Monomer Polymerized In Bulk In Presence Of Transition Metal Containing Catalyst Patents (Class 526/902)
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Patent number: 5091129Abstract: A method for manufacturing a filter cartridge by polymerization of a polyethylene hydrocarbon with granular elements are set forth. The method involves the preparation of a mixture comprising the hydrocarbon and the granular elements, then introduction of the mixture into a mold which is formed by a first porous wall and a second porous wall, these walls being connected to a jacket, the introduction of the mold in an oven so as to raise the temperature of the mixture and by a thermal polymerization reaction to transform the hydrocarbon into a material binding the granular elements of the mixture, the assembly of the material and granular elements then forming a cartridge, and injection of a chemically inert gaseous composition into the mold through one of the walls to impart fluid permeability to the cartridge.Type: GrantFiled: December 29, 1989Date of Patent: February 25, 1992Assignee: Institut Francais du PetroleInventor: Claude Gadelle
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Patent number: 5086134Abstract: The invention relates to a process for the preparation of a predominantly crystalline ethylene/propylene copolymer having less than 15 mol % of propylene units, which can be carried out in liquid propylene as the suspending agent, if metallocene catalyst components of the formulae I, II or III are employed and the partial pressures of ethylene and propylene have a specific ratio. ##STR1## By means of this process, it is possible to increase the possible uses of polymerization plants which work with liquid propylene.Type: GrantFiled: October 19, 1989Date of Patent: February 4, 1992Assignee: Hoechst AktiengesellschaftInventors: Martin Antberg, Walter Spaleck, Jurgen Rohrmann, Hartmut Luker, Andreas Winter
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Patent number: 5084534Abstract: A process for polymerizing or copolymerizing ethylene, either alone or in combination with other olefins, comprising contacting said ethylene or alpha-olefin, either alone or in combination with other olefins, with a catalyst comprising a cyclopentadienyl-transition metal compound and an alumoxane compound at an elevated temperature and pressure and wherein the ratio of aluminum in the alumoxane to the total metal in the metallocene is in the range of 1000:1 to 0.5:1.Type: GrantFiled: September 10, 1987Date of Patent: January 28, 1992Assignee: Exxon Chemical Patents, Inc.Inventors: Howard C. Welborn, Jr., Charles S. Speed
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Patent number: 5079318Abstract: Disclosed is a method of moderating the catalyst activation characteristics of an alkyl aluminum compound by the use of hydrocarbon substituted acetylene. Preferred compounds are phenylacetylene, hexyne-1-and hexyne-2.Type: GrantFiled: October 12, 1990Date of Patent: January 7, 1992Assignee: Hercules IncorporatedInventors: Andrea E. Martin, John F. L. Newport
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Patent number: 5077367Abstract: Syndiotactic homopolymers of an arylcyclobutene functional monomer and syndiotactic copolymers of an arylcyclobutene functional monomer and a vinylaromatic monomer are prepared by conducting the polymerization in the presence of a catalytic amount of a suitable coordination catalyst such as the reaction product of polymethylaluminoxane and a transition metal compound.Type: GrantFiled: June 22, 1990Date of Patent: December 31, 1991Assignee: The Dow Chemical CompanyInventors: Richard E. Campbell, Jr., Robert A. DeVries
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Patent number: 4948856Abstract: The present invention provides a method for producing addition copolymers of ethylene and cycloolefin monomers of the norbornene-type, such as norbornene and tetracyclododecene. Copolymers having a uniform structure with uniform glass transition temperature values are provided by performing the copolymerization reaction in bulk with a catalyst system soluble in the cycloolefin monomers.Type: GrantFiled: May 22, 1987Date of Patent: August 14, 1990Assignee: B. F. Goodrich CompanyInventors: Robert J. Minchak, James T. Ware
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Patent number: 4943621Abstract: Methods of preparing storage stable components useful for metathesis bulk polymerization of cycloolefin monomers are provided. These components contain cycloolefins with norbornene-functional groups and cocatalysts activated with a halometal compound. In these methods, the cocatalyst is completely formed before the halometal activator is added to prevent the formation of unwanted hydrogen halides, which catalyze undesired crosslinking reactions which destabilize the cocatalyst component. Bulk polymerization systems are provided wherein these storage stable cocatalyst components are paired with catalyst components that together form the complete metathesis catalyst system. For some embodiments, storage stability is aided by the removal of water.Type: GrantFiled: August 4, 1988Date of Patent: July 24, 1990Assignee: The B. F. Goodrich CompanyInventors: Dennis J. Janda, Paul T. Stricharczuk, Robert J. Minchak
