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EPRI Electric Power Research Institute Topics Chemical analysis Construction materials Pyrolysis Combustion products Toxicology--hazards EPRI EL-4939 Protect 2028 15 Interim Report November 1986 Literature Review of Pyrolysis and Combustion Products of Selected Utility Materials Prepared by Midwest Research Institute Kansas C'ty, Missouri 02Q<tl-0 HONS REPORT SUMMARY SUBJECTS T&D- Substations / Hazardous/toxic substances TOPICS Chemical analysis Construction materials Pyrolysis Combustion products Toxicology--hazards AUDIENCE Environmental managers / Distribution engineers 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 EPRI El 4939s BACKGROUND Previous EPRI report EL-4503 presents a literature review of the pyrolysis end combustion products of polychlorinated biphenyl (PCS) substitutes EPRI extended thet work to include thermal-degradation products ol many utility construction materials The expended 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 matenals. 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 protect teem grouped the matenals according to their chemical composition--whether they contained chlorine, fluorine, nitrogen, and sulfur or only carbon, hydrogen, and/or oxygen RESULTS Pentachiorophenol and its sodium salt produce polychlorinated dibenzo-pdioxins and polychlorinated dibenzolurans Several polycyclic aromatic hydrocarbons (PAHs). many of which are known carcinogens are produced from combustion or pyrolysis of polyethylene, chlorosulfonated polyeinyiene styrene, and creosote Indeed, creosote itself comprises aPout 83 Ac PAHs MONS 020411 Thermal degradation of bupnenol A epoxy resin, creosote. cross-tm<ec polyethylene. Kapton. Nomex, polyethylene, polyethylene terephthaiate (Mylar), polystyrene, and polyurethane gives other toxic s*mivolant or solid products of concern These are aromatic amines, phenolic com pounds. or aromatic hydrocarbons. Other materials reviewed include neoprene, six Huormated polymers, tour nylons, dicyandiamide (no thermal-degradation information, however), nnnle rubber, polysuifone Kraft paper, and cross-linked polyethylene One appendix of the report summarizes the more toxic degradation products from materials raviewed either m this report or in a previous EPRi-sponsored literature search, In addition, degradation products from other materials not covered in detail m this review are also sum marized in the first appendix. Another appendix lists the relative volatility, inhalation limits, and other health and safety information tor most of me more than 200 thermal-degradation products listed EPRI PERSPECTIVE This report was initially undertaken as the brat quarterly report lor EPRI research project RP2028-15. However, because of its excellent makeup, it was expanded lor publication as an interim report In addition to its use m selecting pnorities for subsequent laboratory re search, this information should also provide many insights to utility en vironmental engmears for expanding their knowledge of commonly used materials Ona caveat must be observed. There was no effort to categorize materials based on quantity usage PROJECT RP2028-15 EPRI Protect Manager- Gil Addis Electncal Systems Division Contractor Midwest Research Institute For further information on EPRI research programs, call EPRI Technical Information Soecialists 14151 855-24H HONS QZ0<tl2 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 Volter Boulevard Kansas City. Missouri 64110 Authors B L Carson M D Enckson J L McCann Prepared for Electric Power Research institute 3Ji2 Hitiview Avenue Paio Alto California 94304 E=R1 Proiect Manage G Aods 'ansm'SSion Substations 3rcg-er*' E'ectr ca Svsiems >visicn MONS 020413 ORDERING INFORMATION fleauests *or cooes d (ha report should be directed to Research Repots Center (RRC) Bo* 50490 Pato Alio CA 94303. (415) 965-4081 Tnere is no cnarge for reoons requested by EPRi member utilities and affiliates U S utility associations. U S government agencies (federal state, and local), media, and foreign organizations with wn*cn EPRi has an information exchange agreement On request RRC will send a catalog ol EPRi redoes ltci' Pp*ff AtMlfCh IttUult *"0 DPf r#^Wf*c rrrvs 0' c ' c aSie' **rC" '"Stilus *C COOyngnt i *9W Cltc^ic Po*' We#rcn iftftMut* i*C rtgfrt* rftervtc NOT(C= Tni* ifpcn Pow* Rfjtuc* Ov in* 0C*iVlKyN*l ft*rr>*d C* Ow 1} 4n *CC0uiv Ol <-rs i^orserfa Cv n# z t: *f>c ^r>ef PW T^moon o< EPRi tne crQVvz#iC"i$ "irr*o duo* rc i nwiOfl icjng eft O' I^V Cr (if 'rrintt inv wi'flfttv ftaerets O' ~*G tZ if escei 5 ,s* * &crus -^tinjo o*oc** oi*cip**o rf n lecon o -ia iwi- ^se -a -- ftn-tg* ; v*r >*nfo '^nti o* ci nif-riaj i*y nioi^'M iih re*D*c >0 ''e jit ot y c~< "* ,,31? s-iv r*irraiior aoiaa gs fte**oo o' d octsj occ9ec " iftti tec" p'ta*G cv viioiffSt ae*ea or ns, ,, e 'anJJj l&SCw HONS 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, adhes'ves, 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- thty contain chlorine, fluorine, nitrogen, sulfur, or only carbon, hydrogen, and/or oxygen. Pentachlorophenol and its sodium salt produce polychlorinated dibenio-g-dioxins (^COOs) and polychlorinated dibemofurans (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 85X PAHs Thermal degradation of bischenot A epoxy resin, creosote, crossl1n*ed polyethylene, Kapton, Nome*, polyethylene, poly(ethylen# terephthalate) (Mylar), polystyrene, and polyurethane gives other toxic semlvolatile or solid products of concern. These are aromat" amines, phenolic compounds, and/or aromatic hydrocarbons. Other materials re viewed "dude neoorene, six f'uorinated polymers, four nylons, dicyandiamide (no thermal degradation information, noweverj, nitrile uober, pmysui fone, vraft paoer, and crosslinked polyethylene. One appendix summeriies the more toxic degradation products from materials re viewed either in this report or in a previous EPRI-sponsored literature review In sedition, degradation products from otner materials not covered in detail in this -evlew are also summarized in the first appendix Another appendix lists tne -e' 'v volatility, inhalation limits, and other health and safety information for nos: t' the more than 200 thermal degradation products listed MON 5 020*15 ACKNOWLEDGMENTS This report is the product of the efforts of many people. We ere indebted to HRI' 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 E PR I 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 materraIs to be reviewed and tested on this program. MONS 020416 CONTENTS Section 1 INTRODUCTION Background Search Strategy Data Compilation Contents and Organization of the Report Reference 2 CHLORINE-CONTAINING MATERIALS Background Information on Two Well-Studied Chlorinated Compounds (PCBs and PVC) Neoprene Pentachlorophtnol 3 FLUORINE-CONTAINING MATERIALS Halar Teflon Teflon FEP Teflon PFA Tefzel Vlton 4 NITROGEN-CONTAINING MATERIALS Creosote OicyandTamide Kapton Nitrile Rubber Nomex Nylon 6 Nylon 6,6 Nylon 6,10 Nylonll po 1 vuret.hanes 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-j.O 3-12 4-1 4-1 4-6 4-8 4-13 4-14 4-24 4-27 4-30 4-31 4-32 HONS 020417 Section 5 SULFUR-CONTAINING MATERIALS Chiorosulfonated Polyethylene Polysulfon* 6 MATERIALS CONTAINING ONLY C AND H OR C. H, AND 0 Bisphenol A Epoxy Resin Crosslinked Polyethylene Kraft Paper Polyethylene Polyethylene terephthalate)(Mylar) Polystyrene APPENDIX A APPENDIX 6 SUWiARY OF UTILITY MATERIALS PROPOSED FOR EXPERIMENTAL TESTING ANO THEIR TOXIC THERMAL DEGRADATION PRODUCTS HEALTH ANO SAFETY INFORMATION FOR THERMAL DEGRADATION PRODUCTS Page 5-1 5-1 5-3 6-1 6-1 6-5 6-7 6-9 6-23 6-31 A-l B-l hdns 020418 1 TABLES Table 4-1 American Wood-Preservers' Association Specification Pl-78 for Timber-Treating Creosote 4-2 Composition of Coal Tar Creosote 4-3 PAHs in Air Total Solid Particulates Oownwind from Open Burning of Creosote-Treated Railroad Ties Doused with No 2 Fuel Oil 4-4 Nome* Pyrolysis Below 500#C 4-5 Nomex Pyrolysis at 500 to 1000C 4-6 Nomex Combustion 6-1 Polyethylene Pyrolysis 6-2 Polyethylene Combustion or Other Theneooxidative Degradation at Temperatures Up to 700C 6-3 Polyethylene Combustion at 500 to 1000C 6-4 Polyethylene Terephthalate) Pyrolysis 6-5 Polyethylene Terephthalate) Combustion Page 4-2 4-3 4-5 4-19 4-20 4-22 6-14 6-16 6-19 6-26 6-29 HONS 02041^ ix SUMMARY This report presents a review of the literature on the thermal degradation of a large number of materials usad by and of inte-est to alectrical utilities This review supplements a previous Electric Power Research Institute (EPRI) literature review (EPR1 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 (RP2028-15) and at the University of Dayton Research Institute (UDRI) (RP2028-16) to fill some of the gaps in the literature A computerized search of Chemical Abstracts back to 1967 was performed for about 60 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 their volatile thermal decomposition products, the simplest of which are hy drogen chloride, hydrogen fluoride, hydrogen cyanide and mtrogen oxides, and sul'ur sioxioe, -essective'y noweve-, the -olatile oroaucts are of 'esser concern as building and environmental contamination problems after a fire involving electrical equipment than the products of tow volatility (boiling point above about 130C) Materials containing only carbon, hydrogen, ana/or oxygen atoms were therefore re viewed because of their potential, like that of fossil fuels and ce'luiose-Dased fuels, for forming carcinogenic polycyclic aromatic hydrocarbons (PAHs) during thermal degradation Two utility materials, polychlorinated biphenyls (PCBs) and poly(vinylchloride) (PVC), are briefly reviewed as benchmarks for comparison with the other materials reviewed. Data '-ora the primary literature on combustion (heating in air or oxygen) o- oyroij'is (heating in nitrogen, helium, or other inert atmosphere) of the materials were coniQi'ea or an experiment-by-exoenment Pas's and then summarized Data were a'sc come ec rrom secondary sources on tne occuoational exposure limits r. atr and tie ree.ti et-'ects ct most o tne rc-e tr.an Dot oecomoos : on oroaucts oe-t ` ed * KQAIS 0^0420 the materials reviewed may form highly toxic carbon monoxide during combustion Other products identified as being potentially among the most hazardous thermal degradation products of the materials reviewed are grouped by toxic action in Table S*1 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 formulatea neoprene, tnese matt'ials in actual use wit' nave been coir.pounaed witn 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 m 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 report, tne materials are grouped by cnemical composition, with materials containing rluonne, cnlonne. 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 al' products are mentioned in this summary, nor are the conditions for formation givein 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 Table S-l HAZARDOUS THERMAL DECOMPOSITION PRODUCTS (OTHER THAN CARBON MONOXIDE) FROM MATERIALS REVKV'ED Hainjij (htoriw C-- Mil iftnllflcd tl* p'tducl* ar* trim IVi.l rMr*fOi***l *lltl* W N|1 W, *r c St*rtly trrllMlflf I* (ffl, *M". *r HlfWWw 'OKr I VtlitlU W>w|ilHi Cr(lMnlt i**l- *r MCI M, mtallt |gn|*M kemtw |ffr*#u(|lt N*f# . DtNf) 31 ar tl* I it jig IWhitlll t If 1u0 Imr* L f iMrlM^piilnlg HiUrUlt H.ilar (alt* cont*)M C tj m fafl*M 'lyUtr~ IlMEWlIkylfM dKPftllllwi graitw.lt (IMm Not) OM.-h IIP Irf1-) 1* V i Lon m HCI HF *</ Hf.d m nr M,T,r UtrcMtrfdlhMtt' g-4l*ilR UITk VlnylldfRf rtwlde 11 nl ' MHtrl) HONS 0 2 0 4 2 2 X o 2 Ifl o fo o ro oj Table S-l (continued) n11 rr|i I Nilioutn (Viit^tnkou ^4i?'**! ' refMiie (l\o rt>tlni S> ' VoUtlkf* aiicUy* W- Wnjwrloll lj i loUltHni g lttvi4lR lylldi** R i|>lof> lit' lit -4Jf-r Ik--** Mr t.wi 1. * 1'.. |y>'< e (1. - ft I'll |*>lyak JIHl t Mllrfl.f rfl Him T4'*J t r ) HCN Ac tlonitriIt HCN Rtttfnllrllf Cymty* MCN Hl|r([ n|'4t IN fl Ac* 1*411 t*lk* Htlf An kiln* nWMl Ank1in Phtnal Ky1 idtnt \ i, n IrilNIiRf l |yt, .ifclw. %t Kr^kfkUfy |r*rl -- : *' - V1t*U HMnnhlllf _ C<1( ll^ynlc____ "y*i' *i Volatile RmiffoliUlt *Hrnrt <Uf ItrAlggt^ 01*r) * r iMitlil i kt Cri*1 NApfcltultn* m Ndifti(ti| Ph*nl QmIm! In ItllfldlN jk- Ululiikn* PNnI |i(i||Atlr|` (tN ?,M<fiitf lutr inlbm ifilNPf inIKtN l**Hi b>ri tnt lniHilWT*n* Chryim (inwcI) o.**<>]' MlKtKCAt f IwrinlkWN RipdlMlVN * H ' N^lk% lklNl hMl liirifttk) ? )- fhf") I*n9yr*t* Tli4iN fimpnO Iwfflt Idtf HfNI t#!ii*|r1lt Jk^lofillrklf ^lyrtN Ku p*Cl) lflr*K tai,MMrllt I' t*r*n* I k [)intin Aftflln* Muip*Cl) tf|0 fh<Ml (tuipfdl I*!**#** Am t f tllvtly>tt I Illy I lk(oll> I J *i 4 IV | by I pyi (dtiw Qninfl inf Iglwir ? <li i**i ytfttlt k> < limit illf ' ifHf v yir*** I t kehtfnr d' * ow kfktfrN ArrntpMkfN OlfniphkKykfN lfi>l<i(||clr)ryfiif lfm(j jf kw*r MlhfPf li lflakr- Mknf it{ h] *">*! CfN # Ibyhlkal 7 1- nkfRylfN Wr*w QttiNliiW < **tf M lykIdinci I >iO Or** Table S-l (cont inued) lljlr* iil Or j* 4*i> it il |l|1 fwil |l|lllHJ Kell Ch ifratl k 4*t pelyrlhyiffr Itlyh Afalr Sysl r*<c lnrl<llyA Ul *, I*,.<*v*l*| If-' (rllfl HalfMlI Hflfnj AliT A rymwf (CMlIjIll Cl) "flhrl cMfrlrfr liiUI 1 |nlt<| pnfytlhvlent lie# ilm |i(!(.it ir* (wlyf |Ar|r**) ^oljuihrlibe Acrwle in i *n -*n Crttfl HmI Plifttol (emit VfVfrtty IrriUt 1)^ 1ft ty*l, SMi*. #r Vriuktiioni irtcl ' ` i+l\ ;r^ VrlillU HianfUUlf C**c knontnif Al 1 lr Afifultt 1 If Ifprivlf 1 lr Kama l*r*1 Vfl, Olkfr) 5~l ./ Vltflllf If1 liy to Knirw Il4|ih(h|ltnc IraaifiMiiffta l ( *'*p*<l 1 lilwne *iy Ifna Kyrror HuMfclUnf bnlfM Irum fcapMhflfiw {impeci | ft*Ml UuiynO SlyrtAf >> tvlurfl* ltarMI*l|n IrnifHt Miml IfAlfN CMrrtlirfl NfphMfflfM I lljirfft tflWM Ptoaol hatprcU Ac*l*l<tfbyr Actilt ffN hrvlilr MytlliAVt <|fcjrf *icfcr fft** Itfrhyifc !<!( ft H lltlMlfrilrte fcy*f r*1rrftofcjfiv Acrylic Kl| ivlyrfc *C(4 rnffrif 1 ) NtHlItfte larMfrtiHydi hr(t|iMhri' f Iwrtftlhvnf Niffj c oalA/tiw Jpyrfitf Arralrla (l*y! 1t*0*r f*r*U M'l IrlraHyrii f rwi 1 fHfnf Itftyrfc kId C^thylpAffl atilhrfw $ MyrtliclMf (AryStnv f NpMhlrn* ($alpecl) HONS 020H2H fable 5-1 (continue*!) M|rJ #_! Ppyaddd Hlto Hull iiilnll Vil*tlljl> in-..nni` }d*vrry Irritating U (|fff, SfcUt m " <rl Vd IIIlid HqmpUI lid (-i-r-d-M^fnlt voiatlU HoardlilUi a#i-Q4<K 11* Kart'd (Wwl*tn1 Unloy*. Olt*irj * * ** Seal it Vtlaljle Nonrolitila Malarial WlIhMl ItiitH hwi ((Mllmad) Palyl elhy IvN (artphlktild (Mr Ur) fartololn ktlitMydd ikraltU f im 1 dafydl Maphtha Una Irnfdnt laiM>Phy4d MaphthaltM (lliipecl) Style*# hcfalti* Id tu#no Palytlyrrno 0 fkml IkilltMy* Acetic acid fftrailMr^l rti( ld Naphtha lent Pfcdfttl Ionian# lorMlOehy*# *Mtl)fnlk|' cdd " ftt<iif( t IpknR|k|i( 0*nio(f In***# (twtfdcO Ihf yl**d ) tWthfUkl Mlkrne Slyer*# Naphtha tan# (mprcO Phenol Ji-atpecl) l#lto#no Ac map*then# 0ni*J| h 1) porylm# 1 IWI^lcIwl anthren# iPidtKlv th Mill celcm vrri Itletlrd fr MOf^ th*ve In A^*n4lI Wwi# ini lbu dftll (lr('i*l * Ulllflt hilf if Ifn t*t Mivilll li < JO *9/If Mr *lpht (Ml, *M>I Intiolatld* lP&* Is MH ^ li air Itr m a-paturd pifltif #H hf *r lt, M/fr *wm 4r**1 10^1 ii < 4) ftf/lg bw b#alatll ri^iotnti ait iWUM far tit# fui|>oii ol ihiv iludy it Ihotd (^rtwidi ullh balling f**Ini4 Ian Ihni |J0*( (t 9 , CO) or liquid! | 9 )iirn| Hut wild cwfMiii* rabidly ae4 mt Idtad 1 d I Out altrr lira Mffit *rt p*t#t cSHl9l(Hf! and nM<l(|IVf *tw far purpev s f <M* itudy CMpcimila with Milt*? ftiMi frralrr than |JO"t Ikid ar tlquldi (( 9 llyri#l fi t|l|dl la 9 , PMI|) to Ida |w iq'i 4d *ld Ml |rf dM< t*d Id r**|iOMtd qvtcdy IrM a fil'd r**|Plid IK* Ittln fctlwvtn III# Im c Imo Ii iMcwfiat imitrarr tud It hkviHi H| liaftctii) lif #r#ap1r, laMn* |b p lll*C) I* dtifirlitd tl a valitltd ^*1 Id olyrti* |li p - MS*C| It cittyttlnd It a irtUtlitlld JMf rtl(a\|i| r*M lh( palpM* or tram lha pfllyorr ann auiiliirl, r(#cU Kl|h flfatt In Ik lkr'1'9 and afMlytli.il ipparjtuf to |tt lit# llf4 MQNS OZO'tZS CHLORINE-CONTAINING materials Thermal degradation of chlorin-contaimng materials releases long-term residual contaminating products as well as the more immediately hazardous volatiles Tires involving PCBs in electric equipment have contaminated buildings with polychlorin ated dibenzofurans (PCOFs) and, sometimes, when chlorinated benzenes were present, with polychlorinated dlbenzo-g-dioxins (PCDDs). 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 sulfide (n2S), sulfur dioxide < SC2), nonylphencl, pnthalic anhy dride, and toluene. Pentachlorophenol is used to preserve wood construction materials, including util ity poles. Coaibustlon of pentachlorophenol and its sodium salt gave octa-, hepta-. hexa-, and lower chlorodibento-g-dioxins in the volatiles and residues Dcta- and hexachlorodlbenzofuran were also identified. Other combustion products identified were penta* and hexachlorobenzene and decachlorobiphenyl FLUORINE-CONTAINING MATERIALS The fluorinated polymers reviewed include Halar (which also contains chlorine), Teflon, Teflon FEP. Teflon PFA, Tefzel. and Viton These materials are used as wire and cable insulation. Combustion and pyrolysis products reported generally included monomers and other fluorinated to C4 alkanes, alkenes, or cycloalkanes, and nydrogen fluoride (HF) or silicon tetraf1uoriae (SiF4) (presumably formed from reaction of fluoride and glass of the experimental apparatus) Carbon monoxide (CD. carbon dioxide (C02), carbonyl fluoride (C0F2), and tn fl uoroacety 1 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 Vmylidene fluoride, which was emitted from thermal degradation o' Viton as well as from Tefzel, and Teflon fume were otnar oyolysis or combustion products HONS 020*26 NITROGEN-CONTAINING MATERIALS Materials considered in this section include crto*ot; the paper-impregnating sub stance dicyandiamide (cyanoguamdine, colloquially callad "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 polyurethane* 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* PAHs, about 3 to 10% tar acids (phenolic*); 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 beni[a]anthracene, benzo[k]f1uoranthene, benzo[a]pyrene, chrysene, di benz[ath]anthracene, and o-phenylenepyrene (indeno[l,2,3-cd)pyrene) No mfcrmeticn was 'bund :n the combuft'pn or c-o'vsis -' d`c fdi'r.-r -- < * paper impregnated with dicyandiamide. Kapton film is usad to insulate wire and cable, and Kapton molded parts and lami nates may be used in printed wiring boards and integrated circuit carriers C02, CO, HCN, benzene, aniline, phenol, benzonitnle, dibenzofuran, phenyl isocyanate, substituted phthalimides and pyromel1itimides, and a highly conductive cnar were produced by pyrolysis of Kapton. 3yroiysis or nitrile "upper proouceo ammonia (NH3), HCN, the monomers (ac/ion-tnle and butadiene), acetonitrile, other nitriles, various hydrocarbons, dime-s, and trimers Nomex paper is used to insulate dry-type transformers as well as to insulate non performance motors and generators. Nomex is an aramid, that is, an aromatic po'yamide prepared from 1,3-phenylenadiamine and isophthalic acid or isophthaloyl chlo 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 500C), benzor.itr-le. 1.3-pnenylenediamine. benzoic acid, aniline, 1,3-dicyanobenzene (above s00C), and N-(3-aminopheny1)benzamide (600-700C) The charred residue became rcre aromatic between 450 ano 5503 By 1000C, most of the hydrogen and oxvge^ -aa been lost 'rom the cnar In :ontrast to pyrolysis, where 4 mm at '.C00C 020^27 HONS caused only 505 weignt loss, no residue remained by 1000C in air or oxygen Water, carbon dioxide, and/or carbon monoxide wer# major combustion products Nitric oxide (NO), nitrous oxide. HCN, cyanogen, benzene, substituted benzenes, acetone, acetaldehyde, benzoic acid, nitriles, 3-cyanobenzoic acid, alkanes, alkenes, and nitromethane 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 give 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 8QC"C, po'yu" 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 et temperatures below 800C included carbon oxides, nitrous oxide, alkanes, alkenes, and lower aldehydes end elcohols. Between 800 and 1000C, ni triles, aromatic hydrocarbons, and troaiatic N-containing heterocycles such as methylpyridine end quinoline were formed, although lower aldehydes end propene were still abundant at 10004C. Other products et the higher temperatures included tol uene diisocyanate , toluanediamine, and nitriles SULFUR-CONTAINING MATERIALS Chiorosulfonated 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 elkenes, end toluene. 6y about 900C, aromatic products predominated with hign yields of benzene and naphthalene Styrene and several noncarcinogenic PAHs were found in the pyrolyrete Chlorosulfonated poly ethylene may contain additives to reduce the amount of hydrogen chlonae (HC1) emitted on combustion. Sulfur dioxide, which is highly toxic and irritating, is also evolved on combustion along with carbon oxides HONS 020428 Polysulfone (a copolymer of bisphenol A and 4,4'-dich!orodiphenylsulfone) has many electrical and electronic applications including connactors, TV components. capac itor fi'lia, and circuit boards. Combustion of polysulfona at 400C causad a 70% loss in polymer weight but littla smoko and llttlo sansory 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 bispnenol A epoxy resins (although some are crosslinked with amines), crosslinked polyethylene, kraft paper, polyethylene, po)y(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 epichlorohyann 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 4&-kV range. Crosslinked polyethylene wire insulation was practically all volatilized by pyrolysis up to about 480C Pyrolysis and combustion products have not been studied. Volati1lzetion of decom position products of impurities such as the chemical crosslinking agent. cncumyl peroxide (DC?) might be expected during exposure to lower temperatures Decompo sition products that have been identified from OCR included o-methylstyrene, cumene, phenol, end toluene K-aft paper is used for lnsulet-on in oil-immersed equipment such as transformers Kraft paper pyrolysis gives the same products in about the same amounts as do onecel lulosic materials (paper, wood, etc ) Gases included the carpon oxides, nycr-gen. acetylene, methane, ethylene, and other hyorocaroons Heating above SD0C gave lower molecular weight volatiles and cnar HONS 020429 A major use for polyethylene l'n 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 hydrocarbons (olefins, primarily 1-alkenes with lesser amounts of o.ui-dtenes) Combustion gave similar products, especially in the range 350 to 700C Besides C02 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 IX after incineration at 900C. At 950*C. the concentrations of individual PAHs and other aromatics in cold-trapped condensates were less than 1 to about AX Poly(ethylene 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. tower amounts (1-9X1 n* CO, ethvlene, 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 1400*C Other major pyrolysis products included toluene, cr-methylstyrene, cumene, and styrene oligomers Lower aliphatic aldehydes and carboxylic acids were major products along with benzene, toluene, ethylbenzene, styrene, and propyibenzene on comoustior, oeiow aoouc 500C In one stuay, zcspusv.on at 5Qu :: 900*C 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. MQNS 020430 Section 1 INTRODUCTION BACKGROUND The overel! goal of this project is to evaluate th* 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 hat been con ducted to supplement C.'.e lite-ature review previously conducted by the Elect-ic 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 cletr'y shows which materials have been 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. RP202B-15) and UDRI (EPRI Project No, RP2DZ0-16) 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 experiments are highly dependent on the experimental conditions Thus, compar>sens of resu'ts from different studies will be difficult and will require great Care to prevent oven nterpretation of the data. HONS 020431 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 Each 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 mghly toxic volatiles (HC1, HF, HCN, N0x, and $02) were selected for review. Later, materials with only C and H or C, H, and 0 atoms were examinee for their potential to p-oduce P^s 0n exposure t? e'e ated tsmpe''t."-:: Pertinent articles were selected for compilation based on their abstracts. The articles were primarily English languaga, but Russian, Garman, 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 examinee for data compilation data ccmpilaticu Articles that did not identify the decomposition products (for example, those on thermal degradation analysis and differential scanning calorimetry that aid not collect and analyze the volatile products emitted) were generally not examined closely. Combustion toxicity articles were sometimes useful in identifying at least ralativa amounts of carbon monoxide, carbon dioxide, and other toxic gases such as hydrogen cyanide or hydrogen chloride Generally, the more recent art'* 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 oyrciy; : or comoustion experiment was desc'bed on a separate cage using the same `c-me' HONS Q20432 In addition to tht primary literature from which experimental and mechanistic detail* were extrectad, various secondary source* 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 acuta 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 2D0 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 meterials is beyond the scope of this review. Data are not directly comparable among the studies and would require ex tensive critical raview. CONTENTS ANO organization OF THE REPORT The remainder of this report contains prof lias for eech material organized as fol lows Ganeral Information, Thermal Decomposition Mechanisms (not always present), a Sunwary of Experimental Studies Reviewed subdivided into separate discussions for pyrolysis and combustion (when information was available on both processes), and the References citec. The eaterials are grouped by type of hetaro atom present in th*-r molecules Thus, Section 2 contains profiles for chlorint-contaimng polyr s suen as neoprena, Section 2 -s on the fluorine-containing materials. Sec tion - is on materials containing nitrogen atoms, and Section 5 contains informa tion on two polymers containing sulfur atoms. Saction 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 on previously reviewed and their most toxic degradation products, if any thermal degradation literature was available More then 200 products we- identified for the 26 materials profiled Appendix 6 contains toxicity, standards, and physical state information for most of tnese products The starting matenal(s) for each product are identified HONS 020433 reference J. V. Zboiinek, J. R. Marsh, D Guth and A. Bohrnerud (SCS Engineers, Inc ) Stata-of-the-*rt Review of Combustion and Pyrolysis Bv-Products of PCB Sub stitutes E&RI Report No. EL-A5D3. Palo Alto, Calif Electric Power Research Institute, March 19B5 HONS 020434 Section 2 CHLORINE-CONTAINING MATERIALS BACKGROUND INFORMATION On TWO WELL-STUDIED CHLORINATED COMPOUNDS (PCB* and PVC) Polychlorinated biphenyls (PCBs) end poly(vinyl chloride) (PVC) ere 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 witn those from the other materials revieweo 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 (PCDDs), and polychlorinated dibenzofurans (PCDFs) Among these a-e pyrolysis and combustion studies of PCBs and PCB-contaminatea fluids such as mineral oils. This effort is supplemented by reviews and experi mental work on the pyrolysis and combustion of PCBs and other utility materials (1). The recent NIOSH Current Intelligence Bulletin Polychlorinated Biphenyls fPCBsl Potj-tial Health Hazards from Electrical Equipment Fires or Failures (2) ano two crRI*joonsoreo reviews or. fCEs in: other materials 'orm the basis for -.ost of the following discussions on PCBs and PVC oTvc,'1o'-'natec Biphenyls (PCBs) "ne NIOSr Current Intelligence BuMetir 2) gives guidelines to protect the nea'tr o- ene^genc; response and cleanuc workers in the aftermath of PCE-contain:ng e t::-":: -ec. pmert *'rnS tnat nave p-ooucsc wioesoreao ou.lcng oontami nsz 'or MOHS 010^ with PCBs, PCDFs, nd PCDDs. NIOSH recommends that PCBs and 2,3,7,B*tetracHorodibenzo-g-dioxin (2,3,7,B-TCDD) Da regarded at potential human carcinogen* in addttion, PCB*, PCDFs, end/or PCDD* have Dean reported to injure the liver, thymus, and reproductive systems of test animals and to produce chloracne, numbness of the limbs, and other adverse affects in humans (2). 