Including Heating To Higher Temperature Patents (Class 502/107)
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Patent number: 6355593Abstract: A process of enhancing both the activity and the methane selectivity of a Dispersed Active Metal (“DAM”) hydrogenation catalyst is disclosed wherein the DAM undergoes low temperature oxidation in a slurry phase to form an oxidized catalyst precursor that is unique in comparison to those formed by conventional high temperature deactivation processes. The oxidized catalyst precursor, which is stable, is subsequently reduced to form an enhanced catalyst by treatment with hydrogen-containing gas at elevated temperature. The process is useful in a wide variety of DAMs formed by art-recognized techniques. The process is equally applicable to the enhanced catalysts formed from the oxidized precursors and their use in hydrogenation reactions.Type: GrantFiled: September 1, 2000Date of Patent: March 12, 2002Assignee: ExxonMobil Research and Engineering CompanyInventors: Michel A. Daage, Russell John Koveal, Albert L'Vovich Lapidus, Alla Jurievna Krylova, Shawn Paul Brennan
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Publication number: 20020022706Abstract: A novel loop/slurry olefin polymerization process is provided which produces ultra-high molecular weight ethylene homopolymer.Type: ApplicationFiled: August 7, 2001Publication date: February 21, 2002Applicant: Phillips Petroleum CompanyInventors: Max P. McDaniel, Elizabeth A. Benham
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Patent number: 6339136Abstract: A process for homo or copolymerizing propylene, wherein propylene is polymerized in the presence of a catalyst at an elevated temperature in a reaction medium, in which a major part is formed by propylene. The polymerization is carried in at least one slurry reactor in the presence of liquid propylene at a temperature between 80° C. and the critical temperature of the reaction medium and a catalyst system producing within said temperature range a high productivity and essentially constant isotacticity within wide melt index range.Type: GrantFiled: July 13, 1999Date of Patent: January 15, 2002Assignee: Borealis A/SInventors: Sirpa Ala Huikku, Thomas Garoff, Timo Leinonen, Ali Harlin, Fred Bergmann
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Patent number: 6303532Abstract: In the invention a catalyst composition intended for the polymerization of olefins has been provided, which has been prepared by bringing together magnesium chloride, a lower alcohol, a titanium compound and an ester of phthalic acid. The procatalyst composition is active and stereospecific and it simultaneously has a titanium and phthalic acid content as low as possible. These good properties have been achieved by carrying out a transesterification between the lower alcohol and the ester of the phthalic acid, whereby the alkoxy group of the phthalic acid comprises at least five carbon atoms.Type: GrantFiled: April 18, 1995Date of Patent: October 16, 2001Assignee: Borealis Technology OyInventors: Thomas Garoff, Timo Leinonen, Eero Iiskola
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Patent number: 6294494Abstract: A novel loop/slurry olefin polymerization process is provided which produces ultra-high molecular weight ethylene homopolymer.Type: GrantFiled: December 18, 1998Date of Patent: September 25, 2001Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Elizabeth A. Benham
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Patent number: 6291384Abstract: An ethylene-alpha-olefin copolymerization catalyst is prepared by impregnating a silica calcined at elevated temperature sequentially with an organomagnesium compound such as dialkylmagnesium compound, a silane compound which is free of hydroxyl groups, such as tetraethyl orthosilicate. A transition metal component such as titanium tetrachloride is then incorporated into the support. Unexpectedly, the calcination temperature of the silica used to prepare the catalyst precursors has a strong influence on polymer product properties. By increasing the calcination temperature of the silica from 600° to 700° C. or higher temperatures, a catalyst precursor when activated produced ethylene/1-hexene copolymers with narrower molecular weight distributions (MWD) as manifested by a decrease of resin MFR values of ˜3-4 units. Activation of this catalyst precursor with a trialkylaluminum compound results in a catalyst system which is effective for the production of ethylene copolymers.Type: GrantFiled: July 28, 1997Date of Patent: September 18, 2001Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 6268306Abstract: A polymerization catalyst obtained by contacting metallic magnesium with an aromatic halide, RX, under conditions effective to obtain a first reaction product and solid residual products is disclosed. The first reaction product is then separated from the solid residual products. A silane compound containing an alkoxy or aryloxy group is added to the first reaction product between −20° C. to 20° C. to obtain a precipitate which is purified to obtain a second reaction product. Subsequently, the second reaction product is contacted with a halogenized titanium compound, such as, titanium tetrachloride, to obtain a further reaction product. The polymerization catalyst is obtained by purifying the further reaction product. In the aromatic halide, R represents an aromatic group containing from 6 to 20 carbon atoms and X represents a halide. An electron dopor such as dibutyl phthalate may also be present during the titanium addition.Type: GrantFiled: March 13, 2000Date of Patent: July 31, 2001Assignee: DSM N.V.Inventors: Vladimir A Zakharov, Gennadii D. Bukatov, Sergei A. Sergeev
