Containing Hydrides Or Organometallic Of Two Or More Different Component A Metals Patents (Class 502/114)
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Patent number: 5753578Abstract: A catalyst active in the (co)polymerization of .alpha.-olefins is obtained by putting the following components in contact with each other:(i) a "bridged" bis-metallocene derivative of a metal M selected from titanium, zirconium or hafnium, wherein the divalent "bridge" has a rigid structure linked to two .eta..sup.5 -cyclopentadienyl ring with two methylene groups having a distance from each other of less than 3.5 .ANG.;(ii) a co-catalyst consisting of an organic derivative of a metal M' selected from boron, aluminium, gallium and tin.Such a catalyst allows high polymerization rates to be reached and is particularly suitable for high temperature polymerization process and co-polymerization of ethylene with other .alpha.-olefins.Type: GrantFiled: June 21, 1996Date of Patent: May 19, 1998Assignee: Enichem S.p.A.Inventors: Roberto Santi, Giampiero Borsotti, Antonio Proto, Liliana Gila, Karel Bujadoux
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Patent number: 5750454Abstract: A catalyst comprises a composition resulting from mutual contact of the following Components (A), (B), (C) and (D):said Component (A) being a reaction product resulting from mutual contact of components (a), (b) and (c);said component (a) being represented by the formulaMe.sup.1 R.sup.1.sub.p (OR.sup.2).sub.q X.sup.1.sub.4-p-q Iwherein R.sup.1 and R.sup.2 each are a C.sub.1 -C.sub.24 hydrocarbon moieties, X.sup.1 is a hydrogen atom or a halogen atom, Me.sup.1 is titanium, zirconium or hafnium, p and q are 0.ltoreq.p.ltoreq.4, 0.ltoreq.q.ltoreq.4 and 0.ltoreq.p+q.ltoreq.4,said component (b) being represented by the formulaMe.sup.2 R.sup.3.sub.m(OR.sup.4).sub.n X.sup.2.sub.z-m-n IIwherein R.sup.3 and R.sup.4 each are a C.sub.1 -C.sub.24 hydrocarbon moieties, X.sup.2 is a hydrogen atom or a halogen atom, Me.sup.2 is an element of Groups I to III in the Periodic Table, z is a valence of Me.sup.2, and m and n are 0.ltoreq.m.ltoreq.z, 0.ltoreq.n.ltoreq.z and 0<m+n.ltoreq.Type: GrantFiled: May 30, 1996Date of Patent: May 12, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Hiroyuki Shimizu, Akira Sano, Kazuo Matsuura
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Patent number: 5744678Abstract: An oligomerization catalyst according to the invention comprises a nickel compound (A); an organophosphoric compound (B); an organoaluminum compound (C); and a compound of the group consisting of carbon-halogen bond-containing compounds, oxoacid and salts thereof, sulfonic acid and derivatives thereof, and compounds of any of the formulae QX.sup.4.sub.n, QR.sub.n, QR'.sub.n, QX.sup.4.sub.1 R.sub.m, QX.sup.4.sub.1 R'.sub.m, QR.sub.1 R'.sub.m, Q.sup.1 (BR.sub.4).sub.p and R"(BR.sub.4) wherein Q is an element of the group consisting of Mg, Ti, Zr, B and Sn, Q.sup.1 is an element of the group consisting of Li, Na, K, Ca and Zn, X.sup.4 is a halogen or hydrogen atom, R is a C.sub.1 -C.sub.12 hydrocarbon group, R' is a C.sub.1 -C.sub.12 oxygen-containing hydrocarbon group, R" is a C.sub.1 -C.sub.20 hydrocarbon group or an ammonium group, n is a valence of Q, l, m is a natural member that satisfied n=l+m, and p is a valence of Q.sup.1. This catalyst is useful for the production of alpha-olefinic oligomers.Type: GrantFiled: November 1, 1996Date of Patent: April 28, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Fuyuki Aida, Takashi Nakano, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5731253Abstract: Siloxy-aluminoxane compositions which are the reaction products of hydrocarbylsiloxanes substantially-free of Si--OH groups, and aluminoxanes and which have improved solubility and stability in solution even at up to 60 weight percent when compared to the original aluminoxane. The compositions in combination with metallocenes of transition lanithanide and actinide metals form catalysts which can be used in the polymerization of olefins such as ethylene.Type: GrantFiled: July 27, 1995Date of Patent: March 24, 1998Assignee: Albemarle CorporationInventor: Samuel A. Sangokoya
