Containing Two Or More Different Component B Metals Patents (Class 502/113)
  • Patent number: 5393719
    Abstract: Olefins can be polymerized in the presence of a catalyst system composition comprising chromium oxides supported on a inorganic oxide support, a pyrrole-containing compound and a non-hydrolyzed metal alkyl. The use of this type of polymerization catalyst in a polymerization process can produce an olefin comonomer in-situ, resulting in polymers having decreased density and increased branching.
    Type: Grant
    Filed: February 10, 1994
    Date of Patent: February 28, 1995
    Assignee: Phillips Petroleum Company
    Inventors: Ted M. Pettijohn, William K. Reagen, Shirley J. Martin
  • Patent number: 5376612
    Abstract: 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: Grant
    Filed: August 20, 1993
    Date of Patent: December 27, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
  • 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: 5369194
    Abstract: A multiple site solid catalyst component capable of producing polyolefins having a broad or multimodal molecular weight distribution, such as a bimodal molecular weight distribution, is prepared by contacting a particulate solid support with a zirconium compound or complex to bind the zirconium compound or complex to the support, optionally followed by contacting the supported zirconium compound or complex with a Lewis acid to produce an intermediate product, optionally isolating and washing the supported zirconium compound or complex or resulting intermediate product to remove soluble by-products therefrom, and reacting the washed or unwashed supported zirconium compound or complex or intermediate product with a titanium or vanadium compound to produce a solid catalyst component.
    Type: Grant
    Filed: February 24, 1993
    Date of Patent: November 29, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Leonard V. Cribbs, Michael W. Lynch
  • Patent number: 5359015
    Abstract: An improved catalyst system and process of producing polyolefins having a controllable broadened molecular weight distribution utilizing transition metal metallocene catalyst systems, wherein at least one of the metallocenes has at least one cyclopentadienyl ring being substituted by at least one optionally substituent having a 2.degree. or 3.degree. carbon atom with which it is covalently bonded to the cyclopentadienyl ring. The method for forming the catalyst system of this present invention can be either by a physical or a chemical mixing process.
    Type: Grant
    Filed: February 1, 1994
    Date of Patent: October 25, 1994
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Moses O. Jejelowo
  • Patent number: 5350724
    Abstract: A process for preparing a polymerization catalyst useful for the polymerization of olefins is provided comprising contacting a magnesium compound and a transition metal halide to form a solid product; contacting the solid product with an organoaluminum halide to form a first catalyst component, and contacting the first catalyst component with an activating agent to form a catalyst. Other aspects of the invention provide a catalyst prepared by the above described method and a polymerization process employing the thus prepared catalyst.
    Type: Grant
    Filed: May 4, 1993
    Date of Patent: September 27, 1994
    Assignee: Phillips Petroleum Company
    Inventor: Joel L. Martin
  • Patent number: 5346872
    Abstract: 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: Grant
    Filed: January 29, 1993
    Date of Patent: September 13, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
  • Patent number: 5344803
    Abstract: 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: Grant
    Filed: January 29, 1993
    Date of Patent: September 6, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
  • 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: 5334567
    Abstract: 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: Grant
    Filed: January 29, 1993
    Date of Patent: August 2, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Raghu Menon, Albert P. Masino, Mark K. Reinking
  • Patent number: 5334566
    Abstract: This is a process for the hydrogenation of conjugated diolefin polymers which comprises polymerizing or copolymerizing at least one conjugated diolefin with an organo alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer, terminating the polymerization by the addition of hydrogen and effecting selective hydrogenation of the unsaturated double bonds in the conjugated diolefin units of the terminated polymer by contacting the polymer with hydrogen in the presence of an organo alkali metal promoter and Tebbe's reagent.
    Type: Grant
    Filed: April 16, 1993
    Date of Patent: August 2, 1994
    Assignee: Shell Oil Company
    Inventors: Carma J. Gibler, Stanley E. Wilson
  • Patent number: 5332706
    Abstract: 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.In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluid bed gas phase.
