Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non Transition Metal Atom Bond Patents (Class 526/132)
  • Patent number: 5151399
    Abstract: A complex alkoxide compound containing magnesium, titanium and boron species comprises the reaction product of elemental magnesium, titanium tetraalkoxide, an alkyl borate ester and alkanol at elevated temperature in an inert diluent. This complex alkoxide compound is contacted with a tetravalent titanium halide, a halohydrocarbon and an electron donor to form an olefin polymerization procatalyst. Contact of the procatalyst with an organoaluminum cocatalyst and a selectivity control agent produces a high activity catalyst for the polymerization of lower .alpha.-olefins to polymer product of good properties in good catalyst productivity.
    Type: Grant
    Filed: October 18, 1990
    Date of Patent: September 29, 1992
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 5132381
    Abstract: A syndiotactic polyolefin is obtained in a high yield by polymerization or copolymerization of an olefin of the formula R.sup.a --CH.dbd.CH--R.sup.b in the presence of a catalyst consisting of a metallocene of the formula I ##STR1## and an aluminoxane. This polyolefin has a very high syndiotactic index. At a low polymerization temperature, a polyolefin having a low average molecular weight and narrow molecular weight distribution is obtained, and at a high polymerization temperature a polymer having a high average molecular weight and a wide molecular weight distribution is obtained.Shaped articles produced from the polymers are distinguished by a high transparency, flexibility, tear strength and excellent surface gloss.
    Type: Grant
    Filed: March 8, 1990
    Date of Patent: July 21, 1992
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Andreas Winter, Jurgen Rohrmann, Martin Antberg, Volker Dolle, Walter Spaleck
  • Patent number: 5112928
    Abstract: The homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of(1) a transition metal catalyst component,(2) an organoaluminum catalyst component and(3) an organohalogen catalyst component.In the homopolymerization or copolymerization, the solid-phase product (VI) used as (1) is the product which has been obtained by a method in which (1.1) first (1.1.1) an inorganic oxidic substance (I) as the carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a vanadium trichloride/alcohol complex and (IIc) a silicon or boron compound are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) the intermediate (IV) obtained in (1.1) and (1.2.2) a dissolved organoaluminum compound (V) are combined with the formation of a suspension, the solid-phase product (VI) obtained as the suspended substance being the transition metal catalyst component (1).
    Type: Grant
    Filed: October 3, 1989
    Date of Patent: May 12, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Roland Saive, Guido Funk, Robert Bachl
  • Patent number: 5112927
    Abstract: A method for producing a stereoregular polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, wherein a catalyst system is employed which comprises (i), (ii) and (iii): (A) a solid catalyst component obtained by reacting to a uniform solution containing (i) at least one member selected from the group consisting of metallic magnesium and an organic hydroxide compound and an oxygen-containing organic magnesium compound, (ii) a compound of Group IIIB of the Periodic Table, and (iii) an oxygen-containing organic silicon compound, (iv) at least one aluminum halide, to obtain a solid product, and reacting to the solid product, (v) an electron donative compound, and (vi) a titanium halide compound; (B) at least one member selected from the group consisting of organometallic compounds of metals of Groups IA, IIA, IIB, IIIB and IVB of the Periodic Table; and (C) an electron donative compound.
    Type: Grant
    Filed: December 21, 1989
    Date of Patent: May 12, 1992
    Assignee: Tosoh Corporation
    Inventors: Daiji Hara, Mitsuhiro Mori, Yozo Kondo
  • Patent number: 5087677
    Abstract: Polymers of polycyclic olefins of the formulae I to IV having a viscosity number greater than 20 cm.sup.3 /g and a glass transition temperature above 100.degree. C. are obtained without ring opening at a high polymerization rate and at polymerization temperatures advantageous from the technical point of view by means of a catalyst which is composed of a stereo-rigid, chiral metallocene compound of groups IVb to VIb of the Periodic Table of the Elements and an aluminoxane.
    Type: Grant
    Filed: July 5, 1990
    Date of Patent: February 11, 1992
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Michael-Joachim Brekner, Jurgen Rohrmann, Walter Spaleck, Martin Antberg
  • Patent number: 5086134
    Abstract: The invention relates to a process for the preparation of a predominantly crystalline ethylene/propylene copolymer having less than 15 mol % of propylene units, which can be carried out in liquid propylene as the suspending agent, if metallocene catalyst components of the formulae I, II or III are employed and the partial pressures of ethylene and propylene have a specific ratio. ##STR1## By means of this process, it is possible to increase the possible uses of polymerization plants which work with liquid propylene.
