# US 5,705,578 A · Method for making and using a supported metallocene catalyst system > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,578 A - Document ID: US5705578A - Status: Granted - Kind: A - Application number: 08/434,232 - Filed: 1995-05-04 - Granted: 1998-01-06 - Earliest claimed: 1995-05-04 - Assignees: Phillips Petroleum Company - Inventors: Bernd Peifer; Helmut G. Alt; M. Bruce Welch - Web page: https://patentgrep.com/patent/US5705578A ## CPC - C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond - C08F 4/61912: {in combination with an organoaluminium compound} - C08F 4/61922: {containing at least two cyclopentadienyl rings, fused or not} - C08F 110/02: Ethene - C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers - Y10S 526/943: Polymerization with metallocene catalysts - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract Methods are disclosed for preparing a highly active solid metallocene-containing catalyst system and its use in the polymerization of olefins. The solid catalyst system is prepared by combining an aluminoxane with a metallocene having a substituent which has internal alkynyl 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 last reaction product mixture. Also polymerization of olefins using the inventive solid catalyst system is disclosed. ## Claims ### Claim 1 A process for polymerizing ethylene comprising preparing a solid metallocene-containing catalyst system by (a) combining an organoaluminoxane and at least one metallocene having a ligand having at least one substituent with an internal alkyne functionality in a liquid to form a liquid catalyst system, (b) conducting prepolymerization of ethylene in the presence of said liquid catalyst system to produce a prepolymerized solid catalyst, and (c) separating the resulting solid from the liquid and the components dissolved in the liquid to yield said solid metallocene-containing catalyst system, and contacting ethylene under slurry polymerization conditions in the presence of an alkane liquid diluent and said solid metallocene-containing catalyst system. ### Claim 2 (depends on 1) 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 3 (depends on 2) A method according to claim 2 wherein an aromatic solvent is used for forming the liquid catalyst system. ### Claim 4 (depends on 3) A method according to claim 3, wherein the solvent that is used for forming the liquid catalyst system is toluene. ### Claim 5 (depends on 4) 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 6 (depends on 5) A method according to claim 5, wherein said particulate support is silica. ### Claim 7 (depends on 4) 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 8 (depends on 7) A method according to claim 7, wherein an alkane is used in the washing. ### Claim 9 (depends on 4) A process according to claim 4, wherein the prepolymerization involves the prepolymerization of ethylene. ### Claim 10 (depends on 9) A process according to claim 9, wherein the prepolymerization involves the prepolymerization of a mixture of ethylene and 1-butene. ### Claim 11 (depends on 1) 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 12 (depends on 11) A method according to claim 11, wherein said particulate support is an inorganic oxide. ### Claim 13 (depends on 1) A process according to claim 1, wherein step (a) is conducted in the presence of a metallocene selected from the group consisting of bridged metallocenes represented by the formula R(Z)(Z)MeQ.sub.k and unbridged metallocenes of the formula (Z)(Z)MeQ.sub.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, benzofluorenyl, and fluorenyl ligands; 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, halogens, and organoradicals; k is a number sufficient to fill out the remaining valances of Me; with the further proviso at least one of said Z's or R has at least one internal alkynyl substituent attached to it. ### Claim 14 (depends on 13) A method according to claim 13, wherein said internal alkynyl substituent is selected from phenylethynyl, n-butylethynyl, t-butylethynyl, and methylethynyl. ### Claim 15 (depends on 1) A process according to claim 1, wherein the metallocene is selected from the group consisting of (2,7-di(phenylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(phenylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7-di(t-butylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(t-butylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7-di(n-butylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(n-butylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7-di(methylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(methylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, 