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Supported catalyst systems
Assignee: Honeywell International Inc
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Filing: 2004-10-14
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Granted: 2005-12-06
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Expires: 2024-10-14
Abstract
Abstract Disclosed are methods of producing supported organic catalyst systems which find particular use in polymerization reactions. The methods comprise generally, the steps of (a) providing an organic catalyst solution comprising an organic catalyst dissolved in a solvent; (b) contacting the organic catalyst solution with a solid support material; and (c) removing the solvent from the support material by using one or more supercritical-like solvents.
Inventors
- 👤 Raymond H. P. Thomas
- 👤 Roy Robinson
- 👤 David Nalewajek
- 👤 Kane D. Cook
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 00:00
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/02; B01J31/12; B01J31/14; B01J31/146; B01J31/16; B01J31/1616; B01J31/22; B01J31/2282; B01J31/2295; B01J37/00; B01J37/02; B01J37/03; B01J37/031; C; C08; C08F; C08F10/00; C08F4/00; C08F4/02; C08F4/025; B01J21/00; B01J21/02; B01J21/04; B01J21/06; B01J21/08; B01J2531/00; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/49; B01J2531/80; B01J2531/84; B01J2531/842; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65908; C08F4/6592; C08F4/65922; C08F4/65925; C08F4/65927; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/54
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
68 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising an hafnium metallocene catalyst dissolved in a supercritical-like solvent at a temperature of from about −10° C. to about 200° C.; (b) contacting a support material with said metallocene catalyst solution; and (c) removing substantially all of said supercritical-like solvent from said metallocene catalyst and said support material.
Claim 2
Independent Claim
68 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising an hafnium metallocene catalyst dissolved in a supercritical-like solvent at a temperature of from about −10° C. to about 200° C.; (b) contacting a support material with said metallocene catalyst solution; and (c) removing substantially all of said supercritical-like solvent from said metallocene catalyst and said support material.
Claim 3
Dependent Claim
14 words
The method of claim 1 wherein said hafnium metallocene catalyst comprises halfnium (IV) compounds.
Claim 4
Dependent Claim
14 words
The method of claim 2 wherein said hafnium (IV) compound is dimethylbis(t-butylcyclopentadienyl) hafnium (IV).
Claim 5
Dependent Claim
16 words
The method of claim 1 wherein said supercritical-like solvent is a solvent in its supercritical state.
Claim 6
Dependent Claim
53 words
The method of claim 1 wherein said supercritical-like solvent comprises a liquid solvent in a subcritical state selected from the group consisting of methane, ethane, ethylene, propylene, trifluorochloromethane, difluoromethane, isomers of tetrafluoroethane, pentafluoroethane, isomers of trifluoroethane, isomers of pentafluoropropane, difluorochloromethane, isomers of tetrafluorochloroethane, carbon dioxide, ammonia, and mixtures of two or more thereof.
Claim 7
Dependent Claim
13 words
The method of claim 5 wherein said liquid solvent comprises liquid carbon dioxide.
Claim 8
Dependent Claim
31 words
The method of claim 1 wherein said providing step (a) comprises dissolving said metallocene catalyst in said supercritical-like solvent at a temperature of from about 30° C. to about 100° C.
Claim 9
Dependent Claim
31 words
The method of claim 1 wherein said providing step (a) comprises dissolving said metallocene catalyst in said supercritical-like solvent at a pressure of from about 25 psia to about 5,000 psia.
Claim 10
Dependent Claim
31 words
The method of claim 8 wherein said providing step (a) comprises dissolving said metallocene catalyst in said supercritical-like solvent at a pressure of from about 100 psia to about 3,500 psia.
Claim 11
Dependent Claim
13 words
The method of claim 1 , wherein said metallocene catalyst comprises a co-catalyst.
Claim 12
Dependent Claim
30 words
The method of claim 10 , wherein said co-catalyst is selected from the group consisting of tri-(n-butyl) ammonium tetrakis (pentafluorophenyl) boron, tris (pentafluorophenyl) borane, an alumoxane, methylalumoxane and mixtures thereof.
Claim 13
Dependent Claim
26 words
The method of claim 1 wherein said support material is selected from the group consisting of alumina, silica and silica treated with a halogenated organic compound.
Claim 14
Dependent Claim
14 words
The method of claim 12 wherein said support material comprises a plurality of particles.
Claim 15
Independent Claim
89 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising a transition metal metallocene catalyst dissolved in a supercritical-like solvent at a temperature of from about −10° C. to about 200° C., wherein said transition metal is selected from the group consisting of Group 4, Group 5, and Group 6 transition metals; (b) contacting a support material with said metallocene catalyst solution; and (c) removing substantially all of said supercritical-like solvent from said metallocene catalyst and said support material.
Claim 16
Independent Claim
89 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising a transition metal metallocene catalyst dissolved in a supercritical-like solvent at a temperature of from about −10° C. to about 200° C., wherein said transition metal is selected from the group consisting of Group 4, Group 5, and Group 6 transition metals; (b) contacting a support material with said metallocene catalyst solution; and (c) removing substantially all of said supercritical-like solvent from said metallocene catalyst and said support material.
Claim 17
Dependent Claim
19 words
The method of claim 1 wherein said removing step (c) comprises converting said supercritical-like solvent to a gaseous state.
