Including Plural Additions Of Component A Patents (Class 502/110)
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Patent number: 5863853Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst system of the invention provides for a supported bulky ligand transition metal catalyst system which when utilized in a polymerization process substantially reduces the reactor fouling and sheeting particularly in a gas phase polymerization process.Type: GrantFiled: February 24, 1997Date of Patent: January 26, 1999Assignee: Exxon Chemical Patents, Inc.Inventors: George Alan Vaughan, Anthony Nicholas Speca, Patrick Brant, Jo Ann Marie Canich
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Patent number: 5858903Abstract: Catalysts consisting ofA) an alcoholate of the rare earths, a carboxylate of the rare earths, a complex compound of the rare earths with diketones and/or an addition compound of the halides of the rare earths with an oxygen or nitrogen donor compound,B) an aluminium trialkyl, a dialkyl aluminium hydride and/or an alumoxane,C) another Lewis acid andD) an inert, particulate inorganic solid with a specific surface of greater than 10 m.sup.2 /g (BET) and a pore volume of 0.3 to 15 ml/gare eminently suitable for the polymerization of conjugated dienes, more particularly butadiene, in the gas phase.Type: GrantFiled: September 18, 1997Date of Patent: January 12, 1999Assignee: Bayer AGInventors: Gerd Sylvester, Hugo Vernaleken
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Patent number: 5763549Abstract: Metallocene catalysts and their preparation and use in the polymerization of olefins. Specifically, the catalysts and processes relate to polymerization of olefins in which an aluminum ionizing agent containing a triphenylcarbenium ion is utilized in preparing the catalyst. The preparation of an olefin polymerization catalyst comprising a metallocene-type catalyst and triphenylcarbenium tetrakis(pentafluorophenyl)aluminate is disclosed.Type: GrantFiled: June 4, 1992Date of Patent: June 9, 1998Assignee: Fina Technology, Inc.Inventors: Michael J. Elder, John A. Ewen
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Patent number: 5753577Abstract: A novel class of olefin polymerization catalyst system based on specific organo-transition metal compounds and which are effective for controlling in particular the width and mode of the molecular weight distribution of the resulting polyolefins, and processes of olefin polymerization using the novel catalyst systems are disclosed.Type: GrantFiled: February 21, 1997Date of Patent: May 19, 1998Assignee: Tosoh CorporationInventors: Satoshi Hamura, Toru Yoshida, Morihiko Sato
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Patent number: 5739224Abstract: Procedure for the preparation of a solid catalyst component which is active in the polymerization of olefins, comprising the steps:a) contacting a silylated silica support with a solution of Mg-halide or Mg-alkyl-halide or a mixture of both,b) contacting the catalyst-precursor obtained in (a) with Mg-alkyl or Mg-alkyl-halide or a mixture of both, optionally in presence of electron-donors (Lewis bases),c) halogenating the catalyst-precursor obtained in (b) by contact of said activated support with halogenating agents,d) titanating the catalyst-precursor obtained in (c) with Ti-tetrahalide in the presence of electron-donors,e) recovering the solid catalyst-component from the reaction products of step (d).The catalyst component, which is obtained according to the above procedure, may also be used together with Al-trialkyl or Al-alkyl-halides and a Lewis base, as a catalyst for the polymerization of olefins.Type: GrantFiled: November 8, 1996Date of Patent: April 14, 1998Assignee: PCD Polymere Gesellschaft m.b.H.Inventors: Luciano Luciani, Wolfgang Neissl, Birgit Wenidoppler
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Patent number: 5733979Abstract: Catalytic solids based on titanium trichloride complex, usable for the stereospecific polymerisation of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of the liquid material resulting from bringing TiCl.sub.4, pretreated with an electron-donor compound, into contact with a composition (C) corresponding to the general formulaAlR.sub.p (Y).sub.q X.sub.3-(p+q)in whichR represents a hydrocarbon radical or a hydrogen atom;Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrogen atom;X represents a halogen;p is an arbitrary number such that 0<p<3; andq is an arbitrary number such that 0<q<3;the sum (p+q) being such that 0<(p+q).ltoreq.3.These catalytic solids of controllable porosity permit the production of a wide range of propylene polymers, in particular the propylene and ethylene copolymers known as "block" copolymers.Type: GrantFiled: February 18, 1993Date of Patent: March 31, 1998Assignee: Solvay (Societe Anonyme)Inventors: Jean-Louis Costa, Sabine Pamart
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Patent number: 5726262Abstract: A solid titanium catalyst component ?Ia! containing magnesium, halogen, titanium and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a catalyst and a prepolymerized olefin-containing catalyst prepared by using the solid titanium catalyst component ?Ia!; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used. A catalyst and a prepolymerized olefin containing catalyst prepared by using a solid titanium catalyst component ?Ib! containing magnesium, halogen, titanium and a specific electron donor (a1), and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used.Type: GrantFiled: December 24, 1996Date of Patent: March 10, 1998Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Tetsunori Shinozaki
