INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1953
(178) Trent, C. H., and Zucrow, M. J., IND.ENG.CHEM.,44,2668-73 (1952). (179) Von Fuchs, G. H., Claridge, E . L., and Zuidema, H. H., Am. Soc. Testing Materials, Bull. 186, pp. 43-6 (December 1952). (180) Wadsworth, F. T. (to Pan-American Refining Corp.), U. S. Paten’12,586,128 (Feb. 19, 1952). (181) Ibid., 2,589,648 (March 18, 1952). (182) , . Wadsworth. F. T.. and Smith. F. J.. IND. ENG. CHEM..45. 217-21 (i953). ’ (183) Wagner, E. (to Deutsohe Gold-u-Silber Scheideanstalt Y. Roessler), U. S. Patent 2,605,168 (July 29, 1952). (184) Walker, F. T., and Mackay, T., J. A p p l . Chem., 2, 344-52 (1952). I
,
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(185) Walker, P. L., Jr., and Wright, C. C., J . Am. Chem. Soc., 74, 3769-71 (1952). (186) Ibid., 75,750-1 (1953). (187) Wan, Shen-Wu, IND.ENG.CHEM.,45,234-8 (1953). (188) Weber, Geo., Oil Gas J., 51, No. 29, 118-19 (1952). (189) Weisblat, D. I . , and Magerlein, B. J. (to The Upjohn Co.), U. 5.Patent 2,615,040 (Oot. 21, 1952). (190) Wibant, J. P., and Strang, A., Koninkl. Ned. A k a d . Wetenschap., Proc., Ser. B,55, 207-18 (1952). (191) Withrow, L. L., and Bowditch, F. W., S.A.E. Quart. Trans., 6 , 724-52 (1952). (192) Wood, W. S., Chemistry &Industry, 1953,2-6. (193) Young, H. D., Petroleum Engr., 25, C-10-20 (1953). (194) Young, R. S., and Benfield, D. A,, J . A p p l . Chem., 2, 320-53 (1952).
POLYMERIZATION mg
CHARLES C. WINDING and HERBERT F. WIEGANDT CORNELL UNIVERSITY, ITHACA, N. Y.
The number of 1959 publications dealing with polymerization” was approximately the same as For the previous year. The polymeric soil conditioners received much attention, but other less-publicized developments may be even more important. New catalysts end continuous processes For synthetic rubber indicated that marked changes are certain to occur in this field. The disposal of the government rubber plants moved one more step toward reality. The newer fibers began to reach the ultimate consumer in relatively large quantities and brought to light many new problems. The epoxy resins gained a foothold among the coating and adhesive resins. Behind the more sDectacular developments was a remarkable increase in Droduction capacity For polyethylene, the vinyls, and nylons.
T
HE number of publications dealing with various phases of the unit process of polymerization appears to be leveling off. The previous review of this series (533) for 1951 covered 585 references; 557 are cited for 1952. However, predictions of present and future production of polymeric materials indicate t h a t plastics, rubbers, fibers, coating materials, and adhesives are all still growing at a remarkable rate and will continue t o do so. Without doubt the most publicized development in the field of of polymers in 1952 was the public announcement of soil conditioners and the race to get them into the hands of the consumer. The resulting controversy over their effectiveness probably will not be settled for years t o come. The rubbers also received considerable attention both because of the imminent disposal of government plants and the announcement of new catalysts and processes. The new fibers reached the more or less confused consumer bringing new problems b u t little or no reduction in proposed new plants and expansion of existing capacity. The few new polymers t h a t emerged from pilot plants appeared t o be headed for specialty uses rather than competition with existing materials. Behind the more spectacular developments was a remarkable increase in production capacity for polyethylene, the vinyls, and nylons. This review attempts to cover 1952 material directly related to the unit process of polymerization, including general theoretical aspects, reaction mechanisms and kinetics, effect of all types of addition agents on reactions, monomeric reactants and resulting polymers, reaction conditions, complete processes, apparatus, and descriptions of existing plants. It does not include publications dealing exclusively with production statistics, uses, applications, structure, properties, or modifications of high polymers. However, many of the references cited may be devoted in part to such subject matter. Eight general reviews (220, 346-347, 978, 288,473, 514) other than the preceding one of this series, appeared during 1952.
CATALYSTS, ACTIVATORS, MODIFIERS, AND INHIBITORS
In the petroleum industry, catalYsts and reaction conditions are selected t o produce low molecular weight polymers; usually dimers, trimers, and tetramers. Anderson (18) used alumina-silica isomerization catalysts followed by aluminum chloride polymerization catalysts t o produce lubricating oils from olefinic FischerTropsch fractions. Bailey (43) polymerized olefins using silica gel impregnated with nickel and aluminum oxides. Boron trifluoride was employed to polymerize propylene (101 ) and, in a n ether complex, to form polyisobutylene (473). Phosphorus pentoxide catalysts were investigated by Kolfenbach and Small ($86)and Meerbott (352). Ortho phosphoric acid was also suggested (98, 270, 876) for olefinic polymerizations. Krug (296) polymerized monoijlefins in the presence of boron phosphate. I n the formation of high polymers by addition polymerization, most catalysts actually initiate the reaction by free-radical or ionic mechanisms rather than by true catalytic action, but many authors do not distinguish between catalysis and initiation. It is beyond the scope of this review t o attempt t o make such distinctions and the words “catalyst” and “initiator” will be used synonymously. Per compounds, azo compounds, and Grignard reagents initiate polymerizations by forming free radicals which react with, and activate, monomers. Three general reviews (856, 346, 400) of this type of initiation were published. Adman and Wagner (26) conducted experiments t o investigate the degree of conversion and molecular weight as a function of type and concentration of initiators. Sengupta and Palit (443) compared induction times and reaction rates at different temperatures for persulfate and peroxide catalysts. Cooper (124, 186) studied the effect of peroxide structures on the rate of the initiation reaction. T h e following peroxide catalysts were proposed: a,a’-dialkylarylmethyl hydroperoxides (607), phthaloyl peroxide (511), acrylyl and cyclic succinyl peroxides (376), peroxides of vinylcyclopentene (68), p-hydroxydialkyl peroxides (63),pinacolone peroxide (376), and alkyltetrahydronaphthalene hydroperoxide (411). Reynolds, Wicklatz, and Kennedy (413) speeded up GR-S
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polymerizations by using the monohydroperoxide of teit-butyl isopropyl benzene plus polyamines. Miller, Dittman. and Reed (340) suggested the use of hydrogen-free perhalogenated peroxides as initiators. Nitrazole rubbers equivalent to cold rubbers were prepared using p-nitrobenzene diazonium p-chlorobenzene sulfonate as a n initiator (28). Azonitrile catalysts were investigated by Arnett and Peterson (38), Breitenbach and Schindler (80)’ and Robertson (416). Reynolds (409) and Tucker and Wells (498) initiated GR-S polymerizations with diazo thioethers. Azo-cyano compounds (163) and azobis(dipheny1methane) (154)were suggested for ethylene polymerizations. Hydrazo compounds (641) and diaeosulfones (491 ) were found t o be effective in catalyzing ethenic polymerizations. The mechanism of ionic initiation was studied by Colclough (120) using radioactive antimony pentachloride. Kolfenbach and Small (284),Schutze (439),and Sparks and Thomas (463) all employed specially prepared aluminum chloride in butyl rubber polymerizations, and Sparks and Thomas (462) used boron trifluoride for the same purpose. Brasch ( 7 9 ) and Loewe (310) found t h a t polymerization could be initiated by irradiation with high speed electrons. Friedman (190) copolymerized ethylene and butadiene using a calcium oxide catalyst. Bullitt ( 9 4 ) employed sodium in liquid ammonia for acrylonitrile polymerizations. Folt (180) catalyzed vinyl polymerizations with compounds yielding sulfite ions. D’Alelio (133) suggested the use of cation exchange resins containing sulfonic acid groups as polymerization initiators. Stabilized redox activators for GR-S polymerizations were proposed by Fryling (192), Fryling and Follett (195), and Uraneck, Tucker, and St. John (506). Kolthoff and Meehan (386) suggested several redox recipes. Gould (216) investigated ferric acetylacetonate activators for vinyl polymerizations. Jordan and Cline (264) found that alcohols accelerated indene and coumarone polymerizations catalyzed by stannic chloride. Luce (313) reported that vinyl acetate polymerizations were activiated b y methallyl maleate. Walsh and Schutze (521) discovered t h a t small amounts of butyl rhloride or bromide promoted Friedel-Crafts catalysts, and Walsh (660) retarded the polymerization of isobutylene with ethylene. Modifiers are added to many polymerizations to reduce the amount of branching and cross linking and t o control the degree of polymerization. Baysal and Tobolsky ( 5 6 ) studied the effect of modifiers during vinyl polymerizations. Franta (189) controlled branching with cyclohexane during the polymerization of ethylene. Methyl iodide was used (50) to modify vinyl chloride polymerizations, and disubstituted amino mercaptans were suggested (466)for GR-S polymerizations. Several inhibitors were suggested as shortstops in the emulsion polymerization of butadiene. Adams and Reynolds (2) used a product of ethylene diamine and sulfur. Dunbrook, Bebb, and Street (160) tabulated the performance of the agents they used. Schulee and Crouch (488) use dithiocarbonate compounds. Miller, Alumbaugh, and Brotherton (337) found that the undesired growth of butadiene polymers in storage or distillation is accelerated in proportion t o the mass of seed. McMillan and Bishop (319) stopped styrene polymerizations short with a tetramethyldihydropyridine. Mack and Bickford (317) found conidendrols to be effective in inhibiting vinyl polymerizations. Acrylonitrile polymerization v-as inhibited with p-benzyloxyphenol by Nichols (366) and with naphthylamine by Stehman (471). Phenylenediamine was suggested as an inhibitor by Evans and Whitney (167) for the polymerization of m-vinylphenol. T o catalyze aldol-type condensations with furfural Mastagli, Floc’h, and Durr (830)discuss the applicability of anion exchange resins in place of sodium hydroxide. Phosphorous acid was reported a s a catalyst for polyamide condensations (458). Molten sodium in xylene served t o form high polymers from
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tlialh~.ldichlorosilanes by a Wurtz-type synthesis (245), Di Giorgio and Safford (140) found various azo compounds to be catalyst. for polysilouanes. Gonikberg (810) offered a theoretical discussion on the effect of pressure on the thermodynamics and kinetics of polymerizntion. Johnson and Wolfangel (258) related the effect of polymerization conditions to the bi anching and cross linking obtained. Stereochemical factors and radical vs. ionic factors were conqidered for the ethylenes by Korshak and Matveeva (291). Bonsall, Valentine, and Melville ( 7 4 ) studied the polymerization rate for methyl methacrylate and several of its copolymers. Foster (186) investigated carbanionic copolymerizations of acrylonitrile with vinyl butyl sulfone, styrene, and methyl methacrylate. Gantmakher, Medvedev and Lipatova (198) presented a general discussion of the mechanism of initiation and the reaction termination of Friedel-Crafts catalyzed polymerizations. One effect of aluminum chloride in radical polymerization was found by Haas and Karlin (221) to be the preferential removal of acrylonitrile in its copolymerization with methyl methacrylate. The mechanism and kinetics of reactions catalyzed by stannic chloride were reported for isobutene by Norrish and Russell (360) and for styrene-chlorostyrene by Overberger, Arnold, and Taylor (373). Vaughan discussed the reaction mechanism and kinetics in the bulk polymerization of styrene (610) and showed the importance of diffusion a s the polymerization mass became viscous (518). Zimm and Bragg (556) based their analysis of the mechanism of the biradical-initiated polymerization of styrene on the rate constants. Merrett and Norrish (334) interpreted the increase in rate for styrene polymerization as the pressure was increased to 5000 atmospheres in terms of possible mechanisms. Wintgen and Sinn (637)discussed the mechanism, Bakker (45)the kinetics and Yurzhenko and Tsvetkov (664)observed the effect of initiatoi concentration in the emulsion polymerization of styrene. Chitani (116) related the chemical structure of CY- and p-methylstyrenes to their polymerization ability. Jordan and Mathieson investigated the mechanism and kinetics of the aluminum chloride-catalyzed polymerization of styrene (262) and amethylstyrene (265). The kinetics of methyl methacrylate polymerizations were investigated by -4rnett (51) and by Shantarovich (444)who catalyzed the reaction with ultraviolet light. Similar information was presented for methacrylic acid by Katchalski and Blauer (272). Bauer (54)proposed a new definition of polymerization based on experiments with methylacrylate and ethylene dichloride. The kinetics and mechanism of the polymerization of vinylacetate were discussed by Polyakov and his coworkers (395’). Wheeler, Lavin, and Crozier (629) found more branching in polyvinylacetate produced in a kettle continuously than batchwise. H a a s and Simon (262) compare the relative reactivities of various monomer pairs such as vinyl acetate and methyl vinyl ketone. Eley and Saunders (160) showed the effects of various side chains in a study of the kinetics of vinyl ether polymerizations catalyzed by iodine. Wooding and Higginson (548) evperimentcd with liquid ammonia and diethylether as solvents for the polymerization of methyl methacrylate, styrene, and butadiene. The latter was found to be insoluble and did not polymerize. They used numerous catalysts. The copolymerization of methyl vinyl sulfoxide with methyl methacrylate and with styrene were studied by Price and Gilbert (396). Wheeler (588)reviewed theories and Paschke, Jackson, and Wheeler (379) studied the kinetics of the thermal polymerization of methyl linoleate. Synthetic latexes and possibilities for their improvement were reviewed by Fowler and Westerhoff (186). They discussed various monomers, molecular sizes, and arrangements of monomer units in copolymers. Wintgen and Jurgen-Lohmann discussed the mechanism of emulsion polymerization of styrene (635)and of chloroprene (656). Gantmakher and bledvedev (197) obtained
September 1953
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
information on the kinetics of isoprene polymerization using stannic chloride a s a catalyst. Orr and Williams (371) determined reactivity ratios for copolymers of isoprene and 2,3-dimethyl butadiene with styrene. Rearrangements and disproportionations in the gas- and liquid-phase polymerizations and copolymerizations of propene, cis and trans butene, and isobutene using Friedel-Crafts catalysts were discussed by Meier (333). Copolymerization was defined and its theories reviewed by McNabb (328). Morton, Salatiello, and Landfield (347) determined the rates of polymerization for butadiene-styrene emulsions. The copolymerization of styrene with other monomers was studied by Armitage and K u t (29) using conjugated acids, by Barb (49) using sulfur dioxide and Brunner and Tucker (91) using tung oil. Rutovskii and Shur (428) investigated the mechanism of the copolymerization of methyl and allyl methacrylates. Reaction rates for polycondensations of the phenol-aldehyde type were studied by Debing, Murray, and Schatz (I%), Gold (209), Hauck (231), Kagawa and Shirai (267), Kakiuchi (268), Kiimmerer (266), and Muller and Muller (349). Wohnsiedler (640) developed a structural theory for urea a n d melamine formaldehyde resins. Marvel and Cripps (327) considered the mechanism of the reaction between hexamethylene dithiol and 1,3-butadiene.
