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A *4 i i tii R. ChartierJ at Assonet VltuM V. C. Pitts at N'ew Haven subject Polyvinyl Chloride - Decomposition Project 8S41-000 NHTIS 74-38, S. 2 iiatk May 10, 1974 mi-r ><> H. Bialecki I. Capuano R. Henderson C. H. Hofrichter R, E. Maizell B. I. C. T, R. C. The attached new material on thermal degradation of polyvinyl chloride has been collected since Mrs. Floto's memo of February IS, 1974. Do you wish us to continue collecting and forwarding such references or should we discontinue this program? VCP/rfd Attachments a./ v/c. Pitts OLI 6132 WHY THJ-5 IF YOU RETAIN* T. SPECIFY A OEtJUIte Hf.TC*TlCM *|60' ONE YCA*--------------- OTHL H_ extreme or apparently inappropriate test conditions, but by so doing, if limiting behaviour can be identified, due account of this can be made in the design specification and the chances of successful performance can be improved. Acknowledgement The author wishes to thank Mr P.I. Vincent for his help and cornmeats during discussion of this paper. References 1 Gotham, K. V. Plastics & Polymers 40 (1972) 59. 1 Gotham, K.V. Ibid 40 (1972) 277. * Vincent, P.I. `Impact tests and service performance of thermo- piastics' Plastics Institute Monograph 1971. 4 Kennedy, A.J. `Processes of creep and fatigue in metali' (Oliver and Boyd, 1962). DECEMBER 197} - WOOLLEY 1 Gotham. K.V. Plastics & Polymers yi (1959) 209. 5 Buchnall. C., Gotham, K.V. and Vincent, P.f. `Polvmer science1 Ed A.D. Jenkins. Vol. I Chap 10 (North-1 Icllaiid Publishing Company, Amsterdam and London). ' Hill, R. `Plasticity' (Clarendon Press, Oxford. 1950). * Peterson, R.E. `Stress concentration design factors' (John Wiley Sc Sons Inc, New York, 1953). Gotham, K.V. and Turner, Polymer Eng. Sci. 13 (1973) 113. id Boogaart, A. van den, and Turner, C.E. Trans, J. Plastics Inst, 31 (1963) 109. u Paris, P.C. and Sih, G.C. `Stress analysis of cracks: fracture and toughness testing and its applications' ASTM Special Technical Publication No. 3SI. '* Marshall, G.P., Culver, L.E. and Williams, J.G. Plastics 4 Polymers 37 (1969) 75. io Vincent, P.I. `Localised plastic deformation and fracture' TR 97 Division of Polymer Science, Case Western Reserve University, Cleveland, Ohio. 14 Watts, N.H. and Bunts, D.J. Polymer Eng. Sci. 7 (1967) 90. __ Toxic products from plastics materials in fires W.D. Woolley BSC, phd, mifiree Firm Research Station, Building Research Establishment, Department of(he Environment andFire Offices' Committee Joint Fire Research Organisation Abstract: Over one-halfofthe fatalities in fires are caused by smoke end toxic gases. Work is inprogress at the Fire Research Station to study the production oftoxic gases when plastics materials are decompos ed under controlled laboratory conditions involving pyrolysis at temperatures up to 1000`C and in fullscale tires using a special compartment with a variable ventilation slit (door) leading to a corridor. When heated above about 190~C. PVC releases the toxic gas hydrogen chloride. At 300JC this dehydtoch/orination is rapid and quantitative. In tires involving wood and PVC fuels the main toxic products are carbon monoxide end hydrogen chloride and the contribution of hydrogen chloride to the over-ell toxicity depends upon the fuel loadings and ventilation. Pyrolysis of flexible polyurethane foam at about 300"C releases 0 polymeric `yellow smoke' which decomposes at temperatures above 800cCin nitrogen (SQO"C in air) to give e range of nitrogen-containing compounds, particularly hydrogen cyanide. Fires involving industrial toads of foam show that temperatures in excess of 1000'C (sufficiently high to decompose the.ye/iow smoke) are attained within e few minutes. During the early stages of the fire the toxic hazard from hydrogen cyanide cen approach the same order of magnitude as that from tha carbon monoxide. 