Utilizing Hydrocarbon Containing Unsaturation Not Part Of Benzene Ring Patents (Class 502/108)
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Patent number: 5332793Abstract: A process for the production of EPRs comprising contacting ethylene, propylene, and optionally, a diene, under polymerization conditions, with a catalyst system comprising:(A) a catalyst precursor comprising:(i) a vanadium compound, which is the reaction product of(a) VX.sub.3 wherein each X is independently chlorine, bromine, or iodine; and(b) an electron donor, which is a liquid, organic Lewis base in which VX.sub.3 is soluble;(ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.Type: GrantFiled: June 28, 1993Date of Patent: July 26, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Kevin J. Cann
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Patent number: 5322830Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefins, in which particles are formed from magnesium halide and alcohol, the particles are reacted with an organometallic compound of any of the metals of the groups I to III, the thus obtained particulate product is activated by means of a titanium(IV) compound, and optionally a prepolymerization is carried out for the activated particles. A problem with this kind of a method is, how to form particles from magnesium dihalide and alcohol having an advantageous structure for the polymerization of ethylene and particularly ethylene with a narrow molecular weight distribution. The problem has in the present invention been solved so that the particles are formed by spray-crystallizing a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol and that titanium(IV) alcoxyhalide has been used as the titanium compound.Type: GrantFiled: September 18, 1991Date of Patent: June 21, 1994Assignee: Neste OyInventors: Pekka Sormunen, Jukka Koskinen, Paivi Waldvogel
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Patent number: 5308818Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is an alkyl or cycloalkyl group containing a primary or secondary carbon atom attached to the silicon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl or cycloalkyl group with a primary or secondary carbon atom attached to the silicon atom. The system has a catalyst efficiency of over 30 kg/g-cat.h as the Si/Ti mole ratio varies from 4-20 in the system. The system easily achieves efficiencies over 30 kg/g-cat.h. The system also exhibits good control over the xylene solubles of the polymer products.Type: GrantFiled: June 8, 1992Date of Patent: May 3, 1994Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David J. Rauscher
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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: 5308811Abstract: A catalyst for polymerizing an olefin which consists essentially of a product obtained by contacting (A) a metallocene-type transition metal compound, (B) at least one member selected from the group consisting of clay, clay minerals, ion exchanging layered compounds, diatomaceous earth, silicates and zeolites, and (C) an organic aluminum compound.Type: GrantFiled: May 1, 1992Date of Patent: May 3, 1994Assignee: Mitsubishi Kasei CorporationInventors: Yoshinori Suga, Yasuo Maruyama, Eiji Isobe, Toru Suzuki, Fumihiko Shimizu
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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: 5278263Abstract: Pure syndiotactic 1,2-polybutadiene is a thermoplastic resin which has double bonds attached in an alternating fashion to its polymeric backbone. Films, fibers and molded articles can be made utilizing syndiotactic 1,2-polybutadiene. It can also be blended into rubbers and cocured therewith. Syndiotactic 1,2-polybutadiene can be made by solution, emulsion or suspension polymerization. It typically has a melting point which is within the range of about 195.degree. C. to about 215.degree. C. However, it is often desirable for the syndiotactic 1,2-polybutadiene to have a melting point of less than about 195.degree. C. This invention discloses a process for preparing syndiotactic 1,2-polybutadiene having a melting point of less than about 195.degree. C.Type: GrantFiled: October 5, 1992Date of Patent: January 11, 1994Assignee: The Goodyear Tire & Rubber CompanyInventor: Gary L. Burroway
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Patent number: 5275992Abstract: A process is disclosed for the particle form polymerization of olefins. The process employs a titanium-containing having hydrocarbon soluble titanium components. The resulting catalyst is pretreated with an organometallic reducing agent prior to the introduction of the catalyst into the polymerization zone to give a catalyst which can be used satisfactorily in a loop reactor with lower levels of cocatalyst.Type: GrantFiled: December 7, 1992Date of Patent: January 4, 1994Assignee: Phillips Petroleum CompanyInventors: Kent E. Mitchell, Max P. McDaniel, M. Bruce Welch, Elizabeth A. Benham, Grover W. Cone
