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INDUSTRIAL AND ENGINEERING CHEMISTRY
(100) Nelson, J. W. (to Sinclrtir Oil and Gas Co.), U. S.Patent 2,640,-
(101) (102) (103) (104) (105)
(106) (107)
(108) (109) (110) (111) (112) (113) (114) (115) (116) (117) .
I
(118)
(119) (120)
(121)
809 (June 2, 1953). Oil Gas J., 52, 136-137 (Sept. 14, 1953). Ibid., p. 66 (Nov. 9, 1953); p. 52 (Nov. 23, 1953). Ibid., pp. 174-8 (Jan. 25, 1954). Orr, R. J., and Williams, H. Laverne, J . Phys. Chem., 57, 92531 (1953). Orzechomski, A,, and AlacCormack, Can. J . Chem., 32, 388-451 (1984). Pahnke, A. J., and associates, 124th Meeting, AC8, Chicago, Sept. 6-11,1953. Pctrolezrm Processing, 8 , 971 (July 1953). Petyoleum Refi72er, 32, No. 6, 133-4 (1953). Ibid., KO.9, 154-8. Ibid., 33, 3-0,4, p. 184. Porter, F., Bumpus, AI., and Cosby, J. N. (to illlied Chem. & Dye Corp.). U. S.Patent 2,513,251 (June 27, 1950). Reidel, J. C., Oil Gas J . , 6G68 (Oct. 28, 1953). Rigon, Lino (to Les Usines de Melle), U. S.Patent 2,658,914 ( S o v . 10, 1953). Ruthruff, R. F., Petioleurn Refiner, 32,113-14 (1953); 33,1557 (1954). Salt, F. E., Chemistiy & I n d u s i i y , 1953, S-46-9 (.lug. 10, 1953). Satterfield, C. N., and Case, L. C.. IKD.ESG. C m x , 46, 9981001 (1954). Satterfield, C. N.. Wilson, R. E., and associates, I b i d . , 46, 100110 (1954). Saunders, R. H. (to Hercules Powdcr Co.), U. S.Patent 2,644,014 (June 30, 1953). Schuber, John, and Kraske, W.4 . , Chem. Eng., 60, KO.9,205-7 (1953). Schweiteer, C. E. (to E. I. du Pont de Neniouis h Co.), U. S. Patent 2,644,837 (July 7 , 1953). Seubold, F. H. (to Shell Development Co.), Ibid., 2,633,476 (March 31, 1953).
Vol. 46, No. 9
(122) Seubold, F. H., Jr., and S’aughan, W. E., J . A m . Ci~e7n.Soc., 75, 3790-2 (1953). (123) Shelmerdine, J., and associates, J . A p p l . Chena., 3, 513-21 (November 1953). (124) Shelton, J. R., and Cox, W.R., IKD.ENG.CHCM.,46, 818-23 (1954). (125) Shelton, J. R., Kherley, F. J., and Cox, IT.L., I b i d . , 4.5, 2080-8 (1953). (128) Sherwood, P. W., Petroleum Pwcessing, 8 , 1348-54, 1543-5, 1722-8 (1953). (127) Sherwood, P . W..Petroleum Refiner, 32, 90-4, 1.41-4 (1953). (128) Ibid.. No. 4. 155-8 11953). (:29j Ibis., 32, KO. 12, 93-7 ii953); 33, NO. 1, 129-33; 33, NO. 2 117-22 (1954) (130) Skellon, J. H., Chemzstru & Imiusfiu, 1953, p. 1027-9 (Oct 3, 1953). (131) Skclly, J. F. (to hI. W,Rcllogg Co.), U. S. Patent 2,649,463 (Aug. 18, 1953). (132) Small, S . J. H., and Ubbelohde, .i.12., J . A p p l . Chem., 3, 193-8 (1953). (133) Smith, E. J., J . Chem. SOC.,1953, pp. 1271-5. (134) Sprauer, J. W. (to E. I. du Pont de Kernours & Co.) U. 6 . Patent 2,657,980 (Nov. 3, 1953). (135) Symonds, F.L. (to Standard Oil Co. of Indiana), Ibid., 2,631,094 (March 10, 1953). (136) Tabel, G. E. (to E. I. d u Pont de Semours & Co.) [bid.. 2,644 $4 1. (137) Thornton, D. P., Petroleum Processing, 8, S o . 7 , 1 0 4 1 4 (1953). (138) Titov, A. I., J. Gen. Chem. ( U S S R ) , 22, 1373-5 (1952). (139) Toland, W.G. (to California Research Corp.), U. S. Patent 2,623,073 (Dee. 23, 1952). (140) Waloutt, C., and associates, 124th Meeting, hCS, Chicago, Sept. G-11, 1953. (141) Weiss, J. AI., Chem. Eng. News, 32, KO. 18, 1820 (1954). (142) Zapp, R. L., and Gessler, A. M., Rubber A g e , 74, No. 2, 243-51 (1953).
HERBERT F. WIEGANDT and RAYMOND G. THORPE SCHOOL OF CHEMICAL AND METALLURGICAL ENSINEERING, CORNELL UNIVERSITY, ITHACA, N . Y.
The number of 1953 publications dealing with polymerizations is approximately 15% fewer than for the previous year. Increased polyethylene production i s alleviating the scarcity of this product. The use of resins in the manufacture of structural items, such as chemical process equipment, as well as the much publicized plastic automobile body, may be another transition in the growth of the industry. Continued interest in synthetic fiber development is indicated b y the large number of formulations For this purpose.
HE most talked about development in 1953 relating t o products of polymerization is the fibrous glass reinforced polyester automobile body. Public enthusiasm has continued t o expand, despite the controversy over mass production economies as compared with steel. Advances in the technique of vacuum forming are contributing t o the expanding use of thermoplastics for signs and displays. High impact polystyrene is being received favorably, and a rapidly increasing portion of the styrene resins is of this type. Rigid polyvinyl chloride, reinforced polyesters, and others are receiving attention in the chemical industry for use as corrosion-resistant pipe and other structural items. Polyethylene output increased sharply as the first of a series of large units went into operation. The predictions are t h a t plastics, rubbers, and coating materials industries will continue t o grow a t a rapid rate. A few fibers faced the slump of the textile industry and also had some production difficulties of their own. Vinyl cyanide polymers and isocyanate polymers show signs of interesting developments. T h e number of publications dealing with the unit process of polymerization has decreased somewhat. The previous review of this series (W5A) for 1952 covered 557 references; 466 are cited
for 1953. This review cover? 1053 material directly related to the unit process of polymerization, including general theory, reaction mechanism and kinetics, effect of all types of addition reagents on reactions, reaction conditions, processes, apparatus, and existing plants. It does not include publications dealing exclusively with production statistics, uses, applications, structural properties, or modifications of high polymers. Many of the references cited, however, are in part devoted t o such subject matter. The development of polyethylene manufacture wab reviewed by Raine (19A). Lever ( I 2 A ) reviewed ethenic copolymerization and Langlois ( Z I A ) considered the various olefin polymerizations with acidic catalysts. Allyl resins were covered by Lynn ( I 3 A ) . Jacini (8A ) wrote about the copolymerization reactions between olefins and drying oils. Ionic polymerization studies leading t o butyl rubber n-eI e reviem-ecl by ;Idams and Buckler (Id). Cooper ( b A ) , Landler (10.4 ), and Fisher ( 6 A ) discussed developments and process variables for synthetic elastomers. Parker ( 1 6 A ) considered emulsion polymerization. Cooper ( 4 A )reviewed the action of various polymerization catalysts and initiators. Polycondensation reactions, including kinetics, mechanism, and structure, were covered b y Champetier (SA), Korshak (OA), and Powers (17A). Goldstein ( 7 A ) reviewed melamine resins. T h e chemistry and polymerization mechanics of polyesters were
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INDUSTRIAL AND ENGINEERING CHEMISTRY
interpreted by Saccenti (ZOA). Specific attention to the fibrous superpolymers was given by Moncrieff (14.4.).
CATALYSTS, ACTIVATORS, MODIFIERS, AND INHIBITORS The formation of low molecular weight polymers in the petroleum industry is accomplished by the proper selection of catalyst and reaction conditions. Corner and Lynch (16B) described the preparation of an olefin polymerization catalyst having high activity and excellent structural strength from heat treated silica gel and orthophosphoric acid. Various unsaturated hydrocarbons were polymerized by Wadsworth (46B), using a boron trifluoride-iodine catalyst combination. Shiba and Ozaki (S5B) studied the catalytic activity of a nickel oxide-clay catalyst in the polymerization of ethylene. Although i t is recognized that the catalyst acts to initiate an addition polymerization reaction by a free radical or ionic mechanism, as opposed to true catalytic action, many authors do not distinguish between catalysis and initiation. This review, therefore, draws no distinction between a catalyst and an initiator. As in past years, those free radical initiators which bring about monomer activation, such as per compounds, azo compounds, and Grignard reagents received some attention. Cooper ( I 4 B ) studied the effect of hydroperoxide structure on the initiation of styrene polymerization and found t h a t aryl groups gave more rapid initiation. Yurzhenko (52B) made a similar study, using tertiary hydroperoxides. The use of organic hydroperoxides in combination with a metallic drier for rapid room temperature polymerization of unsaturates was discussed by Hoppens (24B), while McKennon and Lawrence (29B) suggested hydroperoxy substituted rosin derivatives as initiators. Peresters of nonaromatic carboxylic acids and tertiary alkyl hydroperoxides wer" recommended as catalysts for vinyl and allyl compounds (JIB). Shusman ( 3 7 B ) obtained styrene polymers and copolymers with low residual monomer and low methanol solubles and increased resistance to yellowing and crazing with mixed peroxide catalysts. Sodium 1-tert-butyl-1-monoperphthalatewas used as a catalyst for the emulsion polymerization of styrene ( S B ) . Patterson ( S S B )obtained high molecular weight (up to 220,000) polyacrylonitrile with a peroxydisulfate as the sole catalyst. Methacrylate esters were polymerized to give lube oil additives with a benzoyl peroxide-benzoin-ferric laurate catalyst (42B). Cooper ( I S ) considered the initiation of vinyl polymerization via the decomposition of azo compounds in water by metallic ions; the use of diazonium fluoborates was also presented (SOB). Kolthoff and Dale ( M B )employed ferricyanide-diazo thioethermercaptan initiators in styrene-butadiene copolymerizations. Willis and his associates (60B)described the influence of various diazo initiators on the structure of a 70 :30 butadiene-styrene copolymer made a t 122" F. Stewart ( S 9 B ) formed ethylenic polymers with various redox catalysts, using polyamines. Alkaline nitroprusside-hydroperoxide recipes for the redox emulsion copolymerization of butadiene and styrene were published (27B). Other initiators for GR-S include autoxidized methyl oleate and methyl linoleate ( Q I B ) ,a polyamine carbamate (46B), and hydrazine plus a polyamine carbamate (44B). Underwood and Hill (4SB) utilized a chlorite-sulfite redox system for the polymerization of vinyl chloride. Folt (19B) employed potassium persulfate and silver nitrate in the absence of surface active agents. Smaller and more uniform beads were produced in the suspension polymerization of vinyl and vinylidene monomers with a water-soluble persulfate catalyst (d3B). Stewart (4'33) proposed the use of ferrous gluconate plus an aryl alkyl hydroperoxide or a chlorobenzoyl diperoxide as a redox polymerization catalyst for vinylidene compounds. Caldwell ( 9 B )described the suspension polymerization of vinyl monomers. Park ( 3 B ) examined various vinyl halide polymerization catal y s t ~ ,including succinyl peroxide. Several references dealt with photosensitized systems. Wood-
1871
man (FIB)polymerized methyl methacrylate in aqueous emulsion a t room temperature by glow discharge electrolysis to obtain a 75% yield of polymer in 1 hour in the absence of a catalyst additive. Howard (26B) produced ethylenic polymers by irradiation in the presence of diazo compounds. Bromal, desyl chloride, and desyl bromide were cited as photopolymerization catalysts for methyl methacrylate and styrene (34B). Hicks and Melville ( 2 f B )worked out a technique for external irradiation of the monomer and photosensitizer in the mass polymerizations of styrene. Brown ( 8 B ) developed a low temperature peroxamine polymerization in aqueous emulsion using ammonia. Calfee (IOB) obtained higher yields in the low temperature catalytic polymerization of iso-olefins with a hydroxylated aluminum halide catalyst in an organic halide solvent than with the usual FriedelCraftk catalyst. Boyd (6%) carried out ethylene polymerizations and copolymerizations with 2,2-bis(tert-butylperoxy)butane as catalyst. Carnahan (11B) found t h a t metal molybdite catalysts could be used for the addition polymerization of ethylenic monomers in lieu of peroxides. DeTar and Savat ( I 7 B ) found the action of N-nitrosoacetanilide as a polymerization initiator to be cationic. A number of aromatic hydrocarbons were selectively oxidized by Connor and Lohr ( I I B ) and found to be effective as polymerization catalysts. A mixture of benzenesulfonyl chloride and trichloroacetic acid was utilized as a room temperature catalyst for self-hardening furan resin compounds (18B). Various arsenites were used in small amounts as activators (48B),and Williams and Mitchell (4923) prepared a ferrous complex of (ethylenedinitro1o)tetraacetic acid as a catalyst activator for cold rubber polymerizations. Admixtures of phosphoric acids supported on silica gel and nickel and copper phosphates were employed as promotors for olefin polymerizations (38B). Hamilton ($OB) examined the effect of silver ion as a promoter in the aqueous persulfate-bisulfite redox polymerization of chlorotrifluorethylene. Ethylene oxide was advanced as an accelerator for the hydrogen peroxide catalyzed polymerization of vinyl chloride (5SB),while Lee (28B) found heterocyclic amines effective as accelerators for the polymerization of vinyl or allyl monomers. Antlfinger and Lufter ( 2 B ) discussed the use of shortstops in GR-S polymerizations. Sodium dimethyldithiocarbamate in combination with sulfur or polysulfides was developed as a nondiscoloring shortstop (1B). Breitenbach and Fally ( 7 B ) compared the retardation of methyl acrylate polymerization by various quinones. Few new polycondensation catalysts appeared in the literature this year. Billica (5B) produced polyethylene terephthalate, using antimony trioxide; cobaltous acetate ( 2 M ) and metallic cerium and its oxides and alloys ( 4 B ) were mentioned for the same purpose. West ( 4 7 B ) accelerated the curing of aminoplasts with nitro aliphatic esters of phosphoric acids. Shokal and associates ( J 6 B ) prepared polyethers containing nitrogen for use in curing glycidyl polyethers.
