Abstract: The present invention provides a new type of supported metallocene catalyst system. In one aspect of the invention, an inorganic oxide support, such as silica, is impregnated with a Group XIII element such as B, Al or GA. The support is then contacted with a liquid catalyst system prepared by combining in a liquid an organo aluminoxane and a metallocene having two cyclopetadienyl-type ligands selected from substituted or unsubstituted cyclopentadienyl, indenyl, benzoindenyl, tetrahdroindenyl, benzofluorenyl, octahydrofluorenyl, and fluorenyl ligands to form a supported metallocene catalyst system. In preferred embodiments the process further includes conducting prepolymerization of at least one olefin in the presence of the supported metallocene catalyst system to produce a prepolymerized metallocene catalyst system. The prepolymerized metallocene catalyst system prepared in this manner yields substantially increased activity for the polymerization of olefins.
Type:
Grant
Filed:
December 31, 1998
Date of Patent:
May 29, 2001
Assignee:
Phillips Petroleum Company
Inventors:
David W. Dockter, Bryan E. Hauger, M. Bruce Welch, Randall S. Muninger
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.
Type:
Grant
Filed:
September 14, 1998
Date of Patent:
April 24, 2001
Assignee:
Phillips Petroleum Company
Inventors:
Michael Jung, Helmut G. Alt, Bryan E. Hauger, M. Bruce Welch, David W. Dockter, Syriac J. Palackal, Antoni Jurkiewicz
Abstract: A high clarity film containing three layers wherein the polymer of each outer layer is the same or different polyethylene selected from polyethylenes having a density of at least 0.925 g/cc, and a molecular weight distribution of less than 4, and being further characterized by being substantially free of branches having 6 or more carbon atoms, polyethylenes of the outer layers optionally containing a fluoroelastomer.
Type:
Grant
Filed:
January 15, 1998
Date of Patent:
April 10, 2001
Assignee:
Phillips Petroleum Company
Inventors:
Ashish M. Sukhadia, David C. Rohlfing, Jay Janzen, Paul J. DesLauriers, Jim D. Byers, Louis Moore, Jr., M. Bruce Welch, Syriac J. Palackal, William M. Whitte, William R. Coutant, Kiplin D. Cowan
Abstract: A process is disclosed for the particle form polymerization of olefins. The process employs a titanium-containing having hydrocarbon soluble titanium components. The resulting catalyst is pretreated with an organometallic reducing agent prior to the introduction of the catalyst into the polymerization zone to give a catalyst which can be used satisfactorily in a loop reactor with lower levels of cocatalyst.
Type:
Grant
Filed:
February 27, 1995
Date of Patent:
March 6, 2001
Assignee:
Phillips Petroleum Company
Inventors:
Kent E. Mitchell, Max P. McDaniel, M. Bruce Welch, Elizabeth A. Benham, Grover W. Cone
Abstract: Metallocene having two cyclic dienyl groups connected by a single carbon having an aryl substituent and a terminally unsaturated hydrocarbyl substituent, olefin polymerization catalyst systems prepared therefrom, and the use of such catalyst systems are disclosed.
Type:
Grant
Filed:
February 16, 1999
Date of Patent:
February 13, 2001
Assignee:
Phillips Petroleum Company
Inventors:
M. Bruce Welch, Syriac J. Palackal, Bryan E. Hauger, David W. Dockter, Alexander Köppl, Helmut G. Alt
Abstract: An additive composition is provided that comprises:
(a) tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;
(b) bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite; and
(c) a costabilizer selected from the group consisting of sodium stearoyl lactylate, calcium stearoyl lactylate, calcium lactate, and mixtures thereof. Additionally, polymer compositions are provided that comprise the additive composition and (a) 2-Naphthalenecarboxamide, N,N′-(2-chloro-1,4 phenylene)bis[4-[(2,5-dichlorophenyl)azo]-3-hydroxy- and (b) a stereoregular, branched-mono-1-olefin polymer.
