Document 6MGdRaeRDo6gmK0mNg3VJqZ3

EPRI Electric Power Research Institute Topics: Chemical analysis Construction materials Pyrolysis Combustion products To* icotog y-- hazard s EPRI EL-4939 Project 2026-15 Interim Report November 1986 Literature Review of Pyrolysis and Combustion Products of Selected Utility Materials Prepared by Midwest Research institute Kansas City, Missouri HONS 217866 REPORT SUMMARY SUBJECTS T&D: Substations 1 Huardous/toxic substances TOPICS Chemical analysis Construction materials Pyrolysis Combustion proOucts Toxicology--hazards AUDIENCE Environmental managers / Distribution engineers EPRl E>.-4939s Literature Review of Pyrolysis and Combustion Products of Selected Utility Materials This information on the thermal-combustion products of utility fabrication and construction materials can help utilities evaluate potential hazards of equipment and materials in fire situations. Grouped by chemical composition, the more toxic degradation products are summarized in the report. However, relative abun dance in the utility environment is not taken into account. BACKGROUND Previous EPRI report EL-4503 presents a literature review of the pyrolysis and combustion products of pd^hiorinatad biphenyl {PCB} substitutes. EPRi extended that work to include thermal-degradation products of many utility construction materials. The expanded literature search provides background for laboratory work currently under way under the same research project OBJECTIVES To search the literature for thermal-degradation products of utility materials. To provide background information for selecting materials to be given pri ority in laboratory work. APPROACH Investigators reviewed the published literature--primarily from 1967 to the present--on pyrolysis (heating in nitrogen, helium, or other inert atmo sphere). combustion (heating in air or oxygen), or other thermal degrada tion of 26 utility materials. These materials, including polymers, rubbers, adhesives, films, fluids, coatings, and miscellaneous materials, are used m electrical insulation or construction, such as gaskets and wood preservation The project team grouped the materials according to their chemical composition--whether they contained chlorine. Iluonne. nitrogen, and su'tur or only carbon, hydrogen, and/or oxygen. RESULTS Pentachioropheno! and its sodium salt produce polychlorinated dibenzo-pdioxins and polychlorinated dibenzofurans. Several polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens, are produced from combustion or pyrolysis ol polyethylene, chiorosullonaied polyethylene styrene, and creosote. Indeed, creosote itself comprises about 85% PAHs. HONS 217867 Thermal degradation of bisphenot A epoxy resin, creosote, cross-tmxea polyethylene, Kapion. Nomex, polyethylene, polyethylene terephthaiate (Mylar), polystyrene, and polyurethane gives olher toxic semivoiaMe or solid products of concern. These are aromatic amines, phenolic com pounds, or aromatic hydrocarbons. Other materials reviewed Include neoprene, six fluorinated polymers, four nylons, dicyandlamide (no thermal-degradation information, however), nitrile rubber, polysulfone. kratt paper, and cross-linked polyethylene. One appendix of the report summarizes the more toxic degradation products from materials reviewed either In this report or in a previous EPRI-sponsored literature search. In addition, degradation products from other materials not covered in detail in this review are also sum marized in the first appendix, Another appendix lists the relative volatility, inhalation limits, and other health and safety information for most of the more man 200 thermal-degradation products listed. EPRI PERSPECTIVE This report was initially undertaken as the first quarterly report for EPRI research prpiect RP2028-15. However, because of its excellent makeup, it was expanded for publication as an interim report. In addition to its use in selecting priorities for subsequent laboratory re search, this information should also provide many insights to utility en vironmental engineers for expending their knowledge of commonly used materials. One caveat must be observed: There was no effort to categorize materials based on quantity usage. PROJECT RP2026-15 EPRI Project Manager: Gil Addis Electrical Systems Division Contractor: Midwest Research Institute For further Information on EPRI research programs, call EPRI Technical Information Socialists (4151 855-2411. MONS 217868 Literature Review of Pyrolysis and Combustion Products of Selected Utility Materials EL-4939 Research Project 2028-15 Interim Report, November 1986 Prepared by MIDWEST RESEARCH INSTITUTE 425 Volker Boulevard Kansas City, Missouri 64110 Authors B L Carson M, 0. Enckson J. L. McCann Prepared lor Electric Power Research Institute 3412 Hillview Avenue Palo Alto. California 94304 E"Ri Project Manage G AoPis Transmission Substations =fcoran E ectncal S'/stems D'vtsicn HOWS 217869 ORDERING INFORMATION Reaoests for copies of ims report should oe directed to Research Repons Center (RRC), Bo* 50490 Palo Alto. CA 94303. (415) 965 408t Tnere is no cnarge lo* f#OQrts reauested by EPRI member utilities ana aHihates. U S utility associations. US government agencies (lederat, state, ana local), media, ana foreign organizations with wnicn EPRi nas an information exchange agreement. On request. RRC will send a catalog o! EPRi reoons tcr< Po**r flMvch ii^fUute ito EDP' a>e ngmrtc st?v*c* o` Efc-rtc *t\*r 1 '996 cific Pow* P*s#**en mam**. i*c *>* ngn*s wrvfC *c NOTICE *ms iftscn *& cm#m**o Dv Of3*'*flMyiiir ftimtO Deow rt fcccOi.il 0* a'* S00r$C'*Q Cv me l eC:' : intrtfui# i^c <PP*> ?*#*?>** EPP< 'nemo#** o* EPP* the c*giniiiiiC"fSi '>a'T'eg ~c- r . r,#'*on ac:ng cn o' fchy C 'hem (*v mane* *nv wt'ftrtv e*0'e of "'c-es v t* -escec: o me .se : -- rno'menon aocvnus meinoo of O'OCttl 0<*CIOS#C in fhrf recon Of :.lj: ^Z~ _se -* ~c; n-r-m^e - s4`*.. 3wr^e0 f<jm* of :Ci issues a^t "fcoits foec -o jm or y ?- ;a*^ass T.-hf'q 'c- -i *nv moffr-siior ascara'us Tie:*oo y yocet* o-sccsec ims feceo ^-eoerec o* ^-Oyesi ^sea?c."' ^a^sis wv \i'S$owa HONS 217870 ABSTRACT The published literature, primarily from 1967 to the present, is reviewed on the pyrolysis, combustion, or other thermal degradation of 26 utility materials. These materials include polymers, rubbers, adhesives, films, fluids, coatings, and miscellaneous materials. The materials are used for electrical insulation or construction (gaskets, wood preservation, etc.) Materials reviewed are grouped ac cording to their chemical composition, that is, by whethe' they contain chlorine, fluorine, nitrogen, sulfur, or only carbon, hydrogen, and/or oxygen. Pentachlorophenol and its sodium salt produce polychlorinated dibenzo-g-dioxins (PCODs) and polychlorinated dibenzofurans (PCOFs). Several polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens, are produced from, com bustion or pyrolysis of polyethylene, chlorosulfonated polyethylene, styrene, and creosote. Indeed, creosote itself comprises about B5X PAHs. Thermal degradation of bischenol A epoxy resin, creosote, Crosslinwed polyethylene, Kapton, Nomex, polyethylene, poly(ethylene terephthalate) (Mylar), polystyrene, and polyurethane gives other toxic semivolatile or solid products of concern. These are aromafc amines, phenolic compounds, and/or aromatic hydrocarbons. Other materials res'iewed : ".elude neoprene, six fluorinated polymers, four nylons, dicyandiamide (no thermal degradation information, nowever;, nitrile ruooer, pn iysuifone. kraft paper, and crosslinked polyethylene. One appendix summarizes the more toxic degradation products from materials re viewed either in this report or in a previous EPR1*sponsored literature review. In accition, degradation products from other materials not covered in detail in this review are also summarized in the first appendix. Another appendix lists the -e1 volatility, inhalation limits, and other health and safety information fo mo sc the more than 200 thermal degradation products listed. HONS 217871 acknowledgments This report is the product of the efforts of many people. We are indebted to MR 1' library services, editorial, and word processing staffs for their assistance. We especially thank Lanora Moore, Cindy Melenson, Gloria Sultanik, and Janice Evans, who provided the primary word processing assistance. We also thank EPR1 Project Manager Gilbert Addis and Olin R. Compton, Virginia Power, for their comments on the preliminary draft, and Thomas L. Forrester, Pacific Gas and Electric Co.; J. B. Headrick, Texas Utilities Generating Co.; P. L. Kolarik, EPRI; S. P. Lindenberg, EPRI; R. Nichols, Northeast Utilities Ser vice Co.; and H. A, Onishi, Commonwealth Edison, for their help in prioritizing the materials to be reviewed and tested on this program. HONS 217872 CONTENTS Section 1 INTRODUCTION Background Search Strategy Data Compilation Contents and Organization of the Report Reference 2 CHLORINE-CONTAINING MATERIALS Background Infonnation on Two Well-Studied Chlorinated Compounds (PCBs andPVC) Neoprene Pentachlorophenol 3 FLUORINE-CONTAINING MATERIALS Haler Teflon Teflon FEP Teflon PFA Tefzel Viton 4 NITROGEN-CONTAINING MATERIALS Creosote Oicyandianide Kapton Nitrile Rubber Nomex Nylon 6 Nylon 6,6 Nylon 6,10 Nylon 11 Polyurethanes Page 1-1 1-1 1-2 1-2 1-3 1-4 2-1 2-1 2-6 2-9 3-1 3-1 3-2 3-6 3-8 3-10 3-12 4-1 4-1 4-6 4-8 4-13 4-14 4-24 4-27 4-30 4*31 4-32 MONS 217873 Section 5 SULFUR-CONTAINING MATERIALS Chiorosulfonated Polyethylene Polysulfone 6 MATERIALS containing ONLY c and h or c. H. AND 0 Bisphenol A Epoxy Resin Cross!inked Polyethylene Kraft Paper Polyethylene PolyCethylene terephthalate)(Mylar) Polystyrene APPENOIX A APPENDIX B SUMMARY OF UTILITY MATERIALS PROPOSED FOR EXPERIMENTAL TESTING ANO THEIR TOXIC THERMAL DEGRADATION PRODUCTS HEALTH ANO SAFETY INFORMATION FOR THERMAL DEGRADATION PROOUCTS Page 5*1 5*1 5*3 6-1 6-1 6-S 6-7 6-9 6-23 6-31 A-l B-l HONS 217874 TABLES Table 4-1 American Wood-Preservers' Association SpecificationPl-78 for Timber-Treating Creosote 4-2 Composition of Coal Tar Creosote 4-3 PAHs in Air Total Solid Particulates DownwindfromOpenBurning of Creosote-Treated Railroad Ties Ooused with No. 2 Fuel Oil 4-4 Nome* Pyrolysis Below 500C 4-5 Nome* Pyrolysis at 500 to 1000C 4-6 Nome* Combustion 6-1 Polyethylene Pyrolysis 6-2 Polyethylene Combustion or Other ThermooxidativeDegradation at Temperatures Up to 700C 6-3 Polyethylene Combustion at 500 to 1000C 6-4 Poly(ethylene Terephthalate) Pyrolysis 6-5 PolyCethylene Terephthalate) Combustion Page 4-2 4-3 4-5 4-19 4-20 4-22 6-14 6-16 6-19 6-28 6-29 i x HONS 217075 SUMMARY This report, presents a revie-, of the literature on the thermal degradation of a large number of materials used by and of interest to electrical utilities. This review supplements a previous Electric Power Research Institute (EPRI) literature review (EPRI Report No. EL-4503) on the thermal degradation products from PCB sub stitute fluids. This review will assist utilities in the evaluation of potential hazards of equipment and materials in fire situations. It will also assist scien tists in the design of laboratory experiments in the projects to be done at MRI (RP2028-15j and at the University of Dayton Research Institute (UDRI) (RP202B-16) to fill some of the gaps in the literature. A computerized search of Chemical Abstracts back to 1967 was performed for about 50 utility materials. Useful information was retrieved for about half. The EPRI utility advisors to this project were also canvassed for their recommendations of candidate materials. Materials containing chlorine, fluorine, nitrogen, and sulfur atoms were initially selected for in-depth review because of the dangers associated with tneir volatile thermal decomposition products, the simplest of which are hy drogen chloride, hydrogen fluoride, hydrogen cyanide and nitrogen oxides, and sul fur cipxiae, -escectively, Howeve-. the volatile products are of 'esser concern as building and environmental contamination problems after a fire involving electrical equipment than the products of low volatility (boiling point above about T30C). Materials containing only carbon, hydrogen, and/or oxygen atoms were therefore re viewed because of their potential, like that of fossil fuels and cellulose-based fuels, for forming carcinogenic polycyclic aromatic hyorocarbons (PAHs) during thermal degradation. Two utility materials, polychlorinated biphenyls (PCBs) and poly(vlnylchloride) (PVC), are briefly reviewed as oenchmarks for comparison with the other materials reviewed. Data f'om the primary literature on combustion (heating in air or oxygen) or pyrol ysis (heating in nitrogen, helium, or other inert atmosphere) of the materials were tempi'ea or. an experiment-by-experimeni basis and then summarised. Data were also comp- ec ''-m seccndarv sources on tne octuoational exposure limits in air and the 1 ea;- e-'fects cf most c. the sc-e tr.an 20C decomposition products iae-t-'-eo a HONS 217876 the materials reviewed may form highly toxic carbon monoxide during ccmoustion. Dther products identified as being potentially among the most hazardous thermal degradation products of the materials reviewed are grouped by toxic action in Table S-l. Table S-l may be helpful in evaluating the relative hazard of burning these mate rials, with four caveats. Since the table was compiled without reference to the relative amounts produced, it cannot be used to tell which particular component(s) would be most likely to be responsible for the short-term or the long-term effects Perhaps a larger amount of a less toxic material may determine the toxicity of the total degradation products; in other words, "the dose makes the poison." One must also remember when examining Table S-l the uneven characterization of the thermal degradation products of the materials. For example, thermal degradation products of polystyrene have been much more thoroughly characterized then those from polysulfone. The mere numbers of toxic products listed for the various materials, therefore, cannot be used to judge their relative hazard. Also, as was noted for formulaz.ec neoprene, these materials in actual use will have been comsounaed with plasticizers and other materials whose decomposition products may be as important as those from the virgin, unformulated material. Finally, there has been no attempt to provide perspective on the relative quantities of the materials used in utility systems. In many cases, the amounts manufactured and used for other pur poses completely outweigh any quantities used by electric utilities. The following sections summarize the degradation products found in the literature for the utility materials. As with the body of the reoort, the materials are grouped by cnemical composition, with materials containing fluorine, chlorine, ni trogen, and sulfur discussed in separate sections before the one discussing mate rials containing only carbon or hydrogen or carbon, hydrogen, and oxygen. Not all products are mentioned in this summary, nor are the conditions for formation giver in as much detail as in the body of the report. Remember that the products of thermal degradation are highly dependent on the conditions: pyrolysis vs. com bustion, heating rate, final temperature, amount of material, presence of addi tives, and other factors. HONS 217877 Table S -l HONS 2 1 7 *7 8 oX CD ac < x <z o: --O- O tn 2-' a uj O s*--= --<oc LT\ < 2 Is iU_Jj au.: i s sTf i k, ! Ss s i I l oo i/i <u ;! i. ti *' 21 * J; it *1 =' I 5! 11 i r ^ - i I"* <0 l/t tO X jj * i 55 ~ r i *. * i r'. * tS> --4 f. !1 = i i E a it?* ;* j ill Table 5-1 (co n tin u e d ) HONS 217S 80 t ;j71 *- e c ft *' V" : i 2 ?: ' 5 ;t i t* I 4iJUrii, "a u is ittinmifi |i ] a I ss s <a ? :j ut &x It * * _< J* it i 1 s * *? HONS 2 1 7 8 8 1 chlorine-containing materials Thermal degradation of chlorine-containing materials releases long-term residual contaminating products as well as tne more immediately hazardous volatiles. Fires involving PCBs in electric equipment have contaminated buildings with polychlorin ated dibenzofurans (PCDFs) and, sometimes, when chlorinated benzenes were present, with polychlorinated dibenzo--dioxins (PCDOs). Incinerator emissions of PCDFs and PCDDs have been ascribed to the widely used utility insulation material PVC. Previous reviews on the combustion of PCBs and PVC were briefly summarized. Chlor inated materials reviewed in detail in this section were neoprene (polychloroprene) and pentachlorophenol. Neoprene rubbers are used to coat electric wiring and as cable jackets. All of the neoprene materials reviewed were cured and compounded with numerous additives. Practically all of the thermal decomposition products appeared to be derived from the phthalate plasticizers, although the long-chain hydrocarbon fragments may have come from the polymer itself. Among the products identified were hydrogen cyanide (HCN), hydrogen sulfioe (ri2i), sulfur dioxide (S02), nonyIphencl, pnthalic anhy dride, and toluene. Pentachlorophenol is used to preserve wood construction materials, including util ity poles. Combustion of pentachlorophenol and its sodium salt gave octa-. hepta-, hexa*, and lower chlorodibenzo--dioxins in the volatiles and residues. Octa- and hexachlorodlbenzofuran were also identified. Other combustion products identified were penta- and hexachlorobenzene and decachlorobiphenyl. FLUORINE-CONTAINING MATERIALS The fluorinated polymers reviewed include Haler (which also contains chlorine), Teflon, Teflon FEP, Teflon PFA, Tefzel, and Vlton. These materials are used as wire and cable insulation. Combustion and pyrolysis products reported generally included monomers and other fluorinated Cj to C, alkanes, alkenes, or cycloalkanes, and hydrogan fluoride (HF) or silicon tetrafluorioe ($iF) (presumably formed from reaction of fluoride and glass of the experimental apparatus). Carbon monoxide (CD, carbon cioxide (C02), carbonyl fluoride (CDF,), and tri fluoroacetyl fluoride (CDCOF) were the oxygen-containing products usually reported, although unidenti fied aldehydes, alcohols, and carboxylic acids were detected among the Halar com bustion products, Vinylidene fluoride, which was emitted from thermal degradation o' Viton as well as from Tefzel, and Teflon fume ware other cyolysis or combustion products. HONS 217882 nitrogen-containing materials Materials considered in this section include creosote; the paper-impregnating sup* stance dicyandiamide (cyanoguanidine, colloquially called "dicy"); the polyether imide Kapton; the aromatic polyamide Nomex; nitrile rubber; the four polyamides nylon 6, nylon 6,6, nylon 6,10, and nylon 11; and polyurethanes based on toluene diisocyanate and polyols. Creosote used to protect utility poles from rot and worms is derived from coal tar It comprises about 85% PAMs; about 3 to 10% tar acids (phenolics); and the rest aromatic compounds containing nitrogen (N) (tar bases), oxygen (0), and sulfur (S) Individual PAHs released by burning creosote-treated railroad ties attained concen trations up to 0.3% in the solid particulates of the smoke. The carcinogenic PAHs identified were benz[a]anthracene, benzo(k]fluoranthene, benzo(a]pyrene, chrysene. dibenz[a .hjanthracene. and o-phenylenepyrene (indenofl,2,3-cd]pyrene). No information was found cn the comburt'on or -yo'vsis -f Tc; paper impregnated with dicyandiamide. or -- *.* Kapton film is used to insulate wire and cable, and Kapton molded parts and lami nates may be used in printed wiring boards and integrated circuit carriers. CO?, CO, HCN, benzene, aniline, phenol, benzonitrile, dibenzofuran, phenyl isocyanate, substituted phthalimides and pyromel1itimides, and a highly conductive char were produced by pyrolysis of Kapton. pyrolysis of mtrile ruober prcaucea ammonia (NH3), HCN, the monomers (acyion'trile and butadiene), acetonitrile, other nitriles, various hydrocarbons, dimers, and trimers. Nomex paper is used to insulate dry-type transformers as well as to insulate highperformance motors and generators. Nomex is an aramid, that is, an aromatic poly amide prepared from 1,3-phenylenediamine and isophthalic acid or isophthaloyl cnto ride. Major inorganic pyrolysis products were C02 , water (H20), CO, hydrogen (h;) and HCN with minor amounts of ammonia, nitrous oxide (N=0), and cyanogen. Major organic pyrolysis products of Nomex were benzene, toluene (below 50Q"C), oenzonltr;le. 1,3-phenylenediamine, oenzoic acid, aniline, 1,3-dicyanobenzene (above 500C ) , and N-(3-ami nophenyl)benzamide (60O-7DOC). The charred residue became more aromatic between 450 ana :5CcC. By 1000C, most of the hydrogen and oxygen r.ao been lest from the cnar. In contrast to pyrolysis, where J min at C0Q0oC HONS 217803 caused only 50X weignt loss, no residue remained by 1000C in air or oxygen. Water, carbon dioxide, and/or carbon monoxide were major combustion products. Nitric oxide (NO), nitrous oxide, HCN, cyanogen, benzene, substituted benzenes, acetone, acetaldehyde, benzoic acid, nitriles, 3-cyanobenzoic acid, alkanes, alkenes, and mtromethane were also identified among the Nomex combustion products. Nylons are used for plugs, connectors, wire jacketing, and many other electrical and electronic applications. In general, polyamides thermally degrade to givr ammonia, nitriles, amines, cyclic ketones, esters, CO, C02, and monomers. Nylon 6 gives caprolactam oligomers; nylon 6,6 gives mainly cyclopentanone and less than IX of the theoretically possible amount of HCN at temperatures around 700C or higher. Nylon 6,10 gives caprolactam, mediurn-1ength hydrocarbon chains (six to eight carbon atoms), and long-chain mono- and dinitriles. Nylon 11 behaves similarly on pyrol ysis, hydrocarbons with six and seven carbon atoms being the most abundant. Polyurethane foams are being examined for use as insulating materials for cryogenic cables and unde-ground transmission lines. At temperatures below 80CC, polyur ethanes pyrolyzed by giving off a yellow smoke containing all the nitrogen of the original material and comprising mainly polymeric isocyanates. The other volatile products formed at temperatures below 800C included carbon oxides, nitrous oxide, alkanes, alkenes, and lower aldehydes and alcohols. Between 800 and 1000C, ni triles, aromatic hydrocarbons, and aromatic N-containing heterocycles such as methylpyridine and quinoline were formed, although lower aldehydes and propene were still abundant at 1000C. Other products at the higher temperatures included to 1 uere di isocyanate, toluenediamine, and nitriles. SULFUR-CONTAINING MATERIALS Chlorosulfonated polyethylene is generally crosslinked. Its electrical uses in clude wire and cable coverings. At temperatures below 600C, major pyrolysis prod ucts were lower alkanes, lower alkenes, and toluene. 8y about 900C, aromatic products predominated with high yields of benzene and naphthalene. Styrene and several noncarcinogenic PAHs were found in the pyrolyzate. Chlorosulfonated poly ethylene may contain additives to reduce the amount of hydrogen chloride (HC1) emitted on combustion. Sulfur dioxide, which is highly toxic and irritating, is also evolved on combustion along with carbon oxides. HOMS 217884 Polysulfone (a copolymer of bisphenol A and 4,4'-dichl orodiphenyl sul fone) has many electrical end electronic applications including connectors, TV components, capac* itor film, and circuit boards. Combustion of polysulfone at 400aC caused a 70* loss in polymer weight but little smoke and little sensory irritation in rodents exposed to the volatile products. In a somewhat oxygen-deficient atmosphere, com bustion at temperatures up to 750C produced primarily CO, C02 , sulfur dioxide, and a residue. Intermediate amounts of methane, benzene, and toluene were found with minor amounts of ethylene, ethane, ethylbenzene, and styrene. MATERIALS CONTAINING ONLY C AND H OR C, H, AND 0 Materials reviewed in this section included bisphenol A epoxy resins (although some are crosslinked with amines), crosslinked polyethylene, kraft paper, polyethylene, poly(ethylene terephthalate), and polystyrene. Epoxy resins are used as insulation in transformers and capacitors. New informa tion on a common epoxy resin derived from bispnenol A ana eplchlorohyorin was ex amined and integrated with information from a previous review on epoxy resins (EPRI Report No. EL-4503). Decomposition products from combustion of a bisphenol A epoxy used in transformer coils included phenol, toluene, ethylbenzene, and ben zene. Other experiments previously reviewed used different epoxy material or con founded the results by burning another fuel. In these experiments, thermal decom position products of novolak epoxies based on phenol-formaldehyde resins included phenol, cresol, and methyl chloride. Crosslinked polyethylene has been used since the 1970s to insulate most of the distribution cables installed in the 15- to 46-kV range. Crosslinked polyethylene wire insulation was practically all volatilized by pyrolysis up to about 480C. Pyrolysis and combustion products have not been studied. Volatilization of decom position products of impurities such as the chemical crosslinking agent dicumyl peroxide (DCP) might be expected during exposure to lower temperatures, decompo sition products that have been identified from OCP included cr-me thy 1 styrene, cumene, phenol, and toluene. Kraft paper is used for insulation in oi1-immersed equipment such as transformers Kraft paper pyrolysis gives the same products in about the same amounts as do othece'lulosic materials (paper, wood, etc.). Gases included the carbon oxides, nycr-gen, acetylene, methane, ethylene, and other hydrocarbons. Heating above 500C gave "ower molecular weight volatiles and cnar. HONS 217885 A major use for polyethylene in the electric power industry in the United States is for duct or pipe for installing buried cable. Pyrolysis of polyethylene at temperatures up to 1000C gave saturated hydrocarbons (paraffins, alkanes) and unsaturated hydrocaroons (olefins, primarily 1-alkenes with lesser amounts of o ,iu-dienes). Combustion gave similar products, especially in the range 350 to 700C. Besides COj and water, oxygen-containing products identified included alco hols, aldehydes, ketones, and carboxylic acids. Aromatic product yields increased with increasing temperature, but yields of individual PAHs such as the carcinogen bemo[a]pyrene were only about 0.1X after incineration at 900C. At 950C, the concentrations of individual PAHs and other aromatics in cold-trapped condensates were less than 1 to about 4%. Poly(ethy!ene terephthalate) (PET, Mylar) is the most widely used film for elec trical insulation. Mylar film uses include barrier and insulation tape in cables and dielectric in high-temperature capacitors. Major pyrolysis products included acetaldehyde, C02, benzoic acid, and vinyl benzoate and terephthalate. Lower amounts (1-9*1 n# CO, ethylene, and benzene and trace to minor amounts of alcohols, aldehydes, ketones, cyclic ethers, and hydrocarbons including benzene derivatives were detected. Most of these were identified as combustion products along with dimers through pentamers of the original polymer. Polystyrene gave styrene as the major pyrolysis product in the volatiles at tem peratures up to 1400C. Other major pyrolysis products included toluene, ormethylstyrene, cumene, and styrene oligomers. Lower aliphatic aldehydes and carboxylic acids were major products along with benzene, toluene, ethylbenzene, styrene, and prcoyibenzene on comoustior, oelow scout EOO^C. In one study, ccmoustion at -iUu t; 9C0C gave a soot in 50* yield. More than 100 compounds identified from polysty rene combustion at 800 to 950C included many PAHs. Several of the PAHs identified are carcinogens. MONS 217886 Section 1 INTRODUCTION BACKGROUND ' The overall goal of this project is to evaluate the potential of utility materials to generate toxic or otherwise undesirable thermal degradation products under fire conditions. Solid, liquid, and gaseous materials used by electric utilities could degrade under fire conditions and contribute to the toxic hazard. A wide variety of insulating and structural materials are of concern. The liquids of interest include PCB-substitute dielectric fluids for transformers and capacitors. As part of the evaluation of these materials, this literature review has been con ducted to supplement i.