Method for producing a material for a membrane, material, membrane and use of a membrane

Abstract

The present invention relates to a method for producing a material for a membrane, the method comprising the following steps: - providing at least one starting material, at least one starting material containing at least one monomer or consisting thereof; - synthesizing a polymer from the starting material(s) by way of polyhdroxyalkylation (PHA); and - modifying the synthesized polymer in a subsequent reaction. The invention further relates to a material, a membrane and the use of a membrane.

Description

[0001] DESCRIPTION

[0002] Process for producing a material for a membrane, material, membrane and use of a membrane

[0003] The present invention relates to a process for producing a material for a membrane. Furthermore, the present invention relates to a material produced by such a process, as well as to a membrane comprising or consisting of such a material. Furthermore, the present invention relates to the use of such a membrane.

[0004] As part of the energy transition, alternative ways of generating electricity are increasingly being developed. Fuel cells represent an important area in this regard. These convert the chemical reaction energy of a supplied fuel and an oxidizing agent into electrical energy. In addition, the storage of electrical energy is playing an increasing role. The main focus here is on further developing battery technology so that batteries have both high energy density and high long-term stability.

[0005] Membranes, especially ion exchange membranes, are used particularly in electrochemical processes, such as electrolysis processes, or in electrochemical systems, such as fuel cells or batteries. Such membranes are subject to stringent requirements. Firstly, they must be sufficiently chemically stable with respect to the media surrounding them, depending on their intended application. Furthermore, such membranes are frequently exposed to mechanical stress. Furthermore, electrochemical applications require a certain degree of conductivity combined with a low degree of swelling, i.e., low volume expansion.

[0006] Polymers are typically used as materials for such membranes. These are synthesized from monomers. One group of polymer synthesis processes is polycondensation. The polyhydroxyalkylation (PHA) process belongs to this group of processes.

[0007] Mittels Polyhydroxyalkylierung erzeugte Polymere sind beispielsweise be- schrieben in L.I. Olvera, M.T. Guzmän-Gutierrez, M.G. Zolothukhin, S. Fomine, J. Cárdenas, F.A. Ruiz-Trevino, D. Villers T.A. Ezquerra, E. Prok- horov, „Novel High Molecular Weight Aromatic Fluorinated Polymers from One-Pot, Metal-Free Step Polymerizations“, Macromolecules 46 (2013) 7245- 7256, and in M.T. Guzmän-Gutierrez, 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 and in M.T. Guzmán-Gutiérrez, 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.

[0008] Even though polymers that are fundamentally suitable for use in membranes can be synthesized by polyhydroxyalkylation, there is a permanent need to improve the property profile, specifically the chemical stability, conductivity and mechanical stability.

[0009] The object of the present invention is therefore to provide a process by which materials for a membrane with a favorable property profile can be produced. Furthermore, corresponding materials are to be provided that are characterized by a favorable property profile.

[0010] 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:

[0011] - Providing at least one starting material, wherein at least one starting material contains or consists of at least one monomer;

[0012] Synthesizing a polymer from the starting material(s) by polyhydroxyalkylation (PHA);

[0013] Modification of the synthesized polymer in a subsequent reaction.

[0014] 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:

[0015] Providing a starting material, wherein at least one starting material contains or consists of at least one monomer;

[0016] Modification of at least one starting material in a preliminary reaction;

[0017] Synthesizing a polymer from the starting material(s) by polyhydroxyalkylation (PHA).

[0018] Furthermore, the object underlying the invention is achieved by a substance which is produced by such a process. The invention is therefore based on the fundamental idea of ​​modifying the polymer in addition to polymer synthesis by polyhydroxyalkylation. This allows the properties of the resulting polymer to be further optimized. It is possible to modify the polymer after synthesis by polyhydroxyalkylation by a subsequent reaction. Alternatively or additionally, a modification of the starting material can also take place 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 of the synthesized polymer can take place before and / or after polymer synthesis in order to optimize the properties of the polymer.The polymer synthesized by polyhydroxyalkylation is also called PHA polymer.

[0019] 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 comprises chain molecules or branched molecules. The chain molecules or branched molecules consist of identical units or, for example, in the case of copolymers, of different units.

[0020] Preferably, the starting material contains at least one type of diaryl monomer.

[0021] According to a preferred embodiment, at least one starting material contains or consists of one or more of the following ketones and / or aldehydes:

[0022] 4-Methylpiperazin-2-on, 1-(1-Methylpiperidin-4-yl)ethan-1-on, 1 ,4-Dimethylpi- perazin-2-on, Piperazin-2-on, 1 ,3-Dimethyltetrahydropyrimidin-2(1 H)-on, 1- (1 -Methyl- 1 H-benzo[d]imidazol-2-yl)ethan-1 -on, 2,2,2-T rifluor-1 -(1 -methyl- 1 H-benzo[d]imidazol-2-yl)ethan-1 -on, 1 -(5,6-Dimethyl-1 H-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-1 H-pyrazol-4-yl)ethan-1 -on, Pyr- rolidin-3-carbaldehyd, 1 -(1 H-Pyrazol-3-yl)ethan-1 -on, 1 -(1 H-Benzo[d]imid- azol-6-yl)ethan-1 -on, 1 -(7-Methyl-1 H-benzo[d]imidazol-2-yl)ethan-1 -on, 1 - (1 H-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-1 H-pyrazol-3-yl)ethan-1 -on, 1 - (1 ,2,4-Trimethyl-1 H-imidazol-5-yl)ethan-1 -on, 1 -(1 H-Benzo[d]imidazol-7- yl)ethan-1 -on, 1 -(1 H-Benzo[d]imidazol-2-yl)propan-1 -on, 1 -(1 H-Benzo[d]imid- azol-2-yl)propan-2-on, 1-(1 ,4,5-Trimethyl-1 H-imidazol-2-yl)ethan-1-on, 2,2,2- T rifluor-1 -(1 -methyl-1 H-imidazol-2-yl)ethan-1 -on, 1 -(1 -Methyl-1 H-imidazol-2- yl)ethan-1 -on, 1 -(1 H-lmidazol-5-yl)ethan-1 -on, 1 -(1 H-lmidazo-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-T rifluor-1 -(pyridin-2-yl)ethan- 1 -on, 2,2,2-T rifluor-1 -(pyridin-4-yl)ethan-1 -on, 2,2,2-T rifluor-1 -(pyridin-3- yl)ethan-1 -on, 2,2,2-T rifluor-1 -(piperidin-4-yl)ethan-1 -on, 1 -(Chinolin-8- yl)ethan-1 -on, 1 -(Chinolin-5-yl)ethan-1 -on, 2,2,2-T rifluor-1 -(1 H-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 - y l)-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-Fluor- phenyl)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-Ace- tyl-2,3,5,6-Tetrafluorbenzolsulfonsäure, 1 -(2-Methylpyridin-3-yl)ethan-1 -on, 1 - (Chinolin-7-y l)ethan-1 -on, 1 -(Chinolin-6-yl)ethan-1 -on, Di(pyridin-2-yl)meth- anon, 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-(Dimethyla- mino)phenyl)ethan-1 -on, 1 -(Chinolin-2-yl)ethan-1 -on, 1 -(4-(Dimethyla- mino)phenyl)-2,2,2-trifluorethan-1 -on, 1 -(3-(Dimethylamino)phenyl)-2,2,2-tri- fluorethan-1 -on,1 -(3-Chlorphenyl)2,2,2-trifluorethan-1 -on, 1 -(3-Bromphenyl)-,

[0023] 2.2.2-trifluorethan-1-on, 2,2,2-Trifluor-1-(3-iodphenyl)ethan-1-on, 2,2,2-Tri- fluor-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-trifluoro- ethan-1 -on, 1 -(2-Fluorphenyl)-2,2,2-trifluorethan-1 -on, 1 -(2-Bromphenyl)-

[0024] 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-Chlor- phenyl)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,

[0025] 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-l-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-tri- fluoro-1 -(4-nitrophenyl)ethan-1 -one, 2,2,2-trifluoro- 1 -(3-nitrophenyl)ethan-1 -one, ferrocene carboxaldehyde, formylcobaltocene, formylnickelocene.

[0026] Structural formulas of usable starting materials are shown in the figure below, which are ketones and aldehydes.

[0027] At least one starting material may also contain one or more of the following aryls or aryl groups:

[0028] 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 ‘“-Quater- phenyl, 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 ,T,4‘,1 “-terphenyl, 2‘ ,4‘ , 5‘, 6‘-Tetrafluor-1 ,T:3‘,1 “-terphenyl, 2‘,2“,4‘,4“,5‘,5“,6‘,6“-Octafluor-

[0029] 1 ,T:3‘,1“.3“,1 ‘“-quaterphenyl, 9,10-dihydroacridin, 2,4,6-Triphenylpyridin, 5‘- lod-1 ,T:3‘,1 “-terphenyl, 5‘-Brom-1 ,T:3‘1 “-terphenyl, 5‘-Chlor-1 ,T:3‘,1 “-ter- phenyl, 2‘-Brom-1 ,T:3‘1 “-terphenyl, 2‘-lod-1 ,T:3‘,1 “-terphenyl, 4‘-Brom-

[0030] 1 ,T:2‘,1 “-terphenyl, 9,9-Dimethyl-9,10-dihydroacridin, 2,3,6,7-Tetraphenyl- naphtalin, 2,6-Diphenylpyridin, 2,6-Diphenylpyrazin, 4,6-Diphenylpyrimidin, 3,5-Diphenylpyridin, 2,5-Diphenylpyridin, 2,5-diphenylpyrimidin, 1 ,3-Diphe- nylcyclohexan, 5-Methyl-5,10-dihydrophenazin, 5,10-Dihydrophenazin, 5‘- Phenyl-1 ,T:3‘,1 “-terphenyl, N-N-Dimethyl-[1 ,T: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 ,T:3‘,1 “-terphenyl, 2‘-Me- thyl-1 ,T:3‘,1 “-terphenyl, 4-Methyl-2,6-diphenylpyridin, 2‘,3‘-Dimethyl-

[0031] 1 ,T:4‘,1 “-terphenyl, 2‘,3‘,5‘,6‘-Tetramethyl-1 ,T:4‘,1 “-terphenyl, 2,3,5,6-Tetra- phenylpyrazin.

[0032] Structural formulas for aryls that may be present in a starting material or that may form the starting material are shown in the figure below.

[0033]

[0034]

[0035] One type of monomer of a starting material may comprise an organic radical, wherein the organic radical is 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-dimethylhexahydropyridyl- comprising or consisting of midinyl.

[0036] 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: R2 can stand for hydrogen (H), phenyl, C n H 2n-i with n=1-20, or for C n F 2n-i with n=1-20.

[0037] The radical R3 can be any basic nitrogen-containing organic radical. It can preferably have the following structure:

[0038] (2-R, 3-R, 4-R, 5-R, 6-R)-x-pyridyl with R=H, CI

[0039] Br, I, OMe, C n H 2n-i with n=1-20, C n F 2n-i with n=1-20 NO2, SO3H, SH, SO2-C n H 2n-i with n=1-20 and x=2, 3 or 4

[0040] (2-R, 3-R, 4-R, 5-R, 6-R)-x-pyrimidinyl with R=H,

[0041] CI, Br, I, OMe, Cn H 2n-i with n=1-20, C n H 2n-i with n=1-20 and x=2, 3 or 4

[0042] 1 H-benzo[d]imidazolyl

[0043] 1 -Methyl-1 H-benzo[d]imidazolyl

[0044] 1 H-imidazolyl

[0045] 1-Methyl-1H-imidazolyl

[0046] 1-methylpiperidin-2-,3- or 4-yl

[0047] 1-(4-methylpiperazin-2-, or 3-yl

[0048] Alternatively, the radical R3 can be a halogen-containing organic radical. R3 can preferably have the following structure:

[0049] (CH)kHal with Hal=Cl, Br, I and k = 1-10

[0050] Pentafluorophenyl

[0051] Tetrafluorophenyl

[0052] Trifluorophenyl

[0053] Difluorophenyl

[0054] Fluorophenyl

[0055] According to a preferred embodiment, the process according to the invention can be characterized in that exactly two different starting materials are provided, which in particular each contain or consist of a monomer.

[0056] A first starting material can be a phenyl derivative, in particular a biphenyl or a terphenyl. A preferred embodiment of the process can be characterized in that a first starting material is a phenyl derivative, in particular a terphenyl derivative, preferably m-terphenyl, p-terphenyl, and / or a biphenyl, and a second starting material is an aromatic ketone, in particular an aromatic trifluoroketone, preferably 1,1,1-trifluoro-3-(pyredin-4-yl)propan-2-one.

[0057] According to an alternative embodiment, a first starting material can be a phenyl derivative, in particular a terphenyl, preferably p-terphenyl or m-terphenyl, and / or a biphenyl, and a second starting material can be perfluoroacetophenone. A subsequent reaction can comprise or consist of a sulfonation or a phosphonation, in particular a multiple phosphonation, preferably a double phosphonation.

