DE102022121979A1 - Method for producing a material for a membrane, material, membrane and use of a membrane - Google Patents

Abstract

The present invention relates to a method for producing a material for a membrane, which comprises the following steps: - Providing at least one starting material, at least one starting material containing or consisting of at least one monomer; - Synthesizing a polymer from the starting material (s) by means of polyhydroxyalkylation (PHA);- Modification of the synthesized polymer in a subsequent reaction. The invention further relates to a substance, a membrane and the use of a membrane.

Description

The present invention relates to a method for producing a material for a membrane. The present invention further relates to a material which is produced by such a method, and to a membrane comprising or consisting of such a material. In addition, the present invention relates to the use of such a membrane.

As part of the energy transition, alternative ways of generating electricity are increasingly being developed. Fuel cells are an important area. These convert the chemical reaction energy of an supplied fuel and an oxidizing agent into electrical energy. In addition, the storage of electrical energy is playing an increasing role. The main aim here is to further develop battery technology so that batteries have a high energy density on the one hand and high long-term stability on the other.

Membranes, in particular ion exchange membranes, are used in particular in electrochemical processes, for example in electrolysis processes, or in electrochemical systems, for example in a fuel cell or in a battery. High demands are placed on such membranes. On the one hand, they must be sufficiently chemically stable relative to the media surrounding them in relation to their area of application. In addition, such membranes are often exposed to mechanical stress. In electrochemical applications, a certain conductivity is also required along with a low degree of swelling, i.e. a low volume expansion.

Polymers are usually used as materials for such membranes. These are synthesized from monomers. A group of processes for polymer synthesis are the polycondensation processes. This group of processes includes the polyhydroxyalkylation (PHA) process.

Polymers produced by polyhydroxyalkylation are described, for example, in LI Olvera, MT Guzmán-Gutiérrez, MG Zolothukhin, S. Fomine, J. Cárdenas, FA Ruiz-Trevino, D. Villers TA Ezquerra, E. Prokhorov, “Novel High Molecular Weight Aromatic Fluorinated Polymers from One-Pot, Metal-Free Step Polymerizations”, Macromolecules 46 (2013) 7245-7256 , and in Guzmán-Gutierréz MT, Nieto DR, Fomine S, Morales SL, Zolothukhin MG, Hernandez MCG, Kricheldorf H, Wilks ES, “Dramatic Enhancement of Superacid-Catalyzed Polyhydroxyalkylation Reactions,” Macromolecules 44 (2011) 194-202 and in MT Guzmán-Gutierréz, MH. Rios-Dominguez, FA Ruiz-Treviño, MG Zolothukhin, J. Balmaseda, D. Fritsch, E. Prokhorov, “Structure-properties relationship for the gas transport properties of new fluoro-containing aromatic polymers,” Journal of Membrane Science 385-386 (2011) 277-284 .

Even if polymers that are fundamentally suitable for use in membranes can be synthesized using polyhydroxyalkylation, there is a constant need to improve the property profile, specifically chemical stability, conductivity and mechanical stability.

The object of the present invention is therefore to provide a method by which materials for a membrane with a favorable property profile can be produced. Furthermore, appropriate materials should be provided that are characterized by a favorable property profile.

• - Bereitstellen von mindestens einem Ausgangsstoff, wobei mindestens ein Ausgangsstoff wenigstens ein Monomer enthält oder daraus besteht;
• - Synthetisieren eines Polymers aus dem Ausgangsstoff/den Ausgangsstoffen mittels Polyhydroxyalkylierung (PHA);
• - Modifizierung des synthetisierten Polymers in einer Folgereaktion.

According to a first aspect of the present invention, this object is achieved by a method for producing a material for a membrane, which comprises the following steps:

• - Providing at least one starting material, at least one starting material containing or consisting of at least one monomer;
• - Synthesizing a polymer from the starting material(s) using polyhydroxyalkylation (PHA);
• - Modification of the synthesized polymer in a subsequent reaction.

• - Bereitstellen von einem Ausgangsstoff, wobei mindestens ein Ausgangsstoff wenigstens ein Monomer enthält oder daraus besteht;
• - Modifizierung mindestens eines Ausgangsstoffs in einer Vorabreaktion;
• - Synthetisieren eines Polymers aus dem Ausgangsstoff/den Ausgangsstoffen mittels Polyhydroxyalkylierung (PHA).

According to a second aspect of the present invention, the object is achieved by a method for producing a material for a membrane, which comprises the following steps:

• - Providing a starting material, at least one starting material containing or consisting of at least one monomer;
• - Modification of at least one starting material in a preliminary reaction;
• - Synthesizing a polymer from the starting material(s) using polyhydroxyalkylation (PHA).

Furthermore, the object on which the invention is based is achieved by a material which is produced by such a process.

The invention is therefore based on the fundamental idea of carrying out a modification to the polymer in addition to a polymer synthesis using polyhydroxyalkylation. This allows the properties of the polymer obtained to be further optimized. It is possible to modify the polymer after synthesis using polyhydroxyalkylation by implementing it in a subsequent reaction. Alternatively or additionally, the starting material can be modified in a preliminary reaction before the polymer synthesis step. In this case, the modified starting material is then involved in the polymer synthesis. In other words, a targeted functionalization of a starting material or the synthesized polymer can take place before and/or after the polymer synthesis in order to optimize the properties of the polymer. The polymer synthesized using polyhydroxyalkylation is also called PHA polymer.

Accordingly, the substance according to the invention preferably contains or consists of a polymer or a polymer mixture. A polymer is understood to be a chemical compound that consists of or includes chain molecules or branched molecules. The chain molecules or the branched molecules consist of the same units or, for example in the case of copolymers, of different units.

The starting material preferably contains at least one type of diaryl monomer.

• 4-Methylpiperazin-2-on, 1-(1-Methylpiperidin-4-yl)ethan-1-on, 1,4-Dimethylpiperazin-2-on, Piperazin-2-on, 1,3-Dimethyltetrahydropyrimidin-2(1H)-on, 1-(1-Methyl-1 H-benzo[d]imidazol-2-yl)ethan-1 -on, 2,2,2-Trifluor-1 -(1 -methyl-1H-benzo[d]imidazol-2-yl)ethan-1-on, 1-(5,6-Dimethyl-1H-benzo[d]imidazol-2-yl)ethan-1-on, 1-(5-Methylpyridin-3-yl)ethan-1-on, 1-(5-Methylpyridin-2-yl)ethan-1-on, 2,2,2-Trifluor-1-(4-mercaptophenyl)ethan-1-on, Acetylferrocen, (2,2,2-Trifluoracetyl)ferrocen, 1-(4-(5-Bromopentyl)phenyl)ethan-1-on, 1-(4-Ethylpiperazin-2-yl)ethan-1-on, 1-(1-Methyl-1Hpyrazol-4-yl)ethan-1-on, Pyrrolidin-3-carbaldehyd, 1-(1H-Pyrazol-3-yl)ethan-1-on, 1-(1H-Benzo[d]imidazol-6-yl)ethan-1-on, 1-(7-Methyl-1Hbenzo[d]imidazol-2-yl)ethan-1-on, 1-(1H-Benzo[d]imidazol-2-yl)ethan-1-on, 1-(4-Methylpyridin-3-yl)ethan-1-on, 1-(4-Mercaptophenyl)ethan-1-on, (4-Acetylphenyl)phosphonsäure, 1-(3-Methylpyridin-2-yl)ethan-1-on, 1-(1-Methyl-1H-pyrazol-3-yl)ethan-1-on, 1-(1,2,4-Trimethyl-1Himidazol-5-yl)ethan-1-on, 1-(1H-Benzo[d]imidazol-7-yl)ethan-1-on, 1-(1H-Benzo[d]imidazol-2-yl)propan-1 -on, 1-(1H-Benzo[d]imidazol-2-yl)propan-2-on, 1-(1,4,5-Trimethyl-1H-imidazol-2-yl)ethan-1-on, 2,2,2-Trifluor-1-(1-methyl-1H-imidazol-2-yl)ethan-1-on, 1-(1-Methyl-1H-imidazol-2-yl)ethan-1-on, 1-(1H-Imidazol-5-yl)ethan-1-on, 1-(1H-Imidazo-2-yl)ethan-1-on, 1-(2-Methylpyridin-4-yl)ethan-1-on, 4-Acetylbenzolsulfonsäure, 1-(4-Methylpyridin-2-yl)ethan-1-on, 1-(Pyridin-4-yl)ethan-1-on, 1-(Pyridin-3-yl)ethan-1-on, 1-(Pyridin-2-yl)ethan-1-on, 2,2,2-Trifluor-1 -(pyridin-2-yl)ethan-1-on, 2,2,2-Trifluor-1 -(pyridin-4-yl)ethan-1 -on, 2,2,2-Trifluor-1 -(pyridin-3-yl)ethan-1-on, 2,2,2-Trifluor-1 -(piperidin-4-yl)ethan-1 -on, 1-(Chinolin-8-yl)ethan-1-on, 1-(Chinolin-5-yl)ethan-1-on, 2,2,2-Trifluor-1-(1H-imidazol-2-yl)ethan-1-on, 1-(Chinolin-4-yl)ethan-1-on, 1-(3-Methylpyridin-4-yl)ethan-1-on, 1-(2,3,5,6-Tetrafluor-4-mercaptophenyl)ethan-1-on, 1-(Cyclopenta-2,4-dien-1-yl)ethan-1-on, 1-(4-Hexylphenyl)ethan-1-on, 1-(Cyclopenta-2,4-dien-1-yl)-2,2,2,-trifluorethan-1-on, 1-(4-(5-Chlorpentyl)phenyl)ethan-1-on, 1-(4-Bromphenyl)ethan-1-on, 1-(4-Chlorphenyl)ethan-1-on, 1-(4-Fluorphenyl)ethan-1-on, 1-(4-iodphenyl)ethan-1-on, 1-(6-Methylpyridin-2-yl)ethan-1-on, 1-(6-Methylpyridin-3-yl)ethan-1-on, 3-Acetylbenzolsulfonsäure, 4-Acetyl-2,3,5,6-Tetrafluorbenzolsulfonsäure, 1-(2-Methylpyridin-3-yl)ethan-1-on, 1-(Chinolin-7-yl)ethan-1-on, 1-(Chinolin-6-yl)ethan-1-on, Di(pyridin-2-yl)methanon, 1-(2-(Dimethylamino)phenyl)ethan-1-on, 2,2,2-Trifluor-1-(chinolin-3-yl)ethan-1-on, 1-(3-(Dimethylamino)phenyl)ethan-1-on, 1-(4-(Dimethylamino)phenyl)ethan-1-on, 1-(Chinolin-2-yl)ethan-1-on, 1-(4-(Dimethylamino)phenyl)-2,2,2-trifluorethan-1-on, 1-(3-(Dimethylamino)phenyl)-2,2,2-trifluorethan-1-on, 1-(3-Chlorphenyl)2,2,2-trifluorethan-1-on, 1-(3-Bromphenyl)-2,2,2-trifluorethan-1-on, 2,2,2-Trifluor-1-(3-iodphenyl)ethan-1-on, 2,2,2-Trifluor-1-(3-fluorphenyl)ethan-1-on, 1-(2-Bromphenyl)-2,2,2-trifluoroethan-1-on, 1-(2-Chlorphenyl)-2,2,2-trifluorethan-1-on, 1-(2-lodphenyl)-2,2,2-trifluoroethan-1-on, 1-(2-Fluorphenyl)-2,2,2-trifluorethan-1-on, 1-(2-Bromphenyl)-2,2,2-trifluorethan-1-on, 1-(2-Chlorphenyl)ethan-1-on, 1-(2-lodphenyl)ethan-1-on, 1-(2-Bromphenyl)ethan-1-on, 1-(2-Fluorphenyl)ethan-1-on, 1-(3-Chlorphenyl)ethan-1-on, 1-(3-Bromphenyl)ethan-1-on, 1-(3-lodphenyl)ethan-1-on, 1-(3-Fluorphenyl)ethan-1-on, 2,2,2-Trifluor-1-(4-fluorphenyl)ethan-1-on, 2,2,2-Trifluor-1-(4-Iodphenyl)ethan-1-on, 1-(4-Chlorphenyl)-2,2,2-trifluorethan-1-on, 1-(4-Bromphenyl)-2,2,2-trifluoroethan-1-on, 2,2,2-Trifluor-1-(perfluorphenyl)ethan-1-on, 8-Brom-1,1,1-trifluoroctan-2-on, 1-(Isochinolin-4-yl)ethan-1-on, 1-(Chinolin-3-yl)ethan-1-on, 1-(1,8-Naphthyridin-4-yl)-ethan-1-on, 1-(Perfluorphenyl)ethan-1-on, 1-(lsochinolin-1-yl)ethan-1-on, 2,2,2-Trifluor-1-(4-nitrophenyl)ethan-1-on, 2,2,2-Trifluor-1-(3-nitrophenyl)ethan-1-on, Ferrocencarboxaldehyd, Formylcobaltocen, Formylnickelocen.

