Utilizing High Molecular Weight Synthetic Polymer Patents (Class 502/109)
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Patent number: 6461993Abstract: This invention concerns a method for preparing a hydrogenation catalyst system involving the reaction of a group 4 metallocene (A) with a metal hydride or an organometallic compound (B) at a (B)/(A) molar ratio that is larger than 10 followed by the activation of the resulting catalyst mixture with hydrogen at a hydrogen pressure p (in MPa) and at a temperature T (in ° C.), wherein a neutralising agent (C) that is capable of reacting with the compound (B) is added to the catalyst mixture a) either prior to the activation, or b) within t hours from the activation wherein t equals x divided by (p*T*(B)/(A)), and x=10,000, and a process for the hydrogenation of an olefinically unsaturated compound with hydrogen in the presence of a hydrogenation catalyst system obtained by the method of the invention.Type: GrantFiled: October 8, 1999Date of Patent: October 8, 2002Assignee: Shell Oil CompanyInventors: Harry Van Der Heijden, Hendrik Van De Weg
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Patent number: 6448348Abstract: A catalytic polymerization process for preparing polymer products is provided. The polymerization process is either homopolymerization of olefins or copolymerization of olefins with alpha-olefins. The polymerization process is conducted in the presence of a solid catalyst precursor and a cocatalyst. The catalyst precursor includes a transition metal, a magnesium compound, an aluminum compound and a polyvinylchloride (PVC) support.Type: GrantFiled: June 9, 2000Date of Patent: September 10, 2002Assignee: Saudi Basic Industries CorporationInventors: Akhlaq Moman, Atieh Abu-Raqabah, Orass Hamed, Raju Raghavan
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Patent number: 6444766Abstract: A process for preparing a supported catalyst comprises the steps of (1) preparation of a copolymer having comonomer units which comprise leaving groups; (2) polymer-analogous reaction with a substituted or unsubstituted cyclopentadienyl compound, and (3) reaction of the copolymer of (2) with a mono-Cp-metallocene compound.Type: GrantFiled: November 8, 2000Date of Patent: September 3, 2002Assignees: Basell Polyolefine GmbH, Max-Planck-GesellschaftInventors: Martin Stork, Klaus Müllen, Markus Klapper, Matthias Koch, Heike Gregorius, Ursula Rief, Marc Oliver Kristen
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Patent number: 6444604Abstract: Supported catalysts for the polymerization of olefins comprise the following components: (A) a porous organic support functionalised with groups having active hydrogen atoms; (B) an organo-metallic compound of aluminium containing heteroatoms selected from oxygen, nitrogen and sulphur; and (C) a compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing ligands of the cyclopentadienyl type. These supported catalysts, obtainable in the form of spherical particles, can be used in the polymerization reaction of olefins either in liquid or in gas phase, thus producing polymers endowed with a controlled morphology and with a high bulk density.Type: GrantFiled: June 8, 2000Date of Patent: September 3, 2002Assignee: Basell Technology Company BVInventors: Enrico Albizzati, Tiziano Dall'Occo, Luigi Resconi, Fabrizio Piemontesi
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Patent number: 6432860Abstract: Supported stereospecific catalysts and processes for the stereotactic propagation of a polymer chain derived from ethylenically unsaturated monomers which contain three or more carbon atoms or which are substituted vinyl compounds, such as styrene and vinyl chloride. One application is the stereospecific propagation of C3-C4 alpha olefins, particularly the polymerization of propylene to produce syndiotactic polypropylene over a supported metallocene catalyst comprising a stereospecific metallocene catalyst component incorporating a metallocene ligand structure having two sterically dissimilar cyclopentadienyl ring structures coordinated to the central transition metal atom. Both of the cyclopentadienyl groups are in a relationship with one another by virtue of bridge or substituent groups, which provide a stereorigid relationship relative to the coordinating transition metal atom to prevent rotation of said ring structures.Type: GrantFiled: March 22, 1999Date of Patent: August 13, 2002Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, Margarito Lopez
