Polyolefins prepared with metallocene catalysts having 2-substituted indenyl type ligands
First Claim
1. A compound of the formula I for preparing essentially isotactic olefin polymers in whichM1 is a metal from 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 C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a halogen atom, a C1-C10-alkyl group, which is optionally halogenated, a C6-C10-aryl group, an —
- NR215, —
SR15, —
OSiR315, —
SiR315 or —
PR215 radical in which R15 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and are as defined for R3 and R4, with the proviso that R5 and R6 are not hydrogen, R7 iswhereR11, 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 R11 and R12 or R11 and R13, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, R8 and R9 are identical or different and are as defined 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 R10 are identical or different and are as defined for R11, R12 and R13.
3 Assignments
0 Petitions
Accused Products
Abstract
The novel metallocenes of the formula I
in which, preferably, M1 is Zr or Hf, R1 and R2 are alkyl or halogen, R3 and R4 are hydrogen, R5 and R6 are alkyl or haloalkyl, —(CR8R9)m—R7—(CR8R9)n— is a single- or multi-membered chain in which R7 may also be a (substituted) hetero atom, m+n is zero or 1, and R10 is hydrogen, form, together with aluminoxanes as cocatalysts, a very effective catalyst system for the preparation of polyolefins or high stereospecificity and high melting point. Polyolefins with unique or improved properties are obtained by polymerizing an olefin in the presence of a metallocene combined with a cocatalyst, wherein the metallocene is preferably a zirconocene or a hafnocene, and the Zr or Hf central atom is coordinated with two ligands which are derivatives of 2-substituted indenyl nuclei and which are substituted with at least one and up to four groups (e.g. aliphatic or aromatic groups) on the six-member rings of the indenyl nuclei. The indenyl nuclei are optionally substituted at the 3-position and are joined by a 1,1′-bridge of the formula —(CR8R9)m—R7—(CR8R9)n—, which is a single- or multi-membered chain in which R7 can also be a (substituted) hetero atom, m and n are identical or different and are zero, 1, or 2, and m+n is zero, 1, or 2.
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Citations
17 Claims
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1. A compound of the formula I for preparing essentially isotactic olefin polymers
in which M1 is a metal from 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 C7-C40-arylalkyl group, a C7-C40-alkylaryl group, a C8-C40-arylalkenyl group or a halogen atom, R3 and R4 are identical or different and are a hydrogen atom, a halogen atom, a halogen atom, a C1-C10-alkyl group, which is optionally halogenated, a C6-C10-aryl group, an — - NR215, —
SR15, —
OSiR315, —
SiR315 or —
PR215 radical in which R15 is a halogen atom, a C1-C10-alkyl group or a C6-C10-aryl group, R5 and R6 are identical or different and are as defined for R3 and R4, with the proviso that R5 and R6 are not hydrogen,R7 is where R11, 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 R11 and R12 or R11 and R13, in each case with the atoms connecting them, form a ring, M2 is silicon, germanium or tin, R8 and R9 are identical or different and are as defined 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 R10 are identical or different and are as defined for R11, R12 and R13. - View Dependent Claims (2, 3, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15)
n plus m is zero or 1, and R10 is hydrogen. -
3. A compound of the formula I as claimed in claim 1 wherein the compound is rac-dimethylsilyl(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, rac-ethylene(2-methyl4,5,6,7-tetrahydro-1-indenyl)2zirconium dichloride, rac-dimethylsilyl (2-methyl-4,5,6,7-tetrahydro-1-indenyl)2dimethylzirconium or rac-ethylene(2-methyl-4,5,6,7-tetrahydro-1-indenyl)2dimethylzirconium.
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5. A compound as claimed in claim 1, wherein R1 and R2 are identical or different and are a hydrogen atom, a C1-C3-alkyl group, a C1-C3-alkoxy group, a C6-C8-aryl group, a C6-C8-aryloxy group, a C2-C4-alkenyl group, a C7-C10-arylalkyl group, a C7-C12-alkylaryl group, a C8-C12-arylalkenyl group or chlorine.
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6. A compound as claimed in claim 1, wherein R3 and R4 are identical or different and are a hydrogen atom, a fluorine, chlorine or bromine atom, a C1-C4-alkyl group which may be halogenated, a C6-C8-aryl group, a —
- NR215, —
SR15, —
OSiR315, —
SiR315 or —
PR215 radical in which R15 is a chlorine atom, or a C1-C3-alkyl group or a C6-C8-aryl group.
- NR215, —
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7. A compound as claimed in claim 1, wherein R3 and R4 are hydrogen.
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8. A compound as claimed in claim 1, wherein R5 and R6 are identical.
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9. A compound as claimed in claim 1, wherein R5 and R6 are (C1-C4)-alkyl, which may be halogenated with methyl.
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10. A compound as claimed in claim 1, wherein R11, R12 and R13 are identical or different and are a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a CF3 group, a C6-C8-aryl group, a pentafluorophenyl group, a C1-C4-alkoxy group, a C2-C4-alkenyl group, a C7-C10-arylalkyl group, a C8-C12-arylalkenyl group or a C7-C14-alkylaryl group, or R11 and R12 or R11 and R13, in each case together with the atoms connecting them, form a ring.
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11. A compound as claimed in claim 1, wherein M2 is silicon or germanium.
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12. A compound as claimed in claim 1, wherein R7 is ═
- CR11R12, ═
SiR11R12, ═
GeR11R12, —
O—
, —
S—
, ═
SO, ═
PR11 or ═
P(O)R11.
- CR11R12, ═
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13. A compound as claimed in claim 1, wherein m and n are identical or different and are zero or 1.
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14. A compound as claimed in claim 1, wherein m plus n is zero or 1.
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15. A compound as claimed in claim 1, wherein R10 is hydrogen or C1-C4-alkyl groups.
- NR215, —
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4. A compound as claimed 1, wherein M1 is zirconium, hafnium or titanium.
- 16. A polyolefin made by polymerizing an olefin in the presence of a combination comprising a metallocene compound and a cocatalyst, said metallocene compound being a compound of the formula I:
Specification
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- Resources
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Current AssigneeBasell Polyolefine GmbH (Lyondellbasell Industries NV)
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Original AssigneeTargor Gmbh (BASF SE)
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InventorsWinter, Andreas, Rohrmann, Jürgen, Dolle, Volker, Spaleck, Walter, Antberg, Martin
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Primary Examiner(s)TESKIN, FRED M
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Application NumberUS08/324,260Time in Patent Office2,423 DaysField of Search556/9, 556/11, 556/14, 556/19, 556/20, 556/21, 556/22, 556/43, 556/53, 556/58, 502/103, 502/117, 502/152, 526/129, 526/160, 526/943, 526/348, 526/351US Class Current526/348CPC Class CodesC07F 17/00 MetallocenesC07F 7/0805 comprising only Si, C or H ...C08F 10/00 Homopolymers and copolymers...C08F 110/06 PropeneC08F 4/63912 in combination with an orga...C08F 4/63927 two cyclopentadienyl rings ...Y10S 526/943 Polymerization with metallo...
