Non-metal Material Is Organic Halogen-containing Compound Patents (Class 526/144)
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Patent number: 4410640Abstract: Process for producing a porous acetylene high polymer by lyophilizing a gel-like composition composed of 1 part by weight of an acetylene high polymer having a fibril structure and 1 to 1,000 parts by weight of an organic solvent.Type: GrantFiled: September 11, 1981Date of Patent: October 18, 1983Assignee: Showa Denko K.K.Inventors: Yukio Kobayashi, Hideki Shirakawa, Sakuji Ikeda
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Patent number: 4401799Abstract: A titanium trichloride catalytic complex is produced by reducing titanium tetrachloride with an organo-metal compound and then treating the resulting reduced solids product with a chlorinated saturated aliphatic hydrocarbon having three to eight carbon atoms in the presence of a complexing agent. The resulting titanium trichloride complex composition, when employed as a co-catalyst with an organo-metal compound for Ziegler-type catalysts in polymerization of .alpha.-olefins, results in uniform polymer grains with unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: July 20, 1979Date of Patent: August 30, 1983Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Eiji Sezaki, Naomi Inaba, Tokuo Makishima, Koh Watanabe, Shozo Wada
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Patent number: 4395358Abstract: A titanium trichloride catalyst complex is produced by reducing titanium tetrachloride with an organo-metal compound and then activating the resulting reduced solids by treatment with a chlorinated hydrocarbon and titanium tetrachloride in the presence of a Lewis base complexing agent. The employment of the chlorinated hydrocarbon and titanium tetrachloride in the presence of the Lewis base complexing agent unexpectedly produces a synergistic effect whereby activating conditions, e.g., temperature, time and TiCl.sub.4 concentration can be employed resulting in a titanium trichloride complex having superior alpha-olefin polymerization properties as compared to titanium trichloride catalyst complexes obtained by treatment under the same conditions in the absence of either titanium tetrachloride or chlorinated hydrocarbon. Moreover, unexpectedly high yields of activated catalyst can be recovered without loss of activity.Type: GrantFiled: November 19, 1980Date of Patent: July 26, 1983Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers
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Patent number: 4393182Abstract: An olefin polymerization process comprises contacting the monomer to be polymerized with a catalyst composition comprising: an organoaluminum compound, a first electron donor, and a product obtained by contacting a solid component comprising a magnesium halide in which the atomic ratio of chlorine to magnesium is at least 1.2, a titanium halide and a second electron donor, with a halohydrocarbon and thereafter with a tetravalent titanium compound.Type: GrantFiled: November 5, 1981Date of Patent: July 12, 1983Assignee: Shell Oil CompanyInventors: Brian L. Goodall, Adrianus A. van der Nat, Willem Sjardijn
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Patent number: 4379899Abstract: High molecular weight polybutenes having a viscosity SSU above 1,000,000 at 210.degree. F. are produced by using a three-component catalyst system containing an alkyl aluminium halide, tertiary butyl halide and a metal halide selected from SnCl.sub.4, SnBr.sub.4, TiCl.sub.4, and TiBr.sub.4. The reaction phase is homogeneous and the catalyst components are added as a solution in an inert solvent. The polyisobutene product so produced are useful additives for oil, adhesives and mastics.Type: GrantFiled: October 20, 1981Date of Patent: April 12, 1983Assignee: BP Chemicals LimitedInventor: Christopher R. Marsh
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Patent number: 4379074Abstract: This application relates to a process for the homopolymerization (or copolymerization) of unsaturated compounds, particularly ethylene and higher alpha olefines, to give homopolymers (or copolymers) having a wide molecular weight distribution.The polymerization yields are very high, even at relatively low pressures (10 bars), i.e. such as not to require scrubbing in order to remove the catalytic residue from the polymer.These results are obtained by using, in union with an organometallic aluminium compound, a catalyst in the form of a new titanium trihalide-based chemical composition satisfying the following formula:TiX.sub.3.mM'Y.sub.n.qM"Y'.sub.p.cAlY".sub.3-s R.sub.Type: GrantFiled: December 5, 1980Date of Patent: April 5, 1983Assignees: Anic S.p.A., Snamprogetti, S.p.A.Inventors: Agostino Balducci, Margherita Corbellini, Mirko Osellame
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Patent number: 4378455Abstract: The present disclosure relates to a process for alternating copolymerization of propylene and butadiene in the absence of a polymerization solvent. The disclosure contains information relative to commercial production of the said copolymer and detailed teachings relative to the preparation of catalyst for use in the said process.Type: GrantFiled: February 19, 1980Date of Patent: March 29, 1983Assignee: Maruzen Petrochemical Co., Ltd.Inventors: Akihiro Kawasaki, Tsuyoshi Matsumoto, Masanobu Taniguchi, Isao Maruyama, Masaaki Matsui, Masao Kaneko, Akihiko Imai
