Cyclooctene-benzophenone monomers and cationic polymers, crosslinked polyelectrolytes, composites, membranes, electrodes and electrochemical devices prepared therefrom, such as electrolyzers

Abstract

The present invention relates to e.g. benzophenone monomers, e.g. cyclooctene (COE) benzophenone monomers (1). Also disclosed are e.g. tetraaminophosphonium (tetrakis®) monomers, e.g. isopropyl-methyltetrakis® monomers (2). The present invention also relates to e.g. cationic polymers (polyelectrolytes, ionomers) prepared from said monomers and crosslinked polyelectrolytes prepared therefrom. The present invention also relates to e.g. composites, membranes and membrane electrode assemblies comprising said crosslinked polyelectrolytes. The present invention also relates to e.g. electrochemical devices comprising said membrane electrode assemblies, e.g. electrolyzers.

Description

[Technical field]

[0001] Related Applications This application claims the benefit of U.S. Provisional Application No. 63 / 231,491, filed August 10, 2021, the entire teachings of which are incorporated herein by reference.

[0002] government support This invention was made with Government support under Grant No. 1951215 awarded by the National Science Foundation (NSF) and Grant No. DE-AR0001058 awarded by the Advanced Research Projects Agency of Energy (ARPA-E). The Government has certain rights in this invention. [Background technology]

[0003] 2. Background of the Invention Polymer electrolytes currently used in fuel cells, electrolyzers, redox flow batteries and water purification have low durability, mechanical strength and electrical conductivity. Current materials are not optimized for performance, durability and cost, reducing the commercial viability of new technologies. Therefore, high performance polymer electrolytes are needed that are characterized by high ionic conductivity and durability under harsh chemical conditions and at high temperatures. Summary of the Invention

[0004] Summary of the Invention In a first aspect, the present invention provides a compound of structural formula (I): [ka] wherein: [ka] The portion represented by C 7-8 cycloalkenyl or 7- to 12-membered heterocycloalkenyl; L 1 (OC 1-12 Alkylene)k , (C 1-12 Alkylene-O) k , C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) k , (C 1-12 Alkylene-NH k Selected from; The moiety represented by G has the following structural formula: [ka] , wherein the moiety is selected from the moiety represented by any one of: [ka] is the L of the part represented by G 1 is the point of attachment to; k is an integer from 1 to 6; a is 1 or 2; Y 1 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) or a bond; and further: Each C 1-12 Alkylene, C 6-12 Arylene, C 1-12 Alkyl, C 7-8 Cycloalkenyl and 7- to 12-membered heterocycloalkenyl are independently optionally selected from F, Cl, Br, OH, NH2, C 1-12 Alkyl, C 6-12 Aryl C 1-12 Haloalkyl, C 1-12 Alkoxy, C6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl).

[0005] In a second aspect, the present invention provides a compound of structural formula (II): [ka] a plurality of first repeating units represented by Structural formula (III): [ka] and wherein the polymer comprises a plurality of second repeating units represented by During the ceremony: Q has the following structural formula: [ka] is a portion represented by one of; U has the following structural formula: [ka] is a portion represented by one of; V has the following structural formula: [ka] is a portion represented by one of W is for C 1-12 Alkyl or: [ka] is a moiety represented by one of the structural formulas selected from [ka] is the point of attachment to adjacent repeat units of the polymer; [ka] L 2 is the point of attachment to; [ka] L 3 is the point of attachment to and further: [ka] is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently C 1-3 is an alkylene or a bond; Z 2 -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR 2 In this case, R 1 and R 2 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 6 -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C 6-12 Arylene and CR 4 In this case, R 3 and R 4 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 9 is NR 10 or a combination; R if present 1 and R if present 3 are independently H, C 1-12 Alkyl and C 6-12 aryl; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12 aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atom to which they are attached, 6-12 Forms an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12Alkyl or C 3-12 is cycloalkyl; or R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl; or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5-12 membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) m , (C 1-12 Alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) m and (C 1-12 Alkylene-NH m Selected from; L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) n , (C 1-12 Alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) n , (C 1-12 Alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; b is 1 or 2; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - is F - , Cl - , Br - , O.H. - , NO - 2. CN - , HCO3 - , CO3 2- , PF6 - , BF4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5-16 membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12Aryl and 5- to 12-membered heterocyclyl are independently optionally selected from F, Cl, Br, OH, NH2, oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl).

[0006] In a third aspect, the present invention provides a compound represented by structural formula (IIa) or structural formula (IIb): [ka] a plurality of first repeat units selected from a bridging moiety represented by Structural formula (III): [ka] and wherein the crosslinked polymer comprises a plurality of second repeating units represented by During the ceremony: [ka] is the point of attachment to adjacent repeat units of the polymer; Q has the following structural formula: [ka] is a portion represented by one of; V has the following structural formula: [ka] is a portion represented by one of; W is for C 1-12 Alkyl or: [ka] is a moiety represented by one of the structural formulas selected from T is C for each occurrence independently. 2-8 is alkylene, [ka] is the point of attachment to adjacent repeat units of the polymer; [ka] L 2 is the point of attachment to; [ka] L 3 is the point of attachment to and further: [ka] is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently C 1-3 is an alkylene or a bond; Z 2 -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR 2 In this case, R 1 and R 2 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 6 -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C6-12 Arylene and CR 4 In this case, R 3 and R 4 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 9 is NR 10 or a combination; R if present 1 and R if present 3 are independently H, C 1-12 Alkyl and C 6-12 aryl; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atom to which they are attached, 6-12 Forms an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12 Alkyl or C 3-12 is cycloalkyl; or R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl; or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5-12 membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) m , (C 1-12 Alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C1-12 Alkylene) m and (C 1-12 Alkylene-NH m Selected from; L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) n , (C 1-12 Alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) n , (C 1-12 Alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - is F - , Cl - , Br - , O.H. - , NO - 2. CN - , HCO3 - , CO3 2- , PF6 - , BF4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5-16 membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl and 5-12 membered heterocyclyl are F, Cl, Br, OH, NH2, oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 and optionally substituted with 1 to 6 substituents independently selected from the group consisting of alkyl, aryl, aryl and alkyl.

[0007] In a fourth aspect, the invention is a composite material comprising a reinforcing material and a polymer as described herein with respect to the second aspect and various aspects thereof or a crosslinked polymer as described herein with respect to the third aspect and various aspects thereof.

[0008] In a fifth aspect, the invention is a membrane comprising a film of a polymer as described herein with respect to the second aspect and various aspects thereof, a crosslinked polymer as described herein with respect to the third aspect and various aspects thereof, or a composite material as described herein with respect to the fourth aspect and various aspects thereof.

[0009] In a sixth aspect, the invention is a membrane electrode assembly comprising a membrane and an electrode as described herein with respect to the fifth aspect and various aspects thereof.

[0010] In a seventh aspect, the invention is an electrochemical device comprising a membrane electrode assembly and a current collector as described herein with respect to the sixth aspect and various aspects thereof. [Brief description of the drawings]

[0011] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] FIG. 1 shows the structural formulas of certain Tetrakis®-BXL polymers containing Tetrakis® cations with various patterns of substitution at the phosphonium cation. [Diagram 2] FIG. 2 shows a matrix illustrating the Tetrakis®-BXL polymer composition for an unsupported AEM containing a phosphonium cation with cyclohexyl, methyl substitution. [Diagram 3] FIG. 3 shows a plot showing the through-plane hydroxide conductivity and area surface resistance of the AEM as a function of polymer loading (polymer loading is plotted on the x-axis). [Figure 4] FIG. 4 shows plots showing the through-plane hydroxide conductivity and areal surface resistivity of the AEM as a function of polymer incorporation method. [Diagram 5] FIG. 5 shows a plot of through-plane hydroxide conductivity for various Tetrakis®-BXL rAEMs supported on polypropylene (PP) (Celgard) at room temperature. [Figure 6] FIG. 6 shows a plot of areal surface resistive conductivity for various Tetrakis®-BXL rAEMs supported on PP (Celgard) at room temperature. [Figure 7] FIG. 7 shows a plot of through-plane hydroxide conductivity for various Tetrakis®-BXL rAEMs supported on PP (Celgard) at 80° C. [Figure 8] FIG. 8 shows a plot of areal surface resistive conductivity for various Tetrakis®-BXL rAEMs supported on PP (Celgard) at 80° C. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Detailed Description To commercialize fuel cells, electrolyzers, redox flow batteries, water purifiers and other electrochemical devices, it is necessary to develop anion exchange membranes (AEMs) that contain durable polymer backbones and cationic groups. Alkaline systems hold several advantages over their acidic counterparts, notably less expensive electrodes and bipolar plates and the fabrication of devices with longer lifetimes. Because oxygen reduction is easier at high pH and lower overpotentials are required, alkaline electrochemical devices are an exciting alternative to proton exchange membrane (PEM) devices and allow metals other than platinum to be used as electrocatalysts.

[0013] Disclosed herein are anion exchange ionomers (AEIs) and AEMs containing the AEIs that exhibit desirable chemical durability, ability to absorb water, and low water solubility in harsh alkaline environments. The disclosed AEMs exhibit reduced water absorption at high temperatures compared to state of the art materials. The AEMs maintain high ionic conductivity and low resistivity without loss of mechanical properties.

[0014] I. General Polymers of the Invention In some embodiments, the AEI can be crosslinked to improve the performance of the material. Exemplary components of a crosslinkable AEI (e.g., backbone, repeating unit, cationic moiety, or crosslinkable moiety) are shown in the following paragraphs. The AEI can include any combination of the components disclosed below.

[0015] 1. Crosslinkable part AEIs can be crosslinked, for example, by introducing crosslinkable pendants into some of the repeating units of the polymer, such as type II photoinitiators, such as benzophenone, camphorquinone, isopropylthioxanthone, and thioxanthone (see Allushi et al., Polymer Chemistry, 2017, 8, 1972-1977). Type I photoinitiators, such as dimethoxyphenylacetophenone, α-hydroxyacetophenone, α-aminoacetophenone, benzoylphosphinoxide, and bisbenzoylphosphinoxide, can also be introduced into some of the repeating units of the polymer.

[0016] 2. Polymer backbone A crosslinkable appendage can be incorporated into a polymer by linking it to a repeating unit, for example, the following repeating unit or polymer backbone: [ka] [ka] can be functionalized with a crosslinkable appendage.

[0017] 3. Cationic Moiety The AEI can include a variety of cationic moieties. For example, cationic moieties can be incorporated into the AEI as appendages linked to the polymer backbone. Additionally or alternatively, the polymer backbone can include cationic groups. For example, the following cationic moieties: [ka] [ka] [ka] can be incorporated into the AEI ( [ka] indicates the point of attachment of the cationic moiety to the backbone or to a linker attached to the backbone).

[0018] 4. Repeating Units AEI is: [ka] The repeat unit may comprise a combination of the repeat units:

[0019] II. Specific Examples of Polymers of the Invention The above-mentioned example of AEI has been further investigated. Disclosed herein is a class of polymers containing Tetrakis® cations and benzophenones that can be crosslinked using UV light, the Tetrakis®-BXL series (FIG. 1). The term Tetrakis® has the following structural formula: [ka] In the formula: [ka] is the point of attachment to the polymer or to a linker that is connected to the polymer, and R a , R b , and R c are each independently alkyl or cycloalkyl.

[0020] Using photocatalysis to crosslink polymers is advantageous because the polymers can be synthesized and fabricated in any form of agent (film, powder, solution) required prior to irreversible crosslinking. UV curing of coatings is common in polymer manufacturing and simplifies processing for larger scale fabrication. This is preferred over methods that crosslink in situ or by chemical soaking after fabrication, as these methods are difficult to translate to large scale manufacturing.

[0021] The Tetrakis®-containing polymers are labeled as follows:

[0022] T-xx-yyy has the following structural formula: [ka] %, containing xx mol.% cationic repeating units and having a MWn of yyy,000 g / mol.

[0023] T-xx-yyy-BXLz has the following structural formula: [ka] % benzophenone-containing repeat units, and has a MWn of yyy,000 g / mol.

[0024] IIa. Tetrakis®-BXL AEI and free-standing Tetrakis®-BXL AEM. An example of a Tetrakis®-BXL AEI is T-28-120-BXL2, which does not require purification, has lower water solubility than the previous non-benzophenone-containing Tetrakis®-containing AEI, and maintains high water uptake at 80° C. The benzophenone-containing (BXL) polymers are highly soluble and processable in organic solvents prior to UV curing. After crosslinking, the new AEIs can be formulated as insoluble powder dispersions.

[0025] Unsupported crosslinked BXL-containing AEMs were prepared by copolymerization with Tetrakis®-functionalized cyclooctene, benzophenone-functionalized cyclooctene, and cyclooctene. The benchmark uncrosslinked Tetrakis® prototype was T-23-300, containing 23% cations and a molecular weight of 300,000 g / mol. First, the cation content was investigated and a series of polymers with 15% BXL content and similar molecular weight to T-23-300 were prepared. The resulting polymers were difficult to handle and curled excessively when manipulated and hydrated. Insufficient handling resulted in irreproducible polymer properties due to 1) inconsistencies in the film or 2) unavoidable measurement errors. It was discovered that the combination of high molecular weight and high benzophenone crosslinking (BXL) content (>15%) was undesirable for a freestanding AEM. Thus, a series of polymers with lower molecular weight and crosslink density were prepared and analyzed. T-28-120-BXL2 and T-28-120-BXL5 were identified as promising AEIs for unsupported crosslinked AEM and T-28-120-BXL5. Furthermore, Tetrakis®-BXL AEM and Tetrakis® AEM were compared with commercial AEM. The structural characteristics of Tetrakis® and Tetrakis®-BXL AEM and commercial AEM are shown in Table 1. [Table 1]

[0026] 1. Comparison of non-crosslinked and crosslinked Tetrakis®-containing ionomers. Three ionomers, non-crosslinked T-28-120 and T p The -23-275 and crosslinked T-28-120-BXL2 were tested for several parameters essential to AEM performance. Table 2 summarizes the characterization data. [Table 2]

[0027] T p Both -23-275 and T-28-120-BXL2 have significantly lower water solubility and higher water uptake compared to the benchmark T-28-120.

[0028] T-28-120-BXL2 has been shown to be a versatile AEI. It can be formulated as a 5 wt % solution in n-propanol prior to crosslinking. The material can be fabricated as an ionomer solution into a catalyst ink by photocrosslinking right at the end of electrode fabrication. Additionally, T-28-120-BXL2 can also be formulated as an insoluble powder dispersion in isopropanol if that method is desired in electrode fabrication.

[0029] 2. Comparison of crosslinked Tetrakis®-containing ionomers with commercial ionomers. The crosslinked AEI T-28-120-BXL2 was further compared to commercially available ionomers from Fumatech (Fumion FAA-3-50) and Dioxide Materials (Sustainion® XB-7). Table 3 summarizes the characterization data for T-28-120-BXL2 and the commercial AEI. [Table 3]

[0030] The data in Table 3 show that T-28-120-BXL2 outperforms both the Fumion and Sustainion ionomers.

[0031] 3. Comparison of non-crosslinked and crosslinked Tetrakis®-containing AEMs. Crosslinked AEM T-28-120-BXL5 was compared to Tetrakis®-containing non-crosslinked membranes, T-25-360 and T-23-300. Comparative data is shown in Table 4. [Table 4]

[0032] The data in Table 4 show that the crosslinked version of Tetrakis® AEM (T-28-120-BXL5) exhibited low film swelling and water uptake, enabling high conductivity and low resistivity at room temperature and 80° C. Even at low thickness (30 microns), the handling performance of T-28-120-BXL5 was excellent at room temperature and 80° C. The AEM appeared to be mechanically very robust without being brittle.

