Supported membranes by thermal and UV initiated bulk polymerization

Abstract

Embodiments of the present invention include compositions for forming anion exchange membranes, comprising one or more polycyclic olefinic monomers represented by formula (I) and one or more monomers represented by formula (III), optionally in combination with one or more monomers represented by formula (II). The compositions can be formed as ionomers on suitable membrane supports by bulk vinyl addition polymerization under thermal or photopolymerization conditions. The membrane supports thus formed are suitable anion exchange membranes for the fabrication of various electrochemical devices. More specifically, ionic membranes are formed on various supports containing various lightly crosslinked (less than 5 mol%) quaternary amino-functionalized norbornene monomer units. The membranes thus formed exhibit very high ionic conductivities of 280 mS / cm at 80°C. Electrochemical devices fabricated according to the present invention are useful in fuel cells, gas separators, and the like.

Description

[Technical Field]

[0001] Cross-reference to related applications This application claims the benefit of U.S. Provisional Application No. 63 / 433,981, filed December 20, 2022, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention provides a series of bulk-polymerizable compositions suitable for producing various supported membranes, such as anion-exchange membranes, for use in various electrochemical devices. More specifically, various compositions containing various bulk-polymerizable functionalized norbornene monomers can be used to form porous ionic polymer membranes supported on a variety of membrane supports. The present invention also provides methods for producing anion-exchange membranes supported on various supports for use in various electrochemical devices, such as fuel cells, gas separators, redox flow batteries, and hydrogen-generating water electrolyzers. [Background technology]

[0003] Energy conversion devices using solid polymer electrolytes, such as fuel cells, electrolyzers for producing hydrogen from water, and separation applications, are promising options due to their simplicity, high thermodynamic efficiency, and solid-state design. See, for example, B.C.H. Steele and A. Heinzel, Nature, 2001, 414, 345. These devices are also scalable and can be used in transportation, remote and distributed power, small- and large-scale facilities for electricity and hydrogen production, and the separation of specific chemicals such as carbon dioxide, oxygen, and hydrogen. More importantly, fuel cells are a clean energy conversion technology with the potential to reduce fossil fuel use. More specifically, fuel cells can be used in stationary power generation, portable electronics, and transportation. Furthermore, fuel cells are environmentally friendly, easily replenished, and can have high energy conversion efficiency. Summary of the Invention [Problem to be solved by the invention]

[0004] These energy conversion devices utilize various forms of membrane-like solid polymer electrolytes. Polymer electrolyte membranes fall into at least two broad categories: proton (or cation) exchange membranes (PEMs) and anion exchange membranes (AEMs). Advantages of AEMs or PEMs include the ease of fabricating electrodes with triple-phase boundaries, since there is no need to balance liquid / gas pressures as in liquid electrolyte devices. While there are several commercially available fuel cell vehicles and stationary power generators that use PEM membranes, they are economically unattractive due to the use of platinum-based electrocatalysts and perfluorinated polymer membranes.

[0005] High-pH AEMs offer enhanced oxygen kinetics compared to acidic conductive PEMs, allowing the use of base metal catalysts and reducing fuel crossover. However, early membranes suffered from low ionic conductivity, poor chemical stability at high pH, ​​and high water absorption. More recently, as reviewed by Arges, many researchers have achieved higher conductivities (e.g., 100 mS / cm at 80 °C) and chemical stability (1 M NaOH at 80 °C). See Arges et al., ACS Appl. Energy Mater. 2018, 1, 2991–3012. This significant progress indicates that certain structural moieties can be used to overcome the shortcomings of permeable AEMs.

[0006] Electrolyzers, which produce hydrogen from water, are an emerging enabling technology for the hydrogen economy. Electrochemical separation can enrich or deplete species such as carbon dioxide, oxygen, and hydrogen in gaseous or liquid feedstreams. AEM-based devices offer favorable environments for the kinetics of the Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER), enabling the use of non-platinum-based catalysts and potentially lowering the cost of ownership of these devices compared to PEM-based devices. See, e.g., DR Dekel, Journal of Power Sources, 2018, 375, 158-169.

[0007] Additionally, hydrocarbon-based anion- or hydroxide-ion-conducting polymers that are stable under alkaline conditions can be synthesized using a variety of low-cost monomers, compared to the perfluorinated polymers required for PEM-based electrochemical devices. See, for example, PA Kohl, et al., Energy & Environmental Science, 2014, 7, 3135-3191. Furthermore, perfluorinated polymers are expensive, hazardous to manufacture, and pose significant hazards due to the reactivity of the monomers.

[0008] However, the majority of currently commercially available AEMs do not meet the stringent performance requirements for an ideal AEM, particularly (i) high anion (e.g., hydroxide) conductivity, (ii) long-term alkaline stability at the operating temperatures of the AEM device, (iii) robust mechanical properties to withstand pressure differentials during use and avoid polymer creep under compression, and (iv) control of excess water uptake that would hinder ion transport within the electrodes and membranes. See, for example, S. Gottesfeld, et al., Journal of Power Sources, 2018, 375, 170-184.

[0009] The conductivity and long-term alkaline stability of AEMs depend on the structure of the polymer backbone, the location of the cations in the polymer structure, and the nature of the cations. Polymer backbones containing polysulfone, polyketone, and polyaryl ether moieties are susceptible to hydroxide attack and polymer backbone decomposition, making them unsuitable for AEM formation. See, for example, Zhang, X., et al., Polym. Chem. 2018, 9, 699-711 (AEMs as block-type polyarylene ether sulfone copolymers); Akiyama, R., et al., Macromolecules 2016, 49, 4480-4489 (aromatic copolymers from dimethylaminomethylated monomers).

[0010] Many known AEMs exceed 100 mS / cm (60-80°C), but some have been reported to approach 200 mS / cm at 80°C. See, for example, PA Kohl, et al., Journal of Materials Chemistry A, 2016, 4, 16233-16244; and L. Zhu, TJ Zimudzi, N Li, J. Pan, B. Lin and MA Hickner, Polymer Chemistry 2016, 7, 2464-2475.

[0011] The polymer backbone in block copolymer (BCP) structures has been shown to form efficient ion-conducting channels and exhibit high ionic conductivity. See, for example, PA Kohl, et al., J. Electrochem. Soc., 2020, 167, 054501. However, the synthesis of BCP structures is more difficult and expensive than the synthesis of random copolymers, especially on an industrial scale. Furthermore, these methods require first forming the polymer and then converting it into a film and / or membrane material, making them capital-intensive and difficult to scale up industrially. More importantly, conventional methods use polymers that must be dissolved in a solvent for application to the membrane support. The use of solvents not only raises environmental concerns but also makes industrial scale-up expensive.

[0012] Therefore, as mentioned above, there is still a need to develop AEMs that can be formed without generating industrial waste and that exhibit a better combination of properties, such as high electrical conductivity as well as mechanical properties and long-term stability.

[0013] Therefore, an object of the present invention is to provide a series of bulk-polymerizable compositions that contain various polycycloolefin-based monomers, can be bulk-polymerized by heat or suitable actinic radiation, and can form support films that function as AEMs exhibiting the above-mentioned improved properties.

[0014] Another object of the present invention is to provide a method for producing a support film by thermal and / or actinic radiation-initiated bulk polymerization as disclosed herein.

[0015] Further objects and scope of application of the present invention will be set forth in the detailed description below. [Means for solving the problem]

[0016] Surprisingly, it has been found that compositions comprising one or more monomers of formula (I) and one or more monomers of formula (III), optionally in combination with one or more monomers of formula (II), as described herein, can be bulk polymerized in the presence of a suitable palladium compound of formula (IV) or (V) under suitable heat and / or light irradiation conditions to form a suitable membrane on a substrate, which can be used as, for example, an anion exchange membrane. In particular, the anion exchange membrane of the present invention exhibits properties not previously attainable. More specifically, treatment of a membrane comprising a composition comprising one or more monomers of formula (I) and one or more monomers of formula (III) with a suitable tri(C1-C4)alkylamine results in a membrane containing quaternized ammonium ions in which some of the repeating units are crosslinked, thereby achieving a low water content. The formed membrane exhibits a high ionic conductivity of 200 mS / cm even at 80°C and is stable for a long period of time, such as 1000 hours or more, in a 1 M sodium hydroxide solution at 80°C, making it suitable as a chemically very stable anion exchange membrane (AEM). In some embodiments, the composition used to form the solid article comprising the membrane further comprises one or more monomers represented by formula (II) described herein. The membranes formed from the compositions of the present invention also have a very high ion exchange capacity (IEC), from about 3 meq / g to about 4 meq / g or more. Therefore, the membranes formed by the present invention are useful in a variety of applications, including electrochemical devices such as AEM-type fuel cells and electrolyzers. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 shows the graphical relationship of ionic conductivity at different temperatures for various films according to the present invention. [Figure 2A] FIG. 2A shows a photograph of a polypropylene substrate coated with a composition of the present invention (labeled "Before"). [Figure 2B] FIG. 2B shows a photograph (labeled "After") of a fully bulk polymerized and cured coated polypropylene substrate that can be used to fabricate an AEM according to the present invention. [Figure 3] FIG. 3 shows a SEM (Scanning Electron Micrograph) cross-section of one of the surfaces of an AEM according to the present invention. [Figure 4] FIG. 4 shows a SEM (Scanning Electron Micrograph) cross-section of the Z3030 support. [Figure 5] FIG. 5 shows a SEM (Scanning Electron Micrograph) cross-sectional photograph of the surface of another AEM according to the present invention. [Figure 6] FIG. 6 shows a SEM (Scanning Electron Micrograph) cross-section photograph of a commercially available Pention AEM. DETAILED DESCRIPTION OF THE INVENTION

[0018] Terms used in this specification have the following meanings:

[0019] As used herein, the articles "a," "an," and "the" are deemed to include plural referents unless expressly limited to one referent.

[0020] All numbers, values ​​and / or formulas expressing quantities of ingredients, reaction conditions, and the like described in this specification and the claims appended hereto reflect various uncertainties in the measurements performed to arrive at those numbers, values ​​and / or formulas, and therefore, unless otherwise indicated, are deemed to include the term "about."

[0021] When a range of values ​​is disclosed herein, the range is continuous, including both the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. When multiple ranges are provided to describe a feature or characteristic, such ranges are combinable. Thus, unless otherwise specified, all ranges disclosed herein should be understood to encompass any and all subranges subsumed therein. For example, a range stated as "1 to 10" should be considered to encompass any and all subranges between the minimum value of 1 and the maximum value of 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, and 5.5 to 10.

[0022] As used herein, "hydrocarbyl" refers to a group containing carbon and hydrogen atoms, including, for example, alkyl, cycloalkyl, aryl, aralkyl, alkaryl, and alkenyl. The term "halohydrocarbyl" refers to a hydrocarbyl group in which at least one hydrogen has been replaced with a halogen. The term perhalocarbyl refers to a hydrocarbyl group in which all hydrogens have been replaced with halogens.

[0023] As used herein, the term "alkyl" refers to a straight- or branched-chain saturated hydrocarbon substituent having the specified number of carbon atoms. Particular alkyl groups are methyl, ethyl, n-propyl, isopropyl, tert-butyl, and the like. Derived expressions such as "alkoxy," "thioalkyl," "alkoxyalkyl," "hydroxyalkyl," "alkylcarbonyl," "alkoxycarbonylalkyl," "alkoxycarbonyl," "diphenylalkyl," "phenylalkyl," "phenylcarboxyalkyl," and "phenoxyalkyl" should be construed accordingly.

[0024] As used herein, the term "cycloalkyl" includes all known cyclic groups. Representative examples of "cycloalkyl" include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Derived expressions such as "cycloalkoxy," "cycloalkylalkyl," "cycloalkylaryl," "cycloalkylcarbonyl," and the like, should be construed accordingly.

