Aromatic polymer, process for producing a polymer, membrane and use of a membrane

Abstract

The present invention relates to an aromatic polymer, in particular an ion exchange polymer, preferably an anion exchange polymer or cation exchange polymer, which has at least one aromatic unit in its repeating unit, and wherein the polymer main chain of the polymer does not have any pure heteroatom bridges.

Description

[0001] DESCRIPTION Aromatic polymer, process for producing a polymer, membrane and use of a membrane The present invention relates to an aromatic polymer, in particular ion exchange polymer, preferably anion exchange polymer or cation exchange polymer. The invention further relates to a process for producing a polymer, as well as to a membrane and the use of a membrane. Membranes, in particular ion exchange membranes, are used particularly in electrochemical processes, for example in electrolysis processes, or in electrochemical systems, for example in a fuel cell or in a battery. Such membranes are subject to stringent requirements. Firstly, they must be sufficiently chemically stable with respect to the media surrounding them, depending on their field of application. Furthermore, such membranes are frequently exposed to mechanical stress.For electrochemical applications, a certain degree of conductivity combined with a low degree of swelling, i.e., low volume expansion, is required. One group of polymers that is fundamentally suitable for such applications is aromatic polymers. These contain at least one aromatic compound in their repeating units. Even though such common aromatic polymers have generally proven themselves, they have various disadvantages. First and foremost, a certain rigidity of the polymer chain must be mentioned, which can lead to low solubility in solvents and / or high brittleness of membranes made from such polymers. Another disadvantage is the possible degradation of aromatic polymers due to radical attack, which can occur preferentially adjacent to an ether bridge.Furthermore, hydrolytic degradation can occur, for example, during a sulfonation process. Against this background, the object of the present invention is to provide a polymer that has favorable property profiles and can be used in particular in membranes for electrochemical processes. Furthermore, a membrane and the use of such a membrane, as well as a method for producing such a polymer, are to be created. This object is preferably achieved in the case of an aromatic polymer of the type mentioned above in that it has at least one aromatic in its repeating unit, wherein the polymer main chain of the polymer contains no pure heteroatom bridges.Correspondingly, the process for producing a polymer comprises the following steps: − Providing a first starting monomer; − Providing a second starting monomer; wherein the starting monomers comprise aromatics provided with functional groups for polymerization, − Carrying out a polymerization to form a polymer, wherein the polymer has no pure heteroatom bridges in the polymer main chain. The invention is based on the fundamental idea of ​​avoiding pure heteroatom bridges, for example -O-, -S-, or -S(O2)- or -P(O)(phenyl)- in the polymer main chain. It has been shown that such heteroatom bridges represent a chemical weak point and are thus particularly susceptible to degradation. By avoiding such heteroatom bridges, which function as the exclusive bridge in the polymer main chain, such a chemical weak point can be eliminated.In a further embodiment, the aromatic polymer can have side chains, wherein the side chains in particular contain or consist of alkyl groups, alkyl ether groups, aryl ether groups and / or haloalkyl groups. The side chains can also contain or consist of aromatics or aromatics on alkylene. This can further improve the properties of the polymer. According to a preferred embodiment of the polymer according to the invention, it can contain perfluoroaromatic compounds. These are preferably present in the polymer main chain or coupled to it. At least one, in particular several, preferably two, three or four fluorine atoms of the perfluoroaromatic compound can be nucleophilically substituted by a functional group. It is also possible for 5, 6, 7, 8, 9, 10, 11 or 12 fluorine atoms to be nucleophilically substituted, in particular by a functional group.This can occur, for example, when partially or fully fluorinated biphenyl or terphenyl units are present. This design is based on the idea of ​​substituting at least one, in particular several, fluorine atoms of the perfluoroaromatic compounds. In other words, functional groups take the place of fluorine atoms. This allows the property profile to be adapted to the application, and different properties can be combined in a targeted manner. For example, it is possible to create a polymer with high ionic conductivity that is also low brittleness. By appropriate substitution, it is also possible to create completely fluorine-free polymers, which is particularly advantageous from an ecological point of view. Specifically, the perfluoroaromatic compound can be or comprise a perfluorophenyl and / or a perfluorobiphenyl unit.The perfluoroaromatic compound can in principle also be a perfluoroterphenyl unit or a perfluoroquaterphenyl unit. Preferably, the para and / or at least one ortho position and / or at least one meta position of the perfluorophenyl unit or the perfluorobiphenyl unit or a perfluoroterphenyl unit or a quaterphenyl unit are each substituted by a functional group. In a further embodiment, several fluorine atoms of the perfluoroaromatic compound can be substituted with the same functional group or with different functional groups. In other words, the same functional group can replace several fluorine atoms of the perfluoroaromatic group. Alternatively, different functional groups can also be provided, which can be particularly advantageous for establishing different material properties.Specifically, a functional group can be coupled to the perfluoroaromatic compound in such a way that a fluorine atom is substituted by a sulfur atom. In other words, the functional group can be designed such that a sulfur atom takes the place of a fluorine atom of the perfluoroaromatic compound. For example, a molecule with a thiol group can be used for substitution. Such a thiol group, which is also called a sulfhydryl group, is essentially a functional group that is structured similarly to the hydroxyl group (-OH), but with the oxygen atom replaced by a sulfur atom. Since the sulfur atom is particularly nucleophilic, it can substitute for the fluorine atom. If a thiol group is introduced into an organic compound, as is the case, for example, in the nucleophilic substitution described above, this is referred to as thiolation.In this case, the sulfur atom of the thiol group takes the place of a fluorine atom of the perfluoroaromatic compound. In a further embodiment, a functional group can be a linear and / or branched saturated or unsaturated C. n -body, especially a C2, C3, C6, C8, C 10 -, C 12 -, C 14 -, C 16 - or a C 18 -body that carries a sulfur atom or an oxygen atom at one end, which substitutes for a fluorine atom of the perfluoroaromatic compound. In other words, the sulfur atom that substitutes for the fluorine atom is followed by a corresponding linear or branched C n -body, which may also contain double bonds that are potentially usable for further addition or substitution reactions, for example for cross-linking. At the other end of the C n- body can be a quinuclidinium group or another quaternary N-group, in particular an ammonium, imidazolium, benzimidazolium, piperidinium, piperazinium, guanidinium, 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-, phosphonate R-PO3H-, carbonate CO3 2- , HCO3 -, or coupled with an organic carboxylic acid anion, especially CH3COO-, HCOO-. In other words, at the other end of the C n - body any other quaternary ammonium group NR4 +with R = any alkyl and / or aryl, for example a piperidinium or piperazinium or imidazolium group, benzimidazolium group, pyridinium group, alkylguanidinium group, in particular with a counteranion, in particular mineral acid anions (including halides, sulfates, sulfites, phosphates, carbonates, (per-)chlorates, borates), furthermore organic counteranions (including bis(sulfonyl)imides, carboxylic acid derivatives, sulfonic acid derivatives, phosphonic acid derivatives). Such C n -bodies can have a chain-like structure and are then also called C n -chains. In addition, the functional group can contain a nitrogen atom as a primary, secondary, tertiary or quaternary amine or ammonium group. Such a nitrogen atom can, for example, be present within a linear or branched and optionally unsaturated C n-body. A functional group can be in the form R-SH, R-S-, R-OH, R-NH, R-N- or PO3R2, where R is an alkyl radical, aryl radical, alkyl, aryl, a metal, Si(CH3)3, or H. Any combination is conceivable. Specifically, the first nucleophile, i.e. the first functional group that substitutes the para-fluorine atom, can have the form R-SH, RS-, R-OH, RO-, R-NH2, R-NH, RN-, or PO3R2. Completely independently of this, a second functional group can encompass all forms. The same applies to a third functional group.It is therefore possible that in perfluoroaromatic compounds in which a fluorine atom (for example the 4-F atom in a pentafluorophenyl unit) has already been replaced by one of the aforementioned functional groups, in particular of the form R-SH, RS-, R-OH, RO-, R-NH2, R-NH, RN-, or PO3R2, by means of a nucleophilic substitution reaction, further fluorine atoms can then be substituted by the same or a different functional group, in particular of the form R-SH, RS-, R-OH, RO-, R-NH2, R-NH, RN-, or PO3R2, by means of further nucleophilic substitution reactions. The radical R can differ for the various functional groups. It is therefore entirely possible for the first functional group to have the form R-SH, where R is aryl, and the second functional group to have the form R-OH, where R is a metal.Furthermore, the third functional group can easily have another form, for example, R-NH, where R is an alkyl radical. A functional group can also contain a thiol group, be based on a thiol group, or be prepared from a thiol group. If the functional group has the form SR, with the sulfur atom taking the position of the substituted fluorine atom, the R radical can be formed as shown in the figure below, but this does not limit the types of possible R radicals.