ETHENIC POLYMERS AND COPOLYMERS Ethylene was dissolved in aliphatic solvents and polymeriied under pressure by Boyd (76). Charlesby (11%)discussed the cross linking of polyethylene exposed to neutron and gamma radiation within a n atomic pile. Copolymers which may be cross linked were made by Pinkney, Pratt, and Wayae (389)from ethylene, acrylic esters, and a n unsaturated dicarboxylic acid. Synthetic drying oils were made by Verley (613) from a diolefin and unsaturated fatty-acid products and by Arundale, Gleason, and Barnes (34) from a diolefin and vinyl compound. Synthetic lubricating oils from the polymerization of olefins were described by Fritz (191) and Heinrich (233). Garber and Hollyday (199) polymerized olefins and condensed the polymers with mercaptans to obtain viscosity improvers. Fontana and Kidder (184) reported the effects of operating variables on the polymerization of propene and butene. Isobutene, styrene, and propene were copolymerized (470). Jones (260) and Penn (387) surveyed polymerizations using acenaphthylene. Armitage and Fry (27) and Kauffman and Williams (273) investigated copolymers of acenaphthylene, styrene, and drying oils. Insulating oils were obtained from mixed olefins and diolefins (468). Scott and Gunning (442) studied the polymerization of cyclopropane. Styrene was found t o polymerize in liquid ammonia by Higginson and Wooding (234). Northgraves (361) polymerized dichlorostyrenes. Highet, Salt, and Stanley (236) produced thermal polymers from a-methylstyrene. Feagin and Bandel (172) copolymerized dichlorostyrene with esters of maleic acid. Rowland (424) and Otto and Reiff (372) modified styrene-maleic acid copolymers with organic sulfur compounds. Copolymerization of styrene with allyl compounds was reported by Polly (391, 392) and Shokal and Devlin (446). Glycidil acrylates were copolymerized with styrene by Erickson and Thomas (166) t o produce casting resins. Kropa (294) reacted polydimethyl styrene with acrylonitrile. Styrene and isobutene were the ingredients for copolymers by Schneider, Young, and Goering (437), and Smyers and Young (464). Also reported were copolymers of styrene with m-hydroxy styrene by Novotny and Vogelsang (362),with a trivinyltrichlorobenzene by Ross and Markarian (421), and with a coumarone-indene and aliphatic olefin mixture by Geiser (201). Dreisbach (147) obtained thermoplastic products from dimethylstyrene and p chlorostyrene. The reactions of drying oils with styrene were extensively reviewed by Armitage and K u t (%?),Korfhage (287),and K u t (397). Other references (24, 36, 69, 62,77,107, 388, 418, 4-49,460) were
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concerned with specific examples of the copolymerization of styrene with drying oils, acids, and esters to produce coating resins. Polyvinylacetate of high molecular weight was obtained by polymerization in a tertiary butyl alcohol solvent by Minsk and Taylor (342). Three references (123,323,467) t e a l with the copolymerization of vinyl acetate with the salts or esters of acrylic acid. Port, Jordan, and Hansen (396) reported t h a t true copolymerization takes place between vinyl acetate and longchain f a t t y acids. McGrew and Pinkney (316) copolymerized vinyl acetate with acetylene. The technology of polyvinyl chloride was reviewed by Spurnik (469). Sans (430) prepared polyvinylchloride from the gaseous monomer. Ellingboe (161) copolymerized vinyl chloride with an allyl glycidil ether, and with Rothrock (162) he also included an allyloxyalkanoic acid. Copolymers of vinyl chloride and styrene were produced by emulsion polymerization (211). Wolf and his coworkers (643-647) copolymerized vinyl chloride monomers such ' as isobutene, monovinyl sebacate, diallyl maleate, styrene, or acrylonitrile. Copolymers of vinylidene chloride and acrylonitrile were produced by Pitzl (390) and Reilly (406). Vinylidene cyanide copolymers were extensively studied by Ardis (%), Averill ( C f ) , Folt (181, 1829, Gilbert and Miller (206), and Miller (336) using olefins, diolefins, chloro-olefins, vinyl esters, acrylates, and styrene. H a m and Chapin (225) and Schmidt, Ardis, and Gilbert (436) presented methods for solution polymerization of acrylonitrile. Several monomers were reported suitable for copolymerization with acrylonitrile. Bruson (92) used a n amino alcohol vinyl ether and also a sulfonic acid derivative of a vinyl monomer (93). Conard (122) suggested vinyl sulfide. Vinyl pyridine was employed (166). H a m (224) proposed vinylidine chloride. Lytton (316) investigated amine oxides. Thomas and Price (492) used an acrylamide. Wohnsiedler and Kropa (641) added ethyl acrylate. Rothrock (423) formed a copolymer with an allyloxyethanol. Other nitriles were found t o be suitable for polymerization by Dickey (138) who copolymerized a-acyloxyacrylonitriles with various unsaturates and by Hearne and LaFrance (232) who polymerized a-alkylidine-,&hydroxy proprionitriles. The polymerization of several acrylic esters was studied by Rehberg and Siciliano (403). Polymethyl-a-chloroacrylate (21) and rubbery polymers such as fluorobutyl acrylates (23) were announced. Iuchi (265') polymerized methyl methacrylate in the presence of ammonium polysulfide. The polymerization of alkoxyacrylates was reported (106). Monomers used in copolymerizations with methacrylic acid included diethylaminoacrylate by Alfrey and coworkers (10); Zvinylpyridine by Alfrey a d Morowitz (11) and Jones (269); butadiene by Frank, Kraus, and Haefner (188); and trichloropropene by Ladd (299). Crawford (131) polymerized methyl methacrylate with higher acrylate esters. Dickey and Coover (139) prepared polymers from a-substituted acrylic acids and esters. Copolymers of ethyl acrylate with 2-nitropropane were reported by Fields and Wesp (173) with allyl isocyanate by Kropa and Nyquist (296) and with chloroethylvinyl ether by Mast and Fisher (329). Catlin (f08,109) and Popkin (394) reported on polymerizations to give acrylate copolymers suitable as viscosity-index improvers. Unsaturated polyester resins were reviewed by Parkyn (378). This group of polymers includes the unsaturated polyesters which are subsequently cross linked by an ethenic polymerization. Such resins made from unsaturated alcohols and polycarboxylic acids were reported (367,369). Interpolymers between styrene and unsaturated polyesters were reported by Harrison (.2.29),Hovey (%$(I), Marling ( 3 6 ) .Rubens and Boyer (426), 'schmutzler (436), Tess (489), Wakeford (627), Wakely (618),and Wynstra (660). Agnew (8) copolymerized unsaturated alkyds with diallyl phthalate; Cordier (226) used tritolyl phosphate as well. A number of other combinations for copolymerizatibn were
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reported. Elliot (163)discussed the use of triallyl cyanurate with modified maleic alkyds. Evans, Adelson, and Whitehill (168) used allyl acid maleate and vinyl acetate. Kropa (293) used an acrylamide withunsaturated alkyds. Neher, Bauer, and VanHorne (352, 509) used mixtures o f allyl esters. Tawney used diallyl maleate a n a a 2-alkenvl chloride (481); 2-alkenyl alcohols with polyesters of unsaturated alcohols (482); unsaturated nitrate esters with unsaturated alcohols (484);allyl alcohol with allyl maleate and styrene (485); and diallyl phthalate with allyl alcohol (486). Toy and Brown (497) used unsaturated esters of arylphosphonic acids m ith unsaturated alkyds. Whetstone and Evans (530) used unsaturated polyesters and allyl esters of saturated fatty acids. Ilawai (274) polymerized derivatives o f 3,B-divinyI carbazole. The polymer of 3,6-epoxy-1,2-cyclohexanedicarboxylicacid was reported (459). Harman and Stiles (298) and Morris, Buls, and Ballard (345) copolymerized unsaturated esters of phosphonous acid with diallyl phthalate. Evans and Shokal (169) made fusible polymers from allyl ethers of glycidols. Drechsel and Padbury (146) copolymerized diallylcyanamide with other monomers. The various polymers containing fluorine are grouped together. Three reviews (3,20, 239) appeared on the subject. Caird (97) and Roedel (419) reported methods for the polymerization of chlorotrifluoroethylene. Vinyl acetate was copolymerized with chlorotrifluoroethylene by Joyce (265). Pearson used styrene (583), vinyl acetate (384, and methyl methacrylate (386) for copolymerization with chlorotrifluoroethy1ene. Tetrafluoroethylene was polymerized in colloidal dispersion by Bankoff (47), in suspension by Myers (351), and using a chlorinated peroxide catalyst by Miller (339). This peroxide catalyst was also effective with other haloolefins and perhalodefins (541) Smith and coauthors (453) observed that condensation proceeded simultaneously with the fluorination of hydrofluorocarbons. Miller (558) discussed the preparation polymers from fluoroolefins. Passino (380) polymerized fluoroolefins in a fluoroplasticizer. Halogenated (trifluoromethyl) styrenes were polymerized by Bachman and Lewis (49). T e Grotenhuis and Swart (487) copolymerized substituted styrenes with fluoroethylenes. Austin (39) copolymerized isopropenylfluoride with several monomers. Reid (406)formed polymers from vinyl esters of perfluorocarboxylic acids. Pearson (386) obtained copolvmers from vinyl esters and vinylidene fluorochloride. Several references consider the polymerization of unsaturated ethers. Ladd and Harvey (500) used dihalopropenyl arvl ethers. Luce (312) copolymerized allyl derivatives of hydroxy arids with maleic anhydride. Roach and Wittcoff (414) polymerized unsaturated ethers made from glycerol derivatives and all! 1 chloride. Zoss polymerized vinyl alkyl ethers (557) and carried the reaction further with other unsaturates in the presence of boron trifluoride (BF3) (556). Allyl carbonates and related compounds were polymerized by Adelson and Dannenberg (5), Bralleg and Pope (78), and Muskat and Strain (550). The carbonates of unsaturated diols were polymerized by Adelson (4). vinyltetrahydronaphthalenes were polymerized (86, %77) and copolymerized (85) with other vinyls. blaleic acid or its anhydride waj used in a variety of copolvmerizations. Carlson (102) used polyallyl carbonate esters of bisphenols. Giammaria used styrene, vinvls, and allyl benzoate (204), and esters of itaconic acid (206). Lippincott and coworkers used butadiene monoxide (308), I-octadecene (309), and other olefins (307). Dudley (149) used nonconjugated polyunsaturated compounds. Adachi (1) polymerized 1,5-bis(p-vinylphenyl)pentane. Vinyl phenols (83),2-vinyldibenzo-thiophene (84), and p-vinylbenzeneamide (142)were polymerized. Davies (134) obtained a colorless resin from methyl vinyl ketone. Dickey (137) obtained polymers from derivatives of vinvl carbamic acid. Price copolymerized 2-vinylbenzimidazol with other vinyls (397). Emulsion
Vol. 45, No. 9
polymeriation of isopropenyltoluene with other monomers was performed by Schaffel (433). Thomson and Bloch (493) copolymerized a n aromatic monofulvene with unsaturated hydrocarbons. Bloch and Wackher (78) obtained synthetic drying oils from olefins and carbonyl compounds using hydfluoric acid (HF) as a catalyst. Linville (306) polymerized 1.4-dicyano-2-butene Weisgerber (586) obtained amphoteric copolymers from allylacetamide and ethylenic monomers. Ralston, Vander Wal, and Hal wood (399) produced elastomers from amides of unsaturated acids and unsaturated amines. Malinowski (324) obtained a polymer from hydroxymethylmelamine ethers and cyclopentene. Emulsion polymerizations of olefins and sulfur dioxide were performed by Crouch (132). Coffman (118) produced adhesives from P-methylene-P-propriolactone and vinyl monomers. Izard (953) considered interpolymers of vinyl acetate styrene, and others with allylidene diacetate. Hillyer (636)obtained a resin from 2-furaldehyde refluxed with morpholine. hnders (16) reviewed coumarone resins. Korolev and Leonova (288) studied the polymerization of linseed oil. Robinson and Ropp (417) showed t h a t vinyl esters of rosins give higher polymers than straight rosin. Bloch (69) modified drying oils with olefins.
