GB1123724A - Copolymers of conjugated compounds and unsaturated hydrocarbon compounds and processfor production thereof - Google Patents

Abstract

Alternating 1:1 copolymers consist of a monomer (A) selected from (1) an internal olefinic compound of the formula R1-CH = CR2R3 or <FORM:1123724/C3/1> where R1 and R2 are hydrocarbon or halogen-containing hydrocarbon radicals, R3 and R4 are hydrogen atoms, or as R1 and R2, and R5 is a cyclic hydrocarbon or halogen-containing cyclic hydrocarbon residue and R1 to R5 may contain other inert substituents but no polymerizable linkages; (2) polyene compound containing at least one carbon to carbon double bond having at least two carbon atoms; or (3) an acetylenically unsaturated compound of the formula R6C ­ CR7, where R6 is hydrogen or a hydrocarbon or substituted hydrocarbon radical, and R7 is hydrogen, or hydrocarbon radical containing a polymerizable group or such a group substituted, and a monomer (B) selected from compounds of the formula <FORM:1123724/C3/2> where R1 and R11 are hydrocarbon or halogen-containing hydrocarbon radicals, halogen or hydrogen atoms, and at least one R1 and R11 is hydrogen, Q is a nitrile group or <FORM:1123724/C3/3> group, wherein Y is Z2H, Z2R, Z2Me, <FORM:1123724/C3/4> or a halogen or a hydrogen atom, Z1, Z2, Z3 and Z4 are oxygen or a sulphur atom, R1 and R11 are as defined above, R is a Cl to 20 organic radical, R1 and R11 are H or a Cl to 20 organic radical, RV is a Cl to 20 organic residue, Me is a monovalent metal or an ammonium group, and Me1 is a divalent metal. The copolymers are made by copolymerizing the monomers in the presence of a catalyst comprising (1) an organometal halide of the formula MR111nX3- n, where M is Al or B, R111 is an organic radical, X is a halogen atom, and n is from 1 to 2, or a mixture of at least two compounds having the formulae (A) MR111nX3- n, (B) M1RIV3 and (C) M11X13, where M, M1 and M11 is Al or B, R111 and RIV are organic radicals, X and X1 are halogen, and n is from 1 to 2; or with (2) a catalyst component comprising (a) an organometallic compound of a metal (including boron) of Group II(BETA), III(BETA) or IV(BETA) of the Mendeleef Periodic Table, and catalyst component; (b) a halogen-containing compound of a metal (including boron) of Group III(BETA) or IV(BETA), wherein at least one metal component of (a) and (b) is Al or B, and (a) must be contacted with (b) in the presence of at least the conjugated compound of Group B monomers. The copolymerization may be carried out in bulk or in the presence of a hydrocarbon or halogenated hydrocarbon medium, or in the presence of oxygen or a peroxy compound as a catalyst addition component The Specification contains very extensive lists of monomers and catalyst components. The copolymers are recovered by conventional techniques. Exemplified copolymers are acrylonitrile or methyl acrylate or n-butyl acrylate or CH2 = CH-CO-SCH3, N - ethylacrylamide, and butene-2, methyl acrylate and 2-methyl-butene-2, methyl acrylate and betamethyl-styrene, methyl acrylate and trans-stilbene, acrylonitrile or methyl acrylate and cyclopentene, acrylonitrile and indene, methyl acrylate and 1,4-dihydronaphthalene, methyl acrylate and norbornene, or phenyl-norbornene, or 5 - chloro - norbornene, or alpha - pinene, methyl methacrylate and chloronorbornene, acrylonitrile and 1,3 - pentadiene, CH2 = CH-CO-SCH3 and 1,4-pentadiene, acrylonitrile and isoprene, acrylonitrile and butadiene, N - ethylacrylamide and 2-chloro-1,3-butadiene, methyl methacrylate and p-isopropenyl styrene, methyl acrylate and 4-vinyl cyclohexene or cyclopentadiene, acrylonitrile and cyclooctadiene, acrylonitrile and 5-vinyl-2-norbornene, methyl acrylate and phenylacetylene, and ethyl acrylate and butenylmethyl acetylene.