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• • 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
  • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
  • C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
• • 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
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/78—Graft polymers
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  • 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
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
  • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/122—Ionic conductors
• • 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
  • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
• • 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
  • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
• • 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
  • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• • 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
  • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
• • 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
  • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
  • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
• • 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
  • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
  • H01M8/1086—After-treatment of the membrane other than by polymerisation
  • H01M8/1088—Chemical modification, e.g. sulfonation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/14—Membrane materials having negatively charged functional groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/16—Membrane materials having positively charged functional groups
• • 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
  • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
• • 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
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • 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 invention relates to fuel cell proton conducting membranes having a proton gradient, to processes for producing such membranes and to fuel cell devices comprising such membranes.
• the field of application of the invention is therefore that of fuel cells, and more particularly of fuel cells, comprising as electrolyte, a proton-conducting membrane, such as PEMFC ("Proton Exchange Membrane") fuel cells. Fuel Cell for Proton Exchange Membrane Fuel Cell).
• a fuel cell generally comprises a stack of elementary cells in which an electrochemical reaction takes place between two reactants which are introduced continuously.
• Fuel such as hydrogen, for cells operating with hydrogen / oxygen mixtures, or methanol for batteries operating with methanol / oxygen mixtures, is brought into contact with the anode, whereas the oxidant, generally oxygen, is brought into contact with the cathode.
• the anode and the cathode are separated by an electrolyte of the ionic conductive membrane type.
• the electrochemical reaction whose energy is converted into electrical energy, splits into two half-reactions: - an oxidation of the fuel, taking place at the anode / electrolyte interface producing, in the case of hydrogen cells, H + protons, which will cross the electrolyte in the direction of the cathode, and electrons, which join the external circuit, in order to contribute to the production of electrical energy;
• the electrode-membrane-electrode assembly is a very thin assembly with a thickness of the order of a millimeter and each electrode is fed with the gases, for example using a fluted plate.
• the ionic conducting membrane is generally an organic membrane containing ionic groups which, in the presence of water, allow the conduction of the protons produced at the anode by oxidation of hydrogen.
• This membrane is generally between 50 and 150 microns and results from a compromise between the mechanical strength and the ohmic drop.
• This membrane also allows the separation of gases.
• the chemical and electrochemical resistance of these membranes allows, in general, a battery operation over periods greater than 1000 hours.
• the polymer constituting the membrane must therefore fulfill a number of conditions relating to its mechanical, physicochemical and electrical properties which are, inter alia, those defined below.
• the polymer must first be able to give thin films, 50 to 150 micrometers, dense, without defects.
• the mechanical properties, elastic modulus, tensile strength, ductility, must make it compatible with assembly operations including, for example, clamping between metal frames.
• the properties must be preserved by changing from dry to wet.
• the polymer must have good thermal stability to hydrolysis and have good resistance to reduction and oxidation. This thermomechanical stability is appreciated in terms of variation of ionic resistance, and in terms of variation of the mechanical properties.
• the polymer must finally have a high ionic conductivity, this conductivity being provided by acidic groups, such as carboxylic acid, phosphoric acid or sulfonic acid groups connected to the polymer chain.
• acidic groups such as carboxylic acid, phosphoric acid or sulfonic acid groups connected to the polymer chain.
• Membranes prepared with these products are inexpensive but do not have sufficient hydrogen stability at 50-60 ° C for long-term applications.
• sulfonated polystyrene derivatives have a higher stability than sulfonated phenolic resins, but can not be used at more than 50-60 ° C.
• acceptable performance is obtained from polymers consisting of a perfluorinated linear main chain and a side chain carrying a sulfonic acid group.
• the membranes currently used and in particular the membranes of the NAFION® type have a limit to the level of the order using a temperature of 90 0 C, the phenomenon of aging after 3000-4000 hours of use and finally insufficient proton conduction.
• the inventors therefore proposed to put in place membranes that solved the problems and, in particular, membranes with better proton conduction than existing membranes such as NAFION® membranes.
• the invention relates to a proton conducting membrane for a fuel cell comprising a grafted (co) polymer comprising a main chain and grafts covalently linked to said main chain, said grafts comprising at least one proton attracting group and at least one proton donor group.
