Elemental Oxygen Or Nonmetallic Inorganic Oxygen-containing Material, Other Than Water Patents (Class 502/120)
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Patent number: 5661095Abstract: A catalyst component useful in the polymerization of olefins which includes a support formed of a copolymer of an olefin and a silane monomer having at least one unsaturated hydrocaryl substitutent. A process for making the catalyst component as well as a catalyst composition which includes the catalyst component is also set forth.Type: GrantFiled: June 6, 1995Date of Patent: August 26, 1997Assignee: Quantum Chemical CorporationInventors: Craig C. Meverden, Emory A. Ford
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Patent number: 5654249Abstract: Chromium catalyst compositions are provided. These chromium catalyst compositions comprise at least two chromium catalyst systems that have a certain amount of chromium and a support that comprises silica and titania. the supports have certain pore volumes and surface areas. These catalyst compositions are useful for homopolymerizing ethylene or copolymerizing ethylene with a comonomer. The resins produced are useful in film applications.Type: GrantFiled: May 25, 1995Date of Patent: August 5, 1997Assignee: Phillips Petroleum CompanyInventors: Kent W. Rollmann, Elizabeth A. Benham, William M. Whitte, Max P. McDaniel, William R. Coutant, F. Wallace Bailey
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Patent number: 5648308Abstract: Inorganic and organic impurities are removed from a metallocene catalyst compound comprising the steps of (a) separating inorganic impurities from said compound by forming a solution of said compound in an organic solvent medium which is substantially a non-solvent for said inorganic impurities, (b) treating the solution of said compound with a particulate absorbing material so as to absorb and remove organic impurities from said solution, and (c) separating the solid material, including said particulate absorbing material, from said solution. Optionally, water can be removed by adding a drying agent.Type: GrantFiled: August 10, 1995Date of Patent: July 15, 1997Assignee: Albemarle CorporationInventors: John Y. Lee, Steven P. Diefenbach
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Patent number: 5648310Abstract: Metallocene-containing catalyst compositions that include inert filler, a method for their preparation, and a method for their use in production of polyolefins are disclosed and claimed. The catalyst compositions contain solid particles of a mixture comprising a) a metallocene catalyst; b) a cocatalyst capable of activating said metallocene catalyst; and c) particulate filler material having an average particle size of less than about 10 micrometers that is unreactive with the metallocene catalyst and the cocatalyst. They are prepared by spray drying a slurry of the constituents.Type: GrantFiled: June 26, 1995Date of Patent: July 15, 1997Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Eric Paul Wasserman, Mark Wilton Smale, Timothy Roger Lynn, Robert Converse Brady, III, Frederick John Karol
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Patent number: 5643847Abstract: The invention is directed to a catalyst composition suitable for addition reactions of ethylenically and acetylenically unsaturated monomers comprising a metal oxide support having covalently bound to the surface thereof directly through the oxygen atom of the metal oxide an activator anion that is also ionically bound to a catalytically active transition metal cation compound. The invention includes a preparation process for the invention catalyst composition exemplified by reacting a Lewis acid, such as trisperflourophenyl boron with residual silanol groups of a silica support, preferably then reacting with a Lewis base such as diethylaniline, so as to prepare a silica bound anionic activator that when combined with a suitable transition metal compound will protonate it so as to form the ionic catalyst system. Use of the invention catalyst to polymerize alpha-olefins is exemplified.Type: GrantFiled: June 7, 1995Date of Patent: July 1, 1997Assignee: Exxon Chemical Patents Inc.Inventor: John Flexer Walzer, Jr.