Abstract: A method for producing a low density copolymer of ethylene and 1-hexene having a density in the range of about 0.915 to about 0.930 grams/cc in a continuous loop reactor under slurry phase reactor conditions in the presence of a liquid diluent comprising (a) using a prepolymerized solid particulate metallocene catalyst system, (b) combining the catalyst system with a liquid diluent, and (c) agitating the mixture of (b) to form a liquid mixture containing catalyst system particles that are substantially uniform in size, (d) passing this liquid mixture into the loop reactor, (e) not adding any hydrogen, (f) employing the temperature in the range of about 170.degree. F. to about 180.degree. F., (g) employing ethylene in an amount equal to about 5 to about 6 weight % of the liquid diluent and the loop reactor, and (h) employing 1-hexene in an amount equal to about 1.5 to about 2.5 weight % of the liquid diluent in the loop reactor.
Type:
Grant
Filed:
February 26, 1998
Date of Patent:
December 26, 2000
Assignee:
Phillips Petroleum Company
Inventors:
Elizabeth A. Benham, Carleton E. Stouffer, Jose M. Dionisio, Steven J. Secora, John N. DeGood, III, Robert W. Bohmer, Michael C. Carter
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:
May 28, 1998
Date of Patent:
December 19, 2000
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
Abstract: A prepolymerized solid catalyst is prepared by reacting a suitable support base with an organoaluminum compound and then reacting that product with an activity promoting amount of water and then reacting the resulting solid cocatalyst with a metallocene and then subjecting that product to prepolymerization in the presence of hydrogen. The prepolymerized solid catalyst is useful in the polymerization of olefins.
Type:
Grant
Filed:
September 9, 1998
Date of Patent:
December 12, 2000
Assignee:
Phillips Petroleum Company
Inventors:
M. Bruce Welch, Alexander Koppl, Helmut G. Alt
Abstract: The present invention provides polymers of ethylene having ethyl branches, a narrow molecular weight distribution, no substantial amount of branches longer than any comonomer employed in the polymerization, and an unusually low branching to density ratio. In one embodiment the polyethylenes are substantially free of any branches having more than 2 carbon atoms, i.e. ethyl branches, and the molar percent of ethyl branches is substantially the same for molecular fractions across the molecular weight distribution. In another embodiment the polyethylenes have other branches having 3 or more carbons and the molar percent of the ethyl branches is substantially the same for molecular fractions across the molecular weight distribution.
Type:
Grant
Filed:
December 2, 1998
Date of Patent:
November 28, 2000
Assignee:
Phillips Petroleum Company
Inventors:
M. Bruce Welch, Helmut G. Alt, Bernd Peifer, Syriac J. Palackal, Gary L. Glass, Ted M. Pettijohn, Gil R. Hawley, Darryl R. Fahey
Abstract: Processes are provided that produce organo-aluminoxane compositions. Said processes comprise: desiccating a first mixture, where said first mixture comprises organo-aluminoxane molecules intermixed with a solvent, to produce a first composition, where said first composition comprises organo-aluminoxane molecules; mixing said first composition with a solvent to produce a second mixture, where said second mixture comprises organo-aluminoxane molecules and said solvent; contacting said second mixture with a insolublization agent to produce said organo-aluminoxane compositions. A polymerization process using a catalyst that comprises an organo-aluminoxane composition is also provided.
Type:
Grant
Filed:
September 9, 1997
Date of Patent:
August 1, 2000
Inventors:
Syriac J. Palackal, M. Bruce Welch, Rolf L. Geerts
Abstract: Novel Si--N--Si bridged metallocenes of the formula [L--Si--Me.sub.2 NRSiMe.sub.2 L]MX.sub.2 wherein L is a C.sub.5 H.sub.4, C.sub.9 H.sub.6, or C.sub.13 H.sub.8 radical, R is alkyl and M is zirconium, titanium, or hafnium, and X is selected from the group consisting of chlorine, bromine, iodine, methyl and diethyl amine, are provided via a novel amine elimination reaction followed by cyclization of the ligand sphere of the amino silyl functionalized metallocene dichloride complex. Further, there is provided novel unbridged metallocene precursors of the formula [RNH--SiMe.sub.2 --L].sub.2 MX.sub.2. Such Si--N--Si bridged metallocenes in combination with an organometallic compound of metals of Group IA, IIA, and IIB form a catalyst system which is highly active in the polymerization of alpha-olefins.