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Patent number: 5629390Abstract: A method for producing a polyolefin in the presence of a catalyst comprising a transition metal compound and an organometallic compound, wherein a catalyst system is used which comprises: (A) a solid catalyst component prepared by reacting a uniform solution containing (I) at least one member selected from the group consisting of metal magnesium and a hydroxylated organic compound, and oxygen-containing organic compounds of magnesium, (II) an electron donative compound and (III) an oxygen-containing organic compound of titanium, with (IV) at least one aluminum halide compound to obtain a solid product, adding to this solid product (V) at least one compound selected from the group consisting of oxygen-containing organic compounds of one or more transition metals of Group IVa of the Periodic Table, and then treating the mixture with (VI) an aluminum halide compound, and (B) at least one catalyst component selected from the group consisting of organoaluminum compounds.Type: GrantFiled: May 16, 1996Date of Patent: May 13, 1997Assignee: Tosoh CorporationInventors: Sadaki Nishimura, Yutaka Naito, Toshikazu Chikusa, Mitsuhiro Mori, Yozo Kondo
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Patent number: 5610114Abstract: A supported solid catalyst which can be used for the polymerization and copolymerization of conjugated dienes having as its basis the reaction product of:A) a solid MgCl.sub.2 support,B) an ether, preferably THF, as swelling agent for the support,C) a metal salt selected from among metals having an atomic number of between 57 and 71 or 92 in the periodic table of elements and, if the metal salt is not a halide,D) a halogenation agent selected from the group consisting of a halogenated compound of aluminum and a halogenated compound not containing aluminum, the reaction solid being free from the swelling agent, plusE) an organic derivative of aluminum which is obligatory when the halogenation agent is not a halogenated compound of aluminum and optional when the halogenation agent is a derivative of aluminum.Also, a method of preparing this catalyst.Type: GrantFiled: August 2, 1995Date of Patent: March 11, 1997Assignees: Compagnie Generale Des Estab. Michelin-Michelin & Cie, Elf Atochem S.A.Inventors: Pierre Robert, Roger Spitz
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Patent number: 5608018Abstract: An .alpha.-olefin polymerization catalyst system having so high a catalytic activity and stereoregularity that the catalyst residue and amorphous polymer need not be removed and a process for producing an.alpha.-olefin polymer using the catalyst system, said catalyst system consisting essentially of:(A) a trivalent titanium compound-containing solid catalyst component prepared by reducing a titanium compound, represented by the general formula Ti(OR.sup.1).sub.a X.sub.4-a in which R.sup.1 represents a hydrocarbon group having 1 to 20 carbon atoms; X represents a halogen atom; and a represents a numeral satisfying 0<a.ltoreq.Type: GrantFiled: November 30, 1994Date of Patent: March 4, 1997Assignee: Sumitomo Chemical Company, LimitedInventors: Takeshi Ebara, Teruyosi Kiyota, Akio Imai
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Patent number: 5602067Abstract: A support containing methylalumoxane and derivatives thereof is described which is formed by an incipient impregnation technique. The most preferred support is silica. Incipient impregnation in accordance with the invention provides a supported alumoxane, methylalumoxane, which substantially eliminates the problem of fluidized bed reactor fouling when methylalumoxane is introduced into the reactor during its operation. In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluidized bed gas phase operation.Type: GrantFiled: November 3, 1994Date of Patent: February 11, 1997Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
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Patent number: 5589555Abstract: A solution process for the preparation of high molecular weight polymers of alpha-olefins selected from the group consisting of homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 higher alpha-olefins is disclosed. Ethylene and/or mixtures of ethylene and C.sub.3 -C.sub.12 higher alpha-olefins are polymerized under non-isothermal conditions in a tubular reactor or in a system of reactors which operate under different conditions, in the presence of a catalytic amount of a titanium-containing coordination catalyst in an inert solvent at a temperature in excess of 105.degree. C. The improvement is characterized in that:(a) the catalyst is activated with a solution of a mixture of aluminum alkyl and alkoxy aluminum alkyl in inert solvent; and(b) the process is controlled by adjusting the ratio of aluminum alkyl to alkoxy aluminum alkyl in the mixture of (a). The aluminum alkyl is of the formula AlR.sub.n X.sub.3-n and the alkoxy aluminum alkyl is of the formula AlR'.sub.m OR".sub.Type: GrantFiled: July 7, 1995Date of Patent: December 31, 1996Assignee: Novacor Chemicals (International) S.A.Inventors: Vaclav G. Zboril, Stephen J. Brown
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Patent number: 5587440Abstract: A process for the preparation of ultrahigh molecular weight polyethylene having a high bulk density by polymerization of ethylene in the presence of a mixed catalyst, the catalyst comprising an organic aluminum compound and a titanium component prepared by reduction of a Ti(IV) compound and after-treatment of the reduction product thereof with an organic aluminum compound.Type: GrantFiled: February 26, 1996Date of Patent: December 24, 1996Assignee: Hoechst AktiengesellschaftInventors: Jens Ehlers, Jutta Walter
