JP2009293045A - Proton-conducting polymer membrane comprising polymer with sulfonic acid group and use thereof in fuel cells - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a proton-conducting polymer membrane suitable for polymer electrolyte membranes and the like. <P>SOLUTION: The proton-conducting polymer membrane comprises polymers containing sulfonic acid groups and has the conductivity of at least 0.001 S/cm. The membrane is obtainable by a method comprising the steps of: (A) mixing a vinyl-containing sulfonic acid with one or more aromatic polycarboxylic acids, their esters, their acid halides, and their acid anhydrides, and one or more of aromatic tetra-amino compounds, or mixing the vinyl-containing sulfonic acid with one or more aromatic and/or heteroaromatic diaminocarboxylic acids, their esters, their acid halides, or their acid anhydrides; (B) heating the mixture obtainable according to step (A) under inert gas to temperatures of up to 350°C, to form polyazole polymers; (C) applying a layer to a support, using the mixture according to step (A) and/or (B); and (D) polymerizing the vinyl-containing sulfonic acid present in the sheetlike structure obtainable according to step (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a proton conducting polymer electrolyte membrane comprising a sulfonic acid group-containing polymer, which can be used in a variety of applications due to its remarkable chemical and thermal properties, particularly in PEM fuel cells. It is suitable as an electrolyte membrane (PEM).

A fuel cell typically includes an electrolyte and two electrodes separated by the electrolyte. In a fuel cell, one of the two electrodes is supplied with a fuel such as hydrogen gas or a methanol / water mixture and the other electrode is supplied with an oxidant such as oxygen gas or air, so that the fuel The chemical energy from the oxidation of is directly converted into electrical energy. In the oxidation reaction, protons and electrons are formed.
The electrolyte is permeable to hydrogen ions, ie protons, but not hydrogen gas or reactive fuels such as methanol and oxygen gas.

Fuel cells generally include two or more individual cells known as MEAs (membrane electrode assemblies), each including an electrolyte and two electrodes separated by the electrolyte.
The electrolyte used in the fuel cell includes a solid such as a polymer electrolyte membrane or a liquid such as phosphoric acid. In recent years, polymer electrolyte membranes have attracted attention as electrolytes for fuel cells. In principle, polymer membranes can be divided into two categories.

  The first category includes cation exchange membranes constructed from a base comprising a polymer containing covalently bonded acid groups, preferably sulfonic acid groups. Sulfonic acid groups release hydrogen ions and convert them to anions, thereby conducting protons. Proton mobility and, therefore, proton conductivity is directly related to water content. Due to the very high miscibility of methanol and water, such cation exchange membranes have high methanol permeability and are therefore not suitable for direct methanol fuel cell applications. For example, if the membrane dries as a result of the high temperature, the membrane conductivity, and thus the performance of the fuel cell, is dramatically reduced. The operating temperature of a fuel cell comprising such a cation exchange membrane is therefore limited to the boiling point of water. Fuel humidification is a major technical issue in the use of polymer electrolyte membrane fuel cells (PEMFC) in which a general-purpose sulfonated membrane such as Nafion is used.

Thus, for example, perfluorosulfonic acid polymers are used as materials for polymer electrolyte membranes. Perfluorosulfonic acid polymers (eg, Nafion) are generally composed of tetrafluoroethylene and trifluorovinyl with attached side chains containing sulfonic acid groups, such as side chains containing sulfonic acid groups attached to perfluoroalkylene groups. It has a perfluorinated hydrocarbon backbone such as a copolymer.
The cation exchange membrane preferably comprises an organic polymer containing covalently bound acid groups, in particular sulfonic acid. Methods for sulfonating polymers are described in F.W. Kucera et al., Polymer Engineering and Science 1988, Vol. 38, no. 5, 783-792 (Non-patent Document 1).

Listed below are the main types of cation exchange membranes that have gained commercial importance for use in fuel cells.
The most important representative is the perfluorosulfonic acid polymer Nafion (Nafion) (Patent Document 1). As described in US Pat. No. 4,453,991 (Patent Document 2), this polymer can be dissolved and used as an ionomer. Cation exchange membranes can also be obtained by filling a porous support material with such ionomers. A preferred support material is expanded Teflon (registered trademark) (Patent Document 3).

Another perfluorinated cation exchange membrane can be produced by copolymerization of trifluorostyrene and sulfonyl-modified trifluorostyrene as described in US Pat. No. 5,422,411. A porous support material filled with an ionomer made of such a sulfonyl-modified trifluorostyrene copolymer, particularly a composite membrane made of expanded Teflon (registered trademark) is described in US Pat. No. 5,834,523 (Patent Document 5).
US 6110616 describes copolymers of butadiene and styrene and their subsequent sulfonation to produce cation exchange membranes for fuel cells.

  A further class of partially fluorinated cation exchange membranes can be made by radiation grafting followed by sulfonation. In this case, as described in EP 667983 (Patent Document 7) or DE 19844645 (Patent Document 8), the grafting reaction is preferably carried out on a pre-irradiated polymer film using styrene. In the subsequent sulfonation reaction, the side chain is sulfonated. Cross-linking may be performed simultaneously with grafting, which can modify the mechanical properties.

In addition to the membranes, a further class of non-fluorinated membranes has been developed by sulfonated thermoplastic resins having high temperature stability. For example, sulfonated polyether ketone (DE4219077 (patent document 9), EP96 / 01177 (patent document 10)), sulfonated polysulfone (non-patent document 2: J. Membr. Sci. 83 (1993) p.211) or sulfone. A film of polyphenylene sulfide (Patent Document 11: DE19527435) is known. Ionomers produced from sulfonated polyether ketones are described in WO 00/15691 (Patent Document 12).
In addition, as described in DE 19817374 (Patent Document 13) or WO 01/18894 (Patent Document 14), an acid-base blend membrane produced by a mixture of a sulfonated polymer and a basic polymer is known. Yes.

  In order to further improve the membrane properties, it is possible to mix prior art cation exchange membranes with polymers having high temperature stability. Cation exchange consisting of a blend of a sulfonated PEK and a) polysulfone (DE 4422158 (Patent Document 15)), b) aromatic polyamide (DE 4244264 (Patent Document 16)) or c) polybenzimidazole (DE 19851498 (Patent Document 17)). The manufacture and properties of the membrane are described.

  The disadvantage of all these cation exchange membranes is the fact that the membrane must be humidified, the operating temperature is limited to 100 ° C. and the membrane has a high methanol permeability. The reason for these disadvantages is the membrane conductivity mechanism in which proton transport is linked to water molecule transport. This is known as “vehicle mechanism” (Non-Patent Document 3: K.-D. Kreuer, Chem. Mater. 1996, 8, 610-641).

As a second category, a polymer electrolyte membrane including a complex of a basic polymer and a strong acid has been developed. For example, WO 96/13872 (Patent Document 18) and the corresponding US Pat. No. 5,525,436 (Patent Document 19) treat a basic polymer such as polybenzimidazole with a strong acid such as phosphoric acid or sulfuric acid. A method for producing a proton conductive polymer electrolyte membrane is described.
J. et al. Electrochem. Soc. Vol. 142, no. 7, 1995, pp. L121-L123 (Non-Patent Document 4) describes doping polybenzimidazole in phosphoric acid.

  In the case of basic polymer membranes known from the prior art, the mineral acid (usually concentrated phosphoric acid) used to obtain the required proton conductivity is usually added after the polyazole film is formed. The polymer serves in this case as a support for an electrolyte consisting of highly concentrated phosphoric acid. The polymer membrane in this case performs a more important function. In particular, it is required to have high mechanical stability and to act as a separator for the two fuels.

  The main advantage of this type of phosphoric acid doped membrane is that fuel cells in which this type of polymer electrolyte membrane is used operate at temperatures above 100 ° C without otherwise humidifying the required fuel It is a fact that can be made. This ability is attributed to the properties of phosphate that can transport protons without further water by the so-called Grotius mechanism (K.-D. Kreuer, Chem. Mater. 1996, 8, 610-641). is there.

  The ability to operate at temperatures above 100 ° C. opens up additional advantages for fuel cell systems. First, the sensitivity of the Pt catalyst to gas contamination, particularly CO, is greatly reduced. CO is produced as a by-product in reforming natural gas, carbon-containing compounds such as methanol or benzine to hydrogen-rich gases, or as an intermediate in the direct oxidation of methanol. Typically, the CO content of the fuel at temperatures below 100 ° C. must be lower than 100 ppm. However, at temperatures in the range of 150-200 ° C., even 10000 ppm CO or higher can be tolerated (NJ Bjerrum et al., Journal of Applied Electrochemistry, 2001, 31, 773-779). . This leads to a substantial simplification of the upstream reforming process and thus to a lower cost of the entire fuel cell system.