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Patent number: 5266544Abstract: In accordance with the present invention, there are provided olefin polymerization solid catalysts comprising[A] a solid titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients, said catalyst component having supported thereon[B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and, if necessary,[C] an organoaluminum oxy-compound.In accordance with the invention, there are also provided olefin polymerization solid catalysts comprising[i] a solid containing a transition metal compound containing a ligand having a cycloalkadienyl skeleton, said solid having supported thereon[ii] a titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients and, if necessary,[iii] an organoaluminum oxy-compound.Type: GrantFiled: May 27, 1992Date of Patent: November 30, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Takashi Ueda
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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: 5247032Abstract: The present invention relates to solid catalyst components for olefin polymerization formed by prepolymerizing at least two types of .alpha.-olefin on an olefin polymerization catalyst comprising a solid titanium catalyst component, an organometallic compound catalyst component, and if necessary, an electron donor, to olefin polymerization catalyst comprising said solid catalyst component for olefin polymerization, an organometallic compound catalyst component, and if necessary, an electron donor, and to processes for olefin polymerization using said olefin polymerization catalyst.According to the present invention, there can be manufactured olefin polymer particles having low adhesive among the polymer particles as well as good particle distribution and excellent granular properties even when they contain a large amount of an amorphous olefin polymer portion.Type: GrantFiled: May 20, 1992Date of Patent: September 21, 1993Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Takashi Ueda
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Patent number: 5244990Abstract: A prepolymerized olefin polymerization catalyst, its preparation, and use are disclosed. The catalyst is prepared by contacting a solid particulate transition metal-containing olefin polymerization catalyst with an olefin in a confined zone under suitable conditions wherein the prepolymerization is conducted under conditions such that the olefin is added to the confined zone at a rate such that the pressure in the confined zone increases no more than about 0.5 psig/sec. during the olefin addition.Type: GrantFiled: January 7, 1992Date of Patent: September 14, 1993Assignee: Phillips Petroleum CompanyInventor: Kent E. Mitchell
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Patent number: 5240894Abstract: The invention relates to a novel process for producing a supported metallocene catalyst system useful for the polymerization and/or copolymerization of olefins, alpha-olefins, and/or diolefins which results in a catalyst product which during polymerization, produces minimal to no reactor fouling and polymer of controlled morphology. The invention is particularly useful for but not limited to polymerizing propylene or copolymerizing propylene with olefins having two or more carbon atoms. The novel support technique described herein results in a catalyst which will obtain polymer product having controlled, uniform particle size, narrow molecular weight distribution, high bulk density and depending upon the metallocene employed and monomers polymerized, stereoregularity.Type: GrantFiled: May 18, 1992Date of Patent: August 31, 1993Assignee: Exxon Chemical Patents Inc.Inventors: Terry J. Burkhardt, Masahide Murata, William B. Brandley
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Patent number: 5241025Abstract: This invention relates to catalyst systems, and a method for using such system, for the enhanced production of homo and copolymer products of olefin, diolefin and/or acetylenically unsaturated monomers. This invention catalyst system comprises a Group III-A element compound for improving the productivity of an olefin polymerization catalyst which is the reaction product of a metallocene of a Group IV-B transition metal and an ionic activator compound comprising a cation capable of donating a proton which will irreversibly react with at least one ligand contained in the Group IV-B metal compound and an anion which is bulky, labile and noncoordinateable with the Group IV transition metal cation produced upon reaction of the metallocene and activator compound to form the catalyst component of the catalyst system.Type: GrantFiled: October 2, 1992Date of Patent: August 31, 1993Assignee: Exxon Chemical Patents Inc.Inventors: Gregory G. Hlatky, Howard W. Turner