[0025] The term "perhaloalkyl" as used herein refers to an alkyl as defined above, wherein all hydrogen atoms of the alkyl group are replaced with halogen atoms selected from fluorine, chlorine, bromine, or iodine. Illustrative examples include, for example, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, pentafluoroethyl, pentachloroethyl, pentabromoethyl, pentaiodoethyl, as well as linear or branched heptafluoropropyl, heptachloropropyl, heptabromopropyl, nonafluorobutyl, nonachlorobutyl, undecafluoropentyl, undecachloropentyl, tridecafluorohexyl, tridecachlorohexyl, etc. The derived expression "perhaloalkoxy" should be interpreted accordingly. Furthermore, some of the alkyl groups described herein, such as "alkyl," may be partially fluorinated, i.e., only a portion of the hydrogen atoms of the alkyl group are replaced with fluorine atoms, and should be interpreted accordingly.

[0026] As used herein, the term "acyl" has the same meaning as "alkanoyl" and may also be structurally represented as "R-CO-," where R is an "alkyl" as defined herein having the specified number of carbon atoms.

[0027] Additionally, "alkylcarbonyl" has the same meaning as "acyl" as defined herein. Specifically, "(C1-C4) acyl" means formyl, acetyl, or ethanoyl, propanoyl, n-butanoyl, etc. Derived expressions such as "acyloxy" and "acyloxyalkyl" should be construed accordingly.

[0028] As used herein, the term "aryl" refers to substituted or unsubstituted phenyl or naphthyl. Specific examples of substituted phenyl or naphthyl include, for example, o-, p-, m-tolyl, 1,2-, 1,3-, 1,4-xylyl, 1-methylnaphthyl, 2-methylnaphthyl, and the like. "Substituted phenyl" or "substituted naphthyl" includes any of the possible substituents further defined herein or known in the art.

[0029] As used herein, the term "arylalkyl" refers to an aryl, as defined herein, further bonded to an alkyl, as defined herein. Representative examples include, for example, benzyl, phenylethyl, 2-phenylpropyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.

[0030] As used herein, the term "alkenyl" refers to an acyclic, linear or branched hydrocarbon chain having the specified number of carbon atoms and containing at least one carbon-carbon double bond, and includes ethenyl, straight-chain or branched propenyl, butenyl, pentenyl, hexenyl, and the like. Derived expressions "arylalkenyl" and 5- or 6-membered "heteroarylalkenyl" should be construed accordingly. Illustrative examples of such derived expressions include, for example, furan-2-ethenyl, phenylethenyl, 4-methoxyphenylethenyl, and the like.

[0031] As used herein, the term "heteroaryl" includes all known heteroatom-containing aromatic radicals. Representative 5-membered heteroaryl radicals include furanyl, thienyl, or thiophenyl, pyrrolyl, isopyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isothiazolyl, and the like. Representative 6-membered heteroaryl radicals include pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like. Representative examples of bicyclic heteroaryl radicals include, for example, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, cinnolyl, benzimidazolyl, indazolyl, pyridofuranyl, pyridothienyl, and the like.

[0032] "Halogen" or "halo" means chlorine or chloro, fluorine or fluoro, bromine or bromo, and iodine or iodo.

[0033] As used herein, the term "ionomer" refers to an anion-conducting solid polymer electrolyte as the ion-conducting medium between the electrodes and the ion-conducting medium within the electrodes as the conduit for ions between the electroactive material and the electrolyte.

[0034] The term "actinic radiation" or "photopolymerization conditions" refers to exposing the compositions of the present invention to suitable "electromagnetic radiation" which may be emitted from a laser, a digital processing (DLP) projector, a lamp, a light emitting diode (LED), a mercury arc lamp, fiber optics, or a liquid crystal display (LCD), or the like.

[0035] In its broadest sense, the term "substituted" is intended to include all permissible substituents of organic compounds. In some of the specific embodiments disclosed herein, the term "substituted" means substituted with one or more substituents independently selected from the group consisting of (C-C) alkyl, (C-C) alkenyl, (C-C) perfluoroalkyl, phenyl, hydroxy, -COH, ester, amide, (C-C) alkoxy, (C-C) thioalkyl, (C-C) perfluoroalkoxy, -NH, Cl, Br, I, F, -NH-lower alkyl, and -N(lower alkyl). However, any other suitable substituents known to those of ordinary skill in the art can also be used in these embodiments.

[0036] Here, the term "derived from" means that the polymer repeat units are bulk polymerized (formed) from polycyclic norbornene-type monomers, for example, according to formula (I), (II), and / or (III), where the resulting polymer is formed by two or three sequences of norbornene-type monomers, as shown below: [ka]

[0037] Such polymerizations are also commonly known as vinyl addition polymerizations, which are typically carried out in the presence of organometallic compounds such as organopalladium or organonickel compounds, as will be described in more detail below.

[0038] Thus, in accordance with the practice of the present invention, there is provided a composition comprising: a) one or more monomers represented by formula (I): [ka] where: Y and Y′ are the same or different and are each independently selected from the group consisting of —CH—, —CH—CH—, and —O—; m is an integer from 0 to 3, At least one of R1, R2, R3, and R4 is a group represented by the formula RX; However, R is (C1~C 10 ) alkylene, (C3-C8) cycloalkylene, (C1-C 10 ) alkylene (C3-C8) cycloalkylene, (C1-C 10 ) Alkylene (C3-C8) Cycloalkylene (C1-C 10 ) alkylene, (C1-C 10 ) Alkylene (C6-C 10 ) arylene, and (C1-C 10 ) Alkylene (C6-C 10 )Arylene (C1-C 10 ) alkylene, X is halogen, hydroxy, (C1-C 10 ) alkoxy, and (C6-C 12 ) aryloxy; The remaining R1, R2, R3, and R4 are each independently hydrogen, methyl, ethyl, straight-chain or branched (C3 to C 10 ) alkyl, (C3-C8) cycloalkyl, (C1-C 10 ) alkyl(C3-C8) cycloalkyl, and (C1-C 10 ) Alkyl (C6-C 10 ) selected from the group consisting of aryl; b) one or more monomers represented by formula (III): [ka] where: a is an integer of 0, 1, or 2; b is an integer from 1 to 10, K and K′ are the same or different and are each independently selected from the group consisting of —CH—, —CH—CH—, —O—, and —S—; c) A palladium catalyst selected from the group consisting of a thermally activated vinyl addition palladium catalyst and a photoactivated vinyl addition palladium catalyst.

[0039] In some embodiments, the compositions of the present invention include only one monomer represented by formula (I) and only one monomer represented by formula (III). In other embodiments, the compositions of the present invention include two different monomers represented by formula (I) and one monomer represented by formula (III).

[0040] Surprisingly, it has been found that the composition of the present invention, when containing one monomer of formula (I) above and one monomer of formula (III) above in appropriate amounts, can be bulk polymerized to form a suitably crosslinked polymer exhibiting the properties required for producing a membrane according to the present invention.

[0041] In another embodiment, the composition of the present invention further comprises one or more monomers represented by formula (II): [ka] where: Z and Z′ are the same or different and are each independently selected from the group consisting of —CH—, —CH—CH—, and —O—; n is an integer from 0 to 3, R8, R9, R 10 , and R 11 are the same or different and each independently represent hydrogen, methyl, ethyl, straight-chain or branched (C3 to C 10 ) alkyl, (C3-C8) cycloalkyl, (C1-C 10 ) alkyl(C3-C8) cycloalkyl, and (C1-C 10 ) Alkyl (C6-C 10 ) aryl.

[0042] The composition of the present invention can be used with any known vinyl addition polymerization catalyst, as long as it initiates bulk polymerization of the composition under thermal and / or photopolymerization conditions. In some embodiments, the palladium catalyst used is a thermally activated catalyst. Examples of such catalysts include palladium compounds represented by the following formula (IV): [ka] where: R 12 , R 13 and R 14 At least two of the tertiary carbons are identical and are attached to phosphorus through a tertiary carbon. 12 ) alkyl, 1-(C1-C5) alkyl (C3-C8) cycloalkyl, 1-(C5-C 12 ) Bicycloalkyl, 1-(C8-C 12 ) tricycloalkyl, (C6-C 10 ) aryl, and (C6-C 10 ) aryl(C1-C3) alkyl; Remaining R 12 , R 13 or R 14 is methyl, ethyl, straight or branched chain (C3-C 12 ) Alkyl, (C6-C 10 ) aryl, and (C6-C 10 ) aryl(C1-C3) alkyl; R 15 and R 16 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C3 to C 20 ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C3-C 20 ) perfluoroalkyl.

[0043] The thermally activated palladium catalyst also includes an activator compound represented by the following formula (VI): M d + Z - (VI) where: M d + is a cation selected from lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C1-C4) alkylammonium; Z - is B(C6F5)4 -, B[C6H3(CF3)2]4 - , B(C6H5)4 - , [Al(OC(CF3)2C6F5)4] - , BF4 - , PF6 - , AsF6 - , SbF6 - , (CF3SO2)2N - , (CF3SO2)3C - 、 and CF3SO3 - is a weakly coordinating anion selected from the group consisting of:

[0044] In another embodiment, the palladium catalyst used is a photoactivated palladium catalyst. Any known photoactivated palladium vinyl addition catalyst can be used in the composition of the present invention. Such catalysts include, for example, palladium compounds represented by formula (V): Pd(OCOR 17 )2(P(R 18 )3)2(V) R 17 are each independently methyl, ethyl, linear or branched (C3-C6) alkyl, and (C6-C 12 ) aryl; R 18 are each independently (C3 to C 10 ) cycloalkyl, and (C6-C 12 ) aryl.

[0045] The photoactivatable composition of the present invention further comprises a photoinitiator selected from the group consisting of: A compound represented by the following formula (VII): [ka] and A compound represented by the following formula (VIII): [ka] a photoinitiator selected from the group consisting of: where: d is an integer from 0 to 5, An - is Cl - , Br - , I - , BF4 - , tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1 -propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, PF6 - , SbF6 - , AsF6 - , n-C4F9SO3 - , CF3SO3 - 、 (CF3SO2)2N - , (CF3SO2)3C - , and p-CH3(C6H4)-SO3- selected from the group consisting of R 19 , R 20 , R 21 , R 22 , and R 23 are the same or different and each independently represent a halogen, methyl, ethyl, a linear or branched (C3 to C 20 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C6-C 10 )-aryloxy, (C6-C 10 ) thioaryl, (C1-C6) alkanoyl (C6-C 10 ) thioaryl, (C1-C6) alkoxy (C6-C 10 ) aroyl(C1-C6) alkyl, and (C6-C 10 ) Thioaryl-(C6-C 10 ) diallylsulfonium salts.

[0046] Thus, in some embodiments, the compositions of the present invention include: m, n, and a are each 0 or 1; b is an integer from 3 to 8; Y, Y', Z, Z', K, and K' are each CH2; At least one of R1, R2, R3, and R4 is a group represented by the formula RX; However, R is (CH2) c , (CH2) c Cyclohexylene, (CH2) cCyclohexylene (CH2) c , (CH2) c Phenylene, and (CH2) c Phenylene (CH2) c and c is an integer from 1 to 10. X is bromine; the remaining R1, R2, R3, and R4 are each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, and benzyl; R8, R9, R 10 , and R 11 are each independently selected from the group consisting of methyl, ethyl, straight or branched chain propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, and benzyl; R 12 , R 13 , and R 14 at least two of are the same and are selected from the group consisting of tert-butyl, 1-norbornyl, 1-bicyclo[2.2.2]octyl, and 1-adamantyl; Remaining R 12 , R 13 , and R 14 is selected from the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexyl; R 15 and R 16 are the same or different and are each independently selected from the group consisting of methyl, ethyl, n-propyl, and n-butyl; R 17 are each independently methyl or ethyl; R 18 are each independently selected from the group consisting of cyclopentyl, cyclohexyl, cycloheptyl, and phenyl.

