Monomer Polymerized In Vapor State In Presence Of Transition Metal Containing Catalyst Patents (Class 526/901)
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Patent number: 5436304Abstract: The invention is directed toward polymerizing or copolymerizing alpha-olefins either alone or in combination with one or more other alpha-olefins in a gas phase reactor having a fluidized bed and a fluidizing medium such that the fluidizing medium entering the reactor comprises a gas and a liquid phase.Type: GrantFiled: October 3, 1994Date of Patent: July 25, 1995Assignee: Exxon Chemical Patents Inc.Inventors: John R. Griffin, Marc L. DeChellis
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Patent number: 5434228Abstract: The present invention relates to a gas phase fluidized bed reactor (1) comprising an upright tubular portion (2) having a fluidization grid (4) in the lower part thereof. According to the invention the upright tubular portion (4) is provided with an external conduit (13) which connects a lower orifice (14) which is above the fluidization grid (4) and an upper orifice (15) which is a height above the lower orifice (14). The invention also relates to a gas phase polymerization process carried out in the reactor.Type: GrantFiled: July 16, 1993Date of Patent: July 18, 1995Assignee: BP Chemicals LimitedInventors: Frederic R. M. M. Morterol, Charles Raufast
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Patent number: 5432236Abstract: According to the present invention, in a vapor phase polymerization of olefins, there is provided an efficient polyolefin manufacturing process capable of preventing the formation of a sheet-like polymer and allowing an olefin polymerization reaction to be started stably.Type: GrantFiled: February 18, 1994Date of Patent: July 11, 1995Assignee: Nippon Oil Company, LimitedInventors: Akira Sano, Kunimichi Kubo, Kazuo Matsuura
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Patent number: 5428118Abstract: An improved method for polymerizing one or more polyolefins in the presence of a transition metal catalyst in at least one gas phase reactor having an expanded section, the improvement comprising generating a tangential flow of gas or gas-solids in the expanded section of the gas phase reactor to reduce fines entrainment into the gas cycle system and to reduce or remove solid particle build-up on one or more interior surfaces of the expanded section of the reactor.Type: GrantFiled: July 15, 1994Date of Patent: June 27, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Roger B. Painter, Billy J. Garner, Gyung-Ho Song
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Patent number: 5420220Abstract: A film of a linear low density copolymer of ethylene (LLDPE) having excellent processability, optical properties and impact strength, which exhibits a density of at least 0.900.Type: GrantFiled: March 25, 1993Date of Patent: May 30, 1995Assignee: Mobil Oil CorporationInventors: Subrahmanyam Cheruvu, Frederick Y. Lo, S. Christine Ong
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Patent number: 5418308Abstract: Copolymers of propylene and a non-conjugated diene or triene of the formula (I): CH.sub.2 =CH(CHR.sup.4).sub.n CR.sup.1 =CR.sup.2 R.sup.3, where R.sup.1 and R.sup.2 are hydrogen or alkyl, but are not both hydrogen; R.sup.3 is alkyl or alkenyl of the formula (II): --(CHR.sup.8).sub.m CR.sup.5 =CR.sup.6 R.sup.7, where R.sup.5 and R.sup.6 are as defined for R.sup.1 (above), but are not both hydrogen; R.sup.7 is alkyl; each R.sup.8 is as defined for R.sup.4 (below); and m is 1 to 5; R.sup.4 is hydrogen or alkyl especially methyl; and n is from 2 to 5, can be made using highly stereospecific Ziegler-Natta polymerisation catalysts. The copolymers have 99.9 to 60, particularly 99.5 to 85, mole % propylene residues and 0.1 to 40, particularly 0.5 to 15, mole % diene residues. The copolymers have unexpectedly low solubility in organic solvents such as xylene and can be cross-linked, vulcanised or cured to give polymers having improved high temperature performance.Type: GrantFiled: January 15, 1995Date of Patent: May 23, 1995Assignee: BASF AktiengesellschaftInventor: James L. Harvie
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Patent number: 5414063Abstract: A process control scheme for temporarily slowing or killing the production of polypropylene while idling the reactor using a fourth generation catalyst system containing a solid magnesium chloride supported titanium tetrachloride catalyst component containing an internal strong electron donor in combination with a silicon compound, and an organoaluminum compound (cocatalyst) is disclosed. This process entails the introduction of an amount of an external strong electron donor to the ongoing polymerization reaction. The polymerization reaction can be restarted by introducing an additional amount of the organoaluminum compound.Type: GrantFiled: March 30, 1993Date of Patent: May 9, 1995Assignee: Huntsman Polypropylene CorporationInventors: Horst K. Seeger, Yao-Ching Liu, LeVoy G. Haight, Luis A. Pagan, Kimberly R. Payne, Jeffrey J. Vanderbilt
