Including Heating To Higher Temperature Patents (Class 502/107)
  • Patent number: 5747407
    Abstract: A composition which can be used in, for example, slurry polymerization of an olefin such as, for example, ethylene is produced by a process comprising: (1) combining a first transition metal compound and a metal halide to form a solution; (2) contacting the solution with a precipitating agent to form a solid catalyst intermediate; (3) contacting the solid catalyst intermediate with a second transition metal compound to produce a catalyst composition; and optionally (4) depositing a prepolymer onto the catalyst composition. The precipitating agent comprises a sufficient amount of both a Lewis acid and an ether to effect the precipitation of a solid. Also disclosed is the use of the composition in polymerization of an olefin.
    Type: Grant
    Filed: August 29, 1996
    Date of Patent: May 5, 1998
    Assignee: Phillips Petroleum Company
    Inventor: Joel L. Martin
  • Patent number: 5739226
    Abstract: The solid catalytic component according to the invention is obtained bya) treatment of a catalytic component support with ZrCl.sub.4 or HfCl.sub.4 in the gas phase, followed by ab) treatment with a solution or suspension of a compound capable of grafting a group containing the cycloalkadienyl skeleton to the Zr or Hf contained in the support. Polymerization of olefins in the presence of such a catalytic component results in polymers with low polydispersities, which polymers are obtained with high productivities.
    Type: Grant
    Filed: October 18, 1995
    Date of Patent: April 14, 1998
    Assignee: Elf Atochem S.A.
    Inventors: Roger Spitz, Veronique Pasquet, Jerome Dupuy, Jean Malinge
  • Patent number: 5733979
    Abstract: Catalytic solids based on titanium trichloride complex, usable for the stereospecific polymerisation of alpha-olefins, obtained by heat treatment, in the presence of a halogenated activating agent, of the liquid material resulting from bringing TiCl.sub.4, pretreated with an electron-donor compound, into contact with a composition (C) corresponding to the general formulaAlR.sub.p (Y).sub.q X.sub.3-(p+q)in whichR represents a hydrocarbon radical or a hydrogen atom;Y represents a group chosen from --OR', --SR' and --NR'R", in which R' and R" each represent a hydrocarbon radical or a hydrogen atom;X represents a halogen;p is an arbitrary number such that 0<p<3; andq is an arbitrary number such that 0<q<3;the sum (p+q) being such that 0<(p+q).ltoreq.3.These catalytic solids of controllable porosity permit the production of a wide range of propylene polymers, in particular the propylene and ethylene copolymers known as "block" copolymers.
    Type: Grant
    Filed: February 18, 1993
    Date of Patent: March 31, 1998
    Assignee: Solvay (Societe Anonyme)
    Inventors: Jean-Louis Costa, Sabine Pamart
  • Patent number: 5731451
    Abstract: A process is disclosed for forming an aluminoxane composition comprising methylaluminoxane by mixing trimethylaluminum, or a mixture of trimethylaluminum and one or more other trihydrocarbylaluminum compounds, with an organoaluminum compound containing a trialkylsiloxide moiety and then oxygenating the mixture to form the aluminoxane. Oxygenation can be carried out by controlled hydrolysis or by treatment with an organic compound containing carbon-oxygen bonds, such as carbon dioxide. A preferred trialkylsiloxide moiety is of the formula --OSi(CH.sub.3).sub.3, such as in a compound of the formula (CH.sub.3).sub.2 AlOSi(CH.sub.3).sub.3.
    Type: Grant
    Filed: July 12, 1996
    Date of Patent: March 24, 1998
    Assignee: Akzo Nobel NV
    Inventors: Gregory M. Smith, Dennis B. Malpass, Stanley W. Palmaka
  • Patent number: 5728640
    Abstract: A process for preparing a supported metallocene/aluminoxane solid catalyst comprises preparing a water-in-oil emulsion of water and an inert solvent by using an emulsifier, adding dropwise the emulsion to a solution of an organoaluminium compound in an inert solvent to carry out the reaction to obtain a suspension of the particulate aluminoxane, followed by adding a solution of a metallocene to the above suspension to support the metallocene on the aluminoxane. The solid catalyst thus obtained can be used in the polymerization and copolymerization of olefins. Polymerization can be carried out by slurry polymerization, bulk polymerization, gas phase polymerization, etc.
    Type: Grant
    Filed: July 10, 1996
    Date of Patent: March 17, 1998
    Assignee: China Petrochemical Corp. and Research Institute of Petroleum Processing Sinopec
    Inventors: Bing Lu, Jinmei Wang, Xiaoyu Hong, Zhenhua Jing
  • Patent number: 5710229
    Abstract: The invention relates to a method for preparing polyolefins by polymerizing an olefin with a procatalyst composition prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester. The invention also relates to a polyolefin obtained by polymerizing an olefin in the presence of a procatalyst prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester, as well as to a procatalyst composition suitable for the preparation of a large-pore polyolefin, which composition has been prepared by bringing together MgCl.sub.2, a lower alcohol, a titanium compound and a phthalic acid ester.
