WO2011151775A1 - Polyazoles mécaniquement stabilisés - Google Patents

Polyazoles mécaniquement stabilisés Download PDF

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Publication number
WO2011151775A1
WO2011151775A1 PCT/IB2011/052366 IB2011052366W WO2011151775A1 WO 2011151775 A1 WO2011151775 A1 WO 2011151775A1 IB 2011052366 W IB2011052366 W IB 2011052366W WO 2011151775 A1 WO2011151775 A1 WO 2011151775A1
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Prior art keywords
acid
membrane
solution
polyazole
weight
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PCT/IB2011/052366
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English (en)
Inventor
Friederike Fleischhaker
Anna Cristadoro
Jörg BELACK
Oliver Gronwald
Francisco Javier Lopez Villanueva
Bernd Bruchmann
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Basf Se
Basf (China) Company Limited
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Priority to KR1020127032362A priority Critical patent/KR20130129328A/ko
Priority to JP2013513027A priority patent/JP2014500567A/ja
Priority to EP11789338.8A priority patent/EP2576670A4/fr
Priority to CN201180026972.2A priority patent/CN104080842A/zh
Publication of WO2011151775A1 publication Critical patent/WO2011151775A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • B01D67/00113—Pretreatment of the casting solutions, e.g. thermal treatment or ageing
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • H01M8/103—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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • 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 mechanically stabilized polyazoles, especially to acid-doped, mechanically stabilized polyazoles, to processes for preparation thereof and to the use thereof in polymer electrolyte membranes (PEMs), membrane electrode units (MEUs) and PEM fuel cells, which are particularly at the forefront in the context of the present invention.
  • PEMs polymer electrolyte membranes
  • MEUs membrane electrode units
  • PEM fuel cells which are particularly at the forefront in the context of the present invention.
  • the mechanically stabilized polyazoles can be used advantageously in many further applications.
  • PEMs Polymer electrolyte membranes
  • sulfonic acid-modified polymers especially perfluorinated polymers
  • a prominent example thereof is NafionTM from DuPont de Nemours, Willmington USA.
  • NafionTM from DuPont de Nemours, Willmington USA.
  • the necessary water content but also the stability of the polymer in conjunction with acidic water and the hydrogen and oxygen reaction gases, limits the operating temperature of the PEM fuel cell stack typically to 80-100°C. Under pressure, the operating temperature can be increased to >120°C. Otherwise, higher operating temperatures cannot be achieved without a loss in performance of the fuel cell.
  • WO 96/13872 discloses the use of acid-doped polybenzimidazole membranes which are produced by a casting process.
  • the film is doped with a strong acid and used.
  • the acid-containing polyazole membranes obtained exhibit an improved mechanical stability compared to unbridged acid-containing polyazole membranes, with simultaneously good conductivity.
  • the present invention therefore provides a process for preparing mechanically stabilized polyazoles, comprising the following steps:
  • the present invention discloses particularly advantageous options for mechanical stabilization of polyazoles, preferably of acid-doped polyazoles, especially of acid- containing and proton-conducting polyazole membranes.
  • the high molecular weight polyazoles known to date were unstabilized; the polyazoles which have been modified by bridging and/or crosslinking and are known to date do not include high molecular weight polyazoles.
  • polyazoles especially acid-containing, proton-conducting, high molecular weight polyazole polymers which have an Improved modulus of elasticity and improved elongation at break. Both properties are of great significance especially for use in polymer electrolyte membranes for fuel cells.
  • conductivities of the inventive polymers which are preferably in the form of a membrane comprising at least one inventive polymer, are exceptionally high.
  • inventive polymers which are preferably in the form of a membrane comprising at least one inventive polymer, are notable for an improved compression stability, especially at temperatures in the range from 20°C to 200°C.
  • the achievement of the present invention can be implemented on the industrial scale and inexpensively in a comparatively simple manner, and is absolutely safe from a health point of view.
  • Polyazoles in the context of the present invention are understood to mean those polymers in which the repeat unit in the polymer comprises preferably at least one aromatic ring with at least one nitrogen atom.
  • the aromatic ring is preferably a five- or six-membered ring with one to three nitrogen atoms, which may be fused to another ring, especially another aromatic ring. Individual nitrogen heteroatoms may also be replaced by oxygen, phosphorus and/or sulfur atoms.
  • the heterocyclic aromatic rings are preferably in the main polymer chain, but may also be in the side chain.
  • the inventive polyazoles have at least one amino group in a repeat unit.
  • the amino group may be present as a primary amino group ⁇ NH 2 group), as a secondary amino group (NH group) or as a tertiary group, which is either part of a cyclic, optionally aromatic structure or part of a substituent on the aromatic unit.
  • the polymer Due to the amino group in the repeat unit, the polymer is basic, and the repeat unit can react preferentially via the amino group with the stabilizing reagent (polyether).
  • the amino group in the repeat unit is preferably a primary or secondary amino group, more preferably a cyclic secondary amino group, which appropriately forms part of the ring of the azole repeat unit.
  • the process according to the invention serves especially for preparation of mechanically stabilized polymer membranes based on polyazole.
  • the process according to the invention comprises the following steps: a) producing a film comprising at least one polyazole with at least one amino group in a repeat unit,
  • step b) treating the film from step a) with a solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent, the total content of stabilizing reagents in the solution being in the range from 0.01 to 30% by weight, c) performing the stabilization reaction in the membrane obtained in step b)
  • step d) optionally additionally doping the membrane obtained in step c) with a strong acid or concentrating the strong acid present by removing water present, using at least one high-functionality polyether as the stabilizing reagent.
  • the production of a film or of a foil comprising polyazoles is already known.
  • the preparation is effected, for example, as described in WO 2004/024797 and comprises the steps of:
  • heteroaromatic diaminocarboxylic acids in polyphosphoric acid to form a solution and/or dispersion
  • step B) applying a layer using the mixture from step A) to a support
  • step C) heating the flat structure/layer obtainable according to step B) under inert gas to temperatures of up to 350°C, preferably up to 280°C, to form the polyazole polymer,
  • step D) hydrolyzing the polymer film formed in step C) (until it is self-supporting),
  • step E) detaching the polymer film formed in step D) from the support
  • the aromatic and heteroaromatic tetraamino compounds used in accordance with the invention are preferably 3,3'A4'-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1 ,2,4,5-tetraaminobenzene, 3,3',4,4'-tetraaminodiphenyl sulfone, 3,3',4,4'- tetraaminodiphenyl ether, 3,3',4,4'-tetraaminobenzophenone, 3,3 ⁇ 4,4'- tetraaminodiphenylmethane and 3,3 4,4Metraaminodiphenyldimethylmethane and salts thereof, especially the mono-, di-, tri- and tetrahydrochloride derivatives thereof.
  • aromatic carboxylic acids used in accordance with the invention are dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids, or the esters thereof or the anhydrides thereof or the acid chlorides thereof.
  • aromatic carboxylic acids likewise also comprises heteroaromatic carboxylic acids.