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Patent number: 6423660Abstract: Supported catalysts for the polymerization of olefins comprise the following components: (A) a porous organic support functionalised with groups having active hydrogen atoms; (B) an organo-metallic compound of aluminium containing heteroatoms selected from oxygen, nitrogen and sulphur; and (C) a compound of a transition metal selected from those of groups IVb, Vb or VIb of the Periodic Table of the Elements, containing ligands of the cyclopentadienyl type. These supported catalysts, obtainable in the form of spherical particles, can be used in the polymerization reaction of olefins either in liquid or in gas phase, thus producing polymers endowed with a controlled morphology and with a high bulk density.Type: GrantFiled: January 9, 1998Date of Patent: July 23, 2002Assignee: Basell Technology Company BVInventors: Enrico Albizzati, Tiziano Dall'Occo, Luigi Resconi, Fabrizio Piemontesi
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Patent number: 6417320Abstract: The production of linear polyester by the interchange of ester radicals or esterification and polycondensation of multivalent alcohols with multivalent carboxylic acids takes place by means of catalysts. In order that the catalyst features the lowest possible content of catalytically active metal compound, the carrier substance that forms the heterogeneous phase comprises particles of the finest grain and of porous structure and features a surface of great inner, reactive and/or coordinated centers, whereby a catalytically active metal compound is adsorbed in the pores.Type: GrantFiled: February 25, 2000Date of Patent: July 9, 2002Assignee: Zimmer AktiengesellschaftInventors: Brigitta Otto, Karl Ulrich Thiele, Xiaogang Guo
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Patent number: 6413901Abstract: A catalyst composition for alpha olefin polymerization is provided. The catalyst composition is prepared by a process including treating PVC containing particles with an organomagnesium compound in an inert solvent, contacting the treated PVC containing particles with a transition metal compound from the group TiCl4, VCl4 or ZrCl4, in the absence of an electron donor, and activating the product particles with a cocatalyst. An organoaluminum compound can also be mixed with the organomagnesium compound prior to treating the PVC containing particles.Type: GrantFiled: June 9, 2000Date of Patent: July 2, 2002Assignee: Saudi Basic Industries CorporationInventors: Akhlaq Moman, Atieh Abu-Raqabah, Navin Nallaveerapan
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Patent number: 6403519Abstract: Process for the preparation of a catalyst for the polymerization of alpha-olefins involves contacting a porous polyolefin support with a solution containing an activator (ii) to form a suspension. The suspension is evaporated in a reactor fitted with a stirrer comprising a scraping element. The scraping element follows the walls of the reactor at a distance from 2 to 200 times the mean particle diameter of the support. The catalyst includes a compound of a transition metal (i) from Groups 4 to 6 of the Periodic Table and at least one optionally substituted cyclopentadiene ligand and an aluminoxane activator (ii). The aluminoxane activator (ii) and transition metal compound are supported on the porous polyethylene support (iii). The walls of the reactor show no traces of crusting.Type: GrantFiled: December 21, 1999Date of Patent: June 11, 2002Assignee: Solvay Polyolefins Europe-Belgium (Societe Anonyme)Inventors: Philippe Francois, Serge Bettonville, Dominique Marchand
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Patent number: 6384159Abstract: The present invention relates to a process to produce polyethylene through homopolymerization or copolymerization of ethylene with alpha-olefins in the presence of a titanium amide catalyst supported by an organic polymer material, for the production of moldings, such as through extrusion, injection molding, film blowing, sintering under pressure or ram extrusion. The catalyst according to the present invention contains a partially chloromethylated styrene divinyl benzene copolymer as the organic polymer material, a complex compound supported by it, which contains Mg, Al and Ti.Type: GrantFiled: April 21, 2000Date of Patent: May 7, 2002Assignee: Buna Sow Leuna Olefinverbund GmbHInventors: Jürgen Schellenberg, Heinz-Jürgen Kerrinnes, Gerd Fritzsche, Gerd Lohse
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Patent number: 6383969Abstract: Disclosed is for the preparation of a catalytic composition for the polymerization of alpha-olefins. The catalyst comprises a compound of a transition metal (i) of Groups 4 to 6 of the Periodic Table, containing at least one possibly substituted cyclopentadiene ligand, and an activator (ii) chosen from aluminoxanes and ionizing agents supported on a support (iii) consisting of porous particles of polyolefin(s). Preparation includes a preliminary polymerization which includes contact with an alpha-olefin, under polymerizing conditions, in a diluent whose kinematic viscosity, measured at 20° C., is from 3 to 3000 cSt (centistokes) from 3 to 3000 mm2/s, such as mineral oil which may be derived from coal tars and petroleum fractions, to form from 0.01 to 50 g of polyolefin per g of catalyst containing compounds (i), (ii) and (iii).Type: GrantFiled: December 21, 1999Date of Patent: May 7, 2002Assignee: Solvay Polyolefins Europe - BelgiumInventors: Philippe Francois, Serge Bettonville, Dominique Marchand
