Substance, membrane, use of a membrane, and method for producing a substance

Abstract

The present invention relates: to a substance, in particular functionalised oligomer or polymer, wherein the substance contains oligomeric or polymeric chains to which perfluoroaromatic compounds are coupled or which contain perfluoroaromatic compounds; and to a membrane, in particular a blended membrane; and to a method for producing a substance, comprising the following steps: providing a starting substance, which contains oligomeric or polymeric chains to which perfluoroaromatic compounds having a plurality of fluorine atoms are coupled or which contain perfluoroaromatic compounds having a plurality of fluorine atoms; nucelophilic substitution of at least two, in particular of precisely two, three, four or five fluorine atoms of the perfluoroaromatic compound by one functional group in each case.

Description

[0001] DESCRIPTION

[0002] Fabric, membrane, use of a membrane and method for producing a fabric

[0003] The present invention relates to a substance, in particular a functionalized oligomer or polymer, wherein the substance contains oligomers or polymer chains to which perfluoroaromatic compounds are coupled or which contain perfluoroaromatic compounds. Furthermore, the invention relates to a membrane containing such a substance and to the use of a membrane. Furthermore, the invention relates to a process for producing such a substance.

[0004] 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 surrounding medium, depending on their application. Furthermore, such membranes are frequently exposed to mechanical stress. In electrochemical applications, a certain degree of conductivity combined with a low degree of swelling, i.e., low volume expansion, is also required.

[0005] Oligomers and polymers from which such membranes are made can contain perfluoroaromatic compounds. These can be coupled to oligomers or polymeric chains or be part of the chain backbone. It is also possible to attach such perfluoroaromatic compounds to a base material. To improve the properties of such an oligomer / polymer, various options exist for substituting a fluorine atom of a perfluoroaromatic compound with a functional group. Specifically, it is already known to nucleophilically substitute the 4-fluorine atom in poly(pentafluorostyrene) (PPFSt) with various functional groups, also known as nucleophiles.

[0006] From Noy-JM; Li, Y.; Smolan, W.; Roth, PJ Azide-para-Fluoro Substitution on Polymers: Multipurpose Precursors for Efficient Sequential Postpolymerization Modification. Marcomolecules 2019, 52, 3083-3091 It is previously known to replace the 4-F atom of polypentafluorostyrene with an NH2 molecule. A functionalized polymer is prepared in two steps starting from polypentafluorostyrene. In a first step, the 4-F atom is replaced by an N3 molecule. In the second step, this Ns molecule is converted into an NH2 molecule. The reaction in the second step is shown in the figure below, with the NH2-functionalized polymer shown on the left.

[0007] Chen, J.; Dumas, L.; Duchet-Rumeau, J.; Fleury, E.; Chariot, A.; Portinha, D. Tuning h-bond capability of hydroxylated-poly(2, 3,4,5, 6-penta- fluorostyrene) grafted copolymers prepared by chemeselective and versatile thiol-para-fluoro “click-type” coupling with mercapatoalcohols. J. Polym. Sei. A. Polym. Chem. 2012, 50, 3452-3640 also report a simple nucleophilic substitution of the 4-F atom. In this case, a functional group is coupled to the perfluoroaromatic compound in such a way that a fluorine atom is substituted by a mercaptothiol group. The structure of the resulting material is shown below. Another simple nucleophilic substitution of a fluorine atom is reported by Sych, G.; Simokaitiene, J.; Lygaitis, R.; Jatautiene, E.; Pahsazadeh, R.; Buika, G.; Grazulevicius, J.V. Structure-properties relationship of tetrafluorostyrene-based monomers and polymers containing different donor moieties. Reactive and Functional Polymers 2019, 143, 104323. In this case, a nitrogen atom occupies the position of a fluorine atom in the perfluoroaromatic compound. The structure is shown in the figure below.

[0008]

[0009] DE 10 2019 008 024 A1 discloses further nucleophilic substitutions of perfluoroaromatic compounds in oligomers or polymers. Specifically, a nitrogen atom replaces the fluorine atom in the perfluoroaromatic compound. The resulting structure is shown below. Further simple nucleophilic substitutions are described in

[0010] Sych, G.; Simokaitiene, J.; lygaitis, R.; Jatautiene, E.; Pahsazadeh, R.; Buika, G.; Grazulevicius, J.V. Structure-properties relationship of tetrafluorostyrene- based monomers and polymers containing different donor moieties. Reactive and Functional Polymers 2019, 143, 104323;

[0011] Cho, H.; Atanasov, V.; Krieg, H.M.; Kerres, J.A. Novel Anion Exchange Membrane Based on Poly(Pentafluorostyrene) Substituted with Mercaptotetrazole Pendant Groups and its Blend with Polybenzimidazole for Vanadium Redox Flow Battery Applications. Polymers (Basel) 2020, 12;

[0012] Atanasov, V.; Bürger, M.; Lyonnard, S.; Porcar, L; Kerres, J. Sulfonated poly(pentafluorostyrene): Synthesis & characterization. Solid State Ionics 2013, 252, 75-83; und

[0013] Atanasov, V.; Kerres, J. Highly Phosphonated Polypentafluorostyrene. Macromolecules 2011 , 44, 6416-6423.

[0014] While such polymers can be provided with a functional group, this makes it difficult to achieve certain property profiles. For example, polypentafluorostyrene, whose 4-F atom is substituted with phosphonic acid groups, is very brittle. This precludes the use of this material as a membrane in a fuel cell. The mechanical properties can be improved, for example, by converting it into an acid-base blend with a mechanically and chemically stable basic polymer, such as polybenzimidazole (PBI). However, this conversion reduces the number of free phosphonic acid groups through ionic crosslinking between the acidic phosphonic acid groups and the basic imidazole groups of the PBI. This leads to a reduction in ionic conductivity, which is undesirable.

