r Reference1

NBS

PUBLICATIONS

NATL INST. OF STAND & TECH

NBSIR 85-326tL^

AlllDS Tfi37fiE

A Summary of the NBS Literature

Reviews on the Chemical Nature and

Toxicity of the Pyrolysis and

Combustion Products from Seven

Plastics: Acrylonitrile- ButadieneStyrenes (ABS), Nylons, Polyesters,

Polyethylenes, Polystyrenes, Poly(Vinyl

Chlorides) and Rigid Polyurethane Foams

Barbara C. Levin

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Fire Research

Gaithersburg, MD 20899

June 1986

Sponsored in part by:

g Consumer Product Safety Commission

sda. MD 20207

100

.056

85-3267

1986
4
NBS

RESEARCH

INFORf/ATION CENTER

NBSIR 85-3267

A SUMMARY OF THE NBS LITERATURE

REVIEWS ON THE CHEMICAL NATURE AND

TOXICITY OF THE PYROLYSIS AND I COMBUSTION PRODUCTS FROM SEVEN

PLASTICS: ACRYLONITRILE-BUTADIENESTYRENES (ABS), NYLONS, POLYESTERS,

POLYETHYLENES, POLYSTYRENES, POLY(VINYL

CHLORIDES) AND RIGID POLYURETHANE FOAMS

Barbara C. Levin

U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Fire Research

Gaithersburg, MD 20899

June 1 986

Sponsored in part by:

The U.S. Consumer Product Safety Commission

Bethesda, MD 20207

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS. Ernest Ambler. Director

Table of Contents

Page

Abstract 1

1.0 Introduction 2

2.0 Scope 3

3.0 Thermal Decomposition Products 4

4.0 Toxicity 9

5.0 Conclusion 13

6.0 Acknowledgements 14

References 15

iii
List of Tables

Page

Table 1. Results of Bibliographic Search 17

Table 2 . Thermal Degradation Products 18

Table 3. Test Methods Used to Assess Toxicity of the Thermal

Decomposition Products of Seven Plastics 26

Table 4. LC^q Values 27

iv
A Summary of the NBS Literature Reviews on the Chemical Nature and Toxicity of

the Pyrolysis and Combustion Products from Seven Plastics: Acrylonitrile

Butadiene -Styrenes (ABS) , Nylons, Polyesters, Polyethylenes , Polystyrenes,

Poly(Vinyl Chlorides), and Rigid Polyurethane Foams

Barbara C . Levin

Abstract

A series of literature reviews was undertaken by the National

Bureau of Standards to examine the toxicity and chemistry of the

effluents produced when seven plastics were decomposed under

various thermal and atmospheric conditions. These plastics are:

acrylonitrile -butadiene- styrenes , nylons, polyesters, polyethylenes, polystyrenes, poly(vinyl chlorides), and rigid

polyurethane foams. The English language literature on each of

these was reviewed and published as a separate report of the

National Bureau of Standards . Over 400 different thermal

decomposition products, many common to more than one plastic, were

identified. The toxicity of most of these individual products is

unknown and an assessment of the toxicity of the multitude of

possible combinations is not feasible at this time. Therefore, a variety of bioassay toxicity protocols have been used to assess the

toxicity of the gaseous atmospheres generated by the thermal

decomposition of these plastics. In general, these seven plastics

did not produce unusually or extremely toxic pyrolysis or combustion products when compared to those of other synthetic or natural materials. In a few cases involving additives, toxic

products of concern were produced.

Ke)rwords : ABS plastics; chemistry; combustion products; literature

reviews; nylon; polyester; polyethylene; polystyrene; polyvinyl

chloride; pyrolysis products; polyurethane foams; rigid foams.

1
1.0 Introduction

More people per capita die in the United States and Canada as a result of

fires than in any other industrialized nation [1]^. Eighty percent of these

fatalities are attributed to the inhalation of smoke and toxic gases, not to

burns [2]. Therefore, the need to determine the degree of toxicity produced

from materials thermally decomposed under various fire conditions is evident.

In addition, the increased variety of plastics in buildings and homes has

raised the issue of whether synthetic materials may produce unusually or

extremely toxic combustion products. At least one case has been documented in

which a non- commercial fire retarded rigid polyurethane foam produced an

unusual toxic combustion product [3]; to a large extent, it was this case which

flamed the widespread interest in the field of fire toxicology.

Based on use in consumer products, the Consumer Product Safety Commission

(CPSC) prepared a list of the major types of plastics found in residences,

where the majority of fire deaths occur. Under joint sponsorship with CPSC,

the National Bureau of Standards (NBS) undertook a series of literature reviews

to examine the toxicity and chemical identification of the gases produced when

seven of the predominant synthetic materials [acrylonitrile-butadiene-styrenes

(ABS) , nylons, polyesters, polyethylenes , polystyrenes, poly(vinyl chlorides)

(PVC) , and rigid polyurethane foams] were decomposed under various thermal and

atmospheric conditions.

^ Numbers in brackets refer to the literature references listed at the

end of this report.

2
2.0 Scope

This report summarizes the major findings of reviews of the literature

conducted by NBS on the chemical nature and toxicity of the pyrolysis and

combustion products of seven plastics: acrylonitrile -butadiene -styrenes (ABS)

,

nylons, polyesters, polyethylenes , polystyrenes, poly(vinyl chlorides) (PVC)

,

and rigid polyurethane foams. For specific details, the reader is referred to

these reviews [4-10] and to the original literature referenced therein.

Prior to writing these reviews, a total of ten data bases (Chemical

Abstracts, Environmental Abstracts, Excerptica Medica, FRIS Library, Medline,

NTIS, RAPEIA, RTECS, TRIS , and Toxline) were searched for pertinent publications

on ten common plastics (those listed above plus acrylics, phenolics, and

polypropylenes). A summary of this literature search, including the number of

citations found for each selected plastic in each data base, is shown in Table

1. Recent articles were found through manual searching of current journals and

additional references were identified in the bibliographies of the acquired

reprints. Following completion of the computer and library searches, detailed

reviews were conducted of the research published in English on the seven

plastics noted above. Bibliographies and pertinent reprints on the remaining

three plastics, acrylics, phenolics, and polypropylenes, were compiled and sent

to CPSC, where detailed reviews of these were conducted.

3
3.0 Thermal Decomposition Products

The thermal decomposition products generated during the pyrolysis or

combustion of polymers depend upon their chemical composition, molecular

structure, and polymer formulation, which may include a variety of additives,

such as plasticizers, stabilizers, flame retardants, cross-linking agents,

fillers, and blowing agents. In addition, the conditions of thermal degradation, e.g, temperature, oxygen availability and ventilation, will affect the

nature of the generated effluent. The number and type of compounds detected

and reported in the literature also depend on the chemical techniques employed

and the combustion products of special interest to the investigators performing

the studies.

Table 2 shows that over 400 different thermal decomposition products have

been measured from these seven plastics and many of these products are common

to more than one of the plastics [4-10]. In general, these products were

detected through the use of the following analytical techniques: gas chromatography alone or in combination with mass spectrometry, infrared spectroscopy,

specific ion electrodes, high pressure liquid chromatography, wet chemical

procedures, colorimetric techniques, and colorimetric indicator tubes (Draeger

tubes). The absence of a product from this table or from the list for a

^ Certain commercial equipment, instruments, or materials are identified

in this paper in order to adequately specify the experimental procedure. In no case does such identification imply recommendation or endorsement by the

National Bureau of Standards, nor does it imply that the equipment or material

identified is necessarily the best available for the purpose.