  A major advantage of fuel cells is the fact that during the electrochemical reaction, the energy of the fuel is converted directly into electrical energy and heat. At the cathode, water is generated as a reaction product. In addition, heat is generated as a by-product in the electrochemical reaction. For example, in automotive applications or applications that only use electricity to drive an electric motor as an alternative to various storage battery systems, it is necessary to remove heat to prevent the system from overheating. Cooling requires additional energy consuming equipment that further reduces the overall electrical efficiency of the fuel cell. In static applications, such as for concentrated or unconcentrated electricity and heat generation, heat can be effectively utilized by existing technologies such as heat exchangers. In such cases, higher temperatures are required to increase efficiency. If the operating temperature exceeds 100 ° C and the temperature difference between the ambient temperature and the operating temperature is large, the fuel cell system is more efficient than a fuel cell that must be operated below 100 ° C due to membrane humidification. It is possible to cool or use a smaller cooling area and to dispense with further equipment.

  However, in addition to these advantages, this type of fuel cell system also has disadvantages. For example, the durability of films doped with phosphoric acid is relatively limited. Its lifetime is considerably reduced, especially by operating the fuel cell below 100 ° C., for example at 80 ° C. In that sense, however, it should be noted that fuel cells must be operated at their temperatures when starting and stopping.

  Furthermore, the production of membranes doped with phosphoric acid is relatively expensive. This is because usually a prepolymer is first formed and subsequently cast with the aid of a solvent to form a film. After the film is dried, it is doped with acid in the last step.

A further problem is the relatively low mechanical stability of polyazole films doped with phosphoric acid. Thus, if the mechanical stability is too low, the membrane may be damaged by the pressure generated by the gas flowing into the fuel cell used as fuel.
In addition, performance, such as the conductivity of known membranes, is relatively limited.

  Furthermore, known membranes doped with phosphoric acid cannot be used directly in methanol fuel cells (DMFC). Nevertheless, such batteries are particularly interesting. This is because a methanol / water mixture can be used as the fuel. If known membranes based on phosphoric acid are used, the fuel cell will stop working after a very short time.

US Pat. No. 3,692,569 US Pat. No. 4,453,991 US Pat. No. 5,653,041 US Pat. No. 5,422,411 US Pat. No. 5,834,523 US Pat. No. 6,110,616 European Patent Application No. 667983 German Patent Application Publication No. 1844645 German Patent Application No. 4219077, International application EP 96/01177 German Patent Application Publication No. 19527435 International Publication No. 00/15691 German Patent Application Publication No. 19817374 International Publication No. 01/18894 German Patent Application Publication No. 4422158 German Patent Application Publication No. 4,245,264 German Patent Application Publication No. 19851498 International Publication No. 96/13872 US Pat. No. 5,525,436

F. Kucera et al., Polymer Engineering and Science 1988, Vol. 38, no. 5,783-792 J. et al. Membr. Sci. 83 (1993) p. 211 K. -D. Kreuer, Chem. Mater. 1996, 8, 610-641 J. et al. Electrochem. Soc. Vol. 142, no. 7, 1995, pp. L121-L123 N. J. et al. Bjerrum et al., Journal of Applied Electrochemistry, 2001, 31, 773-779.

  Therefore, the present invention is based on the object of providing a new type of polymer electrolyte membrane that achieves the aforementioned object. In particular, it is possible to extend the operating temperature from below 0 ° C. to 200 ° C. without reducing the life of the fuel cell very rapidly.

A further object is to provide a polymer electrolyte membrane that can be used in many different fuel cells. Thus, the membrane would be suitable for fuel cells utilizing hydrogen alone and a number of carbon-containing fuels, particularly natural gas, benzine, methanol and biomass as their energy sources. In particular, the membrane can be used in hydrogen fuel cells and direct methanol fuel cells (DMFC).
Also, the membrane of the present invention is inexpensive and easy to manufacture. In addition, it is therefore an object of the present invention to provide a polymer electrolyte membrane that exhibits high performance, particularly high conductivity over a wide temperature range. Conductivity will be achieved without further humidification, especially at high temperatures.

A further object is to provide a polymer electrolyte membrane that exhibits high mechanical stability such as, for example, high modulus, high tensile strength and high fracture toughness.
Accordingly, another object of the present invention is to provide a membrane that has low permeability to various fuels, such as hydrogen or methanol, even in operation.

  These objects are achieved by a proton conducting polymer membrane comprising a sulfonic acid group-containing polymer having all the features of claim 1. Furthermore, the underlying object is achieved by an electrode having a proton-conducting polymer coating based on polyazole having all the features of claim 19.

The present invention
A) a vinyl-containing sulfonic acid with one or more aromatic tetraamino compounds comprising one or more aromatic carboxylic acids, esters thereof, acid halides or acid anhydrides thereof having at least two acid groups per carboxylic acid monomer; Mixing and / or mixing the vinyl-containing sulfonic acid with one or more aromatic and / or heteroaromatic diaminocarboxylic acids, their esters, their acid halides or their anhydrides,
B) The mixture obtained by step A) is heated under inert gas to a temperature of up to 350 ° C. to form a polyazole polymer,
C) using the mixture according to step A) and / or B) to apply a layer to the support,
D) Provided is a proton conductive polymer membrane containing a sulfonic acid group-containing polymer, which can be obtained by a method comprising a step of polymerizing a vinyl-containing sulfonic acid present in the sheet-like structure obtained by step C).

The membranes of the present invention exhibit high conductivity over a large temperature range that is achieved without further humidification. Furthermore, the fuel cell comprising the membrane of the present invention can thereby be operated at low temperatures, for example at 80 ° C., without significantly reducing the life of the fuel cell.
The polymer electrolyte membrane of the present invention has very low methanol permeability and is therefore particularly suitable for use in DMFC. Thus, it is possible to operate a fuel cell for a long time with a very large number of fuels such as hydrogen, natural gas, benzine, methanol or biomass.
Moreover, the membrane of the present invention can be produced easily and inexpensively. In particular, it is not necessary to use a large amount of an expensive and harmful solvent such as dimethylacetamide.
Furthermore, the films of the present invention exhibit high mechanical stability, in particular high modulus, high tensile strength and high fracture toughness. These membranes additionally have a surprisingly long lifetime.

  Vinyl-containing sulfonic acids are known in the art. These are compounds containing at least one carbon-carbon double bond and at least one sulfonic acid group. Preferably, at least two, preferably three, groups are attached to the two carbon atoms forming the carbon-carbon double bond, which results in low steric hindrance of the double bond. In particular, these groups contain hydrogen atoms and halogen atoms, in particular fluorine atoms. In the present invention, polyvinyl sulfonic acid is a polymerization product obtained by polymerizing vinyl-containing sulfonic acid alone or with additional monomers and / or crosslinking agents.

  The vinyl-containing sulfonic acid can contain 1, 2, 3 or more carbon-carbon double bonds. The vinyl-containing sulfonic acid can further comprise 1, 2, 3 or more sulfonic acid groups. Generally speaking, vinyl-containing sulfonic acids contain 2 to 20, preferably 2 to 10 carbon atoms.

The vinyl-containing sulfonic acid used in step A) preferably comprises a compound of the formula:

[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula

[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula

Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² , and / or R ² , where R ² is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, ethylene a group or C5~C20 aryl or heteroaryl group, wherein the group consisting of halogen, -OH, COOZ, -CN, may be substituted by NZ _2,
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a divalent C5-C20 aryl or heteroaryl group. , -OH, COOZ, -CN, NZ ₂ may be substituted,
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
z is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. ]

Preferred vinyl-containing sulfonic acids are alkenes containing sulfonic acid groups such as ethenesulfonic acid, propenesulfonic acid, butenesulfonic acid; for example, 2-sulfomethylacrylic acid, 2-sulfomethylmethacrylic acid, 2-sulfomethylacrylamide And acrylic acid and / or methacrylic acid compounds containing sulfonic acid groups such as 2-sulfomethylmethacrylamide.
Particular preference is given to using commercially available vinyl sulphonic acids (ethene sulphonic acids) as can be obtained, for example, from Aldrich or Clariant GmbH. Preferred vinyl sulfonic acids have a purity of more than 70%, in particular 90%, more preferably more than 97%.

  The vinyl-containing sulfonic acid can be used in the form of a derivative that can be converted to an acid later, and the conversion to the acid can also be performed in a polymerized state. Such derivatives include in particular salts, esters, amides and halides of vinyl-containing sulfonic acids.

  The mixture prepared in step A) preferably comprises at least 1% by weight, in particular at least 5% by weight, more preferably at least 20% by weight, based on the total weight of the vinyl-containing sulfonic acid. According to one particular embodiment of the invention, the mixture prepared in step A) is based on a total weight of not more than 60% by weight of polyazole preparation monomer, in particular not more than 50% by weight of polyazole preparation monomer, more preferably 30%. Contains no more than% by weight of monomer for polyazole preparation.

  According to one particular embodiment of the invention, the mixture according to step A) comprises a vinyl-containing phosphonic acid. The addition of vinyl-containing phosphonic acid surprisingly can improve the high temperature properties of the membrane. By using only a relatively small amount of these phosphonic acids, the membrane of the present invention can be operated for a short time without resulting in destruction of the membrane without humidification. If the fraction of vinyl-containing phosphonic acid increases, the performance increases with increasing temperature, and this capability is obtained without humidification.