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Titanium trichloride catalytic component and method for homo- or co-polymerization of .alpha.-olefin
Patent number: 4361498Abstract: A highly active titanium trichloride catalytic component to be used for polymerization of .alpha.-olefin has highly uniform particle size the mean value of which is adjustable to a desired value between 10 and 500.mu.; and a method for manufacturing an .alpha.-olefin polymer having extremely uniform particle diameter by using a catalyst which is prepared by combining the above stated catalytic component with an organo-aluminum compound. In the manufacture of the olefin polymer, deashing processes can be either omitted or simplified. Further, the pelletizing process on the catalytic component or the polymer also can be omitted.Type: GrantFiled: December 1, 1980Date of Patent: November 30, 1982Assignee: Toyo Stauffer Chemical Co., Ltd.Inventors: Yoichi Sunada, Yoshikazu Takahashi, Masaru Takitani -
Patent number: 4355143Abstract: The invention concerns a process for the production of polyolefins with a wide range of distribution in respect of molecular masses.The process comprises polymerizing ethylene, which is optionally accompanied by one or more other olefins, in contact with a catalytic system comprising:(a) a catalyst comprising a solid compound of titanium, magnesium and a halogen such as chlorine or bormine(b) one or more organometallic compounds of a metal of groups II and III of the periodic table of elements(c) one or more halogenated ethylenic hydrocarbons.The resulting polyolefins are particularly suitable for being shaped by means of extrusion-blowing.Type: GrantFiled: September 17, 1979Date of Patent: October 19, 1982Assignee: NaphtachimieInventors: Dominique Lassalle, Laszlo Havas
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Patent number: 4330433Abstract: 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: GrantFiled: January 15, 1981Date of Patent: May 18, 1982Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers, deceased
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Patent number: 4330647Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to 320.degree. C. with a catalyst comprising a component (A) and an organometal component (B), the component (A) being produced by reacting a hydrocarbon-soluble organomagnesium component (i) of the formula,M.sub..alpha. MgR.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2 D.sub.t.alpha., p, q, r, s and t each independently is O or a number greater than 0,p+q+r+s=m.alpha.+2O.ltoreq.(r+s)/(.alpha.+1)<2,m is the valence of M, M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 is a hydrocarbon group having 1 to 20 carbon atoms, R.sup.2 is a secondary or tertiary alkyl group having 3 to 20 carbon atoms,X.sup.1 and X.sup.2 each independently is a hydrogen atom or an organic electronegative group containing O, N or S,D is an electron donor,with a compound (ii) of the formula,R.sub.a.sup.3 C Y.sub.4-awhereinR.sup.Type: GrantFiled: August 13, 1980Date of Patent: May 18, 1982Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4329253Abstract: An olefin polymerization catalyst composition comprising:(a) a reaction product of an organo aluminium compound and an electron donor, and(b) a product obtained by contacting a solid component comprising a magnesium halide in which the atomic ratio of chlorine to magnesium is at least 1.2, a titanium halide and an electron donor, with a halohydrocarbon and with a tetravalent titanium compound.Type: GrantFiled: April 25, 1980Date of Patent: May 11, 1982Assignee: Shell Oil CompanyInventors: Brian L. Goodall, Adrianus A. Van der Nat, Willem Sjardijn
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Patent number: 4321346Abstract: A titanium trichloride catalytic complex is produced by reducing titanium tetrachloride with an organo-metal compound and then treating the resulting reduced solids product with a chlorinated saturated hydrocarbon having two carbon atoms in the presence of a complexing agent. The resulting titanium trichloride complex composition, when employed as a co-catalyst with an organo-metal compound for Ziegler-type catalysts in polymerization of .alpha.-olefins, results in uniform polymer grains with unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: July 20, 1979Date of Patent: March 23, 1982Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Naomi Inaba, Tukuo Makishima, Koh Watanabe, Shozo Wada
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Patent number: 4319011Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins at temperatures above 140.degree. C. are provided by reacting a transition metal compound such as tetra(isopropoxy)titanium, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium.x triethylaluminum and a hydrogen halide or an active hydrocarbyl halide such as t-butyl chloride. 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.Type: GrantFiled: September 16, 1980Date of Patent: March 9, 1982Assignee: The Dow Chemical Co.Inventors: Kirby Lowery, Jr., George W. Knight, James A. May, Jr.