^ The use of colorimetric tubes, such as Draeger tubes provides

unreliable and, at best, semiquantitative results [11].

4
particular plastic only means that none of the investigators whose work was

reviewed detected that compound. Lack of detection may indicate that the

compound was not produced under the selected experimental conditions , that the

particular analytical techniques were not suitable for that compound, or that

the investigator did not specifically analyze for that compound. For example,

benzene was found in the combustion atmospheres of all the reviewed plastics

except ABS . However, since benzene was one of the reported compounds from

polystryrene and ABS contains styrene, it is extremely likely that ABS would

also generate benzene.

Knowledge of the chemical composition, molecular structure and formulation of the polymer under study can provide some indication of the gaseous

products which may or may not be generated under specified experimental

conditions. For example, under vacuum or inert atmospheres,^ polymers whose

chemical formulation does not include oxygen, e.g., ABSs, polyethylenes

,

polystyrenes, and PVCs, would not be expected to produce oxygenated thermal

degradation products. (In some cases, such products were detected and probably

indicate the presence of leaked or trapped air or oxygen- containing additives

in the compounds [4,5,6].) On the other hand, polymers containing oxygen in

their molecular structure (e.g., polyesters, rigid polyurethane foams, and

nylons) would be expected to produce oxygenated volatile gases, such as carbon

monoxide (CO) and carbon dioxide (CO2 ), even in the absence of oxygen in the

^ Examination of materials under oxygen- free conditions does not simulate

real fire situations. However, such studies provide information on the

generation of thermal decomposition products under controlled experimental

conditions and possible effects of vitiated atmospheres which are common in

fires. In actuality, many of the products produced under inert atmospheres are also detected in oxidative environments.

5
atmosphere. ABSs, rigid polyurethanes, and nylons would be expected to produce

nitrogen-containing compounds, such as hydrogen cyanide (HCN) , regardless of

the atmosphere under which they were decomposed; whereas, PVC would not be

expected to produce such nitrogeneous compounds. As shown in Table 2, some

PVCs were found to generate nitrogen- containing products, including HCN. These

most likely indicate the presence of a nitrogen- containing additive or possible

contaminant. For example, Levin et al . examined a PVC containing zinc ferrocyanide (an additive designed to suppress smoke) which produced large amounts

of HCN [9,12]. Hydrogen cyanide has also been detected in the decomposition

products of some non-nitrogen- containing PVC copolymers, for example, a vinyl

chloride-vinylidene chloride copolymer [13]; therefore, one should be cautious

when examining generic materials of unknown formulation. In a similar fashion,

based on molecular structure, PVC is the only one of these seven plastics which

would be expected to produce chlorinated degradation products. However,

widespread usage of halogenated fire retardants in plastic formulations makes

predicting materials which will produce halogenated combustion products

extremely difficult.

Complete combustion in excess oxygen of a polymer containing carbon,

hydrogen, oxygen, and nitrogen yields CO2

, water (H2 O) and nitrogen dioxide

(NO2

) . It is during incomplete combustion under various atmospheric conditions

in either flaming or non- flaming modes that the many compounds listed in Table

2 are generated. When oxygen is limited, the primary gases formed during the

combustion of most materials are CO, CO2 and H2 O. In addition to CO, which is

a major toxicant produced by all seven plastics, other principal thermooxidative products of toxicological concern as noted in these reviews were HCN from

6
ABSs, nylons, and rigid polyurethane foams; ammonia (NH3 ) and NO2 from nylons;

acrolein from polyethylenes ; styrene from polystyrenes; and hydrogen chloride

(HCi) and benzene from PVC [4-10] . While the toxicity of these chemicals is

fairly well documented, the toxicity of many of the other individual compounds

listed in Table 2 is unknown.

Temperature plays an important role in influencing the production of

decomposition products. In general, as the temperature and thus the rate of

decomposition increases, the quantity of the more complex compounds and heavier

hydrocarbons decreases and the concentrations of CO and CO2 increase [4-10]

.

The generation of HCN has also been shown to increase as a function of temperature [4,7,10]. Another example is HCi, the detection of which begins when

stabilized PVC is heated to approximately 200°C; rapid dehydrochlorination then

occurs at 300° C [9]

.

The evolution of NO2 also increases with increasing

decomposition temperatures [7]. In contrast to these studies, however, more

acrolein was generated under lower temperature, non- flaming conditions than

under higher temperature, flaming conditions [6].

The presence of fire retardants, either additive or reactive, In plastics

can Influence the nature of the thermal degradation products . Halogenated

products will be generated when chlorine- and bromine -containing fire

retardants are used. With the exception of these two statements, it is

difficult to make generalizations about the effects of fire retardants on the

generation of combustion products and their resultant toxicity (see also

Section 4.0). This difficulty arises because, in most cases in the literature,

neither the exact formulation of the fire retardant nor that of the plastic has

7
been specified. In addition, the thermal decomposition conditions between

studies are usually so variable that comparison of results is not feasible.

Although large-scale room tests would better simulate real fire

situations, most of the reviewed studies have been conducted under small-scale

laboratory conditions. The large-scale room burns that were examined for these

reviews were usually complicated by the presence of multiple materials and

changing fire conditions [7,8]. Both of these factors prevent the assignment

of specific combustion products to individual materials or to particular

experimental conditions. On the other hand, small-scale tests are performed

under a variety of conditions which attempt to simulate different fire

scenarios. For example, non- flaming oxidative pyrolysis may represent the

early stages of a fire when the oxygen levels are high (>16%) and the heat flux

is low. Under these conditions, the gaseous effluents are complex and contain

many high molecular weight chemical species. Fires close to flashover can be

simulated in flaming tests conducted under higher heat fluxes and possibly low

oxygen conditions. In such tests, the combustion products are distinguished by

higher concentrations of thermally stable compounds (such as the aromatics) and

low molecular weight compounds (such as CO and CO2

)

.

When single materials are burned in large-scale tests and specific

toxicants are examined, such as in the work by Kuhn et al . cited in the review

on polyethylene [6], interesting and important information may be obtained.

For example, they found that acrolein concentrations in the large-scale tests

were too low to be of toxicological concern, whereas CO levels were at least

three times the amount needed to kill rats in 30 minutes.

8
Most of the reviewed studies did not examine the particulate matter which

is produced when these materials were thermally decomposed. The smoke

particulate and condensible matter are important for two reasons. First, many

of the thermal degradation products may condense or be absorbed by the soot

particles and be transported with the smoke. Hydrogen chloride is one example

of a compound that may be transported in such a fashion or may form a corrosive

acid mist in moist air [9] . One study of the particulate matter which formed

during the smoldering decomposition of a rigid polyurethane foam showed that

many compounds detected in the soot fraction were not found in the volatile

fraction [14]. Second, the particulate matter may interfere with the escape

and rescue of individuals from burning buildings by causing the obscuration of

vision and upper respiratory distress.

