Utilizing High Molecular Weight Synthetic Polymer Patents (Class 502/109)
  • Patent number: 5275993
    Abstract: An olefin polymerization catalyst which is obtained by contacting the following components (A) and (B): component (A): a product of contacting the following components (A.sub.1) and (A.sub.2):component (A.sub.1): polyolefin powder having specific values of pore diameter, pore volume, average pore diameter and average particle diameter,component (A.sub.2): a solid component for a Ziegler catalyst comprising titanium, magnesium and a halogen as the essential components;component (B): an organoaluminum compound.The supporting state of the catalyst is improved, and a contaminant-free polymer having a satisfactorily large particle diameter without the lowering of the activity or the stereoregularity of the catalyst is successfully obtained.
    Type: Grant
    Filed: June 26, 1992
    Date of Patent: January 4, 1994
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Takashi Fujita, Kazuyo Kitagawa
  • Patent number: 5262372
    Abstract: A process for the production of a highly active olefin polymerization vanadium catalyst, comprising a vanadium compound and an organophosphorous compound combined on a catalyst support, which is capable of producing a broad range of polymer products. The polymer product's molecular weight distribution may be tailored to suit a desired application by controlling the P/V ratio of the catalyst.
    Type: Grant
    Filed: February 3, 1992
    Date of Patent: November 16, 1993
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Gerald D. Malpass, Jr.
  • Patent number: 5244855
    Abstract: Catalyst components for the polymerization of olefins obtained by reacting a tetravalent titanium halide or halogen alcoholate and an electron-donor compound with a porous polymer support on which is supported a magnesium dihalide or a magnesium compound which does not contain Mg--C bonds and can be transformed into a dihalide, characterized in that the Mg content before and after the reaction with titanium compound ranges from 6 to 12% by weight.
    Type: Grant
    Filed: March 24, 1992
    Date of Patent: September 14, 1993
    Assignee: Himont Incorporated
    Inventors: Giampiero Morini, Enrico Albizzati
  • Patent number: 5237019
    Abstract: Metal-containing, shaped, polymeric, tertiary and/or secondary organosiloxane amine compounds are introduced which contain the metals Pd, Pt, Ru, Rh individually or in combination as well as optional promotors and/or moderators. The organosiloxane amine functioning as carrier for the metals contains the units ##STR1## and/or units ##STR2## in which R.sup.1 to R.sup.5 are a group ##STR3## with R.sup.6 as a double-bonded group bound to N and Si (e.g. an alkylene group) and X is an amine group such as The carrier substance can 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. A method of production is disclosed which can be carried out in several variants as well as the use of the metal-containing product as catalyst for hydrogenation reactions and oxidation reactions.
    Type: Grant
    Filed: March 27, 1992
    Date of Patent: August 17, 1993
    Assignee: Degussa Aktiengesellschaft
    Inventors: Stefan Wieland, Peter Panster, Bertrand Despeyroux, Klaus Deller
  • Patent number: 5139985
    Abstract: Catalyst components for the polymerization of olefins comprising a titanium or vanadium compound supported on a porous particulate polymeric support which particles have a porosity greater than 0.3 cc/g and a pore distribution such that at least 40% of the pores have radius greater than 150 .ANG..The catalyst components are prepared by impregnating the polymeric support with a solution of the Ti or V compound and evaporating the solvent.
    Type: Grant
    Filed: February 20, 1991
    Date of Patent: August 18, 1992
    Assignee: Himont Incorporated
    Inventors: Pier C. Barbe', Luciano Noristi, Gianni Pennini, Enrico Albizzati
  • Patent number: 5126303
    Abstract: Catalysts for the polymerization of olefins, comprising the product of the reaction between:A) a cyclopentadienyl compound of Ti, Zr or Hf;B) an alumoxane compound of formula: ##STR1## in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, the same or different from each other, are alkyl, alkenyl or alkylaryl radicals having 2 to 20 carbon atoms.
