Utilizing High Molecular Weight Synthetic Polymer Patents (Class 502/109)
  • Patent number: 6461993
    Abstract: 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: Grant
    Filed: October 8, 1999
    Date of Patent: October 8, 2002
    Assignee: Shell Oil Company
    Inventors: Harry Van Der Heijden, Hendrik Van De Weg
  • Patent number: 6448348
    Abstract: 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: Grant
    Filed: June 9, 2000
    Date of Patent: September 10, 2002
    Assignee: Saudi Basic Industries Corporation
    Inventors: Akhlaq Moman, Atieh Abu-Raqabah, Orass Hamed, Raju Raghavan
  • Patent number: 6444766
    Abstract: 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: Grant
    Filed: November 8, 2000
    Date of Patent: September 3, 2002
    Assignees: Basell Polyolefine GmbH, Max-Planck-Gesellschaft
    Inventors: Martin Stork, Klaus Müllen, Markus Klapper, Matthias Koch, Heike Gregorius, Ursula Rief, Marc Oliver Kristen
  • Patent number: 6444604
    Abstract: 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: Grant
    Filed: June 8, 2000
    Date of Patent: September 3, 2002
    Assignee: Basell Technology Company BV
    Inventors: Enrico Albizzati, Tiziano Dall'Occo, Luigi Resconi, Fabrizio Piemontesi
  • Patent number: 6432860
    Abstract: 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: Grant
    Filed: March 22, 1999
    Date of Patent: August 13, 2002
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, Margarito Lopez
  • Patent number: 6423660
    Abstract: 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: Grant
    Filed: January 9, 1998
    Date of Patent: July 23, 2002
    Assignee: Basell Technology Company BV
    Inventors: Enrico Albizzati, Tiziano Dall'Occo, Luigi Resconi, Fabrizio Piemontesi
  • Patent number: 6417320
    Abstract: 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: Grant
    Filed: February 25, 2000
    Date of Patent: July 9, 2002
    Assignee: Zimmer Aktiengesellschaft
    Inventors: Brigitta Otto, Karl Ulrich Thiele, Xiaogang Guo
  • Patent number: 6413901
    Abstract: 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: Grant
    Filed: June 9, 2000
    Date of Patent: July 2, 2002
    Assignee: Saudi Basic Industries Corporation
    Inventors: Akhlaq Moman, Atieh Abu-Raqabah, Navin Nallaveerapan
  • Patent number: 6403519
    Abstract: 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: Grant
    Filed: December 21, 1999
    Date of Patent: June 11, 2002
    Assignee: Solvay Polyolefins Europe-Belgium (Societe Anonyme)
    Inventors: Philippe Francois, Serge Bettonville, Dominique Marchand
  • Patent number: 6384159
    Abstract: 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: Grant
    Filed: April 21, 2000
    Date of Patent: May 7, 2002
    Assignee: Buna Sow Leuna Olefinverbund GmbH
    Inventors: Jürgen Schellenberg, Heinz-Jürgen Kerrinnes, Gerd Fritzsche, Gerd Lohse
  • Patent number: 6383969
    Abstract: 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: Grant
    Filed: December 21, 1999
    Date of Patent: May 7, 2002
    Assignee: Solvay Polyolefins Europe - Belgium
    Inventors: Philippe Francois, Serge Bettonville, Dominique Marchand
  • Patent number: 6358876
    Abstract: 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: Grant
    Filed: April 19, 2000
    Date of Patent: March 19, 2002
    Assignee: Wacker-Chemie GmbH
    Inventors: Helmut Alt, Frank Baumann, Johann Weis, Alexander Köppl
  • Publication number: 20020013217
    Abstract: 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: Application
    Filed: March 31, 1993
    Publication date: January 31, 2002
    Applicant: Hans-Friedrich Herrmann
    Inventors: HANS-FRIEDRICH HERRMANN, BERND BACHMANN, BERNHARD HIERHOLZER, WALTER SPALECK
  • Patent number: 6340771
    Abstract: 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: Grant
    Filed: December 22, 1999
    Date of Patent: January 22, 2002
    Assignee: Nova Chemicals (International) S. A.
