At Least One Group Ivb Metal Atom (ti, Zr, Hf) And At Least One Group Vb Meta L (v, Nb, Ta) Patents (Class 526/116)
  • Patent number: 4981928
    Abstract: A catalyst component useful for (co)polymerizing ethylene under high temperatures and pressures comprising the reaction product obtained by treating a magnesium halide supported titanium halide precursor with Lewis acid, thoroughly washing the solid reaction product therefrom and prepolymerizing the washed solid product with an alpha-olefin having from 4-12 carbon atoms.
    Type: Grant
    Filed: October 20, 1988
    Date of Patent: January 1, 1991
    Assignee: Exxon Research and Engineering Company
    Inventor: Agapios K. Agapiou
  • Patent number: 4972033
    Abstract: There is disclosed a catalyst composition for the polymerization of olefins, particularly alpha-olefins. The composition is prepared by synthesizing a catalyst precursor and then combining it with a conventional catalyst activator. The precursor is synthesized by: (a) contacting a solid, porous carrier with an aluminum compound; (b) contacting the resulting product with a mixture of vanadium and titanium compounds; (c) contacting the product with an alkyl ether and, (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound.The catalyst composition is used without a halogenating agent in the polymerization medium to produce narrow molecular weight distribution HDPE and LLDPE products, or with a halogenating agent in the polymerization medium to produce broad molecular weight distribution LLDPE and HDPE products.
    Type: Grant
    Filed: February 10, 1989
    Date of Patent: November 20, 1990
    Assignee: Mobil Oil Corporation
    Inventor: Nemesio D. Miro
  • Patent number: 4939217
    Abstract: A process for producing a polyolefin having a multimodal molecular weight distribution wherein the polymerization is conducted in the presence of hydrogen and a catalyst system containing aluminoxane and at least two different metallocenes each having different olefin polymerization termination rate constants in the presence of hydrogen, and the process of producing the catalyst system.
    Type: Grant
    Filed: April 3, 1987
    Date of Patent: July 3, 1990
    Assignee: Phillips Petroleum Company
    Inventor: Phil M. Stricklen
  • Patent number: 4937299
    Abstract: Polyolefin reactor blends obtained by polymerization of ethylene and higher alpha-olefins in the presence of a catalyst system comprising two or more metallocenes and alumoxane.
    Type: Grant
    Filed: February 1, 1985
    Date of Patent: June 26, 1990
    Assignee: Exxon Research & Engineering Company
    Inventors: John A. Ewen, Howard C. Welborn, Jr.
  • Patent number: 4935474
    Abstract: Polyolefins having a broad molecular weight distribution are obtained by polymerizing ethylene or higher alpha-olefins in the presence of a catalyst system comprising two or more metallocenes each having different propagation and termination rate constants and alumoxane.
    Type: Grant
    Filed: April 26, 1985
    Date of Patent: June 19, 1990
    Assignee: Exxon Research & Engineering Company
    Inventors: John A. Ewen, Howard C. Welborn, Jr.
  • Patent number: 4918038
    Abstract: A process for the production of an ethylene homopolymer or copolymer comprising passing ethylene with or without at least one alpha-olefin comonomer having 3 or more carbon atoms into contact with a mixed catalyst system, under polymerization conditions, said mixed catalyst system comprising:(a) the reaction product of (i) a vanadium halide having the formula VX.sub.3 wherein X is chlorine, bromine, or iodine and each X is alike or different; (ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a and (iii) an electron donor(b) one of the following:(i) a complex having the formula ZrMg.sub.b X.sub.c (ED).sub.d ; or(ii) a vanadium oxy compound having the formula VOX.sub.3, VOX.sub.2, VOX, or VO.sub.2 X wherein X is as defined above, or VO(OR).sub.3(c) a hydrocarbyl aluminum cocatalyst; and(d) a halocarbon promoter having the formula R.sub.e CX.sub.
    Type: Grant
    Filed: October 29, 1987
    Date of Patent: April 17, 1990
    Assignee: Union Carbide Chemicals and Plastics Company Inc.
    Inventors: Sari-Beth Samuels, Frederick J. Karol
  • Patent number: 4918039
    Abstract: A metathesis polymerization catalyst composition comprising a binuclear catalyst, wherein said binuclear catalyst is a mixture of at least two transition metal components, wherein a first transition metal component is a halide complex of tungsten, an oxyhalide complex of tungsten or a mixture thereof and a second transition metal component is a halide complex of a transition metal selected from the group consisting of high valent transition metals belonging to Groups IV or V of the Periodic Table, from about 1 to about 3 moles of phenolic compound per mole of tungsten component, activated by a metathesis catalyst activator and containing a rate moderator.