[0033] 4. Comparison of cross-linked Tetrakis®-containing AEM with commercially available AEM. Cross-linked AEM, T-28-120-BXL5, was used with Xergy (Xion Durion TM Further comparisons were made with commercially available membranes from Fumatech (FAA-3-50 & FAS-50), Dioxide Materials (Sustainion® X37-50), and others. The comparative data is shown in Table 5. The structural characteristics of the commercial AEMs are listed in Table 1. [Table 5]

[0034] With the exception of T-28-120-BXL5 and Pention 72-30-15, the AEMs absorbed excessive amounts of water at 80° C. High water uptake and swelling in the AEMs results in lower electrical conductivity at elevated temperatures in addition to softening and difficulty in handling.

[0035] Xion Durion is a cross-linked and reinforced material that is reported to have high water uptake at room temperature (RT) and 80°C. TMThis was observed for 215-30. Pention 72-30-15 is also crosslinked and reinforced with a polytetrafluoroethylene (PTFE) support. In contrast, T-28-120-BXL5 is crosslinked but not reinforced. The ability of T-28-120-BXL5 to achieve low expansion and high conductivity without reinforcement is an advantage for manufacturing, as it requires less processing, resources and development. Furthermore, Pention 72-30-15 requires a chemical crosslinking process in which the film is immersed in an amine solution. This type of chemical crosslinking can be difficult to achieve reproducibly at a consistent scale. T-28-120-BXL5 AEM exhibits excellent in-plane and through-plane hydroxide ion conductivity at 80° C. as well as low area-specific resistance (ASR). Thus, water uptake can be low enough for excellent device performance.

[0036] IIb. Reinforced Tetrakis®-BXL AEM (rAEM). The advantage of increasing the AEM charge density is diminished if the polymer affinity for water is too high. Although some water uptake is necessary for proper ion transport, too much swelling has a negative effect. This reduces the mechanical properties of the unsupported AEM, and 3D swelling reduces ionic conductivity by increasing the distance the ions travel. Large changes in polymer dimensions during humidity cycling increase stress on the membrane, which is especially problematic for fuel cell electrolytes. Additionally, AEMs can become water soluble at very high IEC. Reinforced AEMs (composites) are less susceptible to mechanical problems, but water solubility remains an issue. Increasing the polymer molecular weight is easily achieved by the disclosed polymerization procedure, but further modifications are necessary to inhibit water solubility at optimal IEC values. Crosslinking of the polymer is a common method to prevent solubility altogether.

[0037] To make AEMs even more compelling, it is important to reduce the thickness of the electrolyte layer to reduce the overall resistance by increasing ionic conductivity without sacrificing mechanical strength. Traditional methods of increasing conductivity include increasing the ionic content or IEC in the polymer. This strategy is easily achieved with ROMP technology. However, higher ionic content results in higher water uptake and excessive swelling of the polymer electrolyte, resulting in mechanical failure. Although certain AEMs are non-brittle flexible films at reduced thickness, swelling of such membranes in water at high temperatures can make them highly viscoelastic. Including additional aspects to the system that simultaneously allow for higher IEC of thinner electrolytes, mechanical strength and reduced dimensional change in hydrated electrolytes results in the desired AEM product.

[0038] 1. Porous support This disclosure provides a method to infuse AEM materials into unoccupied spaces within various porous polymer structural supports. The structural rigidity and mechanical strength of the supports were successfully matched with the electrochemical properties of the polymer electrolyte. The resulting composites were fully characterized to analyze the level of polymer impregnation, water uptake level, thermal properties and electrochemical performance. Polymer materials from several international companies such as polyethylene (PE) and polypropylene (PP) were obtained.

[0039] There is an optimal amount of void space remaining in the dried AEM composite after fabrication. Essentially, the bare porous support has a certain amount of pore volume. During fabrication, the AEM material is dissolved in a solvent compatible with the support and then the mixture is applied to the support to fill the pores of the support material. When the solvent is removed, the dried composite has a new void volume. The reinforced AEM is hydrated prior to use in an electrochemical device, and the polymer embedded in the support expands and many of the void spaces are once again filled. A certain amount of void space is required in the dried AEM to maintain a high density of cations for ion transport, but also includes an appropriate amount of space for water. The exact amount of void space is specific to each type of polymer electrolyte and porous support combination.

[0040] BET can be used to analyze how the void volume changes from the bare support and the dried composite. The key variables for adjusting the void space are the solvent identity and concentration of the polymer in the solution, as well as the method of introducing the solution into the support matrix. The solvent selected must be compatible with the support polymer and must solubilize the AEM to the desired level. Often, co-solvent mixtures are also investigated. The concentration must also be optimized, as too high a concentration may prevent the AEM from reaching the support, and if too low not enough AEM will penetrate the support. A rheometer can be used to characterize the viscosity of the polymer solution, and a Zetasizer can be used to analyze the uniformity and dispersion of the polymer particles. Measuring these solution properties that affect the amount and distribution of AEM in the support aids in composite optimization. Ionic conductivity can be measured in relation to void volume to establish a link between physical properties and electrochemical performance.

[0041] Porous polymer supports are typically designed for filtration and separation of solids, liquids and gases or for sterilizing biological solutions, and are not optimized to be filled with another polymer to create high performance components for electrochemical devices. Optimizing support specifications for these applications generally does not provide sufficient overlap for the classes of supports required for composites. Therefore, it is important to develop polymer supports that are specifically designed with composites in mind as the final application.

[0042] The first requirement for custom designing a support for a composite is to determine what polymeric material to use. PE and PP are polymers with high chemical resistance. The best thermal properties are observed with PTFE, but it is a very expensive raw material, is not recyclable, and processing methods for making porous materials from PTFE are limited to expanding. Both PE and PP are significantly less expensive than PTFE, they are both recyclable, and can be processed using many different methods.

[0043] The next requirement for designing a custom support is the choice of fiber and the method of fabricating the fibers into a mat or sheet of material. The method may be limited to a few polymers, for example, only PTFE may be spread into sheets. PE and PP films can be prepared by a variety of polymer fabrication methods. The type of fabrication has a significant effect on the morphology and alignment of the polymer strands. These characteristics affect the performance of the composite, as they can affect how the polymer electrolyte interacts with the support and how easily it fills voids. In addition, the mechanical properties of the support will vary based on the diameter of the fibers used and how the fibers are aligned relative to each other, affecting the durability of the composite. Both characteristics must be considered to obtain the best properties in the final material. The overall thickness of the support must also be designed. Preliminary results show that AEMs with lower thicknesses also have lower resistance (57 μm thick AEMs had a resistance of 256 mΩ and 74 μm thick AEMs had a resistance of 458 mΩ).

[0044] Additional features of the porous support that can be customized include pore size and porosity. Pore size simply indicates how large the average pore size is in a given section of the support. Porosity indicates how much of the volume within a given area is free volume versus that absorbed by the support. Porosity is another way to characterize the free volume of a bare support. Both of these features affect how the polymer electrolyte fills the voids in the support and the resulting mechanical strength of the composite.

[0045] The pore size and porosity of the supports are measured by BET before and after filling with polymer electrolyte to validate the fabrication method and to support the development of optimized composites. Dynamic light scattering (DLS) with Zetasizer and rheological measurements are useful to characterize the dip-coating solutions and catalyst ink formulations.

[0046] A summary of the porous supports investigated is provided in Table 6. [Table 6]

[0047] The Gurley value is the time required for a specific amount of air to pass through a separator of a specific area in a battery under a specific pressure. The Gurley value reflects the tortuosity of the pores when the separator porosity and thickness are fixed.

[0048] In some embodiments, the desired thinner electrolyte comprises a composite AEM by filling a porous polymer support with AEM material. PE and PP structural supports were used as support materials. In addition to allowing higher IEC, the porous composite can provide a less tortuous path to facilitate the passage of anions through the electrolyte layer, further improving performance without compromising mechanical structure or stability. Using a support allows a wider range of thicknesses by casting the membrane onto a thin composite material.

[0049] 2. How to prepare rAEM. Various fabrication methods for rAEMs were investigated using several types of commercially available mesoporous supports and Tetrakis®-BXL AEI. A summary of the prepared polymer compositions is shown in Figure 2. Two rAEMs with high conductivity, low ASR, low to moderate water uptake and excellent mechanical properties were prepared using polypropylene supports. Additionally, one rAEM showing promising conductivity and low ASR was prepared using polyethylene support material. There is an optimum value for how much polymer should be incorporated into the support material for best rAEM properties. Experiments suggested that void volume may enhance the properties of the rAEM and that filling the support material may not produce the best rAEM at all. Very high polymer loadings resulted in poor handling of the materials, making them difficult to use in various conditions. Many of the commercially available AEMs "bend" excessively into a tight locked DNA-like helical structure and cannot be unfolded, giving them insufficient flexibility and mechanical robustness. The data in FIG. 3 show that the conductivity and ASR of the AEM plateau (x-axis) at high polymer loading.

[0050] Dip-coating, drop-casting and spray-coating were evaluated as methods of incorporating the polymer into the support. For the drop-casting method, multiple solution viscosities were examined, both more viscous solutions with more polymer solids and less viscous solutions with less polymer solids, to improve penetration into the support. However, it was discovered that this method results in a thick coating of polymer on the surface of the support material and does not maximize the amount of polymer incorporated. As a result, the spray-coating method was selected for its potential as a scalable technique. The spray-coating method uses a directional force to apply the polymer solution, rather than allowing the incorporation to be driven slowly by gravity. Spray-coating produces rAEMs with excellent uniformity at a much larger scale than current unsupported films. Spray-coating was selected as the method to incorporate Tetrakis®-BXL polymer into the support material and produce rAEMs. The method provides good incorporation by providing a gentle and consistent force that pushes the polymer into the support.

[0051] The following parameters were identified as important for the fabrication of AEMs via spray coating:

[0052] i. Percent solids of polymer in casting solution Solutions with 4 wt% polymer solids (Tetrakis®-BXL series) are low viscosity and compatible with spray coating. Several layers of polymer are easily administered by spray coating techniques, offering many advantages over other coating methods. This advantage of Tetrakis®-BXL is due to the following factors:

[0053] 1) The presence of benzophenone makes the polymer partially more hydrophobic. When a solvent mixture (including water) is added to the BXL series of polymers, the polymer forms small dense balls that result in a uniform, homogeneous suspension with low viscosity. By adding a more hydrophobic component, the polymer becomes less well soluble in the hydrophilic solvent instead of forming a uniform suspension;

[0054] 2) The incorporation of benzophenone helps break up the aggregation of cationic segments in the polymer. In polymers without benzophenone, the cationic portions of the polymer chains strongly prefer one another, and they aggregate, reducing "solubility" or increasing viscosity. Adding the benzophenone hydrophobic segments breaks up the cationic aggregation, resulting in lower viscosity.

[0055] ii. Solvent Selection A 2:1 water:n-propanol co-solvent was identified as an effective solvent system for spray coating the Tetrakis®-BXL series of polymers onto a variety of mesoporous substrates. The solvent system works well with PP (polypropylene) and PE (polyethylene) and dries easily with a short drying step (1 hour at 80°C).

[0056] iii. Selection of support material PP and PE are highlighted as non-fluorinated support materials. There are several commercially available options with a variety of properties to evaluate and inform custom support design.

[0057] iv. Preparation of Support Material Prior to rAEM Fabrication Washing the PP and PE substrates with ethanol provides improved rAEM characteristics.

[0058] v. Methods for incorporating polymers into supports and creating rAEMs Spray coating with the following parameters: Manual vs. Automated 3D Printing Single vs. double sided coating Spray speed Number of coatings was investigated.

[0059] In addition to better uniformity and handling, the spray coating technique produced rAEMs with relatively low ASR (Figure 4). The double coating method offered a small improvement and was the method of choice for the current development.

[0060] Tetrakis®-BXL AEM offered unexpected processing advantages. Polymers containing benzophenone are significantly more solvent processable, even at small levels of incorporation. Tetrakis®-BXL polymers are easily solution cast from mixtures of n-propanol and water. The boiling points of water (100° C.) and n-propanol (98° C.) are relatively low and similar to one another, providing simplified uniform drying. This is an improvement over more typical solution casting from dimethylformamide (DMF), which has a boiling point of 153° C. AEM and rAEM cast from DMF required a two-step drying system: 1) several hours at 80° C. / ambient pressure, followed by 2) overnight at 125° C. / vacuum.

[0061] 3. Characterization of Tetrakis®-BXL rAEM The following tests were performed to characterize rAEM: - The through-plane hydroxide conductivity and ASR of the rAEM were measured. - Values ​​at ambient temperature were compared for support selection and fabrication optimization. - Tensile tests were performed to determine the stress and strain at failure for selected rAEMs. - Water uptake and swelling tests of rAEM were performed. - In-plane hydroxide conductivity of selected rAEMs was performed. - IEC of selected rAEM was performed.

[0062] A. Characterization studies were performed that focused on the following variables: polymer loading, polymer volume, and rAEM thickness.

[0063] The following materials were evaluated:

[0064] ia. T-28-120-BXL2 spray coated and UV crosslinked PE (Teijin) In the range of substrate thicknesses evaluated (20-80 μm), lower ASRs corresponded to thinner rAEMs (dry and wet at RT). In the range of polymer loadings evaluated (1.0-5.3 mg / cm2), lower ASRs generally tended to be accompanied by lower loadings and polymer volumes, with a preferred value of 3 mg / cm2. 2 The low ASR is followed by the low conductivity - ASR takes precedence over conductivity.

[0065] iia. T-46-120-BXL2 spray coated and UV crosslinked PE At RT, higher polymer volumes resulted in lower ASR and higher conductivity in the range of polymer volumes evaluated (582-743 mg / cm3; 1.5 mg / cm2, respectively). At 80°C, the trend disappeared and ASR was the same for all polymer volumes. Z-direction swelling (thickness) appeared to be the same at RT and 80°C. Thin rAEMs were produced with dry thicknesses less than 30 μm. Conductivity and ASR appear to track inversely - lower ASR pairs with higher conductivity. Gurley number and porosity of the support do not appear to affect rAEM properties.

[0066] iiia. PP spray coated with T-28-120-BXL2 and UV crosslinked (Celgard) The rAEMs prepared with the Celgard PP support tended to be uniform in properties - higher polymer loadings resulted in higher polymer volumes, leading to higher dry and wet thicknesses. The trends may suggest an advantage for fabrication with the PP support. Higher loadings (0.2-4.0 mg / cm)2 ) resulted in higher conductivity and lower ASR.

[0067] B. Substrate Further tests were conducted to evaluate the properties of PP (Celgard) based rAEM as a function of Gurley value and polymer composition.

[0068] ib. T-28-120-BXL2 spray coated and UV crosslinked PP (Celgard): Substrate selected based on Gurley variation Mesoporous PP substrates with a range of Gurley values ​​were evaluated, with the lowest Gurley value shown to result in both the lowest ASR and the highest conductivity. A PP substrate with a Gurley value of 100 sec / dL was selected for further fabrication and polymer composition evaluation. Higher porosity generally resulted in lower ASR and higher conductivity. No clear trends were observed for substrate thickness, wet thickness, or polymer volume.

[0069] iib. Evaluation of polymer composition in PP (Celgard) The effect of cation content in Tetrakis®-BXL polymers on rAEM performance was investigated (Figures 5-8). Across the polymer compositions, higher loadings resulted in higher conductivity and lower ASR. At RT, higher conductivity and lower ASR were observed with increasing cation content in the polymer; however, the trend at 80°C was less clear. Optimization of cation content and crosslink density requires evaluation beyond conductivity and ASR, such as water uptake and mechanical properties. Higher crosslink density in rAEMs with 70% cation content resulted in higher conductivity and lower ASR at 80°C. Increased water uptake / swelling was also observed with increasing crosslink density, but values ​​were similar between RT and 80°C.