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Patent number: 5641843Abstract: A process for producing an alpha-olefin polymer, which comprises polymerizing an alpha-olefin in the presence of a catalyst formed from(A) a solid catalyst component comprising an inorganic carrier and deposited thereon a compound of a transition metal of Group IVB of the periodic table treated with an organometallic compound, and(B) an aluminoxane.Type: GrantFiled: November 17, 1995Date of Patent: June 24, 1997Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Akinori Toyota, Norio Kashiwa
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Highly active catalysts for olefin polymerization and a polymerization process using these catalysts
Patent number: 5629255Abstract: Highly active catalysts, for olefin polymerization, from tetraneophylzirconium and partly hydroxylated metal oxides from group IIa, IIIa, IVa or IVb of the Periodic Table, which are essentially free from by-products.Type: GrantFiled: September 21, 1995Date of Patent: May 13, 1997Assignee: PCD Polymere Gesellschaft m.b.H.Inventors: Norbert Hafner, Wilfried T oltsch, Hans Ledwinka, Wolfgang Neissl -
Patent number: 5629253Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported bulky ligand transition metal catalyst which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting particularly in a slurry phase polymerization process.Type: GrantFiled: January 16, 1996Date of Patent: May 13, 1997Assignee: Exxon Chemical Patents, Inc.Inventor: Main Chang
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Patent number: 5627246Abstract: A supported catalyst system that is obtained bya) reacting a finely divided carrier with an a-trisalkoxy-silyl-.omega.-haloalkyl compound,b) adding a metallocene complex of the indicated formula I to the reaction product of a);c) reacting the product of b) with a quaternizing agent; andd) optionally adding an open-chain or cyclic alumoxane compound.The catalyst system can be used to prepare polymers of C.sub.2 -C.sub.10 -alk-1-enes.Type: GrantFiled: March 1, 1995Date of Patent: May 6, 1997Assignee: BASF AktiengesellschaftInventors: Franz Langhauser, David Fischer, J urgen Kerth, G unther Schweier, Elke Barsties, Hans-Herbert Brintzinger, Stefan Schaible, Werner Roell
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Patent number: 5624877Abstract: A process is provided to produce polyolefins having a multimodal molecular weight distribution at the molecular level by contacting at least one mono-1-olefin in a polymerization zone, under polymerization conditions, with two different types of supported chromium catalyst systems. The first catalyst system comprises a chromium oxide catalyst system which comprises chromium oxide supported on an inorganic oxide. The second catalyst system comprises a chromocene catalyst system which comprises chromocene supported on an inorganic oxide. The resultant, recovered polymer has a multimodal, or at least a bimodal, molecular weight distribution.Type: GrantFiled: June 2, 1995Date of Patent: April 29, 1997Assignee: Phillips Petroleum CompanyInventors: Joseph J. Bergmeister, Scott E. Kufeld, Max P. McDaniel
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Patent number: 5614455Abstract: Olefin polymerization catalyst, process for its preparation, and its useA supported polymerization catalyst which is applicable in all polymerization processes is comprised of the reaction product of (A) a supported organoaluminum compound and (B) a metallocene catalyst component.Type: GrantFiled: June 7, 1995Date of Patent: March 25, 1997Assignee: Hoechst AktiengesellschaftInventors: Hans-Friedrich Herrmann, Bernd Bachmann, Walter Spaleck
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Patent number: 5604172Abstract: A process is provided for preparing a shape-shifted catalyst component comprising (1) contacting a dihydrocarbyloxide magnesium compound with carbon dioxide in the presence of a slurrying agent to form a slurry of a carboxylated dihydrocarbyloxide magnesium compound; (2) adding a filler to the slurry either before or after the carboxylation of step (1); (3) spray drying the slurry of step (2) to evaporate the slurrying agent and to produce solid particles of the carboxylated dihydrocarbyloxide magnesium compound incorporating the filler; and, optionally, (4) heating the solid particles to remove carbon dioxide to produce a shape-shifted dihydrocarbyloxide magnesium compound component. A catalyst system using the component and a polymerization process employing the catalyst system are also provided.Type: GrantFiled: February 2, 1996Date of Patent: February 18, 1997Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Burkhard E. Wagner, Daniel P. Zilker, Jr., Robert J. Jorgensen
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Patent number: 5604171Abstract: Catalytic composition which may be used for the polymerization of alpha-olefins, comprising:(a) a solid catalyst comprising on titanium trichloride (TiCl.sub.3),(b) a non-halogen-containing cocatalyst comprising at least one non-halogen-containing organoaluminium compound,characterized in that the non-halogen-containing cocatalyst additionally contains at least one aminoalane containing no active hydrogen.Such a catalytic system may additionally contain a tertiary constituent chosen from oxygenated organosilicon compounds.Type: GrantFiled: November 4, 1994Date of Patent: February 18, 1997Assignee: Solvay (Societe Anonyme)Inventors: Herve Collette, Sabine Pamart
