Non-metal Material Is Inorganic Halogen-containing Material Patents (Class 526/137)
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Patent number: 4525549Abstract: A new process is described for polymerizing and copolymerizing conjugate diolefins characterized by the use of a catalytic system comprising at least one compound of Group III B of the periodic system, at least one non-halogenated aluminium alkyl, at least one compound containing one or more hydroxyls of acid or neutral type, and possibly an inorganic compound containing Cl or Br in ionizable form or an organic halogen derivative.The new process allows the preparation, both in the absence and in the presence of an inert diluent, of polydiolefins of essentially entirely 1,4-cis structure which even in the absence of a purification stage contain a very small quantity of catalytic residues.Type: GrantFiled: April 14, 1983Date of Patent: June 25, 1985Assignee: Enoxy Chimica S.p.A.Inventors: Antonio Carbonaro, Domenico Ferraro
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Patent number: 4522989Abstract: Diene polymers having a high content of cis-1,4 addition are prepared by polymerizing a 1,3-diene monomer in a hydrocarbon solvent in the presence of a catalyst composition comprising (a) a carboxylated metal oxy aluminate compound in which the metal is nickel or cobalt, (b) an organometallic compound of a metal of Groups I, II, and III of the Periodic System, and (c) one or more fluorine containing compounds selected from the group consisting of boron trifluoride complexes with ethers, alcohols or mixtures thereof; hydrogen fluoride; hydrogen fluoride complexes with ethers, alcohols, or mixtures thereof and mixtures of said compounds.The resultant polymers exhibit good green strength and tack and are particularly suitable for use as tire rubbers.Type: GrantFiled: June 4, 1984Date of Patent: June 11, 1985Assignee: The Firestone Tire & Rubber CompanyInventor: Jung W. Kang
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Patent number: 4514512Abstract: A method for the production of a solid titanium trichloride catalyst by the steps of preparing a titanium trichloride composition comprising a solid reduction product obtained by reducing titanium tetrachloride with an organoaluminum compound represented by the formula, R.sup.1.sub.n AlY.sub.3-n (wherein R.sup.1 is a hydrocarbon group having 1 to 18 carbon atoms; Y is a halogen atom or a hydrogen atom; and n is a number satisfying the equation, 1<n.ltoreq.3), or a solid product obtained by thermally treating said solid reduction product at a temperature of not more than 150.degree. C.; reacting said titanium trichloride composition in an aromatic hydrocarbon solvent with a mixture consisting of a halogen compound represented by the formula, X.sub.2 (wherein X is Cl, Br, or I), or an interhalogen compound represented by the formula, XX'.sub.a (wherein X and X' are each Cl, Br, or I, and a is 1 or 3), and an ether compound represented by the formula, R.sup.2 --O--R.sup.3 (wherein R.sup.2 and R.sup.Type: GrantFiled: March 31, 1983Date of Patent: April 30, 1985Assignee: Sumitomo Chemical Company, LimitedInventors: Akinobu Shiga, Yukio Naito, Toshio Sasaki, Junpei Kojima, Hiroshi Yoshioka, Akira Nunose
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Patent number: 4508843Abstract: A catalyst component for polymerizing ethylene alone or with another alpha-olefin having from 3 to 18 carbon atoms at temperatures greater than about 150.degree. C. which catalyst component is the product obtained by treating at least one dehydrated particulate support material, such as silica, having an average particle size from about 0.05 to about 20 microns, preferably 1.0 to 10.0 microns, with(a) at least one dihydrocarbyl magnesium compound wherein the hydrocarbyl groups can be the same or different, such as butyl ethyl magnesium,(b) a transistion metal compound of Groups IVa, Va, or VIa of the Periodic Table, such as, for example, titanium tetrachloride, and (c) ethyl aluminum dichloride. In a preferred embodiment the particulate support material is treated with a halogenating agent prior to treatment with the transition metal compound.Type: GrantFiled: August 8, 1983Date of Patent: April 2, 1985Assignee: Exxon Research & Engineering Co.Inventors: Bradley P. Etherton, Anthony D. Hamer
