Nonmetallic Organic Oxygen Containing Patents (Class 502/125)
  • Patent number: 5518973
    Abstract: A TiCl.sub.3 catalyst system is disclosed employing the electron donor, dicyclopentyldimethoxysilane ("DCPMS"). Additionally disclosed is a process for polymerizing olefins in the presence of a catalyst system employing a titanium trichloride catalyst, an alkylaluminum cocatalyst, and dicyclopentyldimethoxysilane is provided. The polymerization process comprises providing a prepolymerized titanium trichloride catalyst, and polymerizing an .alpha.-olefin in the presence of the prepolymerized catalyst, a trialkylaluminum co-catalyst and dicyclopentyldimethoxysilane. The catalyst system of the invention provides increased catalyst activity for a TiCl.sub.3 catalyst and a very broad polymer molecular weight distribution.
    Type: Grant
    Filed: October 15, 1993
    Date of Patent: May 21, 1996
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Nemesio D. Miro, William M. Chien
  • Patent number: 5514634
    Abstract: An ethylene polymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a dialkylmagnesium compound, contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as tetraalkoxysilanes, e.g. tetraethyl orthosilicate, and incorporating a transition metal component, such as titanium tetrachloride, in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with dimethylaluminum chloride as a cocatalyst results in a catalyst system which is effective for the production of ethylene copolymers with multimodal molecular weight distributions.
    Type: Grant
    Filed: June 10, 1994
    Date of Patent: May 7, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
  • 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: 5506184
    Abstract: A catalyst composition for olefin polymerization and copolymerization which contains a transition metal complex with a bidentate or a tridentate ligand and a cocatalyst mixture containing dialkylaluminum halide and dialkylmagnesium.The transition metal complexes with bidentate ligands L have the empirical formula LMX.sub.2, LMXY or L.sub.2 M where M is Ti, V, Zr or Hf; X is an alkoxy group, an aryloxy group, or a halogen atom; Y is a mono- or double-bonded ligand different from X.The bidentate L ligands are described by general formulasZ--R--Z OR Z--R--W--R--Zwhere R is an alkylene group, a cycloalkylene group, an arylene group (unsubstituted or alkyl-substituted) or an alkylarylene group; W is CH.sub.2, O, S, N--R', or SiR'.sub.2 where R' is an alkyl or an aryl group; and Z is an oxygen atom, a sulfur atom, an N--H group or a C(.dbd.O)--O group.
    Type: Grant
    Filed: June 22, 1994
    Date of Patent: April 9, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Yury V. Kissin, Robert I. Mink
  • 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: 5498770
    Abstract: A catalyst for the polymerization of olefins comprising (A) a solid catalyst component essentially containing magnesium, titanium, an electron donor compound, and a halogen which is prepared by contacting a magnesium compound, a titanium halide compound, and an electron donor compound, (B) an organoaluminum compound, and (C) an organosilicon compound and a process for polymerizing an olefin using the same are disclosed, the organosilicon compound (C) being represented by formula (I): ##STR1## wherein R.sup.1 and R.sup.2, which may be the same or different, each represents an alkyl group having from 1 to 3 carbon atoms; R.sup.3 and R.sup.4, which may be the same or different, each represents an alkyl group having from 1 to 3 carbon atoms, or a halogen atom; and m and n each represents 0 or an integer of 1 or 2. A polyolefin having high stereoregularity and broad molecular weight distribution can be obtained in high yield.
    Type: Grant
    Filed: September 20, 1994
    Date of Patent: March 12, 1996
    Assignee: Toho Titanium Co., Ltd.
    Inventors: Motoki Hosaka, Kenji Goto, Masahiko Matsuo
  • Patent number: 5496783
    Abstract: Process for oligomerizing ethylene into light alpha olefins, mainly 1-butene, 1-hexene, 1-octene and 1-decene, in which the ethylene is contacted with a catalyst obtained by mixing a zirconium compound with an organic compound chosen from within the class of acetals and ketals and with a chlorine or bromine-containing compound of aluminium hydrocarbyl.
    Type: Grant
    Filed: June 2, 1994
    Date of Patent: March 5, 1996
    Assignee: Institut Francais du Petrole
    Inventors: Yves Chauvin, Dominique Commereuc, Francois Hugues, Helene Olivier, Lucien Saussine
  • Patent number: 5494872
    Abstract: A novel catalyst and solid catalyst component useful for preparing polyolefins having a broad molecular weight distribution and high stereoregularity.
    Type: Grant
    Filed: July 27, 1994
    Date of Patent: February 27, 1996
    Assignee: Toho Titanium Company, Ltd.
