Material Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non-transition Metal Atom Bond Patents (Class 526/159)
  • Patent number: 4127504
    Abstract: A process for the production of a catalyst component for use in the polymerization of .alpha.-olefins, which comprises reducing titanium tetrachloride with an organo aluminum compound having the general formula Al Rn X.sub.3-n wherein R represents a hydrocarbon group having 1 to 18 carbon atoms, x represents a halogen atom and n represents a suitable numeral between o<n.ltoreq.3, to thus obtain a reduced solid, then removing aluminum compounds contained in said reduced solid and activating with a mixture or a complex of titanium tetrachloride and a dialkyl ether of the general formula R'OR" wherein R' and R" are (a) alkyl groups having 1-4 carbon atoms, (b) normal alkyl groups having five carbon atoms, or (c) alkyl groups having 6-20 carbon atoms.
    Type: Grant
    Filed: November 24, 1976
    Date of Patent: November 28, 1978
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Hiroshi Ueno, Naomi Inaba, Tokuo Makishima, Shozo Wada
  • Patent number: 4125698
    Abstract: Method for the polymerization of alpha-olefins, e.g., ethylene and its higher homologs, to produce high molecular weight polymers by contacting the alpha-olefin or an alpha-olefin mixture to be polymerized with a catalyst formed from a mixture of a first and second component, the first component essentially consisting of a dialkyl, diaryl organoaluminum compound, or aluminum hydride, and preferably a dialkyl aluminum halide, e.g., diethyl aluminum chloride, and the second component essentially consisting of a salt, freshly precipitated oxide or hydroxide of a Group IVB, VB, VIB or VIII of the Periodic System, and most preferably a salt, such as titanium chloride.
    Type: Grant
    Filed: October 29, 1958
    Date of Patent: November 14, 1978
    Assignee: Studiengesellschaft Kohle M.b.h.
    Inventors: Karl Ziegler, Heinz Breil, Heinz Martin, Erhard Holzkamp
  • Patent number: 4123386
    Abstract: An olefin polymerization catalyst is prepared in two steps. In the first step, a chemically reducing solid is prepared by polymerizing an olefin in contact with solid particles of a compound of a transition metal from sub-groups IV A, V A and VI A in a lower valency state in the presence of an organomagnesium compound and terminating the polymerization when the quantity of olefin polymerized is from 50 mg.-50 g. per mg-atom of transition metal. In the second step, the chemically reducing solid prepared in the first step is contacted with reducible compounds of transition metals from sub-groups IV A, V A and VI A to effect reduction thereof.
    Type: Grant
    Filed: December 9, 1976
    Date of Patent: October 31, 1978
    Inventors: Michel M. Avaro, Pierre M. Mangin
  • Patent number: 4120820
    Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are provided by reacting a trivalent titanium halide complex such as an alcohol complex of titanium trichloride, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and halide source such as a hydrogen halide or an alkyl aluminum halide. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.
    Type: Grant
    Filed: December 1, 1976
    Date of Patent: October 17, 1978
    Assignee: The Dow Chemical Company
    Inventor: Donald F. Birkelbach
  • Patent number: 4115319
    Abstract: New catalyst components comprising compounds containing titanium, magnesium and halogens, and catalysts for polymerizing olefins obtained by mixing said components with organometallic Al compounds are disclosed.
    Type: Grant
    Filed: September 17, 1976
    Date of Patent: September 19, 1978
    Assignee: Montedison S.p.A.
    Inventors: Umberto Scata, Luciano Luciani, Pier Camillo Barbe
  • Patent number: 4110524
    Abstract: High bulk density modification III of isotactic polybutene-1 is directly prepared by polymerizing butene-1 at 100.degree.-200.degree. C, preferably 140.degree.-160.degree. C., with a catalyst of: (a) titanium trichloride and (b) an alkyl aluminum compound.
    Type: Grant
    Filed: April 24, 1974
    Date of Patent: August 29, 1978
    Assignee: Chemische Werks Huels A.G.
    Inventor: Albert Frese
  • Patent number: 4108942
    Abstract: High temperature polymers are prepared by effecting reaction in the presence of an alkyl aluminum halide-titanium halide catalyst between a difunctional acetylene compound and a monofunctional acetylene compound. These polymers can be used for making composites with heat-resistant fibers, such as graphite fibers, glass fibers, etc., useful in airplane construction and in turbines.
