Utilizing Water Or Compound Containing Hydroxy Bonded To Carbon Patents (Class 502/111)
  • Patent number: 4814310
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the gas phase polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 6 to about 10 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an aluminum trialkyl solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added and the resulting material dried to free flowing powder. The dry free flowing powder may then be used as a supported metalllocene alumoxane catalyst complex for gas phase polymerization of olefins.
    Type: Grant
    Filed: December 17, 1987
    Date of Patent: March 21, 1989
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 4814313
    Abstract: A method for the production of a catalyst carrier for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X for a halogen atom, and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M for a boron, carbon, silicon, aluminum, or phosphorus atom, R.sup.1 for a hydrocarbon group having 1 to 20 carbon atoms, and m for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied, to contact (D) a halogen-containing alcohol.
    Type: Grant
    Filed: December 14, 1987
    Date of Patent: March 21, 1989
    Assignee: TOA Nenryo Kogyo Kabushiki Kaisha
    Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
  • Patent number: 4814312
    Abstract: A method for the production of a catalyst component for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X for a halogen atom], and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M for a boron, carbon, silicon, aluminum, or phosphorus atom, R.sup.1 for a hydrocarbon group having 1 to 20 carbon atoms, and m for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied], to contact (D) a halogen-containing alcohol and then contact (E) an electron donor type compound and (F) a titanium compound.
    Type: Grant
    Filed: December 14, 1987
    Date of Patent: March 21, 1989
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
  • Patent number: 4784983
    Abstract: A catalyst system for use in olefinic polymerization and copolymerization is comprised of components (A), (B) and (C). The catalyst component (A) consisting essentially of titanium, magnesium, halogen, polycarboxylic acid esters and organic phosphorus compounds is a solid product, being prepared by mixing titanium tetrahalide and auxiliary precipitant with a homogeneous solution of magnesium halide in a solvent system consisting essentially of an organic epoxy compound and an organic phosphorus compound to form a solid product which is then treated with a polycarboxylic acid ester and titanium tetrahalide. Component (B) is an organic aluminum compound, and component (C) is an organic silicon compound. The catalyst system has a very high activity, and the resultant polymers have very high stereospecificity and good granular appearance.
    Type: Grant
    Filed: September 15, 1986
    Date of Patent: November 15, 1988
    Assignee: Beijing Research Institute of Chemical Industry
    Inventors: Bingquan Mao, Aichun Yang, Ying Zheng, Juxiou Yang, Zhulan Li
  • Patent number: 4695558
    Abstract: Disclosed are catalysts for the polymerization of ethylene and of mixtures thereof with olefins, comprising the product obtained by reacting the following components:(a) an Al-alkyl compound;(b) an electron-donor compound containing at least a nitrogen atom, said compound being reactive towards MgCl.sub.2, but not towards Al-triethyl; and(c) the reaction product between a titanium compound containing at least a titanium-halogen bond and an anhydrous magnesium halide.The obtained (co)polymers have a very narrow molecular weight distribution which renders them particularly suitable for some applications, such as injection molding.
    Type: Grant
    Filed: March 19, 1985
    Date of Patent: September 22, 1987
    Assignee: Montedison S.p.A.
    Inventors: Enrico Albizzati, Enrico Pettenati, Umberto Zucchini, Illaro Cuffiani
  • Patent number: 4683215
    Abstract: A process for removing one or more contaminants of the formula TiCl.sub.3 OR, in which R is an alkyl or aryl group, from a liquid phase comprising TiCl.sub.4, characterized in that the contaminants are reacted with an organic acid halide ##STR1## in which R' is an aryl or alkyl group, to precipitate an addition complex of the formula ##STR2## in which n is a number of from 0.3 to 3.0, and the addition complex is separated from the liquid phase.
    Type: Grant
    Filed: May 8, 1986
    Date of Patent: July 28, 1987
    Assignee: Shell Oil Company
    Inventors: Jean L. Bilhou, Brian L. Goodall
  • Patent number: 4673661
    Abstract: Catalysts for polymerization and copolymerization of olefins to form polymers having a high degree of isotacticity and fast rate of crystal transformation. The catalysts embody a component made by chlorinating a magnesium alkyl with chlorine or a mixture of chlorine and alkyl chloride to form a carrier, contacting the carrier first with liquid TiCl.sub.4, then with a Lewis base, and after that at least once with TiCl.sub.4 in the absence of Lewis base.
