Patent EP0685495A1 successfully refreshed from Google Patents.
EP0685495A1
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Method for making and using a supported metallocene catalyst system
Assignee: Phillips Petroleum Co
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Filing: 1995-05-31
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Granted: —
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Expires: 2015-05-31
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 Pfeifer
- 👤 Syriac J. Palackal
- 👤 Gary L. Glass
- 👤 Ted M. Pettijohn
- 👤 Gil R. Hawley
- 👤 Darryl R. Fahey
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-11-02 17:29
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: 18
Claim 1
Independent Claim
81 words
A process for preparing a solid metallocene-containing catalyst system comprising the following steps: (a) combining an organoaluminoxane and at least one metallocene having at least one cyclopentadienyl-type ligand having at least one olefinically unsaturated substituent in a liquid to form a liquid catalyst system, (b) conducting prepolymerization of at least one olefin in the presence of said liquid catalyst system to produce a prepolymerized solid catalyst, and (c) separating the resulting solid from the liquid and components dissolved in said liquid.
Claim 2
Dependent Claim
67 words
A process according to claim 1, wherein the metallocene is selected from 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-(cyclopent-2-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(alpha-methylvinyl)-(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 3
Dependent Claim
30 words
A process 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
21 words
A process according to claim 3, wherein an aromatic solvent, in particular toluene, is used for forming the liquid catalyst system.
Claim 5
Dependent Claim
46 words
A process according to claim 4, wherein a solid particulate support, in particular silica, 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 6
Dependent Claim
37 words
A process 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, in particular an alkane, and then drying the washed solid.
Claim 7
Dependent Claim
22 words
A process according to claim 4, wherein the prepolymerization involves the prepolymerization of ethylene or of a mixture of ethylene and 1-butene.
Claim 8
Dependent Claim
33 words
A process according to claim 1, wherein step (a) is conducted in the presence of a particulate support, in particular an inorganic oxide, that is insoluble in the liquid employed in step (a).
Claim 9
Dependent Claim
112 words
A process 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 wherein n is 1 or 0; R iv is Si, Ge, C, or Sn; each R' is individually selected from hydrogen and hydrocarbyl radicals having 1 to 10 carbons; R'' is selected from hydrocarbyl diradicals containing 1 to 10 carbons; R''' is selected from hydrogen or hydrocarbyl groups containing 1 to 10 carbons; and each Z is the same or different and is selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, and fluorenyl radicals.
Claim 10
Dependent Claim
35 words
A process according to claim 1, wherein two different metallocenes each having at least one olefinically unsaturated substituent, more particularly at least one of the metallocenes being 5-(fluorenyl)-5-(cyclopentadienyl)-hexene-1 zirconium dichloride, are present during the prepolymerization.
Claim 11
Dependent Claim
27 words
A process according to claim 10, wherein at least two different bridged metallocenes are employed each having olefinic unsaturation in a branch extending outwardly from the bridge
Claim 12
Dependent Claim
31 words
A process for polymerizing an olefin comprising contacting said olefin under suitable polymerization conditions with a solid metallocene-containing catalyst system produced by the process of any of claims 1 to 11.
Claim 13
Dependent Claim
105 words
A process according to claim 12, 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 wherein n is 1 or 0; R iv is Si, Ge, C, or Sn; each R' is individually selected from hydrogen and hydrocarbyl radicals having 1 to 10 carbons; R'' is selected from hydrocarbyl diradicals containing 1 to 10 carbons; R''' is selected from hydrogen or hydrocarbyl groups containing 1 to 10 carbons; and each Z is the same or different and is selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, and fluorenyl radicals.
Claim 14
Dependent Claim
27 words
A process according to claim 13, wherein n is 1 and R'' is a saturated alkylene diradical having 2 to 10 carbon atoms in its main chain.
Claim 15
Dependent Claim
13 words
A process according to claim 14, wherein R iv is C or Si.
Claim 16
Dependent Claim
37 words
A process according to claim 12, wherein the polymerization is conducted under slurry polymerization conditions, and/or wherein the polymerization is conducted in a continuous loop reactor and isobutane is used as a liquid diluent for the polymerization.
Claim 17
Dependent Claim
31 words
A process according to claim 16, wherein ethylene is polymerized in the presence of an alkane liquid diluent, and/or wherein said solid metallocene-containing catalyst system is prepared from 5-(9-fluorenyl)-5-(cyclopentadienyl)-hexene-1 zirconium dichloride.
Claim 18
Dependent Claim
60 words
A process according to claim 16, 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, in particular a liquid essentially consisting of an aromatic liquid, (b) prepolymerizing ethylene in the resulting liquid, in the presence of silica, and (c) separating the resulting solid from the liquid.
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