1 Introduction Last year in the United Kingdom approximately 1000 persons died as a direct result of fire. Evidence indicates that over one-half of the fatalities were caused by the combined effects of smoke and toxic gases and that the remainder were due to burns and other injuries. In addition, many thousands of persons were involved in potentially hazardous fire situations. The effects of smoke and toxic gases can be considered separately. The main effect of smoke is that it reduces visibility and hence hinders escape, whereas the effect of toxic gases, coupled with oxygen depletion of the atmos phere and heat exposure, is to kill. Certain toxic gases at sub-lethal levels can directly hinder escape by producing Dr W.D. Woolley is a Principal Scientific Officer at tha Fire Researcn Station. Boreham Wood. Herts. He graduated in chemistry at St Andrews in 1901 and spent two years with the National Research Council ol Canada studying photochemical reactions. Flaitttl 4 Pjlymtrt DtCEMICR 197]. MINTtO IN CHEAT HVTAIN severe eye and inhalation irritancy. Other toxic gases that are odourless kill rapidly without warning. This paper will outline the current work being carried out at the Fire Research Station to study the release of toxic products when building and furnishing materials are involved in fires. As examples the paper will report the results of two well known and topical materials, namely polyvinyl chloride (PVC) and polyurethane foam. Essentially, the research is divided into two main areas involving, first, small-scale laboratory decomposition experiments under simulated fire conditions, and, secondly, full-scale fire tests. It is relevant in this report to discuss the experimental facilities and procedures and then give a broad survey of the results. 2 Experimental procedures 2.1 Laboratory experiments In the laboratory studies, smali samples of material are decomposed in a furnace system under the conditions likely to be encountered in fires, ie temperatures up to and in excess of 1CKXVC in environments ranging from air to a serious deficiency of oxygen. This is in fact a study of the OLX 6133  i C"/---- TOXIC PRODUCTS FROM PLASTICS MATERIALS IN FIRES thermal and thermal-oxidative decomposition of materials. The volatile products released from the de composition are collected in a refrigerated trap coupled on-line to a research gas-chromatograph/mass-spectrometcr unit. In this way the products released under various decomposition conditions can be identified quantitatively and qualitatively. From this information it is possible to make an appraisal of the toxic species likely to be en countered in fires. As shown later in this report, a further important feature of the laboratory studies is the elucidation of the decomposition mechanisms and the evaluation of de composition kinetics. Information obtained from laboratory tests is vital in the design and evaluation of experiments involving the full-scale fire rig. 2J Full-scalefire experiments A schematic diagram of the experimental fire compart ment with corridor is shown in figure 1; it consists of a compartment (approximately 3 x3m in area and 2-5m high) with a variable ventilation slit (door) leading to a corridor (1 -3m wide and 12-6m long). Basically it is designed to represent a fire situation in a compartment adjacent to an escape route. The rig can be loaded directly with plastics materials or alternatively lined with plastics wall linings (either inside the compartment or inside the corridor) with a cellulosic fucl crib. Alternatively, specific items (eg chairs or beds) can be introduced directly into the compartment for tests. The rig is fully instrumented for monitoring the com partment and corridor gas temperatures, for measuring the smoke evolution and for sampling gases at various points for subsequent analysis of toxic products. Carbon monoxide and oxygen concentrations in the fire gases are monitored in all tests. Other toxic species are monitored as required. 