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Patent number: 6358876Abstract: The invention relates to particles comprises of organopolysiloxane microgel particles having a diameter of 5 to 200 nm and organo-aluminum compounds immobilized thereon. The particles can be used as cocatalysts together with metal compounds of the 4, 5, 6 and 8-10 sub-groups of the periodic table for oligomerization, cyclization of polymerization of olefins.Type: GrantFiled: April 19, 2000Date of Patent: March 19, 2002Assignee: Wacker-Chemie GmbHInventors: Helmut Alt, Frank Baumann, Johann Weis, Alexander Köppl
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Publication number: 20020013217Abstract: The present invention relates to a supported catalyst for the polymerization of olefins, which can be prepared by reacting the reaction product formed from an aluminoxane and at least one metallocene with a microporous, polymeric support.Type: ApplicationFiled: March 31, 1993Publication date: January 31, 2002Applicant: Hans-Friedrich HerrmannInventors: HANS-FRIEDRICH HERRMANN, BERND BACHMANN, BERNHARD HIERHOLZER, WALTER SPALECK
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Patent number: 6340771Abstract: Aluminoxanes are used as activators for the gas, solution or slurry phase polymerization of olefins in the presence of single site catalysts. Aluminoxanes contain residual aluminum alkyls which may poison the catalysts. The residual aluminum alkyls may be bound an/or removed from the aluminoxanes by treatment with carbohydrates such as cellulose, starch or sugar.Type: GrantFiled: December 22, 1999Date of Patent: January 22, 2002Assignee: Nova Chemicals (International) S. A.Inventors: Peter Phung Minh Hoang, Dusan Jeremic, Jason Roy Kearns, Iain McLaren Coulter, Robert D. Donaldson
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Publication number: 20010044374Abstract: A process for the preparation of a supported catalyst is disclosed, comprising the steps ofType: ApplicationFiled: January 31, 2001Publication date: November 22, 2001Inventor: Marc John Payne
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Patent number: 6268453Abstract: A solid cocatalyst is prepared by reacting a suitable support base with an organoaluminum compound and then reacting that product with an activity promoting amount of water. The solid cocatalyst can be combined with a polymerization catalyst to form a catalyst system useful for the polymerization of olefins.Type: GrantFiled: October 18, 1999Date of Patent: July 31, 2001Assignee: Phillips Petroleum CompanyInventors: Alexander Köppl, Helmut G. Alt, Syriac J. Palackal, M. Bruce Welch
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Patent number: 6255244Abstract: A catalyst for polymerization of olefins or styrenes, which is prepared by contacting (A) a transition metal compound, (B) at least one material selected from the group consisting of oxygen-containing compounds and compounds which react with a transition metal compound to form an ionic complex, and optionally (C) an alkylating agent with each other, and contacting these materials (A), (B) and (C) with an adsorbing substance (D), during or after the contact of materials (A), (B) and (C) with each other, followed by removing the adsorbing substance (D) from the contacted materials (A), (B) and (C).Type: GrantFiled: September 8, 1999Date of Patent: July 3, 2001Assignee: Idemitsu Petrochemical Co., Ltd.Inventor: Nobuhiro Yabunouchi
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Publication number: 20010004657Abstract: An olefin (co-)polymer composition including 0.01 to 5.0 weight parts of high molecular weight polyethylene which is an ethylene homopolymer or an ethylene-olefin copolymer containing 50 weight % or more of an ethylene polymerization unit; and 100 weight parts of an olefin (co-)polymer other than the high molecular weight polyethylene, wherein said high molecular weight polyethylene has an intrinsic viscosity [&eegr;E] of 15 to 100 dl/g measured in tetralin at 135° C. or more, and said high molecular weight polyethylene exists as dispersed fine particles having a numerical average particle size of 1 to 5000 nm.Type: ApplicationFiled: September 14, 1998Publication date: June 21, 2001Applicant: CHISSO CORPORATIONInventors: JUN SAITO, HIDEO NOBUHARA, SHINGO KIKUKAWA, HITOSHI SATO, AKIRA YAMAUCHI
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Patent number: 6239060Abstract: 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: GrantFiled: December 31, 1998Date of Patent: May 29, 2001Assignee: Phillips Petroleum CompanyInventors: David W. Dockter, Bryan E. Hauger, M. Bruce Welch, Randall S. Muninger
