Patent GB-789781-A (GB)
Title: Improvements in or relating to a process for polymerizing olefins
Inventor: EDWIN JAMES VANDENBERG
IPC: C08F10/00
Filed: 1956-04-05
Abstract: Polymerization catalysts comprise a composition of (1) the hydrocarbon insoluble reaction product of a compound of a Group IV (a), V (a), VI (a) or VIII metal or of manganese with an organometallic compound of an alkali, alkaline earth, earth or rare earth metal or of zinc, and (2) an organometallic compound of an alkali, alkaline earth, earth or rare earth metal or of zinc. The organometallic compounds of (1) and (2) may be the same or different; examples are alkali metal alkyls and aryls such as butyl and phenyl lithium and amyl and phenyl sodium; calcium alkyls, dimethyl-magnesium, diethylmagnesium, diethylzinc, butyl magnesium chloride, phenyl magnesium bromide; trimethyl-, triethyl-, tripropyl-, triisobutyl-, trioctyl-, tridodecyl-, and triphenyl-aluminium; dimethyl aluminium chloride, diethyl aluminium chloride and bromide, ethyl aluminium dichloride, aluminium sesquichloride, dripropyl aluminium- and diisobutyl aluminium - fluorides, diethyl aluminium hydride, ethyl aluminium dihydride, diisobutyl-aluminium hydride, sodium aluminium tetraethyl and lithium aluminium tetraoctyl.  The Groups IV (a), V (a), VI (a) or VIII metal or manganese compound may be a halide such as a chloride, an oxyhalide, acetylacetonate, oxyacetylacetonate or an ester such as tetrabutyl titanate. Component (1) is said to be a reduction product of the Groups IV (a), V (a), VI (a) or VIII metal or manganese compound and may be formed in situ or may be aged before use, e.g. at up to 100 DEG  C. Molar ratios of the catalyst components used in the preparation of (1) and of the components (1) and (2) are given.  In examples the polymerization reaction is terminated with ethanol or butanol.ALSO:Ethylenically unsaturated hydrocarbons are polymerized by contacting with a catalyst composition of (1) the hydrocarbon-insoluble reaction product of a compound of a Group IVA, VA, VIA or VIII metal or of manganese with an organometallic compound of an alkali, alkaline earth, earth or rare earth metal or of zinc, and (2) an organometallic compound of an alkali, alkaline earth, earth or rare earth metal or of zinc.  Unsaturated hydrocarbons specified are ethylene, propylene, 1- and cis-butenes, hexene, heptene, octene, octadecene, dodecene, isobutylene, diisobutylene, t - butylethylene, methylheptenes, tetramethylethylene, styrene, a -methyl styrene, vinylcyclohexane, hexadiene-1,4, 6 - methylheptadiene - 1,5, isoprene, butadiene, pentadiene, cyclopentadiene, cyclohexene, 4 - vinylcyclohexene - 1, b  - pinene and mixtures thereof.  The organometallic compounds of components (1) and (2) may be the same or different and exemplified are alkali metal alkyls and aryls such as butyl and phenyl lithium and amyl and phenyl sodium; calcium alkyls, dimethyl magnesium, diethyl magnesium, diethyl zinc, butyl magnesium chloride, phenyl magnesium bromide; trimethyl-, triethyl-, tripropyl-, triisobutyl-, trioctyl-, tridodecyl- and triphenyl-aluminium; dimethyl aluminium chloride, diethyl aluminium chloride and bromide, ethyl aluminium dichloride, aluminium sesquichloride, dipropyl aluminium-and diisobutylaluminium-fluorides, diethyl aluminium hydride, ethyl aluminium dihydride, diisobutylaluminium hydride, sodium aluminium tetraethyl and lithium aluminium tetraoctyl.  The Group IVA, VA, VIA or VIII metal or manganese compound may be a halide such as a chloride, an oxyhalide, acetylacetonate, oxyacetylacetonate or an ester such as tetrabutyl titanate. Component (1) is said to be a reduction product of the Group IVA, VA, VIA or VIII metal or manganese compound and may be formed in situ or may be aged before use, e.g. at up to 100 DEG  C.  Molar ratios of the catalyst components used in the preparation of (1) and of the components (1) and (2) are given.  The polymerization may be carried out in bulk or in hydrocarbon diluents which may also be used in the preparation and isolation of catalyst component (1) and also in the separation of the polymer.  Listed diluents are hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzenes, chloronaphthalenes, decahydronaphthalene and mixtures thereof.  Polymerization may be batchwise or continuous and the monomer and/or catalyst or components thereof may be added incrementally or continuously.  In examples the reactions are terminated with ethanol and butanol and the products are washed with materials such as ethanol (which may contain phenyl-b -naphthylamine), butanol, methanol, water, heptane, and methanolic hydrochloric acid.  The polymers obtained are crystalline insoluble products or rubbery soluble materials or mixtures thereof.