Material Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non-transition Metal Atom Bond Patents (Class 526/159)
  • Patent number: 4370449
    Abstract: A transition metal composition has the formula:TiCl.sub.3 (AlR.sub.x X.sub.3-x).sub.n E.sub.a L.sub.bwhere E is an ether or thioether; L is a defined ester, an amine or a ketone; and a and b are each greater than 0.001 and not more than 0.50. The composition has a low surface area, typically less than 50 m.sup.2 /g. The composition can be prepared by reacting titanium tetrachloride with an organo-aluminium compound, optionally heating the reaction product, contacting the reaction product at an elevated temperature with at least one of E and L and washing the product subsequent to the treatment with E. In the composition, E is conveniently di-n-butyl ether or di-isoamyl ether and L can be tetramethylethylenediamine; ethyl benzoate; benzophenone; glycerol monostearate; glycerol triacetate; glycerol tripalmitate; glycerol trimethacrylate; pentaerythritol tetra-acrylate or ethyl phenyl acetate. The composition can be used as a component of a catalyst for the polymerization of olefine monomers such as propylene.
    Type: Grant
    Filed: November 1, 1979
    Date of Patent: January 25, 1983
    Assignee: Imperial Chemical Industries Limited
    Inventor: Ashley D. Bye
  • Patent number: 4368304
    Abstract: A process for producing .alpha.-olefin polymers is provided, which comprises: reacting an organoaluminum compound with an electron donor in a specified ratio in a solvent at a specified temperature to obtain a solid product (I); reacting solid product (I) with TiCl.sub.4 at a specified temperature in a specified ratio of Al/Ti and then removing a liquid portion from the resulting material followed by washing to obtain a solid product (II) having no free TiCl.sub.4 ; reacting solid product (II) with an electron donor and an electron acceptor in a specified ratio at a specified temperature to obtain a solid product (III); and polymerizing .alpha.-olefin(s) in the presence of a catalyst comprising a combination of solid product (III) with an organoaluminum compound. This process provides a catalyst having a high storing and thermal stability and a polymer having a uniform particle size.
    Type: Grant
    Filed: February 4, 1981
    Date of Patent: January 11, 1983
    Assignee: Chisso Corporation
    Inventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
  • Patent number: 4361714
    Abstract: A process for preparing linear alpha olefins and waxes having a total product M.sub.n in the range 200 to 700 which includes polymerizing an ethylene-containing gas in the presence of the reaction product of a zirconium halide with R.sub.2 Zn, wherein R is an alkyl group having about 1 to about 20 carbon atoms, in the presence of a diluent at a temperature of about 50.degree. to 200.degree. C. and an ethylene pressure above about 3.5 MPa, wherein the M.sub.n of said reaction product is controlled by the molar ratio of said R.sub.2 Zn/ZrCl.sub.4, said molar ratio being less than about 1.
    Type: Grant
    Filed: December 14, 1981
    Date of Patent: November 30, 1982
    Assignee: Exxon Research and Engineering Co.
    Inventors: Arthur W. Langer, John J. Steger, Terry J. Burkhardt
  • Patent number: 4357452
    Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminum compound of the general formula, AlR.sup.1.sub.n Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.
    Type: Grant
    Filed: July 16, 1980
    Date of Patent: November 2, 1982
    Assignee: Mitsubishi Chemical Industries Limited
    Inventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
  • Patent number: 4342854
    Abstract: Solid polymers of olefins having at least three carbon atoms per molecule and methods of making such polymers with a chromium-containing catalyst or organometal catalyst system.
    Type: Grant
    Filed: September 16, 1971
    Date of Patent: August 3, 1982
    Assignee: Phillips Petroleum Company
    Inventors: John P. Hogan, Robert L. Banks
  • Patent number: 4330433
    Abstract: Polyolefin granules having an average particle size diameter greater than 600 microns, preferably about 1000 microns or greater are obtained by polymerizing monoolefins in the presence of a titanium catalyst having an average particle size diameter of greater than about 35 microns and preferably 40 to 65 microns. The titanium catalysts are obtained by reducing titanium tetrahalide in the presence of a suitable organometallic reducing compound such as diethylaluminum chloride under controlled conditions of temperature, reduction rate and concentrations to obtain a titanium halide reduced solids product seeds having an average particle size diameter of about 20 microns or greater and thereafter simultaneously and without interruption adding to the seeds containing system titanium tetrahalide and organometallic reducing compound such as diethyl aluminum halide at a rate such that the reduction of titanium tetrahalide to titanium trihalide is about 6.times.10.sup.-4 to about 0.
    Type: Grant
    Filed: January 15, 1981
    Date of Patent: May 18, 1982
    Assignee: Exxon Research & Engineering Co.