    Type: Grant
    Filed: October 19, 1989
    Date of Patent: February 4, 1992
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Martin Antberg, Walter Spaleck, Jurgen Rohrmann, Hartmut Luker, Andreas Winter
  • Patent number: 5075394
    Abstract: Olefin polymerization catalysts, processes for preparing the catalysts and processes for producing polyolefins utilizing the catalysts are provided. The catalysts are basically comprised of a pentadienyl derivative-transition metal complex adsorbed on an activated inorganic refractory compound.
    Type: Grant
    Filed: June 7, 1990
    Date of Patent: December 24, 1991
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Paul D. Smith
  • Patent number: 5066740
    Abstract: This invention pertains to the use of pyridinium isopoly and heteropoly molybdates and tungstates as catalysts in a metathesis catalyst system in polymerization of norbornene-type monomers by ring opening polymerization. Polymerization can be by reaction injection molding in absence of a solvent whereby a thermoset polymer is produced or by solution polymerization in presence of a suitable solvent whereby a thermosetting or a thermoplastic polymer is produced. The monomers are selected from polycycloolefins containing at least on enorbornene group and mixtures thereof.
    Type: Grant
    Filed: December 26, 1989
    Date of Patent: November 19, 1991
    Assignee: The B. F. Goodrich Company
    Inventor: Larry F. Rhodes
  • Patent number: 5037908
    Abstract: An improved process for polymerizing butene-1 in the presence of a polymerization catalyst composed of (a) a catalyst component containing titanium and halogen as essential constituents and (b) an organometallic compound, wherein the improvement comprises bringing said catalyst component into contact with an activity inhibitor when said catalyst component is activated or after said catalyst component has been activated with said organometallic compound, and subsequently polymerizing butene-1.
    Type: Grant
    Filed: December 19, 1985
    Date of Patent: August 6, 1991
    Assignee: Toa Nenryo Kogyo K.K.
    Inventors: Mamoru Tachikawa, Satoshi Ueki, Masato Sakuma, Makoto Miyazaki
  • Patent number: 5026798
    Abstract: The invention is a catalytic process using a Group IV B transition metal component and an alumoxane component to polymerize .alpha.-olefins to produce high crystallinity and high molecular weight poly-.alpha.-olefins.
    Type: Grant
    Filed: September 13, 1990
    Date of Patent: June 25, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Jo Ann M. Canich
  • Patent number: 4923936
    Abstract: This invention pertains to the use of organoammonium, organophosphonium, organoarsonium heteropolymolybdates and heteropolytungstates, and mixtures thereof, as catalysts in a metathesis catalyst system in polymerization of cycloolefin monomers by ring opening polymerization. Polymerization can be by reaction injection molding in absence of a solvent whereby a thermoset polymer is produced or by solution polymerization in presence of a suitable solvent whereby a thermosetting or a thermoplastic polymer is produced. The cycloolefin monomers are selected from monocycloolefins except cyclohexane, polycycloolefins containing at least one norbornene group, and mixtures thereof.
    Type: Grant
    Filed: February 21, 1989
    Date of Patent: May 8, 1990
    Assignee: The BFGoodrich Company
    Inventors: Brian L. Goodall, Larry F. Rhodes
  • Patent number: 4910272
    Abstract: A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent, a mixture of (A) an inorganic oxide, (B) an organomagnesium material, (C) an organic hydroxyl-containing material, (D) a reducing halide source, and (E) a transistion metal compound.
    Type: Grant
    Filed: November 29, 1988
    Date of Patent: March 20, 1990
    Assignee: The Dow Chemical Company
    Inventors: Gary R. Marchand, Ricardo Fuentes, Jr., William M. Coleman, III
  • Patent number: 4746712
    Abstract: A process for producing an olefin copolymer rubber by slurry-polymerizing ethylene, at least one .alpha.-olefin and at least one non-conjugated diene in a poor solvent for the copolymer in the presence of a catalyst consisting of an organometallic compound (the first component) and a transition metal compound (the second component), characterized by using, an organoaluminum compound as the first component of the catalyst, and using, as the second component, a modified vanadium compound obtained by contacting a vanadium compound with at least one compound selected from the group consisting of the compounds represented by the following formulas: ##STR1## wherein R is a hydrocarbon group of 1 to 20 carbon atoms and X.sub.1, X.sub.2 and X.sub.3 are independently halogen atoms or alkoxyl groups. This process can prevent a gel from being formed during polymerization.
    Type: Grant
    Filed: February 17, 1987
    Date of Patent: May 24, 1988
    Assignee: Japan Synthetic Rubber Co., Ltd.
