Document R4aDdEEanOGyXvqYz40NEq68

v** "v - _j Z. 2- R. Chartier ,vi Assonet i>.\ii:^May 10, 1974) i itciM (V. C. Pitts')^ New Haven infv in H. Bialecki I. Capuano sl'eject (^Polyvinyl Chloride - Decomposition^ R. Henderson Project 854l-0t0 C. H. Hofrichter NHTIS 74-38, S. 3 R. E. Maizell f" f"T.Tv/,n *8 V'/, ;i " if * . r' (' > 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 15, 1974. Do you wish us to continue collecting and forwarding such references or should we discontinue this program? VCP/rfd Attachments /C. Pitts dJL-'h iviAY 1 < 1974 TEC!. IiviO. idh. MW4 OU 7499 < *- d f- r t i j q^roirv a LTrN7:ot< PfmetD ON? YFAfi.. OTHi f kkom V. C. Pitts at New Haven subject Polyvinyl Chloride - Decomposition Project 8541-000 NHTIS 74-38, S. 3 COPY TO 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 15, 1974. Do you wish us to continue collecting and forwarding such references or should we discontinue this program? VCP/rfd Attachments VflC. Pitts r.^\ l v 1974 OLI 7500 WHY FILE THIS COPYI IF YOU MUST RETAIN IT. SPECIFY A DEFINITE RETENTION PCRIODi ONE YEAR__________ OTHER 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 com ments during discussion of this paper. References 1 Gotham, K.V, Plastics & Polymers 40 (1972) 59. 2 Gotham, K.V. /6i'rf40 (1972) 277. * Vincent, P.I. 'Impact tests and service performance of thermo plastics' Plastics Institute Monograph 1971. 4 Kennedy, A.J. `Processes of creep and fatigue in metals' (Oliver and Boyd, 1962). DECEMBER 1973 - WOOLLEY 5 Gotham, K.V. Plastics & Polymers 37 (1969) 309. 6 Bucknall, C., Gotham, K.V. and Vincent, P.I. `Polymer science' Ed A.D. Jenkins, Vol. I Chap 10 (North-Holland Publishing Company, Amsterdam and London). 7 Hill, R. `Plasticity' (Clarendon Press, Oxford, 1950). * Peterson, R.E. `Stress concentration design factors" (John Wiley & Sons Inc, New York, 1953). * Gotham, K.V. and Turner, Polymer Eng. Set. 13 (1973) 113. 10 Boogaart, A. van den, and Turner, C.E. Trans. J. Plastics Inst. 31 (1963) 109. 11 Paris, P.C. and Sih, G.C. `Stress analysis of cracks: fracture and toughness testing and its applications' ASTM Special Technical Publication No. 381. 12 Marshall, G.P., Culver, L.E. and Williams, J.G, Plastics & Polymers 37 (1969) 75. 13 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 Burns, D. J. Polymer Eng. Sci. 7 (1967) 90. __ y Toxic products from plastics materials in fires W.D. Woolley bsc, phd, mifiree Fire Research Station, Building Research Establishment, Department ofthe Environment and Fire Offices' Committee Joint Fire Research Organization Abstract: Over one-hall of the fatalities in fires are caused by smoke and toxic gases. Work is in progress at the Fite Research Station to study the production of toxic gases when plastics materials are decompos ed under controlled laboratory conditions involving pyrolysis at temperatures up to 7000 'C and in fullscale fires using a special compartment with a variable ventilation slit (door) leading to a corridor. When heated above about 190C, PVC releases the toxic pas hydrogen chloride. At 300^C this dehydro chlorination is rapid and quantitative, in fires involvino wood end PVC fuels the main toxic products are carbon monoxide and hydrogen chloride and the contribution of hydrogen chloride to the over-all toxicity depends upon the fuel loadings and ventilation. Pyrolysis of flexible polyurethane foam at about 300'-C releases a polymeric 'yellow