Magnesium Containing Patents (Class 502/115)
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Patent number: 6245705Abstract: The invention relates to unsupported or supported catalyst compositions for alpha-olefin (ethylene and/or propylene) polymerization which comprises (1) a metallocene compound, (2) an inorganic aluminum compound Al(OH)xOy, wherein x is a number from 0 to 3, wherein x+2 y=3, (3) trimethylaluminum, wherein Al(OH)xOy is used in an amount sufficient to provide an Al(OH)xOy:metallocene molar ratio of 5 to 10,000, wherein trimethylaluminum is used in an amount sufficient to provide a trimethylaluminum:metallocene molar ratio of 50 to 10,000, and wherein the two aluminum compounds, (2) and (3), are used in amounts to provide a molar ratio of trimethylaluminum to Al(OH)xOy in the range of from 0.1 to 100.Type: GrantFiled: January 21, 1997Date of Patent: June 12, 2001Assignee: Univation TechnologiesInventor: Yury V. Kissin
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Patent number: 6228952Abstract: Catalytic composition effective in the hydrogenation of olefinic double bonds prepared by reaction between: (A) at least one cyclopentadienyl complex of a transition metal having general formula (I) (R)(R1)M1(R2)(R3) wherein R is an anion containing an &eegr;5-cyclopentadienyl ring coordinated to M1; M1 is selected from titanium, zirconium and hafnium; R2 and R3, the same or different, are organic or inorganic anion groups bound to M1; R1 is selected from cyclopentadienyl and R2; (B) an alkylating composition essentially consisting of: (b1) an organometallic compound having general formula (II) M2 (R4)(R5), wherein M2 is selected from Zn and Mg; (b2) an organoderivative of aluminum having general formula (III) Al(R6)3.Type: GrantFiled: November 2, 1998Date of Patent: May 8, 2001Assignee: Enichem S.p.A.Inventors: Gian Tommaso Viola, Andrea Vallieri, Claudio Cavallo
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Patent number: 6228791Abstract: The present invention is a solid catalyst component for polymerization of olefins prepared by contacting a magnesium compound, a tetravalent halogen-containing titanium compound, a diester of an aromatic dicarboxylic acid, an aromatic hydrocarbon and an organic aluminum compound containing a hydroxyl group represented by the following general formula (R1CO2)mAl(OH)3-m or aluminum hydroxide. The catalyst for polymerization of olefins comprising said solid catalyst component, an organic aluminum compound represented by the general formula R2pAlQ3-p and an organic silicon compound represented by the general formula R3qSi(OR4)4-q can retard the rate of forming a polymer having a low molecular weight or a low stereoregular polymer which is soluble in a polymerization solvent in slurry polymerization and can obtain a high stereoregular polymer in a high yield, and also can obtain a copolymer having an excellent property in a high yield in the copolymerization of olefins.Type: GrantFiled: July 6, 1999Date of Patent: May 8, 2001Assignee: Toho Titanium Co., Ltd.Inventors: Takuo Kataoka, Masayoshi Saito, Isa Nishiyama
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Patent number: 6228792Abstract: Supported Ziegler-Natta catalyst component adapted for the polymerization of ethylene is provided. More specifically, certain organomagnesium compounds (e.g., dibutylmagnesium) which do not contain an oxygen linkage between the organo moiety and the magnesium are impregnated into a porous inorganic oxide support (e.g., agglomerated silica particles) to form a first reaction product. The first reaction product is halogenated, e.g., with HCl, to convert the organomagnesium derived component to MgCl2 thereby forming a second reaction product. The second reaction product is then treated with a transition metal compound (e.g., TiCl4), a particular type of electron donor (e.g., 2,6-dimethyl pyridine) and optionally at least one Group 2 or 13 organo metal compound (e.g., diethylaluminum chloride). The combination of the particular organomagnesium compounds and electron donor impart a low melt flow ratio and enhanced activity to resulting catalyst component.Type: GrantFiled: February 27, 1998Date of Patent: May 8, 2001Assignee: W. R. Grace & Co.-Conn.Inventor: Michael John Carney
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Patent number: 6214759Abstract: The present invention relates to a method for producing a Ti/V supported catalyst useful in polymerization of ethylene and copolymerization of ethylene and &agr;-olefin. The method includes a treatment, by a titanium compound and a vanadium compound, of the magnesium-containing carrier, which is obtained by reaction of an organomagnesium compound of the structure of MgPh2.nMgCl2.mR2O (n=0.37˜0.7; m≧1; R2O=ether; Ph=phenyl) with an organic chloride compound in a mole ratio of organic chloride compound/Mg≧0.5, at −20˜80° C. According to the method for producing the catalyst, it is possible to provide a catalyst which can control the distribution of molecular weight, and when polymerization is performed using this catalyst, it is possible to restrain the inactivation and to secure a sufficient activity. Moreover, the polymer produced by the use of this catalyst proves to have a high bulk density and an adjusted particle size distribution.Type: GrantFiled: April 14, 1999Date of Patent: April 10, 2001Assignee: Samsung General Chemicals Co., Ltd.Inventors: Ho-Sik Chang, Youn-Kyung Kang