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Patent number: 5414064Abstract: Homopolymers of ethylene or copolymers of ethylene with minor amounts of other C.sub.3 -C.sub.12 -alk-1-enes are prepared by catalytic polymerization in a suspension or in the gas phase in the presence of an antistatic agent at from 50 to 120.degree. C. and from 5 to 50 bar by a process in which the antistatic agent used is a mixture of the following substances:a) a metal salt of medialanic acid of the formula (I) ##STR1## b) a metal salt of an anthranilic acid of the general formula (II) ##STR2## where the organic radical R.sup.1 is either.alpha.)--CO--(CH.sub.2).sub.x --CH.sub.3 (II.alpha.)or.beta.)--CO--(CH.sub.2).sub.y --CH.dbd.CH--(CH.sub.2).sub.z --CH.sub.3(III.beta.)and x, y and z are each an integer and are from 6 to 18 for x, from 1 to 16 for y, from 1 to 16 for z and from 4 to 17 for y+z, andc) a polyamine obtainable by reacting epichlorohydrin and an aliphatic primary monoamine or an N-alkylalkylenediamine of the general formula (IV)R.sup.2 NH--R.sup.3 --NH.sub.2 (IV),whereR.sup.2 is C.sub.8 -C.Type: GrantFiled: July 14, 1994Date of Patent: May 9, 1995Assignee: BASF AktiengesellschaftInventors: Martin Lux, Guido Funk, Roland Saive, Hans-Helmut Goertz, Rainer Konrad
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Patent number: 5410003Abstract: A process for the production of a homogeneous polyethylene comprising contacting ethylene, one or more alpha-olefins, and one or more unconjugated dienes, under polymerization conditions, with a catalyst system comprising:(A ) a modified supported vanadium based catalyst precursor;(B) an alkylaluminmn halide cocatalyst; and(C) a promoter consisting of an unsaturated aliphatic halocarbon or a haloalkyl substituted aromatic hydrocarbonwith the proviso that sufficient unconjugated diene is present to provide in the homogeneous polyethylene about 0.01 to less than about one percent by weight diene.Type: GrantFiled: March 31, 1994Date of Patent: April 25, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Xinlai Bai
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Patent number: 5410002Abstract: The present invention relates to a process for the production of homopolymers of ethylene and copolymers of ethylene with olefins CH.sub.2 .dbd.CHR, wherein R is an alkyl or aryl radical having a number of carbon atoms of from 1 to 10, and having a density greater than 0.86 g/cm.sup.3, comprising at least one (co)polymerization step in the gas phase, in the presence of an active catalyst obtained from a titanium compound supported on a magnesium halide in active form and an Al-alkyl compound. The process is characterized in that a small amount compared with the polymer is fed to the gas-phase reactor of a polyfunctional compound having at least two groups, the same or different, capable of reacting with the alkyl aluminum compound and capable of selectively inhibiting the reactivity of the polymer particle fines compared with the average granulometric size of the polymer present in the bed of a gas-phase polymerization reactor.Type: GrantFiled: January 29, 1993Date of Patent: April 25, 1995Assignees: Spherilene S.r.l., Himont IncorporatedInventors: Gabriele Govoni, Giovanni Patroncini
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Patent number: 5405922Abstract: The invention is directed toward polymerizing alpha-olefins either alone or in combination with one or more other alpha-olefins utilizing a bulky ligand transition metal catalyst in a gas phase fluidized bed polymerization reactor operating in condensed mode.Type: GrantFiled: March 22, 1994Date of Patent: April 11, 1995Assignee: Exxon Chemical Patents Inc.Inventors: Marc L. DeChellis, John R. Griffin, Michael E. Muhle
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Patent number: 5399638Abstract: The method of forming a catalytic component for use in the polymerization of ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin in a gas-phase comprising impregnating a porous metal oxide support with at least one titanium compound, magnesium compound, and chlorine compound, and prepolymerizing ethylene or a copolymer of ethylene and a C.sub.3 to C.sub.12 alpha olefin, a least partially in suspension, in the presence of said porous metal oxide support and at least one alkylaluminum compound until a degree of prepolymerization is reached which is suitable for the subsequent gas-phase of fluidized bed polymerization, and the method of polymerizing olefins utilizing the catalysts formed by the prepolymerization.Type: GrantFiled: January 10, 1992Date of Patent: March 21, 1995Assignee: AtochemInventors: Claude Brun, Auguste Cheux, Eric Barthel
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Patent number: 5391656Abstract: A method of recovering and recycling monomers from a gas phase olefins polymerization reactor through the use of the monomer feed stream. A high pressure monomer source is reduced in pressure so as to reduce the temperature of the monomer source. The monomer source is then used to cool and condense monomers contained in various vent gas streams. The condensed monomers are then separated from the gas stream and recycled back to the reactor.Type: GrantFiled: September 24, 1993Date of Patent: February 21, 1995Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: David W. Campbell, Randall L. Force, Kelli L. Campbell
