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WO2006107205A1 - Membranes conductrices de protons - Google Patents

Membranes conductrices de protons Download PDF

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Publication number
WO2006107205A1
WO2006107205A1 PCT/NL2006/050073 NL2006050073W WO2006107205A1 WO 2006107205 A1 WO2006107205 A1 WO 2006107205A1 NL 2006050073 W NL2006050073 W NL 2006050073W WO 2006107205 A1 WO2006107205 A1 WO 2006107205A1
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WO
WIPO (PCT)
Prior art keywords
proton conducting
conducting membrane
membrane composite
composite according
pyrimidine derivative
Prior art date
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Ceased
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PCT/NL2006/050073
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English (en)
Inventor
Lucia Daniela Ionescu
Andre Wakker
Michiel De Heer
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Energy Research Centre of the Netherlands
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Energy Research Centre of the Netherlands
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Publication of WO2006107205A1 publication Critical patent/WO2006107205A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/1062—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the physical properties of the porous support, e.g. its porosity or thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • 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 present invention relates to proton conducting membranes comprising a pyrimidine derivative and a process for preparing such proton conducting membranes.
  • the present invention provides a proton conducting membrane composite comprising a polyalkene membrane and a pyrimidine derivative with a proton carrying capability. These proton conducting membranes are very suitable for use in fuel cells.
  • the currently most used proton conducting membranes are based on Nafion® perfluorosulfonic acid ionomers having the general structure (Butler, G. B.; O'Driscoll, K.F.; Wilkes, G.L. JMS-Rev. Macromol Chem. Phys. 1994, C34(3), 325 - 373):
  • the main problem with the Nafion® membrane is that it needs 100% water saturation (i.e. a 100% RH environment) to achieve the required (high) proton conductivity.
  • water is the proton conducting phase in the Nafion® membrane.
  • FC Fluel Cell
  • CO tolerance of the PEM FC even increases dramatically with increasing operating temperature.
  • Typical target temperatures also depending on the cooling concept, are in the range of about 120 0 C up to about 150 0 C.
  • PBI means polyimidazole
  • PBI membranes doped with phosphoric acid are another, and promising, technology option, and do indeed operate without any humidification and typically at temperatures of 150 0 C or higher, it is in fact a quasi- PAFC ("Phosphoric Acid Fuel Cell”), with similar draw-backs: large cathode losses, limited thermal cyclability and life issues related to the leaching of the acid.
  • PBI based MEA' s are currently being co-developed by Celanese and Hyundai, and are restrict on the market.
  • US 6.514.561 discloses a high molecular weight polyethylene membrane marketed under the trade name Solupor®. This polymer has a high porosity and high mechanical strength and is therefore available as thin films which are excellent substrates for proton conducting membranes.
  • WO 2006/016805 discloses copolymers of 2,5- and/or 2,6-disubstituted phenols which are very useful in the manufacture of proton conducting membranes.
  • the object of the present invention is to overcome the drawbacks indicated above.
  • the present invention provides a new class of proton conducting membranes that can be used for high temperature PEM fuel cell applications. Summary of the invention
  • the present invention provides a proton conducting membrane composite comprising:
  • the present invention further provides a process for the manufacture of a proton conducting membrane composite comprising:
  • step (b) contacting the solution as obtained in step (a) with a polyalkene membrane;
  • ambient temperature is to be understood as a temperature prevailing under normal conditions of operation as will be apparent to those skilled in the art.
  • the term "pyrimidine derivative" is to be understood as to encompass compounds comprising at least one fully unsaturated six-membered ring structure comprising at least two nitrogen atoms, wherein the remaining atoms of the ring structure are carbon atoms.
  • the compounds may comprise other ring structures condensed to the at least one unsaturated six-membered ring structure comprising at least two nitrogen atoms, e.g. five-membered, six-membered or seven- membered ring structures, wherein these five-membered, six-membered or seven- membered ring structures may comprise one or more heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur. It is, however, preferred that such an heteroatom is nitrogen.
  • pyrimidine derivatives encompass derivatives of pyrimidine (1,3-diazine), pyrazine (1,4-diazine), 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,3,5-oxadiazine, quinazoline, 1,4- benzodiazine, guanine, adenine, cytosine, uracil, thymine, guanamine and melamine.
  • the polyalkene comprises a homopolymer of ethene or a copolymer of ethene and a C3-C12 ⁇ -olefin, or a homopolymer of propene or a copolymer of propene and ethylene and/or a C3-C12 ⁇ -olefin, or mixtures thereof.
  • suitable ⁇ -olefins are propene, 1-butene, 2-methyl-l-pentene, 1-hexene, 1- octene, 1-decene and 1-dodecene.
  • the homopolymers or copolymers may be prepared by well known techniques including Ziegler-Natta catalysed or metallocene catalysed polymerizations which can be conducted in the gas phase or in solution. These polymerisations may be carried in one or more, i.e. serial, reactors.