-.e literature review previously conducted ty the Electric Power Research Institute (EPRI) (1). This review serves several purposes. The existing literature provides a great deal of information on the products of pyrol ysis (thermal degradation in the absence of oxygen, usually in an inert atmosphere such as nitrogen or helium) and combustion (burning, thermal degradation in the presence of air or oxygen) and in itself is a valuable resource for utilities and electrical equipment manufacturers for evaluating potential hazards of equipment in fire situations. For work on this and the companion project at University of Dayton Research Institute (UDRI), the review clearly shows which materials have oeen studied in detail and wnich have not. Furthermore, the review gives a general indication of the products that may be anticipated from the laboratory experiments to be conducted on the current projects. Thus, Midwest Research Institute (MRI) (EPRI Project No. RP2028-15) and UDRI (EPRI Project No. RP2028-16) researchers can utilize this knowledge to design the experiments and also to specifically searcn for previously identified decomposition products. This literature review also illustrates that the results of thermal decomposition rxoeriments are highly dependent on the experimental conditions. Thus, comparisens of results from different studies will be difficult and will require great care to prevent overinterpretation of the data. MONS 217887 SEARCH strategy Chemical Abstracts Service Registry Numbers (CASRNs) were sought for all the mate rials listed in the RFP to avoid the use of numerous synonyms in a computerized search of Chemical Abstracts. CASRNs were found for most of the materials. Those CASRNs not readily available in printed lists were sought in the Registry File of CAS ONLINE. Eacn CASRN or compound name was coupled with a set of terms based on variations of the following words: pyrolysis, combustion, thermolysis, fire, burn, thermal degradation, thermal decomposition, and thermal oxidation. The search statements were used in the CA (Chemical Abstracts) File of CAS ONLINE. Abstracts were searched from 1967 to the present, except for polystyrene whose search was limited to the last 5 years because there was so much available literature. Materials previously reviewed (1), those proposed for this review, and those ac tually completed in this review are identified in Appendix A. Initially materials known to release highly toxic volatiles (HC1, HF, HCN, NOx, and SOj) were selected for review. Later, materials with only C and H or C, H, and 0 atoms were examined for their pc tent tel to p-cduce PH' on evbssure t? t'eated tsmpe-^turi:. Pertinent articles were selected for compilation based on their abstracts. The articles were primarily English language, but Russian, German, and French articles were selected for acquisition if the methods used were likely to allow identifica tion of specific decomposition products. A further selection process, based on the actual contents of the article, was performed when the documents were examined for data compilation. DATA compilation Articles that did not identify the decomposition products (for example, those on thermal degradation analysis and differential scanning calorimetry that did not collect and analyze the volatile products emitted) were generally not examined closely. Combustion toxicity articles were sometimes useful in identifying at least relative amounts of carbon monoxide, carbon dioxide, and other toxic gases such as hydrogen cyanide or hydrogen chloride. Generally, the more recent arti cles and those that identified products by mass spectrometry were examined most closely and provided the most useful data. Data sheets we-e used as a guide for extracting the information. Each pyrjiys'i or combustion exoeriment was deserved on a seoarate oage using the same fens-. HONS 217886 1n addition to the primary literature from which experimental and mechanistic details were extrected, various secondary sources were used such as the Modern Plastics Encyclopedia and the Encyclopedia of Polymer Science and Technology to supplement general handbook information on uses, structures, and electrical, other physical, and chemical properties. Some of this information was later used to prepare the text of this report. Data for acute toxicity, carcinogenicity, and standards or recommendations for standards for workplace exposure in air were extracted for separate decomposition products from two sources: The OSHA Industrial Hygiene Technical Manual and the Registry of Toxic Effects of Chemical Substances. These data are presented along with CASRNs and information on the relative volatility of most of the more than 200 thermal degradation products identified. Compiling data on the animal toxicity of the total volatile and particulate material released during standardized com bustion or pyrolysis tests of the subject materials is beyond the scope of this review. Oata are not directly comparable among the studies and would require ex tensive critical review. CONTENTS AND ORGANIZATION OF THE REPORT The remainder of this report contains profiles for each material organized as fol lows: General Information, Thermal Decomposetion Mechanisms (not always present), a Summary of Experimental Studies Reviewed subdivided into separate discussions for pyrolysis and combustion (when information was available on both processes), and the References citec. The materials are grouped by type of hetero atom present in the`;r molecules. Thus, Section 2 contains profiles for chlorine-containing polyr s sucn as neoprene. Section 2 * s on the fluor-lne-containing materials. Sec* tion - is on materials containing nitrogen atoms, and Section 5 contains informa tion on two polymers containing sulfur atoms. Section 6 contains profiles on mate rials that contain only C and H or whose only other component is oxygen. Appendix A includes the materials proposed for review or previously reviewed and their most toxic degradation products, if any thermal degradation literature was available. More than 200 products we- identified for the 26 materials profiled. Appendix B contains toxicity, stanoards, and physical state information for most of these products. The starting material(s) for each product are identified. MOMS 217889 REFERENCE 1. J. V. Zbozinek, J. R. Marsh, 0. Guth and A. Bohrnerud (SCS Engineers, Inc.). Stata-of-the-Art Review of Combustion and Pyrolysis Bv-Products of PCB Sub' stitutes. EPR1 Report^o. EL-4503. Palo Alto, Calif : Electric Power Research Institute, March 1965. HONS 217890 Section 2 CHLORINE-CONTAINING MATERIALS BACKGROUND INFORMATION ON TWO WELL-STUDIED CHLORINATED COMPOUNDS (PCBs and PVC) Polychl orinated biphenyls (PCBs) and poly(vinyl chloride) (PVC) are two widely used utility materials whose thermal decompositions have been extensively studied and reviewed. Although PCBs and PVCs are not primary subjects of this literature review, work on these materials is briefly summarized here to orovide a basis for comparing their thermolysis products with those from the other materials reviewed r this report. The Electric Power Research Institute (EPRI) has an extensive ongoing researcn pro gram to determine the degree of the utility industry problem regarding PCBs, poly chlorinated dibenzo-g-dioxins (PCOOs), and polychlorinated dibenzofurans (PCDFs). Among these are pyrolysis and combustion studies of PCBs and PCB-contaminateo fluids such as mineral oils. This effort is supplemented by reviews and experi mental work on the pyrolysis and combustion of PCBs ana other utility materials (1). The recent NIOSH Current Intelligence Bulletin 45 Polychlorinated Biphenyls (CBs): Potential Health Hazards from Electrical Eouipment Fires or Fai1ures (2) ano two ErRI-jponsoreo reviews or. ?C6s I) = nr other materials f) form the basis for tost of the following discussions on PCBs and PVC. 3o1vcr1onated Biphenyls (PCBs) "re NIOSH Current Intelligence Bu^'etlr. .2) gives guidelines to protect the nee 1th emergency response and cleanuc corke-s in the aftermath of PCE-Containmc e 11'. : t' sc - pmer.t `ires tnat nave pr;;ucsc w'oesoreao pu-. icing contami rat1 or HONS 217891 witti PCBs, PCDFs, and PCOOs. NIDSH recommends that PCBs and 2,3,7,B-tetracnlorodibenzo--dioxin (2,3,7,8-TCDO) be regarded as potential human carcinogens. In addition, PCBs, PCDFs, and/or PCDDs have been reported to injure the liver, thymus and reproductive systems of test animals and to produce chloracne, numbness of the limbs, and other adverse effects in humans (2). Between 1932 and 1979, when the U.S. Environmental Protection Agency (EPA) issued restrictions on the manufacture and commercial use of PCBs, 135,000 PC8*containing transformers were put into service. Many of these transformers and PCB-containing capacitors are still in use. EPA estimated that by the end of 1964, approximately 107,000 PCB-containing transformers were in use or being stored for reuse; more tnan two-thiros of these transformers were used in or near puDlic builcings Is Q result of the mandated selective EPA phase-out schedules, these numbers have de creased significantly. In 1981 there were about 3.3 million capacitors containing more than 3 lb (0.7 kg) PCBs. In addition, past manufacturing and transformer sen vicing practices have contaminated mineral oil-filled equipment with trace amounts of PCBs (2,3). Some commercial PCS mixtures manufactured in the United States contained up to 6 ppm PCDFs, and PCBs from Eurooe and Japan contained uo to about 20 Dpm PCDFs (3) PCDFs have been found in almost all measurements of contamination after fires in electrical equipment containing PCBs. A total of 2,163 ppm PCDFs was determined i soot from the combustion of transformer fluid comprising PCBs and chlorinated ben zenes during the Binghamton (New York) State Office Building fire (2,3). The NIOSH dociaent summarizes the concentration of PCBs, PCDDs, and PCDDs in the soot and surface wipes after 11 U.S. fires involving electrical capacitors or transformers, PCOOs were found in the soot from five of these fires in concentra tions ranging from 0.16 to 19,9 ppm. The highest level was from the Singnamton fire (2). Other chlorinated aromatics detected (but not quantitated) from fires involving PCB-containing electrical equipment were polychlorinated bipnenylenes (PCBPs), polychlorinated pyrenes (PCPYs), and polychlorinated chrysenes (PCCYs). Some PCB samples themselves contain PCBP, PCPYs, and PCCYs (3). HOMS 217892 PCBPs PCPYs PCCYs Neither ordinary working conditions nor long-term overload (180C maximum damages the insulation rapidly) for electrical equipment containing PCBs is conducive to formation of PCOOs and/or PCDFs. Optimum conditions for formation of PCDFs from PCBs are 8% excess oxygen and about 675C for at least 0.8 sec. Thase conditions produced percent levels of PCOFs (relative to the amount of PCBs combusted) from mineral oil or silicone oils contaminated with at least 5 ppm PC8s (5). The major combustion products formed from fires starting as a result of arcing in airless transfcrme-s or capacitors are PCBPs. PCOFs. PCPYs, end PCCYs are also detected. PCBPs do not form in externally initiated fires; PCDFs are the major product with smaller amounts of PCPYs and PCCYs. PCOOs form only If chlorobenzene or chlorophenols are present in the transformer askarel (2) since formation from a PCB would require breakage of the biphenyl link. Other known or suspected environmental sources of PCOOs and PCDFs include the manu facture of trichlorophenoxyacetic acid (2,4,5-T), pentachlorophenol, and other chlorinated phenols; municipal and industrial incineration of chlorinated compounds ana plastics ano deacneo ana unoleacnea caper; copper smelting; steel-production; and. to a lesser degree, fuel combustion in coal-fired power plants and wood ana peat burners (6). Poly(vinyl chloride) (PVC) The pyrojysis and combustion of PVC [ -4-CHClCH2 4^ ] and PVC formulations with stabilizers, plasticizers, fillers, dyes, and other additives have been studied extensively. Two recent books review thermal degradation of PVC (7,8), Benzene and hydrogen chloride are the major pyrolysis products. Other pyr.lysis products identified in the range 400 to B00C are toluene, ethylbenzene, o-xylene, styrene, naphthalene, 2-methylnaphthalene, chlorobenzene, o- and jj-dichlorobenzene, and 1,2,4- and 1,3.5-trichlorobenzene (4). Only trace amounts of c1- orobenzenes and ::ner cMori ne-pontaining hydrocarbons are formed during PVC pyrolysis (9). HONS 217893 Degradation products are similar for pyrolysis and combustion except that combus tion gives CO, COj, and H20. Very small amounts of vinyl chloride are evolved. The major aliphatic compounds, formed in very small amounts, are Cj to C6 alkanes and alkenes (8). Combustion of PVC mixed with wood chips in the range 570 to 1130"C produced chlo rinated benzenes, octach!orostyrene, and PCBs. Combustion and arcing produced phosgene (C0C12) (). Chlorinated benzenes are known precursors of PCOOs and PCOFs. Other chlorinated polyaromatic hydrocarbons (PAHs) might also be expected to form, and PVC is a sus pected source of the PCOOs and PCOFs fou-d in municipal and industrial incinerator emissions (3), Conflicting reports have appeared in the literature. Rappe and coworkers (10.11) reported that PVC pyrolysis produced hexa- and hepta-CDOs, PCOFS containing 4 to 7 Cls, and other PCDOs and PCOFs, The total amount of PCOOs and PCOFs produced at 800C was about 1 ppm based on the weignt of PVC. However, Karasek ano coworkers (12) reported in 193 tnat neither tne concentrations nor the pattern of separate PCOOs and PCOFs in the fly ash from an energy-recovering municipal incinerator changed significantly by adding three times as much PVC as usual to the incinerator feed. Such results do not support the contention that PVC is a direct source of PCOOs and PCOFS in incinerator emissions. In fact, in 1984 Karasek and coworkers (13) stated that neither of the two chlorinated aro matics detected by gas chromatography-mass spectrometry after combustion of PVC under incinerator conditions at 800 to 95D"C had chlorine atoms attached to an aro malic nucleus. The two chlorinated ai kylbenzenes detected were chlorinated on z.nt alkyl side group. Among the PAHs found were acenaphthylene, anthracene, b*nz[a]anthracene, benzoCjjfluoranthene, benzo[c]pnenanthrene, benzo[a]pyrene, benzo[e]pyrene, biphenyl, chrysene, dihydroanthracene, fluorene, fluoranthene, indene, pnenanthrene, pyrene, and methyl- and phenyl-substituted derivatives of the pre ceding compounds. The only oxygen-containing species reported was pnenol. Octachlorodibenzo-g-dioxin was specifically sought and not found, although no detect': limit was given. PVC might supply the chlorine needed to produce chlorinated phenols, which are more likely direct PCDD precursors than PVC or chlorinateo oe-zenes. Combustion of vegetable materials (presumably the phenol source in mur-, cal refuse) with PVC or other chlorine source has been reported to give emiss containing choropheno 1 s, PCOOs. and PCOFs (1). HONS 217894 References 1. J, Guertin end G. Addis. PCB: the EPRI Effort. Prpc. Am. Power Conf,. 47, 701-705 (19B5), 2. National Institute for Occupational Safety and Health. NiCSH Current Intel* liqance Bulletin 45. Polychlorinated Biphenyls (PCB1s):~ Potential Health Hazaras from Electrical Equipment fires or failures. DHHS (NIOSH) Publication No. 86-111. Atlanta, GA; NIOSH, Centers for Disease Control, 1906, 25 pp. 3. J. Vuceta, J. R. Harsh, S. Kennedy, L. Hiideavann, and S. Wiley. State*of*theArt Review: PCDOs and PCQFs in Utility PC8 Fluid. EPRI CS-33O0. Palo Alto, CA: Eiectric Power Research Institute, 1983. 4. Zbozinek, J.V., J. R. Marsh, D. Guth, and A. Bohrnerud (ScS Engineers, Inc.), State-of-the-Art Review of Combustion and Pyrolysis By-Products of PCB Substi tutes" EPRI EL-45Q3. Palo Alto, Cali f : Electric Power Research Institute. March 1986. 5. M. D. Erickson. Analytical Chemistry of PCBs. Boston, MA: Butterworth Publ i sners, 1986. 6. C. Rappe. Global Distribution of Polycnlorinatcd Dioxins and Dibenzofurans. prec. Pap Natl. Meet., Div. Environ, them., Air., them. Soc. , 26(1), 86-87 (1986). 7. E. 0 Owen, Editor. Degradation and Stabilisation of PVC. London: Elsevier Applieo Science, 1904. Q. J. Wypych. Polyvinyl Chloride Degradation. Amsterdam: Elsevier, 1985. 9. R. P. Lattimer and W. J. Kroenka. The Formation of Volatile Pyroiyzates from Poly(viny! Chloride). J, Appl, Polymer Sci. . 25, 1D1-110 (1900). 10. S. Marklund, L.-0, Kjeller, C, Rappe, C. Ryan, J. deKanel, and R, C. Dougherty. Combustion of Polychlorinated Organics. II. Identification of CDFs sno PCDDs in Pyrolysis Products. reor. Pao. Natl- Meet., Div, Environ. Chem. . Am. Chem. Soc. , 25(1), 130*121 ,1935). 11. C. Ryan, J, deKanel, R, C. Dougherty, S. Mark'.and, *.-0. Kjeller, and C. Rappe. Combustion of Polychlorinated Organics I: Laboratory Models for Municipal Refuse and Hazardous Waste Incineration. Preor. Pap. Natl, Meet., t-'v. Environ, Chem,. Am. Chem. Soc. , 25(1), 127*131 (1985) 12. F. w. Karasek, A, C. Viau, G. Guiochon, and M. F. Gonnord. Gas Chromato* grapbic-Mes* Spectrometric Study on the Formation of Polychlorinated Dibenzo* j>-didxin$ and Pdlychlorobenzenes from Polyvinyl Chloride in a Municipal Incinerator. J. Chromatogr , 270, 227-234 (1983) IS. R. A. Hawley-Fedder, M. L. Parsons, and F. W. Karasek. Procucts Obtained Du^-ng Combustion of Polymers under Simulated Incinerator Conditions. III. P:l_vv'n\' Chloride. J Chromatodr. . 315, 211*221 (1984). '.o A. . 1 d e - i . G. Gorett' , and M. V. Russo. PCDC and PCDF Formation in tne Comdusl on of vegetapli. wastes, memosonere 12(45), 661*66; ( 1983 ). HONS 217895 NEOPRENE CASRN; 9010-98-4 Synonyms: Polychloroprene; Poly(2-chloro-l,3-butadiene); Neoprene GN (same as GR'M--govemment rubber, monowinylacetylene), Neoprene G types (interpolymerized, with sulfur and contain thiuram stabilizer); W types (no sulfur or thiuram) (1). Insulation Materials; Neoprene* 118 (eulticonductor power cable); Neoprene-84 (single-conductor nigh-voltage cable); Neoprene-007 (welding cable); Neoprene-435 (high-voltage, high-amperage cable) (2). Trade Names (producers); DuPrene (DuPont) General Information Molecular Formula; (C*HsCl)n Structure of Monomers and Polymer: CHj;CC1CH:CM4 2-chloro-1,3-butadiene; chloroprene Cl CHjCH2 h Cl CH,- \/ Cs c V/ c=c \/ c-- c /\ /N /\ -ch2 H Cl CH2CHj H Neoprene (head-to-tai 1) trans structure shown is consistent with x-ray diffraction fiber analysis (3), Ci_s-1,4-polymerization, 1,2-polymerization, and 3,4-polymerization give small amounts of other structures. About SX is present in neoprene Polymerized at -40C; - 30* at 100C. About 10 to 15* each of "head-to-head" and "tail-to-tai1" moieties are present in a typical polychloroprene according to NMR evidence (1). Uses: Neoprene is used for wire and cable belts, hose, extruded goods, coatings, molded and sheet goods, adhesives, automotive gaskets and seals, petroleum and chemical tank linings (4), and coatings for electric wiring (5). Neoprene is not MONS 217896 suitable as electrical insulation, but it is used as a cable jacket because of ex cellent resistance to lignt, moisture, fire, chemicals, and oils. Neoprene cable jackets replace the cotton braids, natural-rubber jackets, and lead sheaths for merly used on rubber cables. However, chlorosulfonated polyethylene is preferred for cables for fixed installations (6). Neoprene has several shortcomings, including greater expense and lowar chemical resistance than poly(vinyl chloride) or polyethylene, as a cable sheath material (7). However, neoprene has apparently found some commercial use in multiconductor power cable; single-conductor high-voltage cable; high-voltage, high-amperage cable and welding cable (Z). Thermal Decomposition Mechanisms No information was found on unformulated neoprene. Neoprene formulations give the largest variety of pyrolysis products at a radiant flux of S W/cm2. Cyclic and heterccyc'.ic ccnpcunds, some with nitrogen in the ring, predominate and originate from decomposition of plasticizers. At a radiant flux of 8 W/cm-, liquid degrada tion products decrease. Aromatic compounds are formed by cracking o* the polymer followed by recombination of smallar into larger hydrocarbons, HC1 evolution is retarded by the presence of basic additives. Neoprene formulations form a char layer during burning at a faster rate at higher radiant flux exposures, possibly insulating the material from rapid degradation (2). Summary of Experimental 5tudies Reviewed pyrolysis. Pyrolysis of a cured neoprene ruoPer useo ss a nose cove- cave trie fol lowing mass spectral peaks (percent relative intensity) attributed to the neoprene: 36 (y 14*; HC1), 38 6*), 86 (' 12*; monomer). 80 (< 6*), 141 (- 3S), 176 (. 3*; dimer), and 178 ('> 3X). Oioctyl phthalate plasticizer and phenyl-fi'naphthylamine were also identified (8). Pyrolysis of a W-type (no sulfur) neoprene at tempera tures up to 300*C gave ions with mass peaks arranged in order of increasing inten sity: 55, 91, 67, 69, 81. 73, 129, A G-type (sulfur-containing) neoprene pyrolyzed at temperatures up to 35CC gave ions with mass peaks: 53. 31, 88, 105, 77, 141 and 79; at temperatures up to 430C, the peaks were 91, 41, ICS, 129, 141, 15; and 179. Peaks found at 239 and 285 were attributed to the presents of resin and oeaks at 60, 73, and 254 were due to fatty acid processing agents (9). Pyrograms (gas chromatographic peaks) have been publisnea (10,11), but products were not ioentif'ee. HONS 217897 Combustion. Virgin neoprene began to decompose at 240C when heated at the rate of 40eC/min. The weight loss due to HC1 and other volatile decomposition products was 4SX; no char formed. Under these conditions, various formulated neoprene in sulation materials showed 18 to 4EX weight loss due to HC1 and other volatiles and formed a char representing 6 to 48% of the original weight (2). Alvares et al. (19B3) (2) identified products from combustion of a formulated neo prene insulation material. Many of the products were probably du* to decomposi tion of the phthalate plasticizer. Products evolved during dehydrochlorination included 1-octanol (CHjCHjCHjCHjCHjCHjCHjCHjOH, assuming a straight chain), pnthalic anhydride, nonylphenol CC9Hj9CtHH0H), dioctyl phthalate, 4,5-dimethyl-l-o-gmetnoxyBenzoyloxy-g-methoxybenzy1idene-1, ll*N-dicyclocosane [sic], n-nonacosane, 2-(methylthio)benzothiazole, 3-ethy 1-5-(2-ethyl butyl)octadecane, n-heptacosane, 1-methylbutyl isobutyrate, and phthalanil. Products evolved after dehydrochlori nation included n-hexadecane, squalene, dioctyl phthalate, diisobutyl phthalate, palmitic acid, 7-n-butyldocosant, 3-ethyl-5-(2-ethylbutyl)oct*decane, and norpentylthiol [sic] acetate. Products from combustion at 200 to 800C identified in the air of a combustion toxicity chamber were 5,510 ppm carbon monoxide (CO) and 3,170 ppm methane with a char yield of 34.3S (12). (The combustion products killed the test animals within 25 min compared to 15 min for Douglas fir.) CO and HC1 were major products from flaming combustion of ntoprene seat padding and hose materials. HCN was a minor product. S0; and FUS in minor amounts were evolved from the neoprene sample mat naa apparently peer vulcanized with zulfur (13). References 1. C. A. Hargreaves and D. C. Thompson "2-Ch1oroDutadiene Polymers" in: Encyclopedia of Polymer Science and Technology, Vol. 3. H. F. Marx and N. M. 01ka1e) , Editors. New Yorx: wiley, 196S, pp. 705-730. 2. n. j. Alvares. A. E. Lipfka-Quinn, and H. K, Hasegawa. Thermal Oegradat'.on of Cable and Wire Insulations. ASTM Soec. Tech, PuOl., S16(Behav. polvm. Mater, Fire), 42-66 (1983). 3. M. Windholz, Editor. The Merck Index, 10tn ed. Rahway. N.J.: Me'ck anc - Company, Inc,, 1983. A J, E. hauck, Editor. 1974 Materials Selector. Vol. 78(4). Stamford. Conn. Feinnolc PuPlisning Company, 1573. ; G. G. awley. The Condensed Chemical Dictionary. 10th ed. New T;r>-.: van `icitrana Reinnold Company, 1961. HONS 217898 6. J. . Hogan. "Wire and Cab)* Coverings" in: Kirk-Qthmer Encyclopedia of Guernica) Techno), 3rd *d.. Vol. 13. New York; interscience Puolisners, a Division of Jonn Wiley and Sons, 1981, pp. 564-590. 7 T, Tanaka and A. Greenwood. Advanced Power Cab)* Technology, I. Sasic Con cepts and Testing. 8oca Raton, Ft: CRC Press, 1983. 8. J. B. Pausch, R. P. Lattimer, and H, L. C. Meuzelaar. A New Look at Direct Compound Analysis Using Pyrolysis Mass Spectrometry. Rubber Chem. Techno 1,. 56(5), 1031-1044 (1983). 9. A. J. Pidduck, Mass Spectrometric Analysis of Halogenated Polymers, J, Anal. Aop1. Pyrolysis, 7(3), 215*229 (1985). 10. J. C-A. Hu. Chromatography Analysis of Rubbers and Other High Polymers. cnromatogr. Sci., 19(12), 634-638 (1981). 11. G. Di Pasouale and T. Capaccioli. Identification of Elastomers by HighResolution Pyrolysis-Gas Chromatography and Multiple Selective Oetectors. J. Chromatoqr. . 279, 151*156 (1983). 12. C. J. Hilado and C. J. Casey. Pyrolysis of Polymeric Materials. I. Effect of Chemical Structure, Temperature, Heating Rate, and Airflow on Char Yield and Toxicity. J. Fire F1ammabi1ity, 10, 140-167 (1979). 13. 0. Gross, J. J. Loftus, T. G. Lee, and V. E. Gray. Smoke and Gases Produced bv Burning Aircraft Inte-ior Materials. Building Science Series 18. National Bureau of Standards, 1969. PENTACHL0R0PHENOL CASRN: 87-86-5 (Na salt: 131-52-2) Synonyms: Pent*; PCP; ptnChlorol; salt: Na pentachlorophenoxid*. Trade Names (producers)' Santophen 20; salt: iantoorite; Dowicioe 0. General Information Molecular Formula: C*HCls0, mol. wt. 266.35 C - 27.05*, H - D. 38*, Cl - 66.56*, 0 - 6.01* Structure: HOMS 217*99 Uses; Bactericide, fungicide, and slimicide, primarily used to preserve wood, wood products, and other materials. It has also been used as an herbicide, insecticide, and mollusciclde (1). Thermal Decomposition Mechanisms The following equations represent reactions leading to polychlorinated diphenyl ethers, octachlorodibemo-g-dlo*in, and hexachlorobeniene fro* pentachlorophenol (2). Summary of Experimental Studies Reviewed Pyrolysis. Thermal decomposition of bulk POP at 2S0"C for about 12 hr in a sealed tube gave v SOX conversion, primarily to 2-(2',3'.4',5',6'-hexachlorophenoxy)3,4,5.5-tecracnloropnenol (I) plus small amounts of octa-CDO (II); Na PCP reached at 360C within about 20 *in to give 100X octa-CDD (3), Combustion. Technical grade pentachlorophenol (PCP) or its sodium salt (Na PCP) may contain chlorinated dibenio-g-dioxins (CDDs) (hexa*. hepta-, and octa-). Com* bustion experiments almost always give detectable octachlorod1benio-g*dioxin (octaCDD). In experiments burning technical pentachlorophenol at 515 to 600*C, with controlled aaounts of 02, *aximum amounts of hepta- and octa-CDO formed at the lowest temperature; the amount of hexa-CDD was somewhat higher at higher tempera ture'. Higher amounts of CDDs were formed during open burning (mostly hepta- and octa-CDD). With only 1. SX Oj, almost twice as much total CDDs was formed at 660C as from open burning. Major products in reduced' oxygen atmospheres were pentaand hepta-CDDs; the level of TCDD (tetre-CDD) was higher than from the other ex periments (a). Open burning of a pure Na salt of pentachlorcphenol gave octa-, *ecta-, and hexa-CODs 'n snaroly decreasing amounts (5), Comoustion results were 3-10 HOMS 217900 compared for materials (wood or paper) treated with pure Na salt, impure Na salt or peritachlorophenol. The highest amounts of octa-CDD were in combustion products of the Na salt-treated materials; but in the burned residues, high amounts of octaCDD were found in the PCP-treated samples. Amounts of unburned residue were higher at lower temperatures (6). A 1985 report of an analysis of combustion products at 600C by high resolution gas chromatography-mass spectrometry (HRGC-MS) listed the following products: octa-CDD, octa- and hexachlorodibeniofuran, decachlorobiphenyl, octachloronephthalene, pentachlorobeniene, hexachlorobenzene, and products identified only by formulas--C6Cla0, CloCl|0, and C14Cl]O0 (7). These latter formulas may be only frag ments. 2,3,7,8-tcdd was specifically said to be absent, but the only COD detected was the COD usually present in the highest amounts: octa-CDD. References 1. U.S. Environmental Protection Agency. Ambient Water Quality Criteria for Pentachiorspnenc1. eESl-117764, Springfield. VA: National Technical Infor mation Service, October 1980. 2. G. G. Choudhry and 0. Hutzlnger. Mechanistic Aspects of the Thermal Forma tion of Halooenated Drqanic Compounds Including Polychlorinated Dibenzo-pDioxins. hew York: Gordon and Breach Science Publishers, 1983. 3. H. G. Langer, T. p. Brady, l. A, Oalton, T, W. Shannon, and P. R. Briggs. Thermal Chemistry of Chlorinated Phenols. Advan. Chem. Ser.. 120, 26-32 (1973), . B. Jansson, G. Sundstrom, and B. Ahling. Formation of Polychlorinated Oibenio-o-dioxins During Combustion of Chlorophenol Formulations. Scf. Total Enwon. , 10(3), 2D9-217 (1978). 5. C. Rappe, S. Marklund, H. R. Buser, and H. P. Bosshardt. Formation of Poly chlorinated Dibenzo-p-dioxins (PCDDs) and Dibenzofurans (PCDFs) by Burning or Heating Chlorophenates. Chemosphere, 7(3), 2S9-281 (1978). . R. H. Stehl, R. R, Papenfuss, R. A. Bredeweg, and R. W, Roberts. Stability of Pentachlorophenol and Chlorinated Dioxins to Sunlight, Heat, and Combus tion. Advan. Chem. Ser,, 120, 119-125 (1973).7 7 E, S. Lahaniatis, . Clausen, 0. Sieniek, and F. Korte. Formation of 2,3,7,8 Tetrachlorodibenzofuran During Thermolysis of Selected Chlorinated Organic Compounds. Chemosphere. 14(2), 233-238 (1985). MONS 217901 Section 3 fluorine-cdntaining materials HALAR CASRN: ZS1D1-4S-5 Synonyms: 1.1 Ethylene-chlorotn'fluoroethylene copolymer; ECTFE. Trace Names (producers): Halar (Allied Chemical); General Purpose Halar 300 or 500 or 502 [but Halar 2D0 is poly(ch1orotrlfluoroethylene), CASRN 90D2-83-9]; Halar 555 (blown). General Information . Molecular Formula: (CHH4C1F3)n Structure of Monomers and Polymer: CH2:CH2 + CFjiCFCl -KH2CH2CF2CF)^ C1 Uses: The primary use of Haiar is for wire ano cable; otner uses incluoe injection molded products, tubing, binders, and coatings for chemical process apparatus, Its biggest use in wire and cable is for plenum cable, coaxial cable, cable in mass transit cars, appliance wire, motor lead wire, and wire for lighting fixtures. Powders are used as binders for chlorine cell diaphragms and as mold release agents. Film is used for cases for LI I pacemaker batteries, tapes for wire and cable insul ation, and solar energy laminates. Monofilament is used for mist eliminators, braided sleeving, and filter fabric (1). Halar is also used for nuclear control ana instrumentation cable (it has excellent nuclear radiation resistance), back oanei wire for computers end automatic telephone switching equipment, cathodic pro tection cable, and oil-well logging and submersible pump cable (2). HONS 217902 Thermal Decomposition Mechanisms No specific information was found. Summary of Experimental Studies Reviewed Pyrolysis. No information was found on pyrolytic products from Halar. Combust ion. No information was found on identified organics lost on combustion. Thermal oxidation of a Soviet 1:1 ethylene-chlorotrifluoroethylene copolymer (m, p, 215C) gave alcohols, aldehydes, and carboxylic acids at temperatures up to 275C. Long-term oxidation at 270C caused profound destruction giving low molecular weight products with aldehyde and carboxy end groups (3), Concentrations of HC1, HF, CO, and sometimes C0Ft generated in combustion toxicity experiments are too low to be the cause of the toxic symptoms observed in the test animals. Something other than these inorganics must cause the toxicity under some conditions (4). References 1. Modern Plastics Encyclopedia. Vol. 59, No. 10A. J. Agranoff, Editor. New York: McGraw-Hill, Inc., 1982. 2. A. B. Robertson and E. C. Lupton, Jr. "FIuorinated Plastics: Chlorotri- fluoroethylene Copolymers with Ethylene" in: Encyclopedia of Polymer Science and Technology. Vol. Suppl. 1. H, F. Mark and N. M, B1 kales, Editors. New York: Wiley, 1976, pp. 279-287. 3. A. I. Tsvetkova, L. I. Tarutina, Ts. S. Ounaevskaya, T. V. Kreitser, G. P. `'akarova. sno T, (. Ceienxova. Structural Changes in a Trifluorocnlorcetnyiene ano Etnyiene Copolymer at Hign Temperatures. Yvsoxomol. 3oeo;n., Ser. B, 11(12), 865-888 (1969). 4. H. L. Kaplan, A. F. Grand, W. G. Switzer, and S. C. Gad. Acute Inhalation Toxicity of the Smoke Produced by Five Halogenated Polymers. J. Fire Sci. . 2(2), 153-172 (1984). TEFLON CASRN: 9002-84-0 Synonyms: Polytetrafluoroethylene (PTFE); TFE; Polytef; Tetrafluoroethene homo polymer; Tetrafluoroethylene polymer; Polytetraf1uoroethylene resin (1). 7-ade Names (producers): Tefion (. I. du Pont de Nemours); Huon (ICI Americas) , -luo'-of'ex (2); Haicn (unfilled and filled) (Allied Corporation); Fluorocomo HONS 217903 (filled) (Liquid Nitrogen Processing Corporation); Tetreloy (filled) CI Cl Americas); Hostaflon (Hoechst); Algoflon (Montedison); Soreflon (Ugine Kuhimann); and Polyflon (Daikin) (3). General Information Molecular Formula: (C,Ft) (76% F, 24% C) Structure of Polymer: n Uses: Teflon is used as an electrical insulator, especially in high frequency ap plications (1). Electrical uses include coaxial spacers, insulators, wire coating, and tape in electrical and electronic fields (4). Coated glass fibers are also used for conveyor belting, electrical tape, and laminations for electrical uses (3). Teflon may be used to Insulate hook-up wire. Films are used to insulate wire and as sheet insulation (5). Other uses include protective clothing (1), gaskets, liners, seals, flexible hose; ablative coatings for rockets and space vehicles; chemical process equipment; aerospace coatings; bearings, seals, piston rings; antistick coatings for cooking vessels and utensils; felts and packing; coating glass fibers for architectural structure composites (4); and filtration fabrics (1). "henna! Decomposition Mechanisms Teflon depolymeriies to monomer (CFjiCFj), perfluoroi.obutylene E(CFa )aC:CFz], and carbonyl fluoride (C0Fa). The latter hydrolyzes to give C02 and HF (6). Thermal degradation proceeds by homolytic statistical chain cleavage (7). CO; and CF4 result from the disproportionation of C0Fz. Kexafluoroethane, CF3CFJt and higher perf1uoroalkanes apparently form by reaction of C0F2 with the corresponding perfluoroalkenes. 1- s MOMS 217904 The S1f4 probably arises from reaction of HF with the glass of the infrared gas cell wall or of the gas sampling tube. The hydrogen source is apparently trace moisture (Hz0) (8), Trif1uoroacetic acid, CFiCOIH, and HF may form In oxidative pyrolysis from tri* fluoroacetyl fluoride (9). [Isolated as CFjCOjCa after treating the pyrolyiate with Ca(0H)2 solution. ] The mechanism according to Morisaki (1978) (10) for products having formula (CF,) *R is as follows; " 2 CF, CFjjCF, 2 CF,:CF2 rF F -I---- 1--F --s-CFjCFiCFj CFj: FF CF2:CFz CFj:-----> CFjCF:Cf2 CFjCF:CF2 * CF2: ------1 CFjCFjCF:CF2 or (CF,)2C:CF2 and higher homo logs and higher homologs Atkinson and Atkinson (1957; cited by Morisaki, 1978) (10) proposed that C2F# is a decomposition product of perf1uoroisobutylene at > 700C, but stated that such a mechanism cannot be used to produce C3F8 or C4F10. C,FS> CsFa, and C,Fl0 may come from decomposition of higher molecular weignt Huorocarsons. C-,F:H, and C3F5h may occur from reaction with contaminant water. HONS 217905 COF; forms from the reaction of CF2: and Q;. Summary of Experimental Studies Reviewed Pyrolysi s. The monomer tetraf luoroethylene (.CF2: CF2 or C2F4) was an intermediate to major product in pyrolyses at atmospheric pressure (7, 9-11). Major pyrolysis products usually included carbon tetrafluoride (CF4) (7,10), octa* fluorocyclobutane (cyclic-C4F,) (9,11), and hexafluoropropylene (CF3CF-.CF2 or c2F6) (7,9,10). Morisaki (1978) (10) reported numerous other pyrolysis products includ ing octafluoroisobutylene C(CF3}2C:CF2] and decafluorobutane (C4F10). Hydrogen fluoride was seldom reported as a pyrolysis product (2). At low pressure the monomer was the only important pyrolysis product. Monomer yield _in vacuo was highest near 500C (96.6X) and decreases with increasing tem perature (91.20* at 800C and 78.10* at 1200C) (12). Compustion. The flash*ignition temperature of Teflon is 560C: the self*ignition temperature is 580C (6). CF4, Sir,, C0F2 , and C02 were generally present among combustion products of Teflon and were usually major (9,10,13). Monomer was a major product (60*) from combustion at 700C (13). Morisaki (1978) (10) found hexafluoropropylene (C3FS) to be the most abundant fluorocarbon from combustion at 450 to 790C. Trifluoroacetyl fluoride (CFaC0F) was reported from comoustion at 600 to 650C (9). Other combustion products reported were octaf1uoropropane (u3Fg), octafluoroisobutylene (CFa), and octafluorocyclobutane (C,Fa) (9,10). References 1. M. Windholi, Editor. The Merck Index. 10th ec. Rahway, N.J.: Merck and Company , Inc. , 1983. 2. K. Wiessner. Survey on the Toxicology of Poly(tetraf luoroa thy lene) and Its Pyrolysis Products During Preparation. Processing, and Use. Plaste kautsch. , 27(6), 330-333 (1980). 3. Modern Plastics Encyclopedia, vol. 59. Mo. 10A. J. Agranoff. Editor. New Yorx: HcGraw-Hi 11 , Inc. , 1982. i G. G. Hawley. The Condensed Chemical Dictionary. 10th ed. New York: Von Nostrand Reinhoid Company. 1981. R. N. Sampson, "Insulation. Electric" in Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ad., Vo'. 13. M. Grayson, Editor. New orx: Intersciencs Pudiisners. a Division of John Wiley & Sons, 1981, pp 534-553, HONS 217906 6. J. Troitzsch. international Plastics F1 ammab ill tv Handbook. New York: MacMi1lan, 1983. 