for the production of numerous types of products. However, high—
purity products are more difficult to obtain since water, suspension
stabilizers, and unreacted initiator, tend to be contaminants. The added
466
-------
TABLE 165. MAJOR U.S. PRODUCERS OF POLYSTYRENE
Cana.’ft ’ s of J..1 7 1, 1981
(Thousand Metric Tono )
General
Pur 1 ose Expandable
Producer and Impact Bead Total
A6E Plastik Pak Co.
A6E Plastics Division
City of Industry, CA 15.9 0 15.9
American Hoechst Corp.
Plastics Division
Chesapeake, VA 118.2 0 118.2
L.eominster, MA 54.5 0 54.5
?eru, ii . 77.3 36.4 113.6
COMPANY TOTALS 250.0 36.4 286.4
American Petrofina Inc.
Cosden Oil & Chemical Co.,
subsIdiary
Big Spring, TX
Calumet Ctty IL. 77.3
Orange, CA 27.3
WiI2dsor, ‘U 54;4
Atlantic Richfield Co.
ARCO Polymers, Inc., sub.
Beaver Valley, PA 54./. 1 59 1 b 213.6
RASP Wyandotte Corp.
Po1yi ers Groups
Styropor Division
Jamesburg, NJ 0 79.5C 79.5
Dow Chemical USA
Allyn’s Point, CT N/A N/A 86.4
Ironton, Oil N/A N/A 8t ,.4
Joliet, IL N/A N/A 63.6
Midland, 141 N/A N/A 100.0
Torrance, CA N/A N/A g 0 9 d
COMPANY TOTALS 418.2 427.3
N/A — Not Available.
(continued)
467
-------
TABLE 165 (continued)
Capacity as of July 1 1981
(Thousand Metric Tons)
Ceneral
Purpose Expandable
Producer I . ct — Bead
Carl Gordon Industries, Inc.
Hammond Plastics
Oxford Dlvi to
Oxford MA 43.5 0 45.5
Hammond Plastics Midvest, Inc.
Ovenaboro, KY 22.7 0 22.7
COMPANy TOTALS 68.2 ii2
Gulf Oil Corporation
Cuif Oil Chemicals Co.
Plastics Division
Marietta, OH 140.9’ 0 140.9
Nuntsman-Coodson Chemical
Corp.
Troy, OH 9.1 0 - 9.1
Kama Corp.
Haseftown, PA 11.4 0 11.4
Mobil Corp.
Mobil Oil Corp.
Mobil Chemical Co.,
Diyt jo
“etrochemicals Divi i
Nol.yoke, MA 40.9 0 40.9
Jollet, fl 18.2 0 i8.2
Santa Anna, CA 29.3 0 29.3
COMPANY TOTALS
Nonoan j Co.
Monsanto Plac tici and
Resins Co.
Addy jton, OH 136.4 0 136.4
Decatur, AL 4 .5 0
Long Beach, CA 22.7 0 22.7
Springfield, MA 136.4 0 136.4
COMPANY TOTALS 340.9 4 J
(continued 1
468
-------
TABLE 165 (continued)
Capacity as of July 1, 1981
(Thousand Metric Tons)
General
Purpose Expandable
Producer and Impact Bead Total
Polysar Group
Polysar Inc.
Resins Division
Copely, OH 54.5 0 54.5
Forest City, NC 18.2 0 18.2
Leominster, MA 54.5 0 54.5
COMPANY TOTALS 127.3 0 127.3
Shell Chemical Co.
8elpre (Marietta), OH 136.4 0 136.4
Standard 011 Co. (IN)
AMOCO Chemical Corp., sub.
Joliet, IL 136.4 0 136.4
Torrance, CA 15.9 0 15.9
hlilou Springs, IL 40.9 0 40.9
COMPANY TOTALS 193.2 0 19 .2
i ’ ..yrene Pisotics, Inc.
FOLt Worth, TX 0 22.7 22.1
U.S. Steel Corp.
USS Chemicals Division
Haverhill, OH 9.18 0 9.1
Vltltek Inc.
Delano, CA C 2.3 — 2.3
T(IT L 2,068.2 309th 2,377.3
auth b.gln production of expandable PS at this location by the end of
19R1, • t1mated capacity - 18,200 metric tons per year.
hr ,mpgny Intends to increase expandable PS capacity to a total of 227,0S)
r trtc tong per year.
(cont i.ius’d)
469
-------
TABLE 155 (continued)
Ccompany will add expandable PS production capacity of 20500 metric tons
per year by 1983.
dOne production train was put on standby ir . August 1981.
eCo npany viii increase capacity to 200,000 metric tons per year by early
I 83.
company capacity will h increased by 118,200 r tric tons per year by
early 1983.
8Pactlity was cloge 1 in September 1980 with the exception of this small
amount of impact kegin produced.
hCeorgja Tacific Corp. plans to complete 29,500 metric tone per year of
its exp&ndable PS capacity in Paineeville, CA by 1982.
Sources: Cnemical Economics }andbook , updated annually, 1981 Data.
Directory of Chemical Producers , 1981.
470
-------
TABLE 166. POLYSTYRENE PRODUCERS WHICH ARE ALSO
MAJOR STYRENE-BUTADIENK LATEX PRODUCERS
Dow Chemical USA
Allyn’s Point, CT
Dalton, GA
Freeport, TX
Midland, MI
Pitts”rgh, CA
Polysar Group
Polysar Inc.
Po ysar Latex
Beaver Valley, PA
Chattann’ga, TN — 2 plants
U.S. Steel Corp.
USS Chemicals DivisIon
Scotts Bluff, LA
Source: Chemica] Economics Handbook , updated annually, 1981 Data.
471
-------
TABLE 167. CONSUMPTION 0? POLYSTYRENE FOR 1980
Thousand Metric Tons
Packaging 568.2
Housewares, furniture, and
furnishing, consumer products 181.8
Electrical/electronic uses,
ap?1 Lances 168.2
Toys, sporting good ., recreational
articles 140.9
COflst ru tjo 136.4
Servicevaze and flatware 109.1
Miscellaneous commercial and
industrial molding 81.8
Other uses (medical/dental and
other laboratory article., combs,
brushes, eyeglasses, signs,
vrtt r utensils, office and
choo1 supplies, novelties and
miscellaneous uses’ 104.5
1,490.9
Source: Chemical Economics Handbook , updated annually, 1981 Data.
472
-------
cost for the water, stabilizers, and wastewater treatment also make mass
polymerization a more favorable process as the operating costs of a
polystyrene plant tncrease.12 , l47J Due to the narrowing price increase
from styrene moncmer to polymer, mass polymerization will proba )ly become
the major process used for polystyrene production in the future.(147J
Tables 168 and 169 present typical input materials and operating parameters
for theqe processes. Specialty chemicals and other input materials are
listed in Table 170.
General purpose polystyrene is produced by the polymerization of
sryrene. The reaction y ,c. init iated with heat, but a free—radical ini-
tiator Is typically used. The free—radical initiator (K ) reacts with the
styrene monomer to start the polymerization reaction. As other styrenr
monomers combine ith the styrene radical, the polymer chain is propagated.
Polymerization terminates when the radical reacts with an electron accepting
group (R’ ), which is called chain transfer. Termination also occurs when
two radical groups react with each other, or by disproportionation. T jpical
molecular weights for polystyrene range from 200,000 to 300,000.(l7J The
polymerization sLepa are depicted below:
nttLaUo , ,
CII.CN 2 I
ii I II I
I
I .w .c,q
2 2
i i I ‘ ‘ii I
T.r.1n.p L’,.i
rLsdIr.I Cn tnitLo,,
• •
I rjqcs I
rh.In Tra,u ,,
I
iQ • i’.
‘I
• I..
473
-------
TABLE 168. TYPICAL INPUT MATERIALS TO GENERAL PURPOSE POLYSTYRENE
PRODUCTION PROCESSES IN ADDITION TO MONOMER AND INITIATOR
Organic Suspension B1 ving
Process Water Sol; Stabilizer
Su3pengion X X X
Mat, c,
Solution X
‘For the production of expandable bead polystyrene.
TABLE 169. TYPICAL OPERATING PARAMETERS FOR GENERAL r.’RPoSE
POLYSTYRENE PRODUCTION PROCESSES
Process Tea.perature Pressure 5 Rea ti.in Tim .
Mac is 80 — 2 ( 10°C Slightly reduced 12—18 hours
to 10—20 mm Hg (batèh)
2—8 hours
(continuous)
Suspension 110—110°C Reduced 5—9 hours
! ,1utton 90—130°c Atmoqph.rtc to 6—8 flours
10—20 mis Hg
5 lncluding devolstjjfzatfon step.
Sources: Lyle 7. Albright, Processes for Plaint Addition—Tip. Plastics and
Their Monomers, 1914.
Encyclopedia of Polymer SeieI.’!e and Technolcgy , 1971.
474
-------
TABLE 170. INPUT MATERIALS USED IN GENERAL PURPOSE POLYSTYRENE
MANUFACTURE (IN ADDItION TO STYRENE MONOMER)
Free Radical Initiators azobisisobutyronitrile
benzoyl peroxide
dimethylanjljne 5
di—tert—butyl peroxide
tert—butyl hydroperoxide
Chain Transfer Agents alkyl mercaptans
—methyl styrene diner
carbon tetrabromide
carbon tetrachioride
ethylbenzene
Retardants and Inhibitors benzoquinone
1, l—diphenyl-2—picrylhyjrazy l
ferric salts
oxygen
sulfur
tert—butylcatechol
tert—butyl—pyrocatechol
Solvents ethylbenzene
Suspension Stabilizers alkaline earth phosphates,
(protective colloids) carbonates, and/or silicates
gelatin
magnesium silicates
methyl cellulose
pectin
polyacrylic acid and its salts
polyvinyl alcohol
polyvinyl pyrrolidone
starch
sulfonated polystyrene
zinc oxide
Flame Retardants alkyl phosphates
antimony oxide
aryl phosphates
hydrated aluminum oxide
(continued)
475
-------
TARL,E 170 (continued)
Lubricant mineral oil
phenol
aUsed only in conjunction with benzoyl peroxide at low teaperat ures. -
Sources: Encyclopedia of Polymer Science and Technol 7 , 1911.
Lyle P. Aibright, Processes for Major Addition Type Plastics and
Their Monomer ., 1974 .
476
-------
Disproport tonatian
CHCH 2 R CHCH 2 R CH 2 Ch 2 z C I.CHR’
+ -, +
k )
Oxygen reacts with the free radical initiators used, thus making a peroxide
radical shov below:
R. +
which slows the reaction rate. Polymerization is performed in a nitrogen
atmosphere to minimize this reaction.
Suspension Polymerization
Suspension polymerization of general purpose polystyrene uses water and
a suspending agent to separate the monomer into droplets for the polymeriza-
tion process. The major advantage of suspension polymerization as compared
to other methods is the production of the polymer in small beads which are
easily separated from the aqueous phase. Although the polymerization rate
is slower, tP ’e coRt Is higher, and the contamination more severe for suspen-
sion polymerl ation than mass or solutioii polymerization. The advantages of
this proce s over mass or solution polymerization include: excellent heat
transfer, no solvent recovery problems, fewer safety hazards, simpler temp-
erature control, and -aarrnwer range particle size control possible. Another
advantage of this process is the capability to produce both general purpose
resins and expandable bead polystyrene in the same reaction train.
As illustrated in Figure 52, the styrene monomer is stripped of the
inhibitor, which is added to prevent polymerization during shipping and
storage, prior to entering the reactor. The stripper water is sent to
wastewater treatment while the monomer is combined with a monomer soluble
initiator and fed to an agitated reactor filled with water. A dispersing
agent and a suspension stabilizer are added to maintain the monomer as
aqueous phase droplets.
A typical recipe for suspension polymerization of CPPS includes the
following: 12J
Material Parts by Weight
Styrene (monomer) 7.27
Water 8.825
Additives not specified
477
-------
Vent
Figure 52. Polystyrene production using the suspension polymerization process.
Source: Encyclopedia of Polymer Science and Technology .
LIKIIITOS
STIIPPU S
TANK
To
V t
I,
TASK
-J
To Wstsl(1.r
Tr ea t. . nt
Polystyr 00
To WasC.w . P•11.ts
P03 vs tyren.
Bead.
-------
If expandable polystyrene beads are desired, a blowing age it, such as
n—pentane, is also fed to the renctor where it is absorbed in the organic
phase and remains in the polymer beads. Expandable polystyrene bead
production is illustrated In Figure 53. The dried polymer beads typically
contain 5 to 7 percent pentane.I1j When heated, these beads expand to form
molded products or, more recently, foam insulation.
After polymerizatton, the polymer beads are washed with acid to remove
any remaining initiator ,i and suspension stabilizers. The vash water is sent
to wastevater treatment while tie slurry of polymer beads is centrifu çed.
The water removed during centrifugation is combined with the other waste—
water while the beads are dried. The polymer beads are fed to a devolatili—
zation extruder where any remaining monomer is removed during pelletization
and recycled to the reactor.
Typical water to monomer ratios range from 1:1 to 4:1 and the particle
size of the monomer ranges from 0.1 to I .(l7 Final polymer volatile
concentrations as low as 0.5 percent can be produced using devolatilization
extrusion at reduced pressure, 10 to 20 me Hg. Reactors are typically
aluminum, stainless steel, or stainless steel clad matérial.. Copper is not
used since it diacol rs the polymer. I
Mass Polymerization
Mass polymerization is the simplesé process by which polystyrene can be
made and prod•ices a polymer of high clarity having good electrical—insula-
tion properties. The major disadvantage of this process is the difficulty
in controlling the polymerization reaction due to it. highly exothermic
nature and the increasing viscosity of the polymerizing mass. However, mass
polymerization of polystyrene results in little contamination of the polymer
since water and organic solvent. are not used.
Mass polymerization, as depicted in Figure 54, consists of four basic
steps: prepolymerization, polymerization, devolatilization, and extrusion.
Prior to polymerization, the .tyrene monomer is stripped of the inhibitor
uaed t prevent polymerization during shipping. The styrene is fed to the
reactor while the stripper water is sent to vastevater treatment.
The equipment ubed in the prepolymertzation step con i .t. of a stirred
reactor with a reflux condenser operating under reduced pressure. Thin
enables control of the reaction temperature by removing a portion of the
vaporized monomer and returning the condensed liquid atyrene to the reactor.
If peroxidic initiators are used, the reaction may h e carried out at a lover
temperature (80’C) than that used for thermal Initiation (130C). The
polymer content of the resulting mixture vbries from 25 to 35 percent.
From the prepolymerization section, the monomer—polymer mixture is fed
Into a series of stirred reflux reaction kettles or reaction towers. The
temperature I. progressively rais d through the reaction zone to prevent
fall off in polymerization rate and to reduce the viscosity of the polym—
erizing mans. Typical final temperature in the polymerization section range
from 150 to 200°C.(2, 17J Materials of construction for the reactors are
479
-------
Vent
INHLSITO I
Figure 53. Expandable bead polystyrene production using• the suspension polynerization process.
Source: Encyclopedia of Polyxer Science and Technology .
TMI
Th Va.tsiist.,
TaII
0
To Hen lsw.I.,
P1y etyr. .
lead.
-------
Luw J L uj i
Vent
Figure 54. Polystyrene productton via nasa polynerization.
Sources: ..yle F. Aibright, Processes for Major Addition Type Plastics and Their Manufacture , 1974.
Encyclopedia of Polynar Science and Technology .
DEVQLATILIZLR
Pellet.
-------
aluminum, stainless steel, or stainiess—steel clad material.. Copper is not
used since it causes discoloration of the polymer.
In order to remove unreacted monomer and low molecular weight polymers,
the reaction mixture is then fed to a static devolatilizer where the vola—
tiles are flaethed off and distilled. The styrene monomer and oligomers are
recycled while the low molecular weight polymers are sent to a landfill. The
purified polymer is then extruded through a vented extruder and pellettzed.
A typical recipe for mass polymerization of GPPS was not found in the
literature. However, it was reported that the recipe for mass polymeri’a—
tion is similar to that for solution polymerization.
Solution Polymerization
Solution polymeri-ation of polystyrene has several advantages over the
masi polymerization process. The viscosity of the polymerization medium is
lower, the temperature control is more precise, and the molecular veig it of
the polymer is lower. Although this process allows better heat disoipation,
the solvent reacts with the polymer chain, res’llbLng in a more contaminated
product.
A typical recipe for solution polymerization of GPPS ii shown below:
lAibrighti
Material Parts by Veikht
Styrene (monomer) 997
Ethylbenzene (solvent) 4 (makeup)
Addttivea 23.4
3lueing Dye 0.2
As illustrated in Figure 55, the styrene monomer is washed to remove
the inhibitor added ti, prevent polymerization during shipping and storage.
The wash water is sent to vastewater treatment while the styr.n. is diluted
with ethylbensene and fed to a series of agitated reactors with heat
exchange zoneu. After polymerization, the unreacted styrene and solvent are
removed from the polymer aid recycled. The purified polymer is then
extruded into strands and cut into pellets.
The .thylbenzene concentration of the incoming solution to the reactors
ranges from S to 25 percent. Temperatures in the reactors start at 110 to
130’C in the first stage and increas, to 105 to 170C in the last stag..
Devolatiltza;Ion temperature, under reduced pressure, is usually 250C.
Small amounts of lubricant such as mineral oil (about 3 percent) may be
added.(208J Reactors are aluminum, stainless steel, or stainless—steel clad
materials. Copper is not used since it discolors the resulting polymer.
Energy Requirements
The energy required for polystyre .. production is listed below by
technology:1208, 209, 21 1J
482
-------
Figure 55. Polystyren. production via solution po1y erization.
Source ncyclopedta of Poly.er Science and Technology .
imi i i ro
Sf! PP
To W at.w.tor
1-
Vent
YStyf ne
•01 1 .
-------
Unit/Metric
Technology Energy Required Ton of Product
Cosden Technology, Electricity 6.30 x 108 Joules
Inc. Fuel 1.26 x iO Joules
Gulf Oil Chemicals Electricity 9.01 x i08 Joule.
Co. Steam 0.4 metric ton
Societe Chimique Electricity 4.86 x IO Joules
deaCharbonnages Net Fuel 4.19 x l0 Jóules
(CdF)——The BaJger
Co., Inc.
ENVIRONMENTAL CONSIDERATIONS
None of the chemicals which have been identified as inputs to poly-
styrene processing are known human carcinogens. However, there is some
evidence from tests conducted and reported to NIOSH of polystyrene and
styrene causinS tumors in test animals. Although these results are not
conclusive, standards have been set for styrene and polystyrene exposure.
Three other input materials to polystyrene processing are suspected human or
known’ animal carcinogens: carbon tetrachlride, a chain transfer agent;
polyvInyl alcohol, a suapension stabilizer; and antimony oxide, a flame
retardant. Other highly toxic inputs include tert—butyl hydroperoxid., a
free radical initiator, and bànzoquinone, a retardant.
One environae itally significant portion of polystyrene pricessing is
the devolatilization step. Residual styrenc monomer in the polymer 1.
typically reduced to less than one percent,, thereby reducing the exposure
risk and rendering the polymer usable for food applications such as meat
qya, egg cartons, and wrap for non—fatty foods.
. .,. er Distribution and Emissions Release Points
We have estimated worker distribution for polystyrene production by
rorrelating major equipment manhour requirements with the process flow
diagrams in Figures 52 through 55. Estimates are given in Table 171.
No majo emission point sources are associated with polystyrene pro—
d iction. Although there are no major air emission point sources, fugiti
emissions may pose a signif leant etwironmental and/or worker health proM ..
depending on the components in the stream, operating condition, for the
proc..., engineering and administrative cont’ols, and maintenance programs.
Procene sources of fugitive eni.siona are listed in Table 172. Typical
Inhibitors, stabilizers and initiators are listed in Table 170. Ethylbes—
zene Is the solvent generally used in solution polymerization. Particulate
emission, from centrifugation, drying and extrusion operation may contain
harmful additives and may produce elevated nuisance dust level..
484
-------
TABLE 171. WORKER DISTP.IBUT1O 1 ESTiMATES FOR GENERAL PURPOSE
PQLYSTYRENE PRODLJCTI N
Process Unit Worker /Unlt/8hOUt Shift
Suspension Pclymerizatiofl Steam Stripper 0.25
(Pellets and Beads) Batch Reactor 1.0
Batcii Mixer 1.0
Washing 0.25
centrifuge 0.25
Dryer 0.i
Extruder 1.0
Mass Polyinertzati fl Steam Stripper 0.25
Batch Reactor 1.0
Distillation Column 0.25
Devolatiltzer 0.25
Extruaer 1.0
Solution Polymerization Steam Stripper 0.25
Batch Reactor 1.0
Flash Tank 0.125
Extruder 1.0
48S
-------
TARLE 172. SOURCES OF FUGITIVE EMISSIONS FROM POLYSTYRENE MANUFACTURE
Process
Source Constituent Suspension Mass Solution
Inhibitor Inhibitor X X X
Stripper Vent
Styrena X I
Mixing Tank Styrene I
Vent
Initiator I
Reactor Vents tyrene I X X
Initiators I I
Suspension I
StabilJrer.
Solvents
Was). Tank Vent Styrene I
Centrifuge Polystyrene and
Vent Styrene Particulate.
dnd Emissions I
Disti l latinn Styrene I
Column Vent
Polymer lead Polystyrene and
Drying Vent Styrene Particulate.
and Emissions X
Entruder Vent Polystyrene and
Styrene articulates
and Emissions I
436
-------
Health effects information about inpat materials of partIcular concern
is provided in the paragraphs below. Table 10 summarized available toxicity
infr,rmation for major input materials. Additive information is provided in
!PPEU Chapter lOb.
Ranges of vlatile organIc emissions from which employee exposure
potential to volatile rganlc compounds may be e tia ated are shown in Table
173 for expand.ible bead prodt ctjon via suspension po t yilerjzatjon and Table
174 for sass an.i 1ution polymerization.
Health_Fffe t’
The input materials used In general purpose polystyrene ma’ufacture
include three si spected human or known aiiirnal carcinogens. They art carbon
tetrachioride, used as a chain transfer agent; polyvinyl alcohol, a suspen—
3ion stabilizer; and the the flame retardant, antimony oxide. Other input
rnaterta g that n y pose a significant health risk to plant employees due to
high toxicitieg are tert—butyl hydroperoxide, a free radical initiator, and
the retardant benzoquinone. The reported health effects of exposure to each
of these substances are summarized below.
Antim”ny Oxioe is a suspected carcinogen (5J which has also produced
positive resilts in tests for mutagenic effects. [ 156J Animal testing of
this substance Is limited, however, and no epidemiological da i exist.
Carbon Tetrachlorlde is a suspected human carcinogen [ 108J which is
also extremely toxic upon inhalation or ingestion of small quanttties.(241J
The toxic hazard pcsed by skin ab orption is slight for acute exposures, but
nigh for c’-rontc exposures.124I The toxicity of carbon tetr8ch uride
appears to be primarily due tG its fat solvent action h’ch destroys the
selective permeability of tissue membranes and allows escape of certain
essential substances such as pyridine nhlcleotides.1781 The OSHA air
standard is 10 ppm (8 hour TWA) tth a 25 ppm ceiling. [ 67J
Senzoguinone is a tumorigeric and a mutagenic agent, but testing has
produced Indefinite results for carclnogenicjty.fio5J The substanL. is
currently undergoing additional tests for carcitiog.neg(g by standard
hloessay orotr,. o1 under the s onsorhip of the National Toxfcology Program.
Renzoqutnone is very toxic; the probable and lethal oral dose for humans is
51) to 500 mg/kg. [ 85 The OSHA air standard is 0.1 ppm (8 hour TWA).167J
Stj,rene has been linked with iicreaged rater of chromogomal aberrations
in persons expc ed In an occupational aetting. 107J Animal test data
strongly support c idemfo ogical evidence of its mutagenic Potential.f233J
Styrene also produces t.imorg and affects reproductive fertI1 ty in labora-
tory anIm 1q.F2331 Tnxfr effects of exposure to styrenc jausily jnvolv the
central nervous system.f233J The OSHA air standard Is 100 ppm (8 hour TWA)
with a ceiling of 200 ppm.f67J
Terr—ButyJ H peroxIde ha produced symptoms of severe depression,
Ir ‘)rdlnatjr ,n, “yanosjs, and respiratory arrest in laboratnrj animals. [ 243J
Skin conL.lct Is associated with severe local reactions. L [ is(ted animal test
687
-------
TABLE L73. CHARACTERISTICS OF VENT STREAMS FROM EXPAN’ABLE POLYSTYRENE BEAD
PRODUCTION VIA SUSPENSION POLYMERIZATION
‘mission
rate,
5trean kg VCC/Mg Composition,
Name Nature product Wt.Z
Mix tank vents Intermittent 0.123 0.73 Styrene
0.53 Acrylonitrile
98.72 Air
Reactor vents intermittent 1.14 58.8 VOCa
1.4 Styrene
39.8 Air
Holding tank vents Intermittent 0.055 0.66 VOC 5
99.34 Air
Wash tank vents Continuous 0.024 0.35 voca
99.65 Air
Dryer vents ‘ ontinuous 2.89 0.066 0.21 VOC
99.934 — 99.13 Air
Product Improvement vents Intermittent —— 0.022 VOC
99.998 Air
Storage vents Continuous 0.746 0.002 VOC 5
99.998 Air
Total Emission Rate 4.98
agI , ,jng agent.
Soiree: Polymet Manufacturing Industry Ba. kground Information for Proposed
Standards , September P983.
488
-------
TABLE 174. CHARACTERISTICS OF VENT STREAMS FROM THE POLY,TYRENE
MASS OR SOLUTION POLYMERIZATION PROCESSES
Emission
rate,
Stream kg VOC/Mg Coui .osition,
Name Nature product Wt.Z
Monomer storage & feed Continuous 0.09 100 Styrene
dissolver
Reactor drum vent Intermittent 0.12—1.35 6.9 Styrene
35.0 Water
58.1 Air
Devolatilizer condenser Continuous 0.25-0.75 3 Styrene
vent 97 Air
Extruder quench vent Continuous 0.15—0.3 Styrene & steam
Total Emisbion Rate 0.61—2.5
Source: Polymer Manufacturing Industry Background Information for Proposed
Standards , September 1983.
489
-------
data also indicate mutagenic effects. No epidemiological data are avail-
able, however to evaluate the toxic hazard to humans.
Air Emissions
The sources of VOC fugitive emissions for polystyrene production are
listed in Table 172. A3l of these sources are vents. Cnttrol of emissions
from these vents may include routing the stream to flare to incinerate
hydrqcarbons or routing the stream to b1owdown.(7 5J Other fugitive VOC
emissions result from leaks in process equipmerc, such as flanges, valves,
cooling towers, open drains, and pumps. Alt’.ough control of these emissions
may be accomplished by equipment modificar. on, a routine inspection and
maintenance program may be the best coi’trol.
The sources of fugitive parti..ulates are also listed in Table 172.
Control of these sources may be *ccoapli .hed by venting these streams to
either a baghouse or electrost ,tic precipitator for particulate collection.
EPA estimates that only 30 people are affected by hydrocarbon emissions aid
2 are affected by part icula .es in the 100 person pe’ square km population
surrounding a polystyrene ,lant.(286J
Wastevater Sources
There are several wastewater sources associated with the various poly-
styrene production processes as shown th Table 175. The major vastewater
sources result from suspension polymerization which uses water to suspend
the reaction mi.ture and vash the polymer. The aqueous phase of the
polymerizatj •. mixture is removed from the polymer beads by centrifugation.
ThIs wa’-., along with the polymer wash water, is reported to contain 20 kg
of polystyrene per metric ton produced.(93J As Table 175 shows, all poly-
styrene processes generate water from monomer stripping and routine clean-
ing. Mas. and solution polymerization have vastevater from only these two
sources.
Ranges of several vastevater parameters for wastevaters from poly-
styrene production are shown below. Values for the vastevater from the
three CPPS pr ductton pr’cesses and the processes presented in the IPS
section were nt’t distingilshed by process or resin type by EPA for the
purpose of establishing effluent limitation. for the polystyrene
industry. [ 284J
Polystyrene
Wastewater Unit/Metric Ton
Characteristics of Polystyrene
Production o — 141.8 m 3
30D 5 0—2.2kg
COD 0—6.0kg
TSS 0—8.4kg
490
-------
TABLE 175. SOURCES OF WASTEWATER FROM POLYSTYRENE MANUFACTURE
Source Suspension Mass Solution
Monomer Steam Stripping. X X X
Polymer Bead Washing X
Centrifugatton X
Routine Cleaning Water X X X
491
-------
Solid Wastes
The solid wastes generated during polystyrene production include
substandard resins or beads which cannot be blended and collected particu—
lates, and low molecular weight polymers from mass polymerization. One
report estimates losses from mass polymerization processes to be 2 per—
cent.(93j No information is available in the literature regarding the
quantity of particulateg collected from air emission control devices. These
wastes are. not hazardous; therefore, their disposal should not pose an
environmental problem.
Environmental Regulation
Effluent limitations guidelines have been set for the polystyrene
industry. 3PT, MT, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New nource performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 !ayp. -
Carbon tetrachioride, a chain transfer agent, has been listed as a
hazardous waste and designated U211 (45 Federal Register 3312, Play 19,
1980). Disposal of carbon tetrâchloride or polystyrene resins which contain
residual amounts of this compound must comply with the guidelines see forth
Ii h. Resource Conservation and Recuvery Act (RCRA).
492
-------
SECTION 22
POLYSTYRENE (IMPACT)
L.PA Source Classification Code—Polyprod. General 3—Ol-01802
INTRODUCTION
Impact, or rubber modified, polystyrene (IPS) is a translucent to
opaque v ite polymer whfch is resistant to wear and exhibits high impact
strength. IPS has less gloss and clarity than general purpose polystyrene
(GPPS), but exhibitp increaaed impact strength when compared to GPPS and
displays the rigidity and ease of fabricatiun of the general purpose
resin.(146J The production of IPS is achieved by the addition of either
polybutadiene or styrene—butadjene rubber to the styrene monomer. The
rubber remains as diacret particles dispet; ’l in the polymer after polymer—
ization.1171 Althou 1 !, the impact strength of the modified polymer is
improved, the tensile strength and hardness are lowered, and the softening
point is reduced by the addition of the rubbec. This section describes the
manufacture of rubber modified polystyrene; the section on general purpose
puiystyr .iie presents the types of proceases usec ii. the manufacture of the
homopolymer.
Tables A—3O and A—3 1 in Appendix A include some typical properties for
impact polystyrene. As these tables show, IPS has low specific gravity and
good thermal stabiliLy. IPS is usually classified a: ording to rubber con-
tent a3: ue um 1mp ct, with 3 to 10 percent rubber; high impact, with 5 to
10 percent rubber; and super impact, wtth up to 25 percent rubber.
The ease with which polystyrene can be fabricated using heat makes
polystyreie products low In ost. Its excellent thermal and electrical
properties render polystyrene useful for manufacturing interf or doors,
lighting covers, air conditioning housing, and shutters. Other applications
includ2 flower pots, margarine tube. . app, closures, dLsposable cutlery,
drain pipes, toys, drinking cups, and egg cartons. In 1980, impact poly-
styrene accounted for 51 percent of the total polystyrene produced. General
purpose polystyrene and expandable beads captured the remaining 49 percent.
[ 35J
Rubber modified polystyrene is produced via mass polymerization, sus-
pension polymerization, or solution polymerization. The rubber can be added
by: blending the rubber latex with the polystyrene latex followed by coagu-
lation and drying; mech .nLcally mil! ng the dry rubber with the dry poly-
styrene; arid grafting of preformed nsaturated rubber with styrene in mass,
suspension, or solution polymerization processes. The copolymertzatioy
493
-------
process is often referred .. , as graft polymerization and is the most widely
used nince it produces superior products with less rubber.(17J
INDUSTRY DESCRIPTION
The polystyrene industry is comprised of 18 producers of general pur-
pose and/or impact polysryrene, three of which also produce atyrene—buta
diene latexes in additha to the polystyrene. Publiehed information does not
disclose which producers manufacture impact polystyrene. These 18’ producers
have 44 sites, 17 of which are in Ohio, Michigan, Illinoia, and
Pennyalvania, and another 8 in California. The remaining plants are located
in the east and southeast. Polystyrene producers are listed in Table 176
and styrene—butadiene latex producers are presented in Table 177.
Polystyrene is used in consumer related industries, such as construc-
tion, appliances, and packaging. Therefore, polystyrene consumption follows
the trend set by housing starts and consumer spending. After a production
peak of 1,820,000 metric tons in 1979, a drop to 1,490,900 metric tons
occurred in 1980.(35, 65j Most of the expaision planned is for expandable
polystyrene. Excess capacity for impact polystyrene is sufficient to sup-
port industry growth for the near future. Therefore, no new plants for
impact polystyrene are expected to be built.
PRODUCTION AND END USE DATA
In 1980, total polystyreie sales were 1,490,900 metric tnns.(35j Poly-
styrene is used for packaging, toys, foam insulztion, electrical and elec-
tronic uses, and serviceware, which includes the familiar cups. Table 178
presents the 1980 conrumption of polysty ene. These products can be classi-
fied as either molding resins, extrusion resins, or expandable beads.
Impact po1 utyrene contributes 64 and 51 percent of the total polystyrene
produced for molding and extrusion resins, reepectively.(333
PROCESS iESCRIPTIONS
Impact polystyrene is produced by suspension, mass, or solution polym-
erization. According to one esttmate, over half of the impact polystyrene
produced is manufactured using a suspension process where the pr.polymerlza—
tion is carried to 20 to 40 percent completion in a bulk reactor and the
remaining conversion is performed by suspension polyuerization.(17J The
remainder of the impact polystyrene production is performed by sass or solu—
Lion polymerization. Suepcnsion polymerization as a method of manufacturing
impact polystyrene offers excellent versatility for the production of
numerous types of products; however, high—purity products are more difficult
to obtain since water, suspens on stabilizers, and unreacted initiators are
contaminants. The added cost for the addition of stabilizers and vastewater
treatment also make mass polymerization a sore favorable process.12, l47J
Due to the narrowing price increase from styren. monomer to polymer, mass
p&ymerization will probablg become the major process used. ,(l47J
Alt’ ough the rubber can be incorporated into the polystyrene by
mechanical seams, polymerization of the rubber with the polystyrene (often
494
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TABLE 176. MAJOR U.S. PRODUCERS OF POLYSTYRENE
Capacity as oE July 1, 1981
(Thousand Metric Tons)
General
Purpoce Expandable
Producer and Impact Bead — Total
A&E Plastik Pak Co.
A&E Plastics Division
City of Industry, CA 15.9 0 15.9
American Hoechst Corp.
Plastics Divisjo
Chesapeake, VA 118.2 0 118.2
Leomtngter, MA 54.5 0 54.5
Peru 1 IL 77.3 36.4 113.6
COMPANY TOTALS 250.0 36.4 286.4
American Petrofina Inc.
Ccsden Oil & Chemical Co.,
subsidiary
Big Spring 1 TX
Calumet City, IL 77.3
,Orange, CA 27.3
Windgrz, NJ 54.4
Atlantic Richfield Co.
ARGO Polymers, Inc., sub.
Beaver Valley, PA 34.4 159. lb 213.6
BASF Wyandotte Corp.
Polymers Grou g
Styropor Division
Jameeburg, NJ 0 79,5C 79.5
Dow Chemical USA
Allyn’s Point, CT N/A N/A 86.4
Ironton, OH H/A N/A 86.4
Joliet, I L. N/A N/A 63.6
Mid’and, MI N/A N/A 100.0
Torrance, CA N/A N/A 9 0.9d
COMPANY T’)TALS 418.2 427.3
N/A — Not Available
(continued)
495
-------
TABLE 176 (continued)
Capacity as of July 1, l 9 8i
(Thousand Metric Tons)
Genera
Pt rpoae Expandable
Producer and Tmp ct Bead Total
Carl C.,rdon Industries, Inc.
Hammond Plastics
Oxford Division
Oxford, MA 45.5 0 45.5
Hammond Plastics Midwest, tic.
Ovensboro, KY 22.7 0 22.7
COMPANY TOTALS 68.2 0 68.2
Gulf Oil Corporatiou
Gulf Oil Chemicals Co.
Plastics Division
Marietta, OH l40.9e o 140.9
Hunt sman—Goodson Chemical
Corp.
Troy, OH 9.1 0 9.1
Kama Corp.
Hazeltown, PA 11.4 0 11.4
Mobil Corp.
Mobil Oil Corp.