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Patent number: 6221802Abstract: The invention comprises a catalyst support containing an &agr;-olefin polymer which is in the form of particles of mean size from 5 to 350 &mgr;m in which the pore volume generated by the pores of radius from 1,000 to 75,000 Å is at least 0.2 cm3/g. A catalyst usable for the polymerization of &agr;-olefins, including a compound containing at least one transition metal belonging to groups IIIb, IVb, IVb and VIb of the Periodic Table, bound in or on this support, is also described.Type: GrantFiled: January 16, 1998Date of Patent: April 24, 2001Assignee: Solvay Polyolefins Europe-BelgiumInventors: Jean-Louis Costa, Vincent Laurent, Philippe Francois, Dirk Vercammen
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Patent number: 6218331Abstract: The present invention is directed to a process of preparing a novel supported Ziegler-Natta catalyst useful for the polymerization of &agr;-olefins. More specifically, the supported Ziegler-Natta catalyst of the present invention comprises a particulate functionalized copolymeric support, at least one organometallic compound or complex and at least one transition metal compound. A novel method of preparing the particulate functionalized copolymeric support of the instant invention is also provided.Type: GrantFiled: June 27, 1997Date of Patent: April 17, 2001Assignee: Equistar Chemicals, L.P.Inventors: Anthony-J. DiMaio, Craig C. Meverden, Peter D. Becker
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Patent number: 6197985Abstract: A low-bulk density solid aluminoxane has an average particle diameter of 210 to 10,000 &mgr;m and a bulk density of from 0.01 to 1.0 g/cc. Representative solid aluminoxanes may be prepared from polymethylaluminoxane or mixed alkyl group aluminoxanes. The solid aluminoxanes are useful as catalyst carriers. When used to support a metallocene, the combination may be used, for example, as catalyst for olefin polymerization Also disclosed is a prepolymerized catalyst having an average particle diameter of from 500 to 5,000 &mgr;m, useful for olefin polymerization. An olefin is pre-polymerized in the presence of a metallocene catalyst component and a solid low bulk-density aluminoxane and, optionally, an organoaluminum compound.Type: GrantFiled: September 1, 1998Date of Patent: March 6, 2001Assignee: Mitsui Chemicals INCInventors: Atsuo Kobata, Kazuhito Gotoh, Shigeru Isayama, Tetsuhiro Matsumoto
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Patent number: 6100353Abstract: Supported catalyst systems are obtainable bya) application of a mixture ofA) at least one metallocene complex andB) at elast one metal compoundto a carrier which, if required, may have been pretreated, andb) subsequent activation by reaction with a solution or suspension of a compound forming metallocenium ions.Type: GrantFiled: September 6, 1995Date of Patent: August 8, 2000Assignee: BASF AktiengesellschaftInventors: John Lynch, David Fischer, Franz Langhauser, Hans-Helmut Gortz, Jurgen Kerth, Gunther Schweier
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Patent number: 6100214Abstract: The described invention provides a low fouling, high particle density polymerization process and an olefin polymerization catalyst composition comprising the reaction product of a) an organic polymeric support i) having a surface area of from about 1 to 10 m.sup.2 /g and ii) functionalized with an acidic proton-containing ammonium salt of a non-coordinating anion, and b) an organometallic transition metal compound having ancillary ligands, at least one labile ligand capable of abstraction by protonation by said ammonium salt and at least one labile ligand into which an olefinic monomer can insert for polymerization. In a preferred embodiment, the polymeric support has a surface area of .ltoreq.10 m.sup.2 /g and is particularly suitable for use with high activity organometallic, transition metal catalyst compounds.Type: GrantFiled: June 5, 1998Date of Patent: August 8, 2000Assignee: Exxon Chemical Patents Inc.Inventors: John F. Walzer, Jr., Anthony J. Dias, Jean M J Frechet, Stephen B. Roscoe
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Patent number: 6063725Abstract: An olefin polymerization catalyst system comprising an organic transition metal compound and a support, wherein an organic transition metal compound is soluble in an inert organic solvent and a support which is insoluble in the inert organic solvent, and the support comprises an organic high molecular weight compound which contains a specific carbonyl-containing group. The catalyst system can polymerize an olefin in a high activity, provides polymer with high stereoregularity, prevents adhesion or fouling of the polymer generated in the course of polymerization or an organic aluminum oxy compound on the inner wall of the reactor, leads to high bulk density of the polymer and very reduced level of fisheye and/or gel generation on the processed item, can maintain high productivity, can manufacture high quality product, and thus provides extremely high contribution in industry.Type: GrantFiled: November 4, 1996Date of Patent: May 16, 2000Assignee: Mitsui Chemicals, Inc.Inventors: Tadahiro Sunaga, Yukio Ishii, Tadashi Asanuma
