Polymerization Process Of Ethylenic Monomers Using Manipulative Technique Patents (Class 526/922)
  • Patent number: 8183331
    Abstract: In a process for producing water-absorbing polymeric particles which comprises generating droplets comprising monomers, polymerizing the monomers in a heated gas phase surrounding the droplets and flowing the gas through the polymerization reactor, the temperature of the gas leaving the polymerization reactor is closed-loop controlled.
    Type: Grant
    Filed: October 29, 2007
    Date of Patent: May 22, 2012
    Assignee: BASF SE
    Inventors: Dennis Lösch, Marco Krüger, Matthias Weismantel, Wilfried Heide
  • Patent number: 8119755
    Abstract: A process for producing water-absorbing polymer particles by neutralizing the monomer and cooling it by means of an indirect heat exchanger, wherein the specific cooling performance of the heat exchanger is less than 10 W/m2.
    Type: Grant
    Filed: July 6, 2009
    Date of Patent: February 21, 2012
    Assignee: BASF SE
    Inventors: Matthias Weismantel, Rüdiger Funk, Leigh R. Blair, Kevin D. Heitzhaus
  • Patent number: 6891003
    Abstract: The present invention relates to a fiber coated with a water blocking material that includes an essentially water free dispersion comprising a superabsorbent polymer and a dispersing medium. The fibers made according to this invention may be used, for example, as fiber reinforcing material used in the manufacture of cables, and in particular in yarns for fiber optical cables that use optical light wave guides for optical communication transmissions.
    Type: Grant
    Filed: December 12, 2002
    Date of Patent: May 10, 2005
    Assignee: E.I. du Pont de Nemours and Company
    Inventors: Serge Rebouillat, Friedrich V. Pfister
  • Patent number: 6841636
    Abstract: The present invention relates to a dispersion of polymer particles, the particle containing, on average, more than 1 living radicals each, the radicals not being chemically protected. The invention is also directed to a free radical polymerization process resulting in a dispersion containing polymer particles having on average one or more living radicals. The process involves carefully regulating the polymerization conditions to produce small size particles under monomer-starved conditions containing, on average, more than one living radical in every particle. These living polymer radicals can be further reacted to form polymers with a controlled architecture.
    Type: Grant
    Filed: August 1, 2003
    Date of Patent: January 11, 2005
    Assignee: National Starch and Chemical Investment Holding Corporation
    Inventors: Yadunandan Dar, Smita Shah
  • Patent number: 6825290
    Abstract: A subject-matter of the present invention is a process for the preparation of a latex by radical aqueous emulsion polymerization in the presence of at least one ethylenically unsaturated monomer, of at least one radical polymerization initiator and of at least one surface-active block copolymer comprising at least one hydrophilic block and at least one hydrophobic block which is prepared by a “living” or “controlled” preparation process, the said copolymer exhibiting a number-average molecular mass of between 2 000 and 20 000, preferably between 4 000 and 16 000, a glass transition temperature of the hydrophobic block of less than 30° C., preferably of less than 25° C., and greater than −100° C., and a surface tension of less than 60 millinewtons per metre (mN/m), preferably of less than 50 mN/m, measured at a concentration in demineralized water of less than or equal to 10−4 mol/l at 20° C.
    Type: Grant
    Filed: May 2, 2002
    Date of Patent: November 30, 2004
    Assignee: Rhodia Inc.
    Inventors: Hervé Adam, Wan-Li Liu
  • Patent number: 6660814
    Abstract: In the process and a correspondingly appropriate device for preparing homo- or copolymers of at least one of the, polymerizable monomers of the group consisting of styrene, butadiene, vinyl chloride, vinyl acetate, vinylidene chloride, alkyl (meth)acrylatc (meth)acrylic acid, (meth)acrylonitrile and (meth)acrylamide reaction is carried out at at least 40° C. in the presence of a dispersing auxiliary and of a free-radical polymerization initiator such that at least 85% by weight of the polymer is formed from these monomers.
    Type: Grant
    Filed: September 30, 1997
    Date of Patent: December 9, 2003
    Assignee: BASF Aktiengesellschaft
    Inventors: Huberrus Kröner, Wolfgang Klanig, Bradley Ronald Morrison, Rainer Klostermann, Holger Schöpke, Walter Kastenhuber
  • Publication number: 20030206835
    Abstract: Tubular reactor apparatus and processes are provided for improved polymerization including using chain transfer agents and multiple monomer feeds spaced lengthwise along the tubular reactor providing high conversions of monomer into polymer. The invention also relates to polymers made from such a tubular reactor apparatus and processes including those polymers having a low haze value, a density over 0.92 g/cm3 and/or having terminal carbonyl groups. The apparatus and methods uncouple or reduce the dependency between the monomer concentration and transfer agent concentration. The uncoupling in other embodiments may also be varied leading to multiple desirable effects.