    Inventors: Yoshihide Yamazaki, Kazumi Uchimura, Satoshi Yamashita, Mikio Takeuchi
  • Patent number: 4740570
    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: November 13, 1986
    Date of Patent: April 26, 1988
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Ulrich Klabunde, Rolf Mulhaupt
  • Patent number: 4737555
    Abstract: A process for producing a catalyst component for polymerization of olefins which comprises contacting (a) a metal oxide with (b) an organomagnesium compound represented by the formula RMgR' wherein R denotes a hydrocarbyl group and R' denotes a hydrocarbyl group or a halogen atom, contacting the resulting contacting product with (c) carbon dioxide, and further contacting the resulting contact product with (d) a titanium compound. Optionally, the carbon dioxide contacted contact product can be treated with the halogen-containing compound prior to contact with the titanium compound.
    Type: Grant
    Filed: April 22, 1987
    Date of Patent: April 12, 1988
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Mamoru Tachikawa, Satoshi Ueki, Masato Sakuma, Chihiro Imai, Tokuo Makishima
  • Patent number: 4727123
    Abstract: Conjugated dienes are polymerized by a catalyst system comprised of a transition metal complex consisting of at least one binucleating ligand attached to at least one transition metal containing nucleus; and at least one organometallic cocatalyst containing at least one element of Group IA, IIA or Group IIIA.
    Type: Grant
    Filed: April 14, 1983
    Date of Patent: February 23, 1988
    Assignee: The Standard Oil Company
    Inventors: Raymond J. Weinert, Jr., Kenneth C. Benton, Michael J. Desmond
  • Patent number: 4695614
    Abstract: A process for producing an olefin copolymer rubber by slurry-polymerizing ethylene, at least one .alpha.-olefin and at least one non-conjugated diene in a poor solvent for the copolymer in the presence of a catalyst consisting of an organometallic compound (the first component) and a transition metal compound (the second component), characterized by using, an organoaluminum compound as the first component of the catalyst, and using, as the second component, a modified vanadium compound obtained by contacting a vanadium compound with at least one compound selected from the group consisting of the compounds represented by the following formulas: ##STR1## wherein R is a hydrocarbon group of 1 to 20 carbon atoms and X.sub.1, X.sub.2 and X.sub.3 are independently halogen atoms or alkoxyl groups. This process can prevent a gel from being formed during polymerization.
    Type: Grant
    Filed: April 7, 1986
    Date of Patent: September 22, 1987
    Assignee: Japan Synthetic Rubber Co., Ltd.
    Inventors: Yoshihide Yamazaki, Kazumi Uchimura, Satoshi Yamashita, Mikio Takeuchi
  • Patent number: 4678767
    Abstract: A process for producing a catalyst component for polymerization of olefins which comprises contacting (a) a metal oxide with (b) an organomagnesium compound represented by the formula RMgR' wherein R denotes a hydrocarbyl group and R' denotes a hydrocarbyl group or a halogen atom, contacting the resulting contacting product with (c) carbon dioxide, and further contacting the resulting contact product with (d) a titanium compound. Optionally, the carbon dioxide contacted product can be treated with the halogen-containing compound prior to contact with the titanium compound.
    Type: Grant
    Filed: November 27, 1985
    Date of Patent: July 7, 1987
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Mamoru Tachikawa, Satoshi Ueki, Masato Sakuma, Chihiro Imai, Tokuo Makishima
  • Patent number: 4629714
    Abstract: An intermetallic compound is disclosed. The compound is formed by reacting a first reaction product, the first reaction product being the product of reaction of a polymeric transition metal oxide alkoxide with a reducing metal having a higher oxidation potential than the transition metal, the polymeric transition metal oxide alkoxide being the product of the controlled partial hydrolysis of a transition metal alkoxide, with a first halide activator to produce a second reaction product. The second reaction product, in turn, is reacted with a second halide activator to form the intermetallic compound. The intermetallic compound is useful as a catalyst component in a catalyst system for the polymerization of alpha-olefins. The catalyst system includes, in addition to the intermetallic compound, a cocatalyst, an organic compound which includes an element selected from the group consisting of aluminum and boron.
    Type: Grant
    Filed: October 25, 1985
    Date of Patent: December 16, 1986
    Assignee: National Distillers and Chemical Corporation
    Inventor: Javan Shelly
  • Patent number: 4613579
    Abstract: A catalyst component for the polymerization of olefins which is prepared by contacting a reaction product of dihydrocarbyl magnesium and a halogen-containing alcohol held in contact with a titanium compound.