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Patent number: 5728641Abstract: According to the present invention there are provided a catalyst component, a catalyst using the catalyst component and a process using the catalyst, for the preparation of olefin polymers high in molecular weight and relatively wide in molecular weight distribution, using an extremely small amount of a modified organoaluminum compound such as methylaluminoxane and in high yield. The catalyst component is prepared by contacting at least the following constituents (1), (2), (3) and (4) with one another:(1) a compound represented by the general formula Me.sup.1 R.sup.1.sub.p (OR.sup.2).sub.q X.sub.4-p-q where R.sup.1 and R.sup.2 are each independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf, p and q are each an integer in the ranges of 0.ltoreq.p.ltoreq.4 and 0.ltoreq.q.ltoreq.4, provided 0.ltoreq.p+q.ltoreq.4;(2) at least one compound selected from the group consisting of compounds represented by the following general formulas 1 to 4:General formula 1: Me.sup.Type: GrantFiled: June 21, 1995Date of Patent: March 17, 1998Assignee: Nippon Oil Company, LimitedInventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5728784Abstract: Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure which comprises polymerizing vinylaromatic monomers, alone or mixed with at least one other monomer, in the presence of a catalytic system essentially consisting of:a) a complex of titanium or zirconium selected from those having general formula:MR.sub.1 R.sub.2 R.sub.3 R.sub.4, A.sub.1 MR.sub.1 R.sub.2 R.sub.3, A.sub.1 A.sub.2 MR.sub.1 R.sub.2 (I)b) a co-catalyst selected from an alkylalumoxane and a compound of boron having formula (II):BX.sub.1 X.sub.2 X.sub.3 (II)or one of its salts;c) a derivative of tin having general formula:SnR.sub.5 R.sub.6 R.sub.7 R.sub.Type: GrantFiled: November 27, 1996Date of Patent: March 17, 1998Assignee: Enichem S.p.A.Inventors: Riccardo Po', Nicoletta Cardi, Roberto Santi
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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: 5707914Abstract: A process for the polymerization of olefinic hydrocarbons is carried out in the presence of a catalyst comprising a catalyst component derived from reacting a compound of the formula Me.sup.1 R.sup.1.sub.n X.sup.1.sub.4-n, a compound of the formula Me.sup.2 R.sup.2.sub.m X.sup.2.sub.z-m, an organocyclic compound having two or more conjugated double bonds and a carrier of inorganic or polymeric material, and a modified organoaluminum compound having Al--O--Al bonds, the resulting polyolefins having a relatively wide molecular weight distribution, a relatively narrow composition distribution and increased bulk density.Type: GrantFiled: June 5, 1995Date of Patent: January 13, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Naoki Kataoka, Yosuke Numao, Takashi Seki, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5703180Abstract: An ethylene/.alpha.-olefin copolymer obtained by copolymerizing ethylene with an .alpha.-olefin of 3 to 20 carbon atoms in the presence of a catalyst for olefin polymerization comprising an organoaluminum oxy-compound (a) and at least two kinds of transition metal compounds (b). This ethylene/.alpha.-olefin copolymer has high melt tension and high flowability.Type: GrantFiled: March 19, 1996Date of Patent: December 30, 1997Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Mamoru Takahashi, Akira Todo
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Patent number: 5693583Abstract: A catalyst composition for copolymerizing ethylene and alpha-olefins is prepared by treating a silica carrier, in a non-polar hydrocarbon solvent, with a dialkyl magnesium compound, a halogen-containing compound and titanium tetrachloride, to form a catalyst precursor and activating the precursor with dimethylaluminum chloride.Also disclosed is a process for copolymerizing ethylene and alpha-olefins in the presence of the catalyst of the invention. The polymer products have multimodal molecular weight distributions unlike unimodal molecular weight distributions of polymers prepared with similar catalyst precursors but activated with different alkylaluminum activators, e.g., triethylaluminum or trimethylaluminum.Type: GrantFiled: February 11, 1997Date of Patent: December 2, 1997Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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Patent number: 5670587Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound-based polymer composition which catalyst comprises (A) at least two different transition metal compounds each having one .pi.-ligand and (B) an ionic compound comprising a noncoordinate anion and a cation and/or an aluminoxane, and (C) a Lewis acid to be used as the case may be; and a process for producing an aromatic vinyl compound-based polymer composition having a high degree of syndiotactic configuration in its aromatic vinyl chains which process comprises polymerizing an (a) aromatic vinyl compound and (b) an olefinic compound and/or a diolefinic compound in the presence of the above catalyst.Type: GrantFiled: January 23, 1996Date of Patent: September 23, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu, Masahiko Kuramoto