    Type: Grant
    Filed: September 21, 1988
    Date of Patent: April 17, 1990
    Assignee: Hercules Incorporated
    Inventor: Andrea E. Martin
  • Patent number: 4912074
    Abstract: There is disclosed a catalyst composition for the polymerization of olefins, particularly alpha-olefins. The composition is prepared by synthesizing a catalyst precursor and then combining it with a conventional catalyst activator. The precursor is synthesized by: (a) contacting a solid, porous carrier with an aluminum compound; (b) contacting the resulting product with a mixture of vanadium and titanium compounds; and, (c) contacting the product with an ether.The catalyst composition is used with a conventional activator and, preferably, a halogenating agent in the polymerization medium to produce broad molecular weight distribution, high molecular weight HDPE or medium density, broad molecular weight distribution, high molecular weight resins which can be made into high strength films.
    Type: Grant
    Filed: October 5, 1988
    Date of Patent: March 27, 1990
    Assignee: Mobil Oil Corporation
    Inventor: Nemesio D. Miro
  • Patent number: 4866021
    Abstract: Broad molecular weight distribution, and high molecular weight olefin polymers, are prepared by polymerizing at least one olefin in the presence of a vanadium - and a titanium-containing catalyst composition. A catalyst precursor is synthesized by contacting a solid, porous carrier sequentially with a metal or a compound of a metal of Group IIB of the Periodic Chart of the Elements, e.g., a zinc compound, a halogen-containing aluminum compound, a vanadium compound and a titanium compound. The precursor is then combined with a suitable co-catalyst and a halogenating agent to produce the catalyst composition used to polymerize olefins.
    Type: Grant
    Filed: January 15, 1988
    Date of Patent: September 12, 1989
    Assignee: Mobil Oil Corp.
    Inventors: Nemesio D. Miro, Thomas E. Nowlin
  • Patent number: 4864005
    Abstract: A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by polymerization of the monomer or monomers using a Ziegler catalyst system comprising (1) a transition metal catalyst component and (2) an organoaluminum catalyst component, in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first bringing (1.1.1) a finely divided, porous, inorganic oxidic substance (I) as the carrier, and (1.1.2) a solution (II), as obtained on combining (IIa) an alcohol and (IIb) a transition metal composition, into contact with one another to form a suspension (III), evaporating this suspension to dryness (formation of a solid-phase intermediate (IV)) and (1.2) then (1.2.1) bringing the solid-phase intermediate (IV) obtained from stage (1.1), and (1.2.
    Type: Grant
    Filed: November 3, 1983
    Date of Patent: September 5, 1989
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Warzelhan, Wolfgang Ball, Robert Bachl
  • Patent number: 4831090
    Abstract: Homopolymerization and copolymerization of ethene are carried out using a Ziegler catalyst system consisting of (1) a transition metal catalyst component prepared by a method in which (1.1) first (1.1.1) an inorganic oxide substance (I) as a carrier and (1.1.2) a solution (II) of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if desired, (IIb3) a zirconium tetrahalide, are combined with formation of a suspension (III), the latter is evaporated down to form a solid-phase intermediate (IV), (1.2) then (1.2.1) the solid-phase intermediate (IV) obtained from (1.1), and (1.2.2) a dissolved organoaluminum compound (V), are combined with formation of a suspension, the resulting suspended substance being a solid-phase product (VI), (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component.
    Type: Grant
    Filed: October 15, 1987
    Date of Patent: May 16, 1989
    Assignee: BASF Aktiengesellschaft
    Inventors: Robert Bachl, Guido Funk, Konrad Richter, Rainer Hemmerich, Roland Saive
  • Patent number: 4831000
    Abstract: There is disclosed a catalyst composition for the polymerization of olefins, particularly alpha-olefins. The composition is prepared by synthesizing a catalyst precursor and then combining it with a conventional catalyst activator. The precursor is synthesized by: (a) contacting a solid, porous carrier with an aluminum compound; (b) contacting the resulting product with a mixture of vanadium and titanium compounds; (c) contacting the product with an ether; and, (d) pre-activating the product of step (c) with a mixture of a halogenating agent and an aluminum compound.The catalyst composition is used without a halogenating agent in the polymerization medium to produce narrow molecular weight distribution HDPE and LLDPE products, or with a halogenating agent in the polymerization medium to produce broad molecular weight distribution LLDPE and HDPE products.
    Type: Grant
    Filed: January 15, 1988
    Date of Patent: May 16, 1989
    Assignee: Mobil Oil Corporatiion
    Inventor: Nemesio D. Miro
  • Patent number: 4822763
    Abstract: A catalyst component for polymerization of olefin, comprising a contact product of a component (A) which is a solid component containing titanium having at least one OR.sup.1 group (where R.sup.1 represents a hydrocarbon residue) and magnesium and a halogen as the essential components; a component (B) which is an acid halide compound; a component (C) which is a compound having an OR.sup.2 group (where R.sup.2 represents a hydrocarbon residue or hydrogen atom); and a component (D) which is a halide compound of silicon. When an olefin is polymerized by use of this as the transition metal component of a Ziegler type catalyst, an olefin polymer with high activity and high I.I and excellent polymer properties can be obtained.