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Patent number: 4308369Abstract: Olefins are polymerized in the presence of a catalyst prepared by reacting tetravalent 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 or 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: GrantFiled: June 2, 1980Date of Patent: December 29, 1981Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
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Patent number: 4299936Abstract: A transition metal compound containing at least one .pi.-bonded arene is contacted with an inorganic oxide, hydroxide, oxyhalide, hydroxyhalide or halide. The transition metal compound can be a compound such as titanium(O)ditoluene or TiCl.sub.2.2AlCl.sub.3 durene. The inorganic compound is preferably of high surface area and this may be inherent in the compound or can be achieved by a grinding procedure. The inorganic compound can be treated with a halogen containing compound either before, during or after the contacting with the transition metal compound. The product of the contacting is useful either as catalyst for the polymerization of unsaturated hydrocarbon monomers or as a component of such a catalyst. When used as a component of an olefine polymerization catalyst, the transition metal product can be mixed with an organo-aluminum compound and a Lewis Base compound such as an ester.Type: GrantFiled: August 7, 1978Date of Patent: November 10, 1981Assignee: Imperial Chemical Industries LimitedInventors: John P. Candlin, Keith C. Wilson, Ronald Pearce
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Patent number: 4287091Abstract: Polymerization, catalysts, and preparation thereof comprising milling magnesium metal, an organic halide, and titanium tetrahalide or the milled product in the presence of at least one of magnesium oxide, a triaryl phosphite, a polymeric material, titanium tetrahalide, vanadium tetrahalide, silicon tetrahalide, and an aluminum trihalide. The milled catalyst component can be heat treated prior to activation. The milled titanium catalyst component is activated with an organoaluminum activator producing a catalyst for olefin polymerization.Type: GrantFiled: August 3, 1979Date of Patent: September 1, 1981Assignee: Phillips Petroleum Co.Inventor: Charles M. Selman
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Patent number: 4276394Abstract: Novel telechelic halogenated polymers of cationically polymerizable olefin monomers are formed carrying from 2 to about 6 terminal halogens. The telechelic halogenated polymers are formed by reacting the monomer with an initiator transfer agent, carrying at least two tertiary halogens, and under cationic polymerization conditions. Additionally, novel thermoplastic elastomer block copolymers are formed from these telechelic halogenated polymers by reacting the latter with vinyl aromatic monomers in the presence of a coinitiator.Type: GrantFiled: September 10, 1979Date of Patent: June 30, 1981Assignee: The University of AkronInventors: Joseph P. Kennedy, Robert A. Smith, Louis R. Ross, Jr.
