Utilizing Water Or Compound Containing Hydroxy Bonded To Carbon Patents (Class 502/111)
  • Patent number: 5106805
    Abstract: The present invention relates to a process for preparing a Ziegler-Natta type catalyst based on vanadium and titanium. The process comprises (1) contacting within a liquid hydrocarbon a spheroidal support comprising (i) MgCl.sub.2 free from any Mg-C bond and (ii) an electron-donor (D1) free from labile hydrogen, successively with an electron-donor (D2) containing labile hydrogen and then with an organometallic compound capable of reducing vanadium and titanium compounds, (2) washing of the solid product with a liquid hydrocarbon and (3) then contacting the washed solid product with a vanadium compound and a titanium compound, both being soluble in the liquid hydrocarbon. The catalyst consists of spheroidal particles without fines, is very active in olefin polymerization and is particularly suitable for producing elastomeric copolymers of propylene.
    Type: Grant
    Filed: December 17, 1990
    Date of Patent: April 21, 1992
    Assignee: BP Chemicals Limited
    Inventors: Jean-Claud A. Bailly, Patrick Behue
  • Patent number: 5104837
    Abstract: A catalyst useful for polymerizing olefins is prepared by contacting a highly porous magnesium-containing aluminum oxide support with an alcohol, then contacting the resulting solid with a mixture of titanium tetrachloride and dialkyl phthalate, and then contacting the resulting solid with additional titanium tetrachloride.
    Type: Grant
    Filed: March 16, 1990
    Date of Patent: April 14, 1992
    Assignee: Phillips Petroleum Company
    Inventors: Gil R. Hawley, Max P. McDaniel
  • Patent number: 5100849
    Abstract: A process for producing a catalyst component for olefin polymerization is provided, which process comprises spraying a solution of a magnesium compound e.g. MgCl.sub.2 and an alcohol such as MgCl.sub.2. nROH (wherein R is 1-10 C alkyl and n is 3-6) into a cooled spray column to obtain a spherical solid component (carrier) without any substantial vaporization of the alcohol, followed by partly drying the component for a time till a specified ratio of the alcohol/MgCl.sub.2 is attained, and then subjecting the resulting component to treatment with a titanium halide and an electron-donating component, the resulting component having a large particle diameter, without any dispersion of the solvent content in the component particles and also without any breakage of the particles when subjected to treatment with the titanium halides.
    Type: Grant
    Filed: August 28, 1990
    Date of Patent: March 31, 1992
    Assignee: Chisso Corporation
    Inventors: Shinya Miya, Masami Tachibana, Yuuji Karasawa
  • Patent number: 5098875
    Abstract: The present invention relates to a process for preparing a Ziegler-Natta type catalyst based on a vanadium compound. The process comprises sequentially contacting within a liquid hydrocarbon a spheroidal support comprising (i) MgCl.sub.2 free from any Mg-C bond and (ii) an electron-donor D1 free from labile hydrogen, an electron-donor D2 containing labile hydrogen and an organometallic compound capable of reducing a vanadium compound, (2) washing the solid product with a liquid hydrocarbon resulting from the contacting, and (3) contacting the washed solid product with one or more vanadium compounds soluble in the liquid hydrocarbon, comprising halogen atoms and alkoxy radical, both being bonded to the same or different vanadium atoms. The catalyst which consists of spheroidal particles without fines, is very active in olefin polymerization and is particularly suitable for producing elastomeric copolymers of propylene.
    Type: Grant
    Filed: December 17, 1990
    Date of Patent: March 24, 1992
    Assignee: BP Chemicals Limited
    Inventors: Jean-Claude A. Bailly, Patrick Behue
  • Patent number: 5091353
    Abstract: An improved process for producing an ethylene copolymer composed of a major proportion of ethylene and a minor proportion of an alpha-olefin having 3 to 10 carbon atoms and having a density of 0.910 to 0.945 g/cm.sup.3 and an ethylene content of 85 to 99.5 mole %. The use of a titanium catalyst component (A) which meets a parametric combination of specific requirements is essential in this process. The process can industrially advantageously give a low to medium density ethylene copolymer of high quality with high productivity while advantageously circumventing the operational troubles which have been difficult to avoid by conventional processes.
    Type: Grant
    Filed: October 17, 1989
    Date of Patent: February 25, 1992
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Mamoru Kioka, Norio Kashiwa
  • Patent number: 5086025
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the slurry or liquid phase polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 10 to about 50 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an aluminum trialkyl solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added. The resulting material can either be used in this slurry state for slurry polymerization or can be used for liquid phase polymerization of olefins.
