Monomer Polymerized In Vapor State In Presence Of Transition Metal Containing Catalyst Patents (Class 526/901)
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Patent number: 4703094Abstract: A process and apparatus as shown in FIG. 1 for the production of polyolefins by the polymerization of alpha-olefins in the gas phase, in several stages, in at least two polymerization reactors interconnected by a transfer device making it possible to transfer the polyolefins resulting from the first reactor into the second reactor, in which the polymerization is continued under conditions identical to or different from those of the first reactor.Type: GrantFiled: February 12, 1986Date of Patent: October 27, 1987Assignee: BP Chemicals LimitedInventor: Charles Raufast
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Patent number: 4692501Abstract: In a process for producing an olefin polymer which comprises continuously polymerizing an olefin in the presence of a catalyst composed of a transition metal compound component and an organometallic compound component in at least two independent polymerization zones connected in series by a pipeline while feeding the olefin and the catalyst into an upstream zone of polymerization and withdrawing the resulting polymer from a downstream zone of polymerization; the improvement wherein(1) the polymerization in the upstream polymerization zone is carried out in a liquid medium under conditions for slurry polymerization,(2) the solid polymer-containing slurry discharged from the upstream polymerization zone is fed into a liquid medium exchanging zone through an upper feed opening (A) in its upper portion, said liquid medium exchanging zone being provided between the upstream polymerization zone and the downstream polymerization zone and connected to these zones by pipelines, and an additional supply of the liquid mType: GrantFiled: July 31, 1985Date of Patent: September 8, 1987Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Hideo Mineshima, Haruyuki Koda, Ryoichi Yamamoto
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Patent number: 4684703Abstract: A catalyst formed from selected organo aluminum compounds and a precursor composition of the formulaMg.sub.m Ti.sub.l (OR).sub.n X.sub.p [ED].sub.qwhereinED is a selected electron donor compoundm is .gtoreq.0.5 to .ltoreq.56n is 0 or 1p is .gtoreq.6 to .ltoreq.116q is .gtoreq.2 to .ltoreq.85R is a C.sub.1 to C.sub.14, aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, andX is selected from the group consisting of Cl, Br, I, or mixtures thereof, which catalyst is in particulate form and diluted with an inert carrier material; a process for preparing such catalyst; a process for using said catalyst to readily prepare ethylene homopolymer having a density of about .gtoreq.0.958 to .ltoreq.0.972 and a melt flow ratio of .gtoreq.22 to .ltoreq.32 in a low pressure gas phase process at a productivity of .gtoreq.50,000 pounds of polymer per pound of Ti. Novel polymers and molded articles are prepared.Type: GrantFiled: March 7, 1983Date of Patent: August 4, 1987Assignee: Union Carbide CorporationInventors: Burkhard E. Wagner, Frederick J. Karol, George L. Goeke, Robert J. Jorgensen, Nils Friis
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Patent number: 4665141Abstract: Process of polymerizing a monomer charge including ethylene by (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least about 0.5 mol, per mol of surface hydroxyl groups, of at least one organometallic compound corresponding to the formula R.sub.x MR'.sub.y R".sub.z, wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 molar proportion, per mol of organometallic compound, of a vanadium component consisting essentially of a mixture of about 10-90 mol percent of VOCl.sub.Type: GrantFiled: March 25, 1985Date of Patent: May 12, 1987Assignee: Cities Service Oil & Gas Corp.Inventor: David E. Aylward
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Patent number: 4665140Abstract: Process of polymerizing a monomer charge including ethylene by (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R.sub.x MR'.sub.y R".sub.z, wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound corresponding to a formula selected from (RO).sub.n VOX.sub.3-n and (RO).sub.m VX.sub.4-m, in which formulas R represents a C.sub.1 -C.Type: GrantFiled: March 25, 1985Date of Patent: May 12, 1987Assignee: Cities Service Oil & Gas Corp.Inventors: B. Timothy Pennington, Paul V. Roling, John T. T. Hsieh
