US5470927A
Expired / Lapsed
US
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Ionic metallocene catalyst compositions
Assignee: Exxon Mobil Corp
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Filing: 1994-10-05
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Granted: 1995-11-28
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Expires: 2014-10-05
Abstract
Abstract A method is disclosed for polymerizing olefins, diolefins, or acetylenically unsaturated monomers containing two or more carbon atoms, either alone or in combination with each other or with other polymerizable monomers, comprising contacting the monomers with an ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by the olefin, diolefin and/or acetylenically unsaturated monomer during polymerization. The process provides means of producing narrow molecular weight polyolefin polymers, increasing comonomer incorporation in copolymers and avoiding metal impurities in the polymer products.
Inventors
- 👤 Howard W. Turner
- 👤 Gregory G. Hlatky
- 👤 Richard R. Eckman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 17:48
CPC Classifications
C; C08; C08F; C08F10/00; C07; C07F; C07F17/00; C08F110/00; C08F110/02; C08F110/04; C08F110/06; C08F210/00; C08F210/04; C08F210/06; C08F210/16; C08F210/18; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/6592; C08F4/65922; C08F4/65925; C08F4/65927; Y; Y10; Y10S; Y10S526/00; Y10S526/943
Claims Analysis
Total Claims: 24
Claim 1
Independent Claim
84 words
A method for polymerizing olefins, diolefins, or acetylenically unsaturated monomers containing two or more carbon atoms, either alone or in combination with each other or with other polymerizable monomers, comprising contacting the monomers with an ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin, diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 2
Independent Claim
84 words
A method for polymerizing olefins, diolefins, or acetylenically unsaturated monomers containing two or more carbon atoms, either alone or in combination with each other or with other polymerizable monomers, comprising contacting the monomers with an ionic polymerization catalyst comprising (1) a cation derived from a bis(cyclopentadienyl) Group IV-B metal compound by abstracting a ligand to create a positively charged species and (2) a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin, diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 3
Dependent Claim
40 words
The method of claim 1 wherein the bis(cyclopentadienyl)metal compound of the catalyst i) is a pure enantiomer or racemic mixture of two enantiomers of a rigid, chiral metallocene; or ii) contains a covalent bridging group between two substituted cyclopentadienyl radicals.
Claim 4
Dependent Claim
10 words
The method of claim 1 wherein the catalyst is zwitterionic.
Claim 5
Dependent Claim
10 words
The method of claim 1 for the homopolymerization of ethylene.
Claim 6
Independent Claim
13 words
The method of claim F for the polymerization of propylene or higher α-olefins.
Claim 7
Dependent Claim
58 words
The method of claim 1 wherein the polymerization takes place at a temperature of about 0° C. to about 100° C., a pressure of from about 15 psig to about 1500 psig, for about 1 to 60 minutes and the catalyst is used in a concentration from about 10 -5 to about 10 -1 moles/liter of solvent used.
Claim 8
Dependent Claim
43 words
The method of claim 1, wherein said cation comprises hydrocarbyl substituted cyclopentadienyl radicals, the hydrocarbyl substitutions containing from 1 to about 20 carbon atoms including straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radical, aromatic radicals and alkyl-substituted aromatic radicals.
Claim 9
Dependent Claim
17 words
The method of claim 7, wherein said substituted cyclopentadienyl radicals are joined by a covalent bridging group.
Claim 10
Dependent Claim
10 words
The method of claim 8, wherein said metal is hafnium.
Claim 11
Dependent Claim
18 words
The method of claim 1, where said olefins comprise ethylene and α-olefins having 3 to 6 carbon atoms.
Claim 12
Dependent Claim
11 words
The method of claim 10, additionally comprising one or more diolefin.
Claim 13
Dependent Claim
13 words
The method of claim 2, where used for the preparation of isotactic polypropylene.
Claim 14
Independent Claim
66 words
A method for polymerizing an olefin, diolefin, and/or acetylenically unsaturated monomers comprising the step of contacting one or more of said monomers under polymerization conditions with an ionic polymerization catalyst comprising a cation derived from a hydrolyzable bis (cyclopentadienyl) Group IV-B metal compound and a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 15
Independent Claim
66 words
A method for polymerizing an olefin, diolefin, and/or acetylenically unsaturated monomers comprising the step of contacting one or more of said monomers under polymerization conditions with an ionic polymerization catalyst comprising a cation derived from a hydrolyzable bis (cyclopentadienyl) Group IV-B metal compound and a stabilizing non-coordinating anion, said anion being sufficiently labile to permit displacement by an olefin diolefin and/or acetylenically unsaturated monomer during polymerization.
Claim 16
Dependent Claim
43 words
The method of claim 13, wherein said cation comprises hydrocarbyl substituted cyclopentadienyl radicals, the hydrocarbyl substitutions containing from 1 to about 20 carbon atoms including straight and branched alkyl radicals, cyclic hydrocarbon radicals, alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and alkyl-substituted aromatic radicals.
Claim 17
Dependent Claim
15 words
The method of claim 13, wherein said bis(cyclopentadienyl) Group IV-B compound comprises a bridging group.
Claim 18
Dependent Claim
21 words
The method of claim 14, wherein said cation comprises at least one polycyclic cyclopentadienyl ligand bound to the Group IV-B metal.
Claim 19
Dependent Claim
24 words
The method of claim 16, wherein said cation is a pure enantiomer or racemic mixture of two enantiomers of a rigid, chiral metal compound.
Claim 20
Dependent Claim
12 words
The method of claim 16, wherein said Group IV-B metal is hafnium.
Claim 21
Dependent Claim
22 words
The method of claim 16, wherein said bis(cyclopentadienyl) Group IV-B compound comprises a bridging group selected from those comprising carbon or silicon.
Claim 22
Dependent Claim
13 words
The method of claim 18, wherein said metal compound is dimethylsilylbis(indenyl) hafnium dimethyl.
Claim 23
Dependent Claim
14 words
The method of claim 15, wherein said bridging group comprises methylene, ethylene, or silicon.
Claim 24
Dependent Claim
16 words
The method of claim 18 wherein said Group IVB compound comprises a bridging group containing silicon.
References Cited (Backward Citations)
EP0129368A1
Cited
EP0200351A2
Cited
US4752597A
Cited
EP0323454A1
Cited
US5153157A
Cited
EP0277004A1
Cited
US5241025A
Cited
EP0277003A1
Cited
US5384299A
Cited
US5278119A
Cited
US5198401A
Cited
EP0478913A1
Cited
US5084534A
Cited
US5017714A
Cited
US5223468A
Cited
US5155080A
Cited
US5162278A
Cited
US5223467A
Cited
WO1991002012A1
Cited
US5064802A
Cited
EP0423100A2
Cited
EP0427696A2
Cited
EP0427697B1
Cited
EP0426638A2
Cited
EP0426637B1
Cited
EP0468651A1
Cited
EP0495375A2
Cited
WO1993005082A1
Cited
WO1993008221A2
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1998-11-27 | 1999-05-29 | 1999-11-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2002-11-27 | 2003-05-29 | 2003-11-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2006-11-27 | 2007-05-29 | 2007-11-28 | $7700.00 | Window Closed / Lapsed |