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Patent number: 4497905Abstract: A highly active and stereoselective olefin polymerization catalyst component is obtained by halogenating a magnesium compound of the formula MgR'R" wherein R' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon, and contacting the halogenated product with thionyl chloride and a tetravalent titanium compound.Type: GrantFiled: October 13, 1983Date of Patent: February 5, 1985Assignee: Shell Oil CompanyInventor: Kenzie Nozaki
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Patent number: 4483971Abstract: A process for producing terpolymers of propylene (as a main monomer), ethylene and another .alpha.-olefin having superior and well-balanced physical properties, almost without forming soluble polymer is provided.This process is characterized by preliminarily activating a catalyst consisting of a titanium trichloride composition and a specified organoaluminum halide, with a small amount of an .alpha.-olefin of 2 to 12 carbon atoms, a trialkylaluminum and an aromatic ester, and copolymerizing specified amounts of propylene, ethylene and an .alpha.-olefin of 4 to 12 carbon atoms in the presence of the preliminarily activated catalyst obtained above.Type: GrantFiled: February 25, 1983Date of Patent: November 20, 1984Assignee: Chisso CorporationInventors: Akihiro Sato, Takeshi Suzuki, Kazutsune Kikuta, Hiromasa Chiba, Toshihiro Uwai, Kenji Matsuda, Tohru Hanari
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Patent number: 4471066Abstract: A catalyst useful for polymerizing olefins which comprises a solid catalyst component [A] and an organometallic component [B], the solid catalyst component [A] being obtained by reacting (1) an organometallic compound with (2) a transition metal compound selected from the group consisting of a titanium compound, a vanadium compound, a mixture of a titanium compound and a vanadium compound and a mixture of a titanium compound and a zirconium compound, in the presence of (3) a solid reaction product of (a) an organomagnesium compound of the formulaM.sub..alpha. MgR.sub.p X.sub.q.D.sub.rwherein.alpha., p, q and r each independently is 0 or a number greater than 0,p+q=m.alpha.+20.ltoreq.q/(.alpha.Type: GrantFiled: February 3, 1983Date of Patent: September 11, 1984Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4468477Abstract: A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride or silicon tetrachloride and a specified transition metal compound. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.Type: GrantFiled: July 1, 1980Date of Patent: August 28, 1984Assignee: Imperial Chemical Industries PLCInventors: Anthony D. Caunt, Paul D. Gavens, John McMeeking
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Patent number: 4461881Abstract: In a process for producing a homopolymer or a copolymer of propylene comprising polymerizing propylene or copolymerizing propylene and at least one other unsaturated hydrocarbon monomer in liquid propylene using a catalyst system containing activated titanium trichloride (a) and an organoaluminum compound (b), the activated titanium trichloride (a) being prepared by reducing titanium tetrachloride with an organoaluminum compound followed by activation, to produce a polymer slurry; introducing the polymer slurry produced into the top of a counter-current washing tower; and washing the polymer slurry by counter-currently contacting the polymer slurry with liquid propylene introduced into the bottom of the washing tower, the improvement which comprises purifying the homopolymer or copolymer of propylene by feeding an epoxide in a molar amount of about 1 to about 15 times the molar amount of the total of activated titanium trichloride (a) and organoaluminum compound (b), to a part of said washing tower, thereby dType: GrantFiled: October 23, 1981Date of Patent: July 24, 1984Assignee: Sumitomo Chemical Co., Ltd.Inventors: Akinobu Shiga, Kiyoshi Matsuyama, Masahiro Kakugo, Yukio Naito, Takatoshi Suzuki
