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RCSVD mar 05 ^74 ANALYSIS OF THE VOLATILE COMBUSTION PRODUCTS OF VINYL PLASTICS ' E. A. Boettner, Gwendolyn Ball, and Benjamin Weiss Department of Industrial Health School of Public Health The university of Michigan Ann Arbor, Michigan The use of plastics at elevated temperatures in confined spaces has created an. interest in the possible toxicity of their combustion products. We have examined pure and formulated vinyl plastics to determine the com- . position&nd toxicity of their combustion products. " Differential thermal analysis and thermal gravi metric analysis were used to determine the temperatures at which chemical and physical changes take place. The products of combustion were then determined qualitatively ' ' using infrared spectroscopy.and a combination of gas chromatography and mass spectroscopy. Quantitative analy ses were performed on the' products produced under con trolled combustion conditions. A comparison of the products of the formulated and virgin resins, is given, as wall as some toxicity in formation. resulting from animal.exposures.. ucc 037^68 * , ANALYSIS OF THE VOLATILE COMBUSTION PRODUCTS OF VINYL PLASTICS by E. A. Boettner, Gwendolyn Ball, and Benjamin Weiss INTRODUCTION The use of plastics for applications that can result in high temperatures in confined spaces has made it necessary for the environmental health scientist to become knowledgeable of the na ture and toxicity of the products of combustion of these plastics. The pyrolysis products of various polymers have been reported by others 3'^, but much of this work has been carried out in inert atmospheres for the purpose of gaining information about polymer structure. Those workers concerned with the combustion of vinyl chloride polymers examined these plastics to determine primarily the amounts of HCl, C02, CO and other gross products given off and the temperatures at which they were produced. Five (4-8) such papers were published recently in German publications In 1963, we began a program* to determine the volatile combustion products of various plastics and to carry out animal ex posure studies to determine the toxicity of these products. The combination of analytical data and acute toxicity studies will allow the determination of whether the compounds shown to be pres ent can account for the overall toxicity of the decomposition products or whether synergistic effects may also be a factor to be taken into consideration. A prior knowledge of the physical nature and chemical composition of these pyrolytic products will also provide a necessary guida for animal exposures, both as to the extent of exposure and to the possible nature of the toxic effects. *This investigation was supported in part by public Health Service Research Grant No. UI-00485 from the National Center for Urban and Industrial Health. UCC -2- This paper describes oar results in the examination of polyvinyl chloride polymers and plastics. This particular group was selected first because of its wida application in electrical insulation and construction materials, second, because of exten sive work done in the pyrolysis of the basic polymers by otners, and tnird, because only limited knowledge is available on the quantities of compounds formed in combusting plastic products of tnis type under various combustion conditions . The procedure used in our work consisted of two parts. The first part was di rected toward a qualitative and quantitative analysis of the prod ucts of combustion. The second was concerned witn tne determina tion of the toxicity of the combustion products. All combustion took place in controlled amounts of air. The analytical portion of tne study was carried- out in tnree phases: 1) The temperatures at which chemical and physical changes take place in a controlled air supply ware determined. 2) The compounds liberated at these temperatures were * identified or characterized. 