CA2494611A1 - Catalyst comprising bridged indeno[1,2-b]indolyl metal complex - Google Patents
Catalyst comprising bridged indeno[1,2-b]indolyl metal complex Download PDFInfo
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- CA2494611A1 CA2494611A1 CA002494611A CA2494611A CA2494611A1 CA 2494611 A1 CA2494611 A1 CA 2494611A1 CA 002494611 A CA002494611 A CA 002494611A CA 2494611 A CA2494611 A CA 2494611A CA 2494611 A1 CA2494611 A1 CA 2494611A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for making ethylene copolymers is disclosed. Ethylene copolymerizes with an .alpha.-olefin in the presence of a catalyst system comprising an activator and a silica-supported, bridged indenoindolyl metal complex having "open architecture." The supported complex incorporates comonomers with exceptional efficiency, and the process gives ethylene copolymers having high molecular weights (Mw > 100K) and very low densities (< 0.910 g/cm3). Open architecture catalysts that include bridging through the indolyl nitrogen of the indenoindolyl framework are also described. Additionally, supported and unsupported indeno[1,2-b]indolyl catalysts provide exceptional activities in the preparation of elastomeric polypropylene and ethylene copolymers.
Claims (28)
1. A process which comprises copolymerizing ethylene with at least one .alpha.-olefin selected from the group consisting of 1-butene, 1-hexene, and 1-octene in the presence of a catalyst system which comprises an activator and a silica-supported, indenoindolyl Group 4-6 transition metal complex having open architecture to produce an ethylene copolymer having a density less than about 0.910 g/cm3.
2. The process of claim 1 wherein the .alpha.-olefin is 1-hexene.
3. The process of claim 1 wherein the activator is selected from the group consisting of alumoxanes, ionic borates, ionic aluminates, alkylaluminums, and aluminoboronates.
4. The process of claim 1 wherein the complex incorporates a Group 4 transition metal.
5. The process of claim 1 wherein the complex has the general structure:
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, R is alkyl, aryl, or trialkylsilyl, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, R is alkyl, aryl, or trialkylsilyl, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
6. The process of claim 5 wherein M is a Group 4 transition metal, L is alkylamido, and G is dialkylsilyl.
7. The process of claim 5 wherein M is Ti or Zr, L is t-butylamido, G is dimethylsilyl, and X is halide or alkyl.
8. The process of claim 1 wherein the complex has the general structure:
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
9. The process of claim 8 wherein M is a Group 4 transition metal, L is alkylamido, and G is dialkylsilyl.
10. The process of claim 8 wherein M is Ti or Zr, L is t-butylamido, G is dimethylsilyl, and X is halide or alkyl.
11. The process of claim 1 wherein the silica support is pretreated with an alumoxane.
12. The process of claim 1 wherein the ethylene copolymer has a Mw >
400,000.
400,000.
13. The process of claim 1 wherein the ethylene copolymer has a density less than about 0.900 g/cm3.
14. The process of claim 1 wherein the ethylene copolymer has a density less than about 0.890 g/cm3.
15. The process of claim 1 wherein the ethylene copolymer has a Mw/Mn < 3Ø
16. The process of claim 1 wherein the ethylene copolymer has a Mw >
1,000,000.
1,000,000.
17. A catalyst system which comprises:
(a) an activator; and (b) a bridged indenoindolyl Group 4-6 transition metal complex having open architecture in which bridging to the indenoindolyl group occurs through the indolyl nitrogen.
(a) an activator; and (b) a bridged indenoindolyl Group 4-6 transition metal complex having open architecture in which bridging to the indenoindolyl group occurs through the indolyl nitrogen.
18. The catalyst system of claim 17 wherein the activator is selected from the group consisting of alumoxanes, ionic borates, ionic aluminates, alkylaluminums, and aluminoboronates.
19. The catalyst system of claim 17 wherein the complex incorporates a Group 4 metal.
20. The catalyst system of claim 17 wherein the complex has the general structure:
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
21. The catalyst system of claim 20 wherein M is Ti or Zr, L is t-butylamido, G is dialkylsilyl, and X is halide or alkyl.
22. A catalyst system which comprises:
(a) an activator; and (b) a bridged indeno[1,2-b]indolyl Group 4-6 transition metal complex having open architecture.
(a) an activator; and (b) a bridged indeno[1,2-b]indolyl Group 4-6 transition metal complex having open architecture.
23. The catalyst system of claim 22 wherein the activator is selected from the group consisting of alumoxanes, ionic borates, ionic aluminates, alkylaluminums, and aluminoboronates.
24. The catalyst system of claim 22 wherein the complex incorporates a Group 4 transition metal.
25. The catalyst system of claim 22 wherein the complex has the general structure:
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, R is alkyl, aryl, or trialkylsilyl, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
in which M is a Group 4-6 transition metal, G is a linking group, L is a ligand that is covalently bonded to G and M, R is alkyl, aryl, or trialkylsilyl, X is alkyl, aryl, alkoxy, aryloxy, halide, dialkylamino, or siloxy, and n satisfies the valence of M.
26. The catalyst system of claim 25 wherein M is a Group 4 transition metal, L is alkylamido, and G is dialkylsilyl.
27. The catalyst system of claim 25 wherein M is Ti or Zr, L is t-butylamido, G is dimethylsilyl, and X is halide or alkyl.
