Abstract: A process for preparing polynuclear metallocenes by reacting a metallocene in which one of the cyclopentadienyl-containing radicals has a substituent having olefinic or acetylenic unsaturation with a second metallocene having a metal which comes from groups IVb to VIb of the periodic table and a metal-hydride bond. The use of the resulting metallocenes in the polymerization of olefins is disclosed, including techniques for using such metallocenes to produce solid prepolymerized metallocene-containing catalyst systems suitable for use in the polymerization of olefins.
Type:
Grant
Filed:
May 12, 1995
Date of Patent:
November 3, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Bernd Peifer, Helmut G. Alt, M. Bruce Welch
Abstract: Unbridged metallocenes of titanium, zirconium and hafnium having an unsubstituted cyclopentadienyl radical and an indenyl radical having in at least one of the 1, 2, or 3 positions a substitutent selected from hydrocarbon radicals and trialkylsilyl radicals, and their use in the polymerization of olefins.
Type:
Grant
Filed:
March 29, 1996
Date of Patent:
July 14, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Claudia Schmid, Helmut G. Alt, M. Bruce Welch
Abstract: Double bound metallocenes, i.e. metallocenes having a cyclopentadienyl-containing radical that is bound to a transition metal both by a pi bond and by a sigma carbon bond of a substituent of that same cyclopentadienyl-containing radical can be prepared by reducing metallocenes having a cyclopentadienyl-containing radical having at least one an unsaturated substituent. Also a process for producing polymers comprising contacting at least one olefinic monomer under suitable polymerization conditions with such double bound metallocenes.
Type:
Grant
Filed:
March 7, 1997
Date of Patent:
June 23, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Bernd Peifer, Helmut G. Alt, M. Bruce Welch
Abstract: A process for preparing a polymer of ethylene having a flow activation energy higher than that of a substantially linear ethylene polymer of the same molecular weight involving using bridged sandwich-bonded fluorenyl-containing metallocenes and the polymers resulting therefrom.
Type:
Grant
Filed:
March 3, 1995
Date of Patent:
January 20, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Syriac J. Palackal, M. Bruce Welch, David C. Rohlfing, Jay Janzen
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.
Type:
Grant
Filed:
May 4, 1995
Date of Patent:
January 6, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Bernd Peifer, Helmut G. Alt, M. Bruce Welch
Abstract: A catalyst system comprising an unbridged bis(2-aryltetrahydro-indenyl) metallocene and a cocatalyst and its use in the polymerization of olefins, especially olefins having 3 or more carbon atoms.
Type:
Grant
Filed:
July 17, 1996
Date of Patent:
January 6, 1998
Assignee:
Phillips Petroleum Company
Inventors:
Gil R. Hawley, Timothy M. Ramsey, Ronald L. Halterman, Darryl R. Fahey
Abstract: In accordance with the present invention, there is provided an organoaluminoxy product prepared by the process comprising reacting an organoaluminoxane with an ene-ol compound. In another embodiment, the organoaluminoxane can be prepared in situ by the process comprising reacting a hydrocarbylaluminum compound, water, and the ene-ol compound. Further there is provided olefin polymerization catalyst systems comprising the organoaluminoxy product and at least one transition metal-containing catalyst. Optionally, the catalyst system is prepolymerized in the presence of at least one olefin to form a prepolymerized catalyst system. Still further there is provided processes for the polymerization of olefins using the catalyst systems.
Type:
Grant
Filed:
February 8, 1995
Date of Patent:
September 23, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Rolf L. Geerts, M. Bruce Welch, Syriac J. Palackal, Helmut G. Alt, Bernd Peifer, Harold R. Deck
Abstract: A catalyst system and process for polymerizing olefins employing a cocatalyst and specific ethylene bridged fluorenyl-containing metallocenes having substituents which result in high yields of polyethylene and/or high molecular weight polyethylene.
Type:
Grant
Filed:
July 11, 1996
Date of Patent:
September 16, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Peter Schertl, Helmut G. Alt, M. Bruce Welch
Abstract: Double bound metallocenes, i.e. metallocenes having a cyclopentadienyl-containing radical that is bound to a transition metal both by a pi bond and by a sigma carbon bond of a substituent of that same cyclopentadienyl-containing radical can be prepared by reducing metallocenes having a cyclopentadienyl-containing radical having at least one an unsaturated substituent. Also a process for producing polymers comprising contacting at least one olefinic monomer under suitable polymerization conditions with such double bound metallocenes.
Type:
Grant
Filed:
May 30, 1995
Date of Patent:
August 5, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Bernd Peifer, Helmut G. Alt, M. Bruce Welch
Abstract: Group IVB metal metallocenes of bis(1-methyl fluorenyl) diphenyl silane and bis(1-methyl fluorenyl) dimethyl tin are disclosed, plus their use in the production of polyolefins, including isotactic polypropylene.