    Inventor: Harry J. Wristers, deceased
  • Patent number: 4328121
    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: August 4, 1980
    Date of Patent: May 4, 1982
    Assignee: Phillips Petroleum Company
    Inventor: Charles E. Capshew
  • Patent number: 4326988
    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: August 12, 1980
    Date of Patent: April 27, 1982
    Assignee: Phillips Petroleum Company
    Inventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
  • Patent number: 4325837
    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 under an olefin atmosphere and prepolymer is formed on said catalyst to yield a catalyst capable of producing low fines content polymer.
    Type: Grant
    Filed: August 12, 1980
    Date of Patent: April 20, 1982
    Assignee: Phillips Petroleum Company
    Inventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz
  • Patent number: 4311752
    Abstract: Copolymers of ethylene and higher 1-olefins which are suitable for the manufacture of thin films, are preferably prepared in a two-step process, the first step yielding a polymer having a high molecular weight, the second step giving a polymer having a low molecular weight. The films obtained from these copolymers have improved mechanical properties as compared to films manufactured from known corresponding raw materials. The mechanical properties are furthermore uniform in longitudinal and in transverse direction.
    Type: Grant
    Filed: November 13, 1979
    Date of Patent: January 19, 1982
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Bernd Diedrich, Ludwig Bohm, Olaf Heine
  • Patent number: 4302567
    Abstract: A catalyst for the polymerization of olefins is described wherein a titanium(IV) compound is reduced with an organoaluminum compound in the presence of atactic poly-.alpha.-olefin. Polymerization with the catalyst is also disclosed.
    Type: Grant
    Filed: October 20, 1980
    Date of Patent: November 24, 1981
    Assignee: Ruhrchemie Aktiengesellschaft
    Inventors: Mufit Bahadir, Wolfgang Payer
  • Patent number: 4282341
    Abstract: A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers at relatively low temperatures under relatively low pressures by means of a Ziegler-Natta catalyst comprising (I) a titanium chloride component and (II) an aluminumalkyl component, wherein the titanium chloride component (I) employed is obtained by exposing a conventional catalyst component consisting, or substantially consisting, of titanium trichloride or titanium tetrachloride, to a carbon dioxide atmosphere under specific conditions. Catalysts obtained from titanium chloride components (I) which have been treated in this way exhibit a relatively long induction period.
    Type: Grant
    Filed: September 12, 1979
    Date of Patent: August 4, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Klaerner, Gerhard Staiger, Klaus Bronstert
  • Patent number: 4277588
    Abstract: A process for the preparation of acetylene copolymers by catalytic polymerization of a mixture of acetylene and dialkynes or polyalkynes, using Ziegler catalysts. The novel polymers may be used as colored pigments, as colored coatings for metal, glass or plastics, and for the production of electrical or magnetic components.
    Type: Grant
    Filed: March 13, 1980
    Date of Patent: July 7, 1981
    Assignee: BASF Aktiengesellschaft
    Inventors: Herbert Naarmann, Klaus Penzien, Helmut Doerfel, Albrecht Eckell
  • Patent number: 4264472
    Abstract: A catalyst for preparing an .alpha.-olefin polymer having a broad molecular weight distribution and excellent physical properties, which comprises a solid catalyst component (A) and an organometal compound (B), the solid catalyst component (A) being obtained by reduction with an organomagnesium solution of the thermal decomposition solid product of special titanium compounds.
    Type: Grant
    Filed: August 29, 1979
    Date of Patent: April 28, 1981
    Assignee: Asahi Kasei Kogyo Kabushiki Kaisha
    Inventors: Tadashi Ikegami, Hisaya Sakurai, Yoshihiko Katayama, Shigeo Tsuyama, Yukitoshi Iwashita
  • Patent number: 4263170
    Abstract: A catalyst comprising the product obtained by bringing into contact (a) a compound of magnesium comprising at least one species selected from the group consisting of magnesium monohalides (MgX), halo-magnesium hydrides (HMgX) and magnesium hydride (MgH.sub.2), X being a halogen and the said species MgX or HMgX being obtained by thermal decomposition of a powdery organo-magnesium halide R.sub.1 MgX wherein R.sub.1 is an organic radical; and (b) at least one halide of a transistion metal selected from the group consisting of titanium and vandium, the valency of said metal in said halide being lower than or equal to 3, the quantities of (a) and (b) being such that the atomic ratio of magnesium to said transistion metal is between 1 and 25, and a catalyst system including the catalyst that is suitable for use in the polymerization of olefins and particularly ethylene.