Mobil Chemical Co.,
Division
Petrochemicals Division
Holyo e, MA 40.9 0 40.9
Joliet, IL 18.2 0 18.2k
Santa Anna, CA 29.3 0 29.3
COMPANY TOTALS .—o. en
Monsanto Co.
Monsanto Plastics and
Rvatns Co.
.ddyston, OH 136.4 0 136.4
Decatur, AL 45.5 0 45.5
Long Beach, CA 22.7 0 22.7
Springfield, MA 136.4 0 136.4
COMPANY TOTALS 340.9
(continued)
496
-------
TABLE 176 (continued)
Capacity as of July 1, 1981
(Thousand Metric Tons)
General
Purpose Expandable
Producer and Impact Bead Total
Polysar Group
Polysar Inc.
Resins Division
Copely, OH 54.5 0 54.5
Forest City, NC 18.2 0 18.2
Leominster, MA 54.5 0 54.
COMPANY TOTALS 127.3 0 127.3
Shell Chemical Co.
Belpre (Marietta), 011 136.4 0 136.4
Standard Oil Co. (IN)
AMOCO Chemical Corp., aub.
Joliet, IL 136.4 0 136.4
Torrance, CA 15.9 0 15.9
Willow Springo, IL 40.9 0 40.9
COMPANY TOTALS 193.2 0 193.2
Texatyrene Plastics, Inc.
Fort Worth, TX 0 22.7 22.7
U.S. Steel Corp.
USS ChemLcaie Division
Haverhill, OH 9.18 0 9.1
Vititek Inc.
Delano, CA — 0 2.3 2.3
TOTAL 2,068.2 3 0 9• 1 h 2,377.3
auth begin production of expandable PS at this location by the end of
1981; eRrtmated capacity — 18,200 metric tons per year.
bCompany intend. to increase expandable PS capacity to a total o 227,300
metric tons per year.
(continued)
497
-------
TABLE 176 (continued)
CCompany viii add expandable PS production capacL., of 20,500 metric tons
per year by 1933.
done production train was put on standby in August 981.
ecompan, viii increase capacity to 200,000 metric tona per year by earij
1983.
company capacity vi .l be !ncreased by 118,200 metric Lone per year by
early 1983.
STaciiLt was closed in Septenter 1980 vith the exception of this smell
amnunt of impact resin produced.
hGeorgja Pacific Corp. plans to complete 29,500 metric tons per year of
its expandable PS capacity in Painesvilie, CA by 1982.
Sources: Chenical Economics Handbook , updated annually, 1981 flata.
Directory ot Chemical Producers , 1981.
498
-------
TABLE 177. POLYSTYRENE PRODUCERS WHICH ARE ALSO
MAJOR STYRENE- BUT.%DIENE LATEX PRODUCERS
Dow Chemical USA
Allyn ’s Point, CT
Dalton, GA
Freeport, TX
Midland, MI
Pitt .burgh, CA
Polysar Group
Poly.ar Inc.
Polysar Latex
Beaver Valley, PA
Chattanooga, TN — 2 plant.
U.S. Steel Corp.
USS Chemical. Diviglon
Scott. Bluff, LA
Source: Chemical Economic. Handbook , ‘pdated annually, 1981 Data.
499
-------
TABLE 178. CONSUMPTION OF PULYSTYRENE FOR 1980
Thousand Metric Tons
Packaging 568.2
Housewares, furniture, and
furnishing, consumer products 181.8
Electrical/electronic uses,
appliances l6 .2
Toys, sporting goods, recreational
articles 140.9
Con,tructtoi 136.4
Serviceware and flatware 109.1
Miscellaneous commercial and
industrial solding 81.8
Other uses (medical/dental and
other laboratory articl s, combs,
bru bes, eyeglasses, sig ie,
writing utenefle, office and
choo1 supplies, novelties and
miscellaneous uses) 104.5
1,490.9
Source: Chemical Economtce Handbook , updated annually, 1981 Data.
500
-------
referred to as graft polymerization) is the typical process. Copolymeriza—
tion of the tubber and the styrene produces more homogeneouq products with
less rubber.f17J Tables 179 anc 180 present typical input materials’and
operating parameters for these processes. Specialty chemicals used in this
process are listed in Table 181.
Impact polystyrene is produced by the polymerization of styrene in the
presence of rubber. The reaction may be initiated by heat, but a rAdical
initiator is typically used. The polymerization of impact polystyrene dif-
fers from polymerization of general purpose polystyrene since the unsatu-
rated rubber molecule also becomes a radical group which then reacts with
the styrene monomers and polymers. The free—radical initiator (R ) reacts
with the rubber molecule, typically polybutadiene, to e’art the polymeriza-
tion reaction. As styrene monomers and polymers combine with the polybuta—
diene radicals, the poljmer chain is propagated. Polymerization terminates
when the rAdical reacts with an electron accepting group CR’ ) , which is
called chain transfer. Termination also occurs when two radical groups
react with each other, or by disproportionatjon. Molecular weights of com-
mercial impact polystyrene grades range from 54,000 to 416000.(147J The
polymerization steps are depicted below:
Zn it tat to %
5• • C9 2 CH.CHCiI 2 — III • CXC 5 Ciic 2
Ptop. t to , ’
CHCN_C)1C5 2 *... +
1ICH.CHCH
CR—CS -
[ 62]
. o
n
501
-------
TABLE 179. TYPICAL INPUT MATERIALS TO IMPACT POLYSTYRENE PPODUCTION
PROCESSES IN ADDITION TO STYRENE MONOMER AND RUBBER
Organic Suspension
Process Water Initiator Solvent Stabilizers
Suspension X X X
Mass X
Solution X X
TABLE 180 • TYPICAL OPERATING PARMETERS POR IMPACT POLYSTYRENE
PRODUCTION PROCESSES
Process Temperature Pressure 8 Reaction Tim .
Suspension 110—170°C Reduced 5—9 hour.
‘lass 80 — 200°C Slightly reduced 12—18 1 rs
to 10—20 mm Hg (betch)
2—8 hours
(continuous)
Solution 90—130°C Atmospheric to 6—8 hours
10—20 ims Hg
5 Includin 5 dev 1ati1tzation step.
Sources: Lyle P. Aibright, Processes for Major Addition—Type Plastics and
Their Monomers , 1976.
Encyclopedia of Polymer Science and Techn. U .
502
-------
TABLE 181. INPUT MATERIALS USED IN IMPACT POLYSTYRENE MANUFACTURE
(IN ADDI’ION TO STYRENE MONOMER AND RUBBER)
Free Radical Initiators azobisisobutyronitri].e
benzoyl peroxide
dimethylaniljnea
di—tert—butyl peroxide
tert—butyl hydroperoxide
Chain Transfer Agents alkyl mercaptans
—methyl styrene dimer
carbon tetrabromjde
carbon tetrachioride
e thylbenzene
Retardants ard Inhibitors tert—buty l—pyrocatechol
benzoquinone
sulfur
ferric salts
1 ,l—diphenyl—2—picrylnydrazyj
oxygen
tert—butylcatechol
Solvents ethylbenzene
Suspension Stabilizers alkaline earth phosphates,
(procective colloids) carbonates, and/or silicates
gelatin
magnesium silicates
methyl cellulose
pectin
polyacrylic acid and its salts
polyvinyl alcohol
polyvinyl pyrrolidone
starch
sulfonated polystyrene
zinc oxide
Flame Retardants alkyl phosphates
antimony oxide
aryl phosphates
hydrated aluminum oxide
(continued)
503
-------
TABLE 181 (continued)
Lubricant mineral oil
Antioxidant 2 , 6 —dL(tert—bIltyl)—4..methyl..
phenol
aused only in conjunction vith beuzoyl peroxide at by temperatures.
Sources: Lyle F. Albright, Processes for Major Addition Type Plastics aLd
Their Monomers, 1974.
El cyclopedja of Polymer Science and Technology .
504
-------
T.r inat ion
Radical Co ibinaC ton
CHCIICI*CH 2 +
[ r2 J
CK 2 CR.CRCJH 0
C)iain Transfer
r McH 2
+ VR” ‘ [ zo] n
(II ( I
I H a 4 H2_Q
DlBproportionation :
‘.CHCH—CHCH 2 -.
.CHCH-CHCH ... ‘ .C1ICI-CUCH ... CHCR-C1ICH
2 2 • 2
• r II 2
t ’O} +
L H
+ R’S
505
-------
Oxygen reacts with the free radical initiators used, thus making a peroxide
radical shown below:
.
RI + O -*RO 2
This slows the reaction rate. Polymerjzatiom is performed in a nitrogen
atmosphere to minimize this reaction.
Suspension Polymerization
Suspension polymerization of impact polystyrene uses water and a aus—.
pending agent to separate the monomer into droplets for the polymerization
process. The major advantage of this process as compared to other methods
is the production of the polymer in small beads which may be easily
sep.lrated. Although the polymerization rate is slower, the cost higher, and
tbe contamInation more severe for suspension polymerization than mass or
solution polymeriz tjo , the advantages of this process include: excellent
heat transfer, no solvent recovery problems, fewer safety hazards, simpler
temperature control, and narrower range particle size control possible.
Aa illustrated in Figure 56, the styrene monomer is stripped to remove
the inhibitor added to prevent polymerization during shipping and storage.
The stripper water is sent to vastevater treatment while the styrene is
combined with a monomer—soluble free radical initiator. The resulting
mixture is fed to an agitated reactor filled with water where a dispesjng
agent and a suspension stabilizer (which maintain the styrene mixture as
aqueous phase droplets) are added with the rubber. After the droplets have
polymerized, the polymer beads are washed with acid to remove any residuals
or contaminants. The wash water is sent to vastevater treatment while the
wet polymer beads are centrifuged and dried. The water removed during
centrifugation is combined with the other wastewater produced by this
process. Any remaining unreacted atyrene compounds and contaminant. are
removed from the polystyrene in the devolattlization extruder.
A typical recipe for auspengion polymerization of IFS is given below
for both the prepolymeriza j 05 and polymeriza j step .:f2J
Prepolymerization — Quantities of each material are unknown.
Styrene—gubber Mixture (6Z rubber) (monomer)
Di(tert_buty1)pa o j (initiator)
Antioxidant
C 12 Mercaptan (molecular weight regulator)
Refined Hydrocarbon Oil. (lubricant and plasticizer)
S 06
-------
Figure 56. Polystyrene production using the suspension polymerization process.
Source: Encyclopedia of Polymer Science and TechnoloM .
INHI alma
STazpp :
TAN&
te
V t
rAzz
“ S
0
.1
t I
Po2y yr .n . PO1y s styr e
To Wa .t t.t Bead. POllet.
Tr. .t ot
-------
Polymerization
Material Parts by Weight
Prepolynerized Solution 100
Water 200
Surfacta4t 0.25
Calciun Chloride (stabilizer) 0.15
Acrylic Acids and Other Acrylates (comonolner) 0.25
Typical water to monomer ratios range from 1:1 to 4:1 and the particle
size of the monomer ranges from 0.1 to 1 mm.(l10J Final polymer volatile
concentrations as 1ev as 0.5 percent can be produced using devo.Latllization
extrusion at reduced pressure, typically 10 to 20 me Eg.(18J Reactors are
aluminum, stainless steel, or stainless steel clad material.. Copper is not
used since it discolors the polymer,
Mass Polymerizat o
Mass (or bulk) polymerization j the simplest process by which impact
polystyrene can be made. The polymer chain ii modified with the rubber
molecules to form a copolymer which has slightly reduced clarity and gloss
when compared to general purpose grades but e,hibits improved impact
strength. The polymerization of polystyrene is difficult to control due to
its highly exothermic naturø, and ma ss polymerization is the moat difficult
of the processes used since the viscosity of the polymerizing mass increases
-as the convereton increase;. Hovever, mass polymerization of polystyrene
results in little contamination of the polymer by water, solvent, me
susperisto- stabilizers.
)‘aas polymerization as depicted in Figure 57, consists of four basic
steps prepolymerigation, polymerization, devolatiiizatton, and extrusion.
Prior to polymerization, the styrene monomer is stripped of the inhibitor
used to prevent polymerization during shipping. The styrene is fed to the
reaceor while the stripper water is.seat to vastevater treatment. A typical
recipe fo: mass polymerization of IFS was not found in the literature;
however, it was reported to be similar to that used in the prepolymerigation
‘reaction described above.
The equipment used In the prepolyiserjzatjon step consists of a atirrad
reactor with a ref lux condenser operating under reduced pressure. This
enables control of the reaction temperature by removing a portion of the
vaporized monomer and returning the condensed liquid s yrene to the reactor.
If peroxidtc initiators are used, the reaction may be carried out at a lower
temperature (80’c) than that used for thermal initiation (130°C). The
polymer content rf the resulting mixture varies from 25 to 35 percent.
From the prepolymertzatjon section, the monomer—polymer mixture is fed
into a serie of stirred eflux reaction kettles or reaction Lovers, The
temperature is progressIvely raised through the reaction zone to prevent
508
-------
Vtrnt
Figure 57. Polystyrene production via mus polymerization.
Sources Lyle F. Aibright, Processes for Major Addition Type Plastics and Their Manufacture , 1974.
Encyclopedia of Polymer Science and Technology .
INH IB1TUIi
srai vu
to Wm.tsw.i.r
U’
C,
V .it
• Disi 1LLA 1OLI
Luw Ik I uj r
Lghc Pulymur
To Looij(j11
DLVOLATI.IZLa
Ire ne
PeLlet.
-------
fall of I is polymerization rate and to reduce the viscosity of the polymer—
izing mass. Typical final temperatures In the polymerization section range
from 150 to 200’C.(2, 17J Materials of construction for the reactors are
aluminuis, stainless steel, or stainless steel clad material.. Copper is not
used since it causes discoloration of the polymer.
In order to remove unreacted onoser and low molecular weight pol7mers,
the reaction mass is then fed to a static devolatiliger wher, the volatiles
are flashed off and distilled. The styrene monomer and oligomers are
recycled while the low molecular weight polymers are sent to a landfill. The
purified polymer is then extruded through a vented extruder and peUetized.
Solution Polymerization
Solution polymerization of impact polystyrene has several advantages
over the mass polymerization process. The viscosity of the polymerization
medium is lower, the temperature control is easier, and the molecular weight
of the polymer is lower. Although this process allows better heat dissipa-
tion, the solvent reacts with the polymer chain, resulting in more contami-
nation of the product.
As illustrated Lu Pigure 58, the etyrene monomer is stripped to remove
the inhibitor added to prevent polym.rjzation during shipping and storage.
The stripper water is sent to vastevater treatment whil, the styrene is
diluted with ethylbenzene and fed along with the rubber to a series of
agitated reactors, or a tower reactor, with heat exchange zones. After
polymerization, the unreacted etyrene, rubber, and solv nt are removed from
the polymer and recycled. The purified polymer is than extruded into
strands and cut into pellots.
The ethylbensen, concentration of the incoming solution to the reactors
ranges from 5 o 25 percent. Temperatures in the reactors start at 110 to
130C in the first stage and increase to 150 to 170C in the last stage.
Devolatiligation temperature, under reduced pressure, is usually 230’C418J
Small amounts of a lubricant such as mineral oil (about 3 percent) may be
added.(208J Reactors are aluminun, stainless—steel, or stainless steel clad
materials. Copper is not used since it discolors the resulting polymer.
A typical recipe for solution polymerization of Ifl is given belows 123
Material Parts by Vejahi
Styren. (monomer) 2,079
Polybueadje e (r’thb,r) 121
Ethylbengene (solvent) 220
Mineral Oil (lubricant and plasticia , ) smell amount
2 ,6—Di(tert—buty l)—4...ethyl phenol
(antioxidant)
S—methylstyren. (.ol!cular weight regulator)
510
-------
Figure 58. Polystyretie production via eolutjo polymerization.
Source: Encyclopedia of Polymer Science and Technology .
INHIIITOR
STRIppgg
To Wastewater
Treatuient
REACTOR(.)
Vent
Po1yacyre 0
Pellets
-------
Energy Reg tre.en
The energy required for polystyrene production is listed below by
technology: [ 208, 209, 21lJ
Unit/Metric
Techno1o Energy kequired Ton of Product
C.sden Technology, Ele.trjcity 6.30 x i 8 Joule.
Inc. Fuel 1.26 x Joules
Gulf Oil Chemicals Electrici 1 .y 9.01 x 108 Joule.
Co. Steam 0.4 metric ton
Socløte Chimique E! .ectricity 4.86 x 108 Joules
des Charbonnage. Net Fuel 4.19 x 108 Joule.
(CdF)——rhe Badger
Co., Inc.
E TR0Nj yr AND INDUSTRIAL. HEALTH CONSIDERATIONS
None of the chemLcal, which have been ,identjfied as inputs to poly-
styrene prOcessing are known human carc inogens. However, there is some
evidence, from tests conducted and reported’ to NIO$lr of polystyrene and
styrene causing tumors in test auima l .. [ 232J Although these results are not
conclusive, standards have been set for atyrene and polystyrene exposure.
Three other inputs to polystyrene proces ing are suspected human or known
nniisal carcinogens: carbon tetrachloride,a chain transfer agent; polyvinyl
a lcoho l,a suspenel.on stabilizer; and antimony oxide, a flame retardant.
Other highly toxic inputs include a free radical initiator, tert—butyl
hydroperoxide, and a retardant, benzoquinone.
One environmentally significant portion of polystyrene processing i
the devolatilization step. Residual monomer in the polymer is typically
reduced to less’, than one percent,, thereijy reduciag the exposure risk and
rendering the po1ymer usable for food app1ica ons such as meat trays, egg
cartons, and vrap for non—fatty foods.
Worker Distribution and Emissions Release Point .
We have estimated worker distribution for polystyrene production by
correlating major equipment manhour requirements with the process flow
diagrams in Figures 56 through 58. Estimates are given in Table 182.
No major emission point sources are associated with polystyrene pro-
duction. Although there are no major air emission point sources, f’ gitive
emissions may pose a significant ervironmental and/or worker health problem
depending on the components in the stream, operating conditions for the
process, engineering and administrative controls, nd maintenance programs.
512
-------
TABLE 182. WORKER DISTRIBUTION ESTIMATES FOR
IMPACT POLYSTYRENE PRODUCTION
Procegg Unit Workers/unjt/8—hour Shift
Suspension Polymerization Stea. Stripper 0.25
Batch Reactor 1.0
Batch Mixer 1.0
Washing 0.25
Cent:ituge 0.25
Dryer 0.5
Extr’ider 1.0
Mass Polymerization SteaL Stripper 0.25
Batch Reactor 1.0
Distillation Column 0.25
Devolatjljzer 0.25
Extruder 1.0
Solution Polymerization Steam Stripper 0.25
Batch Reactor 1.0
Flash Tank 0.125
Extruder 1.0
513
-------
Process eoures of fugitive emissions are listed in Table 183. Typical
inhibitors stabilizers and initiators are listed in Table 181. Ethylben—
zene is the elvent generally used in sOlution polymerization. Particulate
emission. from centrifugation, drying and extrusion operation may contain
harmful additiveg and may produce elevated nuisance dust levels.
Health effects information about input materials of particular concern
is provided in the paragraphs below. Table 10 summarized available toxicity
information for major input materials. Additive information is provided in
IPPEU Chapter lOb.
Health Effects
The input materials ised in impact polystyrene manufacture include
three suspected human or nown animal carcinogens. They are carbon tetra—
chloride, used as a chain transfer agent; polyvinyl alcohol, a suspension
stabiliz r; and the the flame retardant, antimony oxide. Other input
materials that nay pose a significant health risk to plant employees due to
high toxicities are tert—butyl hydroperoxide, a free radical initiator, and
the retardant beezoquinone. The reported health effects of exposure to each
of these substances are briefly summarized below.
Antimony Oxide is a suspected carcinogen (51 which has algo produced
positive resultiin tests for mutagenic effects.(156J Animal testing cC
this substance is. limited, however, and no epidemiological data aziet.
Carbon Tetrachloride is a susp ect ed human carcinogen 1108J which is
also extremely toxic upon inhalation or ingestion of small quantities.f241J
The toxic hazard posed by skin absorption is slight for acute exposures, but
high for chronic expogureg.(24jJ The toxicity of carbon tetrachioride
appears to be prImarily due to its fat solvent action which destroys the
seleceive permeability of tissue membranes and allows escape of certain
essential substances such as pyridtne nucleotides.(78J The OSHA air stand-
ard is 10 ppm (8 hour TWA) with a 25 ppm ceiling.(67J
p nzoquinoiae is a tumorigenic and a nutagenic agent, but testing has
g,roduced indefinite results for carcinogenicity.flo5j The substance is cur-
rently undergoing additional tests for carcinogenesis by standard bioassay
protocol under the sponsorhip ot the National Toxicology Program. Benso—
quinone is very toxic; the pobable and lethal oral dose for humans is 50 ta
500 sg/kg.(85J The OSHA air standard is 0.1 pP. (8 hour TWA)467j
Styrene ha. been linked with increased rates of chromogomal aberrations
in persons exposed in an occupational aetting.(1O7J Animal test data
strongly support epidemiological evidence of its mutagenic potenttal.(233J
Styrene also produces tumors and affecta reproductive fertility in labora-
tory aniisal3. [ 233J Toxic effects of exposure to styrene usually invol.e the
central nervous system. [ 233J The 0SH/ air standard is 100 ppm (8 hour TWA)
with a ceiling of 200 ppm.(67J
514
-------
TABLE 183. SOURCES OF FUGITIVE EMISSIONS FROM POLYSTYRENE MANUFACTURE
Process
Source Constituent Suspension Mass Solutiii
Inhibitor Styrcne X X X
Stripping Vent
Inhibitor X X X
Mixing Tank Styrene X
Vent
Initiator
Reactor Vents Styrene X X X
Initiators X X X
Suspension X
Stabilizers
Solventa X
Wash Tank Vent Styrene X
Centrifuge Polystyrene, Styrene,
Vent and Rubber Part j e w-
lates and Emissions x
Distillation Styrene X
Column Vent
Polymer Bead Polystyrene, Styrene,
Drying end Rubber Particu—
latee and Emiasiong X
Extruder Polystyrene, Slyrene,
and Rubber Particu-
lates and Emissions X X
515
-------
Tert—Butyl HydroperOXidn has produced symptoms of severe depress ian,
incoordination, cyanosis, and respiratory arrest in laboratory animals.(2 43 1
Skin contact Is associated with severe local reactions. Limited animal test
data also indicate mutagenic effects. No epidemiological data are. avail-
able; however, tO evaluate the toxic hazard to humans.
Air Emissions
The sources of VOC fugitive emissions for polystyrene production are
listed in Table 183. All of these sources are vents. Cont”ol of emissions
from these vents may include routing the stream to a flare to incinerate
hydrocarbons or routing the stream t bliwdown.12851 Other fugitive VOC
emi sions result frum leaks in process .quipment, such as flanges, valves,
cooling towers, open drains, and pumps. Although control of these emissions
nay be accomp1t ’ed by equipment modification, a routine inspection and
naintenance program may be the best control.
The sources of fugitive particulates are also listed in Table 183.
Control of these sources may be accomplished by venting these streans to
either a baghou3e or electrostatic precipitator for particulate collection.
EPA estimates that only 30 people are affected by hydrocarbon emissions and
2 are affected by particulates in the 100 person per square km population
surrounding a polystyrene p1ant.( 28 ô
Wastewa ter Sources
There ire’ several sources of vastevater associated with the various
polystyrene projuctiofl processes as shown In Table 184. The major waste
water sources result from suspension polymerization which uses water to
suspend the rea ’tion mixture arid w 5 eh the polymer. The aqueous phase of the
polymertzattOn mistute is removed from the polymer beads by centrtfugation.
This water, alon g with the polymer wash water, is rrported to contain 20 kg
of polystyrene per metric ton produced.(931 As Table 184 shows, all pnlr
styrene processes generate water from monomer stripping and routine clean
trig. Mass and solution polymerization !%ave vagtewater frum only these two
sources.
Ranges of several vaatewater parameters for vastewaters from polysty-
rene production are shown below. Values for the wastewater from the three
IPS production processes and the processes presented in the GPPS section
were not distinguished by process or rosin type by EPA fr the purpose of
establilihing effluent limitations for the po1ysty ene industry.(284J
Polystyrene
Wastevatet Unit/Metric Ton
Characteristic! of Polysty ene
ProductIon 0 - 141.8 m 3
BOD 5 0—2.2kg
COD 0-6.0kg
TSS 0—8.4kg
,l6
-------
TABLE 184. SOURCES OF WASTEWATER FROM POLYSTYRENE MANUFACTURE
Source Suspension Mass Solution
Monomer Steam Stripping X X X
Polymer Bead Washing X
Centrifugation X
RoutLne Cleaning Water X X X
517
-------
Solid Wastes
The solid wastes generated during polystyrene production include
substandard resins or beads which cannot be blended and collected particu—
lates, and low molecular weight polymers from mass polymerization. One
report estimates losses from mass polymerization processes to be 2 per—
cent.(93J No information is available in the lieterature regarding the
quantity of particles collected from air emission control devices. These
wastes are not hazardous; therefore, their disposal should not pose an
environmental problem.
Environmental Regulation
Ef fluent limitations guidelines have been set for the polystyrene
industry. BPT, M I, and NSPS call for the pH of the effluent to fall
between 6.0 and 9.0 (41 Federal Register 32587, August 4, 1976).
New source performance standards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include;
• Safety/release valves must not releaie more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
Carbon tetrachioride, used as a chain transfer agent, has been tested
as hazardous and designated U211 (45 Federal Register 3312, May 19, 1980).
Disposal of carbon tetrachioride or polystyrene containing residual amounts
of this compound must comply with the guidelines established in the Resource
Conservation and Recovery Act (RCRA).
518
-------
SECTION 23
POLYURETHANE FOAM
EPA Source Classification Code — Polyprod. General 3-01—018-02
INTRODUCTION
Polyurethane foams are cellular plastics produced by the reaction of a
polyol and a polyisocyanate in the presence of a blowing agent, catalyst,
and surfaetant. [ 65J Many multifunct±onal alcohols (polyols) may be used to
produce a wide range of products. Flexible and rigid polyurethane foams are
used in furniture, bedding, seating, construction, refrigeration, and auto-
motive parts. [ 217J Polyurethane foam constitutes 90 to 95 percent of the
polyurethane produced. [ 179J
0
I”
In addition to urethane groups (—N—C—0—), a typical urethane polymer
may contain aliphatic and aromatic residuals from the polyol used as well as
ester, ether, amide, or urea groups These groups do not necessarIly repeat
in any regular order. The degree of polyol functionality, reactant molecu-
lar weight and type, isocyanate structure, catalysis, and reaction condi-
tions all effect the resulting polymer’s form and physical properties. [ 217J
Typical properties for polyurethane foams of various formulations are listed
in Table A—32 in Appendix A. In general, as the molecular weight of the
polymer increases, the solubility decreases while a corresponding increase
occurs in the tensile strength, melting point, elongation, elasticity, and
glass—transitiou temperature of the polymer.1178, 179J The density of the
foam is controlled by regulating the water content, i.e., low density foams
require more water if the foam is water blown. Other blowing agents are
mainly halocarbons, such as dichlordifluoromethane and methyiene chloride.
Polyurethane foams are typically categorized as either flexible or
rigid. Flexible foams are evaluated in terms of recovery from compression,
or set, since they are used primarily in seating cushions, bedding and rug
underlays. Good recovery from compression allows use of the product over a
long period without deterioration in firmitesa or shape.
Rigid polyurethane foams have desirable properties which enable their
use n construction and refrigeration applications. These properties
include: excellent thermal Insulation, especially when blown with luoro—
carbons; a ct.4bination of high strength and light weight; good heat resis-
tance; good energy absorption for use in sound deadening or vibration
dampening; and excellent adhes 1 on to wood, metal 1 glass, ceramic, and fiber
surfaces.1178, 179J Thc use of polymeric isocyanates in the manufacture of
rigid foam give improved heat and flame resistance.
519
-------
Polyurethane foam is made by the prepolymer, quasi—prepolymer, and
one—shot processes. Virtually all of the polyurethane foam produced is I rom
the one—shot process; therefore, this process will be the only one
presented. ( 1133
INDUSTRY DESCRIPTION
The polyurethane foam industry is comprised of 24 producers with 64
plants in 25 states. Three regions contain almost tvo—third8 of the plants:
the sout!heaátern states (EPA Region IV), the Great Lakes states (EPA Region
V) and ‘the southwestern states (EPA Region I X) contain 17, ‘22, and 27
percent of the plants, respectively. Polyurethane foam producers and their
locations are listed in Table 185.
Polyurethane foam is used in the msnufacture of consumer hard—goods,.
including furniture and appliances, and the construction industry. In 1981,
U.S. polyurethane foài. saler. totaled 787,000 metric tons. Polyurethane
flexible foam sales rCacheda peak in 1978 of 655,000 metric tons vh ile
‘rigidioam sales reached a eak in 1981 of 256,000 metric tonó.(65 3 Total
‘polyurethane foam sales peakàd in 1978 at 891,000 metric tons. The current
capacity, as seen from the 1978 production lev. l, is adequate to enable
industry growth in the near future.
PRODUCTION AND END USE DATA
In .1981-,- U.S. eal e of polyurethane foam totaled 187,000 metric
tons. [ 65J Polyurethane foam’s many uses include:(178, 179, 2173
• Molded foam automotive parts, including safety pads, sun visors, arm
rests, bucket seats, seat cushioning, instrument panel trim, floor
mats, underlay., roof insulation, weather stripping, and air
filters;
• Rigid foam for use in the aircraft industry, as insulation for
household and commercial refrigerators, and in the flotation,
trane ortation, and furniture industries which includes decorative
pat. ., mirror frames, and chair shells;
• Flexible foa, for mattresses, furniture cushions, carpet underlay;
• Bonding material for fabric;
• Insulation for refrigerated trucks; and
• Foam for use in ,the construction industry, including curtain—wall
construction, preformed rigid panels, spray—applied wall
construction, and roofing insulation.
Table 186 lists polyurethane foam consumption for 1981 according to foam
type and market area.
520
-------
TABLE 185. U.S. POLYURETHANE FOAM PRODUCERS
Producer Location
Applied Plastics Co., Inc. El Segundo, CA
E. P. Carp;. ter Co., Inc. Conover, NC
La Mirada, CA
Richmond, VA
Riverside, CA
Russeliville, KY
Temple, TX
Tupelo, MS
Cook Faint and Varnish Co. Milpitas, CA
North Kansas City, MO
J)ov Chemical U.S.A. Ironton, Ohio
The Firestone Tire & Rubber Co.
Firestone Foam Products Division Conover, NC
Corry, PA
Elkhart, IN
Mili n, TN
Thomasvitte, CA
‘eneral Latex and Chemical Corp. Ashland, OH
Cambridge, MA
Cucamonga, CA
Dalton, GA
Geceral Motors Corporation
Inland DivisLn Dayton, OH
The BF Goodrich Co.
SF Goodrich Engineered Products Group
Fabricated Polymers Division Akron, OH
The Goodyear Tire & Rubber Co.
Chemical Division Bakersfield, CA
Logan, (‘H
Luckey, OH
Great Western Carpet Cushion Co., Inc. Orange, CA
(continued)
521
-------
TABLE 185 (continued)
Producer Location
Gulf Oil Corporation
Milinaster Onyx Group, subsidiary
Apache Building Products Co.
Division Belvidere, IL
Jackson, MS
Linden, NJ
North Salt Lake, UT
Mobay Chemical Corporation
Polyurethane Division Santa Ana, C&
Olin Corpàration
Olin Chemicals Group Fngelsville, PA
Plastic Management Corporation
G.F.C. Fo a Corporation, subsidiary Bridgeviev, IL
Carlstadt, NJ
East Rutherford, NJ
Hazieton, PA
Reeves Bros. Inc.
Curon Division Corneluis, NC
N.H. Robertson Co.
Freemen Chemical Corporation,
subsidiary Burlington, IA
Scott Paper Co.
Foam Division Eddystone, PA
Fort Wayne, IN
Sheller—Globe Corporation Tupelo, MS
D. Sobek Co. Fremont, CA
Textron Inc.
Industrial Product Group
Burkart/Randall Dibision Cairo, IL
St. Louis, MO
(continued)
522
-------
TABLE 185 (conttnuetf)
Producer Location
United Foam Ccrporation Boise, ID
City of Commerce, CA
Denver, CO
Fresno, CA
Hayward, CA
Honolulu, HA
National City, CA
Phoenix, AZ
Portland, OR
Sacramento, CA
Salt Lake City, UT
Seattle, WA
United Merchants & Manufacturers, Inc.
Glascoat Midwest Division Elkhart, IN
Glascoat Southwest Division Miami, FL
Thalco Division Los Angeles, CA
The Upjohn Co.
CPR Division Columbus, OH
Torrance, CA
Polymer Chemicals Division La Porte, TX
Witco Chemical Corporation
Isocyanate Products Division Chicago, IL
New Castle, DE
Source: Directory of Chemical Producers , 1982.
523
-------
TABLE 186. U.S. CONSUMPTION 0? POLTURETHiJE FOAMS
Market 1981 Thousand Metric Tons
Flexible Foam
Bedding 72
Furniture 200
Rug UnderlayA 52
Transportaton 130
Other _ 77
FLEXiBLE FOAM TOTAL 531
RIGID FOAM
Insulation 140
Furniture 10
Household and Commercial Refrigeration 50
Industrial Insulation 23
Transportation 22
Other 11
RIGID FOAM TOTAL 256
TOTAL 787
a1 e. not include 120,000 metric tons of rebondad underlay.
Source: Modern Plastics , January 1982.
524
-------
PROCESS DESCRIPT;ON
Polyurethane foam is predominantly manufactured via the one—shot pro-
cess. Although the prepolyiner and quasi—prepolymer systems have been used,
the one—shot process, which combines all of the Input materials simultane-
ously to products the foam, is the only commercial process now in use.(113,
178]
Polyurethane foam is produced by a polycondensation reaction between an
Isocyanate and a polyol. The react .on is influenced by the n1 ructure,
functionality, and type and location of substituents of the isocyanate;
structure of the polyol, presence of impurities or trace. of acid in the
isocyanate; and the reaction temperatt re , especially if it exceeds lOO’C.
Although choice of temperature, isocyanate, and polyol give some control
over the reaction, the choice of catalysts exerts the most control.f 178)
The polyurethane condensation reaction can be very complex since the input
materials and products may also act as catalysta for this process.
If no cacalyst is used, the polycondensation reaction between an
isocyanate and a polyol to form a urethane would appear as shown below:
R’NÔO + RON. f’N.c—O
I i°
L M
RON H ft 0
I - I \/1 II
R’N-C-OI .1 0 — R’NH-C-OR + ROB
a I IR’N-C-O
I
H RJ I 0
L/
ft H
If a basic catalyst is used, the reaction will proceed as shown below:
[ R-N.’C”OR-NaC 4 -0J + Basa— ft-N-C-0 1
ia. . ’]
I H R’
I \+/
R-N—C-0 R’OH I 0 0
Base+ 1 R—N—ç-0 RNH C_OR1 + Base
L se
525
-------
If an acid catalyst is used, the reaction proceeds as shown below:
R’NCO + H—Acid-*(R’—N—C-O• H”AcidJ
The progresson of urethane to polyurethane foam is depicted below. The
urethane molecule reacts with isocyanat. groups to form the polyurethane
chain. Carbon dioxide, which in turn acts as a blowing agent, is produced
by reacting water with isocyanates. Trace amountsi of free NH 2 and OH end
grnu i. ar. iiM In Phe polyurethane foam.
0 0
I’ II
O—C-N—R-NH—C-O-R’-O—C—NH-R—N-C-O + 2R(NcO) 2 + fl 2 0 r
0 0 0
II I I II
R’-O-C-NH-R-NH-C-NH-R-MH-C-NH-R-NH-C-NH-R-R’ +
The highly reactive —N—C ) group which charactertzes an iaocyanate also
leads to two important side react tons. One is the reaction with urea t’
farm a biuret and the other is reaction with a urethane molecule to form an
allophanate. These reactions are depicted below.
Urea
Biuret
0
II
RNCO + RNH-C-NHR -øR1 -CONHft
t 0NHR
Urethane Allophanate
0
RNCO + RHN-C-0R’—1u.R 1 -COOR’
ONHR
Rot’
0
I
R’NR-C-OR + 11—Acid
•0 .
526
-------
Tables 187 and 188 list typical input matecials and o erating param-
eters used for po!yurethane foam manufacture.
