Elemental Oxygen Or Nonmetallic Inorganic Oxygen-containing Material, Other Than Water Patents (Class 502/120)
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Patent number: 5332706Abstract: A support containing methylalumoxane and derivatives thereof is described which is formed by an incipient impregnation technique. The most preferred support is silica. Incipient impregnation in accordance with the invention provides a supported alumoxane, methylalumoxane, which substantially eliminates the problem of fluid bed reactor fouling when methylalumoxane is introduced into the reactor during its operation.In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluid bed gas phase.Type: GrantFiled: December 28, 1992Date of Patent: July 26, 1994Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
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Patent number: 5330949Abstract: A method for producing a polyolefin is disclosed which comprises polymerizing an .alpha.-olefin in the presence of a catalyst composition comprising (A) a solid catalyst component prepared by contacting (a) a solid component comprising a magnesium alkoxide and/or a magnesium salt of a fatty acid supported on an inorganic oxide composed of at least one member selected from the group consisting of oxides of elements belonging to Groups II, III and IV of the periodic table and/or a composite inorganic oxide containing at least one member selected from the group consisting of oxides of elements belonging to Groups II, III and IV of the periodic table, the inorganic oxide or composite inorganic oxide having a surface hydroxide concentration of 3 .mu.mol/m.sup.2 or less, (b) an electron donating compound and (c) a titanium halide, (B) an organic metal compound, and (C) an electron donating compound.Type: GrantFiled: April 26, 1990Date of Patent: July 19, 1994Assignee: Idemitsu Petrochemical Company, Ltd.Inventors: Hideo Funabashi, Akira Tanaka, Rikuo Ohnishi, Toshikazu Kasahara, Takashi Yamawaki
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Patent number: 5328877Abstract: A solid catalyst component for alkene polymerization comprising a magnesium halide, an electron donor and a phenoxy-titanium halide, the latter being a dihalophenoxy-titanium halide or a dialkoxyphenoxy-titanium halide in which the alkoxy groups each have from 1 to 8 carbon atoms.Type: GrantFiled: January 19, 1993Date of Patent: July 12, 1994Assignee: Shell Oil CompanyInventors: John C. Chadwick, Alan Villena, Ronald P. C. Van Gaalen
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Patent number: 5324698Abstract: A problem in the conventional olefin polymerization catalyst systems, the procatalysts of which are based on a solid carrier and a titanium compound and an electron donor on its surface, is that unsufficiently high activities are achieved by the morphology of the carrier. Moreover, the active age of such a catalyst in the polymerization is too short. These problems have now been solved by the olefin polymerization catalyst system according to the invention, the procatalyst of which comprises a solid carrier and a layer on its surface consisting of a titanium compound, a magnesium compound and an electron donor. The advantages of the invention become more emphasized when using monocyclopentadienyl titaniumtrichloride as the titanium compound.Type: GrantFiled: September 21, 1992Date of Patent: June 28, 1994Assignee: Neste OyInventors: Sirpa Ala-Huikku, Ulf Palmqvist, Marjaana Lommi, Eero Iiskola
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Patent number: 5320996Abstract: Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a cyclopentadienyl Group 6b metal compound having at least one oxo, thio, imido or phosphido group bonded directly to the Group 6b metal, and at least one organic radical bonded to the Group 6b metal through a carbon atom, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound cocatalyst.Type: GrantFiled: November 6, 1992Date of Patent: June 14, 1994Assignee: Chevron Research and Technology CompanyInventors: Michael J. Carney, David L. Beach
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Patent number: 5310716Abstract: A supported solid component of catalyst, for the stereospecific polymerization of propylene and other .alpha.-olefins, is obtained by making a non-activated silica interact in succession with: (i) a magnesium dialkyl or halide of magnesium alkyl; (ii) a halogenating agent selected from silicon, tin and antimony halides; (iii) a titanium tetrahalide; and (iv) a Lewis base. A catalyst for the stereospecific polymerization of propylene and other .alpha.-olefins is composed of: (A) the solid component of catalyst; (B) an aluminium trialkyl or aluminium alkyl halide; and (C) an electron donor compound, capable of forming a complex compound with component (B).Type: GrantFiled: July 22, 1992Date of Patent: May 10, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Ludiano Luciani, Federico Milani, Renzo Invernizzi, Italo Borghi, Antonio Labianco