    Type: Grant
    Filed: December 28, 1992
    Date of Patent: July 26, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
  • Patent number: 5332707
    Abstract: 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: Grant
    Filed: July 31, 1992
    Date of Patent: July 26, 1994
    Assignee: Amoco Corporation
    Inventors: Nicholas M. Karayannis, Steven A. Cohen, Julie L. Ledermann
  • Patent number: 5330950
    Abstract: Ethylene polymers or copolymers having very broad molecular weight distributions in a broad range of melt-indicies are produced by using mixtures of MgO-supported Ziegler catalyst and a chromium oxide catalyst in which the usual poisoning of the catalysts does not occur.
    Type: Grant
    Filed: August 14, 1989
    Date of Patent: July 19, 1994
    Assignee: Mobil Oil Corporation
    Inventor: John T. T. Hsieh
  • Patent number: 5331070
    Abstract: Olefins can be polymerized in the presence of a catalyst system composition comprising chromium supported on an inorganic oxide support, a pyrrole-containing compounds, and a metal alkyl. The use of this type of polymerization process can produce an olefin comonomer in-situ, resulting in polymers having decreased density and increased branching.
    Type: Grant
    Filed: November 13, 1992
    Date of Patent: July 19, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Ted M. Pettijohn, William K. Reagen, Shirley J. Martin
  • Patent number: 5320996
    Abstract: 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: Grant
    Filed: November 6, 1992
    Date of Patent: June 14, 1994
    Assignee: Chevron Research and Technology Company
    Inventors: Michael J. Carney, David L. Beach
  • Patent number: 5320994
    Abstract: The process comprises, in a first step, the reduction of a titanium (IV) compound in an .alpha.,.omega.-dihalogenoalkane using a molar excess of at least one halogenated organoaluminium compound in the absence of an ether, and then in a second step, the addition of a reaction mixture of a compound capable of forming a magnesium halide in-situ, without additional reduction of the titanium compound obtained in the first step. The catalyst contains at least one titanium compound, at least one halogenated organoaluminium compound and at least one inorganic magnesium compound in suspension in at least one .alpha.,.omega.-dihalogenoalkane; the titanium cmpound is essentially a titanium (III) compound, the total titanium (II) and titanium (IV) content being less than or equal 15% to the total titanium content. It may also contain at least one vanadium compound, an inert solvent, at least one partially polymerized .alpha.
    Type: Grant
    Filed: March 4, 1992
    Date of Patent: June 14, 1994
    Assignee: Norsolor
    Inventors: Karel Bujadoux, Jean-Michel Brusson, Francis Petit, Andre Mortreux
  • Patent number: 5310834
    Abstract: Mixed catalyst compositions comprised of a first supported chromium-containing catalyst component and a second supported chromium-containing catalyst component and which additionally have one or more metallic or non-metallic catalytic agents associated therewith are provided. The additional metallic or non-metallic elements associated with the catalyst components can be aluminum, titanium, zirconium, boron, phosphorous or combinations thereof. The pore volume of the silica supports used for the first and second catalyst components differs by at least 0.3 cc/g. The mixed catalyst compositions of the invention are useful for the preparation of polyolefins. They are particularly useful of polymerization of ethylene in particle form polymerizations to produce high density polyethylene blow molding resins having good processability and physical properties. The improved particle form polymerization process and products obtained thereby using the above-described mixed catalyst compositions are also described.
    Type: Grant
    Filed: December 16, 1992
    Date of Patent: May 10, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Stanley J. Katzen, Thomas J. Pullukat, Michael W. Lynch, Louis J. Rekers
  • Patent number: 5300597
    Abstract: A method is disclosed for preparing an olefin polymerization catalyst of improved particle size from a solution of magnesium containing component and a transition metal containing component which is reacted with an organoaluminum halide compound. The improved particle size is provided by employing the organoaluminum halide compound in conjunction with a silicon compound, such as for example an alkyl silicate or a polysiloxane.
