..^
«J. DETWTHWT OF CQHUEICE
560275007
INVESTIGATId OF SIUECIED PWWIM. ENVIW1MEHTAL
CONTAMINANTS
CHLORINATED PARAFFINS
SYRACUSE UNIVERSITY RESEARCH CORPORATION
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
NOVEMBER 1975
-------
EPA-580^75-007 :,''[ PB 248 634
INVESTIGATION OF SELECTED
POTENTIAL ENVIRONMENTAL CONTAMINANTS:
CHLORINATED PARAFFINS
Reproduced by
NATIONAL TECHNICAL
INFORMATION SERVICE
US Department of Commerce
Springfield, VA
November 1075
i . i
FINAL REPORT
Office of Toxic Substances
U.S. Environmental Protection Agency
-------
TECHNICAL REPORT DATA
(Please read Inunctions on the reverse before completing)
RLPORT NO.
EPA 560/2-75-007
3. RECIPIENT'S ACCESSION-NO.
TITLE AND SUBTITLE
Investigation of Selected Potential Environmental
Contaminants: Chlorinated Paraffins
5. REPORT DATE
November 1975
6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
Philip H. Howard, Joseph Santodonato, Jitendra Saxena
8. PERFORMING ORGANIZATION REPORT NO
TR 75-622
9 PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
Life Sciences Division
Syracuse University Research Corporation
Merrill Lane, University Heights
Syracuse, New York 13210
11. CONTRACT/GRANT NO.
EPA 68-01-3101
12 SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Technical Report
4. SPONSORING AGENCY CODE
15 SUPPLEMENTARY NOTES
16. ABSTRACT
This report reviews the potential environmental hazard from the
commercial use of chlorinated paraffins. Chlorinated paraffins, in most cases,
contain 10 to 30 carbon atoms and a chlorine content of 40 - 70%. They are used
as lubricating oil additives, secondary plasticizers, and flame retardants.
Information on physical and chemical properties, production methods and quantities,
commercial uses and factors affecting environmental contamination, as well as
information related to health and biological effects, are reviewed.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Chlorinated paraffins
Chlorowax
Oil additives
Plasticizers
Flame retardants
b.lDENTIFIEHS/OPEN ENDED TERMS 0. COSATl! iclcl/Croup
Ti. DISTRIBUTION STATEMENT ' " "
Document is available to public through
the National Technical Information
Service, Springfield, Virginia 22151.
19. SECURITY CLASS (fals Riport) [ 21. NO.
20. SECURITY CLASS (Thti page>
ISA form 2230-1
-------
EPA-560/2-75-007 TR 75-622
INVESTIGATION OF SELECTED POTENTIAL
ENVIRONMENTAL CONTAMINANTS:
CHLORINATED PARAFFINS
Philip H. Howard
Joseph Santodonato
Jitendra Saxena
November 1975
Final Report
Contract No. 68-01-3101
Project L1259-05
Project Officer
Frank Kover
Prepared for
Office of Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
Document is available to the public through the National Technical Information
Service, Springfield, Virginia 22151
-------
NOTICE
This report has been reviewed by the Office of Toxic Substances, EPA, 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.
ii
-------
TABLE OF CONTENTS
Executive Summary
I. Physical and Chemical Data 1
A. Structure and Properties 1
1. Chemical Structure 1
2. Physical Properties of Commercial Materials 8
3. Principal Contaminants 12
B. Chemistry 16
1. Reactions Involved in Uses 16
2. Hydrolysis 17
3. Oxidation 17
4. Photolysis 18
5. Other 19
II. Environmental Exposure Factors 21
A. Production and Consumption 21
1. Quantity Produced 21
2. Producers, Major Distributors, Importers, Sources of 23
Imports and Production Sites
3. Production Methods and Processes 27
4. Market Prices 29
5. Market Trends 29
B. Uses 32
1. Major Uses 32
2. Minor Uses 43
3. Discontinued Uses 45
4. Projected or Proposed Uses 45
5. Possible Alternatives to Uses 46
C. Environmental Contamination 50
1. General 50
2. From Production 50
3. From Transport and Storage 52
4. From Use 53
5. From Disposal 55
6. Potential Inadvertent Production of Chlorinated 55
Paraffins in Other Industrial Processes
7. Potential Inadvertent Production in the Environment 56
iii
-------
Table of Contents
(continued)
D. Current Handling Practices and Control Technology 59
1. Special Handling in Use 59
2. Methods for Transport and Storage 59
3. Disposal Methods 60
4. Accident Procedures 61
5. Current Controls 61
6. Control Technology Under Development 61
E. Monitoring and Analysis 62
1. Analytical Methods 62
2. Monitoring 73
III. Health and Environmental Effects 75
A. Environmental Effects 75
1. Persistence 75
a. Biological Degradation, Organisms, and Products 75
b. Chemical Degradation in the Environment 80
2. Environmental Transport 80
3. Bioaccumulation 82
4. Biomagnification 84
B. Biology 86
1. Absorption 86
2. Excretion 87
3. Transport and Distribution in Living Organisms 87
4. Metabolic Effects 87
5. Pharmacology 87
C. Toxicity - Humans 87
1. Controlled Studies 88
2. Epidemiology 89
3. Occupational Studies 89
D. Toxicity - Birds and Mammals 89
1. Acute 89
2. Subacute 91
3. Sensitization 91
iv
-------
Table of Contents
(continued)
r
91
4. Teratogenicity 91
5. Mutagenicity 92
6. Carcinogen!city 92
7. Chronic Studies 92
8. Behavioral Effects 92
9. Possible Synergisms
92
E Toxicity - Lower Animals
94
F. Toxicity - Plants
94
G Toxicity - Microorganisms
94
H Effects on Inanimate Objects and Structures
95
IV Regulations and Standards
95
A Current Regulation
96
B Consensus and Similar Standards
97
V Summary and Conclusions
102
REFERENCES
-------
LIST OF TABLES
lumber Page
1 Composition of Paraffins Obtained by Dechlorination of 2
Different Chlorinated Paraffin Preparations
2 Effect of Chlorine Atom on Reactivity of Hydrogen Atoms in 3
n-Butane
3 Nonane Chlorination Distribution 5
4 Percent Distribution of Chlorinated Paraffins (C2fi) at 5
Different Degrees of Chlorination
5 Distribution of Chlorinated Paraffins 6
6 Effect of Total Chlorine and Oil Content on Percent 7
Labile Chlorine
7 Physical Properties of Commercial Chlorinated Paraffins 9
8 Solubility of Chlorinated Paraffins 11
9 Metal Analyses of Diamond Shamrock Chlorowax 14
10 Stabilizers Used with Chlorinated Paraffins 15
11 Product Yields from Reductive Dechlorination of 20
Commercial Chlorinated Paraffin Products
12 United States Chlorinated Paraffin Production and Sales 22
13 Capacities, Major Producers, and Sites of Production 24
of Chlorinated Paraffins
14 Producers of Chlorinated Paraffin During 1959-1974 25
15 Chlorinated Paraffin Distributors 26
16 Major Applications of Chlorinated Paraffins 33
17 Formulations of Chlorinated Paraffins for Cutting and 35
Extreme Pressure Oils
18 Non-Lubricant Applications and Markets for Chlorinated 36
Paraffins
19 Flame Retardant Chemicals Market 39
VI
-------
List of Tables
(continued)
Number
20 U.S. Consumption of Miscellaneous Flame Retardants 39
for Polymers (million Ibs.)
21 Minor Uses of Chlorinated Paraffins 43
22 Possible Replacements for Flame Retardant Applications 49
of Chlorinated Paraffins
23 Comparison of PCB and Chlorinated Paraffin Physiochemical 51
Properties Relevant to Environmental Contamination
Considerations
24 Applications of PCB's and Chlorinated Paraffins 53
(percentage of total)
25 Plasticizer Performance of PCB's and Chlorinated 54
Paraffins in PVC
26 Organic Compounds That are Produced By Direct 57
Chlorination
27 Paraffinic Hydrocarbons Identified in Industrial 58
Effluents
28 Analytical Methods of Chlorine Detection 65
29 Effect of Alumina Chromatography on the Apparent Chlorine 70
Content in Various Biological Samples
30 Recovery of Chlorinated Paraffins from Hexane 71
31 Summary of the Biodegradation Studies with Commercial 76
Preparations of Chlorinated Paraffins
32 Oxygen Consumed in BOD Bottle Test and Warburg Respirometer 78
with Chlorowaxes
33 Biodegradation of Chlorinated Paraffins in Spiked Sediments 79
34 Uptake of Chlorinated Paraffins and PCB from Suspended Solids 82
and Food by Juvenile Atlantic Salmon
35 Summary of Acute Animal Toxicity of Chlorinated Paraffins 90
36 Acute Fish Toxicity of Chlorowax Preparations 93
vii
-------
LIST OF FIGURES
Number Page
1 Gas Chromatograph of the Hydrocarbons Resulting from 2
Reductive Dechlorination of CP44
2 Solidification Temperature of Chloroparaffins as a 8
Function of the Chlorine Content
3 Process Plant for the Chlorination of Paraffin Wax 28
4 Average Unit Price/Lb. of Chlorinated Paraffins 30
viii
-------
Executive Summary
Commercial chlorinated paraffins are extremely complex mixtures that
are similar in physical properties and commercial applications to the widely
recognized environmental contaminant, polychlorinated biphenyls (PCB's).
However, chlorinated paraffins are considerably less chemically stable relative
to PCB's.
V-
Approximately 74 million pounds of chlorinated paraffins were produced
in the United States in 1973 and the market for these compounds continues to
^
rise (>10% increase per year). Major applications of chlorinated paraffins
i- include uses as lubricating oil additives (45% of total production) , second-
ary vinyl plasticizers (24%), flame retardants in rubber, plastics, and
paints (27%), and traffic paint additives (4%). Applications of PCB's as oil
additives and plasticizers have been suggested as major sources of environmental
contamination. However, the quantities of chlorinated paraffins released to
u_ the environment are unknown and there are no published monitoring data from
i which estimates could be made. The lack of monitoring data is directly attributable
\_
to the lack of a specific and sensitive analytical method. The best method pres-
ently being used is capable of measuring only 0.5 ppm and can only be used with
certain commercial products. However, some monitoring data from Great Britan
are expected to be published relatively soon, which use an analytical method that
is sensitive to approximately 0.05 ppm. Conclusive studies have not been conducted
~~ to determine the environmental fate and persistence of the commercial formulations,
although there is evidence that degradation occurs with some formulations, based
upon oxygen consumption by microorganisms or loss of the parent compound. From
the available information, it appears that chlorinated paraffins are probably
less persistent than PCB's. No information is available on metabolites that
ix
-------
might be formed. The potential for bioaccumulation of chlorinated paraffins
in fish appears to be quite small based u]bn experimental results, but the
possibility of metabolite bioaccumulation has not been ruled out. Chlorinated
paraffins exhibit a low degree of acute toxicity when administered by oral,
dermal, or inhalational routes. However, lacking is any information on long
term, low level exposures, although some preliminary subacute investigations
with fish have produced significant mortality and numerous sub-lethal effects.
These results suggest the value of exploring subacute effects in higher animals.
In summary, because of the limited data available, a conclusive environ-
mental hazard assessment of chlorinated paraffins is not possible. No published
monitoring data are available yet; the chemical structure, bioaccumulation potential,
and toxicity of the environmental degradation products are unknown; and the
available toxicity data on the commercial products are completely inadequate
for assessing potential detrimental effects from trace contamination. However,
from the available data, it can be concluded that chlorinated paraffins are
(1) produced in larger quantities than PCB's, (2) are likely to be released
to the environment, (3) are less mobile and persistent than PCB's, and (4)
are less acutely toxic.
-------
This report reviews commercially important chlorinated paraffins, which,
in most cases, have 10 to 30 carbon atoms and a chlorine content of 40-70%
(Hardie, 1964). Other chlorinated aliphatic compounds, such as chlorinated
fatty acids, long-chained alcohols, alkylaromatic compounds, and polyethylene,
are considered only when warranted by the available information.
I. Physical and Chemical Data
A. Structure and Properties
1. Chemical Structure
As the term implies, chlorinated paraffins are chlorinated de-
rivatives of paraffinic hydrocarbons. In terms of the number of isomers, these
formulations exceed such complicated commercial mixtures as polychlorinated
biphenyls (PCB's) and chlorinated naphthalenes. This is due to the mixture of
parent paraffinic hydrocarbons (usually various chain lengths) which are used
commercially in the chlorination process. In contrast, only one parent hydro-
carbon, i.e., biphenyl or naphthalene, is used with polychlorinated biphenyls
and chlorinated naphthalenes, respectively.
In the United Kingdom, a distinction is made between chlorinated
paraffins that are derived from liquid paraffins as opposed to those made from
solid parent material, the latter being referred to as chlorinated-paraffin
waxes (Hardie, 1964). In America, the term chlorinated paraffins refers to
"chlorinated, mainly straight-chain, saturated hydrocarbons of the CJQ ~ C30
range" (Hardie, 1964). The broader American term will be used in this review.
The commercial chlorinated paraffins are usually produced from
a mixture of n-paraffins of varying chain lengths. This is illustrated by the
-------
work of Zitko (1974b) and Panzel and Ballschmiter (1974). These investigators
reductively dechlorinated some commercial chlorinated paraffins and then analyzed
the resulting hydrocarbons by gas chromatography . Zitko 's (1974b) results are
depicted in Table 1 and Panzel and Ballschmiter's (1974) results are presented
in Figure 1.
Table 1. Composition of Paraffins Obtained by Dechlorination
of Different Chlorinated Paraffin Preparations
(Zitko, 1974b)
Percent
Chlorinated Paraffin C? \ C??
C?s C?ft C?
Chloroparaffin, 40%
Clorafin 40
CP 40
Cereclor 42
Chloroparaffin, 50%
4.5 10.0 15.7 19.3 18.5 15.3 9.8 6.7
3.7 8.2 14.0 17.5 19.2 17.4 12.4 7.6
3.9 9.1 14.9 19.2 19.8 18.0 15.1
3.6 8.8 14.7 18.6 19.5 17.2 11.5 6.0
7.4 14.9 20.7 23.1 19.9 14.0
0 ->
220
Figure 1. Gas Chromatograph of the Hydrocarbons Resulting from
Reductive Dechlorination of CP44 (Panzel and Ballschmiter,
1974). Permission granted by Springer-Verlage.
-------
The number and position of the substituted chlorines is de-
pendent upon the amount of branching or other non-paraffinic structures in the
parent hydrocarbon mixture and the extent of chlorination. The reactivity of
aliphatic hydrogens during free-radical chlorination is dependent upon the acidity
of the substituted hydrogen; the more acidic the less replaceable. Thus,
tertiary carbons are chlorinated faster than secondary followed by primary
(Bratolyubov, 1961). Since the paraffinic hydrocarbon mixtures used commercially
contain mostly straight chained saturated hydrocarbons, secondary and primary
carbons are primarily available. Therefore, the chlorines are probably randomly
distributed, up to a point, along the methylene (-CH2-) groups of the carbon
chain. Two chlorines attached to the same carbon is unlikely, since
the first chlorine substitution decreases the reactivity of the other hydrogens
on the carbon attached to the chlorine. Table 2 illustrates this decrease in
reactivity caused by the inductive effect of the chlorine atom. This inductive
C C
effect also inhibits vicinal substitution ( ) whenever other sites of
\j J6 uJ6
reaction are possible. As the commercial product approaches 70% chlorine,
the chain will approach the condition where one atom of chlorine is attached
to each carbon atom.
Table 2 . Effect of Chlorine Atom on Reactivity of Hydrogen
Atoms in ri-Butane (Bratolyubov, 1961)
Position of CH atom. Ct^ 3 62 Ct CH
% Substituted on 27 47 22 7
chlorination
Relative Reactivity 2.6 6.7 3.2 1
of H Atom
-------
This distribution of chlorine along the paraffinic chain is
supported by some experimental evidence. For example, chlorination of a
paraffin can be continued until the chlorine content is slightly more than 70%
(~.e., C2oH22c^2o)» thereafter, chlorine can be introduced only with difficulty
(Hardie, 1964). This corresponds to substitution of one chlorine on every
carbon atom. Zitko and Arsenault (1974) noted that the lack of CC&2 groups
"was confirmed experimentally from NMR spectra of chlorinated paraffins with
less than 60% chlorine (Gusev et al., 1968) and of chlorinated polyethylene
(Heintke and Keller, 1971)". Heisele and Colelli (1965) have suggestive evidence
that mixtures that are less than fully chlorinated contain all the statistically
possible isomers. From a chlorinated nonane (99.7 mole percent) mixture, they
ware able to count all the 25 possible dichlorononane compounds, although the
quantities of the isomers present varied greatly. Gas chromatography was used
for determining the number of peaks, and the disubstituted structure was assigned
by relative retention time on a non-polar column.
The chlorinated paraffins, besides containing various isomers
of mono-, di-, trichloro-, etc. compounds, also contain various ratios of the
mono-, di-, trichloro-, etc. compounds as well as unchlorinated paraffin. The
relative ratios are dependent upon the degree of chlorination. The study by
Heisele and Colelli (1965) measured by gas chromatography the amount of nonane
and mono-, di-, and trichlorononane at various chlorination percentages. These
results are noted in Table 3.
-------
Table 3 . Nonane Chlorination Distribution
(Heisele and Colelli, 1965)
Chlorine Concentration (%)
T fi 12 17 21 29 35 42
48
Nonane
Mono
Di
Tri
80 59
20 37
4
43
41
16
26
46
26
2*
20
46
30
4*
10
39
41
10*
32-
25 9 -
47
28*
* Estimate
Similar studies were reported by Koennecke and Hahn (1962) and Teubel et al.
