Contains Non-transition Elemental Metal, Hydride Thereof, Or Carbon To Non-transition Metal Atom Bond Patents (Class 526/121)
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Patent number: 4304891Abstract: A process for producing .alpha.-olefins is provided which comprises:milling (A) a trivalent metal halide together with (B) a divalent metal compound, in a specified ratio of (A) to (B), and reacting them to obtain a solid product (I);reacting with this product (I), (C) an electron donor and (D) an electron acceptor, (C) and (D) being respectively reacted once or more up to ten times, and TiCl.sub.4 being employed as the electron acceptor at least once, to obtain a solid product (II);combining with this product (II), (E) a trialkylaluminum and (G) a reaction product of an electron donor with an electron acceptor, and in this combination, subjecting a part or the whole of the catalyst components (product (II), (E) and (G)) to polymerization treatment by reacting (F) an .alpha.-olefin at least in the presence of the product (II) and trialkylaluminum, to obtain a preliminarily activated catalyst; andpolymerizing an .alpha.-olefin in the presence of this catalyst.Type: GrantFiled: April 28, 1980Date of Patent: December 8, 1981Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Kazutsune Kikuta, Yoshiharu Higuchi
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Patent number: 4298717Abstract: A process for polymerizing ethylene under high pressure and temperature in at least one reactor having at least one reaction zone. A catalyst system is used that comprises (a) an activator selected from trialkylaluminums, hologenodialkylaluminums, and alkylsiloxalanes, (b) a halogen compound of a transition metal of groups IV to VI A, and (c) a complexing agent that is injected into the reactor in such a manner that its concentration in the reactor may be adjusted independently from the concentration of (b). The complexing agent may be selected from silicone oils and from compounds having the formula X(OR).sub.n, wherein X is hydrogen or a metal, n is the valence of X, and R is an alkyl radical of up to 20 carbon atoms.Type: GrantFiled: August 1, 1978Date of Patent: November 3, 1981Assignee: Societe Chimique des Charbonnages-CdF ChimieInventor: Jean-Pierre Machon
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Patent number: 4297462Abstract: For the polymerization of ethylene, as such or with one or more alpha-olefines, a novel catalyst composition is suggested, which has a high yield of polymer per weight unit of catalyst. Such compositions are prepared from a titanium compound in which the valency of Ti is 3 or more, said compound being reacted with the vapors of one or more metals of the group consisting of Al, Cr, Mn, V, Ti, Zr, Mo, Zn and Ca in the presence of a halogen donor which is preferably an organic halide, certain inorganic halides being capable of being used provided that the halide metal has at least two degrees of valency. The composition is used in association with an aluminium hydrocarbyl halide. Yields as high as 30,000 grams of polymer per gram of elemental Ti can be obtained.Type: GrantFiled: September 25, 1979Date of Patent: October 27, 1981Assignees: Snamprogetti S.p.A, Anic S.p.AInventors: Margherita Corbellini, Alberto Greco, Mirko Osellame
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Patent number: 4287328Abstract: A method for producing .alpha.-olefin polymers is provided. According to this method, particularly the catalyst stability is improved, resulting in polymers having a higher crystallinity, a narrower range of molecular weight, improved shape of polymer particles with a higher yield per a solid product component and per a transition metal component of the catalyst. Said catalyst is obtained by reacting a trivalent metal halide with a hydroxide, an oxide, a carbonate of a divalent metal, a double compound containing any of these compounds or a hydrate of a compound containing a divalent metal to form a solid product (I); reacting said solid product with one or more electron donors and one or more electron acceptors separately or simultaneously each in one to 10 steps but using TiCl.sub.Type: GrantFiled: March 21, 1979Date of Patent: September 1, 1981Assignee: Chisso CorporationInventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
