Patent GB-957473-A (GB)
Title: Catalysts for polymerising unsaturated organic compounds, and a process for their manufacture
IPC: C08F4/16
Filed: 1961-04-19
Abstract: Ethylenically unsaturated compounds may be polymerized by means of a catalyst prepared by reacting a fluid hydrogen-silicon polymer containing 10 to 100 mol per cent of units of the formula RnHmSiO 4-n-m/2 where R is a monovalent hydrocarbon or halogenohydrocarbon radical, m has an average value of 1 to 3, n has an average value of 0 to 2 and n+m is less than 4, and up to 90 mol per cent of units of formula SiO 4/2 , RSiO 3/2 , R2SiO or R3SiO 1/2 where R has the meaning aforesaid, with a compound of boron, aluminium, gallium, indium or thallium in amount of 0.001 to 10 mols per mol of the polysiloxane unit containing hydrogen-silicon, at a temperature within the range 10 to 200 DEG C., and reacting the product with a compound of a metal of subgroup IVa, Va, VIa or VIIa or Group VIII of the Mendel<\>aeef Periodic Table. Specified monomers are olefins, styrene, substituted styrenes, vinylcyclohexane, vinyl acetate, vinyl chloride and acrylic acid derivatives, and polymerization may be effected batchwise or continuously.  Many suitable radicals R are specified including alkyl, cycloalkyl, alkenyl, aryl, aralkyl and alkaryl radicals and the halogenated derivatives thereof.  Many suitable compounds of Group III elements are specified, including halides, alkoxides, halogen alkoxides, aryloxides, halogen aryloxides, trialkylsiloxy halides, organo halides, organo hydrides, alkoxide hydrides, organo compounds, organo oxides, and complexes thereof with metal halides and alkyl halides.  Many suitable compounds of Group IV-VIII metal compounds are specified, including halides, oxyhalides, oxyhalogen alkoxides, alcoholates, acetates, acetylacetonates and cyclopentadienyl halides.  Catalyst formation and polymerization may be effected in an inert solvent, e.g. n-pentane, n-heptane, isooctane, ligroin, benzine, cyclohexane, benzene, xylene, trichlorethylene, perchlorethylene, bromobenzene and chlorobenzene; and optionally in the presence of an inert catalyst carrier such as finely divided polyethylene, polypropylene, polystyrene, sodium chloride, silica or carbon black.  The activity of the catalysts may be increased by ageing. Examples describe the polymerization of (1-65 and 69-83) ethylene, (67, 69 and 84) propylene, (68 and 84) vinyl chloride and (84) butene-1, octene-1, vinyl acetate, styrene, a -methyl styrene and vinyl-cyclohexane in the presence of catalysts formed by reacting trimethylsilyl blocked methylhydrogen-siloxanes with (1-53, 57, 58, 61, 63-65 and 68) aluminium trichloride and titanium tetrachloride, a polyethylene carrier being employed in (49, 50 and 64), (54) aluminium isopropylate and titanium tetrachloride, (55) aluminium trichloride, titanium tetrachloride and ferric chloride, (56) aluminium trichloride and vanadium oxychloride, (60) aluminium trichloride, titanium tetrachloride and violet titanium trichloride, (62) aluminium trichloride, titanium tetrachloride and vanadium oxychloride, (66) aluminium trichloride and butyl titanate and (67) aluminium trichloride, titanium dichloride and titanium trichloride; a trimethylsiloxy blocked polysiloxane containing 54 mol per cent of CH3SiHO- units and 45 mol per cent of dimethyl siloxane units with (69) aluminium trichloride and titanium tetrachloride; a linear methylhydrogen polysiloxane containing 30 silicon atoms with (70-79) aluminium trichloride and titanium tetrachloride, (82) titanium tetrachloride and aluminium butylate, trimethylsiloxy aluminium dichloride, tripropylsiloxy aluminium dibromide, aluminium tribromide, diethoxy aluminium chloride, aluminium propylate, hexyloxy aluminium dichloride, an aluminium trichloride-titanium trichloride complex, boron halides, gallium trichloride, dimethyl boron bromide, diethoxy boron chloride, dimethoxy boron hydride, dimethyl diborane, [(CH3)2B]2O, phenyl boron dichloride or tripropyl boron, and (83) aluminium trichloride and zirconium tetrachloride, vanadium tetrachloride, molybdenum pentachloride, ferrous chloride, ferric chloride, cobaltous bromide, chloride or fluoride, butoxy titanium trichloride, zirconium oxychloride, vanadium oxychloride methoxide, diethoxymolybdenum trichloride, alkyl or aryl zirconates or titanates, zirconium tetraacetate, titanium dichloro diacetate, zirconium, cobalt and chromium acetylacetonates and chloro-bis(cyclopentadienyl) compounds of titanium, zirconium, vanadium and chromium; a