With Group Ivb Transition Metal Compound (ti, Zr, Hf) Patents (Class 526/158)
  • Patent number: 4208497
    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 trichloride component and (II) an aluminum-alkyl component, wherein the titanium trichloride component (I) employed is obtained by exposing a conventional catalyst component consisting, or substantially consisting, of titanium trichloride, to a carbon monoxide atmosphere under specific conditions. Catalysts obtained from titanium trichloride components (I) which have been treated in this way exhibit a relatively long induction period.
    Type: Grant
    Filed: March 3, 1978
    Date of Patent: June 17, 1980
    Assignee: BASF Aktiengesellschaft
    Inventors: Klaus Bronstert, Peter Klaerner, Gerhard Staiger
  • Patent number: 4194992
    Abstract: A novel catalyst system for the polymerization or copolymerization as the case may be, of alpha-olefines is disclosed, which comprises a cocatalyst which is an aluminum-organic compound and a catalyst proper which is obtained by reacting metal vapors (such as vapors of Mg, Al, Ti, V, Cr, Mn, Fe or their alloys) with Ti or V compounds, a halogen donor and a hydrocarbonaceous inert diluent being possibly present. Another aspect of the invention is the conduct of the polymerization, or copolymerization, run proper. Numerous examples of practical application of the catalyst preparation and use are given and the advantages of the novel approach shown.
    Type: Grant
    Filed: July 20, 1978
    Date of Patent: March 25, 1980
    Assignee: Snamprogetti, S.p.A.
    Inventors: Margherita Corbellini, Alberto Greco
  • Patent number: 4163831
    Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins are provided by reacting compound of titanium, e.g., a titanate such as tetra(isopropoxy)titanium, an organomagnesium compound or complex such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium 1/6 triethylaluminum and an alkyl aluminum halide. The organomagnesium component is highly concentrated in hydrocarbon diluent at the time it reacts with the metallic halide. The resulting catalysts when used in slurry polymerization processes produce polyolefin powders having higher bulk densities than those produced using conventional high efficiency catalysts.
    Type: Grant
    Filed: October 26, 1976
    Date of Patent: August 7, 1979
    Assignee: The Dow Chemical Company
    Inventor: Donald E. Gessell
  • Patent number: 4151337
    Abstract: Polyolefin is prepared by polymerizing an olefin by using a catalyst system combining an auxiliary catalytic component of an organoaluminum compound and a solid catalytic component obtained by reacting a mixture of a vanadium trichloride ether complex and a titanium trichloride ether complex with an aluminum halide and/or a boron halide.
    Type: Grant
    Filed: May 25, 1977
    Date of Patent: April 24, 1979
    Assignee: Mitsubishi Chemical Industries Ltd.
    Inventors: Natsuki Kanoh, Toru Tanaka, Nobuo Enokido
  • 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: 4120823
    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 titanium trichloride/aluminum trichloride complex and (b) a particular ether with one another, in which process (1) a vibratory ball mill producing a particular milling acceleration is used, (2) until from 6 to 85% of the aluminum trichloride originally present in a bonded form in the titanium-containing compound (a) have been eliminated from the said compound (a). Polyolefins of high stereoregularity can be obtained in a high specific yield by means of the catalyst component manufactured according to the invention.
    Type: Grant
    Filed: November 30, 1977
    Date of Patent: October 17, 1978
    Assignee: BASF Aktiengesellschaft
    Inventors: Heinz Mueller-Tamm, Hans Schick, James F. R. Jaggard, Johann Nickl
  • Patent number: 4110524
    Abstract: High bulk density modification III of isotactic polybutene-1 is directly prepared by polymerizing butene-1 at 100.degree.-200.degree. C, preferably 140.degree.-160.degree. C., with a catalyst of: (a) titanium trichloride and (b) an alkyl aluminum compound.
    Type: Grant
    Filed: April 24, 1974
    Date of Patent: August 29, 1978
    Assignee: Chemische Werks Huels A.G.
