EP1554032A2 - Membrane polymere conductrice de protons comprenant des polyazoles contenant des groupes acide phosphonique et utilisation de cette membrane dans des piles a combustible - Google Patents

Membrane polymere conductrice de protons comprenant des polyazoles contenant des groupes acide phosphonique et utilisation de cette membrane dans des piles a combustible

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Publication number
EP1554032A2
EP1554032A2 EP03775169A EP03775169A EP1554032A2 EP 1554032 A2 EP1554032 A2 EP 1554032A2 EP 03775169 A EP03775169 A EP 03775169A EP 03775169 A EP03775169 A EP 03775169A EP 1554032 A2 EP1554032 A2 EP 1554032A2
Authority
EP
European Patent Office
Prior art keywords
acid
group
aromatic
heteroaromatic
groups
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.)
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Application number
EP03775169A
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German (de)
English (en)
Inventor
Oemer Uensal
Joachim Kiefer
Gordon Calundann
Michael Sansone
Brian Benicewicz
Eui Wong Choe
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 Fuel Cell Research GmbH
Original Assignee
Pemeas GmbH
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Filing date
Publication date
Application filed by Pemeas GmbH filed Critical Pemeas GmbH
Publication of EP1554032A2 publication Critical patent/EP1554032A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
    • 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

Definitions

  • Proton-conducting polymer membrane comprising polyazoles containing phosphonic acid groups and their use in fuel cells
  • the present invention relates to a proton-conducting polymer electrolyte membrane comprising polyazoles containing phosphonic acid groups, which, owing to its excellent chemical and thermal properties, can be used in many different ways and is particularly suitable as a polymer electrolyte membrane (PEM) in so-called PEM fuel cells.
  • PEM polymer electrolyte membrane
  • a fuel cell usually contains an electrolyte and two electrodes separated by the electrolyte.
  • one of the two electrodes is supplied with a fuel, such as hydrogen gas or a methanol-water mixture, and the other electrode with an oxidizing agent, such as oxygen gas or air, and chemical energy from the fuel oxidation is thereby converted directly into electrical energy. Protons and electrons are formed in the oxidation reaction.
  • the electrolyte is for hydrogen ions, i.e. Protons, but not permeable to reactive fuels such as hydrogen gas or methanol and oxygen gas.
  • a fuel cell typically includes a plurality of single cells, so-called MEA 's (membrane electrode assembly), each of which contains an electrolyte and two electrodes separated by the electrolyte.
  • MEA 's membrane electrode assembly
  • Solids such as polymer electrolyte membranes or liquids such as phosphoric acid are used as the electrolyte for the fuel cell.
  • Polymer electrolyte membranes have recently attracted attention as electrolytes for fuel cells. In principle, one can differentiate between two categories of polymer membranes.
  • the first category includes cation exchange membranes consisting of a polymer structure which contains covalently bound acid groups, preferably sulfonic acid groups.
  • the sulfonic acid group changes into an anion with the release of a hydrogen ion and therefore conducts protons.
  • the mobility of the proton and thus the proton conductivity is directly linked to the water content. Due to the very good miscibility of
  • Such cation exchange membranes have a high methanol permeability in methanol and water and are therefore unsuitable for applications in a direct methanol fuel cell. Dries the membrane, e.g. As a result of high temperature, the conductivity of the membrane and consequently the performance of the fuel cell decrease drastically. The operating temperatures of fuel cells containing such
  • Cation exchange membranes are thus limited to the boiling point of the water.
  • the humidification of the fuels represents a major technical challenge for the Use of polymer electrolyte membrane fuel cells (PEMBZ), in which conventional, sulfonated membranes such as Nafion are used.
  • PEMBZ polymer electrolyte membrane fuel cells
  • perfluorosulfonic acid polymers are used as materials for polymer electrolyte membranes.
  • the perfluorosulfonic acid polymer (such as Nafion) generally has a perfluorocarbon backbone, such as a copolymer
  • Tetrafluoroethylene and trifluorovinyl and a side chain having a sulfonic acid group attached thereto, such as a side chain having a sulfonic acid group attached to a perfluoroalkylene group.
  • the cation exchange membranes are preferably organic
  • cation exchange membranes listed commercial for use in fuel cells have gained importance: The most important representative is the perfluorosulfonic Nafion ® (US 3,692,569). This polymer can be brought into solution as described in US Pat. No. 4,453,991 and then used as an ionomer. Cation exchange membranes are also obtained by filling a porous support material with such an ionomer. Expanded Teflon is preferred as the carrier material (US 5635041).
  • Another perfluorinated cation exchange membrane can be prepared as described in US5422411 by copolymerization from trifluorostyrene and sulfonyl-modified trifuorostyrene.
  • Composite membranes consisting of a porous carrier material, in particular expanded Teflon, filled with ionomers consisting of such sulfonyl-modified trifluorostyrene copolymers are described in US5834523.
  • US6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation for the production of cation exchange membranes for fuel cells.
  • Another class of partially fluorinated cation exchange membranes can be
  • Radiation plugging and subsequent sulfonation can be produced.
  • a grafting reaction is preferably carried out on a previously irradiated polymer film, preferably with styrene.
  • the sulfonation of the side chains then takes place in a subsequent sulfonation reaction.
  • crosslinking can also be carried out and thus the mechanical
  • cation exchange membrane can be mixed with a high temperature stable polymer.
  • the production and properties of cation exchange membranes consisting of blends of sulfonated PEK and a) polysulfones (DE4422158), b) aromatic polyamides (42445264) or c) polybenzimidazole (DE19851498) are described.
  • Solvent dissolved and then reacted with an aggressive sulfonating reagent, such as oleum or chlorosulfonic acid.
  • an aggressive sulfonating reagent such as oleum or chlorosulfonic acid.
  • This reaction is relatively critical, since the sulfonating reagent is a strong oxidizing agent, so that degradation of the PEK cannot be ruled out, the mechanical properties of the polymer in particular being adversely affected.
  • the sulfonated polymer is isolated in a further process step and converted into the neutral form. The polymer is then brought back into solution. Among other things, a polymer film can be cast from this solution.
  • the solvent used for this purpose for example N-dimethylacetamide, must then be removed. Accordingly, the process for producing such membranes is complex and therefore expensive.
  • Sulfonated polybenzimidazoles are also known from the literature. Thus US-A-4634530) describes sulfonation of an undoped polybenzimidazole film with a sulfonating agent such as sulfuric acid or oleum in the temperature range up to
  • the polymer precipitates sulfonating agent to the PBI / DMAc solution.
