Polymerization In The Presence Of A Liquid Co2 Diluent Patents (Class 526/942)
  • Patent number: 9469723
    Abstract: A particle manufacturing method of the present invention includes: ring-opening-polymerizing a ring-opening-polymerizable monomer after bringing the ring-opening-polymerizable monomer into contact with a first compressible fluid; and granulating a polymer obtained in the ring-opening-polymerizing by jetting the polymer and the first compressible fluid.
    Type: Grant
    Filed: September 27, 2013
    Date of Patent: October 18, 2016
    Assignee: Ricoh Company, Ltd.
    Inventors: Keiko Osaka, Chiaki Tanaka, Taichi Nemoto
  • Patent number: 7410620
    Abstract: A method for carrying out the continuous polymerization of a monomer in a carbon dioxide reaction medium comprises the steps of: (a) providing an apparatus including a continuous reaction vessel and a separator; (b) carrying out a polymerization reaction in the reaction vessel by combining a monomer and a carbon dioxide reaction medium therein (and preferably by also combining an initiator therein), wherein the reaction medium is a liquid or supercritical fluid, and wherein the reaction produces a solid polymer product in the reaction vessel; then (c) withdrawing a continuous effluent stream from the reaction vessel during the polymerization reaction, wherein the effluent stream is maintained as a liquid or supercritical fluid; then (d) passing the continuous effluent stream through the separator and separating the solid polymer therefrom while maintaining at least a portion of the effluent stream as a liquid or supercritical fluid; and then (e) returning at least a portion of the continuous effluent stream t
    Type: Grant
    Filed: April 22, 2005
    Date of Patent: August 12, 2008
    Assignee: North Carolina State University
    Inventors: Paul A. Charpentier, Joseph M. DeSimone, George W. Roberts
  • Patent number: 7351478
    Abstract: A heat-seal polymer film and method of forming such film is provided. The heat-seal film is formed from metallocene-catalyzed isotactic random copolymers of propylene and at least one other C2 to C8 alpha olefin, such as ethylene random. Such films show improved heat-seal characteristics, such as reduced seal initiation temperatures (SIT's) and improved heat-seal strength, as well as other improved properties.
    Type: Grant
    Filed: March 16, 2001
    Date of Patent: April 1, 2008
    Assignee: Fina Technology, Inc.
    Inventors: Aiko Hanyu, Scott D. Cooper, Mark Miller
  • Patent number: 7063839
    Abstract: A method for continuously separating polymer from a high pressure fluid stream comprises subjecting the high pressure fluid stream comprising polymer particles to a filter, wherein the filter segregates the high pressure fluid stream from the polymer particles; subjecting the polymer particles to a rotating device which transports the polymer particles away from the filter, wherein the polymer particles are exposed to thermal conditions sufficient to melt the polymer particles and form a seal surrounding at least a portion of the rotating device; and separating the molten polymer from the rotating device. The method is carried out such that the separation of polymer from the high pressure fluid stream occurs under steady-state.
    Type: Grant
    Filed: October 18, 2004
    Date of Patent: June 20, 2006
    Assignee: North Carolina State University
    Inventors: Joseph R. Royer, George W. Roberts
  • Patent number: 6914105
    Abstract: A method for carrying out the continuous polymerization of a monomer in a carbon dioxide reaction medium comprises the steps of: (a) providing an apparatus including a continuous reaction vessel and a separator; (b) carrying out a polymerization reaction in the reaction vessel by combining a monomer and a carbon dioxide reaction medium therein (and preferably by also combining an initiator therein), wherein the reaction medium is a liquid or supercritical fluid, and wherein the reaction produces a solid polymer product in the reaction vessel; then (c) withdrawing a continuous effluent stream from the reaction vessel during the polymerization reaction, wherein the effluent stream is maintained as a liquid or supercritical fluid; then (d) passing the continuous effluent stream through the separator and separating the solid polymer therefrom while maintaining at least a portion of the effluent stream as a liquid or supercritical fluid; and then (e) returning at least a portion of the continuous effluent stream t
    Type: Grant
    Filed: November 9, 2000
    Date of Patent: July 5, 2005
    Assignees: North Carolina State University, The University of North Carolina at Chapel Hill
    Inventors: Paul A. Charpentier, Joseph M. DeSimone, George W. Roberts
  • Patent number: 6806332
    Abstract: A method for continuously separating polymer from a high pressure fluid stream comprises subjecting the high pressure fluid stream comprising polymer particles to a filter, wherein the filter segregates the high pressure fluid stream from the polymer particles; subjecting the polymer particles to a rotating device which transports the polymer particles away from the filter, wherein the polymer particles are exposed to thermal conditions sufficient to melt the polymer particles and form a seal surrounding at least a portion of the rotating device; and separating the molten polymer from the rotating device. The method is carried out such that the separation of polymer from the high pressure fluid stream occurs under steady-state.
