EPA 560/2-78-008
Investigation of Selected Potential
Environmental Contaminants:
Butadiene and Its Oligomers
By:
Lynne M. Miller
December 1978
Final Report
Project Officer:
Frank J. Letkiewicz
Prepared For:
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Franklin Research Center
A Division of The Franklin Institute
The Benjamin Franklin Parkway. Phila., Pa. 19103 (215) 448-1000
-------
EPA 560/2-78-008
Investigation of Selected Potential
Environmental Contaminants:
Butadiene and Its Oligomers
By:
Lynne M. Miller
December 1978
Final Report
Document is available to the
public through the
National Technical Information Service
Springfield, Virginia 22151
Prepared For;
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Franklin Research Center
A Division of The Franklin Institute
The Benjamin Franklin Parkway. Phila., Pa. 19103 (215) 448-1000
-------
NOTICE
This report has been reviewed by the Office of Toxic Substances,
U.S. Environmental Protection Agency. and approved for publication.
Approval does not signify that the contents necessarily reflect the
views and policies of the Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement
or recommendation for use.
-------
PREFACE
TABLE OF CONTENTS
LIST OF TABLES
LIST OF FIGURES
EXECUTI VE SUMMARY
1.
PHYSICAL AND CHEMICAL DATA
A.
Chemical Structure
B.
Properties of Pure Material
C.
Properties of the Commercial Material
D.
Chemical Reactions Involved in Use
1.
Butadiene
a.
Polymerization
b.
Dimerization to Vinylcyclohexene and Cyclooctadiene
c.
Tr~erization to Cyclododecatriene
d.
Diels-Alder Reaction with Other Adducts
e.
Other Reactions
f.
Photochemistry
2.
o ligomers
II. ENVIRONMENTAL EXPOSURE FACTORS
A.
Production Processes
1.
Production
a.
Butadiene
1)
2)
Roudry Processes
Oxidative Dehydrogenation
3)
4)
Co-Product in Ethylene Production
Extractive Distillation
ii
Page
viii
ix
xi
xiii
1
1
3
6
8
8
8
8
11
12
12
13
15
17
17
17
17
17
22
23
25
-------
B.
b.
o ligomers
25
29
3.
Quantity Produced
29
1.
Domestic Producers and Production Sites
2.
b.
c.
3.
31
Foreign Importers and Producers
33
5.
Market Pri ce
36
Market Trends
4.
37
Butadiene
37
2.
4.
6.
Use
1.
g.
h.
2.
a.
Styrene - Butadiene Copolymers
39
b.
44
Polybutadiene
c.
Chloroprene/Neoprene
44
d.
Nitrile Rubber
48
e.
Adiponitrile/HMDA
48
f.
Acrylonitrile-Butadiene-Styrene Resins
49
Miscellaneous Uses
50
Projected Uses
52
i.
Alternatives to Use
53
Oligomers
53
C.
Entry Into the Environment
From Production
54
54
From End Product Manufacture
54
a.
Workroom Levels
54
Air Emissions
60
Water Effluent
64
From Product Use
65
,- ,
From Storage and Transport
65
Hi
-------
S.
From Other Sources
65
a.
b.
c.
d.
Gasoline
66
Urb an Air
66
Cigarette Smoke
69
Fire
69
71
D.
Waste Handling
75
E.
Fate and Persistence in the Environment
7S
1.
Degradation in the Environment
7S
b.
2.
a.
Biological Degradation
Chemical Degradation
7S
1)
2)
Atmospheric Reactions
7S
Reaction with Water
80
1.
2.
Transport and Persistence
80
F.
Analytical Detection Methods
80
Butadiene
80
a.
In Air
80
b.
In Water
83
c.
In Polymers
83
d.
In Biological Material
84
e.
In Process Streams
84
Impurities in Butadiene
85
III.
BIOLOGICAL EFFECTS
89
A.
Humans
1.
2.
89
Acute Toxicity
89
a.
Signs and Symptoms
89
b.
Effects on Psycho-motor Tests
91
Organoleptic Thresholds
92
iv
-------
3. Occupational Exposure 93
a. Butadiene 93
b. Vinylcyclohexene 100
B. Nonhuman Mammals 100
1. Toxicolo~y 101
a. Butadiene 101
1) Acute Toxicity 101
a) Lethal Doese 101
b) Narcotic Effects 101
2) Subacute Toxicity 104
a) Inhalation Exposure 104
b) Oral Administration 109
3) Chronic Toxicity 110
a) Inhalation Exposure 110
b) Oral Administration 116
b. Butadiene Containing Mixtures 1.17
1) Butadiene-a Methylstyrene 114
2) Butadiene-Toluene 121
c. Viny1cyclohexene 121
1) Acute Toxicity 121
2) Chronic Toxicity 123
3) Carcinogenic Potential 123
d. Cyclooctadiene and Cyclododecatriene 123
2. Biological Fate 125
a. Butadiene 125
1) Absorption 125
2) Dis tribu tion 125
v
-------
3)
Metabo lism
126
b.
Cyclooctadiene
128
C.
Other Animals
129
D.
Plants
129
IV. SPECIAL EFFECTS
V.
132
A.
Mutagenicity
132
1.
Butadiene
132
2.
Possible Metabolites
135
B.
Carci nogenic i ty
136
1.
Butadiene
136
2.
Possible Metabolites
136
3.
Oligomers
136
REGULATIONS AND STANDARDS
140
A.
Federal Regulations
140
1.
Occupational Safety and Health Administrations
140
2.
Department of Transportation
140
3.
Environmental Protection Agency
140
4.
Food and Drug Administration
141
B.
State Regulations
141
1. Workplace
2. Food Contact
3. Water Quality
4. Air Emissions
141
141
141
145
C.
Foreign Countries
145
1.
United Kingdom
145
2.
West Germany
146
3.
Japan
146
vi
-------
4.
Canada
146
5.
Others
147
D.
Other Standards
147
E.
Handling and Storage Practices
147
1.
Handling, Storage, and Transport
147
2.
Personnel Exposure
148
3.
Accident Procedures
149
VI. EXPOSURE AND EFFECTS POTENTIAL
150
A.
Butadiene
150
B.
o ligomers
152
TECHNICAL SUMMARY
154
BIBLIOGRAPHY
159
CONCLUSIONS AND RECOMMENDATIONS
174
APPENDIX A - Sources Employed
176
vii
-------
PREFACE
This report is a survey and a summary of the literature on butadiene and
its oligomers available through June, 1978.
Major aspects of chemistry, com-
mercial production, environmental exposure, biological effects and regulations
are reviewed.
Appendix A lists sources of information employed.
This document was prepared by the Franklin Research Center for the U.S.
Environmental Protection Agency unger ~ontract number 68-01-3893.
viii
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Table
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
LIST OF TABLES
Nomenclature and Other Identifiers of Butadiene and Its
Oligomers
Physical Properties of Butadiene
Physical Properties of Butadiene Oligomers
Specifications and Typical Inspections for 1,3-Budatiene
Inhibited with R-Tertiary Butyl Catechol
Impurities in Pure-Grade 1,3-Butadiene
Structure of Several Butadiene-Containing Polymers
Products of Photochemical Reactions of Butadiene
Composition of Products from Photosensitized Dimerization of
Butadiene
1,3-Butadiene Producers in the United States
Typical Ultimate Yields of Butadiene from a Normal Butane
Peed Stream (Houdry Process)
Average Yield of By-Product Butadiene from
Ethylene Feedstocks
Reaction Conditions and Selectivity in the Production of
Cyclooctadiene and Cyclododecatriene
U.S. Production and Sales of Butadiene
Imports of Butadiene into the United States
Butadiene Supply in the United States
European Butadiene Capacity and Production for 1978
Butadiene Demand in the United States
Producers and Capacities for Major Products Using Butadiene
Exports of U.S. Butadiene Monomer
Derivatives of Cyclooctadiene and Possible Uses
Derivatives of Cyclododecatriene and Possible Uses
ix
Page
1
4
5
6
7
9
14
14
18
21
23
28
30
32
34
35
38
40
51
55
55
-------
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
Air Concentration of Butadiene Oligomers and Other Compounds
in a Passenger Tire Curing Room
Levels of Butadiene in the Workplace at Production Facilities
in the U.S.S.R
Atmospheric Emission Source Summary from SBR
Analysis of Automobile Exhaust for 44 Hydrocarbons,
Including 1,3-Butadiene
Ambient Air Levels of 1,3-Butadiene
Ambient Air Analyses for 44 Hydrocarbons, Including
1,3-Butadiene, from the Central Los Angeles Business District
Characterization of Waste Streams from Butadiene Manufacture
Samples of Ambient Air Analyzed for Butadiene
Photooxidation of 1,3-Butadiene and Nitric Oxide
Gas Chromatographic Analysis of Butadiene Process Streams
and Gas Phase Effluent from an Ethylene Plant Using
Naphtha Feedstock
Effect of Temperature on Vinylcyclohexene Formation in
Gas Chromatograph Vaporizer
Epidemiology Studies for Rubber Workers
Acute Lethal Concentration (LC) Values for 1,3-Butadiene
Effect of Inhaling Varying Mixtures of Butadiene-oxygen
in Mice
Effect of Inhaling Butadiene in Rabbits
Serum Protein in Rats After Chronic Exposure to Butadiene
Serum Cholinesterase Activity in Rabbits After Chronic
Inhalation Exposure to Butadiene
Effect of Chronic Inhalation of Butadiene by Rats, Rabbits,
and Guinea Pigs
Chronic Feeding of Butadiene to Rabbits for 7 Months:
Effect on Serum Fructose-Diphosphate Aldolase Activity
and Hemoglobin
Effect of Chronic Inhalation of Mixtures of Butadiene-
Alpha-Methylstyrene in Rats
x
59
61
62
67
68
70
72
76
78
86
88
94
102
102
103
112
112
113
117
119
-------
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
Figure
1.
2.
3.
4.
5.
Range-Finding Toxicity Data for 4-Vinylcyclohexene
Distribution of Butadiene After Exposure to LC50
Distribution of Butadiene in the Brain and Liver of
Rats at Several Time Intervals After Acute Exposure
Distribution of Butadiene in the Central Nervous System
and Liver of Acutely Intoxicated Cats
Excretion of Conjugates in Urine of Rats and Rabbits after
Oral Dosing with 1,5-Cyclooctadiene
Effect of Butadiene with Either Ozone or Oxides of Nitrogen
on Plants
Mutagenic Effect of Butadiene on Strains of Salmonella
typhimurium in the Presence and Absence of a Fortified
S-9 Fraction
Carcinogenicity of Butadiene Monoxide and Diepoxybutane in
Male Swiss-Millerton Mice
Carcinogenicity Testing of Vinylcyclohexene and the
Rydroperoxide of VCR in Male Swiss-Milleton Mice
Effluent Limitations for the Manufacture of Budatiene by
Oxidative Dehydrogenation
Regulations for Butadiene Food Contact and Workplace
Standards in Selected States
Water Standards for Butadiene in Selected States
Air Standards for Butadiene in Selected States
LIST OF FIG1JRES
Solubility of Butadiene
Houdry Process for the Dehydrogenation of n-Butane
A Process for the Production of Ethylene
Phillips Furfural Extraction Process for Butadiene
Toyo Soda (Japan) Process for Cyclooctadiene and
Cyclododecatriene
xi
122
127
127
128
129
131
134
137
139
142
142
143
144
Page
3
21
22
26
27
-------
6.
7.
8.
9.
10.
11.
Production of Emulsion Polymerized Rubber and Resultant
Wastewater Generation
42
Production of cis-Po1ybutadiene
45
Production of Cloroprene from Butadiene
47
Butadiene Production Process Identifying Waste Emission
57
Effect of Butadiene on Cholinesterase Activity of
Whole Blood of Rats Exposed Continuously to
Butadiene for 81 Days
106
Effect of Butadiene on Blood Pressure of Rats Exposed
Continuously to Butadiene for 81 Days
107
xii
-------
EXECUTIVE SUMMARY
Butadiene (BD) is a reactive gas used primarily in the production of rub-
bers and resins.
Over 3 billion pounds are produced annually in the U.S.
Among other reactions it undergoes self-condensation to form cyclic oligo-
mers,
such as 4-vinylcyclohexene, 1,5,9-cyclododecatriene and 1,5-cyclo-
octadiene.
The latter is used primarily as a precursor to nylon; the other
oligomers are less important commercially.
Vinylcyclohexene, however, is a
contaminant in butadiene.
Limited monitoring data indicate that low levels of butadiene enter the
environment during production, end-product use, storage and transport.
It has
been identified as a minor constituent of urban air and gasoline.
The high
degree of chemical reactivity of butadiene, including reactions with light,
ozone, and nitrogen oxides, precludes environmental persistence.
In humans, exposure to butadiene vapor may result in lethargy and drowsi-
ness, as well as irritation to the eyes and mucous membranes.
Skin contact
may cause frostbite due to rapid evaporation.
There have been no reports in
the U.S. or Western Europe of long-term effects of butadiene arising from
occupational exposure.
Poorly documented cases of gastrointestinal tract, and
circulatory and nervous system disorders have been reported in Russian syn-
thetic rubber workers; butadiene has been implicated as a causative factor.
Based primarily on law toxicity to laboratory animals, occupational
exposure in the U.S. is limited to 1,000 ppm BD (2,200 mg/m3) (8-hour
time-weighted average).
In laboratory mammals, butadiene intoxication may
cause narcosis.
In long-term studies, few adverse effects were reported by
American investigators who exposed animals to high levels of butadiene (up to
3
14,807 mg/m ) for as long as 8 months.
Several Russian investigators,
xi:.i
-------
however, reported adverse effects in rats exposed to only 30 mg/m3 for less
than 3 months.
Some of these changes included decreased weight gain,
decreased activity, enzyme and blood alterations, and organ changes
(especially in the lung, spleen, kidney and heart).
No tests for
carcinogenicity are available for butadiene.
In a recent study, butadiene showed mutagenic activity in two of 6 bac-
terial strains tested.
Butadiene has a low toxicity to plants.
Its effects
on marine animals are unknown.
Few toxicity data are available for butadiene oligomers.
Toxic effects on
the skin have been noted for vinylcyclohexene, cyclooctadiene and cyclododeca-
triene in mammals.
xiv
-------
1.
PHYSICAL AND CHEMICAL DATA
A.
Chemical Structure
1,3-Butadiene is a conjugated diene of the following structure:
CRZ =CR-CR=CRZ .
Cis and trans conformations are in equilibrium at room
temperature, but trans predominates (Aston and Szasz, 1946).
Bond distances
were reported by Almenningen et ale (1958), among others, as:
C-H, 0.1082 nm
C-G, 0.1483 nm; and C=C, 0.1337 nm.
Butadiene reacts with itself in the presence of free-radical inhibitors
yielding low molecular weight cyclic oligomers.
Examples of butadiene
oligomers are given below:
4-Vinylcyclohexene (VCR)
~
1,5,9-Cyclododecatriene (CDT)
u
1,5-Gyclooctadiene (COD)
o
1,Z-Divinylcyclobutane
0:
Synonyms and other identifiers of butadiene and its oligomers are given in
Table 1.
1
-------
Table 1
Nomenclature and Other Identifiers of Butadiene and OligomerB
Chemical Abstracts Service
9th Collective Index name:
1,3-Butadiene
Cyc lobutane,
1-2-diethenyl
1,5,9-Cyclododeca-
trienea
1,5-Cyclo-
octadiene
CAS Registry No.1
106-99-0
EPA Toxic Substance
Substance Control Act
List NOI
R037-0754
Synonyms:
Alpha,GalDDa-
Butadiene
Biethylene
Bivinyl
Buta-l, J-Diene
Butadiene
Divinyl
Erythrene
Pynolylene
Vinylethylene
Cyc 1 ohe xene ,
4-Ethenyl-8
100-40-3
ROJO-6445
Butadiene Dimer
l-Ethenyl-
cyc1 ohexene
1,2,3,6-Tetra-
hydrostyrene
4-Vinyl-l-
cyc lohexene
I-Vinylcyc1o-
hexene
I-Vinyl-J-
cyclohexene
I-Vinyl-Cyc1o-
hexene-J
VCH
2422-65-7; cia:
16177-46-1 ;
trans:
655J-46-6
111-78-4; Z,Z:
1552-12-1 E,ZI
5259-71-2
4904-61-4; Z,Z,Z:
47J6-46-5; E,Z,Z:
2765-29-9; E,E,Z:
706-31-0; E,E,E:
676-22-2
R161-6363
8041-6655
Divinylcy-
c10butane
CDT
COD
Molecular Formula: C4"6 Ca"l2 Ca")2 C12"16 CaH12
WiBweaaer Line 1U 2 UI L6UTJ 0101 L4TJ AWl BIUl L-12-U EU lUTJ L8U EUTJ
Notation: L4TJ AWl CWI
LUTJ AWl XlUl
a referred to in text 8S 4-vinylcyclohexene or vinylcyclohexene
b referred in 8th collective index as t,t,t for Z,Z,Z; c,t,t for E,Z,Z; c,c,t for E,E,Z; c,c,c for E,E,E
-------
B.
Properties of the Pure Material
Butadiene is a colorless gas at room temperature with a mild aromatic
odor.
It is only slightly soluble in water (Figure 1), more soluble in
methanol and ethanol but readily soluble in acetone, ether, benzene, carbon
tetrachloride, chloroform, furfural etc. (Kirshenbaum and Kahn, 1964).
It is
extremely flammable, forming explosive mixtures with air at about 2.0 to 11.5
percent by volume (explosive range).
Ignition can occur readily as the flash
point is below OOC.
Physical properties of butadiene and its oligomers are
summarized in Tables 2 and 3.
0.22
0
0.20 .
z
...J
0 0.18
en
01 0.16
0
0
, 0.14
01
.; 0.12 .
t-
== 0.10
en
:;:)
...J 0.08
0
en ./;.
0.06
0.04 /.~
0.02
0 - -
-40 -20 0 20 40 60 80
TEMPERATURE (OC)
Figure L
Solubilit] of Butadiene. Closed Circle: solubility of
water in liquid butadiene; Open Circle: solubility of
gaseous Dutadiene at 760 rom Hg in water. (adapted from
Bailey, 1971)
-3
-------
Table 2
Physical Properties of Butadiene
(Kirshenbaum and Kahn, 1964)
Boiling Point, 760 mm Hg
Critical Temp.
Critical Press.
Density
20°C
25°C
Flash Point
Flammable Limits
Freezing Point, 760 mm Hg
Heat of Formation, 25°C
gas
liquid
Melting Point
Molecular Weight
Solubility in Water
Vapor Density
Vapor Pressure
% Volatile
Weight/U.S. gallon, l60c
Conversion Factors
Colorless gas
mild aromatic
- 4.4130C
152°C
42.7 atm.
or liquid,
odor
Appearance
0.6211 g/ml
0.6149 g/ml
< -18°C
2-11.5% by
-108.9150C
volume in air
26.33 kcal/mole
21. 21 kcal/mole
-108.91
54.09
0.037 wti. at 10°C
1. 88 (air = 1)
1900 mm, 20°C
100%
5.229 lbs.
1 ppm = 2.21 mg/m3
1 mg/m3 = 0.45 ppm
4
-------
Boiling Point (OC)
Flash Point
Freezing Point
Melting Point
Molecular Weight
In
Refractive Index,
nD20
Solubility
Vapor Pressure
Weight/U.S. Gallon, 160C
a
Properties for
(t,t = 1.4975;
at 22 mm Hg
at 760 nun Hg
at 10 nun Hg
at 127 nun Hg
b
c
d
e
Table 3
Physical Properties of Butadiene Oligorners
(Wilke, 1963; Weast, 1975; Bengelsdorf et al., 1960,
McAuliffe, 1966; Coffey, 1968)
Vinylcyclohexene
50-52b
145c
21°C, open cup
-109°C
-101°C
108.18
1.4915
inuniscible with
water, miscible
with ether, ben-
zene and methanol;
solubility in
water: 50 t 5
g/106g H20
20 nun at 31°C
1,5,9-Cyclododecatriene
Z,Z,Z Z,Z,E
96d
98d
80°c for mixture of
isomers
+34°c
-16.8oC
162.27
162.27
1.5005
1. 5078
soluble in hydrocarbons
7.35 lb.
7.35 lb.
isomers not specified except for refractuve index
c,c = 1.4910
,E,E,Z
106d
-9 to -8oC
162.27
1.5129
7.35 lb.
1,5-Cyclooctadienea
91. Se
37.8
-70
1 08 . 1 8
(a)
soluble in
hydrocarbons
5 nun Hg at 20°C
7.35 lb.
-------
C.
Properties of the Commercial Material
Commercial grade butadiene is >98% pure.
Specifications for butadiene
available from one manufacturer are given in Table 4.
Vinylcyclohexene is
present as an impurity at a maximum of 0.2%.
Other impurities include vinyl
acetylenes, aldehydes, Cs hydrocarbons, peroxides, sulfides and nonvolatile
matter.
DiCorcia et ale (1977) identified 20 impurities in pure-grade
butadiene (Table 5).
An inhibitor of peroxide formation (usually 100 ppm
£-tertiary butyl catechol) is added when butadiene is offered for shipment.
Table 4
Specifications and Typical Inspections
for 1,3-Butadiene Inhibited with
R-Tertiary Butyl Catechol (Exxon, 1973)
Specification
Typical
Inspections
Acetylenes, alpha, as vinyl acetylenes (ppm)
Acetylenes, vinyl (ppm)
Appearance Clear and Free of
Butadiene Dimer (weight percent)
Carbonyl, as acetaldehyde (ppm)
Conjugated Diene, as 1,3 butadiene (wt %)
Hydrocarbons - Cs (weight percent)
Nonvolatile Matter (weight percent)
Peroxides, as hydrogen peroxide (ppm)
Sulfur, as hydrogen sulfide (ppm)
500 Max
10 Max
Suspended Matter
0.2 Max
SO Max
99.0 Min
0.05 Max
0.1 Max
10 Max
10 Max
150 Max
0-5
0.01
<20
99.1
0.01
0.01
Nil
Nil
Vinylcyclohexene is available as technical grade (95% purity) or research
grade (99% purity).
The most likely contaminants are cyclooctadiene and the
hydroperoxide of vinylcyclohexene (1-hydroperoxy-4-vinylcyclohexene) (lARC,
1976).
Non-volatiles are present at 0.03% by weight.
An oxidation inhibitor
(50 ppm t-butylcatechol) is added.
1,5,9-Cyclododecatriene and 1,5-cyclooctadiene are available commercially
at a purity of 98% by weight.
Both products are inhibited with
6
-------
Table 5
Impurities in Pure-Grade
(DiCorcia et al., 1977, DiCorcia
1,3-Butadiene
and Samperi, 1975)a
Impuritiesb Levels (ppmJ
methane 10
ethane 7
ethylene 12
acetylene 0.3
cyclopropane 0.4
propane 5
propene 46
propadiene 70
propyne 13
isobutane n.r.
neo-pentane n.r.
butane 210
I-butene 5500
isobutene 2500
1,2-butadiene n.r.
2-cis-butene 270
2-trans-butene 390
I-butine n.r.
I-butene-3-ine n.r.
a List of impurities taken from both references; levels are repor~ed in
DiCorcia and Samperi (1975) only, so levels for all impurities in Table
5 are not known, and identified as n.r. (not reported).
b Identification was carried out us~ng a gas chromatograph equipped with
a flame ionization detector.
7
-------
t-butylcatechol (at 60 ppm and 50 ppm, respectively).
Commercial cyclodo-
decatriene consists of the trans, trans, trans (56%) and the cis, trans, trans
isomers (36%).
Vinylcyclohexene is an impurity in commercial cyclooctadiene
(Reichel et al., 1963), and nonvolatiles total 0.03% by weight (Citco, 1969).
Reactions Involved in Use
D.
1.
Butadiene
Butadiene is probably one of the most thoroughly investigated chemicals;
several thousand reactions of butadiene have been recorded in the literature
(Baily, 1971).
Commercial use primarily involves polymerization, but other
industrial reactions are also summarized in the sections which follow.
a.
Polymerization
Butadiene polymers include polybutadiene, styrene-butadiene rubber and
latices (SBR), acrylonitrile-butadiene or nitrile rubber, and acrylonitrile-
butadiene-styrene (ABS) resins.
Structures of these butadiene polymers are
shown in Table 6.
Manufacture and use are discussed in Section II-A.
b.
Dimerization to Vinylcyclohexene and Cyclooctadiene
Butadiene undergoes a wide variety of Diels-Alder reactions, the addition
of an activated olefin (dienophile) to the 1,4 positions of a diene forming a
six numbered ring.
An example is dimerization, in which butadiene acts as
both a diene and a dienophile to form 4-vinylcyclohexene.
Catalysts are not
required for dimerization nor is the reaction inhibited by t-butylcatechol,
the peroxide inhibitor added to commercial butadiene (Saltman, 1965).
Vinylcyclohexene is always found as an impurity in butadiene and is a common
8
-------
Table 6
Structure of Several Butadiene-Containing Polymers
Name
Structure
Polybutadiene
-CH2 CH:zicH2 CH2 t CH:z CH2-
\ / \ I \ /
CW=CH CH=CH CH=CH
x
cis-l,4-Polybutadiene
r'l:l
1.2-Polybut3diene
f~~~C\H 1
l CH2 x
trans-I.4-Polybutadiene
Styrene-Butadiene
[ H H. H H. 1
-c-c=-c-C-C-C-
H. H I
o
Acrylonitrile-Butadiene-
Styrene
-Ii Hd-H H H Hi-fi H~
I I I I \ \ I I
-c -c=c-c -c
I I I I I I
H CN H H 'I H C H .
,.
.\cryloDitrile Butadi.... Sty~.
9
-------
problem in handling and storage.
The rate of dimer formation is a function of
temperature, as shown below (Exxon, 1974):
temperature
wt % butadiene dimerized/hr
(oC)
20
0.00015
40
0.0014
60
0.013
80
0.12
100
1.1
At 460C, about 1.6% of butadiene is dimerized after 30 days storage, but
about 16% of butadiene is dimerized at 750C after this period.
Because of
this, butadiene is usually stored at low temperatures (Exxon, 1974).
The dimerization reaction has been used commercially to prepare
vinylcyclohexene by heating butadiene under pressure (Hillyer and Stallings,
1956) :
2CH =CH-CH=CH .~
2 2
v
Stahly (1951) reported improved yields using a metal naphthenate salt
catalyst.
Butadiene was heated in liquid phase at 150-l60oC and 40-100
a~ospheres for a few minutes in the presence of a metal naphthenate salt
catalyst, to yield more than 60% vinylcyclohexene by weight of butadiene
treated.
Johnson (1949) prepared the dimer by heating butadiene in the vapor
phase to 37S-4500C in the presence of silicon carbide.
Candlin and Janes
(1968) reported high yields at 1000 using iron carbonyls.
Other catalysts
described in the patent literature include dicyclopentadienyl nickel and
nickel dicarbonylphosphite complexes (Bailey, 1971).
According to Tkatchenko
10
-------
(1977) the most selective catalyst systems are based on cobalt, rhodium or
platinum.
Besides six-membered rings formed by Diels-Alder reactions, butadiene also
forms rings of other sizes.
The cyclodimerization of butadiene results in
1,5-cyclooctadiene (COD).
Ziegler prepared mixtures containing
vinylcyclohexene and 15% COD (Ziegler and Wilms, 1947).
Reed (1954) reported
yields of 30-40% cis,cis COD and 10% vinylcyclohexene in a reaction time of 4
hours us~ng Reppe catalysts based on nickel carbonyl.
Wilke (1963) attempted
to improve yields by further developing the nickel catalyst system.
Nickel
reduced in the presence of triphenylphosphine catalyzed cyc1odimerization to
yield a mixture of 70% COD, 10% cyc1ododecatriene and 20% viny1cyc1ohexene.
A
number of other nickel catalysts have been described; among them are nickel
tetracarbony1 with tri-~-cresyl phosphite and also acrylonitrile and
tri-~-to1y1 phosphite (summarized in Baily, 1971).
Thermal dimerization
without catalysts will yield primarily cis,cis-cyclooctadiene,
4-vinylcyclohexene and trans-1,2-diviny1cyc1obutane (Huybrechts et al., 1977)
c. Trimerization to Cyclododecatriene
Trimerization of butadiene will yield cyc1ododecatriene (CDT) in the
presence of metal-a1kyl-transition metal catalysts.
Wilke (1963) prepared CDT
in a 90-95% yield from butadiene in the presence of a diethy1aluminum hydride
catalyst at 400C and normal pressure.
Other catalysts described by Wilke
(1963) for obtaining high yields were prepared from calcium hydride, aluminum
chloride in both benzene and titanium tetrachloride and from chromyl chloride
and triethy1aluminum in benzene.
Several stereoisomers of cyclododecatriene
are possible (Table 3); the products depend primarily on the catalyst system.
11
-------
Diels-Alder Reaction with Other Adducts
d.
In addition to dlinerization, other Diels-Alder reactions are of commercial
importance.
Butadiene reacts urea maleic anhydride to form
1,2,5,6-tetrahydrophthalic anhydride (TEPA) which is used in the preparation
of the fungicide Captan (Kittleson, 1951):
(Xc/0 (X!?
I '0 NH. , I tH
CI C
-But:~d~~?e-male~£ ~ ~
anhydride add_~ct
CI,CSCI
/P
cf
ex >SCCI3
C~
~O
Captan
Another commercial product based on a Diels-Alder reaction of butadiene is the
insecticide Phygon (Kittleson, 1951):
CN°
I 1+
CI
o
CH =CHCH=CH
2 2
-Yvr
C~
o Phygon
Also of use commercially is the reaction of butadiene and naphthalene in the
producti.on of anthraquinone (Weyker et al., 1960).
There is a large
literature on Diels-Alder dienophiles that react with butadiene but these are
primarily of laboratory interest; Baily, (1971) lists over 300 dienophiles in
his review of butadiene.
e.
Other Reactions
Chlorination or hydrocyanation of butadiene is used in the manufacture of
adiponitrile, an intermediate in the production of nylon 6,6 (See Section
II-B-l-e) .
Butadiene is also chlorinated to make chloroprene (See II-B-l-c).
The reaction of butadiene and dihalocarbenes is used in the synthesis of
vinyldihalocyclopropanes.
