INDUSTRIAL AND ENGINEERING CHEMISTRY
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(120) Sweeney, M-.J., 1x11. ENG.CHEY.,43, 2717 (1961). (121) Swern, D., and Knight, H. B. (to United States of America), U. S. Patent 2,572,892 (Oct. 30, 1951). (122) Thomas, J. R.. and Crandall, 1-1. IT-., IND.EEG.C H E x . , 43, 2761-3 (1951). (123) Toland, K.G., Jr. (to California Research Corp.), U. S. Patent 2,574,511 (Kov. 13, 1951). (124) Ibid., 2,574,512 (SOT.13, 1951). (125) Topps, J. E. C., J . Inst. Petroleunz, 37, 535-53 (1951). (126) Ulmer, R. C . , and Wood, R. JT., Inditstrli n n d Power, 61,92 6, 135 (1951). (127) Xalcutt, C.. a n d Rifkin, E. I added. Fordham and TTillianis (186) studied t h e mechanism and rate of the cuniene hydi*operoxide-iron reaction in the redoucatalyzed polymerization of acrylonitrile. Kolthoff, Medalia, and Youse (300) discussed the effectiveness of various sugars and their degradation products as activators for emulsion polymerizations. Kolthoff and Medalia (298, $99) reported the use of dihydroxyacetone and freshly preripitat ed ferrous sulfide in redox
September 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
recipes. Kolthoff and Ferstandig (896) employed electrolytic reduction of persulfates and peroxides t o activate t h e polymerization of acrylonitrile. Marvel and Meinhardt (341) described a redox recipe which includes oxygen and 1-alkanesulfinic acids. Jacobson (879)used sulfinic acids and per compounds. Fordham and Williams (186) gave rate constants for t h e oxidation of ferrous iron by persulfates in acrylonitrile solutions. Neklutin (374) used ferrous silicate in redox recipes, and Loritsch (318) employed ascorbic acid plus peroxides. Howard (253) described catalysts composed of titanous and hydroxylamino compounds. Hill and Burkholder (641) carried out vinyl chloride polymerizations initiated by hypochlorous acid-chlorine-sulfurous acid mixtures. Uraneck (642) activated low-temperature emulsion polymerizations with heavy metal derivatives of heterocyclic nitrogen compounds. Schulze and Crouch (482) suggested the use of monoalkyl or aryl ethers of ethylene glycol as activators, and Loritsch (317) employed mixtures of sulfites and organophosphorous compounds. Hamilton (227) catalyzed t h e polymerization of trifluorochloroethylene with bisulfites, persulfates, and silver ions. Vandenberg (644) described the use of oxygen as a n activator in the emulsion copolymerization of butadiene and styrene. Various azo compounds are effective in supplying free radirals t o initiate polymerization reactions. Fryling and Reynolds (195) and Reynolds (445) used diazothio ethers. Overberger, Fram, and Alfrey (397) studied t h e effectiveness of 2,2’-azobis(isobutyronitrile) as a catalyst for styrene polymerizations, and Johnston and Pease (276) and Roedel (458) employed t h e same compound t o catalyze vinyl fluoride, styrene, and acrylic esters. Pease and Robertson (409) suggested a,a’-azobis( a-arylnitriles) as general catalysts for ethenic polymerizations. H u n t (%59) found t h a t addition polymerizations were initiated by hydrazodisulfonates plus an oxidizing agent; Park and Walter (408) used cyanuric triazide; and Wicklatz (560) employed 1,3,btriaryI1,4-pentadiazine. Addition polymerizations are also initiated by ionic mechanisms, usually employing catalysts of the Friedel-Crafts type, Dornte (149, 150, 151) described complex compounds of metal halides and aromatics, ethers, and olefins for low-temperature olefin polymerizations, and Dornte and McKay (152) suggested Friedel-Crafts catalysts plus SO2 and so3 for the same purpose. Evans (175) found t h a t BF3 requires the presence of water or alcohol t o catalyze the polymerization of isobutylene. Marvel and his coworkers (334) carried out cationic copolymerizations of butadiene and styrene a t low temperatures in an unsuccessful attempt t o produce linear polymers. Young (576) patented the use of a double salt catalyst of the type AIBr3.AIOBr. Heiligmann (239) compared t h e effectiveness of various catalysts in t h e polymerization of or-methylstyrene, Chapiro (108) initiated t h e polymerizahtion of various ethenic monomers with y-rays, and Schmitz and Lawton (479) employed high-energy electrons. Sachs and Bond (466) catalyzed t h e photopolymerization of vinyl compounds with I-( chloromethy1)naphthaleneand acyl halides. Holgberg (247) found t h a t N-substituted glycocyamidines are polymerization catalysts. D a y and Solak (137) reported t h a t phosphomolybdic acid catalyzes t h e bulk polymerization of styrene. Crouch (192) discovered t h a t small amounts of 1,a-butadiene increased t h e effectiveness of sodium as a catalyst for diene polymerizations. Castan and Haggar (105) used aromatic sulfinic acids for vinyl polymerizations. Brechbuhler and Magat (76) employed 1,2-dimethyl-5,6-benzacridine, a fluorescent dye, as a catalyst and determined the residues in the polymer by the amount of fluorescence. Modifiers are added t o many polymerizations t o reduce the amount of branching and crosslinking and t o control the degree of polymerization. T h e following compounds are reported t o be effective modifiers for butadiene-styrene copolymerizations: mercapto monoesters (328), tertiary-alkylmercaptans (126), thioather esters (127), diazothio ethers (446), cadmium mercaptides (483), trithiocarbonates (59), and reaction products of
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mercaptans and olefin sulfides (501). Thompson and Schmerhng (658)modified ethylene polymerizations with p-thioethyl-substituted carbonyl compounds and Schmerling (477) employed substituted phenols and p-phenylenediamine. Portser ( 4 S 4 ) added cyclohexane and lactic acid t o diolefin polymerizations. Breitenbach and Karlinger (80) discussed the use of carbon tetrachloride and tetrabromide as chain transfer agents in t h e polymerization of styrene, and Basu, Sen, and Palit (39) investigated the action of solvents as chain-transfer agents. Inhibitors are necessary in many commercial processes involving polymerization. The synthetic rubber industry employs inhibitors to stop polymerization so t h a t excess monomers may be recovered more easily and has called these inhibitors short stops. The following were patented for this use: N-aryl alkylolamines (25), trialkylphenols plus hydroxylamine (24), di-tert-butyl trisulfide (1%3),2,2’-(2-naphthylimino)diethanol(254), biacetyl (S52), alkyl polyhydroxy phenols plus small amounts of acetic acid (426),reaction products of a phenol and an iso-olefin (526), and lignin (564). Provost (4%) discovered t h a t t h e initial polymerization rates for diene copolymers could be reduced by adding small amounts of ethylenediamine tetracetic acid. He also found (437) rates of copolymerization of butadiene and styrene could be controlled by adding alkali tartrates and citrates, and t h a t these materials prevented latex discoloration when ferrous activators were used (438). Hammond and Bartlett (228) discussed t h e mechanism of inhibition of allyl acetate polymerizations by nitro compounds, and Barrett (30)suggested theuse of nitro compounds as retarders in the copolymerization of ethenic monomers. Goertz (212) reported t h a t phenothiazine and p-tertbutyl catechol are more effective when used together t o inhibit chloroprene polymerizations than either alone. Richards (460)inhibited t h e polymerization of acrylonitrile by adjusting the p H during emulsion polymerization. Brice and his coworkers (83) found t h a t soaps with high nickel contents caused low conversions when used as emulsifiers. Relatively few references dealt with catalysts for polycondensations, since many of these reactions require only acids or bases as catalysts. Gerhart (203) promoted t h e formation of alkyds with aldehyde-amines. Prochazka (433) catalyzed polyamide formation from Iactams with lactic acid, and Genas (202) used hypophosphites for polyamide condensations. Auspos and Dempster (12) found t h a t germanium dioxide catalyzed t h e condensation of ethylene glycol and terphthalic acid. The use of aluminum alkoxides for the condensation of alkyl or aryl silanes is reported (153).
REACTION MECHANISMS AND KINETICS Breitenbach (78) reviewed t h e mechanisms of peroxide-catalyzed addition polymerizations. H e also studied (77) t h e mechanism by which methyl acrylate polymerizes and investigated (79) the copolymerization of styrene and chloranil. Arlman and Melville (14) considered t h e mechanisms of copolymerization of styrene and butyl acrylate. Crauwels and Smets (120) followed changes in nitrogen content of the polymer with variations in the temperature of polymerization of methacrylamide. Morton and Salatiello (363)carried o u t a quantitative study of the effect of polymerization temperature on t h e amount of branching and cross linking in butadiene polymers. The mechanism of emulsion polymerization of isoprene was investigated b y Phillips and Clark (416). Orr and Williams (392) studied the role of or-ketols in low temperature copolymerizations. Denbigh (140) applied t h e kinetics of continuous reaction processes to polymerizations. Ginell (208) suggested the use of both polymerization and depolymerizat,ion rate constants t o avoid the inclusion of cessation reactions. Salomon and Koningsberger (467) analyzed the kinetics of t h e formation of large molecules. Burrell, Majury, and Melville (91 ) followed polymerization reactions b y measuring dielectric constants. Elly, Hawwd, and
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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
Sinipson ( 17 0 ) discussed the factors affecting rates of reaction in the industrial polymerization of styrene. Jordan and Mathieson (286)investigated the kinetics of styrene polymerization in carbon tetrachloride when aluminum chloride was used as a catalyst. Matheson, Auer, Bevilacqua, and H a r t (345) give rate constants for initiation, propagation, and t'ermination reactions in the polymerization of styrene. Mayo, Gregg, and Matheson (548)measured the variation in rates and degree of polymerization with concentration of benzoyl peroxide in styrene polymerizations. Osberg and LeRoy (399)studied rates of propagation and termination in the photopolymerization of styrene. Harvard and Simpson (253)investigated the effect'of various peroxide and azo catalysts on the rates of polymerization of styrene. . Kolthoff and Medalia (697) followed the variation in rates of butadiene-styrene copolymerization with changes in redox recipes, and Kolthoff, Meehan, and Carr (501) measured changes caused by adding emulsifiers and seeding with latex. Storey and Williams (518) st,udied the effect of changing butadiene-styrene ratios on rates of copolymerization. Kogerman (294) investigated the kinetics of copolymerization of butadiene and limonene. Breitenbach and Tschamler (86) followed the copolymerization of styrene and chloranil by infrared spectra. Matheson and Auer (346) determined propagation and termination rate constants for methyl acrylate a t several temperatures. Bengough and Sorrish (50) discussed the kinetics of peroxide-catalyzed polymerizations of vinyl chloride, and Burnett and Melville ( 9 0 ) gave results for rates of photopolymerization of vinylidene chloride. Wiener (562)obtained rate constants for the polymerization of vinylidene chloride using persulfate catalysts. Pauw and Smets (408)determined rate constants for the polymerization of vinglmesitylene and its copolymerization with acrylonitrile, methyl methacrylate, and p-chlorostyrene. Three general reviews of copolymerization appeared ($51 418, 549). Orr and Williams (391) studied the effect of modifiers on the relative reactivities of butadiene and styrene in emulsion copolymerizations a t 18"C. Walling and Davison (651) obtained the relative reactivity of butadiene in copolymerizations with acrylates and vinylidene chloride. Embree, Mitchell, and Killianis (172)gave relative reactivities of butadiene and acrylonitrile. Melville, Bonsall, and Valentine (350) investigated the copolymerization of styrene Tvith various ethenic monomers, and Me]ville and Valentine (351) discussed the kinetics of the copolgmerization of styrene and methyl methacrylate. Price and Greene (430)studied the early stages of t h e copolymerization of styrene and vinyl pyridene, and Price and Walsh (43f)did the same for styrene and methyl methacrylate. Bonsall, Valentine, and Melville (68) investigated the kinetics of styrene-p-methoxystyrene and (67) styrene-methyl methacrylate and styrene-butyl acrylate copolymerizations. Crauwels and Smets (181) gave relative reactivities for the copolymerization of methacrylic acid, methyl methacrylate, and methacrylamide. Four general discussions (97, 582-584) of the chemistry of phenol-formaldehyde condensation reactions were published. Zigeuner, Schaden, Gabriel, and Weisenberger (581) studied the mechanisms involved in the crosslinking of phenolics. Powers (429) discussed possible reaction mechanisms in the condensation of phenol, formaldehyde, and rosin in the production of rosinmodified phenolics. Raff and Silverman (439) investigated the kinetics of the condensation of resorcinol and formaldehyde in dioxane solutions, and Stedry (517) used ultraviolet absorption measurements to follow the kinetics of the same reaction. Zigeuner (580) discussed the mechanism of the urea-formaldehyde condensation reaction. The previous references deal with special aspects of polymerization processes. I n addition, a large number of articles and patents involving the polymerization of specific monomers were published. Usually such references are concerned with one or more subjects such as raw materials, method of preparation, properties, and uses. I n some cases they are limited to the discussion of a
Vol. 44, No. 91
single polymer; in others, they may embrace a series of derivatives, isomers or copolymerization with one or more other monomers. For convenience, such references have been classified into ethenic polymers, elastomers, and condensation polymers.