    Type: Grant
    Filed: August 14, 1990
    Date of Patent: February 4, 1992
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 5081088
    Abstract: Ziegler-Natta-type catalyst systems contain as active constituentsa) atitanium-containing solid component which contains titanium, magnesium, halogen and a norbornadienedicarboxylate of the formula I ##STR1## as electron donor, where R.sup.1 and R.sup.2 are each C.sub.1 -C.sub.8 -alkyl or 5- to 7-membered cycloalkyl which in turn can carry C.sub.1 -C.sub.10 -alkyl groups,b) an aluminum component andc) another electron donor component,and are particularly suitable for preparing polypropylene and copolymers of propylene with minor amounts of other .alpha.-olefins with 2 to 8 carbon atoms.
    Type: Grant
    Filed: September 20, 1990
    Date of Patent: January 14, 1992
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Koelle, Juergen Kerth
  • Patent number: 5070051
    Abstract: A solid catalyst component for the low-pressure polymerization of ethylene and C.sub.3 -C.sub.10 alpha-olefins into very high molecular weight polyolefins is in the form of a spherical granular solid having a surface area of between 20 and 40 m.sup.2 /g, a mean pore radius of between 5,000 and 40,000 .ANG. and a porosity of between 40 and 90 vol %, and is definable by the following formula (in atomic proportions:X (1), Mg (1-8), Al (0.2-0.8), Cl (5-20), (Et+OEt+OR) (1-3);where: X=Hf or Zr; Et=ethyl group; OEt=ethoxy group; and OR=alkoxy group containing from 2 to 8 carbon atoms in the linear or branched alkyl portion.Such a catalyst component is obtained by preparing a solid spherical granular support by spray-drying an ethanolic solution of magnesium chloride, reacting said support with a hafnium or zirconium alkoxide or halogenalkoxide, and finally reacting the thus treated support with an alkyl aluminum chloride.
    Type: Grant
    Filed: February 22, 1991
    Date of Patent: December 3, 1991
    Assignee: Enichem Anic S.p.A.
    Inventors: Francesco Masi, Angelo Moalli, Renzo Invernizzi, Francesco Menconi, Cesare Ferrero, Stefano Malquori, Lia Barazzoni, Mario Polesello
  • Patent number: 5064798
    Abstract: This invention provides new supported catalyst compositions for the polymerization of 1-olefins, together with processes for preparing and using the catalysts. The catalyst compositions include two catalyst components. The first catalyst component is formed by reacting a halogen-containing compound of the formula: H.sub.a M.sup.1 X.sup.1.sub.b R.sup.1.sub.(c-b-a) wherein M.sup.1 is boron, carbon, silicon or mixtures thereof; X.sup.1 is Cl, Br or mixtures thereof; R.sup.1 is a hydrocarbyl or alkoxy radical; with a mixture produced by contacting a finely divided porous inorganic oxide support in an inert solvent with a solution made by combining a magnesium dihydrocarbyloxide dissolved in an inert solvent, and of the formula: Mg(OR.sup.2).sub.2 wherein R.sup.2 is a hydrocarbyl radical, with a transition metal hydrocarbyloxide of the formula: M.sup.2 (OR.sup.3).sub.y wherein M.sup.2 is a transition metal from Group IVB, VB, and VIB of the Periodic Table; and R.sup.3 is a hydrocarbyl radical.
    Type: Grant
    Filed: March 12, 1990
    Date of Patent: November 12, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 5064797
    Abstract: A process for producing a polyolefin having a multimodal molecular weight distribution wherein the polymerization is conducted in the presence of hydrogen and a catalyst system containing aluminoxane and at least two different metallocenes each having different olefin polymerization termination rate constants in the presence of hydrogen, and the process of producing the catalyst system.
    Type: Grant
    Filed: March 6, 1990
    Date of Patent: November 12, 1991
    Assignee: Phillips Petroleum Company
    Inventor: Phil M. Stricklen
  • Patent number: 5061667
    Abstract: A catalytic component for olefin polymerization, produced by a process which comprises causing (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl group, an aryl group, or a cycloalkyl group each having 1 to 20 carbon atoms and X for a halogen atom], and (C) a compound represented by the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M for a boron, carbon, aluminum, silicon, or phorphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, m for the valency of M, and m>n.gtoreq.