    Type: Grant
    Filed: March 22, 1972
    Date of Patent: August 22, 1978
    Assignee: General Electric Company
    Inventors: Alan J. Chalk, Alfred R. Gilbert
  • Patent number: 4107416
    Abstract: There are disclosed new starting components for use in preparing catalysts for the polymerization and copolymerization of olefins. The new starting components are compounds having the general formulae R.sub.2 AlOR" and/or RAl (OR").sub.
    Type: Grant
    Filed: July 8, 1976
    Date of Patent: August 15, 1978
    Assignee: Montedison S.p.A.
    Inventors: Umberto Giannini, Enrico Albizzati, Sandro Parodi
  • Patent number: 4107417
    Abstract: A process is described whereby homopolymers and copolymers of isobutylene are prepared by effecting the polymerization at a temperature in the range of -100.degree. to 30.degree. C in the presence of a catalyst system including:(a) a compound selected from the group consisting of: AlCl.sub.3, AlBr.sub.3, AlEtCl.sub.2, TiCl.sub.4, SnCl.sub.4, SiCl.sub.4, VCl.sub.4, BF.sub.3, Al.sub.2 Et.sub.3 Cl.sub.3, SbCl.sub.5, SbF.sub.5, FeCl.sub.3, VOCl.sub.3, ZrCl.sub.4, AlI.sub.3, GaCl.sub.3 ; and(b) a compound adapted to react with the compounds of group (a) and selected from the group consisting of: SnR.sub.4, SnRX.sub.3, SrR.sub.4, TiX.sub.2 (OR).sub.2, Ti(OR).sub.4, PbR.sub.4, Ti(OR)X.sub.3, VO(OR).sub.3, Ti(OR).sub.3 X, (C.sub.5 H.sub.5).sub.2 Ti(C.sub.6 H.sub.5).sub.2, (C.sub.5 H.sub.5).sub.2 Ti(CH.sub.3).sub.2, Ti(Acac).sub.4, SnCl.sub.2 (acetate).sub.2 in which R is a hydrocarbon radical with from 1 to 10 carbon atoms and X is a halogen atom.
    Type: Grant
    Filed: September 6, 1974
    Date of Patent: August 15, 1978
    Assignee: Snamprogetti, S.p.A.
    Inventors: Aldo Priola, Sebastiano Cesca, Giuseppe Ferraris
  • Patent number: 4105585
    Abstract: A process for making a Ziegler catalyst by reacting together magnesium metal and a halogen-containing titanium compound in the presence of an alcohol. The magnesium metal is preferably magnesium powder and the alcohol preferably contains 1-6 carbon atoms. The catalyst is employed together with conventional co-catalysts.
    Type: Grant
    Filed: May 18, 1977
    Date of Patent: August 8, 1978
    Assignee: BP Chemicals Limited
    Inventor: Ian Alastair Matheson
  • Patent number: 4098979
    Abstract: Easily pourable polyolefin granules are obtained by polymerizing an olefin in the presence of a polymerization catalyst system comprising a compound having a main catalyst component supported on a spheroidal particle, 1 to 1,000 .mu. in diameter, of a high molecular compound used as a carrier, and an organometallic compound under a pressure of 100 kg/cm.sup.2 or less and at a temperature lower than both of the melting points of the resulting polymer and the said high molecular compound used as a carrier. The granule diameter of the said polyolefin can be controlled very easily by changing the particle size of the high molecular compound used as a carrier, the loading rate of the main catalyst component on the high molecular compound used as a carrier, or the catalyst efficiency. The granule size distrubution can be controlled by controlling the particle size distribution of the high molecular compound used as a carrier. The polyolefin granules obtained have a bulk density of 0.4 to 0.