  • the aromatic dicarboxylic acids are preferably isophtha!ic acid, terephthalic acid, phthalic acid, 5- hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthallc acid, 5- aminoisophthalic acid, 5-N,N-dimethylaminoisophthalic acid, 5- ⁇ , ⁇ - diethylaminoisophthalic 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, 3-fluorophthalic acid, 5-fluoroisophthalic acid, 2- fluoroterephthalic acid, tetrafluorophthalic acid, tetrafluoroisophthalic acid, tetrafluoroterephthalic acid,1 ,4-naphthalenedicarboxyiic acid, 1 ,5- naphthalenedicar
  • aromatic tri-, tetracarboxylic acids or the C1-C20-alkyl esters or C5- C12-aryl esters thereof or the acid anhydrides thereof or the acid chlorides thereof 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 the C1 -C20-alkyl esters or C5-C12-aryl esters thereof or the acid anhydrides thereof or the acid chlorides thereof are preferably 3,5,3',5'-biphenyltetracarboxylic acid, benzene-1 ,2,4,5-tetracarboxylic 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 in accordance with the invention are heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids, or the esters thereof or the anhydrides thereof.
  • Heteroaromatic carboxylic acids are understood to mean aromatic systems which contain at least one nitrogen, oxygen, sulfur or phosphorus atom in the aromatic ring.
  • pyrldine-2,5- dicarboxylic acid pyridine-3,5-dicarboxylic acid, pyridlne-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedlcarboxylic acid, 3,5- pyrazoledicarboxylic acid, 2,6-pyrimidinedicarboxyl!c acid, 2,5-pyrazinedicarboxylic acid, 2 ,4,6-pyridinetricarboxylic acid, benzlmidazole-5,6-dicarboxylic acid, and also the C1-C20-alkyl esters or C5-C12-aryl esters thereof, or the acid anhydrides thereof or the acid chlorides thereof.
  • the content of tricarboxylic acid or tetracarboxylic acid is between 0 and 30 mol%, preferably 0.1 and 20 mol%, especially 0.5 and
  • aromatic and heteroaromatic diaminocarboxylic acids used in accordance with the invention are preferably diaminobenzoic acid and the mono- and dihydrochloride derivatives thereof.
  • step A mixtures of at least 2 different aromatic carboxylic acids are used.
  • mixtures which comprise, as well as aromatic carboxylic acids, also heteroaromatic carboxylic acids are used.
  • the mixing ratio of aromatic carboxylic acids to heteroaromatic carboxylic acids is between 1 :99 and 99:1 , preferably 1 :50 to 50:1.
  • N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids are especially mixtures of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids.
  • Nonlimiting 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'
  • the polyphosphoric acid used in step A) comprises commercial polyphosphoric acids as obtainable, for example, from Riedel-de Haen.
  • the polyphosphoric acids ⁇ ⁇ + 2 ⁇ 3 ⁇ + ⁇ (n>1) typically have a content, calculated as P 2 0 5 (by acidimetric means) of at least 83%.
  • P 2 0 5 by acidimetric means
  • the mixture obtained in step A) has a weight ratio of polyphosphoric acid to the sum of all monomers of 1 :10 000 to 10 000:1 , preferably 1 :1000 to 1000:1 , especially 1 :100 to 100:1.
  • the layer is formed in step B) by means of measures known per se (casting, spraying, knife-coating), which are known from the prior art for polymer film production.
  • Suitable supports are all supports which can be described as inert under the conditions. In addition to these inert supports, however, other supports are also suitable, for example polymer films, wovens and nonwovens, which bond with the layer formed in step B) and form a laminate.
  • phosphoric acid cone, phosphoric acid, 85%
  • This can adjust the viscosity to the desired value and facilitate the formation of the membrane.
  • the layer obtained in step B) has a thickness matched to the subsequent use and is not subject to any restriction.
  • the layer formed has a thickness between 1 and 5000 pm, preferably between 1 and 3500 pm, especially between 1 and 100 pm.
  • Ar are the same or different and are each a tetravalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 1 are the same or different and are each a divalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 2 are the same or different and are each a di- or trivalent aromatic or
  • heteroaromatic group which may be mono- or polycyclic
  • Ar 3 are the same or different and are each a trivalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 4 are the same or different and are each a trivalent aromatic or heteroaromatic group which may be mono- or polycyclic
  • Ar 5 are the same or different and are each a tetravalent aromatic or heteroaromatic group which may be mono- or polycyclic
  • Ar 6 are the same or different and are each a divalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 7 are the same or different and are each a divalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 8 are the same or different and are each a trivalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 9 are the same or different and are each a di- or tri- or tetravalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • Ar 10 are the same or different and are each a di- or trivalent aromatic or
  • heteroaromatic group which may be mono- or polycyclic
  • Ar 1 are the same or different and are each a divalent aromatic or heteroaromatic group which may be mono- or polycyclic,
  • X is the same or different and is oxygen, sulfur or an amino group which bears a hydrogen atom, a group having 1-20 carbon atoms, preferably a branched or unbranched alkyl or alkoxy group, or an aryl group as further radical,
  • R is the same or different and is hydrogen, an alkyl group or an aromatic group
  • n, m are each an integer greater than or equal to 10, preferably greater than or equal to 100.
  • Preferred aromatic or heteroaromatic groups derive from benzene, naphthalene, biphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, quinoline, pyridine, bipyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, pyrrole, pyrazole, anthracene, benzopyrrole, benzotriazole, benzoxathiadiazole, benzoxadiazole, benzopyridine, benzopyrazine,
  • benzopyrazidine benzopyrimidine, benzopyrazine, benzotriazine, indolizine, quinolizine, pyridopyridine, imidazopyrimidine, pyrazinopyrimidine, carbazole, aciridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridizine, benzopteridine, phenanthroline and phenanthrene, which may optionally also be substituted.
  • Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 is as desired; in the case of phenylene, for example, Ar 1 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 , Ar 11 may be ortho-, meta- and para-phenylene. Particularly preferred groups derive from benzene and biphenyiene, which may optionally also be substituted.
  • Preferred alkyl groups are short-chain alkyl groups having 1 to 4 carbon atoms, for example 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 may be substituted.
  • Preferred substituents are halogen atoms, for example fluorine, amino groups, hydroxy groups or short-chain alkyl groups, for example methyl or ethyl groups.
  • the polyazoles may in principle also have different repeat units which differ, for example, in their X radical. However, it preferably has only identical X radicals in one repeat unit.
  • polyazole polymers are polyimidazoles, polybenzothiazoles, polybenzoxazoles, polyoxadtazoles, polyquinoxalines, polythiadiazoles,
  • the polymer comprising repeat azole units is a copolymer or a blend which comprises at least two units of the formulae (I) to (XIV) which differ from one another.
  • the polymers may be in the form of block copolymers (diblock, triblock), random copolymers, periodic copolymers and/or alternating polymers.
  • the polymer comprising repeat azole units is a polyazole which comprises only units of the formulae (I) and/or (II).
  • the number of repeat azole units in the polymer is preferably an integer greater than or equal to 10.
  • Particularly preferred polymers comprise at least 100 repeat azole units.
  • the azole units and the two fluorinated components may be joined to one another in any sequence.
  • the preparation can be effected as a polymer, random copolymer or block copolymer.
  • n and m in the above formulae may each independently be an integer greater than or equal to 10, preferably greater than or equal to 100.
  • the inventive teaching is suitable in principle for all polyazoles irrespective of molecular weight. However, it has been found to be 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 notable for a high molecular weight which, measured as the intrinsic viscosity, is at least 1.8 dl/g, preferably at least 2.0 dl/g, especially preferably at least 2.5 dl/g.
  • the upper limit is preferably not more than 8.0 dl/g, more preferably not more than 6.8 dl/g, especially preferably not more than 6.5 dl/g.
