Patent GB-873656-A (GB)
Title: Polymerization process and catalysts therefor
IPC: C08F10/00
Filed: 1957-04-25
Abstract: A polymerisation catalyst comprises a multimetallated organic compound "1" with or without a Friedel Crafts compounds "2b," a modifying polar compound "2a" and/or a carrier component "3," subject to the condition that when the metal of "1" is solely Na, K or Mg, at least one of the other components is present.  Component "1" is defined as containing at least two metal atoms bonded to the same hydrocarbon moiety by carbon-metal bonds; said moiety may be polymeric or non-polymeric, while the metal atoms are selected from Li, Na, K, Rb, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn and Pb, compounds formed by addition of an alkali metal or p  hydride thereof to the unsaturated bond(s) of non-polymeric or dimeric organic compounds being specifically excluded.  Component "2b" comprises halides, oxyhalides and halide complexes with halogen acids of Mg, Zn, Cd, Hg, B, Al, Ga, Ti, Zr, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, U, Te, 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and azo-compounds being also specified; such donor compounds include those in which active hydrogen atoms have been replaced by metals.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 organic or inorganic solid not detrimental to the polymerisation 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 ethylene, propylene, isobutylene, butadiene, isoprene, styrene, a -methylstyrene and vinyltoluene are homo- or copolymerized (including terpolymerization) in the presence of catalysts containing components selected from the following: "1" : a -methylstyrenetrimertrisodium, alkalimultimetallated xylenes especially p-xylene di- Na, -Li or -K, Namultimetallated mesitylene, dimethylnaphthalene, polyvinyltoluene and polyisoprene : "2a" : i-Pr-ONa, (i-Pr)2CO, N-phenyl-N1-cyclohexyl-p-phenylenediamine, pyridine, diethyl carbonate, butyraldehyde, morpholine, diethyl ether and the BF3, AlCl3 and TiCl4 etherates thereof; "2b": AlCl3, TiCl4, ZrCl4VCl4 and CrO2Cl2; "3": the respective alkali-metal halides accompanying the preparation of components "1."  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 olefines; conjugated dienes and trienes; acetylenes and low polymers thereof.  Specifications 873,658, 873,660 and 873,663 are referred to.  Reference has been directed by the Comptroller to Specification 821,971.ALSO:A polymerization catalyst comprises a multimetallated organic compound "1" with or without a Friedel Crafts compounds "2b", a modifying polar compound "2a" and/or a carrier component "3", subject to the condition that when the metal of "1" is solely Na, K or Mg, at least one of the other components "2a", "2b" or "3" is present.  Component "1" is defined as containing at least two metal atoms bonded to the same hydrocarbon moiety by carbon-metal bonds; said moiety may be polymeric or non-polymeric, while the metal atoms are selected from Li, Na, K, Rb, Cs, Cu, Ag, Be, Mg, Ca, Sr, Ba, Zn, Cd, Hg, B, Al, Sc, Yb, La, Ga, In, Tl, Ti, Zr, Th, Ge, Sn and Pb, compounds formed by addition of an alkali metal or hydride thereof to the unsaturated bond(s) of nonpolymeric or dimeric organic compounds being specifically excluded.  Component "2b" comprises halides, oxyhalides and halide complexes with halogen acids of Mg, Zn, Cd, Hg, B, Al, Ga, Ti, Zr, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, U, Te, 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 organic or 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, ethylene, propylene, isobutylene, butadiene, isoprene, styrene, a -methylstyrene and vinyltoluene are homo- or copolymerized (including terpolymerization) in the presence of catalysts containing components selected from the following:-"1":a -methylstyrenetrimertrisodium, alkalimultimetallated xylenes especially p-xylene di-Na, -Li or -K, Na-multimetallated mesitylene, dimethylnaphthalene, polyvinyltoluene and polyisoprene; "2a":i-PrONa1(i-Pr)2CO, N-phenyl-N1-cyclohexyl-p-phenylenediamine, pyridine, diethyl carbonate, butyraldehyde, morpholine, diethyl ether and the BF3, AlCl3 and TiCl4 etherates thereof; "2b": AlCl3, TiCl4, ZrCl4, VCl4 and CrO2Cl2; "3"; the respective alkali-metal halides accompanying the preparation of components "1".  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 873,658, 873,660 and 873,663 are referred to.  Reference has been directed by the Comptroller to Specification 821,971.