According to a preferred embodiment, at least one starting material contains or consists of one or more of the following ketones and/or aldehydes:

• 4-Methylpiperazin-2-one, 1-(1-Methylpiperidin-4-yl)ethan-1-one, 1,4-Dimethylpiperazin-2-one, Piperazin-2-one, 1,3-Dimethyltetrahydropyrimidin-2(1H )-one, 1-(1-methyl-1H-benzo[d]imidazol-2-yl)ethan-1 -one, 2,2,2-trifluoro-1-(1-methyl-1H-benzo[d ]imidazol-2-yl)ethan-1-one, 1-(5,6-dimethyl-1H-benzo[d]imidazol-2-yl)ethan-1-one, 1-(5-methylpyridin-3-yl )ethan-1-one, 1-(5-methylpyridin-2-yl)ethan-1-one, 2,2,2-trifluoro-1-(4-mercaptophenyl)ethan-1-one, acetylferrocene, (2, 2,2-Trifluoroacetyl)ferrocene, 1-(4-(5-Bromopentyl)phenyl)ethan-1-one, 1-(4-Ethylpiperazin-2-yl)ethan-1-one, 1-(1-Methyl- 1Hpyrazol-4-yl)ethan-1-one, pyrrolidin-3-carbaldehyde, 1-(1H-pyrazol-3-yl)ethan-1-one, 1-(1H-benzo[d]imidazol-6-yl) ethan-1-one, 1-(7-Methyl-1Hbenzo[d]imidazol-2-yl)ethan-1-one, 1-(1H-Benzo[d]imidazol-2-yl)ethan-1-one, 1-(4-Methylpyridin-3-yl)ethan-1-one, 1-(4-Mercaptophenyl)ethan-1-one, (4-acetylphenyl)phosphonic acid, 1-(3-Methylpyridin-2-yl)ethan- 1-one, 1-(1-Methyl-1H-pyrazol-3-yl)ethan-1-one, 1-(1,2,4-trimethyl-1Himidazol-5-yl)ethan-1-one, 1- (1H-Benzo[d]imidazol-7-yl)ethan-1-one, 1-(1H-Benzo[d]imidazol-2-yl)propan-1 -one, 1-(1H-Benzo[d]imidazole -2-yl)propan-2-one, 1-(1,4,5-trimethyl-1H-imidazol-2-yl)ethan-1-one, 2,2,2-trifluoro-1-(1-methyl -1H-imidazol-2-yl)ethan-1-one, 1-(1-Methyl-1H-imidazol-2-yl)ethan-1-one, 1-(1H-imidazol-5-yl)ethan-1 -one, 1-(1H-Imidazo-2-yl)ethan-1-one, 1-(2-methylpyridin-4-yl)ethan-1-one, 4-acetylbenzenesulfonic acid, 1-(4-methylpyridin-2- yl)ethan-1-one, 1-(Pyridin-4-yl)ethan-1-one, 1-(Pyridin-3-yl)ethan-1-one, 1-(Pyridin-2-yl)ethan-1 -one, 2,2,2-trifluoro-1 -(pyridin-2-yl)ethan-1-one, 2,2,2-trifluoro-1 -(pyridin-4-yl)ethan-1 -one, 2 ,2,2-Trifluoro-1 -(pyridin-3-yl)ethan-1-one, 2,2,2-Trifluoro-1 -(piperidin-4-yl)ethan-1 -one, 1-(Quinolin- 8-yl)ethan-1-one, 1-(quinolin-5-yl)ethan-1-one, 2,2,2-trifluoro-1-(1H-imidazol-2-yl)ethan-1-one, 1-(Quinolin-4-yl)ethan-1-one, 1-(3-Methylpyridin-4-yl)ethan-1-one, 1-(2,3,5,6-Tetrafluoro-4-mercaptophenyl)ethane -1-one, 1-(Cyclopenta-2,4-dien-1-yl)ethan-1-one, 1-(4-Hexylphenyl)ethan-1-one, 1-(Cyclopenta-2,4-dien- 1-yl)-2,2,2,-trifluoroethan-1-one, 1-(4-(5-chloropentyl)phenyl)ethan-1-one, 1-(4-bromophenyl)ethan-1-one, 1 -(4-Chlorophenyl)ethan-1-one, 1-(4-Fluorophenyl)ethan-1-one, 1-(4-iodophenyl)ethan-1-one, 1-(6-Methylpyridin-2-yl)ethane -1-one, 1-(6-methylpyridin-3-yl)ethan-1-one, 3-acetylbenzenesulfonic acid, 4-acetyl-2,3,5,6-tetrafluorobenzenesulfonic acid, 1-(2-methylpyridin-3-yl )ethan-1-one, 1-(quinolin-7-yl)ethan-1-one, 1-(quinolin-6-yl)ethan-1-one, di(pyridin-2-yl)methanone, 1-( 2-(Dimethylamino)phenyl)ethan-1-one, 2,2,2-trifluoro-1-(quinolin-3-yl)ethan-1-one, 1-(3-(Dimethylamino)phenyl)ethan-1- one, 1-(4-(Dimethylamino)phenyl)ethan-1-one, 1-(Quinolin-2-yl)ethan-1-one, 1-(4-(Dimethylamino)phenyl)-2,2,2- trifluoroethan-1-one, 1-(3-(Dimethylamino)phenyl)-2,2,2-trifluoroethan-1-one, 1-(3-chlorophenyl)2,2,2-trifluoroethan-1-one, 1- (3-Bromophenyl)-2,2,2-trifluoroethan-1-one, 2,2,2-trifluoro-1-(3-iodophenyl)ethan-1-one, 2,2,2-trifluoro-1-( 3-fluorophenyl)ethan-1-one, 1-(2-bromophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-chlorophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-iodophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-fluorophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-bromophenyl)-2, 2,2-trifluoroethan-1-one, 1-(2-chlorophenyl)ethan-1-one, 1-(2-iodophenyl)ethan-1-one, 1-(2-bromophenyl)ethan-1-one, 1 -(2-Fluorophenyl)ethan-1-one, 1-(3-Chlorophenyl)ethan-1-one, 1-(3-Bromophenyl)ethan-1-one, 1-(3-iodophenyl)ethan-1-one , 1-(3-fluorophenyl) ethan-1-one, 2,2,2-trifluoro-1-(4-fluorophenyl)ethan-1-one, 2,2,2-trifluoro-1-(4-iodophenyl)ethan-1-one, 1- (4-Chlorophenyl)-2,2,2-trifluoroethan-1-one, 1-(4-Bromophenyl)-2,2,2-trifluoroethan-1-one, 2,2,2-Trifluoro-1-(perfluorophenyl )ethan-1-one, 8-bromo-1,1,1-trifluorooctan-2-one, 1-(isoquinolin-4-yl)ethan-1-one, 1-(quinolin-3-yl)ethan-1 -one, 1-(1,8-naphthyridin-4-yl)-ethan-1-one, 1-(perfluorophenyl)ethan-1-one, 1-(isoquinolin-1-yl)ethan-1-one, 2 ,2,2-trifluoro-1-(4-nitrophenyl)ethan-1-one, 2,2,2-trifluoro-1-(3-nitrophenyl)ethan-1-one, ferrocene carboxaldehyde, formylcobaltocene, formylnickelocene.

Structural formulas of usable starting materials are shown in the figure below, which are ketones and aldehydes.

• 1,2'-Binaphtalin, 1,1'-Binaphtalin, 2,2'-Binaphtalin, 1,1'-Biphenyl, 1,1'.4,1''-Terphenyl, 10-Methyl-9,10-dihydroacridin, 9,10-Diphenylanthracen, 1,4-Diphenylnaphthalin, 1,1':4',1''.4'',1'''-Quaterphenyl, 1,1':3',1''.3'',1'''-Quaterphenyl, 1,1':3',1''-Terphenyl, 9,9,10-Trimeathyl-9,10-dihydroacridin, 2,4,6-Triphenyl-1,3,5-triazin, 2,3-Diphenylnaphtalin, 2',2'',3',3'',5',5'',6',6''-Octafluor-1,1':4',1''.4'',1'''-quaterphenyl, 2',3',5',6'-Tetrafluor-1,1',4',1''-terphenyl, 2',4', 5', 6'-Tetrafluor-1,1':3',1''-terphenyl, 2',2'',4',4'',5',5'',6',6''-Octafluor-1,1':3',1''.3'',1'''-quaterphenyl, 9,10-dihydroacridin, 2,4,6-Triphenylpyridin, 5'lod-1,1':3',1''-terphenyl, 5'-Brom-1,1':3'1''-terphenyl, 5'-Chlor-1,1':3',1''-terphenyl, 2'-Brom-1,1':3'1''-terphenyl, 2'-Iod-1,1':3',1''-terphenyl, 4'-Brom-1,1':2',1''-terphenyl, 9,9-Dimethyl-9,10-dihydroacridin, 2,3,6,7-Tetraphenylnaphtalin, 2,6-Diphenylpyridin, 2,6-Diphenylpyrazin, 4,6-Diphenylpyrimidin, 3,5-Diphenylpyridin, 2,5-Diphenylpyridin, 2,5-diphenylpyrimidin, 1,3-Diphenylcyclohexan, 5-Methyl-5,10-dihydrophenazin, 5,10-Dihydrophenazin, 5'-Phenyl-1,1':3',1''-terphenyl, N-N-Dimethyl-[1,1':3',1''-terphenyl]-5'-amin, N-N-Dimethyl-[1,1':3',1''-terphenyl]-2'-amin, 6,6'-Diphenyl-2,2'-bipyridin, 2,4-Diphenyl-1,3,5-triazin, 1,4-Diphenylcyclohexan, 1,2-Diphenylcyclohexan, 5,10-Dimethyl-5, 10-dihydrophenazin, 5'-Methyl-1,1':3',1''-terphenyl, 2'-Methyl-1 ,1':3',1''-terphenyl, 4-Methyl-2,6-diphenylpyridin, 2',3'-Dimethyl-1,1':4',1''-terphenyl, 2',3',5',6'-Tetramethyl-1,1':4',1''-terphenyl, 2,3,5,6-Tetraphenylpyrazin.

At least one starting material can also contain one or more of the following aryls or aryl groups:

• 1,2'-binaphthalene, 1,1'-binaphthalene, 2,2'-binaphthalene, 1,1'-biphenyl, 1,1'.4,1''-terphenyl, 10-methyl-9,10-dihydroacridine , 9,10-Diphenylanthracene, 1,4-Diphenylnaphthalene, 1,1':4',1''.4'',1'''-Quaterphenyl, 1,1':3',1''.3'',1'''-quaterphenyl,1,1':3',1''-terphenyl, 9,9,10-trimeethyl-9,10-dihydroacridine, 2,4,6-triphenyl-1,3,5 -triazine, 2,3-diphenylnaphthalene, 2',2'',3',3'',5',5'',6',6''-octafluoro-1,1':4',1''.4'',1'''-quaterphenyl,2',3',5',6'-tetrafluoro-1,1',4',1''-terphenyl,2',4',5', 6 '-Tetrafluoro-1,1':3',1''-terphenyl, 2',2'',4',4'',5',5'',6',6''-octafluoro-1, 1':3',1''.3'',1'''-quaterphenyl, 9,10-dihydroacridine, 2,4,6-triphenylpyridine, 5'lod-1,1':3',1'' -terphenyl, 5'-bromo-1,1':3'1''-terphenyl, 5'-chloro-1,1':3',1''-terphenyl, 2'-bromo-1,1': 3'1''-terphenyl, 2'-iodo-1,1':3',1''-terphenyl, 4'-bromo-1,1':2',1''-terphenyl, 9,9- Dimethyl-9,10-dihydroacridine, 2,3,6,7-tetraphenylnaphthalene, 2,6-diphenylpyridine, 2,6-diphenylpyrazine, 4,6-diphenylpyrimidine, 3,5-diphenylpyridine, 2,5-diphenylpyridine, 2, 5-diphenylpyrimidine, 1,3-diphenylcyclohexane, 5-methyl-5,10-dihydrophenazine, 5,10-dihydrophenazine, 5'-phenyl-1,1':3',1''-terphenyl, NN-dimethyl-[ 1,1':3',1''-terphenyl]-5'-amine, NN-dimethyl-[1,1':3',1''-terphenyl]-2'-amine, 6,6'- Diphenyl-2,2'-bipyridine, 2,4-diphenyl-1,3,5-triazine, 1,4-diphenylcyclohexane, 1,2-diphenylcyclohexane, 5,10-dimethyl-5, 10-dihydrophenazine, 5'- Methyl-1,1':3',1''-terphenyl, 2'-Methyl-1,1':3',1''-terphenyl, 4-methyl-2,6-diphenylpyridine, 2',3'-Dimethyl-1,1':4',1''-terphenyl,2',3',5',6'-tetramethyl-1,1':4',1''-terphenyl, 2,3,5 ,6-Tetraphenylpyrazine.