3 Results 3.1 Polyvinyl chloride 3.1.1 Laboratory tests. PVC is now widely used in buildings both in the structure and in the furnishings. Concern has been expressed that when involved in fires PVC releases a number of highly toxic species such as phosgene. Recent work at the Fire Research Station has done much to eliminate the concern over phosgene.1 The release of the toxic gas hydrogen chloride from the thermal decomposition of PVC is now well established. This dehydrochlorination becomes significant at tem peratures above about 190'C, and the higher the tempera ture the more rapid is the release of hydrogen chloride. Air tends to increase the rate of dehydrochlorination for a given temperature. At high temperatures there is a virtually quantitative release of all the available chloride as hydrogen chloride. From consideration of the kinetics of dehydrochlor ination2 for a typical rigid (unplasticized) PVC it has been shown that the extent of dehydrochlorination for a given temperature is given by (100-P)-* = O-l+i&f (0 where P is the extent of dehydrochlorination (as a per centage of the theoretical), t is the decomposition time in minutes, and k is the rate constant, given by logiofc = 15-27-9-13 x 103 (1/7'; (2) for inert atmospheres and log10k = 12-93 -7-86 x 103 (1IT) (3) for air atmospheres. T is the decomposition temperature in degrees absolute. The times for various percentages of dehydrochlorination in inert and air atmospheres as calculated from eqns 1,2 and 3 are given in table 1. Tabic 1 Calculated time Tor 20-60 per cent of theoretical dehydrochlorination in nitrogen and air between 2001 and 300' C TEMPERA TURE EXTENT OF dehydrochlorination 20% 40% 60% NITRO GEN AIR NITRO GEN AIR NITRO GEN AIR c min min min min rr.in min 200 251-4 114-9 619 S 233-3 1237-3 5C-5-.S 220 41-4 24-3 102-1 600 204 0 M9-S 240 7-9 5-3 19-4 14-3 33-7 2S-6 260 i-69 1-55 4-16 3-32 8-31 7-62 230 0-41 0-45 1-00 1-12 2-00 2-23 300 Oil 014 0-27 0-36 0-53 0 71 OLI 6134 Under non-isothermal dehydrochlorination conditions (ie where the temperature rises as a function of time) as in fires, a time interval summation process has been used for calculating the total hydrogen chloride released as a function of time from a knowledge of the temperature/ time profile of the PVC. The equation for this process is f-- n (100--/*)-* =* 0-1 + i J/ 2 *<ml> (4) 1-1 where Pn is the total hydrogen chloride (as a percentage of the theoretical) released at the end of the nth interval. At is the time interval in minutes and fc<mu is the rate constant at the mean temperature of the ith interval as calculated from eqn 2 or 3. A comparison between the experimental and calculated dehydrochlorination of PVC subjected to a tempera* ture rise from 190 to 2S6C in about 20min is, given in figure 2. As can be seen, there is good agreement between the experimental and theoretical behaviour except that the experimental curve lags behind the theoretical curve. This lag is due to the experimental collection delay. The potential of this method in studies ofreal fire situations is at present being evaluated. After dehydrochlorination of PVC has taken place, the residue has a conjugated polyene structure which itself decomposes to give a complex mixture of products; these have been identified by gas chromatography and mass spectrometry1 as consisting of saturated and unsaturated hydrocarbons with a predominance ofaromatic materials, particularly benzene. The presence ofair during decompo sition acts as a catalyst and increases the yields of the hydrocarbons but without the formation of any oxy DECEMBER 1971 - WOOLLEY genated organic species. Oxidation does ofcourse produce oxides of carbon. From the laboratory studies, it is concluded that the main toxic risks from PVC arise from carbon monoxide and hydrogen chloride. Contrary to certain popular belief, there are no significant quantities of phosgene, chlorine or organic halides. The hydrocarbons themselves make little contribution to over-all toxicity but the aromatics are dearly precursors of smoke formation. 