ELASTOMERS Two general reviews (422, 429) of elastomers were published, two reviews (58,475) were limited to synthetic rubber. Coffman (119) produced a hard rubber from butadiene using either redox or sodium activation. Reynolds and Fryling (410) polymerized several dienes, including butadiene, a t temperatures below 0' C. Westfahl and Sears (527) prepared and polymerized 2-carboalkoxy-1,3-butadiene. Wiseman (538)studied the emulsion polymerization of 2,3-difluoro-1,3-butadiene, and Crane and Eberly (130)did the same for l,l-dichloro-1,3-butadiene. Beatty and Zwicker (57) and Howland, Neklutin, Brown, and Werner (243) reviewed the effect of reaction variables on GR-S copolymers. Betts, McCracken, Rose. and Wood (64) copolymerized butadiene and styrene to latices having a high concentration of solids. Gilbert and Williams (207) obtained relative reaction ratios for butadiene and styrene, isoprene, and dimethyl butadiene. Uraneck and Landes (505) produced copolymers of butadiene and styrene using hydroperoxide catalysts containing 6 t o 30 carbon atoms. Strain (474) condensed butadiene with alkyl benzenes and then copolvmerized the resulting adduct n-ith stvrene. Reich, Schneider, and Taft (404)studied the catalysis of butadiene-styrene copolymerizations with sodium. Gleason and Jaros (208) prepared drying oils from butadiene-styrene copolymerizations. Marvel. Fukuto, Berry, Taft, and Labbe (328) prepared copolgmers of butadiene with acrylic and methacrylic acids, tetrahydiofurfuryl acrylate, and 2-ethoxyethyl methacq late. Swart (477) copolvmerized butadiene and methvl o-chlorocinnamate, hrundale and Bascom (38)obtained concentrated nitrile rubber latexes from the copolymerization of butadiene and acrylonitrile. Vanderbilt and Bascom (508) described the preparation of hutadienemethacrrlonitrile copolymers. Romeyn and ILIcCleaI v (420) found that t h r gel content of nitrile rubbers could be controlled by adding a small amount of divinyl benzene to the polymerization. Agnew ( 9 ) investigated the dispersion polymerization of dienes and unsaturated polyesters. Doak and Wilzbach (143) made copolymers from butadiene and esters of methylene malonic acids. Three patents (70, 354, 553) dealt with the low temperature copolymerization of isobutylene and butadiene using FriedelCrafts catalysts. Jasper and Welch (256) copolymerized isobutylene and styrene a t low temperatures. Geiser and DeRosset (202) obtained rubbery materials by partially polymerizing isobutylene and then copolymerizing the product with butadiene or styrene. Sparks, Thomas, and Field (464) studied the low temperature polymerization of hexadiene isomers to form rubbers. Gerhart
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INDUSTRIAL AND ENGINEERING CHEMISTRY
($03) copolymerized cyclopentadiene with various vinyl monomers. Aelterman and Smets (7) compared the polymerization and structure of three isomeric chloroprenes. Polysulfide rubbers were obtained (302, 402) from the reaction between dichlorides and alkali polysulfides. The announcement (19) and description of properties (525) of a vulcanizable chlorosulfonated polyethylene received considerable attention.
CONDENSATION POLYMERS
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1
Phenolic resins were covered in two reviews (96, 381). Pritr chett and Barnett (398) used alkaline catalysts followed by rapid neutralization t o prepare phenolic resins. Duroux (167) condensed phenol, cresols, and formaldehyde t o produce coating materials. Kvalnes (898) investigated the reaction between polymethyloiphenols and phenol or urea. Messina (335) described the condensation of phenol and hexamethylene tetramine in diluents. T a a t and Korndorffer (480) improved hardening rates of cast phenolics by adding maleic anhydride and glycols. Mixed aldehyde-phenol condensates were prepared (44). Cavier (110) produced a resin by first condensing phenol and formaldehyde and then heating the product with urea, formaldehyde, and a mixed metallic catalyst. Jones (861) and Niederl (556) described condensations of para substituted phenols to produce coating resins. Rhodes (413) and Spahr (461) developed mixed phenol-resorcinol-formaldehyde condensates. Sargent (431) condensed methylol phenols with amides. Speier (466) made phenolic resins from silylphenols and hexamethylenetetramine. Evans (166) polymerized vinyl phenols with cyclopentadiene, coumarone, or indene and cross linked the product with hexamethylenetetramine. Teot (488)alkylated phenol with styrene and condensed the product with aldehydes. Morini (844) reviewed the synthesis of ion exchange resins. Runk (427) investigated the condensation of p-tert-butyl phenol, diphenyl propane, and formaldehyde. Other aldehyde condensates received some attention. Brown (88) and Reineck (407) reviewed phenol-fnrfural resins. Mixtures of cresols and furfural were condensed (87) and combined with polyvinyl formal resins. The furfural-ketone reaction and the polymerization of the product were investigated by Harvey (250). Bisterfeld (66) produced resins from phenol and acetaldehyde, and Brown (89) used various dialdehydes. Three reviews (577, 582, 451) of urea-formaldehyde resins were published. Coating compositions were obtained (61) by heating urea and formaldehyde in alcoholic solutions. Auten and hleunier (40) produced water-soluble resins from urea, formaldehyde, and dimethylamine. Cornwell (127) impregnated cellulosic fillers with urea and reacted them with gaseous formaldehyde t o give molding compositions. Cherrier (114) made artificial leather by heating urea, formaldehyde, glycerol, and vegetable oils in a solution of polyvinyl alcohol. Two references (136, 441) described the production of resins from urea, thiourea, and aldehydes in the presence of organic bases such as pyridine. Bloch and Thompson (71) heated polyketones and urea to make thermosetting resins. White (531) prepared mixed urea-melamine resins. Kohler and Enzensberger (282)reviewed the chemistry of melamine resins. The reaction of melamine and formaldehyde under controlled p H conditions was investigated (305). Jackson (254) added salicylic acid to melamine and formaldehyde to obtain water-soluble resins. The use of sodium sulfite to modify melamine resins was suggested (14, 75). Niles (357) modified melamine resins with phenolsulfonic acid, and Thurston and Adams (494) used sulfonated aromatic-substituted melamines. Keller and Hansen (275) produced condensation products of melamine and tris(hydroxymethy1)acetaldehyde. Polyamines were condensed with urea and formaldehyde (171, 668). Simons (447) reacted furfuryl ureas with formaldehyde and Schappel (434) condensed sulfon6s with urea. Upson (604)obtained borourea polymers from boric acid esters and substituted diureas.
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Von Fischer (515) reviewed polyesters for coating resins. DuPuisand Wright (166) produced shore-oil alkyds containing amine inhibitors. Runk (426) studied the effect of the composition on properties of oil-modified glyceryl phthalate resins. Blair (67) made demulsifiers from glycols and dicarboxylic acids. Tess and Mika (490) improved alkyd resins by adding p-tert-butyl benzoic acid. Auer (38)modified polyester resins with ethylcellulose, Sarin, Kapur, and Aggarwal (432) substituted dimerized linoleic acid for part of the phthalic anhydride in the preparation of alkyds. Morton and West (348) obtained synthetic lubricating oils by condensing dicarboxylic acids, monohydric alcohols, and polyglycols. Brintzinger and Orth (81) prepared alkyd resins from tetrachlorophthalic acid. Earhart and Davis (159) condensed the adduct of rosin and maleic acid with glycerol monochlorohydrin. Dihydric alcohols and unsaturated dibasic acids were heated (13) with polyfunctional alcohols to give alkyd resins Snyder (456) partially condensed dimethyl terephthalate with ethylene glycol and then continued the reaction with dimethyl sebacate and additional ethylene glycol. Allison (19) produced bonding resins from pentaerythritol and dimethyl terephthalate. Lum and Carlston (314) investigated polyesters of glycols and isophthalic acids. Drewitt and Lincoln (148) reacted hydroquinone diacetate with adipic acid to form filaments. Elwell (164) obtained drying oils from the condensation of polyhydric alcohols, cyclic dicarboxy acids, and fatty acids. The preparation of thermosetting resins from dicarboxy acids and polyhydric alcohols was reported (158). Wittcoff and Roach (539) prepared coating resins from pentaerythritol, glycerol monochlorohydrin, and abietic acid. Armitage and Sleightholme (SO) formed films by condensing unsaturated f a t t y acids with polyhydric alcohols and then polymerizing the product with styrene. Polyesters were produced (99) from 4-vinylcyclohexene dioxide and phthalic anhydride. Hutchinson (849) made resins by heating carboxyalkyl ethers and polyhydric alcohols. Lombard (311) studied the polymerization of 11-hydroxyundecanoic acid. Knight (881) obtained plasticizers by esterifying 9,lOdihydroxystearic acid and phthalic anhydride. Flory and Leutner (177-179) described the preparation of polyesters from dicarboxylic acid chlorides and various glycols. The use of terephthalic acid chloride and ethylene glycol was also suggested (534). Guenther (219) reacted glycerol a n d diamines with perfluorosebacic acid t o produce coating resins. Ashar and Champetier (36) prepared polyamides from 9,lOdihydroxy-l,l&octadecanedioic acid and hexamethylenediamine. May and Fisher (331) obtained high molecular weight polyamides for fiber formation from dicarboxy acids and 1,4-bis(3-aminopropoxy)cyclohexane. Speyer (467) studied the preparation of polyamides from dimerized and trimerized unsaturated fatty acids and ethylenediamine. Korshak and Rogozhin (292) condensed 4,4'-diaminodiphenylethane and dicarboxy acids in a cresol solvent. Cowan and Teeter (129) made polyamides from alkylene diamines and adducts of alkyl oleates and maleic anhydride. Mixed bicyclic and monocyclic lactams were used (250) to form polyamides. Carello (100) described the production of polyamides starting with furfural and ammonia. Fisher, May, and Wheatley (174) condensed sulfone dicarboxylic acids and hydrazine. Tullock (499) reacted phosgene with amino acids to give polyamides. The use of amino acid arihydrides for the production of polyamides was reported (226). Kleinschrod and Fisher (279) investigated the formation of polyaminotriazoles and the production of polyurethans was described (111,238,416). Silicones were the subject of four reviews (358, 359, 516, 625). The following catalysts were suggested for the hydrolysis-condensation step in the formation of silicones: molten sodium (117), bentonite ( I & ) , basic metal oxides (445), and alkali alcoholates (524). Inert solvents (61, 366), organic solvents (66),toluene (116, 176, ala), alcohols (261), and methylene chloride-water mixtures (815), were all suggested as media for carrying out the hydrolysis-condensation reaction. MacMullen (320) heated
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
water-soluble metal salts of organosilane triols in acidified aqueous solutions to obtain silicone polymers. Barra and Gilkey (52) prepared lubricants by condensing tolj lsesquisiloxane isomers. Hirsch (257)made molding compositions from mixtures of phenyl and ethyl trichlorosilanes. The condensation of methylchloroand methyloxysilanes (543)and of equal mixtures of methyl- and phenyltrichlorosilanes and methylphenyldichlorosilanes(452)was reported. Tiganilc (495) partially hydrolyzed arylsilanes before condensation with alkylsilanes. Tyler (602, 603) described the formation of mixed silicone polymers. Goodwin and Hunter (214) produced chloroaryl and alkyl polysiloxanes. Several authors (95, b13, 248, 504,601) prepared copolymers of silicones and polyesters of the alkyd type by introducing hydroxyl or carboxyl groups on the organic radicals attached to the silicon atoms. Swiss and Arntzen (478, 479) made polysiloxanes containing allyl groups which could be polymerized. Sommer (460) formed organosilicon polyamides. Bayes ( 6 5 ) , Martin (526),and Supler (476) reviewed epoxy resins. Carpenter, Reeder, and Wallsgrove (103) formed epoxy resins from epichlorohydrins and aromatic dihydroxg compounds. Greenlee ( $ 2 7 ) condensed bisphenol and epichlorohydrine, and (218) dihydric phenols and diepoxides. IClcKabb and Payne (362) modified epoxy resins by copolymerizing with styrene and castor oil. Koroly (289) reacted diepoxides with polycarboxylic acids and glycols, and (290) polyepoxides with aconitic acid. Carpenter, Reeder, and Waters (104) described the condensation of dithiols and epichlorohydrin. The condensation of epichlorohydrin with diamines and aminohydroxyl compounds was also reported (105, 128). Alkenyl (365, 365, 368) and aryl (196) epoxyalkyl ethers were polymerized and copolymerized. Reineck (408) reviewed resins from furfuryl alchohol and Brown (90) and Dunlop and Stout (161) produced resins from furfuryl alcohol and formaldehyde. Miscellaneous resins were prepared by condensing formaldehyde with chloroaminotriazine (16), sulfonamids (60), isopropyl xylene (170), adipic dihydrazide (175))substituted binuclear aromatics (267),Cashew nutshell liquid (269),tannin (318),cyclohexanone (496),and triphenylborate (500). Kardos (271) reacted alkylene diamines with aldehydes and Walton (622) condensed alkylene polyamines with methylol phenols. Aelion (6) obtained resins from the polycondensation of hydroxyamino acids. Other condensates were made from qlyoxals and glycerol (113) and benzene and ethylene chloride (283).