    Type: Grant
    Filed: January 29, 1990
    Date of Patent: June 30, 1992
    Assignee: Hinmont Incorporated
    Inventors: Luigi Resconi, Umberto Giannini, Enrico Albizzati
  • Patent number: 5118648
    Abstract: Supported olefin, e.g., alpha-olefin, polymerization catalyst compositions, such as Ziegler-Natta catalysts, are modified by using porous, polymer particles having an average pore diameter of at least about 10 .ANG. as the catalyst support. The resulting catalyst composition is more active than refractory oxide-supported catalysts and it is not susceptible to deactivation by catalyst poisons, such as oxygen or water. Additionally, the polymer particles need not be calcined prior to the catalyst synthesis.
    Type: Grant
    Filed: July 9, 1990
    Date of Patent: June 2, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Allan B. Furtek, Binnur Z. Gunesin
  • Patent number: 5102841
    Abstract: A process for the production of polyethylene comprising contacting ethylene or a mixture comprising ethylene and one or more alpha-olefins and, optionally, one or more diolefins, under polymerization conditions, with a catalyst system comprising:(a) a particulate catalyst precursor based on titanium or vanadium;(b) polypropylene support particles to which the catalyst precursor particles are bonded; and(c) a hydrocarbyl aluminum cocatalyst.
    Type: Grant
    Filed: December 11, 1990
    Date of Patent: April 7, 1992
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Kevin J. Cann, Robert C. Brady, III, Yimsan Gau
  • Patent number: 5077250
    Abstract: An olefin polymerization catalyst comprising:(A) a solid catalyst component containing a trivalent titanium, which is represented by the composition formulaMg.sub.m Ti(OR).sub.n X.sub.p [ED].sub.q(wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, ED is a electron donative compound, and m, n, p and q are each a number satisfying 1.ltoreq.m.ltoreq.51, 0<n.ltoreq.5, 5.ltoreq.p.ltoreq.106 and 0.2.ltoreq.q.ltoreq.2) obtained by reducing a titanium compound represented by the general formula Ti(OR.sup.1).sub.a X.sub.4-a (wherein R.sup.1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom and a is a number satisfying 0<a.ltoreq.
    Type: Grant
    Filed: April 24, 1990
    Date of Patent: December 31, 1991
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Yoshihiro Miyoshi, Hiroyuki Shiraishi, Takeshi Ebara, Toshio Sasaki, Kiyoshi Kawai
  • Patent number: 5075270
    Abstract: A process for preparing a transition metal component for a catalyst system wherein a specified aluminosiloxane derivative is reacted with a monohalopenated, alkylated, or alkoxylated compound of magnesium and the reaction product is chlorinated and reacted with a transition metal; a catalyst system comprising such transition metal component and a cocatalyst selected from organometallic compounds of a metal of Groups I through III of the Periodic Table; and the process of synthesizing olefin homopolymers and copolymers utilizing such catalyst system.
    Type: Grant
    Filed: June 9, 1986
    Date of Patent: December 24, 1991
    Assignee: Atochem
    Inventors: Claude Brun, Jean-Loup Lacombe
  • Patent number: 5049535
    Abstract: Catalysts for the polymerization of olefins, obtained from special zirconocenic compounds and from alkyl-Al compounds.
    Type: Grant
    Filed: January 30, 1990
    Date of Patent: September 17, 1991
    Assignee: Himont Incorporated
    Inventors: Luigi Resconi, Umberto Giannini, Enrico Albizzati
  • Patent number: 5021380
    Abstract: A method for the preparation of biaryl compounds is disclosed which comprises contacting an aryl halide with a tertiary-alkyl organometallic reagent (or the precursor components thereof) in the presence of a catalyst comprising a nickel compound and a coordinating ligand under conditions suitable for the formation of biaryl compound.In an alternate embodiment of the present invention, nickel(O) compounds are prepared from nickel(II) compounds by contacting a nickel(II) compound with a combination of an organophosphine and a bidentate nitrogen-containing coordinating ligand, and a tertiary-alkyl organometallic reagent (or the precursor components thereof) in an aprotic, non-polar, ether-containing solvent system for a time and under conditions suitable for the formation of nickel(0) compound.