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Patent number: 4272404Abstract: Large particle size polyolefin is obtained by polymerizing mono-olefins in the presence of a supported olefin catalyst which has been ball milled in the presence of small quantities of polytetrafluoroethylene (PTFE) powder in order to trap, i.e., entangle, the supported catalyst in a web of PTFE submicroscopic fibers.Type: GrantFiled: July 10, 1979Date of Patent: June 9, 1981Inventor: Harry J. Wristers
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Patent number: 4272405Abstract: Particle size is increased and particle size range can be decreased, i.e., narrower particle size distribution can be obtained for Ziegler transition metal halide catalysts by working the catalysts with very small quantities of a fibrillatable polytetrafluoroethylene (PTFE) powder in order to trap, i.e., entangle the catalyst in a web of PTFE submicroscopic fibers.Type: GrantFiled: August 27, 1979Date of Patent: June 9, 1981Inventors: Harry J. Wristers, deceased, by Joy K. Wristers, sole beneficiary
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Patent number: 4267292Abstract: A process for polymerizing alpha-olefins in the presence of a Ziegler-type catalyst wherein at least one of dichloroethane, dichloropropane and chlorine gas is added to the process after the polymerization has been initiated. This invention is especially useful when the olefin is propylene and the catalyst is a titanium trichloride complex.Type: GrantFiled: December 26, 1979Date of Patent: May 12, 1981Assignee: The Standard Oil CompanyInventors: Kenneth C. Benton, James F. White, Curtis E. Uebele, Raymond J. Weinert, Jr.
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Patent number: 4262104Abstract: A titanium trichloride catalyst complex is produced by reducing titanium tetrachloride with an organo-metal compound and then activating the resulting reduced solids by treatment with a chlorinated hydrocarbon and titanium tetrachloride in the presence of a Lewis base complexing agent. The employment of the chlorinated hydrocarbon and titanium tetrachloride in the presence of the Lewis base complexing agent unexpectedly produces a synergistic effect whereby activating conditions, e.g., temperature, time and TiCl.sub.4 concentration can be employed resulting in a titanium trichloride complex having superior alpha-olefin polymerization properties as compared to titanium trichloride catalyst complexes obtained by treatment under the same conditions in the absence of either titanium tetrachloride or chlorinated hydrocarbon. Moreover, unexpectedly high yields of activated catalyst can be recovered without loss of activity.Type: GrantFiled: February 12, 1979Date of Patent: April 14, 1981Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers
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Patent number: 4260709Abstract: This invention is addressed to catalysts for use in the polymerization of olefins comprising compounds of magnesium and one or more transition metals of groups IVa, Va and VIa, which are at least partially reduced, with the catalysts being prepared by reaction of magnesium, at least one mono-halogenated hydrocarbon and a compound of a transition metal having a valence of at least 4. The catalysts can be used for the polymerization of olefins, such as ethylene, in the low-pressure process.Type: GrantFiled: August 24, 1978Date of Patent: April 7, 1981Assignee: NaphthachimieInventors: Daniel C. Durand, Pierre M. F. Mangin
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Patent number: 4252670Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with an halogenating agent such as silicon tetrachloride or hydrogen chloride, and then reacting the product with a Lewis Base compound, particularly an ester and finally with titanium tetrachloride. The product obtained is combined with an organo-aluminium compound preferably together with a Lewis Base and used to polymerize an olefine monomer. The catalyst has a high activity and is stereospecific.Type: GrantFiled: March 26, 1979Date of Patent: February 24, 1981Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens
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Titanium trichloride catalytic component and method for homo- or co-polymerization of .alpha.-olefin
Patent number: 4251388Abstract: A titanium trichloride catalytic component obtained by separating it out of a solution consisting of titanium tetrachloride, an organic ether compound and an organo-aluminum compound dissolved in a solvent. The solvent is a mixture consisting of a saturated aliphatic hydrocarbon and/or an alicyclic hydrocarbon with 20 to 70% by volume of a concomitant aromatic hydrocarbon halide included therein. The organo-aluminum compound, the titanium tetrachloride and the organic ether compound is added to this mixed solvent at a solvent temperature not exceeding 55.degree. C. Following this, the solvent temperature is raised up to a value between 45.degree. and 150.degree. C. over a period of 10 minutes to 24 hours with an organic ether compound and/or titanium tetrachloride further added during this temperature raising process to obtain thereby a titanium trichloride catalytic component having average particle diameter between 10 and 1000.mu. . Then homo- or co-polymerization of .alpha.Type: GrantFiled: June 19, 1979Date of Patent: February 17, 1981Assignee: Toyo Stauffer Chemical Co., Ltd.Inventors: Yoshikazu Takahashi, Yoichi Sunada, Masaru Takitani -
Patent number: 4250288Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins at temperatures above 140.degree. C. are provided by reacting a transition metal compound such as tetra(isopropoxy)titanium, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum, e.g., di-n-butylmagnesium.x triethylaluminum and a hydrogen halide or an active hydrocarbyl halide such as t-butyl chloride. 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.Type: GrantFiled: February 3, 1977Date of Patent: February 10, 1981Assignee: The Dow Chemical CompanyInventors: Kirby Lowery, Jr., George W. Knight, James A. May, Jr.