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Patent number: 4262105Abstract: This invention relates to the polymerization of .alpha.-olefins and to catalysts and cocatalysts for that purpose wherein the polymerization is carried out in the presence of a catalyst comprising an organometallic compound of a metal of Groups IA, IIA, IIB, IIIA, and IVA of the Periodic Table and a cocatalyst comprising the reaction product of a derivative of a transition metal of Groups IVB, VB, and VIB of the Periodic Table and a fluorinated reaction product having an atomic ratio of fluorine/divalent metal greater than 1, said fluorinated reaction product being formed by reacting a fluorinating agent with an oxygenated compound of a divalent metal at a temperature between about 150.degree. to 450.degree. C. for a time sufficient to form said reaction product. The invention also comprises the method of making the cocatalysts.Type: GrantFiled: December 26, 1979Date of Patent: April 14, 1981Assignee: Solvay & CieInventors: Andre Delbouille, Jean-Louis Derroitte
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Patent number: 4258159Abstract: A process for low temperature polymerization and copolymerization of alpha-olefins comprising conducting the polymerization in the presence of a catalytic system comprising an organic compound of a metal of Group IA, IIA, IIB, IIIA and IVA of the Periodic Table and a solid catalytic complex which is prepared by reacting a compound of a metal of Groups IVB, VB and VIB of the Periodic Table with a porous aluminum oxide on which a magnesium compound is deposited.Type: GrantFiled: December 4, 1975Date of Patent: March 24, 1981Assignee: Solvay & CieInventor: Charles Bienfait
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Patent number: 4250284Abstract: Polymerization and copolymerization is carried out in the presence of an improved transition metal based catalyst. The catalyst is obtained by activating with an organometallic compound, the solid product which results from the reaction of a halogen containing transition metal compound with an alkoxy metal compound of the formula X.sub.m-n M(OR).sub.n wherein M is at least one metal selected from the elements of Groups Ia, IIa, IIb, IIIa and VIIb of the Periodic Table, X is a monovalent inorganic radical, R is a monovalent hydrocarbon radical, m is the valence of M and n is an integer such that 1 .ltoreq. n .ltoreq. m.Type: GrantFiled: February 24, 1975Date of Patent: February 10, 1981Assignee: Solvay & CieInventors: Andre Delbouille, Jean L. Derroitte
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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: 4233182Abstract: High activity alpha-olefin polymerization catalysts comprising an organometallic promoter and a component prepared from at least one compound of a Group IVB, VB, or VIB metal, at least one support material which is a divalent metal salt of a phosphorus acid ester having at least one phosphorous acid ester group bonded to metal through oxygen or sulfur, and at least one alkylaluminum halide.Type: GrantFiled: December 26, 1978Date of Patent: November 11, 1980Assignee: Standard Oil Company (Indiana)Inventors: Glen R. Hoff, Peter Fotis
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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: 4196097Abstract: A Ziegler catalytic system comprising an organometallic compound of a metal of Groups I to III of the Periodic Table and a compound of a heavy metal of Groups IV to VI supported on a carrier, the latter being an activated amorphous alumina or alumino-silicate containing from 0.3 to 30% by weight of salts of metals of Groups IIb, IIIa, VIb and VIII with oxygenated inorganic anions, or of a mixture of the latter with salts of said metals of Groups IIb, IIIa, VIb and VIII with non-oxygenated inorganic anions, said salts being introduced into the carrier by contacting the latter with one or more solutions of said salts and the carrier being then activated by calcination at 250.degree.-700.degree. C.Type: GrantFiled: October 6, 1977Date of Patent: April 1, 1980Assignee: Euteco S.p.A.Inventors: Ferdinando Ligorati, Renzo Invernizzi, Carlo Collu, Maurizio Fontanesi
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Patent number: 4191816Abstract: A process for the preparation of catalysts for the polymerization of olefines, e.g. ethylene and propylene. This process comprises essentially the two following steps:(1) A compound (A) of an element selected from groups Ia, Ib, IIa, IIb, IIIa, IIIb, VIa and VIIb of the Periodic Table of Elements is heated and milled under the protection of an inert gas with an organic acetoxy compound; then the volatile portions of the mixture are eliminated by distillation.(2) The solid resulting from the first step is dissolved or dispersed in a non-polar hydrocarbon and an activator (B) is added, mixed and heated with said solution or dispersion until a homogeneous solution or dispersion of activated catalyst is obtained. (B) is selected from compounds of elements IVa, IVb and Vb of the Periodic Table.This catalyst is used in admixture with a polymerization promoter (C) selected from organo-metallic additives, e.g. aluminum-organic compounds for the polymerization of olefines at relatively low temperatures and pressures.Type: GrantFiled: May 12, 1977Date of Patent: March 4, 1980Assignee: Battelle Memorial InstituteInventor: Alfred Columberg