Polyuret).tne foam is produced primarily by the one—shot process, which
mixes all ingredients si’ ultaneouely. The polyol, polyisocyanate, catalyst,
surfactant, and water (or other blowing agent) are combined in a reactor
which is kc t veil agitated. Once the ingredients are uniformly mixed,
represented by the cream time, the contents of the reactor are emptied. The
reacting mixture which will gel to form the foam is poured onto a moving
conveyor, inclined 5 to 10 degrees above the horizontal to keep the liquid
from falling into the foam. The resulting slab is treated with heat or
steam to cure the surface, then baked in a curing oven to cure the polymer.
This process is illustrated in Figute 59.
Variations in the foam are achieved by altering the foam formulation.
The use of polymeric isocyanates gives a wide range of obtainable foam
properties which minimizes the need for compounding, a foam which can be
cold cured, and a reduced risk of isocyenate emissions due to the lover
vapor pressure of these compounds when compared to toluenediisocyanate
(TDI).(178J TDI is used almost exclusively in polyurethane foam manufac—
ture. [ 1791 Choice of polyol also gives a variety of foam types. For exam-
ple, encapsulating foams are obtained by using castor oil as the polyol.
A recipe to produce a typical furniture grade flexible polyurethane
foam is given below: (277J
Material Parts by Weight
Polyether Triol 100
Tolueiie Dtisocyanate 50
Water 4
Stannous Octoate (catalyst) 1
Silicone Copolymers (surfa tant) 1.5
T:Jchlorofluoromethane (blowing agent) 3
Po1yurethan ’ foam may be produced as slab stock, molded, sprayed, or
foamed into a retatni’ g cavity, such as a rnfrigerator housing. For a more
de aLled descriptioti i.f “foaming fn place”, see IPP U Chapter lOa, Section
10.
Energy Requirements
N data were found in the literature consulted listing energy required
for polyurethane foam production.
ENVIRONMENTAL AND INDUSTRIAL HEALTH CO ’lSIDERATIONS
Several chemicals associated with the production of polyurethane foam
have been listed as hazardous under RCRA: di—n-hutyl phthalate, dichioro—
difluoromethar e, dimethyl phthalate, dioctyl phthalate, ethyenediamine,
hydrocyanic acid, pyridine, resor inol, toluene diisocyanate, trichloro —
fluoromethane, and tris(2,3—d bromooropyl) phosphate. Isocyanates are
generally regarded to be skin sensitizers and irritants.
527
-------
TABLE 167. TYPICAL INPUT MATERIALS TO POLYURETHANE FOAM PRODUCTION
Function
Isocya nate dianisidine diisocyanate
2 5—dichiorophenyl isocyanate
3 4—dichiorophenyl. isocyanate
44 ‘—diphenylmethane diisocyanate
ethyl lsocyanate
hexaaethylene diisocyanate
hydrogenated methylene diphenyl
isocyanate
isophorone diiso.yanate
m—ehlorophenyl isocyanate
m—zylene ddsocyanate
methyl ieocy nate
met hylene diphenyl iaocyanate (MDI)
obutyl isocyanate
n—propyl isocyanat.
o—chlorophenyl isocyanate
octadecyl isocyanate
p-chlorophenyl isocyanate
phenyl ieocyanate
toll dine diisocyanate
toluene diisocyanate (TDI)
Poly ls poly(oxypropylene) adducte of glycerol
poly(oxypropylene) adducts of 1,2 ,6—
hexanetriol
poly(ozypropylene) adducts of
pentaerythritol
poly(oxypropylene) adducta of sorbitol
poly(ozypropylene) adduct. of
trimethylol propane
poly(oxypropylene) gi ycol.
poly( oxypropylene—b-ozyethylene) adducts
of ethylenediamine
poly( oxypropylene—b—oxyethylene) adduct
of trimethylolpropane
poly( oEypropylene—b—oxyethylene) glycola
Polyester. Polyesters made from:
adipic acid
I ,3—butylcne glycol
1 4-butjlene glycol
caprolactone
diethylene glycol
ethylene glycol
phthalic glycol
propylene glycol
(continued)
528
-------
TABLE 187 (continued)
Function Compound
Polyethers propylene oxide adducts of
a —methylglucoside
ethylenediamine
glycerol
pentaerythri tol
sorbitol
sucrose
trimethylol propane
Catalysts
Acid boron trifluoride etherate
hydrogen chloride
Tin dibutyltin diacetate
dibutyl tin salts used vith low concen-
trations of the following anticxi—
dante; catechol, resorcinol, t—butyl
catechol, or tartaric acid
dimethyltin dichioride
di—n—butyltin dilaurate
n—butyltin trichioride
stannic chloride
etannous chloride
stannous octoate
etannous oleate
trimethyltin hydroxide
tri—n—butyltin acetate
tetra—n—butyltin
Amines and Other
Organic Catalysts benzyltrimethylammonium hydroxide
bie(2—dimethyl aminoethyl) ether
cobalt benzoate
cobalt 2—ethyihexoate
cobalt naphthenate
cobalt octoate
d Iethyl cyclohexylamthe
dimethylaminoethyl piperazina
4—dimethy1 mine pyridine
dimethylethanolamine
lead benzoate
lead 2—ethyihexoate
lead oleate
(continued)
529
-------
TABLE 187 (continued)
Function Compound
Amines and Other
Organic Catalysts
(Continued) lithium acetate
manganese 2—ethyl’ exoate
manganese linoresinate
manganese naphthenate
methylmorpholine
N—aiainoethyl piperasine
N—ethylened lam Inc
N—ethyl morpholine
N—methyl morplioline
N—tetraisethylenedia.ine
N—tetramethylenedjai.jne—l,3—butape —
diamine
N, N—dimethylbenzylamjne
N ,N—dime thylcyc lohexylamine
N ,N—dimethylethanolamjne
N,N,N’ ,N’—tetrakis(2—hydroxypropyl)
ethylene diamine
N,N,N’ ,N’—tetrainethyl butane dia2ine
oxybis(dimathylaminoethane)
potassium oleate
pyr idine
sodium propionate
tetramethyl guanidlne
triethylenediaml ne
1 . 2 1 4 —trimethylpiperazine
zinc 2—ethyihexoate
zinc naphthenate
zirconium 2—ethyihexoata
zirconium naphthenate
zirconium toluens
Other antimony pentachloride
antimony trichlortde
Blowing Agents barium azodicarbozylate
benasne sulfonyl hydrazide
chlorofluorocarbone
dichiorodi fluoromethan.
trich lorofluoroi.ethane
diazoami nobenzene
ethyl chloride
methyl chloride
methylene chloride
(continued)
530
-------
TABLE 187 (conttnued)
Function Compound
Flame Retardants amnonium polyphosphate
(Phosgard P/30S)
chlorinated paraf fins (with antimony
trioxide)
fine grade alumina trihydrate
o ,O—eiethyl—N ,N—bis—(2—hydroxyethyl)
aminomethyl phosphonate
tris(2—chloroethyl)phosphate
tris(2 , 3—dlbromopropyl)phosphate
(tris”)
tris(2 3-dichloropropyl)phosphate
zinc borate
Surfactant alkylsilicone—peroxyalkylene copolymers
peroxyalkylene—polydimethyl si] oxane
organos ilicones
dimethyl silicone polymer
Cell Size Control
Agent mineral oil
Color Enhancer
(Color Stabilizer) triphenyl phosphite
zinc dibutyl tricarbonat
UV Light Stabilizer benzophenones
Clarifier copper salts
Flow Control Agent cellulose acetate butyrate
Gloss Control colloidal silicas
silica aerogela
Pigments acetylene black
aniline dyes
antimony eilico colors
antimony trioxide
benzidine toners
cadmium colors
carbon black
brome oxides
(continued)
531
-------
ThBLE 187 (continued)
Function Compound
Pigments (Continued) chromium colors
dioxazine colors
fluorecent zirconium dioxide
hydroxyazo-inetal chelate
iron oxides
Lake toners
Lithol tonere
molybdenum colors
nickel azo colors
phtha locyanines
Quinacridine colors
strontium colors
titanium dioxide
titanium zirconates
zirconium dioxides
Fillers ct-cellulose fiber
aluminum silicates
asbest me
barium sulfate (barytes)
barium zirconate
barium zirconate silicate
calcium carbonate
calcium silicate
calcium zirconate silicate
cellulosics
China clay (Kaolin)
chopped glass fibers
glass beads
glass flake
graphite
hydrated alumina
mangesium zirconium silicate
mica, natural and synthetic
nylon fiber
pearlite
polyester fiber
polypropylene fiber
silica, natural and treated
talc
vermiculite
zirconium silicate
zirconium spinel
(continued)
532
-------
TABLE 187 (continued)
Function Compound
Plasticizers adipates
didecyl adipate
dioctyl adimpate
aromatic oils
chlorinated diphenyls and polyphenyls
chlorinated waxes or paraff ins
phosphates
cresyl diphenyl phosphate
octyl diphenyl phosph&te
tributyl phosphate
tricesyl phosphate
trioctyl phoeph te
triphenyl phosophate
tria(2—chloroethyl) phosphate
tris( 2—chiorphenyl) phosphate
tria( 2—chioropropyl) phosphate
phthalatee
butyl/benzyl phthalate
dibutyl phthalate
dicapryl phthalate
didecyl phthalate
dilsobutyl phthalate
diisooctyl phthalate
dimethyl phthalate
dioctyl phthalate
Stabilizers benzaldehyde
hydroquinone
pyrogallol
resore inol
t—butyl catechol
Blocking Agents
Low Temperature acetyl acetone
bisphenols
dimethylamino methyl phenols
ethyl acetoacetate
ethyl malonate
hydrocyanic acid
novolaks
(coat inu.d)
533
-------
TABLE 187 (continued)
Function Compound
Medium Temperature caprolacta.
imidea
mouocthylaniline
phenol mercaptans
phenolic tertiary amines
pyrocatechol
quarternary amines
High Temperature diphenyl amine
hydrozy biphenyl
isooctyl phenol
phenol
pyrrolidone
Sources: Advances in Urethane Science and Technology, H. C. Friech, editor,
Anna W. Crull, Polyurethane and Other Foams , 1979.
Anna V. Crull, Polyurethane: Developments, Processes , 1978.
E. N. Doyle, The Development an 1 Use of Polyurethane Products ,
1971.
Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science md Technology.
Polyurethane Technology , Paul F. Bruins, editor, 1969.
534
-------
t BLE 188. TYPICAL OPERATING PARAMETERS FOR POLYURETHANE
FOAM PRODUCTION
Parameter Value
Premix Temperature 18 — 22C
Isocyanate Teilperature 18 — 22C
Cream Timea 10 sec
Gel Time 45 sec
Rise Tiee 90 sec
aTime required to achieve uniform mixing.
Source: Polyurethane Technology , Paul F. Bruins (ed), 1969.
535
-------
Vent
MIXING
TANK
Polyurethane
F ,am to
Curing Ovens
Figure 59. Polyurethane foas prodiction using the one—shot process.
Source: Encyclopedia of Polyaer Science and Technology .
Isocyanate
Pol .yol
Catalyst
Blowing Agent (Water)
Additives k
T
C)
Heat or
Stea
/ (OPt tonal)
CONVEYOR ( )
536
-------
Tris(2 ,3—dibronopropyl) phosphate, tris(2—chloromethyl phosphate),
antimooy oxide, and dioctyl phthalate (DOP) are suspected human carcinogens.
Other input materials posing a significant health risk include hydrocyanic
acid, pyrocatechol, phenol, antimony trichioride, triethylamine, hydro—
quinone, resorcinol, and methyl isocyanate.
Worker Distribution and Emissions Release Points
Worker distribution estimates for polyurethane production, derived by
correlating major equipment manhour requirements with the process illu-
strated in Figure 59, are shc wn ‘elov;
Unit Workers/Unit/8—hour Shift
Batch Reactor 1.0
Conveyor 0.5
No major air emission point sources are associated vith the one—shot
process. However, fugitive and process emissions result from the mixing
tank vent and from the formation and cure of the foam. Control of the
reactor vent stream may be accomplished by venting to a flare to incinerate
the remaining hydrocarbon. or to blov&wn.(2851 Control of fugitive emis-
sions from valves, fl ’nges, and pumps could result from equipment modifica-
tion. A routine inspection and mainterance program may be the best control
available.
Of major concern in polyurethane manufacture is employee expos re to
toluene—2,4—diisocyanate, methylene bisphenyl isocyanate or other i:ocyanate
compounds. The effects of acute and chronic exposute to these compounds are
discussed in the “Health Effects” portion of this section.
Available toxicity information on the numerous additives which may be
incorporated into polyurethane is provided in IPPEU Chapter lOb.
Little data are available in the literature from which employee expo-
sure potential may be estimated. However, one source gives an emission
factor of 14—420 g hydrocarbon/kg product for polyurethane foam production
[ 286J.
Health Effects
The production of polyurethane foam involves the use of over 190 input
materials, some of which are toxic, nutagenic, and/or teratogenic. Three
flame retardants are suSpected carcinogens: tris(2,3—dibromopropyl) phos-
phate, tris(2—chloroethyl) phosphate, and antimony trioxide. In addition to
these, some of the input chemicali are known to produce tumors in laboratory
animals and are currently being ‘.est2d for carcir geneais. Other chemicals
which could pose a significant ‘iealth risk to plant employees if exposure
occurs include: three blocking agents—— hydrocyanic &cid, pyrocatechol, and
phenol; three catalysts——antimony pentachioride, antimony trichloride, and
triethylainine; hydroquinone, which is used as a stabilizer; the antioxidant
resorcinol, which i used in low concentrations; and methyl isocyanate. The
537
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reported health effects of exposure to these substances are summarized
below.
Several organometallic compounds also are used in th. production of
polyurethane foam. Included among these are five compounds of tin which
are used am catalysts, for which OSHA has set an air standard of 0.1
mg(Sn)/m 3 (8 hour TWA). These are tributyltin acetate, tri.etbyltin
hydroxide, dimethyltin dichioride, dibutyltin diacetate, and tetrabutyltin.
OSHA has set an air standard of 2 mg(Sn)/m 3 (8 hour TWA) for stannous
chloride and stannic chloride.
Antimony Oxide is a suspected carcinogen (5J which has also produced
positive results in tests for autagenic effects.f 156) Animal testing of
this substance is liatied, however, and no epidemiological data exist.
Antimony Pentachioride is extremely toxic (851 and can cause systemic
damage upon acute exposure by ingestion or inhalation. (242j The fumes from
reaction with moisture are also toxic.(157J Animal test data suggest that
this substance, in addition to being highly toxic, is a mutagenic agent.
(23 J The OSHA air standard is 0.5 mg(Sb)/m 3 (8 hour TWA).(67j
Antimony Trichioride , like antimony pentachloride, is extremely toxic.
(85) It is reported to irritate not only the upper respiratory tract, but
to produceslightly delayed abdominal pain and loss of appetite indicative
of effects over’ and above that of hydrochloric acid, believed to be the
major hydrolytic product from contact with mâist tissue.(5 ) Toxic effects
have been reported in humans after inhalation of a dose equivalent to 73
mg/a 3 .(20) The OSRA air standard is 0.5 mg/rn 3 (8 hour TVA).(67j
• HydIocyanic Acid is highly toxic by ingestion, inhalation, and skin
absorption (242); the pr’ ,able oral lethal dose for humans is less than 5
mg/kg, or just a taste.L83 1 Inhalation of vapors causes toxic effects and
death within several minutes to several hours, dep nding upon the concen—
traeion.(833 Syiptows of poisoning include giddiness, hyperpnea, headache,
palpitation, cyanosis, and unconsciousness; asphyxial convulsions may
precede death483j The OSHAstandard in air is 10 ppm (8 hour TVA). [ 67J
Hydroguinone has exhibited potential as a tumorig.nie, mutagenic, and
teratogenic agent in animal tests.(233J Carcinogenesis tests have poduced
indefinite results, but the substance is currently being tested by the
National Toxicology Program for carcinogenicity. [ 233j Hydroquinone is also
highly toxic. Fatal human doses have ranged from S to 12 grams, although
300 to 500 milligrams have been ingested dailT for 3 to S months without ill
effects.(8 5J The OSHA air standard is 2 mg/m 3 (8 hour TIJA).(67J
Methylene Bisphenyl Isocyanate is a strong irritant and nay cause
systemic damage via skin absorption.(242j Animal data indicate that the
substance is also very toxic by ingestion and inhalation. (2333 The OSHA air
standard is 0.02 ppm (8 hour TWA).(67J
Phenol is extremely toE. by ingestion, inhalation, and skin
absorption. (85j Approximateiy half of all reported cases of acute phenol
538
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poisoning has resulted in death.(278J Chrontc poisoning may also occi r from
industrial contact and has caused renal and hepatic damage.(149J Evidence
indicates that phenol is also a tumorigenic, mutagenic, and teratogenic
agent; however, a recent carcinogenesis bioassay by the National Cancer
Institute produced negative results.(233j The OSHA air standard is 5 ppm
(TWA). (67 j
Polyurethane 1 in the form of foam, has produced positive results in
animal tests for carcinogenicity.(1o7J However, very little animal data and
no human data exist in the available literature with which to evaluate the
potential for other adverse effects in humans following exposure to this
substance.
Pyrocatbchol is very toxic, probably 1.5 to 3.0 times wore toxic than
phenol, depending on the route of administration. (4J Symptoms of exposure
are similar to those associated with exposure to phenol (e.g., vasoconstrica
tion causing rise in blood pressure, b]ood dyacrasias, renal and bepatic
damage, convulsions), but convulsions are more frequ.nt.(853 Pyrocatechol
exhibits tumorigenic and wutagenic potential, and is currently being tested
for carcinogenesis by the National Toxicology Program. (233J
Resorcinol is a tumorigen and a mutegen according to animal test data
12331; however, carcinogenic testing has produced indefinite results. [ 105J
The chemical is currently being tested for carcinogenesis under the Na’ 4 onal
Toxicology Program. Rasorcinol is also highly toxic by ingestion. An oral
exposure of 29 mg/kg has caused death in humans.(52j
Toluene—24—Diisocyanate (TDI ) is a strong irritant of the eyes, mucous
membranes and skin. Acute exposure to TDI produces coughing, choking, chest
pain, nausea, and pulmonary edema. The importance of acute effects of TDI
overexposure is overshadowed by its ability as a potent respiratory tract
sensithe-. In sensitized individuals, severe asthmatic symptoms may occur
within n utes of exposure. The 080* air standard is a ceiling value of
0.02 ppm. The Aaerican Conference of Governmental Indua frial Hygienists
(ACCIN) has retoi.mended a Threshold Limit Value (TLV) of 0.005 ppm (8 hour
TWA).
Triethylamine is highly toxic by ingestion and inhalation anJ
moderately toxic via denial routes.f243j It is a strong irritant to tisse.
At least one animal study ‘ias shown that triethylamin, produced mutagenic
effects in rats at the low dose of 1 mg/w 3 .(96J The OSHA air standard is
25 ppm (8 hour TWA). [ 67j
Tri(2—Chloroethyl) Phosphate , a suspected carcinogen 161. is currently
undergoing additional tists for carcinogenesis b7 the National Toxicology
Program.(233J Very little animal and human toxicity data exist in the
available literature with which to evaluate toxic effects of acute or
chronic exposure to this substance.f233J
Tris(2,3—Dibromopropy l) Phosphate is classified as a suspected human
carcinogen by the International Agency for Research on Cancer.(108J Posi-
tive results on a Natic al Cancer Institute carcinogenesis bioassay confirm
539
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the carcinogenic potential of this substance.(233j Substantial evidence
also exists of its mutagenic and teratogenic potential.(233J It is a skin
and eye irritant and is moderately toxic by ingestion.(233J
Air Emissions
Chiorofluorocarbon emissions from flexible polyurethane foam slabstock
production are approximately 0.03 kg/kg of foam and emissions from molded
flexible foam production are approximately 0.02 kg/kg of foam.(282J These
emissions may result in a significant ànvironaental or worker health problem
depending on the stream components, operating parameters for th processs,
engineering and administrative controls, and maintenance programs. Accord-
ing to EPA estimates, the population exposed to polyurethane foam emissions
in a 100 km 2 area around a polyurethane foam plant is: 326 persons
exposed to hydrocarbons and 2 persons exposed to particuiates. 1286J
dastewater Sources
The only was,tewater source asSociated with polyurethane foam production
is routine cleaning water. No vastevater data were found in the literature
consulted.
Solid Wastes
The solid waste generated Ly this proc.ss is substandard foam which
cannot be blended. This waste may be recycled and reused by adding glycol
to the foam or used to form carpet backing. This process is emission free,
‘rnt seneitive to product mixes, and the dettved polyol may be completely
recycled. [ 276J
Environmental Regulation
Effluent limitations guidelines have not been set for the polyurethane
foam industry.
Hew source performance ctandards (proposed by EPA on January 5, 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves most not release more than 200 ppm above
background, except in emergency pressure releaseN, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous wastes (46
Federal Register 27476, May 20, 1981):
di—n—butyl phthalate — 11069
d ich lorodif luorO mpthane — 11075
dtmethyl phthalate — U102
540
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dioctyl phthalate (DOP) — U107
cthylenediamine — P053
hydrocyanic acid — P063
methyl isocyanate — P064
phenol — U188
pyridine — U196
resorciriol — U201
toluene dilsocyanate (TDI) — U223
trichiorofluoromethane — U229
tris(2,3—dibromopropyl) phosphate — U235
Disposal of these compounds or polyurethane foams containing residual
amounts of these compounds must comply with the provisions set forth in the
Resource Conservation and Recovery Act (RCRA).
541
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SECTION 24
POLYVINYL ACETATE
EPA Soiree Classification Code — Polyprod. Ceneral 3-01-018-02
INTRODUCTION
Polyvinyl acetate (PVAc) is a tasteless, odorless polymer which is
transparent, and is brittle at low temperatures. It has excellent aging
qualities since it is resistant to oxidation and inert to the effects of
ultraviolet and visible light.(234j These characteristics make polyvinyl
a .etate ideal for applicatioas such as latex paints, adhesives, surface
coatings, and textile finishings. It is also used as an intermediate in the
mau’ facture of polyvinyl alcohol. The most familiar application of poly-
vinyl acetate is the white glue used in many homes and schools.1651 Poly-
vinyl acetate production in the United States for 1980 totaled 452,700
metric tons.
Polyvinyl acetate is produced by polymerizing vinyl acetate using a
radical initiator. The formula
(CH 2 —cH )
represents the iepeating group which provides the backbone of the polymer
chain. With the introduction of additives, polyvinyl acetate and polyvinyj,
acetate emulsions exhibit the physical proserties listed in Tables A—33 and
A—34 in Appendix A.
Polyvinyl acetate has physical properties very similar to those of
aliphatic esters, which are generally soluble in organic solvents such is
ether, chloroform, and benaene. Polyvinyl acetate is insoluble in water but
soluble in moat organic solvents including methanol and alcohols containing
more than five carbon atoms. The addition of water to ethanol, propanol,
and butanol enhances the solubility of polyvinyl acetate in these low
alcohol solventi. Table A—35 in Appendix A presents the solubiltty of
polyvinyl acetate in selected chemicals.
The properties of polyvinyl acetate can be altered by copolymerizatjon
with another monomer. For example, vinyl acetate—ethylene and vinyl
acetate—vinyl pivalate copolymers are resistant to hydrolysis.(1383 The
solubili..y of polyvinyl acetate polymers in a desired medium is also
influenced by copolymerization.
542
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Polyvinyl acetate is prciuced by four different polymerIzation tech-
nologies; emulsion, solution, suspension, and mass polymerization. Emulsion
p)lymerization accounts for as much as 90 percent of the polyvinyl acetate
and vinyl acetate copolyiners. The production of polyvinyl acetate in emul-
sions makes it very versatile in the production of paints, adhesives, and
textile and paper coatiiigs. [ 234J
INDUSTRY DESCRIPTION
The polyvinyl acetate industry is comprised of a diverse group of
chemical and petrochemical companies, which are listed in Table 189. There
are 55 polyvinyl acetate manufacturers in the United States. Of the 110
sites listed in Table 189, California, New Jersey, and Illinois contain 16,
15, and 13 sites, respectively, which total 38 percent of the total number
of sites. Ohio, Texas, and Georgia have 7, 7, and 6 sites, respectively.
New York and Massachusetts have five sites each, with the other fifty
production sites being diversely located.
The polyvinyl acetate industry currentl , uses four processes: emul-
sion, suspension, solution, and mass (or bulk) polymerization. There is no
information in the literature concerning plant capacity or a correlation
between the plants listed in Table 189 and the processes discussed.
However, two producers, Air Products at Calvert City, Kentucky and Monsanto
t Sprin fie]d, Massachusetts, also manufacture polyvinyl alcohol at the
same site and DuPont produces polyvinyl alcohol at another (LaPorte, Texas)
site.(35J These three plants may use suspension or solution polymerization
to manufacture PVAc since these processes are preferentially used for the
producticri f polyvinyl acetate for polyvinyl alcohol production.
The polyvinyl acetate industry is consumer oriented. Paints, adhe-
sives, and coatings are used in the construction, consumer goods, and
textile and pa ’rer Industries. PVAe production peaked in 1979 at 328,600
metric tons and dropped to 303,500 metric tor.a in 1980, which is still above
the 286,400 metric ton level of 1976. [ 65J Since PVAc i. used in many
consumer goods, its production level reflects the general economic trends.
With the extra 25,100 metric ton capacity, from 1979 to 1980, no new plants
are likely in the near future.
PRODUCTIOd AND END USE DATA
In 1980, the sales of polyvinyl acetate resin. were 303,.iOO metric tons
65J. An additional 134,000 metric tong of capacity were available for
polyvir.yl acetate hydrolysis to polyvinyl alcohol. Total 1980 polyvinyl
acetate production was 452,700 mc ric tons. [ 35, 65J
Excluding polyvinyl alcohol production, polyvinyl acetate is used
as: [ 138J
• Emulsions for adhesives;
• fnoersinn resir nr amu1 Iona for paints;
543
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TABLE 189. MAJOR POLYVINYL ACETATE MANUFACTURERS
Manufacturer (Division) Location
AD O Chemical Company, Inc. Newark, NJ
Air Products and Chemicals, Inc.
Polymer Chemicals Division Calvert City, KY
City of Industry, CA
Cleveland, OH
Clkton, MD
South Brunswick, NJ
AZS Corporation
AZS Chemical Company Division Atlanta, GA
Bennett’s Salt Lake City, UT
Borden, Inc.
Borden Chemical Division
Adhesives and Chemicals
Division — east Bainbridge, NY
Thermoplastic Products Bainbridge, NY
Compton, CA
Demopolis, AL
Ilitopolis, IL
Leominster, MA
California Resin and Chemical, Co., Vallejo, CA
Inc.
Celanese Corporation
Celanese Plastics and Specialities
Co., subsidiary
CelaneseResiria Division Los Angeles, CA
Newark, NJ
Colloids, Inc.
North Chemical Co., Inc.,
subsidiary Marietta, CA
Conchemo, Inc.
Baltimore.flperat ions Baltimore, MD
Kansas City Operations Kansas City, MD
(continued)
544
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TABLE 189 (continued)
Manufacturer (Division) Location
Peter Cooper Corporation Dallas, TX
Gowanda, NY
Pineville, NC
Dan River Inc.
Chemic 1 Products Division Danville, VA
De Soto, Inc. Chicago Heights, IL
Garland, TX
Diamond Shamrock Corporation
Proess Chemicals Division Cedartown, Gha
Dutch Boy, Inc.
Coatings Group Baltimore, MD
E.I. du Pont de Nemours & Co., mr.
Plastics Products and Resin
Department Senece, IL
Enkay Chemical Co. Elizabeth, NJ
Esmark Inc.
Swift & Co., subsidiary Gresham, OR
Hammond, IN
Houston, TX
Los Angeles, CA
Tampa, Ft.
Foy—Johnston, Inc. Cincinnati, OH
Franklin Chemical Co. Columbus, OH
H. B. Fuller Co.
Polymer Division Edison, NJ
Atlanta, GA
Blue Ash, OH
General Latex z d Chemical Corp. Ashland, OH
Cambridge, MA
Charlotte, NC
Dalton, GA
(continued)
545
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UBLE 189 (continued)
Manufacturer (Division )
V. k. Grace and Co.
Dewey and’ Almy Cheeical Division
Orgaiic Cheaicals Division
Gulf Oil Corporation
Milisaster Onyx Group, subsidiary
Lyndal Chenical Division
Hart Products Corporation
H A N cheaical Coapany
Ineilco Corporation
Sinclair Paint Co. Division
International Minerals lad Che.ical
Corporation
INC Industry Group, Inc.,
subsidiary
INC McVhorter Resins Division
Jones—Blair Co.
Kelly-Moore Paint Co.
Kohler—McLister Paint Co.
McCloskey Varnish Co.
Monsanto Co.
Monsanto Plastics & Resins Co.
Benjamin Moore & Co.
Napko Corporation
National Casein Co.
Carpentersville, IL
Melville, NY
Dallas, TX
San Canoe, CA
Hurst, TX
Denver, CO
Los Angeles, CA
Philadelphia, PA
Portland, OR
Springfield, MA
Los Angeles, CA
Meiros. Park, IL
Newark, NJ
St. Louis, NO
Houston, TX
Chicago, IL
Location
Owensboro, KY
South Acton, MA
Lyndhuret, NJ
Jersey City, NJ
Totowa, NJ
Los Angeles, CA
(continued)
546
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TABLE 189 (continued)
Manufacturer (Division )
National Starch and Chemical Corp.
Resins Division
Charles S. Tanner Co. Division
Norris Paints & Varnish Co.
The O’brien CorporatIon
The O’Brien Corp. — Central Region
The O’brien Corp. — Eastern Region
The O’Brien Corp. — Western Region
Onyx Oils & Resins, Inc.
Philip Morris, Inc.
Polymer Industries, Inc.,
subsidiary
Adhesives and Liquid Coatings
Division
Textile Chemicals Division
Raffi and Swanson, Inc.
Polymeric ResIns Division
Reichhold Chemicals, Inc.
The Sherwin—Williams Co.
Coatings Group
Stanchem, Inc.
Location
Meredosia, IL
Plainfield, NJ
Enoree, SC
Salem, OR
South Bend, IN
Baltimore, MD
South San Francisco, CA
Brooker, FL
Stamford, cr
Greenville, SC
Wilmington, MA
Azusa, CA
Charlotte, NC
Kansas City, KS
Morris, IL
South San Francisco, CA
Tacoma, WA
Cheswold, DE
Elvood, NJ
Chicago, IL
Huron, OH
Reading, PA
San Francisco, CA
(continued)
Emulsion Polymers Division
Scholler Brothers Inc.
ScM Corporation
Glidden Coatings & Resins Division
Chicago, IL
East Berlin, CT
547
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ThBLE 189 (continued)
Manufacturer (Division) Location
Squibb Corporation
Life Savers Inc., subsidiary Canajoharte, NYa
Sybron Corporation
Jersey State heisical Co. Division Haledon, NJ
Syncon Resins Inc.
Parnow, Inc. Division South Kearny, NJ
Union Carbide Corporation
Chenicale and Plastics Division Alsip, IL
Garland, TX
Somerset, NJ
South Charleston, WV
Torrance, CA
Tucker, CA
Union Oil Co. of California
Union Chemicals Division Bridgeviev, IL
Charlotte, NC
Corning, NJ
La Mirada, CA
Lemont, IL
Newark, CA
United Merchants and Manufacturers,
Inc.
Raichem Chemical Division Langly, SC
Valepar Corp.
Baltimore Operation. Baltimore, MD
Tenkin—Majestic Paint Corpo:ation
Ohio Polychemicals Co. Division Columbus, OH
ami . plant manufactures resins for chewing gum.
Sources: Chemical Economics Handbook , updated annually, 1980
data.
Directory of Chemical Producers , 1981.
548
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• Emulsions for paper and textile coating;
• Emulsions or dispersion resins for cement, concrete sealer, and tile
cement;
• Emulsions for binding nonvoven fabrics; and
• Resins for chewing gum 5a,ies.
Table 190 delineates the sales and captive use of vinyl acetate for poly-
vinyl acetate production.
23.4 PROCESS DESCRIPTIONS
Polyvinyl acetate is produced by emulsion, suspension, solution, and
mass (or bulk) polymerization. O these methods, emulsion polymerization
produces most of the polyvinyl acetate which is not used for hydrolysis to
polyvinyl alcohol. PVAc is used as an emulsion in adhesives, paints,
cement, concrete sealer, tile cement, nonvoven fabric binders, and paper and
textile coatings; therefore, producing a PVAc emulsion is the most useful
process for these end uses. Suspension and solution polymerization are used
to produce polymer beads or a polymer solution which is in a convenient form
to hydrolyze polyvinyl acetate to polyvinyl alcohol, although these resins
may be used for other applications.(138, 234] Mass (or bulk) polymerization
is used mainly for the production of low molecular weight resins since
increasing the molecular weight of the pnlymerizing mass makes temperature
control and pumping the mixture very difficult.(234] Tables 191 and 192
present typical input materials and operating parameters for these pro-
cesses. Specialty chemicals for PVAc production are listed in Table 193.
An important economic consideration for the four PVAc processes is that
because of the high monomer tu polymer conversion (99.5+2), monomer strip-
ping of the PVA is not required.
In the polymerization of vinyl acetate, the vinyl acetate monomer
reacts with a free—radical initiator (Re) to start the polymerization reac-
tion. As other vinyl acetate monomer molecules combine with the vinyl
acetate radical, the polymer chain is propagated. Polymerization terminates
when the radical reacts with an electron accepting group (chain transfer).
The chain length is affected by the temperature of the reaction and the
availability of chain transfer agents. Commercial polyvinyl acetate grades
have molecular weights ranging from 11,000 to approximately 1.5 million.
(138, 234] The polymerization reaction is depicted below:
Initiation I
I
2 0C0 3 + R. RCH 2 -CH-OCOCH 3
Propagation
OCOCH3
I I
RCH 2 -CH-OCOCH 3 + CE 2 CHOCOCH 3 *RCH 2 C1FCR2 -CH-OCOCH
549
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TABLE 190. 1980 SALES AND CAPTIVE USE OP POLTYINYL ACETATE
E d Product or Use Metric Tons
E u1sion Paint 97,200
Adhesives 113,600
Paper 38,300
Textile 14,300
Non—Woven Binders 13,400
Other 18800
TOTAL U.S. SALES 295,600
Export 7900
TOTAL SALES 303,500
aTbese figures do not include polyvinyl acetate produced for polyvinyl
alcohol.
Source: Pacts and Figures of the Plastics Industry , 1981.
550
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TABLE 191. TYPICAL INPUT MATERIALS TO POLYVINYL ACETATE
PRODUCTION PROCESSES IN ADDITION TO MONOMER
Organic Protective
Process Water Initiator Solvent Surfactants Colloids
Emulsion X X X
Suspension x X X
So1utio X X X
Mass X
TABLE 192. TYPICAL OPERATINC PARAMETERS FOR POLYVINYL ACETATE
PRODUCTION P OCESSES
Process Temperature Reaction Time
Emulsion 80 — 90°C 4 — 5 hours
Suspension 70°C 2 hours
Solution io — 80°C
Mass 70 — 80°C ———a
aReaction times vere not available in literature sources.
Sources: Encyclopedia of Polymer Science and Technology.
Marshall Sittig, Vinyl Monomers and Polymers, 1966.
551
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TABLE 193. INPUT MATERIALS USED IN POLYVINYL ACETATE MANUFACTURE
‘ Function Compound
Cononomer Acrylic Acid
Alkyl Acrylates
Butyl Acrylate
Crotonic Acid
DLalkyl Maleates
Dibutyl Funarate
Dibutyl Maleate
Di—2—Ethylhexyl Funarate
Di ’2—Ethylbexyl Maleate
Ethyl Acrylate
Ethylene
2—Ethyihexyl Acrylate
N—M thy1ol Acrylamide
Sodium Ethylenegulfonate
Vinyl Caproate
Vinyl Pumarate
Vinyl Maleate
Vinyl Laurate
Vinyl Vereatate
Surfactants Anionic Sulfates
Aaionic Sulfonates
PrQtective Colloids Hydroxyethyl Cellulose
Polyvinyl Alcohol
Free Radical Initiators Ammonium Persulfate
Bensoyl Peroxide
Hydrogen Peroxide
Organonetallic Compounds
Peroxydisulfates
Potassium Persulfate
Buffers Acetate Salts
Bicarbonate Salt.