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Patent number: 4460757Abstract: A process for producing highly crystalline .alpha.-olefin polymers of good particle form with high yield is provided, which comprises polymerizing .alpha.-olefin in the presence of a preactivated catalyst obtained by reacting a reaction product (I) of organoaluminum compound (A.sub.1) with electron donor (B.sub.1), with TiCl.sub.4 to obtain a solid product (II); further reacting (II) with electron donor (B.sub.2) and electron acceptor to obtain a solid product (III); during or/and after the reaction step for obtaining (II) or/and during or/and after the reaction step for obtaining (III), subjecting (II) or (III), to polymerization treatment with .alpha.-olefin; and combining the resulting final solid product with organo-aluminum compound (A.sub.2) and a reaction product (G) of organo-aluminum compound (A.sub.3) with electron donor (B.sub.3) to obtain a preactivated catalyst; and preferably, in this combination, further subjecting a part or the total of the catalyst to polymerization treatment with .alpha.Type: GrantFiled: July 29, 1982Date of Patent: July 17, 1984Assignee: Chisso CorporationInventors: Akihiro Sato, Masami Tachibana, Toshihiro Uwai, Kenji Matsuda, Yoshiharu Higuchi
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Patent number: 4455386Abstract: A catalyst and method in which the catalyst is used in association with an aluminum cocatalyst in the polymerization and interpolymerization of 1-olefins. The catalyst is prepared by (1) reacting a mono- or polyfunctional phosphorus compound with silica, alumina or the like having surface hydroxyl groups, or a mixture thereof, in which the phosphorus compound reacts with these surface hydroxyl groups, followed by (2) reacting the product of this with a Group IIa (e.g. Mg) compound and further (3) reacting this product with a Group IVB, VB or VIB (e.g. Ti) compound. Alternatively, (1) is reacted with (3) and then with (2).Type: GrantFiled: March 29, 1982Date of Patent: June 19, 1984Assignee: Chemplex CompanyInventors: Michael W. Lynch, Thomas J. Pullukat
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Patent number: 4451574Abstract: Ethylene is homopolymerized or copolymerized with another olefin monomer in the presence of a catalyst system comprising organo metal cocatalyst and a titanium-containing catalyst component, such titanium-containing catalyst component being obtained by reacting together a porous particulate material, an organo magnesium compound, a halogen or interhalogen compound and titanium tetrachloride.Type: GrantFiled: January 31, 1983Date of Patent: May 29, 1984Assignee: Exxon Research & Engineering Co.Inventor: Burnett H. Johnson
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Patent number: 4438019Abstract: The invention is addressed to solid catalysts comprising essentially compounds of magnesium and of transition metals selected from the sub-groups IVa, Va and VIa of the periodic table, applicable to the polymerization of olefins and particularly ethylene, in which the catalyst is obtained by first preparing a solid compound of magnesium, monohalogenated hydrocarbon and halogen and/or organic derivatives of the transition metal in a state of valency of at least 4 and then reacting the solid compound of magnesium and transition metal with an oxidizing compound.Type: GrantFiled: March 10, 1981Date of Patent: March 20, 1984Assignee: BP ChimieInventors: Daniel C. Durand, Pierre M. Mangin