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Procatalyst composition for homo- and copolymerization of alpha olefins, its preparation and its use
Patent number: 5583083Abstract: A procatalyst composition which is suitable for the homo- and copolymerization of alpha olefins together with an organometallic cocatalyst compound and which is prepared by treating an inorganic carrier with a component system containing a complex of a magnesium halide and a tetraalkyl titanate, and a chlorinating compound which does not contain a transition metal compound. In order to raise the Mg:Ti ratio, the component system additionally contains an organomagnesium compound.Type: GrantFiled: July 10, 1995Date of Patent: December 10, 1996Assignee: Neste OyInventors: Sirpa Ala-Huikku, Marjaana Lommi -
Patent number: 5567665Abstract: A process is provided for preparing a shape-shifted catalyst component comprising (1) contacting a dihydrocarbyloxide magnesium compound with carbon dioxide in the presence of a slurrying agent to form a slurry of a carboxylated dihydrocarbyloxide magnesium compound; (2) adding a filler to the slurry either before or after the carboxylation of step (1); (3) spray drying the slurry of step (2) to evaporate the slurrying agent and to produce solid particles of the carboxylated dihydrocarbyloxide magnesium compound incorporating the filler; and, optionally, (4) heating the solid particles to remove carbon dioxide to produce a shape-shifted dihydrocarbyloxide magnesium compound component. A catalyst system using the component and a polymerization process employing the catalyst system are also provided.Type: GrantFiled: May 23, 1995Date of Patent: October 22, 1996Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Burkhard E. Wagner, Daniel P. Zilker, Jr., Robert J. Jorgensen
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Patent number: 5552359Abstract: Disclosed are catalyst components for the polymerization of olefins which include magnesium halide in active form, and, supported thereon, a titanium halide or titanium halogen alcoholate and an electron-donor compound selected from the group diamines of formula ##STR1## wherein the radicals R.sub.1 to R.sub.10 are the same or different and are hydrogen or C.sub.1 -C.sub.18 hydrocarbon radicals, with the proviso that at least one of the R.sub.7 and R.sub.8 radicals and at least one of the R.sub.9 and R.sub.10 radicals are not hydrogen. Also, disclosed are catalysts obtained from the catalyst components and an Al-alkyl compound, as well as catalysts obtained by reaction of an Al-alkyl compound and a diamine of formula (I) with a solid catalyst component including a titanium halide or a titanium halogen alcoholate, and an electron-donor compound having particular characteristics of extractability with Al-triethyl, supported on magnesium halide in active form.Type: GrantFiled: February 21, 1995Date of Patent: September 3, 1996Assignee: Montell North America Inc.Inventors: Giampiero Morini, Luisa Barino, Raimondo Scordamaglia, Elisabetta Barbassa, Giovanni Baruzzi
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Patent number: 5529965Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst of the invention provides for a supported mixed metallocene/non-metallocene catalyst useful in a process for polymerizing olefins.Type: GrantFiled: October 28, 1994Date of Patent: June 25, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang
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Patent number: 5506183Abstract: Polyolefins having better particle properties are obtained by polymerizing olefins in the presence of a catalyst comprising a solid catalyst component and an organometallic compound, the said solid catalyst component being prepared by reacting the following components [I] and [II] and further reacting the resulting reaction product with the following component [III]:[I] a reaction product obtained by reacting:(1) a silicon oxide and/or an aluminum oxide, and(2) a titanium compound, or a titanium compound and a vanadium compound, and further reacting the resulting reaction product with:(3) an organoaluminum compound;[II] a reaction product obtained by the reaction of:(1) a magnesium halide, and(2) a compound represented by the general formula Me(OR).sub.n X.sub.z-n wherein Me represents an element of Groups I to IV in the Periodic Table, z represents the valence of the element Me, n is 0<n.ltoreq.Type: GrantFiled: August 9, 1994Date of Patent: April 9, 1996Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Takeichi Shiraishi, Sinichi Yanahashi, Hiroyuki Shimizu, Kazuo Matsuura
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Patent number: 5492983Abstract: This catalyst consists of the reaction product, with at least one organomagnesium compound and/or organolithium compound R.sup.1 Li (R.sup.1 =alkyl) or ArLi (Ar=phenyl or benzyl), of the reaction product of (Cp).sub.2 MX.sub.2 Li(OR.sub.2).sub.2 (M=lanthanide, Sc, Y; (Cp)=optionally substituted cyclopentadienyl; and R=alkyl), with at least one bidentate ligand, such as .beta.-diketone or .beta.-keto imine CZ.sub.3 COCHZCDCZ.sub.3, Z selected from halogen, alkyl and H, D=O, NH or NR.sup.3 (R.sup.3 =alkyl or aryl); and phosphorus ylid R.sup.2.sub.3 P.dbd.CA--CO--R.sup.2, R.sup.2 chosen from alkyl and aryl; A=alkyl or H. It advantageously takes the form of a solution at least partially containing an aromatic hydrocarbon. The process for the polymerization of ethylene may be carried out at 20.degree.-250.degree. C. at a pressure which may range up to approximately 200 bars, in solution or in suspension in an at least C.sub.Type: GrantFiled: June 7, 1994Date of Patent: February 20, 1996Assignee: ECP Enichem Polymeres FranceInventors: Xavier Olonde, Karel Bujadoux, Andre Mortreux, Francis Petit, deceased