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Patent number: 5385991Abstract: A process for producing polyolefin with a vapor-phase fluidized-bed reactor, wherein the reaction is started after filling the reactor with particles which contain moisture and/or molecular oxygen and can form a fluidized bed in order to prevent the formation of molten resin which is liable to occur at the start of the reaction and to attain a smooth operation of the reactor.Type: GrantFiled: March 27, 1992Date of Patent: January 31, 1995Assignee: Nippon Petrochemicals Company, LimitedInventors: Yoshihisa Yamaguchi, Shinjiro Suga, Masatoshi Morikawa, Kunimichi Kubo, Motokazu Watanabe, Yasuhiko Sano
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Patent number: 5382638Abstract: A process for polymerizing olefins in a gas-phase fluidized-bed reactor comprising a reactor body (1), optionally surmounted by a disengagement chamber (2), in which fine particles entrained by the gas mixture leaving the top of the reactor are separated from the gas and recycled to the upper portion of the reactor body. Polymer is withdrawn from the reactor body (1) via at least two polymer outlets, at least one of which (15) is in the lower portion of the reactor body (1) and at least one of which (16) is in the upper portion of the reactor body at a position below the top of the fluidized bed. The invention includes apparatus for polymerizing olefins and the use of the apparatus.Type: GrantFiled: February 7, 1992Date of Patent: January 17, 1995Assignee: BP Chemicals LimitedInventors: Xavier Bontemps, Laszlo Havas, Andre Martens, Frederic R. M. M. Morterol
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Patent number: 5376742Abstract: Unreacted monomer present in an ethylene/C.sub.3 -C.sub.8 alpha-olefin copolymer product produced in a catalyzed fluid bed polymerization process is purged with a gaseous stream obtained by subjecting a portion of the gaseous effluent from the fluidized bed to a partial condensation, separating the liquid phase from the gaseous phase obtained and employing the gaseous phase as the gas to purge unreacted monomer from the copolymer product.Type: GrantFiled: September 23, 1993Date of Patent: December 27, 1994Assignee: Quantum Chemical CorporationInventor: Stephen J. Krause
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Patent number: 5376743Abstract: A process for the production of EPM or EPDM comprising contacting ethylene, propylene, and, optionally, one or more dienes, in a fluidized bed, at a temperature at or above the sticking temperature of the product resin, under polymerization conditions, with(i) a prepolymer containing a transition metal catalyst precursor with the proviso that the prepolymer is not sticky at the process temperature;(ii) a hydrocarbyl aluminum and/or a hydrocarbyl aluminum halide cocatalyst,; and, optionally,(iii) a halocarbon promoter; and, optionally,(iv) an inert particulate material having a mean particle size in the range of about 0.01 to about 150 microns wherein the particulate material is either contained in the prepolymer or is independent of the prepolymer,wherein the amount of prepolymer or the combined amount of prepolymer and inert particulate material is sufficient to essentially prevent agglomeration of the fluidized bed and the product resin.Type: GrantFiled: March 11, 1993Date of Patent: December 27, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Edgar C. Baker, Jose F. Cevallos-Candau, Fathi D. Hussein, Kiu H. Lee, Allen Noshay
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Patent number: 5367037Abstract: A process for the production of EPDM comprising reacting ethylene, propylene, ethylidene norbornene, and hydrogen, in the gas phase, in a fluidized bed, under polymerization conditions, in the presence of a catalyst system comprising:(a) the reaction product of a vanadium compound and a electron donor;(b) at least one modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.a wherein each R is alkyl or aryl and is alike or different; each X is independently chlorine, bromine, or iodine; and a is 0, 1, or 2,wherein components (a) and (b) are impregnated into an inorganic support;(c) a halocarbon promoter; and(d) a hydrocarbyl aluminum cocatalyst with the following proviso:(i) the partial pressure of ethylene is in the range of about 25 to about 200 psi;(ii) the molar ratio of propylene to ethylene is in the range of about 0.2:1 to about 2:1;(iii) the molar ratio of hydrogen to ethylene is in the range of about 0.0001:1 to about 0.01:1; and(iv) the amount of ethylidene norbornene is about 1.Type: GrantFiled: March 31, 1994Date of Patent: November 22, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kiu H. Lee, Mahmoud R. Rifi, Mark J. Kriss, Han-Tai Liu