2,3,7,B-TCD0 Between 1932 and 1979, when the U.S Environmental Protection Agency (EPA) issued restrictions on the manufacture and commercial use of PCBs, 135,000 PCB-conteinmg transformers were put into service. Many of these transformers and PCS-contaimng capacitors are still in use. EPA estimated that by the end of 19B4, approximately 107,000 PCB'Contalning transformers were in use or being stored for reuse, more tnan two-thiros of these transformers -ere used in or near puolic buiIcings s a result of the mandated selective EPA phase-out schedules, these numbers have de creased significantly. In 1981 there ware about 3,3 million capacitors containing more than 3 lb (0.7 kg) PCBs. In addition, past manufacturing and transformer ser vicing practices have contaminated mineral oil-filled equipment with trace amounts of PCBs (.3). Soma commercial PCB mixtures manufactured in the United States contained up to 6 ppm PCDFs, and CBs from Europe and Jaoan contained uo tc about 20 dpi* PCOFs (3) PCOFs have been found in almost all measurements of contamination after fires in electrical equipmant containing PCBs. A total of 2,163 ppm PCOFs was determined in 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 document summarizes the concentration of PCBs, PCDDs, and PCDDs in the soot and surface wipas after 11 U S. fires involving electrical capacitors or transfonaars. PCDDs ware 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 Bingnamton fire (2). Dther chlorinated aromatics detected (but not quantitated) from fires involving PCB-conteming electrical equipment were polychlorinated tnpnenylenes (PCBPs), polychlorinated pyrenes (PCPYs), and polychlorinated enrysenes (PCCYs) Some PCB samples themselves contain PCBP, PCPYs, and PCCYs (3) HONS 020436 Cl PCBPs pcpys Neither ordinary working conditions nor long-term overload (180CC maximum damages the insulation rapidly) for electrical equipment containing PCBs is conduciva to formation of PCDDs and/or PCDFs. Optimum conditions for formation of PCOFs from PCBs art 8X excess oxygen and about 67S*C for at laast 0.8 sac. Thasa conditions producad parcant levels of PCOFs (relative to tha amount of PCBs combustad) from minaral oil or silicona oils contaminated witfi at laast 5 ppm PCBs (S). The major combustion products formed from fires Starting as a result of arcing in airless transformers or capacitors are PCBPs. PCOFs, PCPYs, and PCCYs art also detected. PCBPs do not form in externally initiated fires; PCOFs are tne major product with smallar amounts of PCPYs and PCCYs. PCOOs form only if chlorobenzene or ciilorophenols ere present in the transformer askarel (Z) since formttion from a PCS would require breakage of the biphenyl link. Other known or suspected environmental sources of PCOOs end PCOFs include the manu facture of trichlorophenoxyacetic acid (2,4,5-T), pentachlorophenol, and othtr chlorinated phenols; municipal and industrial inclnaration of chlorinated compounds ano plastics ano tleacneo ano unoltacneo caoer, cooper smelting, steel- production, and, to a lesser degree, fuel combustion in coal-fired power plants and wood ano peat burners (6) Po)y(vinyl chloride) fPVC) The pyrolysis and combustion of PVC -^-CHClCH2 J and PVC formulations with stabilizers, plasticizers, fillers, dyes, and other additives have been studied extensively Two recent books review tnermal degradation of PVC (~,8) Benzene and hydrogen chloride are the major pyrolysis products. Other pyr lysis products 'Certified in the range 400 to 800C are toluene, ethylbenzene, o-xylene, styrene, naDfithalene, 2-methylnaphthalene, chlorobenzene, o- and -dichlorobtnzent, and I 2,4- and 2,3.5-tnchlorobenzene (*) Only trace amounts of c'-'orobenzenes and ether chlori ne-con taming hydrocarbons are formed during PVC pyrolysis (9) MOHS 020437 Degradation products are similar for pyrolysis and combustion except that combus tion gives CO, C02, and H20. Very small amounts of vinyl chloride are evolved The major aliphatic compounds, formed in very small amounts, are C, to Ce alkanes and alkenes (8) Combustion of PVC mixed with wood chips in the range 570 to 1130C produced chlonnated benzenes, octachlorostyrene, and PC8s. Combustion and arcing produced phosgene (C0C12) (4) Chlorinated benzenes are known precursors of PCDDs and PCDFs Other chlorinated polyaromatic hydrocarbons (PAHs) might also be expected to form, and PVC is a sus pected source of the PCOOs and PCDFs 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-CDDs, PCDFS containing 4 to 7 Cls, and other PCOOs and PCDFs. The total amount of PCOOs and PCDFs produced at 800C was about 1 ppm based on the weight of PVC However, Karesek ana coworkers (12) reported in 19E3 that neither the concentrations r.o> the pattern of separate PCOOs and PCOFs in the fly ash from an energy-recovanng municipal incinerator changed significantly by adding three times as much PVC as usual to the incinerator faed. Such results do not support the contention tnat 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 950*C had chlorine atoms attached to an aronatic nucleus. The two chlorinated aikyIbemenes detected were chlorinated on t'e alkyl side group. Among the PAHs found were acenaphthylene, antnracene, benz[a> anthracene, benzo[^]fluoranthen#. benzo[cJphenanthrene , benzo[a}pyrene, benzo[e]pyrene, biphenyl, chrysene, dihydroanthracene, fluorene, f1uoranthene, indent, phenanthrene, pyrane, and methyl- ana pheny1-supstituted derivatives of the pre ceding compounds The only oxygen-containing species reported was pnenol Qctachlorodlbenzo-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 like'y direct PCDO precursors than PVC or chlorinates ;- zen*s Combustion of vegetable materials (presumably the phenol source in Tun : pal refuse) with PVC or other chlorine source has been reported to give emiss containing cnloropneno1s, PCDDs, and PCDFs (If) MOWS 020438 References I J Guertin end G Addis PCB the EPRI Effort Proc Am Power Conf f 47, 701-705 (1985) Z National Institute for Occupation*) Safety and Health NIOSH Current Intel ligence Bulletin 45 Polychlorinated Biphenyls (PCB's) Potential Health Hazaras from Electrical Equipment Fires or failures DHHS (NIOSH) Publication No 86-111, Atlanta, GA. NIOSH, Centers for Diseast Cont-o), 1986, 25 pp 3 j vueeta, J R. Marsh, S. Kennedy, L Hildemann, and S Wiley State-of*theArt Review PCPDs and PCDFs in Utility PCS Fluid EPRI CS-3308. Palo Alto, CA Electric Power Research Institute, 19B3 A Zbozintk, J V , J R Marsh, 0. Guth, and A Bohrnerud (SC3 Engineers, Inc ) State-of-the-Art Review of Combustion and Pvrolysis By-Products of PCB Substi tutes EPRI l-4503 Palo Alto, Calif Electric Power Research Institute, March 1986 5 MO Erickson. Analytical Chemistry of PCBs Boston, MA Butterworth Publishers, 1986 6 C Rappe Global Distribution of Polychlorinated Dioxins and Oibenzofurans. *eo P*o Natl Meet , Div Environ Chest . Air. Chem Soc, , 26(1), 86*87 (1986) 7 ED Owen, Editor Degradation and Stabilisation of PVC London- Elsevier Applied Science, 1984. 8 J Wypych Polyvinyl Chloride Degradation. Amsterdam. Elsevier, 1985 9. R P Lattimer and W J. Kroanke The Formation of Volatile Pyroiyzates from Po)y(viny) Chloride) J Appl Polymer Sci . 25, 1D1-11Q (1980). 10 S. Marklund, L.-0. Kjeller, C. Rappe, C Ryan, J deKanel, and R. C Dougherty Combustion of Polychlorinated Organics II. Identification of CDF$ sno PCDOs m Pyrolvsis Product*. reor Pao Natl Meet , Div Environ Chem Am, Chem See . .15(1), 130-121 ,1995) II C Ryan, J deKanel, R. C Oougherty, S Ma-k.and, . -0. Kjeller, and C Raooe Co-bustion of Polychlorinated Drganies I, Laboratory Models for Municipal Refuse and Hazardous Waste Incineration Preor Pao Nat) Meet . C-'v Environ Chem.. Am, Chem Soc . 25(1), 127-131 (1985) 12 r W Karasek, A, C. Vlau, G Guiochon, and M F Gonnord Gas Chromato graphic-Mass Spectrometnc Study on the Formation of Polyeniorinated Dibenze-d oxins and Polychlorobenzenes from olyvinyl Chloride in a Municipal Inc-erator J Chromatogr . 27D, 227-234 (1983) 11 R A Hawley-Fedder, M L Parsons, and F W Xarasek Procucts Obtained Dur-ng Combustion of Polymers unde- Simulated Incinerator Conditions III Piiyv'n* Chloride J Chromatogr . 315, 211*221 (1984) 14 * ,, ce".., G Gorett . and M V Russo PCD0 ana PCOF Formation in the ComDus. or, or Vegetable waste; '`heinosone-e 12(45). 651-651 (1983) MON5 020439 neoprene CASRN. 9010-98-4 Synonyms Polychloroprene; Poly(2-chloro-1,3-butadiene), Neoprene GN (same as GR-M--governnent rubber, monovinylacetylene) Neoprene G typas (interpolymenzed, with sulfur and contain a thiura* stabilizer), W typas (no sulfur or thiuram) (1) Insulation Materials: Neoprene-118 (multiconductor power cabla), Neoprene-84 (single-conductor high-voltage cable); Neoprene-007 (welding cable), Neoprene-435 (high-voltage, high-amperage cable) (2). Trade Names (producers) DuPrene (DuPont) General Information Molecular Formula: (C.H.Cl), Structure of Monomers and Polymer. CH2:CC1CH:CH2 2-chloro-l,3-butad1ene; chi oroprene Cl \ / -CHj CHjCHj H ch2- ^/ c c=c \ /v \/ c=c /V H Cl CHjCH2 H Neoprene (head-to-tai1) Trans structure shown is consistent with x-ray diffraction fiber analysis (3) Ci_s-1,4-polymerization, 1,2-polymerization, and 3,4-polymeri zation gi ve small amounts of other structures. About SX is present in neoprene polymerized at -4QC, * 3OX at !O0C. About 10 to 15X each of "head-to-head" and "tai1-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 ana chemical tank linings (4), and coatings for electric wiring (5) Neoprene is no: MOWS 020440 suitable as electrical insulation, but it is used as a cable jacket because of ex* ce'lent resistance to light, 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 hes several shortcomings, including greater expense and lower chemical resistance than po1y(vinyl chloride) or polyethylene, as a cable sheath material (7) However, neoprene has apparently found soaie commercial use in multi conductor power cable; single-conductor high-voltage cable; high-voltage, high-amperage cable and welding cable (2) Thermal Oecomoos'tlon Hechanisms No information was found on unfonaulated neoprene. Neoprene formulations give the largest variety of pyrolysis products at a radiant flux of 5 W/cm2 Cyclic and heterocyclic cc-pcund?, some with nitrogen in the ring, predominate and originate from decomposition o' plasticizers. At a radiant flux of B W/cm:, liquid degraoaHon products dtcreast. Aromatic compounds are formed by cracking o' the polymer followed ty recombinetion of smaller into larger hydrocarbons. HC1 evolution is retarded by the presence of basic additives. Neoprene formulations form a char layer during burning et a faster rate at highar radiant flux exposures, possibly insulating the material from rapid degradation (2) Summary of Experimental Studies Reviewed Pvrolvsis. Pyrolysis of a eureo neoprene ruober useo ;s & nose cove- gave me 'al lowing mass spectral peaks (percent relative intensity) attributed to the neoprene 36 (* 14*, HC1), 38 (v K), 88 12*; monomer), 90 (< 6*), 141 {- 3S), 176 (*- 3*. dimer), snd 178 3*). Dioctyl phthalata plasticizer and phenyl-B-naphthylamine were also idantifiad (8). Pyrolysis of a w-type (no sulfur) neoprene at tempera tures up to 300*C gave ions with mass peaks arranged m order of inc-easing inten sity 55, 91, 67, 69, 81, 73, 129 A G-type (sulfur-containing) neoprene pyrolyied at temoeratures up to 350C gave ions with mass peaks S3. 71. 88, 105, 77, 141 and 79, at temperatures up to 43DC, the peaks were 91, 41, 1C5, 129, 241, 152 and 179 Peaks found at 239 and 285 war* atcnouted to the presence of resin and peaks at 60, 73, and 254 were due to fatty acid processing agents (9) Pyrograms (gas cnromatographie ptaks) have been publisned (10,11), but products we-e -ot 'otnti'ec MONS QiQWl Combustion Virgin neobrene began to decompose et 240C when heated at the rate of 40C/min The weight loss due to HC1 and other volatile decomposition products was 45X, no char formed. Under these conditions, various formulated neoprene in sulation materials showed 18 to 46X weight loss due to HC1 and other volatiles and formed a char representing 6 to 4SX of the original weight (2). Alvares et al (1983) (2) identified products from combustion of a formulated neo prene insulation material. Many of the products were probably due to decomposi tion of the phthalate plasticizer Products evolved during dehydrochlorination included 1-octarvol (CHjCHjCHjCHjCHjCHjCHjCHjOH, assuming a straight Chain), pnthalic anhydride, nonylphenol (CeH1#C#H^0H), dioctyl phthalate, 4,5-dimethyl-l-a-jimethoxybenioyloxy-g-methoxybeniylidene-1, 11-N-dicyclocosane [sic], n-nonacosane, 2*(methylthio)beniothiazole, 3-ethyl-5-(2-ethy1 butyl)octadecane, n*hep tacosane, 1-methyl butyl isobutyrate, and phthalanil. Products evolved after dehydrochlonnation included n-hexadecene, squalene, dioctyl phthalate, diisobutyl phthalate, palmitic acid, 7-n-butyldocosane, 3-ethyl-5-(2-ethy1buty1loctadecane, and norpentyltmol [sic] acetate. Products from combustion at 200 to 8Q0C identified in the air of a combustion toxicity chamber were 5,510 ppm carbon monoxide (CO) and 3,170 ppm methane (CH,;r with a char yield of 34.3* (12). (The combustion products killed the test animals within 25 min compared to 15 min for Douglas fir.) CO end HC1 were major products from flaming combustion of neoprene seat padding and hose materials HCN was a minor product. SO; and H2S in minor amounts were evolved from the neoprene sample that naa apparently tee- vulcanized with sulfur 'll) References 1 C A Hargreaves and D. C Thompson "2*Chlorobut3diene Polymers" in Encyclopedia of Polymer Science and Technology, Vol. 3. H. F Mark and n M. 91 kales, Editors. New Yorn Wiley. 19657 PP 705-730 2 N J Alvares, A Lipska-Quinn, and H K Hasegawa Thermal Oegnadat on of Cable and Wire Insulations ASTM Soec Tech Pub! , 816(6ehav oivin Hater Fire), 42-66 (1983) C MWindholz,Editor The Merck Index 10th ed Rahway, N J Me-c< arc Company, Inc , 1583 4 J Hauck,Editor 1974 Materials Selects- Vol 78(4) Stamfo-d , C C nn fieinholo Puplishing Company, 19*3 5 GO hawleyThe Condensed Chemical Q.ct ma-v 10th ed hestrano neinnold Comoary, 1961 New i;-> .a- HONS 020442 6 J Hogan "Wirt and Cablt Coverings" in Kirk-Othme- Encvclooadia of Chemical Tecnnol 3rd d., Vol, 13. New York Interscience Puol1sntrs , a Division of Jonn Wiley and Sons, 1981, pp 564-590 7 T Tanaka and A. Greenwood Advanced Power Cable Technology I Basic Con cepts and Testing 8oca Raton, Fl. CRC Press, 1983 8 J 8. Pausch, R P. Lattimer, and H l C, Meuzeltar A New Look at Direct Compound Analysis Usmg Pyrolysis Mass Spectrometry Rubber Cham, Tecnnol . 56(5), 1031-1044 (1983). 9 A J Pidduck Mass Spactrometric Analysis of Halogenated Polymers. J Anal Aopl Pyrolysis. 7(3), 215-229 (1985). 10 J C-A Hu. Chromatography Analysis of Rubbers and Other High Polymers J_ Chromatoqr Sci. . 19(12), 634-63E (1981). 11 G Oi Pasouale and T. Capaccioli Identification of Elastomers by HighResolution Pyrolysis-Gas Chromatography and Multiple Selective Detectors 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 Flammabi iitv, 10, 140-167 (1979). 13 0, Gross, J. J. Loftus, T, G. Lee, and V. E Gray. Smoke and Gases Produced by Burning Aircraft Inte-ior Materials Building Science Senes 18, National Bureau of Standards, 1969. PENTACHL0R0PHENOL CASRN 87-86-5 (Na salt; 131-52-2) Synonyms Panta; PCP, psnchlorol, salt Na pentachlorophenoxide Trade Names (producers) Santophen 20, salt Santoorite, Cowicioe 6 General Information Molecular Formula CSHC1$0, mol. wt 266.35 C - 27.05X, H - 0 38S. Cl - 66 5oX, 0 - 6 01* Structure HONS 020443 Uses Bactericide, fungicide, and sllmicide, primarily used to preserve wood, wood products, and other osaterials. It has also been used as an herbicide. Insecticide, and molluscicide Cl). Thermal Decomposition Mechanisms The following equations represent reactions leading to polychlorinated diphenyl ethers, octachlorodibenzo-g-dioxin, and hexachlorobenzene froe pentachlorophenol (2). Summery of Experimental Studies Reviewed Pyrolysi s Thermal decomposition of bulk PCP at 2S0C for about 12 hr in a sealed tube gave n. 5QS conversion, primarily to 2-(2`,3'.4',6'-hexach1orophnoxy)- 3,4,5,0-tetracnloropnenol (1) plus small amounts or oeta-COO (11); PCP reacted at 360C within about 20 min to give 100X octa*CDD (3). Combustion. Technical grade pentachlorophenol (PCP) or Its sodium salt (Na PCP) may contain chlorinated dlbenzo-g-dloxins (CODs) (hexa-, hepta-, and octa-). Com bustion experiments almost always give detecteble octachlorodlbenzo-g-dioxm (octaC00) In experiments burning technical pentachlorophenol at 515 to BOO*C, with controlled amounts of 0t, maximum amounts of hepta- and octa-COO formed at the lowest temperature; the amount of hxa*C00 was somewhat higher at hightr tempera* ture' Higher amounts of CODs were formed during open burning (mostly hepta- and octa-COO) With only 1 5% Dx, almost twice as much total CODs was formed at 660C as from open burning. Major products in reduced oxygen atmospheres were pentaand hepta-CDQs, the level of TCDO (tetra*C0D) was higher than from the other ex periments {) Open burning of a pure Na salt of pentachlorcohenol gave octa-. -ecta-, anc hexa-CODs in sharoly oecreasmg amounts (5) Comoustion results -ere ,0 HONS G20444 compared for materials (wood or paper) treated with pure Na salt, injure Na salt, or pentachlorophenol The highest amounts of octa-CDO were in combustion products of the Na salt-treated materials, but in the burned residues, high amounts of octaCDD were found in the PCP-treatad 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-CDO, octa- and hexachlorodibeniofuran. decachlorobiphenyl, octachloronaphthalene, pentachlorobemene, hexachlorobeniene, and products identified only by formulas--C9Cle0. C10C1*0, and Cl4Cllo0 (7). These latter formulas may be only frag ments 2.3,7,8-TC0D was specifically said to be absent, but the only CDD detected was the CDD usually present in the highest amounts: octa-CDD References 1. U.S. Environmental Protection Agency. Ambient Water Quality Criteria for Pentachloroonenc1. BS1-117764, Springfield, VA: National TechnicaT'fnformation Service, October I960. 2 G. G. Choudhry and 0. Hutilnger. Mechanistic Aspects of the Thermal Forma tion of Halooenated Organic CoecounOs Including Polychlorinated Dibemo-pDioxins New York: Gordon and Breach Science Publishers, 1983 3 H G. Langer, T p Brady, L. A. Dalton, T. W. Shannon, and P. R Briggs Thermal Chemist-y of Chlorinated Phenols, Advan. Chem. Ser . 120, 26-32 (1973). i B Janssen, G. Sundstrom, and B. Ahling. Formation of Polychlorinated Dibemo-o-dioxins During Combustion of Chloroohenol Formulations. Sc: Total environ. , 10(2), 209"C17 (1978). 5 C Rappe, S. Marklund, H. R. Buser, and H. P. Bosshardt, Formation of Poly chlorinated Qibenio-p-dioxins (PCDDs) and Ofbeniofurans (PCDFs) by Burning or Heating Chlorophenates. Chemosohere. 7(3), 269-2B1 (1978) R H Stahl, R. R, Papenfuss, R A. Bredtweg, and R, w Roberts Stability of Pentachlorophenol and Chlorinated Dioxins to Sunlight, Heat, and Combus tion Advan. Chem. Ser,. 120, 119-125 (1973). 7 S Lahaniatis, E, Clausen, 0. Bieniek, and F Korte, Formation of 2,3,7,6Tetrachlorodibeniofuran During Thermolysis of Selected Chlorinated Orgame Compounds Chemosohere. 14(2), 233-238 (1985) HONS 020445 Section 3 fluorine-containing materials HALAR CASRN 25101-45-5 Synonyms. 1.1 Ethylene-chlorotrifluoroethylene copolymer; ECTFE, Trade Names (producers). Haler (Allied Chemical); General Purpose Malar 300 or 500 or 502 [but Halar 200 is poly(chlorotr1fluoroetftylene), CASRN 9002-83-9), Malar 555 (blown). General Information Molecular Formula. (CH4H4ClF3)n Structure of Monomers and Polymer: CHZ: CHj * CF2: CFC1 ---eCH2CHzCF2CF^C1 Uses The primary use of Malar is for wire ana 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 Lil 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 panel win for comoutars and automatic telephone switching equipment, cathodic pro tection cable, and oil-well logging and submersible pump cable (2) MOAiS 020446 Thermal Decomposition Mechanisms No specific information was found Summary of Experimental Studies Reviewed Pyrolysis No information was found on pyrolytic products from Halar. Combustion No information was found on identified organics lost on combustion Thermal oxidation of a Soviet 1.1 ethylene-chlorotrifluoroethylene copolymer (m p 21SC) gave alcohols, aldehydes, and carboxylic acids at tesiperatures up to 275C Long-term oxidation at 270*C caused profound destruction giving low molecular weight products with aldehyde and carboxy end groups (3). Concentrations of HC1, HF, CO, and sometimes C0Fz 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. 10*. J. Agranoff, Editor New York McGraw-Hill, Inc. , 1982. 2. A. 8. Robertson and E. C. Lupton, Jr "Fluorinated Plastics Cftlorotn- fluoroethylene Copolymers with Ethylene" in: Encyclopedia of Polymer Science and Technology. Vol. Suppl. 1. H. F. Mark and N. M. 8ikales, Editors New York: Wiley, 1976, pp. 279-287. 3 A I Tsvetkova, L I, Tarutina, Ts. S, Dunaevskaya. T V Kreitser, G P ''akarova, ano T, t Celenxova, Structural Changas ,n a Tnfluorocrlorcettiyiene ano Etnyiene Copolymer at Hign Temperatures, Wsoxomol. Soeo n Ser B. 11(12), B85-B88 (1969). 4 H L Kaplan, A. F. Grand, W G. Switier, and S, C Gad Acuta Inhalation Toxicity of tha Smoke Produced by Five Halogenated Polymers J Fire Sci . 2(2), 153-172 (1984). TEFLON CASRN- 9002-84-0 Synonyms Polytetraf1uoroethylene (PTFE). TFE, Polytef, Tetraf1uoroethene nomopolymer, Tetrafluoroethylene polymer, Polytetrafluoroethylene resin (1) T-aae Names (produce-s) Teflon (E I du Pont de Nemours), Huon (1C1 Amer-;as) ; uo-oflex (C), Halcn (unfi'led and filieo) (allied Corporation), FluOrocomD HONS 020447 (fillid) (Liquid Ni trogen Processing Corporation); Tetraloy (filled) (Id Americas); Hostaflon (Hoechst); Algoflon (Montedison), Soreflon (Ugine Kuhlmann), and Polyflon (Oaikin) (3) General Information Molecular Formula' (C,F) (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, mire 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 (X), gaskets, liners, seals, flexible hose; ablative coatings for rockets and space vehicles; chemical process epulpewnt; 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 (X). Thermal Decomposition Mechanisms Teflon depolymen zes to monoeter (CFI;CFI), perfluoroiiobutylene (CF, )tC. CF,], and carbonyl fluoride (COF,). The latter hydrolyzes to give COj and HF (6) Thermal degradation proceeds by homolytic statistical chain cleavage (7) CC; and CF* result from the disproportionation of C0F2 Hexafluoroetnana, CFjCF,, and higher perfluoroalkanes apparently form by reaction of COF 2 with tfie corresponding perf luoroalkenes MOWS 020446 Thi SiF probably arises from reaction of HF with the glass of tha infrared gas cell wall or of the gas sampling tuDe The hydrogen source is apparently trace moisture (HjO) (8). Tn f l uoroacetic acid, CF2C02H, and HF may form In oxidative pyrolysis from tnfluoroacetyl fluoride (9). [Isolated as CF2C02Ca after treating the pyrolyiate with Ca(0H)2 solution, ] The mechanism according to Morisaki (1978) (10) for products having formula <CF2) is as follows - Bf-CF2-CF2-CF2^--a Rf-CFj- + n CF2. 2 CF2. -- CF2:CF2 2 CF2:CF2 FF CFjCF: CF2 + CF2. FF CF2: CFj CF2:----- * CF,CF.CF2 CFjCF, CF2 + CF2 ------a CFjCF2CF-CF2 or (CF2)2C:CF2 and higher homologs and higher homologs FF F--1-------- F---------fr CF, F F-- ,F --F F-| \ f FF Atkinson and Atkinson (1957, cited by Morisaki, 1978) (10) proposed that C2FS is a decomoosltion product of perfluoroisobutylene at > 700C, but stated that such a mechanism cannot be used to produce CjF, or CFt0 C4FS, CsFtl and CsFj0 may coma from decomposition of higher molecular weight f1uorocarsons C2F2H2 and C3F5h may occur from reaction with contaminant water MONS 020449 C0F2 forms from tht reaction of CF2- and 0, Summary of Experimental Studies Reviewed Pyrolysi s The monomer tetrafluoroethylene (CF2.CF2 or C2F^) was an intermediate to major product m pyrolyses at atmospheric pressure (7, 9-11) Major pyrolysis products usually Included carbon tetraf1uoride (CF4) (7,10), octafluorocyclobutan# (eye 1ic*C,F() (9,11), and hexafluoropropylene (CF3CF.CF2 or C3F6) (7,9,10). MorisaKi (1978) (10) reported numerous other pyrolysis products includ ing octafluoroisobutylene [(CF3)2C: CF2] and decafluorobutane (C,F,,,) Hydrogen fluoride was seldom reported as a pyrolysis product (2) At low pressure the monomer was the only important pyrolysis product. Monomer yield hi vacuo was highest near 500*C (96.6X) and decreases with increasing tem perature (91 2OX at 800"C and 78.10X at 1200C) (1) Combustion The flash-ignition temperature of Teflon is 5o0C. the self-ignition temperature is 56Q*C (6). CF4l Si'4, C0F2, and C02 were generally present among combustion products of Teflon and were usually major (9.10.13). Monomer was a major product (60X) from combustion at 700C (13). Monsaki (1978) (10) found hexafluoropropylene (C3F,) to ba the most abundant fluorocarbon from combustion at 450 to 790*C. Tnfluoroacetyl fluoride (CF3C0F) was reported from comoustion at 600 to 650C (9) Other combustion products reported were octaf1uoroproDtne (C,F,>, octafluoroisobutylene {CF4), and octafluorocyclobutane (CF,) (9,10) References 1 M Windholz, Editor Tht Merck Index 10th ec Rahway, H.J. Merck and Company, Inc., 1983, ------ I K. Wiessner Survey on the Toxicology of Poly(tetrafluoroethylene) and Its Pyrolysis Products Ouring Preparation. Processing, and Use Plaste Kautsch , 27(6), 330-333 (I960). J Modern Plastics Encyclopedia, vol 59, ho 10A J Agranoff, Editor New Yorx McGraw-Hill, Inc., 1982. 4 G C Hwle>' The Condensed Chemical Dictionary 10th ed New York Von Nost-ana Remhoid Company, 1981 ; R H Sampson "Insulation, Electric" in Kirk-Qtnmer Encvc ooedia of Chemical Tethnology 3rd ed , Vol 13 M Grayson, Editor New York Intersciencs Puo 11sners a Division of John Wiley 4 Sons, 1981, pp 534-563 HONS 020450 6 J Troitisch. International Pasties Fiammabi11 tv Handbook. New York MaeMi1 lan, 1963 7 H. J, Kretzschmar, D. Gross, and J Kelm, Pyrolysis-Gas Chromatography and Spectroscopic Identification of Fluorine Polymers Anal. Pyrolysis. Proc Int. Symp , 3rd, Meeting Oete 1976. C E. Jones and C A, Cramers, Editors Amsterdam, Hetn. Elsevier, 1977, pp. 373-382. 6 S L Madorsky Thermal Degradation of Organic Polymers New York John W.ley & Sons, 1964 9, H Anto and R Soda. Pyrolysis Products of Polytetrafluoroethylene and Polyfluorosthylenepropylene with Reference to Inhalation Toxicity. Ann Occuo. Hvo . 20(3). 247*255 (1977) 10 S. Monsaki Simultaneous Thermogravimetry-Mass Spectrometry and PyrolysisGas Chromatography of Fluorocarbon Polymers Themocftim. Acta, 25(2), 171 183 (1978). 11 C N, Cascaval and R E Florin. Pyrolysis Gas Chromatography of Some Fluorine-Containing Polymers. J. Fluorine Cham,, 14(1), 65*70 (1979) 12. N A. Xhaltunnskii and N N. Berlin. "High-Temperature Pyrolysis of The-moplastic Polymers" m, Qeoradation and Stabi 1 liation of Polymers vol 1 H H G. Jellinek, Editor Amsterca-, Neth Eisevs- 1967- -p 269-77? 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 Fluormated ethylene-propylene copolymer, Hexafluoropropylene-et-arluoroethviene cooolymer Trade Names (producers): Teflon FEP, Teflon 100 (Du Pont) Gene-al Information Molecular Formula; ^CSF10) [Same elemental composition as PTFE. 76X F, 24% I tin - Structure of Monomers and Polymer Tg-''a<luorot.H'^ieis 5'"/'uOroorooyl6ne or "exa* w.O'3-rooy' en = HONS 020451 uses Teflon FEP Is used for plenum signel end fire ilirn ciola, for insulation for oil well logging cabla, end for a wide variety of otner electric*! nd elec tronic uses (1) Major electric*! uses for Teflon tnd Teflon FEP h*ve been in military electronics, aircraft, and missiles for their space-saving caoabilities Their excellent mechanical and dielectric characteristics allow internal wiring of computers and industrial controls to be miniaturized They are also used m highfrequency cables Fluonnated ethylene-propylene coatings arc applied to polyimide film for cable insulation tapes. After winding of the coated film tape on the con ductor, the assembly Is heated to fuse the lower-melting coating (2) Thermal Decomposition Mechanisms Teflon FEP deoolymeri2es to monomers (3). "Homolytical statistical chain cle*v*ge!` gives uncharacteristic fragments. Pyrolysis of branched CF, groups gives high yields of perf1uoropropylene (CF3CF CF,, CjF#) (4). See discussion from reference B in preceding subsection on Teflon. ms oete-mineo oy thermogravimetric analysis coupled with mass spectrometry r~G-M$) m helium, the first-stage degradation gives mainly CFaCFCF2, which may be liber ated directly or evolved vi* the reaction of CFjCF. and CF2:. C2F4 and C3F# evolu tion at the second stage corresponds to the '-eactions given in the Teflon discus sion Perf1uoro-2-butene or perfluoroisobutylene (C4F#) may b* formed m both stages by the reaction. CF.CF F. + CF, CF,CF,CF:CFj or (CF,),C CF2 Dunne pyrolysis, most C2F4 is formed at 450 to 550oC by the reaction CFjCF:CF2----- CF, CFa * CF, Reactions in air include formation of carbonyl fluoride, carbon dioxide, and carpon tetrafluoride: ZCF, - 0,----- * 2C0Fj 2C0F,----- C02 - CF4 HONS 020452 Summary of Experimantal Studies Reviewed Pvrolysis Major pyrolysis products for Taflon FEP between 400 and 700C war* the monomers CFaCF.CF2 (CaFt) and/or Cf2 CF2 (there ere conflicting reports for results rom similar pyro!ysts*GC experiments) Other fluorocarbons produced included CF,, (CFj)2C CF2 (C4Ft) or CFaCF2CF;CF2 (C^F,}, and perfluorocydobutane (C4Fg) [Morisaki (1978) (5) doubted its presence] (3-6) SiF4 (formed from reaction of HF end glass apparatus with traces of moisture the apparent source of hydrogen atoms), CO, and CO} evolved above 650C (5) Combustion. Major products in moist air or oxygen were CaFgl CF4, S1F4, C0F2, CO}, and tnfluoroacetyl fluoride (CFjCOF) (5,6). However, thermogravimetnc analysis at 400 to 600C revealed no 5iF4 and little CaFg and CF4 Other "combustion" prod ucts at 450 to 790C included octafluoropropane (CaFg, CFaCF2CFa), decaf 1uorobutane (C4F,o), C4F. (none by TG*MS), and cyclic-C4Ft (5) References1 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 lork. Interscience Publishers a Oivision of John Wiley & Sons, 1981, pp. 564*590 3 A J, Pidduck Mass Spectrometnc Analysis of Halogenated Polymers J_ Anal Aopl. Pyrolysis. 7(3), 215*229 (1985). 