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Patent number: 4762898Abstract: A process for polymerizing or copolymerizing ethylene comprises contacting ethylene or ethylene and at least one of .alpha.-olefins with a catalyst consisting essentially of a combination of (A) a solid catalyst component containing at least titanium, magnesium and chlorine, (B) an organoaluminum compound, and (C) an organic compound selected from the group consisting of a compound having P-O-C bond, a compound having B-O-C bond and a compound having C-O-R bond, at a temperature not lower than 125.degree. C. and under a pressure not lower than 200 kg/cm.sup.2.Type: GrantFiled: September 28, 1987Date of Patent: August 9, 1988Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Katsumi Hirakawa
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Patent number: 4742131Abstract: Disclosed herein is a method for controlling the polymerization temperature in a polymerization apparatus equipped with a cooling system in which steam, which has occurred in the presence of a volatile liquid medium in a reaction system, is condensed in a reflux condenser and the resulting noncondensable gas and condensate are then returned to the reaction system, thereby removing the polymerization heat. A portion of the noncondensable gas is recirculated to the cooling system. The flow rate of the noncondensable gas to be recirculated and the flow rate of a cooling medium to be introduced into the reflux condenser are controlled in accordance with the temperature of the reaction system.Type: GrantFiled: December 9, 1986Date of Patent: May 3, 1988Assignee: Mitsui Toatsu Chemicals, IncorporatedInventors: Tadashi Asanuma, Mitsuru Ito, Kaneo Ito, Yoshiyuki Funakoshi, Akihiko Nakajima
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Patent number: 4719270Abstract: A novel process for production of polyethylene comprises polymerizing ethylene or a mixture of ethylene and a copolymerizable comonomer in the presence of a Ziegler-type catalyst at a pressure of 200 atm or more and at a temperature of 125.degree. C. or more, wherein an organic peroxide is added to the resulting polymerization product taken out of a reaction zone to deactivate the remaining catalyst. Formation of undesired oligomers or low-molecular polymers is prevented because the reaction does not proceed in the polymerization product taken out of the reaction zone. There is almost no retardation of the polymerization reaction even by the recycled use of the monomer separated and collected from the polymerization product.Type: GrantFiled: March 17, 1986Date of Patent: January 12, 1988Assignee: Mitsubishi Petrochemical Company LimitedInventors: Yukimasa Miwa, Takeo Shimada, Shigekazu Hayashi, Yoshio Kobayashi, Yoshiteru Kageyama
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Patent number: 4710563Abstract: A circulation loop is provided between a point next to the outlet of an amorphous polyalphaolefin polymerization zone and a flash zone, carrying a stream of molten devaporized polymer product.Type: GrantFiled: August 15, 1986Date of Patent: December 1, 1987Assignee: El Paso Products CompanyInventor: Steven L. Oetting
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Patent number: 4621124Abstract: A catalyst system for use in the polymerization of ethylene under high pressure and temperature containing an alkyl-aluminum or alkylsiloxalane activator and a compound of the formula:(TiCla) (MgCL.sub.2).sub.y (AlCl.sub.3)z (RMgCl).sub.bin whicha is from 2 to 3;y is 2 or more;z is from 0 to 1/3;b is from 0 to 1; andR is an aliphatic or aromatic hydrocarbon radical.Type: GrantFiled: September 16, 1985Date of Patent: November 4, 1986Assignee: Societe Chimique des Charbonnages-CdF ChimieInventors: Jean-Marie Neyer, Jean-Pierre Machon, Karel Bujadoux
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Patent number: 4533705Abstract: A process for producing .alpha.-olefin polymers having high crystallinity and good particle form, with a high yield is provided. The polymerization therefor is carried out in the presence of a preactivated catalyst suitable particularly to gas phase polymerization or gas phase polymerization following slurry or bulk polymerization.The catalyst is prepared by reacting a reduction solid prepared by reducing TiCl.sub.4 with an organoaluminum compound, with an electron donor and an electron acceptor to obtain a solid product, andcombining this solid product with an organoaluminum compound, an .alpha.-olefin and a reaction product of an organoaluminum compound with an electron donor.Type: GrantFiled: July 21, 1983Date of Patent: August 6, 1985Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Toshihiro Uwai, Kenji Matsuda, Nobutaka Hattori