    Inventor: Albert Frese
  • Patent number: 4098907
    Abstract: A method of preparing reformed titanium trichloride catalyst for .alpha.-olefin polymerization which comprises simultaneously pulverizing an organoaluminum compound and a crystalline titanium trichloride compound, the latter comprising titanium trichloride and aluminum trichloride, subsequently treating the pulverized mixture with a solvent selected from oxygen-containing organic compounds, and finally treating the thus treated titanium trichloride with a halide of a metal selected from the groups IV and V of the periodic table.
    Type: Grant
    Filed: December 9, 1976
    Date of Patent: July 4, 1978
    Assignee: Toyo Stauffer Chemical Co., Ltd.
    Inventors: Shoichi Tokunaga, Atsumi Kato, Yoshikazu Takahashi, Kiyoshi Yamane
  • Patent number: 4093790
    Abstract: A high molecular weight polymer characterized by chains of benzene rings comprising alternatively di-substituted rings and tri-substituted rings, wherein the di-substituted rings comprise a major part of 1,3 (meta)- and a minor part of 1,4 (para)- di-substituted rings, and the tri-substituted rings are members of the group consisting of 1,3,5-, 1,2,4- and mixtures of 1,3,5- and 1,2,4- tri-substituted rings, these tri-substituted rings being substituted by 1 to 3 chains of benzene rings, each of the other substituents being a benzene ring which is unsubstituted or is substituted by a radical of the group consisting of alkyl, aryl and halogen radicals.
    Type: Grant
    Filed: January 5, 1972
    Date of Patent: June 6, 1978
    Assignee: Labofina S.A.
    Inventor: William J. I. Bracke
  • Patent number: 4079175
    Abstract: A method for the polymerization or copolymerization of .alpha.-olefin wherein .alpha.-olefin is polymerized or copolymerized in the presence of a catalyst essentially comprising a reformed titanium trichloride and an organoaluminum compound. The reformed titanium trichloride is prepared by simultaneously pulverizing an organoaluminum compound and a crystalline titanium trichloride compound, the latter comprising titanium trichloride and aluminum trichloride, treating the pulverized mixture with a solvent selected from aromatic hydrocarbons, aromatic hydrocarbon halides and organic ethers, separating the treated material from the solvent, and heating the separated material.
    Type: Grant
    Filed: August 30, 1976
    Date of Patent: March 14, 1978
    Assignee: Toyo Stauffer Chemical Co., Ltd.
    Inventors: Shoichi Tokunaga, Atsumi Kato, Teruhiro Setoguchi, Shoji Mizuno
  • Patent number: 4048419
    Abstract: Butene-1 optionally in the presence of up to 10% by weight of propene or like comonomer, is polymerized in excess butene-1 or liquid C.sub.4 fraction at 60.degree.-120.degree. C. to form a polybutene suitable for forming transparent films by employing as the polymerization catalyst (a) TiCl.sub.3 . nAlCl.sub.3 (n = 0.2 to 0.6) and (b) a mixture of 85 - 99.9 molar percent of dialkyl aluminum monochloride and 0.1 - 15 molar percent of trialkyl aluminum.
    Type: Grant
    Filed: May 27, 1975
    Date of Patent: September 13, 1977
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Albert Frese, Walter Dittmann, Wolfgang Kilian
  • Patent number: 4011384
    Abstract: For preparing crystalline, thermoplastic, low-pressure terpolymers of ethene with 0.1-5 mol % butene-1 and 0.1-3 mol % butene-2 having a density of 0.94-0.96 g./cm.sup.3, a liquid phase monomer mixture consisting essentially of ethene, 0.05-10 mol % butene-1 and 20-98.9 mol % butene-2 is polymerized with a mixed polymerization catalyst comprising (a) TiCl.sub.3 . nAlCl.sub.3 wherein n is 0.2-0.6, and (b) isoprenylaluminum in a molar ratio Al : Ti of about 2-20 to form said terpolymer.
