Nonmetallic Organic Phosphorus Containing Patents (Class 502/121)
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Patent number: 6284701Abstract: The new metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene compound is a transition metal compound, which is coordinated with a main ligand such as cyclopentadienyl group, and an ancillary ligand. The functional groups in the compound are selected from the group consisting of a hydroxyl group, an alkyl or aryl magnesium halide, a thiol group, a primary amine group, a secondary amine group, a primary phosphorous group, a secondary phosphorous group, etc. The metallocene catalysts according to the present invention have a structure in which an ancillary ligand of a metallocene compound is bonded to the functional groups of a compound having at least two functional groups. A structure of the metallocene catalysts can be varied with the type of a metallocene compound and a compound having at least two functional groups, and the molar ratio of each reactant.Type: GrantFiled: April 20, 1999Date of Patent: September 4, 2001Assignee: Samsung General Chemicals Co., Ltd.Inventors: Keun-Byoung Yoon, Seok Chang, Won-Cheol Jung, Yi-Yeol Lyu
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Patent number: 6274529Abstract: A catalytic system with an increased activity for the (co)polymerization of alpha-olefins comprises a catalyst of the metallocene type, which is capable of polymerizing olefins without aluminoxane, and a weak coordinating compound, which, when used in a polymerization process, enables a higher productivity than an analogous process carried out with the metallocene type catalyst per se.Type: GrantFiled: October 22, 1996Date of Patent: August 14, 2001Assignee: Enichem S.p.A.Inventors: Roberto Fusco, Luca Longo, Antonio Proto, Diego Vigliarolo, Gianfranco Guglielmetti, Liliana Gila
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Patent number: 6211313Abstract: A catalyst composition that is the combination of or the reaction product of ingredients including an iron-containing compound, a hydrogen phosphite, and an aluminoxane. This catalyst composition is useful for polymerizing conjugated diene monomers and is particularly useful for polymerizing 1,3-butadiene into syndiotactic 1,2-polybutadiene.Type: GrantFiled: November 12, 1999Date of Patent: April 3, 2001Assignee: Bridgestone CorporationInventor: Steven Luo
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Patent number: 6184316Abstract: A catalyst for the polymerization of vinylaromatic monomers, and particularly styrene, with a high yield and a high syndiotacticity index, comprises the product consisting of the following two components in contact with each other: A) an &eegr;5-cyclopentadienyl complex of titanium; B) an organo-oxygenated compound of aluminum; and contains a sufficient amount of at least one carboxylated product having the following general formula: R—COO—G (I) wherein R—COO is a carboxylic group comprising the organic radical R having from 1 to 30 carbon atoms, and G represents a hydrogen atom, an aliphatic or aromatic hydrocarbon group having from 1 to 20 carbon atoms or a metal atom, possibly substituted, linked to said carboxylic group.Type: GrantFiled: February 25, 1998Date of Patent: February 6, 2001Assignee: Enichem S.p.A.Inventors: Francesco Masi, Riccardo PO′, Francesco Menconi, Giuseppe Conti, Francesco Ciardelli, Angelina Altomare, Federico Orsini, Roberto Santi, Nicoletta Cardi
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Supported catalyst system, process for its preparation and its use for the polymerization of olefins
Patent number: 6177526Abstract: The present invention relates to a supported catalyst system which comprises at least one metallocene component and at least one cocatalyst component and at least one modified inorganic oxide of silicon, aluminum or mixtures thereof, wherein the modified oxide contains organic silicon radicals containing at least one of the groups nitrogen, fluorine, phosphorus or sulfur.Type: GrantFiled: June 5, 1997Date of Patent: January 23, 2001Assignee: Targor GmbHInventor: Cornelia Fritze -
Patent number: 6177376Abstract: The present invention relates to a process for preparing a metallocene catalyst system, which comprises reacting a metallocene starting compound in a solvent with a compound capable of transferring hydrocarbon radicals and converting the resulting metallocene compound which is &sgr;-substituted by one or more hydrocarbon radicals in solution without isolation into a polymerization-active catalyst system by means of an activator.Type: GrantFiled: January 29, 1998Date of Patent: January 23, 2001Assignee: Targor GmbHInventors: Cornelia Fritze, Hans Bohnen, Frank K{umlaut over (u)}ber
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Patent number: 6165929Abstract: A process is provided to produce a composition of matter. The process comprises contacting at least one organometal compound, at least one solid mixed oxide compound, and at least one organoaluminum compound to produce the composition.Type: GrantFiled: May 18, 1998Date of Patent: December 26, 2000Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Shirley J. Martin, Kathy S. Collins, Marvin M. Johnson