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Patent number: 5308816Abstract: The present invention relates to a solid catalyst composed of a specific solid catalyst component [A-1], the catalyst containing the solid catalyst and the olefin polymerization process using the solid catalyst, in which the solid catalyst component [A-1] comprises; (a-1) a particulate carrier composed of a specific oxide of a metal; (a-2) an organoaluminum oxy compound; and (a-3) a specific transition metal compound containing a specific ligand, wherein the organoaluminum oxy compound (a-2) and the transition metal compound (a-3) are supported on the particulate carrier (a-1).The catalysts are applicable to a suspension polymerization and a vapor phase polymerization, and capable of preparing spherical olefin polymers excellent in particle characteristics at high polymerization activity.Type: GrantFiled: May 29, 1992Date of Patent: May 3, 1994Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Kunio Yamamoto
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Patent number: 5298474Abstract: A solid component of catalyst for the (co)polymerization of ethylene is composed of a silica support and of a catalytically active part containing titanium, magnesium, chlorine and alkoxy groups, and is obtained by:(i) activating a silica support by contact with a solution of magnesium dialkyl, or magnesium alkyl chloride, in a liquid, aliphatic hydrocarbon solvent;(ii) impregnating the activated silica with a solution, in a liquid aliphatic or aromatic ester, of titanium tetrachloride and tetra-alkoxide in equimolecular or almost equimolecular quantities, and magnesium chloride; and(iii) treating the solid obtained in step (ii) with a proportioned quantity of aluminium alkyl sesquichloride.Type: GrantFiled: July 10, 1992Date of Patent: March 29, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Luciano Luciani, Federico Milani, Renzo Invernizzi, Maddalena Pondrelli
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Patent number: 5296430Abstract: A so-called Ziegler catalyst composed of a titanium halide-containing solid ingredient and an organoaluminum compound for the polymerization of olefins can be imparted with greatly improved storage stability by first subjecting the catalytic composition to a pre polymerization treatment and then to a contacting treatment with carbon dioxide and/or carbon monoxide. The catalytic activity is almost unchanged even after storage of the stabilized catalyst for 90 days or longer in nitrogen gas. The stabilized catalyst can also be used advantageously in a continuous-process polymerization of propylene by continuously introducing the monomer carrying the catalyst owing to absence of blocking of the pipe line with the polymer formed in-line.Type: GrantFiled: April 7, 1993Date of Patent: March 22, 1994Assignee: Idemitsu Petrochemical Company, Ltd.Inventors: Hideo Funabashi, Yoichi Matsuo, Shigeo Iwasaki
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Patent number: 5296432Abstract: Solid component of catalyst for the (co)polymerization of ethylene, including magnesium, halogen and titanium, obtained by:(i) dissolution, in an inert organic solvent, of a magnesium dialkyl, or a magnesium alkyl halide, a tin halide (IV) and possibly also an alkyl halide and their contact until a granular solid precipitates from the solution;(ii) contact of said granular solid and its interaction with a titanium halide, alkoxide or halo-alkoxide, to form a solid component of catalyst.Type: GrantFiled: July 9, 1992Date of Patent: March 22, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Federico Milani, Luciano Luciani, Maddalena Pondrelli
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Patent number: 5290745Abstract: A catalyst system of the Ziegler-Natta type suitable for producing ethylene copolymers having a reduced hexane extractable content comprising (a) an organoaluminum component and (b) a titanium trichloride component which has been prepared by reducing titanium tetrachloride with magnesium metal.Type: GrantFiled: August 10, 1992Date of Patent: March 1, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Robert J. Jorgensen, Elton D. Fowler, George L. Goeke
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Patent number: 5281567Abstract: An improved high activity olefin polymerization catalyst catalyzes the production of polymeric lower .alpha.-olefin having good properties and a relatively narrow particle size distribution. The catalyst is produced from an organoaluminum cocatalyst, a selectivity control agent and a novel olefin polymerization procatalyst which is prepared by contacting a tetravalent titanium halide, a halohydrocarbon, an electron donor and the solid procatalyst precursor obtained by heating an adduct of a carbonated magnesium ethoxide and a phenolic compound of enhanced acidity.Type: GrantFiled: June 29, 1992Date of Patent: January 25, 1994Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5278117Abstract: A supported Ziegler-Natta catalyst active in ethylene polymerization and in the copolymerization of ethylene with alpha-olefins consists of:(A) a cocatalyst in the form of an organometallic compound of aluminium, and(B) a solid catalyst component obtained by:(i) impregnating a granular solid support with a solution of a titanium alcoholate and magnesium chloride in a liquid aliphatic hydrocarbon, followed by evaporation of the hydrocarbon solvent;(ii) impregnating the support treated in (i) with a solution of magnesium chloride in a liquid aliphatic ester, followed by evaporation of the ester solvent; and(iii) activating the support treated in (ii) by contact with an alkyl aluminium halide.In a preferred embodiment, measured quantities of a silicon halide are introduced in stage (i) and/or (ii), this considerably improving catalytic activity.Type: GrantFiled: March 8, 1991Date of Patent: January 11, 1994Assignee: Montedipe S.r.l.Inventors: Luciano Luciani, Renzo Invernizzi, Francesco Masi, Maddalena Pondrelli, Mario Polesello, Italo Borghi