    Type: Grant
    Filed: July 31, 1985
    Date of Patent: September 23, 1986
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Hiroyuki Furuhashi, Tadashi Yamamoto, Masafumi Imai, Hiroshi Ueno
  • Patent number: 4605715
    Abstract: Olefins are polymerized in the presence of, as a catalyst therefor, the catalytic reaction product resulting from heating a mixture of(A) at least one hydrocarbon soluble organomagnesium material;(B) at least one epihalohydrin;(C) at least one reducing halide source; and(D) at least one transition metal (Tm) compound.
    Type: Grant
    Filed: September 20, 1982
    Date of Patent: August 12, 1986
    Assignee: The Dow Chemical Company
    Inventor: Gary K. Lund
  • Patent number: 4577001
    Abstract: Olefins are polymerized in the presence of catalysts prepared from titanium compounds prepared by reacting a titanium compound such as titanium tetraisopropoxide with a compound containing at least one aliphatic hydroxyl group.
    Type: Grant
    Filed: November 13, 1984
    Date of Patent: March 18, 1986
    Assignee: The Dow Chemical Company
    Inventors: William M. Coleman, III, Morris S. Edmondson
  • Patent number: 4559318
    Abstract: A vanadium dichloride-ether complex is carried on a porous support. This complex can be produced by either forming VCl.sub.2 and thereafter complexing the material with an ether or forming an ether complex with VCl.sub.4 or VCl.sub.3 and thereafter reducing the vanadium compound to VCl.sub.2. It is also possible to carry out the complexing reaction and the reduction essentially simultaneously. The resulting catalyst in combination with a cocatalyst is capable of giving high activity in olefin polymerization and demonstrates good sensitivity to molecular weight control agents, thus allowing the production of a broad spectrum of polymers so far as molecular weight is concerned.
    Type: Grant
    Filed: December 17, 1984
    Date of Patent: December 17, 1985
    Assignee: Phillips Petroleum Company
    Inventors: Paul D. Smith, Joel L. Martin
  • Patent number: 4554333
    Abstract: Olefins are polymerized in the presence of catalysts prepared from titanium compounds prepared by reacting a titanium compound such as titanium tetraisopropoxide with a compound containing at least one aliphatic hydroxyl group.
    Type: Grant
    Filed: November 13, 1984
    Date of Patent: November 19, 1985
    Assignee: The Dow Chemical Company
    Inventors: William M. Coleman, III, Morris S. Edmondson
  • Patent number: 4528339
    Abstract: Olefins are polymerized in the presence of catalysts prepared from titanium compounds prepared by reacting a titanium compound such as titanium tetraisopropoxide with a compound containing at least one aliphatic hydroxyl group.
    Type: Grant
    Filed: December 27, 1983
    Date of Patent: July 9, 1985
    Assignee: The Dow Chemical Company
    Inventors: William M. Coleman, III, Morris S. Edmondson
  • Patent number: 4522988
    Abstract: Diene polymers having a high content of cis-1,4 addition are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated metal oxy borate compound in which the metal is nickel or cobalt, (b) an organometallic compound of a metal of Groups I, II, and III of the Periodic System, and (c) one or more fluorine containing compounds selected from the group consisting of boron trifluoride complexes with ethers, alcohols or mixtures thereof; hydrogen fluoride; hydrogen fluoride complexes with ethers, alcohols, or mixtures thereof and mixtures of said compounds.The resultant polymers exhibit good green strength and tack and are particularly suitable for use as tire rubbers.
    Type: Grant
    Filed: June 4, 1984
    Date of Patent: June 11, 1985
    Assignee: The Firestone Tire & Rubber Company
    Inventors: Jung W. Kang, James E. Hall
  • Patent number: 4496699
    Abstract: A process is disclosed for polymerizing an olefin to provide a polyolefin of high melt index which comprises contacting the olefin with a catalyst system obtained by heat activating a supported organophosphoryl chromium compound obtained by the reaction of chromium trioxide with an organophosphorous compound having the formula: ##STR1## wherein R is alkyl, aralkyl, aryl, cycloalkyl, or hydrogen, but at least one R is other than hydrogen, and combining the heat activated supported material with a melt index increasing amount of at least one organoborane catalyst modifier having the formula: ##STR2## wherein m and n each is zero or 1, R.sub.1 and R.sub.2 are each a hydrocarbyl group of from 1 to 10 carbon atoms, or one of R.sub.1 and R.sub.2 is hydrogen, or together R.sub.1 and R.sub.2 constitute a hydrocarbyl group of from 2 to 10 carbon atoms.