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Patent number: 6048817Abstract: A particulate phyllosilicate mixture comprising a mixture containing a phyllosilicte belonging to the smectite group and a phyllosilicate belogning to the mica group, the phyllosilicate particle having a content of the phyllosilicate belonging to the smectite group of 0.1 to 50% by weight and optionally satisfying the following requirements (a) to (c):(a): the average particle diameter is 20 to 1000 .mu.m with not more than 20% of the total number of particles being accounted for by particles having a particle diameter of not more than 10 .mu.m;(b): the crushing strength of the particle is not less than 0.5 MPa as measured with a microcompression tester and(c): the bulk density of the particle of not less than 0.6 g/cm.sup.3.Polymerization of olefins with catalyst comprising the particulate phyllosilicate mixture as a carrier or support for the catalysts is also disclosed.Type: GrantFiled: April 24, 1998Date of Patent: April 11, 2000Assignee: Mitsubishi Chemical CorporationInventors: Takehiro Sagae, Yumito Uehara
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Patent number: 6040260Abstract: The present invention concerns prepolymerized catalyst composition for polymerization of .beta.-olefins, a process for the preparation thereof and a process for polymerization of .beta.-olefins. According to the polymerization process a procatalyst composition containing a transition metal is prepolymerized with a monomer in order to produce a prepolymerized Ziegler-Natta type catalyst composition and said catalyst composition is contacted with an alpha-olefin monomer, in particular with ethylene or propylene, for preparing a polymer. According to the invention the procatalyst composition is preferably prepolymerized in a medium which is inert to the catalyst components, the viscosity of the medium being so high that the catalyst does not substantially settle in this medium. Because the catalyst composition according to the invention does not have to be dried before being fed into the medium, its activity is high before and during polymerization.Type: GrantFiled: June 16, 1997Date of Patent: March 21, 2000Assignee: Borealis A/SInventors: Ismo Pentti, Pauli Leskinen
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Patent number: 6013594Abstract: This invention relates to catalyst supports made by spray drying an emulsion polymerized latex and the novel supported catalysts utilizing these supports. This invention further relates to a method for forming supported catalysts by spray drying a latex of microparticles containing catalyst or catalyst components. The polymizerable monomers used in the latex are e.g. styrenes, vinyl benzenes, vinyl cyclohexane and vinyl cyclohexene and can form homo- or copolymers which may be crosslinked. The catalysts supported include metallocenes as well as Ziegler-Natta catalysts. Processes of polymerizing olefins using such catalysts are also described.Type: GrantFiled: April 29, 1998Date of Patent: January 11, 2000Assignee: Exxon Chemical Patents, Inc.Inventors: Henry Wu-Hsian Yang, Anthony Nicholas Speca
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Patent number: 5990035Abstract: 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: GrantFiled: October 21, 1997Date of Patent: November 23, 1999Inventors: Alexander Koppl, Helmut G. Alt, Syriac J. Palackal, M. Bruce Welch
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Process for producing polymers of vinyl aromatic compounds using polymer-containing catalyst systems
Patent number: 5922819Abstract: Polymers of vinylaromatic compounds are prepared at from 0 to 150.degree. C. in the presence of catalyst systems which comprise as active constituentsA) compounds of the formula IXM(Z.sup.1).sub.z.sbsb.1 (Z.sup.2).sub.z.sbsb.2 (Z.sup.3).sub.z.sbsb.3 (I)where the substituents and indices have the following meanings:X is C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalky,C.sub.1 -C.sub.10 -alkoxy, C.sub.6 -C.sub.15 -aryl or a cyctopentadienyl group,M is a metal of transition groups II to VIII of the periodic Table of the Elements,Z.sup.1 to Z.sup.3are polymers of vinylaromatic compounds, dienes, acrylates or mixtures thereofandZ.sup.1 to Z.sup.3are 0, 1, 2 or 3, where 1.ltoreq.Z.sub.1 +Z.sub.2 +Z.sub.3 .ltoreq.3,andB) linear or cyclic aluminoxane compoundorcompounds which form metallocenium ions and are selected from the group consisting of strong, uncharged Lewis acids, ionic compounds having a Lewis-acid cation and ionic compounds having a Bronsted acid as cation.Type: GrantFiled: July 14, 1997Date of Patent: July 13, 1999Assignee: BASF AktiengesellschaftInventors: Josef Wunsch, Martin Lux, David Fischer -