Hydrogenation of butadiene gives butenes and
butane, the ratio depending on the catalyst used (Kirchenbaum and Kahn, 1964).
12
-------
A cyclization reaction of industrial significance is the formation of
Butadiene reacts with S02 under pressure to yield a cyclic
sulfone, which yields tetramethylene sulfone on reduction:
sulfolane.
CH2 =cHCH=CH2 + S02
~o-)
S
O2
Q
O2
Sulfolane is used as a solvent for aromatics extraction and purification of
acid gas.
f.
Photochemistry
The photochemistry of butadiene is quite complex.
It can be made to
decompose via one of 5 primary processes or to dimerize in one of four ways,
depending on whether the photolysis is carried out in the gas phase or in
solution, and whether sensitization or direct absorption is involved (Table
7).
Some of the resulting products undergo secondary photolysis (Srinivason,
1966).
The dimerization of butadiene has been studied in the liquid phase, mostly
by irradiation in the presence of photosensitizers (carbonyl compounds that
excite butadiene to the lowest triplet state).
Three products are formed:
i)
cis-divinylcyclobutane, ii) trans-divinylcyclobutane and, iii)
viny1cyclohexene.
The proportion of products formed depends on the sensitizer
used, as shown in Table 8 (Liu et al., 1965; Hammond et al., 1961, 1963).
The direct irradiation of 253.7 nm solutions of butadiene (i.e., no
photosensitizer) results in less than 10% conversion to dimers.
The dimers
obtained, in order of decreasing yield, are:
2-vinylbicyclo-hexane;
1,2-divinylcyclobutane; 1,S-cyclooctadiene; and an unidentified dimer
-------
Table 7
Products of Photochemical Reactions
of Butadiene (Srinivason, 1966)
Type of reaction
Primary products
Phase in which
observed
Dimerization
cis-, trans-1,Z-divinylcyclobutane;
4-vinylcyclohexene; vinylbicyclo-
hexane
Solution
Valence tautomerization
Bicyclobutane, cyclobutene
Solution
Hydrogen migration
CZHZ and CZH4' 1,Z-butadiene
Vapor
Dehydrogenation
HZ + vinyl acetylene
Vapor
Table 8
. . Composition of .Products from Photosensitized
Dimerization of Butadienea (Liu et a1., 1965)
Percentage distribution of dimers
trans-1,Z- cis-1,Z- 4-
Divinyl- Divinyl- Vinyl-
Semsitizerb cyc1o- cyclo- cyclo-
butane butane he xene
Benzaldehyde 80 16 4
Anthraquinone 77 19 4
8-Naphthaldehyde 71 17 1Z
Fluorenone 44 13 43
Pyrene -30 -10 -60
Eosine 60 17 Z3
a 28 sensitizers listed in original reference.
b Sensitizer was 0.1 M in ether.
14
-------
When butadiene is irradiated (253.7 nm) in a dilute solution, a mixture of
bicyclobutane and cyclobutene is formed by a valence tautamerization
reaction.
When irradiation is carried out in the vapor phase, several
reaction products form as a result of hydrogen migration and dehydrogenation,
including hydrogen and possibly vinylacetylene (Srinivasan, 1966).
2.
Oligamers
Typical industrial reactions of butadiene oligamers have been discussed in
Citco (1969) and Bengelsdorf et al. (1960) and are summarized below.
Company
product bulletins list several uses of vinylcyclohexene, such as in
preparation of some insecticidal preparations:
vinylcyclohexene + Ethylene
Chlorohydrin
50-1500
4 hr
) a
S-Chloroether (Product A)
Product A + NaCNS
copper powdeI)
isobutyl
methyl ketone
a Thiocyanate
(unspec ified)
The products of the following reactions of vinylcyclohexene are used ~n or as
plasticizers:
vinylcyclohexene + 12 NHCl
) monohydrochloride + dihydrochloride
vinylcyclohexene + H2 + CO
22S-3750F
2000-4000
solvent
)
png
3-Ethylcyc1ohexyl carbinol
+ 4 ethylcyclohexyl carbinol
Vinylcyclohexene can be oxidized to produce tricarboxylic acids.
The OXO
reaction produces a ten-carbon diacid, dialdehyde or diol.
It is a useful
intermediate in preparing aromatic compounds from aliphatic hydrocarbons
because it can be easily dehydrogenated to an aromatic derivative (Stanley,
19S1) .
Products useful as anti-oxidants are formed from the reaction of
vinylcyclohexene and resinous condensate ((CH3)2CO-(C6HS)2NH).
Vinylcyclohexene is used to prepare 4-vinyl-1-cyclohexene di-epoxide which is
15
-------
further used in the manufacture of polyesters, coatings or hard, clear
plastics.
The di-epoxide can be formed during a two step process whereby
vinylcyclohexene is treated with calcium hypochlorite and the resulting
dichlorohydrin mixture is dehydrohalogenated:
~ Ca(OClh IDiChl?rOhY~~
~ II11Xture 2S'
H20
15 mia.
«
xv
4- Vinyl-l-cyclohexene
di-epoxide
Cyclooctadiene and cyclododecatriene are produced from butadiene (see
section II-A-1-b).
These oligomers are used as raw materials in
fire-retardants and in nylon production, and have other possible applications
(See section II-B-2).
For example, cyclooctadiene may be a third monomer in
ethylene-propylene terpolymer (NordelTM).
Cyclododecatriene is used to
produce a feedstock for nylon 12.
16
-------
II.
ENVIRONMENTAL EXPOSURE FACTORS
Aspects of commercial production, use, environmental contamination and
degradation are considered in the following sections.
The discussion is
primarily on butadiene, as little information is available for the oligomers
on these topics.
A.
Production Processes
1.
Production
a.
Butadiene
In the United States three ma~n routes are used commercially to obtain
butadiene from refinery streams.
Two are dehydrogenation processes; via
either n-butane or n-butene.
The third route is as a co-product of ethylene
manufacture.
All processes require final recovery of butadiene by extractive
distillation.
Table 9 shows the process and recovery systems currently used
by the domestic butadiene producers.
During 1977, the ratio of dehydrogena-
tion to coproduct butadiene was 45:55 (Anon, 1978a).
There is a trend, how-
ever, to phase out dehydrogenation in favor of co-product capacity (Section
II-A-6).
1)
Houdry Process:
Dehydrogenation of n-Butane
Normal butane can be catalytically dehydrogenated to butadiene.
In the
widely-used Houdry Process (Table 9) dehydrogenation is accomplished in one
step over a chromia-alumina catalyst.
The feed can be any complex mixture of
hydrocarbons (Baily, 1971); a typical butane stream and yield are shown in
The feed is preheated to 6200C and then passed to a series of
Table 10.
o
fixed-bed reactors containing shallow beds of the catalyst held at 600-620 C
and 150 mm Hg absolute pressure (Figure 2).
The first reactor is on-line for
about 5-10 minutes.
The feed is then passed to the next reactor so that the
17
-------
A.
Butadiene by
Company
Arco Chemical
Channelview, Tx.
Copolymer Rubber &
Chern.
Baton Rouge, La.
......
(X)
El Paso Products
Odessa, Tx.
Firestone
Orange, Tx.
B.F. Goodrich Chern.
Port Neches, Tx.
Petro-Tex Chemical
Pasadena, Tx.
Table 9
1,3-Butadiene Producers in the United States
(Anon, 1977a; Ericksson, 1977; Anon., 1976a
Amoco, 1978; Firestone, 1978; Texas U.S., 1978)
Dehydrogenati on
Process
Capacity
(millions of pounds/yr.)
Recovery System
Houdry Catadiene
Phillips Furfural
140
Petro-Tex Oxid.
Dehydrog.
Exxon Cuprous Ammonium
Acetate
160
Houdry Catadiene
Exxon Cuprous Ammonium
Acetate
205
Houdry Catadiene
Petro-Tex. Oxid.
Dehydrog.
Shell Acetonitrile,
Exxon Cupious Ammonium
Acetate
Exxon Cupious Ammonium
Acetate
248
Dow Catalyst
Petro-Tex Oxid.
Dehydrog.
Phillips Furfural
Phillips Furfural
360
(Houdry Catadiene
Petro-Tex Oxid.
Dehydrog.
Phillips Furfural)b
Phillips Furfural
880
a Feed, process and recovery system data primarily from Ericksson, 1977.
b Shut down in January, 1977; these units will be converted to by-product extraction equipment (Anon,
1976b ).
-------
I
~
i
~
-j
.}
Table 9 (Con't)
1,3-Butadiene Producers in the United States
(Anon, 1977a; Ericksson, 1977; Anon., 1976a
Amoco, 1978; Firestone, 1978; Texas U.S., 1978)
1
~
~
j
Company
Process
Recovery System
Phillips Petroleum
Borger, .Tx.
(Phillips Butane to
Butylene Dehydrog.
Phillips Oxide Dehydrog.
Phillips Furfural)d
Phillips Furfural
~
Texas-U.S. Chemicalc
Port Neches, Tx.
Phillips Furfural
Dow Catalyst Process
Petro-Tex Oxide
Dehydrog.
B.
Extraction Processes
Company
Recovery System
I-'
I.D
Arco Chemical
Channelview, Tx.
AMOCO Chemicals
Alvin, Tx.
Shell Acetonitrile
Corpus Christi Petrochem. Co.
Corpus Christi, Tx.
Dow Chemical
Freeport, Tx.
Plaquemine, La.
Shell Acetonitrile
c Joint owner of Neches Butane Products with B. F. Goodrich.
d Plants shut down according to Green & Pennington, 1977.
e On stream in late 1979, early 1980 (Anon., 1977b).
f New olefin plant to come on stream by 1980, adding 250 million
Capacity
(millions of pounds/yr.)
310
250
Capacity
(millions of pounds/yr)
260
190
_e
135
pounds to Exxon capacity (Anon., 1977a).
-------
Table 9 (Conlt)
1,3-Butadiene Producers in the United States
(Anon, 1977a; Ericksson, 1977; Anon., 1976a,
Amoco, 1978; Firestone, 1978; Texas U.S., 1978)
Company
Recovery System
(millions of pounds/yr)
Exxon Chemi ca 1
Baton Rouge, La.
Exxon cuprous ammonium acetate
Nippon Zeon dimethyl
formamide system
340f
Mobil Chemical
Beaumont, Tx.
Phillips Furfural
80
Monsanto Co.
Chocolate Bayou, Tx.
Monsanto Furfural -
methoxypropionitrile
120
Neches Butane Productsg
Port Neches, Tx.
360
N
o
Puerto Rico Dlefins
Ponce, P.R.
Shell Acetonitrile
210
She 11 Chemical
Deer Park, Tx.
Shell Acetonitrile
280
Union Carbide
Penuelas, P.R.
Seadrift, Tx.
Taft, La.
Texas City, Tx.
315
(150)
(45)
(65 )
(55)
f New olefin plant to come on stream by 1980,
g Facility jointly owned by Texas-U.S. and B.
h By mid 1978, Shell will add 90 million lbs.
expected by 1979 (Anon., 1977a). A unit will
(Anon., 1977c).
adding 250 million pounds to Exxon capacity (Anon., 1977a).
F. Goodrich.
to capacity; additional capacity of 250 million lbs.
be built in Norco, La. to recover 500 million lb./year
-------
Producl
EItroctloft
To Fuel Gas
To Fuel Gel Com pronor.
(~
~
-
Wasto Hoa I
Bailor
Produ~t
Stabilize,
Stripper
Figure 2.
Houdry Process for the Dehydrogenation of n-Butane CAnon., 1971)
Reprinted by permission from Gulf Publishing Co., Houston, Texas
Table 10
Typical Ultimate Yields of
Butadiene from a Normal
Butane Feed Stream CHoudry
Process) CAnon., 1971)
Component
Feed
C% by weight)
Butadiene
Net Products
C% of fresh feed)
Fuel Gasa Unrecovered
Dry Gas
16.3
Isobutane
1.0
Isobutylene
0.5
0.3 2.5
99.0 1.8
64.4 0.6
1.6 12
n-Butylenes
n-Butane
Butadiene
C" Coke,
C and H2 to
CO, C02 and
H20
a Butane-butylene fraction may be used in fuel gas manufacture.
-1
-------
catalyst in the first reactor can be regenerated.
During the regeneration
process, the catalyst is covered with carbon and vacuum-purged to remove
hydrocarbons, after which the deposited carbon is burned-off.
The catalyst is
then at reaction temperature and ready to sustain dehydrogenation.
At least
three reactors are required:
one on stream, one being regenerated, and one
being steam purged after regeneration.
Most plants have five or more reactors
(Lowenheim and Moran, 1975).
The hot effluent from the reactor is cooled in a quench tower, stripped of
heavy materials and light ends, then passed to a stabilization system.
The
stabilized product stream ~s now ready for product extraction (Subsection
a-4 ) .
Some butylenes are formed which may either be recycled to the reactor
or used in aviation gasoline manufacture (Lowenheim and Moran, 1975; Anon,
1971) .
2)
Oxidative Dehydrogenation:
Dehydrogenation of n-Butene
Another dehydrogenation process is one which uses normal butenes rather
than normal bu tane.
This process, referred to as oxidative dehydrogenation,
oxydehydrogenation or OXD, was commercialized by Petro-Tex in 1965 and is in
use at production sites listed in Table 9A.
The advantage of this process is
the savings in fuel; OXD is an exothermic rather than an endothermic process
and therefore, uses less energy than other dehydrogenation processes.
Hutson et ale (1974) described the process used by the Phillips Petroleum
Co.
Steam, air, and normal butenes are introduced into the OXD reactor and
then passed over a fixed catalyst bed at 900-ll00oF (482-5930C).
As
butenes are dehydrogenated, the hydrogen that is released forms water, after
reacting with oxygen in the air.
Removal of hydrogen from the reaction
environment permits the dehydrogenation reaction to proceed to a greater
extent than in ordinary dehydrogenation.
The catalyst is regenerated in situ
in the presence of steam and air in the reactor.
Phillips reported
22
-------
per-pass butadiene yields in a pilot plant of 70%.
Catalytic dehydrogenation of butenes was used until several years ago, but
now dehydrogenation plants employ an oxidative dehydrogenating agent.
3)
Co-Product in Ethylene Production
The production of ethylene from the cracking of hydrocarbons (e.g. naptha,
ethane, propane, gas oil etc.) results in C4 streams from which butadiene
can be extrac ted.
Figure 3 shows a typical process for producing ethylene.
The hydrocarbon
feedstock is pre-heated and cracked in the presence of steam; the resulting
product is passed to the pyrolysis/quench system.
From the quench system, the
raw gas is compressed; carbon dioxide and hydrogen sulfide are removed.
The
stream is then passed through a series of fractionators (Anon., 1977d) with
the mixed C4 stream being recovered.
extracted depends particularly on the hydrocarbon feedstock used (Table 11)
The amount of butadiene that can be
and on the cracking operation.
The recovery processes used are listed in
Table 9 and described in the next section.
Table 11
Average Yield of By-Product
Butadiene From Ethylene
Feedstocks (Lowenheim and Moran,
1975)
Ethylene Feedstock
By-Product Butadiene
Yield (kg/lOa kg ethylene
produced)
Ethane
Propane
Butane
Medium-Range Naphtha
Atmospheric Gas Oil
Light Vacuum Gas Oil
2.5
7.1
8.7
13.6
17.6
24.7
23
-------
Figure 3.
A Process for the Production of Ethylene (Anon., 1977d)
Reprinted by Permission from Gulf Publishing Co., Houston,
Texas
24
-------
4)
Extractive Distillation
In the 3 commercial processes just described (dehydrogenation of n-butane;
dehydrogenation of n-butene; co-product of ethylene manufacture) butadiene
must be isolated from other hydrocarbons in the product mixture.
This cannot
be accomplished b~ simple distillation because the boiling points of other
C4 hydrocarbons in the mixtures are very close to that of butadiene.
tractive distillation is often employed, and involves the use of a polar sol-
Ex-
vent to change the relative volatility of the components being distilled.
Widely used solvents are furfural and acetonitrile, in processes developed by
Phillips Petroleum Co. and Shell Chemical, respectively.
Other recovery pro-
cesses in use are Exxon's Cuprous Ammonium Acetate System, Nippon Zeon's Di-
methyl Foramide System and Monsanto's Furfural-Methoxypropionitrile System
(Table 9).
A flow chart for Phillip's Furfural Separation System for butadiene ex-
trac~ion is shown in Figure 4 (Peters and Rogers, 1968).
In this process C4
from an ethylene plant and furfural are fed into the extractive distillation
tower.
Heat is then supplied at the base of the tower and the overhead
product is withdrawn (primarily butanes, butenes, allene, methyl acetylene and
light weight hydrocarbons).
A solvent-butadiene mixture, C4 acetylenes and
2-butenes are withdrawn from the bottom and fed to a stripper tower where C4
components are removed.
The product is then sent to a conventional distil-
2-butene, C4 acetylenes, 1,2-butadiene and carbonyls are
withdrawn from the base; high-purity 1,3-butadiene is removed overhead (Peters
lation tower where
and Rogers, 1968).
b.
Oligomers
Small quantities of vinylcyclohexene, cyclododecatriene and cyclooctadiene
are produced commercially from butadiene.
25
-------
- - - - --- - - --- -- . ----
------- - -------.
~- -- -----
EXTRACTIVE
DISTILLATION
STRIPPER
CONVENTIONAL
DISTILLATION
.
I.,... .
~'
BUTANES, BUTENES,
ALLENE,METHYL
ACETYLENE Ii LIGHTS
BUTADIENE
BUTENE.2 EHTYL ACETYLENE,
VINYL AcETYLENE Ii HEAVIES
'- ~-~ . . ~ - ---
Figure 4.
Phillip's Furfural Extraction Process
(Peters and Rogers, 1968). Reprinted
Publishing Co., Houston, Texas
for Butadiene
by Permission from Gulf
Vinylcyclohexene is produced as a byproduct of either butadiene or cyclo-
octadiene/cyclododecatriene manufacture (Henderson, pers. comm., 1978).
The
dimerization reaction of butadiene to form vinylcyclohexene is discussed in
section 'I-D-l-b).
Butadiene is selectively dimerized to cyclooctadiene and trimerized to
cyclododecatriene.
Conventionally, Ziegler catalysts or organo nickel com-
plexes have been used.
Ono and Kihara (1967) reported that several new
catalysts have been developed in Japan:
bisacrylonitrile nickel to produce
cyclododecatriene and bisacrylonitrile nickel-triphenyl phosphine or tetra-
phenyl isonitrile nickel-triphenyl phosphite to produce cyclooctadiene or mix-
tures of cyclooctadiene and cyclododecatriene (Figure 5).
Butadiene, a
non-polar solvent, and the catalyst are introduced into the reactor which is
held at 800C and a maximum pressure of 10 kg/cm2.
After the reaction, the
product solution undergoes successive recovery processes for the separation of
unreacted butadiene, solvent, by-products and vinylcyclohexene.
After this,
26
-------
REACTOR
BUTADIENE
RECOVERY
TOWER
CATALYST a
POLYMER
SEPARATOR
STORAGE
SOLVENT
RECOVERY
TOWER
VCH
RECOVERY
TOWER
COD
PURIFICATION
TOWER
COT
PURIFICATION
TOWER
SOLVENT
RECYCLE
PRODUCT COD
RECOVERY
CHV
PRODUCT COT
CATALYST
e BUTADIENE
RESIDUE
RESIDUE
Figure S.
Toyo Soda (Japan) Process for Cyclooctadiene and Cyclododecatriene
Manufacture (Ono and Kihara, 1967). Reprinted by Permission from
Gulf Publishing Co., Houston, Texas
cyclooctadiene and cyclododecatriene are purified and then recovered.
The
r~tio of cyclooctadiene to cyclododecatriene produced depends on the catalyst
used (Table 12).
With the 3 catalysts described by Ono and Kihara (1967), the
cyclododecatriene produced is predominantly the trans, trans, trans-isomer
(Ziegler type catalysts produce mainly the trans, trans, cis-isomer).
Morikawa et al. (1972) described a process for producing cyclodecatriene
using a mixed C4 stream rather than pure butadiene as a starting material.
The C4 stream may contain as much as 35 wt./% butadiene.
Per-pass yields
range from 75 to 80% of maximum for cyclododecatriene.
In this process, buta-
diene is cyclotrimerized to form 3 isomers of cyclododecatriene, the configur-
ation produced being dependent on the catalyst composition.
Cyclododecatriene
is then hydrated to cyclododecane used to make nylon-12, a polyamide plastic.
As in the process described by Ono and Kihara (1967) an unwanted side reaction
is the formation of vinylcyclohexene, which can, however, be removed by
disti llation.
27
-------
Catalyst
So 1 vent
Temperature
(OC)
Maximum
pressure
(kg/cm2)
Conversion
(%)
Selectivities
(%)
VCR
COD
CDT
Ligh ts
He~vies
Table 12
Reaction Conditions and Selectivity
in the Production of Cyclooctadiene
(COD) and Cyclododecatriene (CDT)
(Ono and Kihara, 1967)
Ni(AN) 2 Ni(AN) 2/p. ph3
= 1/1.6
COD COD
80 80
9.8 10.3
96.5 94.5
6.0
7.1
80.4
1.1
5.4
6.2
53.9
35.2
0.9
3.8
Ni(AN) 2/p. ph3
= 1/3.2
COD
80
10.3
95.4
6.5
84.9
4.5
0.7
3.4
AN = acrylonitrile
ph = phenyl
28
-------
Quantity Produced
Butadiene ranks 30th in a list of all chemicals with respect to quantity
2.
produced (U.S. Int. Tariff Comm., 1976).
During the first quarter of 1978
production of butadiene was at 82% of name-plate capacity (4.3 billion
pounds/year) or at 91% of effective (practical maximum) capacity (Anon.,
1978b).
U.S. production of butadiene during 1978 is predicted to be 3.3
billion pounds, up about 6% from 1977 (Anon., 1977e).
U.S. butadiene is about
40% of worldwide production (8.8 billion pounds) (Anon., 1978a).
The U.S. International Trade Commission reports production figures for
rubber-grade butadiene and for butadiene and butylene fractions.
As shown in
Table 13 A, production of rubber-grade butadiene steadily increased during the
last decade until 1975, when a sharp decrease occurred as part of the general
. .
econom~c recess~on.
Production recovered during 1976 but not as much as fore-
casted for two reasons:
i) the U.S. rubber strike and ii) steam cracking
operations produced 'less coproduct butadiene than expected (Anon., 1976b).
Data for butadiene and butylene fractions appear in Table 13 B; butadiene from
this source is presumably used in non-rubber applications.
The U.S. Inter-
national Trade Commission does not list production figures for butadiene
o ligomers .
3.
Domestic Producers and Production Sites
There are 8 domestic producers of 1,3-butadiene us~ng dehydrogenation pro-
cesses (Table 9 A) and 8 different producers using extraction processes (Table
9 B).
Total dehydrogenation capacity is about 2.6 billion pounds, with
Phillips and Petro-Tex being the largest producers.
Extraction capacity is
currently 2.3 billion pounds, lead by Exxon and Neches Butane.
Summing both
processes, total butadiene capacity is about 4.90 billion pounds from 20
production sites: 14 in Texas, 4 in Louisiana and 2 in Puerto Rico (Table 9).
29
-------
Table 13
U.S. Production and Sales of Butadiene:
A) Rubher-Grade Butadiene and B) Butadiene and
Butylene Fractionsa
Value of
Produc ti on Sales Sales Average Cost,
(million lbs.) (million lbs.) (1,000 $) Cents/Pound
A) Rubber-Grade Butadiene
1977b 3,187
1976 3,507.3 2,188.7 387,018 17.6
1975 2,597.0 1,887.3 310,574 16.5
1974 3,682.1 2,500.8 363,932 14.6
1973 3,643.5 2,416.5 196,552 8.1
1972 3,527.4 2,230.0 173,844 7.8
1971 3,340.3 2,022.6 167,274 8.3
1970 3,101.4 1,947.2 163,967 8.4
1969 3,123.0 1 , 98 1. 9 167,312 8.4
1968 2,928.7 1,942.6 171,917 8.8
1967 2,660.3 1,620.8 154,266 9.5
B) Butadiene and Butylene Fractions
1976 1,398.7 406 . 7 35,670 8.7
1975 756.2 284.8 29,408 10.3
1974 757. 7 362.1 21,337 5.9
1973 535.2 450.3 12,310 2.7
1972 568.0 436.2 11,817 2.7
1971 687.2 429.8 11 , 808 2.7
1970 743.5 409.3 12,846 3.1
1969 1,264.2 280.4 8,281 3.0
1968 1,042.9 245.4 7,217 2.9
1967 894.2 238.6 6,997 2.9
aSource: u.s. Int. Trade Comm. 1973-1977
u.s. Tariff Camm. 1967-1972
bpre liminary
30
-------
Crude vinylcyclohexene used to be offered for sale on an "as is" basis by
Texas-U.S. Chemical Company (i.e., no sales specifications); the customer
could use the material as it was or redistill it.
Due to a limited market and
captive needs, Texas U.S. no longer offers it in the merchant market (Rodde,
pers. comm., 1978); vinylcyclohexene is not made intentionally.
CTC Organics
(Atlanta, Ga.) offers it for sale on an "as-needed" basis; they purchase crude
byproduct stream and purify it (Liu, pers. comm., 1978).
Also, Cities Service
Co. offers 97% pure vinylcyclohexene as a byproduct of butadiene or cyclo-
octadiene/cyclododecatriene manufacture (Henderson, pers. comm., 1978).
Puri-
fied (99%) vinylcyclohexene can be purchased from the Aldrich Chemical Co. in
500 g or 2 kg quantities.
Cyclooctadiene is manufactured by the Cities Service Co., Inc. (Lake
Charles, La.).
The annual capacity is 25 million pounds; however, actual pro-
duction figures are unavailable (Henderson, pers. comm., 1978).
Cyclododeca-
triene can also be produced by Cities Service at the Lake Charles Plant, but
DuPont is currently the only cyclododecatriene producer in the U.S.
(Henderson, pers. comm., 1978).
DuPont's cyclododecatriene is used captively
and no up-to-date capacity figures have been published.
In 1972, DuPont's
capacity for cyclododecatriene was rated at 2.2 million pounds, but the plant
has since expanded (Simpson, pers.
comm. ,
1978; Anon., 1972).
4.
Foreign Importers and Producers
Imports of 1,3-butadiene into the U.S. totalled 595 million pounds during
1976 and came primarily from the Netherlands (42.3%) and the United Kingdom
(22%), with smaller amounts from Belgium, France, Italy, Japan and West Ger-
many (Table 14; U.S. Bureau of the Census, 1976).
Imports have increased more
than 65% from 1972 levels.
Since that time Canada, Finland and Mexico also
exported small amounts of butadiene into the United States (Table 14; U.s.
31
-------
Table 14
Imports of Butadienea into the United Statesb
1976 1975 1974 1973 1972
Total Quantity Gallons 113,910,892 107,305,733 114,593,177 70,112,451 68,052,945
Poundsc 595,640,005 561,101,677 599,207,722 366,618,006 355,848,849
Country of Origin (%)
Belgium 1.6 1.3
Canada 1.9 0.2 4.9 11.4
Finland 1.0
France 10.7 13.6 18.9 12.6 3.5
Italy 8.8 4.5 4.9 9.2 2.6
Japan 10.5 27.2 24.6 35.3 59.6
Mexico 3.0
Netherlands 42.3 33.1 43.0 32.3 17.7
U. Kingdom 22.0 10.7 5.3 3.0 5.2
W. Germany 4.1 5.0 1.8 2.7
IJ.J
N
a Commodity number 4295020.
b Source: U.s. Bureau of Census 1972-1976.
c Using conversion facter 1 gallon = 5.229 Ibs. (At 600F).
-------
Bureau of the Census, 1972-1976).
Ericksson (1976) expects imports to in-
crease from now until the early 1980's.
Producers such as Exxon, Shell and
Arco expect butadiene imports to increase to 1 billion pounds or more by the
early 1980's (Prescott, 1976).
However, Debreczeni (1977) forecasts imports
to remain at about 500 million pounds through 1990.
He predicts imports will
represent a slowly decreasing percentage of total U.S. butadiene supply (12%
1977; 8% 1990) as domestic extraction capacities are increased (Table 15).
In Western Europe all butadiene capacity is by extraction (Driver, 1976).
Current butadiene capacities and production figures for several European coun-
tries appear in Table 16.
The annual rate of growth for butadiene production
in these countries is expected to be about 8.2% per year (Klaus, 1977).
P. N.
Collinswood of B. P. Chemicals Ltd. predicts a potential growth surplus of
butadiene in Europe of almost 750,000 tons/year by 1990, up considerably from
levels in 1974-1975 (250,000 tons/year).
He forecasts that outlets for this
European surplus will not exist by about 1985 (Anon., 1977f).
The U.S. Bureau of the Census does not list import data for butadiene
oligomers.
Major European manufacturers of cyclooctadiene and/or cyclododeca-
triene are Hulls (cyclododecatriene capacity of 26 million pounds) and Shell
Chemie (Berre, France; cyclododecatriene/cyclooctadiene capacity of 22 million
pounds) (Anon., 1972).
5.
Market Price
In January 1978 the market price of butadiene ranged from 20.5 to 22.75
cents per pound (f.o.b., Gulf Coast) (Petro-Tex Chem. Corp., 1978), up from
18.25-18.5 cents per pound quoted during early 1977 (Anon., 1977g).
According
to Ericsson Chemical Services (Anon., 1977h), recent price increases reflect:
i) increased domestic demand for butadiene, ii) reduced operating rates for
European and Japanese ethylene plants and iii) the shut-down by Petro-Tex of
33
-------
Table 15
Butadiene Supply in the United States (Debreczeni, 1977)a
Billions of Pounds
1977 1980 1985 1987 1990
Extraction by Ethylene 1. 2 (29%) b 1. 5 (34%) 2.1 (42%) 2.4 (46%) 2.8 (45%)
Producers
Extraction by Butadiene 0.6 04%) 1.1 (25%) 1. 9 (38%) 2.1 (40%) 2.9 (47%)
Producers
Dehydrogenation of Butane 1. 9 (45%) 1. 3 (30%) 0.5 00%) 0.2 (4%) 0 (0%)
and/or Butylene
Imports 0.5 02%) 0.5 (11%) 0.5 00%) 0.5 00%) 0.5 (8%)
Total 4.2 4.4 5.0 5.2 6.2
a Data in bar graphs in original reference.
b Percent of total supply.
l.V
.p..
