Hydrogenated side-chain functionalized polynorbornene-anion exchange polymers as membrane materials for alkaline water electrolysis and fuel cells

Abstract

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

Description

[0001] Hydrogenated side-chain functionalized polynorborn anion exchange polymers as membrane materials for alkaline water electrolysis and fuel cells

[0002] INTRODUCTION

[0003] The present invention relates to water-insoluble polymer membranes (AEMs) based on novel side-chain functionalized copolymers of hydrogenated polynorbornenes 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 copolymer building blocks used to produce the novel water-insoluble polymer membranes, as well as methods for producing the copolymers and polymer membranes according to the invention.

[0004] BACKGROUND

[0005] In alkaline water electrolysis, water is split into hydrogen and oxygen by applying an electric potential. At the anode, oxygen is produced through the consumption of four equivalents of hydroxide and the release of electrons (oxidation). At the cathode, hydrogen is produced through the uptake 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:

[0006] Anode:

[0007] Cathode:

[0008] Overall reaction:

[0009] Maintaining the two half-reactions of electrolysis and fuel cell operation therefore requires the transport of hydroxide ions from the cathode to the anode. The presented invention, as a water-insoluble polymer membrane (AEM), fulfills precisely this purpose while simultaneously spatially separating the electrochemical half-cells.

[0010] To be used as an electrolyte in alkaline water electrolysis or alkaline fuel cells, the polymers must be stable under the prevailing aggressive conditions (alkaline environment, electrical potential, nucleophilicity of the hydroxide, pressure differences, temperatures). Furthermore, the materials used must exhibit high hydroxide conductivity to enable high current densities. STATE OF THE ART

[0011] Compared to proton-conducting 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 like Nation™ for acidic applications. The alkaline environment places special demands on polymer stability, and furthermore, anion-compatible functionalizations are required in AEMs.

[0012] 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 a!., Tuning the properties of poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes and their performance in H 2 / 02 fuel cells, Energy Environ. Sci., 2018, 11, 435-446.; S.Miyanishi et al., Highly conductive mechanically robust high Mw poly fluorene 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.).

[0013] Furthermore, polymers with side-chain separated anion exchange groups exhibit increased alkaline stability and improved cycle stability in alkaline fuel cells and / or electrolysis. The desired mechanical behavior of membranes can be described as mechanically robust 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).

[0014] Accordingly, various side chains can be introduced to modify the membrane's behavior. These side chains can be aromatic, aliphatic, or olefinic, and may also contain heteroatoms, such as ether bridges.

[0015] Commercially available membranes for alkaline applications include those 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.).

[0016] These membranes can be used in reinforced or unreinforced versions, 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.).

[0017] 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 (AD Mohanty et al., Systematic Alkaline Stability Study of Polymer Backbones for Anion Exchange Membrane Applications, Macromolecules, 2016, 49, 3361-3372).

[0018] Furthermore, 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.).

[0019] Quaternized polybenzimidazoles, which are used as membrane materials for alkaline electrochemical processes, are chemically stable only 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.).

[0020] 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). Membranes made of poly(4-vinylbenzyl chloride-co-styrene) are also frequently used. The Sustainion® membrane from Dioxide Materials is commercially available, in which the benzylic chloride group in poly(4-vinylbenzyl chloride-co-styrene) is 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. Sei., 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. I. Masel 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.).

[0021] Although Sustainion® achieved better performance in alkaline water electrolysis compared to other materials, the low alkaline 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. Sei. 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.).

[0022] German patent application DE10 2014 009 170 A1 describes ion exchange membranes for use in electrochemical processes, which are available in the form of blend membranes. It describes covalently and / or ionically crosslinked polybenzimidazole (PBI) blend membranes made from halomethylated and optionally sulfonated and / or phosphoned polymers. These blend membranes can be further covalently crosslinked by adding a low- and / or macromolecular crosslinker. The blend membranes described are characterized by the fact that they contain halomethylated polymers, i.e., monomer units functionalized with a Hal-CH2 group. Table 1 of DE10 2014 009 170 A1 also provides an overview of known (non-commercial) AEMs: Table 1: Relevant membranes for use in fuel cells

[0023] German patent 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. It describes how the conversion of the Hal-CH2 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 further describes how steric shielding of the anion exchange groups of AEMs can significantly improve their alkaline stability, as this hinders the nucleophilic attack of the OH- counterions on the quaternary ammonium group.However, DE 10 2016 007 815 A1 also describes that improving the chemical stability of AEM always depends on the combination of the anion exchange group and the polymer backbone, since the stability of the anion exchange group always depends on the polymer backbone, and it is not easy to predict which polymer backbone will be more stable. Another way to stabilize AEM is through crosslinking. Furthermore, DE 10 2016 007 815 A1 describes that the systematic increase in the hydrophobicity of the AEM ammonium groups, via the increase in the length of the alkyl chains bound to the quaternary ammonium ion from trimethylbenzylammonium via 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 covers such blend membranes which 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.

[0024] Polybenzimidazoles are also known to be used as blending materials for blending membranes, for example for membranes based on the anion exchange ionomer FAA3 (Konovalova et al., Blend membranes of polybenzimidazole and an anion exchange ionomer (FAA3) for alkaline water electrolysis: Improved alkaline stability and conductivity, J. Membr. Sei. 2018, 564, 653-662.).

[0025] Further matrix polymers and their use in the production of N-dimethylpiperidine (DMP)-based AEM blend membranes are described by He et al., who also investigated isatin polymers such as polyoxindolebiphenylene (POB) for their suitability as blend polymers. In the studies described therein, the addition of the isatin polymer polyoxindolebiphenylene (POB) led to a reduction in the stability of the DMP-based AEM membrane in alkaline conditions (He et al., Insight into alkaline stability of N-heteroatom on N-dimethylpiperidinium based anion exchange membranes (AEMs) for alkaline water electrolysis, J. Membr. Sei., 2023, 688, 122109).

[0026] In summary, numerous polymers and copolymers have already been used in anion-conducting polymer membranes (AEMs). However, many of them suffer from insufficient chemical stability under alkaline conditions. German patent DE102022120196, along with the corresponding WO2024 / 033429A1, describes an approach to solving these problems by providing side-chain functionalized polystyrenes as membrane materials for alkaline water electrolysis. Specifically, DE102022120196 and WO2024 / 033429A1 describe polystyrene-based and quaternized polymers / copolymers and their use in water-insoluble, anion-conducting 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 the provision in the form of blended membranes with polybenzimidazoles, is also described.

[0027] Polynorbornenes are also known in the literature as membrane materials. For these membranes, norbornene is usually copolymerized with a norbornene derivative that has a quaternary ammonium group, e.g., a quaternary trimethylamine group, linked via an alkyl chain of varying 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. 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).

[0028] Other monomers used to date are based on norbornene with a large aromatic substituent originating 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 (SC 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.).

[0029] The use of aromatic substituents instead of unfunctionalized norbornene enhances the mechanical properties by reducing water uptake. While the resulting membranes are easy to handle, the ionic conductivity decreases, rendering them unsuitable for use as anion-conducting 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).

[0030] Copolymerization of norbornene with ether-functionalized norbornene increases water uptake, resulting in gel-like behavior. While this increases conductivity, 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).

[0031] Copolymerization of norbornene with norbornene derivatives containing quaternized alkyl chains also results in unusable, unreinforced materials. While cross-linking compensates for this, sufficient conductivity is only achievable with very high IECs (> 3.1 meq. / g). The disadvantage lies in the high water absorption, which impairs the mechanical properties (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; S. Huang, et al., Facile selfcrosslinking to improve mechanical and durability of polynorbornene for alkaline anion exchange membranes, Int. J. Hydrog. Energy, 2020, 45, 13068-13079).

[0032] 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 which have been observed to reduce glass transition properties compared to materials with alkyl side chains (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.).

[0033] Sun et al. have described copolymers of alkyl side-chain functionalized norbornene monomers with anthracene monomers in which the polymer bond was hydrogenated following the ring-opening polymerization reaction (X. Sun et al., Remarkable impact of chain backbone on the performance of Poly (norbornene derivatives)-based anion exchange membranes, J. Membr. Sei, 2024, 703, 12280).

[0034] Furthermore, the international application WO 2024 / 245731 A1 also describes polymer membranes and their monomer and copolymer building blocks based on polyoxyethylene side-chain functionalized norbornene derivatives and their use in anion-conducting polymer membranes.

[0035] Polynorbornenes have the advantage that, unlike commercial membranes, they do not have 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.

[0036] They possess diverse functionalizability due to the wide range of monomer structures, which can be synthesized, among other methods, via Diels-Alder reactions of an aikene with dicyclopentadiene. Polymers based on norbornenes derivatives can be extensively modified to achieve a balance between stability and flexibility while simultaneously achieving high conductivity. Chemical stability is ensured by the absence of imidazole rings or aryl ether compounds (S. Martinez-Arranz et al., Versatile Route to Functionalized Vinylic Addition Polynorbornenes, Macromolecules, 2010, 43, 7482-7487).

[0037] Thus, polynorbornenes exhibit promising properties for potential use in AEMs, but so far they are limited to AEMs that are either chemically stable or highly conductive.

[0038] A disadvantage of the polynorbornene anion exchange polymers described so far is that they still exhibit double bonds in the main chain after the polymerization process. These double bonds increase the brittleness of the polynorbornene anion exchange polymers, and it has also been shown that, due to their chemical reactivity, the C-C double bonds impair chemical stability, particularly in alkaline applications such as alkaline membrane electrolysis or alkaline membrane fuel cells.

[0039] The provision of anion exchange polymers with an optimized combination of good mechanical properties and high ionic conductivity, especially those with improved chemical and mechanical stability, as well as reduced water absorption, is therefore desirable.

[0040] TASK STATEMENT

[0041] The object of the present invention was to provide novel alkaline anion exchange membrane materials that do not exhibit the disadvantages described above. Furthermore, an 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. In particular, an object of the invention was to provide improved anion exchange polymers with an optimized combination of good mechanical properties and high ionic conductivity, especially those with improved chemical and mechanical stability, as well as reduced water absorption.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-conducting 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 (DI water = fully demineralized water)), 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 discovered suitable norbornene derivatives for the production of norbornene-based copolymers and polymer membranes derived therefrom, exhibiting high stability and simultaneously good anion conductivity, and thus for their use in alkaline (anion exchange) membranes. In particular, the inventors have developed novel norbornene-based copolymers and polymer membranes derived therefrom, in which a further improvement in the chemical stability of the polymers in alkaline environments can be achieved through hydrogenation of double bonds in the polymer backbone. Thus, the copolymers and polymer membranes according to the invention are characterized by a combination of selected, particularly advantageous polynorbornenes and their hydrogenation in the polymer backbone to form novel hydrogenated, side-chain functionalized polymer membranes based on selected norbornene monomer units.

[0042] DESCRIPTION OF THE INVENTION

[0043] The problems of the present invention were surprisingly solved by providing new water-insoluble polymer membranes (AEMs) based on hydrogenated (saturated) polymers or copolymers, which contain quaternized norbornene derivative monomer units of the following formula (I) and norbornene-based comonomers of the following formula

[0044] (Exo-1 ,4,4a,9,9a,10-Hexanehydro-9,10-benzeno-1 ,4-methanoanthracene).

[0045] The monomer units of formula (I), which is also referred to as the norbornene derivative monomer (EM), contain the substituent R. 1 for an ether or polyether chain - (CH2OCH2-)L (with L = 1 to 10), which together with a -CH2 group, via which a quaternary ammonium group from an amine base A 1The monomer unit (I) is attached as a kind of spacer or spacer chain between the norbornene-based polymer backbone and the quaternary amine base. Chemically particularly stable and highly conductive water-insoluble anion-conducting polymer membranes (AEMs) can be formed from polymers or copolymers that have such monomer units (I) and in which double bonds in the polymer backbone are (completely) saturated by hydrogenation, particularly by copolymerization with Exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene as the norbornene-based comonomer.

[0046] The present invention is described in more detail below and includes in particular the following aspects:

[0047] [1] Water-insoluble polymer membrane (AEM) containing a hydrogenated copolymer with a) quaternized norbornene derivative monomer units (EM) of the following formula (I), wherein

[0048] R 1a (-CH2OCH2-)I ether or polyether chain with L = 1 to 10, preferably > 1 to <

[0049] 6, or > 1 to < 4; and

[0050] A 1 an amine base, selected from the group: where the binding 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

[0051] (exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene).