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Patent number: 4665138Abstract: Process of polymerizing a monomer charge including ethylene by (1) drying an inorganic oxide having surface hydroxyl groups, e.g. silica, alumina, magnesia, etc. to remove adsorbed water (2) reacting the surface hydroxyl groups with at least a stoichiometric amount of an organometallic compound having at least one alkyl group attached to a Group III metal, e.g., a trialkylaluminum, (3) reacting the thus-treated inorganic oxide with a vanadium halide, such as (a) VOCl.sub.3, VOBr.sub.3, and/or mono-, di-, and/or trihydrocarbyloxy derivatives thereof and/or (b) VCl.sub.4, VBr.sub.4, and/or mono-, di-, tri-, and/or tetrahydrocarbyloxy derivatives thereof, (4) reacting that reaction product with at least about 0.1 mol, per mol of organometallic compound, of an ether-alcohol corresponding to the formula R"[OCHR'(CH.sub.2).sub.n CHR].sub.Type: GrantFiled: March 21, 1985Date of Patent: May 12, 1987Assignee: Cities Service Oil & Gas CorpInventors: Paul V. Roling, Richard L. Veazey, David E. Aylward
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Patent number: 4665139Abstract: Process of polymerizing a monomer charge including ethylene by (1) drying an inorganic oxide having surface hydroxyl groups to form a support that is substantially free of adsorbed water, (2) reacting the surface hydroxyl groups of the support with at least a substantially stoichiometric amount of at least one organometallic compound corresponding to the formula R.sub.x MR'.sub.y R".sub.z, wherein M is a metal of Group III of the periodic table, R is an alkyl group containing 1 to 12 carbon atoms, R' and R" are independently selected from the group consisting of H, Cl, and alkyl and alkoxy groups containing 1 to 12 carbon atoms, x has a value of 1 to 3, and y and z both represent values of 0 to 2, the sum of which is not greater than 3-x, (3) reacting the thus-treated support with at least about 0.001 mol, per mol of organometallic compound, of at least one vanadium compound prepared by reacting one molar proportion of VOCl.sub.3 and/or VOBr.sub.3 with about 0.Type: GrantFiled: March 21, 1985Date of Patent: May 12, 1987Assignee: Cities Service Oil & Gas Corp.Inventors: Richard L. Veazey, B. Timothy Pennington
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Patent number: 4611038Abstract: A process is provided for the polymerization of olefins in the gas phase wherein olefins are contacted with a catalyst system consisting of an active solid hydrocarbon having been prepared by forming a pulverulent composition by mixing a transition metal component, a porous organic or inorganic solid support and an organometallic compound of the organo-Al, organo-Mg or organo-Zn type, and polymerizing a controlled amount of one or more C.sub.2 to C.sub.12 olefins in the gas phase in contact with the pulverulent composition with a specific hourly conversion of the olefins to produce the active solid hydrocarbon.Type: GrantFiled: July 18, 1985Date of Patent: September 9, 1986Assignee: AtochemInventors: Claude Brun, Auguste Cheux, Robert Pelletier
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Patent number: 4564660Abstract: A method for smoothly and reliably initiating polymerization of ethylene with a supported chromium oxide catalyst, with smaller amounts of catalyst and in substantially shorter periods of time then heretofore required, by adding an alkylaluminum compound and a hydroxyl-containing compound to the reactor of a polymerization reaction system prior to the commencement of polymerization and subjecting said alkylaluminum compound and hydroxyl-containing compound to suitable conditions of temperature and pressure for a time sufficient for said alkylaluminum compound to react completely with the moisture present in said reactor and said hydroxyl-containing compound.Type: GrantFiled: June 30, 1983Date of Patent: January 14, 1986Assignee: Union Carbide CorporationInventors: Gary H. Williams, Frederick J. Karol
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Patent number: 4533705Abstract: A process for producing .alpha.-olefin polymers having high crystallinity and good particle form, with a high yield is provided. The polymerization therefor is carried out in the presence of a preactivated catalyst suitable particularly to gas phase polymerization or gas phase polymerization following slurry or bulk polymerization.The catalyst is prepared by reacting a reduction solid prepared by reducing TiCl.sub.4 with an organoaluminum compound, with an electron donor and an electron acceptor to obtain a solid product, andcombining this solid product with an organoaluminum compound, an .alpha.-olefin and a reaction product of an organoaluminum compound with an electron donor.Type: GrantFiled: July 21, 1983Date of Patent: August 6, 1985Assignee: Chisso CorporationInventors: Akihiro Sato, Kazutsune Kikuta, Toshihiro Uwai, Kenji Matsuda, Nobutaka Hattori
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Patent number: 4532311Abstract: A process for reducing sheeting during production of polyolefins by polymerization of alpha-olefins utilizing titanium based polymerization catalysts wherein the static electric charges in the reactor at the site of possible sheet formation are maintained below static voltage levels which would otherwise cause sheet formation.Type: GrantFiled: September 14, 1984Date of Patent: July 30, 1985Assignee: Union Carbide CorporationInventors: Bernard D. Fulks, Steven P. Sawin, Collin D. Aikman, John M. Jenkins, III