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Patent number: 6200921Abstract: The objective of the present invention is to provide a solid catalyst component and a catalyst for polymerization of olefins, which shows a high activity, can lower the rate of forming a polymer having a low molecular weight or a low stereoregular polymer which is soluble in a polymerization solvent and can obtain a high stereoregular polymer in a high yield. The present invention is a solid catalyst component(A) for polymerization of olefins prepared by contacting (a) dialkoxymagnesium, (b) a titanium compound, (c) a diester of an aromatic dicarboxylic acid, (d) an aromatic hydrocarbon and (e) an organic silicon compound containing a hydroxyl group, and a catalyst for polymerization of olefins prepared from the solid catalyst component (A) , an organic aluminum compound (B) represented by the general formula R2pAlQ3-p and an organic silicon compound (C) represented by the general formula R3qSi(OR4)4-q.Type: GrantFiled: October 26, 1999Date of Patent: March 13, 2001Assignee: Toho Titanium Co., Ltd.Inventor: Takuo Kataoka
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Patent number: 6194339Abstract: An ethylene polymerization catalyst and a catalyst system which provides an ethylene copolymer which, when formed into a film, is characterized by the combination of high stiffness and impact strength. The ethylene polymerization catalyst is formed by contacting a support with an organosilicon compound. The so-treated support is thereupon contacted, in a second step, with a dialkylmagnesium compound or complex. In a third step, the product of the second step is contacted with an alcohol or silane compound. This product, in turn, in a fourth step, is contacted with a transition metal compound. Finally, in a fifth and concluding step, the product of the fourth step is contacted with a Group 13 metal-containing compound. The second and third, as well as the third and fourth contacting steps may be reversed.Type: GrantFiled: November 17, 1999Date of Patent: February 27, 2001Assignee: Equistar Chemicals, LPInventor: William J. Sartain
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Patent number: 6177377Abstract: This invention relates to polymer blends and the process for preparing naturally compatibilized polyolefin blends using a “one-pot” polymerization of a single monomer, whereby two homopolymers having different structures are produced as well as a third block copolymer having alternating sequences of the two structural segments of the two homopolymers. The formation of the block copolymer is established by solvent extraction and 13C-NMR spectroscopy. The catalyst compositions enabling the direct synthesis of naturally compatibilized polymer blend is prepared by combining four components. The first two components are organometallic complexes of Group IVB or VIIIB elements. The third component is a cocatalyst which irreversibly reacts with at least one ligand on the transition metal complexes. The fourth component is a hydrocarbyl or oxyhydrocarbyl compound of Group IIIA metals, which functions as a cross-over agent.Type: GrantFiled: December 18, 1996Date of Patent: January 23, 2001Assignee: Amherst Polymer Technology, Inc.Inventor: James C. W. Chien
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Patent number: 6174971Abstract: A new synthesis of a Ziegler-Natta catalyst uses a multi-step preparation which includes treating a soluble magnesium compound with successively stronger chlorinating-titanating reagents. The catalyst may be used in polymerization of olefins, particularly ethylene, to produce a polymer with low amount of fines, large average fluff particle size and narrow molecular weight distribution. The catalyst has high activity and good hydrogen response.Type: GrantFiled: January 28, 1997Date of Patent: January 16, 2001Assignee: Fina Technology, Inc.Inventors: Hong Chen, Tim J. Coffy, Edwar S. Shamshoum
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Patent number: 6171993Abstract: The present invention provides an ethylene copolymer resin that has unique melt elastic properties not observed in ethylene copolymers heretofore known. Specifically, the ethylene copolymer resin of the present invention when in pelletized form has a reduction in melt elasticity (ER) of 10% or more to a final value of 1.0 or less upon rheometric low shear modification or solution dissolution. Moreover, the resin of the present invention when in reactor-made form exhibits at least a partially reversible increase of 10% or more in ER when pelletizing the same. An ethylene polymerization catalyst, a process of preparing the ethylene copolymer resin and a high-impact film are also provided herein.Type: GrantFiled: December 4, 1998Date of Patent: January 9, 2001Assignee: Equistar Chemicals, LPInventors: Harilaos Mavridis, Mark K. Reinking, Ramesh N. Shroff, Joel A. Mutchler, Charles S. Holland, Keta M. Lindstrom, Kiran M. Gupte, Michael H. Treptau, Francis M. Mirabella