Phosphate Salts
(continued)
552
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TABLE 193 (continued)
Function Conpound
Plasticizers Dibutyl Phthalate
Tricresyl Phosphate
Butyl Benzyl Phthalate
Diethyl Phthalate
Di. ethyl Phthalate
Diethylene Glycol Dibenzoate
Dipropylene Glycol Dibenzoate
Butyl Carbitol Acetate
Cresyl Diphenyl Phosphate
Triphenyl Phosphate
Chain Transfer Agents Aldehydes
Carbon Tetrach]orjde
Thiols
Sources: Encyclopedia of Chemical T’ chno1ogy , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
4arshal1 Sittig, Vinyl Monomers and Polymers , 1966.
553
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Termination via Chain Transfer
I OcOCRjJ
I I
R’R + R CH -cff fncH2cH-ocOdH 3
I ? ‘ 1
R’.+ RfCH 2 Q1 JncH2c11K
where R’ and R represent monomers, reacting polymers, o: any electron
acczpting group.
Emulsion Polymerization
Emulsion polymerization produces two types of products: a fine—
particle—size emulsion with 0.1 to 0.2 micron particles, used for paper
coating; and a large—partie1e siz. emulsion with a 0.5 to 3.0 micron
particles used for adhesives.(138j The production of fine particle size
emulsions utilizes anionic and nonionic surfactants and no protective
colloid, while the large particle size emulsions are produced using pru—
tective colloids. Dispersion of the monomer in the aqueous phase without a
protective colloid may reduce the number of micelles which also react to
form polyvinyl acetate, since the function of he protective colloid is to
keep the droplets from agglomerating.
In addition to particle size, other factors which determine the type of
emulsion prepared are: the stability of the emulsion under mechanical
shear, change of temperature, compounding, and passage of time; and the
characteristics of the coalesced resin after application such as smooth-
ness, opacity, and water resistance as veil as characteristics of the mul—
sion as it is being used, such as flow properties and settling tiae. [ 234J
The advantages of emulsion polymerization over mass, solution, and suspen-
sion polymerization processes include: ability to obtain a high solids
content with a minimal increase in viscosity and excellent ability to
maintain constant temperature during polymerization.
Figure. 60 and 61 present process flow diagrams for emulsion polymeri-
zation processes. In Figure 60, the vinyl acetate monomer enters a feed
tank which may have a nitrogen atmosphere. Depending on the initiator used,
oxygen may inhibit the reaction. After the monomer is agitated in the feed
tank, it is fed to the polymerization reactor where it is combined with a
protective colloid/water mixture which may contain a surfactant. Most
polyvinyl acetate emulsion processes use continuous monomer feed during the
course of the reaction if small particles are desired. ‘atch feeding of tLe
monomer to the reactor results in larger particles.(234J During polymeri-
zation, the reaction temperature is controlled by means of a ref lux
condenser, thereby removing a portion of the heat of reaction. When the
polymerization is complete, the polyvinyl acetate emulsion is removed from
the vented reactor and used either in this form or as spray dried resins.
554
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Figure 60. Polyvinyl acetate production using euiulsion polynerization.
Source: Encyclopedia of Polymer Science and Technology .
Pro ct iv .
ColLold
V I
U’
VI
Polyvinyl Acetate
Einul iun
-------
V.nt
Figure 61. Polyvinyl acetat i using coOtinuous el!ulsion polylulerisation.
Source: Encyclopedia of Poly.er Science and Technology .
“I
U I
a’
Vent
Seeding
Additive.
VinL .htng
Paactor
Polyvinyl
ate
-------
Figu’e 61 presents a process flow diagram for Continuous polymerization
of polyvinyl ac2tate. Monomer, water, catalyst, protective colloid, and
emulsifier are fed to the seeding reactor, which operates at about 70 to
75°C. The reaction mixture is then fed to a polymerization reactor where
more water, monomer, and a buffer are added. The polymerization reactor
operates at 80 to 85°C. Upon leaving the polymerization reactor, the
polymer mixture is combined with additives, which may include plasticizers,
additional stabilizers, and antifoaming agents, [ 138J to make the polyvinyl
acetate emulsion. Each reactor is equipped with a vent.
In emulsion polymerization processes, vinyl acetate comprises 30 to 60
percent of th charge to the reactor.(234J Up to 3 percent of the charge
may be an enulstfier. [ 234J Since less than 0.5 percent of the mor.omer is
present In the resulting polymer, monomer stripping of the polyr .r lq
unnecessary. [ 1381
Comonomers may be used to alter the chemical and physical properties of
the polymer, such as hydrolysis, solubility, and water resistance. In addi-
tion to the i’ put materials listed in Table 193, formulations for polyvinyl
acetate emulsions may include solvents, thickeners, antifoamtni, agents,
biocides, pigments, and fillers. More detail on the formulatin of poly-
vinyl acetate can be found in IPPEU Chapter lOa.
!.gitated 8lass—llned or stainless steel reactors used range in size
from 2 to 30 m , the size depending on the efficient removal of heat from
the reaction nixture. [ 138, 234J Impellers may be turbIne—type with flat,
curved vertical, or 450 blades for low—viscosity emulsions and anchor—type
agitators for h!gh—viscosity eoiulslons.(138J Most emulsion polymerization
proce9ses ar” perfr r r d 3t c ph ric pressure, [ 234J and Moynoa. pumps are
rep’rtedly best for pumping the resulting polymer emulsion. [ 138J Polyvinyl
acecate emulsions may be spray dried to produce a redispersible resin which
may be used Ira non-emulsion paints.(138J
A typical recipe for a large particle size emulsion follows: [ 125j
Material Parts by Weight
Water 42.75
Vinyl Acetate (monomer) 55.00
Hydroxyethyl Cellulose (protective
colloid) (Cellogize WP-09,
Union Carbide) 2.00
Tergitol NPX (Union Carbide)
(surfactant) 0.05
Potassium peroxydisulfate (initiator) 0.05
Sodium bicarbonate (buffer) 0.15
The Cellosize, which acts as a protective cclloid, Tergitol (surfac—
tant), and water are heated to 80°C for one hour, then cooled to 30°C.
After cooling, 10 percent of the vinyl acetate monomer, the potassium
peroxydisulfate (initiator), and sodium bicarbonate (! iuffer) are added.
557
-------
This mixture is heated to 70 to 75°C. The remaining monomer is added in
increments over the next four hours while the reaction temperature is
maintained at 80°C. At the end of the monomer addition, the temperature is
raised to 90°C for 30 minutes, cooled, and filtered. The resulting solids
content of the emulsion is 56 to 57 percent, with a viscosity of 3,000 cP
and a pH of 5.0.1138 1
Suspension Polymerization
The major advantage of producing polyvinyl acetate using suspension
polymerization is the manufacture of polymer beads which can be easily
removed by filtration from the reaction mixture. However, the large bead
size also renders the polymer unsuitable for use in many emulsion or disper-
sion type products. The equipment used for suspension polymerization,
depicted in Figure 62, is similar to that used in the emulsion polymeriza-
tion process.(138J The batch process is started by mixing monomer, water,
and initiator (benzoyl peroxide or diacetyl peroxide) in a reactor and
heating the mixture tc about 70°C. After approximately 10 minutes, the
protective colloid (polyvinyl alcohol) ii added to the mixture and the
resultant mixture reacts for abeut two hours. The beads are removed from
the reactor, filtered, washed, and dried.
Wastewater generated by this process includes: the aqueous phase from
the suspension after the beads have been separated in the filter, and the
polymer wash water. Each of these streams may contain a small amount of:
vinyl acetate, initiator, protective collâid, and polyvinyl acebate. Since
the reaction is c&rried to high monomer conversion very little vinyl acetate
is present in the vastewater. Similarly, the small amountS of protecti
“lloid and initiator used preclude large amounts of this maL. rial being
released in the wastewater.
Some VOC emissions are expected from the reactor vent and the drier
outlet gas. Again, high monomer conversion and small input concentrations
keep emissions of vinyl acetate, initiator, and protective colloid very
small.
A typical suapension polymerization recipe follov.:1l3 J
Material Parts by Weight
Vinyl Acetate (monomer) 100
Water zoo
Benzoyi peroxide (Initiator) 0.3
Partially Hydrolyzed Polyvinyl
Alcohol (protective colloid) 0.03
Solution Polymerization
• Vinyl acetate is polymerized in sciution mainly for use in polyvinyl
alcohol productio.i. 138J Soivens include methanol, butanol, ethyl a et ce,
ethanol with S to 10 percent water, methyl zcetate propionaldehyde, and
‘558
-------
Vent
Figure F2. PfJfvInvJ ar.tare using iun4pPnqiofl pn1ynt’r1 atton.
Source: n cpe4ia of Pr4jmc.r ScIenr. and T.rhnology .
Polymer (ZaP io’u
Reactor
W.t er
Treatment
Jast.vater :o
treatment
DTY5T Outlit
Air
Polyvtnyl Ar.tatI
Deeds
-------
ketones. [ 138, 234J Initiators used include bensoyl peroxide, lauroyl
peroxide, t—butyl hydroperoxide, and azobisisobutyronitrj le.( 138 1 Protec-
tive colloids, such as partially hydrolyzed polyvinyl alcohol, may be used.
The major advantage of solution polymerization is the production of the
polymer in a solution which can then be either reacted or formulated on
site. However, the cost of the solvent is the primary disadvantage. As
illustrated in Figure 63, vinyl acetate and propionaldehyde are mixed and
charged to the first of two polymerizat.jon reactors in series. Ethyl
acetate and initiator are combined in the catalyst solution tank and also
charged to the first reactor. loth reactors, are equipped with vents. Polym-
erization occurs at 70 to 80°C.f256J The reaction temperature is controlled
by cooling a portion of the reaction solution in a ref lux condenser, thereby
removiflg a portion of the heat generated by the reaction. The solution is
then fed to af ter—polymeri za jo tanks where additional ethyl acetate and
methanol are added, if the solution is shipped to another location for
further processing. The resulting solution is filtered before use in
polyvinyl alcohol production.
A typical production recipe for •olution polymertgatgon of PYAc 1
shown belov:f54J
Material Part, by Weight
Vinyl Acetate (‘monomer) 6,523
Methanol (solvent makeup) 544
Benzoyl PPrI NI4C (initiator makeup) 60
Water (makeup) 86
Inhibitor
Mass Polymerization
Mass (or bulk) polymerization of vinyl acetate is used to manufacture
smaller amounts of the polymer than solution, suspension, or emulsion
polymerization. The major advantage of this process is the production of
low molecuiar weight polymers. Tb. primary disadvantage of low molecular
weight polymer, is ‘he difficulty in removing heat as the viscosity of the
polymerizing monomer/polymer mixture increases.(234J
A conttnuo aass polymerization process is illustrated in Figure 64.
Vinyl acetate and the initiator may be combined under a nitrogen atmosphere
d pend1ng upon ‘he Initiator used, in an initiator solution tank. The
tePultfnn mixture is passed through s icreen filter before entering a mixing
tank where the initiator solution is combined with additional vinyl acetate.
The monomer mixture can be placed into storage for metered feed to the reac-
tor. The ntnred monomer is filtered before it is charged to th. reactor
which is fitted with a vent. Polymerization js performed at or near atmos-
pheric preequre and within the 70 to 80’C temperature range.(255J The
reaction temperature is controlled by cooii.ig a portion of the reaction mix—
tiare In a ref lux -condenser, thereby remo ing a portion of the heat .ge&erated
by the reaction. When the polymerization is complete, the polymer is fed to
a cutter which renders the polyvinyl aeet.t. suitable for further use.
560
-------
Figure 63. Polyvinyl acetate production via COntlnuou solution polymerization.
Source: Encyclopedia of Polymer Science and Technoj.!a .
Vt”’
Iby1
£. ta(. tutiját , ,
ML iii
J .
Po1 .Iii,1 £c.i.t.
I a SOIUILUSI
Ing Tanks
-------
Pigure 64. Polyvinyl acetate production via continuoug mais pOl ept ti .
!o,jrceg EnS lopedja of Poly5er Science and Technolog 1 .
m i t tator
3o1utiøi
Tank
It
I.fluaz
562
-------
A typical production recipe for mass polymerizatLon of PVAc va not
found in the literature.
Energy Requirements
No data giving the energy required for polyvinyl acet ite production
were found in the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Polyvinyl acetate is nontoxic. However, the ACGII 1 has recommended a
TLV of 10 ppm (8 hour TWA) for vinyl acetate. A significant point concern-
ing vinyl acetate is that PVA production processes are carried to very high
conversions (99.5+Z). This higt conversion eliminates the need for monomer
5trtpoing steps and minimizes the potential for vinyl a..etate emissions o:
losses from downstream processing. Low monomer concentrations in the
polymer also reduces vinyl acetate emissions from polymer bead drying in
suspension polymerization processes.
Worker Distribution and Emissions Release Points
Worker distribution estimates for each of the five commercially viable
pro eqsn for polyvinyl acetate productioi are shown in Table 194. We made
the estimates by correlating major equipment manhour requirements with the
process flow diagrams in Figures 60 through 64.
Although there are no point source air emissions from PVAc production,
the fui tive emissions may pose a a1gnfft. ant environmental and/or vcrker
health problem based on tl e strea& constituents, process operating param-
eters, engineering and administrative controls, and maintenance programs.
Proces, sources of fugitive emissions from PVAc manufacture are listed
In Tabe 195. In addition to vinyl acetate, numerous additives (see Table
193) may be emitted from reactor and monomer storage tank vents. Nitrogen,
upcd as a reactor purge, Is a simple asphyxiant and may be present in reac-
tor vent emissions. Solvents typically used in solution polymerization
include is.rFjI, butyl anc ethyl alcohols, ethyl and methyl acetate propton—
aid.hyde, and various ketone compounds. trying and cutting operations may
produce polymer particulate conrentrstIon that pose a nuisance dust •xpo—
sure hazprd.
Available health effects information for input materials to PVAe
product Ion a’e disc’igqed in the paragraphs below, Table 10 and in IPPEU
Chapter lOb.
lealrh ff ctq
The nanufa tuir of po;yvinyl acetate Involves the use of input
material, that could adversely affert the health of workers if Ingestion,
inh.4latifun, or skin contact occurs. The substances that pose the hl&hest
health risk du. to carcin)gentc, Isiutageni , tera’.igenic, or toxic properties
563
-------
tABLE 194 • WORKER DISTRIBUTION ESTIMATES FOR POLYVINYL ACETATE PRODUCTION
Process Unit Workers/Unit/S—hour Shift
Emulsion Polymerization Storage Tank 0.125
Batch Mixer i.o
Batch Reactor 1.0
Condenser 0.125
Continuous Emulsion Continuous Reactor 0.5
Polymerization
Suspension Polymerization Batch Reactor 1.0
Filter 0.25
Washing 0.25
Dryer 0.5
Solution Polymerization Storage Tank 0.125
Batch Reactor 1.0
Ref lux, Condenser 0.125
Batch Mixer 1.0
Filter 0.25
Mass Polymerization Storage Tank 0.125
Filter 0.25
Continuous Reactor 0.3
ContInuous M izcr 0.3
Refiux Condenser 0.125
Cutting 0.25
364
-------
TABLE 195. SOURCES OF FUGITYVE EMISSIONS FROM
POLyVINY . ACETATE MANUFACTURE
Source Constituent Emulsion Suspension Solution Mass
Reactor Vents Vinyl Acetate x X X X
Initiators x X X X
Emulsifiers X
Protective X X X
Colloids
Solvents X
Monomer Storage Vinyl Acetate x X X
Tanks and
Iflhibtt tg
Polymer Be.]d Polyvinyl Acetate X
Drying and Vinyl Acetate
Particulate. and
Emissions
Adjusting Tanks Soivetita X
Po1ym r Cutting Polyvinyl Acetate Z
and Vinyl Acetate
Part icul tpp
565
-------
include the com000mers acrylic acid and ethyl acrylate; polyvinyl alcohol,
which is used as a protective colloid; and the chain transfer agent, carbon
tetrachioride. A synopsis of the reported health effect, resulting from
exposure to these subsanees follows.
jj c Acid is a severe skin and respiratory irritant 1170) and is one
of the most serious eye injury chemicals. [ l37j Ingestion may produce epi—
gastric pain, nassea, vomiting, circulatory collapse, and in severe cases,
death due to shock.(85J Although the data are not sufficient to make a
carcinogenic determination, the chemical has been aseociated with tumori—
genie and teratogenic effects in laboratory animals.
Carbon Tetrachioride i a suspected human carcinogen iio j which is
also extremely toxic uj i inhalation or ingestion of small quantities.(24lJ
The toxic hazard posed by akin absorption is slight for acute exposures, but
high for chronic exposure..(24lJ The toxicity of carbon tetrachloride
appears to be primarily due to iti fat solvent action which destrc , the
selective permeability of tissue membranes and allow, escape of cirtain
essential substances such as pyridine nucleottdes.(78J The OSHA sir
standard ii 10 ppm (8 hour TWA) with a 23 ppm ceiling. (67J
Eth?l Acrylatc £ 5 currently being tested by the National Toxicology
Program for carciflogenesi . by standard bioassay protocol. Previous test
data led to indefinite resufts.11o7p It is very toxic by injestion,
inhalation, or skin absorption (242), producing symptoms of hypersoenja and
couvulstons.(149J The OSIIA air standard is 23 p C I hour NA).(67J
Polyvinyl Alcohol has produced positive results in animal testing for
carcinogencfey.(loyJ It. single dose toxicity, however, is presumably low.
(85) ImplantatIon of PTA sponge as a breast prosthesis has been essoc at.d
only with foreign body type of reaction 1101); neutral solutions for PTA
have also been used in eyedrops on human eyes without difficufty.(slj
Air Emissions
Source, of fugitiv, emissions from polyvinyl acetate processing are
summarised in Table 195 by process and constitwent type. Th. majority of
fugitive erissioni from polyvinyl acetAte processing are generated from
reactor vents. These emissions are reported to contain 1.5 kg of vinyl
acetate per metric eon of polyvinyl acet.t..(9jJ Reactor vent emissions may
also rontain plasticizes , unreacted initiatoti, and, for suspension and
emulsion polymerization processes, emulsifiegs and protective colloid,.
These emissions may be reduced by Touting the vented stream to a flare for
in i e gtio of the s drocarb ft or to blowdosm. (2 15 1
Polyvinyl acetate and vinyl acetate particulate, result from the drying
step in suspension polymerization and the cutting step in th. mass polymeri-
zation, as shown In Table 195. These pert i cul ate , y be controlled by
venting tt.ese stream, to a bsghouie or ele:tro,tatic precipitator for per—
ticulat. collect ion.
-------
Wastewater Sources
Polyvinyl acetate generates several wastewater sources associated with
the various production processes as shown in Table 196. The major waste—
water source from polyvinyl acetate production results from the steam strip-
ping of the vinyl acetate monomer prior to processing. Steam stripping is
utilized to remove any inhibitor which may have been added to prevent polym-
erization during shipping and storage. The usual inhibitor is hydroquinone,
and vinyl acetate will polymerize if the concentration is reduced to less
than 50 ppm. [ 268J The steam, when condensed, typically contains 20 kg of
vinyl acetate and 0.5 kg of hydroquinone per metric ton of polyvinyl
acetate. ( 93
Other wastewater streams during polyvinyl acetate production result
from filtration operations, washing the polymer beads during suspension
polymerization, and routine cleaning.
Ranges of basic wagtevater parameters for vastevaters from the four
production processes shown below were not separated by process by EPA for
the purpose of establishing effluent limitations for the polyvinyl acetate
lndu’.try: [ 284J
Unit/Metric. Ton of
Characteristic Polyvinyl Acetate
Product ton 0 — 25.03 .3
ROD 5 0—2kg
COD 0—3kg
TSS 0—2kg
The control technologies common to polyvinyl acetate facilities are:
equalization, chemical treatment, activated sludge, clarification, and
polishing. This va atevater treatment system has been demonstrated to
effectively treat the biologically degradabl, portions of the vast.. (284)
Sol!d U qt s
The solid wastes generated 4iirtng polyvinyl acetate production include
sut atandard polyvinyl acetate emulsions stored In containers or beads which
crlnn.iL t adlJai ed by blendf ;. Th.se w.e!.. are not hazardous; therefore,
their disposal should not pose an environmental problem.
F.nvironir.entsi Regulation
Eff}u nt limitations gul4ellnes have been met for the polyvinyl acetate
industry. RPT, RAT, and liSPS call for the pH of the cffluent to fall
botv on 6.’) and 9.0 (41 F d,’ral Register 32581, August 4, 19Z6).
New source performance standards (proposed by EPA on January 5, 1981)
for v iatll organic carbon (VCC) fugitive emissions include:
-------
TABLE 196. SOURCES OF WASTEWATER FROM POLYVINYL ACETATE MANUFACTURE
Source E mu leion Suepenaion Solution Maae
Monomer Steam Stripping X X X X
Filtration X
Polymer Bead Waihing X
Routine Cleaning Water X X X X
568
-------
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous (45 ‘ederal
Re lster 3312, May 19, 1980):
Carbon tetrachioride — U211
Di—n—butyl phthalate — U069
Dimethyl phthalate — U102
Ethyl acrylate — U113
Di pos il of these compounds and PVAc resin containinb residual amounts ot!
these compounds must comply with the provisions set forth in the Resource
Conservation and Recovery Act (RCRA).
569
-------
SECTION 25
POLYVINYL ALCOHOL
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Polyvinyl alcohol (PVA) is a water sensitive polymer that is white to
yellow in color. PVA is an unusual polymer in that it is n t manufactured
from the vinyl alcohol monomer. The theoretical monomer, 01 2 —CHOH,
rearranges to acetaldehyde, CH3$H . Consequently, the polymer, which is
shown below, is obtained by the hydrolysis of polyvinyl acetate (PYAc).
(CH 2 CHOH) 5
The properties of PVA are primarily determined by the molecular weight
of the parent polyvinyl acetate and the extent of hydrolysis of the poly-
vinyl alcohol. The molecular weight of PVA ranges from a few thousand to
almost one million.(222J The degree of ‘hydrolysis, or how many of the
acetate groups are hydrolyzed to hydror.yl groups, determines the properties
of the resulting resin. -
Polyvinyl alcohol with a small percentage of the acetate groups hydro-
lyzed has greater flexibility, dispersingpower, water sensitivity, and
adhesion to hydrophobic surfaces when compared to the highly hydrolyzed
polymer. Similarly, polyvinyl alcohol with a high percentage of hydroxyl
groups has increased tensile strength, solvent resistance, solubility in
water with resistance to additional hydrolysis, and adhesion to hydrophilie
surfaces in contrast to the properties of the polymer with less than 80
percent hydrolysis.
Physical properties of fully hydrolyzed polyvinyl alcohol are listed in
Table A—36 in Appendix A. Polyvinyl alcohol is typically classified as one
of three types: partially acetylated vhi h is 87 to 89 percent hydrolyzed;
fully hydrolyzed, in which 98 percent of the acetate groups have been con-
verted to h ’droxy1 groups; and super hydrolyzed, which is 99.7 percent con-
verted. Table A—37 in Appendix A gives density as a function of PVA acetate
content. Solubility of PVA in various organic solvents is presented in
Table A—38 In Appendix A.
The major uses for polyvinyl alcohol include textile warp sizing,
adhesives, suspension aids in polymerization, paper coatings, cosmetic
manufacture, optical appllcatton , membranes, sponges, paint, and soil
erosion control. Coating, casting, and dipping applications comprise the
majority of polyvinyl alcohol uses. PVA is also sed in the production of
570
-------
polyvinyl butyral. In 1980, PVA production totaled 63,900 metric tons.(65]
Table 197 presents consumption of polyvinyl alcohol for 1978.
INDUSTRY DESCRIPTION
Polyvinyl alcohol is not polymerized from the vinyl alcohol monomer,
which rearra .aes to acetaldehyde. Rather, polyvinyl acetate is hydrolyzed
to make polyvinyl alcohol. Similarly, some of the polyvinyl alcohol
produced goes to polyvinyl butyral production. This sequence is pictured
below:
Polyvinyl Polyvinyl Polyvinyl
Acetate Alcohol Butyral
Production Production Prod ct ion
End Uses End Uses End Uses
The polyvinyl alcohol industry is comprised of three companies, each of
which produces the polymer for polyvinyl butyral production as well as for
various end uses. The manufacturers for polyvinyl alcohol are listed in
Table 198. Nameplate capacity of polyvinyl alcohol in 1980 was 102,000
metric tons. [ 35, 56J Of this capacity, 22,000 metric tons were available
for captive polyvinyl butyral production.
The P’1A industry currently uses polyvinyl acetate produced by tvo pro-
cesses: suspenaion and solution polymerization. Suspension po ymerization
i typicaliy u3ed to manufacture medium to high molecular weight (100,000 to
1,000,000) polymer while solution polymerization typically produ-eg low
molei ular weight (10,000 to 50,000) polyvinyl alcohol. Th: h)d Olysis is
usually not a true hydrolysis reaction, where a stoichiometr:c qualtity of
base and the presence of water are required, but rather an ester interchange
reaction. Alkaline conditions are usually used for solution polymerized
polyvinyl acetate, and acidic conditions for suspension polymerized poly-
vinyl acetate. The former process is sensitive to the presence of water;
therefore, it is more suited for solution polymerization productg.(137J
Since process type used for polyvinyl alcohol production is not published,
there is no correlation between the plants listed in Table 198 and the
processes discussed.
PVA products are primarily consumer oriented. Adhesives, textile and
paper coatings, and paints are affected by the economy. The use of PVA as a
protective colloid in suspension and emulsion polymerization processes will
reflect the general trend of other polymers. PVA production peaked in 1979
t 67,100 metric tong, then dropped to 63,900 metric tons in 1980, but is
still above the 56,100 metric tor. level of 1976. With an excess of 38,100
metric tons of capacity, no new plants are likely in the ne r future.
571
-------
tABLE 197. 1978 CONSUMpTION 0? POLYVINYL ALCOHOLa
Use Thousand Metric Tons
Textile Warp Sizing 28
Adhesives 15
Polymerization Aid 8
Paper Sizings and Coatings 3
Miscellaneous 4
Exports 6
66
agXC lUdifl 8 PVA for polyvinyl butyral.
Source: Chemical Economies Handbook , updated annually, 1978 data.
572
-------
TABLE 198. POLYVINYL ALCOHOL PRODUCERS AND NANEPLATE CAPACITY
Capacity
Producer j tric Tona )
Air Produetg, Calvert City, , KY 25,000
[ uPont, LaPorte, TX 57,CO0
1onsanto, Springfield, MA 20,000a
TOTAL 102,060
aThie capacity includea 11,000 metric tone of PVA produced for pølyvinyl
butyral production.
Sourcee: Chemical Economice Handbook , updated annually, 1978 data.
Directory of Chemical Producere , 1981.
573
-------
PRODUCTION AND END USE DATA
In 1980, production of PVA resins were 63,900 metric ton..1651 Of the
102,000 netric tone of PVA capacity In 1981, 22,000 metric tone were avail-
able for subsequent manufacture of polyvinyl butyral.(35, 56j
In addition to polyvinyl butyral production, PVA is used iis: [ 133, 137,
2221
• Protective coilold In emulsion and euspension polymerizatj)n;
• Warp sizing in the textile industry;
• Component in aqueou, adhesives;
• Binder for phosphorescent pigments and dyes in television tubes;
• Polarizing lenses;
• Film vhich dissolve, in water for premeasured detergent packets;
• Ion exchange membranes;
• Sponge for medicinal use.;
• Paper coating to give a smooth, glossy finish which receive, ink
well;
• Antifogging agent for gas masks;
• Component in paint;
• Binder for sand molding;
• Photographic film baa. or coating;
• Sausage casing.;
• Soil stabilizers; and
• Cosmetics.
PROCESS C€SCRIPTIONS
Polyvinyl alcohol is produepd from the hydrolysis of polyvinyl ae.eat.
since the theoretical vinyl alcoh,l monomer rearranges to acetaldehyde,
Vinyl acetate is fI .t polymerised to form polyvinyl acetata (so. the sec-
tion on polyvinyl acetate for the appropriate polymerization chemistry),
which is then hydrolyzed with ethanol in eit”,r an acidic or alkaline
environment to produce polyvinyl alcohol and methyl acetate.
574
-------
2CH0C0CH 3 ) 1 + nCH30H- - fl CHOH jj + nCH3OCOCH 3
The percentage of acetate groups replaced by hydroxyl groups gives the
degree of hydrolysis, which can be controlled to produce the desired
properties in the ‘nal product.
Polyvinyl acetate which is used for polyvinyl alcohol production is
made y suspension or solution polymerization. Most polyvinyl alcohol
processes are continuous, although there are batch processes in use.j137J
If the PVA is c inpounded or used in polyvinyl. butyral production at another
site, the resin is dried and shipped in powder or granular form. [ l33J
Comonotners say be added to produce high solvent resistant films. Tables 199
and 200 list typical input materials and operating parameters for these pro-
cesses. Input materials used in addition to polyvinyl acetate for polyvinyl
alcohol production and si’bsequent formulation are listed in Table 201.
Suspension Polymerization and Hydrolysis
Suspension polymerization of PVAc is typically used to produce medium
to high molecular weight (100,000 to 1,000,000) polyyinyl alcohol.(133J As
Illustrated in Figure 65, vinyl acetate suspended in water is polymerized in
the presence of a catalyst. The polyvinyl acetate beads produced are sent
to a surge tank before drying. The water removed during drying is recycled
to che reactor or sent to vastevater treatment. Methanol, dried beads, and
the hydrolysis medium are combined to hydrolyze the polyvinyl acetate to
polriinyl alcohol. Alkaline hydrolysis results in a gel which i. broken up
by agitation. The polyvinyl alcohol mixtut is fed to a solve’it recovery
column where the methanol and by—product methyl acetate are removed and
either recycled, sold as paint solvent f211J, or sent to an extractive
distillation column where water I . added to aid in the separation. Methanol
and water are removed from the bottom of the column while methyl acetate and
water taken from the top of the column are hydrolyzed to methanol and acetic
acid. The medium and high molecular weight polyvinyl alcohol produced is
removed from the solvent recovery ‘ o1umn free of excess solvent 1 hydrolysis
medium, and by—product. If the re gis is ahipped to another location for
further processing, it may be dried.
A stoichionetric quantity of base and the presence of water are neces-
sary for hydrolysis, while In solution. polymavizatjon, only a catalytic
amount of base and the presence of an alcohol are required. [ 137J
Solution Polymerization
The PVAc from which low molecvlar weight (10,000 to 50,000) polyvinyl
alcohol is made Is usually produced by solution polymerization. Zn this
process, as presented in Figure 66, methanol and vinyl acetate are fed,
along with a catalyst, to a reactor. The polyvinyl acetate produced 1.
cerried along with the metl’anol to the hydrolyzer.
575
-------
TABLE 199. TYPICAL INPUT MATERIALS If) P )LYVINYL ACETATE
(POLYVINYL ALCOHOL) PRODW?tON PROCESSES
IN ADDITION TO MONOMER All’) INITIATOR
Polymerization Organic Protective
- Proces. Water Solvent Surfactants Colloids
Suspension X I
Solution I I
TABLE 200. TYPICAL INPUT MATERIALS AND OPERATING PARAMETERS FOR
POLYVINYL ALCOHOL PRODUCTION PROCESSES
Interchange
Process Acid Base ‘ Reaction Time
Alkaline Room temprature Rapid
Acidic I 51—59C 3 hours
Sources: Lncyclopedta of Cheiiical Technology , 2nd Edition.
Encyclo?edia of Polymer Science and technology .
576
-------
TABLE 201. INPOT MATERIALS AND SPECIALTY CHEMICALS USED IN POLYVINYL
ALCOHOL MANUFACTURE IN ADDITION TO POLYVINYL ACETATE
Cro ’slinking Agents dialdehyde starch
diepoxides
dihydroxy diphenyl sulfone
diisocyanates
dimethylolurea
dtviriyl s’ 1fone
glutara ldehyde
glyoza l
oxalic acid
polyacrolein
tr(methylolsie laajne
Solvents vater 5
Dyes Congo red
Pontamjne Bordeaux B
Pontaeine Brown D3GN
P ntamjne Geat Red F
Pontamine Green 2GB
Ponta fne Orange 1
Plast icizers dihityl phthalate
2 1 2—dj ethyl—i ,3—propanediol
ethoxylated phosphoric acid butyl
ester
ethyl acid phthalgte
glycols
eethy1 la ed cyclic ethylen. urea
onopheny1ethcr of poly(oxyethylexe)
sorbitol
trie(chloroethyl )phosphate
trie(tetrahydrof rfur,l ho.phat.
urea
Cononomers acrylaeid,
acrylati esters
aeryionitr lle
a
carbamrlyieethyt rieethyjammoniua
hydrochloride
chloromethylester and trimethylamin.
or pyrrtdine
crotonic acid
I . 2 -epoxy—J—d1ethylamfnopro n .
ethylene
(continued)
571
-------
TABLE 201 (continued)
Comonomers (continued) ethylene oxide
ethylentetne
formaldehyde and salicyclic acid
nethyl methacrylate
polyfunctional acid.
styrenesulfonic acid
hiourea
vinyl acetate
vinyl butyl ether
vinyl chloride
vinylene carbniate
vinyl ketone
vinyl versatate
Alkaline Hydrolysis Levi. bases
Media mathanolic sodium methoxide
potassi’.a. hydroxide
sodium hydroxide
Acidic Hydrolysis hydroc.iloric *cid
Media Levis acid.
2 —naphthalenesulfonic acid
sulfuric acid
See T jl A-37 in Appendix A fo’ additional •olubllity information. Sea
pol,:inyt acetate, Section 23 tn a list of solvents used In solution
polyme-iaatjc,n.
Sources: Encyclopedia of Clienical Teehno1og , 2nd EdItion.
Encyclopedia of Polymer Science and Technoloiy .
1. C. Prichard, Polyvinyl Alcohol: Basic Properties snd Uses ,
1970.
578
-------
Methanol and Wdter
to Wa tewat.r
I reatment
Figure 6 .
Co tt uoua polyvinyl alcoho. production using the suspension polyaterization process.
Sources: Hydroca b n Processin 1 , Noveeber 1981.
Polyvin’,l Alcohol: Properties and Applications 1 1973.
MeIha,uI
and A etji
Acid
Water to
Vent Wastewater
Treat nt
- .4
To Waceewater
I I at nt
hater to
thlnn.r
Mediu and Nigh
‘ioL cular Weight
Polyvtnyl Alcohol
-------
Vant
and
A id
0
Figure 66. Continuous polyvinyl alcohol production using the solution polyaerizetion process.
Sources: Hydrocarbon Processing , Novesbor 1981.
P lyviny1 Alcohol: Properties and Applications 1973.
V in,
A •1 all
Acid or
I a n.
Lan ?bL.cuIa , W.I ht
PuIy%inyI Alohol
SoI,.nt
IWlhano .fld W1.r I)
utan.ter Tveat..nt
-------
A typical recipe for the production of polyvinyl acetate by the
solution process is: [ 54J
Material Parts by Weight
Vinyl Acetate Monomer 6,511
2,2 ‘—Azobisisobutyrnitrile (catalyst) 24
Methanol (solvent) 4,350
Methyl Acetate (solvent) 6
The product from the polyvinyl acetate process Is used along with the
medium, which is either an acid or a base, in the following recip.. to
produce polyvinyl alcohol by the solution process: 54J
Material Parts by Weight
Sodium Hydroxide (catalyst) 455
Methanol (solvent) 2,585
Methyl Acetate (solvent) 4
Water 21
The resulting polyvinyl alcohol mixture is sent to a solvent
recovery column where the by—product methyl acetate, the solvent methanol,
and the hydr3lysis medium are removed and either recy.led, sold as paint
snivent, or sent t., an extract lye distillatinu column. The low molecular
weight polyvinyl alcohol product is then free from excess solvent nd
by—product. If the resin is shipped to another location for further
proces;ing, it may be dried.
energy ReguiremenLs
Data for the energy required during polyvinyl alcohol production were
not found In the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
Polyvinyl alcohol 1. an inert compound which has been approved by the
FDA for use In cosmetics, bacteriostatic agents, food wrap, and other exter-
nal uses. Polyvinyl alcohol film shows no ill effects when used in surgery
or as a carrier for medtcatlun.1133J However, in one study performed on
rats, polyvinyl alcohol exposed subcutaneously in rats caused a statfati—
cally sIgnificant increase in the incidence of metastasizing tumors in the
test anisals.12321 Low molecular weight PVA is absorbed by the liver and
kidneys in some test animals.(137J
Sinre PVA Is not converted from the monomer, but rather from PVAc,
there are very few monomer amissions from the reactor. Polyvinyl acetate is
I.,w in vinyl acetate, thereby reducing the possibility of vinyl acetate
eaissions durtn PVA resin drying.