[0015] The object of the present invention is therefore to provide a substance that has favorable property profiles and can be used, in particular, in membranes for electrochemical processes. Furthermore, a process for producing such a substance is to be created.

[0016] This object is achieved in a substance of the type mentioned at the outset in that several, in particular two, three, four or five fluorine atoms of the perfluoroaromatic compound are each nucleophilically substituted by a functional group.

[0017] Accordingly, the process according to the invention for producing such a substance comprises the following steps:

[0018] - Providing a starting material which contains oligomers or polymeric chains to which perfluoroaromatic compounds having several fluorine atoms are coupled or which contain perfluoroaromatic compounds having several fluorine atoms;

[0019] - nucleophilic substitution of at least one or more, in particular of exactly two, three, four or five fluorine atoms of the perfluoroaromatic compound by one functional group each.

[0020] The invention is therefore based on the idea of ​​using the perfluoroaromatic compounds in a starting material to substitute not just one fluorine atom, but several fluorine atoms with functional groups. 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 simultaneously exhibits low brittleness, so that it can be used as a membrane in an electrochemical application, for example in a fuel cell, electrolysis, or a redox flow battery. The substance can be an intermediate product, particularly in the production of a membrane.

[0021] Specifically, the perfluoroaromatic compound can be or comprise a perfluorophenyl and / or a perfluorobiphenyl unit. A perfluorophenyl unit or a perfluorobiphenyl unit is typically docked to an oligomeric or polymeric backbone and generally comprises several fluorine atoms, in special applications, 4 or 8 fluorine atoms. The perfluoroaromatic compound can also, in principle, be a perfluoroterphenyl unit or a quaterphenyl unit.

[0022] Preferably, the para and 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 quaterphenyl unit are each substituted by a functional group. The prior art shows that a functional group tends to initially substitute the para position on the perfluorophenyl unit or the perfluorobiphenyl unit. Therefore, if multiple functional groups are provided on a perfluoroaromatic compound, the fluorine atom will certainly be substituted first in the para position. A further functional group will then be coupled in an ortho position and / or a meta position. If three fluorine atoms are each substituted by a functional group, in addition to the para fluorine atom, an ortho fluorine atom and the meta fluorine atom opposite it can be substituted.

[0023] The perfluoroaromatic compound can be contained in the main and / or side chain of the oligomeric or polymeric chain or form a side chain. In other words, a perfluoroaromatic compound can be contained in the backbone or coupled to it. Thus, the incorporation of perfluoroaromatic compounds into the main and / or side chain of the polymer molecule enables subsequent multiple functionalization of the polymer.

[0024] In a further embodiment, the oligomeric or polymeric chains can contain cation exchangers and / or anion exchange groups. Furthermore, the oligomeric or polymeric chains can contain a repeating unit that contains or consists of pentafluorostyrene.

[0025] In a further embodiment, the multiple 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 multiple fluorine atoms of the perfluoroaromatic compound. Alternatively, different functional groups can also be provided, which can be particularly advantageous for adjusting different material properties.

[0026] 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 containing a thiol group can be used for substitution. Such a thiol group, also called a sulfhydryl group, is essentially a functional group similar in structure 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, the process is called thiolation.In this case, the sulfur atom of the thiol group takes the place of a fluorine atom of the perfluoroaromatic compound.

[0027] In a further embodiment, a functional group can be a linear and / or branched saturated or unsaturated C n -body, in particular a C2, C3, Ce, Cs, C10, C12, C14, C16 or a C11 body, which carries at one end the sulfur atom which substitutes a fluorine atom of the perfluoroaromatic compound. In other words, the sulfur atom which substitutes 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-, PO43-, HPO42-, H2PO4-, SO3 2 -, SO3H-, phosphonate R-PO3H-, carbonate COs 2 ', HCOs'' or 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 Cn chains.

[0028] In addition, the functional group may contain a nitrogen atom as a primary, secondary, tertiary, or quaternary amine or ammonium group. Such a nitrogen atom may, for example, be present within a linear or branched C chain containing optionally unsaturated groups. n -body.

[0029] A functional group can be in the form R - SH, R -S-, R -OH, R -NH, R - N- or PO3R2, where R is alkyl, aryl, alkyl, aryl, a metal, Si(CHs)3 or H.

[0030] Any combination is conceivable. Specifically, the first nucleophile, i.e., the first functional group substituting the para-fluorine atom, can have the form R-SH, RS-, R-OH, RO-, R-NH2, R-NH, RN-, or PO3R2. Completely independent of this, a second functional group can encompass all forms. The same applies to a third functional group.

[0031] 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 are subsequently 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.

[0032] The R radical can vary 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.

[0033] A functional group may also contain a thiol group or be based on a thiol group or be prepared from a thiol group.

[0034] If the functional group has the form SR, where the sulfur atom occupies the position of the substituted fluorine atom, the radical R can be formed as shown in the figure below, but this does not limit the types of possible radicals R.

[0035]

[0036] 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, in particular 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-, HCOs' or an organic carboxylic acid anion such as CH3COO-, HCOO-. The radical or the 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).

[0037] It can be provided that the functional group is coupled to several, in particular two, perfluoroaromatic compounds of two organic oligomeric or polymeric chains, so that the functional group crosslinks the chains. This design is based on the idea of ​​not functionalizing the oligomeric or polymeric 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 material.

[0038] The chains to be cross-linked can be identical oligomers or polymeric chains or different chains.