    Type: Grant
    Filed: June 18, 1987
    Date of Patent: April 18, 1989
    Assignee: Mitsubishi Petrochemical Company Limited
    Inventors: Mitsuyuki Matsuura, Takashi Fujita
  • Patent number: 4774300
    Abstract: A method of producing a polymerization catalyst component suitable for use in the polymerization of alpha-olefins, which method comprises forming an active component by co-comminuting an inorganic Lewis acid, a first organic electron donor, a support base selected from the group consisting of the Group IIA & IIIA salts and the salts of the multivalent metals of the first transition series with the exception of copper, and a polymerization active tri-, tetra-, or penta- valent transition metal compound of a Group IVB-VIB metal, and heating the active component in an inert hydrocarbon solvent to produce the polymerization catalyst component. The active component can be heated in the inert hydrocarbon solvent in the presence of an additional polymerization active tri-, tetra-, or penta- valent transition metal compound of a group IVB-VIB metal. In addition, a second organic electron donor may be incorporated in the active component.
    Type: Grant
    Filed: October 17, 1985
    Date of Patent: September 27, 1988
    Assignee: Phillips Petroleum Company
    Inventors: Agapios Agapiou, Felix I. Jacobson, John L. H. Allan
  • Patent number: 4769428
    Abstract: A solution process, and a catalyst therefor, for the preparation of high molecular weight polymers of alph-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.. The catalyst is obtained from titanium tetrahalides, vanadium oxytrihalides and organoaluminum compounds, in which an admixture of catalyst components is heat-treated at 150.degree.-320.degree. C., and activated with an aluminoxane. The catalyst has good activity and the polymer obtained has improved color.
    Type: Grant
    Filed: October 16, 1986
    Date of Patent: September 6, 1988
    Assignee: Du Pont Canada Inc.
    Inventors: Vaclav G. Zboril, Rolf Mulhaupt
  • Patent number: 4739022
    Abstract: The process for (co)polymerization comprises polymerizing ethylene and optionally minor amounts of 1-alkenes and/or dienes at a temperature greater than 180.degree. C. in the presence of a catalyst system prepared by combining at least two components, A and B, which components comprise:A: one or more titanium compounds and one or more vanadium compounds, mixed with one or more organoaluminum compounds in such an amount that the atomic ratio of aluminum to the sum of titanium and vanadium is at least 3,B: one or more organoaluminum compounds,wherein one or both components A and b contain a chloride, and wherein the two components are fed, separately or in combination, direct to the reaction vessel in such an amount that the atomic ratio of the chlorine from components A and/or B to the sum of titanium and vanadium of component A is at least 6.
    Type: Grant
    Filed: December 10, 1986
    Date of Patent: April 19, 1988
    Assignee: Stamicarbon B.V.
    Inventors: Johannes Blenkers, Luc M. C. Coosemans
  • Patent number: 4710552
    Abstract: Homopolymers and copolymers of ethene are prepared using a Ziegler catalyst system comprising (1) a transition metal catalyst component, (2) an organoaluminum catalyst component and (3) an organohalogen catalyst component, by a method in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first combining (1.1.1) an inorganic oxidic substrate (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide or titanium trihalide/alcohol complex and, if required, (IIb3) a zirconium tetrahalide to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) combining the solid-phase intermediate (IV) obtained from (1.1) with (1.2.
    Type: Grant
    Filed: June 18, 1986
    Date of Patent: December 1, 1987
    Assignee: BASF Aktiengesellschaft
    Inventors: Robert Bachl, Volker Warzelhan, Guenther Schweier, Hans Gropper, Wolfgang Ball
  • Patent number: 4705835
    Abstract: .alpha.-Monoolefins are polymerized using a Ziegler catalyst system comprising (1) a transition metal catalyst component and (2) an organoaluminum catalyst component, in which (1) is a solid-phase product (VI) obtained by (1.1) first combining (1.1.1) an inorganic oxidic substance (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) an organic solvent and (IIb) a transition metal composition to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV), and (1.2) then (1.2.1) combining the solid-phase intermediate (IV), obtained from (1.1), with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase product (VI) being the transition metal catalyst component (1).
