Contains Elemental Transition Metal Or A Non-oxide Compound Of A Transition Metal Patents (Class 526/96)
  • Patent number: 5034364
    Abstract: An olefin, particularly alpha-olefin, polymerization catalyst composition, supported on a refractory oxide support comprises two chromium specie: (1) CrO.sub.3 or any chromium compound calcinable to CrO.sub.3 ; and (2) at least one silylchromate compound. The composition is prepared by sequentially depositing specie (1) and (2) onto the same support.
    Type: Grant
    Filed: November 9, 1989
    Date of Patent: July 23, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Bohumil V. Kral, Grace O. Tsien, Chisung Wu
  • Patent number: 5032651
    Abstract: Olefinic polymer exhibiting high environmental stress crack resistance are produced by contacting the olefin charge stock in a single reactor with a compatible mix of two transition metal catalyst systems. One component of the catalyst system comprises chromium oxide supported on an aluminophosphate material. Hydrogen can be used as adjuvant for the hexavalent chromium component of the catalyst mixture. The second catalyst component consists essentially of a beta-stabilized tetrahydrocarbyl zirconium compound supported on inorganic support material. The catalysts can be premixed before use in the reactor, or can be added to the reactor separately. A suitable cocatalyst can be utilized.
    Type: Grant
    Filed: May 29, 1990
    Date of Patent: July 16, 1991
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Paul D. Smith
  • Patent number: 4665263
    Abstract: Olefin polymerization catalysts are described which are based on solid inorganic oxides (such as silica) and polychromium complexes (such as octakis(.mu.-trimethylsilylmethyl) tetrachromium(II)). Linear low density ethylene homopolymers with specific short chain branching as well as polymerization processes to make these polymers using the specific catalyst described are also disclosed.
    Type: Grant
    Filed: March 21, 1986
    Date of Patent: May 12, 1987
    Assignee: Phillips Petroleum Company
    Inventors: Paul D. Smith, Eric T. Hsieh
  • Patent number: 4622371
    Abstract: Density and flexural modulus of olefin polymers can be controlled using a chromium catalyst on a iron and aluminum phosphate and/or polyphosphate gel base.
    Type: Grant
    Filed: January 4, 1985
    Date of Patent: November 11, 1986
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4619980
    Abstract: Polymerization catalyst consisting essentially of treated silica support and zerovalent chromium compound is provided, as well as process for preparation and polymerization process with the invention catalyst. Silica treatment involves contacting a predominantly silica-containing support with at least one compound selected from the group consisting of Group IIA oxide or compounds convertible to the oxide form, a Group VA or VB oxide or compounds convertible to the oxide form or sulfuric acid, and calcining prior to contacting the treated support with a zerovalent chromium compound, thereby producing an active polymerization catalyst.
    Type: Grant
    Filed: April 1, 1985
    Date of Patent: October 28, 1986
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Paul D. Smith
  • Patent number: 4590246
    Abstract: A method of polymerizing olefins comprising contacting an olefin or mixture of olefins with a catalyst prepared with large pore volume zirconia-silica catalyst supports. The supports are prepared by reacting a zirconium compound of the formula M.sub.4 Zr(C.sub.2 O.sub.4).sub.4.nH.sub.2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A.sub.2 SiO.sub.3, where A is an alkali metal, in an aqueous solution at a pH equal to at least 11, then adding an acidic solution to a pH of about 5-9 to produce a hydrocogel. The hydrocogel is then aged and washed free of soluble by-products with an aqueous washing agent. Water is removed from the washed hydrocogel by azeotropic distillation or by washing with a water miscible solvent and then calcining the resulting xerocogel.
    Type: Grant
    Filed: January 27, 1982
    Date of Patent: May 20, 1986
    Assignee: Norchem, Inc.
    Inventors: Robert A. Dombro, William Kirch
  • Patent number: 4547557
    Abstract: A silica-titania cogel is produced in a two-step process wherein in the first step an alkyl polysilicate and/or a tetraalkyl silicate is partially hydrolyzed in an alkaline organic solvent using insufficient water to complete hydrolysis and thereafter a tetraalkyl titanate and an excess of water are added to complete the hydrolysis. The resulting product is as good or better than silica-titania cogels made by expensive prior art techniques and offers the advantage of not requiring washing step to remove alkali metal ions and thus also does not require an azeotrope drying step to remove water.
