Patent GB-876659-A (GB)
Title: Polymerisation catalyst compositions
IPC: C08F36/04
Filed: 1960-04-20
Abstract: A catalyst composition for the polymerization of an ethylenically unsaturated monomer comprises crystals containing or consisting of a salt of cobalt, magnesium or cerium or a mixture thereof that have been coated on the surface with a thin layer of titanium, vanadium, cobalt or zirconium or a mixture thereof.  The salt may be a halide, sulphide, phosphide or silicide, and the crystals preferably have a size of 0,025-23 mm.  Polymerization is effected under anhydrous conditions and in an inert atmosphere (e.g. nitrogen or methane), by mixing the components at a temperature of 25 DEG -110 DEG C. and under a pressure of atmospheric to 1,000 p.s.i.  Apart from the monomer and the crystalline catalyst there may also be present (a) a co-catalyst, e.g. an alkyl of a metal such as aluminium, tin, lithium, sodium, titanium, zinc, cadmium, zirconium or cobalt; (b) a solvent such as octane, iso-octane, n-heptane, xylene or benzene; (c) additives to increase the polymerization rate or control molecular weight, e.g. hydrogen, oxygen, acetylene, pyridine, ethyl acetate, tributyl phosphite and phenols; and (d) titanium halides.  In the Examples, (1) propylene is polymerized in heptane and under nitrogen using titanium- or cobalt-coated cobaltous chloride and aluminium triethyl as co-catalyst; (2) propylene is polymerized as in (1) but using titanium-coated magnesium chloride; (3) propylene is polymerized as in (1) but using vanadium-coated cobaltous bromide or magnesium chloride; (4) propylene, a 1 : 1 mixture of propylene/ethylene or a 1 : 1 mixture of propylene/butene-1 are polymerized (or co-polymerized) in heptane using vanadium-coated cerium trichloride and aluminium triethyl as co-catalyst; (5) propylene is polymerized in heptane using zirconium-coated magnesium chloride and aluminium triethyl as co-catalyst; (6) propylene, ethylene, styrene, butadiene or isoprene are polymerized in heptane using zirconium-coated cobaltous chloride and aluminium triethyl as co-catalyst; (7) methyl methacrylate or a 1 : 1 mixture of methyl methacrylate/butyl methacrylate are polymerized (or co-polymerized) in benzene using titanium-coated cobaltous chloride and, as co-catalyst, aluminium-triethyl, -triisobutyl, or -diethyl chloride; (8) vinyl chloride is polymerized in benzene using titanium-coated cobaltous chloride and aluminium-triethyl or -diethyl chloride as co-catalyst; (9) methacrylic acid or a 3 : 1 mixture of methacrylic acid/acrylic acid are polymerized (or copolymerized) in benzene and under nitrogen using titanium-coated cobaltous chloride and aluminium triethyl as co-catalyst; (10) methyl acrylate is polymerized in benzene using titanium-coated cobaltous chloride and aluminium triethyl as co-catalyst; (11) propylene is polymerized as in (1) but using cobaltous chloride coated with titanium plus vanadium or titanium plus zirconium; (12) propylene is polymerized as in (1) but using crystals of sodium chloride plus cobaltous chloride, lithium chloride plus cobaltous chloride or barium sulphate plus cobalous chloride, coated with titanium.  It is stated that the following monomers may also be polymerized: isobutylene, isoamylene, hexylene, decene, dodecene, octadecene, methyl pentadiene, dimethyl butadiene, piperylene, butyl acrylate, propyl acrylate, vinylidene bromide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl butyrate, divinyl succinate, divinyl adipate, divinyl phthalate, diallyl phthalate, vinyl allyl pimelate, vinyl acrylate, allyl acrylate, vinyl crotonate, vinyl methacrylate, diallyl ether, allyl butyl ether, vinyl allyl ether, vinyl butyl ketone, vinyl ethyl ketone, the esterification product of ethylene glycol, glycerine or hexanetriol with acrylic or methacrylic acid, and the triallyl ether of glycerol or of hexanetriol.ALSO:A catalyst composition for the polymerisation of an ethylenically unsaturated monomer comprises crystals containing or consisting of a salt of cobalt, magnesium or cerium or a mixture thereof that have been coated on the surface with a thin layer of titanium, vanadium, cobalt or zirconium or a mixture thereof. The salt may be a halide, sulphide, phosphide or silicide, and the crystals preferably have a size of 0.025-23 mm.  Polymerisation is effected under anhydrous conditions and in an inert atmosphere (e.g. nitrogen or methane), by mixing the components at a temperature of 25 DEG -110 DEG C. and under a pressure of atmospheric to 1000 p.s.i. Apart from the monomer and the crystalline catalyst there may also be present (a) a co-catalyst, e.g. an alkyl of a metal such as aluminium, tin, lithium, sodium, titanium, zinc, cadmium, zirconium or cobalt, (b) a solvent such as octane, isooctane, n-heptane, xylene or benzene, (c) additives to increase the polymerisation rate or control molecular weight, e.g. hydrogen, oxygen, acetylene, pyridine, ethyl acetate, tributyl phosphite and phenols, and (d) titanium halides.  Catalysts used in the examples are as follows, using AlEt3 as co-catalyst except where otherwise indicated: -(1) titanium- or cobalt-coated cobaltous chloride, (2) titanium-coated magnesium chloride, (3) vanadium-coated cobaltous bromide or magnesium chloride, (4) vanadium-coated cerium trichloride, (5) zirconium-coated magnesium chloride, (6) zirconium-coated cobaltous chloride, (7) titanium-coated cobaltous chloride, and aluminium-triethyl, -triisobutyl, or -diethyl chloride, (11) cobaltous chloride coated with titanium plus vanadium or titanium plus zirconium, (12) crystals of sodium chloride plus cobaltous chloride, lithium chloride plus cobaltous chloride or barium sulphate plus cobaltous chloride, coated with titanium.ALSO:A catalyst composition for the polymerization of an ethylenically unsaturated monomer comprises crystals containing or consisting of a salt of cobalt, magnesium or cerium or a mixture thereof that have been coated on the surface with a thin layer of titanium, vanadium, cobalt or zirconium or a mixture thereof.  The coating may be effected by vacuum evaporation, the crystals being heated under vacuum to clean them before the coating metal is evaporated, or by decomposition of organometallic compounds.  The salt may be a halide, sulphide, phosphide or silicide, and the crystals preferably have a size of 0.025-23 mm.  The examples refer to the production of coatings of titanium on crystals of cobaltous chloride, sodium chloride, lithium chloride or barium sulphate, containing cobaltous chloride, and magnesium chloride; vanadium on cobaltous bromide, magnesium chloride and cerium trichloride; cobalt on cobaltous chloride; zirconium on magnesium chloride and cobaltous chloride; and titanium/vanadium and titanium/zirconium on cobaltous chloride.