    Type: Application
    Filed: June 4, 2003
    Publication date: November 6, 2003
    Inventor: Jan Cyriel Donck
  • Patent number: 6610798
    Abstract: Non-Newtonian fluids, such as partially polymerized monomers or solutions of polymer in monomer may be pressure atomized below the free surface of a continuous liquid phase to produce a dispersed phase. A uniform or customized droplet size distribution can be obtained by imposing a required pressure pulsation on a flowing monomer upstream the atomizer inlet. This initial particle size distribution can be maintained or modified during subsequent polymerization process in a low shear, controlled turbulence flow pattern, created without mechanical agitation within the continuous liquid, by continuously or periodically injecting an inert gas at selected locations within the reactor.
    Type: Grant
    Filed: October 8, 2002
    Date of Patent: August 26, 2003
    Assignee: Nova Chemical Inc.
    Inventors: Karel Cornelis Bleijenberg, Grazyna Petela
  • Patent number: 6596241
    Abstract: Tubular reactor apparatus and processes are provided for improved polymerization including using chain transfer agents and multiple monomer feeds spaced lengthwise along the tubular reactor providing high conversions of monomer into polymer. The invention also relates to polymers made from such a tubular reactor apparatus and processes including those polymers having a low haze value, a density over 0.92 g/cm3 and/or having terminal carbonyl groups. The apparatus and methods uncouple or reduce the dependency between the monomer concentration and transfer agent concentration. The uncoupling in other embodiments may also be varied leading to multiple desirable effects.
    Type: Grant
    Filed: December 19, 2001
    Date of Patent: July 22, 2003
    Assignee: ExxonMobil Chemical Patents Inc
    Inventor: Jan Cyriel Donck
  • Patent number: 6525149
    Abstract: A novel liquid phase polymerization process for preparing a polyolefin product having preselected properties is disclosed. The process includes the steps of providing a liquid feedstock which contains an olefinic component and a catalyst composition consisting of a stable complex of BF3 and a complexing agent therefor. The feedstock may comprise any one or more of a number of olefins including branched olefins such as isobutylene, C3 to C15 linear alpha olefins and C4 to C15 reactive non-alpha olefins. The feedstock and the catalyst composition are introduced into a residual reaction mixture recirculating in a loop reactor reaction zone provided in the tube side of a shell and tube heat exchanger at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the added feedstock and the added catalyst composition.
    Type: Grant
    Filed: September 20, 2000
    Date of Patent: February 25, 2003
    Assignee: Texas Petrochemicals, LP
    Inventors: C. Edward Baxter, Jr., Gilbert Valdez, Christopher Lobue, Timothy Lowry, Armen Abazajian
  • Publication number: 20030032740
    Abstract: A novel liquid phase polymerization process for preparing a polyolefin product having preselected properties is disclosed. The process includes the steps of providing a liquid feedstock which contains an olefinic component and a catalyst composition consisting of a stable complex of BF3 and a complexing agent therefor. The feedstock may comprise any one or more of a number of olefins including branched olefins such as isobutylene, C3 to C15 linear alpha olefins and C4 to C15 reactive non-alpha olefins. The feedstock and the catalyst composition are introduced into a residual reaction mixture recirculating in a loop reactor reaction zone provided in the tube side of a shell and tube heat exchanger at a recirculation rate sufficient to cause intimate intermixing of the residual reaction mixture, the added feedstock and the added catalyst composition.
    Type: Application
    Filed: July 30, 2002
    Publication date: February 13, 2003
    Applicant: Texas Petrochemicals LP
    Inventors: C. Edward Baxter, Gilbert Valdez, Christopher Lobue, Timothy Lowry, Armen Abazajiah
  • Patent number: 6472486
    Abstract: Controlled stable free radical emulsion polymerization processes employ nitroxide control agents having an alpha carbon atom bearing a destabilizing substituent such as hydrogen. The emulsion polymerizations have living characteristics, including the re-initiation of polymer chains, and provide a high degree of control over molecular weight, particle size, polydispersity and polymer composition and architecture. The processes are useful for the preparation of polymer emulsions, including block copolymers, star and graft copolymers, telechelics and macromonomers from a wide range of monomers.
    Type: Grant
    Filed: July 2, 1999
    Date of Patent: October 29, 2002
    Assignee: Symyx Technologies, Inc.
