WO2013085463A1 - Électrolyte polymère - Google Patents

Électrolyte polymère Download PDF

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Publication number
WO2013085463A1
WO2013085463A1 PCT/SE2012/051366 SE2012051366W WO2013085463A1 WO 2013085463 A1 WO2013085463 A1 WO 2013085463A1 SE 2012051366 W SE2012051366 W SE 2012051366W WO 2013085463 A1 WO2013085463 A1 WO 2013085463A1
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WO
WIPO (PCT)
Prior art keywords
polymeric material
formula
relates
spacer
acidic groups
Prior art date
Application number
PCT/SE2012/051366
Other languages
English (en)
Inventor
Shogo Takamuku
Patric Jannasch
Original Assignee
Shogo Takamuku
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shogo Takamuku filed Critical Shogo Takamuku
Publication of WO2013085463A1 publication Critical patent/WO2013085463A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the obtained polymer according to the present invention has a synthetically controlled morphology.
  • the morphology obtained enables the polymerized monomers having specific structural units to be polymerized into a polymer with a polydispersity index of about 2 in theory, insuring a lengthy ionic sequence with a precisely given length, if polycondensation is applied using the novel ionic macromonomers disclosed in the present invention.
  • the present invention relates to a polymeric material comprising structural elements of the following general formula (I):
  • Ph 1 , Ph 2 and Ph 3 independently are phenylenes comprising acidic groups with or without a spacer or the salts thereof;
  • step b) polycondensation or nickel-catalyzed coupling reaction of the substituted arylene sulfone monomer of step a) during the formation of a sulfonated, phosphonated, carboxylated and/or borated polymer.
  • the monomer produced in step a) mentioned above is produced from the monomer derivative which may be obtained through an additional reaction, followed by metalation-oxidation.
  • Figure 1 1 shows the 1 H NMR spectra of oligomer (9) before and after end capping by hexafluorobenzene.
  • the present invention relates to polyelectrolytes comprising structures with aromatic groups connected with sulfone bridges, wherein at least some of the aromatic groups comprise at least one ionic group.
  • the aromatic groups are preferably arylene sulfones comprising substituent(s) on the phenylene group, at least one ionic group.
  • the present invention relates to polyelectrolytes which e.g. may be used for fuel cells, reverse osmosis, diapers and surfactants.
  • the present invention discloses new polymeric materials comprising substituted poly(phenylenes) featuring the structural element Formula (I):
  • the phenylene rings comprise at least one acidic group or its salt attached directly onto the rings or via a spacer such as aliphatic or aromatic chains, wherein said phenylene rings are bridged by either sulfoxides or sulfones, as well as their synthesis and use.
  • poly(arylene sulfone)s containing one or several structural elements of the Formula (I), wherein X 1 , X 2 , X 3 and X 4 independently are identical or different from each other, and chosen from O, S, SO2, SO and a direct bond.
  • X 1 may also be a H termination when Formula (I) relates to side chains of the polymeric material.
  • phenylenes in a ortho position to any other linkages than SO or SO2 bridges e.g., Ph-Ph covalent bond, ether, thioether, amin, alkyl spacer
  • This will lead to cyclization with an adjacent phenylene having an acidic group or salt thereof in a similar meta position.
  • the acidic groups would be located closely and thus easily reacted and forming a cyclic bonding via the meta and para positions.
  • any at least one acidic group or salts attached to the phenylene rings in contact with a SO or SO2 group is in an ortho or meta position in relation to said SO or SO2 group.
  • any acidic groups or the salts thereof attached to a phenylene ring within F 1 or F 2 in contact with another bridging group like O, S, SO or a direct bond may be in a meta position in relation to said bridging group.
  • the above mentioned monomer units may be used to form homopolymers, statistical and gradient copolymers or di-, tri-, multiblock copolymers in both main chain and side chain type polymer structures.
  • the solution was heated at 160 ° C for 4 h for dehydration by removing the toluene. The temperature was then increased to 175 ° C for 3 days to complete the polycondensation, before the polymer product was precipitated in IPA, followed by a wash in deionized water. The obtained polymer was filtered and dried at 60 ° C in a vacuum oven for 24 h.
  • DCDPS (0.3720 g, 1 .2955 mmol), monomer (3) (0.4493 g, 0.4879 mmol), biphenol (0.3321 g, 1 .7835 mmol), K 2 C0 3 (1 .2324 g, 8.9174 mmol), dimethyl sulfoxide (DMSO) (5.0 ml_) and cyclohexane (5.0 ml_) were put in a two-neck flask (50 ml_) equipped with a magnetic stirrer, a N 2 inlet, a Dean- Stark trap filled with cyclohexane and a condenser fit with a CaC trap.
  • DMSO dimethyl sulfoxide
  • cyclohexane 5.0 ml_