ETHENIC POLYMERS AND COPOLYMERS Several references (240, 561, 465, 488,487) dcsc,ribc. tlic polymerization of olefins to produce synthetic lubricating oils. Maschwitz and Henderson (.944) review the polymerization of hydrocarbon gases to produce motor fuels. Thc controlled-vapor polymerization of gaseous olefins t o liquids was reported (540). Rlurray and Galloway (370)produced a drying oil from an octene gasoline fraction by first treating vr-ith HF, followed b)- a silicaalumina catalyst, and then passing vapors over a phosphoric acid catalyst'. Hoffman (846)obtained cyclic poiyolcfins by treating an octene fraction with HF. Giamniaria (206,207 j Fynthesized lubricating oils by copolymerizing olefins and esters of unsaturated acids. Richards (452) reviewed the polymerization of ethylene. Elwell and Meier (171)and Young and Smyers (577) copolyinerized et'hylene and styrene. Pinkney (416) produced copolymers from ethylene, vinyl esters, and ethyl acrylat,e. Thinius (535) published a review of polyisobutylene. Schulze and Mahan (484) described the dimerization of isobutylene and Grosse (821) synthesized compounds containing up to 32 carbon atom:: by the successive liquid-phase dimerization of isobutylene and the resulting olefins. Hollydag and Sparks (848) copolymerized isobutylene and halogenated aryl olefins. Lieber ( S f l ) made copolymers of isobutylene and dihydronaphthalene. Hulse (655) reported the production of copolymers of isobutylene and abietyl esters of dicarboxy acids. Garber ( 196) obtainel interpolymers of isobutylene, styrene, and p-chlorostyrene. Slotterbeck and Young (495) copolymerized iso-olefins and dienes in a one-to-one ratio t o produce coating resins. Leyonmark and Hardy (510) produced drying oils from propylene and butadiene. Garber, Sparks, and Young (197)synthesized a drying oil by copolymerizing diisobutylene and an olefinic petroleum fraction. The polymerization and copolymerization of styrene and its derivatives received comiderable attention, particularly for the production of coating resins. Yang and Guile (575) studied the variables affecting the emulsion polymerization of styrene. Vakeford and Hewitt (549)produced low molecular weight polystyrene by polymerizing a t 180' C. in a solvent cont,aining terpenes. Staudinger (514 ) polymerized styrene and its derivatives in a nonsolvent diluent. Carr (104)carried out styrene polymerizations in formamide to produce formamide emulsions. Amos (7) copolymerized styrene with small amounts of divinyl compounds to improve the heat resistance of the product. Dickey and Stanin (148) found that amide or sulfonamide groups improved the heat resistance of styrene polymers. Irany and Landau (268) produced copolymers of' styrene and alkyl or aryl vinyl sulfones t o give a niat,erial wvit,h good heat resistance. Pepper (410) and Signer and Demagistri (493) diecussed the polymerization of styrene followed by eulfonation to produce ion eschange resins, Sleightholme and Kakeford (494) describe the copolymerization of styrene with various unsaturated and aromatic petroleum extracts. Sparks and Young (511) obtained copolymers of styrene and 2-methylpentadiene. JTesp (558)COpolymerized styrene and a-methylstyrene. Mills and Butler (357) produced copolymers of styrene and phenyl allyl alcohol. Wrigley and his coworkers (574) made copolymers for baking lacquers from styrene and allyl starch. Schertz (474) described the production of coating resins from styrene and abietyl esters of unsaturated acids. Minter (558) investigated interpolymers of styrene, acrylonitrile, maleic anhydride, and diallyl esters. Meyer (555) obtained interpolymers from styrene, allyl alcohol, and diallyl esters. Several references (62, 56, 156, 165, 178, 884,
September 19.92
INDUSTRIAL AND ENGINEERING CHEMISTRY
389,453,471, 533,550) deal with t h e copolymerbation of styrene with drying oils, acids, and esters to produce coating resins. Sturrock and Lawe (520)produced dimethyl styrene polymers. Markarian (327) polymerized pentachlorostyrene t o hard, nonflammable resins. Hayes (237) used a low-temperature solvent method t o polymerize a-chloromethylstyrene. Bachman and Carlson ( 1 5 )found t h a t free radicals would initiate the polymerization of or-methylstyrene containing sulfide or sulfone groups. Malinowski (325) copolymerized a-methylstyrene, maleic anhydride, and unsaturated oils. Mowry and Seymour (368) described the copolymerization of cyclohexylstyrene and other ethenic monomers. McMillan (324) reported the copolymerization of 2,5-dichlorostyrene and maleic acid. Platzer (420) reviewed polyvinyl acetate, alcohol, and acetals. H a m and JIowry (226)produced copolymers of vinyl acetate and vinyl-p-chlorobenzoate, and vinyl acetate and allyl N-aryl urethane (365). Lundquist (319 ) made stable emulsions containing copolymers of vinyl acetate and maleates. Richards (451) copolymerized vinyl acetate and butadiene. Two reviews (129, 250) of polyvinylidene chloride were published. O'Hara and Prutton (386)obtained stable dispersions of polyvinyl chloride by bubbling the gaseous monomer through a sodium persulfate solution. Nie (381) copolymerized vinyl chloride and vinylidene chloride in a n emulsion using a hydrogen peroxide initiator; Condo and Naps (118) produced a copolymer of vinyl chloride and 2-chloropropylene. Terpolymers of vinyl chloride, vinylidene chloride, and acrylates were investigated (43). Smith (497) cast clear films from a suspension of a n interpolymer containing the same monomers. Wolf (572) produced interpolymers of vinyl chloride, acrylates, and vinyl esters of aromatic acids. Ellingboe ( 168) copolymerized vinyl chloride, allyl glycidyl ethers, and an allyl oster of a hydroxy acid. Acrylonitrile was copolymerized with acrylamide (6), N-allyl urea (99), isobutylene (320), 1,3-dibromopropane ( 1S), and unsaturated esters (372). Caldwell ( 9 8 )investigated interpolymers of acrylonitrile, fumaric acid, and vinyl acetate or methyl acrylate for fiber production. Howard (252)used emulsion polymerization t o make interpolymers of acrylonitrile, vinyl chloride, and methyl methacrylate. Pitzl (419 ) produced heat-sealable coatings for cellophane by copolymerizing acrylonitrile, vinylidene chloride, and vinyl acetate, followed by hydrolysis of the acetate groups. Naps and Condo (371) obtained copolymers of methacrylonitrile and a-methylstyrene. Hogshed (246) dimerized methacrylonitrile b y heating under pressure for short intervals. Staudinger and Hutchinson (516)prepared clear polymers from methyl methacrylate containing divinyl compounds. Wolf (871 ) produced interpolymers from alkyl acrylates, styrene, and vinyl esters of monocarboxylic acids. Kugler and Lundquist ($07) obtained coating compositions by emulsion copolymerization of esters of acrylic acid and maleic acid. Powell (426) made interpolymers from ethyl acrylate, 2-chloroethyl vinyl ether, and divinylbenzene. Barrett (32) investigated heteropolymers of alkyl acrylates, vinyl aromatic compounds, and esters of Unsaturated dicarboxylic acids. Barnes (28) polymerized methyl a-chloroacrylate containing small amounts of ethylene glycol monoacrylate. Erickson (274) found t h a t glycidyl acrylates would polymerize through the ethenic group with peroxide catalysts and by opening the epoxy ring with Friedel-Crafts catalysts. .4dams, Johnson, and Englund ( 2 ) studied the polymerization of a-acetamidoacrylic acid and its methyl ester. Kenyon, Laakso, and Unruh (288) copolymerized a-acyloxyacrylates with styrene. Tawney (530) produced soluble copolymers from 2-aIly1 oxyethyl acrylates and 2,3-dichloropropylene. Roedel (467) obtained polymers containing formal side chains from monomers such as methoxymethoxyethyl methacrylate. Cox and Wallace ( 119)investigated the polymerization of acrylate esters containing carbonate groups. Jones (278, 279) prepared and polymerized substituted acrylamides, and Dalton ( 130) polymerized methylenebis(metharry1amide).