    Type: Grant
    Filed: May 1, 1995
    Date of Patent: January 20, 1998
    Assignee: Borealis Holding A/S
    Inventors: Thomas Garoff, Timo Leinonen, Eero Iiskola
  • Patent number: 5670439
    Abstract: 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: Grant
    Filed: January 5, 1996
    Date of Patent: September 23, 1997
    Assignee: Quantum Chemical Corporation
    Inventors: Linda N. Winslow, Raghu K. Menon
  • Patent number: 5663248
    Abstract: Olefin polymerization catalysts the procatalyst component of which comprises a transition-metal compound on a magnesium chloride support material are known to all. Now the procatalyst component has been improved by incorporating a manganese (II) halide into it at a rate of at minimum approx. 0.1% and at maximum approx. 50% of the total molar amount of magnesium chloride and manganese (II) halide. The new polymerization catalyst has, among other things, the excellent special property that it yields a polyolefin with a broad molecular weight distribution.
    Type: Grant
    Filed: June 1, 1994
    Date of Patent: September 2, 1997
    Assignee: Borealis Holding A/S
    Inventors: Thomas Garoff, Timo Leinonen, Eero Iiskola
  • Patent number: 5643849
    Abstract: The present invention relates to novel palladium/bismuth/carbon catalysts which increase selectivity and activity and lower color (i.e., provide greater purity of reaction products when the catalyst is used in the oxidation reaction of an aldose to a salt of aldonic acid).In one embodiment, the invention is concerned with a method of preparing the catalyst. In another embodiment, the invention is concerned with use of the novel catalyst to obtain superior yields (e.g., 97% and greater). In yet another embodiment of the invention, stability of catalyst (i.e., activity over time) is enhanced when using aldehyde during the oxidation of aldose to salt of aldonic acid.
    Type: Grant
    Filed: July 25, 1994
    Date of Patent: July 1, 1997
    Assignee: Lever Brothers Company, Division of Conopco, Inc.
    Inventor: Van Au
  • Patent number: 5631334
    Abstract: Catalytic solid for the (co)polymerisation of at least one olefin, comprising a coprecipitate of magnesium and of at least one transition metal, obtained by means of a process comprising the preparation of a mixture of a magnesium compound, such as the chloride or a magnesium alcoholate, and of a compound denoted by one of the formulae MY.sub.x (O--R').sub.t-x and M'O.sub.y (O--R").sub.s-2y and the treatment of the resulting mixture with a complex of formula M"(A)Al.sub.2 (X',X").sub.8 where X' and X" denote halogens, M and M' transition metals of groups IVB and VB, M" a transition metal of group IVB, A an aromatic hydrocarbon, Y a halogen or a group (O--R'"), and R', R" and R'" an alkyl, aryl or cycloalkyl group.
    Type: Grant
    Filed: March 27, 1995
    Date of Patent: May 20, 1997
    Assignee: Solvay (Soci et e Anonyme)
    Inventor: Nicola Zandona
  • Patent number: 5618770
    Abstract: Magnesium chloride, titanium chloride and at least an electron donor are introduced in a plasma torch. These chlorides being in solution or in suspension in a liquid that can be an electron donor. A very fine granulometry powder is collected after cooling. The powder is very fine, it has a controlled morphology and it can be used as catalyst for alpha-olefins polymerization.
    Type: Grant
    Filed: November 18, 1994
    Date of Patent: April 8, 1997
    Assignee: Fina Research, S.A.
    Inventors: Jean-Pierre Dath, Guy Debras
  • Patent number: 5614456
    Abstract: The interaction of silica, previously calcined at 600.degree. C., with dibutylmagnesium (DBM), 1-butanol and titanium tetrachloride and a solution of methylalumoxane (MAO) and (BuCp).sub.2 ZrCl.sub.2 provides a catalyst that, in the absence of a trialkylaluminum (AlR.sub.3) cocatalyst, produces polyethylene with a bimodal MWD.
    Type: Grant
    Filed: November 3, 1994
    Date of Patent: March 25, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Robert I. Mink, Thomas E. Nowlin, Sandra D. Schregenberger, Pradeep P. Shirodkar, Grace O. Tsien
  • Patent number: 5610114
    Abstract: A supported solid catalyst which can be used for the polymerization and copolymerization of conjugated dienes having as its basis the reaction product of:A) a solid MgCl.sub.2 support,B) an ether, preferably THF, as swelling agent for the support,C) a metal salt selected from among metals having an atomic number of between 57 and 71 or 92 in the periodic table of elements and, if the metal salt is not a halide,D) a halogenation agent selected from the group consisting of a halogenated compound of aluminum and a halogenated compound not containing aluminum, the reaction solid being free from the swelling agent, plusE) an organic derivative of aluminum which is obligatory when the halogenation agent is not a halogenated compound of aluminum and optional when the halogenation agent is a derivative of aluminum.Also, a method of preparing this catalyst.