REACTION MECHANISMS AND KINETICS The complex reactions t h a t form macromolecules have again been explored by many workers. I n some instances the observations have been simultaneous with the development of new techniques or materials. Melville (62C) discussed in general the cross-linking reaations of resins, while Rehner (65C) considered the relation between rate constants, frequency factors, and activation energies. Barb ( 7 C )studied the reactivity of polymeric free radicals. Chain transfer studies were carried out by Fox (JSC) and Kapur (46C) and were discussed by Wheeler ( S I C ) . The behavior of alfin catalysts was described by Cooper ($$C). Russell and Tobolsky (67C) studied the thermal polymerization of styrene, while the mechanism and rates for several different
e
1872
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
catalysts v m e investigated by Clark (18C), Dainton (27C), Garten ( 3 7 C ) , Jordan (44C), Peppcr ( 6 1 C ) , Pepper and Sommerfield (62C), Park (58C-6OC), and Plesch ( 6 3 C ) . Rates in the suspension polymerization of styrene were reported by Kaghan and Shreve (45C). Koton ( 4 8 C ) compared the polymerization of o-vinylbiphenyl with that of styrene. The relative reactivities in the copolymerization of styrene with substituted styrenes (67C) and with other vinyl compounds (64C) were investigated. Immergut (4ZC) explained the formation of a popcorn nucleus as a free radical process. T h e use of urea complex formation was suggested for the investigation of polymerization of long-chain monomers by Swern and Port (77C). Mechanisms for vinyl polymerizations were analyzed by Bamford, Barb, and Jenkins (SC). Vinyl chloride and vinylidene chloride polymerizations catalyzed b y bis(methylsulfony1) chlorides were studied b y Jones and Friedrich (43C). Burnett and FJ7right ( 1 5 C ) determined the kinetics of polymerization for vinyl benzoate and vinyl propionate. A two-stage catalysis for vinyl monomers was considered by D'Alelio (26C). Initiation rates for vinyl polymerizations were discussed by Tobolsky and Baysal (79C). Koton and Kiseleva ( 4 9 C ) related the structures of vinyl derivatives of naphthalene to their reactivity. Thermal and photo catalysis were used by Bamford and Jenkins ( 4 C ) , x-rays by Collinson and Dainton ( 1 9 C ) , and gamma rays by Berstein and associates (9C)in analyzing the kinetic behavior of acrylonitrile. Dickey and Coover (30C) considered alkyl acid phosphites for ethylenic polymerizations. Corner and Lynch ( 2 4 C ) observed the effect of modifying a deposited phosphoric acid catalyst and Saylor (69C) observed the influence of chlorofluorallranes as solvents for aluminum chloride in the polymerization of olefins. The general reaction mechanisms in the polymerization of ethylene and propene were summarized ( S 4 C ) . Special interest was aroused by the irradiation of polyethylene by Charlesby ( 1 7 C ) in which cross linking takes place. Seitzer, Goeckermann, and Tobolsky ( 7 0 C ) made a rate study of p r a y induced polymerization of qtyrene and methyl methacrylate. R a t e studies of polymethacrylate formation were made by Burnett and associates (I.@, 16C) and by Conix and Gmets (21C). Bonsall, Valentine, and Melville ( 11C) investigated the termination step in the polymerization of methyl methacrylate. llelville and Watson ( 6 3 C ) found that polymethyl methacrylate initiates the monomer reaction. The inhibiting action of oxygen in polymerization Tvas studied by Smeltz and Dyer (73C), using acrylonitrile, by Rutovskil (68C),using methyl methacrylate, and by Gregg and Mayo ( 3 8 C ) , using styrene. Rate studies in the polymerization of chlorotrifluorethylene were carried out by Elliott, Meyers, and Roedel (S5C) and by Thomas and O'Shaughnessy ( 7 8 C ) . Klaasens and Gisolf ( 4 7 C ) found explosive reactions with styrene and indene a t extreme pressures. The influence of temperature x i s correlated by Condon (20C) for the polymerization of butadiene and by Cragg and Fern ( 2 5 C ) for the low temperature copolymerization of butadiene and styrene. Morton, Salatiello, and Landfield (64C) determined a propagation rate constant for butadiene. Other kinetic Ftudies of the butadiene-styrene copolymerization were those of Brown and IF'inkler ( I W C ) , Helin and coworkers ( Q I C ) ,and Stewart and Williams (76C). I n other reactions utilizing styrene as a copolymer, Rehner, Zapp, and Sparks ( 6 6 C ) used isobutene in a low-temperature study, Barb ( S C ) , using sulfur dioxide, observed depropagation reactions, and K u t (6OC) discussed the action of unsaturated fatty acids. BoelhouiTer (1OC) studied the polymerization of linseed oil with sulfur dioxide as a catalyst. A reaction mechanism for the copolymerization of ethylene and carbon monoxide was suggested by Barb (6C). Hayes (4OC) reported on graft copolymerization between vinyl monomer3 and vinyl polymers. Alfrey and Berdick (2C) studied cross linking in the copolymerization of vinyl acetate with a diallyl ester.
Vol. 46, No. 9
I'arious activities and solut,ion behavior were compared by Aggarwal and Long ( 1C ) for combinations of copolymers taken from methyl acrylate, 2-viriylpj-ridine. and dichlorostyrene. T h e mechanism of phenol-formaldehyde condensations vias studied by Durr and Wendling ( S I C ) , Ehlers (32C, f9SC), Sofcr, Dietz, and Hauser (75C), who used ult,rasonic pulse propagations in their study, Davis, Hayes, and Hunter (29C), H a Xeville ( S S C ) , Oschatz (56C),and Briigel ( 1 3 C ) . The last two vorkers also reported on urea-formaldehyde. Bender (8C)compared the reactivity with formaldehyde of various isomeric biphenols. Investigations concerned with the rate of urea or melamine condensations m r e those of Cordier (%E), Smythc (74C), and Wohnsiedler ( 8 2 C ) . The following workers investigated the kinetics of polyester formation-Davies and Hill (28C),Lombard (61C), and Shkol'man and Zeldler (71C, 72C, 8SC). Vergoz (80C)reported on the kinetics of polyamide formation from an amino acid. Sarracott (65C) discussed epoxide resin mechanisms.
ETHYLENIC POLYMERS Although polyethylene is of great current interest and sevcral plants are under construction, with more projected, to make this one of the fastest growing polymeric materiais, very little basic information has been published on the polymerization of ethylenr. Peters and Evering ( 2 0 2 0 ) polymerized et'hylene in the vapor phase a t 1000 pounds per Equare inch over cobalt deposited 011 carbon t o obtain low yields of high polymers. Barry ( 1 2 0 ) incorporated a free radical catalyst and water in a high t'emperature, high pressure polymerization of ethylene. Lipscomb ( 7 5 0 ) investigated the polymerization reactions between sulfur dioxide and carbon monoxide with ethylene. Schneider and Brakeley ( 1 1 6 0 ) observed the inhibitory effect,.: of n-butenes on the low temperature polymerization of isobutene. Schneider and Goering ( 1 1 7 0 ) selectively polymerized isobutene from an unsaturated refinery naphtha. De Vault ( S 6 D ) found that palladium on silica-alumina was an effective catalyst for producing gasoline from low boiling olcfins. Aluminum chloride was used as the catalyst by Garber and Sparks ( 4 4 0 ) for making unsaturated polymers from diolefins and by Heinrich ( 6 0 0 )for polymerization of heavy alpha olefins. Bloch ( 1 9 0 ) used hydrofluoric acid for the polymerization of polyolefins and Pines (103D) included cycloparaffins as a reactant to give nonaromatic cyclic polymers. Kaufman and William( 6 9 D )produced acenaphthalene resins by thermal polymerization. Brothman ( 2 1 0 ) obtained good optical properties for polystyrene by catalyst selection and thermal control. Park (9513) recommended catalysts and conditions for emulsion polymerimtion. Styrene was also polymerized using aluminum chlorid(, ( 1 2 6 0 ) and ferric and stannic chloride ( 1 2 3 0 ) . Several othcr vinyl aromatic compounds were polymerized-Werkema (14211) used a-methylstyrene catalyzed by sodium; Henson ( 6 1 D ) cited advantages of vinyltoluene over styrene for use with polyesters ; Milne, Faulkner, and Hollis ( 8 9 0 ) derived polymers from p vinylbenzamide; and Dickey and Stanin ( 3 8 0 ) used a sulfamyl styrene to obtain a heatiresistant product.. A series of styrene copolymers were produced-Barb ( 9 0 ) used sulfur dioxide; Barrett ( 1 1 0 ) and Bamford ( 7 D ) used maleic anhydride; Amos and Miller ( S D ) used a-methylstyrene; Bilton and Segall (27L)) used acrylic and related acids; Ross and Markarian ( 2 1 1 0 ) used a trichlorotrivinylbenzene; Tobolsky and Baysal ( 1 3 8 0 ) used disulfides; indene-coumarone ( 6 S D ) was used; and unsaturated esters ( 9 3 D ) Kere used to give a product reactive with drying oils. Sparks and Young (125D) prepared a tripolymer from a polyene, alkene, and styrene, and Long ( 7 6 0 ) combined styrene with an unsaturat,ed rubber and unsaturated dimers. Heatresistant polymers were obtained by Schulken and Boy ( 1 1 9 0 ) from methylstyrene and methacrylonitrile. Wehr and Kagle (1400)found that good flovi properties were obtained when dimeric a-alkenyl styrenes were used with styrene and acryloni-
September 1954
I N D U S T R I A L A N D E N G I N E E R I WG C H E M I S T R Y
trile polymers and copolymers. A number of copolymers of o- and rn-vinylphenols with vinyl monomers, dienes, unsaturated acids, and drying oils were produced ( 2 0 0 ) . Synthetic drying oils were obtained by Gleason ( 4 8 0 ) from butadiene, styrene, and a little maleic anhydride, by Carlin ( 2 6 0 ) and Tawney (183D) from styrene and unsaturated esters, and by Nelson and Gleason ( 9 1 0 ) from styrene, isobutene, and cyclopentadiene. Several studies were conducted on the polymerization of vinyl chloride in aqueous dispersion of Bankoff and Shreve ( 8 0 ) , Hohenstein, Haward, and Elly ( 6 2 0 ) , and Park ( 9 8 0 ) . Vinyl chloride was also first polymerized in emulsion and then copolymerized with other ethylenic monomers ( 9 4 0 ) . Drinberg and Bocharova ( 3 9 0 ) studied the formation of tridimensional polyvinyl chloride by means of thermal treatment. Shekleton (1220) produced a polyvinyl methyl ether a t low temperatures. The copolymerization of vinyl acetate with cyclic disulfides was studied by Stockmayer, Howard, and Clarke (2300). Vinyl acetate was copolymerized with maleic anhydride by Upton (1590) and with unsaturated amino compounds by Marsh (810). Copolymers of vinyl chloride and vinylidene chloride were produced in emulsion a t low p H by LeFevre and Mall ( 7 3 0 ) . Rolf ( 1 4 4 0 ) combined three monomers, vinyl chloride, vinyl acetate, and 2-ethylhexyl acrylate. McGrew and Pinkney ( 7 9 0 )polymerized vinyl monomers with acetylene a t elevated pressures. Allyl esters of stabilized rosin acids were copolymerized with ethylenic compounds by Gould (49D),and diallyl esters of dimerized unsaturated fatty acids were copolymerized with diallyl phthalate ( 9 5 0 ) . Tawney ( 1 3 6 0 ) produced an unsaturated interpolymer from diallyl esters and allylic alcohols or chlorides. Several ethylenic unsaturated compounds were copolymerized with vinylidene cyanide. Gilbert and Miller ( 4 6 0 ) used alkyl vinyl ketones and dichlorodifluoroethylene; jointly with Folt ( 4 7 0 ) , they used esters of unsaturated acids in a multistage operation; and Carlson ( 2 7 0 ) used unsaturated acids. Acrylonitrile and its copolymers