[0070] C. PP-supported Tetrakis®-BXL rAEM, unsupported cross-linked Tetrakis®-BXL AEM and uncross-linked Tetrakis® were characterized for several key AEM parameters (Table 7). [Table 7-1] [Table 7-2]

[0071] D. PP-supported Tetrakis®-BXL rAEM was also compared to the commercially available AEM (Table 8). [Table 8-1] [Table 8-2]

[0072] The structural features of Xion Durion are listed in Table 1. Versogen rAEM is an AEM reinforced with a microporous ePTFE support and has the following structure: [ka] Includes AIE.

[0073] definition Definitions of specific functional groups and chemical terms are described in more detail below. Chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Edition, inside cover, and specific functional groups are generally defined as described therein. In addition, general principles of organic chemistry and specific functional moieties and reactivities are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March, March's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; and Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987.

[0074] The compounds described herein may contain one or more asymmetric centers, and therefore may exist in various stereoisomeric forms, such as enantiomers and / or diastereomers.For example, the compounds described herein may be in the form of individual enantiomers, diastereomers or geometric isomers, or may be in the form of a mixture of stereoisomers, such as racemic mixtures and mixtures enriched with one or more stereoisomers.Isomers can be isolated from mixtures by methods known to those skilled in the art, such as chiral high pressure liquid chromatography (HPLC) and the formation and crystallization of chiral salts; or preferred isomers can be prepared by asymmetric synthesis. See, e.g., Jacques et al., Enantiomers, Racemates and Resolutions, Wiley Interscience, New York, 1981; Wilen et al., Tetrahedron 33:2725 (1977); Eliel, EL Stereochemistry of Carbon Compounds, McGraw-Hill, NY, 1962; and Wilen, SH, Tables of Resolving Agents and Optical Resolutions p. 268, EL Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972. The present invention further encompasses the compounds as individual isomers substantially free of other isomers and alternatively as mixtures of various isomers.

[0075] During the ceremony, [ka] is a single or double bond.

[0076] When a range of values ​​is listed, it is intended to encompass each value and subrange within the range.

[0077] For example, "C 1-6 Alkyl" is C1, C2, C3, C4, C5, C6, C 1-6 , C1-5 , C 1-4 , C 1-3 , C 1-2 , C 2-6 , C 2-5 , C 2-4 , C 2-3 , C 3-6 , C 3-5 , C 3-4 , C 4-6 , C 4-5 and C 5-6 Alkyl is intended to be included.

[0078] The term "alkyl" refers to the radical of a linear or branched saturated hydrocarbon group having 1 to 18 carbon atoms ("C 1-18 In some embodiments, an alkyl group has 1 to 12 carbon atoms ("C 1-12 In some embodiments, the alkyl group has 1 to 8 carbon atoms ("C 1-8 In some embodiments, the alkyl group has 1 to 6 carbon atoms ("C 1-6 In some embodiments, the alkyl group has 1 to 3 carbon atoms ("C 1-3 In some embodiments, the alkyl group has 2 to 6 carbon atoms ("C 2-6 "Alkyl"). C 1-6 Examples of alkyl groups include methyl (C1), ethyl (C2), propyl (C3) (e.g., n-propyl, isopropyl), butyl (C4) (e.g., n-butyl, tert-butyl, sec-butyl, iso-butyl), pentyl (C5) (e.g., n-pentyl, 3-pentanyl, amyl, neopentyl, 3-methyl-2-butanyl, tertiary amyl), and hexyl (C6) (e.g., n-hexyl). Further examples of alkyl groups include n-heptyl (C7), n-octyl (C8), and the like. Unless otherwise specified, each instance of an alkyl group is independently unsubstituted ("unsubstituted alkyl") or substituted ("substituted alkyl"). In some embodiments, an alkyl group is an unsubstituted C 1-12 Alkyl (e.g. unsubstituted C 1-6Alkyl, e.g., -CH3(Me), unsubstituted ethyl (Et), unsubstituted propyl (Pr, e.g., unsubstituted n-propyl (n-Pr), unsubstituted isopropyl (i-Pr), unsubstituted butyl (Bu, e.g., unsubstituted n-butyl (n-Bu), unsubstituted tert-butyl (tert-Bu or t-Bu), unsubstituted sec-butyl (sec-Bu), unsubstituted isobutyl (i-Bu)). In some embodiments, the alkyl group is a substituted C 1-12 Alkyl (e.g., substituted C 1-6 alkyl, for example -CF3, Bn).

[0079] The term "haloalkyl" refers to a substituted alkyl group in which one or more of the hydrogen atoms are independently replaced by a halogen, such as fluoro, bromo, chloro, or iodo. In some embodiments, the haloalkyl moiety has 1 to 12 carbon atoms ("C 1-12 In some embodiments, the haloalkyl moiety has 1 to 6 carbon atoms ("C 1-6 In some embodiments, the haloalkyl moiety has 1 to 4 carbon atoms ("C 1-4 In some embodiments, the haloalkyl moiety has 1 to 3 carbon atoms ("C 1-3 In some embodiments, the haloalkyl moiety has 1 to 2 carbon atoms ("C 1-2 Examples of haloalkyl groups include, -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CF3, -CF2CF2CF3, -CCl3, -CFCl2, -CF2Cl, and the like.

[0080] The term "alkoxy," as defined herein, refers to an alkyl group attached to the parent molecular moiety through an oxygen atom. In some embodiments, the alkoxy moiety has 1 to 12 carbon atoms ("C 1-12 In some embodiments, the alkoxy moiety has 1 to 6 carbon atoms ("C 1-6 In some embodiments, the alkoxy moiety has 1 to 4 carbon atoms ("C 1-4In some embodiments, the alkoxy moiety has 1 to 3 carbon atoms ("C 1-3 In some embodiments, the alkoxy moiety has 1 to 2 carbon atoms ("C 1-2 Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy, and tert-butoxy.

[0081] In some embodiments, "cycloalkyl" is a radical of a monocyclic or polycyclic saturated hydrocarbon group having 3 to 18 ring carbon atoms ("C 3-18 In some embodiments, a cycloalkyl group has 3 to 12 ring carbon atoms ("C 3-12 In some embodiments, a cycloalkyl group has 3 to 8 ring carbon atoms ("C 3-8 In some embodiments, a cycloalkyl group has 5 to 12 ring carbon atoms ("cycloalkyl"). 5-12 In some embodiments, a cycloalkyl group has 4 to 6 ring carbon atoms ("C 4-6 In some embodiments, a cycloalkyl group has 5 to 6 ring carbon atoms ("C 5-6 In some embodiments, a cycloalkyl group has 5 to 7 ring carbon atoms ("C 5-7 Polycyclic cycloalkyl groups can be, for example, bicyclic, tricyclic, or tetracyclic. Polycyclic cycloalkyl groups can include fused cycloalkyl rings. Polycyclic cycloalkyl groups can be spirocyclic or bridged cycloalkyl groups. 5-6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C6). 3-6 Examples of cycloalkyl groups include the above-mentioned C 5-6 Cycloalkyl groups include cyclopropyl (C3) and cyclobutyl (C4). 3-8 Examples of cycloalkyl groups include the above-mentioned C 3-6Cycloalkyl groups include cycloheptyl (C7) and cyclooctyl (C8). Unless otherwise specified, each instance of a cycloalkyl group is independently unsubstituted ("unsubstituted cycloalkyl") or substituted with one or more substituents ("substituted cycloalkyl"). In some embodiments, the cycloalkyl group is an unsubstituted C 3-12 In some embodiments, the cycloalkyl group is a substituted C 3-12 In some embodiments, the cycloalkyl group is an unsubstituted C 5-12 In some embodiments, the cycloalkyl group is a substituted C 5-12 It is cycloalkyl.

[0082] In some embodiments, a "cycloalkenyl" is a non-aromatic radical of a monocyclic or polycyclic hydrocarbon group having at least one double bond and 4 to 18 ring carbon atoms ("C 4-18 In some embodiments, a cycloalkenyl group has 4 to 12 ring carbon atoms ("C 4-12 In some embodiments, a cycloalkyl group has 4 to 8 ring carbon atoms ("C 4-8 In some embodiments, a cycloalkenyl group has 5 to 12 ring carbon atoms ("cycloalkenyl"). 5-12 In some embodiments, a cycloalkenyl group has 7 to 8 ring carbon atoms ("C 7-8 Polycyclic cycloalkenyl groups can be, for example, bicyclic, tricyclic, or tetracyclic. Polycyclic cycloalkenyl groups can include a cycloalkenyl ring fused to another cycloalkenyl ring, a cycloalkyl ring, or a heterocyclyl ring. Polycyclic cycloalkenyl groups can be spirocyclic or bridged cycloalkenyl groups. Exemplary cycloalkenyl groups include, without limitation, cyclooctenyl, bicyclooctenyl, and norbornenyl.

[0083] The term "aryl" refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10 or 14 pi electrons shared in the cyclic array) having 6 to 14 ring carbon atoms and 0 heteroatoms provided in the aromatic ring system (e.g., having 6, 10 or 14 pi electrons shared in the cyclic array). 6-14 In some embodiments, an aryl group has 6 ring carbon atoms ("C aryl"; e.g., phenyl). In some embodiments, an aryl group has 10 ring carbon atoms ("C 10 Aryl"; e.g. naphthyl, such as 1-naphthyl and 2-naphthyl). In some embodiments, the aryl group has 14 ring carbon atoms ("C 14 "Aryl"; e.g., anthracyl). "Aryl" also includes ring systems in which an aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups, and the point of radical or attachment is on the aryl ring, and in such instances, the number of carbon atoms continues to indicate the number of carbon atoms in the aryl ring system. Unless otherwise specified, each instance of an aryl group is independently unsubstituted ("unsubstituted aryl") or substituted with one or more substituents ("substituted aryl"). In certain embodiments, an aryl group is an unsubstituted C 6-12 In some embodiments, the aryl group is a substituted C 6-12 It is aryl.

[0084] The term "aryloxy," as defined herein, refers to an aryl group attached to the parent molecular moiety through an oxygen atom. In some embodiments, the aryloxy moiety has 6 to 12 carbon atoms ("C 6-12 In some embodiments, the aryloxy moiety has 6 to 10 carbon atoms ("C 6-10 Representative examples of aryloxy include, but are not limited to, phenoxy and naphthoxy.

[0085] The term "heterocyclyl" or "heterocyclic" refers to a radical of a 3- to 16-membered saturated, unsaturated, non-aromatic or aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen and sulfur (a "5- to 16-membered heterocyclyl"). In heterocyclyl groups that contain one or more nitrogen atoms, the point of attachment may be at a carbon or nitrogen atom where valence permits. Heterocyclyl groups can be either monocyclic ("monocyclic heterocyclyl") or polycyclic (e.g., fused, bridged, or spiro ring systems, such as bicyclic ("bicyclic heterocyclyl") or tricyclic ("tricyclic heterocyclyl"). Heterocyclyl polycyclic ring systems can contain one or more heteroatoms in one or both rings. "Heterocyclyl" also refers to ring systems in which the heterocyclyl ring is fused to one or more cycloalkyl groups as defined above, with the point of attachment being either on the cycloalkyl or heterocyclyl ring, or a ring system in which the heterocyclyl ring is fused to one or more cycloalkyl groups as defined above. In some embodiments, the heterocyclyl group is fused to one or more aryl groups as in the embodiment shown, and the point of attachment is on the heterocyclyl ring, in which case the ring member numbering continues to indicate the ring member numbering in the combined fused ring system. Unless otherwise specified, each instance of heterocyclyl is independently unsubstituted ("unsubstituted heterocyclyl") or substituted with one or more substituents ("substituted heterocyclyl"). In some embodiments, the heterocyclyl group is an unsubstituted 5-12 membered heterocyclyl. In some embodiments, the heterocyclyl group is a substituted 5-12 membered heterocyclyl.

[0086] In some embodiments, a heterocyclyl group is a 5-10 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-10 membered heterocyclyl"). In some embodiments, a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-8 membered heterocyclyl"). In some embodiments, a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-6 membered heterocyclyl"). In some embodiments, a 5-6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, a 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, the 5- to 6-membered heterocyclyl has one ring heteroatom selected from nitrogen, oxygen, and sulfur.

[0087] As used herein, the term "heterocycloalkenyl" refers to an unsaturated non-aromatic heterocyclyl group containing one or more double bonds as described above. In some embodiments, a heterocycloalkenyl group is a bicyclic bridged moiety. In some embodiments, a heterocycloalkenyl group is a bicyclic fused moiety. Exemplary heterocycloalkenyl groups include, but are not limited to, 7-oxabicyclo[2.2.1]hept-2-ene, 7-azabicyclo[2.2.1]hept-2-ene, and 7-methyl-7-azabicyclo[2.2.1]hept-2-ene.

[0088] Exemplary 3-membered heterocyclyl groups containing one heteroatom include, but are not limited to, aziridinyl, oxiranyl, and thiiranyl. Exemplary 4-membered heterocyclyl groups containing one heteroatom include, but are not limited to, azetidinyl, oxetanyl, and thietanyl. Exemplary 5-membered heterocyclyl groups containing one heteroatom include, but are not limited to, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary 5-membered non-aromatic heterocyclyl groups containing one heteroatom include, but are not limited to, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary 5-membered heterocyclyl groups containing two heteroatoms include, but are not limited to, dioxolanyl, oxathiolanyl, and dithiolanyl. Exemplary 5-membered heterocyclyl groups containing three heteroatoms include, but are not limited to, triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6-membered heterocyclyl groups containing one heteroatom include, but are not limited to, piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl. Exemplary 6-membered heterocyclyl groups containing two heteroatoms include, but are not limited to, piperazinyl, morpholinyl, dithianyl, and dioxanyl. Exemplary 6-membered heterocyclyl groups containing three heteroatoms include, but are not limited to, triazinyl. Exemplary 7-membered heterocyclyl groups containing one heteroatom include, but are not limited to, azepanyl, oxepanyl, and thiepanyl. Exemplary 8-membered heterocyclyl groups containing one heteroatom include, but are not limited to, azocanyl, oxecanyl, and thiocanyl.Exemplary bicyclic heterocyclyl groups include, but are not limited to, indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, tetrahydrobenzothienyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, decahydroisoquinolinyl, octahydrochromenyl, octahydroisochromenyl, decahydronaphthyridinyl, decahydro-1,8-naphthyridinyl, octahydropyrrolo[3,2-b]pyrrole, indolinyl, phthalimidyl, naphthalimidyl, chromanyl, chromenyl, lH-benzo[e][1,4]diazepine, 1H-benzo[e][1,4]diazepam ... pyranyl, 1,4,5,7-tetrahydropyrano[3,4-b]pyrrolyl, 5,6-dihydro-4H-furo[3,2-b]pyrrolyl, 6,7-dihydro-5H-furo[3,2-b]pyranyl, 5,7-dihydro-4H-thieno[2,3-c]pyranyl, 2,3-dihydro-1H-pyrrolo[2,3-b]pyridinyl, 2,3-dihydrofuro[2,3-b]pyridinyl, 4,5,6,7-tetrahydro-1H-pyrrolo[2,3-b]pyridinyl, 4,5,6,7-tetrahydrofuro[3,2-c]pyridinyl, 4,5,6,7-tetrahydrothieno[3,2-b]pyridinyl, 1,2,3,4-tetrahydro-1,6-naphthyridinyl, and the like.