[0002] Furthermore, a functional group SO3 can be reacted with a counter cation, in particular with a metal counter cation or with an ammonium counter cation in the form NR4 +with R = H, alkyl, aryl, or with another N-basic cation, especially imidazolium, benzimidazolium, guanidinium. A functional group can contain C5NH10, where the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound. A residue or counteranion can be coupled, in particular via the nitrogen atom, where the residue is preferably a halide (F-, Cl-, Br-, I-) or SO4. 2- , HSO4-, PO4 3- , HPO4 2- , H2PO4-, SO3 2- , SO3H-, phosphonate R-PO3H-, carbonate CO3 2-, HCO3- or an organic carboxylic acid anion such as CH3COO-, HCOO-. The radical or the counteranion can in particular be mineral acid anions (including halides, sulfates, sulfites, phosphates, carbonates, (per-)chlorates, borates), or organic counteranions, preferably bis(sulfonyl)imides, carboxylic acid derivatives, sulfonic acid derivatives, phosphonic acid derivatives). At least one fluorine atom of the perfluoroaromatic compound can be substituted by an S, N, O, C and / or P nucleophile. Such nucleophiles are often negatively charged or have at least one free electron pair, in particular in a relatively high-energy orbital. In a further embodiment, the aromatic polymer according to the present invention can have acidic groups, in particular sulfonic acid groups and / or phosphonic acid groups. Such acidic groups can be coupled to an electron-deficient aromatic compound.In particular, it can be an electron-poor aromatic compound due to appropriate functional groups. Examples of suitable functional groups include fluorine-free sulfone groups. At least one atom on the aromatic compound, in particular a hydrogen atom, can be electrophilically substituted. This can be a nitration or a sulfonation. It is also possible for an atom on the aromatic compound to be electrophilically substituted by Friedel-Crafts acylation. In principle, it can also be a halogenation. The polymer preferably has fluorinated building blocks. In a further embodiment, sulfonic acid side chains, in particular alkylic sulfonic acid side chains, can be present on the fluorinated building blocks. The polymer can also have a fluorene unit. Preferably, at least one, in particular several, sulfonic acid groups are present on the fluorene units. These can be attached, for example, by electrophilic substitution.It is also possible for the polymer to be phosphonated, where, for example, fluorine atoms are or have been substituted by a phosphonic acid group. Furthermore, fluorine atoms can be thiolated using a free thiol and subsequently oxidized to sulfonic acid. In principle, preferred starting monomers are 1,2,4,5-tetrafluorobenzene, octafluorobiphenyl, or 9,9-di-N-alkyl-2,7-dibromofluorene, or polymers prepared using these starting monomers. The polymer can be a polyfluorene, in particular a partially fluorinated polyfluorene, and / or a polyphenylene, in particular a partially fluorinated polyphenylene. The polymer can be a copolymer, in particular a block copolymer.This has at least two, in particular exactly two different polymer blocks, wherein one polymer block consists in particular at least predominantly of a polyphenylene and another polymer block consists at least substantially of a polyfluorene. In other words, the block copolymer contains at least two different types of polymer blocks, wherein one polymer block is a polyphenylene and another polymer block is a polyfluorene. The polymer chains of the polymer according to the invention can be covalently cross-linked with one another. In particular, the polymer chains can be covalently cross-linked with one another via a dithiol and / or a dithiophenol. This embodiment is based on the idea of ​​adapting the properties to requirements by cross-linking the polymer chains.In particular, a functional group that is coupled to several, in particular two, perfluoroaromatic compounds of two different polymeric chains can crosslink the polymer chains. The polymer can be produced by means of an arylation polymerization, in particular by means of palladium-catalyzed arylation polymerization. In a further embodiment, it can be polymerized from a fluoroaromatic and a dihaloaromatic. This means that two different starting monomers are used for the polymerization. Preferably, the two starting monomers contain functional groups on their aromatics, which are used for the polymerization. In other words, the polymerization of the different starting monomers with one another proceeds via the functional groups. This means that the functional groups react chemically with one another.The polymer is preferably designed such that the functional groups on the various aromatics are located at different positions on the aromatics. This results in angled polymer main chains, which improves the solubility of the polymers in solvents. To accelerate the reaction during polymer production, the polymer can be polymerized in a microwave reactor. In other words, the polymerization takes place under the influence of microwaves. In this way, the polymerization reaction can be significantly accelerated. The modification of the polymer can take place under the influence of microwaves and / or in a microwave reactor. The object underlying the invention is further achieved by a membrane, in particular an ion exchange membrane, preferably a cation exchange membrane or anion exchange membrane, which contains or consists of a polymer as described above.This can also be a blend membrane. The invention further relates to the use of such a membrane in an electrochemical system, in particular in a fuel cell or a battery, or in an electrochemical process, in particular in an electrolysis process or an electrosynthesis process. The process according to the invention can be designed such that the functional groups of the first starting monomer are arranged or coupled at different positions on the aromatic compound than the functional groups of the second starting monomer. This results in polymer main chains that are not straight but angled. In this way, the solubility of the polymer in solvents can be increased. The functional groups can, for example, also be individual atoms or a single proton. The second starting monomer can contain a fluoroaromatic compound or consist of a fluoroaromatic compound.The first starting monomer may contain or consist of a dihaloaromatic compound. In other words, the starting monomers may be two monomers with different structures. Examples of fluoroaromatic compounds that may be present in the second starting monomer or that form the second starting monomer are shown in the figure below. In particular, the fluoroaromatics which the second starting monomer contains or from which the second starting monomer consists are a benzene or benzenes, preferably fluorobenzene, particularly preferably tetrafluorobenzene, and / or biphenyls, preferably octafluorobiphenyl, and / or anthracenes, preferably octafluoroanthracene, and / or naphthalenes, preferably hexafluoronaphthalene, and / or phenyls, preferably terphenyls, and / or quaterphenyls, particularly preferably hexadecafluoroquaterphenyls, and / or biphenyls, particularly preferably octafluorobiphenyls, and / or phenanthrenes, preferably octafluorophenanthrene or hexafluorophenanthrene. Examples of the halogenoaromatics which the first starting monomer contains or from which the first starting monomer consists are shown in the figure below.