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Patent number: 4525552Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of a catalyst system comprising the combination of at least one organometallic compound with a transition metal compound supported on a solid carrier, said solid carrier being obtained by the reaction of (a) a magnesium halide, (b) a compound represented by the formula: Al(OR).sub.n X.sub.3-n, where R is a hydrocarbon residual group having 1 to 24 carbon atoms, X is a hydrogen atom, and n is 0<n.ltoreq.3, and (c) a compound represented by the formula: Si(OR').sub.m X.sub.4-m, where R' is a hydrocarbon residual group having 1 to 20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4. The resulting polymers are characterized by a large bulk density and a narrow range of molecular weight distribution.Type: GrantFiled: February 8, 1984Date of Patent: June 25, 1985Assignee: Nippon Oil Co., Ltd.Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mitsuji Miyoshi
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Patent number: 4522987Abstract: A process for copolymerizing ethylene with another monoolefin is described wherein the other monoolefin is incorporated into the polymer at very high efficiencies and in several instances the copolymer produced contains a higher concentration of the comonomer than the gas phase in the polymerization zone. A novel ethylene/1-hexene copolymer having very high relative comonomer dispersities (99% or higher, and even above 100%) is also described.Type: GrantFiled: July 9, 1982Date of Patent: June 11, 1985Assignee: Phillips Petroleum CompanyInventors: John P. Hogan, Eric T. Hsieh, James C. Randall
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Patent number: 4521573Abstract: Film grade ethylene copolymers are prepared by copolymerizing ethylene with at least one C.sub.3 to C.sub.8 alpha olefin employing a catalyst formed from an organo aluminum activator compound and a precursor composition impregnated in very fine particle sized porous silica, said precursor composition having the formulaMG.sub.m Ti.sub.1 (OR).sub.n X.sub.p [ED.sub.q ]wherein R is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical; X is selected from the group consisting of Cl, Br, I or mixtures thereof; ED is an electron donor compound; m is .gtoreq.0.5 to .ltoreq.56; n is 0, 1 or 2; p is .gtoreq.2 to .ltoreq.116; and q is .gtoreq.2 to .ltoreq.85; and said organo aluminum activator compound having the formulaAl(R").sub.c X'.sub.d H.sub.ewherein X' is Cl or OR'"; R" and R'" are the same or different and are C.sub.1 to C.sub.14 saturated hydrocarbon radicals; d is 0 to 1.5; e is 1 or 0; and c+d+e=3.Type: GrantFiled: July 25, 1983Date of Patent: June 4, 1985Assignee: Union Carbide CorporationInventors: Kiu H. Lee, Gary S. Cieloszyk
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Patent number: 4518752Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of an improved catalyst comprising a solid catalyst component and an organometal compound, said solid catalyst component being obtained by the reaction of: (a) a magnesium halide, (b) a compound represented by the formula: Me(OR).sub.n X.sub.z-n where Me is any of the Group I-VIII elements of the Periodic Table, excluding Al, Si, Ti and V, R is a hydrocarbon residual group having 1-24 carbon atoms, X is a halogen atom, z represents the valence of Me and n is 0<n.ltoreq.z, and (c) a compound represented by the formula: Si(OR').sub.m X.sub.4-m where R' is a hydrocarbon residual group having 1-20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4, and (d) a titanium compound and/or a vanadium compound. The resulting polymers are characterized by a large bulk density, a narrow range of molecular weight distribution, and small amounts of hexane extraction.Type: GrantFiled: November 15, 1983Date of Patent: May 21, 1985Assignee: Nippon Oil Co., Ltd.Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura
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Patent number: 4507448Abstract: A process for the homopolymerization or copolymerization of olefins is disclosed, which is carried out in the presence of a catalyst system comprising the combination of at least one organometallic compound with a component resulting from the reaction of (a) a magnesium halide, (b) a compound represented by the formula, Al(OR).sub.n X.sub.3-n, where R is a hydrocarbon residual group having 1 to 20 carbon atoms, X is a hydrogen atom, and n is 0.ltoreq.n.ltoreq.3, (c) a compound represented by the formula, Si(OR').sub.m X.sub.4-m, where R' is a hydrocarbon residual group having 1 to 20 carbon atoms, X is a halogen atom, and m is 0.ltoreq.m.ltoreq.4, and (d) a titanium compound and/or a vanadium compound. The resulting polymers have a large bulk density and a narrow range of molecular weight distribution.Type: GrantFiled: May 4, 1982Date of Patent: March 26, 1985Assignee: Nippon Oil Co., Ltd.Inventors: Nobuyuki Kuroda, Toru Nakamura, Yutaka Shikatani, Kazuo Matsuura, Mitsuji Miyoshi