[0047] In some embodiments, the compositions of the present invention comprise a compound of formula (VI): M d+ is lithium, Z - But B(C6F5)4 - , B[C6H3(CF3)2]4 - , B(C6H5)4 - , (CF3SO2)2N - , and (CF3SO2)3C - A compound selected from the group consisting of:

[0048] Generally, as described above, a combination of a compound represented by Formula (VI) and a palladium compound represented by Formula (IV) is used in a vinyl addition polymerization carried out under thermal conditions. For example, a composition comprising one or more monomers represented by Formula (I), one or more monomers represented by Formula (III), a palladium compound represented by Formula (IV), and a compound represented by Formula (VI), and optionally one or more monomers represented by Formula (II), can be heated to a suitable temperature and processed under bulk vinyl addition polymerization conditions to form a solid, including a film or membrane material, in accordance with the present invention. Temperature conditions are preferably in the range of about 80°C to 120°C. In some embodiments, the temperature used for bulk polymerization is preferably in the range of about 90°C to 110°C. However, when using the compositions of the present invention to form three-dimensional objects, any temperature conditions that affect bulk polymerization may be used.

[0049] Thus, the compositions of the present invention can include a thermally activated palladium compound and can also include other catalysts capable of promoting bulk vinyl addition polymerization of the compositions as described herein. All such catalyst components are encompassed by the present invention. For example, palladium compounds represented by formula (IVa) are effective as thermally activated vinyl addition polymerization catalysts. [ka] where: L is selected from the group consisting of acetonitrile, propionitrile, n-butyronitrile, tert-butyronitrile, benzonitrile (CHCN), 2,4,6-trimethylbenzonitrile, phenylacetonitrile (CHCHCN), pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2,6-di-t-butylpyridine, 2,4-di-t-butylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, pyrazine, 2,3,5,6-tetramethylpyrazine, diethyl ether, di-n-butyl ether, dibenzyl ether, tetrahydrofuran, tetrahydropyran, and benzophenone; Z a - is BF4 -, tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri-1 -propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, PF6 - , SbF6 - , AsF6 - , n-C4F9SO3 - , CF3SO3 - 、 p-CH3(C6H4)-SO3 - , (CF3SO2)2N - , and (CF3SO2)3C - is selected from the group consisting of: R 12 , R 13 , R 14 , and R 15 is as already described.

[0050] In other embodiments, the compositions of the present invention are bulk polymerized under photopolymerization conditions. That is, the compositions of the present invention undergo bulk vinyl addition polymerization upon exposure to suitable actinic radiation. To promote such bulk polymerization, the palladium compound used in the composition must be capable of inducing bulk polymerization conditions in response to suitable actinic radiation. Thus, in some embodiments, the palladium compound used in the composition is a palladium compound represented by formula (V) that exhibits activity to promote bulk vinyl addition polymerization upon exposure to suitable actinic radiation under certain conditions. Generally, such conditions can include one or more photoactivatable compounds, i.e., one or more photoinitiators and / or photosensitizers, as described above.

[0051] In some embodiments, the compositions of the present invention can include, together with the photoinitiator, a photosensitizer compound that further promotes the formation of an active catalyst upon exposure to suitable actinic radiation. For this purpose, if necessary, the compositions of the present invention can include a suitable photosensitizer compound that activates the photoinitiator and / or the palladium compound represented by Formula (V). Suitable photosensitizer compounds include anthracene, phenanthrene, chrysene, benzopyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene, thioxanthen-9-one, and mixtures thereof. In some exemplary embodiments, the suitable photosensitizer component is selected from the group consisting of compounds represented by Formula (IX) and compounds represented by Formula (X). [ka] where: R 24 , R 25 , and R 26 are the same or different and each independently represent hydrogen, halogen, hydroxy, NO2, NH2, methyl, ethyl, linear or branched (C3 to C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C14 ) tricycloalkyl, (C6-C 10 ) Aryl, (C6-C 10 )aryl(C1-C3)alkyl, (C1-C 12 )Alkoxy, (C3-C 12 ) cycloalkoxy, (C6-C 12 ) bicycloalkoxy, (C7-C 14 ) Tricycloalkoxy, (C6-C 10 )aryloxy(C1-C3)alkyl, (C6-C 10 )-aryloxy, C(O)(C1-C6) alkyl, COOH, C(O)O(C1-C6) alkyl, and SO2(C6-C 10 ) aryl; R 27 and R 28 are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C3 to C 12 ) Alkyl, (C3-C 12 ) cycloalkyl, (C6-C 12 ) Bicycloalkyl, (C7-C 14 ) tricycloalkyl, (C6-C 10 ) aryl, and (C6-C 10 )aryl(C1-C3)alkyl.

[0052] The compositions of the present invention may also employ palladium compounds or other catalyst systems that affect bulk vinyl addition polymerization under thermal and / or photopolymerization conditions. That is, when the compositions of the present invention are used to form films under thermal conditions, thermally activated catalysts that affect bulk vinyl addition polymerization are used. On the other hand, when the compositions of the present invention are used to form objects such as films under photopolymerization conditions, photoactivated catalysts that participate in bulk vinyl addition polymerization are used.

[0053] Various photoactivatable palladium compound-containing compositions effective as UV-activated catalysts for use in the compositions of the present invention have been reported in the literature. See, e.g., co-pending U.S. Patent Application No. 17 / 854,026. See also U.S. Patent Application Publication No. US20210198392A1 and U.S. Patent Application Publication No. US20210198393A1, all of which are incorporated herein by reference in their relevant portions.

[0054] Representative examples of monomers of formula (I) that may be used in the compositions of the present invention are, without any limitation, as follows: [ka] [ka]

[0055] Representative examples of the monomers of formula (II) used in the composition of the present invention are as follows, without any limitation: [ka] [ka] [ka] [ka]

[0056] Representative examples of the monomers represented by formula (III) used in the composition of the present invention are as follows, without any limitation: [ka]

[0057] Representative examples of palladium compounds of formula (IV) are selected, without limitation, from the group consisting of: [ka]

[0058] Representative examples of palladium compounds represented by formula (IV) are selected, without any limitation, from the group consisting of: Bis(tricyclopentylphosphine)palladium diacetate; Diacetatebis(tricyclohexylphosphine)palladium (Pd785); Diacetate bis(tricycloheptylphosphine)palladium; and Palladium diacetate bis(triphenylphosphine).

[0059] Such compounds represented by formula (IV) include, for example, without any limitation, those selected from the group consisting of: Lithium tetrafluoroborate; Lithium triflate; Lithium tris(trifluoromethylsulfonyl)methanide; Lithium tetrakis(pentafluorophenyl)borate (LiFABA); Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA).

[0060] Representative examples of compounds represented by formula (VII) are selected, without any limitation, from the group consisting of: [ka] [ka] [ka]

[0061] Representative examples of compounds represented by formula (VIII) are selected, without any limitation, from the group consisting of: [ka] [ka]

[0062] Representative examples of compounds represented by formula (IX) are selected, without any limitation, from the group consisting of: [ka] [ka] [ka]

[0063] Representative examples of compounds represented by formula (X) are selected, without any limitation, from the group consisting of: [ka]

[0064] Various examples of compositions of the present invention can be listed below without limitation. A mixture of 5-propylbicyclo[2.2.1]hept-2-ene, 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)propane, 5-(3-bromopropyl)bicyclo[2.2.1]hept-2-ene, diacetate(n-butyldi-1-adamantylphosphine)palladium(H2O) (Pd601), and lithium(diethyl ether)tetrakis(pentafluorophenyl)borate (LiFABA); A mixture of 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), (n-butyldi-1-adamantylphosphine)palladium(H2O) diacetate (Pd601), and lithium (diethyl ether)tetrakis(pentafluorophenyl)borate (LiFABA); A mixture of 5-pentylbicyclo[2.2.1]hept-2-ene, 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)propane, 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene, diacetate(n-butyldi-1-adamantylphosphine)palladium(H2O) (Pd601), and lithium (diethyl ether)tetrakis(pentafluorophenyl)borate (LiFABA); A mixture of 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), diacetate bis(tricyclohexylphosphine)palladium (Pd785), tolylcumyliodonium tetrakis(pentafluorophenyl)borate, and 2-isopropyl-9H-thioxanthen-9-one; A mixture of 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), (n-butyldi-1-adamantylphosphine)palladium(HO) diacetate (Pd601), and lithium (diethyl ether)tetrakis(pentafluorophenyl)borate (LiFABA); and A mixture of 1,8-di(bicyclo[2.2.1]hept-5-en-2-yl)octane (NBOctylNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), (n-butyldi-1-adamantylphosphine)palladium(HO) diacetate (Pd601), and lithium (diethyl ether)tetrakis(pentafluorophenyl)borate (LiFABA).

[0065] That is, it has been found that suitable combinations of the compositions of the present invention can be used to manufacture various electronic and / or electrochemical devices, as well as various other industrially useful products. In some embodiments, the compositions of the present invention comprise at least one monomer represented by Formula (I), at least one monomer represented by Formula (III), and a heat-activated bulk vinyl addition polymerization catalyst. When the compositions of the present invention are used for such purposes, any known heat-activated bulk vinyl addition polymerization catalyst can be used. For example, a heat-activated vinyl addition polymerization catalyst can be one in which a compound represented by Formula (IV) is used in combination with a compound represented by Formula (VI). The heat-activated compositions of the present invention undergo bulk vinyl addition polymerization at suitable temperatures to form three-dimensional objects, such as films.

[0066] Similarly, the compositions of the present invention can be prepared so that they can be irradiated with suitable actinic radiation to form three-dimensional objects. Thus, in some embodiments, the compositions of the present invention comprise at least one monomer represented by Formula (I), at least one monomer represented by Formula (III), and a photoactivatable vinyl addition polymerization catalyst. When the compositions of the present invention are used for such purposes, any known photoactivatable vinyl addition polymerization catalyst can be used. For example, the photoactivatable vinyl addition polymerization catalyst typically comprises a compound represented by Formula (V) in combination with a compound represented by Formula (VII) or a compound represented by Formula (VIII). When the photoactivatable compositions of the present invention are irradiated with suitable actinic radiation, they undergo bulk vinyl addition polymerization to form three-dimensional objects, such as films.

[0067] As described above, surprisingly, the composition of the present invention, which is a suitable combination of at least one compound represented by formula (I) and at least one compound represented by formula (III), a photoactivatable palladium catalyst represented by formula (V), and at least one compound represented by formula (VII) or formula (VIII), can initiate bulk vinyl addition polymerization and form a solid object such as a film when irradiated with suitable actinic rays (generally about 240 nm to 410 nm, typically medium- to long-wave ultraviolet light).

[0068] That is, surprisingly, the compositions of the present invention are stable at temperatures from below room temperature (below 20°C) to room temperature (about 20°C to 40°C), providing excellent storage stability. As used herein, "stable" means that the compositions of the present invention remain clear and do not increase in viscosity when stored at temperatures below room temperature, as defined herein, particularly when stored in a dark place, such as an amber or brown container without light. Thus, in some embodiments, the compositions of the present invention exhibit no change in viscosity even after storage at temperatures below 20°C for at least two days. Thus, in some embodiments, the compositions of the present invention exhibit a viscosity increase of 5% or less after storage at temperatures below 25°C for about one to six hours. That is, the viscosity of the compositions of the present invention remains essentially unchanged when stored at room temperature, but as shown by UV-DSC measurements, when the compositions of the present invention are exposed to suitable thermal conditions and / or suitable actinic radiation, bulk vinyl addition polymerization occurs immediately, with the heat of polymerization remaining unchanged even with extended storage periods.

[0069] In the compositions of the present invention, the amount of the palladium compound represented by formula (IV) for a thermally activated composition or the palladium compound represented by formula (V) for a photoactivated composition may be any amount as long as the desired effect is achieved. Generally, the total molar ratio of the monomer represented by formula (I), the monomer represented by formula (III), and the monomer represented by formula (II) to the compound represented by formula (IV) or the compound represented by formula (V) is 10,000:1 to 5,000:1 or less. In other embodiments, the molar ratio of the monomer to the palladium compound represented by formula (IV) or the palladium compound represented by formula (V) is 15,000:1 or 20,000:1 or more. Similarly, in the thermally activated compositions of the present invention, the amount of the compound represented by formula (VI) combined with the palladium compound represented by formula (IV) may be any amount as long as the desired effect is achieved. Generally, the molar ratio of the palladium compound represented by formula (IV) to the compound represented by formula (VI) is in the range of 1:2 to 1:5. In the photoactive composition of the present invention, the molar ratio of the palladium compound represented by formula (V): the photoacid generator represented by formula (VII) or formula (VIII): the photosensitizer represented by formula (IX) or formula (X) is in the range of 1:1:0.5 to 1:2:2, or 1:2:1, 1:4:1, 1:2:4, 1:1:2, 1:4:2, etc.