3) The quantities of the products were determined either at the temperatures covering each decomposition step or for a sample collected over the entire combustion process. The temperatures at which changes take place were deter mined by differential thermal analysis (DTA) and thermogravi- metric analysis (TGA). In the second phase of the analysis, which involved identification of the compounds liberated at the decom position temperatures, two different! approaches were taken. The gases collected from either the TGA apparatus or combustion fur nace were analyzed directly for the major compounds by infrared absorption spectroscopy or mass spectroscopy. For positive iden- fication of the minor constitutents, it was necessary to collect the gases from a larger sample than the 200 mg that can be handled UCC 3 by the TGA apparatus. To do this, a combustion furnace with con trolled temperature and air supply was used to carry out the com bustion on a ten-fold scale (2g) but under the same conditions as in the TGA apparatus. The gaseous products were either collected in two phases (compounds boiling below -74c and above -74C) or were collected as a single gas sample and separated further by gas chromatography. The individual chromatographic peaks were col lected by condensation at liquid air temperature, and these frac tions were analyzed by mass spectroscopy. The third phase, the quantitative analysis or the identi fied products, was carried out by infrared spectroscopy for the .principal constitutents and by gas chromatography for the minor constituents. In the toxicity portion of the study, rats were exposed to the volatile thermal decomposition products of the plastics in small chambers. The products were generated in the same combus tion furnace used in the analytical study. As in the analytical study, the individual exposures were made using the same combus tion temperature range and heating rate, so that the exposure con ditions could be correlated with tho analytical data-. "The toxic- ty data is described in Another paper ------ 'Four polymers produced by two companies were analyzed, as were three formulations using three of these polymers. These poly mers are as follows: Polymer A: A polyvinyl chloride homopolymer, polymer B: Similar to A but a later production, polymer C: Similar to A & B, but produced by another company. Copolymer D: A copolymer of vinyl chloride and vinyl acetate in the ratio of 85 to 15 respec tively. plastic E: A formulation commonly used for wire insula tion using Polymer C. Plastic F: A formulation used for floor tiles, using copolymer D. Plastic Gs A wire insulation formulation; using polymer B. ucc 4 With one exception, the polymers and formulations were standard commercial materials furnished by the polymer manufac turers . The last product. Plastic G, was formulated for us in a development lab of one manufacturer, using a "typical" wire in sulation formula. RESULTS: Breakdown Process. Differential thermal analysis (DTA) was used to determine the temperatures at which chemical and physi cal changes take place. With this apparatus, we obtained a record as shown in Figure 1 for Polymer C when heated in an excess of air. This record shows the heat absorbed (from an endothermic change) (down) or liberated (from an exothermic change) (up) as y\ T plotted against the temperature of the sample. Of signifi cance here is the endothermic peak with a maximum at about 300c, which (according to Cobler) results from the release of the chlo rine atoms in the polymer; unfortunately it is obscured here in the start of the continually increasing exothermic peak from 300C to 600C, at which temperature the samples is completely combusted. The dehydrochlorination peak varies in position by - 20C, and as this variation seems tobe erratic and independent of the sample, it is assumed that it is associated with some experimental param eter, such as sample packing, etc. Figure 2 shows the DTA record of plastic E which was for mulated from polymer C. The only gross difference is the steeper slope in the exothermic peak at 325C. Because of the limited amount of interpretation that we could extract from the curves, the information derived from the DTA technique was not as helpful to our study as was thermogravimetric analysis, where one obtains a recording of weight loss with temperature. Figure 3 shows a TGA record for Polymer C. Here one finds a rapid weight loss at 300.C, corresponding to the endothermic peak in the DTA record. On collecting the combustion gases up to 300C and analyzing them by infrared