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Patent number: 5578537Abstract: A supported polymerization catalyst which is applicable in all polymerization processes is comprised of the reaction product of (A) a supported organoaluminum compound and (B) a metallocene catalyst component.Type: GrantFiled: October 7, 1994Date of Patent: November 26, 1996Assignee: Hoechst AktiengesellschaftInventors: Hans-Friedrich Herrmann, Bernd Bachmann, Walter Spaleck
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Patent number: 5567665Abstract: A process is provided for preparing a shape-shifted catalyst component comprising (1) contacting a dihydrocarbyloxide magnesium compound with carbon dioxide in the presence of a slurrying agent to form a slurry of a carboxylated dihydrocarbyloxide magnesium compound; (2) adding a filler to the slurry either before or after the carboxylation of step (1); (3) spray drying the slurry of step (2) to evaporate the slurrying agent and to produce solid particles of the carboxylated dihydrocarbyloxide magnesium compound incorporating the filler; and, optionally, (4) heating the solid particles to remove carbon dioxide to produce a shape-shifted dihydrocarbyloxide magnesium compound component. A catalyst system using the component and a polymerization process employing the catalyst system are also provided.Type: GrantFiled: May 23, 1995Date of Patent: October 22, 1996Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Burkhard E. Wagner, Daniel P. Zilker, Jr., Robert J. Jorgensen
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Patent number: 5561091Abstract: A catalyst composition for producing linear low density polyethylene with relatively narrower molecular weight distributions is described. The catalyst is formed by treating silica having reactive OH groups with a dialkylmagnesium in a solvent for said dialkylmagnesium; then adding to said magnesium-containing support a mixture of ROH and SiCl.sub.4 to form an intermediate which is subsequently treated with a transition metal to form a transition metal-containing intermediate, the catalyst precursor. The catalyst precursor is activated with a trialkylaluminum compound.Type: GrantFiled: May 2, 1995Date of Patent: October 1, 1996Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 5547675Abstract: This invention comprises a catalyst system and a process using such catalyst system for the production of high molecular weight polyolefins, particularly polyethylene and higher poly-.alpha.-olefin, and copolymers of ethylene and/or .alpha.-olefins with other unsaturated monomers, including diolefins, acetylenically unsaturated monomers and cyclic olefins. The catalyst system comprises three components, a monocyclopentadienyl Group IV B transition metal compound, an alumoxane, and a modifier. The catalyst system is highly active, at low ratios of aluminum to the Group IV B transition metal, hence catalyzes the production of a polyolefin product containing low levels of catalyst metal residue.Type: GrantFiled: November 30, 1994Date of Patent: August 20, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Jo Ann M. Canich
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Patent number: 5543377Abstract: An olefin polymerization catalyst of the present invention comprises (A) a metallocene compound, (B) an organoaluminum oxy compound, and (C) at least one kind of carbonyl-containing compound selected from ketoalcohol and .beta.-diketone, and optionally (D) an organoaluminum compound, and therefore, the catalyst is excellent in polymerization activity per catalyst unit weight, and is capable of giving olefin (co)polymers having high molecular weight.A supported olefin polymerization catalyst and its olefin prepolymerized catalyst of the present invention are excellent in polymerization activity per catalyst unit weight, and is capable of giving olefin (co)polymers having uniform particle size.Type: GrantFiled: June 1, 1995Date of Patent: August 6, 1996Assignee: Mitsui Petrochemical Industries Co., Ltd.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu
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Patent number: 5543376Abstract: A process is provided to produce polyolefins having a multimodal molecular weight distribution at the molecular level by contacting at least one mono-1-olefin in a polymerization zone, under polymerization conditions, with dual site supported chromium polymerization catalyst systems. Such a polymerization catalyst system comprises an inorganic oxide supported chromium oxide catalyst system and a chromocene compound, wherein the supported catalyst system and chromocene compound are contacted in a polymerization reactor. The resultant, recovered polymer has at least a bimodal, or broad, molecular weight distribution.Type: GrantFiled: April 13, 1995Date of Patent: August 6, 1996Assignee: Phillips Petroleum CompanyInventor: Joseph J. Bergmeister