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Patent number: 6255245Abstract: The invention relates to a process for the preparation of supported polymerization catalyst systems comprising the steps of: a) dissolving at least one different transition metal complex in a mixture of at least two different solvents having different boiling points to form a solution, b) contacting said solution with at least one different support material, the volume of the solution being sufficient to form a slurry with the support material, the volume of the higher-boiling solvent being less than or equal to the total pore volume of the support, c) removing more than 90% of the solvent boiling at the lower temperature, and d) adding at least one co-catalyst.Type: GrantFiled: June 10, 1999Date of Patent: July 3, 2001Assignee: Bayer AktiengesellschaftInventors: Hans-Rafael Winkelbach, Peter Schertl, Wolfgang Nentwig
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Patent number: 6248685Abstract: A method of making a catalyst suitable for the polymerization of olefins includes the steps of mixing an ether having a total number of carbon atoms equal to or greater than 8, with hydrated magnesium chloride, to produce partially activated magnesium chloride; mixing an alkyl aluminum with the partially activated magnesium chloride to form unwashed activated magnesium chloride; and washing the activated magnesium chloride with an inert saturated hydrocarbon liquid, to obtain an activated magnesium chloride-containing slurry. A plurality of alcohols are mixed with the activated magnesium chloride-containing slurry to form an activated magnesium chloride/alcohol complex. Titanium tetrachloride is mixed with the activated magnesium chloride/alcohol complex, to form a magnesium chloride supported titanium catalyst.Type: GrantFiled: April 1, 1999Date of Patent: June 19, 2001Assignee: Sasol Technology PTY LimitedInventors: Dawid Johannes Joubert, Ignatius Hendrik Potgieter, Ioan Tincul
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Patent number: 6232256Abstract: A catalyst composition is provided, which is prepared by contacting a cycloalkadienyl compound, a transition metal amide of the formula M(NMe2)mXn, an aluminoxane, and optionally a solid support at a temperature of 0 to 100° C.Type: GrantFiled: November 5, 1999Date of Patent: May 15, 2001Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Xinmin Yang, Walter Thomas Reichle, Frederick John Karol
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Patent number: 6225428Abstract: The present invention relates to the production of high density polyethylene homopolymers or copolymers having a broad and monomodal molecular weight distribution wherein the polymerization process is conducted in the presence of supported metallocene-alumoxane catalysts wherein the metallocene is bridged, comprises at least a hydrogenated indenyl or fluorenyl and is isolated on its support under the form of all its conformers.Type: GrantFiled: June 18, 1999Date of Patent: May 1, 2001Assignee: Fina Research, S.A.Inventor: Abbas Razavi
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Patent number: 6218330Abstract: A process for the preparation of supported metallocene-alumoxane catalysts comprising the steps of: a) reacting a metallocene with an alumoxane at a temperature comprised between 15 and 50° C., b) recovering a mixture comprising an alkylmetallocenium cation and an anionic alumoxane oligomer, c) reacting said mixture with a support, and d) recovering a supported metallocene-alumoxane catalyst as a dry solid, the reaction with the support being carried out at a temperature comprised between 85° C. and 110° C., preferably between 90 and 130° C., and their use for the polymerization or copolymerization of olefins.Type: GrantFiled: April 21, 1999Date of Patent: April 17, 2001Assignee: Fina Research, S. A.Inventors: Abbas Razavi, Guy Debras
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Patent number: 6207607Abstract: Disclosed is the homogenous reaction at 40-200° C. of MgX12−nR1OH (where n=2.0-6.4) with TiX24 and a higher (C6-C20) alkyl ester of a carboxylic acid, optionally in the presence of a solvent. In such a completely homogenous reaction, no carrier appears. In order to obtain a product in the liquid stage, the molar ratio between the ester and the MgX12.nR1OH should be at least 0.8/j wherein j is the number of carboxyl groups in the ester. If the ester has two carboxyl groups, for instance, j is 2 and the molar ratio should be at least 0.8/2, that is, 0.4.Type: GrantFiled: December 23, 1998Date of Patent: March 27, 2001Assignee: Borealis A/SInventors: Thomas Garoff, Timo Leinonen, Sirpa Ala-Huikku