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Patent number: 6165928Abstract: Procedure for the preparation of a solid catalyst component which is active in the polymerization of olefins, comprising the steps:a) contacting a dehydrated silica support with a solution of Mg-halide or Mg-alkyl-halide or a mixture of both, optionally in the presence of and Ti-alkoxyde or Ti-halogen-alkoxyde or a mixture of both,b) contacting the catalyst-precursor obtained in (a) with Mg-alkyl or Mg-alkyl-halide or a mixture of both, optionally in presence of electron-donors (Lewis bases),c) halogenating the catalyst-precursor obtained in (b) by contact of said activated support with halogenating agents,d) titanating the catalyst-precursor obtained in (c) with Ti-tetrahalide in the presence of electron-donors,e) recovering the solid catalyst-component from the reaction products of step (d).The catalyst component, which is obtained according to the above procedure, may also be used together with Al-trialkyl or Al-alkyl-halides and a Lewis base, as a catalyst for the polymerization of olefins.Type: GrantFiled: December 2, 1996Date of Patent: December 26, 2000Assignee: Borealis G.m.b.H.Inventors: Luciano Luciani, Wolfgang Neissl, Birgit Wenidoppler
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Patent number: 6156691Abstract: In catalyst systems of the Ziegler-Natta type modified during their preparation and comprising as active constituentsa) a titanium-containing solid component which is obtained by reacting a compound of titanium with a compound of magnesium, a halogen, an inorganic oxide as support, a C.sub.1 -C.sub.8 -alkanol and a carboxylic ester as electron donor compound,and also as cocatalystb) an aluminum compound andc) if desired, a further electron donor compound,the titanium-containing solid component a) is prepared by first, in a first stage, admixing an inorganic oxide as support with a solution of a chlorine-free compound of magnesium in an inert solvent, stirring this mixture for from 0.5 to 5 hours at from 10 to 120.degree. C. and subsequently reacting it while stirring continually in an inert solvent with a C.sub.1 -C.sub.8 -alkanol in an at least 1.Type: GrantFiled: September 12, 1997Date of Patent: December 5, 2000Assignee: BASF AktiengesellschaftInventors: Stephan Huffer, Ulrich Moll, Ian David McKenzie, Franz Langhauser, Peter Kolle, Roland Hingmann, Gunther Schweier, Rainer Hemmerich, Jurgen Kerth
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Patent number: 6147024Abstract: The present invention provides a catalyst for the polymerization of olefin that exhibits improved selectivity and broader molecular weight distribution in the polymer product. The catalyst is a conventional supported Ziegler-Natta catalyst in combination with a mixture of at least two electron donors, both having the general formula SiR.sub.m (OR').sub.4-m where R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a vinyl group; R' is an alkyl group; and m is 0-3, wherein when R is an alkyl group, R may be identical with R'; when m is 0, 1 or 2, the R' groups may be identical or different; and when m is 1, 2 or 3, the R groups may be identical or different. This catalyst produces polypropylene having xylene solubles of 1-7 to 5.1 wt % and a molecular weight distribution of about 10.Type: GrantFiled: July 12, 1999Date of Patent: November 14, 2000Assignee: Fina Technology, IncInventors: Edwar S. Shamshoum, David John Rauscher, Douglas Alan Burmaster
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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: 6133189Abstract: An .alpha.-olefin polymerization catalyst which comprises:(A) a solid catalyst component containing a tetra-valent titanium obtained by treating a magnesium compound having an Mg--O bond in its molecule with a titanium halide;(B) an organoaluminum compound; and(C) an organosilicon compound represented by the general formula R.sup.1 R.sup.2 Si(OR.sup.3).sub.2wherein R.sup.1 represents a hydrocarbon group having 4 to 30 carbon atoms wherein a carbon bonded directly to Si is a tertiary carbon, R.sup.2 represents a straight chain hydrocarbon group having 2 to 10 carbon atoms and R.sup.3 represents a hydrocarbon group having 1 to 10 carbon atoms, or the general formula R.sup.4 R.sup.5 Si(OR.sup.6).sub.2wherein R.sup.4 and R.sup.5 are hydrocarbon groups having an alicyclic hydrocarbon having 5 carbon atoms as a basic structure, R.sup.4 and R.sup.5 may be the same or different, and R.sup.6 represents a hydrocarbon group having 1 to 10 carbon atoms, and a process for producing .alpha.-olefin with said catalyst.Type: GrantFiled: June 6, 1996Date of Patent: October 17, 2000Assignee: Sumitomo Chemical Company, LimitedInventors: Yasuki Fujiwara, Makoto Satoh, Akio Imai
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Patent number: 6124412Abstract: The present invention relates to a new olefin polymerization catalyst composition, and methods of preparing and methods of using the catalysts to polymerize various olefinic monomers in either gas or slurry phase reactions. The principal advance over the previous art of record involves using alumoxanes or combinations of alumoxanes as catalyst preactivators. Polymers prepared from these catalysts posses productivity increased as high as 40 percent. At the same time, the bulk density remains relatively constant. Additionally, the total amount of cocatalyst species needed to effectively practice the invention is relatively low.Type: GrantFiled: December 29, 1997Date of Patent: September 26, 2000Assignee: Saudi Basic Industries CorporationInventors: Abdulmalik Bin-Taleb, Raju Raghavan, Abdulwhab Al-Sadoon
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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: 6084042Abstract: The present invention provides a Ziegler-Natta catalyst based on titanium and vanadium useful in solution processes for the polymerization of olefins having a low amount of aluminum and magnesium. The catalysts of the present invention have a molar ratio of magnesium to the first aluminum component from 4.0:1 to 8.0:1 and molar ratio of magnesium to titanium and vanadium from 4.0:1 to 8.0:1. The invention provides a novel catalyst preparation method to substantially increase the polymer molecular weight in the high temperature ethylene polymerization process.Type: GrantFiled: June 29, 1998Date of Patent: July 4, 2000Assignee: Nova Chemicals (International) S.A.Inventors: Isam Jaber, Stephen John Brown
