Transition Metal Is Ib, Iiib, Viib Or Atomic Number 58-71, 88, 90 Or Higher Patents (Class 526/164)
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Patent number: 6037297Abstract: 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: GrantFiled: December 15, 1998Date of Patent: March 14, 2000Assignee: Exxon Research and Engineering Co.Inventors: Robert T. Stibrany, Donald N. Schulz, Smita Kacker, Abhimanyu O. Patil
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Patent number: 6018007Abstract: 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: GrantFiled: September 22, 1997Date of Patent: January 25, 2000Assignee: Bridgestone CorporationInventor: Thomas J. Lynch
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Patent number: 6001478Abstract: 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: GrantFiled: August 8, 1997Date of Patent: December 14, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Maria Angelica Apecetche, Kevin Joseph Cann, Minghui Zhang
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Patent number: 5977270Abstract: 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: GrantFiled: January 26, 1998Date of Patent: November 2, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Timothy Todd Wenzel
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Patent number: 5965678Abstract: 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: GrantFiled: June 12, 1998Date of Patent: October 12, 1999Assignee: Bayer AGInventors: Sigurd Becke, Heike Windisch, Joachim Scholz, Steffen Kahlert
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Patent number: 5958820Abstract: 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: GrantFiled: October 2, 1997Date of Patent: September 28, 1999Assignee: Bayer AGInventors: Rudolf Taube, Steffen Maiwald, Thomas Ruhmer, Heike Windisch, Jurgen Giesemann, Gerd Sylvester
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Patent number: 5942589Abstract: 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: GrantFiled: August 1, 1997Date of Patent: August 24, 1999Assignee: BASF AktiengesellschaftInventors: Josef Wunsch, Michael Schiessl, Ralph Diener
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Patent number: 5914377Abstract: 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: GrantFiled: March 4, 1997Date of Patent: June 22, 1999Assignee: Bayer AGInventors: Gerd Sylvester, Hugo Vernaleken
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Patent number: 5877109Abstract: 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: GrantFiled: November 10, 1997Date of Patent: March 2, 1999Assignee: Bayer AGInventors: Karl-Heinz Reichert, Peter Marquardt, Christopher Eberstein, Birgit Garmatter, Gerd Sylvester
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Patent number: 5854363Abstract: An (omega-alkenyl) (cyclopentacarbyl) metallocene compound is provided. Polymerization processes therewith are also provided.Type: GrantFiled: November 24, 1997Date of Patent: December 29, 1998Assignee: Phillips Petroleum CompanyInventors: Michael Jung, Helmut G. Alt, M. Bruce Welch
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Patent number: 5789502Abstract: 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: GrantFiled: April 22, 1997Date of Patent: August 4, 1998Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher, Theodore Harris, The Vu, Margarito Lopez
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Patent number: 5756612Abstract: 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: GrantFiled: September 10, 1996Date of Patent: May 26, 1998Assignee: Idemitsu Kosan Co., Ltd.Inventors: Yoshiaki Aoyama, Norio Tomotsu
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Patent number: 5747613Abstract: 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: GrantFiled: January 2, 1996Date of Patent: May 5, 1998Assignee: Idemitsu Kosan Co., Ltd.Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu
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Patent number: 5747620Abstract: 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: GrantFiled: August 21, 1995Date of Patent: May 5, 1998Assignee: Idemitsu Kosan Co., Ltd.Inventors: Shuji Machida, Haruo Shikuma, Ayami Hoshino, Yutaka Takakura
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Patent number: 5741869Abstract: 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: GrantFiled: June 7, 1995Date of Patent: April 21, 1998Assignee: The B.F. Goodrich CompanyInventors: Brian Leslie Goodall, George Martin Benedikt, Lester Howard McIntosh, III, Dennis Allen Barnes, Larry Funderburk Rhodes
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Patent number: 5733988Abstract: 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: GrantFiled: November 1, 1996Date of Patent: March 31, 1998Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Maria Angelica Apecetche, Bai Xinlai, Kevin Joseph Cann
