US5696045A — Process for the preparation of polyolefins

Claim 1

Independent Claim 848 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the formula I and at least one zirconocene of the formula Ia ##STR11## in which R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 to alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group or a halogen atom, R 3 is a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkyloxy group, a C 8 -C 40 arylalkenyl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, where at least one R 4 radicals per indenyl ring is different from hydrogen, or two or more R 4 radicals form a ring system with the atoms connecting them, R 5 and R 6 are identical or different and are a halogen atom, a C 1 -C 10 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkyloxy group, a C 8 -C 40 arylalkenyl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, R 7 is ##STR12## --Ge--, --Sn--, --O--, --S--, ═SO, ═SO 2 , ═CO, or P(O)R 11 , where R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 or R 11 and R 13 each form a ring with the atoms connecting them, M 1 is tin, or R 7 is ##STR13## ═BR 11' , ═AlR 11' , ═NR 11' or ═PR 11' where R 11' , R 12' and R 13' are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 flouroalkyl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11' and R 12' or R 11' and R 13' each form a ring with the atoms connecting them, M 1' is silicon or germanium, R 8 and R 9 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 8 and R 9 each form a ring with the atoms connecting them, R 14 and R 15 are identical or different and are unsubstituted or substituted cyclopentadienyl which form a sandwich structure with the zirconium atom and optionally are substituted with the substituents defined in the definition of R 4 , m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2.

Claim 2

Dependent Claim 848 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the formula I and at least one zirconocene of the formula Ia ##STR11## in which R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 to alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group or a halogen atom, R 3 is a hydrogen atom, a halogen atom, a C 1 -C 10 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkyloxy group, a C 8 -C 40 arylalkenyl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, R 4 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, where at least one R 4 radicals per indenyl ring is different from hydrogen, or two or more R 4 radicals form a ring system with the atoms connecting them, R 5 and R 6 are identical or different and are a halogen atom, a C 1 -C 10 alkyl group, which may be halogenated, a C 6 -C 10 aryl group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkyloxy group, a C 8 -C 40 arylalkenyl group, an --NR 2 10 , --OR 10 , --SR 10 , --OSiR 3 10 , --SiR 3 10 or --PR 2 10 radical, in which R 10 is a halogen atom, a C 1 -C 10 alkyl group or a C 6 -C 10 aryl group, R 7 is ##STR12## --Ge--, --Sn--, --O--, --S--, ═SO, ═SO 2 , ═CO, or P(O)R 11 , where R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 or R 11 and R 13 each form a ring with the atoms connecting them, M 1 is tin, or R 7 is ##STR13## ═BR 11' , ═AlR 11' , ═NR 11' or ═PR 11' where R 11' , R 12' and R 13' are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 flouroalkyl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11' and R 12' or R 11' and R 13' each form a ring with the atoms connecting them, M 1' is silicon or germanium, R 8 and R 9 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 8 and R 9 each form a ring with the atoms connecting them, R 14 and R 15 are identical or different and are unsubstituted or substituted cyclopentadienyl which form a sandwich structure with the zirconium atom and optionally are substituted with the substituents defined in the definition of R 4 , m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2.

Claim 3

Dependent Claim 86 words

The metallocene mixture as claimed in claim 1 wherein the formula (Ia) is (±)-phenyl(methyl)silyl(indenyl) 2 zirconium dichloride, phenyl (methyl)methylene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl)(cyclopentadienyl) zirconium dichloride, (±)-dimethylsilyl-1(2,3,5-trimethyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylgermyl(indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(indenyl) 2 zirconium dimethyl, (±)-phenyl(vinyl)silyl(indenyl) 2 zirconium dichloride, (±)-phenyl(vinyl)silyl(indenyl) 2 -zirconium dimethyl, (±)-dimethylsilyl(2,4-dimethylcyclopentadienyl) 2 zirconium dichloride, (±)-diphenylsilyl(2,4-dimethyl-1-cyclopentadienyl)zirconium dichloride, (±)-isopropylidene(indenyl) 2 -zirconium dichloride, (±)-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, (±)-ethylene(indenyl) 2 zirconium dichloride, (±)-methylene(3-t-butyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylsilyl(4,7-dimethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(2-methyl-1-indenyl) 2 -zirconium dichloride, (±)-phenyl(methyl)silyl(2-methyl-1-indenyl)zirconium dichloride, (±)-dimethylsilyl(2-ethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(4-phenyl-1-indenyl) 2 zirconium dichloride, or mixtures thereof.