    Inventors: Motoki Hosaka, Minoru Terano, Kazuhiro Ishii
  • Patent number: 5492876
    Abstract: 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: Grant
    Filed: February 1, 1994
    Date of Patent: February 20, 1996
    Assignee: Novacor Chemicals (International) S.A.
    Inventors: Daniel J. Gillis, Vaclav G. Zboril, Millard C. Hughson
  • Patent number: 5484754
    Abstract: 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: Grant
    Filed: January 21, 1993
    Date of Patent: January 16, 1996
    Assignee: Elf Atochem, S. A.
    Inventors: Roger Spitz, Maryse Patin, Jean Malinge
  • Patent number: 5476825
    Abstract: A catalyst for polymerization of olefin, which is capable of producing an olefin polymer with high stereoregularity and narrow molecular weight distribution, and which comprises (1) a solid catalyst component essentially containing titanium, magnesium and halogen, 2) an organoaluminum compound, and (3) a contact product of (A) an organometallic compound and (B) an organosilicon compound; and a process for producing a polymer using the above catalyst.
    Type: Grant
    Filed: July 6, 1993
    Date of Patent: December 19, 1995
    Assignee: Showa Denko K.K.
    Inventors: Masaki Fushimi, Toshio Fujita, Minoru Suzuki
  • Patent number: 5470812
    Abstract: An ethylene copolymerization catalyst is prepared by impregnating a porous support, such as silica, with an organomagnesium compound such as a magnesium alkyl and contacting the magnesium-containing support with a silane compound which is free of hydroxyl groups, such as a tetraalkyl orthosilicate, e.g. tetraethyl orthosilicate (TEOS). A transition metal component such as titanium tetrachloride is then incorporated into the support in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with a trialkylaluminum compound results in a catalyst which is effective for the production of ethylene copolymers.
    Type: Grant
    Filed: November 15, 1993
    Date of Patent: November 28, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Robert I. Mink, Thomas E. Nowlin
  • Patent number: 5468703
    Abstract: Disclosed is a titanium catalyst component for ethylene polymerization obtained by contacting [A] a solid magnesium aluminum complex containing magnesium, halogen, aluminum and an alkoxy group and/or alcohol having at least 6 carbon atoms, with [B] a tetravalent titanium compound. The solid magnesium aluminum complex [A] is obtained by contacting (a-1) a magnesium solution formed from a halogen-containing magnesium compound, an alcohol having at least 6 carbon atoms and a hydrocarbon solvent, with (a-2) an organoaluminum compound. Also disclosed is a process for ethylene polymerization comprising polymerizing ethylene or copolymerizing ethylene with an .alpha.-olefin having 3 to 20 carbon atoms in the presence of a catalyst for ethylene polymerization comprising [I] the above-mentioned titanium catalyst component for ethylene polymerization and [II] an organoaluminum compound catalyst component.
    Type: Grant
    Filed: October 4, 1993
    Date of Patent: November 21, 1995
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Mamoru Kioka, Tsuneo Yashiki
  • Patent number: 5468698
    Abstract: The invention relates to a method for preparing a particulate carrier for an olefin polymerization procatalyst comprising a complex of an organic compound/transition metal compound as a carrier. In the method a melt MgCl.sub.2 --C.sub.2 H.sub.5 OH-complex is provided containing on average 3.3 to 5.5 C.sub.2 H.sub.5 OH-molecules per each MgCl.sub.2 -molecule, the melt MgCl.sub.2 -complex is sprayed through a nozzle dispersing it into a chamber, wherein a particulate carrier is formed of it and the particulate carrier is removed from the chamber. Unlike prior known methods to produce a carrier having an optimal C.sub.2 H.sub.5 OH content in this invention the removal rate--by the aid of heat--of C.sub.2 H.sub.5 OH from the MgCl.sub.2 --C.sub.2 H.sub.5 OH-complex in connection with the spraying that the particulate carrier is controlled. As a result, the particulate carrier obtained possesses on average 2.0 to 3.2 C.sub.2 H.sub.5 OH molecules per each MgCl.sub.2 molecule. Such a carrier has a suitable C.sub.2 H.
    Type: Grant
    Filed: May 11, 1994
    Date of Patent: November 21, 1995
    Assignee: Borealis Holding A/S
    Inventors: Jukka Koskinen, Thomas Garoff
  • Patent number: 5468704
    Abstract: Disclosed is a catalyst for the polymerization of olefins, which includes the product of the reaction between an Al-alkyl compound and a solid catalyst component containing a magnesium halide in active form, a titanium compound and an electron-donor selected from the 1,3-diketones of formula: ##STR1## wherein the radicals R are the same or different, the radicals R.sup.I are the same or different, and R and R.sup.I are C.sub.1 -C.sub.20 alkyl, C.sub.3 -C.sub.20 cycloalkyl, C.sub.6 -C.sub.12 aryl, C.sub.7 -C.sub.20 arylalkyl or alkylaryl radicals or hydrogen, with the proviso that at least one of the R radicals is not hydrogen and can be bonded with the other R radical to form a cyclic structure, and at least one of the R.sup.I radicals, which are not bonded to one another to form a cyclic structure, is a branched alkyl, cycloalkyl or aryl radical, or is bonded to one or both R radicals to form a cyclic structure.
