Patterned alkali exchange membranes

Abstract

The present disclosure relates to patterned anion exchange membranes comprising cross-linked and non-cross-linked segments. The present disclosure further relates to methods for fabricating the patterned anion exchange membranes, and electrochemical devices comprising the disclosed patterned anion exchange membranes.

Description

[Technical Field]

[0001] Related Applications This application claims the benefit of priority to U.S. Provisional Application No. 63 / 442,617, filed February 1, 2023, the entire teachings of which are incorporated herein by reference. [Background technology]

[0002] Background of the Invention Alkaline exchange membrane (AEM)-based electrolyzers and fuel cells are cost-effective and commercially important alternatives to proton exchange membrane (PEM) and conventional alkaline exchange devices.

[0003] The AEM provides an ionic network for anion transport in the membrane electrode assembly (MEA), facilitates water management within the cell, and acts as a binder for catalyst adhesion and overall mechanical integrity between the layers of the MEA.

[0004] Therefore, there is a need for high performance AEMs that are resistant to thermal and chemical decomposition under the harsh chemical environments and high temperatures of devices such as fuel cells and electrolyzers. Summary of the Invention

[0005] Summary of the Invention In a first exemplary embodiment, the present disclosure relates to a polymeric film comprising a first plurality of volumes and a second plurality of volumes: Each volume of the first plurality of volumes comprises a crosslinkable precursor ionomer and each volume of the second plurality of volumes comprises a crosslinked product ionomer, wherein each of the crosslinkable precursor ionomer and the crosslinked product ionomer has: a plurality of first repeat units, wherein each first repeat unit has the following structural formula: [ka] represented by; and a plurality of second repeat units, wherein each first repeat unit has the following structural formula: [ka] and moreover: The crosslinkable precursor ionomer has the following structural formula: [ka] and one or more crosslinkable moieties represented by any one of: The crosslinked product ionomer has the following structural formula: [ka] and one or more bridging moieties represented by any one of where for each occurrence of a crosslinkable moiety, the symbol [ka] L 2 represents the point of attachment to the bridging moiety, and for each occurrence of the bridging moiety, the symbol [ka] L 2 represents the point of attachment to [ka] represents the point of attachment to the first repeat unit or the second repeat unit; moreover: [ka] has the following structural formula: [ka] is a part represented by one of; [ka] has the following structural formula: [ka] a portion represented by any one of W is C 1-12 Alkyl or the following structural formula: [ka] is a part represented by one of; In the formula, the symbol [ka] L 3 represents the point of attachment to [ka] represents a double or 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; R 1 is H, C 1-12 Alkyl and C 6-12 aryl; Z 4 is a bond or C 6-12 is arylene, or Z 4 is CH and R 1 and Z 4 together with the C2 alkylene to which they are attached, form a C 5-12 Forms a cycloalkyl or 5- to 12-membered heterocyclyl; Z 6 is -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; R 3is H, C 1-12 Alkyl and C 6-12 aryl; Z 8 is a bond or C 6-12 arylene and CH, or Z 8 is CH and R 3 and Z 8 together with the C2 alkylene to which they are attached, form a C 5-12 Forms a cycloalkyl or 5- to 12-membered heterocyclyl; Z 9 is NR 10 or is a bond; R 5 , R 6 and R y 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, C6-12 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 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; R x and R z are independently H, F, Cl, Br, OH, NH2, NO2, CN, and C 1-12 Alkyl, C 6-12 selected from aryl, 5- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl; Ar 1 is C 6-12 aryl or 5- to 12-membered heterocyclyl; Ar 2 is C 6-12 arylene or 5- to 16-membered heterocyclylene; L 2 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C1-12 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(O)(OC 1-12 alkylene) m , OC(O)(C 1-12 alkylene) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m , (NH)C(OC 1-12 alkylene) m , (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(O)(OC 1-12 alkylene) n , OC(O)(C 1-12 alkylene) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12alkylene) n , (NH)C(OC 1-12 alkylene) n , (NH-C 1-12 alkylene) n , (C 1-12 alkylene-NH n and bond; m is an integer from 1 to 6; n is an integer from 1 to 6; Y 2 -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 - and C 1-12 carboxylates; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl, where: Each C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl, 5-12 membered heteroaryl, 5-12 membered heterocyclyl, C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5- to 16-membered heterocyclylene, and 5- to 12-membered heteroarylene are independently optionally selected from the group consisting of F, Cl, Br, OH, NH, NO, oxo, CN, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, 5-16 membered heterocyclyl, 5-12 membered heteroaryl, NH(C 1-12alkyl), N(C 1-12 alkyl)2, OC(O)(C 1-12 alkyl), C(O)O(C 1-12 alkyl), S(O)2(C 1-12 alkyl), S(O)2(C 6-12 aryl), NHC(O)(C 1-12 alkyl) and C(O)NH(C 1-12 and substituted with 1 to 6 substituents independently selected from the group consisting of alkyl.

[0006] In a second exemplary embodiment, the present disclosure relates to an electrode comprising a catalyst / ionomer layer, the catalyst / ionomer layer comprising a polymer film as described herein with respect to the first embodiment and various aspects thereof.

[0007] In a third exemplary embodiment, the present disclosure relates to a composite material comprising a polymer film as described herein with respect to the first embodiment and various aspects thereof or an electrode as described herein with respect to the second embodiment and various aspects thereof and a support, wherein the polymer film or electrode is disposed on the support.

[0008] In a fourth exemplary embodiment, the present disclosure relates to a membrane electrode assembly (MEA) comprising a polymer film as described herein with respect to the first embodiment and various aspects thereof, an electrode as described herein with respect to the second embodiment and various aspects thereof, or a composite material as described herein with respect to the third embodiment and various aspects thereof.

[0009] In a fifth exemplary embodiment, the present disclosure relates to a fuel cell including an MEA, a fuel source, and an oxidant as described herein with respect to the fourth embodiment and various aspects thereof.

[0010] In a sixth exemplary embodiment, the present disclosure relates to an electrolyzer including an MEA and an electrolyte source described herein with respect to the fourth embodiment and various aspects thereof.

[0011] In a seventh exemplary embodiment, the present disclosure provides: a) providing a precursor film comprising a crosslinkable precursor ionomer; b) applying a mask to the film, thereby providing a partially protected film; c) exposing the partially protected film to ultraviolet radiation for a time sufficient to crosslink the crosslinkable ionomer, thereby producing a polymer film. The present invention relates to a method of making a polymer film as described herein with respect to the first embodiment and various aspects thereof, including: [Brief explanation of the drawings]

[0012] BRIEF DESCRIPTION OF THE DRAWINGS [Figure 1] FIG. 1 is a schematic representation of patterned crosslinking of AEMs. [Figure 2] Figure 2 shows an image of a cross-linked, patterned AEM under a 70-mesh stainless steel mask. The AEM was swollen in water and dried overnight, revealing a persistent surface pattern. [Figure 3] FIG. 3 is an AEM image of a 70 mesh stainless steel mask that was heated at 50° C. for 45 minutes while placed on the surface with a 20 g weight, then swelled in water and dried overnight at room temperature. [Figure 4] Figure 4 shows an image of the cross-linked, patterned AEM under a 500 mesh stainless steel mask. The AEM was then swollen in water and dried overnight, revealing a persistent surface pattern. [Figure 5] FIG. 5 is a bar graph showing polarization curve data at 1.8 and 2.1 V for AEM electrolyzer devices using patterned and unpatterned films. [Figure 6] FIG. 6 is a graph showing electrochemical impedance spectroscopy data collected from the AEM electrolyzer test shown in FIG. DETAILED DESCRIPTION OF THE INVENTION

[0013] Detailed Description Developing anion exchange membranes (AEMs) containing durable polymer backbones and cationic groups is required for commercialization of fuel cells, electrolyzers, redox flow batteries, water purifiers, and other electrochemical devices. Alkaline systems have several advantages over their acidic counterparts, particularly because device fabrication requires less lossy electrodes and bipolar plates and offers longer lifetimes. At high pH, ​​oxygen reduction is more facile and lower overpotentials are required, making alkaline electrochemical devices an attractive alternative to proton exchange membrane (PEM) devices and allowing the use of metals other than platinum as electrocatalysts.

[0014] Alkaline exchanged ionomers (AEIs) are cationic polymers capable of conducting hydroxide anions within the MEA of electrolyzer and fuel cell devices. Suitable AEIs for water electrolyzers and fuel cells are often characterized as having high hydroxide conductivity, moderate water absorption, and solubility in organic solvents.

[0015] Disclosed herein are patterned AEMs containing crosslinked AEI and non-crosslinked AEI fragments. The disclosed AEMs are prepared from AEIs with cationic and crosslinkable moieties. The AEMs are prepared by covering a membrane containing UV-crosslinkable AEI with a mask and then exposing it to UV light. This procedure selectively crosslinks the ionomer in the areas not covered by the mask. The resulting partially crosslinked AEM has a pattern of non-crosslinked fragments extending in all directions from the surface through the membrane thickness. These fragments correspond to the areas covered by the mask during UV exposure, while the crosslinked fragments correspond to the voids in the mask (see Figure 1). As a result, the patterned AEMs have low and high ion-conducting volumes due to the difference in water content between the crosslinked and non-crosslinked fragments. Highly crosslinked regions have reduced water content, resulting in reduced ionic conductivity in these regions, while non-crosslinked regions have lower water content, forming ion channels. The high ion density in the ion channels creates concentrated pathways for ions. For the same overall ionic content, polymers with ion channels have higher ionic conductivity compared to polymers without ion channels (shown for ionic / nonionic block copolymers vs. random copolymers of the same composition).

[0016] Poor performance or durability in electrochemical devices, such as electrolyzers or fuel cells, can often be attributed to either chemical or mechanical degradation of the AEI. During operation, MEA components are subjected to pressure and electrochemical forces from the flowing electrolyte, inflowing and outflowing gases, heat, and applied voltage. These forces cause physical changes (swelling or deformation) in the AEI layers, resulting in delamination. Delamination results in loss of electrical and ionic contact, manifesting as increased resistance and poor overall device performance.

[0017] The disclosed patterned AEMs, which combine crosslinked and non-crosslinked volumes, have a three-dimensional texture that resists repeated swelling and dehydration, which improves the durability of the AEMs by preventing delamination.

[0018] The present disclosure describes patterned AEMs formed with AEIs containing cationic and UV-crosslinkable moieties. Examples of such AEIs are described in International Patent Application Publication WO 2023 / 018765, which is incorporated herein by reference in its entirety. The patterned AEMs are obtained by exposing a partially covered AEI film to UV light. This process does not require the use of external crosslinkers, such as dithiols or dialdehydes, to achieve a mechanically robust electrode. This eliminates the need to subject the AEM to organic reagents after fabrication or rely on reactions occurring in a slurry after coating. This also allows for selective masking of precursor films (i.e., AEI films containing uncrosslinked UV-crosslinkable moieties) to reinforce specific regions of the AEM, for example, for mechanical, chemical, or thermal durability.

[0019] The disclosed approach to preparing patterned AEMs extends film "cure time" indefinitely without the risk of generating interactive materials. The process also provides for curing upon the use of UV light, eliminating the risk of premature curing. Using UV activation to crosslink ionomers is advantageous because they can be synthesized and fabricated in any form (film, powder, solution) required prior to irreversible crosslinking. UV curing of coatings is common in polymer manufacturing and simplifies processing for larger-scale production. This is preferable to methods that crosslink in situ or by post-preparation chemical immersion, as these methods are difficult to scale up to large-scale manufacturing. Furthermore, UV curing offers complete control of the AEM pattern based on mask parameters, whereas controlling the curing of selected sections of the film is difficult when using thermal or chemical crosslinking initiation.