[0089] In some embodiments, the term "heterocyclyl" refers to a radical of a 5-16 membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10 or 14 pi electrons shared in a ring array), also referred to as "heteroaryl", having ring carbon atoms and 1-4 ring heteroatoms provided within the aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur. In heteroaryl groups containing one or more nitrogen atoms, the point of attachment may be a carbon or nitrogen atom, if valence permits. Heteroaryl polycyclic ring systems may contain one or more heteroatoms in one or both rings. "Heteroaryl" includes ring systems in which a heteroaryl ring is fused with one or more carbocyclyl or heterocyclyl groups as defined above, and the point of attachment is on the heteroaryl ring, and in such instances, the numbering of the ring members continues to indicate the numbering of the ring members of the heteroaryl ring system. "Heteroaryl" also includes ring systems in which a heteroaryl ring is fused to one or more aryl groups as defined above, with the point of attachment being on either the aryl or heteroaryl ring, and in such instances the ring member numbers refer to the ring member numbers of the fused polycyclic (aryl / heteroaryl) ring system. Polycyclic heteroaryl groups, where one ring does not contain heteroatoms (e.g. indolyl, quinolinyl, carbazolyl, etc.), the point of attachment can be on either ring, i.e. either ring with a heteroatom (e.g. 2-indolyl) or ring without a heteroatom (e.g. 5-indolyl).

[0090] In some embodiments, a heteroaryl group is a 5-12 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided within the aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-12 membered heteroaryl"). In some embodiments, a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided within the aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-8 membered heteroaryl"). In some embodiments, a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided within the aromatic ring system, where each heteroatom is independently selected from nitrogen, oxygen, and sulfur ("5-6 membered heteroaryl"). In some embodiments, a 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, a 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, a 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, and sulfur. Unless otherwise specified, each instance of a heteroaryl group is independently unsubstituted ("unsubstituted heteroaryl") or substituted with one or more substituents ("substituted heteroaryl"). In some embodiments, a heteroaryl group is an unsubstituted 5-14 membered heteroaryl. In some embodiments, a heteroaryl group is a substituted 5-14 membered heteroaryl.

[0091] Exemplary 5-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyrrolyl, furanyl, and thiophenyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include, but are not limited to, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include, but are not limited to, triazolyl, oxadiazolyl, and thiadiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include, but are not limited to, tetrazolyl. Exemplary 6-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyridinyl. Exemplary 6-membered heteroaryl groups containing two heteroatoms include, but are not limited to, pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to, triazinyl and tetrazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to, azepinyl, oxepinyl and thiepinyl. Exemplary 5,6-bicyclic heteroaryl groups include, but are not limited to, indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzimidazolyl, benzoxazolyl, benzoisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzoisothiazolyl, benzothiadiazolyl, indolizinyl and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include, but are not limited to, naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl and quinazolinyl. Exemplary tricyclic heteroaryl groups include, without limitation, phenanthridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenothiazinyl, phenoxazinyl, and phenazinyl.

[0092] The terms "unsaturated" or "partially unsaturated" refer to a moiety that contains at least one double or triple bond.

[0093] The term "saturated" refers to a moiety that does not contain any double or triple bonds, ie, the moiety contains only single bonds.

[0094] The addition of the suffix "-ene" to a group indicates that the group is a divalent moiety, for example, alkylene is a divalent moiety of alkyl, arylene is a divalent moiety of aryl, cycloalkylene is a divalent moiety of cycloalkyl, and heterocyclylene is a divalent moiety of heterocyclyl.

[0095] The term “C x-y " when used in reference to a chemical moiety such as acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy, is meant to include groups containing x to y carbons in the chain. For example, the term "C x-y "Alkyl" refers to substituted or unsubstituted saturated hydrocarbon groups, such as straight chain alkyl and branched chain alkyl groups containing x to y carbons in the chain, and haloalkyl groups, such as trifluoromethyl and 2,2,2-trifluoroethyl. C0 alkyl refers to hydrogen where the group is in a terminal position, and a bond if internal.

[0096] A group is optionally substituted unless expressly provided otherwise. The term "optionally substituted" refers to being substituted or unsubstituted. In certain embodiments, alkyl, cycloalkyl, cycloalkenyl, heterocyclyl, heterocycloalkenyl, aryl and heteroaryl groups and corresponding divalent moieties are optionally substituted. "Optionally substituted" refers to a group that can be substituted or unsubstituted (e.g., "substituted" or "unsubstituted" alkyl, "substituted" or "unsubstituted" cycloalkyl, "substituted" or "unsubstituted" cycloalkenyl, "substituted" or "unsubstituted" heterocyclyl, "substituted" or "unsubstituted" heterocycloalkenyl, "substituted" or "unsubstituted" aryl or "substituted" or "unsubstituted" heteroaryl group). In general, the term "substituted" means that at least one hydrogen present on the group is replaced with an acceptable substituent, for example, a substituent that upon substitution results in a stable compound, for example, a compound that does not spontaneously undergo transformation, such as by rearrangement, cyclization, elimination or other reaction. Unless otherwise indicated, a "substituted" group has a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituents are either the same or different at each position. The term "substituted" is intended to include substitution with all permissible substituents of organic compounds, including any of the substituents described herein that result in the formation of a stable compound. The present invention contemplates any and all such combinations to achieve a stable compound. For purposes of this invention, heteroatoms such as nitrogen may have hydrogen substituents and / or any suitable substituents described herein that satisfy the valence of the heteroatom and result in the formation of a stable moiety. It is not intended that the present invention be limited in any manner to the exemplary substituents described herein.

[0097] Exemplary carbon atom substituents include, but are not limited to, halogen, -CN, -NO2, -N3, -OH, F, Cl, Br, I, oxo, -SO2H, -SO3H, -OR aa , -NH(R aa )2, -N(R aa )2, -N(R aa)3 + X - , -SH, -SR aa , -C(=O)R aa , -COH, -CHO, -COR aa , -OC(=O)R aa , -OCO2R aa , -C(=O)N(R aa )2, -OC(=O)N(R aa )2, -NR aa C(=O)R aa , -NR aa CO2R aa , -NR aa C(=O)N(R aa )2, -C(=NR aa )R aa , -C(=O)NR aa SO2R aa , -NR aa SO2R aa , -SO2N(R aa )2, -SO2R aa , -SO2OR aa , -OSO2R aa , -S(=O)R aa , -OS(=O)R aa , -Si(R aa )3, -OSi(R aa )3, C 1-12 Alkyl, C 1-12 Haloalkyl, 3-16 membered heterocyclyl and C 6-12 aryl, where X - is the counterion and R aa Each example is independently H, -OH, C 1-10 Alkyl, C 1-10 Haloalkyl, C 3-12 Cycloalkyl, 5-16 membered heterocyclyl and C 6-12 aryl, or two R aa The groups are linked to form a 3- to 16-membered heterocyclyl.

[0098] Numerical ranges include the numbers that define the range. Measurements and measurable values ​​are understood to be approximate, taking into account the effective numbers and errors associated with the measurements. As used herein, the terms "about" and "approximately" have their art-understood meanings; the use of one and the other does not necessarily imply a different range. Unless otherwise indicated, numerical values ​​used herein, with or without a modifying term such as "about" or "approximately", should be understood to encompass standard deviations and / or variations as would be understood by a person skilled in the relevant art. In some embodiments, the term "approximately" or "about" refers to a range of values ​​that is within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or less in either direction (greater or less) of the stated reference value, unless otherwise indicated or clear from the context (except where such number exceeds 100% of possible values).

[0099] As used herein, the term "composite material" refers to a material made from two or more constituent materials with significantly different physical or chemical properties that are separated by a distinct interface. When combined, the two or more constituent materials produce a composite material that has characteristics that differ from the individual components. Composite materials are distinguished from mixtures and homogeneous solutions because the individual components remain separate and distinct within the composite material.

[0100] As used herein, the term "reinforcement" refers to any material that can provide mechanical support to a polymer without interfering with the function of the polymer. For example, the reinforcement can be mixed with, impregnated with, or coated with a polymer to provide a composite material. The reinforcement can be an inorganic material such as a ceramic material, a polymer, or a composite of an inorganic material and a polymer, e.g., fiberglass.

[0101] As used herein, "support material" refers to a material having mechanical strength and chemical durability that can be impregnated and / or coated with a polymer to provide a composite material. The support material can be made of, for example, ceramic materials or polymers such as polyolefins, polysulfones or polyamides. In some embodiments, the support comprises polyimide, polybenzimidazole, polyphenylsulfone, polyphenylether, cellulose nitrate, cellulose diacetate, cellulose triacetate, polypropylene, polyethylene, polyvinylidene fluoride, poly(phenylene sulfide), poly(vinyl chloride), polystyrene, poly(methyl methacrylate), polyacrylonitrile, polytetrafluoroethylene, polyether ether ketone, polycarbonate, polyvinyltrimethylsilane, polytrimethylsilylpropyne, poly(etherimide), poly(ether sulfone), polyoxadiazole or poly(phenylene oxide), or combinations or copolymers thereof. The support material can be in the form of a film.

[0102] As used herein, the term "porous material impregnated with a polymer" refers to a porous material that contains a polymer in its pores. The porous material can be impregnated with a polymer, for example, by immersing the material in a solution of the polymer or by spraying the porous material with a solution of the polymer. Alternatively, the porous material can be impregnated with a solution of one or more monomers, followed by a polymerization reaction in the pores of the material. Furthermore, once the porous material is impregnated with a polymer, the polymer can undergo further chemical transformation, such as crosslinking, in the pores of the material.

[0103] As used herein, the term "repeating unit" (also known as monomeric unit) refers to a chemical moiety that repeats itself periodically such that sequential linking of repeating units together produces a complete polymer chain (excluding the end groups). A polymer may contain one or more different repeating units.

[0104] As used herein, a "main chain" of a polymer or a "backbone" of a polymer is a series of linked atoms that together produce a continuous chain of the molecule. As used herein, a "side chain" of a polymer is a series of linked atoms that are pendant from the main chain of the polymer.

[0105] As used herein, the term "cross-linked polymer" refers to a polymer in which two or more non-adjacent repeat units of the same backbone are linked via bridging moieties. The term "cross-linking polymer" also refers to two or more different backbones that are linked via multiple bridging moieties.

[0106] As used herein, the term "bridging moiety" refers to a multivalent, e.g., divalent or trivalent, repeating unit that forms a covalent bond with one or more non-adjacent repeating units of the same polymer backbone or with one or more repeating units of different backbones.

[0107] The term "degree of crosslinking," as used herein, refers to the fraction of repeating units that can form crosslinks compared to the total number of repeating units in a polymer. The degree of crosslinking is generally expressed as a mole percent with respect to the total number of repeating units in the polymer.

[0108] The phrase "number average molecular weight" refers to the total weight of a polymer divided by the total number of molecules. The number average molecular weight is the common average of the molecular weights of the individual polymer molecules. It is determined by measuring the molecular weights of n polymer molecules, adding up the molecular weights and dividing by n.

[0109] In some embodiments, the polymers disclosed herein are ionomers. As used herein, the term "ionomer" refers to a polymer composed of both electronically neutral repeating units and repeating units that contain charged moieties (i.e., cations or anions) covalently attached to the polymer backbone as pendant groups.

[0110] In some embodiments, the polymers provided herein are polyelectrolytes. As used herein, the term "polyelectrolyte" refers to a polymer that, under a particular set of conditions, has a net positive or negative charge due to the presence of charged repeating units. In some embodiments, the polyelectrolyte is or comprises a polycation; in some embodiments, the polyelectrolyte is or comprises a polyanion. A polycation has a net positive charge, and a polyanion has a net negative charge. The net charge of a given polyelectrolyte may depend on the surrounding chemical conditions, such as pH. As used herein, "ion exchange capacity" refers to the total number of active sites or functional groups responsible for ion exchange in the polyelectrolyte. The ion exchange capacity for hydroxide-exchange polyelectrolytes can be calculated according to Equation 1 based on the experimentally determined number of hydroxide ions exchanged within the polymer. Since the mass of the sample is the sum of the dry weight of the support + polymer, the ion accessibility is instead measured for the polyelectrolyte-containing composite membrane and calculated according to Equation 2.

number

[0111] As used herein, "ionic conductivity" refers to the ability of a material, such as a polyelectrolyte, to facilitate the movement of ions through the material. For example, the through-plane ionic conductivity of a polyelectrolyte membrane can be calculated based on the bulk resistance (R), membrane active area (L), and membrane thickness (A) according to Equation 3.

number

[0112] As used herein, "porosity" refers to the fraction of empty volume compared to the total volume of a material. Porosity is a measureless value between 0 and 1 or a percentage between 0% and 100%.

[0113] As used herein, the term "void space" or "void volume" refers to the porosity of a composite that includes a porous material saturated with a polymer. The void space is different from the porosity of a porous material because some of the pore volume of the porous material is occupied by the polymer deposited within the pore system of the material. The void space can be about 1%, about 2.5%, about 5%, about 7.5%, about 10%, about 12.5%, about 15%, about 17.5%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, or about 50%.

[0114] As used herein, the term "polyolefin" refers to a polymer resulting from the polymerization of organic molecules that contain carbon-carbon double bonds. The backbone of a polyolefin comprises a saturated chain of carbon-carbon bonds. In some embodiments, the carbon atoms in the backbone of a polyolefin can be substituted with hydrocarbyl groups. For example, the carbon atoms in the backbone of a polyolefin can be substituted with alkyl, cycloalkyl, or aryl groups. In some embodiments, the carbon atoms in the backbone of a polyolefin can be substituted with halogens, such as fluorine.

[0115] As used herein, "perfluorinated polyolefin" refers to a polyolefin in which all of the hydrogen atoms have been replaced with fluorine.

[0116] As used herein, "inorganic material" refers to a material that does not contain a chain of carbon-carbon bonds, excluding elemental carbon allotropes such as graphite, graphene, diamond, or carbon nanotubes contained in inorganic materials. Examples of inorganic materials include glasses, ceramic materials, and metal oxides such as TiO2, Al2O3, and ZnO.

[0117] The term "ceramic material" as used herein refers to a crystalline or amorphous oxide, nitride, or carbide of a metal or nonmetal element. Ceramic materials are generally hard, brittle, heat resistant, and corrosion resistant. Examples of ceramic materials include SiC, Si3N4, TiC, ZnO, ZrO2, Al2O3, and MgO.

[0118] The term "current collector," as used herein, refers to an electrical conductor between an electrode in an electrochemical device, such as a battery cell, and an external circuit.

[0119] In some embodiments, the reinforcing material comprises a polymer, an inorganic material, or a combination thereof. For example, the reinforcing material comprises a polyolefin, a polyphenylene, a polyester, a polyamide, or a polysulfone. For example, the reinforcing material comprises a polyolefin, such as polyethylene or polypropylene. For example, the reinforcing material comprises a perfluorinated polyolefin, such as polytetrafluoroethylene. For example, the reinforcing material comprises a polyimide, a polybenzimidazole, a polyphenylsulfone, a polyphenylether, a polytetrafluoroethylene, a cellulose nitrate, a cellulose diacetate, a cellulose triacetate, a polypropylene, a polyethylene, a polyvinylidene fluoride, a poly(phenylene sulfide), a polyvinyl chloride, a polystyrene, a poly(methyl methacrylate), a polyacrylonitrile, a polyether ether ketone, a polycarbonate, a polyvinyl trimethylsilane, a polytrimethylsilylpropyne, a poly(etherimide), a poly(ether sulfone), a polyoxadiazole, a poly(phenylene sulfide) or a poly(phenylene oxide), or a combination or copolymer thereof. The composite material may include polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride or polyvinyldifluoroethylene. Alternatively or additionally, the reinforcing material includes fiberglass or a ceramic material.