[0039] In a specific embodiment, such a functional group can be chain-like and have a sulfur atom at each end, which nucleophilically substitutes a fluorine atom of the perfluoroaromatic compounds. Between the two sulfur atoms, the functional group can have one or more C n -body and / or a repeating unit.

[0040] The object underlying the invention is further achieved by a membrane, in particular a blend membrane, containing a substance as described above. In a further embodiment, the membrane can be an ion exchange membrane, preferably a cation exchange membrane or an anion exchange membrane.

[0041] The invention further relates to the use of such a membrane in an electrochemical system, in particular in a fuel cell, preferably a hydrogen fuel cell or a direct fuel cell, or in a battery, in particular in a redox flow battery, or in an electrochemical process, in particular in an electrolysis process, in particular in acidic or alkaline or bipolar membrane electrolysis. Furthermore, such a membrane can be used as an ion-conductive membrane in electrosynthesis applications.

[0042] The process according to the invention can be configured in such a way that the perfluoroaromatic compound of the starting material is or comprises a perfluorophenyl or perfluorobiphenyl unit. In the nucleophilic substitution, preferably the para and at least one ortho position and / or at least one meta position of the perfluorophenyl unit or the perfluorobiphenyl unit are substituted by a functional group. The perfluoroaromatic compound can, in principle, also be a perfluoroterphenyl unit or a quaterphenyl unit.

[0043] Examples of suitable starting materials are shown in the figure below.

[0044]

[0045]

[0046] Each of the starting materials presented contains perfluoroaromatic compounds / building blocks with multiple fluorine atoms, where nucleophilic substitution reactions can occur. This means that multiple fluorine atoms can be substituted by functional groups.

[0047] The starting material can also be a partially fluorinated polyether or polythioether or polysulfone, or a sulfonated, partially fluorinated, or a phosphonated partially fluorinated polymer. Furthermore, the starting material can be a polymer of o-, m-, or p-terphenyl or o-, m-, or p-quaterphenyl and / or perfluoroacetophenone or another (partially) aromatic and partially or perfluorinated ketone. The starting material can also be characterized by containing fluorinated and / or unfluorinated alkaline spacers in the oligomeric or polymeric chains, particularly in the backbone (in the polymer main chain). Alternatively, the starting material can be a terphenyl polymer or a quaterphenyl polymer, particularly made of angled terphenyl and / or quaterphenyl monomers. The chains of the starting material can contain partially fluorinated terphenyl and / or quaterphenyl units. Furthermore, the starting material can contain fluorene-based backbones.

[0048] According to one embodiment of the process according to the invention, the starting material can be prepared by coupling perfluoroaromatic compounds to a base material, in particular to a polymer. In other words, a base material can be used to which perfluoroaromatic compounds, in particular perfluorophenyl units or perfluorobiphenyl units, are specifically coupled. The perfluoroaromatic compound, in particular a perfluorophenyl unit or a perfluorobiphenyl unit, can be coupled to the base material by a Suzuki-CC coupling, in particular under the action of a perfluoroaromatic and / or partially fluoroaromatic boronic acid.

[0049] As a base material, for example, a halogenated aromatic polymer can be used which is substituted on the aromatic group in particular with I and / or Br and / or CI.

[0050] The process according to the invention can be characterized in that the nucleophilic substitution of several fluorine atoms of the perfluoroaromatic compound takes place in one step. The nucleophilic substitution can preferably take place under the action of a base.

[0051] Alternatively, the nucleophilic substitution of multiple fluorine atoms can occur in several consecutive steps. Preferably, the fluorine atom is substituted first at the para position (in the case of a pentafluorophenyl residue) before at least one, in particular exactly one, fluorine atom is substituted at the ortho position. Substitution of the fluorine atom at the ortho position may subsequently result in a substitution at the opposite meta position.

[0052] The two steps can take place under the same or different ambient conditions. For example, the first step, in which a para-fluorine atom is substituted, can take place at room temperature. It is also conceivable for the first step to take place at a temperature between 60°C and 100°C, in particular at a temperature of at least 70°C and / or at most 85°C. The reaction time can vary considerably, from a few minutes to several days. The second step, in which at least one further fluorine atom is substituted by a functional group, can take place at a higher temperature than the first step. In particular, the temperature can be at least 70°C, preferably at least 80°C. The duration of the substitution reaction can likewise vary from a few minutes to several days.

[0053] 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.

[0054] It is also conceivable that a first substitution reaction takes place during evaporation of a solvent, which preferably takes place at a temperature below 150°C. For substitution, a molecule with a linear or branched, saturated or unsaturated C n-body, in particular with a C2, C3, C6, C8, C10, C12, C14, C16, or a cis-body, which carries a thiol group at one end, can be used. Preferably, an S atom of the thiol group then substitutes an F atom of the 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.

[0055] 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-, phosphonate R-PO3H-, carbonate CO3 2 -, HCOs'' or with an organic carboxylic acid anion, in particular CH3COO-, 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.

[0056] For the process according to the invention, a molecule in the form R-SH, R-S-, R-OH, R-NH, R-N- or PO3R2 can be used for substitution. Furthermore, a thiol with a terminal sulfonate group can be used for substitution. Furthermore, a molecule C5NH10 can be used for substitution, wherein 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, wherein 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 COs 2 ', HCOs' or an organic carboxylic acid anion, especially CH3COO-, HCOO-. The residue can in principle contain any anion as counterion, whereby anions such as halide (F-, Cl-, Br-, I ) or SO4 2 ', HSO4-, PO4 3 -, HPO42 -, H2PO4-, SO3 2 -, SO3H-, phosphonate R-PO3H-, carbonate CO3 2 -, HCOs', or an organic carboxylic acid anion such as CH3COO-, HCOO- are preferred. 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.

