Process for the preparation of cycloolefin polymers
AssigneeHoechst Aktiengesellschaft
InventorsMichael-Joachim Brekner, Jurgen Rohrmann, Walter Spaleck, Martin Antberg
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Abstract
Polymers of polycyclic olefins of the formulae I to IV having a viscosity number greater than 20 cm.sup.3 /g and a glass transition temperature above 100.degree. C. are obtained without ring opening at a high polymerization rate and at polymerization temperatures advantageous from the technical point of view by means of a catalyst which is composed of a stereo-rigid, chiral metallocene compound of groups IVb to VIb of the Periodic Table of the Elements and an aluminoxane. ##STR1##
Claims6
A process for the preparation of a cycloolefin polymer by polymerizing 0.1 to 100% by weight, relative to the total amount of the monomers, of at least one monomer of the formulae I, II, III or IV ##STR17## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are identical or different and denote a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical, it being possible for identical radicals in the various formulae to have a different meaning, 0 to 99.9% by weight, relative to the total amount of the monomers, of a cycloolefin of the formula V ##STR18## in which n is a number from 2 to 10, and 0 to 99.9% by weight, relative to the total amount of the monomers, of at least one acyclic 1-olefin of the formula VI ##STR19## in which R.sup.9, R.sup.10, R.sup.11 and R.sup.12 are identical or different and denote a hydrogen atom or a C.sub.1 -C.sub.8 -alkyl radical, in solution, in suspension, in a monomer melt or in the gas phase, at a temperature of -78.degree. to 150.degree. C., under a pressure of 0.5 to 64 bar, and in the presence of a catalyst which is composed of a metallocene as the transition metal component and an aluminoxane of the formula VII ##STR20## for the linear type, and/or of the formula VIII ##STR21## for the cyclic type, R.sup.13 in the formulae VII and VIII denoting a C.sub.1 -C.sub.6 -alkyl group or phenyl or benzyl and n being an integer from 2 to 50, which comprises carrying out the polymerization in the presence of a catalyst the transition metal component of which is a compound of the formula IX ##STR22## in which M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
- R.sup.14 and R.sup.15 are identical or different and denote a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.6 -C.sub.10 -aryloxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.7 -C.sub.40 -alkylaryl group or a C.sub.8 -C.sub.40 -arylalkenyl group,
- R.sup.16 and R.sup.17 are identical or different and denote a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure together with the central atom M.sup.1,
- R.sup.18 is ##STR23## .dbd.BR.sup.19, .dbd.AlR.sup.19, --Ge--, --Sn--, --O--, --S--, .dbd.SO, .dbd.SO.sub.2, .dbd.NR.sup.19, .dbd.CO, .dbd.PR.sup.19 or .dbd.P(O)R.sup.19 ;
- R.sup.19, R.sup.20 and R.sup.21 being identical or different and denoting a hydrogen atom, a halogen atom, a C.sub.1 -C.sub.10 -alkyl group, a C.sub.1 -C.sub.10 -fluoroalkyl group, a C.sub.6 -C.sub.10 -fluoroaryl group, a C.sub.6 -C.sub.10 -aryl group, a C.sub.1 -C.sub.10 -alkoxy group, a C.sub.2 -C.sub.10 -alkenyl group, a C.sub.7 -C.sub.40 -arylalkyl group, a C.sub.8 -C.sub.40 -arylalkenyl group or a C.sub.7 -C.sub.40 -alkylaryl group or R.sup.19 and R.sup.20 or R.sup.19 and R.sup.21, in each case with the atoms linking them, forming a ring, provided that when R.sup.16 and R.sup.17 are identical and R.sup.18 is ##STR24## R.sup.19 and R.sup.20 are not hydrogen or C.sub.1 -C.sub.10 -alkyl;
- and M.sup.2 is silicon, germanium or tin.
Dependencies are inferred from the claim text.