581
-------
Worker Distribution and Emissions Release Points
Worker distritution estimates have been made using factors developed by
correlating equipment manhour requirements with the pi.ocess operations shovu
In Figures 65 and 66. Estimates for suspenson and solution polymerization
processes are shown in Table 202.
No major air emission point sourcas are associated with polyvinyl
alconol production processes. Fugitive emtszion sources, however, may,
significantly impact environmental residuals and/or worker health. The
degree to which these ‘impact the worker’s environment are determined by the
stream constituents, process operating parameters, engineering and
administrative controls, and maintenance programs.
Table 203 lists process sources of fugitive emissions from polyvinyl
alcohol production.. Inttiatois, protective colloids and other additives
potentially emitted from reactor vents are listed in Table 203. Toxicity
information for major additives is discussed in detail in IPPEU Chapter lOb.
Ethylene, a comonomer, and nitrogen, used as an inertirg agent, are
simple aephyxiants and their presence poses a hazard because it may limit
the amount of oxygen available in the atmosphere. Typically—used solvents
include methyl, butyl, and ethyl alcohols, ethyl and methyl acetate,
propionaldehyde and various ketone compounds.
Health effects information regarding Input materials of particular
concer i are discuoied in the following paragraphs. Available toxiciPy and
regulatory information for major input materials is summarized in Table 10.
Health Effects
Several of the eomonomers used in polyvinyl alcohol manufacture pose a
significant health risk to plant employees if exposure to even relatively
low doses occurs. These comonomer. Include vinyl chloride, ethylene oxide,
acrylonitr le, ethylenetmine, thiour.a, formaldehyde, and acrylamide. The
cross—linking agent divJnyl •ulfone Is also a highly toxic compound. A
synopsis of tie reported health effects resulting from exposure to these
substances follows.
AcEylamide is a ,‘eurotoxin, causirtg symptoms of ataxia, hypersomnia,
end vertlgo.(170J Although the polymer is nontoxic, absorption of acryla—
mide through skin or dusts is associated with serious neurilogical conse—
quences488j Animal test data indicate that exposure to acrylamide might
also cause mutagenic and taratogenic effect.. The OSRA air standard is hl) 3
sglm 3 (8 hour T A).f6’j
Acrylonitrite , a suspected human carcinogen I107J, causes Irritation of
the eyes and nose, weakness, labored breathing, dizziness, impaired judg-
ment, cyanosis, nausea, and convulsions in humans. Piutagenle, teratogenic,
and tunorigenic effects have been reported in the literature. The OSIIA air
standard is 2 ppm (8 hour TWA) with a 10 ppm ceiLtng.(69J
582
-------
TABLE 202. WORKER DtSTRIBUTION ESTIMATES FOR POLYVINYL ALCOHOL PRODUCTION
Process Unit Workers/Unit/8—hour Shift
Suspension Polymeriza’tion Continuous Reactor 0.5
Surge Tank 0.125
Water Removal 0.25
Hydrolyzer 0.5
Solvent Recovery 0.25
Distillation Column 0.25
SoluiJon Polyaerization Continuous Reactor 0.5
Hydrolyzer 0.5
Solvent Recovery 0.25
Distillation 0.25
583
-------
tABLE 203. SOURCES OP FUGITIVE DUSSIONS FROM PVA MANUFACTURE
Process
Source Constituent ! ioa Solution
Reactor Vents Vinyl Acetate X
Initiators X X
Protective Colloids X X
Solvents Z
Surge Tank Vent Vinyl Acetate X
Sokvent Recovery Solvents *
Vents
Methanol X I
Extractive Distil— Methanol I I
lation Colunn
Vent
Product Dryinga ‘linyl Acetate X I
Solvents I
Particulates I I
5 1f the product is shipped.
584
-------
Divinyl sulfone can cause severe skin and eye burns similar to those
from mustard gas. [ 87J By condensing with amino acids and other groups, it
can also cause injury and enzyme inhibition. [ 87J When heated to decomposi-
tion, or on contact with acid or acid fumes, it emits sulfur oxide
fumes. [ 2421
Ethylene oxide exposure of 500 ppm has been associated with convul-
sions, gastrointestinal tract effects, and pulmonary system effects in
humans. [ 58J Although testing for carcinogenic effects is Inconclusive,
ethylene oxide causes tumorigenic, mutagenic, and teratogenic effects. The
current OSHA air standard Is 50 ppm (8 nour TWA). [ 67J
Ethyleneimine has shown carcinogenic effects in animal tests. [ 101J
Exposure can cause severe eye, skin, and nose irritation; ethyleneimine is
extremely toxic if ingested with the possible lethal oral dose for humans
set between 5 and 50 mg/kg. [ 85J The current OSHA air standard is 1 mg/n 3
(8 hou’ TWA). [ 67J
Formaldehyde poses a high toxic hazard upon ingestion, inhalation, or
skin contact [ 49J with human effects reported at doses as low as 8 ppm. [ 127J
This suspected carcinogen is a potent mutagen and teratogen. The OSHA air
standard is 3 ppm (8 hour TWA) with a 5 ppm ceiling. [ 67J
Polyvinyl alcohol has produced positive results in animal testing for
carcinogenicjt 7 . [ 107J Its single dose toxicity, however, is presumably
low. [ 85J Implantation of PVA sponge as a breast prosthesis has been
associated only with foreign body type of reaction [ 107J; neutral srlutions
of PVA have also been used in eyedrops on human eyes vithoii iifficulty.(87j
Thiourea has also shown carcinogenic effects in animal tests [ 1001 as
well as possibly causing mutagenic effects. Death has occurred when the
human exposure i vel reached 147 mg/kg.(8J
Vinyl chloride is a proven human carcinogen [ 1071 which may cause per-
manent injury or death after inhalation, even if the exposure is relatively
short. [ 242J Human reproductive effects occur at concentrations as low as 30
mg /rn 3 [ 126J; both tumorigenic and mutagenic effects have been observeci in
humans as well as test animals. The OSHA air standard for vinyl chloride is
I ppm (8 hour TWA) with a 5 ppm ceiling. [ 68J
Air Emissions
Sources of fugitive VOC emissions are listed in Table 202. All of
these sources are vents which may be controlled by routing the vented stresm
to a flare to incinerate the remaining hydrocarbons or to blowdown. 2d5J
Other ‘ugitive VOC emissiong may arise from leaks in process equipment.
Alth(,u h equipment modification may be used to reduce emissions from these
sources, a routine inspection and maintenance may be the best control.
Fugitive particulateg result from this process only whe, the product s
shipped. Venting the product dryer stream to either a bagho.ise or an elec-
trostatic precipitator will control particulates.
585
-------
Wastevater Sources
Polyvinyl alcohol production processes generate two major vastevater
streams: one from hydrolysis and one from solvent recovery. The water
removed from the beads in the suspension polymerizatjo process may be
recycled or combined vith these other streams. These sources are listed in
Table 204. The data found in the sources consulted listed vastevater value.
for a combined wastewater stream from the hydrolysis and solvent recovery
sections of a polyvinyl alcohol process of an unspecified type.(93J These
values are listed below.
Amount/Metric Ton of
Wastevater Component of Polyvinyl Alcohol
Methanol 0.3 kg
Acetic Acid 50 kg
Ethyl Acetate 25 kg
Sodium Sulfate 250 kg
Methyl acetate genersted is converted to methanol and acetic acid; there-
fore it is not expected to be a major constituent in the wastewater.
Solid Wastes
The solid wastes generated during PVA production include substandard
PVA which cannot be salvaged by blending. These wastes are not hazardous;
therefore their disposal should not pose an environmental problem.
Environmental Regulation
Effluent limitations guidelines for polyvinyl alcohol have not been
established.
New source performance standards (proposed by EPA on 3 January 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except In emergency pressure releases, which should no
last more than five days; and
• Leaks (which are defined by VOC emission, greater than 10,000 ppm)
must be repaired within 15 days.
The following compounds have been listed as hazardous (45 Federal
Register 3312, May 19, 1980):
Acrylamide — 11007
Acrylonitrile — 11009
Di—n—butyl phthalate — 11069
Ethylene oxide — 11115
Formaldehyde — 11122
386
-------
TABLF 204. SOURCES OF IJASTEWATER FROM POLYVINYL Al COHOL MANUFACTURE
Frocega
Source S 9p naion Solution
Water Removal X
Hydrolyzer X K
Solvent Recovery Train X
587
-------
Methanol — U154
Methyl methacrylate — U 162
Thiourea — U2l9
Vinyl chloride — 43
Diapoaal of thee. coepound. or PVA reetna contaitiing residual a ounta of
these conpounds nust conply with the provisions set forth in the Resource
Conservation and Recovery Act (RCRA).
583
-------
SECTION 26
POLYVINYL CHLORIDE
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTI ON
Polyvinyl chloride (PVC) is a very strong, moderately rigid, chemically
inert, non—toxic polymer. It is also lightweight compared to metals and
impact resistant when properly modified. Because of these characteristics
it is used to produce a wide variety of consumer goods and industrial
materials. The major use for PVC is in building and construction, which
uses 50 percent of the total product. Other PVC uses include transporta-
tion, upholstery, packaging, electrical tapes, and consumer goods. PVC
polymer (homopolyner) and copolymer sales in 1981 totaled 2,551,000 metric
tons with the homopolymer representing 80 percent of the U.S. production.
(40, 172J
PVC is manufactured from the polymerization of vinyl chloride monomer
tt prodiic th fc ,liowtng repeating vinyl chloride atructure
( CH 2 —CHC1 )
With the introduction of modifiers, a wide range of properties can be
achieved. Table A—39 in Appendix A presents typical properties of PVC in
the rigid and plasticized form.
INDUSTRY DESCRIPTION
PVC is one of the largest segments of the plastics and resins industry.
In 198C, the production of PVC was second only to low density polyethylene.
(65 J
There are 21 major PVC manufacturers which had a combined annual PVC
manufacturing capacity of 3,589,000 metric tons (7,896 x j 6 pounds) in
1980. The projected 1981 U.s. annual capacity was 3,938,000 metric tons
(8,664 x 106 pounds) or a 10 percent increase in capacity. Major U.S. k’VC
manufacturers and their respective capacities are listed in Table 205.
PVC is produced by four different polymerization technologies; mass,
solution, suspension, or emulsion polymerization. The literature does not
specify which polymerization technology is utilized by each PC manufac-
turer. However, in 1981, PVC manufactured using suspension polymerization
comprised 83 percent of the United Srateg market, PVC via emulsion po ymeii—
zation added 8 pc rcent, PVC mass polymerization contributed 7 percent, and
the remaining 2 percent was manufactured by solution polymerization. [ 40J
589
-------
VJLE 205. MAJOR POLYVINYL QILORIDE MANUPACTURERS
Capacity as
of October
1980 (1000
Manufacturer Location ( Metric Tons )
Air Products and Chemicals, Inc.
Plastics Division Calvert City, KT 100
!ensacola, FL 91
100
Borden, Inc.
Borden Chemical Division
Thermoplastic Products Illiopolis, II 154
Leominster, Pt A 84
GeisMr, j
1 I
Certain—Teed Corp. Lake Charles, LA 86
86
conoco inc.b
Conoco Chemicals Division Aberdeen, PG 161
Oklahoma City, OR lee
17 1
Diamond SPuimrockd
industrial Chemicals and
Plastics Unit
Plastics Division Deer Park, TX 213
Dela,are City, bE 55
268
Ethyl Corp.
Chemicals Croup Baton Route, LA 82
Formosa Plastics, U.S.A. Point Comfort, TX oe
The Gereral Tire and Rubber Co.
Chemical/Plastics Division
GTR Chemical Co. Ashtabula, OH 1 37
Point Pleasant, W ‘.1
(continued)
590
-------
TABLE 205 (continued)
Capacity as
of October
1980 (1000
Manufacturer Location ( Metric Tons )
Georgia—Pacific Corp.
Chemicals Division Plaquemine, LA 318
318
The B. F. Goodrich Co.
8. F. Goodrich Chemical
Division Avon Lake, 011 1368
Convent, LA 08
Henry, IL 91
Long Beach, CA 68
Louisville, KY 170
Pedricktovn, NJ 688
Plaquemine, LA 86
619
The Coodyear Tire .ind R.ibber Co.
Chemical Division Ni ara Falls, NJ 32
Xeysor Corp. Sangus, CA 23
23
Occidental Petroleum Corp.
Hooker Chemical Corp., I
subsidiary
RUCO Division Burlington, NJ 86
Plastics Croup
Plastics Division Baton Rouge (Addle), LA 100
Perryville, p
Pottctovn, PA 109 h
413
Pantasote Inc.
FilmlCompound Divisi Passaic, NJ 25
Point Pleasant, WV 39
Rico Chemical Corp. Guayanilla, PR 76
76
Shintech Inc. Freeport, TX l S O i
150
(continued)
591
-------
TABLX 205 (continued)
Capacity as
of October
1980 (1000
Manufacturer Location ( Metric ‘Toni )
Stauffer Chemical Co.
Pl istics Division Delaware City, DX 127
Long Beach (Carsc.n), CA 64
191
Tallyraad Chemcals, inc.i New Bedford, MA
Tenneco, Inc.
Tenneco Chemicals Inc. Burlington, NJ 73
Plemington, NJ 47
Pasadena, TX 2181
UnLon Carbide Corp.
Chemicals and Plastics South Charleston, WV 23
Division Texas City, TX 57
80
W f taker Corp.
Great American Chemical,
subsidiary Fitchburg, NA 34
TOTALtm 3,589
•r any has announced plans to build a 136,000 metric ton. per ,ear plant
at th’is location to bà complete i i 1983.
bcoapany viii expand total PVC capacity to 325, 0’) metric ton. per year in
1981 .
Cflete is some doubt as to the actual capacity of this plant. It vas
reported as three dJfferent values.
dAn expansion of 34,000 to 45.000 metrtc tons per year is scheduled to
become effective by the end of 1981.
(continued)
592
-------
TABLE 205 (continued)
eA 241,000 metric ton per year plant is scheduled for completion in early
1982 at this location.
capacity at this plant will be expanded to 68,000 metric tons per
year by the fourth quarter of 1982.
SPlant expansions and constructions have been announced as follows:
Avon Lake — 45,000 metric tons expansion for fourth quarter 1981,
Pedricktovn — 91,000 metric tons expansion for fourth quarter 1981,
Convent — new 500,000 metric tons plant with plans to have first phase on
stream by thl’d quarter 1983, complete by 1985, has been put on
indefinite hold.
hThe acqutsit ton of tnese pLants from Firestone was announced in September
1980.
t Plans have been announced to double capacity by mid 1981.
i i. plant was reported under Tallyrand Chemicals in one source and
International Materials Corporation in another source.
kCapecity to total 45,000 metri.. tons per year in 1981.
‘Total capacity at Pasadena announced to be 341,000 m’tric toni per year
by mid—1901.
mDoes not add to total of numbers isted due to roun i—off errors.
Sources: Chemical Economics Handbook , updated annually, 1980 data.
Directory of Chemical Producers , 1981.
Modern Plagtica , January 1982.
Organic Chemical Producers Data Base.
593
-------
The major producers of PVC are major petroleum and petrochemical
companies. Ten of these companies represent over 80 percent of the PVC
production capacity 1 with other chemical and compounding companies account-
ing for the remainder. These companies produce PVC both for captive use and
for merchant sales to PVC compounder..
Approximately 37 percent of the PVC production capacity is located ia
the states of Texas and Louisiana (9 sites). Another 20 percent of the
capacity is located in the New Jersey, Pennsylvania, Maryland, and Delaware
area (10 sites).
As important environmental aspe t of P•JC production at large, inte-
grated far.ilities is that many waste management options exist. PVC wastes
may be treated either befors or after combination with the rest of the plant
wastes. Treating PVC wastes before combination with the remaining plant
wastes allows the removal of potentially troublesome pollutant , from a
relatively small stream. The treated stream is then either discharged or
conDined with the plant wastes sent to the plant treatment system. Waste
management options are, therefore, very site and facility specific.
Since PVC is used in so many segments of the U.S. economy, the PVC
market f3llows the general trends in the U.S. economy. With the recent
dovnturns in the American automobile and housing markets, the PVC market has
shov’ a similar decline. Presently about 35 percant of the available PVC
manufacturing capacity is unused. These two factors suggest that new PVC
facilities and process expansions will not be contemplated in the near term.
PRODUCTtON AND END USE DATA
The polyvinyl chloride segment of the plastics and resins industry is
the second largest after low density polyethylena.(65J PVC production was
2,551,000 metric tons (5,612 i 106 pounds) during 181.
The largest markets for PVC products are construction related. Approx-
imately 55 percei’t of the construction products are manufactured from rigid
PVC md 45 percent are manufactured from plasticized PVC. Porty percent of
the total resin used is for piping: inc1ud ng pressure (thickwall) pipe for
water supply, irr gation, and chemical processing; and non—pressure (thin-
wall) pipe for drains, sever systems and electrical conduits. Other uses
f or PVC are in the production of flooring, wall coverings, upholstery,
appliances, housewares, automotiv. wire, meat wrap, blister pecks, and
phonograph records.
Th. markets, corresponding production volumes, and polymer processing
operations used for PVC end product manufacture are presented in Table
206 •
apor an explanation of various polymer processing operations see IPPEU
Chapter 1t 1 )a, Plastics and Resins Processing.
594
-------
tABLE 206. MAJOR MARKETS FOR POLYVINYl. ChLORIDE
_______ 1981
Market i,000 Metric Tons
CALENDER! NC
Building 6 construction
Flooring 68
Paneling 11
Pool—pond liners 16
Roof nembranes 9
Other building 2
Transportation
Auto upholstery/trim 32
Other upholstery/trim 8
Auto tops S
Packaging: sheet 36
Electrical: tapes 4
Consjmer & instItutional
Spi.rting/recrea j 05 10
Toys 15
Baby pants 2
Footwear 14
Handbags/ c 5 5 e 5 1!
Luggage 9
Bookbinding 2
Tablecloths, mats 17
Hospital & healtheare 7
Credit cards 8
Decorative file (adhesive back) 5
Stationery, novelties 2
Tapes, labels, etc. 6
Purni ture/furnishi ngs
Upholstery 34
Shover curtaIns 5
Window shades/blinds/a ing. S
Waterbed sheet 4
Vailcovertag 14
Other calendering 8
TOTAL CALENDERING 369
(Continued)
595
-------
TABLE 206 (contftuel)
1981
Market 1,000 Metric Tons
EXTRUSION
Building & construction
Pipe 6 conduit
Pressure
Water 354
Gas 9
Irrigation 111
Other 9
Drain/waste/vent 104
Conduit 168
Sever/drain 141’
Other 27
Siding & accessories 82
Window profiles
All-vinyl windove 7
Composite windows 23
Mobile howe skirt 7
Gutters/dovnspouts 2
Foam moldings 14
Weatherstripping 11
Lighting 8
Trans port at ion
Vehicle floor mats 8
lumper strips 4
Packaging
FIlm 123
Sheet 13
Electrical: wire and cable 170
Consumer & institutional
Carden hose 18
Medical tubing 16
Blood/solution bags 20
Stationary/novelties 4
13
TOTAL EXTRUSION 1,473
(continued)
596
-------
TABLE 206 (continued)
1981
Market 1 00O Metric Tons
]‘NJECTION MOLDING
Building & construction
Pipe fittings 50
Other building 3
Transportation: bumper parts 5
Electrical/electronics
Plugs, connectors, etc. 30
Appliances, business machines ii
Consumer & institutional
Footwear 20
Hospital & heaiLh’ are 7
Other injection 15
TOTAL INJECTION MOLDING 147
BLOW MOLDING: bottles 45
COMPRESSION MOLDING: sound records 49
DISPERSION MOLDING
Transportation 16
Packaging: closures 14
Consumer & institutional
Toys 3
Sporting/recreatIon 8
Footwear 6
Har.dleg, grips 6
Appliances 6
Industrial: traffic cones 6
Adhesives, etc.
AIheqives 5
Sealants 4
Miqeellaneoug 5
Other dispersion 3
TOTAL DISPERSION MOLDING 84
(continued)
597
-------
TABLE 206 (contijued)
1981
Market 1,000 Metric Tons
DISPERSION COATING
Building: flooring 61
Transportation
Auto upholstery/trim 12
Other upholstery/trim 2
Ant icorrosion coatings 5
Consumer & institue ona1
Apparel/outerwear 6
Luggage 4
Tablecloths, mats 4
Hospita l/healthcare 3
Furniture/furnishings
Upholstery 8
Window shades/blinds/awnings 6
Valicoverings 6
Carpet backing 7
Other 15
TOTAL DISPERSION COATING - 139
SOLUTION COATING
Packaging: cans 4
Adhesives/coatings 21
TOTAL SOLUTION COATING 25
VINYL LATEXES: adhesives/gealants 25
EXPORT 195
GRAND TOTAL 2,551
Source: Modern Plastics , January 1982.
598
-------
PROCESS DESCRIPTIONS
PVC is produced by mass, solution, suspension, or emulsion polymeriza-
tion. OE the 2,551,000 metric tons sold in 1981, PVC manufactured by sus-
pension polymerization comprised 83 percent of the United States inarket. [ 40,
172J Emulsion, mass, and solution polymerization contributed the remaining
8, 7, and 2 percent, respectively, to the PVC market. [ 40J Tables 207 and
208 present typical input materials and operating parameters for the9c pro-
cesses. Specialty chemicals and other input materials used are licted in
Tabie 209.
Suspension polymerization is used to manufacture resins for most PVC
app]ications, such as extrusion of pipe and siding and sheet. Although mass
polymerization may also be used to produce PVC for the same applications,
the polymer beads manufactured by suspension polymerization are easily sepa-
rated from the aqueous medium while mass polymerization produces a resin
which must be chopped, cut, or pelletized before use. Emulsion polyineriza—
tion provides PVC for use in dispersion resins since the small particles may
be uqed either in emulsion form or may be spray dried for inclusion in a
dispersion. Due to the high cost of solvents, solution polymerization is
used for very few PVC applications. I
In PVC production, vinyl chloride monomer is polymerized to make the
homopolymer, and copolymer3 are made from the polymerization of vinyl
chloride plus a comonomer. Initially, vinyl chloride becomes reactive after
combining with an initiator radical, R’. The vinyl chloride radical then
react8 wit’ other abori n ers to form the polymer chain.
Initiation
+ R.-øRCH 2 -CRC1
Propagation
• •
RCH 2 -CHCI + n(CH 2 CHC1)—*R-1- Cli 2 —CRC1 ) CH 2 —CHC1
rhe reaction can terminate in one of three ways: by radical combination,
chain transfer, or disproportionation.
Radical Combination
• S
RCR 2 —CHC1 + RCH 2 —CHC I — RCH 2 —CRCl—CHCl—CH 2 R
Chain Transfer
S
R’R + RCH 2 —CHCi- RCH 2 —CHClR + R’.
where R’R” represents a chain transfer agent.
Disproportionat ion
• •
R-CH 2 —CHC1 + R’ -CH 2 -C}IC1 — R-CN 2 —CE 2 Cl + V -CH—CHC1
599
-------
TA3LE 207. TYPICAL INPUT MATERIALS TO PVC PRODUCTION PROCESSES
IN ADDITION TO MONOMER AND INITIATOR
Input
Organic Suspension
Process Water Solvent Emulsifier Stabilizer
Suspension x X
Emulsion x X X
Mass
Solution X
(Precipitation)
avery small concentrations, which do not provide a true emulsion, may be
used.
TABLE 208. TYPICAL OPERATING PARMETERS FOR PVC PRODUCTION PROCESSES
Process Temperature Reaction Time Conversion
Suspension 45° — 55°C 12 hours 85 — 902
Emulsion 45° — 60°C (1 hour 602
Mass 40° — 10°C 8—12 hours 80 — 902
Solution 40° — 60°C 90 — 952
(Precipitation)
5 Only one producer uses this process in the United States. Only reaction
temperatures were available.
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of PVC , 19Th4977.
Iydrocsrbon Processing , March 1980.
Hydrocarbon Processing , November 1979.
Marshall Sittig, Vinyl Chloride and PVC Manafacture , 1978.
U.S. Environmental Protection Agenty, Source Assessment:
Polyvinyl Chloride , 1978.
(p00
-------
tABLE 209. INPUT MATERIALS FOR PVC MANUFACTURE
Function Compound Process
Suspension Stabilizer Gelatin Suspension
Hydropropyl methyl cellulose Emulsion
Methyl cellulose
Polyvinyl alcohol
Radical Initiator Acetal benzoyl peroxide Suspension
Acetyl cyclohexyl sulfonyl Emulsion
peroxide Mass
t—Amyl peroxyneodecanoate Solution
Azobisisobutyronitri le (Precipitation)
t—Butyl peroxyneodecanoate
t—Butyl peroxypivalate
ci—Cumyl peroxyneodecanoate
c*—Cumyl peroxypivalate
Dibenzoyl peroxide
Dibutyl peroxide
Di—2—ethylhexyl peroxydi—
carbonate
Dii sononanoyl peroxide
Dilsopropyl peroxydicarbonate
Dilauroyl peroxide
Di—n— ropyl peroxydiearbonats
Hydrogen peroxide
Isopropyl peroxydicarbonate
Lauroyl peroxide
Peroxydisulfates
Alkaline Buffer Sodium bicarbonate Suspension
Sodium carbonate Emulsion
Sodium phosphate
Comonomers Acrylic ester Suspension
Acrylonitrile Emulsion
Cetyl vinyl ether Mass
Ethylene Solution
Propylene (Precipitation)
Vinyl acetate
Vinylidene chloride
Plasticizers Phthalates Suspension
Butyl benzyl Emulsion
Butylhexyl Mass
Diallyl Solution
Di—n—amyl (Precipitation)
Dibenzyl
Din—buty l
Dicapryl
601 (continued)
-------
TABLE 209 (continued)
! !mction Coapound Process
Plait ici sers DicyC1 oh. 1
(continued) Diethy l
Di .(2—e thy lbutyl)
D1( 2 . .ethy lhe,pj l)
Din—he y1
Dilauryl
Dimethyl
Di nocty l
Dinpropyl
Sebacates
Dibensyl
Di-(2—butoxy.thyl)
Dibutyl
Dinethyl
Di(2ethylhexyl)
Dihazyl
Phosphate.
Tributyl
Tricresyl
Tri(2—eth,lhe l)
Tripheny l
Dibutyl Iauraa id.
Dieapryl dtgly Ol1.t.
Diuctyl leate
Diocty; thiodlglycol lat.
Ethylen. glycol dipelargonste
E ulsjfjers Alkyl sulfates Suspension
Alkyl snlfonat. .
Fatty ether sulfates
Long chain fatty acid
soaps of alkali ..t.i,
Molecular Weight Alkylene bi.—(.srcspto..
Regulators alkanoates)
POlybrom butenes
Chain Transfer Agents Carbon tetrachiorid. Solution
Dodecanethiol
(co ntinu .d)
602
-------
TABLE 209 (continued)
Function Conpouz d Procega
Solventa Acetone Precipita—
Benzene tion
n—Butane
Met hanoi
Methanol/water
n—Pentane
1,1,2 ,2—tetrafiuoro—
dichioroethane
Chiorobeozene Solution
Cyclohexane
1 , 2 —Dichtoroethane
Tetrahydrofuran
Source.: Encj’clopedia of Chenical Technology , 2nd Edition.
Modern Plastics , February 1981.
- S. Pein, PVC Tec no1og , 1972.
Marshall Sittig, Vinyl Chloride and PVC Manufacture , 1978.
603
-------
Both mechanisms are present in all of the processes discussed. Radical
combination prevails in the monomer rich phase, which is within the droplets
in suspension and micelles in emulsion polymerization and within the reac-
tion medium in solution and mass polymerization. Chain transfer mechanisms
dominate in a polymer system where other compounds are present to react with
the radical group.
Suspension Polymerization
In suspension polymerization, th radical initiator is dissolved in the
vinyl chloride monomer which is maintained as aqueous phase droplets by
means of vigorous agitation and a suspension stabili..e (or protective
colloid). The suspension stabilizer is added to minimize coalescence of the
droplets and appreciably increases the viscosity of the water phase without
changing the surface tension. The stabilizer is water soluble but insoluble
in vinyl chloride. An alkaline buffer is added to neutralize hydrochloric
acid as it is formed as a reaction by—product. Three recipes for suspension
polymerization of PVC are listed in Table 210.
The advantages of this process over other polymerization processes
include: lower cost of water as compared to organic solvents, excellent
heat transfer, no solvent recovery problems fever safety hazards due to no
volatile solvents, simpler temperature control, and less contamination of
the polymer. The major disadvantage of this process is the need to separate
the large amount of water from the product and the large excess reactor
volume required, since 60 to 80 percent of a batch is water.
As illustrated in Figure 67, vinyi chloride monomer, an initiator,
water, a suspension stabilizer, and a buffer are charged to the reactor.
Ratios of water to vinyl chloride range from t.5:1 to 4:l.(29J Low ratios
facilitate larger production volumes while high ratios allow better
temperature control, higher conversions,, and produce a •ore porous resin.
Suspension sLabilizers are typically used in èoncentrations of 0.03 to 0.5
parts per hundred parts of monomer.(293 Radical initiators are employed in
concentrations of 0.03 to 0.1 parts per hundred.(29j
The polymerization is performed in large agitated reactors. The reac-
tion is carried to 85 to 90 percent conversion in either stainless steel or
glass—lined carbon steel reactors ranging from 76 to 132 cubic meters (2,000
to 35,000 gallons). The polymerization rate is slower for suspension poly.—
erixation than emulsion, mass, or solution polymerization.
Since oxygen inhibits the polymerization, the reaction is normally
carried out in a nitrogen atmosphere. The nitrogen atmosphere also serves
to decree.. the hydrochloric acid evolved and increase the polymer
stability.
After the vinyl chloride droplets, which are 100 to 150 microns in
diameter, have polymerized, the mixture is stripped of unreacted monomer in
a flash tank and the polymer is sent to a blending tank. Air emissions may
result from the blending tank vent. The blended polymer mixtuL is eentri—
fuged to remove water. The resulting resin, with a water cont ’at of 18 to
04
-------
TABLE 710. RECIPE FOR PVC PRODUCTION USING SVSPENSION POLYMERIZATION
Parts by Weight
Material Process 1 Process 2 Process 3
Water 150 — 200 170 — 200 225 — 350
Vinyl Chloride 100 100 100
Lauroyl Peroxide (initiator) 0.1 — 0.5 0.1 — 0.3 0.2 — 0.4
Polyvinyl Alcohol (stabilizer) 0.03 — 0.06
Gelatin (stabilizer) 0.3 — 0.6
Methyl Cellulose (stabilizer) 0.2 — 0.9
Emulsifier 0.01 — 0.05 0.01 — 0.03
Sulfated Ester (emulsifier) 0.05 — 0.1
Buffer o.i — 0.3 0.1 — 0.3
Source: U. S. Penn, PVC Technology , 1972.
605
-------
Figure 67. pvc production using the suspension polynsrizatjon process.
Sources: Hydrocarbon Processing , Ilarch 1980.
Hydrocarbon Processing 1 Novesber 1981.
NI
Safety
Vent.
0
Water to
Treatment
Li,
Produce
-------
25 percent f27J, is dried in a dryer. Both rotary and fluidized bed dryers
are used. The dried PVC resin, which has less than 0.3 percent water(27),
is then ready for bagging. Polymer fines which remain in the dryer off gas
are removed in a cyclone separator, resulting in the recovery of additional
PVC product.
Emulsion Polymerization
Emulsion polymerization is similar to the suspension process except
that larger amounts of emulsifying agents are used. An advantage of the
emulsion polymerization process is that high—molecular—weight polymers are
produced at more rapid rates than in suspension polymerization. Vinyl
chloride monomer is emulsified by means of surface active agents in vater
whtc’ distribute most of the monomer in the aqueous phase as droplets. In
contrast to suspension polymerization, the emulsion process uses a water
soluble radical initiator to start the polymerization reaction.
The emulsifier content in the reactor is typically 1.25 to 3.0 percent.
(60J Temperatures in the reactor range from 45’ to 60 ’C. [ 32J The reaction
time can be as short as one—half hour. Conversion is usually held below 60
percent to ensure continued life of the emulsion.(60J Polymerization con-
tinues until the total solids content reaches 50 to 55 percent. Uniform
particles are prouuced which range in size from 0.05 to 10 microns.
A typical recipe for emulsion polymerization of PVC is shown belov:(11j
Material Parts by Weight
Water 15$
Vinyl Chloride 100
Azobisisobutyronitril. (initiator) I
Sodium Dodecyt Sulfate (emulsif 1.’:) 1.58
Cetyl Alcohol (emulsifier) 2
As shown in Figure 68, the emulsifier, initiator, and buffer are
dissolved in deionized water, then fed ri the polymerization reactor.
Inlaibitor free vinyl chloride is measured into the reactor and the mixture
agitated to form an emulsion. Polymerization is carried Out to 90 percent
conversion or greater.
Following polymerization, the polymer latex is strained and the polymer
separated fro. the monomer and other impurities. The latex is sent to a
blend tank before it is combined with a stabilizer solution and spray dried.
The dried resin is collected and separated according to particle size before
being bagged for shipment.
The impurities removed from the polymer latex are decanted, coalesced,
and sent to a surge tank before entering the purification column. Water
mixed with some vir’vl chloride monomer is recycled to the caustic decanter
while the vLi 1 j chloride monome is reycled to the polymerization reactor.
607
-------
Figure 68. PVC production ue ng the enulsion polynerisatton proc .. ..
Source: U.S. Environ.ental Protection Agency, Scurce Assee&eent: Polyvinyl Chloride , 1978.
0
S btLl
,t..
“C
Product
-------
Although using an emulsion allows fa3ter rates of reaction at lover
temperatures than other processes, the residual et ulsifier, about 2 to 5
percent, contaminates the polymer. 286J This contamination renders the
polymer more sensItive to heat and shear stress and reduces polymer clarity,
compatibility with compounding agents, electrical—insulation properties,
water resistance, and weatherIng ability.
Mass Polymerization
Mass polymerization is, in principle, the simplest process by which PVC
can be made since vinyl chloride and an initiator are the only input
materials.(70J The polymer produced his high porosity and clarity, uniform
shape and size, greater transparency, better impact strength, higher heat
and light stability, and improved electrical—insulation properties due to
the absence of contaminants. This process has lover capital and operating
ccsts s nce suspension agents and organic solvents are not required. The
primary disadvantage of mass polymerization is that it produces a resin
which must be chopped, cut, or pelletized. The raw materials used include
those listed in Table 210.
Two recipes for mass polymerization of PVC are shown below (113:
Parts b Wei ht
MaterIal Recipe 1 Recipe #2
Vinyl Chloride 100 100
• Azobisisobutyronitrtle (initiator) 0.016 0.02
Dilsopropyl Perca:bonate (ir itlator) 0.00005
There are two different mass polymerization processes for PVC: the
one—step process and the two—step process. The two—step process has
replaced the earlier one—step process aince the reactor size can be reduced
using two reactors in series. This process consists of four major unit
processc : pre’olyiserization, polymerization, devolatilizatjon, and
screening.
In the two—step process illustrated in Figure 69, the vinyl chloride
monomer and low concentrations (0.03 percent) of radical initiator are fed
to the prepo1 ’merization reactor. The prepolymerization reactor is designed
to provide vigorous agitation for reaction time. which approach three hours.
[ 213J When the PVC concentration reaches 7 to 12 percent, the monomer—
polymer mixture is transferred to another reactor to complete the polymeri-
zation. Temperatures in the prepolymerization and polymerization stages
range from 40’ to 70°C and pressures range from 483 to 1,172 kPa (70 to 170
ps!a). (255J The reaction time ranges from five to nine hours in either a
vertical or horizontal reactor which is agitated at lower speeds. The
reaction temperature is controlled by cooling a portion of the unreacted
vinyl chloride monomer in a reflux condenser, thereby removing a portion of
the heat generated by the polymerization reaction.
When the cor’version has reached 80 to 90 percent, the mixture is sent
to a devolatilizer where the unreacted vinyl chloride monomer is removed
-------
Figure 69. PVC production using the mass polymerigation process.
Sources: Hydrocarbon Processing , March 1980.
Hydrocarbon Proce8sj , November 1981.
613
Dust
tsi..i.ii.