    Type: Grant
    Filed: November 12, 1982
    Date of Patent: January 29, 1985
    Assignee: National Distillers and Chemical Corporation
    Inventors: Louis J. Rekers, Stanley J. Katzen
  • Patent number: 4451573
    Abstract: A catalyst suitable for use in the polymerization of olefins is disclosed. This catalyst contains:[A] a solid catalyst component obtained by calcining a reaction product of (a) at least one compound selected from an amine compound, a phosphoric acid amide, a hydrocarbyloxy compound of titanium, vanadium, hafnium or zirconium, and a germanium compound having the general formula:R.sup.1 R.sup.2 R.sup.3 R.sup.4 Gewherein (i) R.sup.1, R.sup.2 and R.sup.3 are each independently a hydrocarbon group having 1 through 10 carbon atoms, and R.sup.4 is a hydrogen atom, a halogen atom, a --OH group, or a --OGeR.sup.1 R.sup.2 R.sup.3 group, or (ii) R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently --OR.sup.5 wherein R.sup.5 is a hydrocarbon group having 1 through 10 carbon atoms, or a halogen atom, and a tin compound having the general formula:R.sup.1 R.sup.2 R.sup.3 R.sup.6 Snwherein R.sup.1, R.sup.2 and R.sup.3 are the same as defined above and R.sup.
    Type: Grant
    Filed: June 4, 1982
    Date of Patent: May 29, 1984
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Tadashi Ikegami, Katsuhiko Takaya, Haruyuki Yoneda
  • Patent number: 4415712
    Abstract: Alpha-olefins are polymerized in the presence of a catalyst which is the catalytic reaction product of(A) the reaction product or complex formed by mixing at a temperature for a time sufficient to provide a color change(a) a transition metal compound having at least one hydrocarbyloxy group attached to said transition metal and(b) a boron compound;(B) a magnesium halide resulting from the reaction of(a) an organomagnesium component and(b) a halide source; and(C) an organoaluminum compound, if required.
    Type: Grant
    Filed: March 1, 1982
    Date of Patent: November 15, 1983
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Larry E. Freyer
  • Patent number: 4410640
    Abstract: Process for producing a porous acetylene high polymer by lyophilizing a gel-like composition composed of 1 part by weight of an acetylene high polymer having a fibril structure and 1 to 1,000 parts by weight of an organic solvent.
    Type: Grant
    Filed: September 11, 1981
    Date of Patent: October 18, 1983
    Assignee: Showa Denko K.K.
    Inventors: Yukio Kobayashi, Hideki Shirakawa, Sakuji Ikeda
  • Patent number: 4396533
    Abstract: A supported Ziegler catalyst prepared by the following steps:(A) heating together at a temperature in the range of 250.degree. to 1100.degree. C. a refractory oxide support material having surface hydroxyl groups and one or more halogen-free metal derivatives which are hydrides and/or organic derivatives of the metal.(B) reacting the product from (A) with one or more organometallic compounds having the feneral formula MR.sup.1.sub.a Q.sub.b-a wherein M is a metal atom, R.sup.1 is a hydrocarbon group, Q is a halogen or an oxyhydrocarbyl group, b is the valency of M and a is an integer from 1 to b and wherein the metal atom M is aluminium, boron, lithium, zinc or magnesium,(C) impregnating the solid product from step (B) with one or more halogen-containing transition metal compounds wherein the transition metal or metals comprise titanium and/or vanadium and/or zirconium.
    Type: Grant
    Filed: January 27, 1982
    Date of Patent: August 2, 1983
    Assignee: BP Chemicals Limited
    Inventor: Alexander Johnstone
  • Patent number: 4381252
    Abstract: A catalyst suitable for polymerizing an .alpha.-olefin, comprising a solid catalyst component [A] and an organometal compound [B], the solid catalyst component [A] being prepared by reacting an organomagnesium compound (1) soluble in a hydrocarbon medium and represented by the general formula,MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.Z.sub.swhereinR.sup.1 is a hydrocarbon group having 2 to 3 carbon atoms;R.sup.2 is a hydrocarbon group having 4 to 20 carbon atoms and the difference in number of carbon atoms between R.sup.1 and R.sup.2 is at least 2;X is an electronegative group having an oxygen atom, a nitrogen atom or a sulfur atom;Z is an organometal compound of aluminum, boron, beryllium, zinc, silicon or lithium;p and q each is a number above 0 to 1;r is a number from 0 to 1;p+q+r=2; ands is a number from 0.02 to 0.09,with a titanium and/or vanadium compound (2) having at least one halogen atom; and a process for polymerizing an .alpha.-olefin employing the same catalyst.
