Nonmetallic Organic Oxygen Containing Patents (Class 502/125)
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Patent number: 5061666Abstract: A process for preparing a solid catalyst component which comprises halogenating a magnesium compound in the formula MgRR.sup.1.nCO.sub.2 l in which R and R.sup.1 are the same or different alkoxy or phenoxy groups and n is a number of from 0 to 2 with a halide of tetravalent titanium in the presence of dialkylester of a dihydric aromatic carboxylic acid and an inert hydrocarbon diluent by reacting at a temperature of from 120.degree. to 136.degree. C. and recovering the solid reaction product from the reaction mixture.Type: GrantFiled: April 24, 1990Date of Patent: October 29, 1991Assignee: Shell Research LimitedInventors: John C. Chadwick, Bart J. Ruisch
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Patent number: 5059571Abstract: The invention concerns a catalytic composition resulting from placing at least one divalent nickel compound into contact with at least one hydrocarbylaluminum halide and at least one epoxy compound, in any order. It also concerns the use of the catalytic composition in a process of oligomerizing monoolefins.Type: GrantFiled: August 1, 1990Date of Patent: October 22, 1991Assignee: Institut Francais du PetroleInventors: Yves Chauvin, Dominique Commereuc, Alain Forestiere, Gerard Leger
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Patent number: 5057475Abstract: The invention is a supported catalyst system including an inert support material, a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer.Type: GrantFiled: September 13, 1990Date of Patent: October 15, 1991Assignee: Exxon Chemical Patents Inc.Inventors: Jo Ann M. Canich, Gary F. Licciardi
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Patent number: 5055438Abstract: The invention is a polymerization catalyst system including an alumoxane and a Group IV B metallocene having a heteroatom ligand. The catalyst system can be employed to polymerize olefins to produce a high molecular weight polymer.Type: GrantFiled: June 4, 1990Date of Patent: October 8, 1991Assignee: Exxon Chemical Patents, Inc.Inventor: Jo Ann M. Canich
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Patent number: 5053467Abstract: A catalyst comprising (A) a solid catalyst component obained by reacting a homogeneous solution containing (i) at least one member selected from the group consisting of a combination of metallic magnesium and a hydroxyl organic compound, and an oxygen-containing organic compound of magnesium, (ii) an electron donor compound and (iii) an oxygen-containing organic compound of titanium with (iv) at least one aluminum halide compound and further reacting the obtained solid product with (v) an electron donor compound and (vi) a titanium halide compound, (B) at least one member selected from the group consisting of organic metal compounds of metals of the groups Ia, IIa, IIb, IIIb and IVb of the periodic table, and (C) an electron donor compound, is valuable as the catalyst for preparing a stereoregular polyolefin by homopolymerization or copolymerization of an .alpha.-olefin having at least 3 carbon atoms.Type: GrantFiled: May 14, 1990Date of Patent: October 1, 1991Assignee: Tosoh CorporationInventors: Yozo Kondo, Mitsuhiro Mori, Toshikazu Chikusa
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Patent number: 5045612Abstract: Olefins are polymerized under solution polymerization conditions in the presence of the solid catalytic product resulting from removing the liquid components from the product resulting from admixing in an inert diluent and in an atmosphere which excludes moisture and oxygen (A) at least one hydrocarbon soluble organomagnesium compound; (B) at least one organic hydroxyl-containing compound; (C) at least one reducing halide source; (D) at least one transition metal (Tm) alkoxide.Type: GrantFiled: April 18, 1990Date of Patent: September 3, 1991Assignee: The Dow Chemical CompanyInventors: Joseph G. Schell, Jr., Larry A. Meiske, Gary R. Marchand
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Patent number: 5037910Abstract: A method of manufacturing a polyolefin using a catalyst system of an ingredient (A) and ingredient (B), with ingredient A being obtained through successive reaction steps. Ingredient A is prepared by forming a mixture of (1) the combination of (a) metallic magnesium or an oxygen-containing organic compound of magnesium with (b) a mixture of a monohydroxylated organic compound and a polyhydroxylated organic compound, and (2) oxygen-containing organic compounds of titanium. The resulting solution is reacted in sequence with (3) at least one first halogenated aluminum compound, (4) at least one silicon compound and (5) at least one second halogenated aluminum compound. Compounds 3 and 5 are added at temperatures not exceeding about 25.degree. C. Ingredient B is an organometallic compound of metals from Group Ia, IIa, IIIa or IVa of the Periodic Table. The resulting free-flowing polyolefin is characterized by a large average particle size and small amount of fine particles.Type: GrantFiled: October 17, 1989Date of Patent: August 6, 1991Assignee: Paxon Polymer Company, L.P.Inventors: Gregory A. Cook, Theodore R. Engelmann