absorption, it was found that the- 60% weight loss was almost entirely due to the removal of chlorine in the form of uoc 037572 / 5 hydrogen chloride gas, and by calculation it appeared that the amount corresponded to almost all of the chlorine atoms in the polymer. AbCve 300C, the TGA record shows a slower but grad ually increasing rate of weight loss up to &00c, corresponding to the exothermic peak in the dta record. It will be noted that this weight loss appears to take place in five stages: The first is the rapid loss up to 280, the second, a decrasing rate of loss up to 350, the third, a slow constant rate of loss to 430, the fourth, a mdre rapid rate of loss to 510, and finally, a faster rate of loss for the remainder of the sample. These par ticular temperature ranges are used later (Table IV) in describing the change in composition of the combustion products with the tem perature. Figure 4 shows a similar record for plastic E, which con tains Polymer c. It will be noted that the height of the 300 step, attributed in Figure 2 to the removal of chlorine, is as high here, although this plastic contains only 57% of the polymer. The remainder of the weight loss is due to the bpiling-off of the plasticizer, a phthalate which has a boiling point of about.280C. , Figure 5 is the TGA record of the copolymer D, and it can be seen that its yeight loss proceeds quite the pame as the pre vious polymer, except that here the initial weight loss is due to both the removal of chlorine atoms and acetate groups. Figure 6 is of plastic F, the floor tile formulation that contains about 35% of Polymer D. This formulation contains a cqnsiderable amount of inorganic minerals,* such as asbestos, which ip the reason for the limited amount of weight loss up to 600C. QUALITATIVE ANALYSIS: . If one analyses the products of combustion! by infrared spectroscopy, collecting the total products in gas form and intro ducing them into long-path gas cells, absorption bands of HCl, CO,,, CO, and C,H- will be found, along with other bands in the 2t oQ ., 3000 cm region, indicating the presence of compounds containing C-H groups. It was evident from this that the identification of ucc U37573 6 other compounds should be carried out by separating them from the mixture and collecting them in individual quantities that would permit identification by infrared or mass spectroscopy. For this, gas chromatography was used, using sufficiently large columns to permit the introduction of up to 30 ml of air containing combus tion products. To separate the low boiling compounds, i.e. those boiling at temperatures less than 0C, a Porapak Q column was used, while to separate- the higher boilers, a column of 5% Squalane on Chromosorb p was "used. On the column outlet of the chromatograph is a stream splitter which passes one hundredth of the gas through a hydrogen flame detector. The remaining 99 parts emerge from the column through a two-way valve so that it can be diverted into a U-tube when a particular compound is emerging. The U-tube is filled with glass beads and is cooled with liquid air to condense out everything except the carrier gas, which is He. The U-tube and its cooling flask is then transferred to the inlet system of the mass spectrometer. As indicated earlier, HCl, CO, C02 and CgHg were identi fied in the gross product by infrared spectroscopy. Other low boiling compounds, were separated on the porapak column. Figure 7 shows the separation of the first 8 compounds. These are primarily the parafins and olefins up through butane. The peaks are identi fied in Table I according to peak number. These peaks were iden tified by using the collection technique described to transfer the compound to the mass spectrograph. The mass spectrographic iden tification was then cr'oss-checked by injecting the pure compound on the chromatograph to establish that its elution time was the same as the collected peak. Higher boiling compounds were separated using the squalane column. A chromatogram of this column is shown in Figure 8. Here, in addition to the straight chain parafins and olefins, one finds both branched and cyclic compounds. These are again identified in Table I. There are a minimum of 58 volatile products of combustion, totaling the threo