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Patent number: 4104199Abstract: A novel supported catalyst for polymerization of ethylene or its mixtures with C.sub.3 to C.sub.8 terminal olefins composed of (a) the solid reaction product of a titanium (IV) or vanadium (V) alkoxide, a hydrated magnesium stannate and an alkylaluminum dichloride, and (b) an organo-aluminum compound promoter. The catalyst produces polyolefin in good yield without any substantial production of polymer fines and the catalyst is quite sensitive to hydrogen induced chain termination processes leading to improved molecular weight control and rheology of the polymer product.Type: GrantFiled: April 25, 1977Date of Patent: August 1, 1978Assignee: Standard Oil Company a corporation of IndianaInventor: Glen R. Hoff
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Patent number: 4103078Abstract: Polymers of .alpha.-olefin such as polyethylene, polypropylene, copolymers of ethylene with propylene, butene-1 or styrene, are produced by the (co-) polymerization using a catalyst obtained by mill-mixing an oxide of a metal belonging to I, II, III, VII or VIII Group of the Periodic Table of Elements such as MgO or SiO.sub.2 or B.sub.2 O.sub.3, with a trivalent metal halide such as AlCl.sub.3, then reacting the resultant mixture with a transition metal compound such as TiCl.sub.4 in the presence of an aromatic compound such as xylene, and activating the resultant solid reaction product with an organoaluminum compound such as triethyl aluminum.In the preparation of the present catalyst, no dehydrochlorination occurs. The present catalyst has an excellent utilization efficiency of transition metal compound in the polymerization. Further, no polymer film forms on the wall surface of the polymerization vessel.Type: GrantFiled: March 13, 1973Date of Patent: July 25, 1978Assignee: Chisso CorporationInventors: Akihiro Sato, Shiro Konotsune, Atsuyuki Kachi, Hiroshi Shimizu
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Patent number: 4088812Abstract: This invention discloses an improved catalyst for the polymerization or copolymerization of olefins, and a process for preparing polyolefins which comprises polymerizing or copolymerizing olefins using the said catalyst. According to the invention there is provided a process for preparing polyolefins by polymerizing or copolymerizing olefins using as a catalyst at least one compound selected from the group consisting of a titanium compound and a vanadium compound supported on a solid carrier, and an organometallic compound, said solid carrier comprising a product obtained by treatment with SO.sub.3 of at least one member selected from the group consisting of an oxide of Group II-IV metals of the Periodic Table and a double oxide of the said oxide and other oxide, which other oxide may be another oxide of Group II-IV metals of the Periodic Table or may be an oxide of other Group metals of the same Table.Type: GrantFiled: December 20, 1976Date of Patent: May 9, 1978Assignee: Nippon Oil Company, LimitedInventors: Kazuo Matuura, Masaomi Matsuzaki, Humiaki Oshimi, Nobuyuki Kuroda, Mituji Miyoshi
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Patent number: 4081589Abstract: Adding a finely divided oxide to a terminal olefin polymerization catalyst comprising a hydrocarbon-soluble transition metal compound and a Group II or III metal organic compound reduces the amount of fibrous polymer produced.Type: GrantFiled: December 20, 1976Date of Patent: March 28, 1978Assignee: The Standard Oil CompanyInventors: Edwin F. Peters, David E. Boone
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Patent number: 4076923Abstract: According to the present invention, there is provided a process for preparing polyolefins which comprises polymerizing or copolymerizing olefins using as catalyst a component consisting of a solid carrier and a titanium compound and/or a vanadium compound supported thereon, and an organometallic compound, said solid carrier consisting of a product obtained by mixing and heating an aluminum oxide and an ammonium sulfate.Type: GrantFiled: March 22, 1976Date of Patent: February 28, 1978Assignee: Nippon Oil Company, LimitedInventors: Kazuo Matsuura, Masaomi Matsuzaki, Fumiaki Oshimi, Nobuyuki Kuroda, Mituji Miyoshi
