Material Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non-transition Metal Atom Bond Patents (Class 526/159)
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Patent number: 5070160Abstract: Disclosed is a process for drying aluminoxane, which comprises drying a viscous solution containing aluminoxane, while applying a shearing force sufficient to keep said viscous solution in polydispersive state, so as to make the solution to be a solid-state polydispersoid. Also disclosed is a process for producing a polymer which comprises polymerizing a polymerizable monomer, using the aluminoxane obtained by the process of the present invention.According to the process of the present invention, aluminoxane in uniform powder which is easy to treat can be efficiently obtained in an industrial scale, and polymers can be produced at high efficiency.Type: GrantFiled: April 25, 1990Date of Patent: December 3, 1991Assignee: Idemitsu Kosan Co., Ltd.Inventors: Norio Tomotsu, Hiroshi Maezawa, Koji Yamamoto
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Patent number: 5037908Abstract: An improved process for polymerizing butene-1 in the presence of a polymerization catalyst composed of (a) a catalyst component containing titanium and halogen as essential constituents and (b) an organometallic compound, wherein the improvement comprises bringing said catalyst component into contact with an activity inhibitor when said catalyst component is activated or after said catalyst component has been activated with said organometallic compound, and subsequently polymerizing butene-1.Type: GrantFiled: December 19, 1985Date of Patent: August 6, 1991Assignee: Toa Nenryo Kogyo K.K.Inventors: Mamoru Tachikawa, Satoshi Ueki, Masato Sakuma, Makoto Miyazaki
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Patent number: 5036148Abstract: High strength, substantially linear, highly crystalline, high molecular weight-polyolefin shaped structure having a tenacity of greater than 15 g/den and an initial modulus of greater than 500 g/den by drawing never-processed polyolefin at a temperature of 60.degree. C. to 145.degree. C.; and processes for making never-processed polyolefin and such shaped structures.Type: GrantFiled: October 25, 1989Date of Patent: July 30, 1991Assignee: E. I. Du Pont de Nemours and CompanyInventors: Henri D. Chanzy, Bruno Rotzinger, Paul Smith
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Patent number: 5032650Abstract: A process for producing a styrene-based polymer having a high syndiotactic configuration, which comprises polymerizing a styrene-based monomer with addition of catalyst in such amounts that the conversion at 30 minutes after the polymerization starts becomes 2 to 50%, and then continuing the polymerization with additions of the catalyst when the conversion exceeds 10%.According to the process, the productivity can be improved while easily attaining safe running of the reactor and successful controlling of reaction heat.Type: GrantFiled: March 9, 1990Date of Patent: July 16, 1991Assignee: Idemitsu Petrochemical Co., Ltd.Inventors: Koji Yamamoto, Kazutoshi Ishikawa, Hideo Teshima
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Patent number: 5028673Abstract: High activity olefin polymerization catalysts based on organolithium compounds and transition metal compounds are disclosed. In one catalyst system an organolithium compound is employed in combination with titanium tetrachloride and the Li/Ti ratio is in the range of about 20 to about 50. In another catalyst system the organo lithium compound is combined with a rare earth metal halide. For best results these catalyst systems are employed at pressures of at least about 100 psi. In ethylene polymerization an ethylene partial pressure of at least about 100 psi is preferred.Type: GrantFiled: June 11, 1990Date of Patent: July 2, 1991Assignee: Phillips Petroleum CompanyInventors: Ted M. Pettijohn, Henry L. Hsieh
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Patent number: 5023304Abstract: Disclosed is a process for producing a styrene-based polymer by contacting a styrene-type monomer with alkylaluminoxane previously, adding a transition metal compound and then polymerizing of the styrene-type monomer.By using the process of the present invention, polymerization of a styrene-type monomer can be carried out with a high catalytic activity, and a styrene-based polymer having high syndiotacticity can be obtained with high efficiency.The sytrene-based polymer having a high degree of syndiotactic configuration of this invention has various excellent physical properties such as heat resistance and chemical resistance, and can be effectively and widely utilized for various applications.Type: GrantFiled: March 7, 1990Date of Patent: June 11, 1991Assignee: Idemitsu Kosan Co., Ltd.Inventors: Mizutomo Takeuchi, Masahiko Kuramoto
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Patent number: 4983696Abstract: A polyacetylene with excellent stretchability can be obtained by a process which comprises polymerizing acetylene with a Ziegler-Natta catalyst consisting of a tetraalkyl titanate and a trialkylaluminum, wherein in the Ziegler-Natta catalyst at least one of the tetraalkyl titanate and the trialkylaluminum has a long chain alkyl group and the molar ratio of al to Ti is 1.5-10.Type: GrantFiled: January 16, 1990Date of Patent: January 8, 1991Assignee: Matsushita Electric Industrial Co., Ltd.Inventors: Mamoru Soga, Shu Hotta, Nobuo Sonoda