    Type: Grant
    Filed: February 25, 2002
    Date of Patent: October 19, 2004
    Assignee: North Carolina State University
    Inventors: Joseph R. Royer, George W. Roberts
  • Patent number: 6693159
    Abstract: Highly cross-linked, maroporous/mesoporous polymer monoliths are prepard using supercritical carbon dioxide (scCO2) as the solvent and porogen for the polymerisation of monomers having more than one polymerisable group, at a monomer concentration in CO2 of more than 40 vol %. The procedure allows the direct formation of dry, solvent-free, macroporous/mesoporous cross-linked monoliths with large surface area and well-controlled pore size distribution.
    Type: Grant
    Filed: September 28, 2001
    Date of Patent: February 17, 2004
    Assignee: Cambridge University Technical Services Limited
    Inventors: Andrew Bruce Holmes, Andrew Ian Cooper
  • Patent number: 6660818
    Abstract: A method for producing a fluoropolymer, which comprises polymerizing a monomer containing a fluoromonomer having a polymerizable double bond, using an initiator, in a medium containing fluoroform and water, under a condition such that fluoroform is in a supercritical state.
    Type: Grant
    Filed: September 26, 2002
    Date of Patent: December 9, 2003
    Assignees: Asahi Glass Company, Limited
    Inventors: Yoshio Okahata, Toshiaki Mori, Yuri Tsuchiya
  • Patent number: 6642330
    Abstract: Pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSA can be solubilized or dispersed in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, using an organic cosolvent such as toluene. PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.
    Type: Grant
    Filed: September 26, 2001
    Date of Patent: November 4, 2003
    Assignee: Nitto Denko Corporation
    Inventors: Vincent D. McGinniss, Bhima R. Vijayendran, Kevin B. Spahr, Kazuhiko Shibata, Takayuki Yamamoto
  • Patent number: 6590053
    Abstract: Pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSA can be solubilized or dispersed in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, using an organic cosolvent such as toluene. PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.
    Type: Grant
    Filed: September 26, 2001
    Date of Patent: July 8, 2003
    Assignee: Nitto Denko Corporation
    Inventors: Vincent D. McGinniss, Bhima R. Vijayendran, Kevin B. Spahr, Kazuhiko Shibata, Takayuki Yamamoto
  • Patent number: 6555635
    Abstract: Polymeric compositions of matter are described comprising olefin polymer chains having Mn of about 400 to 75,000, a ratio of vinyl groups to total olefin groups according to the formula vinyl ⁢   ⁢ groups olefin ⁢   ⁢ groups ≥ [ comonomer ⁢   ⁢ mole ⁢   ⁢ percentage + 0.
    Type: Grant
    Filed: November 6, 2001
    Date of Patent: April 29, 2003
    Assignee: ExxonMobil Chemical Patents Inc.
    Inventor: Eric J. Markel
  • Patent number: 6444772
    Abstract: Pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSA can be solubilized or dispersed in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, using an organic cosolvent such as toluene. PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.
    Type: Grant
    Filed: October 28, 1998
    Date of Patent: September 3, 2002
    Assignee: Nitto Denko Corporation
    Inventors: Vincent D. McGinniss, Bhima R. Vijayendran, Kevin B. Spahr, Kazuhiko Shibata, Takayuki Yamamoto
  • Publication number: 20020037987
    Abstract: Pressure sensitive adhesive (PSA) polymers, especially low Tg, high tack, nonpolar and polar polymers useful in formulating PSA can be solubilized or dispersed in a supercritical fluid (SCF), such as liquid CO2 or supercritical CO2, using an organic cosolvent such as toluene. PSA polymers can be polymerized in SCF fluids to make unique adhesive products. Inclusion of a fluorinated reactant in the SCF polymerization process yields a PSA with improved resistance to mineral oil.
