At Least One Atom Of Group Iiia Metal (al, Ga, In, Tl) In Elemental Form Or Bonded To Hydrogen Or Carbon Atom Patents (Class 526/151)
Two or more group iiia metals in elemental form or bonded to hydrogen or carbon atom (Class 526/153)
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Patent number: 4329256Abstract: A catalyst system of such high efficiency that the purification of the polymer can be dispensed with is obtained by first reacting a magnesium halide with an electron donor and/or a cyclopolyene, bringing the product obtained into contact with a TiCl.sub.3 -containing compound and using a stereoregulator. The system has a high stereospecificity whereby the proportion of atactic polymer is kept low. No excess amount of transition metal halides is required and the polymer obtained has uniform coarse particles and a very low halogen content. spThis is a continuation, of application Ser. No. 54,922 filed July 5, 1979, now abandoned.Type: GrantFiled: March 9, 1981Date of Patent: May 11, 1982Assignee: Hoechst AktiengesellschaftInventors: Kurt Rust, Ludwig Brinkmann, Paul Lutz
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Patent number: 4324691Abstract: A component for an olefin polymerisation catalyst which component is the product of treating a particulate support material with (a) an organomagnesium compound, (b) a transition metal compound of Groups IVA, VA or VIA, e.g. bis-butoxy titanium dichloride, (c) a pacifying agent, e.g. HCl and (d) optionally an aluminium compound, e.g. ethyl aluminium dichloride, an organometallic compound, e.g. zirconium tetrabenzyl, a halogenating agent e.g. silicon tetrachloride, or a Lewis Base compound, e.g. ethyl benzoate.Type: GrantFiled: July 1, 1980Date of Patent: April 13, 1982Assignee: Imperial Chemical Industries LimitedInventors: Angus J. Hartshorn, Eric Jones
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Patent number: 4323665Abstract: .alpha.-Olfins, particularly higher olefins, are polymerized in the presence of a catalyst prepared by reacting (A) tetravalent tianium compounds such as titanium tetraalkoxide, (B) an organoaluminum compound, (C) an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an organoaluminum compound such as triethyl aluminum and, (D) as a halide source, a tetravalent tin compound such as tin tetrachloride. Polymers prepared by this process provide higher efficiencies than polymers prepared from a process utilizing catalysts employing HCl as the halide source.Type: GrantFiled: April 14, 1980Date of Patent: April 6, 1982Assignee: The Dow Chemical Co.Inventors: Kirby Lowery, Jr., Donald F. Birkelbach, Randall S. Shipley
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Patent number: 4322514Abstract: According to this invention, there is provided a process for preparing a non- or low-crystalline soft copolymer, characterized in that 50 to 98 mole % of propylene, 0.2 to 30 mole % of ethylene and 0.2 to 45 mole % of a straight-chained .alpha.-olefin having not less than four carbon atoms are copolymerized using a catalyst, said catalyst comprising (1) a solid substance containing magnesium and titanium and (2) an organometallic compound.Type: GrantFiled: February 20, 1980Date of Patent: March 30, 1982Assignee: Nippon Oil Company, LimitedInventors: Mituji Miyoshi, Kazuo Matsuura, Yoshio Tajima
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Patent number: 4321347Abstract: An alpha olefin is polymerized to obtain highly crystalline polymers by subjecting the alpha olefin to polymerization conditions using as a catalyst therefor the reaction product of (A) an aluminum hydrocarbyl treated with an electron donor compound and (B) a support containing chlorine, bromine and magnesium, wherein the molar ratio of bromine to chlorine ranges between about 1:99 to about 50:50, preferably between about 2.5:97.5 to about 20:80, and most preferably between about 2.5:97.5 to about 15:85, obtained by reacting an organo magnesium compound with a mixture of chlorinated and brominated aluminum compounds, the support having been additionally treated with an electron donor compound and with titanium tetrachloride. The molar ratio of magnesium to combined chlorine and bromine in the support is not critical but generally ranges between about 1:1.6 and about 1:2.0, preferably between about 1:1.8 and about 1:2.0.Type: GrantFiled: December 29, 1980Date of Patent: March 23, 1982Assignee: Gulf Research & Development Co.Inventors: David L. Beach, Adolfo Zambelli