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Patent number: 5541271Abstract: A polyolefin having superior particle properties such as an extremely high bulk density, a large average particle diameter and a narrow particle size distribution, and having a narrow molecular weight distribution, is obtained in high yield, by polymerizing an olefin, using a catalyst comprising a solid catalyst component and an organometallic compound, the solid catalyst component being obtained by reacting a) a silicon oxide and/or an aluminum oxide, the reaction product of an organomagnesium compound and a compound of the general formula Me(OR).sub.n X.sub.Z-n, and a titanium compound, in the presence of ROH, and further reacting the resulting reaction product with a compound of the general formula AlR.sub.q X.sub.3-q.Type: GrantFiled: January 30, 1995Date of Patent: July 30, 1996Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Shiraishi Takeichi, Kunihiro Suzuki, Mitsuo Okamoto, Katsumi Usui, Hiroyuki Shimizu, Kazuo Matsuura
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Patent number: 5529965Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported mixed metallocene/non-metallocene catalyst useful in a process for polymerizing olefins.Type: GrantFiled: October 28, 1994Date of Patent: June 25, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang
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Patent number: 5521135Abstract: A solid component of catalyst for the (co)polymerization of ethylene is composed of a silica carrier and a catalytically active part including titanium, magnesium, chlorine and alkoxylic groups and is obtained: by suspending an activated silica in a solution of magnesium chloride and titanium tetraalcoholate in a liquid aliphatic acid ester; eliminating the aliphatic acid ester from the resulting suspension to recover a solid; and making this solid react with an aluminium alkyl chloride. It is preferable to add also some measured quantities of a silicon halide to the solution in aliphatic acid ester.Type: GrantFiled: December 14, 1993Date of Patent: May 28, 1996Assignee: ECP Enichem Polimeri s.r.l.Inventors: Luciano Luciani, Maddalena Pondrelli, Renzo Invernizzi, Italo Borghi
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Patent number: 5516737Abstract: This invention is generally directed toward a catalyst system useful for polymerizing olefins. The catalyst system of this invention comprises a supported bulky ligand transition metal compound and a separately supported cocatalyst or activator for the compound.Type: GrantFiled: June 6, 1995Date of Patent: May 14, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Moses O. Jejelowo
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Patent number: 5514634Abstract: An ethylene polymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a dialkylmagnesium compound, contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as tetraalkoxysilanes, e.g. tetraethyl orthosilicate, and incorporating a transition metal component, such as titanium tetrachloride, in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with dimethylaluminum chloride as a cocatalyst results in a catalyst system which is effective for the production of ethylene copolymers with multimodal molecular weight distributions.Type: GrantFiled: June 10, 1994Date of Patent: May 7, 1996Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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Patent number: 5506183Abstract: Polyolefins having better particle properties are obtained by polymerizing olefins in the presence of a catalyst comprising a solid catalyst component and an organometallic compound, the said solid catalyst component being prepared by reacting the following components [I] and [II] and further reacting the resulting reaction product with the following component [III]:[I] a reaction product obtained by reacting:(1) a silicon oxide and/or an aluminum oxide, and(2) a titanium compound, or a titanium compound and a vanadium compound, and further reacting the resulting reaction product with:(3) an organoaluminum compound;[II] a reaction product obtained by the reaction of:(1) a magnesium halide, and(2) a compound represented by the general formula Me(OR).sub.n X.sub.z-n wherein Me represents an element of Groups I to IV in the Periodic Table, z represents the valence of the element Me, n is 0<n.ltoreq.Type: GrantFiled: August 9, 1994Date of Patent: April 9, 1996Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Takeichi Shiraishi, Sinichi Yanahashi, Hiroyuki Shimizu, Kazuo Matsuura