7. H. J. Kretzschmar, D. Cross, and J. Kelm. Pyrolysis-Gas Chromatography and Spectroscopic Identification of Fluorine Polymers. Anal. Pyrolysis. Proc. Int. Symp. , 3rd, Meeting Date 1976. C, E. Jones and~T! a"! Cramers. Editors. Amsterdam, Neth.: Elsevier, 1977, pp. 373-382, 8. S. L. Madorsky. Thermal Degradation of Organic Polymers. New York: John Wiley & Sons , 1964. 9. H. Arito and R. Soda. Pyrolysis Products of Polytetrafluoroethylene and Polyfluoroethylenepropylene with Reference to Inhalation Toxicity. Ann. Occup. Hyp.. 20(3). 247-255 (1977). 10. S. Morisaki. Simultaneous Thermogravimetry-Mass Spectroaietry and PyrolysisGas Chromatography of Fluorocarbon Polymers. Thermocftim. Acta, 25(2). 171 183 (1978). 11. C. N. Cascaval and R. E. Florin. Pyrolysis Gas Chromatography of Some Fluorine-Containing Polymers. J. Fluorine Chef*. , 14(1), 65-70 (1979). 12. N. A, Khalturinskii and N. N. Berlin. "High-Temperature Pyrolysis of The-moplastic Polymers" in: Degradation and Stabilization of Polymers, vol. 1. H. H. G. Jellinek, Editor. Amjtercar, Neth.: E'seve', 1?S3. -c. 289-'76. 13. S. J. Williams and F. 8. Clarke. Combustion Product Toxicity: Dependence on the Mode of Product Generation. Fire Mater, , 7(2), 96-97 (1983). TEFLON FEP CASRN: 25067-11-2 Synonyms: Fluorinated ethylene-propylene copolymer; Hexafluoropropylenetetrafiuoroethvine copolymer. Trade Names (producers): Teflon FEP; Teflon 100 (Du Pont). General Information Molecular Formula: <,CsFt0) [Same elemental composition as PTFE: 76* F, 24S C Cl)] - Structure of Monomers and Poiymer: _/* ''v. 'e-'a^luoroetnyieie cF x>c' r Ur, 5e-j:ucrooropy 1ene I/ \ HONS 217907 Uses: Teflon FEP is used for plenum signal and fire alarm cable, for insulation for oil well logging cable, and for a wide variety of other electrical and elec tronic uses (1), Major electrical uses for Teflon and Teflon FEP have been in military electronics, aircraft, and missiles for their space-saving capabilities. Their excellent mechanical and dielectric characteristics allow internal wiring of computers and industrial controls to be miniaturized. They are also used in highfrequency cables. Fluorinated ethylene-propylene coatings are applied to polyimide film for cable insulation tapes. After winding of the coated film tape on tns con ductor, the assembly is heated to fuse the lower-melting coating (2). Thermal Decomposition Mechanisms Teflon FEP depolymerizes to monomers (3). "Homolytical statistical chain cleavage" gives uncharacteristic fragments. Pyrolysis of branched CFa groups gives high yields of perfluoropropylene (CFjCF:CF2, C3FS) (4). See discussion from reference 8 in preceding subsection on Teflon. As oete-mined by t.nermograv imetric analysis coupled with mas; soect-ometry f'G-MS) in helium, the first-stage degradation gives mainly CFjCFiCFj, which may be liber ated directly or evolved via the reaction of CF2CF: and CF2:. CjF4 and C2FS evolu tion at the second stage corresponds to the reactions given in the Teflon discus sion. Perfluoro-2-butene or perfluoroisobutylene (C,FS) may be formed in both stages by the reaction: CF.CF:F. + CF,:----- * CF,CF,CF: CF2 or (CF,).C:CF2 During pyrolysis, most CjF4 is formed at 450 to 550C by the reaction: CFjCF: CF, -- CF,:CFj * CF,: Reactions in air include formation of carbonyl fluoride, carbon dioxide, and carbon tetrafluoride: ZCF,: r 0,----- ZC0F2 2C0F, HONS 217908 Summary of Exper-mentai Studies Reviewed Pvrolys is. Major pyrolysis products for Teflon FEP between 400 and 700C were the monomers CF3CF:CF; (C3F6) and/or CF2:CF2 (there are conflicting reports for results 1rom similar oyrolysis-GC experiments). Other fluorocarbons produced included CF, , (CF3)jC:CF2 (C,F,) or CF3CF2CF:CF2 (C4F4), and perfluorocyclobutane (C,Fa) [Morisaki (197B) (5) doubted its presence] (3*6). SiF, (formed from reaction of HF and glass apparatus with traces of moisture the apparent source of hydrogen atoms), CO, and C02 evolved above 650C (5). Compustion. Major products in moist air or oxygen were C3F*, CF4, SfF4, C0F2, C02, and tri fluoroacetyl fluoride (CF3C0F) (5,6). However, thermogravimetric analysis at 400 to 600C revealed no SiF, and little C3F8 and CF4, Other "combustion'1 prod' ucts at 450 to 790C included octafluoropropane (C3F8, CF3CF2CF3), decaf 1uorobutane (C4F10), C4F8 (none by TG-MS), and cyclic-C4Fa (5). References 1. Modern Plastics Encyclopedia. Vol, 59, No, 10A. J. Agranoff, Editor. New York: McGraw-Hill, Inc., 1982. 2. J. E. Hogan, "Wire and Cable Coverings" in Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 13. New York: Interscience Publishers: a Division of John Wiley & Sons, 1981, pp. 564-590. 3. A. J. Pidduck. Mass Spectrometric Analysis of Halogenated Polymers. J Anal. Aopl. Pyrolysis, 7(3), 215-229 (1985). 4. H. J. Kretzschmar, 0. Gross, and J. Kelm. Pyrolysis-Gas Chromatography and Soectroscooic Identification of Fluorine solymers. Anal. ttvrolvsis. Proc. Inc. Cyme., Ire. 'ieet'no Cate 1S75. I. -. vones ana C. Cramers, edi tors. Amsterdam, Neth.: Elsevier, 1977, pp. 373-382. 5. S. Morijaki, Simultaneous Thermogravimetry-Mass Spectrometry and PyrolysisGas Chromatography of Fluorocarbon Polymers. Theraochlm, Acta. 25(2), 171*183 .(1978). 6. H. Arlto and R. Soda. Pyrolysis Products of Polytetrafluoroethylene and Polyfl uoroethylenepropylene with Raference to Inhalation Toxicity. Ann. Occup. Hvo. . 20(3), 247-255 (1977). TEFLON PFA CASRN: [Dependent on particular co-monomer used with tetrafluoroethylene.] Synonyms: serfluoroalkoxy resin. MOMS 217909 Trade Names (producers): Teflon PFA (. I. du Pont de Nemours). Two meltviscosity grades TE-9704 and TE-9705 (1)- General Information Molecular Formula: [Dependent on alkyl group.] Structure of Monomers and Polymer; Uses: Teflon PFA is used for injection molded wafer baskets that allow automated production of electronic components in calculators, computers, etc.; for valves, fittings, and injection molded complex shapes for components that require the properties of PTFE; and for heat shrinkable and convoluted tubing, roll covers, electric wire insulation, and other electrical industry components (2). Besides wire and cable insulation, Teflon PFA is used in molded insulating pares such as connector inserts or insulator bushings and standoff insulators. In 1976, develop ing uses were electrical spaghetti tubing and film for flexible circuits, flat cable, and melt bonding. It is also used for lined valves, pipes, and tanks in chemical processing apparatus and has heat-exchanger applications (1). Thermal Decomposition Mechanisms No specific information was found. Summary of Experimental Studies Reviewed Only one article (3) was found on thermal decomposition of Teflon PFA, and it h*d no experimental details. The toxic decomposition product was thought tc be par tially degraded polymer in particulate form. References 1. R. 1. Johnson. "Fluorinated Plastics: Tetraf 1 uoroethylene Copolymers" in: Encyclopedia of Polymer Science and Technology. Voi. Suppl. 1. H. F. Mark ano N. M. Bikales, Editors. New York: Wiley, 1976, pp. 260-278. 2. Modern Plastics Encyclopedia. Vol. 59, No. 10A. J. Agranoff, Editor. New Vork: McGraw-Hill, Inc., 1982. HONS 217910 3. R, S. Waritz. Industrial Approach to Evaluation of Pyrolysis and Combustion Hazard*. Environ. Haalth Perspect.. 11, 197-202 (1975). TEFZEL CASRN: 25030-71-5 Synonyms: Ethy 1 ene-tetraf 1 uoroethy 1 ana copolymer; TFE. Trade Names (producers): Tefzel (modified ETFE) (Du Pont); Ftorlon 40 (USSR); Hostaflon ET (Hoechst, Germany). T-200 grade is general purpose. T-280 for more severe mechanical use. General Information Molecular Formula: Structure of Monomers and Polymer; Uses: ETFE is used for high performance wire and cable insulation, back panel wiring in computers, hookup wire for aircraft and mass transit applications (loco motives and cable cars), and wiring in nuclear power plants. Injection molded parts of ETFE are used as components in pumps, valves, and other chemical process apparatus; tie wraps; tower packings; and seals and other electronic device compo nents (1). It '$ specified for wire insulation ;n U.5. Navy Mi 1-W-S1822/13. a specification on solderless wrap wire, and in Mi 1-W-22759/16, /17, /18, and 719, joint services specification for aircraft wire. ETFE can be applied over bare as well as plated conductors or used as a protective jacket over multiple bundles or coaxial cable (2). Thermal Decomposition Mechanisms Tefzel releases minute amounts of HF at processing temperatures of 300 to 320C. It does not undergo an autocatalytic decomposition with elimination of HF at high temperatures. Tefzel undergoes oxidative crosslinking in air above its melting point and undergoes random chain scission above 400C ratner than "unzippering." Its noncharring behavior is typical of a polymer that degrades to low-molecul arweight fractions instead of leaving a residual carbonaceous skeleton by splitting out small molecules (2), Tefzel produces far less smoke under current overload 3-10 HONS 217911 than do PVC-nylon, poly(vinylidene f 1 uoriae)-jacketed polyethylene. or other sinii lar insulations. Two routes are needed to explain the presence of tetrafluoroethylene and vinylidene fluoride (CF2:CH2) in the decomposition products (3): Summary of Experimental Studies Reviewed Pyrolysis. Pyrolysis at 70DC for 1C sec gave three major and several other un identified products whose retention times on the gas chromatogram were different from those of other fluorinated polymers. The pattern of minor products was typi cal of that from polyethylene, representing n-alkanes, o-olefins, and or,ui-olefins (11. Combustion. Minor amounts of HF were lost during processing at 300 to 320C, but 20-hr exposure to 3DDC led to - 30% weight loss; at 400C, % 40% of the initial weight was lost within 2 hr (5), The only products identified from combustion in the 530 to 580C range were HF, CO, and C0F2; but some other component was responsiple for the toxicity (6). Random chain scission at 650C for 15 sec gave mostly vinylidene fluoride, CH2;CF2. with minor amounts of the monomers and HF. Alkanes, various C3 compounds, and higher boiling substances were identified (3,7). References 1. Mooern Plastics encyclopedia, Vol. 59, .No. 10A. J. Agranoff, Editor. .New York: McGraw-Hi11, Inc., 1982, 2. R. L. Johnson, "Fluorinated Plastics: Tetrafluoroethylene Copolymer;" in: Encyclopedia of Polymer Science and Technology. Vol. Suppl, 1. H. F, Mark anc N, M. Bikales, Editors. New YorK: Wiley, 1976, pp. 260-278. 3. G. S. Popova, 8. I, Saxhir., and N. E Shadrina. Study of Products of tne The*mal Degradation of a Tetraf1uoroethylene-Ethylene Copolymer by the Method of Pyrolytic Gas Chromatooraphy. Vvsoxomol. Soedin.. Ser. B, 21(10), 758-761 (1979). H. J. Kretischmar. D. Gross, and J. Kelm. Pyrolysis-Gas Chromatography and Soectroscopic Identification of Fluorine Polymers. Anal. Pyrolysis. Proc. lot. Symo., 3rd, Meeting Date 1976. R, C. E. Jones and C. A. Cramers, Edi tors. Amsterdam, Neth.: Elsevier, 1977, pp. 373-382.5 5. S. Barron. An Investigation of the Effects of High Temperatures Upon Various Inaustnal Polymers. J. Fire FlammapiHtv. 7{July), SST-^OO (1976). HONS 217912 S. H. L. Kaplan, A. F. Grand, W. G. Switier, and S. C. Gad. Acuta Inhalation Toxicity of the Smoke Produced by Five Halogenated Polymers. J, Fire Sci. . 2(2), 153-172 (1984). 7. N. E. Shadrina, P. 0. Gol'dln, B. I. Saihin, G. S. Popova, and M. S. Kleshcheva. Mathematical Hodellng in the Study of Properties of the TFE-E Copolymer by Pyrolytic Gas Chromatography. Plast. Massy. (9), 47-48 (1981). VJTON CASRN: 9011-17-0 Synonyms: Vinylidene fluorlde-hexafluoropropylene copolymer; vinylidene fluoride hexafluoropropene copolymer. Trade Names (producers); Viton; Viton A; Viton V (E. I. du Pont de Nemours, Inc. Refset Fluorel; Fluorel (3M) (no additives); Radar Viton; Viton LM (low-molecular weight); Oai-El (Oaikin); Tecnoflon (Montedison). General T"*crmef:on Molecular Formula: [Dependent on relative amounts of the two monomers.] Structure of Monomers and Polymer: CHj:CF j CF3CF: CFa- (head-to-tai1; major) (heso-to-heao; mi nor) Uses: viton fluoroelastomers are used in gaskets, seals (especially 0-rings), tubing, diaphragms, aerospace and automotive components, high vacuum equipment, 1ow-temperature equipment, and radiation equipment (1). Thermal Decomposition Mechanisms No specific information was found. HOMS 217913 3-12 Summary of Experimental Studies Reviewed Pyrolysis. Pyrolysis at B0QC for 4 sec gave the monomers, trifluoromethane (ChF3), and hexaf 1 uoropropylene-vinyl idene fluoride oligomers (2). Pyrolysis at SO to 460C gave CF3C+FCH:CFj (m/i = 163) and other smaller fragments. The stable product was not identified since the mass spectral "fingerprints" of pyroysis pro ducts from other f 1 uori ne-containing polymers were simply being compared. Other products included CHF3, HF, and various oligomers and polymer fragments with weights up to 369 amu (3). Combustion. At 314 to 415C, the major combustion products identified were CO, CHF3, anc CH2:CFj plus fluorinated C7 to C* saturated and unsaturated hydrocarbons (4). weight loss was 60S after < 1 hr at 40QC. Volatiles were generated at tem peratures as low as 200C (5). At 85QC, combustion gave only CO and C02; no HF, F-containing compounds, aldehydes, or carbon aerosols were detected using infrared and gas chromatographic methods (6). References 1. G. G. Hawley. The Condensed Chemical Dictionary. 10th ed. hew York: Van Nostrand Re inhold Company, 1961. 2. J. T. Blackwell. Quantitative Determination of the Monomer Composition in Hexafluoropropylene/Vinyl idene Fluoride Copolymers by Pyrolysis-Gas Chroma tography. Anal. Chem. . 4B{13), 1883-1885 (1976). 3. A. J. Pidduck. Mass Spectrometric Analysis of Halogenated Polymers. J. Anal. Aopl. Pyrolysis. 7(3), 215-229 (1985). 4 L. A, Oksent'evich and A. N, Pravednikov. Thermal Degradation of Poly(viny'icene Fluoride) ana a Vinylidene Fluoride Copolymer with Hexafluoropropylene. Vvsoxomol. Soeoin., Ser. 3, 10(1), F9-52 (1968). 5. S, Barron. An Investigation of the Effects of High Temperatures Upon various Industrial Polymers. J. Fire Flammability, 7(July), 387-400 (1976). 6. L. T. Poddubnaya, A. I. Eitlngon, L. S. Naumova, T. A. Shashina, and N. N. Korobeinikova. Study of the Composition and Toxicity of Thermodestruction Products of Fluorine-Containing Synthetic Materials. Giq. Sanit. , (12), 61-63 (1981). HONS 217914 Section 4 nitrogen-containing materials CREOSOTE CASRN: 8001-58-9 Synonyms; Coal tar creosote [to distinguish from beechwood creosote, which is used for medical purposes]; creosote from coal tar; creosote oil [Chemical Ab stracts Service assigns this substance a separate registry number]; dead oil; liquid pitch oil; tar oil (1). Trade Names (Producers): Preserv-o-sote [creosote oil] (Crowley Tar Products Company, inc.) (C). Nelson's C-ecsote Wood D-eservative (B.F. Nelson Manufacturing Company) (3); Lacco Creosote A.W.P.A. (Los Angeles Chemicals) (3). General Information Molecular Formula; Unspecified. Composition; Coal tar creosote is a high-boiling distillate of coal tar produced by high-temperature carbonization of bituminous coal (4). Residual oils from refining coal tar include heavy naphtha, dephenolated carbolic oil, naphthalene drain oii, wasn oil, straineo anthracene oil, ano heavy oil. These fractions are blended to give "creosotes" or "creosote oils" conforming to specifications sucn as Standard Pl-78 of the American Wood-Preservers' Association (AWPA) (4,5) (see Table 4-1). Timber-preservation creosote is a blend of primarily wash oil or light creosote (boiling range 224-291C), drained anthracene oil (boiling range 247:55C), and heavy oil or heavy creosote (boiling range 285-395C). Besides the c-eosote defined by AWPA Standard Pl-78, AwPA has standards for creosote blended with 20, 20, and 40% coal tar (6,7). a-: HONS 217915 Table 4-1 AMERICAN WOOD-PRESERVERS' ASSOCIATION SPECIFICATION Pl-78 FOR TIMBER-TREATING CREOSOTE (4.S) F-action Oisti11inq 2.0% 12.0% 10.0-35.0% 40.0-65.0% 60.0-77.0% Components of Fraction Unidentified PAHs Naphthalenes Acenaphthene, fluorene, dibenzofuran, phenanthrene, anthracene Chrysene, fluoranthene, pyrene Distillation Range. C < 210 < 235 200-270 < 270 < 315 270-355 < 355 > 355 The chenical composition of creosote varies according to the coking temperature and the source of the coal used. Longer carbonization times and higher tempera tures favor PAH formation. Products called creosote that are distilled from sources otner than coal are very different in composition from coal tar creosote ;&). The remainder of this oiscussion is restricted to coai tar creosote. The word creosote is used unmodified. Creosote's chemical composition has been characterized by Lijinsky et al. (1963) (9), Lorenz and GJovik (1972) (5), Nestler (1974) (10), and others. Table 4-2 lists many of the components, but it is not exheustive; 162 individual components had been Identified by 1962 (10). Creosote contains about 85% polycyclic aromatic hydrocarbons (PAHs), up to 3% tar acids (phenolic compounds), about 5% tar bases (nitrogen-containing compounds), and about 5% benzothiophene and dibenzofuran (S and-0 analogs, respectively, of the PAH fluorene). Five PAHs--phenanthrene, fluor anthene, fluorene, acenaphthene, and pyrene--account for about 50% of the mass although several other PAHs have been identified and/or quantitated (5,8-13). t- > MOMS 217916 Table 4-2 COMPOSITION Of COAL TAR CREOSOTE Component Formul a Polycyclic aromatic hydrocarbons (PAHs) Phenanthrene Fluoranthene Fluorene Acenaphthene Pyrene Methyl anthracenes Chrysene Methylfluorenes Methylphenanthrenes Naphthalene Anthracene Benzof1uorenes Dimethyl naphthalenes 2-Methyl naphtha 1ene 1-Methy1 naphtha 1ene Biphenyl Benz[a]anthracene 8enzofa]pyrene Benzo[j]fluoranthene Benzo[k]f1uoranthene Benzo[e]pyrene Benzo[b]chrysene Perylene Unidentified PAHs Acenaphthylene Indene PAH analogs containing O & S Benzothioohene Dibenzofuran Tar bases (N-containing components) Acridine Aniline Bemonitri le Carbazole Indole n-N*phtfryl urine B-Naphthyl Mi ne Quinoline o-, m-, i g-Toluidine Xylidines C,,H, o OjsMio CiaHlO 0i2^10 0ieHio CHj-C14H, 0ihi2 CH<j Ci3^9 CH3-Ci4H# Oioii* Ci,Hl0 0iTW12 (CH3)2C10H CHj-Ci0H7 OHj-Cio^t CHs'0eHs ^20^12 0aoH12 C20H12 CjjH14 C20H12 CiaH# C*Ht C,H,S l|jHjO (continued) Concentratii *- 85 21.0 10.0 10.0 9.0 8.5 4.0 3.0 3.0 3.0 3.0 2.0 2.0 2.0 1.2 0.9 0.8 0. 3 0.02. o.: 0.03 0.02 0.02 0.005 0.004 <2 7 >5 5.0 <5 2.0 Reference 1 5, 10 5, 10 ?. 15 5, IB 5. 10 5, 10 5, 10 5, 10 5, 10 I. 10 5, 10 5. 10 5. 10 l,5, 10 10 5, 10 9 9 ,`U "9 9 9 9 9 5 12 10, 12 10, 12 5 10 10 10 10 S. 10 -10 10 10 10 8, 10 B, 10 4-3 MOWS 217917 Table 4-2 (continued) Component Formula Tar acids (phenolics) Phenol Cresols Xyleno! s Trlmethy 1 phenols 3-Ethyl-5-methyIphenol 2,3,5,6-Tetramethylphenol; Durenol Naphthols C*Hs0H ch3choh (CH3)iCH30H (CHjJjC.HjOH CH3(C2Hs)C*H30H (CHj)4CH0H CioH70H Concentration X < 3, 10 Reference 13, 10 6. 10 6, 10 6, 10 10. 12 10. 12 10, 12 6, 10 Uses. Creosote is used for impregnating wood such as railroad ties, utility poles, and marine pilings to protect from rot and worms. In 1978, 34,100,000 gal, creo sote; 8,400,000 gal. creosote-coal tar solutions, and 30,200,000 gal. creosote* petroteum were sold for wood-preserving applications, It is also used as a water proofing agent, a fuel oil constituent, a lubricant for die molds, pitch for roof ing, and manufacture of read binders, norticulcute' winter wash oils, cneoicaii, and lampblack (carbon black) (1.7,13.14). Summary of Experimental Studies Reviewed Pyrolysis. No specific information was found. Combustion. Concentrations of PAHs sampled downwind from open burning of creosotetreated railroad ties doused with No. 2 fuel oil were much higher than from similar ournng of green wood. The burning produced large quantities of olack smoxe. The PAHs determined in the total solid particulate (TSP) included acenaphthene, beni[a]anthracene, acenaphthylene, benzo[a]pyrene, dibenz[a,h]anthracene, benzotb]fluoranthene, pyrene, chrysene, benio[k]fluoranthene, phenanthrene, benzo[g,rO]perylene, and o-phenylenepyrene (indeno[l,2.3-c,d]pyrene) (listed in approximate order of decreasing yield). Fluorene and naphthalene we-e detected but not quanti tated. Product yields are listed in Table 4-3 (15). Of the PAHs released by burning, benzo[a]pyrene and dibenz[a,h]anthracene are the strongest carcinogens. Benz(a]anthracene, benzo[k]fluoranthene, chrysene, and ophenylenepyrene were the other carcinogenic PAHs identified (IS). Creosote itseinas been associated with human skin cancers and is an animal carcinogen; however, creosote*impregnated wood poses little or no danger to humans (1,8). j-j MONS 217918 Table 4-3 PAHs IN AIR TOTAL SOLID PARTICULATES DOWNWINO FROM OPEN 8URNING OF CREOSOTE-TREATED RAILROAD TIES OOUSED WITH NO. 2 FUEL OIL (15) Components Formula . Acenaphthene CtjHl0 Benzfa]anthracene Acenaphthy lent c12h. Benzo[b]fluoranthene Benzo[a]pyrene C20hi2 C2oH12 DibenzTa.hJanthracene C22Hit Pyrene ~ ~ Cishio Chrysene Benzofk]fluoranthene CiHu CjqHjJ Benzo[5,h ,^]pery1 ene C22Hi2 Phenanthrene Ci4H10 o-Phenyl enepyrene; C22hU " Indeno[l,2,3-cdjpyrene FI uorene Ct3HlO Naphthalene* 1 2 3 4 5 6 Concentration in Total* Solid Particulate, ppm ^ 1380-3380 *- 550-1260 * 29D-840 v 10-690 * 10-690 10-690 - 1C-690 *. 50-470 v 5-230 v 50-130 v 50-130 v 50-130 Not Quantitated Not ouantitated Carcinooenic no yes no yes yes yes no yes no no no yes no susrect *Range given for three or four runs based on the ratio of the specific PAH concen tration to the concentration of total solid particulates in air. References 1. G, G. Hawley. rhe Condensed Chemical Dictionary. 10th d. New York: Van Nostrano Reinnoid Company, 1981. 2. J. H. Kuney. Chemcyclopedii 86. Vol. 4. Washington, DC: American Chemical Society, 1985. 3. R. E, Gosselln, H. C. Hodge, R. P. Smith, and M. N. Gosselin. Clinical Tox icology of Commercial Products. 4th Ed. Baltimore, MO: Williams and Wilkins Company, "T57T----------------------------- 4. American Wood-Preservers' Association. "Pl-78 (Revised) Standard for Coal Tar Creosote for Land and Fresh Water Use," American Wood-Preservers' Association Standards. Washington, OC, 1978. 5. L. F. torenz and L. R. Gjovik. Analyzing Creosote by Gas Chromatography. Am, Woofl-Preserv, Assoc. . 68, 32-42 (1972). 6. 0. McNeil. "Tar and Pitch" in: Kirk-Othmer Encyclopedia of Chemical Science and Technology. 2nd Ed. A. Standen, Executive Editor. New YorlT: Inter science Publishers, a Division of John Wiley and Sons, 1969, pp, 652-582. d-t HONS 217919 7. 0. McNeil. "Tar and Pitch" in: Kirk-Othmer Encyclopedia of Chemical Sc-ence and Technology. 3rd Ed. M. Grayson, Executive Editor. New fork: Inter* science Publishers, a Division of John Wiley and Sons, 1983, pp. 564-600. 8. U.S. Environmental Protection Agency. Wood Preservative Pesticides Creosote, Pentachlorophenol and the Inorganic Arsenical (Wood Uses). Position Document 273. EPA-54079-82*004, PB82-29956, Springfield. VA: National" technical Information Service, 1982. 9. W. lijinsky, I. Domsky, G. Mason, H. Y. Ramaki, and T. Safani. The Chromato graphic Determination of Trace Amounts of Polynuclear Hydrocarbons in Petro latum, Mineral Oil, and Coal Tar. Anal. Cham.. 35, 952*956 (1963). 10. F. H. K. Nestler, The Characterization of Wood-Preserving Creosote by Physical and Chemical Methods of AnalyTiT LfSDA Forest Service Research Paper FPL 195. 1*31~ AC"78T4544/8GA, Springffe 1 d, VA: National Technical Information Service, 1974, 11. J. J. Black. Movement and Identification of a Creosote-Oerived PAH Complex Below a River Pollution Point Source. Arch, Environ. Contain. Toxicol., 11(2), 161-166 (1982). 12. D. F. Goerliti, P. J. Colberg. J. 1. Schnoor, 0. Wanner, A. J. 0. Zehnder, and R. P. Schwarienbach. Migration of Wood-Preserving Chemicals in Contam inated Groundwater in a Sand Aquifer at Pensacola, Florida. Environ, Sci. Techno!., 19(10), 961-968 (1985). 13. M. Windholi. The Merck Index. 10th Ed. Rahway, NJ; Merck and Company, 1983. 14. M. Sittig. Hazardous and Toxic Effects of Industrial Chemicals. Park Ridge, NJ: Noyes Data Corporation, 1979. 15. 0. Becker, G. Eckhardt, J. Seitz, and T. Johnson. "Open Burning of Creosote Treated Rail Ties: A Case Study in Health Risk Assessment" in: Proceedings of the APCA Annu. Meet., 77th, vol. 6, 84-102.6, 1984, 14 pp. iicyanoiamioe CASRN: 461-58-5 Synonyms'. Cyanoguanidine; dicyanodiamide; dicy. General Information Molecular Formula: C2H4N, Structure: NH II NH2CNHCN "-o HONS 217920 Paper web is impregnated with dicyandiamide and may (1) or may not (2) be heated (e.g. , 50C for 0.5 hr) to dry. Heating in air for 15 hr at 135C may cause some chemical bonding to the cellulose (< 20X). N-containing compounds like dicy "block carbonyl groups and inhibit the chain reaction of oxidation and the thermal de struction of cetluiose." Amino groups "block aldehyde groups " (3). Uses: Cicyanciamide is used in the manufacture of melamine, barbiturates, guani dine derivatives, fertilizers, dyes, explosives, fire-proofing compounds, case hardening preparations, cleaning compounds, and soldering compounds. It is used as a stabilizer for nitrocellulose and detergent compositions, as a modifier for starch products, and as a catalyst for epoxy resins (4,5). Paper products produced from 1ignocel1ulose pulps are conmonly used to insulate various electrical apparatus, e.g., as dielectric spacers in caoacitors or insulat ing sheet for transformer windings. The entire capacitor or transformer winding is typically immersed in a liquid dielectric such as petroleum oil, waxes, or chlori nated hydrocarbons. Various U.S. patents describe methods in which the thermal stability of insulating papers are improved by treating or impregnating with N-contaming compounds (such as dicyandi amide or melamine) and/or a protein such as casein or soybean protein (1). Oicyandiamide is preferred because It is "a particularly good nitrogen-donor to cellulose and therefore a good thermal stabilizer, it is readily available, and it is economical" (1). Optimal concentration of dicyandiamide is 2% based on the weight of the paoer (3). Thermal Decomposition Mechanisms No information was found. Summary of Experimental Studies Reviewed No information was found on the pyrolysis or combustion of paper impregnated with dicyandiamide or on pyrolysis or combustion of dicyandiamide itself. References 1. f. S. Sadler, P. r. Hettwer, V. H. Viet, and C. R. Acker (McGraw-Edison Co ), Elect-ical .nsu'itmi Paper. U.S. Patent US 4407697, October 1963, 6 pp.3 3. Wesf'nghouse Electric Corp. Oi cvandiamide-Imprebnated Thermally Stable Elec- t-icai Insu'ation Paoer. Brit. Patent G6 1113960, v>uly 1368. 4 pp. HONS 217921 3 M. B. Samaryanova and V. A. Sokol'nikava, Increase in the Heat Resistance of Cable Paper. Soversh. Tekhnol, Buffi., K. A. Veinov, Editor. Moscow, USSR: "Lesneya Promyshlennost,1'1 1972, pp. 122-131. 4, H. Windholz, Editor. The Merck Index. 10th ed. Rahway, N.J.: Merck and Company, Inc., 1983. 5. G. G, Hawley. The Condensed Chemical Dictionary, loth ed. New York; Von Nostrand Reinhold Company, 1981. KAPTON . CASRN: 25036-53-7 Synonyms: PyromelHtic acid-bis(g-aminophenyl ether) copolymer, polyimide SRU; Poly[(5,7-dihydro-l,3,5,7-tetraoxobenzo[ 1,2-c: 4,5-c`]d1 pyrrole-2,6(lH,3H)-diyl)1,4-phenyleneoxy-1.4-phenylene] (9CI); Poly[(oxydi-g-phnylene)(pyromel1(tic diiaide)]; Benzo[ 1,2-c:4,5-c1 ]dipyrrole, aeriv. . polymer (9CI); Bis(4-ainophenyl) ether-pyromel1itic anhydride polymer, SRU; 4,41-Diaminodiphenyl ether-pyromel1itic acid copolymer, polyimide SRU; 4,4`-Oxydiani1ine-pyromel1itic anhydride polymer SRU; Boly[N . N1-(oxvoi-c-phenyl enejpyromel 1 i t imide]; Polyme- SP; ool\[N.N'-,'t:.r'oxydiphenylene)pyromel11timide]; Polyimide PM; PM (polyimide). Trade Names (producers): Kapton, Kapton H (OuPont); Vespet SP-1 (DuPont). General Information Molecular Formula: (C^HioNjOs),, Structure of Monomers ano Polymer: 4,4'-Oiaminodiphenyl ether HONS 217922 Uses: Thermoset polyimides are advantageous in thin-film products. Major applica tions are those requiring hign quality and performance such as the aerospace and electronics markets. Electrical applfcations--Vespe1 (molded parts) and/or other polyimides such as Kinel (molded parts) and Kerimid 601 (laminates) are used in high-reliability printed wiring boards, integrated circuit carriers as a substi tute for ceramics, and automotive parts that require thermal insulation such as wires in electric motors. Kapton film is used in electric motors "where size is important." It is used to insulate aircraft and missile wire cable, flat flexible cable, and magnet wire, and used as spaghetti tubing. Polyimides may also be used to coat semiconductor devices and electrical components (1). "DuPont's Vespel SP-1...has been used as an insulating material in molten salt electrochemical power sources which operate at internal temperatures in excess of 4C0C" (2). Thermoplastic polyimides may be used as fibers, film, laminates, or foams. Elec trical uses include laminates for printed circuit boards. Cast films are being cevelopeo for use in flexible printed circuits and insulation for wire, cable, and electric motors (1). Thermal Decomposition Mechanisms Pvrolysls. Thermal degradation occurs very drastically in the first few minutes and gradually levels off. Onset of the two stages of pyrolysis depends on the heating rate. Most weight loss (^ 40JS) occurs during the first stage (below 700C). The second stage occurs at v 900C and is associated with n. 4.5X weight loss (3). Pirst-stage reactions include cleavage of C-N and ether C-0 bonds. Homolytic cleavage of C-N bonds might be followed by CO elimination and formation of nitrene and teniyne intermediates (3). "'Jncyc 1 ized rings" (that is, monomer units wherein an imide ring did not form and a free carboxyl group is present) may make a "soecial contribution to the degradation reactions of polyimides." There appears to be one uncycliied ring per 8 to 9 poly mer units. Polyamic acids may dehydrate or decarboxylate on heating. Hydrolytic sc'ssicn w'th release of C02 may occur wnen water is present. The proposed mecha nism aces not account for the presence of methane in the products formed from c .--q lysis at 700C. Hydrogen may be stripped from aromatic rings at temperatures 60C: (4). 4-9 MONS 217923 The following mechanism was proposed to account for the products formed on pyroly sis at 512C in nitrogen. Loss of CCj from the imide carbonyl groups leaves free radical -C:N- linkages, which ultimately leads to bond breaking and formation of free nitriles. Loss of CO from one imide carbonyl group leaves the polymer intact with the remaining amide linkage. Free radical cleavage of the ether linkage of the polymer followed by H atom abstraction gives N-hydroxyphenyl substituted imide molecules (5). The second stage of pyrolysis may involve formation of a highly conjugated aro matic network from dimerization and trimerizatton of benzyne intermediates. This network may be responsible for the very stable, electrically conducting material formed by pyrolyzing Kapton [conductivity is 12 (ohm-ca)*1] (3). A large fraction of the original N content is still present after pyrolysis even at 800C; therefore, graphitization is minimal (6). Combustion. Ho information was found on combustion of Kapton, but its thermal oxidative degradation at - 400*C has been studied. Film aged at 4O0C in air for a short time undergoes extensive crosslinking during the early stages ;f oxicc:or. Crosslinks are too stable to be amide functions. The aryl-ether bond is possibly broken (7), The major crosslinking reaction apparently occurs through coupling of the diphenyl ether units either by a direct dehydrogenation reaction or by cleavage of the aryl-ether bonds to give phenolic groups that undergo subsequent reactions. The pyromel1itimide ring is degraded, forming phthalimlde and other ring structures (8). During oxidation at 400C, loss of the diphenyl ether units is the fastest pro cess, with 50X of the units having reacted at only 2 to 3X weight loss. This supports the crosslinking mechanism. Within the first 3 hr, ether cleavage, dehydrogenation, and pyromel11timide destruction reactions all proceed at approxi mately the same rate. After that time, the yield of insoluble polyamines remains about the same, but the yields of soluble aminophenols and modified pyromelliti mide units increase up to about 10 hr before leveling off. The polyamines, con taining the ether linkage, are probably intermediates in the formetion of the aminophenols. Since these reactions are much aster than volatilization loss, tne degradation products are from "chemical structures completely different from those of the original polymer," Volatiles come largely from the modified structure (9). i-10 HONS 217924 Besides inducing free radical crosslinking, 02 may react with polymer to give a quinort* structure in the aromatic ring attached to the imide N. Further oxidation cleaves that ring to a dicarboxylic acid; heat converts the quinone structure to a char plus carbon monoxide (5). Summary of Experimental Studies Reviewed Pyroly si 5, Most weight loss (% 40%) occurred below 700C within the first few minutes of heating [at least at that high a temperature], A second stage of ther mal decomposition began about 900C but was associated with only *v 4.5% weight loss (3). Weight loss was low (S 5%) after heating for 75 hr at 300 to 350C but became "catastrophic" (-v ZOX) by 400C within SO hr (10). Heacock and Barr (1965) (11) reported that Kapton completely disappeared after heating at 500C [time not given in secondary reference]. The only mechanistic explanation for the source of the major pyrolysis products, C02 and CO, was given by Arnold and Borgtnan (1972) (5), who suggested they came from two imide groups and one imide carbonyl group, respectively. Other inorganic gases formed at 350 to 700C were hydrogen (He), water (H20), and hydrogen cyanide (HCN). Benzene (C#H(), phenol (C#HB0H), and benjoni t-i1 (CfHjCN) wws reoorted in this ranoe, too. Methane (Ch4) was reDo-;n"1 in the volatiles after pyrolysis at 700C (4), Two reports mention detection of terephthalonitrile (l,4-dicyanob*n2*ne) [C#H4(CN)2] at 350-470*0 (5) and 600*C (12) . Arnold and Borgman (1972) () tentatively identified the mass peaks 16B-170 as dibenzofuran after pyrolysis at 350 to 470*C. Additional products identified by Hummel et al. (1977) (12) after pyrolysis at 600C were -a*tnophenol (H2NC#H40H). phenyl isocyanate (C*H#NC0), phthalimide and five substituted phthalimides, -aminophenyl phenyl ether (H2NCsH40C*Hs), three substituted pyromellitimides, and a char, The fact that pyrolysis of Kapton above 700C gives a highly conductive material suggests that a highly conjugated aromatic network forms, resulting from dimeriza tion and trimerization of benzyne intermediates (3). The char formed from H film pyrolysis at 800C contained 7% N, 12% 0, and 3% H (13). Combustion. Information on combustion products was not found. Most studies on thermal oxidation of Kapton and other forms of the same polymer focused on the mechanisai. After the polymer was haated in air at 300*C for 7 hr, 7.9% of its weight was lost; 95% of the loss was evolvtd in the first half hour. The liquid distillate comprised reaction solvent (dimethylacetamide), polymeric material, and traces of water. Gases evolved were CO and C02. Part of the oxygen consumed was retained by the polymer (14). Crosslinking accompanied by 50% loss of the diphenyl ether units occurred within 5 hr at 400C while only 2 to 3% of the polymer's t-ll MONS 217925 weight had been lost- At 40QC, the pyrome11itimide structure degraded before volatiles were emitted (9). References 1. Modern Plastics Encyclopedia. 