| 摘要 |
1,259,519. Alternating copolymers. BRIDGESTONE TIRE K.K. 1 Aug., 1969 [2 Aug., 1968; 8 Aug., 1968; 18 Oct., 1968; 7 March, 1969], No. 38792/69. Heading C3P. Alternating copolymers are prepared by copolymerizing at least one C 4-10 conjugated diene and at least one of acrylonitrile, methacrylonitrile andα,#-unsaturated carboxylic acid esters at a temperature of -78‹ to 100‹ C. in the liquid state in the presence of a catalyst prepared from (A) at least one compound of the transition metals of Groups IV and V excluding chelate compounds and (B) at least one halide of the formula ZnX 2 , AlH n X 3-n or AlH n X 3-n .L wherein X is halogen, L is an ether group having up to 20 carbons and n is 0, 0À5, 1À0 or 2; the transition metal atom in (A) being present as 10<SP>-6</SP> to 2 gm. atom per gm. atom of the metal atom in (B), the total amount of metal atoms in the catalyst system being 10<SP>-5</SP> to 1 gm. atom based on 1 mole of fed monomers, and the molar ratio of conjugated dienes to other monomers being 1/10 to 10/1. A further catalyst component (C) comprising, as a free radical initiator, an organic peroxide, an azonitrile compound or a trialkylboron-oxygen system, may be present, the molar ratio of (C) to the fed monomers being 0À00005 : 1 to 0À05 : 1. A molecular weight regulator chosen from mercaptans and carbon polyhalides having at least one bromine or iodine atom may also be present, the molar ratio of said regulator to the fed monomers being 10<SP>-8</SP> : 1 to 0À05 : 1. In the examples copolymers of butadiene and acrylonitrile, isoprene and acrylonitrile, butadiene and methylmethacrylate, and butadiene, acrylonitrile and n-butylacrylate are prepared. The catalysts exemplified are (A) vanadyl trichloride, pentaethoxytantalum, tetraisopropoxy titanium, zirconium oxydichloride, (tritertiary butyl)vanadyl, zirconium tetrachloride, tetrapropoxy zirconium, (B) anhydrous zinc chloride, aluminium trichloride, aluminium trichloride diethyl etherate, aluminium tribromide and aluminium hydride dichloride diethyl etherate. The components (C) exemplified are benzoyl peroxide, 2,2<SP>l</SP>-azo-bisisobutyronitrile, diisopropyl peroxydicarbonate, tertiary butyl peroxy pivalate and triethylboron/oxygen, and the exemplified molecular weight inhibitors are carbon tetrabromide, iodoform and n-dodecylmercaptan.
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