    Type: Grant
    Filed: July 9, 1984
    Date of Patent: October 15, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4540758
    Abstract: A process for the polymerization or copolymerization of an olefinically unsaturated monomer which comprises contacting the monomer with a chromium metal catalyst composition which is the product obtained by adsorbing a chromium metal complex which contains allyl hydrocarbon radicals with an inert inorganic oxide support which has --OH groups on its surface and which is free from adsorbed water, said monomer being an olefinically unsaturated monomer other than a polar vinyl monomer.
    Type: Grant
    Filed: September 15, 1975
    Date of Patent: September 10, 1985
    Assignee: Union Carbide Corporation
    Inventors: Robert N. Johnson, Frederick J. Karol
  • Patent number: 4505969
    Abstract: The present invention relates to heat sealable laminar thermoplastic films which may be heat sealed over a wide range of temperatures. The resultant heat seals exhibit a high heat seal strength. Such laminar structures comprise at least two layers of thermoplastic film, one of the layers being an oriented base layer and the other layer a heat sealable skin layer. Preferably the base layer is an alpha olefin such as polypropylene or copolymers thereof and the skin layer is preferably a linear, low-density polyethylene copolymer, comprising ethylene which has been copolymerized with another alpha olefin in the presence of a stereospecific catalyst.
    Type: Grant
    Filed: February 9, 1982
    Date of Patent: March 19, 1985
    Assignee: Mobil Oil Corporation
    Inventor: Milton L. Weiner
  • Patent number: 4442275
    Abstract: A titanium hydrocarbyloxide is solubilized by reacting with a water soluble polyhydroxy organic compound and the resulting product then combined with a strong acid to form a water soluble titanium composition which is combined with an inorganic catalyst support such as silica. The resulting composition is ideally suited as a support for a chromium olefin polymerization catalyst. The procedure results in an inexpensive way of producing a catalyst capable of giving high melt flow polymer under slurry conditions.
    Type: Grant
    Filed: September 29, 1982
    Date of Patent: April 10, 1984
    Assignee: Phillips Petroleum Company
    Inventor: Joel L. Martin
  • Patent number: 4418187
    Abstract: A process for the preparation of electrically conductive polymers by polymerizing acenaphthylene, N-vinyl-heterocyclics, eg. N-vinylcarbazole or N-vinylpyridine, or N,N-divinylaniline at from -80.degree. to +100.degree. C. in the presence of a cationtic catalyst, wherein from 1 to 50 percent by weight of an oxidizing Lewis acid, preferably FeCl.sub.3, FeBr.sub.3, SbCl.sub.5, SbF.sub.5, AsF.sub.5 or CF.sub.3 -SO.sub.3 H, or a combination of AlCl.sub.3 or TiCl.sub.4 with the said compounds or with CrO.sub.3 or OsO.sub.4 is used as the catalyst. In a preferred embodiment of the process, thin films of the monomers to be polymerized, applied to glass or to a polymeric base, preferably to a plastic film, are treated with gaseous SbCl.sub.5, SbF.sub.5 or AsF.sub.5.
    Type: Grant
    Filed: April 15, 1981
    Date of Patent: November 29, 1983
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Muench, Herbert Naarmann, Klaus Penzien
  • Patent number: 4405768
    Abstract: A catalyst suitable for olefin polymerization is produced by combining an inorganic support with a titanium polymer to produce a support for chromium-containing catalyst. The resulting chromium-containing catalyst is activated in a conventional manner. This process allows incorporation of relatively high concentrations of titanium which is beneficial in achieving high melt index values in slurry polymerization systems.
    Type: Grant
    Filed: September 24, 1982
    Date of Patent: September 20, 1983
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4369295
    Abstract: A chromium catalyst supported on a silica-containing base is prepared having chromium present in both the hexavalent state and a lower valent state by anhydrously impregnating a second chromium compound onto the base which already has a chromium compound having a different chromium valence than said second chromium compound. For instance, a silica titanium cogel containing a chromium compound calcined to give hexavalent chromium can be anhydrously impregnated with a .pi.-bonded organochromium compound such as dibenzene chromium or dicumene chromium. Resulting polymers have broad molecular weight distribution and can be made in slurry systems at a sufficiently high melt flow to be useful in applications such as blow molding of bottles and other hollow articles.