[0120] In some embodiments, the composite material is a mixture of a reinforcing material and a polyelectrolyte. Alternatively or additionally, the reinforcing material is a first layer; the electrolyte is a second layer; the first layer is in contact with at least one second layer. Alternatively or additionally, the reinforcing material is a porous material; the porous material is saturated with the electrolyte.

[0121] In some embodiments, the reinforcing material is a porous material, and the porous material has a porosity of about 40% to about 90%, such as about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85% or about 90%. For example, the porous material has a porosity of about 70% to about 85%, such as about 73%.

[0122] In some embodiments, the reinforcing material is a porous material, and the average size of the pores of the porous material is about 50 nm to about 500 μm, for example, about 50 nm, about 100 nm, about 200 nm, about 300 nm, about 400 nm, about 500 nm, about 600 nm, about 700 nm, about 800 nm, about 900 nm, about 1 μm, about 1 μm, about 1 μm, about 1 μm, about 10 μm, about 25 μm, about 50 μm, about 100 μm, about 150 μm, about 200 μm, about 250 μm, about 300 μm, about 350 μm, about 400 μm, about 450 μm, or about 500 μm. For example, the average size of the pores is about 100 nm to about 10 μm, for example, about 300 nm to about 1 μm. For example, the average size of the pores is about 450 nm.

[0123] In some embodiments, the composite material is a film having a thickness of about 1 μm to about 300 μm, such as about 1 μm, about 5 μm, about 10 μm, about 20 μm, about 30 μm, about 40 μm, about 50 μm, about 60 μm, about 70 μm, about 80 μm, about 90 μm, about 100 μm, about 120 μm, about 140 μm, about 160 μm, about 180 μm, about 200 μm, about 220 μm, about 240 μm, about 260 μm, about 280 μm, or about 300 μm. For example, the composite material is a film having a thickness of about 25 μm to about 75 μm, such as about 50 μm.

[0124] In a first aspect, the present invention provides a compound having structural formula (I): [ka] wherein: [ka] The portion represented by C 7-8cycloalkenyl or 7- to 12-membered heterocycloalkenyl; L 1 (OC 1-12 Alkylene) k , (C 1-12 Alkylene-O) k , C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) k , (C 1-12 Alkylene-NH k Selected from; The moiety represented by G has the following structural formula: [ka] , wherein the moiety is selected from the moiety represented by any one of: [ka] is the L of the part represented by G 1 is the point of attachment to; k is an integer from 1 to 6; a is 1 or 2; Y 1 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) or a bond; and further: Each C 1-12 Alkylene, C 6-12 Arylene, C 1-12 Alkyl, C 7-8 Cycloalkenyl and 7- to 12-membered heterocycloalkenyl are independently optionally selected from F, Cl, Br, OH, NH2, C1-12 Alkyl, C 6-12 Aryl C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl).

[0125] In a first aspect of the first embodiment, [ka] The part represented by C 7-8 cycloalkenyl, the moiety represented by G has the following structural formula: [ka] and L 1 is C 1-12 Alkylene, (OC 1-12 Alkylene) k or (C 1-12 Alkylene-O) k It is.

[0126] In a second aspect of the first embodiment, [ka] is a 7-12 membered heterocycloalkenyl, and the moiety represented by G is represented by the following structural formula: [ka] and L 1 is C 1-12 Alkylene, (OC 1-12 Alkylene) k or (C 1-12 Alkylene-O) kThe remainder of the features and example features of the second aspect are as described above for the first aspect of the first embodiment.

[0127] In a third aspect of the first embodiment, a is 1 or 2. For example, a is 1. Alternatively, a is 2. The remainder of the features and exemplary features of the third aspect are as described above for the first to second aspects of the first embodiment.

[0128] In a fourth aspect of the first embodiment, [ka] The part represented by C 7-8 cycloalkenyl, the moiety represented by G has the following structural formula: [ka] and L 1 is C 1-12 Alkylene, (OC 1-12 Alkylene) k or (C 1-12 Alkylene-O) k The remainder of the features and example features of the fourth aspect are as described above for the first to third aspects of the first embodiment.

[0129] In a fifth aspect of the first embodiment, [ka] is a 7-12 membered heterocycloalkenyl, and the moiety represented by G is represented by the following structural formula: [ka] and L 1 is C 1-12 Alkylene, (OC 1-12 Alkylene) k or (C 1-12 Alkylene-O) kThe remainder of the features and example features of the fifth aspect are as described above in relation to the first to fourth aspects of the first embodiment.

[0130] In a sixth aspect of the first embodiment, Y 1 is -C(=O)-, O, S. For example, Y is -C(=O)-. For example, Y is O. For example, Y is S. The remainder of the features and example features of the sixth aspect are as described above in relation to the first to fifth aspects of the first embodiment.

[0131] In a seventh aspect of the first embodiment, Y 1 is NH or N(C 1-12 For example, Y is NH. For example, Y is N(C 1-12 The remainder of the features and exemplary features of the seventh aspect are as described above for the first through sixth aspects of the first embodiment.

[0132] In an eighth aspect of the first embodiment, Y 1 is a bond. The remainder of the features and example features of the eighth aspect are as described above in relation to the first to seventh aspects of the first embodiment.

[0133] In a ninth aspect of the first embodiment, [ka] The moiety represented by the following structural formula: [ka] A portion represented by any one of During the ceremony: R a , R b and R c are each independently H or C 1-12 is alkyl; Z is CH2, O, NH and N(C 1-12 alkyl); X - F - , Cl- , Br - , O.H. - , NO - 2. CN - , HCO3 - , CO3 2- , PF6 - , BF4 - , C 1-12 Carboxylate and C 1-12 The remainder of the features and example features of the ninth aspect are as described above for the first through eighth aspects of the first embodiment.

[0134] In a tenth aspect of the first embodiment, [ka] The part represented by [ka] For example, [ka] The part represented by [ka] The remainder of the features and example features of the tenth aspect are as described above in relation to the first to ninth aspects of the first embodiment.

[0135] In an eleventh aspect of the first embodiment, R a is H. The remainder of the features and example features of the eleventh aspect are as described above in relation to the first through ninth and tenth aspects of the first embodiment.

[0136] In a twelfth aspect of the first embodiment, R a is C 1-3 For example, R a is methyl. The remainder of the features and exemplary features of the twelfth aspect are as described above for the first through eleventh aspects of the first embodiment.

[0137] In a thirteenth aspect of the first embodiment, [ka] The part represented by [ka] The remainder of the features and example features of the thirteenth aspect are as described above in relation to the first to ninth aspects of the first embodiment.

[0138] In a fourteenth aspect of the first embodiment, Z is CH2. Alternatively, Z is O, NH or N(C 1-12 The remainder of the features and exemplary features of the fourteenth aspect are as described above for the first through thirteenth aspects of the first embodiment.

[0139] In a fifteenth aspect of the first embodiment, R b is H or Me. For example, R b is methyl. Alternatively, R b is H. The remainder of the features and example features of the fifteenth aspect are as described above in relation to the first through fourteenth aspects of the first embodiment.

[0140] In a sixteenth aspect of the first embodiment, [ka] The part represented by [ka] The remainder of the features and example features of the sixteenth aspect are as described above for the first through fifteenth aspects of the first embodiment.

[0141] In a seventeenth aspect of the first embodiment, [ka] The part represented by [ka] The remainder of the features and example features of the seventeenth aspect are as described above for the first through sixteenth aspects of the first embodiment.

[0142] In an eighteenth aspect of the first embodiment, R c is C 1-3 For example, R c is methyl. The remainder of the features and example features of the eighteenth aspect are as described above for the seventeenth aspect of the first embodiment.

[0143] In a nineteenth aspect of the first embodiment, L 1 (OC 1-12 Alkylene) k or (C 1-12 Alkylene-O) k For example, L 1 is -CH2O- or -OCH2-. The remainder of the features and example features of the nineteenth aspect are as described above for the first through eighteenth aspects of the first embodiment.

[0144] In a twentieth aspect of the first embodiment, k is 1, 2, 3, 4, 5 or 6. For example, k is 1. The remainder of the features and example features of the twentieth aspect are as described above in relation to the first to nineteenth aspects of the first embodiment.

[0145] In a twenty-first aspect of the first embodiment, L 1 is C 1-12 For example, L 1 is C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, C9 alkylene, C 10 Alkylene, C 11 Alkylene or C 12 The remainder of the features and exemplary features of the twenty-first aspect are as described above for the first through twentieth aspects of the first embodiment.

[0146] In a twenty-third aspect of the first embodiment, the compound is: [ka] is selected from.

[0147] In a second aspect, the present invention provides a compound of structural formula (II): [ka] a plurality of first repeating units represented by Structural formula (III): [ka] and wherein the polymer comprises a plurality of second repeating units represented by During the ceremony: Q has the following structural formula: [ka] is a portion represented by one of U has the following structural formula: [ka] is a portion represented by one of V has the following structural formula: [ka] is a portion represented by one of W is for C 1-12 Alkyl or: [ka] is a moiety represented by one of the structural formulas selected from [ka] is the point of attachment to adjacent repeat units of the polymer; [ka] L2 is the point of attachment to; [ka] L 3 is the point of attachment to and further: [ka] is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently 1-3 is an alkylene or a bond; Z 2 -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR 2 In this case, R 1 and R 2 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 6 -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C 6-12 Arylene and CR 4 In this case, R 3 and R 4 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 9 is NR 10 or a combination; R if present 1 and R if present 3 are independently H, C 1-12Alkyl and C 6-12 aryl; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12 aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atom to which they are attached, 6-12 Forms an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12 Alkyl or C 3-12 is cycloalkyl; or R 18 and R19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl; or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5-12 membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) m , (C 1-12 Alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) m and (C 1-12 Alkylene-NH m Selected from; L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC1-12 Alkylene) n , (C 1-12 Alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) n , (C 1-12 Alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; b is 1 or 2; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - is F - , Cl - , Br - , O.H. - , NO - 2. CN - , HCO3 - , CO3 2- , PF6 - , BF4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5-16 membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl and 5- to 12-membered heterocyclyl are independently optionally selected from F, Cl, Br, OH, NH2, oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl).

[0148] In a first aspect of the second embodiment, U has the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] It is the part represented by:

[0149] In a second aspect of the second embodiment, U has the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the second aspect are as described above for the first aspect of the second embodiment.

[0150] In a third aspect of the second embodiment, U has the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the third aspect are as described above for the first to second aspects of the second embodiment.

[0151] In a fourth aspect of the second embodiment, U has the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the fourth aspect are as described above with respect to the first through third aspects of the second embodiment.

[0152] In a fifth aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the fifth aspect are as described above in relation to the first through fourth aspects of the second embodiment.

[0153] In a sixth aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the sixth aspect are as described above in relation to the first through fifth aspects of the second embodiment.

[0154] In a seventh aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the seventh aspect are as described above in relation to the first through sixth aspects of the second embodiment.

[0155] In an eighth aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the eighth aspect are as described above in relation to the first through seventh aspects of the second embodiment.

[0156] In a ninth aspect of the second embodiment, Q has the following structural formula: [ka] and U is a moiety represented by the following structural formula: [ka] and V is a moiety represented by the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the ninth aspect are as described above in relation to the first through eighth aspects of the second embodiment.

[0157] In a tenth aspect of the second embodiment, Q has the following structural formula: [ka] and U is a moiety represented by the following structural formula: [ka] and V is a moiety represented by the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the tenth aspect are as described above in relation to the first through ninth aspects of the second embodiment.

[0158] In an eleventh aspect of the second embodiment, Q has the following structural formula: [ka] and U is a moiety represented by the following structural formula: [ka] and V is a moiety represented by the following structural formula: [ka] and W is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the eleventh aspect are as described above in relation to the first through tenth aspects of the second embodiment.

[0159] In a twelfth aspect of the second embodiment, Q has the following structural formula: [ka] A moiety represented by any one of During the ceremony: R 20 , R 21 , R 22 , R 24 , R 26 , R 29 , R 30 、 R 31 and R 33 are each independently C 1-12 is alkyl; R 25 and R 32 are each independently C 6-12 is aryl; R27 is H or C 1-12 is alkyl; R 28 is H, C 1-12 Alkyl or C 6-12 is aryl; R 36 and R 35 are each independently C 1-12 alkyl or R 36 and R 35 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; Z 10 and Z 11 are each independently C 1-3 is an alkylene or a bond; Z 12 and Z 13 are independently CH2, O, NH and N(C 1-12 The remainder of the features and exemplary features of the twelfth aspect are as described above for the first through eleventh aspects of the second embodiment.

[0160] In a thirteenth aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the thirteenth aspect are as described above for the first through twelfth aspects of the second embodiment.

[0161] In a fourteenth aspect of the second embodiment, Q has the following structural formula: [ka] For example, Q is a moiety represented by the following structural formula: [ka] Alternatively, Q is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the fourteenth aspect are as described above for the first through thirteenth aspects of the second embodiment.

[0162] In a fifteenth aspect of the second embodiment, Z 10 and Z 11 are each independently C 1-3 Alkylene. For example, Z 10 is C2 alkylene, Z 11 is a C alkylene. The remainder of the features and example features of the fifteenth aspect are as described above for the first through fourteenth aspects of the second embodiment.

[0163] In a sixteenth aspect of the second embodiment, R 27 is H or methyl. The remainder of the features and exemplary features of the sixteenth aspect are as described above for the first through fifteenth aspects of the second embodiment.

[0164] In a seventeenth aspect of the second embodiment, Q has the following structural formula: [ka] For example, Q is a moiety represented by the following structural formula: [ka] Alternatively, Q is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the seventeenth aspect are as described above in relation to the first through sixteenth aspects of the second embodiment.

[0165] In an eighteenth aspect of the second embodiment, Z 12 is CH2, O, NH or N(C 1-12 For example, Z 12 is CH2 or O. Alternatively, Z 12is NH or N(C 1-12 The remainder of the features and exemplary features of the eighteenth aspect are as described above for the first through seventeenth aspects of the second embodiment.

[0166] In a nineteenth aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the nineteenth aspect are as described above with respect to the first through eighteenth aspects of the second embodiment.

[0167] In a twentieth aspect of the second embodiment, Q is [ka] The remainder of the features and example features of the twentieth aspect are as described above in relation to the first through nineteenth aspects of the second embodiment.

[0168] In a twenty-first aspect of the second embodiment, Z 13 is CH2, O, NH or N(C 1-12 For example, Z 13 is CH2 or O. Alternatively, Z 13 is NH or N(C 1-12 The remainder of the features and exemplary features of the twenty-first aspect are as described above for the first through twentieth aspects of the second embodiment.

[0169] In a twenty-second aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the twenty-second aspect are as described above for the first through twenty-first aspects of the second embodiment.

[0170] In a twenty-third aspect of the second embodiment, R 28is H or methyl. For example, R 28 is H. Alternatively, R 28 is methyl. The remainder of the features and exemplary features of the twenty-third aspect are as described above for the first through twenty-second aspects of the second embodiment.

[0171] In a twenty-fourth aspect of the second embodiment, Q has the following structural formula: [ka] The remainder of the features and example features of the twenty-fourth aspect are as described above in relation to the first through twenty-third aspects of the second embodiment.