[0020] In some embodiments, one or more masks can be applied to (e.g., to cover) selected portions of a precursor film comprising an AEM that is not crosslinked to prevent selected portions of the AEM material from crosslinking. The one or more masks are preferably configured to substantially prevent exposure of the crosslinkable polymer to UV light that would otherwise crosslink the crosslinkable polymer. For example, a substantially UV-opaque mask applied to a UV-crosslinkable polymer substantially prevents the crosslinkable polymer from crosslinking upon treatment with UV radiation by shielding the covered portions from UV radiation.

[0021] In some embodiments, the UV light can be focused on selected portions of the crosslinkable polymer to prevent unselected portions of the crosslinkable polymer from crosslinking, hi some embodiments, only the portions of the crosslinkable polymer that come into contact with the focused UV light can be crosslinked.

[0022] Ionomers of the Invention Exemplary components (e.g., backbone, repeating units, cationic moieties, or crosslinkable moieties) of crosslinkable AEIs that can be used in the AEMs of the present disclosure are provided in the following paragraphs. The AEIs can include any combination of the components disclosed below.

[0023] 1. Ionomer backbone Crosslinkable or cationic moieties can be incorporated into the polymer by linking them to the repeating units. For example, the following repeating units or ionomeric backbones can be functionalized with crosslinkable or cationic moieties: [ka] [ka] [ka]

[0024] 2. 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 ionomer backbone. Additionally or alternatively, the ionomer backbone can include cationic groups. For example, the following cationic moieties can be incorporated into the AEI: [ka] indicates the point of attachment of the cationic moiety to the backbone or to a linker connected to the backbone): [ka] [ka] [ka] [ka]

[0025] 3. Crosslinkable part AEIs can contain crosslinkable moieties in some of the repeating units of the polymer. The crosslinkable moieties can include, for example, 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, benzoylphosphine oxide, and bisbenzoylphosphine oxide, can also be incorporated into some of the repeating units of the ionomer.

[0026] In some embodiments, the crosslinkable ionomers of the present disclosure include a Type II photoinitiator, such as benzophenone. For example, the ionomers can be prepared by copolymerizing cyclooctene substituted with a benzophenone-containing moiety, cyclooctene substituted with a cationic moiety, and unsubstituted cyclooctene to yield, for example, the following copolymer: [ka] The copolymers shown are random copolymers.

[0027] Upon exposure to UV light, the benzophenone appendages in the ionomer undergo UV-activated C,H-insertion reactions to form covalent C-C bonds with polymer fragments containing aliphatic C-H bonds. Thus, the benzophenone-containing moieties can be covalently bonded to C-H-containing groups in the polymer backbone or side-chain appendages. For example, after UV exposure, the benzophenone-based bridging moieties can be attached to i) the backbone, ii) the cationic moieties; or iii) alkylene, alkyl, or cycloalkyl groups in the linkers that attach the cationic or benzophenone moieties to the backbone. Such crosslinks can be intramolecular (covalent bonds formed via C,H-insertion within the same polymer chain) or intermolecular (covalent bonds formed via C,H-insertion within different polymer chains). Thus, upon exposure to UV light, ionomers containing benzophenone-containing repeating units form crosslinked polymer networks. The networks can include, for example, the following crosslinking moieties: [ka]

[0028] In some embodiments, the AEIs of the present disclosure can include a diazerene-containing crosslinkable moiety. The diazerene fragment decomposes upon exposure to UV light to a carbene, which allows for crosslinking of essentially any organic polymer via C—H activation: [ka]

[0029] Additionally, the AEIs of the present disclosure can include bridging moieties that undergo UV-initiated [2+2] and [4+4] cycloadditions, as shown below: [Table 1]

[0030] In some embodiments, the AEIs of the present disclosure can include an azide-containing crosslinkable moiety. The azide fragment decomposes into a nitrene upon exposure to UV light, which allows for crosslinking of organic polymers via C—H activation or recombination of two nitrenes to form a diazo crosslinker: [ka]

[0031] 4. Repeating Unit In some embodiments, the crosslinkable ionomers of the present disclosure may include the following combinations of repeating units: [ka] [ka] [ka] , where each R a independently, C 1-12 Alkyl or C 3-12 It may be cycloalkyl.

[0032] 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. Further, 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, 5 thEdition, 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.

[0033] 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., University 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.

[0034] During the ceremony, [ka] is a single or double bond.

[0035] When a range of values ​​is listed, it is intended to encompass each value and subrange within the range. For example, "C 1-6 "Alkyl" refers to C1, C2, C3, C4, C5, C6, C 1-6 , C 1-5 , 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.

[0036] 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 1-6Examples 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 certain embodiments, an alkyl group is an unsubstituted C 1-12 Alkyl (e.g., unsubstituted C 1-6 Alkyl, 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 substituted C 1-12 Alkyl (e.g., substituted C 1-6 alkyl, for example -CF3, Bn).

[0037] The term "haloalkyl" refers to a substituted alkyl group in which one or more of the hydrogen atoms is independently replaced with 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 1-2Examples of haloalkyl groups include -CHF2, -CH2F, -CF3, -CH2CF3, -CF2CF3, -CF2CF2CF3, -CCl3, -CFCl2, -CF2Cl, and the like.

[0038] 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 1-4 In 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.

[0039] 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 5-6In 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 contain fused cycloalkyl rings. Polycyclic cycloalkyl groups can be spirocyclic or bridged cycloalkyl groups. C 5-6 Examples of cycloalkyl groups include cyclopentyl (C5) and cyclohexyl (C6). 3-6 Examples of cycloalkyl groups include the aforementioned C 5-6 Cycloalkyl groups include cyclopropyl (C3) and cyclobutyl (C4). 3-8 Examples of cycloalkyl groups include the aforementioned C 3-6 Cycloalkyl 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, a 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.

[0040] 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, the 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, but are not limited to, cyclooctenyl, bicyclooctenyl, and norbornenyl.

[0041] 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 ("C 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 the aryl ring, as defined above, is fused with one or more carbocyclyl or heterocyclyl groups, and the radical or point of attachment is on the aryl ring; 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.

[0042] 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.

[0043] The term "heterocyclyl" or "heterocyclic" refers to the 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 containing one or more nitrogen atoms, the point of attachment may be at a carbon or nitrogen atom, if valence allows. Heterocyclyl groups can be either monocyclic ("monocyclic heterocyclyl") or polycyclic (e.g., fused, bridged, or spiro ring systems, such as bicyclic systems ("bicyclic heterocyclyl") or tricyclic systems ("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 on either the cycloalkyl or heterocyclyl ring, or and the point of attachment is on the heterocyclyl ring; in such instances, the number of ring members continues to indicate the number of ring members 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 certain embodiments, the heterocyclyl group is an unsubstituted 5- to 12-membered heterocyclyl. In certain embodiments, the heterocyclyl group is a substituted 5- to 12-membered heterocyclyl.

[0044] In some embodiments, a heterocyclyl group is a 5- to 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- to 10-membered heterocyclyl"). In some embodiments, a heterocyclyl group is a 5- to 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- to 8-membered heterocyclyl"). In some embodiments, a heterocyclyl group is a 5- to 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- to 6-membered heterocyclyl"). In some embodiments, a 5- to 6-membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen, and sulfur. In some embodiments, a 5- to 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.

[0045] 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.

[0046] 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, 1H-benzo[e][1,4]diazepine ... 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.

[0047] In some embodiments, the term "heterocyclyl" refers to a radical of a 5- to 16-membered monocyclic or polycyclic (e.g., bicyclic, tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in the cyclic array), also referred to as "heteroaryl," having ring carbon atoms and 1 to 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; in such instances, the number of ring members continues to indicate the number of ring members in the heteroaryl ring system. "Heteroaryl" also includes ring systems in which a heteroaryl ring, as defined above, is fused to one or more aryl groups, and the point of attachment can be on either the aryl or heteroaryl ring; in such instances, the number of ring members indicates the number of ring members in the fused polycyclic (aryl / heteroaryl) ring system. In 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., the ring containing the heteroatom (e.g., 2-indolyl) or the ring without the heteroatom (e.g., 5-indolyl).

[0048] In some embodiments, a heteroaryl group is a 5- to 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 (a "5- to 12-membered heteroaryl"). In some embodiments, a heteroaryl group is a 5- to 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 (a "5- to 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.

[0049] 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, but are not limited to, phenanthridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenothiazinyl, phenoxazinyl, and phenazinyl.

[0050] The terms "unsaturated" or "partially unsaturated" refer to a moiety that contains at least one double or triple bond.

[0051] The term "saturated" refers to a moiety that does not contain any double or triple bonds, ie, the moiety contains only single bonds.

[0052] 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, heteroarylene is a divalent moiety of heteroaryl, cycloalkylene is a divalent moiety of cycloalkyl, and heterocyclylene is a divalent moiety of heterocyclyl.

[0053] 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, or a bond if internal.

[0054] A group is optionally substituted unless expressly provided otherwise. The term "optionally substituted" refers to 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 may be substituted or unsubstituted (e.g., a "substituted" or "unsubstituted" alkyl, a "substituted" or "unsubstituted" cycloalkyl, a "substituted" or "unsubstituted" cycloalkenyl, a "substituted" or "unsubstituted" heterocyclyl, a "substituted" or "unsubstituted" heterocycloalkenyl, a "substituted" or "unsubstituted" aryl, or a "substituted" or "unsubstituted" heteroaryl group). Generally, the term "substituted" means that at least one hydrogen atom present on the group is replaced with an acceptable substituent, e.g., a substituent that, upon substitution, results in a stable compound, e.g., a compound that does not spontaneously undergo transformation by rearrangement, cyclization, elimination, or other reaction, etc. Unless otherwise specified, 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 stable compounds. The present invention contemplates any and all such combinations in order to achieve stable compounds. 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. The present invention is not intended to be limited in any manner by the exemplary substituents described herein.

[0055] Exemplary carbon atom substituents include, but are not limited to, halogen, —CN, —NO 2 , —N 3 , —OH, F, Cl, Br, I, oxo, —SO 2 H, —SO 3 H, —OR aa , -NH(R aa )2, -N(R aa )2, -N(R aa)3 + X - , -SH, -SR aa , -C(=O)R aa , -CO2H, -CHO, -CO2R 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- to 16-membered heterocyclyl and C 6-12 aryl, or two R aa The groups are linked to form a 3- to 16-membered heterocyclyl.

[0056] Numerical ranges are inclusive of the numbers defining the range. Measurements and measurable values ​​are understood to be approximate, taking into account the significance and error associated with the measurements. As used herein, the terms "about" and "approximately" have their technically understood meanings; the use of one versus 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 understood by those 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).

[0057] Disclosed herein are catalyst / ionomer compositions prepared from ionomers containing Tetrakis® cations. The term Tetrakis® refers to a compound having the following structural formula: [ka] In the formula, [ka] is the point of attachment to the polymer or to a linker connected to the polymer, and R a , R b and R c are each independently alkyl or cycloalkyl.

[0058] As used herein, a polymer "backbone" or polymer "backbone" is a series of bonded atoms that together produce a continuous chain of polymer molecules. As used herein, a polymer "side chain" is a series of bonded atoms that are pendant from the polymer backbone.

