Section 3, Reference 8
DYNAMAC
CORPORATION
ASSESSMENT OP 8PICHLOROHYDRIN USES,
OCCUPATIONAL EXPOSURE AND RELEASES
March 28. 1984
Revised May 31, 1984
Final Draft July 11, 1984
Prepared Under Contract No. 68-02-3952
Submitted to:
The Economics and Technology Division
Office of Toxic Substances
U.S. Environmental Protection *yer ;y
Washington. D.C. 20460
TS-779
Submitted by:
Dynamac Corporation
Enviro Contro] Divison
The Dynamac Building
11140 RocJcville Pike
RockviLle, MD 20852
-------
ASSESSMENT OF EPICHLOROHYDRIN USES,
OCCUPATIONAL EXPOSURE AND RELEASES
March 28, 1984
Revised May 31, 1984
Final Draft July 11, 1984
Prepared Under Contract No. 68-02-3952
Submitted to: The Economics and Technology Division TS-779
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Submitted by: Dynamac Corporation
Enviro Control Divison
The Dynamac Building
11140 Rockville Pike
Rockville, MD 20852
-------
DISCLAIMER
This document is draft final report. It has not been released
formally by the Office of Toxic Substances, U.S. Environmental Protection
Agency, and should not be construed to represent Agency policy. It is
being circulated for information to those who cooperated in its pre-
paration. Mention of trade names or commercial products does not
constitute endorsement or recommendations for use by the U.S.
Environmental Protection Agency. Any technical errors are the respon-
sibility of George E. Parris.
PREFACE
This report was prepared by Dynaraac Corporation of Rockville, MD for the USEPA
under Contract No. 68-02-3952. The EPA Project Officer was Mr. James Cottrell
and the EPA Task Leader was Mr. George Heath.
The report was prepared by:
Dr. George E. Parris, Dynamac Corporation
Dr. Geneva S. Hammaker, Development Planning
and Research Associates, Inc.
Mr. Marcus Sittenfield, P.E., Romar Associates
We acknowledge the cooperation of the Dow Chemical Company, the Shell chemical
Co. and Hercules, Inc.
This manuscript was typed by Ms. Chanletta Ketchum and proofed by Ms. Mary
Grant Cruz.
Ms. Kathleen Walsh and Ms. Ann Engelkemeir drew the chemical structures,
process diagrams and other art work.
iii
-------
TABLE OF CONTENTS
Page
EXECUTIVE SUMMARY 1
1.0 INTRODUCTION 4
1.1 Objectives 4
1.2 Scope 4
1.3 Approach 5
2.0 CHEMICAL AND PHYSICAL INFORMATION ON EPICHLOROHYDRIN 6
2.1 Identification 6
2.2 Physical Properties 6
2.3 Chemical Properties 7
2.3.1 Hydrolysis and Other Ring-Opening Reactions. ... 1
2.3.2 Other Reactions of Epichlorohydrin 11
3.0 MANUFACTURERS AND PRODUCTS 12
3.1 Production Volume and Supply 12
3.1.1 Manufacturers and Production volume 14
3.1.2 Imports and Importers 14
3.1.3 Exports and Exporters 15
3.1.4 Net Domestic Supply 16
3.2 Markets 16
3.2.1 Epoxy Resins 16
3.2.2 Glycerin 19
3.2.3 Miscellaneous derivatives 20
3.2.4 Exported Epichlorohydrin 22
3.3 End-Use Products Derived from Incorporating ECH 22
3.3.1 Epoxy Resins 23
3.3.2 Glycerin 26
3.3.3 Elastomers 28
3.3.4 Wet-Strength Resins 29
3.3.5 Water Treatment Polymers 29
3.3.6 Other Uses 30
4.0 SUBSTITUTES FOR EPICHLOROHYDRIN 31
4.1 Physical/Chemical Properties Required for Each
Epichlorohydrin Use 31
4.2 Alternate Processes for Synthesis of Epoxy Resins .... 33
iv
-------
TABLE OF CONTENTS (continued)
4.2.1 Alternate Process Chemistry 34
4.2.2 Alternate Process Engineering 38
4.2.3 Comparative Cost of Manufacturing Epoxy Resins
by the Epichlorohydrin Method and the Proposed
Alternate Method 45
4.2.4 Substitutes for Epichlorohydrin-Based Epoxy
Resins 47
4.3 Alternate Processes for Synthesis of Glycerin 54
4.3.1 The Acrolein Process 56
4.3.2 The Propylene Oxide Process 56
4.3.3 The Invert Molasses Process 57
4.3.4 Comparison of Synthetic Glycerin Processes .... 57
4.4 Substitutes for Epichlorohydrin Elastomers 58
4.5 Substitutes for Epichlorohydrin Wet-Strength Resins ... 61
4.6 substitutes for Epichlorohydrln-Based Water
Treatment Chemicals 62
4.7 Substitutes for Alkyl Glyceryl Ether Sulfonates 66
4.8 Substitute for Epichlorohydrin-Based Anion Exchange
Resins 68
4.9 Substitutes for Fyrol 2 69
5.0 EPICHLOROHYDRIN MANUFACTURING AND PROCESSING 71
5.1 Manufacture of Epichlorohydrin 72
5.1.1 Process Chemistry 73
5.1.2 Process Engineering 78
5.1.3 Alternate Process for Manufacture of
Epichlorohydrin 85
5.2 Processing Methods for Epichlorohydrin 85
5.2.1 Manufacture of Epoxy Resins from Epichlorohydrin . 85
5.2.2 Manufacture of Glycerin from Epichlorohydrin . . . 105
5.2.3 Manufacture of Epichlorohydrin Elastomers Ill
5.2.4 Epichlorohydrin-based Wet-Strength Resins 117
5.2.5 Epichlorohydrin-Based Ion Exchange Resins 123
5.2.6 Fyrol 2 125
5.2.7 Alkyl Glycidyl Ether Sulfonates 125
5.2.8 Epichlorohydrin-Based Water-Treatment Chemicals. . 127
6.0 OCCUPATIONAL EXPOSURE TO EPICHLOROHYDRIN 129
6.1 Exposure Associated with Manufacture of Epichlorohydrin
and Glycerin 129
-------
TABLE OF CONTENTS (continued)
6.1.1 Dow's Epichlorohydrin-Glycerin Plant 129
6.1.2 Shell's Epichlorohydrin-Glycerin Plant 132
6.1.3 Dermal Exposure to Epichlorohydrin at
Epichlorohydrin Glycerin Plant 132
6.2 Exposure Associated with Manufacture of ECH-Epoxy Resins. 132
6.2.1 Dow's Epoxy Resin Plant 135
6.2.2 Shell's Epoxy Resin Plant 135
6.2.3 Celanese's Epoxy Resin Plant 136
6.2.4 Ciba-Geigy's Epoxy Resin Plant 136
6.2.5 Dermal Exposure to Epichlorohydrin during
Manufacture of Epoxy Resins 139
6.3 Exposure Associated with the Use of Epoxy Resins 139
6.3.1 Inhalation Exposure 139
6.3.2 Dermal Exposure 144
6.4 Exposure Associated with the Manufacture and Use
of ECH-Elastomers 144
6.4.1 inhalation Exposure 144
6.4.2 Dermal Exposure 145
6.5 Exposure Associated with Wet-Strength Resins 145
6.5.1 Manufacturing 145
6.5.2 Possible Exposure during Use 147
6.6 Dermal Exposure to Epichlorohydrin 14*7
REFERENCES 154
vi
-------
EXECUTIVE SUMMARY
Epichlorohydrin (ECH) is a liquid (b.p. 117°C), which is irritating and
systemically toxic by oral, percutaneous, and respiratory routes of exposure
(ACGIH, 1977). It is a known mutagen and there is evidence of carcinogenic
potential in rats (Tassignon et al.r 1983). In rats, ECH causes infertility
(Milby et al., 1981). This report summarizes uses of ECH, substitutes for ECH
in each use, occupational exposure to ECH and releases of ECH from plants
where it is manufactured or processed.
ECH is currently produced domestically by Dow Chemical U.S.A. at
Freeport, TX and Shell Chemical Company at Deer Park, TX and Norco, LA. The
combined annual U.S. production capacity is 640 million pounds and the
combined U.S. production in 1982 is estimated to be 336 million pounds
(Cogswell et al., 1983).
Commercial production of ECH began circa 1950 when it was found that a
convenient way to eliminate excess water during the manufacture of glycerin
from allyl chloride was to generate ECH and isolate it from the agueous
reaction mixture before converting it to glycerin. During the 1950s and
1960s, new uses were found for ECH and the demand for synthetic glycerin
decreased in the 1970s. Thus, although ECH plants are closely integrated with
glycerin plants, the production of glycerin from ECH currently can probably be
attributed in part to the use of the glycerin process to dispose of low grade
ECH which cannot be used for other products as well as to provide synthetic
glycerin when market demand warrants.
The major products produced from ECH are glycerin, epoxy resins,
elastomers, wet-strength resins, water treatment polymers (coagulants), the
flame retardant Fyrol 2, ion exchange resins, and alkyl glyceryl ether
sulfonate surfactants (Cogswell, 1983). In each case, ECH is an intermediate
that is consumed in manufacture of the product leaving only residues (usually
less than 1000 ppm) in the product. Uses of ECH in which it would not be
consumed In the manufacturing process are discouraged by the manufacturers.
-------
Epoxy resins are typically manufactured by reacting ECH with a diol
(usually bisphenol A). Residues of ECH in most resins are controlled to 5 ppm
wt/wt by the manufacturers because it has been shown that this level of
residue in the resins will not lead to violation of the atmospheric standards
(5 ppm v/v) set by OSHA (Shell. 1982). Some special resins (particular those
containing reactive diluents or glycidyl esters) may contain ECH residues up
to the range of 1000 ppm wt/wt. The highest exposures to ECH appear to be
associated with spray painting epoxy resins containing high levels of ECH
under conditions of poor ventilation.
The methods used to manufacture glycerin from ECH and remove excess
water suggest that the product should not have detectable levels of ECH.
Elastomers made by catalytic polymerization of ECH by itself or with
ethylene oxide may have residual ECH. However, there are indications that
once the elastomer is compounded, the ECH is either destroyed or immobilized
(Kirk-Othmer, I979a).
There are too few data to evaluate the residues of ECH in other products
quantitatively, but in most cases the reaction conditions suggest that ECH
residues will be below detectable levels (e.g., sub-ppm), although some ECH
hydrolysis products may be present.
Substitutes for ECH have been examined for many of its important
products. Two approaches to substitution have been considered: synthesis of
the product using reactants other than ECH, and substitution of equivalent
products for ECH-based products. In most cases, subsitution appears to be
technically feasible although cost of the alternate products or alternate
synthetic routes are probably higher than the current ECH-dependent technology.
The biggest area of ECH consumption is in manufacture of epoxy resins.
The most likely alternate synthetic pathway involves reation of the diol with
allyl chloride followed by peracid epoxidation or hydrochlorination-
epoxidation to yield the epoxy resins. On the surface this process might be
able to compete economically with ECH-epoxy resins, but the technology asso-
ciated with manufacture of ECH is closely intertwined with other processes so
-------
that major changes in the production volume of ECH could affect the economics
of other material (e.g., allyl chloride, glycerin). Thus, the actual cost of
implementing the alternate synthesis is quite difficult to calculate.
A series of industrial hygiene surveys for NIOSH (Bales, 1978) showed
that worker exposure to ECH during manufacture and processing is rather well
controlled. In these situations TWA exposures are below the OSHA standard of
5 ppm v/v. There is one reported case where workers were spray painting large
structural steel sections in a poorly ventilated building and very high (e.g.,
up to 82 ppm TWA) exposure levels were found (Chrostek and Levin, 1981). This
situation seems to be exceptional and the epoxy being used probably contained
reactive diluents with high ECH levels (unlike the basic bisphenol A-ECH
resins).
Dermal contact with ECH is recognized as the mode of exposure most
likely to produce acute reaction. The major manufacturers attempt to educate
their own employees and the employees of their customers regarding these
hazards.
-------
1.0 INTRODUCTION
1.1 Objectives
The objectives of this report are to summarize the uses, occupational
exposure and environmental releases of epichlorohydrin. The health effects of
epichlorohydrin (ECH) are well known and have been documented in other reports
(NIOSH, 1976; EPA, 1983). The exposure and release data can be used in
combination with the health effects data by EPA to evaluate the risks
presented by current Industrial uses of ECH. The use data will allow EPA to
evaluate various options to control the risks.
1.2 Scope
This review was limited to approximately 1,300 hours of professional
labor over a 4-month period. The health effects of ECH have been discussed
elsewhere (NIOSH, 1976; EPA, 1983) and are not considered here. The occupa-
tional exposure to ECH has been studied by NIOSH (Bales, 1978 and supporting
documents; Lewis, 1980; Chrostek and Levine, 1981); and the EPA Office of Air
Quality Planning and Standards (Anderson et al., 1981; PRI, 1972; SAI, 1982)
has examined atmospheric releases of ECH. Releases of ECH from manufacturing
plants were also discussed by Santodonato et al. (1980). The current study
does not include any field work, so our occupational exposure and environ-
mental release discussions are limited to analysis of existing data.
In the context of this project, "use" includes the industrial uses of
ECH, the economics of those uses and the potential substitutes and the
economics of those substitutes for ECH in those uses. In addition, since ECH
is an intermediate used to produce a variety of products, the levels of ECH
residues in each type of product are an important consideration in evaluating
exposure beyond the manufacturing and processing steps. Uses of ECH have been
discussed by Santodonato et al. (1980) and Chen et al. (1981), but relatively
little work was done on substitutes or residues in these reports.
-------
1.3 Approach
Our approach to this project has been to absorb as much information
as possible from previous reports on ECH prepared for EPA and other Federal
Agencies and to conduct a search of the computerized data bases to obtain
additional information to update and fill gaps in the information of particular
interest here. Contacts with manufacturers, processors and users of ECH have
been conducted with emphasis on determining residues of ECH in various pro-
ducts. Most of the original work in this project has centered on evaluation
of substitutes for ECH. This area has not been investigated in depth in
previous studies (Santodonato et al., 1980; Chen et al., 1981; Mathtech, 1983).
-------
2.0 CHEMICAL AND PHYSICAL INFORMATION ON EPICHLOROHYDRIN
2.1 Identification
Name; Epichlorohydrin
Synonyms: (Chloromethyl)oxirane (9CI name)
l-Chloro-2,3-epoxypropane
3-Chloro-l,2-epoxypropane
(Chloromethyl)ethylene oxide
2-(Chloromethyl)oxirane
Chloropropylene oxide
3-Chloro-l,2-propylene oxide
2.3-Epoxypropyl chloride
CAS No.; 106-89-8
NIOSH No.; TX4900000
Empirical Formula; C3H5C10
Structural Formula; o
H C-CH-CH Cl
Molecular Weight; 92.53
2.2 Physical Properties
Description; Epichlorohydrin is a colorless liquid with a
characteristic chloroform-like odor (Dow, 1980). Its odor
index is 160 and its average threshold odor concentration
is about 10 ppm with a range of 0.08 to 100 ppm
(Verschueren, 197"7).
Freezing Point; -57.1°c (Dow, 1980).
Boiling Point; 116.1°C at 760 mmHg (Dow, 1980)
117.9°C at 760 mmHg (Merck, 1976)
Vapor Pressure; 17.25 mmHg at 25°C (Dow, 1980)
Specific Gravity; 1.173 at 25/25°C (Dow, 1980)
Solubility in Water; 6.6 g/100 g H2O at 20°C (Dow, 1980)
Water Solubility in ECH; 1.47 g/100 g ECH at 20°C (Dow, 1980)
Solubility in Organic Solvents: Miscible with polar (e.g., methanol)
and nonpolar (e.g., heptane) organic
solvents (Dow, 1980)
Log Octanol/Water Partition Coefficient; 0.30 (Chen et al., 1981)
-------
2.3 Chemical Properties
2.3.1 Hydrolysis and Other Ring-Opening Reactions
Epoxides are much more reactive than ordinary ethers because the carbon
and oxygen bond angles are forced to be about 60° rather than the preferred
angles of about 109° normally adopted by non-cyclic aliphatic compounds
(Flippen-Anderson and Gilardi, 1981).
109° 109°
C * — ^ 0 <£ — ± C
\ / \
c -*-? c
109
60°
Normal Ether Bonds Epoxide Bonds
The "abnormal" bond angles found in epoxides result in lower bond energies for
the C-0 and C-C bonds in the three-membered ring and the difference between
the normal and abnormal bond energies can be interpreted as "strain energy"
associated with the ring. Reactions that lead to opening of the epoxy ring
are enhanced because they allow the C-C-O and C-O-C bond angles to change to
their preferred dimensions.
The main reactions of commercial interest involve opening the epoxide
ring by displacing the oxygen from one of the carbons by a nucleophile. The
mechanisms for this reaction have been discussed by a number of authors. In
the case of epichlorohydrin (ECH) reacting in normal solvent media (i.e.,
excluding the possibility of highly acidic media), the ring opening reaction
can be described as shown below (Prichard and Siddiqui, 1973):
-------
\
C1CH2 - CH - CH2
_Y
+ H
0
/ \
- CH — CH.
OH
C1CH.. — CH — CH_ — N
C1CH - CH — CH2 - N
-H
rapid
In this scheme, ECH is subject to a rapid, reversible protonation re-
action. The extent of protonation depends upon the pH of the medium. Both
the unprotonated and protonated forms of ECH can be attacked by nucleophiles
(N) causing displacement of the oxygen from a carbon and opening the ring. Tn
general, the rate constant k is much greater than k ; protonation of the
a n
epoxide ring catalyzes ring opening. Because nucleophilic attack with con-
current displacement of the leaving group (S 2) generally is now rapid at
the carbon with fewer substituents, the nucleophile will usually attach to the
terminal carbon of the propyl group.
The overall ring-opening rate (R) is equal to the sum of the rates of
the uncatalyzed (R ) and catalyzed (R ) process (Mabey and Mill, 19T8):
n ci
R = k [ECH] [N]
R = k [ECH-H+] [N]
d cl
R = (k [ECH] + k [ECH-H+]) [N]
n a
The concentration of "ECH-H+" is dependent upon the equilibrium constant (K)
for the protonation reaction:
-------
[ECH-H+] = K [ECH] [H+]
Thus,
R = (k + k K [H+]) [ECH] [N].
n a
When water (H_0) is the nucleophile N in water solvent at 298°C, the values
of k and k K are as follows (Mabey and Mill, 1978):
n s
kn= 9.8 x IP"7 s"1 = 1.76 x 10~8 M"1^'1
bt>.6 M
kaK = 8.0 x 10~4 H^-s"1 = 1.44 x 10~5 n~2's~l
bb.b M
Thus, above pH 3 (i.e.. [H+] = 10~ ) the uncatalyzed reaction (k^) is
the most important contribution to hydrolysis. It should be noted that above
pH 7, the concentration of OH (hydroxyl anion) starts to become significant
and the reaction of this nucleophile with ECH starts to become an important
contribution to the overall hydrolysis rate. Mabey and Mill (1978) calculate
the pseudo-first order half-life for ECH in water at pH 7 and 25°C as 197
hours. More recently, Piringer (1980) calculated half-lives of ECH in water
at 20°C with the following results:
pH half-life of ECH
pH 2.5 79 hours
pH 7 148 hours
pH 12 62 hours
At pH 2.5, the half-life is determined by reaction between both protonated and
unprotonated ECH and HO. At pH 7, the half-life is determined by reaction
between unprotonated ECH and HO and at pH 12, by reaction between
unprotonated ECH and both H_o and OH.
Piringer (1980) also tabulated the rate constants (k ) for reaction of
a variety of nucleophiles with unprotonated ECH in water at 20°C. The rate
constants are listed in Table 2.3.1A.
-------
Table 2.3.1A. Rate Constants for Reaction of Nucleophtles with Epichlorohydrin
in Water at 20°C.
Nucleophile
H20
N05
HC03
CH3CC>2
Cl~
Br~
CO?,"
OH~
CNS~
I~
Rate Constant (kn)
M-l- S-l
2.3 x 10~8
1.9 x 10~7
2.9 x 10~6
6.2 x 10~6
1.2 x 10~5
6.2 x 10~5
1.0 x 10~4
1.8 x 10~4
6.3 x 10~4
1.0 x 10~3
Adapted from Piringer (1980).
10
-------
The relative order of reaction rates of nucleophiles with ECH in water
listed in Table 2.3.1A is typical of these nucleophiles in protic solvents.
Note that hydroxyl anion (HO ) Is about 10,000 times more reactive than
water (H20).
The phenoxide ion (PhO ), which is relevant to formation of bisphenol
A propylchlorohydrin ether as an intermediate for epoxy resins, usually has
about the same reactivity as bromide (Br ) anion (March, 1968). Enikolopyan
et al. (1982) have discussed the kinetics of the reaction of bisphenol A with
ECH. The reactions are complex but follow the same principles discussed above.
The data cited above can be used to predict the half-life of ECH in
water under a variety of conditions. Unfortunately, the rates of ring-opening
reactions have not been studied in nonaqueous media such as glycerol or
solvents which would simulate epoxy resins. Thus, although epichlorohydrin
should react with glycerin and hydroxyl groups in epoxy resins, we can not
accurately predict the rate of these reactions.
2.3.2 Other Reactions of Epichlorohydrin
Direct nucleophilic displacement of the chlorine from ECH is not an
important process relative to the rate of opening the epoxy ring.
Free radicals can abstract hydrogens from ECH (Santodonato et al.,
1980), but no commercial users of these reactions are known. Oilling et al.
(1976) examined the atmospheric chemistry of ECH. From these results, the
estimated half-life of ECH in bright sunlight in the southern U.S. is 42
hours. The main mode of degradation under these conditions is hydroxyl
radical oxidation. Direct photolysis of ECH should not be important at the
wavelengths of light reaching the earth's surface (i.e., ECH does not have a
chromaphore that absorbs energy at the relatively long wavelengths of light
reaching the earth's surface).
11
-------
3.0 MANUFACTURERS AND PRODUCTS
Over 350 million pounds of epichlorohydrin (ECH) is produced annually
in the United States. All ECH is produced by two companies, Dow Chemical,
U.S.A. and Shell Chemical Company.
Approximately 75 percent of the ECH produced is used captively to
produce epoxy resins, synthetic glycerin and miscellaneous lower volume
products. Approximately 15 percent is used by other chemical companies to
produce the major end product, epoxy resins, and other lower volume
products including elastomers, wet-strength and anion exchange resins and
water treatment polymers. The remaining 10 percent is exported.
As shown in Table 3.1 these ECH-derived materials are in turn used to
manufacture products for a variety of uses in the automotive, construction,
drug, food products, and pulp and paper industries.
3.1 Production Volume and Supply
Since ECH is now produced domestically by only two companies, recent
ECH production data are unavailable from the United States Department of
Commerce or the United States International Trade Commission. Estimates of
the production volume of crude ECH are made from published data and trade
estimates of production of unmodified epoxy resins and glycerin (Chemical
Purchasing, June 1982). For the years 1978-1982 the production estimates
were as follows:
Crude-ECH*
Year Production
(million Ibs)
1978 347
1979 412
1980 397
1981 397
1982 375 (est.)
* Yield refined ECH is 97 percent crude ECH; all ECH is refined prior to
use.
Source: 1978-81, U.S. Department of Commerce, Bureau of Census; 1982
estimate, Chemical Purchasing (June 1982).
12
-------
Table 3.1. Epichlorohydrin Products, United States Consumption and Product End-uses.
Product
Annual ECH
consumption (1982)
Percent
Major uses
Epoxy Resins
Bisphenol A (DGEBPA)
Aliphatic
Polyether
Epoxy Novolac
Phenoxy Epoxy and other Epoxy
Synthetic Glycerin
Wet-Strength Resins
Water Treatment Polymers
Elastomers
(million Ibs.)
172-175
87-90
10-15
12
7-9
56
surface coatings, laminates/composites
castings/molding, flooring
29
adhesives
ingredient for food/beverage, cosmetics,
drugs; hunectant in tobacco; plasterizer
for cellophane and reactant in alkyd
resin, urethane polymers, triacetin
explosives production
paper industry, for paper sizing
water clarification, waste water treatment
flocculating agents
seals, gaskets, jackets for wire and cable,
hoses, belts, rubberized fabrics
Anion Exchange Resins
Alkyl Glyceryl Ether Sulfonates
Glycidyl Ethers
Glycidyl Esters
Fyrol FR-2
Total (approximate)
<1
3-5
3
<1
2
311
0.2
1
1
0.2
0.6
surfactants ; shampoos ,
reactive diluents for
epoxy resins
flame retardant
liquid detergents
Source: Arnold (1984b), Cogswell (1983).
13
-------
The decrease in production since 1979 is attributed primarily to the
recessionary economy and the resulting decline in demand for ECH-derived
end products. For 1983, analysts projected gains of 5 to 8 percent over
1982 levels for the large volume end products; however, even with these
anticipated increases, production requirements would still be below the
record high of 1979.
3.1.1 Manufacturers and Production Volume
ECH is produced domestically by Dow Chemical, U.S.A. and Shell
Chemical Company. Dow has a production facility at Freeport, Texas. Shell
has two plants in operable condition, but has consolidated its ECH
production at one facility. The plant locations shown below have a
combined annual capacity of 640 million pounds (SRI, 1983; Chemical
Purchasing, June 1982).
Company Plant Location Annual Capacity
Dow Chemical, U.S.A. Freeport, TX 420
Shell Chemical Co. Deer Park, TX 220
Norco, LA
In recent years, capacity utilization has ranged from 60 to 65 percent.
Trade forecasts indicate that the present rated capacity will be adequate
to meet projected ECH demand until the late 1980s (Chemical Purchasing,
1982).
3.1.2. Imports and Importers
Imports of ECH contribute little to the domestic supply. ECH imports
shown below for 1978 to 1983 represent less than one percent of the
domestic production.
14
-------
Year Imports
(million Ibs.)
1978 3.4
1979 2.4
1980 1.9
1981 3.0
1982 2.1
1983 1.8 (January through September)
Source: Cogswell et al. (1983); U.S. Department of Commerce (1983)
The primary country of origin is Japan. In 1981 and 1982 over 98 percent
of imported ECH came from Japan. Importers of ECH identified in the TSCA
Inventory are Marubeni America Corporation, Shell Oil Company, Mitsubishi
International Corporation, Nichimen Company, Inc. and Hercules Inc. (Math
Tech, 1983).
3.1.3 Exports and Exporters
Exports of ECH typically amount to 10 to 15 percent of United States
output. Total quantities exported have declined from a high of almost 52
million pounds in 1979, as shown below.
Year Exports
(million Ibs.)
1978 21.8
1979 51.9
1980 47.3
1981 37.4
1982 26.7
1983 12.1 (January to September only)
Source: U.S. Department of Commerce, Bureau of Census (1983)
The growth in exports through 1979 has been attributed in part to the
lower domestic price of raw materials and the greater efficiency of the
large United States ECH plants; the decline since 1979 has been attributed
to the world recession and the strong dollar, which hurts the
competitiveness of U.S. ECH abroad.
15
-------
A number of countries import ECH from the United States as shown in
Table 3.2. Major importing nations are Japan, Mexico, Canada, Brazil, and
India. A cursory examination of the quantities imported by several
countries, including Brazil, Netherlands, Australia, and the Republic of
South Africa, show that their imports have declined sharply since 1981.
However, other countries are now importing ECH. Reasons for these
individual trends have not been investigated.
3.1.4 Net Domestic Supply
The net domestic supply of ECH is summarized in Table 3.3. The net
domestic supply has remained fairly constant at about 350 million pounds
since 1979.
3.2 Markets
Currently for all uses, crude ECH is first refined. Of the total U.S.
production of ECH, epoxy resins typically consume 50-55 percent, synthetic
glycerin 25-30 percent, and miscellaneous derivatives and exports 10
percent each (MCP, 1982).
3.2.1. Epoxy resins
Approximately 50 percent of total ECH production is consumed for the
manufacture of epoxy resins. In 1982 an estimated 172-175 million pounds
of ECH was consumed to produce the following epoxy resins:
Bisphenol A (DGEBPA)
(25068-38-6, 25036-25-3)
Aliphatic (31921-70-7, 25038-04-4, etc.)
Polyether (39443-66-8, etc.)
Epoxy Novolac (29690-82-2, etc.)
Phenoxy Epoxy and other Epoxy
16
-------
Table 3.2. U.S. Exports of Epichlorohydrin, by Country of Destination,
1981-1983
Country of destination
1981
1982
1983 I/
Canada
Mexico
Haiti
Columbia
Venezuela
Brazil
Argentina
Netherlands
India
Japan
Australia
Republic of South Africa
Republic of Korea
China - Mainland
China - Taiwan
Saudi Arabia
New Zealand
Hong Kong
Guatemala
Other
Total
4,392
4,345
154
219
572
7,630
1,326
7,406
446
5,455
2,706
2,670
—
—
—
—
—
—
—
102
37,425
-(thousand pounds
954
3,542
—
263
780
10,978
1,531
3,307
1,311
3,628
216
—
—
—
—
—
—
—
—
179
26,691
— _____
1,010
2,715
—
68
210
2,645
574
795
1,767
216
*
375
1,428
219
2
36
*
11
—
12,072
\_/ January through September only.
Due to rounding these totals may not add.
* Less than 500 pounds.
Source: U.S. Department of Commerce, Bureau of Census (1983)
17
-------
Table 3.3. U.S. Epichlorohydrin Production, Exports, Imports, and Net
Domestic Supply, 1978-1983
Year Production Exports Imports
/ 'IT* T i«» ^
1978 346.8 21.8 3.4
1979 411.9 51.9 2.4
1980 397.3 47.3 1.9
1981 397.4 37.4 3.0
1982 375 a,b/ 26.7 2.1
1983 c/ a/ 12.1 1.8
Net domestic
supply
328.4
362.4
351.9
363.0
350
a/ Information confidential; only two producers.
b/ Estimated (Chemical Purchasing, June, 1982).
c/ January through September only.