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Patent number: 5492876Abstract: A solution process, and a catalyst therefor, for the preparation of high molecular weight polymers of alpha-olefins viz. homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 alpha-olefins, is disclosed. The process is operated under solution polymerization conditions at 105.degree.-320.degree. C. The catalyst is obtained from titanium tetrahalides, vanadium oxytrihalides and organoaluminum compounds, in which an admixture of catalyst components is heat-treated at 180.degree.-250.degree. C. and subsequently cooled to a temperature of less than 150.degree. C. Additional vanadium oxytrihalide is then added. The resultant catalyst solution is activated with an aluminum compound. The catalyst has good activity, showing superior activity to catalysts in which additional vanadium oxytrihalide is not added or added at temperatures above 150.degree. C.Type: GrantFiled: February 1, 1994Date of Patent: February 20, 1996Assignee: Novacor Chemicals (International) S.A.Inventors: Daniel J. Gillis, Vaclav G. Zboril, Millard C. Hughson
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Patent number: 5484754Abstract: A process for the polymerization of ethylene or the copolymerization of ethylene with an alpha-olefin, in suspension or in gas phase, in the presence of a catalyst consisting essentially of a cocatalyst and a catalytic component based on at least Mg, Ti and Cl, with the catalytic component being constituted of at least one derivative of magnesium and one chlorinated derivative of titanium in its form III and/or IV, which was subjected, prior to its use, to a reduction treatment and then to treatment with a chlorinated transition metal compound, with the said catalytic component being characterized in that the magnesium derivative is in the form MgCl.sub.2.MgO.Type: GrantFiled: January 21, 1993Date of Patent: January 16, 1996Assignee: Elf Atochem, S. A.Inventors: Roger Spitz, Maryse Patin, Jean Malinge
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Patent number: 5480850Abstract: A catalyst system comprising:(a) a catalyst precursor consisting essentially of the reaction product of vanadium (acetylacetonate).sub.3 and a compound having the formula AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is independently chlorine, bromine, or iodine; and a is 1 or 2; the atomic ratio of aluminum to vanadium in the precursor is 1:1 to 3:1; and the oxidation state of the vanadium in the reaction product is plus 2;(b) optionally, a support for said precursor; and(c) a halide substituted hydrocarbyl aluminum cocatalyst; and(d) optionally, a promoter, which is a chlorinated ester having at least 2 chlorine atoms; a saturated or unsaturated aliphatic halocarbon having at least 3 carbon atoms and at least 6 halogen atoms; or a haloalkyl substituted aromatic hydrocarbon wherein the haloalkyl substituent has at least 3 halogen atoms.Type: GrantFiled: June 28, 1993Date of Patent: January 2, 1996Assignee: Union Carbide Chemical & Plastics Technology CorporationInventors: Kevin J. Cann, James W. Nicoletti, Sergey A. Vasnetsov
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Patent number: 5480849Abstract: The invention relates to a process for the preparation of a solid procatalyst composition of a catalyst system for the polymerization of olefins wherein a magnesium halide such as magnesium chloride is dissolved and/or suspended into an alkyl ester of a monocarboxylic acid such as ethyl acetate, impregnated to a carrier, treated with an organometallic compound or a silicon compound and thereafter with a transition metal compound. The invention also relates to a procatalyst composition and its use together with a cocatalyst for the polymerization of olefins. The activity has been enhanced according to the invention by the use of a carrier containing hydroxyl groups, which carrier is kept at a temperature of at most about 200.degree. C. prior to the impregnation so that the hydroxyl groups are retained in the carrier to an essential extent until the impregnation step. The carrier is preferably silica which is treated thermally at 100.degree.-200.degree. C.Type: GrantFiled: August 16, 1993Date of Patent: January 2, 1996Assignee: Borealis Holding A/SInventors: Bill Gustafsson, Arja Kostiainen, Pekka Sormunen
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Patent number: 5453473Abstract: A process for producing EP and EPDM polymers with a reduction in fouling is provided, which process comprises polyemrizing ethylene, an alpha-olefin and a nonconjugated diolefin (if utilized) in a polymerization medium comprising a hydrocarbon diluent at a temperature of from about -50.degree. C. to about 150.degree. C. in the presence of a catalyst system comprising (a) a vanadium compound, (b) diethyl aluminum chloride, ethyl aluminum sesquichloride or ethyl aluminum dichloride and (c) an organo aluminum compound of the formula R.sub.3 Al wherein R is an alkyl group having from 8 to 12 carbon atoms and, optionally, triethyl aluminum, the molar ratio of chloride in diethyl aluminum chloride to the total aluminum content in (b) and (c) being from about 0.7:1 to about 0.95:1, the molar ratio of the chloride in ethyl aluminum sesquichloride to the total aluminum content in (b) and (c) being from about 0.7:1 to about 1.Type: GrantFiled: November 9, 1993Date of Patent: September 26, 1995Assignee: Bayer Rubber Inc.Inventors: Thomas F. Knauf, Akhtar Osman, Dilipkumar Padliya