    Type: Grant
    Filed: March 12, 1990
    Date of Patent: June 4, 1991
    Assignee: Eastman Kodak Company
    Inventor: Thomas A. Puckette
  • Patent number: 5021382
    Abstract: High density polymers of ethylene are produced in improved yields employing a solid Ziegler type transition metal-containing catalyst component and an organoaluminum cocatalyst in the presence of a small amount of an aliphatic diene having at least 4 carbon atoms and a terminal double bond. The amount of diene is from about 0.01 to about 3000 mole per gram atom of transistion metal in the catalyst component. The catalyst component variously may be pretreated with the diene before using the component for homopolymerization, may be prepolymerized with ethylene in the presence of the diene, may be prereduced in the presence of the diene, or the diene may be added to the polymerization reaction. Preferred dienes are .alpha.-.omega.-dienes.
    Type: Grant
    Filed: February 28, 1990
    Date of Patent: June 4, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Gerald D. Malpass, Jr.
  • Patent number: 4940682
    Abstract: A solid catalyst component for olefin polymerization which comprises a catalyst component comprising at least titanium and chlorine fixed onto a porous substance of which the pore volume, at a pore radius in a range of from 200 to 2,000 .ANG., is 0.3 cc/g or more, said pore volume is 35% or more of the pore volume at a pore radius in a range of from 35 to 75,000 .ANG., the average particle diameter is from 5 to 300 .mu.m, the geometrical standard deviation of the particle size distribution is 2 or less and the solubility in toluene at 100.degree. C. is 30 wt. % or less.
    Type: Grant
    Filed: October 26, 1988
    Date of Patent: July 10, 1990
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Toshio Sasaki, Takeshi Ebara, Kiyoshi Kawai
  • Patent number: 4921825
    Abstract: This invention is a catalyst for polymerization of olefins, comprising a compound of a transition metal of Group IVB of the periodic table, an aluminoxane and a particulate organic or inorganic compound carrier.This catalyst shows very high activity in the polymerization and copolymerization of olefins and gives polymers having a high bulk density, a uniform particle size, a low content of fine particles and a narrow molecular weight distribution and in the case of copolymers, a narrow composition distribution as well.
    Type: Grant
    Filed: August 23, 1988
    Date of Patent: May 1, 1990
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Mamoru Kioka, Norio Kashiwa
  • Patent number: 4900706
    Abstract: A solid catalyst component for .alpha.-olefin polymerization containing as catalyst components at least titanium, magnesium and chlorine which are impregnated into an organic porous polymer carrier having a mean particle diameter of 5 to 1,000 .mu.m and a pore volume of 0.1 ml/g or above at a pore radius of 100 to 5,000 .ANG., a catalyst system comprising at least said solid catalyst component (A) and an organoaluminum compound (B), as well as a process for producing .alpha.-olefin polymers using said catalyst system.
    Type: Grant
    Filed: March 11, 1988
    Date of Patent: February 13, 1990
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Toshio Sasaki, Takeshi Ebara, Hiroyuki Kora, Kiyoshi Kawai, Mituharu Yamasaki, Syozo Kawamata
  • Patent number: 4767735
    Abstract: A process for pretreating a Ziegler-type catalyst for use in olefin polymerization reactions. An olefin monomer is aded to a fluid carrier stream containing a Ziegler-type catalyst. The carrier stream containing the monomer and the catalyst is passed through an elongated tubular reactor at a flow rate sufficient to provide a residence time in the tubular reactor of less than 1 minute and under temperature conditions to prepolymerize the catalyst within the tubular reactor without plugging of the reactor. In a specific embodiment the residence time within the reactor is no more than 10 seconds, and more particularly, no more than 2 seconds.
    Type: Grant
    Filed: February 2, 1987
    Date of Patent: August 30, 1988
    Assignee: Cosden Technology, Inc.