    Type: Grant
    Filed: December 12, 1973
    Date of Patent: July 4, 1978
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Kenichi Maemoto, Takezo Sano, Akio Kobayashi
  • Patent number: 4098980
    Abstract: A process for the non-aqueous dispersion polymerization of a conjugated diolefin monomer, for instance, butadiene or isoprene, in a liquid hydrocarbon dispersion medium, for instance, n-butane or n-pentane with a Ziegler Natta catalyst, for instance, triisobutylaluminum/titanium tetrachloride while said conjugated diolefin is in the presence of a block copolymer dispersion stabilizer. The block copolymer dispersion stabilizer is a copolymer which contains at least two blocks of polymer linked by chemical valences, at least one block (A block) is soluble in liquid organic dispersion medium and at least another block (B block) is insoluble in the dispersion medium and the stabilizer acts to disperse polymers of conjugated diolefins which are formed in the stabilizer's presence. The A block is exemplified by polyisoprene, poly(t-butyl styrene) and poly(vinyl toluene). The B block is exemplified by polystyrene, poly(.alpha.
    Type: Grant
    Filed: June 24, 1976
    Date of Patent: July 4, 1978
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Richard A. Markle, Richard G. Sinclair
  • Patent number: 4097659
    Abstract: A process for polymerizing .alpha.-olefins in the liquid phase is disclosed, wherein the olefins are polymerized in the presence of a catalyst prepared by first reacting as aluminum-halogen compound with an organomagnesium compound and thereafter reacting the resulting reaction mixture with a transition metal compound and then activating the resulting catalyst system with an organo-aluminum compound. The homopolymers and copolymers of .alpha.-olefins produced by this process find use in the normal applications of such polymers.
    Type: Grant
    Filed: April 15, 1976
    Date of Patent: June 27, 1978
    Assignee: Stamicarbon, N.V.
    Inventors: Henricus M. J. C. Creemers, Renier J. L. Graff, Hendrinus M. Verschoor
  • Patent number: 4093790
    Abstract: A high molecular weight polymer characterized by chains of benzene rings comprising alternatively di-substituted rings and tri-substituted rings, wherein the di-substituted rings comprise a major part of 1,3 (meta)- and a minor part of 1,4 (para)- di-substituted rings, and the tri-substituted rings are members of the group consisting of 1,3,5-, 1,2,4- and mixtures of 1,3,5- and 1,2,4- tri-substituted rings, these tri-substituted rings being substituted by 1 to 3 chains of benzene rings, each of the other substituents being a benzene ring which is unsubstituted or is substituted by a radical of the group consisting of alkyl, aryl and halogen radicals.
    Type: Grant
    Filed: January 5, 1972
    Date of Patent: June 6, 1978
    Assignee: Labofina S.A.
    Inventor: William J. I. Bracke
  • Patent number: 4091082
    Abstract: Hydrocarbon-soluble compositions useful as the transition metal component in the Ziegler polymerization of .alpha.-olefins are provided by reacting molecular nitrogen or hydrogen with a transition metal compound such as titanium trichloride to form a dinitrogen or dihydrogen complex of the transition metal compound.
    Type: Grant
    Filed: June 4, 1976
    Date of Patent: May 23, 1978
    Assignee: The Dow Chemical Company
    Inventors: Donald Earl Gessell, Kirby Lowery, Jr.
  • Patent number: 4067822
    Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins are provided by mixing a dinitrogen and/or dihydrogen complex of a transition metal such as titanium with a conventional Ziegler catalyst such as the reaction product of titanium tetrachloride and aluminum triethyl. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics.
    Type: Grant
    Filed: June 23, 1976
    Date of Patent: January 10, 1978
    Assignee: The Dow Chemical Company
    Inventors: Donald Earl Gessell, Gaylon Le Roy Dighton, Luis Daniel Valenzuela-Bernal
  • Patent number: 4065444
    Abstract: Elastomeric butadiene-piperylene copolymers in which the butadiene is mainly in high cis-1,4-addition, low vinyl configuration, prepared in solution using iodine-containing catalyst based on organomagnesium compound and titanium tetrahalide. Graft copolymers of resin-forming monomers (e.g., styrene, acrylonitrile) on the butadiene-piperylene elastomer have good low temperature impact strength.
    Type: Grant
    Filed: September 2, 1975
    Date of Patent: December 27, 1977
    Assignee: Uniroyal, Inc.
    Inventors: Edward A. Delaney, Norman J. Pinkowski, Walter Nudenberg
  • Patent number: 4065609
    Abstract: Polymerization of a mono-.alpha.-olefine monomer is effected by contacting the gaseous monomer with a solid phase comprising polymer and catalyst at a pressure and temperature which are such that the temperature is in the range from tp + 0.1.degree. C up to tp + 5.0.degree. C, where tp is the temperature at which the monomer condenses at a pressure which is equal to the monomer partial pressure within the polymerization vessel.