3.1.2 Full-scale tests. A typical full-scale fire test, to study the behaviour of PVC in fires, involves a wooden crib (127 kg) as the main fuel source in the compartment, the walls being lined with 100 kg of rigid PVC, and having a ventilation slit 700mm wide. A comparative experiment is carried out with wood alone (127 kg) in the compartment. Figure 3 shows the gas temperatures in the com partment as a function of time for these tests. The experi ment with PVC gives a higher temperature for a longer period than wood alone, due to the extra heat contri bution from the PVC. Typical concentrations of carbon monoxide and hydrogen chloride recorded during these tests are given in figure 4. The concentration scales are adjusted in the ratio of 2:1 to show equivalent toxicities since carbon monoxide is directly hazardous to life at 3000 ppm- and hydrogen chloride at 1500 ppm. With hydrogen chloride there is the added problem that it is a -- - wood - - - * wood and PVC fiQ 4 Toxic gas production front wood and PVC fires --' -- Carbon fttonoxlJc f^oovl) OLI 6135 TOXIC PRODUCTS (ROM PLASTIC'S MATERIALS IN FIRES severe eye and inhalation- irritant, and concentrations as low as 100 ppm have been reported as intolerable to breathe.3 * From tests of this kind a number of broad conclusions can be reached for fires involving wood and PVC fuels:4 (a) If the ventilation is low the fire develops slowly; carbon monoxide production is important and hydrogen chloride is released relatively late and slowly. (b) With high ventilations the fire develops rapidly; carbon monoxide production is relatively low and hydrogen chloride is released relatively early and rapidly. (c) If PVC is present in the fire load (eg as in furnish ings) hydrogen chloride will be released earlier and more rapidly than if the PVC is present as a wall lining. 3.2 Polyurethanefoams 3.2.1 Laboratory tests. Polyurethane foam is used in flexible form in furnishings and in rigid form in certain applications within the structures of buildings. There has been concern that toxic products containing nitrogen (such as hydrogen cyanide) could be released in fires involving polyurethane foams, although until recently there has been little information to substantiate this view. In fact, early decomposition studies have tended to support the view that virtually no nitrogen-containing materials are released during thermal decomposition and that the nitrogen content of the foams remains in the non-volatile residue. The first consideration in studies of the decomposition behaviour of polyurethane foams was to monitor the nitrogen losses during thermal decomposition and to compare these with the corresponding weight losses. This was effected by decomposing samples of both rigid and flexible polyurethane foams in a furnace for 15-min intervals at fixed temperatures and analysing the residues by elemental ultratnicroanalysis (for the determination of the weight percentages ofcarbon, hydrogen and nitrogen). Figure 5 shows the comparisons between the weight and nitrogen losses for a typical MDI rigid polyurethane foam (prepared from diphenyl methanc4,4'diisocyanate) showing a general decomposition behaviour with only little evidence of any extra nitrogen retention in the residue. Figure 6 shows the equivalent data for samples of TDI polyester and polyether flexible foams (prepared from tolylene diisocyanate). In each case there is identical behaviour and a preferential loss of a nitrogen-rich material, and at 300eC there is a virtually complete loss of the nitrogen content of each foam with a corresponding weight loss ofabout 30 per cent. Because of this behaviour and of the wide use ofTDI flexible foams within buildings, recent research efforts have been devoted to the flexible foams and will be extended to rigid foams at a later date. It is now known that the behaviour of the TDI flexible (polyester