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Patent number: 4250286Abstract: Compositions consisting of the reaction product or complex resulting from the mixing of a transition metal compound such as a tetraalkoxy titanium compound and a zinc compound such as a dialkyl zinc compound are useful in the preparation of catalysts for polymerizing .alpha.-olefins as ultra-high efficiencies at high polymerization temperatures.Type: GrantFiled: September 28, 1979Date of Patent: February 10, 1981Assignee: The Dow Chemical CompanyInventor: Randall S. Shipley
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Patent number: 4248988Abstract: The process described herein comprises the polymerization of a conjugated diene, such as butadiene-1,2, isoprene, etc., in an anhydrous hydrocarbon solution and in intimate contact with a catalyst system comprising a cobalt or nickel component, a hydrocarbyl aluminum compound and a halogenated hydrocarbon, such as CCl.sub.4, CH.sub.2 Cl.sub.2, CBr.sub.4, CHCl.sub.3, CHBr.sub.3, etc., containing 1-10 carbon atoms and 1-6 halogen atoms per molecule, with at least one of said halogen atoms being attached to an aliphatic carbon atom. Analysis shows that the polymer product has cyclic structure and this is confirmed by the determination of residual unsaturation which is found generally to be less than 20 percent of the normal unsaturation of the polymeric diene. The products are useful in molding compositions.Type: GrantFiled: October 18, 1979Date of Patent: February 3, 1981Assignee: The Firestone Tire & Rubber CompanyInventor: Adel F. Halasa
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Patent number: 4246384Abstract: Magnesium metal is contacted with an organic halide in the absence of an ether or other complexing diluent to produce a magnesium reducing agent for converting titanium tetrahalide to titanium trihalide. In a first embodiment, the magnesium metal, organic halide, and titanium tetrahalide are introduced into a mill and milled. In a second embodiment, the organic halide is metered dropwise onto the magnesium metal in the absence of any extraneous diluent, and the resulting magnesium reducing agent is thereafter added to a titanium tetrahalide and milled. In a third embodiment, an organic halide containing the titanium tetrahalide is metered dropwise onto magnesium metal in the absence of any extraneous diluent. In each instance the resulting titanium trihalide catalyst component is contacted with an organoaluminum compound activator and used for the polymerization of olefins, preferably the polymerization of propylene.Type: GrantFiled: November 8, 1978Date of Patent: January 20, 1981Assignee: Phillips Petroleum CompanyInventor: Charles M. Selman
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Patent number: 4246136Abstract: A supported titanium catalyst is produced by cogrinding, in combination, a magnesium halide, tetravalent titanium halide, organic acid ester, and a halogen compound selected from organic halogen compounds and halogen-containing compounds of Group IVa elements of the Periodic Table except carbon, and then treating the resulting titanium-containing solid with a hydrocarbon and/or a halogen compound as described above. The resulting supported titanium catalyst, when employed as a titanium component with an organo aluminum catalyst component for the catalyst system in a process for stereoregular polymerization of .alpha.-olefins results in unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: April 11, 1979Date of Patent: January 20, 1981Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Masafumi Imai, Naomi Inaba, Makoto Yoda, Shozo Wada
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Patent number: 4242230Abstract: A supported titanium catalyst, adaptable for use in the stereoregular polymerization of .alpha.-olefins, is produced by treating a supported titanium-containing solid, obtained by cogrinding a magnesium halide, tetravalent titanium halide and organic acid ester, with a hydrocarbon, organo halogen compound or mixture thereof with heating. The resulting supported titanium catalyst, when employed as a titanium component with an organo aluminum catalyst component for the catalyst system in a process for stereoregular polymerization of .alpha.-olefins, produces high polymerization activity and unexpectedly high stereoregular polymer yielding ratios.Type: GrantFiled: April 11, 1979Date of Patent: December 30, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Masafumi Imai, Naomi Inaba, Makoto Yoda, Shozo Wada