methyl-hydrogen polysiloxane containing 6 silicon atoms with (80) aluminium trichloride and titanium tetrachloride; and a methyl-hydrogen polysiloxane containing 100 silicon atoms with (81) aluminium trichloride and titanium tetrachloride. Specification 906,425 is referred to.ALSO:Catalysts for the polymerization of ethylenically unsaturated compounds are prepared by reacting a fluid hydrogen-silicon polymer containing 10-100 mol per cent of units of the formula <FORM:0957473/B1-B2/1> where R is a monovalent hydrocarbon or halogenohydrocarbon radical, m has an average value of 1 to 3, n has an average value of 0 to 2 and n+m is less than 4, and up to 90 mol per cent of units of the formula SiO 4/2 , RSiO 3/2 , R2SiO or R3SiO 1/2 where R has the aforesaid meaning, with a compound of boron, aluminium, gallium, indium or thallium in amount of 0,001-10 mols per mol of the polysiloxane unit containing hydrogen-silicon, at a temperature within the range 10-200 DEG C., and reacting the product with a compound of a metal of subgroups IVa, Va, VIa or VIIa or Group VIII of the Mendel<\>aeeff Periodic Table.  Many suitable radicals R are specified, including alkyl, cycloalkyl, alkenyl, aryl, aralkyl and alkaryl radicals and the halogenated derivatives thereof.  Many suitable compounds of Group III elements are specified, including halides, alkoxides, halogen alkoxides, aryloxides, halogen aryloxides, trialkyl siloxy halides, organo halides, organo hydrides, alkoxide hydrides, organo compounds, organo oxides, and complexes thereof with metal halides and alkyl halides.  Many suitable Group IV-VIII metal compounds are specified, including halides, oxyhalides, oxyhalogen alkoxides, alcoholates, acetates, acetylacetonates and cyclopentadienyl halides. The reactions are preferably effected in the presence of inert solvent, e.g. n-pentane, n-heptane, isooctane, ligroin, benzine, cyclohexane, benzene, xylene, trichlorethylene, perchlorethylene, bromobenzene and chlorobenzene; and optionally in the presence of an inert finely divided solid carrier, e.g. polyethylene, polypropylene, polystyrene, sodium chloride, silica and carbon black.  The activity of the catalysts may be increased by ageing.  Examples describe the preparation of catalysts by the reaction in paraffins of a trimethylsilyl blocked methylhydrogen-siloxane with (1-53, 57, 58, 61, 63-65 and 68) aluminium trichloride and titanium tetrachloride, a polyethylene carrier being employed in (49, 50 and 64), (54) aluminium isopropylate and titanium tetrachloride, (55) aluminium trichloride, titanium tetrachloride and ferric chloride, (56) aluminium trichloride and vanadium oxychloride, (60) aluminium trichloride, titanium tetrachloride and violet titanium trichloride, (62) aluminium trichloride, titanium tetrachloride and vanadium oxychloride, (66) aluminium trichloride and butyl titanate, and (67) aluminium trichloride, titanium dichloride and titanium trichloride; a trimethyl-siloxy blocked polysiloxane containing 54 mol per cent of CH3SiHO- units and 45 mol per cent of dimethyl siloxane units with (69) aluminium trichloride and titanium tetrachloride; a linear methylhydrogenpolysiloxane containing 30 silicon atoms with (70-79) aluminium trichloride and titanium tetrachloride, (82) titanium tetrachloride and aluminium butylate, trimethylsiloxy aluminium dichloride, tripropylsiloxy aluminium dibromide, aluminium tribromide, diethoxy aluminium chloride, aluminium propylate, hexyloxy aluminium dichloride, an aluminium trichloride-titanium trichloride complex, boron halides, gallium trichloride, dimethylboron bromide, diethoxyboron chloride, dimethoxyboron hydride, dimethyl diborane, [(CH3)2B]2O, phenylboron dichloride, or tripropylboron, and (83) aluminium trichloride and zirconium tetrachloride, vanadium tetrachloride, molybdenum pentachloride, ferrous chloride, ferric chloride, cobaltous bromide, chloride or fluoride, butoxy titanium trichloride, zirconium oxychloride, vanadium oxychloride methoxide, diethoxymolybdenum trichloride, alkyl and aryl zirconates and titanates, zirconium tetraacetate, titanium dichloro diacetate, zirconium, cobalt and chromium acetylacetonates and chloro-bis(cyclopentadienyl) compounds of titanium, zirconium, vanadium and chromium; a methylhydrogen polysiloxane containing 6 silicon atoms with (80) aluminium trichloride and titanium tetrachloride; and a methylhydrogen polysiloxane containing 100 silicon atoms with (81) aluminium trichloride and titanium tetrachloride.  Specification 906,425 is referred to.