    Inventors: John A. Ewen, Alan H. Bitzer
  • Patent number: 4713430
    Abstract: Finely divided ethene polymers are prepared by means of a Ziegler catalyst system composed of (1) a titanium-containing catalyst component obtained by precipitation in an organic liquid from (1.1) a solution of titanium tetrachloride in a hydrocarbon, (1.2) a solution of a certain organoaluminum compound in a hydrocarbon, and a catalyst component which contains (1.
    Type: Grant
    Filed: December 22, 1986
    Date of Patent: December 15, 1987
    Assignee: BASF Aktiengesellschaft
    Inventors: Juergen Kerth, Heinz Vogt
  • Patent number: 4661411
    Abstract: This invention discloses improved heterogeneous acid catalysts and a method for preparing these catalysts. A heterogeneous acid catalyst has been prepared by treating a carrier material with a solution containing a fluorocarbonsulfonic acid polymer dissolved in a suitable solvent, removing the solvent, and heat treating the coated carrier in such a way so as to prevent the polymer from being leached off the carrier. The final heat treatment of the composition to prevent the polymer from redissolving comprises an improvement in the preparation of a heterogeneous catalyst.
    Type: Grant
    Filed: February 25, 1986
    Date of Patent: April 28, 1987
    Assignee: The Dow Chemical Company
    Inventors: Charles W. Martin, Bobby R. Ezzell, John D. Weaver
  • Patent number: 4649128
    Abstract: A method is disclosed for controlling the activity of or deactivating a transition element olefin polymerization catalyst by contacting the catalyst with a deactivating polymer comprising a homopolymer of an unsaturated polar organic compound or a copolymer of an alpha-olefin and an unsaturated polar organic compound.
    Type: Grant
    Filed: November 21, 1985
    Date of Patent: March 10, 1987
    Assignee: National Distillers and Chemical Corporation
    Inventors: Louis J. Rekers, Anthony N. Speca, Harry W. Mayhew
  • Patent number: 4632912
    Abstract: Ziegler-Natta catalysts which are polymer supported compounds or complexes of elements of the d-block transition metals, lanthanide or actinide series are disclosed. An example of the polymer support is chloromethylated polystyrene-divinyl benzene copolymer covalently bonded to catechol. An example of the compound or complex of an element of the transition metal, lanthanide or actinide series is that which results when catechol which is covalently bonded to the polymer is contacted with titanium tetraisopropoxide. These catalysts are useful in preparing polymers with reduced halide content which reduces corrosion in polymer processing equipment.
    Type: Grant
    Filed: December 10, 1985
    Date of Patent: December 30, 1986
    Assignee: The Dow Chemical Company
    Inventors: Stephen A. Bedell, William R. Howell, Jr., William M. Coleman, III
  • Patent number: 4623707
    Abstract: .alpha.-Olefins are polymerized in the presence of Ziegler-Natta catalysts which are polymer supported compounds or complexes of elements of the d-block transition metals, lanthanide or actinide series. An example of the polymer support is chloromethylated polystyrene-divinyl benzene copolymer covalently bonded to catechol. An example of the compound or complex of an element of the transition metal, lanthanide or actinide series is that which results when catechol which is covalently bonded to the polymer is contacted with titanium tetraisopropoxide.
    Type: Grant
    Filed: December 10, 1985
    Date of Patent: November 18, 1986
    Assignee: The Dow Chemical Company
    Inventors: Stephen A. Bedell, William M. Coleman, III, William R. Howell, Jr.
  • Patent number: 4618595
    Abstract: A catalyst, a process of forming the catalyst, and polymerizing at least one alpha-olefin with the catalyst, said catalyst produced by precipitating a composition from a solution of a metal halide, for example, magnesium dihalide, and a transition metal compound, for example, titanium tetraalkoxide, in the presence of a particulate diluent, for example, polymeric fibrils, with an agent selected from among specified organometallic compounds, metal halides and oxygen-containing metal halides, hydrogen halides and organic acid halides. The composition is preferably further treated with a halide ion exchanging source, for example, titanium tetrahalide to form a particularly active catalyst. The catalyst is preferably used in combination with a cocatalyst comprising a metal hydride or organometallic compound selected from an element of Periodic Groups IA, IIA and IIIA.