(1962), except that they separated the mixture into various fractions by
chromatography on silica and used paraffins containing larger numbers of carbons,
Their results are presented in Tables 4 and 5 From these studies, it can be
seen that as the degree of chlorination approaches 50%, the amount of paraffin
and monochlorinated paraffin becomes very small.
Table 4. Percent Distribution of Chlorinated Paraffins (C2e)
at Different Degrees of Chlorination
(Koennecke and Hahn, 1962)
Paraffin (C26)
Monochloro-
Dichloro-
Polychloro-
17.2
10.6
27.3
20.1
40.6
Df?
22.6
3.6
14.5
17.6
63.0
ree of
27.2
1.4
7.8
10.5
79.4
Chlprin.ation (wt% chl
32.9
0.34
1.8
4.0
93.1
36.0
0.27
0.7
1.4
96.5
39.5
0.08
0.6
0.68
97.9
orine)
42.8
-
0.1
0.38
98.9
46.8
-
-
-
99.1
-------
Table 5 . Distribution of Chlorinated Paraffins
(Teubel et al., 1962)
C19 C20 ~ C30
mol. CJl/mol. paraffin
0
1
2
3
4
5
6
>6
26% chlorine
(vol%)
4.4
17.8
27.8
28.9
11.2
7.7
-
26.1% chlorine
(vol%)
1.1
3.7
11.0
14.2
24.1
25.2
12.5
8.2
Because the commercial chlorinated paraffins are made from
commercial paraffin waxes, it is likely that non-ri-paraffinic hydrocarbons,
such as alicyclic and aromatic compounds, will be present in small amounts
in the parent paraffin waxes. Chlorination of these materials may result in
very unstable carbon-chlorine linkages, such as benzylic and tertiary carbon-
chlorine bonds. Tertiary chlorines are very likely when isoparaffins are
present, because tertiary carbons are chlorinated faster than primary or
secondary. The order of stability of carbon-chlorine linkages is: primary
C£> secondary C&> alicyclic C£> benzylic C£>, allylic CSL, tertiary CH. Wein-
traub and Mottern (1965) have studied the relative amount of labile chlorine
atoms in Chlorowax 40 and 70 by testing the chlorinated paraffins with silver
nitrate reagent and weighing the silver chloride precipitate. Based partially
on the data in Table 6, they concluded that "the labile chlorine was pro-
portional to the oil and/or to the naphthenic (alicyclic) content of the
wax, and inversely proportional to the total chlorine content."
-------
Table 6 . Effect of Total Chlorine and Oil Content on
Percent Labile Chlorine (Weintraub and Mottern,
1965)
Labile C£
Oil (%) Cfc (Wt. %) (Wt. %)
' --*-- --*--
128
128
126
126
Chlorowax 40
Chlorowax 70
0.7
0.7
15.0
15.0
<1.0
"<1.0
60.0
67.0
44.0
58.6
40
70
9.5
3.7
38.9
15.7
45.3
1.4
The high percentage of labile chlorine for Chlorowax 40 is difficult to explain.
One possibility is that the initial dehydrochlorination produces allylic and
benzylic chlorine atoms, and this perpetuates the instability. Inductive
stability may be provided to tertiary chlorine atoms by vicinal chlorine atoms in
the higher chlorinated materials, resulting in less labile chlorines in Chloro--
wax 70. Whatever the explanation, it appears that small amounts of tertiary,
allylic, and/or benzylic chlorines are'present in the commercial chlorinated paraffins.
In summary, commercial chlorinated paraffins are complex mixtures
containing numerous isomers and varying numbers of chlorines per molecule. The
starting hydrocarbon material usually contains mostly n-paraffins with varying
numbers of carbon atoms (e.g., C9 - C]2 or C20 - C2s). However, some small
amounts of isoparaffins or aromatics may be present. The highest chlorinated
paraffins (approximately 70% chlorine by weight) roughly correspond to one
chlorine atom substituted on each carbon atom.
-------
2. Physical Properties of Commercial Materials
Because of the wide variety of starting paraffin mixtures and
degrees of chlorination possible, the physical properties of the commercial
chlorinated paraffins cover a broad range. Competitive formulations are grouped
together and illustrated in Table 7. The properties having the most industrial
significance are the viscous character (lubricant applications), non-flammability
(flame retardant applications), relatively low toxicity, miscibility with plasti-
cizers (secondary plasticizer applications), and the ability, at elevated tem-
peratures, to split off small quantities of hydrogen chloride (extreme-pressure
lubricant applications) (Hardie, 1964).
For any given paraffin feedstock, the viscosity and specific
gravity increase with the chlorine content. Both liquid chlorinated paraffins
as well as brittle, resinous solids are possible. Initially, as the chlorine
content increases, the solidification point decreases as is illustrated in
Figure 2. However, at a certain chlorine content, a point of inflection is
reached and, thereafter, the solidification point increases with increasing
chlorine content. The point of inflection will vary with different paraffin
feedstocks.
60
^ SO
!W
§ 30
§ 10
'§
i-»
&
\
\
#
0 S 10 15 20 25 30 35 HO f5 50 55
Chlorine content in % by wt.
Figure 2. Solidification Temperature of Chloroparaffins as a
Function of the Chlorine Content (Asinger, 1967)
Permission granted by Pergamon Press Ltd.
-------
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As might be expected, the specific gravity increases as the
average number of chlorine atoms per molecule increases. This correlation is
frequently taken advantage of in order to provide rough estimates of the chlorine
content.
The chlorinated paraffins have a "characteristic slight, and
not unpleasant, odor" (Hardie, 1964). This is probably due to small quantities
of lower molecular products, which provide small, but measurable vapor
pressures. For example, the vapor pressure of a 023 paraffin chlorinated
to 42, 48, or 54% was 2 x 10~5 mm Hg when measured at 65°C (Hardie, 1964).
The industry routinely measures the volatility of their commercial products
in terms of evaporation rate (g/cm2/hr at 100°C) (see Table 7).
The color of the commercial chlorinated paraffins is usually
found in the yellow range, varying from light amber to pale yellow, honey,
or yellow color. However, color is not a constant characteristic since
it is dependent upon manufacturing (high temperatures increase the color)
and subsequent storage conditions (Hardie, 1964).
As noted earlier, the solubility properties of chlorinated
paraffins have considerable significance. None of the chlorinated paraffins
are soluble in water or the lower alcohols (Hardie, 1964). However, many
of the products can be emulsified with water (approximately 70/30 chlorinated
paraffin to water) and are used in that form mostly for flame retardancy appli-
cations. The following formulations are water dispersions: Rez-0-Sperse A-l,
3, A-4 (Dover), Delvet 65, 65-S (Diamond-Shamrock) and Unichlor 70-65 (Neville).
Table 8 summarizes the solubility of various chlorinated paraffins
in organic solvents and oils. Formulations containing over 40% chlorine are
10
-------
compatible "with natural rubber, chlorinated rubber, synthetic rubber, polyester
resins, and many alkyl resins, as well as with such common plasticizing compounds
as dioctyl or dibutyl phthalate and tricresyl phosphate" (Hardie, 1964). This
compatibility with common resins and plastics, especially polyvinyl chloride, and
with common plasticizers allows chlorinated paraffins to be used as plasticizer
extenders (secondary plasticizer).
Table 8 . Solubility of Chlorinated Paraffins
(Roberts, 1949; Hardie, 1964)
% Chlorine
- 28% - Soluble in mineral and lubricating
oils
42-54% - Soluble in normal aliphatic and
aromatic hydrocarbons, chlorinated
solvents, and ether
- Miscible with vegetable oils and
mineral oils
-70% - Soluble in vegetable and mineral
oils, chlorinated solvents, esters,
ketones, aromatic hydrocarbons, and
terpenes
- Insoluble in alcohols, aliphatic
hydrocarbons, and ethers
11
-------
3. Principal Contaminants
Because commercial chlorinated paraffins are extremely
complex mixtures, it is difficult to distinguish between commonly occurring
isomers and contaminants. For example, are the tertiary chlorine substi-
tuted products formed from isoparaffins contaminants or not? What about the
heavy olefins formed during thermal dehydrohalogenation? Chlorinated aromatic
impurities resulting from aromatics in the paraffin feed stock are somewhat more
clear cut since they are certainly not paraffins. Zitko and Arsenault (1974)
examined the ultraviolet spectra (absorbance at 275 mm) of Cereclor 42,
Clorofin 40, and Chlorez 700 and concluded that the concentration of
chlorinated aromatic hydrocarbons was probably not very high. Similarly,
Ligezowa et al. (1974) used infrared spectrometry with a technical chlorinated
paraffin (-26 C atoms) that had been separated by column chromatography to
prove the absence of large amounts of unsaturated material.
During chlorinated paraffin manufacture, some chlorinated
solvents are used to increase the rate of chlorination. This is especially
true with high percentage chlorine products where the increase in viscosity
due to added chlorine results in slow chlorination rates. Carbon tetrachloride
is the most common solvent that is used, although hexachlorobutadiene has
been reported (Hardie, 1964). Harnagea and Crisan (1974) have developed a
rapid infrared spectrophotometric method for determining carbon tetrachloride
in chlorinated paraffins containing 70% chlorine. Heisele and Colelli (1965)
suggest that carbon tetrachloride as well as methylene chloride, chloroform,
and perchloroethylene may be formed from cracking during chlorination. These
materials may be found in trace amounts in the final product. It is unlikely
that large amounts will remain following the hydrogen chloride removal step
(see Section 1II-A-3, p. 27).
12
-------
Chlorination catalysts are rarely used, although one process
has reportedly used calcium oleate or benzoate (Hardie, 1964). Metal
catalysts are avoided since they may promote decomposition of the chlorinated
paraffins. The Diamond Shamrock Chemical Company has analyzed its Chlorowax
product line for a number of metals by atomic absorption spectrometry. The
analyses are presented in Table 9. It is unknown whether other product lines
would have similar elemental concentrations.
Stabilizers are frequently added to chlorinated paraffins
to inhibit decomposition, especially when the product is intended for
elevated temperature use. Table 10 lists the compounds that have reportedly been
used as stabilizers. Since the dehydrohalogenation process is not catalyzed
by oxygen, antioxidants are not used as stabilizers. Other additives
are combined with chlorinated paraffins to increase their flame retardancy
(e.g., antimony oxide). These will be discussed in Section II-B, p. 32.
13
-------
Table 9. Metal Analyses of Diamond Shamrock Chlorowax
Parts Per Million (ppm)
Resinous
CHLOROWAX 70
Element
Lead
Cadmium
Mercury
Chromium
Iron
Copper
Vanadium
Titanium
Calcium
Magnesium
Sodium
Potassium
Barium
Silver
Cobalt
Molybdenum
Bismuth
Aluminum
Zinc
Tin
An t imony
Pb
Cd
Hg
Cr
Fe
Cu
V
Ti
Ca
Mg
Na
K
Ba
Ag
Co
Mo
Bi
Al
Zn
Sn
Sb
Minimum
Detection
Limit "ppm"
0.002
0.040
0.025
0.001
0.006
0.001
0.080
0.240
0.150
0.025
0.050
0.200
0.090
0.150
2.00
0.50
1.10
0.50
0.03
1.9
1.6
Average
Detected
"ppm"
0.01
(Less than
0.12
0.07
0.88
0.02
(Less than
(Less than
1.35
0.17
0.76
0.76
(Less than
0.21
(Less than
(Less than
(Less than
1.1
0.06
5.2
5.3
Maximum
Detected
"ppm"
0.02
0.040)
0.12
0.12
1.14
0.03
0.080)
0.240)
2.0
0.23
0.80
0.85
0.090)
0.34
2.00)
0.50)
1.10)
1.2
0.08
7.4
6.5
Liquid
All Grades
Average
Detected
"ppm"
0.02
(Less than
0.07
0.01
0.94
0.02
(Less than
(Less than
1.08
0.08
0.92
0.70
0.24
0.25
(Less than
(Less than
(Less than
1.0
0.04
2.6
3.0
Maximum
Detected
"ppm"
0.04
0.040)
0.15
0.02
1.65
0.10
0.080)
0.240)
2.50
0.24
2.10
2.80
0.70
0.87
2.00)
0.50)
1.10)
1.25
0.12
6.3
9.5
14
-------
Table 10. Stabilizers Used with Chlorinated Paraffins
Reference
Roberts (1949)
Asinger (1967)
Hardie (1964)
Compagnie Francaise de
Raffinage (1972)
Hirashima & Miyasaki
(1972)
Krockenberger (1972)
Nishimura et al, (1972)
Compounds
Hydrocarbons of the terpene or pinene groups
Triethanolamine
Phenoxypropylene oxide
Acrylated ethylenimines
Ethylene oxide
Lead oxide (about 10% added)
Ethylene glycol
1,2- and 1,3-Dihydroxypropane
Glycerol
Pentaerythritol
Organometallic compounds of tin
Pyrimidine compounds
3-Phenoxy-l,2-epoxypropane
Certain compounds of lead or cadmium
Phosphates
Propylene glycol
Ethylenediaminetetraacetic acid (EDTA)
di-Na EDTA
Nitrilotriacetic acid
Poly (4-vinylpyridine)
Isoquinoline
Acetonitrile
Alkanediol diglycidyl ethers
Alkaline earth hydroxide
15
-------
B. Chemistry
1. Reactions Involved in Uses
There are three major applications of chlorinated paraffins:
(1) as a secondary plasticizer, (2) as a lubricant and cutting fluid additive,
and (3) as a flame retardant. The last two applications depend upon the
ability of chlorinated paraffins to release hydrochloric acid at elevated
temperatures. Actually, the thermal stability of chlorinated paraffins at
normal processing temperatures is quite high. The conventional industrial
test for heat stability consists of heating the sample to 347°F (175°C) for
4 hours and measuring the liberated hydrogen chloride. Results from this
test for various formulations are presented in Table 7. In all the form-
ulations noted, less than 0.5% HC£ is liberated. However, at elevated
temperatures or by adding accelerators (e.g., iron oxides, zinc oxides, zinc
carbonates and zinc borates, Scheer, 1944), the decomposition process is
considerably increased. Above 300°C dehydrochlorination is rapid and
intense blackening occurs (Hardie, 1964). This release of hydrochloric acid
can be used in two ways: (1) to react with metal surfaces to form a thin
but strong solid film of metal chloride lubricant (chlorides also make the
material act more brittle which is advantageous for cutting) (Matthijsen and
Van Den Brekel, 1967) or (2) to inhibit the radical reactions in a flame.
In contrast to lubrication and flame retardancy uses, many
applications depend upon the stability of chlorinated paraffins at lower
temperatures. For example, if the material is to be used as a secondary
plasticizer, it should not decompose and turn black during the processing of
16
-------
the plastic (thermal molding is frequently used). Dehydrochlorination of
chlorinated paraffins is accelerated by hydrogen chloride, zinc, tin, and
antimony chloride "which indicates that it proceeds by an ionic mechanism"
(Zitko and Arsenault, 1974). Stabilizers, which are added to chlorinated
paraffin formulations, are based upon disruption of the decomposition reaction.
Thus, the stabilizers listed in Table 10 attempt to bind the hydrochloric
acid or complex the possible metal catalyst contaminants. Weintraub and
Mottern (1965) have suggested that the amount of hydrogen chloride evolved
during the thermal stability test at 175°C is proportional to the non-n-paraf-
finic content of the starting hydrocarbon mixture.
2. Hydrolysis
Under ambient and neutral conditions, chlorinated paraffins
appear to hydrolyze very slowly. In fact, many formulations consist of water
emulsions of chlorinated paraffins. However, under pressure, and with aqueous
or alcoholic alkali, dehydrochlorination takes place accompanied by poly-
merization (Hardie, 1964). Replacement of chlorines by hydroxyl groups has
only been reported at elevated temperatures using alkali and alkaline earth
hydroxides (Hardie, 1964). Roberts (1949) has reported that chlorinated
unsaturated alcohols have been prepared from chlorinated paraffins by treat-
ment with aqueous alkali metal hydroxides or carbonates under pressure with
heating.
3. Oxidation
Oxygen apparently has no catalytic effect on the decomposition
of chlorinated paraffins (Roberts, 1949). The substances are highly resistant
17
-------
to oxidizing agents and antioxidants are of no value as stabilizers. Possible
products from oxidation at elevated temperatures have not been determined.
4. Photolysis
Information on the photochemistry of chlorinated paraffins is
somewhat contradictory. It has long been known that chlorinated paraffins
exposed to direct sunlight will decompose at ordinary temperatures and evolve
hydrogen chloride (Roberts, 1949; Hardie, 1964). This may be due to small
amounts of impurities in the commercial product. In fact, formulations con-
taining substantial quantities of branched-chain paraffins (allowing formation of
unstable tertiary chlorides) may show unusually low light stability (Hardie, 1964).
However, the chlorinated paraffins must exhibit considerable
photochemical stability since they are usually manufactured in the presence
of light. Friedman and Lombardo (1975) have taken advantage of this relative
photolytic stability to eliminate chlorinated aromatic interferences during
analysis (see Section II-E, p. 62). They felt that since chlorinated paraffins
are poor absorbers of UV irradiation, the substances should not undergo appreciable
photochemical decomposition. They photolyzed a variety of chlorinated paraffins
(Chlorowax 500, Unichlor 70LV, Cereclor S-45 and S-52) in petroleum ether
using high energy light (13% of the light energy was in the 220-280 nm region).
No decompostion was noted. Although these conditions are considerably different
than sunlight (>290 nm) irradiation of the concentrated chlorinated paraffin,
it is unlikely that a substance that does not photodegrade under high energy
light will degrade under lower energy light, especially since the high energy
light contains wavelengths comparable to lower energy light. Thus, it appears
that chlorinated paraffins do not photodegrade, although in the concentrated
form, some decomposition may be noted (increased color and hydrogen chloride
evolution) probably due to small amounts of contaminants.