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Patent number: 4065612Abstract: An improved chromate ester catalyst useful for preparing, at relatively low temperatures, ethylene polymers which have a relatively lower molecular weight and which are more stable against oxidation is prepared by treating a silica supported chromate ester first with a phenol compound and then with a strong reducing agent.Type: GrantFiled: March 30, 1976Date of Patent: December 27, 1977Assignee: Union Carbide CorporationInventors: Anthony David Hamer, Frederick John Karol
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Patent number: 4027087Abstract: Ethylene can be polymerized or copolymerized by the use of a catalyst prepared by mixing a trivalent metal halide with a metal carbonate or/and a metal hydrogen carbonate, reacting the resulting mixture with a transition metal compound in the presence of an aromatic compound, and activating the resulting solid product with an organoaluminum compound.By substituting said metal carbonate or/and metal hydrogen carbonate for metal salt hydrates, sulfide hydrates, hydroxides or hydroxide hydrates, or metal oxides in our prior art, drawbacks such as dehydrochlorination in the preparation of catalyst or difficulty in removal of catalyst residue from polymer can be overcome while various advantages in our prior art are still maintained.Type: GrantFiled: October 30, 1972Date of Patent: May 31, 1977Assignee: Chisso CorporationInventors: Akihiro Satoh, Shiro Konotsune, Atsuyuki Kachi, Hiroshi Shimizu
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Patent number: 3998996Abstract: A mixed catalyst for the low pressure polymerization of 1-olefines is prepared by reacting a chromium-III compound containing water of crystallization with a metal alcoholate and by mixing the obtained chromium complex with an activator. The catalyst excels by allowing a simple preparation method and by a very good activity.Type: GrantFiled: March 19, 1975Date of Patent: December 21, 1976Assignee: Hoechst AktiengesellschaftInventor: Tibor Toth
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Patent number: 3989880Abstract: This invention relates to the polymerization and copolymerization of .alpha.-olefins and to catalysts and cocatalysts for that purpose wherein the polymerization is carried out in the presence of a catalyst composition comprising an organometallic compound and the cocatalyst reaction product of a halogenated transition metal compound and an organic compound of a divalent metal containing oxygen and nitrogen and being substantially free from hydroxyl groups attached to the divalent metal.Type: GrantFiled: February 11, 1972Date of Patent: November 2, 1976Assignee: Solvay & CieInventors: Eugene Berger, Pol Gerard, Andre Delbouille, Jean-Louis Derroitte
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Patent number: 3989879Abstract: The present invention relates to catalytic complexes for the polymerization and copolymerization of olefins comprising the reaction product of a halogenated derivative of a transition metal with a chelate organic oxygenated bivalent metal compound substantially free of hydroxyl groups; to the catalyst compositions formed by activating such complexes with an organometallic compound; and to the processes of forming such catalytic complexes and polymerizing and copolymerizing olefins utilizing such catalyst compositions.Type: GrantFiled: July 10, 1972Date of Patent: November 2, 1976Assignee: Solvay & CieInventors: Eugene Berger, Andre Delbouille, Pol Gerard, Jean-Louis Derroitte
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Patent number: 3987233Abstract: In a method for producing a polymer or a copolymer of ethylene carried out in the presence of a catalyst obtained by a combination of a solid product containing a transition metal of the fourth a or fifth a group and an organoaluminum compound, an improvement has been made to provide a catalyst having such an efficiency as being capable of omitting ash-removal step and providing a high production yield of polymer per unit volume of polymerization vessel per hour and a polymer having a high B.D. Said catalyst can be obtained by (1) reacting a halide of trivalent metal (A) with a divalent metal compound or its derivative (B) such as hydroxide, oxide or carbonate thereof, or hydrate of these, to produce a solid product (I); (2) reacting said solid product (I) with a chain or cyclic polysiloxane having a general formula of ##EQU1## WHEREIN R.sub.1 and R.sub.Type: GrantFiled: April 29, 1975Date of Patent: October 19, 1976Assignee: Chisso CorporationInventors: Akihiro Sato, Hiroshi Shimizu, Atsuyuki Kachi