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Patent number: 5234880Abstract: A method of manufacturing a polyolefin using a catalyst system of an ingredient (A) and ingredient (B), with ingredient A being obtained through successive reaction steps. Ingredient A is prepared by forming a mixture of (1) the combination of (a) metallic magnesium or an oxygen-containing organic compound of magnesium with (b) a mixture of a monohydroxylated organic compound and a polyhydroxylated organic compound, (2) oxygen-containing organic compounds of titanium and (3) at least one alpha-olefin having at least 4 carbon atoms, such as 1-hexene. The resulting solution is reacted in sequence with (4) at least one first halogenated aluminum compound, (5) at least one silicon compound and (6) at least one second halogenated aluminum compound. Ingredient B is an organometallic compound of metals from Group Ia, IIa, IIIa or IVa of the Periodic Table. The resulting free-flowing polyolefin is characterized by a large average particle size and small amount of fine particles.Type: GrantFiled: May 18, 1992Date of Patent: August 10, 1993Assignee: Paxon Polymer Company, L.P.Inventors: Gregory A. Cook, Theodore R. Engelmann
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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: 5225501Abstract: A process for producing a propylene random copolymer comprising the repeating units (I)-(III) in quantities of 70-99.9 molar % of (I), 0-15 molar % and 0.1-30 molar %, respectively, which comprises contacting monomers which afford the following repeating units: ##STR1## m denotes 0 or an integer of 2-10, R.sub..alpha., R.sub..beta. and R.sub..gamma. independently represent a hydrogen atom or a hydrocarbyl group having 1-5 carbon atoms, at least one of R.sub..beta. and R.sub..gamma. being the hydrocarbyl group, and n denotes an integer of 1-5, with a polymerization catalyst to copolymerize, the polymerization catalyst comprising:component (A) which is a transition metal compound represented by the formula:Q.sub.a (C.sub.5 H.sub.5-a-b R.sup.1.sub.b)(C.sub.5 H.sub.5-a-c R.sup.2.sub.c)MeXYwherein R.sup.1 and R.sup.Type: GrantFiled: May 1, 1992Date of Patent: July 6, 1993Assignee: Mitsubishi Petrochemical Company LimitedInventors: Takashi Fujita, Toshihiko Sugano, Hideshi Uchino
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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: 5204303Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefines, in which particles are formed of magnesium dihalide and alcohol, the particles are reacted with an organic compound of a metal from the groups I-III, the thus obtained particulate product is activated by means of a titanium and/or vanadium compound and optionally a donor, and optionally a prepolymerization is carried out for the activated particles. A problem of such a method is how to form particles of magnesium dihalogenide and alcohol having a structure advantageous for the polymerization of olefins. The problem has in the present invention been solved so that the particles are formed by spray crystallizing (spray freezing) a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol. The hydroxyl content of the particles so obtained is much greater than earlier, which results in a much more active procatalyst than the preceding ones.Type: GrantFiled: September 16, 1991Date of Patent: April 20, 1993Assignee: Neste OyInventors: Inkeri T. Korvenoja, Arja-Liisa Kostiainen, Fero I. Iiskola, Pekka J. E. Sormunen, Bill B. B. Gustatsson, Hilkka R. Knuuttila, Ulf Palmqvist
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Patent number: 5194415Abstract: Prepolymer-containing catalysts compositions and processes for making and using such catalysts are disclosed. These catalysts compositions are particularly useful for polymerizing 4-methyl-1-pentene to poly(4-methyl-1-pentene) and to improve the optical properties of polyolefins.Type: GrantFiled: December 12, 1991Date of Patent: March 16, 1993Assignee: Phillips Petroleum CompanyInventors: Phil M. Stricklen, Francis X. Mueller, Jr., Kenneth W. Willcox, Joyce K. Snow
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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: 5192730Abstract: A process for preparing chemically stable compositions of tetra(hydrocarbyl)metallic compounds in solution, and an improved process for the preparation of active 1-olefin polymerization catalysts.Type: GrantFiled: November 13, 1991Date of Patent: March 9, 1993Assignee: E. I. Du Pont de Nemours and CompanyInventors: Steven D. Ittel, Frederick N. Tebbe