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Patent number: 6200923Abstract: A novel soluble composition containing magnesium, titanium, a halogen and a carboxylic acid ester has been invented. The composition has mainly the composition according to Formula (I): (MgX32)xTiX44(R(COOR′)n)y (I) wherein X3 is a halogen, X4 is a halogen, R(COOR′)n is a carboxylic acid higher alkyl ester containing at least 8·n carbon atoms, wherein R is an n-valent substituted or unsubstituted C1-C34 hydrocarbon group, R′ is a C1-C20 alkyl group, and n is an integer from 1 to 4, x is between 0.5 and 4.0, and y is between 0.8/n and 2.4/n.Type: GrantFiled: November 30, 1998Date of Patent: March 13, 2001Assignee: Borealis Technology OyInventors: Thomas Garoff, Timo Leinonen, Sirpa Ala-Huikku
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Patent number: 6175025Abstract: A di-substituted metallocene compound having good quality can be synthesized completely at a low cost in a high yield in a easy manner by reacting a metallocene dihalide with a Grignard reagent which is a compound represented by formula (I): RMgX (wherein R represents an aryl, benzyl or diaryl phosphinomethylene group which may have a substituent and X represents a halogen element) under specified conditions.Type: GrantFiled: February 23, 2000Date of Patent: January 16, 2001Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Yuichi Kitagawa, Koji Otaka, Tomoya Kubo, Eiji Takeichi
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Patent number: 6140264Abstract: The present invention provides a novel process for preparing a catalyst, preferably free of electron donor, useful in gas phase polymerization of olefins having a broad polydispersity.Type: GrantFiled: May 12, 1998Date of Patent: October 31, 2000Assignee: Nova Chemicals Ltd.Inventors: Mark Kelly, Dusan Jeremic, Victoria Ker, Charles Russell
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Patent number: 6133188Abstract: A preparation process for a catalytic support, based on a special alumina modified with varying quantities of magnesium chloride is described, a higher rate of MgCl.sub.2 leading to a lesser quantity of heavy molecular chains in the final polymer. The support, prepared by milling the special alumina together with the MgCl.sub.2 previously treated with ethyl benzoate, is impregnated with TiCl.sub.4 in order to create the catalyst. The resulting catalysts show high activity, which enables the metallic residue and chloride eliminating stage to be avoided in the resin so created. Furthermore the types of molecular weight distribution and of mechanical properties are different for the polymers produced.Type: GrantFiled: June 7, 1995Date of Patent: October 17, 2000Assignees: Petroleo Brasileiro S.A. - Petrobras, Polialden Petroquimica S.A.Inventors: Juan Raul Quijada Abarca, Dellyo Ricardo dos Santos Alvares
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Patent number: 6127305Abstract: An active catalyst in the polymerization of alpha-olefins is obtained by:(i) bringing a dialkyl magnesium, or an alkyl magnesium halide into contact with a silicon or tin halide, in solution in an inert organic solvent, until a granular solid precipitates off;(ii) suspending said solid precipitate in an inert organic solvent and bringing it into contact with a compound which can be defined by the formula: ##STR1## wherein M represents a metal from Group IVB of the Periodic Table of Elements, and each R and C.sub.p has the meaning as reported in the disclosure, in order to form a granular solid catalyst; and(iii) recovering said solid catalyst from the resulting suspension.Type: GrantFiled: October 3, 1996Date of Patent: October 3, 2000Assignee: Enichem S.p.AInventors: Federico Milani, Luciano Luciani, Bruno Pivotto, Antonio Labianco
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Patent number: 6124229Abstract: Disclosed is a process for preparing a supported metallocene catalyst by introducing, in a first stage, a gas stream comprising an organoaluminum compound, an inert support material and water, into a first gas phase reactor; allowing the mixture to react under conditions effective to form an aluminoxane supported on said inert support material; metering a second gas stream comprising a metallocene into said gas phase reactor; allowing said mixture to react under conditions effective to form a supported metallocene catalyst; and drying, in a second stage, said supported metallocene catalyst, wherein said drying is carried out in a gas phase reactor.Type: GrantFiled: August 22, 1996Date of Patent: September 26, 2000Assignee: Witco GmbHInventors: Ralf-Jurgen Becker, Rainer Rieger
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Patent number: 6107243Abstract: The present cluster-included material characterized by utilizing a porous host material for clusters having a pore larger in size than that of zeolite. The cluster-included material is obtained by forming a cluster in a pore of a mesoporous material having a pore size of 1.3 to 10 nm. When the mesoporous material is particularly a mesoporous material having a pore volume of not less than 60% of a total pore volume within a pore size range of -40 to +40% of a pore size which shows a maximum peak in a pore size distribution curve, a granular cluster having a uniform particle size or a fine-linear cluster having a uniform diameter is obtained. The cluster-included material performs the various quantum effects.Type: GrantFiled: September 9, 1997Date of Patent: August 22, 2000Assignee: Kabushiki Kaisha Toyota Chuo KenkyushoInventors: Shinji Inagaki, Noriaki Sugimoto, Tatsumi Hioki, Yoshiaki Fukushima, Masaru Ichikawa