Claim 4

Dependent Claim 138 words

A metallocene mixture which is (±)-dimethylol(2-methyl-4-phenyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 ZrCl 2 and diphenyl(fluorenyl)-(cyclopentadienyl)ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 ZrCl 2 and dimethyl-C(fluorenyl)(cyclopentadienyl)ZrCl 2 ; (±)-dimethylSi(2-methyl-4,6-diisopropyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylGe(indenyl) 2 ZrCl 2 ; (±)-phenyl(methyl)Si(2,4,6-trimethyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylC(indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-isopropyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(2,3,5-trimethyl-1-cyclopentadienyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4,5-benzo-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 -ZrCl 2 ; (±)-phenyl(methyl)Si(2-methyl-α-acenaphth-1-indenyl) 2 -Zr dimethyl and (±)-phenyl(vinyl)Si-(indenyl) 2 -Zr dimethyl; (±)-dimethylSi(2-5,6-trimethyl-1-indenyl) 2 -ZrCl 2 and (±)-phenyl 2 Si(2,4-dimethyl-1-cyclopentadienyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4,5-benzo-1-indenyl) 2 -ZrCl 2 ; and (±)-dimethylSi(4,5-benzo-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-phenyl-1-indenyl) 2 -ZrCl 2 and (±)-dimethylSi(4-phenyl-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 -ZrCl 2 and (±)-dimethylSi-(2,4,6-tri-methyl-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-phenyl-1-indenyl) 2 ZrCl 2 , (±)-dimethylSi(2,4,6-tri-methyl-1-indenyl) 2 ZrCl 2 or (±)-ethylidene(indenyl) 2 -ZrCl 2 .

Claim 5

Dependent Claim 138 words

A metallocene mixture which is (±)-dimethylol(2-methyl-4-phenyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 ZrCl 2 and diphenyl(fluorenyl)-(cyclopentadienyl)ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 ZrCl 2 and dimethyl-C(fluorenyl)(cyclopentadienyl)ZrCl 2 ; (±)-dimethylSi(2-methyl-4,6-diisopropyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylGe(indenyl) 2 ZrCl 2 ; (±)-phenyl(methyl)Si(2,4,6-trimethyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylC(indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-isopropyl-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(2,3,5-trimethyl-1-cyclopentadienyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4,5-benzo-1-indenyl) 2 ZrCl 2 and (±)-dimethylSi(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 -ZrCl 2 ; (±)-phenyl(methyl)Si(2-methyl-α-acenaphth-1-indenyl) 2 -Zr dimethyl and (±)-phenyl(vinyl)Si-(indenyl) 2 -Zr dimethyl; (±)-dimethylSi(2-5,6-trimethyl-1-indenyl) 2 -ZrCl 2 and (±)-phenyl 2 Si(2,4-dimethyl-1-cyclopentadienyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4,5-benzo-1-indenyl) 2 -ZrCl 2 ; and (±)-dimethylSi(4,5-benzo-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-phenyl-1-indenyl) 2 -ZrCl 2 and (±)-dimethylSi(4-phenyl-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-(1-naphthyl)-1-indenyl) 2 -ZrCl 2 and (±)-dimethylSi-(2,4,6-tri-methyl-1-indenyl) 2 -ZrCl 2 ; (±)-dimethylSi(2-methyl-4-phenyl-1-indenyl) 2 ZrCl 2 , (±)-dimethylSi(2,4,6-tri-methyl-1-indenyl) 2 ZrCl 2 or (±)-ethylidene(indenyl) 2 -ZrCl 2 .

