Inorganic Oxygen Containing Aluminum Compound Patents (Class 526/156)
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Patent number: 4650842Abstract: Novel high pore volume, high purity alumina gels and catalysts prepared therefrom are provided by a unique alumina gel preparation comprising hydrolyzing an aluminum alcoholate in a medium of a mixture of water and acetone, aging the resultant product and thereafter washing with acetone. Processes for the polymerization of olefins utilizing the afore-described alumina gels are also included herein.Type: GrantFiled: April 15, 1985Date of Patent: March 17, 1987Assignee: National Distillers and Chemical CorporationInventors: Anthony N. Speca, Roger D. Laib
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Patent number: 4640964Abstract: A catalyst support based on aluminum polyphosphate or polyphosphoric acid-impregnated alumina is provided by two alternative techniques. In the first embodiment, an aluminum polyphosphate composition is heated in a dry atmosphere and thereafter impregnated with a zerovalent chromium component under anhydrous conditions. The resulting catalyst is active for olefin polymerization. In the second embodiment, alumina is impregnated with a polyphosphoric acid composition. This resulting polyphosphoric acid impregnated alumina can be used as a support for zerovalent chromium or can be impregnated with a chromium component and oxidized to give an active hexavalent chromium species. The resulting catalysts are advantageous because of their unusual sensitivity to hydrogen thus allowing great leeway in molecular weight control.Type: GrantFiled: June 5, 1985Date of Patent: February 3, 1987Assignee: Phillips Petroleum CompanyInventors: Marvin M. Johnson, Max P. McDaniel
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Patent number: 4634752Abstract: Alpha-olefin polymerization catalysts are prepared by heating a solid porous carrier having reactive OH groups in the atmosphere of an oxygen-containing gas. The resulting catalysts exhibit higher productivity and produce ethylene polymers or ethylene/C.sub.3 -C.sub.10 copolymers having higher bulk density than similar catalysts prepared with the carriers heated in an atmosphere of nitrogen.Type: GrantFiled: September 3, 1985Date of Patent: January 6, 1987Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Irena B. Petsche, Kenneth G. Schurzky
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Patent number: 4629771Abstract: A suspension which comprises an inert liquid medium, a solid material, a transition metal compound and an agglomeration aid is dried using a spray-drying technique. The spray-drying is effected under conditions of temperature and pressure which are such as to cause evaporation of the liquid medium. The solid material is preferably in a finely-divided form and may consist essentially of a transition metal compound or may be a transition metal compound which is supported on a suitable solid inert matrix material. Alternatively, a suspension of a solid support material in a solution of a transition metal compound may be used. The agglomeration aid may be polystyrene dissolved in the inert liquid medium. The dried solid is obtained as an agglomerated solid which can be mixed with an organic compound of a non-transition metal to give an olefin polymerization catalyst system.Type: GrantFiled: August 22, 1983Date of Patent: December 16, 1986Assignee: Imperial Chemical Industries, plcInventors: John P. Candlin, Anthony D. Caunt, John W. Kelland, Peter L. Law
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Patent number: 4618595Abstract: A catalyst, a process of forming the catalyst, and polymerizing at least one alpha-olefin with the catalyst, said catalyst produced by precipitating a composition from a solution of a metal halide, for example, magnesium dihalide, and a transition metal compound, for example, titanium tetraalkoxide, in the presence of a particulate diluent, for example, polymeric fibrils, with an agent selected from among specified organometallic compounds, metal halides and oxygen-containing metal halides, hydrogen halides and organic acid halides. The composition is preferably further treated with a halide ion exchanging source, for example, titanium tetrahalide to form a particularly active catalyst. The catalyst is preferably used in combination with a cocatalyst comprising a metal hydride or organometallic compound selected from an element of Periodic Groups IA, IIA and IIIA.Type: GrantFiled: June 5, 1985Date of Patent: October 21, 1986Assignee: Phillips Petrolem CompanyInventor: Richard E. Dietz
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Patent number: 4605638Abstract: There is disclosed a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid support, containing magnesium, in a liquid medium with a transition metal compound, e.g., a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers. Also disclosed are methods of preparing polymers with the catalyst composition and the resulting polymers.Type: GrantFiled: July 24, 1984Date of Patent: August 12, 1986Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Klaus P. Wagner