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Patent number: 5491207Abstract: Disclosed is a process for preparing high molecular weight ethylene-.alpha.-olefin elastomers, preferably an ethylene-propylene elastomer, by liquid phase polymerization of the requisite monomers in the presence of a metallocene/alumoxane catalyst complex. Preferably, the process is carried out as a slurry polymerization utilizing the metallocene/alumoxane catalyst in supported form on a silica gel support with the .alpha.-olefin monomer maintained in liquid state and used in excess to serve as a polymerization diluent. The metallocene component of the catalyst by which the process is practiced is of the formula: ##STR1## wherein M is zirconium, titanium or hafnium; R.sup.1 and R.sup.2 are independently a C.sub.1 -C.sub.20 linear, branched or cyclic alkyl group; X an alkyl, aryl, halide, hydride or oxygen bridge of a zirconocene dimer; "y" and "z" are independently numbers 0, 1 or 2; and M is preferably zirconium.Type: GrantFiled: December 14, 1993Date of Patent: February 13, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Elvin L. Hoel
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Patent number: 5480850Abstract: A catalyst system comprising:(a) a catalyst precursor consisting essentially of the reaction product of vanadium (acetylacetonate).sub.3 and a compound having the formula AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is independently chlorine, bromine, or iodine; and a is 1 or 2; the atomic ratio of aluminum to vanadium in the precursor is 1:1 to 3:1; and the oxidation state of the vanadium in the reaction product is plus 2;(b) optionally, a support for said precursor; and(c) a halide substituted hydrocarbyl aluminum cocatalyst; and(d) optionally, a promoter, which is a chlorinated ester having at least 2 chlorine atoms; a saturated or unsaturated aliphatic halocarbon having at least 3 carbon atoms and at least 6 halogen atoms; or a haloalkyl substituted aromatic hydrocarbon wherein the haloalkyl substituent has at least 3 halogen atoms.Type: GrantFiled: June 28, 1993Date of Patent: January 2, 1996Assignee: Union Carbide Chemical & Plastics Technology CorporationInventors: Kevin J. Cann, James W. Nicoletti, Sergey A. Vasnetsov
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Patent number: 5474961Abstract: Metallocene catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alkenes are obtainable by deactivation of a preactivated metallocene catalyst system which contains, as active components, a metallocene complex of a metal of subgroup IV or V of the Periodic Table and an oligomeric alumoxane compound and, if required, subsequent reactivation.Type: GrantFiled: March 8, 1994Date of Patent: December 12, 1995Assignee: BASF AktiengesellschaftInventors: Rueger Schlund, Meinolf Kersting, Klaus-Dieter Hungenberg
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Patent number: 5474962Abstract: The present invention provides a powder catalyst composition for producing by gas-phase polymerization olefin polymers having excellent polymer qualities and good particle properties in a high yield.The powder catalyst composition comprises fine particles of the following Component (B) coated with the following Component (A), and is characterized in that the ratio of the Component (A) to the Component (B) based on percent by weight ranges from 5:50 to 95:50: Component (A): an inorganic compound in the form of fine particles having an average particle diameter of 0,003-1 .mu.m and mainly comprising an inorganic oxide, and Component (B): a solution or dispersion in a hydrocarbon of the following Sub-components (i) and (ii): Sub-component (i): a compound of a transition metal belonging to the IVB group of the Periodic Table, and Sub-component (ii): an alumoxane, a Lewis acid, or an ionic compound which can convert the Sub-component (i) upon reaction therewith into a cation.Type: GrantFiled: September 22, 1993Date of Patent: December 12, 1995Assignee: Mitsubishi Petrochemical Company LimitedInventors: Tadashi Takahashi, Kazuhiro Yamamoto, Katsumi Hirakawa
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Patent number: 5473028Abstract: A support containing methylalumoxane and derivatives thereof is described which is formed by an incipient impregnation technique. The most preferred support is silica. Incipient impregnation in accordance with the invention provides a supported alumoxane, methylalumoxane, which substantially eliminates the problem of fluid bed reactor fouling when methylalumoxane is introduced into the reactor during its operation. The process comprises providing methylaluminoxane in particulate form for use as a catalytic component in the fluidized bed gas phase polymerization process.In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluid bed gas phase.Type: GrantFiled: April 19, 1994Date of Patent: December 5, 1995Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
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Patent number: 5470812Abstract: An ethylene copolymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a magnesium alkyl and contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as a tetraalkyl orthosilicate, e.g. tetraethyl orthosilicate (TEOS). A transition metal component such as titanium tetrachloride is then incorporated into the support in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with a trialkylaluminum compound results in a catalyst which is effective for the production of ethylene copolymers.Type: GrantFiled: November 15, 1993Date of Patent: November 28, 1995Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 5466649Abstract: This invention is generally directed toward a catalyst system useful for polymerizing olefins. The catalyst system of this invention comprises a supported bulky ligand transition metal compound and a separately supported cocatalyst or activator for the compound.Type: GrantFiled: October 15, 1993Date of Patent: November 14, 1995Assignee: Exxon Chemical Patents Inc.Inventor: Moses O. Jejelowo