Patent number: 5854164Abstract: A solid catalyst component (A) for olefin polymerization comprising Mg, Ti, a halogen and a cyclic organic nitrogen compound (C), a solid catalyst comprising the solid catalyst component and an organoaluminum compound, and a process for producing an olefin polymer with the catalyst.According to the present invention, there can be provided an olefin polymerization catalyst having a high catalyst activity per titanium enough to make the removal of catalyst residues unnecessary and a process for producing an olefin polymer having a low content of low molecular weight component with the catalyst.Type: GrantFiled: October 15, 1996Date of Patent: December 29, 1998Assignee: Sumitomo Chemical Company, LimitedInventors: Hiroyuki Shiraishi, Eiji Nakaishi, Takahiro Hino, Akio Imai
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Patent number: 5847055Abstract: A catalyst system of the formula I X M (Z.sup.1).sub.z.sbsb.1 (Z.sup.2).sub.z.sbsb.2 (Z.sup.3).sub.z.sbsb.3 IwhereX is C.sub.1 -C.sub.10 -alkyl, 5- to 7-membered cycloalkyl, C.sub.1 -C.sub.10 -alkoxy, C.sub.6 -C.sub.15 -aryl or a compound of the formula II ##STR1## where R.sup.1 to R.sup.5 are substituents as defined in the specification,M is a metal of transition groups II to VIII of the Periodic Table of the Elements,Z.sup.1 to Z.sup.3 are polymers of vinylaromatic compounds, dienes, acrylates or their mixturesand.sub.Z1 to .sub.Z3 are 0, 1, 2 or 3, where.ltoreq..sub.Z1 +.sub.Z2 +.sub.Z3 .ltoreq.3.Type: GrantFiled: August 22, 1997Date of Patent: December 8, 1998Assignee: BASF AktiengesellschaftInventors: Josef Wunsch, Walter Maier
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Patent number: 5744414Abstract: The present invention relates to a process for the preparation of a solid catalytic component of a catalyst of Ziegler-Natta type, comprising contacting (i) at least one compound (A) of a transition metal (TM) with (ii) a solid product (B) comprising a magnesium compound and having a reducing power for the transition metal (TM), in the presence of (iii) at least one olefin under conditions such that the olefin at least partially polymerizes during the contacting. The solid catalytic component is particularly useful for producing ethylene (co-)polymers in a gas phase process and for improving the statistical distribution of the comonomer in the copolymer structure.Type: GrantFiled: June 28, 1994Date of Patent: April 28, 1998Assignee: BP Chemicals LimitedInventor: Charles Jenny
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Patent number: 5733989Abstract: The present invention concerns prepolymerized catalyst composition for polymerization of .alpha.-olefins, a process for the preparation thereof and a process for polymerization of .alpha.-olefins. According to the polymerization process a procatalyst composition containing a transition metal is prepolymerized with a monomer in order to produce a prepolymerized Ziegler-Natta type catalyst composition and said catalyst composition is contacted with an alpha-olefin monomer, in particular with ethylene or propylene, for preparing a polymer. According to the invention the procatalyst composition is preferably prepolymerized in a medium which is inert to the catalyst components, the viscosity of the medium being so high that the catalyst does not substantially settle in this medium. Because the catalyst composition according to the invention does not have to be dried before being fed into the medium, its activity is high before and during polymerization.Type: GrantFiled: March 27, 1997Date of Patent: March 31, 1998Assignee: Borealis A/SInventors: Ismo Pentti, Pauli Leskinen
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Patent number: 5728640Abstract: A process for preparing a supported metallocene/aluminoxane solid catalyst comprises preparing a water-in-oil emulsion of water and an inert solvent by using an emulsifier, adding dropwise the emulsion to a solution of an organoaluminium compound in an inert solvent to carry out the reaction to obtain a suspension of the particulate aluminoxane, followed by adding a solution of a metallocene to the above suspension to support the metallocene on the aluminoxane. The solid catalyst thus obtained can be used in the polymerization and copolymerization of olefins. Polymerization can be carried out by slurry polymerization, bulk polymerization, gas phase polymerization, etc.Type: GrantFiled: July 10, 1996Date of Patent: March 17, 1998Assignee: China Petrochemical Corp. and Research Institute of Petroleum Processing SinopecInventors: Bing Lu, Jinmei Wang, Xiaoyu Hong, Zhenhua Jing
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Patent number: 5705578Abstract: 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: GrantFiled: May 4, 1995Date of Patent: January 6, 1998Assignee: Phillips Petroleum CompanyInventors: Bernd Peifer, Helmut G. Alt, M. Bruce Welch