and polycther) polyurethane foams represents a depolymerization process,5 namely that the foams decompose to give the parent polyol and TDf. For tunately the TDI (a highly toxic material) is not released in `free' form but mainly as a yellow smoke (probably a polymeric form of TDD which has been isolated in the laboratory. The yellow smoke from the polyester foam appears to be identical with that obtained from the polyether material. Its elemental composition is appro,xi- fig 5 Decomposition data for MDI rigid polyether foam O Nitrogen lou AiWeifbt ton fig 6 Decomposition data for TDI flexible polycihcr and polyester fi-.uns Q yiteQfcn loss, polyester O Weight lew. pr>i>c<trr Nitrogen lu*s, pol>cthcr u Weight lo. puly-ihcr maicly 64 per cent carbon, 6 per cent hydrogen and 17-5 per cent nitrogen, the remainder being oxygen. The ycllowsmoke is relatively stable to thermal decomposition and will volatilize unchanged from furnace systems at OLI 6136 tempcratuies up to 800'C but will decompose readily above that temperature. Chromatograms (flame ionization detection) of the decomposition products of tUe yellow smokes obtained from the polyester and polyether foams and decomposed atSSO'C are shown in figure 7. The similarities between the `finger print' chromatograms are evident and confirm the chemical similarities between the two smokes. The identifications of the decomposition products obtained by coupled gas-chromatography/mass-spectrometry are listed inT able 2. The main nitrogen-containing materials are hydrogen cyanide, acetonitrile, acrylonitrile, pyridine and benzonitrile, and of these hydrogen cyanide pre dominates. The yields of hydrogen cyanide increase with temperature, and at 1000C (maximum temperature used) approximately 70 per cent of the theoretically available nitrogen of each polyurethane foam is released, via the yellow smoke intermediate, as hydrogen cyanide. The yields of cyanides obtained either directly from the decomposition of the foams or indirectly from the de composition of an equivalent weight of yellow smoke are in good agreement. In air atmospheres the decompo sition proceeds by the same yellow smoke intermediates as those observed during pyrolysis experiments. Further, the intermediates release the same nitrogen-containing materials (of which hydrogen cyanide again predomi nates) but they decompose at a much lower temperature. The yields of hydrogen cyanide from the polyester yellow smoke, decomposed either directly or via the decomposition of the foam in inert and air atmospheres, are shown in Figure 8. Table 2 Identifications of the decomposition products of the yellow smokes by mass spectrometry (see Fig 7) PEAK NOMENCLATURE a b c d e f c h i j kl m n o P q r s t u V w X A B C D E F G MASS-SPECTROMETRIC INTERPRETATION Nitrogen* Carbon dioxide Ethylene Ethane Water Propane Hydrogen cyanide Not identified Butync or butadiene Acetonitrile Acrylonitrile Propionitrilc Methyl acrylonitrile or vinyl acetonitrile Benzene Methyl acrylonitrile or vinyl acetonitrile Not identified Pyrrole Pyridine Toluene Methyl pyridine Methyl pyridine Cycloociatetrene or styrene Vinyl pyridine Benzonitrile or benzamide Not identified Indene Methyl cyanobcnzcnet Methyl cyanofccr.zcne* Not identified Not identified Naphthalene Quinoline or isoquinoline Not identified `Furnace carrier gas. tOihcr possibilities, phenyl acetonitrile or indotc. DECEMBER 197*3 - WOOLLEY" no 7 Chromatograms of the decomposition products of yellow smokes at SJO'C (a) from polyether foam (b) from polyester foam (For idattiftettions Me Tibi* 1) fig 8 Yields of hydrogen cyanide from polyester yellow smoke and foam in nitrogen and air ---------Yellow imokc, nitrogen ------- Foam, nitrogen -- -- Yellow smoke, air ----Foam, air OLI 6137 iu,.