[0059] As used herein, the term "repeating unit" (also known as monomeric unit) refers to a chemical moiety that occurs multiple times in the backbone of a polymer, linking repeating units together in succession to make up a complete polymer chain (excluding end groups). Repeating units are typically shown in brackets with an open valence indicating the point of attachment to the adjacent repeating unit in the backbone: [ka]

[0060] A polymer can contain one or more types of repeating units with different chemical structures. A polymer containing two or more different types of repeating units is known as a copolymer. A copolymer can be a block copolymer, where a first type of repeating unit forms a continuous main chain, i.e., a first homopolymer subunit, and a second type of repeating unit forms a continuous main chain, i.e., a second homopolymer subunit, for a required number of homopolymer subunits. Various homopolymer subunits are linked via covalent bonds to form a block copolymer. In some embodiments, the ionomer of the present disclosure is a block copolymer.

[0061] The copolymer may be a statistical copolymer, also known as a random copolymer, in which the different types of repeating units are randomly distributed along the backbone. In a random copolymer, repeating units of the same type need not be linked to each other in the backbone. In some embodiments, the ionomers of the present disclosure are random copolymers.

[0062] As used herein, the term "crosslinked polymer" refers to a polymer in which two or more non-adjacent repeating units of the same backbone or two or more repeating units of different backbones are linked via bridging moieties. The term "crosslinked polymer" also refers to two or more different backbones that are linked via multiple bridging moieties. A crosslinked polymer, such as a crosslinked ionomer, can include multiple backbones linked by multiple bridging moieties to form an interconnected polymer network.

[0063] As used herein, the term "bridging moiety" refers to a multivalent, e.g., divalent or trivalent, moiety that forms a covalent bond with two or more non-adjacent repeat units of the same polymer backbone or with one or more repeat units of different backbones.

[0064] As used herein, the term "radical initiator" refers to a compound that can generate radical species to promote radical chain reactions such as radical polymerization. Examples of radical initiators include azo compounds and organic peroxides, such as 2,2'-azobis(2-methylpropionitrile), azobisisobutyronitrile, azobisdimethylvaleronitrile, and benzoyl peroxide.

[0065] As used herein, the phrase "catalyst supported on carbon" refers to a catalyst-containing material in which catalyst particles are disposed on the surface of activated carbon. Carbon as a support material for the catalyst allows for the dispersion and stabilization of small metal particles on the surface.

[0066] As used herein, the term "Raney nickel" refers to a solid catalyst composed of fine particles of a nickel-aluminum alloy. A typical catalyst is about 85% nickel by weight, corresponding to about two atoms of nickel for every atom of aluminum.

[0067] 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 individual polymer molecules. It is determined by measuring the molecular weights of n polymer molecules, adding up the molecular weights, and dividing by n.

[0068] In a first aspect, the present disclosure relates to a polymeric film comprising a first plurality of volumes and a second plurality of volumes: Each volume of the first plurality of volumes comprises a crosslinkable precursor ionomer and each volume of the second plurality of volumes comprises a crosslinked product ionomer, the crosslinkable precursor ionomer and the crosslinked product ionomer each having: a plurality of first repeating units, wherein each first repeating unit has the following structural formula: [ka] represented by; and a plurality of second repeating units, wherein each first repeating unit has the following structural formula: [ka] and moreover: The crosslinkable precursor ionomer has the following structural formula: [ka] and one or more crosslinkable moieties represented by any one of: The crosslinked product ionomer has the following structural formula: [ka] and one or more bridging moieties represented by any one of where for each occurrence of a crosslinkable moiety, the symbol [ka] L 2 represents the point of attachment to the bridging moiety, and for each occurrence of the bridging moiety, the symbol [ka] L 2 represents the point of attachment to [ka] represents the point of attachment to the first repeat unit or the second repeat unit; moreover: [ka] has the following structural formula: [ka] is a part represented by one of; [ka] has the following structural formula: [ka] a portion represented by any one of W is C 1-12 Alkyl or the following structural formula: [ka] is a part represented by one of; In the formula, the symbol [ka] L 3 represents the point of attachment to [ka] represents a double or 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; R 1 is H, C 1-12 Alkyl and C 6-12 aryl; Z 4 is a bond or C 6-12 is arylene, or Z 4 is CH and R 1 and Z 4 together with the C2 alkylene to which they are attached, form a C 5-12 Forms a cycloalkyl or 5- to 12-membered heterocyclyl; Z 6 is -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; R 3 is H, C 1-12 Alkyl and C 6-12 aryl; Z 8 is a bond or C 6-12 arylene and CH, or Z 8 is CH and R 3 and Z 8 together with the C2 alkylene to which they are attached, form a C 5-12 forming a cycloalkyl or 5- to 12-membered heterocyclyl; Z 9 is NR 10 or is a bond; R 5 , R 6 and R y 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 3-12cycloalkyl 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 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; R x and R zare independently H, F, Cl, Br, OH, NH2, NO2, CN, and C 1-12 Alkyl, C 6-12 selected from aryl, 5- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl; Ar 1 is C 6-12 aryl or 5- to 12-membered heterocyclyl; Ar 2 is C 6-12 arylene or 5- to 16-membered heterocyclylene; 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(O)(OC 1-12 alkylene) m , OC(O)(C 1-12 alkylene) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m , (NH)C(OC 1-12 alkylene) m , (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(O)(OC 1-12 alkylene) n , OC(O)(C 1-12 alkylene) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) n , (NH)C(OC 1-12 alkylene) n , (NH-C 1-12 alkylene) n , (C 1-12 alkylene-NH n and bond; m is an integer from 1 to 6; n is an integer from 1 to 6; Y 2 -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 - and C 1-12 carboxylates; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl, where: Each C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12Cycloalkyl, C 6-12 Aryl, 5-12 membered heteroaryl, 5-12 membered heterocyclyl, C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5- to 16-membered heterocyclylene, and 5- to 12-membered heteroarylene are independently optionally selected from the group consisting of F, Cl, Br, OH, NH, NO, oxo, CN, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, 5-16 membered heterocyclyl, 5-12 membered heteroaryl, NH(C 1-12 alkyl), N(C 1-12 alkyl)2, OC(O)(C 1-12 alkyl), C(O)O(C 1-12 alkyl), S(O)2(C 1-12 alkyl), S(O)2(C 6-12 aryl), NHC(O)(C 1-12 alkyl) and C(O)NH(C 1-12 and substituted with 1 to 6 substituents independently selected from the group consisting of alkyl.

[0069] In a first aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] and W is C 1-12 Alkyl or the following structural formula: [ka] and Each bridging moiety is represented by structural formula (I).

[0070] In a second aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] and W is C 1-12 Alkyl or the following structural formula: [ka] and Each bridging moiety is represented by structural formula (I): The remainder of the features and exemplary features of the second aspect are as described above for the first aspect of the first embodiment.

[0071] In a third aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] and W is C 1-12 Alkyl or the following structural formula: [ka] and each bridging moiety is represented by Structural Formula (I). The remainder of the features and exemplary features of the third aspect are as described above for the first and second aspects of the first embodiment.

[0072] In a fourth aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] wherein each third repeat unit is a C alkylene and each bridging moiety is represented by Structural Formula (I). The remainder of the features and exemplary features of the fourth aspect are as described above for the first through third aspects of the first embodiment.

[0073] In a fifth aspect of the first embodiment, [ka] 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 first embodiment.

[0074] In a sixth aspect of the first embodiment, [ka] 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 first embodiment.

[0075] In a seventh aspect of the first embodiment, [ka] 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 first embodiment.

[0076] In an eighth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the eighth aspect are as described above with respect to the first through seventh aspects of the first embodiment.

[0077] In a ninth aspect of the first embodiment, the first crosslinked ionomer further comprises a plurality of third repeat units, each third repeat unit having the following structural formula: [ka] and where Z10 and Z 11 are each independently C 1-3 is an alkylene or a bond; R 20 is H, C 1-12 Alkyl or C 6-12 It is aryl. In some examples, at least one third repeat unit comprises: [ka] The bridging moiety is connected to a bridge represented by a point of attachment on the bridge shown as

[0078] In a tenth aspect of the first embodiment, each first repeat unit has the following structural formula: [ka] wherein each second repeat unit has the following structural formula: [ka] wherein each third repeat unit is a C alkylene and each bridging moiety is represented by Structural Formula (I). The remainder of the features and exemplary features of the tenth aspect are as described above for the first through ninth aspects of the first embodiment.

[0079] In an eleventh aspect of the first embodiment, each first repeat unit has the following structural formula: [ka] wherein each second repeat unit has the following structural formula: [ka] wherein each third repeat unit is a C alkylene and each bridging moiety is represented by structural formula (I). For example, R 13 , R 14 , R 15and R 16 is methyl, and the molar ratio of the first repeat unit, the second repeat unit, and the third repeat unit is 1:14:5. The remainder of the features and exemplary features of the eleventh aspect are as described above for the first through tenth aspects of the first embodiment.

[0080] In a twelfth aspect of the first embodiment, [ka] has the following structural formula: [ka] and During the ceremony: R 20 , R 22 , R 24 , R 26 and R 31 are each independently C 1-12 is alkyl; R 21 is C 1-12 alkyl or R 21 is the nitrogen atom to which it is attached and L 2 together with at least one atom of the formula (I) to form a 5- to 12-membered heterocyclyl; 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 35 is C 1-12 alkyl or R 35 is the nitrogen atom to which it is attached and L 2 together with at least one atom of to form a 5- to 12-membered heterocyclyl; Z 10 and Z 11 are each independently C1-3 is an alkylene or a bond; Z 12 and Z 13 are each 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 first embodiment.

[0081] In a thirteenth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirteenth aspect are as described above with respect to the first through twelfth aspects of the first embodiment.

[0082] In a fourteenth aspect of the first embodiment, [ka] has the following structural formula: [ka] For example, [ka] has the following structural formula: [ka] Alternatively, [ka] has the following structural formula: [ka] The remainder of the features and example features of the fourteenth aspect are as described above with respect to the first through thirteenth aspects of the first embodiment.

[0083] In a fifteenth aspect of the first embodiment, Z 10 and Z 11 are each independently C 1-3 Alkylene. For example, Z 10 is a C2 alkylene, and Z 11 is a C alkylene. The remainder of the features and exemplary features of the fifteenth aspect are as described above for the first through fourteenth aspects of the first embodiment.

[0084] In a sixteenth aspect of the first 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 first embodiment.

[0085] In a seventeenth aspect of the first embodiment, [ka] has the following structural formula: [ka] For example, [ka] has the following structural formula: [ka] Alternatively, [ka] has the following structural formula: [ka] The remainder of the features and example features of the seventeenth aspect are as described above with respect to the first through sixteenth aspects of the first embodiment.

[0086] In an eighteenth aspect of the first embodiment, Z 12 is CH2, O, NH or N(C 1-12 alkyl). For example, Z 12 is CH2 or O. Alternatively, Z 12 is 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 first embodiment.

[0087] In a nineteenth aspect of the first embodiment, [ka] 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 first embodiment.

[0088] In a twentieth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the twentieth aspect are as described above with respect to the first through nineteenth aspects of the first embodiment.

[0089] In a twenty-first aspect of the first embodiment, Z 13 is CH2, O, NH or N(C 1-12 alkyl). For example, Z 13 is CH2 or O. Alternatively, Z 13is 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 first embodiment.

[0090] In a twenty-second aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the twenty-second aspect are as described above with respect to the first through twenty-first aspects of the first embodiment.

[0091] In a twenty-third aspect of the first embodiment, R 28 is 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 first embodiment.