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Patent number: 4503203Abstract: Granular stereoregular butene-1 polymers having a high isotactic content, and an extractables content of no more than about 15 weight percent in boiling ethyl ether, are produced over a continuous extended period of time in a low pressure gas phase fluidized bed process, in the absence of liquid diluent components, with a stereospecific olefin polymerization catalyst under a selected set of operating conditions.Type: GrantFiled: December 20, 1983Date of Patent: March 5, 1985Assignee: Union Carbide CorporationInventors: Nancy M. Golembeski, Robert J. Jorgensen, Robert D. Cleland, Allen Noshay
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Patent number: 4482687Abstract: Ethylene copolymers having a density of about 0.91 to 0.94 and a melt flow ratio of about .gtoreq.26 to .ltoreq.40 are readily produced in a low pressure gas phase process at a productivity of .gtoreq.500,000 pounds of polymer per pound of Ti with a catalyst formed from selected organo aluminum compounds and a composition prepared by copulverizing magnesium dihalide with a complex obtained by contacting a titanium compound of the structure Ti(OR).sub.a X.sub.b with an ether, ester, ketone or amine,wherein R is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, or COR' where R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical,X is Cl, Br, I or mixtures thereof, a is 0 or 1, b is 2 to 4 inclusive and a+b=3 or 4.Type: GrantFiled: June 24, 1983Date of Patent: November 13, 1984Assignee: Union Carbide CorporationInventors: Allen Noshay, Frederick J. Karol, Robert J. Jorgensen
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Patent number: 4469855Abstract: Ethylene is copolymerized in the gas phase, for example in a fluidized bed, using a gaseous mixture comprising ethylene, at least one olefine monomer containing at least 4 carbon atoms, an inert gaseous diluent and, optionally, hydrogen at a total absolute pressure of at least one MN/m.sup.2. The comonomer preferably contains 6 or 8 carbon atoms. The partial pressure of the comonomer may be in the range from 1 kN/m.sup.2 up to 550 kN/m.sup.2. The inert gaseous diluent typically has a partial pressure of at least 250 kN/m.sup.2 and forms 20% molar of the gaseous mixture. The inert gaseous diluent may be nitrogen and is preferably ethane.Type: GrantFiled: May 23, 1983Date of Patent: September 4, 1984Assignee: Imperial Chemical Industries PLCInventor: Richard R. Cooper
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Patent number: 4448944Abstract: Polyolefins having a broad molecular weight distribution are obtained in a very high yield even using a catalyst based on a reaction product of a magnesium alcoholate with titanium tetrachloride, if the hydrocarbon-insoluble product of the reaction of the magnesium alcoholate with titanium tetrachloride is heated to a fairly high temperature with a chloroalkoxytitanate, in order to split off alkyl chlorides.Type: GrantFiled: June 14, 1982Date of Patent: May 15, 1984Assignee: Hoechst AktiengesellschaftInventors: Joachim Berthold, Bernd Diedrich, Rainer Franke, Jurgen Hartlapp, Werner Schafer, Wolfgang Strobel
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Patent number: 4447587Abstract: Polyolefins having a broad molecular weight distribution are obtained in a very high yield even using, as the catalyst, a product from the reaction of a magnesium alcoholate with titanium tetrachloride, if the reaction between the magnesium alcoholate and the titanium tetrachloride is carried out at a relatively low temperature and the reaction mixture is then heated to a fairly high temperature in order to split off alkyl chlorides.Type: GrantFiled: June 14, 1982Date of Patent: May 8, 1984Assignee: Hoechst AktiengesellschaftInventors: Joachim Berthold, Bernd Diedrich, Rainer Franke, Jurgen Hartlapp, Werner Schafer, Wolfgang Strobel
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Patent number: 4442271Abstract: The disclosure is directed to an improvement in the gas phase polymerization of propylene using a Ziegler-Natta catalyst in the presence of hydrogen wherein the gaseous propylene is withdrawn from the reactor, cooled and condensed and returned as a liquid to the reactor in order to regulate the polymerization temperature. The amount of the gaseous phase in the condenser-cooler-accumulator system is kept constant by regulating the amount of gaseous phase returned to the reactor.Type: GrantFiled: May 26, 1982Date of Patent: April 10, 1984Assignee: BASF AktiengesellschaftInventors: Wolfgang Rau, Helmut Klamann, Peter Hennenberger