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Patent number: 6080828Abstract: An ethylene polymer having small values of Mw/Mn and Mz/Mw, a small proportion of long-chain branches, a high melt tension and a high swell ratio, and a process for preparing the ethylene polymer are disclosed. A solid titanium catalyst component obtained by initially bringing a solid titanium composite which is obtained by the contact of a solid magnesium aluminum composite containing magnesium, halogen, aluminum, and an alkoxy group of 6 or more carbon atoms and/or alcohol of 6 or more carbon atoms with a tetravalent titanium compound into contact with an organometallic compound, and then bringing the resulting product into contact with oxygen is further disclosed. An ethylene polymerization catalyst comprising the above catalyst component and an organometallic compound catalyst component is furthermore disclosed. Therefore, the ethylene polymer is excellent in moldability, and a molded article obtained therefrom is excellent in rigidity and impact resistance and free from poor appearance.Type: GrantFiled: May 13, 1999Date of Patent: June 27, 2000Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Shin-ichi Kojoh, Mamoru Kioka
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Patent number: 6037296Abstract: The invention relates to a catalyst component which is a tract product of reagents comprising silica which has a pore volume which exceeds 2.9 cc/gram and an average pore diameter which exceed 400 Angstroms;a metallocene of a first transition metal, activated by an alumoxane,a contact product of dialkylmagnesium and trialkylsilanol,a second transition metal source which exhibits a hydrogen response which is different from that of the metallocenean olefin of 4 to 20 carbon atoms. This catalyst component is activated by an aluminum alkyl activator.Type: GrantFiled: April 24, 1998Date of Patent: March 14, 2000Assignee: Mobil Oil CorporationInventors: John T. T. Hsieh, Sandra D. Schregenberger
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Patent number: 6034026Abstract: The invention relates to a process for the preparation of a high activity procatalyst for the production of ethylene polymers. The process according to the present invention comprises the following steps:(a) contacting the inorganic support with an alkyl metal chloride which is soluble in non-polar hydrocarbon solvents, and has the formula(R.sub.n MeCl.sub.3-n).sub.m (1)wherein R is a C.sub.1 -C.sub.20 aklyl group, Me is a metal of group III(13) of the periodic table, n=1 or 2 and m=1 or 2, to give a first reaction product,(b) contacting said first reaction product with a compound or mixture containing hydrocarbyl and hydrocarbyl oxide linked to magnesium which is soluble in non-polar hydrocarbon solvents, to give a second reaction product, and(c) contacting said second reaction product with a titanium compound which contains chlorine, having the formulaCl.sub.x Ti(OR.sup.IV).sub.4-x (2)wherein R.sup.IV is a C.sub.2 -C.sub.20 hydrocarbyl group and x is 3 or 4, to give said procatalyst.Type: GrantFiled: January 28, 1998Date of Patent: March 7, 2000Assignee: Borealis Polymers OYInventors: Thomas Garoff, Solveig Johansson, Ulf Palmqvist, Daniel Lindgren, Marita Sutela, Paivi Waldvogel, Arja Kostiainen
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Patent number: 6028149Abstract: Procedure for the preparation of a solid catalyst component which is active in the polymerization of olefins, comprising the steps:a) contacting a silylated silica support with a solution of Mg-halide or Mg-alkyl-halide or a mixture of both and Ti-alkoxide or Ti-halogen-alkoxide or a mixture of both, optionally in the presence of Ti-tetrahalide,b) contacting the catalyst-precursor obtained in (a) with Mg-alkyl or Mg-alkyl-halide or a mixture of both, optionally in presence of Lewis base,c) halogenating the catalyst-precursor obtained in (b) by contact of said activated support with halogenating agents,d) titanating the catalyst-precursor obtained in (c) with Ti-tetrahalide in the presence of electron-donors,e) recovering the solid catalyst-component from the reaction products of step (d).The catalyst component, which is obtained according to the above procedure, may also be used together with Al-trialkyl or Al-alkyl-halides and a Lewis base, as a catalyst for the polymerization of olefins.Type: GrantFiled: September 30, 1996Date of Patent: February 22, 2000Assignee: PCD Polymere Gesellschaft m.b.H.Inventors: Luciano Luciani, Wolfgang Neissl, Birgit Wenidoppler