    Type: Grant
    Filed: June 18, 1986
    Date of Patent: November 10, 1987
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Warzelhan, Robert Bachl, Wolfgang Ball, Guido Funk, Martin Laun
  • Patent number: 4704376
    Abstract: A catalyst system is disclosed as a combination of at least two components comprising: component A which is one or more titanium compounds and one or more vanadium compounds mixed with one or more organoaluminum compounds in such in amount that the atomic ratio of aluminum to the sum of titanium and vanadium is at least 3; and component B which comprises one or more organoaluminum compounds,wherein one or both of components A and B contain a chloride, and wherein during use such two components are fed, separately or in combination, directly to the reaction vessel in such an amount that the atomic ratio of the chlorine from components A and/or B to the sum of titatium and vanadium of component A is at least 6. The catalyst system is suitable for copolymerizing ethylene and optionally minor amounts of 1-alkenes and/or dienes at high polymerization temperatures.
    Type: Grant
    Filed: April 11, 1986
    Date of Patent: November 3, 1987
    Assignee: Stamicarbon B.V.
    Inventors: Johannes Blenkers, Luc M. C. Coosemans
  • Patent number: 4680351
    Abstract: A highly active catalyst suitable for the polymerization of olefins and its use are disclosed, said catalyst being prepared by(1) co-comminuting an aluminum halide; at least one electron donor; a Group IVB-VIB transition metal compound; and a support base selected from the group consisting of the Group IIA and IIIA salts and the salts of the multivalent metals of the first transition series with the exception of copper to produce a coground solid;(2) extracting said coground solid with an organic liquid; and(3) separating the solid from the liquid under such conditions that at least 5 weight percent of the aluminum in the coground solid is removed.
    Type: Grant
    Filed: October 10, 1986
    Date of Patent: July 14, 1987
    Assignee: Phillips Petroleum Company
    Inventors: Nemesio D. Miro, Floyd E. Farha, Charles E. Capshew
  • Patent number: 4672096
    Abstract: A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with an organomagnesium composition and contacting the thus-formed magnesium-containing carrier with a solution of at least one tetravalent vanadium compound. Alternatively, the solution may also contain at least one tetravalent titanium compound in addition to the vanadium compound, thereby producing catalysts containing both, vanadium and titanium. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalysts of the invention.
    Type: Grant
    Filed: October 16, 1985
    Date of Patent: June 9, 1987
    Assignee: Mobil Oil Corporation
    Inventor: Thomas E. Nowlin
  • Patent number: 4663403
    Abstract: A first reactant selected from arylsilanol, hydrocarbyl amine, hydrocarbylphosphine oxide, and hydrocarbyloxyphosphite is combined with a second reactant selected from halogenated transition metal compound and an organometal compound to form a product which is catalytically active for olefin polymerization after optionally first having been deposited on a particulate diluent.
    Type: Grant
    Filed: September 19, 1984
    Date of Patent: May 5, 1987
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4659685
    Abstract: Catalyst compositions are disclosed which are a combination of a supported titanium compound such as titanium tetraisopropoxide supported on magnesium dichloride and at least one other supported metallic catalyst such as dicyclopentadienyl zirconium dichloride supported on alumina and a cocatalyst such as aluminoxane. These catalysts are useful in the polymerization of .alpha.-olefins.
    Type: Grant
    Filed: March 17, 1986
    Date of Patent: April 21, 1987
    Assignee: The Dow Chemical Company
    Inventors: William M. Coleman, III, Gregory F. Schmidt, Richard E. Campbell, Jr., Mark S. Delaney
  • Patent number: 4656151
    Abstract: An intermetallic compound is disclosed formed by(a) mixing a compound having the structural formula R(R')Mg where R and R' are the same or different and are hydrocarbyl of 1 to 10 carbon atoms with a compound having the structural formula R.sup.1.sub.m Si(OR.sup.2).sub.n X.sub.4-(m+n) where R.sup.1 and R.sup.
    Type: Grant
    Filed: July 15, 1985
    Date of Patent: April 7, 1987
    Assignee: National Distillers and Chemical Corporation
    Inventors: Javan Shelly, Louis J. Rekers
  • Patent number: 4618595
    Abstract: A catalyst, a process of forming the catalyst, and polymerizing at least one alpha-olefin with the catalyst, said catalyst produced by precipitating a composition from a solution of a metal halide, for example, magnesium dihalide, and a transition metal compound, for example, titanium tetraalkoxide, in the presence of a particulate diluent, for example, polymeric fibrils, with an agent selected from among specified organometallic compounds, metal halides and oxygen-containing metal halides, hydrogen halides and organic acid halides. The composition is preferably further treated with a halide ion exchanging source, for example, titanium tetrahalide to form a particularly active catalyst. The catalyst is preferably used in combination with a cocatalyst comprising a metal hydride or organometallic compound selected from an element of Periodic Groups IA, IIA and IIIA.