4.0 Toxicity

The surveyed literature showed that eight main toxicity protocols plus a

number of miscellaneous methods were used to assess the toxicity of the thermal

decomposition products from the seven plastics under review (Table 3) . These

methods are described briefly in the NBS reviews of the individual plastics [4-

10] . Detailed descriptions of the methods may be found in the book by Kaplan,

Grand and Hartzell [15] as well as in the original literature cited in the NBS

reviews

.

Two major problems hindered the review and assessment of the extensive

toxicological literature on this subject. First, pure materials were generally

9
not tested. In the majority of cases, materials were given generic

designations since their exact formulations were considered proprietary

information by their manufacturers. Additives commonly used in plastic

formulations, such as plasticizers, smoke suppressants, flame retardants,

cross-linking agents, stabilizers, etc., were usually unspecified and, many

times, unknown. Therefore, the likelihood of the same material being examined

by two or more investigators is extremely low. Only in a few cases, as in the

interlaboratory evaluation of the NBS Toxicity Test Method, were the identical

materials examined by a number of laboratories. Second, the variations in the

test methods were extensive and included different combustion systems,

temperatures of decomposition, heat fluxes, animal species, methods of animal

exposure, exposure durations, sizes of exposure chambers, types of exposure

(dynamic or static), air flow rates, biological endpoints and chemical measurements. Since the generated combustion atmosphere is dependent upon the above

factors and the resultant toxicity depends upon the gas concentrations in those

atmospheres, toxicological results from different test methods should not be

compared.

All the LCjq values (regardless of test methods, materials, animal

species, exposure times, etc.) for the selected generic classes of materials

were compiled in Table 4. The data in this table have to be examined with

caution and should be recognized as not being statistically representative.

For example, the LC^q values range from 3.8 to >320 mg/i and while these values

were both obtained with the University of Pittsburgh test method, the exposure

times were different (i.e., 30 min vs 10 min). Therefore, it would be

incorrect to assume the first material was two orders of magnitude more toxic

10
than the second.

There are no safe combustion atmospheres; they are only more or less

toxic when compared to those generated by other products or combinations of

products. Materials, therefore, can be classed in reference to each other or

to a specific material (Douglas fir and other species of wood have been

extensively used in the published literature for this purpose.) Toxicologists

have traditionally distinguished materials or compounds as being

toxicologically significantly different when their biological figures of merit

differ by an order of magnitude [16].^ Alarie and Anderson, for example, have

used this approach in designing their classification scheme for materials [17].

The toxicological data obtained in this series of reviews were analyzed

to determine if any of these seven plastics produce unusually or extremely

toxic thermal degradation products when compared to those produced by other

materials manufactured for the same end use. (For the purpose of this report,

unusually toxic refers to those cases where unexpected adverse physiological or

biological effects are produced; whereas, extremely toxic refers to those

situations where very small amounts of material relative to that from other

materials produce measurable toxicity.) This summary will not reiterate the

detailed findings which are provided in the reviews [4-10] , but rather will

concentrate on those materials which have been shown to be of toxicological

concern.

^ This statement should not be interpreted to infer that the quantitative

values obtained within a test method are also statistically significant only if

they differ by an order of magnitude. The statistical significance between

values within any one test method should be determined by each investigator in

his laboratory. He will most likely find it is less than an order of magnitude

11
The thermal degradation or combustion products of these seven plastics

generally do not appear to be xmusually or extremely toxic when compared to

those produced by other materials under similar laboratory conditions.

However, a few cases, involving additives, do stand out. For example, the case

mentioned in the introduction of this summary is a prime example of an unusual

toxic thermal degradation product. This product formed from a PAPI/propoxylated trimethylolpropane rigid polyurethane foam containing the reactive

fire retardant 0 , 0-diethyl-N,N-bis- (2-hydroxyethyl)aminomethyl phosphonate

[10]. The combination of this foam and this fire retardant, when decomposed

under non- flaming conditions, produced a highly toxic bicyclic phosphate ester,

which caused adverse and unexpected neurological effects in exposed rats.

A smoke suppressant, zinc ferrocyanide , has also been shown to increase

the toxicity of materials [9,10,12]. The decomposition products of a rigid

polyurethane foam with zinc ferrocyanide were twice as toxic as those found for

the foam without this additive [10]. When testing a zinc ferrocyanide -PVC

formulation. Levin et al . found that both the non-flaming and flaming decomposition products from a mass loading equivalent to 30 mg/i caused deaths of

100% of the rats exposed for only 10 minutes . Under the same experimental

conditions, this PVC formulation without zinc ferrocyanide killed only 8% of

the exposed animals [12]. This PVC with zinc ferrocyanide was classified by

Alarie and Anderson in their most toxic category, i.e., "much more toxic than

wood" [18], as was a polychloroprene which also contained zinc ferrocyanide

[17,18]. In both of these cases, the increased toxicity was attributed to the

generation of HCN. Neither of these products was ever commercially available.

12
5,0 Conclusion

The toxicity of the thermal decomposition products from most of the

tested synthetic materials that have been reviewed here appears to be

comparable to that from other synthetic or natural materials formulated for

similar end uses. The existence of the few exceptions, however, generates

concern about the possibility that other untested materials or future formulations may produce unusually or extremely toxic thermal degradation products.®

Based upon the data presented in the reviewed literature, it is not presently

possible to determine the toxicity of the thermal effluents of current products

or to predict that of new materials without some form of toxicity testing. It

Is, therefore, essential to have a means to assess the acute inhalation

toxicity of a material's combustion products.

Although it was beyond the scope of these reviews to examine total toxic

hazard, it is important to realize that it is the toxic hazard generated by a

material in a specific end use that must be evaluated before decisions are made

as to a material's acceptability for that use. Although toxicity is one of the

important factors in a toxic hazard assessment, other factors which must be

considered include: the quantity of material, its configuration, the proximity

of other combustibles, the volume of the compartments to which the combustion

products may spread, the ventilation conditions, the ignition and combustion

® The results presented here refer specifically to the seven plastics

reviewed. There is at least one other documented case of a material which was not reviewed and which produces extremely toxic pyrolysis and combustion

products [12]

13
properties of the material ( s) , the presence of ignition sources, the presence

of fire protection systems, and the building occupancy [12].

6 .

0

Acknowle dgement s

The author gratefully acknowledges the help of Ms. Robin Breese, who

compiled the information in Table 2. This study was supported in part by the

Consumer Product Safety Commission, Dr. Rita Orzel, Project Officer, under CPSC

Task Order No. 84-8.

14
References

1. Fire in the United States, 2nd Ed., Federal Emergency Management Agency,

Report FEMA-22, July 1982.

2. Birky, M. M. , Halpin, B. M. , Caplan, Y. H. , Fisher, R. S., McAllister, J.

M. , and Dixon, A. M. , Fire fatality study. Fire & Matls. 3:211-217

(1979) .

3. Petajan, J. H., Voorhees , K. J., Packham, S. C. , Baldwin, R. G. , Einhorn,

I. N., Grunnet, M. L. , Dinger, B. G., and Birky, M. M. , Extreme toxicity

from combustion products of a fire-retarded polyurethane foam. Science

1^:742-744 (1975).