again maintained the interest of a number of investigators, who in many instances incorporated relatively small amounts of dye receptive ingredients. Some of the monomers recommended were allyl amines by Chaney ( Z S D ) , allyl chloroacetate ( 5 5 0 ) and heterocyclic monomers containing nitrogen ( 5 6 0 ) by Ham, unsaturated derivatives of nicotinamides by H a m and Craig ( 5 8 0 ) , unsaturated imines by Kropa and Malmberg (70D), allyl alcohol by Kropa and Nyquist ( 7 1 D ) , 1-butene derivatives by Lytton ( 7 8 0 ) , vinyl amino aromatics by Padbury ( 9 7 0 ) ,vinylpyridine b y Rothrock (1120),formylated polyvinyl alcohol by Stanin and Dickey ( 1 2 7 0 ) , and acryloylalanyl methanediamines by Zerner and Pollock ( 1 4 6 0 ) . Similarly, Culhane, and Rothrock ( 3 3 0 ) incorporated vinylpyridine in a copolymer of vinyl chloride and acrylonitrile. Stiehl (1290) studied the copolymerization of acrylonitrile with butadiene. Alkyl esters of allyl phosphonic acids were used by Dickey and Coover ( 3 7 0 ) and allyl chlorides were used by Caldwell ( 6 6 0 ) for copolymerization with acrylonitrile. Price copolymerized the following with acrylonitrile-N-alkenyl-o-alkylisourea (1060), unsaturated quaternary ammonium compounds (1070), and n’-alkyl-o-allylisourea (1080). Basdekis (130)carried out emulsion copolymerization of acrylonitrile with vinyl acetate in the presence of mercapto monocarboxylic acids. Coover and Dickey ( 2 9 0 ) polymerized acrylonitrile in a polyvinyl acetate emulsion. Stanton and coworkers (1280) polymerized acrylonitrile in solution with nonsolvent salts present in an aqueous phase. Acrylic polymers received somewhat less attention than in recent years. Leonard, Szlachtun, and Cort ( 7 4 0 ) studied the polymerization of acrylates using sodium in liquid ammonia. The effect of water on the induction period for methyl methacrylate was reported by Schoonover, Brauer, and Sweeney (1180). Burnett and Nordlander ( 2 4 0 )oxygenated acrylic ester monomers as a preliminary step; another technique ( 9 2 0 ) calls for complete absence of oxygen but with free radical generation by means of rupturing existing polymers by agitation. Polymers of sev-
1873
eral acrylic acid derivatives were prepared. Ellery and Todd ( 4 0 0 ) polymerized a hydroxymethyldioxolane ester of acrylic acid. Tessmar ( 1 3 7 0 ) investigated the preparation and polymerization of or-chloroacrylates, Patai and associates (1000) polymerized aryl methacrylates and N-arylmethacrylamides. Copolymers of methacrylic acid and methacrylamide were studied by Pinner ( 1 0 4 0 ) . The ester derived from sodium glycerophosphate and methacrylic chloride was polymerized to give an adhesive ( 3 5 0 ) . Alfrey, Overberger, and Pinner ( 2 0 ) investigated the copolymerization behavior of methacrylic acid, diethylaminoethyl acrylate, and acrylonitrile. Bauer, Seher, and Van Horne ( 1 4 0 ) found that maleic esters copolymerized with polyalkyl methacrylates to give pourpoirit depressants. Drying oils may be produced by a n ethylenic cross-linking polymerization of unsaturated polyesters. The following investigaBrunner tors used styrene as a cross-linking agent: Arvin (6D), (22D), Griess (530), Kass ( 6 8 0 ) , Meeske (83D), and Rubens and Boyer (1130). Styrene and fatty acid drying oils were copolymerized by -4rmitage ( 4 0 ) , Greiss and Teot ( 5 4 0 ) , Kanning and Hartmers ( 6 6 0 ) , and Sample ( 1 1 5 0 ) . Geiser ( 4 6 0 ) used polymer gasoline in place of styrene. Unsaturated polyesters were also crosb linked by D a y and Affleck (340),who used triallyl cyanurate and Rust and Canfield ( 1 1 4 0 ) , who used vinylimides. Since vinylimides do not polymerize above their melting point, the latter produce has a long shelf-life when stored hot. Styrene, maleic anhydride, alcohols, and drying oils were copolymerized (ID) Swern and Jordan (1320) combined diallyl phthalate with allyl esters of fatty acids. Harman and Stiles ( 5 9 0 ) polymerized unsaturated esters of phosphonoalkyl ethers. Divinylbenzene was used as a cross-linking agent by Seymour ( l 2 1 D ) in the copolymerization of styrene and maleic anhydride Welch (141D ) prepared copolymers from divinylbenzene and isobutylene. Loshaek and Fox ( 7 7 0 ) investigated the use of divinyl compounds for the cross-linking copolymerizations of methyl methacrylate and similar compounds. The various polymers containing fluorine are grouped together. I’rober (109D) made an extensive study of the preparation and polymerization of fluorinated styrenes. Miller copolymerized tetrafluoroethylene with chlorotrifluoroethylene ( 8 7 0 ) and also prepared solid polychlorotrifluoroethylene (860). Polymerization conditions for the latter compound were investigated by Miller and Maynard (88D),and it was copolymerized with I-chloro-1-fluoroethylene by Pearson (1010). Other fluorinated polymerizations were investigated by Berry (150), who produced a dispersed polyfluoroethylene, by Bittles ( 1 8 0 ) , who used fluorinated alkyl acrylates, by Lawson ( 7 2 0 ) , who used vinyl chlorotrifluoroethyl ether, and by Miller and Calfee (840), who polymerized vinylidine fluoride. Folt and Carlson ( 4 3 0 )made interpolymers of dichlorodifluoroethylene, butadiene, and vinylidene chloride. Sulfur dioxide was copolymerized in emulsion with olefins by Crouch and Cotton ( S I D ) ,Crouch and Harris ( 3 2 0 ) ,and Howe ( 6 4 0 ) . Sulfur dioxide was copolymerized with butadiene ( 0 6 D ) Strain (1310) copolymerized diallyl phthalate with N-substituted maleic acid imides. Coover, Dickey, and Shearer (SOD) polymerized 3-methylenephthalide. N-vinylcaprolactam wap polymerized ( J 2 4 0 ) . Tawney ( 1 3 4 0 ) obtained copolymers from trichloroalkenes and other ethylenic monomers; from 2-alkenyl2-alkenoates with 2-alkenyl chlorides he obtained unsaturated curable products (1350). Gregg ( 5 0 0 ) prepared flame-resistant copolymers from 2-alkenoxyalkyl esters and bromomethanes. Radzitzki and Smets ( 1 1 0 0 ) studied the polymerization of 1and 2-phenylbutadiene. Marvel and Wright ( 8 2 0 ) investigated a series of copolymers derived from dimethyl 1-propene-2-phosphonate and from 1-phenylvinylphosphonic acid. Gresham ( 5 1 0 ) obtained polymethylenes catalytically at high pressures from carbon monoxide, hydrogen, and water; similarly, Gresham and Hill ( 6 2 0 ) obtained long-chain alcohol.
1874
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
from butadiene and carbon monoxide. Xantor and Osthoff ( 8 7 D ) decomposed diazomethane catalytically to obtain polymethylene. Arundale and Banes (60)produced lubricant additive8 froin alkyl maleates and vinyl esters. Barney ( 1 0 0 ) prepared vinylidene bis(hydrocarbon sulfones) which then were copolymerized with other ethenic monomers. Ethylenimine was combined with unsaturated esters by Bestian ( 1 6 0 ) . Brus and coworkers ( 2 S D ) investigated the polymeric reactions of vinyl abietate. Engelhardt ( 4 1 0 ) suggested alkoxypentadienoic esters for use in copolymerizations. Ezrin and associates ( 4 2 0 ) prepared polymers from vinylhydroquinone and related compounds. Ham ( 5 7 0 ) polymerized amides derived from acryloyl chloride and cyclic amines. Polymers soluble in organic solvents were obtained by Hulse ( 6 5 0 ) from methyl isopropenyl ketone and butadiene. Marhofer and Hillyer (SOD) improved drying oils by copolymerization with butadiene. Miller and Rothrock ( 8 5 0 ) copolymerized acrolein with other unsaturates in the presence of a neutral alcohol. Resinous polyacetals were obtained by Neher and Bauer ( 9 0 0 ) with Friedel-Crafts catalysts a t low temperature from vinyl hydroxyalkyl ethers. Plas and Dijk ( 1 0 5 0 )prepared low molecular weight copolymers from olefins and unsaturated aliphatic carboxylic esters. Allyloxyphenyl isocyanates were polymerized by Wystrach (146D). Emulsifiable copolymers were produced by iT7ilson (1480) from salts of maleic acid monoalkyl esters with vinyl esters of aliphatic acids. Segall and Dixon ( I d O D ) polymerized 4-vinylcyclohexene diepoxide and used it to treat a styrene-acrylic acid copolymer.
ELASTOMERS St. John and Uraneck (ZZE) investigated the low temperature copolymerization of butadiene and styrene in emulsions containing highly soluble salts. Faragher ( 7 E ) reported on a process for the same high temperature copolymerization in emulsion or in solution of ethylbenzene, using dimerization of butadiene to 4vinylcyclohexene, followed by dehydrogenation of the vinylhexene and ethylbenzene to styrene. Alkali metals and alkali metal halides were used by Crouch (SE)to produce vulcanization plasticizers from 1,3-butadiene or isoprene, and by St. John (WIE)from pentadienes. A study (16E) was made of the copolynieiization of butadiene with cinnamic acid and other related compounds. Marvel and associates (18E)utilized the mutual GR-S recipe to copolymerize benzalacetophenone and other ketones with butadiene, replacing potassium persulfate with azobisisobutyronitrile as the initiator a t 50' C. Serniuk (d5E) copolymerized diolefins and aromatics below 0" C., using a Friedel-Crafts catalyst. Lynch (13-73) prepared elastomeric materials from the emulsion copolymerization of liquid polybutadiene, butene, and sulfur dioxide. Howland and Chambers (11E) made a superior arctic rubber by copolymerizing small amounts of a vinyl pyridine homolog with butadiene in emulsion. Improved tackiness and solubility were obtained by copolymerizing butadiene and methyl methacrylate in the presence of a natural rubber latex (6E). Fryling, Troyan, and Pritchard (10E) prepared high Mooney viscosity type rubbers from various aliphatic conjugated dienes and copolymerizable monomers in aqueous dioxan. Electrical grade rubber substitutes were obtained ( Z E )by the copolymerization of 1,3-butadiene with the adduct of p-vinyldiphenyl sulfide and B-vinylcarbazole. Marvel and Fuller (16E) described the polymerization of 2methyl-3-alkyl-l,3-butadiene. Parrish (d0E) developed vulcanizable copolymers having better processibility and lower cold flow than butyl rubber by replacing isoprene in the GR-I reaction with substituted fulvenes. Nuclearly di- and trisubstituted a-methylstyrenes were copolymerized in emulsion with monovinyl compounds, using cumene hydroperoxide as a catalyst ( 2 7 8 ) . Mahan (14E) prepared copolymers of styrene and isobutene for use as rubber plasticizers. Sparks and Thomas
Vol. 46, No. 9
(26E) employed solution polymerization with aluminum chloride to produce tripolymers of isobutene, cyclopentadiene, and divinylbenzene. Vulcanizable copolymers of acrylonitrile with acrylic esters ( 8 E )and alkyl acrylates with dienes ( 9 E )were reported, Several patents (ISE, B E ) covered elastometric isocyanatemodified polyesters. Seeger and coworkers ($423) discussed polyescttr urethans. Iwakura (12E) reacted tetramethylenebis(chloroethylurethan) and sodium monosulfide t o yield a rubberlike thiourethan. Bloch ( 1 E ) treated polyolefinic cyclic hydrocarbons with sulfur to produce polyolefinic rubber substitutes containing sulfur. David ( 4 E ) catalyzed the polymerization of cyclic disulfides with ammonia. Other rubbers were obtained by the copolymerization of vinylsulfonic acid derivatives with butadiene, isoprene, and styrene (1723). It was suggested that true polymerization occurs to a limited extent via free radical formation during the vulcanization of rubber ( 6 E ) .
