Cycloolefin block copolymers and a process for their preparation

Claim 1

A process for the preparation of a cycloolefin block copolymer, comprising a) 0.1 to 95% by weight, with respect to the total amount of monomers employed, of at least one monomer of the formulae I, II, III, IV, V or VI ##STR10## in which R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and are a hydrogen atom or a C 1 -C 8 - alkyl radical, wherein it being possible for the same radicals in the various formulae to have different meanings, b) 0 to 95% by weight, with respect to the total amount of monomers employed, of a cycloolefin of the formula VII ##STR11## in which n is a number from 2 to 10, and c) 0 to 99% by weight, with respect to the total amount of monomers employed, of at least one acyclic olefin of the formula VIII ##STR12## in which R 9 , R 10 , R 11 and R 12 are identical or different and are a hydrogen atom or a C 1 -C 8 -alkyl radical, are polymerized at temperatures of -78° to 150° C. and a pressure of 0.01 to 64 bar, in the presence of a catalyst comprising an aluminoxane of the formula (IX) ##STR13## for the linear type and/or of the formula (X) ##STR14## for the cyclic type, wherein, in the formulae (IX) and (X), the radicals R 13 are identical or different and are a C 1 -C 6 -alkyl group, a C 6 -C 18 -aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, and a metallocene of the formula XI ##STR15## in which M 1 is titanium, zirconium, hafnium, vanadium, nioblum or tantalum, R 14 and R 15 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 6 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 - aryloxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 4 -C 40 -alkyl aryl group or a C 8 -C 40 -arylalkenyl group, R 16 and R 17 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M 1 , R 18 is ##STR16## =BR 19 , AlR 19 , --Ge--, --Sn--, --O--, --S--, =SO, =SO 2 , =NR 19 , =CO, =PR 19 , or P(O)R 19 , where R 19 , R 20 and R 21 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -fluoroaryl group, a C 6 -C 10 -aryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -aralkenyl group, or a C 7 -C 40 -alkylaryl group or R 19 and R 20 , or R 19 and R 21 , form a ring, in each case with the atoms linking them, and M 2 is silicon, germanium or tin, and, in each case at a molecular weight distribution M w /M n of less than 2, always with respect to the polymer block forming, the reaction conditions are changed one or more times in such a way that the monomer/comonomer ratio changes by at least 10% or a further polymerizable monomer of the formulae I-VIII is metered into the monomer or the monomers.