4 H J. Kretischmar, 0. Gross, and J Kelm Pyrolys's*Gas Chromatography and Soecfoscooic Identification of eluorme solyme-s Anal Qyrolvsis Proc Int iymp , Ire. leeting Cate '.575 R : l. uones ano C. - Cramers. ;d`tors. Amsterdam, Neth . Elsevier, 1977, pp, 373-382 5 S Morisaki. Simultaneous Thermogravimetry-Mass Soectrometry and PyrolysisGas Chromatography of Fluorocarbon Polymers Thermochim Acta. 25(2), 171-183 (1978) 6 H Arlto and R. Soda. Pyrolysis Products of Polytetrafluoroethylene and Polyfluoroethylenepropylene with Reference to Inhalation Toxicity Ann Occup Hvo. . 20(3), 247-255 (1977) TEFLON PFA CASRN [Dependent on particular co-monomer used with tetrafluoroethylene ] Synonyms Perducrcal koxy resin MQNS 020^53 Trade Names (producers) Teflon PFA (E I du Pont de Nemours). Two melt* viscosity grades TE*9704 and TE-9705 (1). General Information Molecular Formula [Oepandant on alkyl group ] Structure of Monomers and Polymer: R1 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 parts 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 haat*exchanger applications (1) Thermal decomposition Mechanisms No soecific information was found. Summary of Experimantal Studies Reviewed Only one article (3) was found on thermal decomposition of Teflon PFA, and it had no exoenmental details. The toxic decomposition product was thought tc be par* tially deg*aded polymer in particulate form References 1 PL Johnson "Fluorinated Plastics, Tetraf luoroethylene Copolymers'* in Encyclopedia of Polymer Science and Technology Vol Suppl 1 H F Mark ano N M Sikales, Editors New York Wiley, 1976, pp 260*278 2 Modern Plastics Encyclopedia. Vol 59, No 10A J Agranoff, Editor New York McGraw-Hill, Inc . 1982 MONS 020*5* 3 R S Weritz Industrial Approach to Evaluation of Pyrolysis and Combustion Hazards. Environ. Health Ptrsptct,. 11, 197-202 (1975). TEFZEL CASRN 25038-71-5 Synonyms: Ethylene-tetrafluoroethylene copolymer, ETFE. Trade Names (producers): Tefiel (modified ETFE) (0u 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' (C4H4F4) n Structure of Monomers and Polymer- CH2:CH2 + CF2:CF2 ------- -tCH2CH2CF2CF24-n 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 saals and other electronic device compo nents (1) It 's soecified for wire insulation ,n U S Navy !1i 1-W-S1822/13. a specification on solderless wrap wire, and in Mil-W-22759/16, /17, /18, and /19, 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 decomoosition 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 noncharnng benavior is typical of a polymer that degrades to low-molecularweight fractions instaad of leaving a residua! carbonaceous skeleton by splitting out small molecules (2) Tefzel produces far less smoke under current overload :-io HONS 020455 than do PVC-nylon, poly(vinylidene fluoride)-jacketed polyethylene, or other simi lar insulations. Two routes are needed to explain the presence of tetrafluoroethylene and vinylidene fluoride (CF2:CH2) in the decomposition products (3). --CFj-CFirCHt-CHJ'CF2-CF2TCH2-CHr- -------- * n CH2 CH2) + m CF2 CF2 l --CF;*CF2-CH2-CH2-CF2-CF2-CH2tCHj- --------> cf2 ch2 Summary of Experimental Studies Reviewed pyrolysis Pyrolysis at 700C for 10 sec gave three major and several other un identified products whose retention times on the gas chroautogram were different from those of other fluonnated polymers. The pattern of minor products was typi cal of that from polyethylene, representing n-alkanes, o-olefins, and o,iu-olefins (4) Combustion Minor amounts of HF were lost during processing at 300 to 320C, but 20*hr exposure to 300C led to - 30* weight loss, at 400C, 40* of the initial weight was lost within 2 hr (5). The only products identified from combust-on in the 530 to 580C range were HF, CO, and C0C2; but some other component was respon sible for the toxicity (6) Random chain scission at 650C for 15 sec gave mostly vinylidene fluoride, CHjiCFj, with minor amounts of the monomers and HF Alkanes, various C3 compounds, and higher boiling substances were identified (3,7) References _ Mooe-n Plastics encyclopedia. Vol 59, No, I0A. J. AgranoTf, Editor hew Yorx' "Mc6raw-Hi11, Inc., 1982 2 R l Johnson "Fluorinated Plastics. Tetrafluoroethylene Copolymer;1' in. Encvdooena of Polymer Science and Technology. Vol. Suppl 1. H. F Mark ana N M, 8ikales, Editors" New York) Wi ley, 1976, pp. 260*278 3 G S Popova, 8. I. Sazhir, and N E Shadrma, Study of Products of the The-mal Degradation of a Tetrafluoroethylene-Ethylene Copolymer by the Method of Dyrolytic Gas Chromatography VvsoKomol Soedin., Ser B. 21(10), 758-761 (1979). -, h J Kretischmar, 0. Gross, and J. Kelm Pyrolysis-Gas Chromatography and Spectroscopic Identification of Fluorine Polymers. Anal. Pyrolvsis. Proc. ]nt Symo , 3rd, Meeting Date 1976. R C E Jones and C A. Cramers, Edi tors Amsterdam, Neth Elsevier, 1977, pp. 373-382 \ S Barron An Investigation of the Effects of High Temperatures Upon Various Industrial Polymers J Fire F1ammaoi1itv. 7(July), 387-400 (1976) MO NS 020*56 6 H L. Kaplan, A. F, Grand, W G. Switzer, and S. C. Gad. Acuta Inhalation Toxicity of the Smoke Produced by Five Halogenated Polymer* J. Fire Sci . 2(2), 153-172 (1984). 7. N E Shadnna, P. 0. Gol'dln, B. I. Sazhin, G. S. Popova, and M. S. Kleshcheva Mathematical Modeling in the Study of Properties of the TFE-E Copolymer by Pyrolytic Gas Chromatography Plast Massy. (9), 47-46 (1981) VITON CASRN- 9011-17-0 Synonym*. Vinyl tdene fluorlde-hexafluoropropylene copolymer; vinylidene fluondehexafluoropropene copolymer. Trade Names (producers); Vlton; Vlton A; Vlton V (E. I. du Pont de Nemours, Inc ), Refset Fluorel; Fluorel (3M) (no additives); Radar Viton; Vlton LM (low-molecularweight); Oai-El (Daikin), Tecnoflon (Montedison). General Tn*ormation Molecular Formula: [Dependent on relative amounts of the two monomers.] Structure of Monomers and Polymer- (had-to-tai 1, mejor) (heao-to-neaa, mi nor) Uses Viton fluoroelattomers are used in gaskets, seals (especially 0-rings), tubing, diaphragms, aerospace and automotive components, high vacuum equipment, low-temperature equipment, and radiation equipment (1) Thermal Decoeioosition Mechanisms No specific information was found. HONS 020457 3-12 Summary of Exprimtnttl Studies Reviewed Pyrolysis Pyrolysis at 800C for 4 sec gave the monomers, tnfluoromethane (CMFj), and hexafluoropropyl#ne-vinylidene fluoride oligomers (2). Pyrolysis at SO to 460C gave CF,C+FCH-CFS (m/z * 163) and other smaller fragments. The stable product was not identified since the mass spectral "fingerprints" of pyroysls pro ducts from other fluorine-containing polymers were simply being compared. Other products included CHFa, MF, and various oligomers and polymer fragments with weights up to 369 amu (3). Combustion At 314 to 41SC, th* major combustion products identified were CO, CMF j, and CHj.CFj plus fluormated C7 to Ct saturated and unsaturated hydrocarbons (4). weight loss wes 60* after < 1 hr at 400C. Volatiles were generated at tem peratures as low as 200C (5). At 850C, combustion gave only CO and COj, no HF, F-contaimng compounds, aldehydes, or carbon aerosols were detected using infrared and gas chromatographic methods (6). References 1. G G Hawley, The Condensed Chemical Pictionary. 10th ed New York,: Van Nostrand Reinhold fompany, 19&1. 2. J T Blackwell. Quantitative Determination of the Monomer Composition in HexafTuoropropylene/Vinylidene Fluoride Copolymers by Pyrolysis-Gas Chroma tography. Anal. Chem.. 48(13), 1883-1885 (1976) 3. A, J. Pidduck. Mass Spectrometric Analysis of Halogenated Polymers. J. Anal Appl PyrolysTS, 7(3), Z1S-229 (1985). fl LA 0ks#nt`evich and A, N. Pravedmkov. Thtrmai Degradation of Po)y(vmy'loene :luoride) ano a Vinyliden# Fluoride Cooolymer with Hexafluoropropylene Vysoxcmoi Soegin,, Ser 3, 10(1), 49*:2 (1?68). 5 S. Barron. An Investigation of the Effects of High Temperatures upon Various Industrial Polymers. J. Fire Flammability. 7{Juiy), 387-400 (1976). 6 i T. Poddubnaya, A I. Eitingon, L. S. Naumova, T A Shashina, and N N, Korobeinikova. Study of the Composition and Toxicity of Thermodestruction Products of Fluorine-Containing Synthetic Materials Gig Samt. . (12), 61-63 (1981). 1. 1 5 HONS 020458 Section 4 nitrogen-containing materials CREOSOTE CASRN. 8001-50-9 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 ) (Z) Ne'sor's C-ecsote Wood "rese-vative (0 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 oil, wasn oil, strained anthracene oil, ana heavy oil These factions ar* blended to give "creosotes" or "creosote oils" conforming to specifications such as Standard PI-78 of the American Wood-Preservers1 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 247Z550C), and heavy oil or heavy creosote (boiling range 285-395C) Besides the c-eosote defined by AWPA Standard PI-78, AWPA has standards for creosote blended with 20, 30, and 40% coal tar (6,7). 02G**9 HGNS Table 4-1 AMERICAN WOOO-PRESERVERS1 ASSOCIATION SPECIFICATION Pl-78 FOR TIMBER-TREATING CREOSOTE (4.5) F-action Distilling S 2.OX S 12 OX 10.0-35 OX 40.0-65.OX 60.0-77.OX Components of Fraction Unidantifiad PAHs Naphthalenes Acenaphthene, fluorene, dibenzofuran, phenanthrena, anthracene Chrysene, fluoranthene, pyrene Olstil lanon Rj < 210 < 235 200-270 < 270 < 315 270-355 < 355 > 355 The chemical 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 other than coal are very different in coaoosition from coal tar creosote VS). The remainder of this aiscussion is restricteo to coal tar creosote Tne word creosote is used unmodified. Creosote's chemical composition has been cnaractenzed by Lijinsky et al (1963) (9). Lorenz and Gjovlk (1972) (5), Nastier (1974) (^0), and others Table 4-2 lists many of the components, but it is not exhaustive. 162 individual components had been Identified by 1962 (10). Creosote contains about 85X polycyclic aromatic hydrocarbons (PAHs), up to 3% tar acids (phenolic compounds), about 5X tar bases (nitrogen-containing compounds), and about 5X benzothiophene and dibenzofuran (S and-0 analogs, respectively, of the PAH fluorene). Five PAHs--phenanthrene, fluor anthene, fluorene, acenaphthene, and pyrenc'-account for about 50X of the mass although several other PAHs have been identified and/or quantitated (5,8-13) HONS 0204i60 Tabic 4-2 COMPOSITION OF COAL TAR CREOSOTE Component. Formula Polycyclic aromatic hydrocarbon* (PAhi) Phenanthren# Fluoranthene Fluorene Accnaphthenc Pyrene Methyl anthracene* Chrysene Methylfluorene* Methylphenanthren** Naphthalene Anthracene Benzofluorene* Dimethyl naphtha)*n*s 2-Methylnaphthalene 1-Me thy 1 naphtha1ena Biphenyl Benz[a]anthracene Benzofajpyren* Benzo[j]fluoranthene Benzo[k]f1uoranth*ne Benzo[e]pyrene B*nio[b]chry*en# Perylen* Unidentified PAH* Acenaphthylene Indene PAH analogs containing 0 & S Benzothioohene Oibenzofuran Tar bases (N-contalnlng components) Acridine Aniline Benzonitrlle Carbazole Indole o-Naphthyl amine 9-Naphthyl amine Quinoline o-, m-, & g-Toluidlne Xylidines 0)4^10 Cio ClaHI0 c14hi0 CHj-C14Hf CHH1S CHj-C13Ht CH3-Cl4H* C10N* On^io (CHa)aCl0H4 CHj-Cv0Ht CHj-C.qH, C.HS-C.HS Oi*Hia CoHia C*oHii Cjo^ia CjoH12 ClaHl4 CJ0Hia C*.Hn* C,H,S Ci-HsO CuH,N C,HjNHa CeH,CN CiaH,N c,htn Cl0HaNMa Ci0H7NHj C*H-jN CHjC,H4NHa (CH3)2C,HaNHa (continued) Concentration, X - 85 21.0 10.0 10.0 9.0 B.S 40 3.0 3.0 3.0 3.0 2.0 2.0 2.0 1.2 09 08 0.3 0.02, 0,3 0,03 0 02 0.02 0.00S 0.004 <2 > 1 S0 <5 20 Reference 10 5, 10 5. I* s 5. T5 5, 10 5. 10 ! ia 1-12 I. 10 5. 10 5, 10 S, 10 5. 10 5, 10 5, 10 5, 10 9 9. 11 9 5 9 9 9 5 12 10. 12 .10 12 5 :o 10 10 10 5, 10 "10 10 1 10 8. 10 8, 10 HONS 020*61 4-3 Table 4-2 (continued) Component Formula Ter iclds (phenolics) Phenol Cresol s Xylenols Trimethylphenols 3-Ethy1-5-methylphenol 2,3,5,6-Tetramethylphenol; Ourenol Naphthols C*Hs0H CH,C(H0H (CH3)sC,HjOH (CHj)jC^h^OH CHj(C,Hs)CtH3OH (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 Tor 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, 66,400,000 gal. creosote-coal tar solutions, and 30,200,000 gal. creosotepetroleum were sold for wood-preserving applications. It 1$ also used as a water proofing agent, a fuel oil constituent, a lubricant for die molds, pitch for roof ing, and manufacture of road binders, ns-t culture" winter wasn oils, cnemicais, 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 then from similar ourr.ing of green wood. The burning proouceo large quantities or olack smoxe lie PAHs determined in the total solid particulate (TSP) included acenaphthene, benz[a]anthracene, acenaphthylene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[b]f1uoranthene, pyrene, chrysene, ben*o(k]fluorenthene, phenanthrene, benzoCg.h,^)perylene, and o-phenylenepyrene (indeno[1.2,3-c,d]pyrene) (listed in approximate order of decreasing yield). Fluorene and naphthalene we-e detected but not quant tated. Product yields ere listed in Teble 4-3 (15) Of the PAHs released by burning, benzo(a]pyr#ne and dibenz(a,h]anthracene are the strongest carcinogens. 8enz[a]anthracene, benzo(k]fluoranth#ne, chrysene, and gphenylenepyrene were the other carcinogenic PAHs identified (IS) Creosote itse has been associated with human skin cancers and is an animal carcinogen, however, creosote-impregnated wood poses little or no danger to humans (1.8) U-J HONS 020462 Tabic 4*3 PAHs IN AIR TOTAL SOHO PARTICULATES DOWNWIND FROM OPEN BURNING OF CREOSOTE-TREATEO RAILROAO TIES DOUSED WITH NO. 2 FUEL OIL (15) Components Formula . Acenaphthene Beni[a]anthracen* CijHjo Acenaphthylene Benzo[b]fluoranthene Benzo(a]pyrcnc CszHa CaoHjj CJ0Hlj Oibtftz^i,h]anthracenc Pyrene Chrysene BenzoCk]f1uoranthene B#nzo[g,h, ijperylen# CiiHi* CJ0Hia CjjHjj Phcnantfirtnc o* Phcny 1 ene pyrene; CjjHjj ~ Indenb[l,2,3-cd)pyrene FI uorene Naphthalene Cl3H10 Concentration in Total1 Solid Particulate, ppm *- 1360-3380 n* 550-1260 - 290-840 ' 10-690 v 10-690 n* 10-690 10-690 % 50-470 v 5-230 v 50-130 v 50-130 v 50-130 Not quantitated Not cuantitated Carcinogenic no yes no yes yes yes no yes no no no yes no susrect aRange 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 Tht Condensed Chemical Dictionary 10th a New York.-. Van Nostranc Neinnoid Company, i81. 2. J H Kuney. Chemcyclqpedia 86. Vol. 4. Washington, DC: American Chemical Society, 1985. 3. R. E. flosselln, H. C. Hodge, R, P. Smith, and M N Gosselin. Clinical Tox icology of Commercial Products. 4th Ed. Baltimore, MO Williams and Wilkin* Company, 1976. i American Wood-Preservers` Association. "Pl-70 (Revised) Standard for Coal Tar Creosote for Land and Fresh Water Use " American Wood-Preservers' Association Standards. Washington, DC, 1978. 5 L. F. Lorenz and L. R. Gjovik. Analyzing Creosote by Gas Chromatography. Am Wopd-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 York.*1 Inter science Publishers, a Division of John Wiley and Sons, 1969, pp 653-582 HONS 020463 j-s 7 0 McNeil "Ter end Pitch" in' Kirk-Qthmer Encyclopedia of Chemical Scence end Technology. 3rd Ed M. Grayson, Executive Editor. New fork: inter science Publishers, e Division of John Wiley end Sons, 1983, pp 564-600 8 US. Environmentel Protection Agency. Wood Preservative Pesticides Creosote. Pentechloroohenol end the Inorganic Arsenicel (Wood Uses) Position Document. 2/3, EPA-540/9-82-004, PB82-229956, Springfield, VA. National Technical Information Service, 1982. 9 W Lijinsky, I Oomsky, G Meson, H. Y Ramaki, end T. Safam. The Chromato graphic Determination of Trace Amounts of Polynuclear Hydrocarbons in Petro latum, Mineral Dll, and Coal Tar. Anal. Cham,, 35, 952-956 (1963), 10 f H M. Nastier. The Characterization of Wood-Preserving Creosote by Physical and Chemical Methods of Analysis. USDA Forest Service Research Paper FPL 195, 1-31, AD 78,4S44/8GA, Springfield, 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 Contam Toxicol . 11C1. 161-166 (1982). 12 D. f. Goerliti, P. J. Colberg, J. L Schnoor, 0 Wanner, A. J 8. Zehnder, and R. P Schwarzenbach Migration of Wood-Preserving Chemicals in Contam inated Groundwater in a Sand Aquifer at Pensacola, Florida. Environ. Sci Techrol , 19(10), 961-968 (1985) 13 M. Windholz The Merck Index. lDth 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. D. 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. JIC'/AHOIAMIDE CASRN, 461-58-5 Synonyms Cyanoguanidine, dicyanodiami de, dicy. General Information Molecular Formula: C2H,N4 Structure- NH It NHjCNHCN 4.-0 HONS 020464 Paper web is impregnated with dicytndiamide and may (1) or may not (2) be heated (a g , 50C for 0,5 hr) to dry Heating in air for 15 hr at 135C may causa some chemical cording to the cellulose (< 20*) N-containing compounds like dicy "block carbonyl groups and inhibit the chain reaction of oxidation and the thermal de struction of cellulose " Ammo groups "block aldehyde groups" (3) Uses' Oicyandiamide 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 1Ignocellulose pulps are comaonly used to insulate various electrical apparatus, t.g. , as dielectric spacers in caoacitors or insulat ing sheet for transformer windings. The entire capecitor 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 lapregnating with N-contaming compounds (such as dicyandiamide or malamine) and/or a protein such as casein or soybean protein (1). Dicyandiamide 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 dicyandiamida is 2X 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 dicyendiemide or on pyrolysis or combustion of dicyandiamide itself References i F S Sadler, P F Hettwer. V H Viet, and C R. Acker (HcGraw-Edison Co ) E^ctrical Irsu'itinc Paoer U.S Patent US 4407697. October 1983, 6 pb C rfestinghousa Elect-ic Corp Qicvandiamide-Impregnated Thermally Stable Elac- t-'cal insulation Paoer Brit Patent 08 1119980, ju y 1968. 4 pp HONS 020465 3 M, B. Samaryanova and V A. Sokol1nikova. Incraasa In tha Haat Resistance of Cable Paper. Soversh. Tekhnol. Bum. . K. A. Veinov, Editor Moscow, USSR "Lesnaya Promyshlennost,1' 1972, pp. 122-131. 4 M. Windholi, Editor. The Merck Index. ICth ed. Rahway. N.J.: Merck and Company, Inc , 1983 5 G G. Hawley. The Condensed Chemical Dictionary. 10th ed New York: Von Nostrand Re inhold Company, 1981 ~ KAPTON CASRN. 25036-53-7 Synonyms. Pyromellitic acid-bis(g-aminopheny1 ether) copolymer, polyimide SRU, Poly[(5,7-dihydro-1.3,5,7-tetraoxobenio[l,2-c 4,5-c']d1pyrrole-2,6(lH,3H)-diyl}1,4-pheny1eneoxy-1,4-phenylene] (9CI); Poly[(oxydi-g-phenylene)(pyromel1itic dnmide)], Benio(l,2-c: 4,5-c')dipyrrole, oeriv , polymer (9CI); Bis(4-ammophenyl) ether-pyromel1 Stic anhydride polymer, SRU; 4,4'-Diaminodiphenyl ether-pyromel1itic acid copolymer, polyimide SRU; A.a'-Oxydianiline-pyromellitic anhydride polymer SRI'. Pol,v[N,N'-(okydi-c-phenylenejpyromel 1 iturnde]; Polyme' SP; poK'N N'-'c r`oxydiphenylene)pyromel1itimida]; Polyimide PM; PN (polyimide). Trade Names (producers)' Kapton, Kapton H (OuPont); Vespel SP-1 (DuPont) General Information Molecular Formula: (C22H10N(Os)n Structure of Monomers ano Polymer- 0a oo Pyromel 1 itic anhydride 0 0 4,4'-Diaminodiphenyl ether e- - 3 HOMS 020466 Uses. Thermoset polyimides ere advantageous in thin-film products Major applica tions are those requiring high quality and performance such as the aerospace and electronics markets Electrical appl1cations--Vespel (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 earners as a substi tute for ceramics, and automotive parts that require thermal insulation such as wires in electric eiotors Kapton film is used in electric motors "where sue is important " It is used to insulate aircraft and missila wire cable, flat fltxible 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-l..,has been used as an insulating matanal in molten salt electrochemical power sources which operate at Internal temperatures in excess of 400C" (2) Thermoplastic polyimides may be used as fibers, film, laminates, or foams Elec trical usas include laminates for printed circuit boards. Cast films art being oevelopea for use in flexible printed circuits and insulation for wire cabl and electric motors (1). Thermal Decomposition Mechanisms Pyrolysis 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 (% 40*) occurs during the first stage (below 700C). The second stage occurs at ' 900C and is associated with *>, 4 6X weight loss (3) Pirst-sttge 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 mtrene and beniyne lntermadiates (3). "Uncyclijed 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 uncyclized ring per 8 to 9 poly mer units Polyamic acids may dehydrate or decarboxylate on heating. Hydrolytic sti5s`cn w th release of C02 may occur wnen wattr is presant. The proposed mecha nism does net account for the presence of methane in the products formed from c-oiysis at 700C Hydrogen may be stripped from aromatic rings at temperatures 6oc: (4) HONS 02046? 4-? The following mechanism was proposed to account for the products formed on pyroly sis at 512*C in nitrogtn Loss of CO* from the imide carbonyl groups leaves free radical -C.N- linltagts, 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 dlmentation and trimerization of benryne Intermediates. This network may be responsible for the very stable, electrically conducting material formed By pyrolyzlng Rapton [conductivity Is 12 (ohm-cm)*1) (3). A large fraction of the original N content is still present after pyrolysis even at 80QC, therefore, graphitization is minimal (6). Combustion. No information was found on combustion of Kapton, but its thermal oxidative degradation at - 400C has been studied. Film aged at 400C m air for a short time undergoes extensive crosslinking during the early stages cf ox.cct Crosslinks are too stable to be amide functions The aryl-ether bond is possibly broken (1). The major crosslinking reaction apparently occurs through coupling of the diphenyl ether units either by a direct dehydrogenation reaction or by cleavage of tie aryl-ether bonds to give phenolic groups that undergo subseduent reactions Tne pyromellitimide ring is degraded, forming phthalimide and other ring structures (&) Curing oxidation at 400C, lots of the diphenyl ether units is the fastest pro cess, with 50% of the units having reacted at only 2 to 3% weight loss. This supports the crosslinking mechanism. Within the first 3 hr, ather cleavage, dehydrogenation, and pyromt*.litimida destruction reactions all proceed at approxi mately the same rate. After that time, the yield of insoluble polyammes remains about the seme, but the yields of soluble aminophtnols and modified pyromeViti mid* units increase up to about 10 hr before leveling off. The polyammes. con taining the ather linkage, art probably intermediates In the formation of the aminophenols. Since these reactions a-e much aster than volatilization loss, me degradation products are from "chemical structures completely different from those of the original polymer " Volatiles come largely from the modified structure (9) o-iO HONS 020468 Besides inducing free radical crosslinking, 02 may react with polymer to give a quinone structure in the aromatic ring attached to the imide N, Further oxidation cleaves that ring to a dlcarboxytic acid, heat converts the quinant structure to a char plus carbon monoxide (5). Summary of Experimental Studies Reviewed Pyrolysis 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 900*C but was associated with only % 4.5% weight loss (3) Weight loss was low (s 5%) after heating for 7S hr at 300 to 35C*C but became "catastrophic" (% 20%) by 400C within 50 hr (10). Heacock and Berr (1965) (11) reported that Kapton completely disappeared after heating at 500C [time not given in secondary reference]. The only machanistic axplanation for the source of the major pyrolysis products, C02 and CO, wet given by Arnold and Borgman (1972) (5), who suggested they came from two imide groups and one imide carbonyl group, respectively. Other inorganic gasas formed at 350 to 700C war* hydrogen (h2), water (H20), and hydrogen cyanide (HCN). Benzene (C4H#), phenol (C^HjQH), and benzonit-i i# (CfH.CN) w*-f reoorted in this range, too Methane (Th4) was rono-te-' in the volatiles after pyrolysis at 700C (4). Two reports mention detection of terephthalonitrile (1,4-dicyanobenzana) [C*H4(Cf<)2] at 350-470C (5) and 600*C (12) Arnold and Borgman (1972) (5) tentatively identified the mess peaks 168-170 as dibenzofuran after pyrolysis at 350 to 470C. Additional products identified by Huomel et #1. (1977) (12) after pyrolysis at 600C ware -ammophenol (H2NC*H40H), phenyl isocyanate (C*HjNC0), phthalimide and five substituted phthalimides, -aminophenyl phenyl ether (H2NC*K40C4H4), three substituted pyromallitimides, and a char. The fact that pyrolysis of Kapton above 700C gives a highly conductive material suggasts that a highly conjugated aromatic networx forms, resulting from dimeriza tion and trimenzation 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 studias on thermal oxidation of Kapton and other forms of the sane polymer focused on the mechanism. Aftar the polymer was heated In air at 300C for 7 hr, 7.9% of its weight was lost, 95% of the loss was evolved 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) Crosslmking accompanied by 50% loss of the diphenyl ether units occurred within 5 hr at 400C while only 2 to 3% of the polymer's i-U wqns q2Q469 weight had Peen lost. At 400C, the pyromellitimide structure degraded before volatiles were emitted (9) References 1 wodem Plastics Encyclopedia, 1965-1966. Vol 62, No 10A J Agranoff. Editor New York. McGraw-Hill, Inc., 1985 2 R P Clark. Thermal Decomposition of Poly(4,4'-oxydiphenylene pyromellit* imide) Thermochimica Acta, 6(5), 473-480 (1973). 3 J W P Lin,A J. Epstein, L. P Dudek, and H. Roeeeelmann Pyrolysis and Electrical Properties of Poly[N,N'-(p,p' -oxydiphenylene)pyro*el1itiaide] Or; Coat Plast Chem . 43, 482-485 (1980) 4 0. P Bishop and D. A Smith. Coeibined Pyrolysis and Radiochemical Gas Chromatography for Studying the Thermal Degradation of Epoxide Resins and Pwlyiendes II. Degradation of Polyimide*. J. Appl Polym. Sci . 14(2), 345-354 (1970) 5 C Arnold, Jr and L. K. Borgman. Chemistry and Kinetics of Polyimide Degra dation. Ind Eng, Chem., prod. Res. Oeveloo , 11(3), 322*325 (1972) 6 PE. Cassidy and N. C. Fawcett. "Polyimides" m: Kirk-Qthmer Encyclopedia 0' Chemical Technology. Vol 18 Gravson. Editor New York inte** science Puolisners, a Oivision of uonn Wiley ano Sons, 1553, pp 704-715 7 R. A Dine-Hart, D. 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 Dine-Hart, D B. V Parker, and W W. Wright. Oxidative Degradation of a Polyimide Film. II Studies Using Hydraiine Hydrate Br Polym. 0 , 3(5), 226*234 (1971). 9 R A Cine-Hart, 0. B V Parker, and W W. Wright Oxidative Degradation of a Polyimide Film. Ill Kinetic Studies. Br Polym J., 3(5), 234-236 !1971) 10 S. 3a--on. An Investigation of the Effects of Hign Temperatures Upon Various Industrial Polymers J Fire Flammability. 7(July), 3B7-400 (1976) 11. J F Heacock and C E Be-r Polyimides--N#w High Temperature Polymers h-film a Polypyromel1itimide Film. 5PE Transactions. 5(2), 105-110 (1965) 12 D. 0. Hummel, H, J Duessel, and H, Rosen. Decomposition Behavior of Thermo stable Polymers as Studied by Pyro-Field Ion Mass Spectrometry Adv Chem Therm. Stable Polvm [Invited Main tact. Int Conf. Therm Stable Polym ], 1st, Meeting Date 1975. Z. Jedlinski, Editor Warsaw Panst Wydawn Nauk , 1977, pp. 99-11B. 13. R 7 Conley and R. A Guadiana. "Thermal and Thermo-Qxidative Degradation of Polyamides, Polyethers, and Related Polymers" in: Thermal Stabi11 tv o' Poivmers. Vol' 1 R. T Conley, Editor New York Marcel Oekker, Inc , 19>C, pp 347-456 14 L C Scaia and W M Hickam The Benavio* 0* Polypyrome11itimioe Res ns a; uicr Temperaiu-es .. appl oiyme* Sc~ . 9. 245-266 1.1965) HONS 0204^0 NITRILE rubber CA5RN 9003*18-3 Synonyms Acrylonitrile-butadiene copolymer; NBR rubber; ni'tM le-butadiene rubber Trade Name* (producers): Paracril (Uniroyal); Hycar (8. F Goodrich) General Information Molecular Formula- (CTH*N)n Structure of Monomer* and Polymer: CHj:CHCN + Acrylonitrile CHjjCHCH-CH,------- --fCHjCH:CHCH2CH3CH)-- Butadiene 'CN Uses; High acrylonitrile content: oil wall parts, fuel tank liners, fuel hose, gaskets, packing oil seals, hydraulic equipment. Medium acrylonitrile content: oene*?1 j-u-r1''* nil-resistant aoolications. shoe so^s, 1`tchen ireti, sink tocp'rs, printing rolls. Low acrylonitrile content: gaskets, grommets, O-rings (flexible at a very low temperature), adhesives. 8inder fuel in solid rocket propellants (I) Thermal Decomposition Mechanisms No information was found. Summary of Experimental Studies Reviewed Prolvsis. Major loentified products after pyrolysis at 390C were NH3 ano HCN (each in -y 5X yield). Traces of hydrogen (Hj), methane (CM4), and C3 to C7 hydro carbons (mostly Cj to C4) were detected in the gases A liquid product (generally produced in y 50 to ' 7GX yield) contained unidentified chain fragments. The resi due was not characterized (2). The monomers were generally detected after pyroly sis at 500 to 1000*C. Czybulka et al. (1981) (3) who pyrolyied nitrile rubber at 500C, gave the most extensive list of other products: HCN; acetonitrile (CHaCN), propiom tri le (CHaCHjCN); and C3 to C,0 hydrocarbons including toluene (CHsCHj), styrene (CsHaCH.CHa), ethylbenzene (C(H$CIHJ), cyclopentene or pentadiene, and pentane At 590C, Shlmono et al. (1980) () found Ct to C3 hydrocarbons; buta diene (CM, CHCH-CHj), acetonitrile (CHSN), and methacrylonitrile [CHa C(CHa)CN] among the pyrolysis products 4-13 MQNS 020471 Pyrolysis at 610C of a nitrile rubber containing 33X acrylom tri la (,,N) gave the monomers (more butadiene [80] than AN), AN dimer and trimer, BD dimer and trimer. an AN-BD fragment, and a BD-AN-BO fragment (5). Monomers and vinylcyclohexene, as a minor product, were determined in the products from pyrolysis at 770C (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 Re inhold Company, 19B1. 