PVC
-------
using low pressures and recycled. The devolatilizer uses low temneratures
(—35°C) for condensation since no water is present. [ 172J
The polymer is ground into particles and screened before baggL 1 g. The
average particle size of the product ranges from 50 to 200 m.icrons. [ 138J
Solution and Precipitation Polymerization
Solution and precipitatioa polymerization processes are similar since
both use an organic solvent as the polyaerization medium. The polymer
formed by solution polymerization is soluble in the solvent used, while the
polymer is insoluble in the solvent uaed and precipitates out of solution in
precipitation polymerization. Solvents for solution polymerization include:
chlorobenzene, chiorohexane, tetrahydrofuran, and l2—dichloroethane. Sol-
vents for precipitation polymerization include: n—butane, n—pentane, metha-
nol, benzene, acetone, methanol/water, and 1,1,2 ,2—tetrafluoriodichloro—
ethane.
Solution or precipitation polymerization has several advantages over
the mass polymerization process. The viscosity of the polymerization medium
is lower, the temperature control is more precise, and the molecular weight
of the polymer is lower. An advantage of solution or precipitatin polymer-
ization over suspension and emulsion polymerization processes is the purity
of the resin since no emulsifying or suspension agents are needed. The cost
of the solvent makes the production costs higher than for mass, suspension,
or emulsion polymerization. These processes are used mostly for the produc-
tion of PVC—polyvinyl acetate copolymers for applications in the phonograph
record industry which require pure resin trades as input.
As shown in Figure 70, the vinyl chloride monomer, solvent, and initi-
ator (from 0.01 to 0.5 percent) enter a series of agitated reactors at 40°C
to 60 C.(2l5J After polymerization, the unreacted monomer and solvent are
removed from the polymer in a flash tank and recycled. The PVC is filtered
from the slurry and the cake is dried by flash evaporation. Solvent removed
is sent to solvent recovery. The dried resin is sent to baggiog.
Figure 71 depicts precIpitation polymerization. As in solution polym-
erization, vinyl chloride monomer, solvent, and initiator (from 0.01 to 0.5
percent) enter a series of agitated reactors at 40 to 60’C.f215J After the
polymer beads have precipitated, they a’e separated from the solvent in a
centrifuge and dried. The solvent is recycled to the reactors while the
dried resin is bagged.
Energy Requirements
Energy rt quiremerits for PVC are listed below according to technology:
(214, 215, 26, 217, 2181
611
-------
Vinyl
To Solvent
Recovery
To Solvent
Recovery
Figure 70, PVC production using the solution pol ’iertzation process.
Source: U.S. Environmeacci. Protection Agency, Source Aseessusut: Polyvinyl Chloride , 1978.
Vpnt
PVC Product
-------
Figure 71. Pvc production ueing the precipitation polymerization process.
Sources: Encyclopedia of Chemical Techno1c v , 2nd Edition.
U.S. Environmental Protection Agency, Source L sesement:
Polyvinyl Chloride , 1978.
613
P VC
Product
-------
Unit/Metric
Energy Required Ton of Product
Ato Chimie Electricity 4.3 x 108 Joules
Steam 1 metric ton
Hoechst AG Electricity 7.9 x 108 Joulas
Steam 1.1 metric tons
Mitsui Toatsu Electricity 1.2 * 108 Joules
Chemicals Steam 1.0 metric tons
Lonza Ltd. Electricity 10.8 x 108 Joules
Steam 1.5 metric tons
Rhone Poulenc Electricity 5.4 x 108 Joules
Steam (6 atm.) 0.4 metric torts
ENVIRONMENTAL AND INDUSTRIAL HEALTH CONSIDERATIONS
A major consideration in the production and use of PVC resins and their
products is the potential exposure to at least one material that is a known
human carcinogen and four suspected human carcinogens. Therefore, potential
human exposure to these chemicals represents the greatest environmental
concern with PVC processing.
Worker Distribution and Emissions Release Points
Wo!ker distribution estimates for polyvinyl chloride production are
shown in Table 211. Estimates vera made by correlating major equipment man-
hour requirements with the process flow diagrams in Figures 67 through 71.
Point and fugitive emission sources associated with PVC production are
shown in Tables 212 and 213, respectively. Although several potentially
hazardous compounds may be emitted, the contaminant of extreme concern is
vinyl chloride monomer (VCN). If control strategies and respiratory and
personal protective equipment programs are directed toward minimizing
exposure to VO , exposure to other compounds will be controlled as well.
Health effects Information for major contaminants from PVC production
processes is discussed below and summarized in Table 10. IPPEU Chapter lOb
contains health effects information for process additives.
Control strategies in PVC manufacturing plants are among the most
stringent in the inAustry.(280J For this reason, the controls discussion in
Section 1 uses PVC production as an exampla.
Health Effects
Four of the input materials used in the maaufacture of PVC are offici-
ally classified by the International Agency for Research on Cancer (IAIC) as
suspected human carcinogens. They are acrylonitrile, which is a comonomer
614
-------
TABLE 211. WORUR DISTRIBUTION ESTIMATES FOR PVC PRODUCTION
Process Unit Workers/Unjt/8—hour Shift
Suspension Polymerization Batch Reactor 1.0
Steam Stripper 0.25
Blending Tank 1.0
Centrifuge 0.25
Dryer 0.5
Cyclone 0.125
Emulsion Polymerization Storage Tank 0.125
Decanter 0.25
Batch Reactor i.o
Strainer 0.25
Centrifuge 0.25
Batch Mixer 1.0
Spray Dryer i.o
Recycle Purification 0.25
Recovery Coalescer 0.25
Screens 0.25
Collector o.s
Mass Polymerization Batch Reactor i.o
Devolatilizer 0.25
Condenser 0.125
Crinding 0.25
Screecs 0.25
Solution Polymerization Batch Reactor 1.0
Flash Tank 0.125
Filter 0.25
Evaporator 0.25
Precipitation Polymeriza— Batch Reactor
tion Flash Tank 0.123
Centrifuge 0.25
Dryer 0.5
615
-------
MBLE 2i2. SOURCES OP AIR EMISSIONS FROM PVC MANUFACTURE
VcM Emissions in kg/100 kg PVC Prcc’uced
Source Suspension Emulsion Mass Solution
Fugitive EmIssions 1.50 1.13 0.48 0.03
Opening Loss — Reactor 0.14 0.13 0.08 0.50
Opening Loss — Monomer 0.32 1.23 — 0.05
Recovery Vessela
Monomer Recovery yenta 0.48 0.50 1.50 0.31
Slurry Blend Tank Vent 0.42 0.34 — —
Centrifuge Vent 0.13 — — —
Silo Storage Vent 0.70 2.41 — 0.83
Reactor Safety Valve Vents 0.20 0.22 0.10 0.06
Bagger Area Emissions — —— 0.23 —
Emissions From Process 0.03 0.03 .01 .01
Water and Reactor
Washingsb
Total 3.92 6.01 2.40 1.78
aThe monomer recovery vessel is either a stripper, devolatilizer or a
flash tank.
bThe only vastevater associated vith the mass and solution polymerization
processes results from reactor vashing.
Source: Marshall Sittig, Vinyl Chloride and PVC Manufacture , 1978.
616
-------
TABLE 213. SOURCES OF FUGITIVE EMISSIONS FROM PVC MANUFACTURE
Process
Source Constituents Suspension Mass Emulsion Solution
Agitator Vinyl Chloride X X X X
Seals Solvent X
Pump Seals Vinyl Chloride X X X X
Solvent X
Valves Vinyl Chloride X X X X
Solvent X
Leaks in Vinyl Chloride X X X X
PolyTneri— Solvent X
zat ion
Equipment
Dryer Vent Vinyl Chloride X X
Parttculates X X
Bagging Particulates X K I X
Process
(Pi oduct
Prepa ra-
tion)
Cutting/ I
Grinding/
Screening
Emulsion Vinyl Chloride I
Blend Tank
Filtration Vinyl Chloride I
Solvent X
Evaporation Vinyl Chloride x
Solvent x
Source: Marshall Sittig, Vinyl Chloride and PVC Manufacture , 1978.
617
-------
in the process; carbon tetrachioride, which is used as a chain transfer
agent; and the two solvents benzene and 1,2—dichloroethane. In addition,
polyvinyl alcohol, a suspension stabilizer, and vinylidene chloride, a
comonomer, are known animal carcinogens. Although health effects data are
relatively limited for the solvent tetrahydrofuran, the substance is con—
aidered highly toxic. The paragraphs below summarize the reported health
effects of exposure to these substances.
Acrylonitrile , a suspected human carcinogen (1071, causes irritation
of the eyes and nose, weakness, labored breathing, dizziness, impaired
judgae’tt cyanosis, nausea, and convulsions in humans. Mutagentic,
teratogonic, and tumorigenic effects have been reported in the literature.
The OSHA air standard is 2 ppm (8 hour TWA) with a 10 ppm ceiling. (69J
Bensene is a suspected human carcinogen (1011 which alsoezhibits
mutagenic and teratogenic properties. It poses a moderate toxic hazard for
acute exposures and a high hazard for chronic exposures through ingestion,
inhalation, and skin adsorption.(242J Effects on the central nervous system
have been observed in humans upon exposure to concentrations of 100 ppm.
(98j Intermittent exposure to 100 ppm over 1( years has been linked with
the development of cancers in humans. (271J The OSRA standard in air is 10
ppm (8 hour TWA) with a ceiling of 25 ppm.(67J
Carbon tetrachioride is a suspected human carcinogen (108j which is
alsn extremely toxic upon inhalation or injection of small quantities.(241J
The toxic hazard posed by skin adsorpt ton is slight for acute exposures, but
high fo chronic exposures. (241j The toxicity of carbon tetrachloride
eppears to be.ptimorlly due to its fat solvent action which destroys the
selective permeability of tissue membranes and .illovs escape of certain
essential substances such as pyridine nucleotides.(781 The OSHA air standard
is 10 ppm (8 hour TWA) with a 25 ppm ceiling(67J.
1,2—Diehioroethane is a suspected human carcinogen (1001, in addition
to exhibiting mutagenic properties. It is several imes more toxic than
carbon tetrachioride when takes in a single oral dose.(170j Toxic effects
include ga trointestina1 tract upset, central nervous system áepre..ion,
mental contusion, dizziness, nausea, and vomiting.(1703 Liver, kidney, and
adrenal injuries may occur at subacute levels.(170J Deaths from accidental
ingestion and from inhalation have been reported.(4J The OSEA air standard
is 50 ppm (8 hour TWA) with a ceiling of 100 ppm.(67J.
Polyvinyl alcohol has produced positive results in animal testing for
carcinogenicicy.(1073 Its single dose toxicity, however, is rr.sumably
low. (85J Implantation of PVA sponge as a breast prostheols has been
associated only with foreign body type of reaction (IE’J; neutral solutions
of PVA have also been used in eyedrops on human eyes without difficulty. (87j
Polyvinyl chloride is a suspected human carcinogen.(107J Although the
finished foam resin may cause allergic dermatitis, it is generally free from
health hazard unless comminuted or strongly heated.f278j ft burns readily
and ftivee off objectionable smoke.(278J Several cases of angiosarcosa of
t1 e liver have been detected among long—time workers in plants that make
polyvinyl chloride from monomeric vinyl chloride.(85j
618
-------
Tetrahydrofuran is very toxic by ingestion and inhalation. [ 242J When
heated to decomposition, it emits toxic fumes and it can react with oxidiz-
ing materials. [ 242J The OSRA air standard is 200 ppm (8 hour TWA). [ 67J
Vinyl Chloride is a proven human carcinogen [ 107) which may cause per-
manent injury or death after inhalation, even if the exposure is relatively
short.(242J Human reproductive effects occur at concentrations as low as 30
mg/ r n 3 [ 126J; both tumo’igenic and mutagenic effects have been observed in
humans as well as test animals. The OSHA air standard for vinyl chloride is
I ppm (8 hour TWA) with a 5 ppm ceiling.(68j
Vinylidene chloride has produced mutagenic, teratogenic, and carcino-
genic effects in laboratory animals.(107J In adiUtion, concentrations as
low as 25 ppm have been associated with systemic effects In humans. 37J If
ignited, the highly toxic hydrogen chloride will likely evolve. [ 157j
Air Emissions
Air emissions for suspension, emulsion, mass, and solution polymeriza-
tion are listed in Table 212. The values listed are reported to be the
average value of the data collected from surveys of PVC procc.aLng plants
and producer reported data. [ 255J
Of the’four processes used, ezulsion polymerization emits the greatest
amount of vinyl chloride monomer from point sources followed by suspension,
mass, and solution polymerization. ree ectively. However, solution polym-
erization has added solvent emissions, not only from point sources, but also
from fugitive emission sources. Alth’ugh these two polymerization processes
produce more emissions than suspension or mass polymerization, only 10
percent of the PVC produced is manufactured by these processes.
Considering the data cited in Table 212 and the fact that suspension
polymerization accounts for 83 percent of the PVC production, fugitive
emissions associated with the suspension polymerization process would appear
to be the significant air emission issue for PVC processes. Fugitive emis-
sions account for approximately 38 percent of the VOl emissions associated
with the suspension polymerization process. In addition, fugitive emissions
are the source of greatest concern from a worker exposure perspective.
Sources of fugitive emissions from nc processing ar.pra;cnted in
Table 213. Major fugitive emission sources are the valves, pump seals, and
dryer vent.
Wastevater Sources
In addition to air emissions, PVC production generates several waste—
water sources associated with the different processes listed in Table 214.
Suspension and emulsion polymerization processes produce large quantities of
wastevater since both of these processes use water in the reaction to s—
pend the monomer droplets. This vat r is separated from the polymer beads
in suspension polymerization and contains trace amounts of suspension
stabilizers. PVC emulsions may be shipped as such, or the resin may be
6 9
-------
&SLE 214. SOURCES OP WASTEWATER PROM PVC M&NUPAC URE
Sue— Emul— Solu— Proc .pi—
Source p!nsion sion Mass tion tation
Centri u1e X N/A N/A N/A N/A
Mouo er Stripping X N/A N/A N/A N/A
Polymer Screening N/A I N/A N/A N/A
Drier - I I N/A N/A N/A
Reactor Washing I I X I I
— Not applicable
620
-------
removed from the aqueous phase in a spray drier. If the resin is dried, the
resulting drier of f gases, when condensed, may contain trace amounts of
einulsifiers as well as suspension stabilizers. The only vastevater associ-
ated with mass and solution polymerization processes is from reactor
washing.
PVC reactor wash waters and monomer stripping vastevater viii contain a
certain small amount of vinyl chloride. Plasticizers, buffers, and comono-
mers viii also be present iu small amounts, if used in the polymerization.
In solution polymerization, a small amount of solvent will be present in the
reactor wash water.
Ranges of basic wastevater parameters for waters from the tour pro-
cesses, which were not separated by process for the purpose or establishing
effluent limitations for the industry, are as follovs:12841
Characteristic Unit/Pig PVC Produced
Wa tewater Production 2.5 — 41.72 m 3
ROD 5 0.1 — 48 kg
COD 0.2—100kg
TSS 1—33kg
Due to the volume of wastewater generated by suspension and emulsion polym-
erization, these processes, which comprise over 90 percent of the industry,
have the potential for providing the greatest impact to receiving waters.
Solid Wastes
The solid wastes generated by this process are mostly PVC. Solid waste
streams arise from reactor cleaning, product blending, particulate removal,
and spillage. The quantity of these wastes range from 0.001 to 0.03 kg of
PVC per kg of PVC product. The related vinyl chloride losses range from
0.0001 to 0.003 kg of vinyl chloride per kg of PVC product.f255J Solid
wastes resulting from off—grade product are less than 2 percent of PVC
produced. ( 61J
Environmental Regulation
New source perforiuauc standards proposed by EPA on January 5, 1981 for
volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• leaks (which are defined as VOC emissions greater than 10,000 ppm)
must be repaired within 15 days.
Proposed regulations for vinyl chloride provide a limitation of 0.2 g
of vinyl chloride per kg PVC produced for reactor emissions. Included in
621
-------
these regulations are the following limits for emissions occurring after the
reaction process:
• In polyvinyl chloride plants using stripping technology (Incinera-
tors): 2 000 ppm for polyvinyl chloride dispersion resins
(excluding latex resins); 400 ppm for all other polyvinyl chloride
resins, including latex resins, averaged separately for each type of
resin.
t n polyvinyl chloride plants without strippers or with technology in
addition tp strippers: 2 grams/kilogram (0.002 lb/lb) of product
from the strippers (or reactors if strippers are not used) for dis-
persion polyvinyl chloride resins, excluding latex, with the product
determined on a dry solids basis; 0.4 g/kg (0.0004 lb/lb) product
for all other polyvinyl resins, including latex.
The .miasions standards for vinyl chloride sources also include
specific operational and control requirements designed to reduce
fugitive emissions to no more than 10 pp. of vinyl—chloride/exhaust
gas.
Additional standards are required for EPA or state—approved leak detection
and elimination programs. Plant personnel must perform continuous
monitoring and recordkseping procedures.
- Effluent limitations guidelines have been set for the polyvinyl
chloride industry. $PT, UT, and NSPS call for the effluent to fall within
a pH range of 6.0 to 9.0 (41 PR 32581, August 4, 1916).
The following compounds are listed as hazardous wastes (46 FR 27476,
May 20, 1981):
Acetone — 11002
Acrylonitrile — 0009
Benzene — 0019
Carbon tetrachloride — 0211
Ch lorobenzene — 11037
Di—n—butyl phthalate — 11069
l,2—Dichloroethane — 11077
Dimethyl phthalate — 0102
Di—n—octyl phthalate — UlO l
Methnnol — 0154
Tetrahydrofuran — U213
Vinyl chloride — 0043
Vinlyidene chloride — 11078
All disposal of these materials or PVC which contains residual amounts of
these materials must comply with the provisions set forth in the Resource
Coneerva’ion and Recovery Act (RCRA).
622
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SECTION 27
POLYVINYUDENE QiL.ORIDE (PVDC)
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Polyvinylidene chloride (PVDC) is a thermally stable, chemical resis-
tant polymer which exhibits high impermeability to gases and vapors.
Although the homopolymer has these valuable properties as well as combustion
resistance, the difficulties encountered during homopolymer processing led
to the development of three major copolymers: vinylidene chloride—vinyl
chloride, vinylidene chloride—alkyl acrylate, and vinylidene chloride—
acrylonitrile. The incorporation of the comonomers permits polymer pro-
cessing at lover melt temperatures due to decreased polymeric crystalllnity.
These products were originally marketed under the Saran trademark. In the
United States, Saran is nov a generic term for PVDC and its copolymers;
however, Saran is still a registered trademark outside the United States.
The homopolyiner, Saran A, is not commercially produced de to the dif-
ficulties encountered during processLng. Saran 3, Saran C, and Saran F are
de ignationg for vinylidene chloride—vinyl chloride, vinylidene chloride—
alkyl acrylates, and vinylidene chloride—acrylonitrile copolymers, respec-
tively. Other commercially available grades of PVDC contain more than one
comonomer; the third monomer is introduced to improve the processability,
improve the solubility, or modify the specified end—use properties of the
polymer.(292J PVDC copolymer compositions range frot’i 73 to 95 percent
vinylidene chloride, with a typical content being 85 percent. 247j Typical
properties of PVDC are listed in Table A-’O in Appendix A.
Polyvinylidene chloride is produced on a commercial scale using
emulsion and suspension polymerizition processes. Emulsion polymerization
products are used either in the latex as coating vehicles or as a powder
when separated from the latex and dried. Suspension polymerizition polymers
are typically used in molding and extrusion applications. Each of these
processes offers different advantages. for example, emulsion polymeriiation
reaction times are shorter; however, suspension polymerization requires
fewer additive3 that detract from the polymer properties. [ 292, 293J
PJDUSTRY DESCRIPTION
Three chemical manufacturers comprise the polyvinylidene chloride
i ustry: Bordei., Dow Chemical, and W. R. Grace. Borden and Dow Chemical
produce vinylidene chloride—vinyl chlorice copoly-mers while V. R. Grace is
classified as a polyvinylidene chloride manufacturer.(56J Production
623
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facilities are located in California, Illtn j , Kentucky, and Michigan.
Table 215 lIsts these producers and their locations.
Production of POlyViflyiid . chloride polyu ers and copolymers totale
approxilutely 78 OoO metric tons in l 980 . [ 65j Miscellaneous vinyl resin
production, which includes PVDC as veil as polyvinyl butyral and polyvjny
formal, has been generally declining since 1976.
PRODUCI’ION AND END USE DATA
In 1980, total POlyvinylidene chloride production was 78,000 metric
tons.(65 1 FO yvtnyljdene chloride is used primarily as a film or coating
flexible surfaces for food packaging since it exhibits high oxygen imperme
ability and oil resistance. Other uses include;f 24, 65, 292, 293j
• Unit dose packaging;
• Drum and pack liners;
• Laminating;
• Cheujeal resistant molding, pipe, and tubing as well as chemical
resistant tubing and pipe liners;
• Fire resistant fiber for draperies;
• Combustion modifiers for foams;
• Wire coating, cable Jaclieting, and other low temperature uses;
Film coating to give resistance to fats, oils, oxygen, and water
vapor while remaining inert,tastelees and nontozic;
• Binders for iron—oxide pigmented coatings of magnetic tapes, such as
audio, video, and computer tapes;
• Binders for paint3 and non—woven fabrics; and
• Fiber for screen cloth, furniture and automotive upholste ,
furnitur webbing, Venetian blind tape, filter cloth, agricu1 u 5
shade cloth, vindov awning fabrics, brugh bristles, doll hair,
duat mops, and Industrial fabrics.
PROCESS DESCRIPTIONS
POlyvlnyijjene chloride copolymurs are manufactured on a commercial
scale u3ing emulsion or suspension polymerization. The end use intended for
the polymer determines, in part, which process is used.
Polyvinyjidene hlorjde is produced by free radical polymerization.
The reaction steps include initiacion, propagatfon, and termination of the
624
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TABLE 21 . U.S. POLYVINYLIDENE CHLORIDE PRODUCERS
Producer Location
Borden, Inc.
Borden Chemical Division
Thermoplastic Products Compton, CA
Illiopolis, IL
Dow Chemical, USA Midland, MI
W. R. Grace & Co.
Industrial Chemicals Group
Organic Chemicals Division Owensboro, KY
Suurce Directory of Chemical Fro ucers , 1982.
625
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polymer chain. Saran 3 is used in the following discussion to illustrate
the reaction chemistry.
The reaction begins with the decomposi j of a free radical initiator.
During initiation, the comonomers vinylideoe chloride and vinyl chloride
combine with the free radical (a.) to begin the formation of the polymer
chain:
C a 2 Cd 2 + RS— g — CH 2 CC 1 2 .
*inyljdene chloride
Ca 2 — QIC1 + R• *R — C11 2 a1C1.
vinyl chloride
During propagation, reactive com000mers combine with additional comonomer
molecules as the radical is transferred along the polyiser chain. The units
add in a head to tail fashion:
— 2 CCl ’+ Ca 2 Cd 2 + Ca 2 • caci
& — 2 CCi 2 — Q. 2 CC 1 2 — Ca2CRC1.
Polymerization is terminated when the free radical is consumed by either
radical combination or chain transfer. In combination, two reactive
copolymers combine as shown below:
R-CH 2 CC1 2 .-cii 2 CC1 2 —CR 2 CHC I.+ It’ CH2CC1r.CR2CC1 2 ..CR 2 CC1 2 .
R_CH2cCl2_2cCl 2 _Ca 2 CaCl Cl 2 Ca 2 ClCaCClCa
pOlyviflylidene chloride
A chain transfer agent (R’—r) may accept the radical, terminating the
growing polymer chain as illustrated below:
R’ —R. + R—Ca 2 CC12—CH2CCI 2 _CR 2 CHC1. —•*
ft• + I —CH2CCl 2 _c3 2 cclZ_ca 2 CpCl_R
polyvinylide e chloride
Oxygen reacts with the vinylidena chloride monomer used, making a peroxide
radical shown below:
C3 2 —CC1 2 + 02 *Qj 2 CC1 2 O 2 .
This slows the reaction rate. Monomer storage and polymeri a jo are
performed in an inert atmosphre to minimize this reaction.
626
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Tables 216 and 217 list typical input materials and operating param-
eters for polyvinylidene chloride processing. Other input materials used in
these processes such as free radical initiators, redox initiation systems,
emulsifiers, and specialty chemicals are listed in Table 218.
Emulsion Polymerization
Emulsion polymerization is used to produce either a polyvinylidene
chloride latex or, mo.e commonly, a powder which may be used in other appli-
cations. The latex is used in lacquers, bindings, and coatings while the
recovered polymer is uaed in other products. Emulsion polymerization typi-
cally takes only one-fourth to one—eighth of the reaction time required for
suspension polymerization, and reaches a higher percentage conversion.(292J
However, the additives used in emulsion polymerization (for example, the
emulsifier or surfactant) decrease the stability and increase the water
sensitivity of the polymer.
This process has two major manufacturing advantages: high molecular
weight polymers may be produced since the initiation and propagation reac-
tion steps may be controlled more independently; and the monomer may be
added during the polymerization to control the comonomer distribution along
the chain. [ 292J These advantages are off set by the reduction in polymer
properties, as mentioned above. Recovery of the polymer from the emulsion
improves the heat stability, light stability, water resistance, and
electrical properties.
As shown in Figure 72, the monomer, comonomer, and specialty chemicals
needed for this rea’ on are fed to a reactor which contains water and an
inert atmosphere. The monomer and comonoiner are distributed as an emulsion
through the aqueous phase by the protective colloid and emulsifier. A
typical recipe for the production of PVDC by the batch emulsion process is
given below: [ 59J
Material Parts by Weight
Vinylidene Chloride (monomer) 78
Vinyl Chloride (comonolfler) 22
Water 180
Potassium Persulfate (Initiator) 0.22
Sodium Bisulfite (activator) 0.11
Dihexyl. Sodium Sulfosuccinate, 80% (emulsifier) 3.58
Nitric Acid, 69% (pH control) 0.07
The reaction is carried to a high conversion before the emulsion is
discharged. Normally, the polymer is recovered by coagulation, then washed
and dried. Reaction temperatures are kept I elow 80°C since polymer degrada-
tion occurs at this temperature. Relatively short reaction times at these
low temperatures are attained by using redox initiator systems. [ 292, 293J
627
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TABLE 216. TYPICAL INPUT M&TERIALS TO POLYVINYLIDENE CHLORIDE PROCESSING
Protective
Process Water Monomer Surfactant Colloid Initiator
Emulsion 2 X X 2 2
Suspension 2 2 2 2
TABLE 217. TYPICAL OPERATING PARAMETERS FOR POLYVINYLIDENE CHLORIDE
PROCESSING
Process Temperature Conversion Reaction Time
Emulsion 30°C 95 — 982 7—8 hours
Suspension 60°C 85 — 902 30-60 hours
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
628
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TABLE 218. INPUT MATERIALS AND SPECIALTY CHEMICALS USED IN
POLYVINYLID P1E CHLORIDE MANUFACTURE
Function Compound
Monomer vinylidene chloride
Comonomer acrylates
acrylate esters
acrylic acid
acrylonitrile
alkyl maleates
allyl chloride
U—alkylacrylates
a—methyl styrene
butadiene
1—chloro—l—bromoethylene
chioroprene
diallyl fumarate
ethyl acrylate
glycidyl methacrylate
isobutylene
isopropenyl acetate
methacrylic acid
methyl acrylate
methyl methacrylate
(2—methacryloylozyethyl )—diethyl—
ammonium methyl sulfate
N—(2—formamidoethyl)acrylam ide
styrene
c richioroethylene
vinyl acetate
vinyl chloride and other vinyl halide.
vinyl esters
vinylidene bromide
5—vinyl—2—picoline
Plasticizer dibutyl sebacate
diisobutyl adipate
Heat Stabilizer epoxides
tetrasodium pyrophosphate
Reinforcing Agent calcium carbonate
glass
vollaatonite
(continued)
629
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TABLE 218 (continued)
? unct ion
Initiator ammonjum persulfate
azo compounds
organic peroxides
lauroyl peroxide
percarbonates
peroxydisulf ate
potassium persulfate
Redox System ammonium persulfate — sodium
mePabjsulfjte
Organometallic butyllithium
Emulsifier dihexyl sodium sulfosuccinate, 80Z
sodium lauryl sulfate
Suspension Stabilizer carboxymethylcel luj 0 5 5
(Protective Colloid) gelatin
P!41.hyl(hydroxypropyl )cellulose
polyvinyl alcohol
Tergitol W35 (Union Carbide Corp.)
Initiator Activator sodium bisuif ite
sodium formaldehyde sulfoxylate
pH Control nitric acid
Stabilizer acid acceptors
alkaline — earth salts
heavy metal salts
barium facty acid salts
cadmium fatty acid salts
lead fatty acid salts
epoxy compounds
epoxidized soybean oil
glycidyl esters
glycidyl ethers
organot in compounds
organotin mercaptides
salts of carboxyije acids
UV Absorber benzopheno7le derivatives
benzotrjazole derivatives
resorcyljc acid derivatives
s licylic acid derivatives
(continued)
630
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TABLE 218 (continued)
Function Compound
Antioxidant phenols
2 , 6 —di—t-butyl—4—methylphenol
substituted bisphenola
organic phoephites
organic sulfur compounds
Solvent for Lacquer
Coatings acetone
dimethjlformamjde
ethyl acetate
methyl ethyl ketone
methyl isobutyl ketone
tetrahydrofuran
toluene
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science anc Technology.
! lodern Plastics Encyclopedia , 1981—1982.
631
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Inert Gas - Vent
V
I
Coe nome r
Faulsiiie i POLYMER—
Electroiyte
Protective IZATION
___________ Vent
Collold REAC1 OR
Initiator
COAGULATION
Water
TANK
T To st ater Treatment
Polyvinyl idene
Vent Vent
Chloride Latex
WASH
Water DRYER
TANK
To
Wastevater
Treatment
Polyvinylidene
Chloride Powder
Figure 72. Polyvinylidene chloride production using emulsion
polymerization.
Sources: Encyclopedia 3f Chemical Technology , 2nd !“4tion.
Encyclopedia of Polymer Science and Technology .
632
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Suspension Polymerization
Suspension polymerization is typically used to produce extrusion and
molding resins of polyvinylidene chloride. Fewer inputs to the reactor
reduce the adverse effects on polymer properties as well as the cost. Gen-
erally, water sensitivity is less than that of emulsion polymerized resins,
but the stability is improved. An added advantage of the suspension polym-
erization process is the manufacture of pjlymer beads which are easily
separated, dried, and used in the production of polyvinylidene chloride end
products. The major disadvantages of this process are the increased
reaction times and lower molecular weight polymers. [ 292)
The suspension polymerization process is shown in Pigure 73. The mono-
mer and comonomer are fed to a polymerization reactor where, with the aid of
a suspension stabilizer, they are wuspended as droplets in an aqueous
medium. The inert gas prevents polymerization of vinylidene chloride before
the desired iniciatc,r a added. Due to the inability to control the initia-
tion and propagation steps as easily as in the emulsion polymerization
process, the conversion only r.aches 85 to 90 percent.
The monomer is removed by vacuum distillation, condensed, and recycled
while the polymer beads are centrifuged and dried in a flash or fluidized
bed dryer. The suspension polymerization process is typically a batch
process as compared to the emulsion polymerization process that may be
either batch or continuous.
A typical recipe for the production of PVDC by the suspension process
Is given below:159j
Material Parts by Weight
Vinylidene Chloride (moromer) 85
Vinyl Chloride (comonomer) 15
Water 200
(Methyl)(Hydroxypropyl) Cellulose, 400 cp
(protective colloid) 0.05
Lauroyl Peroxide (initiator) 0.3
Energy Requirements
No data for the energy required for polyvinylidene chloride production
were found in the literature consulted.
ENVIRONMENT/.L ANT) INDUSTRIAL HEALTH CONSIDERATIONS
Although PVDC and its copolymers are considered to be nontoxic, several
of the input materials used have been listed as hazardous under RCRA: ace-
tone, acrylic acid, acrylonitrile, ethyl acetate, ethyl acrylate, methyl
ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, toluene, trichloro—
ethyl e, vinyl cM.oride, and vinylidene chloride. Vinylidene chloride is
highly volatile; inhalation of the vapor is consideed tn be hazardous, but
633
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Figure 73.
Polyvinylidene chloride production ueing suspension
polyl!erizat ion.
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
.Vent
To
Wastevater Polyviny].idene
Tree t nt Chloride Beads
634
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is readily controlled by precautions commonly taken in the chemical indus-
try. Chioroprene and acrylonitrile (comonomers) are suspected human car-
cinogens. Other potential carcinogens include vinylidene chloride, tn—
chioroethylene, and polyvinyl alcohol. Acrylic acid, ethyl acrylate, methyl
acrylate, styrene, and toluene all pose significant health hazards.
Worker Distnibu 1on and Emissions Release Points
We have estimated worker distribution for PVDC production by corre-
lating major equipment manhour requirements with the process flow diagrams
in Figures 72 and 73. Estimates are shown in Table 219.
No major point source air emissions are associated with PVDC proces-
sing. However, fugitive and process air emissions from such sources as
reactor vents, wash tank vents, and dryer vents may pose a significant
environmental and/or worker health problem based on the components present
in the stream, operating parameters for the process, engineering and
admirustrat ve controls, and maintenance programs.
Process sources of fugitive emissions are listed in Table 220.
Numerous compounds nay be used as comonounera and additives (see Table 218).
Emissions of nitrogen gas, used as an inerting agent in the reactor, may
pose a simple asphyxiation hazard if elevated levels reduce the cixygen
concentration of workplace air. Particulate emissions from centrifuging and
drying operations may result in elevated nuisance dust concentrations.
Health effects information for contaminants of concern is provided in
the paragraphs below, in Table 10 and in IPPEU Ch ipter lob.
Health Effects
The manufacture of polyvinylidene thionide involves the use of two
suspected human carcinogens. They are chioroprene and acrylonitrile, both
coisonomers in the process. Three other input materials or specialty chemi-
cals have produced positive results in animal testing for carcinogenicity——
vinylidene chloride, a monomer; trichloroethylene, a comonomer; and the
suspension stabilizer, polyvinyl alcohol. Several other process chemicals
are currently being tested for carcinogenic potential. Highly toxic eub—
stances used by the industry include four comonomers——acrylic acid, ethyl
acrylate, methyl acrylate, and styrene——and the solvent toluene. The
reported health effects of exposure to these substances are sumoarized
be 1 ov.
Acrylic Acid is a severe skin and respiratory irritant 11701 and is one
of the most serious eye injury chemicals.(157J Ingestion may produce epi—
gastric pain, nausea, vomiting, circulatory collapse, and in severe cases,
death due to shock. [ 85J Although the data are not sufficient to make a
carcinogenic determination, the chemical has been associated with tumori—
genic and teratogenic effects in laboratory animals.
635
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TABLE 219. WORKER DISTRIBUTION ESTIX IES FOR PVDC PRODUCTION
Process Unit Workers/Untt/8—hour Shift
Emulsion Polymerization Batch or
Continuous Reactor 1.0 or 0.5
Coagulation Tank 1.0
Washing 0.25
Dryer 0.5
Suspension Polymerization Batch Reactor 1.0
Condenser 0.125
Distillation Columu 0.25
Centrifuge 0.25
Dryer 0.5
636
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TABLE 220. SOURCES OF FUGITIVE EMISSIONS FROM PVDC MANUFACTURE
Process —
Source Constituent Emulsion Suspension
Reactor Vent Vinylidene Chloride X X
Comonomer X X
Coagulation Tank Vent Vinylidene Chloride *
Comonomer *
Electrolyte *
Wash Tank Vent Vinylidene Chloride *
Comonomer *
Monomer Condenser
Vent Vinylidene Chloride X
Co’ ‘omer X
Centrifuge Vent Particulates X
Vinylidene Chloride *
Comonomer *
Dryer Vent Particulates X X
Vinylidene Chloride * *
Comonoiner * *
*Trace amounts expected due to high conversion in the reactor.