  • the molecular weight is thus well above that of the commercial polybenzimidazole (IV ⁇ 1.1 dl/g).
  • the intrinsic viscosity is determined as described below: for this purpose, the polymer is first dried at 160°C over the course of 2 h. 100 mg of the polymer thus dried are then dissolved in 100 ml of concentrated sulfuric acid (min. 96% by weight) at 80°C over the course of 4 h. The inherent or intrinsic viscosity is determined from this solution to ISO 3105 (DIN 51562, AST D2515) with an Ubbelohde viscometer at a temperature of 25°C.
  • the mixture according to step A) also comprises tricarboxylic acids or tetracarboxylic acid, this achieves branching/crosslinking of the polymer formed along the main chain. This contributes to improvement of the mechanical character.
  • heating of the mixture from step A) to temperatures of up to 350°C, preferably up to 280°C, can already bring about the formation of oligomers and/or polymers. Depending on the temperature and duration selected, it is subsequently possible to partially or entirely dispense with the heating in step C).
  • This variant too is suitable for production of the films required for step a), comprising preferably high molecular weight polyazoles.
  • 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-dicarboxyllc acid, pyridine-2,6- dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5
  • the polymer layer obtained in step C) can be treated to produce the film required for step b) in several ways.
  • the polyphosphoric acid or phosphoric acid present Is left in the membrane since it is not disruptive in the further processing.
  • the polymer layer produced in step C) is treated in the presence of moisture at temperatures and for a duration sufficient for the layer to possess sufficient strength for the intended end use.
  • the treatment can be effected to such an extent that the membrane is self-supporting, such that it can be detached from the support without damage (step E).
  • Steps D) and E) can also be effected simultaneously or in quick succession.
  • the hydrolysis in step D) can be effected by treating the polymer film formed in step C) with the solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent, where the total content of stabilizing reagents in the solution is in the range of 0.01 to 30% by weight.
  • the performance of the stabilization reaction in step c) can be combined with a thermal drying or concentration of the acid present.
  • the polymer film is treated in step D) at temperatures above 0°C and less than 150°C, preferably at temperatures between 10°C and 120°C, especially between room temperature (20°C) and 90°C, in the presence of moisture or water and/or water vapor and/or water-comprising phosphoric acid of up to 85%.
  • the treatment is effected preferably under standard pressure, but can also be effected under pressure. It is essential that the treatment occurs in the presence of sufficient moisture, as a result of which the polyphosphoric acid present contributes to reinforcement of the polymer film as a result of partial hydrolysis to form low molecular weight polyphosphoric acid and/or phosphoric acid.
  • a sol-gel transition occurs, which is found to be responsible for the particular form of the membrane.
  • the partial hydrolysis of the polyphosphoric acid in step D) leads to a reinforcement of the polymer film, such that it becomes self-supporting, and also leads to a decrease in the layer thickness.
  • the intra- and intermolecular structures present in the polyphosphoric acid layer according to step B) lead, in step C), to ordered membrane formation which is found to be responsible for the good properties of the polymer film formed.
  • the upper temperature limit of the treatment in step D) is generally 180°C. In the case of extremely brief action of moisture, for example of extremely superheated steam, this vapor may also be hotter.
  • the essential factor for the upper temperature limit is the duration of the treatment.
  • the partial hydrolysis ⁇ step D) can also be effected In climate-controlled chambers in which the hydrolysis can be controlled under defined action of moisture.
  • the moisture content can be adjusted in a controlled manner via the temperature or saturation of the contact environment, for example gases such as air, nitrogen, carbon dioxide or other suitable gases, or water vapor.
  • the treatment time depends on the parameters selected above. In addition, the treatment time for the membrane depends on the thickness.
  • the treatment time is between a few seconds and minutes, for example under the action of superheated steam, or up to whole days, for example under air at room temperature and low relative air humidity.
  • the treatment time is preferably between 10 seconds and 300 hours, especially 1 minute to 200 hours.
  • the treatment time is between 1 and 200 hours.
  • the polymer film obtained in step D) is preferably configured so as to be self- supporting, i.e. it can be detached without damage from the support in step E) and then optionally further processed directly.
  • step C) is further processed on the support, for example to give a composite membrane, it is possible to entirely or partially dispense with step D).
  • step C) the treatment of the film in step b) can be performed in a hydrolysis bath analogously to step D).
  • the polyphosphoric acid or phosphoric acid present in the membrane is replaced completely or at least partially by the solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent.
  • the stabilization reaction in step c) can be performed in the hydrolysis bath or thereafter, preferably immediately thereafter.
  • the treatment in the hydrolysis bath can be effected on a support, or else the support may already have been removed beforehand, such that step E) can optionally be dispensed with or brought forward.
  • the polyphosphoric acid or phosphoric acid present is removed from the membrane.
  • the polymer layer obtained in step C) is treated in the presence of moisture at temperatures and for a duration sufficient for the layer to have sufficient strength for further handling.
  • the hydrolysis in step D) and the detachment in step E) can also be effected simultaneously. This simplification of the hydrolysis is possible especially when the polyphosphoric acid or phosphoric acid present is to be removed completely and need not be present for the treatment in step b) since a fresh solution comprising a strong acid is supplied again later in step b).
  • step F this can be accomplished by means of a treatment liquid within the temperature range between room temperature (20°C) and the boiling temperature of the treatment liquid (at standard pressure).
  • the treatment liquids used in the context of the invention are solvents which are present in liquid form at room temperature [i.e. 20°C] and are selected from the group of the alcohols, ketones, alkanes (aliphatic and cycloaliphatic), ethers
  • the treatment liquid introduced in step F) is removed again.
  • This is accomplished preferably by drying, in which case the parameters of temperature and of ambient pressure are selected as a function of the partial vapor pressure of the treatment liquid.
  • the drying is effected at standard pressure and
  • the film comprising polyazoles can also be produced by means of variation of the above method. In this case, the following steps are carried out:
  • aromatic carboxylic acids or esters thereof which comprise at least two acid groups per carboxylic acid monomer, or one or more aromatic and/or heteroaromatic diaminocarboxylic acids in the melt at temperatures of up to 350°C, preferably up to 300°C,
  • step ii) dissolving the solid prepolymer obtained in step i) in polyphosphoric acid, iii) heating the solution obtainable in step ii) under inert gas to temperatures of up to 30O°C, preferably up to 280°C, to form the dissolved polyazole polymer, iv) forming a membrane using the solution of the polyazole polymer according to step iii) on a support and
  • step iv) treating the membrane formed in step iv) until it is self-supporting.
  • the formation can also be produced by the following steps:
  • step II) heating the solution obtainable in step I) under inert gas to temperatures of up to 400°C, III) forming a membrane using the solution of the polymer according to step II) on a support and
  • step IV treating the membrane formed in step III) until it is self-supporting.
  • step v) or IV) is followed by steps E) and F), for which both variants A) and B) are also possible.
  • the process according to the invention comprises the following steps:
  • A' preparing a solution or dispersion of at least one polyazole with at least one amino group in a repeat unit in orthophosphoric acid and/or polyphosphoric acid,
  • step A' mixing the solution or dispersion from step A') with a solution comprising (I) at least one strong acid and (ii) at least one stabilizing reagent, the total content of stabilizing reagents in the solution being in the range from 0.01 to 30% by weight,
  • step C) performing the stabilization reaction in the solution or dispersion obtained in step B') directly and/or in a downstream processing step by heating to a temperature greater than 25°C,
  • step D' optionally additionally doping the polymer obtained in step C) with a strong acid or concentrating the strong acid present by removing water present,
  • the solution or dispersion can be prepared in step A') by simply mixing the components.