    Type: Grant
    Filed: November 3, 1981
    Date of Patent: January 18, 1983
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4345055
    Abstract: In accordance with a first embodiment of this invention, a silica xerogel is aqueously impregnated with a titanium compound which is resistant to hydrolysis. In accordance with a second embodiment of this invention, a silica hydrogel containing a titanium compound resistant to hydrolysis is dried. In this embodiment, the hydrogel preferably also contains a pore preserving agent. This invention makes possible the use of aqueous impregnation of titanium and conventional drying techniques to give a catalyst having characteristics associated with azeotrope dried silica-titanium coprecipitated catalyst. The catalysts of this invention are useful in olefin polymerization processes, particularly in the polymerization of predominantly ethylene monomer systems under slurry conditions.
    Type: Grant
    Filed: May 20, 1981
    Date of Patent: August 17, 1982
    Assignee: Phillips Petroleum Company
    Inventor: Gil R. Hawley
  • Patent number: 4331789
    Abstract: A process comprising treating silica with at least one of selenium or tellurium under nonoxidizing conditions at a temperature of at least 370.degree. C. and a subsequent second step wherein the thus-treated silica is contacted with an oxidizing ambient at a temperature within the range of 370.degree.-900.degree. C. The silica can contain a chromium compound in which case the resulting product is suitable as a catalyst for the production of higher melt flow olefin polymers suitable for such applications as injection molding, and the like requiring a relatively narrow molecular weight distribution.
    Type: Grant
    Filed: May 6, 1981
    Date of Patent: May 25, 1982
    Assignee: Phillips Petroleum Company
    Inventor: Gil R. Hawley
  • Patent number: 4325839
    Abstract: A chromium catalyst supported on a silica-containing base is prepared having chromium present in both the hexavalent state and a lower valent state by anhydrously impregnating a second chromium compound onto the base which already has a chromium compound having a differnt chromium valance than said second chromium compound. For instance, a silica titanium cogel containing a chromium compound calcined to give hexavalent chromium can be anhydrously impregnated with a .pi.-bonded organochromium compound such as dibenzene chromium or dicumene chromium. Resulting polymers have broad molecular weight distribution and can be made in slurry systems at a sufficiently high melt flow to be useful in applications such as blow molding of bottles and other hollow articles.
    Type: Grant
    Filed: December 21, 1979
    Date of Patent: April 20, 1982
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4303770
    Abstract: A new catalyst and a method of polymerizing olefins in which the catalyst is prepared (1) by forming a mixture by dispersing on a finely divided, difficult to reduce, inorganic support of silica, alumina, thoria, zirconia, titania, magnesia or mixtures of these a tetravalent or lower valent organic chromium compound, (2) calcining the mixture of (1) in an oxidizing or inert atmosphere and at an elevated temperature to produce a chromium compound on the support, (3) reacting the product of (2) with an alkyl ester of titanium, boron, vanadium or mixtures thereof or boric acid at an elevated temperature, and (4) activating the product of (3) with a dry gas that contains oxygen by heating at an elevated temperature the product of (3) in this dry gas.
    Type: Grant
    Filed: July 7, 1980
    Date of Patent: December 1, 1981
    Assignee: Chemplex Company
    Inventors: Thomas J. Pullukat, Mitsuzo Shida
  • Patent number: 4298722
    Abstract: A fractionable, elastomeric polymer of 1-butene consisting essentially of 30% to 80%, by weight, of an ether-soluble fraction having an intrinsic viscosity exceeding 1.5 and an infrared crystallinity value of about 1% to 15%; and 20% to 70%, by weight, of an ether-insoluble fraction having an infrared crystallinity value of about 20% to 55%; said polymer having an nmr isotacticity of about 20% to 50% and an intrinsic viscosity exceeding 1.5; elastomeric copolymers of 1-butene; polymer blends containing said elastomeric polymers; and a catalytic process for making said elastomeric polymers.