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Patent number: 5342907Abstract: A process comprising contacting a mixture comprising ethylene, propylene, and, optionally, a diene, in the gas phase, under polymerization conditions, with a catalyst system comprising:(a) a catalyst precursor, in independent or prepolymer form, consisting of vanadium (acetylacetonate).sub.3 ;(b) optionally, a support for said precursor;(c) a cocatalyst consisting essentially of (i) an alkylaluminum halide having the formula AlR.sub.(3-a) X.sub.a wherein each R is independently alkyl having 1 to 14 carbon atoms; each X is independently chlorine, bromine, or iodine; and a is 1 or 2, and (ii) optionally, a trialkylaluminum provided that the molar ratio of alkylaluminum halide to trialkylaluminum is at least about 1.Type: GrantFiled: June 28, 1993Date of Patent: August 30, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Kevin J. Cann, Fathi D. Hussein, Kiu H. Lee, Daniel P. Zilker, Jr., James W. Nicoletti, Xinlai Bai
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Patent number: 5332793Abstract: A process for the production of EPRs comprising contacting ethylene, propylene, and optionally, a diene, under polymerization conditions, with a catalyst system comprising:(A) a catalyst precursor comprising:(i) a vanadium compound, which is the reaction product of(a) VX.sub.3 wherein each X is independently chlorine, bromine, or iodine; and(b) an electron donor, which is a liquid, organic Lewis base in which VX.sub.3 is soluble;(ii) a modifier having the formula BX.sub.3 or AlR.sub.(3-a) X.sub.Type: GrantFiled: June 28, 1993Date of Patent: July 26, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: Kevin J. Cann
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Patent number: 5324805Abstract: The present invention relates to a novel ethylene/pentene-1 copolymer whose molded film has a good balance between impact resistance and tear properties and high transparency, also is prominently reduced in a variation of the transparency even after subjected to a heat treatment, and further shows high blocking resistance, provided that the copolymer fulfills specific requisites. The invention also relates to a process for the preparation of the above-mentioned ethylene/pentene-1 copolymer and a formulation of the ethylene/pentene-1 copolymer composition using a stabilizer. According to the invention, there can be obtained an ethylene/pentene-1 copolymer composition which is excellent in heat stability in the molding stage, long-term heat stability and weatherability.Type: GrantFiled: February 27, 1991Date of Patent: June 28, 1994Assignee: Mitsui Petrochemical Industries, Ltd.Inventors: Mamoru Kioka, Takashi Ueda, Masaya Yamada, Masaki Kohyama, Seiichi Ikeyama, Yoshinori Akana, Kenji Iwata, Hiroshi Nishikawa, Kazumitsu Kawakita, Hideki Sakai
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Patent number: 5317036Abstract: Gas phase polymerization processes are disclosed which utilize unsupported soluble transition metal coordination catalysts. The catalysts are introduced into the reactor as a solution.Type: GrantFiled: October 16, 1992Date of Patent: May 31, 1994Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Robert C. Brady, III, Frederick J. Karol, Timothy R. Lynn, Robert J. Jorgensen, Sun-Chueh Kao, Eric P. Wasserman
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Patent number: 5310833Abstract: A process for feeding a powder catalyst with a gas intermittently to a high-pressure fluidized bed reactor for the vapor phase polymerization of olefin, wherein the cross section of a catalyst feed pipe is reduced midway through the pipe to thereby make continual catalyst feeding possible and prevent the formation of a lump polymer.Type: GrantFiled: February 22, 1993Date of Patent: May 10, 1994Assignee: Nippon Petrochemicals Company, Ltd.Inventors: Kunimichi Kubo, Motokazu Watanabe, Mamoru Yoshikawa, Masatoshi Morikawa, Yoshihisa Yamaguchi
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Patent number: 5306792Abstract: The present invention relates to a continuous process for the polymerization of an alpha-olefin having from 2 to 12 carbon atoms, which is carried out in a gas phase polymerization reactor by bringing a gaseous reaction mixture containing the alpha-olefin to be polymerized into contact with a catalyst based on chromium oxide associated with a catalyst based on chromium oxide associated with a granular support and activated by a heat treatment in which the polymerization reactor is fed with (a) alpha-olefin and (b) catalyst at constant rates.Type: GrantFiled: August 16, 1991Date of Patent: April 26, 1994Assignee: BP Chemicals LimitedInventors: Laszlo Havas, Claudine Lalanne-Magne
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Patent number: 5283278Abstract: The present invention relates to an alpha-olefin prepolymer catalytically active in an alpha-olefin (co-)polymerization comprising a transition metal, an organometallic compound and an antistatic agent. The prepolymer can be prepared by contacting the antistatic agent with a catalyst comprising the transition metal and the organometallic compound before or during an alpha-olefin prepolymerization. It can also be prepared by contacting the antistatic agent with an alpha-olefin prepolymer after a prepolymerization. It can also be prepared by a combination of the two methods. The prepolymer can be introduced into a gas phase (co-)polymerization medium for preparing polyolefin directly in a dry powder form, with a reduced amount of sheeting and agglomerates.Type: GrantFiled: April 8, 1991Date of Patent: February 1, 1994Assignee: BP Chemicals LimitedInventors: Erick Daire, John G. Speakman
