GB1336770A - Catalyst and its use in polymerising alpha-monoethylenically unsaturated compounds - Google Patents

Abstract

1336770 Activated titanium trichloride in olefin polymerization catalyst MITSUI PETROCHEMICAL INDUSTRIES Ltd 15 June 1971 [15 June 1970 13 July 1970(2) 17 July 1970(3)] 28079/71 Heading C3P Olefins are polymerized using a catalyst comprising (A) an organo-aluminium compound, and (B) a titanium trichloride component obtained by (a) reacting titanium tetrachloride with hydrogen, silicon, metallic aluminium or metallic titanium to produce the trichloride, (b) pulverizing the product of (a) in the presence of a separately added aluminium or antimony trihalide until there is substantially no free trihalide, such pulverization being carried out additionally in the presence of an auxiliary component (1) when only solvent component (2) is used in the extraction step (c) below and which is any one of the solvent components (2), (3), (i), (ii) or (iii) below or titanium tetrachloride or a component 3 (iv) which is an organic phosphorus compound, i.e. an aliphatic or aromatic phosphine or phosphite, (c) extracting the pulverizate with an inert solvent which is (2) an aromatic or aliphatic hydrocarbon or halohydrocarbon, an alicyclic hydrocarbon or carbon disulphide, or a mixture of (2) with 3 (i) an ether, carboxylate ester, alcohol, phenol, aldehyde, carboxylic halide or acid, or ketone, 3 (ii) a nitrogen-containing heterocyclic compound, amine, or aromatic nitrile, isocyanate or azo compound, or 3 (iii) an organic silicon compound, and (d) separating the extracted titanium trichloride composition from the solvent or solvent mixture. In the examples, propylene, ethylene and propylene, or 4-methyl-pentene-1 are polymerized using (B) TiCl 4 reduction products pulverized with the various Sb and Al halides, in some cases with (1) n-butylacetate, anisole, o-bromoanisole, benzonitrile, titanium tetra-halide, octamethylcyclotetrasiloxane and like siloxanes or silanes (Table 12), carbon disulphide, benzophenone, toluene, trichloroethylene or ethanol and the product extracted with (2) and (3) toluene/anisole, /alphapicoline, /silicone oil, /carbon disulphide, /trichloroethylene, /benzophenone mixtures, or when (d) is present, with toluene, trichloroethylene, chlorobenzene or carbon disulphide alone, and (A) ethylaluminium dichloride, diethylaluminium chloride or ethyl ethoxyaluminium chloride. In comparative experiments the extraction step is not included or barium chloride is substituted for the aluminium or antimony trihalide. Additional catalyst ingredients exemplified are n-butylallylether and potassium titanium fluoride. The titanium trihalide reduction product may be washed before pulverizing and the pulverizing and washing steps may be repeated.