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Patent number: 5707913Abstract: 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: GrantFiled: June 6, 1995Date of Patent: January 13, 1998Assignee: BASF AktiengesellschaftInventors: Ruger Schlund, Martin Lux, Frank Edelmann, Ulrike Reissmann, Wolfgang Rohde
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Patent number: 5571881Abstract: 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: GrantFiled: June 7, 1995Date of Patent: November 5, 1996Assignee: The B. F. Goodrich CompanyInventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes, Larry F. Rhodes
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Patent number: 5569730Abstract: 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: GrantFiled: November 15, 1994Date of Patent: October 29, 1996Assignee: The B. F. Goodrich CompanyInventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes, Larry F. Rhodes
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Patent number: 5567784Abstract: 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: GrantFiled: September 20, 1995Date of Patent: October 22, 1996Assignee: Bayer AGInventors: Wolfgang Wieder, Dieter Kuhlmann, Wolfgang Nentwig
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Patent number: 5510434Abstract: 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: GrantFiled: November 23, 1994Date of Patent: April 23, 1996Assignee: Idemitsu Kosan Co., Ltd.Inventor: Mizutomo Takeuchi
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Patent number: 5502126Abstract: 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: GrantFiled: October 28, 1994Date of Patent: March 26, 1996Assignee: The Goodyear Tire & Rubber CompanyInventors: Anthony J. Bell, Barry A. Matrana, Adel F. Halasa
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Patent number: 5468819Abstract: 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: GrantFiled: November 16, 1993Date of Patent: November 21, 1995Assignee: The B.F. Goodrich CompanyInventors: Brian L. Goodall, George M. Benedikt, Lester H. McIntosh, III, Dennis A. Barnes
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Patent number: 5453474Abstract: 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: GrantFiled: October 8, 1993Date of Patent: September 26, 1995Assignee: The Dow Chemical CompanyInventors: Thomas H. Newman, Karen K. Borodychuk
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Patent number: 5428119Abstract: 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: GrantFiled: November 9, 1993Date of Patent: June 27, 1995Assignee: Polysar Rubber CorporationInventors: Thomas F. Knauf, Akhtar Osman
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Patent number: 5428120Abstract: 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: GrantFiled: October 8, 1993Date of Patent: June 27, 1995Assignee: The Dow Chemical CompanyInventors: Thomas H. Newman, Karen K. Borodychuk
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Patent number: 5405815Abstract: 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: GrantFiled: June 17, 1993Date of Patent: April 11, 1995Assignee: The Goodyear Tire & Rubber CompanyInventors: Anthony J. Bell, Barry A. Matrana, Adel F. Halasa
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Patent number: 5208304Abstract: 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: GrantFiled: October 7, 1991Date of Patent: May 4, 1993Assignee: Board of Trustees, Leland Stanford Junior UniversityInventor: Robert M. Waymouth
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Patent number: 4990573Abstract: 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: GrantFiled: February 13, 1990Date of Patent: February 5, 1991Assignee: Enichem Elastomeri S.p.A.Inventors: Piero Andreussi, Renzo Bianchi, Mario Bruzzone
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Patent number: 4931376Abstract: 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: GrantFiled: July 28, 1989Date of Patent: June 5, 1990Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Takeshi Ikematsu, Yasuo Hattori, Yoshihiro Inoki, Mitsuhiro Tanaka
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Patent number: 4727123Abstract: 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: GrantFiled: April 14, 1983Date of Patent: February 23, 1988Assignee: The Standard Oil CompanyInventors: Raymond J. Weinert, Jr., Kenneth C. Benton, Michael J. Desmond
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Patent number: 4699960Abstract: 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: GrantFiled: June 24, 1986Date of Patent: October 13, 1987Assignee: Enichem Elastomeri, S.p.A.Inventors: Silvano Gordini, Antonio Carbonaro, Stanislao Spina
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Patent number: 4699962Abstract: 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: GrantFiled: January 30, 1984Date of Patent: October 13, 1987Assignee: Phillips Petroleum CompanyInventors: Henry L. Hsieh, Gene H. C. Yeh
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Patent number: 4689368Abstract: 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: GrantFiled: August 4, 1986Date of Patent: August 25, 1987Assignee: Enoxy Chemical LimitedInventor: Derek K. Jenkins
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Patent number: 4663405Abstract: 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: GrantFiled: April 16, 1986Date of Patent: May 5, 1987Assignees: The Goodyear Tire & Rubber Company, Enichimica S.p.A., Enichem PolimeriInventor: Morford C. Throckmorton
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Patent number: 4619982Abstract: 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: GrantFiled: March 31, 1983Date of Patent: October 28, 1986Assignee: Enoxy Chemical LimitedInventor: Derek K. Jenkins
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Patent number: 4575538Abstract: 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: GrantFiled: December 20, 1984Date of Patent: March 11, 1986Assignee: Phillips Petroleum CompanyInventors: Henry L. Hsieh, Gene H. C. Yeh
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Patent number: 4544718Abstract: 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: GrantFiled: September 13, 1984Date of Patent: October 1, 1985Assignee: Phillips Petroleum CompanyInventors: Gene H. C. Yeh, Joel L. Martin, Henry L. Hsieh
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Patent number: 4533711Abstract: 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: GrantFiled: September 7, 1983Date of Patent: August 6, 1985Assignees: Bridgestone Tire Company Limited, Japan Synthetic Rubber Co., Ltd.Inventors: Yasumasa Takeuchi, Mitsuhiko Sakakibara, Nobuo Tagata, Masaki Ogawa, Yasushi Hirata, Shigeru Tomihira
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Patent number: 4429089Abstract: 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: GrantFiled: July 15, 1981Date of Patent: January 31, 1984Assignee: Anic, S.p.A.Inventors: Ugo Pedretti, Gabriele Lugli, Sergio Poggio, Alessandro Mazzei
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Patent number: 4384982Abstract: 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: GrantFiled: May 18, 1981Date of Patent: May 24, 1983Assignee: Phillips Petroleum CompanyInventor: Joel L. Martin
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Patent number: 4327201Abstract: 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: GrantFiled: October 22, 1980Date of Patent: April 27, 1982Assignee: The University of AkronInventors: Joseph P. Kennedy, Kurt C. Frisch, Jr.
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Patent number: 4296214Abstract: 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: GrantFiled: April 11, 1980Date of Patent: October 20, 1981Assignee: Mitsubishi Rayon Co., Ltd.Inventors: Kazumasa Kamada, Yoshio Nakai, Kazunori Abe
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Patent number: 4242232Abstract: 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: GrantFiled: July 3, 1979Date of Patent: December 30, 1980Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4167615Abstract: 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: GrantFiled: January 16, 1978Date of Patent: September 11, 1979Assignee: The Dow Chemical CompanyInventors: Donald E. Gessell, Kirby Lowery, Jr.
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Patent number: 4166167Abstract: 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: GrantFiled: June 20, 1977Date of Patent: August 28, 1979Assignee: Imperial Chemical Industries LimitedInventors: Ashley D. Bye, John E. Priddle, Victor A. Wilson
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Patent number: 4145497Abstract: 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: GrantFiled: May 31, 1977Date of Patent: March 20, 1979Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4125698Abstract: 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: GrantFiled: October 29, 1958Date of Patent: November 14, 1978Assignee: Studiengesellschaft Kohle M.b.h.Inventors: Karl Ziegler, Heinz Breil, Heinz Martin, Erhard Holzkamp
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Patent number: 4107416Abstract: 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: GrantFiled: July 8, 1976Date of Patent: August 15, 1978Assignee: Montedison S.p.A.Inventors: Umberto Giannini, Enrico Albizzati, Sandro Parodi
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Patent number: 4091082Abstract: 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: GrantFiled: June 4, 1976Date of Patent: May 23, 1978Assignee: The Dow Chemical CompanyInventors: Donald Earl Gessell, Kirby Lowery, Jr.