Document MMoXp5xm4YY41mED1mvY77qdL

rOftM 0M.I0009 *tv. Ml f 1 ji t! AT Afetfonet " * >v f. ;x:. ,/; /yvu DATE ^28 February 197 3>' (yTc ~Pitts; & __ _______ AT Hew Haven _ copy to W. Boswell A. C. Bridge /TOLYVINYL CHLORIDE - Current Awareness*) _ _ __ J*. C. Collyer PROJECT 7' ---------------------- ' OLlN-RECElVt.1^- J- Flanagan NHTIS 73-11 - Supplement I B. M. Lederer (see also HHTIS 72-3, and 71-30) ,/ , - CULZ-U Ca~~zt . , , ,~7. `i' i ' J. H. Ludes R. E. Maizell (w/o att R. N. Williams t* :. -r nr-v Mr'' |it.':riJ. A. Wood lUi J. v'. 'V q Attached is our most recent collection of patents and articles on poly vinyl chloride. As in the past, we will obtain copies of abstracted articles or full copies of those in which only the first page has been included as you request them. Prepared by V. CS Pitts Accepted by R. E. Maizell REM:rfd Attachments SOURCES: F&S Index of Corporations & Industries, December 5, 1972 Trends in End-Use Markets for Plastics, December 1972 Modern Plastics, November-December 1972 Plastics World, October 1972 . Kunstoffe-German Plastics, September-October 1972 Plastics & Rubber Weekly, October-December 29, 1972 Modern Packaging, December 1972 Europlastics, November 1972 OLI 7540 WHY PILE THIE C PVt IF V U MUIT RETAIN IT. SPECIFY A DEFINITE RETENTION PERI Di ONE YEAR. THER. 16 By J.L. Throne" and R.G. Griskeyf He.iR vaSuas and thsrmochomical properties c? plastics No extensive tabulation of heating values or heats of combustion exists for plastics. This report was prepared at the suggestion of Modern Plastics to fill this important need. It gives thermochemical data for most common plastics and the methods used to compute these data. Heating values for common fillers, additives, monomers, and crosslinking agents also are included. Heating values for several common plastics exceed the heating values of some conventional fuels. A technical feature Gordon M. Kline, technical editor that cncrgv is given off when these plastics are burned. Note that we are assuming here that sulhiicnt .nr is avail able for complete oxidation of the plastic. In practice, the presence of CO. HCI, HF. NOs, and the like in flue gases indicates that incomplete combustion is taking place. More vigorous stirring of the combusting waste, higher in cinerator operating temperatures, and adequate air supply arc some of the methods that have been recommended to insure complete combustion (3). In Table 1 we have tabu lated the standard heats of combustion, calculated assum ing complete combustion to their final products. Note that heat of combustion is based on the moleculai weight of the mer or repeat unit of the polymer. To obtain the heating value, we converted the heat of combustion to B.t.u./lb. as follows: Heat i hr value. Il.l.u. / III. = --AH," X 11 SI ill/ MW) The critical theme of our times is environmental impact (1-3)*. Nowhere is this more evident than for plastics. The durability and elfectiveness of plastics seem to be a draw back because of the difliculty in disposing of them. This, however, is not necessarily correct because plastics are ma terials with high heating values. In fact, they are not only where MW is the molecular w eight of the repeat unit. The values obtained here correlate well with calculations made by others (5). The total number of moles of oxygen (ON) required from the combustion air for stoichiometric combustion was obtained from the stoichiometric equation: eomparable to most fuels, but in some eases exceed the heating values of commercial fuels For