• (co) polymer is meant a polymer comprising the same repeating units or a copolymer comprising different repeating units.
• graft is meant a side chain covalently linked to the main chain of the (co) polymer, said graft comprising both a proton attractor group and a proton donor group.
• proton attracting group is meant a group capable of fixing a proton, this binding being done by sharing a doublet free of an atom of said group with the proton or by electrostatic attraction with a negatively charged group.
• the proton attractor group has an atom bearing a free doublet and / or is negatively charged.
• groups bearing proton-withdrawing free doublets may be amino groups, such as primary amine groups (-NH 2 ), secondary amine groups (-NH-) included in a hydrocarbon linear chain. or included in an imidazole group, guanidine.
• Negatively charged proton attractant groups may be salts of the carboxylic acid functions -CO 2 H, sulfonic acid -SO 3 H and phosphonic acid -PO 3 H 2 , functions -O-, S-.
• proton donor group is meant a group capable of dissociating by releasing a proton. From a chemical point of view, these groups may be an acid group -CO 2 H, -SO 3 H or -PO 3 H 2 , a group -OH, -SH, an amino group salt, such as a salt of primary amine (-NH 2 ), secondary amine (-NH-) included in a hydrocarbon linear chain or included in a group such as an imidazole, guanidine group.
• these groups may be an acid group -CO 2 H, -SO 3 H or -PO 3 H 2 , a group -OH, -SH, an amino group salt, such as a salt of primary amine (-NH 2 ), secondary amine (-NH-) included in a hydrocarbon linear chain or included in a group such as an imidazole, guanidine group.
• proton donor and donor groups are respectively the members of a conjugated acid / base pair, characterized by a pK (dissociation constant) value in water.
• the proton attractor group will be in a basic form while the proton donor group will be in acidic form, which means, in terms of pK values, that the pK of proton attractor group will be less than the pK of the proton donor group.
• the pK value in water for a proton attractor group ranges from -15 to 6 (preferably from 3 to 5) while the pK value in water for a proton donor group ranges from 8 to 15 (preferably from 8 to 11).
• the difference between the pK value of the donor group and the pK value of the attracting group is at least 0.5 and typically 5. This difference is manifested by a transfer of the protons from the proton donor group to the group. proton attractor, thus generating a proton gradient.
• the abovementioned grafts may correspond to a hydrocarbon group, saturated or unsaturated, cyclic or acyclic, which may comprise one or more heteroatoms such as O, N and S and optionally substituted, such as by halogen atoms, such as fluorine, being understood that said hydrocarbon group will comprise both at least one proton attracting group and at least one proton donating group.
• the grafts may correspond to an aliphatic hydrocarbon group, such as an alkyl group, preferably comprising from 1 to 22 carbon atoms, preferably from 6 to 16 carbon atoms, optionally substituted with one or more fluorine atoms.
• this chain may be intercalated one or more oxygen atoms -0-, in which case it may be described as polyether chain.
• the grafts may also correspond to an aromatic hydrocarbon group comprising one or more aromatic rings optionally comprising one or more heteroatoms such as O, N and S (in which case the chain may be described as a heterocyclic chain).
• the grafts may comprise at least one amide linkage group of formula -NHCO-.
• the grafts also include both at least one proton attracting group and at least one proton donor group.
• Particular grafts according to the invention may be amino acid residues or peptide sequences.
• amino acid conventionally means a hydrocarbon compound comprising both an organic acid function and an amine function, the most well-known representatives being ⁇ -amino acids. natural (carrying a carboxyl function -CO2H and an amino function -NH2). It may also be amino acids carrying a function analogous to the carboxyl function (for example -SO3H, -PO3H2) and an amino function -NH 2 .
• amino acid residue is meant the amino acid residue resulting from the reaction of an -NH 2 function of the amino acid with a carboxyl function or the like of another compound to form an amide linkage (the other compound being, in this case, in our case, the main chain of the (co) polymer before grafting) or a function - CO2H or the like with an amino function or the like of another compound to form a amide bond (the other compound being, in this case, in our case, the main chain of the (co) polymer before grafting).