28. A silica-supported catalyst system of claim 22.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA2758167A CA2758167C (en) | 2002-08-02 | 2003-07-10 | Copolymerization of ethylene using constrained geometry indenoindolyl complexes |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/211,085 | 2002-08-02 | ||
US10/211,085 US6559251B1 (en) | 2002-08-02 | 2002-08-02 | Process for making low-density polyolefins |
US10/382,233 US6838410B2 (en) | 2002-08-02 | 2003-03-05 | Catalysts for making polyolefins |
US10/382,233 | 2003-03-05 | ||
PCT/US2003/021540 WO2004013194A2 (en) | 2002-08-02 | 2003-07-10 | Catalysts and process for making polyolefins |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2758167A Division CA2758167C (en) | 2002-08-02 | 2003-07-10 | Copolymerization of ethylene using constrained geometry indenoindolyl complexes |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2494611A1 true CA2494611A1 (en) | 2004-02-12 |
CA2494611C CA2494611C (en) | 2012-01-24 |
Family
ID=31498031
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA2494611A Expired - Fee Related CA2494611C (en) | 2002-08-02 | 2003-07-10 | Catalyst comprising bridged indeno[1,2-b]indolyl metal complex |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1525228A2 (en) |
KR (1) | KR20050034728A (en) |
CN (1) | CN100429240C (en) |
AU (1) | AU2003248919A1 (en) |
BR (1) | BR0313308A (en) |
CA (1) | CA2494611C (en) |
MX (1) | MXPA05001075A (en) |
WO (1) | WO2004013194A2 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6818713B1 (en) * | 2003-08-11 | 2004-11-16 | Equistar Chemicals, Lp | Process for making polyethylene |
EP1735354A1 (en) * | 2004-04-16 | 2006-12-27 | Exxonmobil Chemical Company Inc. | Heterocyclic substituted metallocene compounds for olefin polymerization |
US6995220B2 (en) * | 2004-04-29 | 2006-02-07 | Equistar Chemicals, Lp | Ethylene polymerization process |
US7273914B2 (en) * | 2005-08-03 | 2007-09-25 | Equistar Chemicals, Lp | Olefin polymerization methods |
US7868197B2 (en) | 2005-12-14 | 2011-01-11 | Exxonmobil Chemical Patents Inc. | Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization |
US7429635B2 (en) | 2006-09-28 | 2008-09-30 | Equistar Chemicals, Lp | Preparation of ultra high molecular weight linear low density polyethylene |
US7812104B2 (en) | 2008-01-18 | 2010-10-12 | Exxonmobil Chemical Patents Inc. | Production of propylene-based polymers |
CA2760264C (en) | 2011-12-05 | 2018-08-21 | Nova Chemicals Corporation | Passivated supports for use with olefin polymerization catalysts |
CN112920227B (en) * | 2021-02-18 | 2022-09-23 | 山东京博石油化工有限公司 | Indenoindole structure-containing metallocene compound, preparation method and application thereof, and preparation method of alpha-olefin |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5495035A (en) | 1994-06-01 | 1996-02-27 | University Of Iowa Research Foundation | Synthesis of ANSA-metallocene catalysts |
HUP0001331A2 (en) | 1997-11-12 | 2000-08-28 | Montell Technology Company B.V. | Metallocenes bridging ligands and catalysts for olefin-polymerization and process for polymerization olefines |
US6239062B1 (en) * | 1999-09-02 | 2001-05-29 | Equistar Chemicals, L.P. | Olefin polymerization catalysts containing indolyl-amido ligands |
US6232260B1 (en) | 1999-10-14 | 2001-05-15 | Equistar Chemicals, L.P. | Single-site catalysts for olefin polymerization |
ES2326537T3 (en) * | 2000-01-18 | 2009-10-14 | Basell Polyolefine Gmbh | BINDING FOR A METALOCENE CATALYST TO MANUFACTURE POLYMERS BASED ON PROPYLENE AND METHOD OF OBTAINING THE SAME. |
US6559251B1 (en) * | 2002-08-02 | 2003-05-06 | Equistar Chemicals, Lp | Process for making low-density polyolefins |
-
2003
- 2003-07-10 CN CNB038185245A patent/CN100429240C/en not_active Expired - Fee Related
- 2003-07-10 KR KR1020057001862A patent/KR20050034728A/en not_active Application Discontinuation
- 2003-07-10 EP EP03766850A patent/EP1525228A2/en not_active Withdrawn
- 2003-07-10 MX MXPA05001075A patent/MXPA05001075A/en active IP Right Grant
- 2003-07-10 BR BR0313308-7A patent/BR0313308A/en not_active IP Right Cessation
- 2003-07-10 WO PCT/US2003/021540 patent/WO2004013194A2/en active Application Filing
- 2003-07-10 CA CA2494611A patent/CA2494611C/en not_active Expired - Fee Related
- 2003-07-10 AU AU2003248919A patent/AU2003248919A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
CN1681848A (en) | 2005-10-12 |
KR20050034728A (en) | 2005-04-14 |
AU2003248919A8 (en) | 2004-02-23 |
BR0313308A (en) | 2005-07-12 |
WO2004013194A3 (en) | 2004-07-15 |
CA2494611C (en) | 2012-01-24 |
WO2004013194A2 (en) | 2004-02-12 |
AU2003248919A1 (en) | 2004-02-23 |
EP1525228A2 (en) | 2005-04-27 |
CN100429240C (en) | 2008-10-29 |
MXPA05001075A (en) | 2005-06-06 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKLA | Lapsed |
Effective date: 20150710 |
|
MKLA | Lapsed |
Effective date: 20150710 |