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Patent number: 5034484Abstract: The invention concerns:a catalytic solid containing magnesium, a halogen, titanium and silicon, this catalytic solid also containing aluminium and being microporous;a process for preparing this catalytic solid;use of this catalytic solid for polymerizing alpha-olefines.Type: GrantFiled: February 22, 1989Date of Patent: July 23, 1991Assignee: Solvay & Cie (Societe Anonyme)Inventors: Leopold Demiddeleer, Yvan Kempeneer, Laurence Desvachez
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Patent number: 5034366Abstract: A vanadium-based catalyst is treated with a polysiloxane oil as a means of enhancing catalyst activity and polymer productivity.Type: GrantFiled: December 29, 1989Date of Patent: July 23, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Frederick J. Karol, Sun-Chueh Kao
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Patent number: 5034361Abstract: Normally sparingly soluble magnesium alkoxide is solubilized in alkanol by the additional presence of certain acidic materials. The resulting solution is used to produce a mixture of substantially spherical particles, substantially free of fines, containing an adduct magnesium alkoxide. The particles are converted by conventional methods to a procatalyst precursor of an olefin polymerization catalyst of good activity and good selectivity to stereoregular polymer whenever appropriate, which catalyst produces polymer product of good morphology.Type: GrantFiled: May 24, 1990Date of Patent: July 23, 1991Assignees: Shell Oil Company, Union Carbide Chemicals and Plastics Company, Inc.Inventors: Robert C. Job, Daniel P. Zilker, Jr., John C. Chadwick
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Patent number: 5032562Abstract: There is disclosed a supported olefin polymerization catalyst composition comprising a precursor and a catalyst activator. The precursor comprises a magnesium compound, e.g., dibutylmagnesium, a cyclopentadienyl group-containing zirconium compound, and a titanium and/or a vanadium compound, e.g., TiCl.sub.4, and an organic compound, e.g., an alcohol. The catalyst activator is a mixture of a conventional Ziegler/Natta co-catalyst and a zirconium sites activator, e.g., methylaluminumoxane. The catalyst is used in the presence of small amounts of hydrogen to produce polymers having multimodal molecular weight distribution in a single reactor.Type: GrantFiled: December 27, 1989Date of Patent: July 16, 1991Assignee: Mobil Oil CorporationInventors: Frederick Y. Lo, Thomas E. Nowlin, Pradeep P. Shirodkar
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Patent number: 5032563Abstract: Ziegler polymerization of .alpha.-olefins is disclosed which is characterized by a solid catalyst component used in the Ziegler-type catalyst. The solid catalyst component, Component (A), comprises Component (i) which is a solid catalyst component for a Ziegler-type catalyst comprising Ti, Mg and a halogen; Component (ii) a silicon compound of a formula:R.sup.1 R.sup.2.sub.3-n Si(OR.sup.3).sub.nwherein R.sup.1 -R.sup.3 are each hydrocarbyl group characterized by R.sup.1 which has a branched hydrocarbyl group;Component (iii) a halogen compound of W or Mo; and Component (iv) an organometal compound of a metal of Groups I to IV of the Periodic Table.Type: GrantFiled: November 17, 1989Date of Patent: July 16, 1991Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Toshihiko Sugano, Kazuo Nakamura
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Patent number: 5030605Abstract: A vanadium-based catalyst is treated with certain alkylaluminum alkoxide compounds as a means of narrowing and effectively regulating the molecular weight distribution of the polymers produced with the catalyst.Type: GrantFiled: December 29, 1989Date of Patent: July 9, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Sun-Chueh Kao, Frederick J. Karol
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Patent number: 5028574Abstract: A catalyst and method is provided for the production of ultra-high molecular weight polymers characterized as having an inherent viscosity of above 12.0 by contacting ethylenically unsaturated monomers with a dual electron donor catalyst under polymerization conditions.Type: GrantFiled: March 14, 1990Date of Patent: July 2, 1991Assignee: Conoco Inc.Inventors: Donald E. Gessell, Donald P. Hosman