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Patent number: 5276117Abstract: A catalyst for producing styrene-based polymers, containing (A) a titanium compound, (B) a contact product of an organoaluminum compound and water, and (C) an organic polyhydroxy compound, or (A) a titanium compound and (B) a contact product of an organoaluminum compound, water and a organic polyhydroxy compound, and a process for producing styrene-based polymers by the use of the above catalyst.Type: GrantFiled: September 15, 1992Date of Patent: January 4, 1994Assignee: Idemitsu Kosan Co., Ltd.Inventors: Norio Tomotsu, Hiroshi Maezawa
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Patent number: 5275991Abstract: A novel catalyst support and a method for preparation thereof, characterized by the presence of selected amounts of a hydrocarbon soluble magnesium-containing compound applied to the support relative to solvent, wherein a surface uniformly and essentially continuously moistened with the solvated magnesium compound in a condition of incipient precipitation to permit the formation of a regular essentially continuous distribution of the magnesium compound onto and conforming to the support material. The drying process under these conditions is effective in maintaining to a high degree the effective surface area and pore volume of the material. The support containing the adsorbed magnesium is then dried in a controlled manner to essential incipient wetness conditions providing a regular spatial distribution of stacked reticular magnesium values at a level of one to five molecular monolayers on the support.Type: GrantFiled: November 30, 1992Date of Patent: January 4, 1994Assignee: Quantum Chemical CorporationInventors: Charles K. Buehler, Albert P. Masino, Raghu Menon
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Supported vanadium catalyst for prodution of polyolefins of controlled molecular weight distribution
Patent number: 5262372Abstract: A process for the production of a highly active olefin polymerization vanadium catalyst, comprising a vanadium compound and an organophosphorous compound combined on a catalyst support, which is capable of producing a broad range of polymer products. The polymer product's molecular weight distribution may be tailored to suit a desired application by controlling the P/V ratio of the catalyst.Type: GrantFiled: February 3, 1992Date of Patent: November 16, 1993Assignee: Exxon Chemical Patents Inc.Inventor: Gerald D. Malpass, Jr. -
Patent number: 5260245Abstract: A catalyst for producing higher flow index linear low density polyethylene with relatively narrower molecular weight distributions is described. The catalyst is formed by treating silica having reactive OH groups with a dialkylmagnesium in a solvent for said dialkylmagnesium; then adding to said solvent a carbonyl containing compound to form an intermediate which is subsequently treated with a transition metal to form a catalyst precursor. The catalyst precursor is activated with triethylaluminum.Type: GrantFiled: October 19, 1992Date of Patent: November 9, 1993Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 5258345Abstract: The invention relates to catalysts which produce linear low density polyethylene with a bimodal molecular weight distribution, particularly those containing a high molecular weight fraction. The catalysts are formed by contacting a carrier with an organomagnesium compound to incorporate magnesium into the carrier, and subsequently contacting the carrier containing the incorporated magnesium with a silicon compound and subsequently with a transition metal source; the transition metal containing intermediate is again treated with an organomagesium compound to form a catalyst precursor, and the catalyst precursor is activated with dimethylaluminum chloride.Type: GrantFiled: November 20, 1992Date of Patent: November 2, 1993Assignee: Mobil Oil CorporationInventors: Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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Patent number: 5252529Abstract: A solid catalyst for olefin polymerization comprising [A] a particulate carrier composed of (i) an oxide of at least one element selected from among those belonging to the groups of II, III and IV of the periodic table, and containing (ii) at least 1.0% by weight of water, [B] an organoaluminum oxy compound, and [C] a transition metal compound of a metal belonging to the group IV B of the periodic table containing a ligand having a cyclopentadienyl skeleton,wherein the organoaluminum oxy compound [B] and the transition metal compound [C] are supported on the particulate carrier [A].Type: GrantFiled: May 20, 1992Date of Patent: October 12, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Takashi Ueda, Kazunori Okawa