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Unfortunately, the term polyester has been applied to entirely different classes of polymeric materials. True polyesters are formed by polycondensation reactions and are included under condensation polymers. Within the last few years important polymers have been made from soluble unsaturated polyesters which are first condensed and then dissolved and copolymerized in ethenic monomers. The final reaction is a n addition polymerization so these esters are included in this classification. I n some cases, polymers having ester groups on linear chains, in a manner similar to the acrylates or acetates, are also called polyesters. These materials are usually formed by the polymerization of alkyl esters of unsaturated dibasic or of olefinic esters of saturated acids or b y copolymerization of such monomers. Several references deal with such polymers containing ester side chains. Polymers of vinyl esters of monocarboxylic acids are discussed in four references (22, 230, 422, 423). Gaylord and Eirich ( 199) studied the polymerization of isopropenyl acetate. Marple and Shokal (329) copolymerized unsaturated esters with diallyl diglycolates. Peters (412 ) produced copolymers of unsaturated esters and cyclopentadiene. Barrett ( 3 2 ) made resins for coatings by copolymerizing maleic esters of secondary alcohols with styrene; and Otto, Reiff, and Barrett (395) reacted maleic anhydride, styrene, and alcohols to produce a copolymer with ester side chains. Robinson (456) and Frilette (193) obtained copolymers from styrene and esters of unsaturated monobasic acids and polyhydric alcohols. Toy (639)described the copolymerization of dially esters of saturated dicarboxylic acids and diallyl arylphosphonates. Weaver (556) dissolved esters of polymethylene glycols and unsaturated dicarboxy acids in diallyl phthalate and then carried out a copolymerization. Gerhart and Lycan (204) produced polyester compositions by copolymerizing unsaturated polyesters and styrene with special catalysts. Adams ( 1 ) obtained coating resins by copolymerizing an ethenic monomer with a polyester made from maleic anhydride, rosin, linseed oil fatty acids, and a polyfunctional alcohol. Roat (454) described an interpolymer of styrene, maleic anhydride, and linseed oil diglyceride. Bartlett (38) made pour point depressants by polymerizing unsaturated esters of tricarboxylic acids. Although many allyl monomers are esters, polymers of all allyl compounds have been grouped together since there are a considerable number of references topolymersof this type. Methods of polymerizing allyl alcohol are discussed in three references ($0, 40, 131). Adelson and Gray ( 3 ) first polymerized allyl alcohol and then esterified the product to produce a coating resin. Tawney (526) copolymerized allyl alcohol and diallyl maleate. He also investigated (527) copolymers of allyl alcohol and diallyl itaconate. Nichols (379) produced an adduct of allyl alcohol and butadiene, esterified it with a dicarboxy acid, and polymerized the product. Polymerizable monomers were obtained by reacting allyl alcohol with various esters (48). Scheibli, Morris, and Shokal (473) produced polymers from the allyl ester of p-tert-butyl benzoic acid. Several patents (44, 63, 133, 184, 187, 219, 506, 529, 531, 569) refer to polymers and copolymers of diallyl esters of dicarboxylic acids. Gaylord and Eirich (200) discussed the relative ease of polymerization of allyl chloride and allyl acetate. Tawney (532)produced a copolymer of allyl chloride and diallyl itaconate. Hulse (266) obtained polymers of 2-chloromethyl allyl chloride. Butler and Ingley ( 9 4 ) reviewed the preparation and polymerization of allyl phenyl ethers. Dannenberg and Adelson (132) prepared linear polymers from allyl ethers of trihydric alcohols. Tawney (534) copolymerized methallyl ethyl ether and methyl methacrylate. Vaughan and Rust (546) reacted diallyl ether and hydrogen sulfide to form terminally unsaturated polythio ethers. Snyder (502) obtained copolymers of dimethallyl ether and alkyl acrylates. Butler and Ingley ( 9 3 ) discussed the polymerization of halogenated allyl amines. Tawney (528) produced copolymers from allyl acetate and crotonaldehyde. Rochow (456) prepared and polymerized tetrallyl silane. Bralley ( 7 4 ) made hard glass-
2056
INDUSTRIAL AND ENGINEERING CHEMISTRY
like polymers from chlorophenyl allyl carbonates. Phillips (414) copolymerized diallyl compounds and aldehydes. Gleim (209 j investigated the polymerization and copolymerization of dicarbonates containing two allyl groups. The various polymers containing fluorine are grouped together for easy reference. Barrick (33)polymerized tetrafluoroethylene in para& or cycloparaffin solutions. Miller (364-356) and Padbury and Tarrant (399) described the polymerization of trifluorochloroethylene. Irwin ( 2 7 0 ) obtained copolymers of tetrafluoro- and trifluorochloroethylene. Berry (53, 54) produced stable dispersions of polyt,etrafluoroethyIene McBee and Sanford (321) reported the preparation and polymerization of tnifluoromethylst,yrene. Denison and Goldschmidt ( 14 1 ) investigated the solvent polymerization of trifluoromethyl-suhstituted olefins. Sauer (470) polymerized hexafluoropropylene in aqueous emulsions. Prober (432) obtained copolymers of butadiene and 1,1,2-trichloro-3,3,3-trifluoropropylene. GoldSchmidt ($13) described the polymerizat'ion of 3,3,3-trifluoropropylene. Dickey and McKally ( 147) copolymerized p, p'difluoroacrylates and ethenic monomers. Kropa and Padbury (306j produced polymers and copolymers of various unsaturated esters of tetrafluorosuccinic acid. Dickey (145) and Dickey and Coover ( 14 6 ) produced polymers of fluoromethyl acrylonitriles and acrylamides. Jones (282) copolymerized vinylcyclopropene with various ethenic monomers. Bondhus and ,Johnson (66), Burroughs (92), and Johnson and Stuart (275) investigated the polymerization of vinylcyclohexene. Polymerization of vinylmethylnaphthalenes (85), acenaphthalene ( 183), bifluorene (273), and vinyl formate (546)was reported. Two references deal with coumarone-indene polymers ($01, 564). Rowland (461) and Thomas (536) produced furfuryl alcohol polymers. Elliot. (169) prepared and polymerized 2-vinylbenzofuran. Polymers and copolymers of vinyl alkyl ethers were prepared b y several authors (21, 95, 222, 364, 585). Miscellaneous polyniers involving drying oils were patented (188,302,360). Crouch and Howe (125) and Frey (191) produced polymers from olefins and sulfur dioxide. Otto and Barrett (394) describe copolymers from thiophene or substituted thiophenes and maleic anhydride. Zerner and Gradsten (679) and Kropa (304) obtained copolymers from triazines, and Kropa (305) copolymerized cyanuric triesters with polyhydric alcohols. Polymers were prepared from N-vinylpyrroles ( 190) and vinylpyrazines (291). Rowland (462) investigated interpolymers of azolines, maleic anhydride, and various ethenic monomers. Jackson (271 ) produced copolymers of vinylpyridine and divinylbenzene. Reynolds and Kenyon (444) obtained polymers containing lact'am rings by reacting X-vinylphthalimide and maleic anhydride followed by hydrolysis and addition of hydrazine. Gleim (211 ) reported the polymerization of the reaction product of urea and allyl chloroformate. Damschroder and Gates (234) copolymerized ebhenic monomers and unsaturated substituted proteins. Caldwell ( 100) polymerized N-acrylylsulfanilamides. Upson (541) investigated polymers of dialkyl vinyl p h o s p h a h . Schmerling (478) produced polymers from 3,Cepoxy-1-butene. Wilder and Herman (563) describe the copolymerization of vinyl tertiary hydroxy ketones with various monomers. Polymers were obtained from muconic acid derivatives (459) and l,Cdibronio-2-butene (192).
ELASTOMERS Proske (435)presented an historical reviex of synthetic rubber, and Watts (565) reviewed recent publications on elastomers. Reynolds, Johnson, and Clark (448)discussed the emulsion polymerization of isoprene. Reid (441) and Hiliyer and Wilson (243) described polymerizations of butadiene. Overberger and his coworkers (3.96)studied the polymerization and properties of 2-alkyl-1,3-butadienes. Bishop and Sullivan (67) polymerized various hexadienes.
Vol. 44, No. 9
Smith and his coworkers (499) reviewed recent developniente in low-temperature copolymerizations of butadiene and styrene. Bevan ( 5 5 )and D'Ianni, Heas, and hlast (144)presented reviews of copolymers for coatings containing relatively large amounts of styrene. Orr and Williams (390)studied the effect of activators, initiators, soaps, antifreeze, and reaction conditions on butadiene-styrene copolymers. Morris, Hollister, and Shew (362) prepared low-styrene copolyniers for low-temperature service. Marvel and Keplinger (335)and St. John, Uraneck, and Fryling (466) investigat,ed the effect of addition agents on butadienestyrene copolymerizations. Wakefield (548) copolymerized styrene with 2,3-difluorobutadiene and2-chloro-3-fluorobutadiene. Rose and Vanderbilt (460)produced copolymers of butadiene and acrylonitrile containing less than 25'jZ0 acrylonitrile. Bachmaii and his coworkers ( 1 6 ) prepared copolymers of butadiene and 38 ethenic monomers. Perry ( 4 1 1 ) obtained elastomers from isoprene and styrene by solvent copolymerization. WIo Seymour (367) describe the emulsion copolymerization of dienes and isopropenylbiphenyls. Hays (238)copolymerized butadiene and chloromaleic anhydride. Marvel, ;\IcCorlile, Fukuto, and JVright (338) produced copolymers of butadiene and benzylideneacetophenone. Rlarvel and his coworkers (331-333, 336, 339, 340, 34W) made an extensive investigation of dithiol polymers and copolymers. Sparks and Thomas (510) copolymerized isobutylene with cyclopentadiene and cyclohexadiene. Parrish (404) prepared a copolymer of isobutylene and 1-vinyl-3-cyclohexene. Eberly and Reid (106) obtained elastomers from the emulsion polymerization of isobutylene, acrylonitrile, and butadiene. Jorczak and Fettes (284) discussed the preparation and properties of liquid polysulfide polymers. Patrick (406)produced an odorless polysulfide rubber. Polysulfides were obtained from alkyl halides containing epoxy groups (434). Mochel (369) used 1-dodecanethiol to catalyze chloroprene polymerizations.
CONDENSATION POLYMERS Three reviews (180, 257, 369) of the chemistry of phenolic resins were published. Shreve and Golding (491) discuss the preparat,ion and properties of substituted phenolics for varnish resins. Bloch (60-62) produced modified phenolics by alkylating a mixture of xylene and phenol with ethylene chloride and then condensing the product with formaldehyde. Eijnsbergen and Pleysier (167) also prepared modified phenolics for varnishes. De Groote and Keiser (139) condensed alkyl phenols, salicylic acid, and aliphatic aldehydes. Hartough and Schick ( 2 3 1 ) made phenolic resins suitable for wrinkleproofing textiles. Xovotny and Vogelsang (583) condensed phenol, furfural, and formaldehyde. Low-temperature molding resins were obtained (373) b y condensing phenol and formaldehyde and then adding resorcinol. Allen and Kerr (4) produced varnish resins by condensing phenol, formaldehyde and an oil containing indene. Blake (58) employed solvents in the condensation of polyhydroxy aromatic compounds and polyhydric alcohols. Barr (29) and Gleim (210)modified phenolics by adding aromatic amines during condensation. Llazzucchelli and Urich ( 3 4 9 )reacted 2-aminobiphenyl and additional formaldehyde with phenolic condensates. Sorenson (508) produced modified phenolics by adding ketene polymers of fatty acids. Schrinipe (480) and Vogelsang (647) condensed ketones and formaldehyde, then reacted the product with phenol and formaldehyde. Landn (308) made chlorinated phenolics. Zenftman and XcGillivray (.578) investigated the condensation of dihydroxy aromatics and cycloparaffinic phosphony1 dichlorides. Amine-aldehyde condensates received considerable attention. Grosskinsky (223) reviewed the production of ureas. Suen (526) described a method of condensing urea and formaldehyde, and (563, 524) of producing modified ureap. Barsky and Straus (36) condensed urea, dimethylolurea, and formaldehyde. Parker