18
-------
5. Other
Information on other chemical reactions of chlorinated
paraffins is very limited. Hardie (1964) states that chlorinated paraffins
will condense with aromatic compounds such as benzene, toluene, xylenes,
naphthalenes, and phenol in the presence of anhydrous aluminum chloride.
Paraflow, a pour-point depressant, is produced in this manner by Friedel-
Crafts condensation of a chlorinated paraffin (10-12% Ctf.) with naphthalene
(Roberts, 1949). Addition of Paraflow to lubricating oils reduces the pour-
point, making the lubricant suitable for low temperature applications
(Scheer, 1944).
Both Zitko (1974b) and Panzel and Ballschmiter (1974) have used
the reductive dechlorination by sodium bis(2-methoxyethoxy)aluminum hydride
as a confirmatory analytical technique for chlorinated paraffins. The
hydride usually reacts with aliphatic and aromatic organohalogen compounds
to yield the parent hydrocarbons for monosubstituted alkanes and the respec-
tive alkenes for the vicinally disubstituted alkanes. Typical reaction yields
from hydride reduction of commercial chlorinated paraffin preparations are
indicated in Table 11. Unexpectedly, hydroxyl olefins were isolated in the
reduced product. Zitko (1974b) suggests that the hydroxyl groups may be due
to addition of water to the double bonds formed by chlorine elimination from
vicinal carbon atoms.
19
-------
Table 11. Product Yields From Reductive Dechlorination of Commercial
Chlorinated Paraffin Products (Zitko, 1974b)
Formulation Parent Hydrocarbons (%) Hydroxyl Qlefin (%)
Chloroparaffin (40% C£) 20.8
C P 40 16.0
Clorafin 40 (preparative 40 22
run)
Cereclor 42 37.0
Chloroparaffin (50% CR.) 9.0
Chlorez 700 not detectable 75
20
-------
II. Environmental Exposure Factors
A. Production and Consumption
1. Quantity Produced
The liquid chlorinated paraffins were first used in sizable
quantities during World War I. They were used as a solvent for Dichloroamine
T in antiseptic nasal and throat sprays (Scheer, 1944). In 1932, the in-
corporation of chlorinated paraffins as an extreme pressure additive in
lubricants provided the first large volume commercial use of chlorinated
paraffins. However, the largest expansion in chlorinated paraffin production
occurred during World War II. According to the U.S. Tariff Commission, the
production in 1945 amounted to 50 million pounds, mostly due to the increase
in use for weather and flameproofing of tent fabrics and camouflage netting
(Roberts, 1949). Hardie (1964) noted that the output of chlorinated paraffins
from January 1, 1944, to June 30, 1945, amounted to 63 million pounds. However,
after the war production fell drastically, reaching approximately 14 million
pounds by 1946. In the following years the production of chlorinated paraffins
slowly increased, as is noted in Table 12, until it presently exceeds wartime
production by about 25 million pounds.
Information on world production of chlorinated paraffins is
not very plentiful or exact. Hardie (1964) reports an established world
production of 75-100 million pounds for 1961 based upon natural and synthetic
raw materials. This is approximately two to three times the U.S. production
for that year.
21
-------
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2. Producers, Major Distributors, Importers, Sources of Imports
and Production Sites
In the United States, there are eight producers of chlorinated
paraffins. These companies along with their plant locations and reported
capacities are listed in Table 13. New capacities that have been announced
are included in Table 13. The capacities noted are extremely flexible and,
therefore, show only relative market positions of the various companies.
Negotiations have been reported between Ansul Corp. and ICC Industries, Inc.,
of New York for the sale of Ansul's $5 million chlorinated paraffins business
(Anon., 1974b).
Many of these producers have been manufacturing chlorinated
paraffins for a considerable number of years. This is reflected in Table 14,
which lists the producers of chlorinated paraffins during 1959-1974. Hooker
Chemical Corporation has a plant in Niagara Falls, N.Y., with a rate capacity
of 10 million pounds per year (Chemical Marketing Reporter, 1969), but for
the last couple of years the company has only been producing chlorinated
paraffins containing less than 35% chlorine, and recent references do not list
the company as a producer (Dover Chemical Co., no date, a; SRI, 1974, 1975).
Table 15 lists the names and addresses of chlorinated paraffin
suppliers. Many of the suppliers are known producers.
Imports of chlorinated paraffins are considered to be negligible,
During 1964-67, the average total imports of chlorinated paraffins, chloro-
methane, 3-chloropropene, 1,1,1-trichloroethane, and other chlorinated hydro-
carbons were 300,000 pounds (U.S. Tariff Commission, 1969).
23
-------
Table 13. Capacities, Major Producers, and Sites of Production
of Chlorinated Paraffins
Capacity (X 10blbs.)
1975
Company
The Ansul Corp.
Dover Chem. Corp. (subsid.)
Ferro Corp.
Keil Chem Div.
Site
Dover, Ohio
Hammond , Ind .
SRI, 1974
1975
26
26
Dover Chemical Corp.
(no date a)
26
25
1976
26
25
***
Diamond-Shamrock Corp.
Diamond-Shamrock Chem. Co.
Electro-Chem. Div.
I.C.I. United States, Inc.
Plastics Div.
Pearsail Chemical Co.
Hercules, Inc.
Coatings and Specialty
Products Dept.
Neville Chem. Co.
Chlorinated Prod. Div.
Plastifax, Inc.
Painesville, Ohio 18
Bayonne, N.J.
10
Phillipsburg, N.J. 5
LaPorte, Texas
Parlin, N.J.
Sante Fe Springs, Ca. 5
Neville Island, Pa.
Gulfport, Miss.
22
10
9
22
10
9*
- 12
10
**
TOTAL
95
103
120
Anon. (1975a)
** Anon. (1974a)
***
The Diamond Shamrock Corporation has announced plans for a 90 million Ib. per-year
chlorinated paraffins plant near Houston, Texas. The new plant is scheduled to be
operating in late 1977 (Anon., 1975e).
24
-------
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25
-------
Table 15. Chlorinated Paraffin Distributors
(Chemical Marketing Reporter, 1974)
Company
Agvar Chemicals, Inc.
Amoco Solvents & Chemicals Co.
Cron Chemical Corp. ^
Diamond Shamrock Chemical Co.
Electro Chemicals^Division
Dover Chemical Corp.
1CI America Inc.
Intsel Corp. ^
Keil Chemical Co., Inc.
Neville Chemical Co., ^
Chlorinated Prod. Div.
O'Connor-Boyles Chemicals, Inc.
Ohio Solvents & Chemicals Co.
Pearsall Chemical Corp.
Plastifax, Inc.
Sea Land Chemical Co.
Stanalchem, Inc.
Stevenson Brothers & Co., Inc.
Thompson-Hayward Chemical Co.
E.F. Whitmore & Co.
Location
New York, New York
Lakeview, California
Houston, Texas
Cleveland, Ohio
Dover, Ohio
Wilmington, Delaware
New York, New York
Hammond, Indiana
Pittsburgh, Pennsylvania
Santa Fe Springs, California
Southfield, Michigan
Cleveland, Ohio
Phillipsburg, New Jersey
Gulfport, Mississippi
Cleveland, Ohio
New York, New York
Philadelphia, Pennsylvania
Kansas City, Kansas
San Marino, California
Noted producers
26
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3. Production Methods and Processes
Chlorinated paraffins are manufactured by liquid phase
chlorination with chlorine gas at a temperature at which the viscosity of
the paraffin is sufficiently low to allow rapid chlorination and hydrogen
chloride evolution and at which decomposition of the product is not extensive
(Hardie, 1964). Depending upon the paraffin feed stock, the temperature
may range from 50° to 150°C, and the reaction is sometimes carried out at
elevated pressures (15-100 psig) (Sittig, 1968). As the chlorine content
in the product increases, it becomes so thick that chlorination above
approximately 54% (Roberts, 1949) becomes slow and difficult. To decrease
the viscosity and increase the chlorination rate, a solvent is usually added,
and thus the highly chlorinated products are frequently produced by chlorination
with solvent under reflux. Carbon tetrachloride is the most frequently used
solvent, but other solvents such as hexachlorobutadiene have been reported
(Hardie, 1964).
Configurations of the production plant may vary considerably.
Both batch and continuous reactors can be used, although the continuous re-
actors usually consist of batch reactors in series. The reaction is exo-
thermic so the reactor must be cooled. Since chlorination is a radical
reaction, the reaction can be catalyzed by UV light or by radical initiators
(e.g. azodiisobutyronitrile) (Zitko and Arsenault, 1974).
The flow diagram in Figure 3 is typical of a three stage
operation consisting of three combined reactors and disengaging tank units
which are so positioned that the chlorinated material will flow counter-
current to the flow of chlorine gas (25, 20, and 15 in Figure 3). In this
27
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three stage reactor, progressive stages of chlorination are accomplished. For
example, the weight percent of chlorine in the chlorinated paraffin product
withdrawn via lines 14, 19, and 24 are 22%, 45%, and 58%, respectively. The
final chlorinated paraffin product is separated from the chlorine gas and
hydrogen chloride by-product by blowing air or sometimes nitrogen or carbon
dioxide (Scheer, 1944, Roberts, 1949, Sittig, 1968) through the product.
Following removal of residual chlorine and hydrogen chloride, and solvent with
the higher chlorinated paraffins, the product is stabilized.
4. Market Prices
The price of chlorinated paraffins can be a very important
factor in determining whether these materials are used in various applications.
This is especially true for secondary plasticizer applications where price may
be an overriding factor (see Section II-B, p. 32). Figure 4 illustrates the
relatively steady price history of chlorinated paraffins. For comparison
purposes, the price history of di-2-ethylhexylphthalate (DEEP), one of the most
widely used primary plasticizers, has also been plotted.
In 1973 the sales value of chlorinated paraffins totalled
approximately $11.5 million. The chlorinated paraffins containing 35-64% chlorine
totalled $7.9 million.
5. Market Trends
As Table 12 demonstrates, the production and sales of
chlorinated paraffins have been on a steady increase. During the ten year
period from 1963 to 1973, production has almost doubled (annual growth rate
of approximately 7 per cent for the ten year period), but most of the growth
occurred in 1963-66 and 1971-73. This is also reflected in the increase in
the plant capacities. The capacity will be well over 100 million pounds per
29
-------
D
I
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.40--
.30--
3
O
o.
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.10--
Chlorinated Paraffins
Total
oooo oooo 35%-65%
..-. All Others
Di-2-Ethylhexyl Phthalate
'59 '60 '61 '62 '63 '64 '65 '66 '67 '68 '69 70 '71 '72 '73 '74 '75 '76
Year
Figure 4. Average Unit Price/Lb. of Chlorinated Paraffins
(U.S. Tariff Commission, 1959-1973;1974-Dover Chemical
Corp. (no date a)
30
-------
year in 1976 and has grown from 50 million in 1965 (Chemical Marketing
Reporter, 1965), to 69 million in 1968 and 1969 (Chemical Marketing Re-
porter, 1968, 1969) and 95 million in 1974-75 (SRI, 1974, 1975).
The three major applications of chlorinated paraffins are
lubricating and cutting oil additives (-45%), secondary plasticizers (24%),
and flame retardancy uses in paint, rubber, and plastics (27%) (see Section
II-B, p. 32). The market for oil additives seems to have matured and industrial
sources suggest that the growth will probably not exceed 5% per year. In
contrast, flame retardancy applications appear to have a bright future mostly
due to growing public awareness and legislative requirements governing flame
retardancy. Industrial sources suggest a possible growth rate of chlorinated
paraffins for this application of approximately 35% per year. Other marketing
surveys seem to confirm this optimism. Frost and Sullivan, Inc. (1975)
suggest that the flame retardant market will double by 1978, and a spokesman
for U.S. Industrial Chemicals Company estimated that the market for flame
retardant plastics will grow at an average annual rate of 13 to 15% (Anon.,
1975b). The market for secondary plasticizer applications is less defined,
because the price of primary plasticizers has become more competitive. How-
ever, in cases where less chlorinated paraffin is required than the primary
plasticizer that is replaced or where flame retardancy is a desirable asset,
chlorinated paraffins will continue to be used as secondary plasticizers.
Thus, overall it is likely that the market for chlorinated paraffins will
continue to grow at a considerable rate.
31
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B. Uses
1. Major Uses
Information on the quantities of chlorinated paraffins used
in various applications is not very exact. However, the major applications
appear to be as oil additives (-45%), as secondary plasticizers (-24%), and
as flame retardant additives (-27%).
The first large commercial use of chlorinated paraffins was
during World War II. At that time, these materials were selected as impreg-
nating compositions "for treating canvas duck, camouflage nets and strips and
other textiles materials to make them flame resistant, waterproof and mildew-
proof" (Scheer, 1944). Fabrics that were treated included cotton duck and
burlap, jute, and osnaburg strips. Presently, textile applications are only
a small part of the chlorinated paraffin market because they are not as
resistant as other flame retardants [e.g., tetrakis (hydroxymethyl)phosphonium
chloride] to washing and dry cleaning (Noble, 1974). Drake (1966) noted that
the chlorinated paraffin - antimony oxide flame retardant finish is "more
suitable for use on very heavy fabrics such as tents, tarpaulins, awnings,
etc., and is not suitable for use on clothing, interior decorations, and the
like". A small amount of chlorinated paraffins is still used for military
applications, such as with tents (Noble, 1974).
Table 16 presents a breakdown of chlorinated paraffin appli-
cations for 1965-1973. Some trends are apparent from the data, but the difference
between the 1973 figures and 1965, 1968, and 1969 figures is probably more
attributable to the different sources of the information rather than par-
ticular trends.
32
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Table 16. Major Applications of Chlorinated Paraffins
Percentage of Total Market
1965* 1968* 1969* 1973**
Lubricating Oil Additives 65 35 35 45
Cutting & Drawing Oils 45
Other Lube Uses 20
Secondary Vinyl Plasticizer 20 35 35 24
Miscellaneous Solvent and 15 20 20 27
Plasticizer (mostly flame
retardancy uses)
Resinous Material for Coatings 10 10
and Industrial Use
Traffic Paints 4
* Chemical Marketing Reporter, 1965, 1968, 1969
* * Industry Sources
Oil additive applications are still a major portion of the
total market, although their share has declined since the 1960's. This decline
will probably continue since the oil additives market is considered to be
relatively mature compared to the other applications.
Chlorinated paraffins are added to lubricating oils because
of their viscous nature, their compatibility with oils, and gradual liberation
of hydrogen chloride at elevated temperatures (Hardie, 1964). For the most
part, only the liquid chlorinated paraffins are used. Chlorinated paraffins
can provide both boundary lubrication (physical film formed) and extreme pressure
activity (chemical reaction involved). If only extreme pressure activity is
desired, a lower molecular weight or lower viscosity product is suitable and
more economical. Chlorinated paraffins function as extreme pressure additives by
slowly decomposing at elevated temperatures found near cutting surfaces or other
33
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surfaces requiring lubrication to yield hydrogen chloride. The hydrogen
chloride reacts with the metal surface and with the tool surface (in cutting
oils). The reaction provides a high-melting, inorganic (iron chlorides)
lubricant film on the metal surface which prevents massive welding and break-
down (Lee and Booser, 1967). With cutting oils, this results in a decrease of
the cutting force, an increase in tool life, improved surface roughness, and
smaller errors in dimensioning (Matthijsen and Van Den Brekel, 1967). When
additional boundary lubrication is required, only the higher molecular weight,
higher viscosity products can be used because of their greater film strength
(Keil and Thompson, 1969). Typical formulations for cutting and extreme
pressure applications are presented in Table 17. Added incentives for using
chlorinated paraffins as oil additives are: (1) their relatively low cost as a
source of chloride and (2) their ability to prevent corrosion, especially in
low carbon steels.
Chlorinated paraffins are also used in drawing and stamping
compounds. The high viscosity products, which are most frequently used, can
be applied straight or diluted to a broad range of concentrations (Keil and
Thompson, 1969).
Keil and Thompson (1969) conclude that chlorinated paraffins
used as cutting fluids and drawing and stamping compounds are "highly effective,
light in color and relatively free from smoking and gumming compared to metal-
working fluids based on sulfurized fats".
Derivatives of chlorinated paraffins are also sometimes used
as oil additives. Paraflow, a product made by reacting a 14% chlorine con-
taining chlorinated paraffin with naphthalene, has been used as a pour-point
depressant for lubricating oils (Hardie, 1964; Scheer, 1944; Roberts, 1949;
Michel, 1968). Also, although more expensive, excellent lubricants are
34
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Table 17. Formulations of Chlorinated Paraffins for Cutting and
Extreme Pressure Oils (Keil and Thompson, 1969)
Chlorinated
Paraffin
Low or High Viscosity
High Viscosity
Low Viscosity
Low Viscosity
Low Viscosity
High Viscosity
Cutting Oils
Application
3-10
5-15
5-15
General purpose for ferrous and non-ferrous
Heavy duty, low speed, metal gouging
Surface grinding oils (high alloy steels)
Extreme Pressure Soluble Oils
5-10 General purpose for ferrous and non-ferrous
5-15 Surface grinding solubles (high alloy steels)
20 Heavy duty E.P. solubles
provided by condensing C20 - C25 chlorinated paraffins with benzene, toluene,
or the xylenes.
The other two major applications, use as a secondary plasticizer
and as a flame retardant, are approximately equal in volume but frequently over-
lap. For example, chlorinated paraffins used as secondary plasticizers in
polyvinyl chloride (PVC) frequently are used because they impart flame
retardancy. Table 18 summarizes the non-lubricant applications and markets
for chlorinated paraffins.