-------
Table 16
European Butadiene Capacity and Production
for 1978 (Klaus, 1977)
Country
1978 Estimated Effective
Capacity
(Millions of pounds)a
1978 Estimated
Production
(Millions of pounds)a
Belgium, Netherlands, and
Luxembourg
1124
849
Federal Republic of
Germany
1356
ll5a
France
794
662
Italy
540
443
United Kingdom
838
617
Spain
198
198
a Original units in metric tons.
35
-------
more than half of their butadiene facility.
Debreczeni (1977) predicts that the price of butadiene will rema~n high
enough to keep dehydrogenation plants operating until demand can be satisfied
from extraction units.
That is, if the price of either imported or extraction
butadiene falls below the "breakeven" point of dehydrogenation, the dehydro
producer could be forced to close.
Debreczeni further forecasts that when
sufficient coproduced butadiene becomes available (perhaps by 1987) the price
of butadiene will likely decrease but concomitant increases in the price of
ethylene and/or propylene can be expected.
Historically, the average price of butadiene increased in the u.s. from
8.4 in 1969 to 14.6 cents per pound in 1974 (Table 13).
Driver (1976)
analyzed butadiene pricing in Western Europe for that tDne period and con-
cluded that these increases reflected the performance of butadiene derivatives
rather than changes in the cost of production and extraction.
That is, the
upper limit on the price of butadiene is determined by what the major deriva-
tives can bear before their competitive position in their ~~ markets is
threatened.
For example, as the price of styrene-butadiene rubber (SBR) in-
creased, so did the price of butadiene.
Cyc1ooctadiene, vinylcyclohexene and cyclododecatriene are available from
Citco in 1 and 5 gallon cans for $1.00 per pound.
The first two compounds are
also available at the same price in drum quantities (400 pounds/drum).
Lower
prices are quoted for cyclooctadiene for truckload drum, ($0.85/lb., minimum
20,000 lbs.) and tank truck ($0.75/lb.; minimum 30,000 lbs.) quantities
(Citco, 1977).
6.
Market Trends
The average annual growth of butadiene has been about 2% during the period
from 1967-1976.
Future growth of 4% per year is forecasted through 1981
(Anon., 1977a) when butadiene demand will reach 4.5 billion pounds (Greene and
36
-------
Pennington, 1977).
Butadiene's future will depend particularly on basic tire
rubbers, since about 85% of its consumption goes into tires and other rubber
products.
Forecasted butadiene demand for end-products are discussed in the
next section and summarized in Table 17.
The supply or sources of butadiene will continue to reflect increasing
co-product capacity.
During the 1960's all domestic butadiene was produced. by
the dehydrogenation of butane and/or of butylenes.
By 1970, 80% of production
was via dehydrogenation, but this had decreased to about 50% by 1977 as sup-
plies from co-product streams have increased (Table 15).
The percentage of
co-product butadiene supply available by 1985 has been forecasted between 80%
(Debreczeni, 1977) and 67% (Ericksson, 1977).
Total phase-out of dehYdro
capacity is predicted by 1990 (Table 15).
Factors underlying this phase out
are the economic and efficiency advantages of extraction.
According to
Ericcson (1976), this decrease does not mean a closing of dehydro units but
rather, a conversion to extraction capacity.
The extraction equipment at
dehydro plants will be converted to recover butadiene from crude C4 hydro-
carbon streams brought from steam crackers.
The type of ethylene feedstock used is an important factor in co-product
availability.
As discussed (section 1-a-3) lower butadiene yields are
obtained from ethane, propane or butane feedstocks than from naptha or gas
oil.
Indi- cations are for a growing importance of heavy feedstocks in
ethylene manufac- ture.
Of 14 announced ethylene plants or expansions, most
(85%) will be based on heavy feeds.
Thus, more coproduced butadiene will be
available (Greene and Pennington, 1977).
B.
Use
1.
Butadiene
The major uses of butadiene include styrene-butadiene rubber (537.), poly-
butadiene rubber (18%), neoprene (7%), nitrile rubber (3%), adiponitrile (8%),
37
-------
Tab1 e 17
Butadiene Demand in the United States
(Debreczeni, 1977)a
Billions of Pounds
1977 1980 1985 1987 1990
SBR & SBR Latex 2.0 (48%)b 2.0 (46%) 2.1 (42%) 2.2 (42%) 2.3 (39%)
Polybutadiene Elastomer 0.8 (19%) 0.8 (18%) 0.9 (18%) 1. 0 (19%) 1. 0 (18%)
Nitrile & Polyisoprene 0.6 (14%) 0.8 (18%) 0.9 (18%) 0.9 (17%) 1. 0 (18%)
Elastomers
Nylon 66 & other O. 7 (17%) 0.7 (16%) 1.0 (20%) 1. 0 (19%) 1.2 (21%)
Chemicals
Mis ce 11 aneous & Exports 0.1 (2%) 0.1 (2%) 0.1 (2%) 0.1 (2%) 0.2 0.5%)
Total 4.2 4.4 5.0 5.2 5.7
w
00
a Data in bar graphs in original reference.
b percent of total demand.
-------
acrylonitrile-butadiene-styrene res~ns (6%) as well as miscellaneous uses (5%)
(Anon., 1977 a).
The uses and produces of these products (Table 18) are dis-
cussed in the sections which follow.
a.
Styrene-Butadiene Copolymers
The largest use of butadiene is in the production of styrene-butadiene
rubber (SBR) and latex, accounting for 53% of domestic butadiene demand (2.12
billion lbs/year) (Anon., 1977a).
One type of SBR is used in tires (68% of
total use).
Other uses of SBR include:
molded and extruded goods (13%),
sponges (4%), footwear (3%) and miscellaneous uses (12%) such as foam rubber
products and carpet backing (Anon., 1977i; Ericksson, 1977).
SBR is produced by solution and emulsion polymerization; the ratio of
butadiene to styrene is generally 77:23 (Uraneck, 1968).
A typical emulsion
SBR process is shown in Figure 6.
There are several hundred types of SBR,
depending on details of the process; 2 maj or categories are "hot SBR" and
"cold SBR" referring particularly to polymerization temperature's of 600C and
sOC, respectively.
A typical formulation for cold SBR is given below
(Sal tman, 1965):
Typical Formulation for a "Cold" SBR
Parts by Weight
Butadiene
Styrene
tert-dodecyl mercaptan
diisopropylbenzene monohydroperoxide
ferrous sulfate
potassium pyrophosphate
rosin acid soap
water
72
28
0.2
0.08
0.14
0.18
4.0
180
(polymerization goes to 60% conversion at 5°C after 12 hours)
39
-------
Table 18
Producers and Capacities for Major Products
Using Butadiene
Producer
Capacity
(Millions of lbs./year)
Reference
~
o
Styrene-butadiene Rubbera
American Synthetic Rubber, Louisville, Ky.
AShland, Bay town, Tex.
Copolymer, Baton Rouge, La.
Firestone, Lake Charles, La.
Orange, Tex.
General Tire, Odessa, Tex.
B. F. Goodrich, Port Neches, Tex.
Goodyear, Houston, Tex.
Phillips, Borger, Tex.
Texas-US, Port Neches, Tex.
TOTAL
276
132
276
712
100
212
320
867
275
399
3629
Anon., 1917i
Polybutadiene Rubberb
American Synthetic, Louisville, Ky.
Firestone, Orange, Tex.
Goodrich, Orange, Tex.
Goodyear, Beaumont, Tex.
Phillips, Borger, Tex.
TOTAL
168
230
134
246
146
924
Anon., 1976c
Neoprene
DuPont, La Place, La.
DuPont, Louisville, Ky.
Petro-Tex, Houston, Tex.
TOTAL
80
300
66
440
Anon., 1976d
a Dry SBR; some capacity figures include carbon black and extender oils.
b Net rubber basis of solution polymerized polybutadiene.
-------
-'"
I-'
Producers and
Table 18 (Cont.)
Capacities for Major
Using Butadiene
Products
Producer
Nitril e Rubberc
Copolymer, Baton Rouge, La.
Firestone, Akron, Ohio
Goodrich, Akron, Ohio
Goodrich, Louisville, Ky.
Goodyear, Akron, Ohio; Houston, Tex.
Uniroyal, Painesville, Ohio
TOTAL
Capaci ty
(Millions of lbs./year)
Reference
11
11
31
63
68
56
240
Anon., 1976e
Adiponitril ed
DuPont, Laplace, La.
DuPont, Orange, Tex.
DuPont, Victoria, Tex.
SRI, 1975
Acrylonitrile-Butadiene-Styrene Resinse
Abtec, Louisville, Ky.
Borg-Warner, Ottawa, Ill.
Borg-Warner, Washington, W. Va.
Dow, Gales Ferry, Conn.
Dow, Midland, Mich.
Dow, Torrance, Calif.
Hammond Plastics, Worcester and Oxford, Mass.
Mons anto, Addys ton, Ohi 0
Monsanto, Muscatine, Iowa
Rexene, Joliet, Ill.
Uniroyal, Baton Rouge, La.
TOTAL
65
230
290
65
70
20
11
275
125
55
200
1406
Anon., 1977j
c Capacities are flexible in plants where other elastomers such as styrene-butadiene, styrene-butadiene-
vinylpyridine or PVC blends with nitrile may also be produced.
d DuPont is the only producer making adiponitrile from butadiene. Other adiponitrile manufacturers
are: Celanese Corp. (Bay City, Tex.), El Paso Natural Gas Co. (Odessa, Tex.) and Monsanto Co. (Decatur,
Ala.; Pensacola, Fla.).
e Capacity of styrene-acrylonitrile (SAN) resin included in some figures; SAN capacity considered
proprietary.
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Solution polymerization techniques are used to make thermoplastic SBR, a block
polymer of styrene and butadiene.
An outstanding characteristic is that the
polymer is a rubber when cold, a plastic when hot (Allan, 1972).
Table 18 shows that the capacities of the major SBR producers exceed 3500
million pounds per year.
The annual capacity of SBR latex is about 700
million pounds per year, Goodyear and Firestone being the largest producers
(SRI, 1975).
During 1976, 2967 million pounds of SBR rubber and latex were
produced in the U.S., up 12% from 1975 figures but below peak 1973 production
(3334 million lbs.) (Dept. of Comm. 1977).
Figures for 1977 will probably
show a surge of production as a result of the rubber strike of 1976 (Anon.,
1977e) .
The future of SBR (and also polybutadiene) is highly dependent on tire
demand.
Expected growth in the tire industry is only about 2% per year
(Anon., 1977 a) .
One factor in this modest growth is the trend to smaller cars
and slower highway speeds.
Also, most new cars come equipped with radial
tires which give 40% better mileage than bias tires and 20% more than belted
ones;
therefore, tire replacement is less frequent.
In 1970 only 1% of the
new cars came equipped with radial tires but by 1985 this figure is expected
to reach 90% (Prescott, 1976).
Furthermore, when a conventional tire is re-
placed by a radial tire as much as 14% less SBR is used (Greene and
Pennington, 1977).
There has also been a decline in passenger car travel
mileage.
In the past, mileage has increased about 5% per year but this rate
may drop to 2%.
Based on tire demand and other uses, Greene and Pennington
(1977) forecast that dry SBR use will grow at the rate of 2.5% per year
through 1981.
43
-------
b.
Polybutadiene
About 720 million pounds of butadiene were consumed during 1977 in the
production of polybutadiene, accounting for 18% of butadiene demand (Anon.,
1977a).
Approximately 85% of the total polybutadiene supply is used in auto
and truck tires (Anon., 1976c), usually in blends with SBR or natural rubber.
Polybutadiene enhances the resilience of SBR which reduces heat buildup in
tire treads (Allan, 1972).
The rest of the polybutadiene supply is used in
high impact resins among other uses (Anon., 1976c).
Polybutadiene is made primarily by solution polymerization.
By using dif-
ferent stereoregulating catalysts, polybutadienes can be made ranging from
almost 100% cis to 100% trans.
A solution polymerization process developed by
Phillips Petroleum Co. to produce high cis content polybutadiene (>80% cis)
consists of four basic steps (Figure 7):
1) butadiene and solvent purification; 2) reaction and concentration; 3)
blending and solvent removal and 4) drying and packaging.
The over-all con-
version of butadiene to cis- polybutadiene is >98% (Anon., 1977k).
Polybutadiene is produced at 5 sites by four producers with a total annual
capacity of 905 million pounds (Table 18).
A total of 781 million pounds of
po1ybutadiene elastomer, including latex, were produced domestically during
1976, an increase of about 18% over 1975 when production was depressed
(Department of Commerce, 1977).
Demand for polybutadiene is expected to in-
crease 2-3% per year through 1980; however, there is a trend to substitute
polybutadiene for natural rubber in tire sidewalls which would increase
projected demand further (Anon., 1976c).
c.
Chloroprene!Neoprene
Chloroprene (2-chloro-1,3-butadiene) is manufactured from butadiene,
accounting for 7% of the total domestic butadiene demand (or about 280 million
44
-------
Figure 7.
Production of cis-Polybutadiene (Anon., 1977k) Reprinted by
Permission from Gulf Publishing Co., Houston, Texas
45
-------
pounds/year) (Anon., 1977a).
It is used in the production of polychloroprene
synthetic elastomers under the trade name of Neoprene.
Neoprene is used in
applications requiring high gum strength or chemical, oil and weather resis-
tance (Hargreaves, 1968; Bauchwitz et al., 1971).
A major breakdown of Neo-
prene markets would include:
exports (30%). industrial rubber goods (Z4.57.),
automotive (19.6%), wire and cable (9.1%), construction (7%), adhesives (5.6%)
and miscellaneous uses (4.Z%).
Future growth is forecasted to be Z.4% per
year but could be slightly higher if potential applications are accepted (e.g.
full-foam seats for commercial use; Anon., 1976d).
Chloroprene production utilizes butadiene as a starting material in a
i,)
Chlorination of Butadiene
CRZ=CH-CR=CHZ + CIZ---7 Cl-CRZ-CH=CR-CRZ-Cl + CRZ=CR-CHCI-CRZ-Cl
'3utadiene
1,4-dichlorobutene-Z
3,4-dichlorobutene-l
ii. )
Isomerization of Dichlorobutenes
Cl-CRZ-CR=CR-CRZ-CI ~ CRZ=CH-CHCl-CRZ-Cl
cis and trans
1,4-aicillorobutene-2 3,4-dichlarobutene-l
The 1,4-dichlorobutene-Z is isomerized to 3,4-dichlorobutene-1 for chloro-
prene but can also be used in adiponitrile manufacture (See II-B-1-e)
iii.)
Dehydrochlorination of 3,4-Dichlorobutene-1
CRZ=GR-CRCI-CRZ-CI + NaOR ----t CHZ=GH-CCI=CHZ + H20 + NaCl
.
3,4-Dichlorobutene-1
Chloroprene
A simplified flow diagram for chloroprene production appears in Figure 8.
Overall yields of 80-95% based on butadiene input have been reported
(Bauchwitz et al., 1971).
46
-------
Until about 10 years ago all chloroprene capacity was based on the cata-
lytic dimerization of acetylene to vinylacetylene and subsequent hydrochlorin-
ation (Bellringer and Hollis, 1968).
There are two producers of neoprene:
DuPont (La Place, La.; Louisville,
Ky.) and Petro-Tex (Houston, Tex.).
Their capacities total 440 million
pounds/year.
This capacity should be adequate for the foreseeable future
(Anon., 1976d).
DRIER
HCI SCqUtlBER
H20
I
OEHYQRCCHLORINIITOR
CHlORO::..::I.E PURIFIER
.... BUTAQ:E1:E
....
BUTAOIEPJE
eUTADIENE
HCI
~
AQUEOUS HCI
PURE
CHLORC?RENE
.... CHLO~I~JE
....
I-oiLORO-
BUTAOIENE
AQUEOUS
NoOH
3,4-DICHLCRoeUTENE -I
DICHLOR03JT!NES
CHLORINATOR DEGASSER
HIGH BOILERS
lSOMEf!IZER
AQUEOUS Noel
AQUEOUS STRIPPER
Figure 8.
Production of Chloroprene from butadiene (Bellringer and Hollis,
1968). Reprinted by Permission from Gulf Publishing Co., Houston,
Texas.
47
-------
d.
Nitrile Rubber
About 3% of the butadiene supply is used in nitrile rubber, a copolymer of
acrylonitrile and butadiene. The acrylonitrile content is about 3Z% but may
range from 18 to 50% (Sal tman, 1964). The main advantage of nitrile rubber ~s
the oil resistance imparted by the acrylonitrile component.
Among uses of
nitrile rubber are applications in latex (20%), hose (20%), seals and gaskets
(15%), footwear (4%), adhesives and binders (8%), exports (18%) and miscellan-
eous mechanical goods (15%) (Anon., 1976e).
Nitrile rubber is produced by emulsion polymerization techniques similar
to SBR manufacture (Section II-B-1-a).
There are four major producers (Co-
polymer, Firestone, Goodrich and Uniroyal) with an annual capacity of
240 million pounds (Table 18).
During 1976 about 170 million pounds of
nitrile rubber (including latex) were produced domestically, 27 million pounds
below peak 1974 production rate (Department of Commerce, 1977).
Growth is
predicted at 3.5% per year through 1980 (Anon., 1976e). .
e.
Adiponitrile/HMDA
DuPont uses butadiene to make adiponitrile, which is hydrogenated to form
hexamethylenediamine (HMDA), an intermediate in the manufacture of nylon 6,6.
DuPont uses two processes to make adiponitrile.
The older four-step process, used since 1950, is employed at 2 of 3 DuPont
plants (Victoria, Texas and La Place, Louisiana).
The main steps are summar-
ized below (Pervier et al., 1974b):
L)
Chlorination
CHZ=cHCH-CHZ + Cl2 ---?CHZCI-CHCI-CH=CHZ + CHZCI-CH=CH-CHZCl
Butadiene 3,4-Dichloro-l-Butene 1,4-dichloro-Z-butene
iL)
Cyanation
) NC-CHZ-CH(CN)-CH=CHZ + ZNaCl
3,4-Dicyano-l-Butene- Sodiu!!l.
Chloride
CH2CI-CHCI-CH=CHZ
3,4-Dichloro-
I-Butene
+ ZNaCN
SodiUI'1
Cyanide
48
-------
iii. )
Isomerization
NC-CHZ-CH(CN)=CHZ ~NC-CRZ-CH=CH-CHZ-CN
3,4-Dicyano-1-Butene 1,4-Dicyano-Z-Butene
iv. )
Hydrogenation
NC-CHZ-CR=CH-CHZ-CN + HZ ~NC-(CHZ)4-CN
1,4-Dicyano-Z-Butene Adiponitrile
In reaction i.) above, the products can also be used in the manufacture of
polychloroprene (2-chloro-1,3-butadiene) (Ericksson, 1977).
Both chloroprene
and adiponitrile are produced at DuPont's Victoria, Texas plant (SRI, 1975).
At the newer plant in Orange, Texas, butadiene is mixed with hydrogen
cyanide in the presence of copper chromate catalysts, which forms the
adiponitrile precursor, 1,4-dicyano-Z-butene by direct hydrocyanation
(Drinkard, 1970).
The first adiponitrile plant in Europe (104 metric
tons/year capacity) using this process has just been completed at Chalampe,
France by Butachimie, licensed by DuPont (Anon., 1978c; Prescott, 1976).
With
this one exception, other companies besides DuPont do not use butadiene to
produce adiponitrile, but rather use cyclohexane or acrylonitrile as a start-
ing material (Pervier et al., 1974b).
Capacity figures for DuPont's adiponitrile plants are unavailable.
About
8% of the total domestic butadiene demand (or about 3Z0 million lbs/year) is
used by DuPont in adiponitrile manufacture (Anon, 1977a).
f.
Acrylonitrile-Butadiene-Styrene Resins
About 6% of the total domestic demand for butadiene (or 240 million
pounds) goes into Acrylonitrile-Butadiene-Styrene (ABS) resins.
ABS resins
are usually produced by "graft" polymerization.
A rubber is made by the poly-
merization of butadiene.
Styrene and acrylonitrile monomers are then polymer-
ized (grafted) directly onto the rubber.
Major markets for ABS resins include pipe (29%); automotive (18%); appli-
ances (18%); recreational vehicles (8%); business machines and telephones
49
-------
(S.2%); furniture, luggage and packaging (6.1%); exports (3.2%) and miscellan-
eous uses (ll.S%).
Among newer markets is use in recreational vehicles and
smoke detec tors.
Growth is forecasted at 7.S% per year through 1981 (Anon.,
1977j).
ABS is made by 7 producers at 11 sites for a total annual capacity (Table
18) of 1406 million pounds.
Planned expanS1.ons have been announced by all
producers except for Rexene Styretics, and when operational should increase
total ABS capacity by at least 400 million pounds/year by 1979 (SRI, 1977;
Anon., 19771, 1977m, 1977n).
g.
Miscellaneous Use
Miscellaneous uses account for about S% (or 200 million pounds) of the
domestic butadiene demand.
About 76 million pounds of domestically produced
butadiene were exported from the U.S. during 1976, primarily to Canada
(43.6%), Mexico (37.4%) and the Korean Republic (15%) (U.S. Bureau of Census,
1976).
Total exports have increased during the last 5 years (Table 19).
Included among miscellaneous uses of butadiene are several derivatives.
For example, butadiene is used in the preparation of the fungicide Captan and
the insecticide Phygon.
It is also used to prepare Sulfolane, a product used
as a process solvent.
These reactions were discussed in Section I-D-1.
As
discussed (Section II-A-1-b) small amounts of butadiene are used in the
manufacture of cyclooctadiene, and cyclododecatriene.
----_.-v-_------
Another use of butadiene is in methyl methacrylate-butadiene-styrene (MBS)
terpolymers used as impact modifiers in rigid poly(vinyl chloride) compounds.
MBS has major applications in packaging and in building and construction.
A
typical MBS formulation contains 75 parts butadiene to 25 parts styrene as a
substrate; the final polymer contains 60 parts substrate, 20 parts styrene,
and 20 parts methyl methacrylate (Purcell, 1976).
50
-------
Table 19
Exports of U.S. Butadiene Monomera
1976 1975 1974 1973 1972
Total Quanti ty (l be.) 76,106,471 73,019,505 70,180,555 64,201,585 28,428,748
Where Exported (%)
Argentina 0.4 0.5 <0.1 0.2
Aua tralia 1.8
Brazi 1 0.9 4.7 18.8
Canada 43.6 29.9 32.9 19.4 0.8
Japan 0.6
Korean Republic 15.0
Ln
~ Mexico 37.4 46.7 67.0 61. 7 99.0
Netherlands 16.3
Others 0.1 <0.1 0.1 0.2
a Commodity number 5120996
Source: U.S. Bureau of Census
(1972-1976)
-------
Butadiene is also used in the production of polybutadiene by the Arco
Chemical Co.
This is a liquid resin containing 85-100% butadiene, either as a
homopolymer or as a copolymer with styrene or acrylonitrile.
Polybutadiene is
also referred to as an hydroxyl terminated polybutadiene.
Carboxyl terminated
polybutadienes are called Hycar, a trademark of B.F. Goodrich (Buchoff, 1975).
Small amounts of butadiene were used in the manufacture of nitrile barrier
res~ns .
The use of these resins, which contained acrylonitrile (a suspected
carcinogen), has been banned by the FDA for beverage containers (Kennedy.
1977).
Two barrier resins which contained butadiene were (Nemphos et al.,
1976) :
Barex (Sohio), a 90% copolymer of 74% acrylonitrile and 26% methylacrylate
+ 10% butadiene rubber graft
Cycopac (Borg-Warner), a 90% copolymer of 74% acrylonitrile and 26% sty-
rene + 10% butadiene rubber graft.
h.
Projected Uses
BASF (Ludwigshafen, W. Germany) and DuPont are studying the feasibility of
producing adipic acid from butadiene.
BASF has reported a 49% yield of adipic
acid using a rhenium-chloride-catalyzed carbonylation of butadiene (Prescott,
1976 ).
Snam Progretti (Milan, Italy) has developed an ethylene-butadiene copoly-
mer (EDM) (Bruzzone, 1973).
Advantages of EDM are good thermal and solvent
stability.
Brownstein (1976) speculated that butadiene could be used commercially to
make styrene in a Diels-Alder reaction.
This would be possible if benzene,
the principal raw material for styrene, increased in price to exceed the price
of butadiene.
Currently, however, butadiene is not cheap enough to be con-
sidered a serious alternative starting material for styrene production.
52
-------
A new butadiene polymer, syndiotactic 1,2-polybutadiene, has been de-
veloped by the Japan Synthetic Rubber Co. with potential applications in
thermoplastics, thermosetting, resin, coating, rubber and adhesives.
(Takeuchi et al., 1974a and 1974b).
Specific uses could include plastic
stretch film, cellular sponge shoe soles, and as a matrix in a letterpress
plate system.
i.
Alternatives to Use
According to Eiicksson (1977) natural rubber could replace a synthetic
elastomer in 'some uses.
He suggests that a synthetic elastomer is preferred
irt 60% of all end-uses while natural rubber is preferred in 20% of
uses.
The
balance of uses can swing between the two depending on price.
Price has been
an important factor, for example, in the use of SBR.
SBR has few major tech-
nical advantages over natural rubber and is inferior to it in several
respects.
Its prevalence, according to Allan (1972) is due to economic
factors:
its stable price and particularly that it can be bought as an
oil-extended material.
Oligomers
2.
As discussed in the section on chemical reactions (I-D), vinylcyclohexene
can be used in some preparations for insecticides and plasticizers and as an
intermediate in preparing aliphatic hydrocarbons and antioxidants.
Cyclododecatriene is the starting material for nylon 12 production; cyclo-
dodecatriene i~ converted to dodecanolam, the precursor of nylon 12.
Cyclodo-
decatriene is also used in nylon 6/12 and Qiana nylon fiber production.
It is
first converted to dodecanedioic acid.
DuPont produces both Qiana and nylon
6/12 (Anon., 1972).
Another use of cyclododecatriene is in the production of
hexabromocyclododecane, a chemical used in flame retardants for expanded poly-
styrene.
In the U.S., hexabromocydododecane is manufactured by the Michigan
Chemical Corporation (St. Louis, Mich.) (S.R.I., 1975).
53
-------
The major use of cyclooctadiene is as a third monomer in
R
ethylene-propylene terpolymer such as DuPont's Nordel .
DuPont's capacity
for Nordel is 120 million pounds at Beaumont, Texas (SRI, 1975).
Other uses
or potential applications of cyclooctadiene cyclododecatriene are listed in
Tables 20 and 21.
c.
Entry into the Environment
Limited monitoring data indicate that butadiene monomer c~ enter the
environment during several aspects of production and use.
In ~dition, buta-
diene has been identified as a component of urban air.
Butadiene and oligo-
mers have been identified in the workroom of synthetic rubber facilities.
Monitoring studies are discussed in sections which follow.
1.
From Production
Figure 9 shows emission points for gaseous, solid and liquid wastes gen-
erated during butadiene manufacture.
In addition fugitive emissions can occur
at valves, seals, vents and leaks in equipment.
Unfortunately, the chemical
constituents of these wastes have not been quantified.
In the absence of
monitoring data, it is difficult to assess the likelihood of environmental
contamination by butadiene or oligomers during manufacture.
2.
From End Product Manufacture
a.
Workroom Levels
Occupational exposure levels to butadiene and oligomers have not been ex-
tensively reported in the U.S. and Western European literature.
In the U.S.,
workroom exposure to butadiene is limited by the Occupational Safety and
Health Administration (OSHA) to an 8-hour time-weighted average of 1,000 ppm
(2,200 mg/m3) (29 CFR 1910.1000).
No OSHA standards exist for butadiene
oligomers.
54
-------
Derivative
Name
Octyl Lactam
Epoxy-cyclooctene
Tetrahalo-cyclooctane
Suberic Acid
Octamethylene Diamine
Table 20
Derivatives of Cyclooctadiene and
Possible Uses (Ono and Kihara, 1967)
Possible Uses
Structure
o
II
r-C
(CH2tr I
L.-.NH
Nylon 8
0=0
Paints,
Adhesives
x~x
x~x
Fire-
retardant
HOOC (CH2) 6COOH
Polyesters,
Poly ami des ,
Plasticizers
NH2(CH2)8NH2
Polyamides,
Diisocyanate
OCN-(CH2)8-NCO
Octamethylene Diisocyanate
4-octenedioic Acid
Ter-monomer
Polyurethanes
HOOC(CH2)2CH=CH(CH2)2COOH
Unsaturated
Polyesters,
Alkydes
For EPT
Rubber
55
-------
Table 21
Derivatives of Cyclododecatriene
and Possible Uses COno and Kihara, 1967)
Name
Hexahalo, Cyclododecane
Epoxy-cyclo dodecadiene
Lauryl lac tam
Dodecanedioic acid
Dodecamethylene diamine
Dodecamethylene diisocynate
4,8-Dodecadienedioic acid
Structure
~
I
~
o
II
r-C
(CH2)" I
L.-NH
HOOC (CH2 ) lOCOOH
NH2(CH2) 12NH2
OCN-(CH2) 12-NCO
HOOC(CH2CH2CH=CH)2CH2CH2COOH
56
Possible Uses
Fire-
retardant
Paints,
Adhesives
Nylon 12
Polyesters,
Polyamides,
Plasticizers
polyamides,
Diisocyanate
Polyurethanes
Unsaturated
Polyesters;
alkydes
-------
l c. CUT FROM
ETHYLENE PLANT
lJl
--..J
o
o
L
GaseOU5 Emissions
501 id Waste
Liquid Haste
[TO SALES J
GO SALES]
H2
SOLVENT
SEPARATION
AND
PURIFICATION
12
[ BUTENES J
FROM
REFINERY
[:~~::EALF:OA~ ]
PLANT
REGENERATION
GASES
CATALYST
[TO SALES]
BUTANE
DEHY DROGEtiA TlON
13
BUTENES
DEHYDROGENA nON
14
...
