Transition Metal Is Ib, Iiib, Viib Or Atomic Number 58-71, 88, 90 Or Higher Patents (Class 526/164)
  • Patent number: 6037297
    Abstract: The invention is directed towards a metal complex having the formula LMX.sub.1 X.sub.2. L is a bidentate nitrogen-containing ligand with more than two nitrogen atoms. M is copper, silver, or gold. X.sub.1 and X.sub.2 are independently selected from the group consisting of halogens, C.sub.1 through C.sub.12 straight chain, branched, or cycloalkyl or aryl, C.sub.1 through C.sub.12 straight chain, branched, or cycloalkoxy, hydride, triflate, trifluoroacetate, trisperfluorotetraphenylborate, and tetrafluoroborate. Such metal complexes have a tetrahedral or pseudo-tetrahedral structure. The invention relates to a catalyst composition of the reaction product of the metal complex and an activating cocatalyst. The invention is also directed towards a method for forming polymers and copolymers using such catalyst compositions, especially copolymers having segments formed from olefinic monomers and monomers having at least one hydrocarbyl polar functional group.
    Type: Grant
    Filed: December 15, 1998
    Date of Patent: March 14, 2000
    Assignee: Exxon Research and Engineering Co.
    Inventors: Robert T. Stibrany, Donald N. Schulz, Smita Kacker, Abhimanyu O. Patil
  • Patent number: 6018007
    Abstract: The invention provides a catalyst composition, comprising: (a) an organolithium compound; and, (b) an organic acid salt of lanthanide series element; wherein: (1) only components (a) and (b) are required to promote the synthesis of 1,4-trans-polybutadiene; (2) the ratio of component (a) to component (b) is selected to maximize formation of the trans structure of said 1,4-trans-polybutadiene; and, (3) components (a) and (b) are selected for enabling further diblock synthesis. The invention further contemplates a process for using the catalyst to synthesize 1,4-trans-polybutadiene and other polymers and copolymers having trans configuration in the conjugated diene monomer contributed units.
    Type: Grant
    Filed: September 22, 1997
    Date of Patent: January 25, 2000
    Assignee: Bridgestone Corporation
    Inventor: Thomas J. Lynch
  • Patent number: 6001478
    Abstract: There is provided a process for preparing a polydiene comprising polymerizing a diene selected from the group consisting of butadiene, isoprene, or a mixture thereof under polymerization conditions in a gas phase reactor optionally in the presence of an inert particulate material and in the presence of a catalyst comprising (i) a rare earth metal component, (ii) a transition metal component selected from the group consisting of nickel compound, cobalt compound or titanium compound, and (iii) cocatalyst.
    Type: Grant
    Filed: August 8, 1997
    Date of Patent: December 14, 1999
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Maria Angelica Apecetche, Kevin Joseph Cann, Minghui Zhang
  • Patent number: 5977270
    Abstract: There is provided a polymerization process for the production of olefin polymers using a catalyst composition comprising: a) (i) a catalyst containing at least one cycloalkadienyl ligand substituted with at least one electron donor residue and coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals; or (ii) a catalyst containing two cycloalkadienyl ligands coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals, said cycloalkadienyl ligands connected by a bridging group comprising at least one Group IVA element and at least one electron donor residue; and b) an activating cocatalyst of the formula R.sub.x M', wherein R is alkyl, aryl, or hydride; M' is a Group I, II, or IIIA metal or a Group I, II, or IIIA metal complexed with oxygen, nitrogen, or a halide; and x is equal to the valence of M'.
    Type: Grant
    Filed: January 26, 1998
    Date of Patent: November 2, 1999
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventor: Timothy Todd Wenzel
  • Patent number: 5965678
    Abstract: The present invention relates to a catalyst system based on monoazadiene metal complexes of the formula ##STR1## and a co-catalyst suitable for activating the metal complex, and to the use of the catalyst system for the polymerization of unsaturated compounds, especially for the polymerization and copolymerization of olefins and/or dienes.The novel catalyst system is characterised in particular by its ease of access, its lack of sensitivity to external influences and its ease of handling.