    Type: Grant
    Filed: August 2, 1995
    Date of Patent: March 11, 1997
    Assignees: Compagnie Generale Des Estab. Michelin-Michelin & Cie, Elf Atochem S.A.
    Inventors: Pierre Robert, Roger Spitz
  • Patent number: 5607655
    Abstract: A generally dipyramidal-shaped catalyst precursor is prepared by dissolving magnesium dichloride and a suitable alcohol in a suitable solvent and then cooling to obtain a precipitate of the desired shape. The use of the precursor to prepare catalysts and the use of the catalysts to prepare polymers is also disclosed.
    Type: Grant
    Filed: March 6, 1995
    Date of Patent: March 4, 1997
    Assignee: Phillips Petroleum Company
    Inventors: Joel L. Martin, Gil R. Hawley
  • Patent number: 5602067
    Abstract: A support containing methylalumoxane and derivatives thereof is described which is formed by an incipient impregnation technique. The most preferred support is silica. Incipient impregnation in accordance with the invention provides a supported alumoxane, methylalumoxane, which substantially eliminates the problem of fluidized bed reactor fouling when methylalumoxane is introduced into the reactor during its operation. In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluidized bed gas phase operation.
    Type: Grant
    Filed: November 3, 1994
    Date of Patent: February 11, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
  • Patent number: 5596069
    Abstract: A cobalt/aluminum catalyst for the polymerization of polyesters of terephthalic acid and an ethylene glycol, and a process for the preparation of such catalysts.
    Type: Grant
    Filed: March 25, 1996
    Date of Patent: January 21, 1997
    Assignee: E. I. Du Pont de Nemours and Company
    Inventor: George R. Goodley
  • Patent number: 5585447
    Abstract: This catalyst has the general formula VX.sub.3, mAIX.sub.3, nZ, wherein X is a halogen atom, Z is at least one at least partially halogenated, branched or unbranched, saturated hydrocarbon, m is between 0.1 and 10, and n is between 1 and 300. To prepare it, a vanadium halide VX.sub.2 and/or VX.sub.3 is coground with an aluminum halide AlX.sub.3, and then at least one halogenated hydrocarbon Z is added to the mixture obtained in proportions corresponding to the chosen values of m and n. The invention also relates to the (co)polymerization of alpha-olefins at 20.degree.-350.degree. C. in the presence of a catalyst system comprising at least one catalyst as defined above and at least one organometallic activator.
    Type: Grant
    Filed: August 14, 1995
    Date of Patent: December 17, 1996
    Assignee: ECP-Enichem Polymeres France S.A.
    Inventors: Emmanuel Adisson, Karel Bujadoux, Michel Fontanille, Alain Deffieux
  • Patent number: 5567665
    Abstract: A process is provided for preparing a shape-shifted catalyst component comprising (1) contacting a dihydrocarbyloxide magnesium compound with carbon dioxide in the presence of a slurrying agent to form a slurry of a carboxylated dihydrocarbyloxide magnesium compound; (2) adding a filler to the slurry either before or after the carboxylation of step (1); (3) spray drying the slurry of step (2) to evaporate the slurrying agent and to produce solid particles of the carboxylated dihydrocarbyloxide magnesium compound incorporating the filler; and, optionally, (4) heating the solid particles to remove carbon dioxide to produce a shape-shifted dihydrocarbyloxide magnesium compound component. A catalyst system using the component and a polymerization process employing the catalyst system are also provided.
    Type: Grant
    Filed: May 23, 1995
    Date of Patent: October 22, 1996
    Assignee: Union Carbide Chemicals & Plastics Technology Corporation
    Inventors: Burkhard E. Wagner, Daniel P. Zilker, Jr., Robert J. Jorgensen
  • Patent number: 5554704
    Abstract: The invention relates to a novel process for producing a supported metallocene catalyst system useful for the polymerization and/or copolymerization of olefins, alpha-olefins, and/or diolefins which results in a catalyst product which during polymerization, produces minimal to no reactor fouling and polymer of controlled morphology. The invention is particularly useful for but not limited to polymerizing propylene or copolymerizing propylene with olefins having two or more carbon atoms. The novel support technique described herein results in a catalyst which will obtain polymer product having controlled, uniform particle size, narrow molecular weight distribution, high bulk density and depending upon the metallocene employed and monomers polymerized, stereoregularity.
    Type: Grant
    Filed: July 1, 1994
    Date of Patent: September 10, 1996
    Assignee: Exxon Chemical Patents, Inc.
    Inventors: Terry J. Burkhardt, Masahide Murata, William B. Brandley
  • Patent number: 5543374
    Abstract: A catalyst composition is prepared by a method comprising impregnating alumina with at least one platinum compound, followed by calcining, reducing treatment, and heating with gaseous aluminum chloride and gaseous titanium tetrachloride. The thus-prepared catalyst composition is employed in the isomerization of saturated C.sub.4 -C.sub.8 hydrocarbons (alkanes and/or cycloalkanes), preferably n-butane.
