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Unit Processes Review
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Polymerization by Frank H. Bolton, The Dow Chemical Co., Midland, Mich.
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Interest continues high in the preparation of stereospecific polymers Search for inorganic polymers of practical utility was widespread Graft copolymers were prepared by free radical polymerization in a solution of preformed polymers
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unprecedrnted deluge of publications dealing \vith stereospecific polymerizations by Ziegler-type catalysts has spilled over into the whole broad area of ionic polymerization. LVhile there have been great advances in the understanding a n d commercial utilization of free radical polymerization in the past 20 years, this may be the decade of ionic, polvmerization. During the 1959 review year many of the more interesting advances came in the fields of ionic catalysis and stereoregular polymers. initiation of polymerization by radiation, a n d the preparation of block a n d graft copolymers. T h e search continued for inorganic polymers of practical utility. There \yere two reviews of the inorganic polymer field (70.9, 7 72).
catalysts \\’ere prepared from cyclopentadienyl (74) a n d alkoxy (7. 29) titanates. T h e anisoie etherates of trialkylaluminums. in contrast with the diethyl etherates, were reported to be excellent accelerators for Ziegler polyeth>lene production ( 4 7 ) . Sonpyrophoric catalysts were prepared from a titanium halide, aluminum, a n d a saturated aliphatic halide ( 4 ) . Catalyst variations included Tic14 plus organolithium compounds ( 5 9 ) ,CH3TiCl (from Tic212 and CHSMgCl) (704), azoalkanes plus TiClr i72)> and trialkylaluminums plus CrC13 (42). Ziegler-catalyzed copolymerizations included ethylene-propylene ( 7 8 ) and e t h y l e n e 1 -butene ( 8 6 ) . Crystalline syndiotactic 1,2-polybutadiene was prepared with a triethylaluminum-vanad i u m triacetylacetonate catalyst (, 8 s, ) . while trans-l,4(2:3-dimethylbutadiene) \vas prepared by Ziegler catalysis and by g a m m a ray-initiated polymerization of the thiourea-monomer complex ( 729). Stereospecific polymers were prepared from vinylcyclohexanes I
Stereospecific Polymers T h e catalytic reactivity a n d stereospecificity of organometal~iccompounds in olefin polymerization \\’ere cornPared (3~3).T h e relatioriships between swucture and properties were discussed Cor poly-olefins (75, 79) and polystyrenes
Highly elastic polymers of acetaldehyde were prepared with a calcined alumina catalyst ( 3 2 ) . Several studies were made of the chromia on silicaalumina (Phillips) catalysts in the polymerization of olefins (68>776, 777) and dienes ( 7 731. ~I
Ionic Polymerization Novel developments were the homopolymerization of monoisocyanates by sodium ( 707) and of electronegative
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Ziegler Catalysis I t was difficult to select a sampling from the many publications dealing n i t h Ziegler catalysts. Mechanism a n d kinetics continued to receive attention (83. 871, and grneral revielvs appeared (77, 80). Crystalline complexes weie isolated from the heterogeneous catalyst mixture (88, 727). T h e usual trialkylaluminum-Tic14 system was studied (25. 93’1, and soluble
Heterogeneous Catalysis
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Crystalline polymers Lvere prepared k o m methyl methacrylate (77), iertbutyl acrylate (69). and several alkyl acrylates (38).
(84. 702). Laboratory (708) and commercial (30) continuous Ziegler polymerizations were described. I t was reported that molecular weight fractionation of Ziegler polyethylene could be achieved bv particle size fractionation ( 2 4 ) .
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( S j ) . vinvl ethers ( 8 2 ) , heterocyclics (fuI a n . ‘-methylfuran, and thiophene) ( 7 75). monoallylsilane (85), and a large number of vinylaromatic monomers
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The complete bibliography and tables of the Polymerization Review for 1959, b y Bolion.
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JANUARY 1961
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d Unit Processes Review
97) and the solution polymerization of Organic hypoacrylonitrile (779). nitrites were recommended as lo\v temperature catalysts (6). Trialkylborons (35, 67) and dialk>-lcadmiums ( 3 4 ) react with oxygen to form the peroxides which a r e the actual polymerization catalysts. Poly(vin)l chloride) prepared a t -40" C . with triethylboron is said to have superior mechanical properties (706).
monomers by metal ketyls ( 5 3 ) . Styrene-methyl methacrylate (90) and styrene-isoprene (56, 7 74) copolymerization reactivities were used to determine the radical a n d ionic contributions to lithium-catalyzed polymerizations. Kinetic studies were m a d e of the anionic (butyllithium) polymerization of styrene (97) and the polymerization of methacrylonitrile by lithium in liquid ammonia (96). Catalyst coniposition a n d structure affected the polymerization of butadiene a n d styrene by organosodium reagents (75). Epoxides were polymerized by sodium alkoxides ( 4 0 ) ; Lewis acid metal halides (27) and alkoxides (70. 9 4 ) ; alkvlaluminums (27, 54) ; diethylzinc-alumina ( 3 6 ); diethylzinc with water, oxygen, o r alcohols ( 3 7 ) ; a n d by cobalt(I1) naphthenate ( 4 4 ) Monomeric epoxides were useful in lieu of peroxides for unsaturated ester polymerization (8).