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Patent number: 4390669Abstract: In a process for polymerizing olefins in the gaseous phase in a first gas-phase polymerization zone and a second gas-phase polymerization zone, which are provided independently from each other, in the presence of a catalyst composed of a transition metal catalyst component and an organometallic compound of a metal of Groups I to III of the periodic table while feeding the catalyst-containing polymer formed in the first zone to the second zone; the improvement wherein(i) a suspension zone for forming a suspension of the polymer from the first zone in an easily volatile hydrocarbon medium which is liquid under the conditions of feeding the polymer is provided in a feed passage for feeding the polymer from the first zone to the second zone, and(ii) the suspension of the polymer in said liquid medium formed in the suspension zone is fed to the second zone.Type: GrantFiled: May 22, 1981Date of Patent: June 28, 1983Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Yoshinori Morita, Shinzi Hayata, Akifumi Kato, Hideo Nara, Tohru Watanabe
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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: 4383095Abstract: A catalytic process for preparing ethylene polymers having a density of .gtoreq.0.95 to .ltoreq.0.97 and a melt flow ratio of about .gtoreq.22 to .ltoreq.32 in a low pressure gas phase process at a productivity of .gtoreq.50,000 pounds of polymer per pound of Ti with a catalyst formed from selected organoaluminum compounds and a precursor composition of the formulaMg.sub.m Ti.sub.1 (OR).sub.n X.sub.p [ED].sub.qwherein ED is a selected electron donor compoundm is .gtoreq.0.5 to .ltoreq.56n is 0, 1 or 2p is .gtoreq.2 to .ltoreq.116q=1.5 m+2R is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, or COR' wherein R' is a C.sub.1 to C.sub.14 aliphatic or aromatic hydrocarbon radical, andX is selected from the group consisting of Cl, Br, I or mixtures thereof,which catalyst is in particulate form and impregnated in a porous inert carrier material.Type: GrantFiled: November 20, 1981Date of Patent: May 10, 1983Assignee: Union Carbide CorporationInventors: George L. Goeke, Burkhard E. Wagner, Frederick J. Karol
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Patent number: 4383093Abstract: A tubular polymerization reactor comprising a feed opening for a polymerizable material at one end portion, a withdrawal opening for the resultant polymer at the other end portion, a tubular reaction space within the reactor extending from said feed opening to said withdrawal opening, and a rotary conveying member disposed within the reaction space and extending therealong with some clearance from the inner wall surface of the polymerization reactor; characterized in that(i) the length-to-diameter ratio of the tubular reaction space is about 20 or more, and(ii) the rotary conveying member is of a tubular coil-like shape;and a process for polymerization using the aforesaid tubular polymerization reactor.Type: GrantFiled: June 3, 1981Date of Patent: May 10, 1983Assignee: Mitsui Petrochemical Industries Ltd.Inventors: Shigemi Shiraki, Saiji Nakano
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Patent number: 4370456Abstract: Ethylene copolymers having improved resistance to pinstriping and gel streaking when extruded into film can be produced by continuously copolymerizing ethylene with one or more higher alpha olefin monomers in a low pressure gas phase reaction with a catalyst composition prepared by forming a precursor composition from a magnesium compound, titanium compound, and electron donor compound; diluting said precursor composition with a silica support which has been treated with a dialkylzinc compound; and activating the diluted precursor composition with an organoaluminum compound.Type: GrantFiled: November 23, 1981Date of Patent: January 25, 1983Assignee: Union Carbide CorporationInventor: Kathleen F. George
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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: 4368291Abstract: In a low pressure process for polymerizing ethene using a Ziegler mixed catalyst comprising (a) a titanium compound, a vanadium compound or a mixture thereof and (b) an aluminum-organic compound or a mixture thereof, an improvement is provided wherein the process is carried out in multi-stages comprising:polymerizing, in a first polymerization stage, in the liquid phase in a dispersion medium of a C.sub.3 - to C.sub.6 -hydrocarbon, andpolymerizing, in a last polymerization stage, in the gas phase.Type: GrantFiled: January 26, 1979Date of Patent: January 11, 1983Assignee: Chemische Werke Huels, A.G.Inventors: Albert Frese, Fritz Baxmann