    Type: Grant
    Filed: May 4, 1979
    Date of Patent: April 21, 1981
    Assignee: Societe Chimique des Charbonnages - CdF Chimie
    Inventor: Karel Bujadoux
  • Patent number: 4259466
    Abstract: A titanium trichloride-catalyzed process for stereospecific polymerization of alpha-olefins, particularly propylene, to produce polymers of relatively high bulk density comprises employing as the TiCl.sub.3 catalyst component, used with an aluminum alkyl cocatalyst, a 0.1 to 30 millimicron fraction of a TiCl.sub.3 composition produced by(a) reacting TiCl.sub.4 with a complexing agent in a molar ratio of from 1:0.3 to 1:2;(b) reacting an organo-aluminum compound with a complexing agent in a molar ratio of at most 1:0.25;(c) reducing the complexed TiCl.sub.4 with the complexed organo-aluminum compound over a period of less than one hour at a temperature within the range 60.degree. to 110.degree. C. to produce TiCl.sub.3 particles having an average particle size of from 50 to 500 .mu.m;(d) subjecting the TiCl.sub.3 particles to a treatment to reduce the average particle size thereof to less than 50 .mu.m, and(e) classifying the TiCl.sub.
    Type: Grant
    Filed: November 8, 1979
    Date of Patent: March 31, 1981
    Assignee: Shell Oil Company
    Inventors: Andras G. T. G. Kortbeek, Adrianus A. Van Der Nat
  • Patent number: 4258161
    Abstract: Propylene is polymerized in the presence of a catalytic system of the type which comprises a solid titanium trichloride-based complex serving as a catalyst, said complex having an atomic ratio of aluminum to titanium in the range of below 0.15:1 and containing a complexing agent, and an organic aluminium compound of the general formula, AlR.sub.n.sup.1 Cl.sub.3-n wherein R.sup.1 represents an n-propyl group or an n-hexyl group and n is a value of 1.95-2.10. The catalytic system may further comprise an electron-donor compound as a third catalytic component.
    Type: Grant
    Filed: January 22, 1979
    Date of Patent: March 24, 1981
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Genjiro Kakogawa, Masayoshi Hasuo, Yoshinori Suga, Hisashi Kitada, Yumito Uehara
  • Patent number: 4246134
    Abstract: A catalyst according to the present invention for di-, oligo-, co- and poly- merization of vinyl monomers consists of an active phase comprising a compound of a transition metal of Groups IV-V of the periodic system deposited onto a polymeric carrier, viz, a macroporous copolymer of vinyl and divinyl monomers with a specific surface area of 30 to 700 m.sup.2 /g and a co-catalyst such as an organo-aluminum compound. The catalyst according to the present invention makes it possible to obtain dimers in high yields of more than 6,000 kg as calculated for 1 g of the transition metal for 2 hours and polymers in yields of up to 72 kg per 1 g of the transition metal. The catalyst according to the present invention makes it possible to control the particle size of the resulting (co) polymer which enables the use of the (co) polymer avoiding the stage of granulation.
    Type: Grant
    Filed: November 27, 1978
    Date of Patent: January 20, 1981
    Inventors: Boris A. Uvarov, Valentina I. Tsvetkova, Fridrikh S. Dyachkovsky, Oleg M. Zvyagin, Vladimir P. Konovalov, Elvira A. Uvarova, Elena I. Ljustgarten, Ljudmila A. Novokshonova, Olga I. Kudinova, Tatyana A. Maklakova
  • Patent number: 4238355
    Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are prepared by reacting tetravalent or trivalent titanium compounds such as a titanium tetraalkoxide, an anhydrous zinc compound such as diethyl zinc, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and a halide source such as a hydrogen halide or an alkyl aluminum halide and an aluminum compound if the halide source of organomagnesium component does not contain sufficient quantities of aluminum. Polymerization processes employing this catalyst composition do not require conventional catalyst removal steps in order to provide polymers having suitable color and other physical characteristics and these catalysts produce polymers having broader molecular weight distributions than do corresponding catalysts without the anhydrous zinc compound.
    Type: Grant
    Filed: September 10, 1979
    Date of Patent: December 9, 1980
    Assignee: The Dow Chemical Company
    Inventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
  • Patent number: 4233182
    Abstract: High activity alpha-olefin polymerization catalysts comprising an organometallic promoter and a component prepared from at least one compound of a Group IVB, VB, or VIB metal, at least one support material which is a divalent metal salt of a phosphorus acid ester having at least one phosphorous acid ester group bonded to metal through oxygen or sulfur, and at least one alkylaluminum halide.
    Type: Grant
    Filed: December 26, 1978
    Date of Patent: November 11, 1980
    Assignee: Standard Oil Company (Indiana)
    Inventors: Glen R. Hoff, Peter Fotis
  • Patent number: 4224185
    Abstract: Solid catalyst particles are made into a form and shape that is easier to handle, without changing their surface area or adversely affecting their activity by "matting" the catalyst particles with a fibrillatable polymer by mechanical shearing action and subsequently shaping the "mat", followed by controlled sizing and shaping into the form of pellets, tablets, and the like by known mechanical means. Activity is not impaired, and shaped polymer can be produced in those reactions where the catalyst determines the shape of the product. The practice of this invention is particularly useful to shaped Ziegler-type catalysts.
