Polyphenylene, and manufacturing method and use of the same

Abstract

To provide an ionomer designed to accurately control positions and the number of anionic groups used in a hydrocarbon-based proton exchange membrane intended for an electrochemical purpose.SOLUTION: An anionic oligomer and a polymer are provided which are obtainable from a reaction between a cyclopentadienone compound in which a phenyl group having anionic groups is substituted, and diethynyl benzene.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] <Related Application> This application claims the benefit of Provisional Application No. 62 / 483,668, filed on April 10, 2017, the disclosure of which is hereby incorporated by reference in its entirety.

[0002] <Background of the Invention>

[0003] Hydrocarbon-based proton exchange membranes (PEMs) and ionomers intended for electrochemical applications (e.g., fuel cells, electrolyzers, water treatment) have been actively investigated as alternatives to conventional perfluorosulfonic acid (PFSA) ionomers due to their ease of synthesis, low cost, low gas crossover, high Tg, and low environmental concerns. Various ion-containing polymers have been studied, especially sulfonated derivatives of polymers incorporating aromatic groups in part of the polymer backbone, such as poly(arylene ether), poly(arylene ether ketone), poly(arylene sulfone), poly(imide), and poly(benzimidazole). However, hydrocarbon-based ionomers to date have suffered from the problem of high sensitivity to oxidative degradation in ex situ (e.g., Fenton reagent tests) and / or in situ (e.g., PEM fuel cells). Therefore, recently, efforts have been focused on the rational design of hydrocarbon ionomers with improved chemical and mechanical stability.

[0004] As reported by Stille, Mullen, and others, polyphenylene has inherent chemical stability and mechanical strength. More recently, attention has been focused on the route to branched polyphenylene with ionic functionality. Sulfonated phenylated polyphenylene (sPPPs) has been of particular interest as a PEM because it has inherent chemical and mechanical stability derived from its fully aromatic backbone. The sulfonated type of branched polyphenylene can be prepared by post-sulfonation of polyphenylene, and thus polymers for electrochemical membranes can be prepared. Membranes incorporating these polymers have been reported to be mechanically robust and have high ionic (proton) conductivity. Recently, these polymers have been tested for use as proton exchange membrane fuel cells (PEMFCs), and post-quaternized ammonium derivatives have been tested for use as anion exchange membrane fuel cells (AEMFCs).

[0005] Nevertheless, reports on sulfonated polyphenylene are relatively few. This is because it is difficult to form rigid and sterically hindered aryl-aryl bonds, and there is a need to introduce ionic functionality later in a polar medium for polymers that are difficult to process in close proximity. Examples of sulfonated polyphenylene are structurally ill-defined and relatively disordered. This is because in post-sulfonation, it is uncertain whether the phenyl bond will be a meta-bond or a para-bond, and bonding at multiple positions on multiple phenyl rings is possible (see, for example, Fujimoto, C. H.; Hickner, M. A.; Cornelius, C. J.; Loy, D. A. Macromolecules 2005, 38, 5010). Therefore, research in this field has been severely limited by the difficulty of synthesizing a well-defined polymer backbone consisting of sterically hindered and rigid aryl-aryl bonds, low solubility in polar solvents, and the ill-defined molecular structure as a result of the commonly practiced post-sulfonation technique. These difficulties result in a random distribution of ionic groups on multiple phenyl rings and an uncertain ratio of meta:para bonds between the phenyl rings and the polymer backbone.

[0006] Precise control of the polymer structure and precise placement of ionic functions along the polymer backbone can improve the ordering of ion channels over short and long ranges, and thus it is possible to improve ionic conductivity. Through high-level molecular control, control of the spatial arrangement of sulfonic acid groups on the polymer can be achieved - however, such control is difficult, if not impossible, by post-sulfonation of polyphenylene.

[0007] Therefore, it is necessary to control anionic (e.g., sulfonated) monomers and synthesize anionic (e.g., sulfonated) oligophenylene and polymers using them while precisely controlling the position and number of anionic (e.g., sulfonic acid) groups. The present application meets these requirements and provides further advantages. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] <SUMMARY OF THE INVENTION> This summary is provided to introduce a series of concepts in a simplified form that will be further described in the following detailed description. This summary is not intended to identify the key features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter. In one aspect, the present application discloses a polymer comprising a repeating unit represented by formula (I):

[0009] [Chemical formula]

[0010] {In the formula, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are independently aryl or heteroaryl, each optionally C1-6 Alkyl, halo, nitro, cyano, SO3 - X + , PO3 2- X + 2, and COO - X + is substituted with 1, 2, 3, 4, or 5 substituents independently selected from, and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F of which at least two are independently substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3 - X + , PO3 2- X + 2, and COO - X + and is aryl or heteroaryl; R 1G and R 1H are independently H, aryl, or heteroaryl, and the aryl and heteroaryl are each optionally C 1-6 alkyl, halo, nitro, cyano, SO3 - X + , PO3 2- X + 2, and COO - X + substituted with 1, 2, 3, 4, or 5 substituents independently selected from, and X + is H + or a cation; A1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A2 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L1 is an optionally substituted linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L2 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl and heteroaryl} Provided that the repeating unit of formula (I) is not the following.