smoke' which decomposes at temperatures above BOO'C in nitrogen (500C in air) to give a range of nitrogen-containing compounds, particularly hydrogen cyanide. Fires involving industrial toads of foam show that temperatures in excess of lOOO'C (sufficiently high to decompose the.yellow smoke) ere attained within a few minutes. During the early stages of the fire the toxic hazard from hydrogen cyanide can approach the same order of magnitude as that from the 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 the Fire Research Station. Boreham Wood, Herts. He graduated in chemistry at St Andrews in 1961 and spent two years with the National Research Council of Canada studying photochemical reactions. plasties & Polymers DECEMBER 1973. EIUKTED IN GREAT RRTTAIN 280 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 QLI 7501 2.1 Laboratory experiments In the laboratory studies, small 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 1000C in environments ranging from air to a serious deficiency of oxygen. This is in fact a study of the TOXIC PRODUCTS FROM PLASTICS MATERIALS IN FIRES Combuttibl# lining* ttachtd to walls External opamng a* raqvirad fig 1 Compartment and corridor for fire tests Fir* load Construction ralractory Slab* 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-spectro meter unit. In tliis 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. 2.2 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 (l-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 fuel 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 OLI 7502 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 190PC, 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-R)- = 0-l + ittr (1) 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 = 15-27-9-13xl03(i/r) (2) for inert atmospheres and logiofc = 12 -93 --7 -86 x 103 (1 /T) (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 t a b l e 1. Tabic 1 Calculated time for 20-60 per cent of theoretical dchvdrochlorination in nitrogen and air between 200 and 300'C TEMPERA TURE EXTENT OF DEHYDROCHLORINATION 20% 40% 60% NITROGEN AIR NITRO GEN AIR NITRO GEN AIR c min min min min min min 200 251-4 114-9 619-8 283-3 1237-8 565-8 220 41-4 24-3 102 1 600 2040 119-8 240 7-9 5-8 19 4 14-3 38-7 28-6 260 I 69 1-55 4-16 3-82 8-31 7-62 280 0-41 0 45 100 1-12 2-00 2-23 300 Oil 0 14 0-27 0-36 0-53 0-71 tc t DECEMBER 197 3 - WOOLLEY Under non-isothermal dehydrochlorination conditions genated organic species. Oxidation does of course produce (ie where the temperature rises as a function of time) as in oxides of carbon. fires, a time interval summation process has been used for From the laboratory studies it is concluded that the calculating the total hydrogen chloride released as a main toxic risk*-from PVC arise from carbon monoxide function of time from a knowledge of the temperature/ and hydrogen chloride. Contrary to certain popular time profile of the PVC. belief, there are no significant quantities of phosgene, The equation for this process is chlorine or organic halides. The hydrocarbons themselves make little contribution to over-all toxicity but the I (100--Pn)-* = 0* 1 + i At 2 &{mi) /<*! (4) aromatics are clearly precursors of smoke formation. 