Cycloolefin copolymers, a process for their preparation and the use thereof and catalysts

A process for the preparation of cycloolefin copolymers by polymerization of

• a) at least on cycloolefin of the general formula (I)
• in which n is 0 or 1, m is 0 or a positive integer, R1, R2, R3, R4, R5, R6 independently of one another, are selected from the group consisting of hydrogen, halogen, cyclic and acyclic branched and straight-chain aliphatic hydrocarbon groups, aromatic hydrocarbon groups and alkoxy groups, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, independently of one another, are selected from the group consisting of hydrogen and aliphatic hydrocarbon groups, R17, R18, R19, R20, independently of one another, are selected from the group consisting of hydrogen, halogens and aliphatic hydrocarbon groups, it also being possible for R17 and R19 to be bonded to one another in such a way that they form a single ring or a ring system comprising a plurality of rings, it being possible for the ring or the rings to be saturated or unsaturated, with
• b) at least one 1-olefin of the formula (II)
• in which R21 and R22, independently of one another, are selected from the group consisting of hydrogen and C1-20alkyl groups,
• the cycloolefin and the comonomer being polymerized in the presence of a catalyst system which contains a metallocene compound selected from the group consisting of
• wherein the cycloolefin copolymer contains racemic diads of repeating polycyclic units, which produce signals of about 29.44 ppm and about 31.24 ppm in a 13C-NMR spectrum, and additionally contains racemic triads of repeating polycyclic units, which produce signals from about 34.5 to 40.5 ppm in the 13C-NMR spectrum.

A cycloolefin copolymer prepared by non-ring-opening polymerization of:

• a) at least one cycloolefin of the general formula (I)
• in which n is 0 or 1, m is 0 or a positive integer, R1, R2, R3, R4, R5, R6 independently of one another, are selected from the group consisting of hydrogen, halogen, cyclic and acyclic branched and straight-chain aliphatic hydrocarbon groups, aromatic hydrocarbon groups and alkoxy groups, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, independently of one another, are selected from the group consisting of hydrogen and aliphatic hydrocarbon groups, R17, R18, R19, R20, independently of one another, are selected from the group consisting of hydrogen, halogens and aliphatic hydrocarbon groups, it also being possible for R17 and R19 to be bonded to one another in such a way that they form a single ring or a ring system comprising a plurality of rings, it being possible for the ring or the rings to be saturated or unsaturated, with
• b) at least one 1-olefin of the formula (II)
• in which R21 and R22, independently of one another, are selected from the group consisting of hydrogen and C1-20-alkyl groups, wherein the cycloolefin copolymer contains racemic diads of repeating polycyclic units and additionally racemic triads of repeating polycyclic units, wherein the cycloolefin copolymer has signals from 34.5 to 40.5 ppm in its 13C-NMR spectrum;
• and wherein further the cycloolefin and the comonomer are polymerized in the presence of a catalyst system which contains metallocene compounds of the general formula (IV)
• in which M is a metal of group IIb, IVb, Vb and VIb of the Periodic Table of the Elements, R313 and R313a, independently of one another, are selected from the group consisting of hydrogen, C1-C2-alkyl and aryl, R311 is selected from the group consisting of isopropanyl and phenyl, and R312 is selected from the group consisting of hydrogen and C1-C4-alkyl, and the radicals R311, R312, R313 and R313a being selected so that the metallocene compound has no Cs symmetry in relation to the centroid-M-centroid plane.

A process for the production of moldings, comprising

• a) providing a cycloolefin copolymer of
• i) at least one cycloolefin of the general formula (I)
• in which n is 0 or 1, m is 0 or a positive integer, R1, R2, R3, R4, R5, R6 independently of one another, are selected from the group consisting of hydrogen, halogen, cyclic and acyclic branched and straight-chain aliphatic hydrocarbon groups, aromatic hydrocarbon groups and alkoxy groups, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, independently of one another, are selected from the group consisting of hydrogen and aliphatic hydrocarbon groups, R17, R18, R19, R20, independently of one another, are selected from the group consisting of hydrogen, halogens and aliphatic hydrocarbon groups, it also being possible for R17 and R19 to be bonded to one another in such a way that they form a single ring or a ring system comprising a plurality of rings, it being possible for the ring or the rings to be saturated or unsaturated, with
• ii) at least one 1-olefin of the formula (II)
• in which R21 and R22, independently of one another, are selected from the group consisting of hydrogen and C1-20-alkyl groups,
• wherein the cycloolefin copolymer contain racemic diads of repeating polycyclic units and additionally racemic triads of repeating polycyclic units, and wherein the cycloolefin copolymer has signals from 34.5 to 40.5 ppm in its 13C-NMR spectrum;
• and
• b) forming a molding from the cycloolefin copolymer;
• wherein the cycloolefin and the comonomer are prepared by polymerization in the presence of a catalyst system which contains metallocene compounds of the general formula (IV)
• in which M is a metal of group IIb, IVb, Vb and VIb of the Periodic Table of the Elements, R313 and R313a, independently of one another, are selected from the group consisting of hydrogen and C1-C4-alkyl, and aryl, R311 is selected from the group consisting of isopropanyl and phenyl, and R312 is selected from the group consisting of hydrogen and C1-C4-alkyl, and the radicals R311, R312, R313 and R313a being selected so that the metallocene compound has no Cs symmetry in relation to the centroid-M-centroid plane.