    Type: Grant
    Filed: April 1, 1976
    Date of Patent: December 27, 1977
    Assignee: Imperial Chemical Industries Limited
    Inventor: Bruce Albert Edward Willmore
  • Patent number: 4064069
    Abstract: This invention relates to a catalyst composition for polymerization of propylene, having high activity and producing polypropylene of high stereoregularity and having a low particle size distribution, which comprises;1. reducing TiCl.sub.4 by diethylaluminum chloride (DEAC), thereby forming a reduced solid (TiCl.sub.3),2. removing the aluminum compounds from the reduced catalyst,3. treating the said reduced solid with the mixture or complex of TiCl.sub.4 and diisoamylether (IAE) and4. separating the solid catalyst from the mixture.The aluminum compounds may be removed by washing with a complexing agent therefor; in a preferred embodiment the complexing agent is di-n-butyl ether.
    Type: Grant
    Filed: July 6, 1976
    Date of Patent: December 20, 1977
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Hiroshi Ueno, Naomi Inaba, Tokuo Makishima, Shozo Wada
  • Patent number: 4063010
    Abstract: Novel amorphous copolymers of mono-olefins or of mono-olefins and non-conjugated dienes with unsaturated derivatives of imides are disclosed. These copolymers containing from 99.9 to 80% by weight of non-polar units derived from at least two mono-olefins containing 2 to 18 carbon atoms, particularly ethylene and propene or ethylene and butene-1, and possibly one or more non-conjugated dienes, and from 0.1 to 20% units derived from an imide having the formula ##STR1## wherein Z is an alkenyl radical containing 2 to 16 carbon atoms, andA designates a saturated or unsaturated divalent hydrocarbon radical which contains 2 to 12 carbon atoms and which may possibly carry amino, halogeno or carboxyl groups.Some of said copolymers may be used as polymer additives in lubricating compounds to improve their viscosity index and to disperse the slurry which they may contain.
    Type: Grant
    Filed: December 3, 1975
    Date of Patent: December 13, 1977
    Assignee: Societe Nationale Elf Aquitaine (SNEA)
    Inventors: Gilbert Marie, Andre Lang, Gilbert Chapelet
  • Patent number: 4062804
    Abstract: The invention relates to a method for preparing a catalyst composition for polymerization of propylene, having high activity and producing polypropylene of high stereoregularity in narrow particle size distribution, which comprises:1. reducing TiCl.sub.4 by a mixture of diethylaluminum chloride (DEAC) and ethylaluminum dichloride (EADC), thereby forming a reduced solid (TiCl.sub.3),2. removing the aluminum compound from the reduced solid;3. treating the said reduced solid with a mixture or complex of TiCl.sub.4 and diisoamylether (IAE), and4. separating the solid catalyst from the solution.Preferably step 2 is performed by washing with a complexing agent for the aluminum compound.
    Type: Grant
    Filed: July 8, 1976
    Date of Patent: December 13, 1977
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Hiroshi Ueno, Naomi Inaba, Tokuo Makishima, Shozo Wada
  • Patent number: 4063009
    Abstract: Alpha olefins are polymerized alone or in admixture at comparatively low pressures to produce polymers employing a two-component catalyst wherein one component is an organozinc or organomagnesium compound, e.g. zinc diethyl, magnesium diphenyl, propyl magnesium chloride, etc. The other component is a salt, oxide or hydroxide of a metal of Group IV-B, V-B or VI-B of the Periodic System, including thorium and uranium.
    Type: Grant
    Filed: July 1, 1958
    Date of Patent: December 13, 1977
    Assignee: Studiengesellschaft Kohle m.b.H.
    Inventors: Karl Ziegler, deceased, Heinz Breil, Erhard Holzkamp, Heinz Martin
  • Patent number: 4060593
    Abstract: Solid titanium trichloride in the form of fine granules having low aluminum compound content, which is suitable as a catalyst for polymerization of .alpha.-olefins, especially, propylene is obtained as a precipitate by heating liquefied titanium trichloride in the presence of a liberating agent, and separating the thus formed precipitate. The liquefied titanium trichloride is preferably prepared with an reducing titanium tetrachloride by organic aluminium compound in the presence of ether and hydrocarbon.
