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Acrylonitrile-Butadiene-Styrene Copolymers (ABS): Pyrolysis and Combustion Products and Their Toxicity-A Review of the Literature

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Acrylonitrile-Butadiene-Styrene Copolymers (ABS): Pyrolysis and Combustion Products and Their Toxicity-A Review of the Literature FIRE AND MATERIALS, VOL. 10,93-105 (1986) Acrylonitrile-Butadiene-Styrene Copolymers (ABS): Pyrolysis and Combustion Products and their Toxicity-A Review of the Literature Joseph V. Rutkowski and Barbara C. Levint us Department of Commerce, National Bureau of Standards, National Engineering Laboratory, Center for Fire Research, Gaithersburg, MD 20899, USA A review of the literature was undertaken to ascertain the current knowledge of the nature of the thermal decomposition products generated from ABS and the toxicity of these evolved products in toto. The literature review encompasses English language publications available through June 1984. This literature surveyed showed that the principal ABS thermooxidative degradation products of toxicologic importance are carbon monoxide and hydrogen cyanide. The experimental generation of these and other volatile products is principally dependent upon the combustion conditions and the formulation of the plastic. The toxicity of ABS thermal degradation products has been evaluated by five methods. The LCso (30 min exposure + 14 day post-exposure period) values for flaming combustion ranged from 15.0 mg 1- 1 to 28.5 mg 1-1. In the non-flaming mode of combustion, the LCso values ranged from 19.3 mg 1- 1 to 64.0 mg 1- 1. Therefore, no apparent toxicological difference exists between the flaming mode and the non-flaming mode. The toxicity of ABS degradation products was found to be comparable with the toxicity of the thermal decomposition products of other common polymeric materials. Keywords: ABS plastics; carbon monoxide; combustion products; hydrogen cyanide; literature reviews; thermal decomposition; toxicity. Acrylonitrile Butadiene INTRODUCTION H H H H I 1 I I Although the hazard posed by toxic gases and vapors C=C-C!!NI I C=C-C=CI I I generated in a fire environment has long been re• H H H H H cognized, 1 information regarding the toxic agent(s) gen• (m.w. = 53.03) (m.w = 54.09) erated from ABS which are responsible for fire deaths not attributable to burns is relatively sparse. The growth of Styrene the science of combustion toxicology over the last ten years has resulted in the generation of a large quantity of information regarding the thermal decomposition pro• O~C=C-H ducts of many natural and synthetic materials, and the I H relative toxicity of those materials' decomposition pro• ducts in toto. This paper is a review of the English (m.w. = 104.14) literature, available through June 1984, on the thermal Figure 1. Chemical structure of ASS monomers. decomposition products from acrylonitrile-butadiene• styrene (ABS) terpolymers and an evaluation of the predominant atomic species (atomic weight/molecular toxicity data from animals exposed to those products. weight). The only source of nitrogen in the plastic is The ABS plastics are of particular interest since they are acrylonitrile, which contains approximately 26% nitro• found in numerous household items, such as telephones, gen. The weight percentage of hydrogen is relatively small. appliances, luggage and piping, as well as in automobile Acrylonitrile is a colorless liquid characterized by a and aircraft interior structures. strong odor. The boiling point of acrylonitrile is 77.3 °C and its freezing point is approximately - 83.55 0c. Acry• CHEMICAL STRUCTURE AND lonitrile is soluble in most solvents, both polar and non• THERMOPHYSICAL PROPERTIES polar. Water solubility increases with temperature. 2 Acry• lonitrile is capable of undergoing many chemical reac• tions, the majority of which occur at the carbon-carbon ABS polymers are synthesized from three monomeric double bond. It is at this site that the homopolymerization chemicals: acrylonitrile, butadiene, and styrene (Fig. 1); of the acrylonitrile monomer occurs. This reaction takes from which the acronym is derived. The atomic compo• place readily in the presence of initiators through either a nents of these three chemical compounds are, exclusively, free radical mechanism or an anionic mechanism of carbon, nitrogen and hydrogen, with carbon being the polymerization.3 The resultant polymer, polyacrylonit• t Author to whom correspondence should be addressed. rile, is a crystalline-type compound, which is not soluble in 0308-0501j86j030093-13$07.50 Received 20 February 1986 © U.S. National Bureau of Standards Accepted 24 July 1986 94 1. V. RUTKOWSKI AND B. C. LEVIN most common solvents, e.g. acids, greases, oils, water and the finished products, generally termed ABS, has been hypochlorite solutions. It will, however, degrade when reported as 466 °ell and between 500 and 575 0c.l3 ABS exposed to concentrated cold or hot dilute alkaline polymers burn readily with the generation of dense solutions, as well as warm 50% sulfuric acid. Although the smoke, which is characteristic of polymers containing acrylonitrile monomer is significantly toxic by either aromatic