    Inventors: Gerrit Klaerner, Adam Safir, Ralph B. Nielsen, Bernd Jandeleit, Peter Huefner
  • Patent number: 6348635
    Abstract: A process for starting up a reaction for the polymerization of an olefin in the gas phase carried out using a catalyst based on chromium oxide in a fluidized bed reactor through which moves a reaction gas mixture containing the olefin, wherein in the start-up of the reaction, the olefin is introduced into the reactor until the desired production of polymer is reached by means of a two-stage process, during the first stage of which the introduction of the olefin is carried out so as to maintain a constant partial pressure of olefin in the reactor and during the second stage, the introduction of olefin is regulated at a constant flow rate.
    Type: Grant
    Filed: June 15, 2000
    Date of Patent: February 19, 2002
    Assignee: BP Chemicals, Limited
    Inventor: Marc Herzog
  • Patent number: 6107420
    Abstract: The present invention generally relates to the use of certain ruthenium and osmium complexes that are substantially inactive at a first temperature (preferably about room temperature) but become progressively more active at a higher second temperature. This difference in reactivities allows the reaction mixture to be formed and manipulated at the first temperature until polymerization is desired. When appropriate, the reaction mixture is heated to a suitable temperature (preferably greater than 50.degree. C.) to activate the catalyst and to initiate polymerization. Because both the initiation and the rate of polymerization may be controlled with temperature, the inventive methods are especially suitable for ring opening metathesis polymerization ("ROMP") reactions and for molding polymer articles that require extended pot-lives.
    Type: Grant
    Filed: July 26, 1999
    Date of Patent: August 22, 2000
    Assignee: California Institute of Technology
    Inventors: Robert H. Grubbs, Thomas E. Wilhelm
  • Patent number: 6040399
    Abstract: An ethylene base polymer and a preparation method of an ethylene base polymer characterized in use of a catalyst comprising a chromium amide compound, a solid inroganic oxide calcined at 100 to 500.degree. C. and alumoxane. According to the present invention, an ethylene base polymer with a wide molecular weight distribution, excellent shock and environmental stress cracking resistances, causing no melt fracture, and suitable for film forming and blow molding can be effectively prepared.
    Type: Grant
    Filed: March 30, 1998
    Date of Patent: March 21, 2000
    Assignee: Japan Polyolefins Co., Ltd.
    Inventors: Takashi Monoi, Masakazu Yamamoto, Hidenobu Torigoe, Yasunori Takemoto
  • Patent number: 5156914
    Abstract: This invention relates to an anhydrous, liquid phase process for entrapping droplets of a silicon compound in an organic polymer which involves precharging a reactor at between about 50.degree. and about 80.degree. C. with a polymerization initiator and a non-polar solvent in which the silicon compound is soluble; adding to the precharged reactor, silicon compound under vigorous agitation and gradually introducing from about 50 to about 99 wt. %, based on silicon compound, of a polymerizably precipitatable, aliphatically unsaturated monomer at a controlled rate; continuously polymerizing the monomer component, under vigorous agitation with the silicon compound, at between about 50.degree. and about 165.degree. C. while maintaining a desired monomer level of not more than 10% in the reactor and recovering a solid particulate product of silicon droplets entrapped in said polymerized monomer.
    Type: Grant
    Filed: May 6, 1991
    Date of Patent: October 20, 1992
    Assignee: ISP Investments Inc.
    Inventor: Jenn S. Shih
  • Patent number: 5126381
    Abstract: A process and apparatus are disclosed for producing polymerized beads containing actives such as perfumes and pesticides, by forming droplets from a solution of monomers and the actives. The solution is subjected to ultraviolet light to initiate polymerization. The droplets are caused to fall through a reaction vessel as polymerization continues so as to polymerize substantially spherical beads containing the actives. In one embodiment, the droplets are irradiated as they fall through the reaction vessel. In a second embodiment, the solution is irradiated prior to droplet formation and the fall. The beads are collected and can be cured if necessary. The process is preferably performed in an inert gas environment which most preferably is nitrogen. A nitrogen stream can serve as a carrier for the monomers and active ingredients. The nitrogen environment is maintained in the reaction vessel, and in the curing structure, if present.
    Type: Grant
    Filed: December 19, 1988
    Date of Patent: June 30, 1992
    Assignee: Dow Corning Corporation
    Inventor: Cristina Liscomb
  • Patent number: 5013801
    Abstract: Polymer having a polymodal MWD ethylene copolymer are prepared by conducting the polymerization in a substantially mix free reactor using an essentially transfer agent free reaction mixture, the reaction being carried out in a manner such that the propagation of essentially all copolymer chains is initiated simultaneously. In carrying out the process of this invention, the catalyst components are premixed and aged prior to introduction into the reactor. The process is preferably carried out in a tubular reactor using VCl.sub.4 and aluminum sesquichloride as the catalyst system.