    Type: Grant
    Filed: August 29, 1990
    Date of Patent: October 29, 1991
    Assignee: Tog Nenryo Kogyo KK (Tonen Corporation)
    Inventors: Masahide Murata, Seizaburo Kanazawa, Hiroyuki Furuhashi, Kouji Maruyama, Masafumi Imai, Hiroshi Ueno
  • Patent number: 5045517
    Abstract: Syndiotactic polymers of vinyl aromatic monomers are prepared by conducting the polymerization in the presence of a catalytic amount of the reaction product of polymethylaluminoxane and a cyclopentadienyl/titanium complex.
    Type: Grant
    Filed: January 5, 1990
    Date of Patent: September 3, 1991
    Assignee: The Dow Chemical Company
    Inventors: Richard E. Campbell, Jr., John G. Hefner
  • Patent number: 5045612
    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: April 18, 1990
    Date of Patent: September 3, 1991
    Assignee: The Dow Chemical Company
    Inventors: Joseph G. Schell, Jr., Larry A. Meiske, Gary R. Marchand
  • Patent number: 5032562
    Abstract: There is disclosed a supported olefin polymerization catalyst composition comprising a precursor and a catalyst activator. The precursor comprises a magnesium compound, e.g., dibutylmagnesium, a cyclopentadienyl group-containing zirconium compound, and a titanium and/or a vanadium compound, e.g., TiCl.sub.4, and an organic compound, e.g., an alcohol. The catalyst activator is a mixture of a conventional Ziegler/Natta co-catalyst and a zirconium sites activator, e.g., methylaluminumoxane. The catalyst is used in the presence of small amounts of hydrogen to produce polymers having multimodal molecular weight distribution in a single reactor.
    Type: Grant
    Filed: December 27, 1989
    Date of Patent: July 16, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Frederick Y. Lo, Thomas E. Nowlin, Pradeep P. Shirodkar
  • Patent number: 5024982
    Abstract: Method for making crystalline polymerization catalysts is disclosed which comprises contacting the soluble complex prepared from the combination of a metal dihalide and a transition metal compound with a particulate material comprising silica to produce a solid, and then reacting the solid with an organoaluminum halide. The resulting catalyst component can be further contacted with a halide ion exchanging source selected from halides of Groups IVA and VA. Novel catalysts prepared in accordance with the invention method, polymerization processes therewith and novel polymers, having high bulk density, low levels of polymer fines, and well defined particle size and shape are also disclosed.
    Type: Grant
    Filed: December 14, 1988
    Date of Patent: June 18, 1991
    Assignee: Phillips Petroleum Company
    Inventors: Gil P. Hawley, Max P. McDaniel
  • Patent number: 5023222
    Abstract: A catalyst for producing styrene-based polymers having mainly syndiotactic configuration which comprises (A) a titanium compound and (B) a contact product of a methyl group-containing organoaluminum compound and water, wherein the contact product (B) has a high magnetic field component of not more than 50% in the methyl proton signal region due to an aluminum-methyl group (Al-CH.sub.3) bond as determined by the proton nuclear magnetic resonance absorption method.
    Type: Grant
    Filed: October 1, 1990
    Date of Patent: June 11, 1991
    Assignee: Idemitsu Kosan Company Limited
    Inventors: Hiroshi Maezawa, Norio Tomotsu, Masahiko Kuramoto
  • Patent number: 5021381
    Abstract: This invention reveals a technique for preparing syndiotactic 1,2-polybutadiene latex. It more specifically discloses a process for synthesizing syndiotactic 1,2-polybutadiene latex by polymerizing 1,3-butadiene in an aqueous medium in the presence of (1) at least one emulsifier, (2) a catalyst emulsion composition which is prepared by a microfluidization or microemulsification process, and (3) at least one member selected from the group consisting of carbon disulfide and phenyl isothiocyanate. Such syndiotactic 1,2-polybutadiene latices can be utilized in preparing blends of syndiotactic 1,2-polybutadiene with rubbers which are prepared by emulsion polymerization.
    Type: Grant
    Filed: November 13, 1989
    Date of Patent: June 4, 1991
    Assignee: The Goodyear Tire & Rubber Company
    Inventors: Gary L. Burroway, George F. Magoun, Ramesh N. Gujarathi
  • Patent number: 5008228
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the slurry or liquid phase polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 10 to about 50 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an aluminum trialkyl solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added. The resulting material can either be used in this slurry state for slurry polymerization or can be used for liquid phase polymerization of olefins.