2. N Grassie and A. Heaney. Thermal Degradation of Copolymers of Butadiene and Acrylonitrile. Eur, PoTym. J., 10(5), 415-424 (1974), 3. G. Czybulka, H Dunker, H. J. Duessel, H. Logemann, and D. 0. Hummel Studies on Vulcanized ano Uhvuicanized Rubbers with Small Concentrations ot Components (Comonomers, Accelerators, Matal Oxidas, Antioxidants) by Pyro-Field Ion Mass Spectromatry. Anatw. Makromol. Chea., 100, 1-21 (19B1) 4. T. Shimono, M. Tanaka, and T, Shono. Pyrolysis-Gas Chromatography of Butadiena Co-polymers. Anel. Chlm, Acte, 96(2), 359-365 (1978) 5. J. B. Peusch, R. P. Lattimer, end H. L. C. Meuzelear A New Look at Direct Compound Analysis Using Pyrolysis Mass Spectrometry. Rubber Chew Technol . 56(5), 1031-1044 (1983). 6 K. V. Alekseeva end L. S. Solomttine. Identification and Determination of the Quantitative Comoosition of Butaoiene-Nitnle Rubbers py Pyroiytic Gas Chromatograpny. Kaucn. Rezina. (8), 5**-56 (1978). 7 H. D R. Schueddemage and D. 0. Hummel Characterization of High Polymer* by Pyrolysis within the Field-Ionization Hass Spectrometer Advan Mass Soectrom.. 4, 857-866 (1968). NQMEX CASRN: 24938-60-1 Synonyms Poly(i1no-1,3-phenyleneiminocarbonyl-1,3-phenylenecarbonyl), Poly* (immo-m-pneny 1 eneiminoisophthaloyl); Poly(m- isophthalamide), m-Ph*nylenedi amineisophthalic acid polymer, SRU (structural repeating unit); Isophthaloyl chloridem-ph#nylenediamine polymer SRU; Phenylone polymer, Nylon HT 4-14 MONS 020472 Trade Names: Nomex; Nomex 410, Nomax 450, Artsrld KS 305; Aramid K5 105; Contx; Konnekkusu; APH 50. General Information Molecular Formula' (CmH^NjOj^ Structure of Monomers and Polymer, Isophthallc acid (R = OH) Isophthaloyl chloride (R Cl) 1,3-Phenylenedlamine -u uurn rn Jn Nomex Uses: Nomax paper, with or without mice flakes. Is used to insulate high perfor mance electrical motors, special transformers (t.g. , high-voltage dry-type trans formers), end aircreft generators. The nonmelting, self-extinguishing Nomex paper is useful up to 190*C Noeiex 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 Pyrolysis Water loss may occur from chain crosslink-ng during Nomex pyrolysis at 300 to 40QeC. Possible reactions are condensations between terminal amino and carboxyl groups, between chain aatide or amino end groups and carboxyl groups, be tween amide and isoimide groups (tautomeric forms of amide groups), and between two carboxylic acid-terminated chains to give anhydrides. In this temperature range, decarboxylation of end carboxyl groups is the most likely explanation for carbon dioxida evolution (5,6). At leest some, if not all, of the water evolved below about 4Q0C is probably due to water adsorbed by the polymer (6. 2) 4-15 MQNS 020473 Products appearing at 400 to 430C--benzoic acid, 1,3-phenylenediamine, amine, benzanilide, and N-(3-aminophenyl)pizamiae--can be accounted for by hetero lytic degradation of chain end and penultimate amide groups and by homolytic amide bond cleavage. Beruomtnle, which is also produced in this range, forms from homo lytic 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 H:0 ] The latter sequence of reactions could also give additional aniline, benzanilide, and N-(3-aminophenyl)ben:amide (5), Oehydration of amide groups can also account for formation of 1,3-dicyanobenzene (isophthalonitrile) and 3-cyenobenzoic acid (6). At 475 to 500*C, 1,3-dicyanobenzene is evolved, probably from the same kind of reaction seguenct that produces benzomtn le. Larger amounts of water an also evolved (5) Ehlers et al. (1) proposed a major route for tht initial thermal degradation of a-amids that involved cleavage of the C-C bond between the aromatic ring and the carbonyl group carbon to give an aromatic isocyanate. Brown and Powf-* (5) consid ered this mecntnism unlikely since no isocyanates were detected in tne proouc.s Chatfield et al. (6) did not consider isocyanate formation at all. The following reections were proposed by Chatfield et al. (6) for thermal degrada tion of Nome* (I), [Hote: In all formulas, CaH4 represents en -phenylene group --=-NHC0CeH4C0NHCeH4 rn 1) Cleavage^ 2) H atom abstraction ---NHC0CgH4C0NHj + CH----(II) H Dehydration^ -nhcoc.H^CN - NCC*H4CN * H,0 1,3-Dicyanobenzene I + H.O -----------------> -NHC0C*H4C02H + h2nc6h4- * III Decarboxylation ,,NHCCr6Hs IV * C02 Hi 1) Cleavage `--------------^ NCCsH4C02h 2) H atom abst-action j-Cyanobenzoic acid **16 HONS 020474 I Cleavage^ . NHC0C*H4C0` * IV NHCSHNH IV ------------------ > ~whcoc*h4' + CO Combustion. Molecular oxygen apparently reacts extensively with Nomax during thermal degradation in air. For example, at 550cC recovered products contained *2.SX oxygen based on the weight of the original sample, whereas the original sample contained only 12 S% oxygen. CO, C0a, 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 Nomtx pyrolysis according to most reports. Ehlers et al (7) and Chatfiald et al.(6), however, reported that thorough drying of Nomex samples before pyrolysis would preclude water loss during pyrolysis, et least up to 3S0eC, Hydrogen and hydrogen cyanide ware major inorganics evolved from pyroiysis acove 500 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 S00*C were benzene, toluene, banzomtrile, 1,3-phenylenediamine. benzoic acid, and aniline. Above 500C, toluene became a minor product and 1,3* dievanobenzene became a frequently determined, and often major, product N*(3Aminopneny i Ibenramiue ana 1,3-pnenyieneaiamme were najor prooucts -`rom oyroiysis at 600 and 700eC. Trace to amor organics reported included Cj 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 end 550C. Loss of most of the hydro* gen and cxygen by 1,00DC left a cha- whose molecular formula approximated C,3NH The chamea residue comprised apout 50X of the original polymer weight after 4 min at 1,000C under helium (6,8) 4*17 MOHS 020475 Product* and their yield* for the temperature ranges 300 to 481C end 500 to 1,000`C ere given in Tables 4*4 and 4-5, respectively Combustion During thermal degradation tn air or oxygen, Nomex lo*t weight rapidly in the range 400 to 6Q0#C and wa* entirely consumed by 1,000C (6) Volatile prod ucts recovered from degradation at 300 to 1,000C were primarily water, carpon dioxide, and/or carbon monoxide. HCN at 1.2 weight X (based on the weight of the original sample), acetone at 4.2 weight X, and an unidentified compound of molec ular formula Cl0H12 at 7.2 weight X were recovered from flaming combustion and represent the only other product* 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 alkenes, mtromethane, NO. H20, and cyanogen comprised most of the remaining combustion products Gets'is are given in Table 4-6 HONS 010476 Table 4-4 NOHEX PYROLYSIS BELO" 500C f* fh.*( k *>* !!iili*#*>-'' .1*1 > nm ""*wsij 5 4 IT tl** Hrf |ln hl-Mbp tl bi IMIIA- t****( n w* rttkw't it ** J*l *! 1% ' > aaq ^ _l IB* IMK* -- *h n m**' Mm nl^ in H1 HONS 0 2 0 4 7 7 '**f4 v> (rlfln' l# I. t ba, n IN* 1t 1xl Table 4-5 imHrx ptrnoLfsis at soo to ioooc ainp *** ImhI) t*"t I # ^ tt4*t M lLAf * *1-|*rin ]9W||* 01 01 - 01 __ ( ( Jitf4c' |fttM Ita at* 0) lire -P WPfMl 1PI<N (ire Tt 1% all- N tK I la w/w*pi.r*-e ** rt~ I *** let *1- 21 wr* ' M U ill .w -OU, __Ol __ _ 1*1 _ _tl_ . <p*t lakatlln tra hi^ (Hi WIM ml*Wh (mPm MailAl (aiha hr^Ht" U' a^any (tn|!V IfHVff* A*+*at# C* ta, a M K* If M / 4 4 4 UIj *SnI tt tf n it na pJ**n !* IltAewr* *l f*4`4p'(aC iltl*l|**rf Wa(ar 111)1*4 aiP>* HrlUx c4 HlaafllHM NalfSaa* `V*i c,4 p p1 klPrl<w M. (* o t#a lalMf C,i# AlU 14 **fW fU/CM, in k K laa* lfl anwil IMAM AiiPwiitm %rta*H#llr V IriMlIrllt i a* 1 laltaPlilPi <M CB.f* Olg (ft* (^n * <4*S Ila'K*ornI ItKIl PI* Alw m*# lalww at Irlra* l>*nh m 14 litpANalit wH IntMlIlIU Pfctwl toltlM 1 f PPta|Tw4lMlNa t PahaM|lMWf I ta**a?1dfltr 1 1 ItfrM^iait^ 1 Cy*M*+>> 1 inlMiirll* T fl*p*|in*l* M (|I| MS <A. #"K>Pa (A(liK (A(naii faa*P (4tM IA Ctft.fr, tAIOI* (* (au TRjt^l (.,, inii* lalfia '>*1* Im in in JHr. n*t" i* m - * in -PM a IPI U}A HMalll* tA'MA <P taPM**rll tmiaalAi HONS 0 2 0 * 7 6 HONS 0 2 0 4 7 9 Table 4-5 (continued) r. II tl I )` kn]il* (raMllIllpryttla*Uf cji.mi, tn----- nrvt --w-wc IwMlwdfiH l > (iiitf t* r*'i) t n *V .1*1 -,,ii _ _l*l_ i*L *( lWt I* < I Slit* H *fkftul H IN* liltl *lfM fmi4i dwd ** mm < *4 * b< wt rNI Uni4Nt rHHffNl rKipi 4t'4 h(M V fKtft <4(H tM(4 M* -< I vr ***<r U* _ *~rnt*l*itn^t#ii_<__n__r_r J jj p r |jj o X in o fNJ o * CP o Table 4-6 NOHEX COHRUSTWifl Pi tat M| wl^t hit Mfti MIN *-l*ili |M MU*v WIM iMMfhtw (*M* MMlft CrM* Mf %** fVrt mIHpThI* Mlkit ul* (t l C, t*f**lri iMfth (ft & H fttft ar ivibw alii wa mm fe rlflaif (!**(- *XI, lielllMr* hllb ft M fa tlft* lita RrelwIlilU IrtflftU'll* 1 hfftt'Kf 1 * ? MftM'llf ImtHt hlmr * lyltft SlffHt ftiHittfw i* * * pmieipiwn IMfftltlN nal lNMft K laf ItMftalli M| 1 1 ftlfMMftl--- hlftlt'lli ) (ift^t.rth c li ii, (|ft{ (.* Uii flyllft **, CftfPftTft, CM* (,! IK, Clftft (jftttft U*. (Ad, C^tCft.l, l^tii (a, C.**C,h. (4l.n1 (A^. oAl,(a Pac.ft.Ci it iii* tM| tn I IK Iptt'ftof t*l lift* !* nr( ** . J* wrt I alb1 ll 4 * sin * * HU ,, ' /si nw ti m i ft 1u s4s*<c Ti)4 4in|*.*<( mfi**(; n nu HmI*! ~ H t ' *S i i n ii in*J. tfftKsinl w** * H a* / H1 IfMVt' un c) n* / ** *n i ft iv n r rt i it > it > It a in - * it I'M*.* irMt ft wt' ll Mil If Hit* lir* l'**tt* N** VI* l'|t **m** ;/ Itrfim**. ft 141* l'rtV i *n* / \ It in in i fitm in v PI li i i i it i ltm i it* i pi in in i* 4|it *. ** I *(** wi^l %4r4 n Ht | |] |.(|| >tl|(|r , '*4 tM. Ih | *hn| |*l ail 1 * *r/.M H Reference* 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, 1981, pp, 534*563. 2 J Preston. "Aramid Fibers" in' Kirk-Qthmer Encyclopedia of Chemical Tech nology 3rd ed. , Vol. 3. M, Grayson, Editor. New York. Interscience Publishers, Oivislon of John Wiley & Sons, 1978, 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 6 Sons, 1960, pp. 146'166. 4, L 0 Kaser Dry-Type Transformers in the United States. Paper presented at the 4th 8EAMA International Electrical Insulation Conference, Brighton, England, Hay 11, 1962. 5 JR. 6rown and A. J. Power. Thermal Degradation of Aramids: Part 1*Pyrolysis/Gas Chromatography/Mass Spectrometry of Poly(l,3-phenylene Iso* phthalaende) and Poly(l,4-pheny1ene Terephthalamide). Polym. Degradation Stab.. 4, 379-392 (1982). 6 DA. Chatfleld, I. N. Einhorn, R. W. Ml eke Ison, and J. H. Futrell. Analysis of the Products of Thermal Decomposition of an Aromatic Polyamide Fabric j Pa 1 vm trj Pcivfi r^m Ej ; I7t 1367-I7P1 ''197?) 7. G. F. L. Ehlers, K. R. Fisch, and W. R. Powell. Thermal Degradation of Polymers with Phenylene Units In the Chain. IV Aroaietlc Polyamides and Polyiaides. J. Polym Sci.. 8(12), 3511*3527 (1970). 8 Y. P Khanny, E. M. Pearce, 0. T. 6. Saiith, H. Surkltt, H Njuguna, 0 M Hindenlang, and 8. 0 Forman. Aromatic Polyamides. II. Thermal Degradation of Some Aromatic Polyamides and Their Model Diamides. J, Polym Sci., 19, 2817-2834 (1981). 9 E P, Krasnov, V. H. Savlnov, L. 6. Sokolov, V I. Logunova, v K. Belyakov, and T A. olyakova. Thermal Degradation of Isomeric Aromatic Polyamides YvsQKomoi Soed. , 8(3), 380-286 (1966). ID. H J. Kretischmar end D. Gross. Pyrolysis-Gas Chromatography of Polyamides Kunststoffe, 65(2), 92*94 (1975). 11, P Perlsteln, Identification of Fibers and Fiber Blends by Pyrolysis Gas Chromatography, Anal. Chin. Acta. 155, 173*181 (1983) 12 L. . Reshetnlkova, L. I. Slyusareva, T. N Shuvalova, and S. I Kirsh. Analysis of the Composition of Polymer Material Combustion Products by Gas* Liquid Chroaiatography. Fii -Khlrn Osn. Sint, Pererab Polim.. 3, 96*101 (1978) 13 M Day, T, Suprunchuk, and D M Wiles. A Combustibility Study of tne Gaseous Pyrolyiates Produced from Some High-Performance Fabrics J Appl Polym Sci , 28(12), 3681-3693 (1983) 4-23 HONS 020481 NYLON 6 :ASJ?N; 25038-54-4 Synonyms. PolyCiminocarbonylpentamethylene); polycaprolactam; polycaproamide, caprolactam polymar Trade Names (producers). Capron (Allied Corp ); Fosta (American Hoechst), Lilt rami d (Badische Corp.), CRI (Bemis Co,), Firestone (Firestone), Enkalon, Crilon (Emser wrk*), Mirlon; Perlon, Phrilon; Amilen (Toray Ind,, Inc,), General Information Molecular Formula; (C*HuN0)n Structure of Monomer and Polymer- c-Caprolactam Nylon 6 Uses, Nylon 6 is used in bearings, gears, bushings, coil forms, brush backs, tubing, and tape (1). It is widely used m meat packaging (2) Nylon plastics are used in numerous consumer products, including tire cord, fishing lines, tow ropes, garden hose, and wovtn fabrics (3). In ganeral, nylons have their biggest -ar-ers -n tne automotive Industry for aoplications such as electrical connectors wire jackets, emission cannisters, ano lignt-auty gaars Electrical ano e-act-cric applications use large amounts of nylons. Fire retardant (UL94 V-0) nylons are usea in th* electronic and electrical fields. Nylons are used for plugs, connec tors, wire devices, terminals, cable ties, wfre jacketing, antenna mounting de vices, and power tool housings (2). In wire and cable applications, nylons are used as jackating unda-which tha primary insulation is polyethylene or poly(vinyi chloride) (4), Thermal Decomposition Mechanisms Based on mass spectral data, water elimination (-18 amuj, loss of the acid a.nee group (-44 emu) after rearrangement, and loss of methylene groups from longer oo'.amides (-42 or -55 amu) by cs*lmination form most of the decomposition products HONS 020482 Polyamides end copolyamides with a large number of methylene groups favor decompo sition by cis-eliainitlon and cleavage of the amide bonds (S) 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 Pyrolysis Recent reviews list thermal decomposition products of polyamides as carbonaceous residue and volatile products such as NH3, nitriles, amines, cyclic ketones, esters, CO, C02, H20, hexamethyleneimine (haxahydro-lH-azepine), hexylaenne, heptylamine, and methylamina (7,8). Ohtam et al (1982) (9) gane rail zed about the kinds of products generated from pyrolysis of verious nylons ct 550C. The major diffarencas ware that cyclopentanone is a prevalent degradation product if adipic acid was one of the starting materials and that those mononitriles formed that contain one amioe group nave different structures depending on the starting materials If the nylon has been manufactured from an ur ami nocarboxylic acid, tne mononitrile with one amide group has th* CN group in the N-alkyl portion of the molecule (I end II) CHl(CH1)||tCONH(CHj)nCN (I) CH,:CH(CH,)m_,CONH(CH,)rCN (II) If the nylon is a condensation product of a diamine and a dicarboxyl'c acid, the mononitrile with one amide group has the CN groups in the carboxylic acid group of the amide (III and IV)- CH3(CHa)^NHC0(CHj)nCN (III) CH,'CH(CH,)m^1NHCO(CH!)riCN (II/) Other products of nylon pyrelysis iclude saturated hydrocarbons, a-olefins (which give the strongest intensities of tne hydrocarbons), uj-dienes, monomtnles with either a saturated carbon chain or an j-olefln chain, lactams, dimtriles, and HONS 020483 hya roc a roo ns with on* amiae grouo with an w-double bond in me carooxyi grouo ana with or without an w-double bond in th* alkyl substituent (9) Pyrolysis of nylon 6 (polycaprolactaei) at 530C gave a strong peak for caprolactam and lesser peaks for C9 mononitriles and for monom tri les with one amide group (91 Other studies report nylon 6 pyrolysis products that include caprolactam dimers. trimers, tetramers, etc (10,11) [at 30 to 400C] Sahr et al. (1964) (5) found oligomers containing up to 16 repeating units (M) in the pyrolysis products from nylon 6 degraded at SO to 600C Most products took the forms [M31| * Na]*, [M K]*, and [M H]*. Th* most abundant [M + Na]* had n * 5 to 7 n+ n n* Na~* H20] , the most abundant species had n * 6 or 9. For [m 'i ~ Combustion No specific information was found on nylon 6 combustion products The flash-ignition temperature of nylon 6 is 420C, th* self-igmtion temperature is 450C (7) References 1 J. E. Hauck, Editor 1974 Materials Selector Vol 78(4), Stamford, Conn fiemnold Puclishir; Conpa-y, 1?L: 2 Modern Plastics Encyclopedia. Vol, 62, No 10A. J. Agranoff, Editor New York: McGraw-Hi11, Inc., 1985 3 M Windholi, Editor. The Merck Index. 10th ed. Rahway, N.J Merck and Company, Inc., 1983 4 R J Welgos. "Polyamide Plastics" in: Kjrk-Othmer Encyclopedia of Chem ical technology. 3rd ed., Vol. 18. M. Grayson, Editor New Yorx. Inter science Publishers, a Oivision of John Wiley and Sons, 1982, pp. 406-425. 5 u 8ahr I. '.ued*"wald. 9. Mueller, and H. 9 Schulten ?vrolvs*.s F-e'd jescrction Mass Soect'onetry of Polymers III 41;onat*.c 5oiyamaes Anoew Makromol, Chem.. 120, 163-175 (1984) 6 h. H G. Jelllnek and S. R. Ounkle. "Hydrocyanic Acid Evolution from Poly amides, Polyurethanes, and Polyimides and a Survey of Their Thermal ar. Oxi dative Degradation" in. Degradation and Stabi1ization of Polymers Vc1 1 H H G. Jellinek, Editor. Aaistergam, Neth Elsevier, 1SS3, pp 66-161 7 J Troitisch. International Plastics Flammability Handbook New York MacMillan, 1983. e R. E Putscher "Polyamides" m Kirk-Dthmer Encyclopedia of Chemical Technology. Vol. 18. M Grayson, Editor New York- Interscience Pub lishers. a Division of John Wiley and Sons, 1982, PP 328-371 4-26 HONS 020464 9 H Ohtjm , T. Nagaya, y Sugimura, and S Tsuga. Studias on the Tnermal Oegredetion of Aliphatic Polyemides by Pyrolysis-Glass Capillary Gas Chroma tography. 3, Anal. Appl. Pyrolysis. 4(2), 117-131 (1982). 10 RE. Adams. Positive and Negetive Chamical I on nation Pyrolysis Hass Spec trometry of Polyaiars, 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 Poly(haxamathy1ene adipamide); hexamethylenediemine-edipic acid copoly mer; poly(iminocarbonylbuty1enecarbonyl iminohexemethylene) Trade Names (producers). Celanase (Celanesa Corp.); Zytel (DuPont), Vydyne (Mon santo), Maranyl (Imperial Chemical Industries). General Information Molecular Formula- (C,-,H*--N*,0--) n Structure of Monoaiers and Polyawr: H2N(CHj),NHa Hexane thy1enediamine K0aC(CHa)4C0jH Adipic acid Usas Nylon 6,6 is used for beerings, gears, bushings, coil forms, brush backs, rod, and tubirg (1). Thermal Decomposition Mechanisms General information for nylons is discussed under nylon 6, above Cyclopantanone may be produced after chain scission of the carbonyl-nitrogen and methylenecaroonyl links give the requisite 5-carbon precursor or from cleavage of an endgroLic adipic acid followed by decarboxylation and cycluation Hydrolysis gener ates some of the products At lower temperatures, cnain scission predominates, with production of cyclopentanone and CO Temperatures around 60OC produce 4-27 HONS Q204B5 cyclohexane, olefins, and fragments with intact amide group* (all fragments with m/a 140). Jellinak and Dunk)* (2) presented the following schema for thermal degradation of nylon 6,6: Lower temperature*: O' ' 0 . 0 1 o * II II (I r^C -- NH(CH2),NH^C(CHa)4 --CNH ~r (CKa), -- KHC-- 'I -'NH(CH2)6)NH' * C(CNj)3CHi * CNHCCH2)#NHC~ *~CNW' a CMCH.MHC--' I II III IV " V *H I - -- NHj(CHj)#NHj m co NH(CHa),NHC 0 HaN{CHa),NHC ^ IV HM 0II IV ------ v'CNHj --cn + h,o 0 ii R1C0jH f? CHa:CH{CHa)4NHC l-i 0 stC0i.H * 4*NH. R1H + CCa Higher temperature* (> 600C): 0. li 00 i> u 0 II CNH --CHj -- CH2(CH2)4NHC(CHj)4CNH(CHj)sNHC -- 00 HCN * -"CNH, + ---CNH--(CHa), -- NH-- a CHj VI 0 II --CNH, C + NHa or -UN * HjO oVI and/or CH, CH(CH,)*CM3 a h20 * -*CN ~-28 HONS 020*86 Summary of Experiment!1 Studies Reviewed Pyrolysis. Ohtani et il. (1982) (3) found cyclopentanone as the iwjor nylon 6,6 pyrolysis product at 550C Minor products include caprolactam and a C, dinitnle 8ahr et 1. (1964) (4) pyrolyied nylon 6,6 at SO to 600C, identifying peaks corre sponding to [Mj_s * h] , [MjiS * Na] , [Mj * 2Na]i+, and a very weak [M + Na - h20] Main fragments corresponded to (M + Na - 44] + , im * Na - 04]"" and IM * + 2 n '' 1n Na - 110) where 44 is a loss of CONHj, 84 is a loss of (CHa)4C0, and 110 is a ' loss of (CHa)4C0 and CN. After Burns and Renschler (1964) (5) pyrolyied nylon 6.6 yarn at 500C, they identified major products as cyclopentanone, adipomtrile (ten tatively), and a ''composite of caprolactam and an apparent homolog u Adams (1983) (6) reported the presence of the following mass spectral peaks (abun dance relative to cyclopentanone as 100X) after nylon 6,6 pyrolysis at 30 to 400C 143 (16X), 183 (15X), 22? (IBS) (227 is the weight of the repeating unit), 343 (47X), 369 (31X), 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 reports identified them by mass spectral ana'vsis) Combustion Jellinek and Ounkle (1983) (2) studied the evolution of HCN from ny lon 6,6 films during flash degradation at 289 to 69SC in air. The amount of HCN evolved reached a maximum of 14% of theoretical at500C within 16 min. At 695C, HCN evolution was much less than 1% of theoretical because of its oxidation, which began at 575C. References 1 v e Hauck, Editor 1974 Materials Selector Vol 78(4) Stamford, Conn Remhold Publishing Company, 197$. 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" in1 Degradation and Stabilization of Polvmers. Vol 1 H H. G, Jellinek, Editor. Amsterdam, Netn. Elsevier, 1983, pp 66-161 3 h Ohtani, T. Nagaya, V. Sug'mura, and S Tsuge, Studies on the Thermal Degradation of Aliphatic Polyamides by Pyrolysis-Glass Capillary Gas Chro matography. J. Anal Appl Pvrolysis, 4(2), 117-131 (1982) 4 L) Bahr, I Luederwald, R Mueller, and H. R Schulten Pyrolysis Field 0-sorption Mass Spectrometry of Polymers III Aliphatic Polyamides Rr. Mak-omol Cham , 120, 163-17S (1984) 5 F . Burns and C L Renscnle- Monitoring of Degradation of Thermally Age; Nylon 6,6 II Pyrolysis*Gas Chromatography J Aopl Polvm Sci , 28(4; , 1133-1139 (1964) HONS 02048? 6. R, E. Adams. Positive and Negative Chemical Ionization Pyrolysis Mass Spec trometry of Polymer*. Anal Cham,. 55, 414*416 (1983). NYLON 6,10 CASRN 9008-66-6 Synonyms: Hexamethy1enediamine*sebacic acid copolymer Trade Names (producers). Tynax General Information Molecular Formula. (CteH3oN302)n Structure of Monomers and Polymer: HjN(CHj)#NHj Hexametnylenediamine H02C(CHj)(COjH Sebacic acid --fMHCO (CHa)(CONH(CHj )s JjjUses- Jacketing for wire and cable, special molded parts (1). Thermal Decomposition Mechanisms No specific information was found for nylon 6,10. Summary of Experimental Studies Reviewed Pvrolysis. Ohtani at al. (1982) (2) found the following compounds in the products from pyrolysis of nylon 6,10 at 550C. caprolactam, Ct to C4 hydrocarbons (C6 major), Ct to Ct mononitriles (C4 major), 1,10-decanedimtrile, and C14 to ClS mononitriles with one amide group (Clt major) Combustion. No specific information was found. References 1 J E. Hauek, Editor 1974 Materials Selector Reinhold Puolishing Company, 1973 Vol. 78(4) Stamford, Conn J- ir. HONS 020*88 2 H Ohtani, T. Nagaya, V. Sugimura, and S Tsuga Studies on tn* Thermal Degradation of Aliphatic Polyamides by Pyrolys1s-Glass Capillary Gas Chro matography. J. Anal. Appl, Pyrolysis. 4(2), 117-131 (1982) NYLON 11 CASRN' 25038-74-8 Synonyms. Poly(w-undecanamide) Trade Names (producers): Rilsan (Rilsan Corp.) General Information Molecular Formula. (CjxH^NO) Structure of Monomers and Polymer; HjN(CHj)1oC02H ur Amtnoundecanoic acid -fNHCO(CH2)10-J^Nylon 11 Uses: Electrical insulation and other nylon uses where low moisture absorption is needed (1). Mainly used for pressure moldings and fibers (2). 'harms 1 Decomposition Mechanisms No specific information was found for nylon 11 Summary of Experimental Studies Reviewed Pvrolysis Ohtani et al. (1982) (3) pyrolyzed nylon 11 at S50"C The lactam pro duced from undecanamide gave the weakest peak. Other weak peaks were ascribed to C14 to C-o mononitriles with one amide group and C3 to C2l hydrocarbons with one amide group Intermediate-to-strong peaks were ascribed to C to Cu mo-onitn les with the C:t species predominant. C and CT hydrocarbons were the mast abundant of s11 species identified. Ca to C10 hydrocarbons were present in intermediate abun dance Co-ibustion No specific information was found 4-31 References 1. J. E Hauck, Editor. 1974 Materials Selector Reinhold Publishing Company, 1973 Vol 78(4). Stamford, Conn. Z RE Putschtr. "Polyamides" In: Kirk-Othmer Encyclopedia of Chemical Tech no logy. Vol. 18. M. Grtyson, Editor. New rork: Interscience Puoluntrs, a Oi vision of John Wiley and Sons, 1982, pp. 328-371. 3 H. Ohtani, T. Nagaya, Y Suglmura, and S. Tsugt. Studios on the Thermal Degradation of Aliphatic Polyamidas by Pyrolysis-Glass Ctplllary Gas Ch-omatography. J Anal. Appl. Pyrolysis. 4(2), 117-131 (1982). POLYURETHANES CASRN. Dependent on monomers Synonyms Urethane polymers General Information Molecular Formula: Variable Structure of Monomers and Polymer: Polyurethanes contain the carbamate or ure thane group -NHCOO* and are produced by reacting diisocyanates, e.g., toluene2, 4-diisocyanate [CHjCeHjtNCOJj], with a so-called polyol or macroglycol based on polyethers and/or polyesters or with a combination of macroglycol and a shortchain glycol extender. Linear, thermoplastic polyurethanes may have the general structure: 00 i * -fCOCNHC CNHCOJ^-' ill J Cross linked theneoiet polyurethanes are prepared from isocyanates and polyols of functionality > 2. Crosslinking can also occur from secondary reactions to give urea linkages [-MHCONHj and biuret linkages [-NHCON(CONH-)-]. The latter reac tions are common in water-blown polyurethanes (evolving C05 acts as a blowing agent) (1). Rigid foams are derived primarily from polymethylene polypheny) isocyanate (PMOI). often linked with polyester polyols Rigid foam from PMOI is preferred for commercial refrigeration Insulation, but household refrigerators use a rigid foam based on toluene diisocyanatc (TDI). --32 HONS 020490 PMQIs are crude product* containing 40 to SOX 4,4'-*ethyl*nebis(phenyl isocyanate) (HOI) Pure MOI is used in elastomers. OCN CHj NCO MO I Flexible foam* are primarily bated on polyether polyol*. TDI, PMOI, or PMDI-TOI i.e^a a-e c'tfc.i c: V't ';rr. arete About SOX of polyurethane coating* are based on TOI with polyether* or polyesters Polyurethane alkyds, moisture-cured polyurethanes, and self-cross 1 inking aqueous polyurethane dispersions arc other coating types (1). Uses1 Flexible polyurethane foams are used in furniture, transportation, bedding, cerpet unoerlay, textile laminates, and packaging (listed here in order of decreas ing U.i consumotion in 19811 Rigid foams are used in building and construction. refrigeration, tarn, and pipe insulation, transportation, packaging, ano fur- ture (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 several other synthetic resins are available for the purpose, polyurethanes or epoxies are chosen when chemical resistance is important (Z) 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 bean studiec (3) A European reference (4) listed polyurethane among commercially jjai'a; e organic caols msulatior and jac<et mate-'s's HONS 020491 Thermal Decomposition Mechanisms Thrae pathways wart propostd by Saun<j*rs (1959; citad by Hileman at al , 1975) (S) (a) dissociation to tht original polyol and isocyanatt; (b) cltavagt by a concerted reaction, producing a carbamic acid (which further decomposes to an amne and C02) and an olefin from the polyol; and (c) loss of C02 probably accompanied by intra molecular recombination of the olefin and primary amine to give a secondary amine When Hileman et al. (1975) (5) pyrolyied a polyol-TOI polyurethane, only pathway (a) appeared to be operative below 300C. Pathways (a) and (b) were operative above 300*C plus other secondary decoaipositions Lack of volatile secondary or tertiary amines seemed to indicate that if pathway (c) were operative, it occurred without polymer chain cleavage. Grayson et al. (1982) (6) proposed the following scheme for combustion of polyure thane foams: Polyurethane j heat --* Char heat Isocyanate Yellow Smoke 0, heat heat Alkenes Alkynes H-.0 Polyol H;0 ' Da heat Aldehydes Ketones Acids r neat -r Black Smoke HCN + ch3cn CH-. CHCN, etc Summary of Exoarimental Studies Pcviewea All tha information found was on flexible oolyurethana foams, ir jtlv based on TDI and polyether polyols HONS 020492 Pyrolysis. At 300C, flexible polyurethane foams based on TDI and a polyether polyol avolved a yellow smoke containing all of tha nitrogen from tha polymer About 3OX of the original polymer weight is lost (7) Tha yellow smoke, which was stable up to % 800*C, appeared to contain compounds with polyether linkages, iso cyanate groups, and possibly ureido linkages and amino groups (6). CO was also evolved at 300*C with e two-step pyrolysis at 300*C, then 1000C, giving less CO then If the polymar was heated in one step at 1000C (7). The major volatile products (other than tha yellow smoke) observed by Hileman et a). (1975) (S) when a polyurethane was pyrolyied at 300*C were H20, propene (CHaCH;CHa), and C0a (m order of increasing amounts). At 500*C, C0a, acetaldehyde (CHaCH0), proplonaldehyde (CHaCKaCH0), 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 CHjCHjOH}, CO, COj, CM,, H;0, C1 to Ca saturated and unsaturated hydrocarbons, acetaldehyde, and propionaldehyde (5), Pyrolysis at 800 to 100P*C gave KCN, benionitrile, acatonitrile, pyridine, and ,,.,i /^tT w ' U^eUl\. 