• amino acids which may constitute, after the amidation reaction, grafts according to the invention in the form of amino acid residues, the following naturally occurring ⁇ -amino acids: arginine, asparagine, aspartic acid, glutamic acid, glutamine, histidine, lysine, these amino acids after grafting all constituting amino acid residues carrying both a proton attractor group
• the amide bond can be done by reacting an NH 2 group of the amino acid (which is the case for arginine, asparagine, glutamine, histidine, lysine) or a -CO2H group of the amino acid (which is the case for aspartic acid, glutamic acid).
• amino acid residues derived from unnatural amino acids having acid functions other than a carboxyl function said amino acids possibly being chosen from the following amino acids:
• amino acid residues will have both a proton attracting group and a proton donating group.
• amino acids capable of constituting grafts according to the invention are lysine, arginine, histidine in which case the grafts will correspond to the following amino acid residues of formulas (I) to (III):
• the grafted (co) polymer may comprise other grafts which do not meet the definition given above (that is to say, not comprising at the same time a group proton attractor and a proton donor group). Grafts that do not meet the definition given above may be amino acid residues derived from amino acids, such as cysteine, proline, serine, threonine, tyrosine, of non-natural amino acids, such as those of the following formulas:
• the grafted (co) polymers may comprise grafts corresponding to an amino acid residue derived from taurine, which grafts correspond to the following formula (IV):
• the grafts may also correspond to a peptide sequence, namely a sequence resulting from a sequence of amino acid residues linked by amide bonds, in particular of natural ⁇ -amino acids, by an amidation reaction, being understood that the peptide sequence will comprise at least one proton attracting group and at least one proton donor group.
• Amino acids that may be part of the constitution of said peptide sequences may be chosen from the amino acids listed above, and most particularly from lysine, aspartic acid, histidine and arginine.
• Grafts corresponding to peptide sequences according to the invention may correspond to one of the following formulas:
• the main chain of the graft (co) polymers constituting the membranes of the invention may be a hydrocarbon chain, aliphatic or aromatic, optionally comprising one or more heteroatoms, such as O, N, S, a halogen atom, preferably fluorine.
• the backbone may advantageously be a backbone comprising a heterocyclic repeating unit, on which, in all or part, grafts as defined above are covalently bound.
• the skeleton can thus be a polypyrrole skeleton.
• constituent copolymers of the membranes of the invention may comprise the following repeating units:
• membranes according to the invention can be one of the following membranes:
• membranes are particularly advantageous in that they combine both the electronic conductivity of the polypyrrole backbone and the proton conductivity of the grafts. Moreover, these membranes, compared to NAFION® membranes for example, have a thermal stability beyond 90 0 C, stable mechanical properties in the presence of solvents such as water.
• the backbone can consist of repeating units resulting from the polymerization of vinyl monomers, such as acrylic acid, vinylamine, which, before grafting, by their pendant functions -COOH and -NH2 are likely to form a covalent bond of the type amide with grafts of the "amino acid residue" or "peptide sequence” type.
• the aforementioned vinyl monomers may advantageously comprise one or more fluorine atoms, the advantage being that a skeleton resulting from the polymerization of such monomers is resistant to corrosion, has good mechanical properties and low gas permeation.
• the membranes of the invention can be constituted exclusively grafted (co) polymers as defined above.
• the membranes of the invention comprise a polymeric support matrix comprising through pores, which pores are filled with graft (co) polymers as defined above.
• the polymer support matrix is advantageously a polymer chosen from polyurethanes, polyolefins, polycarbonates and polyethylene terephthalates, these polymers being advantageously fluorinated or even perfluorinated.
• fluorinated (co) polymers that may be suitable, mention may be made of polyvinylidene fluoride, copolymers of tetrafluoroethylene and tetrafluoropropylene (known by the abbreviation FEP), copolymers of ethylene and tetrafluoroethylene (known by the abbreviation ETFE) copolymers of hexafluoropropene and of vinylidene fluoride (known under the abbreviation HFP-co-VDF).
• the support matrices made of a fluorinated (co) polymer are particularly advantageous in that they exhibit corrosion resistance, good mechanical properties and low gas permeation. They are therefore particularly suitable for entering into the constitution of fuel cell membranes.