    Type: Grant
    Filed: March 11, 1980
    Date of Patent: November 3, 1981
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: John W. Collette, Charles W. Tullock
  • Patent number: 4279780
    Abstract: A method of preparing large pore volume zirconia-silica catalyst supports, the resulting supports and a method of polymerizing olefins comprising contacting an olefin or mixture of olefins with a catalyst prepared with these supports. The supports are prepared by reacting a zirconium compound of the formula M.sub.4 Zr(C.sub.2 O.sub.4).sub.4.nH.sub.2 O, where M is an alkali metal or ammonium ion and n equals 0 to 10, with a silicon compound of the type A.sub.2 SiO.sub.3, where A is an alkali metal, in an aqueous solution at a pH equal to at least 11, then adding an acidic solution to a pH of about 5-9 to produce a hydrocogel. The hydrocogel is then aged and washed free of soluble by-products first with water, then with aqueous ammonium nitrate and again with water. The water is removed from the washed hydrocogel by azeotropic distillation or by washing with a water miscible solvent, then residual water is removed by chemically reacting this water with a ketal of the formula RC(OR).sub.
    Type: Grant
    Filed: April 18, 1980
    Date of Patent: July 21, 1981
    Assignee: Chemplex Company
    Inventor: Robert A. Dombro
  • Patent number: 4263422
    Abstract: Alpha-olefins are polymerized in the presence of at least two independently supported catalysts, one of which is an inorganic halide supported titanium and/or vanadium Ziegler type catalyst and at least one other is inorganic oxide supported, chromium catalyst. This dual catalyst increases catalyst efficiency and/or provides more flexible control of the properties of the resulting polymers.
    Type: Grant
    Filed: December 31, 1979
    Date of Patent: April 21, 1981
    Assignee: The Dow Chemical Company
    Inventors: Kirby Lowery, Jr., Fred L. Vance, Jr.
  • Patent number: 4246139
    Abstract: A method of producing silica compositions from hydrogels in which the hydrogel is washed in a first water-soluble organic liquid to remove a principal portion of the water. The washed composition is then washed in at least one second water-soluble organic liquid and the second organic liquid is removed from the composition by venting the second organic liquid from the composition at a temperature above the critical temperature of the second organic liquid to produce a silica composition.
    Type: Grant
    Filed: September 15, 1975
    Date of Patent: January 20, 1981
    Assignee: Phillips Petroleum Company
    Inventor: Donald R. Witt
  • Patent number: 4238353
    Abstract: Olefin polymerization catalysts are prepared by depositing an organophosphoryl chromium product and a non-volatile aluminum-containing product obtained from the reaction of an aluminum alkoxide and an aluminum salt of a lower aliphatic monocarboxylic acid on an inorganic support material and heating the support material in a non-reducing atmosphere at a temperature above about 300.degree. C. up to the decomposition temperature of the support material.
    Type: Grant
    Filed: June 8, 1979
    Date of Patent: December 9, 1980
    Assignee: National Petro Chemicals Corp.
    Inventor: Anthony N. Speca
  • Patent number: 4228263
    Abstract: In the production of elastomeric polypropylene by polymerizing propylene in the presence of a catalyst system which is the reaction product of a metal oxide and and an organometallic compound of Zr, Ti or Hf under conditions such that the reaction medium contains liquid propylene, a fluid, mobile slurry of polypropylene in propylene is formed by mixing the components of the catalyst system together in the presence of the propylene to be polymerized.
    Type: Grant
    Filed: June 20, 1978
    Date of Patent: October 14, 1980
    Assignee: E. I. Du Pont de Nemours and Company
    Inventors: Edward G. Howard, Jr., Christos Sarafidis
  • Patent number: 4188471
    Abstract: A particulate catalyst support such as silica or a silica-titania cogel is impregnated with a titanium compound from a nonaqueous solution and the resulting composition heated to activation temperature and thereafter impregnated with a .pi. bonded organochromium compound. Finally the chromium-containing support is heated to reactivate same. Such catalysts are particularly suitable for polymerizing at least one mono-1-olefin containing 2 to 8 carbon atoms per molecule.