4. Rutkowski, J. V. and Levin, B. C., Acrylonitrile -butadiene -styrene

copolymers (ABS) : pyrolysis and combustion products and their toxicity - A review of the literature. Nat. Bur. Stand, Gaithersburg, MD, (U.S.),

NBSIR 85-3248, December 1985.

5. Gurman, J. L. , Baier, L. , and Levin, B. C., A literature review of the

chemical nature and toxicity of the thermal degradation products of

polystyrenes. Nat. Bur. Stand., Gaithersburg, MD (U.S.), NBSIR 85-3277,

March 1986.

6. Paabo, M. and Levin, B. C. , A literature review of the chemical nature

and toxicity of the decomposition products of polyethylenes . Nat. Bur.

Stand., Gaithersburg, MD, (U.S.), NBSIR 85-3268, January 1986.

7. Braun, E. and Levin, B. C., Nylons: A review of the literature on products of combustion and toxicity. Nat. Bur. Stand. , Gaithersburg, MD,

(U.S.), NBSIR 85-3280, February 1986.

8. Braun, E. and Levin, B. C. , Polyesters: A review of the literature on products of combustion and toxicity. Nat. Bur. Stand, Gaithersburg, MD,

(U.S.), NBSIR 85-3139, June 1985.

9. Huggett, C. and Levin, B. C., Toxicity of the products of combustion of

poly (vinyl chloride) in fires: A literature assessment. Nat. Bur.

Stand., Gaithersburg, MD (U.S.), NBSIR 85-3286, April 1986.

10. Paabo, M. and Levin, B. C., A review of the literature on the gaseous

products and toxicity generated from the pyrolysis and combustion of

rigid polyurethane foams. Nat. Bur. Stand., Gaithersburg, MD (U.S.),

NBSIR 85-3224, December 1985.

11. Standard Guide for Measurement of Gases Present or Generated During

Fires. ASTM E800-81, American Society for Testing Materials,

Philadelphia, PA (1984).

15
12. Levin, B. C. , Fowell, A. J., Birky, M. M. , Paabo, M. , Stolte, A., and

Malek, D. , Further development of a test method for the assessment of the

acute inhalation toxicity of combustion products. Nat. Bur. Stand,,

Gaithersburg, MD, (U.S.) NBSIR 82-2532, June 1982.

13. Michal, J., Toxicity of pyrolysis and combustion products of poly(vinyl

chloride). Fire and Matls. 1:57-62 (1976).

14. Joseph, K. T. and Browner, R. F. , Analysis of particulate combustion

products of polyurethane foam by high performance liquid chromatography

and gas chromatography - mass spectrometry. Anal. Chem. 52 : 1083-1085

(1980)

.

15. Kaplan, H. L. , Grand, A. F. , and Hartzell, G.E., Combustion Toxicology,

Principles and Test Methods. Technomic Publishing Co., Inc., Lancaster,

PA, 1983.

16. Casarett and Doull's Toxicology, 2nd Edition, Ed. by J. Doull , C. D. Klaassen, and M. 0. Amdur, Macmillan Publishing Co,, Inc, New York, 1980.

17. Alarie, Y. and Anderson, R, C., Toxicological classification of thermal

decomposition products of synthetic and natural polymers. Tox. & Appl.

Pharm. 57:181-188 (1981).

18. Anderson, R. C., and Alarie, Y. C., Screening procedure to recognize

"super toxic" decomposition products from polymeric materials under

thermal stress. J, Comb. Tox. 5:54-63 (1978).

19. Anderson, R. C., Croce, P. A., Sakura, J. D, , Study to assess the

feasibility of incorporating combustion toxicity requirements into

building material and furnishing codes of New York State. Final report

to Dept, of State, Office of Fire Prevention and Control, Albany, NY,

A.D. Little, Inc. Reference #88712, May 1983.

20. Alarie, Y. , The toxicity of smoke from polymeric materials during thermal

decomposition. Ann. Rev. Pharmacol. Toxicol. 25,: 325-347 (1985).

16
Number

of

Articles

From

Each

Database

Environmental

Excerptica

Chemical

Toxllne

FRIS

Medline

RTECS

Abstracts

NTIS

Medlca

RAPRA

Abstracts

Total

Materials

1966-84

Library

1966-84

1979-84

1971-84

1964-84

TRIS

1974-84

1972-84

1972-84

-a* <r>. -a

-a

O'

in

00o

fNj «a 00o

o

c^ m(N|

r>4

rsi

o es o O' 00 o O' <r rJ r>j cn ^a fN* <N| m

0) 1 c >>

0) V) 0) u

C 0) u S u tA c 0) O 0) >> c U o 4J o. c

> -H u 0) •w 0) c« w u 0] c 1 ^ 0 1 >» 0) •O £ u

0 >s o >v >» c >* >v Cu >v V ^ JS 0 U c/3 ^ o OO 0) c O pC o 0 U o 0 u o $

Pu U Qu z Qu 0) Qu < 3 ou a 04 o: 0 o H

17

0

-

No

articles

found

to

date

General

-

Articles

which

cover

more

than

one

plastic
TABLE 2. THERMAL DEGRADATION PRODUCTS [4-10,13]