    Type: Grant
    Filed: June 5, 1985
    Date of Patent: October 21, 1986
    Assignee: Phillips Petrolem Company
    Inventor: Richard E. Dietz
  • Patent number: 4582816
    Abstract: Method for the production of milled supports useful for the preparation of mono-1-olefin polymerization catalysts is provided by comminuting Mg(O)mX.sub.2 -m or Mn(O)mX.sub.2 -m, and high density ethylene polymer, optionally in the presence of an aromatic phenol and/or an aluminum halide to produce a composite catalyst support prior to further comminution with a tetravalent titanium halide to produce a first catalyst component and finally admixture of the first catalyst component with an organoaluminum catalyst compound. Polymerization process employing the novel catalyst system thus produced is also provided.
    Type: Grant
    Filed: February 21, 1985
    Date of Patent: April 15, 1986
    Assignee: Phillips Petroleum Company
    Inventor: Nemesio D. Miro
  • Patent number: 4579836
    Abstract: An exhaustively prepolymerized supported olefin polymerization catalyst component comprises solid, hydrocarbon-insoluble, magnesium-containing, titanium-containing catalyst particles which have been contacted with an olefin monomer and an organo-aluminum co-catalyst under exhaustive prepolymerization conditions at an Al/Ti atomic ratio such that the weight of prepolymer formed is less than 10 times the weight of such catalyst particles and the resulting prepolymerized catalyst particles essentially are inactive to further polymerization.
    Type: Grant
    Filed: May 22, 1985
    Date of Patent: April 1, 1986
    Assignee: Amoco Corporation
    Inventors: Gregory G. Arzoumanidis, Sam S. Lee, Benjamin S. Tovrog
  • Patent number: 4568730
    Abstract: An olefin polymerization catalyst component produced by impregnating polyethylene with a pulverized solid olefin polymerization catalyst containing a Group 4b or 5b transition metal, for example a pulverized magnesium chloride containing titanium is impregnated in low molecular weight polyethylene by copulvering, then subjecting the impregnated polymer particles to shear in an inert medium at about the softening point of the polyethylene, which when used as a cocatalyst with an organoaluminum compound produces polymers of improved morphology having a more regular shape and higher bulk density than pulverized catalyst alone.
    Type: Grant
    Filed: August 13, 1984
    Date of Patent: February 4, 1986
    Assignee: Exxon Research & Engineering Co.
    Inventor: Victoria Graves
  • Patent number: 4560671
    Abstract: Solid polyolefin catalysts are adapted for use in low pressure gas phase fluid bed polymerization processes by being mixed with selected particulate organic support materials in a high speed bladed finishing device so as to cause the catalysts materials to become embedded in, and/or adhered to, softened particles of the support material.
    Type: Grant
    Filed: April 18, 1985
    Date of Patent: December 24, 1985
    Assignee: Union Carbide Corporation
    Inventors: Laurence H. Gross, Allen Noshay
  • Patent number: 4558023
    Abstract: Process for the preparation of an active solid hydrocarbon which can be used to polymerize olefines.This process comprises forming a pulverulent composition by mixing a transition metal component, a porous organic or inorganic solid support and an organometallic compound of the organo-Al, organo-Mg or organo-Zn type, and polymerizing a controlled amount of one or more C.sub.2 to C.sub.12 olefines in the gas phase in contact with the pulverulent composition with a specific hourly conversion of the olefines to produce the active solid hydrocarbon.The above active solid hydrocarbon can be used, by itself or together with an organometallic cocatalyst, as a catalytic system for polymerization of olefines, in particular in the gas phase.