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Patent number: 4242231Abstract: A supported titanium catalyst is produced by cogrinding, in combination, a magnesium halide, tetravalent titanium halide, organic acid ester, and an organic halogen compound. The resulting supported titanium catalyst, when employed as a titanium component with an organo aluminum catalyst component for the catalyst system in a process for stereoregular polymerization of .alpha.-olefins, produces high polymerization activity and unexpectedly high stereoregular polymer yielding ratios.Type: GrantFiled: April 11, 1979Date of Patent: December 30, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Masafumi Imai, Naomi Inabe, Makoto Yoda, Shozo Wada
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Patent number: 4240928Abstract: A titanium trichloride catalytic complex is produced by reducing titanium tetrachloride with an alkylaluminum halide composition at low temperature and then treating the resulting reduced solids product by contacting it at elevated temperature with a dialkyl ether having alkyl groups of 4 to 5 carbon atoms and with hexachloroethane, the proportion of dialkyl ether being at least 1 mol per 1 mol of hexachloroethane and the proportion of hexachloroethane being at least greater than about 0.5 mol per 1 gram atom of titanium in the reduced solids product. The resulting titanium trichloride complex composition, when employed as co-catalyst with an organo-metal compound for Ziegler-type catalysts in polymerization of .alpha.-olefins, results in uniform polymer grains with unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: July 25, 1978Date of Patent: December 23, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Naomi Inaba, Tukuo Makishima, Koh Watanabe, Shozo Wada
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Patent number: 4235745Abstract: A titanium trichloride catalytic component suitable for preparing highly stereospecific polymers having highly uniform particle diameters from .alpha.-olefins is prepared by precipitating such catalytic component from a solution of TiCl.sub.4 in a solvent comprising a saturated aliphatic hydrocarbon and/or an alicyclic hydrocarbon. Such solution is obtained by dissolving TiCl.sub.4, an ether and an organo-aluminum compound having the formula AlR.sub.n X.sub.3-n (wherein R, X and n are as defined hereinafter) in the solvent. The organo-aluminum compound is added at a solvent temperature not exceeding 55.degree. C. in the concomitant presence of an aromatic hydrocarbon halide; subsequently, the temperature of the resulting system is raised to 45.degree.-150.degree. C. over a period of 10 minutes to 24 hours to precipitate the catalytic component which has a uniform particle diameter between 10 and 1000.mu..Homo- or co-polymerization of .alpha.Type: GrantFiled: December 20, 1978Date of Patent: November 25, 1980Assignee: Toyo Stauffer Chemical Co., Ltd.Inventors: Yoshikazu Takahashi, Yoichi Sunada, Masaru Takitani
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Patent number: 4232140Abstract: Trichlorofluoromethane is used as a promoter in the polymerization and copolymerization of ethylene with supported Ziegler-type vanadium compound/alkylaluminum compound catalysts in the presence of hydrogen. The use of the promoter leads to the formation of non-rubbery, semi-crystalline polymers in high yields, does not alter the basic molecular weight distribution of the polymers, permits independent control of molecular weight by hydrogen, and imparts no significant level of halogen to the product.Type: GrantFiled: October 23, 1978Date of Patent: November 4, 1980Assignee: Cities Service CompanyInventor: Morris R. Ort
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Patent number: 4224185Abstract: 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: GrantFiled: March 26, 1979Date of Patent: September 23, 1980Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers
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Patent number: 4224183Abstract: A special process for the preparation of a titanium component for polymerization catalysts of the Ziegler-Natta type, wherein (1) in a first stage (1.1) an alcoholate of the formula Mr(OR).sub.2, where R is lower alkyl and (1.2) a chlorotoluene of the formula ##STR1## where X is chlorine or hydrogen, are milled together in a particular molar ratio in a vibratory ball mill under particular milling conditions, especially a relatively low temperature, in the absence of a diluent, thereafter (2) in a second stage (2.1) the material resulting from stage (1) is brought together with (2.2) titanium tetrachloride in a particular ratio, the batch is kept for some time at an elevated temperature, with constant mixing, and the resulting solid is isolated, excess titanium tetrachloride being separated off, and finally (3) in a third stage (3.1) the solid resulting from stage (2) is again brought together with (3.Type: GrantFiled: July 5, 1979Date of Patent: September 23, 1980Assignee: BASF AktiengesellschaftInventor: Gerhard Staiger