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Patent number: 5448621Abstract: In a cellular communication system where satellite nodes are moving with respect to the earth's surface, frequencies and time-slots are dynamically reallocated between cells in response to demand for services. When a particular cell is at or near its capacity because of a high demand for services, or is projected to be at or near capacity, spectral capacity is reallocated from nearby cells to meet the increase in demand. The reallocation in capacity is based on both real time cell loading data and historical cell loading information based on previous experiences.Type: GrantFiled: August 2, 1993Date of Patent: September 5, 1995Assignee: Motorola, Inc.Inventor: John T. Knudsen
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Patent number: 5424378Abstract: The catalyst for olefin polymerization of the present invention contains R.sup.1.sub.k R.sup.2.sub.1 R.sup.3.sub.m M(SO.sub.3 R.sup.4) (M=Zr, Ti or Hf; R.sup.1-3 =a group having a cyclopentadienyl skeleton) as a catalyst component of a transition metal compound. According to the catalyst of the invention, an olefin polymer having excellent particle properties can be prepared with high polymerization activities, and further a copolymer having a narrow composition distribution can be prepared when two or more monomers are copolymerized. Of the above-mentioned transition metal compounds, a compound represented by the following formula is a novel compound unknown so far and shows excellent catalytic properties. ##STR1## (Cp=a group having a cyclopentadienyl skeleton, X=SO.sub.3 R, a halogen atom, R, OR, NR.sub.n, S(O).sub.q R, SiR.sub.3 or P(O).sub.q R.sub.3, n=1, 2 or 3; q=0, 1 or 2).Type: GrantFiled: July 28, 1994Date of Patent: June 13, 1995Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Junichi Imuta, Takashi Ueda
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Patent number: 5391660Abstract: Polyolefins having a high molecular weight, an appropriate molecular weight distribution and a relatively narrow composition distribution are prepared in high activity.The polymerization of an olefin or olefins is performed in the presence of a catalyst comprising a catalyst component and a modified organoaluminum compound, the catalyst component being prepared by mutually contacting (1) a compound of the general formula Me.sup.1 R.sup.1.sub.n X.sup.1.sub.4-n and (2) an alkali metal salt of cyclopentadiene or indene and optionally (3) a compound of the general formula Me.sup.2 R.sup.2.sub.m X.sup.2.sub.3-m, and the modified organoaluminum compound and water and containing Al--O--Al bond(s).Type: GrantFiled: January 12, 1993Date of Patent: February 21, 1995Assignee: Nippon Oil Company, LimitedInventors: Yosuke Numao, Yoshio Tajima
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Patent number: 5376612Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.Type: GrantFiled: August 20, 1993Date of Patent: December 27, 1994Assignee: Phillips Petroleum CompanyInventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
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Patent number: 5350816Abstract: A polymerization catalyst system is formed by combining an organometal compound and a transition metal compound to produce a catalyst A; and combining catalyst A and a catalyst B comprising a rare earth complex having a formula Cp.sub.n MX.sub.4-n.M'L.sub.x, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, M is yttrium, scandium or a rare earth metal having an atomic number in the range of 57 to 71, M' is an alkali metal, L is a suitable electron donor ligand, X is a halogen, n is 1 or 2, and x is a number corresponding to the value needed to form a stable complex.Optionally catalyst A is contacted with a rare earth metal halide.Optionally catalyst B is contacted with an alkali or alkaline earth metal alkyl.Optionally a hydrocarbyl aluminum compound can be contacted with catalyst B or with the catalyst system.Type: GrantFiled: July 29, 1993Date of Patent: September 27, 1994Assignee: Phillips Petroleum CompanyInventor: Ted M. Pettijohn
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Patent number: 5350724Abstract: A process for preparing a polymerization catalyst useful for the polymerization of olefins is provided comprising contacting a magnesium compound and a transition metal halide to form a solid product; contacting the solid product with an organoaluminum halide to form a first catalyst component, and contacting the first catalyst component with an activating agent to form a catalyst. Other aspects of the invention provide a catalyst prepared by the above described method and a polymerization process employing the thus prepared catalyst.Type: GrantFiled: May 4, 1993Date of Patent: September 27, 1994Assignee: Phillips Petroleum CompanyInventor: Joel L. Martin
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Patent number: 5342907Abstract: A process comprising contacting a mixture comprising ethylene, propylene, and, optionally, a diene, in the gas phase, under polymerization conditions, with a catalyst system comprising:(a) a catalyst precursor, in independent or prepolymer form, consisting of vanadium (acetylacetonate).sub.3 ;(b) optionally, a support for said precursor;(c) a cocatalyst consisting essentially of (i) an alkylaluminum halide having the formula AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is independently chlorine, bromine, or iodine; and a is 1 or 2, and (ii) optionally, a trialkylaluminum provided that the molar ratio of alkylaluminum halide to trialkylaluminum is at least about 1.Type: GrantFiled: June 28, 1993Date of Patent: August 30, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kevin J. Cann, Fathi D. Hussein, Kiu H. Lee, Daniel P. Zilker, Jr., James W. Nicoletti, Xinlai Bai