[0003] The first starting monomer is preferably a dibromoaromatic compound, in particular a dibromobenzene, a dibromobiphenyl, a dibromoterphenyl, a dibromofluorene, a dibromodibenzofuran, a dibromodihydroxanthene, a dibromotrimethyltetrahydroacryline, a dibromophenanthrene, or a dibromoanthracene. The first starting monomer is preferably a fluorene derivative. For example, it can be 3,6-dibromo-9,9-dialkylfluorene or 2,7-dibromofluorene. It is preferably a fluorene derivative that has two alkyl side chains in the 9-position. The alkyl side chains are preferably terminated with phenyl or pentafluorophenyl end groups.Bei dem ersten Ausgangsmonomer kann es sich auch um 4,4-Dibrombiphenyl, 3,3-Dibrombiphenyl, 2,7-Dibrom-9-Methyl-9H-Carbazol, 3,6-Dibrom-9,9,10-Trimethyl-9,10-Dihydroacridin, 3, 6-Dibrom-10-Methyl-9,10-Dihydroacridin, 2,7-Dibrom-9,9,10-Trimethyl-9, 9,10-Dihydroacridin, 2,7-Dibrom-10-Methyl-9,10-Dihydroacridin, oder um 2, 7-Dibrom-9-Methyl-9H-Carbazol handeln. Als erstes Ausgangsmonomer kann 4,4‘-Dibrom-1,1‘-biphenyl, 3,3‘-Dibrom-1,1‘-biphenyl, 1,4-Dibromobenzen, 4,4'-Dibrom-1,1'-biphenyl, 3,3'-Dibrom-1,1'-biphenyl, 4,4"-Dibrom-1,1';4',1"-terphenyl, 4,4"-Dibromo-1,1';3',1"-terphenyl, 3,3"-Dibrom-1,1';3',1"-terphenyl, 3,3"-Dibrom-2',4',5',6'-tetrafluoro-1,1';3',1"-terphenyl, 3,7-Dibromdibenzo[b,d]furan, 3,6-Dibrom-1a,9a,dihydro-9H-xanthen, 2,7-Dibrom-4a,9a-dihydro-9H-xanthen, 3,7-Dibromdibenzo[b,d]thiophen, 2,7-Dibrom-9-methyl-9H-carbazol, ein Monomer mit einer der nachstehenden Strukturen , oder 3,6-Dibrom-4a,9a-dihydro-9H-thioxanthen, 5 2,7-Dibrom-4a,9a,dihydro-9. H-thioxanthene, 3,6-dibromo-9,9,10-trimethyl-4a,9,9a,10-tetrahydroacridine, a monomer having one of the following structures, or 10 2,7-Dibromo-9-(4-(3-bromopropyl)phenyl)-9-(trifluoromethyl)-4a-9a-dihydro-9H-xanthene, 2,7-dibromo-9,9,10-trimethyl-4a-9,9a-10-tetrahydroacridine, 2,7-Dibromo-10,methyl-4a,9,9a,10-tetrahydroacridine, 3,6-dibromophenanthrene, 2,7-dibromomphenanthrene, 2,7-dibromo-9-(4-(3-bromopropyl)phenyl)-9-(trifluoromethyl)-4a,9a-dihydro-9Hthi 15 oxanthene, 3,6-Dihydro-10-methyl-4a-9-9a-10-tetrahydroacridine, 2,7-Dibromo-9,9-diphenyl-9H-fluorene, 2,7-Dibromo-9,9-bis(perfluorophenyl)-9H-fluorene, or 2,7-Dibromo-9-methyl-9H-carbazole may be used, or a monomer having one of the following structures may be used: The use of more highly fluorinated components creates more opportunities to introduce additional functional groups, which positively influences both the electrochemical and mechanical properties. Furthermore, this can positively influence the solubility behavior for the subsequent production of a membrane. The second starting monomer is particularly preferably 1,2,4,5-tetrafluorobenzene, and the first starting monomer is 2,7-dibromo-9,9-dialkyl-9H-fluorene. The second starting monomer is preferably an angled phenylene. The second starting monomer can contain a fluoroaromatic or consist of a fluoroaromatic. As a second starting monomer, 2,2',2'',3,3',3'',5,5',5'',6,6',6''-dodecafluoro-1,1':4',1''-terphenyl, 2,2'',3,3'',5,5'',6,6''-octafluoro-1,1':4',1''-terphenyl, 1,3,4,5,6,8,9,10-octafluorophenanthrene, 2,2'',3,3'',5,5'',6,6''-octafluoro-1,1':3',1''-terphenyl 2,2',2'',3,3'',4',5,5',5'',6,6',6‘‘-Dodecafluor-1,1‘:3‘,1‘‘-terphenyl, 2,2',2"3,3',3",5,5',5",6,6',6"-Dodecafluor-1,1';4',1"-terphenyl, 2,2',2",3,3',3",4,4",5',6,6',6"-Dodecafluor-1,1';4',1"-terphenyl, 1,2,4,5,6,8,9,10-Octafluoranthracen, 2,2",3,3",5,5",6,6"-Octafluor-1,1';3',1"-terphenyl, 2,2',2",3,3",4',5,5',5",6,6',6"-Dodecafluor-1,1';3',1"-terphenyl, 2,2',2",2"',3,3"',4',4",5,5',5",5"',6,6',6",6"'-Hexadecafluor-1,1';3',1";3",1"'-quater phenyl, 1,2,4,5,6,8-Hexafluornaphthalen, 1,2,4,5,7,8-Hexafluornaphthalen, 1,2,3,4,6,7-Hexafluornaphthalen, 2,2",3,3",4,4",6,6"-Octafluor-1,1';4',1"-terphenyl, 1,2,3,4,5,6,7,8-Octafluoranthracen, 1,2,3,4,6,7,9,10-Octafluoranthracen, 1,2,4,5,7,8-Hexafluoranthracen, 2,2",3,3",5,5",6,6"-Octafluor-1,1';4',1"-terphenyl, 1,3,4,5,6,8,9,10-Octafluorphenanthren, 1,2,4,5,7,8,9,10-Octafluorphenanthren, 1,3,4,5,6,8-Hexafluorphenanthren, 1,2,4,5,7,8,9,10-Octafluoranthrancen, 2,3,4,5,6,7,9,10-Octafluorphenanthren, 2,3,6,7-Tetrafluorphenanthren, 1,2,4,5,6,8-Hexafluoranthracen, oder 2,2',2",2"',3,3'',4,4',4",4"',5',5",6,6',6",6"'-hexadecafluoro-1,1';3',1";3",1"'-quaterphenyl can be used. The second starting monomer can be a fluorinated phenylene compound. These are preferably partially fluorinated phenylene compounds, which in particular can have at least three aromatic rings linked to one another. The aromatic rings are preferably not, partially, or fully fluorinated. The second starting monomer can preferably be 2,2',2'',3,3',3'',5,5',5'',6,6',6''-dodecafluoro-1,1':4',1''-terphenyl, 2,2'',3,3'',5,5'',6,6''-octafluoro-1,1':4',1''-terphenyl, 1,3,4,5,8,9,10-octafluorophenanthrene, 2,2'',3,3'',5,5'',6,6''-octafluoro-1,1':3',1''-terphenyl, or 2,2',2'',3,3'',4',5,5',5'',6,6',6''-dodecafluoro-1,1':3',1''-terphenyl. By using angled phenylenes, etc., the solubility behavior during polymerization can be positively influenced to achieve higher molecular weights. This also enables the processability of the polymers into a membrane. Furthermore, the use of specific side chains can have positive effects on the mechanical properties. The number of possible sites for introducing functional groups can be increased. The higher number of functional groups can positively influence the electrochemical properties required in the application. In addition, the second starting monomer can be 2,2',3,3',5,5',6,6' - octafluoro - 1,1' - biphenyl, and the first starting monomer can be 2,7-dibromo-9,9-dihexyl-9H-fluorene. The polymerization preferably takes place as an arylation polymerization.in particular as a palladium-catalyzed arylation polymerization. In a further embodiment, the polymerization can take place in a microwave reactor and / or under the influence of microwave radiation. This increases the reaction rate. The process can further comprise one or more modifications of the polymer formed. The modification can take place after polymerization on the polymer formed. In principle, it is also possible for one or more starting monomers to be modified beforehand, so that a modified polymer is formed directly. The modification can be a nucleophilic substitution of at least one, in particular of several, preferably of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 fluorine atoms of a perfluoroaromatic compound which is contained in the polymer main chain or is coupled to it.by a functional group. Nucleophilic substitution can occur to form a polymer as described above. Examples of nucleophiles for reaction with the fluorine atoms of perfluoroaromatic compounds are shown in the figure below:

[0004] Further preferred examples of nucleophiles for reaction with the fluorine atoms of perfluoroaromatic compounds are: - Pyridine-4-thiol - Pyridine-3-thiol - Pyridine-2-thiol - Pyrazin-2-thiol - Pyrimidine-2-thiol - 1-(4-mercaptophenyl)ethan-1-one - 4-mercaptophenylsulfonic acid - - Piperidine-4-thiol - 2,2,2-Trifluoro-1-(4-mercaptophenyl)ethan-1one - Alkylthiols with C=1-20 - 4-Bromophenylthiol - 4-Chlorophenylthiol - 4-Iodophenylthiol - Thiophenol - 4-Fluorothiophenol - Pentafluorothiophenol - 3-(Dimethylamino)propane-1-thiol The modification can also comprise a thiol click reaction on a perfluoroaromatic compound. The perfluoroaromatic compound can be or comprise a perfluorophenyl and / or a perfluorobiphenyl unit and / or a perfluoroterphenyl unit and / or a perfluoroquaterphenyl unit. The modification can comprise an electrophilic aromatic substitution with an aromatic ring, in particular on a hydrogen atom of an aromatic ring. In particular, a nitration and / or a sulfonation and / or a Friedel-Crafts acylation can take place. Halogenation with bromine, iodine, or chlorine is also possible. An example of the electrophilic sulfonation of a fluorene polymer is shown in the following reaction scheme.The modification can also involve a reaction of the polymer with NaSH and a thiophenol. The mixing ratio between NaSH and the thiophenol can be continuously varied so that the nucleophilic substitution of the fluorine atoms occurs either completely or partially. The order of addition of the two S compounds (NaSH, thiophenol) can also be chosen arbitrarily or can occur simultaneously. The modification can take place using DBU, triethylamine or trimethylamine, or K2CO3. Furthermore, the modification can take place under the influence of solvents, in particular protic solvents such as water or alcohol, dipolar aprotic solvents such as DMSO, NMP, DMAc, DMF, NEP, and / or ether solvents such as THF, glyme, diglyme, diethyl ether, and / or mixtures of the aforementioned solvents. After modification, the polymer can be oxidized with an oxidizing agent. In this case,Sulfone bridges can form from the thio bridges, and sulfonic acid groups from the thiol groups. In this way, a high acid strength of the sulfonic acid groups can be achieved via the -M effect of the sulfone bridge. The lower the pKa value, the higher the proton conductivity of the SO3H groups. The more acidic the sulfonic acid groups are, the higher their hydrolytic stability. If necessary, the same modified polymer can also be subjected to electrophilic aromatic substitution, for example, nitration or Friedel-Crafts acylation and / or halogenation. The modification can also comprise covalent crosslinking of polymer chains with one another, in particular via a dithiol and / or a dithiophenol. According to a further embodiment, the modification can comprise sulfonation. ClSO3H or oleum can be used as the sulfonating reagent. ClSO3H can be dissolved in CHCl3. To carry out the sulfonation,The polymer may in particular be dissolved in CHCl3. In particular, the modification may comprise one or more steps. The modification may comprise several of the previously described modifications in succession. In principle, any combination of the previously described modifications is conceivable. The process according to the invention may further comprise blending the polymer with another polymer to form a blended polymer or polymer blend. In other words, the polymer may be mixed with at least one other polymer. For further details of the invention, reference is made to the dependent claims and to the following description of several exemplary embodiments with reference to the figures. The polymers or processes for producing polymers shown in the exemplary embodiments according to the present invention are advantageous embodiments of polymers according to the invention or of processes for producingof polymers. The reaction parameters mentioned in the various reaction schemes (for example, temperature, auxiliaries, or the like) are preferred embodiments of the processes according to the invention. The figures show: Figure 1 shows a reaction scheme for the preparation of a polyphenylene by direct arylation with a palladium catalyst (Exemplary Example 1); Figure 2 shows a reaction scheme for the preparation of a polyfluorene by direct arylation with a palladium catalyst; Figure 3 shows a first part of a reaction scheme for the modification of polyphenylene with NaSH and a thiophenol (Exemplary Example 2); Figure 4 shows a second part of the reaction scheme of polyphenylene with NaSH and thiophenol; Figure 5 shows a reaction scheme for the modification of a fluorene polymer by Friedel-Crafts acylation and further subsequent reactions (Exemplary Example 3); Figure 6 shows the modification of a sulfonated polyfluorene polymer in the form of a covalent crosslinking(Embodiment 4); Figure 7 shows a reaction scheme for the preparation of a polymer according to the invention (Embodiment 5); Figure 8 shows a 1H-NMR spectrum of the polymer from Figure 7; Figure 9 shows a 19F-NMR spectrum of the polymer P12; Figure 10 shows reaction schemes for the preparation of polymers according to the invention (Embodiment 6); Figure 11 shows the NMR spectra of the copolymers from Figure 10; Figure 12 shows a 19F-NMR spectrum of the copolymer from Figure 10; Figure 13 shows a reaction scheme for the preparation of a polymer according to the invention (Embodiment 7); Figure 14 shows a 1H-NMR spectrum of the polymer obtained according to the reaction scheme from Figure 13 after complete thiolation with thiophenol; Figure 15 shows a reaction scheme for the nucleophilic substitution of fluorine by mercaptopropanesulfonic acid in a fluorene polymer (Exemplary Example 8); Figure 16 shows a 1H-NMR spectrum of the polymer from Figure 15; Figure 17 shows a 19F-NMR spectrum of the polymer from Figure 15; Figure 18 shows a reaction scheme for the modificationof a polymer according to the invention (Exemplary Embodiment 9); Figure 19 shows a further reaction scheme for the modification of a polymer according to the invention; Figure 20 shows a 1H NMR spectrum of a sulfonated polyfluorene; Figure 21 shows a reaction scheme for the covalent crosslinking of a polymer according to the invention (Exemplary Embodiment 10); and Figure 22 shows a reaction scheme for the preparation of a further polymer according to the invention (Exemplary Embodiment 11); Figure 23 shows a reaction scheme for the preparation of a further polymer according to the invention (Exemplary Embodiment 12); Figure 24 shows a reaction scheme for the preparation of a further polymer according to the invention (Exemplary Embodiment 13); Figure 25 shows a reaction scheme for the preparation of a further polymer according to the invention (Exemplary Embodiment 14); Figure 26 shows a reaction scheme for the preparation of a further polymer according to the invention (Exemplary Embodiment 15); Figure 27 shows a reaction scheme for the preparation of another polymer according to the invention(Embodiment 16); Figure 28 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 17); Figure 29 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 18); Figure 30 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 19); Figure 31 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 20); Figure 32 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 21); Figure 33 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 22); Figure 34 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 23); Figure 35 shows a reaction scheme for the preparation of a further polymer according to the invention (Embodiment 24); Figure 36 shows a reaction scheme for the preparation of aanother polymer according to the invention (Exemplary Embodiment 25); Figure 37 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 26); Figure 38 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 27); Figure 39 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 28); Figure 40 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 29); Figure 41 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 30); Figure 42 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 31); Figure 43 shows a reaction scheme for producing another polymer according to the invention (Exemplary Embodiment 32); Figure 44 shows a reaction scheme for modifying an inventive polymer (Exemplary Embodiment 33); Figure 45 anotherReaction scheme for modifying a polymer according to the invention (Exemplary Embodiment 34); Figure 46 shows an alternative reaction scheme for modifying the polymer according to the invention from Figure 45; Figure 47 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 35); Figure 48 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 36); Figure 49 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 37); Figure 50 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 38); Figure 51 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 39); and Figure 52 shows a reaction scheme for producing a further polymer according to the invention (Exemplary Embodiment 40). Where R1, R2 and R3 appear in the reaction schemes, these are possible compounds for R.R1, R2 and R3 are examples of the side chains designated by the letter R. R1 can be hexyl (C6H 13 ), R2 can be octyl (C8H 17 ), R3 can be dodecyl (C 12 H 25). In principle, other alkyl chains are also conceivable here, as already described above. Embodiment 1 Figure 1 shows the reaction in the process according to the invention for producing a polymer. Two starting monomers are provided, each containing dihaloaromatics. One starting monomer is 4,4'-bromobiphenyl and another starting monomer is 3,3'-bromobiphenyl. A further starting monomer is 1,2,4,5-tetrafluorobenzene. A polymer according to the present invention is produced by direct arylation polymerization. It can be seen that due to the use of different variants of the monomers, in this case the two variants of the dihaloaromatics, the polymer main chain does not run in a straight line but has kinks, which improves the solubility of the resulting polymer in solvents.A further embodiment of a process according to the invention is shown in Figure 2. Tetrafluorobenzene and fluorene halogenated at various points are used as starting monomers. By means of an arylation polymerization, specifically a palladium-catalyzed arylation polymerization, a block copolymer according to the present invention is produced, which also has kinks in the polymer main chain that lead to improved solubility in solvents. Embodiment 2 Figure 3 shows the reaction of the fluorine atoms of a polyphenylene with NaSH and a thiophenol (in Figures 3 and 4, R1 stands for SO2 and R2 for SO3H). The mixing ratio between NaSH and the thiophenol can be varied practically continuously, so that the nucleophilic substitution of the fluorine atoms occurs either completely or partially.DBU, triethylamine, trimethylamine, or K2CO3 can preferably be used as bases for the deprotonation of the sulfur compounds. The solvents used in the modifications of a polymer according to the invention described above are protic solvents such as water and alcohols, dipolar aprotic solvents such as DMSO, NMP, DMAc, DMF, NEP, and the like, or ether solvents such as THF, glyme, diglyme, diethyl ether, and / or mixtures of the solvents mentioned. After the polymer has been reacted, it can be oxidized with an oxidizing agent to convert the thiol bridges into sulfonic bridges, and the thiol groups into sulfonic acid groups. This reaction is shown in Figure 3 below. The -M effect of the sulfonic bridge results in a high acid strength of the sulfonic acid groups, with the proton conductivity of the SO3H groups increasing with the lower pKa value. Using the ACD software, a pK.AThe cationic value of the sulfonic acid groups attached to an electron-deficient aromatic compound can be calculated with values ​​between -1 and -2. It has been shown that the more acidic the sulfonic acid groups are, the higher the hydrolysis resistance of the sulfonic acid groups. In the example shown in Figures 3 and 4, 4-fluorothiophenol was used. The fluorine atom of the 4-fluorothiol