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Patent number: 4414373Abstract: In a process for producing polypropylene comprising polymerizing propylene in the presence of hydrogen and a catalyst system comprising (A) titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound and reacting the reduced solid with an ether represented by the formula:R.sup.1 --O--R.sup.2wherein R.sup.1 and R.sup.2 are defined hereinbefore, and a halogen compound selected from the group consisting of (i) halogen or interhalogen compounds of the formula, X.sup.1 X.sup.2.sub.a (wherein X.sup.1, X.sup.2 and a are defined hereinbefore), (ii) titanium halides, and (iii) organic halogen compounds, simultaneously or successively and (B) an organoaluminum compound, the improvement which comprises supplying ethylene together with propylene to the polymerization system such that the ethylene concentration in the vapor phase of the system based on the total amount of propylene, ethylene and hydrogen in the vapor phase of the system is 0.15 to 1.Type: GrantFiled: July 16, 1982Date of Patent: November 8, 1983Assignee: Sumitomo Chemical Co., Ltd.Inventors: Akinobu Shiga, Kiyoshi Matsuyama, Masahiro Kakugo, Yukio Naito, Seiichiro Ima, Katsuyoshi Yamashita
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Patent number: 4407727Abstract: A process is provided for transforming a polyolefin powder into a suitable substrate for the preparation of transition metal catalysts. A powder polyolefin such as polyethylene or polypropylene is treated with a solution of a magnesium alkyl. The solvent is removed by any suitable procedure such as vacuum drying. The powder is then treated with gaseous HCl or other agent suitable for decomposition of the magnesium alkyl. The powder thus prepared is an effective support for preparing high efficiency catalysts such as taught in U.S. Pat. No. 4,136,058. These catalysts give polymers of increased particle size. Polyolefin powder in the absence of such treatment is not effective as a catalyst support and will not give polymers of increased particle size.Type: GrantFiled: October 8, 1982Date of Patent: October 4, 1983Assignee: Atlantic Richfield CompanyInventors: James J. Harris, Donald E. Hostetler
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Patent number: 4396748Abstract: Alpha olefins are polymerized in the presence of catalyst compositions which are the catalytic reaction products of (A) the reaction product or complex resulting from the mixing of (1) a mixture of a transition metal compound such as a tetraalkoxy titanium compound and an alcohol and (2) an essentially non-reducing alkylating agent such as a dialkyl zinc compound and (B) a magnesium halide.Type: GrantFiled: October 22, 1981Date of Patent: August 2, 1983Assignee: The Dow Chemical CompanyInventor: Randall S. Shipley
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Patent number: 4387200Abstract: A process for polymerizing olefins employing as a catalyst therefor, the reaction product of (A) the reaction product of (1) the reaction product of (a) an alkyl magnesium compound such as dibutylmagnesium, with (b) an oxygen-containing and/or nitrogen-containing compound such as n-propyl alcohol, or isopropylamine, with (2) a halide source such as titanium tetrachloride or silicon tetrachloride; and (B) a transition metal compound such as titanium tetrachloride and (C) a reducing agent such as triisobutylaluminum. The polymers which are produced in the presence of this catalyst and a cocatalyst such as triethylaluminum have a low catalyst support to transition metal ratio and therefore, the catalyst efficiency based on quantity of polymer per quantity of total catalyst is very high resulting in a polymer having good color and very little, if any, corrosion.Type: GrantFiled: March 22, 1982Date of Patent: June 7, 1983Assignee: The Dow Chemical CompanyInventors: Donald E. Gessell, Ronald L. Gibbs, Ricardo Fuentes, Jr.