Source: U.S. Department of Commerce, Bureau of Census (1983); Chemical
Purchasing (June 1982).
18
-------
Large volume markets for ECH-derived materials are the automotive and
construction industries. Growth of ECH is tied directly to expansion in
these markets and the relative price and performance characteristics of
ECH-derived materials and possible substitutes.
Projected growth rate for the period 1982-1987 for ECH consumed for
epoxy resins is 5 to 7 percent (Cogswell, 1983).
3.2.2 Glycerin
ECH is produced and used captively for the production of synthetic
glycerin. The estimated consumption of ECH for synthetic glycerin in 1982
was 87-90 million pounds (Arnold, 1984b; Cogswell, 1983) . The consumption
of ECH for production of synthetic glycerin varies somewhat from year to
year depending on the competition from natural glycerin.
Although government sources no longer report synthetic glycerin
production separately, approximately one-third of the total 1982 U.S.
glycerin production (synthetic and natural) of 232 million pounds (77
million pounds) was estimated to be synthetic glycerin. All synthetic
glycerin is now produced by Dow from ECH (Kovats, 1983). Dow's synthetic
glycerin capacity at the Freeport, Texas facility is rated at 115 million
pounds (CMR, 1981). FMC previously produced synthetic glycerin from
propylene oxide at its Bayport, Texas facility, but ceased production on
July 1, 1982. The plant capacity was 40 million pounds, but an industry
source reported that the plant was operating at only about 50 percent for
the year prior to its closing. Thus, its closing had relatively little
impact on the overall glycerin market (Kovats, 1983). An FMC
representative (Fisher, 1983) indicated the plant closure was due primarily
to the combined effects of decreased demand for glycerin and increased
energy costs for this energy intensive process.
In recent years, natural glycerin has taken over a larger share of the
total glycerin supply (Fisher, 1983). The natural glycerin producers have
an estimated total capacity of 200-260 million pounds. In addition, Emery
19
-------
Industries, Inc., a subsidiary of National Distillers and Chemical Corp.,
has announced a $50 million expansion at its Cincinnati, Ohio production
complex that is scheduled to be completed in early 1984 (SRI, 1983).
From 1962 to 1980 the United States was a net exporter of glycerin.
However, this situation has changed and since 1981 imports have become more
important in overall glycerin availability as shown in Table 3.4 (The Soap
and Detergent Association, 1983).
Future demand for ECH for synthetic glycerin is difficult to predict
because of its dependence on the somewhat erratic availability and
economics of natural glycerin that are in turn dependent on the demand for
fatty acids produced from natural glycerides. SRI (Cogswell et al., 1983)
has, projected slow growth, averaging less than 1 percent annually through
1987, in the consumption of glycerin and thus of ECH for glycerin.
3.2.3 Miscellaneous derivatives
Other important uses of refined ECH include elastomers, water
treatment polymers, wet-strength and anion exchange resins, alkyl glyceryl
ether sulfonates and glycidyl ethers and esters. The estimated annual
consumption of refined ECH in 1982 for each of these materials is shown
below.
ECH Consumption (1982)
million pounds
Elastomers (24969-06-0, etc.) 9
Wet-Strength Resins (25212-19-5, etc.) 15
Water Treatment Polymers 12
Anion Exchange Resins (25014-13-5, etc.) <1
Alkyl Glyceryl Ether Sulfonates 3
Glycidyl Ethers (2426-08-6, etc.) 3
Glycidyl Esters (106-90-1, 106-91-2, etc.) <1
Fyrol FR-2 (13674-87-8) 2
Markets include the paper industry and a variety of industries that
require high performance materials for marine applications, appliances,
20
-------
Table 3.4. U.S. Natural and Synthetic Glycerin Production Exports and
Imports, 1978-83.
n
Year
1978
1979
1980
1981
1982
1983*
Crude
atural & synthetic
production Exports Imports
/ '11* TV* \
302.6 41.5 7.7
345.7 53.7 0.6
301.1 57.1 19.3
280 30.1 40.4
232 14.1 32.3
7.4 23.9
* January through October. U.S. Department of Commerce, Bureau of Census
(1983).
Source: The Soap and Detergent Association, Statistics, Glycerin GL-3b,
April 12, 1983.
21
-------
coil steel, pipe, electrical parts, circuit boards, and water treatment.
Growth of ECH is tied directly to expansion in these markets and the
relative price and performance characteristics of ECH-derived materials and
their possible substitutes. SRI (Cogswell et al., 1983) recently published
projected growth rates for the period 1982-1987 for ECH consumed in
products for these markets:
Elastomers 6 to 8 percent
Other Domestic Users 3.5 to 6.5 percent
3.2.4 Exported Epichlorohydrin
Approximately 10 percent of the total U.S. ECH production is currently
exported as ECH. SRI (Cogswell et al., 1983) projected an increase in
demand for ECH by 1987 of 22 to 66 million pounds in Europe; the current
European ECH capacity is just sufficient to meet that demand. The current
Japanese capacity is about 120 million pounds per year and their current
production is about 105 million pounds per year. Since the U.S. capacity
is 640 million pounds per year and projected U.S. 1987 domestic consumption
is under 430 million pounds, U.S. exports could increase. Based on ECH
supply and demand data for Western Europe and Japan (Cogswell, 1983),
Dynamac projects U.S. exports (especially to Japan) could increase at a
rate of up to 10 percent per year, if the foreign market continues to grow.
In addition to direct ECH exports, annual United States exports of
ECH-derived epoxy resins total about 35 million pounds (USITC, 1983). By
contrast, imports of epoxy resins were 5.0 and 4.6 million pounds in 1981
and 1982, respectively.
3.3 End-Use Products Derived From Or Incorporating ECH
The primary end uses of ECH are for production of synthetic glycerin
and epoxy resins. Other lower volume end uses are wet-strength resins,
wastewater treatment polymers, elastomers, and a variety of miscellaneous
uses. These products, quantities of ECH consumed, and their uses,
summarized in Table 3.1, are described in detail below.
22
-------
3.3.1 Epoxy Resins
The most important epoxy resins are produced from ECH and bisphenol A.
The resins vary in properties depending on the ratio of ECH and bisphenol
A. Epoxy resins are not finished products but are reactive materials that
are combined with other materials to yield products that can be converted
to a predetermined thermoset structure. Annual ECH consumption for these
materials is approximately 175 million pounds.
Epoxy resins are cured by crosslinking agents. Cured epoxies are
generally characterized by outstanding mechanical and electrical
properties, dimensional stability, resistance to heat and chemicals, and
adhesive to a wide range of materials.
The two major epoxy producers, Dow and Shell, have over 75 percent of
the total epoxy capacity of 647 million pounds. Both produce ECH
captively. Epoxy resins producers, their plant locations and capacities
are listed in Table 3.5.
The epoxy total capacity, production and exports are shown in Table
3.6 for 1979-1983. Estimates are given for 1984. Imports during this
period amounted to less than 2 percent of production. In 1981 and 1982,
for example, imports were 5.0 and 4.6 million pounds, respectively.
Although the effective capacity is considerably below the nameplate
capacity shown above because of complications in switching production of
different grades, the producers have sufficient capacity for increased
production. If the projected 1984 production of 340 million pounds is
attained, the operating rate will be approximately 60 percent.
For the past decade premium quality thermoset epoxies have been
projected to benefit from quality improvement campaigns in the automotive,
electronic and other durable markets. In practice, however, these gains
have been intermittent and have been noticeably impacted by recessions.
Even though epoxy resin production dropped 21 percent during the 1979-83
23
-------
Table 3.5. Epoxy Resin Producers, Plant Locations and Capacities.
Company
Plant location
Product Annual
name capacity Remarks
Celanese Corp.
Celanese Plastics and
Specialties Co.,
Specialty Resins
Ciba-Geigy Corp.
Plastics & Additives
Div. Resins Dept.
Dow Chemical U.S.A.
Reichhold Chemicals,
Inc.
Shell Chemical Co.
Union Carbide Corp.
Coatings Materials
Div. Specialty Chems.
& Plastics Div.
Total
Louisville, KY
Toms River, NJ
Freeoort. TX
Andovef, MA
Azusa, CA
Detroit, MI
Houston, TX
Deer Park, TX
Bound Brook, NJ
Taft, LA
(Epi-Rez)
(Araldite)
(D.E.R.)
(Epotuf)
(Epon)
(Bakelite)
(million Ibs)
25
60*
230
32
270
10 .
20
647
Phenoxy resins
Cycloaliphatic
epoxy resins
* Ciba-Geigy is closing this 60 million pound plant at Toms River, New
Jersey and adding 100 million pound capacity at Mclntosh, Alabama.
Epoxies, C&EN November 21, 1983, p. 10.
Sources: SRI International estimates as of January 1, 1983; 1983 Directory
of Chemical Producers, United States, pp. 816-817. (The Society
of the Plastics Industry, Inc. Facts and Figures of the U.S.
Plastics Industry 1982 Edition also lists Morton Industries as a
producer).
24
-------
Table 3.6. Annual Epoxy Resin Capacity and Production.
Year
1979
1980
1981
1982
1983
1984
Capacity
405*
405*
580
580
580
600
Production
i • -I -i • -I •• »
361
315
332
286
310 (est.)
340 (est.)
Exports
36
36
41
40
35 (est.)
* Liquid only.
Sources: Chemical & Engineering News, Key Chemicals, Epoxies November 21,
1983, p. 10; August 30, 1982, p. 12; September 28, 1981, p. 18;
and Society of the Plastics Industry, Inc. 1982 Edition, Facts &
Figures of the U.S. Plastics Industry, pp. 34-35.
25
-------
period, this decline was the lowest among major thermoset resins. Even
with the increase in production of 8 to 12 percent for both 1983 and 1984
that has been projected by industry analysts, the 1984 epoxy production
level will be below the record 1979 production.
The major end uses of epoxies are coatings, 45 percent; laminates and
composites, 25 percent; castings and molded items, 10 percent; commercial
flooring, 5 percent; and adhesives 5 percent (C&EN, November 21, 1983).
The largest epoxy resin coating use is for the interior of containers,
particularly cans for mildly corrosive materials such as beer, soft drinks
and some foods. Prospects for growth of epoxies in container coatings are
low in that most of the basic market penetration has already taken place.
Other major epoxy coating uses are for high performance materials for
industrial maintenance, marine parts, automobile undercoats and primers,
electrical products, and powder coatings of appliances and outdoor metal
furniture. The second largest use of epoxies is for laminates and
composites materials (i.e. products layered for high tension strength and
dimensional stability) for electrical parts and electronic circuit boards.
These materials are desirable in these uses because of their dielectric
strength, low shrinkage upon cure, good adhesion and ability to retain
properties under varying environmental conditions (Math Tech, 1983). Uses
of epoxies for adhesives is divided between mature, slower growing general
manufacture and consumer repair kit markets and faster growing specialty
industries like aerospace. Other uses of epoxies are for commercial
flooring and for tooling resins in the automobile and aerospace industry
(CSEN, November 1983; August 1982).
3.3.2 Glycerin
End uses of glycerin and its products are diverse and involve many
markets; the largest use (tobacco) is only 18 percent of the total (See
Table 3.7). Synthetic glycerin produced from ECH is essentially
interchangeable with natural glycerin (Kovats, 1983). Of the current uses
of synthetic and natural glycerin shown in Table 3.7, those processes
having moisture limitations and requiring 99.5-99.7 percent glycerin had
26
-------
Table 3.7. Natural and Synthetic Glycerin End-use Survey, Calendar Year
1982.
Year 1982
(thousand pounds)
Alkyd resins (for paints) 19,823
Cellophane and meat casings 9,018
Tobacco, including triacetin 43,645
Explosives and military use 4,181
Drugs, including toothpaste 39,333
Cosmetics 20,346
Monoglycerides and foods 25,190
Urethane foams 19,789
Distributor sales 39,039
Crude consumed as crude
(except for refining) 699
Miscellaneous 17,304
Total 238,367
NOTE: These data are based on reports of sales and captive uses submitted
by fourteen participating companies, which are producers of refined
glycerin or import brokers. While The Soap and Detergent
Association believes that the statistical methods and procedures
used to compile this report are reliable, it does not warrant the
accuracy or completeness of the data.
Source: The Soap and Detergent Association (June 2, 1983)
27
-------
been restricted to synthetic glycerin. (Natural glycerin typically is 96
percent.) Synthetic glycerin has been used exclusively for polyols and
urethane foams because of its lower moisture content. However, Proctor &
Gamble Company can now supply 99.5 percent minimum and Emery has 99.5
percent and 99.7 percent minimum natural glycerin (Emery Sales, 1984) which
means this natural product is now suitable for most of these uses also
(Kovats, 1983). The price of $0.81 per pound, tank car delivered, for both
99.5 percent minimum kosher natural glycerin and 99.5 percent minimum
synthetic glycerin (Wittwer, 1984) reflects this substitutability.
3.3.3 Elastomers
Epichlorohydrin-based elastomers or rubbers may be either the ECH
homopolymer, polyepichlorohydrin, or copolymers with ethylene oxide or
other simple oxiranes. Uses of these elastomers are based on their
low gas permeability, retention of physical and dynamic properties over
temperature range of -40 to 300°F, good tear and impact strengths and good
resistance to solvents, fuels, oil, and ozone. Major uses of these
elastomers are in seals, gaskets, hose, belting, wire, and cable jackets.
In these uses, ECH elastomers compete with neoprene and nitrile rubbers
(see Section 4.4) (Blast., January, 1983; Houston, July, 1975).
The volume of the ECH specialty engineering elastomer market in the
western world was projected to grow by 66.7 percent during the period
1981-86. During that same time period the growth of the major volume
engineering elastomers, nitrile rubber and neoprene, was projected to slow
or decline slightly (European Rubber Journal, February 1983).
ECH consumption for elastomers was 7-9 million pounds in 1982. ECH
elastomers are produced by Herculesl/ Inc. and the B.F. Goodrich Chemical
Co. (SRI, 1983). Plant locations and capacities are shown below:
28
-------
Plant
Location
The B.F. Goodrich Co.
B.F. Goodrich Chemical Group Avon Lake, OH
Product
name
Hydrin
Annual
capacity
(million Ibs)
Hercules, Inc.
Operations Division
Hattiesburg, MS Herclor
11
3.3.4 Wet-Strength Resins
Wet-strength resins derived from ECH are widely used in the paper
industry for paper sizing (Dow, 1980). The consumption of ECH for these
resins is 10-15 million pounds of ECH annually (Arnold 1984b; Cogswell,
1983). These resins are cured at neutral to alkaline pH which eliminates
acid-catalyzed degradation and embrittlement of paper, provides softer,
more absorbent paper and reduces machine corrosion. ECH-derived resins are
also effective creping aids in absorbent papers (Kirk-Othmer, 1981). Slow
growth for these wet-strength resins is predicted for the years ahead
(Cogswell, 1983) .
Major producers of ECH-based we,t-strength resins are Hercules, Inc.,
and Georgia-Pacific Corporation.
3.3.5
Water Treatment Polymers
Epichlorohydrin-derived polymers are used as cationic flocculating
agents by industries such as the pulp and paper industry. These water
treatment polymers are used for wastewater treatment and for reclamation of
materials during manufacture. Approximately 12 million pounds of ECH are
consumed annually for these polymers (Arnold, 1984b).
These polymers are in competition with other polymers that may be
tailor-made to predetermined specifications for treatment of specific
process or waste stream conditions (Arnold, 1984c). No indication of
growth trends due to this competition was found.
29
-------
3.3.6 Other Uses
Each of the remaining uses'of ECH consumes less than 5 million pounds
/"~^ "~^S
of ECH annuallyf(Arnold, 1984b) :\
The production of alkyl glyceryl ether sulfonates for
surfactants, primarily by Proctor £ Gamble, consumes about 3-5 y
million pounds annually. Proctor & Gamble uses these materials
in shampoos, light-duty liquids and toilet bars. Consumption is
projected to decrease due to the relatively high cost of these
materials (Cogswell, 1983).
The production of glycidyl ethers and esters consumes less than 4
million pounds annually. These materials are utilized as
reactive dilutents for some of the epoxy resins discussed above.
A relatively minor use of ECH is in the flame retardent Fyrol
FR-2 [tris (l,3-dichloro-2-propyl) phosphate]. Fyrol FR-2,
produced by,Stauffer Chemical, consumes approximately 2 million
pounds of ECH annually. Fyrol FR-2 is utilized as a flame
retardant in flexible foams that are used primarily for
automobile and furniture cushions (Morey, 1984). J
Anion exchange resins, produced by the reaction of ECH and
"ethylehediamine and higher homologues by Rohm and Haas CompanyJ)
and IXLamojid_S^amrpck__Corj>oration, consume less~than—one~miTlion
pounds annually.
In addition, ECH may have minor compounding uses including in
corrosion inhibitors, asphalt improvers, and as a stabilizer in
pesticide formulations (Math Tech, 1983).
30
-------
4.0 SUBSTITUTES FOR EPICHLOROHYDRIN
A feasible substitute for a commercial chemical like epichlorohydrin
(ECH) must be functionally equivalent, economically competitive and
toxicologically/environmentally acceptable. Epichlorohydrin (ECH) is used
exclusively as a chemical intermediate in Industry. Thus, substitution for
ECH is a matter of finding alternate processes to make the same products or
alternate products for the same uses. Direct substitution of a compound like
epibromohydrin for ECH would probably work for most uses, but the cost would
definitely be higher and the substitute would probably retain many of the
hazardous properties associated with ECH.
In this chapter some possible ways to substitute other chemicals for ECH
will be discussed. However, in most cases the approaches are speculative.
Almost without exception, substitution would require new capital investment,
process development and more expensive raw materials. The substitutes may
also cause toxicological or environmental hazards that are not evaluated
here. Notes on the hazards of some chemicals mentioned as substitutes for ECH
or in alternate process chemistry are listed in Table 4.1A.
4.1 Physical/Chemical Properties Required for Each Epichlorohvdrin use
Because epichlorohydrin is an Intermediate rather than an end product,
it is more important from the standpoint of substitutability to look at its
functional equivalents rather than structural analogues.
The two main uses of ECH are manufacture of epoxy resins and manufacture
of glycerin. Several alternate processes for making glycerin have been well
established (Lowenheim and Horan, 1975) although the ECH process seems to be
the only method of making synthetic glycerin that can compete economically
with natural glycerin Isolated as a byproduct of soap manufacture. Alternate
methods for manufacture of bisphenol A epoxy resins do not appear to have been
seriously considered, although some patents (e.g., Thigpen and Taylor, 1976)
hint that alternate procedures have been considered.
31
-------
Table 4.1A Hazards associated with chemicals that might substitute directly
of indirectly for Epichlorohydrin or be required for alternate
processes.
Chemical
acetone
acrolein
LDso (mg/kg)
Oral3 Dermalb
9,750 20,000
46 562
LCso (ppm)
Inhalation
66/6hc
Comments
mutagenic
Irritant,
mutagenic
acrylonitrile
allene (1,2-
propadiene)
allyl chloride
82
250
576/4hd
no information found
2,200
irritant,
mutagenic
carcinogenic
irritant
mutagenic
turaorigenic
arat
brabbit
cmouse
^guinea pig
Source: RTECS (1983)
32
-------
In the manufacture of synthetic glycerin, the intermediate is likely to
be a three carbon compound with substituents or multiple bonds that can be
oxidized or hydrolyzed to the product. Examples of such compounds include:
CH2=CH-CH2-C1 allyl chloride
CH2=CH-CH=0 acrolein
CH2=CH-C=N acrylonitrile
CH =C=CH allene
H-CEC-CH methylacetylene
«3
o
ir
CH -C-CH_ acetone
The utility of acrolein (see 4.3.1) and allyl chloride (see 5.0) in
manufacture of glycerin have been discussed. The other chemicals listed here
are more farfetched but are possible candidates.
The manufacture of epoxy resins of bisphenol A and other phenols and
alcohols requires a method for introducing a glycidyl ether group. Here again
the intermediate should be a three carbon unit with two or more substituents
(i.e., one substituent to form the ether linkage; the other substituent to
form the epoxy moiety). The same compounds listed for glycerin manufacture
are possible intermediates.
4.2 Alternate Processes for Synthesis of Epoxy Resins
The major commercial use of epichlorohydrin (ECH) is manufacture of epoxy
resins (i.e., monomeric and oligomeric glycidyl ethers). We have identified
two approaches to synthesis of glycidyl ethers that do not require ECH (Figure
4.2A). These approaches appear to be technically and economically plausible.
The key intermediates and reactions are discussed in patents for similar uses.
Determination of the actual feasibility of these processes is beyond the scope
of the current report and would require laboratory chemical and engineering
research. In this section, we will discuss the process chemistry, process
engineering and economics of the alternate processes in terms of the general
concept. For comparison, the current methods are discussed in section 5.2.1.
33
-------
4.2.1 Alternate Process Chemistry
The key intermediate in the alternate synthetic schemes shown in Figure
4.2A is the diallyl ether of bisphenol A (DAEBPA):
CH,=CH-CH,-0-(( )>-C-<( )>-0-CH2-CH =
This compound is listed in the non-confidential TSCA Inventory under CAS No.
3139-61-1. In 1911, it was produced at a rate of 10,000 to 100,000 Ib/year
by 3M Corporation. In a telephone call with Dr. Bill Paterson of 3M
(Sittenfield, 1984), it was found that the chemical is produced in a batch
process for use as an intermediate for consumption by 3M. They would manu-
facture and sell the compound in lots of about 10,000 pounds at a price
between $4 and $5 per pound. Information obtained with a sample of the
product indicated that likely starting materials were bisphenol A and allyl
chloride with toluene as solvent.
A search of the patent literature revealed that DAEBPA is mentioned in
several patents: duPont (Fielding and Richards, 1967) reported synthesis of
DAEBPA by refluxing a mixture of bisphenol A (27.9 parts) and allyl bromide
(33 parts) with potassium carbonate (35 parts, to absorb acid) in acetone (45
parts) for 1 hour. The acetone was removed (by distillation) and the product
was dissolved in diethyl ether. The organic solution was washed with aqueous
sodium hydroxide, dried and filtered to yield 35 parts of DAEBPA (93% yield
based on bisphenol A) after evaporation of the solvent. In this same patent
(Fielding and Richards, 1967), the authors prepared analogous compounds by
substituting 2,3-dichloropropene, l,3-dichloro-2-butene and 1,2-dichloro-
3-butene or l-chloro-2-butene for allyl bromide. Apparently, good yields were
obtained in each case. These results indicate that substituting allyl chloride
for allyl bromide would probably yield the diallyl bisphenol A ether without
difficulty. A Russian patent (Savoslkin et al., 1979) describes preparation
34
-------
C1-CH2-CH=CH2
dichloropropanols
ally! chloride
bisphenol A
base
R-0-CH2-CH=CH2
base
A
C1-CH2-CH-CH2
epichlorohydrin
bisphenol A
base
OH
R-0-CH2-CH-CH2-C1
Proposed
Process B
S
C12/H20
peracid
CH3C03H
Proposed
Process A
base
R-0-CH2-CH-CH2
diglycidyl ether
bisphenol A
Figure 4.2A. Alternate pathways to the diglycidyl ether of bisphenol A.
35
-------
of DAEBPA and other aromatic allyl ethers by the reaction of allyl chloride
with the phenol in butyl alcohol at 80-90°C using KOH to make the phenolate
salt as an intermediate.
Braun and Lee (1976) report that reaction of bisphenol A (115 g) with
allyl chloride (38 g) in 300 mL of alcohol with sodium hydroxide (20 g) for
7 h yielded the diallyl ether (21 g) and the monoallyl ether (38 g) of
bisphenol A. The mole ratio of bisphenol A to allyl chloride was 1:1 and this
limited formation of the diallyl ether. Nonetheless, it is likely that
reactions involving allyl chloride and sodium hydroxide in an alkyl alcohol
solvent yield substantial byproduct of the allyl alkyl ether. In the experi-
ment by Braun and Lee (1976), the bisphenol ethers only account for 55% of the
allyl chloride. Brady et al. (1975) describe a similar synthesis of the
diallyl ether of bisphenol A, but do not report the yield.
Reaction of a phenol with an allyl chloride has been used on a large
scale to make industrial chemicals. For example, FMC Corporation reacts
2-nitrophenol with l-chloro-2-methyl-2-propene as the first step in the
synthesis of the pesticide carbofuran (Protzel, 1981). Thus, commercial
preparation of DAEBPA appears to be technically feasible. The only side
reactions expected
to possibly lower the yield of this reaction would be the C-alkylation of the
phenol that might occur if a non-polar reaction solvent were used (Roberts and
Caserio, 1965). At high temperature (above 200°C), the allyl ether might
rearrange to the ortho-allyl phenol (Claisen rearrangement) (Roberts and
Caserio, 1965).
It is noteworthy that the diallyl ether of bisphenol A has potential
economic applications beyond formation of epoxy resins. Fielding and Richards
(1967) describe its use as a fungicide to protect sugarcane from Rhizoctonia.
Brady et al. (1975) used it to prepare bis(2,3-dibromopropyl) bisphenol A
ether which was found to be useful as a flame retardant. It has also been
used as a crosslinking agent in photocurable lacquers (Guthrie and Rendalic,
1975) and in azo dye reactive dyeing of cotton (Wolf and Weissenborn, 1971).
Heating the diallyl ether of bisphenol to about 200°C results in rearrangement
to the 0,0'-diallyl bisphenol A (Claisen rearrangement; Roberts and Caserio,
1965) that may have uses including formation of unsaturated epoxy resins
36
-------
(Zahir and Wyler, 1977). High production of the diallyl ether of bisphenol A
(as would be the case if it were used instead of ECH to make epoxy resins)
would probably make it more available for these types of uses.
Two options for conversion of the diallyl ether of bisphenol A (DAEBPA)
to the diglycidyl ether of bisphenol A (DGEBPA) are shown in Figure 4.2A. The
practicality of the two methods will be compared in section 4.2.3. The first
method involves chlorination of the diallyl ether in alkaline solution to
initially produce the bis(propylchlorohydrin) ether of bisphenol A (CAS No.
4809-35-2), which is not stable under alkaline conditions and is an inter-
mediate in the ECH method of forming epoxy resins (see Figure 5.2.1.1A). From
that point, formation and isolation of the diglycidyl ether is identical to
the ECH-epoxy resin process.
The second option for formation of the diglycidyl ether from the diallyl
ether is reaction of the allyl groups with peracetic acid. This process has
been described in a patent assigned to Celanese Corporation (Thigpen et al.f
1976). Brown and Lee (1976) also used peracetic acid to convert the monoallyl
ether of bisphenol A into the monoglycidyl ether.
The process described in the Celanese patent (Thigpen et al., 1976)
calls for generating peracetic acid by passing acetaldehyde (bp 21°C) and
oxygen (95% O , 5% N ) in a mole ratio of 1:10 through an aluminum reactor
at 85°C to produce peracetic acid:
A vapor mixture containing 9.9 mole % peracetic acid, 23.4 mole % acetic
acid and 66.7 mole % acetaldehyde was generated and fed at a rate of 4.65
moles per hour to the bottom of a 45-plate distillation column. The column
was maintained at 100°C and 250 mmHg (absolute pressure). The diallyl ether
of bisphenol A was added to the top of the column at a rate of 0.325
equivalents per hour.
37
-------
The diallyl ether trickled down through the column and was epoxidized by
the counter current of peracetic acid. It then passed through a stripper
section below the column that was heated to 150°C to remove acetic acid. The
product rapidly cooled and exited the reactor at 30°C.
The crude product contained 5.7 weight % acetic acid and had an oxirane
oxygen content of 4.3 weight %. The theoretical oxirane oxygen content of the
diglycidyl ether of bisphenol A is 9.41 weight %; after correcting for acetic
acid, the product only seems to have had about 48% of the theoretical amount
of oxirane oxygen. Nonetheless, it seems likely that the reaction conditions
could be optimized to obtain much higher yields of the diglycidyl ether.
Epoxidation of olefins in solution is a more common approach especially
for small scale syntheses (Fieser and Fieser, 1967). Commercial solutions of
peracetic acid are typically 40% peracetic acid, 5% hydrogen peroxide, 39%
acetic acid, 1% sulfuric acid and 15% water (e.g., 0.77 mole peracetic
acid/100 mL). Before use, the strong sulfuric acid is usually neutralized by
adding 7.7 g of sodium acetate trihydrate per 100 mL of solution. The strong
sulfuric acid would cause excessive hydrolysis of the epoxide moiety in the
product, if it were not neutralized. The peracetic acid solution is usually
added over a short period of time to a solution of the olefin in cool (20°C)
methylene chloride or chloroform. The reaction mixture is usually allowed to
warm slowly for about a day before washing with 5% aqueous sodium hydroxide
followed by drying the organic phase and evaporating the solvent to obtain the
product. Yields of purified products are usually 70-75%.
4.2.2 Alternate Process Engineering
In this section we will outline two general processes for commercial-
scale manufacture of bisphenol A epoxy resins. For Proposed Process A, we
envision a two-step synthesis of the diglycidyl ether of bisphenol A from
allyl chloride, bisphenol A and peracetic acid via the diallyl ether of
bisphenol A (Figure 4.2A). For Proposed Process B, we envision a three-step
synthesis in which allyl chloride and bisphenol A are converted to the diallyl
ether, the diallyl ether is converted to the chlorohydrin and the chlorohydrin
is converted to the diglycidyl ether (Figure 4.2A).
38
-------
The first step in the proposed alternate process is summarized in
Figure 4.2.2A. The process is based on the duPont patent (Fielding and
Richards, 1967) with allyl chloride replacing allyl bromide. This
substitution is based on the higher availability and lower cost of allyl
choride compared to allyl bromide. The reaction with allyl chloride would
probably require a longer reaction period but no reduction of yield.