    Type: Grant
    Filed: November 15, 1994
    Date of Patent: August 6, 1996
    Assignee: Phillips Petroleum Company
    Inventor: An-hsiang Wu
  • Patent number: 5532326
    Abstract: Process for preparing elastomeric copolymers of ethylene with .alpha.-olefins CH.sub.2 .dbd.CHR, optionally containing minor proportions of a diene, characterized by the use during the polymerization of a catalyst comprising the reaction product of:(I) a solid component comprising VCl.sub.3 supported on a magnesium dihalide in spherical or spheroidal shape, in active form;(II) an alkyaluminum compound;(III) optionally a halohydrocarbon.VCl.sub.3 is precipitated on said magnesium dihalide by heating VCl.sub.4 solutions in inert hydrocarbon solvents.
    Type: Grant
    Filed: November 14, 1994
    Date of Patent: July 2, 1996
    Assignee: Montell Technology Company bv
    Inventors: Tiziano Dall'Occo, Floriano Guglielmi, Umberto Zucchini, deceased
  • Patent number: 5496781
    Abstract: In accordance with the present invention, there is provided catalyst systems and processes for preparing such catalyst systems comprising reacting a metallocene compound, a solid organoaluminoxy product, and an organometal compound. Further there is provided processes for the polymerization of olefins using the catalyst systems.
    Type: Grant
    Filed: May 16, 1994
    Date of Patent: March 5, 1996
    Assignee: Phillips Petroleum Company
    Inventors: Rolf L. Geerts, Syriac J. Palackal, Ted M. Pettijohn, Robert M. Infield
  • Patent number: 5492876
    Abstract: A solution process, and a catalyst therefor, for the preparation of high molecular weight polymers of alpha-olefins viz. homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 alpha-olefins, is disclosed. The process is operated under solution polymerization conditions at 105.degree.-320.degree. C. The catalyst is obtained from titanium tetrahalides, vanadium oxytrihalides and organoaluminum compounds, in which an admixture of catalyst components is heat-treated at 180.degree.-250.degree. C. and subsequently cooled to a temperature of less than 150.degree. C. Additional vanadium oxytrihalide is then added. The resultant catalyst solution is activated with an aluminum compound. The catalyst has good activity, showing superior activity to catalysts in which additional vanadium oxytrihalide is not added or added at temperatures above 150.degree. C.
    Type: Grant
    Filed: February 1, 1994
    Date of Patent: February 20, 1996
    Assignee: Novacor Chemicals (International) S.A.
    Inventors: Daniel J. Gillis, Vaclav G. Zboril, Millard C. Hughson
  • Patent number: 5484754
    Abstract: A process for the polymerization of ethylene or the copolymerization of ethylene with an alpha-olefin, in suspension or in gas phase, in the presence of a catalyst consisting essentially of a cocatalyst and a catalytic component based on at least Mg, Ti and Cl, with the catalytic component being constituted of at least one derivative of magnesium and one chlorinated derivative of titanium in its form III and/or IV, which was subjected, prior to its use, to a reduction treatment and then to treatment with a chlorinated transition metal compound, with the said catalytic component being characterized in that the magnesium derivative is in the form MgCl.sub.2.MgO.
    Type: Grant
    Filed: January 21, 1993
    Date of Patent: January 16, 1996
    Assignee: Elf Atochem, S. A.
    Inventors: Roger Spitz, Maryse Patin, Jean Malinge
  • Patent number: 5480848
    Abstract: A catalyst system comprising a transition metal-containing polymerization catalyst and a solid organoaluminoxy product produced by contacting a solution of an organoaluminoxane with an organic borane compound which is free of acidic hydrogen. The use of the catalyst system for the polymerization of olefins is also included.
    Type: Grant
    Filed: May 2, 1994
    Date of Patent: January 2, 1996
    Assignee: Phillips Petroleum Company
    Inventor: Rolf L. Geerts
  • Patent number: 5468698
    Abstract: The invention relates to a method for preparing a particulate carrier for an olefin polymerization procatalyst comprising a complex of an organic compound/transition metal compound as a carrier. In the method a melt MgCl.sub.2 --C.sub.2 H.sub.5 OH-complex is provided containing on average 3.3 to 5.5 C.sub.2 H.sub.5 OH-molecules per each MgCl.sub.2 -molecule, the melt MgCl.sub.2 -complex is sprayed through a nozzle dispersing it into a chamber, wherein a particulate carrier is formed of it and the particulate carrier is removed from the chamber. Unlike prior known methods to produce a carrier having an optimal C.sub.2 H.sub.5 OH content in this invention the removal rate--by the aid of heat--of C.sub.2 H.sub.5 OH from the MgCl.sub.2 --C.sub.2 H.sub.5 OH-complex in connection with the spraying that the particulate carrier is controlled. As a result, the particulate carrier obtained possesses on average 2.0 to 3.2 C.sub.2 H.sub.5 OH molecules per each MgCl.sub.2 molecule. Such a carrier has a suitable C.sub.2 H.
