Containing Hydrides Or Organometallic Of Two Or More Different Component A Metals Patents (Class 502/114)
  • Patent number: 5753578
    Abstract: 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: Grant
    Filed: June 21, 1996
    Date of Patent: May 19, 1998
    Assignee: Enichem S.p.A.
    Inventors: Roberto Santi, Giampiero Borsotti, Antonio Proto, Liliana Gila, Karel Bujadoux
  • Patent number: 5750454
    Abstract: 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: Grant
    Filed: May 30, 1996
    Date of Patent: May 12, 1998
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Hiroyuki Shimizu, Akira Sano, Kazuo Matsuura
  • Patent number: 5744678
    Abstract: 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: Grant
    Filed: November 1, 1996
    Date of Patent: April 28, 1998
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Fuyuki Aida, Takashi Nakano, Yoshio Tajima, Kazuo Matsuura
  • Patent number: 5731253
    Abstract: 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: Grant
    Filed: July 27, 1995
    Date of Patent: March 24, 1998
    Assignee: Albemarle Corporation
    Inventor: Samuel A. Sangokoya
  • Patent number: 5728641
    Abstract: 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: Grant
    Filed: June 21, 1995
    Date of Patent: March 17, 1998
    Assignee: Nippon Oil Company, Limited
    Inventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
  • Patent number: 5728784
    Abstract: 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: Grant
    Filed: November 27, 1996
    Date of Patent: March 17, 1998
    Assignee: Enichem S.p.A.
    Inventors: Riccardo Po', Nicoletta Cardi, Roberto Santi
  • Patent number: 5726262
    Abstract: 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: Grant
    Filed: December 24, 1996
    Date of Patent: March 10, 1998
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Mamoru Kioka, Tetsunori Shinozaki
  • Patent number: 5707914
    Abstract: 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: Grant
    Filed: June 5, 1995
    Date of Patent: January 13, 1998
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Naoki Kataoka, Yosuke Numao, Takashi Seki, Yoshio Tajima, Kazuo Matsuura
  • Patent number: 5703180
    Abstract: 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: Grant
    Filed: March 19, 1996
    Date of Patent: December 30, 1997
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Mamoru Takahashi, Akira Todo
  • Patent number: 5693583
    Abstract: 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: Grant
    Filed: February 11, 1997
    Date of Patent: December 2, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
  • Patent number: 5670587
    Abstract: 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: Grant
    Filed: January 23, 1996
    Date of Patent: September 23, 1997
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu, Masahiko Kuramoto
  • Patent number: 5625014
    Abstract: 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: Grant
    Filed: June 6, 1995
    Date of Patent: April 29, 1997
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Naoki Kataoka, Yosuke Numao, Takashi Seki, Yoshio Tajima, Kazuo Matsuura
  • Patent number: 5587439
    Abstract: 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: Grant
    Filed: May 12, 1995
    Date of Patent: December 24, 1996
    Assignee: Quantum Chemical Corporation
    Inventor: Anthony-J. DiMaio
  • Patent number: 5583083
    Abstract: 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: Grant
    Filed: July 10, 1995
    Date of Patent: December 10, 1996
    Assignee: Neste Oy
    Inventors: Sirpa Ala-Huikku, Marjaana Lommi
  • Patent number: 5578540
    Abstract: 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: Grant
    Filed: February 5, 1996
    Date of Patent: November 26, 1996
    Assignee: Enichem Elastomeri S.r.L.
    Inventors: Viviano Banzi, Gianni Loberti
  • Patent number: 5556821
    Abstract: 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: Grant
    Filed: July 19, 1994
    Date of Patent: September 17, 1996
    Assignee: Nippon Oil Company, Limited
    Inventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
  • Patent number: 5527868
    Abstract: 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: Grant
    Filed: November 22, 1994
    Date of Patent: June 18, 1996
    Assignee: BASF Aktiengesellschaft
    Inventors: Kaspar Evertz, Rueger Schlund, Peter Jutzi, Ingrid Mieling
  • Patent number: 5510434
    Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound polymer which catalyst comprises a contact product between an (A) trivalent titanium compound and a (B) compound represented by the general formula (II) or (III)R.sup.1.sub.k M.sup.1 L.sup.2.sub.m (II)R.sup.1.sub.k M.sup.1 X.sup.2.sub.l L.sup.2.sub.m (III)a (C) an ionic compound comprising a noncoordinate anion and a cation, an aluminoxane or an organoboron compound; and optionally a (D) Lewis acid, and a process for producing an aromatic vinyl compound polymer having a high degree of syndiotactic configuration which process comprises polymerizing (a) an aromatic vinyl compound or (b) an aromatic vinyl compound together with an olefin or a diolefin in the presence of the above catalyst.