    Inventors: Peter Phung Minh Hoang, Dusan Jeremic, Jason Roy Kearns, Iain McLaren Coulter, Robert D. Donaldson
  • Publication number: 20010044374
    Abstract: A process for the preparation of a supported catalyst is disclosed, comprising the steps of
    Type: Application
    Filed: January 31, 2001
    Publication date: November 22, 2001
    Inventor: Marc John Payne
  • Patent number: 6268453
    Abstract: 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: Grant
    Filed: October 18, 1999
    Date of Patent: July 31, 2001
    Assignee: Phillips Petroleum Company
    Inventors: Alexander Köppl, Helmut G. Alt, Syriac J. Palackal, M. Bruce Welch
  • Patent number: 6255244
    Abstract: 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: Grant
    Filed: September 8, 1999
    Date of Patent: July 3, 2001
    Assignee: Idemitsu Petrochemical Co., Ltd.
    Inventor: Nobuhiro Yabunouchi
  • Publication number: 20010004657
    Abstract: 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: Application
    Filed: September 14, 1998
    Publication date: June 21, 2001
    Applicant: CHISSO CORPORATION
    Inventors: JUN SAITO, HIDEO NOBUHARA, SHINGO KIKUKAWA, HITOSHI SATO, AKIRA YAMAUCHI
  • Patent number: 6239060
    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
  • Patent number: 6221802
    Abstract: 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: Grant
    Filed: January 16, 1998
    Date of Patent: April 24, 2001
    Assignee: Solvay Polyolefins Europe-Belgium
    Inventors: Jean-Louis Costa, Vincent Laurent, Philippe Francois, Dirk Vercammen
  • Patent number: 6218331
    Abstract: 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: Grant
    Filed: June 27, 1997
    Date of Patent: April 17, 2001
    Assignee: Equistar Chemicals, L.P.
    Inventors: Anthony-J. DiMaio, Craig C. Meverden, Peter D. Becker
  • Patent number: 6197985
    Abstract: 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: Grant
    Filed: September 1, 1998
    Date of Patent: March 6, 2001
    Assignee: Mitsui Chemicals INC
    Inventors: Atsuo Kobata, Kazuhito Gotoh, Shigeru Isayama, Tetsuhiro Matsumoto
  • Patent number: 6100353
    Abstract: 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: Grant
    Filed: September 6, 1995
    Date of Patent: August 8, 2000
    Assignee: BASF Aktiengesellschaft
    Inventors: John Lynch, David Fischer, Franz Langhauser, Hans-Helmut Gortz, Jurgen Kerth, Gunther Schweier
  • Patent number: 6100214
    Abstract: 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: Grant
    Filed: June 5, 1998
    Date of Patent: August 8, 2000
    Assignee: Exxon Chemical Patents Inc.
    Inventors: John F. Walzer, Jr., Anthony J. Dias, Jean M J Frechet, Stephen B. Roscoe
  • Patent number: 6063725
    Abstract: 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: Grant
    Filed: November 4, 1996
    Date of Patent: May 16, 2000
    Assignee: Mitsui Chemicals, Inc.
    Inventors: Tadahiro Sunaga, Yukio Ishii, Tadashi Asanuma
  • Patent number: 6048817
    Abstract: 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: Grant
    Filed: April 24, 1998
    Date of Patent: April 11, 2000
    Assignee: Mitsubishi Chemical Corporation
    Inventors: Takehiro Sagae, Yumito Uehara
  • Patent number: 6040260
    Abstract: 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: Grant
    Filed: June 16, 1997
    Date of Patent: March 21, 2000
    Assignee: Borealis A/S
    Inventors: Ismo Pentti, Pauli Leskinen
  • Patent number: 6013594
    Abstract: 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: Grant
    Filed: April 29, 1998
    Date of Patent: January 11, 2000
    Assignee: Exxon Chemical Patents, Inc.
