CA2494611A1 - Catalyst comprising bridged indeno[1,2-b]indolyl metal complex - Google Patents

Catalyst comprising bridged indeno[1,2-b]indolyl metal complex Download PDF

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Publication number
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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group
catalyst system
transition metal
alkyl
complex
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CA002494611A
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French (fr)
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CA2494611C (en
Inventor
Shaotian Wang
Clifford C. Lee
Mark P. Mack
Gregory G. Hlatky
Sandor Nagy
Barbara M. Tsuie
Craig C. Meverden
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Equistar Chemicals LP
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Priority claimed from US10/211,085 external-priority patent/US6559251B1/en
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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.
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.
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.
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.
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.
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.
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.
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.
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.
CA2494611A 2002-08-02 2003-07-10 Catalyst comprising bridged indeno[1,2-b]indolyl metal complex Expired - Fee Related CA2494611C (en)

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

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ID=31498031

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CA2494611A Expired - Fee Related CA2494611C (en) 2002-08-02 2003-07-10 Catalyst comprising bridged indeno[1,2-b]indolyl metal complex

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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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

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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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