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Patent number: 4593009Abstract: A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with an organomagnesium composition and contacting the thus-formed magnesium-containing carrier with a solution of at least one tetravalent vanadium compound. Alternatively, the solution may also contain at least one tetravalent titanium compound in addition to the vanadium compound, thereby producing catalysts containing both, vanadium and titanium. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalysts of the invention.Type: GrantFiled: April 4, 1984Date of Patent: June 3, 1986Assignee: Mobil Oil CorporationInventor: Thomas E. Nowlin
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Patent number: 4568658Abstract: A catalyst composition for polymerizing alpha-olefins in a gas phase continuous process is prepared by combining a catalyst precursor with a catalyst activator in such proportions that the polymer product comprises about 9.times.10.sup.-7 to about 18.times.10.sup.-7 gram-moles of the activator per gram of the polymer produced. The use of the activator in these proportions lowers the partial pressure of the monomers used in the process without sacrificing quality of the product. The catalyst precursor is prepared by reacting a carrier having OH groups with a stoichiometric excess, with respect to the OH groups, of an organomagnesium composition, and subsequently reacting the product with a transition metal compound.Type: GrantFiled: September 5, 1984Date of Patent: February 4, 1986Assignee: Mobil Oil CorporationInventors: John E. Cook, Thomas J. Giacobbe, Robert O. Hagerty
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Patent number: 4562169Abstract: Alpha-olefin polymerization catalysts are prepared by heating a solid porous carrier having reactive OH groups in the atmosphere of an oxygen-containing gas. The resulting catalysts exhibit higher productivity and produce ethylene polymers of ethylene/C.sub.3 -C.sub.10 copolymers having higher bulk density than similar catalysts prepared with the carriers heated in an atmosphere of nitrogen.Type: GrantFiled: October 4, 1984Date of Patent: December 31, 1985Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Irena B. Petsche, Kenneth G. Schurzky
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Patent number: 4547479Abstract: A catalyst support based on aluminum polyphosphate or polyphosphoric acid-impregnated alumina is provided by two alternative techniques. In the first embodiment, an aluminum polyphosphate composition is heated in a dry atmosphere and thereafter impregnated with a zerovalent chromium component under anhydrous conditions. The resulting catalyst is active for olefin polymerization. In the second embodiment, alumina is impregnated with a polyphosphoric acid composition. This resulting polyphosphoric acid impregnated alumina can be used as a support for zerovalent chromium or can be impregnated with a chromium component and oxidized to give an active hexavalent chromium species. The resulting catalysts are advantageous because of their unusual sensitivity to hydrogen thus allowing great leeway in molecular weight control.Type: GrantFiled: July 2, 1984Date of Patent: October 15, 1985Assignee: Phillips Petroleum CompanyInventors: Marvin M. Johnson, Max P. McDaniel
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Patent number: 4481301Abstract: The present invention relates to a highly active catalyst composition for polymerizing alpha-olefins prepared by treating a support with an organomagnesium composition and contacting the thus formed solid supported magnesium composition in a liquid medium with a tetravalent titanium compound. This catalyst is particularly useful for the production of linear low density polyethylene polymers.Type: GrantFiled: November 24, 1982Date of Patent: November 6, 1984Assignee: Mobil Oil CorporationInventors: Thomas E. Nowlin, Klaus P. Wagner
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Patent number: 4481302Abstract: A catalyst system suitable for olefin polymerization comprising a mixed phosphate base made up of 75-99 mole percent aluminum phosphate and 1 to 25 mole percent of a phosphate of at least one other metal selected from gallium, yttrium, zirconium, lanthanum, neodymium and thorium in conjunction with an organoboron cocatalyst. The resulting catalyst system is capable of giving ethylene polymer having relatively low melt index and at the same time exhibits great sensitivity to molecular weight control agents so as to enable the production of a broad spectrum of polymers so far as melt index is concerned from a single catalyst system.Type: GrantFiled: January 27, 1983Date of Patent: November 6, 1984Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Marvin M. Johnson
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Patent number: 4478987Abstract: A new polymerization catalyst system comprising an aluminum compound and a transition metal compound on an alumina-based aerogel support, a process for preparing the polymerization catalyst system and use of the catalyst system for polymerization and copolymerization of alpha-olefins are disclosed. A heat-activated alumina-based aerogel useful as a catalyst support and having a morphology by transmission electron microcopy comprising extremely thin folded film-like ribbons or plates and having a high BET surface area, high pore volume, and low bulk density is also disclosed.Type: GrantFiled: September 24, 1982Date of Patent: October 23, 1984Assignee: Allied CorporationInventors: Anthony J. Fanelli, Alson K. Price