[0172] In a twenty-fifth aspect of the second embodiment, V has the following structural formula: [ka] [ka] A moiety represented by any one of During the ceremony: R 37 , R 38 , R 39 , R 40 , R 42 , R 45 , R 46 、 R 47 and R 49 are each independently C 1-12 is alkyl; R 41 and R 48 are each independently C 6-12 is aryl; R 43 is H or C 1-12 is alkyl; R 44 is H, C 1-12 Alkyl or C 6-12 is aryl; R 50 and R 51 are each independently C1-12 alkyl or R 36 and R 35 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; Z 14 and Z 15 are each independently C 1-3 is an alkylene or a bond; Z 16 and Z 17 are independently CH2, O, NH and N(C 1-12 The remainder of the features and exemplary features of the twenty-fifth aspect are as described above for the first through twenty-fourth aspects of the second embodiment.

[0173] In a twenty-sixth aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the twenty-sixth aspect are as described above for the first through twenty-fifth aspects of the second embodiment.

[0174] In a twenty-seventh aspect of the second embodiment, V has the following structural formula: [ka] For example, V is a moiety represented by the following structural formula: [ka] Alternatively, V is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the twenty-seventh aspect are as described above in relation to the first through twenty-sixth aspects of the second embodiment.

[0175] In a twenty-eighth aspect of the second embodiment, Z 14 and Z15 are each independently C 1-3 Alkylene. For example, Z 14 is C2 alkylene, Z 15 is a C alkylene. The remainder of the features and example features of the twenty-eighth aspect are as described above for the first through twenty-seventh aspects of the second embodiment.

[0176] In a twenty-ninth aspect of the second embodiment, R 43 is H or methyl. For example, R 43 is H. Alternatively, R 43 is methyl. The remainder of the features and exemplary features of the twenty-ninth aspect are as described above for the first through twenty-eighth aspects of the second embodiment.

[0177] In a thirtieth aspect of the second embodiment, V has the following structural formula: [ka] For example, V is a moiety represented by the following structural formula: [ka] Alternatively, V is a moiety represented by the following structural formula: [ka] The remainder of the features and example features of the thirtieth aspect are as described above in relation to the first through twenty-ninth aspects of the second embodiment.

[0178] In a thirty-first aspect of the second embodiment, Z 16 is CH2, O, NH or N(C 1-12 For example, Z 16 is CH2 or O. Alternatively, Z 16 is NH or N(C 1-12 The remainder of the features and exemplary features of the thirty-first aspect are as described above for the first through thirtieth aspects of the second embodiment.

[0179] In a thirty-second aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the thirty-second aspect are as described above for the first through thirty-first aspects of the second embodiment.

[0180] In a thirty-third aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the thirty-third aspect are as described above for the first through thirty-second aspects of the second embodiment.

[0181] In a thirty-fourth aspect of the second embodiment, Z 13 is CH2, O, NH or N(C 1-12 For example, Z 13 is CH2 or O. Alternatively, Z 13 is NH or N(C 1-12 The remainder of the features and exemplary features of the thirty-fourth aspect are as described above for the first through thirty-third aspects of the second embodiment.

[0182] In a thirty-fifth aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the thirty-fifth aspect are as described above for the first through thirty-fourth aspects of the second embodiment.

[0183] In a thirty-sixth aspect of the second embodiment, R 44 is H or methyl. For example, R 44 is H. Alternatively, R 44is methyl. The remainder of the features and example features of the thirty-sixth aspect are as described above for the first through thirty-fifth aspects of the second embodiment.

[0184] In a thirty-seventh aspect of the second embodiment, V has the following structural formula: [ka] The remainder of the features and example features of the thirty-seventh aspect are as described above in relation to the first through thirty-sixth aspects of the second embodiment.

[0185] In a thirty-eighth aspect of the second embodiment, W is [ka] The remainder of the features and example features of the thirty-eighth aspect are as described above for the first through thirty-seventh aspects of the second embodiment.

[0186] In a thirty-ninth aspect of the second embodiment, Z 9 is NR 10 ;R 7 , R 8 and R 9 are each independently NR 11 R 12 The remainder of the features and example features of the thirty-ninth aspect are as described above for the first through thirty-eighth aspects of the second embodiment.

[0187] In a fortieth aspect of the second embodiment, Z 9 is a bond, and R 7 , R 8 and R 9 are each independently C 6-12 Aryl. For example, R 7 , R 8 and R 9 and are each phenyl. The remainder of the features and example features of the fortieth aspect are as described above for the first through thirty-ninth aspects of the second embodiment.

[0188] In a forty-first aspect of the second embodiment, R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 Cycloalkyl. For example, R 11 is C 1-3 is alkyl, R 12 is C 5-7 Cycloalkyl or C 1-3 For example, R 11 and R 12 are each methyl; or R 11 is methyl, R 12 is isopropyl; or R 11 is cyclohexyl, and R 12 is methyl. The remainder of the features and example features of the forty-first aspect are as described above for the first through fortieth aspects of the second embodiment.

[0189] In a forty-second aspect of the second embodiment, W is [ka] The remainder of the features and example features of the forty-second aspect are as described above for the first through forty-first aspects of the second embodiment.

[0190] In a forty-third aspect of the second embodiment, R 13 is unsubstituted C 6-12 Aryl. For example, R 13 is unsubstituted phenyl. Alternatively, R 13 is independently C 1-12 Alkyl, C 1-12 Alkoxy and N(C 1-12 C substituted with 1 to 3 substituents selected from alkyl 6-12 Aryl. For example, R 13 is independently substituted with 1 to 3 substituents selected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, dimethylamino, or diethylamino; 6-12and aryl, such as phenyl substituted with one to three substituents independently selected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, dimethylamino, or diethylamino. The remainder of the features and exemplary features of the forty-third aspect are as described above for the first through forty-second aspects of the second embodiment.

[0191] In a forty-fourth aspect of the second embodiment, R 14 is C 1-12 For example, R 14 is methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl or tert-butyl. 14 is C 3-8 and cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. The remainder of the features and exemplary features of the forty-fourth aspect are as described above for the first through forty-third aspects of the second embodiment.

[0192] In a forty-fifth aspect of the second embodiment, R 15 and R 16 are each independently C 1-12 For example, R 15 and R 16 are each independently methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, or tert-butyl. For example, R 15 and R 16 are each methyl. The remainder of the features and example features of the forty-fifth aspect are as described above for the first through forty-fourth aspects of the second embodiment.

[0193] In a forty-sixth aspect of the second embodiment, R 15 and R 16 are each independently C 6-12 Aryl. For example, R 15 and R 16 and each are phenyl. The remainder of the features and example features of the forty-sixth aspect are as described above for the first through forty-fifth aspects of the second embodiment.

[0194] In a forty-seventh aspect of the second embodiment, R 15 and R 16 together with the carbon atom to which they are attached, 6-12 Forms an aryl group. For example, R 15 and R 16 together with the carbon atom to which they are attached form a C6 aryl. The remainder of the features and exemplary features of the forty-seventh aspect are as described above for the first through forty-sixth aspects of the second embodiment.

[0195] In a forty-eighth aspect of the second embodiment, W is [ka] The remainder of the features and example features of the forty-eighth aspect are as described above for the first through forty-seventh aspects of the second embodiment.

[0196] In a forty-ninth aspect of the second embodiment, R 17 , R 18 and R 19 are each independently C 1-12 For example, R 17 , R 18 and R 19 are each methyl. The remainder of the features and example features of the forty-ninth aspect are as described above for the first through forty-eighth aspects of the second embodiment.

[0197] In a fiftieth aspect of the second embodiment, R 17 is C 1-12 is alkyl, R 18 and R 19 together with the nitrogen atom to which they are attached form a 5-12 membered heterocyclyl. The remainder of the features and exemplary features of the fiftieth aspect are as described above for the first through forty-ninth aspects of the second embodiment.

[0198] In a fifty-first aspect of the second embodiment, R 17 , R 18 and R19 together with the nitrogen atom to which they are attached form a bicyclic 5-12 membered heterocyclyl. The remainder of the features and exemplary features of the fifty-first aspect are as described above for the first through fiftieth aspects of the second embodiment.

[0199] In a fifty-second aspect of the second embodiment, L 2 is C 1-12 For example, L 2 is C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, C9 alkylene, C 10 Alkylene, C 11 Alkylene or C 12 The remainder of the features and example features of the fifty-second aspect are as described above for the first through fifty-first aspects of the second embodiment.

[0200] In a fifty-third aspect of the second embodiment, L 2 (OC 1-12 Alkylene) m or (C 1-12 Alkylene-O) m For example, L 2 is -CH2O- or -OCH2-. The remainder of the features and example features of the fifty-third aspect are as described above for the first through fifty-second aspects of the second embodiment.

[0201] In a fifty-fourth aspect of the second embodiment, m is 1, 2, 3, 4, 5 or 6. For example, m is 1. The remainder of the features and exemplary features of the fifty-fourth aspect are as described above for the first to fifty-third aspects of the second embodiment.

[0202] In a fifty-fifth aspect of the second embodiment, L 3 is C 1-12 For example, L 3 is C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, C9 alkylene, C 10 Alkylene, C11 Alkylene or C 12 For example, L 3 is methylene. The remainder of the features and example features of the fifty-fifth aspect are as described above for the first through fifty-fourth aspects of the second embodiment.

[0203] In a fifty-sixth aspect of the second embodiment, L 3 (OC 1-12 Alkylene) n or (C 1-12 Alkylene-O) n For example, L 3 is -CH2O- or -OCH2-. The remainder of the features and example features of the fifty-sixth aspect are as described above for the first through fifty-fifth aspects of the second embodiment.

[0204] In a fifty-seventh aspect of the second embodiment, n is 1, 2, 3, 4, 5 or 6. For example, n is 1. The remainder of the features and exemplary features of the fifty-seventh aspect are as described above in relation to the first to fifty-sixth aspects of the second embodiment.

[0205] In a fifty-eighth aspect of the second embodiment, the polymer further has the following structural formula: [ka] and a plurality of third repeat units represented by During the ceremony: Z 18 and Z 19 are each independently C 1-3 is an alkylene or a bond; R 52 , H, C 1-12 Alkyl or C 6-12 The remainder of the features and example features of the fifty-eighth aspect are as described above for the first through fifty-seventh aspects of the second embodiment.

[0206] In a fifty-ninth aspect of the second embodiment, R 52 is H or C 1-3 For example, R52 is H. Alternatively, R 53 is methyl. The remainder of the features and example features of the fifty-ninth aspect are as described above for the first through fifty-eighth aspects of the second embodiment.

[0207] In a sixtieth aspect of the second embodiment, the plurality of first repeat units has the following structural formula: [ka] The remainder of the features and example features of the sixtieth aspect are as described above in relation to the first to fifty-ninth aspects of the second embodiment.

[0208] In a sixty-first aspect of the second embodiment, the plurality of first repeating units has the following structural formula: [ka] The remainder of the features and example features of the sixty-first aspect are as described above in relation to the first to sixtieth aspects of the second embodiment.

[0209] In a sixty-second aspect of the second embodiment, the plurality of second repeat units has the structural formula: [ka] The remainder of the features and example features of the sixty-second aspect are as described above for the first through sixty-first aspects of the second embodiment.

[0210] In a sixty-third aspect of the second embodiment, the plurality of second repeat units has the following structural formula: [ka] For example, the plurality of second repeating units may include a repeating unit represented by the following structural formula: [ka] The remainder of the features and example features of the sixty-third aspect are as described above for the first through sixty-second aspects of the second embodiment.

[0211] In a sixty-fourth aspect of the second embodiment, the plurality of second repeat units has the following structural formula: [ka] wherein Me is methyl, iPr is isopropyl, and Cy is cyclohexyl. The remainder of the features and exemplary features of the sixty-fourth aspect are as described above for the first through sixty-third aspects of the second embodiment.

[0212] In a sixty-fifth aspect of the second embodiment, the plurality of first repeating units has the following structural formula: [ka] and a plurality of the second repeating units include a repeating unit represented by the following structural formula: [ka] The remainder of the features and example features of the sixty-fifth aspect are as described above for the first through sixty-fourth aspects of the second embodiment.

[0213] In a sixty-sixth aspect of the second embodiment, the polymer comprises about 0.5 mol-% to about 50 mol-% of the first repeat unit. For example, the polymer comprises about 2 mol-% to about 20 mol-%, such as about 2 mol-% or about 5 mol-%, of the first repeat unit. The remainder of the features and exemplary features of the sixty-sixth aspect are as described above with respect to the first to sixty-fifth aspects of the second embodiment.

[0214] In a sixty-seventh aspect of the second embodiment, the polymer comprises about 10 mol-% to about 80 mol-% of the second repeat unit. For example, the polymer comprises about 20 mol-% to about 60 mol-%, such as about 28 mol-%, about 46 mol-% or about 70 mol-% of the second repeat unit. The remainder of the features and exemplary features of the sixty-seventh aspect are as described above with respect to the first to sixty-sixth aspects of the second embodiment.

[0215] In a sixty-eighth aspect of the second embodiment, the number average molecular weight (MWn) of the polymer is from about 30,000 g / mol to about 500,000 g / mol. For example, the MWn of the polymer is from about 50,000 g / mol to about 360,000 g / mol. The remainder of the features and exemplary features of the sixty-eighth aspect are as described above for the first through sixty-seventh aspects of the second embodiment. The remainder of the features and exemplary features of the sixty-eighth aspect are as described above for the first through sixty-seventh aspects of the second embodiment.

[0216] In a sixty-ninth aspect of the second embodiment, the polymer is crosslinked. The remainder of the features and example features of the sixty-ninth aspect are as described above for the first through sixty-eighth aspects of the second embodiment.

[0217] In a third aspect, the present invention provides a compound represented by structural formula (IIa) or structural formula (IIb): [ka] a plurality of first repeat units selected from a bridging moiety represented by Structural formula (III): [ka] and wherein the crosslinked polymer comprises a plurality of second repeating units represented by During the ceremony: [ka] is the point of attachment to adjacent repeat units of the polymer; Q has the following structural formula: [ka] is a portion represented by one of V has the following structural formula: [ka] is a portion represented by one of W is for C 1-12 Alkyl or: [ka] is a moiety represented by one of the structural formulas selected from T is C for each occurrence independently. 2-8 is alkylene, [ka] is the point of attachment to adjacent repeat units of the polymer; [ka] L 2 is the point of attachment to; [ka] L 3 is the point of attachment to and further: [ka] is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently C 1-3 is an alkylene or a bond; Z 2 -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR2 In this case, R 1 and R 2 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 6 -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C 6-12 Arylene and CR 4 In this case, R 3 and R 4 together with the carbon atom to which they are attached, 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 9 is NR 10 or a combination; R if present 1 and R if present 3 are independently H, C 1-12 Alkyl and C 6-12 aryl; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12 aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atom to which they are attached, 6-12 Forms an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12 Alkyl or C 3-12 is cycloalkyl; or R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl; or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5-12 membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) m , (C 1-12 Alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) m and (C 1-12 Alkylene-NH m Selected from; L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 Alkylene) n , (C 1-12 Alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 Alkylene) n , (C 1-12 Alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - F - , Cl - , Br - , O.H. - , NO- 2. CN - , HCO3 - , CO3 2- , PF6 - , BF4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5-16 membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl and 5- to 12-membered heterocyclyl are independently optionally selected from F, Cl, Br, OH, NH2, oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl).

[0218] In a first aspect of the third embodiment, the plurality of first repeat units has the following structural formula: [ka] and comprising a bridging moiety represented by Q has the following structural formula: [ka] and V is a moiety represented by the following structural formula: [ka] W is a moiety represented by C 1-12 Alkyl or: [ka] is a moiety represented by one of the structural formulas selected from:

[0219] In a second aspect of the third embodiment, the plurality of first repeat units has the following structural formula: [ka] and Q comprises a bridging moiety represented by the following structural formula: [ka] and V is a moiety represented by the following structural formula: [ka] W is a moiety represented by C 1-12 Alkyl or: [ka] The remainder of the features and exemplary features of the second aspect are as described above for the first aspect of the third embodiment.