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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: 4311816Abstract: A solution polymerization process for the preparation of homopolymers of ethylene and copolymers of ethylene and higher .alpha.-olefins and a coordination catalyst for such a process are disclosed. In the process monomer is polymerized in the presence of the coordination catalyst which consists of a particular admixture of (a) a solution of an organoaluminum compound and an organomagnesium compound, with (b) a solution of a titanium compound and a vanadium compound. The catalyst exhibits relatively high activity in the polymerization of the monomers.Type: GrantFiled: May 5, 1980Date of Patent: January 19, 1982Assignee: E. I. Du Pont de Nemours and CompanyInventors: Alistair N. Mollison, Vaclay G. Zboril
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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: 4297463Abstract: Poly-.alpha.-olefin having an excellent H. I. is produced with an excellent yield by bringing, in the presence of an organic acid ester, a feed, containing at least one .alpha.-olefin having 3 or more carbon atoms, into contact with a catalyst which comprises (A) a solid catalytic ingredient prepared (a) by reacting a Grignard compound with an aluminium halide-tetraalkoxysilane reaction product, (b) bringing the resultant reaction product into a first contact with titanium tetrahalide, (c) treating the resultant titanium-containing solid product with an organic acid ester, and, finally, (d) bringing the treated solid product into a second contact with titanium tetrahalide, and; (B) another catalytic ingredient consisting of a trialkyl aluminium.Type: GrantFiled: May 6, 1980Date of Patent: October 27, 1981Assignee: Ube Industries, Ltd.Inventors: Haruo Ueno, Takefumi Yano, Tokuji Inoue, Shigeru Ikai, Yoshiyuki Kai, Michimasa Shimizu
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Patent number: 4296223Abstract: The present invention comprises a catalyst system, catalyst complex, and a process for the polymerization and copolymerization of alpha-olefins in which the process is carried out in the presence of a catalyst system comprising an organic compound of a metal of Group Ib, IIa, IIIb, or IVb of the Periodic Table and a solid catalyst complex prepared by reacting a divalent metal halide, an organic oxygen compound of a metal of Group IVa, Va, or VIa of the Periodic Table, and an aluminum halide.Type: GrantFiled: October 8, 1980Date of Patent: October 20, 1981Assignee: Solvay & CieInventor: Eugene Berger
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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: 4276191Abstract: Catalyst and process for polymerization of alpha-olefins to predominantly atactic products, such catalyst comprising (A) an organoaluminum component and (B) a solid reaction product of (1) a titanium (IV) component and (2) a hydrocarbon-soluble organomagnesium-organoaluminum complex.Type: GrantFiled: June 4, 1979Date of Patent: June 30, 1981Assignee: Standard Oil Company (Indiana)Inventors: Nicholas M. Karayannis, Harold Grams, John S. Skryantz
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Patent number: 4268418Abstract: A novel olefin polymerization and copolymerization catalyst and method is provided wherein the catalyst is prepared by mixing an alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR).sub.n X.sub.4-n where R is an alkyl group, preferably of 1-6 carbon atoms, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer whereby a reaction product is formed on the particles, and evaporating the solvent. The catalyst is active in the presence of an organometallic co-catalyst.Type: GrantFiled: November 19, 1979Date of Patent: May 19, 1981Assignee: Chemplex CompanyInventor: Raymond E. Hoff
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Patent number: 4264472Abstract: 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: GrantFiled: August 29, 1979Date of Patent: April 28, 1981Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Tadashi Ikegami, Hisaya Sakurai, Yoshihiko Katayama, Shigeo Tsuyama, Yukitoshi Iwashita