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Patent number: 5026889Abstract: A catalyst system comprising(A) a halogen compound of trivalent titanium,(B) an organo-aluminum compound of the formula,R.sub.3-(m+n) AlY.sub.m X.sub.nwhereinY is a group having at least one of oxygen, nitrogen, sulfur and phosphorus atoms linked to the aluminum atom, R is a hydrogen atom, an alkyl having 1 to 18 carbon atoms, an alkenyl having 2 to 18 carbon atoms, a cycloalkyl having 3 to 18 carbon atoms, an aryl having 6 to 18 carbon atoms, or an aralkyl having 7 to 18 carbon atoms,X is a halogen atom, and m and n are numbers satisfying the equations, 0<m<1, 0.ltoreq.n<2, 0<m+n.ltoreq.2, and(C) an electron-donor, and a method for producing an olefin polymer which comprises polymerizing olefins using said catalyst system. According to this method, highly crystalline olefin polymers having a broad melecular weight distribution can be produced.Type: GrantFiled: December 21, 1988Date of Patent: June 25, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Toshio Sasaki, Masahisa Okawa, Hideaki Matsuura
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Patent number: 5023223Abstract: A process for producing a highly stereospecific .alpha.-olefin polymer which comprises homopolymerizing or copolymerizing an .alpha.-olefin or copolymerizing an .alpha.-olefin with ethylene by the use of a catalyst system comprising:(A) a solid catalyst component containing a trivalent titanium compound obtained by reducing a titanium compound represented by the following general formula:Ti(OR.sup.1).sub.n X.sub.4-n(R.sup.1 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom and n represents a number satisfying 0<n.ltoreq.Type: GrantFiled: December 11, 1989Date of Patent: June 11, 1991Assignee: Sumitomo Chemical Company, LimitedInventors: Takeshi Ebara, Toshio Sasaki, Kiyoshi Kawai
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Patent number: 5021382Abstract: High density polymers of ethylene are produced in improved yields employing a solid Ziegler type transition metal-containing catalyst component and an organoaluminum cocatalyst in the presence of a small amount of an aliphatic diene having at least 4 carbon atoms and a terminal double bond. The amount of diene is from about 0.01 to about 3000 mole per gram atom of transistion metal in the catalyst component. The catalyst component variously may be pretreated with the diene before using the component for homopolymerization, may be prepolymerized with ethylene in the presence of the diene, may be prereduced in the presence of the diene, or the diene may be added to the polymerization reaction. Preferred dienes are .alpha.-.omega.-dienes.Type: GrantFiled: February 28, 1990Date of Patent: June 4, 1991Assignee: Exxon Chemical Patents Inc.Inventor: Gerald D. Malpass, Jr.
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Patent number: 5015612Abstract: An olefin polymerization catalyst component subjected to successive preliminary polymerization treatment using each of a straight chain alpha-olefin having 2 to 5 carbon atoms and 3-methyl-1-butene; an olefin polymerization catalyst using the olefin polymerization catalyst component; a process for polymerizing olefin(s) which comprises polymerizing or copolymerizing olefin(s) in the presence of the olefin polymerization catalyst; and a film and an injection-molded article of polypropylene which is prepared by the process are also provided.Type: GrantFiled: September 14, 1989Date of Patent: May 14, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Kenji Doi, Akinori Toyota
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Patent number: 5013803Abstract: Disclosed is a homogeneous vanadium catalyst composition prepared by the reaction of an alkylaluminum dihalide with a solid reaction product produced by reacting (A) a silicon alkoxide, (B) a hydrocarbon soluble vanadium compound, and (C) a trialkylaluminum. The solid reaction product may be produced by complexing the (A) silicon alkoxide first with either the (B) vanadium compound or the (C) trialkylaluminum. The intermediate complex (I) of such reaction is then treated with the remaining reageant (either the vandium compound or the trialkylaluminum as the case may be) whereupon the solid reaction product (II) is formed. The solid reaction product (II) of the silicon alkoxide-vanadium compound/trialkylaluminum reaction is then reacted with (D) an alkylaluminum dihalide to produce a homogeneous hydrocarbon soluble product (III) which is highly active for catalyzing the polymerization of olefines to a polyolefin having a narrow molecular weight distribution.Type: GrantFiled: March 23, 1990Date of Patent: May 7, 1991Assignee: Exxon Chemical Patents, Inc.Inventor: Steven A. Best
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Patent number: 5006620Abstract: Polymers of propene are prepared by means of a Ziegler-Natta catalyst system composed of (1) a titanium component based on a finely divided shape-dictating silica gel and containing titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component, the titanium component (1) being obtained by (1.1) first preparing (I) a carrier material from (Ia) a silica gel, (Ib) an organomagnesium compound (Ic) a gaseous chlorinating agent and (Id) a specific phthalic acid derivative by (1.1.1) first reacting (Ia) with (Ib), then (1.1.2) passing (Ic) into the product of (1.1.1) together with the phthalic acid derivative (Id) and isolating (I), (1.2) preparing a solid-phase intermediate from (I), (II) an alkanol and (III) titanium tetrachloride by (1.2.1) first reacting (I) with (II), then (1.2.2) introducing (III) into the product resulting from (1.2.1), then (1.3) extracting the solid-phase result from (1.Type: GrantFiled: August 30, 1989Date of Patent: April 9, 1991Inventors: Ralf Zolk, Juergen Kerth, Rainer Hemmerich