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Patent number: 5179178Abstract: A process for polymerizing olefins wherin a suitable amount of a fumed refractory oxide is used to improve the flow of particulate catalyst as a slurry of that catalyst is charged to the polymerization zone.Type: GrantFiled: May 15, 1992Date of Patent: January 12, 1993Assignee: Phillips Petroleum CompanyInventors: Elizabeth M. Stacy, M. Bruce Welch, Shirley J. Martin, Max P. McDaniel, Dale E. Pierce
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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: 5166110Abstract: A process is provided for the synthesis of a solid Ziegler catalyst or of a transition metal solid constituent thereof, which entails preparing the solid catalyst or constituent thereof as a suspension in an inert liquid medium by contacting precursors or ingredients of the catalyst or of the constituent in the inert liquid medium in one or more steps, and drying the suspension, and collecting the catalyst or constituent thereof; and wherein the process is conducted in a single multi-function reactor having a longitudinal axis and which can pivot around an axis which intersects perpendicularly with this axis.Type: GrantFiled: December 19, 1990Date of Patent: November 24, 1992Assignee: Elf Atochem S.A.Inventor: Claude Brun
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Patent number: 5166281Abstract: The present invention relates to a catalyst and a process for preparing a catalyst suitable for polymerization of olefins. The process is carried out in a hydrocarbon liquid medium and comprises successively contacting a refractory oxide support with (a) a dialkylmagnesium optionally with a trialkylaluminium, (b) a particular monochloro organic compound, (c) a titanium and/or vanadium compound(s), and then (d) with ethylene optionally mixed with a C.sub.3 -C.sub.8 alpha-olefin in the presence of an organo-aluminium or organozinc compound to form a prepolymerised catalyst. The catalyst has a high activity, particularly in a gas phase polymerization of ethylene, and has a great ability of copolymerizing alpha-olefins with ethylene.Type: GrantFiled: March 6, 1992Date of Patent: November 24, 1992Assignee: BP Chemicals LimitedInventors: Claude Chamla, Erick Daire
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Patent number: 5165998Abstract: The present invention relates to a process for the polymerization of ethylene or copolymerization of ethylene and at least one other alpha-olefin, in the gas phase in a fluidized bed reactor, in the presence of a catalyst comprising chromium compounds associated with a granular support comprising a refractory oxide and activated by thermal treatment, which process is characterized in that the catalyst is used in the form of active particles of prepolymer, obtained by bringing the said catalyst in contact with ethylene, alone, or in a mixture with at least one higher alpha-olefin, in such a way that the prepolymer contains from 4.times.10.sup.-5 to 3 milligram atoms of chromium in the catalyst per gram.Type: GrantFiled: January 2, 1990Date of Patent: November 24, 1992Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, John G. Speakman
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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: 5153158Abstract: The present invention relates to solid catalyst components for olefin polymerization formed by prepolymerizing at least two types of .alpha.-olefin on an olefin polymerization catalyst comprising a solid titanium catalyst component, an organometallic compound catalyst component, and if necessary, an electron donor, to olefin polymerization catalyst comprising said solid catalyst component for olefin polymerization, an organometallic compound catalyst component, and if necessary, an electron donor, and to processes for olefin polymerization using said olefin polymerization catalyst.According to the present invention, there can be manufactured olefin polymer particles having low adhesive among the polymer particles as well as good particle distribution and excellent granular properties even when they contain a large amount of an amorphous olefin polymer portion.Type: GrantFiled: December 27, 1990Date of Patent: October 6, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Masao Nakano, Takashi Ueda
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Patent number: 5151397Abstract: A polymerization catalyst is formed by combining a metal halide compound, a solvent, an effective amount of water to reduce fines and increase particle size, and a transition metal compound to form a first catalyst component and mixing the first catalyst component with a precipitating agent. After mixing the first catalyst component and the precipitating agent, the mixture can be heated to a temperature higher than the mixing temperature to reduce polymer fines. In the alternative prepolymer can be deposited on the catalyst(s) in an amount effective to reduce polymer fines. Optionally the catalyst can be treated with a halide ion exchanging source. The catalyst can also be combined with an organometallic cocatalyst.Type: GrantFiled: December 16, 1991Date of Patent: September 29, 1992Assignee: Phillips Petroleum CompanyInventors: Kent E. Mitchell, Stanley J. Marwil
