Patent GB-795177-A (GB)
Title: Improvements in polymerization of hydrocarbons and catalyst therefor
IPC: C08F2/00
Filed: 1956-02-29
Abstract: A catalyst for polymerizing olefines consist of a mixture of an organo-metal halide and a tri-halide or tetra-halide of a Group IV metal.  The organo-metal halide is of the tppe RnMXy, in which R is alkyl, aryl, or saturated cyclic radical; M is aluminium, gallium, indium, thallium, or beryllium; X is halogen. The second component is a tri- or tetra-halide of titanium, silicon, thorium, zirconium, tin, lead, hafnium, germanium, or cerium.  The catalyst is effective at low temperatures, the range specified being -250 DEG  to +500 DEG F., and preferably -125 DEG  to 200 DEG  F.  Polymerization may be effected under pressure, and in the presence of solvents, e.g. cycloparaffins, or aromatic hydrocarbons.  A preferred catalyst mixture consists of diethyl aluminium chloride or ethyl aluminium dichloride and titanium or zirconium tetrachloride or tetrabromide. A number of examples are given including, as the first catalyst component, organic radicals containing up to 20 carbon atoms, e.g. cyclohexene gallium or indium chloride, C17H35BeI and C20H41GaBr2. Olefines polymerized are: 1-olefines containing up to 8 carbon atoms; branched chain or polyolefines with non-conjugated double bonds, cyclic olefines or aryl olefines.  Co-polymers are referred to.ALSO:Olefines are polymerized with a catalyst consisting of a mixture of an organo-metallic halide and a tri-halide or tetra-halide of a Group IV metal, e.g. in the mol. ratio of 0.05 to 20 : 1.  The organo-metallic halide is of the type RnMXy in which R is alkyl, aryl or a saturated cyclic radical; M is aluminium, gallium, indium, thallium or beryllium and X is halogen.  The second component is a tri- or tetra-halide of titanium, silicon, thorium, zirconium, tin, lead, hafnium, germanium or cerium.  A preferred mixture consists of diethyl aluminium chloride or ethyl aluminium dichloride with titanium or zirconium tetra chloride or tetra bromide.  A number of compounds are specified including, as the first component, organic radicals containing up to 20 carbon atoms, e.g. cyclohexene gallium or indium chloride, C17H35BeI and C20H41GaBr2.  Polymerization may be effected in the gaseous state or in the presence of solvents such as propane, butane, pentane, iso-octane, cyclohexane, methylcyclohexane, benzene and toluene, and in the temperature range -250 DEG  to +500 DEG  F., preferably at -125 DEG  to +200 DEG  F.  Olefines polymerized are: 1-olefines containing up to 8 carbon atoms; branched chain or polyolefines with non-conjugated double bonds; cyclic olefines or aryl olefines, and specified are ethylene, propylene, butene, hexene, octene, isobutylene, alkyl substituted ethylenes, hexatriene, pentadiene, octatriene, cyclohexene, styrene and alkyl substituted styrenes.  Copolymers are referred to.  The monomers and/or the diluent are desirably freed before use from catalyst poisons, e.g. with the use of alkaline pyrogallol.  The polymerization may be batchwise or by continuous flow, and further olefin may be added continuously or intermittently. Following polymerization the catalyst may be destroyed and the product purified by treatment with alcohols, such as isopropyl and butyl alcohols.  In Example IV the temperature used ranges from -45 DEG  to -67 DEG  F. The polymers are of high density and may be moulded to form articles such as bottles, piping and tubing.