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Patent number: 5006499Abstract: A process for the preparation of a solid catalyst of the Ziegler-Natta type comprises precipitating the solid catalyst in a liquid hydrocarbon medium by reacting (A) a solution of a soluble magnesium alkoxide and (B) a transition metal halide which is a halide of Ti (IV), a halide of V (IV) or a halide of VO (III) in the presence of (C) at least one transition metal alkoxide which is free from halogen and soluble in liquid hydrocarbon. The precipitated solid catalyst consists of spheroidal particles having a mean diameter by mass of from 10 to 70 microns and a narrow particle size distribution such that the ratio of mean diameter by mass to the mean diameter by number is greater than 1.2 and smaller than 2.0.Type: GrantFiled: November 21, 1988Date of Patent: April 9, 1991Assignee: BP Chemicals LimitedInventor: Eric Daire
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Patent number: 5002916Abstract: Supported catalysts component for producing ethylene-propylene elastomers comprising a compound represented by the formula:(1) [V.sub.3 O(RCO.sub.2) (ED).sub.3 ].sub.2. V.sub.2 O.sub.2 X.sub.6, or(2) V.sub.3 O(RCO.sub.2).sub.6 (ED).sub.3wherein R is alkyl, cycloalkyl, aryl and haloalkyl,wherein R is alkyl, cycloalkyl, aryl and haloalkyl,ED is an electron donor selected from alkyl esters of aliphatic and aromatic carboxylic acid, aliphatic ketones, aliphatic amines, aliphatic alcohols, alkyl and cycloalkyl ethers, and mixtures thereof; andX is selected from Cl--, Br--, Fl-- or RCO.sub.2.sup.--.Type: GrantFiled: March 2, 1990Date of Patent: March 26, 1991Assignee: Exxon Chemical Patents Inc.Inventors: Terry J. Burkhardt, William B. Brandley
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Patent number: 4999327Abstract: A vanadium-based catalyst is treated with certain silicon-containing compounds as a means of narrowing and effectively regulating the molecular weight distribution of the polymers produced with the catalyst.Type: GrantFiled: December 30, 1988Date of Patent: March 12, 1991Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventors: Sun-Chueh Kao, Frederick J. Karol
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Patent number: 4990478Abstract: An olefin polymerization catalyst system comprises a solid, hydrocarbon-insoluble, magnesium-containing, titanium-containing, electron donor-containing component; an alkyl aluminum compound; and organosilane compound selected from the group consisting of branched C.sub.3 -C.sub.10 alkyl-t-butoxydimethoxysilanes.Type: GrantFiled: September 21, 1989Date of Patent: February 5, 1991Assignee: Amoco CorporationInventors: Charles R. Hoppin, Benjamin S. Tovrog
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Patent number: 4990479Abstract: An olefin polymerization catalyst formed from (A) a solid titanium catalyst component containing magnesium, titanium and halogen as essential ingredients, (B) an organoaluminum compound, and (C) an organosilicon compound containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative derived from any of these groups.A polymerization process which comprises polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst to form a homopolyolefin having a high stereoregularity or a copolyolefin having a narrow composition distribution.Type: GrantFiled: June 15, 1989Date of Patent: February 5, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Naoshi Ishimaru, Mamoru Kioka, Akinori Toyota
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Patent number: 4990477Abstract: A catalyst component (X") obtained by treating an olefin polymerization catalyst (X) formed from (A) a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor as essential ingredients, (B) an organoaluminum compound catalyst component, and as required, (C) an electron donor with an alpha-olefin by preliminarily polymerizing the alpha-olefin in an amount of 0.1 to 500 g per gram of the solid titanium catalyst component (A) in the presence of said catalyst (X), and contacting the treated catalyst (X') with at least 0.1 mole, per gram-atom of titaninum in the treated catalyst (X"), of oxygen. A process for producing the olefin polymerization catalyst component. A catalyst (Y) for olefin polymerization formed from [I] the above catalyst component (X"), [II] an organoaluminum compound catalyst component and as required [III] an electron donor. Also provided is a process for polymerizing olefins in the presence of the olefin polymerization catalyst (Y).Type: GrantFiled: September 13, 1989Date of Patent: February 5, 1991Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Akinori Toyota