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Patent number: 5625014Abstract: A process for the polymerization of olefinic hydrocarbons is carried out in the presence of a catalyst comprising a catalyst component derived from reacting a compound of the formula Me.sup.1 R.sup.1.sub.n X.sup.1.sub.4-n, a compound of the formula Me.sup.2 R.sup.2.sub.m X.sup.2.sub.z-m, an organocyclic compound having two or more conjugated double bonds and a carrier of inorganic or polymeric material, and a modified organoaluminum compound having Al--O--Al bonds, the resulting polyolefins having a relatively wide molecular weight distribution, a relatively narrow composition distribution and increased bulk density.Type: GrantFiled: June 6, 1995Date of Patent: April 29, 1997Assignee: Nippon Oil Co., Ltd.Inventors: Naoki Kataoka, Yosuke Numao, Takashi Seki, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5587439Abstract: The present invention is directed to a supported metallocene catalyst useful in the polymerization of .alpha.-olefins which is obtained by tethering a metallocene catalyst component to the surface of a particulate, functionalized copolymeric support material.Type: GrantFiled: May 12, 1995Date of Patent: December 24, 1996Assignee: Quantum Chemical CorporationInventor: Anthony-J. DiMaio
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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: 5578540Abstract: Solid component of a catalyst for the synthesis of elastomeric Ethylene-Propylene copolymers typically amorphous, basically consisting of a Titanium compound supported on a solid component mainly consisting of MgCl.sub.2, prepared by a process which comprises putting a solution (I), basically consisting of an organometallic compound of Aluminium diluted with aliphatic hydrocarbons, in contact with a solution (II) containingan anhydrous Magnesium halide in a composition of solvents selected from halohydrocarbons and aromatic hydrocarbons and relative mixtures, in the presence of an Aluminium trihalide;a tetravalent Titanium compound having general formula Ti(OR).sub.4-n X.sub.n.Type: GrantFiled: February 5, 1996Date of Patent: November 26, 1996Assignee: Enichem Elastomeri S.r.L.Inventors: Viviano Banzi, Gianni Loberti
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Patent number: 5556821Abstract: According to the present invention there is provide a catalyst capable of affording an olefin homopolymer or copolymer having a high molecular weight and a relatively wide molecular weight distribution, in high yield, using an extremely small amount of a modified organoaluminum compound (particularly methylaluminoxane).The catalyst comprises the modified organoaluminum compound and a catalyst component comprising the following compounds (1) and (2): (1) a compound represented by the general formula R.sub.p MX.sub.4-p where M is a transition metal of Group IVa in the Periodic Table, R is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, or an aralkyl group having 7 to 24 carbon atoms, provided Rs may be bonded together through an alkylene groups having 2 to 8 carbon atoms and/or silylene group, X is a halogen atom, a hydrogen atom or a hydrocarbon residue having 1 to 24 carbon atoms, and p is a number satisfying the condition of 1.ltoreq.p.ltoreq.Type: GrantFiled: July 19, 1994Date of Patent: September 17, 1996Assignee: Nippon Oil Company, LimitedInventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5527868Abstract: Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alk-1-enes contain, as active components,a) a metallocene complex of the general formula I ##STR1## where M is a metal of subgroup III, IV or V of the Periodic Table of Elements or a metal of the lanthanide group,X is halogen, hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.3 -C.sub.10 -cycloalkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl of 7 to 15 carbon atoms or --OR.sup.15,R.sup.15 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,n is the valency of M minus two,R.sup.1 to R.sup.14 are each hydrogen or C.sub.1 -C.sub.10 -alkyl or are each C.sub.3 -C.sub.10 -cycloalkyl which in turn may carry C.sub.1 -C.sub.10 -alkyl as substituent, or are each C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals together may furthermore form a cyclic group of 4 to 15 carbon atoms, or are each Si(R.sup.16).sub.Type: GrantFiled: November 22, 1994Date of Patent: June 18, 1996Assignee: BASF AktiengesellschaftInventors: Kaspar Evertz, Rueger Schlund, Peter Jutzi, Ingrid Mieling