    Type: Grant
    Filed: June 12, 1998
    Date of Patent: October 12, 1999
    Assignee: Bayer AG
    Inventors: Sigurd Becke, Heike Windisch, Joachim Scholz, Steffen Kahlert
  • Patent number: 5958820
    Abstract: A process for polymerizing a gaseous conjugated diene by bringing it in contact with a catalyst consisting of a rare earth allyl compound, an organic aluminum compound, an inorganic support and optionally, the same or a different conjugated diene. The resulting polymers possess elevated proportions of cis-1,4 units.
    Type: Grant
    Filed: October 2, 1997
    Date of Patent: September 28, 1999
    Assignee: Bayer AG
    Inventors: Rudolf Taube, Steffen Maiwald, Thomas Ruhmer, Heike Windisch, Jurgen Giesemann, Gerd Sylvester
  • Patent number: 5942589
    Abstract: Essentially syndiotactic and semicrystalline polymers which comprise vinylaromatic monomers arc prepared from a reaction mixture containing, as components, vinylaromatic compounds, metallocene complexes as catalysts and one or more cocatalysts selected from the group consisting of the strong, neutral Lewis acids, the ionic compounds having Lewis acid cations and the ionic compounds having Bronsted acids as cations, by a process in which the components are premixed before entering the reactor.
    Type: Grant
    Filed: August 1, 1997
    Date of Patent: August 24, 1999
    Assignee: BASF Aktiengesellschaft
    Inventors: Josef Wunsch, Michael Schiessl, Ralph Diener
  • Patent number: 5914377
    Abstract: Diene rubbers are produced in the gas phase by first polymerizing the dienes or diene mixtures in the presence of a catalyst system, which is based on rare earth compounds, at temperatures of from 0 to 150.degree. C. and at pressures of from 1 mbar to 50 bar, so that a pourable diene rubber having a Mooney viscosity ML (1+4', 100.degree. C.) of 70 to 180 Mooney units is obtained, and subsequently subjecting the pourable diene rubber obtained to a chemical or thermal decomposition reaction until a Mooney viscosity of 10 to 70 Mooney units is obtained.
    Type: Grant
    Filed: March 4, 1997
    Date of Patent: June 22, 1999
    Assignee: Bayer AG
    Inventors: Gerd Sylvester, Hugo Vernaleken
  • Patent number: 5877109
    Abstract: Catalysts comprisingA) a rare earth alkoxide, a rare earth carboxylate and/or a rare earth coordination compound with diketones,B) an alumoxane andC) an inert, particulate, inorganic solid with a specific surface area of greater than 10 m.sup.2 /g and a pore volume of 0.3 to 15 ml/gare excellently suited to the polymerisation of conjugated dienes, in particular butadiene, in the gas phase.
    Type: Grant
    Filed: November 10, 1997
    Date of Patent: March 2, 1999
    Assignee: Bayer AG
    Inventors: Karl-Heinz Reichert, Peter Marquardt, Christopher Eberstein, Birgit Garmatter, Gerd Sylvester
  • Patent number: 5854363
    Abstract: An (omega-alkenyl) (cyclopentacarbyl) metallocene compound is provided. Polymerization processes therewith are also provided.
    Type: Grant
    Filed: November 24, 1997
    Date of Patent: December 29, 1998
    Assignee: Phillips Petroleum Company
    Inventors: Michael Jung, Helmut G. Alt, M. Bruce Welch
  • Patent number: 5789502
    Abstract: The present invention provides a process for control of desired properties in the polymer product. The catalyst system used in the process includes a supported metallocene catalyst precursor in combination with an oxyorganoaluminum. The process can be applied to the co-polymerization of propylene and ethylene. The randomness of the ethylene incorporation of the co-polymer product is increased as the amount of ethylene in the feed is increased. The amount of ethylene in the feed is up to 6 wt. % with a resulting amount of ethylene incorporated into the copolymer product up to 4 mole %.
    Type: Grant
    Filed: April 22, 1997
    Date of Patent: August 4, 1998
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, David J. Rauscher, Theodore Harris, The Vu, Margarito Lopez
  • Patent number: 5756612
    Abstract: There is disclosed a process for producing a styrenic polymer, especially, syndiotactic polystyrene, which comprises polymerizing a styrenic monomer by the use of (a) a transition metal compound, (b) a coordination complex compound comprising an anion in which a plurality of radicals are bonded to a metal and a cation or methylaluminoxane, (c) an alkylating agent (alkyl group-containing aluminum, magnesium or zinc compound) and (d) a reaction product between a straight-chain alkylaluminum having at least two carbon atoms and water (alkylaluminoxane). The above process is capable of simplifying the production process and producing high-performance styrenic polymer having a high degree of syndiotactic configuration in high catalytic activity without deteriorating the catalyst activity, increasing the amounts of residual metals in the objective polymer or leaving the decomposition products of the alkylaluminum therein, thereby curtailing the production cost of the objective polymer.