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Patent number: 4988656Abstract: A solid hydrocarbon-insoluble, alpha-olefin polymerization catalyst component with superior activity, stereospecificity and morphology characteristics comprises the product formed by (A) forming a solution of a magnesium-containing species from a magnesium carbonte or a magnesium carboxylate; (B) precipitating solid particles from such magnesium-containing solution by treatment with a transition metal halide and an organosilane; (C) reprecipitating such solid particles from a mixture containing a cyclic ether; and (D) treating the reprecipitated particles with a transition metal compound and an electron donor.Type: GrantFiled: May 12, 1989Date of Patent: January 29, 1991Assignee: Amoco CorporationInventors: Gregory G. Arzoumanidis, Nicholas M. Karayannis, Habet M. Khelghatian, Sam S. Lee, Bryce V. Johnson
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Patent number: 4981826Abstract: Described is a magnesium-transition metal containing catalyst component, comprising a solid reaction product obtained by treating a solid support material in an inert solvent in any order with (A) a halogenated silane compound, (B) an alkoxy-containing magnesium compound, (C) and acyl halide, (D) at least one transition metal compound of a Group IVb-VIb or VIII metal, and optionally (E) treating the magnesium-transition metal containing product with an organometallic compound of a Group IIa, IIb, or IIIa metal. The magnesium-transition metal containing catalyst component, when employed with known Ziegler cocatalyst, provides a catalyst system which have very high catalytic activities for production of polyolefin of high bulk density. The polymerization kinetics of the catalyst system is controllable as a function of the reagent molar ratios selected for production of the magnesium-transition metal containing catalyst component.Type: GrantFiled: November 17, 1989Date of Patent: January 1, 1991Assignee: Exxon Chemical Patents Inc.Inventor: Anthony N. Speca
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Patent number: 4980329Abstract: Disclosed is a component for a catalyst for the polymerization of alpha-olefins to stereoregular polymers having narrow molecular weight distribution. The product is formed by the reaction of a solid catalyst-forming component comprising (1) a Ti compound having at least one Ti-halogen bond and (2) optionally, an electron-donor compound, supported on an anhydrous Mg dihalide in active form, with certain amounts of an organic compound (AH) containing at least one active hydrogen atom, in the presence of a liquid medium which is inert with respect to the Ti compound and the other components of the catalyst component, and which has a dielectric constant greater than 2 at 20.degree. C.Catalysts comprising the reaction product of the solid catalyst component prepared as above described, with an Al-alkyl compound and an electron-donor compound are also disclosed.Type: GrantFiled: May 15, 1989Date of Patent: December 25, 1990Assignee: Himont IncorporatedInventors: Pier C. Barbe, Enrico Albizzati, Umberto Giannini, Giovanni Baruzzi, Luciano Noristi
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Patent number: 4980330Abstract: 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 transition metal compound.Type: GrantFiled: November 30, 1989Date of Patent: December 25, 1990Assignee: The Dow Chemical CompanyInventors: Gary R. Marchand, Ricardo Fuentes, Jr., William M. Coleman, III
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Patent number: 4970185Abstract: A process for the preparation of methanol by contacting CO and H.sub.2 with a novel catalytic system formed by combining (a) a nickel salt having a pK.sub.a <4.70, (b) an alcohol, and (c) a hydride of an alkali metal or of an alkaline earth metal.Type: GrantFiled: May 15, 1989Date of Patent: November 13, 1990Assignee: Shell Oil CompanyInventors: Swan T. Sie, Eit Drent, Willem W. Jager
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Patent number: 4970184Abstract: A catalyst for the copolymerization of ethylene by the gas-phase fluidized-bed method is prepared by a process in which a titanium-containing and magnesium-containing active component, reacted with an alcohol as a complexing agent, is applied to a finely divided silica from homogeneous solution, in the presence of a polysiloxane, by evaporating the solvent, and the resulting homogeneous catalyst intermediate is then preactivated by treatment with the alkylaluminum compound and the Lewis base in an inert hydrocarbon solution, and the copolymers prepared using the above catalyst are employed for the production of films exhibiting little blocking.Type: GrantFiled: May 3, 1989Date of Patent: November 13, 1990Assignee: BASF AktiengesellschaftInventors: Eckard Schauss, Heinz Vogt, Rainer Hemmerich, Guenther Schweier, Rudolf Mueller-Mall