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Patent number: 4983694Abstract: An olefin, particularly alpha-olefin, supported catalyst composition, containing a transition metal or a compound thereof and an activator, has an average pore diameter of about 20 to about 300 Angstroms, at a substantially constant catalyst particle size for a given range of average pore diameters. The catalyst produces polymers having gradually decreasing molecular weight distribution with decreasing pore size of the catalyst at a constant particle size.Type: GrantFiled: September 8, 1989Date of Patent: January 8, 1991Assignee: Mobil Oil CorporationInventor: Allan B. Furtek
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Patent number: 4965330Abstract: Polymerization of norbornene dicarboximide yields polymers of high Tg, e.g. greater than 170.degree. C. Preferred polymers of N-phenyl norbornene dicarboximide exhibit Tg greater than 210.degree.C.Type: GrantFiled: October 7, 1988Date of Patent: October 23, 1990Assignee: Monsanto CompanyInventor: Jawed Asrar
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Patent number: 4925902Abstract: The invention concerns copolymers of propylene and but-1-ene in which the proportion of units derived from but-1-ene is from 10 to 40% by weight and the proportion of isolated ethyl branches which they contain is at least equal to the square of the proportion [P] of units derived from propylene contained in said copolymers. The copolymers of the invention can be used for the production of heat-sealable films.Type: GrantFiled: March 23, 1989Date of Patent: May 15, 1990Assignee: BP Chemicals LimitedInventors: Bernard Desvignes, Daniel Durand, Bernard Milleliri
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Patent number: 4808680Abstract: Polymers of vinyl aromatic monomers having a high degree of syndiotacticity are prepared by contacting with a catalyst comprising a cyclopentadienyl zirconium (IV) complex and polymethylaluminoxane under polymerization conditions.Type: GrantFiled: June 8, 1987Date of Patent: February 28, 1989Assignee: The Dow Chemical CompanyInventors: Gregory F. Schmidt, Richard E. Campbell, Jr.
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Patent number: 4769429Abstract: A supported solid catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier with a transition metal compound. The carrier utilized in the synthesis must have such an average pore diameter that the resulting catalyst composition has an average pore diameter of at least about 170 Angstroms. The catalyst composition has higher productivity than similar catalyst compositions of lower average pore diameter, and it produces polymers of lower density and higher melt and high load melt indexes than such similar catalyst compositions of lower average pore diameter. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalyst of the invention.Type: GrantFiled: October 30, 1986Date of Patent: September 6, 1988Assignee: Mobil Oil CorporationInventor: Allan B. Furtek
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Patent number: 4767735Abstract: A process for pretreating a Ziegler-type catalyst for use in olefin polymerization reactions. An olefin monomer is aded to a fluid carrier stream containing a Ziegler-type catalyst. The carrier stream containing the monomer and the catalyst is passed through an elongated tubular reactor at a flow rate sufficient to provide a residence time in the tubular reactor of less than 1 minute and under temperature conditions to prepolymerize the catalyst within the tubular reactor without plugging of the reactor. In a specific embodiment the residence time within the reactor is no more than 10 seconds, and more particularly, no more than 2 seconds.Type: GrantFiled: February 2, 1987Date of Patent: August 30, 1988Assignee: Cosden Technology, Inc.Inventors: John A. Ewen, Alan H. Bitzer
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Patent number: 4761462Abstract: A packaging transparent propylene copolymer film stretched in at least one direction, which consists of a copolymer of propylene and an .alpha.-olefin having 4 or more carbon atoms or a copolymer of propylene, an .alpha.-olefin having 4 or more carbon atoms and ethylene. The copolymer satisfies the following conditions;(1) the content of the .alpha.-olefin having 4 or more carbon atoms in the copolymer is 8-25 mole %,(2) the content of ethylene in the copolymer is 5 mole % or less,(3) the content of a cold xylene-soluble portion in the copolymer is 15-50% by weight, and(4) the flexural modulus of the copolymer is 2,500-7,000 kg/cm.sup.2.Type: GrantFiled: December 30, 1985Date of Patent: August 2, 1988Assignee: Sumitomo Chemical Company, LimitedInventors: Shuji Kitamura, Kiyohiko Nakae, Tadatoshi Ogawa, Teruaki Yoshida, Hajime Sadatoshi