CONDENSATION POLYMERS The number of published articles dealing with Condensation polymers showed a substantial decrease over 1952. Ravich and Frovola (72F) studied the thermal effects of resin formation in the acid catalyzed rpaction between phenol and formaldehyde. Redfern ( 7 S F ) reported that the initial product of phenol-aldehyde condensations may be advanced without reaching the insoluble, infusible stage by alternately solubilizing with alkali and condensing by heating to give an ethyl alcohol-soluble and watersoluble product. It was stated that the thermosetting character of phenol-formaldehyde resins could be reduced by progressive reaction with ethylene oxide (859'). Resins of improved flexibility and adhesion were produced by the reaction of a polythiol with phenol and formaldehyde (70F). Strum ( 9 1 F ) prepared coating compounds from phenol, cyclic ketones, and aldehydes, using a basic catalyst in alcohol. Smith, Cantrell, and Hill ( 8 3 F ) obtained thermoplastic resins from the reaction of phenol and formaldehyde with a soap. Vogelsang (968') developed resins t h a t cure rapidly with an alkaline catalyst from phenolaldehyde and ketone-aldehyde condensation products. Bloch (4F)made modified phenolic resins from a monoalkenylated phenol and isophorone, and also reacted aldehydes with the condensation product of phenol, alkyl aromatics, and conjugated dienes using an acidic catalyst (6F). Dalton ( 1 4 F ) treated sulfonated tannins n ith formaldehyde and added a filler to form water-resistant plywood adhesives. Frisch and Shroff ( 2 7 F ) prepared triorganosilyl bcnzaldehydcs, which can be condensed with phenols or used as modifiers in phenol-formaldehyde resins. A more efficient method of treating phenol with furfural was outlined by McDonald ( 5 S F ) . Gundermann ( S I P ) condensed xylenol and formaldehyde t o producc adhesives. Embree ( Z S F ) carried out the condensation of 3 acetylcoumarin with ketones and amine salts Gronich ( 3 0 F ) used a zinc dust-hydrochloric acid catalyst to produce paper wet-proofing urea-formaldehyde resins. Liquid urea-formaldehyde resins were described by Kise (4SP) and Xralnes ( $ I F ) . Water-soluble resins were obtained through the prcliminary condensation of urea with a polyhydric alcohol and further reaction with formaldehyde ( S F ) . Other resins were prepared by pretreating the urea with ammonia and then adding formaldehyde under acid conditions ( 4 9 F ) . James and Pings ( 4 0 F ) employed triethanolamine to obtain a cationic urea-formaldehyde condensate. Joffe ( 4 l F ) produced an alcoholmodified urea-formaldehyde resin with an acidified water-soluble sulfonate. Swan (928') formulated nitroparaffin-modified melamine-formaldehyde resins which gave films of good hardness and mar resistance. Barron (WF)reviewed the role played by saturated and unsaturated polyfunctional acids and polyhydric alcohols in the preparation of unsaturated polyesters. Oswald ( 6 9 F ) discussed the processing advantages in the use of dimethyl ieophthalate for alkyd manufacture.
September 1954
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
Linear polyesters were formed by Bock ( 7 F ) from dibasic acids derived from vanillin, and from phenyl propanes, ethylene glycol, and fumaric acid with hydroquinone as catalyst by Kass ( 4 S F ) . Cinnamoyl chloride was reacted with polyvinyl alcohol to yield a light-sensitive unsaturated polyester (488’). Sparks and Young ( 8 6 F ) produced plasticizers from polymerized unsaturated acids and polyglycols. Davis ( 1 5 F ) copolymerized diallyl maleate with the polyhydric alcohol esterification product of unsaturated dicarboxylic acids to give an unsaturated polyeRter which could be condensed with a phenolaldehyde resin. Drying gels were obtained by Cunningham and Polly (128’) from interesterified a-hydroxy acids and polyamines or polyalcohols. Alkyd varnish resins were developed from the reaction of unsaturated drying oil fatty acids and saturated polybasic acids with polyhydroxy and isopropylidenearyloxy alcohols (368’). Shokal and Devlin ( 8 1 F ) esterified allyl alcohol-styrene copolymers with fatty acids. Oil-modified alkyd resins made from degummed soybean oil, pentaerythritol, and phthalic anhydride were discussed by Marling and Hempel (598’). Kneisley (47F) utilized partial esterification of maleic acid with glycols for the production of heat-convertible, water-soluble alkyds. Sanderson ( 7 9 F ) employed monoalcohols of acids as terminating agents in the preparation of synthetic lubricants from diacids and glycols. Alderson ( I F ) polymerized hydroxypivalic acid to obtain fibers, while Mighton ( 6 1 F ) developed orientable fibers and stretchable films from the polymerization of E-caprolactam in a n inert atmosphere over an alkali metal hydride catalyst. The reaction of succinic acid with an aliphatic saturated dihydric alcohol was reported ( 6 8 F ) . Ross and Markarian ( 7 6 F ) condensed diacids with halogenated aromatics containing polyfunctional hydroxyl groups. Polyesters and polyamides were cross linked with N-acyl polylactams such as N,N’-terephthaloylbiscaprolactam (101F). Speck ( 8 7 F ) reported on linear polyamides as heat-stable, high molecular weight materials for filaments from disubstituted malonic acid. Kirby (45F)investigated the preparation of polyamides from the esters of mixed dibasic acids and diamines. MacDonald and Tullock ( 5 5 F ) made polyamides from several amino carboxylic acids. It was noted (54F)that the reaction product of methionine in dioxan polymerizes t o give a condensation polymer of an a-amino acid polyamide. Fisher and Wheatley ( 2 6 F ) produced a condensation polymer of hydrazine with a dicarboxylic acid and with Bates (66F) polymerized sebacic dihydrazide in the presence of hydroquinone to yield a polyaniinotriazol. Polyurethans were formed from his( chloroformates) and diamines ( 4 d F ) . Hermann ($58’) developed resins having very good mechanical properties without plasticizers from the condensation of polyphenols and organic polyisocyanates. Kerr and Hobbs (44P) suggested the use of starch suspended in formamide to give thermoplastics with silanes containing one reactive group and thermosetting resins with silanes containing two reactive groups. Nitzsche ( 6 5 F ) accelerated siloxane polymerizations with aluminum chelates. Polymerizable unsaturated silanes were made by the reaction between trichlorosilane and acetylene (58F, 97F) and from allyl chloride, silicon tetrachloride, and lithium or magnesium (568’). Winslow ( I O d F ) suggested the use and described the preparation of silyl aromatic compounds to produce polymers having good weathering properties. Silyl alcohols were polymerized by Speier (888‘); Nitzsche, Wilberg, and Hertrvig (678‘) hydrolyzed organosilicon halides, and Plueddemann (718‘) cited p,r-alkenylhalosilanes as monomeric reactants. Two patents (103’’ $ I F ) covered the preparation of thienyl-substituted polysiloxanes, while five dealt with methyl polysiloxanes (11F, 17F-I9FJ 66F). MacKenzie and Schoffman (67F) obtained silicones from acyl silanes. Rust (77P) examined copolymers of trichlorosilane and alkylchlorosilanes, while Hunter and Rauner ( J 7 F ) used polybasic acids and a silane alcohol polymer, and Hurd ( 3 8 F ) employed vinylhalosilanes and alkyl- or arylhalosilanes. Other polymers were prepared from aryl- or alkyldialkoxyhalosilanes and glycols
1875
or hydroxy acids ($OF). Sommer (85F) cleaved ketosiloxanes with sulfuric acid and hydrolyzed the sulfates to polysiloxanes. Wrtrrick ( 9 8 F ) polymerized octamethyltetrasiloxane using alkali metal alkaloids and alkali hydroxide complexes as catalysts. Hatcher and Bunnell (34F) prepared resins containing Si-R-Si a procedure for organosiliconlinkages and also patented (39’) modified alkyd resins, Rust (788’) recommended cohydrolysis and codehydration of alkoxysilanes or silicohaloforms with an organic silicohydroxide or halide for the preparation of resins having high heat stability and chemical resistance. Other monomeric materials including silylphenols ( 8 9 F ) , trifluoromethylphenylsiloxanes ( d 8 F ) , and highly condensed siloxanes from the treatment of diorganosiloxanes with alkali in the presence of a nitrile or a substituted amide ( S Q F ) . Dearborn and associates (1627) studied the reactions between polyglycidyl ethers and acid anhydrides to form epoxy resins. D’Alelio ( I S F ) used a Friedel-Crafts reaction to polymerize chloroepoxyalkancs with chloro- or alkyl-substituted phenolaldehyde condensate. Kropa and Thomas (508’) condensed aqueous glyoxal with pentaerythritol, using a sulfuric acid catalyst to yield textiletreating resins. Gresham and Bell (298’)formulated a condensation polymer of trioxepane from formaldehyde and 1,a-dioxalane. Polymer oils formed from aromatic hydrocarbons and formaldehyde under pressure with a catalyst were presented by Feasley (84F). Thermosetting resins were prepared from a heat-hardenable phenol-aldehyde condensate and an ether-type resin obtained from the reaction of a dihydric phenol and a dihalide of polyethylene glycol ( 2 d F ) . Bock and Carlson ( 8 F ) described clear, colorless, thermosetting phenol ether resins obtained from the condensation of dihydric alcohols. Acetaldehyde was polymerized t o a linear polymer with peroxides a t its freezing point (842). Nielsen ( 6 S F ) eliminated some of the problems in the direct polymerization of furfural alcohol by preparing polymers of 12 units which could then be further polymerized. Lantz and Walters ( 6 d F ) worked out a two-stage polymerization of furanacrolein, furfural, and formaldehyde. Bloch and Mammen (68’) condensed benzodihydrofurans with aldehydes and ketones to form thermoplastics. Whetstone and Ballard (100F) investigated the acid-catalyzed reaction of dihydropyrancarboxaldehyde with polyhydroxy compounds. Stoecker and Keil ( 9 0 F ) treated animal protein with aniline and formaldehyde to form thermoplastics. Thurston ( 9 5 F ) reacted aldehydes with the condensation products of triazine derivatives and polyhalogenated compounds. Rose and Swain ( 7 5 F ) heated bis(dicyandiamide) with a diamide to obtain polymeric biguanides. Morgan (61F) insolubilized polymers containing tertiary nitrogen in the chain with compounds containing polyfunctional halogen groups. Boyd and Walter ( 9 F ) obtained thermosetting resins from the condensation of 3-amino-5-pyrazolone with aldehydes or ketones. May and coworkers ( 6 0 F ) treated aliphatic dithiols with formaldehyde to form polymercaptals, convertible to more stable sulfones by heating. Resins were made from thiophene and formaldehyde with ammonium halides and a modifier (80F). Thompson ( 9 S F ) examined the acid-catalyzed reaction of salicylaldehyde and mercaptans, as well as the condensation of dibenzylacetone and hydrogen sulfide in ethyl acetate, using piperidine as a catalyst (948’). Simons ( 8 3 F ) used the basic polymerization of epichlorohydrin and various sulfonamides to form thermoplastics. Linear polyethers were obtained by condensing difunctional phenols with toluene sulfonyl esters of glycols (74F). Waters and Wilson ( 9 9 F ) were able to prepare fiber-forming polythioureas from low purity materials by using multistage heating of carbon disulfide and diamines in the presence of water. PROCESSES, EQUIPMENT, AND P L A N T S The trend in process improvement through the development of continuous polymerization processes continued in 1953. Tegge
1876
INDUSTRIAL AND ENGINEERING CHEMISTRY
( t 7 G ) proposed a continuous three-stage process for the copolymerization of styrene and isobutene a t low temperatures. Feldon, McCann, and Laundrie ( 6 G ) operated a tubular reactor on a pilot plant scale to produce GR-S a t 122" and 41" F. Ronay and Vinograd (2.iG) obtained a patent for the continuous aqueous suspension polymerization of unsaturated compounds. Wenning ( 3 I G ) Forked out the details for the continuous redox polymerization of acrylonitrile. Richards (24G) was succeseful in controlling the molecular weight of polyacrylonitrile by the use of continuous reactant addition and polymer removal. The details of a continuous process for the preparation of phenol-formaldehyde resins were given (4G). Wallman (29G) avoided the necessity for dispersing an aqueous sirup of partially condensed products in a n organic nonsolvent b y the continuous suspension polymerization of ion exchange resins. Pryor, Harrington, and Druesedow (23G) made drastic reductions in the reaction time for cold GR-S in plant operatZion by using improved recipes. Various antifreeze diluents were compared for use in cold GR-S polymerizations ( I d G ) . Vandenburg (28G) worked with several emulsifiers and catalyet,s in the l o ~ v temperature polymerization of unsaturated compounds. High acid copolymers of butadiene and acrylic acid were prepared using Triton X-301 instead of soap ( 7 G ) . Sozaki (2GG) partially polymerized methyl methacrylate a t 100" C. and then completed the polymerization at 25' C. in order t o obtain a polymer of uniform molecular ryeight. Bruner and Kvalnes ( 3 G ) outlined a high temperature, high pressure condensation of melamine and formaldehyde. Hofricht,er (BG) employed a lead oxide-antimony trioxide catalyst for the high t,emperature, low pressure ester interchange in t'he production of polyethl-lene terephthalate and used triphenyl phosphite t o prevent polymer discoloration. Welsh and Holdstock (3OG) devised an improved method for the preparation of polysiloxane resins. Adams ( I G ) formed stable latices in emulsion polymerization b y emulsion inversion. Norris (1DG) recommended continuous monomer and catalyst addition for the format,ion of smooth, st,able polyptyrene emulsions, using a monomer-soluble emulsifier. May and Matheson ( 1 7 G ) developed a technique for the slurry polj-merizat,ion of olefins using a deposited orthophosphoric acid catalyst. Stable dispersions of unsaturated olefin polymers were obtained by passing droplets of monomer through an aqueous emulsifier solution (WIG). Five patents (2G, 5G, 8G, 22G, 26G) disclosed details of processes for the fluidized polymerization of olefins. Nelson (18G) designed an annular reactor for the continuous polymerization of liquid olefins below - 10" C. in contact with a dissolved FriedelCrafts catalyst. Hou-e and HalloTray (12G) recommended a modified reaction mixture to be used in low temperature olefin polymerization in order to obtain specification grade polymer from the initial batches after cleaning a reactor. Manning (16G) described high pressure equipment for ethylene polymerization. Horikx and Hermans (11G)studied the benzol-1 peroxide initiated polymerization of styrene in a tubular reactor. LudeTTig ( I 6 G ) outlined the technical details €or the manufact,ure of polyamide synthetics by batch and simplified continuous (UK) tube processes. Hohenstein (1GG) used mechanical agitation, temperature control, and chilling t o obtain and maint,ain unagglomerated copolymer products. BIBLIOGRAPHY REVIEWS
(14) Adanis, R. J., and Buckler, E. .J,, T r a n s . I n s t . Rubber I d . , 29, 17 (1953). (24) Carey, J. E., M o d e m Plastics, 30, No. 12, 130 (1953). (3-4) Champetier, G., Scieiitia ( M i l a n ) ,88, 130 (1953) (in French). (48) Cooper, W., I n d . Chemist, 34, 82 (1953). (5-4) Cooper, W., Rubber A g e a n d Synthetics, 34, 199 (1953). (6.4) Fisher, H. L., I n d i a Rubber W o r l d , 127, 641 (1953). ( 7 4 Goldstein, R. F., Plastics Inst. ( L o n d o n ) , Trans., 21, N o . 44, 18 (1958).