    Type: Grant
    Filed: June 5, 1985
    Date of Patent: October 21, 1986
    Assignee: Phillips Petrolem Company
    Inventor: Richard E. Dietz
  • Patent number: 4612300
    Abstract: Polymers of .alpha.-olefins having a relatively narrow molecular weight distribution are prepared by employing a Ziegler-Natta magnesium halide supported catalyst containing both titanium and vanadium.
    Type: Grant
    Filed: June 6, 1985
    Date of Patent: September 16, 1986
    Assignee: The Dow Chemical Company
    Inventor: William M. Coleman, III
  • Patent number: 4603183
    Abstract: A method is provided for preparing hydrocarbon soluble magnesium siloxide supports comprising contacting such supports with sufficient aluminum alkoxide or organic ethers to render the supports hydrocarbon soluble. Thereafter the supports are contacted with a transition metal compound and halogenated to obtain polymerization catalysts.
    Type: Grant
    Filed: December 24, 1984
    Date of Patent: July 29, 1986
    Assignee: E. I. Du Pont de Nemours & Co.
    Inventor: Donald E. Gessell
  • Patent number: 4603184
    Abstract: A process for producing .alpha.-olefin polymers is proposed wherein the catalyst prepared and used therein is superior in the shelf stability and heat stability. The process comprises reacting TiCl.sub.4 with a reaction product (I) of an organoaluminum compound with an electron donor to obtain a solid product (II), which is then subjected to polymerization treatment with an .alpha.-olefin, and further reacted with an electron donor and an electron acceptor to obtain a solid product (III), which is then combined with an organoaluminum compound, to obtain a catalyst, in the presence of which .alpha.-olefin(s) are polymerized. The catalyst can be further preactivated with an .alpha.-olefin in advance of its use for the polymerization.
    Type: Grant
    Filed: April 29, 1983
    Date of Patent: July 29, 1986
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Toshihiro Uwai, Masami Tachibana, Kenji Matsuda, Yoshiharu Higuchi
  • Patent number: 4593009
    Abstract: A catalyst composition for polymerizing alpha-olefins is prepared by treating a carrier containing OH groups with an organomagnesium composition and contacting the thus-formed magnesium-containing carrier with a solution of at least one tetravalent vanadium compound. Alternatively, the solution may also contain at least one tetravalent titanium compound in addition to the vanadium compound, thereby producing catalysts containing both, vanadium and titanium. Also disclosed is a process for polymerizing alpha-olefins in the presence of the catalysts of the invention.
    Type: Grant
    Filed: April 4, 1984
    Date of Patent: June 3, 1986
    Assignee: Mobil Oil Corporation
    Inventor: Thomas E. Nowlin
  • Patent number: 4568659
    Abstract: A transition metal catalyst component (1) for Ziegler catalyst systems is prepared by (1.1) first combining (1.1.1) an inorganic oxidic substance (I), as the carrier, with (1.1.2) a solution (II) consisting of (IIa) an organic solvent and (IIb) a transition metal composition to form a suspension (III), evaporating down this suspension to form a solid-phase intermediate (IV) and (1.2) then combining (1.2.1) the solid-phase intermediate (IV) obtained from (1.1) with (1.2.2) a solution of an organoaluminum compound (V) to form a suspension, the resulting suspended solid-phase products (VI) being the transition metal catalyst component (1).The characteristic feature is that the solution (II) employed in stage (1.1) consists of (IIa) a certain oxahydrocarbon and (IIb) a mixture of (IIb1) a vanadium trichloride/alcohol complex, (IIb2) a titanium trihalide and (IIb3) a zirconium tetrahalide.
    Type: Grant
    Filed: October 30, 1984
    Date of Patent: February 4, 1986
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Warzelhan, Rainer Karer, Robert Bachl, Guido Funk
  • Patent number: 4550094
    Abstract: A solid catalyst component for olefin polymerization comprising a hydrocarbon-insoluble product(III) obtained by reacting(A) a silicon compound selected from the group consisting of(1) silicon compounds represented by the general formula R.sup.1.sub.a R.sup.2.sub.b R.sup.3.sub.c Si, wherein R.sup.1, R.sup.2 and R.sup.3 are each an alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, or hydroxyl group or a halogen or hydrogen atom; and a, b and c are numbers defined by the formulas 0.ltoreq.a,b,c,.ltoreq.
    Type: Grant
    Filed: February 9, 1983
    Date of Patent: October 29, 1985
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Katsumi Hanji, Kiyoshi Kawai
  • Patent number: 4537869
    Abstract: A supported vanadium catalyst is provided by impregnating a vanadium compound onto a refractory support, subjecting the resulting support to calcination and thereafter contacting with a titanium component such as titanium tetrachloride. The resulting catalyst is used with a trihydrocarbylaluminum cocatalyst such as triethylaluminum and results in a supported vanadium catalyst having high activity which catalyst is sensitive to molecular weight control agents such as hydrogen.