DILU,ION STEAM
MID A In
CATALYST
REGENERA TlON
GASES
Figure 9.
Butadiene Production Processes Identifying Waste Emissions (Parsons et a1., 1977)
-------
Workroom levels of butadiene and other chemicals used to manufacture
braided hose were measured at the Gates Rubber Company (Denver, Colorado) by
the National Institute for Occupational Safety and Health (Gunther and Lucas,
1973).
In hose manufacture, braided polyester thread reinforcement is applied
to unvulcanized rubber hose.
Charcoal tubes and personal pumps were used for
sampling in the workroom.
Analysis was by gas chromatography, with a sensi-
tivity of 5 mg butadiene/sample.
In 14 samples taken on 2 different days no
butadiene was detected in the workroom.
Other studies reported the presence of butadiene oligomers in workroom
a~r.
Rappaport and Fraser (1977) detected low levels of several oligomers in
the air of a passenger tire curing room, where the tread portion of bias-ply
tires was. vulcanized.
Organic compounds were collected on activated charcoal,
desorbed with carbon disulfide and analyzed by gas chromatography-
The
authors only sampled for those compounds associated with individual products
in the stock formulation, either as add~tives or as degradation products.
Of
six compounds detected, four were butadiene oligomers (Table 22).
These olig-
amers probably originated from cis-polybutadiene rubber used in the tire
formulation.
Rappaport and Frazer (1977) consider the concentrations of com-
pounds identified in Table 22 so low that acute toxicity problems seem
unlikely.
The presence of butadiene oligomers during rubber vulcanization was con-
firmed in the laboratory.
Rappaport and Fraser (1977) developed a procedure
to simulate tire vulcanization.
The stock used in this study was uncured
tread of a bias-ply passenger tire.
Volatile organic compounds released dur-
ing vulcanization were analyzed using gas chromatography-mass spectrometry;
eighteen compounds were identified in the stock effluent, including
4-vinylcyclohexene, 1,S-cyclooctadiene, 1,S,9-cyclododecatrienes and 3 un-
58
-------
Table 22
Air Concentrations of Butadiene Oligomers
and Other Compounds in a Passenger Tire Curing
(Rappaport and Fraser, 1977)
Room
Concentration
Meanc Relative Std.
Compounda Locationb (ppb) Dev. (%)
4-Vinylcyclohexene 1 71.0 11.9
2 92.3 21. 6
1,5-Cyclooctadiene 1 6.27 23.0
2 6.45 18.1
1,5,9-Cyclododecatrienesd 1 7.21 21.1
2 15.8 29.7
Toluene 1 ll20 26.9
2 ll60 17.4
Ethylbenzene 1 78.2 29.0
2 ll2 25.7
Styrene 1 84.6 25.4
2 III 18.2
a Only these compounds were quantified; however, these are not the only
components released during vulcanization.
b Location 1 directly in center of passenger tire curing area;
location 2 at periphery of passenger tire curing area.
C Mean of 9 samples/compound.
d Cis and trans isomers.
59
-------
identified butadiene trimers.
The probable source of these oligomers is the
cis-polybutadiene rubber used in the stock formulation.
In contrast to U.S. and Western European literature, several Russian
papers identified the levels of butadiene in workroom air (Table 23).
Concen-
trations ranged from 15-40 mg/m3 in rubber vulcanization areas, 0.3-400
mg/m3 in areas of synthetic rubber production, and 0.7-1.7 mg/m3 at a
dimethyl terephthalate production facility (Table 23).
The oligomer,
4-vinylcyclohexene, was measured at average levels of 1,200-2,400 mg/m3 (and
a maximum of 3,000 mg/m3) at its site of manufacture (Bykov, 1968 in IARC,
1976a).
b.
Air Emissions
Butadiene has been identified as a minor constituent of atmospheric emis-
sions resulting from SBR production using emulsion polymerization techniques
(Table 24).
Based on information from 3 SBR manufacturers detailing all emis-
sion constituents, Pervier et ale (1974a) identified 2 sources of butadiene
emissions:
i) butadiene absorber vents and ii) fugitive emissions.
The first
source results after polymerization, when unreacted butadiene is flashed off,
compressed, condensed, and recycled.
The non-condensible contaminants (mostly
air) are vented to the atmosphere through an absorption column.
Small amounts
of butadiene, about 0.0001 pounds of butadiene per pound of SBR produced, are
vented along with the non-condensibles.
Fugitive emissions total about .00085 pounds of butadiene per pound of SBR
produced and are attributed to these sources:
lb butadiene/lb SBR
reactor section .00034
monomer recovery .00034
tank farm .00017
60
-------
Table 23
Levels of Butadiene in the
Workplace at Production Facilities
in the U.S.S.R.
Operation
Butadiene Concentration
(mgjm3)
Reference
Rubber Vulcanization
15-20
32-40
Volkova et al., 1970
Volkova et al., 1969
Synthetic Rubber Production
0.3-0.5
Bashirov, 1971
SBR Production
85-236.4
20-400
Lukoshkina et al., 1973
Konstantinovskaja, 1970
exceeded MACa
by 1.5-3.0 times
Babanov, 1960
Dimethyl Terephthalate
Production
0.7-1. 7
Lyashenko and
Sidenko, 1974
a Mean acceptable concentration.
61
-------
Emission
Hydrocarbon
Particulates &
Aerosols
NOx
SOx
0'\
N
co
Monomer
Recovery
.00010
a In weight/weight SBR.
Table 24
Atmospheric Emission Source Summary from
SBR (via emulsion polymerization) (Pervier et al., 1974a)a
Source
Polymer
Extrusion
and Drying
Packaging
Fugitive
Emissions
Carbon Black
Handling
.00100
.00100
.00002
.00010
.00002
.00021
b Total butadiene emissions estimated as .00095 ton/ton SBR (See text for sources).
Heat and
Power Cen.
.00020
Total
.00210b
.00035
o
.00020
o
-------
Tank farm eml.SSl.ons result from butadiene storage tanks (30,000-600,000 gallon
capacity), although many plants recel.ve butadiene by pipe line and have no
facilities to store it (Pervier et aI., 1974a).
The total amount of butadiene emitted is only a small fraction of total
emissions (Table 24).
Pervier et al. (1974a) described the SBR industry as a
"low (air) po lluter" and recommended that no in-depth study of SBR emulsion
polymerization be undertaken.
Ripp (1967) listed several possible sources of environmental contamination
during butadiene manufacture and synthetic rubber end-use in the U.S.S.R.:
polymerization areas; charge preparation and monomer distillation areas; ex-
traction of butadiene by chemoabsorption from a copper-ammonia complex; and
the butadiene storage areas.
Pervier et al. (1974b) evaluated atmospheric eml.SSl.ons from the older
three-step process employed to manufacture adiponitrile from butadiene and
described emissions as "moderate."
Various phases of production were sampled
for hydrocarbons, particulates, CO, NO and SO ,
x x
Nitrogen oxides com-
prised the major portion of detectable air pollutants.
For hydrocarbons, a
total of 0.0254 pounds were emitted per pound of adiponitrile produced.
Buta-
diene comprised only 3.8% of this total.
Small amounts of butadiene were de-
tected in two streams associated with chlorination.
Ripp (1967) sampled the air near a plant in the U.S.S.R. where butadiene
was produced by butane dehydrogenation and then used on-site in rubber produc-
ti on.
Samples were taken during July and August (170 samples; air temp.
25-300 (units of temperature are unspecified) and during November and
December (150 samples; air temp. -7 to -15°).
Three sample sites exceeded 3
3
mg/m (lithe proposed maximum single acceptable value") during July and
August:
50 and 70 meters from the butadiene extraction shop (6.12 and 6
63
-------
mg/m3, respectively) and 30 meters from the monomer distillation shop.
These same sites contained less butadiene during the winter:
3
3.2-3.5 mg/m
at 20 meters; 0.2-0.7 mg/m3 at 500 meters; not detected at 1500-2000
meters.
Ripp (1967) recommended that particular attention be directed toward
"sealing all systems" in the shops, especially during the summer.
c.
Water Effluent
Day (1975) identified liquid emission points from synthetic rubber manu-
facturing processes.
For crumb rubber production, the following processes
result in wastewater generation:
monomer recovery; rubber coagulation; crumb
dewatering; equipment cleanout; and area washdown.
Monomer recovery waste-
water contains butadiene, but the levels were not given; chemical constituents
of the other streams were not given.
In latex rubber manufacture, the princi-
pal liquid effluents are generated by monomer removal, equipment cleanout, and
area washdown.
In monomer removal, excess monomer is steam or vacuum stripped
prior to latex shipment; this wastewater contains butadiene at unspecified
levels.
As for crumb rubber production, the composition of waste streams from
latex rubber is not detailed.
Butadiene was not identified as a constituent of wastewater effluents from
synthetic rubber manufacture in a survey of that industry designed to develop
effluent limitation guidelines.
Since butadiene is recovered and returned to
the monomer supply plant, it has no impact on the wastewater, according to an
EPA report (EPA, 1974a).
Butadiene and other organic compounds were reported
by Bordo (1951) to be constituents of wastewaters from the Hulls Chemical
Works in Germany.
An experimental treatment procedure, involving steam
treatment and filtering, resulted in complete removal of butadiene.
64
-------
3.
From Product Use
The Russian investigators, Sopach and Krotova (1973), studied the migra-
tion of butadiene monomer and other components of butadiene rubber component
constituents into aqueous solutions.
Polybutadiene rubber suspensions (0.3-3
g) were mixed with 10 ml of distilled water and allowed to stand for 18
hours.
The test used to detect butadiene in the solution has been described
(Section II-F; based on interaction of butadiene and p-N02-benzenedizolium
in acetic acid).
Butadiene compounds were detected ~n aqueous solutions at
2-3.3 mg/l when the rubber content of the water was 30%.
No data are available on the release of butadiene under actual or s~mu-
lated use conditions.
4.
From Storage and Transport
Butadiene is often stored in tank farms, which are diked to retain spills
and leakages and to control fire spreads (EPA, 1974a).
Pervier et ale (1974a)
reported emissions from tank farms of .00017 pound butadiene per pound of SBR
produced at a synthetic rubber facility.
Transportation accidents of butadiene would pose a dangerous fire hazard
since butadiene is a gas at ambient temperatures; the flammable limits in air
are 2.0 to 11.5%.
The vapors are heavier than air and may travel a con-
siderable distance to a source of ignition and flash back; therefore butadiene
is shipped as a liquid in pressure-type containers.
A spill of liquid will,
however, float and boil on water, producing a flammable visible vapor cloud
(CHRIS, 1974).
In Section V the formation and hazards of vapor cloud
formation are reviewed.
5.
From Other Sources
Butadiene has been identified as a constituent of gasoline, ambient urban
air and cigarette smoke.
65
-------
a.
Gasoline
since butadiene is made from petroleum feedstocks it is not surprising
that it is found in gasoline.
Stevens and Burleson (1967) measured <0.002
ppm butadiene in liquid gasoline and
0.001 ppm in gasoline vapor which
represented an extremely small fraction of the total compounds detected (total
of all 27 compounds found was 33.15 ppm and 17.04 ppm in liquid and vaporized
gasoline, respectively).
Neligan (1962) measured 0.02-0.06 ppm butadiene in
diluted automobile exhaust.
When samples were irradiated for 4 hours under
ultraviolet light, levels of butadiene ranged from undetectable to 0.01 ppm,
suggesting photochemical breakdown in air (discussed in more detail in Section
II-E-1-b) .
Under both irradiated and nonirradiated conditions, butadiene was
only a small constituent of all hydrocarbons identified (Table 25).
b.
Urban Air
Low levels of butadiene «10 ppb or 0.02 mg/m3; Table 26) have been
me~sured in urban ambient air.
Data have been reported as ppb or ppm, but
have also been converted to mg/m3 in Table 26.
Ne Ii gan (1962) .sugges ts that
a major source of low-boiling hydrocarbons (i.e., butadiene) could be gasoline
from automobile exhaust.
Altshuller et ale (1971) suggested other sources:
gasoline evaporation, natural gas losses, and diffusion through soil from
petroleum deposits.
In this study Altshuller et ale (1971) also measured the hydrocarbon
composition of the atmosphere in downtown Los Angeles and Azusa, California,
taking hourly and daily measurements over several weeks.
The concentration of
butadiene averaged 2 and 1 ppb in Los Angeles and Azusa, respectively (see
Table 26).
Values for 13 other aliphatic hydrocarbons were also reported;
butadiene comprised only 0.04-0.05% of all aliphatic hydrocarbons in both
localities.
66
-------
Table 25
Analyses of Automobile Exhaust for 44 Hydrocarbons,
Including 1,3-Butadiene (Neligan, 1962)
Samplea
1,3 Butadiene
(ppm volume)
All Hydrocarbons
(ppm volume)
Diluted, Nonirradiated
1
2
3
0.02
0.04
0.06
1. 62
2.14
4.57
Diluted, Irradiated
1A
2A
3A
4A
0.005
1.46
1. 65
3.11
2.51
0.01
0.01
aSamples analyzed by gas chromatography; "Representative" automobile exhaust
was obtained from a vehicle operating under normal traffic conditions. The
composition of diluted exhaust was determined for 4 samples by gas chroma-
graphy. Each sample was then irradiated for 4 hours under ultraviolet light.
67
-------
Table 26
Ambient Air Levels of 1,3-Butadiene
Method of Level
Locality Determination ~ mg/m3 Reference
Down t own averaged da ily, 2 0.00442 Al tshuller et al.,
Los Angeles, measured over 14 1971
Calif. days
Azusa, Calif. aver aged da il y, 1 0.00221 A1tshuller et a1.,
measured over 12 1971
days
Riverside, data from 6 <0.1-0.7 <0.000221-0.001547 Stephens and
Ca lif. afternoons during Burleson, 1967
0\ air pollution
00
episode
Riverside, data from 3 2.6-9.0 0.00575-0.01989 Stephens and
Ca lif. early mornings Burleson, 1967
Los Angeles, data from 16 not detected not detected to Neligan, 1962
Ca 1 if . samples on 9 days to 9.0 0.01989
(see Table 27)
-------
Diurnal data for Los Angeles revealed that the midafternoon concentration of
faster reacting hydrocarbons, including 1,3-butadiene, I-butene, isobutene,
xylenes, and 1,2,4-trimethylbenzene decrease by a factor of three from morning
peak hours.
These hydrocarbons together constitute only a few percent of the
total hydrocarbon composition.
Slightly higher butadiene levels were reported by Stephens and Burleson
(1967) for Riverside, California.
On three mornings, butadiene levels were
2.6, 2.4 and 9.0 ppb.
Levels measured during 6 afternoon ranged from
<0.1-0.7 ppb.
In Los Angeles, Neligan (1962) measured up to 9 ppb of buta-
diene (Table 27).
c.
Cigarette Smoke
Osborne et ale (1956) measured 19 components of cigarette smoke.
In
cigarettes made from four kinds of tobacco (Bright, Burley, Cased Burley and a
blend of Bright and Burley) butadiene made up 0.95 g x 10-2 mole % of the
total volume of all gas phase components.
d.
Fire
Insignificant amounts of butadiene might enter the environment during
fires.
For example, the combustion of a piece of rubber foam 7.6 cm square
3
resulted in the evolution of 4 ppm (8.84 mg/m ) butadiene, in a smoke cham-
ber 0.6 x 0.9 x 0.9 meters (Adams, 1977).
The experimental pyrolysis (325-400oC) of polybutadiene in a vacuum
yielded about 1.5 wti. 1,3-butadiene of the total volatile components
(Madorsky, 1964).
No butadiene oligomers were specifically identified as
volatile components but Madorsky (1964) assumed dimer formation.
The actual
yield of butadiene may have been higher; dimerization on standing may have
contributed to the low yields.
69
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Table 27
Ambient Air Analyses for 44 Hydrocarbons, Including
1,3-Butadiene, from the Central Los Angeles
Business District (Ne1igan, 1962)
1,3-Butadiene All Hydrocarbons
Date Sample No.a ppm volume mg/m3 ppm volume
8/12/60 Al _b 0.348
A2 0.469
9/14/60 A3 0.004 0.00884 0.228
A4 0.002 0.00442 0.271
9/27/60 AS 0.956
A6 <0.0005 0.001105 0.921
9/28/60 A7 o. 004 0.00884 0.702
A8 0.005 0.01105 1.238
10/4/60 A10 0.001 0.00221 0.288
10/26/60 All 0.003 0.00663 0.666
A12 0.003 0.00663 0.546
11/1/60 A13 0.005 0.01105 1.117
A14 0.006 0.01326 1.624
11/2/60 A15 0.004 0.00884 0.621
Al6 O. 004 0.00884 0.622
11 / 18/60 A17 0.009 0.01989 1. 341
asamples analyzed by gas chromatography
bdash (-) indicates level below detection limit s
70
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D.
Waste Handling
Butadiene itself is not a major component of wastewaters.
The handling of
wastes from butadiene manufacture is discussed in this section.
Waste waters
are generated during several phases of butadiene manufacture.
For production
via dehydrogenation of n-butane, waste streams are produced from:
i.) scrub-
bing the gases used to periodically burn coke from the catalyst surface, ii.)
from the steam ejector-barometric condenser systems used to produce vacuum in
the reactors, and iii.) from the final recovery of butadiene product (EPA,
1974b) .
Major contaminants include residue gas, tars, oils, and unspecified
soluble hydrocarbons (Gloyna and Ford, 1970).
When butadiene is produced as a
co-product of ethylene manufacture, wastewaters are generated from the final
recovery unit (EPA, 1974b).
The composition of wastewater from several buta-
diene plants is presented in Table 28 for total flow, chemical oxygen demand,
biological oxygen demand and total. organic carbon.
The variation in flow is
due to the use of stream ejectors to produce reactor vacuum (in Table 28
plants 1 and 2, using the Houdry Process, operate at low pressures) (Parsons
et al., 1977).
Several patents describe the treatment of butadiene wastewaters.
However,
actual processes used by the industry have not been described in available
literature.
During 1977, a multimillion dollar secondary wastewater treatment
system went into operation at Firestone's Orange, Texas Petrochemical Center
(Firestone, 1977).
In a patent assigned to the Petro-Tex Chemical Corporation, Woerner (1967)
described a method for the s~ultaneous separation of butadiene from carbonyl
compounds (which are contaminants) and the disposal of boiler blowdown water
(liquid formed during cleaning or purging of boilers and is characterized by
71
-------
Table 28
Characterization of Waste Streams from Butadiene
Manufacture (EPA, 1974b)
Plant Flow CODa BOD5b
No. Process ga1/1,000 lb 1bJT;""000 1b 1b~00 lb
-
(mg/1) (fig/1) (mg/1)
1. Dehydrogenation, 1,160 3.23 2.96
Extractive Distillation (334) (06)
2. Dehydrogena ti on, 1,451 245 72
Extractive Distillation (20,200) (5,960)
3. Co-product of ethylene 88 1.120 0.547
Extractive Distillation (1,525) (745)
4. Co-product Ethylene 339 3.899 1 . 183
....... Extractive Distillation (1,378) (418)
N
5. Co-product of Ethylene 183 1 . 042 0.1 65
Extractive Distillation (683) (102)
aCOD = chemical oxygen demand
bBOD5 = biological oxygen demand at 5 days
cTOC = total organic carbon
TOCC
Wl,OOO lb
(mg/1)
0.554
(755)
1.545
(546 )
0.313
(205 )
-------
high heat, pH and concentration of solids).
Woerner's process involves us~ng
such wastewater as a treating composition to remove oxygenated compounds from
organic compounds such as butadiene.
Otherwise, this liquid must be treated
prior to discharge.
Cunningham (1971), in a patent assigned to Phillips Petroleum, outlined a
process for handling oxygenated by-products (e.g., carboxylic acids, alde-
hydes, ketone) of butadiene manufacture using the oxidative dehydrogenation
process.
Under normal operating conditions, such by-products would be vented
to the atmosphere and/or discharged with wastewater.
The invention involves
condensing oxygenated hydrocarbons with steam and recycling the condensate for
catalyst regeneration.
Hinton and Cottle (1972) developed a process for Phillips Petroleum to
purify effluent containing oxygenated hydrocarbons resulting from oxidative
dehydrogenation processes.
The procedure involves steam stripping and neu-
tralization, and water freed of oxygenated hydrocarbons is converted into
steam for use as a steam stripping medium.
Hutson and Riter (1972; patent assigned to Phillips Petroleum)developed a
process to biologically treat purge water containing oxygenated hydrocarbons.
This water is treated with aerobic microorganisms, then stripped with a hot
gas to reduce the concentration of oxygenated hydrocarbons.
Pruessner and Mancini (1966) suggested treating by-products from petro-
chemical manufacture, including butadiene, by employing an extended aeration
activated sludge system; they reported about 99% removal of BOD after 3 days.
Activated sludge treatment systems are used to treat wastewater resulting from
several processes involving butadiene (summarized in Gloyna and Ford, 1970).
73
-------
The Environmental Protection Agency listed several treatment systems
available to manufacturers of butadiene via dehydrogenation ("best available
technology economically achievable", see Section V) (Train, 1976).
One system
includes steam stripping of the process wastewaters in a closed system to
reduce the organic content of the raw waste load (COD can be reduced by
65-85%), followed by standard biological treatment (e.g., extended aeration or
activated sludge).
Biological treatment can reduce residual COD by 75% and
BOD by 99%.
Another method is the application of activated carbon systems to
biologically treated effluents.
The EPA suggested that a combination of the
above technologies is possible.
An economic impact assessment was carried out
for four combinations (or levels) of treatment alternatives (Singer, 1976).
These alternatives are listed below:
Level I
1.
Steam stripping of the most concentrated wastewater stream.
2.
Combining the stripper bottoms with the remaining wastewater for activated
sludge bio-treatment.
3.
Activated carbon adsorption of the bio-system clarified effluent.
Level II
1.
Steam stripping the entire butadiene plant wastewater-
2.
Activated sludge bio-treatment of the stripper bottoms.
3.
Activated carbon adsorption of the bio-system clarified effluent.
Level III
1.
Steam stripping of the most concentrated wastewater stream.
2.
Combining the stripper bottoms with the remaining wastewater for activated
sludge bio-treatment.
Level IV
1.
Steam stripping the entire butadiene wastewater.
2.
Activated sludge bio-treatment of the stripper bottoms.
74
-------
Level II was found to be the more expens~ve technology according to the
economic report of Singer, 1976.
Fate and Persistence in the Environment
E.
1.
Degradation in the Environment
The biological and chemical degradation patterns of butadiene are reviewed
in this section.
a.
Biological Degradation
One paper was available which suggests the possibility of biological
breakdown.
Watkinson and Somerville (1975) isolated a Nocardia species Csp.
249) from soil samples capable of using butadiene as a sole carbon and energy
source; butadiene oxidation is an inducible system in this organism.
To elu-
cidate the breakdown pathway, the following parameters were measured:
respiration, isocitrate lyase concentrations, lipid fatty acid composition
patterns, and growth.
The autttors conclude that in this Nocardia species
metabolism proceeds via formation of butadiene monoepoxide, a S,y-un-'
saturated a-ketoacid, acrylate, lactate and finally, pyruvate.
b.
Chemical Degradation
1)
Atmospheric Reactions
Photochemical Reactions.
Butadiene participates in atmo-
spheric photolysis reactions.
Stevens and Burleson (1967) collected ambient
air samples, (Riverside, Calif.), in the morning before much photolysis had
taken place.
Three samples initially contained 9.0, 2.6, and 2.4 ppb buta-
diene.
These were subjected to ultraviolet light (blacklite bulbs), and after
1 hour, the amount of butadiene was less than half of the original sample and
was not detectable after 4 hours; 2 samples were measured every hour (Table
29).
Two other samples which had been kept in the dark had relatively
unchanging butadiene concentrations even after 24 hours (Table 29).
75
-------
Table 29
Samples of Ambient Air Analyzed for Butadiene (and -25 Other
Light Hydrocarbons) in Riverside, California and then Exposed
to Ultraviolet Irradiation (A) or Darkness (B)
(Stephens and Burleson, 1967)
A.
Ambient Air Samples Exposed to Ultraviolet Irradiationa
Hours Sample Butadiene Concentrationa
Irrad. with U.V. 12/22/65 3/3/ 66
o (initial) 9.0 2.4
1 2.0 1.0
2 0.6 0.6
4 0.1 0.0
8 0.0 0.0
17 0.0
20 0.0
24 0.0 0.0
(7Pb)b
3 10/66
2.6
0.0
B.
Ambient Air Samples Kept in Darknessa
Hours Sample
Kept in Dark
Butadiene Concentrationc (ppb)b
3/3/66 3/10/66
o (initial)
0.75
24
2.0
1.0
2.0
2.8
2.6
aAll samples taken at the Riverside County Building of Health and Finance
between 07:00-08:25 PST. Weather conditions were as follows: 12/22/65
partly cloudy, calm, 4S-50oF, light haze; 3/3/66 sky clear, wind 5-7 mph
N.W., 40-450F, moderately heavy haze; 3/10/66 sky clear, wind 0-1 mph,
55-60oF, heavy haze
bl ppb = 0.00221 mg/m3
cConcentrations of other light hydrocarbons ranged from 1.3-310.5 ppb on
12/22/65 (x = 41.3, S.D. = 65.0), 1.0-62.4 ppb on 3/3/66 (x = 12.3, S.D. =
16.2), and 1.2-70.5 ppb on 3/10/66 (x = 16.6, S.D. = 21.0)
76
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Reac~ion wi~h Oxides of Ni~rog~~ and Ozone.
The forma-
tion of photochemical smog is triggered by the atmospheric photooxidation of
hydrocarbons in the presence of oxides of nitrogen.
Irridation of air con-
taining hydrocarbons and oxides of nitrogen leads to the oxidation of NO to
NOZ' the oxidation of hydrocarbons and the formation of ozone.
Several in-
vestigators have compared the reactivity of hydrocarbons with nitrogen oxides
under laboratory conditions and found that rates for individual hydrocarbons
vary widely.
Butadiene is one of many hydrocarbons for which data are
available.
Ruess and Glasson (1968) mixed a~r containing 2 ppm butadiene and 1 ppm
nitric oxide, and irradiated the mixture in a smog chamber for 6 hours.
At
the end of this period, 92% of the butadiene had reacted (Table 30).
The rate
of N02 formation in the presence of butadiene and nitric oxide was calcu-
1ated as Z5.0 ppb/minute in two determinations.
For comparison, this rate
varied from 1.6 to 170 ppb/minute in 25 hydrocarbons tested (x = 19.Z ~ 33.6
(SD)).
The following classes of hydrocarbons are given in order of in-
creasing rates of NOZ formation:
benzene, paraffins, monoalkylbenzenes,
terminal ole fins, multialkylbenzenes, 1,3-butadiene, and olefins with internal
double bonds.
Glasson and Tuesday (1970a) determined the reactivity of 81 hydrocarbons,
including butadiene, in the atmospheric photooxidation of nitric oxide.
Analyses were made with a long-path infrared spectrophotometer.
For buta-
diene, the nitric oxide photooxidation rate averaged 4.3 ppb/minute in two
determinations (Table 30).
This rate for 41 olefins tested ranged from 1.5 to
59 ppb/minute (x = 9.5 ~ 12.9 (S.D.)).
The products formed in the photooxidation of butadiene and nitrogen oxide
include the following:
acrolein, aliphatic aldehydes, ethylene, formaldehyde,
77
-------
Table 30
Photooxidation of 1,3-Butadiene and Nitric Oxide
Altshuller
et al.
0966 )a
Ruess and Glasson
(1968)b
Glasson and Tuesday
(1970a )c
Reactants (ppm)
Butadiene 3.3 2 1
Nitric oxide 0.85d 1 0.4
% Butadiene reacted 83% 92% NR
Rate N02 formatione NR 25.0 ppb/min 4.3 ppb/min
03 rate NR 4.05 ppb/min NR
Product Yields (ppm):
Acrolein 1.0 0.73
Aliphatic aldehydes 1.15 NR
Ethylene 0.022 NR
Formaldehyde 0.85 0.80
Ozone NR 0.48
Pero xy acetyl nitrate NR 0.02
NR = not reported
areactants irradiated in a large chamber; average residence time 180 min.
breactants irradiated in a smog chamber for 6 hours at 950F
creactants irradiated in long path cell at 790F
dnitric oxide plus nitrogen dioxide formed by thermal oxidation (5-10%
of total)
eaverage rate to the half-time
78
-------
ozone and peroxyacetyl nitrate (Altshuller et al., 1966; Ruess and Glasson,
1968) .
The yields of these products are given in Table 30.
The data just discussed above are for the photooxidation of nitric oxide.
Glasson and Tuesday (1970b) investigated whether thermal oxidation of nitric
oxide might be important as well.
In particular, the authors wanted to deter-
mine if this reaction might be partially responsible for the night time con-
vers~on of nitric oxide to nitrogen dioxide in polluted atmospheres.
They
determined that for dienes, the photooxidation of nitric oxide is faster than
the corresponding thermal oxidation.
As a measure of reaction time, t1/4
was calculated, defined as the time necessary to convert 25% of the initial
concentration of nitric oxide to nitrogen dioxide.
For butadiene, the t1/4
for thermal oxidation was 311 minutes while for photooxidation
t1/4
equaled 20 minutes (both reactions were carried out at 5 ppm butadiene and 2
ppm NO).
The authors concluded that for butadiene and 5 other dienes
investigated, diene-promoted thermal oxidation. will be relatively un-
important in polluted atmospheres compared to photooxidation.
Ozone forms in the atmosphere when the N02 levels are about 25 times
that of NO.
When ozone concentrations are 0.25 ppm or greater, ozone and
olefins react at appreciable rates (Seinfeld, 1975).
Ranst et al. (1959) de-
termined rate constants for the reaction of ozone with 13 different olefins.
For butadiene, k = 0.012 ppm min-1; for all olefins tested k ranged from
0.0001 to 0.24.
The rate of reaction between ozone and olefin was second
order, being proportional to the product of the concentrations of the two
reactants.
The position of the double bond influences the rate of reaction;
olefins with an internal double bond react more rapidly than those with a ter-
minal double bond (such as butadiene).