    Type: Grant
    Filed: January 21, 1986
    Date of Patent: June 16, 1987
    Assignee: Neste Oy
    Inventors: Barbro U. Lofgren, Luciano Luciani, Hanneli Seppanen, Maria H. Stjernberg, Eero I. Iiskola
  • Patent number: 4668650
    Abstract: A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with a liquid solution containing an excess of an organomagnesium composition with respect to the OH groups and contacting the thus-formed magnesium-containing carrier with a hydrocarbyl alcohol and at least one transition metal compound. Prior to contacting the magnesium-containing carrier with the alcohol, most of the liquid must be removed therefrom, so that it comprises not more than about 6% of the liquid. The amount of the transition metal compound is such that the molar ratio thereof to magnesium in the reaction mixture is about 0.3 to about 0.9. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalyst of the invention.
    Type: Grant
    Filed: January 3, 1986
    Date of Patent: May 26, 1987
    Assignee: Mobil Oil Corporation
    Inventors: Frederick Y. Lo, Thomas E. Nowlin, Margaret M. Wu
  • Patent number: 4663299
    Abstract: A process for preparing spherical particles of a compound with the general formula Mg(OR).sub.2-a (OR').sub.a is disclosed. In the process R is an alkyl group with from 2 to 8 carbon atoms, R' is an alkyl group with from 1 to 7 carbon atoms and a is a number of from 0 to 0.5. The process comprises preparing a homogeneous solution of a compound Mg(OR).sub.2 in an aliphatic alcohol with the general formula R'OH, spray-drying the solution at a temperature of from 15.degree. to 85.degree. C., suspending the spray-dried solid particles in an aliphatic alcohol with the formula ROH in which R is the same alkyl group as present in the said compound Mg(OR).sub.2, heating the suspension in order to remove an alcohol with the formula R'OH from the liquid phase by distillation and separating the solid particles from the liquid phase.
    Type: Grant
    Filed: July 14, 1986
    Date of Patent: May 5, 1987
    Assignee: Shell Oil Company
    Inventors: John C. Chadwick, Jacob C. v. d. Sar
  • Patent number: 4661465
    Abstract: A method for preparing Ziegler catalysts is disclosed wherein a mixture (A) containing the product resulting from mixing in an inert hydrocarbon diluent (1) a hydrocarbon soluble magnesium alkyl compound in said hydrocarbon solvent, (2) an aliphatic alcohol or carbon dioxide and (3) a titanium compound is reacted with (B) a reducing halide source in said hydrocarbon solvent. Components (A) and (B) are mixed at a constant initial temperature. When the magnesium concentration in component (A) and the metal concentration in component (B) are relatively low, the resultant polymer has a relatively narrow particle size distribution whereas when said concentration is relatively high, the resultant polymer has a relatively broad particle size distribution. When the ratio of the number of moles of aliphatic alcohol:total number of hydrocarbyl groups attached to the metal atom in component (1) is relatively low, the resultant polymer has a relatively small average particle size.
    Type: Grant
    Filed: August 7, 1986
    Date of Patent: April 28, 1987
    Assignee: The Dow Chemical Company
    Inventors: Ricardo Fuentes, Jr., Gary R. Marchand, Larry A. Meiske
  • Patent number: 4650778
    Abstract: Metal halide particles useful, among other things, as olefin polymerization catalyst precursors and catalyst supports are prepared by vaporizing the metal halide and then condensing it in the presence of a diluent.
    Type: Grant
    Filed: January 18, 1985
    Date of Patent: March 17, 1987
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Ulrich Klabunde, Rolf Mulhaupt
  • Patent number: 4617284
    Abstract: A catalyst component for polymerization of olefins, which consists essentially of a particulate contact reaction product of an average particle size of 10 to 100 microns, obtained by contacting the surfaces of particles of a product of contact reaction with a magnesium halide and an alkoxy group-containing compound of a metal of Group I, II, III or IV of the Periodic Table with an alcohol compound and contacting the resulting contact reaction product with a liquid titanium halide. This catalyst component has a high activity and provides a polymer having a relatively large particle size and a narrow particle size distribution.
    Type: Grant
    Filed: May 28, 1985
    Date of Patent: October 14, 1986
    Assignee: Mitsubishi Petrochemical Company, Limited
    Inventors: Mitsuyuki Matsuura, Takashi Fujita, Yoshio Sakamoto
  • Patent number: 4601994
    Abstract: Supported Ti.sup.III catalysts are prepared by contacting a slurry of a solid inorganic support such as magnesium chloride in a hydrocarbon medium such as Isopar.RTM. E containing a tetravalent titanium compound containing at least two halogen atoms such as titanium tetrachloride with hydroquinone or a substituted hydroquinone.