September 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
(403), Barsky and Straus ( 3 7 ) , and Garner and Bowman (198) modified ureas with butyl alcohols. Cairns (96) obtained polymers from vinyl a n d divinyl alkylene ureas. Kirby (290) reports resin formation from the condensation of diurea and formaldehyde. Jones and Aiken (281)produced resins b y reacting triehloroethylidinediureide and formaldehyde. Acrolein, urea, a n d formaldehyde were condensed (142) t o produce resins. Lindenfelser (314, 315) and Jones (280) modified melamines b y adding other amines during condensation. H u n t (260) investigated t h e condensation product of melamine, formaldehyde, dicyclopentadiene, and aliphatic alcohols. Resins were produced from dicyandiamide (488, 521). Walter (552) prepared condensates from 2,bdiamino-l,3,4thiadiazine and formaldehyde. Carpenter and Wilson (102) studied the condensation of hexamethylenediamine, triethanolamine, and carbon disulfide. Bacon a n d H a r t ( 1 7 ) condensed 2-chloro-4,6-diamino-1,3,5-triazine, drying oils, and formaldehyde. Castle (106)reviewed t h e chemistry of polyester condensations. T h e formation of alkyds from polybasic acids, polyhydric alcohols, a n d drying oil fatty acids was investigated (45,287,570). Bobalek (65) and Opp and Werner (588)produced styrene-modified alkyds. Martin (330) esterified 4cyclohexene-l,2-dicarboxylic acid. North (582) reviewed the use of pentaerythritol in the production of alkyds, and Rheineck (449) made polyesters from unsaturated dicarboxylic acids, pentaerythritol, and rosin. T h e esterification of isophthalic acid and tetramethylene glycol was reported (566). Irany, Skeist, and Maturi (269) formed polyesters from mixtures of saturated and unsaturated dicarboxy acids and dihydroxy alcohols. Carpenter (103) reacted the copolymer of maleic anhydride and olefins with polyhydroxy compounds to give polyesters. Drewitt and Lincoln (161) condensed diols with dicarboxy derivatives of thiophene, furan, a n d pyrrole. Marvel and Koch (337) and Patrick and Ferguson (407) investigated t h e preparation of polythiolesters. Smith (500) described t h e production of synthetic lubricating oil from dibasic acids, glycols, and alcohols. Polyamides were formed from lactams (267, 292, 387, COO). Carello (101) produced polyamides from diamines and methyl adipic acid obtained from furfural. Jones (283) condensed diamines and 4,4’-sulfonyl divaleric acid. Bradley ( W ) , Wittcoff (568),and Wittcoff, Peerman, Speyer, and Renfew (569)discussed the production of polyamides from diamines and dimerized or ti,imerized unsaturated fatty acids. Substituted amino acids were condensed (116, 117, 421) to produce linear polyamides. Allen and Drewitt ( 5 ) obtained polyamides from oxalic acid esters and diamines. Polyamides were produced (18)from the condensation of diamines and X,N’-dinitro-N,N’-dialkyloxamides. MacDonald (825) condensed the N-carboanhydride of 2-amino-4,6,6-trimethylheptanoicacid with the evolution of carbon dioxide. Mowry and Ringwald (366) prepared polyamides by the condensation of aminodinitriles and formaldehyde followed by hydrolysis of the nitrile groups. Lieser and Nischk (513) and Marvel and Young ( $ 4 9 ) discussed the formation of polyurethans from diisocvanates. Dreyfus (162) condensed diurethans with dihydroxy, diamino, and dicarboxylic compounds. Three reviews of the chemistry of the silicones were published (210, 686, 385). Barry (34) and Hyde (264) discussed the condensation of mixed alkyl-aryl silanes. T h e use of alcohols to hydrolyze chlorosilanes was suggested (159,504j. T h e hydrolysis and condensation of methyl halosilanes was carried out (505) using lead borate as a gelling agent. The low-temperature hydrolysis of mono-organo-dihalosilanes is described (154). Hyde (265) obtained organopolysiloxanes from sodium silanols and alkyl silanes. Methyl siloxanes were made (503) from methyl silylacetates. Mixed methyl-ethyl copolymers were investigated (155, 158) and several alkyl-aryl silanes were copolymerized (86, 88, 189, 553). Barry and Gilkey (35) obtained heat stable copolymers of carboxyphenyl siloxanes and polyhydric alcohols. AIodified silicones were produced (19) from organosilanes by
2057
hydrolysis followed b y a reaction with diisocyanates. Fluorinated polysiloxanes were prepared (87) b y a Grignard reaction. Polymers containing silicon-nitrogen linkages were made ( 109, 110, 512) b y treating silanes with anhydrous ammonia or amines. Methyl silanes were reacted (89, 261) with metallic sodium to produce polymers having silicon-silicon linkages. Clark (114) heated phenyl silanes with, aluminum chloride and (115) phenol with methyl silanes. A review of the production and properties of epoxy resins appeared ( 11 ) . Greenlee (617, 618) describes t h e condensation of phenols and epichlorhydrins to produce polyepoxides. Epoxy resins were obtained (113, 378, 490) from polyhydroxy aromatic compounds and epichlorhydrins. Stanton and Lowry (513 ) reacted aliphatic epoxides with vinylidene chloride. Barkhuff (26, 27) investigated the condensation of thiophene and aldehydes. Johnson (274) used a n alumina-silica catalyst to polymerize thiophene, and Koft (293)condensed thiophene and sulfur monochloride. Evans and Hookway (176) prepared resins from alkylene sulfones and formaldehyde. Kraus, Lendle, and Polaine (303) reviewed the chemistry of sulfonamide resins. Thompson (537) and Bloch and Thompson ( 6 4 ) copolymerized sulfonamides with mono- and dicarbonyls. Bengtsson (51 j produced resins ‘from sulfonamides and formaldehyde. Flory (182) condensed sebacyl chloride and hexene-1,6-thiol. Dazzi (186) obtained polysulfide resins from tertiary alkyl mercaptans and alkylene oxides. Harvey (234, 256) prepared resins from furfuryl alcohol and formaldehyde, and from furfural and mesityl oxide. Evans and Ingrassia (177) investigated furfuryl alcohollignin resins. Dunlop and Stout (164) condensed furfuryl alcohol with ammonium thiocyanate. Acetone was reacted (28, 143, 236) with aldehydes t o produce resins. Pinkston (417) studied the condensation of symmetrical dichloroacetone and aromatics. Hill (242) obtained polymeric azines b y condensing diketones with hydrazine. Lieser and Kemmner (316)produced condensates from hydrazine and ether-nitriles. Schaefer (472) described the production of resins from aminoaryloxytriazines. Resins were obtained (205) from the condensation of indoles and formaldehyde. Owen (398) investigated the condensation of aniline, formaldehyde, and dicyanodiamides. Synthetic lubricating oils were produced from t h e condensation of glycols (41, 229), dihydropyran esters (496), and ketal esters and glycols (128). Polyethers were prepared (46) from epoxide ethers. Woolhouse and Lunn (573) condensed aromatics and formaldehyde in t h e presence of strong sulfuric acid. Hirsch (244) produced resins from phenyl orthosilicate and formaldehyde. D e Groote and Keiser (158)treated substituted phenols with fatty acids.
PROCESSES, EQUIPMENT, AND P L A N T S Samaras and Perry (468) discussed commercial emulsion, suspension, and bulk processes for the polymerization of styrene. Smith, Werner, Westerhoff, and Howland (498) reviewed the newer developments and plant methods in the production of cold rubber. Shunmukham, Hallenbeck, and Guile (492) investigated the effect of agitation on the emulsion polymerization of styrene. They found t h a t increasing agitation decreases t h e rate and degree of polymerization. Seed (485) described a process for .emulsion polymerization of ethylene. Borglin and R a y (69) found t h a t salts of hydrorosin acids were better than other soaps in emulsion polymerization of butadiene and styrene. Special techniques for obtaining stable emulsions were published (47, 614, 515). The addition of monomers a t controlled rates was suggested (107, 157, 624, 225, 580) as means of improving emulsion polymerization processes. Davison and Dunn (135) found t h a t reducing the concentration of the emulsifier gave larger polymer particles. Park (401 ) discovered t h a t polymers could be obtained by direct drying of latexes if amine emulsifiers mere used in relatively low concentrations. Winslow and Matreyek (567) studied the effect of stabilizers
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
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on the production of uniform spheroids by suspension polymerization. The following dispersion agents were suggested for suspension polymerization processes: chlorostyrene and methacrylic acid copolymers ( 4 9 ) , mixed polyvinyl alcohols (70), aliphatic acid esters of polyethylene glycols (71 ), ureaformaldehyde condensates (&$), calcium phosphates (413), alkali hypophosphites (328), and aluminum hydrates, sodium salts of sulfonated polystyrene, and hydroxy methyl cellulose (475). Powers (428) described a suspension polymerization process in which the part,icle size is controlled by the relation between the amount of dispersing agent and the surface area of the particles. Reinhardt (442) developed a suspension polymerization process in which the desired polymer is added in controlled amounts, and no dispersion agent is required. Green (215, 2 1 6 ) and Sparks and Garber (509) described continuous low-temperature processes for the copolymerization of isobutylene and dienes. TTelch and Wilson (557) employed borontrifluoride in vinylidene fluoride as a catalyst for the lowtemperature polymerization of isobutylene. Kelson and Tegge (377) controlled the particle size of butyl rubber slurries by temperature changes during polymerization. Reid (440)obtained uniform copolymers by adding the most reactive monomer at the proper rate. Sargent ( 4 6 9 ) polymerized iY-vinyl compounds in dihalogenated solvents. Hurst and Miller ( 2 6 2 ) developed a process for the condensation of cyclohexanone and formaldehyde in cyclohexane solution. Schildknecht (476) reported t,he use of polar and nonpolar solvents in a process designed to produce granular polyvinyl ethers. Crouch (124) employed a continuous process for the copolymerization of butadiene and styrene in xylene solution. Church ( 1 1 1 ) used chloroform t o aid bubble removal by vacuum in the casting of polymethyl methacrylate. Chynoweth and Wintermute ( 1 1 2 ) and Fields (179)developed a process for casting thin sheets on salt solutions. Selson (37'6) and Powers (427) described equipment for butyl rubber polymerizations. Street and Dunbrook (519) discussed apparatus for continuous GR-S copolymerizations. Equipment required for cont,inuous polymerizations in which the polymer precipitates is described (507). Boyko ( 7 2 ) developed equipment for the production of polymet'hyl met'hacrylate rods. Hutchinson and Staudinger (263) used a column for the continuous production of polystyrene beads. Dunlop and Stout ( 1 6 3 ) employed an elongated tube for the partial polymerization of furfuryl alcohol. Brief descriptions of processes and plants for the production of polyacrylonitrile ( 8 ) , polyvinylpyrrolidene ( 9 ) , and silicones (10) were published. Larson (309) describes the design of a plant for the continuous low-temperature copolymerization of butadiene and styrene.