Structural formulas for aryls that may be contained in or form the starting material are shown in the figure below.

One type of monomer of a starting material may comprise an organic radical, the organic radical being in particular 1,4-arylene or 1,3-arylene or 1,2-arylene or alkyl or 1,4-perfluoroarylene or 1,3-perfluoroarylene or 1 ,2-Perfluoroarylene or perfluoroalkyl or bromoarylene or chloroarylene or iodoarylene or pyridyl or pyrazinyl or pyrimidyl or triazinyl or 9H-fluorenyl or 9-dialkyl-9H-fluorenyl or 9,9-bis(haloalkyl)-9H-fluorenyl or 1,4- Cyclohexyl or 1,3-cyclohexyl or 1,2-cyclohexyl or 1-methylpiperidyl or 1,4-dimethylpiperazinyl or 1,3-dimethylhexahydropyrimidinyl comprises or consists of.

According to a preferred embodiment, a starting material can contain at least one ketone group and/or carbonyl group, in particular several different ketone groups and/or several different carbonyl groups. A ketone group can have the following structure:

R ₂ can represent hydrogen (H), phenyl, C _n H _2n-1 with n=1-20, or C _n F _2n-1 with n=1-20.

• (2-R, 3-R, 4-R, 5-R, 6-R)-x-Pyridyl mit R=H, CI
• Br, I, OMe, C_nH_2n-1 mit n=1-20, C_nF_2n-1 mit n=1-20
• NO₂, SO₃H, SH, SO₂-C_nH_2n-1 mit n=1-20 und x=2, 3 oder 4 (2-R, 3-R, 4-R, 5-R, 6-R)-x-Pyrimidinyl mit R=H,
• CI, Br, I, OMe, C_nH_2n-1 mit n=1-20, C_nH_2n-1 mit n=1-20 und x=2, 3 oder 4
• 1H-benzo[d]imidazolyl
• 1-Methyl-1 H-benzo[d]imidazolyl
• 1H-imidazolyl
• 1-Methyl-1 H-imidazolyl
• 1-methylpiperidin-2-,3- oder 4-yl
• 1-(4-methylpiperazin-2-, oder 3-yl

The radical R ₃ can be any organic radical containing basic nitrogen. It can preferably have the following structure:

• (2-R, 3-R, 4-R, 5-R, 6-R)-x-pyridyl with R=H, CI
• Br, I, OMe, C _n H _2n-1 with n=1-20, C _n F _2n-1 with n=1-20
• NO ₂ , SO ₃ H, SH, SO ₂ -C _n H _2n-1 with n=1-20 and x=2, 3 or 4 (2-R, 3-R, 4-R, 5-R, 6 -R)-x-pyrimidinyl with R=H,
• CI, Br, I, OMe, C _n H _2n-1 with n=1-20, C _n H _2n-1 with n=1-20 and x=2, 3 or 4
• 1H-benzo[d]imidazolyl
• 1-Methyl-1H-benzo[d]imidazolyl
• 1H-imidazolyl
• 1-Methyl-1H-imidazolyl
• 1-methylpiperidin-2-, 3- or 4-yl
• 1-(4-methylpiperazin-2-, or 3-yl

• (CH)kHal mit Hal=Cl, Br, I und k = 1-10
• Pentafluorphenyl
• Tetrafluorphenyl
• Trifluorphenyl
• Difluorphenyl
• Fluorphenyl

Alternatively, the radical R ₃ can be a halogen-containing organic radical. R ₃ can preferably have the following structure:

• (CH)kHal with Hal=Cl, Br, I and k = 1-10
• Pentafluorophenyl
• Tetrafluorophenyl
• Trifluorophenyl
• Difluorophenyl
• Fluorophenyl

The basic reaction scheme of a polyhydroxyalkylation is shown below.

The designation R ₁ stands for any organic radical, which preferably has one of the aforementioned structures. The designations R ₂ and R ₃ have already been explained previously.

The polyhydroxyalkylation preferably takes place under the influence of trifluoromethanesulfonic acid (TFSA). This has the molecular formula CF ₃ SO ₃ H and is a colorless, pungent-smelling, hygroscopic liquid.

In a further embodiment, the polyhydroxyalkylation (PHA) can take place under the influence of a solvent, in particular a chlorinated solvent. Such solvents are commercially available.

The modification of the synthesized polymer in a subsequent reaction and/or the modification of a starting material in a preliminary reaction can each include one or more reactions or reaction steps. It is also possible for the starting material to be modified in a preliminary reaction or in several preliminary reactions before the polymer synthesis using PHA and/or for one or more subsequent reactions to be carried out after the polymer synthesis using PHA in order to modify the synthesized polymer.

The modification of the synthesized polymer in a subsequent reaction and/or the modification of the starting material in a preliminary reaction may include a nucleophilic aromatic substitution reaction or an electrophilic aromatic substitution reaction. An electrophilic aromatic substitution reaction can be a nitration and possible subsequent reactions, a sulfonation and possible subsequent reactions, Friedel-Crafts acylations and possible subsequent reactions, Friedel-Crafts alkylations and possible subsequent reactions, a halogenation, in particular a fluorination, chlorination, bromination or iodization, and a possible subsequent reactions of halogenations, for example lithiations by means of a halogen-metal exchange or Grignard reactions, and possible subsequent reactions of the metalated, for example lithiated, polymers by reactions with any electrophiles.

A nucleophilic substitution reaction can take place in a manner known per se. One or more atoms of an aromatic compound can be substituted. For example, perfluoroaromatic compounds in which one or more fluorine atoms are substituted by a functional group may be present in the synthesized polymer. For example, a perfluorophenyl unit or a perfluorobiphenyl unit may be present in which the para position is initially substituted by a functional group. A further functional group can then also be coupled at an ortho position and/or a meta position.

Several atoms of an aromatic compound can be nucleophilically substituted at the same time in one step. Alternatively, the nucleophilic substitution of multiple atoms can occur in several successive steps.

Every substitution reaction can take place under the influence of other media. This can be a base. Alternatively or additionally, the reaction can take place under the influence of acetone, diazabicycloundecene (DBU), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfate (DMS), CH ₃ I, dimethyl carbonate or mixtures or dilute solutions of these media.

It is also conceivable that a substitution reaction takes place when a solvent is evaporated, which preferably takes place at a temperature below 150 ° C.

For substitution, a molecule with a linear or branched, saturated or unsaturated C _n body, in particular with a C ₂ -, C ₃ -, C ₆ -, C ₈ , C ₁₀ -, C ₁₂ -, C ₁₄ -, C ₁₆ -, or a C ₁₈ body which carries a thiol group at one end. An S atom of the thiol group then preferably substitutes an F atom of a perfluoroaromatic compound. In other words, a saturated or unsaturated hydrocarbon with a thiol group can be used as a substituent. If an unsaturated hydrocarbon is used, it can be used for a subsequent reaction, in particular for a thiol-ene click reaction.

At its other end, the molecule used for substitution can have a quinuclidinium group, or another quaternary N group, in particular an ammonium, imidazolium, benzimidazolium, piperidinium, piperazinium, guanidinium, or pyridinium group, preferably with counterions, in particular with a bis(trifluoromethylsulfonyl)amide anion or a mineral acid anion, ⁱⁿ particular a halide (F-, ^Cl- , Br- ^{, I-} ) or SO ₄ ^2- , HSO _4- , PO ₄ ^3- , HPO ₄ ^{2 -} , H ₂ PO ₄ ^- , SO ₃ ^2- , SO ₃ H ^- , hydrogen phosphonate R-PO ₃ H ^- , phosphonate R-PO ₃ ^2- (R=any organic radical, preferably an aryl radical preferably with electron-withdrawing groups such as F, SO ₂ R, NO, NO ₂ , etc.), carbonate CO ₃ ^2- , HCO ₃ ^- , or with an organic carboxylic acid anion, in particular CH ₃ COO-, CF ₃ COO-, HCOO-. The selection of counterions is not limited to the anions mentioned. Furthermore, the molecule used for substitution can contain a nitrogen atom as a primary, secondary, tertiary or quaternary amine or ammonium group.

A molecule in the form R -SH, R -S-, R -OH, R -NH, R -N- or PO ₃ R ₂ can also be used for substitution. Furthermore, a thiol with a terminal sulfonate group can be used for substitution. In addition, a molecule C ₅ NH ₁₀ (piperidyl radical) can be used for substitution, with the nitrogen atom taking the position of a fluorine atom of the perfluoroaromatic compound. In particular In a further embodiment, a residue (counterion) can be coupled via the nitrogen atom if it is positively charged, the residue preferably being a halide (F ^- , Cl ^- , Br ^- , I ^- ) or SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ² , H ₂ PO ₄ ^- , SO ₃ ^2- , SO ₃ H ^- , hydrogen phosphonate R-PO ₃ H ^- , phosphonate R-PO ₃ ^2- , carbonate CO ₃ ^2- , HCO ₃ ^- or an organic carboxylic acid anion, in particular CH ₃ COO ^- , CF ₃ COO ^- , HCOO ^- . The remainder can in principle contain any anion as a counterion, with anions such as halide (F ^- , Cl ^- , Br, I ^- ) or SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , SO ₃ ^2- , SO ₃ H ^- , hydrogen phosphonate R-PO ₃ H ^- , carbonate CO ₃ ^2- , HCO ₃ ^- or an organic carboxylic acid anion such as CH ₃ COO ^- , CF ₃ COO ^- , HCOO ^- are preferred .

If the molecule used for substitution has the form S - R, with the sulfur atom occupying or intended to occupy the position of the substituted fluorine atom, the radical R may be formed as shown in the figure below.

Furthermore, the molecule SO ₃ ^- used for the substitution can be with a counterion, in particular with a countercation, preferably with a metal countercation or with an ammonium countercation in the form NR ₄ ⁺ with R = H, alkyl, aryl or with another N -basic cation, in particular imidazolium, benzimidazolium, guanidinium, can be/will be substituted. A functional group may contain C ₅ NH ₁₀ , where the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound. In particular, via the nitrogen atom, a residue or counteranion can be formed, the residue preferably being a halide (F ^- , Cl ^- , Br ^- , I ^- ) or SO ₄ ^2- , HSO ₄ ^- , PO ₄ ^3- , HPO ₄ ^2- , H ₂ PO ₄ ^- , SO ₃ ^2- , SO ₃ H ^- , hydrogen phosphonate R-PO ₃ H ^- , phosphonate R-PO ₃ ^2- , carbonate CO ₃ ^2- , HCO ₃ ^- or an organic carboxylic acid anion such as CH ₃ COO ^- , CF ₃ COO ^- , HCOO- is. The remainder or the counteranion can in particular be mineral acid anions (including halides, sulfates, sulfites, phosphates, carbonates, (per-)chlorates, borates), or organic counteranions, preferably bis(sulfonyl)imides, carboxylic acid derivatives, sulfonic acid derivatives, phosphonic acid derivatives).

The substitution that takes place can be designed in such a way that a functional group is coupled to several, in particular to two, perfluoroaromatic compounds of two organic polymeric chains, so that the functional group crosslinks the chains with one another. This embodiment is based on the idea of not functionalizing the polymeric chains independently of one another, but rather functionalizing them in such a way that they are additionally networked with one another. This can particularly influence the mechanical properties of the material.

Specifically, the functional group can be designed like a chain and have a sulfur atom at both ends, which nucleophilically substitutes a fluorine atom of a perfluoroaromatic compound. One or more C _n bodies and/or a repeating unit can be contained between the sulfur atoms.

In a further embodiment of the method according to the invention, further subsequent reactions can take place following the nucleophilic substitution, for which the functional groups form a reaction basis. The residues of the functional groups that were coupled to a perfluoroaromatic compound after the substitution has taken place can be used as a basis for further subsequent reactions. These include, among others, the exchange of the counterions of a positively or negatively charged residue of the functional group, a change in the residues of the functional group or the use of an aromatic/unsaturated residue of the functional group.