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Patent number: 4385161Abstract: A catalyst component is a transition metal composition which is obtained by reacting together an inert particulate material, an organic magnesium compound, a halogen-containing compound such as carbon tetrachloride silicon tetrachloride or boron trichloride and a specified transition metal compound such as VOCl.sub.3, bis(n-butoxy) titanium dichloride or zirconium tetrabenzyl. The catalyst component obtained can be used, together with an organic metal compound, to give an olefin polymerization catalyst. The catalyst can be used to effect the polymerization of olefin monomers, for example, the copolymerization of ethylene with an alpha-olefin monomer such as butene-1 in a fluidized bed reactor.Type: GrantFiled: January 6, 1981Date of Patent: May 24, 1983Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens, John McMeeking
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Patent number: 4383097Abstract: There is disclosed a process for the regulation of the molecular weight of high cis polybutadiene prepared by polymerizing butadiene under solution polymerization conditions employing as the catalyst system a mixture of (a) organoaluminum compounds; (b) organonickel compounds; and (c) fluorine containing compounds; said polymerization being conducted in the presence of nonconjugated diolefins of the formula of the structure ##STR1## wherein R.sub.1 may be; --CH.sub.2 --; --C.sub.2 H.sub.4 --; --C.sub.3 H.sub.6 --; ##STR2## and R.sub.2 may be H, --CH.sub.3, --C.sub.2 H.sub.5 or --C.sub.3 H.sub.7 and R.sub.2 is trans to R.sub.1.Type: GrantFiled: August 21, 1981Date of Patent: May 10, 1983Assignee: The Goodyear Tire & Rubber CompanyInventors: Kenneth F. Castner, Paul H. Sandstrom
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Patent number: 4380507Abstract: Catalysts for polymerizing ethylene to high yields of polyethylene having a controlled particle size are disclosed. The catalysts are prepared from new catalyst-forming components which are the reaction products of solid halogenated titanium compounds, Grignard compounds and halogenating agents. Said components, on mixing with organometallic compounds of metals belonging to Groups I-III of the Mendelyeev Periodic Table result in the catalysts capable of polymerizing ethylene to polyethylene having a controlled particle size.Type: GrantFiled: November 24, 1981Date of Patent: April 19, 1983Assignee: Montedison S.p.A.Inventors: Luciano Noristi, Giovanni Baruzzi
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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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Patent number: 4376064Abstract: Catalyst for production of polyolefins of improved morphology comprises (A) organometallic promoter and (B) product obtained by contacting (1) at least one oxygenated compound of phosphorus with (2) catalytic complex comprising an intimate association of at least one reduced Group IVB-VB metal halide, at least one divalent metal halide and at least one aluminum compound. Oxygenated phosphorus compound is used in an amount effective to improve polymer morphology without substantial adverse effects on other catalytic properties.Type: GrantFiled: May 26, 1981Date of Patent: March 8, 1983Assignee: Standard Oil Co. (Indiana)Inventors: Glen R. Hoff, Peter Fotis
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Patent number: 4370457Abstract: A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of hexavalent sulfur mineral acid or anhydride whereby the amount of n-hexane-soluble polymeric product is decreased.Type: GrantFiled: December 12, 1980Date of Patent: January 25, 1983Assignee: Standard Oil Company (Indiana)Inventor: Nikolaous K. Balint
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Patent number: 4368304Abstract: A process for producing .alpha.-olefin polymers is provided, which comprises: reacting an organoaluminum compound with an electron donor in a specified ratio in a solvent at a specified temperature to obtain a solid product (I); reacting solid product (I) with TiCl.sub.4 at a specified temperature in a specified ratio of Al/Ti and then removing a liquid portion from the resulting material followed by washing to obtain a solid product (II) having no free TiCl.sub.4 ; reacting solid product (II) with an electron donor and an electron acceptor in a specified ratio at a specified temperature to obtain a solid product (III); and polymerizing .alpha.-olefin(s) in the presence of a catalyst comprising a combination of solid product (III) with an organoaluminum compound. This process provides a catalyst having a high storing and thermal stability and a polymer having a uniform particle size.Type: GrantFiled: February 4, 1981Date of Patent: January 11, 1983Assignee: Chisso CorporationInventors: Akihiro Sato, Toshihiro Uwai, Tohru Hanari, Kazutsune Kikuta, Masazumi Miyajima