    Type: Grant
    Filed: February 12, 1993
    Date of Patent: April 5, 1994
    Assignee: Phillips Petroleum Company
    Inventor: Nemesio D. Miro
  • Patent number: 5298579
    Abstract: A method of using a catalyst with a suitable cocatalyst in the polymerization or copolymerization of 1-olefins are disclosed. The catalyst is prepared by: a) contacting a Group IIA organometallic compound, like 2-methylpentanoxymagnesium chloride, or a Group III organometallic compound, like triethylaluminum, or a combination thereof, with a porous or nonporous biodegradable substrate having active surface hydroxyl groups, like cellulose, to provide a modified biodegradable substrate; then b) contacting the modified biodegradable substrate with a transition metal compound, such as a transition metal halide or alkoxide, like titanium tetrachloride or vanadium (V) trichloride oxide, to form discrete catalyst particles. The catalyst particles are used in conjunction with a suitable cocatalyst, like triethylaluminum, in the homopolymerization or copolymerization of 1-olefins. During polymerization, porous biodegradable catalyst particles are fragmented into small solid particles that are trapped within polymer.
    Type: Grant
    Filed: November 13, 1992
    Date of Patent: March 29, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Raymond E. Hoff, Leonard V. Cribbs
  • Patent number: 5296432
    Abstract: Solid component of catalyst for the (co)polymerization of ethylene, including magnesium, halogen and titanium, obtained by:(i) dissolution, in an inert organic solvent, of a magnesium dialkyl, or a magnesium alkyl halide, a tin halide (IV) and possibly also an alkyl halide and their contact until a granular solid precipitates from the solution;(ii) contact of said granular solid and its interaction with a titanium halide, alkoxide or halo-alkoxide, to form a solid component of catalyst.
    Type: Grant
    Filed: July 9, 1992
    Date of Patent: March 22, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Federico Milani, Luciano Luciani, Maddalena Pondrelli
  • Patent number: 5296565
    Abstract: A solid catalyst for olefin polymerization comprising[A] a particulate carrier composed of (i) an oxide of at least one element selected from among those belonging to the groups of II, III and IV of the periodic table, and containing (ii) at least 1.0 % by weight of water,[B] an organoaluminum oxy compound, and[C] a transition metal compound of a metal belonging to the group IV B of the periodic table containing a ligand having a cyclopentadienyl skeleton,wherein the organoaluminum oxy compound [B] and the transition metal compound [C] are supported on the particulate carrier [A].
    Type: Grant
    Filed: April 2, 1993
    Date of Patent: March 22, 1994
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Takashi Ueda, Okawa Kazunori
  • Patent number: 5292837
    Abstract: For the homopolymerization of ethylene or for the copolymerization of ethylene with other 1-olefins, a catalyst is used which comprises a trialkylaluminum compound and the entire product from the reaction of a magnesium alkoxide which is dissolved, suspended or dispersed as a gel in an inert solvent, with a tetravalent transition-metal compound and an organoaluminum compound, washing with an inert solvent and reacting with a halogenated metal compound. A polymer having coarse particles and a high bulk density is obtained.
    Type: Grant
    Filed: August 5, 1992
    Date of Patent: March 8, 1994
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Andreas Heinrich, Ludwig Bohm, Hans-Albrecht Scholz
  • Patent number: 5286694
    Abstract: A polymerization catalyst is formed by producing a solution of a halide of scandium, yttrium, or a rare earth metal and an alcohol; contacting the solution with an organometallic compound to form a soluble complex; and contacting the soluble complex with a halide ion exchanging source. Optionally an ester or an anhydride can also be combined with the halide solution or the soluble complex. The catalyst thus produced can be combined with an organometallic cocatalyst.