Specifically, the counterions of a quaternary ammonium salt or an acid group that are part of the functional group can be exchanged. Unsaturated residues of the functional group can be used for downstream functionalization or crosslinking of the polymer/oligomer with the perfluoroaromatic compound.

The modification of the synthesized polymer in a subsequent reaction and/or the modification of the starting material in a preliminary reaction can also include a polymer-analogous reaction. In a polymer-analog reaction, a functional group is converted into another functional group through a chemical reaction.

The modification in a subsequent reaction and/or in a preliminary reaction can also include an alkylation of basic nitrogen atoms to give tertiary or quaternary N-basic compounds. Furthermore, the subsequent reaction and/or the preliminary reaction can also be microwave-assisted, in particular include a microwave-assisted synthesis. This allows the reaction to be accelerated and, if necessary, the degree of conversion (yield) to be increased. The selectivity of the reaction can also be improved.

Possible modifications in a subsequent reaction and/or in a preliminary reaction can be or include a lithiation reaction on halogenated, preferably chlorinated or brominated or iodinated polymers or monomers. The reaction scheme of a polymer in which bromine is directly attached to the aromatic is shown below.

Alternatively, bromine can be in the benzylic position or bound to an alkylene residue. The corresponding reaction scheme is shown below.

Such a lithiated monomer or a lithiated PHA polymer can be reacted with further reactions, ie further preliminary reactions in the case of a monomer or subsequent reactions in the case of a polymer. This can be, for example, a sulfinate S-alkylation or a Suzuki coupling. Further exemplary subsequent reactions are shown in the following reaction scheme.

According to a preferred embodiment, the lithiated PHA polymer can be reacted with a carbonyl derivative of a di-(cyclopentadienyl) transition metal complex, in particular ferrocenaldehyde, acetylferrocene or ferrocenoic acid chloride. A subsequent partial or complete oxidation of the transition metal central atom of the complex to an anion exchange polymer results in a material with excellent chemical stability. When producing membranes from a solution of the partially oxidized di-(cyclopentadienyl) transition metal complex bound to the polymer in a (preferably) dipolar-aprotic solvent such as DMAc, DMF, DMSO, sulfolane, etc., a magnetic field is used, whereby the field lines of the magnetic field are perpendicular to the membrane surface are aligned, the metal-containing functional groups can be aligned in the direction of the magnetic field, which leads to the formation of ion-conducting channels “through-plane” and thus to a higher conductivity than if the ion-conducting channels are not aligned in the magnetic field (proof of principle of this new type of polymer in the form of partially oxidized vinyl ferrocene see the following study: Xin Liu, Na Xie, Jiandang Xue, Mengyuan Li, Chenyang Zheng, Junfeng Zhang, Yanzhou Qin, Yan Yin, Dario R. Dekel, Michael D. Guiver, Nature Energy 2022, 7, 329-339 , DOI: 10.1038/s41560-022-00978-y).

As a subsequent or preliminary reaction, a benzyl bromination with N-bromo-succinimide (NBS) and a further reaction of the bromomethyl group, in particular a reaction with a tertiary amine, to form an anion exchange polymer can also take place. Lithiation on the methyl group of an aromatic with n-butyllithium is also conceivable, followed by further reactions, in particular the grafting of an anionically polymerizable polymer, in particular polystyrene, poly(4-vinylpyridine) or poly(diethylvinylphosphonate). The corresponding reactions can take place both as a preliminary reaction to modify the starting material and as a subsequent reaction to modify the synthesized (PHA) polymer.

The modification of the synthesized polymer in a subsequent reaction and/or the modification of the starting material in a preliminary reaction may also include a Suzuki-Miyaura coupling reaction and/or an electrophilic sulfonation reaction and/or a phosphonation reaction and/or an amination reaction and/or a thiolation reaction. Concentrated sulfuric acid or TMSA (trimethylsilylacetylene) or chlorosulfonic acid (ClSOH) or oleum (H ₂ SO ₄ with 5-65% SO ₃ ) or trimethylsilyl chlorosulfate (TMS-OSO ₂ -Cl) or a combination of these materials can be used as the sulfonating agent.

By modifying the synthesized polymer in a subsequent reaction or modifying the starting material in a preliminary reaction, ionic and/or covalent crosslinks can also be formed between the individual polymer chains. In principle, this reduces swelling/water absorption, which results in an improvement in the property profile of membranes made from the material. This can take place, for example, by nucleophilic substitution of a pentafluorophenyl residue of a polymer with an aromatic or aliphatic dithiol.

In the case of Friedel-Crafts acylation and/or Friedel-Crafts alkylation, quaternization of the polymer can be carried out with any other tertiary N-basic compound. By way of example, the compounds can be tetramethylimidazole, trimethylamine, N-methylpiperidine, N-methylpiperazine or 3-methyl-3,6-diazaspiro[5.5]undecane-6-i-umbromide. Any nucleophilic aromatic substitutions can be carried out on a pentafluorophenyl residue of the synthesized polymer.

The modification in a preliminary reaction or in a subsequent reaction can also include doping, in particular with phosphoric acid or any phosphonic acid, which has proven to be particularly advantageous for use in high-temperature membrane fuel cells. The membranes doped in this way can be converted into a covalently cross-linked blend membrane by blending with another polymer, in particular with poly(vinylbenzyl chloride) (PVBCI). Specifically, this can be done by reacting the chloromethyl groups of the PVBCI with the N-H-of the imidazole function, or by blending with an acidic sulfonated or phosphonated polymer to form acid-base blend membranes.

The method of the invention may further comprise blending the synthesized polymer with another polymer to form a blended polymer mixture. In other words, it is envisaged that the polymer synthesized by polyhydroxyalkylation, which has corresponding modifications, is mixed with at least one other polymer.

The blending can result in crosslinks, in particular ionic and/or covalent crosslinks, between the polymers. In this way, the mechanical and chemical stability of membranes made from such materials can be improved compared to membranes consisting only of the synthesized polymer. At the same time, the ion conductivity can be increased.

It is also possible that further post-treatment of the blended polymer mixture takes place. Specifically, doping can take place. The blended polymer mixture can be doped with mineral acids, in particular with sulfuric acid or phosphoric acid or any organic phosphonic acid of the structure R(PO ₃ H ₂ ) _x (R=any organic radical, preferably an electron-poor aromatic group such as one with one or more F or one or several other electron-withdrawing groups such as NO, NO ₂ , SO ₂ R etc., because electron-withdrawing groups increase the acidity and thus increasing the ionic conductivity of the phosphonic acid, x=1-12). Furthermore, the aftertreatment can include the introduction of further ion exchange groups, in particular moderately to strongly acidic phosphonic acid and/or acidic sulfonic acid groups and/or strongly acidic sulfonimide groups.

Furthermore, anion exchange groups can be generated on the blinded polymer mixture. Anion exchange groups can be generated by the alkylation (quaternization) of any tertiary N-basic groups contained in the blended polymer mixture and/or by the reaction of halomethyl groups of the form CH ₂ Hal with Hal=Cl, Br, I contained in the blended polymer mixture tertiary N-basic groups. Through these process steps, the properties of the material thus obtained and in particular of a membrane made from this material can be further improved.

A material produced using such a process is characterized by a particularly favorable property profile. Specifically, the substance can be a synthesized polymer that contains halogens Hal directly bound to the aromatics (Hal=CI, Br, I). These can already be contained in the monomers of the starting material or can have been created by a polymer-analogous bromination of the synthesized polymers with elemental bromine, optionally with FeCl ₃ or AlCl ₃ catalysis, or by reaction with NBS (N-bromo-succinimide).

It is also possible for the materials produced by the method according to the invention to be processed into fiber mats, in particular porous fiber mats, which are also referred to as tangled nonwovens, by means of electrospinning or centrifugal spinning. In a further step, the fiber mats can be impregnated with a second polymer, either with a cation exchange or anion exchange polymer according to the invention or with a basic polymer according to the invention, and / or with an inert filler polymer. In this way, composite membranes made of the fiber mat and the infiltrated polymer, in which the fiber mat acts as a mechanical reinforcement and, depending on the type of polymer from which the fiber mat is made, can even be ion-conductive if the material of the fiber mat is made of a cation exchange or a Anion exchange polymer consists or a mixture of an anion exchange polymer with a cation exchange polymer. The mixture of a sulfonated polymer with a basic polymer can also optionally be spun into fibers, whereby the conductivity of the fibers can be adjusted by the molar mixing ratio between the polymers. As long as there is a molar excess of acidic polymer in the polymer mixture, the fibers are cation-conductive. If the molar mixing ratio between acidic and basic polymers is 1:1, i.e. there are no excess cation-conducting groups left, the fibers are no longer cation-conductive.

The object on which the invention is based is further achieved by a membrane which comprises or consists of such a substance, which was produced by a method as described above.

The thickness of the membrane can be less than 100 μm, in particular less than 75 μm, preferably less than 50 μm. To produce the membrane, the material, which was produced using a process as described above, can be dissolved in a suitable solvent and doctored onto a corresponding surface. This results in appropriate membrane thicknesses. In a preferred embodiment, it can be an ion exchange membrane, preferably a cation exchange membrane or an anion exchange membrane.

The invention furthermore relates to the use of such a membrane in a fuel cell, in particular in a high-temperature or a low-temperature fuel cell and/or in a direct alcohol fuel cell, or in a battery, in particular in a redox flow battery, and/or in an electrochemical process , in particular in an electrolysis process or in an electrosynthesis process, preferably in a water electrolysis process, and / or as a proton exchange membrane.

• 1 ein Reaktionsschema eines erfindungsgemäßen Verfahrens gemäß einem ersten Ausführungsbeispiel der vorliegenden Erfindung;
• 2 ein Reaktionsschema von erfindungsgemäßen Verfahren gemäß einem zweiten Ausführungsbeispiel der vorliegenden Erfindung;
• 3 ein Reaktionsschema einer weiteren möglichen Folgereaktion der in der 2 dargestellten Verfahren;
• 4 ein Reaktionsschema eines erfindungsgemäßen Verfahrens gemäß einem dritten Ausführungsbeispiel der vorliegenden Erfindung;
• 5a, 5b Reaktionsschemata von erfindungsgemäßen Verfahren gemäß einem vierten Ausführungsbeispiel der vorliegenden Erfindung;
• 6 ein Reaktionsschema von erfindungsgemäßen Verfahren gemäß einem fünften Ausführungsbeispiel der vorliegenden Erfindung;
• 7 ein Reaktionsschema eines erfindungsgemäßen Verfahrens gemäß einem sechsten Ausführungsbeispiel der vorliegenden Erfindung;
• 8 ein Reaktionsschema des erfindungsgemäßen Verfahrens gemäß einem siebten Ausführungsbeispiel der vorliegenden Erfindung;
• 9 eine alternative oder ergänzende Vorabreaktion zu dem Verfahren aus 8;
• 10 ein ¹H-NMR-Spektrum eines Copolymers aus Paraterphenyl und 1-(1 H-Benzimidazol-2-yl)ethanon (Ausführungsbeispiel 8);
• 11 eine GPC-Kurve des Copolymers aus 10;
• 12 ein ¹H-NMR-Spektrum des vollständig methyliertem Copolymers aus Paraterphenyl und 1-(1 H-Benzimidazol-2-yl)ethanon im Vergleich zum unmethylierten Ausgangspolymer;
• 13 ein ¹H-NMR-Spektrum des Copolymers aus 10, welches mit 1,2-bis-(Chlorethoxy)-Ethan umgesetzt wurde im Vergleich zum Ausgangspolymer;
• 14 ein ¹H-NMR Spektrum des Copolymers aus para-Terphenyl und 1-(1H-Benzimidazol-2-yl)ethanon, welches mit 1,2-Bis-(chlorethoxy)-ethan umgesetzt wurde in DMSO-d₈, welches mit Trimethylamin zu einem Anionentauscherpolymer quarternisiert wurde;
• 15 ein ¹H-NMR-Spektrum des Copolymers aus m-Terphenyl, Biphenyl und 4-Acetylpyridin in CH₂Cl₂ (Ausführungsbeispiel 9);
• 16 ein ¹H-NMR-Spektrum des zu 15% methylierten Copolymers aus 15;
• 17a, 17b eine Grafik mit Coulomb-Effizienz, Spannungs-Effizienz und Energie-Effizienz einer Membran aus den Stoffen des Ausführungsbeispiels 9;
• 18 ein Reaktionsschema eines erfindungsgemäßen Verfahrens gemäß einem zehnten Ausführungsbeispiel;
• 19 das ¹H-NMR-Spektrum des mittels des Reaktionsschemas aus 18 hergestellten Stoffs;
• 20 ein Reaktionsschema einer Vorabreaktion eines erfindungsgemäßen Verfahrens gemäß einem elften Ausführungsbeispiel;
• 21 das ¹H-NMR-Spektrum des Stoffs, welcher durch das Verfahren gemäß dem Reaktionsschema aus 20 hergestellt wurde;
• 22 ein Reaktionsschema einer Polyhydroxyalkylierung, wobei ein Ausgangsstoff mit dem in der 20 dargestellten Verfahren modifiziert wurde;
• 23 ein Reaktionsschema eines erfindungsgemäßen Verfahrens gemäß einem zwölften Ausführungsbeispiel;
• 24 das ¹H-NMR-Spektrum des mittels des in 23 dargestellten Verfahren erhaltenen Stoffs; und
• 25 das ¹H-NMR-Spektrum eines Stoffs erhalten aus einem erfindungsgemäßen Verfahrens gemäß einem 13. Ausführungsbeispiel;
• 26 das ¹⁹F-NMR-Spektrum des Stoffs erhalten durch ein Verfahren gemäß dem 13. Ausführungsbeispiel;
• 27 ein weiteres ¹H-NMR-Spektrum des Ausgangspolymers und des modifizierten sulfonierten Polymers des 13. Ausführungsbeispiels;
• 28 Strukturformeln von Polymeren, die gemäß einem 14. Ausführungsbeispiel eines erfindungsgemäßen Verfahrens hergestellt wurden; und
• 29 ein ¹⁹F-NMR-Spektrum eines doppelt phosphonierten Copolymers aus p-Terphenyl und Perfluoracetophenon (15. Ausführungsbeispiel).