35
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Table 18. Non-Lubricant Applications and Markets for Chlorinated
Paraffins (Dover Chemical Corp., no date, a)
Applications
Aroclor (PCB's) Replacements
Plasticizers - PVC Secondary Plasticizer
Tackiflers
Markets
Resin Modifiers
Flame Retardant - Chlorine
Halogen Donor
Adhesives Aqueous Base; Solvent Base; Hot Melt
Resin Thermoset and Thermoplastic
Tapes Pressure Sensitive
Coatings Exterior Alkyl Modified, Chemical Resistant and Intumescent
Fire-Retardant Paints
Rubber Carpent Backing; Latex Compounding; Automotive Parts
Textile Finishing Drapery, Upholstery and Wall Fabrics
Paper Aluminum Foil to Paper Laminates
Vinyl Plastisols and Custom Coaters
Laminates
Ink
Polymers
Building Products Insulation; Plywood
Electrical
Coatings for Electrical Cable
In order to understand the plasticizer and flame retardancy
applications, one needs to be familiar with the mechanisms of plasticization
and flame retardation. Plasticizers are materials incorporated in a plastic
to increase its workability and its flexibility or distensibility (Darby and
Sears, 1968). Secondary plasticizers are compounds that are not as completely
compatible as primary plasticizers but can be substituted for primary plasticizers
in order to lower the cost of the plasticized resin or to impart a desirable
property to the formulation. PVC is the largest consumer of plasticizers
(80% - Darby and Sears, 1968; Pattison and Hindersinn, 1971), and phthalate
esters used with PVC amount to one-half of the total plasticizer production.
36
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V
In the past, chlorinated paraffins were substituted for phthalate esters because
they were less expensive (see Figure 4, p. 30, and Brighton, 1971; Bell et al.,
1966; and Ball and Kolker, 1969). However, the volume cost estimates of Ball
v-
and Kolker (1969) were based upon a price for diisooctyl phthalate (DIOP) 1.67
v- times the price of chlorinated paraffins (52% CH). The present price structure
(chlorinated paraffins, 50% - $.265/lb; 60% - $.22/lb compared to DIOP = $.265/lb;
"~ Chemical Marketing Reporter, 1975) (Chlorowax 100 = $.27/lb, DIOP = $.26/lb;
Anon., 1975d) would lead to much less, if any, financial savings. Nevertheless,
sizable amounts of 40% -56% Cl (Brighton, 1971) chlorinated paraffins will
^ continue to be used as secondary plasticizers with PVC, especially where flame
retardancy and low temperature properties are important.
^ Although unplasticized PVC is self-extinquishing, the flame-
retardant properties are reduced when it is plasticized with conventional
compounds, such as phthalates and adipates. The phosphate ester plasticizers
L^ that are commonly used for flame retardancy have the disadvantage that the
low-temperature strength of the PVC is considerably reduced (Bell e_t a^., 1966,
~ 1971; Brighton, 1971). Although chlorinated paraffin plasticized PVC has less
low-temperature strength than DIOP-PVC, it is considerably better than the
organophosphate plasticized PVC. Frequently antimony oxide, which is a
,__ synergistic flame retardant in the presence of a halogen source, is added with
the chlorinated paraffins so that the required flame retardant properties can
""" be reached without adding excessive amounts of chlorinated paraffins which
, , might reduce the low temperature strength. Thus, for the above reasons and
V.
because chlorinated paraffins have high thermal stability, low discoloration
37
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at elevated temperatures, low volatility (no more than conventional primary
plasticizers) and are compatible (see Darby and Sears, 1968), the chemicals are
extensively used as a secondary plasticizer with PVC. Major applications of
the resulting PVC include electric cable, calendered film (for use in such
applications as tarpaulins, mine ventilation, tubing, and decorative finishes in
buildings), conveyor belting, and floor tile (Grant and Bilgor, 1966; Ball and
Kolker, 1969; Bell £t al. , 1966). In most instances, the middle chlorination
range (42-56% C&) is used, although the materials with higher chlorine content
are more compatible and, therefore, can be used in larger proportions (Brighton,
The use of chemicals to impart flame retardancy is one of the
fastest growing markets for chlorinated paraffins. This is due to construction
codes and government specifications which are being stiffened continuously.
Building products using plastics have long been subject to stringent codes.
"More recently, the Department of Transportation has imposed standards for
automobiles and passenger vehicles; the Federal Aviation Authority, standards
for internal components in aircraft; and the Department of Commerce, standards
for carpets, mattresses, television, radio, and appliance housings" (Noble, 1974)
Markets for textile flame retardants are probably the fastest growing due to
the 1967 amendment of the 1953 Flammable Fabrics Act (Anon., 1975c, Drake, 1971).
However, the flame retardant chemicals market for textiles is relatively small
compared to that for carpeting (see Table 19) .
38
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Table 19. Flame Retardant Chemicals Market (Anon., 1975c^
Market
Carpeting
Textiles
Plastics, coatings.
Total Lbs.
250 million
10 million
90 million
% of Market
70%
3%
27%
and films
As noted earlier, very little chlorinated paraffins are used for treating
textiles with the exception of very heavy fabrics such as tents, tarpaulins,
and awnings. However, because the textile market is relatively small, it
has little effect on the chlorinated paraffins market.
Table 20 presents the annual estimated consumption of both
additive and reactive intermediate flame retardants. These amounts are not
completely compatible with the percentages in Table 16. For example, in
Table 20. U.S. Consumption of Miscellaneous Flame Retardants for
Polymers (million Ibs.) (Noble, 1974 - based upon data
from Modern Plastics)
1969 1972 1973
Additives
Phosphate Esters
Non-Halogenated
Halogenated
Chlorinated Paraffins
Antimony Oxide
Bromine Compounds
Boron Compounds
Other
Reactive Intermediates
Urethane
Polyester
Epoxy
Other
TOTAL
50.7
9.5
14.0
16.0
1.7
5.7
97.6
9.5
13.0
1.7
5.0
29.2
126.8
53.8
15.0
41.9
17.6
7.1
3.9
10.1
149.4
18.1
11.4
5.3
8.4
43.2
192.6
74.3
24.0
59.0
19.0
11.0
4.9
18.2
210.7
23.1
15.0
8.4
15.0
61.5
272.2
39
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1973, using the amounts in Table 20, flame retardancy applications would
amount to 80% (59/73) of the total production. This is far greater than the
percentage indicated in Table 16 (27%) for that year. However, the amounts
for 1969 correspond fairly well (20% of 60 million Ibs = 12 million Ibs).
Flame retardants are chemicals used to reduce the burning
ability of a particular material. There are four steps involved in burning:
(1) preheating, where an external heating source warms the material, (2) de-
composition, where the material degrades to combustible and volatile compounds,
(3) ignition, where the compounds that are formed in the decomposition step
are further heated and begin to burn, and (4) combustion and propagation, where
the burning of the decomposition products results in enough heating of the
material to provide a self-sustained flame (Pearce and Liepins, 1975; Pattison
and Hindersinn, 1971). Inhibition of any of these steps results in a product
with increased flame retardancy. The mechanism of halogen flame retardancy is
not completely understood, but is frequently suggested to be due to dissipation
by halogens of the highly reactive *OH radicals which are needed for a high
flame velocity. Similarly, no satisfactory theory is yet available to explain
the synergistic effect between antimony compounds and halogenated flame
retardants, but the formation of the volatile antimony trichloride or antimony
oxychloride may be important in inhibiting free radical proliferation. However,
other theories, such as the following mentioned by Pattison and Hindersinn (1971),
may be equally as important as the mechanism for inhibition of radical chain
reactions by halogens.
"Coating Theory - The fire-retardant additives intumesce or cause
the formation of carbonaceous foam or char which acts as a thermal insulator
in addition to preventing access of oxygen.
40
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Gas Theory - Large volumes of incombustible gases are produced
which dilute the oxygen supply. Examples are ammonia, nitrogen, sulfur dioxide,
and halogen acid.
Thermal Theory - The fire retardant decomposes endothermally,
e.g., by fusion or sublimation, or it undergoes an endothermic reaction with
the flammable substrate which reduces the temperature below that at which the
flame is self-sustaining.
Chemical Theory - It is suggested that species are formed which
influence the course of the free-radical propagated combustion, reducing the
ultimate flammability of the system." (Pattison and Hindersinn, 1971)
Flame retardancy can be provided by: (1) introducing additives
prior to the polymer processing, (2) using additives as a finish or surface, (3)
integrating a flame retardant comonomer before the polymerization, and (4)
synthesizing inherently flame resistant structures (Pearce and Liepins, 1975).
Chlorinated paraffins are used as additives which are usually added prior
to the processing step. The ideal additive is inexpensive, colorless, easily
blended, compatible, heat and light stable, efficient, permanent, and has
no negative effects on the physical properties of the polymer (Pattison and
Hindersinn, 1971). Because chlorinated paraffins exhibit high ratings in
many of the above areas, they are used extensively as flame retardant additives.
The largest application of chlorinated paraffins for flame
retardancy is probably in vinyl products (mostly PVC) which have been discussed
previously. However, they also are used with other plastics such as polyesters,
polyolefins (polyethylene and polypropylene), and polystyrene (Bell £t al., 1966)
Frequently, the 70% CH grades of chlorinated paraffins are used with non-PVC
plastics because of their higher compatibility. Chlorinated paraffins have
reportedly been used with acrylics and modacrylics, polyurethane, and cumarone-
indene resins (Hardie, 1964).
41
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Chlorinated paraffins are also used in sizable quantities as
flame retardant additives for rubbers such as chlorinated rubbers and neoprene.
Large quantities of these materials are used for rug underlays and foam backings
of carpets (see Table 19, p. 39) and for latex compounding and automobile parts. The
chlorinated paraffins in many cases serve both as flame retardants and plasti-
cizers.
Chemical resistant and fire retardant paints also provide a
large market for chlorinated paraffins. In 1973> it was estimated that 4% of
the total production of chlorinated paraffins was consumed in traffic paints
(see Table 16, p. 33). The traffic paints, as well as many marine paints that use
chlorinated paraffins, are usually rubber based (Wade, 1948; Ford, 1972;
Jnojewyj and Rheineck, 1971). Chlorinated paraffins are effective as flame
retardants in both solvent and water systems, and are recommended for
both non-intumescent and intumescent paints (Diamond Shamrock Chem. Co., no
date). Intumescent flame retardant paints contain additives which catalyze
the decomposion of the paint film when subject to fire to produce a cellular
(intumescent) char which insulates and protects the substrate. The higher
chlorinated (70% C&) resinous materials are used mostly to decrease the
combustibility of the substrate, whereas the liquid chlorinated paraffins can
serve also as plasticizers. Ford (1972) found that a binder composition of
chlorinated rubber resin, chlorinated paraffin resin (Cereclor 70), and a
liquid chlorinated paraffin (Cereclor 42) performed very well as a marine
paint when field evaluated for four years in salt water. Such uses as traffic
and marine paints and swimming pool enamels result from the improved flexibility
and chemical and water resistance imparted by the chlorinated paraffins.
42
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Chlorinated paraffins also find applications as tackifiers in
aqueous and solvent base and hot melt adhesives. In fact, they have been
suggested as replacements for Aroclor (PCB's) formulations in pressure sen-
sitive adhesives (Dover Chemical Corp., no date b) (see Section II-B-4, p. 45)
2. Minor Uses
A number of minor uses of chlorinated paraffins have been
patented or referred to in the available literature. These uses are tab-
ulated in Table 21, along with the reference and the type of chlorinated
paraffin when available.
Table 21. Minor Uses of Chlorinated Paraffins
Reference
Chlorinated Paraffin Used
Application
Scheer (1944)
Roberts (1949)
<30% Ct
<30% CZ
<30% Ci
Solvent for Dichloramlne T in
antiseptic nasal and throat
sprays
Chewing gum
Emulsion type coatings applied
to citrus fruits for
preservation
Mixture with terepenes as an
insecticide
Breaking petroleum emulsions
Additive to castor oil to render
soluble in mineral oil
Catalyst in chlorination of
methane
Lustering agents in dry-cleaning
fluids for textiles
Substitute for olive oil in
wood carding
Starting point for preparation
of wax modifying agents
Coating citrus fruit for
preservation
Ingredients in oils for water-
proofing hides
Component of foundry-core
binder
Flexible coating for carbon
paper
Component of moisture-resisting
flexible films
43
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Table 21. Minor Uses of Chlorinated Paraffins
(continued)
Reference
Hardie (1964)
Chlorinated Paraffin Used
Application
70% CJl
From: Zitko and Arsenault
(1974)
Ban eit al., (1972)
Komarek and Spahrkaes
(1973)
Prosser (1972)
Nakanlshi and Kobayaskl
(1973)
Buell (1972)
Morlta and Suglyama (1973)
Horvath and Parsons (1972)
Diery e_t al. , (1972)
Chlorinated paraffin
sulfonlc acids
Galloway (1958)
Bradbury and Fox (1958)
Ali et al., (1971)
Cereclor 70
Manufacture of dielectric
fluids and insulating
covering
Adhesive anti-insect
bands for fruit trees
Marking inks
Fumigating mixtures
Surface active agents
Soldering flux
Antistatic agents for
nylon
Components of tanning
composition
Heat protecting coatings
Polysulfide compositions
Abrasive coated products
Soot inhibitors for fuel
oil
Coating for tableted
calcium hypoclorite
for use in treatment
of sewage and swimming
pool waters
Emulsifiers of biocidal
concentrates
Improve effectiveness of
pesticides by adding
chlorinated paraffins
to reduce volatilization
Additive to reduce
phytotoxicity of y-BHO
Hg seed dressings
Wax emulsion with thiourea
to prevent shrinkage
and decay
44
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3. Discontinued Uses
No references in the available literature mention termination
of any major chlorinated paraffin application for health or environmental reasons.
However, the use of chlorinated paraffins as a solvent for nasal and throat
sprays, which was the first large application of chlorinated paraffins (Scheer,
1944), does not appear to be practiced today. The first large volume use of
chlorinated paraffins was for making heavy textiles, especially canvas duck,
flame resistant, waterproof, and mildewproof. Although a relatively small part
of the total market, this application is still commercially important. Similarly,
lubricant additive, plasticizer, and flame retardancy applications have not been
discontinued.
4. Projected or Proposed Uses
Several references have mentioned that chlorinated paraffins may
be a good substitute for some PCB applications. For example, Dover Chemical
Corp. (no date,b) has compared the performance of chlorinated paraffins to the
performance of PCB's in: (1) styrene-butadiene rubber based pressure sensitive
adhesives, (2) thermoplastic type acrylic resin based pressure sensitive ad-
hesives, and (3) crosslinked acrylic resin based pressure sensitive adhesives.
In most instances, creep resistance was equal to or better than PCB formulations,
and the tack and peel strength was maintained. Also, the chlorinated paraffin
formulations exhibited excellent flame retardant character compared to PCB's,
which is not too surprising since aliphatic halogen compounds are well-known
to be more effective than aromatic halogen compounds (Pattison and Hindersinn,
1971). In some formulations, the heat stability of the chlorinated paraffin
products was slightly less than with PCB's.
45
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Ford (1972) Investigated the performance of chlorinated rubber
paints under marine conditions using both PCB or chlorinated paraffin binder
formulations. The paint containing PCB's gave the best results, but the
chlorinated paraffin blend gave good results and was considered to be a high
performance binder.
Based upon the properties of chlorinated paraffins, it seems
likely that the following applications in which PCB's were used in 1970 (Nis-
bet and Sarofim, 1972) may be using chlorinated paraffins: plasticizer applications
in synthetic resins, adhesives, and rubbers; wax extenders; dedusting agents;
inks; lubricants; cutting oils; and carbonless reproducing paper. In contrast,
applications which are dependent upon the high heat stability of PCB's (e.g.,
heat transfer, capacitors, and transformers) are not candidates for chlorinated
paraffin replacement because of the comparitively low thermal stability of the
chlorinated paraffins.
Chiba and Adachi (1970) have patented the use of chlorinated
paraffins as a paper-sizing agent (render the paper more resistant to pene-
tration by liquids, particularly water). It is possible that the chlorinated
paraffins containing 70% chlorine could completely replace the normally used
resin (Vizante £t. al., 1972; Zitko and Arsenault, 1974).
5. Possible Alternatives to Uses
None of the applications of chlorinated paraffins could be
termed as a matter of convenience; the applications are for the most part
essential for the commercial function of the final product. At one time,
chlorinated paraffins were added as a secondary plasticizer to PVC mostly
for economic reasons; chlorinated paraffins were cheaper than the primary plasticizer
46
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However, the flame retardant properties imparted by the chlorinated paraffins
to such products as carpet backing and vinyl tiles are essential now due to
modified building codes and government regulations. Organophosphorus plasticizers
could be used instead, but they appear to be more expensive (Brighton, 1971)
and they reduce the low temperature strength of the plasticized resin compared
to chlorinated paraffins-plasticized PVC (Brighton, 1971; Bell ejt al., 1971).
Other options include using other flame retardant plasticizers or inherently
flame resistant monomers (see Table 22), but again cost is an important factor.
A number of alternatives to lubricant and cutting oil additive
applications of chlorinated paraffins are possible. This is the oldest and
still one of the largest applications for chlorinated paraffins. These
chlorinated compounds can provide both boundary lubrication and extreme pressure
activity. The chlorinated paraffins are part of a group of antiwear agents
which are required to minimize function and wear. Under boundary film conditions,
there are six main groups of chemicals that could be used instead of the
chlorinated paraffins: (1) compounds containing oxygen (fatty acids, esters,
ketones); (2) compounds containing sulfur or combinations of oxygen and sulfur;
(3) organic sulfur compounds (sulfurized fats, sulfurized olefins); (4) compounds
containing both chlorine and sulfur; (5) organic phosphorus compounds (tri-
cresyl phosphate, thiophosphates, phosphites); and (6) organic lead compounds
(Lee and Booser, 1967). Applicability will depend upon the film-forming ability
of the chemical group with specific metals or other materials. Under extreme
rubbing conditions where extreme pressure additives are required, active sulfur,
phosphorus and lead compounds or other halogen compounds might be substituted for
the chlorine compounds (Lee and Booser, 1967; Matthijsen and Van Den Brekel, 1967)
47
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Other chlorinated organic compounds, such as trichloroethylene, tetrachloro-
ethane, carbon tetrachloride, and £-dichlorobenzene, might be considered as
alternatives, but they usually have severe medical and health problems
(Matthijsen and Van Den Brekel, 1967).