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Patent number: 6001764Abstract: A catalyst having a high pore volume, high surface area porous silica support and a non-metallocene, Ziegler-Natta catalytic component incorporated on the silica support is provided for the production of polyolefins from .alpha.-olefins. The porous silica support is made up of silica gel particles having an average surface area of about 600 to about 800 m.sup.2 /g of silica and an average pore volume of about 2.5 to about 4.0 ml/g of silica. Preferably, the silica particles have an average surface area of about 650 to about 750 m.sup.2 /g of silica and an average pore volume of about 2.75 to about 3.25 ml/g of silica. Even more preferably, the silica particles have an average surface area of about 700 m.sup.2 /g of silica and an average pore volume of about 3.0 ml/g of silica. The catalytic component comprises a complex product of a transition metal halide and a metal alkyl which excludes cyclopentadienyl rings.Type: GrantFiled: May 8, 1998Date of Patent: December 14, 1999Assignee: PQ CorporationInventors: Thomas J. Pullukat, Ronald S. Shinomoto, Reinhard H. Witt
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Patent number: 6001766Abstract: Catalyst compositions for homopolymerization and copolymerization of ethylene which comprise two transition metal compounds, one of them a cyclopentadienyl complex of a transition metal and another a non-metallocene derivative of a transition metal are described. The catalysts are activated by alkylalumoxanes that are soluble in non-aromatic hydrocarbons. Bimetallic catalysts of this invention are suitable for the manufacture of ethylene homopolymers and copolymers with broad bimodal molecular weight distributions. The alkyl alumoxanes have at least one [AR(R)--O--] repeating group in which R is an alkyl group of at least two carbon atoms.Type: GrantFiled: December 24, 1997Date of Patent: December 14, 1999Assignee: Mobil Oil CorporationInventors: Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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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: 5948869Abstract: Catalytic composition effective in the selective hydrogenation of olefinic double bonds prepared by the reaction between:(A) at least one bis(cyclopentadienyl)Titanium derivative having the general formula (I) (C.sub.5 H.sub.5).sub.2 Ti(R) (R.sub.1) wherein R and R.sub.1, the same or different, are halogens; the above compound (I) being solid or dispersed in one or more non-solvent diluents;(B) at least one organo derivative having general formula (II) M(R.sub.2) (R.sub.3) wherein M is selected from Zinc and Magnesium, and R.sub.2 and R.sub.3, the same or different, are selected from C.sub.1 -C.sub.16 alkyls;(C) at least one modifier.Type: GrantFiled: June 26, 1997Date of Patent: September 7, 1999Assignee: Enichem S.p.A.Inventors: Andrea Vallieri, Claudio Cavallo, Gian Tommaso Viola
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Patent number: 5948720Abstract: A catalyst for use in the production of flexible polyolefins using a pro-catalyst of (a) a magnesium halide, (b) an aluminum halide, (c) a tetravalent titanium halide, (d) an electron donor comprising at least one of 2,6-lutidine, 6-chloro-2-picoline, or 2,6-dichloropyridine; and (e) a silane having the formula R.sub.1 R.sub.2 Si(OR.sub.3)(OR.sub.4), wherein R.sub.1 and R.sub.2 are each an H, C.sub.1-6 alkyl, C.sub.1-6 aryl, C.sub.5-12 cycloalkane, each of which may be unsubstituted, mono- or di-substituted, and R.sub.3 and R.sub.4 are H, C.sub.1-6 alkane, or a mono- or di-substituted C.sub.1-6 alkane, and a co-catalyst of an organometallic compound, as well as an optional external modifier that may be combined to form a catalyst. Methods for preparing the catalyst, for using the same to produce flexible polyolefin compositions having reduced stickiness and tacticity, and the flexible polyolefin compositions produced thereby are also part of the invention.Type: GrantFiled: January 7, 1997Date of Patent: September 7, 1999Assignee: Huntsman Polymers CorporationInventors: Lixin Sun, George C. Allen, Michael P. Hughes
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Patent number: 5945366Abstract: A solid catalyst component (A1) for polymerization of olefins prepared by contact with a solid component (d) obtained by allowing (1) a solid component (a) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound and (iii) a diester of aromatic dicarboxylic acid to come in contact with one another and (2) a solid component (b) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound, (iii) a diester of aromatic dicarboxylic acid and (iv) a polysiloxane to come in contact with one another, to come in contact with each other, or a solid catalyst component (A2) for polymerization of olefins prepared by allowing said solid component (a) and (3) a solid component (d) obtained by allowing (i) a dialkoxymagnesium or diaryloxymagnesium, (ii) a titanium compound, (iii) a diester of aromatic dicarboxylic acid, (iv) a polysiloxane and (v) an aluminum compound to come in contact with one another, to come in contact with each other.Type: GrantFiled: April 21, 1997Date of Patent: August 31, 1999Assignee: Toho Titanium Co., Ltd.Inventors: Takuo Kataoka, Hidetoshi Umebayashi, Kenji Goto
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Patent number: 5939348Abstract: An ethylene-alpha-olefin copolymerization catalyst is prepared by impregnating a porous support, such as silica, with a contact mixture of an organomagnesium compound such as dialkyl magnesium and 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 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: December 12, 1996Date of Patent: August 17, 1999Assignee: Mobil Oil CorporationInventors: Robert I. Mink, Thomas E. Nowlin