[0058] According to an alternative embodiment, the first starting material may be a terphenyl derivative, in particular p-terphenyl or m-terphenyl, and / or a biphenyl, and the second starting material may be 1-(1 H-benzodimidazol-2-yl)ethan-1-one and a subsequent reaction may comprise or consist of a sulfonation.

[0059] It is also possible that the first starting material is 2,6-diphenylpyridine and a second starting material is 2,2,2-trifluoro-1-(pyridin-4-yl)ethan-1-one and a subsequent reaction can take place with Mel or dimethylsulfate or by reaction with a dihaloalkane.

[0060] According to an alternative embodiment of the process, a first starting material can be an aryl, in particular m-terphenyl, and a second starting material can be or contain a cyclopentadienyl complex, which in particular contains a ferrocene group, and in a subsequent reaction the ferrocene can be partially oxidized. According to an alternative embodiment of the process, in which a modification of at least one starting material takes place in a preliminary reaction, a starting material can be 1-(4-mercaptophenyl)ethan-1-one, and this can be oxidized to 4-acetylsulfonic acid in a preliminary reaction. In a further embodiment, a second starting material can then be a phenyl derivative, in particular m-terphenyl, p-terphenyl, and / or a biphenyl.

[0061] According to an alternative embodiment of the process, which comprises modifying at least one starting material in a preliminary reaction, a first starting material can be a bromohexylterphenyl, in particular 5'-(6-bromohexyl)-1,T:3',1"-terphenyl, which reacts with dibromohexane, in particular 1,6-dibromohexane, in a first preliminary reaction. This modified starting material thus obtained can react with 4-methylpyridine in a second preliminary reaction. The second starting material can be 4-acetylpyridine.

[0062] The basic reaction scheme of a polyhydroxyalkylation is shown below.

[0063] The designation R1 stands for any organic radical, which preferably has one of the aforementioned structures. The designations R2 and R3 have already been explained above. According to an alternative embodiment of the process, in which a modification of at least one starting material takes place in a preliminary reaction, one starting material can be 1-(4-mercaptophenyl)ethan-1-one, which can be oxidized to 4-acetylsulfonic acid in a preliminary reaction. In a further embodiment, a second starting material can then be a phenyl derivative, in particular m-terphenyl, p-terphenyl, and / or a biphenyl.

[0064] According to an alternative embodiment of the process, which comprises modifying at least one starting material in a preliminary reaction, a first starting material can be a bromohexylterphenyl, in particular 5'-(6-bromohexyl)-1,1':3',1"-terphenyl, which reacts with dibromohexane, in particular 1,6-dibromohexane, in a first preliminary reaction. This modified starting material thus obtained can react with 4-methylpyridine in a second preliminary reaction. The second starting material can be 4-acetylpyridine.

[0065] The basic reaction scheme of a polyhydroxyalkylation is shown below.

[0066] The designation R1 stands for any organic radical, preferably having one of the previously mentioned structures. The designations R2 and R3 have already been explained. Polyhydroxyalkylation preferably takes place under the influence of trifluoromethanesulfonic acid (TFSA). This has the molecular formula CF3SO3H and is a colorless, pungent-smelling, hygroscopic liquid.

[0067] In a further embodiment, the polyhydroxyalkylation (PHA) can take place under the influence of a solvent, particularly a chlorinated solvent. Such solvents are commercially available.

[0068] The modification of the synthesized polymer in a subsequent reaction and / or the modification of a starting material in a preliminary reaction can each comprise one or more reactions or reaction steps. It is also possible that a modification of the starting material takes place in one or more preliminary reactions prior to polymer synthesis using PHA, and / or that one or more subsequent reactions are carried out after polymer synthesis using PHA to modify the synthesized polymer.

[0069] The modification of the synthesized polymer in a subsequent reaction and / or the modification of the starting material in a preliminary reaction can comprise a nucleophilic aromatic substitution reaction or an electrophilic aromatic substitution reaction. An electrophilic aromatic substitution reaction can comprise 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 iodination, and a possible subsequent reaction 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 proceed in a conventional manner. One or more atoms of an aromatic compound can be substituted. For example, the synthesized polymer can contain perfluoroaromatic compounds in which one or more fluorine atoms are substituted by a functional group. For example, a perfluorophenyl unit or a perfluorobiphenyl unit can be present, in which the para position is first substituted by a functional group. Another functional group can then also be coupled at an ortho position and / or a meta position.

[0070] Several atoms of an aromatic compound can be nucleophilically substituted simultaneously in one step. Alternatively, the nucleophilic substitution of several atoms can occur in several consecutive steps.

[0071] Any 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), CH3I, dimethyl carbonate, or mixtures or dilute solutions of these media.

[0072] It is also conceivable that a substitution reaction takes place during evaporation of a solvent, which preferably takes place at a temperature below 150°C.

[0073] For substitution, a molecule with a linear or branched, saturated or unsaturated C n -body, especially with a C2, C3, C6, C8, C 10 -, C 12 -, C 14 -, C 16 -, or a C 18-body bearing a thiol group at one end can be used. Preferably, an S atom of the thiol group then substitutes an F atom of a perfluoroaromatic compound. In other words, a saturated or unsaturated hydrocarbon with a thiol group can be used as the substituent. If an unsaturated hydrocarbon is used, it can be used for a subsequent reaction, in particular for a thiol-ene click reaction.

[0074] 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 SO4 2- , HSO4', PO4 3 ', HPO4 2', H2PO4', SO3 2- , SO3H-, hydrogen phosphonate R-PO3H-, phosphonate R-PO3 2 ' (R=any organic residue, preferably an aryl residue, preferably with electron-withdrawing groups such as F, SO2R, NO, NO2, etc.), carbonate CO3 2 ', HCO3'' or with an organic carboxylic acid anion, in particular CH3COO-, CF3COO; 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.

[0075] A molecule in the form R-SH, R-S-, R-OH, R-NH, R-N-, or PO3R2 can also be used for substitution. Furthermore, a thiol with a terminal sulfonate group can be used for substitution. Furthermore, a molecule of C5NH10 (piperidyl residue) can be used for substitution, where the nitrogen atom occupies the position of a fluorine atom of the perfluoroaromatic compound. In particular, via the nitrogen atom, if it is positively charged, a residue (counterion) can be coupled in a further embodiment, where the residue is preferably a halide (F-, Cl-, Br, I) or SO4. 2- , HSO4', PO4 3 ', HPO4 2 , H2PO4', SO3 2- , SO3H-, hydrogen phosphonate R-PO3H-, phosphonate R-PO3 2 ', Carbonate CO3 2 ', HCO3' or an organic carboxylic acid anion, in particular CH3COO-, CF3COO-, HCOO-. The residue can in principle contain any anion as a counterion, with anions such as halide (F-, Cl-, Br, I-) or SO4 2-, HSO4-, PO4 3- , HPO4 2- , H2PO4-, SO3 2- , SO3H-, hydrogen phosphonate R-PO3H-, carbonate CO3 2 ', HCO3- or an organic carboxylic acid anion such as CH3COO-, CF3COO-, HCOO- are preferred.

[0076] If the molecule used for substitution has the form S - R, where the sulfur atom occupies or is intended to occupy the position of the substituted fluorine atom, the radical R can be formed as shown in the figure below.

[0077] Furthermore, the molecule SO3- used for substitution can be substituted with a counterion, in particular with a countercation, preferably with a metal countercation or with an ammonium countercation in the form NR4 + with R =

[0078] H, alkyl, aryl or substituted with another N-basic cation, in particular imidazolium, benzimidazolium, guanidinium. A functional group can be C5NH 10wherein the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound. In particular, a residue or counteranion can be substituted via the nitrogen atom, wherein the residue is preferably a halide (F-, Cl-, Br, I-) or SO4 2- , HSO4-, PO43-, HPO4 2- , H2PO4-, SO3 2- , SO3H-, hydrogen phosphonate R-PO3H-, phosphonate R-PO3 2 ', Carbonate CO3 2 -, HCO3' or an organic carboxylic acid anion such as CH3COO-, CF3COO-, HCOO-. The radical or counteranion can be, in particular, 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).

[0079] The substitution that takes place can be designed in such a way that a functional group is coupled to several, in particular two, perfluoroaromatic compounds of two organic polymer chains, so that the functional group crosslinks the chains. This design is based on the idea of ​​not functionalizing the polymer chains independently of one another, but rather functionalizing them in such a way that they are additionally crosslinked. This can, in particular, influence the mechanical properties of the substance.

[0080] Specifically, the functional group can be chain-like and have a sulfur atom at each end, which nucleophilically substitutes a fluorine atom of a perfluoroaromatic compound. Between the sulfur atoms, one or more C n -body and / or a repeating unit.

[0081] In a further embodiment of the process according to the invention, subsequent reactions can occur 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 can be used as the basis for further subsequent reactions. These include, among other things, 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.

[0082] 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.

[0083] The modification of the synthesized polymer in a subsequent reaction and / or the modification of the starting material in a preliminary reaction can also comprise a polymer-analogous reaction. In a polymer-analogous reaction, one functional group is converted into another functional group through a chemical reaction.

[0084] The modification in a subsequent reaction and / or in a preliminary reaction can also include an alkylation of basic nitrogen atoms to tertiary or quaternary N-basic compounds. Furthermore, the subsequent reaction and / or the preliminary reaction can also be microwave-assisted, in particular, a microwave-assisted synthesis. This can accelerate the reaction and, where appropriate, increase the degree of conversion (the yield). Likewise, the selectivity of the reaction can be improved.

[0085] A modification in a subsequent reaction and / or in a preliminary reaction may include or consist of a lithiation reaction.

[0086] Possible modifications in a subsequent reaction and / or in a preliminary reaction can be or include a lithiation reaction on halogenated, preferably chlorinated, brominated, or iodinated polymers or monomers. The reaction scheme of a polymer in which bromine is directly bonded to the aromatic compound is shown below.

[0087] Alternatively, bromine can be in the benzylic position or bonded to an alkylene radical. The corresponding reaction scheme is shown below.

[0088] Such a lithiated monomer or a lithiated PHA polymer can be subjected to further reactions, ie, further preliminary reactions in the case of a monomer or subsequent reactions in the case of a polymer. These can be, for example, a sulfinate S-alkylation or a Suzuki coupling. Further exemplary subsequent reactions are shown in the following reaction scheme.

[0089]

[0090] 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 ferrocene aldehyde, acetylferrocene, or ferrocenoic acid chloride. Subsequent partial or complete oxidation of the transition metal central atom of the complex to an anion exchange polymer yields a material with excellent chemical stability. In the production of membranes, a solution of the partially oxidized di-(cyclopentadienyl) transition metal complex bound to the polymer is used in a (preferably) dipolar aprotic solvent such as DMAc, DMF, DMSO, sulfolane, etc.If a magnetic field is used, with the field lines of the magnetic field aligned perpendicular to the membrane surface, the metal-containing functional groups can be aligned in the direction of the magnetic field, which leads to the formation of through-plane ion-conducting channels and thus to a higher conductivity than when the ion-conducting channels are not aligned in the magnetic field (for the proof of principle of this novel polymer type in the form of partially oxidized 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).

[0091] As a subsequent or preliminary reaction, benzyl bromination with N-bromosuccinimide (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. Also conceivable is lithiation of the methyl group of an aromatic compound with n-butyllithium, followed by further reactions, in particular the grafting of an anionically polymerizable polymer, especially 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.

[0092] 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 (CISO3H) or oleum (H2SO4 with 5-65% SO3) or trimethylsilyl chlorosulfate (TMS-OSO2-Cl), or a combination of these materials can be used as the sulfonating agent.

[0093] 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. This essentially reduces swelling / water absorption, resulting in an improvement in the property profile of membranes made from the material. This can occur, for example, through nucleophilic substitution of a pentafluorophenyl residue in a polymer with an aromatic or aliphatic dithiol.

[0094] In the case of a Friedel-Crafts acylation and / or a Friedel-Crafts alkylation, quaternization of the polymer can be carried out with any other tertiary N-basic compound. Examples of compounds that can be used are tetramethylimidazole, trimethylamine, N-methylpiperidine, N-methylpiperazine, or 3-methyl-3,6-diazaspiro[5.5]undecane-6-ium bromide. Any desired nucleophilic aromatic substitution can be carried out on a pentafluorophenyl residue of the synthesized polymer.

[0095] 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 particularly advantageous for use in high-temperature membrane fuel cells. Membranes doped in this way can be converted into a covalently crosslinked blend membrane by blending with another polymer, in particular with poly(vinylbenzyl chloride) (PVBCI). Specifically, this can be achieved by reacting the chloromethyl groups of PVBCI with the NH of the imidazole function, or by blending with an acidic, sulfonated, or phosphonated polymer to form acid-base blend membranes.