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Patent number: 4263171Abstract: An olefin polymerization and copolymerization catalyst active in the presence of an alkyl aluminum cocatalyst is prepared by mixing, in the presence of a solvent, particles of a silica or alumina material having reactive surface groups, and a complex of the general formula (MgR.sub.2).sub.m (AlR.sub.3 ').sub.n where R and R' are alkyl groups and m/n is between about 0.5 and 10, inclusive, to form a hydrocarbon insoluble reaction product which is then mixed, in the presence of a solvent, with a titanium, vanadium or zirconium halide, oxyhalide or alkoxyhalide, followed by evaporation of the solvent.Type: GrantFiled: August 1, 1979Date of Patent: April 21, 1981Assignee: Chemplex CompanyInventors: Mitsuzo Shida, Thomas J. Pullukat, Raymond E. Hoff
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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: 4260707Abstract: A catalyst comprising(a) a reaction mixture formed by reacting M(RCO.sub.2).sub.3 with AlR.sub.3.sup.1,(b) AlR.sub.3.sup.2 and/or HAlR.sub.2.sup.2 and(c) a Lewis acidwherein M denotes a trivalent rare earth element with an atomic number of 57 to 71, R denotes a saturated or unsaturated, straight chain or branched chain alkyl group having 1 to 20 C-atoms which may be substituted one or more times with cycloalkyl having 5 to 7-atoms and/or phenyl, the carboxyl group being attached to a primary, secondary or tertiary C-atom; a cycloalkyl group having 5 to 7 ring carbon atoms, which may be substituted one or more times with alkyl groups having from 1 to 5 C-atoms; or an aromatic group having from 6 to 10 ring carbon atoms, which may be substituted one or more times with alkyl groups having 1 to 5 C-atoms, and R.sup.1 and R.sup.2 are identical or different, straight chain or branched chain alkyl groups having from 1 to 10 C-atoms. Said catalyst may be used for polymerizing diene monomers in solution.Type: GrantFiled: February 1, 1980Date of Patent: April 7, 1981Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4250285Abstract: A process for preparing a polymer or copolymer of an olefin having at least 3 carbon atoms which comprises polymerizing or copolymerizing an olefin having at least 3 carbon atoms and containing 0 to 10 mole % of another olefin or diolefin in the presence of a catalyst composed of (i) a solid titanium catalyst component and (ii) an organoaluminum compound; wherein the solid titanium catalyst component is obtained by contacting(1) a magnesium containing copulverization product comprising (A) an aluminum or germanium compound selected from the group consisting of aluminum compounds of the formula AlR.sub.n X.sub.3-n wherein R is a hydrogen atom, or an alkyl, alkenyl, aryl, alkoxy, aryloxy or acyloxy group optionally having a substituent, X is a halogen atom, and O<n.ltoreq.3, and germanium compounds of the formula GeR.sub.m X.sub.4-m wherein R and X are as defined above, and 0.ltoreq.m.ltoreq.Type: GrantFiled: May 4, 1978Date of Patent: February 10, 1981Assignee: Mitsui Petrochemical Industries Ltd.Inventors: Syuji Minami, Akinori Toyota, Norio Kashiwa
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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: 4242232Abstract: A catalyst comprising(a) a reaction mixture formed by reacting M(RCO.sub.2).sub.3 with AlR.sub.3'.sup.1(b) AlR.sub.3.sup.2 and / or HAlR.sub.2.sup.2 and(c) a Lewis acidwherein M denotes a trivalent rare earth element with an atomic number of 57 to 71, R denotes a saturated or unsaturated, straight chain or branched chain aliphatic hydrocarbon group having 1 to 20 C-atoms which may be substituted one or more times with cycloalkyl having 5 to 7-atoms and/or phenyl, the carboxyl group being attached to a primary, secondary or tertiary C-atom; a cycloalkyl group having 5 to 7 ring carbon atoms, which may be substituted one or more times with alkyl groups having from 1 to 5 C-atoms; or an aromatic group having from 6 to 10 ring carbon atoms, which may be substituted one or more times with alkyl groups having 1 to 5 C-atoms, and R.sup.1 and R.sup.2 are identical or different, straight chain or branched chain alkyl groups having from 1 to 10 C-atoms.Type: GrantFiled: July 3, 1979Date of Patent: December 30, 1980Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4238355Abstract: 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: GrantFiled: September 10, 1979Date of Patent: December 9, 1980Assignee: The Dow Chemical CompanyInventors: Randall S. Shipley, Donald F. Birkelbach, Kirby Lowery, Jr.