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Patent number: 5466766Abstract: 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: GrantFiled: November 17, 1993Date of Patent: November 14, 1995Assignee: Phillips Petroleum CompanyInventors: Konstantinos Patsidis, Bernd Peifer, Syriac J. Palackal, Helmut G. Alt, M. Bruce Welch, Rolf L. Geerts, Darryl R. Fahey, Harold R. Deck
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Patent number: 5455316Abstract: The present invention relates to a solid catalyst composed of a specific solid catalyst component [A-1], the catalyst containing the solid catalyst and the olefin polymerization process using the solid catalyst, in which the solid catalyst component [A-1] comprises; (a-1) a particulate carrier composed of a specific oxide of a metal; (a-2) an organoaluminum oxy compound; and (a-3) a specific transition metal compound containing a specific ligand, wherein the organoaluminum oxy compound (a-2) and the transition metal compound (a-3) are supported on the particulate carrier (a-1).The catalysts are applicable to a suspension polymerization and a vapor phase polymerization, and capable of preparing spherical olefin polymers excellent in particle characteristics at high polymerization activity.Type: GrantFiled: February 17, 1994Date of Patent: October 3, 1995Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Kunio Yamamoto
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Patent number: 5424263Abstract: A catalyst component useful in the polymerization of olefins is disclosed. The catalyst component comprises the product obtained by steps of (a) contacting silica with at least one hydrocarbon soluble magnesium-containing compound; (b) contacting the product of step (a) with component (1), a heterocyclic fused ring compound substituted with at least one oxygen atom, and component (2), a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof, with the proviso that components (1) and (2) be present such that the molar ratio of component (2) to component (1) is at least about 4:1; and (c) contacting the product of step (b) with a titanium-containing compound having the structural formula TiX.sub.m (OR).sub.n, where X is halogen; R is hydrocarbyl; m is an integer of 1 to 4; and n is 0 or an integer of 1 to 3 with the proviso that the sum of m and n is 4.Type: GrantFiled: April 23, 1993Date of Patent: June 13, 1995Assignee: Quantum Chemical CorporationInventor: Charles K. Buehler
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Patent number: 5422325Abstract: This invention is generally directed toward a supposed catalyst system useful for polymerizing olefins. The method for supposing the catalyst of the invention provides for a supposed metallocene catalyst able to produce polymers having broader molecular weight distribution and a higher molecular weight. Not only are such polymers easily processable as compared with metallocene polymers produced with other support methods but the methods of this invention provides for a supposed catalyst with increased activity.Type: GrantFiled: September 17, 1993Date of Patent: June 6, 1995Assignee: Exxon Chemical Patents Inc.Inventors: Moses O. Jejelowo, Robert L. Bamberger
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Patent number: 5420090Abstract: A transition metal containing catalyst useful for the polymerization of .alpha.-olefins is prepared by (A) forming in an inert atmosphere which excludes oxygen and moisture a slurry of (1) a porous inorganic oxide support material selected from the group consisting of silica, alumina, or a combination of silica and alumina, said support material containing not greater than about 5 millimoles of hydroxyl groups per gram of support material and a particle size not greater than about 10 microns and a surface area of from about 50 to about 800 m.sup.2 /g in an inert organic liquid medium; (B) mixing said slurry with (2) an alkoxide and stirring the resultant mixture at a temperature of from about -20.degree. C. to about 120.degree. C. for a time sufficient to saturate the surface of the support material: (C) mixing the product form (B) with (3) a titanium compound or a combination of a titanium compound and (4) a vanadium compound and stirring the resultant mixture at a temperature of from about -20.degree. C.Type: GrantFiled: February 24, 1993Date of Patent: May 30, 1995Assignee: The Dow Chemical CompanyInventors: Lee Spencer, Brian W. S. Kolthammer