    Type: Grant
    Filed: March 29, 1988
    Date of Patent: April 16, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 5006500
    Abstract: A high activity alumoxane-metallocene supported catalyst for the polymerization of 1-olefins prepared by reacting undehydrated silica gel with a mixture of trimethylaluminum and triisobutylaluminum to produce a silica-alumoxane product which is then reacted with a Group IVB and/or Group VB metallocene to produce an active catalyst which may be obtained in powder form, suitable for use in gas or slurry phase reactors, by a removal of solvents and drying.
    Type: Grant
    Filed: October 16, 1989
    Date of Patent: April 9, 1991
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 5001099
    Abstract: The present invention disclosure is directed to a catalyst comprising the reaction product of:(a) a silicon-containing compound having the structural formula R.sub.n-4 SiX.sub.n, where R is C.sub.1 -C.sub.10 hydrocarbyl; X is halogen; and n is an integer of 1 to 4;(b) a magnesiumdialkyl having the structural formula R.sup.1 R.sup.2 Mg, where R.sup.1 and R.sup.2 are the same or different and are C.sub.2 -C.sub.10 alkyl;(c) an alcohol having the structural formula R.sup.3 OH, where R.sup.3 is C.sub.1 -C.sub.10 hydrocarbyl;(d) a halide-containing metal compound, said metal selected from the group consisting of titanium, zirconium and vanadium;(e) an aluminum alkoxide having the structural formula A1(OR.sup.5).sub.3, where R.sup.5 is C.sub.2 -C.sub.
    Type: Grant
    Filed: October 25, 1989
    Date of Patent: March 19, 1991
    Assignee: Quantum Chemical Corporation
    Inventor: Javan Shelly
  • Patent number: 4988655
    Abstract: A catalyst useful in the polymerization of olefinic compounds and particularly 4-methyl-1-pentene is disclosed along with its method of preparation and use. The catalyst is prepared by (a) forming a first component by reacting reactants comprising a magnesium dihalide, a phenol, and alkylbenzoate, and a titanium tetrahydrocarbyloxide; (b) reacting the first component with an organoaluminum halide compound to produce a solid product; and (c) then contacting the resulting solid product with an activating liquid comprising titanium tetrachloride and trichlorosilane in a confined zone under pressure of at least 70 psi.
    Type: Grant
    Filed: November 30, 1989
    Date of Patent: January 29, 1991
    Assignee: Phillips Petroleum Company
    Inventors: Kent E. Mitchell, Gil R. Hawley, Don W. Godbehere
  • Patent number: 4980330
    Abstract: A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent, a mixture of (A) an inorganic oxide, (B) an organomagnesium material, (C) an organic hydroxyl-containing material, (D) a reducing halide source, and (E) a transition metal compound.
    Type: Grant
    Filed: November 30, 1989
    Date of Patent: December 25, 1990
    Assignee: The Dow Chemical Company
    Inventors: Gary R. Marchand, Ricardo Fuentes, Jr., William M. Coleman, III
  • Patent number: 4980329
    Abstract: Disclosed is a component for a catalyst for the polymerization of alpha-olefins to stereoregular polymers having narrow molecular weight distribution. The product is formed by the reaction of a solid catalyst-forming component comprising (1) a Ti compound having at least one Ti-halogen bond and (2) optionally, an electron-donor compound, supported on an anhydrous Mg dihalide in active form, with certain amounts of an organic compound (AH) containing at least one active hydrogen atom, in the presence of a liquid medium which is inert with respect to the Ti compound and the other components of the catalyst component, and which has a dielectric constant greater than 2 at 20.degree. C.Catalysts comprising the reaction product of the solid catalyst component prepared as above described, with an Al-alkyl compound and an electron-donor compound are also disclosed.
    Type: Grant
    Filed: May 15, 1989
    Date of Patent: December 25, 1990
    Assignee: Himont Incorporated
    Inventors: Pier C. Barbe, Enrico Albizzati, Umberto Giannini, Giovanni Baruzzi, Luciano Noristi
  • Patent number: 4978730
    Abstract: A process for producing styrene-based polymers having mainly syndiotactic configuration in the presence of a catalyst comprising (A) a titanium compound and (B) a contact product of a methyl group-containing organoaluminum compound and water, wherein the contact product (B) has a high magnetic field component of not more than 50% in the methyl proton signal region due to an aluminum-methyl group (Al--CH.sub.3) bond as determined by the proton nuclear magnetic resonance absorption method.According to this process, styrene-based polymers having mainly syndiotactic configuration can be efficiently and economically produced.
