| 摘要 |
1,186,461. Alternating copolymers of conjugated dienes and conjugated polar monomers. BRIDGESTONE TIRE K.K. 2 July, 1968 [28 March, 1968], No. 31627/68. Heading C3P. Alternating copolymers of conjugated dienes having 4 to 10 carbon atoms and a conjugated polar monomer which is (meth) acrylonitrile or an ester of an α,#-unsaturated carboxylic acid, in which the diene units are substantially (more than 70%) trans-1,4, are obtained by copolymerization in the presence of (A) at least one compound of a transition metal of Group IV or V, and (B) an organoaluminium halide or equivalent mixture. The polymerization may be performed in bulk or solution, the solvents including the usual hydrocarbons, halogenated hydrocarbons and CS 2 . The catalyst components may be complexed with an organic nitrile, an α,#-unsaturated carboxylic acid ester, a benzoate, a tertiary amine or thiophene. The stereoregularity of the copolymers is determined by NMR and IR spectra, elementary analysis and pyrolysis gas chromatography. In the examples, butadiene, isoprene and pentadiene-1,3 are separately copolymerized with each of the following comonomers: acrylonitrile, methyl methacrylate, methyl acrylate, ethyl methacrylate and methacrylonitrile, component (A) of the catalyst being VOCl 3 , VO(OC 4 H 9 ) 3 , VO(OC 4 H 9 ) 2 Cl, VO(OC 4 H 9 )Cl 2 , VO(OC 2 H 5 ) 3 , VCl 4 , VO(AcAc) 2 , V(AcAc) 3 , Ti(OC 4 H 9 ) 4 , TiCl 4 , oxytitanium diacetylacetonate, vanadyl naphthenate, vanadyl diacetate, VO(OC 3 H 7 ) 3 , Ta(OC 2 H 5 ) 5 , and Zr(OC 4 H 9 ) 4 , component (B) is C 2 H 5 AlCl 2 , (C 2 H 5 ) 3 Al 2 Cl 3 , (C 2 H 5 ) 3 Al 2 Br 3 , (i-C 4 H 9 ) 3 Al 2 Br 3 , (CH 3 ) 3 Al 2 Cl 3 , CH 3 .AlCl 2 , and mixtures thereof including AlCl 3 and Al(C 2 H 5 ) 3 , and complexes of these catalyst components with (meth) acrylonitrile, methyl methacrylate, acetonitrile, ethyl benzoate, thiophene, ethyl acrylate, dimethylaniline, benzonitrile, fumaronitrile and triphenylamine. |