[0092] In a twenty-fourth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the twenty-fourth aspect are as described above with respect to the first through twenty-third aspects of the first embodiment.

[0093] In a twenty-fifth aspect of the first embodiment, [ka] has the following structural formula: [ka] and During the ceremony: R 39 , R 40 , R 42 , R 45 , 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 37 is C 1-12 alkyl or R 37 is the nitrogen atom to which it is attached and L 3 together with at least one atom of to form a 5- to 12-membered heterocyclyl; R 38 is C 1-12 alkyl or R 38 is the nitrogen atom to which it is attached and L 3 together with at least one atom of to 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 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 first embodiment.

[0094] In a twenty-sixth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the twenty-sixth aspect are as described above in relation to the first through twenty-fifth aspects of the first embodiment.

[0095] In a twenty-seventh aspect of the first embodiment, [ka] has the following structural formula: [ka] For example, [ka] has the following structural formula: [ka] Alternatively, [ka] has the following structural formula: [ka] The remainder of the features and example features of the twenty-seventh aspect are as described above with respect to the first through twenty-sixth aspects of the first embodiment.

[0096] In a twenty-eighth aspect of the first embodiment, Z 14 and Z 15 are each independently C 1-3 Alkylene. For example, Z 14 is a C2 alkylene, and Z 15 is a C alkylene. The remainder of the features and exemplary features of the twenty-eighth aspect are as described above for the first through twenty-seventh aspects of the first embodiment.

[0097] In a twenty-ninth aspect of the first 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 first embodiment.

[0098] In a thirtieth aspect of the first embodiment, [ka] has the following structural formula: [ka] For example, [ka] has the following structural formula: [ka] Alternatively, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirtieth aspect are as described above with respect to the first through twenty-ninth aspects of the first embodiment.

[0099] In a thirty-first aspect of the first embodiment, Z 16 is CH2, O, NH or N(C 1-12 alkyl). For example, Z 16 is CH2 or O. Alternatively, Z 16 is NH or N(C 1-12The remainder of the features and exemplary features of the thirty-first aspect are as described above for the first through thirtieth aspects of the first embodiment.

[0100] In a thirty-second aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirty-second aspect are as described above with respect to the first through thirty-first aspects of the first embodiment.

[0101] In a thirty-third aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirty-third aspect are as described above with respect to the first through thirty-second aspects of the first embodiment.

[0102] In a thirty-fourth aspect of the first embodiment, Z 13 is CH2, O, NH or N(C 1-12 alkyl). 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 first embodiment.

[0103] In a thirty-fifth aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirty-fifth aspect are as described above with respect to the first through thirty-fourth aspects of the first embodiment.

[0104] In a thirty-sixth aspect of the first embodiment, R 44 is H or methyl. For example, R 44 is H. Alternatively, R 44 is methyl. The remainder of the features and exemplary features of the thirty-sixth aspect are as described above for the first through thirty-fifth aspects of the first embodiment.

[0105] In a thirty-seventh aspect of the first embodiment, [ka] has the following structural formula: [ka] The remainder of the features and example features of the thirty-seventh aspect are as described above with respect to the first through thirty-sixth aspects of the first embodiment.

[0106] In a thirty-eighth aspect of the first embodiment, W is [ka] The remainder of the features and example features of the thirty-eighth aspect are as described above with respect to the first through thirty-seventh aspects of the first embodiment.

[0107] In a thirty-ninth aspect of the first embodiment, Z 9 is NR 10 and;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 with respect to the first through thirty-eighth aspects of the first embodiment.

[0108] In a fortieth aspect of the first 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 are each phenyl. The remainder of the features and exemplary features of the fortieth aspect are as described above for the first through thirty-ninth aspects of the first embodiment.

[0109] In a forty-first aspect of the first 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 alkyl, and R 12 is C 5-7 Cycloalkyl or C 1-3 alkyl. For example, R 11 and R 12 are each methyl; or R 11 is methyl and R 12 is isopropyl; or R 11 is cyclohexyl and R 12 is methyl. The remainder of the features and exemplary features of the forty-first aspect are as described above for the first through fortieth aspects of the first embodiment.

[0110] In a forty-second aspect of the first embodiment, W is [ka] The remainder of the features and example features of the forty-second aspect are as described above with respect to the first through forty-first aspects of the first embodiment.

[0111] In a forty-third aspect of the first embodiment, R 13 is the unsubstituted C 6-12 Aryl. For example, R 13is unsubstituted phenyl. Alternatively, R 13 is C 1-12 Alkyl, C 1-12 Alkoxy and N(C 1-12 C substituted with 1 to 3 substituents independently selected from alkyl)2 6-12 Aryl. For example, R 13 is substituted with 1 to 3 substituents independently selected from methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, propoxy, isopropoxy, dimethylamino, or diethylamino; 6-12 and aryl, e.g., phenyl substituted with 1 to 3 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 first embodiment.

[0112] In a forty-fourth aspect of the first embodiment, R 14 is C 1-12 alkyl. 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 first embodiment.

[0113] In a forty-fifth aspect of the first embodiment, R 15 and R 16 are each independently C 1-12 alkyl. 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 16are each methyl. The remainder of the features and exemplary features of the forty-fifth aspect are as described above for the first through forty-fourth aspects of the first embodiment.

[0114] In a forty-sixth aspect of the first 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 first embodiment.

[0115] In a forty-seventh aspect of the first embodiment, R 15 and R 16 together with the carbon atoms to which they are attached form C 6-12 Forms an aryl. 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 first embodiment.

[0116] In a forty-eighth aspect of the first embodiment, W is [ka] The remainder of the features and example features of the forty-eighth aspect are as described above with respect to the first through forty-seventh aspects of the first embodiment.

[0117] In a forty-ninth aspect of the first 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 exemplary features of the forty-ninth aspect are as described above for the first through forty-eighth aspects of the first embodiment.

[0118] In a fiftieth aspect of the first embodiment, R 17 is C 1-12 alkyl, and R 18 and R 19 together with the nitrogen atom to which they are attached form a 5- to 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 first embodiment.

[0119] In a fifty-first aspect of the first embodiment, R 17 , R 18 and R 19 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 first embodiment.

[0120] In a fifty-second aspect of the first embodiment, 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(O)(OC 1-12 alkylene) m , OC(O)(C 1-12 alkylene) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m , (NH)C(OC 1-12 alkylene) m , (NH-C 1-12 alkylene) mand (C 1-12 alkylene-NH m Selected from: L 2 Each of the moieties representing L may be attached to Q by either end of the moiety. 2 is OC(O)(C 1-12 alkylene) m When L is, it can be attached to Q via an ester or via an alkylene. 2 is C 1-12 alkylene. 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 exemplary features of the fifty-second aspect are as described above for the first through fifty-first aspects of the first embodiment.

[0121] In a fifty-third aspect of the first embodiment, L 2 (OC 1-12 alkylene) m or (C 1-12 alkylene-O) m For example, L 2 is —CH 2 O— or —OCH 2 —. The remainder of the features and exemplary features of the fifty-third aspect are as described above for the first through fifty-second aspects of the first embodiment.

[0122] In a 54th aspect of the first 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 54th aspect are as described above for the first to 53rd aspects of the first embodiment.

[0123] In a fifty-fifth aspect of the first embodiment, L 3 is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C 1-12Alkylene-C 6-12 Arylene, C 1-12 Alkylene-OC 1-12 Alkylene, (OC 1-12 alkylene) n , (C 1-12 alkylene-O) n , C(O)(OC 1-12 alkylene) n , OC(O)(C 1-12 alkylene) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) n , (NH)C(OC 1-12 alkylene) n , (NH-C 1-12 alkylene) n , (C 1-12 alkylene-NH n and a bond. 3 Each of the moieties representing L may be attached to Q by either end of the moiety. 3 is OC(O)(C 1-12 alkylene) n When L is, it can be attached to Q via an ester or via an alkylene. 3 is C 1-12 alkylene. For example, L 3 are 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 alkylene. 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 first embodiment.

[0124] In a fifty-sixth aspect of the first embodiment, L3 (OC 1-12 alkylene) n or (C 1-12 alkylene-O) n For example, L 3 is —CH 2 O— or —OCH 2 —. 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 first embodiment.

[0125] In a fifty-seventh aspect of the first 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 first embodiment.

[0126] In a fifty-eighth aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] wherein each third repeat unit is a C alkylene and each bridging moiety is represented by Structural Formula (I). The remainder of the features and exemplary features of the fifty-eighth aspect are as described above for the first through fifty-seventh aspects of the first embodiment.

[0127] In a fifty-ninth aspect of the first embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] wherein each third repeat unit is a C alkylene, each bridging moiety is represented by Structural Formula (I), and the molar ratio of the first repeat unit, the second repeat unit, and the third repeat unit is 1:14:5.

[0128] In a sixtieth aspect of the first embodiment, the crosslinkable precursor ionomer comprises about 0.5 mol-% to about 15 mol-% of the first repeat unit. For example, the first ionomer comprises about 0.5 mol-% to about 15 mol-%, about 1 mol-% to about 14 mol-%, about 2 mol-% to about 12 mol-%, about 3 mol-% to about 10 mol-%, about 0.5 mol-% to about 10 mol-%, about 0.5 mol-% to about 7 mol-%, about 0.5 mol-% to about 10 mol-%, about 0.5 mol-% to about 10 mol-%, about 1 mol-% to about 10 mol-%, about 1 mol-% to about 7 mol-%, about 1 mol-% to about 5 mol-%, or about 2 mol-% to about 7 mol-% of the first repeat unit. For example, the first ionomer comprises about 0.5 mol-%, about 1 mol-%, about 2 mol-%, about 3 mol-%, about 4 mol-%, about 5 mol-%, about 6 mol-%, about 7 mol-%, about 8 mol-%, about 9 mol-%, about 10 mol-%, about 11 mol-%, about 12 mol-%, about 13 mol-%, about 14 mol-%, or about 15 mol-% of the first repeat unit. For example, the first ionomer comprises about 5 mol-% of the first repeat unit. The remainder of the features and exemplary features of the sixtieth aspect are as described above with respect to the first through fifty-ninth aspects of the first embodiment.

[0129] In a sixty-first aspect of the first embodiment, the crosslinkable precursor ionomer comprises about 20 mol-% to about 98 mol-% of the second repeating units. For example, the first ionomer comprises about 20 mol-% to about 95 mol-%, about 20 mol-% to about 90 mol-%, about 20 mol-% to about 80 mol-%, about 20 mol-% to about 70 mol-%, about 20 mol-% to about 60 mol-%, about 20 mol-% to about 50 mol-%, about 30 mol-% to about 80 mol-%, about 30 mol-% to about 70 mol-%, about 40 mol-% to about 90 mol-%, about 50 mol-% to about 90 mol-%, about 50 mol-% to about 80 mol-%, or about 60 mol-% to about 90 mol-% of the second repeating units. For example, the first ionomer comprises about 20 mol-%, about 25 mol-%, about 30 mol-%, about 35 mol-%, about 40 mol-%, about 45 mol-%, about 50 mol-%, about 55 mol-%, about 60 mol-%, about 65 mol-%, about 70 mol-%, about 75 mol-%, about 80 mol-%, about 85 mol-%, about 90 mol-%, or about 95 mol-% of the second repeat unit. For example, the first ionomer comprises about 28 mol-% of the second repeat unit. The remainder of the features and exemplary features of the sixty-first aspect are as described above with respect to the first through sixtieth aspects of the first embodiment.