[0096] The modification in a preliminary reaction or in a subsequent reaction can also comprise a phosphonation, in particular a single phosphonation or a double phosphonation, and / or a sulfonation, in particular a single or double sulfonation. It is also possible that in a first subsequent reaction, a single or multiple, for example a double, phosphonation takes place first, followed by a sulfonation, in particular a single or multiple, for example a double sulfonation. The phosphonation and / or the sulfonation can each take place as an electrophilic aromatic substitution and / or as a nucleophilic aromatic substitution. In a nucleophilic substitution, a thiolation can take place in a first step, before the formed thiol is highly oxidized to sulfonic acid in a second step.

[0097] The preliminary reaction or the subsequent reaction can also involve functionalization with or to an alkali-stable dication. This can be a nitrogen dication. In particular, a bromine site formed or present on a synthesized polymer or on a polymer modified in a first subsequent reaction can be converted with or to a dication. Such configurations lead to anion exchange polymers with high ion exchange capacities. Surprisingly, it has been shown that such polymers are not water-soluble, so that membranes with high conductivities can be produced.

[0098] The synthesized polymer can, in particular, be a basic polymer. The polymer can be functionalized in a first step. In a further step, a bromine site can be reacted with a compound containing, in particular, a tertiary amino group and a quaternary ammonium ion, such as, for example, 1,1-dimethyl-4-(3-(1-methylpiperidin-4-yl)propyl)piperidin-1-ium, to form a dication.

[0099] In principle, a subsequent reaction can include or consist of an electrophilic aromatic substitution.

[0100] The process according to the invention or the subsequent reaction or a subsequent reaction may further comprise blending the synthesized polymer with another polymer to form a blended polymer mixture. The modification of the synthesized polymer in a subsequent reaction may thus also comprise or consist of blending the synthesized polymer with a second polymer. In other words, it is provided that the polymer synthesized by polyhydroxyalkylation, which in particular has corresponding modifications, is mixed with at least one other polymer.

[0101] In particular, the synthesized polymer can be a sulfonated polymer. It is also possible that the further polymer was produced using the process according to the invention. The further polymer or the synthesized polymer can have haloalkyl side chains.

[0102] The synthesized polymer or the additional polymer can be a cation exchange polymer. It is also possible for the synthesized polymer or the additional polymer to be an anion exchange polymer. Preferably, the synthesized polymer or the additional polymer is a cation exchange polymer, and the other of the two polymers is an anion exchange polymer. The mixing ratio when blending the synthesized polymer with another polymer can be between 99:1 and 1:99, in particular between 95:5 and 5:95.

[0103] It is also possible that the synthesized polymer is a benzimidazole polymer and the further polymer has a bromoalkyl side chain.

[0104] Blending can create crosslinks, particularly ionic and / or covalent crosslinks, between the polymers. This can improve the mechanical and chemical stability of membranes made from such materials compared to membranes consisting solely of the synthesized polymer. At the same time, ionic conductivity can be increased.

[0105] It is also possible that further post-treatment of the blended polymer mixture takes place. Specifically, doping can take place. The doping of the blended polymer mixture can be carried out with mineral acids, particularly sulfuric acid or phosphoric acid, or any organic phosphonic acid of the structure R(PO3H2). x(R = any organic residue, preferably an electron-poor aromatic group such as one with one or more F or one or more other electron-withdrawing groups such as NO, NO2, SO2R, etc., because electron-withdrawing groups increase the acidity and thus the ionic conductivity of the phosphonic acid, x = 1-12). Furthermore, the post-treatment may 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.

[0106] Furthermore, anion exchange groups can be generated in the blended polymer mixture. The generation of anion exchange groups can be achieved by alkylating (quaternizing) any tertiary N-basic groups present in the blended polymer mixture and / or by reacting halomethyl groups of the form CH2Hal with Hal=Cl, Br, I present in the blended polymer mixture with tertiary N-basic groups. These process steps can further improve the properties of the resulting material, and in particular of a membrane produced from this material.

[0107] A substance produced by such a process is characterized by a particularly favorable property profile. The substance is preferably a polymer or a polymer mixture. Specifically, the substance can be a synthesized polymer containing halogens Hal directly bonded to the aromatics (Hal=Cl, Br, I). These can already be present in the monomers of the starting material or can be formed by a polymer-analogous bromination of the synthesized polymers with elemental bromine, optionally under FeCl3 or AlCl3 catalysis, or by reaction with NBS (N-bromosuccinimide).

[0108] It is also possible for the materials produced by the process according to the invention to be processed into fiber mats, in particular porous fiber mats, which are also referred to as random 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 can be produced, in which the fiber mat acts as mechanical reinforcement and, depending on the type of polymer from which the fiber mat is made, can even be ionically conductive if the material of the fiber mat consists of a cation exchange or anion exchange polymer or of a mixture of an anion exchange polymer with a cation exchange polymer.A mixture of a sulfonated polymer with a basic polymer can also be spun into fibers, where the conductivity of the fibers can be adjusted by the molar mixing ratio between the polymers. As long as the acidic polymer is present in a molar excess in the polymer mixture, the fibers are cation-conductive. If the molar mixing ratio between acidic and basic polymers is 1:1, i.e., if no excess cation-conductive groups are present, the fibers are no longer cation-conductive.

[0109] The blended polymer mixture can be an acid-acid blend. One of the two polymers can be a sulfonated, in particular partially fluorinated, polymer, which was produced in particular by polyhydroxyalkylation, and the other of the two polymers can be a phosphonated, in particular partially fluorinated, polymer, which was preferably synthesized by polyhydroxyalkylation. Preferably, additional covalent crosslinking can be present, which takes place in particular by nucleophilic aromatic substitution of fluorine atoms. The nucleophilic substitution can preferably take place by a thiol, in particular a dithiol, preferably an alkanedithiol. In this way, the water absorption of a membrane produced in this way can be limited.

[0110] The object underlying the invention is further achieved by a membrane which comprises such a substance produced by a method as described above or which consists of such a substance.

[0111] The thickness of the membrane can be less than 100 pm, in particular less than 75 pm, preferably less than 50 pm. To produce the membrane, the material produced by a process as described above can be dissolved in a suitable solvent and doctored onto a suitable 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.

[0112] The invention further 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.

[0113] For further details of the invention, reference is made to the dependent claims and 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. The starting materials mentioned in connection with the description of the exemplary embodiments are preferred embodiments of starting materials for the process according to the invention. In some cases, the individual figures show, or the description of the exemplary embodiments relates only to, individual process steps (e.g., the synthesis of a polymer or modifications in the context of a subsequent reaction) of the process according to the invention. The figures show

[0114] Figure 1 shows a reaction scheme of a process according to the invention according to a first embodiment of the present invention; Figure 2 shows a reaction scheme of processes according to the invention according to a second embodiment of the present invention;

[0115] Figure 3 shows a reaction scheme of another possible subsequent reaction of the process shown in Figure 2;

[0116] Figure 4 shows a reaction scheme of a process according to the invention according to a third embodiment of the present invention;

[0117] Figures 5a-b show reaction schemes of processes according to the invention according to a fourth embodiment of the present invention;

[0118] Figure 6 shows a reaction scheme of processes according to the invention according to a fifth embodiment of the present invention;

[0119] Figure 7 shows a reaction scheme of a process according to the invention according to a sixth embodiment of the present invention;

[0120] Figure 8 shows a reaction scheme of the process according to the invention according to a seventh embodiment of the present invention;

[0121] Figure 9 shows an alternative or supplementary pre-reaction to the process of Figure 8; Figure 10 shows a 1 H-NMR spectrum of a copolymer of paraterphenyl and 1-(1 H-benzimidazol-2-yl)ethanone (Example 8);

[0122] Figure 11 is a GPC curve of the copolymer of Figure 10;

[0123] Figure 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;

[0124] Figure 13 a 1H-NMR spectrum of the copolymer from Figure 10, which was reacted with 1,2-bis-(chloroethoxy)-ethane compared to the starting polymer;

[0125] Figure 14 a 1 H-NMR spectrum of the copolymer of para-terphenyl and 1-(1 H-benzimidazol-2-yl)ethanone, which was reacted with 1,2-bis-(chloroethoxy)-ethane in DMSO-d8, which was quaternized with trimethylamine to form an anion exchange polymer;

[0126] Figure 15 a 1 H-NMR spectrum of the copolymer of m-terphenyl, biphenyl and 4-acetylpyridine in CH2Cl2 (Example 9);

[0127] Figure 16 a 1 H-NMR spectrum of the 15% methylated copolymer from Figure 15;

[0128] Figure 17 is a graph showing the Coulomb efficiency, voltage efficiency, and energy efficiency of a membrane made from the materials of Example 9; Figure 18 is a reaction scheme of a method according to the invention according to a tenth example;

[0129] Figure 19 the 1 H-NMR spectrum of the substance prepared according to the reaction scheme in Figure 18;

[0130] Figure 20 shows a reaction scheme of a preliminary reaction of a process according to the invention according to an eleventh embodiment;

[0131] Figure 21 the 1 H-NMR spectrum of the substance prepared by the process according to the reaction scheme of Figure 20;

[0132] Figure 22 shows a reaction scheme of a polyhydroxyalkylation in which a starting material was modified by the process shown in Figure 20;

[0133] Figure 23 shows a reaction scheme of a process according to the invention according to a twelfth embodiment;

[0134] Figure 24 the 1 H-NMR spectrum of the substance obtained by the process shown in Figure 23; and

[0135] Figure 25 the 1H-NMR spectrum of a substance obtained from a process according to the invention according to a 13th embodiment;

[0136] Figure 26 the 19 F-NMR spectrum of the substance obtained by a method according to the 13th embodiment; Figure 27 shows another 1 H-NMR spectrum of the starting polymer and the modified sulfonated polymer of the 13th embodiment;

[0137] Figure 28 Structural formulas of polymers prepared according to a 14th

[0138] embodiment of a method according to the invention;

[0139] Figure 29 a 19 F-NMR spectrum of a doubly phosphonated copolymer of p-terphenyl and perfluoroacetophenone (15th embodiment);

[0140] Figure 30 shows a reaction scheme of a process according to the invention according to a 16th embodiment;

[0141] Figure 31 shows a 1 H-NMR spectrum of the substance obtained by a method according to the 16th embodiment;

[0142] Figure 32 shows the molecular weight distribution of the substance obtained by a method according to the 16th embodiment;

[0143] Figure 33a-c reaction schemes for subsequent reactions of a process according to the invention (17th embodiment);

[0144] Figure 34 shows a reaction scheme for subsequent reactions of a process according to the invention (18th embodiment);

[0145] Figure 35 Structural formulas of alternative PHA polymers for the subsequent reactions of Figure 34; Figure 36 Reaction schemes for subsequent reactions of a process according to the invention (19th embodiment);

[0146] Figure 37 Reaction schemes for subsequent reactions of a process according to the invention (20th embodiment);

[0147] Figure 38 shows a reaction scheme for subsequent reactions of a process according to the invention (21st embodiment);

[0148] Figure 39 shows a structural formula of an alternative PHA polymer for the subsequent reaction shown in Figure 38;

[0149] Figure 40 shows a reaction scheme of a subsequent reaction of a process according to the invention (22nd embodiment);

[0150] Figure 41 shows a structural formula of an alternative PHA polymer for the subsequent reaction from Figure 40;

[0151] Figure 42 shows a reaction scheme for synthesizing a polymer according to a process according to the invention (23rd embodiment);

[0152] Figure 43 shows a reaction scheme of a subsequent reaction of a process according to the invention (24th embodiment);

[0153] Figure 44 shows a reaction scheme of a subsequent reaction of a process according to the invention (25th embodiment);

[0154] Figure 45 shows a reaction scheme of a further subsequent reaction to the subsequent reaction of Figure 44 (26th embodiment); Figure 46 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (27th embodiment);

[0155] Figure 47 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (28th embodiment);

[0156] Figure 48 shows a reaction scheme for synthesizing a polymer by a process according to the invention (29th embodiment);

[0157] Figure 49 shows a reaction scheme for synthesizing a polymer by a process according to the invention (30th embodiment);

[0158] Figure 50 shows a reaction scheme for synthesizing a polymer by a process according to the invention (31st embodiment);

[0159] Figure 51 shows a reaction scheme for synthesizing a polymer by a process according to the invention (32nd embodiment);

[0160] Figure 52 shows a reaction scheme for synthesizing a polymer by a process according to the invention (33rd embodiment);

[0161] Figure 53 shows a reaction scheme for synthesizing a polymer according to a process according to the invention (34th embodiment);

[0162] Figure 54 shows a reaction scheme for synthesizing a polymer according to a method according to the invention (35th embodiment); Figure 55 shows a reaction scheme for synthesizing a polymer according to a method according to the invention (36th embodiment);

[0163] Figure 56 shows a reaction scheme for synthesizing a polymer according to a process according to the invention (37th embodiment);

[0164] Figure 57 shows a reaction scheme for synthesizing a polymer according to a process according to the invention (38th embodiment);

[0165] Figure 58 shows a reaction scheme of a process according to the invention (39th embodiment);

[0166] Figure 59 shows a reaction scheme of a process according to the invention (40th embodiment);

[0167] Figure 60 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (41st embodiment);

[0168] Figure 61 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (42nd embodiment);

[0169] Figure 62 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (43rd embodiment);

[0170] Figure 63 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (44th embodiment); Figure 64 shows a reaction scheme of possible subsequent reactions of a process according to the invention (45th embodiment);

[0171] Figure 65 shows a reaction scheme of possible subsequent reactions of a process according to the invention (46th embodiment);

[0172] Figure 66 shows a reaction scheme of possible subsequent reactions of a process according to the invention (47th embodiment);

[0173] Figure 67 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (48th embodiment);

[0174] Figure 68 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (49th embodiment);

[0175] Figure 69 shows a reaction scheme of possible subsequent reactions of a process according to the invention (50th embodiment);

[0176] Figure 70 shows a reaction scheme of possible subsequent reactions of a process according to the invention (51st embodiment);

[0177] Figure 71 shows a reaction scheme of possible subsequent reactions of a process according to the invention (52nd embodiment);

[0178] Figure 72 shows a reaction scheme of possible subsequent reactions of a process according to the invention (53rd embodiment);

[0179] Figure 73 shows a reaction scheme of a possible subsequent reaction of a process according to the invention (54th embodiment); and Figure 74 shows a reaction scheme of a further subsequent reaction of the polymer shown in Figure 73.