    Type: Grant
    Filed: November 21, 1988
    Date of Patent: December 18, 1990
    Assignee: Idemitsu Kosan Company Limited
    Inventors: Hiroshi Maezawa, Norio Tomotsu, Masahiko Kuramoto
  • Patent number: 4970184
    Abstract: A catalyst for the copolymerization of ethylene by the gas-phase fluidized-bed method is prepared by a process in which a titanium-containing and magnesium-containing active component, reacted with an alcohol as a complexing agent, is applied to a finely divided silica from homogeneous solution, in the presence of a polysiloxane, by evaporating the solvent, and the resulting homogeneous catalyst intermediate is then preactivated by treatment with the alkylaluminum compound and the Lewis base in an inert hydrocarbon solution, and the copolymers prepared using the above catalyst are employed for the production of films exhibiting little blocking.
    Type: Grant
    Filed: May 3, 1989
    Date of Patent: November 13, 1990
    Assignee: BASF Aktiengesellschaft
    Inventors: Eckard Schauss, Heinz Vogt, Rainer Hemmerich, Guenther Schweier, Rudolf Mueller-Mall
  • Patent number: 4960741
    Abstract: A process of the Ziegler-Natta type is prepared using a preactivated support containing (A) from 80 to 95 mol % of magnesium chloride and (B) 5 to 20 mol % of at least one electron donor compound which contains no labile hydrogen and no ester function; the preactivated support consisting of spherical particles having a mass average diameter, Dm of 10 to 100 microns and a particle size distribution Dm/Dn of less than 2. The catalyst is prepared by (i) treating the preactivated support with at least one electron donor compound containing labile hydrogen, (ii) treating the resulting activated support with at least one ester of an aromatic acid, (iii) impregnating the treated support with titanium tetrachloride and (iv) after washing the impregnated catalyst activating it with titanium tetrachloride. The catalyst has a high titanium content and a high activity when used to polymerize olefins.
    Type: Grant
    Filed: February 22, 1989
    Date of Patent: October 2, 1990
    Assignee: BP Chemicals Limited
    Inventors: Jean-Claude A. Bailly, Stylianos Sandis
  • Patent number: 4960743
    Abstract: A method for the production of a catalyst carrier for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX [wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X stands for a halogen atom], and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n [wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M stands for a boron, carbon, aluminum, silicon, or phosphorus atom, R.sup.1 stands for a hydrocarbon group having 1 to 20 carbon atoms, and m stands for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied], to contact (D) a halogen-containing alcohol.
    Type: Grant
    Filed: November 18, 1988
    Date of Patent: October 2, 1990
    Assignee: Toa Nenryo Kogyo K.K.
    Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno
  • Patent number: 4959336
    Abstract: A process is disclosed for improving the productivity of a polymerization catalyst formed from a magnesium ethoxide. The process comprises treating the magnesium ethoxide with a silane alkoxide at or above the temperature at which any alcohol which may be bound to the ethoxide dissociates from the alkoxide prior to subjecting the magnesium ethoxide to metathesis.
    Type: Grant
    Filed: April 7, 1989
    Date of Patent: September 25, 1990
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 4954470
    Abstract: A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a chlorinated alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with an activator. The resulting catalyst composition has high polymerization activity in the polymerization of C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties in the copolymerization of ethylene with the higher alpha-olefins.
    Type: Grant
    Filed: December 21, 1988
    Date of Patent: September 4, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Thomas E. Nowlin, Kenneth G. Schurzky
  • Patent number: 4948770
    Abstract: Disclosed is a method for making crystalline magnesium halide particles usable for preparing catalyst and usable in the polymerization of alpha olefins having the formula MgnEmXp * y ROH wherein y is a value greater than 0 and up to 12, and which comprises the steps of:contacting the components of a magnesium compound of the formula MgnEmXp, wherein Mg is the magnesium component, n is a value from 0.
    Type: Grant
    Filed: August 8, 1988
    Date of Patent: August 14, 1990
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 4937217
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 6 to about 20 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an trialkyl aluminum solution, preferably a mixed trimethylaluminum-triethylaluminum solution, to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added and the resulting material dryed to free flowing powder. The dry free flowing powder may then be used as a supported metallocene alumoxane catalyst complex for gas phase or liquid phase polymerization of olefins.