[0011]

Chemical formula

[0012] In another aspect, the present application is a polymer, a first repeating unit selected from the following and any combination thereof:

[0013]

Chemical formula

[0014] {wherein X + is H + or a cation defined herein}; and a second repeating unit selected from the following and any combination thereof:

[0015]

Chemical formula

[0016] Disclosed is a polymer comprising the above and having a molar ratio of the first repeating unit to the second repeating unit in the range of 1:99 to 99:1.

[0017] In yet another aspect, the present application is a random block polymer, a first block selected from the following and any combination thereof:

[0018]

Chemical formula

[0019] {wherein X + is H + or a cation defined herein}; and a second block selected from the following and any combination thereof:

[0020]

Chemical formula

[0021] {wherein n is an integer from 3 to 100 and m is an integer from 3 to 100} Disclosed is a random block polymer comprising the above and having a molar ratio of the first block to the second block in the range of 1:99 to 99:1.

[0022] In yet another aspect, the present application discloses a compound represented by formula (III).

[0023]

Chemical formula

[0024] {Wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, SO3 - X + 、PO3 2- X + 2, and COO - X + ; X + is H + or a cation; at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3 - X + 、PO3 2- X + 2, and COO - X + ; A1 is arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A2 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl} However, the compound represented by formula (III) is not the following.

[0025]

Chemical formula

[0026] In yet another aspect, the present application discloses a method for producing a random block copolymer, the production method comprising a first polymer represented by formula (VI):

[0027]

Chemical formula

[0028] {wherein R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、R 1F 、R 1G 、R 1H 、R 2A 、R 2B 、R 2C 、and R 2D 、A1, A2, L1, L2, and L3 are as defined above, n is an integer from 3 to 100, A is a first reactive end group} and a second polymer represented by formula (VII):

[0029]

Chemical formula

[0030] {wherein R 3A 、R3B , R 3C , R 3D , R 3E , R 3F , R 3G , R 3H , R 4A , R 4B , R 4C , R 4D , B1, B2, K1, K2, and K3 are as defined herein, m is an integer from 3 to 100, B is a second reactive end group configured to react with A} to prepare a mixture of; reacting A {e.g., alkylene (having reactivity with tetracyclone) or tetracyclone (having reactivity with alkylene)} and B (e.g., tetracyclone or alkylene) to obtain a random block copolymer represented by formula (VIII);

[0031]

Chemical formula

[0032] {wherein the molar ratio of the first block to the second block is in the range of 1:99 to 99:1} comprising.

[0033] In yet another aspect, the present application discloses a method for manufacturing the aforementioned polymer, and the manufacturing method is, preparing a mixture comprising the compound represented by the aforementioned formula (III) and at least one compound represented by formula (IX):

[0034]

Chemical formula

[0035] {wherein, L1 is a linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-) optionally substituted, arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally C 1-6 substituted with 1, 2, 3, or 4 substituents independently selected from C alkyl, halo, nitro, cyano, aryl, and heteroaryl; 1-6 L2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; D3 is H, R 1G , R 1H , R 3G , R 3H , or a protecting group (e.g., silyl protecting group, substituted silyl protecting group, trialkylsilyl protecting group, silyl ether protecting group, trialkylsilyl ether protecting group, trimethylsilyl ether), and R 1G and R 1H are as defined herein, and R 3G and R 3H are as defined herein; D4 is halo}; Reacting a compound represented by formula (III) or formula (III-A) with at least one compound represented by formula (IX) by a Diels Alder reaction to obtain a halogenated intermediate compound; The halogenated intermediate compound is coupled in the presence of an organopalladium catalyst, an organocopper catalyst, an organonickel catalyst, an organomanganese catalyst, an organoplatinum catalyst, an organoruthenium catalyst, or a combination thereof to obtain the polymer of the present application; including this.

[0036] In yet another aspect, the present application discloses an ionomer containing the polymer according to the present application. The ionomer can be incorporated into a cation exchange resin.