Vol. 46, No. 9
(8A) Jacini, G., Olearia, 6, 76 (1953). (SA) Korshak, V. V., U s p e k h i Khiwz., 21, 121 (1952). (10.4) Landler, I., Rec. ge'n. caoutchouc, 30, 647 (1953). (11-4) Langlois, G. E., IKD.ENG.CHEX.,45, 1470 (1953). (1211) Lever, A. E., Plastics, 18, 395 (1953). (1324) Lynn, L., M o d e r n Plastics, 31, No. 2 , 139 (1953). (14.1) hIoncrieff, R. W.. Fibres ( L o n d o n ) , 14, 86 (1953). (l5A) Koll, W., Angew. Chem., 66, 41 (1954). (ISA&)Parker, F. B., C a n . Chem. Processing, 37, No. 13, 30 (1953). (17-4) Powers, P. O., ISD. EKG.Cmnf., 45, 1063 (1953). (18A) Quail, F. J., C a n . Chcm. Processing, 37, No. 10, 62 (1953). (?SA) Raine, H. C., Kunstofe, 43, 503 (1953). (20-4) Saccenti, G., Chimica, e industiia ( W i l a n ) , 34, 412 (1952). (21A) Schrade, J., Kunststofe. 43, 286 (1953). (22A) Studeifiska, L., Przemysl Chem., 31 (8), 382 (1952). (23-4) Ullrich. W., &err. A p o t h . Ztg., 7, 890 (1953). (24-4) Wheeler, R. S . , J . Oil & Colwitr Chemists Assoc.. 36, :305 (1953). ( 2 5 4 Winding, C. C., and TViegandt, H. F., IKD.EXG.CHEX.,45, 2011 (1953). CATALYSTS, ACTIVATORS, MODIFIERS, AND INHIBITORS
(1B) Antlfinger, G. J. (to B. F. Goodrich Co.), C . S. Patent
2,662,876 (Dee. 15, 1953). (2B) Antlfinger, G. J., and Lufter, C. H., IND.ENG.C H m r . , 45, IS2 (1953). (3B) Arcus, C. L., and Hamstead, J., Chemistry & I n d u s t r y , 1953, p. 518. (4B) huspos, L. A., and Dempster, J. B. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,643,989 (June 30, 1953). (5B) Billica, H. R. (to E. I. du Pont de Nemours & Co.), I b i d . , 2,647,885 (Sug. 4, 1963). (6B) Boyd, T. (to Monsanto Chemical Co.), Ibid., 2,650,913 (Sept. 1, 1953). ( i B ) Breitenbach, J. W., and Fally, A , Monatsh., 84,319 (1953). (8B) Brown, R. S. (to United States Rubber Co.), U. S. Patent 2,628,956 (Feb. 17, 1953). (9B) Caldwell, I. R. (to Eastman Kodak Co.), I b i d . , 2,639,279 ( M a s 19. 1953). (10B) Ca1fw-J. D., and Kraus, C. A. (to Standard Oil Development Co.), Ibid., 2,644,798 (July 7, 1953). (11B) Carnahan, J. E. ( t o E. I. du Pont de Xernours & Co.), Ibad., 2,634,260 (April 7, 1953). (12B) Comer, J. C.. J r . . and Lohr, A. D. (to Hercules Powder Co.), I b i d . , 2,632,774 (hIarch 24, 1953). (13B) Cooper, W., Chenzistrg & I n d u s t r y , 1953, p. 407. (14B) Cooper, TV., J . Chem. SOC.,1953, p. 1287. (15B) Corner, E. S.. and Lynch, C. S. (to Standard Oil Development Co.). U. 9. Patent 2,642,402 (June 16, 1953). (18B) Dannenberg, €1. (to Shell Development Co.), Ibid., 2,643,243 (June 2 3 , 1953). (17B) DeTar, D. F., and Savat, C. S., J . Am. Chem. Soc., 75, 5118 (1953). (18B) Edmunds, 8. M., and Sonnabend, L. F. (to Dow Chemical Co.), U. 8.Patent 2,655,491 (Oct. 13, 1953). (19B) Folt, V. L. (to B. F. Goodrich Co.), Ibid., 2,625,539 (Jan. 13, 1953). (20B) Hamilton. J. M., Jr., IND.ENG.CHEM.,45, 1347 (1953). (21B) Hicks, J. A., and llelville, H. W., N a t u r e , 171, 300 (1953). (22B) Hofrichter. C. H., Jr. (to E. I. du Pont de Kemours 8; Co.), U. 5.Patent 2,641,592 (June 9, 1953). (23B) Hohenstein, W. P., and associates, Brit. Patent 690,877 (April 29, 1953). (24B) Hoppens, €1. A. (to Libbey-Owens-Ford Glass Co.), U. 5. Patent 2.642.410 (June 16. 19.53). (25B) Howard, k. G.. Jr. (to E. I. du'Pont de Kemours &- Co.), Ibid., 2,661,331 (Dee. 1, 1953). (26B) Kolthoff, I. hl., and Dale, W.J. (to PhiliiDs Petroleum Co.), I b i d . , 2,625,537 (Jan. 13, 1953). (2iB) Kolthoff, I. hl., and Meehan, E . J., J . Polymer Sci., 1 1 , 71 (1953). (28s) Lee, iLI. LI.,U. S . Patent 2,647,878 (Aug. 4, 1953). (29B) McKennon, F. L., and Lawrence. R. V. (to United States of America), I b i d . , 2,653,992 (Sept. 29, 1953). (30B) Narvel. C . S.. Friedlander. H. Z.. and associates. J . A m . Chem. Soc.. 75, 3848 (1953). (31B) S . I-.de Bataafsche Petroleum Ilaatschappij, Dutch Patent 71,947 (May 16, 1953). (32B) Park, H. F. (to LIonsanto Chemical Co.), U. S. Patent 2,664,416 (Dec. 29, 1953). (33B) . , Patterson. H. T. (to E. I. du Pont de Semours &- C0.i. Ibid.. 2,654,731 (Oct.'6, 1953). (34B) Sachs, C. C., and Bond, J. (to Alexander H. Kerr and Co.), I b i d . , 2,641,576 (.June 9, 195%) I
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INDUSTRIAL AND ENG INEERING CHEMISTRY
September 1954
(35B) Shiba, T., and Ozaki, A , , J . Chem. SOC.Japan, Pure Chem. Sect., 74, 295 (1953). (36B) Shokal, E. C., and associates (to Shell Development Co.), U. S. Patent 2,643,239 (June 23, 1953). (37B) Shusman, T. (to Rlonsanto Chemical Co.), Ibid., 2,647,111 (July 28, 1953). (38B) Standard Oil Development Co., Brit. Patent 690,387 (April 22, 1953). (39B) Stewart, W. D. (to R. F. Goodrich Co.), U. S.Patent 2,631,997 (March 17, 1953). (40B) Ibid., 2,634,258 (April 7 , 1953). (41B) Swern, D., and associates. J . Polymer Sci., 11, 487 (1953). (42B) Tutwiler, T. S. (to Standard Oil Development Co.), U. 8 . Patent 2,628,225 (Feb. 10, 1953). (OB) Underwood, J. E., and Hill, A. (to Diamond Alkali Co.), Ibid., 2,604,468 (July 22, 1952). (44B) Uraneck, C. A., and Goertz, R. J. (to Phillips Petroleum Co.), Ibid., 2,629,708 (Feb. 24, 1953). (45B) Uraneck, C. A., and Rothlisberger, A. C. (to Phillips Petroleum Co), Ibid., 2,629,709 (Feb. 24, 1953). (46B) Wadsworth, F. T. (to Pan American Refining Co.), Ibid., 2,631,996 (March 17,1953). (47B) West, H. J. (to American Cyanamid Co.), Ibid., 2,597,766 (May 20, 1952). (48B) Williams, H . L. (to Polymer Corp., Ltd.), Ibid., 2,655,495 (Oct. 13, 1953). (49B) Williams, H. L., and Mitchell, J. M.(to Polymer Corp., Ltd.), Ibid., 2,631,142 (March 10, 1953). Alliger, G., and associates, IND. ENG.CHEM.,45, (SOB) Willis, J. M., 1316 11953). (5lB) Woodman, J. F. (to Rohm & Haas Co.), U. S. Patent 2,632,729 (March 24, 1953). (52B) Yurzhenko, T. I., Puchin, V. A,, and Grigor’eva, K. S., Doklady Akad. Nauk S.S.S.R., 92,97 (1953). (53B) ZeiliGski, W., and Domanusowa, S., Przemysl Chem., 31 ( 8 ) , 471 (1952) ~
R E A C T I O N M E C H A N I S M S AND KINETICS
(IC) Aggarwal, S. L., and Long, F. A., J . Polymer Sci., 11, 127 (1953). (2C) Alfrey, T., and Berdick, M., Ibid., p. 61. (3C) Bamford, C. H., Barb, W. G., and Jenkins, A. D., Nature, 167, 1044 (1952). (4C) Bamford, C. H., and Jenkins, A. D., PTOC.Roy. SOC.(London), A216, 515 (1953). (5C) Barb, W. G., 6.A m . Chem. Soc., 75, 224 (1953). (6C) Barb, W.G., J . Polymer Sci., 10,49 (1953). (7C) Ibid., 11, 117 (1953). (8C) Bender, H. L., Modern PZastics, 30, No. 6, 136 (1953). (9C) Berstein, I. A , , and associates, J . Chem. Phys., 21, 1303 (1953). (1OC) Boelhouwer, C., Chem. WeekbZad, 49, 197 (1953). (1lC) Bonsall, E. P., Valentine, L., and RIelville, H. W.,Trans. Faraday Soc., 49, 686 (1953). (12C) Brown, R. Rl., and Winkler, C. A,, Can. J . Chem., 31, 13 (1953). (13C) Brugel, W.,Schweiz. Ver. Lack- u. Farben-Chem. u.-Tech. Bull., No. 21, 37 (1953). (14C) Burnett, G. M.,Evans, P., and hlelville, H. W., Trans. Faraday Soc., 49, 1096 (1953). (15C) Burnett, G . M.?and Wright, W. W., Ibid., p. 1105. (16C) Ibid., p. 1108. (17C) Charlesby, A,, Plastics (London), 18, 142 (1953). (18C) Clark, D., Proc. Conf. Univ. Coll., North Staffordshire, England, 1952, p. 99. (19C) Collinson, E., and Dainton, F. S., Discussions Faraday SOC., h-0. 12, 212 (1952). (20C) Condon, F. E., J . Polumer Sci., 11, 139 (1953). (2lC) Conix, A , and Smets, G., Discussions Faraday Soc., No. 10, 525 (1953). (22C) Cooper, W., Rubber A g e and Synthetics, 34, 151 (1953). (23C) Cordier, D. E. (to Libbey-Owens-Ford Glass Co.), U. S. Patent 2,635,083 (April 14, 1953). (24C) Corner, E. S., and Lynch, C. S. (to Standard Oil Development Co.), Ibid., 2,642,402 (June 16,1953). (25C) Cragg, L. H., and Fern, G. L. F., Can. J . Chem., 31, 710 (1953). (26C) D’Alelio, G. F. (to Koppers Co., Inc.), U. S. Patent 2,656,334; 2,656,341 (Oct. 20, 1953). (27C) Dainton, F. S., and associates, Proc. Conf. Univ. Coll., North Staffordshire, England, 1952, p. 80. (28C) Davies, M., and Hill, D. R. J., Trans. Faraday Soc., 49, 395 (1953). (29C) Davis, A. C., Hayes, B. T., and Hunter, R. F., J . A p p l . Chem. (London),3, 312 (1953).