9 * wo ^ c attfC and unsaturated hydrocarbons; other Cj and C3 nitriles and cyanotoluene; the aro matic hydrocarbons benzene, toluene, styrene or cyclooctatetraene, naphthalene, and indene; and the heterocyclic aromatic compounds pyrrole, aiethylpyr cine, vinyl pyridine, 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 1000C. They also *ound more of the other products detected at '>50oC- "-esumably, decomoosition at 1000C was the source of the nitrogenous products reported. TDI, toluenediamire, dicyanobemene, benzonitrile, and other nitriles. Other pyrolysis products were toluene, benzene, styrene, xylene, alcohols, ather alcohols, ethers, and acetone (yields were not calculated although labtled chromatograms are given in the reference) About 50 products from pyrolysis of rigid polyurethane foams wera icentified in a 1985 review (10). Compusdcn Ounng full-scale comOustion of a oolyol-TDI polycethane, the tem perature attained at least 1000C within a few r nutes Hydrogen cyanide (HCN) yields reacned a maximum of C 5% and represented a toxic hazard comparable to that 020^93 mons of the CO generatad within the first 5 min. After that time, HCN yields declined, possibly due to a repid loss of yellow smoke, leaving the polyol residues. The CO concentration (total * 8X) remained steady from * 5 to 20 min of burning (7) Boettner et al (1973) (11) reported that combustion losses of C0t and CO ware 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-containmg heterocycles, and lower and aromatic hydrocarbons) were formed 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 576-606 2. R. N. Sampson. "Insulation, Electric" in: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ad., Vol 13. M. Grayson, Editor. New YorkInterscience Publishers, a Oivision of John Wiley & Sons, 1981, pp 534-563 3. H. Schoenbacher and A. Stolarz-Izycna. Compilation of Radiation Damage Test Data. I. Cable Insulating Material*. CERN-79-04/XPS. Available Springfield, VA: National Technical Information Service, June 1979 A T Tanaka and A. Greenwood. Advanced Power Cable Technology. II. Present and Future. Boca Raton, FL: CRC Press, 1983 : f I Hlernan. ,t. J. Voornees. L. *ojcik, H :i. 3in,y, 5 A 5yan, =nc . N Einnorn. Pyrolysis of a Flexible Urethane Foam. J. Polvm Sci , 13, 571-584 (1975). 6 S J Grayson, J Hume, and D. A Smith Reduction of Smoke and Toxic Gases from Flexible Polyurethane Foams Under Fire Conditions Introductory Review and Chemical Model. Plast Rubber Process Aoo) , 2(2), 111-122 (1982) 7 w. 0. Woolley, Toxic Products from Plastic Materials in fires. Plast Polvm.. 41(156), 280-286 (1973) 8 J Chambers and C. B Reese The Thermal Decomposition of Some Polyurethane Foams Br Polvm J,. 8, 48-53 (1976) 9 ' w D Woolley and P J Fardell The Prediction of Combustion Products f're Research. 1. 11-21 (1977) -- -O HONS 020494 10 H. Paabo and B. C. Levin. A Review of the Literature on tha Gaseous Products and Toxicity Generated from~the Pyrolysis and Combustion of Rigid Polyurethane Foams nBSIR $-3224, PB86-151941. Springfield, VA National Tecnnical Information Service, December 1985. 11. E A. Boattnar, G. 1. Ball, and B Welse Combustion Products from the Incineration of Plastics. PB Rep. No 222001/0. Springfield, VA: U S National Technical Information Service, 1973. 4-3" MONS 020*95 Section 5 SULFUR-CONTAINING MATERIALS See el so creosote in Section 4, Nitrogen-Containing Materials. CHLOROSULFONATEO polyethylene CASRN 900B-08-6 Synonyms Rubber, synthetic, chtorosulfonated polyethylene; Chlorosulfonated poly ethylene synthetic rubber; CSPE. Trade Names (producers)- Hypalon; Hypalon 40 (E, I. du Pont de Nemours, Inc,), Luiaaex General Information Molecular Formula: Best rubber properties: 30 to 352 Cl and 0 B to l.SX sulfonyl sulfur. Structure of Starting Materials and Polymer: cHiCHjCHjCHj - * :ci, * so, -- ' ch-:h,ch,ch ~ Cl o=s=o I Cl * ;hci CSPE nay be crosslinked by use of PbO. MgO, or tribasic lead maleate with a sulfurcontaining accelerator, usually dipentamethylenethiuram 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 and cables can be prepared by the use of metal oxides or hydroxides, rosin acids, and a free-radical scavenger such as a mtrosamine, nitrosohydroxylamine, or hindered phenol (1) Uses Electrical uses include wire and cable (appliance cores, ignition wire, telephone handset cords, ana weatherproof wire) An important use is for flexible. HONS 020496 decorative, end protective coating* for fabric, metal, rubber, masonry, ana other surfaces (1). Chiorosulfoneted polyethylene is preferred over neoprene for jacketing of insulat ing cables for fixed 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 sheathirg oil-dnllfng platform cables instead of polyfvinyl chloride) (3) Other uses include weather stripping and automobile window channels; leether-like coated fabrics, floor tile; automotive products such as distributor caps, sparkplug covers, and ignition wire jacketing, hoses for steam, water, and corrosive chemi cals, chemical tank linings, surfacing of conveyor belts, gaskets or diaphr*gms -earn ring resistance to ozone, the weather, heat, or oils, and adhesives (1) Thermal Decomposition Hechanisms S03C1 groups are lost followed by dehydrochlorination to form a polyene Cross linking may occur by inteneolecular elimination of HC1 and/or a Oiels*Alder type reaction between two dehydrochlormated polymer molecules Thermal degradation then proceeds principally by 1:S hydrogen transfer, This gives C3- to C6 1-elkenes. Limited unripping gives CSH. Secondary pyrolysis occurs above 627C Higher l-a)k*nes formed during primary pyrolysis are degraded to 1ower-mo!ecular- weight products probably by dissociation of free radicals and intramolecular cyclic dissociation, Above 727C. further fragmentation, cyclizatlon, and aromatication occur; nyorogen yie>cs increase, =na C, products decrease orccuction maxi mizes at - 827C, toluene yields decrease aoove 827C, benzene yields plateau m the range - 700 to 1100C; naphthalene yields reach their rnexima about 847C, snc. finally, only small fragmentation products and large polynuclear aromatics are cesent (4) Summary of Experimental Studies Reviewed J^rolysis. At pyrolysis temperatures < 6Z7C , major products include C3 to Cs i-elkenes anc HCi Aor example, major products at 497C -ere reported as ether* and etnane, prcoen* and propane, 1-butene, I,3-Dutadiene, and toluene, at Si7C propene and propane, etnene and ethane, benzene, and toluene Above 527C, z-e l-alkenes breax cown to lower fragments, thus. CHt appeals as a major product Atove c.c zat.cn anc aromat*zst'on procucts are argely o-ecorv nan _ HONS 02Q*97 However, the Cj (*than* and ethane) maximum is - B27C. At 927C, large poly cyclic aromatic hydrocarbons ra among products with high yields of benzene and naphthalene (A)- The large polycyclic aromatic hydrocarbons detected ware acenaphthene, fluorene, anthracene, and phenanthrene. Other products were styrene, toluene, mdene, 2- and 1-methylnaphthalene, biphenyl, and dimethylnaphthalent Combustion. No information was found on organics in combustion products. Combus tion of chtorosulfonated polyethylene (CSP) cable sheath material compounded for reduced acid ges emission gave concentrations of the products in the order CO} > CO > HC1 > SOj. A standard type of CSP cable sheath material that had not been compounded for reduced acid gas emission gave products with concentretions in the order COj > HC1 > CO > S0j (3). References 1 P. J. Centerino, "Ethylene Polymers: Derivatives" in. Encyclopedia of Polymer Science and Technology. Vol, 6. H. F. Mark and N. M. Bikales. Editors New York; Wilev, 1967, pp. 431-454 2 J E. Hogan. "Wire and Cable Coverings" in Kirk-Othmtr Encyclopedia of Chemical Techno!, 3rd ed. Vol. 13. New York: Interscience Publishers a Division of John Wiley & Sons, 1981, pp. 564-590. 3. G. C. Sweet. Offshore Cables - The Role of Different Classes of Elastomers in the Fire Situation. Rubber World. 189(2), 18-22 (1983). 4 0. A. Smith and J. W. Youren. Pyrolysis of Polyole-in Elastomers 8r Polyir. J, . 8(4), 101-117 (1976). o0L'SULFONE C,.RN 25135-SI-7 Synonyms' Sisphenol A - 4.,4'-dichlorodiphenyl sulfone copolymer Trade Names (producers); Udel (Union Carbide) Ge-e-al Information Molecular Formula* (C*7H2sS04)n HONS 020498 3*3 Structure of Honoeiers end Polymer- Bisphenol A 4.4' *Dichlorodipheny1 sulfone Polysulfone Uses Electrical/electronic applications include connectors, auto fuses and switcnes, housing, coll bobbins and cores, TV components, capacitor film, and structural circuit boards. In chemical processing eQuipmant. polysulfone is used for corrosion resistant piping, both transparent end 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 eguioment (1). Thermal decomposition Mechanisms During thermal and thermooxidetive degradation of polysulfone, crosslinking and chain*sci$sion reactions art caustd principally by raactions of frae radicals with the aromatic nuclei. Iron and dipnenylotpropane (OPP) impurities affect the cou-se of thermal degradation of polysulfona. Both iron and OPP accelerate oxidation of alipnetic groups and thermal dtcoaposition. Thermal degradation products of DpP destroy or retard cross)inking, reacting with the polymers as 'ow-molecular-weignt radicals, Iron impurities accelerate crosslinking (2). Summary of Experimental Studies Reviewed Pyrolvni. Pyrolysis at 460 to 520*C caused a 62% weight loss of the polysu''ore sample (3) Radiant pyrolysis of a sample containing up to 1% carbon black for 2 min at 4 cal cm ^ sec * left 31% char (4,5) No chemical products were identi f led MONS 020499 Combustion Thermal oxidation at 350C for SO hr caused less then 10% weight loss In th# same period, " 70% was lost at 400C (6) Combustion for ' 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 deficient in oxygen gave primarily C02, CO, S02, and a residue. The next most abundant volatiles were methane (CH4), benzene (CeHc), and toluene CCcKsCH3) Minor amounts of ethylene (CH2 CH2), ethane (C2H#), ethylbenzene (C*H(C2HS). and styrene (CSHSCH CH2) were determined. Measured products accounted for 92.6% of the sulfur content but only 60% 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, ethylbenzene (or xylene), styrene, methyl ethyl benzene, indene, methylindene, trimethylbenzene , naphthalene, methylnaphthalene, biphenyl, and dimethyInaphthalene. Other oxygen-containing products Included benzaldehyde, benzofuran, methylbeiLOT'crar., c.-ei-c.fi. an, oiphenyl etner (or ;her> Iphen-'), c -ts-1, ttn.'phe-.o'1, and 2-hydroxyphenyl-2-phenylpropane (8). References 1. Modern Plastics Encyclopedia. 1985-1986 Vol 62, Ho IDA j Agranoff, Editor. New York: McGraw-Hill Inc , 1985. 2 A L. Markon, I. I. Levantovskaya. Yu. I. Kotov, 8. E, Konovalova, L. I Reitburd, L M Bolotina, and A. 8. Blyumenfel' d, Effect of Impurities on Degradation and CrosslInking of Polysulfone. Vysokomol Soedin , Ser A, :6(8), 1712-1717 (1984), 3 G. L Ball andE. A, Soettner. Volatile CombustionProducts of Polycarbonate and Polysulfone J. Appl. Polym Sci . 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, Braumen. 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 Flammability, 7, 367-400 (1976) 7 C K Sangha, M Matijak, and Y Alane Toxicologic Evaluation of Thermo plastic Resins At and Above Processing Temperatures Am Ind Hyq Assoc J 42(7). 481-485 (1981) 020500 HONS 8, E. A. Soettner, G. L. 8*11, and 8. Weis* Combustion Products from *ne lncjn*rtlon of Plastics PB Rep. No, 22200l7o Springfield, VA----- Sit1on*l Technic*! Information Service. 1973. MONS 020501 Section 6 materials containing only c and h or c, h, ANO 0 3ISPHENOL A EPOXY RESIN CASRN. 25060-36*6 Synonym*: B1 s(-hydroxypheny1JdimethyImethane-epfch1orohydrin copolymer; 2.2-B1s(g-hydroxypheny1)propane-epichiorohydrin condensate; 01phonylolpropaneepichlorohydrin polymer; Epichlorohydrin-bisphenol A epoxy resin; Oxirane, (chloromethyl)-, polymer with 4,4'-(l-iaethyl*thyl idene)bi ([phenol] ; Phenol. 4,4'-(l-thylethy1id*ne)bis-. polymer with (chloromethyl)oxiran*. Propane, 1-chloro-2,3-epoxy-, polymer with 4,4'-isopropylidenediphenol. Trade Names: Araldite 6005 (or 6010 or 6084 or GY250 or GY260 or GY2B0); Bake lit* PXOA; Casting Resin F; Epikote B2B (or 834 or 836 or 1004 or 1007), Epl-Rez 510; Epon 026 (or B34 or 1001 or 1002 or 1004); Epotuf 37-139; GenEpoxy 190 General Information Molecular Formula: (CltH1#0jCiHtC10)x 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 *ONS 020502 6-1 casting transformer colls used in tha United Statas -aports that roughly 80% of their production for transformer coils may be approximated by the above generali ties. The remainder usa cycloaliphatic compounds in 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 isopropy1ldene linkages in the former are less stable than the methylane linkages of the epoxy novolaks. The structure of a novolak epoxy is as follows (3). Isomerization of terminal epoxide groups before cleavage would give 2-hydroxypropanal [CH3CH(OH)OtO] and propionaldehyde (CHsCKsCH0). Direct cleavage in the end groups would give ethylene oxide and formaldehyde. Acetaldehyde (CHjCHO) could arise from isomerization of ethylene oxide. Chlorosubstituted compounds probably arise *rom impurities -n the glycidyl portion of the resin (4) Summary of Experimental Studies Reviewed Because of the scarcity of information on thermal degradation of bisphenol A eooxy resins, information is also Included on the structurally similar epoxy novolax resins. Pyrolysis Pyrolysis of a novolak epoxy resin at 350C gave toluene (the react'on solvent) and water as major volatiles (94S). Phenol, cresols, and higher phenols ethane, allyl chloride, aldehydes, and ketones were among the pyrolysis products (4) Pyrolysis of a bisphenol A epoxy resin cured with 2 6 parts per hundred res'" HONS 020503 -2 2-ethy 1 imidazole at 300 to 425C gave mostly phenol, diphenyl ether (C#HsQCshs), and CL- to Cs-alkylated phenols and aromatic ethers. Most diphenyl propane deriva tives were g.g1-isomers (5). Pyrolysis of uncured blsphenol A epoxy at 350 to 4S0C gave water (from condensa tion of epoxide groups) and toluene (reaction solvent) es the major products. At 450C, approximately equal amounts of methyl chloride (CHjCl) and acetaldehyde were formed HIgh-boi1ing cresols, phenol, isopropenylphenol [CH3C(CH2)CtH40H], and blsphenol A were in the residue (4). Major products from pyrolysis of a blsphenol A epoxy resin cured with methylenedianiline (H2NC4H4CH2C4H4NH2) were water at 3506C and water, CO, CH3CH0, CH3C1, and CH4 at 450eC Methylcyclopentadiene arose from both cured and uncurad bisphenol A epoxies (4). Pyrolysis of an uncrosslinked novolak epoxy resin at 360 to 1200C volatilized 38 tc 7* c' '.he ......... , 1 t; ECU of the vpi ivies ccTorijed an uncla'acto-'red **<"rial (average molecular weight 350 from pyrolysis at 800*C) Methyl chloride (CHjCl) and ethyl chloride (CSHSC1) were found in the volatile fraction at 360C, but not at higher temperatures. Hydrogen (H2), ethylene (C3H4), and substitutedcytlopentadlenes were detected In the volatile fraction at 800 and/or 1200*C, 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 25.9% at 1200*C) es C02 concentrations decreased (maximum 16 2% in the vclatiles at 360*C). Organics representing more than 3% of the volatiles were methane (CH,, 4 3% ax 1200C), propylene (H,C CHCH3, 6.3% at 360C), benzene (C6h4, 8.1% 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 (CaH2), acetone (CH3C0CH3), propane (C3H4), and ethane (C3H4) (Madorsky and Straus, 1961; cited by Zbozmek, 1985) (1) An epoxy resin used to impregnate tapes and wrapper insulation in dry-type trans formers was pyrolyied at 600 and 100G*C. The prooucts collected (in unreported amounts) were C02 , CH4, C2H4, propylene, butylene (1-butene?), pentane, cyclopentadiene, toluene, phenol, xylene, styrene, moan, indene, naphthalene, and biphenyl (6) HONS 020504 Lum and Feinstein (1981, 1982. cited by Zbozinek, 1985) (1) found benzene, pnenol and cresol In tha thermal dtgradation products of novoiak epoxies (pyrolysis') heated at 300 to 500aC. Combustion Bisphanol 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 reawved from the ignition source. The odo's of phenol, formaldehyde, and hardeners are detected in the smoke (4). Approximately 500 1b (230 kg) bisphanol A epoxy is used m the cast transformer coils of a 3-pnase transformer. The exaiepla is based on a 2,000 kVA model 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 ft' (9 83 m}), 208 ft (5 89 m1) 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 tha resin. When heated for 30 mm at temperatures up to 500eC 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:m3), 2.0 ppm ethylbenzene (CtHjCjHj), and 1,5 ppm benzene (C4H6) The rest of the mass was not accounted for by tha study authors. Estimated con centrations in air were 3 03 mg phenol/m23 (0SHA permissible exposure limit [PEL] 19 mg/m3), 0.30 mg toluene/m3 (PEL = 375 mg/m3), and 0 23 mg ethylbenzene/m3 (PEL 435 mg/m3) (2). Acetylene (CjHj), benzene, toluene, and an aromatic fraction were deteeteo in the gases from combustion of an 800 kVA GEAF0L cast resin transformer at 1Q0G to 1200C The fires were initially fueled by propane and wood, and the gases from the fuels were not separated from the gases evolved from combustion of the trans former (Altmann e* al., 1984; cited by Zbozinak et al . 1985) (1). References 1. J V Zbozinek, Jr , 0 G Marsh, and A Bohrnerud (SCS Engineers, Inc ) Stete-of-the-Art Review of Combustion and Pyrolysis By-Products of PC3 Suostitutes Palo Alto, Canf Electric Power Research Institute, Marci T5a3 2 F S Srugner and A J Jonnatti An Air Pyrolysis Study of Cast Bispnenc' Epoxy Transformer Coils IEEE Trans Power Appar Svst . pAS-102(7), 2201 2207 (19821 HONS 020505 3. J Troitisch. International Plastics flammapilitv Handbook New York Macmillan, 1983, pp. 17-44 and 55-63. fl R T. Conley "Thermosetting Resins" in; Thermal Stability of Polymers. Vol 1. R. T Conley, Editor. New York Marcel Otkkar, In^. , 19K1, 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. Qrbeck. "Flammability Testing of Dry Type Transformer Insulating Materials: in. Proc. Electr./Electron, Insul. Conf.. 12 [unpaginated 3-page reprint] (1975) _ CROSSLINKED POLYETHYLENE CASRN. 68584-45-2 [for radiation croselinked homopolymer; none available for peroxide-cross 1inked homopolymer]. Synonyms: XLPE; Ethane, homopolymer, radiation crosslinked. Trade Names (producers). None found General Information Molecular formula: (CH4)_ Structure of Monomer, Polymer, and Common Peroxide Crosslinking Agent CH3.CH, Ethylene >CHiCH,CHCH2CH2'v "l -CHjCHjCHCHjCHj-v Radi ation-Cross1inked Po1yethy 1ene (XLPE) Dicumyl Peroxide (DCP) in cable manufacture, crosslinking is don* immediately after extrusion of the cable insulation becaut-3 the material cannot be shaped after crosslinking This cress linking is dene almost exclusively by adding peroxioes such as dicumyl peroxide (DCP) to low-density polyethylene granulate and steam curing 'or saout 1 mm at MOMS 020506 aoout C7Q*C. Electron Be** or gamma irradiation are other methods of cross'.inning 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, stea* curing may be replaced by treatment with pressurized, heated inert gas (3) Uses Low-density grades are used for wire and ceble coatings and insulation, high-density grades for pipe and molded fittings Since the 1970*. most of th* distribution power cables Installed in the range 15 to *6 kV have been insulated by chemically crosslmked polyethylene. These XLPE cables are substitutes for oil-impregnated paper-insulated lead-covered cable. 8y 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 th* use of crosslinked polyethylene for communications cables at that time. Use m coaxial and other cables was much less than 100 million pounds s 2.2 x 10 g). Power utilities have widely accepted XLPE-insulated cable for transmission circuits at operating voltages up to at least 138 kV (2) XL-E or the--noset polyethylene ma;1 be used as an integral ccve-ing o--vc . tag* ex plications on very small diameter single-conductor cables (3) Crosslinked poly ethylene may also be used in heat-shrinkable tubing to insulate joints and splices of hook-up wire (4). Thermal Decomposition Hechanism; No specific information was found for crosslinked polyethylene; but since cross linking is involved in thermal degradation of linear and branched polyethylene*, tha the-mai decomposition mechanisms cf TPLE a-e oroDac sv-ilar to -.icse polyechylene (see page 6-12). S.mmarv o* Experiments Studies Reviewed vro1vs-s Unfilled crosslinked polyethylene insulation from a No 1* small w -e lost 3 -X of its initial weignt when heated from room temperature to 393C at me rate o' I0C/min, *6.9%. when heatec to 43C, and 97 55!, when heatea to A~C Another DCP-crossl 1 nked polyethylene sample lost Z 0" o' its weight by 361C an98 7% o,. 481C A sample with 335! filler showed about tne same weight loss mcreas no temoe-atures <5; DC- decomposition products ana aad tives present in the crosslinked polvetnyiere are 1 i ke y to be .denf'iec among oy-olytetes at low temoerat-ras C-css >s. tol/et-- ene '-om three tab'es t.-.at ^aa 'ailec i'te- ? r- ;; ea-: -* ;; ,, HONS 02050? found Vo contain several compounds at tna parts par million 'eve! Acetopnenone, an expected degradation product of DCP, was not found in any of the three samples In one sample, o-mathy1 styrene was the major contaminant and cumene was the second most important contaminant. In the two , ther samples, thiobutyric acid S-decyl ester was ttie major contaminant followed oy phenol and cumyt 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 Denzena Uncross 1 infeed polyethylene from a fourth cable contained thiobutync acid S'decyl aster, phenol, and toluena (all identifications were made by gas chromatography-mass spactrometry) (6). Combustion. No specific information was found on XLPE combustion or other thermal oxidation. References 1 G. G. Hawley The Condensed Chemical Dictionary. ICth ed New York Van 2. T. Tanaka and A. Greenwood. Advanced Power Cable Technology. II. Present and Future. Boca Raton, Ft: CRC Press, 1983 3. J , Hogan. "Wire end Cable Coverings" in- feirfe-Qthaer Encyclopedia of Chemical Technology 3rd ed. , Vol. 13. New York, Interscience Publishers a Division of John Wftey A Sans, 1981, pp. 564-590 4. R N. Sampson. "Insulation, Electric" in. Kirk-Qthmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 13. H. Grayson, Editor. New fork Interscience Publishers, e Division of John Wile;' & Sons, 1981, pp S34-563 3. R R. A. Abou-Shaaoan, J L. Haberftid, S. M iarrall, II, J F jonnson anc A P Simonelli. Characterization of Polymer : Oitlectnc Insulation V Thermal Analysis of Dielectric Insulation, Etr/lene/Propyiena Rubbers, and C'osslinked Polyethylene! Decomposed in a Nitrogen Atmosphere. Polvm Eng Sc- . 16(8), 544-551 (1976). 6 J, Taneka and R. Uuthar Analysis of Cables with Visible Halos Ccnf Rec IEEE Int. Sump. Electr InsuT . 292-295 (1982) KRAFT PAPER General Information Molecular Formula (4o0sJn --.ructjie of Polymer'-gn;n B8 to 91S a l pha-cel l u 1 ose, l to 3% hemicel 1 u lose , and 2 to MQNS 0ZG508 U*t*- Electrical use for kraft paper is for insulation in oil-immersed equipment such as transfonears. To upgrade th# 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). Ci1-impregnated paper is used to insulate overhead distribution cables (2) and is the standard insulation for 1X5*650 kV circuits, whereas extruded solid*dielectric insulation prevails over paper Insulation for Intermediate voltage caeles (15 to 69 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 cnam cleavage Segments decompose to give a syrup whose major component is levoglucosan (1,6anhyCro-0*D-glucooyranose) and its furanosa isomer (1,6-anhvdro-p-Q-glucofuranese) Numerous lower molecular weight products form at temperatures 50QC Ash in trace amounts appears to catalyza condensation, dehydration, and fragmentation reactions, thereby reducing syrup yields. Primary syrup products can be converted to ethylene and othar 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 cc ow moiec..or .veignt gases, c-.ar, ana numerous othe-" products .ov leaoir.g rates and long residence times reduce the yields of more desirable sugar deriva tives () dehydration -v anhydrocel lulose--* char - CO, CO;, H;0 Summary o( Experimental Studies Reviewed pyrolvsis P-oauct gases from pyrolysis of kraft paper are produced in aoout the same amojrts as 'rom py-ol/J's of other ceilu'ose sources, including woods *oe HONS 020509 gases art C02, CO. Kt, CtHt (acetylene), CH4 (methane), C2H4 (ethylene), and other nydrocaroon* (5) Oepotymeriaation gives tht anhydrog 1 ucose product levoglucosan (a glucooyranose derivative) and its furanose analog. Temperatures above 500C give numerous lower molecular weight products and char. Oehydration reactfons give anhydrocellulose, which also decomposes to give char and volatiles (4). Combustion tion Ho information was found on specific products of krjft paper combus References 1 A Miyoshi, New Additive for Improving the Thermal Aging Characteristics of Kraft Insulating Paper. IEEE Trans- Eltctr, Insul.. El10(1), 13-17 (1975) 2 R H. Sampson. "Insulation, Electric" in- Kirk-Qthnar Encyclopedia of Cnemical Technology. 3rd ed., Vol 13. H. Grayson, Editor New Yor* Interseience Publishers, a Division of John Wiley & Sons, 1981, pp. 534-563. 3 J. E. Hogan. "Wire and Cable Coverings" in: Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Vol. 13. New York. Jnterscience Publishers, a Division of John Wiley 1 Sons, 1981, pp. 564-590. 4. M. W. Hopkins, C. DeJenga, and H. J. Antal, Jr. The Flash Pyrolys'. c' Cellulosic Materials Using Concentrated VisibleLight. Sol Energy. 32(4), 547-551 (1984). 5. M. W, Hopkins, M. J. Antal, Jr., and J. G. Kay. Radiant Flash Pyrolysis of Biomass Ueing a Xenoh FI ashtube. J. Appl Polym. Sci.. 29(6), 2163-2175 (1984). POLYETHYLENE CASRN 9002-98-4 Synonyms: Polythene, ethylene homopoTymer; ethane nomopolymer Traoe Names- Agilene; Alathon; Alkathene; Courlene, Lupolen; Platilon, Pylen, Reevon (1) General Information Molecular Formula- (C2H4)n HONS 020510 3*3 NLlH: Methemoglobinemia (13) Acuta systemic effects (4) Suspect carcinogen IAAC CARC: Animal and Human Indefinite, Human Suspect, `82 SKIN IRR Moderate INCtS ACUTE. Mouse LDf0. 520 mg/kg `78 g-Toluidlna (CRE) CASRN: 106-49-0 OESC: Solid, m.p. 45-47*C SKIN IRR: Rabbit: 500 mg/24 H, severe EYE IRR: Rabbit: 20 mg/24 H, severe MUTAGEN ORAL: Rat LDJ0: 56 mg/kg 3-Tolumtrile; m-Tolunitri1e; 1,3-Tolunitrile (NOM) CASRN: 620-22-4 DE.'C: Semi volet i le Liquid EYE IRR: Rabbit: 500 mg/24 H, severe ORAL: Rat L0jO: 4.2 g/kg Trifluoroacetyl fluoride (TEF) CASRN- 354-34-7 Trifluoromethane (NIT) CASRN: 75-46-7 Trlmetbylbenzene (SUL) CASRN: 25551-13-8 STDS: TLV: 25 ppm, 125 mg/* TWA, 35 ppm, 170 mg/m STEL OESC: Semivolatile Liquid NL'rH: Irritation-Lungs, Skin--Marked (14). Cumulative CHS Effects (7). Anemia (12) SKIN IRR: Yes Triphenylene (RE) CASRN; 2J7-59-4 OESC: Solid, m.p. 195-198#C Valeraldehyde; Pentanal; Amyl aldehyde (RE) CASRN: 110-62-3 DESC: Volatile Liquid SKIN IRR: Rabbit- 500 mg/24 H, moderate EYE IRR: Rabbit* 500 mg/24 H, severe ORAL. Rat L0iO: 3200 mg/kg EKIN' Rabbit L0so, 6000 mg/kg HONS 020588 Valerolactone (PE) CASRN: 108-29-2; (d-) 542-28-9 OESC; Sealvoletlie Liquid Vinyl benzoate (PET) CASRN: 769-78-8 OESC; Seaivolatlle Liquid ORAL; Rat LD,e: 3250 mg/kg SKIN IRR: Rabbit; 10 eg/24 H Vinyl cyclohexane (NIT) CASRN: 695-12-5 OESC: Volatile to Start volatile Liquid ORAL; Rat LD,0: 3080 mg/kg IARC CARC: Animal Indefinite, '76. Vinylidene fluoride; 1,1-Dlfluoroethene (TFZ, V]T) CASRN: 75-38-7 OESC; Gas ORAL TUHORIGEN; Rat TDllt: 1930 eg/kg/52 W IHL: Rat ICL 1 128,000ppa/4 H Vinylpyridine (PU) CASRN; (2-itoaer) 100-69-6; (4-) 100-43-6 OESC: Seelvolatile Liquid Viiiyltoluene; Methylstyrene (NON, PET) CASRN: 25013-15-4 STOS: OSHA; 100 ppm, 480 mg/m* TLV: 50 ppa, 240 eg/a3 TWA; 100 ppa, 485 mg/m* STEL OESC: Seel volatile Liquid HLTH: Irritation-Eyes, Nose, Throat, Skin--Moderate (15, Less than 200 ppai) CNS effects (7, Greeter than 200 ppa). INGES ACUTE: Rat LD,0: 4000 mg/kg Xylenes (CSPE, EPO, MOM, PU) CASRN: 1330-20-7 STOS: OSHA; 100 ppa, 435 eg/a3 TLV: 100 ppa, 435 eg/e3 TWA; ISO ppe, 555 eg/e3 STEL OESC: Sealvolatile Liquid HLTH; Irritation-Eyes, Note, Throat, Skin--Moderate (15, Less than 200 ppm) Narcosis (I, Greater than 200 ppe). Xylenols (CRE) 2.3 . CASRN: 526-75-0 OESC. Solid, e.p. 2.4CASRN: 105-67-9 OESC: Solid, m.p. 73-75.5*C 22-23,C/Saaivolatile Liquid 0-40 MONS 020589 CASAN: 95-07-4 OESC: Solid. o.p. 71-73*C 2.6- CASRN: 576-26-1 OESC: Solid, m.p. 45-46*C 3.4CASAN: 95-6S-8 OESC: Solid, o.p. 65-68*C 3.5CASRN: 108-66-9 OESC: Solid, o.p. 65-66*0 Xylidine; 0toothyIon 11 In# (ORE) CA5RN: 1300-73- STDS: OSHA: 5 ppo, 25 og/o* TIV: 2 ppo, 10 mg/a* TWA OESC: Seel volatile Liquid HLTH: Methemoglobinoola (13) Acuto lysttolc toxicity (4) SKIN ABS: Vo* INflES ACUTE: Rato L0fO: 610 mg/kg 2,4-XylIdlne (CAE) CrSRN; ?I 58-; OESC: See'volatile Liquid MUTAGEN IARC CAAC: An tool Indefinite, 170 2,5-XylIdlne (CRE) CASRN: 95-70-3 OESC: Seoivolatile Liquid MUTAGEN ORAL: Rat L0IO: 1297 og/kg I ARC CARC: Anloal IndaflnlU, 70 REFERENCES TO APPENOIX 8 1. R. L. Tatken and R. J. Lewis, Sr. RTECS. Registry of Toxic Effects of Chtoical Substances. 1901-1902. OHMS (NIOSH) Publication No. 83-107. Washington, D C U.S. Government Printing Office, 1983 2. "Appendix A: U.S. Dopartoent of Labor, Occupational Safety and Health AdolnUtrotlon, Chemical Information Table" In: OSHA Industrial Hygiene Technical Manual. Chicago, IL: Commerce Clearing House, Inc.. 1984^ pp. A-l to A-201. 3. Aldrich Chemical Company, Inc. Aldrich Catalog Handbook of Fine Chemicals, 1986-1987 Milwaukee, Wl: Aldrich Chemical Company, Inc., 198i 4 M. Windhola, Editor The Merck Index. 10th ed Rahway, NJ: Merck and Company, Inc., 1983. 5 G. G. Hawley. The Condensed Chemical Dictionary. 10th ed New York: Van Nostrand Remhold Company, 1381 B-Jl HONS 020590 6. ft. C. Weast, Editor. CftC Handoobk of Chasdstry and Phyilci. 6lst ed. loco ftaton, Ft.: CftC Press, Inc., 1980. " 7. National Institute for Occupational Safety and Health. Current Intelllaence Bulletin 41. 1.3-Butedlene CH:CH-CH:CH.. OHHS (NIOSH) ftubl. No. M-20S----W94-198019. Springfield, VA: National Technical Infonaatlon Sarvlca, 1994. 