1965-1966. Vol. 62, No. 10A. J. Agranoff. Editor. New York: McGraw-Hill, Inc., 1965. 2. R. P. Clark. Thermal decomposition of Po!y(4,4'-oxydipheny lene pyromellitimide). Thermochimica Acta. 6(5), 473-480 (1973). 3 J. W. P. Lin, A. J. Epstein, L. P. Dudek, and H. Rommelmann. Pyrolysis and Electrical Properties of Poly[N,N1-(p,p'-oxydiphenylene)pyromel1itimide]. Or:, Coat. Plast. Chem. , 43, 482-485 (1980). 4. D. P. Bishop and 0. A. Smith. Combined Pyrolysis and Radiochemical Gas Chromatography for Studying the Thermal Degradation of Epoxide Resins and Polyimides. II. Degradation of Polyimides. J. Appl, Polym. Sci.. 14(2), 345-354 (1970). 5. C. Arnold, Jr. and L, K. Borgman. Chemistry and Kinetics of Polyimide Degra dation. jnd. Eng. Chem,, Prod. Res. Oeveloo. . 11(3), 322-325 (1972). 6. P. E. Cassidy and N. C. Fawcett. ''Polyimides`' in: Kirk-Qthmer Encyclopedia o* Chemical Technology. Vol. 18. Gravson. Editor. New York: Inte-- science Puolisners, a Division of Jonn Wiley ano Sons, 1S3, pp. 704-715. 7. R. A. Oine-Hart, 0. B. V. Parker, and W. W. Wright. Oxidative Degradation of a Polyimide Film. I. Initial Studies. Br. Polym, J,. 3(5), 222-225 (1971). 8. R. A. Oine-Hart, 0. B. V. Parker, and W. W, Wright. Oxidative Degradation of a Polyimide Film. II. Studies Using Hydrazine Hydrate. Br. Polym. J,. 3(5), 226-234 (1971). 9. R, A. Dine-Hart, 0. B. V. Parker, and W. W, Wright. Oxidative Degradation of a Polyimide Film, III. Kinetic Studies. Br. Polym, J.. 3(5), 234-236 (19711. 10. S. 3a--on. An Investigation of the Effects of Hign Temperatures Upon Various Industrial Polymers. J. Fire Flammabilitv. 7(July), 3B7-400 (1976). 11. 3. F. Heacock and C. E. Be-r. Polyimides--New High Temperature Polymers: H-film a PolypyromelHtimide Film. SPE Transactions. 5(2), 105-110 (1965). 12. D. 0. Hummel, H. J, Ouessel, and H. Rosen. Decomposition Behavior of Thermo stable Polymers as Studied by Pyro-Field Ion Mass Spectrometry. Adv. Chem, Therm. Stable Polvm. [Invited Main Lect. Int. Conf. Therm. Stable Polym.], 1st, Meeting Oate 1975. Z. Jedlinski, Editor. Warsaw: Panst, Wydawn. Nauk. , 1977, pp. 99-118. 13. R. T. Conley and R. A. Guadiana. "Thermal and Thermo-Oxidative Degradation of Polyamides, Polyethers, and Related Polymers" in: Thermal Stability o~' Polymers. Vol. 1. R. T. Conley, Editor. New York: Marcel Dexker, Inc. , 1970, pp. 347-456. 14. C. Scala and W. m. Hickam. The Benavio- o~' Polypyromel 1 itimioe Resins a: Higr, 'emoeratu-es J. Aqq 1 Pp 1 yme- Sc , 5. tae-266 (1965) MONS 217926 NITRILE RUBBER CASRN: 9003-18-3 Synonyms: Acrylonitrile-butadiene copolymer; NBR rubber; nitrile-butadiene rubber. Trade Names (producers): Paracril (Uniroyal); Hycar (8. F. Goodrich). General Information Molecular Formula: (CTHftN)n Structure of Monomers and Polymer: CH2:CHCN + Acrylonitrile CH2: CHCH: CHa------- *> --(CH2CH: CHCHjCHjCH*-- Butadiene 'Lff Uses: High acrylonitrile content: oil well parts, fuel tank liners, fuel hose, gaskets, packing oil seals, hydraulic equipment. Medium acrylonitrile content: aene'?1 -u-r"'* ol1-resistent aDolications. shoe so'es. k'tchen mets, sink tcp?:rp, printing rolls. Low acrylonitrile content: gaskets, grommets, 0-rings (flexible at a very low temperature), adhesives. Binder fuel in solid rocket propellants (1). Thermal decomposition Mechanisms No information was found. Summary of Experimental Studies Reviewed Pyrp1vsis. Major loentified products after pyrolysis at 390C were NHj ana HCN (each in - 5X yield). Traces of hydrogen (H2), swthane (CH4), and Ci to C7 hydro carbons (mostly C2 to C4) were detected in the gases. A liquid product (generally produced in v 50 to % 70* yield) contained unidentified chain fragments. The resi due was not characterized (2). The monoeiers were generally detected after pyroly sis at S00 to 1000C. Czybulka et al. (1981) (3) who pyrolyzed nitrile rubber at 500C, gave the most extensive list of other products: HCN; acetonitrile (CH3CN), propionitrile (CHjCH2CN); and C2 to Cl0 hydrocarbons including toluene (C*HSCH3), styrene (C#HSCH:CH2), ethylbenzene (CtHsC2Hs), cyclopentene or pentadiene, and pentane. At 590C, Shimono et al. (I960) (4) found to C3 hydrocarbons; buta diene (CH j:CHCH:CH2), acetonitrile (CH3N), and methacrylonitrile [CH2:C(CH2 )CN] among the pyrolysis products. 4-13 MOHS 217927 Pyrolysis at 610C of a nitrile rubber containing 33% acrylonitrile (AN) gave the monomer* (more butadiene [BO] than AN), AN dimer and trimer, BO dimer and trimer. an AN-BO fragment, and a B0*AN-B0 fragment (5). Monomers and vinylcyclohexene, as a minor product, were determined in the products from pyrolysis at 77CC (6). After pyrolysis at 1000C, fragments containing one unit of acrylonitrile and one to three units of butadiene predominated over fragments with one to four units of butadiene. The monomers were the major products (7). Combustion. No information was found on combustion of nitrile rubber. References 1. G. G. Hawley. The Condensed Chemical dictionary. 10th ed. New York: Van Nostrand Reinhold Company, 1961. 2. N. Grassie and A. Heaney. Thermal Degradation of Copolymers of Butadiene and Acrylonitrile. Eur. Polym. J. . 10(5), 415-424 (1974). 3. G. Czybulka, H. Ounker, H. J. Ouessel, H. logemann, and 0. 0. Hummel. Studies on Vulcanized ana Ltnvulcanized Rubbers with Small Concentrations or Components (Comonomers, Accelerators, Metal Oxides, Antioxidants) by Pyro-Field Ion Mass Spectrometry, Anqew, Makromol. Cheat. , 100, 1-21 (1981). 4. T. Shimono, M. Tanaka, and T. Shono. Pyrolysis-Gas Chromatography of Buta diene Co-polymers. Anal. Chim. Acta, 96(2), 3S9-365 (1978). 5. J. B. Pausch, R. P. Lattimer, and H. L. C. Meuzelaar. A New Cook at Olrect Compound Analysis Using Pyrolysis Mass Spectrometry. Rubber Chea. Techno!., 56(5), 1031-1044 (1983). 6. K. V. Alekseeva and L. S. Solomatina. Identification and Determination of the Quantitative Composition of Butadiene-Nitrile Rubbers oy Pyrolytic Gas Chromatograpny. Kaucn. Sezma. (8), 54-56 (1978). 7. H. 0. R. Schueddemage and 0. 0. Hummel. Characterization of High Polymers by Pyrolysis Within the Field-Ionization Mass Spectrometer. Advan Mass Spectrom. , 4, 857-866 (1968). N0MEX CASRN: 24938-60-1 Synonyms: Poly(imino-l,3-phenyleneiminocarbonyl-1.3-phenylenecarbonyl); Poly(imino-m-phenyleneiminoisophthaloy1); Poly(flpisophthalamide); m-Phenylenediamineisophthaiic acid polymer, SRU (structural repeating unit); Isophthaloyl chloridem-phenyienediamine polymer SRU; Phenylone polymer; Nylon HT. 4-14 MONS 217928 Trade Names: Nomex; Nomex 410; Nomex 450; Aramid K5 305; Aramid KS 105; Concx; Konnekkusu; APH 50. General Information Molecular Formula: (ChH^NjOj) Structure of Monomers and Polymer; 0 ii RC CP HpN Isopnthalic acid (R = OH) Isophthaloyl chloride (R = Cl) 1,3-Phenylenediamine Nomex Uses: Nomex paper, with or without mica flakes, is used to insulate high perfor mance electrical motors, special transformers (e.g., high-voltge dry-type trans formers), and aircraft generators. The nonmelting, self-extinguishing Nomex paper is useful up to 180C. Nomex fibers are also used for aircraft structures, protec tive garments, and other uses requiring high thermal stability such as filter bags for hot stack gases (1*4). Thermal Decomposition Mechanisms Pyrolysi s. Water loss may occur from chain cross 1 inking during Nomex pyrolysis at 300 to 400*C, Possible reactions are condensations between terminal amino and carboxyl groups, between chain amide or amino end groups and carboxyl groups, be tween amide and isoimide groups (tautomeric forms of amide groups), and between two carpoxylic acid-terminated chains to give anhydrides. In this temperature range, decarboxylation of end carboxyl groups is the most likely explanation for carbon dioxide evolution (5,6). At least some, if not all, of the water evolved below about 4D0C i; probably due to water adsorbed by the polymer (6.7). 4-15 MONS 217929 Products appearing at 40D to 430C--benzoic acid, 1,3-ohenylenediamine, aniline, benzanilide, and N-(3-aminophenyl )be-izamiae--can be accounted for by heterolytic degradation of chain end and penultimate amide groups and by homolytic amide bond cleavage. Benzonitrile, which is also produced in this range, forms from homolytic cleavage of the aromatic C to amido N bond followed by protonation to give the amide and then dehydration to give the cyano group. [The results of Chatfield et al. (6) indicated that the dehydration of amides is the major source of HjO,] The latter sequence of reactions could also give additional aniline, benzanilide, and N*(3-ami nophenyljbenzamide (5). Dehydration of amide groups can also account for formation of 1,3-dicyanobenzene (isophthalonitrile) and 3-cyanobenzoic acid (6). At 475 to 500C, 1,3-dicyanobenzene is evolved, probably from the same kind of reaction sequence that produces benzonitrile. Larger amounts of water are also evolved (5). Ehlers et al. (1) proposed a major route for th* initial thermal degradation of sramids that involved cleavage of the C-C bond between the aromatic ring and the carbonyl group carbon to give an aromatic isocyanate. Brown and Pow*-- (5) consid ered this mecnanism unlikely since no isocyanates were detected in tne proouccs. Chatfield et al. (6) did not consider isocyanate formation at all. The following reactions were proposed by Chatfield et al. (6) for thermal degrada tion of Nomek (I). [Note: In all formulas, CSH4 represents an m-phenylene group.] -~NHCOCsH4CONHCflH4-*m2 1? C~J^va-^---------------- 2) H atom abstraction -*HC0CH4C0NH2 CH----(II) n Dehydration^ .-NHC0CeH*CN - NCC*H4CN + H20 1,3-Oicyanobenzene I + H,,0 -NHC0CaH4C02H + H2NCsH4-III HI Oecarboxylati or^ .,,NHCCC<(1s U CO, III II Cleavaoe; 2) H atom abstraction NCCsH4C02rl 3-Cyanobenzoic acid --16 MOMS 217930 ! Cleavage .. .NHCOC,,H4CO' + 'NHCSH4NH--IV NHC0C6H4'IV ----------------------------- -- * CO Combustion. Molecular oxygen apparently reacts extensively with Nomex during thermal degradation in air. For example, at 550C recovered products contained 42.9X oxygen based on the weight of the original sample, whereas the original sample contained only 12. 5X oxygen. CO, C03, and H20 account for most of the oxygen uptake (6). Summary of Experimental Studies Reviewed Pyrolysis. Carbon dioxide, water, and carbon monoxide were the major inorganics evolved from Nomex pyrolysis according to most reports, Ehlers et al. (7) and Chatfield et al.{6), however, reported that thorough drying of Nomex samples before pyrolysis would preclude water loss during pyrolysis, at least up to 380BC. Hydrogen and hydrogen cyanide were major inorganics evolved from pyrolysis acove SOO or 600C. Minor inorganics included cyanogen, ammonia, and nitrous oxide (5,7). Organics usually found in major amounts among the volatile products evolved during pyrolysis below 500*C were benzene, toluene, benzonitrile, 1,3-phenylenediamine, benzoic acid, and aniline. Above 50QC, toluene became a minor product and 1,3dicyanobenzene became a frequently determined, and often major, product. N-{3~ Aminopnenyi)benzamiae ano 1,2-pneny ieneaiamine were major products 'rom oyrolysis at 600 and 700C. Trace to minor organics reported included C, to C4 alkanes or alkenes, acetylene, nitriles including 3-cyanotoluene (3-tolunitrile), biphenyl and its 3-cyano and 3-amino derivatives, and phenyl isocyanates. The residue became more aromatic between 450 and 55QC. Loss of most of the hydro gen and oxygen by 1,000C left a cha- whose molecular formula approximated C13NH. ~he charred residue comprised aoout SOX of the original polymer weight after 4 min at 1,OCOC under helium (6,8). 4-17 HONS 217931 Products and their yields for the temperature ranges 300 to 481C and 500 to 1,000*0 are given in Tables 4*4 ana 4-5, respectively. Combust!on: Ouring thermal degradation in air or oxygen, Nomex lost weight rapidly in the range 400 to 600C and was entirely consumed by 1,000C (6), Volatile prod ucts recovered ^rom degradation at 300 to 1,000C were primarily water, carbon dioxide, and/or carbon monoxide. HCN at 1.2 weight 5 (based on the weight of the original sample), acetone at 4.2 weight X, and an unidentified compound of molec ular formula Ct0K12 at 7.2 weight X were recovered from flaming combustion and represent the only other products identified in amounts exceeding IX at any tem perature studied. Nitriles, benzene and substituted benzenes, benzoic acid, 3-cyanobenzoic acid, acetaldehyde, acetic acid, alkanes and alkanes, nitromethane. NO, n20, and cyanogen comprised most of the remaining combustion products. Details are given in Tabie 4-6. i-ie MOMS 217932 T itle 4-4 HONS 2 1 7 9 3 3 -ill j | ii ee 0O GOu"> V 09 w-n i>/*l oc r it iij L a V Y*Yc s t;i' * ' ......... 4J i ii l3 i lI fI i i i? l l ii T lI 1I 1l i i1 i ii i - *. .*.. .. j.< fli-Jjirt* \ i i *ir * i * *'l {1*0* Ia i * i 1 1 l t *-19 HONS 2 1 7 9 3 4 i .i is o (J"> UOo"> c r; 3i J r1 !ws J3S- * h* tt ii il >2 *J ttI t tijirli ScliSH If 6 ^ 9 * C t ,i. * I.. 5ss c,, S .^--.ii ji ttiiti iii I -J* ii liVi?' * j h. *&!* n ;tlivii 1| .s4i is ir * i no * s s tm aii!m*eiseInHs -.s *; 5**5 -- *- *<<1*2 t-- m. , tf * * a, Jl iz 1-20 "'1 SU l> *0, ri # r t bij I! d-21 Table 4-S (continued) HONS 2 L 7935 MONS 2 1 7 9 3 6 " IE X r. i.s'r. see b J!Ii;lli ?| ' c-B - : eee.s. ! Hi Hi * T. ;c ! . fSfiVlBSjs ; ** \" * f. : .< ju 4 iijauui A, * ' ^I ta.t * lfc-S* ! fc= r. '- ! ih< IBS ; iu***-*;uj*,, -C r ! * }ii. I ..iH.1.!!! S'h: ,: s5555555s' : -; . i:\ * * t I : 1 : * J i < i i i - : ' TTI t .i i i &-->2 References 1. R. N. Sampson. "Insulation, Electric" in; Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed-, Vol. 13. M, Grayson, Editor. New York; Interscience Publishers, Division of John Wiley & Sons, 1961, pp. 534*563. 2. J. Preston. "Aramid Fibers" in: Kirk-Qthmer Encyclopedia of Chemical Tech no! oqy. 3rd ed. , Vol. 3. M. Grayson, Editor. New York; Interscience Publishers, Oivision of John Wiley & Sons, 1976, pp. 213-242. 3. W. J. Roberts. "Fibers, Chemical" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed., Vol 10. M. Grayson, Editor. New York: Interscience Publishers, Oivision of John Wiley & Sons, 1960, pp. 146-166. 4. L. 0. Kaser. Dry-Type Transformers in the United States. Paper presented at the 4th BEAMA International Electrical Insulation Conference, Brighton, England, May 11, 1962. 5. J, R. Brown and A, J. Power. Thermal Degradation of Aramids: Part 1- Pyrolysis/Gas Chromatography/Mass Spectrometry of Po1y(l,3-phenylene Isophthalamide) and Poly(l,4-phenylene Terephthalamide). Polym. Degradation Stab. . 4, 379-392 (1962). 6. D. A. Chatfield, I. N. E'nhorn, R. W. Mickelson, and J. H. Futrell. Analysis of the Products of Thermal Decomposition of an Aromatic Polyamide Fabric. J. ppiym Fci Pr'vr Chem Fd. , 17, 1367-]??'. '1979). 7. G. F. L. Ehlers, K. R. Fisch, and W. R. Powell. Thermal Degradation of Polymers with Phenylene Units in the Chain, IV. Aromatic Polyamides and Polyimides. J. Polym. Sci.. 8(12), 3511-3527 (1970). 8. Y. P. Khanny, E. M. Pearce, 0. T. 6. Smith, H. Burkitt, H. Njuguna, 0. M. Hindenlang, and 0. 0. Forman, Aromatic Polyamides. II. Thermal Degradation of Some Aromatic Polyamides and Their Model Oiamides. J. Polym. Sci. , 19, 2817*2834 (1981). 9 E. P. Krasnov, V. M. Savinov, L. 8. Sokolov, V. I. Logunova, V. K. Belyakov, and T. A. Polyakova. Thermal Degradation of Isomeric Aromatic Polvamides. YvsoKomol. Soed., 8(3), 380-386 (1966). ' 10. H. J. Kretzschmar and 0. Gross. Pyrolysis-Gas Chromatography of Polyamides. Kunststoffe, 65(2), 92-94 (1975). 11. P. Perlstein. Identification of Fibers and Fiber Blends by Pyrolysis Gas Chromatography. Anal, Chim. Acta, 155, 173-181 (1983). 12. L. E. Reshatnikova, L. I. Slyusareva, T. N. Shuvalova, and S. I. Kirsh. Analysis of the Composition of Polymer Material Combustion Products by GasLiquid Chromatography. Fiz,-Khim. Osn. Sint. Pererab. Poiim.. 3, 9E-101 (1978), 13. M. Oay, T, Suprunchuk, and 0. M. Wiles. A Combustibility Study of tn# Gaseous Pyrolyzates Produced from Some High-Performance Fabrics. J. App 1. Polym, Sci. . 28(12), 3681-3693 (1983). 4-23 HOMS 217^37 nylon 6 CASRN: 25038*54*4 Synonyms: Poly(iminocarbonylpentamethy1ene): polycaprolactam; polycaproamide; caprolactam polymer. Trade Names (producers): Capron (Allied Corp,); Fosta (American Hoechst); Ultramid (Badisehe Corp.); CRI (Bemis Co.); Firestone (Firestone); Enkalon; Grilon (Emser Werke); Mirlon; Perlon; Phrilon; Amilan (Toray Ind. , Inc.). General Information Molecular Formula: (CsHuN0)n Structure of Monomer and Polymer: e*Caprolactam Nylon 6 Uses: Nylon G is used in bearings, gears, bushings, coil forms, brush backs, tubing, and tape (^). It is widely used in meat packaging (2). Nylon plastics are used in numerous consumer products, including tire cord, fishing lines, tow ropes, garden hose, and woven fabrics (3). In general, nylons have their biggest rarrsts ;n tne automotive industry for applications such as electrical connectors, wire jackets, emission cannisters, and lignt*outy gears, electrical ano snc.'in; applications use large amounts of nylons. Fire retardant (UL94 V-0) nylons are usea in the electronic and electrical fields. Nylons are used for plugs, connec tors. wir* devices, terminals, cable ties, wire jacketing, antenna mounting de* vices, and power tool housings (2). In wire and cable applications, nylons are used as jacketing underwhich the primary insulation is polyethylene or poly(vinyl chloride) (4). 1 hernial Oecomposi tion Meehan sms Based on mass spectral data, water elimination (*18 amu), loss of the acid amide group (-44 amu) after rearrangement, and loss of methylene groups from longer po'y amides (*42 or *56 amu) by C' s*elimination form most of the decomposition oroouccs HONS 217938 Polyamides and copolyamides with a large number of methylene groups favor decompo sition by cis-elimination and cleavage of the amide bonds (5). Nylons apparently degrade initially by random chain scissions of bonds between N and carbonyl-group C (the weakest link), between N and methylene-group C beta to a carbonyl group (the second weakest link), and between C's of adjacent methylene groups beta to a carbonyl group. In addition, hydrolysis produces amines and carboxylic acids. Decarboxylation of the latter is the source of most of the C02 evolved, Nitriles arise from dehydration of amides (6). Summary of Experimental Studies Reviewed Pvrplysis. Recent reviews list thermal decomposition products of polyamides as carbonaceous residue and volatile products such as NHa, nitriles, amines, cyclic ketones, esters, CO, C02, Hs0, hexamethyleneinline (hexahydro-lH-azepine), hexylamine, heptylamine, and methylamine (^,fl)- Ohtani et al. (1982) (9) generalized about the kinds of products generated from pyrolysis of various nylons ct 550C. The major differences were that cyclopentanone is a prevalent degradation product if adipic acid was one of the starting materials and that those mononitriles formed that contain one amide group nave different structures depending on the starting materials. If the nylon has been manufactured from an urami nocarboxyl 1c acid, trie mononitrile with one amide group has the CN group in the N-alkyl portion of tha molecule (I and II): CH,(CH,) CONH(CH-) CN * Hr n (I) CH2:CH(CH)m_,C0NH(CH,)nCN CD If the nylon is a condensation product of a diamine and a dicarboxylfc acid, the mononitrile with one amide group has the CN groups in the carboxylic acid grouo of the amide (III and IV): CH3(CH2)|||NHCO(CH2)nCN (III) CH",:CH(CH*,) m"i,NHCO(C*H,)n CN (IV) Dtner products of nylon pyrolysis -.elude saturated hydrocarbons, o-olefins (which give the strongest intensities of tne hydrocarbons), uj-oienes, mononitriles with either a saturateo carbon c.nain or an u-olefin cnain, lactams, oinitriies, and HONS 217939 hyarocaroons ntn one amice groua with an ui-douole bond in to* carooxy1 grouo anc witn or without an uj-double bond in the alkyl substituent (9). Pyrolysis of nylon 6 (polycaprol actam) at 530C gave a strong peak for caprolactam and lesser peaks for Cg mononitriles and for mononitriles with one amide group (9). Other studies report nylon 6 pyrolysis products that include caprolactam dimers, trimers, tetramers, etc. (10,11) [at 30 to 400C]. 8ahr et al. (1984) (5) found oligomers containing up to 16 repeating units (M) in the pyrolysis products from nylon 6 degraded at 50 to 600C. Host products took the forms [M3_l# Na]*, [Mn + K] , and (Mn + H] . The most abundant + Na]+ had n * 5 to 7. For [m * Na - HjO) , the most abundant species had n = 8 or 9, ~ Combustion. No specific information was found on nylon 6 combustion products. The flash*ignition temperature of nylon 6 is 420C; the self-ignition temperature is 450C (7). References 1. J, E. Hauck, Editor. 1974 Materials Selector. Vol. 78(4). Stamford, Conn.: Reinnold Pudishirg Company, 19~". 2. Modern Plastics Encyclopedia. Vol. 62, No. 10A. 3. Agrenoff, Editor. New Torn: McGraw-Hill, Inc,, 1985. 3. M. windholz, Editor, The Merck Index. 10th ed. Rahway, N.J.: Merck and Company, Inc., 1983. 4. R. J. Welgos. "Polyamide Plastics" in: Kirk-Qthmer Encyclopedia pf Chem ical ~echno1oov. 3rd ed. , Vol. 18. M. Grayson, Editor. New Vorn; Inter science Publisher*, a Oivision of John Wiley and Sons, 1982, pp. 406-425. 5. Lt. 8ahr, I. Luederwald. R. Mueller, and H. R. Schulten. Pyrolysis F^eid jescrct'.on HaSi ioectrometrv of =olymers. Cl. hlionatic ^oiyamioes. Anoew. Makromol. Chem. , 120-, 163-175 (1984). S. H, H, G. Jellfnek and S. R. Ounkle. "Hydrocyanic Acid Evolution from Poly amides, Polyurethanes, and Polyimides and a Survey of Their Thermal jr: Oxi dative Degradation1' in-. Degradation and Stabilization of Polymers, Vol. 1. H. H. G. Jellintk, Editor. Amsterdam, Neth.: Elsevier, 1533, pp. 66-161. 7 u. Troitzsch. International Plastics Flammability Handbook. New York: MacMIilan, 1983. . R. E. Putscher. "Polyamides" in: Kirk-Qthmer Encyclopedia of Chemical Technology. Vol. 18. M. Grayson, Editor. New York: Interscience Pubiisners, a Oivision of John Wiley and Sons, 1982, pp. 328-371. 4-26 HONS 217940 9. h. Ohtani, T. Nagaya, y. Sugimura, and S. Tsuge. Studies on the Thermal Degradation of Aliphatic Polyamides by Pyrolysis-Glass Capillary Gas Chroma tography. J. Anal. Appl. Pyrolysis, 4(2), 117-131 (1382). 10. R. E. Adams. Positive and Negative Chemical Ionization Pyrolysis Mass Spec trometry of Polymers. Anal, Chem., 55, 414-416 (1983). 11. I. Luedervald and G. Pernak. Catalytic Thermal Degradation of Nylon 6 j. Anal. Appl. Pyrolysis, 5(2), 133-138 (1983). NYLON 6,6 CASRN: 32131-17-2 Synonyms: Po1y(hexamethy1ene adipamide); hexamethylenediamine-adipic acid copoly mer; poly(iminocarbonyl butylenecarbonyliminohexamethylene). Trade Names (producers): Celanese (Celanese Corp.); Zytel (DuPont); Vydyne (Mon santo)-, Maranyl (Imperial Chemical Industries), General Information Molecular Formula: (C,-H--N0-) ------ n Structure of Monomers and Polymer: H2N(CH2)iNH! Hexamethy1enediamin* H02C(CH2)4C0jH Adipic acid Uses: Nylon 6,6 is used for bearings, gears, bushings, coil forms, brush backs, rod, and tuOirg (1). Thermal Oecoeiposition Mechanisms General information for nylons is discussed under nylon 6, above. Cyclopentanone may be produced after chain scission of the carbonyl-nitrogen and methylenecarponyl links give the requisite 5-carbon precursor or from cleavage of an endgrouc adipic acid followed by decarboxylation and cyclization. Hydrolysis gener ates some of the products. At lower temperatures, cnain scission predominates, with production of cyclopentanone and CO. Temperatures around 600C produce 4-27 HONS 2179*1 cyclohexane, olefins, and fragments with intact amide groups (all fragments with m/e 140). Jellinek and Ounkle (2) presented the following scheme for thermal degradation of nylon 6,6: Lower temperatures: o :o .o : o I' . I! II |l c -- NH(CH2)6NH -- C(CHa -- CNH -T (CHj)* -- NHC* 'NH(CH,)6)NH 1 0 II . C(CH2)jCH2 II 00 4 II CNH(CH2),NHC' III 0II . + *~CNH + 'CH,(CH2)SNH IV * V I NH2(CH2)gNH2 II III CO + NH(CH2)6NHC V. H2N(CH(),NHC- IV HH 0|| IV ------ '^'CNH2 --CN + H,0 0I! CH2:CH(CH2)4NHC ^CNHP.2 - H,0 ---------- - ? ^ CO" n * S2NH, R1C0IH ----------- - RlH + CC Higher temperatures (> 600C): 0 00 0 It n ii n "CNH--CH2 -- CHj(CH2)gNHC(CH2)CNH(CH2)6NHC 00 i n HCN * -"-CNH, + "-CNH -- (CH2 )s -- NH-- VI CH, 0 II "CNH, t --C * NHj or '-CN + H20 oVI and/or CH,;CH(CH, }-CHj + H20 "CN --26 HONS 217942 Summary of Experimental Studies Reviewed Pyrolysis, Ohtani et al. (1982) (3) found cyclopentanone as the major nylon 6,6 pyrolysis product at 5S0C. Minor products include caprolactam and a Cs dinitrile 8anr et al. (1984) (4) pyrolyzed nylon 6,6 at 50 to 600C, identifying peaks corre spending to [M2.b +.H]+, [M2_s r Na]+, [M2 2Na]I-\2 3a4nd a very weak fM + Na h20] . Main fragments corresponded to [M^ * Na - 44]*, (M^ * Na - 84]*7 and [M Na - 110]* where 44 is a loss of C0NH2, 84 is a loss of (CH2)4C0, and 110 is a " loss of (CH2)4C0 and CN. After 8urns and Renschler (1984) (5) pyrolyzed nylon 6,6 yarn at 500C, they identified major products as cyclopentanone, adiponitrile (ten tatively), and a "composite of caprolactam and an apparent homolog." Adams (1983) (6) reported the presence of the following mass spectral peaks (abun dance relative to cyclopentanone as 100%) after nylon 6,6 pyrolysis at 30 to 400C 143 (16%), 183 (15X), 227 (15%) (227 is the weight of the repeating unit), 343 (47%), 369 (3IX), and 409 (25%). Except for the common occurrence of cyclopen tanone, there was little agreement among the references as to the products formed (all three reoorts identified them by mass spectral ane'y?'*!. Combustion. Jellinek and Ounkle (1983) (2) studied the evolution of HCN from ny lon 6,6 films during flash degradation at 289 to 695C in air. The amount of HCN evolved reached a maximum of *>. 14% of theoretical at n. 500C within 16 min. At 69SC, HCN evolution was much less than 1% of theoretical because of its oxidation which began at 57SC. References 1. . Hauck, Editor. 1974 Materials Selector. Vol. 78(4). Stamford, Conn.: Reinhold Publishing Company, 1973. 2. h. H. G. Jellinek and S. R. Ounkle. "Hydrocyanic Acid Evolution from Poly amides, Polyurethanes, and Polyimides and a Survey of Their Thermal and Oxi dative Degradation" in: Degradation and Stabilization of Polymers. Vol. 1 H. ,H. G. Jellinek, Editor. Amsterdam, Neth.: Elsevier, 1963, pp. 66-161. 3. H. Ohtani, T. Nagaya, Y. Sugimura, and S. Tsuge. Studies on the Thermal Degradation of Aliphatic Polyamides by Pyrolysis-Glass Capillary Gas Chro matography. J. Anal. Aopl. Pvrolysis, 4(2), 117-131 (1982). 4. Li. Bahr, I. Luederwald, R. Mueller, and H. R, Schulten. Pyrolysis field C-sorption Mass Spectrometry of Polymers. III. Aliphatic Polyamides. Rr. . Makromol- Chem., 120, 163-175 (1984). 5 : . Burns and C. L. Renschle-. Monitoring of Degradation of Thermally Agee Nylon 6,6. II. Pyrolysis-Gas Chromatography. J. Aopl. Polvm. Sct.. 1133- 1139 ( 1984). - ?c HONS 217943 6. R, . Adams. Positive and Negative Chemical Ionization Pyrolysis Mass Spec* trometry of Polymers. Anal. Chem., 55, 414-416 (1983). NYLON 6,10 CASRN: 9008-66-6 Synonyms1. Hexamethylenediamine-sebacie acid copolymer Trade Names (producers): Tynex General Information Molecular Formula: (Ci*H3oN202)n Structure of Monomers and Polymer: H3N(CH2)eNH2 Hexamethylenediamine H02C(CH2),C02H Sebacic acid --EMHC0(CH2),C0NH(CH2)6 Uses: Jacketing for wire and cable, special molded parts (1). Thermal Decomposition Mechanisms No specific information was found for nylon 6,10. Summery of Experimental Studies Reviewed Pyrolysis. Ohtani at al, (1982) (2) found the following compounds in the product from pyrolysis of nylon 6,10 at 550C: caprolactam, Cs to Ct hydrocarbons (Cs major), C( to Cc mononitriles (C* major), 1,10-decanedinitrile, and C14 to ClS mononitriles with one amide group (CIS major). Combustion. No specific information was found. References J. E. Hauck, Editor. 1974 Materials Selector, vol. 78(4). Stamford, Conn, Reinhold Publishing Company, 1973. *1-30 HONS 217944 2. H. Ohtani, T. Nagaya, Y. Sugimura, and S. Tsuge. Studies on tne Thermal Oegraoatlon of Alipnatic Polyamides by Pyrolysis-Class Capillary Gas Chro matography. J. Anal. Appl. Pyrolysis. *(2), 117-131 (1982). NYLON 11 CASRN: 25038-74-8 Synonyms'- Po1y(uj-undecanami de) Trade Names (producers): Rilsan (Rilsan Corp.) General Information Structure of Monomers and Polymer: H2N(CH2),oC0jH u-Aminoundecanoic acid NHCO ( CHj ) j o"JjJNylon 11 Uses: Electrical insulation and other nylon uses where low moisture absorption is needed (1). Mainly used for pressure moldings and fibers (2). "herrnal Decomposition Mechanisms No specific information was found for nylon 11. Summary of Experimental Studies Reviewed Pyrolysis. Dhtani et al. (1982) (3) pyrolyied nylon 11 at 550"C. The lactam pro duced from undecanamide gave the weakest peak. Other weak peaks were ascribed to CM to C2o mononitri las with one amide group and C3 to C31 hydrocarbons with one amide grouo. Inteneediate-to-strong peaks were ascribed to C6 to C15 mononltriles with the Cn species predominant. C, and CT hydrocarbons were the most abundant of all species identified. C( to C:0 hydrocarbons were present in intermediate abunoance. Combust:on. No specific information was found. 4-21 MOHS 217945 References 1. J. E. Hauck, Editor. 1974 Materiels Selector. Vol. 78(4). Stamford, Conn,: Reinhold Publishing Company, 1973. 2. R. E. Putscher. "Polyamides" in: Kirk-Othmar Encyclopedia of Chemical Tech nology. Vol. 18. M. Grayson, Editor, New York: Interscience Publisners, a Division of John Wiley and Sons, 1982, pp. 320-371. 