79
-------
2)
Reaction with Water
Butadiene does not react appreciably with water (refer to Figure 1, Solu-
bility in Water).
If butadiene contacts a body of water (as in a
transportation accident), it will float and boil on the water, forming a flam-
mable visible vapor cloud.
Vapor cloud formation and hazards are discussed in
Section VI.
2.
Transport and Persistence
Based on limited monitoring data, butadiene is not likely to be released
in large quantities to the environment.
In a situation where the monomer
might be released (i.e., storage tanks, transportation accidents), butadiene
will vaporize and enter the atmosphere.
Butadiene is highly reactive in the
atmosphere, participating in reactions with light, nitrogen oxide, and ozone,
as discussed in the previous section.
If butadiene enters or spills on water
it will float and vaporize rapidly.
Persistence of vaporized material is dis-
cussed in more detail in the section on Exposure and Effects Potential (Sec-
tion VI).
F.
Analytical Detection Methods
Methods of analytical detection for butadiene and impurities in butadiene
are discussed for several media.
In most cases, gas chromatography is
employed.
1.
Butadiene
a.
In Air
A method for determining butadiene in the industrial atmosphere has been
developed by the National Institute for Occupational Safety and Health (NIOSH,
1975).
A known volume of air is drawn through a charcoal tube consisting of 2
sections to trap organic vapors.
A flow rate of 0.05 liter/min. or less and a
80
-------
total volume of 1 liter is recommended for personal sampling pumps.
~e
sample of charcoal from each section is transferred to a separate container
where each is desorbed for 30 minutes with 1.0 ml of carbon disulfide.
An
aliquot of each desorbed sample is injected into a gas chromatograph using the
solvent flush injection technique.
The area of the resulting peak is deter-
mined and is then compared with standards based on mg/1.0 ml carbon disulfide;
corrections must be made for the blank containing solvent alone.
This method was validated over the range of 1065 to 4590 mg/m3 (coeffi-
cient of variation 0.058) at 22°C and 760 mm Hg using a 1 liter sample,
3
although it is probably effective over 200 to 6600 mg/m .
If the desorption
efficiency is adequate this procedure could measure smaller amounts.
NIOSH
cautions that high humidity may decrease the breakthrough volume.
Compounds
with the same retention time as butadiene at the operating conditions used in
this procedure will interfere.
Coker (1977) criticized the NIOSH method, citing several disadvantages:
i) on the spot readings are not possible; ii) the pre-analysis procedure is
time consuming; iii) desorption solvents (e.g., carbon disulfide) are toxic;
iv) solvent peak interferes with the chromatogram; v) recovery is incomplete;
and vi) sampling tubes have a limited capacity and cannot be re-used.
Coker
suggested using heat desorption rather than solvent desorption to overcome
these disadvantages.
Heat desorption was used successfully to determine buta-
diene in butenes and butanes from steam cracker units.
Stephens and Burleson (1967) described a chromatographic procedure for
analyzing atmospheric light hydrocarbons at concentrations below 1 ppb.
A
freeze-trap, which was prepared by filling stainless steel tubing with chroma-
tographic substrate was installed in place of the gas sample loop of a flame
ionization chromatograph.
A sample of 0.1-0.5 liters of air was passed
81
-------
through the trap; the trap had been chilled with liquid oxygen.
The sample
was then injected into the chromatograph.
Altshuller et al., (1971) collected samples of light hydrocarbons in Cali-
fomia, with an automatic tbne sequential air sampler.
Siddiqi and Worley
(1977) sampled hydrocarbons in Texas using a pump or syringe.
Both investiga-
tors analyzed the samples using a gas chromatograph equipped with a flame
ionization detector.
Aliphatic hydrocarbons, including butadiene were
separated using packed columns.
Manita and Ripp (1965) used spectrophotometric methods to determine small
concentrations of 1,3-butadiene in the presence of other compounds (e.g., sty-
rene, isopropylbenzene, butane and butylenes) in the air around a synthetic
rubber plant.
Air was drawn through silica gel and organic substances were
extracted with isooctane.
The optical density of the isooctane solution was
measured at wavelengths of 224 and 245 nm in a quartz cell with an SF-4
spectrophotometer.
For these wavelengths, the Bouger-Lambert-Beer law is
obeyed for concentrations of 1-10 micrograms butadiene/mI.
The concentration
(c) of butadiene (in micrograms/ml) was calculated from this formula:
C = 2.5 (E224-0.47E245)j the latter quantity is the difference in
absorbance.
The sensitivity of this method is 0.125 ~g/ml and the accuracy
is within z 2.6%.
Kreuzer et al., (1972) described a method for detecting butadiene and
other air pollutants at concentrations of a few parts per billion using gas
lasers.
The procedure involves measuring the strength of the absorption of
infrared radiation at several emission wavelengths from carbon monoxide or
carbon dioxide lasers.
For butadiene, the absorption was determined at the
P(13) line (6,Z15.3 nm) using the CO laser and at the P(30) line (10,696.4 nm)
us~ng the C02 laser.
Sensitivities of 1 and 2 ppb were obtained with the CO
and COZ lasers, respectively.
This method allows detection of butadiene
even in the presence of larger concentrations of other absorbing gases.
82
-------
b.
In Water
Webber and Burks (1952) developed a carbon dioxide stripping method to
determine butadiene and other light hydrocarbons in water primarily for the
evaluation of hydrocarbon losses in process cooling water and steam conden-
sate.
This method involves desorbing the hydrocarbons from water by passing
carbon dioxide through the sample; the gas stream is then passed through an
absorber and buret filled with a potassium hydroxide solution in which the
carbon dioxide is absorbed.
The volume of butadiene and other hydrocarbons is
measured in the buret as a vapor.
In four determinations of known amounts of
butadiene in water, the authors reported 93-97% recovery by this method.
Sopach and Krotova (1973) developed, in the U.S.S.R., a method to detect
the presence of butadiene in aqueous solutions.
This procedure is based on
the reaction, in an acetic acid medium, of butadiene with the
p-nitro-benzendiazonium ion, which yields a yellow product whose optical dens-
ity is determined photocolorimetrically.
Acetone, toluene, and methylene
chloride up to 1,000 mg/liter do not interfere.
The sensitivity of the method
for butadiene is 2 mg/liter.
c.
In Polymers
Residual butadiene monomer in polymer or copolymer by-products can be
determined by gas chromatography, either by direct injection or by head-space
analysis.
Steichen (1976) compared the two methods for butadiene and found
solution head-space analysis to be more sensitive (detection limit 0.05 ppm)
than direct injection (detection limit 10 ppm).
Other advantages of
head-space analysis are the prevention of column contamination and the reduc-
tion of interferences.
Head-space analysis involves the equilibration of a
solid polymer in a closed system.
The residual monomer is partitioned between
the polymer phase and the head-space (air above the sample); the monomer con-
83
-------
centration in the head-space is then determined.
Steichen's (1976) procedure
was to equilibrate vials containing butadiene polymer solutions for at least
30 minutes at 900C before head-space sampling using an automated apparatus.
Shapras and Claver (1964) described a gas chromatographic method for de-
termining residual butadiene in acry1onitri1e-butadiene-styrene terpolymer.
The polymer was dissolved in chloroform, then dried.
A gas chromatograph
equipped with a hydrogen flame detector was used to detect less than 10 ppm of
residual monomers in styrene-based polymers.
The ~ount of free butadiene in butadiene rubbers can be determined at
>0.005% concentration using a gas chromatograph equipped with a flame ion-
ization detector (LiGotti et al., 1972).
d.
In Biological Material
Carpenter et al., (1944) developed a method for determining butadiene in
At 200oC, butadiene is
blood based on the reaction with iodine pentoxide.
completely oxidized by iodine pentoxide, with the liberation of 2.2 molecules
of iodine for each molecule of butadiene present.
The liberated iodine is
collected and titrated with sodium thiosulfate, and the amount is used to
calculate the concentration of butadiene.
In 8 trials with known amounts of
butadiene, recoveries averaged 96.3-99.5% us~ng this method.
e.
In Process Streams
Carson, Young and Lege (1972) developed a gas chromatographic column to
analyze butadiene plant process streams and the gas phase effluent from
naphtha feedstock thermal cracking furnaces in an ethylene plant as well as to
analyze commercial grade butadiene.
The column consists of two sections con-
nected in series.
The first section contains 20% dibutyl maleate and the
second contains 10% bis-(2-methoxyethoxy)ethyl ether; both compounds are on
60/80 mesh Chromosorb P-NAW.
The column was used on gas chromatographs using
84
-------
hydrogen flame ionization or thermal conductivity detectors.
In Table 31
appears component identification of butadiene process streams (3la) and gas
phase effluent (3lb) using this column.
The American Society for Testing Materials (ASTM, 1975) described a
standard method to detect 1,3-butadiene in C4 hydrocarbon mixtures.
The
mixture can contain up to 25% butadiene.
The butadiene concentration is cal-
culated from the absorbance of the sample us~ng an ultraviolet spectrometer.
Vinyl acetylene and 1,2-butadiene will interfere if present in amounts of 0.5
and 2%, respectively, of the 1,3-butadiene content.
2.
Impurities in Butadiene
Carson and Lege (1974) caution that depending on the temperature of the
gas chromatographic vaporizer, dimerization of butadiene sample may occur dur-
ing analysis.
This would, therefore, unknowingly increase the amount of dimer
reported in the sample.
Dimer formation in the gas chromatograph vaporizer
varies directly with temperature, as shown in Table 32 for 9 temperature in-
crements between 155 and 325°C.
Because of this, the amount of
4-vinylcyclohexene generally reported to be in butadiene may, in fact, be
somewhat lower.
Vinylcyclohexene can be determined in butadiene concentrates
by gas chromatography (ASTM, 1975).
85
-------
Table 31
Gas Chromatographic Analysis of
A) Butadiene Process Streams and
B) Gas Phase Effluent from an Ethylene
Plant using Naphtha Feedstock
(Carson et al., 1972)
A) Butadiene Process Stream Components
Methane
Ethane + ethylene
Propane
Acetylene
Propylene
Isobutane
Cyclopropane
Propadiene
n-Butane
Neopentane
Butene-1 + isobutylene
Methylacetylene
trans Butene-2
cis Butene-2
1,3-Butadiene
Isopentane
3~ethylbutene-1
n-Pentane
1,2-Butadiene
Ethyl acetyl ene
2 Methylbutene-1
1,4-Pentadiene
trans Pentene-2
Vinyl acetylene
2 Methylbutene-2
2~ethylpentane
Isoprene
Dnnethylacetylene
86
-------
Table 31 (Cont'd)
Gas Chramatographic Analysis of
A) Butadiene Process Streams and
B) Gas Phase Effluent fram an Ethylene
Plant using Naphtha Feedstock
(Carson et al., 1972)
B) Gas Phase Effluent from an Ethylene Plant Using and
Naphtha Feedstock
Component
Weight %
Air
Methane
Ethane + ethylene
Propane
Acetylene
Propylene
I so bu t ane
Propadiene
n-Butane
Butene-1 + isobutylene
Methyl acetylene
trans Butene-2
cis Butene-2
l,3-Butadiene
Isopentane
3 Methylbutene-1
1,2-Butadiene
Ethylacetylene
2 Methylbutene-l
1,4-Pentadiene
trans Pentene-2
Vinylacetylene
2 Methylbutene-2
2 Methylpentane snd
Isoprene
Dimethylacetylene
18.73
35.05
0.69
0.50
19.76
0.04
0.56
0.07
6.17
0.67
0.75
0.58
5.95
0.22
trace
0.41
0.29
0.69
tr ace
0.21
trace
0.44
3.47
trace
The Ethane-Ethylene Ratio as well as the % hydrogen and carbon
dioxide in the above analysis are listed below and were analyzed
on other columns.
Component
Weight %
Hydrogen
Carbon Dioxide
Ethane
Ethylene
0.96
22 ppm
5.36
29.69
87
-------
Effect of
Vaporizer
Temperature
°c
Table 32
Temperature on Vinylcyclohexene
in Gas Chromatograph Vaporizer
(Carson and Lege, 1974)
Formation
Dimer
PPM
Temperature Increase
Above Initial Point
°c
155
170
185
200
215
230
245
260
275
300
325
2
3
3
12
37
70
128
227
407
888
2, 465
o
15
30
45
60
75
90
105
120
145
170
88
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III.
BIOLOGICAL EFFECTS
The available literature on the biological effects of butadiene and its
oligomers are discussed in the sections which follow on toxicity and fate.
A
cursory review of the biological effects of butadiene appears in Parsons and
,
Wilkins (976).
A.
Humans
1.
Acute Toxicitv
Acute exposures to butadiene are discussed in terms of s~gns and symptoms,
and effects on psychomotor function.
No data are available on the toxicity of
butadiene oligomers to humans, although their presence has been detected in
the workroom of rubber plants (see Section III-A-Z).
a.
Signs and Symptoms
Inhalation of butadiene is mildly narcotic at concentrations below the
lower explosive limit (2% or 44,260 mgjm3) and may result in a feeling of
lethargy and drowsiness.
Exposure to the gas can cause minor irritation to
the eyes and the mucous membranes of the upper respiratory tract as well as
asphyxiation by exclusion of oxygen (MCA, 1974; Steere, 1968).
Dermal contact with liquid butadiene causes a sensation of cold followed
by one of burning, the result of rapid evaporation; this may cause frostbite.
Superficial burns can develop from absorption of butudiene through clothing or
skin (MCA, 1974; Lefaux, 1968).
Workers exposed to butadiene vapor in the manufacture of rubber com-
plained of irritation of the eyes, nasal passages, throat and lungs.
In some,
coughing, fatigue and drowsiness developed (Wilson, 1944).
All symptoms dis-
appeared on removal from the vapors.
The concentrations were stated only as
89
-------
"not heavy."
Subsequent exposures resulted in the same symptoms, but as these
were not excessive, Wilson (1944) suggests there is no cumulative action.
Physical and blood examinations and urinalyses were negative.
Two male subjects reported slight smarting of the eyes and difficulty in
focusing on instrument scales during 6-7 hours' exposure to 2,000 and 4,000
ppm butadiene (4,420 and 8,840 mg/m3).
Exposure for 8 hours to a higher
concentration, 8,000 ppm (17,680 mg/m3), was without effect.
The authors
conclude that butadiene in the concentrations inhaled was innocuous (Carpenter
et al., 1944).
Inhalation of a 1% (22,130 mg/m3) mixture of butadiene
in air
for 5
minutes caused no effects on respiration or blood pressure except for a slight
quickening of the pulse, a slight feeling of dryness, and prickling in the
mou th and nos e .
However, 20 exposures for 2 hours each to 140 mg/l (140,000
mg/m3) caused some irritation to the lungs, irritation of the spleen, and
slight hyperplasia of the bone marrow (no other details are given) (Von
Oettingen, 1940). '
A group of 10 or 15 panelists determined eye irritation after exposure to
the photooxidation products of butadiene and nitrogen oxide mixtures
(Altschuller et al., 1966).
Responses were scaled 0-30; the higher the re-
sponse the more severe the eye irritation.
Two indices were calculated:
1)
the average response of all panelists; and 2) the average of the highest con-
secutive responses of all panelists.
For the former index, butadiene-nitrogen
oxide products scored 20; for the latter, a score of 22 was calculated.
These
values were higher than eye irritation indices calculated for several com-
pounds, including ethylene-NO and 1-butene-NO mixtures (average responses
ranged from 0-13).
90
-------
Reuss and Glasson (1968) determined the eye irritation of 25 photooxidized
hydrocarbons including butadiene.
Each hydrocarbon (2 ppm) was added to
nitric oxide (1 ppm) in air and the mixture was irradiated in a smog chamber
for 6 hours* at 950F.
For butadiene, products yields were:
formaldehyde
(0.80 ppm)j acrolein (0.73 ppm)j
oz one
(0.48 ppm)j and peroxyacetylnitrate
(PAN, 0.02 ppm).
Eye irritation was rated on a scale of 0-3 (0 = none, 3 =
severe) after 6 hours by panelists exposed for 4 minutes to reaction
products.
The time until eye irritation was first detected was also
recorded.
Of all hydrocarbons tested, photooxidized butadiene was the most
severe eye irritant.
The time-to-irritation was only 73 seconds; for the
other compounds it ranged from 86-240 seconds (x = 180 seconds).
The
photooxidized butadiene containing air was the only mixture rated 3 for the
eye irritation indexj the other irradiated mixtures ranged from 0.0-2.5 (x =
1.2).
The Russian investigator Ripp (1967) studied the effect of butadiene on
irritation of the eye in four persons (age 20-35 years).
This was determined
while the subjects breathed from a cylinder containing pure air and compared
to that when butadiene was introduced into the cylinder at 4.2-3.6 mg/m3.
3
At 3.6 mg/m there was no change in irritation in any subjects while at 4.2
and 4.0 mg/m3 Ripp reported a "significant increase" in irritation in all
subjects.
The procedure used to measure irritation was not described.
*The English translation reads "light sensitivity", however, as subjects were
exposed in the dark, irritation to the eye was actually being measured.
91
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b.
Effects on Psychomotor Tests
Carpenter et ale (1944) evaluated psychomotor responses of two male sub-
jects inhaling, on different days, 2,000, 4,000 or 8,000 ppm butadiene (4,420,
8,840, or 17,680 mg/m3, respectively) for 6-8 hours/day.
At the two higher
concentrations the subjects performed a steadiness test, while at the highest
concentration a tapping rate test was also performed.
In the latter test, the
number of taps in each 6 second interval of a three minute period were re-
corded.
Results after butadiene inhalation were identical to those obtained
before exposure.
The steadiness test involved holding at arms length a thin
wire in a ring for 3 minutes; the contacts of the wire with the ring were
recorded on a kymograph.
Results for the steadiness test were inconclusive as
the subjects were more unsteady at 4,000 ppm (8,840 mg/m3) (score of 266
compared to 100 for pre-exposure) than at 8,000 ppm (17,680 mg/m3; score of
136) .
The authors attribute this to the fact that "the subj ects were probably
physically or mentally.below par on the 4ay of the 4,000 ppm test"; i.e.,
butadiene was probably without effect.
2.
Organoleptic Thresholds
The Russian investigator Ripp (1967) determined the olfactory threshold of
3
butadiene to be 4 mg/m in 16 persons whose age ranged from 18-36 years.
The following data were obtained in a total of 336 trials:
No. Subjects
Butadiene Concentration (mg/m3)
Minimum Perceptible Maximum Imperceptible
6
6
3
1
4.0
4.2
4.4
4.8
3.8
4.0
4.2
4.4
92
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In addition to odor threshold and light sensitivity, Ripp (1967) also
measured the "threshold of reflex action" of butadiene by electrocortical re-
cording.
Four persons (2 men, 2 women; 18-30 years old) were exposed to buta-
diene at 3, 3.6 and 3.8 mg/m3.
An electroencephalogram recorded reflex de-
synchronization of alpha rhythms at the two higher levels tested.
Few pro-
cedural details were given to enable evaluation of these results.
3.
Occupational Exposure
a.
Butadiene
Although acute exposure to butadiene may occur through accidents and im-
proper handling, there have been no reports in the u.s. or W. European liter-
ature of any chronic effects arising from the industrial use of butadiene.
Epidemiologic studies are available for the rubber industry, which is the
largest user of butadiene monomer.
A number of health hazards have been de-
scribed for rubber workers.
Although the causative agents have not always
been identified, butadiene has not been implicated in any of these studies.
Suspected or causative agents include the following compounds used in the pro-
duction of synthetic rubber:
styrene, cumene hydroperoxide, p-nitroaniline,
phenyl-S-naphthylamine and sodium dimethyl dithiocarbamate (NIOSH, 1976).
Some epidemiologic studies have suggested excess morbidity and mortality in
rubber workers (Table 33).
Among these is the suggestion of excessive mor-
tality from some types of cardiovascular disease, and malignant neoplasms
(including, bladder, stomach, large bowel, lymphatic and hematopoietic tis-
sues, and possibly the central nervous and respiratory systems) (McMichael et
al., 1977).
In the U.S. at least 10 leukemia cases have recently been iden-
tified among styrene-butadiene rubber (SBR) workers.
(Smith and Ellis,
1977).
Since there is no evidence to date in u.S. or Western European liter-
ature that butadiene or its metabolites are responsible for excessive disease
93
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Table 33
Epidemiology Studies for Rubber Workers
Job Description
Major Findings
A. Britain
rubber workers
differences in morbidity
between workers and office
staff based on sickness and
absenteeism
rubber workers
10% mortality excess compared
to national figures
rubber & cable making
industry
excess neoplasms, especially
bronchial neoplasms compared
to national figures
urinary bladder tumors
higher mortality among
production than office
workers
B.
United States
rubber workers
increased rate for malignant
neoplasms of respiratory
system, chronic rheumatic
heart disease, emphysema &
arthritis compared to other
industrial workers
rubber workers
excess death rate from malig-
nant neoplasms (8%); chronic
rheumatic heart disease
(10%); arteriosclerotic
heart disease (15%) compared
to workers in all
manufacturing industries
tire manufacturers
excess malignant neoplasms
of the stomach, prostate
and blood-and-lymph forming
tissues compared to U.S.
national mortality data
94
Authors
Parkes, 1966 in
McMichael et al.,
1976
British Registrar
General, 1929-31 in
McMichael et al.,
1976
Fox et al., 1974
Case and Hosker,
1954
Mancuso et al.,
1968
HEW, 1967 in
McMichael et
al., 1976
HEW 1961-1963
in McMichael et al.,
1976
McMichael et al.,
1976
-------
Job Description
tire curing workers
rubber processing
workers
Table 33 (Cont.)
Epidemiology Studies for Rubber Workers
Major Findings
higher incidence of chronic
bronchitis compared to
nonexposed rubber workers
chronic productive cough
compared to nonexposed
rubber workers
95
Authors
Fine & Peters 1976a
Fine & Peters 1976b
-------
and mortality, these epidemiologic studies will not be reviewed here (see re-
view in McCormick,
1971) .
In contrast to U.S. and Western European investigators, who do not con-
sider butadiene to have chronic toxic effects, Eastern European scientists
have recently reported upon effects possibly resulting from occupational ex-
posure to butadiene.
A number of studies have been conducted on workers
handling butadiene and styrene (or methylstyrene), among other chemicals, dur-
ing synthetic rubber manufacture.
Poorly documented cases of gastrointestinal
tract, respiratory, circulatory and nervous system disorders, among others,
have been reported.
Most of these studies implicate butadiene and styrene as
causative agents because they are the basic monomers used in synthetic rubber
manuf ac ture .
Although such reports also list other major compounds to which
workers were exposed, consideration was not usually given to various initi-
ators, modifiers or antioxidents identified by U.S. and Western European in-
vestigators as possible health hazards.
Many of these studies did not use an
adequate control population or provide adequate details of exposure conditions
(Scala, 1977).
Since workers were exposed to many chemicals, the effects
described in the Eastern European literature for rubber workers cannot be at-
tributed to butadiene alone.
However, since many of these investigators
implicate butadiene as at least one of several possible causative agents, the
Eastern European literature is reviewed in the following sections.
Effec"ts on Gas"troin"tes"tina,l Trac"t and Liver.
A Study of 80 workers
handling butadiene and styrene during the production of SBR in the U.S.S.R.
revealed a higher incidence of chronic gastritis.
Changes in the liver in-
eluded altered detoxification and protein synthesis; changes in the blood pro-
teinfractions (decreased albumin level, increased ~l' ~2 and a
globulins) were also observed (Bashirov, 1968).
A further study of 130 SBR
96
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workers suffering from chronic gastritis revealed that 73% had accompanying
symp toms:
inflamed gallbladder (37%), pancreas (17%) and hepatitis (19%)
(Bashirov,1971).
These workers were exposed to 0.3-0.5 mg/m3 butadiene and
3
0.06-0.12 mg/m styrene.
Other studies have also reported gastric disorders among workers exposed
to butadiene and styrene (Bashirov 1967, 1970, 1973; Batkina, 1966).
Accord-
ing to one investigation, exposure to butadiene, styrene, butane, butylene,
benzene, sulfuric acid and catalysts produced a high frequency of gastric
diseases (66.6%) in a study of 679 synthetic rubber employees.
Workers
exposed to mixtures of butadiene and styrene showed liver enlargement and a
decrease in functional tests of the liver (Quick-Pytel Test) and spinal fluid
(Takata-Ara-Test) (Orlova and Solov'eva, 1962).
Volkova et ale (1970) assessed the health of 60 press operators at an SBR
rubber vulcanization plant in the USSR based on the following workroom
exposures:
3
mg/m
butadiene
26-45
styrene
2-40
oil aerosal
60
formaldehyde
1.1-10
acrolein
1.5
acrylonitrile
1-11
sulfur dioxide,
ammonia, carbon dioxide
not spec ified
Medical examination revealed gastrointestinal tract disturbances, including
heartburn, vomiting and nausea (25%), peptic or duodenal ulcers (12%), chronic
gastritis (13%), gallbladder inflammation (5%), and liver enlargement (13%).
97
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Effects on the Kidney.
A study of 69 workers exposed to butadiene
and styrene during synthetic rubber production revealed
renal dysfunction in
workers with more than 6 years exposure (Konstantinovskaya, 1970).
Faustov
(1972) also reported kidney dysfunction among synthetic rubber workers, but
attributed this (and other toxic effects) to the catalysts used.
Effects on Endocrine Glands.
Endocrine function was examined in 70
Russian Styrene-Butadiene Rubber (SBR) workers handling butadiene and styrene;
most had been employed for more than 10 years (Bashirov, 1969).
The most
frequent symptom (34%) was glucocorticoid insufficiency of the adrenal
cortex.
Thyroid hyperfunction was observed in 24%, while depressed pancreatic
activity of the Islets of Langerhans occurred in 20%.
The longer a worker had
been employed, the more severe the endocrine changes.
Effects on Blood and Circulation.
Batkina (I966) reported a
tendency to hypotension, leukopenia, and increaseq erythrocyte sedimentation
and hemoglobin levels among 100 rubber workers exposed 10-15 years in areas
where butadiene was separated and purified.
Khusainova (1971) found the
following tendencies among 1,406 workers in contact with butadiene and
a-methylstyrene in SBR production compared to 200 controls:
. .
~ncrease U1
hemoglobin, and erythrocytes; leukocytosis; lymphocytosis; decrease in
leukocyte glycogen, lipid and peroxidase; decrease in color index.
Functional disorders of the cardiovascular system were reported among
workers exposed to butadiene and alpha-methylstyrene (Konstantinovskaya,
1971) .
In 60 workers having prolonged contact with butadiene, styrene, and
ethylbenzene, the following was reported:
decreased tonus of the peripheral
vascular system (Alekperov et al., 1971), altered electro - and ballisto-
cardiograms (Alkperov et al., 1970); abnormal myocardial contraction and hypo-
98
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tension (Vinokurova, 1969); and increased capillary permeability and high
resistance to blood flow (Alekperov et al., 1968).
Effect on lipid-Protein Metabolism.
One hundred workers handling
butadiene and styrene during rubber production in the U.S.S.R. were examined
for adverse effects on lipid-protein metabolism (Lukoshkina et a1., 1973).
Levels of butadiene and styrene in the workroom air were 85-236.4 and 2-13.5
3
mg/m , respectively.
Compared to a group of 30 controls, workers exhibited
increased blood cholesterol levels (total, free, and esterified), especially
as a function of age and length of employment.
Effects on Skin.
Of 60 Workers who were exposed to styrene and
butadiene and other rubber processing chemicals, 27% showed occupational der-
matitis and 33% exhibited mucous membrane changes, including dryness, thicken-
ing and pallor (Volkova et al., 1970).
Other investigators also noted skin
disorders among rubber workers, which include:
dry palms (Volkova and
Bagdinov, 1969), dermatosis (Mirzoyan and Tsai 1972) and unspecified skin
diseases (Abdullaeva, 1973).
Effect on Health & Growth of Juveniles.
Klein et al. (1967) com-
pared growth rates and morbidity of 85 apprenticed SBR students with 74
apprenticed agriculture students in Czechoslavakia.
The average age of begin-
ning apprentices was 16, and the training lasted 3 years.
Al though growth
rates did not differ, SBR students showed significantly higher rates of in-
fections, illness, and sore throats.
Effects on Nervous System.
An examination of 60 workers exposed to
butadiene, styrene and other chemicals revealed the following disorders:
sup-
pressed corneal (39%) and peritoneal reflexes (31%), and hyperalgesia (30%)
(Volkova et al., 1970).
Gus'kova (1971) reported adverse effects on the
nervous system in workers exposed to butadiene and styrene, and unspecified
99
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"functional disease" of the nervous system were reported among 39% of 100
rubber workers exposed to butadiene (Batkina, 1966).
Effec~ on Respira~ory Trac~.
A study of 317 workers in a synthetic
rubber plant exposed to butadiene, butane, styrene, benzene, sulfuric acid and
a catalyst revealed a higher rate of respiratory diseases (18.6% of the
workers) among those employed more than 10 years compared to those working
less than 5 years (4.25% of the workers) (Abdullaeva, 1973).
Faustov (1972)
reported inflammation of the mucous membrane among SBR workers exposed to
butadiene, styrene, isoprene, solvents and catalysts.
Employees working in a rubber vulcanization area were exposed to buta-
diene, styrene and other chemicals as well as to heat (Volkova and Bagdinov,
1969 ).
Records of absenteeism were examined and, compared to other workers,
there was a high frequency of influenza and catarrh of the upper respiratory
tract (26.6%) and tonsillitis (10.9%).
Medical examination showed mucosal
changes in the upper respiratory tract, which altered olfactory perception.
Orlova and Solov'eva (1962) reported laryngotracheitis and bronchitis in
workers occupationally exposed to various rubber processing chemicals, in-
eluding butadiene.
b.
Vinylcyclohexene
Russian workers exposed to 4-vinylcyclohexene exhibited keratitis, rhin-
itis, headache, hypotonia, leukopenia, neutrophilia, lymphocytosis and impair-
ment of pigment and carbohydrate metabolism (Bykov, 1968 in IARC 1976a).
B.
Nonhuman Mammals
The available literature on the biological effects of butadiene and its
oligamers is discussed in the sections which follow.
100
-------
1.
Toxicology
a.
Butadiene
1)
Acute Toxicity
a)
Lethal Doses.