  • concentration of H 3 P0 4 and/or polyphosphoric acid- containing compositions with low P2O5 concentration or the dilution of such compositions with relatively high P 2 0 5 concentration, i.e. the removal or the supply of water is also conceivable.
  • the dissolution or dispersion of the polyazole in the orthophosphoric acid and/or polyphosphoric acid is kinetically inhibited.
  • the composition is then still present in inhomogeneous form.
  • there is additionally evaporation of water out of the composition with the result that the concentration of 3PO4 and/or polyphosphoric acid changes with time.
  • the solution or dispersion is prepared in step A') by a process in which
  • At least one polyazole is dissolved and/or dispersed in orthopbosphoric acid
  • the concentration of H 3 P0 4 and/or polyphosphoric acid calculated as P2O5 based on the total amount of H3PO4 and/or
  • polyphosphoric acid and/or water selected being less than 72.0%, preferably less than 71 .7%, more preferably less than %, even more preferably less than 71 .0%, especially less than 70.5%, and
  • concentration of H 3 P0 4 and/or polyphosphoric acid calculated as P 2 0 5 based on the total amount of H3PO4 and/or polyphosphoric acid and/or water, is increased preferably by at least 0.1 %, more preferably by at least 0.5%, especially preferably by at least 1.0%, especially by at least 1.5%.
  • the solution or dispersion from step a') is generally obtainable in a manner known per se, for example by mixing the components. Further preparation methods are described in WO 02/08829.
  • the solution or dispersion from step a') is obtained by hydrolyzing a solution or dispersion which comprises at least one polyazole and polyphosphoric acid.
  • a solution or dispersion can be prepared by polymerizing the
  • the solution or dispersion from step a') comprises, based on the total weight thereof, preferably at least 1.8% by weight, more preferably at least 2.0% by weight, especially in the range from 2.2 to 2.5% by weight, of at least one polyazole with an intrinsic viscosity, measured in at least 96% by weight sulfuric acid, in the range from 3.0 to 8 g/dL.
  • the amount of orthophosphoric acid, water and optionally phosphoric acid is preferably up to 98.2% by weight and is more preferably in the range from 90.0 up to 98.0% by weight, especially in the range from 95.0 to 97.8% by weight.
  • the water is removed in step b') preferably by evaporation, especially by heating the composition from step a') to more than 100°C and/or by applying reduced pressure.
  • evaporation especially by heating the composition from step a') to more than 100°C and/or by applying reduced pressure.
  • Particular preference is given to a procedure in which the composition from step a') is heated to a temperature in the range from greater than 120°C to 240°C, especially in the range from 120°C to 160°C, appropriately for a time in the range from at least 1 h to at most 48 h, especially in the range from at least 2 h to at most 24 h.
  • the composition is prepared by ) initially charging a solution or dispersion of a polyazole with an intrinsic viscosity, measured in at least 96% by weight sulfuric acid, in the range from 3.0 to IB2011/052366
  • concentration of H 3 PO 4 and/or polyphosphoric acid calculated as P 2 0 5 (by acidimetric means) based on the total amount of H 3 PO 4 and/or polyphosphoric acid and/or water, being greater than 72,4%, preferably greater than 73.0%, more preferably greater than 74.0%, even more preferably greater than 75.0%, especially greater than 75.45%,
  • the solution or dispersion from step P) is generally obtainable in a manner known per se, for example by mixing the components. Further preparation methods are described in WO 02/08829.
  • the solution or dispersion from step P) is more preferably obtained by polymerizing the aforementioned monomers in polyphosphoric acid.
  • the solution or dispersion from step P) comprises, based on the total weight thereof,
  • up to 98.2% by weight more preferably in the range from 90.0 up to 98.0% by weight, especially in the range from 95.0 to 97.8% by weight, of polyphosphoric acid and optionally orthophosphoric acid and/or water.
  • the polyphosphoric acid used may be commercial polyphosphoric acid as
  • the polyphosphoric acid l- nOan + i (n>1) preferably has a content, calculated as P2O6 (by acidimetric means), of at least 83%.
  • step ⁇ can be effected either in portions or continuously.
  • the mixture comprises, based on the total weight thereof,
  • up to 98.4% by weight preferably in the range from 90.0 up to 98.2% by weight, especially in the range from 95.0 to 98.0% by weight, of polyphosphoric acid and optionally orthophosphoric acid and/or water.
  • step II' an inhomogeneous mixture forms at first.
  • “Inhomogeneous” refers here to a change in the optical or physical properties which alters the equality of a property over the entire extent of the system, or the homogeneity of the appearances of the solution.
  • the change in the homogeneity of the solution is manifested by interface formation (separation of liquid from the viscous mass), change in the color (typically from green to yellowish), or else the separation of clearly visible particles or solid particles from the smooth solution.
  • the solution is considered to be homogeneous where it appears to be the same as the solution or dispersion of the polyazole in polyphosphoric acid; any differences are merely in viscosity.
  • step III' The homogenization in step III') is effected preferably in a closed system, for example in an autoclave. It is also particularly favorable to condense any water which evaporates and to supply it back to the mixture, preferably by condensing the evaporating water in at least one reflux condenser which is preferably connected directly to the reaction vessel.
  • the solution homogenizes after a certain time, preferably within less than 4 h, especially after no later than 2 h.
  • the solution viscosity of the mixture falls, and an inventive usable composition forms.
  • the process comprising steps A'), B'), C) and D') preferably also serves for production of acid-doped polyazole membranes.
  • the process appropriately comprises the steps of
  • step ii) treating the membrane formed in step i) until it is self-supporting.
  • a blend of one or more preferably high molecular weight polyazoles with a further polymer.
  • the blend component essentially has the task of improving the mechanical properties and of reducing the material costs.
  • a preferred blend component is polyether sulfone as described in German patent application No. 10052242.4.
  • the preferred polymers which can be used as blend components include polyolefins such as poly(chloroprene), polyacetylene, polyphenylene, poly(p-xylylene), polyarylmethylene, polyarmethylene, polystyrene, polymethylstyrene, polyvinyl alcohol, polyvinyl acetate, polyvinyl ether, polyvinylamine, poly(N-vinylacetamide), polyvinylimidazole, polyvinylcarbazole, polyvinylpyrrolidone, pol inyf pyridine, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyhexafluoro- propylene, copolymers of PTFE with hexafluoropropylene, with perfluoropropyl vinyl ether, with trifluoronitrosomethane, with sulfonyl fluoride vinyl ether, with
  • carbalkoxyperfluoroalkoxyvinyl ether polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyacrolein, polyacrylamide, polyacrylonitrile,
  • polycyanoacrylates polymethacrylimide, cycloolefinic copolymers, especially those of norbornene;
  • polymers having C-O bonds in the backbone for example polyacetal,
  • polyoxymethylene polyethers, polypropylene oxide, polyepichlorohydrin, polytetrahydrofuran, polyphenylene oxide, polyether ketone, polyesters, especially polyhydroxyacetic acid, polyethylene terephthalate, pofybutylene terephthalate, polyhydroxybenzoate, polyhydroxypropionic acid, polypivalolactone,
  • polycaprolactone polymalonic acid, polycarbonate
  • polymers having C-S bonds in the backbone for example polysulfide ethers, polyphenylene sulfide, polyether sulfone;
  • polymers having C-N bonds in the backbone for example polyimines,
  • polyisocyanides polyetherimine, polyaniline, polyamides, polyhydrazides, polyurethanes, polyimides, polyazoles, polyazines;
  • liquid-crystalline polymers especially Vectra
  • 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 most preferably at least 180°C. Preference is given here to polysulfones with a Vicat softening temperature VST/A/50 of 180°C to 230°C.