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Patent number: 5147839Abstract: Ziegler polymerization of .alpha.-olefins is disclosed which is characterized by a solid catalyst component. The solid catalyst component, Component (A), comprises Sub-component (i) which is a solid catalyst component for Ziegler catalysts comprising Ti, Mg and a halogen; Sub-component (ii) which is a silicon compound having a plurality of a bond represented by a formula: Si--OR.sup.1R.sup.1.sub.m X.sub.n Si(OR.sup.2).sub.4-n-mwherein R.sup.1 indicates a hydrocarbyl group of 1 to 8 carbon atoms, Sub-component (iii) which is a vinylsilane compound, and Sub-component (iii) which is an organometal compound of a metal of Groups I to IV of the Periodic Table. No need of an outside electron donor may be required, and the polymer produced is improved in its content of a "tacky" polymer.Type: GrantFiled: February 7, 1991Date of Patent: September 15, 1992Assignee: Mitsubishi Petrochemical Company LimitedInventors: Takashi Fujita, Toshihiko Sugano
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Patent number: 5145818Abstract: In accordance with the present invention, there are provided olefin polymerization catalysts comprising[A] a titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients,[B-1] a transition metal compound containing a ligand having a cycloalkadienyl skeleton,[C] an organoaluminum oxy-compound and, if necessary,[D] an organoaluminum compound.Further, in accordance with the invention, there are provided olefin polymerization catalysts comprising[A] a titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients,[B-2] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and an anion compound containing boron, and[C] an organoaluminum compound and/or an organoaluminum oxy-compound.Type: GrantFiled: December 21, 1990Date of Patent: September 8, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Kenji Sugimura, Takashi Ueda
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Patent number: 5143880Abstract: A solid-catalyst component for use in the polymerization of .alpha.-olefins obtained byreducing a titanium compound represented by the following general formula:Ti(OR.sup.1).sub.n x.sub.4-nwherein R.sup.1 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom and n represents a number satisyfing 0<n.ltoreq.4, with an organomagnesium compound in the presence of an organic silicon compound having Si--O bond to produce a solid product,treating the solid product with an ester compound,treating the ester-treated solid product with a mixture of an ether compound and titanium tetrachloride or with a mixture of an ether compound, titanium tetrachloride and an ester compound to obtain a trivalent titanium compound-containing solid catalyst precursor, andtreating the solid catalyst precursor with a small quantity of an olefin in the presence of an organoaluminum compound to obtain a solid catalyst component for use in the polymerization of .alpha.-olefins.Type: GrantFiled: March 11, 1991Date of Patent: September 1, 1992Assignee: Sumitomo Chemical Company, LimitedInventors: Toshio Sasaki, Takeshi Ebara, Kiyoshi Kawai
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Patent number: 5137856Abstract: The invention relates to a method for the preparation of a supported polymerization catalyst in a multi-function reactor (1) which is equipped with a mixer (2) and at the bottom of which there is fitted a downward substantially conically converging sieve tray (3), possibly detachable, and in which there are carried out, as required for the preparation of the catalyst, an activation stage, i.e. the treatment of the catalyst support with a transition metal compound, washing stages using a suitable solvent, and drying stages using an inert gas, and possibly a prepolymerization of a suitable monomer by means of the obtained activated catalyst and a co-catalyst and possible other compounds, for example a polymerization medium.Type: GrantFiled: March 22, 1989Date of Patent: August 11, 1992Assignee: Neste OyInventors: Jukka Koskinen, Eero Iiskola, Pekka Sormunen