  Polyvinylphosphonic acid present in the membrane, which can also be cross-linked by reactive groups, forms an interpenetrating network with polymers having high temperature stability. Thus, erosion of the electrolyte by the product water or in the case of DMFC by the aqueous fuel is significantly reduced. The polymer electrolyte membrane of the present invention has very low methanol permeability and is particularly suitable for use in DMFC. Thus, long-term operation of the fuel cell with multiple fuels such as hydrogen, natural gas, benzine, methanol or biomass is possible. The membrane allows these fuels to exhibit particularly high activity. The oxidation of methanol is possible with high activity at high temperatures. In one particular embodiment, these membranes are suitable for operation in a so-called vapor form DMFC, especially at temperatures in the range of 100-200 ° C.

  As a result of being able to operate at temperatures above 100 ° C., the sensitivity of the Pt catalyst to gas contamination, especially CO, is significantly reduced. CO is produced, for example, as a by-product in the reforming of carbon-containing compounds such as natural gas, methanol or benzine to hydrogen-rich gases, or as an intermediate in the direct oxidation of methanol. Typically, the CO content of the fuel at temperatures above 120 ° C. can be greater than 5000 ppm, yet the catalytic activity of the Pt catalyst is not dramatically reduced. However, at temperatures in the range of 150-200 ° C., more than 10000 ppm CO is acceptable (NJ Bjerrum et al., Journal of Applied Electrochemistry, 2001, 31, 773-779). This leads to substantial simplification of the upstream reforming process and cost reduction of the entire fuel cell system.

  The membranes of the invention with a high phosphonic acid content show a high conductivity over a large temperature range, which is achieved without further humidification. Furthermore, if the sulfonic acid content is relatively high, the fuel cell provided with the membrane of the present invention can be operated at a low temperature, for example, while humidifying at 5 ° C.

Vinyl-containing phosphonic acids are known in the art. These are compounds containing at least one carbon-carbon double bond and at least one phosphonic acid group. Preferably, at least two, preferably three, groups are attached to the two carbon atoms forming the carbon-carbon double bond, which results in low steric hindrance of the double bond. These groups include, among others, hydrogen atoms and halogen atoms, especially fluorine atoms. In the present invention, polyvinyl phosphonic acid is a polymerization product obtained by polymerizing vinyl-containing phosphonic acid alone or in addition with a monomer and / or a crosslinking agent.
The vinyl-containing phosphonic acid can contain 1, 2, 3 or more carbon-carbon double bonds. Further, the vinyl-containing phosphonic acid can contain 1, 2, 3 or more phosphonic acid groups.
Generally speaking, vinyl-containing phosphonic acids contain 2 to 20, preferably 2 to 10 carbon atoms.

The vinyl-containing phosphonic acid used in step A) is preferably a compound of the formula:

[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula

[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula

Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² and / or R ² , wherein R ² is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, ethylene a group or C5~C20 aryl or heteroaryl group, wherein the group consisting of halogen, -OH, COOZ, -CN, may be substituted by NZ _2,
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a divalent C5-C20 aryl or heteroaryl group. , -OH, COOZ, -CN, NZ ₂ may be substituted,
Z, independently of one another, each is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, — May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. ]

  Preferred vinyl-containing phosphonic acids are alkenes having phosphonic acid groups such as ethenephosphonic acid, propenephosphonic acid, butenephosphonic acid; for example 2-phosphonomethacrylic acid, 2-phosphonomethylmethacrylic acid, 2-phosphonomethylacrylamide And acrylic acid and / or methacrylic acid compounds having a phosphonic acid group such as 2-phosphonomethylmethacrylamide.

  Particular preference is given to using commercially available vinylphosphonic acids (ethenephosphonic acids), such as can be obtained, for example, from Aldrich or Clariant GmbH. Preferred vinylphosphonic acids have a purity of more than 70%, in particular 90%, more preferably more than 97%.

  Furthermore, the vinyl-containing phosphonic acid can be used in the form of a derivative that can later be converted to an acid, which conversion can be carried out in the polymerized state. Such derivatives include in particular salts, esters, amides and halides of vinyl-containing phosphonic acids.

  The use of vinyl-containing phosphonic acid is optional. The mixture prepared in step A) preferably comprises at least 20% by weight, in particular at least 30% by weight, more preferably at least 50% by weight, of vinyl-containing phosphonic acid, based on the total weight of the mixture.

  The mixture prepared in step A) can further comprise other organic and / or inorganic solvents. Organic solvents include in particular polar aprotic solvents such as esters such as dimethyl sulfoxide (DMSO), ethyl acetate, and polar protic solvents such as alcohols such as ethanol, propanol, isopropanol and / or butanol. . Inorganic solvents include in particular water, phosphoric acid and polyphosphoric acid.

  These can have a positive effect on the processing characteristics. In particular, the solubility of the polymer formed in step B) can be improved, for example, by adding an organic solvent. The amount of vinyl-containing sulfonic acid in such a solution is generally at least 5% by weight, preferably at least 10% by weight, more preferably 10% to 97% by weight. The amount of vinyl-containing phosphonic acid in such a solution is preferably at least 5% by weight, more preferably at least 10% by weight, particularly preferably 10 to 97% by weight.

  The weight ratio of vinyl-containing phosphonic acid to vinyl-containing sulfonic acid can vary widely. Preferably, the ratio of vinyl-containing phosphonic acid to vinyl-containing sulfonic acid ranges from 1: 100 to 99: 1, in particular from 1:10 to 10: 1. At a ratio of 1: 1 or higher, in particular a ratio of 3: 1 or higher, particularly preferably a ratio of 5: 1 or higher, the membrane can be operated at temperatures above 100 ° C. without humidification.

The mixture prepared in step A) preferably comprises at least 10%, in particular at least 20 to 98% by weight of vinyl-containing sulfonic acid and / or vinyl-containing phosphonic acid.
According to one particular embodiment of the invention, the ratio of vinyl-containing phosphonic acid to vinyl-containing sulfonic acid ranges from 1:99 to 99: 1, preferably 1:50 to 50: 1, on a weight basis. However, the present invention is not limited to this.

  The aromatic and heteroaromatic tetraamino 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′-tetraaminodiphenyl sulfone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenylmethane and 3,3 ′, 4,4′-tetraaminodiphenyldimethylmethane and its salts, in particular its mono-, di-, tri- and tetrahydrochloride derivatives is there.

  The aromatic carboxylic acids used according to the invention are dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids, or their esters, their anhydrides or their acid halides, in particular their acid chlorides. The term “aromatic carboxylic acid” includes heteroaromatic carboxylic acids as well. The aromatic dicarboxylic acid is preferably isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylamino. Isophthalic acid, 5-N, N-diethylaminoisophthalic acid, 2,5-dihydroxyterephthalic acid, 2,6-dihydroxyisophthalic acid, 4,6-dihydroxyisophthalic acid, 2,3-dihydroxyphthalic acid, 2,4-dihydroxy Phthalic acid, 3,4-dihydroxyphthalic acid, 3-fluorophthalic acid, 5-fluoroisophthalic acid, 2-fluoroterephthalic acid, tetrafluorophthalic acid, tetrafluoroisophthalic acid, tetrafluoroterephthalic acid, 1,4-naphthalenedicarboxylic Acid, 1,5-naphthalene dicarboxylic 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'-stilbene dicarboxylic acid, 4-carboxycinnamic acid, and its C1-C20 alkyl ester or C5-C12 aryl ester, or its acid anhydride or its acid chloride. The aromatic tri- and tetracarboxylic acid or its C1-C20 alkyl ester or C5-C12 aryl ester or its acid anhydride or its acid chloride is preferably 1,3,5-benzenetricarboxylic acid (trimesic acid), 1 2,4-benzenetricarboxylic acid (trimellitic acid), (2-carboxyphenyl) iminodiacetic acid, 3,5,3′-biphenyltricarboxylic acid and 3,5,4′-biphenyltricarboxylic acid.

  The aromatic tetracarboxylic acid or its C1-C20 alkyl ester or C5-C12 aryl ester or its acid anhydride or its acid chloride is preferably 3,5,3 ′, 5′-biphenyltetracarboxylic acid, 1,2 , 4,5-benzenetetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 1,2,5 , 6-Naphthalenetetracarboxylic acid and 1,4,5,8-naphthalenetetracarboxylic acid.

  The heteroaromatic carboxylic acids used in accordance with the present invention are heteroaromatic dicarboxylic acids and tricarboxylic acids and tetracarboxylic acids, and their esters or anhydrides. By heteroaromatic carboxylic acid is meant an aromatic system that contains at least one nitrogen, oxygen, sulfur or phosphorous atom in the aromatic moiety. Preferably, pyridine-2,5-dicarboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid 3,5-pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzimidazole-5,6-dicarboxylic acid. Moreover, it is the C1-C20 alkyl ester or C5-C12 aryl ester, its acid anhydride, or its acid chloride.