    Type: Grant
    Filed: November 23, 1994
    Date of Patent: April 23, 1996
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventor: Mizutomo Takeuchi
  • Patent number: 5506183
    Abstract: 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: Grant
    Filed: August 9, 1994
    Date of Patent: April 9, 1996
    Assignee: Nippon Oil Company, Limited
    Inventors: Akira Sano, Takeichi Shiraishi, Sinichi Yanahashi, Hiroyuki Shimizu, Kazuo Matsuura
  • Patent number: 5500397
    Abstract: 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: Grant
    Filed: January 13, 1994
    Date of Patent: March 19, 1996
    Assignee: Montell North America Inc.
    Inventors: Illaro Cuffiani, Umberto Zucchini, deceased
  • Patent number: 5480849
    Abstract: 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: Grant
    Filed: August 16, 1993
    Date of Patent: January 2, 1996
    Assignee: Borealis Holding A/S
    Inventors: Bill Gustafsson, Arja Kostiainen, Pekka Sormunen
  • Patent number: 5468707
    Abstract: 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: Grant
    Filed: July 29, 1994
    Date of Patent: November 21, 1995
    Assignee: Merck Patent Gesellschaft mit Beschrankter Haftung
    Inventors: Ludwig Pohl, Fike Poetsch, Herbert Schumann, Karin Weiss, Karl-Heinz Thiele, Hans-Ludwig Hirsch
  • Patent number: 5451556
    Abstract: 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: Grant
    Filed: February 8, 1995
    Date of Patent: September 19, 1995
    Assignees: Akzo Nobel N.V., Saint Peter S.r.l.
    Inventor: Gualtiero Giovando
  • Patent number: 5407882
    Abstract: 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: Grant
    Filed: August 2, 1993
    Date of Patent: April 18, 1995
    Assignee: Tosoh Corporation
    Inventors: Satoru Yamada, Akihiro Yano
  • Patent number: 5405817
    Abstract: 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: Grant
    Filed: February 12, 1993
    Date of Patent: April 11, 1995
    Assignee: Quantum Chemical Corporation
    Inventors: Chi-I Kuo, Michael W. Lynch
  • Patent number: 5399540
    Abstract: 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: Grant
    Filed: February 12, 1993
    Date of Patent: March 21, 1995
    Assignee: Quantum Chemical Corporation
    Inventors: Chi-I Kuo, Michael W. Lynch
  • Patent number: 5395810
    Abstract: 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: Grant
    Filed: January 27, 1993
    Date of Patent: March 7, 1995
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, Michael J. Elder, Baireddy R. Reddy, David J. Rauscher
  • Patent number: 5330947
    Abstract: 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: Grant
    Filed: October 15, 1991
    Date of Patent: July 19, 1994
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
  • Patent number: 5260244
    Abstract: 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: Grant
    Filed: October 1, 1992
    Date of Patent: November 9, 1993
    Assignee: Phillips Petroleum Company
    Inventor: Ted M. Pettijohn
  • Patent number: 5235071
    Abstract: 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: Grant
    Filed: June 30, 1992
    Date of Patent: August 10, 1993
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Kenji Ueda, Masaaki Okuno, Tatsuya Kawabata, Shinya Tanaka
  • Patent number: 5204304
    Abstract: 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: Grant
    Filed: June 4, 1991
    Date of Patent: April 20, 1993
    Assignee: Quantum Chemical Corporation
    Inventors: Chi-I Kuo, Michael W. Lynch
  • Patent number: 5155079
    Abstract: 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: Grant
    Filed: June 7, 1991
    Date of Patent: October 13, 1992
    Assignee: Quantum Chemical Corporation
    Inventors: Leonard V. Cribbs, Michael W. Lynch
  • Patent number: 5126301
    Abstract: 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: Grant
    Filed: March 12, 1990
    Date of Patent: June 30, 1992
    Assignee: Mitsui Petrochemical Industries, Inc.
    Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Akinori Toyota, Norio Kashiwa
  • Patent number: 5120806
    Abstract: 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: Grant
    Filed: August 22, 1991
    Date of Patent: June 9, 1992
    Assignee: Hercules Incorporated
    Inventor: Andrea E. Martin
  • Patent number: 5114897
    Abstract: 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: Grant
    Filed: May 31, 1991
    Date of Patent: May 19, 1992
    Assignee: The Dow Chemical Company
    Inventors: Joseph G. Schell, Jr., Gary R. Marchand, Larry A. Meiske
  • Patent number: 5068489
    Abstract: 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: Grant
    Filed: December 28, 1989
    Date of Patent: November 26, 1991
    Assignee: Union Carbide Chemicals and Plastics Technology Corporation
    Inventors: David N. Edwards, Robert J. Jorgensen, Kiu H. Lee, Arthur E. Marcinkowsky
  • Patent number: 5057475
    Abstract: 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: Grant
    Filed: September 13, 1990
    Date of Patent: October 15, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Jo Ann M. Canich, Gary F. Licciardi
  • Patent number: 5010151
    Abstract: 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: Grant
    Filed: September 11, 1990
    Date of Patent: April 23, 1991
    Assignee: Idemitsu Petrochemical Co., Ltd.
    Inventor: Norio Tomotsu
  • Patent number: 4943621
    Abstract: 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: Grant
    Filed: August 4, 1988
    Date of Patent: July 24, 1990
    Assignee: The B. F. Goodrich Company
    Inventors: Dennis J. Janda, Paul T. Stricharczuk, Robert J. Minchak
  • Patent number: 4900798
    Abstract: 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: Grant
    Filed: September 16, 1987
    Date of Patent: February 13, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Juergen Kerth, Rudolf Mueller-Mall, Guenther Schweier
  • Patent number: 4871704
    Abstract: 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: Grant
    Filed: October 7, 1988
    Date of Patent: October 3, 1989
    Assignee: Toa Nenryo Kogyo K.K.
    Inventors: Tadanao Kohara, Satoshi Ueki
  • Patent number: 4870043
    Abstract: 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: Grant
    Filed: April 1, 1988
    Date of Patent: September 26, 1989
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Mitsuyuki Matsuura, Takashi Fujita
  • Patent number: 4870042
    Abstract: 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: Grant
    Filed: October 7, 1988
    Date of Patent: September 26, 1989
    Assignee: Toa Nenryo Kogyo K.K.
    Inventors: Tadanao Kohara, Satoshi Ueki
  • Patent number: 4814308
    Abstract: 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: Grant
    Filed: October 21, 1987
    Date of Patent: March 21, 1989
    Assignee: BASF Aktiengesellschaft
    Inventors: Rainer Konrad, Guido Funk, Juergen Schmidt-Thuemmes, Rudolf Mueller-Mall, Guenther Schweier
  • Patent number: 4701432
    Abstract: 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: Grant
    Filed: June 9, 1986
    Date of Patent: October 20, 1987
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Howard C. Welborn, Jr.
  • Patent number: 4640907
    Abstract: 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: Grant
    Filed: August 6, 1984
    Date of Patent: February 3, 1987
    Assignee: Exxon Research & Engineering Co.
    Inventor: Steven A. Best
  • Patent number: 4639428
    Abstract: 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: Grant
    Filed: August 6, 1984
    Date of Patent: January 27, 1987
    Assignee: Exxon Research & Engineering Co.
    Inventor: Steven A. Best
  • Patent number: 4629714
    Abstract: 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: Grant
    Filed: October 25, 1985
    Date of Patent: December 16, 1986
    Assignee: National Distillers and Chemical Corporation
    Inventor: Javan Shelly
  • Patent number: 4618596
    Abstract: 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: Grant
    Filed: July 26, 1985
    Date of Patent: October 21, 1986
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Agapios K. Agapiou, Michael E. Muhle, Myron B. Kurtzman
  • Patent number: 4567154
    Abstract: 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: Grant
    Filed: June 27, 1983
    Date of Patent: January 28, 1986
    Assignee: Chevron Research Company
    Inventor: Robert Bacskai