example, polyeth ylene. which represents 5(T7 of all disposable plastics. has a heating value greater than that of fuel oil. coal, or wood. Heats of formation for nearlv all common plasties are given in the Encyclopedia of Poly mer Science and Tech nology (4). These data form the basis lor the calculation of the heats of combustion, healing values, stoichiometric air requirements, and theoretical flame temperatures given in this report From a standard text on thermochemistry (5), we find that if we completely burn a compound of the fol low ing form: f:,HhHr,t.jdr1.i1\,olls1 C,H,in.,,n,1FlllN,OllS1 + (a + I,/ I + i/2 - h/2) fx.-- Final products Note that if a polymer has oxygen in its repeat unit, we as sume that this oxygen is available to aid in combustion. Thus the oxygen demand from the combustion air is pro portionately reduced. Thus, the stoichiometric oxygen re quirement of polyvinyl alcohol (CviHtO) is smaller than that for polyethylene (CNH.,), The total amount of combustion air required for the stoichiometric combustion is calculated from the total number of moles of O^: Stoiihinmetiic ft.* combustion air/ll), resin = (Moles 0../mole repeat unit) x 392* I to the following final products: CO., k) , II..O (l). lit'/). CL ir) .l\, .g). 1 (s). V, ir) . xOj, <r) (0.21 moles O.,/mole air) x MW repeat unit This value assumes dry air at 760 Torr and 25' C. where (g) = gas. (/) ** liquid, and (s) = solid, we can cal The theoretical flame temperature, as presented in i culate the heat of combustion from: Table I. is the temperature attained when the plastic is AH," = -AH,-91.05 a - 31.10 b - 70.96 i (inKcal./p mole) burned in a stoichiometric amount of combustion air with out gain or loss of heat. In this calculation, we have as sumed mean heat capacities for the combustion products, OLI 7541 Here the heat of combustion is determined by the heat of formation (as shown in Table I). and the heats of forma tion (6) of COa. HjO. and SO?, respectively. All other components are converted to their elemental state. Most of the heats of combustion in Table I are negative, indicating and used the following equation: I I'-25) = I -AH,"+ ill/2) 10.;,)/.* 13.2a + W.ti ib/2) + f 179/21) i.i + b/1 + i/2 - li/2 + r/2] a.I + 12 it /2) + 9.0 ul/2) + 8.3 n'/2) + 10.7 f + 8.1 ,r'2) + 13.0 i ) Associate Professor, r.neigeties Dept. University of Wisconsin-Mil waukee Milwaukee. Wise 533)1. to whom all correspondence should be addressed tDean. College of Engineering and Applied Science, University of Wisconsin-Milssaukee, Milwaukee. Wise 53201. I-Numbers in parentheses designate references at end of article. The third (hracketed) term in the denominator is the total number of moles of nitrogen present in the flue gas. The second term in the numerator represents the amount of heat required to convert H20 (/) into H.O (g) at 25 O. The mean heal capacity values were obtained from stan- KIai lAitwkn r 1 Q79 17 Table I: Thermochemical properties of common plastics and fillers Stoichiometric burning Composition of sub-unit C,H< C,H, C3.J1H4 *3 AH,* AH." <25** C.), (25* C.), Sub-unit Kcal./ Kcal,/ MW g. mole* g. moleb -------- ,----------------- -------- -- 28.05 28.05 32.04 -12.25 -12.79 -14.30 -312.5 -312.0 -360.8 Hatting value, B.t.u./lb. --- ------- 20.050 20.020 20.270 Cu. ft. Moles Oi alr/lb., per mole 760 Torr, compound 26* C. -" -- 3 3 3.46 200 200 202 CjH. CjH C,Ha CiHj CiH,0 CjHio C4H13 C-H. Ce.taH* eo 30 42.08 42.08 56.11 56.11 70.13 70.13 84.16 54.09 56.34 61.59 -18.84 -19.27 -24.13 -21.24 -31.07 -31.64 -38.54 +3.13 +3.0' +3.0' -468.3 -467.8 -625.4 -628.2 -780.8 -780.2 -935.7 -584.3 -604.2 -650.5 20.030 20.010 20.060 20.150 20.040 20.030 20.010 19.440 19.300 19,010 4.5 4.5 6 6 7.5 7.5 9 5.5 5.70 6.17 * 200 200 198 198 198 198 198 189 189 187 53.70 +3.0C -512.6 17,180 4.84 168 C.H, C0H10 CioHft C,HjFj CjF a CjFjQl CjHjCl C^HjClj CiHjO CjO, CH30 (0H4O CiHtO C7H70 CjHeO CjH*0 QjHaO CjH403 CjHeO; CjHjO CifrHi^Oj CiHjOCI, HCN CjHjO^N CjHjN s CjH.SO, C.H.SO, c.h,,so3 CuH.jOj (7) CjH,N,0 (7) C.H.N. (7) C. aH, ,N0, , (7) Cs.f/Ht (B) Ci. *jH30.J7Oa4*jN3 3 (7) 66.12 104.2 104.2 118.2 152.2 46.05 64.04 100.0 116.5 62.50 96.95 56.06 68.03 30.03 44.05 58.06 58.08 58.08 72.11 44.05 72,06 100 1 120.2 254.3 155.0 27.03 73.05 53.06 32.06 106.1 120.2 148.2 224.3 84.09 162.2 130.3 101.6 4 212.1 -6.0 +7.09 +8.27 +7.88 + 27.13 -55.8 -- 116.1 -196.1 -156.9 -22.6 -24.0 -48.2 -737.5 -1033 -1034 -1196 -1429 -238.8 -140.3 +8.01 -31.2 -268.0 -232.4 -370.6 19.490 17.850 17,870 18.220 16.900 9.180 3,940 -144 482 7.720 4,315 11.900 -57.57 -40.93 "44,13 -54.41 -54.78 -49.5 -56.8 -61.53 -85.5 "105.B -31.88 -103.26 -82.8 M4.0 -19.98 + 15.85 + 3.56 -95.4 -101.5 -113.7 -120.0' -60.0' -20.0t -100.0C -33.0c -224.06 -121.4 -280.6 -432,7 -432.3 -437.6 -592.7 -263 2 -333.3 -637.7 -993.8 -1880 -660.7 -150.3 -278.7 - 408.6 -74.5 -462.70 -618.9 -913.5 -1496 -358.8 -749.3 -743.1 -723.2 5,940 7,280 11.470 13,410 13.400 13,560 14,790 10,760 8,330 11,470 14.880 13.310 7,673 10.010 6.B70 13,860 4,180 7,850 9,290 11,310 12.000 7,680 8,310 10.180 12,810 -110.0' -1700.0 14,430 7 10 10 11.5 14.0 2.75 2.5 2 2 2.75 2.5 3.5 2 1 2.5 4 4 4 5.5 2.5 3 6 9.5 18 6.5 1.25 1.75 3.75 1 4.5 6 9 17 3.5 7.5 7.02 6.52 15.53 190 179 179 181 183 112 73 37 32 82 48 117 . 55 62 106 129 129 129 142 106 78 112 148 132 78 86 45 132 58 79 93 114 142 78 120 101 120 137 C.H, 104.2 +24.91 - 1050.6 7,590 (9) 8,520 (9) 18,160 10 70 80 180 Theoretical flame temp.. C./*F. Common name ------------* * " ---------- ------------ ------ 2120/3850 High density polyethylene 2120/3850 Low density polyethylene 2120/3850 Ethvlene/propyiene (69/31) random copolymer 2120/3850 Polypropylene, isotactic orsyndiol 2120/3850 Polypropylene, atactic 2120/3850 Poly*1 -butene, isotactic 2130/3870 Polyisobutylene 2120/3850 Poly-1-pentene. isotactic 2120/3850 Poly-3-methyl-1-butene, Isotactic 2120/3850 Poly-4*methyl-1-pentene, isotactic 2220/4020 Poly-1,4-butadiene, atactic 2220/4020 Butadiene/styrene (8.58%) copoly 2220/4020 Butadiene/styrene (25.5%) copoly (GPS rubber) 2190/3970 Butadiene/acrylonitrile (37%) copolymer 2190/3970 Natural rubber (no sulfur) 2210/4010 Polystyrene, isotactic 2210/4010 Polystyrene, atactic-crystal 2210/4010 Poly-n-methylstyrene 2230/4040 Polyacenaphthalene 1710/3100 Polyvinyl fluoride 1090/2000 Polyvlnylldene fluoride d Polytetrafluoroethylene . 320/615 Potychlorotrifluoroethylene 1960/3550 Polyvinyl chloride 1840/3340 Polyvinylidene chloride 2110/3830 Ethytene/carbon monoxide (1:1) copolymer 2260/3910 Polycarbon suboxide 2050/3750 Polyoxymethylene 2120/3850 Polyethylene oxide 2100/3810 Polypropylene oxide. 