[0052] [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 spacers, wherein R 1 a (-CH2OCH2-)L ether or polyether chain with L = 2 is, according to the following formula (ll)

[0053] (ll), wherein A 1represents an amine base according to

[0001] .

[0054] [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) to form hydrogenated copolymer units (EM-co-AM-h) of formula (11-1),

[0055] EM-co-AM-h

[0056] (ll-l) wherein co is a copolymerized bond and

[0057] A 1 an amine base according to [1] and n and m respectively denote the degree of polymerization.

[0058] [4] Water-insoluble polymer membrane (AEM) according to [1] to [3], further comprising other norbornene-based comonomers selected from the following group:

[0059] or from

[0060] Norbornene-based alkylomers according to the following formula (I-alkyl):

[0061] (I-alkyl) wherein R3 a linear or branched Ci-C2o alkyl chain (alkyl spacer), preferably a Ci-Cs alkyl chain, more preferably a C4-C8 alkyl chain; and wherein

[0062] A x an amine base selected from the group of quaternizing amine bases A 1 as defined herein, or

[0063] A x a departure group A 2 as defined herein, preferably selected from the group of halogens, more preferably from the group comprising CI and Br, of which Br is particularly preferred; and n denotes the degree of polymerization.

[0064] [5] Water-insoluble polymer membrane (AEM) according to [1] to [4], wherein the quaternized norbornene derivative monomer unit (EM) (I) or (II) forms hydrogenated block copolymers with the norbornene-based comonomers and comprises hydrogenated block copolymer units (EM-block-AM-h) of formula (11-11)

[0065] EM-block-AM-h

[0066] (ll-ll) wherein block a block copolymerized bond and

[0067] A 1 an amine base according to [1], and n and m respectively denote the degree of polymerization.

[0068] [6] Water-insoluble polymer membrane (AEM) according to [1] to [5], wherein the amine base A 1 in the quaternized norbomen derivative monomer units selected from the group:

[0069] where the binding to the -R 1 -CH2-Spacer of the norbornene derivative monomer unit via a nitrogen atom to form a quaternary ammonium group.

[0070] [7] Water-insoluble polymer membrane (AEM) according to [1] to [6], wherein the amine base A 1 in the quaternized norbomen derivative monomer units selected from the group: preferred from the group:

[0071] Tetramethylimidazolium and quinuclidinium.

[0072] [8] Water-insoluble polymer membrane (AEM) according to [1] to [7], wherein the copolymers are further reinforced by a) blending with a chemically inert matrix polymer, and / or b) covalent cross-linking, and / or c) cross-linking by non-covalent interactions, comprising ionic

[0073] Interactions, dipole-dipole interactions, hydrogen bonds

[0074] Interactions and van der Waals interactions with a physicochemical reactant, and / or d) chemically inert particles, braids or fibers. [9] Water-insoluble polymer membrane (AEM) according to [1] to [8], which is in the form of a blended membrane with at least one chemically inert matrix polymer, wherein chemically inert matrix polymers are selected from the group

[0075] (i) comprising polybenzimidazoles:

[0076] (ii) comprising from the group of isatin polymers preferred

[0077]

[0010] Water-insoluble polymer membrane (AEM) according to [9], wherein the matrix polymers are selected from the group of isatin polymers.

[0078]

[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 mediators such as block copolymers, catalysts and / or dyes, and mixtures thereof.

[0079]

[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.

[0080]

[0013] Water-insoluble polymer membrane (AEM) according to [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): where

[0081] Y linear or branched Ci-Ci2 alkyl chains, preferably Ci-Cs alkyl chains, more preferably C4-C8 alkyl chains, are; and

[0082] X 1 , X 2 , X 3 and X 4 are each identical or different and independent linear or branched Ci-Cs alkyl chains; or wherein

[0083] 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, creating a diazacylo or diazabicyclo unit; and wherein

[0084] Z are each identical or different and independent linear or branched Ci-C4 alkyl chains, preferably Ci-Cs alkyl chains.

[0085]

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

[0013] wherein the crosslinking reagent (IH-A)

[0086] N,N,N',N'-Tetramethylhexylenediamine (TMHDA) or 1,4-Diazabicyclo[2.2.2] octane and the crosslinking reagent (11-B)

[0087] 1-Methyl-4-[3-(1-methyl-4-piperidyl)propyl] is piperidine.

[0088]

[0015] Copolymer according to one of the following formulas (11-A) and (11-B):

[0089] (HA) (ll-B), wherein

[0090] R 1 = represents a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4;

[0091] A 1 represents an amine base according to [1], [6] or [7];

[0092] A 2Br represents a leaving group; n denotes the degree of polymerization of the monomer and m the degree of polymerization of the comonomer; and co represents a copolymerized bond.

[0093]

[0016] Copolymer according to one of the following formulas (11-C) and (11-D):

[0094] (ll-C) (ll-D) wherein

[0095] R 2 = a (-CH2OCH2-) ether or polyether chain with

[0096] L = 1 to 10, preferably > 1 to 6, or > 1 to s 4;

[0097] A 1 represents an amine base according to [1], [6] or [7];

[0098] A 2 a leaving group Br; n denotes the degree of polymerization of the monomer and m the degree of polymerization of the comonomer; and block represents a block copolymerized bond.

[0099]

[0017] Copolymer according to

[0015] or

[0016] wherein R 2 represents a (-CH2OCH2-) ether or polyether chain with L = 2.

[0100]

[0018] Copolymer according to

[0015] to

[0017] which is present as a cross-linked copolymer.

[0101]

[0019] Copolymer according to

[0018] , which is cross-linked via quaternized diamines (III-A) and / or (III-B) as defined in

[0013] or

[0014] .

[0102]

[0020] Method for producing a water-insoluble polymer membrane (AEM) according to [1] to

[0014] , comprising the steps:

[0103] (a) Polymerization, copolymerization or block copolymerization of norbornene monomers of the following formula (IV-A) and / or (IV-B)

[0104] (IV-A) (IV-B) wherein

[0105] R 2 a (-CH2OCH2-) ether or polyether chain with

[0106] L = 1 to 10, preferably > 1 to 6, or > 1 to 4; and wherein

[0107] A 2a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, A is even more preferred 2 = Br; and wherein

[0108] A 1 an amine base according to [1], [6] or [7]; preferably with norbornene monomers of formula (IV-A) or (IV-B) where L = 2, in particular with those according to the formulas

[0109] (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene) and / or 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];

[0110] (b) possibly substitution of departure group A 2 with an amine base A 1 according to [1], [6] or [7];

[0111] (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes (EM-co-AM-h) according to formula (11-A) or (11-B), wherein R 2 represents a (-CH2OCH2-) polyether chain with L = 2.

[0112]

[0021] Method according to

[0020] , wherein the quaternization with the amine base A 1 according to [1], [6] or [7] via Menschutkin reaction.

[0113]

[0022] Method according to

[0020] and

[0021] , comprising, prior to step (b), an additional cross-linking step at the output 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].

[0114]

[0023] Method according to one of

[0020] to

[0022] , comprising an additional step of blending with one or more chemically inert matrix polymers as defined in [9] or

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

[0115]

[0024] Method for producing copolymers according to

[0017] to

[0019] , comprising steps (a) and (b) as described in

[0020] to

[0022] .

[0116]

[0025] Use of the water-insoluble polymer membrane (AEM) according to [1] to

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

[0117]

[0026] 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.

[0118]

[0027] Use of the water-insoluble polymer membrane (AEM) according to [1] to

[0014] as an electrolyte or as an ionomer.

[0119]

[0028] Use of the water-insoluble polymer membrane (AEM) according to [1] to

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

[0120]

[0029] 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

[0121] As described above, the object of the invention is achieved by novel water-insoluble polymer membranes based on hydrogenated (saturated) copolymers with norbornene derivative monomer units with quaternized ether or polyether chain and selected norbornene-based comonomers.

[0122] I. Water-insoluble polymer membranes based on hydrogenated copolymers of quaternized ether or polyether norbornene derivative monomer units

[0123] The invention relates to a novel water-insoluble polymer membrane (AEM) based on hydrogenated polymers or copolymers with norbornene derivative monomer units (EM) which have a quaternized ether or polyether chain alkyl chain as a spacer and are represented by the following formula (I), wherein

[0124] R 1 a (-CH2OCH2-)L ether or polyether chain, with L = 1 to 10, preferably > 1 to < 6, or

[0125] > 1 to < 4 is; and

[0126] A 1 an amine base selected from the group of quaternizing amine bases; and n denotes the degree of polymerization.

[0127] In accordance with the present invention, a copolymer or the polymer membrane according to the invention is considered to be insoluble in water if it or the copolymer absorbs less than 400 percent water by weight, based on its own weight (dry weight).

[0128] In this, the norbornene derivative monomer units (I) according to the invention are functionalized with a quaternized ether or polyether chain. The quaternization is effected by a quaternary nitrogen group A. 1 , which is linked to the ether or polyether chain via a [-CH2-] unit.

[0129] The polymerization of such functionalized norbornene derivative monomer units according to (I) leads to so-called precursor polymers, which can be present in the membranes according to the invention in the form of block copolymers or statistical copolymers, or which form these membranes. Such precursor polymers generally initially exhibit unsaturated double bonds in the polymer backbone. For clarification, it should be noted that, within the context of the description of the invention, the term "copolymer / copolymers" without further specific specification is to be understood as broadly as technically meaningful and is not limited to, for example, statistical copolymers. That is, the term primarily encompasses both statistical copolymers and block copolymers—unless technically excluded or explicitly specified otherwise.

[0130] Double bonds formed by polymerization / copolymerization are saturated by hydrogenation, preferably with the aim of achieving complete saturation of all double bonds in the polymer backbone. The monomers used can be commercially available or, for example, prepared by a Diels-Alder reaction of dicyclopentadiene and a suitable alkene, as described, for instance, in the unpublished international application PCT / EP2024 / 063160. For use in the AEMs according to the invention, the polymers / copolymers are functionalized in a quaternization reaction with amine bases. The resulting unsaturated precursor polymers with double bonds in the polymer backbone are hydrogenated so that the double bonds are saturated to obtain the hydrogenated polymers / copolymers according to the invention, which are then converted into the anion exchange polymers and membranes according to the invention.

[0131] In principle, it is also possible to introduce other ionic groups or functionalizations. Various mechanisms are available for polymerization, including, for example, cationic polymerization, polymerization via a metallocene complex, vinyl addition polymerization, or ring-opening polymerization (ROMP).

[0132] For the purposes of the invention, an alkyl chain, as mentioned herein, refers to a straight-chain or branched, saturated alkyl chain with 1 to 20 carbon atoms, designated as "Ci-20-alkyl". From the group of straight-chain, saturated alkyl chains, those with 1 to 8 carbon atoms ("C1-8") are preferred, and those with 4 to 8 carbon atoms ("C^s") are more preferred. Examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl, i-pentyl, neo-pentyl, and n-hexyl.

[0133] 2-Methylpentyl, 3-Methylpentyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, n-Heptyl, 2-Methylhexyl,

[0134] 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-methylpentyl 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-Ethylheptyl, 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.,

[0135] Particularly preferred are 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-methylpentyl, 3-Ethyl-3-methylpentyl, 2,2,3,3-Tetramethylbutyl. n-Butyl, n-Pentyl, n-Hexyl, n-Heptyl, and n-Octyl are even more preferred. A linear or branched C&E alkyl group is particularly preferred.

[0136] For the purposes of the invention, an ether or polyether chain, in particular as a substituent R, is defined as an ether or polyether chain. 1 or R 2In the formulas defined herein, straight-chain ether or polyether chains with 2 to 20 carbon atoms and 1 to 10 oxygen atoms are designated "(-CH20CH2-)I-IO". From the group of straight-chain ether or polyether residues, those with 2 to 10 carbon atoms and 1 to 5 oxygen atoms, designated "(-CH2OCH2-)I-5", are preferred; those with 1 to 5 carbon atoms and 1 to 3 oxygen atoms, designated "(-CH2OCH2-)I-3", are more preferred. A chain length of L = 2, i.e., "(-CHzOC^-) / " or "(-CH2OCH2- CH2OCH2-)", is particularly preferred. Examples include (-CH2OCH2-), (-CH2OCH2CH2OCH2-), (-CH2OCH2CH2OCH2CH2OCH2-), (-CH2OCH2CH2OCH2CH2OCH2CH2OCH2-) or (-CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2-). Particularly preferred are (-CH2OCH2-), (-CH2OCH2CH2OCH2-), (-CH2OCH2CH2OCH2CH2OCH2-). Even more preferred is (-CH2OCH2CH2OCH2-).

[0137] If an ether or polyether chain is used as a spacer in the monomer units according to the invention, R 1 or R 2Introduced, this results in an ether or polyether alkyl spacer over which the amine base A 1 (or a departure group A) 2 / A 3 ) is bound and the total chain length of such an ether or polyether alkyl spacer results from the chain length of R 1 or R 2 plus the [-CH2-] group, for example to (-CH2OCH2)-CH2- when R 1 or R 2 (-CH2OCH2-) is or (-CH2OCH2-CH2OCH2-)CH2- if L = 2.

[0138] Amine bases within the meaning of the invention are amino compounds which form a quaternary amino group via a nitrogen group with the ether or polyether chain linked via -CH2-.

[0139] Examples of quaternizing amine bases include:

[0140] where the binding 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.

[0141] Using a tertiary diamine for quaternization allows for simultaneous quaternization and covalent crosslinking of the anion exchange polymer, thereby reducing swelling / water absorption and further improving the mechanical stability of the anion exchange polymer. Tertiary diamines are therefore considered preferred amine bases.

[0142] The group of the following amine bases is preferred according to the invention:

[0143] where the binding 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.

[0144] Further amine bases preferred according to the invention are selected from the group;

[0145] Those from the following group are even more preferred: Particularly favored amine bases are:

[0146] Tetramethylimidazolium and quinuclidinium.

[0147] The copolymers according to the invention can, in principle, be combined with the same or different amine bases A 1 be quaternized. This means that, if necessary, mixtures of different tertiary N-basic compounds (amine bases) can also be used for quaternization.

[0148] The bond between the inventive -R 1 -CH2- or -R 2 -CH2- chain and the amine base A 1 This can, in principle, be done on any quaternizable nitrogen in the amine base.

[0149] 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. A degree of polymerization (n) or (m) > 100 up to < 300 is preferred. The water-insoluble polymer membranes (AEM) based on hydrogenated polymers or copolymers according to the invention are preferably characterized by an average molar mass between 20,000 g / mol and 150,000 g / mol. An average molar mass between 50,000 g / mol and 80,000 g / mol is further preferred.

[0150] 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. Preferably, hydrophobic norbornene-based comonomers are copolymerized in order to improve the stability of the AEMs.

[0151] The copolymers according to the invention comprise at least norbornene-based comonomers (AM) of the following formula:

[0152] (Exo-1, 4, 4a, 9, 9a, 10-hexanehydro-9,10-benzeno-1,4-methanoanthracene).

[0153] However, it is also possible to introduce additional norbornene-based comonomers, selecting from the following group, or mixtures thereof: Such additionally introduceable norbornene-based comonomers can also be those corresponding to the monomers EM according to formula (I) of the invention, wherein, however, instead of the ether or polyether spacer R 1 a Ci-Cpo alkyl chain (alkyl spacer) R 3 is provided for, according to the following formula (I-Alkyl):

[0154] (I-alkyl) wherein

[0155] R 3a linear or branched Ci-C2o alkyl chain, preferably a Ci-Cs alkyl chain, more preferably a C4-C8 alkyl chain; and wherein

[0156] A x an amine base selected from the group of quaternizing amine bases A 1 as defined herein, or

[0157] A x a departure group A 2 as defined herein, wherein departure groups (A X =A 2 ) preferably selected from the group of halogens, more preferably from the group comprising CI and Br, of which Br is particularly preferred; and n denotes the degree of polymerization (the degree of polymerization n > 100 up to < 300 is preferred).

[0158] Preferably, the water-insoluble polymer membranes (AEM) based on hydrogenated polymers or copolymers according to the invention are characterized by an average molar mass between 20,000 g / mol and 150,000 g / mol. A more preferred average molar mass is between 50,000 g / mol and 80,000 g / mol.

[0159] Aromatically 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.

[0160] The combinations according to the invention of ether-functionalized norborne (i.e., those in which the spacer is an ether or polyether chain R) 1 / R 2The combination of a polymer with an aromatically substituted norbornene such as exo-1,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1,4-methanoanthracene and hydrogenated double bonds / saturated bonds in the polymer backbone leads to new copolymers with surprisingly improved properties and their particular suitability as stable, especially alkali-stable, AEMs. Water-insoluble polymer membranes (AEMs) comprising the same or different copolymers can, in principle, be represented by the general formula (11-co):

[0161] (ll-co) where co = represents a copolymerized bond and

[0162] M 1 corresponds to a norbornene derivative monomer unit (I) as defined herein and

[0163] M 2 one of the norbornene-based comonomers defined herein, and n the degree of polymerization of M 1 denoted and m the degree of polymerization of M 2 designated.

[0164] It is also possible to polymerize the copolymers according to the invention as block copolymers and thus provide water-insoluble polymer membranes (AEM) comprising identical or different block copolymers, which in principle can be represented by the general formula (ll-block):

[0165] (ll-block) where block = represents a block copolymerized bond and

[0166] M 1 corresponds to a norbornene derivative monomer unit (I) as defined herein and

[0167] M 2 one of the norbornene-based comonomers defined herein, and n the degree of polymerization of M 1 denoted and m the degree of polymerization of M 2 designated.

[0168] Block copolymers are copolymers that, unlike other copolymers, have a more controlled, strictly determined composition of monomers or comonomers. While copolymers as a whole represent a statistically distributed network of monomer or comonomer units, the order in which, for example, linear block copolymers are formed is characterized by a consistent sequence of the different units, such as the pattern -ABA-, where A and B represent different monomers or comonomers.

[0169] To ensure block copolymerization, the reaction must be more strictly regulated compared to other copolymerizations, for example by bringing the monomers or comonomers into contact with each other step by step.

[0170] Surprisingly, it was found that AEMs according to the invention, based on the hydrogenated block copolymers described herein, already exhibit excellent properties and generally do not require additional reinforcement, e.g., by apertures or cross-linking as described below. The block copolymers according to the invention also proved to be extremely promising with regard to their applicability and long-term stability in AEMs.

[0171] In the copolymers / block copolymers according to the invention, the respective monomers are preferably present in the following proportions:

[0172] EM monomer unit (I) : AM comonomer unit (Exo-1 ,4,4a,9,9a,10-hexanehydro-9,10- benzeno-1 ,4-methanoanthracene) 95 : 5 to 5 to 95, wherein the range between 30 EM : 70 AM to 70 EM to 30 AM is preferred.

[0173] In principle, the hydrogenated (saturated) 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 carried out on the AEMs according to the invention. Possible reinforcements include, for example, modifications of the AEMs by a) blending with chemically inert matrix polymers, b) covalent cross-linking of the polymers according to the invention with cross-linking reagents, c) cross-linking by non-covalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen bond interactions and van der Waals interactions with a physicochemical reactant, and d) reinforcement by the addition of chemically inert particles, fibers or braids.

[0174] In the case of reinforcement with chemically inert particles, fibers, or braids, these can optionally be modified with hydrophilic groups or ion exchange groups, either 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 potential delamination. In principle, combinations of one or more of the aforementioned reinforcements can also be present in AEMs.

[0175] The enhancement has the effect of making the AEMs even more chemically resistant in the anionic environment, further reducing their water absorption and / or additionally increasing their mechanical stability.

[0176] The invention thus also encompasses, in a further aspect, novel water-insoluble polymer membranes (AEMs) in the form of blended membranes, which contain the hydrogenated 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), comprising, for example, the following:

[0177]

[0178] Surprisingly, the inventors have found that, in addition to the aforementioned PBIs, polymers derived from isatin are also ideally suited to enable significant improvements in the chemical and mechanical stability of water-insoluble polymer membranes according to the invention, incorporating the norbornene monomer units according to the invention. Examples of suitable isatin matrix polymers include: Preferred isatin polymers derived from this are polyoxindolediphenylbutane (PODPB) and

[0179] Polyoxindolebiphenyl (POB):

[0180] It is also generally 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.

[0181] When using a blended polymer, the compatibility and miscibility of both polymers (copolymer and matrix polymer) must be ensured. It is also important that the blended polymer is chemically stable and possesses excellent mechanical properties. The polybenzimidazoles and isatin matrix polymers described herein, such as the particularly preferred oxy-polybenzimidazole (OPBI), polyoxindolediphenylbutane (PODPB) and polyoxindolebiphenylene (POB), represent a good choice, and surprisingly it has been found that even small 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.

[0182] It is known from the prior art to use significantly larger quantities 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 surprisingly found that smaller quantities of the matrix polymers, up to a maximum of 10.0 wt.%, are sufficient to achieve a stabilizing effect, and that larger quantities are even detrimental. It was found that above a quantity > 10.0 wt.%, the AEMs no longer become conductive but insulating and are therefore unusable for their intended application. At a quantity of 60 wt.%, as described in the prior art, the matrix polymer swells, forming a bulk effect with insulating properties.

[0183] A surprising finding in the production of blended membranes was that even water-soluble polymers / copolymers (including block copolymers) become sufficiently water-insoluble or hydrophobic to be suitable as AEMs simply by blending (mixing) with suitable matrix polymers described above. In a further aspect of the invention, the water-insoluble polymer membranes (AEMs) can be reinforced by cross-linking and are then present as cross-linked polymers or copolymers (or block copolymers). Cross-linked polymers or copolymers (including block copolymers) are defined as the polymers or copolymers (or block copolymers) according to the invention in which the linear polymer chains in the polymer backbone are cross-linked to one another by a cross-linking reagent. Suitable cross-linking reagents within the meaning of the invention include, in particular, quaternizing diamines (III), especially those according to formulas (III-A) or (III-B):

[0184] / (Y K (XW 2 ) (X^JX 4 )

[0185] (III-A) wherein

[0186] Y linear or branched Ci-Ci2 alkyl chains, preferably Ci-Cs alkyl chains, more preferably C4-C8 alkyl chains, are; and

[0187] X 1 , X 2 , X 3 and X 4 each being the same or different and independently representing linear or branched Ci-Cs alkyl chains; or wherein

[0188] 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, creating a diazacylo or diazabicyclo unit; and wherein

[0189] Z are each identical or different and independent linear or branched C1-C4 alkyl chains, preferably C-, -Cs alkyl chains.

[0190] Regarding the term "alkyl chain", especially as substituent Y and / or as one of the substituents X 1 up to X 4 and / or as substituent Z in formulas (III-A) and (III-B) refers to the definition above.

[0191] Examples of possible cross-linking diamines (III-A) include:

[0192] N,N,N',N'-Tetramethylmethylenediamine, N,N,N',N'-Tetramethylethylenediamine, N,N,N',N'-

[0193] Tetramethylpropylenediamine, N,N,N',N'-Tetramethylbutylenediamine, N,N,N',N'-

[0194] Tetramethylpentylenediamine, N,N,N',N'-Tetramethylhexylenediamine, N,N,N',N'-

[0195] Tetraethylmethylenediamine, N,N,N',N'-Tetraethylethylenediamine, N,N,N',N'-

[0196] Tetraethylpropylenediamine, N,N,N',N'-Tetraethylbutylenediamine, N,N,N',N'-

[0197] Tetraethylpentylenediamine, N,N,N',N'-Tetraethylhexylenediamine, N,N,N',N'-

[0198] Tetrapropylmethylenediamine, N,N,N',N'-Tetrapropylethylenediamine, N,N,N',N'-

[0199] Tetrapropylpropylenediamine, N,N,N',N'-Tetrapropylbutylenediamine, N,N,N',N'-

[0200] Tetrapropylpentylenediamine, N,N,N',N'-tetrapropylhexylenediamine. Particularly preferred is

[0201] N,N,N',N'-Tetramethylhexylenediamine. In the context 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, they form one or two rings, creating a diazacylo or diazabicyclo unit.

[0202] 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.

[0203] 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.

[0204] 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-methyl-4-piperidyl)propyl]piperidin, 1-Ethyl-4-[3-(1-ethyl-4-piperidyl)propyl]piperidin, 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.Particularly preferred are 1-isopropyl-4-[2-(1-isopropyl-4-piperidyl)ethyl]piperidine, 1-methyl-4-[3-(1-methyl-4-piperidyl)propyl]piperidine, 1-ethyl-4-[3-(1-ethyl-4-piperidyl)propyl]piperidine, 1-propyl-4-[3-(1- propyl-4-piperidyl)propyl]piperidine, 1 -isopropyl-4-[3-(1 -isopropyl-4-piperidyl)propyl]piperidine,.

[0205] 1-Methyl-4-[4-(1-methyl-4-piperidyl)butyl]piperidine, 1-ethyl-4-[4-(1-ethyl-4-piperidyl)butyl]piperidine, 1-propyl-4-[4-(1-propyl-4-piperidyl)butyl]piperidine and 1-isopropyl-4-[4-(1 -isopropyl-4-piperidyl)butyl]piperidine, most preferred are 1-methyl-4-[3-(1-methyl-4-piperidyl)propyl]piperidine, 1-ethyl-4-[3-(1-ethyl-4-piperidyl)propyl]piperidine, 1-propyl-4-[3-(1-propyl-4-piperidyl)propyl]piperidine, and 1-isopropyl-4-[3-(1-isopropyl-4-piperidyl)propyl]piperidine.

[0206] The lowest possible proportion of the crosslinker with sufficient stability is preferred (e.g. < 7.5 mol% crosslinker per bromine group).

[0207] 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. Another cross-linking effect can also be achieved through charged hydrogen bonds between the quaternized ammonium groups and suitable existing molecular residues 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 polybenzimidazloene and acceptors according to the invention in the form of oxygens from ether or polyether chains.Dipole-dipole interactions occur between all polar components, and van der Waals interactions occur between all species introduced into the membrane.

[0208] The water-insoluble polymer membranes (AEMs) according to the invention, either in the form of hydrogenated polymers / copolymers according to the invention, in the form of blended membranes or in the form of cross-linked hydrogenated polymers / copolymers according to the invention (comprising hydrogenated block copolymers) or also in mixtures 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 structures or nonwovens.

[0209] Hydrophobic polymer membranes (AEMs) according to the invention may also contain further 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 mediators such as other suitable block copolymers, and other suitable auxiliary and additive materials. It is possible to add individual components or mixtures of components from one or more of these groups.

[0210] The hydrogenated quaternized copolymers 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.

[0211] The water-insoluble polymer membranes (AEMs) according to the invention are characterized either by comprising hydrogenated (i.e., saturated, preferably fully saturated) quaternized copolymers according to the invention with hydrophobic comonomers as defined herein, and / or by optionally (particularly in the case of hydrophilic / water-soluble polymers / copolymers) being in the form of a blend with at least one chemically inert matrix polymer, and / or by the polymer chains of the hydrogenated polymers / copolymers according to the invention being cross-linked with a cross-linking reagent from the group of quaternizing diamines. II. Polymers, copolymers, and block copolymers based on ether- or polyether-functionalized norbornene

[0212] The hydrogenated polymers / copolymers according to the invention are formed with norbornene monomers of the following general formulas:

[0213] (IV-A) (IV-B) wherein

[0214] R 2a (-CH2OCH2-) ether or polyether chain with

[0215] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein

[0216] A 2 a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, even more preferred is

[0217] A 2 = Br; and wherein

[0218] A 1 represents an amine base as defined herein.

[0219] In this context, the term ether or polyether chain, especially as a substituent R, refers to 2 , the same meaning as previously defined, especially in connection with R 1 .

[0220] The term amine base, especially as substituent A 1 , has the same meaning as previously defined.

[0221] The term departure group in the sense of A 2Designates suitable leaving groups, comprising, for example, halogen or pseudohalogen substituents such as chloro, bromo, iodo, azido, cyano, cyanato, isocyanato, fulminato, thiocyanato, and isothiocyanato substituents. Those from the group of halogen substituents, such as chlorine, bromine, or iodo, are preferred; bromine is most preferred.

[0222] A departure group A 2 In principle, the following can also be selected in the aspects of the invention described herein from the group comprising mesylates, tosylates and triflates.

[0223] 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.

[0224] Particularly preferred is 5-[2-(2-bromoethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene:

[0225] 5-[2-(2-bromoethoxy)ethoxymethyl]bicyclo[2.2.1 ]hept-2-en

[0226] 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.

[0227] According to the invention, particularly preferred polymers / copolymers are formed with norborne monomers comprising an ether or polyether chain R 1 or R 2 with the meaning L = 2 and are substituted with a terminal Br leaving group, as with

[0228] (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene) or which with a terminal quaternizing amine base (A 1 are substituted, as with where A 1 represents an amine base as defined herein.

[0229] Another aspect of the invention relates in particular to hydrogenated (i.e., substantially fully saturated) copolymers of the general formula (ll-co),

[0230] (ll-co) wherein

[0231] M1 a norbornene derivative monomer unit (lA) or (lB) corresponds with

[0232] R 2 = a (-CH2OCH2-) ether or polyether chain with

[0233] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2: and wherein

[0234] A 1 an amine base, as defined herein, is and

[0235] A 2 a departure group, as defined herein, is preferably A 2 = Br, and wherein

[0236] M 2 a comonomer as defined herein corresponds to and n is the degree of polymerization of M 1 denoted and m the degree of polymerization of M 2 designated.

[0237] The above definitions refer to the terms ether or polyether chain, amine base and leaving group.

[0238] For the purposes of the invention, M is defined therein as... 2the norbornene-based comonomers according to the invention as defined herein, in particular, for example, the comonomer designated as “AM”. In the case of the formation of polymers / copolymers with different comonomers, as also defined herein, M designates 2 the potentially different comonomers.

[0239] Particularly preferred embodiments of hydrogenated copolymers (11-co) are shown in formulas (11-A) and (11-B), which are formed with the norbornene-based comonomer exo- 1 ,4,4a,9,9a,10-hexanehydro-9,10-benzeno-1 ,4-methanoanthracene:

[0240] (ll-A) (ll-B) wherein

[0241] R 2 a (-CH2OCH2-) ether or polyether chain with

[0242] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 1 an amine base selected from the group of quaternizing amine bases as defined herein; and

[0243] A2 a leaving group as defined herein, preferably selected from the group of halogens or pseudohalogens, wherein halogens are particularly preferred, and 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.

[0244] In a preferred embodiment, the copolymers according to the invention can also be present as cross-linked copolymers. For this purpose, copolymers of formula (1A) or (12-A) are, for example, cross-linked with a cross-linking reagent such as a quaternizing diamine (III), preferably one according to the formulas (13-A) or (13-B) defined above. To obtain quaternized copolymers of formula (1B) or (12-B), the reaction is carried out with a quaternizing amine base as defined herein, wherein such copolymers may additionally exhibit statistical proportions of cross-links.

[0245] Another aspect of the invention relates in particular to hydrogenated block copolymers of the general formula (ll-block),

[0246] (ll-block) wherein

[0247] M 1 a norbornene derivative monomer unit (lA) or (lB) corresponds with

[0248] R 2 = a (-CH2OCH2-) ether or polyether chain with

[0249] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein

[0250] A 1 an amine base, as defined herein, is and

[0251] A 2 a departure group, as defined herein, preferably Br, and wherein M 2 a comonomer as defined herein corresponds to and n is the degree of polymerization of M 1 denoted and m the degree of polymerization of M 2 designated.

[0252] The above definitions refer to the terms ether or polyether chain, amine base and leaving group.

[0253] For the purposes of the invention, M is defined therein as follows: 2 the norbornene-based comonomers according to the invention as defined herein, in particular, for example, the comonomer designated as “AM”. In the case of the formation of block copolymers with different comonomers, as also defined herein, M designates 2 the potentially different comonomers.

[0254] Particularly preferred embodiments of hydrogenated block copolymers (I l-block) are shown in formulas (ll-C) and (ll-D), which are formed with the norbornene-based comonomer exo-1 ,4,4a, 9, 9a, 10-hexanehydro-9, 10-benzeno-1 ,4-methanoanthracene:

[0255] (ll-C) (ll-D) wherein

[0256] R 2 a (-CH2OCH2-) ether or polyether chain with

[0257] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 1 an amine base selected from the group of quaternizing amine bases as defined herein; and

[0258] A 2 a leaving group as defined herein, preferably selected from the group of halogens or pseudohalogens, wherein halogens are particularly preferred, and 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.

[0259] Particularly preferred hydrogenated copolymers and block copolymers (II-A, II-B, II-C and II-D) are characterized by an R 2 -Chain length of L = 2 marked:

[0260]

[0261] (II-C-L2) (II-D-L2)

[0262] III. Production of monomers and comonomers

[0263] Suitable synthesis methods for the production of the monomers and comonomers used to form the polymers / copolymers / polymer membranes according to the invention have been described in the international application PCT / EP2024 / 063160.

[0264] The synthesis of the substituted norbornene derivatives used to produce the AEMs and their copolymers according to the invention can then be carried out via 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. It is important, however, that one of the comonomers bears a halogen group so that a Menschutkin reaction can be carried out on the monomer or on the subsequent polymer. The halogen group may already be present after the Diels-Alder reaction or may be converted into one in subsequent reaction steps. Another possibility for the preparation of monomeric norbornene derivatives arises via the Diels-Alder reaction of norbornadiene (dienophile) with another diene.

[0265] Suitable dienes include, for example, 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 via a Menschutkin reaction, for which, in principle, tertiary N-basic compounds such as the amine bases defined herein (A) are suitable. 1For example, N-methylpiperidine, trimethylamine, quinuclidine or quinuclidinol, or 2,3,4,5-tetramethylimidazole, particularly those identified herein as preferred, can be used. The monomer building blocks thus obtained can then be polymerized to form an (unsaturated) precursor polymer, preferably by transition metal-catalyzed ring-opening polymerization (molybdenum, titanium, tantalum, tungsten, ruthenium) or vinyl addition polymerization. There are no particular restrictions in principle on the selection of the amine bases for quaternization, and those described herein, for example, can be used.

[0266] The manufacturing process can therefore be summarized as follows:

[0267] 1. A Diels-Alder reaction between dicyclopentadiene and an olefinic, hydroxy-substituted ether or polyether chain (V) to form an intermediate (VB).

[0268] 2. Subsequently, the formation of a sulfonic acid ester (VC) from the intermediate (V-B).

[0269] 3. Subsequently, the sulfonic acid ester can be substituted by a leaving group to give the norbornene monomer (IV-A) or by an amine base to give the norbornene monomer (IV-B). Alternatively, the sulfonic acid ester (VC) can be substituted by a leaving group to give the norbornene monomer (IV-A), followed by a further substitution of the leaving group by an amine base to give the norbornene monomer (IV-B). wherein

[0270] R 2 = a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably L = 2; and wherein

[0271] A 1 an amine base, as defined herein, is and

[0272] A 2 a departure group as defined herein, preferably A 2 = Br, and

[0273] A 3 a leaving group selected from sulfonic acid esters, preferably mesylates, tosylates or triflates.

[0274] In this context, the term refers to an ether or polyether chain, especially as a substituent R 2 The formulas (VA), (VB), (VC) and (IV-A) define the same as before.

[0275] For compounds according to (VA), for example, a total chain length for the olefinic, hydroxy-substituted ether or polyether chain (VA) results from the sum of R 2 , the terminal [CH2=CH-] group and the [-CH2-] group, for example (CH2=CHCH2OCH2CH2-) if R 2 (-CH2OCH2-) is or (CH2=CHCH2OCH2CH2OCH2CH2-) if R 2 (-CH2OCH2CH2OCH2-) is.

[0276] Furthermore, an amine base, especially as a substituent A, is designated 1 The formulas (VA), (VB), (VC) and (IV-A) define the same as before.

[0277] A leaving group, especially as substituent A2 In formula (IV-A), the same term is used as defined above. According to the invention, a Br leaving group (i.e., A) is preferred. 2 = Br).

[0278] The substituent A 3 , particularly with regard to the sulfonic acid ester of formula (VC), denotes a leaving group from the group of sulfonates. Mesylate, tosylate and triflate leaving groups are preferred, with mesylate leaving group being particularly preferred.

[0279] 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.

[0280] 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.

[0281] Examples of compounds (VC) include 2-(2-Bicyclo[2.2.1]hept-5-enylmethoxy)ethylmethanesulfonate, 2-[2-(2-Bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethylmethanesulfonate, and 2-[2-[2-(2-Bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethoxy]ethylmethanesulfonate. 2-[2-(2-Bicyclo[2.2.1]hept-5-enylmethoxy)ethoxy]ethylmethanesulfonate is particularly preferred.

[0282] The Diels-Alder reaction according to the invention is preferably carried out under inert conditions between dicyclopentadiene and an olefinic, hydroxy-substituted ether or polyether chain. Since this is a reaction in substance, the reactants themselves form the solvent. Preferably, the Diels-Alder reaction involves an excess of the olefinic, hydroxy-substituted ether or polyether chain (VA). 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. Preferred temperatures are 205 °C, 200 °C, 195 °C, 190 °C or 185 °C. 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; 10–20 h, 10–18 h, or 10–16 h are preferred, and 16 h is particularly preferred. In a subsequent step, the intermediate product (V-B) from the Diels-Alder reaction can be purified by vacuum distillation.

[0283] The intermediate product (VB) can be extracted from ethyl acetate following vacuum distillation and washed, for example with water. In a further step

[0284] In the reaction step, under inert conditions, the intermediate product (VB) can be esterified with a sulfonic acid halide to form a sulfonic acid ester (VC).

[0285] Sulfonic acid halides are preferably selected from the sulfonic acid chlorides; methanesulfonic acid chloride, p-toluenesulfonic acid chloride, or trifluoromethanesulfonic acid chloride are particularly preferred, with methanesulfonic acid chloride being especially preferred. The reaction of the intermediate (VB) with the sulfonic acid halide preferably takes place in chloroform, dichloromethane, chlorobenzene, dichlorobenzene, toluene, or tetrahydrofuran; chloroform and dichloromethane are preferred, with 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. 2 °C, 1 °C, 0 °C, -1 °C, or -2 °C are preferred, and 0 °C is particularly preferred. The sulfonic acid ester (VC) can be purified by reacting it with hydrochloric acid and extracting it from chloroform. In a further reaction step, the sulfonic acid ester (VC) can be reacted with an alkali halide or alkali pseudohalide to give a norbornene monomer of formula (IV-A). Alkali halides or alkali pseudohalides are preferably selected from LiCl, LiBr, Lil, 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, preferably LiCl, LiBr, Lil, particularly preferably LiBr.The reaction of the sulfonic acid ester (VC) to the 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, with acetone being most preferred. Preferably, the reaction of the sulfonic acid ester (VC) to the norbornene monomer (IV-A) involves an excess of the alkali halide or alkali pseudohalide. The alkali halide or alkali pseudohalide is preferably added in a fivefold, fourfold, threefold, or twofold excess, with a threefold excess being preferred. The reaction of the sulfonic acid ester (VC) to the 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. 66 °C, 64 °C, 62 °C, or 60 °C are preferred. 60 °C is particularly preferred.The reaction of the sulfonic acid ester (VC) to the norbornene monomer (IV-A) can be 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. The norbornene monomers (IV-A) thus obtained can be purified by conventional methods, e.g., by dissolving them in water and extracting them with ethyl acetate. The sulfonic acid ester (VC) or the norbornene monomer (IV-A) can be reacted with an amine base to give 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 conditions analogous to the quaternization of the polymers or copolymers described above. In this quaternization process, in addition to the solvents mentioned above, ethyl acetate or acetonitrile can be used as solvents.

[0286] The production of the comonomer (AM) used according to the invention can also be carried out via such a Diels-Alder reaction.

[0287] The synthesis steps for the production of the monomers / comonomers used are shown in Figures 1 and 2.

[0288] IV. Process for the production of hydrogenated copolymers, block copolymers and water-insoluble polymer membranes according to the invention.

[0289] The water-insoluble polymer membranes (AEM) according to the invention can be produced by copolymerization of norbornene monomers according to formulas (IV-A) and (IV-B) with norbornene-based comonomers as defined herein (e.g. also as M 2 (designated) can be obtained:

[0290] (IV-A) (IV-B) wherein

[0291] R 2 a (-CH2OCH2-)I ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably L = 2; and

[0292] A 1an amine base selected from the group of quaternizing amine bases, as defined herein; and

[0293] A 2 a leaving group as defined herein, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, preferably halogens, more preferably A 2 = Br.

[0294] The terms ether or polyether chain, amine base, and leaving group are defined in the preceding text. Various polymerization mechanisms are conceivable. These include cationic polymerization, polymerization via a metallocene complex, vinyl addition polymerization, or ring-opening polymerization. Preferably, water-insoluble polymer membranes according to the invention are obtained from copolymers prepared by ring-opening polymerization (ROMP).

[0295] First, the monomers and comonomers are dissolved in a suitable solvent and, using a catalyst, are converted to the unsaturated (precursor) copolymers via ring-opening polymerization under inert conditions. Inert conditions refer to the exclusion of atmospheric oxygen, for example, by working in an argon atmosphere.

[0296] Suitable solvents for carrying out the ring-opening polymerization of monomers of formula (IV-A) include dichloromethane (DCM), chloroform, chlorobenzene, dichlorobenzene, toluene, and THF. DCM, chloroform, or chlorobenzene are particularly preferred. DCM is most preferred. Suitable solvents for carrying out the ring-opening polymerization of monomers of formula (IV-B) include 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, with ratios of 10:1, 9:1, 8:1 and 7:1 being particularly preferred. Ratios of 10:1 and 9:1 are most preferred. Suitable solvents for precipitating the copolymers include organic solvents such as dichloromethane (DCM), chloroform, chlorobenzene, dichlorobenzene, toluene, THF, methanol, and propanol.

[0297] In principle, all catalysts suitable for the polymerization mechanisms mentioned herein are typically also suitable for the synthesis of the polynorbornenes described herein. 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 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.

[0298] Temperature control can be useful and necessary in the polymerization processes for producing the polymers / copolymers according to the invention. The temperature during the polymerization process can, for example, be regulated in the first few minutes using a cold bath and then increased as the reaction progresses. Temperature ranges of -20 to 50 °C, -20 to 40 °C, -20 to 30 °C, or -20 to 25 °C are possible. 0 to 30 °C or 0 to 25 °C is preferred, and 0 to 25 °C is particularly preferred. The polymerization is usually stopped by adding a polymerization inhibitor. Examples of polymerization inhibitors 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.

[0299] Figure 3 shows a ring-opening polymerization for the production step of an unsaturated precursor polymer of a preferred copolymer according to the invention.

[0300] According to the invention, the double bonds in the precursor polymers obtained in this way are saturated in a hydrogenation step, as shown by way of example in Figure 4 using a precursor polymer that has not yet been quaternized.

[0301] The quaternization of substituent A 2 (Leaving group), as defined herein, is carried out with an amine base from the group of quaternizing amine bases A 1 , as defined herein. Quaternization can be carried out before or after completion of the copolymerization, as well as before or after the hydrogenation step. Quaternization is preferably carried out via the Menschutkin reaction.

[0302] For quaternization, the norbornene monomers and the amine base A chosen for the precursor copolymer step can be used. 1The copolymers are dissolved in 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, dimethyl sulfone, sulfolane, or N-ethylpyrrolidone. THF is a particularly preferred solvent. Quaternization of the (precursor) copolymers via a Menschutkin reaction is preferably carried out at 25–150 °C, 25–125 °C, 25–100 °C, or 25–75 °C. 0 The reaction is carried out at temperatures of 25–75 °C, 30–75 °C, 35–75 °C, or 40–75 °C, preferably 40–60 °C, and most preferably 50 °C. The Menschutkin reaction can be carried out over a period of 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, and particularly preferably 48 h.

[0303] Figure 5 shows an example of quaternization via Menschutkin reaction by introducing an amine base into a precursor copolymer that is not yet hydrogenated, i.e. unsaturated.

[0304] Figure 6 shows an example of quaternization via Menschutkin reaction by introducing an amine base into an already hydrogenated, i.e. saturated, copolymer.

[0305] By appropriate process control, homopolymers of the norbornene derivative monomer units (EM) and the norbornene-based comonomers (AM), as well as copolymers with variable proportions of the different comonomers, can be produced.

[0306] It is also generally 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.

[0307] In contrast to the statistical copolymerization described above, ROMP can also be used to produce block copolymers, which can likewise be converted into hydrogenated copolymers according to the invention in the form of hydrogenated block copolymers by hydrogenation and saturation of the double bonds in the polymer backbone. 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 different arrangements of the comonomers in the polymer can be produced, as illustrated by way of example in Figure 7. Otherwise, the process conditions described above also apply to block copolymerization.Figure 7 shows, in addition to the general block copolymerization, the steps of hydrogenation and subsequent quaternization for the production of a hydrogenated block copolymer preferred according to the invention.

[0308] Particularly in the case of ring-opening polymerization, the hydrogenation of the double bonds still present in the resulting unsaturated precursor polymer within the polymer backbone is an important process step for achieving improved chemical stability of the polynorbornene anion exchange polymers. Hydrogenation of the double bonds can be carried out, for example, using 4-methylbenzene sulfonhydrazide in toluene, as illustrated in Figure 4 [SC Price, X. Ren, AM Savage and FL Beyer, Synthesis and characterization of anion-exchange membranes based on hydrogenated poly(norbornene), Polym. Chem., 2017, 8, 5708-5717].

[0309] It has been shown that the hydrogenation and subsequent quaternization of block polymers according to the invention results in the formation of a nanophase-separated structure consisting of a hydrophobic nanophase (AM) and a hydrophilic nanophase (quaternized EM) [M. Mandat et al.: Anionic multiblock copolymer membrane based on vinyl addition polymerization of norbornenes: Applications in anion-exchange membrane fuel cells, Journal of Membrane Science, 2019, 570-571, 394-402; R. Selhorst et al.: Multiblock CopolymerAnion-Exchange Membranes Derived from Vinyl Addition Polynorbornenes, ACSAppl. Energy Mater, 2021, 4, 10273-10279], wherein the ion conduction takes place in the EM nanophase, and the AM nanophase supports the mechanical stability of the block copolymer. To obtain an anion exchange polymer according to the invention, the quaternization of the brominated hydrogenated precursor polymer can then be carried out in a subsequent process step under the conditions described above.

[0310] As described above, the copolymers according to the invention can be chemically cross-linked for additional stabilization. For this purpose, unsaturated precursor copolymers, e.g., those prepared from norbornene monomers of formula (IV-A), can be cross-linked by a cross-linking reagent (III-A) or (III-B) before quaternization with an amine base and before hydrogenation, for example by reacting <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 cross-linking reagent with the precursor copolymer. Preferred values ​​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%.

[0311] Following the cross-linking of the precursor copolymers, the reaction can then be carried out in a solution of an amine base (A1 ) according to the Menschutkin reaction described above.

[0312] The process of cross-linking is shown schematically in Figure 11 using the example of a brominated precursor polymer with a diamine (shown for TMHDA as a bifunctional tertiary amine and saturation of the remaining Br sites with trimethylamine TMA).

[0313] The inventors of the present invention have surprisingly discovered that the hydrogenated polynorbornenes described herein can be blended with a stable (chemically inert) matrix polymer, such as a polybenzimidazole or a polyisatin, yielding homogeneous (transparent) blend membranes that exhibit surprisingly improved mechanical stability. In particular, the two isatin polymers PODPB and POB have shown good results in experimental testing with the hydrogenated polynorbornene anion exchange polymers according to the invention. The polybenzimidazoles and isatin polymers described herein are suitable as blend polymers.

[0314] To produce the AEMs according to the invention in the form of blended membranes, the hydrogenated 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 (or mixtures thereof), in a suitable solvent, e.g., a solvent from the amide group. Suitable solvents from the amide group include dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), sulfolane, N-methylpyrrolide ion (NMP), and dimethylformamide (DMF). DMAc, DMSO, or NMP are preferred. DMAc is particularly preferred. Surprisingly, it has been found that oxy-polybenzimidazole or isatin polymers are particularly well suited, since they form a homogeneous mixture with the polymers in DMAc.

[0315] For the production of water-insoluble polymer membranes in the form of blended membranes, a proportion of < 10.0 wt.% matrix polymers, based on the total amount of matrix polymer(s) and copolymers, is preferably used. As explained above, this has proven advantageous for the conductivity of the AEMs. Suitable quantity ranges for blended membranes are 1.0 to 10.0 wt.% of the proportion of chemically inert matrix polymers, based on the mixture of matrix polymers and hydrogenated copolymers. Accordingly, 1.0 wt.%, 2.0 wt.%, 3.0 wt.%, 4.0 wt.%, 5.0 wt.%, 6.0 wt.%, 7.0 wt.%, 8.0 wt.%, 9.0 wt.%, or 10.0 wt.% matrix polymer can be used for blending in blended membranes according to the invention. Preferably 1.0 to 5.0 wt.%, particularly preferably 2.5 wt.%.

[0316] Since the hydrogenated block copolymers according to the invention already possess a surprisingly high stability per se, further strengthening, e.g., by cross-linking or blending with matrix polymers, is less relevant than for the copolymers according to the invention. In principle, the measure of additional stabilization, by cross-linking and / or blending, can be selected and, if necessary, carried out individually depending on the respective mechanical and chemical stability properties of the respective polymers / copolymers, as well as the stability requirements for the intended applications.

[0317] In principle, the sequence of the copolymerization and quaternization steps can be varied in the processes described herein, as detailed below. In particular, the hydrogenation step can also be flexibly integrated into the synthesis sequence, allowing quaternization to be performed before or after the hydrogenation step. If additional crosslinking is performed, this can also be carried out before or after hydrogenation. If blending with matrix polymers is planned, the leaving group (e.g., the Br sites) must be quaternized before mixing with the blending polymers. Blending with matrix polymers will generally be the final step.

[0318] Water-insoluble polymer membranes (AEMs) according to the invention, made from the hydrogenated copolymers according to the invention, can be obtained by uniformly spreading the dissolved hydrogenated copolymers onto a smooth surface, e.g. a glass plate, with a doctor blade and subsequently evaporating the solvent.

[0319] The blend membranes according to the invention can also be obtained by applying the solution comprising the polymers / copolymers according to the invention and the chemically inert matrix polymers to a surface such as a glass plate using a doctor blade and subsequent evaporation of the solvent.

[0320] V. Use of the water-insoluble polymer membranes according to the invention

[0321] Due to their advantageous properties, as described in detail above, the water-insoluble polymer membranes (AEMs) according to the invention are particularly well suited as alkaline (anion exchange) membranes or anion-conducting membranes. This also opens up the possibility of using them as binder materials for the production of electrodes or as solid electrolytes, especially in electrolysis processes, electrodialysis processes, diffusion dialysis processes, such as Donnan dialysis, and water electrolysis processes. Furthermore, the water-insoluble polymer membranes (AEMs) according to the invention are particularly well suited for use in fuel cells or (redox) flow batteries.

[0322] The invention also allows for 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 an ionomer.

[0323] It was surprisingly 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 herein as preferred 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 the average molecular weight being between 30 and 100 kg / mol.

[0324] Surprisingly, this made it possible to provide chemically and mechanically more stable membranes compared to the previously known membranes based on polynorbornenes.

[0325] A particular aspect of the invention 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.

[0326] The aspects of the invention described herein are further explained by the figures and the following examples, although the invention is not to be seen as limited thereto.

[0327] VI. Designs

[0328] [1] Water-insoluble polymer membrane (AEM) containing a hydrogenated copolymer with a) quaternized norbornene derivative monomer units (EM) of the following formula (I), wherein

[0329] R 1 a (-CH2OCH2-)I polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4; and A 1 an amine base, selected from the group: where the binding to the -R1 -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

[0330] (exo-1, 4, 4a, 9, 9a, 10-hexanehydro-9,10-benzeno-1,4-methanoanthracene).

[0331] [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 spacers, wherein R 1 a (-CH2OCH2-)I polyether chain with L = 2 is, according to the following formula (ll) where A 1an amine base according to

[0001] . [3] Water-insoluble polymer membrane (AEM) according to one of [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 formula (11-1).

[0332] EM-co-AM-h

[0333] (ll-l) or by forming block copolymers with block copolymer units (EM-block-AM) of the formula (ll-ll)

[0334] EM-block-AM-h

[0335] (Il-Il) wherein co is a copolymerized bond and block is a block copolymerized bond and each

[0336] A 1 an amine base according to [1], and n and m respectively denote the degree of polymerization.

[0337] [4] Water-insoluble polymer membrane (AEM) according to one of [1] to [3], further comprising other norbornene-based comonomers selected from the following group:

[0338] or from norbornene-based comonomers according to the following formula (I-alkyl):

[0339] (I-alkyl) wherein

[0340] R 3 a linear or branched Ci-C2o alkyl chain (alkyl spacer), preferably a Ci-Cs alkyl chain, more preferably a CrCs alkyl chain; and wherein

[0341] A x an amine base selected from the group of quaternizing amine bases A 1 as defined herein, or

[0342] A x a departure group A 2 as defined herein, preferably selected from the group of halogens, more preferably from the group comprising CI and Br, of which Br is particularly preferred; and n denotes the degree of polymerization.

[0343] [5] Water-insoluble polymer membrane (AEM) according to one of [1] to [4], wherein the copolymers are further reinforced by a) blending with a chemically inert matrix polymer, and / or b) covalent cross-linking, and / or c) cross-linking by non-covalent interactions, comprising ionic

[0344] Interactions, dipole-dipole interactions, hydrogen bonds

[0345] Interactions and van der Waals interactions with a physicochemical reactant, and / or d) chemically inert particles, braids or fibers.

[0346] [6] Water-insoluble polymer membrane (AEM) according to one of [1] to [5], which is in the form of a blended membrane with at least one chemically inert matrix polymer, wherein chemically inert matrix polymers are selected from the group

[0347] (i) comprising polybenzimidazoles:

[0348]

[0349] (ii) comprising from the group of isatin polymers preferred [7] Water-insoluble polymer membrane (AEM) according to one of [1] to [6] wherein the copolymers with the monomer units (I) or (II), or copolymers according to formula (II-I) or block copolymers according to formula (11-11) are present as cross-linked copolymers, wherein the copolymers are cross-linked with a cross-linking reagent selected from the group of quaternizing diamines (11-A) and (11-B):

[0350] (III-A) (III-B) where

[0351] Y linear or branched Ci-Ci2 alkyl chains, preferably Ci-Cs alkyl chains, more preferably C4-Cs alkyl chains, are; and

[0352] X 1 , X 2 , X 3 and X 4 are each identical or different and independent linear or branched Ci-Cs alkyl chains; or wherein

[0353] X 1 and / or X 2 each with X 3 and / or X4 together with the nitrogen atom to which they are bonded, form one or two rings, creating a diazacylo or diazabicyclo unit; and wherein

[0354] Z are each identical or different and independent linear or branched Ci-C4 alkyl chains, preferably Ci-Cs alkyl chains; wherein the crosslinking reagent (11-A) is preferably selected from:

[0355] N,N,N',N'-Tetramethylhexylenediamine (TMHDA) 1,4-Diazabicyclo[2.2.2] octane and wherein the crosslinking reagent (III-B) is preferably selected from:

[0356] 1-Methyl-4-[3-(1-methy I-4-pi peridy l)propyl] piperidine.

[0357] [8] Copolymer according to one of the following formulas (11-A) and (11-B): or according to one of the following formulas (I-C) and (I-D): wherein

[0358] R 2 = a (-CH2OCH2-) polyether chain with

[0359] L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4;

[0360] A 1 represents an amine base according to [1] or [6];

[0361] A 2 a leaving group Br; n denotes the degree of polymerization of the monomer and m the degree of polymerization of the comonomer; co represents a copolymerized bond and block a block copolymerized bond; and wherein in formulas (11-A), (11-B), (11-C) and (11-D) L = 2 is particularly preferably

[0362] [9] Method for producing a water-insoluble polymer membrane (AEM) according to one of [1] to [7], comprising the steps:

[0363] (a) Polymerization or copolymerization of norbornene monomers of the following formula

[0364] (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene) or according to the following formula where A 1an amine base according to [1]; 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];

[0365] (b) possibly substitution of the Br leaving group with an amine base A 1 according to [1];

[0366] (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-A) or (11-B), wherein R 2 represents a (-CH2OCH2-) polyether chain with L = 2.

[0367]

[0010] Use of the water-insoluble polymer membrane (AEM) according to one of [1] to [7] as an alkaline anion exchange membrane or as an anion-conducting 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.

[0368] DESCRIPTION OF THE FIGURES

[0369] Fig. 1 : Schematic representation of a synthesis according to the invention via three steps to a norbornene derivative with ether-functionalized side chain and terminal bromine group.

[0370] Fig. 2: Schematic representation of a synthesis of a strongly hydrophobic comonomer according to the invention based on anthracene.

[0371] Fig. 3: Schematic representation of a ring-opening polymerization of an ether-functionalized monomer with an anthracene-based comonomer according to the invention to form an unsaturated precursor copolymer.

[0372] Fig. 4: Schematic representation of a hydrogenation of the double bond in the polymer backbone of the unsaturated precursor copolymer with para-toluenesulfonylhydrazide produced by ring-opening polymerization

[0373] Fig. 5: Schematic representation of the quaternization of an unsaturated precursor polymer for the production of hydrogenated (saturated) anion exchange polymers according to the invention.

[0374] Fig. 6: Schematic representation of the quaternization of an already hydrogenated copolymer according to the invention for the production of hydrogenated (saturated) anion exchange polymers according to the invention.

[0375] Fig. 7: Schematic representation of the synthesis of block copolymers based on the preferred monomers EM and AM by sequential addition and polymerization of the two monomers, followed by hydrogenation and subsequent quaternization

[0376] Fig. 8: (a) 1 ¹H NMR spectrum of the unhydrogenated precursor copolymer with 54 ml% EM in the copolymer. (b) 1 ¹H NMR spectrum of the hydrogenated copolymer (EM-co-AM-h) with 54 mol% EM in the copolymer

[0377] (c) 1 H NMR spectrum of the hydrogenated copolymer quaternized with TMA.

[0378] Fig. 9: GPC curves of the 1st block compared to the GPC curve after addition of the 2nd monomer

[0379] Fig. 10: Comparison of the GPC curves of an unsaturated (not according to the invention; EM-co-AM) and a saturated (according to the invention; EM-co-AM-h) polynorbornene

[0380] Fig. 11 : Schematic representation of a cross-linking of a brominated precursor polymer with a diamine (shown for TMHDA as a bifunctional tertiary amine and saturation of the remaining Br with trimethylamine TMA)

[0381] Fig. 12: Characterization results of anion exchange (blend) membranes according to the invention of a hydrogenated and subsequently TMA-quaternized copolymer with 54 mol% EM and 46 mol% AM:

[0382] (a) Cl' conductivities of blend membranes with different POB contents as a function of temperature

[0383] (b) Conductivity of different membranes according to the invention as a function of the immersion time in 1M KOH at 85 °C

[0384] (c) Water uptake of blend membranes and POB depending on POB content

[0385] (d) Swelling of blend membranes depending on the POB content

[0386] EXAMPLES

[0387] 1. Production of an inventively designed ether-functionalized norbornene-based water-insoluble polymer membrane

[0388] The production of the ether-functionalized norbornene-based polymers was initially carried out as described in the international application PCT / EP2024 / 063160.

[0389] Bromobutylnorbornene was used as the norbornene monomer, which can be produced by a reaction of bromohexene with dicyclopentadiene. To introduce the ether functionality (ether or polyether chain as a spacer R), 1Dicyclopentadiene and allyloxydiethelene glycol are subjected to a Diels-Alder reaction under reflux in an inert atmosphere (see Figure 1, Step 1), with the addition of a side chain to the norbornene monomers. The latter molecule is present in three times the ratio to ensure high conversion. The product is first purified by vacuum distillation. To achieve even higher purity, extraction with ethyl acetate and washing with water are carried out. After drying, the extraction solvent can be removed.

[0390] The terminal hydroxyl 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 1, step 2). For purification, the reaction mixture is added to 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.

[0391] The terminal mesylate group can be substituted with bromine in a third reaction by using lithium bromide at three times the initial ratio (see Figure 1, step 3). The reaction takes place in refluxing acetone under an inert atmosphere. After rotary evaporation of the acetone, the remaining reaction mixture is dissolved in water and extracted with ethyl acetate. After drying the extracted phase, the ethyl acetate is evaporated, yielding the finished monomer. The Menschutkin reaction can then be carried out directly on the polymer.

[0392] The comonomer AM, which is introduced into the copolymers as a nonpolar component, can be synthesized from anthracene and norbornadiene (see Figure 2). 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. Simple filtration followed by washing with heptane is sufficient for purification. The heptane simply needs to be evaporated before the monomer can be polymerized. 1.1 Copolymerization of the monomers EM and AM to the statistically unsaturated precursor copolymer

[0393] The copolymerization of the monomers EM and AM to form a statistical copolymer is shown schematically in Figure 3. 1 The ¹H NMR spectrum of the unsaturated precursor copolymer obtained afterwards is shown in Figure 8(a).

[0394] In the case of ring-opening polymerization, the monomers used are dissolved in dichloromethane under an inert atmosphere. The molar ratio of the monomers is equal to the incorporation ratio. The reaction is initiated by adding the catalyst (e.g., Grubbs third-generation catalyst). For the first few minutes, the reaction proceeds at 0 °C, after which the cooling bath is removed and the remainder of the reaction takes place at room temperature. After 24 hours, the reaction is stopped by the addition of 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 hydrogenation.

[0395] 1.2 Copolymerization of the monomers EM and AM to form the block copolymer

[0396] Figure 7 shows the synthesis of a block copolymer from EM and AM. The NMR spectra of the block copolymer are identical to those of the statistical copolymer (according to Figure 8) when the monomer ratios are identical. Figure 9 clearly shows that after the addition of the second monomer, it polymerizes onto the first block, as the molecular weight increases according to the amount of monomer added.

[0397] To prepare block copolymers, the ether monomer (EM) and the anthracene monomer (AM) are dissolved separately in dry DCM and degassed by repeated freezing with liquid nitrogen and evacuation (3x). A concentration of 0.1 mol / L is established for EM and 0.05 mol / L for AM. The Grubbs catalyst (0.0055 equivalents based on both monomers) is dissolved in dry DCM (10 mg / mL) and stirred for 10 min, then added in one shot to the EM solution. After 10 min, a sample is taken, quenched with ethyl vinyl ether, dried, and analyzed by GPC and NMR. The solution of the polymerized EM monomer is cooled to 0 °C, and then the AM solution is added in one shot. The solution is 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 polymer is dissolved in THF, precipitated again in methanol, and dried under vacuum at 60 °C.

[0398] 1.3 Hydrogenation of the copolymers

[0399] The hydrogenation of the statistical copolymer is shown in Figure 4, and the hydrogenation of the block copolymer in Figure 7. 1The 1H NMR spectrum of the unsaturated precursor copolymer is shown in Figure 8(b). For the hydrogenation, the unsaturated polymer is dissolved in toluene to a concentration of 8 mg / mL. Para-toluenesulfonylhydrazide (6 equivalents based on the number of double bonds present) is then added, and the solution is degassed by passing an argon stream for 30 min. The reaction mixture is then heated under reflux for 24 h in an argon atmosphere. After cooling to room temperature, the solution is filtered through a short Alox column, concentrated by rotary evaporation, and the polymer is precipitated in methanol. The resulting hydrogenated copolymer polymer (EM-co-AM-h) is dried under vacuum at 60 °C.

[0400] Figure 10 shows a comparison of the GPC curves before and after hydrogenation. After hydrogenation, a significantly higher dispersity (1,4) is observed compared to the unsaturated polymer (1,1), as evidenced by the broader curve. Crucially, however, no decrease in molecular weight was detected, indicating that the polymer backbone is not affected during hydrogenation. The increased dispersity is likely due to a change in the hydrodynamic radius.

[0401] 1.4 Quaternization of the brominated and hydrogenated precursor copolymers

[0402] 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 (shown for different process steps in Figures 5, 6, and 7) is carried out at a temperature between 25 and 150°C and a reaction time of 1 to 3 days (depending on the base used). It has been found that functionalization levels of approximately 100% are achievable. The reaction time of the quaternization can be significantly shortened if the process is carried out in a microwave oven 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 fabrication, to crosslink the remaining halogen substituents with a bifunctional amine base (e.g., 1,4-diazabicyclo[2,2,2]octane or 1 / V,1 / V,1 / V,1 / V-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.].

[0403] The quaternization of the monomers can be carried out analogously, with ethyl acetate or acetonitrile being particularly suitable as solvents. The subsequent ring-opening metathesis polymerization is possible analogously to the uncharged monomers, with mixtures of DCM and methanol being suitable as solvents.

[0404] The 1 The ¹H NMR spectrum of the unsaturated copolymer is shown in Figure 8(c). Thus, Figure 8 shows the overall comparison of the 1 ¹H NMR spectra of a copolymer before hydrogenation (EM-co-AM), after hydrogenation (EM-co-AM-h), and after hydrogenation and quaternization (EM-q-co-AM-h). The resonance signals of the protons of the double bonds in the range between 5.0 and 5.6 ppm are no longer detectable after hydrogenation.

[0405] 2. Production of inventive water-insoluble polymer membranes as cross-linked polymer membranes and / or blended membranes

[0406] For further stabilization, the membranes of the quaternized hydrogenated norbornene copolymer obtained according to Example 1 can additionally be converted into blended membranes. For blending, the quaternized polymers from Example 1 were dissolved in DMAc or another dipolar aprotic solvent such as DMF, NMP, NEP, or DMSO.

[0407] Surprisingly, it was found that isatin polymers such as PODB and POB, or polybenzimidazoles such as oxypolybenzimidazole (OPBI), form a homogeneous mixture with the polymers in DMAc or another dipolar aprotic solvent. The membranes were then drawn onto a glass plate using a doctor blade. After the solvent evaporated, the membrane was ready for use. It was also extremely surprising that the copolymers, consisting of the ether- or polyether-functionalized monomer (EM) and the anthracene-based monomer (AM), only need to be blended with small amounts of OPBI or an isatin polymer to obtain a flexible and resilient membrane. The mass fraction of the binding polymer could be reduced, surprisingly, to amounts in the range of 1 to 10 wt%.

[0408] It is also possible to further stabilize the membranes obtained according to Example 1 by cross-linking. In the case of cross-linking, it is necessary to change the sequence of the methodology, since the cross-linking is also carried out on the bromine groups. See the schematic representation of cross-linking as shown in Figure 11. In this figure:

[0409] 1. Cross-linking of the precursor polymer with simultaneous film formation;

[0410] 2. Quaternization of the film into an anion-exchanging membrane.

[0411] If cross-linking occurs via a different mechanism that does not substitute halogens (e.g., double bonds, vulcanization, epoxides, hydrogen bonds), it is possible to place the cross-linking at the end, identical to the blending method.

[0412] In the present production 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 pulled using a doctor blade, and the solvent was evaporated. In the second step, the Menshutkin reaction was carried out similarly to the above, with the difference 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, 2–10 mol% per bromine group, is sufficient for good membrane properties.

[0413] 3. Properties of the inventive membranes and possible uses

[0414] Figure 12 shows characterization results of a selection of anion exchange (blend) membranes according to the invention.

[0415] The conductivity decreases progressively with increasing POB content in the blend (Figure 12a). The conductivity difference between 5 wt% and 10 wt% POB is significantly smaller than that between the membranes with higher POB contents (Figure 12a). The conductivity of the membrane with 5 wt% POB and 10 wt% POB is nearly identical in both chloride and hydroxide forms. This is also reflected in the KOH stability, with the conductivity of both membranes remaining almost unchanged even after 40 days in 1 M KOH at 85 °C (Figure 12b). A cross-linked membrane (2.5 mol% TMHDA) also showed no decrease in conductivity after the same period in 1 M KOH at 85 °C. The 5 wt% POB membrane exhibits twice the water absorption of the 10 wt% POB membrane (Figure 12c). This is also evident in the swelling behavior of the aperture membranes (Figure 12d).

[0416] In summary, it can be said that blend membranes with 10 wt.% POB in the blend exhibit the best combination of conductivity and water absorption / swelling behavior. The 10 wt.% POB membrane was also used for an AEMWE cell experiment, where a voltage of 1.91 V and a current of 2 A cm⁻¹ were applied. -2 This was achieved using only precious metal-free catalysts (NiFe-LDH as the OER catalyst and CoP as the HER catalyst) and a dry cathode. 1 M KOH at 60 °C was used as the electrolyte. Under the same conditions, the membrane outperforms Aemion+® as a commercial reference, with a current of 2 A cm. -2 A voltage of 2.3 V was required.

[0417] 3.1 Mechanical properties / stability

[0418] The investigation of the mechanical properties (stability) of the polymer membranes can be carried out via tensile tests, e.g. according to the following method.

[0419] Seven membrane segments, each measuring 4 cm x 1.5 cm, were pulled to breakage using a Shimadzu tensile tester with a force of 10 mm / s², and the applied force was recorded. All measurements were performed at room temperature.

[0420] The following results were obtained:

[0421] 3.2 O' -Conductivity

[0422] The chloride conductivity was investigated using the following method:

[0423] The chloride conductivity of the membranes of the example membranes listed above in the fully hydrated state was measured using a Zahner Elektrik IM6, employing aqueous 1 M NaCl as the electrolyte. For this purpose, the membranes were placed between two commercial Aemion (AF1-HNN9-50-X) membrane fragments. Subsequently, the impedance of the layer consisting of the two Aemion (AF1-HNN9-50-X) membrane fragments was measured in relation to the membranes of the present invention, and the impedance of only the two Aemion (AF1-HNN9-50-X) membrane fragments was measured without the membrane under investigation. The difference between the two impedances then yielded the impedance of the membrane under investigation. Two identical 0.25 cm² gold electrodes were used as electrodes. 2 Electrode area was used. The impedance was measured in a range from 200 kHz to 8 MHz, and subsequently the conductivity μ of the membrane under investigation was calculated using the following formula, where R sprepresents the specific resistance, which is derived from the measured resistance divided by R sp = results.

[0424] Furthermore, A gives the electrode area (here 0.25 cm²). 2 ) and d the thickness of the membrane: 1 do = - = -

[0425] R,“ R ■ A

[0426] The result is shown in Figure 12a.

[0427] 3.3 OH conductivity

[0428] The hydroxide conductivity was investigated using the following method:

[0429] The hydroxide conductivity was measured using a Scribner MTS 740 membrane test system in water. Prior to measurement, the membranes were converted to the hydroxide form by soaking them in KOH. The resistance was determined by varying the voltage between -0.1 V and 0.1 V and measuring the corresponding current flow using Ohm's law (U = R x I). The conductivity was then calculated using the following formula, where 0.425 cm is determined by the geometry of the measuring body, and d and b correspond to the thickness and width of the membrane, respectively.

[0430] 1 0.425 cm

[0431] <y = — = -

[0432] R." : R • d ■ b 3.4 Water absorption

[0433] The water absorption was investigated using the following method:

[0434] The membranes were weighed in dry form (m³). trOcken) and then immersed in ultrapure water for 24 hours at 85 °C. The membranes were then briefly wiped with a cloth and weighed again (m )eu The water absorption (WA) was then calculated using the following formula:

[0435] The result is shown in Figure 12c.

[0436] 3.4 Source behavior

[0437] The source behavior was investigated using the following method:

[0438] Dry membrane pieces of dimensions (2x2) cm 2 Analogous to the measurement of swelling behavior, the membranes were immersed in ultrapure water for 24 hours at 85 °C. Subsequently, the change in size was determined using calipers, and the swelling behavior was calculated using the following formula, where Lmoist is the length of the moist membrane and Ld is the length of the moist membrane. tro cken represents the length of the dry membrane:

[0439] 4. Comparative trials with commercial membranes AEMION+™

[0440] The stability of the membranes according to the invention as shown in Example 2 was investigated in comparison to corresponding unhydrated membranes (as described in international application PCT / EP2024 / 063160).

[0441] It was demonstrated that the hydrogenated membranes (EM-q-co-AM-h) exhibited improved stability in 1 M KOH at 85 °C compared to unsaturated materials ((EM-q-co-AM)). Both a blend with POB and a cross-linked material (2.5 mol% TMHDA) were investigated, and no decrease in conductivity was observed after 6 W in KOH at 85 °C.