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Patent number: 4530983Abstract: A process for catalytic homo- or co-polymerization of ethylene under the conditions of a pressure of at least 300 kg/cm.sup.2, a temperature of at least 180.degree. C., a contact time with a catalyst of 10 to 150 seconds and substantial absence of a solvent is disclosed. The catalyst used comprises Components A and B where Component A is a solid composition prepared by mixing and pulverizing (1) a magnesium halide, (2) titanium trichloride, and (3) an electron donor and Component B is an organoaluminum compound containing a halogen.Type: GrantFiled: January 18, 1983Date of Patent: July 23, 1985Assignee: Mitsubishi Petrochemical Company LimitedInventors: Mitsuyuki Matsuura, Yoshiteru Kageyama, Akito Hagiwara, Takeo Shimada
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Patent number: 4378455Abstract: The present disclosure relates to a process for alternating copolymerization of propylene and butadiene in the absence of a polymerization solvent. The disclosure contains information relative to commercial production of the said copolymer and detailed teachings relative to the preparation of catalyst for use in the said process.Type: GrantFiled: February 19, 1980Date of Patent: March 29, 1983Assignee: Maruzen Petrochemical Co., Ltd.Inventors: Akihiro Kawasaki, Tsuyoshi Matsumoto, Masanobu Taniguchi, Isao Maruyama, Masaaki Matsui, Masao Kaneko, Akihiko Imai
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Patent number: 4368304Abstract: A process for producing .alpha.-olefin polymers is provided, which comprises: reacting an organoaluminum compound with an electron donor in a specified ratio in a solvent at a specified temperature to obtain a solid product (I); reacting solid product (I) with TiCl.sub.4 at a specified temperature in a specified ratio of Al/Ti and then removing a liquid portion from the resulting material followed by washing to obtain a solid product (II) having no free TiCl.sub.4 ; reacting solid product (II) with an electron donor and an electron acceptor in a specified ratio at a specified temperature to obtain a solid product (III); and polymerizing .alpha.-olefin(s) in the presence of a catalyst comprising a combination of solid product (III) with an organoaluminum compound. This process provides a catalyst having a high storing and thermal stability and a polymer having a uniform particle size.Type: GrantFiled: February 4, 1981Date of Patent: January 11, 1983Assignee: Chisso CorporationInventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
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Patent number: 4363901Abstract: A process for producing high-quality .alpha.-olefin polymers with a higher yield in a long lasting stabilized manner even in the case of gas phase polymerization is provided. In the production process of .alpha.-olefin polymers which comprises reacting a trivalent metal halide with a divalent metal compound to obtain a solid product (I); reacting this product with at least one electron donor (ED) and at least one electron acceptor (EA), once to 10 times, and at that time, using TiCl.sub.4 at least once as the (EA) to obtain a solid product (II); combining this product with an organoaluminum compound (OAl) and an (ED) (these three being referred to as catalyst components), the improvement which comprises subjecting a part or the whole of the catalyst components to polymerization treatment with a small amount of an .alpha.-olefin, at least in the coexistence of the solid product (II) and (OAl), in the combination of the catalyst components to obtain a preactivated catalyst, and subjecting .alpha.Type: GrantFiled: February 12, 1981Date of Patent: December 14, 1982Assignee: Chisso CorporationInventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
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Patent number: 4309521Abstract: A process for producing .alpha.-olefin polymers is provided which comprises:reacting an organoaluminum compound (A.sub.1) with an electron donor (B.sub.1) to obtain a reaction product (I);reacting (I) with TiCl.sub.4 to obtain a solid product (II);reacting (II) with an electron donor (B.sub.2) and an electron acceptor to obtain a solid product (III);combining (III) with an organoaluminum compound (A.sub.2) and a reaction product (G) of an organoaluminum (A.sub.3) with an electron donor (B.sub.3) ((III), (A.sub.2) and (G) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an .alpha.-olefin at least in the presence of (III) and said (A.sub.2) to obtain a preliminarily activated catalyst;andpolymerizing an .alpha.-olefin in the presence of the catalyst.Type: GrantFiled: May 14, 1980Date of Patent: January 5, 1982Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Kenji Matsuda, Toshihiro Uwai, Tohru Hanari