` u. ; j i ivj.'i i i' ii: a r yields after about five minutes is uncertain; it may be associated with an initial and relatively rapid loss of yellow smoke, which subsequently decomposes leaving a polyol residue which continues burning almost as a liquid. fig 9 Gas temperature Tor polyurethane fire Current work is directed towards studies of the pro duction of oxides of nitrogen in air atmospheres and the possible release of free TDI from the foams. 3.2.2 Full-scale tests. A number of full-scale fires involving industrial loads of flexible polycther polyurethane foams have been carried out in the test rig. Figure 9 shows the temperature within the compartment for a foam test of 13S kg (ventilation slit l-15m wide) which is typical of the general fire behaviour of these foams and shows a rapid temperature rise followed by a `steady-state' burning condition. Because of the rapid temperature rise the yellow smoke can survive in the compartment only during the first few minutes of the test. Subsequently, decompo sition takes place within the hot gaseous zone of the compartment. Samples of the fire gases have been extracted from the compartment during the 'steady state' burning and have been analysed in the laboratory. As expected, hydrogen cyanide, acetonitrile, acrylonitrile, benzene, pyridene, toluene and benzonitrile have been detected from the decomposition of the yellow smoke. Further, the relative proportions of these materials are in good agreement with the values expected on the basis of the temperature and oxygen concentration within the compartment. The concentrations of carbon monoxide and hydrogen cyanide (plotted on scales of equivalent toxicides as estimated from toxicological literature6,7) are shown in figure 10. Hydrogen cyanide is taken as being directly hazardous to life at 300 ppm; carbon monoxide is hazardous at 3000 ppm and the scales of figure 10 have been adjusted in the ratio cf 10:1. In the early stages of the fire the hazard from cyanides can approach the same order of magnitude as that from the carbon monoxide. The reason for the rapid decline in the hydrogen cyanide 4 Discussion As has been indicated in this report, the study of toxic gas production from even a single material requires an ex tensive research programme covering the full range of temperatures and atmospheres likely to be encountered in fires. Basically this programme invokes the qualitative and quantitative analysis of the chemical nature of the products formed during both small-scale laboratoryexperiments and full-scale fire tests. This analysis identifies only by chemical nature. There is no instrumentation available which will measure toxicity or irr mney. The assessment of the toxicity of the ci. ..r.ical products is made on the basis of published data3-: ` obtained from human and animal exposures when aval;.,hie. Such data are very limited, and when applied to lire , ,ses they do not necessarily indicate the true over-all toxicay for a number of reasons, particularly (a) that the toxicities of certain chemical species may be as yet unknown; (b) that there may be interactions (synergisms) between the effects of different toxic species, and that mixtures of toxic materials may be more hazardous than expected. The Fire Research Station has therefore recently placed a contract for toxicity studies with the Chemical Defence Establishment at Horton. This work, which is now forming an important addition to the laboratory and full-scale tests, is aimed at evaluating by animal experiments the toxicities of the fire gases from both wood and a number of important plastics. In this way it is hoped to establish whether the toxicities of the fire gases can be attributed to the carbon monoxide present and hence to determine whether there is a significant contribution from other toxic species. Animal experiments of this kind also give the oppor tunity to study synergistic effects of toxic species and to consider other important physiological effects of fire gases such as irritancy. In addition to the Porton contract the Fire Research Station has placed substantial contracts at the