    Type: Application
    Filed: September 26, 2001
    Publication date: March 28, 2002
    Inventors: Vincent D. McGinniss, Bhima R. Vijayendran, Kevin B. Spahr, Kazuhiko Shibata, Takayuki Yamamoto
  • Publication number: 20010034423
    Abstract: This invention relates to a polymerization process comprising combining an olefin in the gas or slurry phase with a spray dried catalyst comprising an activator, a particulate filler and a metal catalyst compound.
    Type: Application
    Filed: May 29, 2001
    Publication date: October 25, 2001
    Inventors: John H. Oskam, Timothy R. Lynn, Vincent P. Morrison
  • Patent number: 6127000
    Abstract: A method of protecting a civil infrastructure substrate from the damaging effects of pollution, noxious fumes, weather, and the like. The method comprises (a) providing a composition comprising carbon dioxide and a fluorocarbon such as a fluoropolyether (preferably a perfluoropolyether) or a fluorocarbon elastomer, optionally having at least one anchoring group such as an amide covalently joined thereto, and then (b) applying that composition to the civil infrastructure substrate to form a protective coating thereon. The applying step is preferably carried out by spraying. Compositions useful for carrying out the process of the invention are also disclosed.
    Type: Grant
    Filed: October 10, 1997
    Date of Patent: October 3, 2000
    Assignees: North Carolina State University, University of North Carolina at Chapel Hill
    Inventors: Ruben G. Carbonell, Joseph M. DeSimone, Florence E. Henon
  • Patent number: 6103844
    Abstract: Polymerization of vinylidene fluoride in carbon dioxide media is effectively initiated by dialkyl(2,2-azobisisobutyrate). Methyl is a preferred alkyl.
    Type: Grant
    Filed: June 8, 1998
    Date of Patent: August 15, 2000
    Assignee: E. I. du Pont de Nemours and Company
    Inventor: Paul Douglas Brothers
  • Patent number: 6051682
    Abstract: Fluoromonomer is polymerized to obtain a fluoropolymer with the polymerization being carried out in a pressurized polymerization reactor containing a polymerization medium comprising liquid or supercritical CO.sub.2. The polymerization medium is withdrawn from the reactor together with the fluoropolymer and flash decompressed to thereby recover the fluoropolymer from the medium.
    Type: Grant
    Filed: December 10, 1997
    Date of Patent: April 18, 2000
    Assignee: E. I. du Pont de Nemours and Company
    Inventors: F. Edward Debrabander, Paul Douglas Brothers
  • Patent number: 6034170
    Abstract: Fluoropolymers containing a specified ratio of hydrogen to fluorine atoms attached to polymer backbone atoms dissolve in carbon dioxide under relatively mild conditions of temperature and pressure. The resulting solutions may be used for coatings or encapsulation.
    Type: Grant
    Filed: October 13, 1998
    Date of Patent: March 7, 2000
    Assignees: E. I. du Pont de Nemours and Company, Johns Hopkins University
    Inventors: William Howard Tuminello, Mark A. McHugh, Robert Clayton Wheland, Gregory Thomas Dee
  • Patent number: 5981673
    Abstract: The present invention provides a process for making fluorinated polymers and copolymers having stable end groups. The process includes (1) contacting a fluoromonomer, an initiator capable of producing stable end groups on the polymer chain, and a polymerization medium comprising carbon dioxide, and (2) polymerizing the fluoromonomer. The polymerization medium preferably comprises liquid or supercritical carbon dioxide. Advantageously, the process may also include the step of separating the fluoropolymer from the polymerization medium. The present invention also provides polymerization reaction mixtures useful in the processes of the present invention.
    Type: Grant
    Filed: March 16, 1998
    Date of Patent: November 9, 1999
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5939502
    Abstract: The present invention provides a process for making fluorinated polymers and copolymers having stable end groups. The process includes (1) contacting a fluoromonomer, an initiator capable of producing stable end groups on the polymer chain, and a polymerization medium comprising carbon dioxide, and (2) polymerizing the fluoromonomer. The polymerization medium preferably comprises liquid or supercritical carbon dioxide. Advantageously, the process may also include the step of separating the fluoropolymer from the polymerization medium. The present invention also provides polymerization reaction mixtures useful in the processes of the present invention.
    Type: Grant
    Filed: May 8, 1997
    Date of Patent: August 17, 1999
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5922833
    Abstract: A process for making a fluoropolymer is disclosed. The process comprises solubilizing a fluoromonomer in solvent comprising a carbon dioxide fluid, and then polymerizing the fluoromonomer to produce a the fluoropolymer. A preferred solvent for carrying out the process is supercritical carbon dioxide; preferred fluoromonomers for carrying out the process are fluoroacrylate monomers such as 1,1-dihydroperfluorooctyl acrylate. The polymerization step is preferably carried out in the presence of an initiator such as azobisisobutyronitrile.
