Patent GB-838227-A (GB)
Title: Improvements in the production of polymerisation products from olefinically-unsaturated hydrocarbons
IPC: C08F2/00
Filed: 1956-11-01
Abstract: Olefines are polymerized using as catalyst a mixture of (1) an organometallic compound containing at least one hydrocarbon radical directly attached to a metallic or semi-metallic element of Group IVb or Vb of the Periodic Table, including phosphorus; (2) a halide or oxyhalide of a metal of the A sub-Group IVa to VIIa or Group VIII: and (3) an organic halogen-containing compound.  As the organometallic compound may be used compounds of the formula MeR2, Me2R6 and MeR4, in which Me represents germanium, tin or lead, and R is a hydrocarbon radical saturated or not.  The radicals R may be partly replaced by groups such as hydrogen, halogen or hydroxyl. Examples given are tin tetraethyl, lead tetraethyl, diethyl tin, hexaphenyl distannane, tetrabutyl tin and lead triethyl chloride. The organometallic compound may also be of the formula MeR2 or MeR5, in which Me represents phosphorus, arsenic, antimony or bismuth and examples given are triphenylarsine, tribenzylphosphine, tri-n-butyl phosphine and triethyl bismuth. These hydrocarbon compounds of Group IVb and Vb may be complexed with an organic or inorganic compound such as iron or nickel carbonyl.  The metal halide component may be titanium tetrachloride or trichloride or the corresponding bromides, titanium tetraiodide, zirconium or thorium tetrabromides, vanadium tetrachloride, pentafluoride or oxytrichloride, chromium trichloride, chromylchloride, tungsten hexachloride, molybdenum hexachloride, uranium oxyhalides, manganese tetrachloride, ferric chloride, nickel dibromide or cobalt chloride.  The organic halogen compound is preferably a hydrocarbon derivative and may contain one halogen atom, e.g. t-butyl or n-butyl chloride or bromide, triphenylchloromethane, ethyl, propyl, octyl, dodecyl or octadecyl chloride, chlorobenzene, allyl bromide or chlorocyclohexanes or may contain more than one halogen atom, such as carbon tetrachloride, trichloroethylene, 1,2 - dichloroethane, chloroform, trichlorobromomethane, trifluoroiodomethane, phenyltrichloromethane, hexachloroethane methylene chloride and 1,2-dichlorobenzene.  The organic halogen compound may also be an organic compound with reactive halogen, e.g. acid halides such as acetyl, benzoyl, terephthalic acid or cyclohexylcarboxylic acid chlorides or propionic acid bromide, di- or tri-chloroacetic acid, p-chlorobenzoic acid, trichloroacetonitrile, ethylenebromhydrin, beta-chlorodiethyl ether or other halogenated ethers or halogenated esters, aldehydes or ketones.  The polymerization may be carried out in the presence of inert diluents or solvents such as hexane, iso-octane, gasoline, cyclohexane, methylcyclohexane, benzene, xylene or toluene.  Specification 811,865 is referred to.ALSO:Olefines are polymerized using as catalyst a mixture of (1) an organometallic compound containing at least one hydrocarbon radical directly attached to a metallic or semi-metallic element of Group IVb or Vb of the Periodic Table, including phosphorus; (2) a halide or oxyhalide of a metal of the A sub-Group IVa to VIIa or Group VIII, and (3) an organic halogen-containing compound.  Olefines specified are ethylene, propylene, butylene, isobutylene and styrene and also conjugated diolefines such as butadiene or isoprene.  As the hydrocarbon compound may be used compounds of the formula MeR2, Me2R6 and MeR4, in which Me represents germanium, tin or lead, and R is a hydrocarbon radical, saturated or not.  The radicals R may be partly replaced by groups such as hydrogen, halogen or hydroxyl. Examples given are tin tetraethyl, lead tetraethyl, diethyl tin, hexaphenyl distannane, tetrabutyl tin and lead triethyl chloride. The hydrocarbon compound may also be of the formula MeR3 or MeR5, in which Me represents phosphorus, arsenic, antimony or bismuth and examples given are triphenylarsine, tribenzylphosphine, tri-n-butyl phosphine and triethyl bismuth. These hydrocarbon compounds of Groups IVb and Vb may be complexed with an organic or inorganic compound such as iron or nickel carbonyl.  The metal halide component may be titanium tetrachloride or trichloride or the corresponding bromides, titanium tetraiodide, zirconium or thorium tetrabromides, vanadium tetrachloride, pentafluoride or oxytrichloride, chromium trichloride, chromylchloride, tungsten hexachloride, molybdenum hexachloride, uranium oxyhalides, manganese tetrachloride, ferric chloride, nickel dibromide or cobalt chloride. The organic halogen compound is preferably a hydrocarbon derivative and may contain one halogen atom, e.g. t-butyl or n-butyl chloride or bromide, triphenylchloromethane, ethyl, propyl, octyl, dodecyl or octadecyl chloride, chlorobenzene, allyl bromide or chlorocyclohexanes or may contain more than one halogen atom such as carbon tetrachloride, trichloroethylene, 1,2-dichloroethane, chloroform, trichlorobromomethane, trifluoroiodomethane, phenyltrichloromethane, hexachloroethane methylene chloride and 1,2-dichlorobenzene.  The organic compound may also be an organic compound with reactive halogen, e.g. acid halides such as acetyl, benzoyl, terephthalic acid or cyclohexylcarboxylic acid chlorides or propionic acid bromide, di- or tri-chloroacetic acid, p-chlorobenzoic acid, trichloroacetonitrile, ethylenebromhydrin, betachlorodiethyl ether or other halogenated ethers or halogenated esters, aldehydes or ketones.  The polymerization may be carried out in the presence of inert diluents or solvents such as hexane, iso - octane, gasoline, cyclohexane, methylcyclohexane, benzene, xylene or toluene.  The polymer product may be purified by washing with alcohols, ethers or ketones, e.g. methanol, ethanol, acetone, dioxane or tetrahydrofurane which may contain organic or inorganic acids, e.g. oxalic, tartaric, hydrochloric, sulphuric or nitric acids.  In the examples, ethylene is added stepwise to the polymerization mixture and methanol is added after polymerization is completed.  Colourless, high molecular weight polymers with high melting-points are obtained which may be used for the production of fibres, threads, foils, pressed masses and injection mouldings.  Specification 811,865 is referred to.