Block and Graft Copolymers T h e preparation of graft copolymers \cas a favorite use for radiation in polymer science. Photoinitiated grafting included vinyl monomers to ccllulose. using anthraquinone dye sensitizers ( 3 9 ) , a n d methyl methacrylate to natural rubber in emulsion (23: 66). I n the latter. iron(II1) salts were used as ultraviolet sensitizers. G a m m a ra>-s ivere used in grafting monomers to polyolefin (5, 78? 50) a n d polytetrafluoroethylene (79) films, as well as for grafting in emulsion (22. 47) and solution ( 7 78). Graft copolymers prepared by free radical polymerization in a solution or preformed polymer included vinyl acctate on vinyl acetate-vinyl chloride copolymer (52). vinyl acetate on pol>.(vinyl alcohol) (46). polystyrene on (vinyl chloride) (72): methyl methlate on polyisoprene (2). a n d methyl methacrylate on natural rubber (78. 7 7 7). Emulsion grafting included vin\'l chloride on poly(buty1 methacrylate) ( 9 ) and vinyl monomers on natural rubber latex (700). Preparation of copolymers by mechanico-chemical reactions was revieived (77. 723). Chemical grafting sites \cere obtained from internal azonitrile groups (722); b>- dehydrochlorination of poly(viny1 chloride) folloLved by
Radiation Catalysis Sensitizers for photopolymerizarion were reviewed (26). Low temperature polymerization of styrene ( 9 2 ) and butadiene ( 3 ) by g a m m a rays appeared to be ionic. Solid additives (e.g.. Z n O ) increased the yield in the ionic radiation polymerization of isobutene (726, 727). -4crylamide was polymerized in the solid state ( 7 , 73). .4crolein (48) a n d ethylene (49) ivere polymerized by radiation.
Free Radical Polymerization Reviews of free radical polymerization included the effect of oxygen (55), end group analysis (77), a n d the correlation of free radical elementary processes with polymer structure ( 9 9 ) . Kinetic studies were m a d e of the thermal polymerization of styrene (7.3.
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oxidation (107); from polyperoxide esters ( 7 0 3 ) ; and from oxidation ol polyhydrocarbons (87). Caprolactam was grafted on poly(methy1 methacrylate) (724) a n d its copolymers (20). Sovel block copolymers \ v e m prcpared by copolymerizing p-propiolactone with vinyl monomers. then hydrolyzing to a polyester which \vas coupled with diisocyanates (62). Styrene and isoprene were alternately added io a buryllithium solution to form block copolymers ( 6 0 ) .
Emulsion and Suspension Polymerization Continuous emulsion polymcrization was described in theory ( 6 4 ) and in practice 176). I n contrast to the usual ivater-soluble catalysts, a n oil soluble peroxide was used to initiate the cmulsion polymerization of styrene (28). Initiation was investigated a t low emulsifier concentrations for vinyl chloride (6.3). Emulsion polymerization kinetics ivere studied for vinylidene chloride (65) a n d methyl methacrylate (737). Rubber-reinforced polystyrene \vas produced by the suspension polymerization of a n elastomer solution in styrene (770). Variables were studied in the suspension polymerization of rnethacrylates (57).
Condensation Polymerization T h e versatile interfacial polycondensation method was reviewed ( 7 4 ) and applied to the reaction of dithiols with dicarboxylic acid chlorides (76). T h e relation of physical properties to the structure of thermoset resins (725) and the distribution of components in condensation interpolymers (70) Ivere discussed. -4 continuous process for making silicones was described (57)! as \vel1 as equipment for the laboratory-scale preparation of polyesters ( 70.5). T h e alkali-catalyzed phenol-formaldehyde rcaction was studied (728), and hi:h melting point aromatic polyanhydrides were prepared (730j. M a n y publications dealt with e caprolactam polymerization. I nitiators included anhydrous HCI (7204 Grignard compounds (43, 98), and thc sodium salt of t-caprolactam ( 4 5 ) . Cyclic oligomers were incorporated into E-caprolactam polymerization ( 3 7 ) .