    Type: Grant
    Filed: October 31, 1997
    Date of Patent: July 13, 1999
    Assignee: The University of North Carolina at Chapel Hill
    Inventor: Joseph M. DeSimone
  • Patent number: 5824726
    Abstract: The present invention provides a multi-phase polymerization process for making a water insoluble polymer. The process includes (1) providing a mixture comprising carbon dioxide and an aqueous phase, and containing a monomer and a polymerization initiator, and (2) polymerizing the monomer in the reaction mixture. The monomer may be a hydrocarbon or a fluorinated monomer. The polymerization initiator may be soluble in the aqueous phase, soluble in carbon dioxide, or insoluble in both the aqueous phase and carbon dioxide, such that the initiator forms a separate phase. The present invention also provides multi-phase polymerization reaction mixtures useful in the process of making water insoluble polymers.
    Type: Grant
    Filed: September 26, 1997
    Date of Patent: October 20, 1998
    Assignee: University of North Carolina--Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5780565
    Abstract: A polymerization process produces polymers that are insoluble in a reaction mixture that was homogeneous before the polymer began to form. A dispersing agent in the polymerizing system (i.e., the reaction mixture plus the dispersing agent) allows a kinetically stable dispersion of the polymer to be formed in this polymerizing system. The polymerization process is performed in a fluid held under superatmospheric conditions such that the fluid is a liquid or a supercritical fluid; the fluid being carbon dioxide, a hydroflurocarbon, a perfluorocarbon, or a mixture of any of the foregoing.
    Type: Grant
    Filed: November 28, 1995
    Date of Patent: July 14, 1998
    Assignee: Minnesota Mining and Manufacturing Company
    Inventors: Robert S. Clough, Cheryl L. Senger, John E. Gozum
  • Patent number: 5739223
    Abstract: A process for making a fluoropolymer is disclosed. The process comprises solubilizing a fluoromonomer in solvent comprising a carbon dioxide fluid, and then polymerizing the fluoromonomer to produce a the fluoropolymer. A preferred solvent for carrying out the process is supercritical carbon dioxide; preferred fluoromonomers for carrying out the process are fluoroacrylate monomers such as 1,1-dihydroperfluorooctyl acrylate. The polymerization step is preferably carried out in the presence of an initiator such as azobisisobutyronitrile.
    Type: Grant
    Filed: September 18, 1995
    Date of Patent: April 14, 1998
    Assignee: The University of North Carolina at Chapel Hill
    Inventor: Joseph M. DeSimone
  • Patent number: 5688879
    Abstract: A process for making a fluoropolymer is disclosed. The process comprises solubilizing a fluoromonomer in solvent comprising a carbon dioxide fluid, and then polymerizing the fluoromonomer to produce a the fluoropolymer. A preferred solvent for carrying out the process is supercritical carbon dioxide; preferred fluoromonomers for carrying out the process are fluoroacrylate monomers such as 1,1-dihydroperfluorooctyl acrylate. The polymerization step is preferably carried out in the presence of an initiator such as azobisisobutyronitrile.
    Type: Grant
    Filed: February 7, 1997
    Date of Patent: November 18, 1997
    Assignee: The University of North Carolina at Chapel Hill
    Inventor: Joseph M. DeSimone
  • Patent number: 5674957
    Abstract: The present invention provides a process for making fluorinated polymers and copolymers having stable end groups. The process includes (1) contacting a fluoromonomer, an initiator capable of producing stable end groups on the polymer chain, and a polymerization medium comprising carbon dioxide, and (2) polymerizing the fluoromonomer. The polymerization medium preferably comprises liquid or supercritical carbon dioxide. Advantageously, the process may also include the step of separating the fluoropolymer from the polymerization medium.The present invention also provides polymerization reaction mixtures useful in the processes of the present invention.
    Type: Grant
    Filed: September 21, 1995
    Date of Patent: October 7, 1997
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5672667
    Abstract: The present invention provides a multi-phase polymerization process for making a water insoluble polymer. The process includes (1) providing a mixture comprising carbon dioxide and an aqueous phase, and containing a monomer and a polymerization initiator, and (2) polymerizing the monomer in the reaction mixture. The monomer may be a hydrocarbon or a fluorinated monomer. The polymerization initiator may be soluble in the aqueous phase, soluble in carbon dioxide, or insoluble in both the aqueous phase and carbon dioxide, such that the initiator forms a separate phase.The present invention also provides multi-phase polymerization reaction mixtures useful in the process of making water insoluble polymers.