    Type: Grant
    Filed: December 4, 1974
    Date of Patent: February 12, 1980
    Assignee: Phillips Petroleum Company
    Inventors: Benny E. Nasser, Jr., Joseph A. Delap
  • Patent number: 4186260
    Abstract: A method for preparing a composition of matter comprising silica and titanium, convertible to a catalyst suitable for olefin polymerization by the addition of chromium and the process performable therewith, the preparation involving adding an alkali metal silicate to an acid containing a titanium compound, and recovering a dry gel for use as a polymerization catalyst upon the addition of chromium.
    Type: Grant
    Filed: August 1, 1978
    Date of Patent: January 29, 1980
    Assignee: Phillips Petroleum Company
    Inventor: Richard E. Dietz
  • Patent number: 4182815
    Abstract: High melt flow olefin polymers suitable for such applications as injection molding, and the like requiring a narrow molecular weight distribution are produced using a catalyst made by reducing and reoxidizing a chromium catalyst on either a titanium-silica cogel or a self-reduced silica-containing composition. In the first embodiment, a cogel formed by coprecipitating silica and titania, and containing a chromium compound, is treated in a nonoxidizing atmosphere, such as CO, hydrogen, N.sub.2 or a material decomposable to these materials, and thereafter reoxidized. In the second embodiment, a titanium-free chromium containing catalyst is first heated in air or the like to dry the catalyst and oxidize the chromium after which it is heated in an inert atmosphere wherein the composition is self-reduced to give chromium in a lower valence state. The resulting self-reduced composition is then heated in a reducing ambient and then reoxidized as in the first embodiment.
    Type: Grant
    Filed: February 6, 1979
    Date of Patent: January 8, 1980
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Melvin B. Welch
  • Patent number: 4173548
    Abstract: A highly active catalyst for polymerizing ethylene to polyethylene and copolymers of ethylene with alpha-olefins having a narrow molecular weight distribution, a method of making the catalyst and a method of polymerizing in which the catalyst is prepared by forming a mixture of a porous support of silica, alumina, zirconia, thoria or mixtures and a chromium compound and an alkyl ester of boron containing 1-7 carbon atoms in the alkyl group or a halide of boron capable of reacting with the chromium compound and activating this mixture at an elevated temperature in a fluidized bed with a substantially dry reducing gas followed by fluidizing with an oxidizing gas at an elevated temperature.
    Type: Grant
    Filed: June 12, 1978
    Date of Patent: November 6, 1979
    Assignee: Chemplex Company
    Inventors: Thomas J. Pullukat, Mitsuzo Shida, Raymond E. Hoff
  • Patent number: 4169925
    Abstract: A process for the manufacture of olefin polymers by polymerizing .alpha.-monoolefins at relatively low temperatures and relatively low olefin pressures by means of a catalyst obtained from a silicate carrier (component a), an aluminum compound (component b) and a chromium compound (component c). The catalyst is obtained by (1) in a first stage, initially (1.1) charging a particular silicate carrier (component a) with (1.2) a mixture of (1.2.1) an aluminum salt or a mixture of an aluminum salt with up to 80 mole%, based on the salt mixture, of a nickel-II salt (component b) and (1.2.2) a chromium compound (component c), this compound being chromium trioxide or a compound which is converted to chromium trioxide under the conditions of stage (2), by treatment with a solution of the mixture (1.2), and (2), in a second stage then maintaining the product, obtained from stage (1), for a certain time at a high temperature in an anhydrous oxygen-containing gas stream.
    Type: Grant
    Filed: April 28, 1978
    Date of Patent: October 2, 1979
    Assignee: BASF Aktiengesellschaft
    Inventors: Wolfgang Gruber, Hans Frielingsdorf, Robert Bachl, Guenther Schweier
  • Patent number: 4152502
    Abstract: A catalyst for the preparation of ethylene polymers having higher melt indexes comprises a silyl chromate deposited on a silica support containing both aluminum and titanium.
    Type: Grant
    Filed: April 12, 1978
    Date of Patent: May 1, 1979
    Assignee: Union Carbide Corporation
    Inventors: Isaac J. Levine, Frederick J. Karol
  • Patent number: 4150208
    Abstract: A new catalyst and method of making polymers therewith and the process of preparing the catalyst in which the catalyst is prepared by dispersing on a finely divided carrier material, particularly a difficultly reducible inorganic support such as silica, a reaction product of (1) a chromium carboxylate reactant and (2) an organic nitrogen cmpound reactant capable of forming a complex such as a chelate with the chromium and activating the resulting mixture by heating at an elevated temperature in a non-oxidizing atmosphere.