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Patent number: 4740570Abstract: Metal halide particles useful, among other things, as olefin polymerization catalyst precursors and catalyst supports, are prepared by vaporizing the metal halide and then condensing it in the presence of a diluent.Type: GrantFiled: November 13, 1986Date of Patent: April 26, 1988Assignee: E. I. Du Pont de Nemours and CompanyInventors: Ulrich Klabunde, Rolf Mulhaupt
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Patent number: 4714553Abstract: The invention relates to apparatus for the elutriation of particles of a Ziegler-Natta type alpha-olefin polymerization catalyst, based on transition metal compound(s) and preferably also comprising magnesium compounds, by means of an elutriation liquid which is a non-polar liquid, for example a hydrocarbon chemically inert in relation to the catalyst. The apparatus comprises a tank (M2) for the preparation of the catalyst suspension and the elutriation column or columns (F1), (F2).Type: GrantFiled: January 12, 1987Date of Patent: December 22, 1987Assignee: BP Chemicals LimitedInventor: Pierre Crouzet
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Patent number: 4713430Abstract: Finely divided ethene polymers are prepared by means of a Ziegler catalyst system composed of (1) a titanium-containing catalyst component obtained by precipitation in an organic liquid from (1.1) a solution of titanium tetrachloride in a hydrocarbon, (1.2) a solution of a certain organoaluminum compound in a hydrocarbon, and a catalyst component which contains (1.Type: GrantFiled: December 22, 1986Date of Patent: December 15, 1987Assignee: BASF AktiengesellschaftInventors: Juergen Kerth, Heinz Vogt
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Patent number: 4690991Abstract: The present invention concerns a procedure for copolymerization of ethylene and alpha olefins with at least eight carbon atoms in the presence of a catalyst of Ziegler-Natta type to become a polymer, in which the quantity of alpha olefin containing at least eight carbon atoms can be regulated between 0.01 and 15% by weight. Polymerization is carried out at a temperature not exceeding 120.degree. C. in a fluid in which the polymer is insoluble. The monomer mixture contains, for increasing the reactivity of the long-chained alpha olefin, 0.01 to 2.0 mol/dm.sup.3 of short-chained alpha olefin with not more than five carbon atoms. The alpha olefin containing not more than five carbon atoms is preferably 1-butylene or propylene.Type: GrantFiled: February 4, 1985Date of Patent: September 1, 1987Assignee: Neste OyInventor: Jukka Seppala
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Patent number: 4680353Abstract: A process for production of styrene polymers of high syndiotactic configuration is disclosed, comprising polymerizing styrene or styrene derivatives by the use of a catalyst comprising: (A) a titanium compound, e.g., at least one compound selected from those represented by the formulae: TiR.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c X.sup.1.sub.4 -(a+b+c) and TiR.sup.1.sub.d R.sup.2.sub.e X.sup.1.sub.3-(d+e) (all the symbols are as defined in the appended claims); and (B) a contact product of an organoaluminum compound and a condensation agent, e.g., a product resulting from modification of trimethylaluminum with water. Because of such high syndiotactic configuration, the styrene polymers are greater in thermal resistance and solvent resistance than conventional atactic polystyrene.Type: GrantFiled: October 23, 1986Date of Patent: July 14, 1987Assignee: Idemitsu Kosan Company LimitedInventors: Nobuhide Ishihara, Masahiko Kuramoto, Michitake Uoi
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Patent number: 4677172Abstract: The invention concerns elastomeric copolymers of ethylene and propylene wherein the proportion by weight of units derived from ethylene is from 34 to 67% and the proportion by weight of units derived from propylene is from 33 to 66%. The copolymers are characterized in that 60% at least of the units derived from propylene are disposed in sequences of at least three successive units and that their fusion enthalpy, as measured after a given heat treatment, is lower than 15 cal/g (calories per gram) and in most cases is from 5 to 10 cal/g. The copolymers of the invention can be used in particular for the production of isotactic polypropylene compositions.Type: GrantFiled: December 6, 1985Date of Patent: June 30, 1987Assignee: BP Chemicals LimitedInventors: Huguette Zimmerman, Jean Vincent, Pierre Mangin
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Patent number: 4672096Abstract: 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: October 16, 1985Date of Patent: June 9, 1987Assignee: Mobil Oil CorporationInventor: Thomas E. Nowlin
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Patent number: 4667005Abstract: Solid copolymers of C.sub.2 -C.sub.8 alphamonolefins and an olefinic benzocyclobutene monomer of the formula ##STR1## where R.sub.1 is hydrogen or CH.sub.3 and R.sub.2 is --CH.sub.2).sub.n where n is 0 to 6 are claimed. Such copolymers can be easily crosslinked at temperatures above about 200.degree. C., resulting in improved dimensional stability above the melting temperatures.Type: GrantFiled: December 23, 1985Date of Patent: May 19, 1987Assignee: Shell Oil CompanyInventor: Pui K. Wong