    Type: Grant
    Filed: July 31, 1975
    Date of Patent: November 29, 1977
    Assignee: Mitsubishi Chemical Industries
    Inventors: Yamaguchi Kazuo, Kakogawa Genjiro, Hasuo Masayoshi, Nobuaki Goko, Yasuo Maruyama
  • Patent number: 4058654
    Abstract: Process for the continuous production of a polymer of an .alpha.-olefin monomer. The monomer is polymerized in bulk, employing a screw conveyor as the reactor. The monomer can be in liquid phase when introduced into the conveyor. By the process, the use of diluents is avoided.
    Type: Grant
    Filed: July 14, 1975
    Date of Patent: November 15, 1977
    Assignee: Bayer Aktiengesellschaft
    Inventors: Hubert Sutter, Reinhard Peuker
  • Patent number: 4058653
    Abstract: The invention provides a process for the preparation of but-1-ene homopolymers or copolymers of but-1-ene containing up to 15% by weight of at least one other .alpha.-olefin by the stereo-specific polymerization, using a Ziegler-Natta catalyst, of but-1-ene in a homogeneous reaction mixture. By employing a homogeneous reaction mixture comprising at least 70% by weight of but-1-ene and from 1 to 30% by weight of an inert hydrocarbon solvent which is capable of dissolving at least 100 g/l of an isotactic polybutene it is possible to employ reaction temperatures of from 35.degree. to 55.degree. C., thereby improving the quality of the resulting but-1-ene polymer while avoiding precipitation of polymer during the course of the reaction.
    Type: Grant
    Filed: September 10, 1973
    Date of Patent: November 15, 1977
    Assignee: Ethylene Plastique
    Inventors: Bernard Boucheron, Emile Gosset
  • Patent number: 4057565
    Abstract: Transition metal compounds of the formulaeM.sup.1 A.sub.3 (1)whereinM.sup.1 is scandium, yttrium, chromium, or rare earth metal, andA is 2-dialkylaminobenzyl or 2-dialkylaminomethylphenyl, or a lower alkyl derivative thereof,M.sup.2 A.sub.2 (2)whereinM.sup.2 is Cr or Mo andM.sup.3 A.sub.4 (3)whereinM.sup.3 is Ti, Zr or HfAre useful as components of coordination catalysts for olefin polymerization. Lithium compounds of the formula LiA are intermediates used in preparing the above compounds. All of the above compounds are also useful as oxygen-scavenging agents.
    Type: Grant
    Filed: July 22, 1975
    Date of Patent: November 8, 1977
    Assignee: E. I. Du Pont de Nemours and Company
    Inventor: Leo Ernest Manzer
  • Patent number: 4053697
    Abstract: A process for producing a homopolymer of propylene or a copolymer of propylene which comprises polymerizing propylene or a mixture of propylene and another unsaturated hydrocarbon monomer such as ethylene in liquid propylene, in the presence of a catalyst system consisting essentially of (a) an activated titanium compound obtained by reducing titanium tetrachloride with an organic aluminum compound and activating the resulting titanium compound and (b) an organic aluminum compound to produce a polymer slurry, introducing the polymer slurry into an upper part of a counter-current washing zone, such as a washing tower, and counter-currently contacting the polymer slurry with liquid propylene which is introduced into a lower part of the washing zone, whereby the polymer and catalyst residues dissolved in the polymer slurry are removed.
    Type: Grant
    Filed: January 16, 1975
    Date of Patent: October 11, 1977
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Mamoru Asada, Akinobu Shiga, Kiyoshi Matsuyama
  • Patent number: 4048409
    Abstract: Articles such as containers made of a highly crystalline olefin polymer having improved transparency and impact strength are obtained by biaxially extending an extruded tubular body of said polymer at an orientation temperature below the melting point thereof to attain an extension magnification ratio of at least 1.5 for each of the longitudinal and lateral directions. The polymer is a statistical random copolymer of propylene and from 1.5% to 5.0%, and preferably from 3.0% to 5.0%, by weight ethylene having a melt index of 0.6 - 3.0 g/10 min. Optionally, from 0.03 to 0.20 part by weight of p-tert. butyl benzoic acid, benzoic acid or sodium benzoate are added to 100 parts by weight of said copolymer.