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Patent number: 5891817Abstract: The present invention provides a catalyst system that exhibits unprecedented catalyst efficiencies and control of desired properties in the polymer product. The catalyst system includes a new generation titanium catalyst in combination with an electron donor described by the formula: ##STR1## wherein R.sub.1 is an alkyl group containing a primary carbon atom attached to the silicon atom; R.sub.2 and R.sub.3 are alkyl or aryl groups; and R.sub.4 is an alkyl group with a primary carbon atom attached to the silicon atom; R.sub.1 and R.sub.4 are the same or different. R.sub.1 and R.sub.4 are preferably chosen from the group consisting of n-propyl, n-butyl and methyl; most preferably n-propyl and n-butyl with R.sub.1 and R.sub.4 being the same or, alternatively, most preferably, R.sub.1 is methyl and R.sub.4 is C.sub.3 or higher. The system has a catalyst efficiency of over 30 kg/g-cat.multidot.h as the Si/Ti mole ratio varies from 4-20 in the system. The system easily achieves efficiencies over 30 kg/g-cat.Type: GrantFiled: June 7, 1995Date of Patent: April 6, 1999Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, David John Rauscher
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Patent number: 5885920Abstract: A process for producing a catalyst carrier for an olefin polymerization comprising:(i) passing a mixture to be emulsified comprised of (A) a halogenated magnesium adduct and (B) a dispersion medium through an emulsifying apparatus comprised of (1) a conduit for passage of the mixture to be emulsified, (2) a vibrator element disposed in the conduit and vibrating in the axial direction of the conduit, and (3) a vibration device for giving the vibration movement to the vibrator element; and(ii) quenching the resultant mixture.Type: GrantFiled: November 22, 1995Date of Patent: March 23, 1999Assignee: Japan Polyolefins Co., Ltd.Inventors: Hirotoshi Takahashi, Yasushi Kuroda, Shinya Waki, Hisayoshi Yanagihara, Koichi Sekiya
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Patent number: 5854164Abstract: A solid catalyst component (A) for olefin polymerization comprising Mg, Ti, a halogen and a cyclic organic nitrogen compound (C), a solid catalyst comprising the solid catalyst component and an organoaluminum compound, and a process for producing an olefin polymer with the catalyst.According to the present invention, there can be provided an olefin polymerization catalyst having a high catalyst activity per titanium enough to make the removal of catalyst residues unnecessary and a process for producing an olefin polymer having a low content of low molecular weight component with the catalyst.Type: GrantFiled: October 15, 1996Date of Patent: December 29, 1998Assignee: Sumitomo Chemical Company, LimitedInventors: Hiroyuki Shiraishi, Eiji Nakaishi, Takahiro Hino, Akio Imai
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Patent number: 5852141Abstract: The present invention relates to a prepolymer for the polymerization of olefins, the said prepolymer achieving a combination of a number of solid catalytic components for the polymerization of olefins. The combination of catalytic components makes it possible to combine two properties within the same polymer, one of the properties being contributed by one of the catalytic components and the other property being contributed by the other catalytic component.Type: GrantFiled: September 17, 1996Date of Patent: December 22, 1998Assignee: Elf Atochem S.A.Inventor: Jean Malinge
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Patent number: 5804679Abstract: Polyolefins exhibiting better particle properties are prepared by polymerizing an olefin or olefins in the presence of a catalyst comprising a solid catalyst component being prepared by the reaction of the following components ?I! and ?II!:?I! a reaction product obtained by reacting the following components (1), (2) and (3) with one another:(1) a silicon oxide and/or an aluminum oxide;(2) a reaction product obtained by the reaction of a magnesium halide and compound represented by the general formula Me(OR).sub.n X.sub.z-n wherein Me represents an element of Groups I to IV in the Periodic Table, z represents the valence of the element Me, n is 0<n.ltoreq.z, X is a halogen atom, and R is a hydrocarbon radical having 1 to 20 carbon atoms; and(3) a titanium compound represented by the general formula Ti(OR).sub.n X.sub.4-n wherein R is a hydrocarbon radical having 1 to 20 carbon atoms, X is a halogen atom, and n is 0.ltoreq.n.ltoreq.Type: GrantFiled: June 25, 1997Date of Patent: September 8, 1998Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Takeichi Shiraishi, Kunihiro Suzuki, Mitsuo Okamoto, Katumi Usui, Hiroyuki Shimizu, Kazuo Matsuura
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Patent number: 5798309Abstract: Process for preparing a poly-1-olefinBy means of a highly active spherical Ziegler catalyst based on a dialkylmagnesium, spherical polymers can be obtained in the polymerization of alpha-olefins. A further advantage of the catalyst of the invention lies in the high catalyst activity, so that only very small amounts of the catalyst are required for the polymerization. The residual titanium and/or zirconium content in the polymers prepared according to the invention is less than 10 ppm. Owing to its good responsiveness to hydrogen, the catalyst is particularly suited to two-stage processes for preparing polymers having a broad bimodal molecular weight distribution. The replacement of sulfur-containing electron donors such as diethyl sulfite by alcohols such as ethanol leads to less odor problems and broadened opportunities for use of the polymer.Type: GrantFiled: December 22, 1995Date of Patent: August 25, 1998Assignee: Hostalen Polyethylen GmbHInventors: Werner Breuers, Rainer Lecht, Ludwig Bohm