3. H. Ohtani, T. Nagaya, Y. Sugimura, and S. Tsuge. Studies on the Thermal Degradation of Aliphatic Polyamides by Pyrolysis-Glass Capillary Gas Ch-omatography. J. Anal. Appl. Pyrolysis, 4(2), 117-131 (1982). POLYURETHANES CASRN: Oependent on monomers Synonyms: Urethane polymers General Information Molecular Formula: Variable Structure of Monomers and Polymer: Polyurethanes contain the carbamate or ure thane group -NHC00- and are produced by reacting diisocyanates, e.g., toluene2,4-dii socyanata [CHsCeHj(NC0)3], with a so-called polyol or macroglycol based on polyethers and/or polyesters or with a combination of macroglycol and a shortchain glycol extander. Linear, thermoplastic polyurethanes may have the general structure: 00 :I : 'I -fCOCNHC -----CNHCD1------ iii n Crossl inked thermosat polyurethanes are prepared from isocyanates and polyols of functionality > 2. Crosslinking can also occur from secondary reactions to give urea linkages [-NHCDNH3 and biuret linkages [-NHCON(CONH-)-]. The latter reac tions are common in water-blown polyurethanes (evolving C03 acts as a blowing agent) (1). Rigid foams are derived primarily from polymethylene polyphenyl isocyanate (PMOI), often linked with polyester polyols. Rigid foam from PMDI is preferred for commercial refrigeration Insulation, but household refrigerators use a rigid foam based on toluene diisocyanate (TDI), 4-22 HONS 217946 Ncn NCO NCO n PMDI PMO[s are crude products containing 40 to 60X 4,4'-methylanebis(phenyi isocyanate) (MDI). Pure MDI is used in elastomers. MDI Flexible foams are primarily based on polyether polyols. TOI, PM0I, or PM0I-T0I About SOX of polyurethane coatings are based on TDI with polyethers or polyesters. Polyurethane alkyds, moisture-cured polyurethanes, and self-crosslinking aqueous polyurethane dispersions are other coating types (1). Uses: Flexible polyurethane foams are used in furniture, transportation, bedding, carpet unOerlay, textile laminates, and packaging (listed here in order of decreas ing U.j consumotion in 1981). Rigid foams are used in building and construction, refrigeration, tan* and pipe insulation, transportation, pacxaging, ana furrture (1). Polyurethanes are used to enamel magnet wire that will be used in soldering applications. Polyurethanes may also be used to replace oil-modified alkyds used in electrical equipment to bond windings for improved vibration resistance. Al though sevaral other synthetic resins are available for the purpose, polyurethanes or epoxies are chosen when chemical resistance is important (2). Polyurethane foam is among the materials that have been proposed as insulation for cryogenic resis tive cable pipe. (A cryogenic resistive cable is an insulated conductor cooled to reduce the electrical resistivity of the conductor. Cables are cooled to cryogenic temoeratures, typically that of liquid nitrogen.) The feasibility of using poly urethane foam to insulate air-cooled underground transmission lines has also been studied (3). A European reference () listed polyurethane among commercially avai'sc'e organic cable insjlaoior and jacket mate-'als HONS 21794? The-mal Decomoosition Mechanisms Three pathways were proposed by Saunders (1959; cited by Hileman et al. , 1975) (). (a) dissociation to the original polyol and isocyanate; (b) cleavage by a concerted reaction, producing a carbamic acid (which further decomposes to an amine and C02) and an olefin from the polyol; and (c) loss of COj probably accompanied by intra molecular recombination of the olefin and primary amine to give a secondary amine. When Hileman et al. (1975) (5) pyrolyzed a polyol-TDl polyurethane, only pathway (a) appeared to be operative below 300C. Pathways (a) and (b) were operative above 300C plus other secondary decompositions. Lech of volatile secondary or tertiary amines seemed to indicate that if pathway (c) were operative, it occurred without polymer chain cleavage. Grayson et al. (19B2) (6) proposed the following scheme for combustion of polyure thane foams: ,,Po,lyuret.h. ane I heat ----l-o--w----h--e--a--t-- ,C,,har heat i 1socyanate vellow Smoke 0. ( CO COw NO heat Alkenes Al'.ynes H,0 1 Polyol H;Q 0, heat Aldehydes Ketones Acids heat neat * Black Smoke HCN h CHjCN CHo:CHCN, etc Summary of Experimental Studies Reviewed AH the information found was on flexible polyurethane foams, ir.stly based on TDI and polyether polyols. HONS 217948 Pyrolysi$, At 300C, flexible polyurethane foams based on TDI and a polyether polyol evolved a yellow smoxt containing all of the nitrogen from the polymer. About 30% of the original polymer weight is lost (7). The yellow smoke, which was stable up to n- 800C, appeared to contain compounds with polyether linkages, iso cyanate groups, and possibly ure'do linkages and amino groups (8). CO was also evolved at 300C with a two-step pyrolysis at 300*C, then 1000C, giving less CO than if the polymer was heated in one step at 1000C (7). The major volatile products (other than the yellow smoke) observed by Hileman et al, (1975) (5) when a polyurethane was pyrolyzed at 300C were H20, propene (CH3CH:CH2), and CO; (in order of increasing amounts). At 500*0, C02, acetaldehyde (CH3CH0), propionaldehyde (CH3CH2CH0), and propene were found (in order of increasing amounts). At 750C, which was still below the temperature at which the yellow smoke decomposed, the products found (in order of increasing amounts) were lower alcohols (CH30H and CHjCH20H), CO, C02, CH4p H-0, Cj to C3 saturated and unsaturated hydrocarbons, acetaldahyde, and propionaldehyde (5). Pyrolysis at 800 to 1000C gave HCN, benzonitrile, acetonitrile, pyridine, and r '" r. r ^ r - predicts , - 5 ,. utf.tr p;pcuc cj i r.cuc&c tc s c tu1. at eG and unsaturated hydrocarbons; other C2 and C3 nitriles and cyanotoluene; the aro matic hydrocarbons benzena, toluene, styrene or cyclooctatetraene, napnthalene, and indene; and the heterocyclic aromatic compounds pyrrole, methylpyr-cine, vinylpyridine, and quinoline or isoquinoline (7,9). Propionaldehyde, propene, and acetaldehyde were the major products found by Hileman et al. (1975) (5) after n- 30% weight loss from pyrolysis at 1000*C. They also `'ound more of the other products detected at ?50C. "-esumably, decomoosition at 1000C was the source of the nitrogenous products raportea: T0I, toluenediami re, dicyanobenzene, benzonitrile, and other nitriles. Other pyrolysis products were toluene, benzane, styrene, xylene, alcohols, ether alcohols, ethers, and acetone (yields were not calculated although labeled chromatograms are given in the reference). About 50 products from pyrolysis of rigid polyurethane foams ware identified in a 1985 review (10). Combust'1 try Ouring full-scale compustion of a oolyol-TOI po tyu-ethane, the tem perature attained at least 1000"C within a few r nutes. Hydrogen cyanide (HCN) yieids reached a maximum of C.3% and represented a toxic hazard comparable to that MOWS 217949 --35 of the CO generated within the first 5 min, After that time, HCN yields declined, possibly due to a rapid loss of yellow smoke, leaving the polyol residues. The CO concentration (total ^ 8%) remained steady from ^ 5 to 20 min of burning (7). Boettner et al. (1973) (11) reported that combustion losses of CO* and CO were higher than those of propene, HCN, and aldehydes. Yields of acetone, hydrocarbons, and methanol were even lower. Woolley (1973) (7) remarked that the same products (HCN, nitriles, N-containing heterocycles, and lower and aromatic hydrocarbons) were formad from combustion as from pyrolysis, but that they were formed at lower temperatures during combustion. About 90 combustion products from rigid polyurethane foam were identified in a recent review (10). References 1. H. Ulrich. "Urethane Polymers'1 in: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed. M. Grayson, Editor. New York: Interscience Publishers, a Division of John Wiley and Sons, 19E3, pp. 576-6DB. 2. R. N. Sampson. "Insulation, Electric" in: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol, 13. M, Grayson, Editor. New York: Interscience Publishers, a Division of John Wiley & Sons, 1981, pp. 534-563. 3. H. Schoenbacher and A. Stolarz-Iiycka. Compilation of Radiation Oamage Test Data. I. Cable Insulating Materials. CERN-79-Q4/XPS. Available Springfield, VA: National Technical Information Service, June 1979. 4. T. Tanaka and A. Greenwood, Advanced Power Cable Technology. II. Present and Future. Boca Raton, FL: CRC Press, 1983. 5. ". I. Hileman. a. J. .'oornees, L. i. *'ojcik, H. !'*. lir^y, 5. w. P.yan, inc . N. Einhorn, Pyrolysis of a Flexible Urethane Foam, J. Polvm. Sci.. 13, 571-584 (1975). 6. S. J. Grayson, J. Hume, and 0. A. Smith, Reduction of Smoke and Toxic Gases from Flexible Polyurethane Foams Under Fire Conditions: Introductory Review and Chemical Model. Plast. Rubber Process. Aool.. 2(2), 111-122 (1982). 7. w. D. Woolley. Toxic Product* from Plastic Materials in Fires. Piast Polya.. 41(156), 280-286 (1973). 6. J. Chambers and C. B. Reese. The Thermal Decomposition of Some Polyurethane Foam*. Br. Pplvm. J. . B, 4B-53 (1976). 9. ' W. 0. Woolley and P. J. Fardel 1. The Prediction of Combustion Products. Fire Research. 1, 11-21 (1977). HONS 217950 10. M. Paabo and 6. C. Levin. A Review of the Literature on the Gaseous Products and Toxicity Generated from the Pyrolysis and Combustion of Rigid Polyurethane Foams. N8SIR 85-3224, PB86-151941. Springfield, VA; National TecnnicaT Information Service, December 1985. 11. . A, Boettner, G. L. Ball, and B. Weise. Combustion Products from the Incineration of Plastics. PB Rep. No. 222001/0. Springfield, VA; IFs. National Technical Information Service, 1973. HONS 217951 4-S7 Section S SULFUR-CONTAINING MATERIALS See also creosote in Section 4, Nitrogen-Containing Materials. CHLOROSULFONATEO POLYETHYLENE CASRN: 9008-08-6 Synonyms: Robber, synthetic, chlorosulfonated polyethylene; Chlorosulfonated poly ethylene synthetic rubber; CSPE. Trade Names (producers): Hypalon; Hypalon 40 (E. I. du Pont de Nemours, Inc.); jOIb3ftX. General Information Molecular Formula: Best rubber properties: 30 to 35X Cl and 0.8 to 1.5X sulfonyl sulfur. Structure of Starting Materials and Polymer: -CHiCH1CH2CH2- :ci. SO, -ch-:h,ch,ch " Cl o=s=o l Cl * ;hci CSPE may be crosslinked by use of PbO, MgO, or tribasic lead maleate with a sulfurcontaining accelerator, usually dipentamethylenethiura* tetrasulfide. It can also be cured with epoxy resins. A crosslinked polymer useful for wire coverings for bare copper or use with lead in hose end cables can be prepared by the use of metal oxides or hydroxides, rosin acids, and a free-radical scavenger such as a nitrosamine, nitrosohydroxylamine, or hindered phenol (1). Lises: Electrical uses include wire and cable (appliance cords, ignition wire, telepnone r-.anoset cords, and weatherproof wire). An important use is for flexible. HONS 217952 decorative, and protective coatings for fabric, metal, rubber, masonry, and otner surfaces (1). Chlorosulfonated polyethylene is preferred over neoprene for jacketing of insulat ing cables for installations. The CSPE jacket replaces part of the conductor insulation. When color coding is desired for open-pit, portable mining cables, pigmented CSPE jackets are used (2). Hypalon is now widely specified for sheathing oil-drilling platform cables instead of poly(vinyl chloride) (3). Other uses include weather stripping and automobile window channels; leather-like coated fabrics, floor tile; automotive products such as distributor caps, sparkplug covers, and ignition wire jacketing; hoses for steam, water, and corrosive enemicals; chemical tank linings; surfacing of conveyor belts; gaskets or diaphragms requiring resistance to olone, the weather, heat, or oils; and adhesives (1). Thermal Decomposition Mechanisms SO,Cl groups are lost followed by dehydrochlorination to form a polyene. Cross linking may occur by intermolecular elimination of HC1 and/or a Diels-Alder type reaction between two dehydrochlorinated polymer molecules. Thermal degradation then proceeds principally by 1:5 hydrogen transfer. This gives Cj- to Cs 1-alkenes. Limited unlipping gives CSH. Secondary pyrolysis occurs above 627C. Higher l-alkenes formed during primary pyrolysis are degraded to lower-molecularweight products probably by dissociation of free radicals and intramolecular cyclic dissociation. Above 727C, further fragmentation, cvclization, and aromatization sccur; nyorogen yie:os increase, C; ana products decrease: C-, prccuction maxi mizes at - 827C; toluene yields decrease above 827C; benzene yields plateau in the range - 700 to 1100C; naphthalene yields reach their maxima about 8478C; ane, finally, only small fragmentation products and large polynuclear aromatics are p-esent (4). Summary of Experimental Studies Reviewed pyrolysis. At pyrolysis temperatures < 627C, major products include C3 to Cs 1-alkenes and HCi. For example, major products at 497C -ere reported as etnen* and ethane, prcoene and propane, 1-butene. 1,3-butadiene, and toluene; at S3'2. propene and propane, ethene and ethane, benzene, and toluene. Above 527C, t.ne 1-alkenes break cown to lower fragments; thus, apoears as a major product Atcve -_.c cn anc aromati cation p-ocutts are largely a recan i nan; MONS 217953 However, the C2 (ethane and ethene) maximum is - 827C. At 927C, large poly cyclic aromatic hydrocarbons are among products with high yields of beniene and naphthalene (A). The large polycyclic aromatic hydrocarbons detected were acenaphthene, fluorene, anthracene, and phenanthrene. Other products were styrene, toluene, indene, 2- and 1-methyl naphthalene, biphenyl, and dimethylnaphthalene. Combustion. No information was found on organics in combustion products. Combus tion of chlorosulfonated polyethylene (CSP) cable sheath material compounded for reduced acid gas emission gave concentrations of the products in the order C02 > CO > HC1 > S02. A standard type of CSP cable sheath material that had not been compounded for reduced acid gas emission gave products with concentrations in the order CO* > HC 1 > CO > S02 (3). References 1. P. J. Canterino. "Ethylene Polymers: Oerivatives" in: Encyclopedia of Polymer Science and Technology, Vol. 6. H, F. Mark and N. M, Bikales, Heitors, hew Vork: Wilev, 1967, pp. 431-454, 2. J. E. Hogan. "Wire and Cable Coverings" in Kirk-Othmer Encyclopedia of Chemical Techno!. 3rd ed. Vol. 13. New York: Interscience Publishers: a Division of John Wiley & Sons, 1961, pp. 564-590. 3. G. C. Sweet. Offshore Cables - The Role of Oifferent Classes of Elastomers in the Fire Situation. Rubber World. 189(2), 18-22 (1983). 4. D. A. Smith and J. W. Youren. Pyrolysis of Polyole-'.n Elastomers. Br. Polyir. J. 8(4), 101-117 (1976). YSUlFONE C,._RN: 25135-51* 7 Synonyms: Bisphenol A - 4,4'-dichlorodiphenyl sulfone copolymer. Trade Names (producers): Udel (Union Carbide). Gera-al Information Molecular Formula: (CjtHj-jSO,) MONS 217954 5-3 Structure of Monomers and Polymer: Bisphenol A 4,4'-Dichlorodiphenyl sulfone Polysulfone Uses: Electrical/electronic applications include connectors, auto fuses and switches, housing, coil bobbins and cores, TV components, capacitor film, and structural circuit boards. In chemical processing equipment, polysulfone is used for corrosion resistant piping, both transparent and glass fiber bonded; for tower packing; and for pumps, filter modules and support plates, and membranes. Poly sulfone is also used for camera and watch cases, battery cell frames and housings, auto and aerospace components, water purification devices, medical instrumentation and trays to hold instruments during sterilization, and food processing equipment (1). Thermal (Decomposition Mechanisms (During thermal and thermooxidative degradation of polysulfone, crosslinking and chain-scission reactions are caused principally by reactions of free radicals with tne aromatic nuclei. Iron and dipnenyioipropane (OPP) impurities affect tne cou-se of thermal degradation of polysulfone. Both iron and OPP accelerate oxidation of aliphatic groups and thermal decomposition. Thermal degradation products of DPP destroy or retard crosslinking, reacting with the polymers as low-molecular-weight radicals. Iron impurities accelerate crosslinking (2). Summary of Experimental Studies Reviewed Pyrolysis. Pyrolysis at 460 to 520C caused a 62% weight loss of the polysulfone sample (3). Radiant pyrolysis of a sample containing up to 1% carbon black for 2 min at 4 cal cm ^ sec ^ left 31% char (.5). Mo chemical products were identified. HONS 217955 Combustion. Thermal oxidation at 350C for 80 hr caused less than 10% weight loss. In the sane period, n* 70S was lost at 400C (6). Combustion for v 0. 5 hr at 400C produced little smoke, and the combustion products caused little sensory irritation in mice (7). Combustion of polysulfone at < 450 to 750C in an atmosphere somewhat oeficient in oxygen gave primarily C02, CO, S02, and a residue. The next most abundant volatiles were methane (CHg), benzene (CgHg), and toluene (CgHsCH3). Minor amounts of ethylene (CK2:CH2), ethane (C2Hg), ethylbenzene (CgHsC1Ms), and styrene (CgHsCH:CH2) were determined. Measured products accounted for 92.6X of the sulfur content but only 60S of the total mass (3). About half of the weight loss from polysulfone combustion was a liquid residue. Some carbonyl sulfide (COS) was detected in the gases after combustion at 490 to 550C, the range where S02 evolution was greatest. Phenol and phenyl g-tolyl ether were the major combustion products at 1000*C. Hydrocarbon products included tolu ene, ethylbemene (or xylene), styrene, methyl ethylbenzene, indene, methyl i ndene, trimethyl benzene, naphthalene, methyl naphthalene, biphenyl, and dimethyl naphtha lene. Other oxygen-containing products included benzaldehyde, benzofuran, methylpenisfuran, c .pe.--cfuran, oiphenyl etner (or pheny 1 pher,,,l). cresul, ttn;. 'pher.ol. and 2-hydroxyphenyl-2*pheny1propane (8). References 1. Modern Plastics Encyclopedia, 1985-1986. Vcl. 62, No. 10A. J. Agranoff, Editor. New York: McGraw-Hill Inc., 1985. 2. A. L. Narkon, I. I. Levantovskaya, Yu. I. Kotov, B. E. Konovalova, L. I. Reitburd, L. M, Bolotina, and A, B. Blyumenfel'd. Effect of Impurities on Degradation and Crosslinking of Polysulfone. Vysokomol. Soedin., Ser, A. 26(8), 1712-1717 (1934). 3. G. L. Ball and E. A. 8oettner, Volatile CombustionProducts of Polycarbonate and Polysulfone. J. Appl. Polym. Sc 1.. 16(4), 855-863 (1972). 4. S. K. Brauman. Char-Forming Synthetic Polymers. 1. Combustion Evaluation. J. Fire Retard. Cham.. 6(4). 249-265 (1979). 5. S. K. Brauman. Char-Forming Synthetic Polymers. 2. Char Characterization. J. Fire Regard. Cham., 6(4), 266-275 (1979). 6. S. Barron. An Investigation of the Effects of High Temperatures upon Various Industrial Polymers. Fire FIammtbi1<ty, 7, 3B7-400 (1976) ' . k, Sangha, M. Matijak, and Y. Alarie, Toxicologic Evaluation of Thermo plastic Resins At and Above Processing Temperatures. Am. Ind. Hyp, Assoc. J . 42(7), 481-485 (1981). HONS 217956 8. E. A. Boettner, G. L. Ball, and B. Weis*. Combustion Products from *oe Incineration of Plastics. PB Rep. No. 22200UW. Springfield, VA:--SJtionai Technical Information Service, 1373. MOMS 217957 Section 6 MATERIALS CONTAINING ONLY C ANO H OR C, H, AND 0 3ISPHEN0L A EPOXY RESIN CASRN; 25068-38-6 Synonyms: Bis(g*hydroxypheny! )diethylmethane*epichlorohydrin copolymer; 2,2-Bis(g-hydroxyphenylJpropane-epichlorohydrin condensate; Diphenylolpropane* epichlorohydrin polymer; Epichlorohydrin-bisphenol A epoxy resin; Oxirane, (chloromethyl)-, polymer with 4,4'-(1-methylethylidene)bis[phenol]; Phenol, 4,4'-(l-methy1ethylidene)bis-, polymer with (chloromethyl)oxirane; Propene, 1-chloro-2,3-epoxy-, polymer with 4,4'-isopropy1idenedipheno1, Trade Names: Araldite 6005 (or 6010 or 6084 or GY250 or GY260 or GY280)-, Bakelite PKDA; Casting Resfn F; Epikote 828 (or 834 or 836 or 1004 or 1007); Epi'Rei 510; Epon 826 (or 834 or 1001 or 1002 or 1004); Epotuf 37-139; GenEpoxy 190. General Information Molecular Formula: (C^HjgOj-CjHjClO)^ Structure of Monomers and Polymer: Most commonly, the polymer shown is cured with a cycloaliphatic anhydride or amine as a hardener to effect crosslinking. "The largest producer of resins for use in 6-1 HONS 217958 casting transformer coils used in the United States reports that roughly 80X of their production for transformer coils may be approximated by the above generali ties. The remainder use cycloaliphatic compounds fn place of bisphenol A (1)." Uses: Epoxy resins are a type of solid dielectric that may "be cast or impregnated into the coils of a transformer; used as films in capacitors; or used as insulation for various parts of transformers, capacitors, or other electrical equipment" (1). Epoxy insulation systems have been used in transformers since the early 1960s (2). Thermal Decomposition Mechanisms Bisphenol A epoxies are less stable than epoxy novolak resins, which are produced from phenol-formaldehyde resins and epichlorohydrin, because the isopropylidene linkages in the former are less stable than the methylene linkages of the epoxy novolaks. The structure of a novolak epoxy is as follows (3): 0 Isomerization of terminal epoxide groups before cleavage would give 2-hydroxypropanal [CHSCH(OH)CHO] and propionaldehyde (CK,CH2CHO), Direct cleavage in the end groups would give ethylene oxide and formaldehyde. Acetaldehyde (CH3CHO) could arise from isomerization of ethylene oxide. Chlorosubstituted compounds probably arise 'rom impurities in the glyciayl portion of the resin (4). Summary of Experimental Studies Reviewed Because of the scarcity of information on thermal degradation of bisphenol A epoxy resins, information is also included on the structurally similar epoxy novolax resins. Pyrolysis. Pyrolysis of a novolak epoxy resin at 350C gave toluene (the reaction solvent) and water as major volatiles (94X). Phenol, cresols, and higher phenols, ethane, ally! chloride, aldehydes, and ketones were among the pyrolysis products (4). Pyrolysis of a bisphenol A epoxy resin cured with 2.6 parts per hundred resin 6-2 HONS 217959 2-ethyl imidazole it 380 to 425C gave mostly phenol, diphenyl ether (CeHs0C8H5), and Ci* to C5-alkylated phenols and aromatic ethers. Most diphenyl propane deriva tives were g,g'-isomers (5). Pyrolysis of uncured bisphenol A epoxy at 350 to 450C gave water (from condensa tion of epoxide groups) and toluene (reaction solvent) as the major products. At 450"C, approximately equal amounts of methyl chloride (CH3C1) and acetaldehyde were formed. High-boiling cresols, phenol, isopropenylphenol [CH3C(CH2)C8H80H]. and blspheno! A were in the residue (4). Major products from pyrolysis of a blsphenol A epoxy resin cured with methylenedianiline (HjNCaH^CHjCgH^NHj) were water at 350C and water, CO, CH3CH0, CH3C1, and CH< at 450C. Methyl eyelopentadiene arose from both cured and uncured bis phenol A epoxies (4). Pyrolysis of an uncross 1 inked novolak epoxy resin at 360 to 1200C volatilized 38 to 7T z` tfe 57 to PCS of the vpi sVles ccmrrised an uncnaractc*'red maf- rial (average molecular weight 350 from pyrolysis at 800C). Methyl chloride (CHjCl) and ethyl chloride (C;HSC1) were found in the volatile fraction at 360C. but not at higher temperatures. Hydrogen (H2), ethylene (CaH4), and substituted- cyclopentadienes were detected in the volatile fraction at 800 and/or 1200C, but not at 360 or 500C. In contrast to what would be expected from combustion, CO concentrations in the volatile fraction increased with increasing temperatures (maximum 25.3* at 1200C) as C02 concentrations decreased (maximum 16. ZS in the vclatiles at 360C). Organics representing more than 3* of the volatiles were methane (CH,; 4.2% at 1200C), propylene (HC:CHCH3; 6,5* at 360C), benzene (C8H8, 8.IX at 1200C), and methyl chloride (CH3C1; 5.1* at 360C). Other organics pres ent at less than 3* of the volatile fraction at one or more pyrolysis temperatures were acetylene (C2H2), acetone (CH3C0CH3), propane (C3Ha), and ethane (C3H6) (Madorsky and Straus, 1961; cited by Zbozinek, 1985) (1). An epoxy resin used to impregnate tapes and wrapper insulation in dry-type trans formers was pyrolyzed at 600 and 1000C. The prooucts collected (in unreported amounts) were C02, CHa, C2Hh, propylene, butylene (1-butene?), pentane, cyclopentadiene. toluene, phenol, xylene, styrene, indan, indene, naphthalene, and biphenyl (6). D HONS 217960 Lum and Feinstein (1981, 1982; cited by Zbozinek, 1985) (1) found benzene, phenol, and cresol in the thermal degradation products of novoiak epoxies (pyrolysis?) heated at 300 to 500C. Combustion. Sisphenol A epoxy resins are more combustible than comparable thermo setting plastics, having a lower tendency to carbonize. The resins continue to burn on their own when removed from the ignition source. The odes of phenol, formaldtnyde, and hardeners are detected in the smoke (4). Approximately 500 lb (230 kg) bisphenol A epoxy is used in the cast transformer coils of a 3-pnase transformer. The example is based on a 2,000 kVA mode? with three high-voltage and three low-voltage coils rated at 12,000 VAC and 480 VAC, respectively. The transformer cabinet with a volume of 347 ftJ (9.83 m5), 208 ftJ (5.89 ) of which is occupied by air, if unventilated (but most utility trans former cabinets are), contained sufficient oxygen to combust only 1,5 lb (0.7 kg) of the resin. When heated for 30 min at temperatures up to 500#C with sufficient oxygen for complete combustion, resin samples produceo 20 identified ana 30 un identified compounds. The latter were in "extremely low" concentrations. The major products were 26.0 ppm (based on resin weight) phenol (C#Hs0H), 2.6 ppm toluene (C,HS'.H3), 2.0 ppm ethylbenzene (C8HSC2HS), and 1.5 ppm benzene (C,H#), The rest of tne mass was not accounted for by the study authors. Estimated con centrations in air were 3.03 mg phenol/m3 (05HA permissible exposure limit [PEL) = 19 mg/m:), 0.30 mg toluene/m3 (PEL = 375 mg/m3), and 0.23 mg ethylbenzene/m3 (PEL 435 mg/m3) (2), Acetylene (C2H2), benzene, toluene, and an aromatic fraction ware detecteo in the gases from combustion of an 800 kVA GEAF0L cast resin transformer at 1000 to 12C0C. The fires were initially fueled by propane and wood, and the gases from the fuels were not separeted from the gases evolved from combustion of the trans former (Altmann el al., 1984; cited by Zbozinek et al., 1985) (1). References 1. J. V. Zbozinek, Jr., 0. G. Marsh, and A. Sohrnerud (SCS Engineers, Inc.) , State-of-the-Art Review of Combustion and Pyrolysis By-Products of PC3 Substitutes. Palo Alto, Calif.: Electric Power Research Institute, Marcn 1985. 2. F. S. Brugner and A. J. Jonnatti. An Air Pyrolysis Study of Cast Bispnenc' A Epoxy Transformer Coils. li Trans. Power Appar. Svst. . PAS* 102(73. 2203* 2207 (198*T. HONS 217961 3. J. Troitisch. International Plastics F1aromaoil-tv Handbook. New York: Macmillan, 1983, pp. 17-44 and 55-63. 4. R. T. Conley. "Thermosetting Resins" in: Thermal Stability of Polymers. Vol, 1. R. T. Conley, Editor. New York: Marcel Oekker, Inc. , 1970, pp. 457-521. 5. J. Vogt. Thermal Analysis of Epoxy-Resins: Identification of Decomposition Products. Thermochim. Acta. 85. 407-410 (1985). 6. B. Vanwert and T. Orbeck. "Flammability Testing of Ory Type Transformer Insulating Materials: in: Proc. Electr./Electron. Insul. Conf., 12 [unpaginated 3*page reprint] (19)5), ~' CROSSUNKED POLYETHYLENE CASRN: 68S84-45-2 [for radiation crosslinked homopolymer; none available for peroxide-crosslinked homopolymer]. Synonyms: XLPE; Ethene, homopolymer, radiation crosslinked. Trade Names (producers): hone found. General Information Molecular Formula: (C2H)n Structure of Monomer, Polymer, and Common Peroxide Crosslinking Agent: CH2;CH, Ethylene n.CfyCHwCHCHjCH!'* *I .CHICHICHCH,CH2'- Radiation-Crosslinked Polyethylene (XLPE) Dicumyl Peroxide (DCP) In cable manufacture, crosslinking is don* immediately after extrusion of the cable 'nsulation because the material cannot be shaped after crosslinking. This cross linking is dene almost ixclusively by adding peroxiaes such as dicumyl peroxide (CCP) to low-oensity polyethylene granulate and steam curing for aoout 1 min at HONS 217962 joout 170"C. Electron beam or gamma irradiation are other methods of crosslinxing polyethylene (1,2). Radiation curing of high-density polyethylene is limited to low-voltage cables with thin insulation. Because moisture degrades the service life of XLPE, steam curing may be replaced by treatment with pressurized, heated inert gas (3). Uses; Low-density grades are used for wire and cable coatings and insulation; high-density grades for pipe and molded fittings. Since the 1970s, most of the distribution power cables installed in the range 15 to 46 kV have been insulated by chemically cross!inked polyethylene. These XLPE cables are substitutes for oil-impregnated paper-insulated lead-covered cable. By mid-1971, the use of poly ethylene for power cables was 400 million pounds (9 x 10 g), the repid growth in this use surpassing the use of crosslinked polyethylene for communications cables at that time. Use in coaxial and other cables was much less than 100 million pounds i.2.2 x 10 g). Power utilities have widely accepted XLPE-insulated cable for transmission circuits at operating voltages up to at least 13B kV (2). XLrE or the--noset polyethylene may be used as an integral covering fc- ", c.-vc cage ex plications on very small diameter single-conductor cables (3). Crosslinked poly ethylene may also ba used in heat-shrinkable tubing to insulate joints and splices of hook-up wire (4), Thermal Cecomoosition Mechanisms No specific information was found for crosslinkad polyethylene; but since cross linking is involved in thermal degradation of linear and branched polyethylene:, the thermal decomnosition mechanisms ;f "(PLE are orooac" - similar to triese polyethylene (see page 6-12). S.mmarv o* Experimental Studies Reviewed vro1 vss. Unfilled crosslinked polyethylene insulation from a No. 14 small wi-e lost l.~\ of its initial weignt when heated from room temperature to 393C at the rate of 10C/min; *8.9%. when heated to 4S3C; and 97,5%, when heated to 46r0C Another DCP-cross 1 i nked polyethylene sample lost 2. OS o'" its weight by 361C anc 93.7% c.. 481C. A sample with 33% filler showed about tne same weight loss increasing temperatures (5;. 3C* decomposition products ano aodltives present in the crosslinked polyethylene are ike'/ to be identi fiC among oyo lyzates at low temperatures Cross' i n*e-. colyet.ni ere '-om three tables tost haa failed s'tr 9 c- 11 ye;-: r' = " ss * MONS 217963 found to contain several compounds at the parts per million level. Acetopnenone, an expected degradation product of DCP, was not found in any of the three samples. In one sample, o-methyl styrene was the major contaminant and cumene was the second most important contaminant. In the two > ther samples, thiobutyric acid S-decyl ester was the major contaminant followed oy phenol anc cumyl alcohol (or vice versa). Other impurities found in one or two of the three samples included cumene, toluene, dipropropylene glycol methyl ether, acetophenone, phthalates, chloroform, and benzene. Uncrosslinked polyethylene from a fourth cable contained thiobutyric acid S-decyl ester, phenol, and toluene (all identifications were made by gas chromatography-mass spectrometry) (6). Combustion. No specific information was found on XlP combustion or other thermal oxidation. References 1. G. G. Hawley. The Condensed Chemical Dictionary. 10th ed. New York: Van 2. T. Tanaka and A. Greenwood. Advanced Power Cable Technology, II. Present and Future. Boca Raton, FL: CRC Press, 1983 3. J. . Hogan. "Wire and Cable Coverings" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 13. New York; Interscience Publishers: a Division of John Wiley & Sons, 1981, pp. 564*590. 4. R. N. Sampson. "Insulation, Electric" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 13. M, Grayson, Editor. New York: Interscience Publishers, a Division of John Wilev & Sons, 1981, pp. 34-563. j. R. R. A. Abou-Shaaoan, J. L. Haberfeid, Z. M. Carrall, II, J. F. Johnson, ano A, P. Simonelli. Characterization of Polymer c Dielectric Insulation, v. Thermal Analysis of Dielectric Insulation, Ethylene/Propylene Rubbers, and C-osslinked Polyethylenes Decomposed in a Nitrcgen Atmosphere. Polvm. Enp. Sci., 16(8), 544-551 (1976). 6. J. Tanaka and R. Luther. Analysis of Cables with Visible halos. Coif. Rec. IEEE Jnt. Svmp. Electr Insul.. 292-295 (1982). KRAFT PAPER General Information Molecular rrrmula: (Cs7 H,o0c) n Itructure of Polymer: 88 to 91j a Ipha-cel 1 ul ose, 1 to 3% hemicel lulose , and 2 to HONS 217964 Use*: Electrical use for kraft paper is for insulation in oi 1-immersed equipment such as transformers. To upgrade the thermal resistance, the kraft paper may be modified by cyanoethylation, amine treatment, etc. Additives such as morpholine, oxyalkylamine, aromatic polyamines, p-toluene sulfone {?), and carbamates have been used or suggested (1). Oi1-impregnated paper is used to insulate overhead distribution cables (2) and is the standard i-sulation for 115-550 kV circuits, whereas extruded solid-dielectric insulation prevails over paper insulation for intermediate voltage cables (15 to 59 kV). Use of paper insulation in the intermediate range will probably continue because of the need to maintain existing installations and its desirable character istics such as long service life (3). Thermal Decomposition Mechanisms Cellulose pyrolyzed at rapid heating rates primarily degrades by chain cleavage. Segments decompose to give a syrup whose major component is levoglucosan (1,6anhydro-0-D-glucoDyranose) and its furanose isomer (1,6-anhydro-B-O-glucof urancse). Numerous lower molecular weight products form at temperatures 50DC. Ash in trace amounts appears to catalyze condensation, dehydration, and fragmentation reactions, thereby reducing syrup yields. Primary syrup products can be converted to ethylene and other important industrial chemicals. Nonspecific thermal decomposition reactions occur. Anhydrosugar derivatives are formed by intramolecular transglycosylation reactions, which compete with dehydra tion, fragmentation, and condensation reactions. These competing reactions lead ss ow noiec,;ar veigno gases, crar, ano numerous other products, tow nesting rates and long residence times reduce the yields of more desirable sugar deriva tives (*). dehydration anhydrocel1ulose--* char - CO, CO-, H;0 cepolymerication Summary o* Experimental Studies Reviewed pyrolysis. P-oouct gases from pyrolysis of kraft paper are produced in aoout the same amount* as Von pyrolysis of other cellulose sources, including woods, "he MONS 217965 gases are COj, CO, H2, C2Hj (acetylene), CH4 (methane), C2H, (ethylene), and other nydrocaroon* (5). Oepolymerlietion giues the anhydroglucose product levoglucosan (a glucopyranose derivative) and its furanose analog. Temperatures above 500C give numerous lower molecular weight products and char. Qehydration reactions give anhydrocel1ulose, which also decomposes to give char and volatiles (a). Combustion. No information was found on specific products of kraft paper combus tion. References 1. A. Miyoshi. New Additive for Improving the Thermal Aging Characteristics of Kraft Insulating Paper. IEEE Trans. Electr, Insul.. EI10{1), 13-17 (1975). 