• polyvinylidene fluoride is chemically inert (particularly resistant to corrosion), has good mechanical properties, has a glass transition temperature, which varies from -42 ° C. to -38 ° C. as a function of the crystalline phase, a melting temperature of 170 ° C. and a density of 1.75 g / cm 3 .
• This polymer is easily extruded and can be in particular in two crystalline forms, depending on the orientation of the crystallites: the ⁇ phase and the ⁇ phase, the ⁇ phase being characterized in particular by piezoelectric properties.
• the through pores of the support matrix are, as indicated above, filled by the graft copolymers as defined above, and connect two opposite faces of the support matrix.
• they are substantially cylindrical in shape. They can have a diameter ranging from 50 to 100 microns, in which case they can be described as micropores. They can also have a diameter ranging from 10 to 100 nm, in which case they can be described as nanopores.
• the support matrices may comprise from 5.10 4 to 5.10 10 , preferably from 10 5 to 5.10 9 pores per cm 2 .
• the membranes of the invention conventionally have a thickness of the order of 100 .mu.m, in particular a thickness ranging from 1 to 50 .mu.m.
• the aforementioned grafted (co) polymers can be prepared according to several alternative embodiments.
• the grafted (co) polymers may be prepared by a process comprising a reaction step of a base (co) polymer comprising pendant functions. X with at least one graft precursor comprising a function A capable of reacting with a pendant function X to form a covalent bond, reaction at the end of which the grafts are found bound to the base copolymer.
• the pendant functions X can be carboxy functions -CO2H, optionally activated, for example, in the form of succinimide ester, while the functions A can be amino functions -NH2.
• the precursors of grafts will be amino acids or peptide sequences comprising a free NH2 function capable of reacting with the carboxyl function optionally activated, to form an amide bond.
• the amino acid or the peptide sequence will include, where appropriate, other functions -NH 2 protected by protective groups, so as to avoid side reactions.
• the functions -NH 2 can be protected, for example, by protecting groups of Boc (t-butyloxycarbonyl), Fmoc (9-fluorenylmethyloxycarbonyl) type.
• the process may comprise a reaction step of a base copolymer whose backbone comprises at least one unit repetitive of the following formula:
• amino acid or peptide sequence comprising a function A as defined above, said amino acid or said peptide sequence being optionally protected at the level of the functions capable of reacting with the group X.
• the method can thus comprise, once the grafting has been obtained, a step of deprotection of the protected functions.
• R representing a graft corresponding to at least one of the formulas (I) to (VI) as defined above, it is possible, in a first step, to react with a base copolymer comprising the following repeating units:
• X representing a group -CO2H, with respectively at least one of the following amino acids or peptide sequences:
• this deprotection step may consist in bringing the graft copolymer into contact with a trifluoroacetic acid solution.
• the grafted (co) polymers may be prepared by a process comprising a step of polymerizing at least one monomer bearing at least one side chain corresponding to the abovementioned grafts.
• graft copolymer is a polyrrole copolymer comprising the following repeating units:
• this copolymer may consist in the copolymerization of the following monomers:
• R representing a graft comprising at least one proton-attracting group and at least one proton-donating group, in particular R possibly being an amino acid residue or a peptide sequence, more precisely still R being a graft corresponding to one formulas (I) to (VI) as defined above.
• R is in position 3 of the ring, ie as follows:
• the monomers capable of reacting to form the above-mentioned (co) polymers have the following formula:
• R representing an amino acid residue or a peptide sequence, R being able to represent, in particular, a group of formulas (I) to (VI) as defined above, R being preferably in position 3 as defined above; above.
• the grafted (co) polymers may be prepared by radiografting, the grafts being made by radical reaction with a previously irradiated polymer thus generating radical centers, this polymer conventionally being in the form of a membrane.
• the irradiation of the polymer can be carried out by subjecting the base polymer to an electron beam (then electron irradiation) or a heavy ion beam.
• the electron irradiation makes it possible to create radical centers throughout the volume of the base membrane. It is therefore possible with this type of irradiation to graft radically proton grafts providing proton proton conduction throughout the volume of the membrane.