  The amount of tricarboxylic acid and / or tetracarboxylic acid (relative to the dicarboxylic acid used) is 0-30 mol%, preferably 0.1-20 mol%, in particular 0.5-10 mol%.

  The aromatic and heteroaromatic diaminocarboxylic acids used according to the invention are preferably diaminobenzoic acid and its mono- and dihydrochloride derivatives.

  In step A) it is preferred to use a mixture of at least two different aromatic carboxylic acids. Particular preference is given to using mixtures which also contain heteroaromatic carboxylic acids in addition to aromatic carboxylic acids. The mixing ratio of aromatic carboxylic acid to heteroaromatic carboxylic acid is between 1:99 and 99: 1, preferably between 1:50 and 50: 1.

  These mixtures are in particular mixtures of N-heteroaromatic dicarboxylic acids and aromatic dicarboxylic acids. Non-limiting examples include 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- Carboxylic acid, pyridine-3,5-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, pyridine-2,4-dicarboxylic acid, 4-phenyl-2,5-pyridinedicarboxylic acid, 3,5-pyrazole dicarboxylic acid, Examples include 2,6-pyrimidine dicarboxylic acid and 2,5-pyrazine dicarboxylic acid.

  If it is desired to increase the molecular weight as much as possible, the carboxylic acid groups can be compared with the amino groups in the reaction of the tetraamino compound with one or more aromatic carboxylic acids and / or their esters containing at least two acid groups per carboxylic acid monomer. The molar ratio is preferably about 1: 2.

  The mixture prepared in step A) preferably contains at least 2% by weight, in particular 5-20% by weight, of monomers for the production of polyazoles.

  The polyazole-based polymer formed in step B) is of the general formula (I) and / or (II) and / or (III) and / or (IV) and / or (V) and / or (VI) and And / or (VII) and / or (VIII) and / or (IX) and / or (X) and / or (XI) and / or (XII) and / or (XIII) and / or (XIV) and / or An azole repeating unit of (XV) and / or (XVI) and / or (XVII) and / or (XVIII) and / or (XIX) and / or (XX) and / or (XXI) and / or (XXII) Including.

[Where:
Ar is a tetravalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic;
Ar ¹ is a divalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ² is a divalent or trivalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic;
Ar ³ is a trivalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ⁴ is a trivalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ⁵ is a tetravalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ⁶ is a divalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic;
Ar ⁷ is a divalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ⁸ is a trivalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic;
Ar ⁹ is a divalent or trivalent or tetravalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic;
Ar ¹⁰ is a divalent or trivalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Ar ¹¹ is a divalent aromatic or heteroaromatic group, each of which may be the same or different and may be monocyclic or polycyclic,
Each X is the same or different and is oxygen, sulfur or a group having a hydrogen atom, 1 to 20 carbon atoms as a further group, preferably an amino group having a branched or unbranched alkyl or alkoxy group or an aryl group. Yes,
Each R is the same or different and is hydrogen, an alkyl group and an aromatic group, and each R is the same or different on the condition that R in Formula XX is a divalent group, and is a hydrogen, an alkyl group and an aromatic group;
n and m are integers of 10 or more, preferably 100 or more. ]

  Preferred aromatic or heteroaromatic groups in the present invention are benzene, naphthalene, diphenyl, diphenyl ether, diphenylmethane, diphenyldimethylmethane, bisphenone, diphenylsulfone, thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, Pyrazole, 1,3,4-oxadiazole, 2,5-diphenyl-1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 2,5-diphenyl- 1,3,4-triazole, 1,2,5-triphenyl-1,3,4-triazole, 1,2,4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole 1,2,3-triazole, 1,2,3,4-tetrazole, Nzo [b] thiophene, benzo [b] furan, indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, Benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, bipyridine, pyrazine, pyrazole, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-triazine , Tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, Phosphorus, pteridine or quinolidine, 4H-quinolidine, diphenyl ether, anthracene, benzopyrrole, benzooxathiadiazole, benzooxadiazole, benzopyridine, benzopyrazine, benzopyrazidine, benzopyrimidine, benzotriazine, indolizine, pyridopyridine, imidazopyrimidine, pyrazino It is derived from pyrimidine, carbazole, acridine, phenazine, benzoquinoline, phenoxazine, phenothiazine, acridine, benzopteridine, phenanthroline and phenanthrene, which may be optionally substituted.

The substitution pattern for Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ and Ar ¹¹ is arbitrary; for example, in the case of phenylene, Ar ¹ , Ar ⁴ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ or Ar ¹¹ can be ortho-, meta- and para-phenylene. Particularly preferred groups are derived from benzene and biphenylene, which may be optionally substituted.

Preferred alkyl groups are short chain alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n- or isopropyl and t-butyl groups.
Preferred aromatic groups are phenyl or naphthyl groups. Alkyl groups and aromatic groups may be substituted.
Preferred substituents are halogen atoms such as fluorine, amino groups, hydroxyl groups, or short chain alkyl groups such as methyl or ethyl groups.

Preference is given to polyazoles comprising a repeating unit of the formula (I) in which the group X is identical within one repeating unit.
Polyazoles can in principle also have different and different repeating units in the group X, for example. However, it is preferred that only one identical group X is present in one repeating unit.

  Further preferred polyazole polymers are polyimidazole, polybenzothiazole, polybenzoxazole, polyoxadiazole, polyquinoxaline, polythiadiazole, poly (pyridine), poly (pyrimidine), and poly (tetraazapyrene).

  In a further embodiment of the invention, the polymer comprising azole repeat units is a copolymer or blend comprising at least two units of formulas (I) to (XXII) which are different from each other. The polymer may be in the form of a block copolymer (diblock, triblock), random copolymer, periodic copolymer and / or alternating polymer.

In one particularly preferred embodiment of the invention, the polymer comprising azole repeat units is a polyazole comprising only units of formula (I) and / or (II).
The number of azole repeating units in the polymer is preferably an integer of 10 or more. Particularly preferred polymers contain at least 100 azole repeat units.

  In the present invention, a polymer containing a benzimidazole repeating unit is preferred. Some examples of very useful polymers containing benzimidazole repeat units are shown by the following formula:

［式中、ｎおよびｍは、各々、１０以上の、好ましくは１００以上の整数である。］

[Wherein, n and m are each an integer of 10 or more, preferably 100 or more. ]

  Polyazoles, in particular polybenzimidazoles, which can be obtained by the described process, are generally characterized by a high molecular weight. Measured as intrinsic viscosity, the molecular weight is preferably at least 0.2 dl / g, more preferably 0.7 to 10 dl / g, in particular 0.8 to 5 dl / g.

If the mixture according to step A) also contains a tricarboxylic acid and / or a tetracarboxylic acid, it causes branching / crosslinking in the polymer formed thereby. This contributes to improved mechanical properties.
The mixture obtained in step A) is subjected to step B) up to 350 ° C., preferably up to 280 ° C., in particular up to 200 ° C., preferably in the range from 100 ° C. to 250 ° C., more preferably in the range from 100 ° C. to 200 ° C. Until heated. During heating, an inert gas such as nitrogen or a noble gas such as neon or argon is used.

The purpose of step B) is to react the carboxylic acid group with an amino group. This reaction releases water. According to one particular embodiment of the invention, the water produced in step B) is removed from the reaction equilibrium. Methods are prevalent in the field. Water can be distilled off, for example. In addition, water can be combined with a desiccant. Depending on the nature of the desiccant, it can remain in the reaction mixture or can be separated from the reaction mixture. As the desiccant, phosphorus pentoxide (P ₂ O ₅ ) or silica gel can be used.

  In one variant of the process, the heating according to step B) can be performed after the sheet-like structure has been formed according to step C).

  In a further embodiment of the invention, monomers capable of crosslinking can be used. Depending on the temperature stability of the monomer, it can be added after the preparation of the mixture of step A) or the polyazole according to step B). Furthermore, monomers that can be crosslinked can also be applied to the sheet-like structure according to step C).

  Monomers that can be crosslinked include, in particular, compounds containing at least two carbon-carbon double bonds. Preference is given to dienes, trienes, tetraenes, dimethyl acrylates, trimethyl acrylates, tetramethyl acrylates, diacrylates, triacrylates and tetraacrylates.

のジエン、トリエン、およびテトラエン、式 Particularly preferred is the formula

Diene, triene, and tetraene of the formula

のジメチルアクリレート、トリメチルアクリレートおよびテトラメチルアクリレート、式

Dimethyl acrylate, trimethyl acrylate and tetramethyl acrylate, of formula

のジアクリレート、トリアクリレートおよびテトラアクリレートである。

Diacrylates, triacrylates and tetraacrylates.