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Patent number: 4224186Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins, particularly higher olefins, are prepared by reacting (A) tetravalent titanium compounds such as titanium tetraalkoxide, (B) an organoaluminum compound, (C) an organomagnesium component such as a hydrocarbon soluble complex of dialkyl magnesium and an organo aluminum compound such as triethyl aluminum and, (D) as a halide source, a tetravalent tin compound such as tin tetrachloride. 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 provide higher efficiencies than those catalysts employing HCl as the halide source.Type: GrantFiled: April 9, 1979Date of Patent: September 23, 1980Assignee: The Dow Chemical CompanyInventors: Kirby Lowery, Jr., Donald F. Birkelbach, Randall S. Shipley
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Patent number: 4223117Abstract: A process for the polymerization of olefins in the presence of a catalyst comprising a titanium compound and/or vanadium compound supported on a solid carrier and an organoaluminum compound, characterized in that said solid carrier comprises a solid product obtained by the reaction of an organomagnesium compound or a reaction mixture resulting from the organomagnesium compound and at least one compound selected from the group consisting of magnesium hydroxide, calcium hydroxide, zinc hydroxide and aluminum hydroxide, with an aluminum halogenide and/or silicon halogenide, whereby there are produced olefine polymers in an extremely large amount per unit weight of catalyst.Type: GrantFiled: April 10, 1978Date of Patent: September 16, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Takezo Sano, Akio Kobayashi, Yasuharu Yamada
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Patent number: 4212961Abstract: A process for producing soft copolymers which comprises copolymerizing ethylene and butene-1 in the presence of a catalyst comprising (1) a reaction product of (A) an organic titanium compound of the formula,Ti(OR).sub.n X.sub.4-nwherein R is a hydrocarbon residue having 1 to 10 carbon atoms, X is a halogen atom and n is a number satisfying the equation 0<n.ltoreq.4, and (B) an organo-magnesium compound, and (2) an organo-aluminum compound of the formula,AlR.sub.m 'X'.sub.3-mwherein R' is a hydrocarbon residue having 1 to 20 carbon atoms, X' is a halogen atom and m is a number satisfying the equation 0<m.ltoreq.3, the content of butene-1 in the copolymers being 10 to 30 mole %.Type: GrantFiled: September 28, 1978Date of Patent: July 15, 1980Assignee: Sumitomo Chemical Company, LimitedInventors: Akio Kobayashi, Kentaro Mashita
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Patent number: 4210738Abstract: Solid catalytic complexes are useful for stereospecific polymerization of .alpha.-olefins to solid crystalline polymers. The complexes are formed by reducing TiCl.sub.4 with an alkylaluminum, treating thus-obtained reduced solid with a complexing agent and contacting the resultant with TiCl.sub.4. They have a specific surface greater than 75 m.sup.2 /g.Type: GrantFiled: March 21, 1972Date of Patent: July 1, 1980Assignee: Solvay & Cie.Inventors: Jean P. Hermans, Paul Henrioulle
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Patent number: 4199473Abstract: A process for preparing a modified titanium chloride component for a titanium-containing Ziegler olefin polymerization catalyst comprising (1) treating an ether-free organo-magnesium compound with an oxygen-containing organic compound other than an ether, or with carbon dioxide or oxygen under anhydrous conditions and (2) reacting the product with titanium tetrachloride.Type: GrantFiled: December 13, 1977Date of Patent: April 22, 1980Assignee: The International Synthetic Rubber Co. Ltd.Inventor: Donald G. Timms
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Patent number: 4194075Abstract: A magnesium reducing agent is prepared by reacting an organic halide with 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 mixed with an organoaluminum halide to form a cocatalyst. The resulting cocatalyst is contacted with a titanium tetrahalide to give a catalyst. This catalyst is suitable for olefin polymerization and particularly suitable for the polymerization of ethylene. In one embodiment, the organic halide is added dropwise to the magnesium metal.Type: GrantFiled: May 2, 1978Date of Patent: March 18, 1980Assignee: Phillips Petroleum CompanyInventors: Richard E. Dietz, Charles M. Selman