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polyethers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

La présente invention concerne un matériau polymère comprenant les motifs structuraux de formule générale (I) suivante : dans laquelle Ph1, Ph2 et Ph3 représentent, indépendamment l'un de l'autre, des phénylènes comprenant des groupes acides dotés ou pas d'une séquence d'espacement ou des sels de ceux-ci ; X1, X2, X3 et X4 représentent, indépendamment l'un de l'autre, O, S, SO, SO2, ou une liaison directe, X1 pouvant également représenter une extrémité H lorsque la formule (I) s'applique à des chaînes latérales du matériau polymère, et au moins deux symboles parmi X1, X2, X3 et X4 représentant SO ou SO2 lorsque la formule (I) s'applique à des chaînes principales du matériau polymère ou au moins un symbole parmi X1, X2, X3 et X4 représentant SO ou SO2 lorsque la formule (I) s'applique à des chaînes latérales du matériau polymère ; m, n et q représentent, indépendamment l'un de l'autre, des nombres entiers et la somme de m+n+q est au moins égale à 3 lorsque la formule (I) s'applique à des chaînes principales du matériau polymère ou la somme de m+n+q est au moins égale à 2 lorsque la formule (I) s'applique à des chaînes latérales du matériau polymère, la somme de m+n+q étant identique pour tous les motifs structuraux du matériau polymère. Lorsque la formule (I) s'applique à des chaînes principales du matériau polymère et quand n'importe lequel des symboles X1, X2, X3 et X4 représente SO ou SO2, alors Ph1, Ph2 ou Ph3, lié à SO ou SO2, comporte au moins l'un des groupes acides dotés ou pas d'une séquence d'espacement ou des sels de celui-ci, positionné en position ortho par rapport à SO ou SO2. L'invention concerne également la production d'un tel matériau polymère.
PCT/SE2012/051366 2011-12-09 2012-12-10 Électrolyte polymère WO2013085463A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE1151177 2011-12-09
SE1151177-1 2011-12-09

Publications (1)

Publication Number Publication Date
WO2013085463A1 true WO2013085463A1 (fr) 2013-06-13

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PCT/SE2012/051366 WO2013085463A1 (fr) 2011-12-09 2012-12-10 Électrolyte polymère

Country Status (1)