    Inventors: Henry Wu-Hsian Yang, Anthony Nicholas Speca
  • Patent number: 5990035
    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
  • Patent number: 5922819
    Abstract: 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: Grant
    Filed: July 14, 1997
    Date of Patent: July 13, 1999
    Assignee: BASF Aktiengesellschaft
    Inventors: Josef Wunsch, Martin Lux, David Fischer
  • Patent number: 5854164
    Abstract: 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: Grant
    Filed: October 15, 1996
    Date of Patent: December 29, 1998
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Hiroyuki Shiraishi, Eiji Nakaishi, Takahiro Hino, Akio Imai
  • Patent number: 5847055
    Abstract: 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: Grant
    Filed: August 22, 1997
    Date of Patent: December 8, 1998
    Assignee: BASF Aktiengesellschaft
    Inventors: Josef Wunsch, Walter Maier
  • Patent number: 5744414
    Abstract: 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: Grant
    Filed: June 28, 1994
    Date of Patent: April 28, 1998
    Assignee: BP Chemicals Limited
    Inventor: Charles Jenny
  • Patent number: 5733989
    Abstract: 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: Grant
    Filed: March 27, 1997
    Date of Patent: March 31, 1998
    Assignee: Borealis A/S
    Inventors: Ismo Pentti, Pauli Leskinen
  • Patent number: 5728640
    Abstract: 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: Grant
    Filed: July 10, 1996
    Date of Patent: March 17, 1998
    Assignee: China Petrochemical Corp. and Research Institute of Petroleum Processing Sinopec
    Inventors: Bing Lu, Jinmei Wang, Xiaoyu Hong, Zhenhua Jing
  • Patent number: 5705578
    Abstract: Methods are disclosed for preparing a highly active solid metallocene-containing catalyst system and its use in the polymerization of olefins. The solid catalyst system is prepared by combining an aluminoxane with a metallocene having a substituent which has internal alkynyl unsaturation in a suitable liquid to form a liquid catalyst system, conducting prepolymerization of an olefin in the liquid catalyst system, and separating the resulting solid metallocene-containing catalyst system from the last reaction product mixture. Also polymerization of olefins using the inventive solid catalyst system is disclosed.
    Type: Grant
    Filed: May 4, 1995
    Date of Patent: January 6, 1998
    Assignee: Phillips Petroleum Company
    Inventors: Bernd Peifer, Helmut G. Alt, M. Bruce Welch
  • Patent number: 5661095
    Abstract: 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: Grant
    Filed: June 6, 1995
    Date of Patent: August 26, 1997
    Assignee: Quantum Chemical Corporation
    Inventors: Craig C. Meverden, Emory A. Ford
  • Patent number: 5641721
    Abstract: 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: Grant
    Filed: December 12, 1995
    Date of Patent: June 24, 1997
    Assignee: Neste Oy
    Inventors: Ismo Pentti, Pauli Leskinen
  • Patent number: 5587439
    Abstract: 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: Grant
    Filed: May 12, 1995
    Date of Patent: December 24, 1996
    Assignee: Quantum Chemical Corporation
    Inventor: Anthony-J. DiMaio
  • Patent number: 5556893
    Abstract: 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: Grant
    Filed: May 24, 1994
    Date of Patent: September 17, 1996
    Assignee: Solvay (Soci et e Anonyme)
    Inventors: Jean-Louis Costa, Vincent Laurent, Philippe Francois, Dirk Vercammen
  • Patent number: 5494871
    Abstract: 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: Grant
    Filed: February 3, 1995
    Date of Patent: February 27, 1996
    Assignee: Elf Atochem S.A.
    Inventors: Claude Brun, Michel Avaro
  • Patent number: 5492978
    Abstract: 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: Grant
    Filed: May 31, 1995
    Date of Patent: February 20, 1996
    Assignee: Phillips Petroleum Company
    Inventors: Bernd Peifer, Helmut G. Alt, M. Bruce Welch, Syriac J. Palackal
  • Patent number: 5461017
    Abstract: 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: Grant
    Filed: March 4, 1994
    Date of Patent: October 24, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Allan B. Furtek, Ronald S. Shinomoto
  • Patent number: 5455214
    Abstract: 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: Grant
    Filed: September 9, 1993
    Date of Patent: October 3, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Allan B. Furtek, Michael J. Krause
  • Patent number: 5409875
    Abstract: 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: Grant
    Filed: March 8, 1993
    Date of Patent: April 25, 1995
    Assignee: Queen's University
    Inventors: Cheng C. Hsu, Lixin Sun
  • Patent number: 5374597
    Abstract: 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: Grant
    Filed: February 12, 1993
    Date of Patent: December 20, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Chi-I Kuo, Michael W. Lynch
  • Patent number: 5352791
    Abstract: 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: Grant
    Filed: September 16, 1993
    Date of Patent: October 4, 1994
    Assignee: Degussa Aktiengesellschaft
    Inventors: Peter Panster, Stefan Wieland
  • Patent number: 5340785
    Abstract: 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: Grant
    Filed: February 26, 1993
    Date of Patent: August 23, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn
  • Patent number: 5308816
    Abstract: 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: Grant
    Filed: May 29, 1992
    Date of Patent: May 3, 1994
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Kunio Yamamoto
  • Patent number: 5290745
    Abstract: 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: Grant
    Filed: August 10, 1992
    Date of Patent: March 1, 1994
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Robert J. Jorgensen, Elton D. Fowler, George L. Goeke