PROCESSES, EQUIPMENT, A N D P LA N T S Continuous processes received considerable attention in 1952 publications. Wall, Delbecq, and Florin (619) studied the continuous emulsion copolymerization of styrene and methyl methacrylate. Wilson (552) developed a continuous process for vinyl acetate, and Haines (223)did the same for st:, pene. Lee and May (303) described the continuous production of drying oils from an olefinic petroleum fraction. Hudson (244)controlled continuous ethenic polymerizations by introducing the catalyst at several places. Lubricating oils were prepared (121)by the simultaneous dehydration and polymerization of ethanol. Padbury and Kropa (374), Rearick (401), and Wrightson (549) proposed continuous polymerizatbn processes for chlorotrifluoroethylene. Bloem and Stel (73) worked out a continuous condensation of phenol and formaldehyde. Fryling and Troyan (194)and Fryling and Uraneck (195)developed low temperature processes for the emulsion copolymerization of butadiene and styrene. Wolf (542)described a method for the emulsion polymerization of vinyl compound. Processes were suggested for the dispersion polymerization of vinyl chloride (370), the copolynierization of vinyl chloride and vinylidene chloride (SSC), and the copolymerization of vinylidene chloride and acrylonitrile (65). Bristol and Turnbull (82) added vinyl acetate a t a controlled rate during emulsion polymeriz,rttion. Banes and
Vol. 45, No. 9
Arundale f46)employed a two-stage process for the emulsion copolymerization of diolefins and acrylonitrile. Dunn (256) produced acrylonitrile-isobutylene copolymers by adding acrylonitrile at a controlled rate. Anderson, Mecorney, and H a m ( 1 7 ) removed and recycled low molecular weight material during diallyiphthalate polymerizations. Bannon ( 4 8 ) and Sparks, Young, and Garber (466)improved methods for the low temperature polymerization of olefins. Garber, Young, and Sparks (2000) used internal cooling with propane for copolymeriaing diisobutylene and butadiene. Hanford (227) developed a process for copolymerizing dichlorodifluoroethylene and ethylene. Mcthods for carrying out condensations of phenol and formaldehyde were described (440,448). The use of buffers for furfuryl alcohol polymerizations was suggested (187). Yokel1 (651) reviewed the design of plants for the production of alkyd resins. van Dijk and Plas (141) proposed a vertical tube reactor for petroleum polymerizations. A multistage reactor was suggested (183)for CSand Cd olefin polymerizations. Ashton and Cooke (37) discussed heat transfer problems and methods in polymerizations. Lancaster (301) gave a. general survey of manufacturing plants for silicone production. A pilot plant for the production of copolymers of ethyl acrylate and chloroethyl vinyl ether was described (242).
BI BL I O G RAPHY Adachi, J., J . Chem. SOC.J a p a n (Pure Chem. Sect.), 73, 103 (1952). Adams, J. W., and Reynolds, J. A. (to United States Rubber Co.), U. S.Patent 2,616,875 (Nov. 4, 1952). Adams, R. M., and Bovey, F. A., J . Polymer Sci., 9, 481 (1 952). Adelson, D. E. (to Shell Development Go.), U. S. Patent 2,563,771 (ilug. 7 , 1951). Adelson, D. E., and Dannenberg, H., Ihid., 2,595,214 (May 6, 1952). Aelion, R. (to SociCti: Organico), Ibid., 2,600,953 (June 17, 1952). Aelterman, M., and Smets, G.. BUZZ.soc. chim. Belges, 60, 469 (1 952). Agnew, R. J. (to Texas Co.), U. S. Patents 2,684,315; 2,584,316 (Feb. 5, 1952). Ibid., 2,595,625 (May 6, 1952). Alfrey, T., ,Jr., Fuoss, R. M., Morowitz, H., and Pinner, H., J . Am. Chem. Soc., 74,438 (1952). Alfiey, T., Jr., and Morowitz, H., Ibid., 74, 436 (1952). Allison, H. V. ( t o Allison Co.), U. S.Patent 2,589,652 (March 18, 1952). American Cyanamid Co., Brit. Patent 656,138 (4ug. 15, 1951). American Cyanamid Co., French Patent 974,657 (Feb. 23, 1951). Ihid., 974,734 (Feb. 26, 1951). Anders, H., Kunststofe, 42, 403 (1952). Anderson, J., Meoorney, J. W., and Ham, G . E. (to Shell Development Co.), U. S.Patent 2,613,201 (Oct. 7, 1952). Anderson, J. A. (to Standard Oil Co. of Indiana), Ihid., 2,620,365 (Dee. 2, 1952). Anon., Chem. Eng. News, 30, 1966 (1952). Ibid.. 30. 2688 (1952). Anon., Chem. W e e k , 70, No. 14, 35 (1952). Ibid., 71, No. 5, 61 (1952). Ibid., 71, KO.15, 31 (1952). Arco Co., Brit. Patent 682,065 (Nov. 5, 1952). Ardis, A. E. (to B. F. Goodrich Co.), U. S. Patent 2,615,866 (Nov. 18, 1952). Arlman, E. J., and Wagner, W. M., J . Polymer Sci., 9, 581 (1952). Armitage, F., and Fry, E. 5.J. (to Sherwin-WilliamsCo.), U. S. Patent 2,589,655 (Nlarch 18, 1952). Armitage, F., and Kut, S.,J. Oil & Colour Chemists' Assoc., 35, No. 383, 195 (1952). Armitage, F., and Kut, S.,Ofic. Dig. Federation Paint & Varnish Production Clubs, No. 333,671 (1952). Armitage, F., and Sleightholme, J. J. (to Sherwin-Williitms Co.), U. S.Patent 2,586,593 (Feb. 19, 1952). Arnett, L. M., J . Am. Chem. Soc., 74,2027 (1952). Arnett, L. AI., and Peterson, J. H., Ibid., 74,2031 (1952). Arundale, E., and Basoom, F. (to Standard Oil Development Co.), U. S.Patent 2,589,919 (March 18, 1952). Arundale, E., Gleason, A. H., and Barnes, F. W. (to Standard, Oil Development Co.), Ibid., 2,586,594 (Feb. 19, 1952).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Arvin, J. A., and Gitchel, W. B. (to Sherwin-Williams Co.), Ibid., 2,580,876 (Jan. 1, 1952). Ashar, K. G., and Champetier, G., Compt. rend., 234, 1555 (1952). Ashton, H. W., and Cooke, M. D., Chemistry & I n d u s t r y , 1951, 962. Auer, L., U. S. Patent 2,589,657 (Maich 18, 1952). Austin, P. R. (to E. I. du Pont de Nemours & Co.), Ibid., 2,585,529 (Feb. 12, 1952). Auten, R. W., and Meunier, V. C. (to Rohm & Haas Co.), Ibid., 2,605,253 (July 29, 1952). Averill, S. J. (to B. F. Goodrich Co.), Ibid., 2,615,872, 2,615,873 (Oct. 28,1952). Bachman, G. B., and Lewis, L. L. (to Purdue Research Foun, dation), Ibid., 2,580,504 (Jan. 1, 1952). Bailey, G. C., and Reid, J. A. (to Phillips Petroleum Co.), Ibid., 2,581,228 (Jan. 1,1952). Bakelite Corp., Brit. Patent 655,689 (Aug. 1, 1951). Bakker, J., Philips Research Repts., 7,344 (1952). Banes, F. W., and Arundale, E. (to Standard Oil Development Co.), U. S. Patent 2,623,032 (Dec. 23, 1952). Bankoff, S. G. (to E. I. du Pont de Nemours & Co.), Ibid., 2,612,484 (Sept. 30,1952). Bannon, J. H. (to Standard Oil Development Co.), Ibid., 2,596,975 (May 20, 1952). Barb. W. G.. Proc. Rou. SOC.(London). 212A. 66 (1952). Barnes, A. W., and Imperial Chemical Industries, Ltd., Brit. Patent 674,060 (June 18, 1952). Barry, A. J. (to Dow Chemical Co.), U. S. Patent 2,590,812 (March 25, 1952). Barry. A. J.. and Gilkey, J. W. (to Dow Corning, Ltd.), Brit. Patent 667,790 (April 9, 1952). Barusch, M. R., and Payne, J. Q. (to California Research Corp.), U. S. Patent 2,605,291 (July 29, 1952). Bauer, W., C h i m i a (Switz.),7, 147 (1951). Bayes, R. E., Paint, Oil,Chem. Rev., 115, No. 24, 24(1952). Baysal, B., and Tobolsky, A. V., J . Polymer Sci., 8, 529 (1952). Beatty, J. R., and Zwicker, B. M. G., IND.ENG. CHEM.,44, 742 (1952). Bebb, R. L., Carr, E. L., Makefield, L. B., Ibid., 44, 724 (1952). Beduneau, H., Rev. prod. chim., 55, 1 (1952). Bengtsson, E. B. (to Aktiebolaget Boforo), U. S. Patent 2,609,356 (Sept. 2, 1952). Berger, L., and Sons, Ltd., Brit. Patent 656,470 (Aug. 22, 1951). Ibid., 675,761 (July 16, 1952). Berry, W., Oswin, C. R., and Rose, R. A. (to British Cellophane, Ltd.), 682,689 (Nov. 12,1952). Betts, J. L., Jr., McCracken, E. A., Rose, H. J., and Wood, R. E. (to Standard Oil Development Co.), U. S. Patent 2,605,242 (July 29,1952). Bidand, A. F., and Ceyzeriat, L. (to Soci6t6 des usines chimiques RhGne-Poulenc),Ibid., 2,584,535 (Feb. 5, 1952). Bisterfeld. E.. Ger. Patent 805.717 (Mav 28. 1951). Blair, C. M., Jr. (to Petrolite Corp.; Lt;.), U. S. Patent 2,599,538 (June 10, 1952). Bloch, H. S. (to Universal Oil Products Co.), Ibid., 2,603,629 (July 15, 1952). Ibid., 2,611,788 (Sept. 23, 1952). Bloch, H. S., and Hoffman, A. E. (to Universal Oil Products Co.), U. S. Patent 2,582,411 (Jan. 15, 1952). Bloch, H. S., and Thompson, R. B., Ibid., 2,594,537 (April 29, 1952). Bloch, H. S., and Wackher, R. C., Ibid., 2,622,108, 2,622,109 (Dec. 16, 1952). Bloem, H., and Stel, M. (to Hartford National Bank and Trust Co.). Ibid.. 2.616.872 (Nov. 4. 1952). (74) Bonsa‘ll, E. P., Valentine, L., and Melville, H. W., T r a n s . Farad a y SOC.,48,763 (1952). (75) Bonzagni, F. A. (to Monsanto Chemical Co.), U. 8. Patent 2,603,623 (July 15, 1952). (76) Boyd, T. (to Monsanto Chemical Co.), Ibid., 2,606,179 (Aug. 5, 1952). (77) Bradshaw, S. E., and Evans, E. M., Brit. Patent 674,155 (June 18. 1952). (78) Bralley, J..A., and Pope, F. B. (to B. F. Goodrich Co.), U. S. Patent 2,587,437 (Feb. 26, 1952). (79) Brasch. A. A.. Brit. Patent 665,262 (Jan. 23, 1952). (80) Breitenbach, J. W., and Schindler, A., Monatsh., 83, 271 (1952). (81) Brintzinger, H., and Orth, H., Deut. Farben-Z., 6,230 (1952). (82) Bristol, J. E., and Turnbull, N. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,614,088 (Oct. 14, 1952). (83) British Resin Products, Ltd., Ger. Patent 807,441 (June 28, 1951).