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Patent number: 5252190Abstract: A harmful substance remover, which is used to remove any of ethylene, mercaptans, amines and aldehydes, is a solid product having a specific surface area of 100 m.sup.2 /g or more obtained by hydrolyzing a metal alkoxide in the presence or absence of a noble metal. The harmful substance remover is utilized by contacting a harmful substance therewith. Such contacting may take place under irradiation of ultraviolet rays.Type: GrantFiled: March 1, 1991Date of Patent: October 12, 1993Assignee: Nippon Zeon Co., Ltd.Inventors: Kenichi Sekiguchi, Tsunehisa Ueda, Tadao Natsuume
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Patent number: 5244854Abstract: Catalyst components for the polymerization of olefins, obtained by reacting a tetravalent titanium halide or halogen alcoholate and an electron-donor compound with a solid comprising a porous metallic oxide containing hydroxyl groups on the surface, on which is supported a magnesium dihalide or a magnesium compound which does not contain Mg-C bonds and can be transformed into a dihalide, characterized in that the quantity of Mg supported on the oxide prior to the reaction with titanium compound, and present in the catalyst component after the reaction with the Ti compound, is from 5% to 12% weight with respect to the weight of the catalyst component.Type: GrantFiled: March 24, 1992Date of Patent: September 14, 1993Assignee: Himont IncorporatedInventors: Luciano Noristi, Antonio Monte
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Patent number: 5240895Abstract: Disclosed is a catalyst system for the homopolymerization and copolymerization of alpha-olefins having 2-8 carbon atoms, said catalyst system comprising a dimeric or tetrameric cyclopentadienyl Group 6b metal compound in which the metal has an oxidation state of +2, said Group 6b metal compound being supported on an inorganic support. The catalyst system may also contain a Group 2 or Group 3 metal alkyl compound cocatalyst.Type: GrantFiled: November 6, 1992Date of Patent: August 31, 1993Assignee: Chevron Research and Technology CompanyInventors: Michael J. Carney, David L. Beach
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Patent number: 5238892Abstract: This invention relates to a supported catalyst composition useful in the polymerization of olefins and to a method for its production. The invention particularly relates to the use of undehydrated silica gel containing from about 6 to about 20 percent by weight adsorbed water as the catalyst support material. The catalyst is formed by first reacting a trialkylaluminum compound with a metallocene, and subsequently reacting the resulting material with the undehydrated silica gel. The resulting supported metallocene-alumoxane catalyst has a level of activity comparable to that of conventionally made supported catalysts which are achieved at active metal loadings which are reduced from the loadings used in the previously known metallocene-alumoxane catalysts by at least 20%, and preferably 50%.Type: GrantFiled: June 15, 1992Date of Patent: August 24, 1993Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang
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Patent number: 5234878Abstract: The present invention provides an olefin polymerization solid catalyst prepared by pre-polymerizing olefin in a suspension containing[A] a component obtainable by bringing a particulate carrier, an organoaluminum compound [A-a] and water into contact with one another,[B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and, if necessary,[C] an organoaluminum compound.Type: GrantFiled: February 12, 1991Date of Patent: August 10, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Takashi Ueda
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Patent number: 5235071Abstract: The invention relates to a catalyst for producing phthalic anhydride by gas phase catalytic oxidation of o-xylene and/or naphthalene with molecular oxygen or gas containing molecular oxygen and, to a process for producing phthalic anhydride by using said catalyst. The catalyst is made by supporting, on a heat-resistant inorganic carrier, a catalytic active substance which comprises: vanadium oxide; anatase type titanium dioxide having specific surface area of 10 to 60 m.sup.2 /g; niobium; at least one element selected from potassium, cesium, rubidium and thallium; phosphorus; and antimony. The catalytic active substance is prepared by using a five-valent antimony compound as an antimony source. The process for producing phthalic anhydride comprises use of said catalyst.Type: GrantFiled: June 30, 1992Date of Patent: August 10, 1993Assignee: Nippon Shokubai Co., Ltd.Inventors: Kenji Ueda, Masaaki Okuno, Tatsuya Kawabata, Shinya Tanaka