compounds identified by direct infrared analysis I !OC 037574 "7- and 52 chromatographic peaks. This is given as a minimum figure, because al: least three of the peaks represent more than one com pound. Of this minimum figure of 58, we have identified 44 com pounds. Of another six, we have determined the molecular weight and established that they are olefins, but because of the simi larity in the molecular weights and the limited mass spectra ref erence data, a positive identification has been difficult. The other eight compounds are higher boilers and are present in very small quantities, i.e. less than 30 ^g/g, and therefore are of limited interest from the standpoint of toxicity. This qualita tive picture was quite similar for all PVC polymers and formula tions tested, with only a few differences found in the higher boiling products, and this is discussed in the next section. QUANTITATIVE ANALYSIS: As indicated earlier, to obtain large amounts of combustion products both for the analytical work and later toxicity tests, a controlled atmosphere combustion furnace was designed and built. The furnace has a vycor gas-tight core which is supplied air from a tank of purified air. The outlet of this core is connected to a' U-tuba submerged in a cooling bath for condensing out some of the emerging compounds. Others pass through or by-pass the tube and are collected in a plastic bag. The furnace is controlled by a commercial programmer-controller. Using this apparatus, we can heat larger samples of the plastic with controlled temperature and air supply to carry out the combustion under the same conditions as the TGA apparatus. One can establish that the products are the same by comparing the gas chromatogram of the furnace products with the chromatogram obtained from the TGA combustion products over the same weight-loss range. The products from the combustion furnace can be collected in several temperature or time fractions, depending on the collection method. One of our "ground rules" from the start was that we would only be concerned with the "volatile products" of combustion, de fining as volatile those compounds boiling up to |130C. As a re sult, wo wore not concerned with tho collection of higher boiling i irn 037575 -8- compounds that either remained in the combustion boat or were de posited in the exit end of the combustion tube, although we at tempted to keep an account of the weight of this remainder to assure that the volatile fraction was all accounted for. As a result, although the TGA record of plastic E (Figure 4) shows a weight loss due to the^boiling off of the phthalate plasticizer, this compound is not listed in our quantitative results. In our quantitative work, various parameters were examined that could affect the quantities of the various compounds of combustion, and these are reported as follows: 1. The variation in quantity within a class of compounds and between classes of compounds for the polymers. 2. Quantitative changes with varying air supply. 3. Quantitative changes with temperature. 4. Quantitative changes with varying heating rates. 5. Quantitative changes between the plastics and their polymers. All the quantitative work was done on the 22 compounds present in the greatest quantities. 1* Variations between combustion compounds of the polymers: As a uniform condition for intercomparing the polymers and formulations of the polymers, the following combustion conditions were adopted: The air supply was 60 c.c. of air a minute, which when in tegrated over the entire run would result in about twice the amount of oxygen necessary ter convert all of the carbon to carbon dioxide. However, this is not true for any particular time in the combustion process, in that first, the carbon is not available to form carbon dioxide until the higher temperatures are reached, and second, the air flow pattern is such that all of its oxygen is not in the imme diate vicinity of the sample. The plastics were heated, (after an initial heating from room temperature) from 20QC to 600C at a rate of 3C degrees a minute. Table II' shows the volatile products of cpmbustion of the Sample B polymer.. The quantities of these products are quite uec 037576 vrs 9 representative of the other two homopolyraers. Also