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Patent number: 5266276Abstract: The present invention relates to a process and apparatus for the gas-phase polymerization of olefins in a fluidized-bed reactor maintained at a temperature T1. A gaseous reaction mixture comprising the olefins to be polymerized passes through the reactor and is recycled to the reactor by means of a recycling line comprising successively a first heat transfer means, a compressor and a second heat transfer means. The present invention consists in introducing a readily volatile liquid hydrocarbon into the inlet of the first heat transfer means or into the recycling line, upstream and in the vicinity of the first heat transfer means. The first heat transfer means cools the gaseous reaction mixture to a temperature T2, below T1, while volatilizing the readily volatile hydrocarbon and without condensing a constituent of the gaseous reaction mixture. The second heat transfer means cools the gaseous reaction mixture to a temperature T3, below T2, for maintaining the fluidized-bed at the desired temperature T1.Type: GrantFiled: March 9, 1993Date of Patent: November 30, 1993Assignee: BP Chemicals LimitedInventors: Jean-Claude Chinh, Andre Dumain
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Patent number: 5264506Abstract: A process for producing sticky polymers at polymerization reaction temperatures in excess of the softening temperatures of the sticky polymers in a fluidized bed reactor in the presence of an inert particulate material which comprises utilizing as a support material for the catalyst, a support which includes silica having an average particle size of from about 60 to about 200 microns.Type: GrantFiled: December 30, 1992Date of Patent: November 23, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Ronald S. Eisinger, Fathi D. Hussein, David N. Edwards, Kiu H. Lee
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Patent number: 5252688Abstract: The present invention relates to a process for preparing a Ziegler-Natta type catalyst based on a vanadium compound. The process comprises sequentially contacting within a liquid hydrocarbon a spheroidal support comprising (i) MgCl.sub.2 free from any Mg-C bond and (ii) an electron-donor D1 free from labile hydrogen, an electron-donor D2 containing labile hydrogen and an organometallic compound capable of reducing a vanadium compound, (2) washing the solid product with a liquid hydrocarbon resulting from the contacting, and (3) contacting the washed solid product with one or more vanadium compounds soluble in the liquid hydrocarbon, comprising halogen atoms and alkoxy radical, both being bonded to the same or different vanadium atoms. The catalyst which consists of spheroidal particles without fines, is very active in olefin polymerization and is particularly suitable for producing elastomeric copolymers of propylene.Type: GrantFiled: December 23, 1991Date of Patent: October 12, 1993Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, Patrick Behue
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Patent number: 5244987Abstract: A process for controlling the continuous gas-phase polymerization of one or more alpha-olefins in a fluidized and/or mechanically stirred bed reactor using a high activity catalyst based on a transition metal of groups IV, V or VI of the Periodic Table comprises introducing into the reactor, continuously and simultaneously, an activity retarder and an activator, in very small amounts, in a molar ratio and at flow rates which are varied with time in order to maintain substantially constant either the polymerization rate or the transition metal content of the polymer produced.Type: GrantFiled: February 28, 1992Date of Patent: September 14, 1993Assignee: BF Chemicals LimitedInventors: Jean-Claude Bernard, Claudine Berruyer, Laszlo Havas
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Patent number: 5241023Abstract: The present invention relates to a process and a device for polymerizing alpha-olefins such as ethylene or propylene in a gas phase. The device comprises a gas phase polymerization reactor (5) into which a suspension of prepolymer particles in liquid saturated hydrocarbon(s) is continuously introduced. The prepolymer suspension is prepared in one or more prepolymerization vessels (14) and is continuously passed to a post-treatment unit comprising a degassing means (10) wherein most of the dissolved unreacted olefinic monomer(s) is separated. Preferably, the post-treatment unit may comprise a particle separation means (11) for removing the finest and/or coarsest prepolymer particles from the suspension and/or a concentration means (11a) for concentrating the suspension.High activity catalyst can be used in the process with reduced amounts of prepolymer agglomerates. Prepolymer can be obtained with a constant quality and a desired size.Type: GrantFiled: March 4, 1991Date of Patent: August 31, 1993Assignee: BP Chemicals LimitedInventors: Daniel Brule, Jean-Marie Iffly, Charles Raufast
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Patent number: 5241024Abstract: A process for producing a butene-1 polymer is disclosed which is characterized in that, in a process for producing a homopolymer of butene-1 or a copolymer of butene-1 and .alpha.-olefin other than the butene-1 in the presence a catalyst obtained from a solid catalyst component (A), an organic aluminium compound (B) and an electron donating compound (C) and under the condition of vapor phase polymerization, the solid catalyst component (A) is a non-layer solid catalyst component obtained by producing a carrier by chlorinating at least one kind of organic magnesium compounds represented by formulaMgR'R" (1)wherein R' and R", which may be the same or different, each represents an alkyl group having 1 to 20 carbon atoms, with at least one kind of chlorinating agents, the carrier produced is contacted in the presence of the electron donor with a titanic halide at a temperature of -25.degree. to +180.degree. C.Type: GrantFiled: May 9, 1991Date of Patent: August 31, 1993Inventors: Takashi Yamawaki, Hideki Imabayashi
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Patent number: 5227438Abstract: A process for terminating or retarding the rate of polymerization of propylene or a mixture comprising propylene and one or more other olefin monomers, in a gas phase reactor, in the presence of a catalyst system comprising (i) a solid catalyst precursor composition which includes magnesium, titanium, halogen, and carboxylic acid ester; (ii) hydrocarbyl aluminum cocatalyst; and (iii) a silicon compound containing at least one silicon-oxygen-carbon linkage, which comprises introducing a phthalate compound at a rate and in a sufficient quantity to substantially retard or terminate the said polymerization reaction.Type: GrantFiled: September 24, 1991Date of Patent: July 13, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventor: David M. Rebhan
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Patent number: 5225458Abstract: A process for (co)polymerizing alpha-olefins in the gas phase in a fluidized bed or mechanically stirred bed reactor using a Ziegler-Natta type catalyst or a heat activated chromium oxide/refractory oxide catalyst wherein the (co)polymerization is carried out in the presence of 0.005 to 0.2 weight %, based on the weight of the (co)polymer bed, of an inert pulverulent inorganic substance (e.g. silica) having a mean particle diameter between 0.5 and 20 microns. The process is capable of being operated at temperatures closer to the softening point of the produced polyolefin than in the absence of the pulverulent solid.Type: GrantFiled: July 19, 1991Date of Patent: July 6, 1993Assignee: BP Chemicals LimitedInventors: Jean-Claude A. Bailly, Joelle Collomb
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Patent number: 5216102Abstract: The present invention provides a process for producing a polyacetylene.In the present process for producing a polyacetylene, acetylene is polymerized with a Ziegler-Natta catalyst consisting of a trialkylaluminum and an alkyl titanate, wherein there is used, as the trialkylaluminum, a trialkylaluminum having an alkyl group of 6 or more carbon atoms, or, as the alkyl titanate, an alkyl titanate having an alkyl group of 6 or more carbon atoms.The polyacetylene obtained according to the present invention is superior in mechanical properties, particularly stretchability.Type: GrantFiled: September 30, 1991Date of Patent: June 1, 1993Assignee: Matsushita Electric Industrial Co., Ltd.Inventors: Mamoru Soga, Shu Hotta, Nobuo Sonoda, Hideki Shirakawa, Kazuo Akagi
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Patent number: 5208109Abstract: The present invention relates to a process for polymerizing or copolymerizing alpha-olefins comprising, on the one hand, a prepolymerization stage by contacting one or more alpha-olefins with a Ziegler catalyst system consisting of a solid catalyst containing essentially atoms of halogen, magnesium and transition metal, and a co-catalyst consisting of an organometallic compound, and, on the other hand, a polymerization or copolymerization stage in a gas phase process by means of a fluidized bed, by contacting one or more alpha-olefins with the prepolymer produced in the first stage, process characterized in that the alpha-olefin prepolymer and polymer or copolymer are in the form of a powder consisting of particles having specific values for the transition metal content and the mean diameter by mass, and characterized in that the particle size distribution of the prepolymer is narrow and easily controlled.Type: GrantFiled: December 9, 1991Date of Patent: May 4, 1993Assignee: BP Chemicals LimitedInventors: Jean C. Bailly, Laszlo Havas, Stylianos Sandis, Alain Blaya, Pierre Crouzet
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Patent number: 5208303Abstract: The present invention relates to a process for preparing a Ziegler-Natta type catalyst based on a vanadium compound precipitated on a MgCl.sub.2 spherical support. The catalyst preparation consists of contacting within a liquid hydrocarbon a vanadium-reducing agent chosen from organometallic compound with a vanadium compound soluble in the liquid hydrocarbon at least one halogen and one alkoxy group, and with a support containing (i) MgCl.sub.2 free from Mg--C bond and (ii) an organic electron donor compound free from labile hydrogen. The support consists of spherical particles having a well-defined diameter and a narrow particle size distribution. The catalyst is particularly suitable for manufacturing in a gas process elastomeric copolymers of propylene.Type: GrantFiled: July 29, 1991Date of Patent: May 4, 1993Assignee: BP Chemicals LimitedInventor: Jean-Claude A. Bailly
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Patent number: 5202396Abstract: A process for feeding a powder catalyst with a gas intermittently to a high-pressure fluidized bed reactor for the vapor phase polymerization of olefin, wherein the cross section of a catalyst feed pipe is reduced midway through the pipe to thereby make continual catalyst feeding possible and prevent the formation of a lump polymer.Type: GrantFiled: March 19, 1992Date of Patent: April 13, 1993Assignee: Nippon Petrochemicals Company, LimitedInventors: Kunimichi Kubo, Motokazu Watanabe, Mamoru Yoshikawa, Masatoshi Morikawa, Yoshihisa Yamaguchi
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Patent number: 5200477Abstract: A process for preventing agglomeration of sticky polymers in a polymerization system which comprises adding to said polymerization system about 0.3 to about 80 weight percent based on the weight of the final product of an inert particulate material having an organo-modified polydimethylsiloxane (OM-PDMS) surface coating thereon.Type: GrantFiled: February 22, 1991Date of Patent: April 6, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Edgar C. Baker, George N. Foster, Aaron S. Rhee
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Patent number: 5200502Abstract: A method is disclosed for controlling the activity of or deactivating a transition element olefin polymerization catalyst by contacting the catalyst with a 1,2-diether organic compound.Type: GrantFiled: August 26, 1992Date of Patent: April 6, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Sun-Chueh Kao, Frederick J. Karol
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Patent number: 5196496Abstract: Essentially syndiotactic crystalline copolymers of propylene with minor proportions of 1-butene, endowed with good mechanical properties, lowered melting point and limited solubility in xylene at 25.degree. C. and the process for their preparation by polymerizing mixtures of propylene with 1-butene, by using catalysts obtained form stereorigid and chiral zirconium and hafnium compounds and from polymethylalumoxane compounds.Type: GrantFiled: June 26, 1991Date of Patent: March 23, 1993Assignee: Himont IncorporatedInventors: Maurizio Galimberti, Enrico Albizzati, Romano Mazzocchi
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Patent number: 5187246Abstract: An improved polymerization process for making essentially non-agglomerated ethylene polymers, especially EPR polymers, based on the use of a high activity vanadium catalyst, which utilizes an alkylated metal chain transfer agent to moderate the kinetics of the polymerization reaction so as to avoid formation of an undesirable amount of agglomerated polymer.Type: GrantFiled: June 26, 1990Date of Patent: February 16, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Edgar C. Baker, Francis G. Stakem, Allen Noshay, Kiu H. Lee, Arthur E. Marcinkowsky
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Patent number: 5187247Abstract: An improved polymerization process for making essentially nonagglomerated ethylene polymers, especially EPR polymers, based on the use of a stage-modified high activity vanadium catalyst, under polymerization conditions that normally would yield an undesirable amount of agglomerated polymer.Type: GrantFiled: June 26, 1990Date of Patent: February 16, 1993Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Edgar C. Baker, John H. Moorhouse, Allen Noshay
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Patent number: 5179180Abstract: The polymerization of certain alpha-olefins in a gas phase involves the problem of agglomeration of the product into particles disadvantageous from the viewpoint of its handling. In the present invention this problem has been solved by means of a new type of process for the homo- or copolymerization of alpha-olefins. In the process the catalyst system is pretreated by contacting and reacting a transition-metal compound which is solid or on a solid carrier with an organoaluminum compound, and possibly an electron donor, in a liquid medium, and by drying the thus formed reaction product to produce a solid catalyst system. The thus pretreated solid and active catalyst system is then fed together with an alpha-olefin in the gaseous state into a gas-phase reactor, and polymerization is carried out by contacting them with each other.Type: GrantFiled: October 30, 1989Date of Patent: January 12, 1993Assignee: Berggren OY ABInventors: Antero Ahvenainen, Hannu Salminen, Jari Tervonen, Tarja Soderberg