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Patent number: 4194076Abstract: An organic halide is reacted with magnesium metal in the absence of an ether or other complexing diluent, preferably in the absence of any extraneous diluent to produce a magnesium reducing agent. In one embodiment, the halide is added dropwise to the magnesium metal. The resulting magnesium reducing agent is then washed with an unreactive liquid hydrocarbon. An organoaluminum compound is mixed with the magnesium reducing agent either before or after the washing. The resulting cocatalyst produced by contacting the magnesium reducing agent with the organoaluminum compound is contacted with a titanium tetrahalide to give a catalyst. This catalyst is useful in the polymerization of 1-olefins and is of particular utility in the polymerization of ethylene at high productivity rates.Type: GrantFiled: April 27, 1978Date of Patent: March 18, 1980Assignee: Phillips Petroleum CompanyInventors: Richard E. Dietz, Oscar D. Nowlin
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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: 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: 4175170Abstract: Manufacture of polymers of .alpha.-monoolefins by polymerization with a Ziegler catalyst system comprising (1) a catalyst component containing titanium and/or vanadium and (2) a particular compound of the metals aluminum, magnesium or zinc. The characteristic feature of the process according to the invention is that the catalyst component (1) containing titanium and/or vanadium is the solid-phase product (VII) contained by first (1.1) bringing a finely divided porous inorganic oxidic material (I), which has the formula Al.sub.2 O.sub.3 or SiO.sub.2.aAl.sub.2 O.sub.3, where a is a number from 0 to 2, into contact with an aluminum compound (II) dissolved in an organic solvent, to form a solid-phase product (III), then (1.2) bringing the solid-phase product (III) obtained in stage (1.1) into contact with a magnesium compound (IV), dissolved in an organic solvent, to form a solid-phase product (V), and finally (1.3) bringing the solid-phase product (V) obtained in stage (1.Type: GrantFiled: September 7, 1976Date of Patent: November 20, 1979Assignee: BASF AktiengesellschaftInventors: Guenther Schweier, Robert Bachl, Heinz Mueller-Tamm, Hans Frielingsdorf, Wolfgang Gruber, Erich Kolk
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Patent number: 4173547Abstract: An improved process for polymerizing .alpha.-alkenes and using Ziegler-type catalyst compositions is described.The Ziegler-type catalyst composition comprises a component consisting of an organoaluminum compound, an organomagnesium compound and a titanium compound or their reaction products on an inorganic porous solid particulate carrier material, wherein the aluminum/magnesium/titanium components are distributed and absorbed onto the inorganic carrier material, in separate steps, with removal of solvent or diluent therein between whereby the final catalyst/carrier composition when used in the polymerization process produces solid particulate polymer products with narrow particle size distributions.Type: GrantFiled: March 8, 1978Date of Patent: November 6, 1979Assignee: Stamicarbon, B.V.Inventor: Renier J. L. Graff
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Patent number: 4172050Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins are provided by reacting an ester of titanium, a so-called 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. 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: May 27, 1975Date of Patent: October 23, 1979Assignee: The Dow Chemical CompanyInventor: Donald E. Gessell
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Patent number: 4168361Abstract: A random copolymer consisting essentially of 40 to 90 mole% of propylene and 60 to 10 mole% of 1-butene, and having (A) a boiling n-heptane-insoluble content of not more than 5% by weight based on the weight of the copolymer, (B) a boiling methyl acetate-soluble content of not more than 2% by weight based on the weight of the copolymer, (C) a melting point, determined by differential thermal analysis, of 40 to 140.degree. C., (D) an intrinsic viscosity, determined in decalin at 135.degree. C., of 0.5 to 6 dl/g, (E) an elongation at break, measured by JIS K6301, of at least 300%, (F) a tensile strength at break, measured by JIS K6301, of at least 50 kg/cm.sup.2, and (G) a haze, measured by JIS K6714, of not more than 40%.Type: GrantFiled: December 19, 1977Date of Patent: September 18, 1979Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Hidekuni Oda, Yozo Yamamoto, Hirokazu Kajiura, Syuji Minami, Takao Ohno