• the base membrane has a large thickness, it may be difficult to graft the heart of the grafts, since the diffusion of the compounds involved in the constitution of the grafts (such as monomers) can be difficult. It is important, in this case, to choose, appropriately, a suitable solvent, so as to reach the membrane in all its volume and including the heart thereof.
• Heavy ion irradiation alters the base membrane only in irradiation traces, from which graft grafting can be performed.
• the compounds likely to enter into the constitution of the grafts are only capable of grafting at the places where the irradiation has created radical centers in the membrane. (ie in the irradiation traces for heavy ion irradiation, in the volume of the membrane for electron irradiation).
• the proton gradient is created by a suitable choice of molecules to be grafted onto the membrane base (eg amino acids or similar molecules). It can therefore be considered that the grafting of such molecules corresponds to a structuring of the base membrane by molecular packing, the molecules being positioned on the membrane so that a proton gradient can appear due to the local concentration of said molecules in the membrane. .
• molecules to be grafted onto the membrane base eg amino acids or similar molecules.
• the proton gradient can be made throughout the mass of the membrane, in which case it will result from the grafting of appropriate molecules following the electron irradiation of a base membrane.
• a base membrane with the following molecules: a first molecule having an acid constant pKai, which diffuses and graft throughout the volume of the base membrane; a second molecule having an acid constant pKa2, which is grafted on one of the faces of the base membrane, this face being the only face to be exposed to this second molecule; a third molecule having an acid constant pKa3, which grafts on a face opposite to the face on which the second molecule is grafted, this opposite face being the only one to be exposed to this third molecule.
• the pKa (pKai, pKa2 and pKa3) are chosen so as to allow proton exchange from one face to the other and thus to create a proton gradient.
• the proton gradient can also be achieved by grafting the appropriate molecules into the latent traces left by the passage of a heavy ion beam.
• symbolized molecules 1, 2, 3 and n respectively having acid constants pKai, pKa2, pKa3 and pKa n knowing that pKai>pKa2>pKa3> pKa n .
• symbolized molecules 1, 2, 3 and n respectively having acid constants pKai, pKa2, pKa3 and pKa n knowing that pKai>pKa2>pKa3> pKa n .
• the process for the preparation of said membranes will conventionally correspond to the processes for preparing said copolymers as explained in the first variant, the second variant or the third variant. variant embodiment.
• the process for preparing such membranes may comprise the following steps: a step of producing said grafted (co) polymers, in particular according to the first variant or the second variant in the through pores of a polymeric support matrix;
• the support matrix may be conventionally removed by destruction with a selective reagent which does not affect the grafted (co) polymers constituting the membranes of the invention.
• the process for preparing said membranes comprises a step of implementing said method for producing (co) graft polymers mentioned above in the through pores of the support matrix.
• the support matrix may be prepared beforehand by irradiation of a base membrane so as to create an organized porosity, which porosity determines the morphological characteristics of the future membrane of the invention, insofar as the preparation of the latter will be carried out within the porosity of the support matrix.
• the irradiation step may be followed by a chemical etching step so as to finalize the structuring of the support matrix.
• the irradiation step may be carried out by ion bombardment, such as xenon bombardment.
• the support matrix may be made of a material chosen from polycarbonate (PC), polyvinylidene fluoride (PVDF) and polyethylene terephthalate (PET).
• PC polycarbonate
• PVDF polyvinylidene fluoride
• PET polyethylene terephthalate
• the through pores of the support matrix will be coated, initially, with a (co) ) base polymer comprising pendant functions X as defined above, then in a second step, the matrix will be brought into contact with a graft precursor comprising a function A as defined above.
• the support matrix is brought into contact with a solution containing the appropriate monomers and the polymerization is conducted until obstruction of the through pores of said support matrix, generally until that the gas permeability is low, preferably close to that of a membrane which does not contain pores or a porosity of not more than 10% or typically equal to 5%. Further details on polymerization in the pores of a matrix can be found in FR 2,770,150.
• the membranes of the invention exhibit, inter alia, improved protonic conduction compared to conventionally used membranes, such as membranes made of NAFION®. It is therefore natural that these membranes can be incorporated in fuel cell devices.
• the invention also relates to a fuel cell device comprising at least one membrane as defined above.