    Type: Grant
    Filed: March 12, 1976
    Date of Patent: September 13, 1977
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Yasunori Sugita, Yasuhiko Itagaki
  • Patent number: 4048415
    Abstract: An improved process for the polymerization of olefins in the presence of catalyst consisting essentially of:A. a titanium trichloride composition obtained by micro-pulverizing a titanium trichloride component prepared by reduction of titanium tetrachloride with a member selected from the group consisting of hydrogen, silicon, metallic titanium and metallic aluminum, in the presence of a complex of aluminum chloride or aluminum bromide with an electron-donor selected from the group consisting of oxygen-containing organic compounds, nitrogen-containing organic compounds and phosphorus-containing organic compounds, the amount of the complex being 0.005 to 0.5 mole per mole of the titanium trichloride component, and extracting the micro-pulverized titanium trichloride component with a solvent selected from the group consisting of saturated aliphatic hydrocarbons, aromatic hydrocarbons and halogenated aromatic hydrocarbons; andB. an organoaluminum compound, and the catalyst therefor.
    Type: Grant
    Filed: September 30, 1971
    Date of Patent: September 13, 1977
    Assignee: Mitsui Petrochemical Industries Ltd.
    Inventors: Norio Matsuzawa, Hidesaburo Oi, Hiroshi Nishimura, Shigeru Wada, Juntaro Sasaki
  • Patent number: 4035560
    Abstract: The polymerization of olefins to form polymers having a molecular weight greater than 50,000 wherein the polymerization is carried out in the presence of a catalyst component formed of a compound of a transition metal of the sub-groups IVa, Va and VIa, and a co-catalyst component of at least one organo-metallic compound of a metal from groups II and III of the periodic table, in which the co-catalyst is in the form of a liquid which is separately introduced into the reaction vessel on a carrier formed of an inert porous powder which is impregnated with the co-catalyst.
    Type: Grant
    Filed: May 24, 1976
    Date of Patent: July 12, 1977
    Assignee: Naphtachimie
    Inventors: Francois Caumartin, Laszlo Havas
  • Patent number: 4028481
    Abstract: In the polymerization of .alpha.-olefins, a titanium trichloride containing catalyst activated by copulverization with at least one additive selected fromI. an organic compound containing oxygen, sulfur or phosphorus such as:A. Organic oxygen compounds selected from ethers, ketones and esters;B. Organic sulfur compounds selected from thioethers, thiophenols and thioalcohols; andC. Organic phosphorus compounds.Ii. an organic compound of (I) containing oxygen, sulfur or phosphorus in combination with an aluminum halide, andIii. a complex or reaction product of an organic compound of (I) with an aluminum halide.Provides substantially improved catalytic activity and reduces amorphous polymeric by-products while enhancing stereoregularity. The catalytic activity of these catalysts is further enhanced by washing with an organic solvent subsequent to copulverization to remove excess additive. Preferred catalysts are those which contain aluminum chloride with the titanium trichloride.
    Type: Grant
    Filed: August 6, 1973
    Date of Patent: June 7, 1977
    Assignee: Mitsui Toatsu Chemicals, Incorporated
    Inventors: Tetsunosuke Shiomura, Akiro Ito, Yoshio Morimoto, Tetsuya Iwao
  • Patent number: 4008177
    Abstract: A catalyst of high activity and stereospecificity in .alpha.-olefin polymerization is obtained when titanium trichloride, prepared by reduction with aluminum alkyl halides, is treated first with an ether and then, without separation of the ether, with an aluminum alkyl halide in the presence of a small amount of a cyclopolyene and/or an olefin.
    Type: Grant
    Filed: February 27, 1975
    Date of Patent: February 15, 1977
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Kurt Rust, Erwin Schrott, Helmut Strametz, Hans-Jurgen Kablitz
  • Patent number: 4008176
    Abstract: A catalyst of high activity and stereospecificity in .alpha.-olefin polymerization is obtained when titanium trichloride, prepared from titanium tetrachloride by reduction with an aluminum alkyl halide, is thermally treated, first with an ether in the presence of a cyclopolyene and the solid reaction product is then treated with an aluminum alkyl halide in the presence of a small amount of a cyclopolyene and/or an olefin. With the catalyst obtained high space-time yields of .alpha.-olefin polymers and copolymers can be produced.