    Type: Grant
    Filed: April 25, 1996
    Date of Patent: September 30, 1997
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5618894
    Abstract: The present invention provides a process for making fluorinated polymers and copolymers having stable end groups. The process includes (1) contacting a fluoromonomer, an initiator capable of producing stable end groups on the polymer chain, and a polymerization medium comprising carbon dioxide, and (2) polymerizing the fluoromonomer. The polymerization medium preferably comprises liquid or supercritical carbon dioxide. Advantageously, the process may also include the step of separating the fluoropolymer from the polymerization medium.The present invention also provides polymerization reaction mixtures useful in the processes of the present invention.
    Type: Grant
    Filed: June 1, 1995
    Date of Patent: April 8, 1997
    Assignee: The University of North Carolina
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5530077
    Abstract: The present invention provides a multi-phase polymerization process for making a water insoluble polymer. The process includes (1) providing a mixture comprising carbon dioxide and an aqueous phase, and containing a monomer and a polymerization initiator, and (2) polymerizing the monomer in the reaction mixture. The monomer may be a hydrocarbon or a fluorinated monomer. The polymerization initiator may be soluble in the aqueous phase, soluble in carbon dioxide, or insoluble in both the aqueous phase and carbon dioxide, such that the initiator forms a separate phase.The present invention also provides multi-phase polymerization reaction mixtures useful in the process of making water insoluble polymers.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: June 25, 1996
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5527865
    Abstract: The present invention provides a multi-phase polymerization process for making a water insoluble polymer. The process includes (1) providing a mixture comprising carbon dioxide and an aqueous phase, and containing a monomer and a polymerization initiator, and (2) polymerizing the monomer in the reaction mixture. The monomer may be a hydrocarbon or a fluorinated monomer. The polymerization initiator may be soluble in the aqueous phase, soluble in carbon dioxide, or insoluble in both the aqueous phase and carbon dioxide, such that the initiator forms a separate phase.The present invention also provides multi-phase polymerization reaction mixtures useful in the process of making water insoluble polymers.
    Type: Grant
    Filed: March 24, 1995
    Date of Patent: June 18, 1996
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5514759
    Abstract: The present invention provides a multi-phase polymerization process for making a water insoluble polymer. The process includes (1) providing a mixture comprising carbon dioxide and an aqueous phase, and containing a monomer and a polymerization initiator, and (2) polymerizing the monomer in the reaction mixture. The monomer may be a hydrocarbon or a fluorinated monomer. The polymerization initiator may be soluble in the aqueous phase, soluble in carbon dioxide, or insoluble in both the aqueous phase and carbon dioxide, such that the initiator forms a separate phase.The present invention also provides multi-phase polymerization reaction mixtures useful in the process of making water insoluble polymers.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: May 7, 1996
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Timothy Romack
  • Patent number: 5506317
    Abstract: The heterogeneous polymerization of water-insoluble polymer in CO.sub.2 is disclosed. The method comprises providing a heterogeneous reaction mixture comprising CO.sub.2, a monomer, and a surfactant, then polymerizing the monomer to form a water-insoluble polymer.
    Type: Grant
    Filed: January 25, 1995
    Date of Patent: April 9, 1996
    Assignee: The University of North Carolina at Chapel Hill
    Inventors: Joseph M. DeSimone, Elise E. Maury, James R. Combes, Yusuf Z. Menceloglu
  • Patent number: 5496901
    Abstract: A process for making a fluoropolymer is disclosed. The process comprises solubilizing a fluoromonomer in solvent comprising a carbon dioxide fluid, and then polymerizing the fluoromonomer to produce the fluoropolymer. A preferred solvent for carrying out the process is supercritical carbon dioxide; preferred fluoromonomers for carrying out the process are fluoroacrylate monomers such as 1,1-dihydroperfluorooctyl acrylate. The polymerization step is preferably carried out in the presence of an initiator such as azobisisobutyronitrile.
    Type: Grant
    Filed: September 27, 1994
    Date of Patent: March 5, 1996
    Assignee: University of North Carolina
    Inventor: Joseph M. DeSimone