For further development of the invention, reference is made to the subclaims and to the following description of exemplary embodiments with reference to the figures. The substances mentioned in the description of the exemplary embodiments, in particular the polymers mentioned, are preferred embodiments of a substance according to the present invention. Show in the figures

• 1 a reaction scheme of a method according to the invention according to a first embodiment of the present invention;
• 2 a reaction scheme of processes according to the invention according to a second embodiment of the present invention;
• 3 a reaction scheme of another possible subsequent reaction in the 2 procedures presented;
• 4 a reaction scheme of a method according to the invention according to a third embodiment of the present invention;
• 5a , 5b Reaction schemes of processes according to the invention according to a fourth embodiment of the present invention;
• 6 a reaction scheme of processes according to the invention according to a fifth embodiment of the present invention;
• 7 a reaction scheme of a method according to the invention according to a sixth embodiment of the present invention;
• 8th a reaction scheme of the process according to the invention according to a seventh embodiment of the present invention;
• 9 an alternative or supplementary preliminary reaction to the procedure 8th ;
• 10 a ¹ H NMR spectrum of a copolymer of paraterphenyl and 1-(1 H-benzimidazol-2-yl)ethanone (Example 8);
• 11 a GPC curve of the copolymer 10 ;
• 12 a ¹ H NMR spectrum of the fully methylated copolymer of paraterphenyl and 1-(1 H-benzimidazol-2-yl)ethanone in comparison to the unmethylated starting polymer;
• 13 a ¹ H NMR spectrum of the copolymer 10 , which was reacted with 1,2-bis-(chloroethoxy)-ethane compared to the starting polymer;
• 14 a ¹ H-NMR spectrum of the copolymer of para-terphenyl and 1-(1H-benzimidazol-2-yl)ethanone, which was reacted with 1,2-bis-(chlorethoxy)-ethane in DMSO-d ₈ , which was reacted with trimethylamine was quaternized to an anion exchange polymer;
• 15 a ¹ H-NMR spectrum of the copolymer of m-terphenyl, biphenyl and 4-acetylpyridine in CH ₂ Cl ₂ (Example 9);
• 16 a ¹ H-NMR spectrum of the 15% methylated copolymer 15 ;
• 17a , 17b a graphic with Coulomb efficiency, voltage efficiency and energy efficiency of a membrane made from the materials of exemplary embodiment 9;
• 18 a reaction scheme of a method according to the invention according to a tenth exemplary embodiment;
• 19 the ¹ H-NMR spectrum of the using the reaction scheme 18 manufactured fabric;
• 20 a reaction scheme of a preliminary reaction of a method according to the invention according to an eleventh exemplary embodiment;
• 21 the ¹ H-NMR spectrum of the substance produced by the process according to the reaction scheme 20 was produced;
• 22 a reaction scheme of a polyhydroxyalkylation, where a starting material with that in the 20 the procedure presented has been modified;
• 23 a reaction scheme of a method according to the invention according to a twelfth exemplary embodiment;
• 24 the ¹ H-NMR spectrum of the using the in 23 material obtained by the process shown; and
• 25 the ¹ H-NMR spectrum of a substance obtained from a method according to the invention according to a 13th exemplary embodiment;
• 26 the ¹⁹ F NMR spectrum of the substance obtained by a method according to the 13th embodiment;
• 27 a further ¹ H-NMR spectrum of the starting polymer and the modified sulfonated polymer of the 13th embodiment;
• 28 Structural formulas of polymers which were produced according to a 14th embodiment of a method according to the invention; and
• 29 a ¹⁹ F NMR spectrum of a doubly phosphonated copolymer of p-terphenyl and perfluoroacetophenone (15th embodiment).

Example 1

The 1 shows a reaction scheme of an exemplary embodiment of a method according to the invention for producing a material for a membrane. A starting material is used which contains 1-(4-methylpyridin-2-yl)ethan-1-one and an m-terphenyl. A polymer is synthesized using polyhydroxyalkylation, which is then lithiated with n-butyllithium. In a further subsequent reaction, 4-vinyl-pyridine is grafted anionically.

Example 2

The 2 also shows a reaction scheme of processes according to the invention. A starting material is provided which contains m-terphenyl and perfluoroacetophenone. In a first step, polymer synthesis takes place using polyhydroxyalkylation. The PHA polymer thus obtained (polymer 2) is then sulfonated in a subsequent reaction, so that polymer 3 is obtained. A modification can then optionally be carried out in a subsequent reaction with basic groups (polymer 3a, polymer 3b), whereby the basic groups can form ionic crosslinking points with the sulfonic acid groups. This reduces the swelling and water absorption of a membrane made from such a polymer, so that the performance properties improve, particularly in electrochemical applications such as fuel cells, PEM electrolysis or redox flow batteries. It is also conceivable to blend the sulfonated polymer 3 with a basic polymer, for example with the polymers 3a, 3b or another basic polymer such as a polybenzimidazole, so that ionically cross-linked acid-base blend membranes are created.

Following the sulfonation, additional phosphonation can take place to improve the proton conductivity, especially at temperatures above 100°. The improvement in proton conductivity results from the intrinsic proton conductivity of the phosphonic acid group (polymer 3c). Based on this, an alkyl side chain can be introduced through a nucleophilic substitution reaction (polymer 3ca), which reduces the brittleness of the resulting polymer.

The sulfonated polymer 3 can, as in the 3 is shown, can also be cross-linked covalently by nucleophilically substituting the 4F atoms of the pentafluorophenyl residue of the polymer with an aromatic or aliphatic dithiol. This then results in the 3 3d illustrated polymer.

Example 3

An alternative method according to the present invention is in 4 shown. A starting material is first modified in a preliminary reaction. Specifically, in a first step, commercially available 1-(4-mercaptophenyl)ethan-1-one is oxidized to 4-acetylbenzenesulfonic acid. In the next step, a polymer synthesis is then carried out using polyhydroxyalkylation with m-terphenyl to give a sulfonated aromatic polymer 4.

Example 4

5a , 5b show various methods for producing a material for a membrane, which in particular include a Friedel-Crafts acylation and/or a Friedel-Crafts alkylation. Starting from polymer 5, which is in the 5 is shown, a corresponding modification can take place (polymers 7 or 6). Starting from polymer 6, any nucleophilic aromatic substitution can then be carried out on the pentafluorophenyl residue (polymer 6a). The polymer 6a in the present case is a cation exchange polymer. Starting from polymer 7, Friedel-Crafts acylation can occur to obtain an anion exchange polymer 7b.

Example 5

The 6 shows a reaction scheme of processes according to the invention, in which 1-(1H-benzo[d]imidazol-2-yl)ethan-1-one is first reacted with p-terphenyl in a PHA polymer synthesis, so that polymer 8 is formed. The NH group can then be deprotonated using LiH and followed by alkylation with methyl iodide to give the anion exchange polymer 8a. Alternatively, starting from the polymer 8, a sulfonation can take place, for example with chlorosulfonic acid, so that the acid-base polymer 8b is formed.

_{It is} also conceivable to dope with phosphoric acid (PA) or any phosphonic acid (PhnA) R(PO ₃ H ₂ ) SO ₂ R etc., x=1-12) in order to be able to use the polymer in high-temperature membrane fuel cells. The PA-doped high-temperature membranes can be converted into a covalently cross-linked blend membrane by blending with poly(vinylbenzyl chloride) (PVBCI) by reacting the chloromethyl groups of the PVBCI with the NH of the imidazole function. Instead of PVBCI, one can also be used for the reactive blending (reaction of the CH ₂ Hal groups with NH) of the PHA polymer from 1-(1 H-benzo[d]imidazol-2-yl)ethan-1-one and p-terphenyl Styrenic polymer can be used which carries the halomethyl group CH ₂ Br or CH ₂ Cl at the end of a side chain which is attached in the 4-position of the aromatic of the polystyrene (for example the polymer obtained by free radical polymerization from 1-(6-chlorohexyl)-4 -vinylbenzene can be produced). Alternatively, it is also conceivable to produce an acid-base blend membrane by blending with an acidic sulfonated or phosphonated polymer.

Example 6

The 7 shows a further exemplary embodiment of a method according to the invention for producing a material for a membrane. An acetylpyridine is combined with a biphenyl and/or terphenyl, in this case 2,2,2-trifluoro-1-(pyridin-4-yl)ethan-1-one, with a pyridine-containing oligophenyl, in this case 2,6-diphenylpyridine a polyhydroxyalkylation to obtain a synthesized, basic PHA polymer (polymer 9). The polymer 9 can then be converted either completely or partially to form the anion exchange polymer 9a. The ratio between pyridine groups and quaternized pyridinium groups can be adjusted so that the property profile is favorable for use in electrochemical membrane processes, for example in redox flow batteries. The quaternization of the polymer 9 to give the anion exchange polymer 9a can take place either by reaction with Mel or dimethyl sulfate or by reaction with a dihaloalkane, for example 1,4-diiodobutane, 1,6-diiodhexane, 1-chloro-6-iodhexane, 1-bromo-6 -iodhexane or the like. The reaction of both halogen atoms of the dihaloalkane simultaneously creates a covalent crosslinking of the resulting anion exchange polymer. If a mixed haloalkane is used, the reaction conditions can be chosen so that only the more reactive halogen (reactivity series of haloalkanes for nucleophilic substitution I>Br>Cl>>F) reacts by quaternization and the more inert halogen is retained and used for further downstream nucleophilic substitution reactions can be used, for example for the quaternization reaction with another tertiary N-basic compound.

It is conceivable that the anion exchange polymer 9a produced by alkylation of the polymer 9 with any basic polymer, for example with the polymer 8 from the 6 , can be blinded in order to optimize the properties such as ionic conductivity, water absorption and mechanical properties for the respective application of a membrane.

Example 7

The 8th shows a reaction scheme of a process according to the invention, by means of which a so-called ferrocene polymer is produced. In this way, novel anion exchange polymers can be synthesized (for the proof-of-principle of this novel type of polymer in the form of partially oxidized poly(vinylferrocene) see the following study: Xin Liu, Na Xie, Jiandang Xue, Mengyuan Li, Chenyang Zheng, Junfeng Zhang, Yanzhou Qin, Yan Yin, Dario R. Dekel, Michael D. Guiver, Nature Energy 2022, 7, 329-339 , DOI: 10.1038/s41560-022-00978-y). According to the invention, cyclopentadienyl complexes such as ferrocene (bis(cyclopentadienyl)iron) in the form of a methyl ketone (acetylferrocene) of its aldehyde (ferrocenaldehyde) are reacted with an aryl in a polyhydroxyalkylation. In the polymer synthesized in this way, the ferrocene at the metal central atom is then partially oxidized to obtain a positively charged polymer with a mixed oxidized state. Since the polymer is paramagnetic because of the iron, the polymer chains can be aligned using a magnetic field, thereby Directed, ion-conductive paths are created in the polymer. Compared to a ferrocene polymer in the form of a poly(vinylferrocene), the one according to the invention, in which 8th Polyferrocene shown is chemically more stable in its polymer main chain because it does not contain any tertiary CH bonds that are vulnerable to radical attack.