    Type: Grant
    Filed: September 30, 1994
    Date of Patent: November 21, 1995
    Assignee: Montell North America Inc.
    Inventors: Giampiero Morini, Enrico Albizzati, Umberto Giannini, Raimondo Scordamaglia, Luisa Barino
  • Patent number: 5461017
    Abstract: An improved catalyst for the polymerization of olefins comprising at least one metallocene and at least one aluminoxane co-catalyst supported on a substrate comprising a cross-linked polymeric, porous, resin wherein at least one of the monomers in the resin has at least one pendant functional group which is not reactive under the conditions of the formation of the substrate, and therefore survives the copolymerization which forms the substrate. One specific cross-linked resin is a copolymer of styrene, divinyl benzene and acetoxy styrene.
    Type: Grant
    Filed: March 4, 1994
    Date of Patent: October 24, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Allan B. Furtek, Ronald S. Shinomoto
  • Patent number: 5457171
    Abstract: Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alkenes contain, as active components, a metallocene complex of a metal of subgroup IV or V of the Periodic Table, an oligomeric alumina compound and a cyclic boron compound of the general formula IV ##STR1## where R.sup.18 to R.sup.20 are each C.sub.1 -C.sub.10 -alkyl which may be monosubstituted to trisubstituted by halogen, C.sub.6 -C.sub.15 -aryl or C.sub.1 -C.sub.10 -alkoxy,C.sub.4 -C.sub.7 -cycloalkyl which may be monosubstituted to trisubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.1 -C.sub.10 -alkoxy,C.sub.1 -C.sub.10 -alkoxy which may be monosubstituted to trisubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.6 -C.sub.15 -aryl, or C.sub.6 -C.sub.15 -aryl which may be monosubstituted to pentasubstituted by halogen, C.sub.1 -C.sub.10 -alkyl or C.sub.1 -C.sub.10 -alkoxy.
    Type: Grant
    Filed: August 3, 1994
    Date of Patent: October 10, 1995
    Assignee: BASF Aktiengesellschaft
    Inventors: Franz Langhauser, Martin Lux, Rolf Muelhaupt, David Fischer
  • Patent number: 5439662
    Abstract: A process for the manufacture of MgCl.sub.2.MgO with narrow granulometric distribution by treatment of hydrated MgCl.sub.2 with an alcohol followed by heat treatment after partial elimination of the alcohol, characterized in that the hydrated MgCl.sub.2 is suspended in the alcohol, and that the molar ratio of the alcohol to the hydrated MgCl.sub.2 is lower than the solutility ratio of these two substances at the temperature of the suspension. The resultant MgCl.sub.2.MgO can be employed as a support in catalytic components for the polymerization of olefins.
    Type: Grant
    Filed: January 21, 1993
    Date of Patent: August 8, 1995
    Assignee: Elf Atochem S.A.
    Inventors: Roger Spitz, Maryse Patin, Claude Brun
  • Patent number: 5432139
    Abstract: Processes for the formulation of Ziegler-type catalysts from a transition metal component, an electron donor and a co-catalyst which are sequentially mixed together. The co-catalyst is initially contacted with either of the transition metal catalyst or the electron donor for a first contact time of 5-120 seconds. This mixture is then contacted with the remainder of the electron donor or transition metal component for a second contact time of less and 110 seconds. The three component system is then used in olefin polymerization. The olefin contacting step can involve an initial pre-polymerization reaction. A specific order of addition involves mixture of the transition metal component and the co-catalyst component for a contact time of 5-120 seconds followed by contact with an electron donor component for no more than 30 seconds. Another order of addition involves initially contacting the electron donor with the co-catalyst.
    Type: Grant
    Filed: March 4, 1992
    Date of Patent: July 11, 1995
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, David J. Rauscher, Shabbir A. Malbari
  • Patent number: 5432244
    Abstract: A process for the polymerization of propylene or a mixture comprising propylene and one or more alpha-olefins and, optionally, one or more diolefins comprising contacting the propylene or the mixture of olefins in at least one reaction zone, under polymerization conditions, with a catalyst system comprising (i) a solid catalyst precursor, which includes magnesium; titanium; a halogen which is chlorine, bromine, or iodine, or mixtures thereof; and a mono- or polycarboxylic acid ester; (ii) a hydrocarbylaluminum cocatalyst; and (iii) a mixture of selectivity control agents comprising a mono- or polycarboxylic acid ester and a silicon compound containing at least one silicon-oxygen-carbon linkage with the proviso that (a) the atomic ratio of aluminum to titanium is in the range of about 5 to about 300; and (b) the molar ratio of the ester to silicon compound in the mixture of selectivity control agents is at least about 1.5:1.