9. National Toxicology Progra*. Toxicology and Carcinogenesis Studlee of 1.3"utadltne (CAS Ho. 106-99*0) In |HC3Fl Mice (Inhalation Studies). Tech fteo. er. 298. ftesearch Triangle FPaerrk, NC: N' at'ionalToxicology Program, 1994. 9. J. E. Huff, ft. L Mel nick, H. A, Solleveld, J. K. Haseaan, and H. Powers. Multiple Organ Carcinogenicity of 1,3-Butadlene In 96C3F1 Mice After 60 Weeks of Inhalation Exposure. Science. 277(4699), S46-S49 (1995). S-42 HONS 020591 Structure of Monomer end Polymer CHs.CH2 Ethylene (ethene) "(-CHjCMj-^- Linear, high-cens1ty polyethylene is produced by polymerization In the presence of transition metal catalysts (e g , chromium oxide or molybdenum oxide on a silicaalumme support) at relatively low temperatures end pressures. Incorporating butene, hexene, or another a-olefin as a comonomer lowers the density of the oroduct Low-density polyethylene, with a relatively high degree of branching, is produced by use of highe- pressures and temperatures and peroxide-type cata lysts Incorporating polar comonomers such as vinyl acetate modifies the properties of the product. Linear low-density polyethylene is produced by copolymerization of ethylene with er-olefins such as butene, hexene, or octene at high or low c-essures High-molecular-weight low-density polyethylene and high-molecular-weight highdensity polyethylene are two other types. The iatter is a linear homopolymer or copolymer with weight average molecular weight 200.000 to 500.000 They have a density greater than 0.541 g/cm3 (2). The density of low-density polyethylene falls in the range 0 910-0 925 g/cm3, tnat of medium-density polyethylene, 0.926-0.940 g/cm3 Copolymer high-density poly ethylene has a oensity 0,941-0.95? 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 , wnethe'- ngn -ecium. o- 'ow pressure was j$eo -icr-o-essjre polyet*"' iene rcludes low-density polyethylene and medium-density polyethylene up to a density c-1 v 0.933 g/cm- Low-pressure polyethylene includes mecium-density polyethylene c'om a density of -* I 933 g/cm3 through high-oensity polyethyienes with densities up t; > 0 96 g/cm3, Msdium-pressure polyethylene have -igh densities (n> 0 95-'- 0 56, (3) Uses PolyeV'y ene uses include coatings, containers, toys, liners, bags, and c'oe and tubing as -e`l as the electrical applications Pes.ns with melt indexes of C 2 to C - g -in a"e used as wi-e and cable coatings in tnictsnes ses rang'ng y 005 to to - :o 13 to 33 mm) Poiyetnviene insulation and ;acx.eting is useu or, -ion .o'tage oower cade te'eonone cab'e, television lead-in cable ano cos' - cao>e - nei- :-oe-s t., pcet-ylene wmc- -s a coool.me- cf et-viene it* HONS 020511 various a-olefins, may lso b used for wire (nd cable Insulation and jacketing Hign-moiecu!ar-weight high-density polyethylene, wnich may be either homooolymers (highest density) or copolymers (typical monomers are butene, hexene, and octene), is used for cable conduit and other pipe (2) Polyethylene, crosslinked polyethylene, ethylane-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 oione and weathering resistance, but it is susceptible to environmental conditions above 75`C 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 the use of polyethylene m distribution power cables since 1967 (4) Crosslinked polyethylene is discussed on page S-5 Polyethylene used in buried underground distribution cables (15,000 to 25,000 V) nas experienceo a nign rate of lncoieraoife 'q lures after service 'or 5 t; 7 yti-s The low cost still makes use of polyethylene att-active. Research continues to f'nd additive* to improve the service life. Polyethylene haa been used for years as low-loss insulation in high-frequency, coaxial cables for electronic applica tions Polyethylene is also used m ocean telephone and telegraph cables and direct-buried cathodic-protection circuits and telephone cables (S) However, polyethylene is impractical for use in high-voltage, power transmission cables Caole .aekets aade of polyethylene are used when moisture resistance is the or'mary requirement, such as for nonleeded dry paper or plastic-insulated telepnone ceoles. U*e of polyethylene jackets for laad-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 cover'ng is to be expoied to weather, a filling of about 2% carbon clack must be aaoec to prevent ultraviolet-radiation cracking (5) Polyethylene can also be used for insulating moldings (6) HONS 020512. Thernia 1 Decomposetion Kachan'sms Pyrply;is. 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 uo to about 700 Thermal cracking of polyethylene gives good yields of high-melting waxes (molecular weights greater than 400) without cnar or tar formation (7) Polyethylene degradation is accompanied by a rapid decrease in the polymer s molec ular weight, tittle monomer is produced by depropagation reactions (i e , the reverse of the free radical addition reaction that produced the polymer) Monoolefms are produced by intramolecular transfer of hydrogen atoms to a caroon 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 eerbonyl groups, chain branches, and unsaturated structures () Combustion. Thermal oxidation of polyolefins and other hydrocarbons (RH; involves generation of a hydrocarbon radical (R ); reaction of the hydrocarbon radical P with oxygen ( 00 ) to give a peroxy radical R00 , prooagation of the reaction by abstracting h' from anothar or tnt same hydrocarbon eolecule, thereby producing a new hydrocarbon radical R' ; and reaction of R' with 00 to give a iew peroxy radical R`00 Peroxy radicals can also abstract H* fro* RH, giving R00H R00H decomposition gives R0' and HO', wnich can also participate m the chain reaction with. RH (7) Summary of Experimental Studies Reviewed Pyrolysis Pyrolysis of polyethylene at temperatures up to 10002 gives satu-ateo (paraffins, alkanes) and unsaturated hydrocarbon; (olefins, alxenes, anc ctenes) The olefins are primarily 1-alkenes (o-olefins) with lesse- amounts of o.-u-d'enes P-oducts having up to 18 caroons nave been lct'tifieo, some studies have -sported products whose chain lengths extended to 30 or more caroons (9 TO HONS 020513 Generally, major paraffin and a-olefin pyrolysis product* throughout tnt tenotriture range studied had no nor* than seven caroon*. Hydrogen was reported to oe a major volatile product at 1000C (11), o,iu*01#fins (o ,j*d1*nes), 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-density 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 320SC. 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 350C but were minor products between 3S0 and 700C, indicating that pyrolytic processes dominated in this region, At 1000'C, 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 1000C). At the higher temperatures, the o-olefms were generally long-chain hydrocarbons, whereas the dienes and paraffins had shorter chains (18) Only one reference (22) reported that carbon dioxide (50 to 74X yield) and carbon monoxida (20 to 21X) were major combustion products, with 19)6 ethylene, about 7% methane, and 1 to 3% acetylene comorising the remaining volatiles oroduced at 700C Soot was also an intermeeiate-to-major combustion product, having yields of 6 to 25X (based on the weight of the dried soot and the weight of the unburned sample) at 600 to 900C, The yields of aromatic products increased with increasing tem perature, They were found mainly in soot and cola-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 020514 o S1S0Z0 (I t X oz v> T t vthn I We**.l Ut% l Itptl.l rrt*4w difilili IlydlffTK I *(if fin* l , C, *nrl/r lUfMt i, l, II*** iM/r illfMt Stmi/mt (Untt 1 (|, all*** entl/ar ilUntt ' (t> <Uhift iml/n i|l<M| ' C,4 l|#Mti n)/r <ILf*| ' tltiivt ml/at (ft I lc lIlMtl tn IlyUHwft III III* 01*f in m alfli|t I I tllfnn) ttfcylfr* Nif#* I I#M|W I Hfiriw I lllthfl IlK nrap*i*|iv| M tm ptyt*-* | UlrOl'l) dc*lylrlt If Alt It | |*ifrnf loiter* I tfirl>-l'-t.r My...* lylttN \ HniMIiiI. m l.uml* I aifeHl i > CrH COt M, III, (*. ifn m C,N, C .* (Jit. MMCMti*(iWt1 nj imi h, i C^H, (0*1*r U [,i f,n rn, ig H (.'Milt,!, t. Hj\kI .<*. + l i.tflyapr Wi#(fit ah l,nwrred l*. 4**t IkOl tf. Ml t t t *1 | ( 1lf.r Table 6-1 POL YCTIIVLLNE PYROLYSIS 4 1 5 |r la tftM1 Wt Hll _ ( u, H1 .70*1. 5W*C M0*( *#n*t 1000't lono'c lltfl Pulic i) I'l. .11*) U*lL -J>>__ n ut M " `it II. J.r ni*y i ; t Iriff Iraa Jrf j ; J 4 M* 10 110 < i J i >* *f `10 Ht !*> IU)*r Ni|ir (to jt H]tr tb}er W- ; t lr*( ll i t / / U IK 41 7* Milter Ulnar Miner Irece Miiwr n tr* Ni|h J temperatures. The yields of individual polycyclic aromatic hydrocarbons (PAHs, condensed benzene derivatives) rose from about 0 01% at 600#C to about 0 1% it 90QC Yields were based on the original polymer sample weight. At 900C, the concentration of benzo[e]pyrene (8[a]P) was 1 06% in the antd soot competed to & 0 041% in urban air particulates It should be noted that although the amount of B[e]P produced per gram of polyethylene was about the seme as that produced per gram of polystyrene, the B[e]P concentration in polyethylene soot was three to four times greater because polystyrene produced three to four times as much soot as did polyethylene (3) 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 Ci4H,0 (anthracene or phenanthrene) Flaming combustion gave a wider variety of PAHs (4), 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 1vner we'ght was nnt given) except for naphthalene at 13 5% () The DAHs 'ce-tified that are carcinogens included benz[a]anthracene, benzo[b]fluoranth*ne (2,3btnzofluoranthene), benzo[c]phenanthrene, benzo[a]pyrene, benzo[e]pyrene, and chrystnt. Studies reviewed on the thermooxidation and combustion of polyethylene are summa rized in Tables 6-2 and 6-3 0-IS HONS 020516 Table 6-2 POI TETUTIENE COHIillSTION OR OIIICR T1ICRM00X1 OAT I VC DTGRADATE ON AT TEMPERATURES UP TO 700C t1 L lP|i h- ME **,*,M* 1 MV HA r*ft -% <1# tf) ||| EM.lt) *r^n 1i imMtutfcp*if w. t im U> lt*M*tet# w. *77, mi >*'* >ft-e it*/ *7*1 i 'tr t e)k>(# Valet E --lEMMilefKitla !#<! i tt irkwti Et* m Hkt| 1'Eteh,#sm (iw-f li^eAK ,leetett. U.ulMf* <pM MW t t 4 / Mefer t i Dm Wtaeie ft* I MTV *E**r4rt an# fa nn / Ma)/te A )* (B, (ITM t Mimf ;t# mi rn irt J *JI 'If' ,**!* <(aA^*la.fm / /7H f~E (l,((Hl),(W Ml r,(!** 1,1 MS I I C* utweleJ # I1,,llr)(tttllfclililAM1 Hly^Unat|>Vt*f // ' T H-t*> *1 bp | IrtM* M*,l ttpf I llne M*r< , #ri p(*m fl.fVN, UTICM IN, (a^Ht(lrii, / / 7* nt ift la / ) IN Eipm/T. Ulee f**N**jll$ *> ,#> * -- - M 1 |lt. tl A. rv4.i I# til <*.e* , <tt.Cfl.lt (lrilia,n Itt.fM'IMjCN.H IN, <WH,N ; j I *-!* TIM l|M t He|we aft iHa Ha Jaa n jaa Ift 1W li U, Mften M I W< t aV / / 4 ttT Haft* I erftei , I mi / i i j t j It MONS 0 2 0 5 1 ? Table 6-2 (continued) H!%**>*tf hN k Hi*-r <lh|lh m Id *1|M IINaN1 upahVriltcllf*erMtertl llltftalli lN *ln1|pie UHIIm lall** H *MtNtatNm/l*r|ii*wHW Nr** NI He*iw )!> 1ln*% t rt lfi*w irflM 1S*X'Ui * u)h*mH Nr w *r .| ^ tell*. \ ||)n, , IIIIMaae fc tiflw * * Kafltl I Itpail <CMtCK,U'l (AA ( I*. . ,, i"l ` t*i* r n(, \m. _jiL <*u<*1 *m l^ (halt t*-ll* Uwl (6|| I- li*i> t*mrw(e <1* Nf**r*rfc II^M lina ll| -* f iipn>w^ IIfM*UlM I IWbtUrbMuW / %IS)"r4<k4>** f IV> 4 ^p*1l>)e 4<a|ta^| ? # *"rA r**,,<cin* % te*k 1*, *(l**%c.Ji tlf r,.*. iMn Ml "lrri^ M|r|Mt * N*hN h$fIc*r* Nu*rlu| rt)tM <L _j> _|tn,_ UL t ii / MTC-TB^f --r r -J*n -- *rr i*ij (Wk |tu (r v IWA // / / t4 i iiI 4/ / ;/ 4 >n ti titi i 4i HONS 0 2 0 5 1 8 Table 6-2 (continuril) Z oz v> o N o U> *c *** 4 4*.m* 1 rwia, e* ' Nl^lwybeaMhtra* 1fc4h<yT 4 S wlh|ilM|b hilt* (|W>mb* UbhM* 44ihT4*^ptb< m * 1 |M1 j<i4**** h*l>*L |m Ir 1 -t*W(K*l!**> I /f | ImiM laeiMo f * ^Mttl mIItm t|A (.A. i, (iA* <.** IN^.A t, (,l,, t,A <4*,T i h*n >M J*rt r^f -- yjrt . M*t. 1U,M| !> *1toM*mf ll>. m u> `( M M*r l> mri IIHA 4* **) p+r Illtaa h*t*4 (he *4#mI * bnr4 am 4b* 4*1*4 **44tfit ' l<w*< W (h *< 'b- m^>(* 'V*i* w Ihr vwl^hl *4 M* P*l***> i^4f *M |*it *M4ni>*4 hne Ml, Ilt4 *4tb rntnaiN tlf* t*rr~ vwt " ~tuv wr wr l i.v JH>* M *! nn 's * ft!tl - I < TibTe 6-3 POLYETHYLENE CON6USTION AT 500 TO IOOOC PFNdMtt wncpe un. ! Mk2 mi! la|*f CwlH Im __ uti__ CMkaitlw --1K1_ UtlyM Utl NilA^/tNr Wt **llll* rfmrt4 Wfc* fitrKtb)f Mrtt VmI C*rfc* BMtiI4i ClfW 41m44* Mtr U CO 1crut<4 *H* tij m iii ->m m **r * MI* l mm Pt> 1W Ifutoh (thiMi Cyclic Ihtr* ftM t,*,0 <I3\ IL--* 1tr4fcpirfttri* t^*'T CMfMrfl r*TMi*H4i AM*** A# WHO J ActtiliMy* OSCHt AcrU|* t pr hlph^ifr * Am* y* HfIMlI (a ct iilwitH m* CN>CtltCH0 (A, CHCHt >.(W tract aulNrlltN C|*Ct| ild*Ny4n C|'C(I ItlMIL AhImk tot* CHjCppi, 0*cr*ii<l *tfl M^i pMtrl iu HtMhftM* OctnftA/CB IfUna Hit 01,(001 CMt nfjCKHfCIllCN, Hi|k Carhifllc mNi fiatc Kid Ac*(1c k<4 *t Afignlc m Id V*r'*< Kl< NCitM HC0,H CljWtH CM,CH,(III CM, COCO, If OMtt MO * f(A*j ImiH) HONS 0 2 0 5 ^ 0 * rOj o ar to o f\> o u> fvj Table 6*3 (continued) Cr*ta)c kU tty4r4|f (HfeaijrOc *c I4i ^iMylttviltrlc c!4 thy*uir) MlhythilMNlc c (4) 1 kIm<t (cyclic Htiri) IdtrratictMt linti Im (iltwi iHyMft/MlCNltl hytlrt) Uwrt-cMU (iMw Cyclic ilUi*t Cyc loyreyf> lifMn (tiy4rKrtfli w litwittl by mk mr Mrt 4*utl< frondi| **tolt*l (-th*r*eil (t-trlyvlMfiMltnt llltktM C,W*llftiM ( IlfWt) Cyclic Uoi Ivnl'CMtA i tUMkl thart'clklin dUwi In jlM|ri tv CM fcydrocif Iiimi |l-c|MId (lUnf lulutnc IttiytlrfoifM* lyltnci Slfi vti ( lhy*iyl|rct(#'nv |l|ritrnyl (mJik li-lriw CHjDI OttO,* C,H*0. C-Mi M- . > 7* t, * ct, C tl, c;v i c*fl Mo Mo CRNI,* 2 7 V?m - Z C**k tlMt MsM, CfcJ*Cil Ch, Mt* CM Mi ti,, C,J1t C, lr*1t ______ lavritarf ImijdeMe tl Indue \ Tltfd___________ _ . "wi wr^wm*t-- wt--rare------mrc iiiL it _oi_ uu! u! mil 7NmMiwim _j*_ liar* |t 09* C liCrtitid l t R lt^ ICrtMtd nth lt^ lU)+r 4 44 Ntjtr 44 4 4 t IrtwwHtU Hintr ItUraedliti tnitraidtitt luleiMdnU IX 4 4 4 I 6<1 M *>* f Inlog CuNilltfl Table 6-3 (continued) |`H|th)i InopMfcoloM 2 - No t tff Inoplitp*1 on* 2`PhowylwopMholt-- IcompMfiyloQo f IwfMN 9-NotPylflooront Ihwwthrm 1,4 Nothy loMpfcmmIPron* Hotliyl-t^---tfcylonopMw tNiheiet Noth/ l|*Mllhriet tnlhrktN lh|flfOMthrK<* f IwrtnllicM fyeow* Molliylpyrt-- MviowUirottnc (tr IrT phony to--1 o*f*| e M*unliitt* 2. 1`Ptwrof 1 norone 1 2'Bomof !** (hryifw 2, n-Ptmuf lwT4tlw* PofttWf * ||fl TNf ir*xo|t IfiyotM* ot,c,^s C.I C,.. C|N|| C|*t C.^,* CitHit o**t r CrJIir uf M**tl TU1I till W!' ui! tm I 711 <a 1 92K <n < it 1 Ml 1**0*C uuL ' u 'iu i i ti < 11 . 11 < 11 X1 0 II til It Ml |R imi) * IS t II < IX < 11 Mm( taln^ f 1mI9 Itt' t,,M,* M M* 17 Ot! $2 4! 611 $ U Minl!1 II 6 Wmtll 1 Ml! * 49*' i $i mm!l WJ 5 6*1* 011 tlM wvlftht f If* *f1|l<uf ptl|ir drl*4 (Ml Voluoo wHN lacrHi^ la^tt ill* h*i*4 on 'Night *1 tall lrtpp*d chMUm yriMjuclt *rl*1<f$ or* btltil i . Ike Jol| vl(lUt mrririd the gel of II* lottor rtlitfvt t* the Inltlot polycthytoM it*^U H not flwi " If* otlghi of t| irlglMl polyoor to^lr */ 1 prrn| but *nt gvMUetfd Hole |*r(*l liitd imi llw tMH In (l* tlrl4blf pt^itlci fron In* tool HONS 0 2 0 5 2 2 References 1 M. Windholz, Editor. The Herck 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 , 1985. 3 T Tanaka and A. Greenwood, Advanced Power Cable Technology Concepts and Testing. Boca Raton, FL CRC Press, 1983. I Basic 4 T Tanaka and A Greenwood Advanced Power Cable Technology II Present and Future. Boca Raton, FL. CRC Press, 19B3. 5 J, E Hogan "Wire and Cable Coverings" in: Klrk-Othmer 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 M Grayson, Editor New York Interscitnce Publishers- A Oivision 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 Oekker", 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, 8. A. Berendeev, and S. S. Ivanchev. Gas-Chromatographic Analysis of Polyeth, lane Pyrolysis Products, Plast Massv. No 12, 34-35 (1984). 10 W. J Irwin. Analytical Pyrolvsis * Comprehensive Guide New York Marcel Oekker, 19B2 11. M Chaigneau. Gas Emitted by the Pyrolysis of Different Plastic Mater-.ais a 1000. C R. Acad. Sci. . Ser C, 278(2), 109-111 (1974) 12 S L. Madorsky Thermal Degradation ot Organic Polymers New York ,,cnn Wiley and Sons, 1964 13 J Mitera, J. Michal, J Kubat. andV Kubelka Analysis of Thermo-Cx'dac ; products of Polypropylene and Polyethylene by Gas Chromatograpny/Mass Spef tromttry Fresemus1 1 Anal Cham., 281(1), 23-27 (1976) 14 J Michal, J Mitera, and S Tardon Toxicity of Thermal Degradation P-oouc of Polyethylene and Poly(proDylene) Fire Mater , 1(4), 160-166 (1976) 15 A Zeman Identification of Some Commercially Availaole Polymers by Thema Degradation m a Mass Spectrometer Anpew Hakromol C~ .-m , 31. 1-24 (It'D 16 v 5acakova. M. Borecka, and P A Leclercq Identification of Therma1 0egradation Products of Polymers by Capillary Gas Chromatograohy R E kaiser, Editor -n: Int S'/mo Capillar-- Chromatocr 4th 35-51 MONS 020523 17, N, Pirard Analysis of the Thermal Decomposition Products of Natural and Synthetic Materials Found in Qwellmgs Ann Mines Bela,, No. 5*6, 203*231 (1983). 18 R A Hawley-Fedder, M, 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,, 0. M. Hercules, a d H. J. Hainan. 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. Appl. Polya Set. . 26, 3409-3423 (1981). 21. J. Mitera and J. Mlchal The Combustion Products of Polymeric Materials. III. GC-MS Analysis of the Combustion Products of Polyethylene, Polypropy lene, Polystyrene, and Polyamide Fire Mater . 9(3), 111-116 (1985) 22 T Morimoto, It Takeyama, and F, Komshi 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 Kenkvusho Hofcoku, 45, 13-24 (1978). 24. M Pasternak, 8. T, 1 inn, and R, F. Browner The Role of Polycyclic Aromatic Hydrocarbons (PAH) in the Formation of Smoke Particulates During the Combus tion of Polymeric Materials. Symp. (Int.) Combust.. [Proc ], Volume Date 1980, 18th, 91-99 (1981). 25. T. Morikawa. Acrolein, Formaldehyde, and Volatile Fatty Acids from Smoldering Coaibustion. 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 R*p. No. 222001/0 Springfield, va u~5 National Technical Information Service, 1973, 27 V, Pacakova, P A. Leclereq, 3 .-to'otik, ana 8eroun A Studv of Oxidative Degradation of Plastics by GC and GC-MS Anal Lett,, 1S(A14), 1759-1775 (1985). 29 J H, Hodgkin, M. N. Galbraith, and Y K. Chong. Combust'on Products from Burning Polyethylene. J Macromol Sci . Chem . A17(l), 35-43 (1982) POLYETHYLENE TEREPHTHALATE) (MYLAR) CASRN. 25038-59-9 Synonyms PET *rade Names (producers) Mylar, Cronar (DuPont), Cetanar (Celanese), Estar (Eastman Kodak), Scotchpar (3M); videne (Goodyear), Avistar (FMC) (1) Products MONS 020524 with carboxy end groups are Oacron, Amilar, and Fiber V Products with methyl ester end groups Include Teryltne, Ololen, Enkalene, Fortrel, Tergal, Terital, Terltnka, Trevira, and Mylar (2). General Information Molecular formula1 (Cl0H*Q)n Structure of Monomers and Polymer1 HOCHjCHjOH Ethylene glycol 00 Terephthalic acid (R = H) Dimethyl terephthalate (R = Me) 00 --f OR Jn where R = H or CH3 Po1y(ethylene terephthalate) Uses: Major markets for polyester films in 1966 included magnetic tape, electri cal, packaging, and photography (1), Poly(ethylene terephthalate) (PET) is the most widely used film for electrical insulation (3). Electrical applications were second only to magnetic tape use in 1966. Polyesters are used for wire and cable insulation, transformer insulation, and in capacitors. Type A Mylar film, which has been biaxially structured and heat set, has numerous electrical uses such as slot liners, wedges, and phase insulation for motor and field coils, magnet wire insulation; a barrier and insulation tape in cables, transformer coil insulation, and backing for mica. Type C Mylar is used as a dielectric in high-temperature capacitors (1), Glass-reinforced PET is the only thermoplastic recognized by Underwriters Labora tory for Class H (180C) systems Class S (130C) and Class F (155C) systems tsv also use PET Many types of coil bobbins, including Class A transformer ballasts are made from reinforced PET (4). 6- 2- HONS 0Z05Z5 Thermal Decomposition Mechanisms Pyrolysis and combustion of PET give similar products and similar product yialds 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 thermooxidative. For most of the decomposition, chain scission 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: v0.. ..Hn 0jCC*H,C X CH02CCeH4C02"- OH --02CCsH<C |i 0 + CH2CH02CC6HC02 Random scission of the ester links gives rise to formation of vinyl ester oligo mers. Scission close to the chain ends will give terephthalic acid, divinyl terephthelate, and vinyl terephthalic acid nonoester (CH2*CH02CC(H4C02H) Decarboxylation of vinyl terephthalic acid monoester will give vinyl benzoate and COj; decarboxylation of terephthalic acid will give benzoic acid and C02; and de carboxylation of benzoic acid will give benzene and C02. Benzene production is not affected by the presence of oxygen. Benzoic acid, divinyl terephthalate, and viny< benzoate yields decrease above aoout 70QC 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 C02 reacts with C above about 70Q8C to give more CO. A likely route for CO production involves scission of the single bond between oxy gen and the carbonyl carbon: 0 I! '-CsH,C0CHjCH2 0 * 'och2ch2'------------ C6H4` * CO + `0CH2CH2'~ 5-25 HONS 020526 At higher pyrolysis temperatures, about as much CO is formad 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. II /p~s\ " H^3}^och. o-c-ZqJiVcochjCHjOC CH, PET 2`0CHZCHZ 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 CHjO II II It I It "V* C#HC0CH=CH2 + HOCC,H~- --------- ~CeH,C(yCH0$CC,H4-- -------- 00 II II C*H4C0CC,H< CHjCHO Acetaldehyde yields are similar during combustion or pyrolysis and decrease above about 600C, 6-26 HONS 02052? Mathane and acatylen* appaar to be produced from very simitar reactions in air or In its absence Reactions proposed that would lead to acetylene and methane for mation are the following: C*H4C0jH + CHMCH ~-c#hco2ch=ch* 0 ii '-v-C,H4CCH3 ^CtHCH=CH2 + COj 00 0 ~CeH4CCHaCH -------- '-C,H4CCH3 + CO 0 II ~-c,h4c + ch3` CH3` + H-R -------- CH + R` These reactions would also account for styrene and acetophenone Secondary decom position of acetaldehyde My 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 700*C Included acetaldehyde, carbon dioxide, divinyl terephthalate, vinyl benzoate, ethylene dibenzoate, and benzoic acid. Products formed in 1 to 9% yield included carbon monoxide, ethylene, acetylene, and benzene Trace to minor amounts of alcohols, aldehydes, ketones, benzene derivatives, ace tylene, Ct to C3 alkenes or alkanes, and 2*methyi-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 dimers and trlmers. 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 diBer.zoate, benzene, terephthalic acid, and hydroxyethyl terephthalate monoester Results are summarized in Table 6-5. 6-27 MONS 020528 6**020 O* L jd * o z c/> Table 6-4 POI Y(ETHVLENE TEREPtITItALATE) PYROLYSIS Wl(OM Ull Wl U reel* Carton nonortO* (Alton IU>I* Wo Ur Melton* Acetylene fIhylene C. * t, lUmtt/iikmi tlbylen* glycol AliMwIl Acrtelclefry(r AlOeftyBes Kelonet 2 HilAifl | ) ^Iqtvlint flfatiUrkrdt OtnUfc AC 14 Ellijrlee* ^ItHfNle Vinyl Wfliealt llr<Y4i]>tlh]r) IMA/oat* Olvinyi |(r^)HiU| lr*|4Hkolol*t Arocailc kUt Benzene Ilium 11 My IbChZCne Styrene VIrty Itolutuv IIgtenyI Acil4fiAt>wAr CO CO, Nt0 CH, t|H, C,H, 0*C" ?M-Iirc * 00*C -i*t- ,_H)_ tw 10 tec* ft t re it I B& Profcjfcly crisllIH <fcor J) u 4m to on o on 2 BIX IOC^CNjOM RUH CH/1U HW CM* C*f' / QICMl , BOX C* II. Clio CtHfdhM c(.,*ii,,c1o0,,0a1i,(tHii,Ja,ccji> ch, oa,cc,ii,i u,tii cm, C,".|CQ,), *rCO,H Ci'l. t.lMMi c.iMi", C..I ' <, Clljt,,l,UI CM, j , 1? six in IU BOX m 7ZX Minor **ir Minor Minor Mi nor Minor - ?oo*t <0 * ' 700"C 10 tec If ox 7 Ml 11 BOX o ;** ?m J 0 i IX 4 IU>*r iMerneOUle Iroco Minor NiMr Treces In Inor Minor Miner Ml Mr IB Ott W 14 )B J is ;re ) SOI 4 4 Very oinor Mnjer Minor MeroNlilc Minor Minor Minor Mimt |ettro*4feU Minor Minor Minor Very oioor Mii*r Minor i >e l*r> <| iyM vf lul*| uvUiit. oesozo thi l> * oz in Table 6 5 PGLY(ETHYLEKE TEREPHTHALATE) COHBUSTION Project **I*M iu tell* rBi>4w/ck4r fOW) m*c l'U JS0*C U_ 4W*C 1W- W*C JU_ i *oo*t M mi* -i*U- -n (*<l4n MDtilll (iiM Util* rWLKM Ar*l)rl*a* Ithjilim tgiMiihkyilr Artll*^* *cri* tMr U4l*i)fil< Mill C# C, Ktt CMtam tw cm.i KQfH Mil *tl I* niff ra-trc Mia *m\ I* rang* M* jar 4 Mi jar Ma Jar IgrtpUMIIc cil etifoic it II nyrir*tivl l*rtOIHalia MMttllf liilgyl Urrpktlullti tflnyl llhylrirt |lti<ti|UU Imi l IrtMTI Ittrixri ItntMrt C%N,(C0,H), HOCRtCHtMcnC0irt C^MCO.CU fB)J C,Mi(OlCll (K, rcH,o,j,airQ,H| t.H. 44 4 44 Ma|*r Hljar 4 4 4 4 4 -V 5I0*C I* IK m 4M W( _jiL- ' IS Hlti ' n > ' IB Mlft ' n Min Irac* ' 1 'll* ^ 4 mI* > ) Hltl I Mil Ifat* ' OfOTr II IK _Ail_ ^ 470*C )0 IN1 > ire io *< SO Ml** 49 l*i lr*c* 77 Milt > OS nld ' M Ml** s 4 Miff ' n Mil* IS Mill ' 00 M* ' Ml** is Mit< M Mlrt ' 20 niff 10 Hltl 4 mIm IlMlft I'lMltl -v |4 mIp* n IB Milt % 7 Mitt > 10 Mlo* > 14 MlM % 2 S Mlvi ' 4 Mlgl - 17 wlti -V I Ml* 7 Hltl ) S mIo* 4 Mitt `fvlyttf hid ' 100 iipfillnf unlit References 1 J. M. Hawthorne and C J Heffelfinger. Encyclopedia of Polymer Science arti Technology, Vol. 11. H, F Mark ana N h 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-Qthmer Encyclopedia of Chemical Technology. 3rd ed , Vol 13 M Grayson, Editor New York Interscience PuPltshers, A Oivision of John Wiley and Sons, 1981, pp 534-563 4. Modern Plastics Encyclopedia. 1985-1986, Vol. 62, No. 10A. 0 Agranoff, Editor New York; McGraw-Hill, Inc., 1985. 5 R. T, Conley and R. A. Gaudiana "Thermal and The-mo-Oxidativ Degradation of Polyamides, Polyesters. Polyethers, and Related Polymers" in- Thermal Stability of Polymers Vol 1 R T Conley, Editor New York Marcel Dekker, 1970, pp. 347-456. 6 HE. Bednas, H. Day, K. Ho, R. Sander, and 0 M Wiles Combustion and Pyrolysis of Polyfethylene Terephthalate). J. The Role of Flame Retaroants on the Products of Pyrolysis. J. Appl Polyw Sci . 26, 277-289 (1981) 7. M. Oay and 0 H. Wiles. Influence of Temperature and Environment on the Thermal Decomposition of Polyfethylene Terephthalate) Fibers With and Without the Flame Retardant Tns(2,3-dibromopropyl) Phosphate. J Anal, Apol Py rolysis, 7(1-2), 66-82 (1984). 8. A Gramow. 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, l553T "" 10 T. SutDsatng, C. A. Wilkie, V, T. Burger, J Carter, and C E Brown Soi'o Products from Thermal Oecomoosition of Po1y(ethylene Tereohthalate) '.rveszigat'on oy CP/KAS Carbon*13-NMR ana Fourier Transrorm-IR, J, Polym Sci Polym, Cham Ed.. 22(4), 945-957 (1984) 11 M Oay. V Parfenov, and 0. M Wilts. Combustion and Pyrolysis of Poly ethylene Terephthalate). Ill, The Effect of Tns(2.3*dibromopropyi) Pnoapnate on the Products of Pyrolysis. J Appl, Polym, Sci., 27(2), 575-589 (1982) 12 0. C. Conway and R. Marak Analysis of Polymers by Pyrolysis/Chermca' Ion ization Mass Spectrometry J Polym Sci . Pplvm Chem Ed , 20(7), 1765* 1774 (1982). 13 T. Morikawa, Acrolein, Formaldehyde, and Volatile Fatty Acids from Smoider* mg Combustion. J. Combust Toxicol . 2(2), 135-150 (1976) 14 R E. Aoams Pyrolysis Mass Spectrometry of Terephthalate Polyesters Negative Ionization, J Po 1 v Sci , Polym Chem Ed . 20(1), 119-129 (1--- 15. A Zeman Identification of Some Commercially Available Polymers by Thern. Degraaation in a Mass Spectrometer Anaew Makromol Chem . 31. 1-2J * ,,j HONS 020531 16. 0 J Carlsson, M. Oay, T, Suprunchuk, and 0 M Wiles Pyrolysis of Poly(ethylene Terephthalate) Fibers: Characterization of Involatile Residues J Appl, Polym, Sci . 28(2), 715-724 (1983) POLYSTYRENE CASRN. 9003-53-6 Synonyms. Styrene polymer; Vinylbenzene polymer, Elhenytbenzene homopolymer Trade Names (producers). Styron 666 U (Oow); Lustrex PIX6 (Monsanto, OK); Dylene, Trycite, Hostyren (fcrican Hoechst); Styrofoam (Oow). [There are more than 100 others.] General Information Molecular Formula1 (C*H&CHCHt)n Structure of Monomer and Polymer- Styrene f-- CHCH,CHCH24 Ui \ J n head-to-tai1 head-to-head-tai1-to-tai1 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 m shipping containers, furniture construction Spheres are used as a radiator leak stopper (1) Ignition-resistant grades, which include halogenated organic compounds and antimony oxide, may be used in appliance business machines, and electronic parts. Impact grades, which have improved re sis tance to hydrocarbon solvents, are acceptable for containers of food products con taining fats and oils. Polystyrene use in magnetic tape csisettes, reels, and other consumer electronic components is a growth market (2), MQNS 020532 Thermal Decomposition Mechanisms Above 330C, polystyrene degrades by the following reactions Chain-end initiation - Random scission of "weak links" (does not directly give volatiles below -v 4A0C) Oepolymeriiation (unlipping) to give monomer. Intramolecular transfers to give dimers, trimers, and higher oligomers. 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 0 to chain end unsaturatfons must be preceded by reactions that create these unsaturations Thus, the first step is removal of benzylic end units as shown (4): PhCH2CH2CHPhCK;CHPhCH{-- CH2:CPhCH2 j-CHPhCHj- PhCH3 + CH2.CPhCH2CHPhCH2' toluene CKZ:C(Ph)CH2 CK2 C(Ph)Cti3 a-methylstyrene depolymerization PhCH CH2 styrene CH(Ph)CHz- intramolecular H transfer -a oligomers intermolecul ar H transfer further chain sclssion 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 a-methyl styrene 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 o-32 HONS 02Q533 benzylic end groups formed from the 6 scissions. Oth*r mechanisms have also been proposed (5). Volatiles include mainly st>rnt and styrene dimer with other volatile oligomers Short-chain fragments Comprii* 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 o-*thylstyrene (3) Three distinct patterns of chain scission occur at subvolatilization temperature (280 to 300aC i_n vacuo) (6): 1. If the polystyrene was prepared anionically, 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 links1' 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 ketore groups (7): UV ~CH2C(Ph){00H)CH2CH(Ph)-- --------------------------------* ----- CH2C(:0)Ph + HjO + PhCHrCH-- Summary of Experimental Studies Reviewed So much work has been don* on the pyrolysis and combustion of polystyrene that only references from the last 5 years were surveyed. 