Patent GB-873657-A (GB)
Title: Polymerization process and catalysts therefor
Inventor: KLOPFER OSKAR E H
IPC: C08F10/00
Filed: 1957-04-25
Abstract: A polymerization catalyst comprises an organo-metallic compound "1" with further components selected from Friedel Crafts compounds "2b," a modifying polar compound "2a" and/or a carrier component "3," as follows: (A) at least one each of "2a," "2b," and "3," provided that when "1" is derived from Al, "3" is other than a metal or metal hydride, or (B) at least three such further components of which at least two are selected from "2a," "2b" or "3" and at least one is selected from a different group of the components "2a," "2b" or "3," or (C) at least one each of "2b" and "3" provided the metal of "1" is from Group Ia of the Periodic Table and this component is derived from a paraffinic hydrocarbon substituted with an aromatic substituent or from a hydrocarbon polymer.  Component "1" is defined as containing a single metal atom bonded to the organic moiety by a carbon-metal bond; said moiety may be polymeric or non-polymeric, while the metal atom is selected from Li, Na, K, Rb, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn, Ph and the rareearth metals.  Component "2b" comprises halides, oxyhalides and halide complexes with halogen acids of Cu, Ag, Mg, Zn, Cd, Hg, B, Al, Ga, Tl, Ti, Zr, Hf, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, U, Te, Mn, Fe, Co and Ni.  Component "2a" consists of organic donor compounds containing one or more of O, N, S, Se, Te, halogens; various classes of such compounds being mentioned and a number of peroxides and azo-compounds being also specified; such donor compounds include those in which active hydrogen atoms have been replaced by metals.  Component "3" is an inorganic solid not detrimental to the polymerization and including shaped materials and carbon.  Many metals and acid radicals suitable as constituents of this component are listed as are many specified oxides.  The usual hydrocarbons and their halogenated derivatives are mentioned as solvents for catalyst formation and polymerization.  In examples, chlorostyrene, 1-trifluoromethyl-1 : 2-dichloroethylene, vinyl chloride, vinylidene chloride, tetrafluoroethylene, acrylonitrile, methyl methacrylate and allyl arylphosphonate are homopolymerized, and ethylene, propylene, isobutylene, butadiene and isoprene homo- and co-polymerized (including terpolymerization), in presence of catalysts containing components selected from the following: "1" : Et3Al, i-Bu3Al, amyl-Na, p-xylene mono-Na, -Li and -K and the mono-Na derivatives of xylenes, mesitylene, dimethylnaphthalene, toluene and a -methylstyrene trimer; "2a" : i-PrONa, (i-Pr)2CO, diethyl ether and the AlCl3, TiCl4 and BF3 etherates thereof, pyridine, diethyl carbonate, n-butyraldehyde, morpholine and N-phenyl-N1-cyclohexyl-p-phenylenediamine; "26" : AlCl3, TiCl4, ZrCl4, UCl4, ZnCl2 and CrO2Cl2; "3" : Al, NaCl and KCl.  The monomers which in general may be polymerized with the above catalyst contain at least one polymerizable ethylenic and/or acetylenic linkage; the monomer may itself form the diluent as an alternative to using a separate diluent.  Numerous monomers are listed in the Specification; these include the following types: -olefines; chloro, fluoro, chlorofluoro and bromo olefines including chloro- and bromo-aryl and alkaryl olefines; aryl and alkaryl olefines; conjugated dienes and trienes; acetylenes and low polymers thereof.  Specifications 817,887, 831,838, 873,658, 873,661 and 873,662 are referred to.ALSO:A polymerization catalyst comprises an organo-metallic compound "1" with further components selected from Friedel Crafts compounds "2b", a modifying polar compound "2a" and/or a carrier component "3", as follows:-(A) at least one each of "2a", "2b" and "3", provided that when "1" is derived from Al, "3" is other than a metal or metal hydride, or (B) at least three such further components of which at least two are selected from "2a", "2b" or "3" and at least one is selected from a different group of the components "2a", "2b" or "3", or (C) at least one of each of "2b" and "3" provides the metal of "1" is from Group IA of the Periodic Table and this component is derived from a paraffinic hydrocarbon substituted with an aromatic substituent or from a hydrocarbon polymer.  Component "1" is defined as containing a single metal atom bonded to the organic moiety by a carbon-metal bond; said moiety may be polymeric or non-polymeric, while the metal atom is selected from Li, Na, K, Rb, Ca, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn, Pb and the rare-earth metals.  Component "2b" comprises halides, oxyhalides and halide complexes with halogen acids of Mg, Zn, Cd, Hg, B, Al, Ga, Tl, Ti, Hf, Zr, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, U, Te, Mn, Fe, Co, Ni, Cu and Ag.  Component "2a" consists of organic donor compounds containing one or more of O, N, S, Se, Te, halogens; various classes of such compounds being mentioned and a number of peroxides and azo-compounds being also specified; such donor compounds include those in which active hydrogen atoms have been replaced by metals. Component "3" is an inorganic solid not detrimental to the polymerization and including shaped materials and carbon.  Many metals and acid radicals suitable as constituents of this component are listed as are many specified oxides.  The usual hydrocarbons and their halogenated derivatives are mentioned as solvents for catalyst formation and polymerization.  In examples, chlorostyrene, 1-trifluoromethyl-1:2-dichloroethylene, vinyl chloride vinylidene chloride, tetrafluoroethylene, acrylonitrile, methyl methacrylate and alkyl acrylphosphonate are homopolymerized, and ethylene, propylene, isobutylene, butadiene and isoprene homo-and co-polymerized (including terpolymerization), in presence of catalysts containing components selected from the following:-"1": Et3Al, i-Bu3Al, amyl-Na, p-xylene mono-Na, Li and K, and the mono-Na derivatives of xylenes, mesitylene, dimethylnaphthalene, toluene and a -methylstyrene trimer; "2a": NaO-i-Pr2(i-Pr)2CO, diethyl ether and the AlCl3, TiCl4 and BF3 etherates thereof, pyridine, diethylcarbonate, n-butyraldehyde, morpholine and N-phenyl-N1-cyclohexyl-p-phenylnediamine; "2b": AlCl3, TiCl4, ZrCl4, VCl4, ZnCl2 and CrO2Cl2; "3": Al, NaCl and KCl.  The monomers which in general may be polymerized with the above catalyst contain at least one polymerizable ethylenic and/or acetylenic linkage; the monomer may itself form the diluent as an alternative to using a separate diluent.  Numerous monomers are listed in the Specification; these include the following types:-a -olefines; chloro, fluoro, chlorofluoro and bromo olefines including chloro and bromo aryl and alkaryl olefines; aryl and alkaryl olefins; conjugated dienes and trienes; acetylenes and low polymers thereof.  Specifications 817,887, 831,838, 873,658, 873,661 and 873,662 are referred to.