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Patent number: 6166170Abstract: A catalyst composition is disclosed. The composition comprises a titanium compound, a complexing agent, hypophosphorous acid or its metal salt, water and optionally a solvent. The complexing agent can be hydroxycarboxylic acid, alkanolamines, aminocarboxylic acids, or combinations of two or more thereof. The solvent can be water, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, isopropylene glycol, butylene glycol, 1-methyl propylene glycol, pentylene glycol, or combinations of two or more thereof. The titanium compound can be combined with a zirconium compound. Also disclosed is a process for using the composition for producing an ester or a polyester. The process comprises contacting a carbonyl compound, in the presence of the composition, with an alcohol under a condition suitable for esterification, transesterification, polymerization, or combinations of two or more thereof.Type: GrantFiled: December 2, 1999Date of Patent: December 26, 2000Assignee: E. I. du Pont de Nemours and CompanyInventor: Donald Edward Putzig
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Patent number: 6160063Abstract: A catalyst composition that is the combination of or the reaction product of ingredients including an iron-containing compound, an organomagnesium compound, and a cyclic hydrogen phosphite. This catalyst composition is particularly useful for polymerizing 1,3-butadiene into binary cis-1,4/1,2-polybutadiene.Type: GrantFiled: December 30, 1999Date of Patent: December 12, 2000Assignee: Bridgestone CorporationInventor: Steven Luo
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Patent number: 6143685Abstract: Catalytic systems particularly suitable for the polymerization of .alpha.-olefins containing from two to 20 carbon atoms, as well as for the copolymerization of ethylene with .alpha.-olefins containing from three to 20 carbon atoms, dienes, and cycloalkenes in processes wherein the catalyst is suspended in a solvent, in processes in gas phase, as well as in mass polymerization processes at high temperatures and pressures, are disclosed. The catalytic system is a mixture of a catalyst component A and a co-catalyst component B. The catalyst component A is formed by a functionalized inorganic porous oxide, by an organoaluminium compound and by an organometallic compound of a metal of the groups 3, 4, 5, or 6 of the periodic table. Functionalization of the inorganic oxide is by introduction of functional groups to be used to strongly fix the organoaluminium compound and the organometallic compound.Type: GrantFiled: April 18, 1997Date of Patent: November 7, 2000Assignee: Respsol Quimica S.A.Inventors: Gerardo Hidalgo Llinas, Begona Pena Garcia, Antonio Munoz-Escalona, Jose Sancho Royo
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Patent number: 6133187Abstract: A catalyst comprising a cocatalyst and a catalyst component obtained by contacting a silicon-containing metallocene compound with an inorganic support to chemically bond the metallocene compound to the inorganic support, wherein the silicon-containing metallocene compound has a formula (I): ##STR1## wherein: M is a metal selected from [the group consisting of] group 4, 5, or 6 of the periodic table;each X is independently selected from the group consisting of hydrogen, halogen, C.sub.1 -C.sub.10 alkyl, C.sub.1 -C.sub.10 alkoxy, C.sub.6 -C.sub.10 aryl, C.sub.6 -C.sub.10 aryloxy, C.sub.2 -C.sub.10 alkenyl, C.sub.7 -C.sub.40 arylalkyl, C.sub.7 -C.sub.40 alkylaryl, and C.sub.8 -C.sub.40 arylalkenyl;A.sub.1 and A.sub.2 are independently selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, fluorenyl, substituted indenyl, and substituted fluorenyl, wherein the substituents are independently C.sub.1 -C.sub.10 linear or branched alkyl, C.sub.5 -C.sub.Type: GrantFiled: October 19, 1998Date of Patent: October 17, 2000Assignee: Repsol Quimica S.A.Inventors: Wilfried Michiels Vega, Pilar Lafuente Canas, Antonio Munoz-Escalona Lafuente, Gerardo Hidalgo Llinas, Jose Sancho Royo, Luis Mendez Llatas
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Patent number: 6130180Abstract: An aminosilane of the formula: ##STR1## where R.sub.1 is a linear or branched C.sub.1-22 alkyl or C.sub.3-22 cycloalkyl, which may be substituted with at least one halogen atom; R.sub.2 is a bis(linear or branched C.sub.1-22 alkyl or C.sub.3-22 cycloalkyl)amino, a substituted piperidinyl, a substituted pyrrolidinyl, decahydroquinolinyl, 1,2,3,4-tetrahydroquinolinyl or 1,2,3,4-tetrahydroisoquinolinyl, with the substituent selected from the group consisting of C.sub.1-8 alkyl, pheny. C.sub.1-8 linear or branched alkylsubstituted phenyl and trimethylsilyl, with the proviso that when the substituent is C.sub.1-8 alkyl, there must be at least two such substituent groups present and R.sub.1 must contain halogen; and R.sub.3 is a linear or branched C.sub.1-8 alkyl or C.sub.3-8 cycloalkyl.Type: GrantFiled: December 23, 1997Date of Patent: October 10, 2000Assignee: Montell North America Inc.Inventors: Constantine A. Stewart, Eric J. Evain