in this table are the same products from the Sample D copolymer. All quantities given are in mg of compound per gram of polymer. It will be noted that in the case of Sample B, the chlorine is almost completely accounted for in the form of HCl gas (582 mg vs 584 possible). The only other chlorine compounds found, methyl chloride and vinyl chloride, are present in quantities less than 1 mg. Some invest!V-Y,, gators have reported finding phosgene intermittently in very small \ ttjT'^jiquantities (O.l'ppm) but, using detector tubes of this sensitivity, JO & we have not found this compound in any of our tests. The next most abundant products are the carbon dioxide and the carbon mon oxide, which are formed at the higher combustion temperatures. The next compound in quantity is benzene, where 35 mg/g are formed. Note that the quantities of these compounds in the copolymer are very similar, except that some of the HCl is replaced by acetic acid. Next in quantity and decreasing with increasing molecular weight are the straight chain aliphatics, starting with methane. The olefins and side-branched aliphatics are generally present in lesser quantities than the corresponding aliphatics. In these samples, the volatile combustion products account for approxi mately 100% of the original polymers, and no residue remained in the combustion boats. 2. Variations with amount of air. One sample (Polymer A) was combusted under three air (or oxygen) conditions, The first was with the amount of air to pro vide a minimum amount of oxygen for complete combustion of all carbon to CO2 (using 30 c.c. air par minute). The second was using about twice this amount (60 c.c. per minute) and the.third air condition was with a large excess of oxygen. The results are shown in Table III. The data shows that all of the hydrocarbons, except for benzene, decrease in quantity with increasing air. The benzene content seems to be independent of the air conditions. The only compound which increased was the vinyl chloride. Although this change in the amount of air affects uce 037577 10 - the quantity of hydrocarbons generated, surprisingly it had little effect on the quantity of CO and CC>2 generated, which showed no trends using these air flows. However, it should be mentioned that the quantities of COj varied erratically in most of our com bustion runs for soma unknown reason. Variations with temperature. Table XV shows the variation in quantities of^products of combustion as a function of tempera ture. The products were collected in five fractions during a single heat run*." The fractions were selected on the basis of the curve inflections on the TGA curve shown in Figure 3. The first temperature fraction, which is the one where most of the chlorine is removed, shows the immediate formation of benzene and a little toluene. In the second fraction, 280-350c, the first CO^' and CO appear, the toluene continues to increase, but the benzene is al ready decreasing, and continues to decrease through the higher ranges. As one would expect, the CO2 and CO reached their maxi mum at the higher temperatures. Methane reached its maximum in the fourth step, but was still generated at the higher temperatures. The other straight chain aliphatica reached their maximum in the third step and were present in the last step in very small quantities. The olefins began to form in the first step, reached their maximum in the third, and did not appear in the last two fractions. Enough chlo rine remained to form some HCl in the second step, but it was here that the maximum amount of vinyl chloride was formed. Quantitative changes with varying heating rates: The data on Table V is representative of what happens when the heating rate is increased considerably. Here one can see that an increase in heating rate results in an increase in hydrocarbon production, but it will also be noted that the unsaturated com pounds increase by a greater amount than the saturates. As a re sult, in an exceptionally fast heating rate, the olefins will be present in greater quantities than the aliphatics. This is illus trated in tho chromatogram shown in Figure 6, where the products 11 were collected from a run in which the controlling thermocouple . i turned out, with the result that a