Contains Elemental Transition Metal Or A Non-oxide Compound Of A Transition Metal Patents (Class 526/96)
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Patent number: 5034364Abstract: 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: GrantFiled: November 9, 1989Date of Patent: July 23, 1991Assignee: Mobil Oil CorporationInventors: Bohumil V. Kral, Grace O. Tsien, Chisung Wu
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Patent number: 5032651Abstract: 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: GrantFiled: May 29, 1990Date of Patent: July 16, 1991Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Paul D. Smith
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Patent number: 4665263Abstract: 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: GrantFiled: March 21, 1986Date of Patent: May 12, 1987Assignee: Phillips Petroleum CompanyInventors: Paul D. Smith, Eric T. Hsieh
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Patent number: 4622371Abstract: 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: GrantFiled: January 4, 1985Date of Patent: November 11, 1986Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4619980Abstract: 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: GrantFiled: April 1, 1985Date of Patent: October 28, 1986Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Paul D. Smith
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Patent number: 4590246Abstract: 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: GrantFiled: January 27, 1982Date of Patent: May 20, 1986Assignee: Norchem, Inc.Inventors: Robert A. Dombro, William Kirch
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Patent number: 4547557Abstract: 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: GrantFiled: July 9, 1984Date of Patent: October 15, 1985Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4540758Abstract: 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: GrantFiled: September 15, 1975Date of Patent: September 10, 1985Assignee: Union Carbide CorporationInventors: Robert N. Johnson, Frederick J. Karol
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Patent number: 4505969Abstract: 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: GrantFiled: February 9, 1982Date of Patent: March 19, 1985Assignee: Mobil Oil CorporationInventor: Milton L. Weiner
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Patent number: 4442275Abstract: 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: GrantFiled: September 29, 1982Date of Patent: April 10, 1984Assignee: Phillips Petroleum CompanyInventor: Joel L. Martin
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Patent number: 4418187Abstract: 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: GrantFiled: April 15, 1981Date of Patent: November 29, 1983Assignee: BASF AktiengesellschaftInventors: Volker Muench, Herbert Naarmann, Klaus Penzien
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Patent number: 4405768Abstract: 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: GrantFiled: September 24, 1982Date of Patent: September 20, 1983Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4369295Abstract: 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: GrantFiled: November 3, 1981Date of Patent: January 18, 1983Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4345055Abstract: 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: GrantFiled: May 20, 1981Date of Patent: August 17, 1982Assignee: Phillips Petroleum CompanyInventor: Gil R. Hawley
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Patent number: 4331789Abstract: 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: GrantFiled: May 6, 1981Date of Patent: May 25, 1982Assignee: Phillips Petroleum CompanyInventor: Gil R. Hawley
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Patent number: 4325839Abstract: 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: GrantFiled: December 21, 1979Date of Patent: April 20, 1982Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4303770Abstract: 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: GrantFiled: July 7, 1980Date of Patent: December 1, 1981Assignee: Chemplex CompanyInventors: Thomas J. Pullukat, Mitsuzo Shida
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Patent number: 4298722Abstract: 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: GrantFiled: March 11, 1980Date of Patent: November 3, 1981Assignee: E. I. Du Pont de Nemours and CompanyInventors: John W. Collette, Charles W. Tullock
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Patent number: 4279780Abstract: 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: GrantFiled: April 18, 1980Date of Patent: July 21, 1981Assignee: Chemplex CompanyInventor: Robert A. Dombro
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Patent number: 4263422Abstract: 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: GrantFiled: December 31, 1979Date of Patent: April 21, 1981Assignee: The Dow Chemical CompanyInventors: Kirby Lowery, Jr., Fred L. Vance, Jr.