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Patent number: 6103655Abstract: Procedure for the preparation of a solid carrier for olefin polymerization catalysts, comprising the steps:a) impregnating a silica with Mg-chloride solubilized in ethylbenzoate, in the presence of further electron donors,b) optionally drying the impregnated silica obtained in (a) and impregnating it with a solution of Mg-alkyls in SiCl.sub.4 at a temperature from -10 to 20.degree. C. and subsequently treating the obtained slurry at a temperature from 40.degree. C. to reflux temperature, optionally adding a further amount of electron donors,c) drying the obtained carrier.The carrier which is obtained according to the above procedure is advantageously used for the preparation of supported catalysts for the polymerization of olefins.Type: GrantFiled: February 13, 1998Date of Patent: August 15, 2000Assignee: Borealis GmbHInventors: Luciano Luciani, Wolfgang Neissl, Norbert Hafner
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Patent number: 6087291Abstract: This invention is generally directed toward a supported catalyst system useful for polymerizing olefins. The method for supporting the catalyst system of the invention provides for a metallocene catalyst and alumoxane activator supported on a porous support using a total volume of catalyst solution that is less than that of which a slurry is formed. The metallocene and alumoxane aer mixed in solution, then the solution is added to a porous support in a volume between the total pore volume of the support and the volume at which a slurry forms. The solvent is then removed, leaving an activated supported metallocene.Type: GrantFiled: October 24, 1997Date of Patent: July 11, 2000Assignee: Exxon Chemical Patents, Inc.Inventors: Anthony Nicholas Speca, Jeffrey Lawrence Brinen, George Alan Vaughan, Patrick Brant, Terry John Burkhardt
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Patent number: 6069108Abstract: Process for preparing a supported metallocene catalyst, in which a hydrophilic, macroporous, finely divided aluminum oxide, silicon oxide, titanium oxide or zirconium oxide or a mixture or mixed oxide thereof is dried at from 110 to 800.degree. C., then reacted with an aluminoxane and subsequently with polyfunctional organic crosslinkers. In a further step, the catalyst support can be mixed with a reaction product of metallocenes and activators, giving a supported metallocene catalyst which is used, in particular, for the polymerization of olefins.Type: GrantFiled: March 4, 1999Date of Patent: May 30, 2000Assignee: Borealis GmbHInventors: Eberhard Ernst, Jens Reussner, Wolfgang Neissl
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Patent number: 6054406Abstract: Disclosed is a polymetallic supported catalyst component comprising an activated anhydrous MgCl.sub.2 solid support which has been treated with at least one treatment of at least two halogen-containing transition metal compounds, wherein one is a halogen-containing titanium metal compound and one is a halogen-containing non-titanium transition metal compound, optionally, in the presence of an electron donor and the processes for producing the component. A catalyst for the polymerization of at least one alpha-olefin of the formula CH.sub.2 =CHR, where R is H or a C.sub.1-12 branched or straight chain alkyl or substituted or unsubstituted cycloalkyl, by reacting this supported catalyst component with an organometallic cocatalyst, optionally in the presence of an electron donor, and the polymerization of at least one alpha-olefin with the catalyst are also disclosed.Type: GrantFiled: April 27, 1993Date of Patent: April 25, 2000Assignee: Montell North America Inc.Inventor: Crystal A. Smith
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Patent number: 6051523Abstract: Catalyst systems of the type comprising the Ziegler-Natta catalysts contain, as active components,a) a titanium-containing solid component which contains titanium, magnesium, halogen and a carboxylic ester as an electron donor, and, as a cocatalyst,b) an aluminum compound andc) if required, a further electron donor, a compound of the following formula IR.sub.m.sbsb.1 Al--(OCOR.sup.1).sub.m.sbsb.2 (I)whereR and R.sup.1 are identical or different and are each hydrogen or C.sub.1 -C.sub.8 -alkyl andm.sub.1 and m.sub.2 are each 1 or 2 and sum to give 3, being used as aluminum compound b) in the preactivation of the titanium-containing soild compound a) with the cocatalyst.Type: GrantFiled: June 20, 1997Date of Patent: April 18, 2000Assignee: BASF AktiengesellschaftInventors: Meinolf Kersting, Klaus-Dieter Hungenberg, Peter Kolle, Jurgen Kerth
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Patent number: 6046126Abstract: The present invention provides a novel process for preparing a catalyst, preferably free of electron donor, useful in gas phase polymerization of olefins having a broad polydispersity.Type: GrantFiled: May 12, 1998Date of Patent: April 4, 2000Inventors: Mark Kelly, Dusan Jeremic, Victoria Ker, Charles Russell
