Cycloolefin block copolymers and a process for their preparation
First Claim
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1. A process for the preparation of a cycloolefin block copolymer, comprisinga) 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 R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1 -C8 - 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 R9, R10, R11 and R12 are identical or different and are a hydrogen atom or a C1 -C8 -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 R13 are identical or different and are a C1 -C6 -alkyl group, a C6 -C18 -aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, and a metallocene of the formula XI ##STR15## in which M1 is titanium, zirconium, hafnium, vanadium, nioblum or tantalum,R14 and R15 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C6 -C10 alkoxy group, a C6 -C10 aryl group, a C6 -C10 - aryloxy group, a C2 -C10 -alkenyl group, a C7 -C40 -arylalkyl group, a C4 -C40 -alkyl aryl group or a C8 -C40 -arylalkenyl group,R16 and R17 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M1,R18 is ##STR16## =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 a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -fluoroaryl group, a C6 -C10 -aryl group, a C1 -C10 -alkoxy group, a C2 -C10 -alkenyl group, a C7 -C40 -arylalkyl group, a C8 -C40 -aralkenyl group, or a C7 -C40 -alkylaryl group or R19 and R20, or R19 and R21, form a ring, in each case with the atoms linking them, andM2 is silicon, germanium or tin, and, in each case at a molecular weight distribution Mw /Mn 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.
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Abstract
Cycloolefin block copolymers, which in particular are suitable as phase promoters, are preferably obtained by copolymerization of polycyclic olefins, such as norbornene, with acyclic olefins, such as ethylene, by, at a molecular weight distribution Mw /Mn of the polymer block forming of less than 2, changing the reaction conditions one or more times in such a way that the monomer/comonomer ratio changes by at least 10 % or a further polymerizable monomer is metered into the monomer or the monomers.
47 Citations
18 Claims
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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 R1, R2, R3, R4, R5, R6, R7 and R8 are identical or different and are a hydrogen atom or a C1 -C8 - 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 R9, R10, R11 and R12 are identical or different and are a hydrogen atom or a C1 -C8 -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 R13 are identical or different and are a C1 -C6 -alkyl group, a C6 -C18 -aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, and a metallocene of the formula XI ##STR15## in which M1 is titanium, zirconium, hafnium, vanadium, nioblum or tantalum,R14 and R15 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C6 -C10 alkoxy group, a C6 -C10 aryl group, a C6 -C10 - aryloxy group, a C2 -C10 -alkenyl group, a C7 -C40 -arylalkyl group, a C4 -C40 -alkyl aryl group or a C8 -C40 -arylalkenyl group, R16 and R17 are a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M1, R18 is ##STR16## =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 a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -fluoroaryl group, a C6 -C10 -aryl group, a C1 -C10 -alkoxy group, a C2 -C10 -alkenyl group, a C7 -C40 -arylalkyl group, a C8 -C40 -aralkenyl group, or a C7 -C40 -alkylaryl group or R19 and R20, or R19 and R21, form a ring, in each case with the atoms linking them, and M2 is silicon, germanium or tin, and, in each case at a molecular weight distribution Mw /Mn 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. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14)
- to 150°
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15. A process for the preparation of a cycloolefin/1-olefin block copolymer, wherein 0.1 to 95% by weight, with respect to the total amount of monomers employed, of at least one cycloolefin is copolymerized with a copolymerizable amount, not exceeding 99% by weight, with respect to the total amount of monomers employed, of at least one 1-olefin, said process comprising a plurality of polymerization stages, said polymerization stages comprising:
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(a) polymerizing, at -78°
to 150°
C. and a pressure of 0.1 to 64 bar in the presence of a co-catalyst system comprising a metallocene and an aluminoxane, a starting monomer mixture comprising 1-olefin and cycloolefin, the starting cycloolefin being norbornene, C1 -C6 -alkyl-substituted norbornene, tetracyclodecene, C1 -C6 -alkyl-substituted tetracyclodecene, or a mixture thereof, and, while the thus-forming polymer block has a molecular weight distribution Mw /Mn of less than 2,(b) changing the cycloolefin/1-olefin monomer ratio of the starting monomer mixture by at least 10% by increasing the amount of a starting monomer of the starting mixture or by metering in an additional cycloolefin monomer or an additional 1-olefin monomer. - View Dependent Claims (16, 17, 18)
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Specification
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Current AssigneeHoechst Aktiengesellschaft (Sanofi )
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Original AssigneeHoechst Aktiengesellschaft (Sanofi )
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InventorsRohrmann, Jurgen, Osan, Frank, Brekner, Michael-Joachim
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Primary Examiner(s)JAGANNATHAN, VASUDEVAN SALEM
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Application NumberUS08/019,094Time in Patent Office516 DaysField of Search525/289, 525/297US Class Current525/289CPC Class CodesC08F 210/02 EtheneC08F 232/00 Copolymers of cyclic compou...C08F 2500/03 Narrow molecular weight dis...C08F 2500/25 CycloolefineC08F 297/08 polymerising mono-olefinsY10S 526/943 Polymerization with metallo...