LITERATURE CITED Adanis, H. E. (to Armstlong Cork Co.), U. S.Patent 2,537,949 (.Tan.. 16. ~- , 1951). ~ , . Adams, R., Johnson, J . L., and Englund, B., J . Am. C i w n . Soc., 72, 5080 (1950). hdelson, D. E., and Gray, H. F., Jr. (to Shell Development Co.), U. S. Patent 2,555,775 (June 5, 1951). Allen, H. L., and Kerr, E. G. (to Allied Chemical & Dye Corp.), Ibid., 2,540,641 (Feb. 6, 1951). Allen, J., and Drewitt, J. G. N. (to Celanese Corp. of America), Ibid.. 2.558.031 (June 26. 1951). Allervelt, A. L. (to American Viscose Corp.), Ibid., 2,560,680 (July 17, 1951). Amos, J. L. (to Dow Chemical C o . ) , Ibid., 2,537,951 (Jan. 16, 1951). Anon., Chem. Eng., 58, N o . 1, 186 (1951). Ibid., 58, No. 6, 176 (1951). .knon., Chemzcal W e e k , 69, No. 18, 29 (1951). Anon., P a i n t , Oil Chem. Rea., 113, No. 23, 15 (1950). Auspos, L. A., and Dempster, J. B. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,578,660 (Dee. 18, 1951). Anthes, J. A. (to American Cyanamid Co.), Ibid., 2,567,836 (Sept. 11, 1951). \-
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Vol. 44, No. 9
(14) Arlman, E. J., and Melville, H. IT., Proc. Royal Soc, (Londoiz), A203, 301 (1950). (15) Bachman, G. B., and Carlson, C. L., J . Am. Chem. Soc., 73, 2857 (1951). (16) Bachman, G. B., Filar, L. J., Finholt, R. W., Heisey, L.V., Hellman, H. A I . , Lewis, L. L., and hlioucci, D. D., ISD. ENG.CHEM.,43, 957 (1951). (17) Bacon, J. L., and Hart, JT. F. (to British Industrial Plastics, L,td.), Brit. Patent 653,827 (May 23, 1951). (18) Badi~che-~4nilinund Sodafabrik, German Patent 802,847 (Feb. 26, 1951). (15) I b i d . , 802,895, 803.078 (Feb. 26, 1951). (20) Ibid., 803,833 (April 12. 1951). (21) Ibid., 805,188 (May 10, 1951). (22) Baer, M. (to Monsanto Chemical C o . ) , C . S. Patent 2,562,852 (July 31, 1951). (23) Bakelite Corp., Biit. Patent 649,304 (Jan. 24, 1931) (24) Banes, F. W., and Arundale. E. (to Standard Oil Dei elopment Co.), U. S. Patent 2,514,363 (July 11, 1950). (25) Banes, F. W., and Swaney, 11. IT. (to Standard Oil Dmelopment Co.), Ihid., 2.514.362 (July 11, 1950). (26) Barkhuff, R. A , , Jr., (t,o Monsanto Chemical C o . ) , Ibid., 2,538,857 (Jan. 23, 1951). (27) Barkhuff, R. A., Jr.. and Debiiig, L. VI. (to Monsanto Chemical C.O.),Ibid., 2,538.753 (Jan. 23, 1951). (28) Barnes. C. E. (to General Aniline & Film C o r p , ) , Ibid., 2,576,821 (h-ov. 27, 1951). (29) Barr, E. A , , Jr. (to Union Carbide & Carbon Corp.), Ibid., 2,552,025 (May 8 , 1951). (30) Barrett, G. R. (to Monsanto Chemical Co.). I b i d . , 2,537,015 (Jan. 9, 1951). (31) I h i d . , 2,537,016 (Jan. 9, 1951). (32) Ibid., 2,537,017, 2,537,018, 2,537,019, 2,537,020 (Jan. 9, 1951). (33) Barrick, P. L. (to E. I. d u Pont de Nemours & Co.), Ibid., 2,540,088 (Feb. 6, 1951). (34) Barry, A. J. (to Don;-Corning Corp.), Ibid., 2,557,931 (June 26, 1951). (35) Harry, A. J., and Gilkey, J. W.(to Dow Corning C a r p . ) , Ihid., 2,570,090 (Oct. 2, 1951). 136),~Barskv. G.. and Straus. F. A , . Ibid.. 2.548.416 (.%aril 10. 19511. . ~~. ( 3 7 ) Ibid., i:i76,711 ( X o v . 27, 1951). (38) Bartlett, J. H. (to Standard Oil Development Co.), Ihid., 2,575,992 (Nov. 23, 1951). (39) Basu. S., Sen, J. N., and Palit, S. R . , Proc. R o y . Soc. (London), A202, 485 (1950). (40) Bataafsche, N. W., de, Petroleum Maatsohappij, Dutch Patent 66,784 (Nov. 15, 1950). (41) Ibid., 66,998 (Dec. 15, 1950). (42) Ihid., 67,013 (Dec. 15, 1950). (43) Ihid., 67,083 (Jan. 15, 1951). (44) Ibid., 67,2?3 (Feb. 15, 1951). (45) Ihid., 67,571 (March 15, 1951). (46) Ibid., 67,705 (ilpril 16, 1951). (47) Ibid., 67,923 (May 15, 1951). (48) Ihid., 68,281 (July 16, 1951). (49) Baudel, D. ( t o Xathieson Chemical Corp.), U. S. I'ateiit. 2,546,207 (March 27, 1951). (50) Bengough, W7. I., and Sorrish, R. G. W., Proc. Rw. Soc. ( L o n d o n ) , A200, 301 (1950). (51) Hengtsson, E. B. (to .kktiebolaget Bofors), Swedish I'atent 133,061 (Sept. 25, 1951). (52) Herger, L., and Sons, Ltd., Takeford, L. E , Armitage, F., and Slightholme, J. 3.. Biit. Patent 654,031 ( (53) Berry, K. L. (to E. I. d u Pont de Xemours & r o . ) , U. 3. Patent 2,559,750 (July 10. 1951). (54) Ibid.. 2,559,752 (July 10, 19.51). (55) Bevan, E. A , , P a i n t T e c h n o l . , 15, 485 (1951). (56) Bezman. I. I.. and Brownina. D. D.. Paint, Oil. C ' h e ~ n .Rc-i,., 114, No. 20, 10B (1951). (57) Bishou. E. T.. and Sullivan, R. D. (to Shell Development Co ), U. S . Patent 2,514,928 (July 11, 1950). (5s) Blake, E. S. (to Monsanto Chemical Co.), Ibid.. 3,544,292, (March 6, 1951). (59) Blake, E. S., and Durland, R., Jr. (to Monsanto Chcmical Co.), Ibid., 2,547,150 (April 3, 1961). (60) Bloch, H. S. (to Universal Oil Products Co.), Ibid.. 2,542,111 (Feb. 20, 1951). (61) Ibid., 2,558,812 (July 3. 1951). (62) Ibid., 2,570,513 (Oct. 9, 1951). (63) Ibid., 2,578,168, 2,578,169 (Dee. 11, 1951). (64) Bloch, H. S., and Thompson, R. B. (to Universal Oil Producte Co.), Ibid., 2,557,935 (June 26, 1951). (65) Bobalek, G. (to A4rcoCo.), Ibid., 2,549,767 (April 24, 1951). (66) Bondhus, F. J., and Johnson, H. L. ( t o Sun Oil Co.), I b i d . , 2,543,092 (Feb. 27, 1951). ~~
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INDUSTRIAL AND ENGINEERING CHEMISTRY
Bonsall, E. P., and Valentine, L., J . Applied Chem. ( L o n d o n ) , 1. 249 (1951). Bonsall, E. P.,'Valentine, L., and Melville, H. W., J . Polymer Sei., 7, 39 (1951). Borglin, J. N., and Ray, P. A4.(to Hercules Powder Co.), U. S. Patents 2,569,447, 2,569,448, 2,569,449 (Oct. 2, 1951). Boyce, C. L. (to Shawinigan Resins Corp.), Ibid., 2,286,555, (May 29, 1951). Boyd, T., and Lucht, F. J. (to Monsanto Chemical Co.), Ibid., 2,580,277 (Dec. 25, 1951). Boyko, J. (to E. I. du Pont de Nemours & Co.), Ibid., 2.576.712 (Nov. 27. 1951). Bradley, T. 'F. (to Shell Development Co.), Zbid., 2,555,111 (May 29, 1951). Bralley, J. A. (to B. F. Goodrich Co.), Ibid., 2,548,141 (April 10, 1951), Brit. Patent 649,121 (Jan. 17, 1951). Brechbtlhler, T., and Magat, M., J . Chem. Phys., 47, 679 (1951) . Breitenbach, J. W., Monatsh., 82, 566 (1951). Ibid., p. 1118 (1951). Breitenbach, J. W., W i e n . Chem.-Ztg., 52, 222 (1951). Breitenbach, J. UT., and Karlinger, H., Monatsh., 82, 95 (1951). Ibid., p. 245. Ibid., p. 304. Breitenbach, J. W., and Tschamler, H., Ibid., p. 179. Brice, B. A,, Ricciuti, C., Willits, C. O., Swain, M. L., and Ault, W. C., J . Am. Oil Chemists' Soc., 28, 85 (1951). Brighton. C. A.. and Staudinger. J. J. P. (to Distillers Co., ctd.), U. S.Patent 2,543,094 (Feb. 27, 1951). British Thomson-Houston Co., Ltd., Brit. Patents 649,040, 649,041 (Jan. 17, 1951). Ibid., 653,257 (May 9, 1951). Ibid., 659,439 (Oct. 24, 1951). Britton, E. C., and White, H. C. (to Dow Chemical Co.), U. 9. Patent 2,571,533 (Oct. 16, 1951). Burkhard, C. A. (to General Electric Co.), Ibid., 2,554,976 (May 26, 1951). Burnett, J. D., and Melville, H. W., Trans. Faraday SOC.,46, 976 (1950). Burrell, C. M., Majury, T. G., and Melville, H. W.,Proc. Roy. SOC.( L o n d o n ) , A205, 309 (1951). Burroughs, S.G. (to Pennsylvania Industrial Chemical Corp.), U. S. Patents 2,567,916, 2,567,917, 2,567,918, 2,567,919, 2,568,216, 2,568,217 (Sept. 18, 1951). Butler, 0. B., and Ingley, F. L., J. Am. Chem. Soc., 73, 895 (1951). Ibid., p. 1512. Butler, G. B., and Nash, J. L., Jr., Ibid., p. 2538. Cairns, T. L. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,541,152 (Feb. 13, 1951). Calderbank, P. H., Brit. Plastics, 24, 356 (1951). Caldwell, J. R. (to Eastman Kodak Co.), U. S.Patent 2,541,011 (Feb. 13, 1951). Ibid., 2,544,638 (March 13, 1951). Ibid., 2,566,162 (Aug. 28, 1951). Carello, F., Italian Patent 459,475 (Sept. 12, 1950). Carpenter, A. S., and Wilson, D. L. (to Courtaulds, Ltd.), U.S. Patent 2,566,717 (Sept. 4, 1951), Brit. Patent 660,905 (Nov. 14, 1951). Carpenter, P. G. (to Hercules Powder Co.), U. S. Patent 2,538,761 (Jan. 23, 1951). Carr, E. L. (to Firestone Tire and Rubber Co.), Ibid., 2,537,644 (1951). Castan, P., and Haggar, 0. (to De Trey freres S. A.), Ibid., 2,567,803 (Sept. 11, 1951). Castle, R., P a i n t Oil Colour J . , 120,852, 921 (1951). Chaney, D. W. (to American Viscose Corp.), U. S. Patents 2,537,030, 2,537,031 (Jan. 9, 1951). Chapiro, A,, J . chim. phys., 47, 747 (1950). Cheronis, N. D., U. S.Patent 2,564,674 (4ug. 21, 1951). Cheronis, N. D. ( 1 / a to E. L. Gustus), Ibid., 2,579,416, 2,579,417, 2,579,418 (Dec. 18, 1951). , Church, J. S., and Tyler, H. R. (to the United States of America), Ibid.,2,559,345 (July 3, 1951). Chynoweth, J. L., and Wintermute, G. E . (to E. I. du Pont de Nemours & Co.). Ibid., 2,537,969 (Jan. 16, 1951). I CIBA, Ltd., Swiss Patent 273,405 (May 16, 1951). (1 14) Clark, H. A (to Dow-Corning Corp.), U. S.Patent 2,557,782 (June 26, 1951). (115) Ibid., 2,563,005 (Aug. 7, 1951). (116) Coleman, D., and Imperial Chemical Industries, Ltd., Brit. Patent 653,597 (May 16, 1951). (117) Compagnie de produits chirniques et electrometallurgiques Alais, Froges et Camarque, French Patent 965,742 (Sept. 20, 1950).