[0070] Furthermore, it has surprisingly been found that anion exchange membranes with desirable properties can be obtained only by employing a suitable combination of at least one monomer represented by Formula (I) and at least one monomer represented by Formula (III). In some embodiments, the amount of the monomer represented by Formula (III) is 0.5 mol% or less. In other embodiments, the amount of the monomer represented by Formula (III) used is 1.0 mol% or less, 1.5 mol% or less, 2.0 mol% or less, 2.5 mol% or less, or 3.0 mol% or less, depending on the desired use and application. Thus, the molar ratio of the monomer represented by Formula (I) to the monomer represented by Formula (III) can range from 99.5:0.5 to 95:5. In some embodiments, the molar ratio of the monomer represented by Formula (I) to the monomer represented by Formula (III) ranges from 99:1 to 96:4; in other embodiments, it ranges from 98.5:1.5, 98:2, 97.5:2.5, 97:3, 96:4, etc. In other words, by using as little as 0.5 mol % of the monomer represented by formula (III), it is possible to form a crosslinked film or support membrane that exhibits extremely excellent ionic conductivity, long-term stability, etc. It is also possible to use at least one or more monomers represented by formula (II) in the composition of the present invention in a desired amount depending on the desired end use. Thus, in some embodiments, either the thermally activated composition or the photoactivated composition described above can optionally contain at least one monomer represented by formula (II).

[0071] In yet another aspect of the present invention, a kit for forming an anion exchange membrane is provided. The kit includes a composition of the present invention. Thus, in some embodiments, the kit includes at least one monomer represented by Formula (I) described herein, at least one monomer represented by Formula (III) described herein, a palladium compound represented by Formula (IV) described herein, and a compound represented by Formula (VI) described herein. The kit may also include at least one monomer represented by Formula (II). In some embodiments, the kit of the present invention includes one monomer represented by Formula (I), one monomer represented by Formula (II), and one monomer represented by Formula (III) in combination with suitable amounts of the palladium compound represented by Formula (IV) and the compound represented by Formula (VI) described herein to achieve a desired result and / or objective.

[0072] In another embodiment, the kit of the present invention includes at least one monomer represented by Formula (I) described herein, at least one monomer represented by Formula (III), a palladium compound represented by Formula (V), a photoinitiator represented by Formula (VII) or a photoinitiator represented by Formula (VIII), and a photosensitizer represented by Formula (IX) or a photosensitizer represented by Formula (X). The kit may also include at least one monomer represented by Formula (II). In some embodiments, the kit of the present invention includes a combination of one monomer represented by Formula (I), one monomer represented by Formula (II), and one monomer represented by Formula (III) with a palladium compound represented by Formula (V), a photoinitiator represented by Formula (VII) or a photoinitiator represented by Formula (VIII), and a photosensitizer represented by Formula (IX) or a photosensitizer represented by Formula (X).

[0073] In another aspect of the kit embodiments of the present invention, the compositions undergo bulk polymerization only upon exposure to suitable temperature conditions, or suitable actinic radiation, or conditions necessary to form a polymer film for a sufficient length of time, meaning that the compositions of the present invention are poured onto a surface or substrate to be coated, such as a surface in the form of a transparent film, where the monomers polymerize to form a transparent polymer, and exposed to suitable heat conditions and / or actinic radiation, whereby the monomers polymerize to form a solid, transparent polymer.

[0074] In some embodiments, the kits of the present invention can include various exemplary compositions described above.

[0075] That is, it has been found that a suitable combination of at least one monomer represented by formula (I) and at least one monomer represented by formula (III), optionally with one or more monomers represented by formula (II), can provide a bulk vinyl addition polymeric material that can impart unique properties to membranes produced therefrom. Thus, in one embodiment of the present invention, a method for forming an anion exchange membrane according to the present invention comprises the steps of: A solution containing the following a) to c) is prepared: a) one or more monomers of formula (I) above; b) one or more monomers of formula (III) above; c) a combination of a palladium compound represented by the formula (IV) and a compound represented by the formula (VI), or a combination of a palladium compound represented by the formula (V) and a compound represented by the formula (IV) or (VIII) and a compound represented by the formula (IX) or (X); applying the solution to a membrane support; heating the coated membrane support at a temperature of about 80°C to about 120°C for about 30 minutes to about 90 minutes; treating the heated membrane support with a tri-(C1-C4) alkylamine at a temperature of about 20°C to about 50°C for about 1 day to about 5 days to form a quaternized anion exchange membrane; washing the quaternized anion exchange membrane with water; and Immersing the quaternized anion exchange membrane in an alkaline solution to form an anion exchange membrane.

[0076] As described above, compositions containing at least one monomer of formula (I) (wherein X is bromine) and at least one monomer of formula (III), optionally in combination with one or more monomers of formula (II), can be used to produce films of the present invention. To form thermally cured films, the compositions must contain a palladium compound of formula (IV) and a compound of formula (VI), or other known thermally activated catalysts as described herein. To form photocured films, the compositions of the present invention contain a palladium compound of formula (V), a photoinitiator of formula (VII) or a photoinitiator of formula (VIII), and a photosensitizer of formula (IX) or a photosensitizer of formula (X), or other known thermally activated catalysts as described herein, in combination as described herein.

[0077] First, as described above, all components are mixed in the desired amounts to form a homogeneous solution of the composition of the present invention. Generally, the monomer represented by formula (I) or the monomer represented by formula (III) does not require the use of an additional solvent; if the monomer represented by formula (II) is liquid, it may function as a solvent for the catalyst and other components. However, in some cases, the catalyst may be dissolved in a solvent and mixed with the monomer to be used. In such cases, any solvent capable of dissolving the catalyst system may be used. Examples of such solvents include alkanes, cycloalkanes, aromatic compounds such as toluene, ester solvents such as ethyl acetate, THF, dichloromethane, dichloroethane, etc., or any combination thereof.

[0078] The solution is then applied to a suitable membrane support using any known method. Typical application methods include dip coating, spraying, doctor blade coating, meniscus coating, inkjet coating, and slot coating. The mixture can also be cast onto a substrate to form a membrane film. Suitable substrates include any suitable substrate that can be used directly or can be used to form a membrane. Examples of membrane supports include, but are not limited to, polypropylene (PP), multilayer polypropylene / polyethylene (PP / PE), polytetrafluoroethylene (PTFE), and the like. Some membrane supports can also be laminated onto polymer films. For example, PTFE filters are commercially available in which PTFE polymer is laminated to a polypropylene membrane support. In such cases, the PTFE expands into a three-dimensional network structure, creating billions of microscopic pores. The surface can also be rendered hydrophobic and / or hydrophilic by appropriate chemical treatment. For example, a PTFE hydrophobic membrane support is commercially available as POREX VITEK® from Porex Filtration Group. Other commercially available PTFE membrane supports are available from Sterlitech and Millipore Sigma under the trade name OMNIPORE®. Similarly, various types of PP membrane supports are commercially available. For example, various porous monolayer PP membrane supports or triple-layer PP / PE membrane supports are available from Celgard.

[0079] The membrane support may be in a form suitable for use depending on the purpose, such as a sheet or a tube. Generally, the membrane support is in a sheet form, and as described above, can be laminated to another support layer or multilayer support.

[0080] As mentioned above, the compositions of the present invention are typically applied to a suitable membrane support by dip coating. That is, by dip-coating the compositions of the present invention onto a membrane support and laminating the coated membrane support with a suitable material, it has been found that the resulting membrane has improved properties. This manufacturing method forms a three-layer laminate of coated membrane supports. Any laminating layer suitable for laminating membrane supports can be used for this purpose. Examples of such laminating layers include, but are not limited to, polycarbonate film, polyethylene terephthalate (PET) film, and the like. Typically, the coated membrane support is sandwiched between two laminating layer sheets to form a laminated membrane sheet. However, various modifications known to those of ordinary skill in the art can be applied.

[0081] The excess coating on the membrane support is gently squeezed out by suitable means, such as a doctor blade. This step not only removes excess composition from the support but also ensures uniform application of the composition to the membrane support. The laminate membrane support is then heated to a suitable temperature to initiate bulk vinyl addition polymerization of the composition of the present invention. Any temperature conditions that result in such bulk vinyl addition polymerization can be used in the present invention. Typically, the laminate membrane sheet is heated to 80°C to 120°C for a sufficient time to ensure complete bulk vinyl addition polymerization of the composition. The time required for complete bulk vinyl addition polymerization of the composition can be as long as one hour or more, e.g., 30 minutes to 2 hours. The laminate layer is then peeled off from the membrane support. Note that the thickness of the membrane support before and after modification generally remains the same, but the weight of the membrane support always increases. This indicates that the composition fully penetrates the porous portions of the support, forming a uniformly coated, three-dimensional membrane support, enhancing membrane properties not achieved by conventional techniques. In some embodiments, the coverage of the porous surface of the support is at least 60% of the available surface area, and in other embodiments, at least 70% or 80% or more. The uniformity and extent of coverage of the support can be measured by any method known in the art. For example, scanning electron microscopy (SEM) can be used to measure both the coating thickness and uniformity.

[0082] If the composition applied to the membrane support includes a photoactivated palladium catalyst, the applied laminate is exposed to suitable actinic radiation as described herein to cause bulk polymerization of the composition.

[0083] It has been found that the bulk polymerized polymers formed from the compositions of the present invention are insoluble in any solvent. This indicates that the bulk polymerized polymers have a molecular weight high enough to be insoluble in most commonly used solvents that dissolve polymers formed by other processes, such as solvent-assisted vinyl addition polymerization processes. In other words, the coated membrane support has a number average molecular weight (M n In another embodiment, the bulk polymerized polymer on the membrane support has a coating of polymer with an M n exceeds 1,000,000. Generally, M n The larger the value, the more stable the polymer coated membrane support.

[0084] The fully cured membrane support is then treated to introduce pendent ionic groups, imparting anion exchange capability to the membrane, i.e., forming an anion exchange membrane. Typically, such pendent ionic groups include quaternary ammonium ions. To form a quaternary ammonium ion-containing membrane, the composition advantageously contains at least one monomer of formula (I) in which X is a halogen atom. When a membrane support is formed using another type of monomer of formula (I) described herein, it can be suitably treated to form pendent groups that are halogens.

[0085] The membrane support is then reacted with a suitable tri-(C1-C4) alkylamine to form a quaternary tri-(C1-C4) alkylammonium bromide. Examples of tri-(C1-C4) alkylamines include, but are not limited to, trimethylamine, dimethylethylamine, methyl-diethylamine, triethylamine, tri-n-propylamine, tributylamine, and the like. Various other tertiary amines substituted with suitable cycloalkyl or phenyl groups can also be used. Ammonia, primary amines, and secondary amines can also be used to form the quaternary ammonium pendent group. Examples of primary amines include, but are not limited to, methylamine, ethylamine, n-propylamine, n-butylamine, sec-butylamine, and tert-butylamine. Examples of secondary amines include, but are not limited to, dimethylamine, methylethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-sec-butylamine, and di-tert-butylamine. It should be noted that certain diamines disclosed below may also be used for quaternization along with some level of surface crosslinking, as detailed below.