    Type: Grant
    Filed: June 21, 1985
    Date of Patent: July 22, 1986
    Assignee: The Dow Chemical Company
    Inventor: William M. Coleman, III
  • Patent number: 4588704
    Abstract: In a catalyst preparation process wherein effluent solvent or diluent is water washed to remove impurities and subsequently recycled to the process, the formation of solids upon mixing organic and aqueous phases is prevented by the admixture in appropriate proportions of effluent portions containing, e.g., an organoaluminum compound such as ethylaluminum sesquichloride and a transition metal tetrahalide such as titanium tetrachloride, respectively, then mixing with water, followed by optional neutralization of the acidic aqueous phase with a chemical base such as NH.sub.4 OH.
    Type: Grant
    Filed: April 30, 1985
    Date of Patent: May 13, 1986
    Assignee: Phillips Petroleum Company
    Inventors: Charles A. Drake, Bill Loffer
  • Patent number: 4588703
    Abstract: An olefin polymerization catalyst prepared by reacting a metal dihalide and a transition metal, then reacting that component with a precipitating agent, and then reacting the resulting solid with an activating component, wherein multiple activation steps are used so that it is possible to obtain a given level of activity with less activating component.
    Type: Grant
    Filed: July 18, 1984
    Date of Patent: May 13, 1986
    Assignee: Phillips Petroleum Company
    Inventors: Kiplin D. Cowan, Dale E. Pierce, Oscar D. Nowlin
  • Patent number: 4585749
    Abstract: An olefin polymerization catalyst prepared by reacting an admixture of anhydrous magnesium dihalide and hydrous magnesium dihalide with reactants including benzoic acid ester, an alkoxytitanium compound, an organoaluminum halide, and a titanium halide.
    Type: Grant
    Filed: September 28, 1983
    Date of Patent: April 29, 1986
    Assignee: Phillips Petroleum Company
    Inventors: Dale E. Pierce, Jerry L. Vaughan, Oscar D. Nowlin
  • 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: 4579834
    Abstract: A vanadium-containing catalyst component useful for the polymerization of olefins to polyolefins having a high molecular weight and a broad molecular weight distribution comprising polymerizing the polyolefins in the presence of a catalyst comprising (A) a vanadium-containing catalyst component obtained by contacting an inert support material with a dihydrocarbyl magnesium compound, optionally an oxygen-containing compound, a vanadium compound, a Group III metal halide, and (B) an aluminum alkyl cocatalyst.
    Type: Grant
    Filed: December 12, 1984
    Date of Patent: April 1, 1986
    Assignee: Exxon Research & Engineering Co.
    Inventor: Steven A. Best
  • Patent number: 4578374
    Abstract: A vanadium-containing catalyst component useful for the polymerization of olefins to polyolefins having a high molecular weight and a broad molecular weight distribution comprising polymerizing the polyolefins in the presence of a catalyst comprising (A) a vanadium-containing catalyst component obtained by contacting an inert support material with a dihydrocarbyl magnesium compound, optionally an oxygen-containing compound, a vanadium compound, a Group III metal halide, and (B) an aluminum alkyl cocatalyst.
    Type: Grant
    Filed: December 12, 1984
    Date of Patent: March 25, 1986
    Assignee: Exxon Research & Engineering Co.
    Inventor: Steven A. Best
  • Patent number: 4568659
    Abstract: A transition metal catalyst component (1) for Ziegler catalyst systems is prepared by (1.1) first combining (1.1.1) an inorganic oxidic substance (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) an organic solvent and (IIb) a transition metal composition to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV) and (1.2) then combining (1.2.1) the solid-phase intermediate (IV) obtained from (1.1) with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase products (VI) being the transition metal catalyst component (1).The characteristic feature is that the solution (II) employed in stage (1.1) consists of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide and (IIb3) a zirconium tetrahalide.
    Type: Grant
    Filed: October 30, 1984
    Date of Patent: February 4, 1986
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Warzelhan, Rainer Karer, Robert Bachl, Guido Funk
  • Patent number: 4565795
    Abstract: Polymerization of olefins in the presence of a catalyst system comprising a titanium-containing component A associated with a chemically treated silica-containing composition and a dihydrocarbylmagnesium compound and a cocatalyst component B comprising metal hydride or organometal compound derived from an element of Groups IA-IIIA of the Periodic Table.
    Type: Grant
    Filed: December 7, 1979
    Date of Patent: January 21, 1986
    Assignee: Phillips Petroleum Company
    Inventors: James N. Short, Max P. McDaniel
  • Patent number: 4551439
    Abstract: A solid catalyst component for olefin polymerization having a high polymerization activity and affording a highly stereoregular polymer having a good particulate form, and a process for producing the same are provided, which component indispensably contains Mg, Ti, Al, halogen and alkoxy group; has two absorption peaks (absorbances A.sub.1 and A.sub.2) at specified wavenumbers within a specified region of spectra according to infrared spectrophotometry, A.sub.1 /A.sub.2 and A.sub.1 /A.sub.3 (A.sub.