TABLE 221. SOURCES OF WASTEWATER FROM PVDC MANUFACTURE
Process
Source Emulsion Suspension
Coagulation Tank x
Wash Tank X
Centrifuge x
Routine Cleaning Water X x
637
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Acrylonitrile , a suspected human carcinogen (107), causes irritation of
the eyes and nose, weakness, labored breathing, dizziness, impaired Judg-
ment, cyanosis, nausea, and convuletons in humans. Mutagenic, teratoganic,
and tumorigenic effects have been reported in the literature. The OSRA air
standard is 2 ppm (8 hour NA) with a 10 ppm ceiling. (69J
Chioroprene has been classified by the International Agency for
Research on Cancer as a suspected humafl carcinogen.(107J It has also pro-
duced mutations in rats at an exposure by inhalation of less than 2 mg/rn 3
over a 16—week period.(233J Pregnant rats given a single oral Jose of 1
mg/kg or an inhaled dose of 4 mg/n 3 for 24 hours have experienced abnormal
development of the fetus.(233J The OSRA air standard is 25 ppm (8 hour
TWA). (67]
Eth)l Acrylate is currently being tested by the National Toxicology
Program for carcinogenesis by standard bioassay protocol. Previous test
data led to indefinite results. [ l07J It is very toxic by injection, inhala-
tion, or skin absorption (242), producing symptoms of hypersomnia and con—
vulsions.(149j The OSRA air standard is 25 pp. (8 hour TWA).f67J
Methyl Acrylate is highly, toxic by ingestion, inhalation, and skin
absorption upon acute exposure to relatively low doses.(242J The monomer is
very irritating to eyes, skin, and mucous membranes; lethargy and convul-
sions may occur if the vapor is inhaled in high concentrationa.(l49J Toxic
effects have been observed in humans at a concentration of 75 ppm. (76)
Methyl acrylate also produces tumors in laboratory animals, but sufficient
data do not exist to make a carcinogenic determination. [ 107 ) The OSRA air
standard is 10 ppn-(8 hour TWA).(67)
Polyvinyl Alcohol has produced positive results in animal testing for
carcinogenicity. [ 107J Its single e se toxicity, however, is presumably low.
[ 85) Implantation of PVA sponge as a breast prosthesis has been associated
only with foreign body type of reaction 1107); neutral solutions of PVA have
also been used in eyedrops on human eyes without difficulty.(37 )
Styrene has been linked with increased rates of chromosornal aberrations
in persons exposed in an occupational secting.(107j Animal test data
strongly support epidemiological evidence of its mutagenic potential. (233J
Styrene also produces tumors and affects reproductive fertility in labora-
tory animals. [ 233J Toxic effects of exposure to styrene usually involve the
central nervous system. [ 233 ) The OSRA air standard is 100 ppm (8 hour NA)
with a ceiling of 200 ppm. [ 67J
Toluene exhibits tumorigenic, mutagenic, and teratogenic potential in
laboratory tests. [ 233J Human exposure data indicate that toluene is also
very toxic. Exposures at 100 ppm have produced psychotropic effects and
central nervous system effects have been observed at 200 pprn. [ 233J Symptoms
of expc sure include headache, nau;ea, vomiting, fatigue, vertigo, paresthe—
sia, anorexia, mental confusion, drowsiness, and loss of consciousness. The
OSRA air standard is 200 ppm (8 hour TWA) with a 300 ppm ceiling. (67)
638
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Trichloroethylene has produced positive results in animal testing for
carcinogenicity. [ 108J It has also produced mutagenic and teratogenic
effects in laboratory animals (233] and is classified as an acute narcotic
which causes death from respiratory failure if exposure is severe and pro—
longed. [ ’,J Since trichloroethylene has a rather long biologic half—life,
major consideration nuqt be given to cumulative effects of this compound.
(31] Sublethal exposure may cause liver and kidney lesions, reversible
nerve damage, and psychic disturban.es.(85J OSHA has set an air standard of
100 ppm (8 hour TWA) with a 200 ppm ceiljn 5 .(67j
Vinylidene Chloride has produced mutagenic, teratogenic, and carcino-
genic effects in laboratory ariimals. [ 107J In addition, concentrations as
low as 25 ppm have been a3soc ated with systemic effects in hunians.(37J If
ignited, the highly toxic hydrogen chloride will likely evolve. [ 157]
In addition to its health hazards, vinylidene chloride is flammable
between 6.5 percent and l .5 percent concentration (by volume) in air.
Vinylidene chloride iil l spontaneously polymerize, forming peroxides and
creating a potentially explosive situation. Vinylidene chloride also reacta
with copper and aluminum; the impuritIes in the monomer form copper acetyl—
ides while aluminum reacts with the monomer to produce aluminum chioralkyls.
Both of these compounds are Pxtrene].y reactive and potentially hazardous.
[ 293]
Air Emjssions
Sourceq of fugitive emissions from PVDC nahufacture are summarized in
Table 220 by process and constituent type. Suspension polymerization does
not carry the reaction to the high level, of conversion achi.. ved in the emul-
sion polymerization process. Therefore, fugitive VOC emissions are expected
downstream of the reactor for the suspension polymerization process while
sources upstream of the reactor in emulsion polymerization are the major
contributors to the fugitive VOC emissions. The remaining hydrocar ,on in
these streams may be removed by venting to either a flare or a blowdown.
[ 285]
Fugitive particulate emission sources are also listed in Table 220.
T’iese particulates nay be collected by venting to a baghouse or electro-
static precipitator.
Wagtev - .ter Sources
The wastewater sources associated with PVDC processing are associated
with removal of the polymer from the aqueous medium. These sources are
listed in Table 221. No data are available in the literatu!-e consulted on
the wastewater produced or the associated parameters.
Solid Waste
The soLid wastes generated by this process nclude polymer lost due to
spillage and reactor cleaning, substandard polyir r which cannot be blended,
and collected partic’jlates.
639
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Environmental Regulation
Effluent limitet’nns guidelines have not been set for the p’ilyvinyli—
dene chloride industry.
New source performance standards (proposed by EPA on January 5, 1981)
for olati1e organic carbon (VOC) fugitive emissions include;
• Safety/release valves must not release more than 200 ppm above
background, except in emergepcy pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
mist be repaired within 15 days.
The following compounds have been listed as hazardous wastes (46
Federal Register 27476, May 20, 1981):
Acetone — 1 1002
Acrylic acid — U008
Acrylonitrile — U009
Ethyl acetate — U112
Ethyl acrylate — Ul13
Methyl ethy1 ketone — U159
Methyl isobutyl ketone — U161
Methyl methacrylate — 1J 162
Phenol — U188
Tetrahydrofuran — L1213
Toluene — U220
Trtchloroethylene — LJ228
Vinyl chloride — U043
Vinylidene chloride — U078
All disposal of these compounds or polyvinylidene chloride resins containing
residual amounts of these compounds must comply with the provisions set
forth in the Resource Conservation and Recovery Act (RCRA).
640
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SECTION 28
STYRENE—ACRYLONITRILE (SAN)
EPA Source Classification Code — Polyprod. General 3-01-018-02
INTRODUCTION
Styrene—acrylonitrile (SAN) resins combine the high clarity and gloss
of styrene with the added chemical resistance, heat resistance, and tough-
ness of acrylonitrile. These rigid, hard, transparent resins are easily
processed and possess good dimensional stability. This combination of
properties is ur.ique for a transparent resin.
SAN is a random copolymer of styrene and acrylonitrile which has an
amorphous structure. The molecular weight and the acrylonitrile content of
the resin play the major role 4 n determining polymer properties. Table A—41
in Appendix A lists some typical properties of SAN resins. Table A—42 in
Appendix A presents tensile strength and elongation as a function of
acrylonitrile content.
SAN is resistant to aliphatic hydrocarbons, alkalies, battery acids,
vegetable oils, foods, and detergents.(64J This insolubility makes SAN
suitable for use in applications requiring contact with petroleum prod—
ucts.(18J SAN is soluble in acetone, chloroform, dioxane, methyl ethyl
ketone, and pyridine. Swelling of the resin occurs on contact with benzene,
ether, or toluene; SAN is insoluble in carbon tetrachloride, ethyl alcohol,
gasoline, kerosene, and lubricating oil.
SAN may be produced using emulsion, suspension, or continuous mass
(bulk) polymerization. The latex manufactured via emulsion polymerization
is used primarily as an input to ABS manufacture. This ‘- tion presents the
polymerization processes used to produce SAN. Acrylon. .rile—butadiene—
styrene (ABS) processes are discussed separately.
INDUSTRY DESCRIPTION
The SAN industry is comprised of two producers that sell the resin on
the merchant market, Dow Chemical and Monsanto. All ABS producers have SAN
production capacity which is normally used in the production of ABS resins.
These companies sell small quantities of SAN resin on the merchant market.
Table 222 lists the location and production capacity of the two SAN
ptoducers.
SAN is used in appliances, automobiles, housewazes, packaging, and
construction. These industries reflect the general trend of the U.S.
641
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TABLE 222. U.S. PRODUCERS OF SAN
January 1, 1982 Capacity
Producer Thousand Metric Tons
Dow Che ica1 USA
Midland, M I 31.8
Pevely, MO 29.5
COMPANY TOTAL 61.3
Monsanto Co.
Monsanto Plastics and Resins Co.
Addyston, 00 22.7
COMPANY TOTAL 22.7
TOTAL 84.0
Sources: Chemical Economics Handbook , updated annually, 1981 data.
Directory of Chemical Producers , 1982.
642
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economy. In 1981, SAN production fell from the 1979 level of 56,400 metric
tons to 51,000 metric tons, which is 400 metric tons below the 1976 produc-
tion level of 51,400 metric tona.f 65, 143] The present SAN capacity of
84,000 metric tons is sufficient to support growth in the near future.
One environmentally significant portion of SAN processing is the
devolatilization step used in continuous mass polymerizaton. Residual
monomer in the polymer is reported to be reduced to 0.7 percent 1 which
reduces the population exposure risk.(153J This reduced risk is offset by
the additional processing step which increases the sources of fugitive VOC
emissions.
PRODUCTION AND EN) USE DATA
In 1981, SAN production totaled 51,000 metric tons. [ 143J Other SAN end
uses are: [ 64, 153]
• Knobs, refrigerator meat and vegetable compartments, blender and
mixer bowls, and other appliance uses;
• Instrument lenses, dash c aponents, and glass—filled support panels
for automotive use;
• Battery eases and meter lenses for electronics applications;
• Tumblers, mugs, and other housewares;
• Syringes blood aspirators, artificial kidney devices, and other
medical products;
• Cosmetic containers, closures, bottles, jars, and other packaging
materials;
• Safety glazing and water filter bowls for construction use; and
• Specialty products, such as brush block and bristles, typewriter
keys, and pen and pencil barrels.
Table 223 list3 the major markets for SAN and the amount contributed to each
for 1981.
PROCESS DESCRIPTIONS
SAN is produced by emulsion, suspension, or mass polymerization. Emul-
sion pOlymerized resins are especially suitable for ABS production; however,
the residual emulsifying ngent makes the polymer less suitable for high
transparency applications. Both mass and suspension polymerization produce
resins which are typically used for molding applications. As with t 1 e
emulsion resins, suspension polymerized resins contain residual suspending
agents which make the resin less desirable for transparent uses. Emulsion
and suspension polymerization may be either batch or continuout processes;
mass polymerization processes used are continuous.
643
-------
tABLE 223. SAN MAJOR MARKETS AND THE 1981 MARKET SHARE
Market Thousand Metric Tons
AppIianc’ s 8
Automotive 4
Batteries (non—automotive) 2
Compounding 8
Housewares 9
Packaging, Molded 6
Other 6
Export 8
51
Source: Mode€n Plastics , January 1982.
644
-------
Mass polymerization has fever waste treatment and environmental impacts
due to the simplified process and the absence of water in the polymeriza-
tion. This process does not require polymer drying 1 which in turn reduces
the energy input to the process. The disadvafltages of this process include:
longer time required to reach steady state and difficult mixing and heat
removal as the viscosity of the polymerizing mass increases with increasing
conversion. [ 153J
SAN is produced by the poly aerizaton of styrene and acrylonitrile. A
free radical initiator (RI) is used to initiate the reaction by reacting
with a styrene molecule. The styreneradjeal then combines with either
styrene or acrylonjtrjle monomers to create the random copolyuier. The
reaction is terminated by either two radical groups combining or the intro-
duction of a chain transfer agent (R’R). The polymerization reaction is
shown below:
Initiation
. ____ .
cu—cu + a .rucu 2 a
O 2 O
Propagation
0
• + —, &i 2 ..CHCU 2 -UICH 2 R
Termination
Radical Combination
0 _ 0
&icx a + u—cucu -cw w - acu 2 cu—cu 2 cu—cucu 2 -cIIcH 2 a
22 b 2 ’
Chain Trungfer
0 _ 0
R R” + X 2 I—CHCH 2 CHCH 2 , - R 0 CH 2 CH 2 —CHCH 2 + .
645
-------
Oxygen reacts with the free radical initiators used, thus making a peroxide
radical shown below, which slows the reaction rate:
Its + O 2 - RO 2 .
Polymerization is performed in a nitrogen atmosphere to minimise this
reaction.
Tables 224 and 225 list typical input materials and operating condi-
tions for the three SAN production processes. Other input materials used in
SAN production such as free radical initiators, exulsifiers, chain transfer
agents, and suspension stabilizers are listed in Table 226.
Emulsion Polymerization
The SAN resin produced by emulsion polymerization may be incorporated
into A3S production as an emulsion or it may be recovered for use in mol(tng
or extrusion processes. As illustrated in Figure 74, emulsion polymeriza-
tion performed batchwise is started by charging the reactor with part of the
necessary monomers, chain transfer agent, initiator, emulsifier, and water.
The reactor is purged with nitrogen and heated to ref lux while the remaining
portion of the input materials are fed to the reactor. After the reactor is
completely charged, the reaction is carried to the desired conversion at
ref lux conditions.
Continuous emulsion polymerization uses two stirred—tank reactors in
series followed by a large hold tank.(153J Either the batch or continuous
process may provide SAN emulsions for use in A3S production. For other
uses, the particles may be recovered by coagulation using an electrolyte,
washed, and dried.
A typical batch emulsion polymerization recipe follova:(153J
Material Parts by Wei ht
Initiator—Emulsifier Solution
Dresinate (rosin soap) 3
K 2 S 2 0 8 (initiator) 0.06
Water 146
Monomer Solution
Styrene 68.5
Acrylonitrile 31.5
Tert—Dodecyl Mercaptan 0.4
(chain transter agent)
Suspension Polymerization
Suspension polymerization differs from emulsion polymerization since
very small amounts (typically 0.01 to 0.05 percent) of a suspending agent
646
-------
T&BLE 224. TYPICAL INPUT MATERIALS TO SAN PRODUCTION PROCESSES
IN ADDITION TO STYRENE, ACRYLONITRILE AND INITIATOR
Chain
Transfer Suspension
Process Water _ • Stablilizer Emulsifier
Emulsion X X X
Suspension 2 2 2
Mass I
TABLE 225. TYPICAL OPERATING PARAMETERS FOR SAN PRODUCTION PROCESSES
Process I ! 2 rc Reaction Time Conversion
Emulsion 70 — 100°ca 1—3 hours 972 or higher
Suspension 60 — 150°C 5 hours
Mass 100 — 200°C 1 hour 40 — 702
awith redox systems, the temperature may be lowered to 38°C.
bNo conversion is given in the literature.
Source: Encyclopedia of Chemical Tec , 3rd Edition.
647
-------
TABLE 226 • INPUT MATERIALS AND SPECIALTY QIEMICALS USED IN SAN MANUFACrURE
(TN ADDITION TO SYTRENE AND ACRYLONITRILE)
Free Radical Initiators Di—tert—butyl peroxide
Potassium peroxydisulfate
(aqueous potassium persul—
fate solution)
Exulsifiers Roam soap
Chain Transfer Agents Dipentene
Tert—dodecyl ercaptan
Suspending Agents Acryclic scid2—ethylhexyl
acrylate (90:10)
Source: Encyclopedia of Chemical Technology , 3rd Edition.
648
-------
Monoenr
So1ut
mit jator•
Emuletf Let
Sotijt ton
poL’
REACTOR
Figure 74. SAN emulsion process.
Source: Encyclopedia of Chemical Technolo , 3rd Edition.
649
Vent
Latex
Coa RtjjanC
to
Driud
SM
-------
are used to maintain the monomer droplets in suspension polymerization.
Emulsifier levels of I to 5 percent are used for emulsion polymeriza-
tion. [ 153J
In the suspension polymerization process shown in Figure 75, the reac-
tor is charged with i nput materials a’ d purged with nitrogen. The reaction
mixture is heated and the reaction priceeds to the desired conversion. The
resulting polymer beads are stripped of unreacted monomer by distillation.
The styr!ne and acrylonitrile monomers are recycled to the reactor while the
polymer Leads are centrifuged and dried.
A typical recipe for suspension polymerization of SAN follows:(153J
Material Parts by Weight
Styrene 70.00
Acrylonitrile 30.00
Dipentene (chain transfer) 1.20
Di—Tert—Sutyl Peroxide (initiator) 0.03
Acrylic Acid—2—Ethylhexy l Acrylate
(90:10) (suspending agent) 0.03
Water 100.00
Mass Polymerf2atjon
Mass polymerization differs from emulsion and suspension polymerization
in that water is not used in the process. Mass polymerization may also be
initiated with a free radical initiator.
As illustrated in Figure 76, styrene, acrylonitrile, and an initiator
are fed to a polymerization reactor. When the reaction Teaches the desired
conversiGn, the polymer melt is pumped to a devolatiliger. Unreacted mono-
mers are removed and recycled to the reactor. The stripped polymer is then
pelletized in an extruder before it is bagged for shipment.
A typical production recipe for mass polymerization of SAN was not
found in the literature.
Energy Requirements
Data for the energy required during SAN production were not found in
the literature consulted.
ENVIRONMENTAL AND INDUSTRIAL HEALTH C NS1DERATI0NS
SAN is a nontoxic compound which is used in medical applications. Sty—
rene is considered to he a relatively safe organic chemical.(17J However,
prolonged or repeated contact with the akin may cause skin irritation and
over exposure to vapors may cause eye and nasal irritation. Styrene odors
are detectable at 60 ppm and are quite strong at 100 ppm. l7j Acrylonitrile
can be handled in industrial processes with relative safety although it is
toxic and a suspected carcinogen.(153J
650
-------
Styrene, Acrylonicrile, Water,
S.spending Agent,
Figure 75. SAN euepenaioa process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
POLYMERIZATION
REACTOR
Vent
SAN
‘II
Effluent to
Wastewdter
Treatment
-------
Monomer
Figure 76. SAN mass process.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
Styrene,
U I
SAN
Pellets
-------
Emulsion polymerization SAN processes carry the polymerization ieaction
to high conversion, 97 percent. Due to this high percentage of monomeis
converted to polymer, the upstream sources of air emissions contribute
significantly more to the total VOC emissions than the sources downstream
from the reactor.
Unreacted monomers are recycled to the reactor in suspension and mass
polymerizat ion. Low conversion (40 to 70 percent) in the mass polymeriza-
tion process makes the reactor vent more suspect as a source of acryloni—
trile and styrene emissions. Similarly, suspension polymerization reactor
vents are also a probable source of significant emissions since the
distillation step recycles unreacted monomers to the reactor.
The lower levels of conversion which are achieved by the mass polym-
erization process require a devolatilization step. Although the mass
polymerization process generates significantly less wastewater, the added
devolatilizatlon stap adøs .iddltional fugitive VOC e’nissio s.
Worker Distribution and Emisg ons Release Points
Estimates of worker distribution for SAN production are shown in Table
227. Estimates were derived by correlating major equipment manhour require-
ments with the pr ess flow diagrams in Figures 74 through 76.
The closed process conditions associated with SAN production minimize
employee exposure potential to hazardous chemical substances and physical
agents. Fugitive emissions from the sources listed in Table 228 and from
leaks in valves, pump and comprersor seals, and drains are the major sources
of workplace contamination.
Styrene and acrylonitjle are the major contaminants of concern associ-
ated with SAN production. Health effects information about these chemicals
is summarized in the paragraphs below. Additionally, nitrogen gas used as
an inerting agent in the reactor may pose a simple asphyxiation hazard if
fugitive emissions result in reduced atmosphertc oxygen.
Health Effects
Sufficient data do not exist with which to evaluate the potential
health impacts of several input materials and specialLy chemicals used in
SAN manufacture. Of the chemicals which have a significant history of
investigation, acrylonitrile and acrylic acid pose the most serious risk to
the health of plant employees. A summary of the reported health effects
resulting from exposure to these substances follows.
Acrylic Acid is a severe skin and respiratory irritant [ 170J and is one
of the most serious eye injury chemicals. [ 157J Ingestion may produce
epigastric pain, nausea, vomiting, circulatory collapse, and in severe
cases, death due to shock. [ 85J Althouguh the data are not sufficient to
make a carcinogenic determination, the chemical has been associated with
tumorigenic and teratogenic effects in laboratory animals.
653
-------
TABLE 227. WORKER DISTRIBUTION ESTIMATES FOR SAN PRODUCTION
Process Unit Workers/Unjt/8—hour Shi. :
Emulsion Polymeriza:ion Batch Reactor or
Continuous Reactor 1.0 or 0.5
Hold Tank 0.125
Coagulation i.o
Washing 0.25
Dewatering 0.25
Dryer o.s
Solution Polymerization Batch Reactor 1.0
Distillation 0.25
Centrifuge 0.25
Dryer 0.5
Masb Polymerization Batch Reactor 1.0
Devolatilizer 0.25
Extruder 1.0
654
-------
TABLE 228. SOURCES OF FUGITIVE EMISSIONS FROM SAN MANUFACTURE
Process
Source Constituent Emulsion SuspenBion Mass
Reactor Vents Styrene X X
Acrylonitrile X X X
Initiators X X
Emulsifiers X
Suspension Stabilizers X
Hold Tank Styrene X
Acrylonitrile X
Dewatering SAN and Monomer
Emissions and
Particulates Xa x
Dryer Vent SAN and Monomer
Emissions and
Particulates xa x
Extruder SAN and Monomer
Emissions and
Particulates X
apresent if the SAM emu 9lon resin is recovered.
655
-------
Acrylnuitrile , a suspected human carcinogen (1O7J, causes irittation of
the eyes and nose, weakness, labored breathing, dizziness 1 impaired judg-
ment, cyaiosis, nausea, and convulsions in humans. Mutageni ,. teracogenic,
and tunorigenje effects have been reported in the literature. The OSRA air
stanaard i?. 2ppm (0 hour NA) with a 10 ppm ceiling.(693
Styrene has been linked with increased rates of chromosomal aberrations
in persons exposed in an occupational etti g. [ lO7J Animal test date
strongly support epideiniological evidence of its mutagenic potential . [ 233j
Styrene also produces tumors and affects reproductive.fer ijj y in labora-
tory animals.(233;J Toxic effects of exposure to styréne usually involve the
central nervous aystem. [ 233J The OSRA air standard i 100 ppm (8 hour TWA)
with a ceiling of 200 ppm.f67J
Air Emissions
Sources of fugitive VOC emissions are listed in Table 228. These
sources are vents and may be controlled by venting these streams to a flare
to incinerate the remaining hydrocarbons or a blovdovn4285j Other equip-
ment sources, including valves, flanges, and pumps, may aiim ’ contribute to
totalVOC einjssjonj. The best control for these sources may be a routine
inspection and maintenance program.
Sources of fugitive particulate. are also listed in Table 228. Partic-
ulate. may be collected by routing these streams to a bsghouse or electro-
static precipitator.
Wastevater Sources
There are several vestevater sources associated with the various SAN
polymerization proeesaes shown in Table 229. The major wase.water sources
result •from emulsion and suspension polymerization which use water as a
proceósmedi for the production of SAN resin. Ranges of several waste—
wat rparamiters for vastevacegs from SAN production are shows below.
Va1ueJ ’f6r, th aitewater from the processes presented were not distin-
guished by• ,rocejg, type by EPA for the purpose of establishing effluent
limitations for the SAN industry:(284j
SAN Wastevater Unit/Metric
Characteristics Ton of ASS
Production 1.67 24.03 m 3
SOD 3 2 — 20.7 kg
Con 5?3.5kg
TSS O30kg
Solid Wastes
The solid wastes generated by this process are mostly SAN. Solid waste
streama originate from reactor cleaning, product blending, particulate
removal, and rpillage.
656
-------
tABLE 229. SOURCES OF WASTEWATER PROM SAN MANUFACTURE
Process
Source Eeulsion Suspension Mass
Polymer Dewatering xa x
Spent Water Bath
Routine Cleaning Water X X X
apregent if the SAN emulsion resin is recovered.
657
-------
Enviroi aental Regulation
Effluent liiaitatione guidelines have been set for the SAN industry.
spr, BAT, and NSPS call for the pH of the effluent to fall between 6.0 and
9.0 (41 Federal Register 32587, August 4, 1976).
New source performance standards (proposed by SPA on January 5 1981)
for volatile organic carbon (VOC) fugitive emissions include:
• Safety/release valves must not release more than 200 ppm above
background, except in emergency pressure releases, which should not
last more than five days; and
• Leaks (which are defined as VOC emissions greater than 10,000 ppm)
suet be repaired within 15 days.
Acrylonitrile ia listed as hazardous waste (46 Federal Register
27476, May 20, 1981); it is deei nated as X 09. All disposal of acrylo-
nitrile or ASS which contains any residual acrylonitrije must comply with
the provisions set forth in the Resource Conservation and Recovery Act
(RCRA).
U 1 I
-------
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680
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APPENDIX A
TYPICAL PHYSICAL AND CHEMICAL PROPERTIES OF POLYMERS
TABLE A-i. TYPICAL PROPFRTIES OF POLYMETHYL !€THACRYLATE
Property Cast Resin
Density, g/cin 3 1.17 — 1.20 1.17 — 1.20
Tensilc Strength, psi 8,000 — 11,000 7,000 — 11,000
Elongation, 2 2.0 — 7.0 2.0 — 10.0
Tensile Modulus, 3.5 — 4.5 .8 — 4.5
psi x 1O
Flexural Strength, 12,000 — 17,000 13,000 — 19,000
psi
I od Impact Strength, 0.3 — 0.4 0.3 — 0.5
ft—lb/in of notch
Rockwell M Hardness 80 — 10’) 85 — 105
Flexural Modilus, 3.90 — 4.75 4.2 — 4.6
psi x
Thermal Conductivity, 4.0 — 6.0 4.0 — 6.0
°C/cm x iO
Coefficient of Linear 5.0 — 9.0 5.0 — 9.0
Thermal Expansion,
x 10
Source: Seymour S. Schwartz and Sidney H. Goodman, Plastics Materials and
Processes , i982.
681
-------
EABLE A—i. TYPICAL PROPERTIES OF POLYMETHYL METHACRILATE
Density, g/cin 3
. ensile Streagth, psi
Elongation, Z
Tensile Modulus,
psi x
Cast Resin
1.17 — 1.20
8,000 — 11.000
2.0 — 7.0
3.5 — 4.5
— 1.20
— 11,000
— 10.0
— 4.5
Source: Seymour S. Schwartz and Sidney 11. Goodman, Plastics Materials and
Processes , 1982.
esin
1 • 17
7,000
2.0
3.8
12,000 — 17,000 13,000 — 19,000
0.3 — 0.4 0.3 — 0.5
Flexural Strength,
psi
Izod Impact Strength,
ft—lb/in of notch
Rockwell N Hardness
Flexural Modulus,
psi x
Thermal Conductivity,
°C/cm x 1O
Coefficient of Linear
Thermal Expansion,
80—100
85—105
3.90 — 4.75
4.2 — 4.6
4.0 — 6.0
4.0 — 6.0
5.0 — 9.0
5.0 — 9.0
682
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TABLE A-2. PROPERTIES OF IMPACT MODIFIED ACRYLIC HOLDING COMPOUNDS
Value
INA— Acrylic
MflA— Impact -Methyl Multi— Acrylic
Property Styrene Acrylic Styrene Polymer PVC
Density, 3/cm 3 1.09 1.11—1.18 1.09—1.16 1.10—1.12 1.35
Tensile Strength, psi 10,000 5,000— 10,000 6,000— 6,500
9,000 8,000
Elongation, 2 3.0 20.O—7fl.0 3.0 3.0—40.0 100
Tensile Modulus, 4.3 2.0—4.0 4.3—4.6 3.1—4.3 3.31—3.35
psi x 13
Flexural Strength, 16.000— 7,000— 12,000— 9,500— 10,700
psi 19,000 13,000 19,000 13,000
Izod Impact Strength, 0.3 0.8—2.5 0.3 1.0—2.0 15.0
ft—lb/in of notch -
Rockwell H Hardness M15 gins— MiS— R108— R99—
R120 p 1104 E 119 abS
Flexural Moc.ulus, 2.6—3.8 2.0—3.8 2.6—3.8 3.0—4.0 3.3—4.0
psi x
Thermal Conducttvity, 4.0—5.0 4.0—5.0 4.0—5.0 5.3 ——
x 1O
Thermal Expansion, 6.0—8.0 5.0—8.0 6.0—8.0 6.0—9.0 —
x
Clarity Trans— Trana— Trans— Trans— Opaque
parent parent, parent parent
can be
tran.—
lucen t
opaque
Source: Seymour S. S hvartz and Sidney H. Goodman, Plastics Materials and
Processes , 1982.
683
-------
VtBLE A-3. TYPICAL PROPERTIES OP ABS RESINS ACCORDING TO RESIN GRADE
Value
hUgh Plediun L Heat
Property ! ! Resistant
mod Impact Strength,
ft—lb/tn 7—12 4—7 2—4 2—6
Tensile Strength,
psi z 1O 3 4.8—6.0 6.0—7.0 6.0—7.5 6.0—7.5
Elongation, 2 15—70 10—50 —30 5—20
Tensile Modulus,
psi x 1O 2.5—3.0 3.0—3.6 3.0—3.8 3.0—3.8
Rockwell Hardness 88—90 95—105 105—1 10 105—110
Density, g/en 3
at 23°C 1.02—1.04 1.04—1.05 1.05—1.07 1.04—1.06
Linear Coefficient
of Thermal E pan—
•ion, (°C) 1 z lO 9.5—11.0 7.88.8 7.08.2 6.59.3
Source: Encyclopedia of. Chemical Technology , 3rd Edition.
684
-------
TABLE A—4. TYPICAL PROPERTIES OF ALKYD MOLDING RESINS
Property Value
Impact Strength, ft—lb 0.3 — 2.0
Flexural Strength, psi 10,000 — 20,000
Tensile Strength, psi 8,000 — 15,000
Density, g/cm 3 1.70 — 2.20
Molecular Weight 24,000 — 35,000
Sources: Encyclopedia of Polymer Science and Technology.
Modern Plastics Encyclopedia , 1981—19g2.
685
-------
ThBLE A-S. TYPICAL PROPERTT.ES OF FILLED AMINO RESIN MOLDED PRODUCES
Value
Urea
Foraald .
hyde
Property Resi is Nelamine—Forualdehyde Resins
0— 0— Maccrated Class
Cellulose Cellulose Fabric Asbestos Fiber
Density, glcrra 3 1.47—1.32 1.47—1.52 1.3 1.7—2.0 1.8—2.0
Tensile Strength, 3.5—7.0 7—13 8—10 5.3—6.5 5—10
pain 10
Elongation, Z 0.5—1.0 0.6-0.9 0.6-0.8 0.3-0.45 N/A
Tensile Nodisltie, 13—14 13.5 14—16 19.3 24
psi x
2ockvell N Rardness 110—120 120 120 110 11.3
Plel’4ral Strcngth, 11—18 12—13 12—15 7.4—10 13—24
x i& 3
Fle ural ModuAue, 14—15 11 14 18 24
p ’ 4 x
Impact 0.27-0.34 0.24-0.33 0.6—1.0 0.3-0.4 0.6—18
ft—lb/ia of notch
Thermal C nductivity, 10.1 1.0—10.1 10.6 13.0—17.0 11.3
1O i al/(sec)
(c.)(C)
Linea& Coefficient of 2.2—3.6 2.0—3.7 2.5—2.8 2.0—4.5 1.3—1.7
Thermal Expansion,
i — 5 x
N/A — Not availebl..
Source: Encyclopedia of ica1 Technolo_nolo , 3rd Edition.
686
-------
TABLE A-6. TYPICAL PROPERTIES OP MODIFIED POLYPRENYLENE OXIDE AND
POLY!’HENYLENE SULFIDE
Value
Property
Density, ft/cm 3
Tensile Strength, psi * IO
Elongation, X
Plexural Modulus, psi x 1O 5
Flexural Stretgth, psi x i0 3
Tensile Modulus, psi x
Rockwell ft Hardness
Compressive Strength, psi x 103
Modified
Polyphenylene
Oxide
1.06 — 1.36
7.8 — 17
4.0 — 60.0
3.6 — 11.0
12.8 — 20.0
3.55 — 12.0
106 — 119
16.0 — 11.9
Polyphenylene
Sulfide
1.34 — 2.67*
10.8
2—3
6 — 11.6
14 — 20
4.8 — 7.0
123 —
16 — 24
*Fjl led.
Source: Seymour S. Schwartz and Sidney H. Goodman, Pl3stics Materials and
Processes , 1982.
687
-------
Th3LE A-i. TYPICAL PROPERTIES OP EPOXY RESINS
Value
Phenol Cyclo—
Encaps’4— Novolak Aliphatic
latin g Epoxy Epoxy Cauting !4olding
Grades Resins Resins Re ins
Density, g/cm 3 1.7—2.1 1.16—1.21 1.16—1.21 1.05—2.0 0.73—2.0
Tensile Strength, 4,000— 6,000— 8,000— 2,000— 2,500
psi 15,000 12,000 12,000 13,000 20,000
Elongation, 2 2.0—6.0 2.0—10.0 13.9-24.9 13.4—15.4
Isond Impact
Strength, ft/lb
per in. of notch 0.3—2.0 0.5—2.0 0.2—1.0 0.13—30.0
Rockvell P1
Hardness 100—112 — —— 55-12) 100—110
Thermal Con-
ductivity,
°C/c. 4.0—10.0 — 4.0—25.0 4.0—30.0
Specific Heat,
caII’CIg 0.20-0.27 0.19
Thermal Expan-
sion 1 (°C) 1
x 10 3.0—6.0 — 2.0—10.0 1.1—3.0
Source: Seymour S. Schvartz and Sidney H. Goodman, Plastics Materials nnd
Processes , 1982.
688
-------
TABLE A—8. TYPICAL PROPERTIES OP PTFE AND PCTFE
Value
Property PTPE PCTFE
Tensile Yield Strength, psi x i0 3 2.8 — 3.0 3. — 3.7
Compressive Strength (at 12 offset),
psi x iO 0.7 1.8 2.0
Tensile Modulus, psi x 0.4 — 0.9 1.9 — 3.0
Compressive Modulus, psi z 10 0.7 — 0.9 1.8
Flex’iral Modulus, psi x i0 5 0.9 2.2
Izod Impact Strength, ft—lb/in
ot notch 2.5 — 4.0 3.5 — 3.6
Coefficient of Thermal expansion,
(Cr’ 10 —s 2.8 — 5.6 2.2
Source: Seymour S. Schvart, and Sidney U. Goodman, Plastics Material, and
Processes , 1982.
689
-------
TABLE A-9. a)MFAP ISON OF DENSITY AND ELONGATION OF FLU0&OP0L1) R$
Value
Property FTP! PCTFE FE? PVDF PET?! PECT? ! PVA !!
DensitY,
g/c& 2.1— 2.10— 2.14— 1.75— 1.70 1.68 2.16 1.38—
2.2 2.15 2.17 1.78 1.57
Elongation,
2 Lllti.ate 250— 125— 160 40— 100— 200 300 110—
400 175 100 400 260
Source: Seylsour S. Schwartz and Sidney H. Goodman, P1aetLc Materials and
Processes , 1982.
690
-------
TABLE A-lO. TYPICAL PROPERTIES OP PHENOLIC MOLDING COMPOUNDS
ACC0RDIN TO GRADE
Resin Grade
General— Heat— Special
Property Purpose Impact Resistant Electrical
Flexural Strength,
psi 7,C00- 7,000— 6,000— 8,000
9,300 9,000 9,000
Tensile Strength,
psi 3,500— 4,000— 4,000— 4000—
,5OO 6,000 4,500 4,500
Izod Impact Strengtn,
ft—lb/in of notch 0.24— 0.8— 0.23— 0.3
0.46 4.0 0.64
Source: Encyclopedia of Chemical Te l Z . 3rd Edition.