    Type: Grant
    Filed: August 2, 1988
    Date of Patent: May 7, 1991
    Inventors: Charles Cozewith, Shiaw Ju, Gary W. Verstrate
  • Patent number: 4794151
    Abstract: A process for the continuous preparation of finely divided homopolymers and copolymers of ethene by catalytic polymerization in a circular tube reactor using a liquid alkane as reaction medium in which the ethene or ethene/comonomer mixture to be polymerized is present in dissolved form and the polymer formed is present in suspended form and running the reaction mixture as a cycle stream to which the feed materials are added by bleeding in and from which the polymer formed is withdrawn by bleeding out reaction mixture, comprising (a) maintaining the mean concentration C.sub.m of polymer in the cycle stream at a value within a certain range and (b) effecting the bleeding out of reaction mixture at a point of the cycle stream at which the concentration of polymer has a value which is lower than the mean concentration C.sub.m by a distinct and definite amount.
    Type: Grant
    Filed: April 8, 1987
    Date of Patent: December 27, 1988
    Assignee: BASF Aktiengesellschaft
    Inventors: Rudolf Mueller-Mall, Guido Funk, Robert Bachl, Peter Hennenberger, Erich Kolk
  • Patent number: 4789714
    Abstract: A method for preparing a polymodal MWD ethylene-alpha olefin copolymer using at least two catalysts to initiate growth of polymer chains that attain different average molecular weights. The polymodal MWD ethylene copolymer comprises at least two different molecular weight modes each mode having a narrow MWD and at least one of two characteristics (1) an Mw/Mn of less than 2 and (2) Mz/Mw of less than 1.8.
    Type: Grant
    Filed: December 26, 1985
    Date of Patent: December 6, 1988
    Assignee: Exxon Research & Engineering Co.
    Inventors: Charles Cozewith, Shiaw Ju, Gary W. Verstrate
  • Patent number: 4786697
    Abstract: Polymodal MWD ethylene copolymer comprising at least two modes of differing molecular weights. Each mode has at least one of M.sub.w /M.sub.n of less than 2.0, and a M.sub.z /M.sub.w of less than 1.8. The polymodal character of the copolymer is achieved by either (1) withdrawing polymer modes from the reactor from at least one takeoff port, and blending such modes with the reactor effluent, or (2) utilizing at least two catalyst species in the reaction to produce modes of differing molecular weights.
    Type: Grant
    Filed: May 4, 1987
    Date of Patent: November 22, 1988
    Assignee: Exxon Research & Engineering Co.
    Inventors: Charles Cozewith, Shiaw Ju, Gary W. Verstrate
  • Patent number: 4696981
    Abstract: Homopolyamino acids and copolyamino acids are prepared by polycondensation of one kind or a mixture of two or more kinds of monoammonium, diammonium, monoamide, diamide or monoamideammonium salts of malic acid and/or maleic acid and/or fumaric acid, one kind or two or more kinds of amino acid being added to said raw materials, respectively, with application of microwaves, the resulting polyamino acids (imide type) being converted to peptide type, homopolyamino acids and copolyamino acids, respectively upon partial hydrolysis. The operation involved in the reaction is simple and the method permits the use of low cost reaction materials. As a result, imide type and also peptide type, homopolyamino and copolyamino acids are produced with uniform quality at a high rate of yield within an extremely short period of time. Accordingly, the method is incomparably superior to those which have been announced in the past.
    Type: Grant
    Filed: March 13, 1986
    Date of Patent: September 29, 1987
    Assignee: Diamond Shamrock Chemicals Company
    Inventors: Kaoru Harada, Akira Shimoyama, Hiroji Mizumoto
  • Patent number: 4540753
    Abstract: The present invention relates to novel copolymers of alpha-olefins comprised of intramolecularly heterogeneous and intermolecularly homogeneous copolymer chains.
    Type: Grant
    Filed: June 15, 1983
    Date of Patent: September 10, 1985
    Assignee: Exxon Research & Engineering Co.