[Wherein R is a C1-C15 alkyl group, a C5-C20 aryl or heteroaryl group, NR ′, —SO ₂ , PR ′, Si (R ′) ₂ , wherein the group is substituted Well,
R ′ are each independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, a C5-C20 aryl or heteroaryl group,
n is at least 2]

  The substituent of the group R is preferably a halogen, hydroxyl, carboxy, carboxyl, carboxyl ester, nitrile, amine, silyl, siloxane group.

  Particularly preferred crosslinking agents are allyl methacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene and polyethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, glycerol dimethacrylate, diurethane dimethacrylate, Trimethylpropane trimethacrylate, epoxy acrylate, such as Ebacryl, N ′, N-methylenebisacrylamide, carbinol, butadiene, isoprene, chloroprene, divinylbenzene and / or bisphenol A dimethyl acrylate. These compounds are commercially available from, for example, Sartomer Company Exton, Pennsylvania under the names CN-120, CN104 and CN-980.

  The use of a cross-linking agent is optional. These compounds are usually 0.05 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight based on the weight of the vinyl-containing sulfonic acid and, if used, the vinyl-containing phosphonic acid. It can be used in the range of 10% by weight.

  The mixture of polymers produced in step A) can be a solution, in which case a dispersed or suspended polymer may be present in this mixture.

  Preferred polymers include poly (chloroprene), polyacetylene, polyphenylene, poly (p-xylylene), polyarylmethylene, polystyrene, polymethylstyrene, polyvinyl alcohol, polyvinyl acetate, polyvinyl ether, polyvinylamine, poly (N-vinylacetamide). , Polyvinyl imidazole, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl pyridine, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinyl difluoride, polyhexafluoropropylene, polyethylene tetrafluoroethylene, hexafluoropropylene, and perfluoropropyl vinyl ether Of carboalkoxyperfluoroal with trifluoronitrosomethane PTFE copolymer with xylvinyl ether, such as polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polyacrolein, polyacrylamide, polyacrylonitrile, polycyanoacrylate, polymethacrylamide, especially cycloolefin copolymer of norbornene Polyolefins; polymers having C—O bonds in the main chain, such as polyacetals, polyoxymethylenes, polyethers, polypropylene oxides, polyepichlorohydrins, polytetrahydrofurans, polyphenylene oxides, polyether ketones, polyether ether ketones, polyethers Ketone ketone, polyether ether ketone ketone, polyether ketone ether ketone ketone, polyester, especially polyester Hydroxyacetic acid, polyethylene terephthalate, polybutylene terephthalate, polyhydroxybenzoate, polyhydroxypropionic acid, polypropionic acid, polypivalolactone, polycaprolactone, furan resin, phenol aryl resin, polymalonic acid and polycarbonate; in the main chain Examples of the polymer having a C—S bond are polysulfide ether, polyphenylene sulfide, polyether sulfone, polysulfone, polyether ether sulfone, polyaryl ether sulfone, polyphenylene sulfone, polyphenylene sulfide sulfone and poly (phenyl sulfide-1,4- Phenylene); polymers having a C—N bond in the main chain, such as polyimines, polyisocyanides, polyetherimines, polyethers Terimide, poly (trifluoromethyl) bis (phthalimido) phenyl, polyaniline, polyaramid, polyamide, polyhydrazide, polyurethane, polyimide, polyazole, polyazole ether ketone, polyurea, polyazine; liquid crystal polymer, especially Vectra; and inorganic polymer For example, polysilane, polycarbosilane, polysiloxane, polysilicic acid, polysilicate, silicone, polyphosphazene and polythiazyl.

In order to further improve the performance characteristics, further fillers can be added to the membrane, in particular proton-conducting fillers and further acids can be added. The addition can be performed, for example, in step A), step B), step C) and / or step D). These additives can also be added after the polymerization according to step D) if they are liquid.
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 , RbSO ₄ , LiN ₂ H ₅ SO ₄ , NH ₄ HSO ₄ ,
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 , Ce (HPO ₄ ) ₂ , Ti (HPO ₄₎ ) ₂ , KH ₂ PO ₄ , NaH ₂ PO ₄ , LiH ₂ PO ₄ , NH ₄ H ₂ PO ₄ , CsH ₂ PO ₄ , CaHPO ₄ , MgHPO ₄ , HSbP ₂ O ₈ , HSb ₃ P ₂ O ₁₄ , H ₅ Phosphates such as Sb ₅ P ₂ O ₂₀ ,
_{H 3 PW 12 O 40 · nH} 2 O (n = 21~29), H 3 SiW 12 O 40 · nH 2 O (n = 21~29), H x WO 3, HSbWO 6, H 3 PMo 12 O 40 , polyacids such as _{H 2 Sb 4 O 11, HTaWO} 6, HNbO 3, HTiNbO 5, HTiTaO 5, HSbTeO 6, H 5 Ti 4 O 9, HSbO 3, H 2 MoO 4,
(NH ₄ ) ₃ H (SeO ₄ ) ₂ , UO ₂ AsO ₄ , (NH ₄ ) ₃ H (SeO ₄ ) ₂ , KH ₂ AsO ₄ , Cs ₃ H (SeO ₄ ) ₂ , Rb ₃ H (SeO ₄ ) selenide and arsenide, such as _2,
Oxides such as Al ₂ O ₃ , Sb ₂ O ₅ , ThO ₂ , SnO ₂ , ZrO ₂ , MoO ₃ ,
Zeolite, zeolite _(NH ⁴ +), sheet silicates, framework silicates, H- Natororaito, H- mordenite, NH ₄ - Anarushin, NH ₄ - sodalite, NH ₄ - gallate, H- silicates such as montmorillonite,
Acids such as HClO ₄ , SbF ₅ ,
Fillers such as carbides, in particular SiC, Si ₃ N ₄ , fibers, in particular glass fibers, glass powder and / or polymer fibers (preferably polyazole-based).

  These additives can be added in normal amounts to proton conducting polymer membranes, but in that case the positive properties of the membrane such as high conductivity, long life and high mechanical stability are very many. It should not be affected too much by adding the additives. In general, the polymerized film according to step D) contains 80% by weight or less, preferably 50% by weight or less, more preferably 20% by weight or less of additives.

The membrane may further comprise a perfluorinated sulfonic acid additive (preferably 0.1 to 20 wt%, more preferably 0.2 to 15 wt%, very preferably 0.2 to 10 wt%). it can. These additives lead to improved performance, increased oxygen solubility and oxygen diffusion near the cathode, and decreased adsorption of phosphoric acid and phosphate to platinum. (Electrolyte additive for phosphoric acid fuel cells. Gang, Xiao; Hjuler, HA; Olsen, C .; Berg, RW; Bjerrum, NJ, Chem. Dep. Ryby, Den. J. Electrochem. Soc. (1993), 140 (4), 896-902, and Perfluorosulfiide as an additive in phophoric acid fuel cell.
DesMarteau, Darryl. D. Singh, S .; Case Cent. Electrochem. Sci. , Case West. Reserve Univ. , Cleveland, OH, USA. J. et al. Electrochem. Soc. (1989), 136 (2), 385-90)

  Non-limiting examples of persulfonated additives include trifluoromethane sulfonic acid, potassium trifluoromethane sulfonate, sodium trifluoromethane sulfonate, lithium trifluoromethane sulfonate, ammonium trifluoromethane sulfonate, potassium perfluorohexane sulfonate, sodium perfluorohexane sulfonate , Lithium perfluorohexanesulfonate, ammonium perfluorohexanesulfonate, perfluorohexanesulfonic acid, potassium nonafluorobutanesulfonate, sodium nonafluorobutanesulfonate, lithium nonafluorobutanesulfonate, ammonium nonafluorobutanesulfonate, nonafluorobutanesulfone Cesium acid, triethylammonium perfluorohexasulfonate Um, a perfluorosulfonate imides and Nafion.

  The sheet-like structure is formed according to step B) by a method known per se (casting, spraying, knife coating, extrusion) known as a technique relating to polymer film production. Thus, the mixture is suitable for forming a sheet-like structure. The mixture can thus be a solution or a suspension and the fraction of low solubility components is limited to such an amount that a sheet-like structure can be formed. Suitable supports are all supports that can be inert under the conditions. These supports include polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyhexafluoropropylene, copolymers of PTFE and hexafluoropropylene, polyimide, polyphenylene sulfide (PPS) and polypropylene (PP) films. Including.

To adjust the viscosity, if appropriate, water and / or an easily evaporable organic solvent can be added to the mixture. Thus, the viscosity is adjusted to a desired value, and the film can be easily formed.
The thickness of the sheet-like structure is generally 15 to 2000 μm, preferably 30 to 1500 μm, particularly 50 to 1200 μm, but is not limited thereto.

  The polymerization in step D) of the vinyl-containing sulfonic acid and, if present, the vinyl-containing phosphonic acid is preferably carried out by radical polymerization. The radicals can be formed thermally, photochemically, chemically and / or electrochemically.