691
-------
TABLE A-Il • TYPICAL PROPERTIES OF POLYACETALS
Value
Copoly.er with
ylene Oxide
Den.ity 1 g/ca 3 1.42 1.41
Tensile Strength (at break, 23’C), 10 8.8
psi z lO
Elongation (at break), % 40 60
Modulus of Elasticity (23°C), 450 410
psi. x iO
Flexural Modulus, psi x 1O 3
23°C 410 375
10°C 260
71°C
Coefficient of Linear Thermal
Expansion, (°C)’ x iO
—30° to +30°C 10.4 8.5
Suurce: Encyclopedia of Chenical Technology , 3rd Edition.
b 2
-------
TABLE A—12. TYPICAL PROPERTIES OF POL.YAMIDE RESINS
Value
Nylon
Density, g/c 3 1.13 1.16
Tensile Strength, psi x iO 11.8 12.5
ElongatIon at Break, 2 50 — 2’)O 40 — 80
Young’s Modulus, over 12 extension 3.5 4.3
at 20C, psi x
Compressive Strength, psi x 1O 14.0 16.0
Shear Strength, psi x 1O 3 8.5 9.5
Izod Impact Strength, ft—lb/0.5 1.1 1.1
In of notch
Source: Encyclopedia of Chemical Technology , 2nd Edition.
693
-------
TABLE A—13. TYPICAL PROPERTIES OF POLYBUTYLENE
Value
D’..naity, g/cm3 0.910 — 0.915
Tensile Strength, psi
Yield 1,990
Break 4,550
Elongation at Break, Z 350
Modulus of Elasticity, psi 3,550
Izod Impact Strength, ft—lb/in no break
Shore D Hardness 55
Environmental Stress Crack Resistance, hours no failure
Source: Encyclope 4 !a of Chemical Technology , 3rd Edition.
694
-------
TABLE A—14. TYPICAL PR3PERTIES OF POLYCARBONATE
Prope! Value
Density, glcm 3 1.200
Linear Coefficient of Thermal Expansion,
(°C) 1 x i0 6.75
Tensile Strength, psi x
Yield 9.00
Ultimate 9.50
Elongation, Z
Yield 6—8
Break 110
Tensile Modulus, psi x i0 3 345
Plexural Strength, psi 13.5
Flexural Modulus, ps 339
Compressive Strength, psi 12.5
Izod Impact Strength, ft—lb/in
Notched 16.1
Unnotched No Failure
Tensile Impact, ft—lb/in 2 226 — 300
Source: Encyclopedia of Chemical Technology , 3rd Edition.
695
-------
TABLE A-15. TYPICAL PROPERTIES OF POLT(ETEER—IMIDE) RESINS
302 Glass Fiber—
Unfilled Reinforced
Melting temperature, ‘C (amphorous) 215 215
Specific gravity 1.27 1.51
Processing temperature range, ‘F 640—800 640—800
Molding pressure range, tO 3 psi 10—18 10—18
Tensile yield strength, psi 15,200 24,500
Co’ pressLve strength, pet 20,300 23,500
mod impact (ft—lb/in) 1.0 2.0
Rardoess, Roc ve1l M109 M 125
Coefficient of linear thermal
expansion, 10—6 in/in/’C 56 20
Thermal conductivity, LO callsec,cm,°C 1.6
Source: Modern Plastics Encycleped*a, 1982—83 Mc rav—Ni1l, Inc.,
New York, October 1982, Vol. 59, No. bA, p. 483.
696
-------
TABLE A—16. TYPICAL PROPERTIES OF PET RESINS
Prope çj Value
Density, g/cm 3 1.2 — 1.4
Specific Heat, cal/(g)(°C) 85
Coefficient of Linear Thermal Expansion, 7
(°C) 1 x
Elongation (break), Z 12 — 130
Rockwell N Hardness 106
Tensii Strength, psi 8,500 — 11,000
Injection Molded Resin
Tensile Strength (Yield), psi 2,350
Tensile Strength, (Break) psi 1,320
Elongation (Break), Z tOO 200
Flexural Modulus, psi
At 20°C 83,580
At 75°C 23,460
Flexural Yield Strength, psi 3,430
Izod Impact Strength, ft—lb/in of notch 1.8
Shear Strength, psi 1,850
Sources: Encyclopedia of Polymer Science and Technology.
Modern Plastics E:yclopedia , 1981—1982.
697
-------
TABLE A—il. TYPICAL PROPERTIES OF POLYSUTTLENE TEREPUTHALATE RESINS
Value
Tensile Strength, psi 7,500 — 19,000
Flexural Modulus, psi 340,000 — 1,200,000
Izod Impact Strength, ft—lb/iL , of notch
Unreinforced resin 1.0
Reinforced resin grade. 1.8 — 2.0
Impact modified uereinforced 16
Impact modified reinforced resin 3.5
Coefficient of Linear Thermal Expansion, 5.94
(°C)’ x i — over the range from
—30 to 30C
Source: Modern Plastics Encyclopedia , 1981—1982.
698
-------
TABLE A-18. CROSSLINKING AGENTS USED FOR UNSATURATED POLYESTER
RESIN PRODUCTION
Important Characteristics
Monomer Relative to Styrene
Styrene
Vinyltoluene 1
60/40 rn/p Lover vapor pressure,
slightly higher
reactivity
Chiorostyrene
67/33 0/p Fast cure, improved hot
strength, better surf ace
t—butylstyrene,
95/5 p/rn Low vapor pressure, high
flash point, high heat—
distortion temperature
Divinylbenzene
(rn—isomer) Increased crosslinking
-methyl styrene Increased storage time
Methyl methacrylate Improved veatherabiljty
when used in a 50:50
ratio with styrene
Methyl acrylate Improved strength and
veatherabi ii ty
Diallyl phthalate Very low volatility
Triallyl cyanurate High temperature
properties
Source: Encyclopedia of Polymer Science and Technology .
699
-------
P.EINFORCED UNSATURATED
ThILE A-19. TYPICAL PROPERTIES OF
POLYESTER RESINS
Flezural Strength, psi z 103
Flezural Modulus, pSi z to3
Inpact Strength, ft—lb/in
Rockwell P1 Hardness
Tensile Strength, psi z 103
Tensile Modulus, psi * 1O’3
Elungation, 2
Value
0.6 — 20.7
0.3 — 660
1.3 — 11.2
O — 111
2.55 — 9.86
0.4 — 870
1.20 — 1.85
Source: Encyclopedia of Polymer Science andj ol g .
700
-------
TABLE A—20. TYPICAL PROPERTIES OP HIGH DENSITY P0LYET1 !LFNE
Property Value
Density, g/cm 3 0.941 — 0.965
Elongatton, 2 15 — 100
Heat Capacity, cal/(°C)(g) 0.55
Impact Strength, ft—lb/in 1.5 — 20
Melt Index, g/l0 mm 0.1 — 4.0
Molecular Weight, veight average 125,000
Tensile Impact Strength, ft—lb/in 2 60
Tensile Modulus, psi x io 0.6 — 1.5
Tensile Strength, psi 3,100 — 5,500
Thermal Conductivity
20C 0.44
5 0C 0.40
100C 0.33
Coefficient of Linear Thermal Expansion,
20—90C, (°C) x 1.7
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
701
-------
TABLE A—21 • DENSITY DEPENDENT PROPERTIES OP RICE DENSITY POLYETHYLENE
0.96 0.95 0.94
Property Value
Stiffness, psi 145,000 113,100 79,800
Tensile Strength, psia 4,400 3,700 2,900
SofPøning Teisperatiare,
Vicat, °C 127 124 121
Shore D Hardness 68 67 63
Elongation, H 20 50 120
Environaenta t 3tress Crack
Resistance, Tiae for O2
of the Seuples to Pail, hours 20 100 700
aAt 2 in/mm.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
702
-------
TABLE A-22 • MOLECULAR WEIGHT D PENDENT PROPERTIES OF HIGH DENSITY
POLYETHYLENEa
Molecular Weight
175,000 142,000 135,000 105,000 90,000
Property Value
Tensile Impact,
ft—lb/in 2 100 64 59 41 30
lnngation at
Break, b 14 4.0 2.0 1.5 1.2
Environmental Stress
Crack Resistance,
Time for 50Z of
the Samples to
Fail, hours 60 14 10 2 1
Brittleness Tempera—
ture, C <—118 <—118 <—118 —101 —73
apor compression melded resin.
bAt 2 to/mm.
Source: Encyclopedia of Chemical Technology , 3rd Edition.
703
-------
TABLE A-23. rIPICAL HIGH DZNSITT POLYETHYLENE PROPERTIES ACCORDING
TO RESIN ‘ RADE
Resin Grade
Injection Blow
Molding Molding Eztr” ion
!122!E.!Z Value
Density, g/cs 33 0.957 — 0.958 0.946 — 0.959 0.944 — 0.955
Yield Stress, psi 4205 — 4350 3480 — 4350 3190 — 3625
Elongation,
(yield), % 12 12 — 14 14 — 16
Ultinate Tensile
Strength, pet 3913 — 4350 4785 — 3800 4640 — 3800
Elongation (rup-
ture), H >500 — >800 >800 >800
Shore D Hardness 68 — 69 64 — 68 60 — 66
5 At 23’C
Source: Encyclopenia of Cheaical Technology , 3rd Edition.
704
-------
TABLE A-24. TYPICAL PROPERTIES OF ULTRA hIGH MOLECULAR WEIGHT—
HIGH DENSITY POLYETHYLENE
Ziegler Catalyst Phillips Catalyst.
Copoly er Homopolymer
Property Vilue
Density, g/cra3 0.94 0.941 C.955
Tensile Strength, pal 5,400 3,000 4,000
Elongation, Z 525 >600 >600
Izod Inpact Strength, ft—lb/in >2O 7 16
5 S eieen deflects but does not break.
Source: Encyclopedia of Polymer Science and Technology .
705
-------
TABLE A-25. NPARISON OP LINEAR LOW DENSITY POLYETHYLENE
AND LOW DENSITY POLYETHYLENE TYPICAL PROPERTIES
t/C!3
Linear Low Density Lob Density
Polyethylene Polyethylene
0.922 0.926 0.918 0.921
Property Value
Tensile Strength, pat 1,885 2,90) 1,740 2,320
Elongation, 2 800 600 550 600
Pleicural Modulus, pet 33,930 73,950 20,010 60,030
Shore D Hardness — 38 — 58
Environisental Stress—
Crack Resistance — 1,000 65
Source: Encyclopedia of Cheisical Technolo 3rd Edition.
706
-------
TABLE A-26. TYPICAL PROPERTIES OF LOW DENSITY POLYETHYLENE
Density, g/cm 3
0.910 — 0.925 0.926 — 0.940
Proper t 1
Tensile Yield Stress, psi
Elongation, Z (yield)
Tensile. Ultimate Stress, psi
Elongation, Z (ultimate)
Shear Strenght, psi
Linear Coefficient of Thermal
Expansion, 20—60C,
(C) 1 x
Heat Capacity, cal/( ’C)(g)
Impact Strength, ft—lb/in
Molecular Weight,
weight average
Tensile Tmpact Strength,
ft_lb/jnZ
Tensile Modulua, psi x tO 5
Tensile Strength, psi
Sources: Encyclopedia of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
Value
20—40
10—20
4 .5 — 24.7
16.0 — 25.4
40’J — 700
100 — 500
15 — 30
0.55
>16
14,000 —
1,400 ;000
180
0.17 — 0.33
1,000 - 2,300
is —
0.5 — >16
14,000 —
1,400,000
60
0.25 — 0.55
1,2C0 — 3,500
7 1)7
-------
TARLE A—27. TYPICAL PROPERTIES OF POLYPROPYLENE
Randow
Property Ro op ymer ! Colyaer
Tensile Strength, psi 4,900 4,000 3,400 — 4,300
Flexural Modulus, psi 200,000 160,000 120,000 — 180,000
Ethylene Content, 2 0 1 — 4 5 — 20
Melt Flow Range,
g/ lOain 3—12 2-10 2—12
Source: Modern Plastics Encyclopedia , 1981—1982.
708
-------
TABLE A—28. TYPICAL PROPERTIES OF POLYPROPYLENE ACCORDING TO RESIN GRADE
Grade
Pipe Injection Coat and
Property and Sheet Film _ L Tubular Film
Melt Flow Rate,
gIl0 minutes 0.25— 1.5— 5—7 7—10
0.35 2.0
Density, glen 3 0.900— 0.900— 0.900— 0.900—
0.905 0.905 0.905 0.905
Tensile Yield
Strength (at 2
inches), psi 4,205— 4,640— 4,785— 4,785—
4,495 4,930 5,073 3,075
Elongation (yield),
2 10—12 10—12 8—10 8—10
Flexural Modulus, 159,300— 188,500— 217,500— 232,000
psi 188500 203,000 232,000 246,500
Izod Impact
Strength, ft—lb/in
at 23°C 0.028— 0.0094— 0.0056— 0.0037—
0.037 0.013 0.0094 0.0056
Rockwell C Hardness 55—60 55—60 60—65 60—65
Coefficient of Linear
Thermal Expanaion,
x
from —30 to 0°C 6.5 6.5 6.5 6.5
from 0 to 30°C 10.5 10.5 10.5 10.5
from 30 to 60°C 14.0 14.0 14.0 14.0
Source: Encyclopedia of Chemical Technology , 3rd Edition.
709
-------
TABLE A—29. TYPICAL PHYSICAL PROPERTIES OF GENERAL PURPOSE POLYSTYRENE
Property Value
Specific Gravity 1.05
Tensile Stress, psi
Yield and Rupture 4,710 — 8,000
Elongation, Z 0.9 — 2.0
Tensile Modulus, psi 400,000 — 570,000
Izod Impact Strenght, ft—lb/in 0.2 — 0.5
Thermal Coefficient of Linear
Expansion, (°C) 1 x 6 — 8
Specific heat, cal/g
0°C 0.283
50°C 0.300
100°C 0.439
Thermal Conductivity, al/(sec)(cm)(°C)
0°C 2.51 x i0 4
50°C 2.78 x
100°C 3.06 x lO
Sources: Modern Plastics Encyclopedia , 1981—1982.
Encyc opedia of Poly.er Science and Technology .
710
-------
TABLE A—30 • TYPICAL PROPERTIES OF RUBBER MODIFIED (IMPACT) POLYSTYRENE
Properçy Value
Density, g/cn 3 1.04 — 1.065
Tensile Modulus, psi 250,000 — 350,000
Izod impact strength, ft—lb/in 0.6 — 4
Elongation, Z 10 — 50
Tensile stress, psi
Rupture 2,820
Yield 2,920
Linear coefficient of thermal expansion
x i0 5 6 — 8
Specific heat, cal/g
0°C 0.283
50°C 0.300
100°C 0.439
Thermal conductivity, cal/(aec)(cm)(°C)
0°c 2.51 x 1O
50°C 2.75 x
100°C 3.06 z
Sources: ! ncIclopedia of Polymer Science and Technology.
Modern Plastics Encyclopedia , 1981—1982.
711
-------
ThBLE A-31. TYPICAL PROPERTIES OF IMPACT (RUBBER MODIFIED)
POLYSTYRENE GRADES
Medium High Super
Impact Impact Impact
Property PS P S PS
Specific gravity 1.05 1.05 1.02
Rubber, Z 3.4 3.1 14.5
Tensile yield, psi 3,700 3,000 2,OUO
Elongation, 2 (rupture) 1.4 33 17
Tensile modulus, psi x iO 4.5 3.4 2.5
Izod impact strength, ft—lb/in 0.6 1.3 4.3
irce: R. jclop.dia of Polymer Science and Technology .
712
-------
TABLE A-32. TYPICAL PROPERTIES FOR POLYURETHANE FOAM FORMULATIONS
Value
High
Medium Load Self
Property High—Density Density Extinguishing
Density, lb/ft 3 2.40 — 2.44 1.80 2.3
Tensile Strength, psi 14.9 - 17.5 19.9 18.7 12
Elongation, Z 107 — 248 258 65 200
Sources: EncyclopediA of Chemical Technology , 3rd Edition.
Encyclopedia of Polymer Science and Technology .
713
-------
tABLE A-33. TYPICAL PROPERTIES OP POLYVINYL ACETALE
Value
Density, glen 3 1.05 to 1.19
Tensile Strength 8 , psi z 4.26 to 7.10
Elongationa,b, Z 10 to 20
Young’s Modu1us , psi z tO 3 1.85 to 3.26
Charpy Inpact Strength 8 , ft—lb/in 2 >47
Thernal Coefficient of linear
ezpanston,(°C)L x 7 to 22
Specific Heat, cal/g’C 0.10
Thernsl conductivity, cal/(sec)(cn)(C) 38 ‘1O
Dielectric constant, 1O 3 Hz 3.15
•20°C
b 02 relative hunidity
Sources:, Encyclopedia of Chenical Technology , 3rd Edition.
Encyclopeâia of Polyner Science and Technology .
714
-------
TABLE A—34. PRYSICAL PROPERTIES OF POLYVINYL ACETATE EMULSIONS
Polyvinyl Polyvinyl
Acetate Acetate for
for Adhesive .p! oa n
Property Units Value Value
Vigcosity Brookfield LVT,a
60 rpm, cP 800 — 1,200 50 — 80
Specific Cavity 1.11 1.09
Average Particle Size Microns 1 — 3 0.15
Average Density g/cc at 20°C 5.35 5.23
‘Thig test measure, the torque produced by the emulsion, resulting from
the rotation of a spindle inside a sample chamber through which the sample
flows.
Source: Encyclopedia of Polymer Science and Techno1oj .
715
-------
TABLE A-35. SOLUSILITY OP POLYVINYL ACETATE IN SELECTED ORGANIC SOI.VENTS
Solvent Soluble or Insoluble
Aronatics Soluble
Butanol Soluble When Heated
Butanol with 5 to 10 percent water Soluble
Carboxylic Acids Soluble
Esters Soluble
Ethanol wIth 5 to 10 percent vater Soluble
Halogenated Hydrocarbons Soluble
Ketone. Soluble
Low Carbon Alcohols (Except Methanoi) Insoluble
Methanol àoluble
Nonpolar Liquids
Ether Insoluble
Carbon Disulfide Insoluble
Aliphetic Hydrocarbons Insoluble
Oils Insoluble
Pats Insoluble
Propanol with 5 to 10 percent water Soluble
Water Insoluble
Rylene Soluble When Heated
Source: Encyclopedia of Chemical Technology , 2nd Edition.
716
-------
ThBLE A-36. PhYSICAL PROPERTIES OF FULLY HYDROLYZED POLYVIN!L ALCOHOL
Property Value
cific gravity 1.19—1.31
Tensile strength, pat up to 22 , 0 0 0 a
Elongation, 2
unp1 st1eized film up to 3OO
plasticized fUn up to 600 a
Thermal coefficient of linear expansion, U—51f C,
plasticized, (°CY 1 xIO 5 7—12
Specific heat, cal/g 0.4
Compression molding temperature, °C 120—150
aAt 50 percent relative humidity.
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
717
-------
TABLE A-37. POLYVINYL ALCOHOL DENS ITT AS A PUNCTION 0?
REMAINING ACETATE GROUPS
I Acetate Density, 3/c a 3
in Resin at 20C
0 1.329
5 1.322
10 1.316
20 1.301
30 1.288
40 1.274
50 1.260
60 1.246
70 1.232
Source: Encyclopedia of Cheaical Techno1o , 2nd Edition.
718
-------
TABLE A-38. SOLUBILITY OF POLYVINYL ALCOHOL Ifl SELECTED ORGANIC SOLVENTS
ACCORDING TO ACETATE CONTENT
Polyvinyl
Alcohol
Sol b1e or Acetate
Chemical Insoluble Co itent
acetone Innoluble Low
acetylene Insoluble Low
anhydrous ethanol Insoluble Low
anhydrous methanol Insoluble Low
benzene Insoluble Low
butane Insoluble Low
l—butanol Insoluble Low
carbon tetrachioride Insoluble Low
chiorofluorocarbons Insoluble Low
cy ’loh xaiioI Insoluble Low
diacetone alcohol Insoluble Low
diethylene glycol Insoluble Low
diethylene glycol monobutyl ether Insoluble Low
(butyl Carbitol)
dionane Insoluble Low
ethyl acetoacetate Insoluble Low
ethylene glycol Insoluble Low
fenchyl alcohol Insoluble Low
formam de Inso’uble Low
furfural Insoluble Low
gasoline Insoluble Low
(continued)
719
-------
TAi LE A—38 (continued)
Polyvinyl
Alcohol
Soluble or Acetate
Chenical Insoluble Content
kerosene Insoluble Low
nethyl acecate Insoluble Low
sethytene dichioride Insoluble Low
sonochlorobenze, j Insoluble Low
propaoe Insoluble Low
sulfur dioxide Insoluble Low
trichioroethylene Insoluble Low
xylene Insoluble Low
acetamide Soluble when Low
heated 8
acetic acid Soluble when Low
heated 8
aetno hydroxy coepounda Soluble when
heated 8 ,b
ethanolaalne salts a d aaides Soluble Low
foruamide Solublea Low
N—(2—hytroxyethyl )acetamide Soluble Low
N—(2—hydroxyethyl)fori ,smide Soluble Low
ethylene glycol Soluble Low
glycerol Soluble’ Low
glycol Soluble when Low
heated 8
(continued)
720
-------
TABLE A—38 (continued)
Polyvinyl
Alcohol
Soluble or Acetate
Chemical Insoluble Content
lower polyethylene glycols Soluble when Low
heateda
phenol Soluble when Low
heated 3
sorbitol Slightly soluble Low
2,2’—thiodiethanol Soluble when Low
heateda
urea Slight soluble 3 Low
cresylic acid Soluble Above 452
liquid sulfur dioxide Soluble Above 802
piperazine Soluble
N—methyl pyrrolidone —c
tris(dlmethylamldo)phosphori.. acid Soluble —c
dimethyl sulfoxide Soluble —c
aporme a gel upon cooling.
bif the phenol contains water, it will s:ay liquid when cooled.
CNo percentage of acetate designation was given.
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
J. C. Prichard, Polyvinyl Alcohol: Basic Properties and Uses ,
1970.
721
-------
TABLE A-39. TYPICAL PROPERTIES OP POLYVUffi. QILORIDE
Specific gravity
Tensile, stre gth,a psi z 103
El ngatto X
Tensile modulu. ,a psi z lO S
Compressj,e atre gth, psi x 1O 3
Plezural yield strength,a
psi z
Izod impact strength,a ft—lb/in
Thermal Conductivity
cal/(sec)(ciu)(C) z 1O 4
Specific heat, cal/(g)(°C)
Linear thermal coeffteient of
ez;ansion (C)’i z 1O 5
Continuous use teiPp, C
Dielectric constant, iø Us
1.35 to 1.45
5.0 to 9.0
2.0 to 40
3.5 to 6.0
8.0 to 13
10 to 16
0.4 to 1.2
3.0 to 7.0
0.2 to 0.28
5.0 to 18.3
66 to
3.0 to 3.3
Plasticized
1.16 to 1.33
1.5 to 3.5
200 to 450
0.9 to 1.7
—a
—-a
3.0 to 4.0
0.3 to 0.5
1.0 to 23
66 to
4.0 to 8.0
5 Structura l properties are reported in English units, according to
COfl”enttoa.
Source: P. Rodriguez, Principles of Polymer Systems , 1970.
722
-------
TABLE A—40. TYPICAL PROPERTIES OF POLYVINYLIDENE CHLORIDE
Value
PVDC Molding
Property PVDC Compounds
Tensile Strength, psi x tO 3
Unoriented 5 — 10
Oriented 30 — 60
Molded 3.5 — 4.5
Elongation, Z
Unoriented 10 — 20
Oriented 15 — 40
Molded 15 — 25
Izod Impact Strength, ft—lb/in 0.5 — 1.0 2 — B
Sources: Encyclopedia of Chemical Technology , 2nd Edition.
Encyclopedia of Polymer Science and Technology .
723
-------
TABLE A—41 • TTPICAL PROPEETtES OF STYRENE—ACRYLONITRILE RESINS
8,300
2.1
520,000
0.30
Sources: Encyclopedia of Cheeical Technology , 3rd Edition.
Encyclopedia of Poly.er Science and Technology .
Value
— 11,000
— 3.7
— 540,000
— 0.45
— 83
Property
Tensile Strength, psi
Elongation, Z
Tens ile Modulus, psi
mod Impact Strength, ft—lb/in.
Rockwell Hardness
Coefficient of Linear Thermal Expunsion
x 10
Specific Heat, cal/(g)(°C)
Density, g/cm 3
6.85 — 6.67
0.31
1.06 — 1.08
724
-------
TABLE A-42. TENSILE STRENGTH AND ELONGATION VALUES FOR STYRENE—
ACRYLONITRILE RESINS WITh VARYING ACRYLONITRILE CONTENT
SAN Acrylonitrile
Content, Z Tensile Strength) psi E1 ifl55tiOfl, Z
5.5 6,130 1.6
9.8 7,922 2.1
14.0 8,321 2.2
21.0 9,259 2.5
27.0 10,511 3.2
Source: Encyclopedia of Chemical Technology , 3rd Edition.
725
-------
APPENDIX I • INPUT MONOMERS
Function
Mononers and Conono0ere Acetaldehyde
Acrylaaide
Acrylates
Acrylate esters
Acrylic acid
Acrylic esters
Acrylonitrile
Adipic acid
Aldehydes
Alkyl acrylates
Alkyl ealeates
Allyl chloride
Allyl esters of dicarbozylic acids
Allyl ethers of dihydric alcohols
Allyl sethacrylate
a—alkylacrylates
a—methyl atyrane
Asino resins
leazoquanasine
2 ,2—bis(4—hydrozyphevyl)l , l—dichloroethylene
Iisphenol—A
3utadL ne
I ,4—butanediol
1-butene
Rutyl acrylate
t—butyiaminoethyl sethacrylate
I ,4—butylen disethacrylate
Carba.oylnethytrtheth lasmonise hydrochloride
Cetyl vinyl ether
l—chloro—l—broi.oethylene
Cnlorouiethylester and :rieethylasin. or
pyrridine
Chl.oroprene
Chiorotriflurorethylene (CTVE)
Cresols
Crotonic acid
Dialkyl fu.arates
Dialkyl .aleates
Diallyl fu.arate
Diallyl phthalata (DAP)
Dibutyl fumarate
Dibutyl insleate
Diathylenetriasine
Di—2—ethylhexyl funarate
Di—2—ethylhezyl ns iate
—caprolacta s
(continued)
726
-------
APPENDIX B (continued)
Function
Monomers and Comon re Dihydroxyethy eneutea
(continued) Dimethylaminoethyl aethacrylate
Di.ethyl terephthalate
1 ,3—dioxolane
2 ,6—Diphenylphenol
Divinyl benzene
Epichiorohydrin
1 ,2—epoxy—3—diethylaminopropafle
Ethyl acrylate
Ethylene
Ethylene glycol
Ethylene oxide
2—ethyihexyl acrylate
Ethylenimine
Formaldehyde
Formaldehyde and salicyclic acid
Furfuraldehyde
Glycidyl aethacrylate
Clycol dimethacrylates
Heza fluoropropylena
aexamethylenediai.ine
I —hexene
High molecular weig’ t fatty acid
2—hydroxyethyl acrylate
N—hydroxymethyl acrylamtde
N—hydroxyaethyl aethacrylamide
I sobutylene
I.opropenyl acetate
Itaconic acid
Methacrylate esters
Methacrylic acid
(2—aethacryloyloxye thyl )—diethylamaoniu.
methyl sulfate
Methyl acrylate
Methyl methacrylate
2—methyl-6—phenylphenol
N—(2—formamidoethyl)actylamide
N—methylol acrylamide
Nonylphenol
1—serene
Octylpheno l
I —pent ene
Phenol
5 hos gene
p—dichlorobei ene
(continued)
727
-------
APPENDIX 3 (continued)
Function Conpound
Mononars and Coaonoiiera Phenolic resins
(continued) Polyurethane
Polyvinyl acetate
p—phenylphenol
Propylene
p—tert—butylphenol
Reso cinol
Sodiua ethylenesulfonate
Sodiua sulfide
Styrene
Styrenesulfonic acid
t—butylphenol
Terephthalic acid
Tetrabromobi sphenol—A
Tetrafljuoroethyl.n. (TIE)
Tatraeethylbisphenol-A
Thiourea
T rtallyl cyanurate
Trichioroethylene
Triethylenatetr aine
Trto ane
Unsaturated polyesters
Vinyl acetate
Vinyl butyl ether
Vinyl caproate
Vinyl chloride
Vinyl esters
Vinyl. fuaarate
Vinyl ketona
Vinyl laurate
Vinyl naleate
Vinyl toluene
Vinyl vereatate
Vinyl.ne carbonate
Vinytidene broaide
Vinylidene chloride
Vinylidene fluoride
5—vinyl—2—picolin.
Zylenole
2 6—zylenol (2,6—dimethylphenol)
(continued)
728
-------
APPENDIX B (continued)
Function Compound
Polybasic Acids Adipic acid
Azelaic acid
Camphoric acid
Chioreodic anhydride
Citric acid
Cyclopentadiene
Diallyl phthalic acids and anhydrides
Dim# rized fatty acid
Fumartc acid
Glutaric acid
Rexahydrophthalic anhydride
Isophthalic e’id
Isosebacic acid
Ma1ei’ acid
Maleic anhydride
0—methyl adipic acid
Nitrophthalic anhydride
Phthalic anhydride
Pimelic acid
Sebacic acid
Succinic acid
Tartaric acid
Terephthalic acid
Tetrachlorophchalic anhydride
Tetrahydrophthalic anhydride
Trimellitic anhydride
Oils China wood
Coconut
Cottonseed
Dehydrated castor
Fish
Linseed
Otticica
Safflower
Soya
Soybean
Sunflower
Tung
Walnut
(continued)
729
-------
APPENDIX B (continued)
Function Cospound
Monobasic Acids Bensoic acid
Patty acts and fractionated fatty
acid . obtained has oila
eleostearic
lauric
licanic
liuoletc
linoleic (conjugated)
lI ole ni
oleic
r cinoLeic
palat tic
stearic
p —tert—butylbengoic acid
Synthetic saturated fatty acids
2—ethyl hesanoic
isodecanoic
leononanoic
isooctanoic
pelargonic
Tall oil fatty acids
Polyols (Palyhydric l,4—butylene glycol
Alcohols) 2,3 —butylia. glycol
Cyclohesanedjol
Diethylene glycol
Dipentaerythrito l
Dipropylene glycol
Ethylene glycol
Glycerol
Mannitol
Neopentylene glycol (2 ,2—disethyl—j ,3—
propanediol)
Penta.rythrjto l
Polyethylene glycol
Poly(ozypropy lene) adduets of glycerol
Poly(oxypropylene) adducts of
1,2 ,6—hexanetriol
Poly(o propy1 ) adduets of psutaerythrftol
Poly(oxypropy lene) adducts of sorbitol
Poly(oxy propyl.ne) adducts of triusthylol
propane
Poly(ozypropylene) glycols
(continued)
730
-------
APPENDIX B (continued)
Function Compound
Polyols (Polyhydric Poly(oxypropyl ne—b—oxyethylene) adducts of
Alcohols) (continued) ethylenediam.Lne
Poly(ozypropylene—b_oxyethylene) adduct of
trimethyloipropane
Poly(oxypropylene—b—oxyethy lene) glycols
Propylene glycol
Sorbitol
Triethylene glycol
Trimethyloletnane (2—(hydrozymethyl)—2—
methyl—i ,3—propanediol)
Trimethyloipropane (2—ethyl—2-(hydroxy—
methy l)—l 3—propanadiol)
Isocyanates dianisidine dilsocyanate
2 • 5—dtchlorophenyl isocyanate
3 ,4—dichlorophenyl isocyanate
44 ‘—diphenylmethane dilsocyanate
ethyl isocyanate
hezamethylene ditsocyanate
hydrogenated methylene diphenyl isocyanate
isophorone diieocyanate
m—chlorophenyl isocyanate
m—icylene diisocyenate
methyl isocyanate
methylene diphenyl isocyanate (ND!)
n—butyl isocyanata
n—propyl isocyanate
o—chlorophenyl isocyanate
octadecyl isocyanate
p—chlorophenyl iaocyanate
phenyl isocyanate
toildine diisocyanate
toluene dilsocyanate (TM)
Polyesters Polyesters made from:
adipic acid
1, 3—butylene glycol
I , 4 —butylene glycol
caprolac tone
diethylenc glycol
ethylene glycol
phthalic glycol
propylene glycol
(continued)
731
-------
APPENDIX B (continued)
Punction
Polyethers Propylene oxide adducte of
a- ethylglucoeide
sthylenedia ine
glycerol
pentaerythrttol
sorbitol
sucrose
trimeth7lol propane
732
-------
APPENDIX C. COMPAt W S THAT PRODUCE PLASTICS
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APPENDIX. C (cootiftued)
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APPENDiX C (contiaued)
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APPLbJDIX
C (continued)
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APPENDIX C (continued)
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(continued)
-------
APPENDIX C (continued)
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(contlnu ,d)
-------
APPENDIX C (continued)
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Raybaato.—Nanlsatt .n , Inc.
— -
— —
—
— — —
—
— — — —
— — —
— — —
lesasa Ito.. Inc.
—
— —
—
lalchhold Cheajcals Inc.
-
—
—
- -
- - -
lico Cbe.ical Corp.
- —
—
— —
. — — .
— —
•
— — —
R ILn.nCorp.
- —
— -
—
—
— — — -
H. H. Iobart.oa Co.
— —
— —
— — •
— —
— — — .
Ro sraCorp.
.
. —
.
— .
—
.
—
.
Roha&UaaaCo.
—
— —
-
— —
Schasactady Dsn.jcajs Inc.
- — — —
- — — - —
Schoti.r Ito.. Inc.
SO Corp.
.-
.
—
—
.
Scott Paper Co.
— —
- —
.
.
.
Sh ak eap.ar.C ’.
— —
. —
—
— — —
— —
—
Shall Chaalcal Co.
—
.
—
—
Sh.llar-Clob. Corp.
I
— —
—
—
—
ee
(coni Inuod)
-------
APPENDIX C (continued)
0
L
I
-I
;. ..
1 .4
4. .11
- ‘
•u Q
H
0
0
.4
S
U
I -. 3 . . 4
I .
Tb.b.r Co.
q4
Sherwin—VUIL. Cu. —
.
Sldiit.ch Inc.
S
S
. .1
U
Ii
S. Sob.k Co.
Soltfk Poly..r Corp.
‘S
S.
0
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3
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Stanclisa Inc.
S
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I .
I
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S.
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U
SoutIi,a.t.rn Maul,.. Cu.
Squibb Corp.
Standard Oil Cu. of IN
I
.
Tb. Standard Oil Co. (ON)
Sun O..ndc .I Corp.
StauIf.r anical Cu.
Sullivan O’ontea l Coajinas
U
Spbroa Corp.
4
S
. 5
.
S
.
. .
-
Syncun loam luc.
Syarap Corp.
.
‘4
- S.
S
S
Syathro. 4 Inc.
TalIyr..d onic.1. Inc.
S
Tsütyr.n,
P 1 .jIc. 4 Inc. -
Tylsr Corp.
.
• -.
Union Cup Corp.
• •
.
5
.
•
Un luuCarbl d acorp.
- - -
5
‘
-
UI II SI SOI IC O. of C I
. • -•
-
•
•
S
S
‘-V
T.nnnco Irc.
Totapol Corp.
.
S
- II*tron Inc.
S
S
S
S
.
I
(conc *nu..J)
-------
APPENDIX C (continued)
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‘I
I ,
S
S
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3
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0
0
0.
.
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H
I J;;
90usd P0.. Corp.
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U
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5
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040.. 0 0
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—5 5
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04_. 0 0
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U
.4
U
UOIL.d Tuchnolopi. . Corp.
U
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0
0.
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0
I.
S
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I
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00
0.0.
a
0
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S
5
. 5
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0
U S. PoLy.,r . bc.
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.4
.
a
S
0
!!!! Upjohn Co
U S. 011 Co.
U
04
.2
I.
U
U
. 4
0
a.
a
S
0.
S
.0
0.
0
U.S. Scs.1 Corp.
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0
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.
.4
4.
S.
0
0
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I .
0
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Su.r. 3cc.
Va1.p.r Corp.
VIttt k.
.
Wa il . n , Inc.
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.
.
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-.
Ma c Co..c £dh. s i,u. Co.
9501 Po1nt..P.pp.rs I.ic.
Vssctii hou.. I1.c crie Corp.
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Usysrh.u..r Co.
.
Whitt.k.r Corp.
S
.
S
S
S
UtIc. Qissic.i Corp.
S
S
S
Uuuc.d Narchonc. a auJfac Ir.r. Inc.
.
S —
Tsnku -Naj.. c1c Psbnt Corp.
S
• S
TOTAL IQ&Mb I5 - is s (.j 5 2 Ii 5 50 2 12 I 2 5 15 26 I . 2 9 £2
IS Nplon 12 PIT
Ii Oih.r 3 PIT
ii . 2..
•
5.. .3
: 1
2
.
S
.
I
.
.
------- |