2. R N. Sampson. "Insulation, Electric" in: Kirk-Othmcr Encyclopedia of Chemical Technology. 3rd ed., Vo). 13. H. Grayson, Editor. New York: Interscience Publishers, a Division of John Wiley & Sons, 1981, pp. 534-563. 3. J, E. Hogan. "Wire and Cable Coverings" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed., Vol, 13. New York: Interscience Publishers, a Division of JohiTwiley & Sons, 1981, pp. 564-590. 4. M. W. Hopkins, C. Oejenga, and M. J. Antal, Jr. The Flash Pyrolys-': Cellulosic Materials Using Concentrated Visible Light. Sol. Energy, 32(4), 547*551 (1984). 5. M. W. Hopkins, H. J. Antal, Jr., and J. G. Kay. Radiant Flash Pyrolysis of Biomass Using a Xenon Flashtube. J. Appl. Polym, Sci. . 29(6), 2163-2175 (1984). POLYETHYLENE CASRN: 9002-88-4 Synonyms: Polythene; ethylene homopclymer; ethene nomopolymer Traae Names: Agiltne; Alathon; Alkathene; Courlene; Lupolen; Platilon; Pylen; Reevon (1). General Information Molecular Formula: (CjH*)^ MOMS 217966 Structure of Monomer and Polymer: CH2: CH2 Ethylene (ethene) -t-CH2CH2-^- Linear, hi gr.-aensity polyethylene is produced by polymerization in the presence of transition metal catalysts (e.g., chromium oxide or molybdenum oxide on a silicaalumina support) at relatively low temperatures and pressures. Incorporating butene, hexene, or another a-olefin as a comonomer lowers the density of the prod uct. Low-density polyethylene, with a relatively high degree of branching, is produced by use of higher pressures and temperatures and peroxide-type catalysts. Incorporating polar comonomers such as vinyl acetate modifies the properties of the product. Linear low-density polyethylene is produced by copolymerization of ethylene with ar-olefins such as butene, hexene, or octene at high or low pressures High-molecular-weight low-density polyethylene and high-molecular-weight highdensity polyethylene are two other types. The latter is a linear homopolymer or copolymer with weight average molecular weight 200,000 to 500,000. They have a density greater than 0.5*1 g/cm3 (2). The density of low-density polyethylene falls in the range 0.910-0.925 g/cm3; that of medium-density polyethylene, 0.926-0.9*0 g/cm3. Copolymer high-density poly ethylene has a aensity 0.9*1-0.959 g/cm3. Homopolymer high-density polyethylene has a density of at least 0.960 g/cm3 (2). Polyethylenes are also categorized according to the manufacturing method, i.e , vnether nign. -ecium, or low pressure was used, -icr-cressure polyethylene :rcludes low-density polyethylene and medium-density polyethylene up to a density o' 0.933 g/cm-. Low-pressure polyetnylene includes meci um-dens ity polyethylene `'em a density of *- 3.933 g/cm3 through high-density polyethyienes with densities ud to > 0.96 g/cm3. ved1um-pressure polyethylene have "igh densities (* 0.95-n- 0.96; (3). Uses: Polyethylene uses include coatings, containers, toys, liners, sags, ana coe and tubino as we'l as the electrical applications. Resins with melt indexes of j.2 to C.l g. 1." tin are used as wire and cable coatings in thicknesses ^ang'ng ;.005 to j.z (0.13 to L; mm). Polyethylene insulation and jacketing 's usee or, nign .oltaoe tower csole, teleonone cable, television lead-in cab''e. ann cas'e. .'lea- ' tw-sensity pelyet-yiene. wnicr. 's a cooo'yme- of et-y'-ene *>:- HONS 217967 various a-olefins, may also be used for wire and cable insulation ana jacketing. Hign-mo'iecu 1 ar-weight hign-aensity polyethylene, wnich may be either homopolymers (highest density) or copolymers (typical monomers are butene, hexene, and octene), is used for cable conduit and other pipe (2). Polyethylene, crosslinked polyethylene, ethylene-propylene rubber, and butyl rubber are used for extruded cable insulation. Polyethylene has a low power dissipation factor, high volume resistivity, high breakdown strength, and ozone and weathering resistance; but It Is susceptible to environmental conditions above 75C. A major use for polyethylene in the electric power industry in the United States is for duct or pipe for installing buried cable. The duct material, called combined duct cable or CO cable, is usually black, low* or medium-density polyethylene (3). Crosslinked polyethylene (XLPE) is widely preferred for extruded cable insulation and accounts for most of the increase in tne use of polyethylene in distribution power cables since 1967 (4). Crosslinked polyethylene is discussed on page 6-5. Polyethylene used in buried underground distribution cables (15,000 to 25,000 V) nas experienced a nign rate of intoieraplt fa. lures after service 'or 5 T yti-s. The low cost still makes use of polyethylene attractive. Research continues to find additives to improve the service life. Polyethylene has been used for years as low-loss insulation in high-frequency, coaxial cables for electronic applica tions. Polyethylene is also used in ocean telephone and telegraph cables and direct-buried catnodic-protection circuits and telephone cables (5). However, polyethylene is impractical for use in high-voltage, power transmission cables. Caoie jackets siade of polyethylene are used when moisture resistance is the pri mary requirement, such as for nonleaded dry paper or plastic-insulated telephone caoles. Use of polyethylene jackets for leed-sheathed underground power cables facilitates pulling the cable into ducts. High-molecular-weight polyethylene (molecular weight about 30,000 amu) is used to avoid stress cracking. If the covering is to be exposed to weather, a filling of about 2% carbon black must be addec to prevent ultraviolet-radiation cracking (5). Polyethylene can also be used for insulating moldings (6). C* - - MOMS 217968 Thermal Decomposition Mechanisms Pyrolysis. In the absence of oxygen. polyethylene undergoes crosslinking at about 200 to 290C and decomposes at temperatures above 290C. Scission reactions com pete with crosslinking reactions and are favored at higher temperatures. Thermal decomposition of polyethylene creates fragments with molecular weights up to about 700. Thermal cracking of polyethylene gives good yields of high-melting waxes (molecular weights greater than 400) without char or tar formation (7). Polyethylene degradation is accompanied by a rapid decrease in the polymer's molec ular weight. Little monomer is produced by depropagation reactions (i.e., the reverse of the free radical addition reaction that produced the polymer). Mono olefins are produced Dy intramolecular transfer of hydrogen atoms to a carbon radical; the six-membered ring transition state favors the formation of 1-hexene. Larger fragments form in intermolecular transfers. Peroxide links present in the polymer from slight oxidation during preparation, storage, and processing facili tate the free radical formation Other weak links in the polyethylene structure are carbonyl groups, chain branches, and unsaturated structures (8). Combustion. Thermal oxidation of polyolefins and other hydrocarbons (RH; involves generation of a hydrocarbon radical (R ); reaction of the hydrocarbon radical R' with oxygen ( 00 ) to give a peroxy radical R00 ; prooagation of the reaction py abstracting H from another or the same hydrocarbon molecule, thereby producing a new hydrocarbon radical R` ; and reaction of R' with 00 to give a new peroxy radical R`00 . Peroxy radicals can also abstract H from RK, giving ROOM. ROQH decomposition gives R0 and HO , wnich can also participate in the chain reaction with SH (71. Summarv of Experimental Studies Reviewed Pvt-q'Ivsi $. Pyrolysis of polyethylene at temperatures up to 1000C gives saturated (paraffins, alkanes) and unsaturated hydrocarbon; (ciefins. alkenes , anc cienes) The olefins are primarily 1-alkenes (a-olefint) with lesser amounts of o.u-cnene; Products having up to 18 carbons have been tot'tifleo, some studies have -eoorteo products whose chain lengths extended to 30 or more car-sons (9.10). HONS 217969 Generally, major paraffin and orolefin pyrolysis products throughout the tenperature range studied had no more than seven caroons. Hydrogen was reported to be a major volatile product at 1000C (11). a.iu-Olefins (a.w-dienes), olefins with non terminal double bonds, and aromatics were generally trace to minor products. Prod ucts with more than 21 carbons were predominantly straight-chain hydrocarbons for low-oensity polyethylene and olefins for high-density polyethylene (10). The experimental pyrolysis studies we reviewed are summarized in Table 6-1. Combustion. Polyethylene may undergo slight thermooxidative degradation at pro cessing temperatures up to 320C. Heating polyethylene below about 300C caused a slight weight loss (up to about 4%). Volatile products largely accounting for the loss were water, ethylene, and low-molecular-weight alcohols, aldehydes, ketones, anc carboxylic acids <20, citing older work). Oxygen-containing compounds were major products up through at least 3S0C but were minor products between 350 and 700C, indicating that pyrolytic processes dominated in this region. At 1000C, two ketones-'hexanone and octanone--were among the major volatile products (21). Olefins and paraffins were intermediate-to-major products throughout the tempera ture range reviewed (S 1Q00C). At the higher temperatures, the or-olefins were generally long-chain hydrocarbons, whereas the dienes and paraffins had shorter chains (18). Only one reference (22) reported that carbon dioxide (SO to 74% yield) and carbon monoxide (20 to 213!) were major combustion products, with 19% ethylene, about 7% methane, and 1 to 3% acetylene comprising the remaining volatiles produced at 7QQC. Soot was also an intermeaiate-to-major combustion product, having yields of 6 to 25% (based on the weight of the dried soot and the weight of the unturned sample) at 600 to 900C. The yields of aromatic products increased with increasing tem perature. They were found mainly in soot and cold-trapped liquids. 6enzene de rivatives without condensed rings, such as styrene and ethylbenzene, were products formed in intermediate yields at 1000C. Their yields were usually minor at lower HONS 217970 o-.; HONS 2 1 7 9 7 1 tr I ! -- gt on on cC= Ol S= ca. f* k k k '*! IS I t; tt 4 I ***** kkVkkkkm aieiiBs * ^ 9 o j iiinni ., ii i........ill .1: iiHjnni;; ~sk: j9ec. -- i i| '" = -:.- li ., * - C i { =t : T V3--}r- :n?h t_-i _-----------------k----".Jl i.#;!--!--:---`v M& t Si iS _;;*](fEf >:.;!-; temperatures. The yields of individual polycyclic aromatic hydrocarbons (PAHs; condensed benzene derivatives) rose from about 0.01% at 600C to about 0.1% at 900C. Yields were based on the original polymer sample weight. At 900C, the concentration of benzo[a]pyrene (8[a]P) was 1.06% in the dried soot compared to 0,041% in urban air particulates. It should be noted that although the amount of B[a]P produced per gram of polyethylene was about the same as that produced per gram of polystyrene, the 6[a]P concentration in polyethylene soot was three to four times greater because polystyrene produced three to four times as much soot as did polyethylene (23). About 50% of the PAHs in the smoke particulates from either flaming or nonflaming (smoldering) combustion of polyethylene was pyrene. The only other major PAH that was formed during nonflaming combustion was C,Hl0 (anthracene or phenanthrene). Flaming combustion gave a wider variety of PAHs (24). At 950C, the concentrations of individual PAHs and other aromatics caught in cold traps were < 1 to about 4% (based on the weight of the total condensate, whose amount relative to the initial DO'v'nen we'Ght w?s net given) except for naphthalene at 13 E% ()fl). The daHs 'de"* tified that are carcinogens included benz[a]anthracene, benzo[b]f1uoranthene (2,3benzofVuoranthene), benzo[c]phenanthrene, benzo[a]pyrene, benzo[e]pyrene, and chrysene. Studies reviewed on the thermooxidation and combustion of polyethylene are summa rized in Tables 6-2 and 6-3. MOMS 217972 S t b t l ? SNOW pSI*S-' e oo S'? in SH < O <-- ir eoc o o is h it 1j *1 n >3 it Ct C h ?" ' f. !> ,S .1*9 2A{~-i-*f-*--- -,**'* Z5** .SJm ill si I S t*! :M 5.5< ! I? Si &SS I1fi1*tn-11111yV__iii i tsi'*:! Ss-siSSil * 5-15 jj i* : ^il5ir Table 6-2 (continued) HONS 2 1 7 9 7 4 ? L. sr= fee S* P t "" '-i~ 11 { I fif s & Wtc ^-.-i--'*i_ . V .... A;y:-~*< 5 Sf$ "5?55$j 11 < n' !! I 1= 11H 1* I* % Yi~i iiUIiliU :.'-.i.n is |j Hitt ;- titif: *l53 U..L.I-, jlJl ! ill-IfJiliili i]i tillt Jitts - I ; Vt aaJ I V -- 6-17 HONS 2 1 7 9 7 5 UD #* H i Sr * Sz ,? <* < < / t t l * k p h j <<!( J J 4 k fJ iL Ii 1i -i t i nt j z itU1r ini iriiiljil Uf,t;*-Ui|-si*It.miii ITT i j^; it 44T7 "-13 Table 6 3 HONS 2 1 7 9 7 6 iii I r* J Hi ft 3 el sI wooo o o o0*1 < o 1/1 ou n 1 I mm 11 33 n s: 6*19 Table 6-3 (continued) HONS 2 1 7 9 7 7 I i ] ]i i L! , r it ll ai i !. i 5 ? k 3 ?* * ^' hi =3 'f ^ tL.i/f = p: I; * *.113sn* VI t j. Hill fi l If:! !8 i* ti * ei bi S' - S.I I Uj*a wi#?vua us* Mu* wi> :.1 u W WWWhJMUS#b iI li I . is UU il(i! Hililt -v t ; ,: iln IV i-` : Hi I W.-ft e <- ip:f : i:LIs] f - Vi ill i 6-30 HONS 2 1 7 9 7 8 rid m ?S I iid 111 43* C C a Of 2 !5fl 3 a H a aa a ?gra --* * <4 f kgfagivl iv-MM W-TtS ^1 UO U W W w Up M w wwUVwwV wWwwwU < m ip T 6-21 References 1. M. Windholz, Editor. The Merck Index. 10th ed. Rahway, NJ: Merck and Company, Inc., 1983. 2. Modern Plastics Encyclopedia. 1985-1986. Vol. 62, No, 10A. J. Agranoff, Editor. New York: McGraw-Hill, Inc., 1986. 3. T. Tanaka and A. Greenwood. Advanced Power Cable Technology, I. 8asic Concepts and Testing. Boca Raton, FL: CRC Press, 1983. 4. T. Tanaka and A, Greenwood. Advanced Power Cable Technology ll. Present and Future. Boca Raton, FL: CRC Press, 1983. 5. J. E. Hogan. "Wire and Cable Coverings" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed. , Vol. 13. New York: Interscience Publishers: A Division of John Wiley and Sons, 1981, pp. 564-590. 6. R. N. Sampson. "Insulation, Electric" in: Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed. , Vol. 13. li. Grayson, Editor. New York: Interscience Publishers: A Division of John Wiley and Sons, 1981, pp. 534-563. 7. R. H. Hansen. "Thermal and Oxidative Degradation of Polyethylene, Polypropy lene, and Related Olefin Polymers" in: Thermal Stability of Polymers. Vol. 1. R. T. Conley, Editor. New York: Marcel Oekner, Inc., 1970, pp. 153-187. 8. N. Grassie and G. Scott. Polymer Degradation and Stabilization. Cambridge. U.K.: Cambridge University Press, 1985. 9. A. V. Bratchikov, B. A. Berendeev, and S. S. Ivanchev. Gas-Chromatographic Analysis of Polyeth lene Pyrolysis Products. Plast. Massv. No. 12, 34-35 (1984). 10. W. J. Irwin. Analytical Pyrolvsis: A Comprehensive Guide. New York: Marcel Oekker, 1982. 11. M. Chaigrseau. Gas Emitted by the Pyrolysis of Different PlasticMaterials a 1000. C.R. Acad. Sci. . Ser. C. 278(2), 109-111 (1974). 12. S. L. Madorsky. Thermal Degradation of Organic PoWmers. New York: Jonn Wiley and Sons, 1964. 13. J. Mitera, J. Michal, J. Kubat, and V. Kubelka. Analysis of Thermo-Ox: daf: Products of Polypropylene and Polyethylene by Gas Chromatograpny/Mass Spec trometry. Fresenius' Z. Anal. Chem, , 281(1), 23-27 (1976). 14. J Michal, J. Mitera, and S. Tardon. Toxicity of Thermal Degradationpr0auc of Polyethylene and Poly(prooylene). Fire Mater,, 1(4), 160-168 (1976) 15. A. Zeman. Identification of Some Commercially Available Polymers ty Therma Degradation in a Mass Spectrometer. Anoew. Hakromol. C~.-m., 31. 1-24 16. v. Pacakova. M. Borecka, and P. A. Leclercq. identification of Therms1 Degradation Products of Polymers by Caoillary Gas Chrcmatograohy. R. E Kaiser, Eaitor -oc. Int. Svmo. Capillary Chromatocr., 4th. 35-51 (193. HONS 217979 27. N. Pirard. Analysis of the Thermal Decomposition Products of Natural and Synthetic Materials Found in Dwellings. Ann. Mines Belg.. No, 5-6, 203-231 (19B3). 18. R. A. Hawley-Fedder, H, L. Parsons, and F. W. Karasek. Products Obtained During Combustion of Polymers Under Simulated Incinerator Conditions, I. Polyethylene. J. Chromatoqr., 314, 263-273 (1984). 19. J. A. Gardella, Jr., D. M. Hercules, a d H, J. Heinen. Mass Spectrometry of Molecular Solids: Laser Microprobe Mass Analysis (LAMMA) of Selected Poly mers. Spectrosc. Lett. . 13(6), 347-360 (1980). 20. A. Hoff and S. Jacobsson, Thermo-Oxidative Degradation of Low-Density Poly ethylene Close to Industrial Processing Conditions. J. AopI. Polym. Sci 26, 3409-3423 (1981). 21. J. Mitera and J. Mfchal. The Combustion Products of Polymeric Materials. Ill: GC-MS Analysis of the Combustion Products of Polyethylene, Polypropy lene, Polystyrene, and Polyamide. Fire Mater.. 9(3), 111-116 (1985). 22. T. Morimoto, K. Takeyama, and F. Konishi. Composition of Gaseous Combustion Products of Polymers. J. Appl. Polym. Sci. , 20(7), 1967-1976 (1976). 23. T. Morikawa. Evolution of Soot and Polycyclic Aromatic Hydrocarbons in Com bustion. Shobo Kenkyusho Hofcoku. 45, 13-24 (1978). 24. M. Pasternak, 8. T. Zinn, and R, F. Browner. The Role of Polycyclic Aromatic Hydrocarbons (PAH) in the Formation of Smoke Particulates Ouring the Combus tion of Polymeric Materials. Symp. (Int. ) Combust,, fProc.']. Volume Date 1980, 18th, 91-99 (1981). 25. T. Morikawa. Acrolein, Formaldehyde, and Volatile Fatty Acids from Smoldering Combustion. J. Combust. Toxicol.. 3(2), 135-150 (1976). 26. E. A, Boettner, G. L. Ball, and B. Weise. Combustion Products from the Incineration of Plastics. PB Rep. No. 222001/0. Springfield, VA: U. S. National Technical Information Service, 1973. 27. V. Pacakova, P. A, Leclercg, 3. Hoiotik, sno l, Beroun. A Study of Oxidative Degradation of Plastics by GC and GC-MS. Anal. Lett. , 18(A14), 1759-1775 (1985). 28. J. H. Hodgkin, M. N. Galbraltn, and V. K. Chong. Combustion Products from Burning Polyethylene. J. Macromol. Sci., Chem., A17(l), 35-43 (1982). POLY(ETHYLENE TEREPHTHALATE) (MYLAR) CASRN: 25038-59-9 Synonyms: PET 'rade Names (producers): Mylar, Cronar (DuPont); Celanar (Celanese); Estar (Eastman Kodak); Scotchpar (3M); Videne (Goodyear); Avistar (FMC) (1). Products O HONS 217980 with carboxy end groups are Dacron, Amilar, and Fiber V. Products with methyl ester end groups include Terylene, Diolen, Enkalene, Fortrel, Tergal, Terita), Terlenka, Trevira, and Mylar (2), General Information Molecular Formula: Structure of Monomers and Polymer: HOCH2CH2OH Ethylene glycol Terephthalic acid (R = H) Dimethyl terephthalate (R * Me) where R - H or CH3 Poly(ethylene terephthalate) Uses: Major markets for polyester films in 19GG included magnetic tape, electri cal, packaging, and photography (1), Poty(sthylent terephthalate) (PET) is the most widely used film for electrical insulation (3). Electrical applications were second only to magnetic tape use in 19GG. Polyesters are used for wire and cable insulation, transformer insulation, and in capacitors. Type A Mylar film, which has been biaxially structured and haat set, has numerous electrical uses such as slot liners, wedges, and phase insulation for motor and field coils; magnet wire insulation; * barrier and insulation tape in cables; transformer coil insulation; and backing for mica. Type C Myiar is used as a dielectric in high-temperature capacitor* (1), Glass-reinforced PET is the only thermoplastic recognized by Underwriters Labora tory for Class H (180C) systems. Class B (130C) and Class F (155C) systems may also use PET. Many types of coil bobbins, including Class A transformer ballasts, are made from reinforced PET (4), 6-24 HONS 217981 Thermal Qecomposition Mechanisms Pyrolysis and combustion of PET give similar products and similar product yields. Thus, the mechanisms will not be discussed separately. This discussion is based on four reviews published from 1970 to 1984 (5-8). Degradation of PET under burning conditions is primarily pyrolytic rather than themooxi dative. For most of the decomposition, chain scis*ion is rate limiting, with the secondary breakdown to small, volatile molecules being faster. The predominant mechanism for chain scission involves proton transfer in a cyclic transition state: 0.. .H 02CCsHC yCH02CC,HC02-~ / 0--yCH2 OH I o2ccshc p 0 + ch2=cho2cc6hco2 Random scission of the aster links gives rise to formation of vinyl ester oligo mers. Scission close to the chain ends will give terephthaltc acid, divfnyl tere phthalate, and vinyl terephthalic acid monoester (CH2=CH02CC*HC02H). decarboxylation of vinyl terephthalic acid monoester will give vinyl benzoate and C02; decarboxylation of terephthalic acid will give benzoic acid and C02; and de carboxylation of benzole acid will give benzene and C02. Benzene production is not affected by the presence of oxygen. Benzoic acid, divinyl terephthalate, and vinyl benzoate yields decrease above aoout 700C due to decomposition. The yield of vinyl benzoate is somewhat higher in the presence of oxygen, but yields of ben zoic acid and divinyl terephthalate have higher yields from pyrolysis. Both CO and C02 arise from decarboxylation following chain scission reactions, but evolution of C02 from PET on pyrolysis decreases somewhat above about 700C. Ap parently COj reacts with C above about 700C to give more CO. A likely route for CO production involves scission of the single bond between oxy gen and the carbonyl carbon: -C,H<C0CH2CH,- 0CH2CH2.' -CsH4' + CO + 'OCHjCHj- 6-25 HONS 217982 At higher pyrolysis temperatures, about as much CO is formed from this process as is C02 from the cyclic scission and decarboxylation reactions described above. On a weight percentage basis, ethylene dibenzoate is a significant thermal decom* position product although on a molar basis, its loss is not large. More is lost from pyrolysis than from combustion. We conjecture that it may be formed in the scission reactions producing carbon monoxide: 0 00 0 Ethylene dibenzoate Formation of volatile acetaldehyde and of the anhydride species detected in non volatile char residues may be accounted for by the following scheme: 00 0 CH3 0 If II II I It C#HC0CH=CHj + HOCCeH4*~ ------- '~C,H4CCFI CHO^ 00 IIII '~C,,HC0CC#H CHjCHO Acetaldehyde yields are similar during combustion or pyrolysis and decrease above about 6Q0C. 6-26 MOHS 217983 Methane and acetylene appear to be produced from very similar reactions in air or in its absence. Reactions proposed that would lead to acetylene and methane for mation are the following: -CeH4C02H + CH* CH --C,H<C0ICH=CH, '-'-CSH,CH=CH1 + C02 00 -- c*hcch2ch ------- "C*H4CCH3 + CO CH, + H-R CH, + R These reactions would also account for styrene and acetophenone. Secondary decom position of acetaldehyde may also account for methane and carbon monoxide. Summary of Experimental Studies Reviewed Pyrolysis. Major products (in yields generally greater than about 10 weight per cent based on the original polymer weight) from PET pyrolysis within the tempera ture range 288C to about 70CC included acetaldehyde, carbon dioxide, divinyl terephthalate, vinyl benzoate, ethylene dibenzoate, and benzoic acid. Products foreted in 1 to 9% yield Included carbon monoxide, ethylene, acetylene, and benzene. Trace to minor amounts of alcohols, aldehydes, ketones, benzene derivatives, ace tylene, Ci to C3 alkenes or alkanes, and 2-methy`.-l,3*dioxolane (the cyclic acetal formed from acetaldehyde and ethylene glycol; see Table 6-4 for structure) were also detected. Table 6*4 summarizes the pyrolysis experiments reviewed. Combustion. Thermal oxidation or combustion of PET in the range 340 to about 730C produced major amounts of carbon monoxide, carbon dioxide, acetaldehyde, acetylene, and PET dlmmrs and trimers. Intermediate amounts of methane, vinyl benzoate, di vinyl terephthalate, and benzoic acid were also reported. Less important products included tetramers, pentamers, formaldehyde, lower carboxylic acids, ethylene di benzoate, benzene, terephthalic acid, and hydroxyethyt terephthalate monoester. Results are summarized in Table 6-5. MONS 217984 6-27 HONS 2 17905 V"l O &- UJ < < ID. ^UJ -*o " ** I StTsH s:w=i ts -s-i s S<* *J* ST 8 s- a rfi -- . W. V # W I. k k k *** M*s u ! 2 * 21 5- c2 s Sgw ga ^ hC I? 54 ;M k 8-1I 14 !w3W ess t N 2S5 ii 8-- m*h* **#> MKr* Jwv -I #M st - r fl H ^ ji Jt I K*: e t 4 T'O S ^ w 2 clh>l( e -- -- * ** oMi < 6*29 HOHS 2 1 7 9 8 6 *** li II S3* ** * ** mi Sl'ft // / i % IJ si ;-i * r ttjl ss;TM fi t fr 6 ii i *C 2 t* t * I a i jij) si] < ,*~=' *fU < a. cLUt Ssi X' X 1-1 2 2 E-4 8* Is +*m I III i u1 t r/t l Mi t ft i * t Ml t iii 22 5-29 ! | | | t 3 b l References 1. J. M. Hawthorne and C. J. Hef f el f 1 nger, Encyclopedia of Polymer Science and ' Technology, Vol. 11- h. F, Hark and N. M. Bikales, Editors. New York: Wiley, 1969. pp. 42-61. 2. M. Windholz, Editor. The Merck Index. 10th ed. Rahway, NJ: Merck and Company, Inc- , 1983. 3. R. N. Sampson. "Insulation, Electric" in; Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed. , Vol. 13. M. Grayson, Editor. New York: Interscience Publishers, A Division of John Wiley and Sons, 1981, pp. 534-563. 4. Modern Plastics Encyclopedia, 1965-1986. Vol. 62, No. 10A. J. Agranoff, Editor. New York: McGraw-Hill, Inc., 1985. 5. R. T. Conley and R. A. Gaudiana. "Thermal and The"no-0xidative Degradation of Polyamides, Polyesters, Polyethers, and Related Polymers" in: Thermal Stability of Polymers. Vol. l. R. T. Conley, Editor. New York: Marcel Oekker, 1970, pp. 347-456. 6. M. E. 8ednas, M. Day, K. Ho, R. Sander, and D. M. Wiles. Combustion and Pyrolysis of Poly(ethylene Terephthalate). I. The Role of Flame Retardants on the Products of Pyrolysis. J. Appl. Polym. Sci.. 26, 277-289 (1981). 7. M. Day and D. M. Wiles. Influence of Temperature and Environment on the Thermal Decomposition of Poly(ethylene Terephthalate) Fibers With and Without the Flame Retardant Tris(2,3-dibromopropyl) Phosphate. J. Anal. Apol, Py rolysis. 7(1-2). 65-82 (1984), 8. A. Granzow. Flame Retardation by Phosphorus Compounds. Acct. Chem, Res. , 11, 177-183 (1978). 9. S. L. Madorsky. Thermal Degradation of Organic Polymers. New York: John Wiley and Sons, 1964. 10. T. Suebsaeng, C. A. Wilkie, V. T. Burger, J. Carter, and C. E. Brown. Solio Products fro* Thermal Decomoositlon of Polyfethv1ene Tereohthalate)- Inves-idacion oy CP/MAS Caroon-13-NMR anc Fourier Transform-IR. J, Polym. Sci . Polym. Chem. Ed.. 22(4), 945-957 (1984). 11. M. Day, V. Parfenov, end 0. M. Wiles. Combustion and Pyrolysis of Poly ethylene Terephthalate). III. The Effect of Tris(2,3-dibromooropyi) Phos phite on the Products of Pyrolysis. J, Appl. Polym. Sci.. 27(2), 575-589 (1982). 12. D. C. Conway and R. Marak. Analysis of Polymers by Pyrotysi s/Chemical Ion ization Mass Spectrometry. J, Polym, Sci., Polvm. Chem. Ed., 20(7), 1765 1774 (1982). 13. T. Morikawa. Acrolein, Formaldehyde, and Volatile Fatty Acids from Smolder ing Combustion. J. Combust. Toxicol. , 1(2), 135-150 (1976). 14. R. E. Aaams. Pyrolysis Mass Spectrometry of Terephthalate Polyesters l/s^c Negative Ionization, J. Polv-. Sci., Polym, Chem. Ed.. 20(1), 119-129 (1951 15. A. Zeman. Identi f ication of Some Commercially Available Polymers by 7hery Degradation in a Mass Spectrometer. Anaew. Makromol. Chem.. 31. l*2i l---- o* : u HONS 217987 16. D. J. Carlsson, M. Day, T. Suprunchuk, and D. M. Wiles. Pyrolysis of Poly- (ethylene Terephthalate) Fibers: Characterization of lnvolatile Residues J. Appl. Polvm. Scl., 28(2), 715-724 (1983), ' POLYSTYRENE CASRN: 9003-53-6 Synonyms: Styrene polymer; Vinylbenzene polymer; EthenyIbenzene homopolymer Trade Names (producers): Styron 666 U (Dow); lustrex P1X6 (Monsanto, UK); Dylene, Trycite, Hostyren (American Hoechst); Styrofoam (Dow). [There are more than 100 others. ] General Information Molecular Formula: (CsMsCHCH2)n Structure of Monomer and Polymer; CH: CHj ------- CHCHjCHCHj-.. Ph Ph . Styrene head-to-tai1 CHjCH- CH-CH,CH,CHCH-CH2J-- i * *I * ?h Ph Ph Ph J head- to-head-tai 1- to-tai 1 Uses: Electrical equipment; packaging; refrigerator doors; air conditioner cases: containers and molded household wares; machine housings; toys; clock and radio cabinets. Foams are used for thermal insulation, light construction (e.g. , boats); ice buckets, water coolers; fillers in shipping containers; furniture construction. Spheres are used as a radiator leak stopper (1). Ignition-resistant grades, which include halogenatcd organic compounds and antimony oxide, may be used in appliances, business machines, and electronic parts. Impact grades, which have improved resis tance to hydrocarbon solvents, are acceptable for containers of food products con taining fats and oils. Polystyrene use in magnetic tape ce'.settes, reels, and other consumer electronic components is a growth market (2). o-;i HONS 217988 Thermal Decomposition Mechanisms Above v 33QC, polystyrene degrades by the following reactions: Chain-end Initiation. Random scission of "weak links" (does not directly give volatiles below v 44QC). Oepolymeriiation (unzipping) to give monomer, > Intramolecular transfers to give dimers, trimers, and higher ol igomers. Intermolecular transfer to give short-chain fragments. The mechanism of polystyrene thermal degradation is still being actively studied (3). Scission by a radical process of C-C bonds 3 to chain end unsaturations must be preceded by reactions that create these unsaturations. Thus, the first step is removal of benzylic end units as shown (4): PhCHjCHjCHPhCHoCHPhCHfCHJ:CPhCH*-j-CHPhCHz'- PhCHj + CH^CPhCHjCHPhCHj* toluene H- CH2:C(Ph)CHj CHj: C(Ph)CH3 or-methyl styrene depolymerization PhCH:CHj styrene CH(Ph)CH2- intramolecuiar H transfer oligomers intermolecular H transfer further chain scission Since the concentration of unsaturated chain ends increases throughout the degra dation, formation of volatiles from depolymerization is accelerated. Regardless of the Initial molecular weight of the polystyrene ( 4000), the ratio of the rates of weight loss and o-methylstyrene evolution is constant throughout the degradation. Since the rate of toluene formation tends to increase throughout degradation, toluene must originate from other reactions besides the initial cleavage of the benzylic end groups. One of the sources is the newly createo 5-32 HONS 217989 benzylfc end groups formed from the {J scissions. Other mechanisms have also been proposed (5). Volatiles include mainly styrene and styrene dimer with other volatile oligomers. Short-chain fragments comprise an oily, high-boiling product. The solid residue comprises a lower molecular weight polymer than the original. Other aromatic hydrocarbons identified in the degradation products are benzene, toluene, ethyl benzene, isopropylbenzene, n-propylbenzene, allylbenzene, and cr-methy 1 styrene (3). Three distinct patterns of chain scission occur at subvolati1fzation temperature (280 to 300C jn vacuo) (6): 1. If the polystyrene was prepared anionlcally. chain scission is simple and random with the degree of degradation directly proportional to the heating time. 2. For polystyrenes polymerized thermally, very rapid scission of a small number of "weak links" occurs, after which the degree of degradation is again proportional to the heating time, 3. Polystyrenes whose polymerization was initiated by free radicals degrade by three processes having different rates: (a) Scission of highly labile "weak links." (b) Scission of fairly weak bonds. (c) "Normal" bond scission. Processing polystyrene in the presence of air gives groups capable of absorbing ultraviolet radiation, presumably hydroperoxy groups, which decompose to form ketohe groups (7): UV ~'-CH2C(Ph)(00H)CH2CH(Ph)---- ------------------------------- ----- CHjp(:0)Ph + HjO + PhCH:CH-- Summary of Experimental Studies Reviewed So much work has been done on the pyrolysis and combustion of polystyrene that only references from the last 5 years ware surveyed. HONS 217990 5-33 Pyrolysis. Styrene is usually reported as a major pyrolysis product (40 to 905 of volatiles) throughout the temperature ranges used in the studies reviewed (60 to 1400C) (8-19). Using ultrathin film samples, Lehrle et al. (1982) (11) found monomer was the only polystyrene degradation product from pyrolysis at 4S0 to 480C Toluene, o-methylstyrene, cumene (isopropylbenzene), dimer (2,4-diphenyl-l-butene) and trimer (2,4,6-tripheny1-1-hexene) are frequently reported (12-1S). Schroeder et al. (1984) (16) identified a triphenyIbenzene after pyrolysis at 292 to 336C, Toluene represents 6X of the volatiles at 510C (17); or-methyl styrene is a major product at 700C (12); dimer and trimer have been reported as major products at 300, 348, and 900C (12,13,18)- Most of the remaining products that have been tentatively identified (^ 100) are mono- through hexapheny1-substituted oligomer chains containing 2 to 14 carbons in the chain and usually some unsaturation. Triphenyl- and tetraphenyl-substituted C9 and Cl0 chains were identified as major products at 700C, and many other products were found in yields surpassing those of toluene and styrene. Relative amounts of pyrolysis products are difficult to judge from the results published by Lai and Locke (1984) (12). In contrast to the results of Lai and Locke (1984) (12), who found numerous prod ucts of the type (poly)phenyl-substituted chains by GC/MS, Smith (1984) (^9) re ported that at 700C, only styrene and or-methylstryene were major products, toluene was formed in Intermediate yield, and the minor products were hydrocarbons given ` as formulas with four to eight carbons and with only one or two unsaturations. Irwin (1982) (20) reviewed sevmra) other pyrolysis studies Indicating that the variation in the product distribution was largely due to the techniques used to pyrolyze the polystyrene sample. The temperatures, however, were not indicated for any of the experiments reviewed. Only two groups (17.18) reported finding any polycyclic aromatic hydrocarbons (indene, methylindene, and methyl naphthalene) and tnese identifications were only tentative. Combustion. Processing polystyrene in air (injection molding, thermoforming. or thermocutting; temperatures not given) produced workplace styrene concentrations v 0.1 to s 1.0 mg/m3 air (well below the OSHA permissible exoosure limit of 10? mg/m:), polyme- fume concentrations < 0.5 to > 1.0 mg/rn3, ana total aider;,des ' 0.1 to ' 0.: mg/m3, Depending on the (.aeration. concentrations of 0.; to ^0.3 mg/m- formaldehyde, acetaldehyde, formic acid, and acetic acid may oe ge-erated. Other oxidized products inc'uded benzaidehyae (CsH5CH0). benzoic =- scetzcnenone ( O^-irCOC^H^) (Vainiotaio. jnoubl i sneo: ctec o HONS 217991 PfSffli, 1984) (3). Major products detected in the liquid residue from polysty rene degradation starting at about 300C and encing with complete combustion at about 450C were styrene, phenol, and toluene. Other products identified were ethyl benzene. benzaldehyde, two methyl styrenes, n-propyIbenzene, indene, methylindene, acetophenone, naphthalene, methyl naphthalene, cinnamyl alcohol, biphenyl or acenaphthene, methylbiphenyl, and diphenylethane (21). Benzaldehyde, phenylacetaldehyde (CsHsCH2CH0), and other aldehydes were detected along with benzene,-toluene, ethylbenzene, styrene, and propylbenzene when flameretarded polystyrene was combusted at temperatures up to 490C (Masarik et al., 1976; cited by Hawley-Fedder et al., 1984) (22). The flash-ignition temperature of polystyrene is 345 to 360C; the self-ignition temperature is 490C (23). Morikawa (1978; cited by Hawley-Fedder et al., 1984) (22) subjected polystyrene to flaming combustion at 600 to 90OC. A soot containing polycyclic aromatic hydrocarbons (PAHs) was obtained in 50% yield based on the initial polymer weight. Most of the PAHs were generally 3- and 4-membered-ring species. Hawley-Fedder et al. (1984) (22) trapped and identified > 100 products, mostly PAHs, after combust ing polystyrene at 800 to 95Q#C. At 95QC, indene, naphthalene, biphenyl, and phenanthrene were the major products along with 29 others. Below 950C, there were eight major peaks in the total ion chromatogram produced by capillary gas chromatography-mass spectrometry. Besides the four PAHs mentioned at 950C, methylstyrene, (g-methylphenyl)phenylacetylene (CHjC6HsCeHsC!CH), and 1- and 2-methyl naphthalene were the major products. Another 40 to 50 compounds were identified. Among the PAHs identified were fluorene and substituted fluorcnes, substituted phenanthrenes and anthracenes, fluoroanthene, benzo[j,k]fluoranthene, benzo[e)pyrene, 3-methylcholanthene, pyrene, benzo[a]fluorene, benzo[b)f1uorene, benzo[g,h,jJperylene, benzo[c]phenanthrene, benz[a]anthracene, and chrysene. References 1. G. G. Hawley. The Condensed Chemical Dictionary. 