    Type: Grant
    Filed: November 14, 1977
    Date of Patent: April 17, 1979
    Assignee: Chemplex Company
    Inventor: Yu-Tang Hwang
  • Patent number: 4147849
    Abstract: A new catalyst and a method of polymerizing olefins in which the catalyst is prepared by forming a mixture by dispersing on a finely divided, difficult to reduce, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia and mixtures or composites thereof, an organic chromium compound pyrolytically decomposable in the substantial absence of oxygen to deposit a catalytically active residue along with a carbon residue as a contaminant on the support, then activating the mixture by subjecting the mixture to non-oxidative pyrolysis to and at a temperature within the range of about 600.degree.-2000.degree. F.
    Type: Grant
    Filed: May 16, 1977
    Date of Patent: April 3, 1979
    Assignee: Chemplex Company
    Inventors: Joseph Liu, Howard L. Grimmett, Yu-Tang Hwang
  • Patent number: 4146694
    Abstract: A catalyst and the method of making same and a method of making polymers of 1-olefins with said catalyst in which the catalyst is prepared by chemically modifying a finely divided, difficultly reducible, inorganic support of the nature of silica, alumina, thoria, titania, magnesia and mixtures thereof by adding to the support a zirconium compound before dispersing on the modified support a chromium chelate derived from a beta-dicarbonyl compound that may be either acyclic or cyclic, the chelate being essentially of the formula ##STR1## WHEREIN R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen
    Type: Grant
    Filed: September 6, 1977
    Date of Patent: March 27, 1979
    Assignee: Chemplex Company
    Inventors: Yu-Tang Hwang, Howard L. Grimmett
  • Patent number: 4128500
    Abstract: A catalyst and the method of making same and a method of making polymers of 1-olefins with said catalyst in which the catalyst is prepared by chemically modifying a finely divided, difficultly reducible, inorganic support of the nature of silica, alumina, thoria, titania, magnesia and mixtures thereof by adding to the support a zirconium compound before dispersing on the modified support a chromium chelate derived from a beta-dicarbonyl compound that may be either acyclic or cyclic, the chelate being essentially of the formula ##STR1## WHEREIN R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen
    Type: Grant
    Filed: April 7, 1976
    Date of Patent: December 5, 1978
    Inventors: Yu-Tang Hwang, Howard L. Grimmett
  • Patent number: 4119773
    Abstract: An olefin polymerization catalyst is prepared by depositing the chromium (III) compound obtained from the reaction of a chromium (III) carboxylate with an aluminum alkoxide upon an inorganic support material and calcining the impregnated support material in a non-reducing atmosphere above 300.degree. C, up to the decomposition temperature of the support material to provide an activated catalyst.
    Type: Grant
    Filed: June 22, 1977
    Date of Patent: October 10, 1978
    Assignee: National Distillers and Chemical Corporation
    Inventor: Anthony N. Speca
  • Patent number: 4117217
    Abstract: A new catalyst and method of making polymers therewith and the process of preparing the catalyst in which the catalyst is prepared by dispersing on a finely divided carrier material, particularly a difficultly reducible inorganic support such as silica, an organic chromium (II) or (III) salt or derivative of a carboxylic acid or an N-substituted carboxylic acid or a nitrogen-heterocyclic carboxylic acid and activating the resulting mixture by heating at an elevated temperature in a non-oxidizing atmosphere.
    Type: Grant
    Filed: May 13, 1977
    Date of Patent: September 26, 1978
    Assignee: Chemplex Company
    Inventor: Yu-Tang Hwang
  • Patent number: 4115639
    Abstract: Supported bis-cyclopentadienyl chromium [II] catalysts are modified with compounds having in their structure the moiety ##STR1## in order to improve the toughness and impact strength of the resulting ethylene polymers made therewith.
