Cycloolefin (co)polymers with a narrow molecular weight distribution and a process for the preparation thereof
First Claim
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 .
1 Assignment
0 Petitions
Accused Products
Abstract
Polymers of polycyclic olefins such as, for example, norbornene or tetracyclododecene, or copolymers of polycyclic olefins with cycloolefins and/or 1-olefins with a very narrow molecular weight distribution are obtained without ring opening by a polymerization in which a catalyst which is composed of an aluminoxane and of a stereorigid, chiral metallocene compound of an element of groups IVb to VIb is used, and in which the reaction is stopped at a time when the molecular weight distribution Mw/Mn of the polymer formed is <2.
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Citations
11 Claims
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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 . - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11)
- to 150°
Specification