    Type: Grant
    Filed: September 10, 1996
    Date of Patent: May 26, 1998
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Yoshiaki Aoyama, Norio Tomotsu
  • Patent number: 5747613
    Abstract: The present invention relates to a process for efficiently producing an aromatic vinyl compound-based copolymer having a high degree of syndiotactic configuration in its aromatic vinyl chain by copolymerizing an aromatic vinyl compound with an olefin, etc. in the presence of a catalyst comprising (A) a transition metal compound, (B) an ionic compound comprising a non-coordinate anion and a cation of a typical metal belonging to the group 4 and (C) a Lewis acid to be used as the case may be. It is made possible by the use of the highly active catalyst according to the above process to efficiently produce an aromatic vinyl compound-based copolymer which is minimized in residual amounts of ash and toxic substances a high degree of syndiotactic configuration in its aromatic vinyl chain, while dispensing with an expensive aluminoxane.
    Type: Grant
    Filed: January 2, 1996
    Date of Patent: May 5, 1998
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu
  • Patent number: 5747620
    Abstract: Ethylene copolymers are disclosed herein which are each derived from ethylene and an olefin of C.sub.3 to C.sub.20 and in which any quaternary carbon atom is not present in a polymeric main chain; the activation energy (Ea) of melt flow is in the range of 8 to 20 kcal/mol; and (1) a ratio between a Huggins coefficient (k.sup.1) of the copolymer and a Huggins coefficient (k.sup.2) of a straight-chain ethylene polymer having the same intrinsic viscosity meets the equation 1.12<k.sup.1 /k.sup.2 .ltoreq.5, or (2) a molar ratio ?CH.sub.3 /CH.sub.2 ! of a methyl group to a methylene group in a molecular chain is in the range of 0.005 to 0.1, and the equation Tm.gtoreq.131-1,340 ?CH.sub.3 /CH.sub.2 ! is met, or (3) Mw and a die swell ratio (DR) meet the equation DR>0.5+0.125.times.log Mw.
    Type: Grant
    Filed: August 21, 1995
    Date of Patent: May 5, 1998
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Shuji Machida, Haruo Shikuma, Ayami Hoshino, Yutaka Takakura
  • Patent number: 5741869
    Abstract: Addition polymers derived from norbornene-functional monomers are terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes and at least one of said carbon atoms has two hydrogen atoms attached thereto. The addition polymers of this invention are prepared from a single or multicomponent catalyst system including a Group VIII metal ion source. The catalyst systems are unique in that they catalyze the insertion of the chain transfer agent exclusively at a terminal end of the polymer chain.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: April 21, 1998
    Assignee: The B.F. Goodrich Company
    Inventors: Brian Leslie Goodall, George Martin Benedikt, Lester Howard McIntosh, III, Dennis Allen Barnes, Larry Funderburk Rhodes
  • Patent number: 5733988
    Abstract: A method for inhibiting polymer build-up in a recycle line and a heat exchanger during a polymerization process of one or more alpha olefins, particularly sticky polymers, or of one or more diolefins such as butadiene, isoprene, styrene, or styrene and butadiene which method comprises introducing as an antifouling agent an alcohol having 1 to 20 carbon atoms, an alkyl or cycloalkyl ether having 2 to 20 carbon atoms, ammonia, an ester of an inorganic acid, a compound of a group IV element of the periodic table, alkyl and aryl amines, a sulfur-containing compound, or a mixture thereof at one or more locations in the recycle gas line in an amount sufficient to inhibit polymer buildup.