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British Thomson-Houston Co., Ltd., Brit. Patent 661,503 (Nov. 21, 1951). Ibid., 664,399 (Jan. 9, 1952). Ibid., 664,675 (Jan. 9, 1952). Ibid., 665,110 (Jan. 16, 1952). ENG.CHEM.,44, 2673 (1952). Brown, L. H., IND. Brown, L. H. (to California Research Corp.), Ibid., 2,621,165 (Dec. 9, 1952). Brown, L. H. (to Quaker Oats Co.), U. S. Patents 2,601,497: 2,601,498 (June 24, 1952). Brunner, H., and Tucker, D. R., J . A p p l . Chem. (London), 1, 563 (1951). Bruson, H. A. (to Industrial Rayon Corp.), U. 5. Patent 2,601,251 (June 24, 1952). Ibid., 2,601,256 (June 24, 1952). Bullitt, 0. H., Jr. (to E . I. du Pont de Nemours & Co.), U. S. Patents 2,603,554, 2,608,555 (Aug. 26, 1952). Bunnell. R. H. (to Libbev-Owens-Ford Glass Co.). ., Ibid.. 2,607,755 (AW. i s , 1952). Cabello, A. S., Ion, 12, 527 (1952). Caird, D. W. (to General Electric Co.), U. S. Patent 2,600,202 (June 10, 1952). California Research Corp., Brit. Patent 681,042 (Oct. 15, 1952). Canadian Industries, Ltd., Ibid., 662,365 (Dec. 5, 1951). Carello, F., Ital. Patent 462,148 (Feb. 27, 1951). Carlson, C. S., Merrington, R. S., and Biribauer, F. A. (to Standard Oil Development Co.), U. S. Patent 2,588,358 (March 11, 1952). Carlson, E. J. (to B. F. Goodrich Co.), Ibid., 2,587,442 (Feb. 26, 1952). Carpenter, A. S., Reeder, F., and Wallsgrove, E. R. (to Courtaulds, Ltd.),Ibid., 2,602,075 (July 1, 1952). Carpenter, A. S., Reeder, F., and Waters, D. J. (to Courtaulds, Ltd.), Brit. Patent 678,576 (Sept. 3, 1952). Carpenter, A. S., and Wallsgrove, E. R., Ibid., 664,271 (Jan. 2, 1952). Casella Farbwerke Mainkur, Ger. Patent 841,795 (June 19, 1951). Cass, W. E. (to General Electric Co.), U. S. Patent 2,609,349 (Sept. 2,1952). Catlin, W. E. (to E. I. du Pont de Nemours & Co.), Ibid., 2,584,968 (Feb. 12,1952). Ibid., 2,613,184 (Oct. 7, 1952). Cavier, D., French Patent 971,269 (Jan. 15, 1951). Celanese Corp. of .America, Brit. Patent 683,504 (Nov. 26, 1952). Charlesby, A., Proc. R o y . SOC.(London), 215A. 187 (1952). Chemische Werke Hus G.m.b.H., Ger. Patent 842,075 (June 23, 1952). Cherrier, R. P., French Patent 970,774 (Jan. 9, 1951). Chitani, T., Chem. High. Polymers ( J a p a n ) , 8, 128 (1951). Clark, H. A. (to Dow Cohing Corp.), U. S. Patent 2,590,937 .(Ami1 . . 1.1952). ~ , ~ Ibi‘d., 2,606,879’(Aug. 12, 1952). Coffman, D. D. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,585,537 (Feb. 12, 1952). Coffman, J. A., IND. ENG.CHEM.,44, 1421 (1952). O., J . PoZymer Sci., 8 , 467 (1952). Colclough, Compagnie francaise de raffinage, French Patent 972,872 (Feb. 5, 1951). Conard, W. R., and Best, C. E. (to Firestone Tire and Rubber Co.), U. S.Patent2,605,256 (July29,1952). Consortium fur elektrochemische Industrie G.m.b.H., Ger. Patent 803,956 (April 12, 1951). Cooper, W., J. Chem.‘Soc., 1951, 3106. Ibid.. 1952. 2408. Cordier, D: E. (to Libbey-Owens-Ford Glass Co.), U. S. Patent 2,623,030 (Dec. 23, 1952). Cornwell, R. T. K. (to American Viscose Corp.), Ibid., 2,595,355 (May 6,1952). Courtaulds, Ltd., Carpenter, A. S., and Wallsgrove, E. R.. Brit. Patent 675.665(Jub 16. 1952). (129) Cowan, J. C., and Teeter, H. M. (to United States of America), U. S. Patent 2,582,235 (Jan. 15, 1952). (130) Crane, G., and Eberly, K. C. (to Firestone Tire and Rubber Co.), Ibid., 2,581,925 (Jan. 8, 1952). (131) Crawford, J. W. C., and Imperial Chemical Industries, Ltd., Brit. Patent 671,936 (May 14, 1952). (132) Crouch, W. W. (to Phillips Petroleum Co.), U. S. Patent 2,602,787 (July 8, 1952). (133) D’Alelio, G. F. (to Koppers Co., Inc.), Ibid., 2,593,417 (April 22, 1952). (134) Davies, R. E. (to Celanese Corp. of America), Ibid., 2,599,616 (June 16,1952). (135) Debing, L. M., Murray, G. E., and Schatz, R. T., IND.ENGI. CHEM.,44,354 (1952).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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(136) Deutsche Gold- und Silber-Scheideanstalt vorm. Roessler, Ger. Patent 803,854 (April 12, 1951). (137) Dickey, J. B. (to Eastman Kodak Co.), U. S. Patent 2,592,254 (Bpril8, 1952). (138) Ibid., 2,611,765 (Sept. 23, 1952). (139) Dickey, J. B., and Coover, H. W. (to Eastman Kodak Co.), U. S. Patent2,563,776 (Aug. 17, 1951). (140) DiGiorgio, P. A,, and Safford, &I. RI. (to General Electric Co.), Ibid., 2,613,199 (Oct. 7, 1952). (141) Dijk, C. P., van, and Plas, F. J. F., van der (to Shell Development Co.),Ibid., 2,618,626 (Nov. 18, 1952). Distillers Co., Ltd., Faulkner, D., Hollis, C. E., and Rlilne, J. N., Brit. Patent 676,376 (July 23, 1952). Doak, K. W., and Wilzbach, K. E. (to United States Rubber Co.), U. S. Patents 2,610,963; 2,610,964 (Sept. 16, 1952). Dow Corning Corp., French Patent 977,435 (April 2, 1951). Dom Corning, Ltd., Brit. Patent 671,774 (May 7, 1952). Drechsel, E. K., and Padbury, J. J. (to American Cyanamid Co.), U. S. Patent 2,550,652 (April 24, 1951). Dreisbach, R. R.(to Dow Chemical Co.), Ibid., 2,620,329 (Dee. 2, 1952). Drewitt, J. G. N., and Lincoln, J. (to Celanese Corp. of America), Ibid., 2,595,343 (May 6 , 1952). Dudley, J. R. (to American Cyanamid Co.), Ibid., 2,595,779 (May 6,1952). Dunbrook, R. F., Bebb, R. L., and Street, J. N. (to Firestone w_ l . 787,360, Ofiic. Tire and Rubber Co.). U. S. Patent. A. Gaz., U . S. Pat. O f i c e , 644, 623 (1951). Dunlop, A. P., and Stout, P. R. (to Quaker Oats Co.), C.9. Patent 2,589,683 (March 18, 1952). Dunn, W.R. (to United States Rubber Co.), Ibzd., 2,806,176 (Aug. 5,1952). Du Pont de Kemours, E. I., & Co., Brit. Patent 849,934 (Feb. 7, 1951). Ihid., 658,893 (Oct. 17, 1951). Ibid., 666,716 (Feb. 20, 1952). DuPuis, R. S.,and Wright, H. J. (to Association of American Soap and Glycerine Producers, Inc.), U. S. Patent 2,609,348 (Sept. 2,1952). Duroux, V., French Patent 972,460 (Jan. 30, 1951). Dynamit-Akt.-Ges. vorm. Alfred Nobel and Co., Ger. Patent 805,187 (May 10,1951). Earhart, K. -4.. and Davis, A. L. (to National Distillers Products Corp.), U. S.Patent 2,581,335 (Jan. 8, 1952). Elev. D. D.. and Saunders. J.. J . Chem. SOC..1952. 4167. Ellkgboe, E. K. (to E. I.'du' Pont de Nemours & Co.), U. S. Patent 2,589,237 (Xarch 18, 1952). Ellingboe, E. K., and Rothrock, H. S., Ihid., 2,607,754 (Aug. 19, 1952). Elliot, P. hl.,Modern Plastics, 29, No. 11, 113 (1952). Elmell, W. E. (to California Research Corp.), U. S. Patent 2,623,056 (Dec. 23, 1952). Erickson, J. G., and Thomas, W.M. (to American Cyanamid Co.), Ihid., 2,580,901 (Jan. 1, 1952). Evans, E. M., and Seager, 3. E. (to British Resin Products, Ltd., London), Ibid., 2,583,638 (Jan. 29, 1952). Evans, E. M., and Whitney, J. E. S. (to British Resin Products, Ltd.), Brit. Patent 670,502 (April 23, 1952). Evans, T. W., Adelson, D. E., and Whitehill (to Shell Development Co.), U. S.Patent 2,612,491 (Sept. 30, 1952). Evans. T. W..and Shokal. E. C. (to Shell DeveloDment Co.). Ibid:, 2,599,817 (June 10; 1952). ' Farbenfabriken Bayer, Ger. Patent 815,543 (Oct. 1,1961). Ibid., 819,404 (Oct. 31, 1951). Feagin. R. C., and Bandel. D. (to Mathieson Chemical Corp.), C. S.Patent 2,603,625 (July 15,1952). Fields, J. E., and Wesp, G. L. (to Monsanto Chemical Co.), Ibid., 2,598,639 (May 27, 1952). Fisher, J. W., May, G. B., and Wheatley, E. W. (to British Celanese, Ltd.), Brit. Patent 676,785 (Aug. 6, 1952). Fisher, J. TV., and Wheatley, E. W. (to Celanese Corp. of .Smerica), U. S . Patent 2,597,467 (May 20, 1952). Fletcher, H. J.. and Hunter, M. J. (to .Dow Corning Corp.), Ibid., 2,599,984 (June 10, 1952). Flory, P. J., and Leutner, F. S. (to Wingfoot Corp.), Ibid., 2,589,687, 2,589,688 (March 18, 1952). Ibid., 2,594,144 (April 22, 1952). lbid., 2,623,034 (Der,. 23, 1952). Folt, V. L. ( t o B. F. Goodrich Co.), Brit. Patent 663,756 (Dee. 27, 1951). Folt, V. L. (to B. F. Goodrich Co.), U. S.Patents 2,615,869; 2,615,870; 2,615,871 (Oct. 28, 1952). Ibid., 2,615,877; 2,615,878; 2,615,879;2,615,880 (Oct. 28, 1952). Fontana, C. AI.,Herold, R. J., Kinney, E. J., and Miller, R. C., IRD.ENG.CHEM.,44, 2955 (1952). Fontana, C. &I.,Kidder, G. A , , and Herold, R. J., Ibid., p. 1688. ~~
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(185) Foster, F. C., J. Am. C h e m Soc., 74,2299 (1952). (186) Fowler, D. E., and Westerhoff, C. B., Bm. Pacnt J . , 37, S o . 10, 74 (1952). (187) Foxon, G. H., and Imperial Chemical Industries, Ltd., Brit. Patent 677.848 (Aue. 20. 1952). (188) Frank, C. E., Kraus, 6.,and Haefner, A. J., Im. ESG.CHEM., 44,1600 (1952). (189) Franta, W,A . (to E. I. du Pont de Nemours & C o . ) , U. S. Patent 2,586,322 (Feb. 19, 1952). (190) Fiiedman, B. S. (to Sinelair Refining - Co.). I b d . . 2 599.249 (June 3, 1952). (191) Fritz, R. J. (to Standard 011 Development Co.), Ibzd., 2,603,666 (July 15,1952). (192) Fryling, C. F. (to Phillips Petroleum Co.), Ibid., 2,581,402 (Jan. 8, 1952). (193) Fryling, C. F., and Follett, -4.E. ( t o Phillips Petroleum C o . ) , Ibid., 2,588,975 (March 11, 1952). (194) Fryling, C. F., and Troyan, J. E. (to Phillips Petroleum Co.), Ibid.,2,609,366 (Sept. 2, 1952). (195) Fryling, C. F., and Uraneok, C . -4.(to Phillips Petroleum Co.), Ibid.. 2.609.362 (Seut. 2. 1952). (196) Furukawa, K'., and Oda, R,., S k . Inst. Chem. Research, Kyoto Unfv.,30, 50 11952). (197) Gantmakher, A. R., and Medvedev, S. S.,Zhur. F i t . Khina., 26,173 (1952). (198) Gantmakher, A. R., Medvedev, S. S.,and Lipatova, T. E., Doklady Aicad. N a u k S.S.S.R., 86, 1109 (1952). (199) Garber, J. D., and Hollyday, W.C., Jr. ('to Standard Oil Development Co.), U. s. Patent 2,581,092 ( J a n . l , 1952). (200) Gmber, J. D., Young, D. W., and Sparks, W.J. (to Standard Oil Development Co.), Ibid., 2,583,420 (Jan. 22, 1952). (201) Geiser, E. M. (to Universal Oil Products Co.), Ibid., 2,582,425 (Jan. 15, 1952). (202) Geiser, E. &I., and DeRosset, 9.J., Ibid., 2,611,764 (Sept. 23, 1952). (203) Gerhart, H. L. (to Pittsburgh Plate Glass Co.), Ibid., 2,601,273 (June 24,1952). (204) Gjammaria, J. J. (to Socony Vacuum Oil Co.), Ibid.,2,615,843; 2,615,844; 2,615,864 (Oct. 28, 1952). (205) Ibid., 2,616,849; 2,616,851; 2,616,853 (Nov. 4, 1952). (206) Gilbert, H., and -Miller, F. F. (to B. F. Goodrich Co.), Ibid., 2,615,866; 2,615,867; 2,615,874; 2,615,875; 2,615,876 (Oct. 28, 1952). (207) Gilbert, R. D., and Williams, H. L., J . Am. Ch,em. SOC., 74, 4114 (1952). (208) Gleason, A. H., and Jaros, S.E. ( t o Standard Oil Development Co.), I-.S.Patent2,581,094 (Jan. 1, 1952). (209) Gold, L., J . Chem. Phys., 20, 1651 (1952). (210) Gonikberg, RI. G., Dokladu Aicad. A'uuk S.S.S.R., 86, 297 (1952). (211) Goodrich, B. F., Co., Brit. Patent 681,285 (Oct. 22, 1952). (212) Goodwin, J. T., Jr. (to DON Corning Corp.); V. S. Patent 2,590,957 (April 1, 1952). (213) Goodwin, J. T., Jr., and Hunter, hI. J. (to Don, Corning Corp.), Ibid., 2,584,340; 2,584,341; 2,584,342; 2,584,343; 2,584,344 (Feb. 5,1952). (214) Ibid., 2,588,243 (March 18, 1952). (215) Gordon, -4.F. (to Dow Corning Corp.), U. 8. Patent 2,622,072 (Dee. 16,1952). (216) Gould, C. W. (to Hercules Powder Co.), Ibid., 2,612,490 (Sept. 30, 1952). (217) Greenlee, 8. 0. (to Devoe & Raynolds Co., Inc.), Ibid., 2,582,985 (Jan. 22,1982). (218) Ibid., 2,592,560 (April 15, 1952). (219) Guenther, R. A. (to Minnesota Mining B Manufacturing Co.), Ibid., 2,606,206 (Aug. 5, 1952). (220) Guillissen, C. J.. and Ganeberg, -4.,Industrie chim. belge, 17, 481 (1952). (221) Haas, H. C., and Karlin, E. R., J . Polymer Sci., 9, 588 (1952). (222) Haas, H. C., and Simon, Ill. S., Ibid., p. 309. (223) Haines, E. C. (to G. D. Wetherill Co.), U. S. Patent 2,602,071 (July 1,1952). (224) Ham, G. E. (to Monsanto Chemical Co.), Ibid., 2,610,173 (Sept. 9, 1952). (225) Ham, G. E., and Chapin, E. C. (to Monsanto Chemical Co.), Ibid., 2,587,485 (Feb. 26, 1952). (226) Hanby, W. E., Waley, S. G., and Watson, J. (to Courtaulds, Ltd.), Ibid., 2,598,372 (May 27, 1952). (227) Hanford, W. E. (to E. I. du Pont de Nemours 65 Co.), Ibid., 2,584,128 (Feb. 5, 1952). (228) Harman, D., and Stiles, A. R. (to Shell Development C o . ) , Ibid., 2,601,520 (June 24, 1952). (229) Harrison, S. A. (to General Mills, Inc.), Ibid., 2,593,444 (April 22,1952). (230) Harvey, M. T. (to Harvel Research Corp.), Ibid., 2,600,408 (Feb. 16, 1952).
