Patent GB-795182-A (GB)
Title: Improvements in or relating to process for the polymerization of unsaturated hydrocarbons
IPC: C08F4/70
Filed: 1956-07-10
Abstract: A two-component catalyst composition for the polymerization of unsaturated hydrocarbons containing a vinyl group comprises a mixture of (1) the reaction mixture of a metal of Group IV (a), V (a), VI (a) and VIII of the Periodic Table or manganese with an organometallic compound from the group consisting of alkali, alkaline earth, earth and rare earth metals and zinc; and (2) a halogen-free organometallic compound from the above group. Specified metal compounds are titanium and zirconium tetrachloride, manganous, nickelous, ferrous and ferric chlorides, tetrabutyl titanate, zirconium and chromium acetylacetonate and vanadium oxyacetylacetonate, while specified organometallic compounds are butylmagnesium chloride, phenylmagnesium bromide, dimethyl or diethylaluminium chloride, diethyl aluminium bromide, ethyl aluminium chloride, aluminium sesquichloride, dipropylaluminium fluoride, diisobutylaluminium fluoride and halogen-free compounds such as diethyl or dimethyl magnesium, butyllithium, amyl or phenyl sodium, diethyl zinc, triethyl or tripropyl or trioctyl or tridodecyl aluminium, diethyl or diisobutyl aluminium, hydride, ethyl aluminium hydride, sodium aluminium tetraethyl and lithium aluminium tetraoctyl.  The reaction between the metal compound and the organometallic compound may be carried out by mixing in the presence or absence of an inert diluent, e.g. hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzenes and chloronaphthalenes or mixtures of these diluents. The molar ratio of organometallic compound to metal compound may vary from 0.1 : 1 to 100 : 1, preferably from 0.5 : 1 to 2 : 1. Specification 789,781 is referred to.ALSO:At least one unsaturated hydrocarbon containing a vinyl group is polymerized by contacting it with a two-component catalyst comprising (1) the reaction mixture of a compound of a metal of Group IV (a), V (a), VI (a) or VIII of the Periodic Table or manganese with an organometallic compound from the group consisting of alkali, alkaline earth, earth and rare earth metals and zinc; and (2) a halogen-free organometallic compound from the above group.  Specfied hydrocarbons are ethylene, propylene, butene, hexene, heptene, octene, octadecene, dodecene, t-butylethylene, 4- and 5-methyl heptenes, styrene, alkylbenzene, vinylcyclohexane, 4 - vinylcyclohexene, hexadiene - 1,4, butadiene, isoprene and pentadiene-1,3.  Specified metal compounds are titanium and zirconium tetrachlorides, manganous, nickelous, ferrous and ferric chlorides, tetrabutyl titanate, zirconium and chromium acetylacetonates and vanadium oxy acetylacetonate, while specified organometallic compounds are butyl magnesium chloride, phenylmagnesium bromide, dimethyl or diethyl aluminium chloride, diethylaluminium bromide, ethyl aluminium chloride, aluminium sesquichloride, dipropylaluminium fluoride, diisobutylaluminium fluoride and halogen-free compounds such as diethyl or dimethyl magnesium, butyl lithium, amyl or phenyl sodium, diethyl zinc, triethyl, tripropyl, triisobutyl, trioctyl or tridodecyl aluminium, diethyl or diisobutyl aluminium hydride, ethyl aluminium hydride, sodium aluminium tetraethyl and lithium aluminium tetraoctyl.  The reaction between the metal compound and the organo metallic compound may be carried out by mixing in the presence or absence of an inert diluent, e.g. hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorbenzenes and chloronaphthalenes, and in a molar ratio of organometallic compound to metal compound of 0.1 : 1 to 100 : 1 preferably from 0.5 to 2 : 1.  The polymerization may also take place in the presence or absence of the inert diluent, and in batch or continuous operation.  Specification 789,781 is referred to.