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Patent number: 6117956Abstract: The instant invention teaches a method for forming a syndiotactic 1,2-polybutadiene product having a higher syndiotacticity and a higher melting temperature than syndiotactic 1,2-polybutadiene produced using chromium catalysts known in the prior art. The method includes polymerizing 1,3-butadiene in solution with a solvent, in the presence of catalytically effective amounts of: (a) a chromium compound; (b) an organomagnesium compound; and, (c) a cyclic hydrogen phosphite.Type: GrantFiled: June 1, 1998Date of Patent: September 12, 2000Assignee: Bridgestone CorporationInventor: Steven Luo
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Patent number: 6107230Abstract: This invention provides compositions for polymerizing at least one monomer to produce a polymer. The compositions are produced by a process comprising contacting at least one organometal compound, at least one organoaluminum compound, and at least one treated solid oxide compound. The treated solid oxide compound is produced by a process comprising contacting at least one solid oxide compound with at least one electron-withdrawing anion source compound and at least one metal salt compound.Type: GrantFiled: May 18, 1998Date of Patent: August 22, 2000Assignee: Phillips Petroleum CompanyInventors: Max P. McDaniel, Kathy S. Collins, Marvin M. Johnson, James L. Smith, Elizabeth A. Benham, Gil R. Hawley, Christopher E. Wittner, Michael D. Jensen
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Patent number: 6080834Abstract: A catalyst composition is disclosed. The composition comprises a titanium compound, a complexing agent, a solvent, and optionally a cocatalyst. The cocatalyst can be a cobalt/aluminum catalyst, an antimony compound, or combinations thereof. Also disclosed is a process for producing the composition. The process comprises combining a titanium compound, a complexing agent, a solvent, and optionally a cocatalyst. Further disclosed is a process for using the composition which comprises contacting a carbonyl compound, in the presence of the composition, with an alcohol under a condition suitable for esterification, transesterification, polymerization, or combinations thereof.Type: GrantFiled: April 16, 1999Date of Patent: June 27, 2000Assignee: E. I. du Pont de Nemours and CompanyInventors: Donald Edward Putzig, Edward Francis McBride, Hiep Quang Do, James Arthur Trainham, Hermann Ludwig Jaeger, Heiner Schulte
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Patent number: 6080697Abstract: A process to produce a composition is provided. Said process comprises: contacting a zeolite component, a silicon component, a Group 14 metal component, and a phosphorus component together to form a first mixture; treating said first mixture to form a second mixture; contacting said second mixture with a binder component to form a third mixture; agglomerating said third mixture to form a fourth mixture; and treating said fourth mixture to form said composition.Type: GrantFiled: October 7, 1998Date of Patent: June 27, 2000Assignee: Phillips Petroleum CompanyInventors: An-hsiang Wu, Charles A. Drake
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Patent number: 6074977Abstract: Catalyst compositions that are highly tolerant of catalyst poisons comprising a cationic or zwitterionic Group 4 metal complex of the constrained geometry type and an organoaluminum hydrocarbyloxide compound according to the formula R.sup.1.sub.2 Al(OR.sup.2),wherein R.sup.1 and R.sup.2 independently each ocurrence are C.sub.1-30 hydrocarbyl,the molar ratio of complex to organoaluminum hydrocarbyloxide compound being from 1:0.1 to 1:100.Type: GrantFiled: September 2, 1998Date of Patent: June 13, 2000Assignee: The Dow Chemical CompanyInventors: Robert K. Rosen, James C. Stevens, John C. Tracy
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Patent number: 6066714Abstract: A catalyst composition is disclosed. The composition comprises a titanium compound, a phosphorus compound, an amine, a solvent and optionally a cocatalyst in which the phosphorus compound has a formula selected from the group consisting of (R.sup.1 O).sub.x (PO)(OH).sub.3-x, (R.sup.1 O).sub.y (P.sub.2 O.sub.3)(OH).sub.4-y, and combinations thereof; the amine is a tertiary amine; each R.sup.1 is independently a linear or branched alkyl radical containing from 1 to about 20 carbon atoms per radical; x is 1 or 2; and y is 1, 2, or 3; and the cocatalyst can be a cobalt/aluminum catalyst, an antimony compound, or combinations thereof. Also disclosed is a process for producing the composition. The process comprises combining a titanium compound, a phosphorus compound, a solvent, an amine, a solvent, and optionally a cocatalyst. The phosphorus compound, amie, and solvent are the same as those disclosed above.Type: GrantFiled: April 15, 1999Date of Patent: May 23, 2000Assignee: E. I. du Pont de Nemours and CompanyInventors: Donald Edward Putzig, Edward Francis McBride, Hiep Quang Do, James Arthur Trainham, Hermann Ludwig Jaeger, Heiner Schulte
