EP2108021A1 - Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible - Google Patents

Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible

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Publication number
EP2108021A1
EP2108021A1 EP07857267A EP07857267A EP2108021A1 EP 2108021 A1 EP2108021 A1 EP 2108021A1 EP 07857267 A EP07857267 A EP 07857267A EP 07857267 A EP07857267 A EP 07857267A EP 2108021 A1 EP2108021 A1 EP 2108021A1
Authority
EP
European Patent Office
Prior art keywords
formulation
acid groups
water
salts
formulations
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07857267A
Other languages
German (de)
English (en)
Inventor
Günter OETTER
Ria Kress
Dennis LÖSCH
Alexander Khvorost
Gerhard Eugen Wahsner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07857267A priority Critical patent/EP2108021A1/fr
Publication of EP2108021A1 publication Critical patent/EP2108021A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • H01M8/103—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. in situ polymerisation or in situ crosslinking
    • 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

  • Aqueous formulations comprising acid groups and / or salts of polyaromatic compounds carrying acid groups, processes for their preparation, further formulations prepared using the aqueous formulations and use of the further formulations in fuel cells
  • the present invention relates to a process for the preparation of aqueous formulations (A) comprising at least one acid groups and / or salts of acid groups carrying, in particular sulfonated, polyaromatic compound and aqueous formulations (A), which are prepared according to the inventive method. Furthermore, the present invention relates to a process for preparing dried formulations (B) by removing the water from the aqueous formulations (A) and the dried formulations (B) themselves.
  • the present invention relates to a formulation (C) comprising the dried formulation according to the invention (B) and water or an aqueous formulation (A) and a water-containing formulation (D) comprising the inventive aqueous formulation (A) or the inventive formulation (C) and additionally at least 2 wt .-% of an organic solvent. Furthermore, the present invention relates to dry formulations (E) which are obtained by removing water from the aqueous formulations (D) according to the invention.
  • a further subject matter of the present invention is the use of the water-containing formulations (D) according to the invention and of the dry formulations (E) obtained therefrom for producing a polymer electrolyte membrane and the polymer electrolyte membrane itself and a membrane electrode assembly (MEA) and a fuel cell, containing the polymer electrolyte membrane according to the invention.
  • D water-containing formulations
  • E dry formulations
  • sulfonated, polyaromatic compounds are known in the art.
  • functionalized polyaromatic compounds are used as or in polymer electrolyte membranes.
  • sulfonated polyaromatic compounds can be used in electrolytic cells, for example chloroalkali cells, as well as in or as catalysts for numerous chemical reactions and in processes such as inverse osmosis or ultrafiltration.
  • Polymer electrolyte membranes prepared from the acid group-bearing, especially sulfonated, polyaromatic compounds are generally prepared by dissolving the polyaromatic compounds bearing acid groups in an organic solvent such as DMAc (N, N-dimethylacetamide), DMF (dimethylformamide), DMSO (dimethyl sulfoxide) or NMP (N-methylpyrrolidone), followed by precipitation or removal of the solvent.
  • an organic solvent such as DMAc (N, N-dimethylacetamide), DMF (dimethylformamide), DMSO (dimethyl sulfoxide) or NMP (N-methylpyrrolidone
  • WO 2005/068542 relates to polymer solutions containing a sulfonated polyaryletherketone or polyarylethersulfone which is not directly soluble in water at a temperature of up to 100 ° C.
  • the solvent in these solutions is at least 90% water.
  • the polymer solutions can be used to prepare electrocatalyst inks and electrocatalyst layers for use in fuel cells.
  • the polymer solutions are prepared by dissolving the sulfonated polymer in a first solvent having a lower boiling point than water, adding water, then removing the first solvent, the polymer surprisingly not precipitating but forming kinetically stable aqueous solutions , According to the description in WO 2005/068542, the solutions have solids contents of> 1 to ⁇ 10% by weight.
  • WO 98/55534 discloses a process for the preparation of aqueous, aqueous and nonaqueous solutions of polymers functionalized with acid groups, the heat required for the preparation of the solution being supplied by microwave radiation.
  • the solutions serve as starting material for the production of gas diffusion electrodes, fuel cells and polymer electrolyte stabilized platinum Nanoparticles.
  • the polymers functionalized with acid groups are, for example, sulfonated polyether ketones (PEK), polyether ether ketones (PEEK) and polyether ether ketone ketones (PEEKK).
  • PEEK polyether ether ketones
  • PEEKK polyether ether ketone ketones
  • aqueous and water-containing formulations containing polyaromatic compounds bearing acid groups it is desirable to provide aqueous and water-containing formulations containing polyaromatic compounds bearing acid groups, without the need for microwave irradiation. It is desirable that the aqueous and aqueous formulations have the highest possible solids content (content of polyaromatic compounds bearing acid groups).
  • aqueous formulations A of acid groups and / or salts of polyaromatic compounds carrying acid groups can be obtained which have high solids contents.
  • the aqueous formulations A are generally solutions or dispersions of at least one acid group and / or salt of polyaromatic compound bearing acid groups.
  • water means water, preferably tap water, with the quantities of impurities customary for tap water It is likewise possible, for example, to use partially or fully demineralized water The addition of further components, such as salts and emulsifiers can be carried out, but not in a preferred embodiment of the method according to the invention.
  • acid groups are preferably sulfonic, phosphoric, carboxyl and / or boric acid groups, where Sulfonic acid groups are particularly preferred.
  • Salts of acid groups are to be understood as meaning preferably the salts of the abovementioned acid groups
  • Suitable salts are the salts of monovalent and polyvalent cations
  • suitable polyvalent cations are Al.sub.3.sup . + , Mg.sup.2 + and Ca.sup.2 + Salts with monovalent cations, wherein the monovalent cations are more preferably selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , NH 4 + and mixtures thereof.
  • the proportion of acid groups and / or salts of acid groups in the polyaromatic compounds is generally 0.5 to 2 mmol acid groups and / or
  • IEC recalculated by elemental analysis
  • the IEC indicates how many mmol of acid groups (and / or salts thereof) are available per gram of polymer.
  • polyaromatic compounds which carry acid groups and / or salts of acid groups in the formulation A prepared according to the invention and polyaromatic compounds which carry acid groups and / or salts of acid groups used for the preparation of the formulation may be either polyaromatic compounds which are exclusively acid groups or polyaromatic compounds which carry only acid group salts.
  • Polyaromatic compounds bearing both acid groups and acid group salts are also encompassed by the term "acid groups and / or acid group-bearing polyaromatic compound" wherein the ratio of the acid groups to the salts of acid groups in the polyaromatic compounds is Generally 100 to 1 to 1 to 100, preferably 50 to 1 to 1 to 50.
  • polyaromatic compound is to be understood as meaning a polymer which has a plurality of arylene groups within the polymer chain, preferably a plurality of phenylene groups.
  • polyaromatic compound is to be understood as meaning a compound selected from the group consisting of polyethers, polyketones, polyaryletherketones, polythioetherketones, polyarylsulphones, polyethersulphones, polythioethersulphones, polyphenylenesulphides, polysulphones, particularly preferably the "polyaromatic compound” selected from polyaryletherketones, Polyarylsulfones, polyethersulfones, polyphenylene sulfides and polysulfones. Very particular preference is given to polyaryl ether ketones.
  • One or more different polyaromatic compounds can be used in the process according to the invention.
  • the polyaromatic compounds may differ in their basic structure, their molecular weight and / or their content of salts from acid groups or other parameters.
  • the polyaromatic compounds which are present in the formulations A and the acid groups and / or salts used in step (i) are selected from polyorganic compounds carrying sulfonic acid, phosphoric acid, carboxyl, boric acid groups and / or salts thereof Polyaryletherketones, polyarylsulfones, polyethersulfones, polyphenylsulfides and polysulfones.
  • the polyaromatic compounds may carry the acid groups on their aromatic nuclei or on side chains.
  • the side chains are, for example, aryl, alkyl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl or alkenyl groups, which are substituted by the acid groups and / or salts of acid groups.
  • the side chains can be linked to each atom of the polymer backbone. Preferably, they are linked to the aromatic nuclei of the polyaromatic compounds. Suitable examples are:
  • X acid group and / or salt of the acid group
  • the preparation of polyaromatic compounds bearing acid groups is carried out by methods known to those skilled in the art. Suitable methods are e.g. in US 2002/0091225, WO 2005/049696, WO 2005/050671, JP 2004-345997 A, US 2004/0149965, EP-A 1 479 714 and EP-A 1 465 277.
  • the partial or complete conversion of the acid groups present in the polyaromatic compounds into the corresponding salts is carried out according to methods known to the person skilled in the art, e.g. by treating the polyaromatic compounds containing acid groups with suitable, preferably aqueous, solutions of the desired salts. In this case, any aqueous solutions of the desired salts are suitable. Examples of suitable solutions are the hydroxide solutions, the carbonate solutions and the halide solutions of the desired salts. Preferred cations of the salts are already mentioned above.
  • the polyaromatic compounds carrying acid groups are particularly preferably sulfonated polyaryl ether ketones.
  • Suitable sulfonated polyaryl ether ketones are all known sulfonated polyaryl ether ketones. These are generally obtained by sulfonation of the corresponding polyaryl ether ketones. Suitable sulfonation processes are known to the person skilled in the art and are described inter alia in EP-A 0 008 895, WO 03/03198, DE-A 3402471, DE-A 3321860, EP-A 0 574 791, EP-A 815 159 and WO 2004 / 076530 discloses.
  • the poly-aryl ether ketones are commercially available or can be prepared by methods known to those skilled in the art. The partial or complete conversion of the acid groups into the corresponding salts takes place - as mentioned above - by methods known to the person skilled in the art.
  • the sulfonated polyaryl ether ketones are preferably selected from the group consisting of sulfonated polyether ketones (sPEK), sulfonated polyether ether ketones (sPEEK), sulfonated polyether ketone ketones (sPEKK) and sulfonated polyether ether ketone ketones (sPEEKK).
  • sPEK sulfonated polyether ketones
  • sPEEK sulfonated polyether ketones
  • sPEKK sulfonated polyether ketone ketones
  • sPEEKK sulfonated polyether ketones
  • the degree of sulfonation of the sulfonated polyaryl ether ketones used according to the invention is generally from 10 to 90%, preferably from 20 to 80%, particularly preferably from 30 to 60%, very particularly preferably from 35 to 55%. Suitable processes for the preparation of sulfonated polyaryl ether ketones having the stated degrees of sulfonation are mentioned in the abovementioned documents.
  • the degree of sulfonation indicates the number of acid functions (and / or the corresponding salts) per repeat unit of the polymer in% (mol%).
  • formulations are preferably prepared which contain polyaromatic compounds carrying 1 to 5 acid groups and / or salts of acid groups, preferably 1 or 2 acid groups and / or salts of polyaromatic compounds carrying acid groups, more preferably 1 acid groups and / or salts of acid groups contain polyaromatic compound.
  • the formulations according to the present application may contain further polymeric compounds, in particular acidic group-bearing polymeric compounds which are not aromatic, e.g. As sulfonated fluoropolymers such as Nafion ®, Aciplex ®, Flemion ® and / or Hyflon Ion ® included. It is z. B. possible that the formulations A by jointly dissolving the at least one acid groups and / or salts of acid groups carrying polyaromatic compound with the other polymeric compound in step i) are prepared.
  • Step i) contacting the polyaromatic compound carrying at least one acid group and / or salt of acid groups with water
  • aqueous formulations A comprising at least one polyaromatic compound bearing acid groups and / or salts of acid groups
  • the polyaromatic compound carrying at least one acid group and / or salt of acid groups is brought into contact with water according to the process of the invention.
  • Step i) is carried out at a temperature of> 170 0 C, preferably from 171 to 350 0 C, more preferably 180 to 250 0 C. If temperatures higher than the stated temperatures are used, the acid groups and / or salts of oxygen are decomposed. regroup bearing polyaromatic compounds. At lower than the temperatures mentioned, the acid groups and / or salts of polyaromatic compounds carrying acid groups do not or only slightly dissolve. The exact decomposition temperature is dependent on the acid groups and / or salts of polyaromatic compound bearing acid groups.
  • the temperature during the treatment in step i) is kept constant.
  • Constant a temperature deviation of +/- 2 0 C to understand. This is a good reproducibility of the solid obtained material contents and the subsequent casting solution reached.
  • Step i) is carried out in a closed reactor which is pressure-stable. Suitable reactors are known to the person skilled in the art.
  • step (i) is carried out in an autoclave.
  • step (i) generally occurs at a pressure which is at least equal to the autogenous pressure formed at said temperatures.
  • the process according to the invention-in order to obtain the highest possible solids contents of the formulations A- is carried out in such a way that water is added to the polyaromatic compound containing at least one acid group and / or its salts used in step (i) and added in a closed reactor the above temperatures is treated.
  • an aqueous formulation A is obtained together with a gel-like solid, the gel-like solid containing polyaromatic compounds which have not dissolved in acid groups and / or salts thereof.
  • the gel-like solid is generally prepared by methods known to those skilled in the art, e.g. B. by centrifugation, decantation, filtration, etc. separated.
  • aqueous formulations A are obtained in which the polyaromatic compound containing at least one acid group and / or salt of acid groups is present in dissolved or dispersed form.
  • the polyaromatic compound bearing acid groups and / or their salts is unchanged, that is, no change in the molecular weight of the acid groups and / or salts carrying acid groups polyaromatic compound is made.
  • the surprisingly improved water solubility of acid groups and / or salts of polyaromatic compounds bearing acid groups with respect to the water solubility of polyaromatic compounds according to the prior art is caused by a polyaromatic compounds bearing acid groups by the inventive treatment of the acid groups and / or salts used achieved modified particle morphology of the acid groups and / or their salts bearing polyaromatic compounds.
  • the polyaromatic compounds bearing acid groups and / or their salts treated according to the invention have other physical properties (particle morphology, water solubility) than polyaromatic compounds according to the prior art which carry acid groups and have the same content of acid groups.
  • the change in the particle morphology of the acid groups and / or their salts carrying polyaromatic compounds carried out in the process according to the invention occurs only from a certain temperature and a certain pressure.
  • the change in the particle morphology leads to an improved "water solubility.” If this temperature is not reached, no improved solubility in water of the polyaromatic compound carrying sulfonic acid groups and / or their salts can be achieved, as described, for example, in Comparative Example 3 disclosed in WO 98/55534
  • the temperature (165 ° C.) selected in this comparative example is not sufficient to achieve an altered particle morphology and thus an improved solubility in water of the polyaromatic compound bearing the acid groups used.
  • the salts of acid groups-carrying polyaromatic compounds are used in the process according to the invention.
  • all acid groups of the respective polyaromatic compounds may be present in their salt form or only a part of the acid groups, so that the polyaromatic compounds carry both acid groups and salts of acid groups.
  • Preferred ratios of acid groups to salts of acid groups and preferred salts have already been mentioned above.
  • step (i) reducing the generally formed in step (i) gel-like solid (residue) and thus increasing the yield of dissolved or dispersed salts of acid groups-carrying polyaromatic compound fertil, wherein the reduced gel load further the effort to
  • One embodiment of the process according to the invention thus relates to the use of salts of polyaromatic compounds bearing acid groups, the reactor being a metal reactor.
  • Suitable salts of acid group-bearing compounds are mentioned above.
  • Suitable metal reactors for. As metal autoclave, are known in the art.
  • the metal of the metal reactor is generally high-alloy steels.
  • a mixture is used in the process according to the invention, in addition to the at least one acid groups and / or salts of acid groups supporting compound and water 0.1 to 5 wt .-%, preferably 0.1 to 2 wt .-%, particularly preferably 0.5 to 1 wt .-%, based on the total amount of the mixture, at least one polar aprotic solvent, preferably selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, methylene chloride, chloroform, EtOAc and mixtures thereof, more preferably N-methyl- 2-pyrrolidone.
  • the solids content ie the content of acid groups and / or salts of polyaromatic compounds carrying acid groups
  • the solids content in the casting solution (see below described formulation D) can be further increased if small amounts of one or more polar aprotic solvents to the in be added to the mixture used in the process according to the invention.
  • the amounts of polar aprotic solvent are so low that their own dissolving power is not sufficient to solve not treated according to the invention treated acid groups and / or their salts bearing polyaromatic compounds.
  • the "water solubility" deteriorates.
  • the inventive addition of small amounts of polar aprotic solvent thus the solids content of the final casting solution (Formulation D) can be further increased.
  • the advantage (e) mentioned above regarding the use of salts of acid groups of polyaromatic compounds is also achieved in this way. It is likewise possible to achieve particularly high solids contents of the casting solution (formulation D) by combining the use of the polyaromatic compounds carrying the salts carrying acid groups with the addition of the polar aprotic solvent.
  • the at least one acid group and / or acid group-carrying polyaromatic compound used in step (i) of the process according to the invention has a residual moisture content of ⁇ 30% by weight, preferably ⁇ 50% by weight preferably from ⁇ 70 wt .-% to.
  • the at least one acid group and / or acid group-carrying polyaromatic compound used in step (i) at no time has a residual moisture content of 30% by weight, preferably 50% by weight, more preferably 70% by weight .-% below.
  • the solids content of Formulation A and of the final casting solution can be increased. Furthermore, the proportion of gel-like solid generally formed in the preparation of Formulation A is reduced.
  • the advantages (a) to (d) mentioned above with regard to the use of salts of acid groups of polyaromatic compounds and with regard to the addition of additional polar aprotic solvent are likewise achieved in this way. It is furthermore possible to Called embodiments combine arbitrarily to achieve very high solids content.
  • step (i) of the process according to the invention When using acid groups and / or salts of polyaromatic compounds bearing acid groups, which have a residual moisture content mentioned above, the step of drying before use in step (i) of the process according to the invention is eliminated, whereby the entire process is very energy efficient.
  • a polyaromatic compound bearing at least one acid group and / or salt of acid groups and having a residual moisture content of ⁇ 30% by weight, preferably ⁇ 50% by weight, more preferably ⁇ 70% by weight is a composition of the at least one polyaromatic compound and To understand water, having a solids content of ⁇ 70 wt .-% and a water content of ⁇ 30 wt .-%, preferably having a solids content of ⁇ 50 wt .-% and a water content of ⁇ 50 wt .-%, more preferably with a solids content of ⁇ 30 wt .-% and a water content of ⁇ 70 wt .-%, wherein the sum of solids content and water content 100 wt .-% results.
  • solids contents of 10 to 70% by weight, more preferably 15 to 50% by weight, very particularly preferably 20 to 30% by weight and water contents of 30 to 90% by weight, particularly preferably 50 to 85% by weight %, most preferably 70 to 80 wt .-%, wherein the sum of solid content and water content 100 wt .-% results.
  • the acid groups and / or salts of polyaromatic compounds containing acid groups with the said residual moisture contents are obtained in accordance with methods known to the person skilled in the art, in that no drying of the polyaromatic compounds produced takes place.
  • the polyaromatic compounds preferably have not fallen below the above-mentioned residual moisture content at any time.
  • step (i) have, in addition to a reduction in the amount of gelatinous solid formed as residue, an influence on the viscosity of the casting solution used for producing the polymer membranes.
  • the resulting casting solutions starting from polyaromatic compounds bearing acid groups and / or their salts which have been treated according to the invention are distinguished by excellent stability. In general, they are stable at temperatures ⁇ 35 ° C for several weeks.
  • the aqueous formulation A obtained according to the process of the invention in step (i) has a high content of the polyaromatic compound bearing at least one acid group and / or salt of acid groups.
  • This is generally 1 to 30 wt .-%, preferably 5 to 25 wt .-%, particularly preferably 10 to 20 wt .-%, most preferably 15 to 20 wt .-%, wherein the sum of the at least one acid groups and / or salts bearing polyaromatic compound and water gives 100 wt .-%.
  • the polyaromatic compound carrying at least one acid group and / or its salts is dissolved or dispersed in the aqueous formulation A.
  • the aqueous formulation obtained in the method according to the invention in step (i) may contain 0.1 to 5% by weight, preferably 0.1 to 2% by weight, more preferably 0.5 to 1 wt .-% of at least one polar aprotic solvent selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile, methylene chloride, chloroform, EtOAc and mixtures thereof, preferably N-methyl-2-pyrrolidone, wherein the sum of the polyaromatic compound carrying at least one acid group and / or its salts, water and the at least one polar aprotic solvent yields 100% by weight.
  • at least one polar aprotic solvent selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, te
  • aqueous formulations A prepared according to the inventive method which preferably contain the following components
  • polar aprotic solvent selected from the group consisting of N-methyl-2-pyrrolidon
  • the novel aqueous formulation A which generally has a content of polyaromatic compounds having acid groups and / or their salts of from 1 to 30% by weight, has a significantly lower viscosity than formulations of sulfonated polyaryl ether ketones with the same amount of sulfonated polyaryl ether ketone in organic solvents such as DMSO (dimethylsulfoxide), DMAc (N, N-dimethylacetamide), DMF (dimethylformamide) or NMP (N-methylpyrrolidone).
  • organic solvents such as DMSO (dimethylsulfoxide), DMAc (N, N-dimethylacetamide), DMF (dimethylformamide) or NMP (N-methylpyrrolidone).
  • the aqueous formulations A according to the present invention have the advantage over organic formulations that water has a lower boiling point than said organic solvents and is also untoxic.
  • stable casting solutions can be prepared from the aqueous formulations A.
  • aqueous formulations obtained in step i) can subsequently be further treated in step (ii).
  • step ii) the water can be removed from the formulation A obtained in step i). In this case, a dried formulation B is obtained.
  • the removal of the water from the aqueous formulations may be accomplished by any method known to those skilled in the art. For example, a removal of the water by applying a vacuum and optionally heating or spray drying is possible.
  • the at least one polar aprotic solvent optionally present in the formulations A according to the invention can be used in step (ii) of the process according to the invention
  • the dried formulation B obtained in step (ii) of the process according to the invention can (a) contain no polar aprotic solvent,
  • the removal of the water in step (ii) of the process according to the invention can likewise be complete or partial.
  • the dried formulation B obtained in step ii), which contains the polyaromatic compound carrying at least one acid group and / or salt of acid groups, is very readily soluble in water even at room temperature. This is surprising since the acid groups and / or salts used in step i) of polyaromatic compounds bearing acid groups are generally water-insoluble. A change in the molecular weights of the acid groups and / or their salts bearing polyaromatic compounds has not occurred according to the analysis by gel permeation chromatography. As already mentioned above, one reason for the good water solubility of the dried formulations B could be an altered morphology of the acid group bearing polyaromatic compounds by the process performed in step i).
  • aqueous formulations A produced by the process according to the invention in step i) comprise at least one polyaromatic compound carrying acid groups and the dried formulations B prepared according to steps i) and ii) containing at least one polyaromatic compound bearing acid groups from the prior art Technique known aqueous or dried formulations containing at least one acid group-bearing polyaromatic compound distinguish.
  • Another object of the present application is therefore a dried formulation B prepared according to the inventive method comprising the steps i) and ii). Suitable process conditions and preferably used components of the formulations are already mentioned above.
  • the dried formulations B according to the invention can be processed further in various ways. On the one hand, it is possible with the aid of the dried formulations B according to the invention to prepare aqueous formulations C which have an even higher solids content of polyaromatic compounds bearing acid groups and / or their salts than the aqueous formulations A obtained according to the process of the invention in step i)
  • aqueous formulations are obtainable which have a content of the at least one acid group and / or their content Salts carrying polyaromatic compound of up to 50 wt .-%, based on the sum of the acid groups and / or their salts bearing polyaromatic compound, water and optionally present polar aprotic solvent having.
  • a further subject of the present application is therefore a formulation C containing
  • the above-mentioned formulation C according to the invention preferably contains from 1 to 50% by weight, more preferably from 5 to 40% by weight, very preferably from 10 to 35% by weight and especially preferably from 25 to 35% by weight of the at least one acid group and / or their salts bearing polyaromatic compound, based on the sum of the at least one acid group and / or their salts bearing polyaromatic compound, water and optionally present polar aprotic solvent.
  • the polyaromatic compound bearing at least one acid group and / or its salts may be derived from the dried formulation B or from the dried formulation B and the aqueous formulation A.
  • (Ca) from 1 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 10 to 35% by weight, very particularly preferably from 25 to 35% by weight, of at least one polyaromatic compound bearing acid groups,
  • water-containing formulations D are of interest, in addition to the possibly already present polar aprotic solvent at least one further polar aprotic solvent or an alcohol.
  • Suitable polar aprotic solvents are, for example, NMP (N-methylpyrrolidone), DMAc (N, N-dimethylacetamide), DMF (dimethylformamide), DMSO (dimethylsulfoxide), tetrahydrofuran, acetonitrile, methylene chloride, chloroform, EtOAc, and alcohols, e.g.
  • methanol As methanol, ethanol, propanol, dialcohols such as ethylene glycol, trialcohols such as glycerol or mixtures thereof.
  • the further polar aprotic solvent and the polar aprotic solvent which may be present in the aqueous formulation A may be the same or different.
  • the ratio of water to the polar aprotic solvent and / or the alcohol in the aqueous formulations D is generally 50: 1 to 1: 5, preferably 6: 1 to 3: 1.
  • a further subject of the present application are therefore water-containing formulations D containing
  • aqueous formulation A as obtained by means of the inventive method according to step (i), or a formulation C, as obtained by adding water or the inventive formulation A to the dried formulation B, and additionally to optionally already present in the aqueous formulation A or the formulation C polar aprotic solvent (Db) at least 2 wt .-%, preferably 2 to 30 wt .-%, particularly preferably 5 to 25 wt .-%, most preferably 10 to 20 wt .-%, based on the total amount of the formulation, at least one other polar aprotic solvent and / or at least one alcohol, wherein the total amount of
  • Suitable polar aprotic solvents and alcohols have already been mentioned above.
  • the proportion of the polar aprotic solvent and / or the alcohol in the aqueous formulation is generally at least 2 wt .-%, preferably 2 to 30 wt .-%, particularly preferably 5 to 25 wt .-%, most preferably 10 to 20 Wt .-%, based on the total amount of the aqueous formulation.
  • the water-containing formulation D according to the invention is prepared by adding at least 2% by weight, based on the total amount of the formulation, of at least one further polar aprotic solvent and / or at least one alcohol to the aqueous formulation A according to the invention, as in step i). of the process according to the invention, or to the formulation C according to the invention, comprising the dried formulation B according to the invention and water or the aqueous formulation A according to the invention.
  • Suitable polar aprotic solvents, suitable alcohols and suitable amounts of the solvents have already been mentioned above.
  • the water-containing formulations D according to the invention can not be prepared by dissolving polyaromatic compounds bearing acid groups and / or their salts in a mixture of water and solvent, owing to the water-insolubility of the polyaromatic compounds bearing acid groups and / or their salts.
  • the aqueous formulations D thus represent excellent casting solutions for the preparation of water-insoluble membranes.
  • a faster drying at low temperatures can be carried out since the boiling point of water is significantly lower than the boiling point of the organic solvents used in membrane production starting from acid groups-carrying polyaromatic compounds according to the prior art the technique can be used.
  • the aqueous formulations according to the invention have a low viscosity, which facilitates filtration during membrane production.
  • higher solids contents can be achieved with the water-containing formulations D according to the invention.
  • a further subject of the present application is therefore a process for the preparation of a dry formulation E comprising at least one polyaromatic compound bearing at least one acid group and / or its salts by drying the aqueous formulation D according to the invention.
  • Suitable drying methods are known to the person skilled in the art, for example drying at elevated temperatures can take place.
  • dry formulations E which generally have a solids content of> 70% by weight, preferably 70 to 90% by weight.
  • Another object of the present application is a dry formulation E prepared according to the inventive method mentioned above.
  • the dry formulation E which is prepared from a water-containing formulation D containing at least 2% by weight of polar aprotic solvent and / or alcohol, has the advantage that it is water-insoluble and thus for the production of membranes can be used for fuel and electrolysis cells.
  • Advantages of membrane preparation starting from the aqueous formulation D have already been mentioned above.
  • water-insoluble membranes can thus be produced, i. H. the water-containing formulation D is used in a preferred embodiment as a casting solution for membrane production.
  • the dry formulation E may additionally contain at least one further polymer and / or further inorganic and / or organic compounds, which may be solid or liquid, which may be added before or after drying of the water-containing formulation D.
  • the water-containing formulation D likewise additionally contains at least one further polymer and / or further inorganic substances.
  • niche and / or organic compounds, which may be solid or liquid, may contain.
  • the additional presence of at least one further polymer in the hydrous formulations D is of interest for the production of blend membranes.
  • mixing of the dry formulation E with the further polymer and / or the inorganic and / or organic compounds is conceivable. It is also conceivable to deposit the further polymers in the form of a film on a membrane prepared from the aqueous formulation D.
  • Suitable further polymers are, for example, water-soluble or water-dispersible polymers such as polyvinylpyrrolidone and polyvinylcaprolactam.
  • dry formulations E which additionally contain at least one further polymer, preferably at least one water-soluble or water-dispersible polymer such as polyvinylpyrrolidone and / or polyvinylcaprolactam, and optionally further inorganic and / or organic compounds.
  • the weight ratio between the at least one polyaryletherketone of the dry formulation and the at least one further polymer is generally from 1: 99 to 99: 1, preferably from 2: 1 to 20: 1.
  • the inorganic and / or organic compounds which are suitable as further constituents are generally low molecular weight or polymeric solids, which, for example, may be capable of absorbing or releasing protons.
  • phyllosilicates such as bentonites, montmorillonites, serpentine, kalinite, talc, pyrophyllite, mica.
  • Aluminosilicates such as zeolites.
  • Non-water-soluble organic carboxylic acids such as those having 5 to 30, preferably 8 to 22, particularly preferably 12 to 18 carbon atoms, with linear or branched alkyl radical, which optionally have one or more further functional groups, wherein as functional groups, in particular hydroxyl groups , CC double bonds or carbonyl groups too are called.
  • Examples which may be mentioned are the following carboxylic acids: valeric acid, isovaleric acid, 2-methylbutyric acid, pivalic acid, caproic acid, enanthic acid, caprylic acid, pelegonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margarine acid, stearic acid, nonadecanoic acid , Arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tubercolostearic acid, palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidonic acid, culanodonic acid and docosahexanoic acid or mixtures of two or more thereof.
  • Polyphosphoric acids as described, for example, in Hollemann
  • non-functionalized polymer is understood as meaning polymers which contain neither perfluorinated and sulfonated (ionomeric) polymers, such as Nafion® or Flemion®, for example, to obtain sufficient proton conductivity with suitable groups, for example -SO 2 -l groups or -COOH groups are functionalized polymers.
  • suitable groups for example -SO 2 -l groups or -COOH groups are functionalized polymers.
  • these non-functionalized polymers which can be used in the context of the present invention there are no particular restrictions as long as they are stable within the scope of the fields of application in which the polymer systems according to the invention are used. If, according to a preferred use, these are used in fuel cells, it is necessary to use polymers which are thermally stable up to 100 ° C. and preferably up to 200 ° C. or higher and have the highest possible chemical stability.
  • Preferably used are:
  • Aromatic backbone polymers such as polyimides, polysulfones, polyethersulfones such as Ultrason®, polybenzimidazoles. Polymers with fluorinated backbone such as Teflon® or PVDF.
  • Thermoplastic polymers or copolymers such as polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate or polyvinylidene carbonate or polyurethanes, as described, inter alia, in WO 98/44576.
  • polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate or polyvinylidene carbonate or polyurethanes, as described, inter alia, in WO 98/44576.
  • - Crosslinked polyvinyl alcohols Vinyl polymers such as
  • Phenol-formaldehyde resins polytrifluorostyrene, poly-2,6-diphenyl-1,4-phenylene oxide, polyaryl ether sulfones, polyarylene ether sulfones, phosphonated poly-2,6-dimethyl
  • Olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, propene, hexene or higher homologs, butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane.
  • Acrylic acid or methacrylic acid esters such as methyl, ethyl, - propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, or Hexafluoropropyl ester or tetrafluoropropyl acrylate or tetrafluoropropyl methacrylate.
  • Vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl,
  • non-functionalized polymers can be used in principle in crosslinked or uncrosslinked form.
  • formulations according to the invention are suitable for numerous applications known to the person skilled in the art. It is essential that with the aid of the method according to the invention formulations are available which can be used as ion-exchanging polymer systems, for example in fuel cells, for example as ionomer or polymer electrolyte membrane, for example in membrane-electrode units (MEA).
  • a further subject of the present invention is therefore the use of a dry formulation E according to the invention as an ionomer or polymer electrolyte membrane as well as ionomers or polymer electrolyte membranes prepared from the dry formulation E according to the invention or the water-containing formulation D according to the invention. It is likewise possible to use the formulations A, B according to the invention , C and D for the preparation of ionomer formulations or polymer electrolyte membranes, optionally after further treatment of the formulations.
  • the preparation of the polymer electrolyte membrane according to the invention can be carried out according to all suitable methods known to the person skilled in the art.
  • the preparation of the polymer electrolyte membrane according to the invention is preferably carried out by preparing a casting solution or casting dispersion containing at least one polyaromatic compound bearing acid groups and / or their salts.
  • the casting solution or casting dispersion may be the water-containing formulation D according to the invention or the dry formulation E according to the invention dissolved in at least one of the abovementioned polar aprotic solvents and / or alcohols.
  • the casting solution or casting dispersion is applied to a suitable support, for example by spreading the casting solution or dispersion with a doctor blade.
  • Suitable carriers are, for example, a glass plate or PET film. It is also possible to apply the casting solution or casting dispersion, for example by dipping, spin coating, roll coating, spray coating, printing and letterpress, gravure, flat or screen printing processes or by extrusion, if necessary, to a carrier material .
  • the further work-up can be carried out in a customary manner, for example by removing the solvent or the mixture of water with a suitable solvent by drying at room temperature or elevated temperature, if appropriate under reduced pressure.
  • the polymer electrolyte membranes according to the invention are generally known to the skilled person using any suitable methods. see and / or organic acids washed (activation). The salts of sulfonic acids which may be present in the membrane are converted into the free sulfonic acids and any residual solvent present is washed out.
  • polymer electrolyte membranes are prepared which have a thickness of 5 to 500 microns, preferably 10 to 500 microns and more preferably 10 to 200 microns (thickness of the dry polymer electrolyte membrane).
  • Another object of the present application is a composite body containing at least a first layer containing at least one acid group-carrying polyaromatic compound in the form of a dry formulation E according to the invention, wherein the optionally present in the inventive formulation salts of sulfonic acids either before or after the preparation of the composite body in the free sulfonic acids, generally by washing with any inorganic and / or organic acids, and such a composite body, the at least one first layer containing at least one acid group-carrying polyaromatic compound in the form of a dry formulation according to the invention in the form of a membrane and further comprising at least one electrically conductive catalyst layer (Catalyst Coated Membrane, CCM).
  • CCM electrically conductive catalyst layer
  • Suitable CCMs include a catalyst layer, e.g. B. composed of a polymer, preferably a dry formulation E, carbon black and a catalyst, preferably a noble metal catalyst or a catalyst layer, which is prepared by application of so-called catalyst ink on the membrane.
  • Suitable catalyst inks contain z.
  • Suitable solvents are water, alcohols (monohydric or polyhydric alcohols, for example alcohols having one, two or three OH groups), DMAc (N, N-dimethylacetamide), DMF (dimethylformamide), DMSO (dimethylsulfoxide) or NMP (N-methylpyrrolidone ).
  • Preferred catalyst inks are the below-mentioned aqueous catalyst formulations.
  • the catalyst inks can, for. B. by spraying, knife coating or printing and other methods known in the art are applied to the membrane.
  • the composite body may comprise one or more gas diffusion layers (GDLs), e.g. B. have a carbon mat.
  • GDLs gas diffusion layers
  • the catalyst layer (s) is (are) arranged on the or the gas distribution layer (s), wherein a membrane electrode assembly (MEA) is obtained.
  • Suitable membrane-electrode assemblies and catalyst-coated membranes and their preparation are known in the art.
  • a suitable MEA is prepared by coating a catalyst ink on a GDL to give a coated GDL. Two coated GDLs are then processed together with a polymer electrolyte membrane interposed between the GDLs to form an MEA, eg by means of a hot pressing process.
  • Preferred catalyst inks and polymer electrolyte membranes are the catalyst inks and polymer electrolyte membranes of the present invention.
  • Suitable processes for the preparation of the MEA are known to the person skilled in the art.
  • this composite body may comprise one or more bipolar electrodes.
  • a further subject of the present application is a fuel cell containing at least one polymer electrolyte membrane according to the invention or a composite body according to the invention.
  • Preferred polyaromatic compounds bearing acid groups have already been mentioned above.
  • novel aqueous and aqueous formulations according to the invention can be used for the preparation of catalyst formulations (polymer electrolyte + carbon black + noble metal catalyst, water and optionally solvent, preferably a water-miscible solvent) and for the application of polyaromatic compounds bearing acid groups to membranes and Gas diffusion electrodes are used.
  • catalyst formulations polymer electrolyte + carbon black + noble metal catalyst, water and optionally solvent, preferably a water-miscible solvent
  • An advantage of the formulations according to the invention is that they allow a higher degree of utilization of the noble metal catalyst due to their altered polymer morphology. As a result, a lower loading of the catalyst with noble metal than in the prior art is possible and the production of noble metal catalysts is thus cheaper.
  • the dissolution of the membrane can be specifically controlled for better contacting between the membrane and the catalyst layer.
  • the above-mentioned aqueous or hydrous catalyst formulations are characterized by a high flammability, which facilitates handling of the pyrophoric catalyst.

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Abstract

L'invention concerne un procédé pour obtenir des formulations aqueuses (A) contenant au moins un composé polyaromatique portant des groupes acides et/ou des sels de groupes acides, ainsi que des formulations aqueuses (A) obtenues d'après le procédé selon l'invention. L'invention porte également sur un procédé pour obtenir des formulations séchées (B) par extraction de l'eau des formulations aqueuses (A), ainsi que sur les formulations séchées (B) elles-mêmes. L'invention concerne aussi une formulation (C) contenant la formulation séchée (B) selon l'invention et de l'eau ou une formulation aqueuse (A) et une formulation aqueuse (D) contenant la formulation aqueuse (A) selon l'invention ou la formulation (C) selon l'invention et au moins 2 % en poids d'un solvant organique. L'invention porte également sur des formulations sèches (E) obtenues par extraction de l'eau des formulations aqueuses (D) selon l'invention. Elle porte aussi sur l'utilisation des formulations aqueuses (D) selon l'invention et des formulations sèches (E) obtenues à partir des premières pour réaliser une membrane électrolytique polymère, sur la membrane électrolytique polymère elle-même, sur une unité électrode-membrane (MEA) et sur une pile à combustible contenant la membrane électrolytique polymère selon l'invention.
EP07857267A 2006-12-28 2007-12-06 Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible Withdrawn EP2108021A1 (fr)

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EP07857267A EP2108021A1 (fr) 2006-12-28 2007-12-06 Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible

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EP06127261 2006-12-28
PCT/EP2007/063406 WO2008080752A1 (fr) 2006-12-28 2007-12-06 Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible
EP07857267A EP2108021A1 (fr) 2006-12-28 2007-12-06 Formulations aqueuses contenant des composés polyaromatiques portant des groupes acides et/ou des sels de groupes acides, leur procédé de fabrication, autres formulations obtenues en utilisant les formulations aqueuses, et utilisation des autres formulations dans des piles à combustible

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CN110724263B (zh) * 2019-10-23 2020-08-14 四川大学 具有中子吸收功能的含硼二维聚芳硫醚材料及制备方法

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JPH02139022A (ja) * 1988-11-18 1990-05-29 Nitto Denko Corp 芳香族ポリスルホン多孔質膜の処理方法
DE19723854A1 (de) * 1997-06-06 1998-12-10 Hoechst Ag Verfahren zur Herstellung von Lösungen mit Säuregruppen funktionalisierter Polymere durch Mikrowellenbestrahlung
DE19743434A1 (de) * 1997-10-01 1999-04-08 Basf Ag Wäßrige Formulierung auf Basis von Arylsulfonsäure-Formaldehyd-Kondensaten oder sulfoniereten Phenol-Formaldehyd-Kondensaten, Tensiden und organischen Komplexbildnern oder anionischen polymeren Dispergiermitteln und ihre Verwendung
GB0400612D0 (en) * 2004-01-13 2004-02-11 Johnson Matthey Plc Polymer solutions
DE102005030970A1 (de) * 2005-06-30 2007-01-11 Basf Ag Wässrige Formulierungen enthaltend Säuregruppen tragende polyaromatische Verbindungen
US20070099054A1 (en) * 2005-11-01 2007-05-03 Fuller Timothy J Sulfonated-perfluorocyclobutane polyelectrolyte membranes for fuel cells
CN100343306C (zh) * 2006-02-20 2007-10-17 扬州天辰精细化工有限公司 聚芳醚腈的工业化生产方法

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JP2010514869A (ja) 2010-05-06
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CA2674114A1 (fr) 2008-07-10
WO2008080752A1 (fr) 2008-07-10
KR20090101468A (ko) 2009-09-28
CN101622301A (zh) 2010-01-06

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