6-33 HONS 02053*1 Pyrolysis. Styrene is usually reported as a major pyrolysis product (10 to 90S of volatiles) throughout the temperature ranges used in the studies reviewed (60 to 1400"C) (8-19). Using ultrathln film samples, lehrle et at (1982) (U) 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-triphenyl-l-hexene) are frequently reported (12-15) Schroede'et al (1984) (16) identified a triphenylbenzene after pyrolysis at 292 to 336C Toluene represents 6X of the volatiles at 510C (17); o-methylstyrene 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 (n- 100) are mono- through hexaphenyl-substituted oligomer chains containing Z to 14 carbons in the chain and usually some unsaturation Triphenyl- and tetraphenyl-substituted Cs 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 Lei and Locke (1984) (12), who found numerous prod ucts of the type (poly)phtnyl-substituted chains by GC/MS, Smith (1984) (19) re ported that at 700*C, only styrane and a-methylstryene wert major products, touene was formad in inttrmtdiate 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 several other pyrolysis studies indicating that the variation in the product distribution was largely due to the techniques used to pyrolyte the solystvrene sample. The temperatures, however were not ndicateo for any of the experiments reviewed. Only two groups (17.18) reported finding any polycyclic aromatic hyd-ocarbons (inqene, methyltndene, and methylnaphthalene) and ,,nese identifications were on'v tentative. Combustion. Processing polystyrene in air (injection molding, thermoforming, or thermocutting; temperatures not given) produced workplace styrene concentrat'o-s V 0 1 to s 1 0 mg/m3 air (well below the 0SHA permissible exposure limit o' 13? mg/m5), polyme- fume concentrations < 0 5 to > 10 mg/m3, and total alaen..oes \ 0 1 to ' 0 : mg/m3 Depending on the coeration, concentrations of v 0 1 to v 0 3 mg/m: formaldehyde, acetaldehyde, formic acid, and acetic acid may oe p-1"' erated Othe- oxidized prooucts mc'uded benzaidehyae (CsHsCH0), benzoic s. ( ,H) i-c scatcphenone ; 3.,-if 3DC,hs) (Va'mctaio jnoubl i snec c tec c HONS 020535 Pfiffli, 1984) (3) Major products detected in th* liquid residue from polysty rene degradation starting at about 30Q*C and enalng with complete combustion at about 450C were styrene, phenol, and toluene. Other products identified were ethylbenzene, benzaldehyde, two methylstyrenes, n-propylbentene, indene, mtthylindene, acetophenone, naphthalene, methylnaphthalene, cinnamyl alcohol, biphenyl or acenaphthene, methylbiphenyl, and diphenylethane (21). Benzaldehyde, phenyl acetaldehyde (C#HsCH2CH0), and other aldehydes were detected along with benzene, toluene, ethylbenzene, styrene, and propylbeniena when flameretarded polystyrene was combusted at temperatures up to 490C (Hasarm et al , 1976; cited by Hawley-Fedder et al., 1984) (22). The flash-ignition temperature of polystyrene Is 345 to 360aC, the self-ignition temperature is 490aC (23) Monkawa (1978, cited by Hawley-Fedder et al , 1984) (22) subjected polystyrene to flaming combustion at 600 to 900C, A soot containing polycyclic aromatic hydrocarbons (PAH$) was obtained in SOX yield based on the initial polymer weight Most of the PAKs were generally 3- and 4-membered-nng species Hawley-Fedder et al (1984) (22) trapped and identified > 100 products, mostly PAHs, after combust ing polystyrene at 800 to 95Q*C. At 950C, 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, (f>-methyIphenyl)phenylacety)ene (Ch3C#HsC4HsC:CH), and 1- and 2-methylnaphthalene were the major products Another 40 to 50 compounds were identified. Among the PAHs ident^ied were fluorene and substituted fluorcnes, substituted Dhenanthrenes and anthracenes, fluoroanthene, benzo[j,k]fluoranthene, benzo[e]pyrene. 3-methylcholanthene, pyrene, beozo[a]fluor#ne, benzo[b]fluorene. benzo[g,h,_iJperylene, benzp[c]phenanthrene, benz[a]anthracene, and chrysene References 1. G. G Hawley. The Condensed Chemical Qict'onary 10th ed New Yorir Van Nostrand Reinhold Co , 1961. ' 2 Modern Plastics Encyclopedia. 1985-1986 Vo 1 62, No. 10A J, Agranoff, Editor. New fork; McGraw-Hill Inc , 1985 3 P Pfiffli Thermodegradation of Styrene-Contaimng Polymers. Prog CW Siol Bes , 141. 203-213 (1984) 4 a Cammo, L, Costa, G Clouet. A. Chiotis. J Brossas. M Bert, and A Gjyot Thermal Degradation of Polystyrene The 3ele of Chain Ends Conu ltal ic wacrompi [Att'L 2, 317-324 (1983) HONS 020536 5, l. Costa, G. Cammo, A. Guyot, M. 8*rt, and A. Chiotis Tha Role of Chain Ends in the Thermal Degradation of Amomc Polystyrene. Polym Otqrad Stab 4(A), 245-260 (1982). 6. G. G. Cameron, W, A. J Bryce, and 1. 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 Stabilization. New York: SpnngerVerlag, 1984 8. T. Rushung and K. J. Voorhees. Analysis of Smoke Aerosols from Nonflammg Combustion by Pyrolysis/Mass Spectrometry Pattern Recoanition. Anal Chem . 56(3). 368-373 (1984). 9. HA Schneider "Survey and Critioue of Thermo-Analytical Method* and Results" in: Depredation and Stabilization of Polymers. Vol. 1 H H G Je Hi nek, Editor^ Amsterdam, Nath.: Elsevier, 1983, pp. 506-553 10 I Ericsson, Influence of Pyrolysis Parameters or Result* in Pyrolysis Gas Chromatography. J Anal App1 Pyrolysis, 8, 73-86 (1985). 11 R. S. Lehrle, R. E. Peakman, and J. C. Robb. Pyrolysis-Gas Liquid Chroma tography Utilized 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 D. C. Locke. Pyrolysis-Fluorescence Spectroscopy, PyrolysisMass Spectrometry and Pyrolysis-Liquid Chromatography of Linear and Crosslinked Polystyrenes. J Chrometoqr.. 314, 283-293 (1984) 13 L. Costa, G. Camino, and L. Trossarelli. A Study of the Thermal Degradation of Polystyrene-Chioroalkane 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 Poly(vinyl Ch.oride) Anal Chem.. 54(13), 2228-2233 (1982) 15 S. K. Brauman, I. J. Chan, and D. P. Matzinger. Polystyrene Degradation During Combustion J. Polya, Sc 1 . Polym Chem Ed. , 21(6), 1831-1845 (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 Volaf'e Compounds. Makromol Chem . 185(5), 991-1001 (1984) 17 V. Pacakova, M. Borecka, and P A. Leclercq. Identification of Thermal Degradation products of Polymers by Capillary Gas Chromatography Prcc Symp. Capillary Chromatoqr . 4tn R. E Kaiser, Editor Sad Duerkhe'm, Fed. Rep. Ger.: Tnst7-Chfomatogr. , 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 Mechanisms of Biomass. f-s$i Organic Matter, and Synthetic Polymers Prepr Pao - Am Chem Soc P1Fuel Chem , 29(2), 20-31 (1984) 5-36 HONS 020537 19. C. G. Smith. '`Practical Analytical Pyrolysis Applications for tha Polymer Industry" In: Analytical Pyrolysis. R J Voorhees, Editor London, UR. Butterworth, 1984, pp. 428*452. 20 W J. Irwin. Analytical Pyrolysis1 A Comprehensive Guide. New York Marcel Dekker, 1982! ~ 21 J, Troitisch. International Plastics Flammability Handbook. New York. Macmillan, 1983. 22 A A. HawleyPeddar, M. L. Parsons, and F. W. Karasek. Products Obtained During Combustion of Polymers under Simulated Incinerator Conditions II Polystyrene J Chromatoor , 315, 201*210 (1984). 23. E. A. Boattnar, G. L. Ball, and 8. Weise Combustion Products from the Incineration of Plastics. PB 222001/0. Springfield, VA: National Technical Information Service, 19^3. HONS 02053 Appendix A SUMMARY DF UTILITY MATERIALS PROPOSED FOR EXPERIMENTAL TESTING AND THEIR TDXIC THERMAL DEGRADATION PRODUCTS HONS 020539 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 materia's 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.) 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PMt CM. c*r PWi PAM* PMt, tM llyrrnt, OCA. * 9 . cM- rtiulH m4 Kit, (Mr. UpklMlw, IttaWlI' pyriM M llwr PMt ' Sarit cotton (frtpAII* In MrpMw riHttn) ()4) llftort, llarlNltX xiillVt utf rUl, line* rfi*a (1J.I4I <m> M'lkiiili MXthyAi, lick, ntlrlUi Malta* AC 1. Malta* lalMa* pMtftat, vinyl (MatlXt MCI. Ukm a* Mt|at, vinyl tfcWrU* vinyl 1 Ota# ctUrlPt (btr<MlH Malta*! <||r|?| Wf H#lt t' - ylatf - ill, IrfriXiP MlY**r pirlkyUt* Mf COT,. ilhytlMM ll,nlM PMs |,Mtadi<n, 4'tlayl<)KlMiM (11 1*1 PAN* M highly U**t prtOirli r*fr(H --tag yntrim ilbMti md ilktatt ||| |9] Ni PMt Imf (Mta KyflrKirMAf NCI. NCN N,f SO, PMtf PAX htMftdvrlrarf rttltto 1 M1( HP, Krylaaltrlt* IMr allrlltf <OAy1Mtn MuoriiJv Hf Mm* InhU h..i. .j1 iHkur tlMr t* Pr**t K|iMh| ItillwU haw Ui* '* l*v *ltlHty (wHwdf U UltrtlvM* HIVW ImU WittUi llk*r CO (iitln flu* Ml* |lv< P'lrOtRT1 Myril) Mjw U)*r (tthflm' C|l)Wrl itpim (h niA> Hfllf fpl|p(rllyUa* t.N.N.t.l t,N,N,0,$ C.H.O W,)( * N * Hi * nm% pm MNi, PM NA, PM PNta CH.ISCM, * trtr.la* 4ni <l MprilH^rA i<(mi MCI, V, (Of, fftravl, fclfMy (IaOhIIv# (Mr MMfU mM, l Mfaacri. pt^irMlic (Mr NCR, btMMif, nUrlli MtlllOrM*> ftrNlA^iM, *crffn MwMM, ll|rt( Ulwflt hwjrl **rcpr*lr o4 (lr4l 190. so )/ PNH PfctNftlc* Mwm4 ^Oulllt (MHF) 'kM. Si * i OCA 11* IM Kfirict *( cRIkIi>IH <AiIki), plklkal lc M*ydr Id* MHKitllft' Olytonyl tlhtr <OI*lClrlc HvM H| *U wm-cor PMmI4 lUnIc?) Itum*4 fmmml IV FOIiaO ff >iT>Uf*4 Ifty Um frrf| CltiftrghHitvwi* |wm , Irl- twl itr J C.Cl.f C.M.C1 s* *' i; OCA, C*f , COO ci. NCI, fl*rl tMUrl* J'ft octyl pMlMl*l( s t OCA (1* Um *r pMMlIc AffOyOrlOt FrMt Frtofl in f.F Cl C.Cl^f , 77 H-tipm, Cl, C*., I* MQNS 0 2 0 5 4 3 HONS 0 2 0 5 4 4 Half ll fcaat iltyfc ftvlcntlar v*lfM SyHt KrbM ||pra*y lblp*h*ny 1 (ttmal) HeihrUlbt dM*yl(Kina ll.l ^Urlr1 mIw I Hl*l ^Mrylltrltil llfhlltc Mltll H bdaitlt trl$tirl) H|irl all HInIk famuli 1 Itinlara IgilfV Marlal. teildtf l Italy l* f*Aac* Harafal Riilteji fra* r trt**" C.N lav Valaltltly Ca^aawJi lifrtrt 1# Llliritarf C.A. SO 1? MHi to n i flMh fhgwh* flmat/ (,M " PM* C.N 7MH Nipfithanic vi It Kit ftiMrtU, Arm >-) fare M r*ttli|rl<w (Uetacal liantfarntr fluid) Nwny|y lyUtiMf Prapyldlptefiyl Falylf`Clvft*) (MO ) ICO Rtfap (n irMllc iant*n<1 MUtw* (paly .Mavlbyl |1Utan*> i*,nut l*Mruorl4a C.H C H Cl C,tl. ............... C.N C.H si. Faint* *"4 Olbfr (dating! Acrylic lacqrt C H 0, [N) - MHi ** i mi CBt COT* KA (If) S- 1 III Trlthlar*' acaHc M SO II PMt so 17 PM* s pm* Ptmatf4 *- or fit! S" Maptk|hJt**t. ItfrMt (?f) 07 1 Halil (lvrl0*t (inlaf prpdttrtt In circuit irealert) 120) PNti 70 H)flM (t)| C*4l laf |Mk *y (HO Nt^ily lavtc Valalllft Oih*r llaa CD Ma litgMy taili fttOaU |M, atalyl ana. Mt atStr faitant Nyifrocirp*n Ivalfag/ Uiwat4 taattag/ laluant^ IIMr*l, ate 4 Ng fattaw (MbiiMt n*r* lade than CO 42)) OffOfftf, tatvena jjl) (.iHhtiil ClCk OCI. a pMiftm, aucapl garla^i l-aa raw* lt(g ttnma/ Itilfag/ lalww^ alcafcalt. earbmytlc Ktft KB, HC0aM Hi banian* (*lv*n* ( *,. *,. s.i,. ii. W,, (CM aulnat* (Irpinfi ma ^rtfca lar hWI KraUtk ftniraa t71) tUUr14( H^r 0i*fW#t | |^iy tiA w4r 1>>IA UdlOfcfit Idimvi MM* iwwl fmul Mi tlwr Plr*tlr fl|rtftli (irt r Nlyttn Mi %l*r iMihr film) u*u*c icN uiir | UMlItm Mi (wwkr (f Ply*r INm# n#r MfMtri) VutliW^ c^rlc t 0.0 fermtl* Liltr|Ui| _|jljj*rt_ N4ffrll ImUIIv LlWIr U (Ur*<Ml lt|lir*Lt IrM Hr/ * L* INtftrt In lUtrrift C.O.N 0 C.M.O C 0.0 f 1 rim ran c n.a t,N, C II 0 0 MA mn. rmt (m mI clur Oil m#>ly U*tf VIU << Q|hc K>w t> Atrfinlirth (fl Itilwj,* lniit|) Imi OkjMMil j!4r {illcy) lrl+4 Kr*U * PW CrnttU (cmUlnf FAN) C l| N 0 C H.O C0 F*H llltfopiawk' Pnlyill lullMtr bn44 Itlldl t%M \%0 C il H)|) FAN MM Hi t Mils Mi 3 (?) 0 a*IJMcrjrlMltll <WI livglKMfl, Our kltylM Mti tlWr lOOilftv, Mjrllitn*, cr*#lp U^tUktlMf. filM- I(m, AM)r *Our MHt. Mp MpMMyl- tmim. coo cur HONS 0 2 0 5 4 5 V Ivy Ml In ttit lf|*rt S - IkhH H SCI l Kid IW rapart <)l IFMlar^Ml Imi Iflilly <IkM llt*c*la m fcpM M (mIftriklt lllrur UlmlM n kill pyrlyal M (MwiUw OKI U lb* jrttfnU i S*n* Mw--II-- l*M | (M IKrritirt, M Muy Hf1 - yvry lllllc k*rllam( l1w(tM Iwl 1* It* liur*lr I * Bi partlatal f*4 l |fet llttrataii hla|( UiM ettUag (tinrc* fialclh IrjMUt jl Kl ^ktlllwltt (2) wltn wlH. l*f*rm*ciM m Uilclty f *wt I IN Mirlill w Ml r**4lty pvall^frl* U iKilittry MweiiF * - Mm taalc tffKli I * SlipM M rv*mikl Im Icily t UiUHy, mnHlt *r trr*w*ril%l lfc(i 4* Ml llrttlM lit* *r r*lt U urlm pfryilcal lNl ) tmn iMlcMy. krill #r Im Imi tfcrapt** 111* v tNH HNr M IrrimtlbN NhIwoI pj 4 fNiIlN awl fry IN v*Mf iNItalli anwpllM to**4 m HHN tM>Nl9k*l data I I * iMimllw la rtilf* r*t>M I* I l flafl l tillafi My N iNirN Mr* bWM IN riFai--C* fl*tt iiyMlU raiNyf far Klt and tNak wytiarf by rMt al tiytr* ^Nt p*)ye ye He Ka<| fc bydracaMpwi PCS* lllycMirlMtN HyNayli PM PM taHlItliif lNr t<*t <0, I, S) iNillNUaf lr uMa I* M *r Mr* rlr*a CM Pl)<klrlNlN 4(Ntr|-IU*lM t a**tf Cff Pf ycfcl*r laal*4 UNNilfrMt ar Mlfi Kl tHbar cMmImIM IfUlOli Sp*<*l*Ur* products buN M Tlrt| tfaitarfil (apcrlaiMal work Ni Nti 4om #r I* I* prpfnrtf OVID Saaplt* N* barn Ml N llla jlara aaarcb u 4m* Oz 1/1 REFERENCES TO APPENDIX A 1. J. V. Zbozinek. J. R. Marsh. D. Guth, and A. Bohrnerud (SCS Engineers, Inc.). State-of-the-Art Review of Combustion and Pyrolysis By-Products of PCS Sub stitutes! EPRI EL-4503. Palo Alto, CA: Electric Power Research Institute. March 1986 2. W, S. Simmons. Toxicity Profiles of PCS 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 Reinnoid Company, 1981. A. T. Monmoto, 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 Dekker, Inc , 1970, pp 457-521 6 S L. Madorsky. Thermal Degradation of Organic 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. 0. R. Schueddemage and D. 0. Hummel. Characterization of High Polymers by Pyrolysis within the Field-Ionization Mass Spectrometer. Adyan. Mass Soectrom. , 4, 857-866 (1968). 9. E. 8raun and B. C. Levin. : A Review of on Products of Combustion and Toxicity. NBilR-&5/3139. Washington, DC: Consumer Product Safety Commission, January 1985. 10 R. A. Wessling. Polyvinylidene Chloride. New York: Gordon and Breach Science Publishers, 19^7. 11. K Hiramatsu. Pvrolysis prooucts of Polymeric Materials by Mass Spectrometry III. Mass Spectroeietric Analysis of the pyrolysis Products of Polyacrylo nitrile and Poly(vinylidene Chloride). Shitsuryo Bunseki. 15(1), 17-28 (1967) 12 P Perlstein Identification of F ores and Fibre Blends by Pyrolysis Gas Chromatography. Anal. Chlm. Acta, 155, 173-181 (1983). 13 A. J. Pidduck. Mess Srectrometric Analysis of Halogenated Polymers J Anal Appl Pyrolysis. 7(3), 215-229 (1985) 14 W W. Wright. "Fluorocarbon Polymers" in. Thermal Stability of o1ymers Vol. 1. R. T, Conley, Editor. New York Marcel Dekker, Inc., 1570, pp. 287-346. 15 L Slusarski and G Janowska Thermal Decomposition of Homo- and Copolymer? of Isobutylene J Therm, Anal . 19(3), 435-447 (1980) 16 N V Schwartz Analysis of Rubber Mixtures and Vulcamzates by Thermo gravimetry and Pyrolysis-Gas Chromatography Gummi. Fasern, Kunstst . 37(6), 274-277 (1984) HONS 02054? A-9 17. N. H. Seidov, ft. Sh. Kuliev. A. I. Basov, and A. M Mustafaev Study of the ` Therm1 Oecomposition of an Ethylene-Propylene Copolymer of Different Com position. Azerb KHm Zh , (4), 99*102 (1977). 18. C. G. Smith. "Practical Analytical Pyrolysis Applications for the Polymer Industry" in: Analytical Pyrolysis X. 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 Vysokowol. Soedin. , Ser A, 27(5), 1107-1112 (1985). 20. W. Noble, B. B. Wheals, and H. M. Whitehouse. Characterization of Adhesives by Pyrolysis Gas Chromatography and Infrarad 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), 3S-40 (1963). 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. ft. Crane, D. C. Sanders, B. ft. 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. Vlrk. Pyrolysis of Unsubstituted Mono-, Di-, and Tri-cycloalkanes. Prepr,, Oiv, 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'sV PotentiaVneaTtn Hazards from Electrical Equipment Fires or Failures DHHriNTOSH Publication No. 86-111. Atlanta, 5a7 NlfiSfl. Centers for Disease Control, 1986, 25 op 26. J, Vuceta, J. ft. Marsh, S. Kennedy, L Hiidemann, and $ Wiley State-of-LheArt fteyiew: PCOOs and PCQFs in Utility PCB Fluid. EPftI CS-3308 Palo A1to, Electric Power Sesearch Institute, lj)83 27 8 Vanwert and T. Orbeck. "Flammability Testing of Dry Type Transformer Insulating Materials" in: Electr /Electron In;ul Conf , 12, [unpaginated, 3*page rapnnt] (1975). 28 T W, Dakin, L. Mandelcorn, and R N Sampson The Past Twenty-P've Years of Elactrical Insulation J Electrochem Soc. , 126, 55C-62C (1979) 29. W J Irwin. Analytical Pyrolysis- A Comprehensive Guide New York Marcel Dakker, 1962. ^ 30 J D Marshall and M. C. Kuklies Fire Retardant Laminates Having Intumesceni Adhesive Layer Comprising Shellac. U S Patent US 4058643. November 17, 1977, 4 pp HONS 0205*8 31. "Appendix A: U.S. Department of Labor, Occupational Safety and Health Administration, Chemical Information Table" in: OSHA Industrial Hygiene Technical Manuel. Chicago, IL. Commerce Clearing House, Inc., 1964, " pp. A-1 to A-281. 32. Metcalfe, 0 Sooth, H. McAndrew, and W, 0. Woolley The Pyrolysis of Organic Nitriles. Fire Hater.. 7(4), 185*192 (1983). HONS 00549 i-' 1 Appendix 8 health ano safety information for thermal degradation products Introduction Exp Itnation of Abbreviations and Health Codes Thermal Degradation Products References HONS 020550 INTRODUCTION This appendix summarizes health and safety information for the product* 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 rooia 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 inwedietely after a fire The appendix includes most of the products from thermal degradation of the mate rials reviewed in this document. The list'ig is not exhaustive because sometimes the degradation products were so numerous from certain materials that 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, tetremers, and fnghe oligomars. To help the reader readily identify which degradation products came from each mate nai -""leweo, the materiel* are 'istea below with a mnemonic -or eacn name Al lowing 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 apptno'x Chlorosulfonated polyethylene Creosote*" Cross linked polyethylenet Bisphenol A epoxy Haler Kipton Kraft paper Neoprene CSPE CRS xlpe EPO HAL KAP PAP NEO 'No products were found for thermal degradation of Teflon PFA, no simple products to list for Nylon 11. **In material itself end/or from thermal degradation products -From aaditive and there were HONS 020551 Nitrile rubber Nomex Nylon 6 Nylon 6,6 Nylon 6,10 Pentachlorophenol Polyethylene Poly(ethylene terephthalate) (Mylar) Polystyrene Polysulfone Polyurethane Teflon Teflon FEP Tefiel Viton NIT NOM NY6 N66 610 PCP PE PET STY SUL PU TEF FEP TFZ VIT 610 CRE CSPE EPO FEP HAL KAP *66 NED NIT NON NY6 PAP PCP PE PET STY SUL PU TEF TFZ VIT XLPE Nylon 6,10 Creosote Chlorosulfonated polyethylene Blsphenol A epoxy resin Teflon FEP Haler Hapton Nylon 6,6 Neoprene Nitrile rubber Nomx Nylon 6 Kraft paper PentachIoropheno 1 Polyethylene Poly(ethylene terephthalate) Polystyrene Polysulfone Polyurethane Teflon Tefzel Viton Cross linked polyethylene Two sources were used for the health and safety information, RTECS, Registry of Toxic Effects of Chemical Substances 1981*1962* (1) and the "Industrial Hygiene Technical Manual, Appendix A" (2). Information from the latter reference Is 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 <65. Note' A 1903-1984 supplement has Peen puolished Put was not used for this repor MOMS 020552 The Chemical Abstract* Service Registry Number (CASRN) follow* mo*t of the product name* In the appendix The CASRN it a unique identifier that greatly facilitates computerized searches Tor compound-spec If1c information in database* that routinely use CASRN* such as CA Search or CAS ONLINE We have included the CASRN* for those reader* who with to find more detailed information about particular products HONS 020553 EXPLANATION OF ABBREVIATIONS ANO HEALTH CODES CARC * Carcinogenic effects Identified. CASRN * Chemical Abstract* Sarvica Registry Nunbar. DESC = Description. Tha physical stata of a substarea at standard temperature and pressure. EYE IRR Eye Irritation. H * Hours of exposure. HLTH * Toxicological properties along with tha appropriate health code IARC = International Agency for Research on Cancer. IHL Toxic dose froat Inhalation; value shows length of exposure. ORAL or INGES ACUTE Ingestion acute, toxic dose from short-term ingestion INGES CHRONIC * Ingestion chronic. IPR * Toxic dose from intraperitoneal administration. IVN * Toxic dose fro* Intravenous administration. LC*o = Concentration in air required to kill half of the test animals L0JO Oose, In mg substance per kg body weight of the test animal, requires to kill half of the test animals. LO, or TD, * Lowest lethal dose or lowest toxic dose reported. Lo Lo NTP National Toxicology Program. OSHA Occupational Safety and Health Administration. PAH Polycyclic aromatic hydrocarbon. SCU = Toxic dose from subcutaneous administration. SKIN or SKIN ABS * Skin absorption, toxic from dermal exposure SKIN IRR = Skin irritation. MQNS 020554 8-5 STDS = Standards: OSHA = Permissible exposure limit TLV = ACGlH-threshold limit value TWA * Time-weignted average STL 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 TLVsB list) A "C" indicates a celling limit of exposure W x Weeks of exposure. The health codes listed below describe the toxicological proparties 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 other than nervous, respiratory, hematologic, 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 Respirator)' Effects Other "han Irritation - Respiratory sensitization (asthma or other). Respiratory Effects Other Than Irritation - Cumulative lung damage. Respiratory Effects - Acute lung oamage/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 o HONS 020555 18 Explosive, Flaaeiable, Safety (No Adverse Effect* 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 020556 9-7 THERMAL DEGRADATION PRODUCTS Acenaphthene [a PAH] (CRE, CSPE?, CASRN: 83-32-9 ESC- Solid, m.p. 93-95C mutagen STY) Acenaphthylene [a PAH] (CRE, CSPE') CASRN: 208-96-8 OESC. Solid, m.p. 88-91*C MUTAGEN Acetaldehyde, Ethane 1 (NOM, PE, PET, PU, STY) CASRN: 75-07-0 STOS: OSHA: 200 ppm, 360 mg/3 TLV. 100 ppm, 180 mg/m3 TWA; 150 ppm, 270 mg/3 STEL OESC: Vo Util* Liquid HLTH Irritation-Eyes, Not*, Throat, Skin--Marked (14). Narcosis (8). Kidney damage (3) SKIN IRR: Mild INGES ACUTE- Rat LDS0: X930 mg/kg Acetic acid; Ethanoic acid (NOM, PE, STY) CASRN: 64-19-7 STDS: OSHA- 10 ppm, 25 mg/m3 TLV: 10 ppm, 25 mg/m3 TWA; 15 ppm. 37 mg/m3 STEL ESC Volatile Liquid HLTH, Irritation-Eyes, Nose, Throat, Skin--Marked (14, Greater than 30 ppm) SKIN IRR: Yes (if concentrated) INGES ACUTE: Human T0L{): 1.47 mg/kg Acetone (EPO, NOM, PU) CASRN: 67-64-1 STDS: OSHA: 1000 ppm, 2400 mg/m3 TLV: 75C ppm, 1780 mg/m3 TWA, 1000 ppm, 2375 mg/m3 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 HONS Q2Q557 Acetonitri1 (NIT, NOM, PU) CASRN: 75-05-8 STDS: OSHA: 40 ppm, 70 mg/m1 TLV: 40 ppm, 70 mg/m1 TWA; 60 ppm, 105 mg/m1 STEL OESC: Volatile Liquid hlTH: Irritatlon-Eyes, Nose, Throat--M11d (16, Less than 50 ppm) Acute Toxicity (Cyanosis) (4, Greater than 50 bpm). SKIN ASS' Yet SKIN IRR: Yes INGES ACUTE Human TD^ 570 mg/kg Acetophenone; Olphenyl ketone (PET, STY, XLPE) CASRN: 98-86-2 OESC: Semivolatlle Liquid (m.p. 19-20C) SKIN IRR. Rabbit: SIS mg, open, mild ORAL: Rat LD0: 900 mg/kg Acetylene; Ethyne (EPO, NOM, PAP, PE, PET, PU) CASRN' 74-86-2 OESC. Gat HLTH: Explosive (18). Asphyxiation (17, Greater than 2500 ppm) ACGIH- E (Simple asphyxiant) Acridine (CRE) CASRN: 260-94-6 OESC: Solid, m.p. 107-110C SCU: Mouse LD|r-,: 400 mg/kg I Vi.': Rabbit LDt0: 100 mg/kg Acrolein (PE, PET) CASRN: 107-02-8 STOS OSHA: 0.1 ppm, 0.2S mg/m1 TLV- 0.1 ppm, 0.25 mg/m1 TWA; 0.3 ppm, 0.8 mg/m* STEL OESC Volatile Liquid HLTH; Irritation-Eyes, Nose, Throat, Lungs, Skm--Marked (14) Mutagen (2). I ARC CARC: Animal Indefinite, '79. SKIN ABS. Rabbit L0(o: 562 mg/kg SKIN IRR- Yes INGES ACUTE: Rabbit L0,o. 7 mg/kg Rat LDt0. 46 mg/kg Acrylic acid (PE) CASRN- 79-10-7 STDS TLV- 10 ppm, 30 mg/m1 TWA OESC- Semivolatlle liquid HLTH- Human Indefinite, '79. SKIN ASS' Rabbit LD10- 280 mg/kg SKIN IRR. Severe INGES ACUTE. Rat LDi0' 340 mg/kg HONS 020558 Acrylonitrile (NIT, NOM, PU) CASRN: 107-13-1 STDS. OSHA. 2 PCM* TI.V: 2 ppm, 4.5 g/mJ TWA OESC. Volatile Liquid HLTH: Suspect carcinogen (2) Reproductive Hazards (5). CNS Depression (7). ACG1H: Ala (Human carcinogen) I ARC CARC: Human Suspect '79, '82. 1 ARC CARC; Animal Positive '79 IARC CARC: Animal Suspect '82. SKIN ABS: Ves SKIN IRR: Yes INGES ACUTE. Rat L0,o: 82 mg/kg Adlponltrlle (N66) CASRN: 111-69-3 OESC: Semivolatile Liquid INGES ACUTE: Rat LDt0- 300 mg/kg Aliens (PU) CASRN: 463-49-0 OESC: Gas 3-Ami nobiphenyl (NOM) CASRN: 2243-47-2 3-Am1no-4-methylphenyl Isocyanate (PU) p-Ami nophenol; 4-Ami nophenol; l-Amlno-4-hydroxybenxene (KAP) CASRN: 123-30-8 OESC: Solid, m.p. 188-190*C SKIN IRR: Rapbit: 12.S00 gg/24 H, mild ORAL: Rat LD0; 375 mg/kg N-(3-Ami nophenyl)b*nza*1de (NOM) CASRN: 16091-26-2 2'Amlnophenyl phenyl ether; 4-Phenoxyani1 in* (KAP) CASRN: 139-S9-3 OESC: Solid, m.p. 82-84*C SKIN IRR: Rabbit: S00 mg/24 H, mild ORAL: Rat LDS0: 1100 mg/kg MQNS 020559 Ammonia (NIT, NOM, PU) CASRN: 7664-41-7 STDS: OSHA. 50 ppm. 35 mg/m* TLV: 25 ppm, 18 mg/mJ TWA; 35 ppm, 27 mg/mJ STEL OESC: Gat HUH: Acuta lung damagt/tdtma or othar (11) Irritation-Eyat, Nosa, Throat, Bronchi, Lung*--Markad (14) SKIN IRR: If concantratad INGES ACUTE: Rat oral LD10: 350 mg/kg Anlllna; Banzanamlnt (CRE. KAP, NOM) CASRN. 62-53-3 STDS: OSHA: 5 ppm, 19 mg/m* TLV- 2 ppm, 10 mg/m* TWA; 5 ppm, 20 mg/m* STEL OESC: Samivolatllt Liquid HLTH. Mathamoglobima (13). Sutpact clrclnogan (2). Acuta Tox1clty--*hort-tarm high rltk affactt (4). IARC CARC: Animal Indafinlta `74. IARC CARC: Human Nagatlva `74. SKIN ASS: Yat INGES ACUTE: Rat L0so: 440 mg/kg Anthracana (CRE, CSPE, PE) CASRN: 120-12-7 OESC: Solid, m.p. 216C SKIN IRR: Mild Sanzaldahyda (STY, SUL) CASRN: 100-52-7 DESC- Semivolatilt Liquid SKIN IRR: Rabbit: 500 ag/24 H, modarata ORAL: Rat LDso: 1300 mg/kg Banzinilida (NOM) CASRN: 93-98-1 DESC. Solid, m.p. 162-164*C Benz[a]anthractna; l,2-8annnthractne (a PAH] (CRE, PE, STY) CASRN: 56-55-3 OESC. Solid, m.p. 157-159*C IARC CARC: Animal Positlva, '73. IVN: Meuta LOLq: 10 mg/kg Benzene (CSPE, EPO, NOM, PCP, PE, PET, PU, STY, SUL, XLPE) CASRN1 71-43-2 STDS. OSHA: 10 ppm TLV1 10 ppm, 30 mg/m* TWA, 25 ppm, 75 mg/m* STEL OESC Volatile Liquid , 1 1 MONS 020560 HLTH: Suspect Leukemogen (2). Cumulative bona marrow damage (12) ACG1H: A2 (Suspect carcinogen) I ARC CARC. Human Suspect `74 & `82 IARC CARC. Human Positive `82. I ARC CARC. Animal Suspect '82 I ARC CARC. Animal '74. Listed In NTP 2nd Annual Report on Carcinogens, SKIN ABS Slight SKIN 1RR- Mild 1NCES ACUTE: Human TO^ : 130 *g/kg '81. Benzo[b]chrysene [a PAH] (CRE) CASRN: 214-17-5 OESC- Solid MUTAGEN SKIN CARE. Mouse T0L : 28 mg/kg 2,3-Benzofluoranthene, 3,4-8enzofluoranthene, Benzo[b?]fluoranthene; Benz[e]acephenanthrylene [a PAH] (CRE, PE) CASRN: 205-99-2 * OESC: Solid, m.p 163-16S*C I ARC CARC. Animal Positive, `73 TUMOR1GEN- House, skin: 88 ng/kg Benzo[j]fluoranthene; 10,11-Benzofluoranthene (a PAH] (CRE, STY?) CASRN: 205-82-3 OESC. Solid, oi.p. 16SC MUTAGEN I ARC CARC. Animal Positive, '73 Benzo[j,k]fluoranthene (a PAH] (STY?) CASRN: Unavailable [Was bento[ j, k]fluorene misnamed?] 3enzc.[n]fluorantnene, 11,12-Benzofluoranthene [a PAH] (CRE, STY?) CASRN; 207-08-9 OESC Solid, m.p 217C MUTAGEN CARC. Mouse skin- TD 2820 mg/kg/47 W-intermittent 3enzofluorenes (CRE) Benzo[a]fluorene- l,2-8enzofluorene [a PAH] (PE, STY) CASRN: 238-84-6 Benzo[b]fluorene, 2,3-8eniofluorene [a PAH] (PE, STY) CASRN 243-17-4 OESC Solid, m p 209-210.5"C 1 MONS 020561 Benzofuran (SUL) CASRN (2,3-Isomer): 271-89-6 DESC: Semivolati it Liquid Benzoic acid (NOH, PET, STY) OESC Solid, m.p. 122C, begin* to sublime SKIN ABS Yes SKIN IRR- SKin Human TD,n: 6 mg/Kg INGES ACUTE: Han LD10. LS0O mg/kg 100C Benzomtrlle (CRE, KAP, NOH, PU) CASRN: 100-47-D OESC Semivolatile Liquid SKIN IRR: Rabbit: 500 mg/24 H, moderate ORAL: Rat LD. : 720 mg/kg IHL: Rat LC.lT 950 pp/8 H ORAL: MouseLEDso: 1400 mg/kg B*nzo[g,h,i]pery1ene [a PAH] (STY) CAS5n" 191-24-2 MUTAGEN Banzo[c]phenanthrane; 3,4-Benzphenanthrana [a PAH] (PE, STY) CASRN: 195-19-7 DESC: Solid, m.p. 68*C SKIN TUHORIGEN: House TO: 940 mg/kg/39 W Btnzo[a]pyrent, B[a]P [a PAH] (CRE, PE) CASRN: 50-32-8 DESC: Solid, m.p. 175-177#C HLTH: IARC CARC: Animal Positive '73. Listed in 2nd NTP Annual Report on Carcinogens, ACCIri- A2 (Susoect carcinogen) '81. Benzo[e]pyrene [a PAH] (CRE, PE, STY) CASRN. 192-97-2 OESC: Solid, m.p. 180-182*C IARC CARC: Animal Suspected, '73. Benzo[b]thiophene; Thianaphthene (CRE) CASRN: 95-15-8 DESC: Solid, m.p. 29-32C Bipnenyl. Diphenyl (CRE, CSPE, EPO, NOH, PE. PET. STY, SUL) CASRN 92-52-4 SIDS OSHA 1 mg/mJ TlV' 0 2 ppm. 1 5 mg/mJ TWA, 0 6 ppm, 4 mg/mJ STEL DESC. Solid, m p 69-72C HONS 0205<>2 HUH: Irritation-Eye, Note, Throat, Bronchi, Lett than 3 ag/m*). CNS Efftctt (7. Greater than 3 mg/m*) INGES ACUTE: Rat LQS0. 