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Patent number: 4478988Abstract: A catalyst and method in which the catalyst is used in association with an aluminum cocatalyst in the polymerization and copolymerization of 1-olefins. The catalyst is prepared by reacting certain organic silicon compounds with silica, alumina or the like having surface hydroxyl groups, or a mixture thereof, in which the silicon compound reacts with these surface hydroxyl groups, followed by reacting the product of this with an organomagnesium compound and further reacting this product with an alcohol or reacting the product with an alcohol and then with an organomagnesium compound and then with a halide or alkoxide of titanium, vanadium, zirconium or mixtures of these.Type: GrantFiled: May 24, 1982Date of Patent: October 23, 1984Assignee: Chemplex CompanyInventors: Thomas J. Pullukat, Raymond E. Hoff
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Patent number: 4446288Abstract: An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups, and a magnesium alkyl or a magnesium alkyl-aluminum alkyl complex of the general formula (MgR.sub.2).sub.m (AlR'.sub.3).sub.n where R and R' are alkyl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with an electron-donating alcohol and a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by removal, such as by evaporation, of the solvent to give a dry, granular, solid catalyst.Type: GrantFiled: January 4, 1982Date of Patent: May 1, 1984Assignee: Chemplex CompanyInventor: Raymond E. Hoff
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Patent number: 4444968Abstract: In accordance with one embodiment of this invention, a zerovalent chromium compound is introduced onto an activated phosphate-containing support and utilized in conjunction with an organometal cocatalyst, such as a trialkylborane. In accordance with another embodiment of this invention, a phosphate-containing xerogel is formed by removing water from an aluminum phosphate-containing hydrogen by means of azeotropic distillation or washing with a volatile, water miscible organic compound, activated and thereafter zerovalent chromium is incorporated therewith. In other embodiments of this invention, a phosphate-containing support is formed by forming aluminum phosphate from an aluminum alkoxide or from a melt, or by phosphating silica or alumina, or by forming an aluminum phosphate/silica combination. A support thus formed is activated and a zerovalent chromium compound added.Type: GrantFiled: September 27, 1982Date of Patent: April 24, 1984Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Marvin M. Johnson
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Patent number: 4442274Abstract: A supported vanadium catalyst comprising a vanadium compound on a phosphate-containing base. This catalyst in conjunction with an organoaluminum cocatalyst is capable of giving good activity and producing a polymer having broad molecular weight distribution. The catalyst system is sufficiently sensitive to hydrogen to allow broad leeway in controlling the molecular weight of the resulting polymers.Type: GrantFiled: September 27, 1982Date of Patent: April 10, 1984Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Marvin M. Johnson
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Patent number: 4435519Abstract: Vanadium compound/organometallic compound/inorganic oxide catalyst compositions useful for the polymerization of ethylene to polymers having a molecular weight distribution that can be controlled by selection of the appropriate member of a particular family of vanadium compounds are obtained by using, as the vanadium component, at least one vanadium compound prepared by reacting one molar proportion of VOCl.sub.3 and/or VOBr.sub.3 with about 0.5 to 1 molar proportion of a diol corresponding to the formula HO-R-OH, wherein R is a divalent hydrocarbon radical having a chain length of 2 to 16 carbon atoms. The molecular weight distributions of polymers formed in the presence of the catalyst compositions are narrowed as the chain length of R is increased. The preferred vanadium compounds are those prepared by reacting VOCl.sub.3 with a diol wherein R is a straight- or branched-chain alkylene group containing 2 to 6 carbon atoms.Type: GrantFiled: November 24, 1982Date of Patent: March 6, 1984Assignee: Cities Service Co.Inventors: Richard L. Veazey, B. Timothy Pennington
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Patent number: 4424139Abstract: In accordance with one embodiment of this invention, a bis-(cyclopentadienyl)chromium(II) compound is introduced onto an activated phosphate-containing support and utilized in conjunction with an organometal cocatalyst, such as an alkylaluminum. In accordance with another embodiment of this invention, a phosphate-containing zerogel is formed by removing water from an aluminum phosphate-containing hydrogel by means of azeotropic distillation or washing with a volatile, water miscible organic compound, activated and thereafter a bis-(cyclopentadienyl)chromium(II) compound is incorporated therewith. In other embodiments of this invention, a phosphate-containing support is formed by forming aluminum phosphate from an aluminum alkoxide or from a melt, or by phosphating silica or alumina, or by forming an aluminum phosphate/silica combination. A support thus formed is activated and a bis-(cyclopentadienyl)chromium(II) compound added.Type: GrantFiled: March 30, 1982Date of Patent: January 3, 1984Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, James N. Short
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Patent number: 4397765Abstract: A catalyst system suitable for olefin polymerization comprising a catalyst component made up of chromium on a phosphated alumina or low phosphorus aluminum phosphate base and optionally an organometal cocatalyst. The resulting catalyst is particularly sensitive to the effects of hydrogen as a molecular weight control agent, thus allowing the production of polymers of having a melt flow varying over a wide spectrum utilizing the same catalyst.Type: GrantFiled: May 5, 1982Date of Patent: August 9, 1983Assignee: Phillips Petroleum CompanyInventor: Max P. McDaniel
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Patent number: 4397761Abstract: A supported vanadium catalyst comprising a vanadium compound on a phosphate-containing base. This catalyst in conjunction with an organoaluminum cocatalyst is capable of giving good activity and producing a polymer having broad molecular weight distribution. The catalyst system is sufficiently sensitive to hydrogen to allow broad leeway in controlling the molecular weight of the resulting polymers.Type: GrantFiled: December 31, 1980Date of Patent: August 9, 1983Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Marvin M. Johnson
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Patent number: 4383096Abstract: An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups, and a complex of the general formula (MgR.sub.2).sub.m (AlR'.sub.3).sub.n where R and R' are alkyl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by evaporation of the solvent.Type: GrantFiled: November 3, 1980Date of Patent: May 10, 1983Assignee: Chemplex CompanyInventors: Mitsuzo Shida, Thomas J. Pullukat, Raymond E. Hoff
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Patent number: 4364841Abstract: In accordance with one embodiment of this invention, a zerovalent chromium compound is introduced onto an activated phosphate-containing support and utilized in conjunction with an organometal cocatalyst, such as a trialkylborane. In accordance with another embodiment of this invention, a phosphate-containing xerogel is formed by removing water from an aluminum phosphate-containing hydrogel by means of azeotropic distillation or washing with a volatile, water miscible organic compound, activated and thereafter zerovalent chromium is incorporated therewith. In other embodiments of this invention, a phosphate-containing support is formed by forming aluminum phosphate from an aluminum alkoxide or from a melt, or by phosphating silica or alumina, or by forming an aluminum phosphate/silica combination. A support thus formed is activated and a zerovalent chromium compound added.Type: GrantFiled: December 31, 1980Date of Patent: December 21, 1982Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Marvin M. Johnson
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Patent number: 4359403Abstract: An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups treated with a fluorine compound and with a compound of magnesiumhydrocarbyl or a complex of the general formula (MgR.sub.2).sub.m (AlR.sub.3 ').sub.n where R and R' are alkyl or aryl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by separation of the solvent. The disclosure also includes a method of making such catalysts and a method of making polymers of one or more 1-olefins by the use of these catalysts under polymerizing conditions.Type: GrantFiled: April 13, 1981Date of Patent: November 16, 1982Assignee: Chemplex CompanyInventors: Raymond E. Hoff, Thomas J. Pullukat, Mitsuzo Shida
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Patent number: 4299936Abstract: A transition metal compound containing at least one .pi.-bonded arene is contacted with an inorganic oxide, hydroxide, oxyhalide, hydroxyhalide or halide. The transition metal compound can be a compound such as titanium(O)ditoluene or TiCl.sub.2.2AlCl.sub.3 durene. The inorganic compound is preferably of high surface area and this may be inherent in the compound or can be achieved by a grinding procedure. The inorganic compound can be treated with a halogen containing compound either before, during or after the contacting with the transition metal compound. The product of the contacting is useful either as catalyst for the polymerization of unsaturated hydrocarbon monomers or as a component of such a catalyst. When used as a component of an olefine polymerization catalyst, the transition metal product can be mixed with an organo-aluminum compound and a Lewis Base compound such as an ester.Type: GrantFiled: August 7, 1978Date of Patent: November 10, 1981Assignee: Imperial Chemical Industries LimitedInventors: John P. Candlin, Keith C. Wilson, Ronald Pearce
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Patent number: 4299937Abstract: A process for the preparation of catalysts of the polymerization of olefines, e.g. ethylene and propylene. This process comprises essentially the two following steps:(1) A compound (A) of an element selected from groups Ia, Ib, IIa, IIb, IIIa, IIIb, VIa and VIIb of the Periodic Table of Elements is heated and milled under the protection of an inert gas with an organic acetoxy compound; then the volatile portions of the mixture are eliminated by distillation.(2) The solid resulting from the first step is dissolved or dispersed in a non-polar hydrocarbon and an activator (B) is added, mixed and heated with said solution or dispersion until a homogeneous solution or dispersion of activated catalyst is obtained. (B) is selected from compounds of elements IVa, IVb and Vb of the Periodic Table. This catalyst is used in admixture with a polymerization promoter (C) selected from organo-metallic additives, e.g. aluminum-organic compounds for the polymerization of olefines at relatively low temperatures and pressures.Type: GrantFiled: September 20, 1979Date of Patent: November 10, 1981Assignee: Battelle Memorial InstituteInventor: Alfred Columberg
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Patent number: 4297461Abstract: 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: April 17, 1980Date of Patent: October 27, 1981Assignee: National Petro Chemicals Corp.Inventor: Anthony N. Speca
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Patent number: 4290914Abstract: Catalysts, especially for olefin polymerization are prepared by coating an aluminum compound on a selected high pore volume silica gel, and calcining the support at temperatures of from about 200.degree. to 2000.degree. F. The preferred catalyst is prepared with an inorganic support material as aforesaid, thereafter depositing an organophosphoryl chromium compound thereon, and activating the thus-treated support by heating in a non-reducing, preferably oxygen-containing, atmosphere at temperatures of from about 800.degree. to 2000.degree. F. The activated, supported catalyst composition may, but need not necessarily, be combined with a metallic and/or non-metallic reducing agent, to provide a catalyst system useful in the polymerization of 1-olefins.Type: GrantFiled: June 16, 1980Date of Patent: September 22, 1981Assignee: National Petro Chemicals Corp.Inventors: Stanley J. Katzen, Louis J. Rekers
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Patent number: 4285834Abstract: A catalyst mixture containing at least two independently supported catalysts, at least one of which is an inorganic halide supported titanium and/or vanadium Ziegler type catalyst and at least one other is an inorganic oxide supported, chromium catalyst.These catalyst mixtures are suitable for polymerizing one or more .alpha.-olefins.Type: GrantFiled: December 31, 1979Date of Patent: August 25, 1981Assignee: The Dow Chemical CompanyInventors: Kirby Lowery, Jr., Fred L. Vance, Jr.
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Patent number: 4265785Abstract: New, highly active catalysts for the polymerization of ethylene and mixtures of ethylene with higher alpha-olefins and/or diolefins, are disclosed. The catalysts are prepared by mixing (a) hydrides or organometallic compounds of metals belonging to Groups I, II or III of the Mendelycev Periodic Table with (b) the products obtained by contacting titanium compounds with activated anhydrous halides of magnesium or manganese, diluted with anhydrous compounds of metals belonging to Group III or IV of said Periodic Table, and which are different from either (a) or the titanium compound of (b).Type: GrantFiled: August 10, 1979Date of Patent: May 5, 1981Assignee: Montecatini Edison S.p.A.Inventors: Umberto Giannini, Paolo Longi, Domenico Deluca, Angelo Pricca
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Patent number: 4263171Abstract: An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups, and a complex of the general formula (MgR.sub.2).sub.m (AlR.sub.3 ').sub.n where R and R' are alkyl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by evaporation of the solvent.Type: GrantFiled: August 1, 1979Date of Patent: April 21, 1981Assignee: Chemplex CompanyInventors: Mitsuzo Shida, Thomas J. Pullukat, Raymond E. Hoff
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Patent number: 4247669Abstract: Alumina-supported halogen-containing transition metal compounds prepared in such manner that (a) the transition metal compound is chemically bound to and supported by an activated alumina having a high surface area and an internal pore volume greater than 0.8 cc/g., (b) the concentration of the transition metal compound chemically bound to the support is greater than 10 grams of transition metal per kilogram of activated alumina, and (c) the atom ratio of halogen to transition metal on the support is higher than that of the halogen-containing transition metal compound which is used and preferably greater than 3:1, have been found to be unusually effective cocatalysts for the polymerization of ethylene and other .alpha.-olefins. These supported cocatalysts, which may be used to produce polyethylene as well as interpolymers of ethylene with other .alpha.-olefins and with diolefins, are prepared by heating an alumina hydrate (such as boehmite) to a temperature in the range from about 500.degree. C. to 900.Type: GrantFiled: December 26, 1979Date of Patent: January 27, 1981Assignee: Solvay & CieInventors: Luigi Reginato, Charles Bienfait, Jacques Stevens
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Patent number: 4241112Abstract: According to the invention, the method for applying a polymer coating onto the surface of a solid filler comprises deposition of a complex organometallic catalyst, containing a compound of a transition metal and an organic compound of a metal of the second or third groups of the periodic system, on the surface of the solid filler and liquid- or gas-phase polymerization of olefins at a temperature of 50.degree. to 170.degree. C. and a pressure of 1 to 60 atm on said catalyst deposited on the surface of the solid filler. The deposition is carried out in two stages. The first stage is gas-phase deposition of the first component of the catalyst, i.e. a compound of a transition metal, on the surface of the solid filler. The second stage is gas- or liquid-phase deposition of the second component of the catalyst, i.e. an organic compound of a metal of the second or third group of the periodic system.Type: GrantFiled: August 8, 1978Date of Patent: December 23, 1980Inventors: Leonid A. Kostandov, Nikolai S. Enikolopov, Fridrikh S. Dyachkovsky, Ljudmila A. Novokshonova, Jury A. Gavrilov, Olga I. Kudinova, Tatyana A. Maklakova, Leonid A. Akopian, Khaim-Mordkhe A. Brikenshtein
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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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Catalyst composition, method for producing same and method for polymerization of 1-olefins with same
Patent number: 4234709Abstract: Supported catalyst compositions incorporating preformed materials comprising the reaction product of organophosphorus compounds such as the organophosphates and organophosphites with chromium trioxide, wherein the organic moiety is a hydrocarbon radical, e.g., alkyl, aralkyl, aryl, cycloalkyl, or the like or combinations thereof. Typical supports constitute an inorganic material of high surface area, especially a high pore volume (>1.96 cc/g) silica xerogel. Catalytically promoted polymerizations of 1-olefins proceed efficiently to products of specially adapted utility for molding, and particularly the production of blow molded articles. The polymerization activity of the catalyst compositions is promoted by heating in a dry, oxygen containing atmosphere. The catalysts are utilized alone or in conjunction with other catalytic ingredients such as organometallic and/or organo non-metallic reducing agents.Type: GrantFiled: May 7, 1976Date of Patent: November 18, 1980Assignee: National Petro Chemicals CorporationInventors: Louis J. Rekers, Stanley J. Katzen -
Patent number: 4223117Abstract: A process for the polymerization of olefins in the presence of a catalyst comprising a titanium compound and/or vanadium compound supported on a solid carrier and an organoaluminum compound, characterized in that said solid carrier comprises a solid product obtained by the reaction of an organomagnesium compound or a reaction mixture resulting from the organomagnesium compound and at least one compound selected from the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide and aluminum hydroxide, with an aluminum halogenide and/or silicon halogenide, whereby there are produced olefine polymers in an extremely large amount per unit weight of catalyst.Type: GrantFiled: April 10, 1978Date of Patent: September 16, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Takezo Sano, Akio Kobayashi, Yasuharu Yamada
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Patent number: 4212765Abstract: A catalyst for the polymerization of 1-olefins is prepared by reacting a chromate ester fixed on a carrier selected from the group consisting of oxides of silicon, oxides of aluminum, and mixtures of said oxides, in the absence of an unsaturated polymerizable hydrocarbon, with an aluminum-organic compound and subsequently activating with aluminum-organic compound. No washing liquids that have to be worked up are obtained and the polymers, obtained in a high yield have a broad molecular weight distribution and contain only a small proportion of high molecular constituents. The films made therefrom are practically free from specks.Type: GrantFiled: January 22, 1979Date of Patent: July 15, 1980Assignee: Hoechst AktiengesellschaftInventor: Klemens Gutweiler
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Patent number: 4187385Abstract: Polymerization of ethylene or .alpha.-olefins using a catalyst comprising a titanium component obtained by copulverizing the starting titanium component of Ziegler catalysts and organoaluminum compound with a small amount of ethylene or .alpha.-olefins, and an organoaluminum component. The titanium catalyst component can be modified by subjecting the copulverized titanium component to a contact with an inert organic solvent or its mixture with a modifier (1) an oxygen-, sulphur-, phosphor-, nitrogen- or silicon- containing organic compound, (2) a combination of such an organic compound and an aluminum halide, (3) an organoaluminum compound or (4) a Lewis acid.Type: GrantFiled: May 16, 1977Date of Patent: February 5, 1980Assignee: Mitsui Toatsu Chemical, Inc.Inventors: Tetsuya Iwao, Heizo Sasaki, Akira Ito, Masahiro Kono
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Patent number: 4184028Abstract: Olefin polymerization catalysts are prepared by depositing an organophosphoryl chromium product and an aluminum compound 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 29, 1977Date of Patent: January 15, 1980Assignee: National Petro Chemicals CorporationInventors: Louis J. Rekers, Stanley J. Katzen, Jerome H. Krekeler
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Patent number: 4154915Abstract: An improved catalyst system is disclosed for use in the polymerization or copolymerization of olefins. The catalyst comprises a transition metal compound, an organometal compound and a composite carrier. This carrier is constituted by a SO.sub.3 treated alumina and a magnesium and/or a calcium compound. The polymerization or copolymerization of olefins such as ethylene, propylene and 1-butene is effected under conditions similar to those for reactions by means of Ziegler catalysts, but the resulting polyolefins have a wider molecular weight distribution, viz, a larger flow parameter as required for extrusion or blow molding.Type: GrantFiled: May 8, 1975Date of Patent: May 15, 1979Assignee: Nippon Oil Co., Ltd.Inventors: Kazuo Matsuura, Masaomi Matsuzaki, Toru Nakamura, Nobuyuki Kuroda, Mitsuji Miyoshi
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Patent number: 4148754Abstract: When reacting the reaction product of silicon dioxide and/or a metal oxide and a Grignard compound with a soluble titanium compound, there is obtained a catalyst for the polymerization of 1-olefins, which gives a very high yield and allows a good control of the molecular weight by means of hydrogen without making necessary a separation of the excess of metallo-organic compounds and/or the excess of titanium compounds from the catalyst carrier.Type: GrantFiled: November 23, 1976Date of Patent: April 10, 1979Assignee: Hoechst AktiengesellschaftInventors: Wolfgang Strobel, Rainer Franke
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Patent number: 4148755Abstract: Ziegler catalytic system comprising an organo-metallic compound of a metal of Groups I to III of the Periodic System and a compound of a heavy metal of Groups IV to VI supported on an alumina carrier, the latter being an activated amorphous alumina containing from 0.3 to 30% by weight of salts of aluminum with oxygenated inorganic anions, or of a mixture of the latter with salts of aluminum with non-oxygenated inorganic anions, said carrier being prepared by precipitating an alumina gel at a pH value of 7-10, introducing the inorganic anions into said gel, drying said gel and calcining the resulting amorphous alumina at 250.degree.-700.degree. C.Type: GrantFiled: October 6, 1977Date of Patent: April 10, 1979Assignee: Euteco S.p.A.Inventors: Ferdinando Ligorati, Renzo Invernizzi, Carlo Collu, Maurizio Fontanesi
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Patent number: 4146695Abstract: The invention is directed to new catalysts consisting of a chromium compound and an organometal compound of an element of Group II or III of the periodic system on a carrier, the process for preparing the catalyst and its use in polymerizing 1-alkenes containing 2 to 8 carbon atoms, optionally admixed with at most 10 mole% of at least one other 1-alkene of 2 to 8 carbon atoms.Type: GrantFiled: May 23, 1977Date of Patent: March 27, 1979Assignee: Stamicarbon, B.V.Inventor: Lambertus J. M. A. VAN DE Leemput
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Patent number: 4142990Abstract: Ziegler catalytic system comprising an organo-metallic compound of a metal of Groups I to III of the Periodic Table and a compound of a heavy metal of Groups IV to VI supported on a carrier, the latter being an activated amorphous alumina or alumino-silicate containing from 0.3 to 30% by weight of salts of aluminum with oxygenated inorganic anions, or of a mixture of the latter with salts of aluminum with non-oxygenated inorganic anions, said inorganic anions being introduced into the amorphous alumina or alumino-silicate by contacting the latter with one or more acid solutions of the inorganic anions and the carrier being then activated by calcination at 250.degree. - 700.degree. C.Type: GrantFiled: October 6, 1977Date of Patent: March 6, 1979Assignee: EUTECO S.p.A.Inventors: Ferdinando Ligorati, Renzo Invernizzi, Carlo Collu, Maurizio Fontanesi
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Patent number: 4121030Abstract: A transition metal compound containing at least one .pi.-bonded arene is contacted with an inorganic oxide, hydroxide, oxyhalide, hydroxyhalide or halide. The transition metal compound can be a compound such as titanium(O)ditoluene or TiCl.sub.2.2AlCl.sub.3 durene. The inorganic compound is preferably of high surface area and this may be inherent in the compound or can be achieved by a grinding procedure. The inorganic compound can be treated with a halogen containing compound either before, during or after the contacting with the transition metal compound. The product of the contacting is useful either as catalyst for the polymerization of unsaturated hydrocarbon monomers or as a component of such a catalyst. When used as a component of an olefine polymerization catalyst, the transition metal product can be mixed with an organo-aluminium compound and a Lewis Base compound such as an ester.Type: GrantFiled: November 24, 1976Date of Patent: October 17, 1978Assignee: Imperial Chemical Industries LimitedInventors: John Paton Candlin, Keith Collier Wilson, Ronald Pearce
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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: 4107414Abstract: There is disclosed a process for the stereoregular polymerization of alpha-olefins or mixtures thereof with ethylene, conducted in the presence of highly active and stereospecific new catalysts. The catalysts are obtained from the reaction of a particular Al-alkyl compound which is at least in part in the form of a complex and/or a substitution reaction product with an ester of an oxygenated organic or inorganic acid, with a supported component characterized by having surface area exceeding certain values or showing a particular X-rays spectrum, and obtained by contacting a Ti halogenated compound, preferably in the form of a complex with an electron-donor compound, with a support comprising a Mg or Mn bihalide.In the catalysts the ratio between the Ti compound, expressed in Ti g-atoms, and the g moles of the ester and the electron-donor compound, when present, is lower than 0.3.Type: GrantFiled: May 18, 1977Date of Patent: August 15, 1978Assignee: Montecatini Edison S.p.A.Inventors: Umberto Giannini, Antonio Cassata, Paolo Longi, Romano Mazzocchi
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Patent number: 4100104Abstract: Catalysts, especially for olefin polymerization are prepared by coating an aluminum compound on a selected high pore volume silica gel, and calcining the support at temperatures of from about 200.degree. to 2000.degree. F. The preferred catalyst is prepared with an inorganic support material as aforesaid, thereafter depositing an organophosphoryl chromium compound thereon, and activating the thus-treated support by heating in a non-reducing, preferably oxygen-containing, atmosphere at temperatures of from about 800.degree. to 2000.degree. F. The activated, supported catalyst composition may, but need not necessarily, be combined with a metallic and/or non-metallic reducing agent, to provide a catalyst system useful in the polymerization of 1-olefins.BACKGROUND OF THE INVENTIONThe modification of silica gels for catalytic activity is known as discussed in Burwell, Chemtech, pp. 370-377 (1974).The use of chromium compounds in the polymerization of olefins is well-known. U.S. Pat. Nos.Type: GrantFiled: January 13, 1977Date of Patent: July 11, 1978Assignee: National Petro Chemicals CorporationInventors: Stanley J. Katzen, Louis J. Rekers
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Patent number: 4088812Abstract: This invention discloses an improved catalyst for the polymerization or copolymerization of olefins, and a process for preparing polyolefins which comprises polymerizing or copolymerizing olefins using the said catalyst. According to the invention there is provided a process for preparing polyolefins by polymerizing or copolymerizing olefins using as a catalyst at least one compound selected from the group consisting of a titanium compound and a vanadium compound supported on a solid carrier, and an organometallic compound, said solid carrier comprising a product obtained by treatment with SO.sub.3 of at least one member selected from the group consisting of an oxide of Group II-IV metals of the Periodic Table and a double oxide of the said oxide and other oxide, which other oxide may be another oxide of Group II-IV metals of the Periodic Table or may be an oxide of other Group metals of the same Table.Type: GrantFiled: December 20, 1976Date of Patent: May 9, 1978Assignee: Nippon Oil Company, LimitedInventors: Kazuo Matuura, Masaomi Matsuzaki, Humiaki Oshimi, Nobuyuki Kuroda, Mituji Miyoshi
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Patent number: 4081589Abstract: Adding a finely divided oxide to a terminal olefin polymerization catalyst comprising a hydrocarbon-soluble transition metal compound and a Group II or III metal organic compound reduces the amount of fibrous polymer produced.Type: GrantFiled: December 20, 1976Date of Patent: March 28, 1978Assignee: The Standard Oil CompanyInventors: Edwin F. Peters, David E. Boone