    Type: Grant
    Filed: December 12, 1990
    Date of Patent: July 11, 1995
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventor: David M. Rebhan
  • Patent number: 5424379
    Abstract: A catalyst for production of 1,4-polybutadiene which comprisesas the catalyst component (A) a transition metal compound represented by the formula M(R).sub.l (OR').sub.m X.sub.n-(l+m), wherein M denotes a transition metal atom, R and R' each denote a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and l, m and n denote numerals satisfying the equations l.gtoreq.0, m.gtoreq.0 and n-(l+m).gtoreq.0, n corresponding to the valence of the transition metal,as the catalyst component (B) an organoaluminum compound represented by the formula AlR.sup.1.sub.a X'.sub.3-a, wherein R.sup.1 denotes a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and a denotes a numeral satisfying the equation 1.gtoreq.a.gtoreq.3, or an aluminoxane obtained by the reaction of said organoaluminum compound with water, andas the catalyst component (C) an organic compound having at least two hydroxyl groups.
    Type: Grant
    Filed: May 16, 1994
    Date of Patent: June 13, 1995
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Kakugo, Tatsuya Miyatake, Koozi Mizunuma, Yoshio Yagi, Kazuhiro Watanabe
  • Patent number: 5424263
    Abstract: A catalyst component useful in the polymerization of olefins is disclosed. The catalyst component comprises the product obtained by steps of (a) contacting silica with at least one hydrocarbon soluble magnesium-containing compound; (b) contacting the product of step (a) with component (1), a heterocyclic fused ring compound substituted with at least one oxygen atom, and component (2), a modifying compound selected from the group consisting of silicon halides, boron halides, aluminum halides, alkyl silicon halides and mixtures thereof, with the proviso that components (1) and (2) be present such that the molar ratio of component (2) to component (1) is at least about 4:1; and (c) contacting the product of step (b) with a titanium-containing compound having the structural formula TiX.sub.m (OR).sub.n, where X is halogen; R is hydrocarbyl; m is an integer of 1 to 4; and n is 0 or an integer of 1 to 3 with the proviso that the sum of m and n is 4.
    Type: Grant
    Filed: April 23, 1993
    Date of Patent: June 13, 1995
    Assignee: Quantum Chemical Corporation
    Inventor: Charles K. Buehler
  • Patent number: 5420089
    Abstract: A catalyst for producing styrene-based polymers, containing (A) a titanium compound, (B) a contact product of an organoaluminum compound and water, and (C) an organic polyhydroxy compound, or (A) a titanium compound and (B) a contact product of an organoaluminum compound, water and a organic polyhydroxy compound, and a process for producing styrene-based polymers by the use of the above catalyst.
    Type: Grant
    Filed: September 22, 1993
    Date of Patent: May 30, 1995
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Norio Tomotsu, Hiroshi Maezawa
  • Patent number: 5409875
    Abstract: A polymer supported catalyst comprises Ziegler-Natta catalysts immobilized on a magnesium-modified polymer support. The catalyst support is prepared by (1) dissolving a carboxyl group-containing polymer in a solvent and precipitating the polymer in a polar non-solvent, (2) wet-grinding the precipitated polymer, and (3) mixing the ground polymer with an organomagnesium compound or a complex of an organomagnesium compound and an organoaluminum compound to give a magnesium-modified polymer support. Optionally, the resulting magnesium-modified support is treated with a halogen-containing silicon compound. The catalysts may be loaded onto the support by reacting the magnesium-modified support with a transition metal compound to form a catalyst constituent, and then combining the catalyst constituent with an appropriate organo-metallic compound.
    Type: Grant
    Filed: March 8, 1993
    Date of Patent: April 25, 1995
    Assignee: Queen's University
    Inventors: Cheng C. Hsu, Lixin Sun
  • Patent number: 5407883
    Abstract: A catalyst for producing a polyolefin having a high melting point and a high stereoregularity, which comprises: (A) a solid catalyst component containing titanium, magnesium and halogen, (B) an organic aluminum compound, and (C) an organic silicon compound represented by formula (1): ##STR1## wherein R.sup.1, R.sup.2, and R.sup.3 each represents a C.sub.1-3 hydrocarbon group.