    Type: Grant
    Filed: November 1, 1996
    Date of Patent: March 31, 1998
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Maria Angelica Apecetche, Bai Xinlai, Kevin Joseph Cann
  • Patent number: 5707913
    Abstract: Catalyst systems which are suitable for the polymerization of olefinically unsaturated hydrocarbons contain, as active components,A) an amidinato metal complex of the formula A ##STR1## where M is a metal from group IIIb, IVb, Vb or VIb of the Periodic Table of Elements or a metal from the lanthanide group,X is a negative leaving atom or a negative leaving group, and the radicals X may be identical or different if (n-m)>1,R.sup.1, R.sup.2 and R.sup.3 are each a C-organic or Si-organic radical,n is the valency of M in the metal complex A andm is from 1 to 5, with the proviso that n-m.gtoreq.0,and,B) an activator in a molar ratio of activator B to metal complex A of from 0.5:1 to 10,000:1.
    Type: Grant
    Filed: June 6, 1995
    Date of Patent: January 13, 1998
    Assignee: BASF Aktiengesellschaft
    Inventors: Ruger Schlund, Martin Lux, Frank Edelmann, Ulrike Reissmann, Wolfgang Rohde
  • Patent number: 5571881
    Abstract: Addition polymers derived from norbornene-functional monomers are terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes and at least one of said carbon atoms has two hydrogen atoms attached thereto. The addition polymers of this invention are prepared from a single or multicomponent catalyst system including a Group VIII metal ion source. The catalyst systems are unique in that they catalyze the insertion of the chain transfer agent exclusively at a terminal end of the polymer chain.
    Type: Grant
    Filed: June 7, 1995
    Date of Patent: November 5, 1996
    Assignee: The B. F. Goodrich Company
    Inventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes, Larry F. Rhodes
  • Patent number: 5569730
    Abstract: Addition polymers derived from norbornene-functional monomers are terminated with an olefinic moiety derived from a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes and at least one of said carbon atoms has two hydrogen atoms attached thereto. The addition polymers of this invention are prepared from a single or multicomponent catalyst system including a Group VIII metal ion source. The catalyst systems are unique in that they catalyze the insertion of the chain transfer agent exclusively at a terminal end of the polymer chain.
    Type: Grant
    Filed: November 15, 1994
    Date of Patent: October 29, 1996
    Assignee: The B. F. Goodrich Company
    Inventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes, Larry F. Rhodes
  • Patent number: 5567784
    Abstract: The production of diene rubbers polymerized by means of Nd catalysts and having reduced cold flow and low intrinsic odor is effected by the polymerization of diolefines adiabatically at temperatures of -20.degree. to 150.degree. C. in the presence of inert organic solvents and in the presence of metallo-organic mixed catalysts based on neodymium carboxylate, by subsequently depressurizing the reaction mixture obtained in this manner by reducing the pressure, and by treating the reaction mixture thereafter with disulphur dichloride, sulphur dichloride and/or thionyl chloride.
    Type: Grant
    Filed: September 20, 1995
    Date of Patent: October 22, 1996
    Assignee: Bayer AG
    Inventors: Wolfgang Wieder, Dieter Kuhlmann, Wolfgang Nentwig
  • Patent number: 5510434
    Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound polymer which catalyst comprises a contact product between an (A) trivalent titanium compound and a (B) compound represented by the general formula (II) or (III)R.sup.1.sub.k M.sup.1 L.sup.2.sub.m (II)R.sup.1.sub.k M.sup.1 X.sup.2.sub.l L.sup.2.sub.m (III)a (C) an ionic compound comprising a noncoordinate anion and a cation, an aluminoxane or an organoboron compound; and optionally a (D) Lewis acid, and a process for producing an aromatic vinyl compound polymer having a high degree of syndiotactic configuration which process comprises polymerizing (a) an aromatic vinyl compound or (b) an aromatic vinyl compound together with an olefin or a diolefin in the presence of the above catalyst.
    Type: Grant
    Filed: November 23, 1994
    Date of Patent: April 23, 1996
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventor: Mizutomo Takeuchi
  • Patent number: 5502126
    Abstract: The subject invention relates to a technique for synthesizing rubbery non-tapered, random, copolymers of 1,3-butadiene and isoprene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire sidewall rubber compounds for truck tires. By utilizing these isoprene-butadiene rubbers in tire sidewalls, tires having improved cut growth resistance can be built without sacrificing rolling resistance. Such rubbers can also be employed in tire tread compounds to improve tread wear characteristics and decrease rolling resistance without sacrificing traction characteristics.