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Patent number: 4970186Abstract: A solid catalyst component prepared by admixing and reacting, with a reaction product which has been obtained by suspending diethoxymagnesium in an alkylbenzene and bringing the suspension into contact with titanium tetrachloride in an amount less than 1 in terms of volume ratio to the alkylbenzene, a phthaloyl dichloride at a temperature within the range between 80.degree. C. and 125.degree. C., washing the resultant solid substance with an alkylbenzene, and reacting the solid substance in the presence of an alkylbenzene with titanium tetrachloride in an amount less than 1 in terms of volume ratio to the alkylbenzene as well as an olefin polymerization catalyst which comprises (A) the above specified solid catalyst component, (B) a silicon compound of the general formula: SiR.sub.m (OR').sub.Type: GrantFiled: December 23, 1988Date of Patent: November 13, 1990Assignee: Toho Titanium Co., Ltd.Inventors: Minoru Terano, Hirokazu Soga, Masuo Inoue
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Patent number: 4970187Abstract: A method for producing a olefin polymer, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst comprising:(A) a solid catalyst component obtained by thermally reacting (a.sub.1) a magnesium compound of the formula Mg(OR.sup.1).sub.n (OR.sup.2).sub.2-n wherein each of R.sup.1 and R.sup.2 which may be the same or different is an alkyl group, and aryl group or an aralkyl group, and n is 2.gtoreq.n.gtoreq.0, (a.sub.2) a titanium compound of the formula Ti(OR.sup.3).sub.4 wherein R.sup.3 is an alkyl group, an aryl group or an aralkyl group and (a.sub.3) a silicon compound of the formula Si(OR.sup.4).sub.4 wherein R.sup.4 is an alkyl group, an aryl group or an aralkyl group and contacting and treating (a) the resulting thermal reaction product with (b) a halogen-containing titanium compound and (c) an electron donative compound, and(B) an organometallic compound of a metal of Groups I-III of the Periodic Table.Type: GrantFiled: November 9, 1989Date of Patent: November 13, 1990Assignee: Mitsubishi Kasei CorporationInventors: Yoshinori Suga, Eiji Tanaka, Yasuo Maruyama
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Patent number: 4960743Abstract: A method for the production of a catalyst carrier for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X stands for a halogen atom], and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M stands for a boron, carbon, aluminum, silicon, or phosphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, and m stands for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied], to contact (D) a halogen-containing alcohol.Type: GrantFiled: November 18, 1988Date of Patent: October 2, 1990Assignee: Toa Nenryo Kogyo K.K.Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
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Patent number: 4960741Abstract: A process of the Ziegler-Natta type is prepared using a preactivated support containing (A) from 80 to 95 mol % of magnesium chloride and (B) 5 to 20 mol % of at least one electron donor compound which contains no labile hydrogen and no ester function; the preactivated support consisting of spherical particles having a mass average diameter, Dm of 10 to 100 microns and a particle size distribution Dm/Dn of less than 2. The catalyst is prepared by (i) treating the preactivated support with at least one electron donor compound containing labile hydrogen, (ii) treating the resulting activated support with at least one ester of an aromatic acid, (iii) impregnating the treated support with titanium tetrachloride and (iv) after washing the impregnated catalyst activating it with titanium tetrachloride. The catalyst has a high titanium content and a high activity when used to polymerize olefins.Type: GrantFiled: February 22, 1989Date of Patent: October 2, 1990Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, Stylianos Sandis
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Patent number: 4959336Abstract: A process is disclosed for improving the productivity of a polymerization catalyst formed from a magnesium ethoxide. The process comprises treating the magnesium ethoxide with a silane alkoxide at or above the temperature at which any alcohol which may be bound to the ethoxide dissociates from the alkoxide prior to subjecting the magnesium ethoxide to metathesis.Type: GrantFiled: April 7, 1989Date of Patent: September 25, 1990Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 4954470Abstract: A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a chlorinated alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with an activator. The resulting catalyst composition has high polymerization activity in the polymerization of C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties in the copolymerization of ethylene with the higher alpha-olefins.Type: GrantFiled: December 21, 1988Date of Patent: September 4, 1990Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Kenneth G. Schurzky