    Type: Grant
    Filed: December 20, 1973
    Date of Patent: September 19, 1978
    Assignee: Union Carbide Corporation
    Inventors: Gary Leigh Brown, Weldon Clifford Cummings, Isaac Jacob Levine
  • Patent number: 4101722
    Abstract: A chromium-containing catalyst utilizing spray dried silica gel containing titanium is used to produce olefin polymers exhibiting an outstanding resistance to environmental stress cracking.
    Type: Grant
    Filed: February 4, 1977
    Date of Patent: July 18, 1978
    Assignee: Phillips Petroleum Company
    Inventors: John P. Hogan, Donald D. Norwood
  • Patent number: 4100105
    Abstract: A catalyst for the preparation of ethylene polymers having higher melt indexes comprises a silyl chromate deposited on a silica support containing both aluminum and titanium.
    Type: Grant
    Filed: January 21, 1977
    Date of Patent: July 11, 1978
    Assignee: Union Carbide Corporation
    Inventors: Isaac Jacob Levine, Frederick John Karol
  • Patent number: 4096093
    Abstract: A new catalyst and method of making polymers therewith and the process of preparing the catalyst in which the catalyst is prepared by dispersing on a finely divided carrier material, particularly a difficultly reducible inorganic support such as silica, a reaction product of (1) a chromium carboxylate reactant and (2) an organic nitrogen compound reactant capable of forming a complex such as a chelate with the chromium and activating the resulting mixture by heating at an elevated temperature in a non-oxidizing atmosphere.
    Type: Grant
    Filed: June 24, 1976
    Date of Patent: June 20, 1978
    Assignee: Chemplex Company
    Inventor: Yu-Tang Hwang
  • Patent number: 4086408
    Abstract: Supported bis-cyclopentadienyl chromium [II] catalysts are modified with compounds having in their structure the moiety ##STR1## IN ORDER TO IMPROVE THE TOUGHNESS AND IMPACT STRENGTH OF THE RESULTING ETHYLENE POLYMERS MADE THEREWITH.
    Type: Grant
    Filed: May 19, 1976
    Date of Patent: April 25, 1978
    Assignee: Union Carbide Corporation
    Inventors: Frederick John Karol, Chi-Sung Wu
  • Patent number: 4086409
    Abstract: Supported bis-cyclopentadienyl chromium [II] catalysts are modified with compounds having in their structure the moiety ##STR1## IN ORDER TO IMPROVE THE TOUGHNESS AND IMPACT STRENGTH OF THE RESULTING ETHYLENE POLYMERS MADE THEREWITH.
    Type: Grant
    Filed: May 19, 1976
    Date of Patent: April 25, 1978
    Assignee: Union Carbide Corporation
    Inventors: Frederick John Karol, Chi-Sung Wu
  • Patent number: 4069124
    Abstract: Method for the cationic polymerization of at least one olefinic monomer and more particularly the homopolymerization of a mono-olefinic monomer such as isobutylene and the copolymerization thereof with a di-olefinic monomer (diene) such as butadiene and optionally another mono-olefinic monomer in the presence of, as initiator of a halide of tetravalent vanadium, titanium and zirconium, an activator and under the influence of visible ultraviolet or infra-red light.
    Type: Grant
    Filed: November 29, 1976
    Date of Patent: January 17, 1978
    Assignee: Ceskoslovenska akademie ved
    Inventors: Miroslav Marek, Ludek Toman, Jan Pecka
  • Patent number: 4069125
    Abstract: Method for the cationic polymerization of at least one olefinic monomer and more particularly the homopolymerization of a mono-olefinic monomer such as isobutylene and the copolymerization thereof with a di-olefinic monomer (diene) such as butadiene and optionally another mono-olefinic monomer in the presence of, as initiator of a halide of tetravalent vanadium, titanium and zirconium, an activator and under the influence of visible ultraviolet or infra-red light.
    Type: Grant
    Filed: November 29, 1976
    Date of Patent: January 17, 1978
    Assignee: Ceskoslovenska akademie ved
    Inventors: Miroslav Marek, Ludek Toman, Jan Pecka
  • Patent number: 4068054
    Abstract: An olefin is polymerized in a hydrocarbon diluent in a turbulent reaction zone to produce particles of polymer which are substantially insoluble in the diluent. Fouling of the reactor by adherence of polymer particles to the walls of the reactor is reduced by adding to the reaction medium a composition which comprises a porphyrin compound, alone or together with a metal alkyl sulfosuccinate. This composition is also useful as an antistatic agent for liquid hydrocarbons and halohydrocarbons.