Compound RPU PEST ABS PE PS PVC NYLON

Acetaldehyde ' X X X

. X X Acetamide X

- - - - - - Acetic acid X X

- X

- - - Acetone X X

- X

- - X Acetonitrile X

- - - - X X

Acetophenone - X X

- X

- - Acetylene X

- - X X

- - p-Acetyl benzoic acid - X

- - - - - p-Acetyl vinyl benzoate - X

- - - - - Acids (-COOH) “ - X

“ “ “

Acrolein X X X X X

- - Acrylaldehyde - - - - X

- - Acrylic acid - - - X

- - - Acrylonitrile X

- X

- - X X Adiponitrile “ “ “ ** X

Aldehydes (total) (HCHO) - - X

- - - - Alkene X

- - - - - - Allene X

- - - - - - Allyl alcohol - X

- - - - - Allylbenzene - “ - • X

“

Allylic chlorides - - - - - X

- Ammonia X

- - - - - X Ammonium carbonate - - - - - - X Aniline X

- - - - - - Aniline hydrochloride X

- - - - - “

Anthracene - - - X

- - - Benzaldehyde - X X

- X X

- Benzene X X

- X X X X Benzene + n-methylpyridine - - - - - - X Benzoanthracene - - “ X

“ “

2 , 13-Benzofluoranthene - - - X

- - -

1 , 2-Benzofluorene - - - X

- - - 2 , 3-Benzofluorene - - - X

- - - Benzo(a)pyrene - - - X

- - - BenzoCc )pyrene - X

“

Benzoic acid - X

- - X

- - Benzonitrile X

- - - - - - Benzoqu incline X

- - - - - - Benzyl alcohol - - - - X

- - Biphenyl * X

* “

Butadiene X X

- X X X X

Butcinal - - - X

- - “ Butanaldehyde - X

- - - - - Butane - X

“ X

- - X Butane + Butene - - - - “ X

n-Butane - - - - - X

- Butene - X

- X

- X X 1-Butene X

- - X X

- -

1 -Butene- 3-yne X

- - - “ - - 2-Butene, cis - - X

“

2-Butene , trans - - - X

- - - Butyr aldehyde X

- - - - - - Butyric acid - - - X

- - - Butyrolactone - - - X

- “ - C^, C^, and species - - “ “ X

18
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS FVC NYLON

c, - C

_ _ _ - X

4 10 Cg H

_ _ - - X

- - Caprolc acid - - - X

- - - Caprolactam “ - - “ ” X Carbon dioxide X X X X X X X

Carbon monoxide X X X X X X X

C^-Acetaldehyde - - - - - - X

Cj-Acetaldohyde - - - - - - X

C^-Alcohols - - - - - - X

C2“benzene - - “ • “ X

Cj-Benzene - - - - - - X C^-lactam - - - - - - X Cg-lactam - - - - - - X

Cjj^-lactam - - - - - - X

Cj^j^-nitrile - - “ • X

Carbon tetrachloride X

- - - - - - Chlorine X - - - - - - Chlorobenzene X - - - - X

- p-Chlorobenzonitrile - - - - - X

- Chloroethane X

- “ - - X

-

Chloroethanol X

- - - - - - Chloroethylene X

- - - - X

- Chlorolsopropanol X

- - - - - Chloromethane X

- - - - X

- Chloronaphthalene - - - - “ X

-

Chloropropeno - - - - - X

- Chloropropyleno X

- - - - - - Chloropyridine - - - - - X

- Chlorostyrene - - - - - X

- Chrysene - • X

• “ “

Cinnamaldehyde - - - - X

- - Cresol - - X

- - - X Crotonlc acid - - - X

- - - Cumene - - - - X

- - Cyanobenzene - - - - - X

Cyc lobutanone - X

- - - - - Cyc loheptanone - - - - - - X

Cyc lohexadl ene - X

- - - X- Cyclohexane - X

- X

- - - Cyc lohexanone X

* • X

Cyc lohexanonoxlme - - - - - - X Cyclohexene - X

- X

- X X Cyc lopentadlene - - - - - X X Cyclopentane - - - - - X

“ Cyc lopentanone • X

” ” X

Cyclopentene - X

- - - X X 2-Cyclopentylidinecyclopentanone - - - - - - X 2-Cyclopentylcyclopentanone - - - - - - X Cyclopropane - - - X

- - - Decadlene “ “ ” “ “ - X

Decanal - - - X

- - - Decane - - - X

- - - Decene - - - - - - X 1-Decene - - - X

- - - Decylnitrile - - - - - - X

19
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS PW NYLON

Diacetyl benzene - x>- 4, 4 ’-Di amino dimethyl diphenylmethane x

- - - - 4,^ ’-Diamino diphenylmethane x

- - - - 4, 4 ’-Diamino methyl diphenylmethane x

- - - -

4, 4 ’-Diamino trimethyl diphenylmethane x

- - - -

“

Diazomethane

Dichlorobenzene

+ diazoethane

x_____ - - - - Dichlorobenzonitrile

p-Dichlorobenzonitrile

Dichlorobutadiene _____ _____ _____

X X

X

X

X

Dichlorobutylene

Dichlorocyclopentene

Dichloroethane x_____ _____ - - - -

X

X

Dichloroethylbenzene

Dichloroethylene _____ _____ X

X

Dichlorofluoromethane x

- - - - Dichloropentadiene

Dichloropentene

Dichloropropene

Dichlorotoluene _____ _____ _____ _____

X

X

X

X

Dihydropyran x

- - - - Dimethylbenzene - - x

- - Dimethyl benzotjuinoline x

- - - - 2,2-Dimethylbutane - - - x

-

X

Dimethylcyclohexene _____ X

2.2-

Dimethyl-cis-3-hexene ---x3.3-

Dimethylheptane - - - x

-

2.4-

Dimethylhexane - - - x

-

2, 3-Dimethyl- 1-hexene - - - x

- Dimethyloxymethane _____ X

2 , 3-Dimethylpentane - - - x

- Dimethylpyridine

2,6-Dimethyl quinoline x_____ - - - - Dimethyl toluidine x

- - - -

X

Dioxane _____ X

p-Dioxane

1,4 -Dioxane x_____ - - - - X

Diphenyl

Diphenyltimine x_____ - - - - X

Diphenylbutylene _____ X

Diphenylethane _____

1.3-

Diphenylpropane - - - - x

1.3-

Diphenylpropene - - - - x Dipropoxy-one-trimethylolpropane x

- - - - Dipropoxy-trimethylolpropane x

- - - -

X

Dipropoxydiene-trimethylolpropane x

- - - “ Dipropoxyene-trimethylolpropane x

- - - - Dipropropylene glycol methyl ether x

- - - - Di-tert-butyl

Divinyl benzenemethyl phenol _____ _____ Divinyl terephthalate - x

- - - Dodecanal - - - x

- Dodecane - - - x

- 1-Dodecene - - - x

- Epoxide - - - X

-

1

1

I

1

1

1

iI

1

1

1

1X

X

X

1

1

1

1

I

20
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS PVC NYLON

Ethanal - - X

- - - - Ethane X X

- X X X X

Ethanol X X

- X

- - X Ethene - X

- - - - X Ethylbenzene X X X X X

Ethylbenzene & xylene - X

- - - - - Ethyl benzoate - X

- “ - - - Ethyl cyclopentene - - - X

- - - Ethylene X X

- X X X X Ethylene & Acetylene “ X

“ “ " " •

Ethylene oxide X

- - - - - - 2-Ethyl-l-hexene - - - X

- - - Ethylmethylbenzene - - X

- X- - A-Ethyl-l-phospha-2,6,7-

trloxablcyclo[2. 2. 2] octane-1-oxlde X

- - - - - [blcycllc phosphate ester]

A -EthylquinoLine X

- - - - - - p-Ethyl toluene - X

- - - - - p-Ethyl vinyl benzoate - X

- - - - - Ethyl vinyl terephthalate “ X

" • •

Fluoranthene - - - X

- - - Fluor ene - X

- - - - - Formaldehyde X

- X X X

- X Formamide X

- - - “ -

Formic acid - - - X X

- - FREON X

- - - - - - Fur an - - - X

- - - Heptadecane - - - X

- - - 1-Heptadecene - - - X

- - -

Heptadiene - - - - - - X 1,3-Heptadiene - - - X

- - -

1 , 6-Heptadlene - - - X

- - - Heptanal - - - X

- - - Heptane “ X

“ “ X

2-Heptanone - - - X

- - - 3-Heptemone - - - - - - X Heptene - - - X

- - X 1-Heptene - - - X

- - - Hexadecane - X

- - -

1-Bexadecene _ - - X

- - - Hexadecylene - - - - - X

- Hexadiene - - - X

- - X 1,3-Hexadiene - - - X

- - - 1,5-Hexadiene - X

- X- - -

Bexamethylenedlamine - - - - - - X Hexamethylenelmine - - - - - - X Hexanal - - - X

- - - Hexane - - - X X

- X n-Hexane - - - - - X X

2-Hexanone - - - X

- - X Hexanltrlle - - - - - - X Hexenaldoxime-octadiene - - - - - - X Hexene - - - X X

- X 1-Hexene - - - X

- - -

21
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS PVC NYLON

1-Hexene, 2-methyl-l-pentene - - - - X

- _ 2-Hexene - - - X

- - -

3 -Hexene - - - X

- - - Hexylamine - - - - - - X Hydrocarbons - - - - X

“ X

Hydrocarbons (C^

)