    Type: Grant
    Filed: December 11, 1991
    Date of Patent: February 15, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Ted M. Pettijohn, Henry L. Hsieh
  • Patent number: 5281679
    Abstract: A catalyst and method of producing polyolefins having broadened molecular weight distributions and enhanced tensile impact strengths utilizing a silica supported metallocene-alumoxane catalyst system, wherein at least one of the metallocenes has at least one cyclopentadienyl ring being substituted by at least one optionally substituted hydrocarbon substituent having a 2.degree. or 3.degree. carbon atom with which it is covalently bonded to the cyclopentadienyl ring.
    Type: Grant
    Filed: April 9, 1992
    Date of Patent: January 25, 1994
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Moses O. Jejelowo, Robert L. Bamberger
  • Patent number: 5278117
    Abstract: A supported Ziegler-Natta catalyst active in ethylene polymerization and in the copolymerization of ethylene with alpha-olefins consists of:(A) a cocatalyst in the form of an organometallic compound of aluminium, and(B) a solid catalyst component obtained by:(i) impregnating a granular solid support with a solution of a titanium alcoholate and magnesium chloride in a liquid aliphatic hydrocarbon, followed by evaporation of the hydrocarbon solvent;(ii) impregnating the support treated in (i) with a solution of magnesium chloride in a liquid aliphatic ester, followed by evaporation of the ester solvent; and(iii) activating the support treated in (ii) by contact with an alkyl aluminium halide.In a preferred embodiment, measured quantities of a silicon halide are introduced in stage (i) and/or (ii), this considerably improving catalytic activity.
    Type: Grant
    Filed: March 8, 1991
    Date of Patent: January 11, 1994
    Assignee: Montedipe S.r.l.
    Inventors: Luciano Luciani, Renzo Invernizzi, Francesco Masi, Maddalena Pondrelli, Mario Polesello, Italo Borghi
  • Patent number: 5276114
    Abstract: A method for making polymerization catalysts is disclosed which comprises contacting a soluble complex prepared from the combination of a metal dihalide and a transition metal compound with a particulate material comprising zirconium phosphate and then reacting the resulting mixture with an organoaluminum halide to produce a catalyst precursor. The catalyst precursor is then contacted with a halogen containing compound selected from halides of Groups IVA and VA to produce the catalyst. Novel catalysts prepared in accordance with the invention method, novel polymerization processes therewith and novel polymers having relatively high melt flow rates while retaining good mechanical strength are also disclosed.
    Type: Grant
    Filed: April 19, 1993
    Date of Patent: January 4, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Gil Hawley, Max McDaniel, Simon Kukes
  • Patent number: 5272229
    Abstract: There are disclosed a process for producing a styrene polymer having a high degree of syndiotactic configuration at a reduced cost and an enhanced efficiency, and a catalyst to be used therefore which comprises (A) a specific transition-metal compound, (B) a specific coordination complex compound and (C) a compound having an alkyl group.The catalyst according to the present invention is inexpensive compared with the conventional catalyst containing aluminoxane as the major ingredient, and exhibits a high activity in polymerizing a styrenic monomer into styrene polymer with a high degree of syndiotacticity as well as a high yield and conversion rate.
    Type: Grant
    Filed: December 2, 1991
    Date of Patent: December 21, 1993
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Norio Tomotsu, Mizutomo Takeuchi, Masahiko Kuramoto
  • Patent number: 5266544
    Abstract: In accordance with the present invention, there are provided olefin polymerization solid catalysts comprising[A] a solid titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients, said catalyst component having supported thereon[B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and, if necessary,[C] an organoaluminum oxy-compound.In accordance with the invention, there are also provided olefin polymerization solid catalysts comprising[i] a solid containing a transition metal compound containing a ligand having a cycloalkadienyl skeleton, said solid having supported thereon[ii] a titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients and, if necessary,[iii] an organoaluminum oxy-compound.