In the 9 Another reaction scheme is shown with which the content of ferrocene groups in a polymer can be increased. To do this, a monobrominated terphenyl monomer can first be substituted with ferrocene groups.

According to the reaction scheme in the 9 The m-terphenyl modified with ferrocene is first synthesized with ferrocene ketone or aldehyde using polyhydroxyalkylation to form a polymer and then, as in 8th is shown, partially oxidized to produce a corresponding ferrocene anion exchange polymer.

Embodiment 8

Poly(terphenyl-co-1-(1H-Benzimidazol-2-yl)ethanone) (Polymer 8)

A terphenyl derivative such as para-terphenyl and an aromatic ketone such as 1-(1H-benzimidazol-2-yl)ethanone are suspended in a halogenated solvent such as dichloromethane, preferably with an excess of the ketone between 1.00 and 2.00 equivalents and particularly preferably with an excess between 1.15 and 1.40 equivalents is worked. The trifluoromethanesulfonic acid is then added, with the reaction mixture being stirred between 0 ° C and 60 ° C. The trifluoromethanesulfonic acid is preferably used in a molar excess in relation to the ketone of 5-20 equivalents, with 8-13 equivalents being particularly preferred. After a preferred PHA reaction time of between 7 hours and 72 hours, the reaction is stopped by pouring the reaction mixture into water. 10 shows the ¹ H-NMR spectrum of the copolymer (8) produced in this way with a clear assignment of all resonance signals to the protons of the polymer. Gel permeation chromatography (GPC) ( 11 ) shows, depending on the reaction time and the molar excess of the ketone, molecular weights (M _n ) between 20,000 g/mol and 300,000 g/mol and dispersities of 1.40 to 2.00 ( ), whereby 0.1 M LiCl DMSO and narrowly distributed PMMA standards were used as solvents for the GPC. Furthermore, thermogravimetric analysis showed a high decomposition temperature of 480 °C.

The copolymer of para-terphenyl and 1-(1H-benzimidazol-2-yl)ethanone can be converted into an anion-conducting polymer by methylating the two nitrogens using suitable methylating agents such as methyl iodide, dimethyl sulfate or dimethyl carbonate. The methylation can be carried out by dissolving the polymer in DMSO and adding K ₂ CO ₃ or NaH to the resulting solution. An excess of the methylating agent is then added. After stirring for 16-30 h at 25°C - 130°C, (partial or complete) methylation of both nitrogens of the benzimidazole ring takes place. Depending on the reaction temperature and reaction time, different degrees of methylation are possible.

When in 12 In the example shown, it was surprisingly found that complete methylation of both nitrogen atoms to the imidazolium cation has taken place, which is evidenced by the complete absence of the resonance signal of the NH protons (12-15 ppm, above, 12 ), the shift of the aromatic signals downfield and characterized by a new signal that belongs to the two introduced methyl groups. The integrals agree completely with the expected protons. The complete methylation of both nitrogen atoms is confirmed when comparing the ¹ H-NMR spectrum of the methylated polymer (8a, top, 12 )) with the ¹ H-NMR spectrum of the original polymer clearly (below, 12 ). The conductivity of the fully methylated polymer in iodide form is 1.7 mS/cm, which further underlines the successful introduction of charged groups and demonstrates the principle applicability of the polymer as an anion exchange material. If the above reaction is carried out with meta-terphenyl instead of para-terphenyl and then the methylation is also carried out as described above, the chloride conductivity increases to 5.7 mS/cm.

In addition to the direct alkylation of the benzimidazole unit to the positively charged imiadzolium, the introduction of the positively charged group is also possible by attaching a flexible side chain. It was surprisingly found that by reacting the copolymer of para-terphenyl and 1-(1H-benzimidazol-2-yl)ethanone with a 5- to 60-fold excess, 1,2-bis-(chlorethoxy)-ethane is formed in the presence a base (e.g. K ₂ CO ₃ , NaH, etc.) at temperatures between 25°C and 150°C selectively only Allows nitrogen to alkylate. Furthermore, it was found that no crosslinking took place either, since the polymers were still soluble in polar aprotic solvents such as N,N-dimethylacetamide or N,N-dimethylformamide or dimethyl sulfoxide. 13 shows the comparison of the ¹ H NMR spectra of the starting polymer with the spectrum of the polymer 8b functionalized with a flexible ether group. The resonance signal of the NH group is no longer detectable, and the integrals of the introduced side chain agree with the expected number of protons. When calibrated to the methyl group of the polymer backbone, it can be seen that, surprisingly, quantitative functionalization has occurred ( 13 ). Following the introduction of the side chain, the chlorine substituent can be reacted with a tertiary amine in a Menschutkin reaction to form an anion-conducting group. Analogous to the functionalization with the described flexible ether side chains, the functionalization with other dihaloalkanes such as dibromohexane or diiodhexane with subsequent quaternization is possible. The separation of the anion exchange group from the polymer backbone by a flexible chain has the advantage of phase separation, which leads to the formation of ionic channels and thus higher conductivities. 14 shows the ¹ H-NMR spectrum of polymer 8b, which was converted into an anion exchange polymer with trimethylamine. The successful quaternization can be recognized by the characteristic signal of the methyl groups of the introduced trimethylammonium group at 2.97 ppm.

Embodiment 9

• Ein Terphenylderivat wie m-Terphenyl und/oder Biphenyl und ein aromatisches Keton wie 4-Acetylpyridin werden in einem halogenierten Lösungsmittel wie Dichlormethan suspendiert, wobei bevorzugt mit einem Überschuss des Ketons zwischen 1.00 und 2.00 Äquivalenten und besonders bevorzugt mit einem Überschuss zwischen 1.10 und 1.40 Äquivalenten des Ketons gearbeitet wird. Anschließend erfolgt die Zugabe der Trifluormethansulfonsäure, wobei die Reaktionsmischung zwischen 0°C und 60 °C gerührt wird. Die Trifluormethansulfonsäure wird bevorzugt in einem molaren Überschuss im Verhältnis zum Keton von 5-20 Äquivalenten verwendet, wobei besonders bevorzugt mit 8 - 13 Äquivalenten gearbeitet wird. Nach einer bevorzugten Reaktionszeit (PHA) zwischen 7h und 48 h wird die Reaktion durch Gießen des Reaktionsgemischs in Wasser abgebrochen. 15 zeigt das ¹H NMR Spektrum des auf diese Weise hergestellten Copolymers mit eindeutiger Zuordnung aller Resonanzsignale zu den Protonen des Polymers. Die Gelpermeationschromatographie (GPC) zeigt in Abhängigkeit von der Reaktionszeit und dem molaren Überschuss des Ketons, Molekulargewichte (M_n) zwischen 10 000 g/mol und 300 000 g/mol und Dispersitäten (Ɖ) von 1,40

Poly(m-terphenyl-co-biphenyl-co-(4-acetylpyridine)) (Polymer 10):

• A terphenyl derivative such as m-terphenyl and/or biphenyl and an aromatic ketone such as 4-acetylpyridine are suspended in a halogenated solvent such as dichloromethane, preferably with an excess of the ketone between 1.00 and 2.00 equivalents and particularly preferably with an excess between 1.10 and 1.40 equivalents of the ketone is worked on. The trifluoromethanesulfonic acid is then added, with the reaction mixture being stirred between 0 ° C and 60 ° C. The trifluoromethanesulfonic acid is preferably used in a molar excess in relation to the ketone of 5-20 equivalents, with 8-13 equivalents being particularly preferred. After a preferred reaction time (PHA) between 7 hours and 48 hours, the reaction is stopped by pouring the reaction mixture into water. 15 shows the ¹ H NMR spectrum of the copolymer produced in this way with a clear assignment of all resonance signals to the protons of the polymer. Depending on the reaction time and the molar excess of the ketone, gel permeation chromatography (GPC) shows molecular weights (M _n ) between 10,000 g/mol and 300,000 g/mol and dispersities (Ɖ) of 1.40

To adjust the water absorption, a partial methylation of the pyridine units in the aforementioned copolymer can be carried out in a subsequent reaction by stirring the polymer dissolved in NMP with a methylating agent (e.g. methyl iodide) for 1h-30h. This in 16 ¹ H-NMR spectrum shown represents such a polymer (polymer 10a) with a degree of methylation of 15%.

Membranes can be produced from the polymers described above using a doctor blade. For this purpose, solutions of the polymers are prepared in NMP, DMAc or DMSO with a mass fraction of the polymer between 1% and 30%. The conductivities, methylation levels and thicknesses of two membranes produced in this way are shown in the table below. Membrane/polymer Methylation level (%) Thickness (µm) σ(m5*cm ^-1 ) 10 MTp-Bp-Pyr-0 0 35 17.4 ± 3.5 10a MTp-Bp Pyr-15 15 32 20.1 ± 0.1

The previously described membranes can potentially be used in various electrochemical applications. An example of such an application is the vanadium redox flow battery. The 17a , 17b established the Coulomb efficiency (CE), the voltage efficiency (VE) and the energy efficiency (EE) as a function of the current density and over the course of 30 cycles at a current density of 80 mA*cm ^-2 of a single cell test with one of the Polymer MTp-Bp Pyr-15 existing membrane.

Embodiment 10

5'-(6-Bromohexyl)-1,1':3',1''-terphenyl

The synthetic route to obtain the starting material or starting monomer is in the 18 shown. 12.56 g (39.8 mmol) of 5'-(6-bromohexyl)-1,1':3',1''terphenyl are taken up in 50 mL THF and cooled to -85 ° C. 16.72 mL (41.8 mmol) of a 2.5 M butyllithium solution in hexane are added and the solution is stirred for 3 hours. 24.1 mL (159.0 mmol) of 1,6-dibromohexane are slowly added dropwise to the reaction mixture using a dropping funnel. The temperature is increased to -20°C and the mixture is stirred for another 16 hours. The reaction is stopped by adding 5 mL of a 10 wt.% HCl solution. The reaction equation for this reaction is in the 18 shown. For processing, the organic and aqueous phases are separated from each other. The aqueous phase is shaken 3x with 10 mL ethyl acetate. The organic phase is dried using magnesium sulfate. THF and ethyl acetate are distilled off under vacuum. The excess dibromohexane is distilled off in a high vacuum at 110°C. The product mixture is purified using flash chromatography. The 19 shows the ¹ H-NMR spectrum of the fraction that was used for the further reaction.

Embodiment 11

4-(7-[1,1':3',1''-terphenyl]-5'-yl)heptyl)pyridine

The synthetic route to obtain the starting material or starting monomer is in the 20 listed. 22 mL of dry THF are placed in a 100 mL Schlenk flask and cooled to -78°C. 2.66 mL (18.9 mmol) of diisopropylamine are added. After about 5 minutes, 7.38 mL of a 2.5 M butyllithium solution in hexane (18.5 mmol) are added. After 30 min, 1.36 mL (13.8 mmol) of 4-methylpyridine are added and the solution is stirred for 1 h. 3.63 g of 5'-(6-bromohexyl)-1,1':3',1''-terphenyl (9.2 mmol) are dissolved in 15 mL of dry THF and slowly added dropwise to the reaction mixture (15 min). The solution is stirred for 1h at -78°C and 4h at RT and then finished by adding 20 mL of saturated ammonium chloride solution and 20 mL of water. For processing, the organic and aqueous phases are separated. The aqueous phase is shaken 3x with 20 mL ethyl acetate. The organic phases are combined and washed twice with 20 mL of water and then dried using magnesium sulfate. THF and ethyl acetate are distilled off under vacuum and the product mixture is purified using flash chromatography (isolated yield: 74%). The 21 shows the ¹ H-NMR spectrum of the product.

Both compounds shown above can be converted into polymers using the polyhydroxyalkylation described above. Initial preliminary experiments on polyhydroxyalkylation of this monomer with 4-acetylpyridine have resulted in molecular masses of around 8,000 g/mol. By optimizing the reaction conditions (mass ratio between the pyridine-modified m-terphenyl and the acetylpyridine, reaction time and temperature) it can be assumed that the molecular mass of the polymers can be further increased.

In the 22 the PHA reaction of 4-(7-([1,1':3',1''-terphenyl]-5'-yl) heptyl)pyridine with 4-acetylpyridine is shown. If the polymer 11 is partially or completely pyridine-alkylated, it can be used both in alkaline applications (AEMWE or AEMFC) and in redox flow batteries.