    Type: Grant
    Filed: October 27, 1988
    Date of Patent: June 26, 1990
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 4935397
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the high pressure polymerization of olefins. The invention particularly relates to the use of silica gel having a particle size less than 10 microns containing from about 5 to about 20 per cent by weight absorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an aluminum trialkyl solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added and the resulting material dried to free flowing powder. The dried free flowing powder may then be used as a catalyst for high pressure polymerization of olefins.
    Type: Grant
    Filed: September 28, 1988
    Date of Patent: June 19, 1990
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 4925821
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 6 to about 20 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to a solution, of trialkylaluminum to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the majority of the alumoxane component requirement of the catalyst system. An alkylalumoxane coated silica gel is formed to which a trimethylaluminum treated metallocene may be added and the resulting material dried to free-flowing powder. The dry free flowing powder may then be used as a supported metallocene alumoxane catalyst complex for gas phase or liquid phase polymerization of olefins.
    Type: Grant
    Filed: November 8, 1988
    Date of Patent: May 15, 1990
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 4918037
    Abstract: A catalyst component for polymerization catalyst of .alpha.-olefines, the polymerization catalyst comprising an organoaluminum compound, an electron donor, as well as the solid catalyst component which is obtained when a compound containing magnesium reacts with a titanium halogen compound. A method for producing the catalyst component is also provided. The catalyst component is manufactured by reacting with a titanium halogen compound in the presence of an internal electron donor, a solid catalyst component which has been produced by the steps of(a) reacting a magnesium alkyl compound with a chlorinating compound,(b) dissolving the chlorinated magnesium alkyl compound in alcohol, after possible washing,(c) adding into the solution, magnesium silicate which has not been calcinated,(d) adding the mixture obtained in step (c) into a cold medium, to precipitate the magnesium compound into and onto the magnesium silicate carrier, and(e) separating the thus-obtained solid carrier component.
    Type: Grant
    Filed: March 8, 1989
    Date of Patent: April 17, 1990
    Assignee: Neste Oy
    Inventor: Hanneli Seppanen
  • Patent number: 4918039
    Abstract: A metathesis polymerization catalyst composition comprising a binuclear catalyst, wherein said binuclear catalyst is a mixture of at least two transition metal components, wherein a first transition metal component is a halide complex of tungsten, an oxyhalide complex of tungsten or a mixture thereof and a second transition metal component is a halide complex of a transition metal selected from the group consisting of high valent transition metals belonging to Groups IV or V of the Periodic Table, from about 1 to about 3 moles of phenolic compound per mole of tungsten component, activated by a metathesis catalyst activator and containing a rate moderator.
    Type: Grant
    Filed: September 21, 1988
    Date of Patent: April 17, 1990
    Assignee: Hercules Incorporated
    Inventor: Andrea E. Martin
  • Patent number: 4914069
    Abstract: Solid catalyst components for use in the polymerization of olefins and having improved activity and selectivity are prepared by:(a) halogenating a magnesium compound containing at least one aryloxy, alkyl carbonate or alkyloxy group with a first halide of tetravalent titanium and a first electron donor;(b.sub.1) contacting the resulting halogenated product with a second halide of tetravalent titanium; and(c) washing a resulting treated halogenated product with an inert hydrocarbon liquid, wherein a second electron donor is used in step (a) or step (b.sub.1) and in that the product of step (b.sub.1) is contacted in a step b.sub.2 with a third halide of tetravalent titanium at a temperature of 40.degree. to 140.degree. C. and thereafter the treated product is washed in step (c).
    Type: Grant
    Filed: August 8, 1988
    Date of Patent: April 3, 1990
    Assignee: Shell Oil Company
    Inventors: Robert C. Job, Steven M. Nestlerode
  • Patent number: 4912075
    Abstract: This invention relates to a process for preparing a supported metallocene alumoxane catalyst for use in the gas phase polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 6 to about 10 percent by weight adsorbed water as the catalyst support material. It has been found that such silica gel may be safely added to an aluminum trialkyl solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane component of the catalyst system. An alumoxane coated silica gel is formed to which a metallocene may be added and the resulting material dried to free flowing powder. The dry free flowing powder may then be used as a supported metallocene alumoxane catalyst complex for gas phase polymerization of olefins.