    Type: Grant
    Filed: February 11, 1985
    Date of Patent: November 5, 1985
    Assignee: Chisso Corporation
    Inventors: Masato Harada, Shinya Miya, Sadahiko Yamada, Makoto Iijima
  • Patent number: 4550093
    Abstract: A new polymerization catalyst system comprising an aluminum compound and a transition metal compound on an alumina-based aerogel support, a process for preparing the polymerization catalyst system and use of the catalyst system for polymerization and copolymerization of alpha-olefins are disclosed. A heat-activated alumina-based aerogel useful as a catalyst support and having a morphology by transmission electron microcopy comprising extremely thin folded film-like ribbons or plates and having a high BET surface area, high pore volume, and low bulk density is also disclosed.
    Type: Grant
    Filed: August 6, 1984
    Date of Patent: October 29, 1985
    Assignee: Allied Corporation
    Inventors: Anthony J. Fanelli, Alson K. Price
  • Patent number: 4544647
    Abstract: A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent a mixture of (A) an organomagnesium material, (B) an organic hydroxyl-containing material, (C) a reducing halide source and (D) a transition metal compound.
    Type: Grant
    Filed: March 6, 1984
    Date of Patent: October 1, 1985
    Assignee: The Dow Chemical Company
    Inventors: Ricardo Fuentes, Jr., Calvin P. Esneault
  • Patent number: 4540680
    Abstract: An intermetallic compound comprising the reaction product of a transition metal and a reducing metal of a higher oxidation potential than the transition metal obtained by the reaction of a polymeric transition metal oxide alkoxide and the reducing metal in the presence of dicarbonyl compound; and catalyst components and systems for the polymerization of alpha olefins.
    Type: Grant
    Filed: February 8, 1984
    Date of Patent: September 10, 1985
    Assignee: National Distillers and Chemical Corporation
    Inventor: Anthony N. Speca
  • Patent number: 4540757
    Abstract: Polymerization of olefins in the presence of a catalyst system comprising titanium-containing component (A) associated with a milled blend of at least two different silica-containing materials having different MI (polymer melt index) potentials in which at least one of the silicas has been treated with a chemical agent which reacts with OH groups on the surface of the silica and a dihydrocarbylmagnesium compound, and a cocatalyst component (B) comprising an organoaluminum compound. Ethylene polymers having broad molecular weight distribution are obtained using the catalysts defined herein.
    Type: Grant
    Filed: October 1, 1984
    Date of Patent: September 10, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4540679
    Abstract: Composition comprising a transition metal component and magnesium hydrocarbyl carbonate. Composition can be prepared by reacting suspension of magnesium alcoholate with carbon dioxide to form a magnesium hydrocarbyl carbonate and reacting magnesium hydrocarbyl carbonate with transition metal component. When the suspending liquid comprises an alcohol, the magnesium hydrocarbyl carbonate dissolves and is subsequently precipitated with an antisolvent comprising metal alkyl or transition metal halide. When the suspending liquid is substantially free of alcohol, the magnesium hydrocarbyl carbonate suspension is reacted with metal alkyl and transition metal compound.
    Type: Grant
    Filed: March 23, 1984
    Date of Patent: September 10, 1985
    Assignee: Amoco Corporation
    Inventors: Gregory G. Arzoumanidis, Sam S. Lee
  • Patent number: 4537870
    Abstract: A catalyst prepared by reacting a dihalide, such as MgCl.sub.2 ; a titanium compound, such as a titanium tetraalkoxide; and an electron donor to form a first catalyst component; then reacting that component with an organoaluminum halide; then reacting the resulting solid with TiCl.sub.4 ; and then reacting the solid after that step with HSiCl.sub.3. Also the use of the catalyst in olefin polymerization is disclosed.
    Type: Grant
    Filed: July 12, 1984
    Date of Patent: August 27, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Gil R. Hawley
  • Patent number: 4536487
    Abstract: An intermetallic compound comprising the reaction product of a transition metal and a reducing metal of a higher oxidation potential than the transition metal obtained by the reaction of a polymeric transition metal oxide alkoxide and the reducing metal in the presence of a mono- or dialkyl phosphate or mixtures thereof in which each alkyl contains up to 10 carbon atoms; and catalyst components and systems for the polymerization of alpha olefins.