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Patent number: 5229344Abstract: An improved high activity olefin polymerization catalyst catalyzes the production of polymeric lower .alpha.-olefin having good properties and a relatively narrow particle size distribution. The catalyst is produced from an organoaluminum cocatalyst, a selectivity control agent and a novel olefin polymerization procatalyst which is prepared by contacting a tetravalent titanium halide, a halohydrocarbon, an electron donor and the solid procatalyst precursor obtained by heating an adduct of a carbonated magnesium ethoxide and a phenolic compound of enhanced acidity.Type: GrantFiled: June 29, 1992Date of Patent: July 20, 1993Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5227354Abstract: A process for making a magnesium-containing supported titanium-containing and vanadium-containing catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins.Type: GrantFiled: April 3, 1992Date of Patent: July 13, 1993Assignee: Amoco CorporationInventors: Nicholas M. Karayannis, Steven A. Cohen, Julie L. Ledermann
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Patent number: 5227440Abstract: The invention is a supported catalyst system including an inert support material, a Group IV B transition metal component and an alumoxane component which may be employed to polymerize olefins to produce a high molecular weight polymer.Type: GrantFiled: August 28, 1991Date of Patent: July 13, 1993Assignee: Exxon Chemical Patents Inc.Inventors: Jo Ann M. Canich, Gary F. Licciardi
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Patent number: 5227439Abstract: A solid component of catalyst for the (co)polymerization of ethylene is composed of a silica carrier and a catalytically active part which includes titanium, magnesium, chlorine and also alkoxy groups, and is obtained: by suspending an activated silica in an ethanolic solution of magnesium chloride; by contact of the suspension with an alkoxy or halogen alkoxyde of titanium and with a silicon halide; by eliminating the ethanol from the resulting suspension in order to recover a solid matter; and by making this solid react with an aluminium alkyl chloride.Type: GrantFiled: July 20, 1992Date of Patent: July 13, 1993Assignee: Ecp Enichem Polimeri s.r.l.Inventors: Luciano Luciani, Maddalena Pondrelli, Renzo Invernizzi, Italo Borghi
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Patent number: 5223466Abstract: A process for making a magnesium-containing supported titanium-containing, alpha-olefin polymerization or co-polymerization catalyst or catalyst component having a large particle size, semi-spherical particle shape and high resistance to attrition.Type: GrantFiled: March 20, 1992Date of Patent: June 29, 1993Assignee: Amoco CorporationInventors: Sam S. Lee, Nicholas M. Karayannis
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Patent number: 5221650Abstract: A novel catalyst support and a method for preparation thereof, characterized by the presence of selected amounts of a hydrocarbon soluble magnesium-containing compound applied to the support relative to solvent, wherein a surface uniformly and essentially continuously moistened with the solvated magnesium compound is achieved in a condition of incipient precipitation to permit the formation of a regular essentially continuous distribution of the magnesium compound onto and conforming to the support material The drying process under these conditions is effective in maintaining to a high degree the effective surface area and pore volume of the material. The support containing the adsorbed magnesium is then dried in a controlled manner to essential incipient wetness conditions providing a regular spatial distribution of stacked reticular magnesium values at a level of one to five molecular monolayers on the support.Type: GrantFiled: March 20, 1992Date of Patent: June 22, 1993Assignee: Quantum Chemical CorporationInventor: Charles K. Buehler
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Patent number: 5206198Abstract: Catalytic solids based on titanium trichloride complex, usable for the stereospecific polymerization of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of the liquid material resulting from bringing TiCl.sub.4, pretreated with an electron-donor compound, into contact with a composition (C) corresponding to the general formulaAlR.sub.p (Y) .sub.q X .sub.3-(p+q)in whichR represents a hydrocarbon radical or a hydrogen atom;Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrogen atom;X represents a halogen;p is an arbitrary number such that 0<p<3; andq is an arbitrary number such that 0<q<3; the sum (p+q) being such that 0<(p+q).ltoreq.3.These catalytic solids of controllable porosity permit the production of a wide range of propylene polymers, in particular the propylene and ethylene copolymers known as "block" copolymers.Type: GrantFiled: October 31, 1991Date of Patent: April 27, 1993Assignee: Solvay S.A.Inventors: Jean-Louis Costa, Sabine Pamart