A reactor equipped with a stirrer, heater and reflux condenser would be
charged with:
Moles
bisphenol A 1 mole,
allyl chloride 2.2 moles,
acetone (solvent),
potassium carbonate 4 moles,
The reaction mixture would be heated and stirred at reflux temperature (about
50°C) for about 10 hours. Carbon dioxide would form from reaction of HCl on
K C0_ and would be vented. At the end of the reaction period, the reaction
mixture would be filtered and the filter would be washed with fresh acetone.
The solids would consist of a mixture of potassium chloride and potassium
carbonate and would be a solid waste. The organic solution would be distilled
at atmospheric pressure to remove acetone and allyl chloride, which would be
recycled to the reactor. It might be possible to crudely fraction the
acetone/allyl chloride mixture and use the acetone-rich fraction for filter
washing while sending the allyl chloride-rich fraction back to the reactor.
The crude product, containing bisphenol A, a few percent acetone and
traces of allyl chloride (and possibly some acetone condensation products),
would be kept above the melting point (est. 50°C) and contacted with aqueous
alkali for several hours to extract bisphenol A and convert allyl chloride to
water soluble allyl alcohol.
39
-------
Allyl Chloride-^
Bisphenol A fe
Potassium
Carbonate
w,
W
-P.
0
CO Acetone
'
^
i
Acetone
T i
Reactor
^
w
and Allyl Chloride (1) Aqueous Caustic
filter wash
f
Filter
fe
w
(2) Wa
^
Still
^
w
ter Water
r v
Washer
—>
Vacuum
Drying
(optional)
I
Potassium CarJxsnate/
Potassium Chloride
Allyl Alcohol/
Sodium Bisphenate
Product
Figure 4.2.2A. Proposed Alternate Synthesis of Bisphenol A Epoxy Resin
Process A, Step 1; Synthesis of Bisphenol A Diallyl Ether.
-------
The alkaline wash would be discarded and the product would be washed one
or more times with pure water to remove base. If necessary, the product would
be heated to about 100°C in vacuo (10 mmHg) to dry it. However, the subsequent
epoxidation reaction does not require dry product. The yield to this point
is expected to be about 90% based on bisphenol A. Also less than 5% of the
starting acetone and 1% of the starting allyl chloride are expected to be
lost. The product might contain traces of allyl chloride, allyl alcohol and
acetone condensation products. These impurities could be effectively reduced
by extending the alkaline treatment process and vacuum drying the final
product.
The second step in Proposed Process A for making the diglycidyl ether
of bisphenol A is peracetic acid epoxidation of the diallyl ether of bisphenol
A. Celanese (Thigpen et al.f 1976) discussed one approach to this epoxidation
in a patent. Our hypothetical process is shown in Figure 4.2.2B. It employs
the conventional solution epoxidation technique (Fieser and Fieser, 1961).
The diallyl ether (obtained as described above) would be dissolved in
methylene chloride in a reactor equipped for cooling (20°C), stirring and
reflux. Peracetic acid (with sodium acetate) would be added over a period of
about 2 hours with cooling to maintain the temperature at about 20°C and about
10% excess peracetic acid would be used. At the end of addition, the reaction
mixture would be agitated for approximately 24 hours.
The product would be isolated by washing sequentially with cold 5%
sodium hydroxide and cold water. The washes neutralize the acid and extract
the acetate salt. The methylene chloride would be distilled at atmospheric
pressure and then the diglycidyl ether of bisphenol A would be heated to about
100°C at 1 mmHg to remove the last traces of methylene chloride. The yield
would be expected to be about 80% based on the diallyl ether. The product
should be relatively free of low molecular weight impurities (e.g., CH2C12
or acetic acid). It might contain the diallyl ether (starting material) and a
mixed allyl/glycidyl ether. There might also be some dihydroxypropyl groups
and acetic esters of dihydroxypropyl group in the product resulting from ring
opening reactions of the epoxide.
41
-------
Bisphenol A Diallyl Ether
Methylene
Chloride
Peracetic Acid
Reactor
Methylene Chloride
(1) Aqueous Alkali
(2) Water
Washing
Decanting
Still
Bisphenol A
Diglycidyl Ether
Agueous Sodium Acetate
Figure 4.2.2B. Proposed Alternate Synthesis of Bisphenol A Epoxy Resin
Process A, Step 2; Peracetic Acid Epoxidation
-------
R-O— CH2 —CH —CH
H20/OH'
OH OH OH OCCH3
R-0-CH2-CH-CH2 R-0-CHa-CH-CH2
Proposed Process B for making the diglycidyl ether of bisphenol A
without using epichlorohydrin is designed to use the cheapest starting mate-
rials possible although it may have lower overall yields and produce more
toxic wastes (Figure 4.2.2C).
The first step of Proposed Process B is reaction of allyl chloride with
bisphenol A. it is based upon the approach of Braun and Lee (1976). A
reactor equipped with a stirrer, heater and condenser would be charged with
bisphenol A dissolved in an excess of allyl chloride. This solution would be
heated to reflux (45°C) and 50% aqueous sodium hydroxide would be added at a
rate which allows the water to distill out as an azeotrope with allyl chloride
(azeotrope bp 43°C, 97% HO). This azeotrope should stay as a single
phase. The hydroxide would form the bisphenoxide anion that would react with
allyl chloride. The reaction would probably require several hours and allyl
alcohol would probably be a major byproduct.
The reaction mixture would be heated to distill off most of the excess
allyl chloride, which would be recovered for the next batch. The residue
would consist of the product, sodium chloride salt and allyl alcohol (bp
97°C). Water would be added to dissolve the salt and extract the allyl
alcohol. The aqueous salt and allyl alcohol solution would be mixed with the
aqueous allyl chloride from the reactor vent and used as a feedstock for
manufacture of glycerin.
43
-------
Allyl Chloride
Bisphenol A
Aqueous Caustic
Allyl Chloride Recovery
Aqueous Allyl Chloride
Water
Water
Hypochlorite
Reactor
Washer
—DAEBPA-
Reactor
Crude Bisphenol A
Diglycidyl Ether
with Salt
(to purification)
Aqueous Salt/
Allyl Alcohol
Figure 4.2.2C. Proposed Alternate Synthesis of Bisphenol A Diglycidyl Ether
Process B, Step 1; Synthesis of the Diallyl Ether of Bisphenol A
(DAEBPA) and the Diglycidyl Ether of Bisphenol A.
-------
After thoroughly washing with water, the diallyl ether would be heated
and stirred and aqueous hypochlorite solution would be added. Excess water
would be distilled from the reaction mixture. The chlorohydrin intermediate
would form and be converted to the diglycidyl ether (Figure 4.2.2C). At the
end of the reaction, the reaction mixture should be similar to the crude
product obtained by reacting ECH with bisphenol A and base in the conventional
epoxy process (Jones and Chandy, 1974). The reaction mixture would be worked
up to isolate the diglycidyl ether of bisphenol A by a procedure very similar
to that described in Section 5.2.1.1.
The yield of product based on bisphenol A should be rather good (e.g.,
80% overall), but as noted above an appreciable amount of allyl chloride would
probably be converted to allyl alcohol in the first step.
4.2.3 Comparative Cost of Manufacturing Epoxy Resins by the
Epichlorohydrin Method and the Proposed Alternate Method
For the purposes of this evaluation we are assuming that a company would
have to buy all starting materials for manufacturing the diglycidyl ether of
bisphenol A from other chemical companies. We also assume that the capital,
labor, waste disposal and energy costs of the two processes are similar.
Thus, our analysis of comparative costs are limited to the costs of raw
materials and solvents to produce equivalent amounts of product.
The results are summarized in Table 4.2.3A. The cost of materials are
based upon recent (late 1983, early 1984) data provided by manufacturers for
large quantity purchases. We have made chemical and engineering estimates of
reaction yields and recoveries of products that are reflected in the
quantities of each feedstock listed.
It is apparent from Table 4.2.3A that the cost of peracetic acid and the
large quantity of potassium carbonate that would probably be required make
Proposed Process A very expensive even though it probably has higher yields
than Process B. Production of peracetic acid onsite from acetaldehyde and
oxygen as described in a Celanese patent (Thigpen et al., 1976) would probably
lower the cost of this process considerably.
45
-------
Table 4.2.3A. Raw Materials Needed to Produce One Pound of OGEBPA
Cost8 Conventional Process Proposed Process A
$/pound pounds" cost($) pounds" cost($)
Ally! chloride 0.61 0.82 0.50 0.61 0.37
(FW 75)
Chlorine 0.08 0.77 0.06
(FW 71)
Caustic (50% sol u.) 0.15 0.87 0.15
(FW 40)
Bisphenol A • 0.67 0.74 0.50 0.93 0.62
(FW 228)
Peracetic acid (35%) 2.66 - - 0.61 1.63
(FW 76)
Potassium carbonate 0.34 - - 2.29 0.78
Proposed Process B
pounds6 cost($)
t.O 0.61
0.53 0.04
0.79 0.12
0.82 0.55
_ _
_ _
(FW 138)
Acetone 0.21
Methyl ene chloride 0.29
Methyl Isobutyl Ketone 0.47
OGEBPA product:
Solid wastes produced:0
-
-
0.09 0.04
1.0 pound/$l.23
2.29 pound
0.15 0.03
0.15 0.04
_
1.0 pound/$3.47
3.74 poundsd
-
-
0.09 0.04
1.0 pound/$l.36
2.23 pounds
aBased on current prices for large volume purchases.
Data for peracetic acid are from FMC. Other data are from CMR (Hamnaker, 1984),
''Based on Oynamac chemical and engineering estimates.
C0isposal cost are not considered here but could be about $0.05/lb.
About one pound of this is C02 vented from the reactor.
46
-------
Even with these crude figures, it seems clear that the conventional ECH
process for making epoxy resins is the most inexpensive. For comparison, the
price for epoxy resin currently listed in Chem. Mkt. Rptr. (1984) is $1.31 to
$1.41 per pound (bulk liquid in tank cars). If the epoxy resin manufacturers
also make many of the feedstocks and coproducts (e.g., glycerin) associated
with the manufacture of epoxy resins via ECH, then the unit cost of the
conventional process would be even less. It should be noted that the raw
material cost of manufacturing bulk epoxy resins from DGEBPA produced in any
process could be less per pound than DGEBPA because excess bisphenol A
($0.67/lb) would be reacted with DGEBPA to make the resins.
4.2.4 Substitutes for Epichlorohydrin-Based Epoxy Resins
In the previous sections (4.2.1-4.2.3), an alternate synthetic scheme
for epoxy resin has been considered. In this section, substitutes for epoxy
resins in various uses will be discussed. Because of the numerous
applications of ECH-based epoxy resins, only a few of the more important areas
can be considered. The major application areas for epoxy resins are listed
below (Kirk-Othmer, 1980a):
Applications
Coatings
Laminated-compos ites
Moldings-castings
Construction
Adhesives
Miscellaneous
4.2.4.1 Substitutes for Epoxy Resin Coatings
Protective coatings is the largest market area for epoxy resins
(Kirk-Othmer, 1980a). The features that make epoxys desirable in these
applications are adhesion, toughness and chemical resistance. Various types
of application include automobile primers and finishes, marine coatings, can
coatings, and maintenance coatings (e.g., in oil refineries). Most epoxy
-------
coating systems are solvent-based, but epoxy resins are adaptable to the
waterborne-hlgh solids and solventless systems. Advantages of epoxy resins
in solventless coatings include the ability to apply thick coats, minimal
surface defects, excellent resistance to heat and chemicals and low overall
application cost. One of the main problems in using epoxy resins as solvent-
less coating is the short "pot life" (i.e., rapid hardening).
The ability to apply thick single coats of epoxy resins is the result of
the fact that epoxies do not require oxygen from the air to set (i.e., dry);
epoxy resins cure by reaction of the epoxy with a curing agent. The type of
curing agent affects the resin coating (Kirk-Othmer, 1979a). The main types
of epoxy resin systems are described below:
o Amine-cured epoxies
- short pot life
- high chemical resistance
- brittle
- chalk when exposed to weather
o Polyamide-cured epoxies
- poorer chemical resistance than amine-cured epoxy
- better weather resistance than amine-cured epoxy
- flexible
- degraded by strong bacterial growth
o Phenolic-epoxies
- heat cured
- most chemically resistant epoxy coatings
o Coal tar-epoxies
- good chemical resistance
- reasonable weather resistance but do chalk
- excellent resistance to water (fresh, salt,
brine, acid, alkaline, anaerobic)
- excellent durability
- black to reddish-brown color
48
-------
These epoxy coatings are compared to other resistant coatings in Table
4.2.4.1A. The cost (1977 data) of various resistant coating materials are
shown in Table 4.2.4.IB.
4.2.4.2 Substitutes for Epoxy Resins in Laminates and Composites
Behind coatings, the next largest market area for epoxy resins is
laminates and composites (Klrk-Othmer, 1980a). Kirk-Othmer (1981b) indicates
that, in principle many polymeric resins that wet reinforcing fibers (glass,
graphite) could be used to make laminates, but in practice most reinforced
plastics in commerce are based on unsaturated polyester, epoxy or
thermoplastic matrix materials.
Unsaturated polyesters and epoxies are both liquids that are
irreversibly cured. In the case of polyester, a prepolymer (oligoraer) is
formed from an anhydride (usually maleic anhydride) and a diol and an
inhibitor (hydroquinone) is added to prevent premature crosslinking. Then the
prepolymer and styrene are mixed with the reinforcing fibers in a mold and
benzoyl peroxide is added to initiate the polymerization in which styrene
crosslinks the prepolymer via the maleic acid moieties. In the case of epoxy
resins, the epoxy is mixed with the reinforcing fibers and a curing agent,
which crosslinks via the epoxide moieties. During hardening, unsaturated
polyesters shrink about 8% in volume and epoxy resins shrink about 4% in
volume. Because the fibers do not shrink, internal stresses are created. The
epoxies are better than the polyesters from that standpoint. Epoxies also
adhere to most surfaces better than polyester, are more resistant to water and
can be cured more precisely than polyesters (Kirk-Othmer, 1981b). However,
polyesters are cheaper than epoxies (Kirk-Othmer, 1981b) and polyesters may
have better electrical resistivity because halogen-containing moieties in
epoxy resins may give rise to ions during curing.
Thermoplastics such as nylon, polycarbonate, polyester, polypropylene
and SAN are also used for forming laminates. Thermoplastic laminates are
particularly useful for Injection molding and extrusion, where unsaturated
polyester and epoxy resins cannot be used.
49
-------
Table 4.2.4.IA. Properties of Resistant Coatings*
Lacauer coatings
Uses of resistant
coatings
Abrasion resistance
Bacterial and fungal
res i stance
Chem i ca 1 res i stance
acid-oxidizing
-nonoxidizing
-organic
alkali
salts-oxidizing
-nonoxidizing
so 1 vent-a 1 i phat i c
-aromatic
-oxygenated
water
Moisture
permeabi 1 ity
Contamination of
contacting materials
food
chemical
decontamination
Friction resistance
(faying surfaces)
Heat resistance, °C
wet
dry
Radiation
resistance, Gy^
Soi 1 resistance
Weather and light
res i stant
Principal hazard
Vinyl chloride-
acetate
copolymer
6
E
BSR
S or F
S or F
1 fatty acid
6
Splash, S
1. 6
E
swe 1 1 s
dissolves
VGI
low
c
VG
VG
48
65
106
G, properly
p i gmented
solvent F
Vinyl -aery-
late
copolymer
G
G
G
F
F
F
0
F or 0
F or D
F
dissolves
dissolves
G
38
65
E
solvent F
Ch 1 or i nated
rubber
G
G
BSR
S or F
S or F
dissolves in
fatty acids
G
F or 0
1. G
G
dissolves
dissolves
VGI
low
water, G
G
38
60
106
G, properly
pi gmented
solvent F
Coal tar-
pitch
(hot melt)
F
G
G
MR
f
NR
G
NR
sea water
G
NR
NR
NR
E
low
water, G
48
65
E
NR
coal tar F
Coreactable coatings
epoxy-
amine
G
G
G
NR
F
Spi 1 lage,
F
G
F
1, G
E
G
NR
VGI
low
G
G
VG
48
95
10?
heavy
cha 1 k i ng
dermatitis
solvent F
epoxy-
poly-
amide
G
NR
G
NR
F
F
G
F
1, G
G
NR
NR
VGI
low
G
G
VG
48
95
108
G
solvent F
Coal
tar-
epoxy
G
G
G
NR
F
NR
G
F
1, G
G
NR
NR
VGI
low
NR
F
NR
48
95
5x10°
G
chalking
dermatitis
solvent F
aG, Good; VG, Very Good; E. Excellent; NR, Not Recommended; BSR, Broad-Spectrum Resistance; I,
Imersion; S, Spray; F, Fumes; D, Ousts.
^G, primer required; critical for immersion.
°G, odorless; tasteless; nontoxic.
<*To convert gray to rad, multiply by 100.
Source: Kirk-Othmer (I979a)
50
-------
Table 4.2.4.IB. Typical High-Performance Coating Material Costs, 1977
Cost/m2
per 25 ym
thickness
($)
Cost/m2
per recommended
thickness
($)
4-coat water tank, vinyl
6-coat v i nyI food Ii n i ng
2-coat h i gh-buiId v i nyI (ext)
2-coat polyamine-epoxy tank lining
3-coat polyamide-epoxy (exterior)
3-coat epoxy-phenoIi c tank Ii n i ng
2-coat coal tar-epoxy
inorganic zinc
0.376
0.495
0.258
0.204
0.247
0.430
0.118
0.398
2.26
4.95
58
04
44
16
93
1.18
Adopted from Kirk-Othmer (I979a).
51
-------
The main applications for epoxies in the areas of laminates and
composites are in electrical laminates (e.g., printed circuit boards) and
filament winding (e.g., filament-wound glass-reinforced pipe). To achieve
flame retardance in electrical applications, the diglycidyl ether of
tetrabromobisphenol A is used as the basic epoxy building block (Kirk-Othmer,
1980a). Some specialized epoxies such as the tetraglycidyl ether of
methylenedi (aniline) cured with diaminodiphenylsulfone are used in the
aerospace industry for their high temperature performance in ablative
materials (reentry vehicles) (Kirk-Othmer, 1980a).
The total market for reinforced polyester laminates and composites was
798,000 metric tons in 1978 while the reinforced epoxy market was relatively
small at 24,000 metric tons (Kirk-Othmer, 1981b). In the electrical area,
polyesters were used at a rate of 73,000 metric tons compared to 10,000 metric
tons for epoxies; and only 9,000 metric tons of epoxies were used in filament
windings while over 100,000 metric tons of polyesters were used in each of
the following areas: marine, transportation, construction, and appliance-
aerospace-consumer. It appears that polyesters dominate the laminate/
composite areas except where specialized epoxies have demonstrated superior
performance and cost is not important.
4.2.4.3 Substitutes for Epoxy Moldings and Castings
Epoxy resins used for molding are generally solids while liquid epoxy
resins are used for casting. The uses of epoxy molding as casting materials
are generally as follows (Kirk-Othmer, 1980a):
Mo1dine
Transfer molding - encapsulation of solid state electrical components
using cresol-novolac solid epoxy resin with phenol
or cresol novolac hardener.
Compression molding - fabrication of large fiber-reinforced parts
(impellers, valves, pipefittings, pump housings).
Casting
Large electrical components including post insulators, bus-bar supports,
switchgear components, transformers, and encapsulated coils for indoor
use and tools.
52
-------
Other resins used for molding include phenolic resins, amino resins and
unsaturated polyester resins. Unsaturated polyesters are used for casting.
Phenolic resins used for molding are usually novolacs in powder or
pellet form cured with hexamethylene-tetramine. Transfer, compression, and
injection molding techniques are used. The cured resins resist high
temperature and solvents and have good electrical properties (dielectric
constant ca. 5.0) and are used for auto distributor caps, relays, brake
pistons, and appliance parts that are exposed to high temperature
(Kirk-Othmer, 1982a).
Amino resin molding compounds are typically urea-formaldehyde or
melamine-formaldehyde methylol compounds combined with alpha cellulose pulp
and dried to a hard popcorn-like intermediate. Catalysts, stabilizers,
colorants and mold lubricants are mixed with the intermediate to form the
molding compound. Amino resin molding compounds are used for decorative
products such as melamine plastic dinner plates; but the excellent electrical
properties, resistance to heat, hardness and strength make them useful in
industrial applications. They currently are more costly than phenolic resins
and they do not resist water as well as phenolic resins (Kirk-Othmer, 19"78a).
Unsaturated polyester resins with high fumarate (replacing maleate)
content along with fillers (clays), thermoplastics and thickeners (metal
oxides) are mixed with a high temperature polymerization initiator (t-butyl
perbenzoate) and used for sheet molding. The sheet molding compound is mixed
with chopped fiber glass and sandwiched between layers of polyethylene film.
The sandwich is stored as a roll until the viscosity of the molding compound
rises (due to crosslinking between the fumarates). The sandwich is finally
cut and molded under high pressure and temperature to yield parts with smooth
glossy surfaces. These parts have most application as sections of automotive
exterior skin (Kirk-Othmer, 1982b).
Unsaturated polyester resins have numerous applications as cast objects
including bowling balls, simulated marble, furniture parts, floor tile,
buttons and electrical encapsulation (Kirk-Othmer, 1982b).
53
-------
4.2.4.4 Substitutes for Epoxy Resins in Construction
Currently the only significant use for epoxy resins considered under the
category of construction is in flooring (Kirk-Othmer, 1982c). Only 8,000
metric tons of epoxy resins were used for this purpose in 1979 as compared to
168,000 metric tons of calendered vinyl and 61,000 metric tons of urethane
foam underlay. The epoxies are probably used in applications where chemical
resistance and heat resistance are required.
4.2.4.5 Substitutes for Epoxy Adhesives
Epoxy, acrylic, urethane, silicone and unsaturated polyesters are
examples of adhesives that "cure" (i.e., undergo chemical reaction) rather
than "set" when applied (Kirk-Othmer, 1978b).
4.3 Alternate Processes for Synthesis of Glycerin
Glycerin is obtained as a byproduct of soap manufacture and from several
synthetic processes (Lowenheim and Moran, 1975). According to Cogswell et al.
(1983), natural glycerin from soap manufacture is available in adequate supply
to meet most demands, although there was a period in the early 1970s when syn-
thetic glycerin dominated the market because of excess ECH capacity (Lowenheim
and Moran, 1975). At that time, three synthetic glycerin processes were used:
glycerin from allyl chloride via ECH (see Section 5.2.2)
- glycerin from propylene via acrolein
- glycerin from propylene via propylene oxide
Prior to 1969, a fourth process involving reduction of molasses was also used.
Statistics compiled by Cogswell et al. (1983) show the impact of
increased cost (e.g., production of glycerin from propylene oxide is energy
intensive (Fisher, 1983)) on the manufacture of synthetic glycerin after the
1973-1974 period. The production of glycerin from each process decreased in a
stepwise fashion:
54
-------
Estimated U.S. Production of Synthetic Glycerin
(millions of pounds)
by
Dow and Shell
via ECH
139
•75
99
78
by Shell
via acrolein
40
33
16
0
by FMC
via propylene oxide
29
33
26
8
1973
1977
1980
1982
Shell stopped production of synthetic glycerin via acrolein in mid-1980; FMC
stopped production via propylene oxide in early 1982 (Fisher, 1983).
The producers of natural glycerin currently have a capacity estimated
at over 200 million pounds per year, and National Distillers and Chemical
Corporation has announced a $50 million expansion at its Cincinnati, OH plant
by 1984 (Hammaker, 1983).
It can be concluded that virtually all current demand for glycerin
(about 290 million pounds per year, Cogswell et al., 1983) could be met by
natural glycerin and synthetic glycerin from sources other than ECH. Cogswell
et al. (1983) project slow growth for the glycerin market through 1987 with a
demand for 300 to 305 million pounds in that year. Based on the projection
that only ECH-derived synthetic glycerin will be used, Cogswell et al. (1983)
predict that the 1987 demand for ECH in this use will be 107-117 million
pounds (1.15 pounds of crude ECH are needed to make a pound of glycerin).
Regulatory restrictions against the use of ECH to manufacture glycerin
or increased pressure to remove residual ECH from synthetic glycerin would not
reduce the availability of glycerin but would probably increase its cost. The
most reasonable approach to avoid potential exposure to ECH residues (if any)
in synthetic glycerin would probably be to direct ECH synthetic glycerin into
manufacture of products like nitroglycerin or alkyd resins in which the
reaction conditions would favor hydrolysis of the oxirane ring.
55
-------
4.3.1 The Acrolein Process
Lowenhelm and Moran (1975) summarize the chemistry and engineering
Involved in manufacture of glycerin via acrolein. The chemical reactions are
as follows:
CH =CH-CH + 0 - ^CH2= CH~CHO
CH2=CH-CHO + (CH3)2CHOH - > CH2=CH-CH2
CH =CH-CH OH + HO - > HOCH CH(OH)CH OH
The yield of the first step is 85%; the yield of the second step is 77%; and
the yield of the third step is 80 to 90%. Thus, the overall yield for the
manufacture of glycerin based on propylene is 52% to 59%.
It should be noted that oxygen and propylene are the only raw materials
needed in this process. Propylene can be converted to isopropyl alcohol in
70% yield:
H SO
CH =CH-CH. + H.O —34 > (CH.)_ CHOH
£• J £, -J £,
and isopropyl alcohol can be used to make hydrogen peroxide in 87% yield
(Lowenheim and Moran, 1975). Thus, using these processes, propylene and
oxygen can be used to produce glycerin with acetone as a byproduct and
hydrogen peroxide and isopropyl alcohol as intermediate reactants.
4.3.2 The Propylene Oxide Process
Glycerin has also been made from propylene by the series of reactions
shown below (Lowenheim and Moran, 1975):
CH2=CH-CH3 + peracid
o
\
56
-------
0
/ \
CH2-CH-CH- - > CH2=CH-CH2OH
CH2=CH-CH2OH + C12 - > C1CH2CHC1CH2OH
C1CH CHC1CH OH + base - >(ECH) - > glycerin
Lowenheim and Moran (1975) indicate that ECH is an intermediate in the process
as shown above. However, it appears that the chlorination step could be
applied in water to yield chlorodihydroxypropane, which would yield glycerin
via glycidyl alcohol rather than ECH.
4.3.3 The Invert Molasses Process
A final process for making glycerin described by Lowenheim and Moran
(1975) involves catalytic reduction of invert molasses to mannitol and
sorbitol. The sorbitol can be split into two moles of glycerin by high
temperature hydrogenolysis:
HOCH2(CHOH)4CH2OH - 2 -
4.3.4 Comparison of Synthetic Glycerin Processes
As discussed by Lowenhein and Moran (1979), synthetic glycerin plants
are integrated with the manufacture of other chemicals and cost are difficult
to determine. The feasibility of manufacturing glycerin will be affected by
the prices of its coproducts. For example, the markets for acrolein,
isopropanol, allyl alcohol, acetone and hydrogen peroxide all affect the
desirability of manufacturing glycerin from propylene via acrolein. We have
not attempted to untangle these many factors, but we note that the net result
was that during the mid-1970s processes used by Dow, Shell and FMC to make
synthetic glycerin were competitive with natural glycerin from soap manu-
facture. Currently, glycerin from epichlorohydrin seems to be the only
syhthetlc glycerin competitive with natural glycerin. This situation may
continue because glycerin manufacture constitutes a method of recycle/reuse
of wastes from manufacture of allyl chloride and epichlorohydrin.
57
-------
4.4 Substitutes for Epichlorohydrin Elastomers
The elastomers made from eplchlorohydrin have many very useful proper-
ties (Houston, 1975; Kirk-Othmer, 1979a; Scheer. 1978). In general, they have
good tear resistance and Impact strength, but the factors that have made them
the materials of choice In certain applications are their resistance to fuels
(especially partially oxidized fuels, unleaded aromatic fuels and methanol
(Gummikunst, 1980)) under conditions of appreciable heat (up to 300°F) and
their ability to retain flexibility at low temperatures (-70°F; CPI Mgmt,
1972). According to ML Zwickert and NC MacArthur of Hercules (cited in R & P
News, 1981), the copolymer of ECH and ethylene oxide (ECO; CAS No. 24969-10-6)
is subject to depolymerization with progressive formation of a lower strength,
solvent-swollen material during prolonged exposure to "sour" (oxidized)
gasoline containing hydroperoxides. The homopolymer of ECH (CAS No. 24969-
06-0) has better resistance to oxidized gasoline and meets General Motors
specification GM 6498M.
The most important limitation on applications of ECH elastomers is loss
of tensile strength during service, although hardness increases less during
aging than with most other elastomers (Gummikunst, 1982). The fatigue life of
ECH-elastomer bonds to metal has been noted as problem in using ECH-elastomers
for shock-absorbing motor mounts (Rubber Age, 1972). The price of ECH-
elastomers has been a limitation to its commercial success. In 1975, the
price of ECH-elastomers was about $1.15/lb (Houston, 1975).
Overall, the uses of ECH homopolymer seem to be in applications where
resistance to heat and fuel are most important, whereas the uses of ECH-
ethylene oxide copolymer seems to be in applications where resistance to fuel
and low temperature flexibility are most important. Some examples found in
the trade literature are as follows:
ECH Homopolvmer (CAS No. 24969-06-0)
Automotive seals and gaskets (R & P News, 1982; Blast., 1977)
Automotive hoses and tubes (R & P News, 1981; Chem. Mkt. R.,
1979)
Liners for hazardous waste (Hercules, 1983a)
ponds (0 to +325°F)
58
-------
ECH-Ethvlene Oxide Copolvmer (CAS No. 24969-10-6)
Wellhead seals for arctic oil
production (world oil, 1976)
Arctic-weather petroleum hose
("Blue Arctic Flexwing") (CPI Hgmt., 1972)
Liners for hazardous waste (Hercules, 1983a)
ponds (-40 to 300°P)
The other ECH elastomers found in the TSCA Inventory seem to have few,
if any, commerical-uses. These elastomers include:
ECH-Polymer CAS No.