group can be nucleophilically substituted after oxidation of the thiol bridge to a sulfone bridge, as shown in Figure 3 by tetramethylguanidine. The guanidinium group can be converted to the anion exchange group guanidinium by N-alkylation. This is shown in Figure 4. If required, the polymer can then be subjected to an electrophilic aromatic substitution, for example a nitration or a Friedel-Crafts acylation and / or a halogenation.Embodiment 3 Figure 5 shows various chemical modifications of a partially fluorinated polyfluorene according to the invention with pentafluorophenylcarbonyl groups and / or with haloalkyl side chains. For example, a side chain containing a fluorinated aromatic is introduced by means of Friedel-Craft acylation. This side chain is then successively further functionalized in subsequent steps. Embodiment 4 Figure 6 shows an exemplary modification of an aromatic polymer according to the present invention. In this case, the partially fluorinated polymers are covalently crosslinked with one another using a dithiol or dithiophenol in a manner known per se. In the present case, a 4,4'-[1,1'-biphenyl]-4,4'-dithiol is used for this purpose. Embodiment 5 Direct arylation polymerizations of 2,7-dibromo-9,9-dialkyl-9H-fluorenes with 1,2,4,5-tetrafluorobenzene.Various 2,7-dibromo-9,9-dialkyl-9H-fluorenes were reacted with 1,2,4,5-tetrafluorobenzene by direct arylation polymerization according to the Ozawa method. The experimental procedure is described below: 3.0 mmol of the alkyl side-chain-substituted fluorene, 3.0 mmol of tetrafluorobenzene, 9.0 mmol of anhydrous potassium carbonate, 2.5 mol% of palladium acetate, and 5 mol% of the phosphine ligand P-tBu2Me-HBF4 were dissolved in 15 mL of toluene under inert gas. 6 mmol of acetic acid was added to the resulting solution, and the mixture was heated to reflux for 72 h. After the reaction mixture cooled to room temperature, it was diluted with toluene, and any solids were removed by filtration. The organic phase was then concentrated and precipitated in methanol, yielding a grey to colourless solid.If the reaction is carried out in a microwave, the above-mentioned initial weights are placed in a glove box in a microwave reaction vessel. The reaction vessel is then sealed, and the mixture is heated to reflux in the microwave at 140 °C for 9 h. After the reaction mixture had cooled to room temperature, it was diluted with toluene, and any solids present were removed by filtration. The organic phase was then concentrated and precipitated in methanol, yielding a gray to colorless solid. The polymerization scheme is shown in Figure 7. The following tables show the experimental conditions for the arylation polymerization of the various dibromofluorenes with tetrafluorobenzene using conventional heating in glass reactors (Table 1) and in a CEM microwave reactor (Discover model) (Table 2), as well as the average molecular masses M obtained in each case.n and the polydispersity index PDI are listed. R1, R2, and R3 are examples of the side chains designated by the letter R in Figure 7. R1 here stands for hexyl (C6H 13 ), R2 stands for octyl (C8H 17 ). R3 stands for dodecyl (C 12 H 25 ). In principle, other side chain lengths are also conceivable here. Table 1: Experimental conditions for the arylation polymerization of the various dibromofluorenes from Example 5 with tetrafluorobenzene using conventional heating in glass reactors. Table 2: Test conditions for the arylation polymerization of the various dibromofluorenes from the first embodiment in a microwave reaction device from CEM (Model Discover) PDI stands for polydispersity, which is a measure of the molecular weight distribution. Tg stands for the glass transition temperature. Both tables demonstrate the significant advantage of conducting the polymerization reaction in the microwave reactor. An acceleration of the arylation polymerization by a factor of 8 is observed in the microwave reactor, and this at comparable M n- and PDI values. In addition, when the polymerization is carried out in the microwave, less catalyst is required, the yield is higher, and fewer by-products are formed. In addition to the influence of microwave-assisted synthesis on the number-average molecular weight, polydispersity, and glass transition temperature, the thermal stability of the produced materials was also investigated. It was found that the length of the side chain has a positive influence on the thermal stability of the polymers, as the longer chains can interact better with each other. Two decomposition stages were observed for each of these materials, the first stage being due to the cleavage of the alkylic side chains. At even higher temperatures, the degradation of the polymer main chain begins.The determined decomposition temperatures and masses can be taken from the following Table 3 depending on the side chains: Table 3: Comparison of the thermal properties depending on the side chains using TGA measurements. Figure 8 shows the 1H NMR spectrum of the polyfluorene with an aliphatic dodecyl side chain. The proton spectra of the other two polyfluorene polymers listed differ only depending on the aliphatic side chain, with minimal changes in the chemical shift / number of protons. Figure 9 shows an exemplary 19F NMR spectrum. However, with regard to the change in the side chain, no change in the chemical shift is observed in the respective NMR spectra, since the tetrafluorobenzene unit remains unchanged. It was also found that the NMR spectra of the conventionally produced materials are identical to those produced in the microwave. Example 6 Comparison of the direct arylation polymerizations of 2,7-dibromo-9,9-dihexyl-9H-fluorene with 1,2,4,5-tetrafluorobenzene and with 2,2',3,3',5,5',6,6'-octafluoro-1,1'-biphenyl.3.0 mmol of the alkyl side-chain-substituted fluorene, 3.0 mmol of tetrafluorobenzene or 3 mmol of octafluorobiphenyl, 9.0 mmol of anhydrous potassium carbonate, 2.5 mol% palladium acetate, and 5 mol% of the phosphine ligand P-tBu2Me-HBF4 were dissolved in 15 mL of toluene under inert gas. 6 mmol of acetic acid was added to the resulting solution, and the mixture was heated to reflux for 72 h. After the reaction mixture had cooled to room temperature, it was diluted with toluene, and any solids present were removed by filtration. The organic phase was then concentrated and precipitated in methanol, yielding a gray to colorless solid. If the reaction is carried out in a microwave, the above-mentioned initial weights are transferred into a microwave reaction vessel in a glove box. The reaction vessel is then closed and the mixture is heated to reflux in a microwave oven at 140 °C for 9 h.After cooling the reaction mixture to room temperature, it was diluted with toluene, and any solids present were removed by filtration. The organic phase was then concentrated and precipitated in methanol, yielding a gray to colorless solid. It was determined that when 2,2',3,3',5,5',6,6'-octafluoro-1,1'-biphenyl was used as the partially fluorinated aromatic compound (starting monomer) instead of 1,2,4,5-tetrafluorobenzene for the direct arylation reaction, the achievable degree of polymerization almost doubled (Table 4). This is likely due to the higher CH acidity of octafluorobiphenyl compared to tetrafluorobenzene. Table 4: Comparison of the degrees of polymerization when using octafluorobiphenyl compared to tetrafluorobenzene. It can also be noted that both reactions could be achieved both conventionally and by microwave-assisted synthesis. By using a microwave, the reaction time can be reduced by a factor of 8 at 140 °C (microwave) instead of 110 °C (conventional), while materials of comparable molecular mass can be obtained. In addition to the degree of polymerization, the materials were investigated by NMR spectroscopy, and their thermal properties were determined using DSC and TGA. A glass transition temperature Tg of 214 °C was determined for the material with the tetrafluorobenzene unit, and a glass transition temperature of the same order of magnitude was determined for the material with the octafluorobiphenyl unit. The two decomposition points for the polymer of tetrafluorobenzene and 2,7-dibromo-9,9-dihexylfluorene can be found in Table 3 above.The polymer of octafluorobiphenyl and 2,7-dibromo-9,9-dihexylfluorene also decomposes in two stages, beginning at 364 °C and 435 °C. The proton NMR spectra of the two materials are identical (see Figure 12), as only the fluorine-containing unit changes, which can only be detected by 19F NMR spectroscopy. Example 7 Nucleophilic substitution of F of the two fluorene polymers (polymer 1: from 1,2,4,5-tetrafluorobenzene; polymer 2: from octafluorobiphenyl) by thiophenol All thiolation reactions were carried out in a water- and oxygen-free atmosphere. For this purpose, the reactants, bases, and solvents listed in Table 5 below were mixed in the specified amounts in such an atmosphere and stirred at 120 °C for 72 h. Anhydrous potassium carbonate was used as the base throughout, and DMF was used as the solvent. Table 5: Reaction conditions for thiolation with thiophenol. Figure 13 shows the general reaction equation for the thiolation reaction described above. The prepared substances were analyzed by NMR spectroscopy. An exemplary 1H NMR spectrum is shown in Figure 14 below. When a polymer containing an octafluorobiphenyl unit is substituted with thiophenol, almost identical chemical shifts and substitution patterns are observed in the 1H NMR spectrum. Complete substitution can also be demonstrated in the 19F NMR spectrum, as no fluorine signals are detected, as all fluorine atoms are replaced by a thioether, ultimately yielding a fluorine-free material. In addition to the degree of substitution determined by NMR, this was also determined by elemental analysis. Complete substitution of the four fluorine atoms was demonstrated for the tetrafluorobenzene-containing polymers.This is shown as an example for the reaction of P6 with thiophenol in Table 6 below. Table 6: Results of the elemental analysis of the nucleophilic substitution of P6 with thiophenol. The degree of substitution of the polymer P6_8F_TP was also investigated using elemental analysis. It was determined that complete substitution was not possible due to steric hindrance. A degree of substitution of 75% (6 of 8 fluorine atoms) was determined. In addition to the structural properties, the thermal properties of the materials were also determined. The thermal stability of selected materials was determined using TGA (see Table 7), as was the glass transition temperature (Tg) of the polymers (see Table 8). Table 7: Results of the TGA measurements of the polymers nucleophilically substituted with thiophenol. The additional step in the P6_TP polymer between 480.42 °C and 537.81 °C is likely a measurement artifact. Overall, analogous to the base polymers, it can be stated that the length of the alkyl side chain influences the thermal stability of the materials. The longer the alkyl side chain, the greater the interaction between them, and consequently, the thermal stability of the polymers increases. There is currently no data available on the thermal stability of the substituted copolymer of octafluorobiphenyl and 2,7-dibromo-9,9-dihexylfluorene; these should behave analogously to the values ​​determined in Application Example 1, regardless of the substitution of the aromatic fluorine atoms with thiophenol. These should also fit into the series shown above. Table 8: Results of the DSC measurements of the polymers nucleophilically substituted with thiophenol. 1 Example 8 Nucleophilic substitution of F by mercaptopropanesulfonic acid in 4F- and 15F-fluorene polymers. All thiolation reactions were carried out in a water- and oxygen-free atmosphere. For this purpose, the reactants, bases, and solvents listed in Table 9 below were mixed in the specified amounts in such an atmosphere and stirred for 72 h at 120 °C. Anhydrous potassium carbonate was used as the base throughout, and DMF was used as the solvent. Table 9: Reaction conditions for the thiolation with the sodium salt of 25 Mercaptopropanesulfonic acid (MPS).