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Patent number: 5204304Abstract: A vanadium-containing catalyst is prepared as the product of admixing an inorganic oxide, inorganic phosphate or mixtures thereof, a zinc-containing composition, and a vanadium-containing composition. An auxiliary compound such as, for example, an aluminum halide compound may optionally be admixed. The catalyst may be combined with a co-catalyst such as an aluminum alkyl and, optionally, a halocarbon promotor to yield an olefin polymerization catalyst system. The resulting catalyst system exhibits high activity, excellent hydrogen response and produces a polymer having a narrow to broad molecular weight distribution with a bimodal profile. The catalyst is especially useful in ethylene homopolymerization and co-polymerization.Type: GrantFiled: June 4, 1991Date of Patent: April 20, 1993Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5202398Abstract: If the transition metal component used in an olefin polymerization catalyst is the product of the reaction between a siloxane-substituted metallocene of titanium, zirconium or hafnium and a hydroxyl group-containing support material, for example silicon dioxide, these metallocene catalysts can be employed in existing polymerization plants which are designed for the suspension process.Type: GrantFiled: December 13, 1989Date of Patent: April 13, 1993Assignee: Hoechst AktiengesellschaftInventors: Martin Antberg, Hartmut Luker, Ludwig Bohm
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Patent number: 5200379Abstract: Olefin polymerization catalysts, processes for preparing the catalysts and processes for producing polyolefins utilizing the catalysts are provided. The catalysts are basically comprised of a pentadienyl derivative-transition metal complex adsorbed on an activated inorganic refractory compound.Type: GrantFiled: November 1, 1991Date of Patent: April 6, 1993Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Paul D. Smith
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Patent number: 5198400Abstract: Mixed catalyst compositions comprised of a first supported chromium-containing catalyst component and a second supported chromium-containing catalyst component and which additionally have one or more metallic or non-metallic catalytic agents associated therewith are provided. The additional metallic or non-metallic elements associated with the catalyst components can be aluminum, titanium, zirconium, boron, phosphorous or combinations thereof. The pore volume of the silica supports used for the first and second catalyst components differs by at least 0.3 cc/g. The mixed catalyst compositions of the invention are useful for the preparation of polyolefins. They are particularly useful of polymerization of ethylene in particle form polymerizations to produce high density polyethylene blow molding resins having good processability and physical properties. The improved particle form polymerization process and products obtained thereby using the above-described mixed catalyst compositions are also described.Type: GrantFiled: March 26, 1991Date of Patent: March 30, 1993Assignee: Quantum Chemical CorporationInventors: Stanley J. Katzen, Thomas J. Pullukat, Michael W. Lynch, Louis J. Rekers
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Patent number: 5192731Abstract: In accordance with the present invention, there are provided carrier-supported titanium catalyst components containing magnesium, aluminum, halogen and titanium as essential ingredients, which are obtained by a reaction of[I] a magnesium containing support obtained by previously bringing a support into contact with an organometallic compound of a metal of the Group II to IIIA of the periodic table having at least one hydrocarbon group attached directly to the metal atom or with a halogen containing compound, followed by contact with a magnesium compound in the liquid state having no reducing ability,[II] a reducing organometallic compound, and[III] a titanium compound in the liquid state, and processes for preparing the same and, at the same time, catalysts containing the above-mentioned catalyst components for use in preparing ethylene polymer and processes for preparing ethylene polymer using the catalyst for use in preparing ethylene polymer.Type: GrantFiled: October 23, 1991Date of Patent: March 9, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Kazumitsu Kawakita, Akinori Toyota
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Patent number: 5188998Abstract: A transition-metal catalyst component for a Ziegler catalyst system, obtainable by1) mixing an inorganic, oxidic carrier with a transition-metal starting component in an organic solvent,2) removing the solvent by evaporation,3) mixing the solid-phase intermediate from step (2) with3.1) an organoaluminum catalyst component of the formula AlR.sub.m X.sub.3-m, whereR is a C.sub.1 - to C.sub.18 -hydrocarbon radical,m is from 1 to 3, andX is OR, chlorine, bromine or hydrogen, and3.2) an organic carboxylate or an organosilicon compound or a mixture thereof in an organic solvent, and4) if desired, isolating the solid-phase intermediate by filtration, washing and drying,and the use thereof for the homopolymerization or copolymerization of ethene are described.Type: GrantFiled: March 19, 1991Date of Patent: February 23, 1993Assignee: BASF AktiengesellschaftInventors: Ulrich Bueschges, Roland Saive
