GB1187105A - Multicomponent Copolymers and Process for the Production thereof - Google Patents

Abstract

1,187,105. Multi-component copolymers. SUMITOMO CHEMICAL CO. Ltd. 6 June, 1967 [6 June, 1966], No. 26039/67. Heading C3P. A copolymer which comprises at least three monomer units selected from (a) at least one unit from the group consisting of (1) compounds of the general formula CH 2 =CR 1 R 2 where R 1 and R 2 each represent a hydrogen or halogen atom or a C 1-20 hydrocarbon or halogensubstituted hydrocarbon radical, (2) internal olefinic compounds of the general formula where R<SP>3</SP> and R<SP>4</SP> each represent a C 1-20 hydrocarbon or halogen-containing hydrocarbon radical, R<SP>5</SP> is H or as R<SP>3</SP> and R<SP>4</SP>, and R<SP>6</SP> is a divalent hydrocarbon residue having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon radical of 1 to 20, (3) polyenic compounds with up to 30 carbon atoms containing at least one carbon to carbon double bond having at least two hydrogen atoms, (4) compounds of the formula R<SP>7</SP>C = CR<SP>8</SP> wherein R<SP>7</SP> is hydrogen, a C 1-20 hydrocarbon radical, R<SP>8</SP> is hydrogen or a polymerizable unsaturated C 2-20 hydrocarbon radical, and (5) carbonyl- or thiocarbonyl-containing compounds of the. general formula where R<SP>9</SP> is an R<SP>12</SP>-, R<SP>12</SP>O-, R<SP>12</SP>S-, or R<SP>13</SP>R<SP>14</SP>N- group, Z is O or S, Y is O or S or an -NR<SP>15</SP> group, R<SP>10</SP> is an unsaturated, polymerizable C 2-20 hydrocarbon radical, R<SP>11</SP> is a divalent organic group residue, R<SP>12</SP> is a C 1-20 hydrocarbon radical and R<SP>13</SP>, R<SP>14</SP> and R<SP>15</SP> are as R<SP>12</SP> or hydrogen, (b) at least one monomeric unit selected from compounds of the general formula where R<SP>1</SP> and R<SP>11</SP> each represent a C 1-20 hydrocarbon or halogen-containing hydrocarbon radical, a halogen or a hydrogen atom, and at least one of R<SP>I</SP> and R<SP>II</SP> being a hydrogen atom and Q is a nitrile or group where Y<SP>1</SP> is a member selected from Z<SP>2</SP>H, Z<SP>2</SP>R, Z<SP>2</SP>Me, MR<SP>1</SP>R<SP>11</SP>, R, and a halogen or hydrogen atom, Z<SP>1</SP> and Z<SP>2</SP> being O or S, R is a C 1-20 organic radical, R<SP>1</SP> and R<SP>11</SP> are H or C 1-20 organic radicals including the case where R<SP>1</SP> and R<SP>11</SP> are bonded other than at nitrogen, and Me represents the monovalent portion of an element of Groups I to III of the Mendeleef's Periodic Table, or an ammonium radical. The copolymers are made by copolymerizing the monomers with (1) an organometal halide of the general formula MR<SP>111</SP> n X 3-n where M is aluminium or boron, R<SP>111</SP> is a hydrocarbyl radical, X is a halogen atom, and n is a number of 1 to 2, or a mixture of at least 2 compounds selected from compounds of the general formula where M, M<SP>1</SP> and M<SP>11</SP> are Al or B, R<SP>111</SP> and R" are hydrocarbyl organic radicals, X and X<SP>1</SP> are halogen atoms and n is a number of 1 to 2, or with (2) an organometal halide complex which is obtained by mixing and contacting, at least in the presence of the above group (b) conjugated monomer, (A) an organometallic compound of a metal of Groups IIB, IIIB and IVB of the Mendeleef's Periodic Table with (B) a halide of a metal of Groups IIIB and IVB of the said Table, at least one of said compounds (A) and (B) being an aluminium or boron compound. The copolymerization may be effected in bulk, or a hydrocarbon or halogenated hydrocarbon solvent. The Specification includes extensive lists of suitable monomers, and catalyst components. The copolymerization may be carried out in the presence of oxygen or peroxy compounds and preferably at low temperatures. Exemplified monomers are Example (I), methyl acrylate, propylene, and vinyl chloride, Example (II), methylmethacrylate, isobutylene, and vinyl acetate, Example (III), methyl acrylate, acrylonitrile, and vinylidene chloride, Example (IV), methyl acrylate, acrylonitrile and styrene, Example (V), methyl thiolacrylate, N-ethylacrylamide, and styrene, Example (VI), methyl acrylate, propylene, and dicyclopentadiene or divinyl benzene or butadiene, Example (VII), acrylonitrile, isoprene, and alpha-methylstyrene, Example (VIII), methyl acrylate, propylene or isobutylene, and 1,5-cyclooctadiene, Example (IX), methyl acrylate, propylene and 4-vinylcyclohexene, and Example (X), ethyl acrylate, 2-butene, and phenylacetylene. Catalysts exemplified are benzoyl peroxide and ethyl-aluminium sesquichloride, tin tetrachloride and triethyl aluminium, and boron trichloride and diethylzinc. The terpolymer of Example (VIII) was sulphur vulcanized using a known recipe.