    Type: Grant
    Filed: May 27, 1992
    Date of Patent: November 30, 1993
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Toshiyuki Tsutsui, Takashi Ueda
  • Patent number: 5260244
    Abstract: A polymerization catalyst system is formed by combining an organometal compound and a transition metal compound to produce a catalyst A; and combining catalyst A and a catalyst B comprising a rare earth complex having a formula Cp.sub.n MX.sub.4-n.M'L.sub.x, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, M is yttrium, scandium or a rare earth metal having an atomic number in the range of 57 to 71, M' is an alkali metal, L is a suitable electron donor ligand, X is a halogen, n is 1 or 2, and x is a number corresponding to the value needed to form a stable complex.Optionally catalyst A is contacted with a rare earth metal halide.Optionally catalyst B is contacted with an alkali or alkaline earth metal alkyl.Optionally a hydrocarbyl aluminum compound can be contacted with catalyst B or with the catalyst system.
    Type: Grant
    Filed: October 1, 1992
    Date of Patent: November 9, 1993
    Assignee: Phillips Petroleum Company
    Inventor: Ted M. Pettijohn
  • Patent number: 5258343
    Abstract: A polymerization catalyst system is formed by producing a solution of a halide of scandium, yttrium, or a rare earth metal and an alcohol; contacting the solution with a halide ion exchanging source to form a solid. The catalyst thus produced can be combined with an organometallic cocatalyst. Polymers with multimodal molecular weight distribution are produced when a diol is used to prepare the catalyst and an organoaluminum halide is used as cocatalyst. Polymers with broad molecular weight distribution of the unimodal type are produced when using a trialkylaluminum compound or an alkyl aluminum hydride.
    Type: Grant
    Filed: December 18, 1991
    Date of Patent: November 2, 1993
    Assignee: Phillips Petroleum Company
    Inventor: Ted M. Pettijohn
  • Patent number: 5258342
    Abstract: A process for the preparation of a solid component of a catalyst active in the (co)polymerization of ethylene and able to form (co)polymers of ethylene having from middle to wide distribution of molecular weight and monomodal distribution of molecular weights, in processes operating in a single step, in suspension or in the gaseous phase. Said solid component of a catalyst contains magnesium, chlorine, silicon, titanium and at least another transition metal on a solid, granular and porous carrier and is obtained by treating the carrier, in succession, with: a compound of a metal selected from hafnium, zirconium or vanadium; a magnesium dialkyl or magnesium alkyl halide; a silicon chloride; and a titanium compound.
    Type: Grant
    Filed: February 26, 1992
    Date of Patent: November 2, 1993
    Assignee: ECP Enichem Polimeri S.R.L.
    Inventors: Luciano Luciani, Federico Milani, Maddalena Pondrelli, Renzo Invernizzi
  • Patent number: 5252529
    Abstract: A solid catalyst for olefin polymerization comprising [A] a particulate carrier composed of (i) an oxide of at least one element selected from among those belonging to the groups of II, III and IV of the periodic table, and containing (ii) at least 1.0% by weight of water, [B] an organoaluminum oxy compound, and [C] a transition metal compound of a metal belonging to the group IV B of the periodic table containing a ligand having a cyclopentadienyl skeleton,wherein the organoaluminum oxy compound [B] and the transition metal compound [C] are supported on the particulate carrier [A].