    Type: Grant
    Filed: August 27, 1993
    Date of Patent: April 18, 1995
    Assignee: Showa Denko K.K.
    Inventors: Masaki Fushimi, Toshio Fujita
  • Patent number: 5405924
    Abstract: An olefin metathesis catalyst system and process for the metathesis polymerization of cyclic olefins, such as dicyclopentadiene, are disclosed. The catalyst system comprises the reaction product of:(a) an imido transition metal halide complex of formula: ##STR1## wherein Ar is C.sub.6-20 aryl, preferably phenyl; M is a transition metal selected from the second and third rows of Groups 5, 6, 7 and 8 of the Periodic Table (IUPAC 1989 convention) and including for example niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium or osmium, preferably tungsten or molybdenum; R is independently halide, C.sub.1-20 alkyl, C.sub.1-12 alkoxy, C.sub.1-12 haloalkyl, C.sub.6-20 aryl, C.sub.6-20 aryloxy, cyano or combinations thereof; L is independently a complexing ligand selected from carbonyl, C.sub.1-12 alkoxy, C.sub.1-12 haloalkoxy, C.sub.1-12 alkyl ethers, including mono-, di- and higher ethers, C.sub.12 alkylnitriles, C.sub.5-20 pyridines, C.sub.
    Type: Grant
    Filed: June 22, 1994
    Date of Patent: April 11, 1995
    Assignee: Shell Oil Company
    Inventor: Donald R. Kelsey
  • Patent number: 5403803
    Abstract: In accordance with this invention, there is provided a living carbocationic polymerization catalyst system comprising: (1) a halide of titanium, tin, vanadium or antimony; (2) an aluminum halide selected from the group consisting of aralkyl aluminum halides and alkyl aluminum halides; and (3) an initiator selected from the group consisting of tertiary alkyl halides, tertiary aralkyl halides, tertiary polymeric halides, and water provided that if the initiator is organic, a proton scavenger is present, or, alternatively, if the initiator consists of water, a secondary or tertiary amine is present. Another aspect of the invention comprises a process for using this catalyst system for the polymerization of olefins and for producing narrow molecular weight distribution polymers in a short reaction time.
    Type: Grant
    Filed: September 28, 1993
    Date of Patent: April 4, 1995
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Timothy D. Shaffer, John R. Ashbaugh
  • 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: 5385993
    Abstract: Ziegler polymerization of C.sub.3 or higher .alpha.-olefins is disclosed which is characterized by a solid catalyst component and an organoaluminum component used in the Ziegler catalyst, and also by the temperature used which is 150.degree. to 300.degree. C. The solid catalyst component, Component (A), comprises Sub-component (i) which is a solid catalyst component for Ziegler catalysts comprising Ti, Mg and a halogen; Sub-component (ii) which is a silicon compound represented by a formula: R.sup.1.sub.m X.sub.n Si(OR.sup.2).sub.4-n-m wherein R.sup.1 indicates a hydrocarbyl group, R.sup.2 which may be the same as or different from R.sup.1 indicates a hydrocarbyl group, X is a halogen atom, and m and n are each a number satisfying equations 0.ltoreq.m.ltoreq.3, 0.ltoreq.n.ltoreq.3 and 0.ltoreq.m+n.ltoreq.3; and Sub-component (iii) which is an organometal compound of a metal of Groups I to IV of the Periodic Table. The organoaluminum component (B) is an organoaluminum compound represented by a formulaR.sup.3.
    Type: Grant
    Filed: October 14, 1993
    Date of Patent: January 31, 1995
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventor: Takashi Fujita
  • Patent number: 5382557
    Abstract: A solid component of catalyst highly active in the (co)polymerization of ethylene containing titanium, magnesium, aluminum, chlorine and alkoxy groups, and obtained by means of a procedure wherein:(i) a solid, granular support of magnesium chloride, obtained by spray-drying an alcohol solution of magnesium chloride, is suspended in a liquid hydrocarbon solvent and an aliphatic alcohol and a titanium tetraalkoxide are added to the suspension thus obtained,(ii) the suspension of step (i) is heated until a homogeneous solution is obtained and the solution is cooled to precipitate a granular solid in a relative suspension,(iii) the granular solid obtained in step (ii), in the relative suspension, is put in contact and reacted with an aluminum alkyl halide, and(iv) the solid component catalyst is recovered from the reaction products of step (iii).
    Type: Grant
    Filed: July 10, 1992
    Date of Patent: January 17, 1995
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Francesco Masi, Renzo Invernizzi, Angelo Moalli, Cesare Ferrero, Francesco Menconi, Lia Barazzoni
  • Patent number: 5378778
    Abstract: A liquid catalyst component which can be used as a component of a catalyst system in combination with an organoaluminum compound (B) for producing ethylene-.alpha.-olefin copolymers.