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Patent number: 6051522Abstract: A catalyst containing the combination which comprises:(a) an aluminoxane, a compound of the formula R.sub.x NH.sub.4-x, BR'.sub.4, R.sub.x PH.sub.4-x, BR'.sub.4, R.sub.3 CBR'.sub.4 or BR'.sub.3, or a mixture thereof wherein X is an integer from 1 to 4 and the radicals R are identical or different and are a C.sub.1 -C.sub.10 -alkyl or a C.sub.6 -C.sub.18 -aryl or 2 radicals R together with the atom joining them form a ring, and the radicals R' are identical or different and are a C.sub.6 -C.sub.18 -aryl which optionally are substituted by alkyl, haloalkyl or fluorine, and(b) a metallocene of the formula VI ##STR1## in which M.sup.1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,R.sup.1 is (C.sub.3 -C.sub.20)alkyl, (C.sub.6 -C.sub.14)aryl, (C.sub.4 -C.sub.10)alkoxy, (C.sub.2 -C.sub.10)alkenyl, (C.sub.7 -C.sub.20)arylalkyl, (C.sub.7 -C.sub.20)alkylaryl, (C.sub.6 -C.sub.10)aryloxy, (C.sub.1 -C.sub.10)fluoroalkyl, (C.sub.6 -C.sub.10)halogenoaryl, (C.sub.2 -C.sub.10)alkynyl; a radical --SiR.sup.6.Type: GrantFiled: June 5, 1995Date of Patent: April 18, 2000Assignee: Targor GmbHInventors: Jurgen Rohrmann, Frank Kuber
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Patent number: 6051524Abstract: A solid, hydrocarbon-insoluble, catalyst component useful in polymerizing olefins containing magnesium, titanium, and halogen further contains an internal electron donor comprising ##STR1## wherein R is selected from C.sub.1 -C.sub.8 alkyl, C.sub.6 -C.sub.9 aryl or C.sub.1 -C.sub.8 alkoxy groups; and wherein X and Y are N-R', O, P(O)(OR'), P(O)R', or S, and R' is selected from hydrogen, C.sub.1 -C.sub.8 alkyl and alkoxy, and C.sub.6 -C.sub.9 aryl groups, provided that up to two Y groups may be CR'.sub.2 groups.Type: GrantFiled: April 22, 1993Date of Patent: April 18, 2000Assignee: BP Amoco CorporationInventors: Nicholas M. Karayannis, Steven A. Cohen, Julie L. Ledermann
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Patent number: 5977270Abstract: There is provided a polymerization process for the production of olefin polymers using a catalyst composition comprising: a) (i) a catalyst containing at least one cycloalkadienyl ligand substituted with at least one electron donor residue and coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals; or (ii) a catalyst containing two cycloalkadienyl ligands coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals, said cycloalkadienyl ligands connected by a bridging group comprising at least one Group IVA element and at least one electron donor residue; and b) an activating cocatalyst of the formula R.sub.x M', wherein R is alkyl, aryl, or hydride; M' is a Group I, II, or IIIA metal or a Group I, II, or IIIA metal complexed with oxygen, nitrogen, or a halide; and x is equal to the valence of M'.Type: GrantFiled: January 26, 1998Date of Patent: November 2, 1999Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Timothy Todd Wenzel
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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: 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: 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: 5948872Abstract: A solid titanium catalyst component ?Ia! containing magnesium, halogen, titanium and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a catalyst and a prepolymerized olefin-containing catalyst prepared by using the solid titanium catalyst component ?Ia!; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used. A catalyst and a prepolymerized olefin containing catalyst prepared by using a solid titanium catalyst component ?Ib! containing magnesium, halogen, titanium and a specific electron donor (al), and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used.Type: GrantFiled: December 12, 1997Date of Patent: September 7, 1999Assignee: Mitsui Chemicals, Inc.Inventors: Mamoru Kioka, Tetsunori Shinozaki
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Patent number: 5928982Abstract: A catalyst for polymerizing an olefin, which comprises (A) a metallocene transition metal compound, (B) (1) an ion-exchanging layered compound other than a silicate or (2) an inorganic silicate prepared by treating a starting ion-exchanging layer compound other than a silicate or a starting silicate with a salt, an acid, or a combination thereof, said component (B) having a water content not higher than 1% by weight which is obtained by heat-dehydrating component (B) under an inert gas atmosphere or under reduced pressure, and (C) an organoaluminum compound.Type: GrantFiled: July 31, 1996Date of Patent: July 27, 1999Assignee: Mitsubishi Chemical CorporationInventors: Yoshinori Suga, Yumito Uehara, Yasuo Maruyama, Eiji Isobe, Yoshiyuki Ishihama, Takehiro Sagae