    Type: Grant
    Filed: June 10, 1975
    Date of Patent: March 8, 1977
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Fritz Baxmann, Johann Dietrich, Walter Dittmann, Albert Frese
  • Patent number: 4000354
    Abstract: Polypropylene can be polymerized with Ziegler-Natta TiCl.sub.3 or TiCl.sub.3 . (AlCl.sub.3).sub.0.2.sub.-0.6 plus chlorine containing organoaluminum compound mixed catalyst using butene-2 or a C.sub.4 -cut comprising butene-2 as the polymerization solvent without the formation of propylene-butene copolymers.
    Type: Grant
    Filed: July 23, 1974
    Date of Patent: December 28, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Fritz Baxmann, Walter Dittmann, Albert Frese, Johann Dietrich, Wolfgang Kilian
  • Patent number: 3990993
    Abstract: Particle size is increased and particle size range is decreased, e.g. narrower particle size distribution obtained of very tiny inorganic catalyst fines, (particles), particularly olefin catalysts by working these fines with very small quantities of polytetrafluoroethylene (PTFE) powder in order to trap the fines in a web of PTFE submicroscopic fibers.
    Type: Grant
    Filed: November 13, 1974
    Date of Patent: November 9, 1976
    Assignee: Exxon Research and Engineering Company
    Inventor: Harry J. Wristers
  • Patent number: 3962130
    Abstract: Ziegler-type hydrocarbon-soluble catalyst systems for the polymerization of conjugated diolefins, or mixtures thereof, to obtain high molecular weight polymers possessing varying proportions of trans-1,4 units, in the range of 50-90%. The catalyst systems are based on a non-reduced salt of titanium, an organometallic compound, and an iodine-containing compound, or iodine corresponding to the generalized formula Ti(halide).sub.4 -M.sub.n I.sub.m -AlR.sub.a X.sub.3 -a, where M is aluminum or tetravalent tin, n is 0 or 1, m is the valence of M and where n is 0, m is 2, X is Cl, Br or I, a is 2 to 3, R is alkyl, halide is Cl, Br or I, and where halide is I, M.sub.n I.sub.m may be omitted.
    Type: Grant
    Filed: January 2, 1975
    Date of Patent: June 8, 1976
    Assignee: Exxon Research and Engineering Company
    Inventors: Erik G. M. Tornqvist, Charles Cozewith
  • Patent number: 3959243
    Abstract: Stabilizing polypropylene to thermal oxidation and ageing by treating polymeric slurry thereof with aqueous solution of a surfactant. Surfactant is fatty acid ester of condensation product of ethylene oxide and sorbitan.
    Type: Grant
    Filed: January 21, 1970
    Date of Patent: May 25, 1976
    Assignee: Montecatini Edison S.p.A.
    Inventors: Franco Mattioli, Oliviero Guanciale, deceased
  • Patent number: 3959409
    Abstract: In a low pressure process for the production of crystalline propene-ethene-butene-1 terpolymers with 0.2 to 10% by weight of ethene and 0.2 to 5% by weight of butene-1 with the aid of mixed catalysts of TiCl.sub.3 or TiCl.sub.3 .sup.. n AlCl.sub.3 (n = 0.2 to 0.6), and chlorine-containing organoaluminum compounds, the improvement comprising conducting the polymerization in butene-2 or in a C.sub.4 -cut containing 20-99% butene-2, containing 0.1 - 2.5% of butene-1, with the addition of 0.2 to 10% of ethene, based on the amount of propene employed.
    Type: Grant
    Filed: October 16, 1974
    Date of Patent: May 25, 1976
    Assignee: Chemische Werke Huls Aktiengesellschaft
    Inventors: Albert Frese, Fritz Baxmann, Walter Dittmann, Johann Dietrich
  • Patent number: 3954909
    Abstract: A method for producing solid polymers having a molecular weight greater than 50,000 from olefins wherein the olefin is polymerized in the absence of a liquid dispersion agent of a nature different from that of the olefin to be polymerized, and in contact with a prepolymer containing a small amount of transition metal of subgroups IV-b, V-b and VI-b having been produced by the polymerization of an olefin in a dispersion liquid containing a Ziegler-type catalyst.
    Type: Grant
    Filed: July 16, 1973
    Date of Patent: May 4, 1976
    Assignee: Naphtachimie
    Inventors: Lazlo J. Havas, Pierre M. Mangin