Butadiene exhibits low toxicity to laboratory animals.
In rats, the two
hour LCSO (concentration lethal to 50% of the organisms) averages 285,000
mg/m3. For mice, the 4 hour LCSO is 270,000 mg/m3. Other lethal con-
centrations appear in Table 34.
b)
Narcotic Effects.
The acute narcotic effect of inhaling high concentrations of butadiene has
been described for mice and rabbits in the older literature (Killian, 1930;
Larinow et al., 1934 as cited in Von Oettingen, 1940; Carpenter et al., 1944).
In one study, white m~ce (sex and number used not reported) were exposed
to several concentrations of butadiene, rang~ng from 10 to 40% ~n oxygen
(Killian, 1930).
At concentrations of 20 to 40% butadiene, narcosis developed
after 6-10 or 0.7-1.0 minutes, respectively.
Excitation often preceeded
narcosis.
The latency to excitation and narcosis is shown in Table 35.
Accompanying symptoms included hyperventilation and twitching at 15-30%
butadiene.
At 40%, all animals died within 11-14 minutes.
101
-------
Table 34
Acute Lethal Concentration (LC) Values for 1,3-Butadiene
Lethal Conc. (L. C. )
(mg/m3)
Duration
Reference
Rata LC16 = 175,000 2 hr Shugaev, 1969
LC50 = 285,000
(219,000-370,000)b 2 hr Shugaev, 1969
LC84 = 460,000 2 hr Shugaev, 1969
Mousec LC16 = 203,000 4 hr Shugaev, 1969
LCSO = 270,000
C251,000-290,000)b 4 hr Shugaev, 1969
LC50 = 259,000 N.R. Batkina, 1968
LC84 = 375,000 4 hr Shugaev, 1969
LC 100 = 300,000 N.R. Batkina, 1966
N.R. = not reported
asex; strain, and number tested not given
b95% confidence limits
csex and number tested not given by either author; albino mice used by
Batkina
Table 35
Effect of Inhaling Varying Mixtures of Butadiene-oxygen in Mice
(Killian, 1930)
Concentration
Butadiene in 02
(%)
Time To
Excitation
(minutes)
Narcosis
(minutes)
10
15
20
25
30
40
5
1
0.5-0.67
6-10
2-3
1-1. 2
0.67-1
0.33-0.5
102
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The Russian investigators, Larionow, Shtessel and Nuselman (1934, as cited
in Von Oettillgen, 1940) reported that 200,000-300,000 mg/m3 of butadiene is
the lowest concentration range necessary to produce narcosis and coma in
mice.
Irritation of the nucous membranes resulting in conjunctivitis, and
nasal and bronchial inflammation were also reported.
Narcotic effects have similarly been described in rabbits.
According to
Larionov et al. (1934, as cited in Von Oettingen, 1940) exposure to a 25%
mixture of butadiene and oxygen caused a loss of labyrinth and motor reflexes
but recovery after exposure was rapid.
Carpenter et al. (1944) exposed 29
rabbits to this concentration of butadiene in air; symptoms and average time
to occurrence are described in Table 36.
Effect
Table 36
of Inhaling Butadiene in Rabbits
(Carpenter et al., 1944)
Symptom
Time of Occurrence
(minutes)
light anesthesia
loss of pupillary reflex to strong light
early pupil dilation
excitation, running, tremors, chewing
1.6
3.8
3.9
4.6
loss of blink reflex to stimulus
dry rales
6.5
7.1
involuntary blinking
marked pupil dilation
death
7.4
11.4
23.0
In about 9 minutes the butadiene concentration of the blood in the femoral
artery was 0.26 mgfml and in the femoral vein, 0.18 mg/ml.
One rabbit sur-
vived 34 daily inductions into deep anesthesia with 20-25% butadiene in air
without pulmonary damage.
103
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2)
Subacute Toxicity
a)
Inhalation Exposure.
A short-term exposure study was conducted by Hazleton Laboratories Europe
to determine dosage levels for a chronic experiment to be sponsored by ISSRP
(International Institute of Synthetic Rubber Products) (Scala, 1977).
Groups
of 40 male and 40 female rats were exposed to atmospheres containing 0, 2200,
4400, 8800 or 18000 mg of butadiene/m3 for 6 hours/day, 5 days/week over 13
weeks.
The concentration of butadiene dimer (4-vinylcyclohexene) in the
18,000 mg/m3 exposure group ranged from 3.32-11.05 mg/m3.
There were no
signs of toxicity attributable to butadiene at any concentration tested.
A
dose-rela~ed decrease in groo~ng behavior, associated with discolored hair-
coat and, in some cases, discolored saliva, occurred after 8 weeks' exposure.
Another effect was a change in neuromuscular function (as measured by a ro-
tating spiral test) in males at the low exposure level (2,200 mg/m3) and in
3
females at 2,200 and 4,400 mg/m .
The changes in the two sexes were in the
opposite direction and did not occur at the high doses; the biological sig-
nificance of the'se data was called "questionable" by Scala (1977).
Scala also
attached no "biological significance" to the increase in red blood cell
cholinesterase activity in all test groups seen at 2, 6, and 13 weeks.
Another finding was a reduction in brain cholinesterase activity in males at
the two highest levels.
In females, receiving the highest dose, the absolute
level of brain cholinesterase was elevated; however, tissue examination re-
vealed spontaneous disease rather than evidence of butadiene-induced effects.
The effects of inhaling much lower levelS' of butadiene have been described
~n a series of papers appearing in the Russian literature.
Groups of 14-15
male albino rats were exposed to butadiene at concentrations of 0 (pure air),
3
1.07 ~ 0.006, 3.08 ~ 0.006, or 30.8 ~ 0.075 mg/m for 24 hours/
104
-------
day for 81 days. Animals at each exposure level were intoxicated as a group
in 0.1 m3 chambers; the butadiene concentration in the chambers was checked
daily via spectrophotometry.
Ripp (1967) described gross and microscopic ef-
fects; data were supplemented by papers on spleen changes (Molodyuk, 1969),
and on hepatic and cardiac effects (Nikiforova et al., 1969).
A reiteration
of these results appears in Ripp (1969).
The changes observed in rats during
and after exposure to butadiene for 81 days are described in the 7 subsections
which follow:
Effects on Demeanor and Weight.
Rats exposed continu-
ously to 30 mg/m3 displayed "a certain unrest" during the first days of in-
toxication.
By the end of the third month, activity was reduced.
Animals
receiving lower levels of butadiene (lor 3 mg/m3) behaved within normal
limits (Ripp, 1967).
3
Weight ga~n was normal for rats exposed to 1 and 3 mg/m , and rats
exposed to 30 mg/m3 gained weight normally until about day 50; after this
time, weights decreased until the end of the experiment (day 81).
Weights at
the beginning and end of the experiment were as follows:
Group
(mg butadiene/m3)
Day 0
(g)
Day 81
( g)
% Increase
o
1
3
30
170
175
172
175
(extrapolated
from graph
258
248
245
230
in text)
51. 8%
41. 7%
42.4%
31.4%
Effect on Blood Indices.
Evaluations were made every 2
weeks on 5 rats/group for erythrocytes, reticulocytes hemoglobin, and leuko-
cy te s .
All values were within normal limits except for a statistically sig-
nificant increase in the leukocyte count on day 80 in rats exposed to 30
3
mg/m .
No data were presented to support this claim.
105
-------
Effec"t on Cholinesterase.
The time (in minutes) for
acetylcholine to be hydrolyzed was used to measure whole blood cholinesterase
activity.
Determinations were made prior to intoxication and every two weeks
during intoxication on 5 rats/group.
The results are presented in Figure 10.
Only in rats inhaling butadiene at 30 mg/m3 was cholinesterase activity in-
creased; this level returned to normal after cessation of treatment.
50
Z
o
!::
U)
o
Q.
:E
o
'Uc
~.E 35
~-
ZQI
::i e 30
0.-
J:~
U 25
~
>-
~
~
U
«
15
o
7
22 38 56
DAY OF INTOXICATION
73 80
Figure 10.
Effect of Butadiene on Cholinesterase Activity of Whole
Rats Exposed Continuously to Butadiene for 81 Days.
Group 1) control; 2) 1 mg/m3; 3) 3 mg/m3; 4) 30 mg/m3
(Ripp, 1967)
Blood of
106
-------
Effec"t on Op"tic Proper"ties of Blood Serum.
As a deter-
mination of serum protein, the optical properties of blood serum were
measured.
The absorption index (optic density) of the serum increased in rats
exposed to 30 mg/m3 (pre-intoxication index, 1.7-1.85; day 30 index, 2.03-
2.36), but not in rats exposed to lower levels of butadiene.
The position of
the absorption bands of the blood serum did not change in any group.
Effec"t on Arterial Pressure.
Arterial pressure of the
tail was measured in 5 rats/group (using a sphygmomanometer)every three weeks
during intoxication.
Arterial pressure was stable in all groups for about 2
months.
However, on the 72nd day of intoxication the arterial pressure in
rats exposed to 30 mg/m3 declined and remained at this level until the end
of treatment and during the recovery period (Figure 11).
-100
C'
:I:
~ 90
I.&J
~ 80
(/')
(/')
~ 70
~
-I
~ 60
a::
I.&J
.-
a::
-------
Effec1:. on Mo1:.or k;1:.ivi1:.g.
The motor activity of 5 rats/
group was recorded during 3 hour periods several times per week in special
chambers to electronically score movement.
The motor activity was unchanged
in rats exposed to butadiene at I and 3 mg/m3 for 81 days.
However, activ-
ity decreased to 60% of pre-exposure activity after seven weeks in rats ex-
3
posed to 30 mg/m .
Effec1:.s on Tissues and Organs.
After 81 days of expo-
sure, tissue sections of liver, kidney, heart, spleen, brain and bone marrow
TN'ere examined.
In all rats the mucous membrane was not intact to some extent;
Ripp (1967) suggests this was the result of "environmental factors" such as
crowd- ing, air, humidity, etc.
Other changes were dose-dependent and are
described below for each organ examined.
in the lung.
Lung. All rats inhaling butadiene showed some changes
At 1 mg/m3 there were "differences in comparison with the con-
t'rol", however, no other details were given.
At 3 mg/m3 there was moder-
ately pronounced interstitial pneumonia as well as small foci of atelectasis
At 30 mg/m3 there was highly developed lymphoid tissue and
and emphysema.
also small foci of atelectasis and emphysema.
Liver. No alterations TN'ere apparent ~n animals sub-
-
jected to 1 or 3 mg/m 3 At 30 mg/m 3 there was a thinning of the trabe-
.
culae and almost total absence of light cells ~n some animals.
Spleen.
In rats subjected to chronic exposures of 1
mg/m3, the spleen contained an excess of erythrocytes.
3
At 3 mg/m , abnor-
mal changes in the spleen included:
indistinct nuclei of the connective
tissue; plethora of vessels; and a reduction of RNA.
More distinct changes
occurred in rats inhaling 30 mg/m3.
The vessel endothelium was swollen;
108
-------
vessels and S1nuses revealed small hemorrhages and were plethoric.
Distri-
buted throughout the follicles were reticular cells, lymphoblasts, and macro-
phages.
In addition, the capsules and trabeculae were loosened and the
lymphoid follicles were enlarged.
Kidney.
Continuous inhalation of 1 mg/m3 of buta-
diene for 81 days resulted in no visible ultrastructural alterations in the
kidneys; however, at 3 mg/m3, butadiene induced these changes:
loosening of
the capsule; accumulation of connective tissue cells; exceSS1ve hyperemia of
the glomerular capillaries; and in some cases, deformation of the epithelial
cell nuclei in the convoluted tubules.
Renal changes were more pronounced at
3
30 mg/m .
These included 1) loosening of the adipose capsule and hyperemia,
2) swelling or enlargement of the glomerula, capsules, lumen and convoluted
tubular epithelia, 3) proliferation of connective tissue, fibroblasts,
macrophages and plasma cells in some areas of the kidney and 4) reduction in
the RNA level" of some tissues.
Heart.
'1
Chronic inhalation of butadiene at 1 mg/mJ
-
resulted in no visible structural alterations of the muscular fibers of the
heart, but some areas of the vessels were hyperemic and infiltrated by leuko-
The heart of rats inhaling 3 mg/m3 exhibited reduced differentiation
cytes.
of the endothelium, deformation of endothelial nuclei, and capillary hyperemia
Rats exposed to 30 mg/m3 exhibited cardiac hypermia, hemo-
and hemostasis.
stasis and hemorrhage; in addition, the RNA level of cell cytoplasm was re-
duced.
b)
Oral Administration.
Tissue and organ changes were observed in 25 rats (sex and strain not
specified) receiving daily oral doses of butadiene of 100 mg/kg in vegetable
oil for 2.5 months; 10 control rats received vegetable oil only (Donetskaya
109
-------
and Shvartsapel, 1970).
Histological and histochemical sections revealed de-
generative, somet~es necrotic, changes in the cytoplasm of cells of the
heart, liver, kidneys, nervous tissue and vascular walls.
These cytoplasmic
changes included granular and hydropic dystropy, cytolysis, neuronophagia, and
altered vessel permeability.
The authors s~ate that these changes are related
to butadiene "to a certain degree"; whether these changes also occurred in
control animals is not clearly stated.
Some circulatory changes, however,
were stated as likely due to butadiene:
venous hyperemia, stasis, hemorrhage,
and edema; these changes were more pronounced in exper~ental animals.
The
authors consider the following changes not due to butadiene administration, as
controls also exhibited these abnormalities:
hyperplasia of hepatic reticular
tissue; proliferation of alveolar epithelium; and infiltration of lymphocytes
in the heart, liver, kidneys, gastrointestinal tract and subcutaneous tissue.
The absence of more detailed data l~it the usefulness of this Russian study.
3)
Chronic Toxicity *
Published studies on the chronic effects of butadiene have appeared in the
U. S. and Russian literature.
In addition a long-term study is currently
underway at Hazleton Laboratories Europe (sponsored by the International In-
stitute of Synthetic Rubber Producers).
In this investigation, groups of 110
male and 110 female rats are being exposed to butadiene at 0, 2200, or 18000
mg/m3 for 6 hours/day,S days per week for 24 months.
No results are avail-
able at this t~e.
a)
Inhalation Exposure.
In a chronic exposure exper~ent
in the U.S.S.R., Batkina (1966) exposed
albino rats and rabbits (no sex, species, or number given) to butadiene at 10,
3
100 or 2,000 mg/m for 4 hours/day for 4 months.
Rats previously trained to
respond to sound showed a slower reaction t~e after long-term exposure to
*defined here as exposure for 90 or more days
110
-------
butadiene; the tbne-to-response was 0.33 seconds in controls, 1.04 seconds in
the 100 mg/m3 group and 0.74 seconds in the 2,200 mg/m3 group.
1iemato-
logical changes observed included reduced leukocyte counts (40% lower in rats
given 2,200 mg/m3) and alterations in serum protein (Table 37).
In rabbits,
chronic exposure resulted in inhibition of serum cholinesterase at the two
higher levels (Table 38), as well as a decrease in the phagocytic activity of
neu troph il s .
In both rats and rabbits, chronic exposure to 10 mg/m3 was
without effect (Batkina, 1966).
The U. S. investigators Carpenter et al. (1944) exposed laboratory animals
to higher concentrations of butadiene for longer periods of tbne than did
Batkina (1966).
A total of 164 rats, guinea pigs, rabbits and dogs were ex-
posed in a dynamic chamber to butadiene vapors at 600, 2300 or 6700 ppm (1326,
4830, 14807 mg/m3) for 7.5 hours/day, 6 days/week for 8 months; controls
were exposed to air only.
An equal number of males and females were used,
except for dogs (females only).
Several parameters were considered, as sum-
marized in Table 39 and described below in the four subsections which follow.
Grow1:h and General Health.
There were no deaths among
experbnental anbnals that could be attributed to butadiene.
About 5% of
exposed rats developed "some extraneous infections", but these were not con-
sidered significant.
For rats and guinea pigs, exposure to butadiene affected
weight gain in a dose-related manner.
At the termination of the experiment,
weights of rats were 90.5, 86.3 and 81.2% of the controls for the 1326, 4830
and 14807 mg/m3 groups, respectively; no comparable data for guinea pigs
were presented.
However, the four female dogs were heavier at the termination
of the experiment for all exposures.
The ratio of body weight to body weight was determined for rats only.
Final ratios were 4.3, 8.7 and 14.8% less than controls for the 1,326, 4,830
and 14,807 mg/m3 groups.
The authors considered this variation normal.
111
-------
Table 37
Serum Protein in Rats after Chronic Exposure
(4 hours/day, 4 mo.) to Butadiene
(Batkina, 1966)
Total Protein
Albumins (gi.)
aI-globulin
a2-globulin
B-globulin
y-globulin
Lipoproteins (g%)
(t
B
y
Control
2200
Concentration of BD
100
10
7. 52 :t 0.17
8.31 :t 0.33*
2.81 :t 0.14
1.01 :t 0.04
0.71 :t 0.02
1.48 :t 0.051
1. 40 :t O. 04
12.2 :t 0.58
29.9 :t 1. 09
57.9 :t 1.37
8. 72 :t O. 1 7*
8.01 :t 0.27
3.58:t 0.26*
O. 88 :t o. 13
0.72 :t 0.02
1.58:t 0.19
1.41 :t 0.20
11.3 :t 1.23
49.3:t 3.38*
39.4:t 3.50*
* p < .05
4.25 :t 0.20*
3.78 :t 0.17*
o. 72 :t 0.15*
0.67 :t 0.11*
1.52 :t 0.15
1.43 :t 0.21
o. 75 :t 0.10
0.59 :t 0.06
1. 44 :t O. 15
1.33 :t 0.19
Concentration
o (Control)
2200
100
10
9.7 :t 0.83*
56.4 :t 2.05*
33.9 :t 2.47*
9.4 :t 0.89*
43. 3 :t 1. 99*
47.3 :t 2.16*
Table 38"
Serum Cholinesterase Activity in Rabbits after
Chronic Inhalation Exposure (4 hours/day,
4 months) to Butadiene (Batkina, 1966)
X
% decompos ed
Acetylcholine
16.4
11.98
11. 94
13. 76
pa
<0.05
<0.05
>0.05
athe author calculated P using a t-test, which, however, should not be used
on percentages.
112
-------
Table 39
Effects of Chronic Inhalation of Butadiene by
Rabbits and Guinea Pigs (7.5 hours/day,
6 days/week for 8 months)a
(Carpenter et al., 1944)
Rats,
Parameterb
ppm
(mg/m3
Deaths attributable to
exposure for all
species
Weight at 8 mo. as %
of control for rats
Weight at 8 mo. as %
of starting weight
for dogs
Ratio of body length
to body weight at
8 mo. as % of control
for rats
Kidney weight for rats
Liver weight for rats
Blood counts and
clinical chemistry
for rats
Litters/female for
rats
Young/litter
rats
guinea pigs
rabbits
Pathology of adrenal,
heart, kidney,
skeletal muscle,
pancreas, spleen,
testis or ovary
for all species
o
o
o
104.4%
normal
normal
normal
3.3
-7.8-7.9
16
24
none
Response/Exposure Group
600 2,300
1,326 4,830
o
o
90 . 5 %
86.3%
111.1%
108.0%
95. 7%
91. 3%
normal
normal
lower than
control
lower than
control
normal
normal
2.72
2.5
8.4
13
(no litter)
7.9
10
(no litter)
none
none
113
6, 700
14,807)
o
81. 2%
114. 7%
85.2%
normal
normal
normal
2.62
7.8
13
27
none
-------
Table 39 (Cont.)
Effects of Chronic Inhalation of Butadiene by
Rabbits and Guinea Pigs (7.5 hours/day,
6 days/week for 8 months)a
(Carpenter et al., 1944)
Rats,
parameterb Response/Exposure Group
ppm 0 600 2,300 6,700
(mg/m3 0 1,326 4,830 14,807)
Pathology of eye none none none none
for dogs and
rabbits
Cloudy swelling of 10 68
liver for all
species (%)
Congestion of liver sporadic sporadic sporadic sporadic
for all species
No. instances
fatty infiltration of 0 1 2 0
guinea pigs
Congestion of lung yes, very yes yes, but yes
for all species frequent not frequent
a exposure in chamber to a total of 164 animals; four groups of 24 albino
rats, 12 guinea pigs, 4 rabbits, and 1 dog.
b data as given in original reference; no additional information available
(Le., a parameter labeled "normal" here was so identified in text).
114
-------
At the end of the exposure period, kidney and liver weights of rats were
determined.
Kidney weights were within normal range for all groups.
The
liver weights for the 1,326 and 4,830 mg/m3 groups were "slightly lower"
3
than those of controls but those of the 14,807 mg/m group were normal.
The
authors attribute these differences to the uncertainty inherent in the method
of sacrifice used (cord sectioned then bled completely).
No data on kidney or
liver weights were presented.
Effects on Blood.
Monthly blood counts on all animals
revealed no abnormalities with respect to hemoglobin, erythrocyte, leukocyte
or differential counts.
For rats and dogs, clotting time, reticulocyte count
and white cell volume were also determined and found to be within the normal
range.
At the end of the experiment, blood urea nitrogen and bilirubin were
normal in all animals.
Urinalyses for albumin, sugar and casts were likewise
normal.
Effects on Fertility and Reproduction.
The number of
litters per female and the number of young per litter were both used as in-
dices of fertility in rats.
Butadiene affected the former measurement only.
Disregarding infertile females, the number of litters per female during the
experimental period was 3.3, 2.72, 2.5 and 2.62 for the 0, 1,326, 4,830 and
3
14,807 mg/m groups, respectively.
The number of young per litter, however,
was unaffected and actually increased in one case:
8.4, 7.9, 7.8, pups/litter
3
for the 1,326, 4,830 and 14,807 mg/m groups, respectively; the control
average was not stated specifically but ranged between 7.9-7.8.
For guinea
pigs and rabbits only the number of young per litter was determined, and was
found to be within normal limits (Table 38).
Pathology.
The eyes of dogs and rabbits were examined
grossly during the course of exposures and microscopically after killing.
No
115
-------
abnormalities were found in the cornea, sclera, retinal ganglion cells, optic
nerve or other retinal layers.
No pathological changes occurred in the adrenal glands, heart, kidneys,
skeletal muscle, pancreas, spleen, testes or ovaries.
Both experimental and
control animals exhibited lung congestion.
Liver congestion was probably a
response to butadiene:
68% of all animals in the 14,807 mg/m3 group showed
light cloudy swelling compared to 10% in controls.
Fatty infiltration oc-
curred in the livers of 3 exposed guinea pigs (2 from the 4,380 mg/m3 and 1
from the 1,326 mg/m3 group).
b)
Oral Administration
The Russian investigator Shvartsapel (1970) administered butadiene to rab-
bits by gavage in a chronic experllnent.
A total of thirty-six rabbits (sex
and strain not given) were given doses of 0.4, 4.0 or 40 mg/kg body weight of
butadiene in vegetable oil for 7 months (the dose schedule was not specified);
controls received vegetable oil only.
Several parameters were measured every
month during intoxication:
whole blood free sulfhydryl (SH) concentration,
serum acetylcholinesterase, cholinesterase and fructose-diphosphate aldolase
activities, and hemoglobin level.
Shvartsapel (1970) observed no changes for
the first three parameters in experimental rabbits (no data are presented).
In rabbits receiving 40 mg/kg, there was a significant ~ncrease in the
activity of the enzyme fructose-diphosphate aldolase during the seventh month,
and a slight decrease in hemoglobin after the fourth month.
Rabbits receiving
lower butadiene doses were unaffected (Table 40).
116
-------
Table 40
Chronic Feeding of Butadiene to Rabbits for 7 Months:
Effect on Serum Fructose-Diphosphate Aldolase (FD)
Activity and Hemoglobin (Hb) (Shvartsapel, 1970)
o 0.4 Dose (mg/kg bw)
4.0 40.0
Month FDa Hbb FD Hb FD Hb FD Hb
o 22.84 11.45 22. 18 11. 6 23.28 12.01 24.10 11.16
1 23.63 12.54 23.81 12.24 23.22 12.19 23.24 12.00
2 21 .48 13.27 21 . 91 13.12 22.83 12.86 23. 72 12. 92
3 26.91 12.48 23.45 11 . 21 28.67 12.74 26.60 12.40
4 24.98 13.0 24.16 13.00 23. 78 12.91 24.61 12.56
5 23.34 13.0 23.89 12.92 22.93 13.06 24.46 12.60
6 27.39 12.88 28.56 12. 99 25.91 12.48 34.96 12.57
7 27.46 12.41 28.39 12.48 30.97 12.11 38.30 11.67
a fructose-diphosphate aldolase activity; the units
unclear, as a translation from the Russian yields
no English equivalent was found.
b hemoglobin expressed in g%
of measurement are
"TB" units, for which
b.
Butadiene Containing Mixtures
Reports are available in the Russian literatur-e on the toxicity of.buta-
diene mixed with one or more compounds.
Observed effects, therefore, are not
necessarily due to butadiene.
For completeness, these studies are included,
but will be discussed only briefly.
1)
Butadiene-a Methylstyrene (BD-MS)
A series of Russian studies are available on the effects of chronic inhal-
ation of butadiene-a-methylstyrene mixtures.
Rats were exposed to these
mixtures for 4 months and the resulting effects were evaluated in several
organ and tissue systems by a number of authors.
One study is discussed in
detail below, followed by a summary of the effects found in similarly exposed
rats.
Fadeeva and Eikhler (1971) reported altered blood-values, oxidation-
reduction reactions, and metabolism as a result of chronic inhalation of
butadiene-alpha-methylstyrene.
Male albino rats inhaled mixtures 6 hours/day,
117
-------
6 days/week for 4 months.
A total of 42 rats was used in 3 experimental
groups:
1)
controls, exposed to air only
mixture of 47.9 z 2.9 mg/m3 butadiene and 2.88 Z 0.2 mg/m3
2)
3)
a-methylstyrene
mixture of 99.8 z 4 mg/m3 butadiene and 5.2 Z 0.3 mg/m3
a-methylstyrene
In rats exposed to the higher level only, the luekocyte and phagocyte count in
the blood and the cholinesterase activity in the blood were reduced from the
control (Table 41).
Blood free sulfhydryl (SH) content at the higher dose was increased 300 to
400 micromoles/100 ml over control values by the end of the second month; this
elevation was maintained to the end of the experiment and for 2 weeks after
cessation of treacnent.
At the lower dose, free SH increased, but to a lesser
degree.
To study the effect of butadiene-alpha-methylstyrene on oxidation-
reduction reactions, urine coproporphyrin elimination was measured from 5 rats
in each group.
After the fourth week there was a significant increase in
coproporphyrin elimination in both experimental groups; however, no data were
presented to support this statement.
As a measure of metabolism, the levels of various vitamins were deter-
mined.
Beginning after 80 days, rats receiving the higher dose showed a sig-
nificant increase in the amount of ascorbic acid in the urine and a tendency
toward reduced levels in the blood (no supporting data were presented).
At the end of the 4 months, rats given the larger dose showed decreased levels
of ascorbic acid in the liver and brain and also a decreased amount of vitamin
B in the liver (Table 41).
There were no changes in the vitamin levels
118
-------
Table 41
Effect of Chronic Inhalation of Mixtures of
Butadiene-Alpha-Methylstyrene in Ratsa
(Fadeeva and Eikhlor, 1971)
Control
47.9 butadiene
+ 2.88 methyl styrene
(mg/m3 )
99.8 butadiene
+ 5.2 methyl styrene
(mg/m3)
Leukocyte Count
Day 0
Mo. 4
Phagocyte CountC
Week 6
Week 7
Week 8
Week 9
Week 10
14, 779 :t 2173
same level as
above a
same as controlb
same as controlb
15,550 :t 1314
9,925 :t 1375
3.02
3.22
3.32
3.52
3.62
3.53
3.42
3.38
3.30
3.26
3.60
3.17
2.96
2.54
2.32
Cho linesterase Activity (micromoles of hydrolyzed acetylcholine)
Day 10 1. 448 :t 0.074 _b 1.578 :t 0.037
Day 20 1.397 :t 0.094 _b 1. 085 :t 0.103
Mo. 4 1.482 :t 0.067 same as contro1b 1.319 :t 0.027
Ascorbic Acid (mg %)
Liver, mo. 4
Brain, mo. 4
Vitamin B (mg %)
Liver, mo. 4
36 .2 :t 1. 98
20.6 :t 1.27
_b
_b
31.3 :t 0.84
15 .0 :t 1. 30
2.27 :t 0.17
_b
1 . 78 :t O. 7
a exposed 6 hours day. 6 days/week, 4 months
b data not given in original text
C data smoothed by method of least squares
119
-------
of these tissues in rats receiving the lower dose.
For both experimental
groups no changes were detected in hemoglobin or nuclei acid levels in the
blood or in body weight throughout the experiment.
Additional effects have been noted by a number of other authors in rats
inhaling up to 100 mg/m3 butadiene and alpha-methylstyrene mixtures for four
months (6 days/week).
Some changes were time dependent, as summarized below:
days 10-30
- myeloid, lymphoid and erythroblastic reactions observed in
bone marrow, lymph glands, and spleen (Molodyuk, 1969).
- in females, the number of primordial and maturing follicles
decreased; the number of eosinophils in the mucous membrane of
uterus increased (Morozov, 1969a).
- alteration of the bronchial epithelium, increased
permeability of blood vessels (Kuz'min, 1969).
day 60
- mature elements of bone marrow were larger; lymphopoiesis
was inhibited in lymph glands and spleen (Molodyuk, 1969).
- restoration of spermatogenesis (Morozov, 1969b).
days 90-120 - blood cell composition began to normalize (Molodyuk, 1969)
in males, inhibited spermatogenesis (Morozov, 1969b).
Other effects were observed at the end of the experimental period including:
a reduction in the number of neutrophils and in serum proteins, and an in-
crease in ~2-globulins (Matusov, 1969); an increase in blood and liver
cholesteroal (Chukreev, 1969); a decrease in the permeability of blood vessels
(Kuzmin, 1969); a decrease of liver glycogen, accumulation of lipids in liver
cells and redistribution of total liver protein (Lambina, 1969a and b); symp-
toms similar to protein dystrophy of the kidneys (Serebrennikov, 1969); and
disturbed hemodynamics (Bul'Bakov, 1969).