Industrial Materials Research Unit (IMRU) of Queen Mary College and at the Rubber and Plastics Research Associa tion (RAPRA) at Shawbury. The work at IMRU involves important fundamental studies of the smoke formation from plastics involved in fires. At RAPRA. the fire hazard of plastics in furniture and furnishings is being considered, and the work initially involves ignition and fire development measurements followed by smoke and toxic gas production from complete items of furniture (composites) rather than individual plastics components. no 10 Toxic gas production from polyurethane fire ...... Carbon monoxide ----- Hydrogen cyanide Acknowledgements This paper is Crown Copyright ami is icpio.1in.od by pcrmic.jnn oi the Controller, JIM Stationery Office. It is contributed by per mission of the Director. Building Research Establisht'cm 11 he I he Research Station i. the Joint I .re Re.cn'vh Ore 1111/the Dcpartnicnt of the Environment attd the l ire <_o:"-nii!eci. It was first presented at the symposium on `Smo'.te tioni binning plastics' organized by the Industrial Materials Rvscatch Unit, Queen Mary College, University of London on 22 February 1973. OLI 6138 2S5 Vl'L in 1 b S- = Jl o = wi-- v THERMAL utGw AGAT I G.M UF- PUl.Y (VINYL CHLORIDE). I. APPARATUS FOR INVESTIGATION FOR EARLY STAGF.S OF THERMAL DEGRADATION AB3AS. KENT ii. V SURVIK, EP-LlNG M. DER. ORG. CHEM. / CHALMERS UNIV. TECHNQL. / GQTEBGRG SWEO. J. APPL. POLYM. SCI. JAPNAii, VOL 17 I$S 12 YR 1973, PGS 3567- 76 //KEYWORDS// THERMAL DfcHYDPUCHLORINATION KINETICS PVC CONDUCT I METRIC DET N HYDROGEN CHLUKIOE r. D O U 800027610N V0L*8O ISS=06 SEC=35 WT* 9 CA447CARD 6 THERMAL DEGRADATION OF POLY(VINYL CHLORIDE). II. DEGRADAT ION MECHANISM BASED ON DECOMPOSITION ENERGETICS GUPTA, V. P. / ST. PIERRE, L. E. DEP. CHEM. / MCGILL UNIV. / MONTREAL / QUE. J. POLYM. SCI., POLYM. CHEM. EO. JPLCAT, VOL 11 ,IS$ 8 , YR 1973, PGS 1841- 50 //KEYWORDS// PVC THERMAL DEGRDN KINETICS CHLOROPRQPENE VINYL CHLORIOE COPOLYMER ( C .0 & o 800083838E VQL=80 I$S16 SEC*35 WT 9 CA447CARD 15 DEGRADATION OF POLY(VINYL CHLORIDE). III. KINETICS OF THE RMAL OEHYQRCICHLQR I NAT ION CATALYZED BY SLOW-DIFFUSING HYDRGG EN CHLORIDE CARENZA, M. / MOISEEV, YU. V. / PALMA, G. LAB. FOTOCHIM. RADIAZ. ALTA ENERG. / CONS.. NAZ. RIC. PADUA / ITALY v" J. APPL. POLYM. SCI. JAPNAB, VOL 17 ,ISS 9 , YR 1973, PGS 2685- 94 //KEYWOFOS// PVC DEHYQROCHLORINATION KINETICS HYDROGEN CHLORIDE DEGRDN CATALYST CATALYST DEHYDPOCHLORINAIION PVC ACS COPYRIGHT 1974,CA-C0NDENSATES ) j O o o 8000603o4H V0L = 60 icr-i > cl i~ PYROLYSIS OF PUL Y( VINYL~CHLnp fJ tn= 9 CA447CARD OMPUUNDS 1VMVL CHLORIDE). FORMATION OF AKOMATIl DpQ,Ap'DNIUr A UDAf TAKttJ SapInAPPL* CHH* 7 0SAKA INST. TECHNOL. / OSAKA EN 01 TL P-'-rima /mvtUs/, 13 ,ISS 13 TM H. "SS 18- 23 Ku^vi,pu^s:Ycs:ri'rs,s OXIDE METAL PVC PYROLYSIS CHLORIDE METAL PVC PYRQLSIS OLI 6139 .lu^t-O.V.clN V'iL=JiO ISS- 12 SC=3b WT = l3 C44V7CAKD 7 THw'-.'AL ufc CO-'iP J j 11 I Oi ; OF A VINYL CHLuR I l)E--PROP VwPC LY M L rv ,v YAKOV* V N / TfiO ITSK 11 * 8 8. USSR TR- KHIi-i. KHIM. TEKHNUL. T KK f A L, VOL ,ISS l , YR //KEYWORDS// THERMAL UcCOMPN VINYL COPOLYMER 1973, PCS 113- 19 VINYL CHLI'R I L'E COPOLYMER OtCUMPN PROPYLENE CO*`ULYMR DECOMPN POLYVINYL CHLORIDE THERMAL CLCOMPN HYUROGEN CHLQhIDL POLYMER DECOMPN MALEIC ANHYDRIDE DECOMPN POLYMER WCprttnw, ** s ** * o o S- 800048535G V0L=80 ISS=10 SEC=35 WT*16 CA447CARD 1 EFFECT CF SOME METAL CHLORIDES ON THE THERMAL DECOMPOSITION o OF POLY(VINYL CHLORIDE) AND POLYtVINYL I DENE CHLORIDE) MYAKOV, V. N. / TRQITSKIJ* B. B. s ussr . .; ;.; o. ! TR. KHIM. KHIM. TEKHNOL. : TKKTAE, VOL ISS 1 YR 1973, PGS 124- 5 - 'j > //KEYWORDS// '| o ! PVC THERMAL DECOMPN POLYVINYLIDENE CHLORIDE THERMAL:DECOMPN DEHYDRCCHLQRINATION MECHANISM PVC G MERCURIC CHLURIOE DEHYDROHLORINATION PVC FERRIC CHLORIDE DEHYDROCHLORINATION PVC - .Q TIN TETRACHLORIDE DEHYDROCHLORINATION PVC o TITANIUM TETRACHLORIDE DEHYDROCHLORINATION PVC INITIATOR DEHYDROCHLORINATION PVC , CATALYST DEHYDROCHLORINATION PVC -- .......................................... ............................................................. ... .) 