US5498581A
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US
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Method for making and using a supported metallocene catalyst system
Assignee: Phillips Petroleum Co
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Filing: 1994-06-01
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Granted: 1996-03-12
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Expires: 2014-06-01
Abstract
Abstract Methods are disclosed for preparing a highly active solid metallocene-containing catalyst system and its use in the polymerization of olefins. The catalyst system is prepared by creating a catalyst system solution by combining an aluminoxane with a metallocene having a substituent which has olefinic unsaturation in a suitable liquid to form a liquid catalyst system, conducting prepolymerization of an olefin in the liquid catalyst system, and separating the resulting solid metallocene-containing catalyst system from the reaction mixture. Also polymerization of olefins using the inventive solid catalyst system is disclosed.
Inventors
- 👤 M. Bruce Welch
- 👤 Helmut G. Alt
- 👤 Bernd Peifer
- 👤 Syriac J. Palackal
- 👤 Gary L. Glass
- 👤 Ted M. Pettijohn
- 👤 Gil R. Hawley
- 👤 Darryl R. Fahey
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 11:13
CPC Classifications
C; C08; C08J; C08J5/00; C08J5/18; C08F; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/6592; C07; C07F; C07F17/00; C08F10/00; C08F10/02; C08F110/00; C08F110/02; C08F210/00; C08F210/16; C08F4/65904; C08F4/65912; C08F4/65916; C08F4/65922; C08F4/65927; C08J2323/00; C08J2323/02; C08J2323/04; Y; Y10; Y10S; Y10S526/00; Y10S526/904
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
91 words
A method for preparing a solid metallocene-containing catalyst system comprising (a) combining in a liquid an organoaluminoxane and at least one metallocene having at least one cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, or fluorenyl ligand having at least one olefinically unsaturated substituent to form a liquid catalyst system, (b) conducting prepolymerization of at least one olefin in the presence of said catalyst system to produce a prepolymerized solid catalyst containing no more than about 95 weight percent prepolymer, and (c) separating the resulting solid from the liquid and components dissolved in said liquid.
Claim 2
Independent Claim
91 words
A method for preparing a solid metallocene-containing catalyst system comprising (a) combining in a liquid an organoaluminoxane and at least one metallocene having at least one cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, or fluorenyl ligand having at least one olefinically unsaturated substituent to form a liquid catalyst system, (b) conducting prepolymerization of at least one olefin in the presence of said catalyst system to produce a prepolymerized solid catalyst containing no more than about 95 weight percent prepolymer, and (c) separating the resulting solid from the liquid and components dissolved in said liquid.
Claim 3
Dependent Claim
30 words
A method according to claim 1 wherein after the solid is separated from the liquid in step (c) the solid is subjected to drying to remove substantially all the liquid.
Claim 4
Dependent Claim
18 words
A method according to claim 2 wherein an aromatic solvent is used for forming the liquid catalyst system.
Claim 5
Dependent Claim
20 words
A method according to claim 3, wherein the solvent that is used for forming the liquid catalyst system is toluene.
Claim 6
Dependent Claim
43 words
A method according to claim 4, wherein a solid particulate support is added to the reaction product of step (b), then a liquid in which the prepolymer is sparingly soluble is added, and the resulting solids are recovered by filtering, washing, and drying.
Claim 7
Dependent Claim
12 words
A method according to claim 5, wherein said particulate support is silica.
Claim 8
Dependent Claim
33 words
A method according to claim 4, wherein the solid is separated from the liquid in step (c) by filtering, then washing the recovered solid with a hydrocarbon, and then drying the washed solid.
Claim 9
Dependent Claim
14 words
A method according to claim 7, wherein an alkane is used in the washing.
Claim 10
Dependent Claim
29 words
A method according to claim 1, wherein step (a) is conducted in the presence of a particulate support that is insoluble in the liquid being employed in step (a).
Claim 11
Dependent Claim
14 words
A method according to claim 9, wherein said particulate support is an inorganic oxide.
Claim 12
Dependent Claim
14 words
A method according to claim 4, wherein the prepolymerization involves the prepolymerization of ethylene.