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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(91) Ibid., 35, 259 (1959). (92) Okamura, S.. Higashimura. T.. Futarni. S., Doitai io Hoshasen 1, 216 119581. \ --,
(93) Orzechowski, A . , J . Polymer Sci. 34, 65 (1959). (94) Osgan. M., Price, C. C.. Ibid., 34, 153 (1959). (95) Overberger, C. G., Mulvaney, J. E., J . .4m. Chem. SOC.81. 4697 (19591. (96) Overberger, C. ‘G., Pe‘arce,’ E. M.. Mayes: N., J . Polymer Sci. 34, 109 (1959). (9’) Patat, F.: Kirchner. K., Z . Elektrochem. 63, 292 (1959). (98) Schaaf, S.. Faserforsch. u Textiltpch. 10, 257 (1959). (99) Schulz, G. V., Angew. Chem. 71, 590 (1959). (100) Sekhar, B. C., J . Rubber Research Inst. Malaya 15, 205 (1959). (101) Shashoua, V . E., J . Am. Chem. Soc. 81, 3156 (1959). (102) Sianesi, D., Macchi, A , . Danusso. F.. Chim. e ind. (Milan)41, 964 (1959). (103) Smets, G.. Poot, A., others, J . Polymer Sei. 34, 287 (1959). (104) SociCtC belge du titane, S.A., Belg. Patent 560,503 (Sept. 30, 1957). 1105) Sopomonvants. Zh. S.. Zhur. Priklad. ‘ K h m z2, 1632 (1959). (106) SOLVIC Sac. anon, Belg. Patents 560,624 (March 6, 1958); 569,632 (Jan. 22, 1959). ( 1 0 7 Ib~d.. (March 26, 1959). , 571.542 , (108) Sommer. S., t\iagener. S.. Ebner. H.. Kunststoffe 49, 500 (1959) 1109) Sowrrbv. D. B.. Audrieth. L. F.. ‘ J.‘Chem. Ed&. 37, 2 (1960). (110) Stein, A . , Walter, R. L., U. S. Patents 2,862,906, 2,862,907 (Dec. 2, 1958), 2,886,553 (May 2, 1959). (1 1l i Swift. P. McL.. J . Abbl. ._ Chem. (London) i, 803 (i958j. (1 12) Thilo, E., Makromol. Chem. 34, 179 (1959). (1 13) Tinyakova, E. I., Dolgoplosk, B. A., others, Doklady Akad. Nauk S.S.S.R. 124, 595 (1959). (114) Tobolsky, A. V.: Rogers, C. E.: J . PolymerSci. 38, 205 (1959). (1 15) Topchiev, A. V., Krentsel, B. A,, Gol’dfarb, Yu. A., Izvest. Akad. Nauk S.S.S.R., Otdel Khim. .Vauk 1959, p. 369. (116) Topchiev, A. V.? Krentsel, B. A.! others, J . Polymer Sci. 34, 129 (1959). (117) Topchiev, A. V., Krentsel, B. A,, others. Izvest. Akad. Nauk S.S.S.R.; Otdel Khim. .Vauk 1959, p. 1079. (118) Turner, D . T., J . Polymer Sci. 35, 17 11959). ~
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(79) Ibid..p. 531. (80) Natta, G., SPE Journal 15, 373 (1959). (81) Natta. G., Beati, E.. Severini. F. J . Polymer Sci. 34, 681 (1959). (82) Natta. G., Dall’Asta, G.; Angerc. Chfm. 71, 205 (1959). (83) Natta. G.. Danusso. F., Pasquon I.. Collrction Czechoslou. Chem. Communs. (Spec. Issue) 22, 117 (1957). (84) Natta. G.. Danusso; F., Sianesi. D., .\;lokromol. Chem. 30, 238 (1959). (85) Natta. G.. Mazzanti, G.. others, Chim. e ind. (Milan) 40, 813 (1958). (86) Natta. G., Mazzanti, G., others, Ibid.. 41, 764 (1959). (87) Natta, G., Pasquon, I., Advances in Catalysis 11, 1 (1959). (88) Natta. G., Pino, P., others, J . Inor,o. & .\’itclear Chem. 8, 612 (1958). ( 8 9 ) Natta. G., Porri, L.. others, Chim. e ind. (.Milan) 41, 526 (1959). (90) O’Driscoll, K . F.. Tobolsky, A. V., J . Polymer Sci. 37, 363 (1959).
1959; No.’12. 18. (122) Vollmert, B., Bolte, H . , Makromol. Chem. 36, 17 (1959). (123) Lt’atson, W.F.. Ibid.: 34, 240 (1959). (124) LVichterle, O., Gregor, V., J . Polymer Sei. 34, 309 (1959). (125) it‘ood. E. H., SPE Tech. Papers 5, Paper No. 40 (1959). (126) Worrall, R., Charlsbv, A , . Intern J . AppI. Radiation and Isotopes 4, 84 (1958). (127) LVorrall, R., Pinner, S. H . , J . Pol.ymer Sci. 34, 229 (1959). (128) Yeddanapalli, L. M., Gopalakrishna. V. V.. Makromol. Chem. 32. 112 11959). (129) Yen, T. F., J . Polymkr Sa.’ 38, ’272 (1959). (130) Yoda, N.. Makromol. Chem. 32, 1 (1959). (131) Zimmt, \V. S., J . Appl. Poljmer Scz. 1, 323 (1959). VOL. 53, NO. 1
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