[0130] In a sixty-second aspect of the first embodiment, the crosslinkable precursor ionomer comprises from about 0 mol-% to about 70 mol-% of the third repeat unit. For example, the first ionomer comprises from about 0 mol-% to about 60 mol-%, from about 0 mol-% to about 50 mol-%, from about 0 mol-% to about 40 mol-%, from about 0 mol-% to about 30 mol-%, from about 0 mol-% to about 20 mol-%, from about 0 mol-% to about 10 mol-%, from about 50 mol-% to about 70 mol-%, from about 5 mol-% to about 50 mol-%, from about 5 mol-% to about 40 mol-%, from about 10 mol-% to about 80 mol-%, from about 10 mol-% to about 50 mol-%, or from about 10 mol-% to about 40 mol-% of the third repeat unit. For example, the first ionomer comprises about 0 mol-%, about 5 mol-%, about 10 mol-%, about 15 mol-%, about 20 mol-%, about 25 mol-%, about 30 mol-%, about 35 mol-%, about 40 mol-%, about 45 mol-%, about 50 mol-%, about 55 mol-%, about 60 mol-%, about 65 mol-%, or about 90 mol-% third repeat units. For example, the first ionomer comprises about 67 mol-% third repeat units.

[0131] The remainder of the features and example features of the sixty-second aspect are as described above with respect to the first through sixty-first aspects of the first embodiment.

[0132] In a sixty-third aspect of the first embodiment, the moiety [ka] has the following structural formula: [ka] For example, the part [ka] has the following structural formula: [ka] The remainder of the features and example features of the sixty-third aspect are as described above with respect to the first through sixty-second aspects of the first embodiment.

[0133] In the sixty-fourth aspect of the first embodiment, the moiety [ka] has the following structural formula: [ka] where 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 first embodiment.

[0134] In a sixty-fifth aspect of the first embodiment, the bridging moiety has the following structural formula: [ka] For example, the bridging moiety may be represented by one of the following structural formulas: [ka] For example, the bridging moiety may be represented by the following structural formula: [ka] The remainder of the features and example features of the sixty-fifth aspect are as described above with respect to the first through sixty-fourth aspects of the first embodiment.

[0135] In a sixty-sixth aspect of the first embodiment, the number average molecular weight (MWn) of the crosslinkable precursor ionomer is from about 30,000 g / mol to about 500,000 g / mol. For example, the MWn of the crosslinkable precursor ionomer is from about 50,000 g / mol to about 360,000 g / mol, e.g., about 120,000 g / mol. The remainder of the features and exemplary features of the sixty-sixth aspect are as described above for the first through sixty-fifth aspects of the first embodiment.

[0136] In a sixty-seventh aspect of the first embodiment, the crosslinkable precursor ionomer comprises from about 10 mol-% to about 80 mol-% of the second repeat unit. For example, the crosslinkable precursor ionomer comprises from about 20 mol-% to about 60 mol-%, e.g., 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 through sixty-sixth aspects of the first embodiment.

[0137] In a sixty-eighth aspect of the first embodiment, R x is H. Alternatively, R x are F, Cl, Br, OH, NH2, NO2, CN and C 1-12 For example, R x are F, Cl, CN and C 1-6 For example, R x are F, Cl and C 1-3 The remainder of the features and exemplary features of the 68th aspect are as described above for the first through 67th aspects of the first embodiment. The remainder of the features and exemplary features of the 68th aspect are as described above for the first through 67th aspects of the first embodiment.

[0138] In a sixty-ninth aspect of the first embodiment, the crosslinkable moiety has the following structural formula: [ka] For example, the cross-linking moiety may be represented by one of the following structural formulas: [ka] For example, the crosslinkable moiety may be represented by structural formula (I): [ka] The remainder of the features and example features of the sixty-eighth aspect are as described above with respect to the first through sixty-fourth aspects of the first embodiment.

[0139] In a seventieth aspect of the first embodiment, the polymer film comprises about 20 wt.% to about 80 wt.% of the crosslinked product ionomer. For example, the polymer film comprises about 20 mol-% to about 70 mol-%, about 20 mol-% to about 60 mol-%, about 20 mol-% to about 50 mol-%, about 30 mol-% to about 80 mol-%, about 30 mol-% to about 70 mol-%, about 40 mol-% to about 80 mol-%, about 40 mol-% to about 70 mol-%, about 40 mol-% to about 60 mol-%, about 40 mol-% to about 50 mol-%, about 50 mol-% to about 80 mol-%, about 50 mol-% to about 80 mol-%, or about 50 mol-% to about 60 mol-% of the crosslinked product ionomer. For example, the first ionomer comprises about 20 mol-%, about 25 mol-%, about 30 mol-%, about 35 mol-%, about 40 mol-%, about 45 mol-%, about 50 mol-%, about 55 mol-%, about 60 mol-%, about 65 mol-%, about 70 mol-%, about 75 mol-%, or about 80 mol-% of the crosslinked product ionomer. For example, the polymer film comprises about 28 mol-% of the crosslinked product ionomer. The remainder of the features and exemplary features of the seventieth aspect are as described above for the first through sixty-ninth aspects of the first embodiment.

[0140] In a second aspect, the present disclosure relates to an electrode comprising a catalyst / ionomer layer, the catalyst / ionomer layer comprising a polymer film and a catalyst described herein with respect to the first aspect and various aspects thereof.

[0141] In a first aspect of the second embodiment, the catalyst is dispersed within the polymer film, e.g., particles of the catalyst are uniformly dispersed throughout the polymer film.

[0142] In a second aspect of the second embodiment, the catalyst is disposed on a polymer film.

[0143] In a third aspect of the second embodiment, the catalyst is: The catalyst may comprise: (i) a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof; and / or (ii) an oxide of a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof. For example, the catalyst may comprise a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof. For example, the catalyst may comprise an oxide of a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof. In some embodiments of the third aspect, the catalyst is supported on carbon. In some embodiments of the third aspect, the catalyst is selected from the group consisting of Pt, Pt supported on carbon (Pt / C), Pt and Ru supported on carbon (PtRu / C), Pd, Pd supported on carbon (Pd / C), Ir, IrO, IrRuO, RuO, Raney nickel (Al / Ni), Ni 0.5 Co 0.5 The catalyst may be selected from Fe2O4, NiCoO2, NiFe, NiFe2O4, NiO, NiMo, Ni and Mo supported on carbon (NiMo / C), FeCoNi, Fe2O3, LaCoO3, LiNiO2, LiCoO2, Co3O4, CoFe2O4, CoO, MnO, Mn2O3, MnO2 and Mn3O4 or combinations thereof. For example, the catalyst may be selected from Pt, Pt / C, Ir, IrO2, IrRuO, RuO2, Ni 0.5 Co 0.5 The catalyst is selected from Fe2O4 and NiCoO2 or a combination thereof. For example, the catalyst is Ni 0.5 Co 0.5 In some embodiments of the third aspect, the catalyst is Raney nickel (Al / Ni), Ni 0.5 Co 0.5The remainder of the features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the second embodiment.

[0144] In a fourth aspect of the second embodiment, the catalyst / ionomer layer comprises about 50-97 wt.% catalyst and about 3-50 wt.% polymer film. For example, the catalyst / ionomer layer can comprise about 50-95 wt.% catalyst and about 5-50 wt.% polymer film, about 60-95 wt.% catalyst and about 5-40 wt.% polymer film, about 70-95 wt.% catalyst and about 5-30 wt.% polymer film, about 60-90 wt.% catalyst and about 10-40 wt.% polymer film, about 65-90 wt.% catalyst and about 10-35 wt.% polymer film, or about 70-90 wt.% catalyst and about 10-30 wt.% polymer film. The fourth aspect includes a polymer film, about 75-90 wt.% catalyst and about 10-25 wt.% ionomer, about 65-95 wt.% catalyst and about 5-35 wt.% ionomer, about 70-95 wt.% catalyst and about 5-30 wt.% polymer film, about 75-95 wt.% catalyst and about 5-25 wt.% polymer film, about 65-85 wt.% catalyst and about 15-35 wt.% polymer film, and about 65-80 wt.% catalyst and about 20-35 wt.% polymer film. For example, the catalyst / ionomer layer includes about 80-90 wt.% catalyst and about 10-20 wt.% polymer film. The remainder of the features and exemplary features of the fourth aspect are as described above with respect to the first through third aspects of the second embodiment.

[0145] In a second aspect, the present disclosure relates to a composite material comprising a polymer film as described herein with respect to the first aspect and various aspects thereof or an electrode as described herein with respect to the second aspect and various aspects thereof and a support, wherein the polymer film or electrode is disposed on the support.

[0146] In a first aspect of the third embodiment, the substrate comprises a polyolefin, polyphenylene, polyester, polyamide, or polysulfone.

[0147] In a second aspect of the third embodiment, the substrate comprises a perfluorinated polyolefin. For example, the substrate comprises polytetrafluoroethylene (PTFE). The remainder of the features and exemplary features of the second aspect are as described above with respect to the first aspect of the third embodiment.

[0148] In a third aspect of the third embodiment, the support comprises polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride, or polyvinyl difluoroethylene. For example, the support comprises polyethylene. Alternatively or additionally, the support comprises polypropylene. Alternatively or additionally, the support comprises PTFE. The remainder of the features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the third embodiment.

[0149] As used herein, the term "polyolefin" refers to a polymer having the following structural formula: [ka] and R a is H, Cl or C 1-12 It is alkyl. R a When R is H, the polyolefin is polyethylene. a When R is methyl, the polyolefin is polypropylene. a When is Cl, the polyolefin is polyvinyl chloride.

[0150] As used herein, the term "polyester" refers to a polymer formed via a condensation reaction between a dicarboxylic acid and a diol, which contains multiple ester groups in the backbone. For example, polyesters can have the following structural formula: [ka] The compound may comprise a repeating unit represented by:

[0151] As used herein, the term "polyphenylene" refers to a compound having the following structural formula: [ka] The term "polymer" refers to a polymer comprising a plurality of repeating units represented by

[0152] As used herein, the term "polyamide" refers to a polymer formed via a condensation reaction between a dicarboxylic acid and a diamine, which contains multiple amide groups in the backbone. For example, a polyamide may have the following structural formula: [ka] The compound may comprise a repeating unit represented by one of:

[0153] As used herein, the term "polysulfone" refers to a polymer that contains multiple "aryl-S(O)-aryl" subunits in the backbone of the polymer. For example, polysulfones have the following structural formula: [ka] [ka] The compound may comprise a repeating unit represented by one of:

[0154] As used herein, the term "polyvinyldifluoroethylene" refers to a polymer having the following structural formula: [ka] The term "polymer" refers to a polymer comprising a plurality of repeating units represented by

[0155] As used herein, the term "polytetrafluoroethylene" refers to a polymer having the following structural formula: [ka] The term "polymer" refers to a polymer comprising a plurality of repeating units represented by

[0156] In a fourth aspect of the third embodiment, the support comprises a support ionomer. For example, the support ionomer is: a plurality of fourth repeat units, wherein each fourth repeat unit has the structural formula [ka] is the part represented by; a plurality of fifth repeat units, each fifth repeat unit having the structural formula [ka] is the portion represented by a plurality of bridging moieties, each bridging moiety having the following structural formula: [ka] wherein for each occurrence of the crosslinked moiety, the symbol [ka] L 2* represents the point of attachment to [ka] represents the point of attachment to the fourth or fifth repeat unit; moreover: [ka] has the following structural formula: [ka] is a part represented by one of; [ka] has the following structural formula: [ka] is a part represented by one of; W * is C 1-12 Alkyl or: [ka] wherein the moiety is represented by one of the structural formulas selected from the symbol [ka] L 3* represents the point of attachment to [ka] represents a double or 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; R 1* is H, C 1-12 Alkyl and C 6-12 aryl; Z 4* is a bond or C 6-12 is arylene, or Z 4* is CH and R 1* and Z 4* together with the C2 alkylene to which they are attached, form a C 5-12Forms a cycloalkyl or 5- to 12-membered heterocyclyl; Z 6* is -CHR 6 -, C 5-12 selected from cycloalkylene and 5- to 16-membered heterocyclylene; R 3* is H, C 1-12 Alkyl and C 6-12 aryl; Z 8* is a bond or C 6-12 arylene and CH, or Z 8* is CH and R 3* and Z 8* together with the C2 alkylene to which they are attached, form a C 5-12 Forms a cycloalkyl or 5- to 12-membered heterocyclyl; Z 9* is NR 10* or is 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; R14* 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 3* At least one atom of, if present, is L 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; R x* are H, F, Cl, Br, OH, NH2, NO2, CN, C 1-12 Alkyl, C 6-12 selected from aryl, 5- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl; L 2* is C 1-12 Alkylene, C 6-12 Arylene, C 6-12 Arylene-C 1-12 Alkylene, C1-12 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(O)(OC 1-12 alkylene) m* , OC(O)(C 1-12 alkylene) m* , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m* , (NH)C(OC 1-12 alkylene) m* , (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(O)(OC 1-12 alkylene) n* , OC(O)(C 1-12 alkylene) n* , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) n*, (NH)C(OC 1-12 alkylene) n* , (NH-C 1-12 alkylene) n* , (C 1-12 alkylene-NH n* and bond; m * is an integer between 1 and 6; n * is an integer between 1 and 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 - and C 1-12 carboxylates; V * W if and only if is a cationic moiety * C 1-12 Assuming it is an alkyl, where: 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, NO, oxo, CN, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, 5-12 membered heterocyclyl, 5-12 membered heteroaryl, NH(C 1-12alkyl), N(C 1-12 alkyl)2, OC(O)(C 1-12 alkyl), C(O)O(C 1-12 alkyl), S(O)2(C 1-12 alkyl), S(O)2(C 6-12 aryl), NHC(O)(C 1-12 alkyl) and C(O)NH(C 1-12 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.

[0157] In a fifth aspect of the third embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] is the part represented by W * is C 1-12 Alkyl or the following structural formula: [ka] and each bridging moiety is represented by the following structural formula: [ka] The remainder of the features and example features of the fifth aspect are as described above with respect to the first through fourth aspects of the third embodiment.

[0158] In a sixth aspect of the third embodiment, [ka] has the following structural formula: [ka] and [ka] has the following structural formula: [ka] is the part represented by W * is C 1-12 Alkyl or the following structural formula: [ka] and each bridging moiety is represented by the following structural formula: [ka] The remainder of the features and example features of the sixth aspect are as described above with respect to the first through fifth aspects of the third aspect, and are described with respect to the first through eighth aspects of the third aspect.

[0159] In a seventh aspect of the third embodiment, [ka] has the following structural formula: [ka] wherein each fifth repeat unit has the following structural formula: [ka] The remainder of the features and exemplary features of the seventh aspect are as described above with respect to the first through sixth aspects of the third embodiment.

[0160] In an eighth aspect of the third embodiment, [ka] has the following structural formula: [ka] wherein each fifth repeat unit has the following structural formula: [ka] where Me is methyl, iPr is isopropyl, and Cy is cyclohexyl. The remainder of the features and exemplary features of the eighth aspect are as described above for the first through seventh aspects of the third embodiment.

[0161] In a ninth aspect of the third embodiment, the support ionomer further has the following structural formula: [ka] wherein: 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 In some examples, at least one sixth repeat unit is [ka] The remainder of the features and exemplary features of the ninth aspect are as described above with respect to the first through eighth aspects of the third embodiment.

[0162] In a tenth aspect of the third embodiment, the support ionomer has the following structural formula: [ka] [ka] [ka] and During the ceremony: R, R 1a , R 2a , R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 11a , R 12a , R 13a , R 14a , R 15a , R 16a , R 17a , R 18a , R 19a , R 20a and R 21a are independently H, C 1-3 Alkyl, C 6-12 Aryl and C 5-12 cycloalkyl; L 4 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) p , (C 1-12 alkylene-O) p , C(O)(OC 1-12 alkylene) p , OC(O)(C 1-12 alkylene) p , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) p, (NH)C(OC 1-12 alkylene) p , (NH-C 1-12 alkylene) p , (C 1-12 alkylene-NH p and bond; p is an integer from 1 to 6; each moiety in brackets represents a repeat unit of the support ionomer. The remainder of the features and exemplary features of the tenth aspect are as described above for the first through ninth aspects of the third embodiment.

[0163] In a fourth aspect, the present disclosure relates to a membrane electrode assembly (MEA) comprising a polymer film as described herein with respect to the first aspect and various aspects thereof or an electrode as described herein with respect to the second aspect and various aspects thereof, and a composite material as described herein with respect to the third aspect and various aspects thereof.

[0164] In a fifth aspect, the present disclosure relates to a fuel cell comprising an MEA as described herein with respect to the fourth aspect and various aspects thereof, a fuel source, and an oxidant.

[0165] In a first aspect of the fifth embodiment, the fuel is humidified.

[0166] In a second aspect of the fifth embodiment, the fuel is selected from hydrogen, methanol, ethanol, and ammonia. The remainder of the features and example features of the second aspect are as described above with respect to the first aspect of the fifth embodiment.

[0167] In a third aspect of the fifth embodiment, the oxidant is oxygen. The remainder of the features and exemplary features of the third aspect are as described above with respect to the first and second aspects of the fifth embodiment.

[0168] In a sixth aspect, the present disclosure relates to an electrolyzer including an MEA as described herein with respect to the fourth aspect and various aspects thereof, and an electrolyte source.

[0169] In a first aspect of the sixth embodiment, the electrolyte source comprises water, a metal hydroxide, ethanol, methanol, ammonia, carbon dioxide, or a combination thereof.

[0170] In a seventh aspect, the present disclosure provides: a) providing a precursor film comprising a crosslinkable precursor ionomer; b) applying a mask to the film, thereby providing a partially protected film; c) exposing the partially protected film to ultraviolet radiation for a time sufficient to crosslink the crosslinkable ionomer, thereby producing a polymer film. The present invention relates to a method of making the polymer film described herein with respect to the first embodiment and various aspects thereof.

[0171] In a first aspect of the seventh embodiment, the crosslinkable moiety has the following structural formula: [ka] and W is represented by the following structural formula: [ka] The part represented by

[0172] In a second aspect of the seventh embodiment, the crosslinkable moiety has the following structural formula: [ka] and W is represented by the following structural formula: [ka] The remainder of the features and example features of the second aspect are as described above with respect to the first aspect of the seventh embodiment.

[0173] In a third aspect of the seventh embodiment, the crosslinkable moiety has the following structural formula: [ka] and W is represented by the following structural formula: [ka] The remainder of the features and example features of the third aspect are as described above with respect to the first and second aspects of the seventh embodiment.

[0174] In a fourth aspect of the seventh embodiment, the crosslinkable moiety has the following structural formula: [ka] and W is 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 seventh embodiment.

[0175] In a fifth aspect of the seventh embodiment, Q, V, W, L 2 , L 3 The crosslinkable moiety and crosslinking moiety are as described in any of the second to sixty-ninth aspects of the first embodiment. The remainder of the features and exemplary features of the fifth embodiment are as described above in relation to the first to fourth aspects of the seventh embodiment.

[0176] In a sixth aspect of the seventh embodiment, the precursor film does not include an external radical initiator. As used herein, the term "external radical initiator" refers to a radical initiator that is not covalently bonded to the ionomer. The remainder of the features and exemplary features of the tenth aspect are as described above with respect to the first through fifth aspects of the seventh embodiment. [Example]

[0177] Example The following examples describe methods of synthesis of ionomer and catalyst / ionomer layers of the present disclosure. The examples also provide methods of fabrication and characterization of MEAs of the present disclosure.

[0178] 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

[0179] 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 stream 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 (1 M), 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). 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 1 M 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).

[0180] Example 2. Synthesis of cyclohexyl-methyl Tetrakis® monomer (3). [ka] Tris(cyclohexyl(methyl)amino)(methylamino)phosphonium hexafluorophosphate (1) was synthesized as detailed in Treichel, M. et al. Macromolecules, 2020, 53, 8509.

[0181] In a 250 mL round-bottom flask, compound 1 (5.0 g, 9 mmol) was combined with chlorobenzene (16 mL). Potassium hydroxide solution (50 wt%, 10.0 g, 178 mmol) was charged, followed by COE-iodide 2 (3.5 g, 14 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 yield a crude oil. The oil was dissolved in a minimum amount of dichloromethane and precipitated into diethyl ether to produce Tetrakis® monomer 3 as an off-white solid (3.5 g).

[0182] Example 3. Synthesis of COE-imidazolium monomer (5). [ka] In a 50 mL round-bottom flask, tetramethylimidazole 4 (3.0 g, 24 mmol) was combined with acetonitrile (16 mL) and potassium carbonate (3.3 g, 24 mmol). COE-iodide 2 (9 g, 36 mmol) was charged to the flask, and the reaction was heated at 80 °C for 19 h. The reaction was cooled, filtered, and concentrated under vacuum to an oil. The recovered oil was dissolved in dichloromethane, extracted with water, and dried over magnesium sulfate. The dichloromethane layer was filtered and precipitated into diethyl ether to produce COE-imidazolium monomer 5 as a tan solid (5.7 g).

[0183] Example 4. Synthesis of Tetrakis®-BXL ionomer containing crosslinkable benzophenone moiety. Tetrakis®-BXL ionomer refers to an ionomer containing a first repeating unit containing a benzophenone moiety and a second repeating unit containing a Tetrakis® cation. Tetrakis® monomer (3) (0.63 g, 1.1 mmol), COE-benzophenone (0.07 g, 0.20 mmol), and cyclooctene (0.30 g, 2.7 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 (10 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 removed to produce 0.96 g of Tetrakis-BXL ionomer (28 mol % cationic units, 5 mol % crosslinkable units).

[0184] Example 5. Synthesis of imidazolium-BXL ionomer containing crosslinkable benzophenone moiety. Imidazolium-BXL ionomer refers to an ionomer containing a first repeating unit containing a benzophenone moiety and a second repeating unit containing an imidazolium cation. COE-imidazolium monomer (5) (0.86 g, 2.3 mmol), COE-benzophenone (0.05 g, 0.16 mmol), and cyclooctene (0.09 g, 0.82 mmol) were dissolved in dichloromethane under an inert atmosphere. Grubbs' Gen II catalyst (4 mg, 0.005 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 (5 mg, 0.007 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 removed to produce 0.82 g of imidazolium-BXL ionomer (70 mol % cationic units, 5 mol % crosslinkable units).

[0185] Example 6. Tetrakis®-BXL polymer membrane synthesis A 4:1 (w / w) stock solution was prepared by combining DI water (40 g) and 1-propanol (10 g). An aliquot (10.8 g) of the water:1-propanol solution was combined with 1.0 g of the Tetrakis® polymer formed in Example 4. The mixture was stirred and heated at 80° C. until dissolved to form an 8.5 wt. % polymer solution (11.8 g).