Embodiment 12

4-Methylpyridine coupling poly-biphenyl-co-7-bromo-1,1,1-trifluoroheptan-2-one

The synthesis of poly-biphenyl-co-7-bromo-1,1,1-trifluoroheptan-2-one is in the 23 shown. 25 mL of dry THF are placed in a 250 mL Schlenk flask and cooled to -78°C. 1.10 mL (7.8 mmol) of diisopropylamine are added. After about 5 minutes, 3.09 mL of a 2.5 M butyllithium solution in hexane (7.74 mmol) are added. After 30 min, 0.51 mL (5.2 mmol) of 4-methylpyridine are added and the solution is stirred for 1 h. 0.50 g (1.3 mmol) of poly-biphenyl-co-7-bromo-1,1,1-trifluoroheptan-2-one are dissolved in 75 mL of dry THF and slowly added dropwise to the reaction mixture (15 min). The solution is stirred at -78°C for 4 hours and at RT for 20 minutes and then finished by adding 2 mL of methanol. The reaction equation for the synthesis of polymer 12 is given in 23 shown. For purification, the product mixture is concentrated to 20 mL under vacuum, precipitated in 200 mL methanol, filtered off, 3 times with fresh Washed with methanol and dried in a drying cabinet at 85 ° C. The 24 shows the ¹ H-NMR spectrum of the product.

Membranes can be produced from the previously described polymer 12 using a doctor blade. For this purpose, solutions of the polymer are prepared in NMP, DMAc or DMSO with a mass fraction of the polymer between 1% and 30% and an optional addition of an organic acid, such as trifluoroacetic acid. Such a membrane with a thickness of 32-35 µm showed a conductivity of σ = 14 mS*cm ^-1 .

Embodiment 13

Sulfonated poly-p-terphenyl-co-perfluoroacetophenone analogous to polymer 3

1.0 equivalents of terphenyl and 1.0 to 2.0 equivalents (preferably 1.1 to 1.4 equivalents) of the ketone in 9-13 equivalents of dichloromethane are placed in a Schlenk flask. 9-13 equivalents of trifluoromethanesulfonic acid are added to the mixture at 0 °C. The resulting mixture is warmed to room temperature and stirred at RT for 48 to 96 h. The polymer is precipitated in methanol and reprecipitated from THF into methanol.

In the 25 is the corresponding ¹ H NMR spectrum and in the 26 the ¹⁹ F NMR spectrum of the resulting polymer (analogous to polymer 2) is shown.

The polymer 2 produced as described above is suspended in a sulfonating agent (e.g. sulfuric acid, chlorosulfonic acid, oleum 20%, oleum 65%, etc.). The mixture is stirred at room temperature for 5 to 96 h. The resulting highly viscous polymer solution is precipitated in ice water. The polymer 3 obtained is filtered off and washed with water. Depending on the sulfonating agent, a degree of sulfonation between 2 and 3 sulfonic acid groups is achieved per repeat unit.

The polymers obtained were characterized using NMR spectroscopy. The successful substitution can be confirmed by the downfield shift of the protons on the substituted aromatic rings. The NMR spectra show a comparison to the starting polymer (see 27 ) shows that there is a mixture of different degrees of sulfonation with respect to a single repeating unit.

Therefore, an average degree of sulfonation is determined using elemental analysis, the results of which are shown in the table below. Table 3: Composition of two sulfanation products determined by elemental analysis. Membrane/polymer C in % There % S in % Degree of sulfonation 3a PTp-PF-Sulf 1 36.12 3.77 7.94 1.8 3b PTp-PF-Sulf 2 37.30 2.55 10.30 2.1

Membranes can be produced from the polymers described above using a doctor blade. For this purpose, solutions of the polymers are prepared in NMP, DMAc or DMSO with a mass fraction of the polymer between 1% and 30%. The conductivities and thicknesses of three membranes produced in this way are shown in the table below. Table 4: Conductivities of membranes made from copolymers of sulfonated-P-terphenyl and perfluoroacetophenone, Membrane/polymer Thickness (µm) σ(mS*cm ^-1 ) 3a PTp-PF-Sulf 1 31 12.60 ± 1.10 3b PTp-PF-Sulf 2 25 22.30 ± 2.81 3c PTp-PF-Sulf 3 30 62.52 ± 10.79

The previously described membranes can potentially be used in various electrochemical applications such as fuel cells and electrolysis. Initial preliminary tests showed the basic suitability of the sulfonated polymer for use in fuel cells.

Example 14

• Im ersten Schritt erfolgt die Herstellung eines PHA-Polymers durch Reaktion von Perfluoracetophenon mit p-Terphenyl, siehe 2. Wenn die Sulfonierung dieses Polymers mit dem starken Sulfonierungsmittel Oleum durchgeführt wird (H₂SO₄ mit 60-65 Gew% gelöstem SO₃), können alle 3 Aromaten der Wiederholungseinheit des Polymers sulfoniert werden. Es wird ein Polymer mit einer lonenaustauscherkapazität von 4,19 meq SO₃H/g Polymer erhalten. Im zweiten Schritt wird ein Polymer aus p-Terphenyl mit 1-(1H-Benzo[d]imidazol-2-yl)ethan-1-on (siehe 6) synthetisiert. Die Strukturen beider Polymere sind mit ihren Summenformeln und Molekularmassen ihrer Wiederholungseinheiten in der 28 aufgeführt.

Ionically cross-linked cation exchange acid-base blend membrane 11 made from a sulfonated terphenyl polymer made from perfluoroacetophenone and terphenyl:

• In the first step, a PHA polymer is produced by reacting perfluoroacetophenone with p-terphenyl, see 2 . If the sulfonation of this polymer is carried out with the strong sulfonating agent oleum (H ₂ SO ₄ with 60-65 wt% dissolved SO ₃ ), all 3 aromatics of the repeating unit of the polymer can be sulfonated. A polymer with an ion exchange capacity of 4.19 meq SO ₃ H/g polymer is obtained. In the second step, a polymer of p-terphenyl is combined with 1-(1H-benzo[d]imidazol-2-yl)ethan-1-one (see 6 ) synthesized. The structures of both polymers with their molecular formulas and molecular masses of their repeating units are in the 28 listed.

1. 1. 48 Stunden bei 90°C in 10% HCl
2. 2. 48 Stunden bei 60°C in vollentsalztem Wasser

Dissolve 2 g of the sulfonated terphenyl polymer in 18 g of dimethyl sulfoxide (DMSO). After dissolution, the sulfonated polymer is neutralized with 0.682 ml of n-propylamine. A 10% by weight solution of the benzimidazole terphenyl polymer is also prepared in DMSO and 12.8 g of it is added to the DMSO solution of the sulfonated terphenyl polymer. Stir until homogenized and then draw a membrane on a glass plate using the film drawing device. The glass plate with the drawn membrane is then placed in a circulating air oven and the solvent is evaporated at a temperature of 140 ° C for a period of 2 hours. The glass plate is then removed and placed in a water bath, whereupon the membrane detaches from the glass plate. The membrane is treated as follows:

1. 1. 48 hours at 90°C in 10% HCl
2. 2. 48 hours at 60°C in demineralised water

The membrane can then be characterized. Its ion exchange capacity (IEC) is 1.5 meq SO ₃ H/g membrane. The polymer can then be covalently crosslinked (see 3 ), by forming a membrane of the polymer in the sulfonic acid salt form (SO ₃ R with R = any ammonium group N(R ₂ ) ₄ ⁺ (R ₂ =H, alkyl) or alkali metal cation such as Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ⁺ ) in a (for example 10% by weight ethanolic solution of an alkanedithiol (example: hexane-1,6-dithiol) or a dithiophenol (example: [1,1'-biphenyl]-4,4'-dithiol) which with Equimolar amounts of a base, for example n-propylamine, have been neutralized, is placed, for example for 24 hours at 90 ° C. The membrane is then rinsed with ethanol until there are no more free dithiophenols or alkanedithiols in the membrane. Then the Membrane placed at 90°C in 10% HCl for 48 hours and then at 60°C in demineralized water for 48 hours to produce the acid form of the membrane again. The advantage of this crosslinking is that no sulfonic acid groups are “sacrificed” for the crosslinking. Need to become.

Example 15

Multiple phosphonated poly-p-terphenyl-co perfluoroacetophenone from the analogue of polymer 2:

The polymer produced in Example 13 using PHA is heated with 5 to 25 equivalents (preferably 10 to 15 equivalents) of tris(trimethylsilyl) phosphite at temperatures between 170 ° C and 200 ° C for 6 to 18 hours. The resulting mixture is diluted with THF and the polymer is precipitated in heptane. The polymer thus obtained is heated to reflux in water and then stirred in warm 1 M hydrochloric acid. Surprisingly, the ¹⁹ F NMR reveals a substitution of the fluorine atoms on the pentafluorophenyl ring in the para position and one of the two ortho positions ( 29 ), so that two phosphonic acid groups could be introduced, which has not yet been observed for phosphonation on polymers containing the pentafluorophenyl group.

The substances produced in this way can be used either as pure membranes or as blend membranes, for example with a basic polymer as a blend component. Covalent cross-linking of membranes made from this phosphonated polymer with alkanedithiols or aromatic dithiophenols is also possible, see also 3 .

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Non-patent literature cited

• L.I. Olvera, M.T. Guzmán-Gutiérrez, M.G. Zolothukhin, S. Fomine, J. Cárdenas, F.A. Ruiz-Trevino, D. Villers T.A. Ezquerra, E. Prokhorov, “Novel High Molecular Weight Aromatic Fluorinated Polymers from One-Pot, Metal-Free Step Polymerizations,” Macromolecules 46 (2013) 7245-7256 [0005]
• M.T. Guzmán-Gutierréz, D.R. Nieto, S. Fomine, S.L. Morales, M.G. Zolothukhin, M.C.G. Hernandez, H. Kricheldorf, E.S. Wilks, “Dramatic Enhancement of Superacid-Catalyzed Polyhydroxyalkylation Reactions,” Macromolecules 44 (2011) 194-202 [0005]
• M.T. Guzmán-Gutierréz, M-H. Rios-Dominguez, F.A. Ruiz-Treviño, M.G. Zolothukhin, J. Balmaseda, D. Fritsch, E. Prokhorov, “Structure-properties relationship for the gas transport properties of new fluoro-containing aromatic polymers”, Journal of Membrane Science 385-386 (2011) 277-284 [0005]
• Xin Liu, Na Xie, Jiandang Xue, Mengyuan Li, Chenyang Zheng, Junfeng Zhang, Yanzhou Qin, Yan Yin, Dario R. Dekel, Michael D. Guiver, Nature Energy 2022, 7, 329-339 [0047, 0073]

Claims (22)