  • the preferred polymers include polysulfones, especially polysulfone with aromatic rings in the backbone.
  • preferred polysulfones and polyether sulfones have a melt volume flow rate MVR 300/21.6 less than or equal to 40 cm 3 /10 min, especially less than or equal to 30 cm 3 /10 min and more preferably less than or equal to 20 cm 3 /10 min, measured to ISO 1133.
  • fillers especially proton- conducting fillers, can be added to the preferably high molecular weight polyazole.
  • Nonlimiting examples of proton-conducting fillers are:
  • sulfates such as: CsHSO 4 , Fe(SO 4 ) 2l (NH 4 ) 3 H(SO )2, LiHSO ) NaHSO , KHSO 4 ,
  • phosphates such as Zr 3 (PO 4 ) 4 , Zr(HPO 4 ) 2 , HZr 2 (P0 4 )3, UO 2 PO 4 .3H 2 0, H 8 UO 2 P0 4 ,
  • phosphides such as ZrP, TiP, HfP
  • silicates such as zeolites, zeolites (NH +), sheet silicates, framework silicates,
  • H-natrolite H-mordenite, NH 4 -analcine, NH 4 -sodalite, NH - gallate, H-montmorillonite, other condensation products of orthosalicic acid Si(OH) and the salts and esters thereof, polysiloxanes of the general formula H 3 Si-(O-SiH 2 -) n -O-SiH 3> and especially also other clay minerals, such as
  • montmorrillonites bentonites, kaolinites, pyrophillites, talc, chlorites, muscovites, mica, smectites, halosites, vermiculites and hydrotalcites.
  • additives such as carbides, especially SiC, Si 3 N 4 , fibers, especially glass fibers, glass powders and/or polymer fibers, preferably based on polyazoles, also partly crosslinked.
  • These additives may be present in customary amounts, although the positive properties, such as high conductivity, high lifetime and high mechanical stability of the polyazole, especially of the membrane, should not be impaired too significantly by addition of excessively large amounts of additives.
  • the polyazole especially the membrane, comprises at most 80% by weight, preferably at most 50% by weight and more preferably at most 20% by weight of additives.
  • the additives may be present in different particle forms and particle sizes, or else mixtures, but more preferably in the form of nanoparticles,
  • the polyazole is treated in step I) with a solution comprising (i) at least one strong acid and (ii) at least one stabilizing reagent.
  • Suitable stabilizing reagents include, in this context, especially all compounds which are capable of mechanically stabilizing the preferably high molecular weight polyazole.
  • the organic compounds used as stabilizing reagents must have a sufficient stability to the strong acid present in the solution. In addition, they must have a sufficient solubility in the strong acid, such that the total content of stabilizing reagents in the solution in step I) is appropriately in the range from 0.01 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.25 to 10% by weight, especially 1 to 5% by weight. To the extent that the stabilizing reagents do not have a sufficient solubility in the strong acid, it is also possible to add small amounts of further inert solubtlizers.
  • solubility should appropriately, however, be sufficient for the solution in step I) to be capable of enabling a total content of stabilizing reagent in the range from 0.01 to 100 mol% of the reagent - based on the polyazole present in the film (per repeat unit of the polyazole polymer) - preferably 10 to 80 mol%, especially 5 to 65 mol%.
  • the proportion of stabilizing reagent selected Is too low, the mechanical strength of the polyazole, especially of the polymer membrane, is not sufficiently improved; when the proportion selected is too high, the polyazole, especially the membrane, becomes brittle and the profile of properties of the polyazole, especially of the membrane, is inadequate.
  • the stabilizing reagent may partly or fully react or interact with the electrolyte. This reaction or interaction likewise results in mechanical and/or chemical stabilization of the membrane, and also stabilization with respect to the phosphoric acid
  • the proton conductivity of the stabilized polyazole, especially of the stabilized membrane, at 160°C is appropriately between 30 and 300 mS/cm, preferably between 90 and 250 mS/cm.
  • the proton conductivities are measured by means of impedance spectroscopy (Zahner IM5 or IM6 spectrometer) and a 4-point test cell.
  • impedance spectroscopy Zahner IM5 or IM6 spectrometer
  • a 4-point test cell A particular procedure is as follows.
  • ⁇ start, middle and end of the sample strip For sample preparation, pieces of approx. 3.5 * 7 cm in size are appropriately cut out, and the membrane samples are rolled a total of 10 times with a roller-shaped weight of 500 g, in order to remove excess acid.
  • the thickness of the samples is favorably determined at 3 points with a itutoyo "Absolute, Digmatic" thickness measuring instrument, and averaged ⁇ start, middle and end of the sample strip).
  • the sample is appropriately fixed in the test cell as shown in Fig. 1.
  • the screws of the test cell are preferably tightened by hand and the cell is favorably transferred into a controlled oven which runs through a temperature-frequency program according to Table .
  • Table 1 Table 1:
  • the oven program is started, and impedance spectra are measured with a Zahner- Elektrik I 6 impedance spectrometer with a 4-point dry test cell at 20°C to 160°C and - in reverse - from 60°C to 20°C, preferably in 20°C steps, favorably with a hold time of 10 min before the measurement.
  • the spectrum is saved and preferably evaluated by the literature method of Bode and Niquist.
  • the proton conductivity is calculated here by:
  • d membrane thickness (cm)
  • R resistance measured (ohms)
  • At least one high-functionality polyether preferably at least one polyetherol, is used as a stabilizing reagent.
  • a high-functionality polyetherol should be understood to mean a product which, as well as the ether groups which form the polymer skeleton, has at least three, preferably at least six and more preferably at least ten OH groups in pendant or terminal positions.
  • the polymer skeleton may be linear or branched. There are in principle no upper limits to the number of terminal or pendant functional groups, but products with a very high number of functional groups may have undesired properties, for example high viscosity or poor solubility.
  • the high- functionality polyetherols which are used in the context of the present invention have usually not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional OH groups.
  • polyetherol for use in accordance with the invention is preferably the condensation product formed from an average of at least 3, more preferably at least 4, further preferably at least 5 and especially at least 6 di-, tri- or higher-functionality alcohols.
  • the condensation product is that formed from an average of at least 3, more preferably at least 4, especially at least 5 and particularly at least 6 tri- or higher-functionality alcohols.
  • the high-functionality polyethers are hyperbranched polyetherols.
  • hyperbranched polyetherpolyols are understood to mean uncrosslinked polymer molecules with hydroxyl and ether groups which are both structurally and molecularly inhomogeneous. On the one hand, they may have a structure analogous to dendrimers proceeding from a central molecule, but with inhomogeneous chain length of the branches. On the other hand, they may also have linear regions with functional side groups.
