Patent GB-855012-A (GB)
Title: Catalytic polymerisation of alpha-ethylenically unsaturated monomers
IPC: C08F10/00
Filed: 1956-12-28
Abstract: Alpha-ethylenically unsaturated monomers are polymerized by contact with a catalyst comprising a slurry in an inert organic solvent of a salt of a metal capable of existing in a plurality of valency states, the metal being present in the slurry in one of its lower valency states, and at least 0,1% by weight based on the salt of a metal hydride, metal alkyl, metal alkyl hydride, metal alkyl halide or metal alkyl ester as an activator.  The salt is of a metal of Groups Ib, IIIb, IV, VI, VII and VIII of the Periodic Table and is reduced in the organic solvent to the lower valency state with metallic sodium, potassium, lithium, calcium magnesium, aluminium or zinc, or an amalgam thereof, to obtain the slurry to which the activator is added.  In examples ethylene, propylene, styrene, vinyl chloride and vinyl fluoride are polymerized in slurries of titanium tetrachloride, chromium trichloride, cobalt trichloride, zirconium tetrachloride, germanium tetrachloride, indium trichloride, manganese trifluoride, molybdenum tetrachloride, osmium trichloride, tin tetrachloride, chromium acetylacetonate, titanium tetrapropionate, ferric chloride, tungsten hexachloride, platinic chloride and zirconium acetylacetonate, all reduced to lower valency states by reduction with sodium amalgam, calcium, magnesium, potassium amalgam, zinc, lithium amalgam, sodium, lithium or aluminium; the activators used are zinc diethyl, sodium boron hydride, lithium ethyl, lithium aluminium hydride, tetraethyl lead, tetraethyl tin, dimethyl zinc, dimethyl tin and triethyl aluminium; the organic solvents are heptane, heavy paraffin oil, tetralin, decane, decalin, cyclohexane, xylene, dioxane and octane.  Lists of salts which may be reduced, activators and solvents are given.ALSO:A polymerization catalyst comprises a slurry in an inert organic solvent of a salt of a metal capable of existing in a plurality of valency states, the metal being present in the slurry in one of its lower valency states, and at least 0.1% by weight based on the salt of a metal hydride, metal alkyl, metal alkyl p  hydride, metal alkyl halide or metal alkyl ester as an activator. The salt is of a metal of Group IB, IIIB, IV, VI, VII and VIII of the Periodic Table and is reduced in the organic solvent to the lower valency state with metallic sodium, potassium, lithium, calcium magnesium, aluminium or zinc, or an amalgam thereof, to obtain the slurry to which the activator is added.  In examples, catalysts comprise slurries of titanium tetrachloride, chromium trichloride, cobalt trichloride, zirconium tetrachloride, germanium tetrachloride, indium trichloride, manganese trifluoride, molybdenum tetrachloride, osmium trichloride, tin tetrachloride, chromium acetylacetonate, titanium tetrapropionate, ferric chloride, tungsten hexachloride, platinic chloride and zirconium acetylacetonate, all reduced to lower valency states by reduction with sodium amalgam, calcium, magnesium, potassium amalgam, zinc, lithium amalgam, sodium, lithium or aluminium; the activators used are zinc diethyl, sodium boron hydride, lithium ethyl, lithium aluminium hydride, tetraethyl lead, tetraethyl tin, dimethyl zinc, dimethyl tin and triethyl aluminium; the organic solvents are heptane, heavy paraffin oil, tetralin, decane, decalin, cyclohexane, xylene, dioxane and octane. Lists of salts which may be reduced, activators and solvents are given.