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Patent number: 4667004Abstract: Solid homopolymers of an olefinic benzocyclobutene monomer of the formula ##STR1## where R.sub.1 is hydrogen or CH.sub.3 and R.sub.2 is --CH.sub.2 --.sub.n where n is 0 to 6 are claimed. Such polymers can be easily crosslinked at temperatures above about 200.degree. C.Type: GrantFiled: December 23, 1985Date of Patent: May 19, 1987Assignee: Shell Oil CompanyInventor: Pui K. Wong
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Patent number: 4666990Abstract: A suspension which comprises an inert liquid medium, a solid material, and a transition metal compound 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. The solid material 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 dried solid is obtained as an agglomerate. The agglomerated solid can be mixed with an organic compound of a non-transition metal to give an olefin polymerisation catalyst system.Type: GrantFiled: September 30, 1985Date of Patent: May 19, 1987Assignee: Imperial Chemical Industries PLCInventors: John P. Candlin, John W. Kelland, Peter L. Law
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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: 4611038Abstract: A process is provided for the polymerization of olefins in the gas phase wherein olefins are contacted with a catalyst system consisting of an active solid hydrocarbon having been prepared by forming a pulverulent composition by mixing a transition metal component, a porous organic or inorganic solid support and an organometallic compound of the organo-Al, organo-Mg or organo-Zn type, and polymerizing a controlled amount of one or more C.sub.2 to C.sub.12 olefins in the gas phase in contact with the pulverulent composition with a specific hourly conversion of the olefins to produce the active solid hydrocarbon.Type: GrantFiled: July 18, 1985Date of Patent: September 9, 1986Assignee: AtochemInventors: Claude Brun, Auguste Cheux, Robert Pelletier
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Patent number: 4600756Abstract: Novel polyacetylene films are disclosed, having the following properties:elongation at break (1/10): higher than 4tensile strength: higher than 100 MPaability of attaining under stretch high levels of molecular orientation in the direction of pull.The process for preparing such polyacetylene films is also described.Type: GrantFiled: July 29, 1983Date of Patent: July 15, 1986Assignee: Enichimica S.p.A.Inventors: Ugo Pedretti, Giovanni Perego, Gabriele Lugli
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Patent number: 4585840Abstract: Solid polyolefin catalysts are adapted for use in low pressure gas phase fluid bed polymerization processes by being mixed with selected particulate organic support materials in a high speed bladed finishing device so as to cause the catalysts materials to become embedded in, and/or adhered to, softened particles of the support material.Type: GrantFiled: April 17, 1985Date of Patent: April 29, 1986Assignee: Union Carbide CorporationInventors: Laurence H. Gross, Allen Noshay
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Patent number: 4579921Abstract: The invention is a process for polymerization of acetylene and of the derivatives thereof by a supported catalyst of the Ziegler type.This catalyst is in suspension in a liquid medium the viscosity of which is between about 10 and 400 centipoises at room temperature.The polyacetylene can be obtained in the form of film, gel, or powder that can be used for electrochemical or photovoltaic applications.Type: GrantFiled: November 27, 1984Date of Patent: April 1, 1986Assignee: Societe Nationale Elf AquitaineInventors: Rene Gouarderes, Gildas Merceur
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Patent number: 4568730Abstract: An olefin polymerization catalyst component produced by impregnating polyethylene with a pulverized solid olefin polymerization catalyst containing a Group 4b or 5b transition metal, for example a pulverized magnesium chloride containing titanium is impregnated in low molecular weight polyethylene by copulvering, then subjecting the impregnated polymer particles to shear in an inert medium at about the softening point of the polyethylene, which when used as a cocatalyst with an organoaluminum compound produces polymers of improved morphology having a more regular shape and higher bulk density than pulverized catalyst alone.Type: GrantFiled: August 13, 1984Date of Patent: February 4, 1986Assignee: Exxon Research & Engineering Co.Inventor: Victoria Graves
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Patent number: 4560671Abstract: Solid polyolefin catalysts are adapted for use in low pressure gas phase fluid bed polymerization processes by being mixed with selected particulate organic support materials in a high speed bladed finishing device so as to cause the catalysts materials to become embedded in, and/or adhered to, softened particles of the support material.Type: GrantFiled: April 18, 1985Date of Patent: December 24, 1985Assignee: Union Carbide CorporationInventors: Laurence H. Gross, Allen Noshay