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Patent number: 6043180Abstract: A supported catalyst component prepared from a support material and an alumoxane, containing 15-40 weight percent of aluminum from the alumoxane (based on the total weight of the support material and alumoxane), said supported catalyst component being obtained by heating said support material and alumoxane under an inert atmosphere at a temperature of from about 85 to about 250.degree. C. for a period sufficient to fix said alumoxane to the support material, to provide a supported catalyst component; wherein not more than about 10 percent aluminum from said alumoxane and present in the supported catalyst component is extractable in a one-hour extraction with toluene at 90.degree. C. using 10 ml toluene per gram of supported catalyst component; and a transition metal compound, and a process for the preparation of the supported catalyst.Type: GrantFiled: August 11, 1997Date of Patent: March 28, 2000Assignee: The Dow Chemical CompanyInventors: Grant B. Jacobsen, Peter L. Wauteraerts, Lee Spencer
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Patent number: 6043182Abstract: A method for preparing an oil soluble catalytic precursor includes the steps of: providing a mixture of a catalytic metal salt in water, wherein the catalytic metal salt contains a catalytic metal selected from the group consisting of alkali metals, alkaline earth metals, transition metals, and mixtures thereof; providing a heavy hydrocarbon phase; forming a water in oil emulsion of the mixture in the heavy hydrocarbon phase; and heating the emulsion at a temperature sufficient to dehydrate the emulsion so as to provide a hydrocarbon containing an oil soluble compound containing the catalytic metal.Type: GrantFiled: May 1, 1998Date of Patent: March 28, 2000Assignee: Intevep, S.A.Inventors: Jose Cordova, Pedro Pereira, Jose Guitian, Antida Andriollo, Alfredo Cirilo, Francisco Granadillo
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Patent number: 6034202Abstract: The invention provides non-antimony containing polymerization catalysts for the condensation of polyesters. The catalyst is in the form of a clear chlorine and/or bromine containing solution of a metal glycoxide and a metal glycolate having a pH in the range of from 0 to about 1, and containing chlorine and/or bromine atoms at a number ratio of chlorine and/or bromine to total metal cations in the catalyst ranging from about 0.5:1 to about 3:1. Polyesters produced with this catalyst have improved melt elasticity, and higher melt viscosity. The former property is desirable for the preparation of large and complex shaped polyester containers, and the latter property is desirable for melt spinning of industrial grade fibers and tire cords.Type: GrantFiled: March 1, 1999Date of Patent: March 7, 2000Assignee: AlliedSignal Inc.Inventors: Shaul Moshe Aharoni, Konstantin Nikolaev Goranov
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Patent number: 6034024Abstract: A process is described which comprises heating a methylalumoxane solution in an aromatic hydrocarbon solvent at a temperature of at least 35.degree. C. for at least 0.5 hour in an inert, dry atmosphere such that the resulting heat-treated composition provides, in a supported metallocene catalyst produced using the heat-treated composition, increased activity as compared to the same supported metallocene catalyst produced in the same way except for using a portion of the methylalumoxane solution that has not been heat-treated. Before the heating the methylalumoxane of the solution contains from about 5 to about 35 mole percent unreacted trimethylaluminum, and was formed by partial hydrolysis of trimethylaluminum with free water in an organic solvent.Type: GrantFiled: April 29, 1998Date of Patent: March 7, 2000Assignee: Albemarle CorporationInventors: Niomi L. Krzystowczyk, Steven P. Diefenbach, Edward A. Burt
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Patent number: 6001765Abstract: Catalytic system which can be used for the polymerization of .alpha.-olefins comprising:a solid based on complexed titanium trichloride of .delta. crystalline form;an organoaluminium compound;an organic oxygenated silicon compound;characterized in that the organoaluminium compound is a non-halogenated compound.Type: GrantFiled: February 6, 1997Date of Patent: December 14, 1999Assignee: Solvay Polyolefins Europe-BelgiumInventors: Jean-Louis Costa, Sabine Pamart
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Patent number: 5994256Abstract: A process is described for forming a catalyst precursor, for copolymerizing ethylene and an alpha-olefin of 3 to 10 carbon atoms, by preparing a contact mixture of an inert solvent, dibutylmagnesium and tetraalkyl orthosilicate which is free of precipitate and adding silica to the contact mixture to form a slurry to form a supported catalyst precursor. Titanium tetrachloride is then incorporated into the support in a specific ratio to the magnesium and silane components. Activation of this catalyst precursor with a trialkylaluminum compound results in a catalyst system which is effective for the production of ethylene copolymers.Type: GrantFiled: January 21, 1998Date of Patent: November 30, 1999Assignee: Mobil Oil CorporationInventors: James F. Lottes, Robert I. Mink, Thomas E. Nowlin, Yury V. Kissin