  • a PBI film was first produced and this was immersed in a dilute sulfuric acid. to The samples were then sulfonated at temperatures of approximately 475 ° C. for 2 minutes.
  • the sulfonated PBl membranes only have a maximum conductivity of 7.5 * 10 "5 S / cm at a temperature of 160 ° C.
  • the maximum ion exchange capacity is 0.12 meq / g. It has also been shown that such sulfonated PBl membranes are not are suitable for use in a fuel cell.
  • Membranes is 10 "3 S / cm and is therefore too low for applications in fuel cells in which 0.1 S / cm are aimed for.
  • Membranes have a high methanol permeability.
  • the cause of these disadvantages is the conductivity mechanism of the membrane, in which the transport of the protons is coupled to the transport of the water molecule. This is called the "vehicle mechanism" (K.-D. Kreuer, Chem. Mater. 1996, 8, 610-641).
  • polymer electrolyte membranes with complexes of basic polymers and strong acids have been developed.
  • WO96 / 13872 and the corresponding US Pat. No. 5,525,436 describe a process for producing a proton-conducting polymer electrolyte membrane, in which a basic polymer, such as polybenzimidazole, is treated with a strong acid, such as phosphoric acid, sulfuric acid, etc.
  • the polymer serves as a carrier for the electrolyte consisting of the highly concentrated phosphoric acid.
  • the polymer membrane fulfills further essential functions, in particular it must have high mechanical stability and as
  • CO is produced as a by-product in the reforming of the hydrogen-rich gas from carbon-containing compounds, e.g. Natural gas, methanol or gasoline or as an intermediate in the direct oxidation of methanol.
  • carbon-containing compounds e.g. Natural gas, methanol or gasoline or as an intermediate in the direct oxidation of methanol.
  • the CO content of the fuel must be less than 100 ppm at temperatures ⁇ 100 ° C. at
  • temperatures in the range 150-200 ° can also be tolerated to 10,000 ppm CO or more (N.J. Bjerrum et. Al. Journal of Applied Electrochemistry, 2001, 31, 773-779). This leads to significant simplifications of the upstream reforming process and thus to cost reductions for the entire fuel cell system.
  • a great advantage of fuel cells is the fact that the energy of the fuel is converted directly into electrical energy and heat during the electrochemical reaction. Water forms as a reaction product on the cathode. Heat is therefore a by-product of the electrochemical reaction.
  • electricity is used to drive electric motors, e.g.
  • the heat must be dissipated to prevent the system from overheating. Additional, energy-consuming devices are then required for cooling, which further reduce the overall electrical efficiency of the fuel cell.
  • the heat can be efficiently used using existing technologies such as Use heat exchanger. High temperatures are aimed at to increase efficiency. If the operating temperature is above 100 ° C and the temperature difference between the ambient temperature and the operating temperature is large, then it becomes possible to cool the fuel cell system more efficiently or to use small cooling surfaces and to dispense with additional devices compared to fuel cells which, due to the membrane humidification, are below 100 ° C must be operated.
  • such a fuel cell system also has disadvantages.
  • the durability of membranes doped with phosphoric acid can still be improved.
  • the service life is significantly reduced, in particular by operating the fuel cell below 100 ° C., for example at 80 ° C. In this context, however, it should be noted that when the fuel cell is started up and shut down, the cell must be operated at these temperatures.
  • the present invention is therefore based on the object of providing a novel polymer electrolyte membrane which achieves the objects set out above.
  • a membrane according to the invention should be able to be produced inexpensively and simply.
  • a membrane according to the invention exhibits a high conductivity over a wide temperature range, which is also achieved without additional moistening.
  • a membrane according to the invention can be produced simply and inexpensively. Large quantities of expensive solvents such as dimethylacetamide can thus be dispensed with.
  • the present invention relates to a proton-conducting polymer membrane comprising polyazoles containing phosphonic acid groups, obtainable by a process comprising the steps A) Mixing one or more aromatic and / or heteroaromatic tetra-amino compounds with one or more aromatic and / or heteroaromatic carboxylic acids or their derivatives, which contain at least two acid groups per carboxylic acid monomer, at least some of the tetra-amino compounds and / or the carboxylic acids at least one
  • the mixture produced in step A) comprises monomers containing phosphonic acid groups for the production of polayzoles. Accordingly, either the tetra-amino compounds necessary for the production of these polymers or the aromatic carboxylic acid with at least two carboxy groups can have phosphonic acid residues. Furthermore, both the tetra-amino compounds and the aromatic carboxylic acids can have phosphonic acid groups.
  • the mixtures can also include tetra-amino compounds and aromatic carboxylic acids which have no phosphonic acid groups.
  • Preferred aromatic and / or heteroaromatic tetra-amino compounds which have at least one phosphonic acid group generally correspond to the formula (A)
  • Ar represents an aromatic or heteroaromatic group
  • Y is a bond or a group having 1 to 20 carbon atoms
  • p is an integer between 1 and 4, where p is the number of bonds or
  • R 1 is hydrogen or 1 to 20 carbon atoms
  • the corresponding salts for example the alkali metal salts, or the esters of the phosphonic acids can also be added to the mixture.
  • the preferred esters include in particular the C1 to C6-
  • Alkyl esters of these compounds for example the methyl and / or ethyl esters.
  • Y represents a bond
  • p and r are each 1 and Z corresponds to the formula (1). If Y represents a bond, p is 1, with the group Z directly attached to the aromatic or heteroaromatic group
  • the number r represents the number of groups Z which are bonded to the aromatic or heteroaromatic group Ar.
  • aromatic groups denote residues of mono- or polynuclear aromatic compounds with preferably 6 to 20, in particular 6 to 12, carbon atoms.
  • Heteroaromatic groups denote aryl radicals in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O, heteroaromatic groups having 3 to 19 carbon atoms.
  • Aromatic or heteroaromatic groups preferred according to the invention are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane,
  • 1 to 20 carbon-containing group denotes residues of organic compounds with 1 to 20 carbon atoms.
  • aromatic and heteroaromatic groups already mentioned above, it includes alkyl, cycloalkyl, alkoxy,
  • Cycloalkoxy, cycloalkylthio, alkenyl, alkanoyl, alkoxycarbonyl groups and heteroalipatic groups The groups mentioned can be branched or not branched.
  • the preferred alkyl groups include the methyl, ethyl, propyl, isopropyl, 1-butyl,
  • the preferred cycloalkyl groups include the cyclopropyl, cyclobutyl, cyclopentyl,
  • Cyclohexyl, cycloheptyl and the cyclooctyl group which are optionally substituted with branched or unbranched alkyl groups.
  • the preferred alkenyl groups include the vinyl, allyl, 2-methyl-2-propene, 2-butenyl, 2-pentenyl, 2-decenyl and the 2-eicosenyl groups.
  • the preferred alkynyl groups include the ethynyl, propargyl, 2-methyl-2-propyne, 2-butynyl, 2-pentynyl and the 2-decynyl groups.
  • the preferred alkanoyl groups include the formyl, acetyl, propionyl, 2-
  • Methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and the dodecanoyl group Methylpropionyl, butyryl, valeroyl, pivaloyl, hexanoyl, decanoyl and the dodecanoyl group.
  • the preferred alkoxycarbonyl groups include the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl group, hexyloxycarbonyl, 2-
  • Methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group are examples.
  • Preferred alkoxy groups include alkoxy groups whose hydrocarbon residue is one of the preferred alkyl groups mentioned above.
  • the preferred cycloalkoxy groups include cycloalkoxy groups whose hydrocarbon radical is one of the preferred cycloalkyl groups mentioned above.
  • the preferred heteroaliphatic groups include the abovementioned preferred cycloalkyl radicals in which at least one carbon unit has been replaced by O, S or a group NR 2 and R 2 is hydrogen, an alkyl having 1 to 6 carbon atoms and one having 1 to 6 carbon atoms Alkoxy or an aryl group means.
  • branched or unbranched alkyl or alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 12, advantageously 1 to 6, in particular 1 to 4 carbon atoms and cycloalkyl or cycloalkyloxy groups having 3 to 20 carbon atoms, preferably 5 to 6 carbon atoms.
  • radicals in the abovementioned radicals can be replaced by halogen atoms, preferably chlorine or fluorine, thiol or hydroxyl groups and groups of the general formula NR 2 R 3 and N + R 2 R 3 R 4
  • the radicals R 2 , R 3 and R 4 independently of one another are hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group, unsubstituted radicals have proven to be particularly expedient.
  • These compounds include, inter alia, 3,3 ', 4,4'-tetraaminobiphenyl-5-phosphonic acid, 3,3', 4,4'-tetraaminobiphenyl-5,5'-diphosphonic acid,
  • Preferred aromatic and / or heteroaromatic tetra-amino compounds which have at least one sulfonic acid group generally correspond to the formula (C)
  • Ar represents an aromatic or heteroaromatic group
  • Y is a bond or a group having 1 to 20 carbon atoms
  • p is an integer between 1 and 4, where p is the number of bonds or
  • R 1 is hydrogen or 1 to 20 carbon atoms
  • the corresponding salts for example the alkali metal salts, or the esters of the phosphonic acids can also be added to the mixture.
  • the preferred esters include in particular the C1 to C6-
  • Alkyl esters of these compounds for example the methyl and / or ethyl esters.
  • Y represents a bond
  • p and r are each 1 and Z corresponds to the formula (1).
  • Such compounds can be obtained particularly easily by sulfonation of known, generally commercially available aromatics or heteroaromatics. If Y represents a bond, p is 1, the group Z being bonded directly to the aromatic or heteroaromatic group Ar. In this case, the number r represents the number of groups Z which are bonded to the aromatic or heteroaromatic group Ar.
  • aromatic and heteroaromatic tetra-amino compounds containing sulfonic acid groups include, among others, 3,3 ', 4,4'-tetraaminobiphenyl-5-sulfonic acid, 3,3', 4,4'-tetraaminobiphenyl-5,5 ' -disulfonic acid, 3,3 ', 4,4'-tetraaminodiphenylsulfone-5-sulfonic acid, 3,3', 4,4'-tetraaminodiphenylsulfone-5,5'-disulfonic acid, 3,3 ', 4,4'-tetraaminodiphenyl ether - 5-sulfonic acid and
  • the mixture may include aromatic and heteroaromatic tetra-amino compounds that do not contain phosphonic acid groups.
  • aromatic and heteroaromatic tetra-amino compounds that do not contain phosphonic acid groups. These include 3,3 ', 4,4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1,2,4,5-
  • Tetraaminobenzene 3,3 ', 4,4'-tetraaminodiphenylsulfone, 3,3', 4,4'-tetraaminodiphenyl ether, 3,3 ', 4,4'-tetraaminobenzophenone, 3,3', 4,4'-tetraaminodiphenylmethane and 3,3 ', 4,4'-tetraaminodiphenyldimethylmethane and their salts, especially their mono-, di-, tri- and tetrahydrochloride derivatives.
  • 3,3 ', 4,4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine and 1,2,4,5-tetraaminobenzene are particularly preferred.
  • the mixture produced in step A) can be aromatic and / or heteroaromatic
  • carboxylic acids and their derivatives that contain phosphonic acid groups include dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their derivatives.
  • the preferred derivatives include the esters, in particular C1-C20-alkyl esters or C5-C12-aryl esters, the anhydrides or the acid halides, in particular the acid chlorides and / or the acid bromides.
  • Preferred aromatic and / or heteroaromatic carboxylic acids or their derivatives which contain at least two acid groups per carboxylic acid monomer generally correspond to the formula (B)
  • Ar represents an aromatic or heteroaromatic group which may optionally have further substituents, for example carboxylic acid groups or their derivatives, for example their esters or their carboxylic acid halides
  • X represents a halogen atom, for example chlorine, iodine or bromine, or a group of the formula OR 2 , in which R 2 represents a hydrogen atom or a group having 1 to 20 carbon atoms, Y is a bond or a group having 1 to 20 carbon atoms, p is an integer between 1 and 4, where p is the number of bonds or
  • R 1 is a hydrogen atom or a group having 1 to 20 carbon atoms.
  • the corresponding salts for example the alkali metal salts, or the esters of the phosphonic acids can also be added to the mixture.
  • the preferred esters include in particular the C1 to C6 alkyl esters of these compounds, for example the methyl and / or ethyl esters.
  • Y represents a bond
  • p and r are each 1 and Z corresponds to the formula (1).
  • the preferred aromatic dicarboxylic acids or their derivatives include 2,5-dicarboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid and 3,5-dicarboxyphenylphosphonic acid.
  • the mixture produced in step A) can comprise aromatic and / or heteroaromatic carboxylic acids and also their derivatives which contain sulfonic acid groups. These include dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their derivatives.
  • the preferred derivatives include the esters, in particular C1-C20-alkyl esters or C5-C12-aryl esters, the anhydrides or the acid halides, in particular the acid chlorides and / or the acid bromides.
  • Preferred aromatic and / or heteroaromatic carboxylic acids or their derivatives which contain at least two acid groups per carboxylic acid monomer generally correspond to the formula (D)
  • Ar represents an aromatic or heteroaromatic group which may optionally have further substituents, for example carboxylic acid groups or their derivatives, for example their esters or their carboxylic acid halides,
  • X represents a halogen atom, for example chlorine, iodine or bromine, or a group of the formula OR 2 , in which R 2 represents a hydrogen atom or a group having 1 to 20 carbon atoms, Y is a bond or a group having 1 to 20 carbon atoms, p is a is an integer between 1 and 4, where p is the number of bonds or.
  • R 1 is hydrogen or 1 to 20 carbon atoms
  • the corresponding salts for example the alkali metal salts, or the esters of the phosphonic acids can also be added to the mixture.
  • the preferred esters include in particular the C1 to C6-
  • Alkyl esters of these compounds for example the methyl and / or ethyl esters.
  • Y represents a bond
  • p and r are each 1 and Z corresponds to the formula (1).
  • Such compounds can be obtained particularly easily by sulfonation of known, generally commercially available aromatics or heteroaromatics.
  • the preferred aromatic dicarboxylic acids or their derivatives include 2,5-dicarboxyphenylsulfonic acid, 2,3-dicarboxyphenylsulfonic acid, 3,4-dicarboxyphenylsulfonic acid and 3,5-dicarboxyphenylsulfonic acid.
  • the mixture may include aromatic carboxylic acids that do not include phosphonic acid groups.
  • aromatic carboxylic acids that do not include phosphonic acid groups.
  • aromatic dicarboxylic acids are preferably isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylaminoisophthalic acid, 5 N, N-diethylaminoisino-2,5-amino acid Dihydroxy terephthalic acid, 2,6 dihydroxy isophthalic acid, 4,6 dihydroxy isophthalic acid, 2,3 dihydroxy phthalic acid, 2,4
  • aromatic tricarboxylic acids or their C1-C20 alkyl esters or C5-C12 aryl esters or their acid anhydrides or their acid chlorides are preferably 1,3,5-benzene-tricarboxylic acid (trimesic acid), 1,2 , 4-benzene-tricarboxylic acid (trimellitic acid), (2-carboxy ⁇ henyl) iminodiacetic acid, 3,5,3'-biphenyltricarboxylic acid, 3,5,4'-
  • aromatic tetracarboxylic acids or their C1-C20-alkyl esters or C5-C12-aryl esters or their acid anhydrides or their acid chlorides, which have no phosphonic acid groups are preferably 3,5,3 ', 5'-biphenyltetracarboxylic acid , 1, 2,4,5-benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 1, 2,5,6-naphthalenetetracarboxylic acid, 1.4 , 5,8-naphthalene.
  • heteroaromatic carboxylic acids which have no phosphonic acid groups are heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or their anhydrides.
  • Heteroaromatic carboxylic acids are understood to mean aromatic systems which contain at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic system. It is preferably pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid,
  • the content of tricarboxylic acid or tetracarboxylic acids (based on the dicarboxylic acid used) is between 0 and 30 mol%, preferably 0.1 and 20 mol%, in particular 0.5 and 10 mol%. This information relates to the sum of the carboxylic acids, regardless of the phosphonic acid content.
  • aromatic and heteroaromatic diaminocarboxylic acids used according to the invention which comprise at least one phosphonic acid group, are preferably 2,3-diamino-5-carboxyphenylphosphonic acid, 2,3-diamino-6-carboxyphenylphosphonic acid and 3,4-diamino-6-carboxyphenylphosphonic acid.
  • the corresponding salts for example the alkali metal salts, or the esters of the phosphonic acids in the mixture can also be used be attached.
  • the preferred esters include in particular the C1 to C6 alkyl esters of these compounds, for example the methyl and / or ethyl esters.
  • the mixture to be prepared according to step A) can also aromatic and heteroaromatic diaminocarboxylic acids which comprise at least one sulfonic acid group.
  • aromatic and heteroaromatic diaminocarboxylic acids which comprise at least one sulfonic acid group. This is preferably 2,3-diamino-5-carboxyphenylsulfonic acid, 2,3-diamino-6-carboxyphenylsulfonic acid and 3,4-diamino-6-carboxyphenylsulfonic acid.
  • the mixture can also contain aromatic and heteroaromatic diaminocarboxylic acids which contain no phosphonic acid groups.
  • aromatic and heteroaromatic diaminocarboxylic acids which contain no phosphonic acid groups. These include diaminobenzoic acid, 4-phenoxycarbonyl-3, '4'-diaminodiphenyl ether and their mono- and dihydrochloride derivatives.
  • step A Mixtures of at least 2 different aromatic carboxylic acids are preferred in step A). Mixtures which contain not only aromatic carboxylic acids but also heteroaromatic carboxylic acids are particularly preferred.
  • the mixing ratio of aromatic carboxylic acids to heteroaromatic carboxylic acids is between 1:99 and 99: 1, preferably 1:50 to 50: 1. This information is independent of the phosphonic acid content of the carboxylic acids.
  • mixtures are in particular mixtures of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids.
  • dicarboxylic acids without a phosphonic acid group are isophthalic acid, terephthalic acid, phthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxyphthalic acid. 3,4-
  • Dihydroxyphthalic acid 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, 1,8-dihydroxynaphthalene-3,6-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone - 4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 4-trifluoromethylphthalic acid, pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-
  • 2,6-dicarboxylic acid pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2,6-pyrimidinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid.
  • Carboxylic acids with phosphonic acid groups can easily be derived from the aforementioned compounds.
  • the molar ratio of carboxylic acid groups to amino groups in the reaction of tetra-amino compounds with one or more aromatic carboxylic acids or their esters, which contain at least two acid groups per carboxylic acid monomer is preferably close of 1: 2.
  • the mixture produced in step A) preferably comprises at least 0.5% by weight, in particular 1 to 30% by weight and particularly preferably 2 to 15% by weight, of monomers for the production of polyazoles.
  • Monomers which are used to prepare polyazoles are generally in the range from 0.5 to 100% by weight, preferably 2 to 80% by weight, particularly preferably 5 to 50% by weight, without being restricted thereby should.
  • Mixtures which contain carboxylic acids containing at least two carboxylic acid groups and tetraamino compounds without phosphonic acid groups are particularly preferred.
  • the content of monomers containing sulfonic acid, based on all monomers which are used to prepare polyazoles, is generally in the range from 0 to 99% by weight, preferably 2 to 50% by weight, particularly preferably 10 to 40% by weight. % without any limitation.
  • the molar phosphorus to nitrogen ratio (P / N ratio), based on the polyazoles obtainable in step B), is between 0.02 and 0.5, preferably between 0.05 and 0.35 and very particularly preferably between 0.07 and 0.25, without this being intended to impose a restriction.
  • the P / N ratio can be measured using elementary analysis.
  • the molar sulfur to nitrogen ratio (S / N ratio), based on the polyazoles obtainable in step B) is between 0.02 and 2, preferably between 0.05 and 1 and very particularly preferably between 0.07 and 0.25, without any limitation.
  • the S / N ratio can be measured using elementary analysis.
  • the molar sulfur to phosphorus ratio (S / P ratio), based on that obtainable in step B)
  • Polyazoles between 0 and 10, preferably between 0.1 and 5 and very particularly preferably between 0.2 and 4, without any intention that this should impose a restriction.
  • the S / P ratio can be measured using elementary analysis.
  • the polyphosphoric acid used in step A) is commercially available
  • Polyphosphoric acids such as those available from Riedel-de Haen, for example.
  • the polyphosphoric acids H n + 2 P n O 3n + ⁇ (n> 1) usually have a content calculated as P 2 O 5 (acidimetric) of at least 83%.
  • a dispersion / suspension can also be produced.
  • a mixture is formed in step A) which contains at least one aromatic group containing phosphonic acid groups Carboxylic acid and at least one amino compound without phosphonic acid groups.
  • a polyazole containing phosphonic acid groups is formed in step B) comprising repeating azole units of the general formula (I) and / or (II) and / or (III) and / or (IV) and / or (V) and / or (VI) and / or (VII) and / or (VIII) and / or (IX) and / or (X) and / or (XII) and / or (XIII) and / or (XIV) and / or (XV) and / or (XVI) and / or (XVI) and / or (XVII) and / or (XVIII) and / or (XIX) and / or (XX) and / or / or (XX) and / or / or (XVIII) and / or
  • Ar are the same or different and are the same or different for a tetra-aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 1 are the same or different and for a divalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 2 are the same or different and for a two or three-membered aromatic or heteroaromatic group which can be mono- or polynuclear
  • Ar 3 are the same or different and for a three-membered aromatic or heteroaromatic group which can be mono- or polynuclear
  • Ar 4 are the same or different and for a three-membered aromatic or heteroaromatic group which can be mono- or polynuclear
  • Ar 5 are the same or different and for a tetra-aromatic or heteroaromatic group which can be mono- or polynuclear
  • Ar 6 are the same or different and for a divalent aromatic or heteroaromatic group, which can be mononuclear or polynuclear
  • Ar 7 are identical or different and represent a divalent aromatic or heteroaromatic group, which may be mono- or polynuclear
  • Ar 8 are identical or different and represent a trivalent aromatic or heteroaromatic group, which may be mono- or polynuclear
  • Ar 9 are identical or are different and are the same or different for a two- or three- or four-membered aromatic or heteroaromatic group, which can be mono- or polynuclear
  • Ar 10 are the same or different and for a di- or tri-bonded aromatic or heteroaromatic group, which can be mono- or polynuclear
  • Ar 11 are the same or different and are for a double-bonded aromatic or heteroaromatic group which can be mononuclear or polynuclear
  • X is identical or different and for oxygen, sulfur or an amino group which has a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as a further radical, R is identical or different for hydrogen , an alkyl group and an aromatic
  • n is an integer greater than or equal to 10, preferably greater than or equal to 100.
  • Y is a bond or a group having 1 to 20 carbon atoms
  • p is independently an integer between 1 and 4, where p is the number of bonds or groups Y via which the group Z is linked to the aromatic or heteroaromatic group
  • r independently of one another is an integer between 1 and 4, where r represents the number of groups Z which are linked to the group Y or, if Y is a bond, to the aromatic or heteroaromatic group
  • Z is a group of the general Formula 1) - PO3H2 (D
  • R 1 is a hydrogen atom or a group having 1 to 20 carbon atoms.
  • n and m which represent the number of repeating units, also include the repeating units which have no phosphonic acid groups.
  • aromatic or heteroaromatic group and “1 to 20 carbon-containing group” were previously explained.
  • the substitution pattern of Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 is arbitrary, in the case of phenylene, for example, Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 are ortho-, meta- and para-phenylene. Particularly preferred groups are derived from benzene and biphenylene, which may also be substituted.
  • Preferred alkyl groups are short-chain alkyl groups with 1 to 4 carbon atoms, such as. B. methyl, ethyl, n- or i-propyl and t-butyl groups.
  • Preferred aromatic groups are phenyl or naphthyl groups.
  • the alkyl groups and the aromatic groups can be substituted.
  • Preferred substituents are halogen atoms such as. B. fluorine, amino groups,
  • Hydroxy groups or short-chain alkyl groups such as. B. methyl or ethyl groups.
  • the polyazoles can also have different recurring units which differ, for example, in their X radical. However, it preferably has only the same X radicals in a recurring unit.
  • Further preferred polyazole polymers are polyimidazoles, polybenzthiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
  • the polymer containing recurring azole units is a copolymer or a blend which contains at least two units of the formulas (I) to (XXII) which differ from one another.
  • the polymers can be present as block copolymers (diblock, triblock), statistical copolymers, periodic copolymers and / or alternating polymers.
  • the polymer containing recurring azole units is a polyazole which contains only units of the formula (I) and / or (II).
  • the number of repeating azole units in the polymer is preferably an integer greater than or equal to 10.
  • Particularly preferred polymers contain at least 100 repeating azole units.
  • polymers containing recurring benzimidazole units are preferred.
  • Some examples of the extremely useful polymers containing recurring benzimidazole units are represented by the following formulas:
  • n and m is an integer greater than or equal to 10, preferably greater than or equal to 100.
  • the numbers n and m which represent the number of repeating units, also include the repeating units which have no phosphonic acid groups. These units are formed by a polyreaction of monomers, in particular aromatic carboxylic acids with at least two acid groups, which do not include a phosphonic acid group.
  • the polyazoles obtainable by the process described, but in particular the polybenzimidazoles, are distinguished by a high molecular weight. Measured as intrinsic viscosity, this is in the range from 0.3 to 10 dl / g, preferably 1 to 5 dl / g. If the mixture according to step A) also contains tricarboxylic acids or tetracarboxylic acids, branching / crosslinking of the polymer formed is achieved in this way. This contributes to the improvement of the mechanical property.
  • step B) the mixture obtained in step A) is heated to a temperature of up to 350 ° C., preferably up to 280 ° C., in particular 100 ° C. to 250 ° C. and particularly preferably in the range from 200 ° C. to 250 ° C. heated.
  • An inert gas for example nitrogen or a noble gas, such as neon, argon, is used here.
  • aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 2,5-dihydroxyterephthalic acid, 4,6-dihydroxyisophthalic acid, 2,6-dihydroxyisophthalic acid, diphenic acid, 1, 8-dihydroxynaphthalene-3, 6-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid,
  • Biphenyl-4,4'-dicarboxylic acid 4-trifluoromethylphthalic acid, pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2 , 5-pyridinedicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2,6-pyrimidinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid, the temperature in step B) in the range from up to 300 ° C., preferably between 100 ° C. and 250 ° C., is favorable , These temperature ranges also apply to the corresponding carboxylic acids containing phosphonic acid groups.
  • the heating according to step B) can take place after the formation of a flat structure according to step C).
  • the mixture produced in step A) and / or step B) may additionally contain organic solvents. These can have a positive impact on processability. For example, the rheology of the solution can be improved so that it can be extruded or squeegee more easily.
  • the mixture produced in step A) and / or step B) can also contain dissolved, dispersed or suspended polymer. Such polymers can also be added to the mixture after step B).
  • the preferred polymers include, inter alia, polyolefins, such as poly (chloroprene),
  • Polyacetylene polyphenylene, poly (p-xylylene), polyarylmethylene, polyarmethylene, polystyrene, polymethylstyrene, polyvinyl alcohol, polyvinyl acetate, polyvinyl ether, polyvinylamine, poly (N-vinyl acetamide), polyvinylimidazole, polyvinylcarbazole, polyvinylpyrrolidone, polyvinylpyridine fluoride, polyvinylpyridine fluoride, polyvinylpyridine fluoride, Copolymers of PTFE with hexafluoropropylene, with perfluoropropyl vinyl ether, with
  • Trifluoronitrosomethane with sulfonyl fluoride vinyl ether, with carbalkoxy-perfluoroalkoxy vinyl ether, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyacrolein, polyacrylamide, Polyacrylonitrile, polycyanoacrylates, polymethacrylimide, cycloolefinic copolymers, in particular from norbornene;
  • Polyacetal polyoxymethylene, polyether, polypropylene oxide, polyepichlorohydrin, polytetrahydrofuran, polyphenylene oxide, polyether ketone, polyester, in particular
  • Polyhydroxyacetic acid Polyethylene terephthalate, polybutylene terephthalate,
  • Polyhydroxybenzoate polyhydroxypropionic acid, polypivalolactone, polycaprolactone,
  • Polymeric C-S bonds in the main chain for example polysulfide ether, polyphenylene sulfide, polyether sulfone;
  • Polyimines polyisocyanides, polyetherimine, polyaniline, polyamides, polyhydrazides,
  • Polyurethanes polyimides, polyazoles, polyazines
  • Liquid-crystalline polymers in particular Vectra and inorganic polymers, for example polysilanes, polycarbosilanes, polysiloxanes,
  • Polysilicic acid Polysilicates, silicones, polyphosphazenes and polythiazyl.
  • the mixture produced in step A) and / or step B) can also comprise polymers with covalently bonded acid groups. These polymers can also be added to the mixture after step B). These acid groups include in particular
  • the polymers modified with sulfonic acid groups preferably have a sulfonic acid group content in the range from 0.5 to 3 meq / g. This value is determined via the so-called ion exchange capacity (IEC).
  • IEC ion exchange capacity
  • the sulfonic acid groups are converted into the free acid.
  • the polymer is treated with acid in a known manner, excess acid being removed by washing.
  • the sulfonated polymer is first treated in boiling water for 2 hours. Excess water is then dabbed off and the sample is dried for 15 hours at 160 ° C. in a vacuum drying cabinet at p ⁇ 1 mbar. Then the dry weight of the membrane is determined.
  • the polymer dried in this way is then dissolved in DMSO at 80 ° C. for 1 h. The solution is then titrated with 0.1 M NaOH.
  • the ion exchange capacity (IEC) is then calculated from the consumption of the acid up to the equivalent point and the dry weight.
  • polymers containing sulfonic acid groups can be prepared, for example, by sulfonating polymers. Methods for sulfonating polymers are described in F. Kucera et. al. Polymer Engineering and Science 1988, Vol. 38, No 5, 783-792. The sulfonation conditions can be selected so that a low degree of sulfonation is produced (DE-A-19959289).
  • Another class of non-fluorinated polymers was developed by sulfonation of high-temperature stable thermoplastics. Thus, sulfonated polyether ketones (DE-A-4219077, WO96 / 01177), sulfonated polysulfones (J. Membr. Sei. 83 (1993) p.211) or sulfonated polyphenylene sulfide (DE-A-19527435) are known.
  • US-A-6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation for use in fuel cells.
  • polymers can also be obtained by polyreactions of monomers which comprise acid groups.
  • Perfluorinated polymers such as in
  • the preferred polymers with acid groups include, among others, sulfonated polyether ketones, sulfonated polysulfones, sulfonated polyphenylene sulfides, perfluorinated polymers containing sulfonic acid groups, as described in US-A-3692569, US-A-5422411 and US-A-
  • fillers in particular proton-conducting fillers, and additional acids can also be added to the membrane.
  • the addition can, for example, in step A), step
  • additives if they are in liquid form, can also be added after the polymerization in step D).
  • Non-limiting examples of proton-conducting fillers are sulfates such as: CsHSO 4 , Fe (SO 4 ) 2 , (NH 4 ) 3 H (SO 4 ) 2 , LiHSO 4 , NaHSO 4 , KHSO 4 , RbSO 4 ,
  • Oxides such as Al 2 O 3 , Sb 2 O 5l ThO 2 , SnO 2 , ZrO 2 , MoO 3 Silicates such as zeolites, zeolites (NH 4 +), layered silicates, framework silicates, H-natrolites, H-
  • Fillers such as carbides, in particular SiC, Si 3 N 4 , fibers, in particular glass fibers, glass powders and / or polymer fibers, preferably based on polyazoles.
  • the membrane after the treatment in step D) comprises at most 80% by weight, preferably at most 50% by weight and particularly preferably at most 20% by weight of additives.
  • this membrane can also contain perfluorinated sulfonic acid additives (preferably 0.1-20% by weight, preferably 0.2-15% by weight, very preferably 0.2-10% by weight).
  • Phosphoric acid and phosphate to platinum are Phosphoric acid and phosphate to platinum. (Electrolyte additives for phosphoric acid fuel cells.
  • Perfluorosulfonimide as an additive in phosphoric acid fuel cell. Razaq, M .; Razaq, A .;
  • persulfonated additives are: trifluomethanesulfonic acid, potassium trifluoromethanesulfonate, sodium trifluoromethanesulfonate,
  • Perfluorohexane sulfonic acid potassium nonafluorobutane sulfonate, sodium nonafluorobutane sulfonate, lithium nonafluorobutane sulfonate, ammonium nonafluorobutane sulfonate,
  • step C takes place by means of measures known per se (casting, spraying, knife coating, extrusion) which are known from the prior art
  • Suitable carriers are all carriers which are inert under the conditions. These carriers include, in particular, films made from polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyhexafluoropropylene, copolymers of PTFE with hexafluoropropylene, polyimides, polyphenylene sulfides (PPS) and polypropylene (PP).
  • PET polyethylene terephthalate
  • PTFE polytetrafluoroethylene
  • PTFE polyhexafluoropropylene
  • copolymers of PTFE with hexafluoropropylene polyimides
  • PPS polyphenylene sulfides
  • PP polypropylene
  • the solution can optionally be mixed with an easily evaporable organic solvent. As a result, the viscosity can be adjusted to the desired value and the formation of the membrane can be facilitated.
  • the thickness of the flat structure according to step C) is preferably between 10 and
  • 4000 ⁇ m preferably between 15 and 3500 ⁇ m, in particular between 20 and 3000 ⁇ m, particularly preferably between 30 and 1500 ⁇ m and very particularly preferably between 50 and 1200 ⁇ m.
  • step D) takes place in particular at temperatures in the
  • Range of 0 ° C and 150 ° C preferably at temperatures between 10 ° C and 120 ° C, in particular between room temperature (20 ° C) and 90 ° C, in the presence of moisture or water and / or water vapor.
  • the treatment is preferably carried out under normal pressure, but can also be carried out under the action of pressure. It is essential that the treatment takes place in the presence of sufficient moisture, whereby the polyphosphoric acid present contributes to the solidification of the membrane by partial hydrolysis with the formation of low molecular weight polyphosphoric acid and / or phosphoric acid.
  • step D) The partial hydrolysis of the polyphosphoric acid in step D) leads to a solidification of the
  • the solidified membrane generally has a thickness of between 15 and 3000 ⁇ m, preferably 20 and 2000 ⁇ m, in particular between 20 and 1500 ⁇ m, the membrane being self-supporting.
  • the hardness of the membrane according to step D) also increases its hardness, which can be determined by means of microhardness measurement in accordance with DIN 50539.
  • the membrane is successively loaded with a Vickers diamond within 20 s up to a force of 3 mN and the depth of penetration is determined.
  • the hardness at room temperature is at least 5 mN / mm 2 and preferably at least 20 mN / mm 2 , without any intention that this should impose a restriction.
  • the membranes are generally self-supporting.
  • the force is then kept constant at 3 mN for 5 s and the creep is calculated from the penetration depth.
  • the creep CHU 0.003 / 20/5 under these conditions is less than 30%, preferably less than 15% and very particularly preferably less than 5%.
  • Microhardness measurement specific module YHU is at least 0.1 MPa, in particular at least 2 MPa and very particularly preferably at least 5 MPa, without this being intended to impose a restriction.
  • the upper temperature limit of the treatment according to step D) is usually 150 ° C.
  • this steam can also be hotter than 150 ° C.
  • the duration of the treatment is essential for the upper temperature limit.
  • the partial hydrolysis (step D) can also take place in climatic chambers in which the hydrolysis can be specifically controlled under the influence of moisture.
  • the humidity can be specifically adjusted by the temperature or saturation of the contacting environment, for example gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
  • gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
  • the duration of treatment depends on the parameters selected above.
  • the treatment time depends on the thickness of the membrane.
  • the treatment time is between a few seconds to minutes, for example under the action of superheated steam, or up to whole days, for example in air at room temperature and less relative
  • the treatment time is preferably between 10 seconds and 300 hours, in particular 1 minute to 200 hours.
  • the treatment time is between 1 and 200
  • the membrane obtained in step D) can be self-supporting, i.e. it can be detached from the carrier without damage and then processed directly if necessary.
  • the concentration of phosphoric acid and thus the conductivity of the polymer membrane according to the invention can be adjusted.
  • the concentration of phosphoric acid is given as mole of acid per mole of repeating unit of the polymer.
  • IM repeating unit of the formula
  • the membrane can still be crosslinked by exposure to heat in the presence of oxygen.
  • This hardening of the membrane additionally improves the properties of the membrane.
  • the membrane can be heated to a temperature of at least 150 ° C., preferably at least 200 ° C. and particularly preferably at least 250 ° C.
  • the oxygen concentration is at this
  • the method step is usually in the range from 5 to 50% by volume, preferably 10 to 40% by volume, without any intention that this should impose a restriction.
  • IR InfraRot, ie light with a wavelength of more than 700 nm
  • NIR Near IR, ie light with a wavelength in the range from approx. 700 to 2000 nm or an energy in the range of approx. 0.6 to 1.75 eV).
  • Another method is radiation with ⁇ -rays. The radiation dose is between 5 and 200 kGy.
  • the duration of the crosslinking reaction can be in a wide range. In general, this reaction time is in the range from 1 second to 10 hours, preferably 1 minute to 1 hour, without this being intended to impose any restriction.
  • the polymer membrane according to the invention has improved material properties compared to the previously known doped polymer membranes. In particular, they perform better than known doped polymer membranes. This is due in particular to an improved proton conductivity. At temperatures of 120 ° C., this is at least 0.1 S / cm, preferably at least 0.11 S / cm, in particular at least 0.12 S / cm.
  • the membranes according to the invention comprise polyazoles with sulfonic acid groups
  • the membranes show a high conductivity even at a temperature of 70 ° C.
  • the conductivity depends, among other things, on the sulfonic acid group content of the polyazoles. The higher this proportion, the better the conductivity at low temperatures.
  • a membrane according to the invention can be moistened at low temperatures.
  • the compound used as an energy source for example hydrogen
  • the water formed by the reaction is sufficient to achieve humidification.
  • the specific conductivity is measured by means of impedance spectroscopy in a 4-pole arrangement in potentiostatic mode and using platinum electrodes (wire, 0.25 mm diameter). The distance between the current-consuming electrodes is 2 cm.
  • the spectrum obtained is evaluated using a simple model consisting of a parallel arrangement of an ohmic resistor and a capacitor. The sample cross section of the phosphoric acid-doped membrane is immediately before
  • the measuring cell is brought to the desired temperature in an oven and controlled via a Pt-100 thermocouple positioned in the immediate vicinity of the sample. After reaching the temperature, the sample is kept at this temperature for 10 minutes before starting the measurement.
  • Possible areas of application of the polymer membranes according to the invention include use in fuel cells, in electrolysis, in capacitors and in battery systems.
  • the present invention also relates to a membrane electrode unit which has at least one polymer membrane according to the invention.
  • a membrane electrode unit which has at least one polymer membrane according to the invention.
  • Electrode units as well as the electrodes, gas diffusion layers and catalysts to be selected are also part of the description.
  • the membrane formation can also take place directly on the electrode instead of on a support.
  • the treatment according to step D) can be shortened accordingly, since the membrane no longer has to be self-supporting.
  • Such a membrane is also the subject of the present invention.
  • Another object of the present invention is an electrode comprising polyazoles containing phosphonic acid groups obtainable by a process comprising the
  • Tetra-amino compounds and / or the carboxylic acids comprises at least one phosphonic acid group, or mixing one or more aromatic and / or heteroaromatic diaminocarboxylic acids, at least some of which comprise phosphonic acid groups, in polyphosphoric acid, with the formation of a solution and / or dispersion
  • step B) heating the mixture obtainable according to step A) under inert gas to temperatures of up to 350 ° C, preferably up to 280 ° C to form the polyazole polymer
  • step C) applying a layer using the mixture according to step A) and / or step B) on an electrode
  • the coating has a thickness between 2 and 3000 ⁇ m, preferably between 2 and 2000 ⁇ m, in particular between 3 and 1500 ⁇ m, particularly preferably 5 to 500 ⁇ m and very particularly preferably between 10 to 200 ⁇ m, without this there should be a restriction.
  • step D) leads to a hardening of the coating.
  • the treatment is carried out until the coating has sufficient hardness to be able to be pressed into a membrane electrode assembly.
  • the hardness is sufficient if a membrane treated accordingly is self-supporting. In many cases, however, a lower hardness is sufficient.
  • DIN 50539 micro hardness measurement
  • Hardness is generally at least 1 mN / mm 2 , preferably at least 5 mN / mm 2 and very particularly preferably at least 15 mN / mm 2 , without any intention that this should impose a restriction.
  • An electrode coated in this way can be installed in a membrane-electrode unit, which may have at least one polymer membrane according to the invention.
  • a catalytically active layer can be applied to the membrane according to the invention and this can be connected to a gas diffusion layer.
  • a membrane is formed in accordance with steps A) to D) and the catalyst is applied.
  • the membrane according to steps A) to D) can also be formed on a support or a support film which already has the catalyst.
  • the catalyst is on the membrane of the invention. These structures are also the subject of the present invention.
  • the present invention also relates to a membrane-electrode unit which has at least one coated electrode and / or at least one polymer membrane according to the invention in combination with a further polymer membrane based on polyazoles or a polymer blend membrane containing at least one polymer based on polyazoles.

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  • Separation Using Semi-Permeable Membranes (AREA)
  • Inert Electrodes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne des membranes polymères conductrices de protons comprenant des polyazoles contenant des groupes acide phosphonique, ces membranes pouvant être obtenues par un procédé comprenant les étapes suivantes : A) mélange d'un ou de plusieurs composés tétra-amino aromatiques et/ou hétéroaromatiques avec un ou plusieurs acides carboxyliques aromatiques et/ou hétéroaromatiques ou des dérivés de ceux-ci contenant au moins deux groupes acide par monomère d'acide carboxylique, au moins une partie des composés tétra-amino et/ou des acides carboxyliques comprenant au moins un groupe acide phosphonique, ou mélange d'un ou de plusieurs acides diaminocarboxyliques aromatiques et/ou hétéroaromatiques, dont au moins une partie comprend des groupes acide phosphonique, dans de l'acide polyphosphorique pour former une solution et/ou une dispersion, B) chauffage de la solution et/ou de la dispersion, obtenues d'après l'étape A), sous gaz inerte à des températures allant jusqu'à 350 °C pour former des polymères de polyazole, C) application d'une couche du mélange obtenu d'après l'étape A) et/ou l'étape B) sur un support, D) traitement de la membrane formée à l'étape C) jusqu'à ce que celle-ci soit autoporteuse.
EP03775169A 2002-10-04 2003-10-02 Membrane polymere conductrice de protons comprenant des polyazoles contenant des groupes acide phosphonique et utilisation de cette membrane dans des piles a combustible Withdrawn EP1554032A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10246459A DE10246459A1 (de) 2002-10-04 2002-10-04 Protonenleitende Polymermembran umfassend Phosphonsäuregruppen enthaltende Polyazole und deren Anwendung in Brennstoffzellen
DE10246459 2002-10-04
PCT/EP2003/010906 WO2004033079A2 (fr) 2002-10-04 2003-10-02 Membrane polymere conductrice de protons comprenant des polyazoles contenant des groupes acide phosphonique et utilisation de cette membrane dans des piles a combustible

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EP1554032A2 true EP1554032A2 (fr) 2005-07-20

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US (1) US7736778B2 (fr)
EP (1) EP1554032A2 (fr)
JP (1) JP4450734B2 (fr)
KR (1) KR20050073477A (fr)
CN (1) CN100556934C (fr)
CA (1) CA2500514A1 (fr)
DE (1) DE10246459A1 (fr)
WO (1) WO2004033079A2 (fr)

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WO2004033079A3 (fr) 2004-09-23
CN100556934C (zh) 2009-11-04
KR20050073477A (ko) 2005-07-13
US20060008690A1 (en) 2006-01-12
JP2006501991A (ja) 2006-01-19
US7736778B2 (en) 2010-06-15
CN1726071A (zh) 2006-01-25
WO2004033079A2 (fr) 2004-04-22
CA2500514A1 (fr) 2004-04-22
JP4450734B2 (ja) 2010-04-14
DE10246459A1 (de) 2004-04-15

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