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Patent number: 5922631Abstract: Olefin polymerization catalysts are described that comprise the reaction product of (a) a metallocene and/or a Ziegler-Natta catalyst compound (TICl.sub.4, etc.,) and (b) a liquid clathrate composition formed from (i) an aluminoxane, (ii) an organic, inorganic or organometallic compound, and (iii) an aromatic solvent. These liquid clathrates are obtained by the reaction, in aromatic solvents, of aluminoxanes such as, methylaluminoxane, with organic, inorganic or organometallic compounds that form stable clathrates with the aluminoxane and the solvent.Type: GrantFiled: April 18, 1997Date of Patent: July 13, 1999Assignee: Albemarle CorporationInventor: Samuel A. Sangokoya
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Patent number: 5834572Abstract: Process for the manufacture of a support containing silica and at least one constituent chosen from alumina and aluminium phosphate, according to which an alcohol, water, a silicon alkoxide and an acid are mixed under conditions such that gelling or precipitation of silica is prevented, an acidic solution of an aluminium compound and/or a solution of a source of phosphate ions are added thereto, a gelling agent is added thereto, a gel is recovered which is washed with water and then by means of an organic liquid, the gel is then dried by atomization until a powder is obtained, and the powder is calcined. Polymerization of olefins in the presence of a catalyst containing chromium on a support as described above.Type: GrantFiled: February 2, 1996Date of Patent: November 10, 1998Assignee: Solvay (Societe Anonyme)Inventors: Helmut Derleth, Benoit Koch, Andre Rulmont, Fabienne Wijzen
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Patent number: 5817590Abstract: A catalyst for olefin polymerization is provided which comprises, as the components, a) a metallocene compound, b) an ionizing ionic compound, c) an organoaluminum compound, and d) a Lewis base compound. This catalyst has a stable active species and improves productivity of an olefin polymer without deterioration of the catalytic activity the metallocene is represented by General Formula (1) or (2) where Cp-containing ligands may be Cp, fluorenyl, indenyl or tetrahydroindenyl and where the metal is a group 4 metal of the periodic table.Type: GrantFiled: March 20, 1996Date of Patent: October 6, 1998Assignee: Tosoh CorporationInventors: Saiki Hasegawa, Hisami Yasuda, Akihiro Yano
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Patent number: 5780378Abstract: A solid titanium catalyst component comprising (a) magnesium, (b) titanium, (c) a halogen, (d) a polyether, (e) a hydrocarbon and (f) an electron donor other than the polyether (d) as essential components is provided. Also a process for preparing a solid titanium catalyst component for olefin polymerization, comprising the steps of contacting a halogenated magnesium compound with a compound selected from the group consisting of an alcohol, an ether and an ester in a hydrocarbon solvent to obtain a magnesium compound solution, contacting the magnesium compound solution with a polyether and contacting the resultant solution with a liquid titanium compound is provided. Further, a catalyst for olefin polymerization comprising the above-mentioned solid titanium catalyst component, an organoaluminum compound catalyst component and an electron donor, and a process for polymerizing an olefin using the catalyst for olefin polymerization are also disclosed.Type: GrantFiled: September 6, 1995Date of Patent: July 14, 1998Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Tetsuya Toida, Tetsunori Shinozaki, Mamoru Kioka
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Patent number: 5780379Abstract: Process for the polymerization of alpha-olefins, which is carried out in the presence of a catalyst system comprising:(1) a solid based on completed titanium trichloride;(2) an organometallic compound of metals of groups IA, IIA, IIB and IIIB of the Periodic Table, and(3) an electron-donor organic compound, the solid (1) based on complexed titanium trichloride having been preactivated by being brought into contact with a preactivator comprising the product of reaction of a trialkylaluminum or alkylaluminum chloride compound (a) and of a compound (b) chosen from hydroxyaromatic compounds whose hydroxyl group is sterically hindered, then isolating the predetermined solid (1) from the medium in which it was found.This process enables propylene to be polymerized with an improved stereospecificity without any significant decrease in catalyst activity.Type: GrantFiled: May 13, 1997Date of Patent: July 14, 1998Assignee: Solvay Polyolefins Europe-Belgium (Societe Anonyme)Inventor: Paul Fiasse