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Patent number: 4306047Abstract: A TiCl.sub.3 olefin polymerization catalyst component is prepared by reducing TiCl.sub.4 with an aluminum trihydrocarbyl compound in a molar ratio of Ti:Al of 2.7:1 to 4.0:1 in the presence of diisoamyl ether and a hydrocarbon solvent by gradually adding TiCl.sub.4 to the aluminum trihydrocarbyl compound and at least a substantial proportion of the diisoamyl ether at a temperature of from 15.degree. to 50.degree. C. during a period of from 0.7 to 2.5 hours to produce a precipitate of TiCl.sub.3, and thereafter converting the precipitate into active TiCl.sub.3 by heating at a temperature of from 80.degree. to 110.degree. C. during at least 30 minutes. The active TiCl.sub.3, when combined with a conventional organoaluminum cocatalyst, provides a stereospecific catalyst for the polymerization of alpha monoolefins having high activity, good morphology and good stereospecificity.Type: GrantFiled: October 17, 1980Date of Patent: December 15, 1981Assignee: Shell Oil CompanyInventors: Andras G. T. G. Kortbeek, Wilhelmina J. M. van der Linden-Lemmers
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Patent number: 4304891Abstract: A process for producing .alpha.-olefins is provided which comprises:milling (A) a trivalent metal halide together with (B) a divalent metal compound, in a specified ratio of (A) to (B), and reacting them to obtain a solid product (I);reacting with this product (I), (C) an electron donor and (D) an electron acceptor, (C) and (D) being respectively reacted once or more up to ten times, and TiCl.sub.4 being employed as the electron acceptor at least once, to obtain a solid product (II);combining with this product (II), (E) a trialkylaluminum and (G) a reaction product of an electron donor with an electron acceptor, and in this combination, subjecting a part or the whole of the catalyst components (product (II), (E) and (G)) to polymerization treatment by reacting (F) an .alpha.-olefin at least in the presence of the product (II) and trialkylaluminum, to obtain a preliminarily activated catalyst; andpolymerizing an .alpha.-olefin in the presence of this catalyst.Type: GrantFiled: April 28, 1980Date of Patent: December 8, 1981Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi
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Patent number: 4298717Abstract: A process for polymerizing ethylene under high pressure and temperature in at least one reactor having at least one reaction zone. A catalyst system is used that comprises (a) an activator selected from trialkylaluminums, hologenodialkylaluminums, and alkylsiloxalanes, (b) a halogen compound of a transition metal of groups IV to VI A, and (c) a complexing agent that is injected into the reactor in such a manner that its concentration in the reactor may be adjusted independently from the concentration of (b). The complexing agent may be selected from silicone oils and from compounds having the formula X(OR).sub.n, wherein X is hydrogen or a metal, n is the valence of X, and R is an alkyl radical of up to 20 carbon atoms.Type: GrantFiled: August 1, 1978Date of Patent: November 3, 1981Assignee: Societe Chimique des Charbonnages-CdF ChimieInventor: Jean-Pierre Machon
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Patent number: 4277589Abstract: There are disclosed new solid catalyst-forming components for use in preparing catalysts for the stereoregular polymerization of alpha-olefins containing at least 3 carbon atoms, mixtures of alpha-olefins with one another and/or with ethylene, said components being obtained by reacting(a) at least one hydrocarbon-soluble halogenated Ti compound;(b) a product comprising a Mg dihalide obtained by decomposition of an adduct of at least a Mg dihalide and an electron-donor compound present in the adduct in an amount of at least 0.5 mole per mole of Mg dihalide, the decomposition product being characterized in that, in its X-rays powder spectrum, instead of the diffraction line of maximum intensity which appears in the X-rays powder spectrum of the normal Mg dihalide, a halo appears whose intensity maximum is shifted with respect to said line, and(c) an electron-donor compound which does not contain active hydrogen atoms.Type: GrantFiled: December 21, 1979Date of Patent: July 7, 1981Assignees: Montedison S.p.A., Mitsui Petrochemical Industries, Ltd.Inventors: Umberto Giannini, Enrico Albizzati, Sandro Parodi
