Improvements in or relating to normally solid copolymers of aryl diolefins and terminally unsaturated olefins and process for preparing them

摘要

Co-polymers are made by co-polymerizing at least one 2-aryl butadiene-1,3 with at least one terminally unsaturated olefine of the general formula where R is a hydrogen, an aliphatic, cycloaliphatic or aromatic hydrocarbon, in the substantial absence of oxygen or moisture. and in the presence of a co-ordination catalyst obtained by mixing in the presence of a diluent, a halide of a polyvalent metal of Group IV(A), V(A) and VI(A) of the Periodic Table with a compound having at least one metal to hydrocarbon bond, preferably in the proportions of 10 parts of the latter to each 0,3 parts of the former. Specified terminally unsaturated olefines are ethylene, propylene, butene-1 and pentene-1. Specified metal halides are titanium and zirconium tetrachloride, vanadium oxytrichloride, molybdenum pentachloride and chromium tribromide Specified compounds having metal to hydrocarbon bonds are lithium aluminium tetraalkyls, phenyl magnesium halides, aluminium trialkyls and tetraalkyl tins. The copolymers of the invention may be cross-linked by heating at temperatures above 150 DEG C. In the examples, co-polymers are made from 2-phenyl butadiene-1,3 and ethylene and/or propylene using co-ordination catalysts made from titanium tetrachloride and lithium aluminium tetraheptyl aluminium trisobutyl and lithium tetracyclohexenylethyl. Specification 776,326 is referred to.ALSO:Co-ordination polymerization catalysts are made by admixing in the presence of a diluent, a halide of a polyvalent metal from Group IVa, Va or VIa of the Periodic Table with a compound having at least one metal to hydrocarbon bond, preferably in the proportions of 10 parts of the latter to each 0.3 part of the former. Specified metal halides are titanium and zirconium tetrachloride, vanadium oxytrichloride, molybdenum pentachloride and chromium tribromide. Specified compounds having metal to hydrocarbon bonds are lithium aluminium tetra alkyls, phenyl magnesium halides, aluminium trialkyls and tetra alkyl tins. In the examples, co-ordination catalysts are made by admixing in the presence of (I) to (III) cyclohexane, (IV) and (V) cyclohexane and xylene, titanium tetrachloride and (I) lithium aluminium tetraheptyl, (II) aluminium tri-isobutyl and (III) to (V) lithium aluminium tetra cyclo hexenyl ethyl. Specification 776,326 is referred to.