    Type: Grant
    Filed: October 28, 1994
    Date of Patent: March 26, 1996
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Anthony J. Bell, Barry A. Matrana, Adel F. Halasa
  • Patent number: 5468819
    Abstract: A single component ionic catalyst consists essentially of an organonickel complex cation, and a weakly coordinating neutral counteranion. The cation is a neutral bidentate ligand removably attached to a Group VIII transition metal in an organometal complex. The ligand is easily displaced by a norbornene-type (NB-type) monomer in an insertion reaction which results in an unexpectedly facile addition polymerization. A NB-type monomer includes NB or substituted NB, or a multi-ringed cycloolefin having more than three rings in which one or more of the rings has a structure derived from NB, and a ring may have an alicyclic alkyl, alkylene or alkylidene substituent. The insertion reaction results in the formation of a unique propagating species more soluble in a polar than in a non-polar solvent and devoid of an available .beta.-hydrogen for termination. The ensuing propagation of a polymer chain proceeds without measurable unsaturation.
    Type: Grant
    Filed: November 16, 1993
    Date of Patent: November 21, 1995
    Assignee: The B.F. Goodrich Company
    Inventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes
  • Patent number: 5453474
    Abstract: A process for preparing syndiotactic vinylidene aromatic polymers comprising contacting one or more vinylidene aromatic monomers with a catalyst comprising a cationic Group 4 metal complex wherein the metal is in the +3 oxidation state formed from the corresponding metal hydrocarbyloxy containing complex in the presence of a hydrocarbylation agent.
    Type: Grant
    Filed: October 8, 1993
    Date of Patent: September 26, 1995
    Assignee: The Dow Chemical Company
    Inventors: Thomas H. Newman, Karen K. Borodychuk
  • Patent number: 5428119
    Abstract: A process for producing high cis-1,4-polybutadienes using a catalyst system based on a rare earth compound that exhibits improved catalytic activity is provided which process comprises polymerizing 1,3-butadiene in a polymerization medium comprising a hydrocarbon solvent at a temperature of from about 0.degree. C. to about 120.degree. C. in the presence of a catalyst system which is a mixture of (1) a rare earth carboxylate selected from the group of neodymium carboxylates wherein the carboxylate has from 4 to 12 carbon atoms, (2) an alkyl aluminum chloride selected from the group of compounds represented by the formulae R.sup.2 AlCl.sub.2, R.sup.2.sub.3 Al.sub.2 Cl.sub.3 and R.sup.2.sub.2 AlCl wherein R.sup.2 is a hydrocarbon residue having from 8 to 12 carbon atoms and (3) an organo aluminum compound of the formula R.sup.3.sub.2 AlH wherein R.sup.
    Type: Grant
    Filed: November 9, 1993
    Date of Patent: June 27, 1995
    Assignee: Polysar Rubber Corporation
    Inventors: Thomas F. Knauf, Akhtar Osman
  • Patent number: 5428120
    Abstract: A process for preparing syndiotactic vinylidene aromatic polymers comprising contacting one or more vinylidene aromatic monomers with tri n-propyl aluminum chain transfer agent under Ziegler-Natta polymerization conditions.
    Type: Grant
    Filed: October 8, 1993
    Date of Patent: June 27, 1995
    Assignee: The Dow Chemical Company
    Inventors: Thomas H. Newman, Karen K. Borodychuk
  • Patent number: 5405815
    Abstract: The subject invention relates to a technique for synthesizing rubbery non-tapered, random, copolymers of 1,3-butadiene and isoprene. These rubbery copolymers exhibit an excellent combination of properties for utilization in tire sidewall rubber compounds for truck tires. By utilizing these isoprene-butadiene rubbers in tire sidewalls, tires having improved cut growth resistance can be built without sacrificing rolling resistance. Such rubbers can also be employed in tire tread compounds to improve tread wear characteristics and decrease rolling resistance without sacrificing traction characteristics.
    Type: Grant
    Filed: June 17, 1993
    Date of Patent: April 11, 1995
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Anthony J. Bell, Barry A. Matrana, Adel F. Halasa
  • Patent number: 5208304
    Abstract: Homogeneous catalyst systems are provided for cyclopolymerization of diolefins, particularly 1,5-hexadiene, which control the stereochemistry, microstructure, and physical properties of the polymers synthesized. The systems comprise homogeneous Ziegler-Natta catalysts based on group 4 metallocenes and methylalumoxane. The cyclopolymers synthesized exhibit different degrees of stereoregularity, which is a function of the polymerization conditions. In addition, the polyolefins can be chiral and optically active. The polymers produced are of high molecular weight and highly flexible.