3.1.2 Full-scale tests. A typical full-scale fire test, to study where Pn is the total hydrogen chloride (as a percentage the behaviour of PVC in fires, involves a wooden crib of the theoretical) released at the end of the nth interval, (127 kg) as the main fuel source in the compartment, the dt is the time interval in minutes and k(mu is the rate walls being lined with 100 kg of rigid PVC, and having a constant at the mean temperature of the /th interval as ventilation slit 700mm wide. A comparative experiment is calculated from eqn 2 or 3. carried out with wood alone (127 kg) in the compartment. A comparison between the experimental and calculated Figure 3 shows the gas temperatures in the com dehydrochlorination of PVC subjected to a tempera partment as a function of time for these tests. The experi ture rise from 190 to 286C in about 20min is,given in ment with PVC gives a higher temperature for a longer figure 2. As can be seen, there is good agreement period than wood alone, due to the extra heat contri between the experimental and theoretical behaviour bution from the PVC. Typical concentrations of carbon except that the experimental curve lags behind the monoxide and hydrogen chloride recorded during these theoretical curve. This lag is due to the experimental tests are given in figure 4. The concentration scales are collection delay. The potential of this method in studies adjusted in the ratio of 2:1 to show equivalent toxicities of real fire situations is at present being evaluated. since carbon monoxide is directly hazardous to life at After dehydrochlorination of PVC has taken place, the 3000 ppm and hydrogen chloride at 1500 ppm. With residue has a conjugated polyene structure which itself hydrogen chloride there is the added problem that it is a 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 of aromatic materials, particularly benzene. The presence of air during decompo sition acts as a catalyst and increases the yields of the 4i hydrocarbons but without the formation of any oxy s * -I 1 fig 3 Gas temperatures for wood and PVC fires ----------wood ~ - -- wood and PVC I -if I 1l FIO 4 Toxic gas production from wood and PVC fires -------- * Carbon monoxide (vtood) --------- Carbon monoxide (wood and PVC) --------- . Hydrogen'chloridc (wood and PN C) TOXIC PRODUCTS [ROM plastics 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 fixpd temperatures and analysing the residues by elemental ultramicroanalysis (for the determination of the weight percentages of carbon, hydrogen and nitrogen). Figure 5 shows the comparisons between the weight and nitrogen losses for a typical MDI rigid polyurethane foam (prepared from diphenyl methane4,4'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 materia], and at 300C there is a virtually complete loss of the nitrogen content of each foam with a corresponding weight loss of about 30 per cent. Because of this behaviour and of the wide use of TDI 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 polyether) polyurethane foams represents a depolymerization process,5 namely that the foams decompose to give the parent polyol and TDI. 