10th ed. New York: Van Nostrand Reinhold to. , 1981. 2. Modern Plastics Encyclopedia. 1985-1986. Vo 1. 62, No. 10A. J. Agranoff, Editor. New York: McGraw-Hi1!Tine. , 1985. 3. P Pfaffli. Thermodegradation of Styrene-Containing Polymers. Prog, Clin. Bid . Res. , 141, 203-213 (1984). 4. 3. Camino, L. Costa, G. Clouet, A. Chiotis. J. Brossas, M. Bert, and A. Gjyot Thermal Degradation of Polystyrene. The Role of Chain Ends. Conv. Ital Hacromp 1, [Atti), 2, 317-324 (1983). HONS 217992 5. L. Cost!, G. Camino, A. Guyot, M. 8ert, and A. Chiotis. The Role of Chain End* in the Thermal Degradation of Anionic Polystyrene. Polym. Oeqrad. Stab. 4(4), 245-260 (1902). 6. G. G. Cameron, W. A. J. Bryce, and I. T. McWalter. Thermal Degradation of Polystyrene * 5. Effects of initiator Residues. Eur. Polym. J,. 20(6) 563-569 (1984). 7. W. L. Hawkins. Polymer Degradation and Stabi11lati on. New York: SpringerVerlag, 1984. 8. T. Rushung and K. J. Voorhees. Analysis of Smoke Aerosols from Nonflaming Combu*tion by Pyrolysit/Mass Spectrometry Pattern Recognition. Anal. Chem 56(3), 368-373 (1984). ------------------- ' 9. H. A. Schneider. "Survey and Critique of Thermo-Analytical Methods and Results" in: Degradation and Stabilization of Polymers. Vol. 1. H. H. G. Jellinek, Editor? Amsterdam, Noth.: Elsevier, 1983, pp. 506-553. 10. I. Ericsson. Influence of Pyrolysis Parameters on Results in Pyrolysis Gas Chromatography. J, Anal. Appl Pyrolysis, 8, 73-86 (1985). 11. R. S. Lehrle, R. E, Peakman, and J. C, Robb. Pyrolysis-Gas Liquid Chroma tography Util fled for a Kinetic Study of the Mechanisms of Initiation and Termination in the Thermal Degradation of Polystyrene. Eur. Polym. J., 18(6), 517-529 (1982). 12. S. T. Lai and 0, C. Locke. Pyrolysi*-Fluorescence Spectroscopy, Pyrolysis- Mess Spectrometry and Pyrolysis-Liquid Chromatography of Linear and Crosslinked Polystyrenes. J. Chromatocr.. 314, 283-293 (1984). 13. L. Costa, G. Camino, and L. Tro*sarelli. A Study of the Thermal Degradation of Polystyrene-Chloroelkane Mixtures by Thermogravimetry-High-Resolution Gas Chromatography. J. Anal. Appl, Pyrolysis, 8, 15-24 (1985). 14. T. H, Risby, J. A. Yergey, and J. J. Scocca. Linear Programmed Thermal Degradation Mass Spectrometry of Polystyrene and Po1y(vinyl Chloride). Anal. Chem.. 54(13), 2228-2233 (1982). 15. S. K. Brauman, I. J. Chen, and 0. P. Matiinger. Po1y*tyrene Degradation During Combustion. J. Polym. Sci.. Polym. Chem. Ed.. 21(6), 1831*1645 (1983) 16. U. K. 0. Schroeder, K. H. Ebert, and A. W. Hamielec. On the Kinetics and Mechanism of Thermal Degradation of Polystyrene, 2. Formation of Volatile Compounds, Makromol. Chem., 185(5), 991-1001 (1984). 17. V. Pacakova, M. Borecka, and P. A. Ledercq. Identification of Thermal Degradation Products of Polymers by Capillary Gas Chromatography. Proc. ;nt Svmo. Capillary Chromatoor,. 4th. R. E. Kaiser, Editor. Sad Duerkheim, Fed. Rep, Ger. Inst, Chromatogr., 1981, pp. 35-51. 18. R. J. Evans, T. A. Milne, and M. N. Soltys. Molecular-Beam Sampling/Mass Spectrometric Studies of the Primary Pyrolysis Hechanisms of Biomass, -ossi' Organic Matter, and Synthetic Polymers. Prepr. Pao. - Am. Chem. Soc.. On. Fuel Chem., 29(2), 20-31 (1984). 5- 36 HONS 217993 19. C. G, Smith. "Practical Analytical Pyrolysis Application* for the Polymer Industry" in: Analytical Pyrolysis. K. J. Voorhees, Editor. London, UK: Sutterworth, 1984, pp. 428-452. 20. W. J. Irwin. Analytical Pyrolysis: A Comprehensive Guide. New York: Marcel Dekker, 1982. 21. J. Troitisch, International Plastics Flammability Handbook. New York: Macmillan, 1983. 22. R. A. Hawley-Fedder, M. L. Parsons, and F. W. KaraseF. Products Obtained During Combustion of Polymers under Simulated Incinerator Conditions. II. Polystyrene. J, Chromatoor.. 315, 201-210 (1984), 23. E. A. Boettner, G. L. Ball, and 8. Weise. Combustion Products from the Incineration of Plastic*. PB 222001/0. Springfield, VA: National Technical In fo rma11 on ~$e rv ice, 1973. HONS 217994 Appendix A SUMMARY OF UTILITY MATERIALS PROPOSED FOR EXPERIMENTAL TESTING AND THEIR TOXIC THERMAL DEGRADATION PRODUCTS MOMS 217995 This appendix lists the utility industry materials that have been proposed for EPRI_sponsored review and/or experimental testing. Most of the materials were listed in the Request for Proposal for the current project. Additional materials such as Nomex and many of the polymeric coating materials were suggested after initiation of the project. In the column "Literature Reviewed," an S indicates that the material's thermal degradation was reviewed in a recent EPRI report by SCS Engineers, Inc. (1). An M indicates the materials reviewed by MRI in the text of the present report. The most toxic thermal degradation products (other than carbon monoxide) that have been reported in the literature or that could be presumed to be formed based on the elemental composition or substructural components of the materials are given in the table. Where MRI or SCS Engineers (1) has reviewed the materials, the products are primarily those listed in these reviews. For other materials, one or more reference citations are given for the known thermal degradation products listed. The products listed in these cases are based on a brief examination of the literature MRI has collected on the unreviewed materials. (For most of these materials, the literature search and acquisition was as comprehensive as that for the materials reviewed in this report.) HONS 217996 HONS 2 1 7 9 9 7 I II C{ Si * r; i; s* i -I Yi i* Hi j C Hil i 21 - *i >- -5! * stl ; 11 ii A-' HONS 2 1 7 9 9 8 * II II a* ; x*ep ! ( 1 r<~, I e i Hs 1 i w X * s! I&I* w s ir 'i I: > U j * j ! f uT * I i V iL I F I :i *I I 4 i| W* u a t If 1 lii ii * A H*| Vi i j I s i | IS t H| i li i i I A. fil *i! sv w i 2II 1 t: s !i *: ii _* i f*c3 * L7 Z 2* i* v iff K 4 -J ~1 A-4 HONS 2 1 7 9 9 9 8 i b b t i * tm E i m e t *1 4 b 5 V r I2 su' I i 4J eii Us <! f 1 . JJf -si 2 2tt 3 11 I e t t 3 I t i ffc 81 is <i ~ -Ji til Z- 23 A-5 I a! *s j ;l ii n w ICIi j! 5 J I | 5 i i* i I 1I |i ! L ; I (ar t t v --* -I 23 |l c? i! I i aa a st S o o o rw a5 c~t *1 V) X o fc * a i* *r .1 I A~S o o Is! jr. w- t s f\ i- i- | \ ]1?1*K II r m SI i iE s * s i * X i F w i! I1 w j \ i I i t s 5a r I ig I i I5 ni l x f n ly f lt ( p tty ffr - C.St It f* m i li 11 iz --i* ^* ;i 1 ii iM* m I I 5 3 ill A-7 t 1 . *1 si tir lV I i Sk 8u mb sHfl. J? 51 iI ;-i - Sj*:t! * S". ;i!.` r s ii Iff1.;! -- fc =" = rif*5t I *t1 * t*:ri %s*si i *:*H| I!-'i *; Si Jill \i iili<? .is=:si U h ri > * i U5ul1 jr*iUi* i-1 _ * " * I -- f S^Jp ii! : s-s.tr i*f!I I ! i 11-hi! J s ? i iSiti. J* I ? fhsss 1 ! IB I I I ** " ft-'N* CB fNJ o o fv oz X A-8 REFERENCES TO APPENDIX A 1. J. V. Zbozinek, J. R. Harsh, D. Guth, and A. Bohrnerud (SCS Engineers, Inc.). State-of-the-Art Review of Combustion and Pvrolysis By-Products of PCB Sub stitutes" EPRI EL-45QJ^ Palo Alto, CA: Electric Power Research Institute, March 1986. 2. W, S. Simmons. Toxicity Profiles of PCB Substitutes. EPRI EA-3567. Palo Alto, CA: Electric Power Research Institute, 1984. 3. G. G. Hawley. The Condensed Chemical Dictionary. 10th ed. New York: Van Nostrand Reinnold Company, 1981. 4. T. Mori moto, K. Takeyama, and F. Konishi. Composition of Gaseous Combustion Products of Polymers. J. Appl, Polym, Sci., 20(7), 1967-1976 (1976). 5. R. T. Conley. '"Thermosetting Resins" in: Thermal Stablity of Polymers. Vol. 1. R. T. Conley, Editor. New York; Marcel DekiTer, The., 1970, pp. 457-521. fi. S. L. Madorsky. Thermal Degradation of Oroanic Polymers. New York: John Wiley and Sons, 1964. 7. A. Alajberg. Products of Non-flaming Combustion of Phenol-Formaldehyde Resin Foam. J. Anal. Appl. Pyrolysis. 9, 255*263 (1986). 8. H. D. R. Schueddemage and 0. 0. Hummel. Characterization of High Polymers by Pyrolysis within the Field-Ionization Mass Spectrometer. Advan. Mass Soectrom,, 4, 857-866 (1968). 9. E. Braun and 8. C. Levin. the Literature on Products of Combustion and Toxicity. NBSIR-85/3139. Washington, DC: Consumer Product Safety Commission, January 1985, 10. R. A. Wessling. Polyvinylidene Chloride. New York: Gordon and Breach Science Publishers, 19??. 11. K. Hiramatsu. Pyrolysis Products of Polymeric Materials by Mass Spectrometry. III. Mass Spectrometric Analysis of the Pyrolysis Products of Polyacrylo nitrile and Polyfvinylidene Chloride). Shitsuryo Bunseki. 15(1), 17-28 (1967). 12. P. Perlstein. Identification of F-ores and Fibre Blends by Pyrolysis Gas Chromatography. Anal. Chim. Acta. 155, 173-181 (1983). 13. A. J. Pidduck. Mass Scactrometric Analysis of Halogenated Polymers. J. Anal. Appl. Pyrolysis. 7(3), 215-229 (1985). 14. W. W. Wright. "Fluorocarbon Polymers" in: Thermal Stability of olymers. Vol. 1. R. T, Conley, Editor. New York: Marcel Dekker, Inc., 1170, " pp. 287-346. 15. L. Slusarski and G. Janowska. Thermal Decomposition of Homo- and Copolymers of IsoDutylene. J. Therm. Anal. . 19(3), 435*447 (1980). 16. N. V. Schwartz. Analysis of Rubber Mixtures and Vulcanizates by Thermo gravimetry and Pyrolysis-Gas Chromatography. Gumffii. Fasern, Kunstst.. 37(6), 274-277 (1984). HONS 21*003 A-9 17. N. M. Seidov, fi. Sh. Kuliev, A. I. 8asov, and A. M, Mustafaev. Study of the Thermal Decomposition of an Ethylene-Propylene Copolymer of Different Com position. Azerb. KMm. Zh. . (4), 99-102 (1977). 18. C. G. Smith. "Practical Analytical Pyrolysis Applications for the Polymer Industry" in: Analytical Pyrolysis. K. J. Voorhees, Editor. London, UK: Butterworth, 1984, pp. 428*452. 19. A. V. Bratchikov, B. A. Berendeev, and A. G, Rodionov. Determination of the Composition of Ethylene-Propylene Copolymers by Pyrolytic Gas Chromatography Vysokomoi, Soedin., Ser, A. 27(5), 1107-1112 (1985). 20. W. Noble, B. B. Wheals, and M, M. Whitehouse. Characterization of Adhesives by Pyrolysis Gas Chromatography and Infrared Spectroscopy. Forensic Sci.. 3(2), 163-174 (1974). 21. M. F. Bakht. Thermal Degradation of Copolymers of Vinyl Alcohol and Vinyl Butyral. Pak. J. Sci. Ind. Res., 26(1), 35-40 (1983). 22. T. Drbeck. New Principles of Fire Hazard Assessment for Fluid-Filled Elec trical Equipment. Presented at 9th International Conference on Fire Safety. 1984, 30 pp. 23. C. R, Crane, D. C. Sanders, B. R. Endecott, and J. K. Abbott. Inhalation Toxicology. 3. Evaluation of Thermal Degradation Products from Aircraft and Automobile Engine Oils, Aircraft Hydraulic Fluid, and Mineral Oil. FAA-AM-83-12. A0-A133221. Springfield, VA: National Technical Information Service, 1983. 24. H. N. Woebcke, A. Korosi, and P. S. Virk. Pyrolysis of Unsubstituted Mono-, Di-, and Tri-cycloalkanes. Prepr., Div. Pet. Chem., Am. Chem. Soc. . 23(3). 1159-1165 (1978), 25. National Institute for Occupational Safety and Health. NIOSH Current Intel ligence Bulletin 45. Polychlorinated Biphenyls (PCB's): Potential Health Hazards from Electrical Equipment Fires or Failures. DHHS'EnIOSh Publication No. fifi-lll, Atlanta, GA: NIOSH. Centers Tor~i)iseese Control, 1906. 25 pp. 26. J. Vuceta. J. R. Marsh, S. Kennedy, L. Hildemann, and S. Wiley. State-of-the* Art Review; PCDOs and PCDFs in Utility PCB Fluid. EPRI CS-3308. Palo Alto. CJ: Electric Power Research Institute", 1983. 27. 8. Vanwert and T. Orbeck. "FIammebi1ity Testing of Dry Type Transformer Insulating Materials" in: Electr./Electron, Infui, Conf. . 12, [unpaginated. 3-pege reprint] (1975). 28. T. W, Dakin, L. Mandelcorn, and R. N. Sampson. The Past Twenty-Sive Years of Electrical Insulation. J. Electrochem. Soc., 126, 55C-62C (1979). 29. W. J. Irwin. Analytical Pyrolysis: A Comprehensive Guide. New York: Marcel Oekker, 1982. ~ 30. J. 0. Marshall and M. C. Kuklies. Fire Retardant Laminates Having Intumesceot Adhesive Layer Comprising Shellac. US. Patent US 4058643. November 17, 1977, 4 pp. HOMS 218004 31. "Appendix A: (J. S. Department of Labor, Occupational Safety and Health Administration, Chemical Information Table" in: OSHA Industrial Hvaiene Technical Manuel. Chicago, IL: Commerce Clearing House, Inc, ------- p-p-'A-I to A-251. 1 32. E. Metcalfe, 0. Booth, H, McAndrew, and W. 0. Woolley. The Pyrolysis of Organic Nitriles. Fire Mater, . 7(4), 185*192 (1903). HONS 218005 j- -1 Appendix B health and safety information for thermal degraoation products Introduction Explanation of Abbreviations and Health Codes Thermal Degradation Products References MOMS 218006 INTRODUCTION This appendix summarizes health and safety information for the products released by thermal degradation or volatilization from several materials used in the elec tric power industry. Besides health and safety information, the physical state of each product at room temperature and pressure is indicated. Solids and semivola tile liquids would require greater decontamination effort after a fire involving these materials than would the gaseous and volatile liquid products, which would largely dissipate during or immediately after a fire. The appendix includes most of the products from thermal degradation of the mate rials reviewed in this document. The listing is not exhaustive because sometimes the degradation products were so numerous from certain materials tnat some prod ucts were grouped in this review as a member of a chemical compound class such as a-olefins or benzoate esters. Other products not specifically listed in the docu ment and/or this appendix were high-molecular-weight trimers, tetramers, and higner oligomers. To help the reader readily identify which degradation products came from each mate rial -evieweo, the materials are 'isteo below with a mnemonic tor eacn name, .-oi1 owing that list is a list with the mnemonics in alphabetical order.* The appro priate mnemonics appear in parentheses by the name of each product in the appena'* Chlorosulfonated polyethylene Creosote** Cross linked polyethylenet Bisphenol A epoxy Halar Kapton Kraft paper Neoprene CSPE CRE XLPE EPO HAL KAP PAP N0 "No products were found for thermal degradation of Teflon PFA. and there were no Simple products to list for Nylon 11. **In material itself and/or from thermal degradation products rFrom additive. HONS 216007 Nitrile rubber Nome* Nylon 6 Nylon 6,6 Nylon 6,10 Pentachlorophenol Polyethyl ene Poly(ethylene terephthalate ) (Mylar) Polystyrene Polysul fone Polyurethane Teflon Teflon FEP Tefzel VI ton NIT NOM NY6 N66 610 PCP PE PET STY SUL PU TEF FEP TFZ VIT 610 CRE CSPE EPO FEP HAL KAP N66 NEO NIT NOM NY6 PAP PCP PE PET STY SUL PU TEF TFZ VIT xlpe Nylon 6,10 Creosote Chlorosulfonated polyethylene Bisphenol A epoxy resin Teflon FEP Halar Kapton Nylon 6,6 Neoprene Nitrile rubber Nomex Nylon 6 Kraft paper Pentachlorophenol Polyethylene Poly(ethylene terephthalate) Polystyrene Polysulfone Polyurethane Teflon Tefzel Viton Cross linked polyethylene sources were used for the health and safety information, RTECS, Registry of ic Effects of Chemical Substances 1981*1982* (1) and the "Industrial Hygiene Technical Manual, Appendix A" (2). Information fro* the latter reference it usu ally more extensive and includes OSHA standards (limits) for exposure to the prod uct In workplace air. Physical property information was derived from the Aldrich Catalog Handbook of Fine Chemicals 1986-1987. (3), the Merck Index (4), the Condensed Chemical Dictionary (5), or the CRC Handbook of Chemistry and Physics (6). Note: A 1983-1984 supplement has been published but was not used for this repor HOMS 21800S The Chemical Abstracts Service Registry Number (CA5RN) follows most of the product name* In the appendix. The CASRN is a unique identifier that greatly facilitates computerized searches for compound-specific information in databases that routinely use CASRNs such as CA Search or CAS ONLINE. W# have included the CASRNs for those readers who wish to find more detailed information about particular products. 3-t HOMS 2iaoo? EXPLANATION OF ABBREVIATIONS ANO HEALTH COOES CARC Carcinogenic effects Identified. CASRN = Chemical Abstracts Service Registry Number. DESC " Description. The physical state of a substance at standard temperature and pressure. EYE IRR Eye Irritation. H s Hours of exposure. HLTH * Toxicological properties along with the appropriate health code. IARC = International Agency for Research on Cancer. INI * Toxic dose from Inhalation; value shows length of exposure. ORAL or INGES ACUTE * Ingestion acute, toxic dose from short-term ingestion. INGES CHRONIC a Ingestion chronic. IPR = Toxic dose from intraperitoneal administration. IVN = Toxic dose from intravenous administration. LCS0 = Concentration in air required to kill half of the test animals. LDS0 = Oose, In mg substance per kg body weight of the test animal, required to kill half of the test animals. LD, or TO, * Lowest lethal dose or lowest toxic dose reported. LO LO NTP * National Toxicology Program. OSHA Occupational Safety and Health Administration. PAH Polycyclic aromatic hydrocarbon. SCll = Toxic dose from subcutaneous administration. SKIN or SKIN ABS * Skin absorption, toxic from dermal exposure. SKIN IRR = Skin irritation. HONS 218010 B-5 STOS = Standards: OSHA = Permissible exposure limit ' TLV = ACGIH-threshold limit value TWA = Time-weighted average STEL - Short term exposure limit Permissible exposure limits are those adopted by OSHA or recom mended by the American Conference of Governmental Industrial Hygienists (ACGIH) (1982 Threshold Limit Values Tlvs list). A "C" indicates a celling limit of exposure. W = Weeks of exposure. The health codes listed below describe the toxicological properties of the chem ical substance. Health Code 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Health Effects Cancer - Currently regulated by OSHA as a carcinogen. Chronic (Cumulative) Toxicity - Known or suspected animal or human carcinogen, mutagen (except Code No. 1 chemicals). Chronic (Cumulative) Toxicity * Long-term organ toxicity othe then nervous, respiratory, heeiatologic, or reproductive. Acute Toxicity - Short-term high risk effects. Reproductive Hazards - Teratogenesis or other reproductive impairment. Nervous System Disturbances - Cholinesterase inhibition. Nervous System Disturbances - Nervous system effects other than narcosis. Nervous System Disturbances - Narcosis. Respiratory Effects Other ''han Irritation - Respiratory sensitization (asthma or other). Respiratory Effects Other Than Irritation - Cumulative lung damage. Respiratory Effects - Acuta lung damage/edema or other. Hematologic (Blood) Disturbances - Anemias. Hematologic (Blood) Disturbances - Methemoglobinemia. Irritation-Eyes, Nose, Throat, Skin - Marked. Irritation-Eyes, Nose, Throat, Skin - Moderate Irritation-Eyes, Nose, Throat, Skin - Mild. Asphyxiants, Anoxiants. HONS 218011 IS Explosiva, Flammable, Safety (No Adverse Effects Encountered When Good Housekeeping Practices are Followed). 19 Generally low Risk Health Effects - Nuisance particulates, vapors, or gases. 20 General Low Risk Health Effects - Odor. HONS 218012 9-7 thermal degradation products Acenaphthene [a PAH] (CRE. CSPE?, CASRN: 83-32-9 DESC: Solid, m.p. 93-9SC MUTAGEN STY) Acenaphthylene [a PAH] (CRE, CSPE?) CASRN: 208-96-8 DESC: Solid, m,p, 88-91C MUTAGEN Acetaldehyde; Ethanal (NOM, PE, PET, PU, STY) CASRN: 75-07-0 STDS: OSHA: 200 ppm, 360 mg/m1 TLV: 100 ppm, 180 mg/m1 TWA; 150 ppm, 270 mg/m1 STEL OESC: Volatile Liquid HLTH: Irritation-Eyas, Nose, Throat, Sk1n--Marked (14). Narcosis (8). Kidney damage (3). SKIN IRR; Mild INGES ACUTE: Rat L010: 1930 mg/kg Acetic acid; Ethanoic acid (NOM, PE, STY) CASRN: 64-19-7 STOS: OSHA: 10 ppm, 25 mg/m3 TLV: 10 ppm, 25 mg/m3 TWA; 15 ppm, 37 mg/m3 STEL OESC. Volatile Liquid HLTH: Irritation-Eyes, hose, Throat, Skin--Markad (14, Greater than 30 ppm). SKIN IRR: Yas (If concentrated) INGES ACUTE: Human T0Lq: 1.47 mg/kg Acatona (EPO, NOM, P'J) CASRN: 67-64-1 STOS: OSHA; 1000 ppm, 2400 mg/m1 TLV: 75C ppm, 1780 mg/m1 TWA; 1000 ppm, 2375 mg/m1 STEL DESC; Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat--Mild (16, Less than 2000 ppm). Narcosis (8, Greater than 2000 ppm). SKIN IRR: Mild INGES ACUTE: Rat LDS0: 9750 mg/kg 8-3 MONS 218013 Acetonitrile (NIT, NQM, PU) CASRN: 75*05-6 STOSi OSHA: 40 ppm, 70 mg/m5 TLV: 40 ppm, 70 mg/m1 TVA; 60 ppm, 105 mg/m1 STL DESC: Volatile Liquid HLTH: Irritation-Eyes, Nose. Throat--HiId (16, Less than 50 ppm). Acute Toxicity (Cyanosis) (4,'Greater than SO ppm). SKIN ASS: Yes SKIN IRR: Yes INGES ACUTE: Human TD : S70 mg/kg Acetophenone; Diphenyl ketone (PET, STY, XLPE) CASRN: 98-B6-2 OESC: Semivolatile Liquid (m.p. 19-20C) SKIN IRR: Rabbit: 515 mg, open, mild ORAL: Rat LDS0: 900 mg/kg Acetylene; Ethyne (EPO, NOM, PAP, PE, PET, PU) CASRN: 74-66-2 DESC: Gas HLTH: Explosive (18). Asphyxiation (17, Greater than 2500 ppm). ACGIH; E (Simple asphyxiant) Acridine (CRE) CASRN: 260-94-6 DESC: Solid, m.p. SCU: Mouse L0r>: IVY1: Rabbit L0so: 107-110C 400 mg/kg 100 mg/kg Acrolein (PE, PET) CASRN: 107-02-8 STDS: OSHA: 0.1 ppm, 0.2S mg/m1 TLV: 0.1 ppm, 0.25 mg/m1 TWA; 0.3 ppm. 0.8 mg/m1 STEL DESC; Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat, Lungs, Skin--Marked (14). Mutagen (2). IARC CARC: Animal Indefinite, '79. SKIN ABS: Rabbit LDS0: 562 mg/kg SKIN IRR: Yes INGES ACUTE: Rabbit LDS0: 7 mg/kg Rat L0so: 46 mg/kg Acrylic acid (PE) CASRN: 79-10-7 STDS: TLV: 10 ppm, 30 mg/m1 TWA OESC: Semivolatile liquid HlTh: Human Indefinite, '79. SKIN ASS: Rabbit LDSo: 280 mg/kg SKIN IRR: Severe INGES ACUTE: Rat LDi0: 340 mg/kg t 3 MOWS 21801* Acryloni tri le (NIT, NOM, PU) CASRN: 107-13-1 STDS: OSHA; 2 ppm TLV: 2 ppm, 4.5 mg/m* TWA OESC: Volatile Liquid HLTH: Suspect carcinogen (2). Reproductive Hazards (5). CNS Depression (7). ACGIH: Ala (Human carcinogen) I ARC CARC: Human Suspect '79, '82. IARC CARC: Animal Positive '79. IARC CARC: Animal Suspect '82. SKIN ABS: Yes SKIN IRR: Yes INGES ACUTE; Rat LDS0: B2 mg/kg Adiponltriie (N66) CASRN: 111-69-3 OESC; Semivolatile Liquid INGES ACUTE; Rat L0so; 300 mg/kg Allene (PU) CASRN: 4S3-49-0 DESC: Gas 3-Aminoblphenyl (NOM) CASRN; 2243-47-2 3-Amfno-4-methyIphenyl Isocyanate (PU) p-Aminophenol; 4-Amlnophenol; 1-Ami no-4*hydroxybenzene (KAP) CASRN: 123-30*8 DESC: Solid, m.p. 188-190C SKIN IRR: Raobit: 12.500 ug/24 H, miid ORAL: Rat LDS0: 375 mg/kg N-(3-Ami nophenylJbenzamlde (NOM) " CASRN: 16091-26-2 -A1nophenyl phenyl ether; 4*Phenoxyani1ine (KAP) CASRN: 139-59-3 OESC; Solid, m.p. 82-84*C SKIN IRR: Rabbit: 500 mg/24 H, mild ORAL: Rat LDS0: 1100 mg/kg 9- 10 HONS 218015 Ammonia (NIT, NOM, PU) CASRN: 7664-41-7 STOS: OSHA: SO ppm, 35 mg/m* TLV: 25 ppm, 18 mg/m* TWA; 35 ppm, 27 mg/m* STEL OESC: Gas HlTH: Acute lung damage/edema or other (11). Irritation-Eyes, Nose, Throat, Bronchi, Lungs--Marked (14). SKIN IRR: If concentrated INGES ACUTE: Rat oral L0so; 350 mg/kg Aniline; Benzenamine (CRE, KAP, NOM) CASRN: 62-53-3 STOS: OSHA: 5 ppm, 19 mg/m* TLV: 2 ppm, 10 mg/m* TWA; 5 ppm, 20 mg/m* STEL OESC: Semivolatile Liquid HLTH: Methemogl obi nia (13). Suspect carcinogen (2). Acute Toxic1ty--short-term high risk effects (4). IARC CARC: Animal Indefinite '74. IARC CARC: Human Negative '74. SKIN ASS: Yes INGES ACUTE: Rat L0so: 440 mg/kg Anthracene (CRE, CSPE. PE) CASRN: 120-12*7 OESC: Solid, m.p. 216C SKIN IRR: Mild Benzaldehyde (STY, SUL) CASRN: 100-52-7 OESC: Semi vo! it Ha Liquid SKIN IRR; Rabbit: 500 mg/24 H, moderate ORAL: Rat LDS0: 1300 mg/kg Benzanilide (NON) CASRN: 93-98-1 DESC: Solid, m.p. 162-164C Benz[a]enthracene; 1,2-Senzanthracene [a PAH] (CRE, PE, STY) CASRN: 56-55-3 OESC: Solid, m.p. 157-159C IARC CARC: Animal Positive, '73. IVN: Mouse U>Lo: 10 mg/kg Benzene (CSPE, EPO, NOM, PCP. PE, PET, PU, STY, SUL, XLPE) CASRN: 71-43-2 STDS: OSHA; 10 ppm TLV: 10 ppm, 30 ag/m* TWA; 25 ppm, 75 mg/m* STEL ESC: Volatile Liquid 0-11 HONS 218016 H|.Th: Suspect Leukemogen (2), Cumulative bone marrow damage (12). ACGIH: A2 (Suspect carcinogen) I ARC CARC; Human Suspect '74 & '82. IARC CARC: Human Positive '82. 1 ARC CARC: Animal Suspect '82. IARC CARC: Animal ' 74. Listed in NTP 2nd Annual Report on Ctrcinogtnt, SKIN ABS: Slight SKIN IRR: Mild JNGES ACUTE: Human TD^: 130 mg/kg '81. 8enzo[b]chrysene [a PAH] (CRE) CASRN: 214-17-5 DESC: Solid MUTAGEN SKIN CARE: Mouse TD^ : 28 mg/kg 2,3-Bentof 1uoranthene; 3,4-Benzo f1uoranthene; Benzofb?]fluorantnene; Benz[e]acepnenanthrylene [a PAH] (CRE, PE) CASRN: 205-99-2 " OESCr Solid, m.p. 163-16SC IARC CARC; Animal Positive, '73. TUMORIGEN: Mouse, skin: 88 ng/kg BenzoCj]fluoranthene: 10,11-Benzofluoranthene [a PAH] (CRE, STY?) CASRN: 205-82-3 OESC: Solid, m.p. 165C MUTAGEN IARC CARC: Animal Positive, '73 8enzo[j,k]fluoranthene [a PAH] (STY?) CASRN: Unavailable [Was benzoQ,_k]fluorene misnamed?] Senzc[k]fluoranthene; 11,12-Senzofluoranthene [a PAH] (CRE, STY?) CASRN: 207-08-9 OESC: Solid, m.p. 217C MUTAGEN CARC: Mouse skin: TO^: 2820 mg/kg/47 W-intermittent Benzofluorenes (CRE) 8enzo[e]fluorene: 1,2-Benzofluorene [a PAH] (PE, STY) CASRN: 238-84-6 8enzo[b]fluorene; 2,3*Benzofluorene [a PAH] (PE, STY) CASRN: 243-17-4 OESC: Solid, m.p. 209-210.5C HONS 21801? Benzofuran (SUL) CASRN (2,3-Isomer): 271-09-6 OESC: Semivolatile Liquid Benzoic acid (NOM, PET, STY) DESC: Solid, m.p. 122C; begins to sublime SKIN ABS: Yes SKIN IRR: Skin Human TD. 6 mg/kg INGES ACUTE: Man L0so: L500 mg/kg 100C Benzonitrile (CRE, KAP, NOM, PU) CASRN: 100-47-0 DESC: Semivolatile Liquid SKIN IRR: Rabbit; 500 mg/24 H, moderate ORAL: Rat LO. : 720 mg/kg IHL: Rat LC.