Brief Description of the Drawings

[0037] Many of the foregoing aspects and attendant advantages of the present invention will be better understood and more readily appreciated by reference to the following detailed description in conjunction with the accompanying drawings.

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[0038] <Detailed Description of the Invention> Disclosed herein are anionic phenylene oligomers and polymers, and devices containing these materials. The oligomers and polymers can be prepared by convenient and well-controlled methods and can be used in cation exchange membranes. Also disclosed are the controlled synthesis of anionic phenylene monomers and their use in the synthesis of anionic oligomers and polymers, with the synthesis being accurately controlled in terms of the position and number of anionic groups.

[0039] <Definition> Throughout various places in this specification, the substituents of the compounds of this application are disclosed in groups or ranges. This application specifically intends to include all possible independent sub-combinations of the compositions of such groups and ranges. For example, the term "C l-6 alkyl" is specifically intended to independently disclose methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl. As an example, the term "optionally substituted with 1, 2, 3, 4, or 5" is intended to independently disclose being optionally substituted with 1, 2, 3, or 4; 1, 2, or 3; 1, or 2; or one substituent.

[0040] It is further intended that the compounds of this disclosure be stable. As used herein, "stable" means a compound having sufficient robustness to isolate the compound from the reaction mixture with a useful degree of purity.

[0041] It is further understood that the specific features of this application described in the context of individual embodiments can also be employed in combination in one embodiment. Conversely, for the sake of brevity, the various features of this application described in the context of one embodiment can also be employed individually or in any suitable sub-combination.

[0042] It is intended that divalent groups such as the linking group (e.g., alkylene, arylene, etc.) between the first part and the second part can be oriented in both the forward and reverse directions with respect to the first part and the second part, unless otherwise specified.

[0043] A "optionally substituted" group can mean, for example, a functional group that is substituted by an additional functional group or is unsubstituted. For example, when the group is unsubstituted, it may be denoted by the name of a group such as alkyl or aryl. When the group is substituted by an additional functional group, it may more generally be denoted as a substituted alkyl or a substituted aryl.

[0044] As used herein, the term "substituted" or "substitution" means replacing a hydrogen atom with a substituent other than H. For example, "N-substituted piperidin-4-yl" means replacing the H atom of the NH of piperidinyl with a substituent other than hydrogen, such as alkyl.

[0045] As used herein, the term "alkyl" means a straight-chain or branched hydrocarbon group. In some embodiments, alkyl has 1 to 10 carbon atoms (e.g., 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom). Representative alkyl groups include methyl, ethyl, propyl (e.g., n-propyl, isopropyl), butyl (e.g., n-butyl, sec-butyl, and tert-butyl), pentyl (e.g., n-pentyl, tert-pentyl, neopentyl, isopentyl, pentan-2-yl, pentan-3-yl), and hexyl (e.g., n-hexyl and isomers) groups.

[0046] As used herein, the term "alkylene" means a connecting alkyl group. As used herein, the term "cycloalkyl" means a non-aromatic carbocyclic ring and includes cyclic alkyl, alkenyl, and alkynyl groups. Cycloalkyl groups include monocyclic or polycyclic (e.g., having 2, 3, or 4 fused rings), including spiro rings. In some embodiments, the cycloalkyl group can have 3 to about 20 carbon atoms, 3 to about 14 carbon atoms, 3 to about 10 carbon atoms, or 3 to 7 carbon atoms. The cycloalkyl group can further have 0, 1, 2, or 3 double bonds and / or 0, 1, or 2 triple bonds. This definition of cycloalkyl further includes sites where one or more aromatic rings are fused to the cycloalkyl ring (i.e., having a common bond), including, for example, benzo derivatives such as pentane, pentene, hexane, etc. A cycloalkyl group having one or more fused aromatic rings can be attached via either an aromatic or non-aromatic moiety. One or more of the ring-forming carbons of the cycloalkyl group can be oxidized, for example, having an oxo or sulfide substituent. Exemplary cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, norbornyl, norpinyl, norcamyl, adamantyl, etc.

[0047] As used herein, the term "cycloalkylene" means a linking cycloalkyl group. As used herein, the term "perfluoroalkyl" means a straight-chain or branched fluorocarbon chain. In some embodiments, perfluoroalkyl has 1 to 10 carbon atoms (e.g., 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom). Representative alkyl groups include trifluoromethyl, pentafluoroethyl, etc.

[0048] As used herein, the term "perfluoroalkylene" means a linking perfluoroalkyl group. As used herein, the term "heteroalkyl" means a straight or branched alkyl group in which one or more carbon atoms are replaced by a heteroatom selected from O, N, or S. In some embodiments, heteroalkyl has 1 to 10 carbon atoms (e.g., 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom).