[0180] Example 1

[0181] Figure 1 shows a reaction scheme of an embodiment of a process according to the invention for producing a material for a membrane. A starting material containing 1-(4-methylpyridin-2-yl)ethan-1-one (first starting material) and an m-terphenyl (second starting material) is used. A polymer is synthesized from this by means of polyhydroxyalkylation, which is then lithiated with n-butyllithium. In a further subsequent reaction, 4-vinylpyridine is grafted anionically.

[0182] Example 2

[0183] Figure 2 also shows a reaction scheme of processes according to the invention. A starting material is provided which contains m-terphenyl (first starting material) and perfluoroacetophenone (second starting material). In a first step, polymer synthesis takes place by means of polyhydroxyalkylation. The PHA polymer thus obtained (polymer 2) is then sulfonated in a subsequent reaction to yield polymer 3. This can then optionally be modified in a subsequent reaction with basic groups (polymer 3a, polymer 3b), whereby the basic groups can form ionic crosslinking sites with the sulfonic acid groups. This reduces the swelling and water absorption of a membrane produced from such a polymer, thus improving the performance properties, 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, e.g. with the polymers 3a, 3b or another basic polymer such as a polybenzimidazole, so that ionically cross-linked acid-base blend membranes are formed.

[0184] Following sulfonation, additional phosphonation can be performed to improve proton conductivity, particularly at temperatures above 100°C. The improvement in proton conductivity results from the intrinsic proton conductivity of the phosphonic acid group (polymer 3c). Starting from this, an alkyl side chain can be introduced through a nucleophilic substitution reaction (polymer 3ca), thereby reducing the brittleness of the resulting polymer.

[0185] The sulfonated polymer 3 can also be covalently crosslinked, as shown in Figure 3, by nucleophilically substituting the 4F atoms of the pentafluorophenyl residue of the polymer with an aromatic or aliphatic dithiol. This then results in the polymer 3d shown in Figure 3.

[0186] Example 3

[0187] An alternative process according to the present invention is shown in Figure 4. In this process, a starting material is first modified in a preliminary reaction. Specifically, in a first step, commercially available 1-(4-mercaptophenyl)ethan-1-one (first starting material) is oxidized to 4-acetylbenzenesulfonic acid. In the next step, a polymer synthesis is carried out by polyhydroxyalkylation with m-terphenyl (second starting material) to yield a sulfonated aromatic polymer 4.

[0188] Embodiment 4 Figures 5a and 5b show various processes for producing a material for a membrane, which in particular comprise a Friedel-Crafts acylation and / or a Friedel-Crafts alkylation. Starting from polymer 5, which is shown in Figures 5a and 5b, a corresponding modification can take place (polymers 7 or 6). Starting from polymer 6, any desired nucleophilic aromatic substitution can then be carried out on the pentafluorophenyl radical (polymer 6a). In the present case, polymer 6a is a cation exchange polymer. Starting from polymer 7, a Friedel-Crafts acylation can take place to obtain an anion exchange polymer 7b.

[0189] Example 5

[0190] Figure 6 shows a reaction scheme of processes according to the invention, in which 1-(1H-benzo[d]imidazol-2-yl)ethan-1-one (first starting material) is first reacted with p-terphenyl (second starting material) in a PHA polymer synthesis to form polymer 8. Subsequently, deprotonation of the NH group can be carried out using LiH, followed by alkylation with methyl iodide to give the anion exchange polymer 8a. Alternatively, starting from polymer 8, sulfonation can take place, for example with chlorosulfonic acid, to form the acid-base polymer 8b.

[0191] Doping with phosphoric acid (PA) or any phosphonic acid (PhnA) R(PO3H2) is also conceivable. x (R = any organic residue, where R is preferably an aromatic residue with electron-withdrawing groups / atoms such as F, NO, NO2, SO2R, etc., x=1-12) in order to be able to use the polymer in high-temperature membrane fuel cells. The PA-doped

[0192] High-temperature membranes by blending with poly(vinylbenzyl chloride)

[0193] (PVBCI) can be converted into a covalently cross-linked blend membrane by reacting the chloromethyl groups of PVBCI with the NH of the imidazole function. Instead of PVBCI, a styrene polymer can be used for the reactive blending (reaction of the CH2Hal groups with NH) of the PHA polymer made from 1-(1H-benzo[d]imidazol-2-yl)ethan-1-one and p-terphenyl. This polymer carries the halomethyl group CH2Br or CH2Cl at the end of a side chain attached to the 4-position of the aromatic group of the polystyrene (for example, the polymer that can be produced by radical polymerization from 1-(6-chlorohexyl)-4-vinylbenzene). Alternatively, the production of an acid-base blend membrane is also conceivable by blending with an acidic, sulfonated or phosphonated polymer.

[0194] Example 6

[0195] Figure 7 shows a further embodiment of a process according to the invention for producing a material for a membrane. In this process, an acetylpyridine (first starting material) is reacted with a biphenyl and / or terphenyl (second starting material), in this case 2,2,2-trifluoro-1-(pyridin-4-yl)ethan-1-one (first starting material), with a pyridine-containing oligophenyl (second starting material), in this case 2,6-diphenylpyridine, in a polyhydroxyalkylation to obtain a synthesized, basic PHA polymer (polymer 9). Polymer 9 can then be converted either completely or partially to the anion exchange polymer 9a. The ratio between pyridine groups and quaternized pyridinium groups can be adjusted such that the property profile is favorable for use in electrochemical membrane processes, for example in redox flow batteries.The quaternization of polymer 9 to form the anion exchange polymer 9a can be carried out either by reaction with Mel or dimethyl sulfate or by reaction with a dihaloalkane, for example 1,4-diiodobutane, 1,6-diiodohexane, 1-chloro-6-iodohexane, 1-bromo-6-iodohexane 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 selected so that only the more reactive halogen (reactivity series of haloalkanes for nucleophilic substitution 1>Br>Cl»F) reacts by quaternization and the less reactive halogen is retained and can be used for further downstream nucleophilic substitution reactions, for example for the quaternization reaction with another tertiary N-basic compound.

[0196] It is conceivable that the anion exchange polymer 9a produced by alkylation of the polymer 9 can be blended with any basic polymer, for example with the polymer 8 from Figure 6, in order to optimize the properties such as ion conductivity, water absorption and mechanical properties for the respective application of a membrane.

[0197] Example 7

[0198] Figure 8 shows a reaction scheme of a process according to the invention, by which a so-called ferrocene polymer is produced. In this way, novel anion exchange polymers can be synthesized (for a proof-of-principle of this novel polymer type 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 (ferrocene aldehyde) (first starting material) are reacted with an aryl (second starting material) in a polyhydroxyalkylation.In the polymer synthesized in this way, the ferrocene is then partially oxidized at the central metal atom to obtain a positively charged polymer with a mixed oxidized state. Since the polymer is paramagnetic due to the iron, the polymer chains can be aligned using a magnetic field, creating directed, ion-conducting pathways within the polymer. Compared to a ferrocene polymer in the form of a poly(vinylferrocene), the polyferrocene according to the invention, shown in Figure 8, is chemically more stable in its polymer main chain because it does not contain any tertiary CH bonds vulnerable to radical attack.

[0199] Figure 9 shows another reaction scheme that can be used to increase the ferrocene group content of a polymer. To do this, a monobrominated terphenyl monomer can first be substituted with ferrocene groups.

[0200] According to the reaction scheme in Figure 9, the ferrocene-modified m-terphenyl is first synthesized with ferrocene ketone or aldehyde by polyhydroxyalkylation to form a polymer and then partially oxidized, as shown in Figure 8, to produce a corresponding ferrocene anion exchange polymer.

[0201] Example 8

[0202] Poly(terphenyl-co-1 -(1 H-Benzimidazol-2-yl)ethanone) (Polymer 8)

[0203] A terphenyl derivative such as para-terphenyl (second starting material) and an aromatic ketone such as 1-(1H-benzimidazol-2-yl)ethanone (first starting material) are suspended in a halogenated solvent such as dichloromethane, preferably with an excess of the ketone of between 1.00 and 2.00 equivalents, and more preferably with an excess of between 1.15 and 1.40 equivalents. The trifluoromethanesulfonic acid is then added, while the reaction mixture is stirred between 0°C and 60°C. The trifluoromethanesulfonic acid is preferably used in a molar excess of 5-20 equivalents relative to the ketone, with 8-13 equivalents being particularly preferred. After a preferred PHA reaction time of between 7 and 72 hours, the reaction is terminated by pouring the reaction mixture into water. Figure 10 shows the 1H-NMR spectrum of the copolymer (8) prepared in this way, with all resonance signals clearly assigned to the protons of the polymer. Gel permeation chromatography (GPC) (Figure 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 from 1.40 to 2.00 (Figure 15). 0.1 M LiCl DMSO and narrowly distributed PMMA standards were used as solvents for GPC. Furthermore, thermogravimetric analysis showed a high decomposition temperature of 480 °C.

[0204] The conversion of the copolymer of para-terphenyl and 1-(1H-benzimidazol-2-yl)ethanone into an anion-conducting polymer is possible by methylating the two nitrogens using suitable methylating agents such as methyl iodide, dimethyl sulfate, or dimethyl carbonate. Methylation can be carried out by dissolving the polymer in DMSO and treating the resulting solution with K2CO3 or NaH. An excess of the methylating agent is then added. After stirring for 16–30 h at 25–130°C, (partial or complete) methylation of both nitrogens of the benzimidazole ring occurs. Different degrees of methylation are possible depending on the reaction temperature and reaction time.In the example shown in Figure 12, it was surprisingly found that complete methylation of both nitrogen atoms to form the imidazolium cation had occurred. This is characterized by the complete absence of the resonance signal of the NH protons (12-15 ppm, top, Figure 12), the downfield shift of the aromatic signals, and a new signal corresponding to the two introduced methyl groups. The integrals are in complete agreement with the expected protons. The complete methylation of both nitrogen atoms is confirmed by comparing the 1 H- NMR spectrum of the methylated polymer (8a, top, Figure 12)) with the 1H-NMR spectrum of the original polymer is clearly visible (below, Figure 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 fundamental applicability of the polymer as an anion exchange material. If the above-mentioned reaction is carried out with meta-terphenyl instead of para-terphenyl, followed by methylation as described above, the chloride conductivity increases to 5.7 mS / cm.

[0205] 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. Surprisingly, it was found that by reacting the copolymer of para-terphenyl and 1-(1H-benzimidazol-2-yl)ethanone with a 5- to 60-fold excess of 1,2-bis-(chloroethoxy)ethane in the presence of a base (e.g., K2CO3, NaH, etc.) at temperatures between 25°C and 150°C, only one nitrogen atom could be selectively alkylated. Furthermore, it was found that no crosslinking occurred, as the polymers remained soluble in polar aprotic solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, or dimethyl sulfoxide. Figure 13 shows the comparison of the 1H 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. Calibration to the methyl group of the polymer backbone reveals that, surprisingly, quantitative functionalization has occurred (Figure 13). Following the introduction of the side chain, the chlorine substituent can be converted into an anion-conducting group with a tertiary amine in a Menschutkin reaction. Analogous to the functionalization with the described flexible ether side chains, functionalization with other dihaloalkanes such as dibromohexane or diiodohexane 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. Figure 14 shows this. 1 H-NMR spectrum of polymer 8b, which was converted into an anion exchange polymer using trimethylamine. Successful quaternization is evident from the characteristic signal of the methyl groups of the introduced trimethylammonium group at 2.97 ppm.