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Patent number: 4363901Abstract: A process for producing high-quality .alpha.-olefin polymers with a higher yield in a long lasting stabilized manner even in the case of gas phase polymerization is provided. In the production process of .alpha.-olefin polymers which comprises reacting a trivalent metal halide with a divalent metal compound to obtain a solid product (I); reacting this product with at least one electron donor (ED) and at least one electron acceptor (EA), once to 10 times, and at that time, using TiCl.sub.4 at least once as the (EA) to obtain a solid product (II); combining this product with an organoaluminum compound (OAl) and an (ED) (these three being referred to as catalyst components), the improvement which comprises subjecting a part or the whole of the catalyst components to polymerization treatment with a small amount of an .alpha.-olefin, at least in the coexistence of the solid product (II) and (OAl), in the combination of the catalyst components to obtain a preactivated catalyst, and subjecting .alpha.Type: GrantFiled: February 12, 1981Date of Patent: December 14, 1982Assignee: Chisso CorporationInventors: Kazutsune Kikuta, Masami Tachibana, Akihiro Sato
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Patent number: 4354009Abstract: The copolymerization of ethylene with other alpha olefins in a low pressure gas phase reaction is improved with the use of a catalyst composition prepared by forming a precursor composition from a magnesium compound, titanium compound and electron donor compound; diluting said precursor composition with an inert carrier material; treating said diluted precursor composition with a hydrocarbyl aluminum dihalide compound; and activating the precursor composition treated in this manner with an organo aluminum compound.Type: GrantFiled: July 30, 1981Date of Patent: October 12, 1982Assignee: Union Carbide CorporationInventors: George L. Goeke, Burkhard E. Wagner, Frederick J. Karol
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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: 4349648Abstract: Ethylene copolymers having improved optical properties in film form are prepared by continuously copolymerizing ethylene with one or more higher alpha olefin monomers in a low pressure gas phase reaction with a catalyst composition prepared by forming a precursor composition from a magnesium compound, titanium compound, and electron donor compound; diluting said precursor composition with an inert carrier material; optionally partially activating the diluted precursor composition with an organo aluminum compound prior to introducing said diluted precursor composition into the polymerization reactor; and completely activating the diluted (and optionally partially activated) precursor composition in the polymerization reactor with a mixture of a dihydrocarbyl aluminum halide compound and a trihydrocarbyl aluminum compound.Type: GrantFiled: July 31, 1981Date of Patent: September 14, 1982Assignee: Union Carbide CorporationInventors: Robert J. Jorgensen, George L. Goeke, Frederick J. Karol
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Patent number: 4343926Abstract: The invention concerns a process for the production of elastomeric terpolymers of ethylene, propylene and dienes by the direct polymerization of the monomeric olefins in the gaseous state, in contact with a catalytic system comprising one or more solid compounds of titanium. The resulting terpolymers which are produced in the form of powders can be used without intermediate transformation for the production of molded or extruded articles.Type: GrantFiled: July 2, 1980Date of Patent: August 10, 1982Assignee: NAOHTACHIMIE Societe AnonymeInventors: Francois Caumartin, Jean L. Vidal, Pierre Mangin
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Patent number: 4338424Abstract: In a process for polymerizing olefins in the gaseous phase in a first gas-phase polymerization zone and a second gas-phase polymerization zone, which are provided independently from each other, in the presence of a catalyst composed of a transition metal catalyst component and an organometallic compound of a metal of Groups I to III of the periodic table and in the co-presence of hydrogen gas while feeding the catalyst-containing polymer formed in the first zone to the second zone; the improvement wherein(i) a dilution zone for diluting a feed flow from the first gas-phase polymerization zone which comprises a mixture of the polymer, the catalyst, the olefin gas and hydrogen gas by feeding a fresh supply of olefin gas thereto is provided in a feed passage for feeding said flow from the first gas-phase polymerization zone to the second gas-phase polymerization zone,(ii) a part of the gas phase in said feed flow diluted in the dilution zone is recycled to the first gas-phase polymerization zone, and remainder iType: GrantFiled: May 22, 1981Date of Patent: July 6, 1982Assignee: Mitsui Petrochemical Industries Ltd.Inventors: Yoshinori Morita, Akifumi Kato, Ryoichi Yamamoto