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Patent number: 4166167Abstract: 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: GrantFiled: June 20, 1977Date of Patent: August 28, 1979Assignee: Imperial Chemical Industries LimitedInventors: Ashley D. Bye, John E. Priddle, Victor A. Wilson
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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: 4148754Abstract: When reacting the reaction product of silicon dioxide and/or a metal oxide and a Grignard compound with a soluble titanium compound, there is obtained a catalyst for the polymerization of 1-olefins, which gives a very high yield and allows a good control of the molecular weight by means of hydrogen without making necessary a separation of the excess of metallo-organic compounds and/or the excess of titanium compounds from the catalyst carrier.Type: GrantFiled: November 23, 1976Date of Patent: April 10, 1979Assignee: Hoechst AktiengesellschaftInventors: Wolfgang Strobel, Rainer Franke
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Patent number: 4146695Abstract: 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: GrantFiled: May 23, 1977Date of Patent: March 27, 1979Assignee: Stamicarbon, B.V.Inventor: Lambertus J. M. A. VAN DE Leemput
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Patent number: 4145497Abstract: Uranium-containing mixed catalysts containing uranium in the formal oxidation state +4 as uranium salts of carboxylic acids, a Lewis acid, and an organometallic aluminum compound are prepared and can be used for stereospecific polymerization of diolefins or mixtures of diolefins and monoolefins.Type: GrantFiled: May 31, 1977Date of Patent: March 20, 1979Assignee: Bayer AktiengesellschaftInventors: Gerd Sylvester, Josef Witte, Gunter Marwede
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Patent number: 4143223Abstract: A process for polymerizing or copolymerizing .alpha.-olefins in the presence of a catalyst composed of (A) a mechanically pulverized solid titanium-containing catalyst component and (B) an organometallic compound of a metal of Groups I to III of the periodic table, wherein said titanium-containing component is a solid halogen-containing titanium catalyst component obtained by reacting a mechanically copulverized solid product in the absence of mechanical pulverization with a titanium compound which is liquid under the reaction conditions, said mechanically copulverized product being derived from (1) a magnesium compound, (2) an organic acid ester, and (3) an active hydrogen-containing compound selected from the group of alcohols and phenols; and a catalyst composition used therefor.Type: GrantFiled: March 1, 1977Date of Patent: March 6, 1979Assignee: Mitsui Petrochemical Industries Ltd.Inventors: Akinori Toyota, Syuji Minami, Norio Kashiwa
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Patent number: 4135046Abstract: A unique high efficiency catalyst has been developed for the polymerization of ethylene. The activity of the catalyst, which uses a mixed magnesium-aluminum alkyl as a reducing agent for tetrabutyltitanate, and hydrogen chloride to deactivate excess reducing agent, is dependent on a specific and unpredicted order of addition of catalyst components.Type: GrantFiled: February 28, 1977Date of Patent: January 16, 1979Assignee: Arco Polymers, Inc.Inventors: James J. Harris, Richard E. Hammond
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Patent number: 4123386Abstract: An olefin polymerization catalyst is prepared in two steps. In the first step, a chemically reducing solid is prepared by polymerizing an olefin in contact with solid particles of a compound of a transition metal from sub-groups IV A, V A and VI A in a lower valency state in the presence of an organomagnesium compound and terminating the polymerization when the quantity of olefin polymerized is from 50 mg.-50 g. per mg-atom of transition metal. In the second step, the chemically reducing solid prepared in the first step is contacted with reducible compounds of transition metals from sub-groups IV A, V A and VI A to effect reduction thereof.Type: GrantFiled: December 9, 1976Date of Patent: October 31, 1978Inventors: Michel M. Avaro, Pierre M. Mangin