  • the homopolymers or copolymers may have an average molecular weight that may vary considerably and preferably is within the range of 10.000 t0 1.000.000.
  • the density (according to ASTM D 1505) is preferably within the range of 0.85 to 0.96 g/cm 3 .
  • the melt index (according to ASTM D 1238, 2.16 kg, 190 0 C) is preferably within the range of 1 to 1000.
  • the comonomer content is preferably 0.1 to 50 wt.%, more preferably 0.1 - 20 wt.% and even more preferably 0.1 to 10 wt.%.
  • the polyalkene is a polyethylene, a polypropene, an ethylene C3 - C 12 ⁇ -olefin copolymer, in particular an ethene-propene copolymer, or a mixture thereof. Even more preferably, the polyalkene is a polyethylene having a weight average molecular weight of 100.000 and 5.000.000.
  • a polyalkene blend which contains a polyethylene having a weight average molecular weight less than 500.000, preferably 100.000 to 500.000, can also contain a polyethylene having a weight average molecular weight greater than 1.000.000, preferably 1.000.000 to 5.000.000. As a result of the presence of the latter polyethylene, a high strength of the membrane is obtained.
  • the membrane made of the polyalkene has a porosity of 30 - 90% by volume. This implies that the volume of the pores within the membrane accounts for 30 - 90 % by volume of the total volume of the total membrane. Porosities lower than 30 % by volume provides in general a low ion conductivity whereas porosities above 90 % by volume reduces mechanical strength undesirably.
  • Suitable polyalkenes that can be used for the production of the membrane is disclosed in US 6.514.561, incorporated by reference herein.
  • the membrane that is manufactured from the polyalkene may be stretched, either uniaxially or biaxially.
  • Membranes that are stretched are for example disclosed in US 5.376.445, incorporated by reference herein.
  • the membrane is most preferably a Solupor® membrane that is available from DSM.
  • the pyrimidine derivative is preferably a pyrimidine derivative that can form at least two hydrogen bridges with a second pyrimidine derivative.
  • a pyrimidine derivative that can form at least two hydrogen bridges with a second pyrimidine derivative.
  • Such compounds are well known in the art and are for example disclosed in R.P. Sijbesma et al. Science 278, 1601, 1997, and US 6.320.018, incorporated by reference herein. More preferably, the pyrimidine derivative is represented by formula (I) or (II) or a tautomer thereof:
  • Ri, R 2 , R 4 , R 5 , R O and R 7 are independently selected from hydrogen, Ci - C 6 linear or branched alkyl, -NH 2 or -OH; and
  • R 3 is hydrogen or a Ci - Ce linear or branched alkyl group, or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen.
  • a preferred group of pyrimidine derivatives is the class wherein R 1 , R 2 , R 4 , R 5 , R 6 and R 7 are independently selected from hydrogen, Ci - C 6 linear or branched alkyl, -NH 2 or -OH; R 3 is hydrogen or a Ci - C 6 linear or branched alkyl group, or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen; and wherein at least one of Ri - R 7 is hydrogen.
  • a more preferred group of pyrimidine derivatives is the class wherein at least one of Ri, R 2 , R 4 , R 6 , R7 and Rs is hydrogen whereas R 3 is hydrogen or a Ci - C 6 linear or branched alkyl group, or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen.
  • An even more preferred group of pyrimidine derivatives is the class wherein R 3 is hydrogen or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen, wherein at least one of Ri, R 2 , R 4 , R 6 , R 7 and Rs is hydrogen.
  • An much more preferred group of pyrimidine derivatives is the class wherein R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen, and wherein at least one of Ri and R 2 is -NH 2 or -OH.
  • R 3 together with R 4 and the adjacent carbon atoms to which they are bonded form an saturated or unsaturated five or six membered ring, it is preferred that they form a saturated or unsaturated five membered ring, said saturated or unsaturated five membered ring preferably comprising one or two nitrogen atoms, most preferably two nitrogen atoms.
  • at least one of Ri, R 2 , R 4 , R 5 , R 6 and R 7 is -NH 2 or -OH.
  • the pyrimidine derivative according to the invention is selected from the group consisting of guanine, adenine, cytosine, uracil, thymine, guanamine and melamine.
  • the pyrimidine derivatives are modified with a proton source.
  • the modification can be accomplished by contacting the pyrimidine derivative with the proton source or by reacting the pyrimidine derivative with a (precursor for) a proton source.
  • the pyrimidine derivative is modified by dissolving the pyrimidine derivative in a suitable solvent or solvent mixture where after the solution is contacted with the proton source, preferably poly(phosphoric acid). To isolate the product, the solvent is subsequently evaporated and the modified pyrimidine derivative is isolated and further processed.
  • the pyrimide derivative is chemically modified, preferably through a phosphonation reaction.
  • this modification is carried out by first providing the pyrimidine derivative with one or more halomethylene groups, wherein the halides are selected from chlorine, bromine or iodine.
  • This first step is preferably a chloromethylation.
  • adenine can be modified as shown below:
  • the pyrimidine derivative provided with one or more halomethylene groups is reacted with a Ci - C 6 trialkyl phosphite, wherein the alkyl groups may independently be different and may be linear or branched.
  • the latter phosphonation reaction is also known in the art as the Michaelis - Arbuzov reaction (cf. for example K. Sasse, Houben-Weyl 12/1, 433, 1963; B.A. Arbuzov, Pure & Appl. Chem. 9, 307, 1964; G.M. Kosolapoff, Org. React. 6, 276, 1951; D. Redmore, Chem. Rev. 71, 317, 1971).
  • the modified adenine from above can be converted into a phosphonated adenine derivative:
  • the present invention provides a process for the preparation of phosphonated pyrimidine derivatives which process includes the following steps:
  • R 1 , R 2 , R 4 , R 5 , R O and R 7 are independently selected from hydrogen, Ci - C 6 linear or branched alkyl, -NH 2 or -OH;
  • R 3 is hydrogen or a Ci - C 6 linear or branched alkyl group, or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen; and wherein at least one of Ri - R 7 is hydrogen; and
  • a preferred group of pyrimidine derivatives for this process is the class wherein at least one of Ri, R 2 , R 4 , R 6 , R7 and Rs is hydrogen whereas R 3 is hydrogen or a Ci -
  • R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen.
  • An even more preferred group of pyrimidine derivatives for this process is the class wherein R 3 is hydrogen or R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen, wherein at least one of Ri, R 2 , R 4 , R 6 , R7 and Rs is hydrogen.
  • An much more preferred group of pyrimidine derivatives for this process is the class wherein R 3 forms together with R 4 and the adjacent carbon atoms to which they are bonded a saturated or unsaturated five or six membered ring, said saturated or unsaturated five or six membered ring comprising one or two heteroatoms selected from the group consisting of nitrogen and oxygen, and wherein at least one of Ri and R 2 is -NH 2 or -OH.
  • R 3 together with R 4 and the adjacent carbon atoms to which they are bonded form an saturated or unsaturated five or six membered ring, it is preferred that they form a saturated or unsaturated five membered ring, said saturated or unsaturated five membered ring preferably comprising one or two nitrogen atoms, most preferably two nitrogen atoms.
  • At least one of Ri, R 2 , R 4 , R 5 , Re and R 7 is -NH 2 or -OH.
  • the pyrimidine derivative according to the invention is selected from the group consisting of guanine, adenine, cytosine, uracil, thymine, guanamine and melamine.
  • the proton conducting membrane composite according to the invention is manufactured by impregnation of the polyalkene membrane with a solution of the modified pyrimidine derivative.
  • the solution comprises 1 to 10 wt.% of the pyrimidine derivative, calculated on the total weight of the solution.
  • the solvent employed may be a single solvent or a solvent mixture and preferably comprises a polar aprotic solvent, e.g. DMSO.
  • the solvent is evaporated, preferably at a temperature between ambient temperature , more preferably about 50 0 C, and the melting point of the polyalkene membrane, preferably 10 0 C below the melting point of the polyalkene membrane.
  • the impregnation of the polyalkene membrane can suitably be conducted according procedures disclosed in US 6.514.561, enclosed by reference herein. Accordingly, the present invention provides a process for the manufacture of a proton conducting membrane composite comprising: (a) forming a solution of a pyrimidine derivative in a solvent or solvent mixture;
  • step (b) contacting the solution as obtained in step (a) with a polyalkene membrane;
  • step (c) evaporating the solvent or solvent mixture at a temperature between ambient temperature and below the melting point of the polyalkene membrane.
  • the pyrimidine derivative employed in step (a) is a phosphonated pyrimidine derivative as disclosed above.
  • the pirimidine derivatives according to the present invention may also be chemically bonded to a polymer or polymer backbone to provide proton conducting polymers.
  • proton conducting polymers are for example disclosed in European
  • Such polymers can for example be prepared by modifying or functionalising the pirimidine derivatives by e.g. the chloromethylation reaction disclosed above. After modification or functionalisation, the pirimidine derivatives can be attached to the polymer main by for example grafting techniques or may be incorporated in the polymer main chain by for example polycondensation.
  • the bischloromethylated compounds disclosed above can be converted in e.g. their isocyanates which in a subsequent step can be reacted in a polycondensation with e.g. diols and optionally other diisocyanates.
  • the present invention therefore also relates to a polymer or copolymer wherein at least one of the pirimidine derivatives according to the invention is covalently bonded to or incorporated in the polymer or copolymer main chain.
  • ZnCl 2 were added. Then, 4 ml thionylchloride were slowly added without allowing the temperature to raise above 25°C. After all thionylchloride was added, the temperature was slowly raised to 60 0 C and the mixture was stirred for 6 h. The ZnCl 2 was then washed out by washing several times the reaction mixture with THF or ethanol and afterwards the product was dried.
  • Example 2 2,8-bis(diethylphosphonyl)adenine An amount of about 2 g 2,8-bis(chloromethyl)adenine was mixed with about 20 g diethyleneglycol diethylether (DEC). Under stirring an excess mount of 3 g (1.1 g in theory) triethylphosphite (TEP) was added to 10 ml DEC. The mixture was slowly heated to 60 0 C and the mixture of 2,8-bis(chloromethyl)adenine was slowly added. The reaction was continued for about 3 hours. Subsequently, some pentane was added the precipitate was filtered off. The product was purified by redissolving the product in dichloromethane and re-precipitation with pentane.
  • DEC diethyleneglycol diethylether
  • TEP triethylphosphite
  • the conductivity results were good (0.02 S/cm at 140 0 C).
  • the conductivity results were better for mixtures that combined phosphonated guanine and cytosine which due to their structure they can better self-organize and form efficient intermolecular hydrogen bridges. All the conductivity results were well reproducible and following the Arrhenius dependence conductivity vs. temperature, (cf. Figure 1).