    Type: Grant
    Filed: March 26, 1979
    Date of Patent: September 23, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventor: Harry J. Wristers
  • Patent number: 4220555
    Abstract: Polyolefins are prepared wherein at least about ninety-five percent of the product is retained on a 100 mesh screen. The polymerization process involves contacting the alpha-olefin with a Ziegler catalyst system wherein the catalyst has been prepared by mixing the active catalytic particles with a fibrillatable polyolefin and a non-fibrillatable polyolefin followed by ballmilling the mixture for a period of time sufficient to cause a fibrous mat to form, entrapping the catalyst particles in the mat which is, in turn, carried by the non-fibrillatable polyolefin.
    Type: Grant
    Filed: September 7, 1978
    Date of Patent: September 2, 1980
    Assignee: Exxon Research & Engineering Co.
    Inventors: Harry J. Wristers, Eugene E. Poirot, Terrence Huff
  • Patent number: 4219633
    Abstract: Random copolymers of ethylene and propylene are prepared by a process comprising contacting under bulk or vapor phase polymerization conditions components comprising (a) a catalyst capable of producing substantially crystalline polypropylene; and (b) ethylene and propylene in an essentially constant ratio of about 0.1 to 1.0 mole percent ethylene to about 99.9 to 99.0 mole percent propylene. The random copolymers produced by this process have high clarity and distribution numbers greater than 90.
    Type: Grant
    Filed: April 9, 1979
    Date of Patent: August 26, 1980
    Assignee: Standard Oil Company (Indiana)
    Inventor: Paul E. Johnson
  • Patent number: 4217245
    Abstract: A novel catalyst system for the polymerization or copolymerization of olefines, more particularly to ethylene is disclosed. For preparing the novel catalyst system, a titanium compound (Ti IV) is previously attached to a solid supporting member, whereafter the so anchored Ti is reacted with vapors of a metal, in the presence of a halogenated compound or not. Very high polymer yields are obtained and examples are given.
    Type: Grant
    Filed: June 2, 1978
    Date of Patent: August 12, 1980
    Assignee: Snamprogetti, S.p.A.
    Inventors: Margherita Corbellini, Alessandro Gamba, Carlo Busetto
  • Patent number: 4210736
    Abstract: Particles of titanium trichlorides usable for the stereospecific polymerization of alpha-olefines, especially propylene, having been dried until their liquid content is less than 1% by weight relative to the weight of titanium trichloride present in said particles, as well as a process for the preparation of such particles and a process for stereospecific polymerization in the presence thereof.
    Type: Grant
    Filed: April 23, 1979
    Date of Patent: July 1, 1980
    Assignee: Solvay & Cie.
    Inventors: Paul Baekelmans, Albert Bernard
  • Patent number: 4208304
    Abstract: A catalyst for producing ethylene polymers in which a first component composed of titanium, vanadium, halogen, and OR groups, wherein R is selected from among alkyl, cycloalkyl, aryl, acyl, and combinations thereof, is combined with an organometallic compound. A method for producing a catalyst system in which an organoaluminum compound component is contacted with a component composition produced by reacting a mixture of titanium and vanadium compounds with an organometallic compound to form a product mixture which is then contacted with titanium tetrachloride. A method for producing polymers of ethylene by contacting ethylene with a catalyst system produced as above under conditions suitable for polymerization.
    Type: Grant
    Filed: May 19, 1978
    Date of Patent: June 17, 1980
    Assignee: Phillips Petroleum Company
    Inventor: Darryl R. Fahey
  • Patent number: 4204981
    Abstract: Ziegler catalytic system for the polymerization of olefins, formed by the combination of an organo-metallic compound and a compound of a heavy metal supported on a carrier.The carrier is an active complex obtained by reacting one or more alloys of metals chosen from Mg, Fe, Al, Ni, Cr and Zn, gaseous hydrogen chloride and one or more alcohols in the liquid or gaseous state, at a temperature of from 60.degree. to 300.degree. C., the said active complex having a content of free alcoholic hydroxyl groups of from 1 to 20% by weight, a chlorine content of from 15 to 70% by weight, a metal content of from 5 to 35% by weight, a porosity of from 0.1 to 1 cc/g and a surface area of from 1 to 200 m.sup.2 /g.
    Type: Grant
    Filed: September 29, 1978
    Date of Patent: May 27, 1980
    Assignee: Euteco S.p.A.
    Inventors: Renzo Invernizzi, Ferdinando Ligorati, Maurizio Fontanesi
  • Patent number: 4200715
    Abstract: A process is provided for the polymerization of an olefin such as ethylene in the vapor phase in a moving bed of particles of the polymerized olefin in which novel means are employed to feed the finely-divided solid polymerization catalyst to the polymerization zone. The process is carried out by pumping into the polymerization zone a Bingham fluid which has the finely-divided solid polymerization catalyst uniformly dispersed throughout a solid continuous phase, which is a mixture of a wax and a hydrocarbon which is a liquid at ambient temperature.