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Patent number: 4954471Abstract: Disclosed is a homogeneous vanadium catalyst composition prepared by the reaction of an alkylaluminum dihalide with a solid reaction product produced by reacting (A) a silicon alkoxide, (B) a hydrocarbon soluble vanadium compound, and (C) a trialkylaluminum. The solid reaction product may be produced by complexing the (A) silicon alkoxide first with either the (B) vanadium compound or the (C) trialkylaluminum. The intermediate complex (I) of such reaction is then treated with the remaining reagent (either the vanadium compound or the trialkylaluminum as the case may be) whereupon the solid reaction product (II) is formed. The solid reaction product (II) of the silicon alkoxide-vanadium compound/trialkylaluminum reaction is then reacted with (D) an alkylaluminum dihalide to produce a homogeneous hydrocarbon soluble product (III) which is highly active for catalyzing the polymerization of olefins to a polyolefin having a narrow molecular weight distribution.Type: GrantFiled: November 28, 1988Date of Patent: September 4, 1990Assignee: Exxon Chemical Patents Inc.Inventor: Steven A. Best
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Patent number: 4952649Abstract: A solid titanium catalyst component (A) of a catalyst system useful in the polymerization of olefins or copolymerization of two or more olefins or one or more olefins and a diene is prepared by contacting a liquid hydrocarbon solution of (i) a magnesium compound, such as magnesium chloride, with (ii) a liquid titanium compound, such as TiCl.sub.4, or a solution of a titanium compound in a hydrocarbon solvent, to form a solid product. The solid product is formed in the presence of (D) an electron donor, e.g. methyl formate, acetic acid, acetic anhydride, acetone, methyl ether, butyl Cellosolve, dimethyl carbonate, methyl silicate. The solid product is also contacted with a polycarboxylic acid ester, e.g. diethyl methylsuccinate. The polymerization or copolymerization of the olefin is carried out in the presence of the solid titanium catalyst (A) and (B) an organometallic compound of a Group I to III metal and (C) an organic silicon compound having an Si--O--C bond.Type: GrantFiled: March 11, 1988Date of Patent: August 28, 1990Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Norio Kashiwa
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Patent number: 4950630Abstract: A method for the production of a catalyst component for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X stands for a halogen atom], and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M stands for a boron, carbon, aluminum, silicon, or phosphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, and m stands for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied], to contact (d) a halogen-containing alcohol and then contact (E) an electron donor type compound and (F) a titanium compound.Type: GrantFiled: November 18, 1988Date of Patent: August 21, 1990Assignee: Toa Nenryo Kogyo, K.K.Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
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Patent number: 4948770Abstract: Disclosed is a method for making crystalline magnesium halide particles usable for preparing catalyst and usable in the polymerization of alpha olefins having the formula MgnEmXp * y ROH wherein y is a value greater than 0 and up to 12, and which comprises the steps of:contacting the components of a magnesium compound of the formula MgnEmXp, wherein Mg is the magnesium component, n is a value from 0.Type: GrantFiled: August 8, 1988Date of Patent: August 14, 1990Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 4948771Abstract: A catalyst composition comprising:(i) a complex comprised of V.sub.2 X.sub.3 (ED).sub.m and AlCl.sub.2 R.sub.2 whereinX=Cl, Br, or I, or mixtures thereofED=an electron donor, which is an ether, a phosphine, a ketone, an isocyanide, or an ester, said electron donor having 2 to 20 carbon atomsR=an alkyl having up to 14 carbon atomsm=an integer from 3 to 6,said complex impregnated into an inorganic oxide support;(ii) sufficient trialkylaluminum compound adsorbed on the inorganic oxide support to provide a molar ratio of adsorbed trialkylaluminum compound to vanadium of about 2.5:1 to about 10:1;(iii) a halocarbon promoter; and(iv) a hydrocarbyl aluminum cocatalyst.Type: GrantFiled: December 7, 1988Date of Patent: August 14, 1990Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventor: Francis G. Stakem
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Patent number: 4946816Abstract: In a solid hydrocarbon-insoluble, alpha-olefin polymerization catalyst component with superior activity, stereospecificity and morphology characteristics comprising the product formed by (A) forming a solution of a magnesium-containing species from a magnesium alkyl (or hydrocarbyl) carbonate or a magnesium carboxylate; (B) precipitating solid particles from such magnesium-containing toluene-based solvent by treatment with a transition metal halide and an organosilane; (C) reprecipitating such solid particles from a mixture containing a cyclic either; and (D) treating the reprecipitated particles with a transition metal compound and an electron donor, the morphology of such component is modified by incorporating a morphology-affecting amount of C.sub.8 -C.sub.10 aromatics within the toluene-based solvent in Step B, Step A, in Step C prior to addition of ether, or combinations thereof.Type: GrantFiled: August 21, 1989Date of Patent: August 7, 1990Assignee: Amoco CorporationInventors: Steven A. Cohen, Gregory G. Arzoumanidis, Nicholas M. Karayannis, Habet M. Khelghatian, Sam S. Lee