    Type: Grant
    Filed: November 19, 1984
    Date of Patent: August 27, 1985
    Assignee: Phillips Petroleum Company
    Inventor: Max P. McDaniel
  • Patent number: 4533705
    Abstract: A process for producing .alpha.-olefin polymers having high crystallinity and good particle form, with a high yield is provided. The polymerization therefor is carried out in the presence of a preactivated catalyst suitable particularly to gas phase polymerization or gas phase polymerization following slurry or bulk polymerization.The catalyst is prepared by reacting a reduction solid prepared by reducing TiCl.sub.4 with an organoaluminum compound, with an electron donor and an electron acceptor to obtain a solid product, andcombining this solid product with an organoaluminum compound, an .alpha.-olefin and a reaction product of an organoaluminum compound with an electron donor.
    Type: Grant
    Filed: July 21, 1983
    Date of Patent: August 6, 1985
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Kazutsune Kikuta, Toshihiro Uwai, Kenji Matsuda, Nobutaka Hattori
  • Patent number: 4525468
    Abstract: High activity catalysts for the polymerization of ethylene and other .alpha.-olefins are made by contacting a soluble magnesium compound of the general formula Mg(OSiR.sup.1 R.sup.2 R.sup.3).sub.2, wherein each of R.sup.1, R.sup.2, and R.sup.3 is, independently, alkyl, alkoxy or aryl with a metal alkoxide, or a mixture of a titanium tetraalkoxide with an alkoxide of another transition metal, in a saturated aliphatic hydrocarbon solution, followed by chlorination and precipitation by a suitable chlorinating agent. These catalysts show high activity for the polymerization of ethylene, especially under slurry polymerization conditions.
    Type: Grant
    Filed: April 28, 1983
    Date of Patent: June 25, 1985
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: Mark P. Mack, Mark L. Shannon
  • Patent number: 4525550
    Abstract: A process for the preparation of homopolymers and copolymers of .alpha.-monoolefins by polymerization of the monomer or monomers using a Ziegler catalyst system comprising (1) a transition metal catalyst component and (2) an organoaluminum catalyst component, in which the transition metal catalyst component (1) employed is a solid-phase product (VI) obtained by (1.1) first bringing (1.1.1) a finely divided, porous, inorganic oxidic substance (I) as the carrier, and (1.1.2) a solution (II), as obtained on combining (IIa) an alcohol and (IIb) a transition metal composition, into contact with one another to form a suspension (III), evaporating this suspension to dryness (formation of a solid-phase intermediate (IV) and (1.2) then (1.2.1) bringing the solid-phase intermediate (IV) obtained from stage (1.1), and (1.2.
    Type: Grant
    Filed: November 3, 1983
    Date of Patent: June 25, 1985
    Assignee: BASF Aktiengesellschaft
    Inventors: Volker Warzelhan, Wolfgang Ball
  • Patent number: 4525552
    Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of a catalyst system comprising the combination of at least one organometallic compound with a transition metal compound supported on a solid carrier, said solid carrier being obtained by the reaction of (a) a magnesium halide, (b) a compound represented by the formula: Al(OR).sub.n X.sub.3-n, where R is a hydrocarbon residual group having 1 to 24 carbon atoms, X is a hydrogen atom, and n is 0<n.ltoreq.3, and (c) a compound represented by the formula: Si(OR').sub.m X.sub.4-m, where R' is a hydrocarbon residual group having 1 to 20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4. The resulting polymers are characterized by a large bulk density and a narrow range of molecular weight distribution.
    Type: Grant
    Filed: February 8, 1984
    Date of Patent: June 25, 1985
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mitsuji Miyoshi
  • Patent number: 4525551
    Abstract: This invention relates to a novel highly active and more efficient catalyst system for polymerizing alpha-olefins to prepare high, medium, and low molecular weight polymers. This highly active olefin polymerization catalyst therefore can be used to prepare both olefin waxes as well as high molecular weight crystalline polyolefins. This highly efficient, highly active catalyst is prepared by reacting a vanadium tetrahalide with a titanium tetravalent member in a hydrocarbon medium. The product of this reaction is then combined with an activating component, such as triethyl aluminum, to form a highly active and efficient polyolefin catalyst.