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Patent number: 4330645Abstract: A process for the preparation of propylene homopolymers or copolymers by polymerizing the monomer or monomers in the gas phase in a centric stirred bed of finely divided polymer, with removal of the heat of polymerization by evaporative cooling, the temperature in the polymerization zone being regulated by measuring the temperature continuously and causing any change therein to trigger a change in the amount of liquid monomer, evaporating in the reaction zone, which is introduced per unit time, in which process(1) the radius and height of the centric stirred bed are in a particular ratio to one another, (2) the finely divided polymer in the centric stirred bed is caused to move upward in the peripheral zone of the bed and downward in the central zone of the bed, (3) the temperature in the polymerization zone is regulated by simultaneously measuring it at (3.1) one or more points of the inner part of the stirred bed and (3.Type: GrantFiled: March 31, 1981Date of Patent: May 18, 1982Assignee: BASF AktiengesellschaftInventors: Dirk Juza, Dieter Stein
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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: 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: 4303770Abstract: A new catalyst and a method of polymerizing olefins in which the catalyst is prepared (1) by forming a mixture by dispersing on a finely divided, difficult to reduce, inorganic support of silica, alumina, thoria, zirconia, titania, magnesia or mixtures of these a tetravalent or lower valent organic chromium compound, (2) calcining the mixture of (1) in an oxidizing or inert atmosphere and at an elevated temperature to produce a chromium compound on the support, (3) reacting the product of (2) with an alkyl ester of titanium, boron, vanadium or mixtures thereof or boric acid at an elevated temperature, and (4) activating the product of (3) with a dry gas that contains oxygen by heating at an elevated temperature the product of (3) in this dry gas.Type: GrantFiled: July 7, 1980Date of Patent: December 1, 1981Assignee: Chemplex CompanyInventors: Thomas J. Pullukat, Mitsuzo Shida
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Patent number: 4287327Abstract: A process for controlling polymer particle size distribution in the vapor phase polymerization of olefins comprises contacting fresh catalyst with a stream of wetting liquid before the catalyst is dispersed in the polymer bed, said wetting liquid being introduced at a wetting liquid flux density greater than about 20.Type: GrantFiled: September 29, 1980Date of Patent: September 1, 1981Assignee: Standard Oil Company (Indiana)Inventors: Glenn O. Michaels, Michael J. Spangler
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Patent number: 4277589Abstract: There are disclosed new solid catalyst-forming components for use in preparing catalysts for the stereoregular polymerization of alpha-olefins containing at least 3 carbon atoms, mixtures of alpha-olefins with one another and/or with ethylene, said components being obtained by reacting(a) at least one hydrocarbon-soluble halogenated Ti compound;(b) a product comprising a Mg dihalide obtained by decomposition of an adduct of at least a Mg dihalide and an electron-donor compound present in the adduct in an amount of at least 0.5 mole per mole of Mg dihalide, the decomposition product being characterized in that, in its X-rays powder spectrum, instead of the diffraction line of maximum intensity which appears in the X-rays powder spectrum of the normal Mg dihalide, a halo appears whose intensity maximum is shifted with respect to said line, and(c) an electron-donor compound which does not contain active hydrogen atoms.Type: GrantFiled: December 21, 1979Date of Patent: July 7, 1981Assignees: Montedison S.p.A., Mitsui Petrochemical Industries, Ltd.Inventors: Umberto Giannini, Enrico Albizzati, Sandro Parodi
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Patent number: 4255542Abstract: A continuous low pressure gas phase process for the production of solid particulate polymers during an exothermic polymerization reaction in a uniform diameter vertical fluidized bed reactor system which comprises feeding a polymerization catalyst and a gaseous stream containing at least one polymerizable monomer to a fluidized bed of polymer particles and removing the exothermic heat of reaction by indirect cooling means in the reactor and removing dry particulate polymer. Also, apparatus for the polymerization process is described.Type: GrantFiled: November 30, 1978Date of Patent: March 10, 1981Assignee: Union Carbide CorporationInventors: Gary L. Brown, David F. Warner, Jae H. Byon
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Patent number: 4241112Abstract: According to the invention, the method for applying a polymer coating onto the surface of a solid filler comprises deposition of a complex organometallic catalyst, containing a compound of a transition metal and an organic compound of a metal of the second or third groups of the periodic system, on the surface of the solid filler and liquid- or gas-phase polymerization of olefins at a temperature of 50.degree. to 170.degree. C. and a pressure of 1 to 60 atm on said catalyst deposited on the surface of the solid filler. The deposition is carried out in two stages. The first stage is gas-phase deposition of the first component of the catalyst, i.e. a compound of a transition metal, on the surface of the solid filler. The second stage is gas- or liquid-phase deposition of the second component of the catalyst, i.e. an organic compound of a metal of the second or third group of the periodic system.Type: GrantFiled: August 8, 1978Date of Patent: December 23, 1980Inventors: Leonid A. Kostandov, Nikolai S. Enikolopov, Fridrikh S. Dyachkovsky, Ljudmila A. Novokshonova, Jury A. Gavrilov, Olga I. Kudinova, Tatyana A. Maklakova, Leonid A. Akopian, Khaim-Mordkhe A. Brikenshtein