ECH polymer with propylene oxide 24969-08-2
ECH polymer with ethylene oxide
and propylene oxide 25931-44-6
ECH polymer with allyl glycidyl ether 24969-09-3
ECH polymer with ethylene oxide
and allyl glycidyl ether 26587-37-1
A Japanese company has a patent to use the last polymer listed above (CAS
No. 26587-31-1) as a cover for rubber pipes and hoses. It is composed of 35
to 80 mole % ECH, 15 to 50 mole % ethylene oxide and 5 to 15 mole % unsaturated
epoxide (allyl glycidyl ether). It is vulcanized with a di- or tri-mercapto-s-
triazine (Fukushima et al., 1980). This ECH terpolymer (ETER) can also be
crosslinked with peroxides (Gummikunst, 1981). It is believed that B.F.
Goodrich calls this polymer Hydrin 400 (Scheer, 1978).
Mohan (1977) summarized the properties and costs of elastomers that are
competing for uses similar to those of polyepichlorohydrin (Table 4.4A). It
can be concluded from the data in Table 4.4A that the polyepichlorohydrin
elastomers do not appear to be essential for any use, but they offer good
properties at moderate prices. For low temperature, fuel-contact
applications, only silicones and ethylene acrylic rubbers offer similar
properties and both of these are much more expensive than the
polyepichlorohydrin rubber.
59
-------
Table 4.4A. Synthetic Rubbers Uses in Hot/Oil Automotive Applications
Type
Polyepichloro-
hydrin
Polychloroprene
Ethy 1 ene
Propylene
(EPDM)
F 1 uoroe 1 astomer
Si 1 icone
Polyacrylate
Ethyl ene Acryl ic
Tradenames
He re lor
Hydrin
Neoprene
(generic)
EPCAR
Epsyn
Nordel
Roya 1 ene
Vistalon
F 1 uore 1
Viton
Si lastic
Rhodors i 1
Cyanacry 1
Hycar
Vamac
Producer
Hercu 1 es
B.F. Goodrich
Denka Chemical
DuPont
B.F. Goodrich
Copolymer Corp.
OuPont
Un i roya 1
Exxon Chem.
Minnesota Mining
DuPont
General Electric
DOM Corning
SWS Si 1 icones Co.
Rhod i a , 1 nc .
Amer. Cyanamid
B.F. Goodrich
DuPont
Properties
Resistant to heat (325°F),
oil, fuel, ozone; good
low temperature flexibility
(-40°F)
Resistant to heat (250°F),
oil, weathering; good
dynamic properties
Resistant to heat (275°F) ,
marginal oil resistance,
good electrical properties,
ozone and weather resistant
Resistant to heat 400°F
constantly, 600°F inter-
m i ttent 1 y , exce 1 1 ent re-
si stance to fuels and oils
Resistant to heat (500°F) ,
oi 1, solvents, good
electrical properties, low
compression set, low
temperature f 1 ex i b i 1 i ty
(-I50°F)
Resistant to heat (350°F),
oi 1 resistant
Resistant to heat (375°F) ,
oil resistant; virbration
Typical Uses
Hose & tubing,
molded products,
diaphragms
Hose, tubes and
covers, V-belts,
molded parts,
sponge seals
Door & window
seals, wire
insulation,
sight shields
0-ring seals,
shaft seals,
carburetor, tips,
diaphragms
Seals, wire
insulation,
spark plug
boots
Oi 1 seals,
valve stem seals
Seals, body
mounts
Typical Cost
(1977) ($/lb)
$1.20-1.40
$0.60-0.80
$0.45-0.63
$12.00
$3.00-5.20
$1.35-1.60
$1.50
damping, low temperature
fI ox i b iIi ty
Butadiene
Acryl on itri le
(nitriti le
rubber, NBR)
Chlorosul fonated
Polyethylene
Chem i gum
FR-N
Hycar
Krynac
Nysyn
Paracri 1
Hypa 1 on
Goodyear
F i restone
B.F. Goodrich
Polysar, Ltd.
Copolymer Corp.
Un i roya 1
DuPont
Resistant to heat (250-
300°F) transmission fluids,
oil, oxidation and ozone
Resistant to heat (300°F),
oil and complete ozone
resistance, weather
res i stant
Transmission,
valve stem and
crankshaft seals
hose tubes
Hose tubes and
covers, ignition
cable jacket,
spark plug boots
$0.60-0.80
$0.73-0.83
Adapted from Mohan (1977), Hawley (1977).
60
-------
4.5 Substitutes for Epichlorohvdrin Wet-Strength Resins
There are two general classes of ECH wet-strength resins; one group is
based on aroinopolyamide resin, the other group is based on polymeric amines
(Kirk-Othmer, 1981a). The newer polymeric amines include polymers of
diallylmethylamine, which contain only tertiary amines and form "perepiquat"
resins with ECH (Van Eenara, 1980). The polyamlne resins do not appear to be
very important commercially (Kirk-Othmer, 1981a). The technology associated
with manufacture and use of these resins is discussed in Section 5.2.4.
The aminopolyamide resins were introduced in 1958 by Hercules, inc. and
the polyamine resins were introduced in the 1970s (Kirk-Othmer, 1981a). They
cost more than urea-formaldehyde and melamine-formaldehyde resins but they
are more efficient and are cured at neutral or alkaline pH, which avoids
embrittlement of the paper, reduces corrosion of the paper making equipment
and provides a softer, more absorbent product (Kirk-Othmer, 1981a).
Kirk-Othmer (1981a) discusses four types of resins that might be used as
substitutes for ECH wet-strength resins:
urea-formaldehyde resins
melamine-formaldehyde resins
aldehyde-modified resins
polymeric amines
As noted above, the formaldehyde resins are functional and cheaper than the
epichlorohydrin resins, but they have undesirable characteristics. Resins
containing free aldehyde moieties can also be used as wet-strength resins
(probably by forming hemi-acetals). However, the wet-strength provided by
these resins decreases upon soaking (probably due to hydrolysis of hemi-
acetals). This property makes these resins suitable for treatment of sanitary
tissues (Kirk-Othmer, 1981a), which can break down to pulp in sewer systems.
Polymeric amines, like polyethyleneimine and chitosan (a polysaccharide based
on glucosamine obtained from the exoskeleton of insects, crabs, etc.) have
been considered but polyethyleneimine Is more expensive and less efficient
than other resins. Chitosan is not available on a large scale although it is
cheap and potentially abundant.
61
-------
Some of the ECH wet-strength resins might be accessible via alternate
synthetic schemes. For example, treatment of a aminopolyamide or polyamine
(like polydiallylmethylamine) (see Section 5.2.4) with allyl chloride would
produce a cationic resin with quaternary ammonium sites. This resin could be
activated prior to treatment of paper either by addition of hypochlorite at pH
11 or peracetic acid. If hypochlorite were used the process should yield very
similar results compared to the current wet-strength resins. A major
advantage of the "perallylquats" compared to "perepiquats" would be complete
absence of a tendency to gel during production or storage. Moreover, the
presence of allyl groups as well as chlorohydrin (incipient glycidyl) groups
in the hypochlorite-activated "perallylquat" resins would give the interesting
property of being able to crosslink cellulose or wool with unsaturated
polyester. Since allyl chloride and hypochlorite are used to make
epichlorohydrin, the cost of obtaining wet-strength resins by this route
should be similar to the usual process. The only limitation on this approach
would be that the allyl-treated polymer should have few unquaternized amino
moieties because these would tend to be oxidized by hypochlorite or peracetic
acid.
4.6 Substitutes for Epichlorohvdrin-Based Water Treatment Chemicals
There are several hundred synthetic flocculants currently available
commercially, but these are composed of a relatively few types of chemicals
(Kirk-Othmer, 1980c). These agents are used to flocculate and coagulate
suspended solids and allow their removal from water by sedimentation or
filtration. Flocculants can be classified according to the source as
inorganic (e.g., alum), synthetic organic or natural (e.g., starch, protein),
but these classifications do not reveal much about their applications, which
will be discussed below. The trends in flocculant useage discussed in
Kirk-Othmer (1980c) seem to indicate that alum and natural products (starch
and protein celloids) are being replaced by synthetic organic polymers. In
1977, the projected annual growth rate for synthetic organic flocculants was 8
to 10% per year through 1985 (U.J. Storch, Chem. Eng. News 56(4):9 (1978)
cited in Kirk-Othmer, 1980c). General economic data for major classes of
flocculants is listed in Table 4.6A.
62
-------
Table 4.6A. Economic Data for General Classes of Flocculants
Chemical U.S. Consumption as Flocculant Price
Alum 0.4 x 106 t in 1978 16£/kg in 1979
Lime 2.0 x 106 t in 1978 3.4tf/kg in 1979
Ferric Chloride 0.06 x 106 t in 1975 9.9^/kg in 1975
Synthetic Organics 0.02 x 106 t in 1977 $2.75 to $5.00
in 1977
Source: Kirk-Othmer (1980c).
63
-------
Selection of Elocculants is always based on cost and performance factors
(Kirk-Othmer, 1980c). The performance of a flocculant is affected by factors
such as pH, temperature and ionic strength of the turbid stream and the con-
centration and nature of the solids to be flocculated. The most important
performance factor in municipal water treatment may be clarity of the final
product, although in mineral recovery settling, rate may be more important.
Kirk-Othmer (1980c) provides a lengthy table of typical uses for various
flocculants. For synthetic organics, the factors that are important in deter-
35 5
mining uses are the molecular weight (low = 10 to 10 , medium = 10 to
10 , high = 1 to 5 x 10 , very high = greater than 5. x 10 ), the charge
density (percentage of monomer units that contribute change)(low = 1 to 10%,
medium = 10 to 40%, high = 40 to 80%, very high = 80 to 100%), the nature of
the charge (cationic or anionic), and whether or not the charge is constant or
varies with pH.
Cationic synthetic organic polymers listed in Kirk-Othmer as commercial
products are presented in Table 4.6B. Two of these are polymers of ECH with
methyl- or dlmethyl-amine. Based on comments in Kirk-Othmer (1980c), the
most important commercial compounds are the poly[N-(dimethylaminomethyl)-
acrylamide] and poly(2-hydroxypropyl-l-N,N-dimethylammonium chloride). These
polymers are expected to be used for municipal and industrial water supply
clarification, thickening iron ore concentrates and tails, and sewage sludge
dewatering. Alum, lime and ferric chloride are all applied for these same
uses. Thus, there are many potential substitutes for ECH-based water-
treatment chemicals.
64
-------
Table 4.66. Principal Commercial Synthetic Organic Polymers Used as Cationic Flocculants
CAS No.
Structure
Garments
po 1 y (ethy 1 eneam i ne)
apol y (2-hydroxypropy 1-
1 -N-ntethy 1 ammon i mu-
ch lor i do)
26913-06-4 -{cH.CH.NHk
OH CH,
31568-35-1 -{CH.CHCH.-NH-V-
0
OH CH,
L. , 1 1 ,
charge density varies with pH
charge density varies with pH
apoIy(2-hydrdoxypropyI
I-N,N-dimethyl-
ansnoniuro chloride)
poIyCM-(dimethyI am ino-
mathyI)aery I ami do]
CH,
25765-48-4 —fcH.CH-
•te-
O=C-NHCH,N(CH,),
strongly cationic, pH-insensitiva,
chIor ine-resi stant
charge density varies with pH
poly(2-vinylimidazolinum
bisulfate)
poly(diallyldimethy(ammonium
chloride)
26062-79-3
-(-CH.CH
x
NH
•CH, ,CH,
®
charge densitsy varies with pH
strong cationic, pH-insensitive,
chIor i ne-res i stant
poly(N,N-dirnethylaminoethyl
methacryIate)
polyCN-(dimethylaminopropyl)-
methaery Iamide]
25145-86-3
CH,
CH,-
-------
4.7 Substitutes for Alkyl Glyceryl Ether Sulfonates
The Proctor and Gamble Company has several patents on various uses o£
alkyl glyceryl ether sulfonates (AGES):
Use U.S. Patent
Ternary synergistic sudsing 3,332,879
detergent composition
Detergent composition having 3,332,874
superior sudsing characteristics
(synergistic mixture)
Detergent tablets 3,318,817
Unbuilt, high-sudsing, light-duty 3,179,599
liquid detergent having special
utility under acid conditions
Personal use lotion 2,999,068
Granular detergent bath 3,798,179
composition
Nonsmearing detergent bar 2,979,511
Cream shampoo 2,979,465
Opaque liquid detergent 2,970,964 and
composition 2,970,963
Liquid detergent composition 2,877,185
(single-phase, liquid, heavy
duty)
Clear liquid detergent 2,877,185
composition
Fabric softener (absorbent 3,843,395
sheet)
Other companies have patented uses outside the household/cosmetic detergent
field:
66
-------
Use Patent Company
Fabric softener in 4,110,678 A.R. Stanley Mfg. Co.
clothes dryer
Photographic coating 3,824,102 Konishiroku Photo ind.
Foaming agent for 3,713,110 Conoco, Inc.
removing material
from well bore holes
No information was found on the essentiality of AGES for these uses. It
can be noted that the composition of AGES is fairly unique among the surfac-
tants commonly employed. Its structure is compared to other surfactants below:
Alkyl glycervl ether sulfonates (AGES)
CH2X
R-0(CH -CH-0) H
2 n
Where R is an alkyl radical containing 8 to 22 carbon atoms, n=l to 4
and X=C1, -OH, or -SO H and at least one X in each compound of the mixture
•J
is a sulfonic acid salt (Whyte and Korpi, 1962).
Alcohol Ethoxy Sulfates (AES)
R-O(CH CH -0) SO M
Where R is typically an alkyl radical with 10 to 18 carbon atoms, n=l to
over 12, and M is usually a sodium cation.
Alpha Olefin Sulfonates (AOS)
R-CH(CH-) CH-SO-Na
I 2 n 2 3
OH
and
R-CH=CH-(CH0) CH0SO,Na
2 n 2 3
67
-------
Compounds with 2 or more sulfonates where R is an alkyl group and n=0,
1, 2. 3, etc.
It seems likely that AES or AOS could substitute for AGES in some or all
uses. AES are known for their immunity to the negative effects of water
hardness, their high foaming capabilities and their "softness" to skin. AOS
are said to give a "soft feeling" to washed fabrics. AOS also has detergency
and foam properties similar to linear alkylbenzenesulfonates (LAS) and may be
superior to LAS in hard water. AOS also has good water solubility (ADL, 197*7)
According to Whyte (1976), AGES is inherently more expensive than
"workhorse" surfactants (e.g., linear alkylbenzenesulfonates (LAS) and tallow
alkyl sulfates) and is not expected to enter the large-volume, heavy-duty
laundry product market. AGES can be used in specialty areas where its
foam-boosting ability and other performance attributes will compensate for
higher cost. It should be noted that Parran et al. (cited in Whyte, 1976)
found that a mixture of 70% sarcosinate and 30% AGES provided a voluminous,
stable lather for shampoos, but hair oils have a negative affect on the
foaming of AGES making it unsuitable as the sole or major surfactant in
shampoos.
4.8 Substitute for Epichlorohydrin-Based Anion Exchange Resins
A very small percentage of ECH goes into ion exchange resins. No
information was found on application of these resins. However, Rohm and Haas
Company (Meteyer and Fries, 1980) claims that ion exchange resins made by
reacting alkylpolyamines (e.g., triethylenetetraamine) with ECH followed by
alkylation of secondary amines with formaldehyde have enhanced stability with
respect to oxidation in test with oxidation by copper/hydrogen peroxide.
These ion exchange resins are described as "weakly basic" ion exchange resins
and probably could be replaced by other weakly basic ion exchange resins
such as Amberlyst A-21 (Rohm and Haas Co.) 4 kg/$96 (Aldrich, 1982).
68
-------
4.9 Substitutes for Pvrol 2
Fyrol 2 (tris(l,3-dichloro-2-propyl) phosphate, CAS. No. 13674-87-8) is
a flame retardant manufactured by the Stauffer Chemical Company. Parris
et al. (1983) classify Fyrol 2 as a plasticizing additive flame retardant and
identified several commercial flame retardants that have similar properties.
These are summarized in Table 4.9A. Fyrol 2, Antiblaze 78 and Thermo1 in 101
are all liquids at 30°C and have low vapor pressures. They are used
principally in urethane foams (e.g., seat cushions). Trls(monochloroalkyl)
phosphates such as
tris(l-chloro-2-propyl) phosphate (CAS No. 13674-84-5)
Stauffer, Fyrol PCF
Mobile, Antiblaze 80
tris(2-chloro-l-propyl) phosphate (CAS No. 6145-73-9)
Pelron, 9338
tris(2-chloroethyl) phosphate (CAS No. 115-96-8)
Pelron, 9500
are inferior because they have higher vapor pressures (Parris et al., 1983).
Fyrol 2 could be synthesized from l,3-dichloro-2-propanol and POCl ,
J
but removal of the HCl byproduct might be a problem. It might also be
possible to refine the crude dichloropropanol stream from ECH manufacture
(waste stream 3B in Figure 5.1.2.B, Saletan. et al., 1977) and react it with
POCl to make a flame retardant mixture that would be similar to Fyrol 2.
69
-------
Table 4.9A. Substitutes for Fyrol 2
Trade name
Manufacturer
Chemical Name/Structure/CAS No.
Garments
Fyrol 2
Ant!blaze 78
Thermolin 101
Stauffer
Mobile
Olin
Tr i s(1,3-d i chIoro-2-propyI)phosphate
[
-------
5.0 EPICHLOROHYDRIN MANUFACTURING AND PROCESSING
The history of the manufacture of epichlorohydrin is relevant to the
current form of the industry. In the 1940s, there was a demand for glycerin
which opened the market for synthetic glycerin. It was known that glycerin
could be obtained from allyl chloride by several pathways (Chera. Eng.
Progress, 1948). Tyrastra (1952) mentions two methods which seem to have been
used at the time:
(1) in the first method, allyl chloride was chlorinated to
1,2,3-trichloropropane, which was hydrolyzed to glycerin.
(2) In the second method, allyl chloride was hydrolyzed to
allyl alcohol, which was hydrochlorinated to chloro-
propylene glycol (monochlorohydrin), which was subsequently
hydrolyzed to glycerin.
Shell Development (Tymstra, 1952) patented a method for conversion of
allyl chloride to the dichlorohydrins (i.e., dichloropropanols) via hydro-
chlorination (i.e., chlorohydrinatlon) followed by hydrolysis to glycerin.
This process required dilute solutions because allyl chloride is not very
soluble in water (0.36% in water by weight at 20°C; Riddick and Bunger,
1970). The main feature of Tymstra's patent was an idea for reducing the
amount of water (and salt) in the final crude glycerin solution by diverting
20 to 75% (preferably 35 to 65%) of the aqueous dichloropropanol solution
through a heated (150-210°F) reactor where epichlorohydrin (ECH) was formed.
The ECH was distilled from the reactor and recombined with the remaining
dichloropropanol stream before final hydrolysis to glycerin.
Another problem that was encountered in this process was the formation of
chloroethers as a byproduct during the hydrochlorination of allyl chloride.
The only way to avoid the formation of chloroethers was to use dilute solu-
tions. The advantages of forming ECH, which could be easily distilled from
water and byproducts, as an Intermediate in glycerin production was noted by
71
-------
Olin Mathieson Chemical Corporation (Thomas, 1958). Olin Mathieson (Thomas,
1958) patented the idea of subjecting the crude dichloropropanol solution to
distillation to obtain about 5 to 15% dichloropropanol/water azeotrope (free
of chloroethers) and using the undistilled aqueous fraction to generate ECH.
As in the Shell Development patent (Tymstra, 1952), the ECH was recombined
with the distilled dichloropropanol before hydrolysis to glycerin. The trends
in manufacture of glycerin, thus, were to convert chloropropanols to ECH as a
convenient method of removing byproducts and minimizing water in the final
crude glycerin product. The current process is discussed in Section 5.2.2.
The first epoxy resins were developed in Germany in the late 1930s
(Kirk-Othmer, 1980a). In the late 1940s, a series of US patents were assigned
to the large US paint manufacturer Devoe and Raynolds. About this time, shell
Development was looking for new markets for ECH, which they were isolating
during glycerin manufacture (Jones and Chandy, 1974). Thus, ECH changed from
being Just an intermediate for glycerin into an important commercial chemical
on its own. ECH-epoxy resins are discussed in Section 5.2.1.
In the late 1950s, Hercules, Inc. patented polyether elastomers made from
ECH (Vandenberg, 1983). These elastomers are discussed in Section 5.2.3.
Hercules also found use for ECH in manufacture of wet-strength resins from
aminopolyamides in the late 1950s (Kirk-Othmer, 1981a). These compounds are
discussed in Section 5.2.4.
In the mean time, other methods of manufacturing synthetic glycerin were
developed (see Section 4.3) and the demand for synthetic glycerin has recently
declined. Even though other synthetic glycerin processes have been forced out
of the market, the demand for ECH for glycerin is only a small part of the
overall demand for ECH. Thus, ECH was once produced incidental to synthetic
glycerin, but now synthetic glycerin is produced incidental to ECH.
5.1 Manufacture of Epichlorohydrin
Manufacture of ECH has historically been tied to manufacture of glycerin
-------
(Tymstra, 1952). Moreover, since the same companies make allyl chloride from
propylene, the complete propylene to glycerin process is tied together
(Lowenheim and Moran, 1975; Chem. Eng. Progress. 1948).
5.1.1 Process Chemistry
The first reaction of interest is the chlorination of propene (propylene)
to yield allyl chloride (Fairbairn et al., 1947; Groggins, 1963). chlorine
can react with propene by addition to the double bond to yield 1,2-dichloro-
propane or substitution for the allylic hydrogen to yield allyl chloride. The
addition reaction could involve an electrophilic mechanism but it and the
substitution reaction both probably involve free radicals since the industrial
reaction is normally conducted at high temperature in the gas phase, under
these conditions chlorine (C12) undergoes homolysis to yield free radical
chlorine atoms which add to double bonds or abstract hydrogen. The total
concentration of reactants and their relative ratios affect the product ratios.
In Figure 5.1.1A we show the principal reactions expected in situations
where the total pressure of gaseous reactants is moderate and the ratio of
chlorine to propene is such that propyl radicals have similar probabilities of
reacting with C12 or propene (Pilorez, 1962; Goldfarb et al., 1980,
Sittenfield et al., 1980).
The most favored reaction is abstraction of the allyl hydrogen which
leads to formation of allyl chloride. As the concentration of allyl chloride
builds up, it reacts with chlorine radicals. A variety of reactions leading
to "heavy" (high boiling) byproducts are not shown in Figure 5.1.1A. These
products result from coupling of the propyl radicals with one another and
addition of these radicals to propene to form chloro-hexanes, -hexenes, etc.
Also at higher temperatures (e.g., 600°C) benzene (C6H6) starts to become
an important byproduct. Benzene probably comes from the propene coupling
products by elimination of HC1 and ring closure. The product ratios achieved
are summarized in Figure 5.1.IB (Fairbairn et al., 1947). Under normal
73
-------
500°C
CI'Free Radical
Propene
Addition
Addition
H Abstraction
CICHj—CH—CH,
Propene / \Clj
/ \
Cl
'CH2— CH — CH,
Cl
I
CH2=CH-CH2-
Propene
Ici2
CICHrCHrCH, CICH2-CH-CH3
l-Chloropropane 1,2-Dichloropropane
Cl
CH,-CH = C -4-
Cl
I
CHj-CH-CH, CH2=CH-CH2CI
2-Chloropropane Allyl Chloride
H Abstraction
CH2=CH-CHCI
Id,
H
CICHj— CH=CHCI
cis-and trans- 1, 3-Dichloropropene
CH2=CH-CHCI2
3. 3-Dichloropropene
Cl
I
CICH2-CH-CH2CI
1,2,3-Trichloropropane
Cl'
CICH—CH-CH2CI
Propene
CICH2—CH2-CH2CI
1.3-Dichloropropane
Figure 5.1.LA. Some significant free radical reactions
involving propene and chlorine.
74
-------
ioo rr
450
500 550
Reoction Temperature , °C
600
Figure 5.1.1.B
Effect of reactant ratio and temperature on products from
chlorination of propene. (Note that propene is present in 3
to 4 times the concentration of chlorine.) This graph shows
the optimum condition for manufacture of allyl chloride and
relative amounts of byproducts and products. Source:
Fairbairn et al. (194"7).
75
-------
operating conditions 1,2-dichloropropane and 1,3-dichloropropene are the
principal byproducts accounting for about 15% of the propene consumed
(Lowenheim and Moran, 1975). They are isolated and used as a soil fumigant
(Telone*, Dowfume N*).
After a series of distillations allyl chloride (b.p. 45°C, yield 80%,
Lowenheim and Moran, 1975) with small amounts of byproducts is isolated and
passed on to manufacture of epichlorohydrin.
The formation of epichlorohydrin (ECH) involves two steps. The first is
reaction with hypochlorite to yield a mixture of l,3-dichloro-2-propanol and
2,3-dichloro-l-propanol with 1,2,3-trichloropropane, chloroether and allyl
alcohol byproducts (Figure 5.1.1C). This is an electrophilic addition to the
double bond and it is conducted in an aqueous solution. According to Thomas
(1958), the final concentration of dichloropropanols (dichlorohydrins) in the
aqueous solution must be kept below 5% by weight to avoid excessive formation
of chloroethers. This requires that fairly dilute solutions be used. Forma-
tion of allyl alcohol from allyl chloride results in a series of byproducts
analogous to those shown in Figure 5.1.1C in which a chlorine is replaced by a
hydroxyl group. For example, reaction of allyl alcohol with hypochlorite
yields dihydroxychloropropanes (monochlorohydrins).
The second step involves ring closure of the dichlorohydrin
intermediates which is catalyzed by base. Santodonato et al. (1980) estimated
that the rate constant for epoxide formation from dichloropropanol at ambient
temperature can be calculated from
1C = 1.3 X 10~6 s"1 + 3.3 X 10~2 M^'s"1 [~OH].
Both of the dichloropropanol isomers yield epichlorohydrin. The ECH is
usually distilled from the reaction mixture to avoid subsequent hydrolysis to
monochlorohydrin.
O OH OH
CH2-CH-CH2CI -^ ^ CH2—CH —CH2CI
76
-------
OH
CIOH +
CH,=CH-CH2CI
.OH
, = CH-CH2OH
OH
CICH2-CH-CH2CI
1,3-Dichloro-2-propanol
CH2—CH-CH2CI
Unstable Intermediate
Cl
HOCHj-CH-CHjCI
2,3-Dichloro-l-propanol
CICHj-CH-CH2CI
1,2.3-Trichloropropane
CICH, CH,CI CICH,
CH-O-CH -f
CICH, SCH2CI
CHCI — CH2CI
CH-O-CH,
CICH
Chloroethers
Figure 5.1.1C. Reaction of ally! chloride with
hypochlon'te.
77
-------
The eplchlorohydrin azeotrope (b.p. 86°C, 75% BCH; Lichtenwalter and
Riesser, 1964) boils near the dichloropropanol azeotrope (b.p. 99°C, 23%
dichloropropanol, Thomas, 1958) and crude ECH contains dichloropropanols.
This material is purified by distillation to obtain 98% pure ECH (Lowenheim
and Moran, 1975).
5.1.2 Process Engineering
The process flow for the manufacture of allyl chloride is given in
Figure 5.1.2A (Pilorez, 1962). Wet propylene from storage is chilled by
passage through a bayonet type cooler immersed in dry propylene. The chilling
causes condensation of water which is subsequently removed in a coalescer.
The separated water is drawn off periodically. The propylene then passes
through a dryer packed with activated alumina where residual water is
removed. The dried propylene then flows to the dry propylene storage tank.
The propylene is vaporized in the dry storage tank providing
refrigeration for chilling the wet propylene feed. The dry, gaseous propylene
flows through a heater prior to mixing with gaseous chlorine and entering the
reactor. Normally the feed will contain about 4 moles of propylene per mole
of chlorine. The reaction temperature is maintained at between 500 and 510°C
and the pressure in the reactor is about 1 atmosphere gauge pressure.
Residence time is a few seconds. It is important to keep residence time short
to minimize the formation of side products (Fairbairn et al., 1947).
Because carbonaceous material accumulates in the reactor, it is
necessary to clean the reactor about once every two weeks. Therefore two
reactors are commonly provided so that one is in operation while the other is
being cleaned.
The reaction product is cooled rapidly and fed directly to a
prefractionator where excess propylene and byproduct hydrogen chloride is
separated as an overhead product from the organic chlorides. Liquid
propylene, cooled to -40°C by self-vaporization in a propylene flash drum, is
78
-------
VO
CD
C5 O
CAUSTIC SCRUBBER IICI ABSDRbKR
LI.)llt Hilda
TANK
(All
Hot Water Ham Hater
Inlat Outlet
LIII/IHINt VAI1IHIKKH
¥5.
PRKPRACTIONATOH DISTILLATION
COLUMN HO. 1
Allyl
Chloride
To Storaqa
Heavy
Enda
DISTILLATION
COLUMN HO. 2
Figure 5.1.2A Chlorinatlon Process for the Manufacture
of Allyl Chloride from Propylene
-------
used as reflux in the prefractionator and to cool the reaction products and to
scavenge unreacted chlorine.
The propylene and hydrogen chloride mixture overhead from the pre-
fractionator flows through an absorber where commercial strength hydrochloric
acid is produced. Additional liquid propylene is used to remove the heat of
absorption in this process and also to extract any residual organic
chlorides. The propylene leaving the absorber is scrubbed with caustic to
remove residual hydrogen chloride, passes through a liquid knockout pot to
remove entrained water before being compressed, liquified, and returned to wet
propylene storage. Gaseous propylene (generated in the propylene flash drum
and during regeneration of the dryers) is also recycled through the compressor
to wet propylene storage.