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Patent number: 4367322Abstract: In a process for producing propylene copolymer containing about 80 to 99 mol % propylene and about 1 to 20 mol % ethylene and/or an .alpha.-olefin having 4 to 18 carbon atoms using a Ziegler-Natta catalyst, the improvement which comprises said Ziegler-Natta catalyst comprising:(A) titanium trichloride prepared by reducing titanium tetrachloride with an organoaluminum compound and activating the product; and(B) an organoaluminum compound;with the molar ratio of (B)/(A) being about 20 to 100.Type: GrantFiled: August 10, 1981Date of Patent: January 4, 1983Assignee: Sumitomo Chemical Company, Ltd.Inventors: Akinobu Shiga, Kiyoshi Matsuyama, Masahiro Kakugo, Yukio Naito, Akira Nunose, Masaharu Nishioka
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Patent number: 4359403Abstract: 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 treated with a fluorine compound and with a compound of magnesiumhydrocarbyl or a complex of the general formula (MgR.sub.2).sub.m (AlR.sub.3 ').sub.n where R and R' are alkyl or aryl 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 separation of the solvent. The disclosure also includes a method of making such catalysts and a method of making polymers of one or more 1-olefins by the use of these catalysts under polymerizing conditions.Type: GrantFiled: April 13, 1981Date of Patent: November 16, 1982Assignee: Chemplex CompanyInventors: Raymond E. Hoff, Thomas J. Pullukat, Mitsuzo Shida
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Patent number: 4355144Abstract: In a process for producing polypropylene comprising polymerizing propylene in the presence of hydrogen and a catalyst system comprising (A) titanium trichloride obtained by reducing titanium tetrachloride with an organoaluminum compound and reacting the reduced solid with an ether represented by the formula:R.sup.1 -O-R.sup.2wherein R.sup.1 and R.sup.2 are defined hereinbefore, and a halogen compound selected from the group consisting of (i) halogen or interhalogen compounds of the formula, X.sup.1 X.sup.2.sub.a (wherein X.sup.1, X.sup.2 and a are defined hereinbefore), (ii) titanium halides, and (iii) organic halogen compounds, simultaneously or successively and (B) an organoaluminum compound, the improvement which comprises supplying ethylene together with propylene to the polymerization system such that the ethylene concentration in the vapor phase of the system based on the total amount of propylene, ethylene and hydrogen in the vapor phase of the system is 0.15 to 1.Type: GrantFiled: April 24, 1981Date of Patent: October 19, 1982Assignee: Sumitomo Chemical Company LimitedInventors: Akinobu Shiga, Kiyoshi Matsuyama, Masahiro Kakugo, Yukio Naito, Seiichiro Ima, Katsuyoshi Yamashita
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Patent number: 4354010Abstract: A solid transition metal compound is ground with an organo-sulphur compound which is a defined aromatic sulphone, sulphonamide or sulphide such as diphenylsulphone, N,N-diethyl-4-phenoxy benzenesulphonamide or phenoxathiin. A Lewis Acid such as titanium tetrachloride can be present during the grinding operation. Alternatively there may be present, during the grinding, an oxidizing agent capable of generating tetravalent titanium in the presence of titanium trichloride, for example carbon tetrachloride or gaseous oxygen. The grinding can be effected in a ball-mill or a vibrating mill. The materials may be added during the grinding and the temperature may be varied during the grinding. A liquid which is a solvent for the organo-sulphur compound or complexes thereof with aluminum chloride may be present during a part of the grinding.Type: GrantFiled: September 24, 1980Date of Patent: October 12, 1982Assignee: Imperial Chemical Industries LimitedInventor: Alan B. Newton
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Patent number: 4347158Abstract: A supported high efficiency catalyst component for polyolefin production and methods of making and using the same are disclosed. An enhanced support made from the materials comprising a support base, an inorganic Lewis acid and an electron donor is combined with an active transition metal compound and optionally a second electron donor to form the catalyst component. Additionally, a dehydrating agent may be pre-combined with the support base in the production of the catalyst support. The methods of producing such catalyst supports and catalyst components are performed by milling in the absence of any solvent. Such catalysts produce polymer of such high quality and quantity that polymer extraction and polymer deashing are not necessary.Type: GrantFiled: May 2, 1980Date of Patent: August 31, 1982Assignee: Dart Industries, Inc.Inventors: Malcolm J. Kaus, Nemesio D. Miro