[0206] Example 9

[0207] Poly(m-terphenyl-co-biphenyl-co-(4-acetylpyridine)) (Polymer 10):

[0208] A terphenyl derivative such as m-terphenyl and / or biphenyl (second starting material) and an aromatic ketone such as 4-acetylpyridine (first starting material) are suspended in a halogenated solvent such as dichloromethane, preferably using an excess of ketone between 1.00 and 2.00 equivalents, and more preferably using an excess of between 1.10 and 1.40 equivalents. The trifluoromethanesulfonic acid is then added, while the reaction mixture is stirred between 0°C and 60°C. The trifluoromethanesulfonic acid is preferably used in a molar excess of 5-20 equivalents relative to the ketone, with 8-13 equivalents being particularly preferred. After a preferred reaction time (PHA) of between 7 and 48 hours, the reaction is terminated by pouring the reaction mixture into water. Figure 15 shows the 1H NMR spectrum of the copolymer prepared in this way with unambiguous assignment of all resonance signals to the protons of the polymer. Gel permeation chromatography (GPC) shows, depending on the reaction time and the molar excess of the ketone, molecular weights (M n ) between 10 000 g / mol and 300 000 g / mol and dispersities (D) of 1 .40

[0209] 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 1-30 hours. The reaction shown in Figure 16 1 H-NMR spectrum shows such a polymer (polymer 10a) with a degree of methylation of 15%.

[0210] Membranes can be produced from the previously described polymers using a doctor blade. For this purpose, solutions of the polymers are prepared in NMP, DMAc, or DMSO with a polymer mass fraction between 1% and 30%. The conductivities, degrees of methylation, and thicknesses of two membranes prepared in this way are shown in the table below. The membranes described above can potentially be used in various electrochemical applications. One example of such an application is the vanadium redox flow battery. Figure 17 shows the Coulomb efficiency (CE), the voltage efficiency (VE), and the energy efficiency (EE) as a function of current density over 30 cycles at a current density of 80 mA*cm 2 of a single-cell assay using a membrane made of the polymer MTp-Bp Pyr-15.

[0211] Example 10

[0212] 5'-(6-Bromohexyl)-1,1':3',1"-terphenyl

[0213] The synthesis route for obtaining the starting material or starting monomer is shown in Figure 18. 12.56 g (39.8 mmol) of 5'-(6-bromohexyl)-1,1':3',1"-terphenyl are dissolved in 50 mL of 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 h. 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 stirring is continued for 16 h. The reaction is terminated by adding 5 mL of a 10 wt.% HCl solution. The reaction equation for this reaction is shown in Figure 18. For workup, the organic and aqueous phases are separated. The aqueous phase is washed 3 times with 10 mL of 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 under high vacuum at 110°C. The product mixture is purified using flash chromatography. Figure 19 shows this. 1 H-NMR spectrum of the fraction used for further reaction. Example 11

[0214] 4-(7-[1,1':3',1"-terphenyl]-5'-yl)heptyl)pyridine

[0215] The synthesis route for obtaining the starting material or starting monomer is shown in Figure 20. 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 approximately 5 min, 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 is 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 1 h at -78°C and 4 h at RT and then quenched by adding 20 mL of saturated ammonium chloride solution and 20 mL of water. For workup, the organic and aqueous phases are separated. The aqueous phase is extracted three times with 20 mL of ethyl acetate.The organic phases were combined and washed twice with 20 mL of water, then dried using magnesium sulfate. THF and ethyl acetate were distilled off under vacuum, and the product mixture was purified using flash chromatography (isolated yield: 74%). Figure 21 shows this. 1 H-NMR spectrum of the product.

[0216] Both of the previously shown compounds can be converted into polymers using the polyhydroxyalkylation described above. Initial preliminary tests on the polyhydroxyalkylation of this monomer with 4-acetylpyridine have yielded molecular masses of approximately 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. Figure 22 shows the PHA reaction of 4-(7-([1,1':3',1"-terphenyl]-5'-yl)heptyl)pyridine with 4-acetylpyridine. If polymer 11 is partially or fully pyridine-alkylated, it can be used both in alkaline applications (AEMWE or AEMFC) and in redox flow batteries.

[0217] Example 12

[0218] 4-Methylpyridine coupling poly-biphenyl-co-7-bromo-1,1,1-trifluoroheptan-2-one

[0219] The synthesis of poly-biphenyl-co-7-bromo-1,1,1-trifluoroheptan-2-one is shown in Figure 23. 25 mL of dry THF is placed in a 250 mL Schlenk flask and cooled to -78°C. 1.10 mL (7.8 mmol) of diisopropylamine is added. After approximately 5 min, 3.09 mL of a 2.5 M butyllithium solution in hexane (7.74 mmol) is added. After 30 min, 0.51 mL (5.2 mmol) of 4-methylpyridine is 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 is dissolved in 75 mL of dry THF and slowly added dropwise to the reaction mixture (15 min). The solution is stirred for 4 h at -78°C and 20 min at RT and then quenched by adding 2 mL of methanol. The reaction equation for the synthesis of polymer 12 is shown in Figure 23.For purification, the product mixture is concentrated to 20 mL under vacuum, precipitated in 200 mL of methanol, filtered, washed 3 times with fresh methanol, and dried at 85°C in a drying oven. Figure 24 shows this. 1 H-NMR spectrum of the product.

[0220] Membranes can be produced from the previously described polymer 12 using a doctor blade. For this purpose, solutions of the polymer in NMP, DMAc, or DMSO are prepared with a polymer mass fraction 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 pm exhibited a conductivity of α = 14 mS*cm- 1 .

[0221] Example 13

[0222] Sulfonated poly-p-terphenyl-co-perfluoroacetophenone analogous to polymer 3

[0223] In a Schlenk flask, 1.0 equivalents of terphenyl and 1.0 to 2.0 equivalents (preferably 1.1 to 1.4 equivalents) of the ketone are placed in 9-13 equivalents of dichloromethane. 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.

[0224] In Figure 25 the corresponding 1 H-NMR spectrum and in Figure 26 the 19 F-NMR spectrum of the resulting polymer (analogous to polymer 2) is shown.

[0225] Polymer 2, prepared as described above, is suspended in a sulfonating agent (e.g., sulfuric acid, chlorosulfonic acid, 20% oleum, 65% oleum, etc.). The mixture is stirred at room temperature for 5 to 96 hours. The resulting highly viscous polymer solution is precipitated in ice water. The resulting polymer 3 is filtered off and washed with water. Depending on the sulfonating agent, a degree of sulfonation of between 2 and 3 sulfonic acid groups per repeating unit is achieved.

[0226] The resulting polymers were characterized by NMR spectroscopy. Successful substitution was confirmed by the downfield shift of the protons on the substituted aromatic rings. Compared to the starting polymer (see Figure 27), the NMR spectra show a mixture of different degrees of sulfonation with respect to a single repeating unit.

[0227] Therefore, an average degree of sulfonation is determined by elemental analysis, the results of which are shown in the table below.

[0228] Membranes can be produced from the previously described polymers using a doctor blade. For this purpose, solutions of the polymers are prepared in NMP, DMAc, or DMSO with a polymer mass fraction between 1% and 30%. The conductivities and thicknesses of three membranes prepared in this way are shown in the table below.

[0229] The membranes described above have potential for use in various electrochemical applications, such as fuel cells and electrolysis. Initial preliminary tests have demonstrated the fundamental suitability of the sulfonated polymer for use in fuel cells.

[0230] Embodiment 14 Ionic cross-linked cation exchange acid-base blend membrane 11 made of a sulfonated terphenyl polymer of perfluoroacetophenone and terphenyl:

[0231] In the first step, a PHA polymer is prepared by reacting perfluoroacetophenone (second starting material) with p-terphenyl (first starting material), see Figure 2. If the sulfonation of this polymer is carried out with the strong sulfonating agent oleum (H2SO4 with 60-65 wt% dissolved SO3), all three aromatics of the polymer's repeating unit can be sulfonated. A polymer with an ion exchange capacity of 4.19 meq SO3H / g polymer is obtained. In the second step, a polymer is synthesized from p-terphenyl with 1-(1H-benzo[d]imidazol-2-yl)ethan-1-one (see Figure 6). The structures of both polymers, along with their empirical formulas and molecular masses of their repeating units, are shown in Figure 28.

[0232] 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 wt% solution of the benzimidazole terphenyl polymer in DMSO is prepared, and 12.8 g of this solution is added to the DMSO solution of the sulfonated terphenyl polymer. Stir until homogeneous, and then a membrane is drawn onto a glass plate using a film drawing device. The glass plate with the drawn membrane is then placed in a convection 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 post-treated as follows:

[0233] 1. 48 hours at 90°C in 10% HCl

[0234] 2. 48 hours at 60°C in deionized water. The membrane can then be characterized. Its ion exchange capacity (IEC) is 1.5 meq SO3H / g membrane. The polymer can then be covalently crosslinked (see Figure 3) by using a membrane of the polymer in the sulfonic acid salt form (SO3R where R=any ammonium group N(R2)4). + (R2=H, alkyl) or alkali metal cation such as Li + , N / a + , K + , Rb + , Cs +) in a (for example 10 wt% ethanolic solution of an alkanedithiol (example: hexane-1,6-dithiol) or a dithiophenol (example: [1,1'-biphenyl]-4,4'-dithiol) that has been neutralized with equimolar amounts of a base, for example n-propylamine, for 24 hours at 90°C. The membrane is then rinsed with ethanol until no free dithiophenols or alkanedithiols are left in the membrane. The membrane is then placed at 90°C in 10% HCl for 48 hours and then at 60°C in deionized water for 48 hours to recreate the acid form of the membrane. The advantage of this crosslinking is that no sulfonic acid groups have to be "sacrificed" for the crosslinking.

[0235] Example 15

[0236] Multiphosphonated poly-p-terphenyl-co perfluoroacetophenone from the analogue to polymer 2:

[0237] The polymer prepared 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 resulting polymer is heated to reflux in water and then stirred in warm 1 M hydrochloric acid. 19 Surprisingly, F-NMR reveals a substitution of the fluorine atoms on the pentafluorophenyl ring in the para position and one of the two ortho positions (Figure 29), so that two phosphonic acid groups could be introduced, which has not been observed so far for any phosphonation on the pentafluorophenyl group-containing polymers.

[0238] The materials 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 crosslinking of membranes made from this phosphonated polymer with alkanedithiols or aromatic dithiophenols is also possible; see also Figure 3.

[0239] Example 16

[0240] Figure 30 initially shows the synthesis of a polymer by polyhydroxyalkylation. A first starting material, in this case a phenyl derivative, in particular m-terphenyl or p-terphenyl, and / or a biphenyl, is provided, and an aromatic trifluoroketone, in particular 1,1,1-trifluoro-3-(pyridin)4-ylpropan-2-one, is provided as a second starting material.

[0241] The phenyl derivative such as m-terphenyl, p-terphenyl, and / or biphenyl and an aromatic trifluoroketone such as 1,1,1-trifluoro-3-(pyridin-4-yl)propan-2-one are suspended in a halogenated solvent such as dichloroethane, preferably using an excess of ketone of between 1.00 and 2.00 equivalents, and particularly preferably using an excess of between 1.10 and 1.40 equivalents. The trifluoromethanesulfonic acid is then added, while the reaction mixture is stirred between 0°C and 80°C. The trifluoromethanesulfonic acid is preferably used in a molar excess of 5-20 equivalents relative to the ketone, particularly preferably using 8-13 equivalents. After a preferred reaction time between 168 h and 504 h, the reaction is stopped by pouring the reaction mixture into water. Figure 31 shows the 1H NMR spectrum of the polymer prepared in this way. Gel permeation chromatography (GPC) shows, depending on the reaction time and the molar excess of the ketone, molecular weights (M n ) between 10,000 g / mol and 300,000 g / mol and dispersities (D) of 1.40 - 2.00. An exemplary molar mass distribution is shown in Figure 32.

[0242] Example 17

[0243] Figures 33a, 33b, and 33c show reaction schemes for the production of blend membranes from a sulfonated PHA polymer and a PHA polymer with haloalkyl side chains. In principle, both polymers can be produced by the process according to the invention. The two polymers can be mixed in virtually any mixing ratio between 95:5 and 5:95. In this way, cation exchanger-anion exchanger acid-base blend membranes can be produced. The blend membranes can be treated with a tertiary amine such as tetramethylimidazole.