    Type: Grant
    Filed: May 11, 1994
    Date of Patent: November 21, 1995
    Assignee: Borealis Holding A/S
    Inventors: Jukka Koskinen, Thomas Garoff
  • Patent number: 5439662
    Abstract: A process for the manufacture of MgCl.sub.2.MgO with narrow granulometric distribution by treatment of hydrated MgCl.sub.2 with an alcohol followed by heat treatment after partial elimination of the alcohol, characterized in that the hydrated MgCl.sub.2 is suspended in the alcohol, and that the molar ratio of the alcohol to the hydrated MgCl.sub.2 is lower than the solutility ratio of these two substances at the temperature of the suspension. The resultant MgCl.sub.2.MgO can be employed as a support in catalytic components for the polymerization of olefins.
    Type: Grant
    Filed: January 21, 1993
    Date of Patent: August 8, 1995
    Assignee: Elf Atochem S.A.
    Inventors: Roger Spitz, Maryse Patin, Claude Brun
  • Patent number: 5420090
    Abstract: A transition metal containing catalyst useful for the polymerization of .alpha.-olefins is prepared by (A) forming in an inert atmosphere which excludes oxygen and moisture a slurry of (1) a porous inorganic oxide support material selected from the group consisting of silica, alumina, or a combination of silica and alumina, said support material containing not greater than about 5 millimoles of hydroxyl groups per gram of support material and a particle size not greater than about 10 microns and a surface area of from about 50 to about 800 m.sup.2 /g in an inert organic liquid medium; (B) mixing said slurry with (2) an alkoxide and stirring the resultant mixture at a temperature of from about -20.degree. C. to about 120.degree. C. for a time sufficient to saturate the surface of the support material: (C) mixing the product form (B) with (3) a titanium compound or a combination of a titanium compound and (4) a vanadium compound and stirring the resultant mixture at a temperature of from about -20.degree. C.
    Type: Grant
    Filed: February 24, 1993
    Date of Patent: May 30, 1995
    Assignee: The Dow Chemical Company
    Inventors: Lee Spencer, Brian W. S. Kolthammer
  • Patent number: 5413979
    Abstract: The invention relates to a method for the preparation of a solid procatalyst composition for a catalyst system intended for the polymerization of olefins, wherein a magnesium halide, such as magnesium chloride, is dissolved and/or slurried in a mono-carboxylic acid alkyl ester, such as ethyl acetate, is impregnated into a support material, dried, treated with an organometallic compound or a silicon compound and thereafter with a transition metal compound. The invention also relates to such a procatalyst composition and its use together with a cocatalyst for the polymerization of olefins. According to the invention it has been possible to increase the activity of the catalyst composition by using a silanated support material, such as silanated silica, which is then treated with an organometallic or silicon compound before treatment with a transition metal compound. The silanated silica is preferably a silicon dioxide which has been heat-treated at 1000.degree.-200.degree.
    Type: Grant
    Filed: June 16, 1992
    Date of Patent: May 9, 1995
    Assignee: Borealis Holding A/S
    Inventors: Arja Kostiainen, Bill Gustafsson, Pekka Sormunen
  • Patent number: 5401816
    Abstract: A polymerization catalyst system is provided comprising a catalyst and a cocatalyst, wherein the catalyst comprises a chromium compound and a transition metal compound, wherein said chromium compound is a cyclopentadienyl compound, wherein the transition metal compound is a titanium hydrocarbyloxide, and wherein said cocatalyst is an organoaluminum-halide compound. Other aspects of the invention provide a process for preparing the catalyst described above, a polymerization process employing the catalyst, and the polymer produced.
    Type: Grant
    Filed: September 27, 1993
    Date of Patent: March 28, 1995
    Assignee: Phillips Petroleum Company
    Inventors: Henry L. Hsieh, Ted M. Pettijohn
  • Patent number: 5399539
    Abstract: Supported olefin polymerization catalyst systems can be produced using waste chromium compounds. Olefin polymers can be prepared using a catalyst system composition comprising a waste chromium compound and an alkyl aluminum compound, both supported on an inorganic oxide support, wherein at least a portion of the waste chromium compound is in a hexavalent state.
    Type: Grant
    Filed: June 24, 1994
    Date of Patent: March 21, 1995
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn
  • Patent number: 5382557
    Abstract: A solid component of catalyst highly active in the (co)polymerization of ethylene containing titanium, magnesium, aluminum, chlorine and alkoxy groups, and obtained by means of a procedure wherein:(i) a solid, granular support of magnesium chloride, obtained by spray-drying an alcohol solution of magnesium chloride, is suspended in a liquid hydrocarbon solvent and an aliphatic alcohol and a titanium tetraalkoxide are added to the suspension thus obtained,(ii) the suspension of step (i) is heated until a homogeneous solution is obtained and the solution is cooled to precipitate a granular solid in a relative suspension,(iii) the granular solid obtained in step (ii), in the relative suspension, is put in contact and reacted with an aluminum alkyl halide, and(iv) the solid component catalyst is recovered from the reaction products of step (iii).