  • dendrimeric and hyperbranched polymers see also P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, 15 No. 14, 2499.
  • hypobranched is understood to mean that the degree of branching (DB), i.e. the mean number of dendritic bonds plus the mean number of end groups per molecule, divided by the sum of the mean number of dendritic, linear and terminal bonds, multiplied by 100, is from 10 to 99.9%, preferably from 20 to 99% and more preferably 20 - 95%,
  • DB degree of branching
  • dendrimeric is understood to mean that the degree of branching is 99.9 - 100%. For a definition of the degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.
  • the trifunctional and higher-functionality alcohols used may, for example, be triols such as trimethylolmethane, trimethylolethane, trimethylolpropane (TMP), 1 ,2,4- butanetriol. It is likewise possible to use tetrols such as bistrimethylolpropane (di- TMP) or pentaerythritol. In addition, it is possible to use higher-functionality polyols such as bispentaerythritol (di-penta) or inositols. In addition, it is also possible to use alkoxylation products of the aforementioned alcohols and of glycerol, preferably with 1 - 40 alkylene oxide units per molecule.
  • triols such as trimethylolmethane, trimethylolethane, trimethylolpropane (TMP), 1 ,2,4- butanetriol. It is likewise possible to use tetrols such as bistrimethylolpropan
  • trifunctional and higher-functionality alcohols aliphatic alcohols and especially those with primary hydroxyl groups, such as trimethylolmethane, trimethylolethane, trimethylolpropane, di-T P, pentaerythritol, di-penta and alkoxylates thereof having 1 - 30 ethylene oxide units per molecule, and also glyceryl ethoxylates having 1 - 30 ethylene oxide units per molecule.
  • the trifunctional and higher-functionality alcohols can also be used in a mixture with difunctional alcohols.
  • suitable compounds with two OH groups comprise ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2- and 1 ,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1 ,2-, 1 ,3- and 1 ,4- butanediol, 1 ,2-, 1 ,3- and 1 ,5-pentanediol, hexanediol, dodecanediol,
  • cyclopentanediol cyclohexanediol, cyclohexanedimethanol, bis(4- hydroxycyclohexyl)methane, bis(4-hydroxycyclohexyl)ethane, 2,2-bis(4- hydroxycyclohexy propane, difunctional polyetherpolyols based on ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, or polytetrahydrofuran. It will be appreciated that it is also possible to use the difunctional alcohols in mixtures.
  • the diols serve for fine adjustment of the properties of the polyetherpolyol. If difunctional alcohols are used, the ratio of difunctional alcohols to the trifunctional and higher-functionality alcohols is fixed by the person skilled in the art according to the desired properties of the polyether. In general, the amount of the difunctional alcohol(s) is from 0 to 99 mol%, preferably 0 - 80 mol%, more preferably 0 - 75 mol% and most preferably 0 - 50 mol% based on the total amount of all alcohols. By virtue of addition of trifunctional and higher-functionality alcohols and diols varying in the course of the reaction, it is also possible to obtain block copolyethers, for example diol-terminated polyethers.
  • monools may, for example, be linear or branched-chain, aliphatic or aromatic monools. They preferably have more than 3 and more preferably more than 6 carbon atoms. Also suitable as monools are monofunctional polyetherols. Preferably not more than 50 mol% of monool, based on the total amount of the trifunctional and higher-functionality alcohol, is added.
  • Polyethers which are very particularly suitable in the context of the present invention can be obtained by reaction of triethylene glycol and pentaerythritol, preferably from a triethylene glycol/pentaerythritol mixture with a molar ratio in the range from 1 :10 to 10:1 , more preferably 1 :5 to 5: 1 , even more preferably 1 :2 to 2: 1 , especially 1.5: 1 to 1 :1.5, most preferably 1 :1.
  • the polyether preferably has a number- average molecular weight in the range from 100 g/mol to 5000 g/mol, especially in the range from 700 g/mol to 1500 g/mol. Its weight-average molecular weight is appropriately in the range from 1000 g/mol to 100000 g/mol, especially in the range from 5000 g mol to 50 000 g mol.
  • high-functionality polyethers based on glycerol are used as a stabilizing reagent.
  • the preparation of polyethers based on glycerol has likewise been described. For example,
  • DE 103 07 172 also discloses the polycondensation of glycerol in the presence of acidic catalysts, for example HCI, H2SO4, sulfonic acid or H3PO4, in the absence of water at temperatures of 200°C to 280°C within 5 to 15 hours.
  • acidic catalysts for example HCI, H2SO4, sulfonic acid or H3PO4
  • EP 141253, DE 4446877 and US 5,728,796 disclose the reaction of trifunctional and higher-functionality alcohols under acidic reaction conditions in the presence of acetone or epoxy compounds.
  • the products obtained are low molecular weight, modified alcohols.
  • WO 2004/074346 discloses the alkaline polycondensation of glycerol and the subsequent reaction of the resulting condensation product under acidic conditions with a fatty alcohol. This affords a fatty alcohol-modified polyglycerol,
  • Hyperbranched polyglyceryl ethers are also described in DE 199 47631 and
  • the preparation is effected here by ring-opening reaction of glycidol, optionally in the presence of a polyfunctional starter molecule.
  • a polyfunctional starter molecule In a further preferred embodiment of the present invention, high-functionality polyethers exclusively based on trimethylolpropane units and/or exclusively based on pentaerythritol units and/or copolymers thereof are used as a stabilizing reagent.
  • Hyperbranched polyetherols can also be prepared as disclosed, for example, in WO 00/56802 by subjecting 1 -ethyl- 1 -hydroxymethyloxetane to ring-opening polymerization with specific catalysts.
  • the polymer structure here consists exclusively of trimethylolpropane units. It is likewise possible to react 3,3- bis(hydroxymethyl)oxetane, according to Nishikubo et al., Polymer Journal 2004, 36 (5) 413, with ring opening to give a highly branched polyether polyol consisting exclusively of pentaerythritol units.
  • the polyazole is stabilized by heating to a temperature greater than 25°C, preferably greater than 50°C, more preferably greater than 100°C, appropriately to a temperature in the range from greater than 100°C to 180°C, especially to a temperature in the range from 120°C to 160°C, favorably for a period of 5 minutes to 120 minutes, preferably 15 minutes to 100 minutes, more preferably 60 minutes.
  • the stabilized film can be postconditioned at temperatures of 20°C to 80°C, more preferably 60°C, in an acid-containing solution for 10 minutes to 60 minutes.
  • the strong acid used in accordance with the invention is aprotic acid, preferably phosphoric acid and/or sulfuric acid.
  • phosphoric acid is understood to mean polyphosphoric acid, phosphonic acid (H 3 PO 3 ), orthophosphoric acid (H 3 PO 4 ), pyrophosphoric acid (H4P2O7), triphosphoric acid (H5P3O10), metaphosphoric acid and derivatives, especially organic derivatives, such as cyclic organophosphoric acids, and derivatives thereof, such as acid esters.
  • the phosphoric acid especially orthophosphoric acid, preferably has a concentration of at least 80 percent by weight, more preferably a concentration of at least 90 percent by weight, even more preferably a concentration of at least 95 percent by weight and most preferably a concentration of at least 98 percent by weight, the concentration figures being based on the effective concentration of the acid in the membrane or in the hydrolysis.
  • the stabilization in step II) may be followed by additional doping of the polyazole, especially of a membrane.