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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: 5744415Abstract: A catalyst composition comprising: a) (i) a catalyst containing at least one cycloalkadienyl ligand substituted with at least one electron donor residue and coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals; or (ii) a catalyst containing two cycloalkadienyl ligands coordinated with a metal selected from the group consisting of scandium, yttrium, and lanthanide metals, said cycloalkadienyl ligands connected by a bridging group comprising at least one Group IVA element and at least one electron donor residue; and b) an activating cocatalyst of the formula R.sub.x M', wherein R is alkyl, aryl, or hydride; M' is a Group I, II, or IIIA metal or a Group I, II, or IIIA metal complexed with oxygen, nitrogen, or a halide; and x is equal to the valence of M'.Type: GrantFiled: December 28, 1995Date of Patent: April 28, 1998Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Timothy Todd Wenzel
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Patent number: 5726262Abstract: A solid titanium catalyst component ?Ia! containing magnesium, halogen, titanium and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a catalyst and a prepolymerized olefin-containing catalyst prepared by using the solid titanium catalyst component ?Ia!; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used. A catalyst and a prepolymerized olefin containing catalyst prepared by using a solid titanium catalyst component ?Ib! containing magnesium, halogen, titanium and a specific electron donor (a1), and a compound having at least two ether linkags with a plurality of intermediately existing bonding atoms; a method for preparing a polyolefin wherein said catalyst or prepolymerized olefin containing catayst is used.Type: GrantFiled: December 24, 1996Date of Patent: March 10, 1998Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Tetsunori Shinozaki
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Patent number: 5721183Abstract: Compositions of matter useful as addition polymerization catalysts comprising a Group 4 metal complex and an adduct of tris(organyl)borane compound with a non-tertiary amine or non-tertiary phosphine compound.Type: GrantFiled: March 10, 1995Date of Patent: February 24, 1998Assignee: The Dow Chemical CompanyInventor: David R. Neithamer
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Patent number: 5696213Abstract: This invention is a solution process for the preparation of ethylene-.alpha.-olefin/diolefin copolymers comprising contacting ethylene, one or more .alpha.-olefin monomer, and optionally one or more diene monomer, with a catalyst system containing a catalyst activator and a Group 4 metallocene compound, comprising a) conducting the polymerization reaction at a temperature of about 60.degree. to 150.degree. C.; b) selecting as the Group 4 metallocene compound one or more members of the group consisting of cyclic monocyclopentadienyl Group 4 metal and covalently bridged (bis)indenyl hafnium metallocene compounds; and c) maintaining the .alpha.-olefin concentration at a molar ratio to that of ethylene of between about 0.3 to 7.0 and a diolefin to ethylene molar ratio of between about 0.01 and 0.4. In a preferred embodiment the process comprises: 1) mixing with a reaction solvent the one or more .alpha.Type: GrantFiled: April 21, 1995Date of Patent: December 9, 1997Assignee: Exxon Chemical Patents Inc.Inventors: Rinaldo Soria Schiffino, Javier Mario Zamora
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Patent number: 5596053Abstract: Diene polymers having a high content of trans-1,4 addition and two distinct melting points in the ranges of 30.degree. C. to 50.degree. C. and 70.degree. C. to 130.degree. C. are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated nickel oxy borate compound; (b) an orKanoaluminum compound; (c) a triaryloxy phosphorus compound and (d) a carboxylic acid preferably a fluorinated carboxylic acid. The resultant polymers are useful as additives to tire rubbers to improve processability by reducing compound Mooney viscosity and reducing the shrinkage of various compound stocks.Type: GrantFiled: May 31, 1995Date of Patent: January 21, 1997Assignee: Bridgestone/Firestone, Inc.Inventors: Jung W. Kang, Jason T. Poulton
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Patent number: 5587439Abstract: The present invention is directed to a supported metallocene catalyst useful in the polymerization of .alpha.-olefins which is obtained by tethering a metallocene catalyst component to the surface of a particulate, functionalized copolymeric support material.Type: GrantFiled: May 12, 1995Date of Patent: December 24, 1996Assignee: Quantum Chemical CorporationInventor: Anthony-J. DiMaio
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Patent number: 5547675Abstract: This invention comprises a catalyst system and a process using such catalyst system for the production of high molecular weight polyolefins, particularly polyethylene and higher poly-.alpha.-olefin, and copolymers of ethylene and/or .alpha.-olefins with other unsaturated monomers, including diolefins, acetylenically unsaturated monomers and cyclic olefins. The catalyst system comprises three components, a monocyclopentadienyl Group IV B transition metal compound, an alumoxane, and a modifier. The catalyst system is highly active, at low ratios of aluminum to the Group IV B transition metal, hence catalyzes the production of a polyolefin product containing low levels of catalyst metal residue.Type: GrantFiled: November 30, 1994Date of Patent: August 20, 1996Assignee: Exxon Chemical Patents Inc.Inventor: Jo Ann M. Canich