Method for producing a material for a membrane, comprising the following steps: - Providing at least one starting material, at least one starting material containing or consisting of at least one monomer; - Synthesizing a polymer from the starting material(s) using polyhydroxyalkylation (PHA); - Modification of the synthesized polymer in a subsequent reaction. Procedure according to Claim 1 , characterized in that before the polymer is synthesized, at least one starting material is modified in a preliminary reaction. Method for producing a material for a membrane, comprising the following steps: - Providing at least one starting material, at least one starting material containing or consisting of at least one monomer; - Modification of at least one starting material in a preliminary reaction; - Synthesizing a polymer from the starting material(s) using polyhydroxyalkylation (PHA). Procedure according to Claim 3 , characterized in that after the polymer has been synthesized, the synthesized polymer is modified in a subsequent reaction. Method according to one of the preceding claims, characterized in that at least one starting material contains at least one type of diaryl monomer. Method according to one of the preceding claims, characterized in that at least one starting material contains at least one ketone group and/or carbonyl group, in particular several different ketone groups and/or several different carbonyl groups. Method according to one of the preceding claims, characterized in that at least one starting material contains or consists of one or more of the following ketones and/or aldehydes: 4-methylpiperazin-2-one, 1-(1-methylpiperidin-4-yl)ethane- 1-one, 1,4-dimethylpiperazin-2-one, piperazin-2-one, 1,3-dimethyltetrahydropyrimidin-2(1H)-one, 1-(1-methyl-1H-benzo[d]imidazole-2- yl)ethan-1-one, 2,2,2-trifluoro-1-(1-methyl-1H-benzo[d]imidazole-2-yl)ethan-1-one, 1-(5,6-dimethyl- 1H-benzo[d]imidazole-2-yl)ethan-1-one, 1-(5-methylpyridin-3-yl)ethan-1-one, 1-(5-methylpyridin-2-yl)ethan-1- one, 2,2,2-trifluoro-1-(4-mercaptophenyl)ethan-1-one, acetylferrocene, (2,2,2-trifluoroacetyl)ferrocene, 1-(4-(5-bromopentyl)phenyl)ethane- 1-one, 1-(4-ethylpiperazin-2-yl)ethan-1-one, 1-(1-methyl-1H-pyrazol-4-yl)ethan-1-one, pyrrolidine-3-carbaldehyde, 1- (1H-pyrazol-3-yl)ethan-1-one, 1-(1H-benzo[d]imidazole-6-yl)ethan-1-one, 1-(7-methyl-1H-benzo[d] imidazole-2-yl)ethan-1-one, 1-(1H-benzo[d]imidazole-2-yl)ethan-1-one, 1-(4-methylpyridin-3-yl)ethan-1-one, 1-(4-mercaptophenyl)ethan-1-one, (4-acetylphenyl)phosphonic acid, 1-(3-methylpyridin-2-yl)ethan-1-one, 1-(1-methyl-1H-pyrazole-3 -yl)ethan-1-one, 1-(1,2,4-dimethyl-1H-imidazol-5-yl)ethan-1-one, 1-(1,2,4-trimethyl-1H-imidazol-5 -yl)ethan-1-one, 1 -(1H-benzo[d]imidazol-7-yl)ethan-1-one, 1 -(1H-benzo[d]imidazol-2-yl)propn-1-one , 1-(1H-benzo[d]imidazol-2-yl)propan-2-one, 1-(1,4,5-trimethyl-1H imidazol-2-yl)ethan-1-one, 2,2, 2-trifluoro-1-(1-methyl-1H-imidazol-2-yl)ethan-one, 1-(1-methyl-1H-imidazol-2-yl)ethan-1-one, 1-(1H-imidazole -5-yl)ethan-1 -one, 1-(1H-imidazo-2-yl)ethan-1-one, 1-(2-methylpyridin-4-yl)ethan-1-one, 4-acetylbenzenesufonic acid , 1-(4-methylpyridin-2-yl)ethan-1-one, 1-(pyridine-4-yl)ethan-1-one, 1-(pyridine-3-yl)ethan-1-one, 1- (pyridine-2-yl)ethan-1-one, 2,2,2-trifluoro-1-(pyridine-2-yl)ethan-1-one, 2,2,2-trifluoro-1-(pyridine-4 -yl)ethan-1-one, 2,2,2-trifluoro-1-(pyridine-3-yl)ethan-1-one, 2,2,2-trifluoro-1-(piperidin-4-yl)ethane -1-one, 1-(quinolin-8-yl)ethan-1-one, 1-(quinolin-5-yl)ethan-1-one, 2,2,2-trifluoror-1-(1H-imidazol- 2-yl)ethan-1-one, 1-(quinolin-4-yl)ethan-1-one, 1-(3-methylpyridin-4-yl)ethan-1-one, 1-(2,3,5 ,6-tetrafluoro-4-mercaptophenal)ethan-1-one, 1-(cyclopenta-2,4-dien-1-yl)ethan-1-one, 1-(4-hexylphenyl)ethan-1-one, 1 -(cyclopenta-2,4-dien-1-yl)-2,2,2,-trifluoroethan-1-one, 1-(4-(5-chloropentyl)phenyl)ethan-1-one, 1-(4 -bromophenyl)ethan-1-one, 1-(4-chlorophenyl)ethan-1-one, 1-(4-fluorophenyl)ethan-1-one, 1-(4-iodophenal)ethan-1-one, 1- (6-methylpyridin-2-yl)ethan-1-one, 1-(6-methylpyridin-3-yl)ethan-1-one, 3-acetylbenzenesulfonic acid, 4-acetyl-2,3,5,6-tetrafluorobenzenesulfonic acid, 1-(2-methylpyridin-3-yl)ethan-1-one, 1-(quinolin-7-yl)ethan-1-one, 1-(quinolin-6-yl)ethan-1-one, Di (pyridine-2-yl)methanone, 1-(2-(dimethylamino)phenyl)ethan-1-one, 2,2,2-trifluoror-1-(quinolin-3-yl)ethan-1-one, 1- (3-(dimethylamino)phenyl)ethan-1-one, 1-(4-(dimethylamino)phenyl)ethan1-one, 1-(quinolin-2-yl)ethan-1-one, 1-(4-(dimethylamino )phenyl)-2,2,2-trifluoroethan-1-one, 1-(3-(dimethylamino)phenyl)-2,2,2-trifluoroethan-1-one, 1-(3-chlorophenyl)2,2, 2-trifluoroethan-1-one, 1-(3-bromophenyl)-2,2,2-trifluoroethan-1-one, 2,2,2-trifluoro-1-(3-iodophenyl)ethan-1-one, 2 ,2,2- trifluoro-1-(3-fluorophenyl)ethan-1-one, 1-(2-bromophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-chlorophenyl)-2,2,2-trifluoroethane -1-one, 1-(2-iodophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-fluorophenyl)-2,2,2-trifluoroethan-1-one, 1-(2- bromophenyl)-2,2,2-trifluoroethan-1-one, 1-(2-chlorophenyl)ethan-1-one, 1-(2-iodoophenyl)ethan-1-one, 1-(2-bromophenyl)ethan- 1-one, 1-(2-fluorophenyl)ethan-1-one, 1-(3-chlorophenyl)ethan-1-one, 1-(3-bromophenyl)ethan-1-one, 1-(3-iodoophenyl) ethan-1-one, 1-(3-fluorophenyl)ethan-1-one, 2,2,2-trifluoro-1-(4-fluorophenyl)ethan-1-one, 2,2,2-trifluoro-1- (4-iodophenyl)ethan-1-one, 1-(4-chlorophenyl)-2,2,2-trifluoroethan-1-one, 1-(4-bromophenyl)-2,2,2-trifluoroethan-1-one , 2,2,2-trifluoro-1-(perfluorophenyl)ethan-1-one, 8-bromo-1,1,1-trifluorooctan-2-one, 1-(isoquinolin-4-yl)ethan-1-one , 1-(quinolin-3-yl)ethan-1-one, 1-(1,8-naphthyridin-4-yl)-ethan-1-one, 1-(perfluorophenyl)ethan-1-one, 1-( isoquinolin-1-yl)ethan-1-one, 2,2,2-trifluoro-1-(4-nitrophenyl)ethan-1-one, 2,2,2-trifluoro-1-(3-nitrophenyl)ethan- 1-one, Ferrocenecarboxaldehyde, Formylcobaltocene, Formlynickelocene Method according to one of the preceding claims, characterized in that at least one starting material contains or consists of one or more of the following aryls: 1,2'-binaphtalene, 1,1'-binaphtalene, 2,2'-binaphtalene, 1,1'- biphenyl, 1,1'.4,1''-terphenyl, 10-methyl-9,10-dihydroacridine, 9,10-diphenylanthracene, 1,4-diphenylnaphthalene, 1,1':4',1''.4 '',1'''-quaterphenyl, 1,1':3',1''.3'',1'''-quaterphenyl, 1,1':3',1''-terphenyl, 9.9 ,10-trimenthyl-9,10-dihydroacridine, 2,4,6-triphenyl-1,3,5-triazine, 2,3-diphenylnaphthalene, 2',2'',3',3'',5', 5'',6',6''-octofluoro-1,1':4',1''.4'',1'''-quaterphenyl, 2',3',5',6'-tetrafluoro- 1,1',4',1''-terphenyl, 2',4', 5', 6'-tetrafluororo-1,1':3',1''-terphenyl, 2',2'',4 ',4'',5',5'',6',6''-octafluoro-1,1':3',1''.3'',1'''-quaterphenyl, 9,10-dihydroacridine , 2,4,6-triphenylpyridine, 5`-iodo-1,1`:3`,1''-terphenyl, 5'-bromo-1,1':3'1''-terphenyl, 5'-chloro -1,1':3',1''-terphenyl, 2'-bromo-1,1':3'1''-terphenyl,2'-iodo-1,1':3',1''-terphenyl,4'-bromo-1,1':2',1''-terphenyl, 9,9-dimenthyl-9,10-dihydroacridine, 2,3,6,7-tetraphenylnaphthalene, 2,6-diphenlypyridine, 2 ,6-diphenylpyrazine, 4,6-diphenylpyrimidine, 3,5-diphenylpyridine, 2,5-diphenlypyridine, 2,5-diphenylpyrimidine, 1,3-diphenylcyclohexane, 5-methyl-5,10-dihydrophenazine, 5,10-dihydrophenazine , 5`-phenyl-1,1`:3`,1''-terphenyl, NN-dimethyl-[1,1':3',1''-terphenyl]-5'-amine, NN-dimethyl-[ 1,1':3',1''-terphenyl]-2'-amine, 6,6'-diphenyl-2,2'-bipyridine, 2,4-diphenyl-1,3,5-triazine, 1, 4-diphenylcyclohexane, 1,2-diphenylcyclohexane, 5,10-dimethyl-5, 10-dihydrophenazine, 5'-methyl-1,1':3',1''-terphenyl, 2'-methyl-1,1':3',1''-terphenyl, 4-methyl-2,6-diphenylpyridine, 2',3'-dimethyl-1,1':4', 1''-terphenyl, 2',3',5',6'-tetramethyl-1,1':4',1''-terphenyl, 2,3,5,6-tetraphenylpyrazine. Method according to one of the preceding claims, characterized in that at least one starting material comprises or consists of a monomer with an organic radical, the organic radical being in particular 1,4-arylene or 1,3-arylene or 1,2-arylene or alkyl or 1,4-perfluoroarylene or 1,3-perfluoroarylene or 1,2-perfluoroarylene or perfluoroalkyl or bromoarylene or chloroarylene or iodoarylene or pyridyl or pyracinyl or pyrimidyl or triacinyl or 9H-fluorenyl or 9-dialkyl-9H-fluorenyl or 9,9- Bis(haloalkyl)-9H-fluorenyl or 1,4-cyclohexyl or 1,3-cyclohexyl or 1,2-cyclohexyl or 1-methylpiperidyl or 1,4-dimethylpiperazinyl or 1,3-dimethylhexahydropyrimidinyl comprises or consists of. Method according to one of the preceding claims, characterized in that the polyhydroxyalkylation takes place under the influence of trifluoromethanesulfonic acid (TFSA). Method according to one of the preceding claims, characterized in that the polyhydroxyalkylation (PHA) takes place under the influence of a solvent, in particular a chlorinated solvent. Method according to one of the preceding claims, characterized in that the modification of the synthesized polymer in a subsequent reaction and/or the modification of the starting material in a preliminary reaction involves a nucleophilic aromatic substitution reaction and/or an electrophilic aromatic substitution reaction and/or a polymer-analog reaction and/or a Alkylation of basic nitrogen atoms to tertiary or quaternary N-basic compounds and/or occurs with microwave assistance. Method according to one of the preceding claims, characterized in that it comprises blending the synthesized polymer with another polymer to form a blended polymer mixture. Procedure according to Claim 13 , characterized in that crosslinks, in particular ionic and/or covalent crosslinks, arise between the polymers during blending. Procedure according to Claim 13 or 14 , characterized in that the blinded polymer mixture is doped. Procedure according to Claim 15 , characterized in that the doping of the blended polymer mixture takes place with mineral acids, in particular with sulfuric acid or phosphoric acid or a phosphonic acid, and/or includes the introduction of further ion exchange groups, in particular acidic sulfonic acid and/or acidic phosphonic acid groups. Procedure according to one of the Claims 13 until 16 , characterized in that anion exchange groups are generated on the blinded polymer mixture. Procedure according to Claim 17 , characterized in that the generation of anion exchange groups by the alkylation (quaternization) of any tertiary N-basic groups contained in the blended polymer mixture and / or by the reaction of halomethyl groups of the form CH ₂ Hal with Hal = CI contained in the blended polymer mixture, Br, I with tertiary N-basic groups. Substance produced by a method according to any one of the preceding claims. Membrane, comprising or consisting of a substance according to Claim 19 . Membrane after Claim 20 , characterized in that the thickness is less than 100 µm, in particular less than 75 µm, preferably less than 50 µm. Using a membrane Claim 20 or 21 in a fuel cell, in particular in a low-temperature fuel cell and/or in a direct alcohol fuel cell, or in a battery, in particular in a redox flow battery, or in an electrochemical process, in particular in an electrolysis process or in an electrosynthesis process, preferably in a water electrolysis process, and/or as a proton exchange membrane.

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