[0244] Specifically, the procedure is to first sulfonate the terphenyl PHA polymer with oleum. After sulfonation, it is converted to the sodium form by neutralization with NaOH. The neutralized polymer is dried and dissolved in a dipolar aprotic solvent such as DMSO or DMAc to a 5 to 20% solution. The biphenyl bromine side-chain PHA polymer is then dissolved in DMSO or similar to a 5 to 20% solution. The two polymer solutions are then mixed in the desired ratio and homogenized. Tetramethylimidazole (TMIm) is then added to the homogenized polymer solution in a 5 mol% excess relative to the bromine content of the biphenyl polymer. Surprisingly, it was found that at room temperature, the TMIm only reacts with the bromoalkyl groups over a period of several hours.so that the membrane can be produced without the risk of crosslinking during the mixing process of the two polymer solutions. The TMIm is allowed to dissolve and then the polymer solution is drawn onto a support such as a glass plate using a doctor blade. The solvent is then evaporated in a circulating air or vacuum drying oven at temperatures of 90 to 140°C. During this time the quaternization reaction takes place. The membrane is then detached from the support under water and post-treated with a 5 to 20% aqueous mineral acid at elevated temperatures in order to carry out the ion exchange and generate the acid-base crosslinking between the sulfonate and the tetramethylimidazolium ions. The membrane must then be rinsed with deionized water until the excess mineral acid is removed from the membrane. In the case of an imidazole that is even more sterically hindered than TMIm, such as TMIm, B. 1-butyl-2-mesityl-4,With 5-dimethyl-1H-imidazole, the quaternization reaction proceeds even more slowly. If more reactive amines such as quinuclidine, trimethylamine, N-methylpiperidine, or similar, which react with the bromine atoms of the side chain to quaternize even at room temperature, are used instead of TMIm, the blend membrane must be prepared using the following procedure: 1) Mix the acidic terphenyl-PHA polymer (can be in the SO3H or sulfonate salt form) and the bromoalkyl-biphenyl-PHA polymer as a solution in a dipolar aprotic solvent (DMSO is preferred because it is N-free); 2) Evaporate the solvent; 3) Place the membrane in the desired tertiary amine (if liquid) or in an ethanolic solution of the tertiary amine (if solid), optionally at elevated temperature to accelerate the quaternization reaction; 4) Rinse the membrane with deionized water,until all excess amine and ethanol are removed from the membrane; 5) the membrane is post-treated with a 5 to 20% aqueous mineral acid at elevated temperatures to perform ion exchange and generate acid-base crosslinking between the sulfonate and tetramethylimidazolium ions; 6) the membrane is rinsed with deionized water until the excess mineral acid is removed from the membrane.

[0245] In this embodiment, the sulfonated PHA polymer shown here can be replaced by any other sulfonated PHA polymers according to the invention. The same applies to the halomethylated blend component.

[0246] Example 18

[0247] Figure 34 shows a reaction scheme for the production of blend membranes from a benzimidazole-PHA polymer and a polymer with bromoalkyl side chains. In other words, the synthesized polymer produced according to the process of the invention can be a benzimidazole polymer. The additional polymer can be a PHA polymer, i.e., synthesized by polyhydroxyalkylation. In the embodiment of Figure 34, a covalently crosslinked anion exchange polymer blend is formed by the alkylation of the imidazole units of the benzimidazole-PHA polymer.

[0248] Specifically, the procedure involves mixing both polymers in a dipolar aprotic solvent (preferably DMSO, as it is nitrogen-free) in the desired ratio. The solvent is then evaporated at elevated temperatures in a circulating air or vacuum drying cabinet. The resulting membrane is then stripped under deionized water. If necessary, the membrane can be post-treated with any tertiary amine to quaternize any bromoalkyl groups still present in the membrane by placing the membrane in the amine (if liquid) or in an ethanolic solution of the amine (if solid). A sterically hindered amine such as quinuclidine or N-methylpiperidine, or a sterically hindered diamine such as DABCO, is preferred. The membrane is then rinsed with deionized water until all residual solvent and amines remaining in the membrane have been removed.The membrane can then be converted to the OH form by immersion in KOH, followed by washing with deionized water previously boiled in nitrogen. The membrane must then be stored under an inert gas atmosphere to prevent it from absorbing CO2 from the air.

[0249] Covalently crosslinked anion exchange blend membranes of this type can also be produced by reacting other imidazole group-containing PHA polymers with other bromine side-chain PHA polymers according to the invention, for example by reacting poly(2-(1-([1,1'-biphenyl]-4-yl)ethyl)-4,5-dimethyl-1H-imidazole) with poly(4-(8-bromooctan-2-yl)-1,1'-biphenyl). These two polymers are shown in Figure 35.

[0250] Example 19

[0251] Figure 36 shows a reaction scheme for the preparation of a polymer blend from a phosphonated terphenyl polymer, which in this case was synthesized from p-terphenyl and perfluoroacetophenone, and a halomethylated polymer (e.g., polyvinylbenzyl chloride) or the polymer from Figure 23. The polymer blend is then quaternized with a tertiary amine, e.g., triethylamine, quinuclidine, tetramethylimidazole, or the like, to form an acid-base blend membrane from the phosphonated polymer and the resulting anion exchange polymer. Specifically, the procedure involves mixing both polymers in a dipolar aprotic solvent (preferably DMSO, since it is nitrogen-free) in the desired ratio, with an excess of the phosphonated blend component being preferred. The solvent is then evaporated off at elevated temperatures in a circulating air or vacuum drying oven. The resulting membrane is then removed under deionized water.The membrane is then immersed in quinuclidine or an alcoholic solution of quinuclidine, optionally at elevated temperature, to achieve quaternization of the quinuclidine. The membrane is then washed in deionized water until all traces of excess quinuclidine or solvent have been washed out of the membrane.

[0252] Instead of the phosphonated PHA polymer of the invention, a sulfonated PHA polymer of the invention can also be selected as the acidic blend component. The same applies to the halomethylated PHA polymer and to the choice of tertiary N-base, where any tertiary N-base can be used for quaternization, or mixtures of tertiary monoamines and diamines, whereby the use of a diamine can also create additional covalent crosslinking sites in the anion exchange blend membrane.

[0253] Example 20

[0254] Figure 37 shows another example of a subsequent reaction by which an acid-acid blend membrane is produced from a sulfonated, partially fluorinated PHA polymer and a phosphonated, partially fluorinated PHA polymer. In addition, covalent crosslinking occurs through nucleophilic aromatic substitution of fluorine atoms by an alkanedithiol, which limits water absorption. Specifically, the procedure involves mixing both polymers in a dipolar aprotic solvent (preferably DMSO, as it is nitrogen-free) in the desired ratio. The solvent is evaporated. The membrane is then placed in an ethanolic solution containing 1-10% octaneedithiol and twice the molar amount of DBU relative to the molar amount of dithiol to completely deprotonate the thiol groups and thus increase the nucleophilicity of the thiol. Alternatively, the membrane can also be placed in pure dithiol, which has been completely neutralized with DBU.The dithiol is allowed to act on the membrane for 15-60 minutes. The reaction is indicated by a discoloration of the membrane. The membrane is then removed from the dithiol bath and rinsed with deionized water until all dithiol and DBU residues are removed. It is then immersed in a 5-20% aqueous solution of a mineral acid (e.g., HCl, H2SO4, HNO3, etc.) to regenerate the acid form of the membrane.

[0255] Of course, dithiols of other chain lengths can also be used as covalent crosslinkers, whereby in the case of HS-(CH2) x -SH x can assume values ​​between 2 and 20. Alternatively, a different base can be used instead of DBU, e.g., triethylamine or trimethylamine, which are easier to wash out of the membrane than DBU due to their smaller molecular mass.

[0256] Example 21

[0257] Figure 38 shows a possible subsequent reaction of a process according to the invention. This involves sulfonation of the basic polymer 12 of Figure 23 with oleum. In this way, an acid-base polymer is produced in which additional ionic crosslinking occurs between acidic and basic groups. In this way, water absorption and swelling can be limited. Specifically, the procedure involves suspending the biphenyl-pyridine-PHA polymer in oleum (sulfuric acid with 60% dissolved free SO3) and allowing it to sulfonate for 24-48 hours at room temperature. The polymer is then carefully precipitated by carefully pouring it dropwise over crushed ice, if necessary while cooling with a cold bath. After all the polymer has been added dropwise, the strongly acidic solution is neutralized to pH 7 by dropwise addition of 10% aqueous NaOH solution while cooling with a cold bath.The water is removed from the solution by rotary evaporation. The dried polymer is then dissolved in a dipolar aprotic solvent (preferably DMSO, sulfolane, or diphenyl sulfone, as it is nitrogen-free) to a 5 to 20% solution. The polymer solution is spread onto a support, such as a glass plate, and the solvent is removed in a vacuum or forced-air drying cabinet at elevated temperature. The membrane is then detached from the support and placed in a dilute solution of a mineral acid in deionized water to protonate the membrane and create the ionic crosslinking sites. The membrane is then washed in deionized water to remove excess acid.

[0258] In principle, another basic polymer synthesized by polyhydroxyalkylation can also be used, for example the polymer shown in Figure 39.

[0259] Example 22

[0260] Figure 40 shows a possible subsequent reaction of the diphosphonated polymer of Figure 29 with an aminothiol. Specifically, this could be 3-(dimethylamino)propane-1-thiol. In this way, an acid-base polymer can be produced, which, due to the corresponding ionic crosslinking sites, is characterized by low swelling / water absorption.

[0261] Specifically, the diphosphonated polymer is dissolved in a dipolar aprotic solvent (preferably DMSO, as it is N-free). In the second step, a membrane is doctor-coated from the polymer solution. The solvent is evaporated at elevated temperature. The membrane is then placed in a 10% solution of 3-(dimethylamino)-propane-1-thiol in ethanol. The same molar amount of the base DBU is added to the solution. The membrane is left in this solution for 15 minutes to 4 hours at room temperature. When the color of the membrane no longer changes, the reaction is complete, and the membrane is removed from the solution. The remaining reagents are rinsed from the membrane by rinsing it with deionized water, if necessary at elevated temperatures of up to 90°C. The membrane is then placed in an aqueous solution of a mineral acid, such asHCl, H2SO4, or HNO3 to generate the acid-base cross-links and convert the membrane into the acid form. The membrane is then rinsed again with deionized water until all excess acid has been washed out.

[0262] Instead of the diphosphonated PHA polymer of p-terphenyl and perfluoroacetophenone, a disulfonated PHA polymer can also be reacted with the aminothiol, see Figure 41.

[0263] The disulfonated polymer shown in Figure 41 can be synthesized by reacting the unmodified PHA polymer from p-terphenyl with NaSH in a dipolar aprotic solvent such as DMSO or DMAc, followed by oxidation with H2O2 in acetic acid / sulfuric acid or trifluoroacetic acid. Embodiment 23

[0264] Figure 42 shows a reaction scheme for synthesizing a polymer from two starting materials, specifically 1-phenylnaphthalene (first starting material) and 7-bromo-1,1,1-trifluoroheptan-one (second starting material) by polyhydroxyalkylation. In other words, Figure 42 shows the process step of synthesizing a polymer from the starting materials by polyhydroxyalkylation.

[0265] Surprisingly, the polymerization described above succeeds in obtaining soluble polymers with a sufficiently high molecular weight. For this purpose, the monomers 1-phenylnaphthalene and 7-bromo-1,1,1-trifluoroheptan-2-one are dissolved in DCM in a ratio of 1:1.02, then treated at 0°C with an elevenfold excess of trifluoromethanesulfonic acid and stirred for 16 h. After the polymer has been precipitated from THF in methanol, it can be used for further reactions (as shown below).

[0266] Example 24

[0267] Figure 43 shows a possible subsequent reaction of the synthesized polymer shown in Figure 42. Specifically, a sulfonation occurs via electrophilic aromatic substitution.

[0268] The starting polymer shown in Figure 43 can surprisingly be sulfonated by electrophilic aromatic substitution by suspending / dissolving the starting material in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0269] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0270] Example 25

[0271] Figure 44 shows an alternative subsequent reaction on the synthesized polymer of Figure 42. This is a sulfonation by means of nucleophilic substitutions.

[0272] According to Figure 44, according to the invention, the terminal bromine atom is replaced by a nucleophilic substitution reaction with a thioacetate group, which is converted into a sulfonic acid by oxidation in a subsequent step.

[0273] To prepare the target structure, 1 equivalent of the starting polymer is initially introduced and dissolved in dimethylacetamide. 1.12 equivalents of potassium thioacetate per equivalent of halogen are added to the solution and stirred at an elevated temperature between 40 and 100 °C for 16 to 24 hours. The polymer is then precipitated from the cooled solution in methanol, filtered off, and dried.

[0274] The resulting polymer is then redissolved in dimethylacetamide, and the solution is cooled to 0 °C. Six equivalents of meta-chloroperbenzoic acid (MCPBA) are then added portionwise over 10 minutes. The mixture is then stirred at room temperature. The polymer is then precipitated in 1 M saline solution, washed with water, and dried.

[0275] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0276] Example 26

[0277] Figure 45 shows a reaction scheme for increasing the degree of sulfonation of the polymer sulfonated according to Example 25 (Figure 44). Specifically, this occurs by means of electrophilic aromatic substitution. In the illustrated example, the ionically conductive polymer shown in Figure 44 is further sulfonated by means of electrophilic aromatic substitution in order to increase the ion exchange capacity and consequently the conductivity.