September 1953
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(231) Hauck, K. H., Rev. gSn. m a t . plastiques, 27, 14 (1951). (232) Hearne, G. W., and LaFrance, D. S. (to Shell Development Co.), U. S. Patent 2,601,659 (June 24, 1952). (233) Heinrich, R. L. (to Standard Oil Development Co.), Ibid., 2,595,140 (April 29, 1952). (234) Higginson, W. C. E., and Wooding, N. S., J . Chem. Soc., 1952, 760. (235) Highet, H. C., Salt, F. E., and Stanley, H. M. (to Distillers Co., Ltd.), U. S.Patent 2,595,581 (May 6, 1952). (236) Hillyer, J. C. (to Phillips Petroleum Co.), Ibid., 2,607,758 (Aug. 19,1952). (237) Hirsch, A. (to Diamond Alkali Co.), Brit. Patent 683,905 (De& 10, 1952). (238) Hochtlen, A., Kunststoffe, 42, 303 (1952). (239) Horn, O., and Starck, W., Angew. Chem., 64,533 (1952). (240) Hovey, A. G., and Jerabek, R. D., Ofic. Dig. Federation P a i n t & V a r n i s h Production Clubs, No. 314,171 (1951). (241) Howard,E. G., Jr. (to E. I. du Pont de Nemours & Co.) U. S. Patents 2,580,919 (Jan. 1, 1952); 2,589,258 (March 18, 1952); 2,594,560 (April 29, 1952); 2,601,293 (June 24, 1952). (242) Howerton, W. W., Dietz, T. J., Snyder, A. D., and Alden, G. E., Rubber Age (Ar. Y.), 72, No. 3, 353 (1952). (243) Howland, L. H., Neklutin, V. C., Brown, R. W., and Werner, H. G., IND. ENQ.CHEM., 44,762 (1952). (244) Hudson, T. B. (to Phillips Petroleum Co.), U. S.Patent 2,590,539 (March 25, 1952). (245) Hultzsch, K., Kunststo,fe, 42, 161 (1952). (246) Ibid., p. 385. (247) Hultzsch, K., M i t t . Chem. Forsch.-Inst. Wirtsch. Osterr., 6, 1 (\I_952) ___,
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(248) Hunter, 31.J., and Rauner, L. A. (to Dow Corning Corp.), U. S. Patent 2,584,351 (Feb. 5, 1952). (249) Hutchinson, W. M. (to Phillips Petroleum Co.), Ibid., 2,598,174 (May 27, 1952). (250) Inventa A.-G. fur Forschung und Patentverwertung, Swiss Patent 280,367 (IMay 16, 1952). (251) Irigai, S.(to Tokyo Shibaura Electric Co.), Japan. Patent 1143 (March 5, 1951). (252) Iuchi, A. (to Shinko Rayon Co,), Japan. Patent 142 (Jan. 23, 1951). (253) Izard, E. F. (to E. I. du Pont de Nemours & Co.), U. S.Patent 2,569,932 (Oct. 2, 1951). (254) Jackson, E. F. (to Monsanto Chemical Co.), Ibid., 2,608,546 (Aug. 26, 1952). (255) Jacobi, B., Angew. Chem., 64, 539 (1952). (256) Jasper, G. E,, and Welch, L. M. (to Standard Oil Development Co.), U. S. Patent 2,615,004 (Oct. 21, 1952). (257) Jennings, R. J. S.,and ‘MTilliams,A. F. (to C. D. Patents, Ltd.), Brit. Patent 680,343 (Oct. 1, 1952). (258) Johnson, B. L., and Wolfangel, R. D., IND.ENG.CHEM.,44, 752 (1952). (259) Jones, G. D. (to General Aniline and Film Corp.), U. S. Patent 2,611,763 (Sept. 23, 1952). (260) Jones, J. I., J . A p p l . Chem. (London), 1, 568 (1951). (261) Jones, J. L. (to Libbey-Owens-Ford Glass Co.), U. S. Patent 2,587,578 (March 4, 1952). (262) Jordan, D. O., and Mathieson, A. R., J . Chem. SOC.,1952, 611. (263) Ibid., p. 2354. (264) Jordan, T. E., and Cline, E. L. (to Allied Chemical and Dye Corp.), U. S.Patent 2,590,771 (March 25,1952). (265) Joyce, R. M., Jr. (to E. I. du Pont de Nemours & Co.), Ibid., 2,599,640 (June 10, 1952). (266) Kammerer, H., Makromol. Chem., 8,72 (1952). (267) Kagawa, I., and Shirai, Z . , J . Chem. SOC.J a p a n ( I n d . Chem. Sect.), 54,64 (1951). (268) Kakiuchi, H., Chem. H i g h Polymers ( J a p a n ) ,8,29 (1951). (269) Kamath, H. R., Indian Patent 42,618 (May 17, 1952). (270) Karchmer, J. H. (to Standard Oil Development Co.), U. S. Patent 2,620,361 (Dec. 2, 1952). (271) Kardos, 0. (to Hanson-VanWinkle-Munning Co.), Ibid., 2,698,209 (March 18, 1952). (272) Katchalski, A., and Blauer, G., Bull. Research Council Israel, 1, 138 (1951). (273) Kauffman, IM., and Williams, A. F. (to C. D. Patents, Ltd.), U. S. Patent 2,595,676 (May 6, 1952). (274) Kawai, S., Yoneshige, K., Oguchi, S., Okajima, M., and Adachi, J., J . Chem. SOC. J a p a n ( P u r e Chem. Sect.), 73, 103 (1952). (275) Keller, K., and Hansen, 0. (to Casella Far’bwerke Mainkur), U. S.Patent 2,603,624 (July 15, 1952). (276) Kemp, J. D., and Brooke, L. F. (to California Research Corp.), Ibid., 2,592,428 (April 8, 1952). (277) Kern, E. A. (to General Electric Co.), Ibid., 2,588,123 (March 4, 1952). (278) Kern, W., Chem.-Ztg., 76, 667 (1952).
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(279) Kleinschrod, F. G., and Fisher, J. W. (to British Celanese, Ltd.), Brit. Patent 682,399 (Nov. 12, 1952). (280) Kline, G. M., Modern Plastics, 30, No. 5, 111 (1953). (281) Knight, H. B. (to the United States of America), U. S.Patent 2,613,157 (Oct. 7, 1952). (282) Kohler, R., and Enzensberger, W., HoZz Roh- u. Werkstof, 10, 51 (1952). (283) Kolesnikov, G. S.,Korshak, V. V., and Smirnova, T. V., Isvest. A k a d . Navlc S.S.S.R., Otdel, K h i m . N a u k , 1951,596. (284) Kolfenbach, J. J., and Small, A. B. (to Standard Oil Development Co.), U. s. Patent 2,603,626 (July 15, 1952). (285) Ibid., 2,614,136 (Oct. 14, 1952). (286) Kolthoff, I. M., and Meehan, E. J., J.Polymer Sci., 9,327,343, 433 (1952). (287) Korfhage, L., Fette u. Seifen, 54, 95 (1952). (288) Korolev, A. Y., and Leonova, K. I., Doklady A k a d . N a u k S.S.S.R., 85,99 (1952). (289) Koroly, J. E. (to Rohm & Haas Co.), U. S. Patent 2,609,357 (Sept. 2,1952). (290) Ibid., 2,623,023 (Dee. 23, 1952). (291) Korshak, V. V.. and Matveeva, N. G., Doklady A k a d . Nauk S.S.S.R., 85,797 (1952). (292) Korshak, V. V., and Rogozhin, S. V., Izvest. A k a d . N a u k S.S.S.R., Otdel. Khirn. N a u k , 1951,593. (293) Kropa, E. L. (to American Cyanamid Co.), U. S. Patents 2,598,663; 2,598,664 (June 13, 1952). (294) Ibid., 2,600,782; 2,600,783 (June 17, 1952). (295) Kropa, E. L., and Nyquist, A. S.(to American Cyanamid Co.), U. S. Patent 2,606,892 (Aug. 12, 1952). (296) Krug, R. C. (to Atlantic Refining Co.), Ibid., 2,620,364 (Dec. 2, 1952).
(297) KUt,-S.’,. P a i n t Technol., 17, 101 (1952). (298) Kvalnes, H. M. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,609,352 (Sept. 2, 1952). (299) Ladd, E. C. (to United States Rubber Co.), lbid., 2,594,184 (April 22, 1952). (300) Ladd, E. C., and Harvey, M. P. (to United States Rubber Co.), Ibid., 2,594,935 (April 29, 1952). (301) Lancaster, D. W., Rubber Age and Synthetics, Suppl., p. 37 (October 1952). (302) Leboine, R., French Patent 974,595 (Feb. 23, 1951). (303) Lee. R. J.. and May. P. D. (to Pan American Refining- Corm). . U. S.Patent 2,614,132 (Oct. 14, 1952). (304) Libbey-Owens-Ford Glass Co., Brit. Patent 663,770 (Dec. 27, 1951). (305) Lindenfelser, R., Kilthan, M. K., Walsh, J., and Thomas, W. J. (to British Industrial Plastics, Ltd.), Brit. Patent 673,742 (June 11, 1952). (306) Linville, R. G. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,592,301 (April 8, 1952). (307), Litmincott. S. B.. and Mikeska. L. A. (to Standard Oil Develooment Co:), Ibib., 2,615,845 (Oct. 28,’1952). (308) Lippincott, S. B., and Popkin, A. H. (to Standard 011 Development Co.), Ibid., 2,582,708 (Jan. 15, 1952). (309) Lippincott, S. B., and Young, D. W. (to Standard Oil Development Co.), Ibid., 2,599,399 (June 3, 1952). (310) Loewe, S.,Science, 114, 555 (1951). (311) Lombard, F., Bull. inst. teztile France, No. 30, 177 (1952). (312) Luce, S.B. (toBwift and Co.), U. S.Patent 2,602,786 (July 8, 1952). (313) Ibid., 2,611,762 (Sept. 23, 1952). (314) Lum, F. G., and Carlston, E. F., IND.ENG.CHEX.,44, 1595 (1952). (315) Lytton, iM. R. (to Chemstrand Corp.), U. S. Patent 2,586,238 (Feb. 19,1952). (316) McGrew, F. C., and Pinkney, P. S. (to E. I. du Pont de Nemows & Co.), Ibid., 2,617,789 (Nov. 11, 1952). (317) Mack, C. H., and Bickford, W. G., J . Am. Oil Chemists’ SOC., 29,428 (1952). (318) MacLean, H., and Gardner, J. A. F., P u l p & Puper Mug. Can., 53, No. 9, 111 (1952). (319) McMillan, F. M., and Bishop, E. T. (to Shell Development Co.), U. S. Patent 2,601,673 (June 24, 1952). (320) MacMullen, C. W. (to Cowles Chemical Co.), Ibid., 2,587,636 (March 4, 1952). (321) McNabb, J. W., Ofic. Dig. Federation P a i n t & V a r n i s h Production Clube, No. 332,605 (1952). (322) McNabb, J. W., and Payne, H. F., IND. ENG.CHEM.,44, 2394 (1952). (323) McQueen, D. M. (to E. I. du Pont de Nemours & Co.),U. S. Patent 2.699.199 (June 3, 1952). (324) Malinowski, T. P. (to Monsanto Chemical Co.), Ibid., 2,619,476 (Nov. 25. 1952). (325) Marling, P. E. (to Monsanto), Zbid., 2,606,161 (Aug. 5, 1952). (326) Martin, M. R., Industrie plastiques mod. ( P a r i s ) , 4, No. 6, 34 (1952). I
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2020
INDUSTRIAL AND ENGINEERING CHEMISTRY
(327) Marvel, C. S., and Cripps, H. N., J . Polymer Sci., 8,313 (1952). (328) Marvel, C. S., Fukuto, T. R., Berry, J. W., Taft, W. K., and Labbe. B. G.. Ibid.. D. 599. (329) Mast, TV: C., and Fisger, C. H. (to the United States of America), U. S. Patent 2,588,398 (March 11, 1952). (330) Mastagli, P., Floc'h, A., and Durr, G., Compt. rend., 235, 1402 (1952). (331) May, G. B., and Fisher, J. W., U. S. Patent 2,577,621 (Deo. 4, 1951). (332) Meerbott, W. K. (to Shell Development Co.), Ibid., 2,619,512 (Nov. 25, 1952). (333) Meier, R. L., J . Chem. Soc., 1950, 3656. (334) Merrett, F. nl.,and Korrish, R. G. W., Proc. R o g . SOC.( L o n d o n ) ,206A, 309 (1951). (335) Messina, A,, Ital. Patent 462,959 (April 11, 1951). (336) Miller, F. F. (to B. F. Goodrich Co.), U. S. Patent 2,615,868 (Nov. 18, 1952). (337) Miller, G. H., Alunibaugh, R. L., and Brotherton, R. J., J . Polymer Scd., 9,453 (1952). (338) Miller, W. T., Y a t l . Nuclear Energu Ser., Div. VII, 1, 567 (1951). (339) Miller, W. T. (to the United States of America), U. S. Patent 2,598,283 (May 27, 1952). (340) Miller, W. T., Dittman, A. L., and Reed, S. K. (to the United States of America), Ibid., 2,680,358 (Dec. 25, 1951). (341) Ibid., 2,586,550 (Feb. 19, 1952). (342) Minsk, L. M., and Taylor, E. W. (to Eastman Kodak Co.), U. S. Patent 2,583,356 (Jan. 8, 1952). (343) Momanto Chemicals, Ltd., Brit. Patent 657,704 (Sept. 26,1951). (344) Morini, M., Materie plastiche, 18, 197 (1952). and Ballard, S. A. (to Shell Develop(345) Morris, R. C., Buls, V. W., ment Co.), U. S.Patent2,577,796 (Dee. 11, 1951). (346) Morton, A. A., Rubber Age ( N . Y.), 72, 473 (1953). (347) Morton, M.,Salatiello, P.P., and Landfield, H., IND.ENG. CHEM.,44,739 (1952). (348) Morton, R. W., and West, H. L. (to Standard Oil Development Co.), Brit. Patent 666,697 (Feb. 20, 1952). (349) Muller, H. F., and Muller. I., Kunststoffe, 42,57 (1952). (350) Muskat, I. E., and Strain, F. (to Columbia-Southern Chemical Corp.), U. S. Patent 2,592,058 (April 8, 1952). (351) Myers, R. M, (to General Electric Co.), Ibid., 2,613,203 (Oct. 7, 1952). (352) Seher, H. T., Bauer, L. N., VanHorne, W. L. (to Rohm & Haas Co.), Ibid., 2,600,419; 2,600,420; 2,600,421 (June 17, 1952). (353) Xeher, H. T., VanHorne, W.L., and Bauer, L. V. N. (to Rohm & Haas Co.), Ibid., 2,623,036 (Dec. 23, 1952). (354) Xelson, J. F., and Welch, L. M. (to Standard Oil Development Co.), Ibid., 2,607,764 (Aug. 19, 1952). (355) Nichols, W.T. (to Monsanto Chemical Co.), Ibid., 2,614,119 (Oct. 14, 1952). (356) Niederl, J. B. (to J. B. Niederl and Associates), Ibid., 2,613,230 (Oct. 7, 1952). (357) . . Niles, G. E. (to Monsanto Chemical Co.). I b i d . , 2,601,055: 2,601,656 (June 24, 1952). (358) Nitzsche, S., K u n s t o f f e , 42, 311 (1952). (359) Nitesche, S., and Wick, hI., Chem. Ztg., 76, 677 (1952). and Russell, K. E., T r a n s . Faraday Soc., 48, (360) Norrish, R. G. W., 91 (1952). (361) Northgraves, W. W. (to Slathieson Chemical Corp.), Brit. Patent 673,967 (June 18, 1952). (362) Kovotny, E. E., and Vogelsang, G. .(I (to Borden Co.), U. 5. Patent 2,594,579 (April 29, 1952). (363) S. V. de Bataafsche, Petroleum Maatschappij, Brit. Patent 1951 I. 660.377 - .-,- . . m o v . 7 ., -_.(364) Ibid., 682,i53(T\;ov.5, i952). (365) N. V. de Bataafsche, Petroleum Maatschappij, Dutch Patent 68,367 (July 15, 1951). (366) Ibid., 68,393 (Aug. 15, 1951). (367) Ibid., 69,114 (Dee. 15, 1951). (368) Ibid., 69,137 (Dec. 15, 1951). (369) Ibid., 70,514 (Aug. 15, 1952). (370) Ibid., 71,057 (Oct. 15, 1952). (371) Orr, R. J., and Williams, H. L., Can. J . Chem., 30, 108, 985 (1952). (372) Otto, F. P., and Reiff, 0. M.(to Socony-Vacuum Oil Co.), U. 6. Patent 2,600,798 (June 17, 1952). (373) Overberger, C. G., Arnold, L. H., and Taylor, J. J., J . Am. Chem. Soc., 73,5541 (1951). (374) Padbury, J. J., and Kropa, E. L. (to American Cyanamid Co.), U. S. Patent 2,602.824 (July 8 . 1952). (375) Park, H. F. (to Monsanto'Chemical Co.), Ibid., 2,593,399 (iipril 22, 1952); 2,620,330 (Dee. 2, 1952). (376) Park, H. F., and Walter, H. A. (to Nonsanto Chemical Co.), Ibid., 2,622,077 (Dee. 16, 1952). (377) Parker, C. H., P a i n t Varnish Production. 42, No. 4,19 (1952).