[0186] The entire polymer solution (11.8 g) was poured onto the surface of a tempered glass plate at 25°C. Using a drawdown bar (RDS, No. 250G), the polymer solution was spread onto the tempered glass to form a uniform polymer film. The film was dried at 25°C for 30 minutes and then transferred to an oven at 120°C for 1 hour. The film was cooled to room temperature and then immersed in deionized (DI) water to peel it off the glass. The released film was air-dried to produce a Tetrakis®-BXL membrane film (approximately 11 x 11 cm, 50 μm thick) with UV-crosslinkable groups.

[0187] Example 7. Formation of UV-patterned Tetrakis®-BXL film (70 mesh mask). An approximately 3x3 cm portion of the 50 μm Tetrakis®-BXL membrane film formed in Example 6 was covered with a 70-mesh stainless steel (SS) mask (0.0065-inch wire, 29.8% open area). The coated membrane was placed under a UV lamp (365 nm wavelength, 100 W) for 45 minutes and then cooled to room temperature. The 70-mesh mask was removed from the Tetrakis®-BXL membrane film and placed in DI water for 5 minutes. The Tetrakis®-BXL membrane film was removed from the DI water and allowed to air dry overnight, producing a film with a well-defined pattern similar to the 70-mesh mask (Figure 2).

[0188] Example 8. Formation of UV-patterned Tetrakis®-BXL film (500 mesh mask). A similar procedure to Example 7 was performed, except that a finer 500 mesh SS mask (0.0010 inch wire, 25% open area) was used to create a patterned Tetrakis®-BXL membrane. As in Example 5, this patterning matched the 500 mesh pattern and persisted after the membrane was swollen in DI water and dried overnight (FIG. 4).

[0189] Example 9. Heat-only treatment of Tetrakis®-BXL membranes A 1x1 cm square Tetrakis®-BXL membrane film formed in Example 6 was placed on a Teflon-coated hot plate. A 70 mesh SS mask (0.0065 inch wire, 29.8% open area) was placed on top of the Tetrakis®-BXL membrane film. A 20 g cylindrical weight was placed on top of the SS mask to provide greater contact between the mask and the Tetrakis®-BXL membrane surface. The coated membrane was heated at 50°C for 45 minutes and then cooled to room temperature. The heat-treated Tetrakis®-BXL membrane film was immersed in DI water for 5 minutes and then dried overnight. Unlike the UV-patterned Tetrakis®-BXL membranes formed in Examples 7 and 8, heat-only treatment failed to provide a persistent pattern after DI water exposure and drying. The surface of the heat-treated (no UV) Tetrakis®-BXL film was consistent with that of the cast film and showed no pattern corresponding to the 70 mesh mask (FIG. 3).

[0190] Example 10. Polarization curve electrochemical impedance spectroscopy measurements. Two 7.5x7.5cm squares of 60µm Tetrakis®-BXL membrane films were cut from the same stock material. A control membrane film (unpatterned) was formed by cross-linking under a lamp (365nm wavelength, 100W) for 45 minutes. A patterned membrane (70 mesh mask) was formed by placing a 70 mesh stainless steel (SS) mask (0.0065 inch wire, 29.8% open area, 2.5x2.5cm) in the center of the film and cross-linking under a UV lamp (365nm wavelength, 100W) for 45 minutes.

[0191] Two membrane films (patterned and unpatterned) were each mounted on a bipolar plate (BPP) with a serpentine flow field, a gas diffusion electrode, and a Teflon gasket (6.25 cm). 2 The films were tested under identical conditions in electrolyzer devices consisting of a 1000-µm active area, DM-type alkaline water electrolyzer cell, 30% cathode compression, and 10% anode compression. For each test, the device was first equilibrated at room temperature with electrolyte flow (12 mL / min) for 60 minutes, followed by preconditioning at 1.8 V for 15 minutes. An external heating pad with both internal and external temperature monitoring was used to heat the device from room temperature to 40°C. The films were tested at 40°C using a current-controlled polarization curve. Electrochemical impedance spectroscopy (EIS) analysis was performed at 1.7 V and 40°C prior to polarization. The frequency range for EIS was set from 100,000 to 0.1 Hz with 10 mV amplitude.

[0192] The data obtained are shown in Figures 5 and 6. The data show that, under the same operating conditions, an increase in current density was observed for devices using patterned films at both 1.8 and 2.1 V compared to unpatterned films. Electrolyzer testing with patterned films resulted in lower high frequency resistance (HFR), reflected in improved device performance relative to unpatterned films.

[0193] 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 can be made therein without departing from the scope of the invention encompassed by the appended claims.

[0194] The teachings of all patents, published applications and references cited herein are incorporated by reference in their entirety.

Claims

1. A polymeric film comprising a first plurality of volumes and a second plurality of volumes, Each volume of the first plurality of volumes comprises a crosslinkable precursor ionomer and each volume of the second plurality of volumes comprises a crosslinked product ionomer, each of the crosslinkable precursor ionomer and the crosslinked product ionomer comprising: a plurality of first repeating units, wherein each first repeating unit has the following structural formula: 【Chemistry 1】 and a plurality of second repeating units, wherein each first repeating unit has the following structural formula: 【Chemistry 2】 and moreover: The crosslinkable precursor ionomer has the following structural formula: 【Transformation 3】 and one or more crosslinkable moieties represented by any one of: The crosslinked product ionomer has the following structural formula: 【Chemistry 4】 and one or more bridging moieties represented by any one of where for each occurrence of a crosslinkable moiety, the symbol 【Transformation 5】 L 2 represents the point of attachment to the bridging moiety, and for each occurrence of the bridging moiety, the symbol 【Transformation 6】 L 2 represents the point of attachment to 【Transformation 7】 represents the point of attachment to the first repeat unit or the second repeat unit; moreover: 【Transformation 8】 has the following structural formula: 【Chemistry 9】 a portion represented by one of: 【Chemistry 10】 has the following structural formula: 【Chemistry 11】 a moiety represented by any one of: W is C 1-12 Alkyl or the following structural formula: 【Chemistry 12】 a portion represented by one of: In the formula, the symbol 【Chemistry 13】 L 3 represents the point of attachment to 【Chemistry 14】 represents 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; R 1 is H, C 1-12 Alkyl and C 6-12 aryl; Z 4 is a bond or C 6-12 is arylene, or Z 4 is CH and R 1 and Z 4 C where they combine 2 Together with alkylene, 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; R 3 is H, C 1-12 Alkyl and C 6-12 aryl; Z 8 is a bond or C 6-12 arylene and CH, or Z 8 is CH and R 3 and Z 8 C where they combine 2 Together with alkylene, C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; Z 9 is NR 10 or a bond; R 5 , R 6 and R y 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 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; R x and R z are independently H, F, Cl, Br, OH, and NH 2 , NO 2 , C.N., C. 1-12 Alkyl, C 6-12 selected from aryl, 5- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl; Ar 1 is C 6-12 aryl or 5- to 12-membered heterocyclyl; Ar 2 is C 6-12 arylene or 5- to 16-membered heterocyclylene; 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(O)(OC 1-12 alkylene) m ,OC(O)(C 1-12 alkylene) m , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m , (NH)C(OC 1-12 alkylene) m , (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(O)(OC 1-12 alkylene) n ,OC(O)(C 1-12 alkylene) n , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) n , (NH)C(OC 1-12 alkylene) n , (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 -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 - and C 1-12 carboxylates; W is C only if V is a cationic moiety 1-12 Assuming it is an alkyl, Where: Each C 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Cycloalkyl, C 6-12 Aryl, 5- to 12-membered heteroaryl, 5- to 12-membered heterocyclyl, C 1-12 Alkylene, C 6-12 Arylene, C 5-12 Cycloalkylene, 5- to 16-membered heterocyclylene, and 5- to 12-membered heteroarylene are independently optionally selected from F, Cl, Br, OH, NH 2 , NO 2 , Oxo, CN, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, 5- to 16-membered heterocyclyl, 5- to 12-membered heteroaryl, NH(C 1-12 alkyl), N(C 1-12 alkyl) 2 ,OC(O)(C 1-12 alkyl), C(O)O(C 1-12 alkyl), S(O) 2 (C 1-12 alkyl), S(O) 2 (C 6-12 aryl), NHC(O)(C 1-12 alkyl) and C(O)NH(C 1-12 A polymer film substituted with 1 to 6 substituents independently selected from the group consisting of alkyl.

2. The crosslinkable precursor ionomer and the crosslinked product ionomer each further comprise a plurality of third repeat units, each third repeat unit having the following structural formula: 【Chemistry 15】 and Z 10 and Z 11 However, each independently C 1-3 is an alkylene or a bond; R 20 But H, C 1-12 Alkyl or C 6-12 The polymer film of claim 1 , wherein the aryl is aryl.

3. The bridging moiety has the following structural formula: 【Chemistry 16】 3. The polymer film of claim 1, wherein the polymer film is represented by one of the following formulas:

4. The bridging moiety is represented by structural formula (I): 【Chemistry 17】 The polymer film of claim 3, wherein the polymer film is represented by:

5. The cross-linking moiety has the following structural formula: [Chemistry 18] 5. The polymer film according to claim 1, wherein the polymer film is represented by one of the following formulas:

6. The cross-linking moiety has the following structural formula: 【Chemistry 19】 6. The polymer film of claim 5, wherein the polymer film is represented by:

7. portion 【Chemistry 20】 has the following structural formula: 【Chemistry 21】 The polymer film according to any one of claims 1 to 6, which is represented by:

8. portion 【Chemistry 22】 has the following structural formula: 【Chemistry 23】 The polymer film according to any one of claims 1 to 7, which is represented by:

9. W has the following structural formula: 【Chemistry 24】 The polymer film according to any one of claims 1 to 8, which is a portion represented by:

10. W has the following structural formula: 【Chemistry 25】 The polymer film according to any one of claims 1 to 8, which is a portion represented by:

11. W has the following structural formula: 【Chemistry 26】 The polymer film according to any one of claims 1 to 8, which is a portion represented by:

12. portion 【Chemistry 27】 has the following structural formula: 【Chemistry 28】 and the part 【Chemistry 29】 has the following structural formula: 【Transformation 30】 is represented by W is C 1-12 Alkyl or the following structural formula: 【Chemistry 31】 and 10. The polymer film of claim 1, wherein each crosslinked moiety is represented by structural formula (I):

13. portion 【Chemistry 32】 has the following structural formula: 【Transformation 33】 and the part 【Transformation 34】 has the following structural formula: 【Chemistry 35】 and W is C 1-12 Alkyl or the following structural formula: 【Transformation 36】 and The polymer film of any one of claims 1 to 8, wherein each crosslinked moiety is represented by structural formula (I):

14. portion 【Chemistry 37】 has the following structural formula: 【Transformation 38】 and the part 【Chemistry 39】 has the following structural formula: 【Chemistry 40】 and W is C 1-12 Alkyl or the following structural formula: 【Chemistry 41】 and each crosslinked moiety is represented by structural formula (I):

15. portion 【Chemistry 42】 has the following structural formula: 【Chemistry 43】 The polymer film according to any one of claims 1 to 14, wherein the polymer film is represented by:

16. portion 【Chemistry 44】 has the following structural formula: 【Chemistry 45】 The polymer film according to any one of claims 1 to 15, which is represented by:

17. portion 【Chemistry 46】 has the following structural formula: 【Chemistry 47】 and the part 【Chemistry 48】 has the following structural formula: 【Chemistry 49】 is represented by Each third repeat unit is C 8 is alkylene, The polymer film of any one of claims 2 to 8, wherein each crosslinked moiety is represented by structural formula (I):

18. portion [Transformation 50] has the following structural formula: 【Chemistry 51】 and the part 【Chemistry 52】 has the following structural formula: 【Chemistry 53】 is represented by Each third repeat unit is C 8 is alkylene, The polymer film of any one of claims 2 to 8, wherein each crosslinked moiety is represented by structural formula (I):

19. portion 【Chemistry 54】 has the following structural formula: 【Transformation 55】 and the part 【Transformation 56】 has the following structural formula: 【Chemistry 57】 is represented by Each third repeat unit is C 8 is alkylene, The polymer film of any one of claims 2 to 8, wherein each crosslinked moiety is represented by structural formula (I):

20. R 13 , R 14 , R 15 and R 16 20. The polymer film of claim 19, wherein each is methyl.

21. Each first repeat unit has the following structural formula: 【Chemistry 58】 The polymer film according to any one of claims 1 to 20, wherein the polymer film is represented by:

22. portion 【Chemistry 59】 has the following structural formula: 【Transformation 60】 The polymer film according to any one of claims 1 to 8, which is represented by:

23. portion 【Chemistry 61】 has the following structural formula: 【Transformation 62】 and 23. The polymer film of claim 22, wherein Me is methyl, iPr is isopropyl, and Cy is cyclohexyl.