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 TDI) which has been isolated in the laboratory. The yellow smoke from the polyester foam appears to be identical with that obtained from the polyelher material. Its elemental composition is approxi- fig 5 Decomposition data for MDI rigid polyethcr foam O Nitrogen loss AiWeight loss TEMPERATURE "#c fig 6 Decomposition data for TDI flexible polyether and polyester foams O Nitrogen loss, polyester Nitrogen loss, polyethcr Weight loss, polyester Weight loss, polyethcr mately 64 per cent carbon, 6 per cent hydrogen and 17-5 per cent nitrogen, the remainder being oxygen. The yellow smoke is relatively stable to thermal decomposition and will volatilize unchanged from furnace systems at 283 temperatures up to 800C but will decompose readily above that temperature. Chromatograms (flame ionization detection) of the decomposition products of the yellow smokes obtained from the polyester and polyether foams and decomposed at 850C 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 in t ab le 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 MA5S-SPECTROMETR1C INTERPRETATION a Nitrogen* b Carbon dioxide c Ethylene d Ethane e Water f Propane g Hydrogen cyanide h Not identified i Butync or butadiene i Acetonitrile k Acrylonitrile 1 Propionitrile m Methyl acrylonitrile or vinyl acetonitrile n Benzene 0 Methyl acrylonitrile or vinyl acetonitrile p Not identified q Pyrrole r Pyridine s Toluene t Methyl pyridine u Methyl pyridine V Cyclooctatetrene or styrene w Vinyl pyridine X Benzonitrile or benzamide y Not identified <o Z Indcnc A Methyl cyanobenzenet B Methyl cyanobenzenet C Not identified D Not identified sJ O E Naphthalene F Quinoline or isoquinoline G Not identified Furnace carrier gas. tOthcr possibilities, phenyl acetonitrile or indole. 284 DECEMBER 1973 -WOOLLEY fig 7 Chromatograms of the decomposition products of yellow smokes at 850;C (a) from polyether foam (b) from polyester foam (For identifications see Table 2} fig 8 Yields of hydrogen cyanide from polyester yellow smoke and foam in nitrogen and air . < Yellow smoke, nitrogen--------Yellow smoke, air ----- -- Foam, nitrogen -- Foam, air I L- -TV J 1 II.J i i_ r\ * a\ l- j i ' i iru-J 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 for 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 polyether polyurethane foams have been carried out in the test rig. Figure 9 shows the temperature within the compartment for a foam test of 135 kg (ventilation slit 1 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 toxicities as estimated from toxicological literature0,7) 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 involves the qualitative and quantitative analysis of the chemical nature of the products formed during both small-scale laboratory experiments and full-scale fire tests. This analysis identifies only by chemical nature. There is no instrumentation available which will measure toxicity or irr.tancy. The assessment of the toxicity of the chemical products is made on the basis of published data3,0 ' obtained from human and animal exposures when available. Such data are very limited, and when applied to fire $ tses they do not necessarily indicate the true over-all toxicity 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 Porton. 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 w hether 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. fig 10 Toxic gas production from polyurethane fire --------- Carbon monoxide --------- Hydrogen cyanide Acknowledgements This paper is Crown Copyright and is repioduced by permission ol the Controller, HM Stationery Office. It is contributed by per mission of the Director, Building Research Establishment (1 lie Eire Research Station is the Joint Fire Research Organization of the Department of the Environment and the Fire Offices' Committee). It was first presented at the symposium on 'Smoke from burning plastics' organized by the Industrial Materials Research Unit, Queen Mary College, University of London on 22 February 1973. 