27% isotacti 2100/3810 Polypropylene oxide, 100% atacth 2130/3860 Polyoxytrimethylene 2120/3850 Polyletrahydrofuran 1980/3600 Polyvinyl alcohol 2075/3770 Poly-0-propiolactone 2070/3760 Polymethyl methacrylate 2200/3990 Polyphenylene oxide 2190/3960 Polycarbonate 1990/3610 Chlorinated polyether 2410/4370 Polyhydrocyamc acid 2670/4830 Polynitroethylene 1860/3380 Polyacrylonitrile 1740/3160 Polysulfur 1970/3570 Polypropene sultone 2000/3640 Poly-1-butene sulfone 2040/3710 Poly-1-hexene sulfone 1860/3380 Phenol-formaldehyde (1:1) 1950/3540 Urea-formaldehyde (1:2) 1990/3610 Melamine-formaldehyde (1:3) 2100/3810 Polyurethanes, ester-based 2250/3910 Unsaturated polyesters (maleic anhydride-based; 1:1 styrene) 2220/4030 Bisphcnol A epoxy (3000 MW; 10% diethylenctriamine) Paper Woodflour Styrene OLI 7542 dard tables (5). The temperature is given in *C\: conver sion to *F. is straightforward. In addition to the conventional plastics, we also present data on fillers, additives, monomers, and crosslinking agents. These data were obtained in the same fashion as the data for the plastics. Note that for some fillers, such as calcium carbonate, we must supply energy to decompose these materials into gaseous products. Flame-retardant ad ditives such as aluminum hydroxide (Al2(OH)e) decom pose endothermically to alumina (AI3O3) and water. This water must then be heated to combustion temperature, thus requiring additional thermal energy. As a result, the heating values for such materials arc negative. For other materials, such as glass fiber and talc, the heating values are zero. This means that plastics filled with these mate rials have a much lower fuel value per pound than the equivalent unfilled plastic. In Table II we compare the heating values of some rep resentative plastics with heating values of other materials. As has been stated by others (3), addition of many types of plastics (in the form of packaging or coatings) to conven tional domestic waste paper or sewage sludge actually in creases its fuel value, thus making it "more burnable." We hasten to add that we are not comparing the rales of com bustion or the ignition temperatures of these materials, only the amount of energy ultimately available to the in cinerator operator for possible use to produce steam and electricity. Rates of combustion and ignition temperatures of these materials must be determined experimentally. The data that are presented here can be used by engineers in the de sign of special incinerators such as hospital incinerators and to objectively evaluate incineration as a viable interim method of solid waste disposal of plastics. References 1) Modern Plastics 48, 44 (July); 76 (Oct.); 18 (Dec. 1971). 2) R.B. Engdahl, "Solid Waste Processing." U.S. De partment of Health, Education and Welfare, Report SW- Table I, cont'd. Stoichiometric burning Composition of sub-unit Sub-unit MW AH' (25* C.), Keal./ g. mole' AH" (25* C.), Kcal./ g. moie*> Heating value, B.t.u./lb. Cu. ft. Moles O, air/lb., per mole 760 Torr, compound 25* C. C.H,, C,F,CI C,H,Br ch,o CjH.O C.H.O, C,HtO, CiH,Oj CjH40 C.H.Oj C,HtO, C.HjOy C,HtOj COCI, C.HjN CjHijOj CaSiO, CiCOy 6aSO, CaSO. MoS3 c 4l,(0H)t CON.H, C,H.Ne 82.15 116.5 107.0 30.03 44,05 86.09 100,1 72.06 56.08 62.07 86.09 98.06 92 10 98.92 43.07 167.2 277.2 116.2 100.1 233.4 136.2 160,1 1201 156.0 60.06 126.2 -9.15 -134.6 + 18.7 -28.2 -46.2 -103.6 -92.7 -80.54 -51.72 -93 1 -75.2 -112.4 -159.8 -53.3 + 30.12 - 58.7 15.35 -896.8 -53.50 -309.3 -134.2 -278.5 -477.6 -650.8 -338 3 -435.4 -300.0 -505.9 -332.1 -395.6 - 40.75 -397.1 -1011 o o o o 0 -34.4 + 21.3 -42.5 + 145,8 -119.6 + 216.4 -94.05 o 0 - 41.6 -188 2 - 520.3 19.650 827 5.200 8,040 12,510 9,985 11.700 8,450 13,970 8,700 10,580 6,100 7,730 742 16.600 7,520 (9) o o o 0 0 234 (5) -331 (5) -736 (5) 1,210(5) -1,800(5) 3,040 (5) 14,110(5) o 0 -500 5,640 11.450 8.5 2 2.75 1 2.5 4.5 6 3 4 2.5 4.5 3.5 3.5 0.5 4.25 ,__ _ __ -- _ -- -- 3.5 10.5 193 32 48 62 106 98 112 78 133 75 98 67 71 10 58 48 