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Patent number: 5188997Abstract: A solid component of a catalyst for the (co)polymerization of ethylene is composed of a silica carrier and a catalytically active part which includes titanium, magnesium, chlorine and also alkoxy groups, and is obtained: by suspending an activated silica in an ethanolic solution of magnesium chloride; by contact of the suspension with an alkoxy or halogen alkoxyde of titanium and with a silicon halide; by eliminating the ethanol from the resulting suspension in order to recover a solid matter; and by making this solid react with an aluminum alkyl chloride.Type: GrantFiled: September 5, 1991Date of Patent: February 23, 1993Assignee: ECP Enichem Polimeri s.r.l.Inventors: Luciano Luciani, Maddalena Pondrelli, Renzo Invernizzi, Italo Borghi
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Patent number: 5189000Abstract: A supported catalyst for the polymerization and copolymerization of olefinically unsaturated compounds is described, comprising an organometallic compound of aluminium and a second component obtained by bringing a titanium, vanadium or chromium compound, at least one compound of a second metal chosen from V, Al, Zr, Hf, Mo and Nd and optionally a magnesium compound into contact with a porous support consisting of microbeads of aerogels of one or more inorganic oxides distinguished by low density, high porosity and the fact that at least 90% of the pores have a diameter lying within a very narrow range of values. The process for the polymerization or copolymerization of olefinically unsaturated compounds based on the use of said catalyst is also described.Type: GrantFiled: March 21, 1991Date of Patent: February 23, 1993Assignees: Montedipe S.r.l., Enichem S.p.A.Inventors: Francesco Masi, Renzo Invernizzi, Antonio Carbonaro, Lorenzo Costa, Angelo Moalli
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Patent number: 5182245Abstract: A catalyst or catalyst component for the polymerization or copolymerization of alpha-olefins in the slurry phase is formed by a process comprising forming a solution of a magnesium-containing species in a liquid and precipitating solid particles from the solution of the magnesium-containing species by treatment with a transition metal halide in the presence of at least one of a tetrabutoxysilane and a tetrabutoxytitanate.Type: GrantFiled: June 26, 1991Date of Patent: January 26, 1993Assignee: Amoco CorporationInventors: Gregory G. Arzoumanidis, Christine Peaches
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Patent number: 5177043Abstract: This invention relates to a catalytic component for the polymerization of .alpha.-olefins and provides a catalytic component of magnesium support type capable of exhibiting a high stereoregularity while maintaining an improved strength as well as a high catalytic activity. The features thereof consist in a catalyst component for the polymerization of .alpha.-olefins obtained by contacting (A) a solid component comprising, as essential components, magnesium, titanium, a halogen and an electron-donating compound with (D) an olefin in the presence of (B) a trialkylaluminum and (C) a dimethoxy group-containing compound represented by the general formula R.sup.1 R.sup.2 Si(OCH.sub.3).sub.2 where R.sup.1 and R.sup.2 are, same or different, aliphatic hydrocarbon groups with 1 to 10 carbon atoms and having a volume, calculated by the quantum chemistry calculation, of 230 to 500 .ANG..sup.3 and an electron density of oxygen atoms in the methoxy group, calculated similarly, ranging from 0.685 to 0.800 A. U.Type: GrantFiled: March 22, 1991Date of Patent: January 5, 1993Assignee: Tonen Chemical CorporationInventors: Naomi Koyama, Hiroyuki Furuhashi, Miyuki Usui, Tomoko Okano, Masahide Murata, Satoshi Ueki, Akira Nakano
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Patent number: 5177042Abstract: A vanadium-based catalyst system is treated with an ether as a means of enhancing catalyst activity and polymer productivity.Type: GrantFiled: December 29, 1989Date of Patent: January 5, 1993Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Kevin J. Cann, James W. Nicoletti
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Patent number: 5173465Abstract: A solid catalyst component for ethylene (co)polymerization, consisting of a particulate silica support and a catalytically active part containing titanium, magnesium, chlorine and alkoxy groups is obtained by a) preparing a solution of magnesium chloride in ethanol; b) impregnating particulate silica with said solution; c) eliminating the unabsorbed ethanol from the suspension; d) eliminating absorbed ethanol from the solid; e) interacting the resultant solid with a titanium chloride, alkoxide or chloroalkoxide; and possibly interacting with an alkylaluminium chloride. In a preferred embodiment in stage e), a silicon halide is added to improve the catalyst activity.Type: GrantFiled: June 14, 1991Date of Patent: December 22, 1992Assignee: Montedipe S.r.l.Inventors: Luciano Luciani, Maddalena Pondrelli, Renzo Invernizzi