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Patent number: 5135995Abstract: A method of manufacturing a polyolefin using a catalyst system of an ingredient (A) and ingredient (B), with ingredient A being obtained through successive reaction steps. Ingredient A is prepared by forming a mixture of (1) the combination of (a) metallic magnesium or an oxygen-containing organic compound of magnesium with (b) a mixture of a monohydroxylated organic compound and a polyhydroxylated organic compound, (2) oxygen-containing organic compounds of titanium and (3) at least one alpha-olefin having at least 4 cargon atoms, such as 1-hexene. The resulting solution is reacted in sequence with (4) at least one first halogenated aluminum compound, (5) at least one silicon compound and (6) at least one second halogenated aluminum compound. Ingredient B is an organometallic compound of metals from Group Ia, IIa, IIIa or IVa of the Periodic Table. The resulting free-flowing polyolefin is characterized by a large average particle size and small amount of fine particles.Type: GrantFiled: October 11, 1990Date of Patent: August 4, 1992Assignee: Paxon Polymer Company, L.P.Inventors: Gregory A. Cook, Theodore R. Engelmann
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Patent number: 5132261Abstract: The present invention relates to a catalyst for the polymerization of olefins, and provides a catalyst component of magnesium support type which has a high catalytic activity as well as improved catalytic grain strength sufficient for practical use and which hardly deteriorates even after storage for a long time. The catalyst component is obtained by contacting(a) metallic magnesium with(b) a hydrocarbon represented by the general formula RX wherein R is a hydrocarbon group of 1 to 20 carbon atoms and X is a halogen atom, then contacting the resulting composition with(c) a compound represented by the general formula X.sup.1 nM(OR.sup.1).sub.m-n wherein X.sup.1 is a hydrogen atom, halogen atom or a hydrocarbon group of 1 to 20 carbon atoms, M is a boron, carbon, aluminum, silicon or phosphorus atom, R.sup.1 is a hydrocarbon group of 1 to 20 carbon atoms, m is the atomic valence of M and m>n.gtoreq.0, and(d) a titanium alkoxide represented by the general formula Ti(OR.sup.2).sub.4 wherein R.sup.Type: GrantFiled: January 7, 1991Date of Patent: July 21, 1992Assignee: Tonen CorporationInventors: Masahide Murata, Hiroyuki Furuhashi, Seizaburo Kanazawa, Teruo Yashiro, Masafumi Imai, Akira Nakano
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Patent number: 5130283Abstract: According to the present invention, there is provided a catalyst component of metal oxide support type which has a high catalytic activity, that is, a little catalyst residue in a polymer, as well as improved catalytic grain strength sufficient for practical use and which hardly deteriorates even after storage for a long time. The catalyst component is obtained by contacting(a) a metal oxide with(b) a dihydrocarbyl magnesium, then contacting the resulting composition with(c) a compound represented by the general formula X.sup.1 .sub.n M(OR.sup.1).sub.m-n wherein X.sup.1 is a hydrogen atom, halogen atom or a hydrocarbon group of 1 to 20 carbon atoms, M is a boron, carbon, aluminum, silicon or phosphorus atom, R.sup.1 is a hydrocarbon group of 1 to 20 carbon atoms, m is the atomic valence of M and m>n.gtoreq.0, and(d) a titanium alkoxide represented by the general formula Ti(OR.sup.2).sub.4 wherein R.sup.Type: GrantFiled: January 7, 1991Date of Patent: July 14, 1992Assignee: Tonen CorporationInventors: Masahide Murata, Hiroyuki Furuhashi, Akira Nakano, Teruo Yashiro, Seizaburo Kanazawa, Masafumi Imai
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Patent number: 5126301Abstract: A solid catalyst for polymerizing an olefin is prepared from an organometallic compound, a fine-particle carrier, an aluminoxane, a compound of group IVB transition metal in periodic table, and an olefin polymer produced in a preliminary polymerization. The catalyst has a high polymerization activity and is capable of producing an olefin polymer having a narrow molecular- weight distribution. When the catalyst is used for producing an olefin copolymer, the resulting copolymer has both narrow molecular-weight distribution and composition distribution.Type: GrantFiled: March 12, 1990Date of Patent: June 30, 1992Assignee: Mitsui Petrochemical Industries, Inc.Inventors: Toshiyuki Tsutsui, Ken Yoshitsugu, Akinori Toyota, Norio Kashiwa
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Patent number: 5124296Abstract: The present invention relates to a catalyst and a process for preparing a catalyst suitable for polymerization of olefins. The process is carried out in a hydrocarbon liquid medium and comprises successively contacting a refractory oxide support with (a) a dialkylmagnesium optionally with a trialkylaluminium, (b) a particular monochloro organic compound, (c) a titanium and/or vanadium compound(s), and then (d) with ethylene optionally mixed with a C.sub.3 -C.sub.8 alpha-olefin in the presence of an organo-aluminium or organozinc compound to form a prepolymerized catalyst. The catalyst has a high activity, particularly in a gas phase polymerization of ethylene, and has a great ability of copolymerizing alpha-olefins with ethylene.Type: GrantFiled: March 25, 1991Date of Patent: June 23, 1992Assignee: BP Chemicals LimitedInventors: Claude Chamla, Erick Daire