    Type: Grant
    Filed: May 19, 1978
    Date of Patent: April 29, 1980
    Assignee: Gulf Oil Corporation
    Inventors: Thomas J. Lynch, Robert J. Rowatt
  • Patent number: 4200717
    Abstract: A solid titanium trichloride, produced by precipitation from a homogeneous solution or mixture with an ether, is treated by prepolymerization with propylene at a partial pressure of less than 1 kg/cm.sup.2. The pretreated titanium trichloride containing a propylene polymer is then admixed with an organoaluminum compound and the admixture is used as a catalyst in the polymerization of propylene.
    Type: Grant
    Filed: March 27, 1978
    Date of Patent: April 29, 1980
    Assignee: Mitsubishi Chemical Industries, Ltd.
    Inventors: Toshizo Abe, Nobuaki Goko, Yasuhiro Nishihara, Yukimasa Matuda
  • Patent number: 4189557
    Abstract: A process for the manufacture of homopolymers and copolymers of .alpha.-monoolefins by polymerizing the monomer or monomers by means of a Ziegler-Natta catalyst comprising (I) a titanium trichloride component and (II) an aluminum-alkyl component, wherein the titanium trichloride component (I) employed is obtained by (1) in a first stage moistening a suitable conventional catalyst component, consisting entirely or substantially of titanium trichloride, with a hydrocarbon mixture comprising a liquid alkane hydrocarbon and a liquid benzene hydrocarbon and (2) in a second stage drying the catalyst component, moistened with the hydrocarbon mixture, under an inert gas, with constant mechanical mixing, within a certain period, at a temperature which is from 5.degree. to 50.degree. C. above the boiling point of the highest-boiling hydrocarbon present in the hydrocarbon mixture which has been used to moisten the component.
    Type: Grant
    Filed: April 28, 1978
    Date of Patent: February 19, 1980
    Assignee: BASF Aktiengesellschaft
    Inventors: Peter Klaerner, Klaus Bronstert, Gerhard Staiger
  • Patent number: 4187385
    Abstract: Polymerization of ethylene or .alpha.-olefins using a catalyst comprising a titanium component obtained by copulverizing the starting titanium component of Ziegler catalysts and organoaluminum compound with a small amount of ethylene or .alpha.-olefins, and an organoaluminum component. The titanium catalyst component can be modified by subjecting the copulverized titanium component to a contact with an inert organic solvent or its mixture with a modifier (1) an oxygen-, sulphur-, phosphor-, nitrogen- or silicon- containing organic compound, (2) a combination of such an organic compound and an aluminum halide, (3) an organoaluminum compound or (4) a Lewis acid.
    Type: Grant
    Filed: May 16, 1977
    Date of Patent: February 5, 1980
    Assignee: Mitsui Toatsu Chemical, Inc.
    Inventors: Tetsuya Iwao, Heizo Sasaki, Akira Ito, Masahiro Kono
  • Patent number: 4182811
    Abstract: A catalyst for the (co)polymerization of ethylene, .alpha.-olefines, conjugated and non-conjugated dienes, a method of preparation, and a mode of using same. The catalyst contains from 0.1 to 50 wt.% of a compound of a transition metal of the IV-VIII Groups chemically combined and distributed over the surface and within the volume of a rubber-like polymeric carrier containing from 1 to 50 wt.% of electron-donor and/or electron-acceptor groups and is in the form of a gel which is swellable, but insoluble in the reaction medium.A co-catalyst comprising an organic compound of a metal of Groups I-III is employed chemically combined and/or non-combined with the catalyst.The catalyst is prepared by mixing the metal compound with said carrier swollen or dissolved in a solvent, and by extracting the resulting compound with a solvent.(Co)polymerization is effected in a solvent such as a hydrocarbon or a hologenated hydrocarbon derivative at a temperature not exceeding 200.degree. C.
    Type: Grant
    Filed: February 27, 1978
    Date of Patent: January 8, 1980
    Inventors: Jury N. Bocharov, Viktor A. Kabanov, Marina A. Martynova, Valery G. Popov, Vladimir I. Smetanjuk, Viktor V. Fedorov
  • Patent number: 4182817
    Abstract: A process is provided for the stereospecific polymerization of an olefin such as ethylene in a liquid medium in which a finely-divided solid polymerization catalyst is fed to the polymerization zone on a truly continuous basis to provide a uniform dispersion of the polymerization catalyst throughout the polymerization zone. The process is carried out by pumping into the polymerization zone a Bingham fluid which has the finely-divided solid polymerization catalyst uniformly dispersed throughout a solid continuous phase, which is a mixture of a wax and a liquid hydrocarbon.