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Patent number: 5169913Abstract: This invention relates to a novel horizontal fluid bed reactor, which in a single unit, provides for the polymerization of monomer to polymer and mixed monomers to copolymers. Within one reactor shell the reactor contains a plurality of polymerization stages which permit the achievement of narrow residence time distribution of the produced polymer. This arrangement also creates a sufficiently tight subdivision of the reactor volume which permits a plurality of gas circulation stages of different gas compositions, as well as, polymerization temperatures.Type: GrantFiled: May 31, 1991Date of Patent: December 8, 1992Assignee: Procedyne Corp.Inventors: H. Kenneth Staffin, David S. Bruce
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Patent number: 5166279Abstract: The present invention relates to a process for (co-)polymerizing ethylene in a gaseous phase, by means of a fluidized and/or mechanically stirred bed reactor, with the help of a catalyst comprising a chromium oxide and a titanium compound, supported on a refractory oxide and activated by a heat treatment. The process is characterized in that the catalyst is introduced into the reactor in the form of a dry powder consisting of particles free from prepolymer and the (co-)polymerization is carried out in the presence of an organoaluminium compound. The (co-)polymer thus obtained has substantially low catalyst residues, and an improved stress cracking resistance.Type: GrantFiled: December 26, 1990Date of Patent: November 24, 1992Assignee: BP Chemicals LimitedInventor: John G. Speakman
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Patent number: 5162465Abstract: Polymers of propene are prepared using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and contains, in addition to titanium, magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an aluminum component and (3) a silane component. In this process, a titanium component (1) is used which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel, (Ib) an alkanol, (Ic) an organomagnesium compound and (Id) a gaseous chlorinating agent by a procedure in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then the mixture obtained in (1.1.1) is combined with (Ic), (1.1.3) then (Id) is passed into the mixture obtained in (1.1.2) and (I) is isolated, (1.2) thereafter a solid-phase intermediate is prepared from (I), (II) an alkanol, (III) titanium tetrachloride and (IV) a phthalic acid drivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.Type: GrantFiled: January 28, 1991Date of Patent: November 10, 1992Assignee: BASF AktiengesellschaftInventors: Juergen Kerth, Ralf Zolk, Rainer Hemmerich
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Patent number: 5162463Abstract: A method for preventing agglomeration of sticky polymers in a fluidized bed which comprises adding to said fluidized bed and 0.3 to about 80 weight percent based on the weight of the final product of an inert particulate material having a PDMS surface coating thereon.Type: GrantFiled: December 10, 1990Date of Patent: November 10, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Edgar C. Baker, George N. Foster, Seung J. Rhee
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Patent number: 5137994Abstract: A process for the simultaneous trimerization of ethylene and the copolymerization of the trimer with ethylene comprising continuously contacting ethylene, the 1-hexene which is formed, and, optionally, hydrogen in a reaction zone, under trimerization and polymerization conditions, with the supported reaction product of one or more bis-triarylsilyl chromates and one or more trihydrocarbylaluminum compounds wherein the atomic ratio of aluminum to chromium is at least about 3 to 1.Type: GrantFiled: May 23, 1991Date of Patent: August 11, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Mark G. Goode, Thomas E. Spriggs, Isaac J. Levine, Wayne R. Wilder, Calvin L. Edwards
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Patent number: 5106927Abstract: A process for the production of EPDM comprising reacting ethylene, propylene, ethylidene norbornene, and hydrogen, in the gas phase, in a fluidized bed, under polymerization conditions, in the presence of a catalyst system comprising:(a) a titanium based catalyst having the formula Mg.sub.a Ti(OR).sub.b X.sub.c (ED).sub.d whereinR is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR' wherein R' is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms;each OR group is alike or different;each X is independently chlorine, bromine, or iodineED is an electron donora is 0.5 to 56;b is 0, 1, or 2;c is 2 to 116; andd is greater than 1.5 a+2;(b) at least one modifier having the formula BX.sub.3 or AlR.sub.(3-b) X.sub.Type: GrantFiled: September 11, 1989Date of Patent: April 21, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Mahmoud R. Rifi, Kiu H. Lee, Mark J. Kriss, Han-Tai Liu
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Patent number: 5106926Abstract: A process for preparing ethylene/1-octene copolymers using a titanium based catalyst system under defined polymerization conditions.Type: GrantFiled: December 11, 1990Date of Patent: April 21, 1992Assignee: Union Carbide Chemicals & Plastics Technology CorporationInventors: Ronald S. Eisinger, Kiu H. Lee