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Patent number: 4533707Abstract: A supported transition metal composition is obtained by suspending a support material in an inert liquid medium, spraying the suspension, collecting a solid material and contacting the sprayed solid with a transition metal compound. The support material may be a metal halide such as magnesium chloride or an inorganic oxide such as silica or alumina. In addition to being contacted with the transition metal compound, the support material may be contacted either before or after the spraying step with other reagents such as organo metallic compounds, halogen compounds, or Lewis Base compounds. The product obtained after contacting with the transition metal compound may be used as a component of a polymerization catalyst system to polymerize an unsaturated monomer such as ethylene or propylene.Type: GrantFiled: June 18, 1984Date of Patent: August 6, 1985Assignee: Imperial Chemical Industries, PLCInventor: Ian D. McKenzie
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Patent number: 4503203Abstract: Granular stereoregular butene-1 polymers having a high isotactic content, and an extractables content of no more than about 15 weight percent in boiling ethyl ether, are produced over a continuous extended period of time in a low pressure gas phase fluidized bed process, in the absence of liquid diluent components, with a stereospecific olefin polymerization catalyst under a selected set of operating conditions.Type: GrantFiled: December 20, 1983Date of Patent: March 5, 1985Assignee: Union Carbide CorporationInventors: Nancy M. Golembeski, Robert J. Jorgensen, Robert D. Cleland, Allen Noshay
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Patent number: 4468477Abstract: A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride or silicon tetrachloride and a specified transition metal compound. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.Type: GrantFiled: July 1, 1980Date of Patent: August 28, 1984Assignee: Imperial Chemical Industries PLCInventors: Anthony D. Caunt, Paul D. Gavens, John McMeeking
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Patent number: 4460757Abstract: A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.Type: GrantFiled: July 29, 1982Date of Patent: July 17, 1984Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Toshihiro Uwai, Kenji Matsuda, Yoshiharu Higuchi
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Patent number: 4452959Abstract: Process for producing easily moldable composition of an acetylene high polymer by polymerizing acetylene using a catalyst system composed of (A) a transition metal compound containing at least one transition metal from Groups IVa, Va, VIa and VIII and (B) an organometallic compound containing at least one metal from Groups IIa, IIb, IIIb and IVb, the polymerization being carried out in a polymerization solvent containing the transition metal compound in a concentration of 0.0001 to 0.1 mole/liter to form a gel-like material consisting of an acetylene high polymer having a fibrous microcrystalline structure and the polymerization solvent.Type: GrantFiled: December 6, 1982Date of Patent: June 5, 1984Assignee: Showa Denko K.K.Inventors: Yukio Kobayashi, Hideki Shirakawa, Sakuji Ikeda
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Patent number: 4451633Abstract: Completely polymerizing olefinic monomer feed, in contact with a coordination catalyst suitable for olefin polymerization, in a mold having the shape of the article, at conditions under which the polymer is produced as a coherent, useful article in the shape of the interior of the mold, and removing the article from the mold. This method permits the production of polyolefin articles which are difficult or impossible to produce from polyolefin powder or pellets by conventional methods, such as articles of polyolefins of such high molecular weight that the polymer would not be processable by a melt process; articles containing extremely high filler loading; articles containing interconnected reinforcement; and articles from molds which require substantial flows through narrow passages.Type: GrantFiled: August 19, 1982Date of Patent: May 29, 1984Assignee: Shell Oil CompanyInventors: Thomas F. Brownscombe, Carl L. Willis
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Patent number: 4434313Abstract: A process for preparing linear alpha olefins and waxes having a total product M.sub.n in the range 200 to 700 comprising at least 90 mole percent linear alpha olefins which includes polymerizing an ethylene containing gas in the presence of the reaction product of a zirconium halide compound with an aluminum cocatalyst selected from the group consisting of dialkyl aluminum alkoxides or aryloxides and dialkyl aluminum disubstituted amides in the presence of a diluent at a temperature of about 50.degree. to 200.degree. C. and an ethylene pressure above about 3.5 MPa, wherein the M.sub.n of said reaction product is controlled by the molar ratio of said aluminum cocatalyst/Zr halide, said molar ratio being less than about 10.Type: GrantFiled: December 29, 1982Date of Patent: February 28, 1984Assignee: Exxon Research and Engineering Co.Inventor: Arthur W. Langer, Jr.