Vol. 45, No. 9
(378) Parkyn, B., Plastics I n s t . ( L o n d o n ) , Trans., 20, No. 41, 36 (1952). (379) Paschke, R. F., Jackson, J. E., and Wheeler, D. H., IXD. ENQ. CHEM.,44,1113 (1952). (380) Passino, H. J. (to &.I.W. Kellogg Co.), U. 8. Patent 2,600,802 (June 17, 1952). (381) Patat, F., Cremer, E., and Bobleter, O., Monatsh., 83, 322 (1952). (382) Patterson, D. G., Detn-iler, E. B., and Suen, T. J., Modern Plastics, 29, No. 7, 151 (1952). (383) Pearson, F. G. (to -4merican Viscose Corp.), U. S. Patent 2,584,284 (Feb. 5, 1952). (384) Ibid., 2,600,683 (June 17, 19.52). (385) I b i d . , 2,600,684 (June 17, 1952). (386) Ibid., 2,610,174 (Sept. 9, 1952). (387) Penn, W.S., Australian Plastics J., 8 , 30 (April 1952). (388) Petit, J., and Fournier, P., BUZZ.soc. chim. France, 1952, 287. (389) Pinkney, P. S., Pratt, B. C., and Wayne, J. W. (to E. I. du Pont de Nemours 8: Co.), U. S. Patent 2,599,123 (June 3, 1952). (390) Pitzl, G. (to E. I. du Pont de Semours & Co.), Ibid., 2,606,884 (Aug. 12, 1952). (391) Polly, 0. L. (to Union Oil Co. of California), Ibid., 2,609,354 (Sept. 2, 1952). (392) Ibid., 2,610,161 (Sept. 9, 1952). (393) Polyakov, M. V., Pavlushina, A. Y . , Kornienko, T. P., and Shalya, V. V., Zhur. Fiz. Khim., 25, 647 (1951). (394) Popkin, A. H. (to Standard Oil Development Co.), U. S. Patent 2,604,453 (July 22, 1952). (395) Port, W. S., Jordan, E. F., Jr., Hansen, J. E., and Swern, P., J . Polymer Sci., 9,493 (1952). (396) Price, C. C., and Gilbert, R. D., J . Am. Chem. Soc., 74, 2073 (1952). (397) Price, J. A. (to American Cyanamid Co.), U. S.Patent 2,606,175 (Aug. 5, 1952). (398) Pritchett, E. G. K., and Barnett, G. (to Union Carbide and Carbon Corp.), Ibid., 2,617,785 (Nov. 11, 1952). Vander Wal, R. J., and Harwood, J. (to ilrmour (399) Ralston, A. W., and Co.), Ibid., 2,617,813 (Nov. 11, 1952). (400) Raeuvaev, G. A , , Ol'dekop, Y . il.,and Fedotova, E. I., Uspekhi Khinz., 21,379 (1952). (401) Rearick, J. S. (to ht. W. Kellogg Co.), U. S. Patent 2,600,804 (June 17,1952). (402) Regie nationale des usines Renault, Brit. Patent 661,362 (Nov. 21, 1951). (403) Rehberg, C. E., and Siciliano, J., IND. EKG.CHEM.,44, 2864 . (1952). (404) Reich, M. H., Sohneider, R. E., and Taft, W. K., Ibid., p. 2914. (405) Reid, T. S. (to Minnesota Mining &- Manufacturing Co.), U. 5. Patent 2,592,069 (April 8, 1952). (406) Reilly, J. H. (to Dow Chemical Co.), Ibid., 2,614,092 (Oct. 14, 1952). (407) Reineck, E. A., Modern Plastics, 29, No. 10, 122 (1952). (408) Ibid., 30, No. 2, 127 (1952). (409) Reynolds, W. B. (to Phillips Petroleum Co.), U. S. Patent 2,583,277 (Jan. 22, 1952). (410) Reynolds, W. B., and Fryling, C. F., Ibid., 2,601,632 (June 24, 1952). (411) Reynolds, W. B., Wicklate, J. E., and Kennedy, T. J., Ibid., 2,584,773 (Feb. 5, 1952). (412) Ibid., 2,606,893 (Aug. 12, 1952). (413) Rhodes, P. H. (to Koppers Co., Inc.), Ibid., 2,589,286 (March 18, 1952). (414) Roach, J. R., and Wittcoff, H. (to General Mills, Inc.), Ibid., 2,585,035 (Feb. 12, 1952). (415) Robertson, J. A. (to E. I. du Pont de Nemours & Co.), Ibid. 2,586,995 (Feb. 26, 1952). (416) Robinson, E. B., and 'VVaters, R. B., J . Oil & Colmr Chemists' Assoc., 34,361 11951). (417) Robinson, J. C., Jr., and Ropp, W. S. (to Hercules Powder Co.), U. S. Patent 2,614,997 (Oct. 21, 1952). (418) Robinson, R. S. (to Reichhold Chemicals, Inc.), Ibid., 2,586,092 (Feb. 19, 1952). (419) Roedel, G. F. (to General Electric Co.), Ibid., 2,613,202 (Oct. 7. 1952). (420) Romeyn, H., Jr., and McCleary, C. D. (to United States Rubber Co.), Lbid., 2,597,951 (May27, 1952). (421) Ross, S.D., and Markarian, M., J . Polymer Sci., 9,219 (1952). (422) Rossem, A.'van. Chenz. Weekblad, 48, 273 (1952). (423) Rothrock, H. S. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,605,258 (July 29, 1952). (424) Rowland, S. P. (to Rohm & Haas Co.), Ibid., 2,606,891 (Aug. 12, 1952). (425) Rubens, L. C., and Boyer, R. F. (to Dow Chemical Co.), I b i d . , 2,609,353 (Sept. 2, 1952).
September 1953
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Runk, R. H., IND. ENQ.CHEM.,44,1124 (1952). Runk, R. H. (to Westinghouse Electric Corp.), U. 8. Patent 2,586,385 (Feb. 19, 1952). Rutovskil, B. N., and Shur, A. M., Zhur. Priklad. Khim., 24, 1173 (1951). Salomon, G., Kautschuk Anwend., 1, 110 (1951). Sans. M. L. (to Societe anon. des manufactures des alaces e t products chimiques de Saint-Gobain, Chauny a n d Cirey), U. S. Patent 2,600,695 (June 17, 1952). Sargent, E. H. G. (to Middlesex Oil and Chemical Works Ltd.), Brit. Patent 678,019 (Aug. 29, 1952). Sarin, K. K., Kapur, S. L., and Aggarwal, J. S., J. Sci. I d . Research ( I n d i a ) , 11B, 31 (1952). Schaffel, G. S. (to General Tire and Rubber Co.), U. S. Patent 2,609,361 (Sept. 2, 1952). Schappel, J. W. (to American Viscose Corp.), Ibid., 2,623,035 (Dec. 23, 1952). Schmidt, R. F., Ardis, A. E., and Gilbert, H. (to B. F. Goodrich Co.), Ibid., 2,589,294 (March 18, 1952). Schmutzler. A. F. (to American Cyanamid Co.), Ibid., 2,590.653; 2,590,694 (March 25,1952); Schneider, H. G., Young, D. W., and Goering, H. G. (to Standard Oil Development Co.), Ibid., 2,604,465 (July 22, 1952). Schulze, W. A,, and Crouch, W. W. (to Phillips Petroleum Co.), Ibid.. 2,602,078 (July 1, 1952). (439) Schutze, H. G. (to Standard Oil Development Co.), Ibid., 2,581,147 (Jan. 1,1952). (440) Schwartzberg, H., U. S. Patent Appl. 713,087, Ofic.Gaz. U.S. Pat. Ofice, 653,859 (1951). (441) Scott, M. F., and Jackson, E. F. (to Monsanto Chemical Co.), U. S. Patent 2,600,698 (June 17, 1952). (442) Scott, R. J., and Gunning, H. E., J . Phys. Chem., 56, 156 (1952). (443) Sengupta, R., and Palit, 5. R., J . Chem. SOC.,1951,3278. (444) Shantarovich, P. S.. Izvest. A k a d . N a u b S.S.S.R., Otdel. Khim. Nauk, 1952, 40. (445) Shaw, C., Smith, W. E., and Emblem, H. G., U. S. Patent 2,580,852 (Jan. 1, 1952). (446) Shokal, E. C., and Devlin, P. A. (to Shell Development Co.), Ibid., 2,588,890 (March 11, 1952). (447) Simons, J. K. (to Libbey-Owens-Ford Glass Co.), Ibid., 2,595,492 (May 6, 1952). (448) Simons, W. G. (to American Cyanamid Co.), Ibid., 2,593,926 (April 22, 1952). (449) Sleightholme, J. J. (to Sherwin-Williams Co.), Ibid., 2,586,571 (Feb. 19, 1952). (450) Sleightholme, J. J., and Hammond, W. T. C. (to SherwinWilliams Co.), Ibid., 2,586,572 (Feb. 19, 1952). (451) Smets, G., and Borzee, A., J. Polymer Sci., 8,371 (1952). (452) Smith, E. J. (to Dow Corning Corp.), U. S.Patent 2,605,194 (July 29, 1952). (453) Smith. F., Stacey, M., Tatlow, J. C., Dawson, J. K., and Thomas, B. R. J., J . A p p l . Chem. (London), 2,97 (1952). (454) Smyers, W. H., and Young, D. W. (to Dow Chemical Co.), U. 8. Patent 2,610,962 (Sept. 16, 1952). (465) Snyder, H. R., and Stewart, J. M. (to Phillips Petroleum Co.), Ibid., 2,620,328 (Dec. 2, 1952). (456) Snyder, M. D. (to E. I. du Pont de Nemours & Co.), Ibid., 2,623,031; 2,623,033 (Dec. 23, 1952). (457) Societe Nobel francaise, Ibid., 976,042 (March 13, 1951). (458) Soci6t6 Organico, Brit. Patent 662,877 (Dec. 12, 1951). (459) Soci6te des usines chimiques RhBne-Poulenc, French Patent 977,286 (March 29, 1951). (460) Sommer, L. H. (to Dow Corning Corp.), U. S. Patent 2,601,793 (Aug. 19, 1952). (461) Spahr, R. J. (to Borden Co.), Ibid., 2,614,096 (Oct. 14, 1952). (462) Sparks, W. J., and Thomas, R. IM. (to Jasco, Inc.), Ibid., 2,585,867 (Feb. 12, 1952). (463) Sparks, W. J., and Thomas, R. M. (to Standard Oil Development Co.), Ibid., 2,612,493 (Sept. 30, 1952). (464) Sparks, W. J., Thomas, R. M., and Field, D. C. (to Standard Oil Development Co.), Ibid., 2,615,881 (Oct. 28, 1952). (465) Sparks, W. J., Young, D. W., and Garber, J. D. (to Standard Oil Development Co.), Ibid., 2,548,503 (April 10, 1951). (466) Speier, J. L. (to Dow Corning Corp.), Ibid., 2,611,777 (Sept. 23, 1952). (467) Speyer, F. B., Paint,Oil,Chem. Rev., 115, No. 1, 7 (1952). (468) Sprague Electric Co., Brit. Patent 683,382 (Nov. 26, 1952). (469) Spurnik, V., Chem. Primysl, 1, (26), 177 (1951). (470) Standard Oil Development Co., Brit. Patent 674,545 (June 25, 1952). (471) Stehman, C. J. (to Monsanto Chemical Co.), U. S. Patent 2,607,795 (Aug. 19, 1952). (472) Stern, H. J., India-Rubber J . , 123,964 (1952). (473) Stevans, D. R., and Bowman, R. S. (to Gulf Research and Development Co.), U. s. Patent 2,591,384 (April l, 1952).