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Patent number: 5798314Abstract: A supported catalyst component for an olefin polymerization catalyst consisting essentially of a solid particulate support and a magnesium halide; and an olefin polymerization catalyst consisting essentially of a solid particulate support and a magnesium halide, a Group 4 or 5 transition metal compound, and a Group 2 or 13 organometallic compound, and wherein a majority of particles of the solid particulate support are in the form of an agglomerate of subparticles.Type: GrantFiled: June 4, 1996Date of Patent: August 25, 1998Assignee: The Dow Chemical CompanyInventors: Lee Spencer, Marc A. Springs
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Patent number: 5773537Abstract: Catalyst systems of the Ziegler-Natta type contain, as active componentsa) a titanium-containing solid component in whose preparation a titanium compound, a compound of magnesium, a halogenating agent and an electron donor component are used,b) an aluminum compound andc) as a further electron donor component, an organosilicon compound of the formula (I)R.sup.1 R.sup.2 Si(OR.sup.3).sub.2 (I)where R.sup.1 is C.sup.1 -C.sub.10 -alkyl or C.sub.3 -C.sub.8 -cycloalkyl, excluding sec-butyl, R.sup.2 is sec-butyl and R.sup.3 is C.sub.1 -C.sub.8 -alkyl. The catalyst systems are particularly suitable for the preparation of polymers of C.sub.2 -C.sub.10 -alk-1-enes.Type: GrantFiled: December 28, 1995Date of Patent: June 30, 1998Assignee: BASF AktiengesellschaftInventors: Patrik Mueller, Klaus-Dieter Hungenberg, Juergen Kerth, Ralf Zolk
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Patent number: 5770540Abstract: The invention relates to a procatalyst for the production of ethylene polymers, which procatalyst comprises an inorganic support, a chlorine compound carried on said support, a magnesium compound carried on said support, a titanium compound carried on said support, whereby the chlorine compound can be different from or the same as the magnesium compound and/or the titanium compound. The activity balance AB of the procatalyst in specified polymerization conditions, isAB>3.2wherein AB=?(A+A'):2!.multidot.?log (MFR.sub.2 ':MFR.sub.2):(A-A')!, A means polymerization activity expressed an kg PE/g cat .multidot.h, MFR.sub.2 means the melt flow rate in g/min units at a load of 2,16 kg, according to the standard ISO 1133, the absence of the upper index ' means low melt flow rate polymerization and the presence of the upper index ' means high melt flow polymerization. This means that the catalyst activity is relatively independent of the presence of chain transfer agents.Type: GrantFiled: June 20, 1995Date of Patent: June 23, 1998Assignee: Borealis Polymers OyInventors: Thomas Garoff, Solveig Johansson, Ulf Palmqvist, Daniel Lindgren, Marita Sutela, Paivi Waldvogel, Arja Kostiainen
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Patent number: 5744414Abstract: The present invention relates to a process for the preparation of a solid catalytic component of a catalyst of Ziegler-Natta type, comprising contacting (i) at least one compound (A) of a transition metal (TM) with (ii) a solid product (B) comprising a magnesium compound and having a reducing power for the transition metal (TM), in the presence of (iii) at least one olefin under conditions such that the olefin at least partially polymerizes during the contacting. The solid catalytic component is particularly useful for producing ethylene (co-)polymers in a gas phase process and for improving the statistical distribution of the comonomer in the copolymer structure.Type: GrantFiled: June 28, 1994Date of Patent: April 28, 1998Assignee: BP Chemicals LimitedInventor: Charles Jenny
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Patent number: 5744678Abstract: An oligomerization catalyst according to the invention comprises a nickel compound (A); an organophosphoric compound (B); an organoaluminum compound (C); and a compound of the group consisting of carbon-halogen bond-containing compounds, oxoacid and salts thereof, sulfonic acid and derivatives thereof, and compounds of any of the formulae QX.sup.4.sub.n, QR.sub.n, QR'.sub.n, QX.sup.4.sub.1 R.sub.m, QX.sup.4.sub.1 R'.sub.m, QR.sub.1 R'.sub.m, Q.sup.1 (BR.sub.4).sub.p and R"(BR.sub.4) wherein Q is an element of the group consisting of Mg, Ti, Zr, B and Sn, Q.sup.1 is an element of the group consisting of Li, Na, K, Ca and Zn, X.sup.4 is a halogen or hydrogen atom, R is a C.sub.1 -C.sub.12 hydrocarbon group, R' is a C.sub.1 -C.sub.12 oxygen-containing hydrocarbon group, R" is a C.sub.1 -C.sub.20 hydrocarbon group or an ammonium group, n is a valence of Q, l, m is a natural member that satisfied n=l+m, and p is a valence of Q.sup.1. This catalyst is useful for the production of alpha-olefinic oligomers.Type: GrantFiled: November 1, 1996Date of Patent: April 28, 1998Assignee: Nippon Oil Co., Ltd.Inventors: Fuyuki Aida, Takashi Nakano, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5728641Abstract: According to the present invention there are provided a catalyst component, a catalyst using the catalyst component and a process using the catalyst, for the preparation of olefin polymers high in molecular weight and relatively wide in molecular weight distribution, using an extremely small amount of a modified organoaluminum compound such as methylaluminoxane and in high yield. The catalyst component is prepared by contacting at least the following constituents (1), (2), (3) and (4) with one another:(1) a compound represented by the general formula Me.sup.1 R.sup.1.sub.p (OR.sup.2).sub.q X.sub.4-p-q where R.sup.1 and R.sup.2 are each independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf, p and q are each an integer in the ranges of 0.ltoreq.p.ltoreq.4 and 0.ltoreq.q.ltoreq.4, provided 0.ltoreq.p+q.ltoreq.4;(2) at least one compound selected from the group consisting of compounds represented by the following general formulas 1 to 4:General formula 1: Me.sup.Type: GrantFiled: June 21, 1995Date of Patent: March 17, 1998Assignee: Nippon Oil Company, LimitedInventors: Fuyuki Aida, Yoshio Tajima, Kazuo Matsuura
