Patent GB-981840-A (GB)
Title: Method of polymerising olefins
IPC: C08F4/70
Filed: 1963-05-31
Abstract: A catalyst for the polymerization of 1-olefines (see Division C3) comprises the reaction product of an organo-phosphine-metal salt complex of formula (R3P)2MX2 and an adipic metal halide of formula M1X1n, or the etherate thereof, wherein R is hydrocarbon; M is Ni, or Co; X is F, Cl, Br, or I, or SCN; M1 is a metal of valency n, whose halides are Lewis acids and X1 is Cl or Br. Suitable hydrocarbon groups, R, are phenyl or butyl; named acidic metal halides are: HgCl2, AlCl3, AlBr3, TiCl4, FeCl2, FeCl3, ZnCl2, SbCl3, SbCl5, BeCl2, ClCl2, CaCl2, BF3, GaCl3, ZrCl3, SnCl4, MoCl5, and ZnBr2, and the etherate, BF3.O(C2H5)2.  The catalyst is prepared by interaction of the metal halide and organo phosphine-metal salt complex in an inert dry solvent such as aliphatic or aromatic hydrocarbons or halogenated hydrocarbons; the phosphine complex is suitably obtained by reaction of the metal salt MX2 with an organo phosphine in, e.g. glacial acetic acid or butanol. Addition of small quantities of a suitable halohydrocarbon enhances the catalytic properties.  Many examples are given for the preparation of the catalytic compounds and their use in polymerizing various 1-olefins or mixtures thereof.ALSO:1-Olefins are polymerized to high molecular weight polymers (average M.W. of at least 10,000), by contacting them in absence of air, water, and active hydrogen containing substances, with a polymerization catalyst comprising the reaction product of an organophosphine-metal salt complex, of formula (R3P)2MX2 and an acidic metal halide, M1 X1n, or etherate thereof, wherein R is hydrocarbon; M is Co or Ni; X is F, Cl Br, I, of SCN; M1 is a metal of valency n, whose halides are Lewis acids; and X1 is Cl or Br (see Division C2). The polymers are preferably homo- or copolymers of butadiene, with more than 40%, especially more than 60%, of the butadiene monomer units having cis-1,4 configuration, but co-polymers of butadiene with isoprene, styrene, isobutylene, and propylene may also be prepared, and homopolymers of these lastnamed monomers.  In the catalyst, R is preferably phenyl or butyl, and M1 is suitably Al, Ti or Br, but many other compounds are given.  Polymerization may also be effected by contacting the monomer with a mixture of the components of the catalyst, i.e. organo-phosphine-metal salt complex and the appropriate Lewis acid.  Catalytic action is greatly enhanced by addition of a halohydrocarbon, suitably n-butyl chloride, methylene chloride, or chlorobenzene.  Examples are given wherein are polymerized: butadiene; isoprene; styrene, isobutylene, and propylylene; and copolymers of butadiene with isobutylene, and butadiene with propylene are also prepared.ALSO:Catalyst components for the polymerization of 1-olefins, particularly butadiene, comprise the reaction product of an organo-phosphine-metal salt complex of formula (R3P)2MX2, and a metal halide of formula M1X1n, or etherate thereof, which is a Friedel Crafts catalyst, wherein R is a hydrocarbon radical, M is Ni or Co, X is F, Cl, Br, I or SCN, X1 is Cl or Br, and M1 is a metal of valence n, whose halide is a Lewis acid (see Division C2), a suitable halohydrocarbon (e.g. n-butyl chloride, chlorobenzene, or methylene dichloride).  The catalyst is employed in the absence of air, water, and any active hydrogen-containing substance. Suitable R groups are phenyl and butyl, Friedel Crafts catalysts listed are: HgCl2, BF3,O(C2H5)2, AlCl3, AlBr3, TiCl4, FeCl2, FeCl3, ZnCl2, SbCl3, SbCl5, BeCl2, CdCl2, CaCl2, BF3, GaCl3, ZrCl3, SnCl4, MoCl5 and ZnBr2.