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Patent number: 4945076Abstract: The activity of olefin polymerization catalysts comprising a Group IVB transition metal compound and an aluminoxane can be improved by the addition of a hydroxysiloxane compound.Type: GrantFiled: July 28, 1989Date of Patent: July 31, 1990Assignee: Akzo America Inc.Inventors: Andrzej M. Piotrowski, Elliot I. Band
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Patent number: 4945142Abstract: A catalyst and method is provided for the production of ultra-high molecular weight polymers characterized as having an inherent viscosity of above 12.0 by contacting ethylenically unsaturated monomers with a dual electron donor catalyst under polymerization conditions.Type: GrantFiled: November 14, 1988Date of Patent: July 31, 1990Assignee: Conoco Inc.Inventors: Donald E. Gessell, Donald P. Hosman
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Patent number: 4940682Abstract: A solid catalyst component for olefin polymerization which comprises a catalyst component comprising at least titanium and chlorine fixed onto a porous substance of which the pore volume, at a pore radius in a range of from 200 to 2,000 .ANG., is 0.3 cc/g or more, said pore volume is 35% or more of the pore volume at a pore radius in a range of from 35 to 75,000 .ANG., the average particle diameter is from 5 to 300 .mu.m, the geometrical standard deviation of the particle size distribution is 2 or less and the solubility in toluene at 100.degree. C. is 30 wt. % or less.Type: GrantFiled: October 26, 1988Date of Patent: July 10, 1990Assignee: Sumitomo Chemical Company, LimitedInventors: Toshio Sasaki, Takeshi Ebara, Kiyoshi Kawai
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Patent number: 4935394Abstract: This invention provides new supported catalyst compositions for the polymerization of 1-olefins, together with processes for preparing and using the catalysts. The catalyst compositions include two catalyst components. The first catalyst component is formed by reacting a halogen-containing compound of the formula: H.sub.a M.sup.1 X.sup.1.sub.b R.sup.1.sub.(c-b-a) wherein M.sup.1 is boron, carbon, silicon or mixtures thereof; X.sup.1 is Cl, Br or mixtures thereof; R.sup.1 is a hydrocarbyl or alkoxy radical; with a mixture produced by contacting a finely divided porous inorganic oxide support in an inert solvent with a solution made by combining a magnesium dihydrocarbyloxide dissolved in an inert solvent, and of the formula: Mg(OR.sup.2).sub.2 wherein R.sup.2 is a hydrocarbyl radical, with a transition metal hydrocarbyloxide of the formula: M.sup.2 (OR.sup.3).sub.y wherein M.sup.2 is a transition metal from Group IVB, VB, and VIB of the Periodic Table; and R.sup.3 is a hydrocarbyl radical.Type: GrantFiled: August 19, 1988Date of Patent: June 19, 1990Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang
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Patent number: 4927797Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a Toho-type, new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is a bulky, basic alkyl or cycloalkyl group containing at least one secondary or tertiary carbon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl group with a primary carbon atom attached to the silicon atom. The system has a catalyst efficiency of at least about 30 kg/g-cat.2h as the Al/Si mole ratio varies from 20-200 in the system. The system easily achieves efficiencies over 60 kg/g-cat.2h. The system also exhibits good control over the xylene solubles, melt flow and molecular weight distribution of the polymer product.Type: GrantFiled: December 2, 1988Date of Patent: May 22, 1990Assignee: Fina Technology, Inc.Inventor: John A. Ewen
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Process for the production of polyethylene with a broad and/or bimodal molecular weight distribution
Patent number: 4918038Abstract: A process for the production of an ethylene homopolymer or copolymer comprising passing ethylene with or without at least one alpha-olefin comonomer having 3 or more carbon atoms into contact with a mixed catalyst system, under polymerization conditions, said mixed catalyst system comprising:(a) the reaction product of (i) a vanadium halide having the formula VX.sub.3 wherein X is chlorine, bromine, or iodine and each X is alike or different; (ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a and (iii) an electron donor(b) one of the following:(i) a complex having the formula ZrMg.sub.b X.sub.c (ED).sub.d ; or(ii) a vanadium oxy compound having the formula VOX.sub.3, VOX.sub.2, VOX, or VO.sub.2 X wherein X is as defined above, or VO(OR).sub.3(c) a hydrocarbyl aluminum cocatalyst; and(d) a halocarbon promoter having the formula R.sub.e CX.sub.Type: GrantFiled: October 29, 1987Date of Patent: April 17, 1990Assignee: Union Carbide Chemicals and Plastics Company Inc.Inventors: Sari-Beth Samuels, Frederick J. Karol