1877
(30C) Dickey, J. B., and Coover, H. W., Jr. (to Eastman Kodak Co.), U. S. Patent 2,652,393 (Sept. 15, 1953). (31C) Durr, A4., and Wendling, R., Proc. XIth Intern. Congr. Pure and Appl. Chem. (London), 1947,5,531 (1953). (32C) Ehlers, J. F., Kolloid-Z., 131, 137 (1953). (33C) Ibid., p. 145. (34C) Eidus, Y. T., and Puzitskii, K. V., Uspekhi. Khim., 22, 838 (1953). (350) Eliiott, ’J. R., hlyers, R. L., and Roedel, G. F., IND.ENG. CHEM.,45, 1786 (1953). (36C) Fox, T. G., and Gratch, S., Ann. N. Y . Acad. Sci., 57, 367 (1953). (37C) Garten, V. A,, 2. Naturforsch., 8b,46 (1953). (38C) Gregg, R. A., and Mayo, F. R., J . Am. Chem. Soc., 75, 3530 (1953). (39C) Harris, T. G., and Neville, H. A., J . Polymer Sci., 10, 19 (1953). (40C) Hayes, R. A., Ibid., 11, 531 (1953). (41C) Helin, A. F., and associates, IND.ENG. CHEM.,45, 1330 (1953). (42C) Immergut, E. H., Makromol. Chem., 10,93 (1953). (43C) Jones, G. D., and Friedrich, R. E. (to Dow Chemical Co.), U. S. Patent 2,619,507 (Nov. 25, 1952). (44C) Jordan, D. O., and Mathieson, A. R., Proc. Conf. Univ. Coil., North Staffordshire, England, 1952, p. 90. (45C) Kaghan, W. S., and Shreve, R. N., IND. ENG.CHmf., 45, 292 (1953). (46‘2) Kapur, S. L., 7 . Polymer Sci., 11, 399 (1953). (47C) Klaasens, K. H., and Gisolf, J. H., Ibid., 10, 149 (1953). (48C) Koton, M. M., Doklady Akad. Nauk S.S.S.R., 93, 825 (1953). (49C) Koton, M. M., and Kiseleva, T. M., Ibid., 88,465 (1953). (50C) Kut, S., Paint Varnish Production, 43, No. 11, 28; No. 12, 33 (1953). (51C) Lombard, F., Makromol. Chem., 8, 187 (1952). (52C) Melville, H. W., Ofic. Dig. Federation Paint & Varnish Production Clubs, No. 336, 24 (1953). (53C) Melville, H. W., and Watson, W. F., J . Polymer Sci., 11, 299 (1953). (54C) Morton, M., Salatiello, P. P., and Landfield, H., Ibid., 8, 215 (1952). (55C) Narracott, E. S., British Plasiics, 25, 120 (1953). (56C) Oschatz, F., Schwsiz. Ver. Lack- u. Farben-Chem. u.-Tech. BUZZ., No. 21, 22 (1953). (57C) Overberger, C. G., Arnold, L. H., and associates, J . A m . Chem. SOC..74. 4848 (1952). (58’2) Park, H. F.(to konsanto Chemical Co.), Ti. S. Patent 2,658,057 (Nov. 3, 1953). (59C) Ibid., 2,659,716 (Kov. 17, 1953). (6OC) Ibid., 2,659,717 (Nov. 17, 1953). (61C) Peaaer. D. C.. Proc. Conf. Univ. Coil.. North Staffordshire. England, 1952, p. 70. (62C) Pepper, D. C.. and Sommerfield, .4.E., Ibid., p. 75. (63C) Plesch, P. H., J . Chem. Soc., 1953, p. 1653. (64C) Price, C. C., Halpern, B. D., and Voong, S.,J . Polymer Sci., 11, 575 (1953). (65C) Rehner, J.,Jr., Ibid., 10, 442 (1953). (66C) Rehner, J., Jr., Zapp, R. L., and Sparks, W.J., Ibid., 11, 21 (1953). (67C) Russell, K. E., and Tobolsky, A. V., J . A m . Chem. Soc., 75, 5052 (1953). (68C) Rutovskii, B. N., and Goncharov, G. S., Zhur. Priklad. Khzm., 26, 434 (1953). (69C) Saylor, J. S.,Jr. (to Standard Oil Development Co.), U. S. Patent 2,644,809 (July 7, 1953). (7OC) Seitzer, W. H., Goeckermann, R. H., and Tobolsky, -4.V., J. Am. Chem. SOC.,75,755 (1953). (71C) Shkol’man, E. E., and Zeldler, I. I., Zhur. Priklad. Khim., 26, 736 (1953). (72C) Ibid., p. 1205. (73C) Smeltz, R. C., and Dyer, E., J . Am. Chem. Soc., 74, 623 (1952). (74C) Smythe, L. E., Ibid., 75, 574 (1953). (75C) Sofer, G. A., Dietz, A. G. H., and Hauser, E. A., IND.EKQ. CHEM.,45,2743 (1953). (76C) Stewart, R. A., and Williams, H. L., Ibid., p. 173. (77C) Swern, D., and Port, W. S., J . Am. Chem. Soc., 74, 1738 (1952). (78C) Thomas, W. M., and O’Shaughnessy, M. T., J . Polymer Sci., 11,455 (1953). (79C) Tobolsky, A. V., and Baysal, B., Ibid.. p . 471. (8OC) Vergoz, R., Ann. chim. (Paris),8, 101 (1953). (81C) Wheeler, 0. L., Ann. N . Y.Acad. Sci., 57, 360 (1953). (82C) Wohnsiedler, H. P., IND.ENG.CHEM.,45, 2307 (1953). (83C) Zeldler, I. I., and Shkol’man, E. E., Zhur. PrikZad. Khim., 26, 840 (1953).
INDUSTRIAL AND ENGINEERING CHEMISTRY
1878 ETHYLENIC POLYMERS
(1D) Adriaan Honig's Kunsthars Industrie N. V., Dutch Patent 72,404 (May 15, 1953). (2D) Alfrey, T., Jr., Overberger, C. G., and Pinner, S. H. J., J . Am. Chem. Soc., 75, 4221 (1953). (3D) Amos, J. L., and Ililler, C. T. (to Dow Chemical Co.), U. S. Patent 2.638.465 (Mav 12.19531. _ . (4D) Armitage, F. (to Lewis Berner and Sons, Ltd.), Brit. Patent 688,755 (March 11, 1953). (5D) Arundale, E., and Banes, F. Tv. (to Standard Oil Development Co.), U. s. Patent 2,628,198 (Feb. 10,1953). (6D) d4r\in, J. A. (to Sherwin Williams Co.), Ibid., 2,627,509 (Feb. 3, 1953). (7D) Bamford, C. H., and Barb, W. G., Discussions Faraday Soc., No. 14, 208, 1953. (8D) Bankoff, S.G., and Shreve, R. N., IKD. ENG.CHEM.,45, 270 (1953). (9D) Barb, W.G., J . Polvmer Sci., 10,49 (1953). (10D) Barney, A. L. (to E. I. du Pont de Nemours & Co.), U. 5. Patent 2,641,594 (June 9, 1953). (11D) Barrett, G. R. (to Monsanto Chemical Co.), Ihtd., 2,640,819 (June 2, 1953). (12D) Barry, A. TV. (to E. I. du Pont de Kemours &. Co.), Ibid., 2,646,425 (July 21, 1953). (13D) Basdekis, C. 8. (to Chemstrand Corp.), Ibid., 2,635,090 (April 14, 1953). (14D) Bauer, L. li.,Neher, H. T., and Van Horne, W, L. (to Rohm & Haas Go.),Ibzd., 2,642,414 (June 16, 1953). (15D) . , Berrv, K. L. (to E. I. du Pont de Kemours & Co.), Ibr;d., 2,662,065 (Dee. 8, 1953). (16D) Bestian, J. (to Farbwerke Hoechst. vorm. Meister Lucius and Bruning), Ibid., 2,626,931 (Jan. 27, 1953). (17n) ,-. -, Rilt,on. ~,.J. . d..and Sezall. G. H. (to Canadian Industries. Ltd.), Ibid.: 2,604,463 (July 22, 1952). (18D) Bittles, J. 8.(to E. I. du Pont de Nemours & Co.), I b i d . , 2,628,958 (Feb. 17, 1953). (19D) Bloch, H. S.(to Universal Oil Products Co.), Ibid., 2,648,640 (Aug. 11, 1953). (20D) British Resin Products, Ltd., Evans, E. RI., and Whitney, J . E. 6 . .Brit. Patents 691,038: 691,040; 691,041; 691,042 (May 6, 1953). (21D) Brothman, A , U. S. Patent 2,632,758 (>larch 24, 1953) (22D) Brunner, H. (to Imperial Chemical Industries, Ltd.), Brit. Patent 698,621 (Oct. 21, 1953). (23D1 Brus, G., and associates, Industrie Plastigues Mod. (Paris), 5, S o . 8, 51 (1953). (24D) Burnett, R.E . , arid Sordlander, B. W. (to General Electric Co.), U. S.Patent 2,628,178 (Feb. 10, 1953). (2513) Caldwell, J. R. (to Eastinan Kodak Co.), I b i d . , 2,656,337 (Oct. 20, 1953). (26D) Carlin, F. J. (to United States Rubber Co.), I b i d . , 2,626,945 (Jan. 27, 1953). (27D) Carlson, E. J. (to B. F. Goodrich Go.), Ibid., 2,657,197 (Oct. 27, 1953). (28D) Chaney, D. W.(to Chemstrand Corp.), Ibid., 2,662,875; 2,662,877 (Dec. 15, 1953). (29D) Coover, H. W., and Dickey, J. B. (to Eastman Kodak Co.), Ibid., 2,649,434 (Aug. 18, 1953). (30D) Coover, H. W., Dickey, J. B., and Shearer, N. H. (to Eastman Kodak Co.), Ibid., 2,663,697 (Dee. 22, 1953). (31D) Crouch, W. W., and Cotton, E. TV. (to Phillips Petroleum Co.), I b i d . , 2,645,631 (July 14,1953). (32D) Crouch, W. W., and Harris, R. K. (to Phillips Petroleum Co.), Brit. Patent 686,446 (Jan. 28, 1953). (33D) Culhane, P. J., and Rothrock, G. &I.(to E. I. du Pont de Nemours & Co.), Ibid., 2,636,023 (April21, 1953). (34D) Day, H. M., and Affleck, J. G., Soc. Plastics B n g r s . J . , 9, No. 2, 22 (1953). (35D) De Trey frbres S. A,, Brit. Patent 687,299 (Feb. 11, 1953). (36D) De Vault, A. N. (to Phillips Petroleum Go.), U. S.Patent 2,656,398 (Oct. 20,1953). (37D) Dickey, J. B., and Coover, H. W.(to Eastman Kodak Co.), Ibid., 2,636,027 (April 21, 1953). (38D) Dickey, J. B., and Stanin, T. E. (to Eastman Kodak Co.), Ibid., 2,618,655 (Kov. 18, 1952). (39D) Drinberg, A. Ya., and Bocharova, A. M,, Zhur. Prildad. Khim., 26, 1056 (1953). (40D) Ellery, E., and Todd, S. M. (to Imperial Chemical Industries, Ltd.), Brit. Patent 695,633 (Aug. 12, 1953). (41D) Engelhardt, V. -4.(to E. I. du Pont de Nemours & Co.), U. S. Patent 2,647,106 (July 28, 1953). (42D) Ezrin, M., and associates, J . Am. Chem. Soc., 75, 1610 (1953). (43D) Folt, V. L., and Carlson, E. J. (to B. F. Goodrich Co.), U. S. Patent 2,657,199 (Oct. 27, 1953). ,
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Vol. 46, No. 9
(44D) Garber, J. D., and Sparks. W.J. (to Standard Oil Development Go.), Ibid., 2,625,523 (Jan. 13, 1953). (45D) Geiser, E. M.(to Universal Oil Products Co.), [bid.,2,624,717 (Jan. 6, 1953) (46D) Gilbert, H , and Xiller, F. F. (to €3. F. Goodrich Co.), Ibid., 2,654,724; 2,654,728 (Oct. 6, 1953). (47D) Gilbert, H., Miller, F. F., and Folt, V. I,. (to B. F.Goodrich Co.), Ibid., 2,650,911 (Sept. 1, 1953). (48D) Gleason, 9.H. (to Standard Oil Development Co.), Ibid., 2.652.342 (SeDt. 15 1953). (49D) Gould, C. W. ?to Hercules Powder Co.), I b z d . , 2,638,273 (May 19, 1953). (50D) Gregg, R. A. (to United States Rubber Co.), I b i d . , 2,636,874 (April 28, 1953). (51D) Gresham. W. F. (to E. I. du Pont de Semours & Co.), Ibid., 2,632,014 (March 17, 1953). (52D) Gresham, W. E'., and Hill, A, J., Jr. (to E. I. du Pont de Kemours &. Co.), [bid., 2,640,074 (May 26, 1953). (53D) Griess, G. A., and Strandoskov, C. V. (to Dow Chemical CO.),I b i d . , 2,639,270, 2,639,271 (Map 19, 1953). (54D) Griess, G. A., and Teot, A. S.(to Dow Chemical Co.), Ibid., 2,659,772 ( l l a y 19, 1953). (55D) Ham, G. E. (to Chemst'rand Corp.), Ibid., 2,G35,092 (April 14. 1953). (56D) I b i d . , 2,643,990 (June 30, 1953). (57D) Ham, G. E. (t,o Monsanto Chemical Co.), Ibid., 2,658,056 (Nov. 3. 1953). (58D) Ham, G. E., and Crais, 4. B. (to Chemstrand Corp.), Ibid., 2,664,412 (Dee. 29, 1953). (5QD) Harman, D., and Stiles, A. R. (to Shell Development Co.), Ibid.. 2,632,756 (March 24, 1953) (60D) Heinrich, R. L. (to Standard 011 Develosmcnt Go.). I b t d . . 2,361,176 (March 10, 1953). (61D) Henson, TV. A, P a i n t , Oil,Chem. n e b . , 116, No. 27, 11 (1953). (62D) Ilohenstein, W.P., Haward, R. T , and Elly, J. (Haward, R. K., and Elly, J., to Hohenstein, W.P.), U. 8. Patent 2,652,392 (Sept. 15, 1953). (63D) Houillbres Bassin-du-Kord Pas-de-Calais, Brit Patent 686,537 (Jan. 28, 1953). (64D) Ilowe, J. F. (to Phillips Petroleum C o ) , U. S Patent 2,637,663 (May 5 , 1953). (65D) Hulse, G. E. (to Hercules P o r d e r Co.), Ihzd.. 2,637,710 (Mav 5 1953). (66D) Kanning, E . IT., and Hartmers, E. G. (to Arco Co.), Ibid., 2,665,488 (Oct. 13, 1953). (67D) Mantor, S. V., and Osthoff, R. C . , J. Am. Cham. Soc., 75, 931 (1953). (68D) Kass, P. (to Atlas Powder Go.), U. S. Patent 2,634,251 (April 27, 1953). (69D) Kaufman, AI., and Williams, A. Y. (to C. D. Patents, Ltd.), Ibid.. 2.632.749 (March 24. 