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Patent number: 5723400Abstract: Process for the preparation of a solid catalyst component for olefins polymerization including (1) a magnesium halide in active form, (2) a titanium compound, and (3) an electron-donor compound selected from particular 1,3-diethers, the process being carried out by reaction between the compounds from (1) to (3), and including at least two additions of electron-donor (3) in the following order:a) one addition prior to or during a reaction with the titanium compound or with a halogenated compound, and thenb) one addition prior to or during a further reaction with the titanium compound.Type: GrantFiled: February 20, 1996Date of Patent: March 3, 1998Assignee: Montell North America Inc.Inventors: Giampiero Morini, Enrico Albizzati, Giulio Balbontin, Giovanni Baruzzi, Antonio Cristofori
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Patent number: 5693583Abstract: A catalyst composition for copolymerizing ethylene and alpha-olefins is prepared by treating a silica carrier, in a non-polar hydrocarbon solvent, with a dialkyl magnesium compound, a halogen-containing compound and titanium tetrachloride, to form a catalyst precursor and activating the precursor with dimethylaluminum chloride.Also disclosed is a process for copolymerizing ethylene and alpha-olefins in the presence of the catalyst of the invention. The polymer products have multimodal molecular weight distributions unlike unimodal molecular weight distributions of polymers prepared with similar catalyst precursors but activated with different alkylaluminum activators, e.g., triethylaluminum or trimethylaluminum.Type: GrantFiled: February 11, 1997Date of Patent: December 2, 1997Assignee: Mobil Oil CorporationInventors: Robert O. Hagerty, Per K. Husby, Yury V. Kissin, Robert I. Mink, Thomas E. Nowlin
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Patent number: 5677256Abstract: An olefin polymerization catalyst composition is prepared by adding an organometallic compound of a group IA to IIIA metal to a procatalyst containing a support impregnated with TiCl.sub.4 but without using free TiCl.sub.4 to impregnate the support. The procatalyst is prepared by stirring a carrier with magnesium dichloride and a titanium tetralkoxide in a hydrocarbon solvent containing an electron donor, evaporating the solvent and the donor to form a free-flowing powder and chlorinating the titanium tetralkoxide with an alkyl aluminum chloride.Type: GrantFiled: January 19, 1996Date of Patent: October 14, 1997Assignee: Neste OyInventors: Sirpa Ala-Huikku, Pekka Sormunen
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Patent number: 5670439Abstract: A vanadium-containing catalyst system particularly suited to the polymerization of olefin polymers. The catalyst system includes a supported, first catalyst component prepared by contacting silica with hexaalkyldisilazane and thereupon with (1) a compound or complex which includes at least one carbon to magnesium covalent bond and (2) a compound which includes at least one carbon to Group 13 metal covalent bond. The sequence of contact of the silica with compound or complex (1) and compound (2) is optional. However, unless the compound or complex (1) and the compound (2) contact the silica simultaneously, the product of this contact is next contacted with whichever of compound (1) or (2) does not initially contact the silica. The product of the step of contacting with compounds (1) and (2) is washed and then contacted with a vanadium compound which includes at least one halogen atom. Finally, the product of the vanadium compound contacting step is contacted with an alcohol.Type: GrantFiled: January 5, 1996Date of Patent: September 23, 1997Assignee: Quantum Chemical CorporationInventors: Linda N. Winslow, Raghu K. Menon
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Patent number: 5670587Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound-based polymer composition which catalyst comprises (A) at least two different transition metal compounds each having one .pi.-ligand and (B) an ionic compound comprising a noncoordinate anion and a cation and/or an aluminoxane, and (C) a Lewis acid to be used as the case may be; and a process for producing an aromatic vinyl compound-based polymer composition having a high degree of syndiotactic configuration in its aromatic vinyl chains which process comprises polymerizing an (a) aromatic vinyl compound and (b) an olefinic compound and/or a diolefinic compound in the presence of the above catalyst.Type: GrantFiled: January 23, 1996Date of Patent: September 23, 1997Assignee: Idemitsu Kosan Co., Ltd.Inventors: Mizutomo Takeuchi, Hajime Shouzaki, Norio Tomotsu, Masahiko Kuramoto