    Type: Grant
    Filed: July 10, 1992
    Date of Patent: January 17, 1995
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Francesco Masi, Renzo Invernizzi, Angelo Moalli, Cesare Ferrero, Francesco Menconi, Lia Barazzoni
  • Patent number: 5376612
    Abstract: Novel chromium-containing compounds, such as, for example, chromium pyrrolides, are prepared by forming a mixture of a chromium salt, a metal amide, and an electron pair donor solvent, such as, for example, an ether. These novel chromium-containing, or chromium pyrrolide, compounds can be used either unsupported or supported on an inorganic oxide support, with a metal alkyl and an unsaturated hydrocarbon, to trimerize, oligomerize, and/or polymerize olefins.
    Type: Grant
    Filed: August 20, 1993
    Date of Patent: December 27, 1994
    Assignee: Phillips Petroleum Company
    Inventors: William K. Reagen, Ted M. Pettijohn, Jeffrey W. Freeman
  • Patent number: 5371053
    Abstract: A process for deactivating Ziegler-Natta and metallocene catalysts or catalyst systems "such systems are typically used for olefin polymerization". The process includes heating the active catalyst or catalyst system to a temperature sufficient to drive off volatile constituents, and to form complexes and compounds that are non-reactive or less reactive with ambient air than the active catalyst or catalyst system. The process includes steps for safe deactivation including scrubbing to substantially eliminate corrosive compounds, and burning volatile chemicals in a flare.This process essentially eliminates the production of hazardous classification waste from conventional water catalyst deactivation techniques.
    Type: Grant
    Filed: May 18, 1993
    Date of Patent: December 6, 1994
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Agapios K. Agapiou, Steve K. Ackerman, David M. LaBorde, Marc L. DeChellis
  • Patent number: 5352658
    Abstract: A novel Phillips catalyst for the homopolymerization of ethylene and the copolymerization of ethylene with .alpha.-olefins contains, as a catalytically active component, a chromium catalyst supported on a finely divided aluminum silicate gel, modified with a fluoride and activated in an oxidizing atmosphere at elevated temperatures. The finely divided aluminum silicate gel (carrier gel) used here has an alumina content of from 0.5 to 6% by weight, the alumina being concentrated in the surface region of the carrier gel particles. The novel Phillips catalyst has high productivity and gives high molecular weight ethylene homopolymers and copolymers which have excellent low temperature impact strength and do not tend to swell in the blow molding process on emergence from the extruder die.
    Type: Grant
    Filed: February 11, 1993
    Date of Patent: October 4, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Kaspar Evertz, Roland Saive, Guido Funk, Peter Koelle, Rainer Konrad, Hans Gropper
  • Patent number: 5332706
    Abstract: A support containing methylalumoxane and derivatives thereof is described which is formed by an incipient impregnation technique. The most preferred support is silica. Incipient impregnation in accordance with the invention provides a supported alumoxane, methylalumoxane, which substantially eliminates the problem of fluid bed reactor fouling when methylalumoxane is introduced into the reactor during its operation.In accordance with the invention, the process comprises providing methylalumoxane activated metallocene compound in particulate form as catalysts in fluid bed gas phase.
    Type: Grant
    Filed: December 28, 1992
    Date of Patent: July 26, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Thomas E. Nowlin, Frederick Y. Lo, Ronald S. Shinomoto, Pradeep P. Shirodkar
  • Patent number: 5322830
    Abstract: The invention relates to a method for the preparation of a supported procatalyst intended for the polymerization of olefins, in which particles are formed from magnesium halide and alcohol, the particles are reacted with an organometallic compound of any of the metals of the groups I to III, the thus obtained particulate product is activated by means of a titanium(IV) compound, and optionally a prepolymerization is carried out for the activated particles. A problem with this kind of a method is, how to form particles from magnesium dihalide and alcohol having an advantageous structure for the polymerization of ethylene and particularly ethylene with a narrow molecular weight distribution. The problem has in the present invention been solved so that the particles are formed by spray-crystallizing a mixture of magnesium dihalide and alcohol to complex particles of magnesium dihalide and alcohol and that titanium(IV) alcoxyhalide has been used as the titanium compound.