    Type: Grant
    Filed: February 8, 1984
    Date of Patent: August 20, 1985
    Assignee: National Distillers and Chemical Corporation
    Inventor: Anthony N. Speca
  • Patent number: 4525554
    Abstract: In a process for polymerizing an olefin in the presence of a catalyst system combining an organoaluminum compound with a hydrocarbon insoluble solid catalytic component prepared by treating a hydrocarbon solution containing a magnesium compound, and a titanium compound with an aluminum halide having the formulaAlR.sub.l.sup.1 X.sub.3-l.sup.1(R.sup.1 represents an alkyl, aryl or cycloalkyl group and X.sup.1 represents a halogen atom, and l is 1.ltoreq.l.ltoreq.2),an improvement characterized in that the magnesium compound is a compound having the formulaMg(OR.sup.2).sub.m X.sub.2-m.sup.2(R.sup.2 represents an alkyl, aryl or cycloalkyl group; X.sup.2 represents a halogen atom; and m is 1 or 2) and the titanium compound is a compound having the formulaTi(OR.sup.3).sub.n X.sub.4-n.sup.3(R.sup.3 represents an alkyl, aryl or cycloalkyl group; X.sup.3 represents a halogen atom; n is 1, 2 or 3).
    Type: Grant
    Filed: March 4, 1981
    Date of Patent: June 25, 1985
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Toru Tanaka, Kazutoshi Iwatani, Nobuo Enokido, Atsushi Murakami, Yukio Yamaguchi
  • Patent number: 4525469
    Abstract: A catalyst composition for the polymerization or copolymerization of olefins composed of(A) a titanium component (a-1) or (a-2),(a-1) a highly active titanium component containing titanium, magnesium and halogen as essential ingredients, or(a-2) a highly active titanium catalyst component obtained by treating component (a-1) with an organic compound containing active hydrogen bonded to oxygen, and(B) an organoaluminum compound component, wherein(i) when component (A) is the component (a-1), component (b) is an organoaluminum compound component obtained by treating a halogen-containing organoaluminum compound having a halogen/Al atomic ratio of at least 1 but less than 2 with a compound selected from the group consisting of water and organic compounds having active hydrogen bonded to oxygen, and(ii) when component (A) is the component (a-2), the component (B) is a halogen-containing organoaluminum compound having a halogen/Al atomic ratio of at least 1 but less than 2, and the ratio of the amount (x) of the or
    Type: Grant
    Filed: October 25, 1983
    Date of Patent: June 25, 1985
    Assignee: Mitsui Petrochemical Industries Ltd.
    Inventors: Takashi Ueda, Norio Kashiwa
  • Patent number: 4517307
    Abstract: Components of catalysts for the polymerization of ethylene and of mixtures thereof with other olefins, in the form of emulsions or dispersions, in an inert liquid medium or in an inert gas phase of a liquid phase, comprising a compound of a metal of Groups IV to VI inclusive, of the Mendelyeev Periodic System, or a composition containing such a compound of the Mendelyeev Periodic System, which compound or composition is immiscible with aliphatic hydrocarbons, or which components are obtained from emulsions or dispersions, in an inert liquid medium or in gas phase, of a precursor of the catalyst component which, in the liquid state, is immiscible with the aliphatic hydrocarbons.An object of this invention is to provide new catalyst components for use in the polymerization of ethylene and of mixtures thereof with olefins and the catalysts obtained therefrom.
    Type: Grant
    Filed: December 22, 1982
    Date of Patent: May 14, 1985
    Assignee: Montedison S.p.A.
    Inventors: Illaro Cuffiani, Paolo Longi, Umberto Zucchini, Gianni Pennini
  • Patent number: 4513095
    Abstract: Polymeric transition metal oxide alkoxides are converted by reaction with a reducing metal having a higher oxidation potential then the transition metal to a catalyst precursor, activated with a halide to form a catalyst component for olefin polymerization. Particularly exemplified are the reaction products of partially hydrolyzed titanium alkoxides with Mg.degree., used as a catalyst component for slurry polymerizations to produce polyethylene resins.
    Type: Grant
    Filed: April 7, 1983
    Date of Patent: April 23, 1985
    Assignee: National Distillers and Chemical Corporation
    Inventor: Anthony N. Speca
  • Patent number: 4506029
    Abstract: A catalytic component for polymerizing olefins comprises a solid support containing magnesium-halogen or manganese-halogen bonds, a transition metal halide of a metal selected from Groups IVB and VB of the periodic table, and electron donors. This catalytic component is obtainable by steps comprising:(a) contacting a mixture comprising a magnesium halide or manganese halide and at least one electron donor with a Ti(OR).sub.4 compound to form a solution, where R is a hydrocarbyl or halogenated hydrocarbyl moiety containing 1 to 20 carbon atoms or a halogen, and(b) reacting the solution with a reagent comprising a transition metal halide selected from Groups IVB and VB of the periodic table,whereby, with a suitable cocatalyst, polyolefin is formed with high activity, showing a high Isotactic Index, and with a narrow range of particle size distribution.