    Type: Grant
    Filed: October 7, 1991
    Date of Patent: May 4, 1993
    Assignee: Board of Trustees, Leland Stanford Junior University
    Inventor: Robert M. Waymouth
  • Patent number: 4990573
    Abstract: The processability of a polybutadiene with a high content of 1,4-cis-structure is improved by means of the addition of PCl.sub.3 before the polymerization reaction is quenched and when Mooney viscosity of polybutadiene has reached a prefixed value, preferably lower than, or equal to 30; the polymerization of butadiene is carried out in a solution in an aliphatic or cycloaliphatic solvent, in the presence of a catalytic system based on rare earths, preferably a neodymium-based catalytic system.
    Type: Grant
    Filed: February 13, 1990
    Date of Patent: February 5, 1991
    Assignee: Enichem Elastomeri S.p.A.
    Inventors: Piero Andreussi, Renzo Bianchi, Mario Bruzzone
  • Patent number: 4931376
    Abstract: A butadiene polymer or a copolymer of butadiene with another conjugated diene having the following structural parameters and physical properties:(a) a content of butadiene moiety in the polymer or copolymer of at least 80% by weight,(b) a content of trans-1,4 linkage in the butadiene moiety of 80% to 95%,(c) a molecular weight distribution (Mw/Mn) of 1.2 to 4.0 as measured by gel permeation chromatography,(d) a melting temperature of the crystal of 40.degree. C. to 130.degree. C.
    Type: Grant
    Filed: July 28, 1989
    Date of Patent: June 5, 1990
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Takeshi Ikematsu, Yasuo Hattori, Yoshihiro Inoki, Mitsuhiro Tanaka
  • 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: 4699960
    Abstract: The present invention relates to the production of 1,4-cis-polybutadiene and of copolymers of butadiene with other conjugated diolefins, by means of the catalytic polymerization or copolymerization of monomer butadiene, by an either continuous or batch process, operating in the presence or in the absence of diluents, and carrying out a portionwise addition, during the polymerization, of a portion of the organometallic compound of aluminum (or of the related hydride derivative), constituiting also one of catalytic components.
    Type: Grant
    Filed: June 24, 1986
    Date of Patent: October 13, 1987
    Assignee: Enichem Elastomeri, S.p.A.
    Inventors: Silvano Gordini, Antonio Carbonaro, Stanislao Spina
  • Patent number: 4699962
    Abstract: A process for producing a novel-highly active lanthanide containing catalyst comprising the product produced by reacting a lanthanide hydride, a Lewis acid, and an electron donor ligand with an organoaluminum cocatalyst component and its use in the polymerization of olefins, especially olefins such as ethylene and 1,3-butadiene.
    Type: Grant
    Filed: January 30, 1984
    Date of Patent: October 13, 1987
    Assignee: Phillips Petroleum Company
    Inventors: Henry L. Hsieh, Gene H. C. Yeh
  • Patent number: 4689368
    Abstract: The invention relates to a catalyst system comprising (a) a compound of a rare earth element and, as cocatalyst, a second component (b) comprising an organomagnesium compound. In the polymerization of a conjugated diene this catalyst gives a polymer having a very high content of trans 1,4 isomer. A third component (c) which is a Lewis acid alters the reaction to give a polymer having a very high content of cis 1,4 isomer. If desired reaction can be initiated using components (a) and (b) alone and component (c) then added at the desired conversion to produce a block polymer having a block of high trans content followed by a block of high cis content.
    Type: Grant
    Filed: August 4, 1986
    Date of Patent: August 25, 1987
    Assignee: Enoxy Chemical Limited
    Inventor: Derek K. Jenkins
  • Patent number: 4663405
    Abstract: Lanthanide and actinide catalyst systems normally appear to be "pseudo-living" when they are used to polymerize conjugated diolefin monomers into polymers. Polymerizations which are catalyzed with such catalyst systems produce polymers which have increasingly high molecular weight as monomer conversions are increased. Consequently, any change in polymerization time or conversion may affect the polymer's ultimate molecular weight. This has made controlling the molecular weight of polymers which are made utilizing lanthanide and actinide catalysts difficult.It has been unexpectedly discovered that vinyl halides can be used as molecular weight regulators for polymerizations which are catalyzed with lanthanide and actinide catalyst systems.