3280 mg/kg Lung*, Skin--Moderate (15, ' 1.2-Butadiene; Methylallene (PE) CASRN' 590-19-2 DESC Gat 1,3-Butadiene (CSPE, NIT, PE, PU) CASRN: 106-99*0 STDS OSHA 1000 ppm, 2200 ag/m3 TLV: 1000 ppa, 2200 mg/a1 TWA, 1250 ppm, 2750 ag/a3 STEl DESC. Cat HLTH. Irrltation-Eyet, Note, Throat--M11d (16, Lett than 3000 pp*) INGES ACUTE: Rat LDt0- S480 mg/kg TERATOGEN (Reference 7) NTP AND OSHA CARC: Aniaal carcinogen by inhalation (References 7-9) n-Butanol (PU) " CASRN: 71-36-3 STDS: OSHA: 100 ppa, 300 ag/a3 TLV: C 50 ppa, C 150 ag/m3 TWA OESC. Volatile Liquid HLTH. Irritatlon-Eyet, Note, Throat--Moderate (15). Heering loti (7). Narcotit (8). SKIN ABS- Yet SKIN IRR: Severe INGES ACUTE: Rat L0so: 790 ag/kg 1-Butene; o-Butylene (CSPE; EPO) CASRN: 106-98-9 OESC. Gat 2-Butenenitrile; Crotonitrile (NOW) CASRN (aixt. of trant- and ci_t*)OESC: Volatile Liquid A786-20-3 3-Butenenitrl1e; l-Butene-4-mtrile, Allyl cyanide (NOM) CASRN: 109-75-1 OESC: Volatile Liquid SKIN IRR: 10 ag/24 H open, mild ORAL Rat LDS0: 115 mg/kg SKIN: Rabbit L0so' M10 mg/kg 3-1*1 HONS 0205^3 Butyraldahyde; Butane1 (PE) CASRN: 123-72-8 DESC: Volatile Liquid IHL: Human TC, 580 mg/m* ORAL Rat L0s? 2490 mg/kg SKIN IRR: Rabbit' 500 mg/24 H, severe Butyric acid; Butanoic acid (PE) CASRN: 107-92-6 OESC: Samivotatila Liquid MUTAGEN SKIN IRR; Rabbit: 10 mg/24 H, savara EYE IRR; Rabbit: 0.25 mg, savera ORAL: Rat L0to: 2940 mg/kg Butyrolactone (PE) R-Butyrolactone; 4-Methyl-2-oxetenone CASRN: 3068-68-0 SKIN IRR; Rabbit: 500 mg, opan ORAL: Rat L0so: 17 g/kg IARC CARC: Animal posltlva, '76 Y'ButyrolactonB CASRN: 96-48-0 DESC; Samivolatlla Liquid IARC CARC: Nagatlva, `76 TllMORIGEN: Mousa, skin: 50 g/kg IPR: Mousa LD,0: 1100 mg/kg Caproic acid; Haxanolc acid (PE) CASRN: 142-62-1 OESC: Samivolatlla Liquid SKIN IRR: Rabbit: 10 mg/24 H. mild ORAL: Rat LD60: 3000 mg/kg SKIN: Rabbit IDS0: 630 mg/kg Caprolactam dust (NY6, N66, 610) CASRN: 105-60-2 STOS. TLV: 1 mg/m* TWA; 3 mg/m* STEL OESC: Solid, m.p. 70-72C HLTH: Irritation-Eyas, Nosa, Throat, Skin--Modarate (15, Less thin 2 mg/m*) CNS Effacts (7, Graatar than 2 g/m*) SKIN A8S: LO. : 1410 mg/kg SKIN IRR: Ml TO INGES ACUTE: Rat L0(o: 2140 mg/kg Caprolactam (NY6, N66, 610) CASRN: 105-60-2 STOS TLV. 5 ppm, 20 mg/m* TWA; 10 ppm, 40 mg/m* STEL OESC. Solid, m p. 70-72C HLTH: Irritation-Eyas, Nosa, 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, ora), ano skin information 6-15 HONS 02056*1 Cerbazole (CRE) CASRN. 86-74-8 DESC- Solid, m.p 245-246*c ORAL: Ret LD. 500 mg/kg IPR: House LoJ. 200 mg/kg Carbon dioxide (CSPE, EPO, FEP, KAP, MOM, PAP, PE, PET, Pi), SOI, TEF, V1T) CASRN 124-30-9 STDS OSHA: 5000 ppm, 9000 g/m* TLV. 5000 ppm, 9000 mg/m' TWA, 15,000 ppm, 27,000 mg/m1 STEL DESC. Gas HLTH: Simple Asphyxiant (17, Less then 10,000 ppm). SKIN. Direct contect with dry ice can cause freezing of tissue Carbon monoxide (CSPE, EPO, FEP, HAL, KAP, NEO, MOM, NY6, PAP, PE. PET, PU, SUL, TFE, TFZ, VIT) CASRN. 630-08-0 STOS' OSHA: SO ppm, 55 mg/m* TLV. 50 ppm, 55 mg/m* TWA; 400 ppm, 440 g/m* STEL DESC: Gas HLTH- Asphyxiation, Chemical anoxia (17, Less than 75 ppm) Carbon tetrafluoride (TEF, FEP) CA5RN: 75-73-0 0E5C-. Gas IHL: Rat LCL : 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. 57-56-3 STOS. OSHA: C 50 ppm, C 240 mg/m* TLV- 10 ppm, 50 mg'm* TWA; 50 ppm, 225 mg/m* STEL OESC: Volatile liquid HLTH Suspect Carcinogen (2), Cumulative liver and kidney damage (:} Narcosis (8). ACGIH: A2 (Suspect carcinogen) IARC CARC: Animal Suspect, '72 IARC CARC: Animal Positive, '70 IARC CARC. Human Suspect, '81. Listed in 2nd NTP Annuel Report on Carcinogens, `81 Chrysene [a PAH] (CRE, PE, STY) ' CASRN. 218-01-9 STDS Tlv Suspect carcinogen OESC Solid, m.p 254-255C IARC CARC Animal Positive '73 SKIN ABS Skin carcinogen Mouse 3 5 rog/Lc HONS 020565 Cinnamyl alcohol (STY) CASRN: 104-54-1 DESC. Solid, m.p. 33-35#C TUMORIGEN- Mouse, ipr: 1400 mg/kg ORAL. Rat LOjo" 2000 mg/kg SKJN IRR- Rabbit. 522 ag/24 H, moderate Crtsol (CRE, EPO, SUL) CASRN- 1319-77*3 STDS- OSHA- 5 ppm, 22 mg/m1 TLV: 5 ppie, 22 mg/m1 TWA OESC. Solid or Semi volatile Liquid (depending on isomer) HLTH- Irritation-Eyes, Skin--Marked (14). Acute Toxicity-(CNS) (4). Cumulative liver, cardiovascular, kidney damage (3). SKIN ABS. Yes SKIN IRR: Yes INGtS ACUTE: Vanes with isomer: Rat LDS0; approximately 200 mg/kg o-Cresol is the most toxic orally Crotomc acid; trans-2-Butenoic acid (PE) CASRN 3724-63-0 OESC: Solid, m.p. 72-74C ORAL. Rat L0so- 1000 mg/kg SKIN: Guinea pig LD(0: 600 mg/kg SKIN IRR: Rabbit: 10 mg/24 H Cumene; Isopropylbeniene (STY, XLPE) CASRN: 98-82-8 STOS. OSHA: SO ppm, 245 mg/m1 TLV- 50 ppm, 245 mg/m1 TWA; 75 ppm, 36S mg/m1 STEL OESC: Semivolatile Liquid HLTH: Narcosis (8). irritation-tyes, :kin--,-tooerate (15. Less than 100 ppmj. SKIN ABS Yes SKIN IRR- Yes, Primery Irritant INGES ACUTE- Rat L0so: H00 mg/kg Cyanoam 1 ines; Aminobenzonltriles (NOM) m-Cyanoam line " CASRN: 2237-30-1 OESC. Solid, m.p. 51-53C o-Cyanoaniline; Anthranilonttrile ~ CASRN- 1885-29-6 OESC Solid, m p 47-49C IPR Moust LQjo 180 mg/kg g-Cyanoanil me CASRN 873-74-5 OESC Solid, m p 83-8SC IPR Moust LOso- 155 mg/kg MONS 020566 3-Cyanobenzoic acid (P0) CASRN: 1877-72-1 DESC: Solid, a.p. 222-224* 3-Cyanobiphenyl (NOH) Cyanogen (NOH) CASRN: 460-19-5 STOS TlV: 10 ppflt TWA OESC. Get WITH: Irritation-Eyes, Nose, Throet--Moderate (15), Acute Toxicity (Cyanosis) (4). N-(3'Cynophanyl)bentam1de (NOH) Cyclopentedlene (EPO) CASRN: 542-92-7 OESC. Volatile Liquid HLTH. Ippltatlon-Eye*, Nose, Thro*t--Moderate (15, Less than ISO ppm). Cyclopentanone (N66) CASRN. 120-P2-2 OtSC: Semi volatile Liquid SKIN IRR: Rabbit: 500 ag/24 H IPR: House L0,o: 1950 fl/Kg SCU: House IDLo: 2600 mg/kq Cyclopropane (P) CASRN; 75-19-4 OESC: Gas Oecachlopobiphenyl (POP) CASRN: 2051-24-3 OESC: Solid, a p 305-306C Decaf!uopobutane (FEP, TEF) CASRN; 355-25-9 01bani[a,h]anthracene; 1,2,5,6-D1benzanthracene [a PAH] (CRE) CASRN: 53-70-3 DESC: Solid, a.p. 266-267*C hutagen IARC CARC: Anfaal Posltlva, '73. IVN: House LD^o: 10 ngJKp Ofbenxofuran (CRE, KAP, SOI) CASRN: 132-64-9 DESC. Solid, m p. 83-84*C 5-28 02056"7 hqns 1,3-Dicyanobeniene; Isophthalonitnte (NOM) CASRN. 626-17-5 STDS. TlV-TWA 5 mg/m1 DESC: Solid, m p. 160-162*C ORAL. Rat lD(0. I860 mg/kg ORAL. Mouse LDS0: 178 ig/kg 1,4-Dlcyanobeniene; Terephthilonitri 1#, g-Dicyanobenient (HAP, Pll) CASRN: 623-26-7 QESC. Solid, m,p. 224-227*C EYE IRR: Rabbit: 500 mg/24 H, mode rata ORAL: Rat LDsoi 21 g/kg Dihydroanthracent (PE) CASRN (9,10-isomer): 613-31*0 OESC: Solid, a.p. 106-110`C Diisobutyl phthelate (NEO) CASRN: 84-69-5 DESC: Semivolatlle Liquid ORAL; Rat LDt0: 20 g/kg CRA, `.:.t 1? ;.'V: SKIN: Guinea ptg lDt0: 10 g/kg DlMthyl ather; Mathyl tthtr (PU) CASRN: 115-10-6 DESC; Gas IHl: Mouse LC,0: 386 pps/15 min Dimethyl naphtha lent (CRE, CSPE, SUL) CASRN; 28504-88-8 OESC: Semi volatile Liquids or Solids 1,6-0imtthvlnaonthalent CASRN: 5T5-43-9 OESC: Semivolatilt Liquid ORAL' Rat LDL(): 5000 eig/kg Dioctyl phthalatt (NEO) DE5C: Semlvolltilt Liquid SKIN IRR: Mild INGES ACUTE: Mouse L0lo: 6S13 mg/kg [Dl-n-octyl phthaUte, CASRN 117-84-0] Rat LD,0. 31 g/kg [Bis(2-etriylhtxyl) phthalate, CASRN 117-81-7] 1,4-Dioxtnt, Diethylene Oloxide (NOM) CSRN 123-91-1 STOS. OSHA: 100 ppm, 360 g/mJ TlV: 25 ppm, 90 eig/m3 TWA; 100 ppm, 360 mg/mJ STEL DESC Volatile Liquid S- * 0 MQNS G2Q56B HLTH: Suspect carcinogen (2). Cumulative liver end Kidney damage (3) Irritation*Eyes, Nose, Throat--Mild (16). IARC CARC, Animal Positive, '76. Listed in 2nd NTP Annuel Report on Carciongens, '81 SKIN ABS. Yes SKIN IRR: Mild INGES ACUTE: Rat LOlo: 4200 mg/kg Diphenylethene (STY) CASRN (1,2-Isomer): 103-29-7 OESC. Solid, m.p. 50-53C Diphenyl ether (EPO, SUL) CASRN 101-84-8 STDS. OSHA- 1 ppm, 7 mg/m1 TLV: 1 ppm, 7 mg/m* TWA; 2 ppm, 14 mg/m1 OESC. Votatile Liquid HLTH: Nausea (7). Irritation-Eyes, Skin--Hild (16) Cumulative liver and kidney damage (3). SKIN IRR: HI Id INGES ACUTE: Rat L0,o: 3370 mg/kg STEL Oipropylene glycol methyl ether (XLPE) CASRN; 34590-94-8 STDS: OSHA; 100 ppn. 600 mg/m1 TLV: 100 ppm, 600 mg/m1 TWA, 150 ppm. 900 mg/m1 STEL OESC: Semi volatile Liquid HLTH: Irritation-Eyes, Nose--Moderate (15). SIight Narcosis (8) SKIN ABS: Yes SKIN IRR: Mild INGES ACUTE: Rat L0,o: 4900 mg/kg Oivinyl terephthalate (PET) CASRN. 94-49-5 Ethane (CSPE, EPO, NOM. PE. PET, PU, CASRN. 74-84-0 OESC: Gas HLTH; Explosive (18). Simple Asphyxiation (17, SUL) IT oxygen level is 18X by volume) 2-Ethoxyetnanol (PU) CASRN. 110-80-5 STDS: OSHA, 200 ppm, 740 mg/m1 TLV- 50 ppm, 185 mg/m1 TWA, 100 ppm, 370 mg/m1 STEL (NOTE- Probable change to 5 ppm, with no STEL. Skin notation wi be continued.) OESC Semivolatile Liquid HLTH Irritation-Eyes. Nose--Moderate (15) Cumulative blood disturbances (12) 3"C? HOMS Q2Q5<>9 SKIN ABS: Yes SKIN IRR; Mild INGES ACUTE' Rat LOso; 3000 m9/k9 Ethyl alcohol, Ethanol (PE, PU) CASRN; 64-17-5 STOS. OSHA. 1000 ppm, 1900 mg/m3 TLV 1000 ppm, 1900 mg/m1 TWA DESC. Volatile Liquid HlTH: Irritation-Eyes, No*t, Throat--Narked (14, lest than 3000 ppm) Narcosis (8). Reproductive impairment (5, Greater than 3000 ppm) SKIN ABS- Rabbit LD, : 20 g/kg SKIN IRR. Severe t0 INGES ACUTE. I0so. 7060 mg/kg Ethylbenzene (P0, NIT, PE, PET, STY, SUl) CASRN. 100-41-4 STOS: OSHA: 100 ppm, 435 mg/m1 TLV: 100 ppm, 435 mg/m1 TWA, 125 ppm, 545 mg/m1 STEl OESC: Semi volatile Liquid HLTH: Irritation-Eye*, Nose, Throat, Skin--Moderate (15, Less than 200 ppm) Narcosis (8). Sk*N ASS: r.aCC 11 ww-jOw sig/Lg SKIN IRR: Mild INGES ACUTE: Rat LDf0: 3500 mg/kg Ethyl chloride; Chloroethane (EPO) CASRN* 75-00-3 STOS. OSHA; 1000 ppm, 2600 mg/m1 TLV: 1000 ppm, 2600 mg/m1 TWA; 1250 ppm, 3250 mg/m1 STEL OESC: Gas HLTH: Narcosis (8, Greater than 5000 ppm). SKIN IRR. Frostbite possible if liquefied gas is spilled on skin. Ethylene; Ethen* (EPO, NON, 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). ACGIH: E (Simple asphyxiants) Ethylene dibemoate (PET) CASRN: 94-49-5 Ethylene glycol, particulate (PET) CASRN 107-21-1 STDS. OSHA* 1 0 mg/m1 TLV 10 mg/m1 TWA DESC Volatile Liquid HLTH Irritation-Eyes. Nose, Throat--Moderate (15) CNS depression C1) S-21 HONS 020570 SKIN ASS. Rabbit LOso: 19.530 mg/kg SKIN IRR: Mild INGES ACUTE: Human L0L(J: 710 ng/kg Ethyiane glycol, vapor (PET) CASRN: 107-21-1 STDS TLV. C SO ppm, C 125 mg/a> TWA OESC. Vapor HLTH: Irritation-Eyes, Noia, Throat--Moderate (15). SKIN ABS: Rabbit LD,0. 19,530 ag/kg SKIN IRR: Mild IHGES ACUTE. Huaan LD : 710 mg/kg CNS depression (7) Ethylaethyiphanol; tthylcrtiol {CRE) CASRN; 1687-61-2 OESC. Solid? 6-Ethy 1--cresol UNKNOWN ROUTE: Rat LDS0: 530 mg/kg EthyIphanol (SUL) 2-Ethyl phenol CASRN' 90-0C-6 OESC: Saaivolatile Liquid CARC: Houia Skin TO. . 3100 ag/kg/12 W, intendttent 3-Ethylphenol CASRN: 620-17-7 OESC: Saaivolatile Liquid 4-Ethylphanol CASRN: 123-07-9 OESC: Solid, a.p. 42-4S*C Fluoranthene ( PAH] (CRE, PE, STY) CASRN: 206-44-0 OESC. Solid, a.p. 1D7-11DC SKIN TUMORIGEN: Mouse TO. : 280 ng/kg/58 W ORAL: Rat LD*0: 2000 ag/Eg Fluorena (a PAH] (CRE, CSPE, PE, STY) CASRN: 86-73-7 OESC: Solid, a.p. 112-115#C Formaldehyde; Mathanal (PE, PET. STY) CASRN: 50-00-0 STDS- OSHA: 3 ppa TLV' 2 ppa, 3 ng/a* TWA OESC Gas HLTH. Irritation-Eyes, Lungs, Skin--Marked (14). Suspect Carcinogen/Mutagen (2). IARC CARC: Animal Positive, '82. IARC CARC: Huaan indefinite, '82. ACGIH- A2 (Suspect carcinogen) Listed in 2nd NTP Annual Report on Carciongens, '81 6-22 HONS 020571 Thlobutyric acid, 5-dacyl attar (XLPE) Toluana; Mathylbanzana (C5PE, EPO, NIT, NOM, PE, PET, PU, STY, SUL, XLPE) CASRN: 108*88*3 STDS: OSHA: 200 ppa TLV: 100 PPM. 375 ag/a* TWA; 150 ppa, 560 ag/a* STEL DESC. Volatlla Liquid HLTH: Irrltatlon-Eyat, Noia, Throat--Nodarata (15). Narcotl* (8). Sutpact taratogan (5). Mutagan (2). SKIN ABS: Yat SKIN IRR: HI 1P I NOES ACUTE: Rat L0*o: 5000 ag/kg 2,4-Toluanadlaaina; 2,4-0iaa1 notoluana (PU) CASRN: 95*80*7 DESC: Solid, a.p. 97-99*C HLTH: IARC CARC: Animal Poiltlva, '78 and '82. Llstad In 2nd NTP Annual Raport on Carclnogam, SKIN 1RR: Mild INGES ACUTE: Rat LDI0: 260 ag/kg '81. Toluana 2,4-dlltoeyanata; TOI; Tolylana 2,4-dlliocyanata (PU) CASRN: 584*84*9 STDS: OSHA- C 0.02 ag/a* TLV: C 0.02 ppa, C 0.14 ag/a* TWA DESC: Saalvolatlla Liquid HLTH: A* that (9). Irrltatlon-Eya*, Noia, Throat, Bronchi, Lung*--Markad (14). Daraatltl* (3). SKIN IRR; Savara INGES ACUTE: LD*0: 6800 ag/kg Toluana 2,6*d1 Itocyanata (PU) CASRN: 91-08-7 DESC: Saalvolatlla Liquid HLTH: Ratplratory laniltlzatlon (Aithma) (9). m-Toluldlna (CRE) " CASRN: 108*44-1 DESC: Saalvolatlla liquid SKIN IRR: Rabbit: 500 ag/24 H, savara EYE IRR: Rabbit: 20 ag/24 H, savara ORAL: Rat LD,,>: 450 ag/kg o-Toluidlna (CRE) " CASRN' 95-53-4 STDS. OSHA: 5 ppm, 22 ag/a* TLV- 2 ppa, 9 g/m* DESC Samivolatlla Liquid a-33 MONS 020587 n-Hexadecane (N0) " CASRN: 544-76*3 OESC: Semlvolatlle Liquid (frj at 16 2C) Hexafluorapropane (FEP, 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 OESC: Gas 680*00*2, Hexafluoropropylene; Hexafluoropropene (TEF, FEP, VIT) CASRN: 116-15-4 OESC: Gat IHL Rat LCL : 20,000 mg/*/2 H Hexanal: Hexaldehyde, Caproaldehyde (FE) CASRN: 66-25*1 DESC: Saul volatile Liquid ORAL: Rat 10IO: 4890 *g/kg IHL: Rat LC. : 2000 pp/4 H SKIN IRR: RMbft: 10 ag/24 H, mid n-H#xana (PE) " CASRN: 110-54-3 STDS: OSHA: 500 pp, 1800 ag/m*/IS min TLV: 50 ppa, 180 mg/in* TLV DESC: Volatile Liquid HLTK; Nervous system dliturfiances--polyneuropathy (7) Nervous system d1sturbanes--narcosis (8). SKIN IRR: Mild IHL: Hunan TCLq: 5000 ppm/10 min Hexene iCSPE, PE) CASRN: 592-41-6 DESC: Volatile Liquid Hydrogen (EPO, KAP, NIT, NON, PAP, PE) CASRN: 1333-74-0 DESC: Gas HLTH; 51aple Asphyxiation (17, If oxygen level is 18X by volume) Explosive (18). Hydrogen chloride (gas. anhydrous) (CSPE. HAL. NEQ) CASRN, 7467-01-0 STDS OSHA: C 5 ppm, C 7 *g/mJ TLV. C 5 ppm, C 7 mq/m* TWA DESC. Gas hlTH1 Irritation- Eyes. Nose, Throat--Marked (14) Lung edema (11) Dental erosion (3) HONS 020573 Hydrogen cyanid* (gat) (KAP, N66, NEO, NIT, NON, PU) CASRN; 74-90-8 STDS: OSKA: 10 ppm, 11 mg/m1 TlV: C 10 ppi, C 10 mg/m1 TWA OESC Git HLTH. Acuta tyttamic toxicity (4). Cumulative tyitaailc toxicity (Cyanosit) (3). Hydrogen fluoride (gat, anhydrout) (HAL, TFZ, VIT) CASRN: 7664-39-3 STDS: OSHA: 3 ppm TLV: 3 ppm, 2.5 mg/m* TWA; 6 ppm, 5 mg/m1 STEL OESC- Gat HLTH. Irrf tation-Eya*. Hota, Throat, Skin--M*rkad (14). Acuta lung damaga (11). Cumulative bona damaga (3) Kydrogan sulfide (NEO) CASRN: 7783-06-4 STDS: DSHA; 20 ppm TLV. 10 ppm, 14 mg/m* TWA; 15 ppm, 21 mg/m1 STL DEED. Cei HLTH: Acuta tyttamic toxicity (4). Irrltatlon-Eya* (Conjunctivitit), Lungt--ttod*rate (15). CHS affect* (7). Hydroxyathyl tarephthalat* monoattar (PET) 2-Hydroxyph*ny1-2-phenylpropane (SUL) Hydroxyvalarie acid (PE) CASRN; 50B53-48-0 DESC. (2-itomar) Solid, m.p. 34#C (sublimat) Indan (EPO, PE) CASRN. 496-11-7 OESC; Samivolatlla Liquid ORAL: Rat U>Lo: 5000 mg/kg [ndtfit (CSPE, EPO, PE, PU, STY, SUL) CASRN: 95-13-6 STDS: TLV. 10 ppm, 45 mg/m1 TWA; 15 ppm, 70 mg/m1 STEL CESC. Semivolatila Liquid HLTH. Irritation-Eyat, Not*, Throat--Modaratt (15). Cumulative livar and kidnay damage (3). HONS 020574 Indolt (CRE) CASRN. 120-72-9 OESC. Solid, m.p. 52-54C ORAL. Rat LDt0: 1000 mg/kg SKIN: Rabbit LD*0: 790 ag/kg Isobutyraldehyde (PE) CASRN. 78-84-2 OESC. Volatllt Liquid IHL: Rat LC. : 8000 ppm/4 H ORAL: Rat LDi0: TM10 ag/kg SKIN IRR: Rabbit: 500 mg/24 H, stvtrt Isoprtnt (CSPE) CASRN: 78-79-5 OESC. Volatllt Liquid (b.p. 34C) Isovaleric acid (PE) CASRN: 503-74-2 CESE Sen volac:'e Liquid ORAL: Rat LDS0: 2000 ng/kg SKIN: Rabbit LDSo: 310 lag/kg SKIN IRR: Rabbit: 500 ag/24 H, moderate Methacrylonltrile (NIT, PU) CASRN: 126-98-7 TLV: 1 ppa, 3 ag/a3 TWA; akin warning OESC: Volatllt Liquid SKIN IRR: Rabbit: 200 ag, aild ORAL: Rat L0*o: 250 ag/kg Methane (CSPE, EPO, KAP, NEO, NIT, WOM, PAP, PE, PET, PU, SUL) CASRN: 74-82-8 OESC: Gas HLTH: Explosive (18). Asphyxiant (17, If oxygen level is 18X by volume), ACGIH: E (Simple asphyxiant) Methyl alcohol; Methanol (NON, PU) CASRN: 67-56-1 STOS: OSHA: 200 ppm, 260 mg/m3 TLV: 200 ppa, 260 mg/n>3 TWA; 250 ppm, 310 mg/m3 STEL OESC: Volatile Liquid HLTH: Cuaulatlve CNS effects (7, Greater than 40D ppa). 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 (2-) Semi volat: le fcuic. (?-) solid, m o 71-79C MONS 020575 Mathylbanzofuran (SUL) CASRN- 25586*38-3 OESC. (2-,3*.5-, or 7-1*oar) Saalvolati1* liquid 4-Mathylblphanyl; 4-Phanyltoluana (STY) CASRN. 644-08-6 DESC: Solid, m.p. 44-47'C ORAL: Rat LDS0: 2570 ag/kg 1-Mathylbutyl Itobutyrata; Propanoic acid, 2-aathyl-, 1-aathylbuty) a*tar (NEO) CASRN: 54340-93-1 Hathyl chlorlda; Chloroaathana (EPO) CASRN: 74-87-3 STDS: OSHA: 100 ppm TLV: 50 pp*. 105 ag/a* TWA; 100 ppa 205 ag/a STEL DESC: Gat HLTM: Acuta CNS affactt (4). Chronic CNS affactt (7). 'j-'ulativa livtr *nd kidnev damaot (3) SKIN ABS. Yat `` 3-Mathylcholanthrana [a PAH] (STY) CASRN: 56-49-5 DESC: Solid, a.p. 178-180*C TUMORIGEN; Oral: Rat TO, : 200 ag/kg TUMORIGEN: Skin: Rat TD^: 700 ag/kg/25 W-intanaittant TERATOGEN L 2-Mathyl-l,3-d1o*o)ana (PET) CASRN- 497-26-7 ESC: Volatila Liquid 4,5-Mathylanaphananthrna (PE) CASRN: 203-64-5 DESC: Saaivolatila Liquid Mathylathylbanxana*; Ethyltoluanat (SUL) 2-Ethyltoluana CASRN: 611-14-3 OESC. Samivolatila Liquid ORAL Rat LD, . 5000 mg/kg 3-Ethyltoluana CASRN. 620-14-4 DESC Samivolatila Liquid 4-Ethyltoluana CASRN, 622-96-8 DESC. Samivolatila Liquid ORAL: Rat LDLq 5000 ag/kg HONS 020576 Mathyl athyl katon*. 2-Butanona; MEK (PE) CASAN' 76*33~3 STDS: OSHA: 200 ppa, 590 ng/m* TLV: 200 ppa, 590 ag/a TWA: 300 ppa, 885 ag/ STEL DESC: Volatile Liquid HLTH: Irritation-Eya*. No**, Throat--Mod*rt* (15). Narcoii* (3). SKIN IRR- Hod*rat* INCES ACUTE Rat LD,0: 2737 mg/kg Methylfluortna* {PAHi] (CRE, PE) CASRN: (1-) 1730-37-6; (9-) 2523-37-7 OESC (1-) Solid, a.p B4-86#C; (9-) Saaivolatil* Liquid Mathylindent (STY, SUL) CASRN: 29036-25-7 DESC: Semivolatile liquid Methy1-4,5-aethylanaphana-thrana; Hathy1-4H-cyc1op*nta{d*f3ph*nanthr*n* (PE) CASRN: 58548-39-3 " l-Hethy'.naohthaltne (CRE, CSTS, TE, 5T:, SL'L) CASRN: 1321-94-4 OESC- Stall vol a til# Liquid INGES ACUTE: Rat LDt0; 4360 ag/kg 2-M*thylnaphthalan* (CRE, CSPE, PE, STY) CASRN: 91-57-6 DESC: Solid, a.p. 34-36#C ORAL: Rat LDL : 5000 ag/kg Mathylphananthrana (PE) L-M*thvl lsoaar CASRN: 832-69-9 MUTAGEN 2-Methyl tsoaar CASRN: 2531-84-2 OESC: Solid, a.p. 57-59*C MUTAGEN 2-Methylpyrldlne; o-Picolin* (PU) CASRN: 109-06-8 DESC: Saaivolatll* Liquid SKIN IRR: Rabbit: 10 ag/24 H, mild EYE IRR; Rabbit. 0 750 mg, severe ' ORAL Rat LDjo-' 790 ag/kg IHL Rat LC, 4000 ppa/4 H SKIN- Rapbit L0,o 410 mg/kg HONS 020577 4-MathyIpyridine; y-Picoline (PU) CASRN: 108-89-4 DESC: SmIvolatile Liquid SKIN mR: Rabbit; 10 mg/24 K, saver* EYE IRR Rabbit; 0.750 eg, severe ORAL. Rat L0so: 1290 mg/kg IHL: Rat LC. . 1000 ppm/4 H SKIN: Rabbit LD,0: 270 mg/kg a-Hettiylstyrenei 2-Ptienyl-l-propene (STY, XLPE) CASRN 98-83-9 STDS; OSHA: C 100 ppm, C 480 mg/*1 TLV; 50 ppm, 240 mg/m* TWA; 100 ppm, 485 eg/** STEL OESC. S**ivolatile Liquid HLTH. Irritation-Eyes, Note. Throat--M11d (15). CNS effeets (7). Narcosis (8). SKIN IRR: Moderate Z-(Methylthio)benzothiazola (N0) CASRN. 615-22-5 DESC SoHH. in - $?; Methyl vinyl ketone (RE) CASRN: 78-94-4 DESC. Volatile Liquid IRR: 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 OESC. Solid, m.o, 80C. sublimes at room temperature HLTH: Irritation-Eyes, Note, Throat--Marked (14). Ocular damaga/Aneaia/CNS damage (3) Suspect carcinogen (2). SKIN IRR: Mild INCES ACUTE. Human LDL<). 74 to 100 mg/kg a-Naphthol; 1-Naphthol (CRE) CASRN; 90-15-3 OESC: Solid, m.p. 95-96#C SKIN IRR. 500 mg/24 H, severe EYE IRR: Rabbit, 1 mg, saver# MUTAGEN ORAL Rat LOjo- 2,400 mg/kg SKIN Rabbit U)it> 880 mg/kg p-Naphthol; 2-Naphthol (CRE) CASRN: 135-19*3 DESC: Solid, m.p. 122~123*C SHIN IRR-. Mild INGES ACUTE: Rat L0to: 2420 mg/kg o-Naphthylamine; 1-Ami nonaphtha lane (CRE) CASRN 13**32*7 STDS- OSHA- 29 CFR 1910.1004 DESC. Solid, m.p. 48-50C HLTH: Cancar-flladder (suspect) (1). IARC CARC* Animal Indefinite, '74 IARC CARC: Human Suspect, '74. SKIN A8S- Yes INGES ACUTE. Rat L0,,,: 779 mg/kg p-Naphthyl arsine, 2-Ami nonaphthalene (CRE) CASRN: 91-59-8 STDS. QSHA: 29 CFR 1910.1009 0ESC. Solid, m.p. 111-113C HLTH: Cancer-Bladder (1). ACGIt-- (Humen Ca-c-ncge1"'. IARC CARC: Animal Positive, '74. IARC CARC: Human Positive, '74 INGES ACUTE; Rat LD,0: 727 mg/kg Nitric oxide (NOM) CASRN: 10102-43-9 STDS: OSHA: 25 ppm, 30 mg/m1 TLV: 25 ppm, 30 mg/m1 TWA: 35 ppm, 45 mg/m1 STEL DESC Gas HLTH: Hethemoglobfnemfa (13, Less than 50 ppm). CNS effects (7, Greater than SO ppm). Oaleyed lung damage (10) Nitromethane (NOW) CASRN 75-52-5 S'IS. OSHA: IDO ppm, 250 mg/m1 TLV: 100 ppm, 250 mg/m1 TWA; 150 ppm, 375 mg/m1 STEL DESC. Volatile Liguid HLTH. Imitation-Eyes, Nose, Throet, Skin--Mild (16, Less then 300 ppm) Narcosis (8, Greater than 300 ppm). Cumulative liver and lung damage (3). INGES ACUTE: RabPit L0U* 750 mg/kg Nitrous oxide (NLM, PU) CASRN. 10024-97-2 DESC. Gas HLTH1 Reproductive Hazard (Male end Female) (5, Greater than IDO ppm) CNS effects (7) MONS 020579 n-Nonacosana (NEO) ~ CASRN: 630-03-5 DESC* Solid, m.p. 66-67*C Nonytphanol (NEO) CASRN: 25154-52-3 OESC: Samfvolatfla lioufd SKIN IRR: Rabbit: 10 mg/24 hr, savara EVE IRR. Rabbit: 0.050 mg, savara Octachlorodfbanro-g-dfoxin (PCP) CASRN: 3268-67-9 DESC: Solid EYE IRR- Rabbit: 2 119, mild SKIN TUMORIGEN: Mousa TO. : 290 mg/kg/60 W IARC CARC: Animal Indafinft*" '77. Octachlorodibenzofuran (PCP) CASRN. 39001-02-0 Octachloronaphthalana; Parchloronaphtnalena (PCP) CASRN: 2234-13-1 STOS: OSHA: 0.1 mg/m* TLV: 0.1 mg/m* TVA; 0.3 mg/m* STEL OESC: Solid, .p. 197-198*C HLTH: Cumulative livar damaga/Chloracna (3). SKIN ASS: Yas Octaf1uoro*l*butene (PEP) CASRN: 360-89-4 OESC. Gas Octalluorocyclobutane; Periluorocyclobutane (FEP, TEF) CASRN. 115-25-3 DISC: Gas Octalluorofsobutylene; Peril uoroi sobutylene (FEP, TEr) CASRN: 382-21-6 Octyl alcohol; l*Octanol (NEO) CASRN: 111-67-5 OESC: Semfvolatile Liquid SKIN IRR: Mild INGES ACUTE: Mousa LDS0: 1790 mg/kg Palmitic acid (NEO) CASRN- 57-10-3 OESC. Solid, m.p 61-64C 2-31 MO NS 02058 SKIN IRR: Human: 75 mg/3 days, mild TUMORIGEN: Mouse (Implant) TO, : 1000 mg/kg IVN: House LD10: 57 mg/kg Pentachlorobeniene (PCP) CASRN: 608-93-5 DESC. Solid, m.p. 86C ORAL: Rat LDI0: 1080 mg/kg 1,4-Pantadfana (PE) CASRN: 591-93-5 DESC: Lfqufd/Gas (b.p. 26C) Pantan# (EPO, PE) CASRN: 109-66-0 STOS: OSHA: 1000 ppm. 2950 mg/m1 TLV: 500 ppm, 1300 mg/m1 TWA; 750 ppm, 2250 mg/m1 STEL DESC: Volatile Liquid HLTH: Flammable (18. Less than 3000 ppm). Narcosis (8, Greater than 3000 ppm). 2-Pentanone (PE) CASRN: 107-87-9 STOS: OSHA: 200 ppm, 700 mg/m1 TLV: 200 ppm, 700 mg/m* TWA; 250 ppm, 87S mg/m1 STEL DESC: Volatile Liquid HLTH: Irritatfon-Eyes, Nose, Throat-Moderate (15, Less than 400 ppm). Narcosis (8, Greater than 400 ppm). 1-Pentene (CSPE, PE) CASRN: 109-67-1 DESC. Liquid/Gas (bo. 29.9-30.;C) Perylene [a PAH] (CRE) CASRN: 198-55-0 DESC: Solid, m.p. MUTAGEN 227-279#C Phenanthrane [a PAH] (CRE, CSPE, PE, STY) CASRN: 85-01-8 DESC: Solid, m.p. 99-101*C INGES ACUTE: Mousa LDi0: 700 mg/kg Phenol (CRE, EPO, KAP, NOM, STY, SUL, XLPE) CASRN: 108-95-2 STDS. OSHA: 5 ppm, IS mg/m1 TLV. 5 ppm, 19 mg/m1 TWA: 10 ppm, 38 mg/m1 STEL DESC. Solid, m.p. 40,5-41.5C (absorbs water from air and liquefies) MQNS 020581 HLTH. Irritation-Eyes, Nose, Throat, Lungs--iarked (14). Acuta and chronic systemic toxicity (4) Suspect carcinogen (2). SKIN IRR: Savara SKIN ASS Yes INGES ACUTE. Human ID^: 140 mg/kg Phcnylacetaldahyda; o-Tolualdehyde; Senzeneacetaldehyde (STY) CASRN. 122-78-1 OE5C: Semi volatile Liquid SKIN IRR: Human: 2X/48 H ORAL Rat LDi0: IS50 mg/kg 1,3-Phenyienediaml ne; 1,3-0iami nobenzene (NOM) CASRN: 108-45-2 OESC. Volatile Liquid IARC CARC. Animal Indafinita, '78 TUMOR1GEN: Rat TO. , scu. 1485 mg/kg ORAL: Rat LDjo- 650 mg/kg n'-phe"viene<111 socvanstf 1.3*01 isocvanatobenzenp (N0K1 ` CASRN 123-61-5 DESC. Solid? IVN: Mouse LDS0: 5.6 mg/kg 2,3-o-Phenylenepyrene; Indano[l,2,3-cd]pyrana [a PAH) (CRE) "CASRN. 193-39-5 OESC' Solid MUTAGEN IARC CARC. Animal Positive `73. Phtnyl 'socyanate (KAP) CASRN: 103-71-9 OESC1 Samiwolatlla Liquid SKIN ABS. Rabbit LD*0: 7130 mg/m* INGES ACUTE. Rat LO,0: 940 mg/kg 2-Phanylnaphthalana (PE) CASRN- 612-94-2 OESC: 5amivolatila liquid N-Phanyl'2-naphthylamine (NEO) " CASRN 135-38-6 DESC Solid, m.p. 10?-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^ 1000 mg/kg HONS 020582 Phany) g-tolyl athar (SUL) CASRN: 1706-12-3 Phthalanl) (HEO) CASRN: 520-03*6 Phthalatas (XLPE) Phthalic anhydrlda (NEO) CASRN: 85-44*9 DESC: Solid, m.p. 132-134*C STDS: OSHA: 2 ppm, 12 mg/*3 TLV: 1 ppM, 6 mg/m3 TWA; 4 ppm, 24 mg/m3 STEL HLTH: Irritation-Eyas, Now, Throat, Lungs--Markad (14). Asthma (9). Contact skin Irritant and sansitizer (3). SKIN IRR- Yas, savart INGE5 ACUTE: Guinaa pig LDt0: 100 mg/kg Phthalfmida (KAP) CASRN: 85-41-6 0E3C: Solid, m.p. 234-236C ORAL: Mousa LDj0; 5000 mg/kg Polystyrena combustion products (800*C) (STY) IHL: Mousa LC,0: 120 mg/mVlO min Polytatrafluoroethylana dacomposltlon product (TEF) CASRN: 9002-84-0 STOS: TLV: 81 (Polytatrafluoroathylane dacomposltlon product) DESC: Varfabta HLTH: Acuta toxic tffacts (Polymar fuma fevar) Y4) IARC CARC: Animal Positlva, '79 IARC CARC: Human Indaflnlta, '79. Polyurathana A combustion products (PU) IHL: Mousa wCM: 38 mg/mVlD min Polyurathana tharmal dacomposltlon products (PU) MUTAGENIC Propana (EPO, PE, PU) CASRN: 74-98-6 STDS OSHA: 1000 ppm, 1600 mg/m3 DESC Gas HLTH: Explosiva (18) CNS effacts (7). Asphyxiant (17). ACGIH' E (Simple asphyxiant) 3-34 HONS 020503 Prop1oneIdehyde; Propant1 (PE. PU) CASRN: 123-38-6 OESC: Volatile Liquid SKIN IRR: Mild INGES ACUTE' Rat L0,o: 800 ag/kg Propionic acid (PE) CASRN: 79-09-4 STDS TLV-TWA: 10 ppa, 30 ag/a3 STEL- 15 ppa, 45 ag/a3 DESC Sealvolatlla Liquid ORAL Rat L0so: 2500 ng/kg SKIN Rabbit L0(O: 500 ag/kg SKIN IRR: Rabbit: 495 ag, open, Propfonftrlla; Ethyl cyanIda (PU) CASRN: 107-12-0 STOS- Crftarfa Document Recommended Exposure: OESC: Volatlla Liquid EYE IRR: Rabbit: 20 ag ORAL: Rat LOso: 39 ag/kQ 14 mg/m3 TWA Propyl alcohol; Propanol (PU) CASRN: 71-23-8 STDS: 05HA: 200 ppa. 500 ag/a3 TLV: 200 ppa, 500 mg/m3 TWA; 250 ppa, 625 ag/a3 STEL OESC: Volatlla Liquid HLTH: Irrltatfon-Eya*, No*a, Throat--M11d (16). Narcosis (8). Sutpaet carclnogan (2). SKIN IRR: Mild SKIN ASS: Ya* INGES ACUTE: Rabbit LD^ : 3500 ag/kg n-Propylbanzana (see atao Cuaana) (STY) " CASRN: 103-65-1 OESC: Saalvolatlla Liquid INGES ACUTE: Rat ID0-' *630 ag/kg Propylena; 1-Propant (CSPE, EP0, NOM, PE, PET, PU) CASRN: 115-07-1 TLV: Asphyxiant DESC: Gat Propyne; Methylacetylana (PE. PU) CASRN: 74-99-7 STDS' OSHA: 1000 ppa, 1650 ng/a3 TLV' 1000 ppm, 1650 mg/a3 TWA; 12SD ppm. 2040 mg/a3 STEL DESC Gas HLTH. Explosive (18, Lass than 2000 ppm). Narcosis (8, Greater than 2000 ppa). HONS 020584 B-25 Pyrene [a PAH] (CR, PE, STY) CASRN: 129*00-0 OESC: Solid, .p. 1<9-151C SKIN IRR: Moderate Pyridine (PU) CASRN: 110-86*1 STDS: OSHA: 5 ppm, 15 mg/m3 TLV: 5 ppm, 15 mg/m3 TWA, 10 ppm, 30 mg/m3 STEL DESC: Volatile Liquid HLTH- Cumulative liver, kidney and bona marrow damage (3). CNS effects (7). SKIN IRR: Mild SKIN ABS: Rabbit L0(o: 1121 mg/kg Pyrrole (PU) CASRN: 109-97-7 DESC: Semfvolatile Liquid SCU: Hou*e LD(0 61 g/kg I PR: Rabbit LDLq: 150 ag/kg Quinoline (CSE, PU) CASRN: 91-22-5 DESC: Semivolatile Liquid MUTAGEN SKIN IRR: Rabbit: 10 mg/24 H. mild EYE IRR: Rabbit: 0.250 mg, severe ORAL: Rat LD10: 331 mg/kg SKIN: Rabbit LD(0: 540 mg/kg Silicon fluoride; Silicon tetrafluoride, Tetrafluorosflane (FEP, TEF) CASRN: 7783-61-1 STDS: OSHA. 2.5 mg (HF)/m* TWA (for hydrolysis product) TLV: 2.5 mg (HF)Zm3 TWA DESC: Gas Squalane (NEO) CASRN: 111-01-3 DESC: Semivolatile Liquid Styrene (CSPE, EPO, NIT, PET, PU, STY, SUL) CASRN: 100-42-5 STDS: OSHA: 10D ppm TLV: SO ppm. 215 mg/mJ TWA: 100 ppm, 425 mg/m3 DESC: Semivotatfle Liquid HLTH: Irritation-Eyes, Nose, Throat--Moderate (15). CNS affects (7). Narcosis (8) Mutagen (2). IARC CARC: Animal Positive. '79. IARC CARC: Animal Suspected, '82. STEL B* 36 HONS 020565 IARC CARC: Human Indefinite, '79 IARC CARC: Hunan Suspected, '62. SKIN ABS: Yes SKIN IRR: Modarata INGES ACUTE- Mouse LD,0: 316 mg/kg Sulfur dioxide (CSPE, NEO, SUL) CASRN- 7446-09*5 STDS: OSHA: 5 ppn, 13 mg/n1 TLV: 2 ppn, 5 g/na TWA; 5 ppm, 10 i DESC: Gas HLTH Irritation-Eyes. Nose. Throat, Lungs Sronchoconstriction (4). Mutagen (2) Suspect reproductive affects (5) Terephthalic acid (PET) CASRN: 100-21-0 DESC. Solid, m.p. > 300*0 Tetrachlorodfbemo-g-dioxfn; TCOO (PCP) "SSC S'-'iC CASRN: (1,2,3,4-isoner) 30*46-58-8; (1,2,3,8-isomer) 53556-02-5; (1,3,6,8-isoner) 33423-92-6; (1,3,7,8-isomer) 50585-46-1; (2,3,6.7-fsonar) 34816-53-0 IARC CARC: Animal Indaflnfta, '77. 2,3,7,8-isoaier CASRN: 1746-01-6 EYE IRR: Rabbit: 2 ng, Modarata TERATOGEN MUTAGEN ORAL: Rat L0so: 22.5 pg/kg IARC CARC: Aninal Indafinlta, '77 NTP/NCI CARC. Positive in nica and rats, '82. Tatrafluoroethylene; Tatrafluoroethene (FEP, TEF, TF2) CASRN. 116-14-3 DE5C. Gas IHL Rat LCS0: 40,000 ppn/4 H Tetrahydrofuran (PE) CASRN: 109-99-9 STOS. OSHA, 200 ppm, 590 *g/mJ TLV: 200 ppn, 590 mg/m* TWA; 250 ppm, 735 mg/n1 STEL OESC volatile Liquid HLTH Irritation-Eyas, Nose, Throat, Skin--Moderate (15). Narcosis (8) Mutagen (2). INGES ACUTE Rat L0Lo 3D0D mg/kg 2.3,5 6-Tetramethylphen'' (CRE) CASRN 527-35-5 o HONS 020586 SKIN IRR: Yes, Sensitization also INGES ACUTE: Rat LD60: 800 mg/Kg Formic acid; Methanoic acid (PE, STY) CASRN: 64*18*6 STDS: OSHA: 5 ppm, 9 *g/ei TLV: 5 ppm, 9 mg/m* TWA 0E5C: VolatfIt Lfpufd HLTH: Irritation-Eyes, Nose, Throat, Skin, Lungs--Marked (14). Mutagen (2) SKIN IRR- Yes, If concentrated INGES ACUTE: Rat ID60: 1100 mg/kg Furan (PE) CASRN: 110-00-0 0SC: Volatile Liquid IHL: Mouse LCS0: 120 mg/m*/lH I PR: Mousa LOso- 7 e^/kg I PR: Rat LD(0: 5.2 mg/kg rifeptacnloroaioanio-p-Qiox.n (FC?) CASRN: 37871-00-4; (1,2,3,4,6,7,8-faomar) 35822-46-9 IARC CARC: Animal Indefinite, '77. n-Heptacosene (NED) " CASRN: 593-49-7 DESC: Solid, .p. S9-61*C 1-Haptana (PE) CASRN: 592-76-7 OESC: Volatila LiQUid Hexachlorobenzene (PCP) CASRN: 118-74-1 DESC. Solid HLTH: IARC CARC: Animal Positive, `79. IARC CARC: Human Suspect, '79. Haxachlorodlbanzo-g-dloxln (PCP) CASRN: 34465-46-8 DESC: Solid, m.p. 227*229C EYE IRR: Rabbit; 2 mg, moderate ORAL: Rat TO. : 100 mg/kg ORAL: House LC;: 1.25 mg/kg IARC CARC. Animal Indefinite, `77 (but a 2'1 mixture of the 1,2.3,7,8,9- and 1,2,3,6,7,6-Isomers was a carcinogen in rats and mice). HexacMorodlbenzofuran (PCP) CASRN 55684-94-1 HONS 020572 5-: 3