• This device comprises one or more electrode-membrane-electrode assemblies.
• the membrane may be placed between two electrodes, for example carbon fabric impregnated with a catalyst.
• the assembly is then pressed to a suitable temperature in order to obtain good electrode-membrane adhesion.
• the electrode-membrane-electrode assembly obtained is then placed between two plates, providing electrical conduction and supply of reagents to the electrodes. These plaques are commonly referred to as bipolar plates.
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a polypyrrole backbone and grafts derived from lysine of the following formula:
• the prepared copolymer thus comprises the following sequence of units:
• n denoting the number of repeating units of the square bracketed pattern and m the number of repeating units of the square bracketed pattern. It is understood that the patterns in square brackets may be arranged randomly in the chain.
• R representing the graft derived from lysine, the formula of which is shown above, the reagents of stage 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and water, while the reagents of step 2 are the amino acid lysine protected on certain functions in the presence of diisopropylethylamine (DIEA) and water for grafting said amino acid and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of the protected functions of the amino acid.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• H-Lys (Boc) - OH is the following structural formula:
• the functionalized polypyrrole copolymer is made in a two-compartment cell on a polycarbonate support matrix.
• the carboxylated polypyrrole base copolymer (comprising pyrrole and pyrrole 3-carboxyl units) is deposited on the polycarbonate support matrix.
• EDC (0.08 M) and NHS (0.16 M) are dissolved in an aqueous medium.
• the two compartments of the cell are filled with 10 mL of the solution and the mixture is cooled to 4 ° C. After stirring for 1 hour at this temperature, the reaction mixture is stirred at room temperature for 3 hours.
• the activated membrane is washed twice with distilled water.
• the protected lysine amino acid (461.24 mg, 1.69 mmol) and DIEA (588 ⁇ L, 3.38 mmol) are dissolved in an aqueous medium and added to both compartments.
• the resulting solution is stirred at room temperature for 12 hours.
• the membrane is washed with water, dried and a solution of TFA / H 2 O / TIS (9.5: 0.25: 0.25) is added to the compartments. After 3 hours at room temperature, the TFA solution is removed and sodium hydroxide (2N) is added.
• a membrane comprising pyrrole and 3-carboxylated pyrrole units is reacted with EDC (0.08 M) and NHS (0.16).
• the protected lysine amino acid (416.24 mg, 1.69 mmol) and DIEA (588 ⁇ L, 3.38 mmol) are dissolved in an aqueous medium and added to both compartments. The resulting solution is stirred at room temperature for 12 hours. The membrane is washed with water, dried and a solution of TFA / H 2 O / TIS (9.5: 0.25: 0.25) is added to the compartments. After 3 hours at room temperature, the membrane obtained is washed again with fresh water and carefully dried at room temperature.
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a polypyrrole backbone and grafts derived from arginine of the following formula:
• the prepared copolymer thus comprises the following sequence of units:
• n denoting the number of repeating units of the square bracketed pattern and m the number of repeating units of the square bracketed pattern.
• R representing the graft derived from arginine, the formula of which is shown above, the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-chlorohydrochloride) dimethylaminopropyl) carbodiimide (EDC) and water, while the reagents of step 2 are the amino acid arginine protected on certain functions in the presence of diisopropylethylamine (DIEA) and water for the grafting of said amino acid and the trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of the protected functions of the amino acid.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• H-Arg (Pmc) - OH is the following structural formula:
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a polypyrrole backbone and grafts derived from histidine of the following formula:
• the prepared copolymer thus comprises the following sequence of units:
• R representing the histidine-derived graft, whose formula is shown above, the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) hydrochloride; carbodiimide (EDC) and water, while the reagents of step 2 are the protected histidine amino acid on certain functions in the presence of diisopropylethylamine (DIEA) and water for the grafting of said amino acid and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of the protected functions of the amino acid.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• H-His (Trt) - OH is the following structural formula:
• Two embodiments of the membrane have been implemented in the context of this example: an embodiment with a support matrix, this embodiment being identical to that set out in the context of example 1, if not is the introduction of the protected histidine amino acid in place of the protected lysine (at the rate of 671.77 mg, 1.69 mmol); an embodiment without a support matrix, this embodiment being identical to that set out in the context of Example 1, except for the introduction of the protected histidine amino acid in place of the protected lysine ( at a rate of 671.77 mg, 1.69 mmol).
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a polypyrrole backbone and grafts derived from lysine, arginine and histidine (in proportions 1: 1: 1) of formulas following:
• the prepared copolymer thus comprises the following sequence of units:
• R represents indifferently a graft derived from lysine, an arginine-derived graft and a graft derived from histidine the three types of grafts being present in the copolymer in proportions of 1: 1: 1.
• the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and water
• the reagents of step 2 are the amino acid lysine, the amino acid histidine and the amino acid arginine protected on certain functions in the presence of diisopropylethylamine (DIEA) and water for the grafting of said amino acids and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of protected amino acid functions.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• the protected amino acid arginine corresponds to the following formula: H-Arg (Pmc) - OH is the following structural formula:
• H-Lys (Boc) -OH is the following structural formula:
• H-His (Trt) OH is the following structural formula:
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a pyrrole backbone and grafts derived from lysine, arginine, histidine and taurine (in proportions 1: 1: 1: 1) of the following formulas:
• the prepared copolymer thus comprises the following sequence of units:
• R is indifferently a graft derived from lysine, a graft derived from arginine, a graft derived from histidine and a graft derived from taurine.
• the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and water
• the reagents of step 2 are the amino acid lysine, the amino acid histidine, the amino acid arginine protected on certain functions and the amino acid taurine in the presence of diisopropylethylamine (DIEA) and water for the grafting said amino acids and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of protected amino acid functions.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• the protected amino acid arginine corresponds to the following formula: H-Arg (Pmc) - OH is the following structural formula:
• H-Lys (Boc) -OH is the following structural formula:
• H-His (Trt) -OH is the following structural formula:
• Two embodiments of the membrane have been implemented in the context of this example: an embodiment with a support matrix, this embodiment being identical to that set out in the context of Example 1, except for the introduction of the protected amino acids lysine, arginine, histidine and the amino acid taurine in place of the protected lysine amino acid only, in the following proportions respectively (104 mg, 4,225.10 -4 mol, 186.15 mg, 4,225.10 -4 mol, 167.9 mg, 4,225.10 -4 mol; 52.8 mg, 4,225.10 -4 mol); an embodiment without a support matrix, this embodiment being identical to that set out in the context of Example 1, except for the introduction of the protected amino acids lysine, arginine, histidine and the amino acid taurine in place of the protected lysine amino acid only, and in the following respective proportions (104 mg, 4,225 ⁇ 10 -4 mol, 186,15 mg, 4,225 ⁇ 10 -4 mol, 167,9 mg, 4,225 ⁇ 10 -4
• This example illustrates the preparation of a membrane, which consists of a graft copolymer comprising a polypyrrole backbone and grafts of the following formula:
• the prepared copolymer thus comprises the following sequence of units:
• n denoting the number of repeating units of the square bracketed pattern and m the number of repeating units of the square bracketed pattern.
• the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and water
• the reagents of step 2 are the appropriate peptide sequence protected on certain functions in the presence of diisopropylethylamine (DIEA) and water for the grafting of said amino acid and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of functions protected from the peptide sequence.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• H-Asp (OtBu) -His (Trt) -Lys (Boc) -OH is the following structural formula:
• H-Lys resin (Boc) -2-chlorotrityl (0.25 mmol) is coupled with the following amino acids (Fmoc- His (Trt), Fmoc-Asp (OtBu)) said amines being present in excess (10 parts) and whose -COOH functions are in the form of N-hydroxybenzotriazole ester in the presence of HBTU and DIEA.
• the peptide resin obtained is placed in a syringe body comprising a sintered filter. A solution of 1% TFA in dry dichloromethane is added. The whole is allowed to act for two minutes and the resulting solution is filtered. The TFA reaction step followed by filtration is repeated 10 times.
• the protected residual peptide sequence is washed to separate it from the resin successively with 3 * 30 ml of dichloromethane, 3 * 30 ml of methanol, 2 * 30 ml of dichloromethane and 3 * 30 ml of methanol. All the filtrates are combined and evaporated under reduced pressure to 5% of the volume. 40 mL of cold water is added and a white precipitate appears. The product is isolated by filtration and washed three times with cold water.
