Metallocenes having benzo-fused indenyl derivatives as ligands, processes for their preparation and their use as catalysts
First Claim
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1. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra --CH═
- CH--Rb, in which R11 and Rh are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR13## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,R1 and R2 are identical or different and are a hydrogen 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 C8 -C40 -arylalkenyl group, an OH group or a halogen atom,the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group,R4 to R10 have the meaning given for R3, or adjacent radicals R6 to R10, with the atoms joining them form an aromatic or aliphatic ring, andR11 is ##STR14## ═
BR12, ═
AlR12, --Ge--, --Sn--, --O--, --S--, ═
SO, ═
SO2, ═
NR12, ═
CO, ═
PR12 or ═
P(O)R12in whichR12 is a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -aryl group, a C6 -C10 -fluoroaryl 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,R13 is a hydrogen atom, a halogen atom, a C4 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -aryl group, a C6 -C10 -fluoroaryl group, a C1 -C10 -alkoxy group, a C2 -C10 -alkenyl group, a C7 -C10 -arylalkyl group, a C8 -C40 -arylalkenyl group or a C7 -C40 -alkylaryl group, or R12 and R13, in each case with the atoms joining the form a ring, andM2 is silicon, germanium or tin.
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Abstract
A very effective catalyst system for olefin polymerization comprises a cocatalyst, preferably an aluminoxane, and a metallocene of the formula I ##STR1## in which, preferably, M1 is Zr or Hf, R1 and R2 are halogen or alkyl, R3 is alkyl, R4 to R10 are alkyl or hydrogen and R11 is a (substituted) alkylene or heteroatom bridge.
36 Citations
20 Claims
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1. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra --CH═
- CH--Rb, in which R11 and Rh are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR13## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
R1 and R2 are identical or different and are a hydrogen 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 C8 -C40 -arylalkenyl group, an OH group or a halogen atom, the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group, R4 to R10 have the meaning given for R3, or adjacent radicals R6 to R10, with the atoms joining them form an aromatic or aliphatic ring, and R11 is ##STR14## ═
BR12, ═
AlR12, --Ge--, --Sn--, --O--, --S--, ═
SO, ═
SO2, ═
NR12, ═
CO, ═
PR12 or ═
P(O)R12in which R12 is a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -aryl group, a C6 -C10 -fluoroaryl 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, R13 is a hydrogen atom, a halogen atom, a C4 -C10 -alkyl group, a C1 -C10 -fluoroalkyl group, a C6 -C10 -aryl group, a C6 -C10 -fluoroaryl group, a C1 -C10 -alkoxy group, a C2 -C10 -alkenyl group, a C7 -C10 -arylalkyl group, a C8 -C40 -arylalkenyl group or a C7 -C40 -alkylaryl group, or R12 and R13, in each case with the atoms joining the form a ring, and M2 is silicon, germanium or tin. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12)
- CH--Rb, in which R11 and Rh are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR13## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
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13. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra --CH═
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR17## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
R1 and R2 are identical or different and are a hydrogen 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 C8 -C40 -arylalkenyl group, an OH group or a halogen atom, the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a C4 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group, R4 to R10 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group, or adjacent radicals R4 to R10, with the atoms joining them form an aromatic or aliphatic ring, and R11 is ##STR18## ═
BR12, ═
AlR12, --Ge--, --Sn--, --O--, --S--, ═
SO, ═
SO2, ═
NR12, ═
CO, ═
PR12 or ═
P(O)R12in which R12 and R13 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 -aryl group, a C6 -C10 -fluoroaryl 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 R12 and R13, in each case with the atoms joining the, form a ring, and M2 is silicon, germanium or tin. - View Dependent Claims (14)
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR17## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
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15. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra --CH═
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR19## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
R1 and R2 are identical or different and are a hydrogen 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 C8 -C40 -arylalkenyl group, an OH group or a halogen atom, the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group, R4 to R10 have the meaning given for R3, or adjacent radicals R4 to R10, with the atoms joining them form an aromatic or aliphatic ring, and R11 is ##STR20## ═
BR12, ═
AlR12, --Ge--, --Sn--, --O--, --S--, ═
SO, ═
SO2, ═
NR12, ═
CO, ═
PR12 or ═
P(O)R12in which R12 and R13 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 -aryl group, a C6 -C10 -fluoroaryl 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 R12 and R13, in each case with the atoms joining the, form a ring, and M2 is germanium or tin. - View Dependent Claims (16, 17)
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR19## in which M1 is a metal of group IVb, Vb or VIb of the periodic table,
-
18. A process for the preparation of an olefin polymer by polymerization or copolymerization of an olefin of the formula Ra --CH═
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR21## in which M1 is a titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten,
R1 and R2 are identical or different and are a hydrogen 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 C8 -C40 -arylalkenyl group, an OH group or a halogen atom, the radicals R3 are identical or different and are a hydrogen atom, a halogen atom, a C1 -C10 -alkyl group, which can be halogenated, a C6 -C10 -aryl group or an --NR2, --SR, --OSiR3, --SiR3 or --PR2 radical, in which R is a halogen atom, a C1 -C10 -alkyl group or a C6 -C10 -aryl group, R4 to R10 have the meaning given for R3, or adjacent radicals R4 to R10, with the atoms joining them form an aromatic or aliphatic ring, and R11 is ##STR22## ═
BR12,═
AlR12, --Ge--, --Sn--, --O--, --S--, ═
SO, ═
SO2, ═
NR12, ═
CO, ═
PR12 or ═
P(O)R12in which R12 and R13 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 -aryl group, a C6 -C10 -fluoroaryl 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 R12 and R13, in each case with the atoms joining the, form a ring, and M2 is silicon, germanium or tin. - View Dependent Claims (19, 20)
- CH--Rb, in which Ra and Rb are identical or different and are a hydrogen atom or a hydrocarbon radical having 1 to 14 carbon atoms, or Ra and Rb, with the atoms joining them, can form a ring, in the presence of a catalyst which is formed from a metallocene, as the transition metal compound, and a cocatalyst, which comprises using a compound of the formula I ##STR21## in which M1 is a titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten,
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Current AssigneeTargor Gmbh (BASF SE)
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Original AssigneeTargor Gmbh (BASF SE)
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InventorsWinter, Andreas, Dolle, Volker, Rohrmann, Jurgen, Kuber, Frank
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Primary Examiner(s)Nagumo, Mark
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Application NumberUS08/470,340Time in Patent Office1,519 DaysField of Search526/127, 526/134, 526/160, 526/943, 502/103, 502/117US Class Current526/160CPC Class CodesC07C 2602/08 the other ring being five-m...C07C 45/46 Friedel-Crafts reactionsC07C 45/67 by isomerisation; by change...C07C 49/67 having two rings, e.g. tetr...C07F 17/00 MetallocenesC08F 10/00 Homopolymers and copolymers...C08F 10/06 PropeneC08F 110/06 PropeneC08F 210/06 PropeneC08F 210/16 Copolymers of ethene with a...C08F 2500/01 High molecular weight, e.g....C08F 2500/03 Narrow molecular weight dis...C08F 2500/12 Melt flow index or melt flo...C08F 2500/15 IsotacticC08F 2500/17 ViscosityC08F 4/63912 in combination with an orga...C08F 4/63927 two cyclopentadienyl rings ...C08F 4/65908 in combination with an ioni...Y10S 526/943 Polymerization with metallo...