    Type: Grant
    Filed: May 20, 1992
    Date of Patent: October 12, 1993
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Takashi Ueda, Kazunori Okawa
  • Patent number: 5244989
    Abstract: A method for producing a stereospecific polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, wherein a catalyst system is used which comprises: (A) a solid catalyst component prepared by reacting (i) a homogeneous solution prepared by reacting (i-1) magnesium and a hydroxylated organic compound, (i-2) an oxygen-containing organic compound of titanium and/or (i-3) an oxygen-containing organic compound of silicon, with an oxygen-containing organic compound of aluminum and/or a boron compound, with (ii) at least one aluminum halide compound to obtain a solid product, reacting to this solid product (iii) an electron-donative compound and (iv) a titanium halide compound to obtain a solid component, and further reacting to this solid component (v) silicon tetrachloride and/or an alkyl-substituted product of silicon tetrachloride, (B) at least one member selected from the group consisting of organometallic compounds of Groups IA, IIA, IIB, IIIB and IVB of th
    Type: Grant
    Filed: February 26, 1992
    Date of Patent: September 14, 1993
    Assignee: Tosoh Corporation
    Inventors: Daiji Hara, Morihiko Sato, Mitsuhiro Mori, Yozo Kondo
  • Patent number: 5242876
    Abstract: This invention concerns a catalyst system comprising at least one homogeneous catalyst and at least one heterogeneous catalyst, specifically, a metallocene catalyst and a conventional Ziegler-Natta catalyst, respectively. This invention is useful in the polymerization of any polymer in which separate polymerizations with a homogeneous catalyst and with a heterogeneous catalyst are possible, but preferably, polymerization of olefins, more preferably, .alpha.-olefins, and, most preferably, propylene. This invention provides a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. This invention produces a polymer with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. Hydrogen can be used to control molecular weight distribution of a polymer produced with this invention.
    Type: Grant
    Filed: September 30, 1991
    Date of Patent: September 7, 1993
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, Michael J. Elder, Baireddy R. Reddy, David J. Rauscher
  • Patent number: 5240895
    Abstract: Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a dimeric or tetrameric cyclopentadienyl Group 6b metal compound in which the metal has an oxidation state of +2, 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: Grant
    Filed: November 6, 1992
    Date of Patent: August 31, 1993
    Assignee: Chevron Research and Technology Company
    Inventors: Michael J. Carney, David L. Beach
  • Patent number: 5238891
    Abstract: A method is disclosed for preparing an olefin polymerization catalyst of improved particle size from a solution of magnesium containing component and a transition metal containing component which is reacted with an organoaluminum halide compound. The improved particle size is provided by employing the organoaluminum halide compound in conjunction with a silicon compound, such as for example an alkyl silicate or a polysiloxane.
    Type: Grant
    Filed: June 15, 1989
    Date of Patent: August 24, 1993
    Assignee: Phillips Petroleum Company
    Inventor: Nemesio D. Miro
  • Patent number: 5237025
    Abstract: A catalyst mixture is disclosed comprising (1) a particulate chromium-containing catalyst comprising inorganic oxide and chromium and (2) a particular type of particulate titanium-containing catalyst. Also disclosed is the use of this catalyst mixture to produce particularly novel olefin polymers.
    Type: Grant
    Filed: October 9, 1990
    Date of Patent: August 17, 1993
    Assignee: Phillips Petroleum Company
    Inventors: Elizabeth A. Benham, Max P. McDaniel
  • Patent number: 5235071
    Abstract: The invention relates to a catalyst for producing phthalic anhydride by gas phase catalytic oxidation of o-xylene and/or naphthalene with molecular oxygen or gas containing molecular oxygen and, to a process for producing phthalic anhydride by using said catalyst. The catalyst is made by supporting, on a heat-resistant inorganic carrier, a catalytic active substance which comprises: vanadium oxide; anatase type titanium dioxide having specific surface area of 10 to 60 m.sup.2 /g; niobium; at least one element selected from potassium, cesium, rubidium and thallium; phosphorus; and antimony. The catalytic active substance is prepared by using a five-valent antimony compound as an antimony source. The process for producing phthalic anhydride comprises use of said catalyst.
    Type: Grant
    Filed: June 30, 1992
    Date of Patent: August 10, 1993
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Kenji Ueda, Masaaki Okuno, Tatsuya Kawabata, Shinya Tanaka
  • Patent number: 5231151
    Abstract: 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: Grant
    Filed: March 20, 1992
    Date of Patent: July 27, 1993
    Assignee: The Dow Chemical Company
    Inventors: Lee Spencer, Brian W. S. Kolthammer, Miriam P. Ripplinger, Jeffrey J. Wooster, Pak-Wing S. Chum, Jacquelyn A. deGroot
  • Patent number: 5231065
    Abstract: A method for making polymerization catalysts is disclosed which comprises contacting a soluble complex prepared from the combination of a metal dihalide and a transition metal compound with a particulate material comprising zirconium phosphate and then reacting the resulting mixture with an organoaluminum halide to produce a catalyst precursor. The catalyst precursor is then contacted with a halogen containing compound selected from halides of Groups IVA and VA to produce the catalyst. Novel catalysts prepared in accordance with the invention method, novel polymerization processes therewith and novel polymers having relatively high melt flow rates while retaining good mechanical strength are also disclosed.