2059
(118) Condo, F. E., and Naps, M. (to Shell Development Co.), U. S. Patent 2,568,692 (Sept. 25, 1951). (119) Cox, F. W., and Wallace, J. M.,Jr. (to Wingfoot Corp.), Ibid., 2,575,585 (Nov. 20, 1951). (120) Crauwels, K., and Smets, G., Bull. soc. chim. Belges, 59, 182 (1950). (121) Ibzd., p. 443. (122) Crouch, W. W. (to Phillips Petroleum Co.), C . S. Patent 2,559,947 (July 10, 1951). (123) Ibzd., 2,574,020 (Nov. 6, 1951). (124) Ibid.. 2.577.677 iDec. 4. 1951). (125) Crouch: W: W.,'and Howe, J. F.( to Phillips Petroleum Co.), Ibid., 2,556,779 (June 12, 1951). (126) Crouch, W. W., and Marhofer, E. G. (to Phillips Petroleum Co.), Ibid., 2,549,961, 2,549,962 (April 24, 1951). (127) Croxall, W. J., and Von Hook, J. 0. (to Rohm & Haas Co.). Ibid., 2,556,134 (June 5, 1951). (128) Ibid., 2,556,135 (June 5, 1951). (129) Dalesch-Paetsch, H., Gummi-Ztg. u. Kautschuk, 4, 17 (1951). (130) Dalton, P. B. (to Sun Chemical Corp.), U. 8. Patents 2,576,501, 2.576.502 (Nov. 27. 1951). (131) Dannenberg,' H., and Adelson, D. E. (to Shell Development Co.), Ibid., 2,541,155 (Feb. 13, 1951). (132) Ibid., 2,545,689 (March 20, 1951). (133) Dannenberg, H., and Bradley, T. F. (to Shell Del-elopment Co.), Ibid., 2,564,395 (-4ug. 14, 1951). Damschroder. R. E.. and Gates, J. W. (to Eastman Kodak Co.), Ibid., 2,548,520 (April 10, 1951). Davison, J. A., and Dunn, W.A. (to the United States Rubber Co.), Ibid., 2,579,908 (Dee. 25, 1951). Daazi, J. (to Monsanto Chemical Co.), Ibid., 2,563,586 (Aug. 7, 1951). Day, J. H., and Solak, T. A . , J . Am. Chem. Sac., 73, 469 (1951). De Groote, M., and Keiser, 13. (to Petrolite Corp., Ltd.), U. S. Patents 2,568,118, 2,568,119 (Sept. 18, 1951). Ibid., 2,571,116, 2,571,117, 2,571,118, 2,571,119, 2,571,120 (Oct. 16, 1951). Denbigh, K. G., J. Applied Chem., 1, 227 (1951). Denison, G. H., Jr., and Goldschmidt, A. (to California Research Corp.), U. S.Patent 2,549,580 (April 17, 1951). Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, German Patent 802,846 (Feb. 26, 1951). Devlin, P. A., Whetstone, R. R., and Shokal, E. C. (to Shell Development Co.), U. S.Patent 2,561,613 (July 24, 1951). D'Ianni, J. D., Hess, L. D., and Mast, W. C., IND.ENG. CHEM.,43, 319 (1951). Dickey, J. B. (to Eastman Iiodak Co.), U. S.Patents 2,541,465, 2 541.466 (Feb. 13. 1951). Dickey,' J. B., and Coover, H. W.,Jr, (to Eastman Kodak Co.), Ibid., 2,559,855 (July 10, 1951). Dickey, J. B., and McNally, J. G. (to Eastman Kodak Co.). Ibid., 2,571,687 (Oct. 16, 1951). Dickey, J. B., and Stanin, T. E. (to Eastman Kodak Co.), Ibid., 2,520,917 (Sept. 5, 1950). Dornte, R. W. (to Standard Oil Development Co.), Ibid., 2,554,245 (May 22, 1951). Ibid., 2,559,062 (July 3, 1951). Ibid., 2,561,729 (July 24, 1951). Dornte, R. W., and McKay, J. F., Jr. (to Standard Oil Development Co.), Ibid., 2,536,841 (Jan. 2, 1951). Dow Chemical Co., Brit. Patent 651,699 (April 4, 1951). Ibid., 654,054 (June 6, 1951). Ibid., 654,099 (June 6, 1951). Ibid., 656,994 (Sept. 5, 1951). Ibid., 658,301 (Oct. 3, 1953). Dow Corning, Ltd., Brit. Patents 659,011, 659,022 (Oct. 17, 1951). Doyle, C. D. (to General Electric Co.), U. S.Patent 2,542,641 (Feb. 20, 1951). Drake, A. E. (to Hercules Powder Co.), Ibid., 2,569,462 (Oct. 2, 1951) Drewitt, J. G. N., and Lincoln, J. (to Celanese Corp. of America), Ibid., 2,551,731, 2,551,732 (May 8, 1951). Dreyfus, H. (to Celanese Corp. of America), Ibid., 2,568,885 (Sept. 25, 1951). Dunloo. A. P.. and Stout. P. R. (to Quaker Oats Co.). Ibid.. 2,570,027 (Oct. 2, 1951). (164) Ibid., 2,570,028 (Oct. 2, 1951). (165) Dyer, E., and Meisenhelder, W. C., J . Am. Chem. Soc., 73, 1434 (1951). (166) Eberly, K. C., and Reid, R. J. (to Firestone Tire and Rubber Co.), U. S. Patent 2,537,626 (Jan. 9, 1951). (167) Eijnsbergen, J. F. H., and Pleysier, J. A., C h i m . pientures, 14, 255 (1951).
.
2060
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INDUSTRIAL AND ENGINEERING CHEMISTRY
(168) Ellingboe, E. K. (to E. I. du Pont de Nemours &: Co.), U. S. Patent 2,562,897 (Aug. 7, 1951). (169) Elliot, E. D., J . Am. C k e m . Soc., 73,754 (1951). (170) Elly, J., Haward, R. S . , mid Simpson, IT.,J . Applied Chem. (Londrm), 1, 347 (1951). (171) Elwell, W. E., and Meier, R. I,. (to California Research Corp.), E. S. Patent 2,563,997 (Sug. 14, 1951). arid Williams, H L., Con. J . (172) Embree, W. H., Mitchell, J. M,, Chem., 29, 253 (1951). (173) Embree, W. H., Spolsky, R., and Williams, H . L., IND. EKG. CHEM.,43,2553 (1951). (174) Erickson, J. G. (to American Cyanamid C o . ) , U. S. Patent 2,556,075 (June 5, 1951). (175) Evans, A. G., J . Applied Chcm. ( L o n d o n ) , 1, 240 (1951). (176) Evans, E. M., and Hookway, H. T. (to British Resin Products, Ltd.), U. S.Patent 2,543,236 (Feb. 27, 1951). (177) Evans, R. S . ,and Ingrassia, A. P. (to Masonite Corp.), Ibid., 2,538,302 (Jan. 16, 1951). (178) Falkenburg, L. B., Hill, W. II., and Wolff, H., J . A n i . Oil Chemistu’ Soc., 28, 496 (1951). (179) Fields, R. T. (to E. I. du Pont de Nemours 8. Co.). U. S. Patent 2,537,970 (Jan 16, 1951). (180) Finn, S. R., Megson, N . J. L., and Whittaker, E. J. K., Chetnbtru and Industrv. 1950. 849. (181) Fisher, G. S., GoldXlatt, L. S., Kniel, I., and Snyder, -l.D., IND.ENG.CHEM.,43, 671 (1951). (182) Flory, P. J. (to Wingfoot Corp.), U. S. Patent 2,510,587 (June 6, 1950). (183) Flowers, R. G., and Elliott, E. D., Jr. (to General Electric Co.), Ibid., 2,563,524 (Aug. 17, 1951). (184) Fluchaire, M. L. A., and Collardean, G. (to SociBtQdes usines chimioues Rhone-Poulenc). Ibid.. 2.570.029 (Oct. 2. 1951). Fordham, J. W. L., and Wiiiiams, ~ H L.,’ : J. Am. Ckkm. SOL, 73, 1634 (1951). Ibid., p. 4855. Foster, F. J. (to United States Rubber Co.), U. S. Patent 2,547,696 (April 3, 1951). Foster, N. C. (to Westinchouse Electric Corp.), Ibid., 2,550,114 (April 24, 1951). (189) Francis, J. D. (to Doiv Corning Corp.), Ibid., 2,573,428 (Oct. 30, 1951). ’ Freudenberg, W. (to General Aniline & Film Corp.) Ibid., 2,546,924 (Mar. 27, 1951). ’ Frey, F. E. (to Phillips Petroleum C o . ) , Ibid., 2,543,842 (March 6 , 1951). Frey, F. E., and Condon, F. E. (to Phillips Petroleum C o . ) , Ibid., 2,562,090 (July 21, 1951). Frilette, V. J., Ibid., 2,568,331 (Sept. 18, 1951). Fryling, C. F., and Follett, h. E., J . PoZUmeT Sei., 6, 59 11951). Fryling,’ C . F., and Reynolds, IT. B. (to Phillips Petroleum Co.), U. S. Patent 2,548,220 (March 27, 1951). Garber, J. D. (to Standard Oil Development C o . ) , Ibid., 2,557,094 (June 19, 1951). Garber, J. D., Sparks, IT. J., and Young, D. W. (to Standard Oil Development Co.), ILid., 2,559.448 (July 3, 1951). Garner, P. J.. and Bowman. R. E. (to Shell Development Co.), Ihid., 2,572,256 (Oct. 23, 1951). Gaylord, N. G., and Eirich, 1:. R., J . Polymer S e i . , 5 , 743 11950). \ - - - - ,
Ibid., 7, 575 (1951). Geiger, L. 31. (to Xeville C o . ) , U. S. Patent 2,565,222 (.lug.
21, 1951). Genas, M. (to Societe Organico), Ihid., 2,564,001 (dug. 14, 1951). Gerhart, H. L. (to Pittsburgh Plate Glass Co.), I b i d . , 2,575,690 (Dee. 18, 1951). Gerhart, H . L., and Lycan, IV. H. (to Pittsburgh Plate Glass Co.), Ibid., 2,554,567 (May 29, 1951). Gesellschaft fur Teerverwertung m. b. H., German Patent 808,594 (June 14, 1951). Giammaria, J. J. (to Socony-Vacuum Oil Co., Inc.), LT. S. Patent 2,543,964 (March 6. 1951). Ibid., 2,570,788 (Oct. 9, 1951). Ginell, R., J . Polymer Sci., 7, 413 (1951). Gleim, C. E. (to Wingfoot Corp.), U. S. Patent 2,541,646 (Feb. 13, 1951). Ibid., 2,545,692 (March 20, 1951). Ibid., 2,579,426, 2,579,427 (Dee. 18, 1951). Goerts, J. R. (to E. I. du Pont de Semours 8. Co.), Ibid.. 2,576,009 (Nov. 20, 1951). Goldschmidt, A, J. Am. Chem. SOC.,73, 2940 (1951). Green, A. D. (to Standard Oil Development Co.), U. S.Patent 2,537,130 (Jan. 9, 1951). lbid., 2,557,910 (Ju:ie 19, 1951).