    Type: Grant
    Filed: December 17, 1987
    Date of Patent: March 27, 1990
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 4910272
    Abstract: A catalyst for polymerizing olefins is the product resulting from mixing in an inert hydrocarbon diluent, a mixture of (A) an inorganic oxide, (B) an organomagnesium material, (C) an organic hydroxyl-containing material, (D) a reducing halide source, and (E) a transistion metal compound.
    Type: Grant
    Filed: November 29, 1988
    Date of Patent: March 20, 1990
    Assignee: The Dow Chemical Company
    Inventors: Gary R. Marchand, Ricardo Fuentes, Jr., William M. Coleman, III
  • Patent number: 4904631
    Abstract: This invention relates to a supported vanadium-alumoxane catalyst for use in gas and liquid polymerization of olefins. The invention particularly relates to the use of silica gel containing from about 6 to about 20 percent by weight adsorbed water as the catalyst support material. The particle size of the silica gel is generally between about 0.1 and 200.0 .mu.u. Such silica gel may be safely added to a trialkylaluminum solution to form by direct reaction with the adsorbed water content of the silica gel catalyst support material the alumoxane cocatalyst component of the catalyst system. An alumoxane coated silica gel is formed to which a vanadium compound is added and the resulting material dried to a free flowing powder. The dry free flowing powder may then be used as a supported vanadium alumoxane catalyst complex for the polymerization of olefins.
    Type: Grant
    Filed: November 8, 1988
    Date of Patent: February 27, 1990
    Assignee: Exxon Chemical Patents, Inc.
    Inventor: Main Chang
  • Patent number: 4876230
    Abstract: A process is disclosed for improving the morphology of a polymerization catalyst formed from a magnesium alkoxide with bound alcohol. The process comprises treating the magnesium alkoxide with an unreactive solvent at or above the temperature at which the alcohol dissociates from the alkoxide prior to subjecting the magnesium alkoxide to metathesis.
    Type: Grant
    Filed: September 6, 1988
    Date of Patent: October 24, 1989
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 4874737
    Abstract: A process is disclosed for improving the productivity of a polymerization catalyst formed from a magnesium alkoxide which normally undergoes poor metathesis towards production of magnesium chloride. The process comprises treating the magnesium alkoxide with a silane alkoxide at or above the temperature at which the alcohol which is formed dissociates from the alkoxide prior to subjecting the magnesium alkoxide to metathesis.
    Type: Grant
    Filed: September 6, 1988
    Date of Patent: October 17, 1989
    Assignee: Shell Oil Company
    Inventor: Robert C. Job
  • Patent number: 4863886
    Abstract: MgO treated with an organic acid, e.g., 2-ethyoxybenzoic acid, is used as a support for an Al-Ti Ziegler catalyst in which the Ti component is the product of an alkanol having 5 to 12 carbon atoms and TiCl.sub.4 to give HDPE with narrow MWD and large particle size for injection molding.
    Type: Grant
    Filed: December 29, 1987
    Date of Patent: September 5, 1989
    Assignee: Mobil Oil Corporation
    Inventor: John T. T. Hsieh
  • Patent number: 4864072
    Abstract: The hydrocarbon solvent contained in a solution of an organoaluminum compound is recovered by a process comprising contacting the solution with water at a volume ration of from about 3:1 to about 8:1. Preferably, the solvent is n-hexane, the organoaluminum compound is triethylaluminum sesquichloride, and the solution has been used in a process for preparing olefin polymerization catalysts.
    Type: Grant
    Filed: July 1, 1988
    Date of Patent: September 5, 1989
    Assignee: Phillips Petroleum Company
    Inventor: Charles A. Drake
  • Patent number: 4855271
    Abstract: A catalyst and its use in polymerizing olefins, wherein the catalyst is prepared by contacting a support with a compound of titanium and/or vanadium.
    Type: Grant
    Filed: June 22, 1987
    Date of Patent: August 8, 1989
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Shirley J. Martin
  • Patent number: 4849389
    Abstract: A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a hydroxyl group-containing compound, e.g., an alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) removing the non-polar solvent to obtain a dry-flowing powder; and, (5) activating the powder with trimethylaluminum. The resulting catalyst composition is extremely active in polymerizing C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefin incorporation properties.