    Type: Grant
    Filed: February 23, 1984
    Date of Patent: December 10, 1985
    Assignee: Atochem
    Inventors: Claude Brun, Auguste Cheux, Robert Pelletier
  • Patent number: 4544646
    Abstract: An olefin polymerization and interpolymerization catalyst composition prepared by reacting at least one novel magnesium silylamide compound with a compound of a transition metal selected from Groups IIIB, IVB, VB and VIB of the fourth and fifth periods of the periodic table, and Groups VIIB and VIIIB of the fourth period.
    Type: Grant
    Filed: March 16, 1984
    Date of Patent: October 1, 1985
    Assignee: Chemplex Company
    Inventors: Thomas J. Pullukat, Raymond E. Hoff
  • Patent number: 4500648
    Abstract: Generally, linear polyethylene containing long chain branching is obtained by polymerizing ethylene in the presence of a catalyst comprising a transition metal compound such as titanium chloride, an organoaluminum compound represented by the formula R.sub.1 R.sub.2 AlR.sub.p wherein R.sub.1 & R.sub.2 are the same or different hydrocarbyl groups having from 1 to 18 carbon atoms and R.sub.p is a polymeric hydrocarbyl group containing long chain branching and an aluminum alkyl cocatalyst.
    Type: Grant
    Filed: April 25, 1983
    Date of Patent: February 19, 1985
    Assignee: Exxon Research & Engineering Co.
    Inventor: Dennis B. Malpass
  • Patent number: 4482638
    Abstract: A process is disclosed for producing, in situ and without milling or grinding, an alpha olefin polymerization catalyst component which comprises adding an olefin to a titanium halide and then adding an electron donor to the mixture of the titanium halide and the olefin.
    Type: Grant
    Filed: July 14, 1983
    Date of Patent: November 13, 1984
    Assignee: Northern Petrochemical Company
    Inventor: Richard W. Fries
  • Patent number: 4477639
    Abstract: A polymer-supported constituent for olefin polymerization catalyst obtained by: mixing in organic solution a chlorine-containing organic polymer and a magnesium compound, removing the solvent, and reacting the resulting magnesium-modified polymer with a titanium halide. An olefin polymerization catalyst is formed by mixing such a polymer-supported constituent with an appropriate organo-metallic compound and optionally also an appropriate selectivity control agent.
    Type: Grant
    Filed: May 27, 1983
    Date of Patent: October 16, 1984
    Assignee: Shell Oil Company
    Inventor: Robert P. Nielsen
  • Patent number: 4465783
    Abstract: A solid material which is a transition metal composition, or a support for a transition metal compound, is suspended in a liquid medium, the mixture is subjected to mechanical action and the treated mixture is spray-dried. If the solid is a support material, it is subsequently contacted with a transition metal compound. The mechanical action can be a grinding process or a process providing simultaneous vigorous agitation and a shearing action. The transition metal composition may be used with an organic metal compound to polymerize an unsaturated monomer to give a polymer of good particle form.
    Type: Grant
    Filed: August 6, 1982
    Date of Patent: August 14, 1984
    Assignee: Imperial Chemical Industries PLC
    Inventor: Ian D. McKenzie
  • Patent number: 4465782
    Abstract: A supported transition metal composition is obtained by suspending a support material in an inert liquid medium, spraying the suspension, collecting a solid material and contacting the sprayed solid with a transition metal compound. The support material may be a metal halide such as magnesium chloride or an inorganic oxide such as silica or alumina. In addition to being contacted with the transition metal compound, the support material may be contacted either before or after the spraying step with other reagents such as organo metallic compounds, halogen compounds, or Lewis Base compounds. The product obtained after contacting with the transition metal compound may be used as a component of a polymerization catalyst system to polymerize an unsaturated monomer such as ethylene or propylene.
    Type: Grant
    Filed: August 6, 1982
    Date of Patent: August 14, 1984
    Assignee: Imperial Chemistry Industries PLC
    Inventor: Ian D. McKenzie