    Type: Grant
    Filed: April 29, 1994
    Date of Patent: January 3, 1995
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Hirofumi Johoji, Hiroyuki Shiraishi, Toshio Sasaki, Kiyoshi Kawai
  • Patent number: 5371157
    Abstract: A high activity olefin polymerization catalyst, useful in the polymerization of lower .alpha.-olefins, comprises the solid product resulting from contacting a complex magnesium-containing, titanium-containing alkoxide compound with alkylaluminum halide, optionally employed in conjunction with a selectivity control agent.
    Type: Grant
    Filed: March 16, 1992
    Date of Patent: December 6, 1994
    Inventor: Robert C. Job
  • Patent number: 5349034
    Abstract: A catalyst for production of 1,4-polybutadiene which comprisesas the catalyst component (A) a transition metal compound represented by the formula M(R)l(OR')m X.sub.n-(l+m), wherein M denotes a transition metal atom, R and R' each denote a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and l, m and n denote numerals satisfying the equations l.gtoreq.0, m.gtoreq.0 and n-(l+m).gtoreq.0, n corresponding to the valence of the transition metal,as the catalyst component (B) an organoaluminum compound represented by the formula AlR.sup.1.sub.a X'.sub.3-a, wherein R.sup.1 denotes a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and a denotes a numeral satisfying the equation 1.ltoreq.a.ltoreq.3, or an aluminoxane obtained by the reaction of said organoaluminum compound with water, andas the catalyst component (C) an organic compound having at least two hydroxyl groups.
    Type: Grant
    Filed: July 22, 1993
    Date of Patent: September 20, 1994
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Kakugo, Tatsuya Miyatake, Koozi Mizunuma, Yoshio Yagi, Kazuhiro Watanabe
  • Patent number: 5336652
    Abstract: There is disclosed a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid support, containing magnesium, with a silane compound of the empirical formulaR.sup.1.sub.x SiR.sup.2.sub.ywherein Si is silicon atom; x is 1, 2, 3, or 4 and y is 0, 1, 2, or 3, provided that x+y is 4; R.sup.1 is R.sub.w --O-- wherein O is oxygen and R.sub.w is hydrocarbyl of 1 to 10 carbon atoms; and R.sup.2 is halogen or hydrocarbyl of 1 to 10 carbon atoms, or hydrogenand a transition metal compound, e.g., a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers. Also disclosed are methods of preparing polymers with the catalyst composition and the resulting polymers.
    Type: Grant
    Filed: November 6, 1991
    Date of Patent: August 9, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Robert I. Mink, Thomas E. Nowlin
  • Patent number: 5334568
    Abstract: The invention concerns:a catalytic solid containing magnesium, a halogen, titanium and silicon, this catalytic solid also containing aluminium and being microporous;a process for preparing this catalytic solid;use of this catalytic solid for polymerising alpha-olefines.
    Type: Grant
    Filed: June 6, 1991
    Date of Patent: August 2, 1994
    Assignee: Solvay (Societe Anonyme)
    Inventors: Leopold Demiddeleer, Yvan Kempeneer, Laurence Desvachez
  • Patent number: 5330949
    Abstract: A method for producing a polyolefin is disclosed which comprises polymerizing an .alpha.-olefin in the presence of a catalyst composition comprising (A) a solid catalyst component prepared by contacting (a) a solid component comprising a magnesium alkoxide and/or a magnesium salt of a fatty acid supported on an inorganic oxide composed of at least one member selected from the group consisting of oxides of elements belonging to Groups II, III and IV of the periodic table and/or a composite inorganic oxide containing at least one member selected from the group consisting of oxides of elements belonging to Groups II, III and IV of the periodic table, the inorganic oxide or composite inorganic oxide having a surface hydroxide concentration of 3 .mu.mol/m.sup.2 or less, (b) an electron donating compound and (c) a titanium halide, (B) an organic metal compound, and (C) an electron donating compound.
    Type: Grant
    Filed: April 26, 1990
    Date of Patent: July 19, 1994
    Assignee: Idemitsu Petrochemical Company, Ltd.
    Inventors: Hideo Funabashi, Akira Tanaka, Rikuo Ohnishi, Toshikazu Kasahara, Takashi Yamawaki
  • Patent number: 5330951
    Abstract: The catalyst of the invention is useful in preparing high density polymers of controlled molecular weight distribution.A supported alpha-olefin polymerization catalyst composition of this invention is prepared in a multi-step process. In the first step, a mixture of a solid, porous carrier having reactive --OH groups and a non-polar solvent is contacted with at least one organomagnesium compound of the formulaR.sub.m Mg R'.sub.n (I)where R and R' are the same or different C.sub.4 -C.sub.12 alkyl groups, m and n are each 0, 1 or 2, providing that m+n equals the valence of Mg. Subsequently, the mixture of the first step is contacted with 1-butanol.