Flame retardancy can be imparted to commercial products in a
number of ways besides using flame retardant additives; for example, (1) use
a flame retardant finish or surface, (2) integrate a flame retardant monomer
into the polymer, or (3) synthesize inherently flame resistant structures
(Pearce and Liepins, 1975). The inherently fire retardant polymers, such as
polybenzimidazoles and aromatic polyamides, are extremely expensive and,
therefore, are not likely to replace sizable portions of the chlorinated
paraffin flame retardant market. However, they are being used in markets,
such as aircraft applications, where the smoke and fumes generally produced
by halogenated flame retardants cannot be tolerated. In fact, Pattison and
Hindersinn (1971) have suggested that the smoke and corrosive fumes generated
when halogenated materials are exposed to fire may limit their future growth.
Flame retardancy is obtained when sufficient quantities of
halogens, phosphorus, nitrogen, or boron are present (Noble, 1974). Thus,
any compounds that contain these elements might be substitutes for chlorinated
paraffins. In addition, compounds that have synergistic flame retardant
effects, such as antimony oxide, may be considered. Factors which have to
be considered in determining replacements for chlorinated paraffins are expense,
color of the additive, ease of formulation, compatibility, heat and light
stability, flame retardant efficiency, permanency, and effect on the physical
effects of the polymer (Pattison and Hindersinn, 1971). Environmental
compatibility is also an important parameter that should be considered. Possible
replacements for chlorinated paraffins are listed in Table 22.
48
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Table 22. Possible Replacements for Flame Retardant Applications of
Chlorinated Paraffins (Pattison and Hindersinn, 1971; Pearce and Liepins, 1975)
Additives
Non-teactive, Organic
Phosphate esters
Halogenated phosphate esters
Halogenated phosphonate esters
Halogenated hydrocarbons
Polyvinyl chloride (physically blended)
Polyvinylidene chloride (physically blended)
Non-reactive, Inorganic
Antimony oxide
Aluminum oxide trihydrade
Zinc borate
Ammonium orthophosphate
Ammonium sulfamate
Reactive
Bromine and/or phosphorus
containing polyols
Halogenated phenols
Example
[CH3(CH2)70]3P=0
(BrCH2CHBrCH20) 3P=0
0
Hexabrotnocyclododecane
Pen tabromo toluene
Tetrahalophthalic anhydride
Phosphonate esters
Dibromopentyl alcohol
Tetrakis(hydroxymethyl)phosphonium
chloride (THPC)
Vinyl chloride or bromide
Vinylidene chloride
A1203-3H20
Zn2B6On
CH2OOCR
CH2OOCR
CH2OOCR
R =
OH
i
CH3(CH2)5CH CH CH-(CH2)-
i i
Br Br
H(OCH2CH2)nOP CH2OH
(BrCH2)2C(CH?OH)?
CH2OH
HOCH2-P- CH?OH
CH2OH
CH2 = CHCi.Br
CH2 = CCi2
-------
C. Environmental Contamination
1. General
Unfortunately very little substantive information is avail-
able which would allow an estimation of the amount of chlorinated paraffins
being released to the environment. No monitoring has been reported, mostly
because adequate analytical techniques have not been developed. Therefore,
almost all of the discussion in this section is based upon speculation. Through-
out this section, comparison will be made between chlorinated paraffins and the
well-known environmental contaminants, polychlorinated biphenyls (PCB's), be-
cause of the similarities in terms of physical properties and some applications.
This comparison was facilitated by the work of Nisbet and Sarofim (1972) and
Zitko and Arsenault (1974).
Zitko and Arsenault (1974) have compared some physical and chemical
properties of the two chemical groups which are relevant to considerations of
environment contamination. Their information as well as some other available
data are summarized in Table 23.
2. From Production
Chlorinated paraffins are manufactured by eight chemical producers
in plants located in ten different cities across the country (see Table 13,
p. 24). Production in 1973 amounted to 74 million pounds (see Table 12, p. 22),
which is about equal to the sales of PCB's for the year 1970 (the largest amount
sold in one year).
Chlorinated paraffins are made by liquid phase chlorination
of either: (1) the liquid paraffin, which is frequently heated to decrease the
viscosity and increase the rate of chlorination, or (2) the paraffin dissolved
in a solvent such as carbon tetrachloride. No contact is made with water,
50
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Table 23. Comparison of PCB and Chlorinated Paraffin Physiochemical
Properties Relevant to Environmental Contamination Considerations
(Nisbet and Sarofim, 1972; Zitko and Arsenault, 1974; Hardie, 1964)
Properties
Vapor Pressure
(mm Hg)
Compounds
Chlorinated Paraffins
_5
Remarks
PCB's
2 x 10 (C23H48 - 42-54%CK.)
10 (Aroclor 1242) The high mole-
1 to cular weight
2 x 10~ (Aroclor 1260) chlorinated
paraffins
(C20~ C3o) are
probably less
volatile than
PCB's. The
Cg-C15, more
volatile.
Water solubility
25-200 ppb
Thermal stability
Extensive decomposition
at 300-400°
Stable up to
800°C
No information
on chlorinated
paraffins. Based
upon solubility
of the parent
hydrocarbon,
probably equal
to or less
soluble than PCB's
PCB's volatilize
before decom-
position.
Chlorinated
paraffins decom-
pose before
volatilization.
51
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and, therefore, loss in water effluents should be negligible. After
chlorination, the product is stripped of solvent (used only with higher
chlorinated products), and air or other gases are blown through the product
to remove residue chlorine gas and hydrogen chloride. This stripping might
result in loss of some of the lower chlorinated isomers, but since the more
volatile chlorine gas and hydrogen chloride are recovered, the loss is suspected
to be very low.
Occasionally the final product will not meet the quality
control standards and will have to be disposed of or reformulated, if
possible. The amount of material that falls into this category is unknown
but is likely not to be very substantial for economic reasons. If it is
recovered, no loss to the environment occurs. Disposal will be discussed
in Section II-C-5, p. 55.
3. From Transport and Storage
Small quantities of the liquid chlorinated paraffins are
transported and stored in 55 gallon drums. Bulk quantities are transported
in insulated and heated tank cars or trucks and stored in insulated and
heated tanks. Disposal of non-returnable drums might result in some environ-
mental release. Also, if storage or transportation tanks are cleaned out for
other chemical use, environmental release might occur. Storage tanks are
vented to the atmosphere (Hardie, 1964), but the low volatility would suggest
negligible losses. Spills may occur, but the high viscosity and water in-
solubility of the material makes cleanup using an absorbent material fairly
easy. The cleaned up material would probably be deposited in a landfill.
52
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4. From Use
The uses of chlorinated paraffins probably provide the major
source of environmental contamination. Many of the chlorinated paraffin
applications are identical to the ones suspected as being the major sources
of PCB contamination. Table 24 compares the applications of PCB's and
chlorinated paraffins.
Table 24. Applications of PCB's and Chlorinated
Paraffins (percentage of total)
Applications PCB's Chlorinated Paraffins
(Nisbet and Sarofim, 1972) (this report)
Electrical and heat transfer 60% 0%
(closed systems)
Plasticizer 25% 24%
Hydraulic fluids and lubricants 10% 45%
Miscellaneous (including surface 5% 31%
coatings, adhesives, printing inks,
and flame retardants)
Using the same assumptions as Nisbet and Sarofim (1972), it is
possible to calculate some approximate losses from plasticizer and oil additive
applications. Nisbet and Sarofim (1972) concluded that lubricants are rarely
reused and, therefore, the amount scrapped each year is approximately equal to
the amount sold for that application (45% x 76 x 106 Ibs. = 34 x 106 Ibs. for
chlorinated paraffins in 1973). A sizable amount of the discarded oil will be
deposited in dumps or landfills. Also, a significant quantity of any chlorinated
paraffin used in automotive and industrial lubricant oils will probably reach
water resources via storm drains (Anon., 1972).
53
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Behavior of chlorinated paraffins compared to PCB's in
plastics can be estimated from some plasticizer performance data provided
by Darby and Sears (1968) (Table 25).
Table 25. Plasticizer Performance of PCB's and Chlorinated
Paraffins in PVC (Darby and Sears, 1968)
Plasticizer
Volatility
plasticizer
loss, %,
24 hr., 87°C
Water
extraction
% loss,
24 hr., 50°C
Kerosene
extraction
% loss,
24 hr., 23°C
Chlorinated (54% C£)
biphenyl
40% PCB
20% DIOP & 20% PCB
9.1
18.4
0.08
0.04
2.6
12.2
Chlorinated (52%
paraffin
6.1
0.01
1.7
Nisbet and Sarofim (1972) estimated the rate of evaporation of PCB's from plastics
was approximately 10 to 20% of sales. Since chlorinated paraffins are somewhat less
volatile (at least with the formulations given by Darby and Sears, 1972), the
chlorinated paraffin loss is probably 10% of sales (.10 x .24 x 76 x 106 Ibs. =
1.7 x 105 Ibs.). The remaining plasticizer (.90 x .24 x 76 x 106 Ibs. = 16.7 x
106 Ibs.) is probably discarded in dumps because of the short useful life of
most plastics.
Sizable releases to the environment from chlorinated paraffin
flame retardant applications are also likely, but more difficult to quantitate.
Chlorinated paraffin flame retardants in plastics are probably susceptible to
the same losses as secondary plasticizer applications. Building materials using
chlorinated paraffin flame retardants probably eventually end up in dumps, but
have a much longer useful life, than plastics.
54
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Loss from leaching of chlorinated paraffins from external,
marine, and traffic paints probably also contribute significantly to environ-
mental contamination.
5. From Disposal
Although the amounts of chlorinated paraffins that are disposed
of every year are unknown, it is likely that disposal methods consist of either
incineration or landfilling. Incineration should result in complete destruction
of chlorinated paraffin materials because of their relatively low thermal
stability. On the other hand, Zitko and Arsenault (1974) have suggested that
the possibility of thermal formation of low molecular weight chlorinated hydro-
carbons from chlorinated paraffins should be investigated, especially in view
of the carcinogenicity of some of the low molecular weight compounds.
There is a high probability that large quantities of chlorinated
paraffins will reach landfills as a result of disposal of such products as
plastics, waste oils, and products that use flame retardants. However, be-
cause of the low water solubility of chlorinated paraffins relative to PCB's
(see Table 23, p. 51, and 25, p. 54), it is likely that much less leaching of
chlorinated paraffins from landfills and dumps will occur.
6. Potential Inadvertent Production of Chlorinated Paraffins
in Other Industrial Processes
Chlorinated paraffins might be produced as a by-product from
chlorination of other hydrocarbon feed stocks, if significant amounts of
paraffin are present as contaminants in the hydrocarbon starting material.
With hexachlorobenzenes and hexachlorobutadiene, inadvertent production
appears to be a major environmental contamination source (Mumma and Lawless,
1975). Since paraffins as well as many other hydrocarbons are derived from
55
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petroleum feed stocks, the possibility of inadvertent chlorinated paraffin
contamination from chlorination of hydrocarbons seems feasible at first
glance.
A large portion (59%) of the chlorine that is consumed in
this country (9.868 billion Ibs./year) is used in chlorinating hydrocarbons
(Mumma and Lawless, 1975). Table 26 lists the major compounds which are
chlorinated and, when available, the quantities of the final product that
are manufactured. In most of these hydrocarbons the possibility of paraffin
contamination seems very remote. Some of the organic compounds are gases
and most of them are distilled or fractionated in some way before chlorination.
Those compounds should have no high molecular weight paraffins because of the
high boiling points of the paraffins. However, some less volatile compounds,
such as a-pinene, naphthalene, and blphenyl, might have small amounts of
paraffins.
Another possible by-product source of chlorinated paraffins
is from the incomplete polymerization of chlorinated ethylene monomers (e.g.,
vinyl chloride, 1,2-dichloroethylene). If the polymerization process is
incomplete, lower-molecular weight products will be formed that closely
resemble the chlorinated paraffins. The quantity of chlorinated paraffins
produced in this way is unknown, but could be quite large considering the
volume of polyvinyl chloride produced every year.
7. Potential Inadvertent Production in the Environment
Although there are approximately 150 naturally occurring
chlorine compounds that have been identified so far (Siuda and DeBernardis,
1973), it does not appear likely that the chlorinated paraffins, with their
56
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Table 26. Organic Compounds That Are Produced By Direct
Chlorination (from Minima and Lawless, 1975)
Starting Material
Acrylic
Methane |
or )
Methanolj
Ethane or Propane
Ethane
Ethylene
Ethanol or Acetaldehyde
Acetylene
Acetylene
1,3-Butadiene
Acetic acid
Cyclic
Benzene
Product
Product
(X in&/y
Toluene
a-Pinene
Cyclopentadiene
Nitrobenzene
Naphthalene
Biphenyls
Methyl chloride 222/1970
Methylene chloride 260/1970
Chloroform 118/1970
Carbon tetrachloride 496/1970
N Perchloroethylene
Carbon tetrachloride
Methyl chloroform
Ethylene dichloride 4420/
Chloral . 31/1969
Perchloroethylene
Trichloroethylene
Chloroprene
Vinyl chloride
1,4-Dichlorobutene 154/1970
Chloroprene 114/1970
Monochloroacetic acid 34/
Trichloroacetic acid 4/
Monochlorobenzene 243/1970
£-Dichlorobenzene 50/1970
p_-Dichlorobenzene 60/1970
Trichlorobenzenes 4.5/1970
Benzene hexachloride I/
(use U.V. light
during synthesis)
Benzyl chloride 43/
Benzal chloride 21
Benzotrichloride 9/
Chlorotoluenes 38/1971
Toxaphene 25
Hexachlorocydopentidiene 25/1971
Monochloronitrobenzenes 444/1970
Pentachloronitrobenzene 1.5/1970
Chlorinated naphthalenes 2.5
Polychlorinated biphenyls 20
57
-------
high chlorine content, will be produced in nature. However, there are
sizable amounts of paraffinic hydrocarbons in the environment that are
formed from natural as well as man made processes (see Table 27). Since
chlorine is used in both waste water and drinking water treatment, it is
possible that chlorinated paraffins could result. Because of the dilute
conditions that prevail, only very low numbers of chlorine atoms per molecule
(mono- or dichloro compounds) seem at all likely.
Table 27. Paraffinic Hydrocarbons Identified in Industrial Effluents
(Abrams _et _al., 1975)
Paraffin Formula
jv-dodecane Cl2**26
ii-docosane ^22^1+6
eicosane ^20^42
hcxadecane
nomane
octadecane
octane
pentadecane C15^32
tetradecane
_n-tridecane
n-undecane
58
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D. Current Handling Practices and Control Technology
1. Special Handling in Use
No special safety precautions are necessary for handling
chlorinated paraffins. Most of the commercial formulations have no effects
on the skin, on repeated or prolonged contact (Hardie, 1964), but protective
gloves are recommended (Diamond Shamrock Chetn. Co., 1972). It is also suggested
that safety glasses and body length clothing be worn and that respiratory pro-
tection equipment be used when working in aerosol mists of liquid chlorinated
paraffins (Diamond Shamrock Chem. Co., 1972). No threshold limit values for
allowed exposure have been established. When working with the higher chlorine-
content paraffins (70%), it is recommended that proper ventilation be provided
because of residual amounts of the highly toxic carbon tetrachloride, which
is frequently used as a solvent in their manufacture (Hardie, 1964).
Temperatures exceeding 400"F and strong bases as well as
exposure to hot or finely divided metals of the third and fourth periods of the
periodic chart should be avoided. Storage temperatures should not exceed 66°C
for more than several hours in vented containers or 40°C in closed vessels
(Diamond Shamrock Chem. Co., 1972).
2. Methods for Transport and Storage
The liquid chlorinated paraffins are transported in drums
(usually 55 gallon) and insulated tank cars or tank trucks. Bulk shipments
may vary from 4,000 - 10,000 gallons.. The solid chlorinated paraffins are
transported in the form of solid broken lumps in lined sacks of paper or
other material.
59
-------
Stainless steel or lead-, glass-, enamel-, or lacquer-lined mild
steel are frequently used as container material for the liquid chlorinated
paraffins, although all-welded mild steel containers can be used if the storage
temperature does not exceed 30°C (Hardie, 1964). When color deterioration is
unacceptable (caused by traces of iron), the drums may be internally lacquered
with a phenol-formaldehyde resin (Hardie, 1964). The sacks for the solid
chlorinated paraffins are lined with polyethylene, at least in the United
Kingdom (Hardie, 1964).
Liquid chlorinated paraffins can be loaded or unloaded by a
pump, by air pressure, or in some cases, by gravity (Diamond Shamrock Chem. Co.,
1974) . When compressed air is used, it should be entirely free of suspended
matter, such as iron rust particles, which may catalyze decomposition and de-
coloration. Since many of the products are very viscous, the tank cars and
trucks as well as storage tanks are frequently insulated and contain heating
coils to facilitate transfer. The Diamond Shamrock Chemical Co. (1974) recommends
that pipes be lined with polyvinylidene dichloride.
As noted earlier, storage temperatures should not exceed 66°C
in vented containers or 40°C in closed vessels.
3. Disposal Methods
No special disposal procedures are recommended. Diamond
Shamrock Chemical Co. (1972) suggests that federal, state and local regulations
regarding health and pollution be followed.
Because chlorinated paraffins decompose at relatively low
temperatures (300-400°C) compared to PCB"s (>800°C), they can be disposed of
with conventional incinerators without the need for special precautions
60
-------
(e.g., afterburners). It is suspected that the chlorinated paraffins would
decompose in an incinerator before significant amounts are volatilized (Zitko
and Arsenault, 1974). Some control of the hydrogen chloride generated would
probably be required.