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Patent number: 4335229Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to about 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.twherein.alpha., p, q, r and s each independently is 0 or a number greater than 0,t is a number greater than 0,p+q+r+s=m.alpha.+2,O.ltoreq.(r+s)/(.alpha.+1)<2,m is the valance of M,M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 and R.sup.2 each independently is a hydrocarbon group having 1 to 20 carbon atoms,X.sup.1 and X.sup.Type: GrantFiled: August 13, 1980Date of Patent: June 15, 1982Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Hisaya Sakurai, Yoshihiko Katayama, Tadashi Ikegami, Masayasu Furusato
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Patent number: 4330646Abstract: A process for polymerizing an .alpha.-olefin comprising contacting the olefin in liquid phase at a temperature of about 120.degree. to about 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 formulaM.sub..alpha. Mg.sub..beta. R.sub.p.sup.1 R.sub.q.sup.2 X.sub.r.sup.1 X.sub.s.sup.2wherein.alpha., p, q, r and s each independently is 0 or a number greater than 0,.beta. is 1 or a number greater than 1,p+q+r+s=m.alpha.+2.beta.,0.ltoreq.(r+s)/(.alpha.+.beta.)<2,m is the valence of M,M is a metal of the 1st to 3rd groups of the Periodic Table,R.sup.1 and R.sup.2 each independently is a hydrocarbon group having 1 to 20 carbon atoms,X.sup.1 and X.sup.Type: GrantFiled: July 21, 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: 4330431Abstract: A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of hydrohalic mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.Type: GrantFiled: March 6, 1980Date of Patent: May 18, 1982Assignee: Standard Oil Company (Indiana)Inventor: Nikolaous K. Balint
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Patent number: 4328121Abstract: A transition metal compound such as titanium tetrahydrocarbyloxides and a metal hydrocarbyloxide compound such as magnesium hydrocarbyloxides are chemically combined to form a first catalyst component which is treated with a second catalyst component comprising an organometallic compound precipitating agent to produce an active olefin polymerization catalyst. High polymer yields are realized per gram of catalyst when the catalyst thus produced is treated with a halide ion exchanging source and used with an organometallic cocatalyst.Type: GrantFiled: August 4, 1980Date of Patent: May 4, 1982Assignee: Phillips Petroleum CompanyInventor: Charles E. Capshew
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Patent number: 4326988Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is mixed with a precipitating agent to form an active olefin polymerization catalyst. The catalyst can be further treated with a halide ion exchanging source to form an active olefin polymerization catalyst. Prepolymer is deposited on the catalyst(s) in an amount effective to reduce polymer fines when the catalyst(s) are used in polymerization processes.Type: GrantFiled: August 12, 1980Date of Patent: April 27, 1982Assignee: Phillips Petroleum CompanyInventors: Melvin B. Welch, Richard E. Dietz, Charles E. Capshew
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Patent number: 4325837Abstract: A transition metal compound and a metal halide compound are chemically combined to form a composition of matter. The composition of matter is rapidly mixed with a precipitating agent to form an active olefin polymerization catalyst under an olefin atmosphere and prepolymer is formed on said catalyst to yield a catalyst capable of producing low fines content polymer.Type: GrantFiled: August 12, 1980Date of Patent: April 20, 1982Assignee: Phillips Petroleum CompanyInventors: Charles E. Capshew, James N. Short, M. Bruce Welch, Richard E. Dietz