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Patent number: 5413979Abstract: The invention relates to a method for the preparation of a solid procatalyst composition for a catalyst system intended for the polymerization of olefins, wherein a magnesium halide, such as magnesium chloride, is dissolved and/or slurried in a mono-carboxylic acid alkyl ester, such as ethyl acetate, is impregnated into a support material, dried, treated with an organometallic compound or a silicon compound and thereafter with a transition metal compound. The invention also relates to such a procatalyst composition and its use together with a cocatalyst for the polymerization of olefins. According to the invention it has been possible to increase the activity of the catalyst composition by using a silanated support material, such as silanated silica, which is then treated with an organometallic or silicon compound before treatment with a transition metal compound. The silanated silica is preferably a silicon dioxide which has been heat-treated at 1000.degree.-200.degree.Type: GrantFiled: June 16, 1992Date of Patent: May 9, 1995Assignee: Borealis Holding A/SInventors: Arja Kostiainen, Bill Gustafsson, Pekka Sormunen
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Patent number: 5411926Abstract: A high activity olefin polymerization catalyst catalyzes the production of polymeric lower .alpha.-olefin having good properties. The catalyst is produced from an organoaluminum cocatalyst, a selectivity control agent and a novel olefin polymerization procatalyst which is prepared by contacting a tetravalent titanium halide, an optional inert diluent, an electron donor and a novel solid procatalyst precursor obtained by contacting (a) a carbonated magnesium alkoxide of the general formula ##STR1## wherein R is a hydrocarbyl group having up to 12 carbon atoms and x is a number from 0.1 to about 2; and (b) at least one halogenating compound which is a non-transition metal halogenated compound or non-metallic halogenated compound. A process for polymerizing one or more .alpha.-olefins utilizing the novel high activity polymerization catalyst.Type: GrantFiled: February 8, 1994Date of Patent: May 2, 1995Assignee: Shell Oil CompanyInventors: Stanley E. Wilson, Richard A. Kemp
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Patent number: 5399539Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.Type: GrantFiled: June 24, 1994Date of Patent: March 21, 1995Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn
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Patent number: 5399636Abstract: A composition is provided comprising a metallocene having the formula of: ##STR1## wherein each Z can be the same or different hydrocarbyl radical selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and mixtures thereof; each X can be the same or different and is selected from the group consisting of hydrogen, fluorine, chlorine, bromine, iodine, R, OR, NR.sub.2, PR.sub.2, or OQ, or mixtures thereof wherein the R is a C.sub.1 -C.sub.20 hydrocarbyl radical and Q is an inorganic moiety selected from the group consisting of silica, alumina, clay, phosphated alumina, and mixtures thereof; each Y can be the same or different and is an alkyl group, hydrogen, fluorine, chlorine, bromine, iodine, or mixtures thereof; E is selected from C, Sn, Si, Ge, B, Al, N, or P; M is a metal selected from Ti, Zr, Hf, Sc, Y, V, or La; m is a number sufficient to fill out the valences of metal M; and n is 1 or 2.Type: GrantFiled: June 11, 1993Date of Patent: March 21, 1995Assignee: Phillips Petroleum CompanyInventors: Helmut G. Alt, Konstantinos Patsidis, M. Bruce Welch, Rolf L. Geerts, Bernd Peifer, Syriac J. Palackal
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Patent number: 5393720Abstract: Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal compound having at least one oxo, thio, imido or phosphido group bonded directly to the Group 6b metal, and at least one organic radical bonded to the Group 6b metal through a carbon atom, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound cocatalyst.Type: GrantFiled: June 13, 1994Date of Patent: February 28, 1995Assignee: Chevron Chemical CompanyInventors: Michael J. Carney, David L. Beach
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Patent number: 5376612Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.Type: GrantFiled: August 20, 1993Date of Patent: December 27, 1994Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
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Patent number: 5348925Abstract: A solid component of catalyst, active in the polymerization of propylene and other .alpha.-olefins in stereoregular polymers, is obtained:(i) by treating a non-activated silica support in particles with a tin tetrahalide, to at least partially block the hydroxylic groups of the silica and to obtain a blocked silica;(ii) by impregnating the blocked silica with magnesium dialkyl or magnesium alkyl halide to make the magnesium compound react with the tin compound and with possible residual hydroxylic groups of the silica and to obtain a support;(iii) by halogenating the support by contact with a halogenating agent selected from the halides of tin, antimonium or silicon to obtain a halogenated support;(iv) by titanating the halogenated support with an excess of a titanium tetrahalide to obtain a titanated support;(v) by putting the titanated support in contact with a Lewis base, to obtain a solid component of catalyst.Type: GrantFiled: February 22, 1993Date of Patent: September 20, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Federico Milani, Luciano Luciani, Antonio Labianco