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Patent number: 5330947Abstract: This invention relates to a catalyst system using a boron alkyl in combination with an aluminum alkyl as a co-catalyst, a process for making the catalyst system and a process using the catalyst system for polymerization of olefins, especially .alpha.-olefins, such as propylene. While both boron alkyls and aluminum alkyls are known as co-catalysts separately, use of a boron alkyl with an aluminum alkyl as co-catalysts in olefin polymerization resulted in an unexpected increase in polymer yield. An increase in yield is accomplished without any increase in the amount of aluminum residue in the polymer product. The preferred boron alkyl is triethyl boron. The preferred aluminum alkyl is TEAl.Type: GrantFiled: October 15, 1991Date of Patent: July 19, 1994Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
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Patent number: 5310716Abstract: A supported solid component of catalyst, for the stereospecific polymerization of propylene and other .alpha.-olefins, is obtained by making a non-activated silica interact in succession with: (i) a magnesium dialkyl or halide of magnesium alkyl; (ii) a halogenating agent selected from silicon, tin and antimony halides; (iii) a titanium tetrahalide; and (iv) a Lewis base. A catalyst for the stereospecific polymerization of propylene and other .alpha.-olefins is composed of: (A) the solid component of catalyst; (B) an aluminium trialkyl or aluminium alkyl halide; and (C) an electron donor compound, capable of forming a complex compound with component (B).Type: GrantFiled: July 22, 1992Date of Patent: May 10, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Ludiano Luciani, Federico Milani, Renzo Invernizzi, Italo Borghi, Antonio Labianco
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Patent number: 5300470Abstract: Solid catalyst components for the preparation of catalysts capable of producing polymers and copolymers of ethylene with ultra high molecular weight are obtained in the form of particles having an average diameter of less than 10 micrometers, by way of reaction, in the presence of H.sub.2 O, between:1) a liquid obtained by reacting:A) a titanium compound containing at least one Ti--OR bond, where R is a C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.20 cycloalkyl, or C.sub.6 -C.sub.20 aryl radical; withB) a magnesium compound selected from the group consisting of: halides; compounds comprising at least one --OR or--OCOR group bonded to the magnesium, where R is a C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.20 cycloalkyl, or C.sub.6 -C.sub.20 aryl radical; organometallic compounds; products of the reaction between the above mentioned compounds and electron-donor compounds; and2) a compound or composition capable of halogenating and optionally reducing (A).Type: GrantFiled: July 15, 1992Date of Patent: April 5, 1994Assignee: Himont IncorporatedInventors: Illaro Cuffiani, Umberto Zucchini
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Patent number: 5296431Abstract: Ziegler-Natta-type catalyst systems containing, as active constituents,a) a titanium-containing solid component which also contains magnesium, halogen and a carboxylic acid ester as electron donor,b) an aluminum component,c) a further electron-donor component, and, as an additional component,d) an organometallic compound of the general formula A or B ##STR1## where M.sup.1 is an element f rom main group I, and M.sup.2 is an element from main group II of the Periodic Table, and R.sup.1 and R.sup.2 are identical or different C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.12 -aryl, C.sub.6 -C.sub.12 -arylalkyl, or 5- to 7-membered cycloalkyl, which may itself carry C.sub.1 -C.sub.8 -alkyl groups,can be used to prepare polymers which have, in particular, a low proportion of very fine grains.Type: GrantFiled: July 30, 1991Date of Patent: March 22, 1994Assignee: BASF AktiengesellschaftInventors: Klaus-Dieter Hungenberg, Juergen Kerth
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Patent number: 5286694Abstract: A polymerization catalyst is formed by producing a solution of a halide of scandium, yttrium, or a rare earth metal and an alcohol; contacting the solution with an organometallic compound to form a soluble complex; and contacting the soluble complex with a halide ion exchanging source. Optionally an ester or an anhydride can also be combined with the halide solution or the soluble complex. The catalyst thus produced can be combined with an organometallic cocatalyst.Type: GrantFiled: December 11, 1991Date of Patent: February 15, 1994Assignee: Phillips Petroleum CompanyInventors: Ted M. Pettijohn, Henry L. Hsieh
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Patent number: 5275992Abstract: A process is disclosed for the particle form polymerization of olefins. The process employs a titanium-containing having hydrocarbon soluble titanium components. The resulting catalyst is pretreated with an organometallic reducing agent prior to the introduction of the catalyst into the polymerization zone to give a catalyst which can be used satisfactorily in a loop reactor with lower levels of cocatalyst.Type: GrantFiled: December 7, 1992Date of Patent: January 4, 1994Assignee: Phillips Petroleum CompanyInventors: Kent E. Mitchell, Max P. McDaniel, M. Bruce Welch, Elizabeth A. Benham, Grover W. Cone