heating rate greater than 1 ' 80c/minute was attained. Also to be noted is that at higher heating rates the production of CC>2 end CO decreases. Variations between plastics and their polymers: A comparison of the products of combustions of the three plastics with the products from their polymers is given in Table VI. Plastic E contains 57% of Polymer C, Plastic G 51% of Polymer B, and Plastic F 35% of polymer D. One thing of note in Plastics E and G is that except for the aromatic compounds which are less, the other 15 hydrocarbons have all increased in quan tity by factors ranging from 1.3 up to 8 times, with the average about 4 times. Likewise, the amount of vinyl chloride is about 5 times as great in these samples that contains only 50%- of PVC polymer. It is possible that some of the increase in hydrocarbons may be attributable to the break-down of the phthalate plasticizer, although the extent of this contribution has not been established. Different results are noted for a floor tile formulation (Plastic F) made from copolymer D. This product contains about 1/3 copolymer D, but the hydrocarbon products generated, espe cially the saturated aliphatics and the benzene are considerably less than 1/3 the amount generated in copolymer D. Likewise, the amount of HCl to CHjCOOH is only 20%, rather than the 33% expected. This product contains about 70% inert material, such as asbestos and calcium carbonate, which may play a part in inhibiting break down of the polymer and the production of hydrocarbons. It should be stated that plastic F has three compounds with boiling points in the vicinity of 120 that have not been identified, which are present in quantities of one to five mg/gram. ucc 0:37579 REFERENCES 1. Madorsky, Samuel L., 1964, Thermal Degradation of Organic Polymers. John Wiley and Sons, New York, 2. David W. Levi, "Literature Survey on Thermal Degradation, Thermal Oxidation, and Thermal Analysis of High Polymers." Picatinny Arsenal, Dover, N. J., June 1963. AD423546, Clearinghouse for Federal Scientific and Technical Infor mation. . 3. Dorothy A. Teetsel and David W. Levi, "Literature Survey on Thermal Degradation, Thermal Oxidation, and Themal Analysis of High Polymers, II. Picatinny Arsenal, Dover, N. J., Jan. 1966, AD631655, Clearinghouse for Federal Scientific and Technical information. 4. Thinius, K., Schroder, Elisabeth and Gustke, A., A Discussion of pyrolysis of Plastics in the Presence of Air,' Plaste and Kautschuk, 11:67-72, 1964. 5. Hagen, E. and Friedrich, G., Analyses of the Composition of the Gases Produced by the Combustion of More Plastics. Plaste und Kautschuk, 12:215-18, 1965. 6* Luther, H. and Kruger,H., The Effect on the Thermal Decom position of Polyvinyl Chloride of the Hydrogen Chloride Formed. Kunststoffe, 56:74-9, 1966. 7. Braun, D. and Thallmaier, M., Measurement of the Evolution of Hydrogen Chloride at Elevated Temperatures. Kunststoffe, 56: 80-3, 1966. 8. Vymazal, Z. and Stepek, J., Studies on the Thermal Degradation of PVC and Vinyl Chloride copolymers. Kunststoffe, 56:86-91, 1966. 9. Boattner, E. A. and Weiss, Benjamin. "An Analytical System for Identifying the Volatile Pyrolysis Products of plastics." Amer. Ind. Hyg. Assn. Jour. 28:535-40, 1967. 10. Survey of Available Information on the Toxicity of the combus tion and Thermal Decomposition Products of Certain Building Materials under Fire Conditions. Underwriters' Laboratories ` Bulletin of Research, No. 53, July, 1963. UCC 037530 ucc Figure 1 Differential thermal analysis of Polymer C CO kJ3 '-- u>o 7^0 0S3O Figure 2 Differential thermal analysis of Plastic E 100 % WT REMAINING 50- POLYMER C 0- 200 C 400 6<5D ucc Figure 3 Thermogravimetric analysis of Polymer C <c:oo Figure 4 Thermogravimetric analysis of Plastic E iOO- % WT REMAINING 50- POLYMER D oC `-'-'I O 0- A1 00 C 600 Figure 5 Thermogravimetric analysis of Copolymer D 100 % WT REMAINING 50- PLASTIC l o- 200 C 400 600 Figure 6 Thermogravimetric analysis of Plastic F Figure using a Porapak Q colurrin ) m. i ft liilLil. t Figure 8 Chromatogram of higher boiling compounds using a squalane column o o Table I:* Identification of Chromatogram Peaks Peak # Identification air 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 ** . Tentative Methane Ethylene