  • the additives mentioned at the outset can be added, or else the degree of doping can be effected by further addition of the strong acids mentioned.
  • water present can be withdrawn from the polyazole, especially the membrane, for example by concentrating the strong acid present. It is possible to add catalysts required in addition for a stabilization reaction and mixtures of different stabilizing agents of the abovementioned groups.
  • the present invention further provides a membrane comprising at least one mechanically stabilized polyazole obtainable by the process according to the invention.
  • the inventive acid-containing polyazole membrane based on stabilized, preferably high molecular weight polyazole polymers forms an acid-based complex with the acid, and is therefore proton-conducting even without the presence of water.
  • This mechanism called the Grotthus conductivity mechanism, enables use in high- temperature fuel cells with a sustained operating temperature of at least 120°C, preferably at least 140°C, especially at least 160°C.
  • the inventive membrane can therefore be used as an electrolyte for electrochemical cells, especially fuel cells.
  • inventive acid-containing polyazole membrane based on stabilized, preferably high molecular weight polyazole polymers is notable for improved mechanical properties.
  • an inventive membrane exhibits a modulus of elasticity of at least 3 MPa, appropriately of at least 4 MPa, preferably of at least 5 MPa, more preferably of at least 6 MPa, desirably of at least 7 MPa, especially of at least 8 MPa.
  • the inventive membranes exhibit an elongation at break of at least 150%, preferably of at least 200%, especially of at least 250%.
  • the tensile strain properties are preferably determined with a Zwick Z010 standard tensile tester, and the procedure which follows has been found to be useful. The samples are first cut appropriately into strips of width 1.5 cm and length 12 cm.
  • the thickness of the samples is preferably determined with a
  • Mitutoyo Absolute Digmatic thickness measuring instrument at 3 points and averaged (preferably at the start, middle and end of the strip).
  • the measurement is preferably carried out as follows.
  • the sample strip is clamped and held at an initial force of 0.1 N for 1 min.
  • the measurement is carried out automatically at a pulling speed of preferably 5 mm min, preferably at RT (25°C), until the modulus of elasticity (MPa) has been determined (automatic procedure by means of the Zwick Software TextExpert (Version 11). Thereafter, measurement is continued with a pulling speed of preferably 30 mm/min until the sample strip tears.
  • the fracture toughness (kJ/m 2 ) and the elongation at break (%) are determined.
  • the conductivity of the inventive acid-containing polyazole membranes based on stabilized, preferably high molecular weight polyazole polymers is preferably at least 50 mS/cm, more preferably at least 100 mS/cm, especially at least 150 mS/cm.
  • inventive acid-containing polyazole membranes based on stabilized, preferably high molecular weight polyazole polymers are additionally notable for an increased stability in the case of use as a proton-conducting membrane in high-temperature fuel cells.
  • the stability of the acid-containing polyazole membranes should be improved further.
  • the inventive membranes are notable for such an improved stability and are preferably insoluble in 99% phosphoric acid over the temperature range from 85°C to 180°C.
  • insoluble means that swelling does not exceed 300% and no dissolution of the self-supporting film occurs in an excess of the acid present.
  • inventive acid-containing polyazole membranes based on stabilized, preferably high molecular weight polyazole polymers have improved compressibility.
  • the relative decrease in membrane thickness is typically less than 40% at 160°C, 120 min according to the Weiser Imprint Test, compared to approx. 80% relative decrease in membrane thickness for a corresponding unstabilized membrane under the same conditions.
  • the Weiser Imprint Test for determination of compressibility is appropriately conducted as follows:
  • membrane samples with an area of 4.91 cm 2 (diameter 2.5 cm) are punched out and placed on a hotplate with a Kapton film as a substrate.
  • the inventive stabilized membranes are additionally notable for an improved long-term stability.
  • Additional applications also include use as an electrolyte for a display element, an electrochromic element or various sensors.
  • the present invention further provides for the preferred use of the inventive polymer electrolyte membrane in a single cell (MEU) for a fuel cell.
  • the single cell for a fuel cell comprises at least one inventive membrane and two electrodes, between which the proton-conducting membrane is arranged in a sandwich-manner.
  • the electrodes each have a catalytically active layer and a gas diffusion layer for supplying a reaction gas to the catalytically active layer.
  • the gas diffusion layer is porous, in order that reactive gas can pass through it.
  • the inventive polymer electrolyte membrane can be used as an electrolyte membrane. It is also possible to produce the electrolyte membrane and a precursor for a single cell (MEU) with one or both catalytically active layers. In addition, the single cell can also be produced by fixing the gas diffusion layer on the precursor.
  • MEU single cell
  • the present invention further provides a fuel cell comprising a plurality of single cells (MEUs), each of which comprises a membrane produced by the above process and two electrodes, between which the membrane is arranged in a sandwich-like manner.
  • MEUs single cells
  • the inventive stabilization can also be performed after production of an MEU from a membrane.
  • doping of the membrane with the stabilizing agent takes place as described above.
  • the stabilization reaction in step II) or c) or the activation of the stabilizing component takes place subsequently within the MEU arranged in the manner of a sandwich.
  • the stabilization takes place at a temperature in the range from greater than 10O°C to 180°C, especially in the range from 120°C to 160°C.
  • the reaction time is from a few minutes up to several hours, according to the reactivity of the reagent.
  • the stabilization reaction in an MEU can be performed in one or more stages (temperature ramp).
  • Example 1 Preparation of a polyether polyol based on pentaerythritol and triethylene glycol
  • the polymerization was performed in a 41 glass flask equipped with a stirrer, reflux condenser and a distillation apparatus with vacuum attachment.
  • the reaction mixture was stirred and water was removed via the distillation system.
  • the water distilled off was collected in a cooled round-bottom flask and weighed, and the conversion was thus determined as a percentage with respect to the theoretically possible full conversion.
  • reaction mixture was allowed to cool under reduced pressure.
  • KOH was added to the reaction solution. Subsequently, the mixture was stripped and cooled.
  • Example 2 Preparation of a polyether polyol based on pentaerythritol, triethylene glycol and neopentyl glycol
  • the polymerization was performed in a 4 I glass flask equipped with a stirrer, reflux condenser and a distillation apparatus with vacuum attachment.
  • the reaction mixture was stirred and water was removed via the distillation system.
  • the water distilled off was collected in a cooled round-bottom flask and weighed, and the conversion was thus determined as a percentage with respect to the theoretically possible full conversion.
  • reaction mixture was allowed to cool under reduced pressure.
  • KOH was added to the reaction solution. Subsequently, the mixture was stripped and cooled.
  • the polymerization was performed in a 4 I glass flask equipped with a stirrer, reflux condenser and a distillation apparatus with vacuum attachment.
  • the reaction mixture was stirred and water was removed via the distillation system.
  • the water distilled off was collected in a cooled round-bottom flask and weighed, and the conversion was thus determined as a percentage with respect to the theoretically possible full conversion. Thereafter, the reaction mixture was allowed to cool under reduced pressure. For neutralization, KOH was added to the reaction solution. Subsequently, the mixture was stripped and cooled.
  • the inventive product was analyzed by gel permeation chromatography with a refractometer as detector.
  • the mobile phase used was hexafluoroisopropanol (HFIP); the standard used to determine the molecular weight was polymethyl methacrylate (P MA).
  • HFIP hexafluoroisopropanol
  • P MA polymethyl methacrylate
  • the OH number was determined to DIN 53240.