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Patent number: 5260244Abstract: A polymerization catalyst system is formed by combining an organometal compound and a transition metal compound to produce a catalyst A; and combining catalyst A and a catalyst B comprising a rare earth complex having a formula Cp.sub.n MX.sub.4-n.M'L.sub.x, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, M is yttrium, scandium or a rare earth metal having an atomic number in the range of 57 to 71, M' is an alkali metal, L is a suitable electron donor ligand, X is a halogen, n is 1 or 2, and x is a number corresponding to the value needed to form a stable complex.Optionally catalyst A is contacted with a rare earth metal halide.Optionally catalyst B is contacted with an alkali or alkaline earth metal alkyl.Optionally a hydrocarbyl aluminum compound can be contacted with catalyst B or with the catalyst system.Type: GrantFiled: October 1, 1992Date of Patent: November 9, 1993Assignee: Phillips Petroleum CompanyInventor: Ted M. Pettijohn
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Patent number: 5254517Abstract: This invention relates to a catalyst system using a diethylaluminum alkoxide-aluminum alkyl cocatalyst and to a process for polymerization of olefins using the catalyst system. Use of this catalyst system increases polymerization yield. The diethylaluminum alkoxide is preferably diethylaluminum ethoxide and the aluminum alkyl is preferably triethyl aluminum. The mole-to-mole ratio of diethylaluminum alkoxide to aluminum alkyl ranges from 0.05 to 0.2. This invention is effective for the aluminum/transition metal ratio for the polymerization of olefins ranges from about 100 to about 500. Polymerization yield increases of greater than 10% are realized.Type: GrantFiled: October 11, 1991Date of Patent: October 19, 1993Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamsoum, David J. Rauscher, Shabbir Malbari
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Patent number: 5237025Abstract: A catalyst mixture is disclosed comprising (1) a particulate chromium-containing catalyst comprising inorganic oxide and chromium and (2) a particular type of particulate titanium-containing catalyst. Also disclosed is the use of this catalyst mixture to produce particularly novel olefin polymers.Type: GrantFiled: October 9, 1990Date of Patent: August 17, 1993Assignee: Phillips Petroleum CompanyInventors: Elizabeth A. Benham, Max P. McDaniel
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Patent number: 5204303Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefines, in which particles are formed of magnesium dihalide and alcohol, the particles are reacted with an organic compound of a metal from the groups I-III, the thus obtained particulate product is activated by means of a titanium and/or vanadium compound and optionally a donor, and optionally a prepolymerization is carried out for the activated particles. A problem of such a method is how to form particles of magnesium dihalogenide and alcohol having a structure advantageous for the polymerization of olefins. The problem has in the present invention been solved so that the particles are formed by spray crystallizing (spray freezing) a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol. The hydroxyl content of the particles so obtained is much greater than earlier, which results in a much more active procatalyst than the preceding ones.Type: GrantFiled: September 16, 1991Date of Patent: April 20, 1993Assignee: Neste OyInventors: Inkeri T. Korvenoja, Arja-Liisa Kostiainen, Fero I. Iiskola, Pekka J. E. Sormunen, Bill B. B. Gustatsson, Hilkka R. Knuuttila, Ulf Palmqvist
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Patent number: 5192731Abstract: In accordance with the present invention, there are provided carrier-supported titanium catalyst components containing magnesium, aluminum, halogen and titanium as essential ingredients, which are obtained by a reaction of[I] a magnesium containing support obtained by previously bringing a support into contact with an organometallic compound of a metal of the Group II to IIIA of the periodic table having at least one hydrocarbon group attached directly to the metal atom or with a halogen containing compound, followed by contact with a magnesium compound in the liquid state having no reducing ability,[II] a reducing organometallic compound, and[III] a titanium compound in the liquid state, and processes for preparing the same and, at the same time, catalysts containing the above-mentioned catalyst components for use in preparing ethylene polymer and processes for preparing ethylene polymer using the catalyst for use in preparing ethylene polymer.Type: GrantFiled: October 23, 1991Date of Patent: March 9, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Kazumitsu Kawakita, Akinori Toyota
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Patent number: 5182244Abstract: A polymerization catalyst system is formed by combining an organometal compound and a transition metal compound to produce a catalyst A; and combining catalyst A and a catalyst B comprising a rare earth complex having a formula Cp.sub.n MX.sub.4-n.M'L.sub.x, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, M is yttrium, scandium or a rare earth metal having an atomic number in the range of 57 to 71, M' is an alkali metal, L is a suitable electron donor ligand, X is a halogen, n is 1 or 2, and x is a number corresponding to the value needed to form a stable complex.Optionally catalyst A is contacted with a rare earth metal halide.Optionally catalyst B is contacted with an alkali or alkaline earth metal alkyl.Optionally a hydrocarbyl aluminum compound can be contacted with catalyst B or with the catalyst system.Type: GrantFiled: December 19, 1991Date of Patent: January 26, 1993Assignee: Phillips Petroleum CompanyInventor: Ted. M. Pettijohn