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Patent number: 5166113Abstract: Ziegler-Natta-type catalyst systems containing, as active constituents,a) a titanium-containing solid component which also contains magnesium, halogen and a carboxylic acid ester, and, as cocatalyst,b) an aluminum compound,wherein the carboxylic acid ester in the solid component is a diester of a carboxylic acid of the formula Ia or Ib ##STR1## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are hydrogen, C.sub.1 - to C.sub.15 -alkyl, C.sub.7 - to C.sub.15 -alkylaryl, or 5- to 7-membered cycloalkyl, which may itself carry C.sub.1 - to C.sub.10 -alkyl groups, are particularly suitable for the preparation of polypropylene and copolymers of propylene containing minor amounts of other .alpha.,.beta.-unsaturated olefinic compounds having from 2 to 12 carbon atoms.Type: GrantFiled: September 17, 1991Date of Patent: November 24, 1992Inventors: Harald Schwager, Peter Koelle, Juergen Kerth, Ralf Zolk
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Patent number: 5162277Abstract: An improved high activity olefin polymerization catalyst catalyzes the production of polymeric lower .alpha.-olefin having good properties and a relatively narrow particle size distribution. The catalyst is produced from an organoaluminum cocatalyst, a selectivity control agent and a novel olefin polymerization procatalyst which is prepared by contacting a tetravelent titanium halide, a halohydrocarbon, an electron donor and the solid procatalyst precursor obtained by heating an adduct of a carbonated magnesium ethoxide and a phenolic compound of enhanced acidity.Type: GrantFiled: October 18, 1990Date of Patent: November 10, 1992Assignee: Shell Oil CompanyInventor: Robert C. Job
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Patent number: 5162465Abstract: Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and contains, in addition to titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. In this process, a titanium component (1) is used which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel, (Ib) an alkanol, (Ic) an organomagnesium compound and (Id) a gaseous chlorinating agent by a procedure in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then the mixture obtained in (1.1.1) is combined with (Ic), (1.1.3) then (Id) is passed into the mixture obtained in (1.1.2) and (I) is isolated, (1.2) thereafter a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid drivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.Type: GrantFiled: January 28, 1991Date of Patent: November 10, 1992Assignee: BASF AktiengesellschaftInventors: Juergen Kerth, Ralf Zolk, Rainer Hemmerich
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Patent number: 5155079Abstract: A multiple site solid catalyst component capable of producing polyolefins having a broad or multimodal molecular weight distribution, such as a bi-modal molecular weight distribution, is prepared by contacting a particulate solid support with a zirconium compound or complex to bind the zirconium compound or complex to the support, optionally followed by contacting the supported zirconium compound or complex with a Lewis acid to produce an intermediate product, optionally isolating and washing the supported zirconium compound or complex or resulting intermediate product to remove soluble by-products therefrom, and reacting the washed or unwashed supported zirconium compound or complex or intermediate product with a titanium or vanadium compound to produce a solid catalyst component.Type: GrantFiled: June 7, 1991Date of Patent: October 13, 1992Assignee: Quantum Chemical CorporationInventors: Leonard V. Cribbs, Michael W. Lynch
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Patent number: 5155078Abstract: In accordance with the present invention, there are provided carrier-supported titanium catalyst components containing magnesium, aluminum, halogen and titanium as essential ingredients, which are obtained by a reaction of[I] a magnesium containing support obtained by previously bringing a support into contact with an organometallic compound of a metal of the Group II to IIIA of the periodic table having at least one hydrocarbon group attached directly to the metal atom or with a halogen containing compound, followed by contact with a magnesium compound in the liquid state having no reducing ability,[II] a reducing organometallic compound, and[III] a titanium compound in the liquid state, and processes for preparing the same and, at the same time, catalysts containing the above-mentioned catalyst components for use in preparing ethylene polymer and processes for preparing ethylene polymer using the catalyst for use in preparing ethylene polymer.Type: GrantFiled: June 17, 1991Date of Patent: October 13, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Kazumitsu Kawakita, Akinori Toyota
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Patent number: 5147949Abstract: This invention relates to a process for polymerizing olefin using a supported metallocene alumoxane catalyst, which can be used in slurry or liquid phase polymerization of olefins. The invention relates to the use of silica gel containing from about 10 to about 50% 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 was 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.Type: GrantFiled: October 18, 1991Date of Patent: September 15, 1992Assignee: Exxon Chemical Patents Inc.Inventor: Main Chang