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Patent number: 5346872Abstract: The present invention relates to a novel catalyst component for ethylene polymerization comprising vanadium and titanium. Moreover, when the vanadium/titanium containing catalyst of the present invention is employed with an aluminum-containing cocatalyst enhanced activity as well as melt index is obtained.The present invention is directed to a novel halosilane cocatalyst component which, when used in conjunction with an aluminum containing cocatalyst, is effective in increasing the activity of a silica supported titanium/vanadium containing solid catalyst component in the polymerization of ethylene and/or .alpha.-olefins. In addition to the increased catalytic activity, the polymers produced by the present invention exhibit improved melt index values compared with melt index values typically obtained using prior art catalyst systems. Thus, the catalyst system of the instant invention represent an advancement in the art in view of the combination of increased activity, i.e.Type: GrantFiled: January 29, 1993Date of Patent: September 13, 1994Assignee: Quantum Chemical CorporationInventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
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Patent number: 5344803Abstract: The present invention is directed to a novel halosilane cocatalyst component which, when used in conjunction with an aluminum containing cocatalyst, is effective in increasing the activity of a supported magnesium/titanium containing catalyst in the polymerization of ethylene and .alpha.-olefins. In addition to the increased catalytic activity, the polymers produced by the present invention are characterized as having an unexpected enhancement in the polymer melt index. Thus, the catalyst system of the instant invention represents an advancement in the art in view of the combination of increased activity, i.e., yield of polymer produced, and physical properties of the polyolefin product.In another aspect of the present invention, a process for polymerizing .alpha.-olefins is disclosed.Type: GrantFiled: January 29, 1993Date of Patent: September 6, 1994Assignee: Quantum Chemical CorporationInventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
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Patent number: 5340785Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.Type: GrantFiled: February 26, 1993Date of Patent: August 23, 1994Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn
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Patent number: 5336652Abstract: There is disclosed a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid support, containing magnesium, with a silane compound of the empirical formulaR.sup.1.sub.x SiR.sup.2.sub.ywherein Si is silicon atom; x is 1, 2, 3, or 4 and y is 0, 1, 2, or 3, provided that x+y is 4; R.sup.1 is R.sub.w --O-- wherein O is oxygen and R.sub.w is hydrocarbyl of 1 to 10 carbon atoms; and R.sup.2 is halogen or hydrocarbyl of 1 to 10 carbon atoms, or hydrogenand a transition metal compound, e.g., a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers. Also disclosed are methods of preparing polymers with the catalyst composition and the resulting polymers.Type: GrantFiled: November 6, 1991Date of Patent: August 9, 1994Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 5334567Abstract: The present invention is directed to a novel halosilane cocatalyst component which may be used in conjunction with an aluminum-containing cocatalyst to provide enhanced catalytic activity of a vanadium based solid catalyst component in the polymerization of .alpha.-olefins. In addition to the enhancement in the catalytic activity obtaining using the present catalyst system, the resultant polymer produced by the present invention exhibits improved physical properties compared with polymers produced by prior art vanadium based catalyst systems. Thus, the catalyst system of the instant invention represents an advance in the art in view of the combination of increased catalytic activity, i.e. yield of polymer produced, and enhanced physical properties of the polyolefin produced.In accordance with the present invention, a catalyst system is provided which comprises a solid catalyst component and a halosilane cocatalyst component.Type: GrantFiled: January 29, 1993Date of Patent: August 2, 1994Assignee: Quantum Chemical CorporationInventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
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Patent number: 5332707Abstract: A magnesium-containing supported titanium-containing and a hafnium-containing and/or zirconium-containing catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins.Type: GrantFiled: July 31, 1992Date of Patent: July 26, 1994Assignee: Amoco CorporationInventors: Nicholas M. Karayannis, Steven A. Cohen, Julie L. Ledermann