1,2-bis-(2,7-di(n-butylethynyl)fluorenyl) ethane zirconium dichloride, and 1,2-bis-(2,7-di(n-butylethynyl)fluorenyl)ethane hafnium dichloride. ### Claim 16 (depends on 1) A method according to claim 1, wherein at least two different metallocenes are present during the prepolymerization. ### Claim 17 (depends on 16) A method according to claim 16, wherein at least two different metallocenes each having at least one internal alkynyl substituent are employed during the prepolymerization. ### Claim 18 (depends on 16) A process according to claim 16, wherein at least one of the metallocene contains a substituted or unsubstituted fluorenyl group. ### Claim 19 (depends on 18) A method according to claim 18, wherein at least two different bridged metallocenes are employed each having at least one internal alkynyl substituent. ### Claim 20 (depends on 1) A process according to claim 1 wherein said solid metallocene-containing catalyst system is prepared using a metallocene containing at least one fluorenyl group. ### Claim 21 (depends on 20) A process according to claim 20 wherein the polymerization is conducted in a continuous loop reactor and isobutane is used as a liquid diluent for the polymerization. ### Claim 22 (depends on 21) A process according to claim 21 wherein the solid metallocene-containing catalyst system used in the polymerization is prepared by (a) combining in a liquid an alkylaluminoxane and at least one metallocene selected from the group consisting of bridged metallocenes represented by the formula R(Z)(Z)MeQ.sub.k and unbridged metallocenes of the formula (Z)(Z) MeQ.sub.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, benzofluorenyl, and fluorenyl ligands; 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, halogens, and organoradicals; k is a number sufficient to fill out the remaining valances of Me; with the further proviso that at least one of said Z's or R has at least one internal alkynyl substituent, (b) prepolymerizing ethylene in the resulting liquid, in the presence of silica, and (c) separating the resulting solid from the liquid. ### Claim 23 (depends on 22) A process according to claim 22 wherein the liquid used in step (a) consists essentially of an aromatic liquid. ### Claim 24 (depends on 22) A process according to claim 22 wherein said solid metallocene-containing catalyst system is prepared using a metallocene selected from the group consisting of (2,7-di(phenylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(phenylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7-di(t-butylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(t-butylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7-di(n-butylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(n-butylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, (2,7- di(methylethynyl)fluorenyl) (cyclopentadienyl) zirconium dichloride, (2,7-di(methylethynyl)fluorenyl) (cyclopentadienyl) hafnium dichloride, 1,2-bis-(2,7-di(n-butylethynyl)fluorenyl) ethane zirconium dichloride, and 1,2-bis-(2,7-di(n-butylethynyl)fluorenyl) ethane hafnium dichloride. ### Claim 25 (depends on 22) A process according to claim 22 wherein R is a saturated alkylene diradical having 1 to 4 carbon atoms in its main chain. ### Claim 26 (depends on 25) A process according to claim 25 wherein R is --CH.sub.2 --. ### Claim 27 (depends on 25) A process according to claim 25 wherein R is selected from divalent dihydrocarbyl silanes. ### Claim 28 (depends on 22) A process according to claim 22 wherein said solid metallocene-containing catalyst system is prepared using (2,7-di(phenyl ethynyl) fluorenyl) (cyclopentadienyl) zirconium dichloride. ### Claim 29 (depends on 22) A process according to claim 22 wherein said solid metallocene-containing catalyst system is prepared using the metallocene (cyclopentadienyl) (2,7-di(t-butyl ethynyl)fluorenyl) zirconium dichloride. ### Claim 30 A process for polymerizing ethylene under slurry polymerization conditions in the presence of an alkane liquid diluent comprising contacting ethylene with a solid metallocene-containing catalyst system produced by the steps comprising: (a) combining an organoaluminoxane and at least one metallocene having a ligand having at least one substituent with an internal alkyne functionality in a liquid to form a liquid catalyst system, (b) conducting prepolymerization of ethylene in the presence of said liquid catalyst system to produce a prepolymerized solid catalyst, and (c) separating the resulting solid from the liquid and the components dissolved in the liquid to yield said solid metallocene-containing catalyst system.