    Type: Grant
    Filed: December 2, 1983
    Date of Patent: June 25, 1985
    Assignee: Eastman Kodak Company
    Inventor: Robert R. Schmidt
  • Patent number: 4518752
    Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of an improved catalyst comprising a solid catalyst component and an organometal compound, said solid catalyst component being obtained by the reaction of: (a) a magnesium halide, (b) a compound represented by the formula: Me(OR).sub.n X.sub.z-n where Me is any of the Group I-VIII elements of the Periodic Table, excluding Al, Si, Ti and V, R is a hydrocarbon residual group having 1-24 carbon atoms, X is a halogen atom, z represents the valence of Me and n is 0<n.ltoreq.z, and (c) a compound represented by the formula: Si(OR').sub.m X.sub.4-m where R' is a hydrocarbon residual group having 1-20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4, and (d) a titanium compound and/or a vanadium compound. The resulting polymers are characterized by a large bulk density, a narrow range of molecular weight distribution, and small amounts of hexane extraction.
    Type: Grant
    Filed: November 15, 1983
    Date of Patent: May 21, 1985
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura
  • Patent number: 4499247
    Abstract: A superior high-rigidity and high-melt-viscoelasticity polypropylene for sheets to be post-processed and for blow molding is provided which polypropylene is produced by subjecting propylene to a multi-stage polymerization into polymer portions of two sections in the presence of a specified Ziegler Natta catalyst, the relationship between the intrinsic viscosities of the polymer portions of the respective sections being regulated within a specified range and also the amount ratio of the polymer portions of the respective sections being regulated.
    Type: Grant
    Filed: June 7, 1983
    Date of Patent: February 12, 1985
    Assignee: Chisso Corporation
    Inventors: Hiromasa Chiba, Kenjiro Obama, Shunji Kawazoe, Takahiro Oka, Akihiro Satoh
  • Patent number: 4489198
    Abstract: A process for polymerizing ethylene in the presence of a catalyst system comprising at least two halogen compounds of transition metals, one of which has the formula (TiCl.sub.3,Y3 AlCl.sub.3)(MY.sub.3).sub.x (MgYZ).sub.y, where M is a transition metal of Group VB or V1B, X is a halogen and 0.3.ltoreq.x.ltoreq.3, 0.ltoreq.y.ltoreq.20, and a Group I to III hydryde or organometallic activator and the mean residence time of the catalyst system in the polymerization reactor is between 2 and 100 seconds.
    Type: Grant
    Filed: March 22, 1983
    Date of Patent: December 18, 1984
    Assignee: CdF Chimie S.A. Societe Chimique des Charbonnages
    Inventor: Karel Bujadoux
  • Patent number: 4483938
    Abstract: A solution process for the preparation of high molecular weight homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 .alpha.-olefins is disclosed. The process involves feeding monomer, a particlar coordination catalyst and hydrocarbon solvent to a reactor, polymerizing the monomer at a temperature of 100.degree.-320.degree. C. and recovering the polymer. The catalyst is obtained by either (i) combining solutions of titanium tetrahalide/vanadium oxytrihalide and of organoaluminum compound at a temperature of less than 30.degree. C., heating the resulting admixture to a temperature of 150.degree.-300.degree. C. for a period of 5 seconds to 60 minutes and combining the thus heat-treated mixture with a solution of an organoaluminum compound or (ii) combining solutions of titanium tetrahalide and of organoaluminum compound at a temperature of less than 30.degree. C., heating the resultant admixture to a temperature of 150.degree.-300.degree. C.
    Type: Grant
    Filed: December 30, 1981
    Date of Patent: November 20, 1984
    Assignee: E. I. Du Pont de Nemours and Company
    Inventor: Richard W. Rees
  • Patent number: 4483971
    Abstract: A process for producing terpolymers of propylene (as a main monomer), ethylene and another .alpha.-olefin having superior and well-balanced physical properties, almost without forming soluble polymer is provided.This process is characterized by preliminarily activating a catalyst consisting of a titanium trichloride composition and a specified organoaluminum halide, with a small amount of an .alpha.-olefin of 2 to 12 carbon atoms, a trialkylaluminum and an aromatic ester, and copolymerizing specified amounts of propylene, ethylene and an .alpha.-olefin of 4 to 12 carbon atoms in the presence of the preliminarily activated catalyst obtained above.
    Type: Grant
    Filed: February 25, 1983
    Date of Patent: November 20, 1984
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Takeshi Suzuki, Kazutsune Kikuta, Hiromasa Chiba, Toshihiro Uwai, Kenji Matsuda, Tohru Hanari
  • Patent number: 4472315
    Abstract: Components of catalysts for polymerizing olefins having the general formula:VCl.sub.n (OR).sub.min which R=a hydrocarbon radical having 1-18 C; or R.sub.p.sup.1 Si(OH).sub.3-p, in which R.sup.1 =a hydrocarbon radical, 1.ltoreq.p.ltoreq.3; 1.5.ltoreq.n.ltoreq.3, m=3-n; with X-ray powder spectrum, in which maximum intensity diffraction lines, which in the spectrum of normal VCl.sub.3 appear at d=5.75 .ANG., d=2.67 .ANG. and d=1.74 .ANG., exhibit a broadening of the half peak breath of at least three times for the diffraction line at d=5.75 .ANG. and of at least four times for the diffraction lines appearing at d=2.67 .ANG. and d=1.74 .ANG., or said diffraction lines disappear.