[0220] In a third aspect of the third embodiment, the plurality of first repeat units has the following structural formula: [ka] and a plurality of the second repeat units include a bridging portion represented by the following structural formula: [ka] The remainder of the features and exemplary features of the third aspect are as described above for the first to second aspects of the third embodiment.

[0221] In a fourth aspect of the third embodiment, the plurality of first repeat units has the following structural formula: [ka] and a plurality of the second repeat units include a bridging portion represented by the following structural formula: [ka] [ka] where Me is methyl, iPr is isopropyl, and Cy is cyclohexyl. The remainder of the features and exemplary features of the fourth aspect are as described above for the first through third aspects of the third embodiment.

[0222] In a fifth aspect of the third embodiment, Q, V, W, L 2 and L 3 is as described in any of the twelfth to fifty-seventh aspects of the second aspect. The remainder of the features and example features of the fifth aspect are as described above in relation to the first to fourth aspects of the third aspect.

[0223] In a sixth aspect of the third embodiment, the crosslinked polymer further comprises the following structural formula: [ka] and a plurality of third repeat units represented by In the formula: Z 18 and Z 19 are each independently C 1-3 alkylene or a bond; R 52 is H, C 1-12 Alkyl or C 6-12 The remainder of the features and exemplary features of the sixth aspect are as described above for the first through fifth aspects of the third embodiment.

[0224] In a fourth aspect, the invention is a composite material comprising a reinforcing material and a polymer as described herein with respect to the second aspect and various aspects thereof or a crosslinked polymer as described herein with respect to the third aspect and various aspects thereof.

[0225] In a first aspect of the fourth embodiment, the reinforcing material is a porous material; the porous material is impregnated with a polymer or a cross-linked polymer.

[0226] In a fifth aspect, the invention is a membrane comprising a polymer as described herein with respect to the second aspect and various aspects thereof, a crosslinked polymer as described herein with respect to the third aspect and various aspects thereof; or a film of a composite material as described herein with respect to the fourth aspect and various aspects thereof.

[0227] In a sixth aspect, the invention is a membrane electrode assembly comprising a membrane and an electrode as described herein with respect to the fifth aspect and various aspects thereof.

[0228] In a seventh aspect, the invention is an electrochemical device comprising a membrane electrode assembly and a current collector as described herein with respect to the sixth aspect and various aspects thereof.

[0229] In a first aspect of the seventh embodiment, the device is an electrolytic device. EXAMPLES

[0230] Working Example The following examples describe methods for the synthesis of the monomers, polymers, and AEIs of the present disclosure. The examples also provide methods for the preparation and characterization of the AEMs and rAEMs of the present disclosure.

[0231] Abbreviation COE Cyclooctene TEA Triethylamine THF Tetrahydrofuran ACN Acetonitrile Grubbs' Gen II catalyst (1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium Crabtree's catalyst (1,5-cyclooctadiene)(pyridine)(tricyclohexylphosphine)-Ir(I) PF6

[0232] Example 1. Synthesis of COE-benzophenone monomer. [ka] COE-OH (10 g, 71 mmol) was combined with triethylamine (8.1 g, 80 mmol) and tetrahydrofuran (anhydrous, 100 mL) in a 250 mL round bottom flask. The solution was cooled to 0° C. in an ice bath and methanesulfonyl chloride was added dropwise under a flow of nitrogen. The reaction was allowed to warm to room temperature and stirred for 24 h. The resulting heterogeneous mixture was filtered to remove solids and the organic layer was concentrated in vacuo to remove tetrahydrofuran. The crude oil was dissolved in diethyl ether and washed with KOH (1M), water and brine. The organic layer was dried over magnesium sulfate and concentrated in vacuo to give COE-OM as a light yellow oil (13.3 g).

[0233] COE-OM (5 g, 23 mmol) was combined with potassium carbonate (7 g, 50 mmol), acetonitrile (50 mL) and 4-hydroxybenzophenone (4.8 g, 24 mmol) in a 250 mL round-bottom flask. The round-bottom flask was fitted with a reflux condenser and the reaction was heated to reflux for 24 h. The reaction was cooled, filtered and concentrated in vacuo to remove acetonitrile. The resulting crude oil was dissolved in ethyl acetate and washed with 1M KOH, water and brine. The organic layer was dried over magnesium sulfate, filtered and concentrated in vacuo to give COE-benzophenone as an off-white waxy solid (4.1 g).

[0234] Example 2. Synthesis of isopropyl-methyl Tetrakis® monomer. [ka] Tris(isopropyl(methyl)amino)(methylamino)phosphonium hexafluorophosphate (1) was synthesized as detailed in Treichel, M. et al. Macromolecules, 2020, 53, 8509.

[0235] Compound (1) (5.0 g, 12 mmol) was combined with chlorobenzene (12 mL) in a 250 mL round bottom flask. Potassium hydroxide solution (50 wt%, 10.0 g, 178 mmol) was charged followed by COE-iodide (2) (4.4 g, 18 mmol). The reaction was heated to 60° C. for 24 h. The reaction was cooled and the layers were separated. The aqueous layer was extracted with dichloromethane and all organic layers were washed with 1 M HCl, saturated potassium hexafluorophosphate and water. The organic layers were dried over magnesium chloride and concentrated under vacuum to give a crude oil. The oil was dissolved in a minimum amount of dichloromethane and precipitated into diethyl ether to give Tetrakis® monomer (3) as an off-white waxy solid (3.9 g).

[0236] Example 3. Synthesis of non-crosslinked benzophenone-containing polyelectrolyte. Tetrakis® monomer (0.62 g, 1.1 mmol), COE-benzophenone (0.10 g, 0.32 mmol) and cyclooctene (0.28 g, 2.5 mmol) were dissolved in dichloromethane under an inert atmosphere. Grubbs' Gen II catalyst (7 mg, 0.01 mmol) was added to the solution and the reaction was stirred for 18 h. The resulting polymer was dissolved in a 2:1 (v:v) dichloromethane:methanol mixture and added to a pressure vessel. Crabtree's catalyst (6.4 mg, 0.01 mmol) was added and the reaction was pressurized to 800 psi of hydrogen and heated to 55° C. for 17 h. The reaction was cooled to room temperature and the solvent was removed to give 0.96 g of Tetrakis-BXL, non-crosslinked polymer.

[0237] Example 4. Crosslinking of benzophenone-containing polyelectrolytes. An AEI containing a Tetrakis® cation with a cyclohexyl, methyl substitution pattern was used in the experiments described below.

[0238] I. Preparation of free-standing cross-linked polyelectrolyte anion exchange membranes (AEMs). A. Drop casting. A solution was made by dissolving 520 mg of polyelectrolyte in 15 mL of the solvent system chloroform:methanol (4:1). While the polyelectrolyte was dissolving, a large casting dish was leveled using a micrometer on the countertop at ambient temperature. When the polyelectrolyte was fully dissolved, it was filtered through a syringe and glass wool to remove any large particulates. The solution was then poured into a large casting dish with a bell jar placed on top to create a dust-free environment. After remaining overnight in the dish, the membrane was crosslinked in the dish with UV light for 1 hour, then lifted out of the dish with water and allowed to air dry. The UV crosslinking procedure was as follows: the membrane was placed flat under the UV light 2 inches from a UV bulb (100W, 365nm) with the center of the membrane ensuring adequate light coverage across the membrane. A cover was placed over the light source and membrane. The membrane was exposed to UV light for 1 hour.

[0239] B. Tape-casting. An 8.5 wt% solution of polyelectrolyte T-28-120-BXL5 in a 3:1 water:n-propanol solvent system was prepared by heating the mixture to 62°C for 1 hour while stirring at low rpm, then heating the mixture at 90°C for 2 hours while stirring at a higher rpm until all the polymer was dissolved. Once the polymer was fully dissolved, the solution was cooled to ambient temperature and filtered through glass wool in a syringe. The solution was then poured onto a pre-cleaned glass sheet and a pre-cleaned drawing bar was activated to draw the polymer solution and create a film of the target thickness. The glass sheet with the membrane was then placed in an oven at 80°C for 3 hours and then transferred to a vacuum oven at 120°C overnight. The membrane was lifted by the addition of water, dried at ambient temperature, and finally crosslinked for 1 hour as described in Part A.

[0240] II. Preparation of reinforced cross-linked polyelectrolyte anion exchange membrane (rAEM). A 4 wt% solution of polyelectrolyte was prepared by dissolving the polyelectrolyte in a 3:1 water:n-propanol solvent system. The solution was gently heated until all the polymer was dissolved, the solution was cooled to ambient temperature, and filtered through glass wool in a syringe. A hot plate covered with a clean sheet of Teflon film was heated to 80°C. The polymer substrate (PP or PE) was cleaned in an ultrasonic bath of pure ethanol at 25°C for 1 hour, then air dried, and then weighed. The substrate was then placed in a spray coating frame and clamped. The polymer solution was added to a spray gun and applied to both sides of the substrate at 30 psi. The saturated substrate was then set to dry on a hot plate for 5 minutes or placed in an oven pre-warmed to 80°C for 2 minutes. The mass and thickness of the saturated substrate was measured, after which another coat of polyelectrolyte was applied. When the final coat was dry, the saturated substrate was placed under UV light for 1 hour to achieve polymer crosslinking according to the procedure described in Section IA above.

[0241] Example 5. Characterization methods for crosslinked membranes. The following method was used with freestanding AEM and rAEM.

[0242] A. In-plane hydroxide conductivity at ambient and variable temperatures Since conductivity is inversely proportional to resistivity, high performance AEMs exhibit relatively low ionic resistivity and high ionic conductivity. Calculating ionic conductivity from measured resistivity simplifies comparison of AEMs by normalizing to a specific area. A Bekktech cell (Scribner Associates) was used to measure in-plane hydroxide conductivity using electrochemical impedance spectroscopy (EIS). Measurements were performed in an environmental chamber purged with inert gas to reduce the complication of carbonate formation during the experiment. Hydroxide conductivity was obtained in liquid water at ambient / room temperature and 80 °C.

[0243] B. In-plane hydroxide conductivity at variable temperature and humidity Conductivity is often measured by immersing the sample in liquid water, which simplifies the setup and makes the results more reproducible. However, AEMs in fuel cells and electrolyzers are exposed to drier conditions with relative humidity (RH) as low as 50%. Measurements in liquid water do not accurately predict the conductivity reduction observed under these dehydrated conditions. Measurements of hydroxide conductivity at 70% RH and 80°C were used to obtain an indication of how the AEM will perform under operating humidity. After modifying the setup by adding a humidified chamber to the CO2-free environmental chamber, electrochemical experiments were performed using similar parameters to the ambient measurements.

[0244] C. Through-plane hydroxide conductivity at variable temperatures High performance AEMs exhibit relatively low ionic resistance and high ionic conductivity. Low through-plane resistance and high conductivity are indicators that the AEM will have good ionic mobility in working devices. Through-plane conductivity measurements have historically been difficult to obtain and reproduce due to a lack of standardized hardware. Through-plane values ​​are often estimated from the through-plane conductivity; however, the anisotropic nature of AEMs limits the accuracy of this method. A through-plane conductivity cell with similar dimensions and design features as the Bekktech cell was used. As with the through-plane measurements, a model circuit was used to calculate the conductivity from EIS.

[0245] Prepare an AEM sample of appropriate dimensions, 1 cm x 1 cm square required for the Ecolectro cell. Exchange the AEM sample for hydroxide using the appropriate technique for the polymer mold. Immediately after exchange, the AEM was quickly loaded into the cell and the cell was placed in liquid water equilibrated to the desired temperature to measure conductivity. Measurements were completed in an environmental chamber purged with inert gas to limit carbonate contamination.

[0246] D. Area-specific resistance (ASR) High performance AEMs exhibit relatively low ionic resistance and high ionic conductivity. Low resistance in the through-plane direction is an indication that the AEM has good ionic mobility in a working device. This particular measurement is known as area specific resistivity (ASR). Using a device for measuring through-plane conductivity, EIS and ASR were measured directly in this configuration. ASR was calculated from the through-plane resistivity.

[0247] E. Mechanical properties AEMs ideally have high mechanical strength when hydrated at high temperatures and sufficient handling properties to be incorporated into membrane electrode assemblies (MEAs). Reporting the stress and elongation at break is a universal method to characterize intrinsic polymer mechanical properties.

[0248] The mechanical properties of the AEMs were measured using a tensile tester at 50°C and 50% RH. The AEM samples were pre-equilibrated for 48 hours before testing the mechanical properties in an environmental chamber at both 50°C and 50% RH. Most of the AEMs were analyzed in their natural halide form.

[0249] F. Alkaline Stability An alkaline stability test was used to evaluate the chemical stability of the AEMs under conditions relevant to an operating alkaline electrolysis device or fuel cell. The disclosed and commercially available AEMs were cut to appropriate dimensions for various analytical techniques.

[0250] The conditions chosen were aqueous 1M KOH at 80°C. The AEM was exchanged into the hydroxide form using the procedure appropriate for each AEM. The samples were immediately immersed in 1M KOH and stored at 80°C for 200-2,000 hours. After 200-2,000 hours, the samples were removed and prepared for analysis following the protocol for the specific analytical technique.

[0251] Three analytical techniques were used to evaluate the AEMs: in-plane hydroxide conductivity at room temperature, and in-plane chloride conductivity at IEC or 80°C.

[0252] G. Water Uptake and Swelling Hydration of the AEM is critical to the mobility of hydroxide ions through the MEA and is an effective reactant. However, excessive swelling can negatively affect the MEA structure by causing large dimensional changes during actuation. To understand the forces that the AEM experiences under actuation conditions, the swelling (i.e., change in dimensions; where X = length; Y = width; Z = thickness) and water uptake (i.e., mass of water absorbed) were determined.

[0253] The dimensions and weight of the dry halide form AEM samples were measured. The AEM was converted to the hydroxide form using a procedure appropriate for the material and then stored in pure water at ambient / room temperature or 80° C. The hydroxide form AEM was measured again after processing and the changes in dimensions and weight were reported relative to the dry halide form.

[0254] H. Ion Exchange Capacity (IEC) The ability to transport ions is a fundamental and unique property of polymer electrolytes. The cationic content in the polymer affects anion mobility as well as swelling and water uptake. The cationic content is typically controlled by the synthetic route, and theoretical values ​​for ion exchange capacity (IEC) can be determined from the synthetic inputs. Theoretical IEC is defined as mmol or meq per gram of polymer. Hydroxide is typically the ion concentration measured, which is converted to the number of cations in the polymer. The measured IEC is lower than the theoretical value when some ionic sites in the polymer sample are blocked and not accessible. Theoretical and measured IEC values ​​are similar to those expected for the polymer identity and fit when all cationic groups in the polymer are involved in ion transport.

[0255] The weight of the dry AEM sample was recorded. The AEM sample was converted to the hydroxide form using a method appropriate for the polymer type. The sample was then immersed in HCl and the hydroxide in the polymer reacted with some acid. The amount of HCl that reacted with the AEM / AEI was determined by titration of the HCl solution, which provided the available hydroxide content and accessible cations in the polymer. The mmol of hydroxide determined from the titration was divided by the weight of the polymer sample to obtain the IEC.