    Type: Grant
    Filed: August 2, 1976
    Date of Patent: January 10, 1978
    Assignee: Phillips Petroleum Company
    Inventor: Kenneth W. Willcox
  • Patent number: 4053437
    Abstract: A new catalyst and a method of polymerizing olefins in which the catalyst is prepared by forming a mixture by dispersing on a finely divided, difficult to reduce, inorganic support of the class consisting of silica, alumina, thoria, zirconia, titania, magnesia and mixtures or composites thereof, an organic chromium compound pyrolytically decomposable in the substantial absence of oxygen to deposit a catalytically active residue along with a carbon residue as a contaminant on the support, then activating the mixture by subjecting the mixture to non-oxidative pyrolysis to and at a temperature within the range of about 600-2000.degree. F.
    Type: Grant
    Filed: March 4, 1976
    Date of Patent: October 11, 1977
    Assignee: Chemplex Company
    Inventors: Joseph Liu, Howard L. Grimmett, Yu-Tang Hwang
  • Patent number: 4041225
    Abstract: The method of making an active catalyst system, the catalyst system and a method of polymerizing olefins in which the catalyst system used is prepared by mixing an inorganic support such as silica with a chromium (III) amine complex and activating by heating the mixture to and at an elevated temperature in a non-oxidizing atmosphere.
    Type: Grant
    Filed: December 29, 1975
    Date of Patent: August 9, 1977
    Assignee: Chemplex Company
    Inventor: Thomas J. Pullukat
  • Patent number: 4041224
    Abstract: A catalyst prepared by (1) forming a mixture of a finely divided support such as silica, alumina, zirconia or thoria and a chromium compound which may be either organic or inorganic followed by (2) adding a titanium compound, then (3) heat activating the reaction product of (2), and then (4) further heating in a gas that comprises oxygen. The disclosure also includes a method of polymerizing olefins with this catalyst and the process of preparing the catalyst.
    Type: Grant
    Filed: November 19, 1975
    Date of Patent: August 9, 1977
    Assignee: Chemplex Company
    Inventors: Raymond E. Hoff, Thomas J. Pullukat, Mitsuzo Shida
  • Patent number: 4035561
    Abstract: A method of polymerizing a monomer comprising ethylene in which a catalyst used is prepared by dispersing on a dry, finely divided, difficultly reducible inorganic oxide support such as silica a reaction product prepared by reacting pinacol with a chromium compound in which the reaction product is fixed to the support by heating at an elevated temperature in a non-oxidizing atmosphere.
    Type: Grant
    Filed: March 1, 1976
    Date of Patent: July 12, 1977
    Assignee: Chemplex Company
    Inventors: Raymond E. Hoff, Mitsuzo Shida
  • Patent number: 4016343
    Abstract: A catalyst for polymerizing one or more 1-olefins prepared by activating with a dry gas that contains oxygen a mixture of a finely divided support and a tetravalent alkoxide of chromium. The disclosure also includes the method of making the catalyst and methods of polymerizing olefins with the catalyst.
    Type: Grant
    Filed: August 22, 1975
    Date of Patent: April 5, 1977
    Assignee: Chemplex Company
    Inventors: Raymond E. Hoff, Mitsuzo Shida
  • Patent number: 4011382
    Abstract: A supported catalyst is used in the low pressure catalytic copolymerization of ethylene with C.sub.3 to C.sub.6 .alpha.-olefins in a fluid bed reactor to produce polymers having a density of less than 0.941 and a melt index of >0.0 to at least about 2.0. The supported catalyst contains about 0.05 to 3.0 weight % of chromium, about 1.5 to 9.0 weight % of titanium and >0.0 to about 2.5 weight % of fluorine.
    Type: Grant
    Filed: March 10, 1975
    Date of Patent: March 8, 1977
    Assignee: Union Carbide Corporation
    Inventors: Isaac J. Levine, Frederick J. Karol