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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: 5641721Abstract: The present invention concerns prepolymerized catalyst composition for polymerization of .alpha.-olefins, a process for the preparation thereof and a process for polymerization of .alpha.-olefins. According to the polymerization process a procatalyst composition containing a transition metal is prepolymerized with a monomer in order to produce a prepolymerized Ziegler-Natta type catalyst composition and said catalyst composition is contacted with an alpha-olefin monomer, in particular with ethylene or propylene, for preparing a polymer. According to the invention the procatalyst composition is preferably prepolymerized in a medium which is inert to the catalyst components, the viscosity of the medium being so high that the catalyst does not substantially settle in this medium. Because the catalyst composition according to the invention does not have to be dried before being fed into the medium, its activity is high before and during polymerization.Type: GrantFiled: December 12, 1995Date of Patent: June 24, 1997Assignee: Neste OyInventors: Ismo Pentti, Pauli Leskinen
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Patent number: 5587439Abstract: The present invention is directed to a supported metallocene catalyst useful in the polymerization of .alpha.-olefins which is obtained by tethering a metallocene catalyst component to the surface of a particulate, functionalized copolymeric support material.Type: GrantFiled: May 12, 1995Date of Patent: December 24, 1996Assignee: Quantum Chemical CorporationInventor: Anthony-J. DiMaio
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Patent number: 5556893Abstract: Catalyst support containing an .alpha.-olefin polymer which is in the form of particles of mean size from 5 to 350 .mu.m in which the pore volume generated by the pores of radius from 1,000 to 75,000 .ANG. is at least 0.2 cm.sup.3 /g.Catalyst usable for the polymerization of .alpha.-olefins, including a compound containing at least one transition metal belonging to groups IIIb, IVb, IVb and VIb of the Periodic Table, bound in or on this support.Type: GrantFiled: May 24, 1994Date of Patent: September 17, 1996Assignee: Solvay (Soci et e Anonyme)Inventors: Jean-Louis Costa, Vincent Laurent, Philippe Francois, Dirk Vercammen
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Patent number: 5494871Abstract: A stable, long-lived catalyst composition, well suited for the polymerization of olefins, e.g., of ethylene, comprises intimate admixture of particulates of an olefin prepolymer and a catalytically effective amount of particles of a metallic olefin polymerization catalyst, such olefin prepolymer particulates having a particle size distribution narrower than the particle size distribution of the metallic catalyst particles.Type: GrantFiled: February 3, 1995Date of Patent: February 27, 1996Assignee: Elf Atochem S.A.Inventors: Claude Brun, Michel Avaro
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Patent number: 5492978Abstract: A polymer bound ligand represented by the formula QM(R).sub.m and process for preparing same are provided, wherein Q is a polystyrene, M is Si, C, Ge, Sn, P, or N, each R is a that at least one R is a cyclopentadienyl-type compound, and m is 2 or 3, said process comprising reacting a metallated polystyrene and an organohalide compound, wherein the polystyrene is metallated with an alkali metal, and wherein said organohalide compound is represented by the formula XM(R).sub.m wherein X is a halide. Other aspects of the present invention include a polymer bound metallocene represented by the formula QM(R).sub.m ZY.sub.n and a process for preparing same, wherein Z is a transition metal, Y is a halide, methyl, hydrogen, or a cyclopentadienyl-type group, and n is 2 or 3. Other aspects of the present invention include a catalyst system comprising the polymer bound metallocene and an organoaluminoxane, a method for preparing same, and a polymerization process employing the catalyst system.Type: GrantFiled: May 31, 1995Date of Patent: February 20, 1996Assignee: Phillips Petroleum CompanyInventors: Bernd Peifer, Helmut G. Alt, M. Bruce Welch, Syriac J. Palackal
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Patent number: 5461017Abstract: An improved catalyst for the polymerization of olefins comprising at least one metallocene and at least one aluminoxane co-catalyst supported on a substrate comprising a cross-linked polymeric, porous, resin wherein at least one of the monomers in the resin has at least one pendant functional group which is not reactive under the conditions of the formation of the substrate, and therefore survives the copolymerization which forms the substrate. One specific cross-linked resin is a copolymer of styrene, divinyl benzene and acetoxy styrene.Type: GrantFiled: March 4, 1994Date of Patent: October 24, 1995Assignee: Mobil Oil CorporationInventors: Allan B. Furtek, Ronald S. Shinomoto