4. Accident Procedures
If liquid chlorinated paraffins are spilled or released, they
should be covered with an oil-absorbent type material, swept up and disposed
of in an acceptable manner. All of the chlorinated paraffin formulations are
considered to be non-flammable, but the liquid products are free flowing,
especially when they are hot, and therefore, should be treated as an oil
in a fire area. In a fire area, noxious and corrosive gases, such as phosgene
and hydrogen chloride may be generated, and therefore, firefighters should
avoid confined areas containing these materials. Furthermore, these gases
may cause rupture of non-vented containing vessels (Diamond Shamrock Chem.
Co., 1972).
The following procedures are recommended for first aid in
case of human contact with chlorinated paraffins (Diamond Shamrock Chem. Co.,
1972):
Skin contact - wash with soapy water
Eye contact - flush with warm water
Ingestion - consult a physician
5. Current Controls
No controls on chlorinated paraffins handling or use have been
located in the available literature. The Interstate Commerce Commission does
not require any special packaging.
6. Control Technology Under Development
None identified in the available literature.
61
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E. Monitoring and Analysis
1. Analytical Methods
Analysis of trace amounts of technical chlorinated paraffins
is difficult due to the complexity of the formulations. Zitko and Arsenault
(1974) have reviewed possible cleanup and analysis techniques that could be
used with chlorinated paraffins. The less applicable techniques that were
reviewed will be briefly discussed here, followed by detailed consideration
of the more promising methods.
The fact that chlorinated paraffins are part of the chlorinated
hydrocarbon family suggests that analytical techniques used with organochlorine
pesticides and PCB's might be applicable for trace detection of chlorinated
paraffins. Determination of chlorine has been shown to be an effective means
of quantitation for the chlorinated paraffins, but the more sensitive or
specific techniques used with pesticides, such as gas chromatography with
electron capture detection (GC-EC) or gas chromatography combined with mass
spectrometry (GC-MS), do not appear to be feasible.
Zitko and Arsenault (1974) stated that the mass spectra of
chlorinated paraffins are of little diagnostic value, except for a few peaks
at low masses. This statement was based upon review of a paper by Valovoi
and Polyakova (1970) as well as a private communication with Hutzinger and
Safe of the National Research Council of Canada. Friedman and Lombardo (1975)
have considered the possibility of using the GC-EC technique for detection of
chlorinated paraffins. Unfortunately, electron capture is relatively
62
-------
insensitive to aliphatic compounds such as chlorinated paraffins (e.g.,
500 yg of Chlorowax 500C was required for ^ full scale deflection - Lom-
bardo £t £l., 1975). As a result, the chlorinated paraffin gas chromatographic
peak pattern is obscured by the commonly found chlorinated aromatic compounds
(e.g., DDT and PCB's), which cause large responses with electron capture
detectors. The UV irradiation cleanup step devised by Friedman and Lombardo
(1975) helped somewhat (e.g., the interfering DDE peaks were totally removed),
but the chlorinated paraffins still only appeared as "a series of poorly
defined bumps on a huge 'solvent1 tail" (Lombardo ej^ al., 1975).
Less sensitive techniques such as infrared spectrometry have
been used to analyze chlorinated paraffins. Roesner and Berthold (1965) used
the 615 cm * C-OL stretching frequency for quantitation. Cachia et al.
(1958) also used infrared spectroscopy to detect chlorinated paraffins in
mixtures of plasticizers. The chlorinated hydrocarbon plasticizers (e.g.,
Cereclor I or Arochlor 1242) were separated from the other plasticizers by
silica gel column chromatography using carbon tetrachloride solvent.
Zitko and Arsenault (1974) have suggested that high pressure
liquid chromatography may have great potential for isolation and quantitation
of chlorinated paraffins if a microcoulometric or electrolytic conductivity
detector were used. This especially applies to the formulations that have
high chlorine content or long carbon chains and thus may decompose at
temperatures required for elution with conventional gas chromatography. So
far, use of the liquid chromatographic technique has not been reported.
63
-------
Determination of chlorine, especially by microcoulometry,
is, so far, the most frequently used method for quantitating trace amounts
of chlorinated paraffins. Zitko and Arsenault (1974) suggest that the
available methods that could be used with chlorinated paraffins include
determination of chlorine, titrimetrically with silver nitrate, by halogen-
selective electrodes, or microcoulometrically. The chlorine may be in the
form of hydrochloric acid, or chloride liberated from the sample either by
combustion or by reduction with metallic sodium (Zitko and Arsenault, 1974).
Table 28 presents some of the chlorine detection techniques that were reviewed
and evaluated by Zitko and Arsenault (1974). However, only the thin layer
silver nitrate - UV detection technique noted in Table 28 has actually been
used with chlorinated paraffins.
Zitko and Arsenault (1974) examined the thin layer chromato-
graphic (TLC) properties of Cereclor 42 and Chlorez 700. The study concentrated
on silica layers because they provided much less diffuse spots than alumina.
Conventional silver nitrate, 2-phenoxyethanol and acetone spray followed by
UV light development resulted in a detection limit of 130 and 2 yg for
Cereclor 42 and Chlorez 700, respectively. By slight modification (spraying
with 1 N AgN03, 0.1% fluorescein in 50% aqueous ethanol and heating to 100°C for
10 min.), the authors increased the limit of detection to 8-10 yg for Cereclor
42. However, the detectable concentration of chlorinated paraffins in lipids
is only 10 and 1% for Cereclor 42 and Chlorez 700, respectively. Thus, in order
to use the TLC procedure, the lipids would have to be separated from the
chlorinated paraffins. Thin layer chromatography with silver nitrate detection
was not considered any further by Zitko and Arsenault (1974) or by any other
investigator.
64
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Zitko (1973) has used a commercially available combustion
furnace and microcoulometer (Dohrman microcoulometric system MCTS-20) with
high-molecular-weight chlorinated paraffins (20 ~ ^2k). The combination
of gas liquid chromatography with microcoulometric detection was not used
because of the low volatility of the formulations. Cereclor 42 (I.C.I.,
42% chlorine) and Chlorez 700 (Dover Chemical, 70% chlorine) were the two
chlorinated paraffins studied. Recovery of chloride from the chlorinated
paraffins was only 40-60% when hexane was used as the solvent for injecti n
(probably due to the rapid evaporation of hexane in the needle). Much
higher yields were obtained (80-90%) when solutions of 20 w/v% diethylhexyl
phthalate (DEHP) or Nujol in hexane are injected. Sensitivity of this
system is 2 ng of chloride (Zitko and Arsenault, 1974).
Unfortunately, determination of chlorine by direct micro-
coulometry is not a specific method for quantitation of chlorinated paraffins.
Sulfur and nitrogen compounds may interfere as well as other organochlorine
compounds, both man-made and natural. For example, Siuda and DeBernardis
(1973) suggest that the number of "naturally occurring" halogenated compounds
total more than 200. Lombardo and coworkers (Friedman and Lombardo, 1975;
Lombardo et al., 1975) have made the microcoulometric detector somewhat
more specific by combining it with a gas-liquid chromatographic column. How-
ever, this technique could only be used with the shorter (Ci2 ~ GI?)
chlorinated paraffins, because the longer chained materials would decompose
on the column. The chlorinated paraffins used by Friedman and Lombardo (1975)
66
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were Chlorowax 500 C (Ci2» chlorine=59%, Diamond Shamrock), Unichlor 70LV
(C12~lif. chlorine=69%, Neville Chem. Co.). Cereclor S-45 and Cereclor
S-52 (C1if-17, chlorine-45% and 52%, respectively, ICI America Inc). Using
this combined technique, Friedman and Lombardo (1975) were able to readily
quantitate chlorinated paraffins at the ppm level. Lombardo et al.
(1975) were able to get h full scale deflection with 300 yg of Chlorowax
500 C (electron capture required 500 yg).
Even combined gas chromatography-microcoulometry is sus-
ceptible to interferences from normally encountered environmental contami-
nants. Furthermore, since it can only be used with the more volatile chlori-
nated paraffin formulations, it has limited applicability. Therefore,
several approaches have been suggested for either cleaning up the sample
before quantitation or chemically modifying the chlorinated paraffin to
allow more specificity during quantitation.
Zitko (1974b) examined the possibility of using a reductive
dechlorinatlon confirmatory test for chlorinated paraffins. Dechlorination
could allow identification by the gas chromatographic peak pattern of
the parent paraffin mixture. Zitko (1974b) used sodium bis(2-methoxyethoxy)-
aluminum hydride as the dechlorinating agent. Yields of the parent hydro-
carbon varied from approximately 15-30% for the formulations containing
40% chlorine, to 9% for the 50% chlorine, to no detectable paraffin for
the 70% chlorine formulation (see Table 11, p. 20). With the hydride used, it
has been shown that vicinally disubstituted alkanes give the respective alkenes,
67
-------
and therefore, it is understandable that reduction of the formulation
containing 70% chlorine (almost one chlorine on every carbon atom) resulted
in no paraffins. The unsaturated products from reduction of the 70% chlorine
product also contain hydroxyl function and fluorescence with an excitation
maximum at 320-340 nm and an emission maximum at 450 nm.
The reduction process can be carried out on relatively
clean samples of chlorinated paraffins as well as in the presence of
lipids (excess reducing agent is used). Alumina column chromatography
was used for removing the lipids after reduction.
This dechlorination procedure followed by gas chromato-
graphic-flame ionization detection (GC-FI) of the paraffinic hydrocarbons
may be used as a confirmatory test for chlorinated paraffins containing
up to 50% chlorine. However, reductive dechlorination of chlorinated
paraffins containing 70% chlorine does not yield paraffin hydrocarbons,
but instead results in unsaturated compounds that may also be used for
confirmatory purposes, especially if their fluorescence spectra are
recorded. As with many confirmatory tests, the dechlorination technique
is much less sensitive than microcoulometric detection. "The limit of
detection for Cereclor 42 is 25 mg/g lipid. At the same concentration of
Chlorez 700, the bluish fluorescence was clearly visible on TLC plates"
(Zitko, 1974b). The reductive dechlorination technique using sodium
bis(2-methoxyethoxy)aluminum hydride and GC-FI has also been used by
Panzel and Ballschmiter (1974) to identify and determine trace amounts
of chlorinated paraffins (see Figure 1, p. 2).
68
-------
Most other approaches to making the detection of
chlorinated paraffins more specific have been directed toward removal
of interfering compounds before quantitation by microcoulometry. Friedman
and Lombardo (1975) developed a photochemical technique for eliminating
chlorinated aromatic interferences. By irradiating the sample contained
in petroleum ether for 90 minutes with high energy ultraviolet light, they
were able to eliminate 100% of the peaks attributed to o,p'-DDE, p,p'-
TDE, perthane, carbophenothion, p,p'-DDT, methoxychlor, Halowax 1099
(chlorinated naphthalene), and Arochlor 1254 (PCB's). However, cycloali-
phatic materials such as toxaphene, chlordane, strobane, and mirex were
not totally destroyed. Quantitation was provided by gas chromatography
with microcoulometric detection. Recovery studies of ocean perch fillets
fortified with 1 and 5 ppm Chlorowax 500C indicated >90% recovery when the
method of Porter ej; al. (1970) was used followed by irradiation. The
procedure of Porter et al. (1970) consists of petroleum ether extraction
of the fish or animal tissue, petroleum ether-acetonitrile partitioning
(to remove lipids), followed by Florisil column chromatography. The 6%
ethyl ether-petroleum ether eluate is the one irradiated in the Friedman
and Lombardo (1975) technique. This same procedure was used by Lombardo
et al. (1975) to detect the amount of chlorinated paraffin in rainbow
trout fed a diet of 10 ppm Chlorowax 500C (612). Recoveries from for-
tified samples were greater than 92% and the sensitivity was at least
0.5 ppm.
69
-------
Zitko (1973) devised a chromatographic procedure which
could clean up biological extracts containing chlorinated paraffins and
also separate PCB's from the chlorinated paraffins. Fortified samples
of herring gull yolk, common seal blubber, and fish food were extracted
with hexane and then the extract was chromatographed on alumina to remove
the lipids. Recovery of the chlorinated paraffins is quantitative. The
elution pattern from the alumina column was affected by the quantity
of lipids present, probably due to deactivation of the alumina by the
lipids (Zitko, 1973). Using silica chromatography on the alumina
column eluate, PCB's and p,p'-DDE (hexane eluate) were separated from
other chlorinated hydrocarbon pesticides and the chlorinated paraffins
being studied (10% ether in hexane eluate). Alumina chromatography
has a tendency to reduce the "apparent chlorine" background (direct micro-
coulometric detection) in the biological samples as noted in Table 29.
Table 29 also illustrates that sizable quantities of "apparent chlorine"
pass through the alumina column but cannot be attributed to PCB or DDT com-
pounds, and this accentuates the non-specificity of direct microcoulometry.
Table 29 . Effect of Alumina Chromatography on the Apparent
Chlorine Content in Various Biological Samples
(data from Zitko, 1973)
yg/g in hexane % PCB and DDT in
yg/g wet wt fraction from hexane fraction from
alumina column alumina column
jctuiy.Lc
Herring gull yolk
Fish food
Seal blubber
214
3.00
94
17.6
1.11
94
57%
20%
71%
70
-------
Zitko and Arsenault (1974) have examined the solvent
partitioning of chlorinated paraffins as well as the extraction re-
coveries of chlorinated paraffin fortified sediment samples. Solvent
partitioning is a frequently used cleanup procedure (e.g., the Porter e^_
al. , 1970, procedure used by Lombardo e_t al. , 1975) and can be used as a
confirmatory technique. Lombardo e^ al. (1975) have demonstrated that the
shorter chain (Cg - Ciy) could be partitioned away from lipids using
petroleum ether and acetonitrile. Zitko and Arsenault (1974) examined the
recovery of the longer chained (C20 ~ C25) chlorinated paraffins from hexane
solution into acetonitrile (MeCN), dimethyl formamide (DMF), and dimethyl
sulfoxide (DMSO). The results of their partitioning study are presented in
Table 30.
Table 30. Recovery of Chlorinated Paraffins from Hexane
(Zitko and Arsenault, 1974)
Cumulative Recovery, %
Cereclor 42 Chlorez 700
Extraction No. MeCN DMF DMSO MeCN DMF DMSO
1 46.9 70.7 33.3 31.6 69.9 88.0
2 66.2 86.3 43.3 59.3 93.1 93.3
3 85.3 59.1 71.4 95.1
71
-------
The results demonstrate that hexane-DMF could be used as a cleanup pro-
cedure to remove lipids. However, Zitko and Arsenault (1974) concluded
that "not enough data are yet available to use solvent partitioning of
chlorinated paraffins as a diagnostic tool."
These same researchers also examined the recoveries of
Cereclor 42 and Chlorez 700 fortified on sediment to 463 and 277 ug/g on a
wet weight basis, respectively. Extraction of wet spiked sediment with
acetone or dimethyl formamide yielded no recovered chlorinated paraffins.
However, elution of air-dried sediment with hexane provided nearly quantitative
recovery. The amount of solvent required could be reduced by using 50%
ether.
In summary, analytical procedures for detecting trace
amounts of chlorinated paraffins are not anywhere near as sensitive or
specific as techniques commonly used with organochlorine pesticides. The
microcoulometric-gas chromatographic technique using petroleum ether ex-
traction, acetonitrile partitioning, and U.V. irradiation cleanup (Friedman
and Lombardo, 1975) seems to be the most specific and sensitive, but can
only be used with the shorter chain (Cg - Cn) chlorinated paraffins.
The procedure is capable of measuring levels of at least 0.5 ppm in
fish flesh (Lombardo et al., 1975). The application of this technique
to biological or other environmental samples requires a great deal of
caution since the specificity of the method is based on gas chromatographic
peak pattern recognition. Lombardo et al. (1975) have demonstrated, at
72
-------
least with Chlorowax 500 C accumulated in fish, that the pattern of peaks
can change considerably due to selective uptake or differential metabolism
and/or elimination.
For the longer chain (C2o ~ £25) ^emulations, the procedure
used by Zitko (1973) appears to be the most sensitive (sensitivity 2 ng of
chloride-measured down to 1 ng/g wet weight of fish food), but very unspecific.
The procedure consisted of hexane extraction, alumina chromatographic
column cleanup (remove lipids), silica column cleanup (remove PCB's), followed
by direct microcoulometric quantitation (20 w/v% DEHP or Nujol in hexane
solution for injection). The lack of specificity limits any application of
this technique to environmental samples. Unfortunately, the confirmatory
test suggested by Zitko (1974b) requires high concentrations of the chlor-
inated paraffin (limit of detection - 25 mg/g of lipid) and relies on gas
chromatographic peak pattern recognition of the paraffin hydrocarbon
(selective degradation, uptake, metabolism, or elimination may obscure the
pattern).
2. Monitoring
No published monitoring information on chlorinated paraffins
in environmental samples has been noted in the United States. However,
communication with Beynon (1975), indicates that some monitoring data for
Great Britain is about to be published and that additional information is
being developed. The details of the information were not available in time
for inclusion in this report, but should be published in a few months.
73
-------
Zitko (1973) has noted a discrepancy between the
total chlorine in herring gull yolk, seal blubber, and fish food and
the chlorine that can be accounted for by PCB's or DDT and metabolites,
even after alumina column cleanup with hexane solvent (see Table 29, p. 70)
74
-------
III. Health and Environmental Effects
A. Environmental Effects
1. Persistence
Chlorinated paraffins placed in the environment may degrade
by one of the following processes: (a) biodegradation - effected by living
organisms, (b) photochemical degradation - non-metabolic degradation re-
quiring light energy, and (c) chemical degradation - non-metabolic
degradation catalyzed or effected by ubiquitous substances, such as oxygen,
water, soil, etc. This section is devoted to biological and chemical
degradation of chlorinated paraffins in the environment; the available
information on photochemical reactions has already been discussed in
Section I-B-4, p. 18.
a. Biological Degradation, Organisms, and Products
Chlorinated paraffins have not been extensively investi-
gated for their environmental fate. Research along these lines has been hampered
by the complex nature of the commercial preparations of chlorinated paraffins,
which makes interpretation of the biodegradation data and identification of
breakdown products extremely difficult.