Claim 18
Dependent Claim
22 words
The method of claim 15 wherein said supercritical-like solvent is converted to a gaseous state by adjusting the temperature of said solvent.
Claim 19
Dependent Claim
22 words
The method of claim 15 wherein said supercritical-like solvent is converted to a gaseous state by adjusting the pressure of said solvent.
Claim 20
Dependent Claim
60 words
The method of claim 1 further comprising the steps of: (d) providing a second metallocene catalyst solution comprising a second metallocene catalyst dissolved in a supercritical-like solvent; (e) contacting said support material with said second metallocene catalyst solution; and (f) removing substantially all of said supercritical-like solvent of said second solution from said second metallocene catalyst and said support material.
Claim 21
Dependent Claim
25 words
The method of claim 18 , wherein said metallocene catalyst solution and said second metallocene catalyst solution are contacted with said support material substantially simultaneously.
Claim 22
Dependent Claim
22 words
The method of claim 18 , wherein said solvent of said second solution is a selective solvent for said second metallocene catalyst.
Claim 23
Independent Claim
82 words
A method for producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising a metallocene catalyst selected from the group consisting of hafnium compounds and ferrocenes dissolved in a first solvent at a temperature of from about −10° C. to about 200° C.; (b) contacting a support material with said catalyst solution; and (c) removing substantially all of said first solvent by contacting said first solvent with a supercritical solvent and evaporating said supercritical solvent.
Claim 24
Independent Claim
82 words
A method for producing a supported metallocene catalyst system comprising the steps of: (a) providing a metallocene catalyst solution comprising a metallocene catalyst selected from the group consisting of hafnium compounds and ferrocenes dissolved in a first solvent at a temperature of from about −10° C. to about 200° C.; (b) contacting a support material with said catalyst solution; and (c) removing substantially all of said first solvent by contacting said first solvent with a supercritical solvent and evaporating said supercritical solvent.
Claim 25
Dependent Claim
14 words
The method of claim 21 , wherein said first solvent is a liquid solvent.
Claim 26
Dependent Claim
73 words
The method of claim 21 further comprising the steps of: (d) providing a second metallocene catalyst solution comprising a second metallocene catalyst dissolved in a second solvent at a temperature of from about −10° C. to about 200° C.; (e) contacting said support material with said second metallocene catalyst solution; and (f) removing substantially all of said second solvent by contacting said second solvent with a supercritical solvent and evaporating said supercritical solvent.
Claim 27
Dependent Claim
25 words
The method of claim 23 , wherein said metallocene catalyst solution and said second metallocene catalyst solution are contacted with said support material substantially simultaneously.
Claim 28
Dependent Claim
15 words
The method of claim 14 , wherein said transition metal is a group 4 metal.
Claim 29
Independent Claim
59 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing an organic catalyst solution comprising a metallocene catalyst dissolved in a solvent comprising a liquid hydrofluorocarbon solvent; (b) contacting a support with said metallocene catalyst solution; and (c) removing substantially all of said liquid hydrofluorocarbon solvent from said metallocene catalyst and said support material.
Claim 30
Independent Claim
59 words
A method of producing a supported metallocene catalyst system comprising the steps of: (a) providing an organic catalyst solution comprising a metallocene catalyst dissolved in a solvent comprising a liquid hydrofluorocarbon solvent; (b) contacting a support with said metallocene catalyst solution; and (c) removing substantially all of said liquid hydrofluorocarbon solvent from said metallocene catalyst and said support material.
Claim 31
Dependent Claim
12 words
The method of claim 25 , wherein said transition metal is titanium.
Claim 32
Dependent Claim
27 words
The method of claim 26 , wherein said metallocene catalyst comprises a metallocene compound selected from the group consisting of zirconium metallocenes, hafnium metallocenes, and ferrocenes system.
Claim 33
Dependent Claim
26 words
The method of claim 28 , wherein said zirconium metallocene is selected from the group consisting of dichlorobis(n-butylcyclopentadienyl) zirconium (IV), dichlorobis(cyclopentadienyl) zirconium (IV) and mixtures thereof.
Claim 34
Dependent Claim
15 words
The method of claim 29 , wherein said hafnium metallocene compound is dimethylbis(t-butylcyclopentadienyl) hafnium (IV).
Claim 35
Dependent Claim
14 words
The method of claim 26 , wherein said metallocene catalyst comprises a co-catalyst system.
Claim 36
Dependent Claim
30 words
The method of claim 31 , wherein said co-catalyst is selected from the group consisting of tri-(n-butyl) ammonium tetra bis(pentafluorophenyl) boron, tris (pentafluorophenyl) borane, an alumoxane, methylalumoxane and mixtures thereof.
Claim 37
Dependent Claim
25 words
The method of claim 26 wherein said support is selected from the group consisting of alumina, silica and silica treated with a halogenated organic compound.
Claim 38
Dependent Claim
13 words
The method of claim 33 wherein said support comprises a plurality of particles.
Claim 39
Dependent Claim
13 words
The method of claim 33 wherein said support comprises a single unitary body.
Claim 40
Dependent Claim
21 words
The method of claim 26 wherein said hydrofluorocarbon solvent has a surface tension of about 22 dynes per centimeter or less.
Claim 41
Dependent Claim
16 words
The method of claim 26 wherein said hydrofluorocarbon contains at least about 65 weight percent fluorine.
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