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Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof

  • US 5,422,409 A
  • Filed: 11/22/1993
  • Issued: 06/06/1995
  • Est. Priority Date: 02/27/1991
  • Status: Expired due to Fees
First Claim
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1. A process for the preparation of a cycloolefin polymer or copolymer with a narrow molecular weight distribution (Mw/Mn) by polymerization of 0.1 to 100% by weight, based on the total amount of the monomers, of at least one monomer of the formulae I, II, III, IV, V or VI ##STR11## in which R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1 -C8 -alkyl radical, identical radicals in the different formulae having the same or a different meaning,0to 99.9% by weight, based on the total amount of the monomers, of a cycloolefin of the formulae VII ##STR12## in which n is a number from 2 to 10, and 0 to 99.9% by weight, based on the total amount of the monomers, of at least one acyclic 1-olefin of the formula VIII ##STR13## in which R9, R10, R11 and R12 are identical or different and are a hydrogen atom or a C1 -C8 -alkyl radical, at temperatures from -78°

  • to 150°

    C. and under a pressure of from 0.01 to 64 bar, in the presence of a catalyst which is comprised of an aluminoxane of the formula IX ##STR14## for the linear type and/or of the formula X ##STR15## for the cyclic type, where the radicals R13 in the formulae IX and X are identical or different and are a C1 -C6 -alkyl group or phenyl or benzyl, and n is an integer from 0 to 50, and of a metallocene of the formula XI ##STR16## in which M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,R14 and R15 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -alkoxy group, a C6 -C10 -aryl group, a C6 -C10 -aryloxy group, a C2 -C10 alkenyl group, a C7 -C40 -arylalkyl group, a C7 -C40 -alkylaryl group or a C8 -C40 -arylalkenyl group,R16 and R17 are mono- or polynuclear hydrocarbon radicals which form a sandwich structure with the central atom M1,R18 is ##STR17## ═

    BR19, ═

    AlR19, --Ge--, --Sn--, --O--, --S--, ═

    SO, ═

    SO2, ═

    NR19, ═

    CO, ═

    PR19 or ═

    P(O)R19, where R19, R20 and R21 are identical or different and are each one of the following substituents;

    a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -fluoraryl group, a C6 -C10 -aryl group, a C1 -C10 -alkoxy group, a C2 -C10 -alkenyl group, a C7 -C40 -arylalkyl group, a C8 -C40 -arylalkenyl group or a C7 -C40 -alkylaryl group, or any one of R19, R20 and R21 is hydrogen, unless R18 is ##STR18## in which case at least one of R19 and R20 is not hydrogen but is a said substituent, or R19 R20 or R19 and R21 each form a ring with the atoms joining them, andM2 is silicon, germanium or tin, which comprises stopping the polymerization at a time when Mw/Mn<

    2 .

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