X

- - - - - - Hydroc arbons (C^Hy

)

X

- - - - - - Hydrogen - X

- - X

- - Hydrogen bromide X

- - - - - - Hydrogen chloride X

- X X

“

Hydrogen cyanide X

- X

- - X X Hydrogen fluoride X

- - - - - - Hydroperoxide - - - X

- - - 1-Hydroxy ethyl benzoate - X

- - - - - Hydroxyvaleric acid - - - X

“

Indazole X

- - - - - - Indene - - - - - 4 X

- Indole X

- - - - - - Indoline + caprylic acid - - - - - - X Isobutanal - - - X

- - -

Isobutene X

- - X

- - - Isobutylene - - - X

- - - Isodecane - - - X

- - - Isononane - - - X

- - - Isooctane “ - - X

- “ “

Isoprene - - - - - - X Isopropropanol X

- - - - - - Isopropylbenzene - - X

- X

- - Isovaleric acid - - - X

- - - Isoxazole X

- - - - “ “

Methane X X

- X X

- X Methanol X

- - X X

- X Methylacetylene X

- - - - - - p-Methyl acetophenone - X

- - - - - Methylanthracenes & Methylfluorenes X

“ “ “ **

Methyl benzoate - X

- - - - -

3 -Methyl benzoquinoline X

- - - - - - Methylbutadiene - - - - “ - X Methylbutane & Methylbutylene - - - - - - X 2-Methylbutane “ “ X

“

2 -Methyl- 1-butene X

- - X

- - - 3-Methyl- 1-butene - - - X X

- - Methylcaprolactam - - - - - - X MethyIcyc lohexane - - - X

- - - MethyIcyc lohexanone “ “ “ - X

MethyIcyc lohexene - - - X

- X

- MethyIcyc lopentane - - - - - - X 3-Methylcyclopentanone - - - - “ X MethyIcyc lopent ene - * - X