    Type: Grant
    Filed: December 16, 1991
    Date of Patent: July 27, 1993
    Assignee: Phillips Petroleum Company
    Inventors: Gil Hawley, Max McDaniel, Simon Kukes
  • Patent number: 5227354
    Abstract: A process for making a magnesium-containing supported titanium-containing and vanadium-containing catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins.
    Type: Grant
    Filed: April 3, 1992
    Date of Patent: July 13, 1993
    Assignee: Amoco Corporation
    Inventors: Nicholas M. Karayannis, Steven A. Cohen, Julie L. Ledermann
  • Patent number: 5210160
    Abstract: Homopolymerization and copolymerization of ethene is carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component. The component (1) used is the solid-phase product (VI) which has been obtained by a method in which (1.1) first (1.1.1) an inorganic oxidic substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex and (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and (IIc) a silicon or boron compound are combined with formation of a suspension (III) and the latter is evaporated to form a solid-phase intermediate (IV) and (1.2) then (1.2.1) the intermediate (IV) obtained in (1.1) and (1.2.
    Type: Grant
    Filed: September 19, 1989
    Date of Patent: May 11, 1993
    Assignee: BASF Aktiengesellschaft
    Inventors: Roland Saive, Guido Funk, Rainer Hemmerich
  • Patent number: 5206197
    Abstract: A catalyst composition for preparation of polymers of vinyl aromatic monomers having high syndiotacticity comprising a cationic coordination complex and a metal hydrocarbyl.
    Type: Grant
    Filed: March 4, 1991
    Date of Patent: April 27, 1993
    Assignees: The Dow Chemical Company, Idemitsu Kosan Co., Ltd.
    Inventor: Richard E. Campbell, Jr.
  • Patent number: 5206198
    Abstract: Catalytic solids based on titanium trichloride complex, usable for the stereospecific polymerization of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of the liquid material resulting from bringing TiCl.sub.4, pretreated with an electron-donor compound, into contact with a composition (C) corresponding to the general formulaAlR.sub.p (Y) .sub.q X .sub.3-(p+q)in whichR represents a hydrocarbon radical or a hydrogen atom;Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrogen atom;X represents a halogen;p is an arbitrary number such that 0<p<3; andq is an arbitrary number such that 0<q<3; the sum (p+q) being such that 0<(p+q).ltoreq.3.These catalytic solids of controllable porosity permit the production of a wide range of propylene polymers, in particular the propylene and ethylene copolymers known as "block" copolymers.
    Type: Grant
    Filed: October 31, 1991
    Date of Patent: April 27, 1993
    Assignee: Solvay S.A.
    Inventors: Jean-Louis Costa, Sabine Pamart
  • Patent number: 5204303
    Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefines, in which particles are formed of magnesium dihalide and alcohol, the particles are reacted with an organic compound of a metal from the groups I-III, the thus obtained particulate product is activated by means of a titanium and/or vanadium compound and optionally a donor, and optionally a prepolymerization is carried out for the activated particles. A problem of such a method is how to form particles of magnesium dihalogenide and alcohol having a structure advantageous for the polymerization of olefins. The problem has in the present invention been solved so that the particles are formed by spray crystallizing (spray freezing) a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol. The hydroxyl content of the particles so obtained is much greater than earlier, which results in a much more active procatalyst than the preceding ones.
