Claims
- 1. An catalyst composition comprising the reaction product of a) a polymeric support functionalized with a covalently bonded protonated ammonium salt of a noncoordinating anion and b) one or more bridged, substituted indenyl metallocene compounds.
- 2. The catalyst composition of claim 1 wherein the support is an aromatic polymeric support.
- 3. The catalyst composition of claim 1 wherein the support is polystyrene.
- 4. The catalyst composition of claim 1 wherein the metallocene is represented by the formula: wherein M is a metal of Group 4, 5, or 6 of the Periodic Table;R1 and R2 are identical or different, preferably identical, and are one of a hydrogen atom, a C1-C10 alkyl 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; R5 and R6 are identical or different, and are one of a halogen atom, a C1-C10 alkyl group which may be halogenated, a C6-C10 aryl group which may be halogenated, a C2-C10 alkenyl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a —NR215, —SR15, —OR15, —OSiR315 or —PR215 radical, wherein R15 is one of a halogen atom, a C1-C10 alkyl group, or a C6-C10 aryl group; —B(R11)—; −Al(R11)—, —Ge—, —Sn—, —O—, —S—, —SO—, —SO2—, —N(R11)—, —CO—, —P(R11)—, or —P(O)(R11)—;wherein:R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C20 alkyl group, a C1-C20 fluoroalkyl group, a C6-C30 aryl group, a C6-C20 fluoroalkyl group, a C1-C20 alkoxy group, a C2-C20 alkenyl group, a C7-C40 arylalkyl group, a C8-C40 arylalkenyl group, a C7-C40 alkylaryl group, or R11 and R12, or R11 and R13, together with the atoms binding them, form one or more ring systems; M2 is silicon, germanium or tin; R8 and R9 are identical or different and have the meanings stated for R11; m and n are identical or different and are zero, 1 or 2, m plus n being zero, 1 or 2; and the radicals R3, R4, and R10 are identical or different and have the meanings stated for R11, R12 and R13 or two adjacent R10 radicals are joined together to form a ring system.
- 5. The catalyst composition of claim 1 wherein the metallocene is selected from the group consisting of:Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH3)2Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zr(CH3)2; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zr(CH3)2; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zr(CH3)2; Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Diphenylsilandiylbis(2-methyl-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zr(CH3)2, and Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zr(CH3)2.
- 6. Composition system of claim 1 wherein the polymeric support is functionalized with an ammonium salt of a noncoordinating anion represented by the formula:[Polymer-(R1)—N(R2)(R3)H]+[NCA]wherein R1 and where R1 in formulas I or II is hydrocarbyl or substituted hydrocarbyl, R2 and R3 are the same or different and are selected from the group consisting of: hydrogen, hydrocarbyl, and a substituted hydrocarbyl; and wherein NCA is represented by the formula:[BAr1Ar2X3X4]−wherein:B is boron in a valence state of 3; Ar1 and Ar2 are the same of different substituted-aromatic hydrocarbon radicals which, radicals may be linked to each other through a stable bridging group; and X3 and X4 are independently selected from the group consisting of hydride radicals, halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals and organometalloid radicals.
- 7. The catalyst system of claim 1 wherein the support is functionalized with a ammonium salt of a noncoordinating anion selected from the group consisting of tetrakis perfluorophenyl borate, tetrakis(3,5-di(tri-fluoromethyl)phenyl borate and tetrakis(di-t-butylmethylsilyl)perfluorophenyl borate.
- 8. A catalyst composition comprising the reaction product of a) an aromatic polymeric support functionalized with a covalently bonded protonated ammonium salt of a noncoordinating anion selected from the group consisting of tetrakis perfluorophenyl borate, tetrakis(3,5-di(tri-fluoromethyl)phenyl borate and tetrakis(di-t-butylmethylsilyl)perfluorophenyl borate and b) one or more metallocenes selected from the group consisting of:Dimethylsilandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH3)2Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)Zr(CH3)2; Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)Zr(CH3)2; Dimethylsilandiylbis(2-ethyl-4-phenyl-1-indenyl)Zr(CH3)2; Dimethylsilandiylbis(2-ethyl-4-naphthyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4-phenyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-(1-naphthyl)-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-(2-naphthyl)-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4,5-diisopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2,4,6-trimethyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-4,6-diisopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-t-butyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4-isopropyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-ethyl-4-methyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2,4-dimethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-(methylbenzo)-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-4,5-(tetramethylbenzo)-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-α-acenaphthyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-4,5-benzo-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2,4,7-trimethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-1-indenyl)Zr(CH3)2, 1,2-Ethandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Diphenylsilandiylbis(2-methyl-1-indenyl)Zr(CH3)2, 1,2-Butandiylbis(2-methyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-ethyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH3)2, Phenyl(methyl)silandiylbis(2-methyl-5-isobutyl-1-indenyl)Zr(CH3)2, Dimethylsilandiylbis(2-methyl-5-t-butyl-1-indenyl)Zr(CH3)2, and Dimethylsilandiylbis(2,5,6-trimethyl-1-indenyl)Zr(CH3)2.
- 9. A method for polymerizing olefins comprising contacting one or more monomers under suitable polymerization conditions in the presence of the catalyst compositions of claims 1 through 8.
Parent Case Info
This application is a continuation-in-part of U.S. Ser. No. 09/092,752, filed Jun. 5, 1998, now U.S. Pat. No. 6,100,214, which application in turn claims priority of U.S. Ser. No. 60/048,965, filed Jun. 6, 1997 and U.S. Ser. No. 60/079,569, filed Mar. 27, 1998.
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Provisional Applications (2)
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Jun 1997 |
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Continuation in Parts (1)
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09/092752 |
Jun 1998 |
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09/184358 |
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