    Inventors: Charles Cozewith, Shiaw Ju, Gary W. VerStrate
  • Patent number: 4299941
    Abstract: An improved process for producing an aqueous emulsion of a vinyl chloride/vinyl ester/ethylene copolymer having a small heat fluidity and excellent strength which comprises continuously adding a solution of a specific polybasic acid polyallyl ester in the vinyl chloride and/or vinyl ester and further at least 60% by weight of the vinyl chloride and vinyl ester to the polymerization system during the polymerization reaction. The copolymer thus produced has a large benzene-insoluble part and the aqueous emulsion thereof is stable and is useful as an adhesive, as for paint compositions, or as a binder for fibers and papers.
    Type: Grant
    Filed: September 24, 1979
    Date of Patent: November 10, 1981
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Shizuo Narisawa, Takeo Oyamada
  • Patent number: 4296225
    Abstract: This invention provides a process for preparing a stable aqueous emulsion composition which has excellent properties for application as a wet abrasion-resistant paper coating binder. The dispersed copolymer of the aqueous emulsion composition comprises a major proportion of vinyl acetate and a minor proportion of an amino-containing vinyl monomer. An important aspect of the emulsion preparation method is the addition of an aqueous solution of the amino-containing vinyl monomer as a separate feedstream, wherein the amine group in the said vinyl monomer is in the form of an amine-acid salt.
    Type: Grant
    Filed: January 4, 1980
    Date of Patent: October 20, 1981
    Assignee: Celanese Corporation
    Inventor: David Rhum
  • Patent number: 4239871
    Abstract: A process for the polymerization of butene-1 in a liquid aliphatic hydrocarbon medium in the presence of a catalyst composed of a titanium trihalide and an organoaluminum compound which comprises initially polymerizing a minor part of the butene-1 at a temperature within a range sufficiently low that a slurry of polymer in said medium is produced and then increasing the temperature of polymerization so that the greater part of the butene-1 is polymerized within a high temperature range higher than that of the initial polymerization but not at a temperature so high that the polymer formed dissolves in said medium, characterized in that (1) the initial polymerization is carried out at a temperature of not more than 20.degree. C. in the presence of said titanium trihalide in an amount of not less than 50 millimoles and up to 1,000 millimoles per liter of said medium, and then (2) the polymerization is carried out in the presence or absence of said medium at a temperature of 25.degree. C. to less than 48.degree.
    Type: Grant
    Filed: November 21, 1979
    Date of Patent: December 16, 1980
    Assignee: Mitsui Petrochemical Industries Ltd.
    Inventor: Kunisuke Fukui
  • Patent number: 4088625
    Abstract: A process for the production of a pulverulent, tricklable mixture of ethylene/vinyl acetate copolymer and polyvinylchloride comprising the steps of mixing a mixture consisting essentially of (a) an ethylene/vinyl acetate copolymer having an acetate content of from 15% to 75% by weight, (b) powdery polyvinylchloride, in a mixture ratio of (a) to (b) of 1:3 to 2:1, and (c) from 0 to 5% by weight of the mixture of additives customary for polymer processing, in a high-speed mixture at temperatures above the softening temperature of said polyvinylchloride and below 170.degree. C., for a time sufficient to effect homogenization, quenching said homogenized mixture with water and removing the water, grinding the quenched product with the addition of from 0.5 to 10 parts by weight of an inert powder having particles in the submicroscopic range, in a high speed mill under passage of an airstream which is heated by friction, and recovering said pulverulent, tricklable mixture; as well as the powdery mixture so produced.
    Type: Grant
    Filed: August 20, 1976
    Date of Patent: May 9, 1978
    Assignee: Wacker Chemie GmbH
    Inventors: Erwin Gubisch, Walter Kudlich, Walter Popp, Herbert Reinicke
  • Patent number: RE30148
    Abstract: 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: Grant
    Filed: July 17, 1978
    Date of Patent: November 13, 1979
    Assignee: Standard Oil Company (Indiana)
    Inventors: James L. Jezl, Edwin F. Peters
  • Patent number: RE38676
    Abstract: The present invention generally relates to the use of certain ruthenium and osmium complexes that are substantially inactive at a first temperature (preferably about room temperature) but becomes progressively more active at a higher second temperature. This difference in reactivities allows the reaction mixture to be formed and manipulated at the first temperature until polymerization is desired. When appropriate, the reaction mixture is heated to a suitable temperature (preferably greater than 50° C.) to activate the catalyst and to initiate polymerization. Because both the initiation and the rate of polymerization may be controlled with temperature, the inventive methods are especially suitable for ring opening metathesis polymerization (“ROMP”) reactions and for molding polymer articles that require extended pot-lives.
    Type: Grant
    Filed: August 21, 2002
    Date of Patent: December 21, 2004
    Assignee: California Institute of Technology
    Inventors: Robert H. Grubbs, Thomas E. Wilhelm