The organic chlorides from the bottom of the prefractionator have the
following approximate composition:
Compound %
mono chloropropenes 80 - 85
allyl chloride.
dichloropropenes 10 - 15
trichloropropanes 5
and propenes
tetrachloropropanes
and propenes
teloraers
The organic chlorides are separated by fractional distillation in two
columns. In the first, light ends such as 2-chloropropene, and very small
amounts of chloropropanes are removed overhead (see boiling point data in
Table 5.1.2A).
The bottoms from the first column are fractionated in the second column
where allyl chloride of 97% purity is obtained. The 3% impurities are trans-1-
chloropropene and di-chloropropenes such as 1,2-dichloropropene and perhaps
traces of trichloropropanes.
80
-------
Table 5.1.2A. Boiling Point Data
Compound Boiling Point (°C)
2-chloropropene 22.65
cis-1-chloropropene 32.8
trans-1-chloropropene 37.4
allyl chloride 44.6
1,2-dichloro-l-propene 76.8
1,2,2-trichloropropane 122
1,1,3-trichloropropane 147
1,1,2,3-tetrachloropropane 156.85
1,1,2,3-tetrachloropropane 180
The still bottoms would contain some allyl chloride together with
substantially all the heavier chlorinated hydrocarbons formed in the reaction.
*•**-.—
A typical process flow diagram for conversion of allyl chloride to ECH
based on Lowenheim and Noran (1975) and other sources cited in this section is
shown in Figure 5.1.2B. Allyl chloride is fed continuously into a reactor
containing a solution of hypochlorous acid at 30-40°C. Hypochlorous acid is
formed in a counter-current absorber column by contacting chlorine and water.
The chlorinatlon reactor effluent is fed to a separator; the upper (aqueous)
ayer is recycled to the chlorine absorber; then is fed to a second agitated
reactor.
In the second reactor, trichloropropane is added to form a two-phase
system in which the chlorohydrins are efficiently converted to ECH by reaction
with lime (CaO) slurry or dilute sodium hydroxide solution. The effluent from
the second reactor is steam stripped to distill ECH as the water azeotrope.
The crude product contains water and small amounts of dlchloropropanols
(Lowenheim and Noran, 1975).
According to Saletan et al. (1977), the organic byproduct distillation
bottoms from this process (waste stream 3B, Figure 5.1.2.B) contain the
following components (weight %):
81
-------
WATER
CO
ro
IIYI'OCIILOROUS ACID RliCYCLK
AQUEOUS PHASE
1IYPOCHLOROUS ACID FEED
^->
2
ALLVL
CHLORIDE'
CIILORINATION
REACTOR
^ '^—^••^
CRUDE CIILOROYDRIN
SEPARATOR
I OIVIAMIC PIIASE
Na Oil Ci<
HYDROXIDE
AtlIC PIIASE
„
^1 1
DEIIYDROCIILORINATIOII
TRICIILOROPROPAtlE
(SOLVENT)
CRUDE
EPICI1LOROIIYDRIN
+ Na OR Ca CHLORIDE
PURIFICATION COLUMNS
WASTE STREAM G
Figure 5.1.2B. Epichlorohydrin from allyl chloride via
dehydrochlorination of dichlorohydrins.
-------
1,2,3-Trichloropropane 51%
2,3-Dlchloro-l-propanol 19%
1,3-Dichloro-2-propanol 7%
Chlorodihydroxypropane 11%
Epichlorohydrin 1%
The Chlorodihydroxypropane content can be up to 45% and ECH can be up to 10%.
According to Pervier et al. (1974, cited in Santodonato et al., 1980), the tri-
chloropropane waste stream was stored. It is likely that it has been used to
recover trichloropropane as a specialty chemical and disposed of as a hazard-
ous waste. More recently, Saletan et al. (1977) proposed using this organic
phase as a solvent for ECH in the production of glycerin by hydrolysis in a
two-phase system. In the Saletan method, the excess water from manufacture of
dichloropropanol is separated by preparing ECH and collecting the organic
bottoms, then the ECH and organic bottoms are fed into the glycerin process
and most of the components of the organic bottoms except the 1,2,3-trichloro-
propane are converted to glycerin. Thus, more product (glycerin) is obtained
and the volume of the trichloropropane waste/byproduct is minimized.
The crude ECH-water azeotrope separates into two phases and the aqueous
phase is sent to a stripper to remove volatile organics. The remaining water
becomes waste stream 5 in Figure 5.1.2B. The organic ECH phase is sent to a
stripper where it is dehydrated and the water that is removed as an overhead
stream becomes waste stream 4 in Figure 5.1.2B. These aqueous waste streams
are likely to contain allyl alcohol and dichloropropanols.
The dehydrated organic ECH layer flows to a series of distillation
columns where allyl chloride and byproducts are separated. The waste streams
from manufacture of ECH from allyl chloride are listed in Table 5.1.2B. The
composition and production rates are based on engineering estimates. The
yield of pure ECH based on allyl chloride is 85 to 90%. Halasa (1976) has
reported the composition of several samples of ECH from various sources. The
results for ECH prepared from propene are listed in Table 5.1.2C.
83
-------
Table 5.1.2B. Waste Streams for Epichlorohydrin Manufacture3
Waste
Stream Type
1 Tail Gas Absorber
vent-Gas to Air
2 Reactor Vent-Gas to Air
3 waste water
4 Waste Water
5 Waste Water
6 Still Bottoms
Chemical
Compounds
chlorine
hydrogen chloride
allyl chloride
allyl chloride
chlorine
trlchloropropane
hydrogen chloride
eplchlorohydrin
calcium chloride
chlorohydrins
allyl alcohol
glycerine
dichlorohydrins
allyl alcohol
dichlorohydrins
allyl alcohol
trlchloropropane
chloroethers
dichlorohydrins
Amount Ib/lb
Ep ich lor ohyd r in
0.0000005
0.0000005
0.002
0.002
0.0000005
0.0005
0.0000005
0.0015
0.598
0.003
trace
0.12
0.004
trace
0.003
trace
0.0371
0.0074
0.0047
aThese waste streams correspond to Figure 5.1.2B and (represent refined ECH?V- '
Crude ECH for glycerin manufacture would be the same except fdr~waste-stream '
"6" which would be carried along as part of the ECH.
84
-------
Table 5.1.2C. Composition of Epichlorohydrin from various sources1
Compound
Percent Composition
Epichlorohydrin (ECH)
Allyl chloride
Chloroform
2,3-Dichloro-l-
propene
1,2, 3^Tr ichloropropane
Dich loropropano 1 s
"Zwiazky nieziden-
tyfikowane"
ZSSR
98.4
0.037
0.018
0.862
0.398
0.225
-
Solvav
98.85
-
-
0.246
0.112
0.237
0.57
Shell
>98.
0.012
-
0.312
0.26
0.218
-
This table is based on a partial translation of an article in an eastern
European language.
Source: Halasa (1976).
5.1.3 Alternate Process for Manufacture of Epichlorohydrin
Although it is unlikely that any process can be cheaper than the current
approach used to make ECH, it is interesting that Interox Chemicals Ltd.
(London) has patented a process for continuous epoxidation of allyl chloride
with perpropionic acid (Hildon and Greenhalgh, 1979).
5.2 Processing Methods for Epichlorohydrin
5.2.1 Manufacture of Epoxy Resins from Epichlorohydrin
There are several types of epoxy resins.
85
-------
The resins can be grouped as follows (Kirk-Othmer, 1980a):
o liquid, unmodified epoxy resins are almost pure diglycidyl ether of
bisphenol A (DGEBPA) and are used in coatings, castings, tooling,
flooring and reinforced pipe.
o liquid, modified epoxy resins are,usually small to moderate
ollgomers of DGEBPA diluted with various glycidyl ethers or esters
and are used in coatings, Impregnation and flooring.
o solid epoxy resins are usually moderate to high molecular weight
oligomers of DGEBPA and are used in fiberglass sizing and various
powder coating systems.
o solution of epoxy resins are usually moderate to high oligomers of
DGEBPA dissolved in xylene, methyl isobutyl ketone, toluene or
brominated acetone (55 to 80% solids) and are used as coatings and
for printed circuited boards.
o specialty epoxy resins include (1) epoxy-phenol novolacs and
epoxy-cresol novolacs used for laboratory bench tops, adhesives and
various types of moldings; (2) polyfunctional epoxldes used in the
aerospace industry; and (3) cycloaliphatic epoxies used for
electrical casting.
The most important resins are based on bisphenol A and the diglycidyl
ether of bisphenol A. The product has the general formula
CHt-CH-CH,-
O-CH,-CH-CH,-
O-CHj-CH-CH,
86
-------
and can be identified by two CAS numbers both of which are listed in the TSCA
Inventory. The CAS No. 25068-38-6 is defined as the epichlorohydrin polymer
with bisphenol A. This definition seems to imply a one-step synthesis of the
polymer from the starting materials. This appears to include epoxy resins
produced by the "Taffy Process". The CAS No. 25036-25-3 is defined as the
polymer of the diglycidyl ether of bisphenol A (CAS No. 1675-54-3) with
bisphenol A. This polymer appears to be produced in two steps from ECH and
bisphenol A by the "Advancement Process".
These two processes are discussed below.
5.2.1.1 The Advancement Process
The advancement process for manufacture of bisphenol A epoxy resins
(Figure 5.2.1.1A) seems to be more versatile and yield more consistent
products than the taffy process. The advancement process can be used to
produce resins with a wide variety of average n-values (0.1 to 16.0) and
physical property data is summarized below (Kirk-Othmer, 1980a). However, it
should be noted that the actual polymers have only even n-values (n=o,
2.4,6...). This is because a diphenol is being added to a diglycidyl ether
(Kirk-Othmer, 1980a).
Properties of Commercial Epoxv Resins Made by the Advancement Process
Average n value
0.1
0.3
0.6
2.2
5.5
14.4
16.0
EPOXY equiv wt
185
210
255
487
950
2250
3250
mp(Durran's),°C
liquid
liquid
liquid
65-75
95-105
125-135
145-155
Approx mol wt
360-380
390-450
360-560
805-1100
1750-2050
4000-5000
5000-8000
The pure diglycidyl ether of bisphenol A (n = 0.0) melts at 43°C (Kirk-Othmer,
1980a).
87
-------
o
CI-CH2-CH-SCH2 -|- HO
base
OH
i
CICH2-HC-CH2-0
OH
I
0-CH2-CH-CH2CI
dichlorohydrin ether of bisphenol A
CAS No. 4809-35-2
base
CH2—CH —CH2-0
0-CH2-CH-CH2
diglycidyl ether of bisphenol A
CAS No. 1675-54-3
Advancement Process
^ diol (HOROH)
CHj-CH-CHj-
OH
0-R-O— CH,-CH-CH2-
0-R-O-CHj-CH-CHj
n = 0, 2. 4, 6,
Figure 5.2.1.1A. The advancement process for making epoxy resins
of Bisphenol A. Note: HOROH represents bisphenol A.
88
-------
The first step in the advancement process is manufacture of the
diglycidyl ether of bisphenol A (DGEBPA, CAS No. 1675-54-3).
o
\
CH2-CH-CH2-0-(( ))-C-(( )>-O-CH2-CH-CH2
The commercial process used to make DGEBPA is probably similar to the method
patented by Shell Development in 1958 (Jones and Chandy, 1974).
The reaction is carried out in a vessel fitted with a heater, stirrer,
thermometer and distilling head. The distilling head is equipped with a
liquid separator which allows the lower layer to be returned to the reaction
mixture. The vessel is charged with a solution of bisphenol A in ECH (10
moles of ECH per mole of bisphenol A).
The reaction mixture is heated to about 100°C (ECH boils at 116°C at 760
mmHg) and maintained at that temperature during addition of a 40% aqueous
solution of sodium hydroxide. A total of 1.90 moles of sodium hydroxide per
mole of bisphenol A is added. The water introduced with the caustic distills
as an azeotrope with ECH (75% ECH, 25% H2O, bp 86°C; Lichtenwalter and
Riesser, 1964). The azeotrope condenses and separates into two layers. The
lower layer is ECH containing about 1.5% HO and the upper layer is water
containing about 6.6% ECH (Dow, 1980). The lower layer is returned to the
reaction mixture. The addition of the aqueous caustic solution is kept at a
rate such that the water is removed and does not build up in the reaction
mixture above the 1.5% level. The addition takes about 2 h.
When all the caustic has been added, the bulk of excess ECH is distilled
and the reaction mixture is heated to 160°C at 1 mmHg to remove residual ECH.
At this point, the reaction mixture consists mainly of the diglycidyl ether of
bisphenol A (mp 43°C) and sodium chloride (salt).
89
-------
Jones and Chandy (1974) describe two methods of isolation of pure DGEBPA
from the reaction mixture. In one procedure, methyl isobutyl ketone and water
are added and two phases form. The aqueous salt solution is removed and the
organic phase is contacted with a solution of aqueous base (5% NaOH) to
complete the epoxidation of the halohydrin intermediate. The organic phase is
again separated and washed with aqueous sodium dlhydrogen phosphate. Finally,
the organic phase is distilled up to a temperature of 160°C at atmospheric
pressure and then the pressure is reduced to 1 mmHg to remove the solvent.
The product from this isolation process is DGEBPA in the form of a pale yellow
liquid containing 0.25% chlorine and 0.521 epoxy equivalents per 100 g and a
molecular weight of 355. Hagnauer (1979) recrystallized DGEBPA from a
commercial product and purified the compound to a chlorine content of 0.051%
and an average molecular weight of 339. The second method of isolating DGEBPA
described by Jones and Chandy (1974) involves filtering the hot reaction
mixture and washing the Nad filter cake with ispropyl alcohol to recover the
product. The isopropyl alcohol is distilled from the filter cake wash and the
DGEBPA is mixed with the portion that came through the filter. No data are
available on the product from this isolation process.
Once relatively pure DGEBPA has been isolated, a variety of products can
be obtained by the advancement process. For example, the TSCA Inventory lists
these polymers of DGEBPA (CAS No. 1675-54-3):
Diol reacted with DGEBPA Bpoxv Resin CAS No.
bisphenol A 25036-25-3
tetrabromobisphenol A 31942-06-0
The TSCA Inventory also lists the polymer of the diglycidyl ether of tetra-
bromobisphenol A with tetrabromobisphenol A (polymer CAS No. 68928-70-1).
5.2.1.2 The Taffy Process
The taffy process for manufacturing epoxy resin is employed to make
resins with n=l to 4 (Kirk-Othmer, 1980a). The polymerization process
involves
90
-------
reacting similar amounts of epichlorohydrin, bisphenol A and base. The crude
product is a highly viscous emulsion of salt water and resin. The product is
Isolated by separating the phases and washing the taffy resin with water
(Jones and Chandy, 1974; Kirk-Othmer, 1980a). Kirk-Othmer (1980a> gives the
following data that indicate the nature of the product obtained with various
ratios of epichlorohydrin to bisphenol A in the taffy process (Figure
5.2.1.2A).
Mole ratio epichlorohydrin-bisphenol A Epoxv equiv wt
2.6 249
2.15 345
1.57 516
1.4 582
1.33 730
1.25 862
1.2 1180
5.2.1.3 Engineering Considerations in Epoxy Resin Manufacture
The plants used for manufacturing bisphenol A epoxy resins by the
advancement process and taffy process are probably similar. The main
differences are associated with the initial ratio of reactants (10 moles of
ECH/mole bisphenol A in the advancement process versus 2.6 to 1.2 moles
ECH/mole bisphenol A in the taffy process> and method of isolating the
product. Here we will outline a typical taffy process plant and identify its
waste streams and vents (Figure 5.2.1.3A). The process described here is
based on a plant designed by M. Slttenfleld for a chemical company.
Bisphenol and an excess of ECH are charged into the reactor. An excess
of sodium hydroxide is added as a 50% aqueous solution over a period of about
3 h while the reactor is maintained at about 110°C. Water and ECH distill as
an azeotrope that separates into a dense ECH phase and light water phase. The
ECH phase (containing about 1.5% H2O) is returned to the reactor. Upon
completion of the reaction, the excess ECH is vacuum stripped at 50 mmHg and a
maximum temperature of 150°C.
91
-------
Cl—CH2—CH—XCH2 —|—
HO
CH,
I
C
OH
CH
chlorohvdrin intermediates
CH,—CH —
OH
I
O - R - 0 — CH2— CH — C H2-
O— R — O - CH2— CH — CH,
-I -n.
n = 0, 1, 2, 3, 4, ....
Figure 5.2.1.2A. Process Chemistry of Taffy Method of
Forming Epoxy Resins.
92
-------
to
OJ
m WASTE wflltn
jL
i
i
HuOII UASII
jJ
1
%
{_
I'RUUUCT
Figure 5.2.1.3A. Typical epoxy resin manufacturing plant.
-------
The reaction product consists of the epoxy resin (liquid or solid
depending upon Initial ratio of ECH to bisphenol A) and sodium chloride salt.
The mixture is cooled to 90°C and a solvent (usually toluene) is mixed with
the reaction product. The mixture is passed to a centrifuge to separate the
salt. The epoxy resin solution from the centrifuge is clarified by filtration
and then vacuum stripped at about 70 mmHg and 150°C to remove toluene and
residual ECH. If desired, the epoxy resin solution can be washed with sodium
hydroxide to reduce ECH residues.
Much of the plant operation is concerned with recovery of solvents and
reactants and disposal of wastes.
• The azeotropic aqueous phase containing about 1.5% ECH from the
reactor is stripped and the ECH mixed with ECH recovered from the
reactor for recycle. The aqueous waste stream can contain up to
about 0.3% ECH.
• There is a vent from the reactor vacuum pump that produces
atmospheric discharge of ECH.
• There are vents on the feed tank and surge tank for the ECH recovery
column.
There is a centrifuge vapor vent and a vent on the salt disposal
unit.
The salt Itself is a major solid waste.
• The filter cake from the clarifier is a solid waste.
• There is a vent on the toluene stripper vacuum pump.
• The toluene stripper wash water is a liquid waste.
The compositions and production volumes of the liquid and solid waste streams
are described in Table 5.2.1.3A.
5.2.1.4 Manufacture of Epoxy Resins, Reactive Diluents and Related
Compounds That Are Not Based on Bisphenol A.
Glycidvl Ethers
Epoxy resins can be prepared from ECH and various diols other than
94
-------
Table 5.2.1.3A. Solid and Liquid Waste Streams from Manufacture of Blsphenol A
Epoxy_Resins.
Waste Stream
Component
Ib/lb of resin product
Epichlorohydrin stripping
column bottoms
salt byproduct waste
Filter cake from clarlfier
water
ECH
sodium chloride
Toluene
ECH
Resin
Sodium hydroxide
Filter aid
Toluene
Resin
ECH
0.36
0.0011
0.35
0.35
0.00068
0.0106
0.0113
0.00163
0.00326
0.00326
neglibile
Toluene stripper wash water
Sodium hydroxide
(variable, no data
available)
Source: H. Sittenfield, private files.
95
-------
bisphenol A. The public TSCA Inventory includes epoxy resins based on
aliphatic diols (31921-70-7, 25038-04-4, etc), polyether diols (39443-66-8,
etc.) and phenol-formaldehyde resins (novolac, 29690-82-2, etc). Aryl
glycidyl ethers are probably prepared by base-catalyzed addition of ECH
followed by epoxIdation of the chlorohydrin with alkali (see 5.2.1.1). Alkyl
glycidyl ethers are probably prepared by acid-catalyzed addition of ECH to the
alcohol followed by epoxidatlon of the chlorohydrin with alkali (see 5.2.7).
Glycidyl Esters
Glycidyl esters are more difficult to prepare than glycidyl ethers.
Dukes and Welch (1975) discuss the processes for manufacturing glycidyl
esters. The methods include:
(1) reaction of glycidol with an acid chloride
(2) epoxidation of allyl esters
(3) reaction of ECH with carboxylic acid (catalytically) followed by
disproportionation of the resulting chlorohydrin ester with excess
ECH.
O OH o
H / / \
R-C-O-CH -CH-CHCl + CH - CH - CH Cl
O O
II / \
R-C-O-CH -CH - CH + dichloropropanol
(4) reaction of ECH with dry potassium salts of carboxylic acids.
(5) reaction of ECH with carboxylic acid (catalytically) followed by
dehydrochlorination of the chlorohydrin ester with alkali.
In a patent assigned to Celanese Coatings and Specialties, Dukes and Welch
(1975) describe a method similar to the last listed above. Their key
improvement seems to be careful control of temperature (at or below 200°F for
the first step and between 90°F and 130°F for the second step).
96
-------
Dukes and Welch (1975) describe a typical reaction as follows:
A reactor was charged with adipic acid (400 parts), ECH (2533 parts) and
tetraraethylammonium catalyst (8 parts). The mixture was agitated and heated
up to 175°F (80°C) where it was held for 90 minutes at which time all the acid
was completely esterified.
The reaction mixture was cooled to 105°F and the reactor was evacuated
to a pressure of 10 mmHg before .beginning the epoxidation. Aqueous 50% sodium
hydroxide solution (438 parts) was added over a period of 315 minutes at this
temperature. ECH-water azeotrope distilled during the addition and the ECH
layer that formed as the azeotrope condensed was returned to the reactor. At
the completion of the reaction, the vacuum was released and water (500 parts)
was added to the reactor to dissolve the byproduct salt. The brine layer was
allowed to separate and was drawn off.
To complete the epoxidation, the organic phase was returned to 100 to
110°F in the reactor at 10 mmHg. An additional 176 parts of 50% sodium
hydroxide solution was added during a period of 115 minutes and ECH that
distilled was returned to the reactor as described above. As in the first
phase of epoxidation, the byproduct salt was dissolved in 1,000 parts of water
and withdrawn from the reactor.
The excess ECH was removed from the product (diglycidyl ester of adipic
acid) by distillation at a pot temperature of 305°F (152°C) and 10 mmHg. The
yield of product was 540 parts (98%) with an epoxide equivalent weight of 144
(theoretical 129) and total chlorine content of 2.12%.
Dukes and Welch (1975) described similar reactions using isophthalic
acid, terephthalic acid, azalaic acid and dimer acids of linseed fatty acids.
They also mentioned other suitable acids including oxalic, sebacic, succinic,
pimetic, phthalic, trimellic and chlorendic.
97
-------
Non-Glvcidyl Bpoxides
ECH Is used to prepare glycidyl epoxy resins. However, there are some
commercial epoxldes that do not contain the glycidyl group. Most of these are
made by epoxldatlon oleflns. The process may Involve peracld epoxldations or
halohydrln epoxldations.
Reactive Diluents
Many of the non-blsphenol A epoxy compounds In commerce are reactive
diluents for epoxy resins. These compounds are usually simple glycidyl ethers
or esters or epoxy cycloaliphatics (Pilny and Mleziva, 1977).
5.2.1.5 Residues of Bpichlorohydrin in Epoxy Resins
Direct data on residues of ECH in epoxy resins has been relatively
difficult to find. While there have been studies of the gross composition of
epoxy resins (Hagnauer, 1979; Braun and Lee, 1976), data on ECH residues have
not been found. The only information on ECH residues Is product specifications
published by manufacturers. We have also not found any distinction between
the residues found in resins made by the advancement process and taffy process.
In Shell's Technical Bulletin SC:106-82 (Shell, 1982). the company notes
that epoxy resins and reactive diluents produced from ECH contain trace
amounts of three relatively volatile impurities:
- eplchlorohydrln
- phenyl glycidyl ether
- diglycldyl ether
Shell lists a number of its Epon resins that are sold under a release
specification that the residual ECH content cannot be greater than 5 ppm
(Table 5.2.1.5A). According to Shell (1982), it is more common for these
resins to have ECH residue levels of 1 to 2 ppm. Eponol resins contain lower
residue levels.
98
-------
Table 5.2.1.5A. Epon Resins with ECH content of 5 ppm, wt, max
Epon Resin
Epon Resin
825
826
828
829
830
834
836
1001 F
1002 P
1004 F
1007 F
1009 F
2002
2002-FC-5
2004
2014
2024
8280
Source: Shell (1982)
Obviously, solutions made by diluting these resins In an Inert solvent
will have even lower ECH levels. However, Shell (1982) stipulates that resins
with reactive diluents (e.g., phenyl glycldyl ether) are not covered by these
specifications. Some specialty resins and reactive diluents have
Substantially higher ECH residue levels. For example, the data In Table
5.2.1.5B was (gTeenedlfrom shell material safety data sheets. Chemische
\_ I
Fabriek Zairtboramel of the Netherlands makes n-butyl and 2-ethylhexyl glycldyl
ethers containing 25 ppm ECH residue (Parbe & Lack, 1982).
99
-------
Table 5.2.1.5B. Residues of ECH in Specialty Resins and Reactive Diluents
Tradename Chemical Family ECH level
Epon 871 flexible epoxy resin 1400 ppm
Epon 815 modified epoxy resin 15 ppm max
(contains 13.5% butyl
glycidyl ether)
100% butyl glycidyl ether ID ppm
Source: Shell Material Safety Data Sheets (1983).
Shell's ECH residue standard for their main line resins (Table 5.2.1.4B)
appears to be based on an evaluation of the ECH residue levels that will
produce vapor concentrations exceeding the OSHA standards. (The regulatory
limits for ECH exposure in the workplace are summarized in Table 6.0A.)
Through experimental work Shell determined the equilibrium concentration of
ECH vapor that can be achieved (i.e., the maximum ECH concentration that can
be achieved) in air in contact with epoxy resins at various temperatures. The
results are shown in Table 5.2.1.5C. Shell (1982) argues that a 5 ppm (wt/wt)
concentration of ECH in the bulk resin will not give rise to a vapor concentra-
tion above the OSHA limit (5 ppm, v/v) except at the maximum recommended
handling temperature (i.e., 200°F, 93°C). It should be noted that the
equilibrium concentrations are independent of the method of application of the
resin (pouring, spreading, spraying); but the rate at which the equilibrium
(i.e., maximum) air concentrations are reached will depend upon the surface
area of resin in contact with air.
These data appear to apply to uncured liquid resins. It should not be
assumed that the solubility of ECH in the cured solid resin is the same as in
the uncured liquid. If ECH is less soluble in the solid cured resin, it would
100
-------
tend to be forced out of the solid (into the air) during curing. The result
would be higher air levels of ECH than expected on the basis of Table
5.2.1.5C. The reaction of ECH residues with the curing agent is a mitigating
factor.
We asked the Dow^Chemical Company to comment on levels of residual ECH
in various products (Haramaker, 1983) and Dow responded with the data
summarized in Table 5.2.1.5D (Arnold, 1984b).
Table 5.2.1.5C ECH Vapor Concentrations above Epoxy Resins at various
Temperatures Under Static Equilibrium Conditions.
ECH levels in resin, ppm, wt. 10 5 1
Temperature, °C(°F)
27 (80)
49 (120)
0.6
2
ECH level in vapor,
0.3
1
ppra, v/v
0.06
0.2
Note: 140°F Recommended handling temperature
71 (160) 5 2.6 0.5
93 (200) 12 6 1.2
Note: 200°F Recommended maximum handling temperature
116 (240)
138 (280)
149 (300)
26
50
64
13
23
32
2.6
5.0
6.4
Source: Shell (1982).
101
-------
Table 5.2.1.5D. Levels of Epichlorohydrin Residues in Typical Epoxy Resins
and Reactive Diluents.
Epoxy Resin
Bisphenol A (DGEBPA)
(25068-38-6, 25036-25-3)
Aliphatic (31921-70-7, 25038-04-4, etc.)
Polyether (39443-66-8, etc.)
Epoxy Novolac (29690-82-2, etc.)
Glycidyl ethers (2426-08-6, etc.)
Glycidyl esters (106-90-1, 106-91-2, etc.)
ECH Residue (ppm)
5 max.
50 max.
10 max.
10 max.
10
1,000
Source: Arnold (19845).
5.2.1.6 Reduction of Residual Epichlorohydrin Levels in Epoxy Resins
As a result of concern about the health effects of ECH and other
volatile epoxy compounds like glycidyl ether, various methods have been
considered for reducing their levels in epoxy resins. Vacuum stripping and
washing with aqueous caustic solution have been used as routine methods for
reducing residues in bisphenol A epoxy resins. Bisphenol A epoxy resin is
relatively insensitive to heat and hydrolysis. Other types of epoxy resins
are more readily destroyed by heat and caustic treatment. Thus, Ciba-Geigy
Corporation (Sury, 1983) has patented a process for reducing ECH residues in
heat sensitive epoxy resins. The method also works for bisphenol A epoxy
resins and probably would work for other types of ECH derivatives.
The method involves heating the product in vacuo as it trickles through
a packed column against a counter current of inert gas (e.g., nitrogen). A
variety of factors (e.g., temperature, vacuum, resin flow rate, N2 flow
rate, length of column) can be varied to achieve the most economical stripping
with respect to achieving a desired final ECH residue level. Results that were
achieved using a laboratory-scale apparatus are presented in Table 5.2.1.6A.
102
-------
Table 5.2.1.6A. Epichlorohydrin Concentrations (ppra) vs. Number of Passes
Through Column.
Resins or
Product3
Temperature
"C
Ratio (g/g)
Na/Resin
(product)
Resin Rate
g/minute
Passes Through
Column
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
A
130
0.10
8.9
5176
1637
529
173
95
35
23
4
0
B
120
0.15
8.1
2882
1548
747
410
262
104
53
31
18
13
9
9
C
120
0.10
11.3
3500
1840
1270
940
515
522
381
285
240
167
93
90
58
42
30
17
5
D
120
0.1
6.3
2269
1025
502
325
250
63
79
50
40
21
31
aA is 2,2-bis(4-glycidyloxyphenyl)propane, ARALDITE 6010.
B is N,N-diglycidyl-5,5-pentamethylenehydantoin.
C is N,N,O-triglycidyl-p-aminophenol.
D is N,N,N',N'-tetraglycidyl-4,4'-methylenedianiline.