    Type: Grant
    Filed: September 18, 1991
    Date of Patent: June 21, 1994
    Assignee: Neste Oy
    Inventors: Pekka Sormunen, Jukka Koskinen, Paivi Waldvogel
  • Patent number: 5320995
    Abstract: 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: Grant
    Filed: October 5, 1992
    Date of Patent: June 14, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Luciano Luciani, Mario Polesello, Federico Milani, Renzo Invernizzi, Giovanni Soverini
  • Patent number: 5310716
    Abstract: A supported solid component of catalyst, for the stereospecific polymerization of propylene and other .alpha.-olefins, is obtained by making a non-activated silica interact in succession with: (i) a magnesium dialkyl or halide of magnesium alkyl; (ii) a halogenating agent selected from silicon, tin and antimony halides; (iii) a titanium tetrahalide; and (iv) a Lewis base. A catalyst for the stereospecific polymerization of propylene and other .alpha.-olefins is composed of: (A) the solid component of catalyst; (B) an aluminium trialkyl or aluminium alkyl halide; and (C) an electron donor compound, capable of forming a complex compound with component (B).
    Type: Grant
    Filed: July 22, 1992
    Date of Patent: May 10, 1994
    Assignee: ECP Enichem Polimeri S.r.l.
    Inventors: Ludiano Luciani, Federico Milani, Renzo Invernizzi, Italo Borghi, Antonio Labianco
  • Patent number: 5288824
    Abstract: Polymers of propene are prepared using a Ziegler-Natta catalyst system comprising (1) titanium component which is based on a finely divided, shape-imparting silica gel and contains titan- ium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. The process employs a titanium component (1) which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel which has a relatively high moisture content, (Ib) an organomagnesium compound and (Ic) a gaseous chlorinating agent in a manner such that (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then (Ic) is passed into the mixture obtained from (1.1.1), (1.2) then a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid derivative in a manner such that (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the mixture resulting from (1.2.
    Type: Grant
    Filed: August 25, 1992
    Date of Patent: February 22, 1994
    Assignee: BASF Aktiengesellschaft
    Inventors: Juergen Kerth, Rainer Hemmerich, Peter Koelle, Patrik Mueller
  • Patent number: 5284926
    Abstract: An ethylene polymerization catalyst system is provided. This catalyst system is produced by the process comprising forming an activated and reduced composition that is substantially free of titania and that comprises a fluorine compound, a chromium compound, and a catalyst support that consists essentially of silica.An ethylene polymerization process is provided. This process uses the ethylene polymerization catalyst system above. This catalyst system is contacted with ethylene, in the presence of hydrogen and trialkylaluminum, under polymerization conditions, to produce a polyethylene resin.
    Type: Grant
    Filed: September 25, 1992
    Date of Patent: February 8, 1994
    Assignee: Phillips Petroleum Company
    Inventors: Elizabeth A. Benham, Joseph S. Shveima, Max P. McDaniel
  • Patent number: 5275991
    Abstract: A novel catalyst support and a method for preparation thereof, characterized by the presence of selected amounts of a hydrocarbon soluble magnesium-containing compound applied to the support relative to solvent, wherein a surface uniformly and essentially continuously moistened with the solvated magnesium compound in a condition of incipient precipitation to permit the formation of a regular essentially continuous distribution of the magnesium compound onto and conforming to the support material. The drying process under these conditions is effective in maintaining to a high degree the effective surface area and pore volume of the material. The support containing the adsorbed magnesium is then dried in a controlled manner to essential incipient wetness conditions providing a regular spatial distribution of stacked reticular magnesium values at a level of one to five molecular monolayers on the support.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: January 4, 1994
    Assignee: Quantum Chemical Corporation
    Inventors: Charles K. Buehler, Albert P. Masino, Raghu Menon
  • Patent number: 5262372
    Abstract: A process for the production of a highly active olefin polymerization vanadium catalyst, comprising a vanadium compound and an organophosphorous compound combined on a catalyst support, which is capable of producing a broad range of polymer products. The polymer product's molecular weight distribution may be tailored to suit a desired application by controlling the P/V ratio of the catalyst.
    Type: Grant
    Filed: February 3, 1992
    Date of Patent: November 16, 1993
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Gerald D. Malpass, Jr.
  • Patent number: 5260244
    Abstract: A polymerization catalyst system is formed by combining an organometal compound and a transition metal compound to produce a catalyst A; and combining catalyst A and a catalyst B comprising a rare earth complex having a formula Cp.sub.n MX.sub.4-n.M'L.sub.x, wherein Cp is cyclopentadienyl or cyclopentadienyl substituted with an alkyl or alkyl silyl radical, M is yttrium, scandium or a rare earth metal having an atomic number in the range of 57 to 71, M' is an alkali metal, L is a suitable electron donor ligand, X is a halogen, n is 1 or 2, and x is a number corresponding to the value needed to form a stable complex.Optionally catalyst A is contacted with a rare earth metal halide.Optionally catalyst B is contacted with an alkali or alkaline earth metal alkyl.Optionally a hydrocarbyl aluminum compound can be contacted with catalyst B or with the catalyst system.