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Patent number: 4246139Abstract: 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: GrantFiled: September 15, 1975Date of Patent: January 20, 1981Assignee: Phillips Petroleum CompanyInventor: Donald R. Witt
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Patent number: 4238353Abstract: 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: GrantFiled: June 8, 1979Date of Patent: December 9, 1980Assignee: National Petro Chemicals Corp.Inventor: Anthony N. Speca
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Patent number: 4228263Abstract: 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: GrantFiled: June 20, 1978Date of Patent: October 14, 1980Assignee: E. I. Du Pont de Nemours and CompanyInventors: Edward G. Howard, Jr., Christos Sarafidis
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Patent number: 4188471Abstract: 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: GrantFiled: December 4, 1974Date of Patent: February 12, 1980Assignee: Phillips Petroleum CompanyInventors: Benny E. Nasser, Jr., Joseph A. Delap
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Patent number: 4186260Abstract: 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: GrantFiled: August 1, 1978Date of Patent: January 29, 1980Assignee: Phillips Petroleum CompanyInventor: Richard E. Dietz
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Patent number: 4182815Abstract: 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: GrantFiled: February 6, 1979Date of Patent: January 8, 1980Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Melvin B. Welch
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Patent number: 4173548Abstract: 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: GrantFiled: June 12, 1978Date of Patent: November 6, 1979Assignee: Chemplex CompanyInventors: Thomas J. Pullukat, Mitsuzo Shida, Raymond E. Hoff
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Patent number: 4169925Abstract: 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: GrantFiled: April 28, 1978Date of Patent: October 2, 1979Assignee: BASF AktiengesellschaftInventors: Wolfgang Gruber, Hans Frielingsdorf, Robert Bachl, Guenther Schweier
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Patent number: 4152502Abstract: 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: GrantFiled: April 12, 1978Date of Patent: May 1, 1979Assignee: Union Carbide CorporationInventors: Isaac J. Levine, Frederick J. Karol
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Patent number: 4150208Abstract: 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: GrantFiled: November 14, 1977Date of Patent: April 17, 1979Assignee: Chemplex CompanyInventor: Yu-Tang Hwang
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Patent number: 4147849Abstract: 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: GrantFiled: May 16, 1977Date of Patent: April 3, 1979Assignee: Chemplex CompanyInventors: Joseph Liu, Howard L. Grimmett, Yu-Tang Hwang
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Patent number: 4146694Abstract: 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 hydrogenType: GrantFiled: September 6, 1977Date of Patent: March 27, 1979Assignee: Chemplex CompanyInventors: Yu-Tang Hwang, Howard L. Grimmett
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Patent number: 4128500Abstract: 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 hydrogenType: GrantFiled: April 7, 1976Date of Patent: December 5, 1978Inventors: Yu-Tang Hwang, Howard L. Grimmett
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Patent number: 4119773Abstract: 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: GrantFiled: June 22, 1977Date of Patent: October 10, 1978Assignee: National Distillers and Chemical CorporationInventor: Anthony N. Speca
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Patent number: 4117217Abstract: 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: GrantFiled: May 13, 1977Date of Patent: September 26, 1978Assignee: Chemplex CompanyInventor: Yu-Tang Hwang
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Patent number: 4115639Abstract: 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: GrantFiled: December 20, 1973Date of Patent: September 19, 1978Assignee: Union Carbide CorporationInventors: Gary Leigh Brown, Weldon Clifford Cummings, Isaac Jacob Levine
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Patent number: 4101722Abstract: 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: GrantFiled: February 4, 1977Date of Patent: July 18, 1978Assignee: Phillips Petroleum CompanyInventors: John P. Hogan, Donald D. Norwood
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Patent number: 4100105Abstract: 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: GrantFiled: January 21, 1977Date of Patent: July 11, 1978Assignee: Union Carbide CorporationInventors: Isaac Jacob Levine, Frederick John Karol
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Patent number: 4096093Abstract: 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: GrantFiled: June 24, 1976Date of Patent: June 20, 1978Assignee: Chemplex CompanyInventor: Yu-Tang Hwang
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Patent number: 4086408Abstract: 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: GrantFiled: May 19, 1976Date of Patent: April 25, 1978Assignee: Union Carbide CorporationInventors: Frederick John Karol, Chi-Sung Wu
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Patent number: 4086409Abstract: 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: GrantFiled: May 19, 1976Date of Patent: April 25, 1978Assignee: Union Carbide CorporationInventors: Frederick John Karol, Chi-Sung Wu
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Patent number: 4069124Abstract: 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: GrantFiled: November 29, 1976Date of Patent: January 17, 1978Assignee: Ceskoslovenska akademie vedInventors: Miroslav Marek, Ludek Toman, Jan Pecka
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Patent number: 4069125Abstract: 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: GrantFiled: November 29, 1976Date of Patent: January 17, 1978Assignee: Ceskoslovenska akademie vedInventors: Miroslav Marek, Ludek Toman, Jan Pecka
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Patent number: 4068054Abstract: 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: GrantFiled: August 2, 1976Date of Patent: January 10, 1978Assignee: Phillips Petroleum CompanyInventor: Kenneth W. Willcox
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Patent number: 4053437Abstract: 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: GrantFiled: March 4, 1976Date of Patent: October 11, 1977Assignee: Chemplex CompanyInventors: Joseph Liu, Howard L. Grimmett, Yu-Tang Hwang
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Patent number: 4041225Abstract: 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: GrantFiled: December 29, 1975Date of Patent: August 9, 1977Assignee: Chemplex CompanyInventor: Thomas J. Pullukat
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Patent number: 4041224Abstract: 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: GrantFiled: November 19, 1975Date of Patent: August 9, 1977Assignee: Chemplex CompanyInventors: Raymond E. Hoff, Thomas J. Pullukat, Mitsuzo Shida
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Patent number: 4035561Abstract: 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: GrantFiled: March 1, 1976Date of Patent: July 12, 1977Assignee: Chemplex CompanyInventors: Raymond E. Hoff, Mitsuzo Shida
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Patent number: 4016343Abstract: 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: GrantFiled: August 22, 1975Date of Patent: April 5, 1977Assignee: Chemplex CompanyInventors: Raymond E. Hoff, Mitsuzo Shida
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Patent number: 4011382Abstract: 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: GrantFiled: March 10, 1975Date of Patent: March 8, 1977Assignee: Union Carbide CorporationInventors: Isaac J. Levine, Frederick J. Karol