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Patent number: 5965478Abstract: A solid catalyst component for polymerization of olefins prepared by reacting a titanium halide, a diester of aromatic dicarboxylic acid and a dialkoxymagnesium having a bulk density of at least 0.25 g/ml and an average particle size of 1 to 100 .mu.m. The average rate of temperature rise from the temperature at which the titanium halide is allowed to come in contact with the dialkoxymagnesium to the temperature at which the reaction is initiated is in a range of from 0.5 to 20.degree. C./min. Such catalyst can further comprise an organic aluminum compound and an organic silicon compound. The use of said catalyst makes it possible to efficiently obtain a polyolefin having a high stereoregularity, a high bulk density and excellent particle properties.Type: GrantFiled: August 13, 1997Date of Patent: October 12, 1999Assignee: Toho Titanium Co., Ltd.Inventors: Kenji Goto, Motoki Hosaka, Akira Saito, Tetsuo Ohtsuka
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Patent number: 5965477Abstract: This invention is directed to a process for the preparation of a supported metallocene catalyst, said process comprising preparing a precursor catalyst material by dissolving a magnesium halide in an electron donor solvent in which the magnesium halide is completely soluble, heating the solution to a temperature in the range of 20.degree. C. to the boiling point of the respective electron donor for a period ranging between 10 to 60 minutes, separately preparing a solution of the metallocene compound into the same electron donor solvent, heating the solution to a temperature in the range of 25.degree. C. to 70.degree. C. for a period ranging between 0.1 to 0.5 hrs., mixing the two solutions to obtain a homogenous solution of catalyst precursor compound, stirring and maintaining this resulting homogenous solution at a temperature in the range of 50.degree. C. to 70.degree. C. for a period of 0.5 to 2 hrs.Type: GrantFiled: May 14, 1997Date of Patent: October 12, 1999Assignee: Council of Scientific & Industrial ResearchInventors: Swaminathan Sivaram, Soumen Sensarma
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Patent number: 5962360Abstract: The present invention is directed to a process for the preparation of a solid magnesium halide supported metallocene catalyst having a transition metal selected from the group consisting of IIIB, IVB, VB and VIB of the periodic table, which comprises preparing a slurry of magnesium metal in an electron donor solvent; heating the slurry of magnesium metal to 0.degree. C. to 50.degree. C. for a period of 10 minutes to 4 hr.; adding a dihaloalkane compound to said slurry to obtain a homogeneous solution of a support (solution A); separately preparing a solution of a metallocene compound in the same electron donor solvent as solution A (solution B); heating the solution B to 0.degree. C. to 50.degree. C. for a period ranging between 10 minutes and 1 hr., adding solution B to solution A over a period ranging between 10 minutes to 2 hrs. while maintaining the temperature in the range of 0 to 50.degree. C.Type: GrantFiled: May 14, 1997Date of Patent: October 5, 1999Assignee: Council of Scientific and Industrial ResearchInventors: Swaminathan Sivaram, Soumen Sensarma
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Patent number: 5962361Abstract: A method of making a solid, substantially dry olefin polymerization procatalyst precursor is disclosed whereby a solid precursor containing magnesium and titanium is formed in a slurry or solution, the solid then is separated from the solution and then dried at a temperature above 50.degree. C. for over an hour. Solid, substantially dry olefin polymerization procatalyst precursors made by the method also are disclosed, whereby the precursors are easier to handle, have better flowability, reduced clumpness and provide catalysts that can be used to produce polymers having improved extrudability, less filter clogging, less "talc"-like polymer particles of <10 micron in size and reduced polymer product segregation in storage.Type: GrantFiled: October 14, 1998Date of Patent: October 5, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Michael Philip Zum Mallen
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Patent number: 5958820Abstract: A process for polymerizing a gaseous conjugated diene by bringing it in contact with a catalyst consisting of a rare earth allyl compound, an organic aluminum compound, an inorganic support and optionally, the same or a different conjugated diene. The resulting polymers possess elevated proportions of cis-1,4 units.Type: GrantFiled: October 2, 1997Date of Patent: September 28, 1999Assignee: Bayer AGInventors: Rudolf Taube, Steffen Maiwald, Thomas Ruhmer, Heike Windisch, Jurgen Giesemann, Gerd Sylvester
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Patent number: 5914289Abstract: The present invention relates to the production of high density polyethylene homopolymers or copolymers having a broad and monomodal molecular weight distribution wherein the polymerization process is conducted in the presence of supported metallocene-alumoxane catalysts wherein the metallocene is bridged, comprises at least a hydrogenated indenyl or fluorenyl and a metal M which may be Ti, Zr or Hf, wherein a plurality of conformers of the metallocene are formed and isolated on the support by reaction of the metallocene with the alumoxane and depositing the product formed on the support at a temperature in the range 85.degree. C. to 110.degree. C.Type: GrantFiled: February 7, 1997Date of Patent: June 22, 1999Assignee: Fina Research, S.A.Inventor: Abbas Razavi