^: 950 ppm/8 H ORAL: Mouse C0so; 1400 mg/kg Benzof^.h,i]perylene [a PAH] (STY) CASRNT 191-24-2 MUTAGEN Benzo[c]phenanthrene; 3,4-Benzphenanthrene [a PAH] (PE, STY) CASRN: 195-19-7 OESC: Solid, m.p. 68C SKIN TUMORIGEN: Mouse TDL : 940 mg/kg/39 W Benzo[a]pyrene, B[a]P [a PAH] (CRE, P) CASRN: 50-32-8 DESC: Solid, m.p. 175-177C HLTH: IARC CARC: Animal Positive `73, Listed in 2nd NTP Annual Report on Carcinogens, ACGIH: A2 (SusDtct carcinogen) '81. Benzo[e]pyrene [a PAH] (CRE, PE, STY) CASRN: 192-97-2 DESC: Solid, m.p. 1B0-1B2C IARC CARC: Animal Suspected, '73. Benjo[b]thiophen#; Thianaphthene (CRE) CASRN: 95-15-8 DESC: Solid, m.p. 29-32C 3 ipneny1, Diphenyl (CRE, CSPE, EPO, NOM, PE. PET, STY, SUL) CASRN: 92-52-4 STDS: OSHA: 1 mg/m3 TlV: 0.2 ppm, 1.5 mg/m3 TWA; 0.6 ppm. 4 mg/m3 STEL OESC: Solid. m,p. 69-72C 0.1 HONS 218018 HLTH: I rotation-Eye. Nose. Throat, Bronchi. Lungs, Skin--Moderate CIS. Less than 3 mg/m1). ' CNS Effects [7. Greater than 3 mg/m*). INGES ACUTE; Rat LDS0: 3280 mg/kg 1,2-Butadiene; Methylallene [PE) CASRN; 590-19-2 DESC: Gas 1,3-Butadiene (CSPE, NIT. PE. PU) CASRN: 10E-99-0 STDS: OSHA: 1000 ppm, 2200 mg/m* TLV: 1O0D ppm, 2200 mg/m* TWA; 1250 ppm, 2750 mg/** STEL DESC: Gas HLTH: Irritation-Eyes, Nose, Throat--M11d (16, Less than 3000 ppm), INGES ACUTE; Rat LDS0; 5*80 mg/kg TERATOGEN (Reference 7) NTP AND OSHA CARC: Animal carcinogen by inhalation (References 7-9) n-Butanol (PU) " CASRN: 71-36-3 STDS; OSHA; 100 ppm, 300 mg/m3 TLV: C 50 ppm, C 150 mg/m3 TWA DESC: Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat--Moderate (15). Hearing loss (7), Narcosis (8). SKIN ASS: Yes SKIN IRR: Severe INGES ACUTE: Rat LDS0: 790 mg/kg 1-Butene; a-Butylene (CSPE; EPO) CASRN: 106-98-9 DESC: Gas 2-Butenenitrile; Crotonitrile (NOM) CASRN (mixt. of trans- and cis-): DESC: Volatile Liquid 4786-20-3 3-Butenenitri le; l-Butene-4-nitrile; Allyl cyanide (NOM) CASRN: 109-75-1 DESC; Volatile Liquid SKIN IRR: 10 mg/24 H open, mild ORAL: Rat LDJ0: 115 mg/kg SKIN: RabPit L0so: 1410 mg/kg 3-1-1 HONS 218019 Butyraldehyde; Butanal (PE) CASRN: 123-72-8 DESC: Volatile Liquid IHL: Human TC. : S80 mg/m* ORAL: Rat LOSo? 2490 mg/kg SKIN IRR: Rabbit: 500 mg/24 H, severe Butyric acid; Butanoic acid (PE) CASRN; 107-92-6 DESC: Semivolatile Liquid mutagen SKIN IRR: Rabbit: 10 mg/24 H, severe EVE IRR: Rabbit: 0.25 mg, severe ORAL: Rat LDS0: 2940 mg/kg Butyrolactone (PE) p-Butyrolactone; 4-Methyl-2-oxetanone CASRN: 3068-88-0 SKIN IRR: Rabbit: 500 mg, open ORAL'. Rat LDS0: 17 g/kg I ARC CARC: Animal positive, '76 y-Butyrolactonl CASRN: 96-48-0 DESC: Semivolatile Liquid IARC CARC: Negative, `76 TUMORIGEN: Mouse, skin: 50 g/kg I PR: Mouse LDS0: 1100 mg/kg Caproic acid; Hexanoic acid (PE) CASRN: 142-62-1 OESC: Samivolatile Liquid SKIN IRR: Rabbit; 10 mg/24 H, mild ORAL: Rat L0so: 3000 mg/kg SKIN: Rabbit LDS0; 630 mg/kg Caprolactam dust (NY6, N66, 610) CASRN: 105-60-2 STOS: TLV: 1 mg/m* TWA; 3 mg/m* STEL DESC: Solid, m,p. 70-72<>C HLTH: Irritation-Eyes, Nose, Throat, Skin--Moderate (15, Less thin 2 mg/m*). CNS Effects (7, Greater than 2 mg/m*). SKIN A8S: LO. 1410 mg/kg SKIN IRR: MitS INGES ACUTE; Rat LDI0; 2140 mg/kg Caprolactam (NV6, N66, 610) CASRN: 105-60-2 STDS: TLV: 5 ppm, 20 mg/ra* TWA; 10 ppm, 40 mg/m* STEL DESC: Solid, m.p. 70-72C HLTH: Irritation-Eyes, Nose, Throat, Skin--Moderate (15, Less than 10 ppm). CNS Effects (7, Greater than 10 ppm). Vapor less irritating than dust to respiratory tract. See Caprolactam dust above for toxic, oral, ano skin information. B-15 HONS 218020 Carbazole (CRE) CASRN: 86-74-0 DESC: Solid, m.p. 24S-246C ORAL: Rat LO, 500 mg/kg IPR: House LOg0: 200 mg/kg Carbon dioxide (CSPE, EPO, FEP, KAP. NOM, PAP, PE, PET, PU. SUL, TEF, VIT) CASRN: 124-36-9 STDS: OSHA; SOOO ppm, 9000 mg/m* TLV: SOOO ppm. 9000 mg/m* TWA; 15.000 ppm. 27,000 mg/m* S7EL DESC: Gas HLTH: Simple Asphyxiant (17, Less than 10.000 ppm). SKIN: Direct contact with dry Ice can cause freezing of tissue. Carbon monoxide (CSPE, EPO. FEP. HAL, KAP, NEO. NON, NY6, PAP, PE, PET, PU. SUL TFE. TFZ, VIT) CASRN: 630-08-0 STDS: OSHA: 50 ppm, 55 mg/m* TLV: 50 ppm, 55 mg/m* TWA; 400 ppm, 440 mg/m* STEL OESC: Gas HLTH: Asphyxiation, Chemical anoxia (17, Less than 75 ppm). Carbon tetrafluoride (TEF, FEP) CASRN: 75-73-0 OESC: Gas IHL: Rat LCLq: 895,000 ppm/15 min Carbonyl fluoride (HAL, TFZ) CASRN: 353-50*4 STOS: TLV: 2 ppm, 5 mg/m* OESC: Gas TWA; 5 ppm, 15 mg/m* STEL Chloroform; Trichloromethane (XLPE) CASRN: 67-56*3 STOS: OSHA: C 50 ppm, C 240 mg/m* TLV; 10 ppm, 50 mg m* TWA; 50 ppm, 225 mg/m* STEL OESC: Volati le Liquid HLTH: Suspect Carcinogen (2). Cumulative liver and kidney damage (1). Narcosis (8). ACGIH: A2 (Suspect carcinogen). IARC CARC: Animal Suspect. '72. IARC CARC: Animal Positive, '70. IARC CARC: Human Suspect, '01. Listed in 2nd NTP Annual Report on Carcinogens, '81. Chrysene [a PAH] (CRE, PE, STr) CASRN: 218-01-9 STOS: TLV: Suspect carcinogen OESC: Solid, m.p. 254-255C IARC CARC: Animel Positive '73. SKIN A0S: Skin carcinogen; Mouse 3.5 mg/kg HONS 218021 Cinnamyl alcohol (STY) CASRN: 104-54-1 OESC: Soil'd, m.p. 33-35C TUMORIGEN: Mouse, ipr: 1400 mg/kg ORAL. Rat LDS0: 2000 mg/kg SKIN IRR: Rabbit: 522 mg/24 h, moderate Cresol (CRE, EPO, SUL) CASRN: 1319-77-3 Si OS: OShA: 5 ppm, 22 mg/m1 TLV: 5 ppm, 22 mg/mJ TWA DESC; Solid or Semivolatile Liquid (depending on isomer). HLTH: Irritation-Eyes, Skin*-Marked (14). Acute Toxicity-(CNS) (4). Cumulative liver, cardiovascular, kidney damage (3). SKIN ASS: Yes SKIN IRR: Yes INGES ACUTE: Varies with isomer: Rat L05O: approximately 200 mg/kg o*Cresol is the most toxic orally. Crotonic acid; trans-2-Butenoic acid (P) CASRN: 3724-65-0 OESC: Solid, m.p. 72-74C ORAL: Rat L0io: 1000 mg/kg SKIN: Guinea pig L0so: 600 mg/kg SKIN IRR: Rabbit: 10 mg/24 H Cumene; Isopropylbenzene (STY, XLPE) CASRN: 90-62-8 STOS: OSHA: SO ppm, 245 mg/mJ TLV: 50 ppm, 245 mg/m* TWA; 75 ppm, 365 mg/mJ STEL OESC: Semivolatile Liquid HLlH: Narcosis (0). Irritation-Eyes, Skin--;-!ooerate <15, Less than 100 ppm). SKIN A0S: Yes ` SKIN IRR: Yes, Primary Irritant INGES ACUTE: Ret LD*0: 1400 mg/kg Cyanoani1ines; Aainobenzonitriles (NOM) m-Cyanoaniline " CASRN: 2237-30-1 OESC: Solid, m.p. 51-53C o-Cyanoanil ine; Anthranilonitri le " CASRN: 1085-29-6 OESC: Solid, m.p, 47-49C 1PR: Mouse LD50: 180 mg/kg 2-Cyanoani 1 i ne CASRN: 873-74-5 OESC: Solid, m.p. 83-S5C IPR: Mouse L0sf): 155 mg/kg HONS 218022 3"Cyanobenzoic acid (P0) CASRN: 1877-72-1 OESC: Solid, m.p. 222-224 3-Cyanobiphenyl (NOM) Cyanogen (NOM) CASRN: 460-19-5 STDS: TLV: 10 ppm TWA OESC: Gas KlTH: Irritation-Eyes, Nest, Throat--Moderate (15). Acute Toxicity (Cyanosis) (4). N-(3-Cyanopheny1)benzamide (NOM) Cyclopentadiene (EPO) CASRN: 542-92-7 OESC: Volatile Liquid HLTH: Irritation-Eyes. Nose, Throat--Modrate (15, Less than 150 ppm). Cyclopentanone (N66) CASRN: 120-92-3 OESC: Semivolatile Liquid SKIN IRR: Rabbit: 500 mg/24 H IPR: Mouse L0to: 1950 mg/kg SCU; Mouse LD^: 2600 mg/kg Cyclopropane (PE) CASRN: 75*19*4 OESC: Gas Oecachlorobiphenyl (PCP) CASRN: 2051-24-3 OESC: Solid, m.p. 305-306C Decafluorobutane (FEP, TEF) CASRN: 355-25*9 Dibenz[a,h]anthracene; 1.2.5,6-01 benzanthracene (a PAH] (CRE) CASRN: 53-70-3 OESC: Solid, m.p. 266-267C MUTAGEN IARC CARC: Animal Positive, '73. IVN: Mouse U>L : 10 mg/kg Dibenzofuran (CRE, KAP, SUL) CASRN: 132*64-9 DESC: Solid, m.p. 83-84C 8-18 MONS 218023 1,3-Oicyanobanzene; 1sophthalonitriTe (NOM) CASRN: 626-17-5 STDS: TLV-TWA: 5 mg/m* DESC: Solid, m.p . 160*162C ORAL: Rat LOSo: I860 mg/kg ORAL: Mouse LD50 : 178 mg/kg l,4-Dlcyanobenz*ne; Terephthalonitri It; g-Dicyanobenzen* (KAP, PU) CASRN: 623-26-7 OESC: Solid, m.p. 224-227C EYE 1Rft: Rabbit: 500 mg/24 H, modarata ORAL: Rat LDS0: 21 g/kg Oihydroanthracene (PE) CASRN (9,10-iscmer); 613-31-0 OESC: Solid, m.p. 1O0-11OC Diisobutyl phthalate (NEO) CASRN: 84-69-5 DESC: Semivolatile Liquid ORAL: CRA.: SKIN: Rat LD$q: 20 g/kg * /sa- /Us- Guinea pig L0jo; io g/Rg Dimethyl ether; Methyl ether (PU) CASRN: 115-10-6 DESC: Gas IHL: Mouse LCt0: 386 ppm/15 ml Dimethyl naphthalan* (CRE, CSPE, SUL) CASRN: 20504-88-8 DESC: Sami volatile Liquids or Solids 1,6*Dimethv1naonthalen* CASRN: 575-43-9 DESC: Sami volatile Liquid ORAL: Rat LDLq: 5000 mg/kg Dioctyl phthalat* (NEO) OESC: Semlvolatil* Liquid SKIN IRR: Mild INGES ACUTE: Mouse L0so: 6S13 mg/kg [01-n-oetyl phthalate, CASRN 117-04-0] Rat L0,o; 31 g/kg [8is(2-*thylh*xvl) phthalate, CASRN 117-81-7] 1,4-Dloxane; Diethylene Dioxide (NOM) CASRN: 123-91-1 STDS: OSHA: 100 ppm, 360 mg/m* TLV: 25 ppm, 90 mg/m* TWA; OESC: V'olati le Liquid 100 ppm, 360 mg/m* STEL a. i o HONS 218024 HLTH: Suspect carcinogen (2). Cumulative liver end kidney damage (3) Irritation-Eyes, Nose, Throat--Mild (16). IAfiC CARC: Animal Positive, `76. Listed in 2nd NTP Annual Report on Carciongens, `81. SKIN A0S: Yes SKIN IRR; Mild INGES ACUTE: Rat LDS0: <200 mg/kg Diphenylethane (STY) CASRN (1,2-isomer): 103-29-7 OESC: Solid, m.p. 50-53C Diphenyl ether (EPO, SUL) CASRN: 101-84-0 STDS: OSHA: 1 ppm, 7 mg/m1 TLV: 1 ppm, 7 mg/mJ TWA; 2 ppm, 14 mg/mJ STEL OESC: Volatile Liquid HLTH: Nausea (7). Irri tation*yes, Skin--Mi 1 d (16). Cumulative liver and kidney damage (3). SKIN IRR: Mild INGES ACUTE: Rat LDS0-' 3370 mg/*9 Dipropylene glycol methyl ether (XLPE) CASRN: 34590-94-8 STDS: OSHA: 100 ppm, 600 mg/m3 TLV: 100 ppm, 600 mg/mJ TWA; 150 ppm, 900 mg/m3 STEL DESC: Semi volatile Liquid HLTH: Irritation-Eyes, Nose--Moderate (15). Slight Narcosis (0). SKIN A8S: Yes SKIN IRR: Mild INGES ACUTE: Rat LDS0: 4900 g/kg Divinyl terephthalate (PET) CASRN: 94-49-5 Ethane (CSPE, EPO, NOM, PE, PET, PU, CASRN: 74-04-0 DESC: Gas HLTH: Explosive (10). Simple Asphyxiation (17, SUL) If oxygen level is 18X by volume). 2-Ethoxyethanol (PU) CASRN: 11D-0O-S STDS: OSHA: 200 ppm, 740 mg/m3 TLV: 50 ppm, 185 mg/m3 TWA; 100 ppm, 370 mg/m3 STEL (NOTE: Probable change to 5 ppm, with no STEL. Skin notation will be continued.) OESC: Semivolatile Liquid HLTH: Irritation-Eyes. Nose--Moderate (15). Cumulative blood disturbances (12). HONS 218025 SKIN A8S: Yes SKIN IRR: Nlld INGES ACUTE: Ret LDS0: 3000 mg/kg Ethyl elcohol; Ethenol (PE, PU) CASRN: 64-17"5 STDS: OSHA: 1000 ppm, 1900 mg/m3 TLV: 1000 ppm, 1900 mg/m3 TWA DESC: Volatile Liquid HLTH: Irritation-Eyes, Nose, Throet--Merked (14, Less than 3000 ppm). Narcosis (6). Reproductive impairment (5, Greater than 3000 ppm). SKIN A8S: Rabbit ID. : 20 g/kg SKIN IRR: Severe L0 INGES ACUTE: L0so: 7060 mg/kg Ethylbenzene (EPO, NIT, PE, PET, STy, SUL) CASRN: 100-41-4 STDS: OSHA: 100 ppm, 435 mg/m3 TLV: 100 ppm, 435 mg/m3 TWA; 125 ppm, 545 mg/m3 STEL DESC: Semivolatile Liquid HLTH: Irritation-Eyes, Nose, Throat, Skin--Moderate (15, Less than 200 ppm). Narcosis (8). SK..N ABS: f.aii i L -JLo rr.g/k; SKIN IRR: Mild INGES ACUTE: Rat L05O: 3500 mg/kg Ethyl chloride; Chloroethane (EPO) CASRN: 75-00-3 STDS: OSHA: 1000 ppm, 2600 mg/m* TLV: 1000 ppm, 2600 mg/m3 TWA; 1250 ppm, 3250 mg/m3 STEL DESC: Gas HLTH: Narcosis (8, Greater than 5000 ppm). SKIN IRR: Frostbite possible if liquefied gas is spilled on skin. Ethylene; Ethene (EPO, NOM, PAP, PE. PET, PU, SUL, TFZ) CASRN: 74-85-1 OESC: Gas HLTH; Simple Asphyxiation (17, If oxygen level is 18* by volume). Explosive (18). ACG1H: E (Simple asphyxiants) Ethylene dibenzoete (PET) CASRN: 94-49-5 Ethylene glycol, particulate (PET) CASRN: 107-21-1 STOS; OSHA: 1.0 mg/m3 TLV: 10 mg/m* TWA OESC: Volatile Liouid HLTH: Irritation-Eves, Nose. Throat--Moderate (15). CNS depression (7). 8-21 MONS 218026 SKIN ASS'. Rabbit LDS0: 19,530 mg/kg SKIN IRR: Mild INGES ACUTE: Human LDL : 710 mg/kg Ethylene glycol, vapor (PET) CASRN: 107-21-1 STDS: TLV; C 50 ppm, C 125 mg/m* TWA DESC: Vapor HLTH: Irritation-Eyes, Nose, Throat--Moderate (15). SKIN ASS: Rabbit L0so: 19,530 mg/kg SKIN IRR: Mild INGES ACUTE: Human LDL : 710 mg/kg CNS depression (7). Ethylmethylphenol; ethylcresoi (CRE) CASRN: 1687-61-2 OESC: Solid? 6-Ethyl-m-cresol UNKNOWN ROUTE: Rat L0sO: 530 mg/kg Ethylphenol (SUL) 2-EthyTphenol CASRN: 90-0C-6 OESC: Semivoletila Liquid CARC: Mouse Skin TO. : 3100 *g/kg/12 W, 3-Ethyl phenol 0 CASRN: 620-17-7 OESC: Semivolatile Liquid 4-Ethyl phenol CASRN: 123-07-9 OESC: Solid, m,p. 42-45C intermittent Fluoranthene [a PAH] (CRE, P, STY) CASRN: 206-44-0 DESC: Solid, m. p. 107-I1DC SKIN TUMQRIGEN: Mouse TO. : 280 mg/kg/58 W ORAL: Rat L0$o; 2000 mg/Rg FTuorene [a PAH] (CRE, CSPE, PE, STY) CASRN: 86-73-7 OESC; Solid, m.p. 112-115C Formaldehyde; Methane1 (PE, PET, STY) CASRN: 50-00-0 STOS: OSHA: 3 ppm TLV: 2 ppm, 3 *g/m* TWA OESC: Gas HLTH: Irritation-Eyes, Lungs, Skin--Marked (14). Suspect Carcinogan/Mutagan (2). IARC CARC: Animal Positive, `82. IARC CARC: Human indefinite, `82. ACGIH; A2 (Suspect carcinogen). Listed in 2nd NTp Annual Report on Carciongens, '81. 8-22 HONS 218027 SKIN IRR: Yes, Sensitization also INGES ACUTE: Rat LDS0: 80D mg/kg Formic acid; Methanolc acid (PE, STY) CASRN: 64*10*6 STDS: DSHA: 5 ppm, 9 mg/mJ TLV: S ppm, 9 mg/m1 TWA DESC: Volatile Liquid HUH: Irritation-Eyes, Nose, Throat, Skin, Lungs**Marked (14). Mutagen (2). SKIN IRR: Yes, if concentrated INGES ACUTE: Rat L0so: 1100 mg/kg Furan (PE) CASRN: 110-00*0 DESC: Volatile Liquid IHL: Mouse LCS0: 120 mg/m/lM I PR: Mouse LDS0; 7 mg/kg IPR: Rat LDS0: 5.2 mg/kg rtfeptacnlorooiDenio-g-oi dx . n (PC') CASRN: 37871-00-4; (1,2,3,4,6,7,8-isomer) 35822-46-9 IARC CARC: Animal Indefinite, '77, n-Haptacosane (NEO) " CASRN: 593-49-7 DESC: Solid, m.p. 59-61C 1-Heptena (PE) CASRN: 592-76-7 DESC: Volatile Liquid Hexachlorobenzene (PCP) CASRN: 118-74-1 DESC: Solid HLTH: IARC CARC: Animal Positive, '79. IARC CARC: Human Suspect, '79. Hexachlorodibanzo-g-dioxin (PCP) CASRN: 34465-46-8 DESC: Solid, m.p. 227-229C EYE IRR: Rabbit: 2 mg, moderate ORAL: Rat TO. : 1DD mg/kg ORAL: Mouse LDj: 1-25 mg/kg IARC CARC: Animal Indefinite, '77 (but a 2:1 mixture of the 1,2,3,7,8,9- and 1.2,3,6.7.8-1somers was a carcinogen in rats and mice). Hexachloroaibenzofuran (PCP) CASRN: 55684-94-1 3-:3 HONS 218028 n-Hexadecane (NEO) " CASRN: 544-76-3 DESC: Semivolatila Liquid (freeza* at 18.2C) Haxafluoropropane (FP, TEF) CASRN: 27070-61-7; (1,1,1,3,3,3-) 690-39-1; (1,1,2,2,3.3-) (1,1,1,2,2.3-) 677-56-5; (1.1,1,2,3.3-) 431-63-0 DESC: Gas 680-00-2; Hexafluoropropylena; Hexafluoropropene (TEF, FEP, VIT) CASRN; 116-15-4 OESC: Gas IHL: Rat LC : 20,000 mg/mV2 H Hexanal; Hexaldehyde; Caproaldehyde (PE) CASRN; 66-25-1 DESC: Seraivolatile Liquid ORAL: Rat L0so: 4890 mg/kg IHL: Rat LC ; 2000 ppm/4 K SKIN IRR: RlBbit: ID mg/24 H, mild n-Hexan (PE) " CASRN; 110-54-3 STDS: OSHA: 500 ppm, 1800 mg/mVIS min TLV: 50 ppm, 180 mg/mJ TLV DESC: Volatila Liquid HLTH: Nervous system disturbancas--polyn*uropathy (7). Nervous system dlsturbances--narcosis (8). SKIN IRR: Mild IML: Human TC,LO : 5000 ppm/lO min 1-Hexene (CSPE, PE) CASRN: 592-41-6 DESC: Volatile Liquid Hydrogen (EPO, KAP, NIT, NOM, PAP, PE) CASRN: 1333-74-0 OESC; Gas HLTH: Simple Asphyxiation (17, If Explosive (18). oxygen level is 18X by volume). Hydrogen chloride (gas, anhydrous) (CSPE, HAL, NEO) CASRN: 7467-01-0 STDS: OSHA: C 5 ppm, C 7 mg/iO TLV; C 5 ppm, C 7 mg/mJ TWA DESC; Gas HLTH: Irritation- Eyes, Nose, Throat--Marked (14). Lung edema (11). Dental erosion (3). MOHS 218029 Hydrogen cyanide (gas) (AAP, N66, NEO, NIT, NOH, PU) CASRN: 74-90-0 STOS: OSHA: 10 ppm. 11 mg/m1 TLV: C 10 ppm. C 10 mg/m* TWA DESC: Gas HLTH: Acute systemic toxicity (4). Cumulative systemic toxicity (Cyanosis) (3). Hydrogen fluoride (gas, anhydrous) (HAL, TFZ, VIT) CASRN: 7664-39*3 STOS: OSHA: 3 ppm TLV: 3 ppm, Z.5 mg/m1 TWA; 6 ppm, 5 mg/m1 STEL DESC: Gas HLTH: Irritation-Eyes, Nose, Throat, Skin--Marked (14). Acute lung damage (11). Cumulative bone damage (3). Hydrogen sulfide (NEO) CASRN; 7783-06-4 STOS: 05HA; 20 ppm TLV: 10 ppm, 14 mg/m3 TWA; 15 ppm, 21 mg/m1 STEL nr;;. HLTH; Acute systemic toxicity (4). Irritation-Eyes (Conjunctivitis), Lungs**Moderate (15). CNS effects (7). Hydroxyethyl terephthalate monoester (PET) 2-Hyd roxyp h e ny 1 -2-phe ny1p ropane (SUL) Hydroxyvaleric acid (PE) CASRN: 50853-48-0 QESC: (2-isomer) Solid, m.p. 34C (sublimes) Indan (EPO , PE) CASRN: 496-11-7 DESC: Semivolatile Liquid ORAL: Rat LO^: 5000 mg/kg Indene (CSPE, EPO, PE, PU, STY, SUL) CASRN: 95-13-6 STOS: TLV: 10 ppm, 45 mg/m1 TWA; 15 ppm, 70 mg/m1 STEL DESC: Semivolatile Liquid hlTH: Irritation-Eyes, Nose, Throat--Moderate (15). Cumulative liver and kidney damage (3). HONS 218030 Indole (CRE) CASRN: 120-72-9 OESC; Solid, m.p. 52-54C ORAL: Rat L0so: 1000 mg/kg SKIN: Rabbit L0so: 790 mg/kg Isobutyraldehyde (RE) CASRN: 78-84-2 OESC; Vol?cile Liquid IHL: Rat LC, : 8000 ppm/4 H ORAL: Rat LD$0: 2810 mg/kg SKIN IRR: Rabbit: 500 mg/24 H, severe Isoprene (CSPE) CASRN: 78-79-5 OESC: Volatile Liquid (b.p. 34C) Isovaleric acid (PE) CASRN: 503-74-2 Ci::.' Se-:ivolati ic Liquid ORAL: Rat LDS0: 2000 mg/kg SKIN-. Rabbit LDSo: 310 mg/kg SKIN IRR: Rabbit; 500 mg/24 H, moderate Methacrylonitrile (NIT, PU) CASRN: 126-98-7 TLV; 1 ppm, 3 mg/m3 TWA; skin warning OESC: Volatile Liquid SKIN IRR: Rabbit: 200 mg, mild ORAL; Rat LDS0: 250 mg/kg Methane (CSPE, EPO, KAP, NEO, NIT, NOM, PAP, PE, PET, PU, SUL) CASRN: 74-82-8 OESC: Cas HLTH: Explosive (18). Asphyxiant (17, If oxygen level is 18X by volume). ACGIH: E (Simple asphyxiant) Methyl alcohol; Methanol (NOM, PU) CASRN: 67-56-1 STOS: OSHA: 200 ppm, 260 mg/m3 TLV: 200 ppm, 260 mg/m3 TWA; 250 ppm, 310 mg/m3 STEL OESC; Volatile Liquid HLTH: Cumulative CNS effects (7, Greater than 400 ppm). Narcosis (8). Irritation-Eyes, Nose, Throat--Mild (16, Less than 400 ppm). Methylanthracenes [PAHs] (PE) CASRN: (2-) 613-12-7; (9-) 779-02-2 OESC: (Z-) Semivolatile Licuic: (9-) solid, m.?. 7i-79*C HONS 21B03I Methylbenzofuran (SUL) CASRN: 25586*38*3 DESC: (2*,3-,5*p or 7-lsomer) Semivolatile liquid 4*Methylbipheny1; 4*Phenyltoluene (STY) CASRN: 644-08*6 DESC: Solid, m.p. 44-47C ORAL: R*t LDjo: 2570 mg/kg 1-Methylbutyl isobutyrate; Propanoic acid. 2-methyl*. l-iathylbutyl aster (NEO) CASRN: 54340-93*1 Methyl chloride; Chloromethane (EPO) CASRN: 74-87*3 STDS: OSHA: 100 ppm TLV: 50 ppm, 105 (#g/iJ TWA; 100 ppm 205 g/* STEL OESC: Gas HLTH; Acute CNS effects (4). Chronic CNS effects (7). '-'ulatlve liver and kidney damaoe (3). SKIN A8S: Yes '' 3*Methylcholanthrene [a PAH] (STY) CASRN: 56-49-5 DESC; Solid, m.p. 178-180#C TUMORIGEN; Oral: Rat TO. : 200 g/kg TUMORIGEN: Skin: Rat T0h: 700 mg/kg/25 W-intermittent TERATOGEN L0 2-Methyl-1,3-dioxolane (PET) CASRN: 497-26-7 DESC: Volatile Liquid 4,5-Methylenephananthrene (PE) CASRN: 203-64-5 DESC: Semivolatlle Liquid Methyl ethylbenzenes; Ethyl toluenes (SUL) 2-Ethyl toluene CASRN: 611-14-3 DESC: Semi volatile Liquid ORAL: Rat LO. : 5000 mg/kg 3-Ethyltoluene CASRN: 620-14-4 OESC: Semivolatile Liquid 4-Ethyltoluene CASRN: 622-96*8 OESC: Semivolatile Liquid ORAL; Rat L0L(): 5000 mg/kg MOMS 218032 Methyl ethyl ketone; 2*8utanone; MEK (PE) STDS: OSHA: 200 ppm, 590 mg/m1 TLV: 200 ppm, 590 mg/m> TWA; 300 ppm. 885 g/m* STEL OESC: Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat--Moderate (15). Narcosis (3). SKlN IRR: Moderate INGES ACUTE: flat LDS0: 2737 mg/kg Methylfluorenes [PAHs] (CRE, PE) CASRN: (1-) 1730-37-6; (9-) 2523-37-7 DESC; (1-) Solid, m.p. 84-86C; (9-) Semivolatile Liquid Methylindene (STY, SUL) CASRN: 29036-25-7 OESC: Semivolatile liquid Methyl-4,5-methylenephen=~threne; Methyl-4H-cyclopenta[def]phenanthrene (PE) CASRN: 58548-39-3 1-Methyl naphthalene (CRE, CITE, Pi, S*Y, SUL) CASRN: 1321-94-4 OESC: Semivolatile Liquid INGES ACUTE: Rat LD$0: 4360 mg/kg 2-Methyl naphthalene (CRE, CSPE, PE, STY) CASRN: 91-57-6 OESC: Solid, m.p. 34-36C ORAL: Rat LD^ : 5000 mg/kg Methylphenanthrene (PE) '.-Methyl isomer CASRN: 832-69-9 MUTAGEN 2-Methyl isomer CASRN: 2531-84-2 DESC: Solid, m.p. 57-59C MUTAGEN 2-Methylpyridine; or-Picoline (PU) CASRN: 109-06-8 OESC: Semivolatile Liquid SKIN IRR: Rabbit: 10 mg/24 H, mild EYE IRR: Rabbit: 0.750 mg, severe - ORAL: Rat L0So: 790 mg/kg IHL: Rat LC. : 4000 ppm/4 H SKIN: Rabbit L0so: 410 mg/kg HOMS 218033 4*Mathylpyridine; y-Picoline (PU) CASRN: 108*69*4 OESC: Semivolatile Liquid SKIN IRR: Rabbit: 10 mg/24 H, severe EYE IRR: Rabbit: 0.750 mg, severe ORAL: Rat LDS0: 1290 mg/kg IHL: Rat LC. : 1000 ppm/4 H SKIN: Rabbit LDS0: 270 mg/kg o-Methylstyrene; 2-Pbenyl-l-propene (STY, XLPE) CASRN: 98-83*9 STDS: OSHA: C 100 ppm, C 480 mg/*1 TLV: 50 ppm, 240 mg/mJ TV/A; 100 ppm, 485 mg/n1 STEL OESC: Semivolatile Liquid HLTH: Irritation-Eyes, Nose, Throat--M11d (15). CNS affects (7). Narcosis (8). SKIN IRR: Moderate 2*(Methylthio)benzothiazole (NEO> CASRN: 615-22-5 OESC- SoKH. m.r 52C Methyl vinyl ketone (PE) CASRN: 78-94-4 DESC: Volatile Liquid IPR: Mouse LD(0: 80 mg/kg Naphthalene (CRE, CSPE, EPO, PE. PET, STY, SUL) CASRN: 91-20-3 STDS: OSHA: 10 ppm, 50 *g/m> TLV: 10 ppm, 50 mg/m TWA; 15 ppm, 75 mg/m* STEL DESC. Solid, m.o. 80oC: sublimes at room temoerature HLTH: Irritation-Eyes, Nose, Throat--Marked (14). Ocular damage/Anemia/CNS damage (3). Suspect carcinogen (2). SKIN IRR: Mild INCES ACUTE: Human LDL0: 74 to 100 mg/kg o-Naphthol; 1-Napftthol (CRE) CASRN: 90-IS-3 OESC: Solid, m.p. 95*96C SKIN IRR: 500 mg/24 H, severe EYE IRR: Rabbit, 1 mg, severe MUTAGEN ORAL: Rat L0So: 2,400 mg/kg SKIN: Rabbit 10SO: 380 mg/kg HONS 218034 Q* *>0 0-Naphthol; 2-Naphthol (CRE) CASRN: 135-19-3 DESC: Solid, m.p. 122-123C SKIN IRR: Mild INGES ACUTE: Rat LD10: 2420 mg/kg a-Naphthyl amine; 1-Aminonaphthalene (CRE) CASRN: 134-32-7 STDS: OSHA: 29 CFR 1910.1004 DESC: Solid, m.p. 48-50oC HLTH: Cancar-Bladder (suspect) (1). IARC CARC: Animal Indefinite, '74. IARC CARC: Human Suspect, *74. SKIN A8S: Yes INGES ACUTE: Rat LDS0: 779 fflg/kg p-Naphthylamine; 2~Aminonaphthe1ene (CRE) CASRN: 91-59-8 STDS: OSHA: 29 CFR 1910.1009 0ESC: Solid, m.p. U1-113C HLTH: Cancer-Bladder (1). ACCIH: ALi 'Human Care'ncjs-'.. IARC CARC: Animal Positive, '74. IARC CARC: Human Positive, '74. INGES ACUTE: Rat LDS0: 727 mg/kg Nitric oxide (NOM) CASRN; 10102-43-9 STDS: OSHA: 25 ppm. 30 mg/m* TLV: 25 ppm, 30 mg/m* TWA: 35 ppm, 45 mg/m* STEL OESC: Gas HLTH: Methemoglobinemia (13, Less than 50 ppm). CN$ effects (7, Greater than SO ppm). Delayed lung damage (10). Nitromethane (NOM) CAFRN: 75-52*5 S'IS: OSHA: 100 ppm, 250 mg/m* TLV: 100 ppm, 250 mg/m* TWA; 150 ppm, 375 mg/mJ STEL DESC: Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat. Skin--Mild (16, Less than 300 ppm). Narcosis (8, Greater than 300 ppm). Cumulative liver and lung damage (3). INGES ACUTE: Rabbit LDL(): 750 mg/kg Nitrous oxide (NOM, PU) CASRN: 10024-97-2 DESC: Gas HLTH: Reproductive Hazard (Male and Female) (5, Greater than 100 ppm). CNS effects (7). MON5 218035 n-Nonacosan* (NEO) ~ CASRN: 630-03-5 OESC: Solid, m.p. 66-67*C Nonylphenol (NEO) CASRN: 25154-52-3 DESC: Semivolatila Liquid SKIN IRR: Rabbit: 10 mg/24 hr, sever* EYE IRR: Rabbit: 0.050 mg, severe Octachlorodlbenio-p-dloxin (PCP) CASRN: 3268-87-9 DESC: Solid EYE IRR: Rabbit: 2 mg, mild SKIN TUMORIGEN: Mouse TD. : 290 mg/kg/60 W IARC CARC: Animal Indefinite? '77. Octachlorodibemofuran (PCP) CASRN: 39001-02-0 Octachloronaphthalene; Parchloronaphthalene (PCP) CASRN: 2234-13-1 STDS: OSHA: D.lmg/m* TLV: 0.1 mg/J TWA; 0.3 g/mJ STEL OESC: Solid, m.p. 197-198C HLTh: Cumulative 11ver damage/Chloracne (3), SKIN ASS: Yes Octaf1uoro-1-butane (FEP) CASRN: 360-89-4 OESC: Gas Octaf1uorocyclobutana; Parfluorocyclobutane (FEP, TEF) CASRN: 115-25-3 OESC: Gas Octaf!uoroiaobutyl ana; Parfluoroisobutylen* (FEP, TEF) CASRN: 382-21-8 Octyl alcohol; 1-Octanol (NEO) CASRN: 111-87-5 OESC: Semivolatile Liquid SKIN IRR: Mild INGES ACUTE: Mouse LDse: 1790 mg/kg Palmitic acid (NEO) CASRN: 57-10-3 OESC. Solid, m.p. 61-64C 5-21 HOMS 210036 SKIN IRR: Human: 7S mg/3 days, mild TUM0R1GEN: Mouse (implant) TO. : 1000 mg/kg 1VN: Mousa L0IO: 57 mg/kg Pentachlorobenzene (PCP) CASRN: 608-93-5 DESC: Solid, m.p. 86C ORAL: Pat LDt0: 1080 mg/kg 1,4-Pentad lane (PE) CASRN: 591-93-S DESC: Liquid/Gas (b.p. 26C) Pentana (PO. PE) CASRN: 109-66-0 STDS: OSHA; 1000 ppm, 2950 mg/m1 TLV: 500 ppm, 1300 mg/a1 TWA; 750 ppm, 2250 mg/m1 STEl OESC: Volatila Liquid HLTH: Flammable (18, Lass than 3000 ppm). Narcos Is (6, Greater than 3000 ppm). 2-Pentanona (PE) CASRN: 107-87-9 STOS: OSHA; 200 ppm, 700 mg/m1 TLV; 200 ppm, 700 mg/m* TWA; 250 ppm, 875 mg/m1 STEL OESC: Volatila Liquid HLTH: I rrl tat Ion-Eyas, Nosa, Throat--Modarata (15, Lass than 400 ppm). Narcosis (8, Graatar than 400 ppm). 1-Pentena (CSPE, PE) CASRN: 109-67-1 DESC: Liquid/Gas (b.o. 29-9-iO. 1C) Perylena [a PAH] (CRE) CASRN: 198-55-0 OESC: Solid, m,p. MUTAGEN 227-279*C Phananthrana [a PAH] (CRE, CSPE, PE, STY) CASRN; 85-01-8 DESC; Solid, m.p, 99-101C INGES ACUTE: Mousa LDS0: 700 mg/kg Phanol (CRE, EPO, KAP, NOM, STY, SUL, XLPE) CASRN: 108-95-2 STOS: OSHA: 5 ppm, 19 mg/m1 TLV: 5 ppm, 19 mg/m1 TWA; 10 ppm, 38 mg/m1 STEL OESC: Solid, m.p. 40.5-41.5C (absorbs water from air and liquefies) HONS 218037 HLTH: Irritation-Eye*, Nose, Throat, Lungs--Marked (14). Acute and chronic systemic toxicity (4). Suspect carcinogen (2). SKIN IRA: Severe SKIN ABS: Yes INGES ACUTE: Human LO^: 140 mg/kg Phenyl acetaldehyde; u-Tolualdehyde; Benzeneacetaldehyde (STY) CASRN: 122-78-1 OESC: Semivolatile Liquid SKIN IRR: Human: 2X/48 H ORAL: Rat LOjo: 1550 mg/kg 1,3-Phenylenediamine; 1,3-Diami nobenzene (NOM) CASRN: 108-45-2 OESC: Volatile Liquid IARC CARC: Animal Indefinite, '78 TUMOR I GEN: Ret TO. , scu: 1485 ag/kg ORAL: Rat LDjo'. 650 mg/kg m-Phenvipnefliisocvanate: 1,3-Diisocvanatohencene (NOM) " CASRN: 123-61-5 OESC: Solid? IVN: Mouse LDso: 5-6 mg/kg 2.3-o-Phenylenepyrene; Indeno[l,2,3-cd}pyrene [a PAH) (CRE) CASRN: 193-39*5 OESC: Solid MUTAGEN IARC CARC: Animal Positive '73. Phenyl isocyanate (KAP) CASRN: 103-71-9 OESC: Semfvolatile Liquid SKIN ABS: Rabbit LDso; 7130 mg/m* INGES ACUTE: Rat L0o: 940 mg/kg 2-phenylnaphthalene (PE) CASRN: 612-94-2 OESC: Semivolatile liquid -Phenyl-2-naphthylamine (NEO) CASRN: 135-88-6 OESC: Solid, m.p. 107-109C HLTH: IARC CARC: Animal Suspect. '78. IARC CARC: Human Indefinite, `78. Metabolizes to 2-naphthyl amine in humans and animals INGES ACUTE: Rabbit LD,L0 : 1000 mg/kg IZ HONS 21803B Phenyl to 1y1 ether (SUL) CASRN: 1706-12-3 Phthalanl1 (NEO) CASRN: 520-03-6 Phthalates (XLPE) Phthalic anhydride (NEO) CASRN: 85-44-9 OESC: Solid, m.p. 132-134C STOS: OSHA: 2 ppm. 12 mg/m1 TLV: 1 ppm, 6 mg/m1 TWA; 4 ppm, 24 mg/m3 STEL HLTH: 1rritation-Eyes , No*#, Throat, Lungs--Hark*d (14), Asthma (9). Contact skin irritant and sensftiier (3). SKIN IRR: Yet, sever* 1NGES ACUTE: Guinea pig LDS0: 100 mg/kg Phthalimid# (KAP) CASRN: 85-41-6 DESC: Solid, m.p. 234-236C ORAL: Mouse L0to: 5000 mg/kg Polystyrene combustion products (6004C) (STY) IHL: Mouse LCI0: 120 mg/mVlO min Polytetrafluoroethylene decomposition product (TEP) CASRN: 9002-84-0 STOS: TLV: 81 (Polytetrafluoroethylene decomposition product) OESC: Variable HLTH: Acute toxic effects (Polymer fume fever) C4). IARC CARC: Animal Positive, '79. IARC CARC: Human Indefinite, `79. Polyurethane A combustion products (PU) IHL: Mouse .Ct0: 38 mg/m1/10 min Polyurethane thermal decomposition products (PU) MUTAGENIC Propane (EPO, PE. PU) CASRN: 74-98-6 STOS: OSHA: 1000 ppm, 1800 mg/m* OESC: Gas HLTH: Explosive (18). CNS effects (7). Asphyxfant (17). ACGIH: E (Simple asphyxiant) B- 34 HONS 210039 Propiontldehyde; Propane1 (PE, PU) CASRN: 123-38-6 DESC: Volatile Liquid SKIN IRR: Mild INGES ACUTE: Rat L0lo: 800 mg/kg Propionic acid (PE) CASRN: 79-09* A STDS: TLV-TWA: 10 ppm, 30 mg/m3 STEL: 15 ppm, AS mg/m3 OESC: Semivolatile Liquid ORAL: Rat LDS0: 2500 mg/kg SKIN: Rabbit LDS0: 500 mg/kg SKIN IRR: Rabbit: 495 mg, opan, severe Propionitrila; Ethyl cyanide (PU) CASRN: 107-12-0 STDS: Criteria Document Recommended Exposure: OESC: Volatile Liquid EYE IRR1. Rabbit: 20 mg ORAL: Rat LDje: 39 mg/kg 14 mg/m3 TWA Propyl alcohol; Propanol (PU) CASRN: 71-23-8 STDS: OSHA; 2D0 ppm, SDO mg/m3 TLV: 200 ppm, 500 mg/m3 TWA; 250 ppm, 625 mg/m3 STEL DESC; Volatile Liquid HLTH: Irrltatlon-Eyes, Nose, Throet-*Mild (16). Narcosis (8). Suspect carcinogen (2). SKIN IRR: Mild SKIN ABS: Yes INGES ACUTE. Rabbit LD^ : 3500 mg/kg n-Propylbeniene (sea also Cumene) (STY) CASRN: 103-65-1 DESC: Semivolatile Liquid INGES ACUTE: Rat LDS0: 4830 mg/kg Propylene; 1-Propene (CSPE, EPO, NOM, PE, PET, PU) CASRN: 115-07-1 TLV: Asphyxiant OESC; Gas Propyne; Methylacetylene (PE. PU) CASRN: 74-99-7 STDS: OSHA: 1000 ppm, 1650 mg/m3 TlV; 1000 ppm, 1650 mg/m3 TWA; 1250 ppm. 2040 mg/m3 STEL OESC: Gas HLTH: Explosive (18, Less than 2000 ppm). Narcosis (B, Greater than 2000 ppm). . B-35 HONS 210040 Pyrene [a PAH] (CRE, PE, STY) CASRN: 129-00-0 OESC: Solid, m.p. 149-151C SKIN IRR: Moderate Pyridine (PU) CASRN: 110-86-1 STOS: OSHA: 5 ppm, IS mg/m1 TLV: 5 ppm, 15 mg/m1 TWA; 10 ppm, 30 mg/m1 STEl DESC; Volatile Liquid HLTH: Cumulative liver, kidney and bone marrow damage (3). CNS effect* (7). SKIN IRR: Mild SKIN AfiS: Rabbit LDS0: 1121 mg/kg Pyrrole (PU) CASRN: 109-97-7 OESC: Semi volatile Liquid SCU: House LDSC 61 mg/kg IPR: Rabbit LD^ : ISO mg/kg Ouinoline (CPE. P(J) CASRN: 91-22-5 DESC: Senivolatil* Liquid HUTAGEN SKIN IRR: Rabbit: 10 mg/24 H. mild EYE IRR: Rabbit: 0.250 mg, severe ORAL: Rat LDt0: 331 mg/kg SKIN: Rabbit L0to: 540 mg/kg Silicon fluoride; Silicon tatrafluoride; Tetrafluorosilane (FEP, CASRN: 7783-61-1 STOS: OSHA: 2.5 mg (HF)/m* TWA (for Hydrolysis product) TLV: 2.5 mg (HF)/m* TWA DESC: Gas TEF) Squalene (NEO) CASRN: 111-01-3 DESC: Semi volatile Liquid Styrene (CSPE, EPO, NIT, PET, PU, STY, SUL) CASRN: 100-42-5 STOS: OSHA: 100 ppm TLV: 50 ppm, 215 mg/m1 TWA; 100 ppm, 425 mg/m* STEL DESC: Samivolatlla Liquid HLTH: Irritation-Eyes, Nose, Throat*-Moderate (15). CNS effects (7). Narcosis (8). Mutagen (2). IARC CARC: Animal Positive. '79. IARC CARC: Animal Suspected. '82. 6-36 HOMS 218041 IARC CARC: Hum in Indefinite, '79. IARC CARC: Human Suspected, '82. SKIN ABS: Yes SKIN IRR: Moderate INGES ACUTE: Mouse LDS,,: 316 mg/kg Sulfur dioxide (CSPE, NEO, SUL) CASRN: 7446-09*5 STDS: OSHA: 5 ppm, 13 g/mJ TLV: 2 ppm, 5 mg/m3 TWA; 5 ppm, 10 g/m* STEl CESC: Gas HLTH: Irritation-Eyes. Nose, Throat, Lungs--Marked (14). Sronchoconstriction (4). Mutagen (2). Suspect reproductive effects (5). Tarephthalic acid (PET) CASRN: 100-21-0 OESC: Solid, m.p. > 300C Tetrachlorodibenio-g-dioxin; TCDD (PCP) !?: S C 1 5 *111 CASRN: (1.2,3,4-isomer) 30746-58-8; (1,2,3,8-isome:') S35S5-D2-5; (1,3,6,8-Isomer) 33423-92-6; (1,3,7.8-isomer) 50585-46-1; (2,3,6,7-isomer) 34816-53-0 IARC CARC: Animal Indefinite. '77. 2,3,7,8-isomer CASRN: 1746-01-6 EYE IRR: Rabbit: 2 mg, Moderate TERATOGEN MUTAGEN ORAL: Rat LDJ0: 22.5 m9^0 IARC CARC: Animal Indefinite. '77. NTP/NCI CARC: Positive in mice and rats, '82. Tetrafluoroethyiene; Tetraf1uoroethene (FEP, TEF, TFZ) CASRN: 116-14-3 OESC: Gas IHL: Rat LCS0: 40,000 ppm/4 H Tetrahydrofuran (PE) CASRN: 109-99-9 STDS: OSHA: 200 ppm, 590 mg/m TLV: 200 ppm, 590 mg/m* TWA; 250 ppm, 735 mg/m* STEL OESC: Volatile Liquid HLTH: Irritation-Eyes. Nose, Throat, Skin--Moderate (15). Narcosis (8). Mutagen (2). INGES ACUTE: Rat lDLq: 30D0 mg/kg 2,3,E.6-Tetrametnylphen: ' (CRE) CASRN: 527-35-5 HONS 218042 Thiobutyric acid, S-dacyl ester (XLPE) Toluene; Methylbeniane (CSPE, EPO, NIT, NOM, PE, PET, PU, STY, SUL, XLPE) CASRN: 108-88-3 STDS: OSHA: 200 ppm TLV: 100 ppm, 375 mg/m3 TWA; 150 ppm, 560 mg/mJ STEL OESC: Volatile Liquid HLTH: Irritation-Eyes, Nose, Throat--Modarate (15). Narcosis (8). Suspect teratogen (5). Mutagen (2), SKIN ASS: Yes SKIN IRR: Hi Id INGES ACUTE: Rat L0IO: 5000 mg/kg 2,4-Toluanediamine; 2,4-Diaminotoluana (PU) CASRN: 95-80-7 DESC: Solid, m.p. 97-99*C HLTH: IARC CARC: Animal Positive, '78 and '82. Listed In 2nd NTP Annual Report on Carcinogens, SKIN IRR: Mild INGES ACUTE: Rat LDI0: 260 mg/kg '81. Toluene 2,4-diIsocyanate; TDI; Tolylene 2,4-diisocyanate (PU) CASRN: 584-84-9 STDS: OSHA: C 0.02 mg/*1 TLV: C 0.02 ppm, C 0.14 mg/m3 TWA OESC: Samivolatlle Liquid HLTH: Asthma (9). Irritation-Eyes, Nose, Throat, Bronchi, Lungs--Marked (14). Darmatitls (3). SKIN IRR: Severe INGES ACUTE: LDI0: 5800 mg/kg Toluene 2,6-diisocyanate (PU) CASRN: 91-08-7 DESC: Samivolatlle Liquid HLTH: Respiratory sensitization (Asthma) (9). m-Toluidlne (CRE) ' CASRN: 108-44-1 DESC: Samivolatlle liquid SKIN IRR: Rabbit: 500 mg/24 H, severe EYE IRR: Rabbit: 20 mg/24 H, savere ORAL: Rat LDt0: 450 mg/kg o-Toluidine (CRE) ~ CASRN: 95-53-4 STDS: OSHA: 5 ppm, 22 *g/m3 TLV: 2 ppm, 9 mg/m1 DESC: Semivolatile Liquid a-33 HONS 218043 HLTH; Methemog1 obinemia (13) Acutt systemic effects (4) Suspect carcinogen I ARC CARC; Animal and Human Indefinite, Human Suspect, '62 SHIN IRR-. Moderate INGE5 ACUTE: Mouse LD(0: 520 mg/kg '78 g-Toluidine (CRE) CASRN: 106-49*0 DESC: Solid, m.p. 45-47C SKIN IRR: Rabbit: 500 mg/24 H, severe EYE IRR: Rabbit: 2D mg/24 H, severe MUTAGEN ORAL; Rat LDS0: 56 mg/kg 3-To)unitrile; m-Tolunitrile; l,3*Tolunitrile (NOM) CASRN: 620-22-4 DE1C: Semivolatile Liquid EYE IRR: Rabbit: 500 mg/24 H, severe ORAL: Rat LDS0: 4.2 g/kg Trifluoroacetyl fluoride (TF) CASRN: 354-34-7 Trifluoromethane (NIT) CASRN: 75-46-7 Trimethylbenzene (SUL) CASRN: 25551-13-8 STOS: TLV: 25 ppm, 125 mg/m* TWA. 35 ppm, 170 mg/mJ STEL OESC: Semivolatile Liquid HLTH: Irri tation-i.ungs , 3kin--Marked (14). Cumulative CNS Effects (7). Anemia U2). SKIN IRR: Yes Triphenylene (PE) CASRN: 217-59-4 DESC: Solid. m,p, 19S-198C Yaleraldthyda; Pentanal; Amyl aldehyde (PE) CASRN: 110-62-3 OESC: Volatile Liquid SKIN IRR: Rabbit: 500 mg/24 H, moderate EY IRR: Rabbit: 500 mg/24 H, severe ORAL: Rat L0so: 3200 mg/kg SKIN: Rabbit L0so; 6000 mg/kg HONS 218044 Valero lactone (PE) CASRN; (ylioflwr) 108-29-2; (o-) 542-28-9 OESC: Samlvolatlla Liquid Vinyl benzoata (PET) CASRN: 769-78-8 DESC; Samlvolatlla Liquid ORAL: Rat L0so: 3250 mg/kg SKIN IRR: Rabbit; 10 mg/24 H VInylcyclohexana (NIT) CASRN: 695-12-5 DESC: Volatile to Samlvolatlla Liquid ORAL: Rat LDt0: 3080 mg/kg IARC CARC: Animal Indaflnita, '76. Vinylldana fluorlda; 1,1-01fluoroathene (TFZ, VIT) CASRN: 75-38*7 OESC: Gat ORAL TUMORIGEN: Rat TO. : 1930 mg/kg/52 W IHL: Rat LC^ : 128,000ppn/4 H Vinylpynaina (PU) CASRN: (2-ltomar) 100-69-6; (4-) 100-43-6 OESC: Samlvolatlla Liquid Vlnyltoluana; Methylstyrene (MOM, PET) CASRN: 25013-15-4 STOS: OSHA: 100 ppm, 480 mg/a TLV: SO ppm, 240 mg/nt> TWA; 100 ppm, 48S mg/m* STEL DESC- Samlvolatlla Liquid HLTH; Irrltatlon-Eyei, Nota, Throat, Skin--Moderate (15, Lett than 200 ppm) CNS affactt (7, Graatar than 200 ppm). INGES ACUTE: Rat LDo' 4000 mg/kg Xylanat (CSPE, EPO, NON, PU) CASRN: 1330-20-7 STDS; OSHA: 100 ppm, 435 mg/m3 TLV: 100 ppm, 435 mg/m3 TWA; 150 ppm, 555 mg/m* STEL OESC: Samlvolatlla Liquid HLTH'. Irrltatlon-Eyei, Note, Throat, Skin-Moderate (IS, Lett than 200 ppm) Narcotit (8, Graatar than 200 ppm). Xylanols (CRE) 2.3- CASRN: 526-75-0 ` DESC: Solid, m.p. 2.4- CASRN: 105-67-9 OESC: Solid, m.p. 2.5- 73-75.5C 22-23C/Sani volati la Liquid 8-40 HONS 218045 CASRN: 95-87-4 DESC: Sol id. m.p. 71-73*C 2,6- CASRN: 576-26-1 DESC: Sol id, m.p. 4$-46#C 3,4- CASRN: 95-65-8 OESC: Sol Id, m.p. 65-68"C 3.5CASRN: 108-68-9 DESC: Sol Id, m.p. 65-66C Xylidine; Oimathylanil i na (CRE) CASRN: 1300-73-8 STDS: OSHA: 5 ppm, 25 g/ma TiV: 2 ppm, 10 mg/ir* TWA DESC: Sami volatlla Liquid HLTH: Mathamoglobinamla (13) Acuta systamic toxicity (4) SKIN ABS: Yas INGES ACUTE: Rata LD,0: 610 mg/kg 2,4-Xylidina (CRE) CASRN: ?r ES-1 DESC; Sem-ivolatlit Liquid MUTAGEN IARC CARC: Animal Indafinita, 178 2,5-Xylldlna (CRE) CASRN: 95-78-3 OESC: Samivolatl1 Liquid MUTAGEN ORAL: Rat LDS0: 1297 g/kg IARC CARC: Animal Indafinita, '78 REFERENCES TO APPENDIX 8 1. R. L. Tatkan and R, J. Ltwi*, Sr. RTECS. Raoistrv of Toxic Effacts of Chamical Substancas, 1981-1982. DHHS (NIOSN) Publication No. 83-1D7. Washington, D.C. U.S. Govarnmant Printing Offlea, 1983. 2. "Appandlx A: U.S. Dapartnant of Labor, Occupational Safaty and Haalth Administration, Chamlcal Information Tabla" In: OSHA Industrial Hvoiane Ttthnlcal Manual. Chicago, IL: Commarce Claarlng Housa, Inc., 1984, pp. A-i to A-281. 3. Aldrich Chamlcal Company, Inc. Aldrich Catalog Handbook of Fina Chemicals, 1986-1987. Mllwaukaa, WI: Aldrich Chamlcal Company, Inc., 1^86. 4. M. windholx. Editor. The Merck Indax, 10th ad. Rahway, NJ: Marck and Company, Inc. , 1983. 5. G. G. Hawley. The Conoansed Chamlcal Dictionary. 10th ad. Naw York: Van Nostrand Reinhold Company, 1981. 8-41 HONS 218046 6. R, C. weast, Editor. CRC Handoobk of Chemistry and Phytic*. 61st ed. Boca Raton, FI: CRC Press, Inc., 1980. 7. National Institute for Occupational Safety and Health. Current intelligence Bulletin 41. 1.3*Butad1ene CH,:CH*CH:CH,. DHHS (NIOSH) Publ. No. 84-205 PB84-198019 Springfield, VA: National Technical Inforeatlon Service, 1984. 8. National Toxicology Program. Toxicology and Carcinogenesis Studies of 1,3Butadlene (CAS No, 106*99-0) in B63F1 Mice (Inhalation Studies). tech. Sep. Ser. 288. Research Triangle Park, NC: National Toxicology program, 1984. 9. J.. E. Huff, R. 1. Melnlck, H. A. Solleveld, J. K. Heseman, and M. Power*. Multiple Organ Carcinogenicity of 1,3-Butadiene In B6C3F1 Mice After 60 weeks of Inhalation Exposure. Science. 277(4686), 548*549 (1985), 3-42 HONS 218047