Ethane propylene Propane (Methyl chloride) * Vinyl chloride 1-Butene (Isobutane - Butadiene) jlutane trans-2-Butene cis-2-Butene 3-Methyl-1-butene Isopentane (1,4-pentadiene) l-pentene Pentane cis- & trans-2-Pentene 2-Methy1-2-butene cis or trans-1,3-pentadiene cis or ^trans-2-Penten-4-yne Cyclopentene Cyclopentane 2-Methylpentane 1-Hexene Hexane 2-Hexene Methylcyclopentane 1-Methylcyclopentene Benzene ' 1-Heptene An olefin, molecular weight 96 Heptane an Ethylcyclopentene * Methylcyclohexane . Ethylcyclopentane An olefin, molecular weight = 96 an Ethylcyclopentene * 1-Methylcyclohexene Toluene at least two compounds here Octane Ethylbenzene p-Xylene m-Xylene o-Xylone Table II: Volatile Combustion Products of Polymer B and Copolymer D Compound HC1 Acetia Acid C02 CO Methane Ethylene Ethane Propylene Propane Vinyl chloride . 1-Butene Butane Isopentane 1-Pentene Pentane Cyclopentene Cyclopentane 1-Hexene Hexane Me thyIcyclopentane Benzene Toluene Poivmer B 583. g 729. 442. 4.6 0.58 2.2 0.47 -84 0.60 0.18 0.28 0.02 0.06 0.16 0.05 0.05 0.05 0.12 0.04 36. 1.3 ^ Copolvme: 500. 96. 1 X 923. 292. 4.4 0.60 2.3 0.56 : 0.88 0.72 0.22 0.29 0.02 0.09 0.21 : 0.05 0.06 / 0.08 0.17 0.05 28. 0.96 Table III: Variation of the Combustion Products of Polymer A with Oxygen Compound co2 CO Methane **., Ethylene Ethane Propylene Propane Vinyl chloride 1-Butene Butane Isopentane 1-Pentene Pentane Cyclopentene Cyclopentane 1-Hexene Hexane Methylcyclopentane Benzene Toluene cc 30 min. air mg 861. g 357. 6.7 0.76 2.6 0.80 1.3 0.51 0.25 0.53 0.02 0.10 0.26 0.07 0.08 0.07 0.16 0.06 35. . 1.5 cc* 60 min. air 619. mg g 429. 4.7 0.53 2.1 0.53 1.0 0.59 0.18 0.31 0.02 0.08 0.20 0.05 0.07 0.06 0.14 0.05 31. 1.1 25 -- ]min.air plus 21 min 814. mg g 401. ' 3.8- 0.28 1.7 .0.28 0.66 0.66 0.06 0.15 0.01 0.04 0.11 0.03 0.03 0.03 0.09 0.03 32. 0.61 ucc 037591 g|tn r Table IV: Variation of combustion Products of Polymer A with Temperature Compound C02 CO Methane Ethylene Ethane Propylene Propane Vinyl chloride 1-Butene Butane Isopentane 1-Pentene Pentane Cyclopentene Cyclopentane 1-Hexene Hexane Methylclopentane Benzene Toluene 25-280C mg ------- g -- -- >.04 -- 0.06 -- 0.04 0.02 -- -- -------- --- -- ---- 24. 0.12. 280-350 C mg 9.7 g 20. 0.20 0.33 0.12 0.11 0.08 0.25 0.04 0.03 ------0.01 0.01 0.02 0.01 0.01 0.01 ------6.6 0.18 350-430 C mg. 181. g 46. 1.3 0.39 0.94 0.31 0.44 0.17 0.08 0.20 0.005 0.03 0.08 0.01 0.02 0.02 0.05 0.02 0.35 0.55 430-510 C m 244. g 151. 1.8 0.41 0.11 0.02 0.02 0.001 --- 0.01 m aaiw 0.01 0.16 0.03 510237 181 0 -- --1 TM --1 o.. ucc 037592 Table V: ^ Variation of Combustion Products of Polymer A with Heating Rate Compound co2 CO Methane Ethylene Ethane Propylene Propane Vinylchloride 1-Butene Butane Isopentane 1-Pentene Pentane Cyclopentene Cyclopentane 1-Hexene J Hexane Methylcyclopentane Benzene Toluene 3c/m.in. mg 619. 429. 4.7 0.53 2.1 0.53 1.0 0.59 0.18 0.31 0.02 0.08 0.20 0.05 0.07 0.06 0.14 0.05 31. 1.1 50c/min 397. * C 269. 8.7 2.3 3.5 1.5 1.3 0 . o4 0.67 0.69 0.02 ; 0.18 . 0.29 0 19 nU XitX 0.13 0.20 0 Uo 43. 3.5 ucc 037593 % h Table VI: Comparison of Combustion Products of the Plastics with the Combustion Products of their Polymers Compound HC1 Polvmer B mg 583. ir Plastic G mo 273. g* Polvmer C mcr 584. g Plastic E mg 333. g Copolymer D mg 500. g Plastic I 73. . Acetic Acid c2 729. -- 616. mt 730. 1182. 96. 923. 20. 456. CO 442. Methane 4.6 Ethylene Ethane 0.58 2.2 Propylene 0.47 Propane 0.84 Vinylchloride, 0.60 1-Butene 0.18 Butane 0.28 Isopentane 0.02 1-Pentene 0.06 Pentane , 0.16 Cycloporftene 0.05 Cyclopentane 0.05 1-Hexene 0.05 Hexane 0.12 Methylcyclopentane 0.14 Benzene 36. Toluene * Residua 1.3 -- .. 67. 6.6 2.3 3.0 2.0 1.7 3.3 1.1 1.1 0.15 0.35 0.58 0.14 0.16 0.24 0.49 0.14 10 .* 0.94 159. 403. 5.8 0.33 2.5 0.56 1.1 0.52 0.28 . 0.39 0.02 0.11 0.27 0.58 0.07 0.09 0.25 0.07 29. 1.1 -- 90. 6.8 2.0 2.9 1.4 1.4 2.6 0.58 0.74 0.04 0.15 0.38 0.07 0.09 0.18 0.35 0.09' 11. 1.0 61. 292. 4.4 0.60 2.3 . 0.56 0.88 ' 0.72 0.22 0.29 0.02 0.09 0.21 0.05 0.06 0.08 0.17 0.05 28. 0.96 -- 31. 0.30 0.13 0.13 0.11 0.10 0.30 0.06 0.05 0.01 0.01 0.02 0.004 0.003 0.01 0.01 ---- 0.86 0.04 709. ^Residue is what remained in combustion boat. It does not include products which condensed at the end of the combustion tube. UCC 037594