# US 6,294,496 B1 · Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 6,294,496 B1 - Document ID: US6294496B1 - Status: Granted - Kind: B1 - Application number: 09/571,542 - Filed: 2000-05-16 - Granted: 2001-09-25 - Earliest claimed: 1997-12-08 - Assignees: Albemarle Corporation - Inventors: Steven P. Diefenbach - Web page: https://patentgrep.com/patent/US6294496B1 ## CPC - C08F 10/02: Ethene - C08F 4/65927: {two cyclopentadienyl rings being mutually bridged} - C08F 110/02: Ethene - 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 Described are solid olefin polymerization catalysts that have, inter alia, very high productivities (at least 18,000 grams of polyethylene per gram of catalyst in one hour) as shown by a standard test procedure for measuring this property or characteristic. Such particulate catalysts can be prepared by prepolymerizing vinylolefin with a Group 4 metallocene-aluminoxane solution, using proportions of vinylolefin (most preferably, ethylene) in the range of about 150 to about 1500, and preferably in the range of about 175 to about 1000, moles per mole of Group 4 metallocene used in forming the solution. The atom ratio of aluminum to Group 4 metal in the solution is in the range of about 150:1 to about 1500:1, and preferably in the range of about 175:1 to about 1000:1. In addition, the Group 4 metallocene ingredient used in forming these highly productive catalysts has in its molecular structure at least one polymerizable olefinic substituent. These particulate catalysts do not contain, and thus are not produced in the presence of, a preformed support such as an inorganic compound (silica or etc.) or a preformed particulate polymeric support. ## Claims ### Claim 1 A self-supported vinylolefin-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst composition devoid of a preformed support and having a productivity, when fresh and if tested in slurry form for productivity with ethylene in a 2-liter autoclave that has been precharged with about one liter of isobutane and that is charged with ethylene to a total pressure of 450 psig at 91.5° C., of at least 18,000 grams of polyethylene per gram of catalyst in one hour, the metallocene having prior to prepolymerization at least one polymerizable olefinic substituent in the molecule. ### Claim 2 (depends on 1) A catalyst composition according to claim 1 wherein the Group 4 metallocene used in forming said composition is a zirconium metallocene containing only 1 atom of zirconium per molecule, and wherein the aluminoxane used in forming said composition is a methylaluminoxane. ### Claim 3 (depends on 1) A catalyst composition according to claim 1 wherein said composition has a productivity, when fresh and if tested for productivity in accordance with claim 1, of at least 25,000 grams of polyethylene per gram of catalyst in one hour. ### Claim 4 (depends on 1) A catalyst composition according to claim 1 wherein said composition has a productivity, when fresh and if tested for productivity in accordance with claim 1, of at least 30,000 grams of polyethylene per gram of catalyst in one hour. ### Claim 5 (depends on 1) A catalyst composition according to claim 1 wherein the Group 4 metallocene used in forming said composition is a zirconium metallocene containing only 1 atom of zirconium per molecule, and wherein the aluminoxane used in forming said composition is a methylaluminoxane that has previously been heated at a temperature of at least about 40° C. ### Claim 6 (depends on 1) A catalyst composition according to claim 1 wherein the metallocene used in forming said composition is 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methane zirconium dichloride, and wherein the aluminoxane used in forming said composition is a methylaluminoxane. ### Claim 7 (depends on 1) A catalyst composition according to claim 1 wherein the Group 4 metallocene used in forming said composition is a hafnium metallocene containing only 1 atom of hafnium per molecule. ### Claim 8 A self-supported ethylene-prepolymerized Group 4 metallocene-aluminoxane particulate catalyst composition devoid of a preformed support and having a productivity, when fresh and if tested in slurry form for productivity with ethylene in a 2-liter autoclave that has been precharged with about one liter of isobutane and that is charged with ethylene to a total pressure of 450 psig at 91.5° C., of at least 18,000 grams of polyethylene per gram of catalyst in one hour, the metallocene having prior to prepolymerization at least one polymerizable olefinic substituent in the molecule. ### Claim 9 (depends on 8) A catalyst