    Type: Grant
    Filed: April 16, 1986
    Date of Patent: May 5, 1987
    Assignees: The Goodyear Tire & Rubber Company, Enichimica S.p.A., Enichem Polimeri
    Inventor: Morford C. Throckmorton
  • Patent number: 4619982
    Abstract: The invention relates to a catalyst system comprising (a) a compound of a rare earth element and, as cocatalyst, a second component (b) comprising an organomagnesium compound. In the polymerization of a conjugated diene this catalyst gives a polymer having a very high content of trans 1,4 isomer. A third component (c) which is a Lewis acid alters the reaction to give a polymer having a very high content of cis 1,4 isomer. If desired reaction can be initiated using components (a) and (b) alone and component (c) then added at the desired conversion to produce a block polymer having a block of high trans content followed by a block of high cis content.
    Type: Grant
    Filed: March 31, 1983
    Date of Patent: October 28, 1986
    Assignee: Enoxy Chemical Limited
    Inventor: Derek K. Jenkins
  • Patent number: 4575538
    Abstract: A process for producing a novel-highly active lanthanide containing catalysts comprising products formed by reacting a lanthanide halide, and an electron doner ligand with an organometal cocatalyst component and its use in the polymerization of olefins, especially olefins such as ethylene, 1,3-butadiene, isoprene and the like. In one embodiment, an organic base is used to increase catalyst activity in those instances where rare earth metal halide-ligand complex is formed with a ligand containing an acidic proton. In another embodiment, diolefins and vinyl aromatics are polymerized in a two-stage process employing a lanthanide complex-organometal cocatalyst in the first stage and a free radical initiator in the second stage.
    Type: Grant
    Filed: December 20, 1984
    Date of Patent: March 11, 1986
    Assignee: Phillips Petroleum Company
    Inventors: Henry L. Hsieh, Gene H. C. Yeh
  • Patent number: 4544718
    Abstract: A process for producing a novel-highly active lanthanide containing catalyst comprising the product formed by admixing a lanthanide hydroxyhalide and an electron donor bidentate organic ligand chosen from among diamines, dihydric alcohols, and diketones with an organoaluminum cocatalyst component and its use in the polymerization of olefins, especially olefins such as ethylene and 1,3-butadiene.
    Type: Grant
    Filed: September 13, 1984
    Date of Patent: October 1, 1985
    Assignee: Phillips Petroleum Company
    Inventors: Gene H. C. Yeh, Joel L. Martin, Henry L. Hsieh
  • Patent number: 4533711
    Abstract: A polybutadiene rubber composition having an improved green strength is disclosed, which comprises a polybutadiene having a content of cis-1,4 bond of at least 70%, an average chain length of 1,4-bond of 110.about.450 and a molecular weight distribution represented by a ratio of weight-average molecular weight to number-average molecular weight of not less than 5.0.
    Type: Grant
    Filed: September 7, 1983
    Date of Patent: August 6, 1985
    Assignees: Bridgestone Tire Company Limited, Japan Synthetic Rubber Co., Ltd.
    Inventors: Yasumasa Takeuchi, Mitsuhiko Sakakibara, Nobuo Tagata, Masaki Ogawa, Yasushi Hirata, Shigeru Tomihira
  • Patent number: 4429089
    Abstract: A novel catalytic system is disclosed which is especially adapted for the polymerization and the copolymerization of aliphatic conjugated diolefines, the system comprising an organic compound of aluminum, a Lewis acid containing at least one halogen, and an organic compound of a lanthanide metal. The catalyst system has outstanding and hitherto unparalleled activity. The method of preparation of the catalytic system is also described in detail.
    Type: Grant
    Filed: July 15, 1981
    Date of Patent: January 31, 1984
    Assignee: Anic, S.p.A.
    Inventors: Ugo Pedretti, Gabriele Lugli, Sergio Poggio, Alessandro Mazzei
  • Patent number: 4384982
    Abstract: A process and catalyst for the polymerization of olefins wherein the catalyst is prepared by reacting scandium, yttrium or rare earth metal halides with certain transition metal compounds, reacting that product with an organometallic compound, and then reacting that product with a halide ion exchanging source.