The salient features of the available microbial degradation
studies with commercial preparations of chlorinated paraffins are summarized in
Table 31. Hildebrecht (1972) conducted a preliminary study to determine the
biodegradability of samples of various chlorinated waxes containing small
proportions of surfactant (formulations supplied by Diamond Shamrock Chemical
Corporation) (see Table 31). Biochemical oxygen demand (BOD) was measured
75
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by Warburg respirometry and by the dilution method. In each method, the
bacterial seed was acclimated to the individual chlorinated paraffin
formulation before the test was run. The results of this investigation are
presented in Table 32. Interpretation of the results of the test is some-
what difficult in view of the shortcomings discussed below.
The measurement of oxygen consumption can provide an
estimate of the extent of biodegradation, when compared to data on the
theoretical oxygen demand (TOD). Hildebrecht (1972) attempted to calculate
the TOD from the measured total organic carbon (TOC). However, since the
oxygen is consumed in producing carbon dioxide from the available carbon as
well as water from the available hydrogen, the TOD calculated in this fashion
will only be approximate. On the other hand, if one assumes that all the
chlorine and hydrogen available in chlorinated paraffins is consumed in the
production of hydrogen chloride, the calculated TOD would be approximately
correct. This difficulty in the derivation of the TOD values makes the experi-
mental results somewhat difficult to interpret. Furthermore, Hildebrecht
(1972) uses arbitrary criteria for defining biodegradability; he defines any-
thing that consumes greater than 35% TOD as biodegradable. The validity of
this assumption is particularly doubtful when chemical mixtures are studied;
35% oxygen consumption can be obtained merely if one component of the mixture
(which may amount to 35% of the total carbon) is completely degraded to
carbon dioxide. Another difficulty encountered in interpretation of the data
is that the author adds unspecified "bionutrients" during the acclimation phase
and during the oxygen consumption test. If these are inorganic nutrients, they
probably have little effect on the test results. However, if organic materials
are included, they can have considerable impact on the interpretation of
the results. For instance, nutrients may be oxidized along with the test
chemical thus complexing the BOD results.
77
-------
Table 32. Oxygen Consumed in BOD Bottle Test and Warburg
Respirometer with Chlorowaxes (Hildebrecht, 1972)
Biological Oxygen Demand
Respirometry (20 hrs) Dilution Method (5 days)
Commercial Preparations K *5 i~*-
Studied (see details Oxygen Consumed % of Theoretrical Measured BOD % of Theoretical
in Table 31) (mgs/1) oxygen demand* (mg/1) Oxygen Demand*
A 484 _ 40 470 39
B 83 17.2 120 25
C 298 17.2 30 2
D 279 17.2 50 3
E 377 46.5 530 65
*The author has based his calculation of theoretical oxygen demand on the total carbon
content of the sample and not on the empirical formula.
In view of the shortcomings in this study, only
qualitative conclusions seem justified. The Chlorowax 500C seems to be
degraded to some extent by microorganisms. The other Chlorowax formulations
are much more stable in the Warburg test, although Chlorowax 40 appears to
degrade somewhat under the dilution BOD bottle conditions. The degradation
products that may be formed could not be determined by this method.
Zitko and Arsenault (1974, 1975) have studied the biodeg-
radation of commercial chlorinated paraffins (Cereclor 42 and Chlorez 700) in
estuarine sediments under anaerobic and aerobic conditions. The test mixtures
were made by charging 25 g of previously spiked sediment, 300 m£ of sea water,
and 10 mSL of a suspension of decomposing organic matter in sea water to a 500 m£
Erlenmeyer flask. The aerobic flasks were aerated while the anaerobic flasks
78
-------
were kept stoppered. After various periods of incubation, the concentration
of chlorinated paraffins in the sediment was determined by air-drying a sample
of sediment followed by hexane-ether (50/50) extraction and direct injection
microcoulometric quantitation. Some of the controls contained microcoulometrically
active interferences. The results are presented in Table 33.
Table 33. Biodegradation of Chlorinated Paraffins in Spiked Sediments
(Zitko and Arsenault, 1974, 1975)
Concentration in Sediment, UK apparent chlorine/g of Sediment, dry weight
Time (days) Aerobic
0
10
21
28
Cereclor 42
596
257
147
377
Chlorez 700
357
76
128
72
Anaerobic
Cereclor 42
596
80
194
98
Chlorez 700
357
41
33
50
In addition, thin-layer chromatography and IR spectrophotometry on hexane/
ether extracts of the remaining sediment dried in vacuum were also used to
follow the loss of chlorinated paraffins. Only traces of the chlorinated
paraffins were found after 30 days of incubation.
Zitko and Arsenault (1974, 1975) concluded that the
chlorinated paraffins are biodegradable in sediment and that the rate was higher
under anaerobic conditions. However, the reproduclbility of the latter con-
clusion is questionable considering the inconsistency of the general trends in
Table 33. For example, under aerobic conditions with Cereclor 42, more
apparent chlorine is detected at 28 days than at 10 or 21 days. Zitko and
Arsenault (1974) also pointed out that the analytical procedures used would
not allow for the measurement of more polar, chlorine-containing transformation
products that might be formed. Thus, the actual mineralization of chlorinated
paraffins (conversion to chloride) may be much less than indicated from the
experimental data.
79
-------
Overall, the results of the studies concerning the
environmental biodegradability of chlorinated paraffins are inconclusive.
Studies of Zitko and Arsenault (1974, 1975) have shown that the detectable amount
of Cereclor 42 and Chlorez 700 in sediment decreases with time; however, the
extent of degradation of these compounds is uncertain. Of the Chlorowax
formulations, only Chlorowax 500C and perhaps Chlorowax 40 appear to be bio-
degradable to some extent (Hildebrecht, 1972). No information is available
on the products of biodegradation.
b. Chemical Degradation in the Environment
The available information on the chemical reactivity of
chlorinated paraffins has already been reviewed in Section I-B, p. 16. The
information presented there would suggest that chlorinated paraffins do not
hydrolyze, oxidize, or otherwise react at significant rates under ambient
temperature and relatively neutral conditions. Thus, it would appear that
these compounds are fairly chemically stable under environmental conditions.
Their use in applications which require chemical resistance, such as traffic
and marine paints, lends support to this conclusion. However, the chlorinated
paraffins can be catalytically dehydrochlorinated in the presence of iron
oxides as well as other inorganic compounds, and the possibility of this
process occurring in nature seems quite feasible. Unfortunately, no experi-
mental data are available on the chemical stability of chlorinated paraffins
under simulated environmental conditions.
2. Environmental Transport
Transport of chemicals in the environment depends upon such
physical processes as adsorption on colloidal substances, volatilization,
80
-------
bioaccumulation and leaching. These processes result in distribution and dilution,
or concentration, of contaminants. Although no experimental data are reported
in the literature, an attempt has been made in this section to look at environ-
mental movement of chlorinated paraffins based on their physical properties.
Considering the low solubility of normal CIQ - CSQ paraffins
in water, and the increasing hydrophobic effect of chlorine substitution, it
appears likely that chlorinated paraffins are insoluble in water and
adsorb readily on suspended particles. A tight binding of chlorinated paraffins
to estuarine sediment is suggested from the fact that Zitko and Arsenault
(1974) failed to extract chlorinated paraffins from wet spiked sediment with
such polar solvents as acetone or dimethyl formamide. This low water solubility
and tight binding to sediment would suggest that chlorinated paraffins probably
are not leached through soils at appreciable rates.
Most commercially available chlorinated paraffin preparations
are non-volatile at temperatures around 20°C (volatility generally < 6 x 10 **
gms/cm2/hr at 100°C. The measured vapor pressure of a C23Hi+e» 42% - 54% CJt,
chlorinated paraffin is reported to be 2 x 10 5 mm Hg, which is similar to
PCB's (see Table 23, p. 51). Thus, because of the low vapor pressure and low
thermal stability (destroyed before volatilized), evaporation and atmospheric
transport probably have a very small role in the distribution of chlorinated
paraffins in the environment.
Chemicals in aquatic systems can be lost to the atmosphere by
co-distillation with water. However, in view of the high molecular weight of
chlorinated paraffins, and the fact that in aquatic systems, these materials
will be adsorbed on the suspended matter, it seems unlikely that these chemicals
will be lost to the atmosphere to a significant extent by co-distillation from
water.
81
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3. Bioaccumulation
In view of the high molecular weight of chlorinated paraffins,
their bioaccumulation potential appears to be limited. The ability of chlorinated
paraffins to strongly adsorb to suspended particulates in water will further
reduce their availability to food chain organisms. Zitko (1974a) has studied the
uptake of chlorinated paraffins (Cereclor 42, and Chlorez 700) by juvenile
Atlantic salmon (Salmo salar). Chlorinated paraffins were administered: (a)
adsorbed on suspended solids simulated by silica, and (b) in food. The results
of this study using both administration methods are presented in Table 34.
Table 34. Uptake of Chlorinated Paraffins and PCB from Suspended
Solids and Food by Juvenile Atlantic Salmon
(Zitko, 1974a)
- In Suspended Soltds -
Time of
Preparation Exposure, hr. Chlorine ug/g
Control 48
Cereclor 42 48
144
Chlorez 700 48
144
Aroclor 1254 24
48
144
Days of Feeding
Diet
Control
Cereclor 42, 10 yg/g
100 pg/g
Chlorez 700, 10 yg/g
100 Mg/g
Aroclor 1254, 10 ug/g
100 ug/g
Concentration in Fish
Mg PCB or Chlorinated
wet wt. Paraffin/g wet wt . Lipid %
0.34
0.44 1.05
0.75 1.79
0.22 0.31
0.46 0.66
19.9
28.3
134
-In Food-
33
Residue*
0.30
0.11
0.51
0.29
0.49
3.86**
13.9**
Lipid%
1.03
1.30
1.22
1.13
1.30
5.09
5.30
109
Residue*
nd+
nd
nd
nd
nd
3.80**
24.0**
Lipid%
0.65
0.69
0.49
0.40
0.56
3.10
2.73
0.99
1.10
1.33
1.56
2.10
1.52
1.86
1.78
181
Residue*
nd+
nd
nd
nd
nd
3.80**
30.0**
Lipid%
0.47
0.49
0.34
0.29
0.92
2.07
2.69
* Expressed as chlorine, Mg/g wet weight
** Expressed as Aroclor 1254
+ Not detectable, < 0.05 jjg/g
82
-------
\ " Although somewhat inconclusive, the results suggest that chlorinated paraffins
U
do not accumulate in significant quantities in juvenile Atlantic salmon under
i
i_ either of the experimental conditions employed. Since the analytical method
used measured chlorine and not chlorinated paraffins, it is uncertain if the
I
levels of chlorine detected were due to chlorinated paraffins. Under similar
; conditions, polychlorinated biphenyls, which were used for comparison, were
found to bioaccumulate to a much greater extent. Since high levels of
i*
.,_ chlorine were not detected when chlorinated paraffins were used, it was con-
cluded that these compounds do not bioaccumulate.
I
^ Lombardo e_t al. (1975) fed fingerling rainbow trout a diet
'; fortified with 10 ppm of Chlorowax 500C. Because Chlorowax 500C contains much
\~.
lower molecular weight isomers than the chlorinated paraffins studied by Zitko
i\ ,
'[___ (1974a), microcoulometric gas chromatography (with ultraviolet irradiation
cleanup - see Section II-E, p. 62) was used for analysis. Samples were taken
i
L~ at 2 week intervals over an 82 day period, and chlorinated paraffin residues
1 of as high as 1.1 ppm on a tissue basis, or 11-18 ppm on a fat basis, were
found. Because of an early termination of the study, Lombardo and coworkers
\_ (1975) were unsure whether an equilibrium level had been reached. However,
the low levels found using a much more specific analytical technique tend to
*"* confirm the conclusion of Zitko (1974a) that chlorinated paraffins bioaccumulate
i much less than PCB's. The study by Lombardo ejt al. (1975) also demonstrated
that bioaccumulation rates for different isomers in the Chlorowax 500C form-
^ ulation are quite different (major differences in the intensities of the GLC
peaks). The authors attributed this difference to differential uptake, metabolism
L- and/or elimination.
83
-------
4. Biomagnification
Biomagnification refers to concentration of a compound through
the consumption of lower organisms by higher food chain organisms with a net
increase in tissue concentration (Isensee ejt a_l., 1973). Although the bio-
magnification potential of chlorinated paraffins has not been studied as such,
some inferences regarding its biomagnification potential can be drawn from the
studies of Zitko (1974a) and Lombardo e£ al. (1975) which deal with the
accumulation of chlorinated paraffins in fish fed chlorinated paraffin
contaminated food. Since the fish in these studies failed to accumulate
significant quantities of chlorinated paraffins from synthetic fish food con-
taining chlorinated paraffins (see Section III-A-3, p. 82), it appears unlikely
that considerable increases in tissue chlorinated paraffin concentrations will
occur through consumption of lower food chain organisms. However, a different
conclusion can be reached by considering the solubility characteristics of
chlorinated paraffins. Based on the solubility of parent hydrocarbons and
solubility decreasing effect of chlorine substitution, Zitko and Arsenault
(1974) have predicted that chlorinated paraffins will be less soluble than
PCS's in water. Metcalf and Lu (1973) have determined the ecological
.-. . . ,concentration in organism-^ e ^^a\ * j -, Jt.
magnification ( a ) for FOB s in a model ecosystem; it
concentration in water ' *
was found to be in the range of 6500-12000 for fish and 6000-60,000 for
snails. Since ecological magnification in the model ecosystem has been
found to increase with an increase in water insolubility (Metcalf and Lu,
1973), the ecological magnification for chlorinated paraffins would be suspected
to be greater than for PCB's; a conclusion which is not supported from the experi-
mental data (see Zitko 1974a; Lombardo et al., 1975). The inability of chlorinated
84
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paraffins to accumulate and biomagnify could be attributed to their higher
molecular weight; the bulkiness of the molecules may prevent them from being
taken up by the living organisms.
Although a number of vital questions concerning bioaccumulation
and biomagnification potential of chlorinated paraffins remain unanswered, the
information available tends to suggest that significant bioaccumulation and
biomagnification of the unaltered chlorinated paraffins in the food chain will
not occur.
85
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B. Biology
Foreign compound absorption, distribution, biotransformation,
and excretion are intimately connected processes in living organisms.
The ultimate physiological action of an administered substance will be
determined not only by the extent to which it is absorbed into the
systemic circulation, but also by the form in which it arrives.
Extensive transformation prior to absorption is often catalyzed by
enzymes of the liver and other tissues, or may result from the action of
gut flora and gastric secretions. The consequences of different routes
of administration can result in extreme variation in the biological
activity of a single compound, based on the sequence of organ systems
through which the substance passes.
1. Absorption
Digestive absorption of chlorinated paraffins in juvenile
Atlantic salmon could not be demonstrated either by feeding concentrations of
10 and 100 ppm of Cereclor 42 (42% chlorine) or Chlorez 700 (70% chlorine) tn
the diet for 181 days, or by exposing fish to these compounds adsorbed on
silica (Zitko, 1974a). In contrast, a PCS preparation, Aroclor 1254, was
readily absorbed under similar conditions (Zitko and Hutzinger, 1972) (for
comparison, see Section III-A-3, p. 82). Chlorinated paraffin levels were
determined by the measurement of chlorine obtained by passing tissue extracts
directly into a microcoulometric detector (see Section II-E-1, p. 62). Un-
fortunately, the method is not specific for chlorinated paraffins but adequately
demonstrates that very little adsorption occurs. Zitko (1974a) noted that the high
molecular weight of chlorinated paraffins may slow down or inhibit their digestive
absorption, which was shown to be the case with normal paraffins (Zitko and
86
-------
Arsenault, 1974). The possible absorption of biotransfonnation products or
fragmented short-chain hydrocarbon impurities was not determined.
Lombardo el: al. (1975) reported that fingerling rainbow trout
fed 10 ppm of Chlorowax 500C (59% chlorine) in the diet for up to 82 days slowly
accumulated chlorinated paraffin residues in their tissues. Chromatographic
evidence (microcoulometric detection) indicated that a differential absorption
or metabolic transformation of the Chlorowax 500C occurred, based on a
comparison of tissue residues to the parent compound in spiked controls.
Further investigations to determine the extent of chlorinated paraffin ab-
sorption in higher animals by either dermal, oral or parenteral routes have
not been encountered in the literature.
2. Excretion
No data are available.
3. Transport and distribution in living organisms
No data are available.
4. Metabolic effects
No data are available.
5. Pharmacology
No data are available.
C. Toxicity - Humans
The approach to human toxicity must take into consideration the
exact nature of a particular compound or commercial product to which man is
exposed. It has been noted that various commercial preparations of chlor-
Inated paraffins may vary significantly with respect to the presence of manu-
facturing impurities in the finished product (Diamond Shamrock Chemical
Company, 1975). Unfortunately, detailed information on identity or toxicity
is not available for the chlorinated acyclic or aromatic hydrocarbons
87
-------
which may be present as impurities in chlorinated paraffins (see Section
I-A-3, p. 12). In addition, low molecular weight chlorinated hydrocarbon
fragments known to result from the decomposition of chlorinated paraffins may
represent a potential hazard in view of the well-known carcinogenic effects
of vinyl chloride (Zitko and Arsenault, 1974).
