Patent GB-1268210-A (GB)
Title: Process for hydrogenating polymers
IPC: C08C19/02
Filed: 1969-04-14
Abstract: 1,268,210. Polymer hydrogenation catalysts. BRIDGESTONE TIRE K.K. 14 April, 1969 [23 April, 1968], No. 19082/69. Heading B1E. [Also in Division C3] Catalyst for the hydrogenation of polymer having hydrogenatable unsaturated bonds is prepared by mixing (1) an iron, cobalt or nickel carboxylate or an iron, cobalt or nickel chelate in which the chelating agent is attached to the iron, cobalt or nickel atom through a pair of oxygen atoms with (2) a reducing agent having the formula MR n  wherein M is at least one metal selected from lithium, magnesium and aluminium, n is the valency of the metal M or the sum of the valencies of the metals M and the or each R is a hydrogen atom, a hydrocarbon radical having from 1 to 12 carbon atoms or an alkoxy radical having from 1 to 12 carbon atoms, such mixing being effected in the presence of hydrocarbon polymer in which at least 5 per cent of the carbon-carbon bonds are double bonds. The Specification discloses numerous examples of catalyst component (1) and of catalyst component (2); the hydrocarbon polymer may be a polymer having butadiene and/or isoprene units, for example polybutadiene, polyisoprene, a butadiene-isoprene copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer, an ethylene-butadiene copolymer, an ethyleneisoprene copolymer or a copolymer or terpolymer of butadiene and/or isoprene with a compatible copolymerizable monomer; a terpolymer of ethylene and propylene with a compatible copolymerizable diolefin, for example 1,7-octadiene, dicyclopentadiene or ethylidenenorbornene; a homopolymer of a diolefin, for example hexadiene, octadiene or cyclooctadiene; or a copolymer of such a diolefin with a compatible polymerizable monomer. The hydrocarbon polymer may be either liquid or solid in which latter case it is used in solution in an inert solvent, for example an aliphatic, cycloaliphatic or aromatic hydrocarbon, an aliphatic, cycloaliphatic or aromatic halohydrocarbon or an ether; solvents exemplified are hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, decalin and tetralin. The catalyst preferably is prepared under an inert atmosphere, for example an atmosphere of nitrogen, helium or argon. Examples relate to catalysts prepared from nickel naphthenate, triethylaluminium and either 18/82 styrenebutadiene random copolymer or polybutadiene or polyisoprene or an ethylene-propylenedicyclopentadiene terpolymer (Example 1); nickel 2-ethylhexanoate, n-butyllithium and either 18/82 styrene-butadiene random copolymer or polybutadiene (Example 2); cobalt naphthenate, triethylaluminium and polybutadiene (Example 3); iron naphthenate, triethylaluminium and either 18/82 styrene-butadiene random copolymer or polybutadiene (Example 4); polybutadiene and either bis(acetylacetone) nickel and diethylmagnesium or nickel cyclohexylcarboxylate and triethylaluminium or nickel octanoate and n-butyllithium or cobalt octanoate and n-butyllithium or cobalt octanoate and triethylaluminium (Example 5); and nickel naphthenate, triethylaluminium and 25/75 styrene-butadiene random copolymer (Example 6), the catalysts being used in the hydrogenation of either 18/82 styrene-butadiene random copolymer (Examples 1, 2 and 4) or polybutadiene (Examples 3 and 5) or 25/75 styrene-butadiene random copolymer (Example 6) in either toluene (Examples 1, 2, 4 and 5) or n-hexane (Examples 3 and 6) solvent.