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Patent number: 4121030Abstract: 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-aluminium compound and a Lewis Base compound such as an ester.Type: GrantFiled: November 24, 1976Date of Patent: October 17, 1978Assignee: Imperial Chemical Industries LimitedInventors: John Paton Candlin, Keith Collier Wilson, Ronald Pearce
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Patent number: 4113654Abstract: There are disclosed catalysts which are highly active in the polymerization of olefins and which are prepared by mixing hydrides or organometallic compounds of metals belonging to Groups I to III of the Mendelyeev Periodic Table with the product of reaction between an organic magnesium halide and a halogenated titanium compound, said reaction product containing titanium in an amount of from 0.05% to 10% by weight. Methods for preparing the aforesaid catalysts and the use of the catalysts in the polymerization of ethylene and mixtures thereof with higher alpha-olefins and/or diolefins are also disclosed.Type: GrantFiled: October 18, 1976Date of Patent: September 12, 1978Assignee: Montecatini Edison S.p.A.Inventors: Adolfo Mayr, Velmore Davoli, Antonio Leccese, Ermanno Susa
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Patent number: 4104198Abstract: Compositions exhibiting high catalytic activity in the polymerization of .alpha.-olefins are provided by reacting a dinitrogen and/or dihydrogen complex of a transition metal such as titanium with an organometallic compound of a divalent metal such as dihydrocarbyl magnesium or hydrocarbyl magnesium halide and a halide source such as 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: July 14, 1976Date of Patent: August 1, 1978Assignee: The Dow Chemical CompanyInventors: James A. May, Jr., Wilbur L. Bressler
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Patent number: 4097659Abstract: A process for polymerizing .alpha.-olefins in the liquid phase is disclosed, wherein the olefins are polymerized in the presence of a catalyst prepared by first reacting as aluminum-halogen compound with an organomagnesium compound and thereafter reacting the resulting reaction mixture with a transition metal compound and then activating the resulting catalyst system with an organo-aluminum compound. The homopolymers and copolymers of .alpha.-olefins produced by this process find use in the normal applications of such polymers.Type: GrantFiled: April 15, 1976Date of Patent: June 27, 1978Assignee: Stamicarbon, N.V.Inventors: Henricus M. J. C. Creemers, Renier J. L. Graff, Hendrinus M. Verschoor
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Patent number: 4063009Abstract: Alpha olefins are polymerized alone or in admixture at comparatively low pressures to produce polymers employing a two-component catalyst wherein one component is an organozinc or organomagnesium compound, e.g. zinc diethyl, magnesium diphenyl, propyl magnesium chloride, etc. The other component is a salt, oxide or hydroxide of a metal of Group IV-B, V-B or VI-B of the Periodic System, including thorium and uranium.Type: GrantFiled: July 1, 1958Date of Patent: December 13, 1977Assignee: Studiengesellschaft Kohle m.b.H.Inventors: Karl Ziegler, deceased, Heinz Breil, Erhard Holzkamp, Heinz Martin
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Patent number: 4056668Abstract: Olefins are polymerized and copolymerized in the presence of a solid catalyst which contains an organometallic compound and a solid material having at the surface thereof catalytic complexes containing a divalent metal, halogen, oxygen and a transition metal having halogenated substituents. The solid material of the catalyst is obtained by reacting a liquid halogenated derivative of a transition metal, such as TiCl.sub.4 or VOCl.sub.3 with a solid support which is a oxygenated compound of a divalent metal and which is substantially anhydrous and also substantially free of hydroxyl groups; examples of such a solid support include calcium, magnesium and zinc oxides and oxygenated salts such as nitrates, sulfates and silicates and organic carboxylate salts including salts of mono- and acetates polycarboxylic acids.Type: GrantFiled: April 29, 1976Date of Patent: November 1, 1977Assignee: Solvay & CieInventors: Eugene Berger, Pol Gerard, Andre Delbouille, Jean-Louis Deroitte