composition according to claim 8 wherein the Group 4 metallocene used in forming said composition is a zirconium metallocene containing only 1 atom of zirconium per molecule, and wherein the aluminoxane used in forming said composition is a methylaluminoxane. ### Claim 10 (depends on 8) A catalyst composition according to claim 8 wherein said composition has a productivity, when fresh and if tested for productivity in accordance with claim 8, of at least 25,000 grams of polyethylene per gram of catalyst in one hour. ### Claim 11 (depends on 10) A catalyst composition according to claim 10 wherein the Group 4 metallocene used in forming said composition is a zirconium metallocene containing only 1 atom of zirconium per molecule, and wherein the aluminoxane used in forming said composition is a methylaluminoxane. ### Claim 12 (depends on 11) A catalyst composition according to claim 11 wherein the metallocene used in forming said composition is 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methane zirconium dichloride. ### Claim 13 A process which comprises: a) mixing together in an inert organic solvent medium at least one Group 4 metallocene having at least one polymerizable olefinic substituent in the molecule, and at least one aluminoxane, to form a catalytic solution; and b) reacting under polymerization conditions a controlled amount of vinylolefin monomer with at least a portion of said catalytic solution formed in a) such that self-supported solid catalyst particles devoid of any preformed support and having a productivity, when fresh and if tested in slurry form for productivity with ethylene in a 2-liter autoclave that has been precharged with about one liter of isobutane and that is charged with ethylene to a total pressure of 450 psig at 91.5° C., of at least 18,000 grams of polyethylene per gram of catalyst in one hour. ### Claim 14 (depends on 13) A process according to claim 13 wherein the mole ratio of vinylolefin to Group 4 metallocene reacted in b) is in the range of about 150:1 to about 1500:1. ### Claim 15 (depends on 13) A process according to claim 13 wherein the mole ratio of vinylolefin to Group 4 metallocene reacted in b) is in the range of about 175:1 to about 1000:1. ### Claim 16 (depends on 13) A process according to claim 13 wherein the atom ratio of aluminum to Group 4 metal in said solution is in the range of about 150:1 to about 1500:1. ### Claim 17 (depends on 13) A process according to claim 13 wherein the atom ratio of aluminum to Group 4 metal in said solution is in the range of about 175:1 to about 1000:1. ### Claim 18 (depends on 13) A process according to claim 13 wherein the mole ratio of vinylolefin to Group 4 metallocene reacted in b) is in the range of about 150:1 to about 1500:1; and Wherein the atom ratio of aluminum to Group 4 metal in said catalytic solution of a) is in the range of about 150:1 to about 1500:1. ### Claim 19 (depends on 13) A process according to claim 13 wherein the mole ratio of vinylolefin to Group 4 metallocene reacted in b) is in the range of about 175:1 to about 1000:1; and wherein the atom ratio of aluminum to Group 4 metal in said catalytic solution of a) is in the range of about 175:1 to about 1000:1. ### Claim 20 (depends on 13, 14, 15, 16, 17, 18, 19) A process according to any of claims 13-19 wherein the Group 4 metallocene is a zirconium metallocene containing only 1 atom of zirconium per molecule; wherein the aluminoxane is entirely or predominately a methylaluminoxane; and wherein the vinylolefin monomer is ethylene. ### Claim 21 (depends on 13, 14, 15, 16, 17, 18, 19) A process according to any of claims 13-19 wherein the Group 4 metallocene is 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methane zirconium dichloride; wherein the aluminoxane is entirely or predominately a methylaluminoxane; wherein the vinylolefin monomer is ethylene; and wherein b) is conducted at a temperature of about 15° C. or below. ### Claim 22 (depends on 13, 14, 15, 16, 17, 18, 19) A process according to any of claims 13-19 wherein the Group 4 metallocene is 1-(9-fluorenyl)-1-(cyclopentadienyl)-1-(but-3-enyl)-1-(methyl)methane zirconium dichloride; wherein the aluminoxane is entirely or predominately a methylaluminoxane; wherein the vinylolefin monomer is ethylene; wherein b) is conducted at a temperature of about 15° C. or below; and wherein said catalytic solution contains in the range of about 4 to about 6.5 wt % of the combination of said metallocene and said aluminoxane and/or a reaction product formed therefrom, with the balance to 100 wt % being the inert organic solvent medium.