24. Each first repeat unit has the following structural formula: 【Transformation 63】 is represented by: portion 【Chemistry 64】 has the following structural formula: 【Transformation 65】 2. The polymer film of claim 1, wherein the polymer film is represented by any one of:

25. Each first repeat unit has the following structural formula: 【Chemical Formula 66】 is represented by: portion 【Transformation 67】 has the following structural formula: 【Transformation 68】 The polymer film according to any one of claims 1 to 8, which is represented by:

26. 26. The polymer film of any one of claims 1 to 25, wherein the crosslinkable precursor ionomer comprises from about 0.5 mol-% to about 15 mol-% of the first repeat unit.

27. 27. The polymer film of claim 26, wherein the crosslinkable precursor ionomer comprises about 5 mol-% of the first repeat unit.

28. 28. The polymer film of any one of claims 1 to 27, wherein the crosslinkable precursor ionomer comprises from about 20 mol-% to about 98 mol-% of the second repeat unit.

29. 30. The polymer film of claim 28, wherein the crosslinkable precursor ionomer comprises about 28 mol-% of the second repeat unit.

30. 30. The polymer film of any one of claims 2 to 29, wherein the crosslinkable precursor ionomer comprises from about 20 mol-% to about 50 mol-% or from about 50 mol-% to about 90 mol-% of the third repeat unit.

31. 31. The polymer film of any one of claims 1 to 30, wherein the crosslinkable precursor ionomer comprises from about 0 mol-% to about 70 mol-% of the third repeat unit.

32. 32. The polymer film of claim 31, wherein the crosslinkable precursor ionomer comprises about 67 mol-% of the third repeat unit.

33. 33. The polymer film of any one of claims 1 to 32, wherein the number average molecular weight of the crosslinkable precursor ionomer is from about 30,000 g / mol to about 500,000 g / mol.

34. 34. The polymeric film of claim 33, wherein the crosslinkable precursor ionomer has a number average molecular weight of about 50,000 g / mol to about 360,000 g / mol.

35. 35. The polymeric film of any one of claims 1 to 34, comprising about 20 wt.% to about 80 wt.% of the crosslinked product ionomer.

36. 36. An electrode comprising a catalyst / ionomer layer, the catalyst / ionomer layer comprising a polymer film according to any one of claims 1 to 35 and a catalyst.

37. 37. The electrode of claim 36, wherein the catalyst is dispersed within the polymer film.

38. 37. The electrode of claim 36, wherein the catalyst is disposed on a polymer film.

39. The catalyst is: (i) a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof; and / or (ii) an oxide of a metal selected from Ni, Fe, Ru, Ir, Co, Mn, Pt, Pd, Mo, and La, or a combination thereof; 39. The electrode of any one of claims 36 to 38, comprising:

40. The catalysts were Pt, Pt supported on carbon (Pt / C), Pt and Ru supported on carbon (PtRu / C), Pd, Pd supported on carbon (Pd / C), Ir, IrO 2 , IrRuO, RuO 2 , Raney Nickel (Al / Ni), Ni 0.5 Co 0.5 Fe 2 O 4 , NiCoO 2 , NiFe, NiFe 2 O 4 , NiO, NiMo, Ni and Mo supported on carbon (NiMo / C), FeCoNi, Fe 2 O 3 , LaCoO 3 , LiNiO 2 , LiCoO 2 , Co 3 O 4 , CoFe 2 O 4 , CoO, MnO, Mn 2 O 3 , MnO 2 or Mn 3 O 4 40. The electrode of any one of claims 36 to 39, comprising:

41. The catalyst is Ni 0.5 Co 0.5 Fe 2 O 4 or NiFe 2 O 4 41. The electrode of claim 40, comprising:

42. 42. The electrode of any one of claims 36-41, wherein the catalyst / ionomer layer comprises about 50-97 wt.% catalyst and about 3-50 wt.% polymer film.

43. 43. The electrode of claim 42, wherein the catalyst / ionomer layer comprises about 80-90 wt.% catalyst and about 10-20 wt.% polymer film.

44. A composite material comprising a polymer film according to any one of claims 1 to 35 or an electrode according to any one of claims 36 to 43 and a support, wherein the polymer film or the electrode is disposed on the support.

45. 45. The composite material of claim 44, wherein the substrate comprises a polyolefin, a polyphenylene, a polyester, a polyamide, or a polysulfone.

46. 45. The composite material of claim 44, wherein the substrate comprises a perfluorinated polyolefin.

47. 45. The composite material of claim 44, wherein the substrate comprises polyethylene, polypropylene, polytetrafluoroethylene, polyvinyl chloride, or polyvinyldifluoroethylene.

48. 45. The composite material of claim 44, wherein the support comprises a support ionomer.

49. The support ionomer is: a plurality of fourth repeat units, wherein each fourth repeat unit has the structural formula 【Transformation 69】 is the portion represented by a plurality of fifth repeat units, wherein each fifth repeat unit has the structural formula 【Transformation 70】 and A plurality of bridging moieties, wherein each bridging moiety has the following structural formula: 【Chemistry 71】 A composite material which is a crosslinked ionomer comprising: For each occurrence of a bridging moiety, the symbol 【Chemistry 72】 L 2* represents the point of attachment to 【Transformation 73】 represents the point of attachment to the fourth or fifth repeat unit; moreover: 【Chemistry 74】 has the following structural formula: 【Chemistry 75】 a portion represented by one of: 【Transformation 76】 has the following structural formula: 【Chemical 77】 a portion represented by one of: W * is C 1-12 Alkyl or: 【Transformation 78】 is a moiety represented by one of the structural formulas selected from In the formula, the symbol 【Transformation 79】 L 3* represents the point of attachment to 【Chemistry 80】 represents 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; R 1* is H, C 1-12 Alkyl and C 6-12 aryl; Z 4* is a bond or C 6-12 is arylene, or Z 4* is CH and R 1* and Z 4* C where they combine 2 Together with alkylene, 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; R 3* is H, C 1-12 Alkyl and C 6-12 aryl; Z 8* is a bond or C 6-12 arylene and CH, or Z 8* is CH and R 3* and Z 8* C where they combine 2 Together with alkylene, C 5-12 forming a cycloalkyl or a 5- to 12-membered heterocyclyl; 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 3* At least one atom of, if present, is L 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; R x* are H, F, Cl, Br, OH, and NH 2 , NO 2 , C.N., C. 1-12 Alkyl, C 6-12 selected from aryl, 5- to 12-membered heterocyclyl, and 5- to 12-membered heteroaryl; 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(O)(OC 1-12 alkylene) m* ,OC(O)(C 1-12 alkylene) m* , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) m* , (NH)C(OC 1-12 alkylene) m* , (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(O)(OC 1-12 alkylene) n* ,OC(O)(C 1-12 alkylene) n* , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) n* , (NH)C(OC 1-12 alkylene) n* , (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 - and C 1-12 carboxylates; V * W if and only if is a cationic moiety * C 1-12 Assuming it is an alkyl, Where: 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 , NO 2 , Oxo, CN, C 1-12 Alkyl, C 6-12 Aryl, C 1-12 Haloalkyl, C 1-12 Alkoxy, C 6-12 Aryl, C 6-12 Aryloxy, 5- to 12-membered heterocyclyl, 5- to 12-membered heteroaryl, NH(C 1-12 alkyl), N(C 1-12 alkyl) 2 ,OC(O)(C 1-12 alkyl), C(O)O(C 1-12 alkyl), S(O) 2 (C 1-12 alkyl), S(O) 2 (C 6-12 aryl), NHC(O)(C 1-12 alkyl) and C(O)NH(C 1-12 49. The composite material of claim 48, wherein said compound is substituted with 1 to 6 substituents independently selected from the group consisting of alkyl.

50. The support ionomer has the following structural formula: 【Chemistry 81-1】 【Chemistry 81-2】 【Chemistry 81-3】 【Chemistry 81-4】 and During the ceremony: R, R 1a , R 2a , R 3a , R 4a , R 5a , R 7a , R 8a , R 9a , R 11a , R 12a , R 13a , R 14a , R 15a , R 16a , R 17a , R 18a , R 19a , R 20a and R 21a However, H and C are independent of each other. 1-3 Alkyl, C 6-12 Aryl and C 5-12 cycloalkyl; L 4 But 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) p , (C 1-12 alkylene-O) p , C(O)(OC 1-12 alkylene) p ,OC(O)(C 1-12 alkylene) p , C 1-12 Alkylene-NH-C 1-12 Alkylene, C 1-12 Alkylene-N(C 1-12 Alkyl)-C 1-12 Alkylene, C(O)(NH-C 1-12 alkylene) p , (NH)C(OC 1-12 alkylene) p , (NH-C 1-12 alkylene) p , (C 1-12 alkylene-NH p and a bond; p is an integer from 1 to 6; 49. The composite material of claim 48, wherein each portion within a bracket represents a repeating unit of a support ionomer.

51. A membrane electrode assembly (MEA) comprising a polymer film according to any one of claims 1 to 35, an electrode according to any one of claims 36 to 43 or a composite material according to any one of claims 44 to 50.

52. 52. A fuel cell comprising the MEA of claim 51, a fuel source, and an oxidant.

53. 53. The fuel cell of claim 52, wherein the fuel is humidified.

54. 54. The fuel cell of claim 53 or 53, wherein the fuel is selected from hydrogen, methanol, ethanol and ammonia.

55. 55. The fuel cell according to any one of claims 52 to 54, wherein the oxidant is oxygen.

56. 52. An electrolyzer comprising the MEA of claim 51 and an electrolyte source.

57. 57. The electrolyzer of claim 56, wherein the electrolyte source comprises water, a metal hydroxide, ethanol, methanol, ammonia, carbon dioxide, or a combination thereof.

58. a) providing a precursor film comprising a crosslinkable precursor ionomer; b) applying a mask to the film, thereby providing a partially protected film; c) exposing the partially protected film to ultraviolet radiation for a time sufficient to crosslink the crosslinkable ionomer, thereby producing a polymer film.

36. A method of making the polymer film of any one of claims 1 to 35, comprising:

59. 59. The method of claim 58, wherein the precursor film does not include an external radical initiator.

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