[0005] Figure 15 shows the general reaction equation for the thiolation reaction described above. The reaction shown can be carried out both conventionally and in a microwave. When carried out in a microwave, the reaction time can be reduced from 72 hours at 120 °C to 4.5 hours at 160 °C. Identical materials are produced, so that, surprisingly, the reaction time is significantly accelerated by a factor of 16. Figures 16 and 17 show exemplary NMR spectra, from which the degree of substitution could be determined to be approximately 50%. The statement regarding the degree of substitution made using NMR spectroscopy can be substantiated by elemental analysis by examining the theoretical and experimentally determined sulfur content of the sample. The data determined for the polymer P6_MPS can be found in Table 10 below.Table 10: Results of elemental analysis of the reaction product of the substitution of P6 with mercaptopropanesulfonic acid. With regard to the copolymer containing an octafluorobiphenyl unit, a degree of substitution of 50% of the fluorine atoms present can also be determined by elemental analysis, which corresponds to four sulfonic acid groups in the side chain in the target material P6_F8_MPS (Table 11). Here, too, the degree of substitution was determined based on the sulfur content. Table 11: Results of the elemental analysis of the reaction product of the substitution of P6_F8 with mercaptopropanesulfonic acid. In addition to the degree of substitution, the glass transition temperatures of the materials shown were determined. These are 127 °C for the P6_MPS polymer and 171 °C for the P6_F8_MPS polymer. Stable membranes could not be produced from pure materials using the sulfonic acid-functionalized materials shown here. For this purpose, the materials were blended with a polybase, which is described in more detail in Example 10. Example 9 Electrophilic Sulfonation with Oleum or Chlorosulfonic Acid Surprisingly, it was shown that both the main chain of the microwave-assisted polymers and the thiophenol side chain introduced in a previous step can be sulfonated. General reaction equations for both reactions are shown in Figures 18 and 19. To sulfonate the respective raw materials, the polymer is either dissolved in chloroform or introduced undissolved.The sulfonation reagent (oleum / chlorosulfonic acid) is carefully added dropwise to the polymer at 0 °C. After the sulfonation reagent has been completely added, the mixture is stirred at room temperature for at least 5 h. The polymer contained in the solution is precipitated in an ice bath and separated. The resulting solid is washed with water until neutral. If chlorosulfonic acid is used as the sulfonation reagent, the polymer is stirred with water to hydrolyze any sulfonic acid chloride groups formed to form free sulfonic acid groups. The sulfonation reactions carried out are listed in Table 12 below: Table 12: Overview of the sulfonation reactions carried out. The sulfonation S1 of the main chain of polymer P12 was successful, with approximately one sulfonic acid group being introduced per repeating unit. This was confirmed both by 1H NMR (degree of substitution approximately 95%) and by elemental analysis. The degree of substitution was also determined by acid-base titration. An IEC direct of 1.03 meq g -1 which, compared with the theoretical IEC of 1.32 meq g -1corresponds to a degree of substitution of at least 75%. The lower IEC with respect to NMR can be attributed to incomplete hydrolysis of sulfonyl chloride groups. In addition to sulfonation of the main chain, polymers with thiophenol side chains could surprisingly be sulfonated. This involves sulfonation of both the side chain and the main chain, resulting in a mixture of sulfonation positions. NMR spectroscopy is difficult to structurally elucidate the nature of this mixture in order to determine the exact degree of sulfonation of the respective positions. It can only provide information about which position is electrophilically aromatically substituted. This hypothesis was also verified by elemental analysis, which showed that successful sulfonation had taken place.It can also be assumed that the thioether bridges were at least partially oxidized to more stable sulfone bridges by the oxidative chlorosulfonic acid. Furthermore, the ion exchange capacity of the polymer was determined by titration. An IEC was used. direct of 2.00 meq g -1 Using the stronger sulfonating agent oleum, an IEC direct of 2.48 meq g -1A membrane was successfully produced from the main-chain sulfonated polyfluorene S1 in a DMSO solution. For this purpose, the polymer was dissolved in DMSO, and the solution was applied to a glass plate using a doctor blade in a defined layer thickness, and the solvent was evaporated to form a membrane. A membrane with a thickness of 18 µm was obtained, which, in the impedance measurement in a sandwich of two Nafion XL membranes and dilute sulfuric acid, exhibited a conductivity of 37.31 + / - 2.25 mS cm. -1 (Compare Nafion XL 46.29 mS cm -1). Furthermore, a water absorption of 6.6% and a swelling of 3.5% were determined. Example of an embodiment 10 Acid-base blends of sulfonated fluorene polymers and OPBI Since some of the materials produced according to the invention do not have sufficient stability in water, they were blended with a polybase (OPBI). For this purpose, the sulfonated polymer was dissolved in a solvent (e.g. DMSO, DMAC, NMP) and then the existing acid groups were neutralized with a base (e.g. triethylamine, triethanolamine) and stirred. After neutralization, the polybase is added to the mixture and stirred until a homogeneous mixture is obtained. This mixture is applied to a substrate in a defined layer thickness using a doctor blade and then the solvent is evaporated so that a homogeneous membrane is obtained.The membranes listed in Table 13 below were prepared from the dihexylpolyfluorenes substituted with mercaptopropanesulfonic acid. The properties of the membranes can also be found in the table. M4 and its derivatives were prepared from poly-dihexylfluorene-co-tetrafluorobenzene substituted with mercaptopropanesulfonic acid, and M5 and its derivatives were prepared from poly-dihexylfluorene-co-octafluorobiphenyl substituted with mercaptopropanesulfonic acid. Table 13: Overview of the membrane properties of M4 from P6_MPS and M5 from P6_8F_MPS and their blends. Blend membranes were also prepared from the sulfonated thiphenol-substituted poly-dihexylfluorene-co-tetrafluorobenzene with OPBI using the above-described procedure. The results obtained are shown in Table 14 below. Table 14: Overview of the membrane properties of M6 from the P6_TP sulfonated in S5. It can be seen from Table 13 and Table 14 that, despite ionic crosslinking of the membranes listed therein, a mass loss still occurs during storage tests in solvents. This mass loss can be further reduced if, according to the invention, in those blends containing a sulfonated polymer that still has all or part of the F of the tetrafluorobenzene or octafluorobiphenyl unit, the sulfonated polymer is additionally covalently crosslinked by reaction with a dithiol or dithiophenol, as shown in Figure 6. Furthermore, in the blends of sulfonated polymer according to the invention and a polybenzimidazole (PBI), it is possible to covalently crosslink the PBI blend component by adding, for example, a diepoxide to the blend solution, which reacts covalently with the NH of the imidazole unit to form a ring-opening crosslink. This can be seen from Figure 21.Embodiment 11 Figure 22 shows an example of a reaction scheme for producing a further polymer according to the invention. The starting monomers used are alkyl-substituted 2,2'-dibromofluorene and dodecafluorotherphenyl. The letter R appearing in the reaction scheme can stand for an alkyl chain. R1, R2, and R3 are exemplary embodiments of R. The second starting monomer (dodecafluorotherphenyl) is shown in detail below in Figure 22. Embodiment 12 Figure 23 shows a further reaction scheme for producing a polymer according to the invention. The first starting monomer used is haloalkyl-substituted 2,2'-dibromofluorene. As in the reaction scheme in Figure 22, dodecafluorotherphenyl is used as the second starting monomer. The halogens can in principle be iodine, chlorine, and bromine.The two halogens at the end of the alkyl chain can be the same or different. Embodiment 13 Figure 24 shows a reaction scheme for the preparation of a further polymer according to the invention. In contrast to Figure 23, no dodecafluorotherphenyl is used as the second