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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: 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: 4309521Abstract: A process for producing .alpha.-olefin polymers is provided which comprises:reacting an organoaluminum compound (A.sub.1) with an electron donor (B.sub.1) to obtain a reaction product (I);reacting (I) with TiCl.sub.4 to obtain a solid product (II);reacting (II) with an electron donor (B.sub.2) and an electron acceptor to obtain a solid product (III);combining (III) with an organoaluminum compound (A.sub.2) and a reaction product (G) of an organoaluminum (A.sub.3) with an electron donor (B.sub.3) ((III), (A.sub.2) and (G) being referred to as catalyst components), and in this combination, subjecting a part or the whole of the catalyst components to polymerization treatment with an .alpha.-olefin at least in the presence of (III) and said (A.sub.2) to obtain a preliminarily activated catalyst;andpolymerizing an .alpha.-olefin in the presence of the catalyst.Type: GrantFiled: May 14, 1980Date of Patent: January 5, 1982Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Kenji Matsuda, Toshihiro Uwai, Tohru Hanari
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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: 4304892Abstract: A process for producing a solid titanium trichloride catalyst which comprisesat a temperature of -40.degree. C. to 40.degree. C. mixing titanium tetrachloride with an organo-aluminum compound of the formula (I):AlR.sub.n X.sub.3-n (I)wherein R has up to 10 carbon atoms and is an aliphatic hydrocarbon group which may be straight chain, branched chain or cyclic, or an aromatic hydrocarbon group; X is a halogen atom or a hydrogen atom; and n is a number satisfying the relation, 1.5.ltoreq.n.ltoreq.3;in the presence of an ether compound of the formula (II):R.sup.2 OR.sup.3 (II)wherein R.sup.2 and R.sup.3, which may be the same or different, each is an alkyl group, an aralkyl group or an alkenyl group, each having up to 10 carbon atoms, to reduce the titanium tetrachloride; maintaining the mixed solution at a temperature of 10.degree. C. to 50.degree. C.Type: GrantFiled: July 8, 1980Date of Patent: December 8, 1981Assignee: Sumitomo Chemical Co., Ltd.Inventors: Akinobu Shiga, Yoshiharu Fukui, Kazuhiro Matsumura, Toshio Sasaki, Masahisa Okawa
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Patent number: 4301029Abstract: A component of a polymerization catalyst is prepared by reacting an organo-magnesium compound, or a complex with an organo-aluminium compound, with a solid, inorganic oxide, then with a 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 olefin monomer particularly propylene or mixtures of ethylene and a 1-olefin containing at least 4 carbon atoms. The catalyst system has a high activity, is stereospecific and has a lower proportion of halogen than some other catalyst systems.Type: GrantFiled: January 10, 1980Date of Patent: November 17, 1981Assignee: Imperial Chemical Industries LimitedInventors: Anthony D. Caunt, Paul D. Gavens
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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: 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: 4262103Abstract: A method for preparing copolymers of a bicycloheptene and 1,3-butadiene is described. The method comprises polymerizing said monomers in a hydrocarbon solvent in the presence of a catalyst mixture comprising:(a) at least one organoaluminum compound of the formula R.sub.3 Al or R.sub.2 AlX wherein R is an alkyl radical containing from one to about 12 carbon atoms, and X is a halogen, and(b) at least one molybdenum salt.These copolymers can be oil extended and vulcanized to high strength rubbers.Type: GrantFiled: December 5, 1977Date of Patent: April 14, 1981Assignee: The B. F. Goodrich CompanyInventor: Robert J. Minchak
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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: 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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Patent number: RE31187Abstract: A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of Group Va or Group VII oxygen mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.Type: GrantFiled: June 8, 1981Date of Patent: March 22, 1983Assignee: Standard Oil Company (Indiana)Inventor: Nikolaous K. Balint
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Patent number: RE31243Abstract: A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of hexavalent sulfur mineral acid or anhydride whereby the amount of n-hexane-soluble polymeric product is decreased.Type: GrantFiled: November 25, 1981Date of Patent: May 17, 1983Assignee: Standard Oil Company (Indiana)Inventor: Nikolaus K. Balint
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Patent number: RE31331Abstract: A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of Group Va or Group VII oxygen mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.Type: GrantFiled: June 8, 1981Date of Patent: August 2, 1983Assignee: Standard Oil Company (Indiana)Inventor: Nikolaous K. Balint