[0256] H. Polymer Loading and Volume Determination for rAEM Fabrication 1) Cut the support to a desired piece and measure X (length, initial) and Y (width, initial). 2) Clean, dry and weigh the support - M (initial) 3) Using the polymer to create rAEM 4) Measure X(final), Y(final), M(final) and Z(thickness) The polymer loading and volume are determined according to the above formula:

number

[0257] While the present invention has been particularly shown and described with respect to illustrative embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims.

[0258] The teachings of all patents, published applications and references cited herein are incorporated by reference in their entirety.

Claims

1. Structural formula (II): 【Chemical 1】 a plurality of first repeating units represented by: Structural formula (III): 【Chemistry 2】 A polymer comprising a plurality of second repeating units represented by: During the ceremony: Q has the following structural formula: 【Chemistry 3】 a portion represented by one of: U has the following structural formula: 【Chemistry 4】 a portion represented by one of: V has the following structural formula: 【Chemistry 5】 is a portion represented by one of W is C 1-12 Alkyl or: 【Chemistry 6】 is a moiety represented by one of the structural formulas selected from 【Chemistry 7】 is the point of attachment to adjacent repeat units of the polymer; 【Chemistry 8】 is L 2 is the point of attachment to; 【Chemistry 9】 is L 3 is the point of attachment to and further: 【Chemistry 10】 is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently C 1-3 is an alkylene or a bond; Z 2 is -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR 2 If Z 4 is CR 2, then R 1 and R 2 together with the carbon atoms to which they are attached form C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; when Z 4 is selected from a bond and C 6-12 arylene, R 1 is selected from H, C 1-12 alkyl and C 6-12 aryl; Z 6 is -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C 6-12 Arylene and CR 4 If Z 8 is CR 4, then R 3 and R 4 together with the carbon atoms to which they are attached form C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; when Z 8 is selected from a bond and C 6-12 arylene, R 3 is selected from H, C 1-12 alkyl and C 6-12 aryl; or R 1 , if present, and R 3 , if present, are each independently selected from H, C 1-12 alkyl, and C 6-12 aryl; Z 9 is NR 10 or a bond; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12 aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atoms to which they are attached form C 6-12 forming an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12 Alkyl or C 3-12 is cycloalkyl; or R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl, and (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl, or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5- to 12-membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 alkylene) m , (C 1-12 alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 alkylene) m and (C 1-12 alkylene-NH m Selected from: L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 alkylene) n , (C 1-12 alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 alkylene) n , (C 1-12 alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; b is 1 or 2; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - is F - , Cl - , Br - , O.H. - , NO - 2 , C.N. - , HCO 3 - , CO 3 2- , P.F. 6 - , B.F. 4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5- to 16-membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl and 5- to 12-membered heterocyclyl are independently optionally selected from F, Cl, Br, OH, NH 2 , Oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl) 2 , C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 substituted with 1 to 6 substituents independently selected from the group consisting of alkyl; polymer.

2. U is a member of the following structural formula: 【Chemistry 11】 The polymer of claim 1 , wherein the moiety is represented by:

3. U is a member of the following structural formula: 【Chemistry 12】 The polymer of claim 1 , wherein the moiety is represented by:

4. Q is a group having the following structural formula: 【Chemistry 13】 and U is a member of the following structural formula: 【Chemistry 14】 and V has the following structural formula: 【Chemistry 15】 and W has the following structural formula: 【Chemistry 16】 The polymer of claim 1 , wherein the moiety is represented by:

5. Q is a group having the following structural formula: 【Chemistry 17】 and During the ceremony: R 20 , R 21 , R 22 , R 24 , R 26 , R 29 , R 30 、 R 31 and R 33 are each independently C 1-12 is alkyl; R 25 and R 32 are each independently C 6-12 is aryl; R 27 is H or C 1-12 is alkyl; R 28 is H, C 1-12 Alkyl or C 6-12 is aryl; R 36 and R 35 are each independently C 1-12 alkyl or R 36 and R 35 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; Z 10 and Z 11 are each independently C 1-3 is an alkylene or a bond; Z 12 and Z 13 are each independently CH 2 , O, NH and N(C 1-12 2. The polymer of claim 1, wherein the aryl group is selected from the group consisting of aryl, arylalkyl, aryl

6. V has the following structural formula: 【Chemistry 18】 and During the ceremony: R 37 , R 38 , R 39 , R 40 , R 42 , R 45 , R 46 、 R 47 and R 49 are each independently C 1-12 is alkyl; R 41 and R 48 are each independently C 6-12 is aryl; R 43 is H or C 1-12 is alkyl; R 44 is H, C 1-12 Alkyl or C 6-12 is aryl; R 50 and R 51 are each independently C 1-12 alkyl or R 36 and R 35 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; Z 14 and Z 15 are each independently C 1-3 is an alkylene or a bond; Z 16 and Z 17 are each independently CH 2 , O, NH and N(C 1-12 2. The polymer of claim 1, wherein the aryl group is selected from the group consisting of aryl, arylalkyl, aryl

7. W is, 【Chemistry 19】 2. The polymer of claim 1, wherein:

8. Z 9 NR 10 and R 7 , R 8 and R 9 However, each independently NR 11 R 12 8. The polymer of claim 7, wherein:

9. R 11 and R 12 However, each independently C 1-12 Alkyl or C 3-12 The polymer of claim 8 which is cycloalkyl.

10. L 2 However, (OC 1-12 alkylene) m or (C 1-12 alkylene-O) m 2. The polymer of claim 1, wherein:

11. L 3 C 1-12 The polymer of claim 1 which is an alkylene.

12. The following structural formula: 【Chemistry 20】 and a third repeat unit represented by: During the ceremony: Z 18 and Z 19 are each independently C 1-3 is an alkylene or a bond; R 52 is H, C 1-12 Alkyl or C 6-12 The polymer of claim 1 which is aryl.

13. The plurality of first repeat units has the following structural formula: 【Chemical formula 21】 The polymer of claim 1 comprising a repeating unit represented by:

14. The plurality of first repeat units has the following structural formula: 【Chemical 22】 14. The polymer of claim 13, comprising a repeating unit represented by:

15. The plurality of second repeating units has the following structural formula: 【Chemical 23】 The polymer of claim 1 comprising a repeating unit represented by:

16. The plurality of second repeating units has the following structural formula: 【Chemistry 24】 The polymer of claim 1 comprising a repeating unit represented by:

17. The plurality of second repeating units has the following structural formula: 【Chemistry 25】 The polymer of claim 1 comprising a repeating unit represented by:

18. The plurality of second repeating units has the following structural formula: 【Chemical Formula 26】 and 2. The polymer of claim 1, wherein Me is methyl, iPr is isopropyl, and Cy is cyclohexyl.

19. The plurality of first repeat units has the following structural formula: 【Chemical 27】 comprising a repeat unit represented by: The plurality of second repeating units has the following structural formula: 【Chemistry 27-1】 The polymer of claim 1 , comprising a repeat unit represented by one of:

20. The polymer of claim 1 comprising from about 0.5 mol-% to about 50 mol-% of the first repeat unit.

21. The polymer of claim 1 comprising from about 10 mol-% to about 80 mol-% of the second repeat unit.

22. The polymer of claim 1 which is crosslinked.

23. Structural Formula (IIa) or Structural Formula (IIb): 【Chemical 28】 a plurality of first repeat units selected from a bridging moiety represented by Structural formula (III): 【Chemical Formula 29】 A crosslinked polymer comprising a plurality of second repeating units represented by: During the ceremony: 【Chemistry 30】 is the point of attachment to adjacent repeat units of the polymer; Q has the following structural formula: 【Chemical 31】 a portion represented by one of: V has the following structural formula: 【Chemical 32】 is a portion represented by one of W is C 1-12 Alkyl or: 【Chemical 33】 is a moiety represented by one of the structural formulas selected from T is independently C for each occurrence 2-8 is alkylene, 【Chemical 34】 is the point of attachment to adjacent repeat units of the polymer; 【Chemistry 35】 is L 2 is the point of attachment to; 【Chemical 36】 is L 3 is the point of attachment to and further: 【Chemical 37】 is a double bond or a single bond; Z 1 , Z 3 , Z 5 and Z 7 are each independently C 1-3 is an alkylene or a bond; Z 2 is -CHR 5 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 4 is a bond, C 6-12 Arylene and CR 2 If Z 4 is CR 2, then R 1 and R 2 together with the carbon atoms to which they are attached form C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 6 is -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; Z 8 is a bond, C 6-12 Arylene and CR 4 If Z 8 is CR 4, then R 3 and R 4 together with the carbon atoms to which they are attached form C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; when Z 8 is selected from a bond and C 6-12 arylene, R 3 is selected from H, C 1-12 alkyl and C 6-12 aryl; or R 1 , if present, and R 3 , if present, are each independently selected from H, C 1-12 alkyl, and C 6-12 aryl; Z 9 is NR 10 or a bond; R 5 and R 6 are each independently H or C 1-12 is alkyl; R 7 , R 8 and R 9 are each independently NR 11 R 12 , C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 10 is C 1-12 is alkyl; R 11 and R 12 are each independently C 1-12 Alkyl or C 3-12 cycloalkyl or R 11 and R 12 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl; R 13 is C 1-12 Alkyl, C 6-12 selected from aryl and 5- to 12-membered heterocyclyl; R 14 is C 1-12 Alkyl or C 3-12 is cycloalkyl; R 15 and R 16 are each independently C 1-12 Alkyl, C 6-12 aryl and 5- to 12-membered heterocyclyl; or R 15 and R 16 together with the carbon atoms to which they are attached form C 6-12 forming an aryl or 5- to 12-membered heterocyclyl; R 17 , R 18 and R 19 are each independently C 1-12 Alkyl or C 3-12 is cycloalkyl; or R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 12-membered heterocyclyl, and (i) R 17 is C 1-12 Alkyl or C 3-12 cycloalkyl, or (ii) R 17 and L if present 3 At least one atom of 3 and R 17 together with the nitrogen atom to which it is attached form a 5- to 12-membered heterocyclyl; or R 17 , R 18 and R 19 together with the nitrogen atom to which they are attached form a bicyclic 5- to 12-membered heterocyclyl; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 alkylene) m , (C 1-12 alkylene-O) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 alkylene) m and (C 1-12 alkylene-NH m Selected from: L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12 Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 alkylene) n , (C 1-12 alkylene-O) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, (NH-C 1-12 alkylene) n , (C 1-12 alkylene-NH n and a bond; m is an integer from 1 to 6; n is an integer from 1 to 6; Y 2 is -C(=O)-, O, S, NH, N(C 1-12 alkyl) and a bond; X - is F - , Cl - , Br - , O.H. - , NO - 2 , C.N. - , HCO 3 - , CO 3 2- , P.F. 6 - , B.F. 4 - , C 1-12 Carboxylate and C 1-12 alkoxides; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl: Each C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5- to 16-membered heterocyclylene, C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl and 5- to 12-membered heterocyclyl are independently optionally selected from F, Cl, Br, OH, NH 2 , Oxo, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl) 2 , C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 substituted with 1 to 6 substituents independently selected from the group consisting of alkyl; Cross-linked polymer.

24. The plurality of first repeat units has the following structural formula: 【Chemical Formula 38】 and a bridging moiety represented by Q is a group having the following structural formula: 【Chemical 39】 and V has the following structural formula: 【Chemistry 40】 and W is C 1-12 Alkyl or the following structural formula: 【Chemistry 41】 24. The crosslinked polymer of claim 23, wherein the moiety is represented by:

25. W is C 1-12 Alkyl or the following structural formula: 【Chemistry 42】 24. The crosslinked polymer of claim 23, wherein the moiety is represented by:

26. The plurality of first repeat units has the following structural formula: 【Chemistry 43】 and a bridging moiety represented by The plurality of second repeating units has the following structural formula: 【Chemical 44】 24. The crosslinked polymer of claim 23, comprising a repeating unit represented by:

27. The plurality of first repeat units has the following structural formula: 【Chemistry 45】 and a bridging moiety represented by The plurality of second repeat units has the following structural formula: 【Chemistry 46】 and comprising a repeat unit represented by one of:

24. The crosslinked polymer of claim 23, wherein Me is methyl, iPr is isopropyl, and Cy is cyclohexyl.

28. 24. A composite material comprising a reinforcing material and the polymer of claim 1 or the crosslinked polymer of claim 23 in contact with the reinforcing material.

29. the reinforcing material is a porous material; 29. The composite material of claim 28, wherein a porous material is impregnated with the polymer or cross-linked polymer.

30. A membrane comprising a film of a polymer according to any one of claims 1 to 22 or a crosslinked polymer according to any one of claims 23 to 27.

31. A membrane electrode assembly comprising the membrane of claim 30 and an electrode.

32. A membrane comprising the composite material of claim 28.

33. A membrane electrode assembly comprising the membrane and electrode described in claim 32.

34. Structural formula (I): 【Chemistry 47】 A compound represented by: During the ceremony: 【Chemistry 48】 The moiety represented by the following structural formula: 【Chemistry 49】 and During the ceremony: R a , R b and R c are each independently H or C 1-12 alkyl; Z is selected from CH2, O, NH and N(C1-12 alkyl); X − is selected from F − , Cl − , Br − , OH − , NO − 2 , CN − , HCO 3 − , CO 3 2− , PF 6 − , BF 4 − , C 1-12 carboxylates and C 1-12 alkoxides; L 1 is selected from (OC 1-12 alkylene) k , (C 1-12 alkylene-O) k , C 1-12 alkylene, C 6-12 arylene, C 6-12 arylene-C 1-12 alkylene, C 1-12 alkylene-C 6-12 arylene, C 1-12 alkylene-OC 1-12 alkylene, C 1-12 alkylene-NH—C 1-12 alkylene, C 1-12 alkylene-N(C 1-12 alkyl)-C 1-12 alkylene, (NH—C 1-12 alkylene) k , (C 1-12 alkylene-NH) k ; The moiety represented by G has the following structural formula: 【Chemistry 50】 and selected from the moieties represented by any one of: 【Chemistry 51】 is the point of attachment of the moiety represented by G to L 1 ; k is an integer from 1 to 6; a is 1 or 2; Y 1 is —C(═O)—, O, S, NH, N(C 1-12 alkyl) or a bond; and further: each C 1-12 alkylene, C 6-12 arylene, C 1-12 alkyl, C 7-8 cycloalkenyl and 7 to 12 membered heterocycloalkenyl is independently optionally substituted with 1 to 6 substituents selected from the group consisting of F, Cl, Br, OH, NH 2 , C 1-12 alkyl, C 6-12 aryl C 1-12 haloalkyl, C 1-12 alkoxy, C 6-12 aryl, C 6-12 aryloxy, NH(C 1-12 alkyl), N(C 1-12 alkyl) 2 , C(O)O(C 1-12 alkyl) and C(O)NH(C 1-12 alkyl); compound.

35. The moiety represented by G has the following structural formula: 【Chemistry 52】 and L 1 is C 1-12 alkylene, (O-C 1-12 alkylene) k or (C 1-12 alkylene-O) k ; 35. The compound of claim 34.

36. The moiety represented by G has the following structural formula: 【Chemistry 53】 and L 1 is C 1-12 alkylene, (O-C 1-12 alkylene) k or (C 1-12 alkylene-O) k ; 35. The compound of claim 34.

37.

54. The part represented by 【Chemistry 55】 or ​ 35. The compound of claim 34, wherein:

38.

57. The part represented by 【Chemistry 58】 or ​ 35. The compound of claim 34, wherein:

39. The compound according to any one of claims 34 to 38, wherein L 1 is (OC 1-12 alkylene) k or (C 1-12 alkylene-O) k . 【Request 40】 【Chemical 60】 35. The compound of claim 34, selected from:

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