    Type: Grant
    Filed: December 20, 1982
    Date of Patent: March 19, 1985
    Assignee: Stauffer Chemical Company
    Inventor: Elliot I. Band
  • Patent number: 4506027
    Abstract: Method of preparing a supported Ziegler-catalyst active in the polymerization of alpha-olefins to polymers particularly suited to working by blow-moulding, by reacting:(A) an organometallic compound of aluminium, and(B) the product of the reaction of titanium and vanadium halides with a solid support obtained by the spray drying of magnesium chloride in a mixed solution of ethanol and methanol, the support containing both ethanolic and methanolic alcoholic hydroxyl groups.
    Type: Grant
    Filed: November 10, 1983
    Date of Patent: March 19, 1985
    Assignee: Enichimica Secondaria S.p.A.
    Inventors: Renzo Invernizzi, Ferdinando Ligorati
  • Patent number: 4503159
    Abstract: An olefin polymerization catalyst prepared by reacting water with a magnesium dihalide in the presence of a phase transfer catalyst and reacting the resulting hydrated magnesium dihalide with reactants including a benzoic acid ester, an alkoxytitanium compound, an organoaluminum halide and a titanium halide.
    Type: Grant
    Filed: August 19, 1983
    Date of Patent: March 5, 1985
    Assignee: Phillips Petroleum Company
    Inventors: Albert P. Masino, Kiplin D. Cowan, Gil R. Hawley
  • Patent number: 4501866
    Abstract: A method for preparing high cis-1,4 polybutadiene by a continuous process which involves the continuous polymerization of 1,3-butadiene in solution under adiabatic conditions is provided. The method comprises the steps of: (I) feeding continuously to a single agitated polymerization reactor: (a) a monomer stream comprising 1,3-butadiene in a hydrocarbon solvent; (b) a preformed .pi. allyl catalyst stream formed by admixing a carboxylated metal oxy borate compound represented by the formulae (RCOOMO).sub.3 B or (ROCOOMO).sub.2 B-OR' wherein R and R' are alkyl radicals containing from 7 to 17 carbon atoms and M is nickel or cobalt, an organo aluminum compound, an alcohol, a small amount of 1,3-butadiene and a hydrocarbon solvent; and (c) a cocatalyst stream comprising a boron trifluoride complex with an alcohol; and (II) withdrawing continuously from said reactor high cis-1,4 polybutadiene at the same rate as said monomer, preformed catalyst and cocatalyst streams are fed to the reactor.
    Type: Grant
    Filed: July 23, 1984
    Date of Patent: February 26, 1985
    Assignee: The Firestone Tire & Rubber Company
    Inventors: David M. Roggeman, Shrikant R. Malani, Jung W. Kang
  • Patent number: 4496660
    Abstract: A catalyst for polymerizing olefins is the reaction product of (A) the reaction product of (1) the reaction product of (a) an alkyl magnesium compound such as dibutylmagnesium, with (b) an oxygen-containing and/or nitrogen-containing compound such as n-propyl alcohol, or isopropylamine, with (2) a halide source such as titanium tetrachloride or silicon tetrachloride; and (B) a transition metal compound such as titanium tetrachloride and (C) a reducing agent such as triisobutylaluminum.Also disclosed is a non-transition metal containing catalyst support for use in preparing olefin polymerization catalysts.The polymers which are produced in the presence of this catalyst and a cocatalyst such as triethylaluminum have a low catalyst support to transition metal ratio and therefore, the catalyst efficiency based on quantity of polymer per quantity of total catalyst is very high resulting in a polymer having good color and very little, if any, corrosion.
    Type: Grant
    Filed: October 1, 1980
    Date of Patent: January 29, 1985
    Assignee: The Dow Chemical Company
    Inventors: Donald E. Gessell, Ronald L. Gibbs, Ricardo Fuentes, Jr.
  • Patent number: 4492768
    Abstract: A catalyst and its method of preparation and use involving reacting a magnesium dihalide, an alkoxytitanium compound and water, followed by reaction with an organoaluminum compound and then with a halide ion exchanging source.
    Type: Grant
    Filed: August 19, 1983
    Date of Patent: January 8, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Gil R. Hawley
  • Patent number: 4477587
    Abstract: This invention comprises a catalytic component for polymerizing olefins comprising a solid support containing magnesium-halogen bonds, a transition metal halide of a metal selected from Groups IVB and VB of the periodic table, and an electron donor obtained by the steps comprising:(a) reacting an organometallic compound whose metal comprise members of Groups I to III of the periodic table with an alcohol, ROH, where R is an alkyl, cycloalkyl, or arylalkyl moiety having 1 to 16 carbon atoms, a polysiloxane, and a transition metal halide to form a solid;(b) treating the solid with a transition metal halide optionally in the presence of a polysiloxane to form a treated solid; and(c) reacting the treated solid with an electron donor and a transition metal halide to form the component.