Claim 6

Dependent Claim 522 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the group I and at least one zirconocene of the formula Ia ##STR14## in which R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group or a halogen atom, R 7 is ##STR15## --Ge--, --Sn--, --O--, --S--, ═SO, ═SO 2 , ═CO, or P(O)R 11 , where R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 10 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 or R 11 and R 13 each form a ring with the atoms connecting them, M 1 is tin, or R 7 is ##STR16## ═BR 11' , ═AlR 11' , ═NR 11' or ═PR 11' where R 11' , R 12' and R 13' are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11' and R 12' or R 11' and R 13' each form a ring with the atoms connecting them, M 1' is silicon or germanium, R 8 and R 9 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 8 and R 9 each form a ring with the atoms connecting them, R 14 and R 15 are identical or different and are unsubstituted or substituted cyclopentadienyl which form a sandwich structure with the zirconium atom and optionally are substituted with the substituents defined in the definition of R 4 , m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2 and the zirconocene of the group I is dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 12 , phenyl(methyl)silanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 ,

Claim 7

Dependent Claim 522 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the group I and at least one zirconocene of the formula Ia ##STR14## in which R 1 and R 2 are identical or different and are a hydrogen atom, a C 1 -C 10 alkyl group, a C 1 -C 10 alkoxy group, a C 6 -C 10 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group or a halogen atom, R 7 is ##STR15## --Ge--, --Sn--, --O--, --S--, ═SO, ═SO 2 , ═CO, or P(O)R 11 , where R 11 , R 12 and R 13 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 10 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11 and R 12 or R 11 and R 13 each form a ring with the atoms connecting them, M 1 is tin, or R 7 is ##STR16## ═BR 11' , ═AlR 11' , ═NR 11' or ═PR 11' where R 11' , R 12' and R 13' are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 11' and R 12' or R 11' and R 13' each form a ring with the atoms connecting them, M 1' is silicon or germanium, R 8 and R 9 are identical or different and are a hydrogen atom, a halogen atom, a C 1 -C 20 alkyl group, a C 1 -C 20 fluoroalkyl group, a C 6 -C 30 aryl group, a C 6 -C 30 fluoroaryl group, a C 1 -C 20 alkoxy group, a C 2 -C 20 alkenyl group, a C 7 -C 40 arylalkyl group, a C 8 -C 40 arylalkenyl group, a C 7 -C 40 alkylaryl group, or R 8 and R 9 each form a ring with the atoms connecting them, R 14 and R 15 are identical or different and are unsubstituted or substituted cyclopentadienyl which form a sandwich structure with the zirconium atom and optionally are substituted with the substituents defined in the definition of R 4 , m and n are identical or different and are zero, 1 or 2, with m plus n being equal to zero, 1 or 2 and the zirconocene of the group I is dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 12 , phenyl(methyl)silanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 ,

Claim 8

Dependent Claim 63 words

2-ethanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-disopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-t-butyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-methyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4-dimethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 1,2-ethanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl1-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-t-butyl-1-indenyl)ZrCl 2 , or dimethylsilanediylbis(2,5,6-trimethyl-1-indenyl)ZrCl 2 .

Claim 9

Dependent Claim 63 words

2-ethanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-disopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-t-butyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-methyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4-dimethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 1,2-ethanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl1-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-t-butyl-1-indenyl)ZrCl 2 , or dimethylsilanediylbis(2,5,6-trimethyl-1-indenyl)ZrCl 2 .

Claim 10

Dependent Claim 207 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the group I and at least one zirconocene of the group Ia wherein the zirconocene of the group I is dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2,4,6-trimethyl-1-indenyl1)ZrCl 2 , 1,2-ethanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl1-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-t-butyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-methyl-1-indenyl1)ZrCl 2 , dimethylsilanediylbis(2,4-dimethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 1,2-ethanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-ethyl-4-phenyl1-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-t-butyl-1-indenyl)ZrCl 2 , or dimethylsilanediylbis(2,5,6-trimethyl-1-indenyl)ZrCl 2 , and the zirconocene of group Ia is (±)-phenyl(methyl)silyl(indenyl) 2 zirconium dichloride, diphenylmethylene (9-fluorenyl)(cyclopentadienyl)zirconium dichloride, phenyl(methyl)methylene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl)(cyclopentadienyl)-zirconium dichloride, (±)-dimethylsilyl(2,3,5-trimethyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylsilyl(indenyl) 2 zirconium dichloride, (±)-dimethylgermyl(indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(indenyl) 2 zirconium dimethyl, (±)-phenyl(vinyl)silyl(indenyl) 2 zirconium dichloride, ##STR17## (±)-dimethylsilyl(2,4-dimethylcyclopentadienyl) 2 zirconium dichloride, (±)-isopropylidene(indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, (±)-ethylene(indenyl) 2 zirconium dichloride, (±)-methylene(3-t-butyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylsilyl(4,7-dimethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(2-methyl-1-indenyl) 2 zirconium dichloride, (±)-phenyl(methyl)silyl(2-methyl-1-indenyl)zirconium dichloride, (±)-dimethylsilyl(2-ethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(4,5-benzo-1-indenyl) 2 zirconium dichloride and (±)-dimethylsilyl(4-Phenyl-1-indenyl) 2 zirconium dichloride.