103
-------
Because a relatively small packed column (0.5 x 18 inches) was used the product
was repeatedly passed through (up to 16 times in one case). It is not clear
whether the starting ECH concentrations were typical of ECH residues in the
various resins or whether the ECH was "spiked" into the resin. However, no
mention of fortifying (spiking) the resins with ECH was mentioned by the
author. In addition to the materials listed in Table 5.2.1.5A, the author
also experimented with triglycidyl isocyanurate with similar results.
Under the conditions employed, no adverse changes in the resins were
noted. The epoxy value and chromatographic properties were unchanged but the
viscosity increased and hydrolyzable chlorine content decreased (Sury, 1983).
It seems likely that other approaches for stripping residual ECH from
products (including epoxy resin, elastomers and wet-strength resins) could be
employed successfully. The main factors preventing stripping of ECH are
probably viscosity of the product, low vapor pressure of ECH and affinity of
ECH for the product. These factors can be overcome by dissolving or melting
the product and exposing a large surface area, lowering the overhead pressure
(applying a vacuum), and introducing an Innocuous solvent with more affinity
for the product than ECH. We envision, for example, dissolving an ECH-con-
taminated product in dimethyl ether, methylene chloride, a freon or similar
solvent and passing it through a heated, packed column in which the solvent is
evaporated and entrains the residual ECH in the vapor.
5.2.1.7 Other Impurities in Epoxy Resins
There are potentially hazardous impurities in epoxy resins other than
ECH. Two of the most important are diglycidyl ether (DGE) and phenyl glycidyl
ether (PGE) (Shell, 1982). According to Shell, DGE has been found in random
samples of Epon resins at levels up to 31 ppm, but it rarely exceeds 5 ppra.
The concentration of PGE in undiluted bisphenol A-ECH Epon resins is typically
5 to 40 ppm with occasional findings as high as 2000 ppm. (Epon resins 1031
and 1030-B-80 have PGE at about 2% by weight as a reactive diluent.) Hagnauer
(1979) also suggests that glycidyl alcohol may be a common Impurity.
104
-------
Glycidyl alcohol and dlglycidyl ether are produced by base hydrolysis
and condensation of ECH. Phenyl glycldyl ether Is produced by reaction of ECH
with phenol impurity in the bisphenol A. Hagnauer (1979) mentioned that
phenol is usually present at less than 0.1 wt% in bisphenol A. Halasa (1976)
reported analyses of various bisphenol A samples with findings of 0.01 to
0.07% phenol. Hagnauer (1979) and Halasa (1976) also discuss other bisphenol
A impurities that effect the performance of the resin, but which are not
volatile enough to be a hazard.
5.2.2 Manufacture of Glycerin from Epichlorohydrin
5.2.2.1. Process Chemistry
Early processes for manufacturing glycerin from allyl chloride involved
(a) chlorinatlon of the allyl chloride to 1,2,3-trichloropropane or (b)
hydrolysis of allyl chloride to allyl alcohol followed by hydrochlorination
(chlorohydrination) to dihydroxychloropropanes (monochlorohydrins) followed in
each case by hydrolysis to glycerin (Tymstra. 1952). The method patented by
Shell Development (Tymstra, 1952) involves the hydrochlorination of allyl
chloride followed by hydrolysis of the dichlorohydrins to glycerin. This
process suffers from the fact that dilute solutions must be used because of
the low solubility of allyl chloride in water and because bis(dichloropropyl)
ethers are formed if the intermediate dichlorohydrins are allowed to build up
(Thomas and Dannels, 1958). This excess water and accompanying salts are
difficult to remove from the product glycerin.
Conversion of part or all of the dichlorohydrins to ECH which can be
readily distilled away from excess water, salt and bis(chloropropyl) ethers
became an efficient method of making the isolation of pure glycerin more
economical. The final reaction is a three-step hydrolysis of ECH as shown
below:
105
-------
0 OH OH
/\ -OH/HO | |
CH2-CH-CH2C1 ^ CH2-CH-CH2C1
OH OH OH 0
| | -OH/H 0 I / \
CH -CH-CH Cl ^- O
OH 0
1 /\
-OH/H20 ^
s
OH OH OH
m—TV—TV
Some polyglycerols can be formed by reactions among the intermediates. For
example,
9H 0 OH OH OH OH
I / \ . | | ||
CH2-CH-CH2 + glycerin ; ^ CH2-CH-CH2-O-CH2-CH-CH2
5.2.2.2 Process Engineering
Shell pioneered the propylene-allyl chloride-epichlorohydrin-glycerin
process. Discussions of the early developments are provided by Fairbairn et
al. (1947) and Chera. Eng. Progress (1948). This work culminated in a patent
by Tymstra (1952). The key engineering problem in manufacture of glycerin is
separation of glycerin from excess water, salt and impurities. Isolation of
ECH was mainly a method for reducing water in the crude glycerin (Tymstra,
1952). Literature descriptions of the actual final purification of glycerin
(Lowenheim and Moran, 1975; Petrol. Refiner, 1955) are vague. However, since
glycerin is very high boiling (182°c at 2 mntHg), virtually all the impurities
except polyglycerols and salt are removed in the light overhead streams.
A process flow diagram is provided in Figure 5.2.2.2A. Crude
epichlorohydrin is reacted with caustic soda at 157-180°C and 1.14 mPa (11.2
atm, 150 psig) in a stirred vessel for up to 30 minutes (minimum 10 min). The
crude diluted glycerin is neutralized with hydrochloric acid and concentrated
to about 80% glycerin in multiple-effect evaporators. The resultant sodium
106
-------
Crude
Epichloro-
hydrin
IDtNaOH
HC1
\/
G-l
1
Multiple
Effect
Evaporator
Centrifuge
^
G-3
1
Vacuum
Evaporator
Centrifuge
G-2
G-4
G-5
Fig. 5.2.2.2A
Glycerine From Epichlorohydrin
Source: Industrial Process Profiles
Lowenheim & Moran (1975) and
Private Files M. Sittenfield.
-------
Table 5.2.2.2A. Sununary Waste Streams
Total*
Estimated
Waste Designation kg waste/ Generation
Description Fig. 5.2.2.2A kg product3 Composition 106 kg/yr
water Condensate G-l
from multiple
effect
evaporators
Water Condensate G-3
from multiple
effect
evaporators
Solid sodium G-2
chloride
Solid sodium G-4
chloride
Toluene recovery G-5
still bottoms
Toluene recovery G-6
overhead
Overhead final G-7
purification G-7
col 'n
4.5 x 10 3 Glycerin
9.5 x 10~3 Glycerin
61.0 x 10~3 Misc. Impurities
431 x 10~3 Sodium chloride
82.5 x 10~3 Sodium chloride
n.d. Toluene and
heavy impurities
4.5 x 10~3 Toluene
0.95 x 10~3 Glycerin
1.55 x 10~3 Toluene
0.17
0.37
2.4
16.6
3.18
0.17
0.04
0.06
alnd Process Profiles, Chapter 6, EPA 600/2-77-023 (1977).
*Based upon estimated U.S. production glycerin from ECH at 85 x 106/lb/yr
(38.6 x 106 kg/yr).
108
-------
chloride-glycerin slurry is centrifuged to remove salt and then further
concentrated in vacuum multiple-effect evaporators to 98 to 99% glycerin.
Additional salt is removed by centrifugation. Color may be removed from the
glycerin by extraction with toluene at this stage. Finally, the product is
steam-vacuum distilled to produce 99+ % pure glycerin.
The waste streams from the process are summarized in Table 5.2.2.2A.
5.2.2.3 Residues of Epichlorohydrin in Glycerin
Dow (Arnold, 1984b) states that jio ECH residues were detected in their
synthetic glycerin (detection limit 1.5 ppm). This is not surprising con-
sidering the rate of base hydrolysis of ECH and the condition of manufacturing
glycerin.
According to Piringer (1980), the rate constant (k) for base hydrolysis
of ECH is given by
k = A exp (-E/RT)
where A = 1.8 x 10° M «s ,
E = 68,000 J/mole,
R = 4.18 x 1.99 J/mole deg,
and T is the absolute temperature (°K)
Under the condition of manufacturing glycerin, the minimum process temperature
is 157°C (sec. 5.2.2.2) this corresponds to 430°K. Thus,
k = 1.8 x 108 M~1«s~1
exp
k = 1.8 x 10° rT^s"1 x 5.54 x 10~9
k = 1.00
-68,000 J/mole
4.18 x 1.99 J/mole"|430 deg
deg
e_~H
109
-------
The solution Into which the ECH is mixed is probably at least 1.0 M in base.
Rate = k[base] [ECH]
= (1.0 M~I'S~1)(1.0 M) [ECH]
= 1.0 S [ECH]
The pseudo-first order rate constant for the reaction under these conditions
(157°C, 1 molar base) is 1.0 s . Thus, the pseudo-first order half-life is
tl/2 = ln 2 = 0.693 = 0.693 s
k 1.0 s-1
Since the minimum contact time is believed to be at least 10 minutes (600s),
it would be very conservative to estimate that, even with problems of mixing,
the minimum contact of ECH with the base solution could be 30 s. This is
equivalent to 43 half-lives. Thus, the concentration of ECH remaining in the
crude product should be no more than
ECH residue = original concentration = original concentration
(2)43 9 x 1012
If it is assumed that the original concentration is about 10 M, then
ECH residue = 10M = 1.1 x 10~12M
9x10^
= (92.5 g ECH/mole) (1.1 x IP"12 mole/L)
(1.26 x 1Q3 g glycerin/L)
= 8 x 10~14 g ECH/g glycerin
ECH residue = less than 1 part per trillion
i
i
i
It is clear from these calculations that if any ECH residues occur in I
crude glycerin it is probably because of poor mixing in the reactor rather
than resistance of ECH to hydrolysis. Because of the several high temperature
distillations that must be used to concentrate and purify crude glycerin
(Figure 5.2.2.2A), ECH residue expected in the final product would be even
less that the level calculated above.
110
-------
5.2.3 Manufacture of Epichlorohydrin Elastomers
In 1957, EJ Vandenberg of Hercules, Inc. discovered catalysts for
obtaining high polymers of epichlorohydrin (i.e., amorphous polyepichloro-
hydrin) (Vandenberg, 1983). Because Hercules was not a rubber company, there
was little initial Interest in marketing the material and some production
rights were licensed to B.P. Goodrich Chemical Company. In 1963, copolymers
of epichlorohydrin and ethylene oxide were prepared. Goodrich began
production of the copolymer in 1965 at its plant in Avon, OH under the
tradename Hydrin. The copolymer had a variety of desirable properties and
Hercules began its own production in 1966 under the tradename Herclor.
However, it was not until 1968 that Hercules began construction of a
commercial plant, which began operating in March 1970. Recently, Hercules and
Goodrich have each expanded their capacities to 24 million pounds per year
(Vandenberg, 1983).
The motivation for Vandenberg1s experimentation described above
(Vandenberg, 1983) seems to have been partly due to the expectation among
polymer chemist that poly(ethylene oxide)-type polyethers would have better
elastomeric behavior than the polyolefln materials available in the 1950s.
However, until Vandenberg1s discovery, only low-molecular-weight, liquid
polyethers had been obtained (Kirk-Othmer, 1979a).
The idealized structures of ECH homopolymer (abbreviated CO by ASTM) and
the ECH-ethylene oxide copolymer (abbreviated ECO) are shown below:
= TcH,-CH-O~l i CH,-CH-0-CH,-CH,-aj
L 2 | Jn L 2 | 2 2 jn
CH2C1 CH2C1
ECH Homopolymer ECH-Ethylene Oxide
(CAS No. 24969-06-0) Copolymer
(CAS No. 24969-10-6)
111
-------
It has been shown that the ECH horaopolyraer has more than 97% head-to-tail ECH
units as shown. Although the 1:1 ECH to ethylene oxide composition is
preferred for the copolymer, there appears to be irregularities in which
strings of ethylene oxide units occur. The end groups of the polymer chains
are normally -CH OH units (Vandenberg, 1967), but these may be crosslink
with the -CH Cl side chains during curing.
The properties of the polymers are summarized in Table 5.2.3A. the
homopolymer has good low temperature flexibility, and excellent resistance to
oils, but is not very rubbery (poor rebound). The copolymer has less
resistance to oils, but excellent low temperature flexibility and good
elasticity. Both polymer have good heat-aging, ozone, and flame resistance
(Kirk-Othmer, 1979a).
5.2.3.1. Process Chemistry
Much attention has been given to the development of the catalysts for
conducting these polymerizations (e.g., Vandenberg, 1983). The catalyst is
prepared by reacting a trialkylaluminum compound such as triisobutylaluminum
with less than a stoichiometric amount of water (0.6 moles of water per mole
of aluminum alkyl) to form a compound with an empirical formula R2A1OA1R2
where R is an alkyl group. Addition of acetylacetone (one mole per mole of
aluminum) to the product yields a more effective catalyst. The formula
usually given for this catalyst is shown below.
O —Al—O—Al—O
112
-------
Table 5.2.3A. Properties of vulcanized Epichlorohydrin Elastomers.
Property
Tensile strength (MPa)a
Ultimate elongation (%)
Shore A hardness
Low temperature
brittleness (T6°C)
Lupke rebound (%)
at 23°C
at 100°C
Volume change after Immersion 1
at 70 hours
in No. 3 oil at 150°C
in fuel A at 23°C
in fuel B at 23°C
in water at 23°C
ECH-Homopolymer
15.9
230
82
-18
26
75
[%)
4
0
8
0
ECH-EO Copolymer
15.0
320
74
-40
67
63
8
1
11
5
aTo convert MPa to psi, multiply by 145.
Source: Kirk-Othmer (1979a).
113
-------
Shlh et al. (1982) discussed preparation of similar Initiators and noted that
their catalysts preparations were not homogeneous. Moreover, more rapid
polymerization was achieved when some of the solid was Included In the
polymerizing mixture.
Both the homopolymer and copolymer are produced by solution polymeriza-
tion processes in benzene, toluene or methylene chloride solvent (Kirk-Othmer,
1979a). Bulk polymerization and use of aliphatic solvents have been
considered, but do not appear to be In commercial application. In the
commercial processes the catalysts and solvent are selected to give the
highest portion of amorphous polymer. The commercial products do not require
separation of crystalline polymer, but this can be achieved on a laboratory
scale by dissolving the amorphous polymer in acetone, In which the crystalline
form has lower solubility. Because ethylene oxide is more reactive with the
catalysts than ECH, an initial composition of 94% ECH and 6% ethylene oxide is
required to obtain the desired 1:1 copolymer. Molecular weight of the polymer
is controlled by use of a carbonium ion precursor.
Vandenberg (Kirk-Othmer, 1979a) notes that a phenolic antioxidant is
added to the polymer solution before solvent is removed. This antioxidant
appears to be B.F. Goodrich's "Good-rite 3125", which is a trifunctional
hindered phenol in finely divided crystalline form (Blast, 1978).
The ECH elastomers are vulcanized (crosslinked) by difunctional
nucleophilic reagents that react with the chloromethyl groups releasing HC1 as
a byproduct (Kirk-Othmer, 1979a). Crosslinking agents such as
CH,CI CH:-X
CH2CI
CH:CI
CH2CI
CH,
H,X . 1
P X -
1
. CH,
v-V°^X0^
CH2-X
+ 2 HCI
'
114
-------
hexamethylenedlamine, 2-mercaptoimidazoline and trlmethylthlourea have been
used. An acid acceptor (such as a stearate salt) must be used to absorb the
HC1. Fillers (such as carbon black) are used to increase the tensile strength
and plasticizers (such as di(n-octyl) phthalate) are used to improve low
temperature flexibility in compounded rubber (Kirk-Othmer, 1979a). Typical
vulcanization formulations are listed in Table 5.2.3.8,
5.2.3.2. Process Engineering
The current commercial plant processes have not been published, but
based on recent comments by Vandenberg (Kirk-Othmer, 1979a). they seem to vary
from the methods described in early patents (Vandenberg 1964a,b,c; 1965;
Robinson. 1962; Robinson and Willis, 1967). The current commercial plants
appear to be designed for continuous solution polymerization usually employing
aromatic hydrocarbon solvents (toluene). A simple process flow diagram is
shown in Figure 5.2.3A. Because ethylene oxide is about seven times more
reactive than ECH (Kirk-Othmer, 1979a) the initial monomer composition for
forming the 1:1 copolymer must be 96% ECH and 4% ethylene oxide. Thus, a
considerable amount of excess ECH must be recovered along with the solvent
when the copolymer is isolated. Steam stripping is used to remove traces of
solvent and ECH monomer from the crude elastomer. According to Vandenberg
(Kirk-Othmer, 1979a), proper selection of the solvent and catalyst allows
production of a polymer that is mainly amorphous so that separation of
crystalline polymer is not required in commercial processes.
Table 5.2.3B. Vulcanizate Formulations.
ECH ECH
Ingredient Homopolymer Ethylene oxide
(parts by wt.) (parts by wt.)
polymer
carbon black
stearic acid
red lead
nickel dibutyldithiocarbamate
2-mercaptoimidazoline (NA-22)
100
50
1.0
5.0
1.0
1.5
100
50
0.75
5.0
1.0
1.5
Source: Kirk-Othmer (1979a).
115
-------
Epichlorohydrin Ethylene Oxide Aluminum Alkyl
^ I r j, Water/Acetylacetone
Monomer
Mixing
Solvent
Catalyst
Preparatior
Solvent & Epichlorohydrin
Reactor
Phenolic Antioxidant
Steam
Water/Solvent/Monomer
Monomer
and
Solvent
Recovery
t
Steam
Stripping
Epichlorohydrin
Elastomer
4
Compounding
Figure 5.2.3A. Likely Epichlorohydrin Elastomer Process Based on
Description of Commercial Process by E.J. Vandenberg
(Kirk-Othmer, 1979).
-------
5.2.3.3. Residues of Epichlorohydrln in Elastomers
There is potential for significant residue of ECH monomer in the crude
ECH elastomers especially the copolymer, which must be prepared with a large
excess of ECH. Reaction of residual ECH with vulcanizing agents (i.e., nucleo-
philes) or stabilizer additives and adsorption of residual ECH by carbon black
filler are credited by Vandenberg (Kirk-Othmer, 1979a) with preventing
excessive ~~
airborne ECH concentration during storage and processing. The actual ECH
residue levels in the elastomers were not stated.
5.2.4. Epichlorohydrin-based Wet-Strength Resins
Natural polymers such as carbohydrate (cellulose/paper) and protein
(hair/wool) often are not highly crosslinked. When exposed to water, which
hydrates the hydrophllic polymer strands, the fibers can change position
(resulting in changes in the size or shape of the object they compose) or they
may become completely separated (Kirk-Othmer, 1981a; Britt, 1970). Thus,
wet-strength resins are used to form a stable polymeric web among the natural
fibers and the web is covalently linked to the natural fibers to give a
permanent organization to the natural fibers without changing their desirable
properties.
Wet-strength resins containing glycidyl groups or incipient glycidyl
groups (i.e., halohydrins) have been prepared by reacting epichlorohydrin with
various polymers containing amino groups (van Eenam, 1980; Kirk-Othmer,
1981a). The ECH wet-strength resins that have had the most commercial
importance are based on amino polyamides. Typical examples found in the TSCA
Inventory include the following:
Wet-strength resin
Amino polyamide modified by ECH CAS No.
N-(2-aminoethyl)-l,2-ethanediaraine
with hexanedioic acid 25212-19-5
117
-------
with pentanedloic acid
with methylenebutanedioic acid
N.N1-bis(2-arainoethyl)-l,2-ethanediamine
with hexanedioic acid
52470-29-8
52404-84-9
26568-79-6
Polyamine modified by ECH
N-raethyldiallylaraine polymer
N-(2-aminoethyl)-N'-[2-(2-amino-
ethyl)amino]ethyl-l,2-ethanediamine
N-(6-aminohexy1)-1,6-hexaned iamine
(hydrochloride salt)
Wet-strength resin
CAS No.
37890-28-1
26658-42-4
67953-56-4
68239-30-5)
The ECH-modified diethylenetriamine hexanedioic acid polymer (CAS No.
25212-19-5) is the most important compound in this group. Its major producer
is Pacific Resins & Chemicals, which produced 13 to 80 million pounds of the
^-r-esln~-in--19j[7__according to the non-confidential portion of the TSCA
Inventory. Other producers include Hercules, Inc. and Georgia-Pacific
Corporation. Diamond Shamrock and Monsantorwere manufacturers of the ,
\—*—
polyamine resins. Kirk-Othmer (1981a) mentions that use of byproduct still
bottoms from hexamethylenediamine production to make wet-strength resins.
Some of these resins appear to be in the TSCA Inventory (CAS No. 68784-97-4,
68958-56-4).
5.2.4.1 Manufacture of Wet-Strength Resins
The conventional method of forming wet-strength resins involves reacting
polyamines with ECH in alkaline solution and monitoring the viscosity of the
reaction mixture (Van Eenam, 1980). The initial reaction between the
polyamine and ECH forms ECH adducts of the type shown below:
HO-CH-CH,CI
118
-------
But some conversion of these Intermediates to glycidyl amines and quarternary
ammonium compounds occurs under the reaction conditions:
The glycidyl groups begin crosslinking the polyaraine resins forming bridges
like the one shown below:
As a result, the viscosity of the reaction mixture begins to rise and unless
acid is added to reduce the pH (and stop formation of glycidyl amine groups)
the mixture will form a gel, which precipitates. SulfurIc acid is used to
stop gel formation in commercial practice (Bales, 1977c). Conventional
wet-strength resins are prepared as acidified solutions that are reactivated
by adding base just before use. Guise and Smith (1982) have studied the
composition of Hercosett 125 (adipic acid-dlethylenetrlamlne-ECH, CAS No.
25212-19-5) and found it to have a number-average molecular weight of 2,100.
Monsanto (Van Eenam, 1980) patented a process for forming "perepiquat"
polymers. The pereplguats are based on polyamlnes containing only tertiary
amino groups. A typical polymer can be formed from dia1lylmethy1amine. The
polymer has the structure shown below:
' CH2 QH;
0
CH,
119
-------
Van Eenara (1980) lists a variety of other polymers and copolymers which
contain only tertiary amines and are suitable for forming perepiquats. In
each case, the perepiquats are formed by reacting the tertiary amine polymer
in a partially protonated cationic form with ECH at 20°C or below. Under
these conditions, almost all the araine groups are quaternized to yield
structures such as shown below:
ra
\ M S
£H,
-CH— CH2CI
OH
Because there are no free amine groups in the polymer, the polymer gels very
slowly after activation with base:
H3C
N
\
CH2—CH-CH2CI
OH
base
H3C
\
N
N
CH2-CH-CH2
V
gel
The perepiquat polymers readily crosslink cellulose when applied and cured at
elevated temperature.
Monsanto (Van Eenara, 1980) compared their perepiquat polymer with a
leading commercial ECH-aminopolyamide "S-2064" produced by Hercules, Inc. by
the conventional method. Both resin solutions (3 to 10% solids) were
activated by adding 7.0 meq of 25% aqueous sodium hydroxide per gram of resin
solid over a period of 15 seconds. The activated resin solutions were stirred
and diluted to 1.2% solids.
120
-------
The wet-strength resin solutions were added to a wood pulp slurry at a
rate of 5 kg solution/metric ton of pulp slurry. The slurry was allowed to
stand at room temperature for 10 minutes before It was formed into sheets and
dried at 96°C for 2 minutes. The pereplquat resins (which had longer gel
times than the conventional resin) produced stronger paper sheets. Similar
tests comparing the Monsanto products with other Hercules products (kymene 551
H and kymene 557 H (see Section 6.5)) gave similar results. Monsanto (Van
Eenara, 1980) seemed to be building an argument that the pereplquat resins
could be used at lower treatment levels than conventional resins to achieve
the same results.
5.2.4.2 Application of Wet-Strength Resins
The wet-strength resins are added at the "wet end" of paper machines
(Figure 5.2.4.2A). They are reactivated by adding base Just before or during
application to the pulp. According to Britt (1970) "The pH of the head box
stock system must be maintained at the proper level for the resin being used.
The flow of resin solution, In proportion to the quantity of fiber must be
closely controlled (in order to meet the wet tensile test required) without
using an excess of resin. The percent resin on basis of fiber varies
considerably, depending on the grade of paper and the wet strength
requirement. Normally the range Is from 0.5 to about 1.0% although for
special purposes It may go as high as 5%.
The paper at the reel normally has not received sufficient exposure to
heat to effect complete cure of resin. For test purposes, a paper sample is
heated at about 125°C for 3 to 5 min and then tested for wet tensile strength.
Natural aging will develop wet-strength In the product after a few days or
weeks. The relationship between the accelerated test and natural aging must
be determined experimentally for each mill and product."
5.2.4.3. Release of Eplchlorohydrln from Wet-Strength Resins
Wet-strength resins are prepared and used as aqueous solutions. Because
of the tendency of conventional resins to form gels, the conversion of ECH is
121
-------
ro
ro
fOU«0«INI[«
Figure 5.2.4.2A. Diagram of Fourdrinier paper machine.
Source: Riegel's Handbook of Industrial Chemistry.
-------
poor and the aqueous solutions probably have considerable amounts of free
ECH. The residual ECH hydrolyzes (see Section 2.3.1) with a half-life of
less than 150 hours in aqueous solution, but because of the gel problem, the
wet-strength resins are probably used before the ECH levels can greatly
dissipate.
It is important to note that sulfuric acid (and not hydrochloric acid)
is used to prevent gel formation in conventional wet-strength resins (Bates,
1977c). If hydrochloric acid were used, the excess ECH would be converted
to dichloropropanols which would be carried with the resin in aqueous
solution. When base is added to activate the resin, the dichloropropanols
would be converted to ECH in situ. The amount of ECH potentially introduced
by this route would be much greater than the expected levels of residual ECH.
5.2.5 Epichlorohydrin-Based Ion Exchange Resins
Little information was found on ECH-based ion exchange resins.
Reactions of epichlorohydrin with ethylenedlamine or higher homologues of
ethylenediamine produced water-insoluble materials that can be used as anion
exchange resins (Dow, 1980). The TSCA Inventory lists a number of these
materials Including:
ECH Polymer with Mnine Cas No.
1,2-ethanediamine 25014-13-5
N-(2-aminoethyl)-l,2-ethanediamine 25085-17-0
N-(2-aminoethy1)-N'-[2-(2-amino- 26658-42-4
ethyl)amino]ethyl-l,2-ethanediamine
N,N'-bis(2-aminoethy1)-1,2-ethanediamine 27754-94-5
N,N'-dimethyl-l,3-propanediamine 27029-41-0
1,2-ethanediamine and dimethylamine 42751-79-1
Rohm and Hass Co. and Diamond Shamrock are manufacturers of ion exchange
resins.
123
-------
Rohm and Haas Company (Meteyer and Pries, 1980) has patented a weakly
basic ion exchange resin made from ECH and the process for making it. The
typical process Involves preparing a solution of ECH (about 200 g/L) and a
suspending agent such as polybutenylsuccinimide polyamines (about 5 g/L) in
chlorobenzene or similar solvent in which the polyamine is not soluble. The
solution is heated to about 35°C with stirring and a solution of an amine like
triethylenetetramine in water (about 50% solution) is added dropwise. The
exothermic nature of the reaction raises the temperature and the reaction is
completed by refluxing for up to about 12 hours.
BCH is used in ratios of 2/3 to 1 1/2 times the stoichioraetric amount of
amine where each amine hydrogen is assumed to react with 1/2 of a mole of ECH
(e.g., one mole of triethylenetetramine is equivalent to three moles of ECH).
If less than 2/3 of the stoichlometrlc amount of ECH is used, the final ion
exchange resin is too weak for commercial use. On the other hand, if more
than 1 1/2 times the stoichiometric amount of ECH is used the final resin is
extensively crosslinked and it is too fragile and the rate of ion exchange is
too slow for commercial use.
After the reaction is complete, the organic solvent is distilled off and
replaced by water at a rate needed to maintain a fluid slurry. The resulting
ECH-polyamine condensation product is alkylated to improve the oxidation
stability of the final resin. Reductive alkylation can be applied by
treatment with formaldehyde/formic acid or exhaustive alkylation can be
applied by treatment with any appropriate alkylating agent (e.g., methyl
bromide, allyl chloride). In either case, a molar excess of alkylating agent
is used to assure conversion of primary and secondary amines to tertiary or
quaternary forms.
A typical alkylation with formaldehyde is achieved by adding
formaldehyde solution to the crude condensate slurry at 55°c and allowing it
to react for about 2 hours before adding formic acid to the mixture. About 2
moles of formaldehyde and formic acid are added for each mole of primary or
secondary amine in the crude condensate slurry, when alkylation is complete,
the resin is isolated, washed and dried and is then ready for packing into an
ion exchange column.
124
-------
5.2.6 Fyrol 2
No details have been found concerning the manufacture of
trls(l,3-dichloro-2-propyl) phosphate (CAS No. 13674-87-8) from ECH and
POCl . The process probably Involves reacting POCl with an excess of ECH
(ECH may be used as solvent) followed by distillation of ECH/solvent. The
resulting product Is probably rather pure and may be passed over a solid base
to neutralize any acid and remove any monoalkyl and dialkyl phosphate esters.
If aqueous alkaline washing Is used, a significant amount of Fyrol 2 will
dissolve In the wash water and the Fyrol 2 probably has to be dried.
5.2.7 Alkyl Glycidyl Ether Sulfonates
Proctor and Gamble Co. (Whyte, 1976) have been the leaders In
development of alkyl glycidyl ether sulfonates (AGES), which are specialty
surfactants that appear to be used In cosmetic and personal hygiene
applications. The composition of AGES Is summarized in this structure
R - 0 (CH_ CH - 0) H
2 | n
CH X
Where R is an alkyl group containing 8 to 22 carbon atoms, n=l to 4 and X=
-Cl, -OH or -SO H (Whyte and K<
public TSCA Inventory Include:
-Cl, -OH or -SO H (Whyte and Korpi, 1963). Some examples found in the
OH
R= M= CAS No.