1 9 3 ) . (70D) Kropa, E. L., and Rlalmberg, E. W.(to American Cyanamid Co.), Ibid., 2,655,494 (Oct. 13, 1953). (71D) Kropa, E. L., and Nyquist, A. 8. (to American Cyanamid Co.), Ibid., 2,624,722 (Jan. 6, 1953). (72D) Lawson, J. K., Jr. (to American T'iscose Corp.), I b i d . , 2,631,975 (March 17, 1953). (73D) LeFevre, W. J., and XIsll. H.W.(to Daw Chemical Co.), Ibzd., 2,640,050 (May 25, 1953). (74D) LeonaId, F., Salachtun, 8. J., and Cort, I., 6.Pulymer Sci., 11. 539 (1953). (75D) Lipwomb, R -5.. (to E. I. du P o n t de Semours & Co.), U. 9. Patent 2,634,254 (April 7, 1933). (76D) Long, J. L. (to Don, Chemical Co.). Ibid.. 2,646,418 (July 21, 1953). (77D) Loshaek, S., and Fox, T. G., J . Am. Chem. Sac., 75, 3544 (1953). (78D) Lytton, 11.R. (to Chemstrand Corp.), U. S.Patent 2,656,338 (Oct. 20, 1953). (79D) McGrew, F. C., and Pinkney, P. S. (to E. I. d u Pont de Nemours & Co.). Ibid., 2,657,200 (Oct. 27, 1933). (SOD) Marhofer, E. G., and Ilillyer, J. C . (to Phillips Petroleum Co.).Ibid.,2,653,956 (Sepz. 29, 1953). (81D) Marsh, F. D. ( t o E . I. du Pont de Semours & Co.), Ibid., 2,628,221 (Feb. 10. 1953). (82D) Marvel, C. S.,and Wright, J. C., J . Polymer Sci.,8, 255 (1952). (83D) Meeske, C. J., and Laganis, D. (to Reichhold Chemicals, Inc.), U. S. Patent 2,647,092 (July 28, 1953). (84D) Miller, C. B., and Calfee, J. D. (to Allied Chemical & Dye Corp.), Ibid., 2,635,093 (April 14, 1953). (85D) Miller, H. C., and Rothrock, H. S. (to E. I. du Pont de Nemours & Co.), Ibid., 2,657,192 (Oct. 23, 1953). (86D) Miller, W. T. (to M. W.Kellogg Co.), Brit. Patent 694,164 (July 1,5, 1953). I
>
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
(87D) Miller, W. T. (to United States of America), U. S. Patent 2,662,072 (Dec. 8, 1953). (8SD) Miller, W.T., and Maynard, J. T. (to the United States of America), Ibid., 2,625,254 (Jan. 20,1953). (89D) Milne, J. N., Faulkner, D., and Hollis, C. E. (to Distillera Co., Ltd.), I b i d . , 2,650,250 (Aug. 25, 1953). (90D) Neher, H. T., and Bauer, L. N. (to Rohm & Haas Co.), Ibid., 2,633,460 (March 31, 1953). (91D) Nelson, J. F., and Gleason, A. H. (to Standard Oil Development Co.), Ibid., 2,650,209 (Aug. 25, 1953). (92D) N. V. de Bataafsche Petroleum Maatschappij, Brit. Patent 679,562 (Sept. 17, 1952). (93D) Ibid., 692,722 (June 10, 1953). (94D) Ibid., 694,408 (July 22, 1953). (95D) N. V. de Bataafsche Petroleum Maatschappij, Dutch Patent 72,216 (April 15, 1953). (96D) Ibid.. 72.670 (Julv 15. 1953). (97Dj Padbury, J. J. (to Bmerican Cyanamid Co.), U. S. Patent 2,656,339 (Oct. 20,1953). (98D) Park, H. F. (to Monsanto Chemical Co.), Ibid., 2,624,724 (Jan. 6, 1953). (99D) Ibid., 2,643,995 (June 30, 1953). (100D) Patai, S., and associates, J . Am. Chem. Soc., 74, 845 (1952). (101D) Pearson, F. G. (to American Viscose Corp.), U. S. Patent 2,631,998 (March 17, 1953). (102D) Peters, E. F., and Evering, B. L. (to Standard Oil Co. of Indiana), Ibid., 2,658,03,9 (Nov. 3, 1953). (103D) Pines, H. (to Universal Oil Products Co.), I b i d . , 2,632,777 (March 24, 1953). (104D) Pinner, S.H., J . Polymer Sci., 10,378 (1953). (105D) Plas, F. J. F. van der, and Dijk, C. P. van (to N. V. de Bataafasche Petroleum Maatschappij), Dutch Patent 72,274 (April 15, 1953). (106D) Price, J. A. (to American Cyanamid Co.), U. S. Patent 2,654,725 (Oct. 6, 1953). (107D) Ibid., 2,654,729 (Oct. 6,1953). (108D) I b i d . , 2,655,493 (Oct. 13,1953). (109D) Prober, M., J . Am. Chem. Soc., 75,968 (1953). (llOD) Radzitzki, P. de, and Smets, G., B u l l . SOC. c h i m . Belg., 62, No. 5, 320 (1953). (111D) Ross, S. D., and Markarian, hi., J . Polymer Sci., 9, 219 (1952). (112D) Rothrock, G. hl. (to E. I. du Pont de Nemours & Co.), U. 8. Patent 2,640,049 (May 26,1953). (113D) Rubens, L. C., and Boyer, R. F. (to Dow Chemical Co.), Ibid., 2,636,018 (April 21, 1953). (114D) Rust, J. B., and Canfield, W. B , Ibid., 2,650,207 (Aug. 25, 1953). (l15D) Sample, J. H. (to Sherwin-Williams Co.), Ibid., 2,650,907 (Sept. 1, 1953). (116D) Schneider, H. G., and Brakeley, P. W., Jr. (to Standard Oil Develooment Co.). Ibid.. 2,637,720 (luau 5, 1953). (117D) Schneider, H. G., ‘and Goering; H. .G. -(to Standard Oil Development Co.), Ibid., 2,657,246 (Oct. 27, 1953). (118D) Schoonover, I. C., Brauer, G. M., and Sweeney, W. T., J. Research Natl. B u r . Standards, 49,359 (1952). (119D) Schulken, R. M., Jr., and Boy, R. E., Jr. (to Eastman Kodak Co.), U. S.Patent 2,652,391 (Sept. 15, 1953). (120D) Segall, G. H., and Dixon, J. F. C. (to Canadian Industries, Ltd.), Ibid., 2,604,457; 2,604,464 (July22, 1952). (121D) Seymour, R. B. (to Monsanto Chemical Co.), Ibid., 2,647,886 (Aug. 4, 1953). (122D) Shekleton, J. F. (to General Aniline & Film Corp.), Ibid., 2,653,923 (Sept. 29, 1953). (123D) Shostakovskii, M. F., and Gladyshevskaya, V. A,, Izvest. Alcad. Nauk S.S.S.R., Otdel. Khim. Nauk, 1953, p. 351. (124D) Shostakovskii, M. F., Sidel’kovskaya, F. P., and Zelenskaya, M. G., Ibid., 1952, p. 690. (125D) Sparks, W. J., and Young, D. W. (to Standard Oil Development Co.), U. s. Patent 2,609,359 (Sept. 2, 1952). (I26D) Standard Oil Development Co., Brit. Patent 688,082 (Feb. 25, 1953). (127D) Stanin, T. E., and Dickey, J. B. (to Eastman Kodak Co.), U. S. Patent 2,649,435 (Aug. 18, 1953). (128D) Stanton, G. W., Lefferdink, T. B., and Davis, C. W. (to Dow Chemical Co.), Ibid., 2,648,647 (Aug. 11, 1953). (129D) Stiehl, R. T., Jr., Univ. Microfilms, Ann Arbor, Mich., Piihl. 6016. 1953. (130D) Stockmayer, ’a.. H., Howard, R. O., and Clarke, J. T., J. Am. Chem. Soc., 75, 1757 (1953). (131D) Strain, F. (to Columbia-Southern Chemical Corp.), U. 8. Patent 2,650,215 (Aug. 25,1953). (132D) Swern, D., and Jordan, E. F., Jr. (to the United States of America), I b i d . , 2,631,141 (March 10,1953). (133D) Tawney, P. 0. (to.United States Rubber Co.), Ibid., 2,617,787 (Nov. 11, 1952).
(134D) (135D) (136D) (137D) (138D)
1879
Ibid., 2,626,252 (Jan. 20, 1953). Ibid., 2,643,991 (June 30, 1953). Ibid., 2,649,437 (Aug. 18, 1953). Tessmar, K., K u n s t o f f e , 44, 9 (1953). Tobolsky, A. V., and Baysal, B., J . Am. Chem. Soc., 75,
1757 (1953). (139D) Upton, W. V. (to National Starch Products, Inc.), U. S. Patent 2,637,712 (May 5, 1953). (140D) Wehr, H. W., and Nagle, F. B. (to Dow Chemical Co.), I b i d . , 2,646,423; 2,646,424 (July 21, 1953). (141D) Welch, L. M. (to Standard Oil Development Co.), I b i d . , 2,609,363 (Sept. 2, 1952). (142D) Werkema, T. E. (to Dow Chemical Co.), I b i d . , 2,658,058 (Nov. 3, 1953). (143D) Wilson, W. K. (to Shawinigan Resins Corp.), I h i d . , 2,643,245; 2,643,246 (June 23, 1953). (144D) Wolf, R. J. (to B. F. Goodrich Co.), Ibid., 2,636,024 (April 21, 1953). (145D) Wystrach, V. P. (to American Cyanamid Co.), Ibid., 2,647,884 (Aug. 4, 1953). (146D) Zerner, E., and Pollock, AM. W. (to Sun Chemical Corp.), I b i d . , 2,627,512 (Feb. 3, 1953). ELASTOMERS
(1E) Bloch, H. S. (to Universal Oil Products), U. S. Patent 2,636,029 (April 21, 1953). (2E) Brooks, L. A., Markarian, M., and Naazewski, M. (to Sprague Electric Co.), Ibid., 2,636,022 (April 21, 1953). (3E) Crouch, W. W. (to Phillips Petroleum Co.), I b i d . , 2,638,460 (May 12, 1953). (4E) David, F. 0. (to Reconstruction Finance Corp.), Ibid., 2,657,198 (Oct. 27, 1953). (5E) Dogadkin, B. A., Pel’dstein, M., and associates, D o k l a d y A k a d . Nauk S.S.S.R., 92, 61 (1953). (6E) Dunlop Rubber Co., Ltd., Jones, F. A., Cooper, W., and Bird, T. B., Brit. Patent 689,570 (April 1, 1953). (7E) Faragher, W. F. (to Houdry Process Corp.), U. S. Patent 2.634.257 (Aaril 7. 1953). Filachidne, E. M., Fitzpakck, T. J., and assooiates, Rubber Age ( N . Y . ) ,72,631 (1953). Fisher, C. H., and Mast, W. C. (to the United States of America, as represented by Secy. of Agr.), U. S. Patent 2,643,247 (June 23, 1953). (10E) Fryling, C. F., Troyan, J. E., and Pritchard, J. E. (to Phillios Petroleum Co.), Ibid., 2,604,466 (July 22, 1952). (11E) Howland, L. H., and Chambers, V. 5. (to United States Rubber Co.), Ibid., 2,640,042 (May26, 1953). (12E) Iwakura, Y. (to Tokyo Institute of Technology), Japan. Patent 1692 (April 20, 1953). (13E) Lynch, C. S. (to Phillips Petroleum Co.), U. S. Patent 2,625,525 (Jan. 13, 1953). (14E) Mahan, M. H. (to Standard Oil Development Co.), Ibid., 2,631,139 (March 10, 1953). (15E) Marvel, C. S., and Fuller, J. A, J . Am. Chem. Soc., 74, 1506 (1952). (16E) Narvel, C. S., McCain, G. H., and associates, IND.ENG. CHEM.,45, 2311 (1953). (17E) Marvel, C. S., Menikheim, V. C., and associates, J . Polymer Sci., 10, 39 (1953). (NE) Marvel, C. S., Peterson, W. R., and associates, IND.ENG. CHEM.,45, 1532 (1953). (19E) Mastin, T. G., and Seeger, N. V. (to Wingfoot Corp.), U. S. Patent 2,625,535 (Jan. 13, 1953). (20E) Parrish, C. I. (to B. F. Goodrich Co.), Ibid., 2,628,955 (Feb. 17, 1953). (21E) St. John, W. M., Jr. (to Phillips Petroleum Co.), Ibid., 2,638,461 (May 12, 1953). (22E) St. John, W. M., Jr., and Uraneck, C. A. (to Phillips Petroleum Co.), Ibzd., 2,615,009 (Oct. 21, 1952). (23E) Seeger, N. V. (to Wingfoot Corp.), Ibid., 2,625,531; 2,625,532 (Jan. 13, 1953). (24E) Seeger, K.V., iMastin, T. G., and associates, IND. ENG.CHEM., 45, 2538 (1953). (25E) Serniuk, G. E. (to Standard Oil Development Co.), U. S. Patent 2,624,726 (Jan. 6, 1953). (26E) Sparks, W.J., and Thomas, R. M. (to Standard Oil Development Co.), I b i d . , 2,626,940 (Jan. 27, 1953). (27E) Te Grotenhuis, T. A., and Swart, G. H. (to General Tire and Rubber Co.), Ibid., 2,645,632 (July 14, 1953). CONDENSATION POLYMERS
(1F) Alderson, T. (to E. I. du Pont de Nemours & Co.), U. Patent 2,658,055 (Nov. 3, 1953). (2F) Barron, H., Rubber A g e a n d Synthetics, 34,211 (1953).