0 0 0 0 0 0 0 -- -- -- 15 156 0 0 -- 109 156 -SH* = heat of formation, from reference 4 S-sh, s heat of combustion s-Veiuo estimateo by authors -Win not support combustion Theoretical flame temp., *C./*F. Common name Cyclohexane Chlorotrifluoroethylene Vinyl bromide Formaldehyde Acetaldehyde Methacrylic acid Methyl methacrylate Acrylic acid Acetone Ethylene glycol Vinyl acetate Malotc anhydride Glycerol Phosgene Ethylenimine Cellulose Sand Quartz Diatomaceous earth (dry) Kaolin (clay) Mica Asbestos Calcium metaslilcate Calcium carbonate Barium sulfate Calcium sulfate Molybdenum sulfide Carbon, graphite Talc Glass, fiber Aluminum hydrate Urea Melamine OLI 7543 __ a -- * IIa, Uane 4 <* ^ O 99 19 cmiMiye miss 4c, Bureau of Solid Waste Management, 1969 Public Health Service Publication No. 1856, 3) C.E. Chastain. "Plastics arc ecologically preferred materials," SPE Antec Preprints 18, Part 1,202-205 (1972). 4) R.M. Joshi, "Thermodynamic properties." Encyclo pedia of Polymer Science and Technology, Vol. 13. 1968, pp. 788-831. 5) O.A. Hougcn. K.M. Watson, and R.A Ragatz, "Chemical Process Principles; Part 1. Material and Energy Balances," John Wiley & Sons. New York, 1954, 2nd Ed,, Chapter 9, p. 293. 6) D.D. Wagman, ed,, "Selected Values of Chemical Thermodynamic Properties," National Bureau of Stan dards, 1953, 7) D.C. Miles add J.H. Briston. "Polymer Technology." Chemical Publishing Co., New York. 1965. 8) H.V. Boenig, "Unsaturated Polyesters; Structure and Properties," Elsevier Publishing Co., New York, 1964. 9) J.L, Throne, ed.. "Combustion Data Book," Brown Thermal Development Co., Elyria, Ohio, 1954-end ' OSTMJ ii: NEW 32" X 32" AND 36" X 36" ALSO AVAILABLE A TGP-QUALET7 PRESS AT A TCGHT-BUE3ET PRICE Reliable designed, engineered and built this rugged, versatile press with quality features you'd expect to pay much more for Features like: 20" diameter ram -18" ram stroke 471 ton capacity & 3,000 psi-4 W diameter rods Cast steel rampot Daylight to customers' requirements Fully guided bolster plate with bronze guide bushings Number and type of platens installed to suit customers' requirements GUARANTEED TO BE RELIABLE Fast Delivery-Phone or Write for Details and Prices n n w r- RUBBER & PLASTICS MACHINERY CO., INC. 2008*14 Union Turnpike, North Bergen, N.J 07047 (201) B65-1073 Circle 100 for reader service J| Table II: Comparison of heating values and theoretical flame temperatures of plastics, fuels, and other materials Material Heating value, B.l.u./lb. Methane 23,590* (5) Butane 21,000* (5) Ethylene 21,400* (5) Propylene 20,750* (5) City gas (MW^20) 10,300* (5) Natural gas (MW=20) 22,700* (5) No. 1 fuel oil 19.800 (9) No. 6 fuel oil 18,300 (9) Bituminous coal (med. volatile, W. Va.) 15,178 (9) Lignite (Texas) 11,084 (9) Peat (Minn.) Wood 9.057 (9) 8,835 (9) Peat 3,586b (9) Oil shale Straw 6,300 (9) 6,700>> (9) Sewage sludge 7,500b (g) Paper 7,590 (9) Polyethylene 20,050 Butadiene/styrene copolymer (GRS rubber) 19,010 Polystyrene 17,870 Polyvinyl chloride 7,720 Polycarbonate 13,310 Phenol-formaldehyde resin 12,000 Unsaturated polyesters 12.810 Epoxies 14,430 Glass-reinforced polyester (70% resin) 8,970 Synthetic marble (30% polyester, 70% calcium carbonate) 3,000 Melamine laminate (50% melamine-formaldehyde resin, 50% paper) 7,950 Chipboard (90% woodflour. 10% urea-formaldehyde resin) 8,715 -At 760 Torr, 60* F. b-A* rc*ivd. Theoretical flame temp., C./*F. 2012/3654 2084/3783 2250/4082 2180/3956 2120/3850 2220/4020 2210/4010 1960/3550 2190/3980 1860/3380 2260/3910 2220/4030 -- 1Q7?