starting monomer, but rather an octafluorobiphenyl. Embodiment 14 Figure 25 shows a further reaction scheme for the preparation of a polymer according to the invention. In contrast to Figure 24, no octafluorobiphenyl is used as the second starting monomer, but rather a tetrafluorobenzene. Embodiment 15 Figure 26 shows a further reaction scheme for the preparation of a polymer according to the invention. The first starting monomer used is a phenyl- / phenylalkyl side chain-substituted 2,2'-dibromofluorene. M can take on values ​​from 0 to 20.Both a side-chain-substituted starting monomer and a phenylalkyl side-chain-substituted starting monomer can be used. Tetrafluorobenzene is used as the second starting monomer. Embodiment 16 The reaction scheme for producing a further polymer according to the invention, which is shown in Figure 27, differs from the reaction scheme in Figure 26 only in that octafluorobiphenyl is used as the second starting monomer instead of tetrafluorobenzene. Embodiment 17 Figure 28 then shows a further reaction scheme for producing a polymer according to the invention. This differs from the reaction schemes in Figures 26 and 27 in that dodecafluoroterphenyl is used as the second starting monomer. Embodiment 18 Figure 29 shows a further reaction scheme for producing a polymer according to the invention.The first starting monomer used is phenyl- / phenylalkyl side chain-substituted 2,2'-dibromofluorene, and the second starting monomer used is tetrafluorobenzene. Embodiment 19 The reaction scheme for producing a further polymer according to the invention, which is shown in Figure 30, differs from the reaction scheme shown in Figure 29 in that octafluorobiphenyl is used as the second starting monomer. Embodiment 20 Figure 31 shows a further reaction scheme for producing a polymer according to the invention. In contrast to Figures 29 and 30, dodecafluoroterphenyl is used as the second starting monomer. Embodiment 21 Figure 32 shows a further reaction for producing a polymer according to the present invention.Alkyl-substituted 2,2'-dibromofluorene is used as the first starting monomer, and 2,2'', 3,3'', 5,5'', 6,6''-octafluoro-1,1':4',1''-terphenyl is used as the second starting monomer. R can, as in some previous figures, stand for any alkyl chains. R1, R2, and R3 represent preferred embodiments for R. Embodiment 22 Figure 33 shows a further reaction scheme for the preparation of a further polymer according to the invention. This differs from the reaction scheme in Figure 32 in that phenyl- or phenylalkyl side-chain-substituted 2,2'-dibromofluorene is used as the first starting monomer. Embodiment 23 Figure 34 shows a further reaction scheme for the preparation of a polymer according to the invention. Unlike in Figure 33, pentafluorophenyl or pentafluorophenylalkyl side chain substituted 2,2'-dibromofluorene is used as the first starting monomer.Embodiment 24 Figure 35 shows a further reaction scheme for producing a polymer according to the invention. 2,2'-dibromofluorene substituted by alkyl side chains is used as the first starting monomer, and 1, 3, 4, 5, 6, 8, 10-octafluorophenantrine is used as the second starting monomer. Embodiment 25 Figure 36 shows a further reaction for producing a polymer according to the invention. Unlike Figure 35, 2,2'-dibromofluorene substituted by phenyl or phenylalkyl side chains is used as the first starting monomer. Embodiment 26 The reaction scheme for producing a polymer according to the invention, which is shown in Figure 37, differs from the reaction scheme of Figure 36 in that pentafluorophenyl / pentafluorophenylalkyl side chain-substituted 2,2'-dibromofluorene is used as the first starting monomer.Embodiment 27 Figure 38 shows a further reaction scheme for producing a polymer according to the invention. Alkyl-substituted 2,2'-dibromofluorene is used as the first starting monomer, and 2,2'', 3,3'', 5,5'', 6,6''-octafluoro-1,1':3',1''-terphenyl is used as the second starting polymer. As in some of the previous figures, R can stand for alkyl chains. The designations R1, R2, and R3 represent preferred alkyl chains. Embodiment 28 Figure 39 shows a further reaction scheme for producing another polymer according to the invention. Unlike in Figure 38, phenyl- or phenylalkyl side-chain-substituted 2,2'-dibromofluorene is used as the first starting monomer. The second starting monomer is identical to that in Figure 38.Embodiment 29 Figure 40 shows a further reaction scheme for producing a polymer according to the invention, which differs from the reaction schemes of Figures 38 and 39 only with regard to the first starting monomer in that pentafluorophenyl- or pentafluorophenylalkyl side-chain-substituted 2,2'-dibromofluorene is used as the first starting monomer. Embodiment 30 Figure 41 shows a reaction scheme for producing a further polymer according to the invention. The first starting monomer used is alkyl-substituted 2,2'-dibromofluorene, and the second starting monomer used is 2,2',2'',3,3'',4',5,5',5'',6,6',6''-octafluoro-1,1':3',1''-terphenyl. Embodiment 31 The reaction scheme for producing a polymer according to the invention, which is shown in Figure 42, differs from the reaction scheme of Figure 41 only with regard to the first starting monomer.Here, 2,2'-dibromofluorene substituted with phenyl or phenylalkyl side chains is used in Figure 42. Embodiment 32 The reaction scheme shown in Figure 43 for preparing a further polymer according to the invention differs from those in Figures 41 and 42 with regard to the first starting monomer. The first starting monomer used here is pentafluorophenyl or pentafluorophenylalkyl side chain-substituted 2,2'-dibromofluorene. Embodiment 33 Figure 44 shows the modification of a polymer according to the invention. Specifically, this is the polymer shown in Figure 25. The aliphatic side chains of the copolymer of dibromofluorene and 1,2,4,5-tetrafluorobenzene are thiolated in a first step. In a further step, the thiol groups are converted into sulfonic acid groups.The specific preparation is described below: 1 equivalent of a fluorene substituted with haloalkyl side chains is 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. The resulting polymer is then redissolved in dimethylacetamide, and the solution is cooled to 0 °C. 6 equivalents of MCPBA are then added portionwise over 10 minutes. The mixture is then further stirred at room temperature. Finally, the polymer is precipitated in 1 M sodium chloride solution, washed with water, and dried. Embodiment 34 Figure 45 shows a further modification of a polymer according to the invention.Specifically, it is a single phosphonation of the pentafluorophenyl residues on the copolymer as 1,2,4,5-tetrafluorophenyl and a 2,7-dibromofluorene modified with pentafluorophenyl groups or alkylpentafluorophenyl groups. The preparation proceeds as follows: 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 off, washed with water until neutral, and dried. Figure 46, in contrast, shows a multiple phosphonation of the pentafluorophenyl residues on the polymer. Embodiment 35 Figure 47 shows a further reaction for producing a polymer according to the invention.The first starting monomer used is 2,7-dibromo-9-methyl-9H-carbazole, and the second starting monomer used is 1,2,4,5-tetrafluorobenzene. Embodiment 36 Figure 48 shows a further reaction scheme for producing a polymer according to the invention. Unlike in Figure 47, 2,7-dibromo-9-methyl-9H-carbazole is used as the first starting monomer. Embodiment 37 Figure 49 shows a further reaction scheme for producing a polymer according to the invention. The starting monomers used are 3,6-dibromo-10-methyl-9,10,dihydroacridine and 1,2,4,5-tetrafluorobenzene. Embodiment 38 Figure 50 shows a further reaction scheme for producing a polymer according to the invention. The starting monomers used are 2,7-dibromo-9,9,10-trimethyl-9,10-dihydroacridine and 1,2,4,5-tetrafluorobenzene. Embodiment 39: Another reaction scheme for the preparation of a polymer according to the invention is shown in Figure 51.The starting monomers used are 2,7-dibromo-10-methyl-9,10-dihydroacridine and 1,2,4,5-tetrafluorobenzene. It is fundamentally conceivable that, in the reaction schemes shown in Figures 47 to 51, octafluorobiphenyl or dodecafluoroterphenyl could also be used as the second starting monomer. Embodiment 40: A further embodiment of a reaction scheme for producing a polymer according to the invention is shown in Figure 52. The starting monomers used are 2,7-dibromo-9-methyl-9H-carbazole and 2,2',3,3',5,5',6,6'-octafluoro-1,1'-biphenyl.