    Type: Grant
    Filed: January 9, 1981
    Date of Patent: September 18, 1984
    Assignee: Montedison S.p.A.
    Inventors: Enrico Albizzati, Enzo Giannetti
  • Patent number: 4471066
    Abstract: A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formulaM.sub..alpha. MgR.sub.p X.sub.q.D.sub.rwherein.alpha., p, q and r each independently is 0 or a number greater than 0,p+q=m.alpha.+20.ltoreq.q/(.alpha.
    Type: Grant
    Filed: February 3, 1983
    Date of Patent: September 11, 1984
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
  • Patent number: 4460757
    Abstract: A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.
    Type: Grant
    Filed: July 29, 1982
    Date of Patent: July 17, 1984
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Masami Tachibana, Toshihiro Uwai, Kenji Matsuda, Yoshiharu Higuchi
  • Patent number: 4451688
    Abstract: Olefins are polymerized in the presence of a catalyst which comprises the combination of:[I] a solid substance obtained by the reaction of at least the following two components:(i) a magnesium compound represented by the general formula R.sup.1.sub.m (OR.sup.2).sub.n MgX.sub.2-m-n wherein R.sup.1 and R.sup.2 are each a hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m.ltoreq.2 and n is 0.ltoreq.n.ltoreq.2, provided 0.ltoreq.m+n.ltoreq.2, and(ii) a titanium compound and/or a vanadium compound;[II] a silicon compound represented by general formula R.sup.1 mSi(OR.sup.2).sub.n X.sub.4-m-n wherein R.sup.1 and R.sup.2 are each hydrocarbon radical having 1 to 24 carbon atoms, X is a halogen atom, m is 0.ltoreq.m<4 and n is 0<n.ltoreq.4, provided 0 m+n 4;[III] an organometallic compound, where said catalyst comprises a product obtained by pre-reacting said silicon compound (II) and said organometallic compound (III).
    Type: Grant
    Filed: September 1, 1982
    Date of Patent: May 29, 1984
    Assignee: Nippon Oil Company, Limited
    Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mituji Miyoshi
  • Patent number: 4431784
    Abstract: A solution process for the preparation of high molecular weight homopolymers of ethylene and copolymers of ethylene and C.sub.3 -C.sub.12 .alpha.-olefins is disclosed. The process involves feeding monomer, a particular coordination catalyst and hydrocarbon solvent to a reactor, polymerizing the monomer at a temperature of 105.degree.-320.degree. C. and recovering the polymer. The catalyst is obtained by combining solutions of titanium tetrahalide and of organoaluminum compound at a temperature of less than 30.degree. C., heating the resulting admixture to a temperature of 150.degree.-300.degree. C. for a period of 10 seconds to 10 minutes and combining the thus heat-treated mixture with a solution of an organoaluminum compound. The catalyst thus obtained is fed to the process, without separation of any components of the catalyst. In an embodiment part of the titanium tetrahalide may be replaced with vanadium oxytrihalide.
    Type: Grant
    Filed: December 30, 1981
    Date of Patent: February 14, 1984
    Assignee: Du Pont Canada Inc.
    Inventors: Michael A. Hamilton, Vaclay G. Zboril
  • Patent number: 4429087
    Abstract: A transition metal compound such as titanium tetrahydrocarbyloxides and a metal hydrocarbyloxide compound such as magnesium hydrocarbyloxides are chemically combined to form a first catalyst component which is treated with a second catalyst component comprising an organometallic compound precipitating agent to produce an active olefin polymerization catalyst. High polymer yields are realized per gram of catalyst when the catalyst thus produced is treated with a halide ion exchanging source and used with an organometallic cocatalyst.
    Type: Grant
    Filed: March 11, 1982
    Date of Patent: January 31, 1984
    Assignee: Phillips Petroleum Company
    Inventor: Charles E. Capshew
  • Patent number: 4410671
    Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is mixed with a precipitating agent to form an active olefin polymerization catalyst. The catalyst can be further treated with a halide ion exchanging source to form an active olefin polymerization catalyst. Prepolymer is deposited on the catalyst(s) in an amount effective to reduce polymer fines when the catalyst(s) are used in polymerization processes.
    Type: Grant
    Filed: February 22, 1982
    Date of Patent: October 18, 1983
    Assignee: Phillips Petroleum Company
    Inventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
  • Patent number: 4405769
    Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is rapidly mixed with a precipitating agent to form an active olefin polymerization catalyst.
    Type: Grant
    Filed: February 22, 1982
    Date of Patent: September 20, 1983
    Inventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz