WO2011003539A1 - Procédé pour stabiliser des polymères contenant de l'azote - Google Patents

Procédé pour stabiliser des polymères contenant de l'azote Download PDF

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Publication number
WO2011003539A1
WO2011003539A1 PCT/EP2010/003973 EP2010003973W WO2011003539A1 WO 2011003539 A1 WO2011003539 A1 WO 2011003539A1 EP 2010003973 W EP2010003973 W EP 2010003973W WO 2011003539 A1 WO2011003539 A1 WO 2011003539A1
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Prior art keywords
acid
membrane
polyazole
stabilizing
film
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PCT/EP2010/003973
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German (de)
English (en)
Inventor
Silvia Rybka-Krafft
Jörg BELACK
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Basf Se
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Publication of WO2011003539A1 publication Critical patent/WO2011003539A1/fr

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    • 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
    • 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
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2287—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
    • H01M8/1041—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method for the stabilization of
  • Electrode units and PEM fuel cells are Electrode units and PEM fuel cells.
  • PEM Polymer electrolyte membranes
  • Sulfonic acid-modified polymers in particular perfluorinated polymers, are frequently used here.
  • Nafion TM by DuPont de Nemours, Willmington USA.
  • proton conduction is a relatively high water content in the membrane
  • the operating temperature of the PEM fuel cell stacks usually limited to 80 - 100 0 C. Under pressure, the operating temperatures can be increased to> 120 ° C. Otherwise, higher operating temperatures can not be realized without a power loss of the fuel cell.
  • MEU membrane electrode assembly
  • the cooling devices can be made much simpler. This means that in fuel cell systems that are operated at temperatures above 100 ° C, the waste heat can be made significantly more usable and thus the fuel cell system efficiency can be increased through electricity-heat coupling. In order to reach these temperatures, membranes with new conductivity mechanisms are generally used. One approach for this is the use of membranes, which show an electrical conductivity without the use of water. A first development in this direction is shown for example in WO 96/13872. Thus, WO 96/13872 discloses the use of acid-doped
  • Polybenzimidazole membranes produced by a casting process Polybenzimidazole membranes produced by a casting process.
  • the mechanical stabilization for example by bridging or
  • Vernetzungsreationen is already well known in polymer technology.
  • first solutions of the polyazole polymers are prepared in an aprotic, polar, organic solvent and the solution with a
  • bridging reagent After formation of a film, the organic solvent is removed and the bridging reaction is carried out. Subsequently, the film is doped with a strong acid and used. The obtained
  • Polyazole membranes show improved physical and chemical
  • acidic polyazole membranes based on polyazole polymers show.
  • the membranes should be relatively inexpensive to produce in a relatively simple manner.
  • the present invention is a process for the stabilization, in particular for bridging and / or crosslinking, of polyazole polymers, comprising the following steps:
  • step b) treating the film of step a) with a solution comprising (i)
  • Membrane in the PEM fuel cell such. B. a membrane-electrode unit
  • step d) if appropriate, additional doping of the membrane obtained according to step c) with a strong acid or concentration of the strong acid present by removal of water present.
  • the method according to the invention can be carried out in a comparatively simple manner on an industrial scale and cost-effectively.
  • polyazoles are understood as meaning those polymers in which the repeating unit in the polymer is preferably
  • the aromatic ring contains at least one aromatic ring having at least one nitrogen atom.
  • the aromatic ring is preferably a five- or six-membered ring having one to three nitrogen atoms which may be fused to another ring, especially another aromatic ring.
  • Individual nitrogen heteroatoms can also be replaced by oxygen, phosphorus and / or sulfur atoms.
  • the heterocyclic aromatic rings are preferably present in the polymer backbone but may be present in the side chain. Particular preference is given to those basic polymers which comprise in the repeat unit unsaturated five-membered or six-membered aromatic units containing in the nucleus 1-5 nitrogen atoms or in addition to nitrogen atoms one or more other heteroatoms.
  • the polyazoles according to the invention have at least one amino group in a repeat unit.
  • the amino group as the primary amino group (NH 2 group), as a secondary amino group (NH group) or as a tertiary group, which are either part of a cyclic, optionally aromatic structure or part of a substituent on the aromatic unit.
  • the polymer is basic and the repeating unit may preferably be substituted by the amino group
  • Repeating unit preferably a primary or secondary amino group, more preferably a cyclic secondary amino group, the
  • step B) applying a layer using the mixture according to step A) on a support
  • step B) heating of the sheet / layer obtainable according to step B) under inert gas to temperatures of up to 350 0 C, preferably up to 280 0 C to form the polyazole polymer,
  • step D) hydrolysis of the polymer film formed in step C) (until it is self-supporting),
  • step E) detaching the polymer film formed in step D) from the carrier
  • the aromatic and heteroaromatic tetra-amino compounds used according to the invention are preferably 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'- Tetraaminodiphenyldimethylmethan and salts thereof, in particular their mono-, di-, tri- and tetrahydrochloride derivatives.
  • the aromatic carboxylic acids used according to the invention are dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids or their esters or
  • Carboxylic acids equally includes heteroaromatic carboxylic acids.
  • the aromatic dicarboxylic acids are um
  • Tetrafluoroterephthalic 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, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4'-stilbenedicarboxylic acid, 4 - Carboxycinnamic acid, or their C1 -C20-alkyl esters or C5-C12-aryl esters, or their acid anhydrides or their acid
  • the aromatic tri-, tetracarboxylic acids or their C 1 -C 20 -alkyl esters or C 5 -C 12 -aryl esters or their acid anhydrides or their acid chlorides are preferably 1, 3,5-benzenetricarboxylic acid (trimesic acid), 1, 2,4-benzenetricarboxylic acid (trimellitic acid), (2-carboxyphenyl) iminodiacetic acid, 3,5,3'-biphenyltricarboxylic acid, 3,5,4'-biphenyltricarboxylic acid.
  • aromatic tetracarboxylic acids or their C 1 -C 20 -alkyl esters or C 5 -C 12 -aryl esters or their acid anhydrides or their acid chlorides are preferably 3,5,3 ', 5'-biphenyltetracarboxylic acid (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-naphthalenetetracarboxylic acid.
  • heteroaromatic carboxylic acids used according to the invention are heteroaromatic dicarboxylic acids and tricarboxylic acids and
  • Tetracarboxylic acids or their esters or their anhydrides Tetracarboxylic acids or their esters or their anhydrides.
  • Heteroaromatic carboxylic acids are aromatic systems which contain at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic.
  • 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-pyrazoldicarboxylic acid, 2,6-pyrimidinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid, 2,4, 6-pyridine tricarboxylic acid, benzimidazole-5,6-dicarboxylic acid and their C1-C20-alkyl esters or C5-C12 aryl esters, or their
  • Acid anhydrides or their acid chlorides are Acid anhydrides or their acid chlorides.
  • the content of tricarboxylic acid or tetracarboxylic acid (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%.
  • aromatic and heteroaromatic diaminocarboxylic acids used according to the invention are preferably diaminobenzoic acid and its mono- and dihydrochloride derivatives.
  • step A mixtures of at least 2 different aromatic carboxylic acids are preferably used. Particular preference is given to using mixtures which, in addition to aromatic carboxylic acids, are also heteroaromatic
  • the mixing ratio of aromatic carboxylic acids to heteroaromatic carboxylic acids is between 1:99 and 99: 1, preferably 1:50 to 50: 1.
  • mixtures are, in particular, mixtures of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids.
  • Non-limiting examples thereof 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-pyrazoldicarboxylic acid, 2,6-pyrimidinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid.
  • the polyphosphoric acid used in step A) is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
  • polyphosphoric acids such as these are available, for example, from Riedel-de Haen.
  • the polyphosphoric acids H n + 2 P n O 3 n + i (n> 1) usually have a content calculated as P 2 O 5 (acidimetric) of at least 83%.
  • P 2 O 5 acidimetric
  • the mixture produced in step A) has a weight ratio of polyphosphoric acid to sum of all monomers of 1: 10,000 to 10,000: 1, preferably 1: 1000 to 1000: 1, in particular 1: 100 to 100: 1, on.
  • the layer formation according to step B) takes place by means of measures known per se (casting, spraying, doctoring) which are known from the prior art for polymer film production.
  • Suitable carriers are all suitable carriers under the conditions as inert.
  • other supports such as polymeric films, fabrics and fleeces, which bond to the layer formed in step B) and form a laminate are also suitable.
  • the solution may optionally be treated with phosphoric acid (concentrated phosphoric acid, 85%). This allows the viscosity to be adjusted to the desired value and the formation of the membrane can be facilitated.
  • the layer produced according to step B) has a thickness which is matched to the subsequent use and is not subject to any restriction.
  • the layer formed has a thickness between 1 and 5000 ⁇ m, preferably between 1 and 3500 ⁇ m, in particular between 1 and 100 ⁇ m.
  • the polyazole-based polymer formed in step C) contains recurring 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)
  • Ar are the same or different and represent a tetravalent aromatic or heteroaromatic group which may be mononuclear or polynuclear,
  • Ar 1 are the same or different and represent 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 may be mononuclear or polynuclear
  • Ar 3 are the same or different and are a trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 4 are the same or different and represent a trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 5 are the same or different and represent a tetravalent aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 6 are the same or different and are for a divalent aromatic or
  • heteroaromatic group which may be mononuclear or polynuclear
  • Ar 7 are the same or different and are for a divalent aromatic or
  • heteroaromatic group which may be mononuclear or polynuclear
  • Ar 8 are the same or different and for a trivalent aromatic or
  • heteroaromatic group which may be mononuclear or polynuclear
  • Ar 9 are the same or different and are a two- or three- or diminuhexige
  • aromatic or heteroaromatic group which may be mononuclear or polynuclear
  • Ar 10 are the same or different and represent a divalent or trivalent aromatic or heteroaromatic group which may be mononuclear or polynuclear,
  • Ar 11 are the same or different and are for a divalent aromatic or
  • heteroaromatic group which may be mononuclear or polynuclear
  • X is the same or different and is oxygen, sulfur or a
  • Amino group which represents a hydrogen atom, a 1-20 carbon atoms group, preferably a branched or unbranched
  • R is the same or different for hydrogen, an alkyl group and a
  • n, m are each an integer greater than or equal to 10, preferably greater than or equal to 100.
  • Preferred aromatic or heteroaromatic groups are derived from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, pyrol, pyrazole, anthracene, benzopyrrole, benzotriazole,
  • Benzopyrazidine benzopyrimidine, benzopyrazine, benzothazine, indolizine, quinolizine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, aciridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridizine, benzophthyne, phenanthroline and phenanthrene, which may optionally be substituted from.
  • 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 optionally also be substituted.
  • Preferred alkyl groups are short chain alkyl groups of 1 to 4
  • Carbon atoms such as. For example, methyl, ethyl, n- or i-propyl and t-butyl groups.
  • Preferred aromatic groups are phenyl or naphthyl groups.
  • Alkyl groups and the aromatic groups may be substituted.
  • Preferred substituents are halogen atoms such as. As fluorine, amino groups, hydroxy groups or short-chain alkyl groups such as. For example, methyl or ethyl groups.
  • the polyazoles can in principle also have different recurring units
  • polyazole polymers are polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadiazoles, polyquinoxalines, polythiadiazoles, poly (pyridines), poly (pyrimidines), and poly (tetrazapyrenes).
  • the polymer containing recurring azole units is a copolymer or a blend containing at least two units of the formulas (I) to (XIV) which differ from each other.
  • the polymers can be present as block copolymers (diblock, triblock), random 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 recurring azole units.
  • polymers containing recurring benzimidazole units are preferred.
  • Some examples of the extremely expedient Polymers contain recurring benzimidazole units and are represented by the following formulas:
  • the azole units and the two fluorinated moieties can be linked in any order.
  • the preparation can be carried out as a polymer, static copolymer or block copolymer.
  • n and m are an integer greater than or equal to 10, preferably greater than or equal to 100.
  • the procedure according to the invention is suitable in principle for all polyazoles, irrespective of the molecular weight. However, it has proven particularly useful for the stabilization of high molecular weight polyazoles, which is not obtainable in any other way.
  • High molecular weight polyazoles, but especially polybenzimidazoles, are characterized by a high molecular weight, which, measured as
  • Intrinsic viscosity at least 1.8 dl / g, preferably at least 2.0 dl / g,
  • the upper limit is preferably not more than 8.0 dl / g, more preferably not more than 6.8 dl / g, particularly preferably not more than 6.5 dl / g.
  • the molecular weight is thus significantly higher than that of commercial polybenzimidazole (IV ⁇ 1, 1 dl / g).
  • the polymer is first dried at 160 ° C. for 2 hours. 100 mg of the polymer thus dried are then heated for 4 h at 80 0 C in 100 ml of
  • intrinsic viscosity is determined from this solution according to ISO 3105 (DIN 51562, ASTM D2515) with an Ubbelhode viscometer at a temperature of 25 ° C.
  • step A) by heating the mixture from step A) to temperatures of up to 350 ° C., preferably up to 280 ° C., the formation of oligomers and / or polymers can already be effected. Depending on the selected temperature and duration, subsequent to the heating in step C) be waived partially or completely.
  • This variant is also suitable for producing the films required for step a), preferably comprising high molecular weight
  • 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,
  • step C) The treatment of the polymer layer produced according to step C) to produce the film required for step b) can be carried out in several ways.
  • variant A the existing polyphosphoric acid or
  • Polymer layer takes place in the presence of moisture at temperatures and for a sufficient time until the layer has sufficient strength for the
  • step E The treatment can be carried out so far that the membrane is self-supporting, so that it can be detached from the carrier without damage (step E).
  • the steps D) and E) can also take place simultaneously or briefly on each other. Furthermore, it is possible to combine steps D) and E) with the measures of steps b), c) and if necessary d).
  • Polymer film with the solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent, in particular at least one
  • the implementation of the stabilization reaction according to step c) can with a thermal drying or concentration of the existing acid can be combined.
  • the treatment of the polymer film in step D) is carried out at temperatures above 0 0 C and below 150 0 C, preferably at temperatures between 10 0 C and 120 0 C, in particular between room temperature (20 0 C) and 90 0 C, in the presence of
  • Training low molecular weight polyphosphoric acid and / or phosphoric acid contributes to the solidification of the polymer film. Due to the hydrolysis step, a SoI-GeI transition takes place, which is responsible for the particular shape of the membrane.
  • step D The partial hydrolysis of the polyphosphoric acid in step D) leads to a
  • the upper temperature limit of the treatment according to step D) is generally 180 ° C. In the case of extremely short exposure to moisture, for example extremely superheated steam, this steam may also be hotter.
  • Upper temperature limit is the duration of the treatment.
  • the partial hydrolysis (step D) can also be carried out in climatic chambers in which the hydrolysis can be controlled in a controlled manner under defined action of moisture.
  • the moisture by the temperature or saturation of the
  • contacting environment such as gases such as air, nitrogen, carbon dioxide or other suitable gases, or steam can be adjusted specifically.
  • gases such as air, nitrogen, carbon dioxide or other suitable gases, or steam
  • the duration of treatment depends on the parameters selected above.
  • the treatment duration of the membrane depends on its thickness. As a rule, the treatment duration is between a few seconds to
  • the treatment time is preferably between 10 seconds and 300 hours, in particular 1 minute to 200 hours.
  • the treatment duration is between 1 and 200 hours.
  • the polymer film obtained according to step D) is preferably self-supporting, i. it can be released from the carrier without damage according to step E) and then optionally further processed directly.
  • step D is further processed, for example, to a composite membrane, step D) can be waived in whole or in part.
  • the treatment of the film in step b) can be carried out in a hydrolysis bath analogously to step D).
  • the polyphosphoric acid or phosphoric acid present in the membrane is completely or at least partially replaced by the solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent, in particular at least one bridging and / or cross-linking reagent.
  • the stabilization reaction according to step c) can be carried out in the hydrolysis bath or afterwards, preferably immediately thereafter.
  • the treatment can be carried out in a hydrolysis bath on a carrier or else the carrier can already be removed beforehand, so that step E) can possibly be omitted or
  • This variant is also the subject of the present invention.
  • step B the existing polyphosphoric acid or phosphoric acid is removed from the membrane.
  • the treatment of the polymer layer produced according to step C) takes place in the presence of moisture at temperatures and for a sufficient time until the layer has sufficient strength for further handling.
  • the hydrolysis in step D) and the detachment in step E) can also take place simultaneously. This simplification of Hydrolysis is particularly possible if the existing polyphosphoric acid or phosphoric acid is to be completely removed and need not be present for the treatment in step b), since a fresh solution comprising a strong acid is fed again later in step b).
  • Phosphoric acid according to step F) to be removed this can be done by means of a treatment liquid in the temperature range between room temperature (20 0 C) and the boiling temperature of the treatment liquid (at atmospheric pressure).
  • liquid present solvent selected from the group of alcohols, ketones, alkanes (aliphatic and cycloaliphatic), ethers (aliphatic and cycloaliphatic), Glycols, esters, carboxylic acids, wherein the above group members may be halogenated, water and mixtures thereof used.
  • C 1 -C 10 alcohols Preferably, C 1 -C 10 alcohols, C 2 -C 5 ketones, C 1 -C 10 alkanes
  • step F) treatment liquid is removed again. This is done, preferably by drying, the parameters
  • Temperature and the ambient pressure depending on the partial vapor pressure of the treatment liquid can be selected. Usually, the drying is carried out at atmospheric pressure and temperatures between 20 0 C and 200 0 C. A gentler drying can also be done in vacuo. Instead of drying can also be blotted into the membrane and thus be freed of excess treatment liquid. The order is not critical.
  • the preparation of the film comprising polyazoles can also be carried out by varying the above method.
  • the following steps are carried out: i) reaction of one or more aromatic tetra-amino acids
  • heteroaromatic diaminocarboxylic acids in the melt at temperatures of up to 350 0 C 1 is preferably up to 300 0 C, ii) dissolving the solid prepolymer obtained in step i) in
  • step iv) treatment of the membrane formed in step iv) until it is self-supporting.
  • step II heating the solution obtainable according to step I) under inert gas
  • steps E) and F) are still carried out after steps v) and IV), whereby both variants A) and B) are also possible.
  • preferably high molecular weight polyazole may also be a blend of one or more, preferably high molecular weight
  • Polyazoles be used with another polymer.
  • the blend component essentially has the task of improving the mechanical properties and reducing the material costs.
  • a preferred blend component is polyethersulfone as described in German Patent Application No. 10052242.4.
  • polystyrene polymethylstyrene
  • polyvinyl alcohol polyvinyl acetate
  • polyvinyl ether polyvinylamine
  • Poly (N-vinylacetamide) polyvinylimidazole
  • polyvinylcarbazole polyvinylpyrrolidone
  • Polyvinylpyridine polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene
  • Polyvinylidene fluoride polyacrolein, polyacrylamide, polyacrylonitrile, polycyanoacrylates,
  • Polyacetal polyoxymethylene, polyether, polypropylene oxide, polyepichlorohydrin,
  • Polyhydroxyacetic acid Polyethylene terephthalate, polybutylene terephthalate,
  • Polyhydroxybenzoate polyhydroxypropionic acid, polypivalolactone, polycaprolactone,
  • Polymers with C-S bonds in the main chain for example polysulfide ethers,
  • Polyimines polyisocyanides, polyetherimine, polyaniline, polyamides, polyhydrazides,
  • Polyurethanes polyimides, polyazoles, polyazines
  • Liquid crystalline polymers especially Vectra and
  • Inorganic polymers for example polysilanes, polycarbosilanes, polysiloxanes,
  • Polysilicic acid Polysilicates, silicones, polyphosphazenes and polythiazyl.
  • blend polymers which have a glass transition temperature or Vicat softening temperature VST / A / 50 of at least 100 ° C., preferably at least 150 ° C. and very particularly preferably at least 180 ° C.
  • polysulfones having a Vicat softening temperature VST / A / 50 of 180 0 C to 230 0 C are preferred.
  • Preferred polymers include polysulfones, especially polysulfone having aromatics in the backbone. According to a particular aspect of the present invention, preferred polysulfones and polyethersulfones
  • a melt volume rate MVR 300/21, 6 is less than or equal to 40 cm 3/10 min, especially less than or equal to 30 cm 3/10 min and particularly preferably less than or equal to 20 cm 3/10 min measured in accordance with ISO 1133rd
  • Non-limiting examples of proton-conductive fillers are:
  • Sulfates such as: CsHSO 4 , Fe (SO 4 ) 2 , (NH 4 ) 3 H (SO 4 ) 2, LiHSO 4 , NaHSO 4 , KHSO 4 ,
  • Phosphates such as Zr 3 (PO 4 ) 4 , Zr (HPO 4 ) 2 , HZr 2 (PO 4 ) 3 , UO 2 PO 4 .3H 2 O, H 8 UO 2 PO 4 ,
  • Phosphides such as ZrP, TiP, HfP
  • Oxides such as Al 2 O 3 , Sb 2 O 5 , ThO 2 , SnO 2 , ZrO 2 , MoO 3
  • Silicates such as zeolites, zeolites (NH 4 +), phyllosilicates, framework silicates, H-natrolites,
  • H-mordenites NH 4 -alcines, NH 4 -sodalites, NH 4 -gallates, H-montmorillonites, other condensation products of orthosilicic acid Si (OH) 4 and their salts and esters, polysiloxanes of the general formula H 3 Si (O-) SiH 2 -) n -O-SiH 3 , especially others
  • Clay minerals such as montmorillonites, bertonites, kaolinites, pyrophillites, talc, chlorites, muscovites, mica, smectites, halosites,
  • Acids such as HCIO 4 , SbF 5
  • Fillers such as carbides, in particular SiC, Si3N4, fibers, in particular
  • the fillers may also be partially or completely modified, based on the aromatic fraction, by charged groups, in which connection sulphonic acid groups,
  • Phosphonic acid groups, phosphate groups or other anionic or cationic charged groups are particularly suitable.
  • the membrane comprises at most 80% by weight, preferably at most 50% by weight and more preferably at most 20%
  • additives may be present in different particle shapes and particle sizes or even mixtures, but more preferably in the form of nano-particles (particles with a size of 1 to 100 nm).
  • the stabilizing reagent used according to the invention is a compound having a functional group which reacts with the polyazole,
  • the stabilizing reagent is a bridging reagent, it preferably has at least two functional groups in the molecule which are capable of reacting with the polyazole, in particular with the amino group. Furthermore, this is an organic compound.
  • the stabilizing reagent is a crosslinking reagent, it preferably has at least three functional groups which are capable of reacting with the polyazole, in particular with the amino group, in the molecule. Furthermore, this is an organic compound.
  • Crosslinking reagent organic compounds used must have sufficient stability against the present in the solution strong acid. Furthermore, they must have sufficient solubility in the strong acid. The solubility must therefore be sufficient for the solution in step b) to be capable of producing a total content of stabilizing reagent, in particular a bridging and / or crosslinking reagent, in the range from 0.01 to 30% by weight, preferably 0, 1 to 25 wt .-%, preferably 0.5 to 15 wt .-%, in particular 1 to 5 wt .-%, to be contained, wherein the total amount of
  • Stabilizing reagents based on the polyazole present in the film, preferably in the range of 0.01 to 100 mol%, preferably 10 to 80 mol%, in particular 15 to 65 mol%.
  • the stabilizing reagent used according to the invention are compounds having a functional group which can react with the polyazole, in particular with the amino group of the polyazole present.
  • the stabilizing reagent used is preferably substances which have at least one epoxide group per molecule.
  • the stabilizing reagents which have at least one epoxide group per molecule are preferably organic compounds of the formula (A)
  • bridging reagents which have at least two epoxide groups, more preferably at least 3, have proven particularly useful
  • R 1 represents a hydrocarbon group of 1 to 30 carbon atoms, preferably a straight-chain or branched one
  • radicals (i) may be substituted by one or more nitro groups, oxygen atoms, epoxide groups or aryl groups, (ii) in which individual, non-adjacent carbon atoms are replaced by heteroatoms, in particular nitrogen, oxygen, And (iii) in which one or more hydrogen atoms, in particular in the epoxide groups, are replaced by a halogen or an alkyl, in particular a lower alkyl, or an alkoxyl, in particular a lower alkoxy, or aryl group, preferably one
  • Aryl group having 4 to 20 carbon atoms, substituted or substituted are also understood as meaning heteroaryls having 4 to 20 carbon atoms, in particular preferred aryls being in particular phenyl, naphthyl and indenyl.
  • lower alkyl or lower alkoxy means an alkyl or alkoxy group having 1 to 15 carbon atoms.
  • aryl or heteroaryl means an aryl or heteroaryl of 4 to 20
  • the heteroatoms are usually from the group of
  • Hydrogen atoms present in the formulas, in particular in the epoxide groups, may be replaced or substituted by a halogen or a lower alkyl group.
  • R 1 examples are the following groups.
  • m, k and I are the same or different and each represents an integer of 1 to 6.
  • the bridging reagents which have at least two epoxide groups per molecule are particularly preferably resorcinol diglycidyl ether (compound formula III, trade name, for example Denacol EX-201)
  • crosslinking reagents which have at least three epoxide groups per molecule are preferably organic compounds of the formula (III)
  • Particularly preferred bridging reagents are bis-phenol-A-glycidyl ether [BPAGDE] and 1,4-butyl diglycidyl ether.
  • the solution according to step b) according to the invention contains 0.01 to 30 wt .-% of stabilizing reagent, in particular bridging and / or crosslinking reagent, wherein the total amount of stabilizing reagents based on the polyazole present in the film preferably in the range of 0.01 to 100 mol%.
  • the proportion of bridging or crosslinking agent chosen too low the polymer membrane is not sufficiently stabilized, the proportion is too high, the membrane is brittle and the fracture toughness is insufficient.
  • the stabilization is preferably carried out by heating, advantageously under inert gas, to temperatures of up to 250 ° C., preferably to temperature ranges from 100 ° C. to 160 ° C., conveniently for a period of 5 minutes to 120 minutes, preferably 5 minutes to 30 minutes, more preferably 10 mins.
  • the stabilized film at temperatures of 20 0 C to 80 0 C, especially preferably 60 ° C. be postconditioned in an acidic solution for 10 minutes to 60 minutes.
  • step c) The implementation of the stabilization reaction, in particular the bridging or crosslinking, according to step c) can also by irradiation with
  • electromagnetic waves e.g., photochemical reaction, IP and / or UV irradiation
  • electrons or thermal.
  • thermal waves e.g., photochemical reaction, IP and / or UV irradiation
  • reaction it is advantageous to carry out the reaction in a temperature range of 20 0 C (room temperature) to 200 0 C.
  • the reaction time is from a few minutes to several hours, depending on the reactivity of the reagent.
  • the stabilization reaction can be carried out in one or more stages.
  • the stabilization is described below by way of example with reference to a modification of a polybenzimidazole with a monofunctional epoxide compound and by means of a bridging with an epoxy compound of the formula (IIa) with the
  • R 1 has the meaning given above.
  • the strong acid used according to the invention are protic acids, preferably phosphoric acid and / or sulfuric acid.
  • phosphoric acid is understood as meaning polyphosphoric acid, phosphonic acid (H 3 PO 3 ), orthophosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H 4 P 2 O 7 ), triphosphoric acid (H 5 P 3 Oio), metaphosphoric acid, and the like
  • Derivatives in particular organic derivatives, such as cyclic organo-phosphoric acids, and their derivatives, such as acid esters.
  • the phosphoric acid in particular orthophosphoric acid, preferably has a concentration of at least 80 wt .-%, more preferably a concentration of at least 90 wt .-%, even more preferably a concentration of at least 95 wt .-% and most preferably a concentration of at least 98% by weight.
  • the data refers to the effective
  • step b) other components (except acid & stabilizing reagent) may be present.
  • the additives mentioned at the outset can be added.
  • additional catalysts for a stabilization reaction can be added, such as small amount of strong acids, starter reagents or activating metal ions, peroxides or other substances that react with the invention
  • positively influence stabilizing reagents For further adaptation for later use, after stabilization or bridging and / or crosslinking, an additional doping of the membrane can take place.
  • the additives mentioned at the beginning can be added or the degree of doping can be carried out by further addition of the stated strong acids.
  • the membrane existing water, for example by concentration of the strong acid present be withdrawn.
  • the acidic polyazole membrane according to the invention based on stabilized, in particular bridged and / or crosslinked, preferably high molecular weight, polyazole polymers forms an acid-base complex with the acid and is therefore proton-conducting even without the presence of water. This so-called
  • Grotthus conductivity mechanism allows use in high-temperature fuel cells, with a continuous operating temperature of min. 120 ° C., preferably min. 140 0 C, in particular min. 160 0 C.
  • the membrane of the invention can therefore be used as an electrolyte for electrochemical cells, in particular fuel cells.
  • a membrane of the invention shows an E modulus of at least 3 MPa, suitably of at least 4 MPa, preferably of at least 5 MPa, more preferably of at least 6 MPa, desirably of
  • the membranes according to the invention exhibit an elongation at break of at least 85%, preferably of at least 200%.
  • the tensile elongation properties are determined preferably with a Zwick Z010 standard tension gauge, whereby the following procedure has proven particularly useful.
  • the samples are first conveniently cut into 1, 5 cm wide and 12 cm long strips. It is preferable to prepare and measure 2 to 3 samples per sample and then to average the results.
  • the thickness of the samples is preferably determined with a Mitutoyo Absolute Digmatic thickness gauge at 3 points and averaged (preferably at the beginning, middle and end of the strip). The measurement is preferably carried out as follows. Of the
  • the proton conductivity of the stabilized membranes is between 50 and 220 mS / cm at 160 ° C., preferably at least 90-220 mS / cm, more preferably between 150 and 220 mS / cm.
  • the proton conductivities are measured by means of impedance spectroscopy (Zahner IM5 or IM6 spectrometer) and a 4-point measuring cell.
  • impedance spectroscopy Zahner IM5 or IM6 spectrometer
  • a 4-point measuring cell A particularly preferred procedure is as follows.
  • Thickness gauge determined and averaged at 3 points (beginning, middle and end of the sample strip).
  • the sample is expediently fixed in the measuring cell, as shown in the figure (FIG. 1).
  • the screws of the test cell are preferably tightened hand-tight and the cell is conveniently transferred to a controlled oven, which proceeds with the according to Table 1 a temperature, frequency program.
  • the oven program is started and there are impedance spectra with a Zahner electrics impedance spectrometer IM6 with a 4-point dry cell at 20 0 C to 160 0 C and - conversely - from 160 0 C to 20 0 C, preferably in 20 0 C.
  • the acidic polyazole membranes according to the invention based on stabilized, especially bridged and / or crosslinked, preferably high molecular weight polyazole polymers are also characterized by increased stability when used as a proton-conducting membrane in high-temperature fuel cells. In the operation of such systems has been shown that, especially in phosphoric acid systems, the stability of the acidic
  • Polyazole membranes should be further improved.
  • the membranes of the invention are characterized by such improved stability and are preferably insoluble in 99% phosphoric acid over the temperature range of 85 ° C to 180 0 C. Insoluble in this context means that in an excess of the present acid, the swelling does not exceed 300% and no dissolution of the self-supporting film occurs.
  • Additional applications also include use as an electrolyte for
  • Display element an electrochromic element or various sensors.
  • Another object of the present invention is also the preferred
  • the single cell for a fuel cell contains at least one membrane according to the invention and two electrodes, between which the proton-conducting membrane is sandwiched.
  • the electrodes each have a catalytically active layer and a
  • Gas diffusion layer for supplying a reaction gas to the catalytically active Shift up.
  • the gas diffusion layer is porous so that reactive gas can pass through.
  • the polymer electrolyte membrane of the present invention can be used as the electrolyte membrane. In addition, you can the electrolyte membrane and a
  • Another subject of the present invention is a fuel cell having a plurality of individual cells (MEU 's ) each containing a membrane prepared by the above method and two electrodes sandwiching the membrane therebetween.
  • MEU 's individual cells
  • the stabilization according to the invention can also be carried out after preparation of an MEU from a membrane.
  • a doping of the membrane with the stabilizing agent preferably takes place as described above.
  • Stabilization reaction according to step c) or the activation of the stabilizing component preferably takes place subsequently within the sandwiched MEU.
  • the stabilization reaction according to step c) can also be carried out here by irradiation with electromagnetic waves (for example photochemical reaction, IR and / or UV irradiation), electrons or thermally.
  • electromagnetic waves for example photochemical reaction, IR and / or UV irradiation
  • electrons or thermally.
  • thermal reaction it is advantageous to the reaction in one
  • the stabilization takes place at 160-200 ° C.
  • Reaction time is from a few minutes to several hours, depending on the reactivity of the reagent.
  • the stabilization reaction in an MEU can be carried out in one or more stages (temperature ramp).
  • a film or a film comprising preferably high molecular weight polyazoles and a strong acid is particularly in a bath with an aqueous solvent, more preferably pure water, at a temperature between 0 ° and 90 0 C. preferably 40 - 70 0 C, inserted.
  • the acid contained in the film is diluted by dilution of solvent or completely washed out. The acid can be exchanged for 1 - 100% percent against water.
  • the film is then placed in another bath which contains an organic solvent, preferably DMAc or NMP, as well as at least one of the stabilizing agents according to the invention.
  • the bath particularly preferably contains 0.01 to 30% by weight of the stabilizing component.
  • a doping of the film takes place by solvent exchange, the previously introduced aqueous solvent being replaced by an organic solution containing at least one stabilizing agent.
  • a temperature of at least 0 ° C., but at most 120 ° C. is used with particular preference.
  • the film remains there for a period of one minute to 24 hours. The temperature must be below the temperature at which the stabilizing agent is activated.
  • the film is then removed from the bath and the supernatant
  • Solvent may be re-absorbed with a cloth but may remain on the surface. Then proceed according to route I a or route I b.
  • the film is then by treatment at 70 - 200 0 C between two carrier films (eg polyethylene terephthalate (250 microns) or glass plates) in a heating oven for a time of one minute to 24 hours, more preferably 100 - 160 0 C at a Duration of up to 10 hours, treated with stabilization taking place.
  • carrier films eg polyethylene terephthalate (250 microns) or glass plates
  • a stepwise increase and / or decrease in the temperature in the oven is possible.
  • the film is carried out after
  • Stabilization taken from the solution and can (i) directly
  • Conditioning is important to adjust the concentration of the acid in the film for specific uses.
  • Route I b stabilization in an acid medium, advantage of higher conductivities of the membranes:
  • the film is then transferred to another bath, which preheated, preferably 70 - 200 0 C 1 contains a strong acid, or an acid mixture and is left there for several minutes to several hours, the
  • Stabilization according to the invention takes place directly in a liquid, acidic medium.
  • concentration of the acid is between 10 and 99%, particularly preferably 30-85%.
  • the film is removed from the solution after stabilization has taken place and can be (i) directly further processed / used or (ii) preferably over a period of 30 minutes to 24 hours in a bath of phosphoric acid with a concentration of 30-99%, particularly preferably 30-85%, are conditioned.
  • This conditioning is important, for example, to adjust the concentration of the acid contained in the film for specific uses.
  • a film or a film comprising preferably high molecular weight polyazoles and at least one strong acid is placed in a bath which contains a strong acid and one of the stabilizing reagents according to the invention.
  • the bath particularly preferably contains 0.01-30% by weight of the stabilizing substance.
  • a doping of the film takes place by solvent exchange, wherein the previously introduced aqueous solvent is exchanged with the acidic solution with the stabilizing agent.
  • a temperature of at least 0 ° C., but at most 120 ° C. is used with particular preference.
  • the film is then removed from the bath and any excess solvent can be re-absorbed, but also remain on the surface of the film. Then proceed according to route IIa or route IIb.
  • the film is then by treatment at 70 - 200 0 C between two carrier films (eg polyethylene terephthalate (250 microns) or glass plates) from one minute to 24 hours, more preferably 100 - 160 0 C for a period of up to 10 hours treated, wherein the stabilization according to the invention takes place.
  • carrier films eg polyethylene terephthalate (250 microns) or glass plates
  • a stepwise increase and / or decrease in the temperature in the oven is possible.
  • the film is removed from the solution after stabilization has taken place and can be (i) directly further processed / used or (ii) preferably over a period of 30 minutes to 24 hours in a bath of phosphoric acid with a concentration of 30-99%, particularly preferably 30-85%, are conditioned.
  • This conditioning is important, for example, to adjust the concentration of the acid contained in the film for specific uses.
  • the film is then transferred to another bath, which preheated, preferably 70 - 200 0 C, a strong acid, or an acid mixture and is left there for several minutes to several hours, the
  • the concentration of the acid is between 10 and 99%, particularly preferably 30-85%.
  • the film is removed from the solution after stabilization has taken place and can be (i) directly further processed / used or (ii) preferably over a period of 30 minutes to 24 hours in a bath of phosphoric acid with a concentration of 30-99%, particularly preferably 30-85%, are conditioned.
  • This conditioning is important, for example, to adjust the concentration of the acid contained in the film for specific uses.
  • Table 1 shows the differences in the conductivities of various membranes which were prepared either by the already known procedure (route Ia; comparison) or else by the method according to the invention (route I b).
  • the stabilized membranes of the invention are further distinguished by improved long-term stability.
  • a membrane electrode assembly (MEA) is prepared from the membrane together with two electrodes (as described below), preferably loaded with Pt catalyst. The membrane is then within the MEU in a single cell measurement strongly oxidative conditions
  • the single measuring cell is heated for the measurement to 160 0 C, supplied with about 3 - 5 L / h of hydrogen gas on the anode side and about 5 L / h of air on the cathode side and retracted.
  • the original voltage of the cell and the cell resistance are measured.
  • the measurement of the original voltage by means of impedance spectroscopy is also known to experts and state of the art.
  • the cell without gas supply is kept at 160 ° C kept under atmospheric conditions.
  • the determination of the OCV is repeated 2 to 3 times a week.
  • An incoming damage to the membrane in the MEA is due to a sinking initial stress and / or increasing cell resistance
  • the stand-by test is terminated when the cell voltage drops below 800 mV. At the beginning of the measurement, this is typically about 1000 mV.
  • the membrane of the invention improves the stability against the
  • a comparison membrane shows a drop in OCV to below 800 mV after approximately 250 h (+/- 50 h) residence time in the cell under the conditions indicated.
  • the stabilized membranes degrade depending on the proportion
  • Table 2 shows the decrease of OCV for standard membranes in an MEA (MEA 1 and MEA 2) compared to a membrane stabilized with 0.5% by weight of pentaerythritol polyglycidyl ether on Route Ia.
  • the decrease to OCV 800 mV takes place on average for the standard membranes at 250 h, while the stabilized membrane drops only after about 1200 h below this value.

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Abstract

La présente invention concerne un procédé pour stabiliser des polymères de polyazole, comprenant les étapes suivantes : a) réalisation d'un film comprenant des polyazoles et présentant au moins un groupe amino dans l'unité récurrente; b) traitement du film issu de l'étape a) avec une solution comprenant (i) au moins un acide fort et (ii) au moins un réactif de stabilisation, notamment au moins un réactif de pontage et/ou de réticulation, la teneur totale en réactif de stabilisation dans la solution valant de 0,01 à 30 % en poids; c) mise en oeuvre de la réaction de stabilisation dans la membrane obtenue en b); d) éventuellement dopage supplémentaire de la membrane obtenue en c) avec un acide fort ou une concentration de l'acide fort présent par extraction de l'eau présente. Les membranes polymères de polyazole ainsi obtenues se caractérisent notamment par une conductivité élevée et une très bonne stabilité. Elles conviennent ainsi particulièrement bien aux applications dans des piles à combustible.
PCT/EP2010/003973 2009-07-09 2010-07-01 Procédé pour stabiliser des polymères contenant de l'azote WO2011003539A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012127311A1 (fr) * 2011-03-24 2012-09-27 Basf Se Procédé de stabilisation mécanique des polymères azotés

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Publication number Priority date Publication date Assignee Title
WO1996013872A1 (fr) 1994-11-01 1996-05-09 Case Western Reserve University Polymeres conducteurs des protons
WO2000044816A1 (fr) 1999-01-27 2000-08-03 Celanese Ventures Gmbh Procede de production d'un membrane polymerique ponte et pile a combustible
DE10052242A1 (de) 2000-10-21 2002-05-02 Celanese Ventures Gmbh Mit Säure dotierte, ein- oder mehrschichtige Kunststoffmembran mit Schichten aufweisend Polymerblends umfassend Polymere mit wiederkehrenden Azoleinheiten, Verfahren zur Herstellung solche Kunststoffmembranen sowie deren Verwendung
WO2002070592A2 (fr) 2001-03-07 2002-09-12 Celanese Ventures Gmbh Procede pour produire une membrane en polymere ponte et cellule electrochimique
WO2002088219A1 (fr) 2001-04-09 2002-11-07 Celanese Ventures Gmbh Membrane conductrice de protons et son utilisation
WO2003022412A2 (fr) * 2001-09-12 2003-03-20 Celanese Ventures Gmbh Membrane conductrice de protons et son utilisation
WO2004024797A1 (fr) 2002-08-29 2004-03-25 Pemeas Gmbh Film polymere a base de polyazoles et son utilisation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996013872A1 (fr) 1994-11-01 1996-05-09 Case Western Reserve University Polymeres conducteurs des protons
WO2000044816A1 (fr) 1999-01-27 2000-08-03 Celanese Ventures Gmbh Procede de production d'un membrane polymerique ponte et pile a combustible
DE10052242A1 (de) 2000-10-21 2002-05-02 Celanese Ventures Gmbh Mit Säure dotierte, ein- oder mehrschichtige Kunststoffmembran mit Schichten aufweisend Polymerblends umfassend Polymere mit wiederkehrenden Azoleinheiten, Verfahren zur Herstellung solche Kunststoffmembranen sowie deren Verwendung
WO2002070592A2 (fr) 2001-03-07 2002-09-12 Celanese Ventures Gmbh Procede pour produire une membrane en polymere ponte et cellule electrochimique
US20040118773A1 (en) * 2001-03-07 2004-06-24 Oemer Uensal Method for producing a membrane made of bridged polymer and a fuel cell
WO2002088219A1 (fr) 2001-04-09 2002-11-07 Celanese Ventures Gmbh Membrane conductrice de protons et son utilisation
WO2003022412A2 (fr) * 2001-09-12 2003-03-20 Celanese Ventures Gmbh Membrane conductrice de protons et son utilisation
WO2004024797A1 (fr) 2002-08-29 2004-03-25 Pemeas Gmbh Film polymere a base de polyazoles et son utilisation

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012127311A1 (fr) * 2011-03-24 2012-09-27 Basf Se Procédé de stabilisation mécanique des polymères azotés

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