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Abstract

La présente invention concerne un composite membranaire conducteur de protons comprenant une membrane de polyalkylène et un dérivé de pyrimidine, le dérivé de pyrimidine étant représenté par la formule (I) ou (II), ou un tautomère dudit dérivé. Dans lesdites formules, R1, R2, R4, R5, R5 et R7 sont indépendamment sélectionnés parmi hydrogène, alkyle C1 - C6 linéaire ou ramifié, -NH2 ou OH ; et R3 représente hydrogène ou un groupe alkyle C1 - C6 linéaire ou ramifié, ou R3 forme avec R4 et les atomes de carbone adjacents auxquels ils sont liés, un cycle à cinq ou six éléments saturé ou insaturé, ledit cycle à cinq ou six éléments saturé ou insaturé comprenant un ou deux hétéroatomes sélectionnés dans le groupe comprenant l'azote et l'oxygène. L'invention concerne également un procédé de fabrication d'un composite membranaire conducteur de protons et son utilisation dans une pile à combustible.
PCT/NL2006/050073 2005-04-04 2006-04-04 Membranes conductrices de protons Ceased WO2006107205A1 (fr)

Applications Claiming Priority (2)

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EP05075771.5 2005-04-04
EP05075771 2005-04-04

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302269A (en) * 1990-06-11 1994-04-12 The Dow Chemical Company Ion exchange membrane/electrode assembly having increased efficiency in proton exchange processes
EP1201295A2 (fr) * 2000-10-30 2002-05-02 Sumitomo Chemical Company, Limited Film poreux, séparateur pour cellule et cellule
WO2005001979A2 (fr) * 2003-06-27 2005-01-06 E.I. Dupont De Nemours And Company Composes de sulfonamide fluore et membranes d'electrolytes polymeres prepares a partir de ces composes en vue d'une utilisation dans des cellules electrochimiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302269A (en) * 1990-06-11 1994-04-12 The Dow Chemical Company Ion exchange membrane/electrode assembly having increased efficiency in proton exchange processes
EP1201295A2 (fr) * 2000-10-30 2002-05-02 Sumitomo Chemical Company, Limited Film poreux, séparateur pour cellule et cellule
WO2005001979A2 (fr) * 2003-06-27 2005-01-06 E.I. Dupont De Nemours And Company Composes de sulfonamide fluore et membranes d'electrolytes polymeres prepares a partir de ces composes en vue d'une utilisation dans des cellules electrochimiques

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