Side-chain functionalized polynorbornenes as ionomers and as membrane materials for alkaline electrolysis of water, and fuel cell

Abstract

The present invention relates to water-insoluble polymer membranes (AEM) on the basis of new side-chain functionalized copolymers and their use as alkaline anion exchange membrane materials, for example in alkaline water electrolyzers, fuel cells or flow batteries.

Description

Side-chain functionalized polynorbornenes as ionomers and membrane materials for alkaline water electrolysis and fuel cells INTRODUCTION The present invention relates to water-insoluble polymer membranes (AEMs) based on novel side-chain functionalized copolymers and their use as alkaline anion exchange membrane materials, for example in alkaline water electrolyzers, fuel cells, or flow batteries. A further aspect of the invention relates to novel norbornene-derived monomer and copolymer building blocks used to produce the novel water-insoluble polymer membranes, as well as processes for producing the monomers, copolymers, and polymer membranes according to the invention. BACKGROUND In alkaline water electrolysis, water is split into hydrogen and oxygen by applying an electrical potential. On the anode side, oxygen is formed through the consumption of four equivalents of hydroxide and the loss of electrons (oxidation). In the cathode compartment, hydrogen is produced through the absorption of electrons (reduction) and the formation of two equivalents of hydroxide. The opposite / complementary electrochemical process to water electrolysis is the alkaline membrane fuel cell. The following electrode reactions take place in the alkaline membrane fuel cell: Anode: 2 H2+ 4 OH' -> 4 H2O + 4e' Cathode: O2+ 2 H2O + 4 e- A 4 OH' Overall reaction: 2 H2+ O2A 2 H2O To maintain the two half-reactions of electrolysis and fuel cell, hydroxide ion transport from the cathode to the anode is therefore necessary. The presented invention, a water-insoluble polymer membrane (AEM), fulfills precisely this purpose while simultaneously spatially separating the electrochemical half-cells. To be used as an electrolyte in alkaline water electrolysis or alkaline fuel cells, the polymers must be stable under the aggressive conditions (alkaline environment, electrical potential, hydroxide nucleophilicity, pressure differences, temperatures). Furthermore, the materials used must exhibit high hydroxide conductivity to enable high current densities. STATE OF THE ART Compared to proton-conductive materials, such as those used in water electrolysis or in PEM fuel cells with polymer membranes under acidic conditions, AEMs are less common under alkaline conditions, and there is no standard material, such as Nation™, for acidic applications. The alkaline environment places special demands on polymer stability, and anion-compatible functionalizations are also required in AEMs. It is known in the literature that the separation of the anion exchange group (usually a quaternary ammonium group) from the polymer backbone increases the conductivity through the resulting micro / nanophase separation (CG Arges et al., Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films, Chem. Mater, 2016, 28, 1377-1389.; H.-S. Dang et al., Exploring Different Cationic Alkyl Side Chain Designs for Enhanced Alkaline Stability and Hydroxide Ion Conductivity of Anion-Exchange Membranes, Macromolecules, 2015, 48, 5742-5751.; H.-S. Dang et al., Anion-exchange membranes with polycationic alkyl side chains attached via spacer units, J. Mater. Chem. A, 2016, 4, 17138- 17153.; YA Elabd et al., Block Copolymers for Fuel Cells, Macromolecules, 2011, 44, 1-11. L. Liu et al., Tuning the properties of poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes and their performance in H 2702 fuel cells, Energy Environ. Sci., 2018, 11, 435-446.; S.Miyanishi et al., Highly conductive mechanically robust high Mw polyfluorene anion exchange membrane for alkaline fuel cell and water electrolysis application, Polym. Chem., 2020, 11, 3812-3820.; J. Pan et al., Constructing ionic highway in alkaline polymer electrolytes, Energy Environ. Sei., 2014, 7, 354-360 ; X. Q. Wang et al., Alkali-stable partially fluorinated poly(arylene ether) anion exchange membranes with a claw-type head for fuel cells, J. Mater. Chem. A, 2018, 6, 12455-12465.). Furthermore, polymers with side-chain-separated anion exchange groups exhibit increased alkali stability and better cycling stability in alkaline fuel cells and / or electrolysis. The desired mechanical behavior of membranes can be described as mechanically resilient yet flexible, with aromatic components typically reducing flexibility and increasing robustness, while aliphatic components have the opposite effect (D. Henkensmeier et al., Overview: State-of-the-Art Commercial Membranes for Anion Exchange Membrane Water Electrolysis, Journal of Electrochemical Energy Conversion and Storage, 2021, 18. DOI: 10.1115 / 1.4047963; W.-H. Lee et al., Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property, ACS macro letters, 2017, 6, 566-570). Accordingly, various side chains can be introduced to modify the behavior of the membrane. The side chains can be aromatic, aliphatic, or olefinic, as well as contain heteroatoms. Commercially available for alkaline applications are, for example, membranes based on polyaromatics with ether bridges in the polymer backbone (Fumasep® FAA3 from Fumatech) and quaternary ammonium substituents as anion exchange groups (D. Henkensmeier et al., Overview: State-of-the Art Commercial Membranes for Anion Exchange Membrane Water Electrolysis, Journal of Electrochemical Energy Conversion and Storage, 2021, 18. DOI: 10. 1115 / 1.4047963; S. Gottesfeld et al., Anion exchange membrane fuel cells: Current status and remaining challenges, Journal of Power Sources, 2018, 375, 170-184.) These membranes can be used reinforced or unreinforced, with the ether bond between the aromatics being a particular weak point under alkaline conditions (D. Henkensmeier et al., Overview: State-of-the Art Commercial Membranes for Anion Exchange Membrane Water Electrolysis, Journal of Electrochemical Energy Conversion and Storage, 2021, 18. DOI: 10.1115 / 1.4047963; S. Gottesfeld et al., Anion exchange membrane fuel cells: Current status and remaining challenges, Journal of Power Sources, 2018, 375, 170-184.; N. Chen et al., Anion exchange polyelectrolytes for membranes and ionomers, Progress in Polymer Science, 2021, 113, 101345.). Such aryl ether bonds in the polymer backbone can be directly attacked by hydroxide ions in a nucleophilic substitution reaction. This inevitably leads to a significant reduction in molecular weight and thus not only to lower conductivity but also to a loss of mechanical integrity (A. D. Mohanty et al., Systematic Alkaline Stability Study of Polymer Backbones for Anion Exchange Membrane Applications, Macromolecules, 2016, 49, 3361-3372). In addition, membranes for alkaline electrolysis based on methylated polybenzimidazole (Aemion™ from lonomr Innovations Inc.) are available (D. Henkensmeier et al., Overview: State-of-the Art Commercial Membranes for Anion Exchange Membrane Water Electrolysis, Journal of Electrochemical Energy Conversion and Storage, 2021, 18. DOI: 10.1115 / 1.4047963; AG Wright et al., Hexamethyl-p-terphenyl poly(benzimidazolium): a universal hydroxide-conducting polymer for energy conversion devices, Energy Environ. Sci., 2016, 9, 2130-2142.). Quaternized polybenzimidazoles, which are used as membrane materials for alkaline electrochemical processes, are only chemically stable if the C2 atom of the benzimidazole is sterically shielded, since the degradation of such membranes occurs through a nucleophilic attack of the hydroxide on the imidazole ring with ring opening (D. Henkensmeier et al., Polybenzimidazolium hydroxides - Structure, stability and degradation, Polymer Degradation and Stability, 2012, 97, 264-272.). Technically, attempts are made to counteract this degradation mechanism by increasing the electron density at the imidazole unit and sterically shielding the imidazole unit (AG Wright et al., Hexamethyl-p-terphenyl poly(benzimidazolium): a universal hydroxide-conducting polymer for energy conversion devices, Energy Environ. Sci., 2016, 9, 2130-2142.). Furthermore, membranes made of poly(4-vinylbenzyl chloride-co-styrene) are frequently used. The Sustainion® membrane from Dioxide Materials is commercially available; the benzylic chloride group in poly(4-vinylbenzyl chloride-co-styrene) has been quaternized with 2, 3,4,5-tetramethylimidazole (JJ Kaczur et al., Carbon Dioxide and Water Electrolysis Using New Alkaline Stable Anion Membranes, Frontiers in Chemistry, 2018, 6, 263; RB Kutz et al., Sustainion Imidazolium-Functionalized Polymers for Carbon Dioxide Electrolysis, Energy Technol., 2017, 5, 929-936; D. Li et al., Durability of anion exchange membrane water electrolyzers, Energy Environ. Sci., 2021, 14, 3393-3419; Z. Liu et al., The effect of membrane on an alkaline water electrolyzer, International Journal of Hydrogen Energy, 2017, 42, 29661-29665.; Z. Liu et al., CO 2 Electrolysis to CO and O 2 at High Selectivity, Stability and Efficiency Using Sustainion Membranes, J. Electrochem. Soc., 2018, 165, J3371-J3377; R.IMasel et al., Anion Exchange Membrane Electrolyzers Showing 1 A / cm 2 at Less Than 2 V, ECS Trans., 2016, 75, 1143-1146; S. D. Sajjad et al., Tunable-High Performance Sustainion™ Anion Exchange Membranes for Electrochemical Applications, ECS Trans., 2017, 77, 1653-1656.; D. A. Salvatore et al., Designing anion exchange membranes for CO2 electrolysers, Nat Energy, 2021, 6, 339-348.). Even though Sustainion® achieved better performance in alkaline water electrolysis compared to the other materials, the low alkali stability of benzylic ammonium groups and the inherent brittleness of polystyrene represent a disadvantage of this membrane (N. Chen et al., Anion exchange polyelectrolytes for membranes and ionomers, Progress in Polymer Science, 2021, 113, 101345.; TH Pham et al., Aromatic Polymers Incorporating Bis- N -spirocyclic Quaternary Ammonium Moieties for Anion-Exchange Membranes, ACS Macro Lett., 2015, 4, 1370-1375.; MR Hibbs, Alkaline stability of poly(phenylene)-based anion exchange membranes with various cations, J. Polym. Sci. Part B: Polym. Phys., 2013, 51, 1736-1742.; Y.-K. Choe et al., Alkaline Stability of Benzyl Trimethyl Ammonium Functionalized Polyaromatics: A Computational and Experimental Study, Chem. Mater., 2014, 26, 5675-5682.). DE10 2014 009 170 A1 describes ion exchange membranes for use in electrochemical processes, which are in the form of blend membranes. It describes covalently and / or ionically cross-linked polybenzimidazole (PBI) blend membranes made from halomethylated and optionally sulfonated and / or phosphonated polymers. By adding a low-molecular and / or macromolecular cross-linker, these blend membranes can be further covalently cross-linked. The blend membranes described therein are characterized by the fact that they contain halomethylated polymers, i.e., monomer units functionalized with a Hal-CHz group. DE10 2014 009 170 A1 also provides an overview of known (non-commercial) AEMs in Table 1: Table 1: Relevant membranes for use in fuel cells DE 10 2016 007 815 A1 also describes cross-linked anion exchange blend membranes in which halomethylated polymers, i.e. those with Hal-CH2 group-functionalized monomer units, are used as blend components. described that the conversion of the Hal-CHU groups (Hal = Cl, Br) into an anion exchange group is achieved by reaction with a tertiary amine such as trimethylamine, pyridine, pentamethylguanidine or an N-alkylated imidazole. It also describes that by sterically shielding the anion exchange groups of AEM, in particular their alkali stability can be significantly improved, since the nucleophilic attack of the OH" counterions on the quaternary ammonium group is then hindered. However, DE 10 2016 007 815 A1 also describes that the combination of anion exchange group and polymer main chain is always relevant for improving the chemical stability of AEM, since the stability of the anion exchange group always depends on the polymer main chain and that it is not easy to predict which polymer main chain is more stable. Another possibility for stabilizing AEM is its cross-linking.Furthermore, DE 10 2016 007 815 A1 describes that systematically increasing the hydrophobicity of the AEM ammonium groups by increasing the length of the alkyl chains bound to the quaternary ammonium ion, from trimethylbenzylammonium to triethylbenzylammonium, tri-n-propylbenzylammonium, tri-n-butylbenzylammonium to tri-n-pentylbenzylammonium, significantly reduces the relative transport number of anions with a large hydration shell, such as sulfate or fluoride ions, compared to anions with a smaller hydration shell, such as chloride or nitrate. Accordingly, DE 10 2016 007 815 A1 relates to blend membranes that contain, as blend components, a halomethylated polymer quaternized with a sterically hindered tertiary nitrogen compound, such as quaternized chloromethylated polystyrene or quaternized bromomethylated polyphenylene oxide. The use of polybenzimidazoles as blend materials for blend membranes is also known, for example for membranes based on the anion exchange ionomer FAA3 (Konovalova et al., Blend membranes of polybenzi midazole and an anion exchange ionomer (FAA3) for alkaline water electrolysis: Improved alkaline stability and conductivity, J. Membr. Sei. 2018, 564, 653-662.). He et al. describe further matrix polymers and their use in the production of N-dimethylpiperidine (DMP)-based AEM blend membranes. Among other things, isatin polymers such as polyoxindole biphenyls (POBP) were investigated for their suitability as blend polymers. In the studies described therein, the addition of the isatin polymer polyoxindole biphenyls (POBP) led to a reduction in the stability of the DMP-based AEM membrane in alkaline environments (He et al., Insight into alkaline stability of N-heteroatom on N-dimethylpiperidinium based anion exchange membranes (AEMs) for alkaline water electrolysis, J. Membr. Sci., 2023, 688, 122109.). In summary, numerous polymers and copolymers have already been used in anion-conductive polymer membranes (AEMs). However, many of them suffer from the problem of not being sufficiently chemically stable under alkaline conditions. DE10 2022 120 196.1 describes an approach to solving these problems by providing side-chain functionalized polystyrenes as membrane materials for alkaline water electrolysis. DE10 2022 120 196.1 specifically describes polystyrene-based and quaternized polymers / copolymers, as well as their use in water-insoluble, anion-conductive polymer membranes. In addition to the synthesis, polymerization, copolymerization, and possible functionalization of the membrane polymer building blocks described therein, the possibility of cross-linking the monomer units within the polymer membrane, as well as their provision in the form of blend membranes with polybenzimidazoles, is also described. Using the polymer membranes described herein and their monomer and copolymer building blocks based on selected functionalized norbornene derivatives, the inventors of the present invention have surprisingly developed new polymers and copolymers with excellent properties for use in anion-conductive polymer membranes. Polynorbornenes are already known in the literature as membrane materials. For these, norbornene is usually copolymerized with a norbornene derivative which has a quaternary ammonium group, e.g. a quaternary trimethylamine group, linked via an alkyl chain of various lengths (e.g. quaternized methylnorbornene) (D. Cao et al., Polynorbornene-based anion exchange membranes with hydrophobic large steric hindrance arylene substituent, Journal of Membrane Science, 2022, 641, 119938; W. Chen et al., Highly Conducting Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Ring Opening Metathesis Polymerization, ACS Appl. Energy Mater., 2019, 2, 2458-2468.; M. Mandal et al., Highly Conductive Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Vinyl Addition Polymerization, ACS Appl. Energy Mater., 2019, 2, 2447-2457). Other monomers used to date are based on norbornene with a large aromatic substituent starting from anthracene (D. Cao et al., Polynorbornene-based anion exchange membranes with hydrophobic large steric hindrance arylene substituent, Journal of Membrane Science, 2022, 641, 119938.) or with a special ether-functionalized aliphatic side chain with additional methyl groups (S.C. Price et al., Synthesis and characterization of anion-exchange membranes based on hydrogenated poly(norbornene), Polym. Chem., 2017, 8, 5708-5717.) or with glycidyl ether side chains S. Huang, et al., Facile self-crosslinking to improve mechanical and durability of polynorbornene for alkaline anion exchange membranes, Int. J. Hydrog. Energy, 2020, 45, 13068-13079.). The use of aromatic substituents instead of the unfunctionalized norbornene enhances the mechanical properties by reducing water uptake. While the resulting membranes are easy to handle, their ionic conductivity decreases, making them unsuitable for use as anion-conductive polymer membranes (D. Cao et al., Polynorbornene-based anion exchange membranes with hydrophobic large steric hindrance arylene substituent, Journal of Membrane Science, 2022, 641, 119938.). The copolymerization of norbornene with ether-functionalized norbornene increases water uptake, resulting in gel-like behavior. While conductivity is increased, the resulting membranes are unstable and unsuitable for practical, especially commercial, applications (SC Price et al., Synthesis and characterization of anion-exchange membranes based on hydrogenated poly(norbornene), Polym. Chem., 2017, 8, 5708-5717). The copolymerization of norbornene with norbornene derivatives containing quaternized alkyl chains also results in unusable materials without reinforcement. Although this is compensated for by cross-linking, sufficient conductivities could only be achieved with very high lECs (> 3.1 meq / g). The disadvantage is the high water absorption, which impairs the mechanical properties (M. Mandat et al., Highly Conductive Anion-Exchange Membranes Based on Cross-Linked Poly(norbornene): Vinyl Addition Polymerization, ACS Appl. Energy Mater., 2019, 2, 2447-2457; S. Huang et al., Facile self-crosslinking to improve mechanical and durability of polynorbornene for alkaline anion exchange membranes, Int. J. Hydrog. Energy, 2020, 45, 13068-13079). In addition to alkyl chain-functionalized norbornene monomers, norbornene monomers with polyoxyethylene side chains are also known, which can be used to produce membrane materials by block copolymerization and for which a reduction in the glass transition properties compared to materials with alkyl side chains has been observed {Singh et al., Synthesis of ABA Triblock Copolymers via Ring Opening Metathesis Polymerization Using a Bimetallic Initiator: Influence of a Flexible Spacer in the Side Chain Liquid Crystalline Block, Macromol., 2006, 39, 8241-8249.) Polynorbornenes have the advantage that, unlike commercial membranes, they do not have any weak points for degradation in alkaline environments: neither unshielded imidazole rings, aryl ether compounds, nor benzylic ammonium compounds or other heteroatom carbon bonds in the polymer backbone. They offer versatile functionalization options due to the wide range of monomer structures, which can be synthesized, for example, by Diels-Alder reactions of an Aiken with dicyclopentadiene. Polymers based on norbornene derivatives can be adapted in a variety of ways to achieve a balance of stability and flexibility while simultaneously achieving high conductivity. Chemical stability is ensured by the absence of imidazole rings or aryl ether bonds (S. Martinez-Arranz et al., Versatile Route to Functionalized Vinylic Addition Polynorbornenes, Macromolecules, 2010, 43, 7482-7487). Polynorbornenes thus exhibit promising properties for potential use in AEMs, but so far they have been limited to AEMs that are either chemically stable or exhibit excellent conductivity. To date, no polymer material based on polynorbornenes has been described that combines good mechanical properties with high ionic conductivity. TASK The object of the present invention was to provide novel alkaline anion exchange membrane materials that do not have the disadvantages described above. In particular, one object of the invention was to provide improved alkaline anion exchange membrane materials in the form of water-insoluble polymer membranes (AEMs) that possess high anion conductivity, in particular hydroxide and / or chloride conductivity, as well as high chemical, thermal, and / or mechanical stability. A further object of the invention was to provide improved membrane materials that are particularly suitable for use as alkaline (anion exchange) membranes or anion-conductive membranes, as electrode materials, as electrolytes, or as ionomers.A further object of the invention was to provide improved membrane materials for use in electrolysis processes, in water electrolysis processes (such as seawater, brackish water or demineralized water electrolysis), in electrodialysis, diffusion dialysis, Donnan dialysis or in fuel cells as well as in (redox) flow batteries. The inventors of the present invention have surprisingly found suitable norbornene derivatives which are suitable for the production of norbornene-based copolymers and polymer membranes obtainable therefrom with high stability and at the same time good anion conductivity and thus for their use in alkaline (anion exchange) membranes. DESCRIPTION OF THE INVENTION The objects of the present invention were surprisingly achieved by providing new water-insoluble polymer membranes (AEMs) based on polymers or copolymers which contain quaternized norbornene derivative monomer units of the following formula (I) and norbornene-based comonomers of the following formula (Exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene). In the monomer units of formula (I), which is also referred to as norbornene derivative monomer (EM), the substituent R 1 for a polyether chain -(CH2OCH2-)I (with I = 1 - 10), which together with a -CH2- group, via which a quaternary ammonium group from an amine base A 1acts as a kind of spacer or spacer chain between the norbornene-based polymer backbone and the quaternary amine base. Chemically stable and excellently conductive water-insoluble anion-conductive polymer membranes (AEMs) can be formed from polymers or copolymers containing such monomer units (I), particularly by copolymerization with exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene as a norbornene-based comonomer. The present invention is described in more detail below and particularly includes the following aspects: [1] Water-insoluble polymer membrane (AEM) containing a copolymer with a) quaternized norbornene derivative monomer units (EM) of the following formula (I), wherein R 1 a (-CH2OCH2-)I polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1is an amine base selected from the group: where the bond to the -R 1 -CH2-spacer of the norbornene derivative monomer unit (I) via a nitrogen atom to form a quaternary ammonium group; and n denotes the degree of polymerization; and b) norbornene-based comonomers (AM) of the following formula (exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene). [2] Water-insoluble polymer membrane (AEM) according to [1], wherein the quaternized norbornene derivative monomer units (EM) of formula (I) have an -R 1 -CH2-spacer, where R 1 a (-CH2OCH2-)I polyether chain with I = 2, according to the following formula (ll) (lD, where A 1 an amine base according to claim [1]. [3] Water-insoluble polymer membrane (AEM) according to [1] or [2], wherein the quaternized norbornene derivative monomer unit (EM) (I) or (II) is polymerized with the norbornene-based comonomer (AM), forming copolymer units (EM-co-AM) of the formula (II-I), (ll-l) where co is a copolymerized bond and A 1 represents an amine base according to [1] and n and m each denote the degree of polymerization. [4] Water-insoluble polymer membrane (AEM) according to [1] to [3], further comprising further norbornene-based comonomers selected from the following group: Water-insoluble polymer membrane (AEM) according to [1] to [4], wherein the quaternized Norbornene derivative monomer unit (EM) (I) or (II) with the norbornene-based Comonomers form block copolymers and block copolymer units (EM-block-AM) of the Formula (ll-ll) where block is a block copolymerized bond and A 1 represents an amine base according to [1], and n and m each denote the degree of polymerization. [6] Water-insoluble polymer membrane (AEM) according to [1] to [5], wherein the amine base A 1 in the quaternized norbornene derivative monomer units is selected from the group: where the bond to the -R 1 -CH2-spacer of the norbornene derivative monomer unit via a nitrogen atom to form a quaternary ammonium group. [7] Water-insoluble polymer membrane (AEM) according to [1] to [6], wherein the amine base A 1 in the quaternized norbornene derivative monomer units is selected from the group: Tetramethylimidazolium and quinuclidinium. [8] Water-insoluble polymer membrane (AEM) according to [1] to [7], wherein the copolymers are additionally reinforced by a) blending with a chemically inert matrix polymer, and / or b) covalent crosslinking, and / or c) crosslinking by non-covalent interactions comprising ionic Interactions, dipole-dipole interactions, H-bonds Interactions and van der Waals interactions with a physicochemical reactant, and / or d) chemically inert particles, meshes or fibers. [9] Water-insoluble polymer membrane (AEM) according to [1] to [8], which are in the form of a blend membrane with at least one chemically inert matrix polymer, wherein chemically inert matrix polymers are selected from the group (ii) from the group of isatin polymers comprising Polyoxindolediphenylbutane (PODPB) Polyoxindolebiphenylene (POBP)

[0010] Water-insoluble polymer membrane (AEM) according to [8], wherein the matrix polymers are selected from the group of isatin polymers.

[0011] Water-insoluble polymer membrane (AEM) according to one of [1] to

[0010] , which contains one or more further components selected from the group comprising crosslinking reagents, organic and / or inorganic nano- or microparticulate flow agents, fillers, support materials, stabilizers, phase compatibilizers such as block copolymers, catalysts and / or dyes, and mixtures thereof.

[0012] Water-insoluble polymer membrane (AEM) according to one of [1] to

[0011] wherein the copolymers with the monomer units (I) or (II), or copolymers according to formula (II-I) or block copolymers according to formula (II-II) are present as cross-linked copolymers.

[0013] Water-insoluble polymer membrane (AEM) according to one of [1] to

[0012] wherein the copolymers are cross-linked with a cross-linking reagent selected from the group of quaternizing diamines (III-A) and (III-B): (IH-A) (lll-B) where Y are linear or branched Ci-Ci2-alkyl chains, preferably Ci-Cs-alkyl chains, more preferably C4-Cs-alkyl chains; and X 1 , X 2 , X 3 and X 4 are each the same or different and independently of one another are linear or branched Ci-Cs-alkyl chains; or wherein X 1 and / or X 2 each with X 3 and / or X 4 together with the nitrogen atom to which they are attached, form one or two rings to form a diazacyclo or a diazabicyclo unit; and wherein Z are each the same or different and independently of one another linear or branched Ci-C alkyl chains, preferably Ci-Cs alkyl chains.

[0014] Water-insoluble polymer membrane (AEM) according to

[0013] wherein the crosslinking reagent (III-A) N,N,N',N'-Tetramethylhexylenediamine (TMHDA) or 1,4-diazabicyclo[2.2.2]octane and the crosslinking reagent (III-B) 1-Methyl-4-[3-(1-methyl-4-piperidyl)propyl] piperidine

[0015] Norbornene monomer according to the following formula: (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene)

[0016] Norbornene monomer according to the following formula wherein A 1 represents an amine base according to [1], [6] or [7].

[0017] Copolymer according to one of the following formulas (II-A) and (II-B): R 2 = a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; A 1 represents an amine base according to [1], [6] or [7]; A 2 represents a leaving group Br; n represents the degree of polymerization of the monomer and m represents the degree of polymerization of the comonomer; and co represents a copolymerized bond.

[0018] Copolymer according to one of the following formulas (II-C) and (II-D): (Il-C) (ll-D) wherein R 2 = a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; A 1 represents an amine base according to [1], [6] or [7]; A 2 represents a leaving group Br; n represents the degree of polymerization of the monomer and m represents the degree of polymerization of the comonomer; and block represents a block copolymerized bond.

[0019] Copolymer according to

[0017] or

[0018] wherein R 2represents a (-CH2OCH2-) polyether chain with I = 2.

[0020] Copolymer according to

[0017] to

[0019] which is present as a cross-linked copolymer.

[0021] Copolymer according to

[0020] , which is cross-linked via quaternized diamines (III-A) and / or (III-B) as defined in

[0013] or

[0014] .

[0022] A process for producing a water-insoluble polymer membrane (AEM) according to any one of [1] to

[0014] , comprising the steps: (a) polymerization or copolymerization of norbornene monomers according to

[0015] and / or

[0016] with the norbornene-based comonomers (AM) according to [1] and optionally with one or more identical or different further norbornene-based comonomers according to [4]; (b) if necessary substitution of the Br leaving group A 2 with an amine base A 1 according to [1], [6] or [7],

[0023] Process according to

[0022] , wherein the quaternization with the amine base A1 according to [1], [6] or [7] using the Menschutkin reaction.

[0024] Process according to

[0022] and

[0023] , comprising before step (b) an additional step of crosslinking at the leaving group A 2 with quaternizing diamines (III-A) and / or (III-B) as defined in

[0013] or

[0014] , followed by quaternization according to step (b) with an amine base A 1 as defined in [1], [6] or [7].

[0025] Process according to one of

[0022] to

[0024] , comprising an additional step of blending with one or more chemically inert matrix polymers as defined in [9] or

[0010] for producing the water-insoluble polymer membranes (AEM) in the form of blend membranes.

[0026] Process for the preparation of copolymers according to

[0017] to

[0021] , comprising steps (a) and (b) as described in

[0022] to

[0024] .

[0027] Process for the preparation of the monomers according to

[0015] and

[0016] by Diels Alder reaction of cyclopentadiene with an olefinic, hydroxy-substituted polyether chain (VA), followed by the substitution of the hydroxy group in (VA) by a leaving group A 3 and if necessary substitution of the leaving group A 3 by a leaving group A 2 : wherein R 2 = a (-CH2OCH2-) polyether chain with I = 2; and where A 1 an amine base according to any one of [1], [6] or [7] and A 2 represents a leaving group Br and A 3 a leaving group selected from sulfonic acid esters, preferably mesylates, tosylates or triflates.

[0028] Process according to

[0027] further comprising a process step for substituting the leaving group A 3 orA 2 by an amine base A 1 according to [1], [6] or [7],

[0029] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] as an alkaline anion exchange membrane or as an anion-conductive membrane.

[0030] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] as a binder material for the production of electrodes or catalyst layers.

[0031] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] as electrolyte or as ionomer.

[0032] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] in electrolysis processes, electrodialysis, (electro-)diffusion dialysis or Donnan dialysis.

[0033] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] in fuel cells, in water electrolysis processes or in (redox) flow batteries. DETAILED DESCRIPTION OF THE INVENTION As described above, the object of the invention is achieved by novel water-insoluble polymer membranes based on copolymers with norbornene derivative monomer units with quaternized polyether chains and selected norbornene-based comonomers. I. Water-insoluble polymer membranes based on copolymers of quaternized polyether-norbornene derivative monomer units The invention relates to a novel water-insoluble polymer membrane (AEM) based on polymers or copolymers with norbornene derivative monomer units (EM) which have a quaternized polyether alkyl chain as a spacer and are represented by the following formula (I), wherein R 1 a (-CH2OCH2-)I polyether chain, with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1 an amine base selected from the group of quaternizing amine bases; and n denotes the degree of polymerization. For the purposes of the present invention, a copolymer or the polymer membrane according to the invention is considered to be water-insoluble if it or the copolymer absorbs less than 400 percent by weight of water, based on its own weight (dry weight). Therein, the inventive norbornene derivative monomer units (I) are functionalized with a quaternized polyether chain. The quaternization is carried out by a quaternary nitrogen group A 1 which is bonded to the polyether chain via a [-CH2-] unit. The polymerization of such functionalized norbornene derivative monomer units according to (I) leads to so-called precursor polymers, which can be present in the inventive membranes in the form of block copolymers or random copolymers or form them. The monomers used can be commercially available or, particularly if they are novel monomers according to the invention, can be prepared, for example, by means of a Diels-Alder reaction of dicyclopentadiene and a suitable alkene. For use in the inventive AEMs, these precursor polymers are functionalized with amine bases in a quaternization reaction and thus converted into the inventive anion exchange polymers. In principle, it is also possible to introduce other ionic groups or functionalizations. Various mechanisms are available for polymerization, including cationic polymerization, polymerization using a metallocene complex, vinyl addition polymerization, or ring-opening polymerization (ROMP). For the purposes of the invention, an alkyl chain, if mentioned herein, refers to a straight-chain or branched, saturated alkyl chain having 1 to 20 carbon atoms, "Ci-2o-alkyl." From the group of straight-chain, saturated alkyl chains, those having 1 to 8 carbon atoms, "Ci-8," are preferred, more preferably those having 4 to 8 carbon atoms, "C4-8." Examples of these are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, neo-pentyl, n-hexyl, 2-Methylpentyl, 3-Methylpentyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, n-Heptyl, 2-Methylhexyl, 3-Methylhexyl, 2,2-Dimethylpentyl, 2,3-Dimethylpentyl, 2,4-Dimethylpentyl, 3,3- Dimethylpentyl, 3-Ethylpentyl, 2,2,3-Trimethylbutyl, n-Octyl, 2-Methylheptyl, 3-Methylheptyl, 4- Methylheptyl, 2,2-Dimethylhexyl, 2,3-Dimethylhexyl, 2,4-Dimethylhexyl, 2,5-Dimethylhexyl, 3,3-Dimethylhexyl, 3,4-Dimethylhexyl, 3-Ethylhexyl, 2,2,3-Trimethylpentyl, 2,2,4- Trimethylpentyl, 2,3,3-Trimethylpentyl, 2,3,4-Trimethylpentyl, 3-Ethyl-2-methyl pentyl 3-Ethyl- 3-methylpentyl, 2,2,3,3-Tetramethylbutyl, n-Nonyl, 2-Methyloctyl, 3-Methyloctyl, 4-Methyloctyl, 2.2-Dimethylheptyl, 2,3-Dimethylheptyl, 2,4-Dimethylheptyl, 2,5-Dimethylheptyl, 2,6- Dimethylheptyl, 3,3-Dimethylheptyl, 3,4-Dimethylheptyl, 3,5-Dimethylheptyl, 4,4- Dimethylheptyl, 3- Ethyl heptyl, 4-Ethylheptyl, 2,2,3-Trimethylhexyl, 2,2,4-Trimethylhexyl, 2,2,5-Trimethylhexyl, 2,3,3-Trimethylhexyl, 2,3,4-Trimethylhexyl, 2,3,5-Trimethylhexyl, 2,4,4- Trimethylhexyl, 3,3,4-Trimethylhexyl, 3-Ethyl-2-methylhexyl, 4-Ethyl-2-methylhexyl, 3-Ethyl-3- methylhexyl, 3-Ethyl-4-methylhexyl, 2,2,3,3-Tetramethylpentyl, 2,2,3,4-Tetramethylpentyl, 2,2,4,4-Tetramethylpentyl, 2,3,3,4-Tetramethylpentyl, 3-Ethyl-2,2-dimethylpentyl, 3-Ethyl-2,3- dimethylpentyl, 3-Ethyl-2,4-dimethylpentyl und 3,3-Diethylpentyl. Bevorzugt sind insbesondere n-Butyl, i-Butyl, n-Pentyl, i-Pentyl, neo-Pentyl, n-Hexyl, 2- Methylpentyl, 3-Methylpentyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, n-Heptyl, 2-Methylhexyl, 3-Methylhexyl, 2,2-Dimethylpentyl, 2,3-Dimethylpentyl, 2,4-Dimethylpentyl, 3,3- Dimethylpentyl, 3-Ethylpentyl, 2,2,3-Trimethylbutyl, n-Octyl, 2-Methylheptyl, 3-Methylheptyl, 4- Methylheptyl, 2,2-Dimethylhexyl, 2,3-Dimethylhexyl, 2,4-Dimethylhexyl, 2,5-Dimethylhexyl, 3.3-Dimethylhexyl, 3,4-Dimethylhexyl, 3-Ethylhexyl, 2,2,3-Trimethylpentyl, 2,2,4- Trimethylpentyl, 2,3,3-Trimethylpentyl, 2,3,4-Trimethylpentyl, 3-Ethyl-2-methyl pentyl 3-Ethyl- 3-methylpentyl, 2,2,3,3-Tetramethylbutyl. Noch bevorzugter sind n-Butyl, n-Pentyl,n-Hexyl, n- Heptyl und n-Octyl. Ganz besonders bevorzugt ist eine lineare oder verzweigte Ce- Alkylgruppe. If an alkyl chain forms a spacer in monomer units described herein, their total chain length results from the chain length of the introduced alkyl chain and the [-CH2-] group via which the amine base A 1 (or a leaving group A 2 / A 3 ) is bonded, for example an n-butyl spacer is present when an n-propyl alkyl chain is introduced. For the purposes of the invention, a polyether chain, in particular as substituent R 1 or R 2In the formulas defined herein, straight-chain polyether chains having 2 to 20 carbon atoms and 1 to 10 oxygen atoms are "(-CH2OCH2-)I-IO". From the group of straight-chain polyether radicals, those having 2 to 10 carbon atoms and 1 to 5 oxygen atoms are preferred, "(-CH2OCH2-)I-5", more preferred are those having 1 to 5 carbon atoms and 1 to 3 oxygen atoms, "(-CH2OCH2-)I.3". A chain length of H2-)2" or "(-CH2OCH2-CH2OCH2-)" is very particularly preferred. Examples of these are (-CH2OCH OCH2-), (-CH2OCH2CH2OCH2CH2OCH2-), (- CH2OCH2CH2OCH2CH2O or (-CH2OCH2CH2OCH2CH2CH2-). Particularly preferred are (-CH2OCH2-), (-CH2OCH2 CH2CH2OCH2CH2OCH2-). Even more preferred is (-CH2OCH2CH2OCH2-). If a polyether chain is used as a spacer in the monomer units according to the invention as R 1 or R 2 introduced, this results in a polyether alkyl spacer via which the amine base A 1 (or a leaving group A2 / A 3 ) and the total chain length of such a polyether alkyl spacer results from the chain length of R 1 or R 2 plus the [-CH2-] group, for example (-CH2OCH2)-CH2- when R 1 or R 2 (-CH2OCH2-) or (- CH2OCH2-CH2OCH2-)CH2- when I = 2. Amine bases in the sense of the invention are amino compounds which form a quaternary amino group via a nitrogen group with the alkyl or polyether chain attached via -CH2-. Examples of quaternizing amine bases include: where the bond to the -R 1 -CH2- or -R 2 -CH2- spacer of the norbornene derivative monomer units via a suitable nitrogen atom to form a quaternary ammonium group. According to the invention, the amine bases are selected from the group; preferred from the group: Particularly preferred amine bases are: Tetramethylimidazolium and quinuclidinium. The copolymers according to the invention can in principle be prepared with the same or different amine bases A 1 quaternized. This means that, if necessary, mixtures of different tertiary N-basic compounds (amine bases) can also be used for quaternization. The bond between the inventive -R 1 -CH2- or -R 2 -CH2- chain and the amine base A 1 can in principle take place at any quaternizable nitrogen in the amine base. In the copolymers according to the invention with the norbornene derivative monomer units (I) shown above, n and m respectively denote the degree of polymerization. In a preferred aspect of the invention, norbornene derivative monomer units (I) are copolymerized with identical or different comonomers from the group of norbornene-based comonomers. Hydrophobic norbornene-based comonomers are preferably copolymerized to thereby improve the stability of the AEMs. The copolymers according to the invention comprise at least norbornene-based comonomers (AM) of the following formula: (Exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene). However, it is also possible to introduce additional norbornene-based comonomers, which can be selected from the following group, or mixtures thereof: Aromatic-substituted norbornene comonomers are particularly preferred. Preferably, two or more different comonomers are used, allowing the IEC and other properties to be controlled and precisely adjusted. The inventive combinations of ether-functionalized norbornene (i.e. those in which the spacer is a polyether chain R 1 / R 2 with an aromatically substituted norbornene such as exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene leads to new copolymers with surprisingly improved properties and their particular suitability as stable, in particular alkali-stable, AEMs. Water-insoluble polymer membranes (AEM) comprising the same or different Copolymers can in principle be represented by the general formula (ll-co): where CO = represents a copolymerized bond and M 1a norbornene derivative monomer unit (I) as defined herein and M 2 corresponds to one of the norbornene-based comonomers defined herein, and n is the degree of polymerization of M 1 and m is the degree of polymerization of M 2 designated. It is also possible to polymerize the copolymers according to the invention as block copolymers and thus to provide water-insoluble polymer membranes (AEM) comprising the same or different block copolymers, which can in principle be represented by the general formula (II-block): (ll-block) where block = a block copolymerized bond and M 1 a norbornene derivative monomer unit (I) as defined herein and M 2 corresponds to one of the norbornene-based comonomers defined herein, and n is the degree of polymerization of M 1 and m is the degree of polymerization of M2 designated. Block copolymers are those copolymers that, in contrast to other copolymers, have a more controlled, strictly determined composition of monomers or comonomers. While copolymers as a whole represent a randomly distributed network of monomer or comonomer units, the order in which linear block copolymers form, for example, is characterized by a consistent sequence of the different units, for example, according to the pattern -ABA-, where A and B each represent different monomers or comonomers. To ensure block copolymerization, the reaction must be regulated more strictly than with other copolymerizations, for example by first bringing the monomers or comonomers into contact with each other step by step. Surprisingly, it was found that inventive AEMs based on inventive block copolymers already exhibit excellent properties and generally do not require additional reinforcement, e.g., by blending or crosslinking as described below. Block copolymers according to the invention also proved extremely promising with regard to their applicability and long-term stability in AEMs. In principle, the copolymers and block copolymers according to the invention are already suitable for use as water-insoluble polymer membranes (AEMs). However, in a further aspect of the invention, additional reinforcements can be made to the AEMs according to the invention. Possible reinforcements include, for example, modifications of the AEMs by a) mixing (blending) with chemically inert matrix polymers, b) covalent crosslinking of the polymers according to the invention with crosslinking reagents, c) crosslinking through noncovalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen-bonding interactions, and van der Waals interactions with a physicochemical reactant, and d) reinforcement through the addition of chemically inert particles, fibers, or meshes. In the case of reinforcement by chemically inert particles, fibers or braids, these can optionally be provided with hydrophilic groups or ion exchange groups either be modified superficially or throughout. This allows the compatibility between the membrane material and these particles, braids, or fibers to be improved or specifically adjusted as needed. This can also counteract possible delamination. In principle, combinations of one or more of the aforementioned reinforcements can also be present in the AEMs. The reinforcement has the effect of making the AEMs even more chemically stable in the anionic environment, further reducing their water absorption and / or additionally increasing their mechanical stability. In a further aspect, the invention thus also encompasses novel water-insoluble polymer membranes (AEM) in the form of blend membranes containing the copolymers according to the invention in a blend (a mixture) with one or more chemically inert matrix polymers. For the purposes of the invention, chemically inert matrix polymers can preferably be selected from the group of polybenzimidazoles (PBIs), including, for example, the following: Surprisingly, the inventors have discovered that, in addition to the aforementioned PBIs, isatin-derived polymers are also excellently suited to enable significant improvements in the chemical and mechanical stability of the inventive water-insoluble polymer membranes containing the inventive norbornene monomer units. Examples of suitable isatin matrix polymers are polyoxindole diphenylbutane (PODPB) and polyoxindole biphenyls (POBP): Polyoxindolediphenylbutane (PODPB) Polyoxindolebiphenylene (POBP) In principle, it is also possible to use mixtures of the matrix polymers shown, for example mixtures of different PBIs, different isatin polymers or mixtures of PBIs with other suitable matrix polymers, such as isatin polymers. When using a blend polymer, attention must be paid to the compatibility and miscibility of both polymers (copolymer and matrix polymer). It is also important that the blend polymer is chemically stable and has excellent mechanical properties. The polybenzimidazoles and isatin matrix polymers described herein, such as in particular the particularly preferred oxy-polybenzimidazole (OPBI), polyoxindole diphenylbutane (PODPB) and polyoxindole biphenyls (POBP), represent a good choice, and surprisingly it has been found that even low mass fractions of these polybenzimidazoles or isatin matrix polymers < 10.0 wt.%, < 9.0 wt.%, < 8.0 wt.%, < 7.0 wt.%, < 6.0 wt.%, < 5.0 wt.%, < 4.0 wt.%, < 3.0 wt.%, < 2.0 wt.%, or < 1.0 wt.% (preferably < 5.0 wt.%) are sufficient to induce excellent mechanical properties. It is known from the prior art to use significantly larger amounts of matrix polymers (60 wt.%) in blend membranes (Konovalova et al., Blend membranes of polybenzimidazole and an anion exchange ionomer (FAA3) for alkaline water electrolysis: Improved alkaline stability and conductivity, J. Membr. Sci. 2018, 564, 653-662). In contrast, the inventors of the present invention have surprisingly found that smaller amounts of matrix polymers, up to a maximum of 10.0 wt.%, are sufficient to achieve a stabilizing effect, or that larger amounts are even detrimental. It was found that at a concentration of > 10.0 wt.%, the AEMs no longer conduct but become insulating and are no longer usable for their intended purpose. At a concentration of 60 wt.%, as described in the prior art, the matrix polymer swells, forming a bulk effect with an insulating effect. What was also surprising in the production of blend membranes was that in such a blend membrane, even water-soluble polymers / copolymers / block copolymers become sufficiently water-insoluble or hydrophobic to be suitable as AEM simply by blending (mixing) with suitable matrix polymers described above. In a further aspect of the invention, the water-insoluble polymer membranes (AEM) can be reinforced by crosslinking and are then present as crosslinked polymers or copolymers (or block copolymers). Crosslinked polymers or copolymers / block copolymers refer to the polymers or copolymers / block copolymers according to the invention in which the linear polymer chains in the polymer backbone are crosslinked to one another by a crosslinking reagent. Suitable crosslinking reagents within the meaning of the invention include, in particular, quaternizing diamines (III), especially those according to the formulas (III-A) or (III-B): / (Yk (XW) (XW) (IH-A) (Hl-B) where Y are linear or branched Ci-Ci2-alkyl chains, preferably Ci-Cs-alkyl chains, more preferably C4-C8-alkyl chains; and X 1 , X 2 , X 3 and X 4 are each the same or different and independently represent linear or branched Ci-Cs-alkyl chains; or wherein X 1 and / or X 2 each with X 3 and / or X 4 together with the nitrogen atom to which they are attached, form one or two rings to form a diazacyclo or a diazabicyclo unit; and wherein Z are each the same or different and independently of one another linear or branched C1-C4 alkyl chains, preferably Ci-Cs alkyl chains. Therein, an “alkyl chain”, in particular as substituent Y and / or as one of the substituents X 1 to X 4and or as substituent Z in formulas (III-A) and (III-B) is the same as previously defined. Examples of possible crosslinking diamines (III-A) include: N,N,N',N'-Tetramethylmethylenediamine, N,N,N',N'-Tetramethylethylenediamine, N,N,N',N'- Tetramethylpropylenediamine, N , N, N', N'-Tetramethylbutylenediamine, N,N,N',N'- Tetramethylpentylenediamine, N,N,N',N'-Tetramethylhexylenediamine, N,N,N',N'- Tetraethylethylenediamine, N , N , N ', N '-Tetraethylethylenediamine, N,N,N',N'- Tetraethylpropylenediamine, N , N, N ' , N'-T etraethylbutylenediamine, N,N,N',N'- Tetraethylpentylenediamine, N,N,N',N'-Tetraethylhexylenediamine, N,N,N',N'- Tetrapropylmethylenediamine, N,N,N',N'-Tetrapropylethylenediamine, N,N,N',N'- Tetrapropylpropylenediamine, N , N, N', N'-T etrapropylbutylenediamine, N,N,N',N'- Tetrapropylpentylenediamine, N,N,N',N'-tetrapropylhexylenediamine. N,N,N',N'-tetramethylhexylenediamine is particularly preferred. For the purposes of the invention, the substituents X 1 and / or X 2 each with X 3 and / or X 4 together with the nitrogen atom to which they are bonded, form one or two rings to form a diazacyclo or a diazabicyclo unit. Examples of such diazacyclic diamines (III-A) include 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,4-dipropylpiperazine, 1,4-diisopropylpiperazine, 1,5-dimethyl-1,5-diazacyclooctane, 1,5-diethyl-1,5-diazacyclooctane, 1,5-dipropyl-1 ,5-diazacyclooctane, 1,5-diisopropyl-1,5-diazacyclooctane, 1,6-dimethyl-1,6-diazacyclodecane, 1,6-diethyl-1,6-diazacyclodecane, 1,6-dipropyl-1,6-diazacyclodecane and 1,6-diisopropyl-1,6-diazacyclodecane. Particularly preferred are 1,4-dimethylpiperazine, 1,4-diethylpiperazine, 1,5-dimethyl-1,5-diazaoctane and 1,5-diethyl-1,5-diazaoctane. Examples of such diazabicyclic diamines (III-A) include 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[3.3.3]undecane, and 1,6-diazabicyclo[4.4.4]tetradecane. 1,4-diazabicyclo[2.2.2]octane is particularly preferred. Beispiele möglicher quervernetzender Diamine (lll-B) umfassen: 1-Methyl-4-[(1-methyl-4-piperidyl)methyl]piperidin, 1 -Ethyl-4-[(1 -ethyl-4- piperidyl)methyl]piperidin, 1-Propyl-4-[(1-propyl-4-piperidyl)methyl]piperidin, 1-lsopropyl-4-[(1- isopropyl-4-piperidyl)methyl]piperidin, 1-Methyl-4-[2-(1-methyl-4-piperidyl)ethyl]piperidin, 1- Ethyl-4-[2-(1-ethyl-4-piperidyl)ethyl]piperidin, 1-Propyl-4-[3-(1-propyl-4- piperidyl)ethyl]piperidin, 1 -lsopropyl-4-[2-(1 -isopropyl-4-piperidyl)ethyl]piperidin, 1-Methyl-4- [3-(1 -m ethy l-4-pi peri dy l)pro py l]p i pe rid i n , 1 - Ethy l-4-[3- ( 1 -ethyl-4-pi peri dyl) p ropy l]p iperid i n , 1 - Propyl-4-[3-(1 -propyl-4-piperidyl)propyl]piperidin, 1-lsopropyl-4-[3-(1-isopropyl-4- piperidyl)propyl]piperidin, 1-Methyl-4-[4-(1-methyl-4-piperidyl)butyl]piperidin, 1-Ethyl-4-[4-(1 - ethyl-4-piperidyl)butyl]piperidin, 1-Propyl-4-[4-(1-propyl-4-piperidyl)butyl]piperidin, und 1- lsopropyl-4-[4-(1-isopropyl-4-piperidyl)butyl]piperidin.Besonders bevorzugt sind 1-lsopropyl- 4-[2-(1 -isopropyl-4-piperidyl)ethyl]piperidin, 1-Methyl-4-[3-(1-methyl-4- pi peri dyl)p ropyl] pi peri di n , 1 - Ethy l-4-[3-( 1 -ethy l-4-pi peri dy I) p ropy I] pi perid i n, 1 -Propyl-4-[3-(1 - propyl-4-piperidyl)propyl]piperidin, 1 -lsopropyl-4-[3-(1-isopropyl-4-piperidyl)propyl]piperidin, 1-Methyl-4-[4-(1-methyl-4-piperidyl)butyl]piperidin, 1 -Ethyl-4-[4-(1 -ethyl-4- piperidyl)butyl]piperidin, 1-Propyl-4-[4-(1-propyl-4-piperidyl)butyl]piperidin und 1-lsopropyl-4-. [4-(1 -isopropyl-4-piperidyl)butyl]piperidin, am meisten bevorzugt sind 1-Methyl-4-[3-(1-methyl- 4- p i pe ridy I) p ropy I] pi peri di n , 1 -Ethyl-4-[3-(1 -ethy I-4- pi peridy I) propy I] pi perid i n , 1 -Propyl-4-[3-(1 - propyl-4-piperidyl)propyl]piperidin, und 1-lsopropyl-4-[3-(1-isopropyl-4- piperidyl)propyl]piperidin. The smallest possible proportions of the crosslinker while still maintaining sufficient stability are preferred (e.g. < 7.5 mol% crosslinker per bromine group). Cross-linking can occur covalently, but cross-linking effects can also be achieved through ionic interactions, dipole-dipole interactions, hydrogen bonds, or van der Waals interactions. Ionic cross-linking effects occur, for example, through attractive interactions between the quaternized ammonium groups and their anionic counterions in the polymer backbone. A further cross-linking effect can also be achieved through charged hydrogen bonds between the quaternized ammonium groups and suitable molecular residues present in norbornene derivative monomer or norbornene-based comonomer units. Hydrogen bonds can form, for example, between donor hydrogen atoms from chemically inert matrix polymers such as polybenzimidazoles and acceptors according to the invention in the form of oxygens from polyether chains.Dipole-dipole interactions occur between all polar components and van der Waals interactions occur between all species introduced into the membrane. The water-insoluble polymer membranes (AEMs) according to the invention, either in the form of polymers / copolymers according to the invention, in the form of blend membranes or in the form of cross-linked polymers / copolymers according to the invention, or in the form of block copolymers or also in mixed forms of the aforementioned, can be in the form of powders, particles, granules, etc. (physical mixtures or powder blends) or in the form of (cast) layers, blocks, films, foils or as porous constructs or nonwovens. Hydrophobic polymer membranes (AEMs) according to the invention can also contain other components. Possible examples of further membrane components include crosslinking agents, organic and / or inorganic nano- or microparticulate flow agents, fillers, support materials, stabilizers, dyes, phase compatibilizers such as other suitable block copolymers, and other suitable auxiliaries and additives. It is possible to add individual components or mixtures of components from one or more of these groups. The quaternized copolymers according to the invention and / or the water-insoluble polymer membranes according to the invention are characterized by at least one, preferably by a combination of at least two of the properties described below. Water-insoluble polymer membranes (AEM) according to the invention are characterized either by the fact that they comprise quaternized copolymers according to the invention with hydrophobic comonomers as defined herein and that they are optionally present (particularly in the case of hydrophilic / water-soluble polymers / copolymers) in the form of a blend with at least one chemically inert matrix polymer, and / or that the polymer chains of the polymers / copolymers according to the invention are cross-linked with a cross-linking reagent from the group of quaternizing diamines. II. Monomers, comonomers, polymers, copolymers and block copolymers based on polyether-functionalized norbornene In a further aspect, the present invention also includes novel norbornene monomers comprising a polyether chain R 1 bw. R 2 with the meaning I = 2 and with a terminal Br leaving group or a terminal quaternizing amine base (A 1) are substituted: (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1 ]hept-2-ene) where A 1 an amine base as defined herein. In principle, norbornene monomers according to the invention can also be represented by the following general formulas: (IV-A) (IV-B) where R 2 a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and wherein A 2 is a leaving group, where leaving groups are preferably selected from the group of halogens or pseudohalogens, preferably halogens, even more preferably A 2 = Br. In this context, the term polyether chain, especially as substituent R 2 in the sense of (IV-A) and (IV-B), has the same meaning as defined above, in particular in connection with R 1 . The term amine base, especially as substituent A 1 in the sense of (IV-B) has the same meaning as defined above. The term leaving group in the sense of A 2 denotes suitable leaving groups, including, for example, halogen or pseudohalogen substituents such as chloro, bromo, iodo, azido, cyano, cyanato, isocyanato, fulminato, thiocyanato, and isothiocyanato substituents. Preferred are those from the group of halogen substituents such as chlorine, bromine, or iodo, with bromine being most preferred. A leaving group A 2 can in principle also be selected from the group comprising mesylates, tosylates and triflates in the aspects of the invention described herein. Examples of possible monomers (IV-A) include 5-(2-bromoethoxymethyl)bicyclo[2.2.1]hept-2-ene, 5-[2-(2-bromoethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene and 5-[2-[2-(2-bromoethoxy)ethoxy]ethoxymethyl]bicyclo[2.2.1]hept-2-ene. Particularly preferred is 5-[2-(2-bromoethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene: 5-[2-(2-bromoethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene Beispiele möglicher Monomere (IV-B) umfassen 2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethyl- trimethylammonium, 2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl- trimethylammonium, 2-[2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethoxy]ethyl- trimethylammonium, 2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethyl-tetramethylimidazolium, 2- [2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl-tetramethylimidazolium, 2-[2-[2-(2- bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethoxy]ethyl-tetramethylimidazolium, 2-(2- bicyclo[2.2.1]hept-5-enylmethoxy)ethyl-chinuclidinium,, 2-[2-(2-bicyclo[2.2.1]hept-5- enylmethoxy)ethoxy]ethyl-trimethyl-chinuclidinium, und 2-[2-[2-(2-bicyclo[2.2.1]hept-5- enylmethoxy)ethoxy]ethoxy]ethyl-trimethyl-chinuclidinium. Besonders bevorzugt sind 2-[2-(2- bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl-trimethylammonium, 2-[2-(2-bicyclo[2.2.1]hept- 5-enylmethoxy)ethoxy]ethyl-tetramethylimidazolium und 2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl-trimethyl-quinuclidinium. Most preferred is 2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyltrimethylammonium. A further aspect of the invention relates in particular to copolymers of the general formula (II-co), (ll-co) wherein M 1 a norbornene derivative monomer unit (lA) or (lB) corresponds (lA) (lB) with R 2 = a (-CH2OCH2-) polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, preferably with I = 2; and wherein A 1 is an amine base as defined herein and A 2 represents a leaving group as defined herein, preferably Br, and wherein M 2 a comonomer as defined herein and n is the degree of polymerization of M 1 and m is the degree of polymerization of M 2 designated. With regard to the terms polyether chain, amine base and leaving group, reference is made to the above definitions. For the purposes of the invention, M 2 a norbornene-based comonomer as previously defined. Particularly preferred embodiments of copolymers (I l-co) are shown in the formulas (II-A) and (II-B), wherein the comonomer from the group of norbornene-based comonomers is exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene: wherein R 2 a (-CH2OCH2-) polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with I = 2; and wherein A 1 an amine base selected from the group of quaternizing amine bases as defined herein; and A 2a leaving group as defined herein, preferably selected from the group of halogens or pseudohalogens, with halogens being particularly preferred, even more preferably A 2 = Br; and where n denotes the degree of polymerization of the monomer and m denotes the degree of polymerization of the comonomer. In a preferred variant, the copolymers according to the invention can also be present as crosslinked copolymers. For this purpose, for example, copolymers of formula (IA) or (II-A) are crosslinked with a crosslinking reagent such as a quaternizing diamine (III), preferably those according to the formulas (III-A) or (III-B) defined above. To obtain quaternized copolymers of formula (IB) or (II-B), the reaction is carried out with a quaternizing amine base as defined herein; such copolymers may additionally contain random amounts of crosslinking. A further aspect of the invention relates in particular to block copolymers of the general formula (II-block), (ll-block) wherein M 1 a norbornene derivative monomer unit (lA) or (lB) corresponds (lA) (lB) with R 2 = a (-CH2OCH2-) polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, preferably with I = 2; and wherein A 1 is an amine base as defined herein and A 2 represents a leaving group as defined herein, preferably Br, and wherein M 2 a comonomer as defined herein and n is the degree of polymerization of M 1 and m is the degree of polymerization of M 2 designated. With regard to the terms polyether chain, amine base and leaving group, reference is made to the above definitions. For the purposes of the invention, M2 a norbornene-based comonomer as previously defined. Particularly preferred embodiments of block copolymers (II-block) are shown in the formulas (II-C) and (II-D), wherein the comonomer from the group of norbornene-based comonomers is exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene: (ll-C) (ll-D) where R 2 a (-CH2OCH2-) polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with I = 2; and wherein A 1 an amine base selected from the group of quaternizing amine bases as defined herein; and A 2 a leaving group as defined herein, preferably selected from the group of halogens or pseudohalogens, with halogens being particularly preferred, even more preferably A 2= Br; and where n denotes the degree of polymerization of the monomer and m denotes the degree of polymerization of the comonomer. Particularly preferred copolymers and block copolymers are characterized by an R 2 -chain length of I = 2. III. Process for the preparation of monomers and comonomers according to the invention Suitable synthesis processes for preparing monomers and comonomers according to the invention are described below. If the monomers and / or comonomers described herein or their preparation processes described herein are new, the scope of the present invention also extends to the new monomers, comonomers and their preparation processes. The synthesis of the substituted norbornene derivatives used to prepare the AEMs and their copolymers according to the invention, as well as the The monomers / comonomers according to the invention can be prepared using several approaches. The route via a Diels-Alder reaction of dicyclopentadiene (diene) requires dicyclopentadiene and another alkene (dienophile) with any number of functional groups. In the case of a linear n-alkene, the norbornene derivative will only have one residue. However, it is important that one of the comonomers carries a halogen group so that a Menschutkin reaction can be carried out on the monomer or on the subsequent polymer. The halogen group can already be present after the Diels-Alder reaction or can only be converted into one in further reaction steps. Another possibility for the preparation of monomeric norbornene derivatives is via the Diels-Alder reaction of norbornadiene (dienophile) with another diene. Examples of suitable dienes are linear dienes such as butadiene, isoprene, 2,3-dimethylbuta-1,3-diene and 2,3-difluorobuta-1,3-diene or cyclic dienes such as cyclohexa-1,4-diene, cyclohepta-1,4-diene or (1Z,5Z)-cycloocta-1,5-diene. In a further step, it is necessary to equip the halogen substituent of the norbornene-based monomers with a quaternary ammonium group by a Menschutkin reaction, whereby tertiary N-basic compounds such as the amine bases defined herein (A 1), e.g., N-methylpiperidine, trimethylamine, quinuclidine or quinuclidinol, or 2,3,4,5-tetramethylimidazole, in particular those identified herein as preferred. The monomer building blocks thus obtainable can subsequently be polymerized to form a precursor polymer, preferably using transition metal-catalyzed ring-opening polymerization (molybdenum, titanium, tantalum, tungsten, ruthenium) or vinyl addition polymerization. In principle, there are no particular restrictions on the selection of amine bases for quaternization, and those described herein can be used, for example. A manufacturing process according to the invention can be summarized in the following three steps: 1. A Diels-Alder reaction between dicyclopentadiene and an olefinic, hydroxy-substituted polyether chain (V) to form an intermediate (VB). 2. Subsequently, the formation of a sulfonic acid ester (VC) from the intermediate (V- B). 3. Subsequently, the sulfonic acid ester can be substituted by a leaving group to form the norbornene monomer (IV-A) or by an amine base to form the norbornene monomer (IV-B). Furthermore, the sulfonic acid ester (VC) can be substituted by a leaving group to form the norbornene monomer (IV-A), followed by further substitution of the leaving group by an amine base to form the norbornene monomer (IV-B): wherein R 2 = a (-CH2OCH2-) polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably I = 2; and wherein A 1 is an amine base as defined herein and A 2 represents a leaving group as defined herein, preferably A is 2 = Br, and A 3a leaving group selected from sulfonic acid esters, preferably mesylates, tosylates or triflates. In this, the term polyether chain, especially as substituent R 2 in formulas (V-A), (VB), (VC) and (IV-A) the same as previously defined. For compounds according to (VA), for example, the total chain length for the olefinic, hydroxy-substituted polyether chain (VA) results from the sum of R 2 , the terminal [CH2=CH-] group and the [-CH2-] group, for example (CH2=CHCH2OCH2CH2-) when R 2 (-CH2OCH2-) or (CH2=CHCH2OCH2CH2OCH2CH2-) if R 2 (-CH2OCH2CH2OCH2-) is. For the purposes of the invention, an amine base, in particular as substituent A 1 in formulas (VA), (VB), (VC) and (IV-A) the same as previously defined. For the purposes of the invention, leaving group, in particular as substituent A 2in formula (IV-A) is the same as defined above. According to the invention, a Br leaving group (ie A 2 = Br). For the purposes of the invention, the substituent A defines 3 in particular, based on the sulfonic acid ester of formula (VC), a leaving group from the group of sulfonates. Preference is given to mesylate, tosylate, and triflate groups, particularly preferred is mesylate, Examples of compounds (VA) include 2-allyloxyethanol, 2-(2-allyloxyethoxy)ethanol, and 2-[2-(2-allyloxyethoxy)ethoxy]ethanol. 2-(2-allyloxyethoxy)ethanol is particularly preferred. Examples of compounds (VB) include 5-(2-hydroxyethoxymethyl)bicyclo[2.2.1]hept-2-ene, 5-[2-(2-hydroxyethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene, and 5-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxymethyl]bicyclo[2.2.1]hept-2-ene. 5-[2-(2-hydroxyethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene is particularly preferred. Examples of compounds (VC) include 2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethyl methanesulfonate, 2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl methanesulfonate, and 2-[2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethoxy]ethyl methanesulfonate. 2-[2-(2-bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethyl methanesulfonate is particularly preferred. The Diels-Alder reaction according to the invention is preferably carried out under inert conditions between dicyclopentadiene and an olefinic, hydroxy-substituted polyether chain. Since this is a reaction in bulk, the reactants themselves form the solvent. In the Diels-Alder reaction, an excess of the olefinic, hydroxy-substituted polyether chain (VA) is preferably present. The substance (VA) is added in a fivefold, fourfold, threefold, or double excess. A threefold excess is preferred. The Diels-Alder reaction is preferably carried out under reflux at 210 °C, 205 °C, 200 °C, 195 °C, 190 °C, 185 °C, 180 °C, 175 °C, or 170 °C. 205 °C, 200 °C, 195 °C, 190 °C, or 185 °C are preferred. 200 °C is particularly preferred. The Diels Alder reaction is preferably carried out for 6 - 24 h, 6 - 22 h, 6 - 20 h or 6 - 18 h, preferably 10 - 20 h, 10 - 18 h or 10 - 16 h, particularly preferably 16 h. In a subsequent step, the intermediate product (VB) from the Diels Alder reaction can be purified using vacuum distillation. Following vacuum distillation, the intermediate (VB) can be extracted from ethyl acetate and washed, for example with water. In a further reaction step, the intermediate (V-B) can be esterified with a sulfonic acid halide to form a sulfonic acid ester (VC) under inert conditions. For the purposes of the invention, sulfonic acid halides are preferably selected from the sulfonic acid chlorides, particularly preferred are methanesulfonic acid chloride, p-toluenesulfonic acid chloride or trifluoromethanesulfonic acid chloride, particularly preferred is methanesulfonic acid chloride. The reaction of the intermediate (VB) with the sulfonic acid halide is preferably carried out in chloroform, dichloromethane, chlorobenzene, dichlorobenzene, toluene, tetrahydrofuran, with chloroform and dichloromethane being preferred, and chloroform being most preferred. The esterification of the intermediate (VB) to the sulfonic acid ester (VC) is preferably carried out in the presence of 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1 or 1.0 equivalents of triethylamine, preferably 1.5, 1.4, 1.3, 1.2, 1.1 or 1.0 equivalents, particularly preferably 1.2 equivalents. The esterification of the intermediate (VB) to the intermediate (VC) preferably takes place at 5 °C, 4 °C, 3 °C, 2 °C, 1 °C, 0 °C, -1 °C, -2 °C, -3 °C, -4 °C or -5 °C. Preference is given to 2 °C, 1 °C, 0 °C, -1 °C or -2 °C, and 0 °C is particularly preferred. According to the invention, the sulfonic acid ester (VC) can be purified by adding it to hydrochloric acid and extracting it from chloroform. In a further reaction step according to the invention, the sulfonic acid ester (VC) can be reacted with an alkali halide or alkali pseudohalide to form a norbornene monomer of the formula (IV-A) according to the invention. Alkali halides or alkali pseudohalides according to the invention are preferably selected from LiCl, LiBr, LiIl, LiN3, LiCN, LiOCN, LiNCO, LiCNO, LiSCN, LiNCS, NaCl, NaBr, Nal, NaN3, NaCN, NaOCN, NaNCO, NaCNO, NaSCN, NaNCS, KCl, KBr, KL, KN3, KCN, KOCN, KNCO, KCNO, KSCN or KNCS, LiCl, LiBr, LiIl is preferred, LiBr is particularly preferred. The conversion of the sulfonic acid ester (VC) to the inventive norbornene monomer (IV-A) is preferably carried out in a suitable solvent selected from acetone, tetrahydrofuran (THF), dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, ethanol, or methanol. Acetone and THF are preferred. Acetone is most preferred. When converting the sulfonic acid ester (VC) to the inventive norbornene monomer (IV-A), an excess of the alkali metal halide or alkali metal pseudohalide is preferably present. The alkali metal halide or alkali metal pseudohalide is added in a fivefold, fourfold, threefold, or double excess. A threefold excess is preferred. The conversion of the sulfonic acid ester (VC) to the inventive norbornene monomer (IV-A) can be carried out under reflux at 70 °C, 68 °C, 66 °C, 64 °C, 62 °C, 60 °C, 58 °C, or 56 °C. Preference is given to 66 °C, 64 °C, 62 °C, or 60 °C. 60 °C is particularly preferred. The conversion of the sulfonic acid ester (VC) to the norbornene monomer (IV-A) according to the invention can be carried out over 6 - 24 h, 6 - 22 h, 6 - 20 h or 6 - 18 h, preferably 10 - 20 h, 10 - 18 h or 10 - 16 h, particularly preferably 16 h. The norbornene monomers (IV-A) thus obtained can be purified by conventional methods, e.g. by adding them to water and extracting with ethyl acetate. In a further aspect of the invention, the sulfonic acid ester (VC) or the norbornene monomer (IV-A) can be reacted with an amine base to form quaternized norbornene monomers (IV-B). The quaternization of the intermediates (VC) or monomers (IV-A) to the norbornene monomer (IV-B) can be carried out under analogous conditions to the previously described quaternization of the polymers or copolymers. A special feature of this quaternization is that, in addition to the solvents mentioned above, ethyl acetate or acetonitrile are particularly preferred solvents. The preparation of the comonomers according to the invention, e.g. anthracene-based comonomers, can also be carried out via a Diels-Alder reaction. Figures 1 to 3 also show synthesis steps for the preparation of particularly preferred monomers / comonomers according to the invention. IV. Process for the preparation of copolymers, block copolymers and water-insoluble polymer membranes according to the invention The water-insoluble polymer membranes (AEM) according to the invention can be obtained by copolymerizing norbornene monomers according to formulas (IV-C) and (IV-D) with norbornene-based comonomers as defined herein. wherein R 1 a (-CH2OCH2-)! polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably I = 2; and A 1 an amine base selected from the group of quaternizing amine bases as defined herein; and A 2 a leaving group as defined herein, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, preferably halogens, even more preferably A 2 = Br. With regard to the terms polyether chain, amine base and leaving group, reference is made to the above definitions. Within the meaning of the invention, various polymerization mechanisms are conceivable for the norbornene monomers and norbornene-based comonomers of the invention for producing the membranes of the invention. These include cationic polymerization, polymerization using a metallocene complex, vinyl addition polymerization, or ring-opening polymerization. Water-insoluble polymer membranes of the invention are preferably obtained from copolymers produced by ring-opening polymerization. Monomers and comonomers according to the invention are dissolved in a suitable solvent and converted into the copolymers according to the invention by ring-opening polymerization using a catalyst under inert conditions. Inert conditions within the meaning of the invention refer to the exclusion of atmospheric oxygen during the synthesis methods according to the invention. According to the invention, this reaction takes place in an argon atmosphere. Suitable solvents for the ring-opening polymerization of monomers of the formula (IV- C) within the meaning of the invention include dichloromethane (DCM), chloroform, chlorobenzene, dichlorobenzene, toluene, THE. Particularly preferred are DCM, chloroform, or chlorobenzene. Most preferred is DCM. Suitable solvents for the ring-opening polymerization of monomers of the formula (IV- D) within the meaning of the invention comprise mixtures of dichloromethane and methanol, in particular ratios of dichloromethane:methanol 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, particularly preferred are 10:1, 9:1, 8:1 and 7:1. Most preferred are 10:1 and 9:1. Suitable solvents for precipitating a copolymer according to the invention include organic solvents such as dichloromethane (DCM), chloroform, chlorobenzene, dichlorobenzene, toluene, THF, methanol, propanol. In principle, all possible catalysts that are suitable for the polymerization mechanisms mentioned herein are typically also suitable for the synthesis of the polynorbornenes of the invention. Examples include the metal complexes developed by Grubbs and Schrock, as well as many other metal complexes based on molybdenum, titanium, tantalum, tungsten, ruthenium, palladium, and nickel. Suitable catalysts for carrying out the ring-opening polymerization according to the invention include Grubbs I (benzylidenebis(tricyclohexylphosphine)dichlororuthenium), Grubbs II (benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro (tricyclohexylphosphine)ruthenium), Grubbs III [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(3-bromopyridine)ruthenium(II), Schrock catalysts and other metal complexes based on Mo, Ti, Ta, W or Ru. Grubbs I and Grubbs II catalysts are preferred. Temperature control may be useful and necessary in the polymerization processes according to the invention. The temperature during the polymerization process according to the invention can be regulated, for example, using a cooling bath in the first few minutes and can increase over the course of the reaction. Temperature ranges of -20-50°C, -20-40°C, -20-30°C, or -20-25°C are possible. 0-30°C or 0-25°C is preferred, with 0-25°C being particularly preferred. The polymerization is usually stopped by adding a polymerization inhibitor. Polymerization inhibitors according to the invention include ethyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, and chloroethyl vinyl ether. Ethyl vinyl ether and ethylhexyl vinyl ether are preferred. Ethyl vinyl ether is particularly preferred. Figure 4 A) shows a ring-opening polymerization of a copolymer particularly preferred according to the invention. In cases where copolymers according to the invention, e.g. those prepared from norbornene monomers of the formula (IV-C), are used, a quaternization of the substituent A 2 (leaving group) with an amine base A 1 , as defined herein, i.e., an amine base from the group of quaternizing amine bases. The quaternization can be carried out before or after copolymerization is complete. Quaternization is preferably carried out using the Menschutkin reaction. In principle, it is possible in the processes described herein to keep the order of the copolymerization and quaternization steps variable, as described in detail herein. For this purpose, the copolymers according to the invention, e.g. those prepared from norbornene monomers of the formula (IV-C), and the amine base A 1in a suitable solvent, e.g. one selected from the group consisting of tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), chloroform, dioxane, tetrahydro-2H-pyran, glyme, diglyme, triglyme, DMSO, dimethylsulfone, sulfolane, or N-ethylpyrrolidone. A particularly preferred solvent is THF. The quaternization according to the invention of copolymers according to the invention, for example those prepared from norbornene monomers of the formula (IV-C), via a Menschutkin reaction is preferably carried out at 25 - 150 °C, 25 - 125 °C, 25 - 100 °C or 25 - 75 °, preferred are 25 - 75 °C, 30 - 75 °C, 35 - 75 °C or 40 - 75 °C, particularly preferred are 40 °C - 60 °C, most preferred is 50 °C. The inventive quaternization of copolymers according to the invention, e.g. those prepared from norbornene monomers of the formula (IV-C), via a Menschutkin reaction is preferably carried out for 24 - 72 h, 24 - 68 h, 24 - 64 h, 24 - 60 h, 24 - 56 h, 24 - 52 h or 24 - 48 h, preferably 24 - 48 h, particularly preferably 48 h. Figure 5 shows a quaternization by means of a Menshutkin reaction by introducing an amine base into a precursor polymer (copolymer) which is particularly preferred according to the invention. Water-insoluble polymer membranes (AEMs) according to the invention made from the copolymers according to the invention can be obtained by uniformly applying the dissolved copolymers to a smooth surface, e.g. a glass plate, with a doctor blade and subsequently evaporating the solvent. According to the invention, AEMs can be prepared from cross-linked copolymers. In such cases, copolymers, e.g., those prepared from norbornene monomers of formula (IV-C), can be cross-linked with a cross-linking reagent (III-A) or (III-B) prior to quaternization with an amine base. In this case, <10.0 mol%, <9.5 mol%, <9.0 mol%, <8.5 mol%, <8.0 mol%, <7.5 mol%, <7.0 mol%, <6.5 mol%, <6.0 mol%, <5.5 mol%, <5.0 mol%, <4.5 mol%, <4.0 mol%, <3.5 mol%, <3.0 mol%, <2.5 mol%, <2.0 mol%, 1.5 mol%, or 1 mol% of the crosslinking reagent is reacted with a polymer or copolymer based on a norbornene derivative monomer unit of the formula (IA). Preferred are <5.0 mol%, <4.5 mol%, <4.0 mol%, <3.5 mol%, <3.0 mol%, <2.5 mol%, <2.0 mol%, <1.5 mol% or <1.0 mol%, most preferred is <2.5 mol%. For the quaternization of precursor polymers or copolymers according to the invention which are cross-linked with a cross-linking agent, the cross-linking can be carried out first and then the cross-linked precursor polymer or copolymer can be quaternized by reaction in a solution of an amine base in one of the solvents previously described for quaternization via a Menschutkin reaction. The quaternization of precursor polymers or copolymers according to the invention via a Menschutkin reaction can be carried out in the same temperature range as previously defined. The quaternization of precursor polymers or copolymers according to the invention via a Menschutkin reaction can also be carried out over the same periods of time as previously defined. The process of cross-linking is shown schematically below: To produce the AEMs according to the invention in the form of blend membranes of the copolymers according to the invention, the copolymers according to the invention are dissolved together with a chemically inert matrix polymer, in particular those defined herein from the group of polybenzimidazoles or isatin polymers, in a suitable solvent, e.g. a solvent from the group of amides. Suitable solvents from the group of amides, which are particularly suitable for blending the polymers or copolymers according to the invention with a chemically inert matrix polymer, include dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), sulfolane, N-methylpyrrolidone (NMP), and dimethylformamide (DMF). DMAc, DMSO, or NMP are preferred. DMAc is particularly preferred. Surprisingly, it was found that oxy-polybenzimidazole or isatin polymers are particularly suitable because they form a homogeneous mixture with the polymers in DMAc. To produce the water-insoluble polymer membranes in the form of blend membranes, a proportion of 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, or 10 wt.% of the chemically inert matrix polymer is preferably blended with the copolymers of the invention. 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, or 5 wt.% is preferred, with 2.5 wt.% being particularly preferred. The blend membranes according to the invention can also be obtained by applying the solution comprising the polymers or copolymers according to the invention and the chemically inert matrix polymers to a surface such as a glass plate using a doctor blade and subsequently evaporating the solvent. By appropriate process control, homopolymers of the norbornene derivative monomer units (EM) and the norbornene-based comonomers (AM), as well as all copolymers with variable proportions of the different comonomers, can be produced. It is also fundamentally possible to prepare homopolymers of the norbornene derivative monomers (EM) according to formula (I) defined herein, preferably those of formula (II), each as defined herein. Such homopolymers also exhibit surprisingly good properties as alkali-stable AEMs. In contrast to the above-described production of copolymers by random copolymerization, block copolymers according to the invention can also be realized using ROMP. For this purpose, one of the two comonomers (EM) or (AM) is first polymerized and, after complete consumption of the monomer, a solution of the second monomer is added. In this way, polymers with the same composition but a different arrangement of the comonomers in the polymer can be produced. Otherwise, the process conditions described above also apply to block copolymerization. Since the block copolymers according to the invention already have a surprisingly high level of stability per se, further reinforcement, e.g., by cross-linking or blending with matrix polymers, is less relevant here than for the copolymers according to the invention and is therefore generally unnecessary. Figure 4 B) shows a block copolymerization of a block copolymer particularly preferred according to the invention. V. Use of the water-insoluble polymer membranes according to the invention Due to their advantageous properties, as described in detail above, the water-insoluble polymer membranes (AEM) according to the invention are particularly suitable as alkaline (anion exchange) membranes or anion-conductive membranes. This also opens up the possibility of use as a binder material for the production of electrodes or as a solid electrolyte, particularly in electrolysis processes, electrodialysis processes, diffusion dialysis processes, such as in particular diffusion dialysis, Donnan dialysis, and water electrolysis processes. In addition, the water-insoluble polymer membranes (AEM) according to the invention are particularly suitable for use in fuel cells or in (redox) flow batteries. The use of the water-insoluble polymer membranes (AEM) according to the invention as a binder material for the production of electrodes or catalyst layers, as well as as an ionomer, is also possible and encompassed by the invention. It has surprisingly been found that membranes with a suitable combination of mechanical stability and conductivity can be produced using the monomers and comonomers described herein, in particular the monomer combinations shown as preferred herein and described in more detail in the examples. Particularly preferred membranes according to the invention are characterized by an ion exchange capacity (IEC) in the range between 1.8 meq / g and 2.6 meq / g, with an average molecular weight between 30 and 100 kg / mol. Surprisingly, this makes it possible for the first time to synthesize the ether chains (R 1 or R 2 ) functionalized norbornene derivatives into a stable membrane. A particular aspect of the invention thus relates to electrodes, catalyst layer materials, fuel cells or flow batteries based on the water-insoluble polymer membranes (AEM) described herein, including in particular the embodiments described herein as blend membranes. The aspects of the invention described herein are further explained by the figures, but the invention is not to be seen as limited thereto. VI. Further aspects in the context of the invention Some further aspects in connection with the present invention are described below, which may represent alternative, supplementary, or specific features and further disclose the invention. A water-insoluble polymer membrane (AEM) containing a polymer or copolymer with a quaternized norbornene derivative monomer unit of the following formula (I), wherein R 1a linear or branched Ci-C2o-alkyl chain, preferably a Ci-C8-alkyl chain, more preferably a C4-C8-alkyl chain; or R 1 a (-CH2OCH2-)I polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1 is an amine base; and n denotes the degree of polymerization. . Water-insoluble polymer membrane (AEM) according to [1] where the amine base A 1 in the quaternized norbornene derivative monomer units (I), selected from the group: where the bond to the -R 1 -CH2-spacer of the norbornene derivative monomer unit (I) via a nitrogen atom to form a quaternary ammonium group; preferably the amine base A 1 selected from: Trimethylammonium, tetramethylimidazolium, and quinuclidinium. Water-insoluble polymer membrane (AEM) according to [1] or [2] further comprising identical or different comonomers, which are norbornene-based comonomers selected from the following group: exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene, and where preferred is: exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene . Water-insoluble polymer membrane (AEM) according to [1] to [3], wherein the quaternized norbornene derivative monomer unit (I) is polymerized with a norbornene-based comonomer to form a copolymer unit of the formula (II), where CO represents a copolymerized bond and M 1 a norbornene derivative monomer unit (I) as defined in [1] to [2] and M 2corresponds to a norbornene-based comonomer according to [3] and n is the degree of polymerization of M 1 and m is the degree of polymerization of M 2 Water-insoluble polymer membrane (AEM) according to [1] to [4], wherein the polymers and / or copolymers are additionally reinforced by e) blending with a chemically inert matrix polymer, and / or f) covalent crosslinking, and / or g) crosslinking by non-covalent interactions comprising ionic Interactions, dipole-dipole interactions, H-bonds Interactions and van der Waals interactions with a physicochemical reactant, and / or h) chemically inert particles, meshes or fibers. . Water-insoluble polymer membrane (AEM) according to [1] to [5], which are in the form of a blend membrane with at least one chemically inert matrix polymer. . Water-insoluble polymer membrane (AEM) according to [6], wherein chemically inert matrix polymers are selected from the group of polybenzimidazoles, including, for example, those from the group: Water-insoluble polymer membrane (AEM) according to [1] to [7], wherein the polymers or copolymers according to formula (I) or (II) are present as cross-linked polymers and / or copolymers. Water-insoluble polymer membrane (AEM) according to [8], wherein the polymers and / or copolymers are cross-linked with a cross-linking reagent selected from the group of quaternizing diamines (III-A) and (III-B): (lll-A) (lll-B) where Y linear or branched Ci-Ci2-alkyl chains, preferably Ci-Cs-alkyl chains, more preferably C4-Cs-alkyl chains, and X 1 , X 2 , X 3 and X 4 are each the same or different and independently of one another are linear or branched Ci-Ca alkyl chains; or wherein X 1 and / or X 2 each with X 3 and / or X 4 together with the nitrogen atom to which they are attached, form one or two rings to form a diazacyclo or a diazabicyclo unit; and wherein Z are each the same or different and independently of one another linear or branched Ci-C4-alkyl chains, preferably Ci-C5-alkyl chains; wherein preferably the crosslinking reagent (III-A) is selected from: N,N,N',N'-tetramethylhexylenediamine (TMHDA) 1,4-diazabicyclo[2.2.2] octane and wherein preferably the crosslinking reagent (II lB) is selected from: 1-methyl-4-[3-(1-methyl-4-piperidyl)propyl] piperidine. Norbornene monomer according to the following formula (IV-A) (IV-A) wherein R 2 a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and wherein A 2 is a leaving group, where leaving groups are preferably selected from the group of halogens or pseudohalogens, preferably halogens, even more preferably A 2 = Br; which is preferably 5-[2-(2-bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene: or norbornene monomer according to the following formula (IV-B) (IV-B) wherein R 2 a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and wherein A 1 an amine base according to [1] to [2]. polymer of formula (II), wherein M 1a norbornene derivative monomer unit (lA) or (lB) corresponds (lA) (lB) with R 2 = a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and wherein A 1 is an amine base according to [1] to [2] and A 2 represents a leaving group as defined in

[0010] and wherein M 2 a comonomer as defined in [3] and n is the degree of polymerization of M 1 and m is the degree of polymerization of M 2 wherein the copolymer is preferably one of the following formulas (I lA) and (II-B): wherein R 2 = a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and wherein A 1 is an amine base according to [1] to [2] and A 2represents a leaving group as defined in

[0010] and n denotes the degree of polymerization of the monomer and m the degree of polymerization of the comonomer. Process for producing a water-insoluble polymer membrane (AEM) according to [1] to [9], comprising the steps: (a) Polymerization or copolymerization of norbornene monomers of formula (IV-C) or (IV-D) (IV-C) (IV-D) where R 1 a linear or branched C-C2o-alkyl chain, preferably a C-C8-alkyl chain, more preferably a C4-C8-alkyl chain; or R 1 a (-CH2OCH2-)I polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1 an amine base as defined above and A 2 represent a leaving group as defined above; with one or more identical or different norbornene-based comonomers as defined above; (b) if necessary, substitution of the leaving group A 2 in polymerized / copolymerized norbornene monomers (IV-C) with an amine base A 1 as defined above; wherein the quaternization with the amine base A 1 preferably by means of the Menschutkin reaction; the order of the polymerization and quaternization steps is variable; (c) optionally comprising an additional step of blending with one or more chemically inert matrix polymers as defined above to produce the water-insoluble polymer membranes (AEM) in the form of blend membranes; and / or (d) optionally comprising a step of crosslinking the polymers / copolymers. Use of the water-insoluble polymer membrane (AEM) according to [1] to [9] as an alkaline anion exchange membrane or as an anion-conductive membrane, as a binder material for the production of electrodes or catalyst layers, as an electrolyte or as an ionomer, in electrolysis processes, electrodialysis, diffusion dialysis or Donnan dialysis, as well as in fuel cells, in water electrolysis processes or in (redox) flow batteries. DESCRIPTION OF THE CHARACTERS Fig. 1: Schematic representation of a synthesis of a monomer with a simple alkyl chain (R 1 = alkyl) and terminal bromine group (A 2 = Br) to illustrate the accessibility of functionalized norbornene derivatives. Fig. 2: Schematic representation of a synthesis according to the invention over three steps to a norbornene derivative with ether-functionalized side chain and terminal bromine group. Fig. 3: Schematic representation of a synthesis of a strongly hydrophobic comonomer according to the invention based on anthracene. Fig. 4: A) Schematic representation of a ring-opening polymerization of an ether-functionalized monomer according to the invention with an anthracene-based comonomer according to the invention. B) Schematic representation of a block copolymerization of an ether-functionalized monomer according to the invention with an anthracene-based comonomer according to the invention. Fig. 5: Schematic representation of a Menshutkin reaction on an inventive Precursor polymer for the preparation of anion exchange polymers according to the invention. Fig. 6: 1 H-NMR spectrum of the inventive monomer bromobutylnorbornene in chloroform. Fig. 7: (a) 1 H-NMR spectrum of the ether-functionalized norbornene derivative with OH end group according to the invention (b) 1H-NMR spectrum of the ether-functionalized Norbornene derivative with sulfonate end group (c) 1 H-NMR spectrum of the ether-functionalized Norbornene derivative with Br end group. Fig. 8: 1 H-NMR spectrum of the inventive comonomer based on anthracene in chloroform. Fig. 9: (a) 1 H-NMR spectrum of the copolymer according to the invention with Br leaving group on the ether-functionalized monomer (b) 1 H-NMR spectrum of the inventive copolymer with quaternized ether-functionalized monomer. Fig. 10: Molecular weight distributions of various copolymers according to the invention based on three monomers according to the invention to illustrate the successful polymerization, measured by GPC with THF as eluent with polystyrenes as Standard; (— EM-copoly = polymer with 65 mol% of the monomer from Figure 7c and 35 mol% of the monomer from Figure 8; — EM-copoly = polymer with 65 mol% of the monomer from Figure 7c and 35 mol% of the monomer from Figure 8; BM-copoly = copolymer of structure (II-B) with R 2 = CsHs andA 1 = TMA with 59 mol% of the monomer from Figure 6 and 41 mol% of the monomer from Figure 8) Fig. 11 : Tensile tests of cross-linked and OPBI-blended blend membranes according to the invention at different temperatures and humidities, each based on ether-functionalized monomers according to the invention copolymerized with anthracene-based monomers according to the invention, with an IEC of 2.0 meq / g. Fig. 12: Exponential behavior of the chloride conductivity of cross-linked and OPBI-blended blend membranes according to the invention upon variation of the IEC, each based on ether-functionalized monomers according to the invention copolymerized with anthracene-based monomers according to the invention, wherein an IEC of 2 or higher reflects suitable conductivities, measured in 1 M NaCl solution at room temperature. Fig. 13: Almost linear behavior of the water absorption of cross-linked and OPBI-blended blend membranes according to the invention upon changing the IEC, each based on ether-functionalized monomers according to the invention copolymerized with anthracene-based monomers according to the invention, wherein an IEC of 2 or higher reflects suitable conductivities. Fig. 14: Measurement of cell voltage over 10 hours at a constant current of 1 A / cm2: Aemion™ = commercial reference; Crossl. = cross-linked membrane according to the invention; Blend = blend membrane according to the invention, each at an IEC of 2.0 meq / g in 1 M KOH at 70 °C and 1 bar. Fig. 15: Polarization curves of membranes according to the invention: Aemion™ = commercial reference; Crossl. = cross-linked membrane according to the invention; Blend = blend membrane according to the invention, each at an IEC of 2.0 meq / g in 1 M KOH at 70 °C and 1 bar. Research Center Jülich GmbH 13.05.2024 EXAMPLES 1. Preparation of an inventive ether-functionalized norbornene-based water-insoluble polymer membrane Bromobutylnorbornene was used as the norbornene monomer, which can be produced by a reaction of bromohexene with dicyclopentadiene (see Figure 1). Both components are refluxed under an inert atmosphere. For purification, vacuum distillation and subsequent flash chromatography with heptane as eluent were used (Figure 6 shows the 1 H-NMR spectrum of the pure product). Bromobutylnorbornene is then ready for use as a monomer if the quaternization by the Menshutkin reaction is carried out only on the polymer, i.e., after copolymerization. For the introduction of the ether functionality (ether chain as spacer R 1To convert the monomers (the monomers containing the amino acid ) as a side chain into the norbornene monomers, dicyclopentadiene and allyloxydiethelene glycol are subjected to a Diels-Alder reaction under reflux in an inert atmosphere (see Figure 2). The latter molecule is present in a threefold ratio to ensure high conversion. Initial purification of the product is achieved using vacuum distillation. To achieve even higher purity, extraction with ethyl acetate and washing with water are performed. After drying, the extractant can be removed. The terminal hydroxy group is converted to a mesylate using methanesulfonyl chloride. The reaction takes place under an inert atmosphere at 0 °C in chloroform with the addition of 1.2 equivalents of triethylamine (see Figure 2). For purification, the reaction mixture is poured into hydrochloric acid and extracted with chloroform. The organic phase is then washed with sodium bicarbonate solution and dried. The product is obtained in pure form after the chloroform is removed using a rotary evaporator. The mesylate group is, in principle, substitutable in a Menschutkin reaction; therefore, the norbornene monomer prepared in the manner described here can already be used for processing into polymers and membranes. The terminal mesylate group can be substituted by bromine in a third reaction by using lithium bromide in a threefold ratio (see Figure 2). The reaction takes place in refluxing acetone under an inert atmosphere. After rotary evaporation of the acetone, the remaining reaction mixture is taken up in water and extracted with ethyl acetate. After drying the extracted phase, the ethyl acetate is evaporated, and the finished monomer is obtained. The Menshutkin reaction can be followed afterwards or carried out first on the polymer (Figure ? shows the 1 H-NMR spectra of the product and the intermediates). The comonomer, which can be introduced into the copolymers as a non-polar component, can be synthesized from anthracene and norbornadiene (see Figure 3). For this purpose, the anthracene is added to the norbornadiene, which is present in a ratio of 5.22 : 1. The reaction takes place at 180 °C under an inert atmosphere. For purification, a simple Filtration followed by washing with heptane is sufficient. The heptane only needs to be evaporated before the monomer can be polymerized (Figure 8 shows the 1 FI-NMR spectrum of the comonomer). In the case of a ring-opening polymerization, the monomers used are dissolved in dichloromethane under an inert atmosphere (see Figure 4 A). The molar ratio of the monomers is also equal to the incorporation ratio. The reaction is started by adding the catalyst (e.g., Grubbs third-generation catalyst). For the first few minutes, the reaction runs at 0 °C, with the cold bath being removed after a few minutes and the remainder of the reaction taking place at room temperature. After 24 h, the reaction is stopped by adding ethyl vinyl ether. The crude polymer is then precipitated in methanol and purified by Soxhlet extraction. After drying, the resulting precursor polymer is ready for the Menshutkin reaction if the monomers do not yet contain amine bases. The successful implementation of this reaction is shown by the GPC data (Figure 10) as well as the 1 FI-NMR spectrum of the copolymer prepared in this way (Figure 9). The introduction of the quaternary ammonium group is achieved by dissolving the obtained precursor polymer (prepared as described above) in a suitable solvent (selected e.g. from THF, DMF, DMAc, chloroform) and subsequent addition of an amine base A 1, as described herein. The quaternization reaction (see Figure 5) takes place at a temperature between 25-150°C and a reaction time of 1-3 days (depending on the base used). It has been found that degrees of functionalization of almost 100% are possible. The quaternization reaction time can be significantly shortened if the reaction is carried out in the microwave above the boiling point of the respective solvent. Furthermore, it is possible to only partially convert the halogen substituents to quaternary ammonium groups and then, after membrane production, to crosslink the remaining halogen substituents with a bifunctional amine base (e.g. 1,4-diazabicyclo[2.2.2]octane or / V,A / ,A / ',A / '-tetramethyl-1,6-hexanediamine) [F. Arslan, K. Chuluunbandi, ATS Freiberg, A. Kormanyos, F. Sit, S. Cherevko, J. Kerres, S. Thiele and T.Böhm, Performance of Quaternized Polybenzimidazole-Cross-Linked Poly(vinylbenzyl chloride) Membranes in HT-PEMFCs, ACS applied materials & interfaces, 2021, 13, 56584-56596.]. The quaternization of the monomers can be carried out analogously, with ethyl acetate or acetonitrile being particularly suitable solvents. The subsequent ring-opening metathesis polymerization is possible analogously to the uncharged monomers, with mixtures of DCM and methanol being used as solvents. Production of block copolymers: To prepare block copolymers based on the monomers according to the invention, 5-[2-(2-bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene is first prepared as a polyether chain-functionalized norbornene monomer (EM) (I) substituted with a Br leaving group. and the anthracene monomer (AM) were dissolved separately in dry DCM and degassed by repeated freezing with liquid nitrogen and evacuation (3x). A concentration of 0.1 mol / L was set for the EM and 0.05 mol / L for the AM. The Grubbs catalyst (0.0055 equivalents based on both monomers) was dissolved in dry DCM (10 mg / mL) and stirred for 10 min. The solution was then added in one shot to the EM solution. After 10 min, a sample was taken, quenched with ethyl vinyl ether, dried, and analyzed by GPC and NMR. The solution of the polymerized EM monomer was cooled to 0 °C, and the AM solution was then added in one shot. The solution was stirred for a further 30 min, quenched with ethyl vinyl ether (5.20 equivalents based on both monomers), concentrated on a rotary evaporator, and precipitated in methanol. The resulting block copolymer is dissolved in THF, reprecipitated in methanol and dried in vacuum at 60 °C.The schematic process is shown in Figure 4 B). 2. Production of inventive water-insoluble polymer membranes as cross-linked polymer membranes and / or blend membranes For further stabilization, the membranes obtained according to Example 1 can be converted into blend membranes. For blending, the quaternized polymers from Example 1 were dissolved in DMAc. Surprisingly, it was found that oxypolybenzimidazole (OPBI) formed a homogeneous mixture with the polymers in DMAc. The membranes were then drawn onto a glass plate using a doctor blade. After the solvent was evaporated, the membrane was ready for use. It was also extremely surprising that the copolymers, consisting of the ether-functionalized monomer and the anthracene-based monomer, only needed to be blended with small amounts of OPBI to obtain a flexible and resilient membrane. The mass fraction of the blended polymer could be reduced to a few percent (1-10 wt%). Alternatively, the isatin polymers described here can also be used for blending. It should be noted that the bromine sites must be quaternized before mixing the polynorbornenes with the isatin matrix polymers. Blends with the isatin polymers also demonstrated significant advantages in terms of chemical and mechanical stability. It is also possible to further stabilize the membranes obtained according to Example 1 by cross-linking. In the case of cross-linking, the sequence of the methodology is necessary, as the cross-linking is also carried out at the bromine groups. See the schematic representation of the cross-linking shown above. Therein: 1. Cross-linking of the precursor polymer with simultaneous film formation; 2. Quaternization of the film to an anion-exchange membrane. If the cross-linking occurs via another mechanism that does not substitute halogens (e.g. double bonds, vulcanization, epoxides, H-bonds), it is possible to place the cross-linking at the end, identical to the blending methodology. In the present preparation example, however, the diamine TMHDA was used. For the first step, the precursor polymer was dissolved in chloroform or DMAc, and the desired amount of TMHDA was added. Immediately afterward, the film was drawn using a doctor blade, and the solvent was evaporated. In the second step, the Menshutkin reaction was performed similarly to the above, except that the entire cross-linked film was immersed in the amine solution. The membranes cross-linked with TMHDA also showed that surprisingly an extremely low proportion of the cross-linker of 2-10 mol% per bromine group is sufficient. 3. Properties of the membranes according to the invention and possible uses The quality of the mechanical properties was demonstrated in the tensile tests described in more detail below (see Figure 11). The chloride conductivity as a function of the IEC of the membrane types according to the present examples is shown in Figure 12. The water absorption of the example membranes is shown in Figure 13. 3.1 Mechanical properties / stability To investigate the mechanical properties (stability), tensile tests were carried out on the polymer membranes of the above examples. The tensile tests were carried out using the following method: Membranes with a length of 5 mm and a width of 7 mm were subjected to tensile tests using a Mettler Toledo DMA 1 at different temperatures and air humidity to determine the Young's modulus as a function of the parameters mentioned above. The following temperatures and humidity values ​​were examined: 0% relative humidity at 70°C, 90% relative humidity at 25°C. Under these conditions, a membrane cross-linked with 2.5 mol% TMHDA and a blend with 2.0 wt% OPBI were investigated. The result is shown in Figure 11. 3.2 Conductivity The conductivity was determined using the following method: The chloride conductivity of the membranes of the above-mentioned example membranes in the fully hydrated state was measured with a Zahner Elektrik IM6, using aqueous 1 M NaCl as the electrolyte. The membranes were placed between Two commercial Aemion (AF1-HNN9-50-X) membrane pieces were placed. The impedance of the layer consisting of the two Aemion (AF1-HNN9-50-X) membrane pieces was then measured with the membranes of the present invention, and the impedance of only the two Aemion (AF1-HNN9-50-X) membranes was measured without the membrane under investigation. The difference between the two impedances then yielded the impedance of the membrane under investigation. Two identical gold electrodes with a diameter of 0.25 cm were used as electrodes. 2 The impedance was measured in a range from 200 kHz to 8 MHz and then the conductivity o of the membrane under investigation was calculated using the following formula, where R sp represents the specific resistance, which is calculated from the measured resistance divided by R sp = results. Furthermore, A gives the electrode area (here 0.25 cm 2 ) and d the thickness of the membrane: 1 d ° ~ Rs " ~ RA The result is shown in Figure 12. This clearly shows that conductivity increases exponentially and that an IEC of 2.0 meq / g or higher is required to achieve good performance. At an IEC of 2.0 meq / g, the cross-linked membrane according to Example 2 has an average conductivity of 12.2 mS / cm, and the blended version according to Example 2 has a conductivity of 9.1 mS / cm. These values ​​initially appear low, but they were measured using 1 M NaCl solution as the electrolyte and at room temperature. Under operating conditions (60-80 °C and 1 M KOH), these values ​​are typically several times higher and are therefore likely well suited for the intended application. 3.3 Water absorption The water absorption was examined using the following method: The membranes were weighed in dry form (mdry) and then immersed in ultrapure water for 24 h at 85 °C. The membranes were then briefly wiped with a cloth and weighed again (nriwet). The water absorption (WA) was then determined using the following formula: The result is shown in Figure 13. Here, it can be seen that the water absorption is not excessively high, which is consistent with the good mechanical properties. Surprisingly, it was found that the increased water absorption is less pronounced than the increase in conductivity with increasing lEC, which clearly demonstrates the potential of these materials. 4. Comparison tests with commercial membranes AEMION™ The membranes according to the invention according to Example 2 were investigated in comparison with a commercially available membrane AEMION™ in the application text. A commercial membrane, AEMION™, is a polybenzimidazole-based membrane distributed by lonomr Innovations Inc. with an ion exchange capacity of 2.40 mmol / g and a thickness of 50 μm. To everyone's great surprise, it was found that the inventive membranes (IEC = 2.0 meq / g, Mn = 50 kg / mol) from Example 2 can compete with the commercial AEMION™ membrane in the application test and in some cases even surpass it. This is clearly evident from the results of the stability test under constant current (see Figure 14). The cross-linked variant according to Example 2 even manages to exhibit a lower voltage increase, which in turn is related to the in-situ degradation during water electrolysis. The polarization curves (see Figure 15) are also very similar for all three membranes tested. In this case, the cross-linked membrane according to Example 2 is even significantly better than the commercial reference. The investigations of cell voltage at constant current and polarization are carried out using the following methods: The membrane electrode assemblies were tested in an anion exchange membrane electrolysis cell for single cell tests with an active area of ​​5 cm 2tested. The bipolar plates, made of Monel, had serpentine flow fields with a channel width of 1 mm and a land width of 0.8 mm. A thin layer of gold was applied to the bipolar plates to protect them from passivation. H2 Match NiFe-LDH catalysts (first generation), provided by 2D Match SL, were used on the anode side together with 10 wt.% Aemion® (AP1-HNN8-00) as a binder. The catalyst ink (1 wt.% solids, solvent ethanol:water 1:1) was applied by spray coating onto a sintered nickel fleece (Bekaert Bekipor 2 NI 18-0.25). A Sono-Tek Exactacoat device was used for this purpose. Platinum on carbon was used as the catalyst on the cathode side. This was also spray-coated onto a carbon gas diffusion substrate (Freudenberg H24C5) using 10 wt.% Aemion (AP1-HNN8-00) as a binder. The catalyst loading was 2.0 mg / cm 2for the anode and 0.5 mg / cm 2 for the cathode. Membrane pieces measuring 5 cm x 5 cm were used for the test. The membranes tested according to the invention were immersed in 1 M KOH at room temperature for 24 h. To produce the membrane electrode assemblies, the catalyst-coated substrates were placed on glass fiber-reinforced PTFE frames, with the membrane placed between the two catalyst substrates. The electrolysis cell was fixed with 12 screws, each with a torque of 10 Nm. The PTFE frames had a thickness of 235 pm. The electrolysis test was carried out at 70 °C and atmospheric pressure on both sides. 1 M KOH was used as the electrolyte on both sides. The measurement protocol included the following steps: 1. Test for electrical short circuit 2. Run in the cell at 1.8 V for 1 h 3. Recording the current-voltage characteristic curve (0.02 - 4 A / cm2 with 3 minutes hold time and impedance measurements between 150 kHz - 1 Hz) 4. Maintain the current at 1 A / cm2. 5. Record a second current-voltage characteristic curve as in 3. 5. Production of ion pair membranes for fuel cell operation The experiments described above surprisingly showed that the anion exchange polymers and anion exchange polymer membranes according to the invention are also excellently suited for fuel cell operation in the temperature range up to 240°C by doping them with phosphoric acid or a phosphonic acid and thus can be used as so-called ion-pair membranes in this temperature range. To obtain these membranes, they are prepared as uncrosslinked or crosslinked pure membranes, or as optionally ionically and / or covalently crosslinked blend membranes, and are placed in phosphoric acid or a phosphonic acid solution after production. The ion pair membrane is then formed by diffusion of the phosphoric acid or phosphonic acid molecules into the membrane. The ion pair consists of the cation of the anion exchange group and a dihydrogen phosphate or hydrogen phosphonate counterion in the first hydration sphere: [Polymer-N + ][H2PO4]- or [Polymer-N + ][H(R)PO3]- Further phosphoric acid or phosphonic acid molecules then attach to the ion pair via hydrogen bonds. A particular advantage of this membrane type is that, in contrast to phosphoric acid-doped polybenzimidazole membranes, the phosphoric acid or phosphonic acid molecules are bound much more strongly to the cation of the anion exchange group (a gain factor of about 8 was calculated [K.-S. Lee, JS Spendelow, Y.-K. Choe, C. Fujimoto and YS Kim, An operationally flexible fuel cell based on quaternary ammonium-biphosphate ion pairs, Nat Energy, 2016, 1. DOI: 10.1038 / nenergy.2016.120; AS Lee, Y.-K. Choe, I. Matanovic and YS Kim, The energetics of phosphoric acid interactions reveals a new acid loss mechanism, J. Mater. Chem. A, 2019, 7, 9867-9876.], which leads to a significantly lower risk of "bleeding" of the phosphoric acid-doped membrane and thus a drop in performance when using the ion pair membranes, for example in fuel cells in the temperature range up to 240°C, than with phosphoric acid-doped polybenzimidazoles.

Claims

PATENT CLAIMS [1] Water-insoluble polymer membrane (AEM) containing a copolymer with a) quaternized norbornene derivative monomer units (EM) of the following formula (I), wherein R 1 a (-CH2OCH2-)I polyether chain with I = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1 is an amine base selected from the group: where the bond to the -R 1 -CH2-spacer of the norbornene derivative monomer unit (I) via a nitrogen atom to form a quaternary ammonium group; and n denotes the degree of polymerization; and b) norbornene-based comonomers (AM) of the following formula (exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene). [2] Water-insoluble polymer membrane (AEM) according to claim [1], wherein the quaternized norbornene derivative monomer units (EM) of formula (I) have an -R 1- CH2 spacer, where R 1 a (-CH2OCH2-)I polyether chain with I = 2, according to the following formula (ll) where A 1 an amine base according to claim [1]. [3] Water-insoluble polymer membrane (AEM) according to one of claims [1] or [2], wherein the quaternized norbornene derivative monomer unit (EM) (I) or (II) is polymerized with the norbornene-based comonomer (AM) to form copolymer units (EM-co-AM) of the formula (II-I), (Il-I) where co is a copolymerized bond and A 1 represents an amine base according to claim [1] and n and m each denote the degree of polymerization. [4] Water-insoluble polymer membrane (AEM) according to any one of claims [1] to [3], further comprising further norbornene-based comonomers selected from the following group: [5] Water-insoluble polymer membrane (AEM) according to any one of claims [1] to [4], wherein the quaternized norbornene derivative monomer unit (EM) (I) or (II) forms block copolymers with the norbornene-based comonomers and has block copolymer units (EM-block-AM) of the formula (II-II) (Il-H) where block is a block copolymerized bond and A 1 represents an amine base according to claim [1], and n and m each denote the degree of polymerization. [6] Water-insoluble polymer membrane (AEM) according to any one of claims [1] to [5], wherein the amine base A 1 in the quaternized norbornene derivative monomer units is selected from the group: where the bond to the -R 1 -CH2-spacer of the norbornene derivative monomer unit via a nitrogen atom to form a quaternary ammonium group; more preferably, the amine base A 1 selected from: Tetramethylimidazolium and quinuclidinium. [7] Water-insoluble polymer membrane (AEM) according to any one of claims [1] to [6], wherein the copolymers are additionally reinforced by i) blending with a chemically inert matrix polymer, and / or j) covalent crosslinking, and / or k) crosslinking by non-covalent interactions comprising ionic Interactions, dipole-dipole interactions, H-bonds Interactions and van der Waals interactions with a physicochemical reactant, and / or l) chemically inert particles, meshes or fibers. [8] Water-insoluble polymer membrane (AEM) according to one of claims [1] to [7], which is in the form of a blend membrane with at least one chemically inert Matrix polymer, wherein chemically inert matrix polymers are selected from the group (i) the polybenzimidazoles comprising: (ii) from the group of isatin polymers comprising Polyoxindolediphenylbutane (PODPB) Polyoxindolebiphenylene (POBP) [9] Water-insoluble polymer membrane (AEM) according to claim [8], wherein the matrix polymers are selected from the group of isatin polymers. [10] Water-insoluble polymer membrane (AEM) according to one of claims [1] to [9] wherein the copolymers with the monomer units (I) or (II), or copolymers according to formula (II-I) or block copolymers according to formula (II-II) are present as cross-linked copolymers. [11] Water-insoluble polymer membrane (AEM) according to claim [10], wherein the copolymers are cross-linked with a cross-linking reagent selected from the group of quaternizing diamines (III-A) and (III-B): (X x NX 2 ) (X 3 NX 4 ) (IH-A) (lll-B) where Y are linear or branched Ci-Ci2-alkyl chains, preferably Ci-Cs-alkyl chains, more preferably C4-Cs-alkyl chains; and X1 , X 2 , X 3 and X 4 are each the same or different and independently of one another are linear or branched Ci-Cs-alkyl chains; or wherein X 1 and / or X 2 each with X 3 and / or X 4 together with the nitrogen atom to which they are attached, form one or two rings to form a diazacyclo or a diazabicyclo unit; and wherein Z are each the same or different and independently of one another linear or branched Ci-C4-alkyl chains, preferably Ci-C5-alkyl chains; wherein preferably the crosslinking reagent (III-A) is selected from: N,N,N',N'-tetramethylhexylenediamine (TMHDA) 1,4-diazabicyclo[2.2.2] octane and wherein preferably the crosslinking reagent (III-B) is selected from: 1-Methyl-4-[3-(1-methyl-4-piperidyl)propyl] piperidine. [12] Norbornene monomer according to the following formula (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1 ]hept-2-ene) or according to the following formula where A 1 an amine base according to claim [1] or [6]. [13] Copolymer according to one of the following formulas (II-A) and (II-B): (HA) (II-B) or according to one of the following formulas (II-C) and (II-D): (HC) (ll-D) where R 2 = a (-CH2OCH2-) polyether chain with 1 = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; A 1 an amine base according to claim [1] or [6]; A 2 represents a leaving group Br; n represents the degree of polymerization of the monomer and m represents the degree of polymerization of the comonomer; co represents a copolymerized bond and block represents a block copolymerized bond; and wherein in formulas (II-A), (IIB), (II-C) and (II-D) it is particularly preferred that I = 2. [14] A process for producing a water-insoluble polymer membrane (AEM) according to any one of claims [1] to [11], comprising the steps of: (e) polymerizing or copolymerizing norbornene monomers according to claim [12] with the norbornene-based comonomers according to claim [1] and optionally claim [4] (f) if necessary substitution of the Br leaving group A 2 with an amine base A 1 as defined in claim [1] or [6]; wherein the quaternization with the amine base A 1 preferably by means of the Menschutkin reaction; the order of the polymerization and quaternization steps is variable; (g) optionally comprising an additional step of blending with one or more chemically inert matrix polymers as defined in claim [8] or [9] for producing the water-insoluble polymer membranes (AEM) in the form of blend membranes; and / or (h) optionally comprising a step of cross-linking the polymers / copolymers. [15] Use of the water-insoluble polymer membrane (AEM) according to any one of claims [1] to [11] as an alkaline anion exchange membrane or as an anion-conductive membrane, as a binder material for the production of electrodes or catalyst layers, as an electrolyte or as an ionomer, in electrolysis processes, electrodialysis, diffusion dialysis or Donnan dialysis, as well as in fuel cells, in water electrolysis processes or in (redox) flow batteries.

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