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Patent number: 4273905Abstract: A process for producing a propylene polymer or copolymer which comprises polymerizing (a) propylene or (b) a mixture of propylene and another unsaturated hydrocarbon monomer in liquid propylene in the presence of a catalyst system of(A) a specified titanium trichloride composition obtained by reducing titanium tetrachloride with an organoaluminum compound and activating the product;(B) an organoaluminum compound having the general formulaR.sub.2 AlXwherein R represents an alkyl group or an aralkyl group, each containing up to 18 carbon atoms, and X represents a halogen atom; and(C) an unsaturated carboxylic acid ester; while adjusting the amount of the polymer produced to at least 8,000 g per gram of the titanium trichloride composition.Type: GrantFiled: January 8, 1979Date of Patent: June 16, 1981Assignee: Sumitomo Chemical Co., Ltd.Inventors: Mamoru Asada, Akinobu Shiga, Kiyoshi Matsuyama, Masahiro Kakugo
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Patent number: 4237254Abstract: A process for producing olefin polymers comprising contacting an ethylenically unsaturated monomer comprising at least one olefin monomer with a catalyst system comprising a combination of a catalyst component I and a catalyst component II as described hereunder:Catalyst component IA solid product obtained by contacting the following constituents (a), (b) and (c) or (a), (b), (c) and (d) together:(a) A solid reaction product of a magnesium compound containing a hydroxyl group attached to magnesium and an organoaluminum compound represented by the formula R.sub.n AlX.sub.3-n wherein R represents a hydrocarbon residue having from 1 to 20 carbon atoms, X represents a halogen atom and n represents a number of greater than zero but not greater than 1.5, i.e. 0<n.ltoreq.1.Type: GrantFiled: April 25, 1978Date of Patent: December 2, 1980Assignee: Mitsubishi Petrochemical Company LimitedInventors: Sadao Kitagawa, Isao Okada, Teruo Saito, Shoichi Masukawa, Yoshihisa Watanabe, Makoto Imanari
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Patent number: 4226963Abstract: 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 electron-donor compound free from ester groups of oxygenated organic and inorganic acids, with a supported component characterized by having surface area exceeding certain values or by showing a particular X-rays spectrum and which is obtained by contacting a halogenated Ti compound, preferably in the form of a complex with an electron-donor compound, with a support comprising a Mg or Mn dihalide in an active state. In the catalysts the ratio between the Ti compound expressed in Ti g-atoms and the g-moles of the electron donor compounds is lower than 0.3.Type: GrantFiled: November 13, 1978Date of Patent: October 7, 1980Assignee: Montedison S.p.A.Inventors: Umberto Giannini, Antonio Cassata, Paolo Longi, Romano Mazzocchi
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Patent number: 4218551Abstract: A polybutene-1 mixture which forms heat sealable, transparent film having good initial tear resistance and resistance to tear propagation are produced by polymerizing liquid butene-1 at 60.degree.-120.degree. C. employing as catalyst a dihalidefree mixture of diethylaluminum monochloride and TiCl.sub.3.nAlCl.sub.3 wherein n is 0.2 to 0.6, and isolating the unfractionated mixture of polymers.Type: GrantFiled: April 6, 1978Date of Patent: August 19, 1980Assignee: Chemische Werke Huls AktiengesellschaftInventor: Albert Frese
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Patent number: 4048419Abstract: Butene-1 optionally in the presence of up to 10% by weight of propene or like comonomer, is polymerized in excess butene-1 or liquid C.sub.4 fraction at 60.degree.-120.degree. C. to form a polybutene suitable for forming transparent films by employing as the polymerization catalyst (a) TiCl.sub.3 . nAlCl.sub.3 (n = 0.2 to 0.6) and (b) a mixture of 85 - 99.9 molar percent of dialkyl aluminum monochloride and 0.1 - 15 molar percent of trialkyl aluminum.Type: GrantFiled: May 27, 1975Date of Patent: September 13, 1977Assignee: Chemische Werke Huls AktiengesellschaftInventors: Albert Frese, Walter Dittmann, Wolfgang Kilian
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Patent number: RE30148Abstract: A melt finish process is disclosed herein for working up solid, particulate polymer from a vapor state polymerization reactor, which reactor employs high yield catalysts, whereby the polymer is moved out of the reactor and into a post polymerization zone characterized by essentially adiabatic polymerization and the heat of such polymerization is used in raising the temperature of and melting said solid, particulate polymer to form molten polymer for further processing.Type: GrantFiled: July 17, 1978Date of Patent: November 13, 1979Assignee: Standard Oil Company (Indiana)Inventors: James L. Jezl, Edwin F. Peters