    Type: Grant
    Filed: December 9, 1992
    Date of Patent: July 19, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Robert I. Mink, Thomas E. Nowlin
  • Patent number: 5324698
    Abstract: A problem in the conventional olefin polymerization catalyst systems, the procatalysts of which are based on a solid carrier and a titanium compound and an electron donor on its surface, is that unsufficiently high activities are achieved by the morphology of the carrier. Moreover, the active age of such a catalyst in the polymerization is too short. These problems have now been solved by the olefin polymerization catalyst system according to the invention, the procatalyst of which comprises a solid carrier and a layer on its surface consisting of a titanium compound, a magnesium compound and an electron donor. The advantages of the invention become more emphasized when using monocyclopentadienyl titaniumtrichloride as the titanium compound.
    Type: Grant
    Filed: September 21, 1992
    Date of Patent: June 28, 1994
    Assignee: Neste Oy
    Inventors: Sirpa Ala-Huikku, Ulf Palmqvist, Marjaana Lommi, Eero Iiskola
  • Patent number: 5322830
    Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefins, in which particles are formed from magnesium halide and alcohol, the particles are reacted with an organometallic compound of any of the metals of the groups I to III, the thus obtained particulate product is activated by means of a titanium(IV) compound, and optionally a prepolymerization is carried out for the activated particles. A problem with this kind of a method is, how to form particles from magnesium dihalide and alcohol having an advantageous structure for the polymerization of ethylene and particularly ethylene with a narrow molecular weight distribution. The problem has in the present invention been solved so that the particles are formed by spray-crystallizing a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol and that titanium(IV) alcoxyhalide has been used as the titanium compound.
    Type: Grant
    Filed: September 18, 1991
    Date of Patent: June 21, 1994
    Assignee: Neste Oy
    Inventors: Pekka Sormunen, Jukka Koskinen, Paivi Waldvogel
  • Patent number: 5320995
    Abstract: A catalyst for the polymerization of olefins, containing magnesium, chlorine, aluminium and at least one transition metal, in a dispersed or emulsified form within an inert diluent, is obtained by:contacting, in an inert diluent, a magnesium dialkyl and aluminium trichloride, in a molar ratio equal or almost equal to 2/1, at a temperature lower than 105.degree. C. to obtain a catalyst precursor in a suspended form, or at a temperature higher than 105.degree. C. to form a catalyst precursor in the form of a colloidal emulsion, in the diluent used; andcontacting said suspended or emulsified precursor with at least one compound of a transition metal to form a catalyst in the form of a suspension or emulsion respectively.
    Type: Grant
    Filed: October 5, 1992
    Date of Patent: June 14, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Luciano Luciani, Mario Polesello, Federico Milani, Renzo Invernizzi, Giovanni Soverini
  • Patent number: 5310716
    Abstract: 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: Grant
    Filed: July 22, 1992
    Date of Patent: May 10, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Ludiano Luciani, Federico Milani, Renzo Invernizzi, Italo Borghi, Antonio Labianco
  • Patent number: 5308818
    Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is an alkyl or cycloalkyl group containing a primary or secondary carbon atom attached to the silicon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl or cycloalkyl group with a primary or secondary carbon atom attached to the silicon atom. The system has a catalyst efficiency of over 30 kg/g-cat.h as the Si/Ti mole ratio varies from 4-20 in the system. The system easily achieves efficiencies over 30 kg/g-cat.h. The system also exhibits good control over the xylene solubles of the polymer products.
    Type: Grant
    Filed: June 8, 1992
    Date of Patent: May 3, 1994
    Assignee: Fina Technology, Inc.
    Inventors: Edwar S. Shamshoum, David J. Rauscher
  • Patent number: 5300470
    Abstract: 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: Grant
    Filed: July 15, 1992
    Date of Patent: April 5, 1994
    Assignee: Himont Incorporated
    Inventors: Illaro Cuffiani, Umberto Zucchini
  • Patent number: 5298579
    Abstract: A method of using a catalyst with a suitable cocatalyst in the polymerization or copolymerization of 1-olefins are disclosed. The catalyst is prepared by: a) contacting a Group IIA organometallic compound, like 2-methylpentanoxymagnesium chloride, or a Group III organometallic compound, like triethylaluminum, or a combination thereof, with a porous or nonporous biodegradable substrate having active surface hydroxyl groups, like cellulose, to provide a modified biodegradable substrate; then b) contacting the modified biodegradable substrate with a transition metal compound, such as a transition metal halide or alkoxide, like titanium tetrachloride or vanadium (V) trichloride oxide, to form discrete catalyst particles. The catalyst particles are used in conjunction with a suitable cocatalyst, like triethylaluminum, in the homopolymerization or copolymerization of 1-olefins. During polymerization, porous biodegradable catalyst particles are fragmented into small solid particles that are trapped within polymer.