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Patent number: 4431784Abstract: A solution process for the preparation of high molecular weight homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 .alpha.-olefins is disclosed. The process involves feeding monomer, a particular coordination catalyst and hydrocarbon solvent to a reactor, polymerizing the monomer at a temperature of 105.degree.-320.degree. C. and recovering the polymer. The catalyst is obtained by combining solutions of titanium tetrahalide and of organoaluminum compound at a temperature of less than 30.degree. C., heating the resulting admixture to a temperature of 150.degree.-300.degree. C. for a period of 10 seconds to 10 minutes and combining the thus heat-treated mixture with a solution of an organoaluminum compound. The catalyst thus obtained is fed to the process, without separation of any components of the catalyst. In an embodiment part of the titanium tetrahalide may be replaced with vanadium oxytrihalide.Type: GrantFiled: December 30, 1981Date of Patent: February 14, 1984Assignee: Du Pont Canada Inc.Inventors: Michael A. Hamilton, Vaclay G. Zboril
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Patent number: 4414371Abstract: Polyolefin granules having an average particle size diameter greater than 600 microns, preferably about 1000 microns or greater are obtained by polymerizing monoolefins in the presence of a titanium catalyst having an average particle size diameter of greater than about 35 microns and preferably 40 to 65 microns. The titanium catalysts are obtained by reducing titanium tetrahalide in the presence of a suitable organometallic reducing compound such as diethylaluminum chloride under controlled conditions of temperature, reduction rate and concentrations to obtain a titanium halide reduced solids product seeds having an average particle size diameter of about 20 microns or greater and thereafter simultaneously and without interruption adding to the seeds containing system titanium tetrahalide and organometallic reducing compound such as diethylaluminum halide at a rate such that the reduction of titanium tetrahalide to titanium trihalide is about 6.times.10.sup.-4 to about 0.Type: GrantFiled: February 8, 1982Date of Patent: November 8, 1983Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers, deceased
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Patent number: 4410750Abstract: A process for preparing linear alpha olefins and waxes having a total product M.sub.n in the range 200 to 700 comprising at least 90 mole percent linear alpha olefins which includes polymerizing an ethylene containing gas in the presence of the reaction product of a zirconium halide compound with an aluminum cocatalyst selected from the group consisting of dialkyl aluminum alkoxides or aryloxides and dialkyl aluminum disubstituted amides in the presence of a pi base and in the presence of a diluent at a temperature of about 50.degree. to 200.degree. C. and an ethylene pressure above about 3.5 MPa, wherein the M.sub.n of said reaction product is controlled by the molar ratio of said aluminum cocatalyst/Zr halide, said molar ratio being less than about 1.Type: GrantFiled: December 29, 1982Date of Patent: October 18, 1983Assignee: Exxon Research and Engineering Co.Inventor: Arthur W. Langer, Jr.