Type:
Grant
Filed:
June 1, 1995
Date of Patent:
June 10, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Konstantinos Patsidis, M. Bruce Welch, Peter P. Chu
Abstract: Group IVB metal metallocenes of bis(1-methyl fluorenyl) diphenyl silane and bis(1-methyl fluorenyl) dimethyl tin are disclosed, plus their use in the production of polyolefins, including isotactic polypropylene.
Type:
Grant
Filed:
June 7, 1993
Date of Patent:
May 20, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Konstantinos Patsidis, M. Bruce Welch, Peter P. Chu
Abstract: Unbridged fluorenyl containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.
Type:
Grant
Filed:
March 22, 1995
Date of Patent:
May 6, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Gil R. Hawley, Paul D. Smith, Syriac J. Palackal, Michael Schmid, M. Bruce Welch, Konstantinos Patsidis, Rolf L. Geerts, Eric T. Hsieh, Max P. McDaniel
Abstract: Fluorenyl-containing silyl bridged metallocenes, the process of using such metallocenes to polymerize olefins, and the resulting unusual syndiotactic polypropylene are disclosed.
Type:
Grant
Filed:
December 9, 1994
Date of Patent:
May 6, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Syriac J. Palackal, Helmut G. Alt, Konstantinos Patsidis, Tara G. Hill, Gil R. Hawley, Peter P. Chu, M. Bruce Welch, Rolf L. Geerts
Abstract: A method is provided for forming a supported cyclopentadiene-type compound comprising contacting a cyclopentadiene-type compound containing an active halogen with an inorganic support having surface hydroxyl group. Also there is provided a method of preparing a supported metallocene comprising reacting the supported cyclopentadiene-type compound with a transition metal compound under suitable conditions. There is also provided a process for producing bridged cyclopentadiene-type ligands having a bridge having branch that has a terminal vinyl group. Also metallocenes of these ligands are provided. Still further there is provided a process for producing bridged cyclopentadiene-type ligands having a bridge having a branch that has a terminal active halogen. The resulting new ligands and supported metallocenes produced therefrom are also provided.
Type:
Grant
Filed:
June 5, 1995
Date of Patent:
April 1, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Konstantinos Patsidis, Bernd Peifer, Helmut G. Alt, Rolf L. Geerts, Darryl R. Fahey, M. Bruce Welch, Syriac J. Palackal, Harold R. Deck
Abstract: 9-substituted fluorenyl-containing metallocenes and their use in the polymerization of olefins is disclosed. In addition, novel 9-cyclohexylfluorenyl or 9-phenylfluorenyl compounds are disclosed. Also methods for preparing such 9-substituted fluorenyl compounds are presented.
Type:
Grant
Filed:
March 23, 1995
Date of Patent:
March 11, 1997
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Syriac J. Palackal, Konstantinos Patsidis, M. Bruce Welch, Rolf L. Geerts, Eric T. Hsieh, Max P. McDaniel, Gil R. Hawley, Paul D. Smith, Jay Janzen, Michael Schmid
Abstract: A generally dipyramidal-shaped catalyst precursor is prepared by dissolving magnesium dichloride and a suitable alcohol in a suitable solvent and then cooling to obtain a precipitate of the desired shape. The use of the precursor to prepare catalysts and the use of the catalysts to prepare polymers is also disclosed.
Abstract: A catalyst system comprising a bridged fluorenyl-containing metallocene, an unbridged metallocene, and a suitable cocatalyst and the use of such catalyst systems to produce olefin polymers. Also novel olefin polymers produced by those processes.
Type:
Grant
Filed:
September 13, 1994
Date of Patent:
January 14, 1997
Assignee:
Phillips Petroleum Company
Inventors:
M. Bruce Welch, Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn
Abstract: Fluorenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.
Type:
Grant
Filed:
February 3, 1994
Date of Patent:
November 5, 1996
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Syriac J. Palackal, Roland Zenk, M. Bruce Welch, Michael Schmid
Abstract: Processes are disclosed for preparing compounds of the formula Z--R--Z where each Z can be selected from cyclopentadienyl type radicals such as substituted or unsubstituted cyclopentadienyl, indenyl, fluorenyl or tetrahydroindenyl or where one Z is Cl, Br, or I by reacting specific Z precursors with a dihaloalkylene compound. Also new cyclopentadienyl-type compounds are disclosed.
Type:
Grant
Filed:
August 15, 1994
Date of Patent:
July 30, 1996
Assignee:
Phillips Petroleum Company
Inventors:
Konstantinos Patsidis, Syriac J. Palackal, Helmut G. Alt
Abstract: Unbridged indenyl-containing metallocenes are disclosed along with methods for making the metallocenes. Also disclosed are methods for using the metallocenes as polymerization catalysts. In addition, polymers resulting from such polymerizations are disclosed.
Type:
Grant
Filed:
June 3, 1994
Date of Patent:
July 30, 1996
Assignee:
Phillips Petroleum Company
Inventors:
Michael Schmid, Helmut G. Alt, M. Bruce Welch