285 O O Q 800083860F VOL=80 ISS=l6 SEC=35 WT= 9 CA^/LflKU LO THERMAL OtGRAUATION UP POLY(VINYL CHLORIDE). 1. APPARATUS Q FOR INVESTIGATION FOR EARLY STAGES OF THERMAL DEGRADATION ABBAS. KENT B. V SORV1K, ERLlNG M. ! DEP. ORG. CHEM. / CHALMERS UNIV. TECHNQL. / GOTEBORG ' O SUED. J. APPL. POLYM. SCI. I JAPNAb, VOL 17 ,ISS 12 , YR 1973, PGS 3567- 76 //KEYWORDS// THERMAL OEHYOPOCHLORINATION KINETICS PVC * I' CONDUCTIMETRIC OETN HYDROGEN CHLORIDE ; 800027610N VQL-80 IS$*06 SEC35 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. , ( * 4. POLYM. SCI., POLYM. CHEM. EO. ' JPLCAT, VOL II ,!SS 8 , YR 1973, PGS 1641- 50 . //KEYWORDS// PVC THERMAL DEGRDN KINETICS CHLOROPROPENE VINYL CHLORIDE COPOLYMER & 80008383 8E V0.L=80 ISS = l6 SEC=35 WT= 9 CA447CARD 15 ' DEGRADATION OF POlYIVINYL CHLORIDE). III. KINETICS OF THE RMAL DEHYDROCHLORI NAT ION CATALYZED BY SLOW-DIFFUSING HYDROG EN CHLCPIDE C- CARENZA. M. / MOISEEV, YU. V. / PALMA, G. LAB. FOTOCHIM. RADIAZ. ALTA ENERG. / CONS. NAZ. RIC PADUA / ITALY c J. APPL. POLYM. SCI. UAPNAB, VOL 17 ,ISS 9 , YR 1973, PGS 2685- 94 .'//KEYWORDS// ( , j PVC DEHYDROCHLORINATION KINETICS !HYDROGEN CHLORIDE DEGRDN CATALYST [CATALYST DEHYDROCHLOR INAT ION PVC OI I ACS COPYRIGHT 1974,CA-CONDENSATES J J ') 5 8 00 060 3 d4 H VOL = 80 l-n <, r PYROLYSIS OF POLY(VINYl'cH) nprnpf^ OMPounus NYL CHL0pi0E). CA447CAR0 6 formation OF AKOMATIl C DEp3'iD,NIU ' II0A' IAKt0 o SapVPPL- CHtM* 7 0SAKA IMI. TtCHNOL. / OSAKA o EN B1 TC PORIMA //KEYMjrdS// 13 ,ISS 13 * YP 1973' PGS HYDROGEN CHLORIDE PVC PYRULYSIS e AROM COMPD PVC PYROLYSIS OXIDE METAL PVC PYROLYSIS CHLORIDE METAL PVC PYRGLSIS 0 18" 23 OLI 7507 1 - 800060368N VGL=C0 ISS=12 SEC=3!> WT = 18 CA447CARD 1 \ O THERMAL OtCGMPuSITION OF A VINYL CHLGRIDE-PRQPYLENE COPGLYM> . er MYAKOV, V. N. / TROITSKII, B. B. "I USSR *V /i TR. KHIM. KHIM. T EKHNUL. . . TKKTAE, VGL ,ISS l , YR 1973, P&S 118- 19 I 0 //KEYWORDS// . r, THERMAL DbCUMPN VINYL COPOLYMER 1 VINYL CHLORIDE COPOLYMER DECOMPN .. 0 PROPYLENE COPOLYMER DECOMPN . ,1 .POLYVINYL CHLORIDE THERMAL DECOMPN . .L V . HYDROGEN CHLORIDE POLYMER DECOMPN . MALEIC ANHYDRIDE DECOMPN POLYMER u :nrunv. nr c- oon*. ftn * ##* I '*' y1 Vr.R -`*V -V-> y 5 o -j 0 G G G 800048535G V0L80 ISS=10 SEC*35 WT*16 CA447CAR0 1 EFFECT OF SOME METAL CHLORIDES ON THE THERMAL DECQMPOSItlQN OF POLY(VINYL CHLORIDE) AND POLYIVINYLIDENE CHLORIDE) MYAKOV, V. N. / TROITSKII# B. B. . USSR TR. KHIM. KHIM. TEKHNOL- V 1- TKKTAE, VOL ISS 1 YR 1973# PGS 124- 5 //KEYWORDS// : PVC THERMAL DECOMPN POLYVINYLIDENE CHLORIDE THERMAL DECOMPN DEHYDRGCHLORINATION MECHANISM PVC MERCURIC CHLORIDE DEHYDRDHLORINATION PVC FERRIC CHLORIDE DEHYDROCHLORINATION PVC TIN TETRACHLORIDE DEHYDROCHLORINATION PVC TITANIUM TETRACHLORIDE DEHYDROCHLORINATION PVC INITIATOR DEHYDROCHLORINATION PVC CATALYST DEHYDROCHLORINATION PVC Wr ` i ^ Y- 74 ,, K;: "* y, . '5 'X- V. ^ i G O e G e j & TTP" 79C126B83Q V0L=79 ISS=22 SEC35 WT= 9 CA447CAR0 5> STUDY OF THERMAL DECOMPOSITION OF PQLY(VINYL CHLORIDE)-TYPE POLYMERS USING MODEL SUBSTANCES. V. PYROLYSIS OF ClS-5-C HLORO-3-HEPTENE AND CIS- AND TRANS-5-ACET0XY-3-HEPTENE IN T: HE GAS PHASE CHYTRY, V. / OBEREIGNER# 6. / KRIVINKOVA, 0. INST. MACROMGL. CHEM. / CZECH. ACAD. SCI. / PRAGUE CZECH. EUR. POLYM. J. EUPJAG, VOL 9 #ISS 7 # YR 1973, PGS 649- 55 //KEYWORDS// PVC THERMAL STABILIITY VIINYL ACETATE POLYMER STABILITY CHLOROHEPTENE PYROLYSIS KINETICS OLI 7508 ACETOXYHEPTENE PYROLYSIS KINETICS DEGRDN PVC HEPTENE DERIV PYROLYSIS KINETICS \ ACS COPYRIGHT vy 1973CA-C ON DEN SATES , >, < '^ `: ' o -- t - j* , O 79ul26895V V0L=79 ISS=22 SEC=35 WT= 9 CA447CARD 6 ^ Gv.