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Patent number: 5180702Abstract: A polymerization catalyst is formed by producing a solution of a Group IIA or Group IIB halide and an alcohol; contacting the solution with an organometallic compound to form a soluble complex; and contacting the soluble complex with a halide ion exchanging source. An ester or an anhydride can also be combined with the halide solution or the soluble complex. The catalyst thus produced can be combined with an organometallic cocatalyst.Type: GrantFiled: December 11, 1991Date of Patent: January 19, 1993Assignee: Phillips Petroleum CompanyInventor: Ted M. Pettijohn
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Patent number: 5155078Abstract: In accordance with the present invention, there are provided carrier-supported titanium catalyst components containing magnesium, aluminum, halogen and titanium as essential ingredients, which are obtained by a reaction of[I] a magnesium containing support obtained by previously bringing a support into contact with an organometallic compound of a metal of the Group II to IIIA of the periodic table having at least one hydrocarbon group attached directly to the metal atom or with a halogen containing compound, followed by contact with a magnesium compound in the liquid state having no reducing ability,[II] a reducing organometallic compound, and[III] a titanium compound in the liquid state, and processes for preparing the same and, at the same time, catalysts containing the above-mentioned catalyst components for use in preparing ethylene polymer and processes for preparing ethylene polymer using the catalyst for use in preparing ethylene polymer.Type: GrantFiled: June 17, 1991Date of Patent: October 13, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Kazumitsu Kawakita, Akinori Toyota
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Patent number: 5151396Abstract: A catalytic component having controlled strucuture for use in combination with a cocatalyst for the polymerization of ethylene, and being the product of the process of subjecting a component consisting essentially of titanium, magnesium, and chlorine to a reduction treatment and after such treatment contacting the component with a transition metal chlorine-containing compound and process of polymerizing ethylene using such catalytic component to produce polymers having a broad molecular weight distribution.Type: GrantFiled: November 13, 1989Date of Patent: September 29, 1992Assignee: AtochemInventors: Roger Spitz, Jean Malinge, Jean-Francois Joly
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Patent number: 5139986Abstract: The invention relates to catalysts for ethylene polymerization or copolymerization to produce film quality product which exhibits improved FDA hexane extractables. The invention also relates to catalysts for ethylene polymerization or copolymerization to produce film quality product which exhibits improved dart impact resistance. The invention relates to catalysts for ethylene polymerization or copolymerization to produce film quality product which exhibits improved MD tear properties.Type: GrantFiled: August 6, 1991Date of Patent: August 18, 1992Assignee: Mobil Oil CorporationInventors: Pam J. Cook, Robert O. Hagerty, Per K. Husby, Thomas E. Nowlin
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Patent number: 5091352Abstract: In accordance with the present invention, there are provided olefin polymerization catalyst components comprising an organoaluminum oxy-compound having less than 10% in terms of Al atom of Al component dissolving in benzene kept at 60.degree. C., and olefin polymerization catalyst containing said olefin polymerization catalyst components. The olefin polymerization catalysts have excellent polymerization activities, and are capable of giving olefin (co)polymers having a narrow molecular weight distribution and a narrow composition distribution.Type: GrantFiled: September 14, 1989Date of Patent: February 25, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Toshiyuki Tsutsui, Akinori Toyota
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Patent number: 5091490Abstract: Silica supported high activity olefin polymerization catalysts, methods of producing the catalysts and methods of using the catalysts in the polymerization of olefins are provided. The methods of producing the catalysts each basically comprise contacting a particulate silica support impregnated with tungsten oxide with the soluble complex produced by heating a mixture of a metal dihalide with a transition metal compound to produce a solid, and then reacting the solid with an organoaluminum halide. The catalysts produced have improved productivities and are less soluble in polymerization media.Type: GrantFiled: June 19, 1991Date of Patent: February 25, 1992Assignee: Phillips Petroleum CompanyInventors: Gil R. Hawley, Simon G. Kukes, Robert L. Banks, deceased
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Patent number: 5075271Abstract: There is disclosed a catalyst composition for the polymerization of olefins, particularly alpha-olefins. The composition is prepared by synthesizing a catalyst precursor and then combining it with a conventional catalyst activator. The precursor is synthesized by: (a) contacting a solid, porous carrier with an aluminum compound; (b) contacting the resulting product with a mixture of vanadium and titanium compounds; (c) contacting the product with an alkyl ether and (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound.The catalyst composition is used without a halogenating agent in the polymerization medium to produce narrow molecular weight distribution HDPE and LLDPE products, or with a halogenating agent in the polymerization medium to produce broad molecular weight distribution LLDPE and HDPE products.Type: GrantFiled: November 5, 1990Date of Patent: December 24, 1991Assignee: Mobil Oil CorporationInventor: Nemesio D. Miro