    Type: Grant
    Filed: September 16, 1991
    Date of Patent: April 20, 1993
    Assignee: Neste Oy
    Inventors: Inkeri T. Korvenoja, Arja-Liisa Kostiainen, Fero I. Iiskola, Pekka J. E. Sormunen, Bill B. B. Gustatsson, Hilkka R. Knuuttila, Ulf Palmqvist
  • Patent number: 5202397
    Abstract: A multiple site solid catalyst component capable of producing polyolefins having a broad or multimodal molecular weight distribution, such as a bimodal molecular weight distribution, is prepared by contacting a particulate solid support with a zirconium compound or complex to bind the zirconium compound or complex to the support, optionally followed by contacting the supported zirconium compound or complex with a Lewis acid to produce an intermediate product, optionally isolating and washing the supported zirconium compound or complex or resulting intermediate product to remove soluble by-products therefrom, and reacting the washed or unwashed supported zirconium compound or complex or intermediate product with a titanium or vanadium compound to produce a solid catalyst component.
    Type: Grant
    Filed: July 31, 1992
    Date of Patent: April 13, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: Leonard V. Cribbs, Michael W. Lynch
  • Patent number: 5198400
    Abstract: Mixed catalyst compositions comprised of a first supported chromium-containing catalyst component and a second supported chromium-containing catalyst component and which additionally have one or more metallic or non-metallic catalytic agents associated therewith are provided. The additional metallic or non-metallic elements associated with the catalyst components can be aluminum, titanium, zirconium, boron, phosphorous or combinations thereof. The pore volume of the silica supports used for the first and second catalyst components differs by at least 0.3 cc/g. The mixed catalyst compositions of the invention are useful for the preparation of polyolefins. They are particularly useful of polymerization of ethylene in particle form polymerizations to produce high density polyethylene blow molding resins having good processability and physical properties. The improved particle form polymerization process and products obtained thereby using the above-described mixed catalyst compositions are also described.
    Type: Grant
    Filed: March 26, 1991
    Date of Patent: March 30, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: Stanley J. Katzen, Thomas J. Pullukat, Michael W. Lynch, Louis J. Rekers
  • Patent number: 5192731
    Abstract: In accordance with the present invention, there are provided carrier-supported titanium catalyst components containing magnesium, aluminum, halogen and titanium as essential ingredients, which are obtained by a reaction of[I] a magnesium containing support obtained by previously bringing a support into contact with an organometallic compound of a metal of the Group II to IIIA of the periodic table having at least one hydrocarbon group attached directly to the metal atom or with a halogen containing compound, followed by contact with a magnesium compound in the liquid state having no reducing ability,[II] a reducing organometallic compound, and[III] a titanium compound in the liquid state, and processes for preparing the same and, at the same time, catalysts containing the above-mentioned catalyst components for use in preparing ethylene polymer and processes for preparing ethylene polymer using the catalyst for use in preparing ethylene polymer.
    Type: Grant
    Filed: October 23, 1991
    Date of Patent: March 9, 1993
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Mamoru Kioka, Kazumitsu Kawakita, Akinori Toyota
  • Patent number: 5189000
    Abstract: A supported catalyst for the polymerization and copolymerization of olefinically unsaturated compounds is described, comprising an organometallic compound of aluminium and a second component obtained by bringing a titanium, vanadium or chromium compound, at least one compound of a second metal chosen from V, Al, Zr, Hf, Mo and Nd and optionally a magnesium compound into contact with a porous support consisting of microbeads of aerogels of one or more inorganic oxides distinguished by low density, high porosity and the fact that at least 90% of the pores have a diameter lying within a very narrow range of values. The process for the polymerization or copolymerization of olefinically unsaturated compounds based on the use of said catalyst is also described.
    Type: Grant
    Filed: March 21, 1991
    Date of Patent: February 23, 1993
    Assignees: Montedipe S.r.l., Enichem S.p.A.
    Inventors: Francesco Masi, Renzo Invernizzi, Antonio Carbonaro, Lorenzo Costa, Angelo Moalli