    Type: Grant
    Filed: November 13, 1992
    Date of Patent: March 29, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Raymond E. Hoff, Leonard V. Cribbs
  • Patent number: 5296431
    Abstract: 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: Grant
    Filed: July 30, 1991
    Date of Patent: March 22, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Klaus-Dieter Hungenberg, Juergen Kerth
  • Patent number: 5288824
    Abstract: Polymers of propene are prepared using a Ziegler-Natta catalyst system comprising (1) titanium component which is based on a finely divided, shape-imparting silica gel and contains titan- ium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. The process employs a titanium component (1) which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel which has a relatively high moisture content, (Ib) an organomagnesium compound and (Ic) a gaseous chlorinating agent in a manner such that (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then (Ic) is passed into the mixture obtained from (1.1.1), (1.2) then a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid derivative in a manner such that (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the mixture resulting from (1.2.
    Type: Grant
    Filed: August 25, 1992
    Date of Patent: February 22, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Juergen Kerth, Rainer Hemmerich, Peter Koelle, Patrik Mueller
  • Patent number: 5281567
    Abstract: An improved high activity olefin polymerization catalyst catalyzes the production of polymeric lower .alpha.-olefin having good properties and a relatively narrow particle size distribution. The catalyst is produced from an organoaluminum cocatalyst, a selectivity control agent and a novel olefin polymerization procatalyst which is prepared by contacting a tetravalent titanium halide, a halohydrocarbon, an electron donor and the solid procatalyst precursor obtained by heating an adduct of a carbonated magnesium ethoxide and a phenolic compound of enhanced acidity.
    Type: Grant
    Filed: June 29, 1992
    Date of Patent: January 25, 1994
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 5280000
    Abstract: The present invention relates to a novel catalyst used for homopolymerization of an olefin of 2 or more carbon atoms or for copolymerization of two or more olefins of 2 or more carbon atoms, as well as to a process for producing an olefin polymer using said catalyst. High molecular olefin polymers can be produced at a high yield, by homopolymerizing an olefin or copolymerizing olefins using a catalyst system consisting of a transition metal compound of the general formula M(R).sub.l (OR').sub.m X.sub.n-(l+m) and an aluminoxane or a catalyst system comprising a transition metal compound of the general formula M(R).sub.l (OR').sub.m X.sub.n-(l+m), an aluminoxane and an organic compound having at least 2 hydroxyl groups.
    Type: Grant
    Filed: August 14, 1991
    Date of Patent: January 18, 1994
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Masahiro Kakugo, Tatsuya Miyatake, Yoshio Kawai, Akinobu Shiga, Kooji Mizunuma
  • Patent number: 5278118
    Abstract: Catalysts for the preparation of copolymers of ethylene and/or alpha-olefins and optionally dienes, are obtained by reacting an Al-alkyl with a solid catalytic component comprising:(A) a magnesium compound containing at least an Mg-halogen bond;(B) a halogenated compound of at least partly trivalent Ti or V, containing at least a Ti--OR or V--OR bond, wherein the Mg/Ti(V), halogen/Ti(V), halogen/Mg and OR/Ti(V) atomic ratios are within determined ranges; and(C) an electron-donor compound.Elastomeric copolymers endowed with improved tension set values are obtained with said catalysts.
    Type: Grant
    Filed: April 8, 1992
    Date of Patent: January 11, 1994
    Assignee: Ausimont, S.p.A.
    Inventors: Illaro Cuffiana, Roberto Fabbri, Gian F. Margelli, Umberto Zucchini
  • Patent number: 5275993
    Abstract: An olefin polymerization catalyst which is obtained by contacting the following components (A) and (B): component (A): a product of contacting the following components (A.sub.1) and (A.sub.2):component (A.sub.1): polyolefin powder having specific values of pore diameter, pore volume, average pore diameter and average particle diameter,component (A.sub.2): a solid component for a Ziegler catalyst comprising titanium, magnesium and a halogen as the essential components;component (B): an organoaluminum compound.The supporting state of the catalyst is improved, and a contaminant-free polymer having a satisfactorily large particle diameter without the lowering of the activity or the stereoregularity of the catalyst is successfully obtained.
    Type: Grant
    Filed: June 26, 1992
    Date of Patent: January 4, 1994
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Takashi Fujita, Kazuyo Kitagawa