  • TMP x 3EO ethoxyJated trimethylolpropane
  • Example 4 Performance of an inventive stabilization (route 1 )
  • Approx. 800 ml_ of a preferably 1 -5% by weight solution of a hyperbranched polyether (based on pentaerythritol and triethylene glycol, preferably as listed in Table 2) in preferably 50%-85% phosphoric acid are prepared in a 1000 mL Schott Duran glass bottle.
  • a piece of approx. A5 size of a standard polyazole membrane with a thickness of 350 pm (CD114), a phosphoric acid concentration of approx. 50% by weight and solids content of polyazole approx. 5% by weight is added to the solution of H 3 P0 4 , heated to 60°C, with 1-5% by weight of the hyperbranched polyether.
  • the residence time in the solution is 1 h.
  • the membrane is subsequently removed from the solution and treated between 2 support materials preferably between 120-160°C in an oven for 1 h. After stabilization has been performed, the membrane is placed into 50% phosphoric acid for a period of preferably 15-30 min.
  • Example 4a Performance of an inventive stabilization (route 2.1)
  • a hyperbranched polyether (based on pentaerythritol and triethylene glycol, preferably as listed in Table 2) is stirred into a solution consisting of preferably 2.0-2.5% by weight of a high molecular weight polyazole in preferably 99-103% phosphoric acid, and the mixture is heated at preferably
  • reaction solution is used to obtain, using a coating knife, a membrane of thickness approx. 350 pm.
  • the latter is treated between 2 support materials preferably between 120-160°C in an oven for 30 min.
  • the membrane After stabilization has been performed, the membrane is placed into 50% phosphoric acid for a period of preferably 15-30 min.
  • Example 4b Performance of an inventive stabilization (route 2.2)
  • a hyperbranched polyether (based on pentaerythritol and triethylene glycol, preferably as listed in Table 2) is stirred into a solution consisting of preferably 2.0-2.5% by weight of a high molecular weight polyazole in preferably 99-103% phosphoric acid, and the mixture is heated at preferably 80-120°C while stirring for 1 h.
  • reaction solution is used to obtain, using a coating knife, a membrane of thickness approx. 350 pm.
  • the latter is placed in 50% phosphoric acid for a period of preferably 15-30 min.
  • the membrane is removed from the solution and treated between 2 support materials preferably between 120-160°C in an oven for 30 min.
  • a hyperbranched polyether No. 3 Tab. 1 at a stirring temperature of 80°C and an oven temperature of 160°C, the following properties are achieved by route 2.2:

Abstract

L'invention porte sur un procédé de préparation de polyazoles mécaniquement stabilisés, comprenant les étapes suivantes : I) le traitement d'au moins un polyazole ayant au moins un groupe amino dans un motif répétitif, par une solution comprenant (i) au moins un acide fort et (ii) au moins un réactif de stabilisation, la teneur totale de la solution en réactifs de stabilisation étant comprise dans la plage de 0,01 à 30 % en poids, II) la mise en œuvre de la réaction de stabilisation, directement et/ou dans une étape de traitement ultérieure, par chauffage à une température supérieure à 25°C, par utilisation, en tant qu'agent de stabilisation, d'au moins un polyéther à haute fonctionnalité. Les polyazoles pouvant être ainsi obtenus sont intéressants, notamment en raison de leur grande conductivité et de leur très bonne stabilité mécanique. Ils sont donc particulièrement appropriés à être utilisés dans des piles à combustible.
PCT/IB2011/052366 2010-05-31 2011-05-30 Polyazoles mécaniquement stabilisés WO2011151775A1 (fr)

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KR1020127032362A KR20130129328A (ko) 2010-05-31 2011-05-30 기계적 안정화된 폴리아졸
JP2013513027A JP2014500567A (ja) 2010-05-31 2011-05-30 機械的に安定なポリアゾール
EP11789338.8A EP2576670A4 (fr) 2010-05-31 2011-05-30 Polyazoles mécaniquement stabilisés
CN201180026972.2A CN104080842A (zh) 2010-05-31 2011-05-30 机械稳定的聚唑

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US34991210P 2010-05-31 2010-05-31
US12/349,912 2010-05-31
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EP10164510 2010-05-31

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US8987357B2 (en) 2011-05-27 2015-03-24 Basf Se Thermoplastic molding composition
WO2016205973A1 (fr) * 2015-06-24 2016-12-29 清华大学 Membrane à échange d'ions amphotères de poly(éther fluorényle oxadiazole) partiellement fluorée et procédé de préparation correspondant
WO2016205972A1 (fr) * 2015-06-24 2016-12-29 清华大学 Membrane à échange de protons de poly(oxadiazole aryl-éther-co-bisphénol fluor) et procédé de préparation correspondant
WO2020056275A1 (fr) 2018-09-14 2020-03-19 University Of South Carolina Membranes en polybenzimidazole (pbi) pour batteries à flux redox
WO2020056268A2 (fr) 2018-09-14 2020-03-19 University Of South Carolina Membranes de polybenzimidazole (pbi) à faible perméabilité pour batteries à flux redox
US11777124B2 (en) 2020-03-06 2023-10-03 University Of South Carolina Proton-conducting PBI membrane processing with enhanced performance and durability
CN112955498B (zh) * 2018-09-14 2024-05-10 南卡罗来纳大学 用于氧化还原液流电池的聚苯并咪唑(pbi)膜

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8987357B2 (en) 2011-05-27 2015-03-24 Basf Se Thermoplastic molding composition
WO2016205973A1 (fr) * 2015-06-24 2016-12-29 清华大学 Membrane à échange d'ions amphotères de poly(éther fluorényle oxadiazole) partiellement fluorée et procédé de préparation correspondant
WO2016205972A1 (fr) * 2015-06-24 2016-12-29 清华大学 Membrane à échange de protons de poly(oxadiazole aryl-éther-co-bisphénol fluor) et procédé de préparation correspondant
WO2020056275A1 (fr) 2018-09-14 2020-03-19 University Of South Carolina Membranes en polybenzimidazole (pbi) pour batteries à flux redox
WO2020056268A2 (fr) 2018-09-14 2020-03-19 University Of South Carolina Membranes de polybenzimidazole (pbi) à faible perméabilité pour batteries à flux redox
CN112955498A (zh) * 2018-09-14 2021-06-11 南卡罗来纳大学 用于氧化还原液流电池的聚苯并咪唑(pbi)膜
EP3850697A4 (fr) * 2018-09-14 2022-07-20 University of South Carolina Membranes en polybenzimidazole (pbi) pour batteries à flux redox
EP3850698A4 (fr) * 2018-09-14 2022-07-27 University of South Carolina Membranes de polybenzimidazole (pbi) à faible perméabilité pour batteries à flux redox
US11482721B2 (en) 2018-09-14 2022-10-25 University Of South Carolina Low permeability polybenzimidazole (PBI) gel membranes for redox flow batteries
US11799112B2 (en) 2018-09-14 2023-10-24 University Of South Carolina Polybenzimidazole (PBI) membranes for redox flow batteries
CN112955498B (zh) * 2018-09-14 2024-05-10 南卡罗来纳大学 用于氧化还原液流电池的聚苯并咪唑(pbi)膜
US11777124B2 (en) 2020-03-06 2023-10-03 University Of South Carolina Proton-conducting PBI membrane processing with enhanced performance and durability

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