rings.l4 ingestion of the liquid or inhalation of the vapor, the In general, the ABS plastics exhibit good durability and homopolymer is considered essentially non-toxic.3 resilience, as well as mechanical strength. In addition, 1,3-Butadiene is a colorless gas. The boiling point of these thermoplastic polymers demonstrate a favorable butadiene is - 4.5 °e and its freezing point is - 108.96 dc. combination of thermal, electrical and mechanical pro• lt is soluble in organic solvents.4 Due to the presence of perties. The different properties may be selectively enhan• two double bonds, butadiene is a very reactive compound, ced for specific applications by modification of the allowing a variety of polymer structures to be formed. All composition and/or relative proportions of the compo• polymerizations require either an initiator or catalytic nents. Such selective production is usually at the expense factor and occur by a free-radical, an ionic or a coordinate of one or more of the other properties.9•lO,lS mechanism. The end result, polybutadiene, is a rubber polymer formed by addition polymerization. S , Styrene is a colorless to yellowish, oily liquid which has THERMAL DECOMPOSITION a penetrating odor. The boiling point range of styrene is 145 to 146°C and the freezing point is - 30.6°C. Styrene is only slightly soluble in water; however, it is soluble in The type and quantity of the thermal degradation alcohol, ether, methanol, acetone and carbon disulfide. products from ABS plastics depends upon the combus• Styrene is not considered very toxic upon ingestion but is tion chamber utilized and the existing combustion con• a significant irritant when applied to the skin, eyes and ditions, as. well as the composition of the plastic. The mucous membranes. The rate of polymerization of the majority of the studies of the chemical analysis of the decomposition products of ABS has employed a combus• styrene monomer is slow at room temperature and tion tube with a ring furnace to decompose the material. increases with heat. Since the polymerization is an This type of combustion system is similar to that used in exothermic process, the reaction can become self• the DIN 53 436 toxicity test method (see below). This accelerating. Styrene homo polymerization can occur apparatus has the advantages of being easy to set up and either by free-radical or ionic reactions. The resultant operate and requiring only a small sample for testing. The polymer, polystyrene, is a clear, crystalline-type combustion atmosphere is easily changed, allowing for compound.6-s ABS polymers (Fig. 2) can be produced by two general pyrolysis studies under inert conditions as well as ther• methods, each of which generates a different type of moxidative degradation experiments. This type of furnace may be programmed either to provide a constant temper• plastic. Type A ABS polymers are produced by a mechan• ical blending of a styrene-acrylonitrile copolymer resin ature zone or to heat at a fixed rate. The disadvantages with a butadiene-based elastomer (butadiene• within this type of system also must be considered. One of acrylonitrile rubber). The production of Type B ABS the most important limitations is the large internal surface involves a grafting of styrene and acrylonitrile onto area on which combustion products may adsorb or react. polybutadiene. The Type B polymer also contains a In addition, the small sample size, listed as an advantage styrene-acrylonitrile copolymer and ungrafted poly• above, may also be considered a disadvantage since it butadiene. The types of plastics are varied further by does not provide enough material to be conducive to a differences in the relative proportions of the monomer flaming test mode. During the actual combustion, air components. The styrene-acrylonitrile copolymer, for and/or other gases are fed into the system in a manner either type of production procedure, can be composed of which is contrary to the natural convective flow of air observed under natural combustion conditions.16 65-76% styrene and 24-35% acrylonitrile.9•lo Since the formulations of ABS plastics are rarely the same and Other furnace systems have been used less frequently in poorly defined in most of the studies examined for this combustion product generation and analysis. Therefore, review, it is difficult to generalize or compare ABS their pertinent advantages and limitations will be ad• samples. dressed when the experiments conducted in these parti• The temperatures at which ABS processing occurs cular systems are initially discussed. range from 325-550°C, depending upon the type and In the following sections, the results of the chemical grade of plastic being produced as well as the technique analyses of the combustion atmospheres of ABS are being used. The melting point range for extrusion grades separated according to the prevailing experimental con• of ABS is 88-120 °C and for the injection molding grades ditions; i.e. inert or oxidative atmospheres. Although real of ABS, 110-125°CY The autoignition temperature of fires occur normally under oxidative conditions, very often (especially in large fires) little or no O2 reaches the polymer surface.
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