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Patent number: 5910463Abstract: Process for preparing a catalyst support, in which a hydrophilic, macroporous, finely divided aluminum oxide, silicon oxide, titanium oxide or zirconium oxide or a mixture or mixed oxide thereof is dried at from 110 to 800.degree. C., then reacted with an aluminoxane and subsequently with polyfunctional organic crosslinkers. In a further step, the catalyst support can be mixed with a reaction product of metallocenes and activators, giving a supported metallocene catalyst which is used, in particular, for the polymerization of olefins.Type: GrantFiled: July 14, 1997Date of Patent: June 8, 1999Assignee: Borealis AGInventors: Eberhard Ernst, Jens Reussner, Wolfgang Neissl
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Patent number: 5902764Abstract: Catalyst systems comprising, on the one hand, a catalytic solid based on complexed titanium trichloride and, on the other hand, a nonhalogenated organolauminium activator.When employed in gas phase olefin polymerization processes, these catalyst systems make it possible to manufacture a wide range of homopolymers and copolymers (random and block) with an isotacticity index which can be adjusted to very low values and with excellent pourability, even in the case of copolymers of high comonomer content.In the absence of transfer agents they also make it possible to synthesise polymers of very high molecular masses, with an increased activity.These polymerization processes yield particularly advantageous results in the case of propylene.Type: GrantFiled: May 4, 1993Date of Patent: May 11, 1999Assignee: Solvay Polyolefins Europe - Belgium (Societe Anonyme)Inventors: Jean-Louis Costa, Sabine Pamart
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Patent number: 5877109Abstract: Catalysts comprisingA) a rare earth alkoxide, a rare earth carboxylate and/or a rare earth coordination compound with diketones,B) an alumoxane andC) an inert, particulate, inorganic solid with a specific surface area of greater than 10 m.sup.2 /g and a pore volume of 0.3 to 15 ml/gare excellently suited to the polymerisation of conjugated dienes, in particular butadiene, in the gas phase.Type: GrantFiled: November 10, 1997Date of Patent: March 2, 1999Assignee: Bayer AGInventors: Karl-Heinz Reichert, Peter Marquardt, Christopher Eberstein, Birgit Garmatter, Gerd Sylvester
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Patent number: 5869417Abstract: The present invention provides a process for preparing a highly active metallocene catalyst by which polyolefin having improved properties can be prepared with a small amount of cocatalyst. A process for preparing a metallocene catalyst of the invention comprises the steps of: modifying the surface of a zeolite or molecular sieve inorganic carrier possessing crystalline pores of 7 to 100 .ANG. size by the addition of an organic solvent and organic aluminum compound under an environment of inert gas and reacting at a constant temperature, and drying; and, impregnating a metallocene compound into the inorganic carrier by the addition of an organic solvent and said metallocene compound, whose diameter is smaller than the diameters of said pores of the inorganic carrier, to the inorganic carrier and reacting at a constant temperature, and drying. In accordance with the present invention, a highly active metallocene catalyst can be prepared in an economical and efficient manner.Type: GrantFiled: September 3, 1996Date of Patent: February 9, 1999Assignee: Korea Advanced Institute of Science and TechnologyInventors: Seong-Ihl Woo, Young-Soo Ko
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Patent number: 5866088Abstract: Disclosed is a process for preparing an anhydrous magnesium halide solution, comprising a step of distilling water off from an oxygen-containing organic solvent solution of hydrous magnesium halide containing at least calcium as an impurity, to prepare an oxygen-containing organic solvent solution of anhydrous magnesium halide, wherein a potassium compound is added in said step to precipitate calcium and potassium, followed by removing the calcium and potassium. According to this process, an anhydrous magnesium halide solution scarcely containing calcium can be prepared from hydrous magnesium halide containing calcium as an impurity. Also disclosed is a process for preparing a solid titanium catalyst component for olefin polymerization, comprising contacting the anhydrous magnesium halide solution obtained by the above process with a liquid titanium compound to precipitate a solid titanium catalyst component.Type: GrantFiled: March 28, 1997Date of Patent: February 2, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Yoshinao Itoh, Masayuki Takeda
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Patent number: 5861352Abstract: A solid catalyst component for the polymerization and copolymerization of ethylene and alpha- olefins, containing a metallocene supported on an inorganic solid carrier constituted by a porous silicon oxide, the supported metallocene having the formula (I): ##STR1## wherein M is a group of metal, R' and R" are dialkylamide groups, R'" has the same definition as R' or is a cyclopentadienyl consisting ligand, and A is an anion containing an .eta..sup.5 -cyclopentadienyl ring coordinated to metal M, and wherein a carbon atom of the .eta..sup.5 -cyclopentadienyl ring of anion A is covalently bonded to the surface of the porous inorganic solid carrier.Type: GrantFiled: January 30, 1996Date of Patent: January 19, 1999Assignee: Enichem S.p.A.Inventors: Liliana Gila, Antonio Proto, Evelina Ballato, Diego Vigliarolo, Gabriele Lugli