    Type: Grant
    Filed: December 20, 1982
    Date of Patent: October 16, 1984
    Assignee: Stauffer Chemical Company
    Inventor: Elliot I. Band
  • Patent number: 4472523
    Abstract: Olefins such as ethylene can be polymerized in high productivities using a catalyst system wherein one catalyst component comprises a precipitated complex of zirconium tetrahydrocarbyloxide and/or titanium tetrahydrocarbyloxide and dihydrocarbylmagnesium. The productivity of the preferred catalyst containing both zirconium and titanium has been found to be substantially higher than the productivity of those catalysts obtained from either only Zr(OR').sub.4 or only Ti(OR").sub.4 and second catalyst component comprises at least one organometallic compound of a metal selected from the Groups I-III of the Mendeleev Periodic Table.
    Type: Grant
    Filed: April 18, 1983
    Date of Patent: September 18, 1984
    Assignee: Phillips Petroleum Company
    Inventors: Melvin B. Welch, Richard E. Dietz
  • Patent number: 4467044
    Abstract: This invention comprises a catalytic component for polymerizing olefins comprising a siliceous support containing magnesium halide, a transition metal halide, and an electron donor obtained by steps comprising:(a) infusing siliceous oxide with magnesium halide complexed with an alcohol to form a support;(b) reacting the support with an organometallic compound of a metal from Groups I to III of the periodic table to form an intermediate;(c) reacting the intermediate complex with an electron donor to form an intermediary complex; and(d) reacting the intermediary complex with a fluid comprising a transition metal halide.
    Type: Grant
    Filed: December 20, 1982
    Date of Patent: August 21, 1984
    Assignee: Stauffer Chemical Company
    Inventor: Elliot I. Band
  • Patent number: 4464478
    Abstract: Catalyst-forming components are prepared from(a) a halogenated Ti compound containing at least a Ti-halogen bond;(b) an electron-donor compound free of active hydrogen atoms;and(c) the solid product of the reaction between at least one electron-donor compound containing active hydrogen atoms and a Mg dihalide or a complex thereof with an electron-donor compound free of active hydrogen atoms, obtained by decomposing organic Mg compounds containing at least one Mg-R or Mg-OR group, in which R is an alkyl, aryl, cycloalkyl or alkenyl radical having 1 to 20 carbon atoms, by means of a halogenating agent different from (a).Catalysts for polymerizing olefins and prepared by mixing the aforesaid catalyst-forming components with an organometallic compound of Al are also disclosed.
    Type: Grant
    Filed: September 30, 1982
    Date of Patent: August 7, 1984
    Assignee: Montedison S.p.A.
    Inventors: Umberto Scata, Enrico Albizzati, Enzo Giannetti
  • Patent number: 4464518
    Abstract: Polymerization of ethylene or copolymerization of ethylene with other .alpha.-olefin is carried out in the presence of a specific catalyst system. The catalyst system is obtained by preparing a reaction product (A) of an organic aluminum compound (I) represented by the formula AlR.sub.n.sup.1 X.sub.3-n where R.sup.
    Type: Grant
    Filed: June 4, 1982
    Date of Patent: August 7, 1984
    Assignee: Nissan Chemical Industries, Ltd.
    Inventors: Takeshi Iwabuchi, Hiroshi Morinaga, Masao Kawahara, Sakae Kamiyama, Terumi Sato, Muneto Yokota
  • Patent number: 4452912
    Abstract: The invention relates to a process for producing a magnesium-containing supported catalyst for the polymerization and copolymerization of .alpha.-olefins. The magnesium is bound via oxygen to a porous metal oxide; e.g. silicon dioxide and/or aluminum oxide, and has alkoxy groups. This solid is reacted with a transition metal compound and one or more organometallic compounds of Groups I to III of the Periodic Table are added.
    Type: Grant
    Filed: November 15, 1982
    Date of Patent: June 5, 1984
    Assignee: Ruhrchemie Aktiengesellschaft
    Inventors: Mufit Bahadir, Wolfgang Payer
  • Patent number: 4450098
    Abstract: Process for preparing and treating a chromium-containing catalyst so that when the catalyst is activated the risk of explosion is substantially reduced. The catalyst comprises a complex of chromium and optionally other transition metal complexes reacted with one or more organometallic compounds of a metal of group II or III of the periodic table, which metal contains hydrocarbyl groups of 1-20 carbon atoms. The reaction product is applied to an inert inorganic support to form the catalyst component which is deactivated by treatment with oxygen or an alcohol to modify or replace residual hydrocarbyl groups. The catalyst component may be activated to form the catalyst by heating in the range 200.degree.-1200.degree. C. The catalyst is used to catalyze a polymerization of alpha-olefins.