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WO (1) WO2013085463A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020091225A1 (en) * 2000-09-20 2002-07-11 Mcgrath James E. Ion-conducting sulfonated polymeric materials
US20030096149A1 (en) * 2001-09-21 2003-05-22 Tohru Koyama Solid polyelectrolyte, assembly of membrane and electrodes, and fuel cell
US20070148518A1 (en) * 2003-12-25 2007-06-28 Sumitomo Chemical Company, Limited Polymer electrolyte and use thereof
JP2007161910A (ja) * 2005-12-15 2007-06-28 Nippon Kayaku Co Ltd 熱架橋性高分子組成物，架橋高分子電解質膜およびその製造方法
US20070292733A1 (en) * 2004-07-23 2007-12-20 Mitsui Chemicals, Inc. Binder for Fuel Cell, Composition for Forming Electrode, Electrode, and Fuel Cell Using the Electrode
US20080176126A1 (en) * 2006-09-18 2008-07-24 Samsung Sdi Co, Ltd. Electrolyte membrane comprising nanocomposite ion complex, manufacturing method thereof, and fuel cell including the same
WO2009066952A1 (fr) * 2007-11-23 2009-05-28 Dongjin Semichem Co., Ltd. Monomère pour polymère conducteur de protons qui comporte un groupe acide dans une chaîne latérale, polymère conducteur de protons obtenu au moyen du monomère, procédé d'obtention du polymère conducteur de protons, membrane électrolytique comportant le polymère conducteur de protons, et ensemble membrane/électrode incluant l'électrolyte
KR20090054614A (ko) * 2007-11-27 2009-06-01 한양대학교 산학협력단 맞춤형 비불소계 촉매 바인더, 막-전극 어셈블리 및 이를포함하는 연료전지
US20090148751A1 (en) * 2007-12-07 2009-06-11 Samsung Sdi Co., Ltd. Membrane electrode assembly for fuel cell, and method of manufacturing the same
US20090208804A1 (en) * 2006-07-04 2009-08-20 Ryuma Kuroda Polymer electrolyte emulsion and use thereof
KR20100120519A (ko) * 2009-05-06 2010-11-16 한양대학교 산학협력단 디카보닐기로 가교된 폴리설폰, 이의 제조방법, 이를 이용한 고분자전해질막 및 이를 채용한 연료전지

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020091225A1 (en) * 2000-09-20 2002-07-11 Mcgrath James E. Ion-conducting sulfonated polymeric materials
US20030096149A1 (en) * 2001-09-21 2003-05-22 Tohru Koyama Solid polyelectrolyte, assembly of membrane and electrodes, and fuel cell
US20070148518A1 (en) * 2003-12-25 2007-06-28 Sumitomo Chemical Company, Limited Polymer electrolyte and use thereof
US20070292733A1 (en) * 2004-07-23 2007-12-20 Mitsui Chemicals, Inc. Binder for Fuel Cell, Composition for Forming Electrode, Electrode, and Fuel Cell Using the Electrode
JP2007161910A (ja) * 2005-12-15 2007-06-28 Nippon Kayaku Co Ltd 熱架橋性高分子組成物，架橋高分子電解質膜およびその製造方法
US20090208804A1 (en) * 2006-07-04 2009-08-20 Ryuma Kuroda Polymer electrolyte emulsion and use thereof
US20080176126A1 (en) * 2006-09-18 2008-07-24 Samsung Sdi Co, Ltd. Electrolyte membrane comprising nanocomposite ion complex, manufacturing method thereof, and fuel cell including the same
WO2009066952A1 (fr) * 2007-11-23 2009-05-28 Dongjin Semichem Co., Ltd. Monomère pour polymère conducteur de protons qui comporte un groupe acide dans une chaîne latérale, polymère conducteur de protons obtenu au moyen du monomère, procédé d'obtention du polymère conducteur de protons, membrane électrolytique comportant le polymère conducteur de protons, et ensemble membrane/électrode incluant l'électrolyte
KR20090054614A (ko) * 2007-11-27 2009-06-01 한양대학교 산학협력단 맞춤형 비불소계 촉매 바인더, 막-전극 어셈블리 및 이를포함하는 연료전지
US20090148751A1 (en) * 2007-12-07 2009-06-11 Samsung Sdi Co., Ltd. Membrane electrode assembly for fuel cell, and method of manufacturing the same
KR20100120519A (ko) * 2009-05-06 2010-11-16 한양대학교 산학협력단 디카보닐기로 가교된 폴리설폰, 이의 제조방법, 이를 이용한 고분자전해질막 및 이를 채용한 연료전지

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DONG JIN YOO ET AL.: "Synthesis, and Structural and Thermal Characterizations of Tetrasulfonated Poly(arylene biphenylsulfone ether) Copolymer Ion Conducting Electrolytes", BULL. KOREAN CHEM. SOC., vol. 32, no. 11, 2011, pages 4041 - 48, XP003031513 *

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