    Type: Grant
    Filed: February 27, 1975
    Date of Patent: February 15, 1977
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Kurt Rust, Erwin Schrott, Helmut Strametz, Hans-Jurgen Kablitz
  • Patent number: 4000354
    Abstract: Polypropylene can be polymerized with Ziegler-Natta TiCl.sub.3 or TiCl.sub.3 . (AlCl.sub.3).sub.0.2.sub.-0.6 plus chlorine containing organoaluminum compound mixed catalyst using butene-2 or a C.sub.4 -cut comprising butene-2 as the polymerization solvent without the formation of propylene-butene copolymers.
    Type: Grant
    Filed: July 23, 1974
    Date of Patent: December 28, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Fritz Baxmann, Walter Dittmann, Albert Frese, Johann Dietrich, Wolfgang Kilian
  • Patent number: 3984387
    Abstract: Ultra high molecular weight, linear .alpha.-olefin polymers are produced without reactor fouling by polymerizing an .alpha.-olefin in the presence of Ziegler catalyst dispersed in an inert diluent and an amount of an inert gas not in excess of that which will dissolve in the inert liquid diluent.
    Type: Grant
    Filed: August 7, 1974
    Date of Patent: October 5, 1976
    Assignee: The Dow Chemical Company
    Inventors: Gordon Y. T. Liu, Donald R. Smith
  • Patent number: 3976630
    Abstract: Rubbery polybutadiene containing at least 85 percent cis 1,4-addition can be made by polymerizing 1,3-butadiene with a catalyst formed from trialkylaluminum, for example, triethylaluminum, and titanium tetraiodide. The rubbery polybutadiene exhibits low hysteresis and is particularly useful in the manufacture of tires.
    Type: Grant
    Filed: April 16, 1956
    Date of Patent: August 24, 1976
    Assignee: Phillips Petroleum Company
    Inventors: David R. Smith, Robert P. Zelinski
  • Patent number: 3974092
    Abstract: For the production of polyalkenamers there are provided catalysts consisting essentially of a catalyst system for the ring-opening polymerization of cyclic olefins consisting essentially of (1) a tungsten or molybdenum compound; (2) an organoaluminum compound; and (3) an ether of vinyl alcohol, of allyl alcohol, or of 2-butene-1,4-diol, the molar ratio of component (1) to component (2) being less than 1 : 1 and the molar ratio of component (1) to component (3) being less than 100 : 1. The catalyst system may also contain a compound containing one or more hydroxyl or sulfhydryl groups in a molar ratio to component (1) of about 0 : 1 to 2 : 1, respectively.
    Type: Grant
    Filed: January 7, 1974
    Date of Patent: August 10, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Roland Streck, Heinrich Weber
  • Patent number: 3974094
    Abstract: Polyalkenamers are produced by a ring-opening polymerization of cyclic olefins employing a catalyst system comprising (1) a tungsten or molybdenum compound; (2) an organoaluminum compound; (3) a vinylic chloride, bromide or iodide; and, optionally, (4) a compound containing a hydroxyl or sulfhydryl group; and conducting the polymerization in the presence of an ethylenically unsaturated halogenated hydrocarbon wherein one of the double bonded carbon atoms is substituted by chlorine, bromine or iodine or halogenated alkyl or aryl and at least one hydrogen atom.
    Type: Grant
    Filed: November 13, 1974
    Date of Patent: August 10, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Roland Streck, Heinrich Weber
  • Patent number: 3972862
    Abstract: Elastomeric copolymers of butadiene and piperylene containing at least 50 mole percent butadiene and having a random distribution of monomer units enchained in a stereo-regulated manner are characterized by, (1) vinyl unsaturation pendant to the main polymer chain which is equal to or less than 10 percent of the total unsaturation present in the polymer; (2) enchainment of at least 95 percent of the piperylene as the 1,2-trans and 1,4-trans-stereoisomers; and (3) selective enchainment of between 50 and 95 percent of the butadiene as the 1,4-trans-stereoisomer. The copolymers, which are prepared from a mixture of the monomers with the aid of an iodine-containing hydrocarbon-soluble catalyst system comprising TiX.sub.n -xMI.sub.n -yI.sub.2 -zAlR.sub.3 -QLB, can be compounded with other elastomers and with process oils, resins, plasticizers and reinforcing agents such as carbon black, silica, talc and the like.