Type:
Grant
Filed:
January 19, 1999
Date of Patent:
July 11, 2000
Assignee:
Hughes Electronics Corporation
Inventors:
Klaus Fottinger, Helmut G. Alt, M. Bruce Welch
Abstract: Polymeric ligands, polymeric metallocenes, and processes for preparing same are provided. The process for preparing polymeric metallocenes comprises reacting a polymeric ligand, a transition metal compound, and an alkali metal compound. In one embodiment, a process for preparing polymeric ligands comprises reacting at least one bridged cyclopentadienyl-type monomer and an initiator under polymerization conditions. In another embodiment, a polymeric ligand is represented by the formula [Q'].sub.n, wherein Q' is a unit containing at least one bridged cyclopentadienyl-type group and wherein n is 1-5000. In another embodiment, a polymeric metallocene is represented by the formula [Q"MX.sub.m ].sub.
Type:
Grant
Filed:
March 26, 1998
Date of Patent:
May 2, 2000
Assignee:
Phillips Petroleum Company
Inventors:
Helmut G. Alt, Peter Schertl, Bernd Peifer, Syriac J. Palackal, M. Bruce Welch
Abstract: A polymerization process comprising contacting at least one olefin under polymerization conditions with a catalyst composition produced by combining an organoaluminoxane cocatalyst and a polymeric metallocene catalyst prepared by (1) forming a fluorine-containing polymer by (a) polymerizing a 2-vinyl fluorenyl compound or (b) polymerizing a fluorenyl compound by reacting it with chloro methyl methyl ether in the presence of zinc dichloride or aluminum trichloride; (2) reacting the fluorenyl-containing polymer with an alkali metal compound; and (3) reacting the product of step (2) with a transition metal-containing compound.
Type:
Grant
Filed:
March 26, 1998
Date of Patent:
March 21, 2000
Assignee:
Phillips Petroleum Company
Inventors:
Bernd Peifer, Syriac J. Palackal, M. Bruce Welch, Helmut G. Alt, Peter Schertl
Abstract: In accordance with the present invention there is provided a new solid aluminoxy composition prepared by reacting aluminoxane with a boroxine. Still further there is provided olefin polymerization catalyst systems incorporating the inventive solid aluminoxy composition. Still further, there is provided processes of polymerization using the inventive solid aluminoxy composition.
Type:
Grant
Filed:
January 17, 1995
Date of Patent:
December 21, 1999
Inventors:
Rolf L. Geerts, Tara G. Hill, Scott E. Kufeld
Abstract: A solid cocatalyst is prepared by combining (1) a first material capable of affixing an organoaluminum compound with (2) an organic liquid and then adding an organoaluminum compound and then contacting that product with water dispersed in an inert gas. Further catalyst compositions prepared from that cocatalyst and the use of such catalyst compositions to polymerize olefins is disclosed.
Type:
Grant
Filed:
October 21, 1997
Date of Patent:
November 23, 1999
Inventors:
Alexander Koppl, Helmut G. Alt, Syriac J. Palackal, M. Bruce Welch
Abstract: A prepolymerized olefin polymerization catalyst, its prepration, and use are disclosed. The catalyst is prepared by contacting a solid particulate transition metal-containing olefin polymerization catalyst with an olefin in a confined zone under suitable conditions wherein the prepolymerization is conducted under conditions such that the olefin is added to the confined zone at a rate such that the pressure in the confined zone increases no more than about 0.5 psig/sec. during the olefin addition.
Abstract: Bridged fluorenyl/indenyl metallocenes having substituents at the 3 position of the indenyl and the use thereof in the polymerization of olefins are disclosed. Also a new method for preparing bridged fluorenyl/indenyl ligands wherein the indenyl has a substituent in the 3 position and the preparation of metallocenes with such ligands.
Type:
Grant
Filed:
September 12, 1997
Date of Patent:
March 23, 1999
Inventors:
Michael Jung, Helmut G. Alt, M. Bruce Welch