120
-------
2)
Butadiene-Toluene
Inhalation for 2 hours of a combination of butadiene (100 mg/l) and to1u-
ene (20 mg/l) resulted in a prolongation of estrous in female rats previously
cycling regularly.
Chronic exposures to lesser amounts (0.1 mg butadiene/l
and 0.05 mg toluene/I, 3-6 hours/day for 2 months) resulted in similar length-
ening; normal estrus was restored in 50% of the rats 5 months after termina-
tion of treatment (Skuja, 1969).
Exposure of rabbits to a mixture of butadiene and toluene 4 hours daily
for two months caused changes in the bone marrow and serum; the total protein
content decreased and the ratio of albumin to globulin increased (Faustov and
Lobeeva, 1970).
c.
Vinylcyclohexene
1)
Acute Toxicity
Smyth et al. (1969) measured several parameters of toxicity for
4-vinylcyclohexene (summarized in Table 42).
In rats, the acute oral LD50
value was determined to be 3.08 ml/kg (equivalent to 2,556 mg/kg)*.
Rats can
inhale "concentrated" vapors for a maximum of 15 minutes before death occurs.
Inhalation of 8,000 ppm (35,360 mg/m3) for 4 hours resulted in 67% mortality
(6 animals tested).
For rabbits, the single skin penetration LD50 was 20 ml/kg (16,598
mg/kg) when retained beneath plastic fibn, contacting the skin for 24 hours.
Vinylcyclohexene caused irritation to the uncovered rabbit belly within 24
hours (graded "4" on a scale of 1, no reaction to 10, necrosis).
When applied
to the cornea of rabbits, it produced a mild reaction (graded "2' on a scale
of 1, slight reaction to 10, severe reaction).
*conversion based on density of vinylcyclohexene (0.8299)
121
-------
Table 42
Range-Finding Toxicity Data for 4-Vinylcyclohexene
(Smyth et al., 1969)
Item
Acute Oral LDSO for
rats
Acute Dermal LDSO
for rabbits
Concentrated vapor
inhalation by rats,
Maximum time for
no dea th
Inhalation of 8,000
ppm (3S,360 mg/m3)
for 4 hours
Topical application:
Uncovered rabbit
be lly
Rabbit cornea
Data
3.08 ml/kg; range
2.49-3.81 (2,556
mg/kg)
20 ml /kg
(16,598 mg/kg)
15 min.
mortality:
4/6
4
2
122
Method
Administered to groups of 5
Carworth-Wistar male rats
(90-120 g) by gavage, observed
for 14 days
Fur clipped in groups of 4 male
albino New Zealand rabbits
(2.5-3.5 kg) and VCR retained
beneath plastic film contacting
skin for 24 hr; observed for
14 days
Groups of 5 male or female
albino rats exposed for
varying time intervals
Exposure of 6 rats in
inhalation chamber; observed
for 14 days
Reaction within 24 hours in
5 albino rats; Grade 1 - no
reaction, Grade 10 - necrosis
from 0.01% solution
Reaction Graded 1 - slight
reaction to 10 - severe
reaction
-------
2)
Chronic Toxicity
3
Inhalation of 1,000 mg/m of 4-vinylcyclohexene for 6 hours/day over 4
months inhibited weight ~ncrease and caused leukocytosis, leukopenia and hemo-
dynamic impairment in rats and mice (Bykov, 1968 in IARC, 1976a).
Long-term skin application in mice is described in the next section.
3)
Carcinogenic Potential
Vinylcyclohexene was tested for carcinogenicity by skin application in
male Swiss-Millerton ~ce, as discussed in the carcinogenicity section
(IV-B-3) .
Because testing was only by skin application, the International
Agency for Research on Cancer stated that it is not possible to evaluate
carcinogenicity in vinylcyclohexene.
The National Cancer Institute plans to
begin a carcinogenesis bioassay on viny1cyclohexene in October 1978 (Chase,
pers.
COIIDD.. ,
1978) .
d.
Cyclooctadiene and Cyclododecatriene
Brawn and Hunter (1968) tested the dermal toxicity of 1,S-cyclooctadiene
and 1,S,9-cyclododecatriene.
The samples tested consisted of 98% w/w of the
cis,cis-isomer of cyclooctadiene with 0.02% 2,6-diterbutyl-4-methylphenol
added as a peroxide inhibitor.
The cyclododecatriene sample contained 90%
cis, trans, trans-isomer with 0.17. of the same inhibitor.
Both samples caused
severe contact dermatitis in laboratory maIIDD.a1s in several tests, as described
in the three subsections which follow.
Skin Irritation Study.
Rabbits were tested in a "covered
test" .
The compounds were applied on shaved skin using a 2 x 2 em bandage,
which was then covered with a sheet of polythene.
The bandage was in place
for 6 hours/day for 3 successive days.
Epidermal sloughing was especially ap-
parent after the application of cyclooctadiene; the skin was grossly injured.
123
-------
A post mortem examination revealed necrosis of the epidermis, and ulceration
and inflammation of the dermis with cyclooctadiene.
Following cyclododeca-
triene application, there were acanthosis and a proliferative epidermal re-
action.
In an "uncovered test", the samples were applied on shorn skin of rabbits,
guinea pigs and hairless mice daily for 4-5 weeks (5 days/week).
With cyclo-
octadiene, an Umnediate erythematous reaction was noted in all species after
the first application, followed by acute contact dermatitis and epidermal
sloughing.
For cyclododecatriene, severe contact dermatitis occurred.
Ulcer-
ation was observed in one mouse on histopathological examination.
Guinea pigs
killed 3 weeks after the last application of the compounds showed epidermal
thickening and considerable acanthosis.
Skin Sen~iza~ion Studies.
Tests were carried out by
topical application and intradermal injection of a 0.1% w/w solution of the
test compounds in light liquid paraffin.
This procedure was performed 3
days/week for 3 weeks on the backs of guinea pigs, followed by no treatment
for 10 days.
Then the test compound was administered again.
The animals were
examined at 24 and 48 hours.
Most an~als showed sensitization, as indicated
below (no data for controls are given):
No. Guinea Pigs Showing Positive
Guinea Pigs Tested
Topical Test
24 hr 48 hr
Reaction/No.
Intradermal Test
24 hr 48 hr
Cyclooctadiene
Cyclododecatriene
10/10
10/10
10/10
10/10
9/10
10/10
9/10
10/10
124
-------
Eye Tests.
When applied to t~e eyes of rabbits, both
cyclooctadiene and cyclododecatriene caused limnediate irritation and conjunc-
tivitis, which faded within 48 hours.
The eyelids became red and swollen and
exuded a purulent discharge.
Both compounds caused blepharitis; this condi-
tion healed in a few days after application of cyclooctadiene but persisted
for a week or more after cyclododecatriene treatment.
2.
Biological Fate
Few studies are available on the absorption, distribution or biotransform-
ation of butadiene or its oligomers.
a.
Butadiene
1)
Absorption
The distribution coefficient of butadiene in vitro between rabbit blood
and air averaged 0.603 (range 0.555-0.662) at 37.50C and 760 mm pressure in
5 determinations.
In vivo, the distribution coefficient averaged 0.654
(range 0..535-0.801) in 10 .determinations.
Since there is good agreement be-
tween in vivo and in vitro blood distribution coefficients, Carpenter et
al. (1944) suggested that the passage of butadiene from inspired air into the
blood is a process of simple diffusion of gas from the alveoli of the lungs.
2)
Distribution
Carpenter et al. (1944) determined the level of butadiene in blood after
inhalation exposure.
In rabbits exposed to 250,000 ppm butadiene (552,500
mg/m3), the concentration of butadiene in the blood after 9 minutes was 0.26
mg/ml in the femoral artery and 0.18 mg/ml in the femoral vein.
A Russian investigator, Shugaev (1969), measured the distribution of buta-
diene in several tissues after inhalation exposure, using gas-liquid chroma-
tography.
3
Rats (strain or sex not given) exposed to 285,000 mg/m for 2
125
-------
hours (LC50) showed a high concentration of butadiene in the perinephric fat
(152 mg %) and lower levels in the brain (51 mg %), liver (51.4 mg %), spleen
(45 mg %) and the kidney (36 mg io) (Table 43) Shugaev also exposed rats to
butadiene at 285,000 mg/m3 for 1 hour.
When determinations were made 0.1
min. after exposure was terminated, levels were about 34 mg i. in brain and
liver tissue; however, no butadiene (or only a trace) was found in these
tissues 90 minutes after exposure (Table 44).
Shugaev (1969) reported a
correlation between butadiene concentration in the brain and narcotic state.
Rats inhaling butadiene (and other hydrocarbons tested) were in a state of
deep narcosis after 1 hour's exposure.
When exposure was terminated, movement
appeared within 4-5 minutes and muscular control was normal after 60 minutes.
Levels of butadiene were also determined in several parts of the nervous
system and in the liver of cats.
Two cats were exposed at a level such that
death occurred within one hour (this level was not reported).
The highest
concentration of butadi~ne was round in the spinal cord and pons (Table 45).
3)
Metabolism
The urine of rabbits inhaling, daily, atmospheres containing 20-25%
(442,000-552,500 mg/m3) butadiene in subacute and chronic experiments (see
Sections III B-1-a) was analyzed for formic acid, oxalic acid, aldehydes, and
materials oxidizable by periodic acid (1,2-glyco1s, glyoxal, glycollic alde-
hyde, pyruvic aldehyde, acetoin, biacetyl and erythritol) as possible buta-
diene metabolites.
No "appreciable differences" were found between the urine
of exposed and control rabbits for these compounds; no data are presented to
support this (Carpenter et al., 1944).
126
-------
Table 43
Distribution of Butadienea After Exposure to
LC50 (Shugaev, 1969)
Organ
Average Butadiene Levels, mg% (95% Confidence Limit)
Ratb Mousec
Brain
50.8
(43.3-58.3)
54.4
09.9-69.0 )
_d
Liver
51.4
(45.3-57.5)
Kidney
36.3
(29.2-43.4)
_d
Spleen
45.0
(39.7-50.3)
_d
Perinephric Fat
152.1
(120.6-183.7)
_d
a precise time of determination
b exposure to 285,000 mg/m3 for
c exPosure to 270,000 mg/m3 for
d not determined
not given
2 hr (LC50); data from 7 or 10 trials
4 hr (LC50); data from 10 trials
Table 44
Distribution of Butadiene in the Brain and Liver
of Rats at Several Time Intervals after Acute
Exposurea (Shugaev, 1969)
Time after Removal Average Concentration, mgi. (95% Confidence Limit)
from Chamber (1 min.) Brain Liver
-
0.1 34.6 33.8
(24.1-42.3) (27.6-39.2)
15 6.7 10.9
(7.1-12.3) (6.2-15.7)
30 4.3 5.9
(3.1-5.3) 0.4-7.6)
60 2.9 3.3
0.8-4.2) (2.7-4.2)
90 0 - traces 0 - traces
a exposure to 285,000 mg/m3 for 1 hour
(LCSO 4 hour = 285,000 mg/m3
127
-------
Distribution
System and
Table 45
of Butadiene in the Central Nervous
Liver of Acutely Intoxicated Cats
(Shugaev, 1969)
Tissue
Butadiene Concentration (mg%)
Cat No.1 Cat No.2
Cortex cerebri in region Gyrus centralis
anterior
Substantia alba in region Capsula interna
Cortex cerebelli
Medulla oblongata
Mesencephalon in region corpora
quadrigemina
Pons Varolii
Spinal cord jugular section
Liver
32 24
42 33
34 22
45 44
36 42
67 50
70 59
31 28
a neither dosage nor precise time of tissue measurement were reported;
exposure set so cats died during 1 hr. exposure
b.
Cyclooctadiene
The metabolism of 1,5-cyclooctadiene was studied in 6 doe rabbits (2.5-3
kg) and 6 female rats (200-250 g) (Waring, 1971).
Oral doses of 1.5 m mol/kg
(162 mg/kg) of 1,5-cyclooctadiene were administered by gavage.
Twenty-four
hour samples were collected and analyzed by gas liquid chromatography and mass
spectrometry.
Metabolites identified in the urine are given in Table 46 and
include the glucuronide and sulfate conjugates, and 2 unidentified mercapturic
acids (perhaps methyl esters of diacetoxycyclo-octyl mercapturic acids).
In a
separate experiment, Waring (1971) showed that the liver is the major source
of sulfur for conjugation to form mercapturic acids.
Rats previously dosed
with 35S were fed 1,5-cyclooctadiene, and then killed 2 hours later.
The
liver was the only tissue in which the content of 35S decreased signifi-
cantly.
This is in agreement with observed decreases in liver glutathione
(GSH).
Female rats (200-2S0 g) were fed 1.S m mole/kg of 1,S-cyclooctadiene.
Total liver glutathione was reduced to 66% of control values after 2 hours and
73% after 3 hours.
128
-------
Excretion
After
Table 46
of Conjugates in Urine of Rats and Rabbits
Oral Dosing with 1,5-Gyclooctadienea
(Waring, 1971)
Conjugates in
Urineb
Rabbit
(N=6)
% Dose (range)
Rat
(N=6)
Glucuronide
53.5 (48.4-58.2)
_c
Ethereal Sulfate
22.8 (18.1-24.6)
_c
Mercapturic Acids
A
B
5.4 (4.3-6.2)
16.304.8-17.7)
5 . 5 (4. 6-6 . 6 )
18.9 (13.4-21.3)
a 1.5 m mole/kg (162 mg/kg)
b 24-hr urine
C no determinations made
C.
Other Animals
No data are available on the toxicity of butadiene or its oligomers to
species other than humans or laboratory mammals.
Several authors have erron-
eously cited data from Garrett (1957) on fish toxicity.
Garrett's paper, how-
ever, mentions 1-cyano-1,3-butadiene and not 1,3-butadiene.
D.
Plants
Several authors have investigated the toxicity to plants of butadiene
monomer and butadiene in the presence of atmospheric constituents (e.g.,
nitrogen oxide, ozone).
While the monomer itself had little effect on the
species tested, products forming in the presence of butadiene may be harmful,
as discussed below.
Haagen-Smit et al. (1952) tested several constituents of smog, including
butadiene, for toxic effects on five crop plants under controlled laboratory
129
-------
conditions.
A mixture of 5 ppm butadiene and 0.15 ppm ozone was used to fumi-
gate the plants over five hours.
Leaf damage was compared to known smog
damage.
"Typical" smog damage was considered to be:
i) metallic sheen, sil-
vering, or bronzing on spinach, endive, and beets; ii) speckled necrosis on
oats and alfalfa; and iii) marginal bleaching on alfalfa.
Atypical damage was
often characterized by wilting, necrotic areas, tip burning, chlorosis,
bleaching or pitting.
In the experiment described above, typical smog damage
occurred to the leaves of endives; typical, but not severe damage occurred to
spinach oats and alfalfa.
Beet leaves were damaged, but not in a manner
typical of smog damage (Table 47).
In a second series of experiments, mixtures of butadiene and oxides of
nitrogen were used to fumigate the indicator plants for 1.5-5 hours (Table
48) .
No damage occurred after exposure to mixtures of 2.0 ppm butadiene - 2.5
ppm N203 or 0.5 ppm butadiene - 4.5 ppm N02.
However, higher concentra-
tions of the latter components (5 ppm butadiene - 7.0 N02) caused typical
smog damage to spinach and endive leaves and typical nonsevere leaf damage to
beets.
Atypical injury to oats and alfalfa occurred.
Altschuller et al.
(1966) subjected 3 species of plants to the irradia-
tion products formed during the first four hours of photooxidation of 3.30 ppm
butadiene and 0.85 ppm nitrogen oxides.
The primary reaction products were
formaldehyde, acrolein, aliphatic aldehydes, and ethylene (0.85, 1.0, 1.15,
and 0.002 ppm by volume, respectively); trace amounts of peroxyacetyl nitrate
(PAN) also formed.
There was no leaf damage to individuals of the tobacco
wrapper (Nicotiana tabacum), petunia (Petunia hybrida), or young pinto beans
(Phaseolus vulgaris).
The authors account for the absence of plant damage to
young pinto beans by the formation of only trace amounts of PAN, a compound to
which these species are particularly sensitive.
130
-------
Table 47
Effect of Butadiene and Either Ozone or Oxides of
Nitrogen on Plants (Haagen-Smit et al., 1952)
Conditions
Results
Mixture of (ppm, vol/vol)
Butadiene 2.6 5.0 0.5 2.0
Ozone 0.15
N02 7 4.5
N03 2.5
Exposure (hours) 5 1.5 4.5 5
Injury to leavesa
Spinach t T 0 0
Endive T T 0 0
Beets A t 0 0
Oats t A 0 0
Alfalfa t A 0 0
a injury scored as follows (refer to text):
T = typical smog damage
t = typical smog damage but not as severe
A = damage not typical of smog damage
o = no injury
Tests have also been conducted on the butadiene monomer alone.
Heck and
pires (1962) tested 14 low molecular weight hydrocarbons, including butadiene,
for effects on plant growth and development.
Fumigation at 1,000 ppm (2,210
mg/kg) butadiene for 7 days produced only slight injury in cotton, cowpea, and
tomato; no injury was reported for coleus, sorghum, or soybean.
In further
tests with butadiene, no easily recognizable injury occurred after a three
week fumigation at 10 ppm (22.1 mg/m3) (for coleus, cotton, and tomato) or
at 100 ppm (221 mg/m3) butadiene (for cotton and tomato). The nature or
frequency of the injuries were not specifically stated.
Heck and pires (1962)
summarized the tests by stating that butadiene resulted in 0% injury at 10 ppm
and <5% injury at both 100 and 1,000 ppm.
131
-------
Butadiene was one of about 35 compounds tested for biological activity and
compared to the action of ethylene in pea seedlings (Pisum sativum) (Burg and
Burg, 1967).
In the Straight Growth Test, ethylene-treated peas first swell
then elongate 50% less than controls, described by Michaelis-Menton kinetics.
In this test, the concentration of ethylene required for half-maximum activity
3
is 0.1 ppm; for butadiene, 500,000 ppm (1,105,000 mg/m ) was required but
this activity may be due to the contamination of the butadiene with 0.2 ppm
ethylene.
Abeles and Gahagan (1968) also compared various compounds, including
butadiene, to the action of ethylene.
The role of 7 compounds in accelerating
petiole abscission was tested in the red kidney bean Phaseolus vulgaris.
Half
max~um stimulation of abscission occurred at about 0.1 ppm ethylene but at
> 10,000 ppm butadiene; butadiene and I-butene were the least active of the
compounds tested.
The percent abscission over controls after 4 hours exposure
depended on the concentration tested, as shown below for butadiene:
Butadiene
Cone. (ppm)
% Abscission over Controls
1
10
100
1,000
10,000
o
2
5
8
18
132
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IV.
SPECIAL EFFECTS
A. Mutagenicity
1.
Butadiene
De Meester et ale (1978) determined butadiene and its possible metabolite,
butadiene monoxide, to be weakly mutagenic in several test strains sensitive
to base-pair substitution mutagens.
The study was prompted by the structural
similarity between butadiene and other monomers known to be mutagenic (e.g.,
vinylidene chloride, 2-chlorobutadiene, styrene, acrylonitrile); these mono-
mers all contain vinylic groups.
The procedure involved adding Salmonella typhimurium (strains TA 1530,
TA 1535, TA 1537, TA 1538, TA 98, and TA 100) to the test chemical, pouring
the mixture onto agar plates and counting the number of revertants to hista-
dine prototrophy (his+) per plate after a period of incubation.
Tests were
performed both in the absence and presence of a metabolic activation system,
fortified S-9 fractions of rat liver homogenate.
The results for butadiene
appear in Table 48.
Strains TA 1530 and TA 1535 showed a direct (in absence
of S-9 fraction) and an indirect (in presence of S-9 fraction) mutagenic re-
sponse to butadiene.
When the S-9 fraction was used, more revertants occurred
at the lower of 2 S-9 concentractions tested, possibly due to an inadequate
composition of S-9 mix.
The other strains showed no mutagenic response either
with or without metabolic the activation.
The number of revertrants was determined over time (0-72 hours) for strain
TA 1530.
During the first hours, the reversion rate was low but increased to
a maximum after about 24 hours; however, the percentage of butadiene in the
abnosphere had decreased by about 25% during this period.
This phenomenon
133
-------
Table 48
Mutagenic Effect of Butadiene on Strains of S. typhimurium in the
Presence and Absence of a Fortified S-9 Fraction
(De Meester et al., 1978)
No. of his+ Revertants/Plate
TA 1530 TA 1535 TA 1537 TA 1538 TA 98 TAI00
Controls
Without S-9 fraction 13 14 7 25 29 158
With S-9 fractiona 13 14 20 24 35 146
Butadieneb
Without S-9 fraction 80 52 11 28 15 118
With S-9 fractionb 43 37 10 34 34 98
Butadieneb
Without S-9 fraction 58 55 15 31 14 108
With S-9 fractionc 65 65 13 23 28 154
a300~l S-9/ml mix used; total incubation
bincubation time in dessicator 20 hours;
in dessicator atmosphere was -70%
c200~l S-9/ml mix used; total incubation
time was 72 hours
at that time percentage of butadiene
time 44 hours
might be related to the low solubility of butadiene in the aqueous phase.
The
authors also carried out mutagenicity tests using the usual Ames standard
plate method (mixed substrate in top agar) and there was no ~ncrease in the
number of revertants compared to controls; no data were presented on this,
however.
For butadiene monoxide there was no mutagenic response in TA 1537, TA 1538
or TA 98 strains at the concentrations tested of (1-250 ~oles/plate).
For
strains TA 1530, TA 1535 and TA 100 reversion to histidine prototrophy oc-
curred without metabolic activation within a range of 60 to 100 ~oles/
plate.
For strain 100, the reversion rate at 100 ~oles plate was twice
134
-------
that of the spontaneous rate.
For strains TA 1530 and TA 1535, the mutation
rate was 10 times the spontaneous reversion rate at 100 ~oles/plate; buta-
diene concentrations higher than this were toxic.
Strains TA 1530 and TA 1535 are sensitive to base-pair substitution
mutagens, suggesting that for both butadene and butadiene monoxide, base-pain
substitutions in the bacterial DNA are involved.
Furthermore, since both
strains were sensitive to the same strains the authors suggest that butadiene
monoxide may be a primary metabolite of butadiene.
2.
possible Metabolites
As discussed above, de Meester et ale (1978) suggest that butadiene mon-
oxide is a possible oxidative metabolite of butadiene.
They showed that
butadiene monoxide induces reversion to histidine prototrophy in several
strains of Salmonella typhemurium.
These researchers also postulated that
diepoxybutane might be another oxidative metabolite of butadiene.
Diepoxybutane was mutagenic in several test systems, as shown below (reviewed
in IARC, 1976b):
induced reverse mutations in strain TA 1535 of S. typhimurium, in
Schizosaccharomyces pombe and in E. coli.
induced reverse mutations in adenine-requiring mutant 38701 of
Neurospora carassa
produced mitotic gene convers~ons in strain D4 of Saccharomyces
cerevisiae
produced sex-linked recessive lethal mutations, visible mutations,
semi-lethal mutations, trans locations and minute mutations in
Drosophila melanogaster.
135
-------
B.
Carcinogenicity
1.
Butadiene
Butadiene was scheduled to be tested by the National Cancer Institute for
carcinogenicity.
However, the contract to the performing organization was
terminated and there are no projected dates to begin testing again (Chase,
pers. comm., 1978).
2.
possible Metabolites
De Meester et ale (1978) speculated that butadiene monoxide (1,2-
epoxybutene-3) and diepoxybutane might be oxidative metabolites of
1, 3-bu tadiene.
This suggestion was based primarily on structural similarities
between butadiene and other monomers (i.e., vinylchloride and styrene), which
form reactive epoxide intermediates.
Butadiene monoxide and racemic forms of
diepoxybutane have been reported to possess carcinogenic properties when ap-
plied to the skin of mice (Van Duuren et.al., 1963).
The data and experi-
mental method appear in Table 49.
In addition, 'subcutaneous injec"tion of
d,I-1,2:3,4-diepoxybutane (0.1 or 1.1 mg in tricaprylin) in female mice once a
week for a year resulted in the development of local fibrosarcomas (5/50 and
5/30 mice for 0.1 and 1.1 mg groups, respectively).
Solvent controls
developed no local sarcomas.
Female Sprague-Dawley rats given 1 mg i.p.
d,I-1,2:3,4-diepoxybutane in tricaprylin once a week also developed local
fibrosarcomas (9/50 animals) (Van Duuren et al., 1966).
3.
Oligomers
The carcinogenic potential of vinylcyclohexene and its hydroperoxide were
evaluated in male Swiss~illerton mice (Van Duuren et al., 1963).
Commercial
vinylcyclohexene was purified to remove oxidation products by distillation.
The hydroperoxide was prepared as a 0.5% solution of VCH.
Application of both
compounds in benzene to the skin of mice 3 times per week for life resulted in
136
-------
Table 49
Carcinogenicity of Butadiene Monoxide and Diepoxybutane in
Male Swiss-Millerton Mice (Van Duuren et a1., 1963)a
Butadiene d1-1,2;3,4- meso-l,2j3-4- Acetone No Treatment
Monoxi de Diepoxybutane Diepoxybutane (control) (control)
10% 10%
none acetone acetone
30 30 30 90 207
237 78 154 134-330 112-624
Concentration
Solvent
No. tested
......
w
"
Median survival
time (days)
Tumor incidenceb
Number
% of Total
Cancer incidencec
Number
% of Total
3 2 6 8 13
10% 6.7% 20% 8.9% 6.3%
1 ] 4 0 ]
3.3% 3.3% 13.3% 0% 0.5%
acompounds
brefers to
crefers to
applied to skin 3 times per wk for life, 100 mg/painting
benign papillomas and squamous cell cancers
squamous cell cancers
-------
extensive skin damage.
The experimental conditions appear in Table SO.
Tumor
frequencies for 150 benzene (control for solvent) and 207 no-treatment con-
troIs were 7.3 and 6.3%, respectively; one animal in each group developed a
cancer.
Of 30 mice tested with vinylcyclohexene, 6 (20%) developed skin
tumors; 1 of these tumors was a squamous cell cancer.
The incidence for the
hydroperoxide was higher; thirteen of 36 m~ce (34%) developed tumors,S of
which were cancerous.
The authors suggest the possibility that the VCR con-
tained a small amount of the hydroperoxide formed by autooxidation.
In another experiment using "oxygen-free" VCR (precluding oxidation), 0.1
ml VCR (in a 10% solution in benzene) was applied to the skin of 30 Swiss-
Millerton mice 3 times/week for life.
No carcinogenic effect was observed
(Van Duuren, 1965).
The International Agency for Research on Cancer (lARC, 1976a) examined the
two studies by Van Duren and concluded that the data do not allow an evalua-
tion of carcinogenic risk as the testing was only by skin application.
138
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Table 50
Carcinogenicity Testing of Viny1cyc1ohexene (VCR) and
the Rydroperoxide of VCR in Male Swiss-Mil1erton
Mice (Van Duuren et a1., 1963)
Solvent
1-Rydroperoxy-4-
VCRa Viny1cyclohexeneb Benzeneb No Treatment
50% 0.5% (control) (contro l)
b enz ene 1 : 1 b enz ene : VCR
30 38 150 207c
375 165-403 262-412 112-624
Concentration
No. tested
Median survival
time (days)
Tumor incidencec
Number
% of total
6 13 11 13
20% 34% 7.3% 6.3%
1 5 1 1
3.3% 13% 0.7% 0.5%
Cancer incidencee
Number of mice
% of total
a applied to skin 3 times/week for life; 45 mg/painting
b applied to skin 3 times/week for life; 100 mg/painting
c not including 60 female GAF mice
d tumor incidence refers to benign papillomas and squamous
e cancer incidence refers to squamous cell cancers
cell cancers
139
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V.
REGULATIONS AND STANDARDS
A.
Federal Regulations
1.
Occupational Safety and Health Administration
The occupational exposure to butadiene is limited by the Occupational
Safety and Health Administration (OSHA, 1970) to an 8-hour time-weighted
average of 1,000 ppm (2,200 mg/m3) (Table Z-l; 29 CFR 1910.1000). This is
the same value recommended by the American Conference of Governmental
Industrial Hygenists (ACGIH, 1977; see Section V-D).
2.
Department of Transportation
Butadiene offered for transport must be inhibited against polymerization.
Regulations pertaining to the transport of inhibited butadiene are contained
in the Hazardous Materials Table promulgated under the Hazardous Materials
Transportation Act (1975; 49 CFR 172.101; PL 93-633).
Butadiene is classified
as a flammable gas.
Requirements for the charging and shipping of compressed
gases are detailed in 49 CFR 173.304 and 173.314-5.
A motor vehicle or rail
car transporting butadiene must be placarded on each side and each end with a
red placard identifying the shipment as a flammable gas.
Inhibited butadiene cannot be shipped by a passenger-carrying railcar or
aircraft.
When shipped by cargo-only aircraft, a maximum of 300 pounds may be
contained in each package shipped.
For cargo vessels, butadiene may be stowed
"on deck" or "under deck", away from living quarters.
3.
Environmental Protection Agency
Effluent limitation guidelines exist for discharges associated with buta-
diene manufactured by any process, which includes the oxidatiue dehydrogena-
tion of butene (40 CFR 414).
Butadiene is the only organic chemical whose
process wastewater is regulated as a point source.
Three levels of control
140
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technology for butadiene manufacture are outlined in title 40 of the code of
Federal Regulations and appear in Table 51.
The first is for the best practi-
cable control technology currently available (BPCTCA).
The second is for the
best available technology economically achievable (BATEA).
Finally, effluent
limitations exist for new sources.
4.
Food and Drug Administration
Butadiene is considered an indirect food additive by the Food and Drug
Administration under 21 CFR parts 174ff.
Food contact use is regulated for
butadiene-containing polymers and copolymers, including use in the following:
adhesives; polymeric coatings; paper and paperboard components; single and
repeated use food contact surfaces; and cellophane.
State Regulations
B.
Agencies in 15 selected states, including those containing production and
major end-use sites, were contacted about state-level regulations.
Their
response appear in Tables 52-54.