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Patent number: 4222895Abstract: Phosphorus oxytrichloride modified titanium trichloride polymerization catalysts of improved efficiency and/or isotacticity are obtained when the modification reaction is carried out in the presence of methylene chloride.Type: GrantFiled: May 4, 1979Date of Patent: September 16, 1980Assignee: Dart Industries Inc.Inventors: John L. H. Allan, Birendra K. Patnaik
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Patent number: 4220555Abstract: 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: GrantFiled: September 7, 1978Date of Patent: September 2, 1980Assignee: Exxon Research & Engineering Co.Inventors: Harry J. Wristers, Eugene E. Poirot, Terrence Huff
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Patent number: 4217245Abstract: 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: GrantFiled: June 2, 1978Date of Patent: August 12, 1980Assignee: Snamprogetti, S.p.A.Inventors: Margherita Corbellini, Alessandro Gamba, Carlo Busetto
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Patent number: 4217432Abstract: A solid catalyst for olefin polymerization which is obtained by the catalytic treatment of a titanium trichloride composition with a mixture of a halogenated hydrocarbon and an ether, the composition being produced by subjecting a solid reduction product, which is obtained by reduction of titanium tetrachloride with an organo-aluminum compound, to heat treatment or to catalytic treatment with a specific organo-aluminum compound, aluminum halide, an ether and the like. In the polymerization of an olefin, combined catalyst systems of this solid catalyst and organo-aluminum compounds as activators can be used for efficient production of olefin polymers having a high crystallinity.Type: GrantFiled: August 2, 1978Date of Patent: August 12, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Kazuhiro Matsumura, Toshio Sasaki, Masahisa Ohkawa
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Patent number: 4207205Abstract: Novel TiCl.sub.3 catalytic complexes for the stereospecific polymerization of alpha-olefins and to a process for preparation of these catalytic complexes which are obtained by reduction of TiCl.sub.4 in the presence of a Lewis base which has preferably been complexed with the reducing agent. Furthermore, the present invention relates to a process for improved polymerization of alpha-olefins to crystalline polyolefins in high yields and high stereospecificity using these catalytic complexes.Type: GrantFiled: February 17, 1978Date of Patent: June 10, 1980Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers
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Patent number: 4189553Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are provided by reacting a trivalent titanium halide complex such as an alcohol complex of titanium trichloride, an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an alkyl aluminum and halide source such as a hydrogen halide or an alkyl aluminum halide. 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.Type: GrantFiled: June 2, 1978Date of Patent: February 19, 1980Assignee: The Dow Chemical CompanyInventor: Donald F. Birkelbach
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Patent number: 4189554Abstract: A magnesium reducing agent is prepared by reacting an organic halide and magnesium metal in the absence of an ether or other complexing diluent, preferably in the absence of any extraneous diluent, to form a magnesium reducing agent which is thereafter milled with an organoaluminum compound to form a cocatalyst. In one embodiment the halide is added dropwise to the magnesium metal. The resulting milled product is thereafter contacted with a titanium tetrahalide to form a catalyst. This catalyst is suitable for olefin polymerization and particularly suitable for the polymerization of ethylene.Type: GrantFiled: March 21, 1978Date of Patent: February 19, 1980Assignee: Phillips Petroleum CompanyInventor: Oscar D. Nowlin