    Type: Grant
    Filed: May 19, 1978
    Date of Patent: January 8, 1980
    Assignee: Gulf Oil Corporation
    Inventors: Thomas J. Lynch, Robert J. Rowatt
  • Patent number: 4167615
    Abstract: Hydrocarbon-soluble compositions useful as the transition metal component in the Ziegler polymerization of .alpha.-olefins are provided by reacting molecular nitrogen or hydrogen with a transition metal compound such as titanium trichloride to form a dinitrogen or dihydrogen complex of the transition metal compound.
    Type: Grant
    Filed: January 16, 1978
    Date of Patent: September 11, 1979
    Assignee: The Dow Chemical Company
    Inventors: Donald E. Gessell, Kirby Lowery, Jr.
  • Patent number: 4166167
    Abstract: Gas-phase polymerization of an .alpha.-olefin, especially propylene, in a stirred or fluidized bed of substantially uniform and approximately spherical carrier particles of an .alpha.-olefin polymer of diameter 100-500 .mu.m, using a catalyst comprising an organo-metallic compound and a solid transition metal compound which has a particle size of less than 5 .mu.m, produces a propylene polymer having unexpectedly good powder flow characteristics. The transition metal compound is conveniently a titanium trichloride-containing material which has been treated with a dialkyl ether solution.
    Type: Grant
    Filed: June 20, 1977
    Date of Patent: August 28, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: Ashley D. Bye, John E. Priddle, Victor A. Wilson
  • Patent number: 4161574
    Abstract: A polypropylene having a strongly reduced melting temperature and improved optical properties is obtained by copolymerization of propylene with small quantities of ethylene and butene-(1).
    Type: Grant
    Filed: August 22, 1977
    Date of Patent: July 17, 1979
    Assignee: Hoechst Aktiengesellschaft
    Inventors: Helmut Strametz, Kurt Rust
  • Patent number: 4158571
    Abstract: Bingham fluid compositions are provided which contain a functional material such as a polymerization initiator dispersed in a solid continuous phase, which is a mixture of a wax and a liquid hydrocarbon. Such compositions are prepared by heating the wax and the liquid hydrocarbon to form a melt and dispersing the functional material in the melt. Upon cooling, the composition solidifies with the functional material being uniformly dispersed throughout the continuous solid phase. The compositions, while solid at ambient temperature and pressure, assume the flow characteristics of a liquid under an applied pressure and can be pumped to feed the functional material to a polymerization reactor or molten polymer on a continuous basis.
    Type: Grant
    Filed: May 19, 1978
    Date of Patent: June 19, 1979
    Assignee: Gulf Oil Corporation
    Inventors: Thomas J. Lynch, Robert J. Rowatt
  • Patent number: 4154700
    Abstract: A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a particular titanium-containing compound, viz.
    Type: Grant
    Filed: November 30, 1977
    Date of Patent: May 15, 1979
    Assignee: BASF Aktiengesellschaft
    Inventors: Heinz Mueller-Tamm, Hans Schick, James F. R. Jaggard, Johann Nickl
  • Patent number: 4154699
    Abstract: A process for the manufacture of a titanium-containing component of a catalyst for the polymerization of monoolefins by the Ziegler-Natta method by milling (a) a particular titanium-containing compound, viz.
    Type: Grant
    Filed: November 30, 1977
    Date of Patent: May 15, 1979
    Assignee: BASF Aktiengesellschaft
    Inventors: Heinz Mueller-Tamm, Hans Schick, James F. R. Jaggard, Johann Nickl
  • Patent number: 4151113
    Abstract: Novel halogenated organoaluminum catalysts are prepared by prereacting a material of the formula:R.sub.m AlX.sub.3-mwherein m is an integer of from 1 to 3 inclusive, R is the same or different alkyl radical of straight or branched chain structure of from 1 to 7 carbons and X is the same or different halogen selected from the group consisting of chlorine and bromine with Y moles of halogen or mixed halogen per mole of aluminum compound wherein the halogen is selected from the group consisting of chlorine and bromine such that (m-Y) is from less than 0.7 to about 0.2. The materials must be prepared sufficiently prior to use to insure extensive reaction of the components to yield an effective polymerization catalyst. Preferably, the components are prereacted for at least 2 minutes, more preferably at least 10 minutes, most preferably at least 4 hours, i.e. (overnight). The catalyst is prepared at any temperature insuring liquid conditions, i.e., -100.fwdarw.+100.degree. C.
    Type: Grant
    Filed: August 29, 1977
    Date of Patent: April 24, 1979
    Assignee: Exxon Research & Engineering Co.