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Patent number: 5122583Abstract: The invention provides a process for increasing the efficiency of pre-polymerized catalysts used in the polymerization of olefins. The invention includes contacting a pre-polymerized catalyst with a cocatalyst or a mixture of cocatalyst and an electron donor prior to introducing the catalyst into a polymerization reaction zone.Type: GrantFiled: November 19, 1990Date of Patent: June 16, 1992Assignee: Fina Technology, Inc.Inventors: John A. Ewen, Alan H. Bitzer, David L. Gressett, Herbert G. Hummel
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Patent number: 5120696Abstract: In accordance with the present invention, there are provided olefin polymerization solid catalysts comprising[A] a solid titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients, said catalyst component having supported thereon[B] a transition metal compound containing a ligand having a cycloalkadienyl skeleton and, if necessary,[C] an organoaluminum oxy-compound.In accordance with the invention, there are also provided olefin polymerization solid catalysts comprising[i] a solid containing a transition metal compound containing a ligand having a cycloalkadienyl skeleton, said solid having supported thereon[ii] a titanium catalyst component containing titanium, magnesium and halogen as its essential ingredients and, if necessary,[iii] an organoaluminum oxy-compound.Type: GrantFiled: December 27, 1990Date of Patent: June 9, 1992Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Toshiyuki Tsutsui, Takashi Ueda
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Patent number: 5115054Abstract: Prepolymer-containing catalysts compositions and processes for making and using such catalyst are disclosed. These catalysts compositions are particularly useful for polymerizing 4-methyl-1-pentene to poly(4-methyl-1-pentene) and to improve the optical properties of polyolefins.Type: GrantFiled: October 12, 1990Date of Patent: May 19, 1992Assignee: Phillips Petroleum CompanyInventors: Phil M. Stricklen, Francis X. Mueller, Jr., Kenneth W. Willcox, Joyce K. Snow
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Patent number: 5112786Abstract: A catalyst for polymerization of olefin monomers, comprising Component (A) which is a solid catalytic compound obtained by subjecting at least the following three compounds to a contact reaction; Sub-component (i) which is a component for Ziegler catalysts comprising titanium, magnesium and a halogen; Sub-component (ii) which is a silicon compound represented by the formula R.sup.1 .sub.4-n SiX.sub.n wherein R.sup.1 is a hydrocarbyl group having 1 to 20 carbon atoms, X is a halogen, and n is a number in the range of 0<n.ltoreq.4, and Sub-component (iii) which is divinylbenzene, the amount of said Sub-component (iii) polymerized in the course of the contact reaction being from 0.01 to 10 g per 1 g of the Sub-component (i), and Component (B) which is an organoaluminum compound.When polymerizing .alpha.Type: GrantFiled: June 19, 1991Date of Patent: May 12, 1992Assignee: Mitsubishi Petrochemical Company LimitedInventor: Takashi Fujita
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Patent number: 5112785Abstract: The method of forming a catalytic component for use in the polymerization of ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin in a gas-phase comprising impregnating a porous metal oxide support with at least one titanium compound, magnesium compound, and chlorine compound, and prepolymerizing ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin, a least partially in suspension, in the presence of said porous metal oxide support and at least one alkylaluminum compound until a degree of prepolymerization is reached which is suitable for the subsequent gas-phase of fluidized bed polymerization, and the method of polymerizing olefins utilizing the catalysts formed by the prepolymerization.Type: GrantFiled: October 30, 1989Date of Patent: May 12, 1992Assignee: AtochemInventors: Claude Brun, Auguste Cheux, Eric Barthel