1.
Workplace Standards
Those states responding to information requested on workplace standards
indicated that they enforce the standards set by the Occupational Safety and
Health Administration (Table 52).
2.
Food Contact
States responding indicated reliance on the regulations of the U.S.D.A.
and F.D.A. (Table 52).
3.
Water Quality
Butadiene is indirectly limited by general water quality standards in many
states (Table 53).
141
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E ££1 uent
Characteristica
Table 51
Effluent Limitations for the Manufacture of Butadiene by
Oxidative Dehydrogenation (40 CFR 414)
Limitationsb
Average of Daily
Values for 30 consecutive
days shall not exceed:
Effluent
Maximum for
Any 1 Day
A. Best Practicable Control Technology Currently Available
BODS 2.3 1.0
TSS 2.3 1.0
pH 6.0-9.0 6.0-9.0
B. Best Available Technology Economically Achievable
COD 7.8 4.2
BODS 0.57 0.27
TSS 0.94 0.50
pH 6.0-9.0 6.0-9.0
C. New Source Standards
COD 7.8 4.2
BODS 0.57 0.27
TSS 0.94 0.50
pH 6.0-9.0 6.0-9.0
a BOD = biological oxygen demand at 5 days
COD = chemical oxygen demand
TSS = total suspended solids
b units = pounds per 1,000 lb product
Table 52
Regulations for Butadiene Food Contact and Workplace Standards in
Selected States in Response to Queries
Food
Contact
*
*
*
Workplace Standards
*
*
*
California
Connecticut
Delaware
Kentucky
Louisiana
Missouri
New Jersey
New York
Ohio
Pennsylvania
South Carolina
Tennessee
Texas
*
*
*
*
*
*
*
*Federal standards followed; dashes indicate no response
142
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Water Standards
State
Table 53
for Butadiene in Selected
Response to Queries
States in
Standard
no response
California
Connecticut
Delaware
Kentucky
Louisiana
Missouri
New Jersey
New York
Ohio
Pennsylvania
South Caro lina
Tennessee
Texas
no specific water quality standards or
requlations; subject to case-by-case technical
permit review by Water Compliance and Hazardous
Substance Unit
not specifically controlled
no response
case-by-case permit rev~ew for discharges
general water quality standards apply
comply with federal discharge requirements
under FWPCA
no water quality standards for BD
general water quality standards apply; State
Law: OAC-3745-1
general water quality standards apply
indirectly limited by general water quality
criteria
general standards for toxic substances and
organics apply
measured indirectly as BODS or COD in
individual discharge permits issued to
manufacturers.
143
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State
Air Standards
Table 54
for Butadiene in Selected
Response to Queries
States in
Standard
California
Connecticut
Delaware
Kentucky
Louisiana
Missouri
New Jersey
New York
Ohio
Pennsyl vania
South Caro lina
Tennessee
Texas
control as "reactive organics" in California basins in
which federal oxidaint standards is exceeded
emissions restricted to 8 lb/hr., 40 lbs/day for
organic solvents; State Law: Section 19-508-20f(2)
general air quality standards apply; State Law: Reg.
I-XXIII of Dept. Nat. Res. & Env. Control (for air
pollution)
no response
regulations for storage of relative organic carbons
may apply
no specific regulations
general restrictions for volatile organic substances
and ambient air quality standards apply; State Law:
NJEPA N.J. Adm. Code Title 7, Chp. 27
processes, exhaust and/or ventilation systems are
regulated under State Law: Industrial Process Air
Pollution Control Rule, part 212
considered photochemically reactive (PR) by the Ohio
Environmental Protection Agency assuming BD in liquid
state with another organic material. Emission
requirements for PR materials is 8 lbs/hour and 40
lbs/day per equipment, machine or article. However,
if the source has a control device (that is at least
85% efficient) the mass emission requirement is waived
for liquid organic materials conducted by flame,
heat-cured or heat-polymerized emission is 3 lbs/hr
and 15 lbs/machine; State Law: OAC 3745-2l-01(C)
no weight rate emission limitations for BD; standards
for organic compounds apply for storage and loading;
State Law: Pa. Air Pollution Control Act
no specific regulations
general process emission standards; State Law:
1200-3-7-.07
State Law: Reg. V rule 505.2 specifically lists
regulations for BD emissions. Waste stream must be
burned at temperature> 13000F in a smokeless
flare or a direct flame incinerator before it may
enter the atmosphere. Regulations provided for
storage of volatile carbon compounds.
144
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4.
Air Emissions
Butadiene emissions are regulated either directly or indirectly in several
states (Table 54).
In Ohio, butadiene is considered photochemically reactive
and by definition,
emissions are
limited to 8 lbs/hour and 40 lbs/day per
equipment, machine, or article.
However, if the source has a control device
that is 85% efficient this emission requirement is waived.
For liquid organic
materials which are contacted by flame, or are heat-cured or heat-polymerized,
emission is limited to 3 lbs/hour and 15 lbs/machine.
In Texas, butadiene
waste streams must be burned at temperatures greater than 13000F in a smoke-
less flare or a direct flame incinerator before it may enter the atmosphere.
In many other states, general air quality or emission standards apply.
C.
Foreign Countries
Agencies in several countries were contacted about butadiene regulations.
In addition, specific laws and regulations were consulted.
1.
United Kingdom
The work place standards in the U.K. for butadiene are the following:
STEt (short term exposure limit) =
3
ppm (2,200 mg/m )
3
1,250 ppm (2,750 mg/m )
TLV (threshold unit value) = 1,000
In general, the U.K. uses exposure units drawn up by the ACGIH (American Con-
ference of Governmeneal Industrial Hygenists).
Air pollution control for industrial processes is under control of HM
Alkali and Clean Air Inspectorate in England and Wales; in Scotland, HM In-
dustrial Pollution Inspectorate under authority of the following:
The Alkali
Act, (6 Edw.7.C.14); the Health and Safety at Work Etc. Act 1974 (1974 Chapter
37); and, the Control of Pollution Act 1974 (1974 Chapter 40).
Control of
butadiene might be effected under these acts, but there are no specific a~r
145
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standards for butadiene.
SUnilarly, while there are no specific water quality
standards for butadiene, control could be accomplished under The Water Act of
1973, among other acts.
2.
West Germany
The maximum allowable workplace concentration (MAK) of butadiene is 1000
ppm (2200 mg/m3) (BNA:MAK, 1977); it is the same in East Germany.
Air emission standards for butadiene and other compounds are contained in
the Air Purity Regulations (6MBI 1974).
In waste gas, butadiene cannot exceed
150 mg/m3) (when flow rate is 3 kg/hr or more).
There are no specific water quality standards for butadiene.
3.
Japan
Butadiene is not listed as a toxic substance under the Air Pollution Con-
trol Law (Law No. 97 of 1968).
The Water Pollution Control Law (Law No. 138 of 1970) sets forth regula-
tions for synthetic rubber manufacturing and other industries in which buta-
diene is used; however, emission of butadiene monomer does not appear to be
controlled.
4.
Canada
Occupational health falls under provinical rather than federal jurisdic-
ti on .
In general, provinical standards reflect ACGIH and/or OSHA recommenda-
ti ons .
The Environmental Protection Service (EPS) in Canada is developing regula-
tions and guidelines to reduce air and water pollution.
Effluent guidelines
are currently being drawn up for the organic chemicals industry (Anon., 1978d)
which might possibly regulate butadiene.
No tolerances have been set for butadiene migration from food-contact
polymers.
146
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5.
Others
Occupational exposure limits in other countries not discussed above are as
follows (Scala, 1977):
USSR
Bulgaria
Czechloslovakia
Finland
Poland
Rumania
Yugoslavia
.EE
45
45
230
1000
45
682
1000
mg/m3
100
100
500
2200
100
1500
2200
D.
Other Standards
In 1971 the American Conference of Governmental Industrial Hygenists
(AIGCH, 1971) recommended a threshold limit value (TLV) of 1,000 ppm (2200
mg/m3) for butadiene based primarily on the low toxicity reported in animals
by Carpenter et al., (1944, see section III).
This TLV appears "to offer a
comfortable margin of safety from effects of exposure".
In 1977, the AICGH
recommended that the Short Term Exposure Limit (STEL) maxUnum for butadiene be
3
1,250 ppm (2,750 mg/m ).
E.
Current Handling Practices
1.
Handling, Storage, and Transport
A manual published by the Manufacturing Chemists Association give the
procedure for the safe handling and transport of butadiene, which is described
as a dangerous fire hazard when exposed to heat, flame or strong oxidizers
(MCA, 1974).
Commercial liquified butadiene is inhibited against peroxide
formation and polymerization, but uninhibited butadinene presents problems of
heat and pressure development at elevated temperatures, as in fire
condi ti ons.
Butadiene vapors are uninhibited and "popcorn" polymers may form
147
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by auto-addition, plugging pipelines or storage tank vents.
A problem is the
handling of butadiene is the formation of butadiene dimer, particularly at
elevated temperatures; no inhibitor for this reaction is known.
Because of
this problem, commercial butadiene is usually stored under conditions of
refrigeration rather than under pressure.
Also, refrigerated storage is
usually more economical than pressure storage (Exxon, 1974).
The liquified
gas is cooled by auto-refrigeration and stored at a temperature yielding vapor
pressure of 1-10 psig; the vapor is then cooled and condensed.
Pressure
storage is used only to store small quantities of butadiene in cylinders and
sample bombs (Exxon, 1974).
These should be stored in an outdoor, detached
place or a well-ventilated cool place.
Cylinders should be stored vertically
(not-stacked) and protected against physical damage (ITll, 1975).
Butadiene is usually shipped in steel cylinders (100 lb. capacity), tank
cars or tank trucks.
Cylinders are shipped by motor freight, rail freight or
railway express (Exxon, 1974).
2.
Personnel Exposure
The Manufacturing Chemists Association (1974) suggested that air-supplied
masks be used during exposures to high concentrations (20-25%) of butadiene
vapors.
Other protective equipment which should be made available for use ~n
case of spills or equipment failure includes goggles, aprons or suits, boots,
emergency deluge showers, and eye wash fountains.
In the case of overexposure to butadiene vapors the victim should be re-
moved to fresh air; oxygen resuscitation may be necessary (MCA, 1974).
In the
case of skin contact with liquid butadiene, the affected area should be placed
in water at 37.SoC until circulation resumes.
(Exxon, 1977).
148
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3.
Accident Procedures
In the event of spills, all ignition sources should be eliminated.
Petro-
Tex (n.d.) suggested covering spills with a foam blanket with water fog.
Leaks should be covered with water fog or a steam blanket.
Spills should be
prevented from entering sewers or low areas.
Small quantities of spilled
butadiene should be vented to the atmosphere or to an open space with adequate
ventilation, whereas "appreciable quantities" should be burned or flared
(Exxon, 1977; Petro-Tex, n.d.).
149
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VI.
EXPOSURE AND EFFECTS POTENTIAL
A.
Butadiene
Environmental exposure to butadiene may occur from several sources:
1)
production 2) end-use; 3) storage; and 4) transport.
Also, butadiene is a
minor component of hydrocarbons in urban air.
For humans, it appears that the
highest exposure potential is in the workplace.
Levels up to 1,000 ppm (2200
3
mg/m ) are allowable in the workroom, as an 8-hour time-weighted average.
This value is based primarily on the low toxicity of butadiene to laboratory
animals (see Section III-B).
Although acute over-exposures may occur through
improper handling and accidents, there have been no reports in the U.S. or
Western European literature of any chronic effects arising from industrial use
of butadiene.
Another consideration of occupational exposure is the extreme
flammability and reactivity of butadiene.
For example, the Manufacturing
Chemists Association (MqA, 1966) describ'ed an industrial accident involving a
ruptured pipeline which released butadiene vapors.
The vapors were ignited by
a gas-engine driven compressor and an employee standing 40 feet from the tank
at the time of ignition received extensive burns.
The leak occurred when a
plug of butadiene "popcorn" polymer ruptured the pipeline; "popcorn" growth is
usually associated with the presence of oxygen.
As mentioned above, exposure may also be possible during several phases of
production and use.
Because only limited monitoring data are available, it is
difficult to adequately assess this potential.
These monitoring data, dis-
cussed in detail in section II, indicate that the butadiene monomer is only a
minor constituent of emissions from production facilities.
In the production
of SBR, small amounts of butadiene enter the atmosphere from the butadiene
absorber vent and as fugitive emissions (Table 23) (Pervier et al., 1974a).
150
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In a study of atmospheric emissions from an adiponitrile production facility,
butadiene comprised 3.8% of the total amount of hydrocarbons emitted (Pervier
et al., 1974b).
Butadiene has been identified in the wastewater of rubber
manufacturing plants by Day (1975), and low levels of butadiene have been
identified in urban air «10 ppb) and gasoline «1 ppb) (see Section
II-C-5).
Another source of butadiene is from monomer storage facilities.
One study
reported that .00017 lb were emitted per 1b of SBR produced during tank farm
storage (Pervier et al., 1974a).
The possibility also exists for environmental contamination during trans-
portation accidents or tank car failure.
Butadiene, a gas at ambient, tem-
perature, is usually shipped under pressure as a liquid.
Release of butadiene
from a pressurized tank failure, for example, will result in flash vaporiza-
tion
of the liquid and the formation of an aerosol.
Slater (1978),in
reviewing the formation and hazards of vapor clouds, found th~t the dispersion
of vapor clouds depends on factors such as micrometeorology, temperature,
topography, thermodynamic properties and aerodynamic effects.
Smaller leaks
are less likely to ignite, because the concentration may fall below the lower
flammable limit before ignition occurs (2% for butadiene).
For larger clouds,
ignition is more likely.
Slater (1978) listed an accident involving a vapor
cloud of butadiene in Rolland during 1971; 8 people were killed and 21 were
injured.
He also mentioned 2 explosion accidents involving light
hydrocarbons:
i) Perris, Netherlands, 1968 in which 2 people were killed and
75 injured; the blast shattered windows 1 mile away and ii) Puerto 1a Cruz,
1969 in which 5 people were killed; there was extensive glass and ceiling
damage in the town.
151
-------
Butadiene present in the atmosphere from any source (i.e., leaks, produc-
tion emission) will not persist.
Butadiene is highly reactive.
It partici-
pates in atmospheric photolysis reactions, and also reacts with nitrogen
oxides and ozone found in the atmosphere.
In a laboratory study,. Stephens and
Burleson (1967) showed that butadiene in air samples will disappear after 4
hours of irradiation with U.V. light.
However, samples kept in the dark still
contain butadiene after 24 hours (Table 29).
Under atmospheric conditions,
the presence of nitrogen oxides and ozone, as well as light, is critical to
removal.
Another approach to assess environmental exposure is one taken by Fuller
et al., (1976).
Using a scoring system based on production, volatility and
toxicity, they examined the potential of 637 organic chemicals, including
butadiene, to enter the atmosphere from industrial sources and pose a toxi-
co logical threat.
For butadiene, a final score of 3 was assigned taking into
account factors of production, properties and toxicity.
A maximum. score of
125 was possible.
The scoring system appears to be most useful when comparing
chemicals.
Scores for several are:
acrylamide, 4; acrylonitrile, 20; ethyl-
ene, 9; ethylene glycol, 11; and propylene, 4.
Only low-level environmental contamination of butadiene may be expected,
except during a spill situation.
The potential hazards from low-level con-
tamination do not appear to be high.
Butadiene is volatile and reactive, thus
subject to chemical degradation.
A short residence time is expected.
b.
Oligomers
Vinylcyclohexene is a contaminant in all butadiene samples, but its forma-
tion is temperature-dependent.
When butadiene vaporizes, as in the tank fail-
ure discussed above, vinylcyclohexene, being less volatile will remain longer
B2
-------
at the spill site.
The persistence of this compound under environmental con-
ditions has not been investigated.
Butadiene oligomers have been dentified in the workroom.
Rappaport and
3
Fraser (1977) detected low levels of vinylcyclohexene (0.313 and 0.408 mg/m
in 2 areas), 1,S-cyclooctadiene (0.0277 and 0.028S mg/m3) and 1,S,9-cyclodo-
decatriene (0.0481 and 0.10S4 mg/m3) in a passenger tire curing room.
These
oligomers probably originated from cis-polybutadiene rubber used in tire manu-
facture.
No other data are available on environmental contamination by
butadiene oligomers.
153
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TECHNICAL SUMMARY
1,3-Butadiene is a basic monomer used to produce styrene-butadiene rubber
(S3%), polybutadiene rubber (18%), neoprene (7%), nitrile rubber (3%), adi-
ponitrile (8%), acrylonitrile-butadiene-styrene resins (6%), as well as other
products (S%) (Anon., 1977a).
About 3.2 billion pounds of rubber-grade buta-
diene were produced during 1977 (U.S. Int. Tariff Comm., 1977) by three
commercial processes (dehydrogenation of n-butane or n-butene, or coproduct of
ethylene manufacture) and by about IS manufacturers at more than 20 loca-
tions.
These locations are in Texas (70%), Louisiana (20%), and Puerto Rico
(10%).
Total capacity is about 4.9 billion pounds.
Butadiene reacts with itself to form cyclic oligomers.
Examples of com-
mercially important oligomers are 4-vinylcyclohexene, 1,S,9-cyclododecatriene
and 1,S-cyclooctadiene.
Cyclododecatriene is used primarily as a precurser to
nylon with DuPont being the only current domestic producer.
Cyclooctadiene is
used in ethylene-propylene terpolymer production and is available from Cities
Service Co.
Vinylcyclohexene is an impurity in butadiene formed by
dimerization; patents have described potential applications for insecticides,
plasticizers and as an intermediate in preparing aliphatic hydrocarbons and
antioxidants.
Vinylcyclohexene is obtained as a byproduct of butadiene
manufacture and not produced directly.
Limited monitoring data indicate that low levels of butadiene can enter
the environment during production, end-use, storage and transport.
Acci-
dental spills and leaks appear to be the greatest potential for environmental
exposure.
Butadiene has been identified as a constituent of urban air «10
ppb or 0.02 mgjm3) (Table 26) and gasoline «1 ppb, Stevens and Burleson,
1967) .
Butadiene oligomers were identified in the workplace of a tire vul-
154
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canization area (Rappaport and Fraser, 1977) but the extent of environmental
contamination is unknown.
Butadiene is a gas at ambient temperature and pressure.
When released
into the environment, butadiene will vaporize rapidly.
In addition to being
volatile, butadiene is highly reactive chemically and will not persist in the
environment.
Butadiene participates in atmospheric photolysis reactions, and
will react with nitric oxide, forming acrolein, aliphatic aldehydes, ethylene,
formaldehyde, and peroxyacetyl nitrate (Altshuller et al., 1966; Heuss and
Glasson, 1967).
These reaction products of butadiene and nitrogen oxides re-
suIted in eye irritation to humans (Altshuller, 1966; Reuss and Glasson,
1967).
Butadiene also reacts with ozone (Hanst et al., 1959).
Analytical methods exist for determing butadiene in several media.
Most
employ gas chromatography.
For humans, butadiene vapors are mildly narcotic and may result in a feel-
ing of lethargy, drowsiness, and irritation of the eyes and mucous membrane.
In one study, CWo males inhaled up to 16,680 mg butadiene/m3 for 8 hours
without visible effects (Carpenter et al., 1944).
No reports of chronic effects arising from the industrial use of butadiene
have been published in u.s. and Western Europe literature.
Reports from
Eastern Europe have suggested adverse effects from occupational exposure to
butadiene, prUnarily in synthetic rubber manufacture.
Poorly documented cases
of gastrointestinal tract, and respiratory, circulatory and nervous system
disorders have been reported.
Butadiene has a low toxicity in laboratory mammals.
For mice and rats,
the 2 hour LC50 averages between 270,000 and 285,000 mg/m3 (Shugaev,
1969).
Narcotic effects have been reported in mice exposed to 20% (200,000
mg/m3) butadiene in the air (Killian, 1930) and in rabbits exposed to 25%
(250,000 mg/m3) (Carpenter et al., 1944).
In a subacute study, rats
155
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inhaling 0, 2200, 4400, 8800, or 18,000 mg/m3 for 6 hr/day, 5 days/week
showed no signs of toxicity, except for a decrease in grooming behavior;
however, some exposure groups showed a decrease in neuromuscular function, but
not in a dose-dependent manner (Scala, 1977).
Chronic exPosures of rats, rabbits, and guinea pigs to 1,326, 4,830, or
14,8Q7 mg butadiene/m3 for 7.5 hr/day, 6 days/week for 8 months resulted in
few changes (see Table 39).
Although histological examination r~vealed no
differences between treated and control animals, cloudy swelling of the liver
was observed at the highest exposure level.
Treated female rats had fewer
litters compared to controls (Carpenter et al., 1944).
A series of Russian papers describes adverse effects in rats inhaling low
levels of butadiene (0, 1, 3, or 30 mg/m3) continuously for 81 days (Ripp,
1967; Molodyuk, 1969; Nikiforova et al., 1969).
Some of the reported effects
at the highest level tested included:
decreased weight gain after 50 days;
leukocytosis; increased serum cholinesterase activity; decreased motor
activity; and changes in the lung, spleen, kidney, and heart.
In a long-term
inhalation study, rats and rabbits exposed to 100 or 300 mg/m3 4 hours/day
for 4 months showed a lower leukocyte count and altered serum protein ratios
(Batkina, 1966).
A chronic gavage study in rabbits receiving 40 mg/kg for 7
months revealed lowered hemoglobin content (Shvartsapel, 1970).
One study in rats indicated that after inhalation, butadiene is found in
the brain, liver, spleen, and particularly, the perinephric fat.
Time sample
measurements for the brain and liver indicated no traces of butadiene 90
minutes after exposure was terminated (Shugaev, 1969).
The mutagenic effect of butadiene was evaluated in 6 strains of Salmonella
typhemurium by de Meester et al. (1978).
Tests were performed both in the
156
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absence and presence of a metabolic activation system.
Two strains showed a
direct (in absence of metabolic activation) and an indirect mutagenic response
to butadiene.
Butadiene monoxide and diepoxybutane have been suggested as possible pri-
mary metabolites of butadiene (de Meester et al., 1978), but this has not been
confirmed.
Both butadiene monoxide and diepoxybutane have been shown to
possess carcinogenic activity (Van Duuren et al., 1963; 1966), and diepoxy-
butane was mutagenic in several test systems (IARC, 1976b).
Little information is available on the toxicity of butadiene oligomers.
Russian workers exposed to 4-vinylcyclohexene exhibited the following:
keratitis, rhinitis, headache, hypotonia, leukopenia, neutrophilia 1ymphocyto-
sis and impaired metabolism (Bykov, 1968 in IARC, 1976a).
The oral LDSO of
vinylcyclohexene in rats is 3.08 ml/kg (2,556 mg/kg).
It caused irritation
when applied to rabbit skin (Smyth et al., 1969), and also produced skin
tumors when similarly applied but this latter effect may have been due to con-
tamination of the sample with the hydroperoxide of vinylcyclohexene (Van
Durren, 1963; 1965).
Cyclooctadiene and cyclododecatriene caused sensitiza-
tion and severe contact dermatitis when applied to the skin of laboratory
mammals (Brown and Hunter, 1968).
In plants, fumigation with butadiene resulted in no injury at 10 ppm (22.1
mg/m3) and <5% injury at 100 or 1,000 ppm (2210 mg/m3) (Heck and Pires,
1962).
Exposure to plants to mixtures of butadiene and ozone and the irradia-
tion products of butadiene and nitrogen oxides usually resulted in typical
smog damage (Haagen-Smit, et al., 1952).
Occupational exposure to butadiene is limited by the Occupational Safety
and Health Administration to an 8-hour time-weighted average of 1,000 ppm
3
(2,200 mg/m ).
The Department of Transportation regulates the transport of
157
-------
butadiene.
The Environmental Protection Agency has set effluent limitation
guidelines for discharges associated with butadiene manufactured by oxidative
dehydrogenation.
Butadiene is regulated as an indirect food additive by the
Food and Drug Administration.
158
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173
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CONCLUSIONS AND RECOMMENDATIONS
A.
Butadiene
The available literature indicates that butadiene is a compound of low
toxicity and minbnal environmental impact.
Additional data would be desirable
to supplement this conclusion, particularly for the following specific areas:
i)
metabolism - metabolites of butadiene have not been positively iden-
tified.
This is potentially important, because two suspected metabolites have
shown carcinogenic activity.
ii)
chronic toxicity - long-term studies would be desirable to resolve
the discrepancy between U.S/Western European reports of few adverse effects at
high concentrations and Eastern European studies showing some toxic effects at
low levels.
Further research, however, should not duplicate the on-going
chronic-exposure study at Hazleton Laboratories Europe, sponsored by the In-
ternational Institute of Synthetic Rubber Producers.
iii)
mutagenicity - additional studies might be considered in other test
systems besides bacteria.
LV)
environmental monitoring - only a few studies measured the amount of
butadiene released during phases of production and use.
Additional studies
would be desirable to determine if a potential problem exists, especially from
fugitive losses.
v)
environmental chemistry - the reactions of butadiene under conditions
other than urban air might be investigated.
B.
Butadiene oligomers
Fewer data are available for butadiene oligomers.
Vinylcyclohexene, be-
cause it is present as an impurity in butadiene, appears to be the more im-
portant oligomer for further study.
possible carcinogenic effects have been
174
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noted in a skin application study (although they may have been due to an im-
purity present in the vinylcyclohexene).
Another carcinogenesis study is
indicated; the National Cancer Institute is planning to begin an assay ~n
October, 1978.
However, additional information would be desirable for all
oligomers in the following broad categories where almost no data exis~
i)
biological effects
ii)
environmental exposure - it currently is not possible to assess the
environmental effects of the oligomers as no data are available.
175
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Appendix A
Summary of Sources Employed
References used in this report were selected from searches of automated
information retrieval systems, indices, standard references works, journals,
books, etc.
Manufacturers, researchers, and federal and state agencies, among
others, were contacted directly.
The following is a list of on-line systems searched:
Biological Abstract
Cancer line
Chemical Abstracts Condensates
Chemical Industry Notes
Economic Information System
Enviroline
Federal Index
Federal Index Weekly
Food and Science and Technology Abstracts
Marketing Abstracts
Marketing Abstracts Weekly
National Technical Information System
Ocean Abstracts
Pollution Abstracts
Smithsonian Science Information Exchange
Science Citation Index
Toxline
Toxback
Water Resources Abstracts
Also, the Technical Information Center data base was searched by the National
Institude of Occupational Safety and Health.
Manually searched indices included:
Biological Abstracts (1959-1970)
Chemical Abstracts (1957-1971)
Excerpta Media
Cancer (1953-1977)
Pharmacology and Toxicology (1965-1977)
Development Biology and Teratology (1965-1976)
Environmental Health and Pollution Control (1972-1976)
Occupational Health and Industrial Medicine (1971-1976)
Index Medicus (1957-1977).
176
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Appropriate books and compendia were examined.
In addition, current
journals were screened.
The literature search is considered complete through
June, 1978.
177
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TECHNICAL REPORT DATA
(PIetISt! read InstrUctions on the revene before completing)
,. REPORT NO. 12. 3. RECIPIENT'S ACCESSION NO.
560/2-78-008
4. TITLE AND SUBTITLE 5. REPORT DATE
December. 1978
Investigation of Selected Potential Environmental 6. PERFORMING ORGANIZATION CODE
Contaminants: Butadiene and Its Oligomers
7. AUTHORCS) 8. PERFORMING ORGANIZATION REPORT NO.
Lynne H. Hiller FRC 80G-C4807-0l
9. PERFORMING ORGANIZATION NAM& AND ADDRESS 10. PROGRAM ELEMENT NO.
Science Information Services Organization 11. CONTRACT/GRANT NO.
Franklin Research Center
20th and Parktvay
PhiladelT'1}.,;'" PA lQl03
12. SPONSORING AGENCY NAMe AND ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED
Office of Toxic Substances "1:'':_-' -
U.S. Environmental Protection Agency 14. SPONSORlfltG AGENCY coDe
Washington, D.C. 20460
15. SUPPl.EMENTARY NOTES
16. ABSTRACT
This report is a survey and summary of the literature on butadiene and its oligomer
}~jor aspects of their biological effect~, environmental exposure, chemistry, production
and use, and regulations are reviewed and assessed. Butadiene is a reactive gas used
primarily in the production of rubbers and resins; over 3 billion pounds are produced
annually in the U.S. Among other reactions, it undergoes self-condensation to form
cyclic oligomers, such as4-vinylcyclohexene, 1,5,9-cyclododectat~iene, and 1,5-cyclo-
octadiene. The latter is used primarily as a precursor to nylon; the other oligomers
are. less important commercially. Vinylcyclohexene, how!,!ver, is a contaminant in
butadiene. Limited manitoring data indicate that low levels or butadiene enter the
environment during production , end-use, storage and transport; it has been identified
as a minor constituent of urban air and gasoline. The high degree of chemical reactivit
of butadiene precludes environmental persistence. In humans, exposure to butadiene vapo
may resultn lethargy and drowsiness, as well as irritation to the eyes and mucous
membranes. There have been no reports in the U.S. or Western Europe of long-term
effects of butadiene arising from occupational exposure. Poorly documented cases of
gastrointestinal tract, and circulatory and nervous system. disorders have been reported
in Russian synthetic rubber workers; butadiene has been implicated as a causitive factor'
Butadiene intoxication may cause narcosis in laboratory mammals; few adverse effects hav
been reproted for chronic exnosures. Few toxicity data are available for the oli2:omers
-
17. KEY WORDS AND DOCUMENT ANAl. YSIS
a. DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS C. COSA TI Field/Group
Butadiene Biological & Med.
-- Sciences
Chemical Industry -biology
Environmental Engineering
lRegulations -clinical medicin~
iToxicology -toxicology
~inylcyclohexene
Cycloocatdiene, Cyclododecatriene
18. DISTRIBUTION STATEMENT 19. SECURITY Cl.ASS (This Report) 21. NO. OF PAGES
Document is available to the public through . 177 PP.
the National Technical Information Service, 20. SECURITY CLASS (Tllu page) 22. PRICe
Springfield, Virginia 22151
EPA Form 2220-1 (Rn.4-77)
PREVIOUS EDITION 1$ OBSOLETE
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