[0086] Quaternization can be carried out by any known method. Generally, a coated, fully cured membrane support formed from a composition containing a monomer of Formula (I) where X is a halogen (e.g., bromine or chlorine) is reacted with a tri-(C1-C4) alkylamine under appropriate conditions in an aqueous medium for a sufficient time to form quaternary ammonium halide (bromide or chloride) pendent groups. The concentration of the tri-(C1-C4) alkylamine in water (or a suitable alcohol, e.g., methanol, ethanol, isopropanol, etc.) is not particularly critical and can range from about 50% to 90% by weight. In some cases, the reaction can be carried out in the tri-(C1-C4) alkylamine (or a suitable diamine) itself, i.e., under solvent-free conditions. Generally, such reactions are carried out at subambient, ambient, or elevated temperatures in the range of about 20°C to 50°C. The time required to complete the reaction can vary depending on the type of pendent group formed. For example, when X is bromine, it will react more quickly with amines to form the corresponding ammonium bromide, whereas when X is chlorine, the reaction time may be longer, as will be understood by those skilled in the art. Generally, the reaction time may range from a few hours to 2 days, or even 5 days or more.

[0087] The resulting quaternized anion exchange membrane is then thoroughly washed with water to remove any remaining halide ions in the AEM. Deionized water can be used for this purpose. Finally, the AEM is immersed in an alkaline solution to exchange all of the pendent halide ion groups in the support for hydroxide ions. This is generally performed at room temperature, but conditions lower or higher than room temperature may be used depending on the desired membrane support. The immersion is generally performed at room temperature (approximately 25°C) for 8 to 24 hours or more.

[0088] Therefore, the anion exchange membrane is made using the composition of the present invention, and the composition is first heated to about 80°C to 120°C to cause bulk polymerization, or is irradiated with suitable actinic rays to cause bulk polymerization, and then treated with tri-(C1-C4) alkylamine to form a quaternized anion exchange membrane.

[0089] In another aspect of the present invention, there is also provided an anion exchange membrane produced by the method of the present invention.

[0090] Surprisingly, by using appropriate amounts of at least one monomer represented by Formula (I) and at least one monomer represented by Formula (III), it is possible to prepare a membrane support having a polymer coating comprising the composition of the present invention, which exhibits properties not achieved by any prior art AEM. First, the composition of the present invention provides a polymer coating that is more stable than membranes reported in the literature. For example, the AEM formed by the present invention is more stable than the AEMs made from norbornene-based block copolymers described in WO 2019 / 191225 and WO 2022 / 026794. Second, the inclusion of a small amount of at least one monomer represented by Formula (III) in the composition of the present invention enables the formation of a crosslinked structure, which is advantageous in controlling the swelling of the membrane support. In other words, the swelling of the membrane support can be easily adjusted by simply adding 0.5 mol% to 3.0 mol% of the monomer represented by Formula (III). As is clear from the following discussion and examples presented herein, controlling the swelling rate is one of the important factors in determining the performance of the membrane, particularly as an AEM.

[0091] Third, the compositions of the present invention can be applied to various three-dimensional objects commonly used as membrane materials, such as tubular composites, hollow fibers, dense membrane flat sheets, or thin film composites.

[0092] As evidenced by the following specific examples, the use of an appropriate amount of a monomer represented by Formula (III) can impart previously unobtainable properties to the resulting AEM. For example, attempts to fabricate membranes without any monomer represented by Formula (III) result in membranes that are too weak (i.e., brittle) to be used as anion exchange membranes. Furthermore, membranes formed without the use of a monomer represented by Formula (III) typically have low ion exchange capacities (IEC), sometimes less than 3 meq / g. Surprisingly, membranes fabricated in accordance with the present invention have IECs of at least 3 meq / g, typically ranging from about 3 meq / g to 3.5 meq / g or greater. In some embodiments, membranes fabricated in accordance with the present invention have IECs of up to 4 meq / g or greater. Furthermore, membranes fabricated in accordance with the present invention have been found to exhibit very high hydroxide ion conductivities of greater than 210 mS / cm at 80°C. In some embodiments, membranes fabricated in accordance with the present invention exhibit hydroxide conductivities ranging from about 100 mS / cm to about 190 mS / cm at 80°C. Thus, in some embodiments, the membranes of the present invention have an ion exchange capacity (IEC) of at least 3 meq / g in an alkaline aqueous medium at temperatures between about 20°C and about 100°C for at least 2000 hours.

[0093] Another advantageous property of the membrane of the present invention is that it exhibits extremely high chemical stability, particularly in alkaline media. Thus, in some embodiments, the membrane of the present invention is stable in an alkaline aqueous medium at a temperature of about 20° C. to about 100° C. for at least 1,000 hours. In other embodiments, the membrane of the present invention is stable in an alkaline aqueous medium at about 80° C. for 2,000 hours.

[0094] Furthermore, by including an appropriate amount of the monomer represented by formula (III), it is possible to introduce sufficient crosslinks into the polymer backbone. Note that not all crosslinks occur intermolecularly (i.e., between two different polymer chains). Some crosslinks may occur intramolecularly (i.e., between two crosslinkable sites on the same polymer chain). Statistically, this is possible, and all of these combinations are included in the present invention. In other words, when the composition of the present invention is bulk polymerized, the monomer represented by formula (III) is crosslinked intramolecularly or intermolecularly.

[0095] In some other embodiments, bulk-polymerized polymers formed from the compositions of the present invention have an ionic conductivity of about 160 mS / cm to about 280 mS / cm at temperatures of 30°C to 100°C.

[0096] The bulk polymerized polymers formed from the compositions of the present invention have very high glass transition temperatures (T g ), i.e., in the range of about 250°C to about 400°C. Bulk polymerized polymers formed from the compositions of the present invention containing flexible alkyl side chains are expected to exhibit T g However, by properly selecting the monomers as described herein, T g The temperature can be increased to above 300°C. Thus, the membranes of the present invention provide additional thermal property advantages. However, pendent quaternary ammonium groups are known to decompose at temperatures below 250°C, but surprisingly, the membranes of the present invention containing such pendent quaternary ammonium groups do not decompose.

[0097] As mentioned above, finding an AEM that combines high conductivity with long alkaline stability to achieve low ohmic resistance loss has long been a challenge. Hydroxide conductivity is a function of ion mobility and ion exchange capacity (IEC). The IEC of an AEM is often limited to a moderate value to avoid high water absorption, which would lead to membrane swelling and reduce ion mobility. Mobility is improved by forming efficient ion-conducting channels (through the use of monomers represented by formula (III) as described above) and preventing excessive water absorption within the membrane. Therefore, membranes facing a dilemma exist between achieving high IEC and suffering the disadvantages caused by water attraction by ions. Crosslinking can suppress excess water uptake, but often results in reduced ion mobility. However, as described herein, this effect can be achieved by appropriately combining monomers of formulas (I) and (III) with monomers of formula (II).

[0098] Furthermore, AEM fuel cells operate at a high pH using two electrodes: a negative electrode (also called an anode) where hydrogen is oxidized, and a positive electrode (also called a cathode) where oxygen is reduced, as shown below. Positive electrode: 2H2O+O2+4e - →4OH - Negative electrode: 4OH - +2H2→4H2O+4e - Pure reaction: O2 + 2H2 → 2H2O (energy is also generated)

[0099] In fuel cells, oxygen or air is supplied to the cathode for the oxygen reduction reaction (ORR), and hydrogen gas is supplied to the anode for the hydrogen oxidation reaction (HOR). Electrons pass through an external circuit to produce useful electrical work. These reactions are known to be sensitive to the relative humidity of the fuel and oxidant streams, as well as to water absorption in the AEM and ionomer. Proper water management in the membrane and electrodes is essential to achieve high power density. In AEM fuel cells, some of the water electrochemically produced at the HOR electrode is consumed at the ORR cathode. Electroosmotic flow associated with anion transport transports water from the cathode to the anode. Water also diffuses back from the anode to the cathode. Insufficient water in the membrane and electrodes reduces ionic conductivity, and low water concentrations increase hydroxide reactivity and promote polymer decomposition. On the other hand, excessive water can easily flood the catalyst layer, hindering the efficient flow of ions through the electrodes and membrane. High internal stress and expansion within the AEM can cause mechanical degradation within the membrane.

[0100] Water electrolysis is a reaction that produces hydrogen gas and oxygen gas, and is the reverse reaction of a fuel cell, as shown below. Positive electrode: 4OH - →2H2O+O2+4e - Negative electrode: 4H2O+4e - →4OH - +2H2 Pure reaction: 2H2O → O2 + 2H2 (energy addition)

[0101] In this case, liquid water is supplied to the cathode where the oxygen evolution reaction (OER) occurs, and hydrogen gas is produced at the anode (HER). It is most desirable to restrict the flow of hydrogen produced at the HER and keep its pressure high. This eliminates the need to pressurize the hydrogen in subsequent processes. For this reason, the membrane must be able to withstand a large pressure difference.

[0102] Similar electrochemical reactions can be used to separate specific components from gas or liquid feed streams. ORR and OER reactions can be used to create oxygen pumps. Positive electrode: 4OH- →2H2O+O2+4e - Negative electrode: 2H2O+O2+4e - →4OH - Net reaction: O2 from the negative electrode is transported to the positive electrode.

[0103] A similar reaction can be used to separate carbon dioxide from an incoming gas stream, and is achieved by reacting hydroxide ions with carbon dioxide to form carbonate salts. Negative electrode: 2H2O+O2+4e - →4OH - 4OH - +2CO2 → 2CO3 2- +2H2O Positive electrode: 2CO3 2- →2CO2+O2+4e - Pure reaction: CO2 from the negative electrode is transferred to the positive electrode.

[0104] Similarly, HER and HOR can be used to transfer hydrogen from one gas stream to another. Positive electrode: 4OH - +2H2→4H2O+4e - Negative electrode: 4H2O+4e - →4OH - +2H2 Net reaction: H2 from the positive electrode side is transported to the negative electrode side.

[0105] In these reactions, anions are transported between the electrodes. To achieve high conductivity, the number of ions (i.e., high ion exchange capacity (IEC)) cannot be increased alone due to the penalty of excessive water absorption, and therefore, efficient ion channels are required in AEMs. Surprisingly, it has been found that by appropriately combining the compositions of the present invention, in conjunction with the fabrication of suitable membranes as described herein, ion channels with high mobility can be formed. Membranes formed according to the present invention not only have high IEC, but also retain this property even after long-term operating conditions lasting from several months to a year or more.

[0106] The nature of the polymer backbone and the type and location of hydrophilic groups in the polymer are also important for the long-term stability of AEMs at high pH. Experiments have shown that polar moieties, such as ether, ketone, and ester bonds in the polymer body and side chains, are susceptible to nucleophilic attack, resulting in backbone degradation. Placing cationic pendent groups at the end of pendant alkyl tethers has also proven to be an effective strategy for mitigating polymer degradation. Quaternary ammonium pendent groups, particularly trimethylammonium cations, have been shown to offer an excellent balance of conductivity and stability, although other conductive groups are also useful.

[0107] In addition to the membrane itself, an ionically conducting polymer is required to form the electrodes. The electrodes are fabricated in three dimensions to provide a very high surface area. In a typical process, an electroactive catalyst is mixed with a portion of an anionically conducting polymer (or a composition of the present invention with the appropriate combination of monomers that form an anionically conducting polymer upon bulk polymerization) to form an ink. The ink is then sprayed onto a gas diffusion layer (GDL), which also serves as a current collector. The two electrodes, which may be of the same composition or contain different catalysts, are then pressed against a solid polymer membrane to create a membrane electrode assembly (MEA). The MEA is placed between solid blocks that distribute the gas or liquid required for the reaction.

[0108] One of the remaining challenges in designing stable and highly conductive AEMs is water absorption. Excessive water absorption can lead to high IEC, flooding the channels and swelling the membrane. This leads to mechanical deformation and softening of the membrane. Materials with high IEC tend to absorb large amounts of water. A certain amount of water is required for the formation of an ion-solvent shell and the dilution of hydroxide salts within the membrane. The absorbed water must be sufficient for ion solvation, but excessive free water is undesirable. Therefore, the amount of water can be divided into bound water (for solvent shell formation) and free water. Therefore, the IEC must be selected to balance the amount of free and bound water in the membrane, maximizing ion mobility (i.e., conductivity) while maintaining the mechanical properties of the AEM.