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Patent number: 5106804Abstract: The present invention relates to a solid catalyst suitable for polymerizing olefins in a heterogeneous process, the catalyst consisting of spheroidal particles having a narrow particle size distribution and comprising (i) a support containing magnesium dichloride and an electron-donor free from labile hydrogen, (ii) a zirconium metallocene, and (iii) optionally an organoaluminium compound which is an aluminoxane preferably. The solid catalyst may be used in the form of a prepolymer comprising a polyethylene or a copolymer of ethylene and an active zirconium metallocene catalyst essentially consisting of atoms of Zr, Mg, Cl and Al, preferably in the form of spheriodal particles. The solid catalyst or the prepolymer may be used for producing polyethylene or copolymer of ethylene having from 0.5 to 20 ppm of zr and a molecular weight distribution from 2 to 5, in the form of a powder having a bulk density from 0.3 to 0.55 g/cm.sup.3, preferably consisting of spheroidal particles.Type: GrantFiled: December 11, 1990Date of Patent: April 21, 1992Assignee: BP Chemicals LimitedInventors: Jean-Claude Bailly, Philippe Bres, Christine Chabrand, Erick Daire
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Patent number: 5104838Abstract: Disclosed is a titanium-containing solid catalyst component which is a contact reaction product of:(i) a magnesium halide such as MgCl.sub.2,(ii) a titanium compound represented by the formula:Ti(OR.sup.1).sub.a X.sub.4-awherein a is a number of 0.ltoreq.a.ltoreq.4, R.sup.1 represents a hydrocarbon residue having 1 to 20 carbon atoms, and X represents a halogen atom, such as Ti(O--nBu).sub.4, and(iii) a coordination titanium compound represented by the formula:R.sup.2.sub.m R.sup.3.sub.n TiX.sub.4-m-nwherein R.sup.2 represents a cyclopentadienyl group or a substituted cyclopentadienyl group, R.sup.3 represents a hydrogen atom, a hydroxyl group, a hydrocarbyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group or a substituted amino group, X represents a halogen atom, and m is a number of 1.ltoreq.m.ltoreq.4 and n is a number of 0.ltoreq.n.ltoreq.3, with the proviso that the condition of 1.ltoreq.m+n.ltoreq.4 is satisfied, such as Cp.sub.2 TiCl.sub.2, i.e.Type: GrantFiled: August 2, 1990Date of Patent: April 14, 1992Assignee: Mitsubishi Petrochemical Company LimitedInventors: Takashi Fujita, Toshihiko Sugano, Takashi Niwa
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Patent number: 5075270Abstract: A process for preparing a transition metal component for a catalyst system wherein a specified aluminosiloxane derivative is reacted with a monohalopenated, alkylated, or alkoxylated compound of magnesium and the reaction product is chlorinated and reacted with a transition metal; a catalyst system comprising such transition metal component and a cocatalyst selected from organometallic compounds of a metal of Groups I through III of the Periodic Table; and the process of synthesizing olefin homopolymers and copolymers utilizing such catalyst system.Type: GrantFiled: June 9, 1986Date of Patent: December 24, 1991Assignee: AtochemInventors: Claude Brun, Jean-Loup Lacombe
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Patent number: 5070056Abstract: Catalyst compositions enabling the production of polyalkenes with improved bulk density are prepared by combining the following catalyst components in the following order of addition: first introducing an electron donor component, then adding a reaction product of a di-alkylaluminium halide and a solid component comprising a magnesium di-halide, an electron donor and a halide of tetravalent titanium and lastly adding a tri-alkylaluminium compound.Type: GrantFiled: October 29, 1990Date of Patent: December 3, 1991Assignee: Shell Internationale Research Maatschappij, B.V.Inventors: Ian G. Carson, Petrus A. Bentvelsen
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Patent number: 5070055Abstract: A supported, electron donor-complexed reduced vanadium.sup.(<3) /zirconium coimpregnated catalyst possessing enhanced activity, the methods of its manufacture and ethylene polymers of broad molecular weight distribution produced therewith.Type: GrantFiled: June 29, 1990Date of Patent: December 3, 1991Assignee: Union Carbide Chemicals and Plastics Technology CorporationInventors: Kathleen D. Schramm, Frederick J. Karol
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Patent number: 5063110Abstract: A process for (co)polymerizing alpha-olefins in the gas phase in a fluidized bed or mechanically stirred bed reactor using a Ziegler-Natta type catalyst or a heat activated chromium oxide/refractory oxide catalyst wherein the (co)polymerization is carried out in the presence of 0.005 to 0.2 weight %, based on the weight of the (co)polymer bed, of an inert pulverulent inorganic substance (e.g. silica) having a mean particle diameter between 0.5 and 20 microns. The process is capable of being operated at temperatures closer to the softening point of the produced polyolefin than in the absence of the pulverulent solid.Type: GrantFiled: July 2, 1990Date of Patent: November 5, 1991Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, Joelle Collomb