• the functionalized polypyrrole copolymer is made in a two-compartment cell on a polycarbonate support matrix.
• the carboxylated polypyrrole base copolymer is deposited on the polycarbonate support matrix.
• EDC (0.08 M) and NHS (0.16 M) are dissolved in an aqueous medium.
• the two compartments of the cell are filled with 10 mL of the solution and the mixture is cooled to 4 ° C. After stirring for 1 hour at this temperature, the reaction mixture is stirred at room temperature for 3 hours.
• the activated membrane is washed twice with distilled water.
• the prepared peptide sequence previously (15.9 mg, 0.02 mmol) and DIEA (173.9 ⁇ L, 1 mmol) are dissolved in an aqueous medium and added to both compartments.
• the resulting solution is stirred at room temperature for 12 hours.
• the membrane is washed with water, dried and a solution of TFA / H 2 O / TIS (9.5: 0.25: 0.25) is added to the compartments. After 3 hours at room temperature, the TFA solution is removed and soda
• EXAMPLE 7 This example illustrates the preparation of a membrane, which consists of a polypyrrole backbone and grafts of the following formula:
• the copolymer prepared in this example thus comprises the following sequence of patterns:
• the reagents of step 1 being N-hydroxysuccinimide (NHS) in the presence of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and water
• the reagents of step 2 are the appropriate peptide sequence protected on certain functions in the presence of diisopropylethylamine (DIEA) and water for the grafting of said amino acid and trifluoroacetic acid (TFA) in the presence of water and triisopropylsilane (TIS) for the deprotection of functions protected from the peptide sequence.
• DIEA diisopropylethylamine
• TIS triisopropylsilane
• amino acids required for the preparation of this peptide sequence are as follows:
• H-Lys (Boc) -2-chlorotrityl resin (0.25 mmol) is coupled with the following amino acids (Fmoc-His (Trt), Fmoc-Asp (OtBu), Fmoc-Lys (Dde ), Fmoc-Asp (OtBu), Fmoc-His (Trt), Fmoc-Arg (Pbf)), said amines being present in excess (10 parts) and whose -COOH functions are form of N-hydroxybenzotriazole ester in the presence N - [(1H- (benzotriazol-1-yl) dimethylamino) methylene] -N-methylmethanaminium hexafluorophosphate (HBTU) and diisopropylethylamine (DIEA).
• HBTU HBTU
• DIEA diisopropylethylamine
• the resulting resin is resuspended in a solution of 2% hydrazine monohydrate in dichloromethane (20 mL / g resin). It is allowed to react for 3 minutes with careful hand shaking and the hydrazine treatment is repeated twice to ensure complete reaction.
• the resin is washed successively with 2 * 20 ml of dimethylformamide, 2 * 20 ml of dichloromethane, 20 ml of methanol, 20 ml of dichloromethane and dried.
• the functionalized polypyrrole copolymer is made in a two-compartment cell on a polycarbonate support matrix.
• the carboxylated polypyrrole base copolymer is deposited on the polycarbonate support matrix.
• 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (0.08 M) and N-hydroxysuccinimide (NHS) (0.16 M) are dissolved in an aqueous medium.
• the two compartments of the cell are filled with 10 mL of the solution and the mixture is cooled to 4 ° C. After stirring for 1 hour at this temperature, the reaction mixture is stirred at room temperature for 3 hours.
• the activated membrane is washed twice with distilled water.
• the previously prepared peptide sequence (15.9 mg, 0.02 mmol) and diisopropylethylamine (173.9 ⁇ L, 1 mmol) are dissolved in an aqueous medium and added to both compartments. The resulting solution is stirred at room temperature for 12 hours. The membrane is washed with water, dried and a solution of TFA / H 2 O / TIS (9.5: 0.25: 0.25) is added to the compartments. After 3 hours at room temperature, the TFA solution is removed and sodium hydroxide (2N) is added. After 2 hours at 80 ° C., the final membrane freed from the polycarbonate matrix is washed again with fresh water and carefully dried at room temperature.

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