[0278] For this purpose, the starting material shown in Figure 45 is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0279] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0280] Example 27

[0281] Figure 46 shows a possible subsequent reaction. This involves a simple phosphonation of a copolymer of 1-phenylnaphthalene and 1,1,1-trifluoro-7-(perfluorophenyl)heptan-2-one using a Michaelis-Arbuzov reaction. Specifically, it is a single phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 46. The preparation proceeds as follows:

[0282] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0283] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0284] Example 28

[0285] Figure 47 shows a possible subsequent reaction, specifically the double phosphonation of a copolymer of 1-phenylnaphthalene and 1,1,1-trifluoro-7-(perfluorophenyl)heptan-2-one using a Michaelis-Arbuzov reaction. Specifically, this is a double phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 47. The preparation proceeds as follows:

[0286] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0287] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0288] Example 29

[0289] Figure 48 shows a reaction scheme for synthesizing a polymer from trifluoroacetophenone and a 2,7-diphenylfluorene modified with 9,9-dihaloalkyl side chains by polyhydroxyalkylation. Figure 48 illustrates the preparation of a polymer according to the invention. Specifically, it shows the polymerization of a copolymer from trifluoroacetophenone and a 2,7-diphenylfluorene modified with 9,9-dihaloalkyl side chains by polyhydroxyalkylation.

[0290] To prepare this polymer, 1 equivalent of fluorene is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of trifluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0291] Example 30

[0292] Another reaction scheme for synthesizing a polymer is shown in Figure 49. Specifically, it involves the preparation of a copolymer from perfluoroacotephenone and a 2,7-diphenylfluorene modified with 9,9-dihaloalkyl side chains by polyhydroxyalkylation.

[0293] Specifically, Figure 49 shows the polymerization of a copolymer of trifluoroacetophenone and a 2,7-diphenylfluorene modified with 9,9-dihaloalkyl side chains by means of a polyhydroxyalkylation.

[0294] To prepare this polymer, 1 equivalent of fluorene is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of perfluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0295] Example 31

[0296] Figure 50 shows the synthesis of a copolymer of trifluoroacetophenone (first starting material) and phenyl-Zphenylalkyl side chain-modified 2,7-diphenylfluorene (second starting material) by polyhydroxyalkylation.

[0297] To prepare this polymer, 1 equivalent of fluorene is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of trifluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0298] Example 32

[0299] Figure 51 shows a reaction scheme of the process step of synthesizing a copolymer of perfluoroacetophenone and phenyl-Zphenylalkyl side chain-modified 2,7-diphenylfluorene by polyhydroxyalkylation.

[0300] To prepare this polymer, 1 equivalent of fluorene is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of perfluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0301] Example 33

[0302] Figure 52 shows the process step of synthesizing a polymer from trifluoroacetophenone (first starting material) and pentafluorophenyl-Zpentafluorophenylalkyl side chain modified 2,7-diphenylfluorene (second starting material) by polyhydroxyalkylation.

[0303] To prepare this polymer, 1 equivalent of fluorene is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of trifluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0304] Example 34

[0305] Figure 53 shows the process step of synthesizing a polymer from perfluoroacetofenone (first starting material) and pentafluorophenyl-Z-pentafluorophenylalkyl side chain-modified 2,7-diphenylfluorene (second starting material) by polyhydroxyalkylation. To prepare this polymer, 1 equivalent of the fluorene is initially charged in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of perfluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0306] Example 35

[0307] Figure 54 shows a reaction scheme of the process step of synthesizing a polymer from 1,2-diphenylperfluoroalkane (first starting material) and trifluoracetophenone (second starting material) by polyhydroxyalkylation.

[0308] To prepare this polymer, 1 equivalent of 1,2-diphenylperfluoroalkane is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of trifluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0309] Example 36

[0310] Figure 55 shows a reaction scheme for the process step of synthesizing a polymer by polyhydroxyalkylation. Specifically, the polymerization of a copolymer of trifluoroacetophenone and a 1,2-diphenylalkane by polyhydroxyalkylation is shown.

[0311] To prepare this polymer, 1 equivalent of 1,2-diphenylalkane is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of trifluoroacetophenone, and cooled to 0°C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0°C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0312] Example 37

[0313] Figure 56 shows a reaction scheme of the process step of synthesizing a polymer by polyhydroxyalkylation.

[0314] Specifically, the polymerization of a copolymer of perfluoroacetophenone and a 1,2-diphenylperfluoroalkane by means of polyhydroxyalkylation is shown here.

[0315] To prepare this polymer, 1 equivalent of 1,2-diphenylperfluoroalkane is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of perfluoroacetophenone, and cooled to 0 °C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0 °C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried under vacuum. Example 38

[0316] Figure 57 shows another reaction scheme of the process step of synthesizing a polymer by polyhydroxyalkylation.

[0317] Specifically, the polymerization of a copolymer of perfluoroacetophenone and a 1,2-diphenylalkane by polyhydroxyalkylation is shown here.

[0318] To prepare this polymer, 1 equivalent of 1,2-diphenylalkane is placed in dry dichloromethane, mixed with 1.05 to 1.5 equivalents of perfluoroacetophenone, and cooled to 0°C. 5 to 20 equivalents of trifluoromethanesulfonic acid are added to the resulting mixture, and the reaction mixture is stirred at 0°C for 8 to 72 hours. After the reaction time has elapsed, the highly viscous solution is carefully poured into methanol, and the polymer is precipitated. The precipitated solid is filtered off and dried in vacuo.

[0319] Example 39

[0320] Figure 58 shows a reaction scheme for the modification of a synthesized polymer in a subsequent reaction. Specifically, the sulfonation of the side chains of the copolymer, which was synthesized according to the reaction scheme in Figure 48, takes place in two steps by means of nucleophilic substitution.

[0321] According to Figure 58, according to the invention, the terminal halogen atoms of the aliphatic side chain, which can have both equally long and differently long haloalkyl chains, are replaced by a thioacetate group by means of a nucleophilic substitution reaction, which is converted into a sulfonic acid by means of oxidation in a subsequent step.

[0322] To prepare the target structure, 1 equivalent of the starting polymer is initially introduced and dissolved in dimethylacetamide. 1.12 equivalents of potassium thioacetate per equivalent of halogen are added to the solution and stirred at an elevated temperature between 40 and 100 °C for 16 to 24 hours. The polymer is then precipitated from the cooled solution in methanol, filtered off, and dried.

[0323] The resulting polymer is then redissolved in dimethylacetamide, and the solution is cooled to 0 °C. Six equivalents of MCPBA are then added portionwise over 10 minutes. The mixture is then stirred at room temperature. The polymer is then precipitated in 1 M saline solution, washed with water, and dried.

[0324] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0325] Embodiment 40 Figure 59 shows a reaction scheme of a modification of a synthesized polymer, in this case the synthesized polymer according to Figure 49. Specifically, a sulfonation of the side chains takes place in a similar manner as described in connection with Figure 58.

[0326] In the embodiment shown, according to the invention, the terminal halogen atoms of the aliphatic side chain, which can have both equally long and differently long haloalkyl chains, are replaced by a thioacetate group by means of a nucleophilic substitution reaction, which is converted into a sulfonic acid by means of oxidation in a subsequent step.

[0327] To prepare the target structure, 1 equivalent of the starting polymer is initially introduced and dissolved in dimethylacetamide. 1.12 equivalents of potassium thioacetate per equivalent of halogen are added to the solution and stirred at an elevated temperature between 40 and 100 °C for 16 to 24 hours. The polymer is then precipitated from the cooled solution in methanol, filtered off, and dried.

[0328] The resulting polymer is then redissolved in dimethylacetamide, and the solution is cooled to 0 °C. Six equivalents of MCPBA are then added portionwise over 10 minutes. The mixture is then stirred at room temperature. The polymer is then precipitated in 1 M saline solution, washed with water, and dried.

[0329] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0330] Example 41

[0331] Figure 60 shows a possible subsequent reaction for modifying a synthesized polymer. Specifically, this is the polymer synthesized according to the reaction scheme in Figure 54.

[0332] In the embodiment shown, according to the invention, the polymer shown in Figure 54 is further sulfonated by means of electrophilic aromatic substitution in order to introduce ionically conductive groups into the polymer.

[0333] For this purpose, the starting material shown in Figure 60 is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0334] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0335] Example 42

[0336] Figure 61 shows a reaction scheme of a possible modification of a synthesized polymer (from Figure 55) in a subsequent reaction. Specifically, this is a sulfonation by electrophilic aromatic substitution.

[0337] In the embodiment shown, according to the invention, the polymer shown in Figure 55 is further sulfonated by means of electrophilic aromatic substitution in order to introduce ionically conductive groups into the polymer.

[0338] For this purpose, the starting material shown in Figure 61 is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0339] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0340] Example 43

[0341] Figure 62 shows a reaction scheme of a subsequent reaction for modifying the synthesized polymer from Figure 56. Specifically, a sulfonation takes place by means of electrophilic aromatic substitution.

[0342] In the embodiment shown, according to the invention, the polymer shown in Figure 56 is further sulfonated by means of electrophilic aromatic substitution in order to introduce ionically conductive groups into the polymer.

[0343] For this purpose, the starting material shown in Figure 62 is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0344] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0345] Example 44

[0346] Figure 63 shows the reaction scheme of a possible subsequent reaction for modifying the synthesized polymer of Figure 57.

[0347] In the embodiment shown, according to the invention, the polymer shown in Figure 57 is further sulfonated by means of electrophilic aromatic substitution in order to introduce ionically conductive groups into the polymer.

[0348] For this purpose, the starting material shown in Figure 63 is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0349] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0350] Example 45

[0351] Figure 64 shows possible subsequent reactions on the synthesized polymer of Figure 56 (Example 37). Specifically, this involves a single or double phosphonation using the Michaelis-Arbuzov reaction on the pentafluorophenyl residues. The preparation of the mono- and di-substituted material proceeds as follows:

[0352] The polymer is suspended in an excess of tristrimethylsilyl phosphite or tris(trimethylsilyl)phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0353] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0354] Example 46

[0355] Figure 65 shows a possible subsequent reaction for modifying a synthesized polymer, in this case the synthesized polymer from Figure 57. This also involves a single or double phosphonation of the pentafluorophenyl residues by means of a Michaelis-Arbuzov reaction.

[0356] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0357] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine. It is then mixed with a dissolved polybase, such as OPBI, and then coated and evaporated in the same way as for the pure membrane. Example 47

[0358] Figure 66 shows a sulfonation of the polymer synthesized according to the reaction scheme of Figure 56 by means of nucleophilic aromatic substitution.

[0359] Specifically, it involves a nucleophilic substitution of the fluorine atom in the para position of the pentafluorophenyl residue with a thiol, followed by oxidation of the thiol to sulfonic acid. The corresponding material is prepared as follows:

[0360] 1 equivalent of the starting polymer is dissolved in degassed dimethylacetamide. In a separate flask, 1.2 equivalents of sodium hydrogen sulfide hydrate are dissolved in dimethylacetamide at elevated temperature. The previously prepared polymer solution is added dropwise to the prepared sulfide solution at elevated temperature. After the polymer solution has been added, the mixture is stirred overnight at room temperature. The resulting solution of the crude product is dialyzed against water to remove the organic solvent.

[0361] After dialysis, the aqueous polymer solution is mixed with a mixture of glacial acetic acid and hydrogen peroxide to oxidize the free thiol to sulfonic acid. The resulting mixture is heated at 50 °C for 24 hours. The mixture is then heated to reflux to destroy the excess peroxide. After the polymer solution has cooled, the polymer is precipitated in methanol and dried. The resulting ionically conductive polymer can be used to produce both a pure membrane and a blend membrane. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and precipitated using a base, e.g.Triethylamine or triethanolamine is neutralized and then mixed with a dissolved polybase such as OPBI and doctored and evaporated analogously to the pure membrane.

[0362] Example 48

[0363] Figure 67 shows a sulfonation of the polymer synthesized according to the reaction scheme of Figure 57 by means of nucleophilic aromatic substitution.

[0364] Specifically, it involves a nucleophilic substitution of the fluorine atom in the para position of the pentafluorophenyl residue by a thiol, followed by oxidation of the thiol to sulfonic acid. The corresponding material is prepared as follows:

[0365] 1 equivalent of the starting polymer is dissolved in degassed dimethylacetamide. In a separate flask, 1.2 equivalents of sodium hydrogen sulfide hydrate are dissolved in dimethylacetamide at elevated temperature. The previously prepared polymer solution is added dropwise to the prepared sulfide solution at elevated temperature. After the polymer solution has been added, the mixture is stirred overnight at room temperature. The resulting solution of the crude product is dialyzed against water to remove the organic solvent.

