PHOSPHINIC COMPLEX OF VANADIUM, CATALYTIC SYSTEM CONTAINING SAID PHOSPHINIC COMPLEX OF VANADIUM AND METHOD FOR (CO)POLYMERIZATION OF CONJUGATED DIENES

摘要

FIELD: chemistry.;SUBSTANCE: invention relates to a catalyst system for (co)polymerization of conjugated dienes. Catalyst system includes: (a) at least one phosphine complex of vanadium having general formula (I) or (II): V(X)₃[P(R₁)_n(R₂)_3-n]₂ (I), V(X)₃[(R₃)₂P(R₄)P(R₃)₂] (II), where X is an anion selected from a halogen, such as chlorine, bromine, iodine; R₁, identical or different from each other, represent a hydrogen atom or are selected from alkyl groups C₁-C₂₀, linear or branched, and C₃-C₆ cycloalkyl groups, n is an integer ranging from 0 to 3; R₂, identical or different from each other, are selected from aryl groups, which are carbocyclic aromatic groups selected from phenyl, naphthyl, phenanthrene and anthracene; R₃, identical or different from each other, represent a hydrogen atom or are selected from alkyl groups C₁-C₂₀, linear or branched, C₃-C₆ cycloalkyl groups and aryl groups, which are carbocyclic aromatic groups selected from phenyl, naphthyl, phenanthrene and anthracene; R₄ is a -NR₅ group, in which R₅ represents a hydrogen atom or is selected from C₁-C₂₀ alkyl groups, linear or branched, or R₄ is an alkylene group -(CH₂)p-, in which p is an integer ranging from 1 to 5; provided that if in general formula (I) n equals 1 and R₁ is methyl, then R₂ differs from phenyl, and (b) at least one co-catalyst selected from organic aluminum derivatives, which are aluminoxanes having general formula (IV): (R₉)₂-Al-O-[-Al(R₁₀)-O-]_q-Al-(R₁₁)₂ (IV). In formula (IV) R₈, R₉ and R₁₀, identical or different from each other, represent a hydrogen atom or a halogen atom, such as chlorine, bromine, iodine, fluorine, or are selected from C₁-C₂₀ alkyl groups, linear or branched, cycloalkyl groups, aryl groups, wherein said groups are optionally substituted with one or more silicon or germanium atoms, and q is an integer ranging from 0 to 1,000. Also disclosed are a method for (co)polymerization of conjugated dienes and a method for polymerization of 1,3-butadiene or isoprene.;EFFECT: disclosed catalyst system enables to obtain (co)polymers of conjugated dienes with predominant content of 1,4-trans and 1,4-cis links.;5 cl, 36 dwg, 4 tbl, 51 ex