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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: 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: 5500397Abstract: Solid catalyst component for the polymerization of ethylene including the product of the reaction between:1) the product obtained by reacting:1A) a halide, halogen alcoholate or alcoholate of titanium, vanadium or zirconium;1B) a small quantity of water, and optionally1C) a compound or composition capable of substituting, in compound 1A, one or more alkoxy groups with a halogen atom; and2) a complex having general formula:MgX.sub.2 .multidot.nAlRX.sub.2 .multidot.pAlX.sub.3where X is chlorine or bromine; R is a hydrocarbon radical containing from 1 to 20 carbon atoms; n is a number from 1 to 4; p is a number from 0 to 1, and n+p from 1 to 4;the catalyst component being in the form or particles having a diameter lower than or equal to 20 micrometers, and an average diameter lower than or equal to 10 micrometers.Type: GrantFiled: January 13, 1994Date of Patent: March 19, 1996Assignee: Montell North America Inc.Inventors: Illaro Cuffiani, Umberto Zucchini, deceased
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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: 5468707Abstract: The invention relates to the use of cyclic organometallic compounds as components in coordination catalyst systems, to corresponding coordination catalyst systems and also to processes for the preparation of polymers by coordination polymerization and of unsaturated hydrocarbons by catalyzed metathesis of alkenes and alkynes using such coordination catalyst systems.Type: GrantFiled: July 29, 1994Date of Patent: November 21, 1995Assignee: Merck Patent Gesellschaft mit Beschrankter HaftungInventors: Ludwig Pohl, Fike Poetsch, Herbert Schumann, Karin Weiss, Karl-Heinz Thiele, Hans-Ludwig Hirsch
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Patent number: 5451556Abstract: An accelerator composition for the curing of unsaturated maleic, allylic, vinylic and epoxy-type polyester resins is disclosed. The accelerator composition includes a complex of a salt of a metal selected from lithium, copper, manganese, magnesium, vanadium, iron and cobalt, with an ammonium salt of a C.sub.2 -C.sub.20 carboxylic acid which is capable of forming a complex with the metal salt. Also disclosed are a curable resin composition including the foregoing accelerators and a curing process employing these accelerators.Type: GrantFiled: February 8, 1995Date of Patent: September 19, 1995Assignees: Akzo Nobel N.V., Saint Peter S.r.l.Inventor: Gualtiero Giovando
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Patent number: 5407882Abstract: A catalyst for polymerization of olefin is provided which comprises (A) a metallocene compound, (B) an organoaluminum compound, and (C) a metal borate or a metal aluminate. The metallocene compound (A) is represented by the general formula (1) below: ##STR1## where Cp.sup.1 and Cp.sup.2 are cyclopentadienyl group; R.sup.1 is an alkylene, arylalkylene, dialkylsilylene, dialkylgermanylene, alkylphosphinediyl, or alkylimino group, R.sup.1 crosslinking Cp.sup.1 and Cp.sup.2 together; m is 0 or 1; M is titanium, zirconium, or hafnium; and R.sup.2 and R.sup.3 are independently hydrogen, halogen, or a hydrocarbon group, an alkoxy group, or an aryloxy group having 1 to 12 carbons, the organic aluminum compound (B) is represented by the general formula (2) below:AlR.sup.4.sub.3 (2)where each R.sup.4 is independently hydrogen, alkyl, alkoxy, or an aryl group, at least one R.sup.4 being an alkyl group, and the metal borate or the metal aluminate (C) being represented by the general formula (3):(C(L).sub.n).sub.b (A).Type: GrantFiled: August 2, 1993Date of Patent: April 18, 1995Assignee: Tosoh CorporationInventors: Satoru Yamada, Akihiro Yano