Claims

CLAIMS 1. Aromatic polymer, in particular ion exchange polymer, preferably anion exchange polymer or cation exchange polymer, which has at least one aromatic in its repeating unit, wherein the polymer main chain of the polymer contains no pure heteroatom bridges.

2. Polymer according to claim 1, characterized in that it has side chains, wherein the side chains contain or consist of alkyl groups, alkyl ether groups, aryl ether groups and / or haloalkyl groups.

3. Polymer according to claim 1 or 2, characterized in that the polymer contains perfluoroaromatic compounds, which are preferably contained in the polymer main chain or are coupled thereto, wherein at least one, in particular several, preferably two, three or four fluorine atoms of the perfluoroaromatic compound are each nucleophilically substituted by a functional group.Polymer according to claim 3, characterized in that the at least one fluorine atom of the perfluoroaromatic compound is / are substituted by an S-, N-, O-, C- and / or P-nucleophile.

5. Polymer according to claim 3 or claim 4, characterized in that the perfluoroaromatic compound is or comprises a perfluorophenyl and / or a perfluorobiphenyl unit and / or a perfluoroterphenyl unit and / or a perfluoroquaterphenyl unit.

6. Polymer according to one of the preceding claims, characterized in that it has acidic groups, in particular sulfonic acid groups and / or phosphonic acid groups.

7. Polymer according to claim 6, characterized in that the acidic groups are coupled to an aromatic, in particular to an electron-poor aromatic, preferably to an aromatic which contains a functional group, in particular a fluorine-free sulfone group.

8. Polymer according to one of the preceding claims, characterized in that at least one atom on the aromatic, in particular a hydrogen atom, is electrophilically substituted, in particular nitrated, sulfonated, halogenated, and / or substituted by Friedel-Crafts acylation.

9. Polymer according to one of the preceding claims, characterized in that the polymer is a polyfluorene, in particular a partially fluorinated polyfluorene, and / or a polyphenylene, in particular a partially fluorinated polyphenylene. 10.Polymer according to one of the preceding claims, characterized in that the polymer is a copolymer, in particular a block copolymer, which has at least two different polymer blocks, wherein one polymer block consists at least predominantly of a polyphenylene and another polymer block consists at least substantially of a polyfluorene.

11. Polymer according to one of the preceding claims, characterized in that the polymer chains are covalently cross-linked with one another, in particular. in particular via a dithiol and / or a dithiophenol, are covalently crosslinked with one another.

12. Polymer according to one of the preceding claims, characterized in that it is produced by means of an arylation polymerization, in particular by means of palladium-catalyzed arylation polymerization.

13. Polymer according to one of the preceding claims, characterized in that it is polymerized from a fluoroaromatic and a dihaloaromatic.

14. Polymer according to one of the preceding claims, characterized in that the polymer is polymerized in a microwave reactor.

15. Membrane, in particular ion exchange membrane, preferably cation exchange membrane or anion exchange membrane, containing or consisting of a polymer according to one of the preceding claims. 16.Use of a membrane according to claim 15 in an electrochemical system, in particular in a fuel cell or a battery, or in an electrochemical process, in particular in an electrolysis process or in an electrosynthesis process.

17. A method for producing a polymer, in particular a polymer according to any one of claims 1 to 14, comprising the following steps: - providing a first starting monomer; - providing a second starting monomer. wherein the starting monomers comprise aromatics provided with functional groups for polymerization, - carrying out a polymerization to form a polymer, characterized in that the polymer has no heteroatom bridges in the polymer main chain.

18. The process according to claim 17, characterized in that the functional groups of the first starting monomer are arranged or coupled at different positions on the aromatic than the functional groups of the second starting monomer.

19. The process according to claim 17 or 18, characterized in that the second starting monomer contains a fluoroaromatic or consists of a fluoroaromatic.

20. The process according to any one of claims 17 to 19, characterized in that the first starting monomer contains a dihaloaromatic or consists of a dihaloaromatic. 21.Process according to one of claims 17 to 20, characterized in that the polymerization takes place as an arylation polymerization, in particular as a palladium-catalyzed arylation polymerization.

22. Process according to one of claims 17 to 21, characterized in that the polymerization takes place in a microwave reactor and / or under the influence of microwave radiation.

23. The process according to any one of claims 17 to 22, characterized in that it further comprises the modification of the polymer formed, wherein the modification of the polymer preferably takes place under the influence of microwaves and / or in a microwave reactor.

24. The process according to claim 23, characterized in that, during the modification, a nucleophilic substitution of at least one, in particular of several, preferably of two, three, or four fluorine atoms of a perfluoroaromatic compound, which is contained in the polymer main chain or coupled thereto, by a respective functional group takes place.

25. The process according to claim 24, characterized in that the perfluoroaromatic compound is or comprises a perfluorophenyl and / or a perfluorobiphenyl unit and / or a perfluoroterphenyl unit and / or a perfluoroquaterphenyl unit. 26.Process according to one of claims 23 to 25, characterized in that the modification comprises an electrophilic aromatic substitution with an aromatic, in particular on a hydrogen atom of an aromatic, wherein in particular a nitration and / or a sulfonation and / or a Friedel-Crafts acylation and / or a halogenation takes place.

27. Process according to one of claims 23 to 26, characterized in that the modification comprises a covalent crosslinking of polymer chains with one another, in particular via a dithiol and / or a dithiophenol.

28. Process according to one of claims 23 to 27, characterized in that the modification comprises a sulfonation reaction, wherein. especially ClSO3H, preferably in CHCl 3, and / or oleum can be used as a sulfonating reagent.

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