With Group Ivb Transition Metal Compound (ti, Zr, Hf) Patents (Class 526/158)
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Patent number: 4208497Abstract: 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: GrantFiled: March 3, 1978Date of Patent: June 17, 1980Assignee: BASF AktiengesellschaftInventors: Klaus Bronstert, Peter Klaerner, Gerhard Staiger
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Patent number: 4194992Abstract: 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: GrantFiled: July 20, 1978Date of Patent: March 25, 1980Assignee: Snamprogetti, S.p.A.Inventors: Margherita Corbellini, Alberto Greco
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Patent number: 4163831Abstract: 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: GrantFiled: October 26, 1976Date of Patent: August 7, 1979Assignee: The Dow Chemical CompanyInventor: Donald E. Gessell
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Patent number: 4151337Abstract: 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: GrantFiled: May 25, 1977Date of Patent: April 24, 1979Assignee: Mitsubishi Chemical Industries Ltd.Inventors: Natsuki Kanoh, Toru Tanaka, Nobuo Enokido
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Patent number: 4135045Abstract: 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: GrantFiled: September 1, 1976Date of Patent: January 16, 1979Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Norio Matsuzawa, Hidesaburo Oi, Hiroshi Nishimura, Shigeru Wada, Juntaro Sasaki
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Patent number: 4120823Abstract: 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: GrantFiled: November 30, 1977Date of Patent: October 17, 1978Assignee: BASF AktiengesellschaftInventors: Heinz Mueller-Tamm, Hans Schick, James F. R. Jaggard, Johann Nickl
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Patent number: 4110524Abstract: 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: GrantFiled: April 24, 1974Date of Patent: August 29, 1978Assignee: Chemische Werks Huels A.G.Inventor: Albert Frese
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Patent number: 4098907Abstract: 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: GrantFiled: December 9, 1976Date of Patent: July 4, 1978Assignee: Toyo Stauffer Chemical Co., Ltd.Inventors: Shoichi Tokunaga, Atsumi Kato, Yoshikazu Takahashi, Kiyoshi Yamane
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Patent number: 4093790Abstract: 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: GrantFiled: January 5, 1972Date of Patent: June 6, 1978Assignee: Labofina S.A.Inventor: William J. I. Bracke
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Patent number: 4079175Abstract: 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: GrantFiled: August 30, 1976Date of Patent: March 14, 1978Assignee: Toyo Stauffer Chemical Co., Ltd.Inventors: Shoichi Tokunaga, Atsumi Kato, Teruhiro Setoguchi, Shoji Mizuno
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Patent number: 4048419Abstract: 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: GrantFiled: May 27, 1975Date of Patent: September 13, 1977Assignee: Chemische Werke Huls AktiengesellschaftInventors: Albert Frese, Walter Dittmann, Wolfgang Kilian
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Patent number: 4011384Abstract: 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: GrantFiled: June 10, 1975Date of Patent: March 8, 1977Assignee: Chemische Werke Huls AktiengesellschaftInventors: Fritz Baxmann, Johann Dietrich, Walter Dittmann, Albert Frese
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Patent number: 4000354Abstract: 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: GrantFiled: July 23, 1974Date of Patent: December 28, 1976Assignee: Chemische Werke Huls AktiengesellschaftInventors: Fritz Baxmann, Walter Dittmann, Albert Frese, Johann Dietrich, Wolfgang Kilian
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Patent number: 3990993Abstract: 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: GrantFiled: November 13, 1974Date of Patent: November 9, 1976Assignee: Exxon Research and Engineering CompanyInventor: Harry J. Wristers
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Patent number: 3962130Abstract: 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: GrantFiled: January 2, 1975Date of Patent: June 8, 1976Assignee: Exxon Research and Engineering CompanyInventors: Erik G. M. Tornqvist, Charles Cozewith
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Patent number: 3959243Abstract: 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: GrantFiled: January 21, 1970Date of Patent: May 25, 1976Assignee: Montecatini Edison S.p.A.Inventors: Franco Mattioli, Oliviero Guanciale, deceased
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Patent number: 3959409Abstract: 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: GrantFiled: October 16, 1974Date of Patent: May 25, 1976Assignee: Chemische Werke Huls AktiengesellschaftInventors: Albert Frese, Fritz Baxmann, Walter Dittmann, Johann Dietrich
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Patent number: 3954909Abstract: 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: GrantFiled: July 16, 1973Date of Patent: May 4, 1976Assignee: NaphtachimieInventors: Lazlo J. Havas, Pierre M. Mangin