1. Controlled Studies
The toxic hazards associated with acute exposure to chlorinated
paraffins appear to be relatively low based on the limited data which are
presently available. This observation is supported by the fact that no cases
of industrial poisoning or contact dermatitis have been reported in workers
involved in the production and handling of these compounds.
Reports supplied by Dover Chemical Corporation (1975a) indicate
that Paroil 142 (40-41% chlorine) and Chlorez 700 (70% chlorine) were not active
as primary local irritants when applied as patches to the skin of two hundred
male and female volunteers for a five day period. Reapplication of the material
for two days beginning three weeks after the initial exposure produced no
allergic or other toxic responses. Similar studies have been reported by
Diamond Shamrock Chem. Co. (1975) indicating that Chlorowax 70 (70% chlorine),
Chlorowax 500C (59% chlorine) and Chlorowax 40 (43% chlorine) did not produce
local irritation or allergic responses when applied to the skin of two hundred
male and female subjects. The period of exposure and amount of chlorinated
paraffin product used in these studies are not known. Results of the above
studies indicate that selected chlorinated paraffin products when applied dermally
do not stimulate a cell-mediated immune response or produce delayed hypersensitivity
88
-------
reactions. It has not been established, however, whether the dose of
chlorinated paraffin employed may have been below the threshold concentration
required for sensitization, as has been demonstrated with known contact allergens
(Rostenberg and Kanof, 1941).
2. Epidemiology
No data are available.
3. Occupational Studies
No data are available.
D. Toxicity - Birds and Mammals
Animal studies on the effects of chlorinated paraffin adminis-
tration have been limited to the observation of gross toxicological
responses to acute oral and dermal exposures. Chronic and acute studies
have not been encountered which report hematological, gastro-intestinal,
or neurological measurements, nor have the effects of parenteral
administration of chlorinated paraffins been investigated.
1. Acute (Table 35)
Single dose oral ingestion of Chlorowax 70 at 50 g/kg in
rats and 25 g/kg in guinea pigs produced no mortalities (Diamond Shamrock
Chem. Co., 1975). Similarly, death did not result from the feeding of
Chlorowax 40 at 10 ml/kg in male rats. The oral LD5Q of Chlorowax 500C in
rats is greater than 21.5 ml/kg of body weight. In tests reported by Dover
Chemical Corporation (1975b), rats given oral doses of 10-50 g/kg of Chlorez 700
all survived a two week observation period, although a 20% mortality occurred
at the 60 g/kg dosage, presumably due to mechanical injury. Guinea pigs given
oral doses of 5-25 g/kg of Chlorez 700 all survived a two-week observation, whereas
a 40% mortality resulted in those animals fed 30 g/kg of body weight.
89
-------
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The dermal LD,-0 in rabbits for Chlorowax 500C was
reported to be greater than 10 ml/kg of body weight (Diamond Shamrock Chera.
Co., 1975). In the same study, a single application of Chlorowax 500C to
the eyes of rabbits produced a mild erythema in four of six test animals.
Inhalation toxicity was not encountered in rats exposed to an air concentration
of 3.3 mg/1 of Chlorowax 500C for a one hour period.
In studies conducted by Abasov (1970) with chlorinated paraffin
KhP-470, an abstract of the original article states that a single oral
dose to mice resulted in death at a minimum concentration of 19 g/kg, with
the LD_0 and LD1QQ being 21.85 and 24.0 g/kg of body weight, respectively.
When administered to rats, mortality was evident at 24.5 g/kg and the LDcQ
and LD _ were 26.1, and 28.0 g/kg, respectively. Although KhP-470 demonstrated
no effect when applied to skin, conjunctivitis resulted from contact with
the mucous membrane of the eye of test animals. While the lethality of
KhP-470 appears to exceed that of other commercial preparations, data are
not available concerning the formulation and chlorine content of this product,
thereby making direct comparison impossible.
2. Subacute
No data are available.
3. Sensitization
No data are available.
4. Teratogenicity
No data are available.
5. Mutagenicity
No data are available.
91
-------
6. Carcinogenicity
i
W<
No data are available.
\
7. Chronic Studies
No data are available.
* 8. Behavioral Effects
i No data are available.
\
9. Possible Synergisms
No data are available.
E. Toxicity - Lower Animals
i
* In a recent report on the accumulation of chlorinated paraffins
in juvenile Atlantic salmon, Zitko (1974a) demonstrated an insignificant
uptake of Cereclor 42 and Chlorez 700 when fish were exposed to these compounds
at levels of 10 and 100 ppm in the diet for an extended period. Mortality
was evident, however, among those fed the chlorinated paraffin contaminated
'-- diet. An LT (number of days to reach 50% mortality) ranging from 39-80 days
was noted, as opposed to the control group with an LT of 138 days. A
determination was not possible of the actual amount of food consumed by
the fish in this experiment, and consequently, the daily dose of chlorinated
L_
paraffin ingested could not be calculated. In a similar study by Lombardo
e_t al. (1975), fingerling rainbow trout were fed a diet containing 10 ppm
of Chlorowax 500C for up to 82 days. Gross toxicological effects were
not evident in treated fish although their increase in average body weight
i
1 throughout the experiment was consistently less than the control group.
92
-------
\
Additional data supplied by Johnson (1975) and summarized in
Table 36 demonstrate that LDen values for various Chlorowax preparations
against bluegills and rainbow trout were consistently greater than 300 mg/1
under standard static toxicity test conditions. Variations in test
temperature between 5 and 25° did not alter the static toxicity of Chlorowax
500C.
Table 36: Acute Fish Toxicity of Chlorowax Preparations
(Johnson, 1975)
SPECIES
Rainbow trout
Bluegill
Rainbow trout
Bluegill
Rainbow trout
Bluegill
Rainbow trout
Fathead minnow
Channel catfish
Bluegill
Rainbow trout
Bluegill
COMPOUND
Chlorowax 40
Chlorowax 40
Chlorowax 50
Chlorowax 50
Chlorowax 70
Chlorowax 70
Chlorowax 500C
Chlorowax 500C
Chlorowax 500C
Chlorowax 500C
Chlorowax LV
Chlorowax LV
SIZE
(g)
0.7
0.5
0.7
0.5
0.7
0.5
0.5
0.8
1.1
0.7
0.7
0.5
TEMP.
(c)
10
20
10
20
10
20
10
20
20
20
10
20
96 hr.
LC 50
(mg/£)
>300
>300
>300
>300
>300
>300
>300
>100
>300
>300
>300
>300
93
-------
In a flow-through test system, LC Q values obtained for bluegills and channel
catfish were greater than 100 mg/1 after 13 days exposure, and likewise for
rainbow trout after 24 days. Various sub-lethal effects, however, were noted
in the flow-through tests with rainbow trout at concentrations down to 40 ug/1-
These effects were manifested as a progressive loss of motor function leading to
immobilization beginning within 15 to 20 days. Where death occurred, it resulted
from debilitation, cessation of feeding, and other secondary effects. Differences
in susceptibility could not be demonstrated among rainbow trout yolk-sac fry,
swim-up fry, and fingerlings. Bluegills and channel catfish did not generally
exhibit these sub-lethal effects.
F. Toxicity - Plants
No data are available.
G. Toxicity - Microorganisms
Very little work has been done concerning the toxicity of commercial
chlorinated paraffins to microorganisms. Hildebrecht (1972) investigated the
effect of Chlorowaxes (Chlorowax 500C, Chlorowax 40, Chlorowax 70 and Exchlor SC)
on oxidative metabolism of sewage seed employing potassium acid phthalate, a
readily biodegradable substance, as substrate. Bottles containing an exact
amount of potassium acid phthalate, bionutrients, and bacteria seed were
incubated for five days and served as controls. The average residual dissolved
oxygen at the end of the incubation period was found to be 4.6 mg/1. When
chlorinated paraffins were added to the system at concentrations of 1.0, 10,
50, 100, and 200 mg/1, the residual dissolved oxygen values after five days
incubation were all less than 1.0 mg/1. These results indicated that
chlorinated paraffins were not toxic enough to alter the oxidizing ability of
the bacteria since the utilization of oxygen was not inhibited, as evidenced
by the decreased dissolved oxygen at the conclusion of the test.
H. Effects on inanimate objects and structures
No data are available.
94
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IV. Regulation and Standards
A. Current Regulation
According to the definitions and regulations as outlined in the
Federal Register of August 12, 1961, the chlorinated paraffins which have thus
far been tested for toxicity do not classify as hazardous substances. The
Commissioner of Food and Drugs has concluded that for a substance to be con-
sidered toxic by oral ingestion it must produce death within 14 days in one-
half of a group of adult rats at a single dose of 0.050-5.0 grams per kilogram
of body weight. Similarly, for dermal toxicity in rabbits, an LD must be
achieved at doses between 0.2 and 2.0 grams per kilogram of body weight. For
inhalation toxicity in rats, an atmospheric concentration of 2.0-200 milligrams
of foreign substance per liter of air must produce 50% mortality. The data
which are summarized in Table 35 indicate that none of the commercial chlorinated
paraffin products tested produced lethal effects at levels below the maximum
dose for toxicity as specified in the federal regulations. In addition, the
Food and Drug Administration has amended the food additive regulations to
provide for the use of "chlorinated liquid n-paraff±ns with chain lengths of
GIO " Cj7 containing 40-70% percent chlorine by weight" as components of food-
packaging adhesives (Anon., 1969). Under this regulation, the contact of
these substances with fatty and aqueous foods is limited to trace amounts at
package seams and edges of packaging laminates. For dry foods, packaging
adhesive contact is limited by the standards of "good manufacturing practice."
Chlorinated paraffins alone have not received approval for direct contact
with foods as regulated under Federal Code 21 CFR 121.2526.
95
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B. Consensus and Similar Standards
The chlorinated paraffins are rated as Class I, "practically non-
toxic" in "Clinical Toxicology of Commercial Products" (Gleason, 1969). This
source states that injury in test animals did not occur short of doses which
w produced intestinal obstruction. Furthermore, a calculated probable lethal
dose in humans was given as greater than 15 grams per kilogram of body weight
or more than one quart for a 70 kilogram man.
^ The American Conference of Governmental Industrial Hygienists, which
assigns threshold limit values to most toxic substances in workroom air does
l not list chlorinated paraffins in its compendium.
The 1974 edition of the "Toxic Substances List" was prepared
by the National Institute for Occupational Safety and Health to identify all
; known toxic substances, and contains some 13,000 unique chemical names. The
chlorinated paraffins are not Included in the list, although this may be due
i
u to insufficient data concerning dosage/effect relationships.
96
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V. Summary and Conclusions
Commercial chlorinated paraffins are extremely complex mixtures of isomers
and analogs of compounds formed when mixtures of n-paraffins (C^Q- C30) are
chlorinated to varying percentages of chlorine (usually 40-70% by weight).
Both liquid products (40-64% chlorine) and solid resins (^70% chlorine) are
commercially available.
In 1973, 74 million pounds of chlorinated paraffins were produced in the
United States by eight manufacturers with plants located at ten different geo-
graphic locations. The product is formed by liquid phase chlorination of the
warmed paraffin feed stock using either batch or continuous reactors. The
free-radical chlorination can be catalyzed by UV light, and the by-product
hydrogen chloride and residue chlorine are removed by blowing air through the
product. With the resinous products (^70% chlorine), a solvent such as carbon
tetrachloride is used to increase the viscosity and chlorination rate.
Major applications of chlorinated paraffins include uses as lubricating oil
additives (45% of total production), secondary vinyl plasticizers (24%), flame
retardants in rubber, plastics, and paints (27%), and traffic paint additives (4%)
Information on the quantities used in the various applications is somewhat
contradictory and could use some clarification. The viscosity of the liquid
formulations and the ability to slowly release hydrogen chloride at elevated
temperatures allows the chlorinated paraffins to be used as boundary and extreme
pressure lubricant additives. Chlorinated paraffins are used as secondary
plasticizers, mostly in polyvinyl chloride (PVC), to reduce the cost and maintain
the flame retardancy of the resin. Other plasticizers, such as diethylhexyl
phthalate, increase the flammability of the final product, and conventional flame
97
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retardant plasticizers, such as organophosphate esters, cause poor low temperature
properties for the resin. Chlorinated paraffins can be used as flame retardants
because they degrade at elevated temperatures to yield hydrogen chloride, which
is effective in retarding combustion. Sizable quantities of chlorinated paraffins
are also used in chemically resistant paints, such as traffic and marine paints.
The chlorinated paraffins have also been suggested as Aroclor (PCB's) replacements,
especially in rubber-based paints and adhesives. These markets for chlorinated
paraffins (especially the flame retardant applications) will likely continue to
grow at appreciable rates (oil additives, V>%/year; others, 10-35%/year).
No published field monitoring data are available on the amounts of chlorinated
paraffins that are released to and accumulate in the environment, although some
monitoring data for Great Britain should be available shortly. Much of this
paucity of information is attributable to the lack of specific and sensitive
analytical methods. Gas chromatography using electron capture detection or
combined with mass spectrometry has been evaluated and considered unacceptable for
chlorinated paraffins. With the shorter chained (Cg - Cjy) chlorinated paraffins,
where the compounds are volatile enough to pass through a gas chromatographic
column, a relatively specific microcoulometric-gas chromatographic technique has
been devised that is capable of measuring 0.5 ppm in fish flesh. With the higher
chained (C2Q - C30) chlorinated paraffins, only the very non-specific direct
injection microcoulometric detection method has been used at 1 ppm concentrations.
Neither of these methods is capable of measuring chlorinated paraffins at back-
ground environmental levels. It has been suggested that a combination of liquid
chromatography with microcoulometric detection would be a very appropriate system
for analyzing trace amounts of chlorinated paraffins.
98
-------
Although there is no conclusive evidence that chlorinated paraffins are
released into the environment, many of their applications are identical to the
ones suspected as being the major source of polychlorinated biphenyl (PCB)
contamination. Release of chlorinated paraffins used as oil additives to
water resources and landfills is probably very sizable, since waste oil is
frequently not recovered and this application is a major market for chlorinated
paraffins. Chlorinated paraffins may also reach the environment as plasticizers
in plastics (discarded in solid waste), by leaching from traffic and other paints,
and as components of materials that have chlorinated paraffins incorporated in
them for flame retardancy (also discarded in solid waste). Some quantitative
estimates of the losses were made in this report but were based only on
speculation.
Only a limited number of studies have been conducted on the fate of
chlorinated paraffins that might reach the environment. The biochemical oxygen
demand for several Chlorowax formulations (aqueous suspensions) has been
determined by the dilution bottle and Warburg technique. One of these formulations
(Chlorowax 500C) seems to be relatively biodegradable based on oxygen consumption,
but it is difficult to assess the extent of degradation or whether only selective
isomers are being degraded. Loss of "apparent chlorine" content (direct injection
microcoulometry) from both anaerobic and aerobic sediments that were spiked with
chlorinated paraffins has been observed. However, no information is available on
the structure of the degradation products and no radiolabelled studies have been
reported.
The chlorinated paraffins that reach the environment are probably less
mobile than PCB's. The chlorinated paraffins are less thermally stable than
99
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i PCB's and, therefore, are most likely destroyed rather than volatilized in
conventional incineration processes. However, experimental data confirming
l this behavior is lacking. The water solubility of chlorinated paraffins has
; not been exactly measured, but is extremely low and is probably lower than
i
PCB's based on molecular weight considerations. This could suggest that
I chlorinated paraffins will probably migrate very slowly through soil (leach
from landfills). Experimental evidence is available demonstrating that
the parent compounds (both lower and higher molecular weight formulations)
are not bioaccumulated by juvenile Atlantic salmon or fingerling rainbow trout
when the chlorinated paraffins are administered by adsorption on silica or by
incorporation in the fish food. The possibility of the bioaccumulation of
degradation products has not been studied.
- Dermal application of chlorinated paraffins to human skin apparently does
not produce local irritation or allergic sensitization. Furthermore, acute
studies in non-human mammals have demonstrated that chlorinated paraffins
possess extremely low toxicity when administered by oral, topical, and inhalation
routes. Clearly lacking in the literature, however, are long term studies and
investigations aimed at the determination of toxic reactions to chlorinated
paraffin impurities and degradation products. Similarly, the question of bio-
transformation and metabolic activation of chlorinated paraffins into potentially
harmful substances has not been answered as yet.
It is known, however, that the addition of chlorinated paraffins to the
diet or in the water of various fish species will produce significant mortality
and numerous sub-lethal effects. Further studies are indicated which should
be designed to characterize and identify the mechanisms of action and true proxi-
mate substance involved in producing these toxic reactions.
100
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Because the only toxicity thus far shown to result from exposure to
chlorinated paraffins has involved subacute (>24 hrs.) administration in
fish, it would seem worthwhile to explore possible subacute effects in higher
animals. This type of study is particularly valuable since subacute administration
more closely resembles environmental exposure. In addition, subacute exposure
often involves different target organs than single dose treatments, and allows
for the assessment of repeated damage to organs and organelles.
Thus, because of the limited data available, a conclusive environmental
hazard assessment of chlorinated paraffins is not possible at this time. How-
ever, from the available information, it seems safe to state that the chlorinated
paraffins pose less of an environmental hazard than PCB's at comparable
contamination levels (a similar conclusion is reached by Zitko and Arsenault,
1974). Chlorinated paraffins are much less persistent, do not appear to
bioaccumulate, and are less acutely toxic. However, there are considerable
gaps in the available information. No published monitoring data are available
yet; the chemical structure, bioaccumulation potential, and toxicity of the environ-
mental degradation products are unknown; and the available toxicity data are
completely inadequate for assessing possible detrimental effects from trace
contamination. Sizable quantities of chlorinated paraffins are probably reaching
the environment. Without the above- mentioned information, the hazard of environ-
mental contamination by chlorinated paraffins cannot be fully evaluated.
101
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