[0057]

[0058] Furthermore, the molecule SO3 used for substitution 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, in particular imidazolium, benzimidazolium, guanidinium. A functional group can contain C5NH10, where the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound. In particular, a radical or counteranion can be substituted via the nitrogen atom, where the radical 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 -, HCOs' or an organic carboxylic acid anion such as CH3COO-, HCOO-. The radical or the 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).

[0059] The process according to the invention, in particular the substitution that takes place, can be configured such that the functional group is coupled to several, in particular two, perfluoroaromatic compounds of two organic oligomeric or polymeric chains, so that the functional group crosslinks the chains. This configuration is based on the idea of ​​not functionalizing the oligomeric or polymeric 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 material.

[0060] Specifically, the functional group can be chain-like and have a sulfur atom at each end, which nucleophilically substitutes a fluorine atom of the perfluoroaromatic compounds. Between the sulfur atoms, one or more C n-body and / or a repeating unit.

[0061] 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 modification of the residues of the functional group, or the use of an aromatic / unsaturated residue of the functional group.

[0062] 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.

[0063] For further details of the invention, reference is made to the dependent claims and the following description of several embodiments with reference to the figures. The figures show:

[0064] Figure 1 shows a reaction scheme for the preparation of a functional group for a substance according to a first embodiment of the present invention;

[0065] Figure 2 shows a reaction scheme of the functional group from Figure 1 with a polymer;

[0066] Figure 3 shows reaction schemes for modifying a lithiated polymer to create a starting material according to a second embodiment;

[0067] Figure 4 shows a reaction scheme for the nucleophilic substitution of the starting material of Figure 3;

[0068] Figure 5 shows a reaction scheme for nucleophilic substitution according to a third embodiment; Figure 6 shows a reaction scheme for nucleophilic substitution in a first step on polypentafluorostyrene according to a fourth embodiment;

[0069] Figure 7 shows a reaction scheme for the nucleophilic substitution of polypentafluorostyrene in a second step;

[0070] Figure 8 shows a reaction scheme for the nucleophilic substitution of a polypentafluorostyrene already substituted in the para position in a second step;

[0071] Figure 9 Reaction schemes for the nucleophilic substitution of a partially or unsulfonated polymer according to a fifth embodiment;

[0072] Figure 10 shows a reaction scheme for nucleophilic substitution of a perfluorinated biphenyl polymer using various methods;

[0073] Figure 11 shows a reaction scheme for the covalent crosslinking of aromatic sulfonated and / or phosphonated blend membranes made of aromatic polymers according to a sixth embodiment;

[0074] Figure 12 shows a reaction scheme for the reaction of a polymer of p-terphenyl and perfluoroacetophenone with piperidine according to a seventh embodiment;

[0075] Figures 13 and 14 show NMR spectra of the polymer from Figure 11 before and after reaction with piperidine; Figure 15 shows reaction schemes for the nucleophilic substitution of the piperidine-modified polymer from Figure 11;

[0076] Figure 16 shows a structural representation of various backbones modified by means of fluorinated and unfluorinated alkylic spacers according to an eighth embodiment;

[0077] Figure 17 Reaction schemes for nucleophilic substitution of a polymer from Figure 15;

[0078] Figure 18 shows a structural representation of terphenyl polymers from angled terphenyl monomers as starting materials;

[0079] Figure 19 shows a structural representation of main chains with partially fluorinated terphenyl / quarterphenyl units; and

[0080] Figure 20 shows a structural representation of fluorene-based backbones as starting materials.

[0081] Example 1

[0082] Figures 1 and 2 show the reactions in the process according to the invention for producing a substance. The starting material, i.e. a polymer to be functionalized with an average molecular weight of approximately 100,000 g / mol, is obtained by polyhydroxyalkylation of p-terphenyl and perfluoroacetophenone. This starting material, which contains perfluorophenyl units, is shown on the left in Figure 2. The production of a functional group, i.e. the production of a molecule for functionalization, is shown in detail in Figure 1 and is carried out starting from dibromohexane. The functional group, which is shown bottom right in Figure 1, carries a halogen at one end and a cationic group at the other end.

[0083] Under the action of a base, the para-fluorine atom and one ortho-fluorine atom are substituted by the functional group, as can be seen in the perfluorophenyl unit shown on the right in Figure 2. The para-fluorine atom is substituted before the ortho-fluorine atom. Double ortho-substitution could not be observed in the NMR spectrum.

[0084] The substance produced by the reaction is transparent, colorless, flexible and has sufficient film-forming properties for the production of membranes.

[0085] Example 2

[0086] The starting point for the second embodiment is commercially available polymers, e.g., PSU Udel, PPSU Radel R (manufacturer: Solvay), Ultrason E, Ultrason P, or Ultrason S (manufacturer: BASF), or polyphenylene oxide (PPO) / polyphenylene ether (PPE). These are first lithiated, as shown in Figure 3 for PSU Udel. Alkyl lithium compounds, such as n-butyllithium, are used for this purpose.

[0087] The substance is then reacted with reactive electrophiles such as acid chlorides, sulfonic acid fluorides, ketones, aldehydes, or other electrophiles containing perfluorinated aromatic moieties. This process is illustrated in Figure 3. The structures shown contain a perfluoroaromatic compound, in this case a perfluorophenyl unit. It has been shown that the perfluoroaromatic electrophiles do not react with the lithium atoms of the lithiated polymer by nucleophilic substitution of one or more of their fluorine atoms.

[0088] In a next step, the resulting starting materials, in this case polymers containing perfluoroaromatic compounds, can be reacted with functional groups, for example. These can be thiols, as in the first embodiment, meaning that a sulfur atom takes the place of a fluorine atom.

[0089] It is also possible that, in a further step, the modified polymers react with tris-trimethylsilyl phosphite to obtain a phosphonated polymer. In a second step, this phosphonated polymer can be further reacted with a thiol, such as the one described in Example 1.

[0090] Alternatively, substitution of the polymer with perfluoroaromatic compounds, as shown in Figure 3, with any functional group containing sulfur would be possible. Likewise, further reaction can be carried out with any molecule containing, for example, a nitrogen atom or an oxygen atom.

[0091] In this case, a first functional group (Nu1) initially substitutes a fluorine atom at the para position of the perfluoroaromatic compound. A second functional group will then, in a subsequent step, substitute one of the two ortho-fluorine atoms (Nu2). Finally, in a third step, the meta-fluorine atom opposite the substituted ortho-fluorine atom can be substituted. The nucleophilic substitution of at least two, in this case three, fluorine atoms takes place one after the other. These can be the same functional group in each case or different functional groups. The functional groups, i.e. the molecules used for the substitution and also referred to as nucleophiles, can have 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 nucleotide, i.e., the first functional group substituting the para-fluorine atom, can have the form R-SH, RS-, R-OH, RO-, R-NH2, R-NH, RN-, PO3R2. Completely independent of this, the second functional group, designated NU2, can encompass all forms. The same applies to a third functional group, designated Nu3.

[0092] The R radical can vary for the various functional groups. It is therefore entirely possible for the first functional group (Nu1) to have the form R-SH, where R is aryl, and the second functional group (Nu2) to have the form R-OH, where R is a metal. Furthermore, the third functional group (Nu3) can easily have another form, for example, R-NH, where R is an alkyl radical.

[0093] Example 3

[0094] Figure 5 shows a polymer according to the invention, for the production of which halogenated aromatic polymers were used as the base material. In Figure 5, top left, there is a halogenated polymer which is substituted with bromine on the aromatic group. In the first step, a Suzuki CC coupling is carried out using a perfluoroaromatic boronic acid. In this way, the polymer is provided with perfluoroaromatic compounds, present in the form of perfluorophenyl units. In two further steps, first the para-fluorine atom and then an ortho-fluorine atom can be substituted one after the other by a functional group, i.e. a nucleophile. This is carried out in each case under the action of a base, whereby the nucleophile itself can also represent the base, as is the case, for example, when piperidine is used for the nucleophilic substitution of the fluorine atom.

[0095] Any functional groups can be used for nucleophilic substitution, in particular the functional groups explained in connection with embodiment 1 and embodiment 2, as well as embodiment 4 described below.

[0096] Example 4

[0097] Figures 6 and 7 show the reaction schemes with respect to a further embodiment according to the present invention.

[0098] First, a polymer to be functionalized is obtained through radical polymerization of pentafluorostyrene. The molecular weight varies between 8,000 and 300,000 g / mol. This starting material is shown schematically in Figure 6 on the left.

[0099] In a first step, a nucleophilic substitution of the para-fluorine atom of the pentafluorophenyl unit takes place. A degree of substitution of up to 100% can be achieved, based on the fluorine atoms in the para position. The molecules used for functionalization possess a thiol group on a saturated hydrocarbon. This means that the sulfur atom of the thiol group occupies the position of the substituted para-fluorine atom, as shown in Figure 6. The possible R radicals are shown on the right in Figure 6. Accordingly, the functional group can be a linear or branched C n -body, for example a Ce-, a Cs-, a C10-, C12-, C10-, C12-, C14-, C16-, or a C18-body. Furthermore, the functional group can contain a nitrogen atom, or at the other end of the C facing away from the sulfur atom n-body may have a quinuclidinium group or any other quaternary N group such as preferably ammonium, imidazolium, benzimidazolium, piperidinium, piperazinium, guanidinium, pyridinium group or an acidic group such as SO3H or PO3H2.

[0100] The substitution of the para-fluorine atom takes place at room temperature over a period of less than 10 minutes, in particular under the action of triethylamine or triethanolamine or diazabicycloundecene (DBU, exact name 1,8-diazabicyclo[5.4.0]undec-7-ene) and / or acetone. In a second step, the substitution of an ortho-fluorine atom takes place. This second step is shown in detail in Figure 7. For this purpose, the temperature is increased, in particular to a value above 60°C, preferably above 70°C, and particularly preferably to a temperature of 80°C. The reaction time is approximately 6 hours. In this way, an ortho-fluorine atom and even a meta-fluorine atom are activated for nucleophilic substitution, as shown in Figure 7.

[0101] Figure 8 shows another reaction scheme. In this case, the para-fluorine atom of a pentafluorophenyl unit has already been substituted with a functional group in the first step. Specifically, the functional group in this case is a phosphonic acid group. In a second step, the ortho-fluorine atom and the meta-fluorine atom are then substituted. The reaction time at a reaction temperature of 80°C is approximately 10 hours, as shown in Figure 8. The functional groups substituting the ortho-fluorine atom and the opposite meta-fluorine atom can be identical or different. The sulfur atom substituting the fluorine atom can be followed by a residue, the design of which is shown as an example in Figure 7. The different functional groups can be the same residue or different.Any combination of the residues from Figures 6 and 7 in the three functional groups provided is possible.

[0102] It has been found that the material produced by the described reaction is transparent, colorless and flexible and has sufficient film-forming properties for the production of membranes.

[0103] Example 5

[0104] In this embodiment, partially and unsulfonated polyethers are used as starting materials. Examples of starting materials are shown on the left in Figure 9. A thiol with a terminal sulfonate group is used as the molecule for the nucleophilic substitution. These are essentially "clicked" onto a perfluorinated biphenyl group by the aromatic substitution reaction described above. The ether bridges in the polymer backbone have a +M effect on the biphenyl group. This reduces the reactivity of the perfluoroaromatic compound towards aromatic nucleophilic substitution. Accordingly, the reaction temperature and reaction time are increased compared to the previously mentioned examples. In the reaction scheme shown above in Figure 9, in which PFS is used as the starting material, the substitution is planned to take place at a temperature of 70°C over a period of, for example, 2 days.In the reaction scheme shown below in Figure 9, which uses SFS as the starting material, the reaction takes place at 85°C over a period of, for example, 2 days. Unlike the reaction scheme shown above, a base is also used. Both reactions preferentially take place in the presence of DBU.

[0105] After the initial substitution at one of the two rings of the perfluorobiphenyl unit, a second substitution occurs in the para position due to the activation of the opposite fluorine atom, as shown in Figure 9. Due to this effect, almost exclusively perfluorinated phenyl rings without substitution or with a double substitution were detected in the NMR spectrum, as shown, for example, in Figure 9 above. The phenyl ring shown on the right is doubly substituted, while the adjacent phenyl ring to the left of the perfluorobiphenyl unit is unsubstituted. The counterions of the sulfonic acid groups can be exchanged by appropriate post-treatment with strong acids, thus converting the ionomer into a corresponding ion-exchange form.

[0106] Adapting the thiols used enables the coupling of a variety of functional groups to a fluorinated ionomer. These are then available for further reactions. Such reactions are illustrated as examples in Figure 10. For example, the functionalization of a perfluorinated biphenyl polymer with aryl mercaptan is shown. The resulting double bond, which is created in a first step, can be used for various subsequent reactions. For example, the functionalized polymer can be reacted with bifunctional crosslinkers, which react with the double bonds either thermally or photochemically activated even after the creation of a polymer solution layer or membrane. For example, crosslinking with a dithiol via a thiol-(alk)ene click reaction is shown here (shown on the left in Figure 10).As a further reaction, coupling with simple thiols or other alkenophiles (for example, in a Diels-Alder reaction) can be carried out. By introducing a thiol with alkyne functionality, further reactions such as copper-catalyzed alkyne-acid couplings are also possible. It is also possible to use the double bond as the starting point for a graft polymerization, as shown in Figure 10 on the right. This allows additional polymer chains to be grafted onto the existing backbone. Figure 10 shows unmodified styrene. For example, additional acidic groups can be introduced by using functionalized monomers.

[0107] Example 6

[0108] In this embodiment, the reaction scheme of which is shown in Figure 11, a sulfonated partially fluorinated and a phosphonated partially fluorinated aromatic polymer are used as starting materials. In a first step, the individual components are dissolved in a solvent, preferably a dipolar aprotic solvent such as NMP, DMAc, DMSO, or DMF. In a further step, the two solutions are combined, with the addition of a dithiol crosslinker in the hydrogen form. The solvent is then evaporated in a convection oven at elevated temperatures of up to 150°C.

[0109] During the evaporation of the solvent, a partial nucleophilic substitution of the thiol groups with a fluorine atom of the perfluoroaromatic compound already occurs.

[0110] After evaporation of the solvent, the membrane is post-treated in a strong alkali, e.g., NaOH, at elevated temperature. This completes the cross-linking reaction, as the thiol anions are significantly more nucleophilic than the thiol groups in the hydrogen form. Cross-linking results in the functional groups being coupled to two perfluoroaromatic compounds of two different oligomeric or polymeric chains. This cross-links the two chains, as shown on the right in Figure 11.

[0111] The functional group used here is a C n -body, specifically a Ce body, with a thiol group attached to both ends. As can be seen in Figure 11, one terminal sulfur atom substitutes for a fluorine atom of a perfluoroaromatic compound, and the other terminal sulfur atom substitutes for a different perfluoroaromatic compound, which, however, belongs to a different chain.

[0112] Example 7

[0113] The starting material chosen here is a polymer of terphenyl and terfluoroacetophenone. This starting material is shown on the left in Figure 12.

[0114] In a first step, the polymer is reacted with piperidine, meaning the para-fluorine atom is substituted accordingly. Surprisingly, this results in 100% substitution of the para-fluorine atom by piperidine, which can be seen in the NMR spectra in Figure 13 (unsubstituted polymer) and Figure 14 with piperidine (substituted polymer).

[0115] The further modification reaction of the corresponding piperidine-substituted polymer is shown in Figure 15. Figure 15, bottom left, shows a further reaction with a thiol group. The functional group shown in Figure 15, bottom left, can be structured like the functional group of the first, third, or fourth embodiment, i.e., in particular, in the form SR, where R can be alkyl, aryl, e.g., (CH2)x with x=1-20. Alternatively, after the first step (modification with piperidine), alkylation of the piperidine residue to form the piperidinium cation can take place, as shown on the right in Figure 15. Subsequently, thiolation can again take place, as previously described.

[0116] Example 8

[0117] Figures 16 to 20 show various configurations, particularly of backbones, some of which are provided with alkylic fluorinated and non-fluorinated spacers. Such spacers can influence the properties of the materials. Specifically, especially with the materials shown in Figure 16, the flexibility of the chain segments is increased, so that the produced membrane is less brittle than a system based purely on aromatic monomer units. Perfluorinated alkylic spacers can also be used, as shown, for example, in Figure 16 in Examples 2 and 4, which improves the chemical stability of the materials.

[0118] Figure 17 shows an inventive nucleophilic substitution of fluorine atoms of the perfluorophenyl or perfluorobiphenyl unit of the two starting materials 1 and 3 from Figure 16. In each case, the para-fluorine atom and one ortho-fluorine atom of the corresponding units are substituted by a functional group in the form SR. Likewise, the substitution can also be formed by functional groups in the form R-OH, R-NH, RM-, or PO3R2, where R is an alkyl radical, aryl radical, alkyl, aryl, a metal, Si(CH3)s, or H. The R radicals, in particular the substitutions at the para position and at the ortho position, can be the same functional group. However, the functional groups can also differ in principle, which means that R stands for different radicals. In addition to the use of alkyl spacers, the use of ortho- and meta-linked terphenyls is also possible. This is shown specifically in Figure 18.Such linked terphenyls have a positive influence on the mechanical properties of the material. Terphenyl copolymers can also be synthesized that contain both linear and angled terphenyl units in the chain. By specifically selecting the mixing ratio between linear and angled terphenyl units, the solubility of the polymers can be improved and their mechanical properties optimized.

[0119] The nucleophilic substitutions of the fluorine atoms described above can also be carried out on these compounds, as described in connection with Figure 17. Both singly and multiply substituted repeat units can be obtained in this way.

[0120] Furthermore, it is possible to replace the terphenyl units with biphenyls or partially fluorinated aromatic systems, resulting in novel structures. Such structures can be seen, for example, in Figure 19.

[0121] By using the partially fluorinated aromatic units, it is possible to make further substitutions on various side chains of the fluorinated units of the backbone in addition to the substitutions on perfluorophenyl units already shown.

[0122] Furthermore, the aromatic portion of the backbone can also be represented by substituted fluorenes. Examples of such structures are shown in Figure 20. The corresponding polymers can be easily substituted according to the invention using a thiol click reaction. This means that fluorine atoms are substituted by corresponding thiol groups in a click reaction. This creates another control factor for influencing the number of side chains, which influences the properties of the resulting substance.

Claims

REQUIREMENTS 1. Substance, in particular a functionalized oligomer or polymer, wherein the substance contains oligomeric or polymeric chains to which perfluoroaromatic compounds are coupled or which contain perfluoroaromatic compounds, characterized in that several, in particular two, three, four or five fluorine atoms of the perfluoroaromatic compound are nucleophilically substituted by a functional group.

2. The substance according to claim 1, characterized in that the perfluoroaromatic compound is or comprises a perfluorophenyl and / or a perfluorobiphenyl unit.

3. The substance according to claim 2, characterized in that the para- and at least one ortho- position and / or at least one meta- position of the perfluorophenyl unit or the perfluorobiphenyl unit is each substituted by a functional group.

4. Substance according to one of the preceding claims, characterized in that the perfluoroaromatic compound is contained in or forms a side chain in the main and / or side chain of the oligomeric or polymeric chain.

5. Substance according to one of the preceding claims, characterized in that the oligomeric or polymeric chains contain cation exchanger and / or anion exchanger groups.

6. Substance according to one of the preceding claims, characterized in that the oligomeric or polymeric chains contain a repeating unit which contains or consists of pentafluorostyrene.

7. Substance according to one of the preceding claims, characterized in that the multiple fluorine atoms of the perfluoroaromatic compound are substituted with the same functional group or with different functional groups.

8. Substance according to one of the preceding claims, characterized in that a functional group is coupled to the perfluoroaromatic compound in such a way that a fluorine atom is substituted by a sulfur atom.

9. Substance according to claim 8, characterized in that the functional group comprises 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 which has at one end the sulfur atom which substitutes a fluorine atom of the perfluoroaromatic compound.

10. Material according to claim 9, characterized in that at the other end of the C n- Body 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-, Cf, 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' , is coupled.

11. Substance according to claim 8 or 9, characterized in that the functional group includes a nitrogen atom as a primary, secondary, tertiary or quaternary amine or ammonium group.

12. Substance according to one of the preceding claims, characterized in that a functional group is formed in the form R - SH, R - S', R - OH, R - NH, R - N' or PO3R2, wherein R is alkyl group, aryl group, alkyl, aryl, a metal, Si(CH3)3 or H.

13. Substance according to one of the preceding claims, characterized in that a functional group contains a thiol group or is based on a thiol group or was produced starting from a thiol group.

14. Substance according to one of the preceding claims, characterized in that a functional group SO3 with a countercation, in particular with a metal countercation or an ammonium countercation in the form NR4 + containing R = H, alkyl, aryl or another N-basic cation, in particular imidazolium, benzimidazolium, guanidinium, which is coupled to a sulfur atom substituting a fluorine atom.

15. Substance according to one of the preceding claims, characterized in that a functional group C5NH 10 contains, wherein the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound.

16. Substance according to claim 15, characterized in that a residue is coupled, in particular via the nitrogen atom, wherein the residue is preferably a halide (F, Ch, Br, F) 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, especially CH3COO', HCOO', is.

17. Substance according to one of the preceding claims, characterized in that the functional group is coupled to several, in particular to two, perfluoroaromatic compounds of two different oligomeric or polymeric chains, such that the functional group crosslinks the chains.

18. The substance according to claim 17, characterized in that the functional group is chain-like and has a sulfur atom at each end which nucleophilically substitutes a fluorine atom of the perfluoroaromatic compounds.

19. Material according to claim 18, characterized in that the functional group comprises one or more C n -body and / or a repeating unit.

20. Membrane, in particular blending membrane, containing a substance according to one of the preceding claims.

21. Membrane according to claim 20, characterized in that it is an ion exchange membrane, preferably a cation exchange membrane or an anion exchange membrane.

22. Use of a membrane according to claim 20 or 21 in an electrochemical plant, 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.

23. A method for producing a substance according to any one of claims 1 to 19, comprising the following steps: - Providing a starting material containing oligomeric or polymeric chains to which perfluoroaromatic compounds with multiple fluorine atoms are coupled or which contain perfluoroaromatic compounds with multiple fluorine atoms; Nucleophilic substitution of at least two, in particular exactly two, three, four or five fluorine atoms of the perfluoroaromatic compound by a functional group.

24. The method according to claim 23, characterized in that the perfluoroaromatic compound of the starting material is or comprises a perfluorophenyl or a perfluorobiphenyl unit.

25. Method according to claim 24, characterized in that the para- and at least one ortho-position and / or at least one meta-position of the perfluorophenyl unit or the perfluorobiphenyl unit is substituted by a functional group.

26. A method according to one of claims 23 to 25, characterized in that the starting material is produced by the polyhydroxyalkylation of p-terphenyl and perfluoracetophenone.

27. Method according to one of claims 23 to 26, characterized in that the starting material is produced by polymerization of pentafluorostyrene, in particular with a molar mass of 8,000 to 300,000 g / mol.

28. A method according to any one of claims 23 to 27, characterized in that the starting material is a partially fluorinated polyether or polythioether or polysulfone.

29. A method according to any one of claims 23 to 28, characterized in that the starting material is a sulfonated partially fluorinated or a phosphonated partially fluorinated polymer.

30. A method according to any one of claims 23 to 29, characterized in that the starting material is a polymer of terphenyl or quaterphenyl and / or perfluoroacetophenone and / or of another partially fluorinated and / or partially aromatic ketone.

31. Method according to one of claims 23 to 30, characterized in that the starting material contains fluorinated and / or non-fluorinated alcanetic spacers in the oligomeric or polymeric chains.

32. Method according to one of claims 23 to 31, characterized in that the starting material is a terphenyl polymer, in particular consisting of bent terphenyl monomers and / or quaterphenyl monomers, and / or that the chains of the starting material contain partially fluorinated terphenyl and / or quaterphenyl units.

33. Method according to one of claims 23 to 32, characterized in that the starting material contains fluorene-based backbones.

34. Method according to one of claims 23 to 33, characterized in that the starting material is produced by coupling perfluoroaromatic compounds to a base material, in particular to a polymer.

35. Method according to claim 34, characterized in that the base material is a halogenated aromatic polymer which is substituted on the aromatic compound in particular with I, Br and / or CI.

36. Method according to claim 35, characterized in that the perfluoroaromatic compound is coupled to the base substance by a Suzuki-CC coupling, in particular under the influence of a partially fluoroaromatic and / or perfluoroaromatic boronic acid.

37. Method according to one of claims 23 to 36, characterized in that the nucleophilic substitution of several fluorine atoms takes place in one step.

38. Method according to claim 37, characterized in that the nucleophilic substitution is carried out under the influence of a base.

39. Method according to one of claims 23 to 38, characterized in that the nucleophilic substitution of several fluorine atoms takes place in several successive steps.

40. Method according to any one of claims 23 to 39, characterized in that a molecule with a linear or branched saturated or unsaturated C is used for substitution. n - Bodies, especially those with a C2, C3, C6, C8, C 10 -, C 12 -, C 14 -, C 16 - or a C 18 - Body which carries a thiol group at one end is used, wherein an S atom of the thiol group substitutes an F atom of the perfluoroaromatic compound.

41. The method of claim 40, characterized in that the molecule has at its other end 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-, phosphonate R-PO3H', carbonate CO3 2 ', HCO3-' or with an organic carboxylic acid anion, especially CH3COO', HCOO'.

42. Method according to claim 40 or 41, characterized in that the molecule includes a nitrogen atom as a primary, secondary, tertiary or quaternary amine or ammonium group.

43. Method according to one of claims 23 to 42, characterized in that a molecule in the form R - SH, R - S', R - OH, R - NH, R - N' or PO3R2 is used for substitution, wherein R is alkyl group, aryl group, alkyl, aryl, a metal, Si(CH3)3 or H.

44. Method according to one of claims 23 to 43, characterized in that a thiol with a terminal sulfonate group is used for substitution.

45. Method according to one of claims 23 to 44, characterized in that a molecule of C5NH is used for substitution. 10 is used, whereby the nitrogen atom substitutes the fluorine atom of the perfluoroaromatic compound.

46. ​​Method according to claim 45, characterized in that a residue is coupled, in particular via the nitrogen atom, wherein the residue is preferably a halide (F-, Ck, Br, I ) or SO4 2 ', HSO4-, PO4 3 ', HPO4 2 , H2PO4-, SO3 2 ', SO3H', phosphonate R-PO3H', carbonate CO32 ', HCO3- or an organic carboxylic acid anion, especially CH3COO', HCOO', is.

47. Method according to one of claims 23 to 46, characterized in that the functional group is coupled to several, in particular to two, perfluoroaromatic compounds of two different oligomeric or polymeric chains, such that the functional group crosslinks the chains together.

48. Method according to claim 47, characterized in that the functional group is chain-like and has a sulfur atom at each end which nucleophilically substitutes a fluorine atom of the perfluoroaromatic compounds.

49. Method according to claim 48, characterized in that the functional group comprises one or more C n-body and / or a repeating unit.

50. Method according to one of claims 23 to 49, characterized in that, following the nucleophilic substitution, subsequent reactions take place for which the functional groups form a reaction basis.

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