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Patent number: 4409126Abstract: Compositions consisting of the reaction product or complex resulting from the mixing of a transition metal compound such as a tetraalkoxy titanium compound and an organo compound of magnesium, aluminum, boron or lithium such as a dialkyl magnesium compound are useful in the preparation of catalysts for polymerizing .alpha.-olefins at ultra-high efficiencies at high polymerization temperatures.Type: GrantFiled: October 22, 1981Date of Patent: October 11, 1983Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach
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Patent number: 4407727Abstract: A process is provided for transforming a polyolefin powder into a suitable substrate for the preparation of transition metal catalysts. A powder polyolefin such as polyethylene or polypropylene is treated with a solution of a magnesium alkyl. The solvent is removed by any suitable procedure such as vacuum drying. The powder is then treated with gaseous HCl or other agent suitable for decomposition of the magnesium alkyl. The powder thus prepared is an effective support for preparing high efficiency catalysts such as taught in U.S. Pat. No. 4,136,058. These catalysts give polymers of increased particle size. Polyolefin powder in the absence of such treatment is not effective as a catalyst support and will not give polymers of increased particle size.Type: GrantFiled: October 8, 1982Date of Patent: October 4, 1983Assignee: Atlantic Richfield CompanyInventors: James J. Harris, Donald E. Hostetler
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Patent number: 4405772Abstract: Solid copolymers of butene-1 and 4-vinylcyclohexene prepared by copolymerizing the monomers in the presence of a titanium halide coordination catalyst have an unobvious balance of properties including a broader molecular weight distribution, shorter crystallization half-time, greater isotacticity and greater crystallinity than butene-1 homopolymers prepared with identical catalysts.Type: GrantFiled: June 23, 1982Date of Patent: September 20, 1983Assignee: Shell Oil CompanyInventors: Pui K. Wong, Carl L. Willis, Thomas F. Brownscombe
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Patent number: 4400494Abstract: A propylene polymerization catalyst comprises (a) a titanium-containing component formed by reducing titanium tetrachloride with an aluminum alkyl, optionally contacting the resulting reduced solid with a pretreatment amount of alpha-olefin monomer under polymerization conditions, and reacting the resulting product with a Lewis base complexing agent and additional titanium tetrachloride, and (b) an alkyl aluminum halide having a halogen/aluminum atomic ratio between 0.89 and 0.98 and preferably between 0.92 and 0.98.Type: GrantFiled: August 28, 1981Date of Patent: August 23, 1983Assignee: Standard Oil Company (Indiana)Inventors: Gregory G. Arzoumanidis, Benjamin S. Tovrog
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Patent number: 4384089Abstract: The hydrocarbon fluid friction reducing properties of copolymers of two or more alpha-monoolefins having 4 to 20 carbon atoms is improved by copolymerizing the monomers in the liquid state by means of a Ziegler catalyst at a temperature of about 0.degree. C. or lower.Type: GrantFiled: October 15, 1981Date of Patent: May 17, 1983Assignee: Atlantic Richfield CompanyInventor: David C. Dehm
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Patent number: 4377720Abstract: A process for preparing linear alpha olefins and waxes having a total product M.sub.n in the range 200 to 700 comprising at least 90 mole percent linear alpha olefins which includes polymerizing an ethylene containing gas in the presence of the reaction product of a zirconium halide compound with an aluminum cocatalyst selected from the group consisting of dialkyl aluminum alkoxides or aryloxides and dialkyl aluminum disubstituted amides in the presence of a diluent at a temperature of about 50.degree. to 200.degree. C. and an ethylene pressure above about 3.5 MPa, wherein the M.sub.n of said reaction product is controlled by the molar ratio of said aluminum cocatalyst/Zr halide, said molar ratio being less than about 1.Type: GrantFiled: December 14, 1981Date of Patent: March 22, 1983Assignee: Exxon Research and Engineering Co.Inventor: Arthur W. Langer
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Patent number: 4374753Abstract: 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: July 29, 1981Date of Patent: February 22, 1983Assignee: Chemplex CompanyInventors: Thomas J. Pullukat, Raymond E. Hoff
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Patent number: 4371680Abstract: A process is disclosed for the polymerization and interpolymerization of propylene, either alone or in admixture with ethylene, to produce polymers and copolymers of propylene. The catalyst employed is a coordination complex comprising at least some divalent titanium, or other transition metal element in lower valent state. The catalysts are prepared by mixing a higher valent titanium (or other transition metal) halide or titanate ester with a reducing agent, which can be any organometallic compound, such as a metal alkyl or aryl, including Grignard reagents, a metal hydride, or a metal including zinc and metals above zinc in the electromotive series. Hydrocarbon media can be employed advantageously for the preparation of the cataysts and for the polymerizations. The polymeric products (both homopolymers and copolymers) are linear and of high molecular weight and are useful as plastics, fibers and elastomers and for production of blends with polyethylene.Type: GrantFiled: January 22, 1968Date of Patent: February 1, 1983Assignee: E. I. Du Pont de Nemours & CompanyInventors: Warren N. Baxter, Nicholas G. Merckling, deceased, by Noelle K. Masukawa, administratrix, Ivan M. Robinson, Gelu S. Stamatoff