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Preparation of supported auxiliary catalysts at elevated temperature and pressure in a closed vessel
Patent number: 5856255Abstract: A slurry is formed from an auxiliary catalyst (e.g., an aluminoxane or organoboron compound), a porous inorganic oxide carrier, and an inert organic solvent. The slurry is enclosed in a closed vessel and the temperature and pressure of the enclosed slurry are increased to a temperature of from about 80.degree. C. to 250.degree. C. and a pressure of from about 5 to 500 psig such that a supported composition is produced in the vessel. After opening the closed vessel, the supported composition and the solvent are separated from each other.Type: GrantFiled: January 22, 1996Date of Patent: January 5, 1999Assignee: Albemarle CorporationInventors: Niomi L. Krzystowczyk, Steven P. Diefenbach, John Y. Lee -
Patent number: 5846895Abstract: A supported metallocene complex of a metal M selected from Ti, Zr or Hf, is prepared by a process comprising, in a first step, the reaction of an inorganic carrier containing hydroxyl groups with a compound (II) containing a cyclopentadienyl group and at least one alkoxysilane group reactive with said hydroxyl groups so as to chemically bind said cyclopentadienyl group to said carrier; and in a second step the reaction with a complex of said metal M capable of reacting with said supported cyclopentadienyl group without carrying out any intermediate metallation of the latter. This process is simple and convenient, and enables high concentrations of metal stably bound to the carrier, to be reached. The complex thus obtained can be used as solid component of a catalyst active in the polymerization of .alpha.-olefins, in the presence of a suitable co-catalyst, preferably consisting of an organo-oxygenated derivative of aluminum.Type: GrantFiled: April 22, 1997Date of Patent: December 8, 1998Assignee: Enichem S.p.A.Inventors: Liliana Gila, Antonio Proto, Evelina Ballato, Diego Vigliarolo, Gabriele Lugli
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Patent number: 5830959Abstract: Process for the preparation of crystalline vinylaromatic polymers with a high degree of syndiotacticity which comprises polymerizing vinylaromatic monomers in the presence of a catalytic system essentially consisting of:a) a complex of titanium selected from those having the general formula:(CpR.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5)TiX.sub.3 (I)wherein the groups R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 represent a hydrogen atom or C.sub.1 -C.sub.10 alkyl groups;X represents a hydrogen atom, a halogen such as chlorine, a C.sub.1 -C.sub.10 alkyl or oxyalkyl radical or a C.sub.6 -C.sub.12 oxyaryl radical;b) an alkylaluminoxane; andc) an organic derivative of tin;characterized in that the alkylaluminoxane is methylaluminoxane (MAO) treated at 20.degree.-80.degree. C. under vacuum for 1-100 hours and the organic derivative of tin is tin tetraphenyl.Type: GrantFiled: October 6, 1997Date of Patent: November 3, 1998Assignee: Enichem S.p.A.Inventors: Riccardo Po', Nicoletta Cardi, Roberto Santi
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Patent number: 5817591Abstract: A method of forming a polyolefin catalyst component which includes chlorinating a magnesium alkoxide, solubilizing the chlorinated magnesium alkoxide into a hydrocarbon solvent utilizing an alcohol, and then precipitating a solid from the solvent by the dropwise addition of titanium tetrachloride. Two more titanation steps follow, the first with an electron donor, the second without an electron donor, to produce a catalyst having an improved yield of polymer.Type: GrantFiled: June 7, 1995Date of Patent: October 6, 1998Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, Christopher G. Bauch
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Patent number: 5789332Abstract: The present invention is directed to a gas phase process of preparing a supported metallocene catalyst wherein an alkylaluminum compound, water, a metallocene and, optionally, an olefin are metered into a fluidized bed reactor containing a fluidized bed of an inert support material in the presence of a gas stream.Type: GrantFiled: August 22, 1996Date of Patent: August 4, 1998Assignee: Witco GmbHInventors: Dirk Kutschera, Rainer Rieger
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Patent number: 5767215Abstract: The invention relates to a method for preparing polyolefins. In the polymerization, a procatalyst composition is being used, which has been prepared by contacting MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester. The polyolefin is given the adequate coarseness by using a procatalyst of the said type, which has been prepared by carrying out a transesterification between the lower alcohol and the phthalic acid ester and by selecting dioctyl phthalate (DOP) as phthalic acid ester.Type: GrantFiled: June 6, 1995Date of Patent: June 16, 1998Assignee: Borealis Holding A/SInventors: Thomas Garoff, Timo Leinonen, Eero Iiskola