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Patent number: 5536689Abstract: The invention is concerned with a catalytic composition resulting from dissolving a nickel complex mixed or complexed with a tertiary phosphine in the medium resulting from mixing at least one quaternary ammonium halide and/or at least one quaternary phosphonium halide, at least one aluminum halide, at least one aromatic hydrocarbon and optionally an aluminum organometallic compound. The invention is also concerned with a process for the dimerization, codimerization and oligomerization of olefins with this composition.Type: GrantFiled: September 21, 1994Date of Patent: July 16, 1996Assignee: Institut Francais du PetroleInventors: Yves Chauvin, Sandra Einloft, Helene Olivier
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Patent number: 5512695Abstract: Processes for hydrocyanation of nonconjugated aliphatic monoolefins or monoolefins conjugated to an ester group utilizing a catalyst precursor composition comprising an unsymmetrical bidentate phosphite ligand and zero-valent nickel, preferably in the presence of a Lewis acid promoter, to produce a terminal organonitrile. Catalyst precursor compositions are also disclosed.Type: GrantFiled: March 7, 1995Date of Patent: April 30, 1996Assignee: E. I. Du Pont de Nemours and CompanyInventors: Kristina A. Kreutzer, Wilson Tam
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Patent number: 5510434Abstract: There are disclosed a catalyst for producing an aromatic vinyl compound polymer which catalyst comprises a contact product between an (A) trivalent titanium compound and a (B) compound represented by the general formula (II) or (III)R.sup.1.sub.k M.sup.1 L.sup.2.sub.m (II)R.sup.1.sub.k M.sup.1 X.sup.2.sub.l L.sup.2.sub.m (III)a (C) an ionic compound comprising a noncoordinate anion and a cation, an aluminoxane or an organoboron compound; and optionally a (D) Lewis acid, and a process for producing an aromatic vinyl compound polymer having a high degree of syndiotactic configuration which process comprises polymerizing (a) an aromatic vinyl compound or (b) an aromatic vinyl compound together with an olefin or a diolefin in the presence of the above catalyst.Type: GrantFiled: November 23, 1994Date of Patent: April 23, 1996Assignee: Idemitsu Kosan Co., Ltd.Inventor: Mizutomo Takeuchi
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Patent number: 5508245Abstract: Spherical components of catalysts for the polymerization of olefins comprising:(a) a vanadium compound selected from the compounds of formula VOX.sub.2 Y or VX.sub.n Y.sub.n-4n, where X is Cl or Br and Y is Cl, Br OR or NR.sup.I.sub.2(b) MgCl.sub.2 in spherical form.Said components have an average diameter greater than 1 .mu.m, a surface area of at least 10 m.sup.2 /g, a porosity of at least 0.1 g/cm.sup.3 and an X-ray spectrum having particular characteristics.Type: GrantFiled: November 20, 1992Date of Patent: April 16, 1996Assignees: Montell Technology Company bv, Montell North America Inc.Inventors: Giampiero Morini, Enrico Albizzati, Umberto Giannini, Matteo Nicolini
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Patent number: 5439862Abstract: The present invention relates to a catalyst suitable for oligomerization of olefins which is prepared by a process which comprises reacting a catalyst precursor ligand having a formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is an alkyl, alkoxy, aryl, or aryloxy group having from about 1 to about 20 carbon atoms, with the proviso that R.sub.1 and R.sub.2 are not both aryl, or R.sub.1 and R.sub.2 together form a divalent hydrocarbon moiety, and X is 1,2-arylene, O--CH.sub.2, S--CH.sub.2, or Se--CH.sub.2 with a deprotonation source, a transition metal compound and a catalyst activator. The invention further relates to an oligomerization process utilizing this catalyst.Type: GrantFiled: October 21, 1993Date of Patent: August 8, 1995Inventor: Richard A. Kemp
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Patent number: 5395810Abstract: This invention concerns a making a catalyst system comprising at least one homogeneous catalyst and at least one heterogeneous catalyst, specifically, a metallocene catalyst and a conventional Ziegler-Natta catalyst, respectively. This invention is useful for making a catalyst for the polymerization of any polymer in which separate polymerizations with a homogeneous catalyst and with a heterogeneous catalyst are possible, but preferably, polymerization of olefins, more preferably, .alpha.-olefins, and, most preferably, propylene. This invention provides a catalyst system which facilitates use of a homogeneous catalyst but eliminates the disadvantages of such a system. This invention produces a polymer with molecular weight distribution (MWD) as broad or broader than the MWD of the heterogeneous catalyst alone. Hydrogen can be used to control molecular weight distribution of a polymer produced with this invention.Type: GrantFiled: January 27, 1993Date of Patent: March 7, 1995Assignee: Fina Technology, Inc.Inventors: Edwar S. Shamshoum, Michael J. Elder, Baireddy R. Reddy, David J. Rauscher