` THERMAL DEGRADATION OF POLY(VINYL CHLORIDE* IN THE PRESENCE OF POL Y(MET HY L METHACRYLATE) EKSTRlN, F. A. / KULIKOVA, A. E. / LYUTO^A, T. M, , -fCrt-r, j-.Vr i.' SHILOV, G. I. G USSR TR. KHIN. KHJM. TEKHNfJL TKKTAE, VOL , ISS 3 , YR 1972, PGS 115- 19 O //KEYWORDS// PVC GRAFTING POLYMETHACRYLATE JH ,V MW Vtii-"* ' THERMAL DEGKON PVC POLYMETHACRYLATE '`1 s? ,"Ji . V *. 7*r-- ' lirV. 78007282^0 VOL= 78 ISS- 12 WT - 9 CA447CARD 20 THERMAL DF GP A OAT ION AND COLOR SHADES OF POLY(VINYL CHLORIDE ) (SPECTROSCOPIC STUDY) SMIRNOV. L V PLATONOVA. N V o KULIKOVA. N P GRACHEV. V I SB NAUCK TR . LENINGRAD INST TEKST LEGK PROM u PFF lH . KHIM 1972. ABSTP NO 9S259 DBMMYC, VOl ,ISS ,YP 71,PGS 210- 15, SEC 35 o //KFYWPBOR// HEAT DFGRDN PVC IR PVC DEGphn ,UV PVC DEGPON G COLOR STABILITY PVC V `vfe *. V" :**".* G "f-Wi t. k- **'* O ' wt; few 1 . ` -a C; c 78007 2 R 7 ? U VOL = 78 ISS= 12 WT= 9 CA447CARD THFR^At STAPILITY TESTING OF POLY(VINYL CHLORIDE) G MITTEBCRGFR. DIETER HOLD. FUDOLF FAR3WEFKF HOFCHST A -G GENODPF GUMMI. ASBFST. KUNSTST r?.. 86, VOL 6-8 ,ISS //KFYWCR DS// (10,YR ),PGS 982- REVIEW THFR MAL STABILITY PVC 4, SEC OLI 7509 W ' `v 3_i; , '*; ! 800083782G V0L=80 ISS=16 SEC=35 WT=11 CA447CARD STUDY OF THE THERMAL DEGRADATION OF P0LY(VINYL CHLORIDE) THERMAL ANALYSIS AND ESR SPECTROMETRY SHIMOKAWA, SHIGEZO / OHNO, YASUHIRO / SOHMA, JUNKICH HIRANO, HARUMOCHI / EAIOOH, KAZUO ,FAC ENG. / HOKKAIDO UNIV. / SAPPORO / JAPAN , . `NIPPON KAGAKU KAISHI NKAKB8, VOL ,ISS 10 , YR 1973, PGS 2016- 20 .//KEYWORDS// r. \V ;"V o 800083781F VOL=80 ISS=16 SEC=35 WT= 9 CA447CARD 8 o COMBUST I 811ITY OF POLYIVINYL CHLORIDE). II. PYROLYSIS OF POLY!VINYL CHLORIDE) CONTAINING PHOSPHATES YOSHINAGA, SHUNICHI / MATSUMQTO, MASARU o NAGAISHI TOSHIYUKI / HARA, YASUTAKE / OSADA, HIDEYO FAC. ENG. / KYUSHU SANGYO UNIV. / FUKUOKA,, / JAPAN NIPPON KAGAKU KAISHI o NKAKB8, VCL //KEYWORDS// ,ISS 10 , YR 1973, PGS 2007- 16 PVC SODIUM PHOSPHATE PYROLYSIS PYROPHOSPHATE SODIUM PVC PYROLYSIS HYDROGEN PHOSPHATE PVC PYROLYSIS . ;'s v- '4 ' Vr-'- 80008383 5B V0L=80 ISS=16 SEC=35 WT= 9 CA447CARD THERMAL DECOMPOSITION OF SOLID POLYMERS BOUCHER, E. A. / EVERETT, D. H. / MILLARD, P. L. SHARMA, K. R. o ^' UNIV. BRISTOL / BRISTOL / ENGL. . REACH V. SOLIDS, PROC. INT. SYMP., 7TH ANDERSON, J. S A, o 27JDAX, VOL ,lSS , YR 1972, PGS 492- 505 //KEYWORDS// . POLYVINYLIDENE CHLORIDE DEHYDR OCHLORI NATION KINETICS ( : POLYMETHYL VINYL KETONE DEHYDRATION MORPHOL POLYMER THERMAL DEGRDN (> O / (* !? 8000712J9X VCL =80 ISS=l4 SEC=35 WT= 9 CA447CARD THERMAL DEGRADATION AND STABILIZATION OF POLYIVINYL CHLGRIU E). XV. ACTIONS AND EFFECTS OF ORGANOBORON COMPOUNDS ON T HE THERMAL DECOMPOSITION OF POLYIVINYL CHLORIDE) MORIKAWA, TAKESHI / y\MANO, TAKAO OSAKA MUNIC. TECH. RES. INST. / OSAKA / JAPAN K06UNSHI KAGAKU KOKAAM, VOL 30 ,ISS 8 , //KEYWORDS// YR 1973, BORATE ESTER PVC DEGRDN BORANE ORGANO PVC DEGRDN ORGANOBORON CQMPD PVC DEGRDN HYDROBORATTON PVC ORGANOBORANE COMPD ACS COPYRIGHT 1974,CA-CONDENSATES j ' ;:i a, - i-...... :..r 4 Vr v' /V . 1 -*1. y fi4,7 ' . - -v I t UU':} r V., I ' *1 Y'-r'v-' iV. ft ' : f&O' : rj . v.' ^ ``v *.*:'v>.; ii.V. s v- u. .7