2-ethylhexyl sodium 58965-18-7
isooctyl sodium 68072-33-3
6-methylheptyl sodium 68959-45-5
octyl sodium 51946-14-6
125
-------
AGES are made in two steps (Hhyte, 1976; Whyte and Korpi, 1962). In the
first step, an alcohol (e.g., the c cut from reduction of coconut oil) is
reacted with excess ECH and an acid (H.SO ) or Lewis acid (SnClJ
24 4
catalyst. This "condensation" reaction produces alcohol-polychlorohydrin
ethers:
CH2C1
R-0 (CH -CH-0) H
2 n
Typically, the mole ratio of alcohol to ECH used in the condensation is about
1:1.4 to ensure that all the alcohol is converted without building excessively
long polychlorohydrin chains (n=l to 4). The reaction time is about 15
minutes at 220°F using 1.5% SnCl. catalyst.
The second step is the sulfonation and can be accomplished by the
Strecker reaction of the chlorohydrin ether with sodium sulfite, or by
conversion to an Intermediate glycidyl ether followed by reaction with sodium
bisulfite. The direct Strecker reaction produces a water-soluble product that
is difficult to separate from the sodium chloride (salt) and the insoluble,
finely-divided basic tin chloride (SnCl.O). The Strecker reaction of
CH X CH Y
I 2 | 2
R-O-CH -CH-O-CH -CH-OH X=X=Cl
yields
50% X=Y= -SO
•J
35% X= -OH , Y= -
15% X= -Cl , Y= -
126
-------
If the manufacturer prefers a salt-free product, the alkyl glycidyl
ether can be formed as an Intermediate that can be washed free of salt and
catalyst before reaction with bisulfite (Whyte, 1976).
5.2.8 EplchlorohydrIn-Based Water-Treatment Chemicals
Two ECH-based flocculants for water treatment were Identified by Kirk-
Othmer (1980b). They are polymers of ECH with methylamlne and dlmethylamine.
poly(2-hydroxypropyl-l-N-methylammonlum chloride) CAS No. 31568-35-1
poly(2-hydroxypropyl-l-N,N-dimethylammonium chloride) CAS No. 25988-97-0
They are both catIonic resins, but the polymer with dlmethylamine is more
important commercially because it has only quaternary ammonium Ions which make
it insensitive to pH and chlorine-resistant (Kirk-Othmer, 1980b).
A request to Nalco Chemical Company for product bulletins on their
BCH-based water treatment resins was answered by data sheets on Nalcolyte
8105, 7135, 8101, and 8100 each of which is described as an aqueous solution
of polyquaternary ammonium chloride (Nalco, 1984). They are light yellow
liquids with slight ammoniacal odor and their pHs vary from 3 to 8. Nalcolyte
8105, 8108, and 8100 are approved by the EPA for treatment of potable water at
an application rate of up to 20 ppm. For Nalcolyte 8100, the manufacturer
recommends (Nalco, 1984):
Application Program Application Rate Use
Conventional clarification 1 to 10 ppm primary coagulant to
or lime softening partially or
completely remove
inorganic salts
127
-------
Clay polymer clarification
direct filtration
filter aid
1 to 10 ppm
0.2 to 2.0 ppm
0.05 to 1.0 ppm
primary coagulant in
a total replacement
for alum or iron
coagulants
primary coagulant
for low turbidity
and colored water
secondary coagulant
to Improve filter
effluent quality
128
-------
-------
6.0 OCCUPATIONAL EXPOSURE TO EPICHLOROHYDRIN
There has been considerable Interest in occupational exposure to
epichlorohydrln as a result of fear of adverse health effects. A summary of
occupational standards for ECH Is presented In Table 6.0A. Tracor Jitco, Inc.
conducted a broad survey of ECH exposure at manufacturing and user sites for
NIOSH (Bales, 1978). In this chapter, we summarize the NIOSH studies and
supplemental data that we have found In the literature.
Dermal exposure to ECH Is not a routine occurence and there are no
standards for dermal contact. In section 6.6, we discuss some aspects of the
problem of dermal exposure.
6.1 Exposure Associated with Manufacture of Bpichlorohydrin and
Glycerin
Tracor Jitco (Bales, 1977d; Doyle and Bales, 1977) conducted industrial
hygiene surveys at the epichlorohydrln-glycerln complexes run by Dow chemical
at Preeport, TX (July, 1976) and Shell Chemical at Deer Park, TX (August,
1976). Shell's glycerin, product i.on_has recently closed down, but they still
make ECH for epoxy resins and sales. Because of the relevance of these plants
to this report, they will be discussed In some detail.
6.1.1 Dow's Epichlorohydrln-Glycerin Plant
Dow's ECH-glycerln plant occupies a block In their large (1,000 acre)
petrochemical complex on the Brazos River near the Gulf of Mexico. The ECH-
glycerln plant has been In operation since 1956 and has a design capacity of
260 million pounds of ECH per year.
Dow's process follows the steps discussed in Sections 5.1 and 5.2.2.
Allyl chloride is produced from propene in an adjacent block and delivered to
the ECH-glycerin plant by pipeline.
129
-------
Table 6.0A. Exposure Limits for Bpichlorohydrln
PELC(OSHA), 1981
TLV4(ACGIH), 1981
RESe(NIOSH), (1978)
Shell Internal Standard (1978)
TWA6
ppm, v/v
5
2
0.5*
1
1 STELb
mg/ma ppm, v/v mg/m3
19
10 5
2* 5
5 3
-
20
19
15
^Time-weighted average, 8-hour day/40-hour week, unless
otherwise noted.
bshort Term Exposure Limit, 15 minutes, max.
Permissible Exposure Limit (Occupational Safety and Health
Administration), updated 1981.
^Threshold Limit Value, (American Conference of Governmental
Industrial Hygienists).
Recommended Exposure Standard (National Institute for
Occupational Safety and Health).
^Tlme Weighted Average, 10-hr day/40-hour week.
Source: Shell (1982).
130
-------
The allyl chloride is reacted with hypochlorous acid to produce
dichloropropanols and the dichloropropanols are reacted with base to yield
ECH. The product is isolated and purified by distillation. ECH is converted
to glycerin by hydrolysis with base.
Dow's ECH-glycerln plant employs 50 persons (Doyle and Bales, 19*77):
supervisory and Technical Staff
Production Staff
Superintendent
Engineers
Laboratory
Secretary
1
4
9
1
Production Foreman
Shift Foreman
Operators
Maintenance
2
4
13
11
Totals
15
35
The supervisory and technical staff and production foremen
have little opportunity for exposure to ECH. Shift foremen
may spend 50% to 100% of their time in the production area.
There are two classes of operators: Control A and Control
C. Control A is the senior operator and is responsible for
monitoring control instruments and making necessary adjust-
ments to maintain production. They spend more than 80% of
the work shift in the control room.
The Control C Operator spends about 50% of the work shift
in the production area; one of his major duties is the
collecting and analysis of the process samples. During the
sampling operation he is required to wear an organic vapor
respirator. At the time of the study (1976), automatic
sampling and analysis equipment was being installed which
will relieve the Control C Operator of the sampling
responsibility.
Maintenance personnel are primarily mechanics and
pipe-fitters. Their exposure to epichlorohydrin is a
function of the time spent in repairing and servicing
epichlorohydrin units.
There is one Head Packaging Operator and four general
operators. The Head Packaging Operator spends most of his
time in supervisory and administrative duties. The four
general operators are responsible for loading epichloro-
hydrin into railroad tank cars, tank trucks, and drums. In
addition, they maintain the warehouse and load trucks with
filled drums.
131
-------
The results of the analyses are summarized in Table 6.1.1A.
6.1.2 Shell's Epichlorohydrln-Glycerin Plant
Shell ECH-glycerin plant is part of a large petrorefining and petrochem-
ical complex located adjacent to the Houston Ship Channel. Manufacture of ECH
began at this site in 1945. The ECH-glycerin plant ("G-plant") began produc-
tion in 1948. Some ECH was delivered to the Deer Park complex by barge from
the Shell plant in Louisiana, but with the end of Shell's synthetic glycerin
production, this has probably stopped.
Shell's ECH-glycerin plant includes the following operators (Bales,
Job Number
Production of allyl chloride (GlOO) 3
Production of ECH and crude glycerin (G200-300 and HTH) 2
Production of refined glycerin (C-plant) 1
Tank farm operator 1
A summary of the analytical results for these operators and other
employees is presented in Table 6.1.2A.
6.1.3 Dermal Exposure to Epichlorohydrin at Epichlorohydrin -
Glycerin Plant
No information was found on frequency, duration or intensity of dermal
exposures to ECH during its manufacture or the manufacture of glycerin. It is
clear from reading the manufacturers literature that such incidents would be
considered to be a major failure of proper handling procedures. Maintenance
of pumps, valves and fittings and filling of drums appear to be the activities
with the most potential for exposure.
6.2 Exposure Associated with Manufacture of ECH-Epoxy Resins
Bales (1977a,b,d) and Doyle and Bales (19T7) conducted industrial
hygiene surveys at several plants where epoxy resins were manufactured from
ECH:
132
-------
Table 6.1.1A. Summary of Atmospheric Samples for Epichlorohydrin and Allyl
Chloride at Dow's Epichlorohydrin-Glycerin Plant (July, 19*76)
Type or Atmospheric Concentration
Shift
1
2
3
1
2
3
1
2
1
2
3
1
1
1
1
1
1
Worker
Control
it
it
Control
it
ii
Control
ii
Sampled
A Operator
ii ii
ii ii
C Operator
ii M
ii ii
C Trainee
ii ii
Shift Foreman
ii
ii
ii
ii
Pipefitter 1
ii
«i
Packing
ii
Packing
2
3
Op. 1 - Drum
ii ^ __ ii
op. 1 - Tank
Car
Duration (ppm)
of Sample Epichlorohydrin Allyl Chloride
TWA
TWA
TWA
TWA
TWA
TWA
TWA
TWA
TWA
TWA
TWA
5 hrs
5 hrs
5 hrs
4 hrs, 20 mln
4 hrs, 20 min
3 hrs, 10 min
0.38
N.D.*
0.23
0.33
N.D.
0.39
0.41
N.D.
0.17
0.1
0.14
N.D.
N.D.
N.D.
N.D.
N.D.
0.28
0.24
N.D.
N.D.
0.68
N.D.
0.11
0.11
0.26
0.3
o.n
N.D.
N.D.
N.D.
N.D.
*Not detectable based on the limit of the analytical method
(0.05 ppra for ECH and 0.1 ppra for allyl chloride) according
to Bales, 1978.
Source: Doyle and Bales (1977).
133
-------
Table 6.1.2.A
Summary of Epichlorohydrin Exposure Levels at Shell's
ECH-Glycerln Plant, C Plant and Shipping (1976).
Job Types
Epichlorohydrin
TWA Exposure Levelsa
No. Median High
Samples (ppra) (ppra)
Glycerine Plant Area
G 100 Operator
G 300 Operator
G 300 Foreman
HTH Operator
G 300 Control Room
Maintenance Foreman
G 300 Area
C Plant Area
C Plant Operator
C Operations Control Room
Shipping
Tank Loading Operator
6
5
6
4
5
2
1
6
1
1
N.D.
N.D.
N.D.
0.30
N.D.
0.29
N.D.
0.18
0.37
0.27
0.26
2.1
0.31
0.92
0.50
0.50
N.D.
0.34
0.37
0.27
aDetection limit 0.05 ppra according to Bales (1978),
Source: Bales (1977d).
134
-------
Dow Chemical, Freeport, Texas, July, 1976
Shell Chemical Co., Houston, Texas, August, 1976
Celanese Coatings and Specialties Co., Louisville, Kentucky,
February, 1976
Ciba-Geigy Corp.. Toms River, New Jersey, May, 1976
In all cases, 1976 exposures were below 1 ppm TWA. Dow had some data from
1975 that showed some cases of potential exposure to about 3 ppm, but these
exposures were mitigated by protective equipment.
6.2.1 Dow's Epoxy Resin Plant
The epoxy resin unit at Dow's Freeport complex is about a mile from the
ECH-glycerin plant. ECH is pumped to the epoxy plant and stored in closed
tanks. Blsphenol A and Novolac resins are prepared by conventional
techniques, the excess ECH is stripped and the resins (in solvent) are pumped
to the resin finishing area. When operators are in the production area, they
are required to wear long-sleeve Jackets, gloves, and eye shields and must
carry an organic vapor respirator for emergency use. During normal operations
there are only two operators In the epoxy resin area. They spend about 80°& of
their time in the control room and 20% in the production area.
Dow provided Doyle and Bales (1977) with some monitoring data for 1973
and 1974. Most of the personnel samples were below 0.03 ppm. In 1974 the
highest level for an operator was 0.90 ppm. Some grab samples, presumably of
areas where leaks or spills were expected, had concentrations up to 15 ppm.
In the study by Doyle and Bales (1977), no detectable levels of ECH were found
(Based on other work by these worker, the detection limit appears to be 0.05
ppm (Bales, 1978)).
6.2.2 Shell's Epoxy Resin Plant
Shell's epoxy resin plant Is similar to Dow's and employs conventional
technology. There are about 9 operators per shift; altogether about 60 people
are routinely employed in the epoxy plant area. Some key Jobs include:
135
-------
2A Kettle Operator - includes process control of manu-
facture of a solid epoxy resin.
3A Kettle Operator - includes process control of the
manufacture of a liquid epoxy resin.
3A Utility Kettle Operator - includes process control in manu-
facture of liquid epoxy resin.
Resin Train Operator - includes process control of liquid
epoxy resins.
Peed and Recovery Operator - includes process control in liquid
epoxy resin manufacture of feed
materials and recycling or recovery.
.Shift Foremen - supervises the epoxy resin processes.
The results of ECH monitoring is summarized in Table 6.2.2A.
6.2.3. Celanese's Epoxy Resin Plant
The Celanese epoxy resin plant studied by Bales (1977b) is located in
the city of Louisville, KY. Epoxy resin production began here in 1952. The
plant was operated by Devoe and Raynolds until 1965. ECH is received in
railroad tank cars and stored in outdoor tanks. As needed, it is pumped to
weighing tanks on the fourth floor of the plant. It is then allowed to flow
by gravity into the reaction kettles where bisphenol A and caustic are added
also via piped connections. Apparently, after the reaction is complete, water
and solvent are added and the aqueous brine is removed. The resin in solvent
is removed and the solvent is distilled. Liquid resins are shipped out in
railroad tank cars and solid resins are shipped in bags.
About 35 employees are directly involved in manufacture of epoxy resins
at this plant. Monitoring data are summarized in Table 6.2.3A.
6.2.4 Ciba-Geigy's Epoxy Resin Plant
In the period 1960 - 1966 Ciba-Geigy produced ECH and epoxy resins at
their Toms River, NJ plant. Now ECH is purchased and received in railroad
tank cars. The ECH facility and process seem to be similar to the Celanese
136
-------
Table 6.2.2.A Summary of Epichlorohydrin Exposure Levels at Shell's Epoxy
Plant, August, 1976.
Job Type
Epichlorohvdrin TWA Exposure Levels
No. Median High
Samples (ppm) (pprn)
Shift Foreman
2A Kettle Operator
3A Kettle Operator
Resin Train Operator
Feed and Recovery Operator
3A Utility Operator
Maintenance Foreman
Finishing Operator
6
5
4
6
4
2
1
2
N.D.
N.D.
N.D.
0.23
0.26
N.D.
N.D.
0.45
0.60
0.10
0.56
0.83
0.52
N.D.
N.D.
0.80
According to Bales (1978) the detection limit is 0.05 ppm ECH.
Source: Bales (1977d).
137
-------
Table 6.2.3A Results of Air Sampling Analyses at Celanese's Epoxy Resin
Plant in Louisville, KY. February. 1976.
Sample
Location/Description
Operation
Epichlorohydr in
Air Concentration
ppm
Resin Kettle Area - 3rd
level. Side of Kettle
(weight scale)
Resin Kettle Area - 3rd
level. Top of Kettle
(Catwalk)
Wet Tank Room
Control Room - 3rd
level
Resin Kettle and Weight
Scale Area - 3rd level
Resin Kettle and Weight
Scale Area - 3rd level
Resin Kettle and weigh
Scale Area - 3rd level
Resin Kettle and weigh
Scale Area - 3rd level
Charge ECH
Draw off
Charge EPI -
Draw off
Normal
Normal
Charge Blsphenol A
Charge ECH
Pressure on
Kettle-Draw off
Charge solvent and
Draw down
0.35
0.59
1.5
N.D.a
0.05
0.07
nil
0.13
0.05
aNot detectable based on an analytical limit of 0.05 ppm ECH.
Source: Bales (1977b).
138
-------
plant discussed above. About 60 people are involved with epoxy resin
production. In 1976, Bales (1977a) did not find any detectable exposures to
ECH at this site. The detection limit appears to be 0.05 ppm based on other
reports by this author (Bales. 1978).
6.2.5 Dermal Exposure to Epichlorohydrin during Manufacture
of Epoxy Resins
There appears to be little opportunity for dermal exposure to pure ECH
during manufacture of epoxy resins. No information on frequency, intensity or
duration of dermal exposures to ECH during the manufacture of epoxy resins was
found.
6.3 Exposure Associated with the Use of Epoxy Resins "•
6.3.X InhalatlbTKjSxposure
We have found one report of very high exposures of employees to ECH
during use of ECH epoxy_resins (Chrostek and Levine, 1981). In this case,
large structural steel members were being coated with a two-part epoxy painlt
by hand spraying in a large enclosed building with poor ventilation. High
levels £f_ECH_and glycidyl ether of blsphenol A were found (Table 6.3A and
6.3B).
Shell (1982) provided some monitoring data that they consider to be
typical of BCH exposure during use of epoxy resins (Table 6.3C). Other
monitoring data have been collected by OSHA. The positive findings from the
OSHA National Inspection Summary Report for June 1, 1979 to March 31, 1983 are
summarized in Table 6.3D. The numerous negative findings are probably similar
to the report by Lewis (1980) who studied workmen who were using epoxy resin
to encapsulate Instruments for measuring water flow in a pipe. In this
process, the epoxy resin and curing agent were mixed using a hand-held mixer
and then poured into a water pipe where the instruments were attached. \No ECH
or phenyl glycidyl ether were found in any time-weighted-average air sample
(detection limits 0.1 mg/sample and 0.04 mg/sample, respectively).
139
-------
Table 6.3A Results of Sampling for Eplchlorohydrin Vapor, Palmer Industrial Coatings, Willlamsport, PA
Job
Date Description
Sept. 9 Foreman
Sprayer
Sprayer
TWA
Sprayer
Sprayer
Sept. 10 Sprayer
Sprayer
TWA
Sprayer
Sprayer
TWA
Sprayer
Sprayer
TWA
Foreman
Foreman
TWA
Sample Period
08:35-15:00
07cl5-10:05
10:05-15:18
07:20-15:30
07:29-15:25
07:10-12:10
12:10-15:25
07:10-12:00
13:25-15:00
07:10-12:00
13:25-15:30
07:25-12:00
12:30-14:55
Airborne
Concentrations*
45.5
88.2
76.7
80.7
2.4
138.9
83.3
82.1
82.8
56.9
104.7
68.2
43.9
42.0
43.3
36.3
42.6
37.8
Remarks
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Operator's
Exposure
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Breathing Zone
Exposure
Exposure
•Denotes milligrams of contaminant per cubic meter of air sampled, detection limit 0.05 mg.
Source: Chrostek and Levin (1981) .
-------
Table 6.3B Results of Sampling for Bisphenol A and Glycidyl Ethers of Bisphenol A at Plainer Industrial
Coatings, Williamsport, PA
Date
09/09
09/10
* Denotes
** Denotes
Worker
Painter
Painter
Painter
Painter
Foreman
Painter
Painter
Painter
Foreman
micrograms
lower limii
Time Period
07:15-10-05
10:05-15:18
07:29-15:25
07:20-15:30
08:30-15:00
07:10-15:30
07:10-15:25
07:10-15:39
07:25-14:25
of contaminant per cubic
t of detection, 6 microgri
Bisphenol A
0.6**
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
meter of air sampled.
jms per sample.
Glycidyl Ethers*
of Bisphenol A
0.6
24.18
4.86
2.27
2.72
28.61
8.19
11.85
5.38
Remarks
OBZ***
OBZ
OBZ
OE****
OBZ
OBZ
OBZ
OE
*** Denotes operator's breathing zone.
**** Denotes operator's exposure.
Source: Chrostek and Levine (1981).
-------
Table 6.3C. ECH Exposures During Industrial Use of Epon Resins
Type of
application
Filament winding of pipe
Coatings manufacture
Encapsulation
Filament winding - pipe
Filament winding - pipe
Filament winding - tape
Bow mfg.
Adheslves mfg.
Epoxy tank spraying
Bpoxy grout application
Simulated field application
Resins formulation
ECH content
of resin (ppm)
1
1. 1.6
1
10
10
1
10 max.
15-88.1
1
16
1100 (spiked)
__
Airborne
ECH (ppm)
N.D.* (0.05)
N.D. (0.05)
N.D. (0.05)
N.D. (O.OS)-O.l
0.1
N.D. (O.OS)-O.l
N.D. (0.05)
N.D. (0.05)-1.6
N.D. (0.05)
0.6-1.1
N.D. (0.05)-0.15
N.D. (0.05)
*N.D. - None detected, 0.05 ppm detection limit.
Source: Shell (1982)
Comment: These results are actual monitoring dates that Shell (1982) consider
to be typical of ECH exposure during use epoxy resins. The data in
Table 5.2.1.5C represent equilibrium (i.e., maximum) concentration
of ECH achieved in static laboratory tests (using various concentra-
tions of ECH in the resin and various working temperatures). The
data in Table 6.3D are the results of investigations of worker
complaints and represent the positive findings culled from 39
investigations involving 300 workers (73 personally sampled).
142
-------
Table 6.3D Summary of Positive Bpichlorohydrin Findings from OSHA Surveys3
June 1977 - March 1983.
Area SIC
Boston 3832
2821
Tampa 3612
Appleton 3991
Milwaukee 3079
Lubbock 3479
Type of Business
Optical instr. & Lenses
PTR Optics Corp.
Plastic Materials, etc.
Wilmington Chera. Corp.
Power, Distr. & Spec. Trans
Instrument and Transformer
Brooms and Brushes
Besh Roller Inc.
Misc. Plastic Products
Lewis Systems Mensha Corp.
Coating, Engraving, etc.
Spincote Plastic Coatings
Number of
Exposed Workers
2
1
•
Co. 18
0
6
0
2
2
2
ECH Levels
(ppm)
TWA 3.8
TWA 0.71
TWA 0.14
TWA 2.66
TWA 3.38
TWA 3.02
TWA 0.01
TWA 3.70
TWA 3.70
aDuring this time period OSHA conducted 39 plant surveys and monitored 79
workers out of 300 potentially exposed. No exposures in excess of the 5 ppm
PEL were observed.
Source: OSHA (1983)
143
-------
6.3.2 Dermal Exposure
Dermal exposure to ECH during use of epoxy resins Is possible mainly for
coating, casting, molding, adhesive and patching applications. In most cases
the ECH levels In the resin are probably below 10 ppm and dermal contact would
be brief. Except for some coating applications, dermal contact should be
limited to the hands and gloves would probably be worn. One report of
dermatlltls due to penetration of gloves by one or more components of Araldlte
MY 750 (a coal tar epoxy resin with glycldyl ether reactive diluent made by
Ciba-Gelgy) was found (Pegura, 1979). Any residual ECH In this product would
probably be the most mobile component, but the reactive diluent might also
penetrate gloves so It cannot be assumed that ECH caused the dermatitis. No
data on the frequency, Intensity or duration of dermal exposure during use of
epoxy resins were found.
6.4 Exposure Associated with the Manufacture arid. Use of ECH-Elastomers
6.4.1 inhalation Exposure
According to Hercules product Information cited by vandenberg
(Klrk-Othmer, 1979a), ECH levels In air have been monitored during
manufacture, storage and processing (at three customer plants). The levels
were generally found to be less than 0.1 ppm, well below the Federal standard
of 0.5 ppm. Data from the Hercules plant collected In July 1977 using the
NIOSH method showed that the time-weighted-average exposure of most workers
(Including operators, helpers, mechanics and laborers) was below the detection
limit (I.e., 0.1 ppm). In three cases, operators working around the
polymerization-vessel -(Including such tasks as changing ECH pump check_valves)
had--TWA exposures of 0.2 ppm (Hercules, 19835). At processing plants, luT
detectable TWA exposures were found. The processing plants included elastomer
weighting, extrusion, two-roll mill mixing, and molding (Hercules, 1983b).
144
-------
6.4.2 Dermal Exposure
Dermal contact with uncured ECH elastomers may occur, but no data were
found on the frequency, intensity or duration of contact. Cured (compounded
and vulcanized) ECH elastomer is not expected to contain significant ECH
residue.
6.5 Exposure Associated with Wet-Strength Resins
6.5.1 Manufacturing
Tracor Jltco (Bales, 1977c) surveyed the Hercules, Inc. plant at
Savannah, GA on June 17, 1976. Het-strength resins of the ECH-aminopolyamide
type have been manufactured here in a two-story semi-enclosed building con-
tinuously since 1952. They are sold under the tradename kymene.
ECH is brought in by tank trucks and transferred to a storage tank
several hundred yards from the kymene plant. The ECH is pumped as needed to
the kymene plant for batch operations. The manufacturing process is carried
out in closed reaction vessels. First the aminopolyamide resin is formed in
one vessel and the polymer is fed into a second reactor where it is diluted
with water. ECH is pumped into the second reactor and the reaction begins as
described in Section 5.2. The reaction is stopped before the crosslinking
becomes too great by adding sulfuric acid, diluting the solution with a large
amount of water and cooling. The aqueous solution of wet-strength resin is
pumped to tank cars, tank trucks or drums for shipping (Bales, 1977c).
The kymene process employs 2 to 5 operators and one supervisor over
three shifts. It was estimated that 50 workers had worked in the kymene
facility at various times between 1952 and 1976. The results of air sampling
are summarized in Table 6.5A (Bales, 1977c). Occupational exposure during
manufacture of wet-strength resins is very minor.
145
-------
Table 6.5A Results of Air Sample Analyses at a Hercules, Inc.
Wet-Strength Resin Plant (1976).
Sample
location
Kymene Building
2nd level
Kymene Building
Kymene Building
Sample
type
GA
TWA
GA
Job/sample
description
Kettle area
Batch 551 H
Kymene operator
Ad 1 . to polymer
Shift
1
1
1
Epichlorohydrin
air concentration
(ppm)
0.36
0.15
N.D.
1st level
Kymene Building GA
1st level
Kymene Building OP BZ
2nd level
Kymene Building TWA
2nd level
Kymene Building GA
2nd level
kettle pump
Kymene kettle
(Total EPI reaction
period) Add EPA to
reaction kill
Kymene operator
Kettle area
Batch 551 H
N.D.
N.D.
0.05
0.42
N.D. - non-detectable based on an analytical limit of 0.05 ppra.
OP BZ - operators breathing zone (near head).
TWA - time-weighted-average personnel sampler.
GA - general area.
Source: Bales (1977c).
146
-------
Bales (1977c) makes the statement that there are no ECH residues in the,
product, but no data are given. If residues of ECH do remain in the product
(or if dichloropropanols in the product are converted to ECH when the resins
are activated by base prior to use, see 5.2.4.3), then there might be ECH
exposure during application of wet-strength resins to paper.
6.5.2 Possible Exposurenduring Use
If residues of ECH are contained in the aqueous wet strength resin
solutions, some exposure to ECH may occur during manufacture of paper. Derma11
exposure to the resin solution is possible but probably slight. The most
likely type of exposure would be to ECH vapor released during the dewatering
and drying steps. It Is very unlikely that free ECH residues remain In
finished paper.
6.6 Dermal Exposure to Bpichlorohvdrin
Both Dow (1980) and Shell (1969) emphasize avoidance of dermal contact
with ECH in their industrial hygiene programs. A specimen label for ECH is
shown In Fugure 6.6A. in particular, It makes the following admonition:
"Wear chemical goggles, rubber gloves, and protective
clothing when handling. Medium or heavy thickness rubber
protective equipment is preferred. Polyethylene, polyvinyl
chloride, and thin rubber give protection for minor liquid
contact only. Epichlorohydrin in continuous liquid contact
penetrates these materials In a relatively short time. Do
not use leather articles, such as shoes or gloves, as they
cannot be decontaminated."
Similarly, Shell (1969) states:
"Keep the liquid off the skin and clothes. The greatest
hazard results from spilling eplchlorohydrin on the skin or
clothing. Consequently, when danger of spillage on the
body exists, workers should wear protective clothing and
face splash guards. Furthermore, since epichlorohydrin
slowly penetrates rubber, rubber clothing that has been in
contact with the liquid should be discarded."
147
-------
LOTTB
EPICHLOROHYDRIM
A HIGHLY REACTIVE CHEMICAL INTERMEDIATE
DANGER & POISON
MAY BE FATAL IF SWALLOWED • CAUSES IRRITATION • PROLONGED
CONTACT CAUSES BURNS • HARMFUL IF INHALED • HARMFUL IF
ABSORBED THROUGH SKIN • VAPOR IRRITATING TO EVES. NOSE.