    Type: Grant
    Filed: October 1, 1992
    Date of Patent: November 9, 1993
    Assignee: Phillips Petroleum Company
    Inventor: Ted M. Pettijohn
  • Patent number: 5258342
    Abstract: A process for the preparation of a solid component of a catalyst active in the (co)polymerization of ethylene and able to form (co)polymers of ethylene having from middle to wide distribution of molecular weight and monomodal distribution of molecular weights, in processes operating in a single step, in suspension or in the gaseous phase. Said solid component of a catalyst contains magnesium, chlorine, silicon, titanium and at least another transition metal on a solid, granular and porous carrier and is obtained by treating the carrier, in succession, with: a compound of a metal selected from hafnium, zirconium or vanadium; a magnesium dialkyl or magnesium alkyl halide; a silicon chloride; and a titanium compound.
    Type: Grant
    Filed: February 26, 1992
    Date of Patent: November 2, 1993
    Assignee: ECP Enichem Polimeri S.R.L.
    Inventors: Luciano Luciani, Federico Milani, Maddalena Pondrelli, Renzo Invernizzi
  • Patent number: 5246900
    Abstract: Olefin polymerization catalysts and processes for preparing and using the catalysts are provided. The catalysts are prepared by forming a particulate gel containing aluminum and magnesium phosphates, calcining the gel and then contacting the calcined gel with a titanium halide and, optionally, an organomagnesium compound.
    Type: Grant
    Filed: August 23, 1991
    Date of Patent: September 21, 1993
    Assignee: Phillips Petroleum Company
    Inventors: Max P. McDaniel, Gil R. Hawley
  • Patent number: 5240894
    Abstract: The invention relates to a novel process for producing a supported metallocene catalyst system useful for the polymerization and/or copolymerization of olefins, alpha-olefins, and/or diolefins which results in a catalyst product which during polymerization, produces minimal to no reactor fouling and polymer of controlled morphology. The invention is particularly useful for but not limited to polymerizing propylene or copolymerizing propylene with olefins having two or more carbon atoms. The novel support technique described herein results in a catalyst which will obtain polymer product having controlled, uniform particle size, narrow molecular weight distribution, high bulk density and depending upon the metallocene employed and monomers polymerized, stereoregularity.
    Type: Grant
    Filed: May 18, 1992
    Date of Patent: August 31, 1993
    Assignee: Exxon Chemical Patents Inc.
    Inventors: Terry J. Burkhardt, Masahide Murata, William B. Brandley
  • Patent number: 5238892
    Abstract: This invention relates to a supported catalyst composition useful in the polymerization of olefins and to a method for its production. The invention particularly relates to the use of undehydrated silica gel containing from about 6 to about 20 percent by weight adsorbed water as the catalyst support material. The catalyst is formed by first reacting a trialkylaluminum compound with a metallocene, and subsequently reacting the resulting material with the undehydrated silica gel. The resulting supported metallocene-alumoxane catalyst has a level of activity comparable to that of conventionally made supported catalysts which are achieved at active metal loadings which are reduced from the loadings used in the previously known metallocene-alumoxane catalysts by at least 20%, and preferably 50%.
    Type: Grant
    Filed: June 15, 1992
    Date of Patent: August 24, 1993
    Assignee: Exxon Chemical Patents Inc.
    Inventor: Main Chang
  • Patent number: 5235011
    Abstract: A process for preparing a polymerization catalyst useful for the polymerization of olefins is provided comprising contacting a metal dihalide compound wherein the metal is selected from Group 2 and Group 12 of the Periodic Table and a transition metal compound which is a hydrocarbyloxide of a transition metal selected from Group 4 and Group 5 to form a first catalyst component; contacting the first catalyst component with at least one organoaluminum precipitating agent, wherein at least at the commencement of this step, the temperature at which such contacting is carried out is greater than about 70.degree. C. to about 150.degree. C. to form a solid product, and contacting the solid product with an activating agent to form a catalyst. Other aspects of the invention provide a catalyst prepared by the above described method and a polymerization process employing the thus prepared catalyst.
    Type: Grant
    Filed: August 31, 1992
    Date of Patent: August 10, 1993
    Assignee: Phillips Petroleum Company
    Inventors: Kent E. Mitchell, David C. Miller, Don W. Godbehere, Gil R. Hawley
  • Patent number: 5234879
    Abstract: When asymmetric olefins or a monomer mixture containing asymmetric monomers is polymerized by a catalyst composition containing esters of carboxylic acid e.g. as a so-called donor, and alcohol the ester group can be transesterified with the alcohol to an ester containing another alkyl group during the preparation and/or polymerization of the catalyst. This is advantageous particularly when an adduct of a so-called spray-crystallized Mg-halide and alcohol is used as the catalyst carrier, because the alkoxy group of the alcohol of the carrier and the alkoxy group of the ester of the donor can be transesterified and thus obtain the preferable effects of both esters on the run of the polymerization reaction. Hereby, a solvent having a high boiling point should be used as the intermediate agent, so that the transesterification reaction can take place. Most preferable have been found hydrocarbons having high boiling points, especially nonane and decane.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: August 10, 1993
    Assignee: Neste OY
    Inventors: Thomas Garoff, Timo Leinonen, Eero Iiskola