  As an example, an initiator solution comprising at least one substance capable of forming radicals can be added to the mixture after the solution and / or dispersion has been heated according to step B). It is also possible to apply an initiator to the sheet-like structure obtained after step C). This can be done by means known per se known as prior art (for example, spraying, dipping, etc.).

  In particular, suitable radical formers include azo compounds, peroxy compounds, persulfate compounds or azoamidines. Non-limiting examples include dibenzoyl peroxide, dicumene peroxide, cumene hydroperoxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, dipotassium persulfate, ammonium peroxydisulfate, 2, 2′-azobis (2-methylpropionitrile) (AIBN), 2,2′-azobis (amidine isobutanoate) hydrochloride, benzopinacol, dibenzyl derivative, methyl ethylene ketone peroxide, 1,1-azobiscyclohexanecarbo Nitrile, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, didecanoyl peroxide, tert-butylper-2-ethylhexanoate, ketone peroxide Id, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, 2,5-bis (2-ethylhexanoylperoxy) -2,5-dimethylhexane Tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, dicumyl peroxide, 1, 1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, cumyl hydroperoxide, Radical formation available from DuPont under the names ert-butyl hydroperoxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, and Vazo®, eg Vazo V50® and Vazo WS® Contains agents.

In addition, a radical former that forms radicals under irradiation can be used. Preferred compounds include α, α-diethoxyacetophenone (DEAP, Upjon Corp), n-butylbenzoin ether (Trigonal-14 (registered trademark), AKZO) and 2,2-dimethoxy-2-phenylacetophenone (Igacure 651 ( 1) -benzoylcyclohexanol (Igacure 184®), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819®) and 1- [4- (2- Hydroxyethoxy) phenyl] -2-hydroxy-2-phenylpropan-1-one (Irgacure 2959®), each of which is available from Ciba Geigy Corp. Commercially available.
It is usual to add from 0.0001 to 5% by weight, in particular from 0.01 to 3% by weight of radical former (based on the total of vinyl-containing sulfonic acid and vinyl-containing phosphonic acid, if used). The amount of radical former can be varied depending on the desired degree of polymerization.

Polymerization can also be carried out by the action of IR or NIR (IR = infrared, ie light having a wavelength above 700 nm; NIR = near infrared, ie wavelength in the range of about 700-2000 nm, or about 0.1. Light having an energy in the range of 6 to 1.75 eV).
The polymerization can also be carried out by the action of UV light having a wavelength of less than 400 nm. This polymerization method is known per se, for example, Hans Joerg Elias, Makromolekule Chemie, 5th edition, volume 1, 492-511; R. Arnold, N.M. C. Baird, J. et al. R. Bolton, J. et al. C. D. Brand, P.M. W. M Jacobs, P.M. de Mayo, W.M. R. Walle, Photochemistry-An Introduction, Academic Press, New York and M.C. K. Misra, Radical Photopolymerization of Vinyl Monomers, J. et al. Macromol. Sci. -Revs. Macromol. Chem. Phys. C22 (1982-1983) 409.

  Polymerization can also be carried out by the action of β, γ and / or electron beams. According to one particular embodiment of the invention, the membrane is irradiated with a radiation dose in the range 1 to 300 kGy, preferably 3 to 200 kGy, very preferably 20 to 100 kGy.

  The polymerization in step D) of the vinyl-containing sulfonic acid and, if used, vinyl-containing phosphonic acid is preferably above room temperature (20 ° C.) and below 200 ° C., in particular between 40 ° C. and 150 ° C., and more. Preferably it is carried out at a temperature between 50 ° C and 120 ° C. The polymerization is preferably carried out under normal pressure, but can also be carried out under the action of pressure. The polymerization leads to solidification of the sheet-like structure, which can be monitored by measuring the microhardness. The increase in hardness caused by the polymerization is preferably at least 20% with respect to the hardness of the sheet-like structure obtained in step B).

According to one particular embodiment of the invention, the membrane has a high mechanical stability. Its magnitude is given by the hardness of the film as determined by microhardness measurements according to DIN 50539. In the measurement, the membrane is continuously exposed to Vickers diamond for 20 seconds with a force up to 3 mN and the penetration depth is measured. According to it, the hardness at room temperature is at least 0.01 N / mm ² , preferably at least 0.1 N / mm ² , very preferably at least 1 N / mm ² , but is not limited thereto. . The force is then held constant at 3 mN for 5 seconds and the creep is calculated from the penetration depth. In preferred membranes, the creep C _HU 0.003 / _20/5 under these conditions is less than 20%, preferably less than 10%, very preferably less than 5%. The elastic modulus YHU determined by microhardness measurement is at least 0.5 MPa, in particular at least 5 MPa, very preferably at least 10 MPa, but is not limited thereto.

  Depending on the desired degree of polymerization, the sheet-like structure obtained after the polymerization is a self-supporting membrane. The degree of polymerization is preferably at least 2, in particular at least 5, very preferably at least 30 repeating units, in particular at least 50 repeating units, very particularly preferably at least 100 repeating units. This degree of polymerization is determined from the numerical average of the molecular weight Mn that can be measured by the GPC method. Due to the problem of isolating the polyvinyl sulfonic acid present in the membrane without causing degradation, this value is calculated without vinyl and without the addition of a polymer and, if used, vinyl containing phosphonic acid and, if used, vinyl containing phosphonic acid. Determined from tests performed by polymerizing the acid. In this case, the vinyl-containing sulfonic acid and, if used, the fraction of vinyl-containing phosphonic acid and radical initiator are kept constant compared to the ratio after dissolution of the membrane. The conversion achieved in the comparative polymerization is preferably at least 20%, in particular at least 40%, particularly preferably at least 75%, based on the vinyl-containing sulfonic acid used and, if used, the vinyl-containing phosphonic acid. is there.

The polymerization in step D) can lead to a reduction in the layer thickness. The thickness of the self-supporting membrane is preferably 15 to 1000 μm, more preferably 20 to 500 μm, especially 30 to 250 μm.
The membrane obtained by step D) is preferably self-supporting. That is, it can be detached from the support without causing damage and can be subsequently further processed directly if desired.

  Following the polymerization according to step D), the film can be thermally, photochemically, chemically and / or electrochemically cross-linked on the surface. This curing of the membrane surface further improves the properties of the membrane.

  According to one particular embodiment, the membrane can be heated to a temperature of at least 150 ° C., preferably at least 200 ° C., particularly preferably at least 250 ° C. Thermal crosslinking is preferably performed in the presence of oxygen. The oxygen concentration in this production process is usually in the range of 5 to 50% by volume, preferably 10 to 40% by volume, but is not limited thereto.

Cross-linking is IR or NIR (IR = infrared, ie light having a wavelength above 700 nm; NIR = near infrared, ie, wavelength in the range of about 700-2000 nm, or in the range of about 0.6-1.75 eV. Can also be performed by the action of UV light. A further method is to perform β, γ and / or electron beam irradiation. The amount of radiation in this case is preferably 5 to 200 kGy, in particular 10 to 100 kGy. Irradiation can be performed in air or under an inert gas. This improves the use properties of the membrane, in particular its durability.
The time for the crosslinking reaction can be varied within a wide range depending on the desired degree of crosslinking. In general, the reaction time is in the range of 1 second to 10 hours, preferably 1 minute to 1 hour, but is not limited thereto.

  According to one particular embodiment of the invention, the membrane comprises at least 3%, preferably at least 5%, more preferably at least 7% by weight phosphorus (as an element) relative to the total weight of the membrane. The phosphorus fraction can be determined by elemental analysis. For this purpose, the membrane is dried under vacuum (1 mbar) at 110 ° C. for 3 hours.

  The polymer film of the present invention exhibits improved material properties compared to doped polymer films known to date. They already exhibit a specific conductivity, in particular compared to known undoped polymer films. This is particularly achieved by the presence of a polymer containing sulfonic and phosphonic acid groups.

  The intrinsic conductivity of the present invention is at least 0.001 S / cm, preferably at least 10 mS / cm, in particular at least 20 mS / cm at a temperature of 70 ° C. To obtain these values, the membrane of the present invention can be humidified. For this purpose, for example, a fraction of water can be supplied to a compound used as an energy source, for example hydrogen or methanol. In many cases, however, the water produced by the reaction is sufficient to provide these conductivity values.

  If the weight fraction of polyvinylphosphonic acid exceeds 10% relative to the total weight of the membrane, the membrane is generally at least 1 mS / cm, preferably at least 3 mS / cm, especially at least 5 mS / cm at a temperature of 160 ° C. Particularly preferably, it exhibits a conductivity of at least 10 mS / cm. These values are achieved without humidification.

  Specific conductivity is measured by impedance spectroscopy in a 4-pole configuration in potentiostatic mode using a platinum electrode (wire, 0.25 mm diameter). The distance between the collecting electrodes is 2 cm. The resulting spectrum is evaluated using a simple model consisting of a parallel arrangement of ohmic resistors and capacitors. The sample cross section of the membrane doped with phosphoric acid is measured immediately before the sample is attached. To measure temperature dependence, the measuring cell is brought to the desired temperature in the oven and adjusted by a Pt-100 thermocouple located immediately adjacent to the sample. After the temperature has reached, the sample is held at that temperature for 10 minutes before starting the measurement.

