EP0685495A1
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EP
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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 11:32
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.
References Cited (Backward Citations)
US4871705A
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