[0109] For example, Chen et al. (RSC Adv. 2015, 5, 63215-63225) reported that an AEM formed from vinyl-added poly(norbornene) exhibited very low conductivity (4 mS / cm at 80 °C) and a slight decrease in conductivity after immersion in 6 M NaOH at room temperature. This AEM also exhibited low ion exchange capacity. Furthermore, this polymer was not a block polymer, but contained ether linkages in the pendent alkyl tethers, which are known to be susceptible to hydroxide attack.

[0110] Another challenge is the aforementioned swelling of membranes during extended use in liquid media, such as aqueous media. Surprisingly, it has been discovered that a controlled level of surface cross-linking mitigates undesired swelling of the membrane and maintains ionic conductivity over extended periods of time. Accordingly, in some embodiments of the present invention, membranes prepared according to the present invention are exposed to a suitable diamine for a sufficient period of time prior to quaternization. Any diamine that provides surface cross-linking can be used for this purpose. Non-limiting examples of these diamines include ethylenediamine, N,N'-dimethyl-1,2-ethanediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, N,N'-dimethyl-1,5-pentanediamine, N,N'-dimethyl-1,6-hexanediamine, and the like. Other known diamines that react similarly can also be used for this purpose. Generally, such surface cross-linking can be achieved by immersing or dipping the membrane in one of the above diamines. Such immersion can include an additional solvent, such as an alcohol, such as isopropanol. For example, the membrane is immersed in a 50% by weight:50% by weight mixture of isopropanol and N,N'-dimethyl-1,6-hexanediamine for a sufficient period of time. For this purpose, periods ranging from about 1 minute to about 4 hours or more can be used. However, it has been determined that immersing the membrane for more than a day may not provide beneficial effects. Thus, in some embodiments, the membrane is immersed in the appropriate diamine solution for a period of about 10 minutes to 3 hours, 30 minutes to 150 minutes, 1 hour to 2 hours, etc.

[0111] That is, it has been found that the degree of membrane swelling can be controlled by forming sufficient crosslinks on the membrane surface. Thus, in some embodiments, a sufficient level of crosslinking on the membrane surface reduces membrane swelling by up to 40%. In other embodiments, sufficient surface crosslinking can reduce membrane swelling by up to 30%, 20%, or 10%. It should be noted that even with such surface crosslinking, the ionic conductivity of the membrane is substantially maintained. For example, membranes that have been surface crosslinked can maintain ionic conductivity up to 80% of their original capacity with minimal swelling over a few days, ranging from one week to ten weeks, fifteen weeks, or even longer.

[0112] Therefore, the membrane of the present invention is useful in various applications, including electrochemical devices. Accordingly, in one aspect of the present invention, there is provided an electrochemical device comprising the membrane of the present invention. In another embodiment, there is also provided a fuel cell comprising the membrane of the present invention.

[0113] The present invention is further described by the following examples, which are provided for illustrative purposes and are not intended to limit the scope of the invention.

[0114] [(General) Example] The following abbreviations have been used herein to describe some of the compounds, devices, and / or methods employed to describe certain embodiments of the present invention. BuNB: 5-butylbicyclo[2.2.1]hept-2-ene, NBBuBr-5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene, NBBuNB-1, 4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane, NBOctylNB: 1,8-di(bicyclo[2.2.1]hept-5-en-2-yl)octane, Pd601: diacetate(n-butyldi-1-adamantylphosphine)palladium(H2O), Pd785: palladium diacetate bis(tricyclohexylphosphine), Pd1206: (acetonitrile)bis(triisopropylphosphine)palladium(acetate)tetrakis-(penta-fluoro-phenyl)borate, LiFABA: lithium tetrakis(pentafluorophenyl)borate (2.5Et2O), DANFABA: dimethylanilinium tetrakis(pentafluorophenyl)borate; Bluesil PI 2074: Tolylcumyl iodonium tetrakispentafluorophenylborate, commercially available under the trade name Bluesil PI 2074 THF: tetrahydrofuran; EtOAc: ethyl acetate, MeOH: methanol, IPA: Isopropyl alcohol, PET film: polyethylene terephthalate film, PTFE: Polytetrafluoroethylene, phr: parts per 100 parts of monomer HPLC: high performance liquid chromatography; DI water: deionized water

[0115] [Examples 1 to 9] AEM film formed by bulk polymerization of the composition of the present invention In Examples 1-9, various films were formed from each composition of the present invention as follows: In separate amber glass bottles, LiFABA (3 molar parts) and Pd601 (1 molar part) were dissolved in 2.5 phr of EtOAc to obtain clear solutions. Similarly, various mixtures of three monomers, BuNB, NBBuNB, and NBBuBr (total of 10,000 molar parts), were prepared, as summarized in Table 1. In each of Examples 1-9, the monomer mixture was then added to the catalyst solution. Each composition in Examples 1-9 was then filtered through a 0.45 μm PTFE syringe filter, doctor-bladed onto a glass plate, and cured on a preheated hotplate at 100°C for 10 minutes to form a film. These films were colorless, flexible, and self-supporting, with thicknesses ranging from approximately 25 μm to 40 μm. Each film thus formed was then vacuum-dried at 100°C for 1 hour.

[0116] The films were quaternized by immersion in a 50 wt% aqueous trimethylamine solution at room temperature for 3 days. The quaternized membranes with bromide counterions were thoroughly washed with DI water. The films were then immersed in a 1 M NaOH solution for 24 hours to exchange the bromide ions for hydroxide ions. The ionic resistance of the films was measured using a four-terminal in-plane probe and a Hewlett-Packard Precision LCR meter (20 Hz–1 MHz). All samples were tested in HPLC-grade water under a nitrogen atmosphere. The in-plane ionic conductivity was calculated using the following equation: σ=L / (WTR) where σ is the ionic conductivity, L is the length between the sensing electrodes, W and T are the width and thickness of the film, and R is the measured resistance.

[0117] Figure 1 shows the ionic conductivity in DI water at various temperatures for bulk-polymerized and quaternized films obtained from each of the compositions of Examples 1-9. These results suggest that the use of a small amount (0.5 mol%) of the monomer represented by formula (III) and a relatively large amount of the monomer represented by formula (I) generally improves the conductivity of the film. That is, the films formed from the compositions of Examples 4 and 9, which contain 0.5 mol% of the monomer represented by formula (III) and 97 mol% of the monomer represented by formula (I), exhibit high conductivity at all temperatures. On the other hand, the film formed from the composition of Example 5, which contains 3 mol% of the monomer represented by formula (III) and 77.5 mol% of the monomer represented by formula (I), exhibits low conductivity at all temperatures.

[0118] [Table 1]

[0119] [Example 10] Storage stability of the composition of the present invention The composition of Example 6 was used in the storage stability test. A portion of the composition of Example 6 was kept at 23°C and monitored for viscosity change over a two-day period. The viscosity of the composition was measured at the specified time intervals, as summarized in Table 2. No significant viscosity change occurred during the initial two-hour measurement period. After two days of storage, the viscosity gradually increased. However, the reactivity of the composition remained nearly constant throughout the test period, indicating that the reactivity of the composition of the present invention remains intact even after storage for one to two days.

[0120] [Table 2]

[0121] [Examples 11 to 14] AEM Manufacturing Supported AEMs were fabricated by dip-coating a porous membrane support. The properties of the supports used in these examples are summarized in Table 3. In Examples 11-14, each porous membrane support was dip-coated using the composition of Example 6. The dip-coated support was then sandwiched between two PET films. After squeezing out excess liquid, the film stack was cured in an oven at 100°C for 1 hour. The PET films were then peeled off, and the resulting composite membrane was vacuum-dried at 100°C for 1 hour. Figures 2A and 2B show photographs of the support material of Example 12, before and after coating and curing, respectively. Figure 3 shows an SEM cross-section of the membrane obtained in Example 12 after curing. A Tescan LYRA-3 Model XMU FIB-FESEM was used for SEM imaging. After curing, the membrane thickness remained unchanged, but the membrane weight increased in proportion to the open pore volume of the support material. This fabrication technique allows for the formation of a continuous polymer phase within the support material, achieving optimal ion transport in an out-of-plane configuration.

[0122] [Table 3]

[0123] The composite membranes obtained in Examples 11-14 were quaternized according to the procedures set forth in Examples 1-9 to obtain various AEMs formed in accordance with the present invention. The AEMs thus formed were then subjected to measurement of ionic conductivity at various temperatures following the same procedures as those set forth in Examples 1-9. The results are summarized in Table 4. For comparison, the ionic conductivity measured for the membrane obtained in Example 6 is also shown in Table 4. As is evident from the data in Table 4, the ionic conductivities of the AEMs prepared in accordance with the present invention are substantially equivalent to the ionic conductivities of the films prepared in accordance with the present invention shown in Examples 1-9. In particular, Figure 1 illustrates the ionic conductivities at various temperatures of various films prepared from the compositions of Examples 1-9.

[0124] [Table 4]

[0125] Ion transport in electrolyzers occurs across the membrane, i.e., in-plane conductivity. In this case, measuring the inter-plane conductivity is preferred for membrane characterization. However, measuring the in-plane conductivity requires a different experimental setup. Based on the AEM composite structures of Examples 11-14, the inter-plane and in-plane conductivities are expected to be comparable because the continuous polymer phase is uniform in all directions.

[0126] [Example 15] In Example 15, the procedures of Examples 1-9 were essentially repeated, except that only NBBuBr and NBOctylNB (99:1 molar ratio) were used to form the composition of the present invention. A supported AEM was then formed on a polypropylene microporous monolayer membrane material (Z3030) substantially following the procedure of Example 11. The ionic conductivity of the supported AEM thus formed was measured at various temperatures, and the results are summarized in Table 5. As is evident from the data in Table 5, the AEM made in accordance with the present invention exhibits excellent ionic conductivity.

[0127] [Table 5]

[0128] [Example 16] AEM formation by UV-initiated bulk polymerization In a glass bottle, the monomer mixture from Example 6 (BuNB / NBBuNB / NBBuBr: 24 / 1 / 75 molar ratio, 10,000 molar parts) was used to dissolve Pd785 (1 molar part), Bluesil PI 2074 (2 molar parts), and ITX (2 molar parts) to prepare a clear solution. Membranes were fabricated substantially according to the procedure of Example 11, except that the coating and lamination were performed using the composition prepared above under a nitrogen inert atmosphere. The same polypropylene microporous monolayer membrane support (Z3030) used in Example 11 was also used in Example 16. After squeezing out excess liquid, the film stack was first exposed to UV light (395 nm, 500 mW / cm). 2 The membrane was irradiated with light for 4 seconds and then placed in an oven at 100°C for 1 hour. The PET film was then peeled off, and the resulting composite membrane was vacuum dried at 100°C for 1 hour. The cured membrane support was quaternized by contacting it with trimethylamine to form an AEM composite membrane. The ionic conductivity of the resulting AEM was measured according to the procedures described in Examples 1 to 9. The results are summarized in Table 6. Even after storage at room temperature for 10 days, no change in viscosity or reactivity of the composition was observed. Therefore, the composition of Example 16 also has excellent storage stability.

[0129] [Table 6]

[0130] [Example 17] The procedure of Example 16 was repeated in much the same way in Example 17, except that the coating and lamination were carried out in air. The ionic conductivity of the resulting AEM was measured at various temperatures, and the results are summarized in Table 7. Interestingly, preparing the AEM in air appears to improve the conductivity of the resulting AEM.

[0131] [Table 7]

[0132] [Example 18] Formation of thick AEMs by UV-initiated bulk polymerization The procedure of Example 17 was repeated in much the same way in Example 18, except that the Z3030 support was bilayered and a monomer mixture of NBBuBr and NBOctylNB (molar ratio 99:1) was used. The ionic conductivity of the resulting AEM was measured at various temperatures, and the results are summarized in Table 8. Figure 4 shows an SEM cross-section of the original Z3030 support used before the application of the monomer mixture, and the microporous structure is clearly visible. Figure 5 shows an SEM cross-section of the membrane obtained in Example 18 after coating with the monomer mixture and curing. The micropores are filled with the polymer obtained by bulk polymerization of the monomer mixture, and there are no gaps between the two support layers, indicating the formation of a continuous norbornene polymer phase throughout the entire thickness of the membrane.