    Type: Grant
    Filed: May 18, 1981
    Date of Patent: May 24, 1983
    Assignee: Phillips Petroleum Company
    Inventor: Joel L. Martin
  • Patent number: 4327201
    Abstract: The method and production of macromolecular monomers from cationically polymerizable monomers and vinyl-substituted hydrocarbon halides is disclosed. These cationically polymerizable monomers may react in the presence of a catalyst with the hydrocarbon halide to produce a macromer retaining a polymerizable headgroup. This compound may be used in a variety of copolymerization processes with a variety of copolymerizable monomers to form graft copolymers.
    Type: Grant
    Filed: October 22, 1980
    Date of Patent: April 27, 1982
    Assignee: The University of Akron
    Inventors: Joseph P. Kennedy, Kurt C. Frisch, Jr.
  • Patent number: 4296214
    Abstract: A methacrylic resin having a high solar radiant energy absorbing property wherein an organic compound (A) containing cupric ion and a compound (B) having at least one P-O-H bond in a molecule are contained into the methacrylic resin selected from poly(methyl methacrylate) or methacrylic polymers containing at least 50% by weight of a methyl methacrylate unit. A process for producing said methacrylic resin is also disclosed.
    Type: Grant
    Filed: April 11, 1980
    Date of Patent: October 20, 1981
    Assignee: Mitsubishi Rayon Co., Ltd.
    Inventors: Kazumasa Kamada, Yoshio Nakai, Kazunori Abe
  • Patent number: 4242232
    Abstract: A catalyst comprising(a) a reaction mixture formed by reacting M(RCO.sub.2).sub.3 with AlR.sub.3'.sup.1(b) AlR.sub.3.sup.2 and / or HAlR.sub.2.sup.2 and(c) a Lewis acidwherein M denotes a trivalent rare earth element with an atomic number of 57 to 71, R denotes a saturated or unsaturated, straight chain or branched chain aliphatic hydrocarbon group having 1 to 20 C-atoms which may be substituted one or more times with cycloalkyl having 5 to 7-atoms and/or phenyl, the carboxyl group being attached to a primary, secondary or tertiary C-atom; a cycloalkyl group having 5 to 7 ring carbon atoms, which may be substituted one or more times with alkyl groups having from 1 to 5 C-atoms; or an aromatic group having from 6 to 10 ring carbon atoms, which may be substituted one or more times with alkyl groups having 1 to 5 C-atoms, and R.sup.1 and R.sup.2 are identical or different, straight chain or branched chain alkyl groups having from 1 to 10 C-atoms.
    Type: Grant
    Filed: July 3, 1979
    Date of Patent: December 30, 1980
    Assignee: Bayer Aktiengesellschaft
    Inventors: Gerd Sylvester, Josef Witte, Gunter Marwede
  • Patent number: 4167615
    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: January 16, 1978
    Date of Patent: September 11, 1979
    Assignee: The Dow Chemical Company
    Inventors: Donald E. Gessell, Kirby Lowery, Jr.
  • Patent number: 4166167
    Abstract: Gas-phase polymerization of an .alpha.-olefin, especially propylene, in a stirred or fluidized bed of substantially uniform and approximately spherical carrier particles of an .alpha.-olefin polymer of diameter 100-500 .mu.m, using a catalyst comprising an organo-metallic compound and a solid transition metal compound which has a particle size of less than 5 .mu.m, produces a propylene polymer having unexpectedly good powder flow characteristics. The transition metal compound is conveniently a titanium trichloride-containing material which has been treated with a dialkyl ether solution.
    Type: Grant
    Filed: June 20, 1977
    Date of Patent: August 28, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: Ashley D. Bye, John E. Priddle, Victor A. Wilson
  • Patent number: 4145497
    Abstract: Uranium-containing mixed catalysts containing uranium in the formal oxidation state +4 as uranium salts of carboxylic acids, a Lewis acid, and an organometallic aluminum compound are prepared and can be used for stereospecific polymerization of diolefins or mixtures of diolefins and monoolefins.
    Type: Grant
    Filed: May 31, 1977
    Date of Patent: March 20, 1979
    Assignee: Bayer Aktiengesellschaft
    Inventors: Gerd Sylvester, Josef Witte, Gunter Marwede
  • 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: 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: 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.