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Patent number: 5405817Abstract: Catalysts useful in olefin polymerization are a mixture of (a) a titanium-containing compound which is (i) Ti(Z.sup.1).sub.t (OZ.sup.2).sub.p-t, (ii) the product of reacting Z.sup.3 --Mg--N(--Z.sup.5)--Si(Z.sup.4).sub.3 or Z.sup.3 --Mg--N(--Z.sup.5)--Si(Z.sup.4).sub.2 --N(--Z.sup.5)--Mg--Z.sup.3 with Ti(Z.sup.1).sub.t (OZ.sup.2).sub.p-t, or (iii) the product of reacting Mg metal, Mg dihalide and Ti(OZ.sup.2).sub.4, wherein Z.sup.1 is halide, Z.sup.2 is C.sub.1-18 hydrocarbyl, p is 3-4, t is 0-p, and Z.sup.3, Z.sup.4 and Z.sup.5 can be C.sub.1-18 alkyl or C.sub.6-14 aryl, and Z.sup.4 can be hydrogen, and Z.sup.5 can be --Si(Z.sup.4).sub.3 ; (b) one or more of V(X.sup.2).sub.c (OR.sup.2).sub.b-c, VO(X.sup.3).sub.d (OR.sup.3).sub.3-d, or VO(X.sup.4).sub.2, wherein X.sup.2, X.sup.3 and X.sup. 4 are halogen, R.sup.2 and R.sup.3 are C.sub.1-18 hydrocarbyl, b is 3-4, c is 0-b, and d is 0-3; and (c) Zn(X.sup.1).sub.2.2Al(R.sup.1).sub.3 and/or both of Zn(X.sup.1).sub.2 and one or more of M(R.sup.5).sub.e (X.sup.5).Type: GrantFiled: February 12, 1993Date of Patent: April 11, 1995Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5399540Abstract: A catalyst useful in the polymerization of olefins, especially ethylene, is disclosed. The catalyst is obtained by admixing a zinc composition, a zirconium composition and a vanadium composition. The catalyst may be combined with a co-catalyst and, optionally, a modifier to yield an olefin polymerization system. The catalyst exhibits extremely high activity, good hydrogen response and produces polymers having broad molecular weight distribution ("MWD") and manifesting bimodal MWD profile.Type: GrantFiled: February 12, 1993Date of Patent: March 21, 1995Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5395810Abstract: This invention concerns a making a catalyst system comprising at least one homogeneous catalyst and at least one heterogeneous catalyst, specifically, a metallocene catalyst and a conventional Ziegler-Natta catalyst, respectively. This invention is useful for making a catalyst for the polymerization of any polymer in which separate polymerizations with a homogeneous catalyst and with a heterogeneous catalyst are possible, but preferably, polymerization of olefins, more preferably, .alpha.-olefins, and, most preferably, propylene. This invention provides a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. This invention produces a polymer with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. Hydrogen can be used to control molecular weight distribution of a polymer produced with this invention.Type: GrantFiled: January 27, 1993Date of Patent: March 7, 1995Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, Michael J. Elder, Baireddy R. Reddy, David J. Rauscher
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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: 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: 5235071Abstract: The invention relates to a catalyst for producing phthalic anhydride by gas phase catalytic oxidation of o-xylene and/or naphthalene with molecular oxygen or gas containing molecular oxygen and, to a process for producing phthalic anhydride by using said catalyst. The catalyst is made by supporting, on a heat-resistant inorganic carrier, a catalytic active substance which comprises: vanadium oxide; anatase type titanium dioxide having specific surface area of 10 to 60 m.sup.2 /g; niobium; at least one element selected from potassium, cesium, rubidium and thallium; phosphorus; and antimony. The catalytic active substance is prepared by using a five-valent antimony compound as an antimony source. The process for producing phthalic anhydride comprises use of said catalyst.Type: GrantFiled: June 30, 1992Date of Patent: August 10, 1993Assignee: Nippon Shokubai Co., Ltd.Inventors: Kenji Ueda, Masaaki Okuno, Tatsuya Kawabata, Shinya Tanaka
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Patent number: 5204304Abstract: A vanadium-containing catalyst is prepared as the product of admixing an inorganic oxide, inorganic phosphate or mixtures thereof, a zinc-containing composition, and a vanadium-containing composition. An auxiliary compound such as, for example, an aluminum halide compound may optionally be admixed. The catalyst may be combined with a co-catalyst such as an aluminum alkyl and, optionally, a halocarbon promotor to yield an olefin polymerization catalyst system. The resulting catalyst system exhibits high activity, excellent hydrogen response and produces a polymer having a narrow to broad molecular weight distribution with a bimodal profile. The catalyst is especially useful in ethylene