Claim 11

Dependent Claim 207 words

A metallocene mixture comprising at least two different zirconocenes with at least one zirconocene of the group I and at least one zirconocene of the group Ia wherein the zirconocene of the group I is dimethylsilanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-(2-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-(1-naphthyl)-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2,4,6-trimethyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2,4,6-trimethyl-1-indenyl1)ZrCl 2 , 1,2-ethanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,6-diisopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl1-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-t-butyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4-isopropyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-methyl-1-indenyl1)ZrCl 2 , dimethylsilanediylbis(2,4-dimethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4-ethyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-α-acenaphth-1-indenyl)ZrCl 2 1,2-ethanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-4,5-benzo-1-indenyl)ZrCl 2 , 1,2-butanediylbis(2-ethyl-4-phenyl1-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-ethyl-4-phenyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , phenyl(methyl)silanediylbis(2-methyl-5-isobutyl-1-indenyl)ZrCl 2 , dimethylsilanediylbis(2-methyl-5-t-butyl-1-indenyl)ZrCl 2 , or dimethylsilanediylbis(2,5,6-trimethyl-1-indenyl)ZrCl 2 , and the zirconocene of group Ia is (±)-phenyl(methyl)silyl(indenyl) 2 zirconium dichloride, diphenylmethylene (9-fluorenyl)(cyclopentadienyl)zirconium dichloride, phenyl(methyl)methylene(9-fluorenyl)(cyclopentadienyl)zirconium dichloride, isopropylidene(9-fluorenyl)(cyclopentadienyl)-zirconium dichloride, (±)-dimethylsilyl(2,3,5-trimethyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylsilyl(indenyl) 2 zirconium dichloride, (±)-dimethylgermyl(indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(indenyl) 2 zirconium dimethyl, (±)-phenyl(vinyl)silyl(indenyl) 2 zirconium dichloride, ##STR17## (±)-dimethylsilyl(2,4-dimethylcyclopentadienyl) 2 zirconium dichloride, (±)-isopropylidene(indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl) 2 zirconium dichloride, (±)-ethylene(indenyl) 2 zirconium dichloride, (±)-methylene(3-t-butyl-1-cyclopentadienyl) 2 zirconium dichloride, (±)-dimethylsilyl(4,7-dimethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(2-methyl-1-indenyl) 2 zirconium dichloride, (±)-phenyl(methyl)silyl(2-methyl-1-indenyl)zirconium dichloride, (±)-dimethylsilyl(2-ethyl-1-indenyl) 2 zirconium dichloride, (±)-dimethylsilyl(4,5-benzo-1-indenyl) 2 zirconium dichloride and (±)-dimethylsilyl(4-Phenyl-1-indenyl) 2 zirconium dichloride.

Claim 12

Dependent Claim 20 words

A catalyst system which comprises the combination of the metallocene mixture as claimed in claim 21 combined with an aluminoxane.

Claim 13

Dependent Claim 111 words

A catalyst system comprising the metallocene mixture as claimed in claim 21 and an aluminoxane of the formula II ##STR18## for the linear type and/or formula III ##STR19## for the cyclic type, in which the radicals R in formulae II and III may be identical or different and are a C 1 -C 6 alkyl group, a C 1 -C 6 fluoroalkyl group, a C 6 -C 18 aryl group, a C 1 -C 6 fluoroaryl group or hydrogen and n is an integer from 0 to 50, or, instead of the aluminoxane, a mixture of the aluminoxane of the formula II and/or the formula III with the AlR 3 compound.

Claim 14

Dependent Claim 12 words

The catalyst as claimed in claim 7, wherein the aluminoxane is methylaluminoxane.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	2000-12-08	2001-06-09	2001-12-09	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	2004-12-08	2005-06-09	2005-12-09	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2008-12-08	2009-06-09	2009-12-09	$7700.00	Window Closed / Lapsed

Process for the preparation of polyolefins

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