“ X X 2-Methyl- 1, 3-dioxane “ “ “ X

A , 5-Methylene phenanthrene - - - X

- - - 2-Methyl-A-ethylhexane - - - X Methyl ethyl cyclopentane - - - - “ X

“ Methyl ethyl ketone X

- - X

“ “ “ 2-Methy 1-3-ethyl pentane - - “ X

“ “ “

22
THERMAL DEGRADATION PRODUCTS (continued)

Compound

2 -Methy 1- 3 - ethy1- 2-pentene 2-Methylheptane

2-Methyl-l-heptene

2-

Methyl-3-hoptone

3-

Methyl- 1-heptene

2-

Methyl- 1-hexene

3-

Methyl- 1-hexene

h -Methyl- 1-hexene

k -Methy1-2-hexene Methyl 1-hydroxyethyl terephthalate

Methyl Indane Methylmethacrylate

Methyl-A, 5-methylene phenanthrene

2-Methylpentane

2-Methyl- 1-pentene

2-Mothyl-2-pontone

2-Methyl-3-pentene

h -Methyl- 1-pentene

Methy1-phenanthrene

MethyIphenol

2-Methyl propane

2-Methyl propenal

2-Methyl-2-propenal

2-Methylpropene

MethyIpyrene

2-

Methylpyridine

MethyIquino line MethyInaphthalene

Methylstyrene

a-Methylstyreno

b-Methylstyrone

p-Methyl vinyl benzoate

Methyl vinyl ketone

Monoproproxy-trimethylolpropane

Naphthalene

Nitric oxide

Nitrogen dioxide

Nitrogen oxides

1.3-

Nonadiene

3-

Nonadlene

Nononal

Nonane

Nonene

1-Nonene Nonenylcyanide

Nonenylcyanide + nomonenylcyanide

Octadecane

1-Octadecene

1.3-

Octadlene

Octanal Octane

Octatriene

Octene Octene-pyridine

1-Octene Olefin

PS PVC NYLON

X

X

X

X

X

X X

X

X

X

X

X

X

X

X

23
THERMAL DEGRADATION PRODUCTS (continued)

Comtsound RPU PEST ABS PE PVC NYLON

Oxygen - - - - X

- - Pentadecanal - - - X

- - - Pentadecane - - - X

- - - 1-Pentadecene - - - X

- - - Pentadecylene - “ - - X

Pentadiene - - - X

- - X 1,3-Pentadiene - X

- X

- - - 1,4 -Pentadiene - X

- X

- - - Pentanal - - - X

- - - Pentane “ - - X X

- X

2-Pentanone - - - X

- - - Pentene - X

- X X X X Pentene-1 - - - - - - X

1-Pentene - - - X

- - - 2-Pentene - - - X

- - -

4-Pentene-l-ol - X

- - - - - n-Pentene - - - - - X

- Phenanthrene - - - X

- - - Phenanthrene & Anthracene - X

- - - - -

3 , 8-Phenathroline X

- - - - - - Phenol X X X

- X

- X

Phenyl cyclohexane - - X

- - - - p-Phenylenedi amine X

- - - - - Phenyl ethanol - - - - X

- - Phenylhutane - - - - - - X 2-Pheny1-2-propanol - - X

“ “ “

3-Phenyl- 1-propene - - X

- - - - N- Phenyl P-toluidine X

- - - - - “ Phosgene - - - - - X

- Pimelonitrile - - - - - - X Polycyclic aromatics X

- - - - “ ~

Propadiene - - - X

- - X Propanal - X

- - - X

- Propanaldehyde - X

- - - - - Propane X

- - X X X X Propanol - - - X

- - - n-Propanol X

“ “ “ “ “

Propene - X

- - - - X Propenitrile X

- - - - - - Propionaldehyde X

- - X

“ - - Propionic acid “ “ “ X

“ “

n-Propylbenzene - - X

- X X

- Propyl benzoate - X

- - - “ - Propylene X X

- X X X X Propylene oxide X

- - “ - - Pryene “ “ X

Pyridine X

- - - - - X Pyrole - - - - - - X Pyrolidine - - - - “ - X Quinoline X

- - - “ Quinone ” X

“

Styrene X X X

- X X X a-Styrene - - - - X

“ “ Styrene monomer - - - - X

“ - Styrene dimer - - - - X

- - Styrene trimer - - - - X

-

Ik
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS PVC NYLON

Styrene tetramer - - - - X

- - Styrene pentamer - - - X

“ “ Styrene hexamer - - “ X

“ Styrene heptaroer “ - - X

Styrene oxide ” “ X

Tertiary butyl methyl phenol - - - - - X

- Tetradecanal - - - X

- - - Tetradecane - - - X

- - - 1-Tetradecene - - - X

- - - Tetradecylene “ " • — “ X

Tetrahydrofuran - X

- X

- - - Tetrapropoxy-trimethylolpropane X

- - - - - - Tetrapropoxydiene-trimethylolpropane X

- - “ - - - Tetrapropoxyene-trimethylolpropane X

- - - - - - Toluene X X

• X X X X

2 , 4 -Toluenedi amine X

- - - - - - Toluene monoisocyanate X

- - - - - - Toluidine X

- - - - - - Toluidine hydrochloride X

- - - - - - N-tolyl butylurethane X

“ “

Tri chlorobenzene - - - - - X

- Trichlorobutylene - - - - - X

- 1,1, 2-Trichloroethane - - - - X

- Trichloroethyl phosphate X

- - - - - - Trichloroethylene “ “ “ “ * X

“

Trichlorofluoromethane X

- - - - - - Tri chloromethane - - - - - - X

Tri ch loropropane - - - - - X

- Tridecanal - “ - X

- - - Tridecane - - - X

“ “ -

1-Tridecene - - - X

- - - Trlmethylbenzene - - - - - X

- Trimethyl benzoqulnone X

- - - - - “ 2 , 3 , 3-Trimethyl-l-butene - - - X

- - - Trimethylcyclopentane - - X

•* X

2,2, 5-Tr imethylhexane - - - X

- - - Trimethylindole X

- - - - - - 2 , 2 , 3-Trimethyl-l-pentane - - - X

- - - 2 , 3 , 4-Trimethylpentane - - - X

- - “ Trimethylpentene • X

“

Trimethylquinoline X

- - - - - - Trimethyltoluidlne X

- - - - - - Triphenylene - - - X

- - - Tripropoxy-trimethylolpropane X

- - - - - - Tripropoxy-one-trimethylolpropane X

—

Tripropoxydiene-trimethylolpropane X

- - - - - - Tripropoxyene-trimethylolpropane X

- - - - - Tripropylene glycol methyl ether X

- - - - - - Undecanal - - - X

- - - Undecane - - - X

“

Undecanitrile + undecenitrile - - - - - - X Undecene + undecane - - - - - - X

1-Undecene - - - X

- - - Urea X

- - - - - - Valerolactone - - - - - - -

25
THERMAL DEGRADATION PRODUCTS (continued)

Compound RPU PEST ABS PE PS PVC NYLON

p-Vinyl acetophenone - X

- - - - - Vinyl benzoate - X

“ - - - -

Vinyl chloride - - - - - X

- Vinylcyclohexene - - - - X

- -

A -Viny1 - 1

- eye lohexene - - X

- - - - p-Vinyl toluene - X

- - - - - p-Vinyl vinyl benzoate - X

“ - - - -

Water X X

- X

- X X Xylene X

- - - - X

-

X: Compound was detected in the thermal degradation products from the designated material. Compound was not detected

RPU: Rigid polyurethane foam

PEST: Polyester

ABS : Acrylonitrile-butadiene-styrene

PE : Polyethylene

PS: Polystyrene

PVC: Poly (vinyl chloride)

26
Table 3

Test Methods Used to Assess Toxicity o£ the Thermal Decomposition Products of Seven Plastics

Test method

DIN

FAA^’

Japanese^

NASA/USF*^

NBS®

Michigan^

Pittsburgh*

Utah^

Misc

ABS Nylon

X X

X

X

X X

X X

X X

X

Materials

Polyester XXXPolyethylene Polystyrene

X

X - X XXXX

FVC

X

X

X

X

X

X

X

X

Rigid

Polyurethane

X

X

X

X

X

X

X

a - Method developed in response to German Coninisslon of Standards

b - Method developed at the Federal Aviation Administration

c - Includes a variety of test methods developed by Japanese

d - Method developed by National Aeronautic and Space Administration and University of

Sein Francisco

e - National Bureau of Standards test method

f - University of Michigan tost methods

g

- University of Pittsburgh tost method

h - University of Utah test method

i - Miscellaneous protocols; For details, see reviews of each material [4-10] X - method used

- - Method not used

27
Table 4

LC50 Values

Material

Test Procedure Animal

Snecies Mode

Exposure

Time

(min)

Post- Exposure

Time

LC^g Value

(mg/i) Reference

ABS

NBS rats F 30 0 15.6-22.1 4 NBS rats F 30 14 days 15.0-28.5 4 NBS rats NF 30 0 22.0-38.0 4 NBS rats NF 30 14 days 19.3-64.0 4 Pittsburgh mice M 30 10 min. 9.3-10.5 4 Michigan® mice NI 240 7 days 12.0-22.0 4 ABS/FR Michigan mice NI 240 7 days 13.3-14.0 4

Nylon

Polyamide NASA/USF mice M 47.5 0 32 7 6 NASA/USF mice M 30 0 11 7 yam Michigan rats M 240 7 days 31 7 fabric Michigan rats M 240 7 days 29 7 6.6 Michigan rats M 240 7 days 25 7 knit Michigan rats M 240 7 days 22 7 yam Michigan rats M 140 7 days 15 7 fabric Michigan rats M 140 7 days 9 7 6.6 Michigan rats M 140 7 days 10 7 knit Michigan rats M 140 7 days 11 7 FR FAA rats NI 30 0 86 7 6.6/FR Michigan rats M 240 7 days 25 7 Michigein rats M 140 7 days 11 7

Polyester

batting NASA/USF mice M 30 14 days 20 8 Pittsburgh mice M 30 10 min. 47 8 fiberfill NBS rats NF 30 14 days 28 8 NBS rats F 30 14 days 31 8 fabric DIN rats NI 30 NI 72 8 NBS rats NF 30 14 days 39 8 NBS rats F 30 14 days 38 8 commercial

resin Pittsburgh mice M 30 10 min. 58 8 experimental

resin Pittsburgh mice M 30 10 min. 96 8 glass fiber

reinforced Pittsburgh mice M 30 10 min. 112 8 U.S. Testing rats NF 30 14 days 122-138 8 U.S. Testing rats NF 30 14 days 63 8 fiber Japanese mice NI 60 7 days 31 8 glass fiber

reinforced/FR DIN rats NI 30 NI 48 8 FR U.S. Testing rats NF 30 14 days 76 8 U.S. Testing rats NF 30 14 days 38 8 Halogenated

resin Pittsburgh mice M 30 10 min. 24 8

28
Table 4 (continued)

Material

Tost Procedure Animal

Species Mode

Exposure

Time

(min)

Post- Exposure

Time

LCgg Value

(mg/f

)

Reference

Folyatfaylan*

Ethafoam 220 Dow rats F 30 14 days .35 6 Dow rats NF 30 14 days 5.3 6 XFS4100 Dow rats F 30 14 days 31.3 6 Dow rats NF 30 14 days - 6.1 6 wire

insulation NBS rats NF 30 14 days >75 6 MBS rats F 30 14 days 46 6 high density CMIR rats F 30 NI 48.4-51.2 6 CMIR rats NF 30 NI 24.7-25.2 6

Folyatyrec* Dow rats NF 30 14 days >40 5 Dow rats F 30 14 days <40 5 Harvard rats NF 20 21 days >128 5 Harvard rats F 20 21 days <128 5 Michigan rats M 240 7 days 19.3 5 Mlchlgem rats M 140 7 days 10.2 5 FM rats NI 30 14 days >60 5 USF/NASA mice NI 30 -- <24 5 Pittsburgh mice M 30 10 min 16.7 5 FR Dow rats NF 30 14 days >40 5 Dow rats F 30 14 days <40 5 Heirvard rats NF 20 21 days <128 5 Harvard rats F 20 21 days >128 5 DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 High Impact GE rats NI 120+ 14 days 12.0 5 GM 47 Utah rats NF 30 14 days >40 5 Utah rats F 30 14 days 27.8 5 Pittsburgh mice M 30 10 min. 9.7 5 GM 49/FR Utah rats NF 30 14 days >40 5 Utah rats F 30 14 days 35.8 5 Pittsburgh mice M 30 10 min. 16.3 5 GM 51 NBS rats NF 30 14 days >40-50 5 NBS rats F 30 14 days 33.0-53.5 5 Utah rats NF 30 14 days >40 5 Utah rats F 30 14 days 33.8 5 Styrofoam Dow rats NF 30 14 days >40 5 Dow rats F 30 14 days <40 5 Styropor P DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor F 200 /FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor F 210/FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor F