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Patent number: 5374597Abstract: Catalysts useful in olefin polymerization are a mixture of (a) (i) one or more compounds Zn(X.sup.1).sub.2 and one or more compounds Al(R.sup.1).sub.3, or (ii) Zn(X.sup.1).sub.2.2Al(R.sup.1).sub.3, wherein X.sup.1 is halide and R.sup.1 is C.sub.1-12 hydrocarbyl; and (b) one or more of V(X.sup.2).sub.c (OR.sup.2).sub.b-c, VO(X.sup.3).sub.d (OR.sup.3).sub.3-d, or VO(X.sup.4).sub.2, wherein X.sup.2, X.sup.3 and X.sup.4 are halogen, R.sup.2 and R.sup.3 are C.sub.1-18 hydrocarbyl, b is 3-4, c is 0-b, and d is 0-3; and can contain (c) one or more of M(R.sup.5).sub.e (X.sup.5).sub.3-e, Al.sub.2 (R.sup.5).sub.3 (X.sup.5).sub.3 or Mg(R.sup.6).sub.f Y.sub.2-f, wherein X.sup.1 and X.sup.2 are halide, R.sup.1, R.sup.5, R.sup.6 and R.sup.9 are C.sub.1- 12 hydrocarbyl, M is Al or B, e is 0-3, Y is halide, O--(C.sub.1-12 hydrocarbyl) or N(SiR.sup.9.sub.3).sub.2, and f is 0-2.Type: GrantFiled: February 12, 1993Date of Patent: December 20, 1994Assignee: Quantum Chemical CorporationInventors: Chi-I Kuo, Michael W. Lynch
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Patent number: 5349034Abstract: A catalyst for production of 1,4-polybutadiene which comprisesas the catalyst component (A) a transition metal compound represented by the formula M(R)l(OR')m X.sub.n-(l+m), wherein M denotes a transition metal atom, R and R' each denote a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and l, m and n denote numerals satisfying the equations l.gtoreq.0, m.gtoreq.0 and n-(l+m).gtoreq.0, n corresponding to the valence of the transition metal,as the catalyst component (B) an organoaluminum compound represented by the formula AlR.sup.1.sub.a X'.sub.3-a, wherein R.sup.1 denotes a hydrocarbon group of 1-20 carbon atoms, X denotes a halogen atom, and a denotes a numeral satisfying the equation 1.ltoreq.a.ltoreq.3, or an aluminoxane obtained by the reaction of said organoaluminum compound with water, andas the catalyst component (C) an organic compound having at least two hydroxyl groups.Type: GrantFiled: July 22, 1993Date of Patent: September 20, 1994Assignee: Sumitomo Chemical Company, LimitedInventors: Masahiro Kakugo, Tatsuya Miyatake, Koozi Mizunuma, Yoshio Yagi, Kazuhiro Watanabe
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Patent number: 5349033Abstract: It is possible to obtain globular polymers in the polymerization of alpha-olefins by means of a highly active, spherical Ziegler catalyst. The polymers have a high bulk density and can be processed very easily.Type: GrantFiled: September 7, 1993Date of Patent: September 20, 1994Assignee: Hoechst AktiengesellschaftInventor: Gerhard Thum
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Patent number: 5324698Abstract: A problem in the conventional olefin polymerization catalyst systems, the procatalysts of which are based on a solid carrier and a titanium compound and an electron donor on its surface, is that unsufficiently high activities are achieved by the morphology of the carrier. Moreover, the active age of such a catalyst in the polymerization is too short. These problems have now been solved by the olefin polymerization catalyst system according to the invention, the procatalyst of which comprises a solid carrier and a layer on its surface consisting of a titanium compound, a magnesium compound and an electron donor. The advantages of the invention become more emphasized when using monocyclopentadienyl titaniumtrichloride as the titanium compound.Type: GrantFiled: September 21, 1992Date of Patent: June 28, 1994Assignee: Neste OyInventors: Sirpa Ala-Huikku, Ulf Palmqvist, Marjaana Lommi, Eero Iiskola
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Patent number: 5320995Abstract: A catalyst for the polymerization of olefins, containing magnesium, chlorine, aluminium and at least one transition metal, in a dispersed or emulsified form within an inert diluent, is obtained by:contacting, in an inert diluent, a magnesium dialkyl and aluminium trichloride, in a molar ratio equal or almost equal to 2/1, at a temperature lower than 105.degree. C. to obtain a catalyst precursor in a suspended form, or at a temperature higher than 105.degree. C. to form a catalyst precursor in the form of a colloidal emulsion, in the diluent used; andcontacting said suspended or emulsified precursor with at least one compound of a transition metal to form a catalyst in the form of a suspension or emulsion respectively.Type: GrantFiled: October 5, 1992Date of Patent: June 14, 1994Assignee: ECP Enichem Polimeri S.r.l.Inventors: Luciano Luciani, Mario Polesello, Federico Milani, Renzo Invernizzi, Giovanni Soverini