    Type: Grant
    Filed: June 1, 1981
    Date of Patent: April 26, 1983
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4380508
    Abstract: Compositions consisting of the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as a tetraalkoxy titanium compound with a non-metallic oxygen-containing compound such as an alcohol and (2) a strongly reducing alkylating agent such as a dialkyl magnesium compound are useful in the preparation of catalysts for polymerizing .alpha.-olefins at ultra-high efficiencies at high polymerization temperatures.
    Type: Grant
    Filed: October 22, 1981
    Date of Patent: April 19, 1983
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Donald F. Birkelbach
  • Patent number: 4339351
    Abstract: A process for producing olefin polymers, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising a solid catalyst component and an organoaluminum compound, said solid catalyst component being a titanium compound and/or a vanadium compound supported on a solid product obtained by the reaction between a Grignard compound and a boron compound represented by the general formula B(OR.sup.1).sub.a R.sup.2.sub.b R.sup.3.sub.c, wherein a, b and c are numbers defined by the formulas 0<a.ltoreq.3, 0.ltoreq.b<3, 0.ltoreq.c<3 and a+b+c=3, R.sup.1 represents a hydrocarbon radical having 1 to 20 carbon atoms, and R.sup.2 and R.sup.3, which may be the same or different, represent each a hydrogen atom, a hydrocarbon radical having 1 to 20 carbon atoms, or a halogen atom.
    Type: Grant
    Filed: December 4, 1980
    Date of Patent: July 13, 1982
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Kentaro Mashita, Katsumi Hanji
  • Patent number: 4330650
    Abstract: Catalysts for polymerization of olefin which comprise a solid catalyst component (A) and an organometallic compound with a heterocyclic carboxylic acid ester (B), wherein the solid catalyst component (A) is obtained by reacting or/and grinding a special magnesium compound (1), a titanium halide (2) and a carboxylic acid ester (3); and the heterocyclic carboxylic acid ester is N-, S- or O-containing heterocyclic compound, and processes for polymerization of olefin employing such a catalyst.
    Type: Grant
    Filed: March 28, 1980
    Date of Patent: May 18, 1982
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Hideo Morita, Masayoshi Miya, Katsuhiko Takaya, Haruyuki Yoneda
  • Patent number: 4330647
    Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to 320.degree. C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula,M.sub..alpha. MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t.alpha., p, q, r, s and t each independently is O or a number greater than 0,p+q+r+s=m.alpha.+2O.ltoreq.(r+s)/(.alpha.+1)<2,m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 is a hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms,X.sup.1 and X.sup.2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S,D is an electron donor,with a compound (ii) of the formula,R.sub.a.sup.3 C Y.sub.4-awhereinR.sup.
    Type: Grant
    Filed: August 13, 1980
    Date of Patent: May 18, 1982
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4330651
    Abstract: A catalyst for the solution polymerization of .alpha.-olefins is prepared by admixing component (A) with an organometal component (B), component (A) being prepared by reacting a specific hydrocarbon-soluble organomagnesium compound with an aluminum compound and contacting the obtained product with a titanium and/or vanadium compound.
    Type: Grant
    Filed: August 13, 1980
    Date of Patent: May 18, 1982
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4308369
    Abstract: Olefins are polymerized in the presence of a catalyst prepared by reacting tetravalent titanium compounds such as a titanium tetraalkoxide, an anhydrous zinc compound such as diethyl zinc, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and a halide source such as a hydrogen halide or an alkyl aluminum halide and an aluminum compound if the halide source or organomagnesium component does not contain sufficient quantities of aluminum. 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 and these catalysts produce polymers having broader molecular weight distributions than do corresponding catalysts without the anhydrous zinc compound.
    Type: Grant
    Filed: June 2, 1980
    Date of Patent: December 29, 1981
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
  • Patent number: 4296222
    Abstract: A process for the manufacture of poly-.alpha.-olefins by polymerizing .alpha.-olefins by means of a catalyst system comprising (1) a titanium-containing component obtained from (1.1) a compound of the formula TiCl.sub.3.1/3AlCl.sub.3 and (1.2) an organic electron donor, containing phosphorus, nitrogen and/or oxygen atoms, which has been milled with the compound of the formula TiCl.sub.3.1/3AlCl.sub.3 (1.1), in order to form a complex compound, the milling being carried out without assistants or additives in a vibratory ball mill under specific acceleration conditions and at a temperature which is from 4.degree. to 10.degree. C. below the temperature at which the particles of the material being ground begin to agglomerate, and (2) an aluminum-containing component, in which process the titanium-containing component (1) of the catalyst system used is one which has been treated, after milling and before polymerization, with (i) titanium tetrachloride and (ii) an ether and/or an ester.
    Type: Grant
    Filed: March 24, 1977
    Date of Patent: October 20, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Gerhard Staiger, Klaus Bronstert
  • Patent number: 4290914
    Abstract: Catalysts, especially for olefin polymerization are prepared by coating an aluminum compound on a selected high pore volume silica gel, and calcining the support at temperatures of from about 200.degree. to 2000.degree. F. The preferred catalyst is prepared with an inorganic support material as aforesaid, thereafter depositing an organophosphoryl chromium compound thereon, and activating the thus-treated support by heating in a non-reducing, preferably oxygen-containing, atmosphere at temperatures of from about 800.degree. to 2000.degree. F. The activated, supported catalyst composition may, but need not necessarily, be combined with a metallic and/or non-metallic reducing agent, to provide a catalyst system useful in the polymerization of 1-olefins.
    Type: Grant
    Filed: June 16, 1980
    Date of Patent: September 22, 1981
    Assignee: National Petro Chemicals Corp.
    Inventors: Stanley J. Katzen, Louis J. Rekers
  • Patent number: 4265785
    Abstract: New, highly active catalysts for the polymerization of ethylene and mixtures of ethylene with higher alpha-olefins and/or diolefins, are disclosed. The catalysts are prepared by mixing (a) hydrides or organometallic compounds of metals belonging to Groups I, II or III of the Mendelycev Periodic Table with (b) the products obtained by contacting titanium compounds with activated anhydrous halides of magnesium or manganese, diluted with anhydrous compounds of metals belonging to Group III or IV of said Periodic Table, and which are different from either (a) or the titanium compound of (b).
    Type: Grant
    Filed: August 10, 1979
    Date of Patent: May 5, 1981
    Assignee: Montecatini Edison S.p.A.
    Inventors: Umberto Giannini, Paolo Longi, Domenico Deluca, Angelo Pricca
  • Patent number: 4264472
    Abstract: A catalyst for preparing an .alpha.-olefin polymer having a broad molecular weight distribution and excellent physical properties, which comprises a solid catalyst component (A) and an organometal compound (B), the solid catalyst component (A) being obtained by reduction with an organomagnesium solution of the thermal decomposition solid product of special titanium compounds.
    Type: Grant
    Filed: August 29, 1979
    Date of Patent: April 28, 1981
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Tadashi Ikegami, Hisaya Sakurai, Yoshihiko Katayama, Shigeo Tsuyama, Yukitoshi Iwashita
  • Patent number: 4258168
    Abstract: In an alpha-olefin polymerization process using a transition metal halide-aluminum alkyl catalyst system, addition of minor, effective amounts of alkyl orthoformates, thiophosphates and borates decreases the amount of low molecular weight or amorphous polymer produced.
    Type: Grant
    Filed: June 16, 1976
    Date of Patent: March 24, 1981
    Assignee: Standard Oil Company (Indiana)
    Inventors: Nicholas M. Karayannis, Sam S. Lee
  • Patent number: 4250284
    Abstract: Polymerization and copolymerization is carried out in the presence of an improved transition metal based catalyst. The catalyst is obtained by activating with an organometallic compound, the solid product which results from the reaction of a halogen containing transition metal compound with an alkoxy metal compound of the formula X.sub.m-n M(OR).sub.n wherein M is at least one metal selected from the elements of Groups Ia, IIa, IIb, IIIa and VIIb of the Periodic Table, X is a monovalent inorganic radical, R is a monovalent hydrocarbon radical, m is the valence of M and n is an integer such that 1 .ltoreq. n .ltoreq. m.
    Type: Grant
    Filed: February 24, 1975
    Date of Patent: February 10, 1981
    Assignee: Solvay & Cie
    Inventors: Andre Delbouille, Jean L. Derroitte
  • Patent number: 4244838
    Abstract: Solid supported catalysts which can be employed for the polymerization of .alpha.-olefins are prepared by (A) reacting in the presence of a diluent such as n-hexane a mixture of (1) the reaction product of (a) an organo magnesium compound such as dibutyl magnesium and (b) at least one of water, carbon dioxide or an organic, oxygen-containing compound such as n-propyl alcohol; and (2) a transition metal halide such as titanium tetrachloride and (B) recovering the solid precipitate such as by decanting and (C) washing the solid with a solvent such as n-hexane. The resultant solid supported catalyst contains sufficient transition metal which when activated with a suitable activating agent serves as a polymerization catalyst for .alpha.-olefins. The polymers prepared employing these catalysts have a relatively narrow molecular weight distribution and low residual amounts of transition metal and halides.
    Type: Grant
    Filed: June 25, 1979
    Date of Patent: January 13, 1981
    Assignee: The Dow Chemical Company
    Inventor: Donald E. Gessell
  • Patent number: 4209601
    Abstract: The present invention discloses improved catalysts for polymerizing or copolymerizing olefins and a process for the production of polyolefins comprising a polymerization or copolymerization of olefins by the use of said catalysts. According to the invention there is provided a process for the production of polyolefins by polymerizing or copolymerizing olefins using as the catalyst a solid component containing a titanium compound and/or a vanadium compound and an organometallic compound, said solid component comprising a substance obtained by co-pulverizing (1) a metal halide selected from the group consisting of magnesium halides and manganese halides, (2) a compound represented by the general formula B(OR).sub.n X.sub.3-n X3 in which n is a number of the range 0<n.ltoreq.3, X represents a halogen atom and R is a hydrocarbon radical containing from 1 to 20 carbon atoms and may be alike or different and (3) a titanium compound and/or a vanadium compound.
    Type: Grant
    Filed: March 16, 1978
    Date of Patent: June 24, 1980
    Assignee: Nippon Oil Company, Limited
    Inventors: Nobuyuki Kuroda, Takeichi Shiraishi, Akio Itoh, Kazuo Matsuura, Mituji Miyoshi
  • Patent number: 4187385
    Abstract: Polymerization of ethylene or .alpha.-olefins using a catalyst comprising a titanium component obtained by copulverizing the starting titanium component of Ziegler catalysts and organoaluminum compound with a small amount of ethylene or .alpha.-olefins, and an organoaluminum component. The titanium catalyst component can be modified by subjecting the copulverized titanium component to a contact with an inert organic solvent or its mixture with a modifier (1) an oxygen-, sulphur-, phosphor-, nitrogen- or silicon- containing organic compound, (2) a combination of such an organic compound and an aluminum halide, (3) an organoaluminum compound or (4) a Lewis acid.
    Type: Grant
    Filed: May 16, 1977
    Date of Patent: February 5, 1980
    Assignee: Mitsui Toatsu Chemical, Inc.
    Inventors: Tetsuya Iwao, Heizo Sasaki, Akira Ito, Masahiro Kono
  • Patent number: 4146695
    Abstract: The invention is directed to new catalysts consisting of a chromium compound and an organometal compound of an element of Group II or III of the periodic system on a carrier, the process for preparing the catalyst and its use in polymerizing 1-alkenes containing 2 to 8 carbon atoms, optionally admixed with at most 10 mole% of at least one other 1-alkene of 2 to 8 carbon atoms.
    Type: Grant
    Filed: May 23, 1977
    Date of Patent: March 27, 1979
    Assignee: Stamicarbon, B.V.
    Inventor: Lambertus J. M. A. VAN DE Leemput
  • Patent number: 4142991
    Abstract: A substantially agglomeration-free, finely divided catalyst component which is suitable for use as a cocatalyst with organoaluminum compounds in the polymerization of alpha olefins, which is formed by grinding a titanium trichloride material, an effective amount of an electron pair donor compound to enhance the performance of said catalyst component, and an effective amount for agglomeration control of an agglomeration control agent. The agglomeration control agent is effective in either reducing the attractive forces between the finely divided particles in the catalyst component or by preventing the close approach of these particles which would result in agglomeration.
    Type: Grant
    Filed: November 8, 1976
    Date of Patent: March 6, 1979
    Assignee: Stauffer Chemical Company
    Inventors: Gregory G. Arzoumanidis, Richard F. Gold, Christian G. Michel
  • Patent number: 4118340
    Abstract: Supported catalyst compositions incorporating preformed materials comprising the reaction product of (1) organoborate compounds such as trialkyl borate, and (2) chromium trioxide. Typical supports constitute an inorganic material of moderate to high surface area, especially a high pore volume (greater than about 1.96 cc/g) silica xerogel. The supported catalysts are utilized alone or in conjunction with other catalytic ingredients such as organometallic and/or organo non-metallic reducing agents for the polymerization of 1-olefins.
    Type: Grant
    Filed: June 7, 1976
    Date of Patent: October 3, 1978
    Assignee: National Distillers and Chemical Corporation
    Inventor: Louis J. Rekers