220 /FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor KR

2180/FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor KR 2180/1/FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Styropor KR

2180/2/FR DIN rats NF 30 NI >50 5 DIN rats F 30 NI <50 5 Pellets USF/NASA mice M 30 0 <240 5 Foam 1 Japanese mice NI 15 3 days >35 5

29
Table (continued)

Exposure PostTest Animal Time Exposure LC^g Value Material Procedure Species Mode (min) Time (ms/-g) Reference

PVC

NBS rats NF 30 14 days .16 12 NBS rats NF 30 14 days 20 12 NBS rats F 30 14 days 15 12 NBS rats F 30 14 days 17.3 12 Vinyl wall

covering NBS rats NF 30 14 days 51.0 19 NBS rats F 30 14 days 39.3 19 Pittsburgh mice M 30 14 days 14.0 19 Conduit NBS rats NF 30 14 days 37.0 19 NBS rats F 30 14 days 29.5 19 Pittsburgh mice M 30 14 days 9.8 19 C-PVC pipe NBS rats NF 30 14 days 9.1 19 NBS rats F 30 14 days 16.0 19 Pittsburgh mice M 30 14 days 4.7 19 Vinyl coated wire Pittsburgh mice M 30 14 days 16.5 19 92% homo- polymer Pittsburgh mice M 30 10 min. 11.7 20

A 6% homo- polymer Pittsburgh mice M 30 10 min. 25.3 20 PVC ZnPeCN Pittsburgh mice M 30 10 min. 3.8 20 NBS rats NF 30 14 days 7.6-11.3 12 NBS rats F 30 14 days 9.4-15 12

Rigid

Folynrethane

GM 29/30 NBS rats F 30 14 days 11.3 10 NBS rats F 30 14 days 13.3 10 NBS rats F 30 14 days >38.4 10 Utah rats F 30 14 days 11.2 10 NBS rats NF 30 14 days 34.0->39.6 10 Utah rats NF 30 14 days >40 10 Pittsburgh mice M 30 10 min. 17.3 10 GM 31 Utah rats F 30 14 days 14.2 10 Utah rats NF 30 14 days >40 10 Pittsburgh mice M 30 10 min. 13.7 10 GM 35 Utah rats F 30 14 days 12.1 10 Utah rats NF 30 14 days >36.7 10 Pittsburgh mice M 30 10 min. 12.5 10 GM 37 Pittsburgh mice M 30 10 min. 13.3 10 Utah rats F 30 14 days 10.9 10 Utah rats NF 30 14 days >36.7 10 GM 39 Utah rats F 30 14 days 16.6 10 Utah rats NF 30 14 days 10.9 10 RPU NBS rats F 30 14 days 11.0 10 PUR 1 DIN rats NF 30 NI 29.0 10 DIN rats NF 30 NI 7.5 10 DIN rats NF 30 NI 6.6 10 PU Pittsburgh mice M 10 5 min. >320 10 PUA Pi ttsburgh mice M 10 5 min. >131 10

30
Legend for Table 4

LAjq value (g) 3

a: Reported values converted to mg/i as follows: 1500 x 10 = mg/i

b: Reported values converted to mg/i as follows:

LC value (g) 3 X 10 = mg/i

(Exposure time, min) (dilution air, i/min)

FNF

NIM

FR

CMIR

DIN Dow

FAA

GE Harvard

Japeinese

Michigan

NASA/USF

NBS Pittsburgh

U. S. Testing

Utah

volume of chamber

flaming

non- flaming not Indicated

mixed mode, goes through both non-flaming and flaming conditions

fire retardant

test developed by Carnegie Mellon Institute of Research

method developed in response to the German Commission of St^mdards

test developed by Dow Chemical Company

test developed by Federal Aviation Administration

test developed by (General Electric Company

test developed at Harvard University

test developed in Japan

test developed at University of Michigan

test developed at University of San Francisco

test developed but not necessarily performed at the National Bureau of Standards

test developed at University of Pittsburgh

test developed by U. S. Testing Company

test developed at University of Utah

31
FORM NBS-1 14A (REV.1 1-84)

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBSIR 85-3267

2. Performing Organ. Report No. 3. Publication Date

June 1986

4. TITLE AND SUBTITLE

A SUMMARY OF THE NBS LITERATURE REVIEWS ON THE CHEMICAL NATURE AND

TOXICITY OF THE PYROLYSIS AND COMBUSTION PRODUCTS FROM SEVEN PLASTICS:

ABS, NYLONS, POLYESTERS, POLYETHYLENES , POLYSTYRENES, PVC, AND RIGID

POLYURETHANE FOAMS

.

5. AUTHOR(S)

B . C . Levin

6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions) 7. Contract/Grant No.

NATIONAL BUREAU OF STANDARDS

U.S. DEPARTMENT OF COMMERCE *• Type of Report & Period Covered

GAITHERSBURG, MD 20899

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City. Stote, ZIP)

U. S. Consumer Product Safety Commission

Bethesda, MD 20207

10.

SUPPLEMENTARY NOTES

I I Document describes a computer program; SF-185, FlPS Software Summary, is attached.

11.

ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here)

A series of literature reviews was undertaken by the National Bureau of

Standards to examine the toxicity and chemistry of the effluents produced when

seven plastics were decomposed under various thermal and atmospheric

conditions. These plastics are: acrylonitrile-butadiene-styrenes, nylons,

polyesters, polyethylenes , polystyrenes, poly(vinyl chlorides), and rigid

polyurethane foams. The English language literature on each of these was reviewed and published as a separate report of the National Bureau of

Standards. Over 400 different thermal decomposition products, many common to

more than one plastic, were identified. The toxicity of most of these

individual products is unknown and an assessment of the toxicity of the

multitude of possible combinations is not feasible at this time. Therefore, a variety of bioassay toxicity protocols have been used to assess the toxicity of

the gaseous atmospheres generated by the thermal decomposition of these

plastics. In general, these seven plastics did not produce unusually or extremely toxic pyrolysis or combustion products when compared to those of

other synthetic or natural materials. In a few cases involving additives,

toxic products of concern were produced.

12. semicolons)

polyester; polyethylene; polystyrene; pol3rvinyl chloride; pyrolysis products;

polyurethane foams; rigid foams.

13. AVAILABILITY

Unlimited For Official Distribution. Do Not Release to NTIS nn Order From Superintendent of Documents, U.S. Government Printing Office, Washington, DC

20402.

1"^] Order From National Technical Information Service (NTIS), Springfield, VA 22161

14. NO. OF

PRINTED PAGES

36

15. Price

$9.95

USCOAAM OC 85-4006