    Type: Grant
    Filed: January 14, 1988
    Date of Patent: July 18, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Thomas E. Nowlin, Kenneth G. Schurzky
  • Patent number: 4843049
    Abstract: A catalyst component is in the form of a granular spherical solid with at least 80% of the granules between 30 and 40 microns in size, a service area of 15 to 30 m.sup.2 /g and a porosity of 40 to 80 volumes % and definable (in atomic proportions) by the formula: ##STR1## where Et denotes the ethyl group; OEt denotes the ethoxy group and OR' is an alkoxy group containing from 1 to 8 carbon atoms in the alkyl portion, and in which the ratio of trivalent titanium to the sum of trivalent and tetravelent titanium is in the range from 0.8/1 to 1/1.
    Type: Grant
    Filed: February 1, 1988
    Date of Patent: June 27, 1989
    Inventors: Renzo Invernizzi, Francesco Masi, Angelo Moalli
  • Patent number: 4833111
    Abstract: A supported alpha-olefin polymerization catalyst composition is synthesized by reacting (1) a slurry of a solid catalyst carrier in a non-polar solvent, e.g., hexane, with a dialkyl organomagnesium composition; (2) contacting the slurry of step (1) with a hydroxyl group-containing compound, e.g., an alcohol; (3) contacting the slurry of step (2) with at least one transition metal compound; (4) contacting the slurry of step (3) with a halogenated alkyl aluminum compound, e.g., ethyl aluminum dichloride, and, (5) activating the product of step (5) with trimethylaluminum. The resulting catalyst composition is extremely active in polymerizing C.sub.2 -C.sub.10 alpha-olefins and exhibits very good higher (C.sub.3 -C.sub.10) alpha-olefins incorporation properties.
    Type: Grant
    Filed: January 14, 1988
    Date of Patent: May 23, 1989
    Assignee: Mobil Oil Corporation
    Inventor: Thomas E. Nowlin
  • Patent number: 4829034
    Abstract: The invention concerns a procedure for manufacturing solid catalyst components for catalysts serving polymerization of alpha-olefines, having a solid carrier substance containing an organic or inorganic magnesium compound and treated with a titanium halide and optionally with an electron donor compound. The magnesium compound or the mixture of magnesium compound and electron donor compounds is sprayed in molten state into a chamber or volume which has been cooled to a temperature at which the catalyst component will solidify from the melt in the form of particles with generally spherical shape, without any substantial evaporation of solvents.
    Type: Grant
    Filed: February 5, 1988
    Date of Patent: May 9, 1989
    Assignee: Neste Oy
    Inventors: Eero Iiskolan, Jukka Koskinen
  • Patent number: 4814309
    Abstract: Catalyst for polymerization of .alpha.-olefines, comprising an organoaluminum compound, an electron donor, as well as a solid catalyst component which is obtained when a compound containing magensium reacts with a titanium halogen compound. A method for producing the catalyst is also provided. The catalyst component is manufactured by reacting with a titanium halogen compound in the presence of an internal electron donor, a solid catalyst component which has been produced by the steps of(a) reacting a magnesium alkyl compound with a chlorinating compound,(b) dissolving the chlorinated magnesium alkyl compound in alcohol, after possible washing,(c) adding into the solution, magnesium silicate which has been calcinated by heating at about 200.degree.-600.degree. C.,(d) adding the mixture obtained in step (c) into a cold medium, to precipitate the magnesium compound into and onto the magnesium silicate carrier, and(e) separating the thus-obtained solid carrier component.
    Type: Grant
    Filed: September 29, 1987
    Date of Patent: March 21, 1989
    Assignee: Neste Oy
    Inventors: Hanneli Seppanen, Outi Krause
  • Patent number: 4814311
    Abstract: A method for the production of a catalyst component for use in the polymerization of an olefin, which method comprises causing a magnesium-containing solid obtained by contact of (A) magnesium metal, (B) a halogenated hydrocarbon represented by the general formula, RX, wherein R stands for an alkyl, aryl, or cycloalkyl group having 1 to 20 carbon atoms and X for a halogen atom, and (C) a compound of the general formula, X.sub.n.sup.1 M(OR.sup.1).sub.m-n, wherein X.sup.1 stands for a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms, M for a boron, carbon, silicon, aluminum, or phosphorus atom, R.sup.1 for a hydrocarbon group having 1 to 20 carbon atoms, and m for the valency of said atom M, providing that m>n.gtoreq.0 is satisfied, to contact (D) a halogen-containing alcohol and then contact (E) a titanium compound.
    Type: Grant
    Filed: December 14, 1987
    Date of Patent: March 21, 1989
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Masahide Murata, Masafumi Imai, Hiroyuki Furuhashi, Kouji Maruyama, Hiroshi Ueno