    Type: Grant
    Filed: July 22, 1974
    Date of Patent: August 3, 1976
    Inventors: Erik G. M. Tornqvist, Albert M. Gessler
  • Patent number: 3972866
    Abstract: An olefine polymerization catalyst includes a complex compound of phosphorus having the general formula ##EQU1## where the various groups are defined. Typical phosphorus compounds include ##EQU2## Catalyst systems containing these phosphorus compounds give a high rate of polymerization together with a low proportion of soluble polymer. The phosphorus compound can be ball-milled with the titanium compound to give an improved effect and the catalyst system may also include an electron donor compound such as triphenylphosphine oxide and tris(dimethylamino)silicon monochloride or a cyclic polyene such as cycloheptatriene.
    Type: Grant
    Filed: November 16, 1973
    Date of Patent: August 3, 1976
    Assignee: Imperial Chemical Industries Limited
    Inventors: Michael Stanley Fortuin, Anthony David Caunt
  • Patent number: 3966637
    Abstract: Catalysts obtained fromA. a reaction product of 1 mol tungsten hexachloride with from 1 to 4 mols of a mixture of 2-chloroethanol and 2,2,2-trichloroethanol in a molar ratio of from 1 : 3 to 3 : 1; andB. from 1 to 20 mol, per mol of tungsten in component (A), of an organometallic aluminium for disproportionation and metathesis of olefin and for ring opening polymerizaton of cyclic olefins.
    Type: Grant
    Filed: November 12, 1974
    Date of Patent: June 29, 1976
    Assignee: Bayer Aktiengesellschaft
    Inventors: Josef Witte, Gunther Lehnert
  • Patent number: 3966697
    Abstract: High molecular weight polybutadiene, polyisoprene and other hydrocarbon polymers having a high vinyl and a low 1,4-trans-double bond content, which are useful in the manufacture of tire treads and carcasses, are produced employing as catalyst system (a) a cobalt compound; (b) a halogen-containing organoaluminum compound; and (c) a tris-(aryl) phosphite of the formula P--(OR.sub.1), (--OR.sub.2),--OR.sub.3 wherein R.sub.1, R.sub.2 and R.sub.3 are monocyclic halogenated aryl, or diaryl, naphthyl, anthracenyl or phenanthryl or the corresponding halogenated and/or alkylated polycyclic aryl; and optionally (d) an H-acidic compound, e.g., water.
    Type: Grant
    Filed: December 9, 1974
    Date of Patent: June 29, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Wolfgang Kampf, Karl-Heinz Nordsiek
  • Patent number: 3962375
    Abstract: A method of preparing polybutadiene polymers utilizing a three-component system consisting of an organoaluminum compound, an organonickel compound and a fluoride compound selected from the group of hydrogen fluoride and its complexes and boron trifluoride and its compounds, the improvement being mixing the catalyst components in the presence of a preforming agent selected from the group of monoolefins, nonconjugated diolefins, cyclic nonconjugated multiolefins, acetylenic hydrocarbons, triolefins, vinyl ethers and aromatic nitriles.
    Type: Grant
    Filed: April 11, 1975
    Date of Patent: June 8, 1976
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Morford C. Throckmorton, Ken W. Donbar, Karl C. Kauffman
  • Patent number: 3959178
    Abstract: Ethylene homopolymers and copolymers are made in a particle form process over a mixed catalyst comprising several portions of the same or different supported chromium components and metal promoted variations thereof in which each portion is activated at a different temperature, thereafter combined, and the composite, or each activated portion before being combined, is post treated with a hydrocarbyl aluminum hydrocarbyloxide. Broad molecular weight polymers are produced having excellent die swell characteristics and acceptable environmental stress cracking resistance and flow properties; this is achieved and while at the same time realizing high productivities.
    Type: Grant
    Filed: March 28, 1974
    Date of Patent: May 25, 1976
    Assignee: Phillips Petroleum Company
    Inventor: John P. Hogan