[0133] [Table 8]

[0134] [Examples 19 to 20] UV-initiated bulk-polymerized AEM with high crosslinking degree The procedure of Example 18 was repeated in almost the same way in Examples 19 and 20, except that a monomer mixture of NBBuBr and NBOctylNB (molar ratios of 98:2 and 97:3, respectively) was used. The ionic conductivity of the resulting AEM was measured at various temperatures, and the results are summarized in Table 9.

[0135] [Table 9]

[0136] [Examples 21 to 22] Surface cross-linking controlled AEM The procedure of Example 11 was repeated in much the same way in Examples 21 and 22, except that a Z3030 support was used in a double layer and only NBBuBr was used as the olefinic monomer. Prior to quaternization, the membranes were immersed in a diamine (a 50 / 50 wt.% solution of N,N'-dimethyl-1,6-hexanediamine / isopropanol) for 0 hours (Example 21) or 3 hours (Example 22) (also summarized in Table 10), followed by washing with isopropanol. The ionic conductivity of the resulting AEMs was measured at various temperatures, and the results are summarized in Table 10. The membrane formed in Example 22 exhibited low conductivity over the entire temperature range measured, as shown in Table 10. However, compared to the membrane of Example 21, the membrane of Example 22 also exhibited approximately 22% less swelling in the x and y directions. This study therefore demonstrates that an appropriate level of surface cross-linking can control or reduce membrane swelling and extend membrane life. It was also found that surface cross-linking substantially reduces the thickness of the ion-resistant layer (i.e., forms a dense network), thereby improving overall conductivity compared to bulk cross-linking. It should be noted that immersion of the membrane in diamine for more than 3 hours significantly reduces conductivity. In Comparative Examples 3 and 4, a significant decrease in conductivity was observed when the membrane was immersed in diamine for more than 1 day.

[0137] [Table 10]

[0138] [Comparative Examples 1 to 2] In Comparative Examples 1 and 2, commercially available AEM Pention-AEM-72_05 (https: / / www.fuelcellstore.com / xergy-xion-composite-pention-aem-72-05-5cl-72600070#:~:text=The%20Xergy%20Pention%2DAEM%2D72, a wide variety of chemistries) with thicknesses of 25 μm and 46 μm, respectively, was used. As described on the vendor's website (URL above), the Pention-AEM membrane is formed from a poly(norbornene)-based resin. The in-plane conductivities of these membranes were measured and are summarized in Table 11. As is evident from the results shown in Table 11, the commercially available membranes have significantly lower ionic conductivities under comparable conditions compared to the AEM prepared according to the present invention.

[0139] [Table 11] Figure 6 shows a cross-sectional SEM image of the 25 μm Pention_AEM used in Comparative Example 1, revealing that the support layer has a very open structure. The open structure means that the continuous polymer phase is only a small part of the overall structure. This is likely to be a limiting factor for ionic conductivity in the membrane channel (i.e., interfacial conductivity), resulting in significantly poor performance in the electrolysis device.

[0140] [Comparative Examples 3 to 4] In Comparative Examples 3-4, the procedure of Example 21 was repeated in substantially the same manner as shown in Table 10, except that the membrane was kept in a 50 / 50 wt % solution of N,N′-dimethyl-1,6-hexanediamine / isopropanol for 1 day (Comparative Example 3) or 1 week (Comparative Example 4), respectively, before quaternization and then washed with isopropanol.

[0141] Although the present invention has been described with reference to the above examples, the present invention is not limited to the examples, but generally encompasses the general scope set forth hereinabove. Various modifications and embodiments may be made without departing from the spirit and scope thereof.

Claims

1. a) one or more monomers represented by formula (I): 【Chemistry 1】 where: Y and Y' are the same or different and each independently represent -CH ２ -, -CH ２ -CH ２ -, and -O-; m is an integer from 0 to 3; R １ , R ２ , R ３ , and R ４ at least one of which is a group represented by the formula R-X, However, R is (C １ ~C １０ ) alkylene, (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene (C １ ~C １０ ) alkylene, (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene, and (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene (C １ ~C １０ ) alkylene; X is halogen, hydroxy, (C １ ~C １０ ) alkoxy, and (C ６ ~C １２ ) aryloxy; The remaining R １ , R ２ , R ３ , and R ４ are each independently hydrogen, methyl, ethyl, straight-chain or branched (C ３ ~C １０ ) alkyl, (C ３ ~C ８ ) cycloalkyl, (C １ ~C １０ ) alkyl(C ３ ~C ８ ) cycloalkyl, and (C １ ~C １０ ) alkyl(C ６ ~C １０ ) selected from the group consisting of aryl; b) one or more monomers represented by formula (III): 【Chemistry 2】 where: a is an integer of 0, 1, or 2; b is an integer from 1 to 10, K and K′ are the same or different and each independently represent —CH ２ -, -CH ２ -CH ２ selected from the group consisting of —, —O—, and —S—; and c) a palladium catalyst selected from the group consisting of thermally activated vinyl addition palladium catalysts and photoactivated vinyl addition palladium catalysts; wherein the amount of the monomer represented by formula (III) present does not exceed 3 mol% relative to the total number of moles of the monomer represented by formula (I) and the monomer represented by formula (III).

2. 10. The composition of claim 1, further comprising one or more monomers represented by formula (II): 【Transformation 3】 where: Z and Z′ are the same or different and each independently represent —CH ２ -, -CH ２ -CH ２ -, and -O-; n is an integer from 0 to 3, R ８ , R ９ , R １０ , and R １１ are the same or different and each independently represent hydrogen, methyl, ethyl, straight-chain or branched (C ３ ~C １０ ) alkyl, (C ３ ~C ８ ) cycloalkyl, (C １ ~C １０ ) alkyl(C ３ ~C ８ ) cycloalkyl, and (C １ ~C １０ ) alkyl(C ６ ~C １０ ) aryl.

3. The palladium catalyst is a) A compound represented by the following formula (IV): 【Chemistry 4】 where: R １２ , R １３ and R １４ At least two of the tert-(C ４ ~C １２ ) alkyl, 1-(C １ ~C ５ ) alkyl(C ３ ~C ８ ) cycloalkyl, 1-(C ５ ~C １２ ) bicycloalkyl, 1-(C ８ ~C １２ ) tricycloalkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl; The remaining R １２ , R １３ or R １４ is methyl, ethyl, straight-chain or branched (C ３ ~C １２ ) alkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, R １５ and R １６ are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C ３ ~C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ ~C ２０ ) perfluoroalkyl; and b) A compound represented by the following formula (VI): M ｄ ＋ Z － (VI) where: M ｄ ＋ is lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C １ ~C ４ ) alkylammonium cations, Z － is B(C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , B(C ６ H ５ ) ４ － , [Al(OC(CF ３ ) ２ C ６ F ５ ) ４ ] － , B.F. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and CF ３ SO ３ － is a weakly coordinating anion selected from the group consisting of:

10. The composition of claim 1, wherein the catalyst is a thermally activated palladium catalyst comprising:

4. The palladium catalyst is a) a palladium compound represented by the following formula (V): Pd(OCOR) １７ ) ２ (P)R １８ ) ３ ) ２ (V) where: R １７ are each independently methyl, ethyl, straight-chain or branched (C ３ ~C ６ ) alkyl, and (C ６ ~C １２ ) aryl; R １８ are each independently ３ ~C １０ ) cycloalkyl, and (C ６ ~C １２ ) selected from the group consisting of aryl; and b) A compound represented by the following formula (VII): 【Transformation 5】 and a compound represented by the following formula (VIII): 【Transformation 6】 a photoinitiator selected from the group consisting of: where: d is an integer from 0 to 5, An － is Cl － ,Br － , I － , B.F. ４ － , tetrakis(pentafluorophenyl)borate, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, tetrakis(2-fluorophenyl)borate, tetrakis(3-fluorophenyl)borate, tetrakis(4-fluorophenyl)borate, tetrakis(3,5-difluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5,6-tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, methyl tris(perfluorophenyl)borate, ethyl tris(perfluorophenyl)borate, phenyl tris(perfluorophenyl)borate, tetrakis(1,2,2-trifluoroethylenyl)borate, tetrakis(4-tri- tetrakis(1-propylsilyltetrafluorophenyl)borate, tetrakis(4-dimethyl-tert-butylsilyltetrafluorophenyl)borate, (triphenylsiloxy)tris(pentafluorophenyl)borate, (octyloxy)tris(pentafluorophenyl)borate, tetrakis[3,5-bis[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]phenyl]borate, tetrakis[3-[1-methoxy-2,2,2-trifluoro-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, and tetrakis[3-[2,2,2-trifluoro-1-(2,2,2-trifluoroethoxy)-1-(trifluoromethyl)ethyl]-5-(trifluoromethyl)phenyl]borate, PF ６ － , SbF ６ － , AsF ６ － , n-C ４ F ９ SO ３ － , C.F. ３ SO ３ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and p-CH ３ (C ６ H ４ )-SO ３ － selected from the group consisting of R １９ , R ２０ , R ２１ , R ２２ , and R ２３ are the same or different and each independently represent a halogen atom, a methyl group, an ethyl group, a linear or branched group (C ３ ~C ２０ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, (C １ ~C １２ ) alkoxy, (C ３ ~C １２ ) cycloalkoxy, (C ６ ~C １２ ) bicycloalkoxy, (C ７ ~C １４ ) tricycloalkoxy, (C ６ ~C １０ ) aryloxy(C １ ~C ３ ) alkyl, (C ６ ~C １０ )-aryloxy, (C ６ ~C １０ ) thioaryl, (C １ ~C ６ ) alkanoyl (C ６ ~C １０ ) thioaryl, (C １ ~C ６ ) alkoxy(C ６ ~C １０ ) Aroyl (C １ ~C ６ ) alkyl, and (C ６ ~C １０ ) thioaryl-(C ６ ~C １０ ) diallylsulfonium salts; 2. The composition of claim 1, wherein the photoactivatable palladium catalyst comprises:

5. m, n, and a are each 0 or 1; b is an integer from 3 to 8; Y, Y', Z, Z', K, and K' are each CH ２ and R １ , R ２ , R ３ , and R ４ at least one of is a group represented by the formula R-X, where R is (CH ２ ) ｃ , (CH ２ ) ｃ Cyclohexylene, (CH ２ ) ｃ Cyclohexylene (CH ２ ) ｃ , (CH ２ ) ｃ phenylene, and (CH ２ ) ｃ Phenylene (CH ２ ) ｃ and c is an integer from 1 to 10; X is bromine; The remaining R １ , R ２ , R ３ , and R ４ are each independently selected from the group consisting of hydrogen, methyl, ethyl, straight or branched chain propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, and benzyl; R ８ , R ９ , R １０ , and R １１ are each independently selected from the group consisting of methyl, ethyl, straight or branched chain propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, methylcyclopentyl, methylcyclohexyl, and benzyl; R １２ , R １３ , and R １４ at least two of are the same and are selected from the group consisting of tert-butyl, 1-norbornyl, 1-bicyclo[2.2.2]octyl, and 1-adamantyl; The remaining R １２ , R １３ , and R １４ is selected from the group consisting of n-propyl, n-butyl, n-pentyl, and n-hexyl; R １５ and R １６ and n are the same or different and are each independently selected from the group consisting of methyl, ethyl, n-propyl, and n-butyl.

6. M ｄ ＋ is lithium, Z － But B (C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － , and B(C ６ H ５ ) ４ － The composition of claim 3 selected from the group consisting of:

7. The monomer represented by formula (I) 【Chemistry 7-1】 【Chemistry 7-2】 10. The composition of claim 1, selected from the group consisting of:

8. The monomer represented by formula (III) 【Transformation 8】 10. The composition of claim 1, selected from the group consisting of:

9. The palladium compound represented by the formula (IV) 【Chemistry 9】 The composition of claim 3 selected from the group consisting of:

10. The palladium compound represented by the formula (V) Diacetate bis(tricyclopentylphosphine)palladium; Diacetate bis(tricyclohexylphosphine)palladium (Pd785); bis(tricycloheptylphosphine)palladium diacetate; and 5. The composition of claim 4, wherein the compound is selected from the group consisting of palladium diacetate bis(triphenylphosphine) palladium.