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(474) Strain, D. E. (to E. I. du Pont de Nemours & Co.), Ibid., 2,603,655 (July 15, 1952). (475) Strand, F., and Kovarik, B., Chem. Prtmysl, 1, (26), 185 (1951). (476) Supler, V., Ibid., p. 193. 1477) . , Swart. G. H. (to General Tire and Rubber Co.). U. S. Patent 2.594.824 (Ami129. 1952). (478) Swiss, J., and k n t z e n , C. E. (to Westinghouse Electric Corp.), Ibid., 2,595,727 (May 6, 1953). (479) Ibid., 2,595,728; 2,595,729; 2,595,730 (May 6, 1952). (480) Taat, W. J.. and Korndorffer, R. W, (to Nederlandsche Organisatie voor Toegepast-Natuurwetenschappelijk Onderzoek). Ibid., 2,609,351 (Sept. 2, 1952). (481) Tawney, P. 0. (to United States Rubber Co.), Ibid., 2,592,211 (April 8, 1952). (482) Ibid., 2,594,825 (April 29, 1952). (483) Ibid., 2,598,316 (May 27, 1952). (484) Ibid., 2,599,027; 2,599,028 (June 3, 1952). (485) Ibid., 2,606,172 (Aug. 5, 1952). (486) Ibid.. 2.612.492 (SeDt. 30. 1952). (487) Te Grotenhuis, T. A,,and Swart, G. H. (to General Tire and Rubber Co.), Ibid., 2,548,504 (April 10, 1951). (488) Teot, A. S. (to Dow Chemical Co.), Ibid., 2,602,076 (July 1, 1952). (489) Tess, R. W. H., Jakob, R. H., and Bradley, T. F. (to Shell Development Co.), Ibid., 2,596,737 (May 13, 1952). (490) Teas, R. W. H., and Mika, T. F. (to Shell Development Co.), Ibid., 2,618,616 (Nov. 18,1952). (491) Theobald, C. W. (to E. I. du Pont de Nemours & Co.), Ibid., 2,584,306 (Feb. 5, 1952). (492) Thomas, W. M., and Price, J. A. (to American Cyanamid Co.), Ibid., 2,595,907 (May 6,1952). (493) Thompson, R. B., and Bloch, H. W. (to Universal Oil Products Co.), Ibid., 2,587,791 (March 4, 1952). (494) Thurston, J. T., and Adams, P. (to American Cyanamid Co.), Ibid., 2,599,142 (June 3, 1952). (495) Tiganik, L. (to Uddeholms Aktiebolag), Swed. Patent 133,541 (Nov. 6, 1951). (496) Tilichenko. M. N.. and Zvkova. L. V.. Zhur. Priklad. Khim.. 25.64 f1952,. ‘ (497) Toy,’A. D. F.;and Brown, L. V. (to Victor Chemical Works), U. 8. Patent 2,586,885 (Feb. 26,1952). (498) Tucker, C. W., and Wells, W. E. (to Phillips Petroleum Co.), Ibid., 2,584,823 (Feb. 5, 1952). (499) Tullock, C. W. (to E. I. du Pont de Nemours & Co.), Ibid.. 2.608.548 (AUK.26. 1952). (500) Twiss, S. B.,’and Sporzynski, A. P. (to Chrysler Corp.), Ibid., 2,623,866 (Dec. 30,1952). (501) Tyler, L. J. (to Dow Corning Corp.), Ibid., 2,601,646 (June 24, 1952). (502) Ibid., 2,605,274 (July 29, 1952). (503) Ibid., 2,611,774 (Sept. 23, 1952). (504) Upson, R. W. (to E. I. du Pont de Nemours & Co.), Ibid., 2.599.144 (June 3.1952). (505) Uraneck, C. A,, and Landes, S. H. (to Phillips Petroleum Co.), Ibid., 2,614,098 (Oct. 14, 1952). (506) Uraneck, C. A,, Tucker, C. M., and St. John, W. M., Jr. (to Phillips Petroleum Co.), Ibid., 2,614,100; 2,614,101 (Oct. 14, 1952). (507) Vandenberg, E. J. (to Hercules Powder Co.), Ibid., 2,610,965 (SeDt. 16. 1952). (508) Vanderbilt,’B. M.,and Bascom, F. (to Standard Oil Development Co.), Ibid,, 2,589,166 (March 11, 1952). (509) VanHorne, W. L., Bauer, L. N., and Neher, H. T. (to Rohm and Haas Co.), Ibid., 2,600,446; 2,600,447: 2,600,448: 2,600,449; 2,600,450; 2,600,451 (June 17, 1952). (510) Vaughan, M. F., J . A p p l . Chem. (London), 2,422 (1952). (511) Vaughan, iM1.F., J . Polymer Sci., 8 , 445 (1952). (512) Vaughan, M. F., Trans. Faraday Sx.,48, 576 (1952). (513) Verley, G. M. (to Sinolair Refining Co.), U. S. Patent 2,623,890 (Dec. 30,1952). (514) Vesely, K., Chem. Prtmysl, 1, 26, 165 (1951). (515) Von Fischer. W.. Finish. 9, No. 6, 31 (1952). (516) Waeser, B., Werkstofe u.Korrosion, 3, 98 (1952). (517) Wakeford, L. E., and Hewitt, D. H. (to Sherwin-WilliamsCo.). U. S. Patent 2,607,749 (Aug. 19, 1952). (518) Wakely, J. S., and Imperial Chemical Industries, Ltd., Brit. Patent 672,224 (May 14, 1952). (519) Wall, F. T., Delbecq, C. J., and Florin, R. E., J . Polymer Sci., 9,177 (1952). (520) Walsh, D. C., Jr. (to Standard Oil Development Co.), U. S. Patent 2,580,490 (Jan. 1, 1952). (521) Walsh, D. C., and Schutze, H. G., Ibid., 2,581,154 (Jan. 1, 1952). (522) Walton, R. K. (to Union Carbide and Carbon Corp.), Ibid. 2,585,196 (Feb. 12, 1952).
INDUSTRIAL AND ENG INEERING CHEMISTRY
2022
(523) Warner, R. R., Rubber A g e ( N . Y . ) , 71, 205 (1952). (524) Warrick, E. L. (to Dow Corning, Ltd.), Brit. Patent 682,541 (Sov. 12, 1952). (525) Warrick, E. L., Hunter, M. J., and Barry, A. J., IKD.ENG. CHEM.,44, 2196 (1952). (526) Weisgerber, C. A. (to Hercules Powder Co.), U. 8. Patent 2.592.218 L4oril8. 1952). (527) Westfahl, J. C.: and'sears', D. S. (to B. F. Goodrich Co.), Ibid., 2,587,558 (Feb. 26, 1952). (528) Wheeler, D. H., O&. Dig. Federation P a i n t & V a r n i s h Production Clubs, No. 322, 661 (1952). (529) Wheeler, 0. L., Lavin. E., and Crozier, R. N., J . Polumer Sci.. 9, 157 (1952). (530) Whetstone, R. R., and Evans, T. W. (to Shell Developnient Co.), U. 9. Patent 2,585,359 (Feb. 12, 1952). (531) White, A. (to Imperial Chemical Industries, Ltd.), Brit. 683,630 (Dee. 3, 1952). (532) Wilson, W. K. (to Shawinigan Resins Corp.), T;. 8. Patent 2,587,562 (Feb. 26,1952). ENG.CHEM.,4 4 , (533) Winding, C. C., and TViegandt, H. F., IND. 2052 (1952). (534) Wingfoot Corp., Brit. Patent 662,682 (Dec. 12, 1951). (535) Wintgen, R., and Jyirgen-Lohmann, L., Kolloid-Z., 122, 143 (\1-Q.51 - - -I., .
(536) Ibid., 123, 11 (1951). (537) Wintgen, R., and Sinn, G., Ibid.. 122, 103 (1951). (538) Wiseman, P. A. (to Firestone Tyre and' Rubber Co., Ltd.), Brit. Patent 675.372 (Julv 9. 1952). (539) Wittcoff, H., and Roach, J."R. (to Geneial lIills), U. S. Patent 2,590,910 1.4prll 1, 1952).
mg
Vol. 45, No. 9
(540) Wohnsiedler, H. P., IND. Exa. CHEaI., 44, 2679 (1952).
(541) Wohnsiedler, H. P., and Kropa, E. L. (to American Cyanamid Co.), U. S. Patent 2,582,303 (Jan. 15, 1952). (542) Wolf, R. J. (to B. F. Goodrich C o . ) , Brit. Patent 674,080 (June 18, 1952). (543) Wolf, R. J. (to B. F. Goodrich Co.), U. 9. Patent 2,594,375 (April 29, 1952). (544) Ibid., 2,605,254 (July 29, 1952). (545) Ibid., 2,608,549 (Aup. 26. 1952). (546) Wolf, R. J., and Nioolay, ,4. 1.(to B.F. Goodrich Co.), Ibid., 2,605,257 (July 29, 1952). (547) Ibid., 2,608,552 (Aug. 26, 1952). (548) Wooding, N. S., and Higginson, SV. C. E., S. Chem. Soc., 1952, 774. (549) Wrightson, J. &I. (to XI. W. Kellogg Co.), U. S.Patent 2,600,821 (June 17, 1952). (550) Wynstra, J. (to Union Carblde and Carbon Corp.), Ibid., 2,600,457 (June 17, 1952). (551) Yokell, S., P a i n t V a r n i s h Production, 42, No. 8, 23 (1952). (552) Yost, R. S.,and rluten, R. W. (to Rohm 6. Haas Co.), U. S. Patent 2,616,874 (Nov. 4, 1952). (553) Young, D. W., Sparks, W. J., and Garber. J. D. (to Standard Oil Development Co.). 2.583.504 (Jan. 22. 1952). (554) Yurshenko, A. I., and Tsvetkov, S. S.,Doklady Acud. Nauk S.S.S.R.,85, 1099 (1952). (555) Zimm, B. H., and Bragg, J. K., J . PoZume, Sci,, 9,479 (1952). (556) Zoss, A. 0. (to General Aniline and Film Corp.), U. S.Patent 2,609,364 (Sept. 2, 1952). (557) Ibid., 2,616,879 (Nov. 4, 1952).
Pyrolysis of Coal and Shale CHARLES H. PRIEN, DENVER RESEARCH
INSTITUTE, UNIVERSITY OF DENVER, DENVER I O , COLO. Papers on coal pyrolysis during the past year included several studies on the mechanism of degradation OF the coal macromolecule during pyrolysis and of the structure of the pitch and tar produced. Patents on fluidized carbonization continued t o appear. Interest i n low temperature carbonization i n the United States has been mounting, as has also interest i n the pro. duction of coal chemicals by l o w temperature carbonization, without simultaneous production of metallurgical coke. The physicochemical processes responsible For benzene production during carbonization and elimination of overlapping standard tests for coke properties were studied, U. S. Bureau of Mines activities o n o i l shale included studies on more efficient methods OF mining, revised estimates of the size of U. S. o i l shale resources, further p i l o t plant &velopment of the gas combustion process and cracking processes, additional cost estimates for commercial operations, and a new entrained-solids high temperature retorting process, Research on kerogen composition included a controlled oxidation with alkaline permanganate and a thermal solution OF the shale with associating and nonassociating solvents at 200" C. A high temperature retorting process For shale fines yields oils high i n aromatic hydrocarbons. Shale tar bases have been successfully polymerized t o aldehyde t y p e resins, using formaldehyde. H i g h pressure catalytic hydrogenation of Colorado shale o i l i s reported t o y i e l d a sulfur- and nitrogen-free product suitable for Further standard petroleum processing.
T IS pertinent t o begin this sixth annual review of paper. published in the field of coal and oil shale pyrolysis by restating
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the scope of the coverage undertaken. Although primary effort is devoted t o coal and shale pyrolysis as such-its niechanism and practice-to complete the survey, it has been extended to related subjects of concomitant concern t o persons in these fields. Bccordingly, an attempt has been made t o include not only references t o high and low temperature carbonization of coal and retorting of oil shale, their mechanisms, kinetics, and applications, but also t o cover related subjects, viz., raw materials, product and by-products characteristics and properties, coke oven equipment and improvements, coke analysis and testing,
The shale revien includes papers on shale properties, shale oil characteristics,retort design, and, briefly, theimal extraction. The majority of references to high-pressure gasification processes, subbituminous and lignite gasification, and underground gasification processes have been deleted, a8 being more properlyclassifiedasunitprocesses other than pyrolysis. Because a clearcut delineation hereto is not possible, however, certain ieferences to combination pyrolysk-gasification processes a l w a y s n e c e s s a r i l y w a r r a n t inclusion. The period under review is essentially that from June 1952 to 1953, except for previous omissions ariving from the normal lag in the publication of paperP and abstracts. The voluminous literature of the period, some 640 separate papers, has necessarily been reduced for illclusion in this revielv.
COAL PYROLYSIS GENERAL
A number of books and revieas of general interest have been issued during the past year. Sttention is called t o a publication of the r a t i o n a l Coal Board of Great Britain (1514) on metallurgical (not gas) coke processes, to the annual coal