Vol. 44, No. 9
(216) Green, A. D., and Palts, W.J. (to Standard Oil Development Co.), Ibid., 2,545,144 (March 13, 1951). (217) Greenlee, S. 0. (to Devoe and Raynolds Co., Inc.), Ibid., 2,542,664 (Feb. 20, 1951). (218) Ibid., 2,588,949 (July 3, 1951). (219) Gregg, R. A. (to United States Rubber Co.), l b i d . , 2,547,701 (hpril 3, 1951). (220) Gregory, J. B., Rubber Age, 70, 211 (1951). (221) Grosse, A . V. ( t o Houdry Process Corp.). U. S. Patent 2.543.016 . (Feb. 27, 1951). (222) Grosser, F. (to General Aniline & Film Corp.), Ibid., 2,547,819 (April 3, 1951). (223) Grosskinsky, O., Ber. Ges. Kohlentech., 5 , 375 (1950). (224) Halbig, P., E.S.Patent 2,570,056 (Oct. 2, 1951). (225) Ham, G. E, (to Monsanto Chemical Co.), Ibid., 2,559,154, 2,559,155 (July 3, 1951). (226) Ham, G. E., and Mowry, D. T. (to hIonsanto Chemical Co.), Ibzd., 2,563,602 (Aug. 7, 1951). (227) Hamilton, J. hl. (to E. I. du Pont de Nemours & Co.), Ibid., 2,569,524 (Oct. 2, 1951). (228) Hammond, G. S.,and Bartlett, P. D., J . Poluma Sci., 6, 617 (1951). (229) Harman, D., and Vaughan, W.E. (to Shell Development Co.), U. S. Patent 2,536,884 (Jan. 2, 1951). (230) Harrison, J . .I.,and Xheeler, D. €I., J . Am. Chem. Soc., 73, 839 (1951). (231) Hartough, H. D., and Schick, J. IT. (to Socony-Vacuum Oil Co., Inc.), U. S.Patent 2,546,946 (March 27, 1951). (232) Haivard. R. S . (to Petrocarbon, Ltd.), Brit. Patent 655,723 (Aug. 1, 1951). (233) Harvard, R. N., and Simpson, W.,Tra?is. F a m d a y Soc., 47, 212 (1951). (234) Harvey, AI. T. (to Harvel Research Corp.), British Patent 650,324 (Feb. 21, 1951). (235) Harvey, hf. T. (to Harvel Research Corp.), U. S. Patent 2,565,685 (Aug. 28, 1951). (236) Harvey, M. T., and Rosamilia, P. L. (to Harvel Research Corp.), Ihid., 2,571,089. (237) Hayes, J. J. (to Mathieson Chemical Corp.), Brit. Patent 659,057 (Oct. 17, 1951). (238) Hays, J. T. (to Hercules Powder Co.). U. S.Patent 2,540,072 (Jan. 30, 1951). (239) Heiligmann, R. G., J . P o l y m e r Sei., 6, 155 (1951). (240) Heinrich, R. L. (to Standard Oil Development Co.), U. 9. Patent 2,540,580 (Feb. 6, 1951). (241) Hill, A , , and Burkholder, K,J. (to Diamond ;ilkali C o . ) , Ibid., 2,555,407 (June 5, 1951). (242) Hill, J. Vi-. (to E. I. du Pont de Kemours & C o . ) ,Ibid., 2,556,876 (June 12, 1951). (243) Hillyer, J. C.. and Wilson, ,J. F. (to Phillips Petroleum Co.), Ibid., 2,550,895 (May 1, 1951). (244) Hirsch, A. (to Diamond Alkali Co.), Ibid., 2,555,489 (June 5, 1951). (245) Hoffman, A. E. (to Universal Oil Products Co.), Ibid., 2,538,001 (Jan. 16, 1951). (246) Hogshed, M. J. (to E. I . du Pont de Nemouis RE Co.), l b i d . , 2,566,203 (Aug. 28, 1951). (247) Holgberg, E. I. (to American Cyanamid Co.), l b i d . , 2,557,911 (June 19. 1951). (248) Hollyday, W. C . , Jr., and Sparks, W. 3. (to Standard Oil Development Co.), Ibid., 2,581,796 (July 24, 1951). (249) Holm, >I. hl., and Langlois, G. E. (to California Research Corp.), lbid., 2.579.433 (Dee. 18, 1951). (250) Hopff, H., and Rautenstrauch, C., Makronzol. Chem., 6 , 39 (1951). (251) Hovey, G., J . Am. Oil Chemists’ SOC.,27, 481 (1950). (252) Howard, E. G., Jr. (to E. I. du Pont de Neniours & Co.), U. S. Patent 2,560,694 (July 17, 1951). (253) Ihid., 2,587,109 (Sept. 4, 1951). (254) Howland, L. H., and Reynolds, J. A. (to United States Rubber C o . ) , Ihid., 2,556,651 (June 12, 1951). (255) Hulse, G. E. (to Hercules Powder Co.), I b i d . , 2.534.447 (Dee. 19, 1950). (256) Ibid., 2,571,883 (Oct. 16, 1951). (257) Hultasch, II. (to Phillips Petroleum Co.), Ibid., 2,557,684 (June 19, 1951). (427) Powers, J. 1%. (to Standard Oil Development Co.), Ibid., 2,561,226 (July 17, 1951). (428) Powers, J. R. (to B. F. Goodrich Co.), I b i d . , 2,520,959 (Sept. 5, 1950). (429) Powers, P. O., IND.ESG. CHEM.,43, 1770 (1951). (430) Price, C. C., and Greene, C. E., J . Polymer Sci., 6, 111 (1951). (431) Price, C. C., and Walsh, J. G.. Ibid., p. 239. (432) Prober, M. (to General Electric Co.), U. S.Patent 2,575,125 (Nov. 13, 1951). (433) Prochazka, J. C. (to Bata narodni podnik), Ibid., 2,551,703 (May 8, 1951). (434) Produits chimiques de RobBcourt, French Patent 966,388 (Oct. 9. 1950). (435) Proske, Cr. E., Gumini ‘u. Asbest, 4, 25 (1951). (436) Provost, R. L. (to United States Rubber Co.), U. S. Patent 2,560,741 (July 17, 1951). (437) Ibid.. 2,577,432 (Dec. 4, 1951). (438) Provost, R. L., and Foster, F. J. (to United States Rubber Co.), Ibid., 2,551,336 (May 1, 1951). (439) Raff, R. -4.T., and Silverman, B. H., IND.ENG.CHEM.,43, 1423 (1951). (440) Reid, J. C., Jr. (to htlantio Refining Co.), U. S.Patent 2,539,523 (Jan. 30, 1951). (441) Reid, R. J. (to Firestone Tire and Rubber C o . ) , Ibid., 2,537,630 (Jan. 9, 1951). (442) Reinhardt, R. C. (to Dow Chemical Co.), Ibid., 2,543,805 (Mar. 6, 1951). (443) Renfrew, A, Plastic I n s t . (London) Trans., 19, S o . 35, 5 (1951). (444) Reynolds, D. D., and Kenyon, W. 0. (to Eastman Kodak Co.), U. S. Patent 2,566,250 (-Lug. 28, 1951). (445) Reynolds, W. B., and Cotten, E. W. (to Phillips Petroleum C o . ) , Brit. Patent 656,727 (Aug. 29, 1951). (446) Reynolds, W.B., and Cotten, E. W.,ISD.ENG.CHEM., 42, 1905 (1950). 1447) Reynolds, W. B., and Crouch, TV. IT., Advances in Chem. Series, 5, 310 (1951). (448) Reynolds, W.L., Johnson, A. L., and Clark, R. H . , Can.J . Technol., 29, 343 (1951). (449) Rheineck, 8 . E. (to Hercules Povder Co.), C . S . Patent 2,569,495 (Oct. 2, 1951). (450) Richards, J. C. (to E , I. du Pont de Semours & C o . ) , Ibid., 2,546,238 (March 27. 1951). (451) Richards, L. hl. (to E. I. du Pont de Nemours & Co.), Ibid., 2,566,251 (Aug. 28, 1951). (452) Richards, R. E., J . Applied Chem. (London), 1, 370 (1951). (453) Roach, J. R. (to General Alills, Inc.), C. S. Patent 2,562,537 (July 31, 1951).
September 1952
INDUSTRIAL AND ENGINEERING CHEMISTRY
2063
(454)Roat, F. B. (to Ellis-Fostei Co.), Ibid., 2,559,465, 2,659,466 (498) Smith, H. S., Werner, H. G . , Westerhoff. C. B., and Howland, (July 3,1951). L. H., IND. ENG.CHEM.,43,212 (1951). (455) Robinson, R. S. (to Beck, Koller, and Co.), Brit. Patents (499) Smith, H. S.,Werner, H. G., Westerhoff, C. B., and Howland, 651,560,651,561 (April 4,1951). L. H., Rubber A g e and Synthetics, 32, No. 1, 15 (1951). (456)Rochow, E. G. (to General Electric Co.), U. 8. Patent 2,538,657 (500) Smith, P. Y., Jr. (to Standard Oil Development Co.), U. S. (Jan. 16,1951). Patents 2,575,195, 2,575,196(Nov. 13,1951). (457) Roedel, M.J. (to E. I. du Pont de Nemours & Co.), Ibid., (501) Snyder, H. R., and Steward, J. M. (to Phillips Petroleum Co.), 2,570,861(Oct. 9,1951). Ibid., 2,574,894(Nov. 13,1951). (458)Ibid., 2,572,951(Oct. 30,1951). (502)Snyder, R. H.(to United States Rubber Co.), Ibid., 2,539,706 (459) Rohm and Haas G. m. b. H., German Patent 803,959 (April (Jan. 30,1951). 12,1951). (503)Soci6t6 des usines chimiques Rhane-Poulenc., Brit. Patent (460)Row, H.J., and Vanderbilt, B. M. (to Standard Oil Develop645,389(Nov. 1, 1950). ment Co.), U. S.Patent 2,554,268 (May 22,1951). (504)&bid., 654,466(June 20,1951). (461)Rowland, C. S. (to Interchemical Corp.), Ibid., 2,553,677 (505)Ibid., 661,737(Nov. 28,1951). (May 22,1951). (506)Soci6t6 des usines chimiques Rhhe-Poulenc, French Patents (462)Rowland, S. P. (to Rohm and Haas Co.), Ibid., 2,543,601, 965,773,965,774(Sept. 21, 1950), U. S. Patent 2,573,001 2,543,602(Feb. 27,1951). (Oct. 30,1951). (463)Rudel, H. W., and Wasson, 6. E. (to Standard Oil Develop(507) Solvay and Cie, German Patent 804,724(April 30,1951). ment Co.), Ibid., 2,561,232(July 17,1951). (508) Sorenson. B. E. (to E. I. du Pont de Nemours & Co.), U. S. (464)Rust, F. F., Stiles, A. R., and Vaughan, W. E. (to Shell DePatent 2,544,365(March 6,1951). velopment Co.), Ibid., 2,536,008(Dec. 26,1950). (509) Sparks, W. J., and Garber, J. D. (to Standard Oil Develop(465) Sachs, C. C., and Bond, J. (to Alexander H. Kerr and Co., ment Co.), Ibid., 2,546,020(March 20,1951). Inc.), Ibid., 2,548,685(April 10,1951), 2,579,095(Dec. 18, (510) Sparks, W.J., and Thomas, R. M. (to Jasco, Inc.), Ibid., 1951). 2,557,822(Dee. 11, 1951). (466)St. John, W. M., Jr., Uraneck, C. A., and Fryling, C. F., J . (511)Sparks, W.J., and Young, D. W. (to Standard Oil DevelopPolyter Sci., 7,159 (1951). ment Co.), Ibid., 2,549,539(April 17,1951). (467)Salomon, G., and Koningsberger, C., Rubber Chem. and Tech(512)Speier, J. L., Jr. (to Dow Corning Gorp.), Ibid., 2,567,131 nol., 24, 463 (1951). (Seth 4.1951). (465) Samaras, N. N. T., and Perry, E., J . Applied Chem. ( L o n d o n ) , (513) Stan&, G. W.; and Lowry, C. E. (to Dow Chemical Co.), 1,243(1951). Ibid., 2,556,048(June 5,1951). (469)Sargent, D. E. (to General Aniline & Film Corp.), U. S. (514) Staudinger, 5. J. P. (to Distillers Co., Ltd.), Ibid., 2,543,306 Patent 2.560.251(Julv 10.1951). (Feb. 27,1951). (470)Sauer, J. d. (to E.'I. du Pont de Nemours & Co.), Ibid., (515) Staudinger, J. J. P. and Cleverdon, D. (to Distillers Co., 2,549,935(April 24,1951). Ltd.), fbid., 2,562,440(July 31,1951). (471) Saunders, S. L. M., and Schiller, D. (to Pinchin, Johnson, and (516) Staudinger, J. 3. P., and Hutchinson, H. SI. (to Distillers Amoiates, Ltd.), Brit. Patent 647,352(Deo. 13,1950). Co., Ltd.), Ibid., 2,539,376, 2,539,337 (Jan. 23,1951). (472)Schaefer. F. C. (to American Cyanamid Co ), U. S. Patent (517)Stedry, P. J., IND. ENG.CHEM.,43, 2372 (1951). 2,560,825(July 17,1951). (518) Storey, E.B., and Williams, H. L., Rubber A g e ( N . Y . ) , 68, (473)Scheibli, J. R.,Morris, R. C,, and Shokal, E. C. (to Shell 571 (1951). Development Co.), Ibid., 2,578,950(Dec. 18,1951). (519) Street, J. N., and Dunbrook, R. F. (to Firestone Tire and (474) Schertz, G. L. (to Hercules Powder Co.), Ibid., 2,574,847 Rubber Go.), C. S. Patent 2,560,027 (July 10, 1951). (Nov. 13, 1951). (520) Sturrock, M. G., and Lawe, T. (to Dominion Tar and Chemi(475)Schick, J. L. (to Dow Chemical Co.), Ibid., 2,538,049,2,538,050, cal Co., Ltd.), Ibid., 2,555,298(May 29,1951). 2,538,051(Jan. 16,1951). (521)Suddentsche Xalkstickstoffe-Werke Akt.-Ges., German Patent (476)Schildknecht, C. E. (to General Aniline & Film Corp.), 804,604(April 26,1951). Ibid., 2,551,467(May 1, 1951). (522)Suen, T.