In a liquid direct methanol fuel cell, the crossover current density when operating with a 0.5 M methanol solution at 90 ° C. is preferably less than 100 mA / cm ² , in particular less than 70 mA / cm ² , more preferably less than 50 mA / cm ² , Very preferably less than 10 mA / cm ² . In a gaseous direct methanol fuel cell, the crossover current density when operating at 160 ° C. in a 2M methanol solution is preferably less than 100 mA / cm ² , in particular less than 50 mA / cm ² , very preferably less than 10 mA / cm ² It is.

In order to measure the crossover current density, the amount of carbon dioxide released at the cathode is measured using a CO ₂ sensor. Using the values obtained for the amount of CO ₂ , P.I. Zelenay, S .; C. Thomas, S .; Gottestred in S. Gottesfeld, T .; F. Fuller “Proton Conducting Membrane Fuel Cells II” ESC Proc. Vol. 98-27 pp. Calculate the crossover current density as described in 300-308.

  Possible fields of use of the inherently conductive polymer membranes of the present invention include use in fuel cells, electrolysis, capacitors and battery systems. Considering these characteristics, the polymer membrane can be preferably used in a fuel cell, particularly a DMFC fuel cell (direct methanol fuel cell).

The present invention provides a membrane electrode assembly comprising at least one polymer membrane of the present invention. Membrane electrode assemblies exhibit high performance even when the amount of catalytically active material such as platinum, ruthenium or palladium is low. For this purpose, a gas diffusion layer provided with a catalytically active layer can be used.
The gas diffusion layer generally exhibits electronic conductivity. Usually, for this purpose, a sheet-like structure that is electrically conductive and acid resistant is used. Such structures include, for example, carbon fiber paper, graphitized carbon fiber paper, carbon fiber fabric, graphitized carbon fiber fabric and / or sheet-like structures, which are electrically conductive by adding carbon black. It has become sex.

  The catalytically active layer includes a catalytically active material. Such materials include noble metals, particularly platinum, palladium, rhodium, iridium and / or ruthenium. These substances can also be used in the form of alloys with each other. Furthermore, these materials can be used as alloys with non-noble metals such as Cr, Zr, Ni, Co and / or Ti, for example. In addition, the above-mentioned noble metal and / or non-noble metal oxides can also be used. According to one particular embodiment of the invention, the catalytically active compound is preferably used in the form of particles having a size of 1-1000 nm, in particular 10-200 nm, preferably 20-100 nm.

Furthermore, the catalytically active layer may contain general purpose additives. These include, for example, fluoropolymers such as polytetrafluoroethylene (PTFE), and surface active materials.
According to one particular embodiment of the invention, the weight ratio of fluoropolymer to catalyst material comprising at least one noble metal and optionally one or more support materials is greater than 0.1, preferably this ratio Is in the range of 0.2 to 0.6.

  According to one particular embodiment of the invention, the catalyst layer has a thickness in the range of 1 to 1000 μm, in particular 5 to 500 μm, preferably 10 to 300 μm. This number represents an average value that can be determined by measuring the thickness of the layers in cross-section with a photomicrograph obtained using a scanning electron microscope (SEM).

According to one particular embodiment of the present invention, the noble metal content of the catalyst layer, 0.1 to 10.0 mg / cm ^2, preferably 0.2~6.0mg / cm ^2, particularly preferably 0.3 it is a ~3.0mg / cm ^2. These numbers can be determined by elemental analysis of the sheet-like sample.

  For further information on membrane electrode assemblies, reference is made to the technical literature, in particular the patent applications WO 01/18894 A2, DE 1950748, DE 19509749, WO 00/26982, WO 92/15121 and DE 19757482. The disclosures in the above documents relating to the construction and production of membrane electrode assemblies and the electrodes, gas diffusion layers and catalysts to be selected are also part of this description.

In another variation, a catalytically active layer can be applied to the membrane of the present invention, which can be coupled to a gas diffusion layer.
In one variant of the invention, the membrane can be formed directly on the electrode instead of on the support. As a result, the process according to step D) can be correspondingly shortened or the amount of initiator solution can be reduced. This is because the membrane no longer needs to be self-supporting. Also provided by the present invention is an electrode coated with this type of membrane and the polymer membrane of the present invention.

  Furthermore, polymerization of vinyl-containing phosphonic acid and vinyl-containing sulfonic acid can also be performed in the laminated membrane electrode assembly. To do so, apply the solution to the electrodes and press the two against a similarly coated second electrode. Subsequently, polymerization is performed in the laminated film electrode assembly as described above.

The coating has a thickness of between 2 and 500 μm, preferably between 5 and 300 μm, in particular between 10 and 200 μm. This enables use in so-called micro fuel cells, in particular micro DMFC fuel cells.
A membrane with this type of coating can be placed on a membrane electrode assembly comprising at least one polymer membrane of the present invention, if desired.

  In a further variant, a catalytically active layer can be applied to the membrane of the invention and this layer can be connected to a gas diffusion layer. For that purpose, a film is formed according to steps A) to D) and a catalyst is applied. In one variation, the catalyst can be applied prior to or in conjunction with the initiator solution. These structures are also provided by the present invention.

In addition, according to steps A) to D), a membrane can be formed on a support or support film that already contains a catalyst. After removal of the support or support film, the catalyst is present on the membrane of the present invention. These structures are also the subject of the present invention.
Similarly, the subject of the invention is at least one coated electrode and / or at least one polymer according to the invention in combination with a polyazole-based further polymer film or a polymer blend film comprising at least one polymer based on polyazole. A membrane electrode assembly including a membrane.

Claims (21)

A) The following formula:

(1)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula:

(2)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10]
And / or formula:

(3)
Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² , and / or R ² ,
Here, R ² is hydrogen, a C1-C15 alkyl group, a C1-C15-alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the above groups are halogen, —OH, COOZ, —CN. , May be substituted by NZ ₂ ,
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group. , COOZ, -CN, NZ ₂ may be substituted,
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
A vinyl-containing sulfonic acid represented by
3,3 ′, 4,4′-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1,2,4,5-tetraaminobenzene, 3,3 ′, 4,4′-tetraamino Diphenylsulfone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenylmethane and 3,3 ′, One or more aromatic tetraamino compounds selected from 4,4′-tetraaminodiphenyldimethylmethane, and isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylaminoisophthalic acid, 5-N, N-diethylaminoisophthalic acid, 2,5-dihydroxyte Phthalic acid, 2,5-dihydroxyisophthalic acid, 2,3-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-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'-dicarbo Acid, 4-trifluoromethylphthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-stilbene dicarboxylic acid, 4-carboxycinnamic acid, or a C1-C20 alkyl ester thereof, C5 Or mixed with one or more aromatic carboxylic acids selected from C12 aryl esters, acid anhydrides or acid chlorides thereof, and / or in the above formulas (1) and / or (2) and / or (3) Represented vinyl-containing sulfonic 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-pyridine carboxylic acid, 3, 5-pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzimidazole-5,6-dicarboxylic acid, and C1-C20 alkyl ester thereof or Mixed with one or more aromatic and / or heteroaromatic diaminocarboxylic acids selected from C5 to C12 aryl esters, acid anhydrides or acid chlorides thereof,
The mixture comprises at least 2% by weight of a monomer that forms a polyazole and at least 10-98% by weight of a vinyl-containing sulfonic acid;
B) The mixture obtained by step A) is heated under inert gas to a temperature of up to 350 ° C. to form a polyazole polymer,
C) Using the mixture according to step A) and / or B), a layer with a thickness of 15 to 2000 μm is applied to the support,
D) The vinyl-containing sulfonic acid present in the sheet-like structure obtained by step C) is added to the mixture after heating in step B) or applied to the sheet-like structure obtained after step C). Then, polymerization is carried out by radical polymerization that forms free radicals thermally, photochemically, chemically and / or electrochemically from a radical-forming agent present in an amount of 0.0001 to 5% by weight of the total amount of vinyl-containing sulfonic acid. A proton conductive polymer membrane comprising a sulfonic acid group-containing polymer having a conductivity of at least 0.001 S / cm at a temperature of 70 ° C. obtained by a method comprising a step performed at a temperature of (20 ° C.) to less than 200 ° C.   As an aromatic carboxylic acid, tricarboxylic acid, its C1-C20 alkyl ester, its C5-C12 aryl ester, its acid anhydride or its acid chloride, or tetracarboxylic acid, its C1-C20 alkyl ester, C5-C12 aryl 2. A membrane according to claim 1, characterized in that an ester, its acid anhydride or its acid chloride is used in step A).   As aromatic carboxylic acids, 1,3,5-benzenetricarboxylic acid (trimesic acid); 2,4,5-benzenetricarboxylic acid (trimellitic acid); (2-carboxyphenyl) iminodiacetic acid, 3,5,3 ′ -Biphenyltricarboxylic acid; 3,5,4'-biphenyltricarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid; naphthalene-1,4,5,8- Tetracarboxylic acid, 3,5,3 ′, 5′-biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyl It is characterized by using tetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid and / or 1,4,5,8-naphthalenetetracarboxylic acid. Film of claim 2 wherein.   The film according to claim 2 or 3, wherein the amount of tricarboxylic acid and / or tetracarboxylic acid is 0 to 30 mol% with respect to the dicarboxylic acid used.   The film according to claim 4, wherein the amount of tricarboxylic acid and / or tetracarboxylic acid is 0.1 to 20 mol% with respect to the dicarboxylic acid used.   The membrane according to claim 1, characterized in that the mixture prepared in step A) and / or step B) further comprises a vinyl-containing phosphonic acid. A vinyl-containing phosphonic acid has the formula:

(4)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the above groups are halogen, —OH, COOZ, —CN , May be substituted by NZ ₂ ,
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula:

(5)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10]
And / or formula:

(6)
Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² and / or R ² ,
Here, R ² is hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the groups are halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a divalent C5-C20 aryl or heteroaryl group. , -OH, COOZ, -CN, NZ ₂ may be substituted,
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, -OH,- May be substituted by CN,
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
The film according to claim 6, wherein the film is a compound represented by the formula:   8. A membrane according to claim 6 or 7, wherein the weight ratio of vinyl-containing phosphonic acid to vinyl-containing sulfonic acid is in the range from 1: 100 to 99: 1.   2. A membrane according to claim 1, characterized in that in step D), a crosslinkable monomer containing at least two carbon-carbon double bonds is polymerized.   2. A film according to claim 1, wherein the polymerization according to step D) takes place by irradiation with IR or NIR light, UV light, β, γ and / or electron beams.   Membrane according to claim 1, characterized in that the mixture produced in step A) and / or step B) comprises a dissolved, dispersed and / or suspended polymer.   2. A film according to claim 1, wherein the film formed by step D) has a thickness of 15 to 1000 [mu] m.   2. The membrane according to claim 1, wherein the support in step C) is an electrode.   2. A film according to claim 1, wherein the heating according to step B) is carried out after step C). A) The following formula:

(1)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula:

(2)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10]
And / or formula:

(3)
Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² , and / or R ² ,
Here, R ² is hydrogen, a C1-C15 alkyl group, a C1-C15-alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the above groups are halogen, —OH, COOZ, —CN. , May be substituted by NZ ₂ ,
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group. , COOZ, -CN, NZ ₂ may be substituted,
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
A vinyl-containing sulfonic acid represented by
3,3 ′, 4,4′-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1,2,4,5-tetraaminobenzene, 3,3 ′, 4,4′-tetraamino Diphenylsulfone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenylmethane and 3,3 ′, One or more aromatic tetraamino compounds selected from 4,4′-tetraaminodiphenyldimethylmethane, and isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylaminoisophthalic acid, 5-N, N-diethylaminoisophthalic acid, 2,5-dihydroxyte Phthalic acid, 2,5-dihydroxyisophthalic acid, 2,3-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-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'-dicarbo Acid, 4-trifluoromethylphthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-stilbene dicarboxylic acid, 4-carboxycinnamic acid, or a C1-C20 alkyl ester thereof, C5 Or mixed with one or more aromatic carboxylic acids selected from C12 aryl esters, acid anhydrides or acid chlorides thereof, and / or in the above formulas (1) and / or (2) and / or (3) Represented vinyl-containing sulfonic 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-pyridine carboxylic acid, 3, 5-pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzimidazole-5,6-dicarboxylic acid, and C1-C20 alkyl ester thereof or Mixed with one or more aromatic and / or heteroaromatic diaminocarboxylic acids selected from C5-C12 aryl esters, acid anhydrides or acid chlorides thereof,
The mixture comprises at least 2% by weight of a monomer that forms a polyazole and at least 10-98% by weight of a vinyl-containing sulfonic acid;
B) The mixture obtained by step A) is heated under inert gas to a temperature of up to 350 ° C. to form a polyazole polymer,
C) Using the mixture according to step A) and / or B), a layer with a thickness of 15 to 2000 μm is applied to the support,
D) The vinyl-containing sulfonic acid present in the sheet-like structure obtained by step C) is added to the mixture after heating in step B) or applied to the sheet-like structure obtained after step C). Then, polymerization is carried out by radical polymerization that forms free radicals thermally, photochemically, chemically and / or electrochemically from a radical-forming agent present in an amount of 0.0001 to 5% by weight of the total amount of vinyl-containing sulfonic acid. An electrode having a proton conductive polymer coating based on polyazole having a conductivity of at least 0.001 S / cm at a temperature of 70 ° C. obtained by a process comprising a step performed at a temperature of (20 ° C.) to less than 200 ° C.   The electrode according to claim 15, wherein the coating has a thickness of 2 to 3000 μm.   A membrane electrode assembly comprising at least one electrode and at least one membrane according to any one of claims 1-14.   A membrane electrode assembly comprising at least one electrode according to claim 15 or 16.   A fuel cell comprising one or more membrane electrode assemblies according to claim 17 or 18. A) The following formula:

(1)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
y is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
And / or formula:

(2)
[Wherein, R is a bond, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the group includes halogen, —OH, COOZ, —CN, Optionally substituted by NZ ₂
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10]
And / or formula:

(3)
Wherein A is a group of formula COOR ² , CN, CONR ² ₂ , OR ² , and / or R ² ,
Here, R ² is hydrogen, a C1-C15 alkyl group, a C1-C15-alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, and the above groups are halogen, —OH, COOZ, —CN. , May be substituted by NZ ₂ ,
R is a bond, a divalent C1-C15 alkylene group, a divalent C1-C15 alkyleneoxy group such as an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group. , COOZ, -CN, NZ ₂ may be substituted,
Each Z is independently hydrogen, a C1-C15 alkyl group, a C1-C15 alkoxy group, an ethyleneoxy group, or a C5-C20 aryl or heteroaryl group, wherein the groups are halogen, —OH, —CN May be replaced by
x is an integer 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10]
A vinyl-containing sulfonic acid represented by
3,3 ′, 4,4′-tetraaminobiphenyl, 2,3,5,6-tetraaminopyridine, 1,2,4,5-tetraaminobenzene, 3,3 ′, 4,4′-tetraamino Diphenylsulfone, 3,3 ′, 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminobenzophenone, 3,3 ′, 4,4′-tetraaminodiphenylmethane and 3,3 ′, One or more aromatic tetraamino compounds selected from 4,4′-tetraaminodiphenyldimethylmethane, and isophthalic acid, terephthalic acid, phthalic acid, 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, 5-aminoisophthalic acid, 5-N, N-dimethylaminoisophthalic acid, 5-N, N-diethylaminoisophthalic acid, 2,5-dihydroxyte Phthalic acid, 2,5-dihydroxyisophthalic acid, 2,3-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-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'-dicarbo Acid, 4-trifluoromethylphthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 4,4′-stilbene dicarboxylic acid, 4-carboxycinnamic acid, or a C1-C20 alkyl ester thereof, C5 Or mixed with one or more aromatic carboxylic acids selected from C12 aryl esters, acid anhydrides or acid chlorides thereof, and / or in the above formulas (1) and / or (2) and / or (3) Represented vinyl-containing sulfonic 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-pyridine carboxylic acid, 3, 5-pyrazole dicarboxylic acid, 2,6-pyrimidine dicarboxylic acid, 2,5-pyrazine dicarboxylic acid, 2,4,6-pyridinetricarboxylic acid, benzimidazole-5,6-dicarboxylic acid, and C1-C20 alkyl ester thereof or Mixed with one or more aromatic and / or heteroaromatic diaminocarboxylic acids selected from C5-C12 aryl esters, acid anhydrides or acid chlorides thereof,
The mixture comprises at least 2% by weight of a monomer that forms a polyazole and at least 10-98% by weight of a vinyl-containing sulfonic acid;
B) The mixture obtained by step A) is heated under inert gas to a temperature of up to 350 ° C. to form a polyazole polymer,
C) Using the mixture according to step A) and / or B), a layer with a thickness of 15 to 2000 μm is applied to the support,
D) The vinyl-containing sulfonic acid present in the sheet-like structure obtained by step C) is added to the mixture after heating in step B) or applied to the sheet-like structure obtained after step C). Then, polymerization is carried out by radical polymerization that forms free radicals thermally, photochemically, chemically and / or electrochemically from a radical-forming agent present in an amount of 0.0001 to 5% by weight of the total amount of vinyl-containing sulfonic acid. A method for producing a proton conductive polymer membrane comprising a sulfonic acid group-containing polymer having a conductivity of at least 0.001 S / cm at a temperature of 70 ° C., comprising a step performed at a temperature of (20 ° C.) to less than 200 ° C.   21. The method according to claim 20, wherein the heating according to step B) is performed after step C).