Claim 13
Dependent Claim
19 words
A method according to claim 11, wherein the prepolymerization involves the prepolymerization of a mixture of ethylene and 1-butene.
Claim 14
Dependent Claim
128 words
A method according to claim 1, wherein step (a) is conducted in the presence of a bridged metallocene having olefinic unsaturation in a branch extending outwardly from the bridge, the ligand of said metallocene having the formula ##STR4## wherein n is 1 or 0; R iv is Si, Ge, C, or Sn; each R' is individually selected from the group consisting of hydrogen and hydrocarbyl radicals having 1 to 10 carbons; R" is selected from the group consisting of hydrocarbyl diradicals containing 1 to 10 carbons; R"' is selected from the group consisting of hydrogen or hydrocarbyl groups containing 1 to 10 carbons; and each Z is the same or different and is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, and fluorenyl radicals.
Claim 15
Dependent Claim
12 words
A method according to claim 13, wherein 5-(9-fluorenyl)-5-(cyclopentadienyl)-hexene-1 zirconium dichloride is employed.
Claim 16
Dependent Claim
86 words
A method according to claim 1, wherein the metallocene is selected from the group consisting of 5-(cyclopentadienyl)-5-(9-fluorenyl)-1 -hexene zirconium dichloride, bis(9-fluorenyl)(methyl)(vinyl)silane zirconium dichloride, bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium dichloride, bis(9-fluorenyl) (methyl)(but-3-enyl)silane zirconium dichloride, bis(9-fluorenyl) (methyl) (hex-5-enyl) silane zirconium dichloride, bis(9-fluorenyl) (methyl)(oct-7-enyl)silane zirconium dichloride, (cyclopentadienyl)(1-allylindenyl) zirconium dichloride, bis(1-allylindenyl) zirconium dichloride, (9-(prop-2-enyl) fluorenyl)(cyclopentadienyl) zirconium dichloride, (9-(prop-2-enyl)(fluorenyl)(pentamethylcyclopentadienyl) zirconium dichloride, bis(9-(prop-2-enyl)fluorenyl) zirconium dichloride, (9-(cyclopent2-enyl)fluorenyl)(cyclopentadienyl) zirconium dichloride, bis(9-(cyclopent-2-enyl)fluorenyl) zirconium dichloride, 5-(2-methylcyclopentadienyl)-5-(9-fluorenyl)- 1-hexene zirconium dichloride, 5-(fluorenyl)-5-(cyclopentadienyl)- 1-hexene hafnium dichloride, (9-fluorenyl)( 1-allylindenyl)dimethylsilane zirconium dichloride, 1-(2,7-di(alphamethylvinyl)-(9- fluorenyl)-1-(cyclopentadienyl)-1,1 -dimethylmethane zirconium dichloride, and 1-(2,7-di(cyclohex- 1-enyl) 9-fluorenyl))- 1-(cyclopentadienyl)-1,1-methane zirconium dichloride.
Claim 17
Dependent Claim
15 words
A method according to claim 1, wherein two different metallocenes are present during the prepolymerization.
Claim 18
Dependent Claim
25 words
A method according to claim 16, wherein at least two different metallocenes each having at least one olefinically unsaturated substituent are employed during the prepolymerization.
Claim 19
Dependent Claim
18 words
A method according to claim 17, wherein at least one of the metallocenes is 5-(fluorenyl)-5-(cyclopentadienyl)-hexene- 1 zirconium dichloride.
Claim 20
Dependent Claim
27 words
A method according to claim 16, wherein at least two different bridged metallocenes are employed each having olefinic unsaturation in a branch extending outwardly from the bridge.
Claim 21
Dependent Claim
27 words
A method for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a solid metallocene-containing catalyst system produced by the process of claim 1.
Claim 22
Dependent Claim
15 words
A method according to claim 20 wherein the polymerization is conducted under slurry polymerization conditions.
Claim 23
Dependent Claim
18 words
A method according to claim 21 wherein ethylene is polymerized in the presence of an alkane liquid diluent.
Claim 24
Dependent Claim
19 words
A method according to claim 22 wherein said solid metallocene-containing catalyst system is prepared from 5-(9-fluorenyl)-5-(cyclopentadienyl)-hexene- 1 zirconium dichloride.