(to American Cyanamid Co.), U. S. Patents 2,554,424 (477) Schmerling, L. (to Universal Oil Products Co.), Ibid., 2,566,537, (May 22,1951),2,559,578(July 10,1951). 2,566,538(Sept. 4,1951). (523) Suen, T.,and Daniel, J. H., Jr. (to American Cyanamid Co.), (478)Ibid., 2,570,601(Oct. 9,19511. Ibid., 2,554,475(May 22,1951). (479) Schmitz, J. V., and Lawton, E. J., Science 113,718 (1951). (524) Suen, T., and Schiller, A. M. (to American Cyanamid Co.), (480) Schrimpe, C. F. (to Union Carbide and Carbon Corp.), C. S. Ibid., 2,565,278(-4ug. 21,1951). Patents 2,538,883,2,538,884(Jan. 23, 1951), 2,545,559 (525)Swaney, M. W., and Banes, F. W. (to Standard Oil Develop(March 20,1951). ment Co.), Ibid., 2,565,998(Aug. 28,1951). (481) Sohouteden, F. L. M., and Tritsmans, R. G . (to Gavaert (526) Tawney, P. 0. (to United States Rubber Co.), Ibid., 2,546,Photo-Producten N.V.), Ibid., 2,565,783(Aug. 28,1951). 798 (Marrh 27.1951). (452)Schulze, W.A., and Crouch, U ' . W. (to Phillips Petroleum (527)Ibid., 2,556,989, 2,556,990(June 12,1951). Co.), Ibid., 2,555,665(June 5,1951). (528)Ibid., 2,560,495(July 10,1951). (483)Ibid., 2,575,135(Nov. 13,1951). (529) Ibid., 2,561,153, 2,561,154(July 17,1951). (484)Schulze, W. A., and Mahan, J. E. (to Phillips Petroleum Co.), (530)Ibid., 2,567,304(Sept. 11, 1951). Ibid., 2,552,692(May 15,1951). (531) Ibid., 2,568,872(Sept. 25,1951). (485)Seed, L.( t o Imperial Chemical Industries, Ltd.), Ibid., 2,542,- (532) Ibid., 2,569,959, 2,569,960(Oct. 2.1951). 783 (Feb. 20,1951). (533) -Tbid.. -,2.57-,-6.245(Nov. 27. 1951). (486)Seger, F. M., Feasley, C. F., and Sachanen, A. N. (to Socony(534)Ibid., 2,579,079(Dec. 18,' i95ij. Vacuum Oil Co.), Ibid., 2,551,640, 2,551,641, 2,551,642, (535) Thinius, K.,Gummi-Ztg. u. K u u t s c h u k , 4,53 (1951). 2,551,643, 2,551,644(May 8,1951). (536) Thomas, B. (to Delrac Corp.), U. S. Patent 2,571,994(Oct. (487)Seger, F. M., and Sachanen, A. N. (to Socony-Vacuum Oii 23,1951). Co., Inc.), Ibid., 2,551,638(May 8, 1951). (537) Thompson, R. B. (to Universal Oil Products Co.), Ibid., (488)Sellet, L., and Dawson, W. 0. (to Jacques Wolf and Co.), 2,545,716(Mar. 20,1951). Ibid., 2,567,238(Sept. 11. 1951). (538) Thompson, R. B., and Schmerling, L. (to Universal Oil Prod(489)Shah, H. A., Leonard, F., and Toblosky, A. W., J . Polymer ucts Co.), Ibid., 2,568,092(Sept. 25,1951). Sci., 7, 537 (1951). (539)Toy, A . D. F. (to Victor Chemical Works), Ibad., 2,538,810 (490)Shokal, E. C., and Mueller, A. C. (to Shell Development Co.), (Jan. 23,1951). U. S. Patent 2,548,447(April 10,1951). (540)Universal Oil Products Co., Brit. Patent 650,831 (Mar. 7, (491) Shreve, R. N., and Golding, B., IND.ENG. CHEM.,43, 134 1951). (1951) . (541)Upson, R.W.(to E. I. du Pont de Nemours & Co.), U. S. (492)Shunmukham, S. R., Hallenbeck, V. L., and Guile, R. L., Patent 2,557,805(June 19,1951). J . Polymer Sci., 6 , 691 (1951). (542)Uraneck, C . A. (to Phillips Petroleum Co.), Ibid., 2,578,910 (493) Signer, R., and Demagistri, A., J . chim. phys , 47, 704 (1950). (Dec. 18,1951). (494) Sleightholme, J. J.,and Wakeford, L. E. (to Lewis Berger and (543) Ushakov, S.N.,Mitsengendler, S. P., and Straikhman, G. A., Sons, Ltd.), Brit. Patent 649,442(Jan. 24,1951). U s p e k h i Khim., 19, 265 (1950). (495) Slotterbeck, 0.C., and Young, D. W. (to Standard Oil De(544) Vandenberg, E. J. (to Hercules Powder Co.), U. S. Patent velopment Co.), U.s. Patent 2,544,273(May 22,1951). 2,569,506(Oct. 2,1951). (496)Smith, C . W. (to Shell Development Co.), I b i d , 2,537.921 (545)Vansheidt. A. A.. and Cheloanova. L. F,. J . Gen. Chem. (U.8.(Jan. 9, 1951). S.R.), 20, 2261 (1950). W. (to B. F. Goodiich Co.), Ibid., 2 563.079(Bug. 7 (497) Smith, (546)Vaughan, W. F., and Rust, F. F. (to Shell Development 1951). Co.), U. S.Patent 2,563,383(Aug. 7,1951). \ _ _ _ ,
~I
e.
.
INDUSTRIAL AND ENGINEERING CHEMISTRY Vogelsang, G. K. (to the Borden Co.), Ibad., 2,576,735 (Sov. 27, 1951).
Wakefield, L. B., IND.ESG. CHEJf., 43, 2363 (1951). Wakeford, L. E., and Hewitt, D. H. (to Sherwin-Williams Co.), U.S. Patent 2,556,488 (June 12, 1951). Ibid., 2,567,137 (Sept. 4, 1951). Walling, C., and Davison, J. A , , J . Am. Chem. SOC.,73, 5736 119511.
M-altei, H. A. (to Monsanto Chemical Co.), U. S. Patent 2,536,521 (Jan. 2, 1951). Varrick, E. L. (to Coining Glass Works), Ibid., 2,560,498 (July 10, 1951). Watson, W.H. (to Polymer Carp.), Ibid., 2,577,390 (Dee. 4. 1
1951).
Watts, J., Ann. Rept. Progress Rubber Technol., 14, 33 (1950). Weaver, W , I. (to Libbey-Owens-Ford Glass Co.), E. S. Patent 2,549,732 (April 17, 1951). Welch, L. M., and Wilson, H. L. (to Standard Oil Development Co.), Ibid., 2,548,415 (April 10, 1951). Wesp, G. L. (to Monsanto Chemical Co.), Ibid., 2,556,459 (June 12, 1951). Whitehill, L. N., and Shokal, E. C. (to Shell Development Co.), Ibid., 2,545,184 (March 13, 1951). Wicklatz, J. E. (to Phillips Petroleum Co.), Ibid., 2,564,632 (Aug. 14, 1951). Wicklatz, J. E., Kennedy, T. J., and Reynolds, W. B., J . Polymer Sci., 6, 45 (1951). Wiener, H., Ibid., 7, 1 (1951). Wilder, R. S.,and Herman, D. F. (to Publicker Industries, Inc.), U. S. Patent 2,540,153 (Feb. 6, 1951). Wille, H., Brennstof-Chem., 32, 238 (1951). Winding, C. C., ISD. ENG.CHEW,43, 1997 (1951). Wingfoot Corp., Brit. Patent 655,377 (July 18, 1951).
Vol. 44, No. 9
(567) Winslou, F. H., and hlatreyek, W., IND.ENG.CHEM, 43, 1108 (1951). (568) Wittcoff, H., M o d e r n Packaging, 24, No. 7 , 111 (1951). (569) Wittcoff, H., Peermau, D. E., Speyer, F. G., and Ronfew, M. M., I n d i a Rubber World, 124, 189 (1951). (570) Tittooff, H., and Roach, J. R. (to General Mills, Inc.), U. S. Patents 2,572,085, 2,5i2,086 (Oct. 23, 1951). (571) Wolf, R. J. (to The B. F. Goodrich Co.). Ibzd., 2,548,186 (April 10, 1951). (572) Ibid., 2,570,900 (Oct. 9, 1951). (573) Woolhouse, T. F., and Lunn, JV., Ibid., 2,568,313 (Sept. 18, 1951). (574) Wrigley, A. N., Siciliano, J., Xast, W.C., and Fisher, C. H., U . S . Dept. Agr., B u r . Agr. I n d . Chem., AIC-266, 7 (1950). (575) Yaiig, P. T., and Guile, R. L., J . Polymer Sci., 6, 881 (1951). (576) IToung, D. W. (to Standard Oil Development Co.), C . S.Patent 2,542,610 (Feb. 20, 1951). ( 5 i i ) Young, D. W., and Smyers, W.H. (to Standard Oil Development Co.), Ibid., 2,563,631 (Aug. 7 , 1951).
(578) Zenftman, H., and McGillivray, R. (to Imperial Chemical
Industries, Ltd.), Brit. Patent 653,489 (May 16, 1951). (579) Zerner, E., and Gradsten, M.A., (to Sun Oil Carp.),U. S.Patent 2,559,694 (July 10, 1951). (580) Zigeuner, G., K u n s t o f e , 41, 221 (1951). (581) Zigeuner, G., Schaden, W., Gabriel, O., and Teisenberger, E., Monatsh., 81, 1108 (1950). (582) Ibid., p. 1017 (1951). (583) Zinke, A., J . Applied Che?n. ( L o n d o n ) , 1, 257 (1951). (584) Zinke, A., Zigeuner, G., \Veiss, G., Leupold-Lowenthall, W.9 and Wiesenberger, E., Mor~atsh.,81, 1098 (1950). (585) Zoss, -4.0. (to General Aniline & Film Carp.), U.3. Patent 2,555,179 (May 29, 1951). R E C E I V E Dfor review J u n e 25, 1952.
ACCEPTED July 8, 1952.
Pyrolysis of
'.
Coal and Shale !@g
CHARLES H. PRIEN
UNIVERSITY OF DENVER, DENVER, COLO.
Papers on coal pyrolysis during the past year have included discussions of the colloidal structure of coal, mechanism of swelling, function of the polar atoms present, and the kinetics of decomposition. The preparation of suitable blends for the oven and the effect of pulverization on coking have been noted. Fluidized bed coking and underground electrocarbonization are described, as is also pyrolysis b y dielectric means. Catalytic action of sodium compounds during low temperature carbonization and a rapid semicoking process employing superheated steam are mentioned. The substitution of calcium sulfate for acid in ammonia recovery is proposed, as is ethylene recovery b y selective solvent absorption. N e w methods of analysis for phosphorus have been devised. Underground gasification with oxygen has been suggested as a substitute for the Ljungstrom electrocarbonization of shale in Sweden. Little new research on the fundamental chemical nature of kerogen has been published. A fluidized vacuum retorting study, research on low temperature depolymerization in the presence of solvents, and an excellent paper on the role of nitrogen in shale oil hydrocarbon formation have been reported. A three-stage fluidization process of retorting has been patented. Hydrogenation studies on Colorado shale oil have been completed. A survey of methods of nitrogen determination in shale oil fractions has been conducted.
HIS is the fifth annual review of papers published in the field of coal and oil shale pyrolysis. Since the inception of this yearly summary in 1948 some 1130 references have been discussed in these pages. T h e growing list of articles which appear during each 12-month period is graphic evidence of the continued interest in this unit process and perhaps an adequate justification of the service which a review of this type can perform. Comments and criticisms as t o means by which this service can be improved and broadened are constantly sought and certainly u-elcomed.
T
I n keeping Rith previously estalilished policy all pertinent subject matter related to the general title has also been surveyed and included in the pages which follon-, T h e period covered, as usual, is primarily t h a t since June of the previous year.
COAL PYROLYSIS GENERAL
X number of general reviens of the field of coal carbonization have appeared during the past y a r . Birka (26) has described retort development in the gas industry over the past 100 years and noted t h a t thermal losses in the oven have been reduced by about 50% during this period. Cooke and Hutt (48)have examined present-day types of coking coal and the cokes therefrom, and the processes of carbonization. T h e relative fuel economy of the various carbonization processes, as vel1 as the raw materials and products suitable to each, in so far as both the gas and coking industry are concerned is indicated b y Townend (275). A history of developments in gas and fuel chemistry in America has appeared (79). See alp0 general reviews by Lang