11. The monomer represented by formula (II) 【Chemistry 10-1】 【Chemistry 10-2】 【Chemistry 10-3】 [Chemistry 10-4] The composition of claim 2 selected from the group consisting of:

12. The compound represented by formula (VI) Lithium tetrafluoroborate; Lithium triflate; Lithium tris(trifluoromethylsulfonyl)methanide; Lithium tetrakis(pentafluorophenyl)borate (LiFABA); Lithium tetraphenylborate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate; Lithium tetrakis(2-fluorophenyl)borate; Lithium tetrakis(3-fluorophenyl)borate; Lithium tetrakis(4-fluorophenyl)borate; Lithium tetrakis(3,5-difluorophenyl)borate; Lithium hexafluorophosphate; Lithium hexaphenyl phosphate; Lithium hexakis(pentafluorophenyl)phosphate; Lithium hexafluoroarsenate; Lithium hexaphenylarsenate; Lithium hexakis(pentafluorophenyl)arsenate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)arsenate; Lithium hexafluoroantimonate; Lithium hexaphenylantimonate; Lithium hexakis(pentafluorophenyl)antimonate; Lithium hexakis(3,5-bis(trifluoromethyl)phenyl)antimonate; Lithium tetrakis(pentafluorophenyl)aluminate; Lithium tris(nonafluorobiphenyl)fluoroaluminate; Lithium (octyloxy)tris(pentafluorophenyl)aluminate; Lithium tetrakis(3,5-bis(trifluoromethyl)phenyl)aluminate; Lithium methyltris(pentafluorophenyl)aluminate; and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate (DANFABA); The composition of claim 3 selected from the group consisting of:

13. 5-Propylbicyclo[2.2.1]hept-2-ene, 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)propane, 5-(3-bromopropyl)bicyclo[2.2.1]hept-2-ene, diacetate(n-butyldi-1-adamantylphosphine)palladium(H ２ 0) (Pd601), and a mixture of lithium (diethyl ether) tetrakis(pentafluorophenyl)borate (LiFABA); 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), (n-butyldi-1-adamantylphosphine)palladium diacetate (H ２ 0) (Pd601), and a mixture of lithium (diethyl ether) tetrakis(pentafluorophenyl)borate (LiFABA); 5-Pentylbicyclo[2.2.1]hept-2-ene, 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)propane, 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene, diacetate(n-butyldi-1-adamantylphosphine)palladium(H ２ 0) (Pd601), and a mixture of lithium (diethyl ether) tetrakis(pentafluorophenyl)borate (LiFABA); 1,8-di(bicyclo[2.2.1]hept-5-en-2-yl)octane (NBOctylNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), diacetate (n-butyldi-1-adamantylphosphine)palladium (H ２ 0) (Pd601), and a mixture of lithium (diethyl ether) tetrakis(pentafluorophenyl) borate (LiFABA); and a mixture of 5-butylbicyclo[2.2.1]hept-2-ene (BuNB), 1,4-di(bicyclo[2.2.1]hept-5-en-2-yl)butane (NBBuNB), 5-(4-bromobutyl)bicyclo[2.2.1]hept-2-ene (NBBuBr), diacetate bis(tricyclohexylphosphine)palladium (Pd785), tolylcumyliodonium tetrakis(pentafluorophenyl)borate, and 2-isopropyl-9H-thioxanthen-9-one; 10. The composition of claim 1, selected from the group consisting of:

14. The compound represented by formula (VII) or the compound represented by formula (VIII) is 【Chemistry 11-1】 【Chemistry 11-2】 【Chemistry 11-3】 【Chemistry 11-4】 The composition of claim 4 selected from the group consisting of:

15. The composition according to claim 4, further comprising a photosensitizer selected from the group consisting of compounds represented by the following formula (IX) or compounds represented by the following formula (X): 【Chemistry 12】 where: R ２４ , R ２５ , and R ２６ are the same or different and each independently represent hydrogen, halogen, hydroxy, NO ２ , N.H. ２ , methyl, ethyl, linear or branched (C ３ ~C １２ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, (C １ ~C １２ ) alkoxy, (C ３ ~C １２ ) cycloalkoxy, (C ６ ~C １２ ) bicycloalkoxy, (C ７ ~C １４ ) tricycloalkoxy, (C ６ ~C １０ ) aryloxy(C １ ~C ３ ) alkyl, (C ６ ~C １０ )-aryloxy, C(O)(C １ ~C ６ ) alkyl, COOH, C(O)O(C １ ~C ６ ) alkyl, and SO ２ (C ６ ~C １０ ) aryl; R ２７ and R ２８ are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C ３ ~C １２ ) alkyl, (C ３ ~C １２ ) cycloalkyl, (C ６ ~C １２ ) bicycloalkyl, (C ７ ~C １４ ) tricycloalkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl.

16. The compound represented by formula (IX) or the compound represented by formula (X) 【Chemistry 13-1】 【Chemistry 13-2】 【Chemistry 13-3】 The composition of claim 12 selected from the group consisting of:

17. 10. An anion exchange membrane comprising the composition of claim 1, wherein the composition is first bulk polymerized by heating to about 80° C. to 120° C. or by exposure to suitable actinic radiation, and then polymerized with tri(C １ ~C ４ ) An anion exchange membrane which is formed by treating with an alkylamine to form a quaternized anion exchange membrane.

18. 1. A kit for forming an anion exchange membrane comprising: a) one or more monomers represented by formula (I): 【Chemistry 14】 where: Y and Y' are the same or different and each independently represent -CH ２ -, -CH ２ -CH ２ -, and -O-; m is an integer from 0 to 3; R １ , R ２ , R ３ , and R ４ at least one of which is a group represented by the formula R-X, However, R is (C １ ~C １０ ) alkylene, (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene (C １ ~C １０ ) alkylene, (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene, and (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene (C １ ~C １０ ) alkylene; X is halogen, hydroxy, (C １ ~C １０ ) alkoxy, and (C ６ ~C １２ ) aryloxy; The remaining R １ , R ２ , R ３ , and R ４ are each independently hydrogen, methyl, ethyl, straight-chain or branched (C ３ ~C １０ ) alkyl, (C ３ ~C ８ ) cycloalkyl, (C １ ~C １０ ) alkyl(C ３ ~C ８ ) cycloalkyl, and (C １ ~C １０ ) alkyl(C ６ ~C １０ ) selected from the group consisting of aryl; b) one or more monomers represented by formula (III): 【Chemistry 15】 where: a is an integer of 0, 1, or 2; b is an integer from 1 to 10, K and K′ are the same or different and each independently represent —CH ２ -, -CH ２ -CH ２ selected from the group consisting of —, —O—, and —S—; c) A palladium compound represented by the following formula (IV): 【Chemistry 16】 where: R １２ , R １３ and R １４ At least two of the tert-(C ４ ~C １２ ) alkyl, 1-(C １ ~C ５ ) alkyl(C ３ ~C ８ ) cycloalkyl, 1-(C ５ ~C １２ ) bicycloalkyl, 1-(C ８ ~C １２ ) tricycloalkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl; The remaining R １２ , R １３ or R １４ is methyl, ethyl, straight-chain or branched (C ３ ~C １２ ) alkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, R １５ and R １６ are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C ３ ~C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ ~C ２０ ) perfluoroalkyl; and d) A compound represented by the following formula (VI): M ｄ ＋ Z － (VI) where: M ｄ ＋ is lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C １ ~C ４ ) alkylammonium cations, Z － is B(C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , B(C ６ H ５ ) ４ － , [Al(OC(CF ３ ) ２ C ６ F ５ ) ４ ] － , B.F. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － 、 and CF ３ SO ３ － is a weakly coordinating anion selected from the group consisting of: Including, wherein the amount of the monomer represented by formula (III) present does not exceed 3 mol% relative to the total number of moles of the monomer represented by formula (I) and the monomer represented by formula (III).

19. 1. A method for forming an anion exchange membrane, comprising: Preparing a solution containing the following: a) one or more monomers represented by formula (I): 【Chemistry 17】 where: Y and Y' are the same or different and each independently represent -CH ２ -, -CH ２ -CH ２ -, and -O-; m is an integer from 0 to 3; R １ , R ２ , R ３ , and R ４ at least one of which is a group represented by the formula R-X, However, R is (C １ ~C １０ ) alkylene, (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene, (C １ ~C １０ ) alkylene (C ３ ~C ８ ) cycloalkylene (C １ ~C １０ ) alkylene, (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene, and (C １ ~C １０ ) alkylene (C ６ ~C １０ ) arylene (C １ ~C １０ ) alkylene; X is halogen, hydroxy, (C １ ~C １０ ) alkoxy, and (C ６ ~C １２ ) aryloxy; The remaining R １ , R ２ , R ３ , and R ４ are each independently hydrogen, methyl, ethyl, straight-chain or branched (C ３ ~C １０ ) alkyl, (C ３ ~C ８ ) cycloalkyl, (C １ ~C １０ ) alkyl(C ３ ~C ８ ) cycloalkyl, and (C １ ~C １０ ) alkyl(C ６ ~C １０ ) selected from the group consisting of aryl; b) one or more monomers represented by formula (III): [Chemistry 18] where: a is an integer of 0, 1, or 2; b is an integer from 1 to 10, K and K′ are the same or different and each independently represent —CH ２ -, -CH ２ -CH ２ selected from the group consisting of —, —O—, and —S—; c) A palladium compound represented by the following formula (IV): 【Chemistry 19】 where: R １２ , R １３ and R １４ At least two of the tert-(C ４ ~C １２ ) alkyl, 1-(C １ ~C ５ ) alkyl(C ３ ~C ８ ) cycloalkyl, 1-(C ５ ~C １２ ) bicycloalkyl, 1-(C ８ ~C １２ ) tricycloalkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl; The remaining R １２ , R １３ or R １４ is methyl, ethyl, straight-chain or branched (C ３ ~C １２ ) alkyl, (C ６ ~C １０ ) aryl, and (C ６ ~C １０ ) aryl (C １ ~C ３ ) alkyl, R １５ and R １６ are the same or different and each independently represent methyl, ethyl, straight-chain or branched (C ３ ~C ２０ ) alkyl, trifluoromethyl, pentafluoroethyl, and linear or branched (C ３ ~C ２０ ) perfluoroalkyl; and d) A compound represented by the following formula (VI): M ｄ ＋ Z － (VI) where: M ｄ ＋ is lithium, sodium, potassium, cesium, barium, ammonium, and linear or branched tetra(C １ ~C ４ ) alkylammonium cations, Z － is B(C ６ F ５ ) ４ － , B[C ６ H ３ (CF ３ ) ２ ] ４ － , B(C ６ H ５ ) ４ － , [Al(OC(CF ３ ) ２ C ６ F ５ ) ４ ] － , B.F. ４ － , P.F. ６ － , AsF ６ － , SbF ６ － , (CF ３ SO ２ ) ２ N － , (CF ３ SO ２ ) ３ C － 、 and CF ３ SO ３ － is a weakly coordinating anion selected from the group consisting of: provided that the amount of the monomer represented by formula (III) present does not exceed 3 mol% relative to the total number of moles of the monomer represented by formula (I) and the monomer represented by formula (III); applying said solution to a membrane support; heating the coated membrane support at a temperature of about 80°C to about 120°C for about 30 minutes to about 90 minutes; The heated membrane support is heated at a temperature of about 20°C to about 50°C for about 2 to about 5 days in a tri-(C １ ~C ４ ) treating with an aqueous alkylamine solution to form a quaternized anion exchange membrane; washing the quaternized anion exchange membrane with water; and immersing the quaternized anion exchange membrane in an alkaline solution to form an anion exchange membrane; A method comprising:

20. 20. An anion exchange membrane produced by the method of claim 19.

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