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Patent number: 4232140Abstract: Trichlorofluoromethane is used as a promoter in the polymerization and copolymerization of ethylene with supported Ziegler-type vanadium compound/alkylaluminum compound catalysts in the presence of hydrogen. The use of the promoter leads to the formation of non-rubbery, semi-crystalline polymers in high yields, does not alter the basic molecular weight distribution of the polymers, permits independent control of molecular weight by hydrogen, and imparts no significant level of halogen to the product.Type: GrantFiled: October 23, 1978Date of Patent: November 4, 1980Assignee: Cities Service CompanyInventor: Morris R. Ort
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Patent number: 4200715Abstract: A process is provided for the polymerization of an olefin such as ethylene in the vapor phase in a moving bed of particles of the polymerized olefin in which novel means are employed to feed the finely-divided solid polymerization catalyst to the polymerization zone. The process is carried out by pumping into the polymerization zone a Bingham fluid which has the finely-divided solid polymerization catalyst uniformly dispersed throughout a solid continuous phase, which is a mixture of a wax and a hydrocarbon which is a liquid at ambient temperature.Type: GrantFiled: May 19, 1978Date of Patent: April 29, 1980Assignee: Gulf Oil CorporationInventors: Thomas J. Lynch, Robert J. Rowatt
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Patent number: 4188470Abstract: Ethylene is polymerized in a gaseous phase and in contact with a Ziegler/Natta type solid catalyst capable of producing polyethylene in the form of granules having an easily controllable and homogeneous granulometric size, the polymerization being conducted in a tubular reactor in which the catalyst and the polymer granules which are formed are carried along the reactor by the flow of the gas.Type: GrantFiled: January 11, 1978Date of Patent: February 12, 1980Assignee: Montedison S.p.A.Inventors: Amilcare Collina, Arrigo Soverini, Francesco Rosati
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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: 4158571Abstract: Bingham fluid compositions are provided which contain a functional material such as a polymerization initiator dispersed in a solid continuous phase, which is a mixture of a wax and a liquid hydrocarbon. Such compositions are prepared by heating the wax and the liquid hydrocarbon to form a melt and dispersing the functional material in the melt. Upon cooling, the composition solidifies with the functional material being uniformly dispersed throughout the continuous solid phase. The compositions, while solid at ambient temperature and pressure, assume the flow characteristics of a liquid under an applied pressure and can be pumped to feed the functional material to a polymerization reactor or molten polymer on a continuous basis.Type: GrantFiled: May 19, 1978Date of Patent: June 19, 1979Assignee: Gulf Oil CorporationInventors: Thomas J. Lynch, Robert J. Rowatt
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Patent number: 4130699Abstract: Vapor phase polymerization of an olefin which comprises conveying inactive high yield titanium catalyst component to a vapor phase polymerization reactor with a liquid comprising recycled quench liquid, reactivating said inactive high yield titanium catalyst component inside the reactor with a metal alkyl reducing agent and polymerizing olefin under gas phase polymerization conditions with reactivated high yield catalyst to form a resinous polymer of an olefin having a low level of catalyst residues.Type: GrantFiled: November 25, 1977Date of Patent: December 19, 1978Assignee: Standard Oil Company (Indiana)Inventors: Glen R. Hoff, John L. Melquist, Peter Fotis
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Patent number: RE30148Abstract: A melt finish process is disclosed herein for working up solid, particulate polymer from a vapor state polymerization reactor, which reactor employs high yield catalysts, whereby the polymer is moved out of the reactor and into a post polymerization zone characterized by essentially adiabatic polymerization and the heat of such polymerization is used in raising the temperature of and melting said solid, particulate polymer to form molten polymer for further processing.Type: GrantFiled: July 17, 1978Date of Patent: November 13, 1979Assignee: Standard Oil Company (Indiana)Inventors: James L. Jezl, Edwin F. Peters