    Inventor: Warren A. Thaler
  • Patent number: 4146693
    Abstract: Improved continuous process for synthesis of cis-1,4 poly(isoprene). In the commercial process for synthesis of cis-1,4 poly(isoprene) only a portion of the monomer charged is polymerized. The polymer, thus obtained, is separated from the unreacted monomer which in turn is recycled with solvent back into the system for conversion to additional polymer. Fresh monomer must be added from a separate feed to this recycle stream in sufficient quantity to replace or "make-up" for that which was converted to polymer. In the improved process of this invention, this "make-up" isoprene monomer is dried and then is introduced into the process subsequent to the initiation of polymerization of the isoprene monomer already present within the system, but prior to deactivation of the polymerization catalyst. Dehydration of "make-up" isoprene prior to its introduction into the process stream at the above juncture avoids deactivation of the still active catalyst with water.
    Type: Grant
    Filed: December 2, 1977
    Date of Patent: March 27, 1979
    Assignee: The B. F. Goodrich Company
    Inventor: Robert E. Beauregard
  • Patent number: 4146695
    Abstract: The invention is directed to new catalysts consisting of a chromium compound and an organometal compound of an element of Group II or III of the periodic system on a carrier, the process for preparing the catalyst and its use in polymerizing 1-alkenes containing 2 to 8 carbon atoms, optionally admixed with at most 10 mole% of at least one other 1-alkene of 2 to 8 carbon atoms.
    Type: Grant
    Filed: May 23, 1977
    Date of Patent: March 27, 1979
    Assignee: Stamicarbon, B.V.
    Inventor: Lambertus J. M. A. VAN DE Leemput
  • Patent number: 4142991
    Abstract: A substantially agglomeration-free, finely divided catalyst component which is suitable for use as a cocatalyst with organoaluminum compounds in the polymerization of alpha olefins, which is formed by grinding a titanium trichloride material, an effective amount of an electron pair donor compound to enhance the performance of said catalyst component, and an effective amount for agglomeration control of an agglomeration control agent. The agglomeration control agent is effective in either reducing the attractive forces between the finely divided particles in the catalyst component or by preventing the close approach of these particles which would result in agglomeration.
    Type: Grant
    Filed: November 8, 1976
    Date of Patent: March 6, 1979
    Assignee: Stauffer Chemical Company
    Inventors: Gregory G. Arzoumanidis, Richard F. Gold, Christian G. Michel
  • Patent number: 4138540
    Abstract: A high molecular weight copolymer of ethylene and a C.sub.3 -C.sub.20 .alpha.-olefin which, after being molded at room temperature and pressure-free tempered at 120 to 250.degree. C. and thereafter cooled, provides molded articles having an ultimate tensile strength of more than 200 kg per square centimeter measured at 120.degree. C. and an impact strength of more than 200 kg cm/cm.sup.2 measured at 23.degree. C.; a process for the preparation of such a copolymer by a Ziegler catalysis which process is characterized in that the catalyst which is employed is one obtained by reducing a titanium-(IV)-halide with an organo-aluminum compound in an inert solvent such that the concentration of titanium-(III)-halide so formed amounts to 30 to 200 m mol/liter solvent, the C.sub.3 -C.sub.20 .alpha.-olefin is employed in an amount of 0.05 to 5 weight percent based upon the weight of the ethylene and the catalyst is either initially contacted with C.sub.3 -C.sub.20 .alpha.
    Type: Grant
    Filed: April 28, 1977
    Date of Patent: February 6, 1979
    Assignee: Ruhrchemie Aktiengesellschaft
    Inventors: Siegfried Lutze, Peter Schneller, Hans-Walter Birnkraut, Josef Berzen, Gunter Hetkamp
  • Patent number: 4135045
    Abstract: An improved process for the polymerization of olefins in the presence of catalyst consisting essentially of:(A) a titanium trichloride composition obtained by micro-pulverizing a titanium trichloride component prepared by reduction of titanium tetrachloride with a member selected from the group consisting of hydrogen, silicon, metallic titanium and metallic aluminum, in the presence of a complex of aluminum chloride or aluminum bromide with an electron-donor selected from the group consisting of oxygen-containing organic compounds, nitrogen-containing organic compounds and phosphorus-containing organic compounds, the amount of the complex being 0.005 to 0.5 mole per mole of the titanium trichloride component, and extracting the micro-pulverized titanium trichloride component with a solvent selected from the group consisting of saturated aliphatic hydrocarbons, aromatic hydrocarbons and halogenated aromatic hydrocarbons; and(B) an organoaluminum compound,And the catalyst therefor.
    Type: Grant
    Filed: September 1, 1976
    Date of Patent: January 16, 1979
    Assignee: Mitsui Petrochemical Industries, Ltd.