homopolymerization and co-polymerization.Type: GrantFiled: June 4, 1991Date of Patent: April 20, 1993Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5155079Abstract: A multiple site solid catalyst component capable of producing polyolefins having a broad or multimodal molecular weight distribution, such as a bi-modal molecular weight distribution, is prepared by contacting a particulate solid support with a zirconium compound or complex to bind the zirconium compound or complex to the support, optionally followed by contacting the supported zirconium compound or complex with a Lewis acid to produce an intermediate product, optionally isolating and washing the supported zirconium compound or complex or resulting intermediate product to remove soluble by-products therefrom, and reacting the washed or unwashed supported zirconium compound or complex or intermediate product with a titanium or vanadium compound to produce a solid catalyst component.Type: GrantFiled: June 7, 1991Date of Patent: October 13, 1992Assignee: Quantum Chemical CorporationInventors: Leonard V. Cribbs, Michael W. Lynch
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Patent number: 5126301Abstract: A solid catalyst for polymerizing an olefin is prepared from an organometallic compound, a fine-particle carrier, an aluminoxane, a compound of group IVB transition metal in periodic table, and an olefin polymer produced in a preliminary polymerization. The catalyst has a high polymerization activity and is capable of producing an olefin polymer having a narrow molecular- weight distribution. When the catalyst is used for producing an olefin copolymer, the resulting copolymer has both narrow molecular-weight distribution and composition distribution.Type: GrantFiled: March 12, 1990Date of Patent: June 30, 1992Assignee: Mitsui Petrochemical Industries, Inc.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Akinori Toyota, Norio Kashiwa
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Patent number: 5120806Abstract: A metathesis catalyst activator composition consisting essentially of an alkoxyalkylaluminum halide and a tin compound in a molar ratio of about 0.15 to 2 moles of the alkoxyalkylaluminum halide per mole of tin compound.Type: GrantFiled: August 22, 1991Date of Patent: June 9, 1992Assignee: Hercules IncorporatedInventor: Andrea E. Martin
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Patent number: 5114897Abstract: 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: May 31, 1991Date of Patent: May 19, 1992Assignee: The Dow Chemical CompanyInventors: Joseph G. Schell, Jr., Gary R. Marchand, Larry A. Meiske
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Patent number: 5068489Abstract: Ethylene copolymers having a very low molecular weight are continuously prepared in a fluidized bed in the presence of reduced concentrations of hydrogen, at improved catalyst activity and polymer productivity, by effecting polymerization in the presence of a dialkylzinc compound.Type: GrantFiled: December 28, 1989Date of Patent: November 26, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: David N. Edwards, Robert J. Jorgensen, Kiu H. Lee, Arthur E. Marcinkowsky
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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: 5010151Abstract: A method of preparing ethylene polymers which comprises polymerizing ethylene, or ethylene and one or more .alpha.-olefins other than ethylene in the presence of a composite catalyst which catalyst comprises:(A) a solid composition prepared by depositing one or more chromium compounds and one or more metal compounds other than said chromium compounds onto an inorganic oxide support material and then calcining the resulting solid; and(B) one or more organometallic compounds that are each independently represented by the following general formula:MR.sup.1 aR.sup.2 bR.sup.3 cwherein M is a metal of Group I, II or III of the periodic table and the R.sup.1, R.sup.2 and R.sup.3 moieties are each independently hydrogen, a hydrocarbon radical of C.sub.1 -C.sub.14, or an alkoxy group of C.sub.1 -C.sub.Type: GrantFiled: September 11, 1990Date of Patent: April 23, 1991Assignee: Idemitsu Petrochemical Co., Ltd.Inventor: Norio Tomotsu
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Patent number: 4943621Abstract: Methods of preparing storage stable components useful for metathesis bulk polymerization of cycloolefin monomers are provided. These components contain cycloolefins with norbornene-functional groups and cocatalysts activated with a halometal compound. In these methods, the cocatalyst is completely formed before the halometal activator is added to prevent the formation of unwanted hydrogen halides, which catalyze undesired crosslinking reactions which destabilize the cocatalyst component. Bulk polymerization systems are provided wherein these storage stable cocatalyst components are paired with catalyst components that together form the complete metathesis catalyst system. For some embodiments, storage stability is aided by the removal of water.Type: GrantFiled: August 4, 1988Date of Patent: July 24, 1990Assignee: The B. F. Goodrich CompanyInventors: Dennis J. Janda, Paul T. Stricharczuk, Robert J. Minchak
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Patent number: 4900798Abstract: Finely divided ethane polymers are prepared using a Ziegler catalyst system consisting of (1) a titanium-containing catalyst component which has been obtained by (1.1) precipitation in an organic liquid comprising (1.1.1) a solution of titanium tetrachloride in a hydrocarbon, (1.1.2) a solution of a certain organoaluminum compound in a hydrocarbon and (1.1.3) an alpha-monoalkene, and (2) an aluminum-containing catalyst component. In this process, the component (1) used is a component where (1.Type: GrantFiled: September 16, 1987Date of Patent: February 13, 1990Assignee: BASF AktiengesellschaftInventors: Juergen Kerth, Rudolf Mueller-Mall, Guenther Schweier
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Patent number: 4871704Abstract: A catalyst for olefin polymerization which comprises: (A) a catalyst component obtained by reacting (a) pentadiene or a derivative thereof with (b) an alkali metal and susequently reacting the reaction product with (c) a titanium compound or zirconium compound, and (B) aluminoxane.Type: GrantFiled: October 7, 1988Date of Patent: October 3, 1989Assignee: Toa Nenryo Kogyo K.K.Inventors: Tadanao Kohara, Satoshi Ueki
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Patent number: 4870043Abstract: A catalyst for the polymerization of olefins cmprising a combination of a solid catalyst component (A) comprising a solid catalytic complex (i) containing titanium, magnesium and a halogen as the essential ingredients with an organoaluminium compound (B), wherein said solid catalyst component (A) is obtained by bringing the following ingredients (ii) and (iii) in contact with said solid catalytic complex (i):Ingredient (ii): a silicon compound represented by the general formula:R.sub.m.sup.1 X.sub.n Si(OR.sup.2).sub.4-m-nwherein R.sup.1 and R.sup.2 each stand for a hydrocarbyl residue, X denotes a halogen, and m and n are such that 0.ltoreq.m.ltoreq.3 and 0.ltoreq.n.ltoreq.3 are satisfied on condition that 0.ltoreq.m.ltoreq.n.ltoreq.3, andIngredient (iii): an organometallic compound selected from the group consisting of organozinc compounds and organomagnesium compounds. The catalyst makes it possible to eliminate what is called "outside electron donor" as a component for making up a final catalyst system.Type: GrantFiled: April 1, 1988Date of Patent: September 26, 1989Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Takashi Fujita
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Patent number: 4870042Abstract: A catalyst for olefin polymerization which comprises:(A) a catalyst component obtained by reacting (a) alkali metal boron hydride represented by the formula MBH.sub.4 (where M denotes an alkali metal) with (b) pyrazole and subsequently reacting the reaction product with (c) a titanium compound or zirconium compound, and(B) aluminoxane.Type: GrantFiled: October 7, 1988Date of Patent: September 26, 1989Assignee: Toa Nenryo Kogyo K.K.Inventors: Tadanao Kohara, Satoshi Ueki
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Patent number: 4814308Abstract: Ethene polymerization by Phillips catalysis is carried out using (1) a supported catalyst, which is laden with chromium, phosphorus and aluminum, and (2) a cocatalyst, (1) being obtained by a method in which (1.1) a catalyst intermediate laden with chromium, phosphorus and aluminum is prepared from a silicate carrier, a selected chromium compound, a selected phosphorus compound and a selected aluminum compound, and then (1.2) the catalyst intermediate is heated in an oxygen-containing gas stream. In this process, the component (1) used is one which is obtained by a method in which, in each case in a specific manner, (1.1) in a first stage, (1.1.1) first a suspension is prepared from (1.1.1.1) a finely divided silicate carrier and (1.1.1.2) an inert organic solvent, (1.1.2) then, (1.1.2.1) in an inert organic solvent, (1.1.2.2) an organic chromium compound is combined with (1.1.2.3) an aluminum trialkyl, (1.1.3) then (1.1.3.1) the suspension resulting from (1.1.1) is combined with (1.1.3.Type: GrantFiled: October 21, 1987Date of Patent: March 21, 1989Assignee: BASF AktiengesellschaftInventors: Rainer Konrad, Guido Funk, Juergen Schmidt-Thuemmes, Rudolf Mueller-Mall, Guenther Schweier
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Patent number: 4701432Abstract: An olefin polymerization catalyst comprising (a) a supported transition metal containing component comprising the support treated with at least one metallocene and at least one non-metallocene transition metal compound, and a cocatalyst comprising an alumoxane and an organometallic compound of a metal of Groups IA, IIA, IIB, or IIIA of the Periodic Table.Type: GrantFiled: June 9, 1986Date of Patent: October 20, 1987Assignee: Exxon Chemical Patents Inc.Inventor: Howard C. Welborn, Jr.
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Patent number: 4640907Abstract: Ethylene and alpha-olefins are homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and a titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, an oxygen containing compound, an acyl halide and titanium tetrachloride and a Group IIIa hydrocarbyl metal dihalide and prepolymerizing the solid with a minor amount of ethylene.Type: GrantFiled: August 6, 1984Date of Patent: February 3, 1987Assignee: Exxon Research & Engineering Co.Inventor: Steven A. Best
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Patent number: 4639428Abstract: Ethylene and alpha-olefins are homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and a titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organic magnesium compound, an oxygen containing compound, an acyl halide and titanium tetrachloride, a Group IIIa hydrocarbyl metal dihalide and Cl.sub.2, Br.sub.2, an interhalogen or mixtures thereof.Type: GrantFiled: August 6, 1984Date of Patent: January 27, 1987Assignee: Exxon Research & Engineering Co.Inventor: Steven A. Best
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Patent number: 4629714Abstract: An intermetallic compound is disclosed. The compound is formed by reacting a first reaction product, the first reaction product being the product of reaction of a polymeric transition metal oxide alkoxide with a reducing metal having a higher oxidation potential than the transition metal, the polymeric transition metal oxide alkoxide being the product of the controlled partial hydrolysis of a transition metal alkoxide, with a first halide activator to produce a second reaction product. The second reaction product, in turn, is reacted with a second halide activator to form the intermetallic compound. The intermetallic compound is useful as a catalyst component in a catalyst system for the polymerization of alpha-olefins. The catalyst system includes, in addition to the intermetallic compound, a cocatalyst, an organic compound which includes an element selected from the group consisting of aluminum and boron.Type: GrantFiled: October 25, 1985Date of Patent: December 16, 1986Assignee: National Distillers and Chemical CorporationInventor: Javan Shelly
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Patent number: 4618596Abstract: Ethylene and alpha-olefins are homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising an organo metal cocatalyst and a titanium-containing catalyst component, said titanium-containing catalyst component being obtained by reacting in the presence of a porous particulate material, a halogen, an organic magnesium compound, an oxygen-containing compound, titanium tetrachloride and treating the solids with an organometallic compound of a Group IIa, IIb or IIIa metal.Type: GrantFiled: July 26, 1985Date of Patent: October 21, 1986Assignee: Exxon Chemical Patents Inc.Inventors: Agapios K. Agapiou, Michael E. Muhle, Myron B. Kurtzman
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Patent number: 4567154Abstract: A catalyst composition for use in polymerizing alpha olefins which comprises a solid supported titanium complex and a cocatalyst comprising a mixture of an alkyl aluminum halide and a dialkyl magnesium or alkyl lithium compound.Type: GrantFiled: June 27, 1983Date of Patent: January 28, 1986Assignee: Chevron Research CompanyInventor: Robert Bacskai