[0366] After dialysis, the aqueous polymer solution is treated with a mixture of glacial acetic acid and hydrogen peroxide to oxidize the free thiol to sulfonic acid. The resulting mixture is heated at 50 °C for 24 hours. The mixture is then heated to reflux to destroy the excess peroxide. After the polymer solution has cooled, the polymer is precipitated in methanol and dried.

[0367] Both a pure membrane and a blend membrane can be produced from the resulting ionically conductive polymer. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine, and then mixed with a dissolved polybase, such as OPBI, and then doctored and evaporated in the same way as for the pure membrane.

[0368] Example 49

[0369] Figure 68 shows two consecutive reactions for modifying the synthesized polymer from Figure 56, a phosphonation followed by sulfonation. Specifically, this is a single phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 68. In a subsequent step, the phenyl rings of the main chain are electrophilically sulfonated. The material is prepared as follows:

[0370] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0371] For this purpose, the previously obtained phosphonated intermediate is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water reaches a neutral pH.

[0372] From the resulting ionically conductive polymer, which is modified with both sulfonic acid groups and phosphonic acid groups, both a pure membrane and a blend membrane can be produced. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc or NMP and neutralized using a base, e.g. triethylamine or triethanolamine, and then mixed with a dissolved polybase such as OPBI and doctor bladed and evaporated in the same way as for the pure membrane.

[0373] Example 50

[0374] Figure 69 shows two consecutive reactions for modifying the synthesized polymer of Figure 57. First, a phosphonation takes place, followed by a sulfonation.

[0375] Specifically, this involves a single phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 69. In a subsequent step, the phenyl rings of the main chain are electrophilically sulfonated. The material is prepared as follows:

[0376] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0377] For this purpose, the previously obtained phosphonated intermediate is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water reaches a neutral pH.

[0378] From the resulting ionically conductive polymer, which is modified with both sulfonic acid groups and phosphonic acid groups, both a pure membrane and a blend membrane can be produced. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc or NMP and neutralized using a base, e.g. triethylamine or triethanolamine, and then mixed with a dissolved polybase such as OPBI and doctor bladed and evaporated in the same way as for the pure membrane.

[0379] Example 51

[0380] Figure 70 shows a possible subsequent reaction for modifying a synthesized polymer. This reaction involves first a double phosphonation followed by a sulfonation of the polymer, which was synthesized according to the reaction scheme in Figure 56.

[0381] Specifically, this involves a single phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 70. In a subsequent step, the phenyl rings of the main chain are electrophilically sulfonated. The material is prepared as follows:

[0382] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190°C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and then refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered off, washed with water until neutral, and dried. For this purpose, the previously obtained phosphonated intermediate is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water has a neutral pH.

[0383] From the resulting ionically conductive polymer, which is modified with both sulfonic acid groups and phosphonic acid groups, both a pure membrane and a blend membrane can be produced. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc or NMP and neutralized using a base, e.g. triethylamine or triethanolamine, and then mixed with a dissolved polybase such as OPBI and doctor bladed and evaporated in the same way as for the pure membrane.

[0384] Example 52

[0385] Figure 71 shows a reaction scheme for modifying the synthesized polymer in subsequent reactions. The previously synthesized polymer is the polymer shown in Figure 57. The subsequent reaction initially involves a double phosphonation followed by a sulfonation.

[0386] Specifically, this involves a single phosphonation of the pentafluorophenyl residues on the copolymer shown in Figure 71. In a subsequent step, the phenyl rings of the main chain are electrophilically sulfonated. The material is prepared as follows:

[0387] The polymer is suspended in an excess of tristrimethylsilyl phosphite and heated to 190 °C for several hours. The cooled polymer solution is then precipitated in heptane. The resulting polymer is dried and subsequently refluxed in water for 24 hours. The polymer is then stirred in 1 M HCl for 24 hours, filtered, washed with water until neutral, and dried.

[0388] For this purpose, the previously obtained phosphonated intermediate is suspended / dissolved in concentrated sulfuric acid, chlorosulfonic acid, or fuming sulfuric acid for several hours. The resulting suspension / solution is poured onto ice to precipitate the polymer. The resulting solid is filtered off and washed with water until the wash water reaches a neutral pH.

[0389] From the resulting ionically conductive polymer, which is modified with both sulfonic acid and phosphonic acid groups, both a pure membrane and a blend membrane can be produced. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and neutralized using a base, e.g., triethylamine or triethanolamine. It is then mixed with a dissolved polybase, such as OPBI, and the resulting membrane is doctored and evaporated. Example 53

[0390] Figure 72 shows a reaction scheme for the modification of the synthesized polymer in a subsequent reaction. The polymer is a copolymer of 1-phenylnaphthalene and 1,1,1-trifluoro-7-(perfluorophenyl)heptan-2-one. Sulfonation occurs via nucleophilic aromatic substitution.

[0391] Specifically, it involves a nucleophilic substitution of the fluorine atom in the para position of the alkylpentafluorophenyl residue by a thiol, followed by oxidation of the thiol to sulfonic acid. The corresponding material is prepared as follows:

[0392] 1 equivalent of the starting polymer is dissolved in degassed dimethylacetamide. In a separate flask, 1.2 equivalents of sodium hydrogen sulfide hydrate are dissolved in dimethylacetamide at elevated temperature. The previously prepared polymer solution is added dropwise to the prepared sulfide solution at elevated temperature. After the polymer solution has been added, the mixture is stirred overnight at room temperature. The resulting solution of the crude product is dialyzed against water to remove the organic solvent.

[0393] After dialysis, the aqueous polymer solution is mixed with a mixture of glacial acetic acid and hydrogen peroxide to oxidize the free thiol to sulfonic acid. The resulting mixture is heated at 50 °C for 24 hours. The mixture is then heated to reflux to destroy the excess peroxide. After the polymer solution has cooled, the polymer is precipitated in methanol and dried. The resulting ionically conductive polymer can be used to produce both a pure membrane and a blend membrane. To produce a pure membrane, the resulting sulfonated polymer is dissolved in DMSO, DMAc, or NMP. The resulting polymer solution is applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent is removed at elevated temperature. To produce an acid-base blend membrane, the resulting acidic polymer is dissolved in DMSO, DMAc, or NMP and precipitated using a base, e.g.Triethylamine or triethanolamine is neutralized and then mixed with a dissolved polybase such as OPBI and doctored and evaporated analogously to the pure membrane.

[0394] Example 54

[0395] Figures 73 and 74 show the reaction steps for modifying a synthesized polymer, in this case a basic polymer, to form an alkali-stable dication. In a first step (Figure 73), a polymer, in this case poly(2-([1,1',4,1"-terphenyl]-4-yl)ethyl)1H-benzo[d]imidazole)), is functionalized with 1,6-dibromohexane before, in a preferred embodiment, in a further reaction step, the bromine site is reacted with a compound which contains, in particular, a tertiary amino group and a quaternary ammonium ion, such as, for example, 1,1-dimethyl-4-(3-(1-methylpiperidin-4-yl)propyl)piperidin-1-ium, to form a dication.

[0396] Surprisingly, the basic polymer described above can be functionalized with 1,6-dibromohexane without crosslinking. Conversion rates are greater than 90%. For this purpose, the starting polymer is dissolved in DMAc, using low-concentration solutions (approx. 2-3 wt%) to avoid crosslinking. An excess of K2CO3 (9 equiv.) is then added, and the mixture is stirred at 80°C for 2 h to deprotonate the benzimidazole unit. After adding a 32-fold excess of 1,6-dibromohexane, the mixture is stirred at 80°C for 48 h. After precipitation in methanol, the precursor polymer is obtained for further functionalization reactions.

[0397] In the next step, the bromine site is converted into a dication with a monocation, such as 1,1-dimethyl-4-(3-(1-methylpiperidin-4-yl)propyl)piperidin-1-ium in Figure 74, resulting in anion exchange polymers with high ion exchange capacities (2.70 mmol / g). Surprisingly, these polymers are not water-soluble, which is why they can be used to produce membranes with high conductivities.

Claims

CLAIMS 1. A process for producing a material for a membrane, comprising the following steps: Providing at least one starting material, wherein at least one starting material contains or consists of at least one monomer; Synthesizing a polymer from the starting material(s) by polyhydroxyalkylation (PHA); Modification of the synthesized polymer in a subsequent reaction.

2. Process according to claim 1, characterized in that before synthesizing the polymer, a modification of at least one starting material takes place in a preliminary reaction.

3. A process for producing a material for a membrane, comprising the following steps: Providing at least one starting material, wherein at least one starting material contains or consists of at least one monomer; Modification of at least one starting material in a preliminary reaction; Synthesizing a polymer from the starting material(s) by polyhydroxyalkylation (PHA).

4. The method according to claim 3, characterized in that after synthesizing the polymer, a modification of the synthesized polymer takes place in a subsequent reaction.

5. Process according to one of the preceding claims, characterized in that at least one starting material contains at least one type of diaryl monomer.

6. Process 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.

7. Process 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)ethan-1 -one, 1,4-dimethylpiperazin-2-one, piperazin-2-one, 1,3-dimethyltetrahydropyrimidin-2(1H)-one, 1 -(1 -methyl-1 H-benzo[d]imidazole-2-yl)ethan-1 -one, 2,2,2-trifluoro-1 -(1 -methyl-1 H-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)ethan-1-one, 1 -(4-ethylpiperazin-2-yl)ethan-1 -one, 1 -(1 -methyl-1 H-pyrazol-4-yl)ethan-1 -one, pyrrolidine-3-carbaldehyde, 1 -(1 H-pyrazol-3-yl)ethan-1 -one, 1 -(1 H-benzo[d]imidazole-6-yl)ethan-1 -one, 1 -(7-methyl-1 H-benzo[d]imidazole-2-yl)ethan-1 -one, 1 -(1 H-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-1 H-pyrazol-3-yl)ethan-1 -one, 1 -(1 ,2,4-dimethyl-1 H-imidazol-5-yl)ethan-1 -one, 1 -(1 ,2,4-trimethyl-1 H-imidazol-5-yl)ethan-1 -one, 1 -(1 H-benzo[d]imidazol-7-yl)ethan-1 -one, 1 -(1 H-benzo[d]imidazol-2-yl)propn-1 -one, 1 -(1 H-benzo[d]imidazol-2-yl)propan-2-one, 1 -(1 ,4,5-trimethyl-1 H-imidazol-2-yl)ethan-1 -one, 2 ,2 ,2-trifluoro-1 -(1 -methyl-1 H-imidazol-2-yl)ethan-one, 1 -(1 -methyl-1 H-imidazol-2-yl)ethan-1 -one, 1 -(1 H-imidazol-5-yl)ethan-1 -one, 1 -(1 H-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-trifluoror- 1 -(piperidin-4-yl)ethan-1 -one, 1 -(quinolin-8-yl)ethan-1 -one, 1 -(quinolin-5-yl)ethan-1 -one, 2 ,2 ,2-trifluoror- 1 -(1 H-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-y l)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-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-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-trifluoroethane-1 -one, 2,2,2-trifluoro-1-(perfluorophenyl)ethan-l-one, 8-bromo-1,1,1-trifluorooctane-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-l -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 8. Process 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-diphenylnaphtalene, 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‘-tetrafluroro-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-tetraphenylnaphtalene, 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, N-N-dimethyl-[1 ,1 ‘ :3‘ , 1 “-terphenyl]-5‘-amine, N-N-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.

9. Process 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, wherein the organic radical is 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.

10. Process according to one of the preceding claims, characterized in that the polyhydroxyalkylation takes place under the influence of trifluoromethanesulfonic acid (TFSA).

11. Process 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.

12. The method according to any 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 comprises a nucleophilic aromatic substitution reaction and / or an electrophilic aromatic substitution reaction and / or a polymer-analogous reaction and / or an alkylation of basic nitrogen atoms to tertiary ary or quaternary N-basic compounds and / or is microwave-assisted.

13. A process according to any one of the preceding claims, characterized in that it comprises blending the synthesized polymer with another polymer to form a blended polymer mixture.

14. The method according to claim 13, characterized in that crosslinks, in particular ionic and / or covalent crosslinks, are formed between the polymers during blending.

15. The method according to claim 13 or 14, characterized in that doping of the blended polymer mixture takes place.

16. The method 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 comprises the introduction of further ion exchange groups, in particular acidic sulfonic acid and / or acidic phosphonic acid groups.

17. Process according to one of claims 13 to 16, characterized in that anion exchange groups are generated on the blended polymer mixture.

18. The method 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 blended polymer mixture containing halomethyl groups of the form CH2Hal with Hal = CI, Br, I with tertiary N-basic groups.

19. A substance produced by a process according to any one of the preceding claims.

20. A membrane comprising or consisting of a material according to claim 19.

21. Membrane according to claim 20, characterized in that the thickness is less than 100 pm, in particular less than 75 pm, preferably less than 50 pm.

22. Use of a membrane according to 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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