    Inventors: Norio Matsuzawa, Hidesaburo Oi, Hiroshi Nishimura, Shigeru Wada, Juntaro Sasaki
  • Patent number: 4134855
    Abstract: A transition metal compound containing at least one .eta..sup.6 -arene is contacted with a compound of the formula MX.sub.n Y.sub.2-n mL; or Z.sub.3 Al[MgZ.sub.2 ].sub.y AlZ.sub.3 where L, M, X, Y, Z, m, n, and y are defined. The transition metal compound can be a compound such as TiCl.sub.2.2AlCl.sub.3 -arene. The compound of the defined formula may be a solid compound which may be insoluble in hydrocarbon liquids when it may be of high surface area which may be inherent in the solid or can be achieved by a grinding procedure. The compound of the defined formula may be Mg(OC.sub.2 H.sub.5).sub.2 ; Mg(CH.sub.3).sub.2 ; Mg(CH.sub.2 C.sub.6 H.sub.5).sub.2 ; (C.sub.2 H.sub.5).sub.3 Al[Mg(C.sub.2 H.sub.5).sub.2 ]-Al(C.sub.2 H.sub.5).sub.3 or (iC.sub.3 H.sub.7 O).sub.3 Al(Mg(OiC.sub.3 H.sub.7).sub.2 ]Al(OiC.sub.3 H.sub.7).sub.3. During or after the contacting with the transition metal compound, treatment with a halogen-containing compound may be effected.
    Type: Grant
    Filed: August 8, 1977
    Date of Patent: January 16, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: John P. Candlin, John A. A. A. G. Segal
  • Patent number: 4133944
    Abstract: Ethylene is polymerised or copolymerised using a transition metal catalyst at a pressure in the range 300-1000 atmospheres and a temperature of at least 100.degree. C in the presence of a volatile inert diluent such as pentane, or at least one 1-olefine comonomer such as buten-1, or both. The catalyst can be a Ziegler type catalyst, an organo-compound of a transition metal such as a substituted silylmethyl, cyclopentadienyl, arene, norbornyl, .pi.-allyl or benzyl compound and may be supported on a suitable support such as silica, alumina, or magnesia. Other catalysts which may be used are supported chromium or molybdenum oxides. If a solid catalyst is used it is preferred to use a material which has been finely dispersed.
    Type: Grant
    Filed: November 25, 1975
    Date of Patent: January 9, 1979
    Assignee: Imperial Chemical Industries Limited
    Inventors: Richard R. Cooper, Kenneth S. Whiteley
  • Patent number: 4130699
    Abstract: Vapor phase polymerization of an olefin which comprises conveying inactive high yield titanium catalyst component to a vapor phase polymerization reactor with a liquid comprising recycled quench liquid, reactivating said inactive high yield titanium catalyst component inside the reactor with a metal alkyl reducing agent and polymerizing olefin under gas phase polymerization conditions with reactivated high yield catalyst to form a resinous polymer of an olefin having a low level of catalyst residues.
    Type: Grant
    Filed: November 25, 1977
    Date of Patent: December 19, 1978
    Assignee: Standard Oil Company (Indiana)
    Inventors: Glen R. Hoff, John L. Melquist, Peter Fotis
  • Patent number: 4128708
    Abstract: A process for preparing cis-polyisoprene which comprises polymerization of isoprene in a medium of a non-polar hydrocarbon solvent at a temperature ranging from 0.degree. to 60.degree. C in the presence of a catalyst comprising a reaction product of titanium tetrachloride and an intracyclic organo-aluminium compound having the formula: ##STR1## wherein R, the same or different, are H, CH.sub.3 ; taken in a molar ratio of 1:1.05-1.1 respectively; weight ratio of isoprene to said catalyst being equal to 100:0.2-0.7.The present invention makes it possible to improve the quality of the thus-obtained cis-polyisoprene and to increase the catalyst capacity by two times due to modification of its properties.
    Type: Grant
    Filed: January 19, 1977
    Date of Patent: December 5, 1978
    Inventors: Alexandr G. Liakumovich, Boris I. Pantukh, Mengzda K. Sultanova, Vasily P. Popov, Genrikh A. Tolstikov, Jury B. Monakov, Valery P. Juriev, Elena Y. Mandelshtam, Boris S. Korotkevich, Jury A. Shmuk
  • Patent number: 4127505
    Abstract: The invention relates to a process for the production of a catalyst component for use in the polymerization of .alpha.-olefins, which comprises reacting titanium tetrachloride with a dialkylaluminum monohalide and monoalkylaluminum dihalide, said dialkylaluminum monohalide being in a proportion of at least equimolar to said titanium tetrachloride, to thus obtain a violet reduced solid, then removing aluminum compounds contained in said reduced solid and further activating with a mixture or complex of titanium tetrachloride and a dialkyl ether of the general formula ROR' wherein R and R' are the same or different and are (a) alkyl groups having 1-4 carbon atoms, (b) normal alkyl groups having 5 carbon atoms or (c) alkyl groups having 6-20 carbon atoms and to a catalyst component prepared by the process of the invention.
    Type: Grant
    Filed: November 23, 1976
    Date of Patent: November 28, 1978
    Assignee: Toa Nenryo Kogyo Kabushiki Kaisha
    Inventors: Hiroshi Ueno, Naomi Inaba, Tokyo Makishima, Shozo Wada