AND THROAT • M AY CAUSE ALLERGIC SKIN REACTION • FLAMMABLE
Do Not Tike Internally • Do Not Gel in Eyet. on Skin, on Clothing • Do
Not Breathe Vapor • U»e Only with Adequate Ventilation • Keep
Container doled • Wa»h Thoroughly Alter Handling • Keep Away From
Heat. Spaiks. and Open Flame • Do Not Cut or Weld Container
FIRST AID: II indue •«» .nduca vomiting immeUi4lei r Dv g<*irig IMU yijNW* wt **li" 4iid
uncontcioul D^'w-
It lnhal«4, remoir s«li«nl to "»1 «ir irro rum ortifn «nu gu.ei Can « DrifML-.jn
i(nm«<]ial»l« II flol S'rjtning giv« tlilicial (PMjiution D'^'v'dO1* fnoutn-lo muuln II
Ofvain.ng .ftU-tt.ei..* (]•*• o«*g«n
18.93 L/5 GAL
HANDLING PRECAUTIONS
Wear chemical oongit.-s fubDn' qiovos. and protective c euu«"JL' <|(uuu
are generally unstable m the presence ol aodic or bjsic suOiinnci.-s
Epicnioronyann. giycidoi and qiycidyl cint-is mjy relict viijurguslv to-
explosively with strong sullunc dC"d .mo with annyjrousnii-i.il h.inufs
These materials should bo handled 'witn due pu-cnunoni oy tMUt-n-
enced and competent personnel
THE DOW CHEMICAL COMPANY
FLAMMABLE
v LIQUID N.O.S.
E378
Figure 6.6A. Specimen Label for Epichlnrnhydrin.
148
-------
Dow's product bulletin for ECH devotes 4 of its 12 pages to
handling procedures for ECH. Dow (1980) also notes:
"Short contact with epichlorohydrin may result in slight
Irritation. Prolonged contact may result in severe Irri-
tation and a superficial burn. These effects may be
delayed, appearing some time after contact. Human expe-
rience has also Indicated that a small percentage of
persons may develop hypersensitivity from repeated con-
tacts.
Epichlorohydrin is readily absorbed through intact skin in
acutely toxic amounts (The LD50 for rabbits is in the
range of 0.5 gm/kg.). Reports in the literature indicate
an appreciable hazard of systemic intoxication from
repeated slight contacts. There is little doubt that one
of the greatest hazards associated with the handling and
use of epichlorohydrin is from contact with the skin.
Proper protective equipment and garments should be worn to
prevent the material from contacting the skin or clothing.
Do not use leather shoes; use rubber shoes or overlays when
working in an area where epichlorohydrin may be contacted.
It is recommended that workers bathe with soap and water
after each work day and wear freshly laundered clothing
each morning (Note: Because epichlorohydrin slowly
permeates rubber, any gloves or rubber garments should be
worn only for a limited time when in gross contact with
epichloro- hydrin). It is desirable to wash rubber gloves
with soap and water each day, and dry them in a moving
stream of air. Discard gloves if they show any sign of
deterioration."
First Aid: If exposure should occur, immediately irrigate
skin with copious amounts of water. Remove all contami-
nated clothing while continuing decontamination with
copious amounts of water for 15 minutes. Obtain medical
attention immediately,"
According to ACGIH (1971), there were no reported instances of serious
injury to industrial workers during the production or handling of
epichlorohydrin through 1971 although several cases of skin burns from contact
with the liquid had occurred. Dermal contact appears to be most likely during
transfers and maintenance operations. Dow and Shell have made efforts to
minimize the risk of such accidents and mitigate their effects if they occur
for their employees and customers.
149
-------
It Is possible to make estimates of the amount of ECH that would
penetrate Intact skin in a spill situation. The calculations that are
presented below do not take into consideration the damage that concentrated
ECH does to skin and so the results probably underestimate the actual exposure
that would occur. As described by Scheuplein (1965) the flux (J) of a
chemical through skin can calculated be as follows:
Flux = J = k C (1)
P
where
J = the amount of solute that penetrates a unit of skin per unit time
mg/cm .s,
k = the permeability constant (cra/h), and
P
3
C = the difference in concentration between outside and inside mg/cm .
It has been found that k is a function of temperature and can be
P
related to the activation energy for diffusion (Blank et al., 1967). The
activation energy for diffusion of polar alcohols through human skin is about
16.5 kcal/mole and the activation energy for non-polar alcohols is about 10.0
kcal mole above 23°C.
If k is available for the substance of Interest, J can easily be
P
calculated using equation (1) for any particular concentration of the
substance applied to the skin surface. However, since k is seldom known,
it is useful to look at a more detailed equation (Idson, 1971):
j = ^ AC (2)
where
150
-------
K = the partition coefficient of solute between skin and the solvent
2
D = the diffusion coefficient of solute in skin (cm /s)
3
C = the concentration difference of solute across skin (rag/cm )
i = thickness of skin (i.e., stratum corneura) in cm.
Overall, the skin seems to have lipophilic character, and since the
solvent for the substance is often water, linear relationships between K
Rl
and the octanol/water partition coefficient (P) have been suggested (Roberts
et al., 1977):
log K = 0.57 log P - 0.1 (3)
m
The diffusion coefficient (D) is also related to molecular properties of
the substance. The molecular size is the only feature generally recognized to
be related to diffusion coefficients, and larger molecules are generally
expected to diffuse more slowly than small ones (Calvert and Billingham, 1979;
Scheuplein and Blank, 1973). Scheuplein (1965) notes that the diffusion
constant is inversely proportional to the cube root of the molecular volume
(i.e., changing the volume by a factor of 4 changes D by a factor of 1.6).
In practice, it is probably most reasonable to assume that chemicals
with similar octanol/water partition coefficients and similar molecular size
will penetrate the skin at similar rates at the same temperature. In Table
6.6A the permeability constants (k ) through human skin and the octanol/
water partition coefficients are listed for a series of alcohols. We noted
that the log octanol partition coefficient for ECH is 0.30 (Chem et al, 1981),
which is similar to log P for propanol. Using the Ic for propanol from
P
Table 6.6A and the density of ECH 1.17 g/cc as the maximum possible
concentration Of ECH (Dow, 1980):
J = flux = (0.004 cra/h) (1.17 g/cm3)
= 4.7 mg/cm .h
151
-------
Table 6.6A. Permeability Constants and Octanol/Water Partition
Coefficients for Alcohols.
Permeability constant3
Alcohol for human skin, 40°C Log P (octanol/water)b
(cra/h)
ethanol 0.001 (-3)° -0.32
propanol 0.004 (-2.4) 0.34
butanol 0.007 (-2.2) 0.88
pentanol 0.040 (-1.4) 1.40
hexanol 0.073 (-1.1) 2.03
heptanol 0.096 (-1.0) 2.41 (est.)
octanol 0.11 (-0.95) 3.15
aExtrapolated and Interpolated from Figure 2 of Blank et al. (1967).
Roberts et al. (1977) provided similar data for several phenols. If
the data from Roberts et al. (1977) Table 1 are corrected from 25°C to
40°C using the log P-dependent extrapolation of Blank et al. (1967), the
results would be similar to these. In general, changing the temperature
from 25°C to 40°C Increases the kp for polar compounds by a factor of
about 10 and nonpolar compounds by a factor of 2.
bLeo et al. (1971).
clog (kp) in parentheses.
152
-------
If we assume a spill might involve 100 cm2 of skin and would be washed
off within 0.1 h (6 minutes)
estimated dose = (4.7 rag/cm2.h)(100 cm2)(0.1 h)
estimated dose = 47 mg of ECH absorbed in spill of neat liquid onto
100 cm2 of skin followed by decontamination in
6 minutes.
Because the k used here assumes steady state diffusion, immediately
cleaning the skin (e.g., with 30 seconds) probably stops exposures before
penetration is achieved (Scheuplein, 1967). At longer exposure times, damage
to the skin probably results in faster permeation. Both these factors point
to the need for immediate decontamination of ECH spills on skin or clothing.
153
-------
REFERENCES
ACGIH. 1979. Documentation of the threshold limit values. American Conference
of Governmental Industrial Hygienists.
ADL (AD Little). 1979. Human Safety and Environmental Aspects of Major
Surfactants. AD Little, Inc. Cambridge, MA. pp. 345, 463.
Aldrlch. 1982. Catalog Handbook of Pine Chemicals. Aldrlch Chemical Co.,
Milwaukee, WI.
Anderson GE, Liu CS, Holman HY, Killus JP. 1981. Human exposure to
atmospheric concentrations of selected chemicals. Systems Applications, Inc.,
San Rafael, CA.
Arnold S. 1984a. Telephone conversation between S. Arnold of Dow Chemical
Company and L. Borghl of Dynamac, January 1984.
Arnold S. 1984b. Letter from S. Arnold of Dow Chemical Company to G. Parris
of Dynamac, January 1984.
Arnold S. 1984c. Telephone Conversation between S. Arnold of Dow Chemical
Comapny and G. Hammaker, January 1984.
Arnold S. 1984d. Letter from S. Arnold of Dow Chemical Company to L. Borghi
of Dynamac Corporation giving Information on uses, consumption and product
residuals of epichlorohydrin. January 18, 1984.
Bales RE. February 1978. Epichlorohydrin manufacture and use industrial
hygiene survey. DHEW (NIOSH) publication No. 78-151, Washington, DC.
Bales RE. March 1977a. Epichlorohydrin industrial hygiene survey Ciba-Geigy
Corp. Toms River Chemical Plant, Toms River, NJ. Tracer Jitco, Inc. Rockville,
MD.
Bales RE. March 1977b. Epichlorohydrin industrial hygiene survey Celanese
Coatings and Specialties company, Louisville, KY. Tracer Jitco, inc.,
Rockville, MD.
Bales RE. March 1977c. Epichlorohydrin industrial hygiene survey report
Hercules, Inc., Savannah, GA. Tracer Jitco, Inc., Rockville, MD.
Bales RE. August 1977d. Epichlorohydrin industrial hygiene survey Shell
Chemical Co.. Deer Park Manufacturing Complex, Houston, TX. Tracer Jitco,
Inc., Rockville. MD.
Blank IH, Scheuplein RJ, MacFarlane DJ. 1967. Mechanism of percutaneous
absorption. III. The effect of temperature on the transport of
non-electrolytes across the skin. J. Investigative Dermatology 49(6):582-370.
Brady DG. Zuech EA, Gray RA. 1975. Brominated 2,2-bis(4-alkenyloxyphenol)
propanes. U.S. Patent 3,895,077 assigned to Phillips Petroleum Company.
154
-------
Braun D, Lee DW. 1976. Uber einige Nebenprodukte bei der Herstellung von
Epoxidharzen aus Bisphenol A und Epichlorohydrin. (on some byproducts from the
reaction of blsphenol A and eplchlorolhydrln.) Angew. Makromol. Chem.
51(766):11-24.
Britt KW. 1910. Handbook of Pulp and Paper Technology, 2nd edit, van Nostrand
Relnhold Company, New York, NY, pp. 377-380.
Calvert PD, Blllingham NC. 1979. Loss of additives from polymers: a
theoretical model. J. Appl. Polym. Sci. 24:357-370.
Chemical & Engineering News, Key Chemicals, 61:10 November 21, 1983; 60:12
August 30, 1982; 59:18 September 28, 1981.
Chemical Eng. Progress. 1948. Synthetic glycerin plant opened at Houston by
Shell. 44(10)-.16-18.
Chemical Marketing Reporter. 1979. March 12. p.58.
Chemical Marketing Reporter. 1981. May 25. NO. 21, chemical Profile: Glycerin.
Chemical Marketing Reporter. 1984. February 20. p.41.
Chemical Purchasing. June 1982. Chemical Briefs 1, Epichlorohydrin, pp. 19-23.
Chen C, Sun C-J, Zafran F, Taylor D, Weinstein G. January 1981. TSCA Section
4 human exposure assessment: Haloalkyl epoxides. JRB Associates, Inc., McLean,
VA.
Chrostek WJ, Levine MS. May 1981. Health hazard evaluation report HHE
80-153-881 Palmer Industrial Coatings, Inc., Williamsport, PA. NTIS No. PB
82-215-336. NIOSH, Cincinnati, OH.
Cogswell SA, Bakker J, Suzuki H. 1983. Epichlorohydrin. 642.3021A. Chemical
Economics Handbook, SRI International, Menlo Park, CA.
Oilling WL, Bredeweg CJ, Tefertiller. 1976. Organic pholtochemistry simulated
atmospheric photodecomposition rates of methylene chloride, 1,1,1-trichloro-
ethane, trichloroethylene, tetrachloroethylene, and other compounds. Environ.
Sci. Technol. 19(4):351-6.
Dow. 1980. Epichlorohydrin, properties, uses, storage and handling by the Dow
Chemical Company.
Doyle H, Bales R. March 1977. Epichlorohydrin industrial hygiene survey
report Dow Chemical USA, Texas Division, Freeport, TX. Tracer Jitco, Inc.,
Rockville, MD.
Dukes CF, Welch RW. 1975. Process for preparing glycidyl esters of
polycarboxylic acids. US Patent 3,859,314 assigned to Celanese Coatings &
Specialities.
155
-------
Elast. April 1977. p. 30.
Blast. May 1978. p. 13.
Elast. January 1983. p. 36.
Emery industries. 1984. Telephone conversation between Emery industries sales
representative and G. Hammaker, DPRA, March 19, 1984.
Enikolopyan NS, Markevitch MA, Sakhononko LS, Rogovina SZ, Oshroyan VG. 1982.
Kinetics of epoxide resins formation from epichlorohydrin and bisphenol A. J.
Polym. Sci. 20:1231-1245.
Environmental Protection Agency (EPA). October 1983. Health assessment
document for epichlorohydrin (Review Draft) EPA 600/8-83-032A, Washington, DC.
European Plastics Journal, February 1983, p. 12.
European Rubber Journal, February 1983, p. 12.
Fairbalrn AW, Cheney HA, Cherniavsky AJ. 1947. Commercial scale manufacture
of allyl chloride and allyl alcohol from propylene. Chera. Eng. Prog.
43(6):280-290.
Farbe & Lack. January 1982. p. 73.
Fielding MJ, Richards BL, Jr. 1967. Pungicidal 2,2-bis(p-allyloxyphenyl)-
propane. U.S. Patent 3,318,765 assigned to E.I. duPont deNemours & Co.
Fieser LF, Fieser M. 1967. Reagents for organic synthesis. John Wiley & Sons,
Inc. New York, NY, pp. 785-791.
Fisher W. 1983a. Telephone conversation between W. Fisher of FMC's Industrial
Chemicals Group and G. Hammaker, November 29, 1983.
Fisher W. 1983b. Telephone call between G. Hammaker, DPRA, and W. Fisher
(215-299-6000) of FMC Corp.
Flippen-Anderson JL, Gilardi R. 1981. Diglycidyl ether of bisphenol A
(DGEBA). Acta cryst. 837:1433-1435.
Fukushima H, Hashimoto K, Inagami M, Maeda A. 1980. composition for cover
rubber of rubber pipes or hoses; terpolymer rubber of epichlorohydrin,
ethylene oxide and an unsaturated epoxide, and a di- or tri-mercapto-s-
triazine as vulcanization agent. U.S. Patent 4,197,382 assigned to Nippon
Zeon Co. Ltd.
Goldfarb AS, Duff WW, Herrick EC, McLaughlin MP. 1980. Identification of
pollutants from chlorlnatlon and related processes. The Mitre corporation,
McLean, VA, pp. 28-30.
156
-------
Groggins PA. 1963. Unit Processes in organic Synthesis. McGraw-Hill, New
York, NY, pp. 271-274.
Guise GB, Smith GC. 1982. Gel permeation chromatography of a polyamide-epl-
chlorohydrin resin and some other cationionic polymers. J. Chromatog. 235:365-
376.
Gumraikunst. March 1980. pp. 156-164.
Gummikunst. March 1981. pp. 136-148.
Gummikunst. October 1982. pp. 563-567.
Guthrie JL, Rendulic FJ. 1975. Photocurable polyene-polythiol lacquer
composition. U.S. Patent 3,908,039, assigned to W.R. Grace & Co. CA
84(4)19377J, CA 83(26)207700n.
Hagnauer GL. 1979. HPLC and GPC analysis of Bpon 828 epoxy resins. NTIS
AD-A080-221, Springfield, VA, 11 pp.
Halasa B. 1976. Wptyw jakosci dianu na wydanosc matoczasteczkowych zywic
epoksydowych. Polimery-Towrzywa wielkoczasteczkowe 21(12):500-502
Hammaker GS. 1983. Letter to S. Arnold of Dow Chemical Company requesting
information on uses, consumption, and product residuals of epichlorohydrin.
December 19, 1983.
Hammaker GS. 1984. Letter to G.B. Parris summarizing price data from industry
and Chemical Marketing Reporter.
Hercules. 1983a. Synthetic rubber for long-life pond liners. Product bulletin
provided by N.C. MacArthur of Hercules, Inc., April 7, 1983.
Hercules. 1983b. Herclor« epichlorohydrin elastomers, hazards associated
with epichlorohydrin monomer in the handling and processing of Herclor
elastomers. Bulletin ORH-24D.
Hlldon AM, Greenhalgh PP. 1979. Epoxidatlon. U.S. Patent 4,172,840 assigned to
Interox Chemicals Ltd. London.
Houston AM. 1975. Epichlorohydrin elastomers resist environmental extremes.
Mater. Eng. 82(l):42-44.
Idson B. 1979. Biophysical factors in skin penetrations. J. Soc. Cosmet. Chera.
22:615-634.
Jones RW, Chandy KT. 1974. "Synthetic plastics," in Riegel's Handbook of
Industrial Chemistry, 7th edit. JA Kent, Editor. Van Nostrand Relnhold Co.,
New York. NY, pp. 238-300.
157
-------
Kirk-Othmer. 1978a. Encyclopedia of Chemical Technology. 3rd edit. Vol. 2,
"Amino resins and plastics," pp. 440-460.
Klrk-Othmer. 19785. Encyclopedia of Chemical Technology. 3rd edit. Vol. I,
"Adhesives," pp. 493-506.
Kirk-Othraer. 1979a. Encyclopedia of Chemical Technology, 3rd edit.. Vol. 8.
"Elastomers, synthetic (polyethers)" by EJ Vandenberg, John Wiley & Sons, New
York, NY, pp. 568-582.
Kirk-Othmer. 1979b. Encyclopedia of Chemical Technology, 3rd edit., Vol. 6,
"Coatings, Industrial, Marine, Resistant," John Wiley & Sons, New York, NY,
pp. 427-479.
Klrk-Othmer. 1980a. Encyclopedia of Chemical Technology, 3rd edit.. Vol. 9,
"Epoxy resins," John Wiley & Sons, New York, NY, pp. 267-289.
Kirk-Othraer. 1980b. Encyclopedia of Chemical Technology, 3rd edit., Vol. 10,
"Flocculating agents," pp 489-523.
Klrk-Othmer. 1981a. Encyclopedia of Chemical Technolgy, 3rd edit.. Vol. 16,
"Papermaklng additives," John Wiley & Sonj, New York, NY, pp. 803-825.
Kirk-Othmer. 1981b. Encyclopedia of Chemical Technology, 3rd edit., Vol. 13,
"Laminated and reinforced plastics," pp. 972-976.
Kirk-Othmer. 1982a. Encyclopedia of Chemical Technology, 3rd edit.. Vol. 17,
"Phenolic resins," pp. 384-412.
Kirk-Othmer. 1982b. Encyclopedia of Chemical Technology, 3rd edit., vol. 18,
"Polyester, unsaturated," pp. 588-592.
Kirk-Othmer. 1982c. Encyclopedia of Chemical Technology, 3rd edit., Vol. 18,
"Plastic building products," pp. 87-97.
Kovats T. 1983. Telephone conversation between T. Kovats of Glyco, Inc., and
G. Hammaker, November 30, 1983.
Leo A. Hanch C, Elkins D. 1971. Partition coefficients and their uses. Chem.
Rev. 71(6):525-615.
Lewis FA. July 1980. Health hazard evaluation determination report, HE
79-141-711, Fischer & Porter Company, Warminster, PA. NIOSH, Cincinnati, OH.
Lichtenwalter GD, Riesser GH. 1964. "Chlorohydrins," Kirk-Othmer Encycl.
Chem. Technol., 5:304-21. Interscience Publishers. New York (cited from
Santodonato et al., 1980).
Lowenheim FA, Moran MK. 1975. Faith, Keyes, and Clark's Industrial Chemistry,
4th edit. John Wiley & Sons, New York, NY. pp. 430-441.
158
-------
nabey W, Mill T. 1918. Critical review of hydrolysis of organic compounds In
water under environmental conditions. J. Phys. Chera. Ref. Data. 7(2):383-415.
Mat. Eng. July 1975. 82(l):42-44.
Mathtech, Inc. February 1983. Economic evaluation: Halogenated alkyl
epoxides. Mathtech, Inc., Arlington, VA.
MCP. 1982. Mannsville Chemical Products. Epichlorohydrin. In: Chemical
Products Synoposis. Cortland, NY, January 1982 (cited from Chen et al., 1981).
Merck. 1976. The Merck Index, 9th edit., Merck and Co. Rahway, NJ.
Meteyer TE, Pries V. 1980. Oxidatively stable ion exchange resins condensation
product of an epichlorohydrin and a polyamine. U.S. Patent 4,184,019 assigned
to Rohm and Haas Company.
Milby TH, Whortom MD, Stubbs HA, Ross CE, Jayner RE, Lipshultz LI. 1981.
Testlcular function among epichlorohydrin workers. Br. J. Indus. Med.
38:372-377
Mohan JG. 1977. shaking up the elastomer batting order. Automot. Ind.,
September 6, 157(4):18-23.
Morey H. 1984. Telephone conversation between J. Wittwer of DPRA and H. Morey
of Stauffer Chemical, March 1984.
Nalco. 1984. Product bulletins and safety data sheets for Nalcolyte 8105,
7135, 8108, 8100.
National Institute for Occupational Safety and Health (NIOSH). September
1976. Criteria for a recommended standard .... occupational exposure to
epichlorohydrin. U.S. Department of Health, Education and Welfare, publication
76-206. Washington, DC.
OSHA. 1983. OSHA Report OHDS 4S. August 26, 1983 for period 6/1/79 and 3/31/83.
Parr is GE, Borghi L, Engelkemeir A. 1983. An overview of the exposure
potential of commercial flame retardants. Dynamac Corporation, Rockville, MD.
pp. 70-106.
Pegum JS. 1979. Penetration of protective gloves by epoxy resin. Contact
Dermatitis, 5:281-283.
Pilny M, Mleziva J. 1977. Reactive Verdunner for Epoxidharze. Kunststoffe 67
(12):783-790
Pilorez BH. 1962. Allyl chloride and derivatives. Chapter 23. JS Sunce
editor, Reinhold Publishing Corp., New York. NY, pp. 698-705.
Petroleum Refiner. 1955. 34(12):158.
Piringer VO. 1980. Die kinetik der Hydrolyse von Epichlorhydrin in Verdunnten
Wasserigen Losungen. Deuts. Lebensmit.-Rundsch. 1:11-13.
159
-------
Pritchard j, Siddiqui IA. 1973. Activation parameters and mechanism of the
acid-catalyzed hydrolysis of epoxides, J.C.S. Perkin II, 452-457.
Protzel A. 1981. Carbofuran Intermediates. IR-244. TSCA Interagency Testing
Committee, Enviro Control (Dynamac), Rockville, HD.
Processes Research, Inc. (PRI). 1972. Air pollution from chlorination
processes. NTIS NO. PB 218 048, Springfield, VA.
R & P News. December 1981. pp. 16-19.
R & P News. October 1982. p. 25.
Riddick JA, Hunger VB. 1970. Organic solvents. John Wiley & Sons, New York,
NY, p. 365.
Roberts JD, Caserio MC. 1965. Basic principles of organic chemistry, W.A.
Benjamin, Inc. New York, NY. pp. 906-908.
Roberts MS, Anderson RA, Swarbrick J. 1977. Permeability of human epidermis to
phenolic compounds. J. Pharm. Pharmacol. 29(ll):677-683.
Robinson AE. 1962. U.S. Patent 3,026,270 assigned to Hercules, Inc.
Robinson AE, Willis WD. 1967. U.S. Patent 3,341,491 assigned to Hercules, Inc.
RTECS. Registry of Toxic Effects of Chemical Substances (RTECS). June 1983.
U.S. DHHS.
Rubber Age. September 1972. pp. 39-48.
Saletan DI, Young RS, Pledger WR. 1977. Process for production of glycerin.
U.S. Patent 4,053,525 assigned to Shell Oil Company.
Saves'kin VH, Gontarevskaya NP, Borbulevich AI, Shevchuk LN, Luner LV. 1979.
Allyl ethers of phenols or bisphenols. USSR patent SU 690000, October 5, 1979.
Chera. Abst. 92(13)110660x.
Santodonato J, Lande SS, Howard PH, Orzel D, Bogyo D. March 1980.
Investigation of selected potential environmental contaminants:
epichlorohydrin and eplbromohydrin. EPA 560/11-80-006. Syracuse Research
corporation, Syracuse, NY.
Scheer E. 1978. Epichlorohydrin elastomers in the vanderbilt Rubber Handbook.
R.O. Babbit editor. RT Vanderbilt Co., Norwalk, CT, pp. 275-294.
Scheuplein RJ. 1965. Mechanism-of percutaneous absorption. I. Routes of
penetration and the influence of solubility. J. Investigative Dermatol
45(5):344-346.
160
-------
Scheuplein RJ. 1967. Mechanism of percutaneous absorption II. Transient
diffusion and the relative importance of various routes of skin penetration.
J. Investigative Dermatol. 48(12):79-88.
Scheuplein RJ, Blank IH. 1973. Mechanisms of percutaneous absorption IV.
Penetration of non-electrolytes (alcohols) from aqueous solutions and from
pure liquids. J. Invest. Dermatol. 60:286-296.
Shell Oil Co. 1969. Technical Bulletin No. 1C 69-16 Epichlorohydrin.
Shell. 1982. Shell Chemical Company Technical Bulletin SC:106-82:7-15.
Shell. 1983. Material Safety Data Sheets for Bpon Resin 828, Epon Resin 871,
Epon Resin 815, and butyl glycidyl ether.
Shih JS, Brandt JF, Zussman MP, Tirrell DA. 1982.
Poly[(2-chloroethyl)oxirane], poly[(3-chloropropyl)oxirane] and
poly[(4-chlorobutyl)oxiranej: New polyether elastomers of improved chemical
reactivity. J. Polyra. Sci. 20:2839-2849.
Sittenfield M, Herbst R, Severn D. 1980. organics pollution study,
hydrocarbon chlorinatlon, Vol. I. Romar Associates, Philadelphia, PA, pp.
3-32, 4-20, Appendix Exhibit A-18.
Society of Plastics. 1983 Edition. Facts and Figures of the U.S. Plastics
Industry. The Society of the Plastics Industry, inc., N.Y.
SRI International. 1983. Directory of Chemical Producers, United States of
America, Menlo Park, CA.
Sury YS. 1983. Process for removing trace amounts of epichlorohydrin from
heat sensitive glycidyl products. U.S. Patent 4,395,542 assigned to Ciba-Geigy
Corporation.
Systems Applications, Inc. (SAI). 1982. Human exposure to atmospheric
concentrations of selected chemicals. Appendix A-13 Epichlorohydrin. EPA
Office of Air Quality Planning and Standards, Research Triangle Park, NC.
Tassignon JP, Bos GD. Cralgen AA, Jacquet B, Kueng HL. Lanouziere-Simon C,
Pierre C. 1983. Mortality in an European cohort occupationally exposed to
epichlorohydrin (ECH). Int. Arch. Occup. Environ. Health 51:325-336.
The Soap and Detergent Association, Statistics. April 12, 1983. Glycerin
GL-3b; June 2, 1983, Glycerin End Use Survey.
Thigpen HH, Taylor WE, Schnizer AW. 1976. Peracetic acid oxidation of amines
to amine oxides. U.S. Patent 3,957,873 assigned to Celanese Corporation.
Thomas RM. 1958. Glycerol production. U.S. Patent 2,858,345 assigned to Olin
Mathieson Chemical Corporation.
161
-------
Tymstra FT. 1952. Production of glycerin. U.S. Patent 2,605,293 assigned to
Shell Development Company.
USEPA. 1977. industrial profiles for environmental use. Chapter 6. EPA
600/2-77-023f. PB281-478.
Vandenberg BJ. 1964a. U.S. Patent 3,158,580 assigned to Hercules, Inc.
Vandenberg EJ. 1964b. U.S. Patent 3,158,581 assigned to Hercules, Inc.
Vandenberg BJ. 1964c. U.S. Patent 3,135,705 assigned to Hercules, Inc.
Vandenberg EJ. 1965. U.S. Patent 3,219,519 assigned to Hercules, Inc.
Vandenberg, EJ. 1967. Hydroxylended copolymers of an epihalohydrln. US Patent
3,310,504 assigned to Hercules. Inc.
Vandenberg EJ. 1983. The development of epichlorohydrin elastomers. Chemtech,
August:474-477.
Van Eenam DN. 1980. Vet strength polymers; epichlorohydrin-tertiary araine
catlonic salt polymer as an additive for celluloslc substrates. U.S. Patent
4,233,417 assigned to Monsanto Co.
Verschueren K. 1977. Handbook of environmental data on organic chemicals. Van
Nostrand Reinhold Co. New York, NY. pp. 13-17.
Whyte DO, Korpl EO. 1962. Alkyl glyceryl ether sulfonate mixtures and
processes for preparing the same. U..S Patent 3,024,273 assigned to Proctor
and Gamble Co.
Whyte DD. 1976. Alkyl glyceryl ether sylfonates. Anionic surfactants (Chapter
14) in Surfactant Science Series Vol 7, part 2 edited by WM Linfield, Marcel
Dekker, New York, NY. pp. 483-94.
Wittwer J. 1984. Telephone conversations between Proctor and Gamble and Dow
Chemical Company sales representatives and J. Wittwer, DPRA, March 14, 1984.
Wolf P, Weissenborn D. 1971. Use of 2,2-bis(4'-allyloxyphenyl)propane for azo
dye reactive dyeing of cotton. Z. Chem. 11(11):425-6.
World Oil. March 1976. pp. 65-68.
Zahir SAC, Wyler S. 1977. Epoxy resin mixtures. German Patent DE 2726821
assigned to Ciba-Geigy A.-G.
162
------- |