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Patent number: 4183826Abstract: A titanium trichloride catalytic complex is produced by reducing titanium tetrachloride with an organo-metal compound and then treating the resulting reduced solids product with a chlorinated saturated aliphatic hydrocarbon having three to eight carbon atoms in the presence of a complexing agent. The resulting titanium trichloride complex composition, when employed as a co-catalyst with an organo-metal compound for Ziegler-type catalysts in polymerization of .alpha.-olefins, results in uniform polymer grains with unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: February 9, 1979Date of Patent: January 15, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Eiji Sezaki, Naomi Inaba, Tokuo Makishima, Koh Watanabe, Shozo Wada
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Patent number: 4182691Abstract: A titanium trichloride catalytic complex is produced by reducing titanium tetrachloride with an organo-metal compound and then treating the resulting reduced solids product with a chlorinated saturated hydrocarbon having two carbon atoms in the presence of a complexing agent. The resulting titanium trichloride complex composition, when employed as a co-catalyst with an organo-metal compound for Ziegler-type catalysts in polymerization of .alpha.-olefins, results in uniform polymer grains with unexpectedly high polymerization activity and high stereoregular polymer yielding ratios.Type: GrantFiled: February 9, 1979Date of Patent: January 8, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Hiroshi Ueno, Naomi Inaba, Tukuo Makishima, Koh Watanabe, Shozo Wada
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Patent number: 4182811Abstract: 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: GrantFiled: February 27, 1978Date of Patent: January 8, 1980Inventors: Jury N. Bocharov, Viktor A. Kabanov, Marina A. Martynova, Valery G. Popov, Vladimir I. Smetanjuk, Viktor V. Fedorov
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Patent number: 4176219Abstract: In the production of 1,2-polybutadiene by contacting 1,3-butadiene with a catalyst composed of (A) a cobalt compound, (B) an organic phosphine compound, (C) trialkylaluminum and (D) water in an amount of 0.25 to 1.5 moles per mole of said trialkylaluminum, the addition of (E) at least one compound selected from the group consisting of allyl halides, alkyl-substituted allyl halides, benzyl halides, alkyl-substituted benzyl halides, and tertiary aliphatic halides to the reaction system enables the molecular weight of the objective 1,2-polybutadiene to be regulated to any desired value without causing any change in microstructure and degree of crystallization of the product and also without deteriorating so much the polymerization activity.Type: GrantFiled: May 30, 1978Date of Patent: November 27, 1979Assignee: Japan Synthetic Rubber Co., Ltd.Inventors: Kenya Makino, Tsunezo Ishikawa, Koei Komatsu
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Patent number: 4165298Abstract: A solid catalyst for polymerization of olefins prepared by treatment of a titanium trichloride composition with a mixture of (1) a halogen, an interhalogen compound or a halogenated hydrocarbon compound, and (2) an ether which, in combination with organoaluminum compounds as activators, can be used to polymerize olefins for the efficient production of highly crystalline olefin polymers.Type: GrantFiled: September 8, 1977Date of Patent: August 21, 1979Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yoshiharu Fukui, Kazuhiro Matsumura, Toshio Sasaki, Masahisa Okawa
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Patent number: 4151112Abstract: A titanium trichloride catalyst complex is produced by reducing titanium tetrachloride with an organo-metal compound and then activating the resulting reduced solids by treatment with a chlorinated hydrocarbon and titanium tetrachloride in the presence of a Lewis base complexing agent. The employment of the chlorinated hydrocarbon and titanium tetrachloride in the presence of the Lewis base complexing agent unexpectedly produces a synergistic effect whereby activating conditions, e.g., temperature, time and TiCl.sub.4 concentration can be employed resulting in a titanium trichloride complex having superior alpha-olefin polymerization properties as compared to titanium trichloride catalyst complexes obtained by treatment under the same conditions in the absence of either titanium tetrachloride or chlorinated hydrocarbon. Moreover, unexpectedly high yields of activated catalyst can be recovered without loss of activity.Type: GrantFiled: June 30, 1977Date of Patent: April 24, 1979Assignee: Exxon Research & Engineering Co.Inventor: Harry J. Wristers