Patent GB-969073-A (GB)
Title: Catalyst and polymerization of ethylenically unsaturated compounds therewith
IPC: C08F4/42
Filed: 1962-04-04
Abstract: A polymerization catalyst composition comprises a pentahydrocarbon ammonium compound and a compound of a heavy metal, boron, silicon, arsenic, or tellurium.  The pentahydrocarbon ammonium compound is generally prepared by the reaction of an organometallic compound e.g. an alkali metal hydrocarbon compound such as sodium benzyl, with a quaternary salt in particular a quaternary halide.  The term "heavy metal" means, the elements set forth on pp. 54 and 55 of Lange's Hand-Book of Chemistry, 5th Ed., Handbook Publishers Inc., 1944, and includes the rare earth elements. Additives such as hexamethyl phosphoramide may be incorporated in the catalyst, and also polymerization modifiers such as alkylamino compounds of silicon and titanium.  The catalyst is used to polymerize ethylenically unsaturated compounds, and the catalyst may be preformed or formed in situ.  The polymerization may be performed batchwise or continuously. The polymers which may be crystalline and isotactic in structure are recovered from the polymerizate by conventional techniques. Specified pentahydrocarbon ammonium compounds are benzyltriphenylmethyl-, 9-fluorenyl - tetramethyl ammonium, benzyl tetrabutyl ammonium, benzyl orthoxylylene dimethyl ammonium, dibenzyl-, benzyl phenyl-, triphenylmethyl benzyl-, triphenylmethyl phenyl-, benzyl tallow-, triphenyl tallow-, 9-fluorenyl phenyl-trimethyl ammonium, and dibenzyl dimethyl tallow ammonium. The heavy metal compound may be titanium di-, tri,- or tetra-chloride, titanium tetrabutoxide, zirconium tetrachloride, zirconium acetylacetonate, vanadium oxytrichloride, ferric chloride, ferrous chloride, antimony pentachloride, antimonyl chloride, bismuth trichloride, stannic chloride, cobaltous chloride, tungsten pentachloride, chromium chloride, nickel chloride, or the reaction product of aluminium and titanium tetrachloride. The catalyst is generally prepared in a hydrocarbon diluent, and reaction of the ingredients is promoted by grinding the catalyst composition. Specified monomers are ethylene, propylene, butene-1, isobutylene, pentene-1, hexene-1, octene-1, 2-methylbutene-1, 2-methylpentene-1, 3-methylpentene-1, 3-ethylpentene-1, cyclopentene, cyclohexene, styrene, alphamethylstyrene, chlorostyrene, divinylbenzene, vinylnaphthalene, butadiene-1, 3, chloroprene, isoprene, 2,3-dimethylbutadiene-1, 3, piperylene, 1-cyanobutadiene, 2-phenylbutadiene, cyclopentadiene, 2-methoxybutadiene, 1,4-pentadiene, 1,4,7-octatriene, vinyl chloride, vinylidene chloride or fluoride, chlorotrifluoroethylene, vinyl pyrrolidone, alkyl acrylates and methacrylates, vinyl acetate, vinyl ethers, vinyl propionate, acrylonitrile, cinnamic acid esters, methacrylonitrile, vinyl pyridines, vinyl carbazole or mixtures. Specification 969,074 is referred to.ALSO:A polymerization catalyst composition comprises a p  pentahydrocarbon ammonium compound and a compound of a heavy metal, boron, silicon, arsenic, or tellurium.  The pentahydrocarbon ammonium compound is generally prepared by the reaction of an organometallic compound, e.g. an alkali metal hydrocarbon compound with a quaternary salt, in particular a quaternary halide.  The term "heavy metal" means the elements set forth on pages 54 and 55 of Lange's Hand-Book of Chemistry, 5th ed., Handbook Publishers Inc., 1944, and includes the rare earth elements.  Additives such as hexamethyl phosphoramide may be incorporated in the catalyst, and also polymerization modifiers such as alkylamino compounds of silicon and titanium.  Specified pentahydrocarbon ammonium compounds are benzyl-, triphenylmethyl-, 9-fluorenyl-tetramethyl ammonium, benzyl tetrabutyl ammonium, benzyl orthoxylylene dimethyl ammonium, dibenzyl-, benzyl phenyl-, triphenylmethyl benzyl-, triphenylmethyl phenyl-, benzyl tallow; triphenyl tallow-, 9-fluorenyl phenyl-trimethyl ammonium, and dibenzyl dimethyl tallow ammonium. The heavy metal compound may be titanium di-, tri-, or tetra-chloride, titanium tetrabutoxide, zirconium tetrachloride, zirconium acetylacetonate, vanadium oxytrichloride, ferric chloride, ferrous chloride, antimony pentachloride, antimonyl chloride, bismuth trichloride, stannic chloride, cobaltous chloride, tungsten pentachloride, chromium chloride, nickel chloride, or the reaction product of aluminium and titanium tetrachloride.  The catalyst is generally prepared in a hydrocarbon diluent. and the reaction of the ingredients promoted by grinding the catalyst composition. Specification 969,074 is referred to.