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Patent number: 5455214Abstract: A catalyst precursor composition comprises the reaction product of a cation exchange resin containing trityl carbonium ions contacted with a metallocene. The process of producing the reaction product of a cation exchange resin containing trityl carbonium ions contacted with a metallocene comprises(1) providing a cation exchange resin which has cations,(2) contacting the cation exchange resin with a solution comprising a trityl halide complex and solvent therefor to form an intermediate; and(3) contacting the intermediate with a metallocene, preferably a zirconocene salt.The resulting composition can be used to form ethylene resins in an alumoxane free system.Type: GrantFiled: September 9, 1993Date of Patent: October 3, 1995Assignee: Mobil Oil CorporationInventors: Allan B. Furtek, Michael J. Krause
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Patent number: 5409875Abstract: A polymer supported catalyst comprises Ziegler-Natta catalysts immobilized on a magnesium-modified polymer support. The catalyst support is prepared by (1) dissolving a carboxyl group-containing polymer in a solvent and precipitating the polymer in a polar non-solvent, (2) wet-grinding the precipitated polymer, and (3) mixing the ground polymer with an organomagnesium compound or a complex of an organomagnesium compound and an organoaluminum compound to give a magnesium-modified polymer support. Optionally, the resulting magnesium-modified support is treated with a halogen-containing silicon compound. The catalysts may be loaded onto the support by reacting the magnesium-modified support with a transition metal compound to form a catalyst constituent, and then combining the catalyst constituent with an appropriate organo-metallic compound.Type: GrantFiled: March 8, 1993Date of Patent: April 25, 1995Assignee: Queen's UniversityInventors: Cheng C. Hsu, Lixin Sun
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Patent number: 5374597Abstract: Catalysts useful in olefin polymerization are a mixture of (a) (i) one or more compounds Zn(X.sup.1).sub.2 and one or more compounds Al(R.sup.1).sub.3, or (ii) Zn(X.sup.1).sub.2.2Al(R.sup.1).sub.3, wherein X.sup.1 is halide and R.sup.1 is C.sub.1-12 hydrocarbyl; and (b) one or more of V(X.sup.2).sub.c (OR.sup.2).sub.b-c, VO(X.sup.3).sub.d (OR.sup.3).sub.3-d, or VO(X.sup.4).sub.2, wherein X.sup.2, X.sup.3 and X.sup.4 are halogen, R.sup.2 and R.sup.3 are C.sub.1-18 hydrocarbyl, b is 3-4, c is 0-b, and d is 0-3; and can contain (c) one or more of M(R.sup.5).sub.e (X.sup.5).sub.3-e, Al.sub.2 (R.sup.5).sub.3 (X.sup.5).sub.3 or Mg(R.sup.6).sub.f Y.sub.2-f, wherein X.sup.1 and X.sup.2 are halide, R.sup.1, R.sup.5, R.sup.6 and R.sup.9 are C.sub.1- 12 hydrocarbyl, M is Al or B, e is 0-3, Y is halide, O--(C.sub.1-12 hydrocarbyl) or N(SiR.sup.9.sub.3).sub.2, and f is 0-2.Type: GrantFiled: February 12, 1993Date of Patent: December 20, 1994Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5352791Abstract: Shaped organosiloxane amine copolycondensates are described which contain Pd, Pt, Ru and/or Rh, as well as optional promotors and/or moderators. The shaped copolycondensate function as a carrier for metals and are made up of units of: ##STR1## and/or units of Y--R.sup.6. R.sup.2 to R.sup.6 are a group represented by the formula: ##STR2## wherein R.sup.7 is a group bound to N, X, or Y (for example, an alkylene group) and R.sup.1 is R.sup.7 --SiO.sub.3/2, H, CH.sub.3, C.sub.2 H.sub.5, or C.sub.3 H.sub.7. X stands for a double-bonded group such as --S--, --S.sub.2 --, --S.sub.3 --, --S.sub.4 --, --HN--CS--NH-- and Y stands for a monovalent groups such as --CN, --SCN, --SH, --S--CH.sub.3, --NH.sub.2, --NH--(CH.sub.2).sub.2 --NH.sub.2. The carrier substance may be cross-linked with cross-linking agents containing Si, Ti, Zr or Al. The metal-containing product is spherical in form and is defined by the parameters of sphere diameter, specific surface and pore volume as well as bulk density.Type: GrantFiled: September 16, 1993Date of Patent: October 4, 1994Assignee: Degussa AktiengesellschaftInventors: Peter Panster, Stefan Wieland
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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: 5308816Abstract: 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: May 29, 1992Date of Patent: May 3, 1994Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Kunio Yamamoto
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Patent number: 5290745Abstract: A catalyst system of the Ziegler-Natta type suitable for producing ethylene copolymers having a reduced hexane extractable content comprising (a) an organoaluminum component and (b) a titanium trichloride component which has been prepared by reducing titanium tetrachloride with magnesium metal.Type: GrantFiled: August 10, 1992Date of Patent: March 1, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Robert J. Jorgensen, Elton D. Fowler, George L. Goeke