S.
INDUSTRIAL AND ENGINEERING CHEMISTRY
1880
(3F) Beck, Koller and Co. (England), Ltd., Brit. Patent 687,310 (Feb. 11, 1953). (4F) Bloch, H. S. (to Universal Oil Products C o . ) , E. S. Patent 2,631,140 (Oct. 20, 1953). (5F) Ihid., 2,656,335 (XIarch 10, 1953). (6F) Bloch, H. S., and Mammen, H. E. (to Uni~ersalOil Products Co.), I b z d . , 2,657,193 (Oct. 27, 1953). (7Fj Bock, L. H. (to Rayonier. Inc.), IbLd., 2,662,871 (Dee. 15, 1953).
(8F) Bock, L. H., and Carlson. L. J. (to Rayonier, Inc.), Ibid., 2.649.436 (Au.ug. 18., 19531. , (9F) Boyd, T., an'd Walter, H. A. (to 11onsanto Chemical Co.), Ibid., 2,631,991 (March 17, 1953). (10F) British Thompson-Houston Co., Ltd.. Brit. Patent 695,462 (-4ug.12, 1953). (11Fj Chevalier, P. J. (to Sociew des usines chimiques RhonePoulenc), U. S.Patent 2,642,411 (June 16, 1953). (12F) Cunningham, 0. D., and Polly, 0. L. (to Union Oil of Calif,), Ibid., 2,652,410 (Seut. 15, 1953). (13F) D'Blelio, .G. F. (to koppers Cb., Inc.), I b i d . , 2,658,884; 2,658,885 (Nov. 10,1953). (14F) Dalton, L. K., B?istralian J . A p p l . Sci., 4, 13G (1953). (l5F) Davis, J. F. (to -imerican Cyanamid Co.), U. S. PatenLs 2,652,382; 2,652,383 (Sept. 15, 1953). (16F) Dearborn, E. C., and associates, IKD.EKG.CHEM.,45, 2715 (1953). (17F) Dereich, 3. E. (to Diamond Alkali Co.), U. 9. Patent 2,637,719 (May 5 , 1953). (18F) Ibid., 2,648,654 (,lug. 11, 1953). (19F) Diamond Alkali Co., Brit. Patent 695,457 (;iug. 12, 1953). (20F) Ibid., 695,823 (hug. 19, 1953). (21F) Di Giorgio, P. A. (to General Electric Co.), U. S. Patent 2,640,818 (June 2. 1954). (22F) Doelling, G. L., and Adams, K. H. (to Mississippi Valley Research Laboratories, Inc.), U. S.Patent 2,625,530 (Jan. 13, 1953). (23F) Embree, H. D., Univ. Xlicrofilms, Ann Arbor, Mich., Publ.
----.----
fi344.1 R5:i
(24F) Feasley, C. 9. (to Socony-Vacuum Oil Co.), U. S. Patent 2,660,572 (Nov. 24, 1953). (25F) Fisher, J. W.,Bates. II., and Wheatley, E. W. (to British Celanese, Ltd.), U. S. Patent 2,657,196 (Oct. 27, 1953). (26F) Fisher, J. W.,and Wheatley, E. W. (to British Celanese, Ltd.),Brit. Patent 693,172 (June 24, 1953). (2iF) Frisch, K. C., and Shroff. P. D. (to General Electric Co.), U. S. Patent 2,641,605 (June 9, 1953). (28Fj Frost, L. W. (to Westinghouse Electric Corp.), Ibid., 2,636,896 (April 29, 1953). (29F) Gresham, W.F., and Bell, C,. D. (to E. I. du Pont de Nemours h Co.),Ibid., 2,625,569 (Jan. 13, 1953). (30Fj Gronich, H . E . (to Allied Chemical & Dye Corp.), Ibid., 2,634,246 (April 7, 1953j. (31F) Gundermann, E., Chem. Tech. ( B e r l i n ) , 5, 40 (1953). (32F) Harris, T . G., Homing, R. H., and Neville, H. -4., Modern PlaS'tkQ, 31, NO. 4. 136 (1953). (33F) Hatcher, D. B., and Bunnell, 11. Ii. (to Libbey-Owens-Ford Glass Co.), U. S. Patent 2,624,720 (Jan. 6, 1953). (34F) Ibid., 2,624,721 (Jan. 6, 1953). (35F) Hermann, F. 3. (to Reichhold Chemicals, Inc.), I h i d . , 2,645,623 (July 14, 1953). (36F) Hoogsteen, H. AI., and Petersen, N. R. (to Dow Chemical Co.), I b i d . , 2,626,939 (Jan. 27, 1953). (37F) Hunter, hl. J., and Rauner, L. A. (to DONCorning Corp.), I b i d . , 2,628,215 (Feb. 10, 1953). (38F) Hurd, D. T. (to General Electric Co.), Ibid., 2,645,628 (July 14, 1953). (39F) Hyde, J. F. (to Dow Corning Corp.), Ibid., 2,634,284 (April 7, 1953). (40F) James. R. W.,and Pings, W,B. (to Imperial Paper and Color Corp.), Ibid., 2,626,251 (Jan. 20, 1953). (41F) Joffe, J. D. (to Allied Chemical & Dye Corp.), Ibid.,2,670,341 (Feb. 23, 1953). (42F) Jones, W. D., and X\IcFarlane, S. B. (to Celanese Gorp, of America), Ibid.,2,660,575 (Nov. 24, 1953). (43F) Kass, P. (to Atlas Powder Co.), Ibid., 2,662,069; 2,662,070 (Dee. 8, 1963). (4457 Kerr, K. R., and Hobbs, K. C., ISD.EKG.CHEM~, 45, 2542 ,. '
(1953).
'
de Semours 'O.), u. J. E. (to E. I' du Patent 2,625,536 (Jan. 13, 1953). (46F) Kise, iM. A. (to Allied Chemical & Dye Corp.), Ibid., 2,652,377 (Sept. 15, 1953). (47F) Kneisley, J. W.(to Hercules Powder Co ), Ibid., 2,646,410 (July 21, 1953). (48F) Kodak. Ltd., Brit. Patent 695,262 (Aug. 5 , 1953).
(45F)
Vol. 46, No. 9
(49I') Kohler, F. (to Deutsche Gold-und Silber-Scheideanstadt vorni. Roessler), U. S.Patent 2,650,910 (Sept. 1, 1953).
(SOT) Kropa, E. L., and Thomas,
American Cyanamid
(to E. I. du Pont de Semours h Co.), I b i d , , (52E') Lantz, TYI J., and Kalters, .J. 11.( t o Electro-Chemical Erlzineering \Ianufg. Co.),I b i d . . 2,660,573 (Sox-. 21, 1953). (53F) McDonald, J. (to Westinghouse Electric Corp.), I b i d . , 2,640,045 (May 26, 193). (54F) XIacDonald, R. N. (to E. I. du Pont de Neinours &- Co.), I b i d . . 2,650,214 (.lug. 24, 1953). (551;) NacDonald, R. N., and Tullock, C. W.( t o E. I. du Pont de 0,423 (-\larch 3, 1953). 3. B. (1)'s to ;\Iontclair Research er Co.). I h i d . , 2,628,246 (Feb
10, 1953). (57F) AIacKenzie, C. A., and Schoflman, 11. (to Llontclair Research Corp. and Ellis-Foster Co.), Ibid., 2,623,832 (Dee.
30, 1952). (58F) Nackenzie. C. A., Spialter, L., and Schoffman, hf. (to hIonr-
clair Research Corp.), Brit. Patent 684,597 (Dec. 24, 19521,
(59F) Marling, P. E., and Hempel, A. R. (to hlonsanto Chemical Co.), U. 6. Patents 2,637,707; 2,637,708 (May 5, 1953). (GOF) Xay, G. B., Wheatley. E. W., and Fisher, J. W.(to BritLh Celanese. Ltd.), Brit. Patent 694,441 (July 22, 1953). (61F) Mighton, H. R. (to E. I. du Pont de Nemours 8. Co.). U. 3 , Patent 2,647,105 (July 28, 1953). (62F) Morgan, P. IT. (to E . I. du Pont de Semours .& C o . ) , Ibid,, 2,631,993 (March 17, 1953). (63F) Sielsen, E. R., SOC.Plastics Engrs. J . , 9, S o . 2, 10 (1953j. (64F) Nile., G . E. (to XIonsanto Chemical Co.), U. 8. Patent
2,632,700 (March 24, 19.53). (65F) Sitzsche, S. (to Alexander Kacker Gesellschaft fiir elcktrochemische Industrie G.m.b.H.), Ihid.. 2,645,629 (July 14,
1953). (66F) Sitesche, S., and Pirson, E. (to Wacher-Chemie G.m.b.H.'~, rbid., 2,647,911 ( ~ u g4. , 1953). (67F) Sitzsche, S.,Wilberg, E., and Hertwig, A , , Ibid., 2,640,063
(Xay 26, 1953). (68F) N. V. de Bataafsche Petroleum Maatschappij, Brit. Patent 685,649 (Jan. 7, 1953). (69F) Oswald, F., Paint, O i l , Chem. Rev.,116, KO.21, 78 (1953). (;OF) Patrick, J. C., and Ferguson, H. R. (to Reconstruction Finance Corp.),U. S.Patent 2,646,415 (July 21,1953). (71F) Plueddemann, E. P. ( t o Libbey-Owens-Ford Glass Co.'), I b i d . , 2,642,447 (June 16. (72F) Ravich, G. B., and Fro\-ola, Dokladg Bizad. Nauh 8.8.S.R., 90, 391 (1953). (73F) Redfern. D. V. (to American-Marietta Co., Adhesive, Iiesiii. and Chemical Division), U. 8. Patent 2,631,098 (March 10. 1953). (74F) Reeder, F., and Wallsgrove, E. R. (to Cortauld's Ltd.), Brit. 8. 1953). Patent 693.980 iJulv ~. ~" (75F) Rose, F. L., and Swain, G. (to Imperial Chemical Industries, Ltd.),U. S.Patent 2,643,232 (June 23, 1953). (76F) Ross, S. D., and Xarkarian, M. (to Sprague Electric C o . " , r b i d . , 2,631,168 (March 10, 1953). (77F) Rust, J. B. (:/%to Xontclair Research Corp. and '/z to EllibFoster Co.),Ibid., 2,628,213 (Feb. 10, 1953). (78F) Rust, J. B. (:;zto hIontclair Research Corp. and 1 1 2 ElliaFoster Co.), Ibid., 2,637,718 (Xay 5 , 1953). (79F) Sanderson, R. T. (to Texas Co.), Ibid., 2,628,974 (Feb. 17, 1953). (80F) Schick, J. V., and Hartough, H. D. (to Socony-Vacuum Oil Co.), I b i d . , 2,625,550 (Jan. 13, 1953). (81F) Shokal, E. C., and Devlin, P. A. (to Shell Development Co.:, Ibid., 2,630,430 (March 3, 1953). (82F) Simons, J. I