Claim 25
Dependent Claim
27 words
A method according to claim 23 wherein the polymerization is conducted in a continuous loop reactor and isobutane is used as a liquid diluent for the polymerization.
Claim 26
Dependent Claim
50 words
A method according to claim 24 wherein the solid metallocene-containing catalyst system used in the polymerization is prepared by (a) combining 5-(9-fluorenyl)-5-(cyclopentadienyl)-hexene-1 zirconium dichloride and methylaluminoxane in a liquid, (b) prepolymerizing ethylene in the resulting liquid, in the presence of silica, and (c) separating the resulting solid from the liquid.
Claim 27
Dependent Claim
19 words
A method according to claim 25 wherein the liquid used in step (a) consists essentially of an aromatic liquid.
Claim 28
Dependent Claim
122 words
A method according to claim 20 wherein said solid metallocene-containing catalyst system is prepared using at least one bridged metallocene having a vinyl terminated branched bridged ligand of the formula ##STR5## wherein n is 1 or 0; R iv is Si, Ge, C, or Sn; each R' is individually selected from the group consisting of hydrogen and hydrocarbyl diradicals having 1 to 10 carbons; R" is selected from the group consisting of hydrocarbyl radicals containing 1 to 10 carbons; R"' is selected from the group consisting of hydrogen or hydrocarbyl groups containing 1 to 10 carbons; and each Z is the same or different and is selected from the group consisting of substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, and fluorenyl radicals.
Claim 29
Dependent Claim
27 words
A method according to claim 27 wherein n is 1 and R" is a saturated alkylene diradical having 2 to 10 carbon atoms in its main chain.
Claim 30
Dependent Claim
11 words
A method according to claim 28 wherein R iv is C.
Claim 31
Dependent Claim
11 words
A method according to claim 28 wherein R iv is Si.
Claim 32
Dependent Claim
12 words
A solid metallocene-containing catalyst system produced by the method of claim 1.
Claim 33
Dependent Claim
12 words
A solid metallocene-containing catalyst system produced by the method of claim 13.
Claim 34
Dependent Claim
12 words
A solid metallocene-containing catalyst system produced by the method of claim 15.
Claim 35
Dependent Claim
12 words
A solid metallocene-containing catalyst system produced by the method of claim 14.
Claim 36
Dependent Claim
15 words
A solid metallocene-containing composition according to claim 31 further characterized by containing an inorganic support.
Claim 37
Dependent Claim
137 words
A method according to claim 1 wherein said liquid catalyst system is formed with at least one metallocene selected from those of the formula R x (Z)(Z)MeQ k wherein each Z is bound to Me and is the same or different and is a ligand selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, and fluorenyl; R is a structural bridge linking the Z's, and Me is a metal selected from the group consisting of IVB, VB, and VIB metals of the Periodic Table. Each Q is the same or different and is selected from the group consisting of hydrogen, halogen, and organo radicals; x is 1 or 0; k is a number sufficient to fill out the remaining valences of Me, further characterized by the fact that the metallocene has at least one olefinically unsaturated substituent.
Claim 38
Dependent Claim
20 words
A method according to claim 36 wherein in the metallocene x is 1 and R includes an olefinically unsaturated substituent.
Claim 39
Dependent Claim
56 words
A method according to claim 37 wherein the olefinically unsaturated substituent attached to R has the formula ##STR6## wherein R" is a hydrocarbyl diradical having 1 to 20 carbon atoms; n is 1 or 0, and each R' is individually selected from the group consisting of organo radicals having 1 to 10 carbon atoms and hydrogen.
References Cited (Backward Citations)
US4871705A
Cited
US5071808A
Cited
US5106804A
Cited
US5169818A
Cited
US5387567A
Cited
US5308815A
Cited
US5240894A
Cited
EP0574370A1
Cited
US5308817A
Cited
EP0586167A1
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1999-03-12 | 1999-09-11 | 2000-03-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2003-03-12 | 2003-09-11 | 2004-03-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2007-03-12 | 2007-09-11 | 2008-03-12 | $7700.00 | Window Closed / Lapsed |