[0442] In the case of unsaturated polymers, conductivity analysis was no longer possible because the membranes mechanically disintegrated when treated with 85 °C KOH.

[0443] Furthermore, the materials were investigated with regard to their conductivity as a function of temperature. The materials according to the invention showed very promising conductivities, and the ex-situ stability also indicates excellent chemical stability. Comparisons of the temperature-dependent conductivity with commercial references such as Aemion® membranes further underscore this. 5. Comparative tests with commercial membranes AEMION+™

[0444] The membranes according to the invention as shown in Example 2 were investigated in application testing in comparison to a commercially available membrane AEMION+™.

[0445] AEMION™ (HWK75) commercial membrane is a polybenzimidazole-based membrane with a thickness of 75 µm, distributed by lonomr Innovations Inc.

[0446] Surprisingly, it was found that the membranes according to the invention (IEC = 2.0 meq / g, Mn = 50 kg / mol) from Example 2 can compete with the commercial membrane AEMION™ in application testing and in some cases even surpass it. To achieve a current density of 2 A cm 2 In the case of a 10 wt% POB membrane with a copolymer containing 54 mol% quaternized EM, a voltage of 1.91 V was required, whereas in the case of the commercial reference, 2.3 V was required at the same current density. This underlines the potential of the membrane concept of the present invention.

[0447] The cell voltage at constant current and the polarization are investigated using the following methods:

[0448] The membrane electrode units were used in an anion exchange membrane electrolysis cell for single-cell tests with an active area of ​​5 cm². 2Tested. Titanium bipolar plates were used on the anode and cathode sides. 4 mg / cm³ 2 CoP / C with 10 wt% of a self-synthesized ionomer (PBIM+) [ACS Energy Lett. 2023, 8, 5, 2387-2394] on a NiP fleece was used as a catalyst on the cathode. NiFe-LDH with 10 wt% PBIm+ as an ionomer on a NiS fleece was used as the anode catalyst. Membrane pieces measuring 5 cm x 5 cm were used for the test. These were immersed twice in fresh 1 M KOH. The electrolysis test was carried out at 60 °C with 1 M KOH on the anode and a dry cathode (dry nitrogen).

[0449] The measurement protocol included the following steps:

[0450] 1. Conditioning of 0.1 A cm 2 up to 2.0 A cm 2

[0451] 2. Potentiostatic impedance spectroscopy at 1.5 V

[0452] 3. Maintaining a current of 2 A cm 2 for 2 minutes.

[0453] 4. Recording the polarization curve

[0454] 5. Potentiostatic impedance spectroscopy at 1.5 V

Claims

1. PATENT CLAIM 1. Water-insoluble polymer membrane (AEM) containing a hydrogenated copolymer with a) quaternized norbornene derivative monomer units (EM) of the following formula (I), wherein R 1 a (-CH2OCH2-)I ether or polyether chain with L = 1 to 10, preferably e 1 to < 6, or > 1 to < 4; and A 1 an amine base, selected from the group: where the binding 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); and wherein the copolymers are further reinforced by blending with a chemically inert matrix polymer, and / or ii. covalent cross-linking, and / or iii. cross-linking by non-covalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen bonding interactions and van der Waals interactions with a physicochemical reactant, and / or iv. chemically inert particles, braids or fibers.

2. Water-insoluble polymer membrane (AEM) according to claim 1, wherein the quaternized norbomen derivative monomer units (EM) of formula (I) have an -R 1 -CH2- spacers, wherein R 1 a (-CH2OCH2-)I ether or polyether chain with L = 2 is, according to the following formula (ll) where A 1 represents 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 formula (11-11) EM-co-AM-h (Hl) or by forming block copolymers with block copolymer units (EM-block-AM) of formula (ll-ll) EM-block-AM-h (Il-Il) wherein co is a copolymerized bond and block is a block copolymerized bond and A in each case 1 an amine base according to claim [1], and n and m respectively 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: or from Norbornene-based comonomers according to the following formula (I-Alkyl): wherein R 3 a linear or branched CrC2o alkyl chain (alkyl spacer), preferably a CrCs alkyl chain, more preferably a CX-Ca alkyl chain; and in which A x an amine base selected from the group of quaternizing amine bases A 1 as defined herein, or A x a departure group A 2 as defined herein, preferably selected from the group of halogens, more preferably from the group comprising CI and Br, of which Br is particularly preferred; and n denotes the degree of polymerization.

5. Water-insoluble polymer membrane (AEM) according to any one of claims 1 to 4, which is in the form of a blended membrane with at least one chemically inert matrix polymer, wherein chemically inert matrix polymers are selected from the group (i) comprising polybenzimidazoles: (ii) comprising from the group of isatin polymers Water-insoluble polymer membrane (AEM) according to any one of claims 1 to 5 wherein the copolymers with the monomer units (I) or (II), or copolymers according to formula (11-1) or block copolymers according to formula (11-12) are present as cross-linked copolymers, wherein the copolymers are cross-linked with a cross-linking reagent selected from the group consisting of quaternizing diamines (11-A) and (11-B): (III-A) (III-B) where Y linear or branched Ci-Ci2 alkyl chains, preferably Ci-Cs alkyl chains, more preferably C^Cs alkyl chains, are; and X 1 , X 2 , X 3 and X 4 are each identical or different and independent linear or branched Ci-Cs alkyl chains; or wherein X 1 and / or X 2 each with X 3 and / or X 4together with the nitrogen atom to which they are bonded, form one or two rings, creating a diazacylo or diazabicyclo unit; and wherein Z are each identical or different and independent linear or branched Ci-C4 alkyl chains, preferably Ci-Cs alkyl chains; wherein the crosslinking reagent (11-A) is preferably selected from: N,N,N',N'-Tetramethylhexylenediamine (TMHDA) 1,4-Diazabicyclo[2.2.2] octane and wherein the crosslinking reagent (III-B) is preferably selected from: 1-Methyl-4-[3-(1-methyl-4-piperidyl)propyl]piperidine.

7. Block copolymer according to one of the following formulas (11-C) and (11-D): wherein R 2 = a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or s = 1 to < 4; A 1 represents an amine base according to claim [1] or [6]; A2 a leaving group Br; n denotes the degree of polymerization of the monomer and m the degree of polymerization of the comonomer and; block represents a block copolymerized bond; and wherein in formulas (11-C) and (11D) L = 2 is particularly preferably 8. A method for producing a water-insoluble polymer membrane (AEM) according to any one of claims 1 to 6, comprising the steps of: (a) Copolymerization or block copolymerization of norbornene monomers of the following formula (IV-A) or (l-VB) (IV-A) (IV-B) wherein R 2 a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 2 a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, A is even more preferred 2 = Br; and wherein A 1 an amine base as defined herein, comprising the norbornene-based comonomers (AM) according to claim 1 and optionally comprising one or more identical or different further norbornene-based comonomers according to claim 4; (b) optionally substitution of the Br leaving group with an amine base A 1 according to claim 1; (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-A), (11-B), (11-C) or (11-D); (d) additional enhancement of the copolymers or block copolymers obtained in step (c) by i. blending with a chemically inert matrix polymer, and / or ii. covalent cross-linking, and / or iii. cross-linking by non-covalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen bonding interactions and van der Waals interactions with a physicochemical reactant, and / or iv. chemically inert particles, braids or fibers.

9. Method for producing a water-insoluble polymer membrane (AEM) according to claim 8, comprising the steps: (a) Block copolymerization of norbornene monomers of the following formula (IV-A) or (l-VB) (IV-A) (IV-B) wherein R 2 a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 2a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, A is even more preferred 2 = Br; and wherein A 1 an amine base as defined herein, with the norbornene-based comonomers (AM) according to claim 1 and optionally with one or more identical or different further norbornene-based comonomers according to claim 4; by i) separately dissolving a norbornene monomer of formula (IV-A) or (IV-B) in a suitable solvent and a norbornene-based comonomer (AM) in a suitable solvent to obtain, respectively, a norbornene monomer solution (L1) and a norbornene-based comonomer solution (L11); and ii) separately polymerizing the solutions (L1) and (L11) by adding a catalyst and stirring; and iii) combining the polymerized solutions (L1) and (L11) and block copolymerizing by continuing to stir; (b) optionally substitution of the Br leaving group with an amine base A 1 according to claim [1]; (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-C) or (11-D); (d) additional reinforcement of the block copolymers obtained in step (c) by i. blending with a chemically inert matrix polymer, and / or ii. covalent cross-linking, and / or iii. cross-linking by non-covalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen bonding interactions and van der Waals interactions with a physicochemical reactant, and / or iv. chemically inert particles, braids or fibers.

10. Method for producing a water-insoluble polymer membrane (AEM) according to one of claims 8 or 9, comprising the steps: (a) Copolymerization or block copolymerization of norbornene monomers of the following formula (IV-A) or (l-VB) (IV-A) (IV-B) wherein R 2 a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 2 a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, A is even more preferred 2 = Br; and wherein A 1 an amine base as defined herein, comprising the norbornene-based comonomers (AM) according to claim 1 and optionally comprising one or more identical or different further norbornene-based comonomers according to claim 4; (b) optionally substitution of the Br leaving group with an amine base A 1 according to claim [1]; (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-A), (11-B), (11-C) or (11-D); (d) further enhancement of the copolymers or block copolymers obtained in step (c) by blending with a chemically inert matrix polymer by i. dissolving the copolymers obtained in step (c) in an aprotic solvent; and ii. dissolving a matrix polymer, preferably a matrix polymer according to claim 5, in the solution obtained in step i.; and iii. evaporating the aprotic solvent to obtain the blend membrane.

11. Method for producing a water-insoluble polymer membrane (AEM) according to one of claims 8 or 9, comprising the steps: (a) Copolymerization or block copolymerization of norbornene monomers of the following formula (IV-A) or (l-VB) (IV-A) (IV-B) wherein R 2a (-CH2OCH2-) ether or polyether chain with L = 1 to 10, preferably > 1 to < 6, or > 1 to < 4, more preferably with L = 2; and wherein A 2 a leaving group, wherein leaving groups are preferably selected from the group of halogens or pseudohalogens, halogens are preferred, A is even more preferred 2 = Br; and wherein A 1 an amine base as defined herein, comprising the norbornene-based comonomers (AM) according to claim 1 and optionally comprising one or more identical or different further norbornene-based comonomers according to claim 4; (b) optionally substitution of the Br leaving group with an amine base A 1 according to claim [1]; (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-A), (11-B), (11-C) or (11-D); (d) further strengthening of the copolymers (11-C) or (11-D) or block copolymers obtained in step (c) by covalent cross-linking by i. dissolving the copolymers (11-C) or (11-D) in a suitable solvent; and ii. dissolving a cross-linking reagent, preferably a cross-linking reagent according to claim 6, in the solution obtained in step i.; and iii. evaporating the solvent to obtain the cross-linked membrane.

12. Method for producing a water-insoluble polymer membrane (AEM) according to any one of claims 9 to 11, comprising the steps: (a) Polymerization or copolymerization or block copolymerization of norbomen monomers of the following formula (5-[2-(2-Bromethoxy)ethoxymethyl]bicyclo[2.2.1]hept-2-ene) or according to the following formula where A 1an amine base according to claim [1]; with the norbornene-based comonomers (AM) according to claim 1 and optionally with one or more identical or different further norbornene-based comonomers according to claim 4; (b) optionally substitution of the Br leaving group with an amine base A 1 according to claim [1]; (c) Hydrogenation of the double bonds in the resulting polymer main chain to obtain fully saturated polynorbornenes according to formula (11-A) or (11-B), wherein R 2 represents a (-CH2OCH2-) ether or polyether chain with L = 2; (d) additional strengthening of the copolymers or block copolymers obtained in step (c) by iv. blending with a chemically inert matrix polymer, and / or v. covalent cross-linking, and / or vi. cross-linking by non-covalent interactions, including ionic interactions, dipole-dipole interactions, hydrogen bonding interactions and van der Waals interactions with a physicochemical reactant, and / or vii. chemically inert particles, braids or fibers.

13. Use of the water-insoluble polymer membrane (AEM) according to any one of claims 1 to 6 as an alkaline anion exchange membrane or as an anion-conducting 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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