    Type: Grant
    Filed: August 5, 1982
    Date of Patent: May 22, 1984
    Assignee: Stamicarbon B.V.
    Inventors: Lambertus J. M. A. van de Leemput, Godefridus A. H. Nooijen
  • Patent number: 4439537
    Abstract: A process for the preparation of the former catalyst component of a catalyst for the polymerization of olefins composed of a titanium-based catalyst component and an organo aluminium compound is disclosed.The former catalyst component can readily be produced by contacting (a) a fatty acid salt of magnesium, (b) an electron donor compound and (c) a titanium halide.In the polymerization of olefins by use of the former catalyst component, both the amount of catalyst residues in the produced polymer and halogen content therein are greatly reduced with high polymerization activity per unit weight of the former catalyst component and with high yield of stereoregular polymer.
    Type: Grant
    Filed: June 22, 1982
    Date of Patent: March 27, 1984
    Assignee: Toho Titanium Co., Ltd.
    Inventors: Atsushi Murai, Minoru Terano, Yoshikazu Hitosugi, Kouhei Kimura, Masuo Inoue, Katsuyoshi Miyoshi
  • Patent number: 4435518
    Abstract: Catalyst compositions which are particularly useful for the preparation of ethylene polymers having a narrow molecular weight distribution are obtained by (1) drying an inorganic oxide having surface hydroxyl groups, e.g., silica, alumina, magnesia, etc., to remove adsorbed water, (2) reacting the surface hydroxyl groups with at least a stoichiometric amount of an organometallic compound having at least one alkyl group attached to a Group III metal, e.g., a trialkylaluminum, (3) reacting the thus-treated inorganic oxide with a vanadium halide, such as (a) VOCl.sub.3, VOBr.sub.3, and/or mono-, di-, and/or trihydrocarbyloxy derivatives thereof and/or (b) VCl.sub.4, VBr.sub.4, and/or mono-, di-, tri-, and/or tetrahydrocarbyloxy derivatives thereof, and (4) reacting that reaction product with at least about 0.1 mol, per mol of organometallic compound, of an alcohol containing 1 to 18 carbon atoms.
    Type: Grant
    Filed: November 24, 1982
    Date of Patent: March 6, 1984
    Assignee: Cities Service Co.
    Inventors: B. Timothy Pennington, Paul V. Roling, John T. T. Hsieh
  • Patent number: 4435519
    Abstract: Vanadium compound/organometallic compound/inorganic oxide catalyst compositions useful for the polymerization of ethylene to polymers having a molecular weight distribution that can be controlled by selection of the appropriate member of a particular family of vanadium compounds are obtained by using, as the vanadium component, at least one vanadium compound prepared by reacting one molar proportion of VOCl.sub.3 and/or VOBr.sub.3 with about 0.5 to 1 molar proportion of a diol corresponding to the formula HO-R-OH, wherein R is a divalent hydrocarbon radical having a chain length of 2 to 16 carbon atoms. The molecular weight distributions of polymers formed in the presence of the catalyst compositions are narrowed as the chain length of R is increased. The preferred vanadium compounds are those prepared by reacting VOCl.sub.3 with a diol wherein R is a straight- or branched-chain alkylene group containing 2 to 6 carbon atoms.
    Type: Grant
    Filed: November 24, 1982
    Date of Patent: March 6, 1984
    Assignee: Cities Service Co.
    Inventors: Richard L. Veazey, B. Timothy Pennington
  • Patent number: 4434242
    Abstract: Catalyst compositions which are particularly useful for the preparation of ethylene polymers having a narrow molecular weight distribution are obtained by (1) drying an inorganic oxide having surface hydroxyl groups, e.g., silica, alumina, magnesia, etc., to remove adsorbed water (2) reacting the surface hydroxyl groups with at least a stoichiometric amount of an organometallic compound having at least one alkyl group attached to a Group III metal, e.g., a trialkylaluminum, (3) reacting the thus-treated inorganic oxide with a vanadium halide, such as (a) VOCl.sub.3, VOBr.sub.3, and/or mono-, di-, and/or trihydrocarbyloxy derivatives thereof and/or (b) VCl.sub.4, VBr.sub.4, and/or mono-, di-, tri-, and/or tetrahydrocarbyloxy derivatives thereof, and (4) reacting that reaction product with at least about 0.1 mol, per mol of organometallic compound, of an ether-alcohol corresponding to the formula R"[OCHR'(CH.sub.2).sub.n CHR].sub.
    Type: Grant
    Filed: November 24, 1982
    Date of Patent: February 28, 1984
    Assignee: Cities Service Co.
    Inventors: Paul V. Roling, Richard L. Veazey, David E. Aylward