7901268830 V0L=79 ISS=22 SEC=35 WT=9 CA447CARD 5> ' STUDY OF THERMAL DECOMPOSITION OF POLYIVINYL CHLORIDE)-TYPE POLYMERS USING MODEL SUBSTANCES. V. PYROLYSIS OF CIS-5-C O HLORO-3-HEPTENE AND CIS- ANO TRANS-5-ACETQXY-3-HEPTENE IN T HE GAS PHASE C CHYTRY, V. / OBEREIGNER, B. / KRIVINKOVA, 0. INST. MACROMOL. CHEM. / CZECH. ACAD. SCI. / PRAGUE i CZECH. - (V EUR. POLYM. J. "O EUPJAG, VOL 9 iISS 7 , YR 1973, PGS 649- 55 //KEYWORDS// PVC THERMAL STA6ILIITY .Q VIINYL ACETATE POLYMER STABILITY CHLORCHEPTENt PYROLYSIS KINETICS ACETOXYhEPTENE PYROLYSIS KINETICS . /". DEGRON PVC HEPTENE DERIV PYROLYSIS KINETICS ,. ; ACS COPYRIGHT 1973,CA-CONOENSATES OLI 6140 I f 79^126895V VOL"79 ISS=22 $EC=35 WT* 9 CA447CAKD 6 JHFRHAL DEGRADATION LlF POLY(VINYL CHLORIQE) IN THE PRESENCE c CF POLY(METHYL MtTHACRYLATE) EKSTRlN, F. A. / KULIKOVA, A. E. / LYUTOVA, T. M. SHILOV, G. I. i j USSR TR. KHIM. KHIM. TEKHNUL. TKKTAE, VGL ,ISS 3 , YR 1972, PGS 115- 19 t\ '\ //KEYWORDS// PVC GRAFTING POLYMETHACRYLATE THERMAL DEGRDN Pv'C POLYMETHACRYLATE o r,:? \ ; 78007282^0 VCL= 78 ISS= 12 WT= 9 CA447CARD 20 THERMAL OFGPAOATION AND COLOR SHADES OF POLY(VINYL CHLORIDE. I (SPECTROSCOPIC STUDY) SMIRNOV- L V ! '.PLATONOVA. N V o KULIKOVA. N P ! GRACHEV. VI- * SB NAUCH TP . LENINGRAD INST. TEKST LFGK PROM o REF 7H . KHIM 1972. ABSTP. NO 9S259 .ORMMYC, VOL ,ISS ,YR 71,PGS 210- 15, SEC 35 o //KFYwnonR// HEAT CEGROM PVC IR PVC DEG?ON ,UV PVC OEGPDN o COLOR STABILITY PVC t] k i'; - 780072R72U VOL= 73 ISS= 12 WT* 9 CA447CARD 27 THERMAL STABILITY TESTING OF POLYIVINYL CHLORIDE) v. mitterbfrger. dieter " . ;HOLD. FUPOLF FAR3WEFKF HOKCHST A -G GENDORF GUMMI. ASOFST. KUNSTST , -P. 86, VOL 6-8 ,ISS <10,YR )-,PGS 982- A, SEC 36 //KEYWORDS// '. REVIEW THFRVAL STABILITY PVC ' ' ' ' ;*x , . ;` , ; .. . j \ j. , ! .[ '> | }.. f. 'T 800083782G V0L=80 ISS=16 SEC = 35 WT=U CA447CARD 9 STUDY OF THE THERMAL DEGRADATION OF POLYtVINYL CHLORIDE) BY THERMAL ANALYSIS AMD ESR SPECTROMETRY SHIMCKAUA, SHIGE20 / UMNO, YASUHIRO / SOHMA, JUNKICHI HIRANO, HARUMUCHL / ENOUH, KAZ.UO .FAC. ENG. / HOKKAIDO UNIV. / SAPPORO / JAPAN NIPPON KAGAKU KA1SHI NKAKB8t*V0l ,ISS 10 , YR 1973, PGS 2016- 20 ^ i OLI 6141 amOt}37alF V0L=30 I5S--14 sec = 35 WT" 9 . CA447CARD 6 CGv``uSTIblLirY ,LjP FGLYIVINYL CHLGP IDS) - II. PYROLYSIS Or '' pcLYt V XYL CHLG? IDS) CGf-iTA I NING PHOSPHATES Y05HIMAGA, SHUN l CHI / MAT SUMQTO , MAjARU ,*>, NAGAlSHlt TOSHIYUKI / HARA, YASUTAKE / OSADA, HIDEYQ ' '* FAC. ENG. / KYUSHU SANGYO UN IV. / FUKUOKA / JAPAN NIPPON KAGAKU KAISHI ;"V NKAKBSt VCL , ISS 10 YR 1973, PGS 2007- 16 //KEYWORDS// PVC SODIUM PHOSPHATE PYROLYSIS . *, ' PYROPHOSPHATE SODIUM PVC PYROLYSIS HYDROGEN PHOSPHATE PVC PYP.OLYSIS O O c 8000838353 V0L=8O ISS=16 SEC=35 WT- 9 THERMAL DECOMPOSITION OF SOLID POLYMERS CA447CARD 14 O. BOUCHER, E. A. / EVERETT. D. H. / MILLARD, P. L. SHARMA, K. R. , UNIV. BRISTOL / BRISTOL / ENGL. .REACT IV. SOLIDS, PROC. INT. SYMP-* 7TH tSfW* 5 ,iss o . YP. 1972, PGS 492-505 Q- o POLYVINYLID6NE CHLOP1D6 DEHYDROCHLORINATION KINETICS pqlymethyl vinyl ketone OEHYORATION MCRPHOL POLYMER THERMAL DEGRDN o c; / ;T, 800071239X VCL=80 ISS=14 SEC=35 WT* 9 CA447CARD 5 THERMAL DEGRADATION AND STABILIZATION OF POLYIVINYL CHLQRIJ E). XV. ACTIONS AND EFFECTS OF ORGANOBORON COMPOUNDS ON T. HE THERMAL DECOMPOSITION OF POLYIVINYL CHLORIDE) MORIKAWA, TAKESHI / AMANO, TAKAO OSAKA MUNIC. TECH. RES. INST. / .OSAKA / JAPAN K06UNSHI KAGAKU KOKAAM, VOL 30 ,ISS 8 , //KEYWORDS// YR 1973, PGS 479- 85 BORATE ESTER PVC DEGRDN BORANE ORGANO PVC DEGRDN ORGANOBORON COMP'D PVC DEGRDN HYOROBORATTON PVC QRGANOBORANE COMPO o o ACS COPYRIGHT 197A,CA-CONOENSATES 0 O O *r- ' -rr. K. OLI 6142 S~C /0 ^ Al'/I `"H !m 7^71^- )sVL**^s^L#~0 Ife (#**i4s* 3* &01R- an. si $yu^ /-XUt-eri St l > * feiL? t-trujfe ^3sL*c^**&e*r^,$*$ csU~i*-*L *L OLI 6143