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
  • H01M8/1069—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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
  • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • 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
  • C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
  • C08F16/32—Monomers containing two or more unsaturated aliphatic radicals
• • 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
  • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
  • C25B13/00—Diaphragms; Spacing elements
  • C25B13/04—Diaphragms; Spacing elements characterised by the material
  • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
• • 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
  • H01M8/1023—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
  • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
• • 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
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • 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

• ion-exchange membranes partially or completely fluorinated are usually chosen for alkali-chloride processes or fuel cells consuming hydrogen or methanol.
• Such membranes are commercially available under trade names like NafionTM, FlemionTM, DowTM.
• Other similar membranes are proposed by Ballard Inc. in application WO 97/25369 that describes copolymers of tetrafluoroethylene and perfluorovinylethers or trifluorovinylstyrene.
• the active monomers from which these copolymers are obtained bear chemical functions that are the precursors of ionic groups of the sulfonate or carboxylate type. Example of such precursors are:
• X is F, Cl or CF 3 ;
• n is 0 to 10 inclusively
• Aromatic polymers of the polyimide or sulfonated polyether sulfone type have also been considered, for example:
• the copolymer containing the above precursors is molded, for example in the form of sheets, and converted into an ionic form through hydrolysis, to give species of the sulfonate or carboxylate type.
• TFE Tetrafluoroethylene
• Non-fluorinated systems like sulfonated polyimides or sulfonated polyether sulfones have the same drawbacks because one must compromise between the charged density, and thus the conductivity, and the solubility or excessive swelling.
• the present invention is concerned with a bifunctional monomer of the general formula
• T and T′ are the same or different and comprise an organic radical bearing at least one polymerization active function such as an insaturation or a cycle susceptible of opening;
• M + comprises an inorganic or organic cation
• Y comprises N or CQ wherein Q comprises H, CN, F, SO 2 R 3 , C 1-20 alkyl substituted or unsubstituted; C 1-20 aryl substituted or unsubstituted; C 1-20 alkylene substituted or unsubstituted, wherein the substituent comprises one or more halogens, and wherein the chain comprises one or more substituents F, SO 2 R, aza, oxa, thia or dioxathia; and
• R 3 comprises F, C 1-20 alkyl substituted or unsubstituted; C 1-20 aryl substituted or unsubstituted; C 1-20 alkylene substituted or unsubstituted, wherein the substituent comprises one or more halogens.
• M + comprises the proton, a metal cation such as an alkaline metal, an alkaline-earth metal, a rare earth or a transition metal; an organometallic cation such as a metallocenium, an arene-metallocenium, an alkylsilyl, an alkylgermanyl or an alkyltin; or an organic cation optionally substituted with one or more organic radicals.
• a metal cation such as an alkaline metal, an alkaline-earth metal, a rare earth or a transition metal
• an organometallic cation such as a metallocenium, an arene-metallocenium, an alkylsilyl, an alkylgermanyl or an alkyltin
• organic cation optionally substituted with one or more organic radicals.
• Examples of preferred organic cations include R′′O + (onium), NR′′ + (ammonium), R′′C(NHR′′) 2 + (amidinium), C(NHR′′) 3 + (guanidinium), C 5 R′′N + (pyridinium), C 3 R′′N 2 + (imidazolium), C 2 R′′N 3 + (triazolium), C 3 R′′N 2 + (imidazolinium), SR′′ + (sulfonium), PR′′ + (phosphonium), IR′′ + (iodonium), (C 6 R′′) 3 C + (carbonium), wherein R′′ comprises:
• an alkyl an alkenyl, an oxaalkyl, an oxaalkenyl, an azaalkyl, an azaalkenyl, a thiaalkyl, a thiaalkenyl, a dialkylazo, a silaalkyl, optionally hydrolysable, a silaalkenyl optionally hydrolysable, each of these being straight, branched or cyclic and comprising from 1 to 18 carbon atoms;
• aliphatic heterocyclic or cyclic radicals comprising from 4 to 26 carbon atoms comprising optionally at least one lateral chain comprising one or more heteroatoms such as nitrogen, oxygen or sulfur;
• an organic cation comprises at least two radicals R′′ different from H
• these radicals can form together a cycle aromatic or not, optionally containing the centre bearing the cationic charge.
• the invention further comprises an ion exchange polymer that is a solid ion conductor obtained from a monomer or a mixture of monomers bifunctional as defined above.
• the monomer or the mixture of monomers can be copolymerized with at least one monofunctional monomer, preferably of formula [T-SO 3 ] ⁇ M + or [T-SO 2 —Y—SO 2 —W] ⁇ M + wherein T, Y and M + are as defined above, and W is a monovalent alkyl, alkenyl, aryl, arylalkyl, alkylaryl of from 1 to 12 carbon atoms optionally comprising one or more substituents oxa, aza or thia.
• the invention further relates to a process for the preparation of a polymer from monomers or a mixture of the monomers mentioned above, wherein the monomers or mixtures of monomers are polymerized in solution in a solvent, the polymer formed remaining plasticized homogeneously by the solvent.
• the monomer or mixture of monomers are preferably polymerized in the form of an emulsion in non-miscible solvents.
• the process of the present invention is particularly advantageous over the prior art processes, because it provides for a polymer that remains plasticized homogeneously in the solvent. This is a rare phenomenon and completely unexpected, which can be explained by the strong interactions between the charges and the solvent.
• the present invention relates to the use of perfluoro-di(vinylethers) bearing imide or sulfone functions highly dissociated, such as di(sulfonylmethane) or tri(sulfonylmethane), as a base for preparing cross-linked ion exchange resins obtained directly in a final form, for example a film or a hollow fiber (hereunder referred to as “membrane”), and having a high ionic functions density, resulting in an increased conductivity.
• the polymerization can be performed in a concentrated solution of the monomer in the form of a salt.
• the polymers obtained do not have the disadvantages of the perfluorinated ionomers of the prior art, because they have a good dimensional stability in the presence of solvents, including water and polar solvents, while maintaining an excellent conductivity because of the high concentration of ionic groups.
• the cross-linking creates an excellent barrier with respect to the diffusion of molecular species, particularly oxygen or methanol, as well as other organic combustibles.
• the presence of TFE is not necessary or can be minimized, thus reducing the risks during the manufacture process.
• the polymers can be converted into extremely thin membranes, i.e. with a thickness on the order of 50 ⁇ m or less, while maintaining a good mechanical behaviour while conventional membranes of the same thickness have no mechanical behaviour at all.
• the process of the present invention therefore represents an efficient use of the monomers costwise.
• the electrochemical applications of the membranes obtained from the cross-linked polymers of the present invention require electrode materials and/or catalysts in intimate contact with the membrane used as the electrolyte.
• the electrode materials can be easily deposited on either one or both sides of the membrane during the fabrication, eventually during the polymerization step.
• the electrode materials can also be applied on a membrane already formed. This coating can be performed by applying a solution of at least one monomer of the present invention in an appropriate solvent, followed by polymerization, or the application of a solution or a suspension of a polymer bearing eventually ionic functions.
• the polymers present on the electrodes advantageously act as a binder for the active materials, conductors or catalysts.
• the imide function i.e. when Y ⁇ N, as well as polysulfonyl carbanions, and to a lesser degree perfluorosulfonate anions having a strong electronic affinity and highly dissociated, allow an increase in the catalytic activity of the cations, specific to several reactions.
• the polymers of the invention are therefore useful as catalyst support.
• the membrane or the material of the membrane for example in the form of a powder or granules, and containing active cations in catalysis, are easily separated mechanically from the reaction medium after completion of the reaction. Examples of reactions that can be catalyzed include Diels-Alder additions, Friedel-Craft reactions, aldol condensation, cationic polymerizations, esterifications, acetal formations, etc.
• Examples of preferred monomers include:
• X represents F, Cl, or CF 3 ;
• n varies between 0 and 10 inclusively
• E is absent, O, S. SO 2 ;
• Z is F or H.
• the monomers of the invention can be obtained from different processes.
• the monomers of the imide type can be obtained in the following manner:
• the tertioalkyl radical in the definition of A above is advantageous because it is the precursor of an alkene eliminating itself from the reaction medium and a proton. For example, if it is a tertiobutyl, the following reaction is observed:
• the trialkylsilyl group is advantageous when the leaving group L is fluorine, because of the high formation enthalpy of the Si-F bond.
• A is a proton or a proton precursor, such as a tertioalkyl radical
• a hindered base such as a tertiary base.
• bases are la triethylamine, di-isopropylamine, quinuclidine, 1,4-diazobicyclo[2,2,2]octane (DABCO), pyridine, alkylpyridines, dialkylaminopyridines, N-alkylimidazoles, imidazo[1,1-a]pyridine, amidines such as 1,5-diazabicyclo[4,3,0]non-5-ene (DBN) or 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), guanidines such as tetramethylguanidine, 1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido-[1,2-a]pyr
• the potassium salts of the monomer of the invention are insoluble or slightly soluble in water, and can be precipitated therein from more soluble salts, i.e. salts H + , Li + or Na + , and subsequently purified by recrystallization.
• the recrystallization can be performed in water, alone or in admixture with a miscible solvent such as acetonitrile, dioxanne, acetone or THF.
• alkylammonium salts particularly the tetraalkylammonium or imidazolium salts, are usually insoluble in water and can therefore be extracted with various solvents, preferably halogenated, such as dichloromethane, dichloroethane, trichloroethane, 1,1,1,2-tetrafluoroethane, etc.
• the perfluorovinylether groups can be halogenated, particularly chlorinated or bromated, to lead to a non-reactive perhaloether.
• the perfluorovinylether is eventually regenerated according to various processes well known to those skilled in the art, for instance through an electrochemical reaction, with a reducing agent such as zinc powder, an alloy of bronze zinc-copper, or the tetrakis(dimethylamino)ethylene.
• M + , Z, Q, X and Y are as defined above, and n and m are identical or the same or different and vary between 0 and 10 inclusively.
• the ion exchange membranes are obtained through homo- or copolymerization of the bifunctional monomers of the present invention.
• the comonomers are advantageously selected from the salts of the functional monomers of the following general formula:
• T′, Y, M + are as defined above and W has the same definition as Q.
• Examples of preferred monofonctional monomers of the present invention for a copolymerization include:
• R′ is a monovalent organic radical comprising from 1 to 12 carbon atoms, preferably perfluorinated, eventually possessing one or more substituents oxa, aza, thia or dioxathia; and p is 1 or 2.
• the polymerization and copolymerization reactions are performed in a solvent of the monomers.
• the monomers are generally soluble in most usual polar solvents, i.e. water, lower aliphatic alcohols, acetone, methyl ethyl ketone, cyclic ketones, propyl and ethyl carbonate, ⁇ -butyrolactone, N-alkylimidazole, fluoroalkane, and mixtures thereof.
• M allows the optimization of the solubility of the monomers because of the cation-solvent interaction. It is understood that after completion of the polymerization, the exchanges of M are carried out according to conventional techniques used in the field of ion exchange resins. Inorganic or organic solid additives in the form of powder or fibers can be added during manufacturing to improve the mechanical properties of the polymers, to act as a pore formation agent, or as a catalyst support (e.g., platinum deposited on carbon particles).
• the organozincic CF 2 ⁇ CFZnBr is synthesized under argon in DMF according to the procedure published in J. of Organic Chemistry, 53, 2714, (1988) starting from CF 2 ⁇ CFBr (10 g) in a thermostated reactor. 18 g of the zinc salt as prepared previously in DMF are added to the solution of the organometallic mixed with 160 mg of benzylideneacetone palladium (0) and 190 mg of triphenylphosphine acting as a co-catalyst, while maintaining the temperature below 65° C. The reaction is carried out for 4 hours at this temperature and the solvent is evaporated under reduced pressure at 80° C.
• the solid residue is washed with water, filtered and treated with 10 g of potassium carbonate in 100 ml of water.
• the white suspension containing the zinc carbonate is evaporated under reduced pressure at 60° C.
• the potassium salt is extracted with a mixture acetonitrile-dimethoxyethane (50:50 v/v), and the solvent is evaporated.
• the potassium salt is extracted with a mixture acetonitrile-dimethoxyethane (50:50 v/v), and the solvent is evaporated.
• [0060] is purified by recrystallization in water and transformed into the lithium salt by double exchange with the lithium tetrafluoroborate in acetonitrile wherein KBR 4 is insoluble.
• a solution of 1 g of the lithium salt of example 1, 10 g of lithium 4-trifluorovinylbenzene sulfonate, 250 mg of Irgacure 651® in 35 ml of a mixture of propylene carbonate and diglyme (bis[methoxyethylether]) (50:50 v/v) are spread in the form of a film of the thickness of 180 microns on a polypropylene support.
• the solution is submitted to UV rays produced by a Hanovia® type lamp having its maximum emission at 254 nm so that the illumination corresponds to 80 mWcm ⁇ 2 .
• the solution polymerizes in the form of an elastic gel.
• Polymerization is carried out for 5 minutes and the film is removed from its support and washed with water and nitric acid 2M at 60° C. to eliminate the organic solvents and the polymerization residues.
• the conductivity of the membrane measured between 60 and 100% humidity is higher than 10 ⁇ 2 Scm ⁇ 1 .
• the membrane dimensions are stable in a wide domain of humidity content as a result of the high concentration of cross-linking knots.
• [0063] is purified by recrystallization in water and transformed into the lithium salt.
• a solution of 8.8 g of this salt and 1 g of the monomer of Example 1 in the form of the lithium salt are dissolved in 40 ml of ⁇ -butyrolactone, spread in the form of a film of 150 microns thick on a polypropylene support and polymerized in the conditions of Example 2.
• the film is removed from its support and washed with water and nitric acid 2 M at 60° C. to eliminate the ⁇ -butyrolactone and perform the exchange Li + H + .
• a high density polyethylene recipient with thick side walls 35 g of CF 2 (Cl)CF(Cl)OCF 2 CF 2 SO 2 F as prepared above, 125 ml of anhydrous THF and 1.74 g of lithium nitride and 36 zircon grinding cylinders (@1 cm 3 ).
• 10 g of the powder of an alloy zinc-copper (10% Cu) are added and agitated and the agitation is carried out for a further 24 hours.
• the final product is filtered and the solvent is evaporated under reduced pressure at 40° C.
• the residue is mixed with a solution of 10% of potassium chloride in water.
• the precipitate is washed, filtered and recrystallized in a mixture water-ethanol (50:50 v/v).
• the lithium salt Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 2 ) 2 N] is obtained by exchange with LiBF 4 in triglyme.
• the radical initiator is trichloroacetyl peroxide in proportion of 1% molar with respect to the monomers.
• the solution is spread on a polypropylene support in order to form a film of a thickness of 100 microns.
• the polymerization/cross-linking step is performed by heating at 80° C. under deoxygenated nitrogen atmosphere.
• the film obtained is removed from its support and washed with water and nitric acid 2M at 60° C. to eliminate the organic solvents and the polymerization residues, as well as for replacing the Li + cations with H + .
• the conductivity of the membrane at 95% humidity is about 10 ⁇ 2 Scm ⁇ 1 .
• the methanol permeation is lower in line-up in order of size by 1 with respect to a Nafion 117® membrane of a similar thickness.
• the lithium perfluoro(4-methyl-3,6-dioxaoct-7-ene)sulfonate is obtained in a similar manner by reaction of lithium silanoate on the sulfonyl fluoride in dibutyldiglyme ([C 4 H 9 OC 2 H 4 ] 2 O).
• a cross-linked membrane is obtained by polymerization of a mixture of 3 g of the divinylic monomer and 18 g of the monovinylic perfluorosulfonate, 800 mg of fumed silica (7 nm) in 50 ml of dibutyldiglyme.
• the solution is spread in the form of a film and the polymerization is carried out with the photoinitiator Irgacure 651®. Under argon sweeping, the solution is submitted to UV rays in the conditions of Example 2.
• the membrane is washed with ethanol and water and the lithium ions are exchanged by HCl 5M in water.
• this monomer is susceptible of homopolymerizing or copolymerizing with tetrafluoroethylene or monofunctional ionic monomers.
• a cross-linked copolymer with the lithium perfluoro(4-methyl-3,6-dioxaoct-7-ene) sulfonate (10:90 molar) is obtained in a similar manner to that of Example 7.
• a high density polyethylene recipient with thick side walls (Nalgene®) are added the dilithiated derivative of the sulfone in THF as prepared, 6.7 ml of tetramethylethylene diamine (TMDA) and 17.5 g of CF 2 (Cl)CF(Cl)OCF 2 CF 2 SO 2 F obtained by adding chlorine on the double bond of the perfluorovinyloxyethanesulfonyl in a manner similar to that of Example 4. 36 zircon grinding cylinders (about 1 cm 3 ) are added to favour the heterogeneous solid-liquid reaction.
• TMDA tetramethylethylene diamine
• CF 2 (Cl)CF(Cl)OCF 2 CF 2 SO 2 F obtained by adding chlorine on the double bond of the perfluorovinyloxyethanesulfonyl in a manner similar to that of Example 4.
• Example 7 Li[(CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 ) 2 N] is treated with 1-methyl-3-ethyl-imidazolium chloride in solution in water. A viscous liquid is decanted and extracted with dichloromethane to give
• [0075] is prepared by exchange in water, as well as the salt of the radical initiator azobis(2-imidazolidium-2-methyl-propane):
• the salts are mixed in molar ratios 8:91:1 bifunctional monomer: monofunctional monomer: radical initiator.
• the viscous mixture is spread on a polypropylene sheet maintained at 40° C. to form a layer of 35 ⁇ m of thickness and the temperature is raised at 80° C. for 2 hours under nitrogen sweeping.
• the membrane thus obtained is removed from its support and the polymerization is completed by heating at 100° C. for two hours.
• the imidazolium ions are exchanged with the sodium ions by treatment with a solution of caustic soda 1 M and ethanol under reflux for 4 hours, leading to the degradation of the organic cation.
• the sodium ions are then exchanged themselves with protons by immersion in a Soxhlet type extractor containing an aqueous solution of hydrochloric acid at the azeotropic composition (20.3% by weight).
• the same bifunctional monomer is copolymerized with the monofunctional monomer of Example 10, Li[CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 N(CSO 2 CF 3 )] and the radical initiator used above.
• the copolymerization is performed by inverted emulsion in decaline under strong mechanical agitation, the ratios of the active components being now 25:74:1.
• the system is purged with argon and after two hours at 90° C., the polymer particles are separated by filtration, washed and exchanged as above.
• the salt Na(BrCF 2 CF 2 O ⁇ SO 3 ) is separated by filtration and the sulfonyl chloride is prepared by adding thionyl chloride in acetonitrile catalyzed with DMF.
• the imidide Na(BrCF 2 CF 2 O ⁇ SO 2 )N is prepared at 0° C. by adding caustic soda to a suspension of the acid chloride in a aqueous solution of ammonium chloride according to the equation:
• a high density polyethylene recipient with thick side walls (Nalgene®) are added 14 g of the imidide Na(BrCF 2 CF 2 O ⁇ SO 2 ) 2 N prepared above, 100 ml of anhydrous DMF and 4 g of a zinc alloy powder and 25 zircon grinding cylinders (about 1 cm 3 ). After 24 hours of agitation in a roll grinder, the solvent is evaporated under reduce pressure at 80° C. The residue is mixed with a saturated solution of potassium chloride in water and the precipitate of K(CF 2 CF 2 O ⁇ SO 2 ) 2 N is purified by crystallization in water.
• This salt can be polymerized by radicalar or thermal initiation or be included in a copolymer with the monomer Na(CF 2 CF 2 O ⁇ SO 3 ) obtained by reduction with zinc of Na(BrCF 2 CF 2 O ⁇ SO 3 ).
• An experimental fuel cell is fabricated from a membrane as prepared in Example 3.
• a nanometric dispersion of platinum on a carbon support (Degussa) is applied on both sides of the membrane by a serigraphy technique from a dispersion of the platinated carbon in a colloidal solution (5% w/w) of Nafion 117® in a mixture of light alcohols (Aldrich).
• the system is treated at 130° C. by applying a pressure of 20 Kgcm ⁇ 2 to ensure cohesion of the Nafion® particles.
• a carbon paper collector (non-woven carbon fibers) is inserted between the electrodes and the grooved stainless steel current collectors to ensure distribution of the gases.
• the experimental cell is tested with feeding of hydrogen saturated with water vapor at 80° C. and in oxygen, both gases being at an ordinary pressure.
• the tension in an open circuit is 1.2 V and the current tension curve measured on this assembly indicates 1 Acm ⁇ 2 are obtained at a tension of 0.65 V.
• An experimental fuel cell is fabricated from a membrane prepared in Example 5.
• the platinated carbon electrode is applied on both sides of the membrane by serigraphy of a suspension (30% by weight) of this material in a solution in diglyme comprising A) 15% by weight of the monomer of Example 4 Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 2 ) 2 N]; B) 15% of the monofunctional monomer of Example 10 Li[CF 2 ⁇ CFOCF 2 CF(CF 3 )OCF 2 CF 2 SO 2 N(CSO 2 CF 3 )]; and C) 1% by weight of the initiator of Example 11.
• the polymerization of the monomer of the electrodes is obtained by heating under nitrogen atmosphere at 90° C. for two hours.
• the assembly electrode/membrane is rinsed abundantly in an aqueous solution of hydrochloric acid 2M to eliminate the organic solvents, the unreacted monomer and the oligomers, as well as to ensure the exchange of the Li + ions of the polymer of the electrode with protons.
• the experimental fuel cell using such an assembly has a tension in open circuit of 1.2 V and the current tension curve measured on the assembly indicates 1 Acm ⁇ 2 are obtained at a tension of 0.72 V.
• Replacing the platinum of the negative electrode with a platinum-ruthenium alloy 50:50 allows the use of methanol as a combustible with a current density of 150 mAcm ⁇ 2 at a tension of 0.6 V at 100° C.
• the permeation of methanol in these conditions is lower than 5 ⁇ moles.cm ⁇ 2 s ⁇ 1 .
• the assembly electrodes/electrolyte of an experimental fuel cell is realized in a single step by co-extrusion of the three corresponding layers in the form of monomers undergoing a co-polymerization/cross-linking.
• the central part is a dispersion of nanoparticles of silicon (1.5 g) in a solution of Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 2 ) 2 N] (4 g), of Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 3 ] (24 g) in 40 ml of triglyme and 1 g of the radical initiator of Example 11.
• the electrodes are made of a dispersion of platinated carbon (10 g), granulated micrometric calcium carbonate (10 g), Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 2 ) 2 N], (2 g), Li[(CF 2 ⁇ CFOCF 2 CF 2 SO 3 ] (12 g) in 40 ml of triglyme and 0.8 g of the radical initiator of Example 11.
• the extrusion thicknesses are adjusted to 60 ⁇ m for the electrolyte and 30 ⁇ m for each of the electrodes.
• the polymerization is immediately carried out after extrusion by heating at 80° C. for 4 hours under nitrogen.
• the assembly is treated in a Soxhlet type apparatus with hydrochloric acid at the azeotropic composition to exchange the metallic ions.
• the dissolution of the calcium carbonate creates a favorable porosity for gaseous exchanges of the electrodes.
• the co-extruded assembly thus obtained can be cut to the desired dimensions to obtain the elements of a modular combustible cell by adding current collectors and gas injectors.
• Electrolysis of sodium chloride is performed in a cell having two compartments separated by a membrane as prepared in Example 7, the anode being of the type DSA (Dimensionally Stable Electrode) and comprising titanium coated with a layer of ruthenium oxide RuO 2 in contact with the membrane, the cathode being made of nickel.
• the ohmic drop for 2 Acm ⁇ 2 is 0.4 V and the permeation of OH— ions through the membrane is lower than 9 ⁇ moles.cm ⁇ 2 s ⁇ 1 .
• Example 4 The membrane of Example 4 is used for the preparation of ozone by water electrolysis on an anode of lead dioxide, the cathode is a grid of platinum, both electrodes are plated on the membrane that has the cathodic side immersed in water.
• the ozone faradic yield is 24% under 5 V.
• Porous ion exchange resins prepared in Examples 3 and 11 are used as chemical reaction catalysts. In the active protonic form after vacuum dehydration, the resin catalyses Friedels-Craft reactions, esterifications, acetalisations etc. To an equimolecular mixture of anisole and acetic anhydride are added 3% by weight of the resin of Example 3 in the acidic form. The formation reaction of the 4-methoxyacetophenone is complete in 45 minutes at room temperature.
• the catalyst is eliminated by simple filtration, and is reusable.

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• 1999
  • 1999-01-29 WO PCT/CA1999/000083 patent/WO1999038842A1/fr active Application Filing
  • 1999-01-29 EP EP03004041A patent/EP1312603A1/fr not_active Withdrawn
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• 2002
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