[0049] As used herein, the term "heteroalkylene" means a linking heteroalkyl group. As used herein, the term "alkoxy" means an alkyl or cycloalkyl group as described herein attached to an oxygen atom. In some embodiments, alkoxy has 1 to 10 carbon atoms (e.g., 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom). Representative alkoxy groups include methoxy, ethoxy, propoxy, and isopropoxy groups.

[0050] As used herein, the term "perfluoroalkoxy" means a perfluoroalkyl or cyclic perfluoroalkyl group as described herein attached to an oxygen atom. In some embodiments, perfluoroalkoxy has 1 to 10 carbon atoms (e.g., 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 or 2 carbon atoms, or 1 carbon atom). Representative perfluoroalkoxy groups include trifluoromethoxy, pentafluoroethoxy, and the like.

[0051] As used herein, the term "aryl" means an aromatic hydrocarbon group having 6 to 10 carbon atoms. Representative aryl groups include the phenyl group. In some embodiments, the term "aryl" includes monocyclic or polycyclic (e.g., having 2, 3, or 4 fused rings) aromatic hydrocarbons, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, and indenyl.

[0052] As used herein, the term "arylene" means an aryl group that connects. For example, the term "phenylene" means a phenyl group that connects. As used herein, the term "aralkyl" means an alkyl or cycloalkyl as defined herein, wherein one of the alkyl hydrogen atoms is substituted with an aryl group as defined herein.

[0053] As used herein, the term "aralkylene" means an aralkyl group that connects. As used herein, the term "heteroaryl" means a monocyclic or bicyclic aromatic 5- to 10-membered ring having 1 to 4 heteroatoms selected from O, S, and N. Representative monocyclic aromatic 5- or 6-membered groups include pyridine, pyrimidine, pyridazine, furan, thiophene, thiazole, oxazole, and isoxazole. Representative bicyclic aromatic 9- or 10-membered groups include benzofuran, benzothiophene, indole, pyranopyrrole, benzopyran, quinoline, benzocyclohexyl, and naphthylpyridine.

[0054] As used herein, the term "heteroarylene" means a heteroaryl group that connects. As used herein, the term "heteroalkyl" means an alkyl or cycloalkyl group as defined herein, wherein one of the alkyl hydrogen atoms is substituted with an aryl or heteroaryl group as defined herein. For example, a representative aralkyl group is the benzyl group.

[0055] As used herein, the term "heteroalkylene" means a heteroalkyl group that connects. As used herein, the term "halogen" or "halo" means fluoro, chloro, bromo, and iodo groups. As used herein, the term "copolymer" means a polymer obtained by polymerizing two or more different monomers. The number and nature of each constituent unit can be individually controlled in the copolymer. The constituent units can be arranged, unless otherwise specified, in a purely random, alternating random, regular alternating, regular block, or random block configuration. A purely random configuration can be, for example...x-x-y-z-x-y-y-z-y-z-z-z... or...y-z-x-y-z-y-z-x-x... An alternating random configuration can be...x-y-x-z-y-x-y-z-y-x-z..., and a regular alternating configuration can be...x-y-z-x-y-z-x-y-z.... A regular block configuration (i.e., block copolymer) has the following general configuration:...x-x-x-y-y-y-z-z-z-x-x-x..., and a random block configuration has, for example, the following general configuration:...x-x-x-z-z-x-x-y-y-y-y-z-z-z-x-x-z-z-z-... or, for example,...x-x-x-y-y-y-y-x-x-y-y-y-x-x-x-y-y...

[0056] As used herein, the term "random copolymer" means a copolymer having a mixture of two or more constituent units that is not controlled. The distribution of the constituent units across the polymer backbone (or main chain) is a statistical distribution of the constituent units or approaches a statistical distribution. In some embodiments, it is preferred to have one or more constituent units.

[0057] As used herein, the term "constituent unit" of a polymer means an atom or group of atoms in the polymer that constitutes part of the chain and, if present, together with the atoms or group of atoms of the side chain constitutes part of the chain. A constituent unit can mean a repeating unit. A constituent unit can mean an end group of the polymer chain. For example, the constituent unit of polyethylene glycol can be -CH2CH2O- corresponding to the repeating unit or -CH2CH2OH corresponding to the end group.

[0058] As used herein, the term "repeating unit" corresponds to the smallest constituent unit and is the repetition that constitutes a normal polymer (or oligomeric molecule or block).

[0059] As used herein, the term "end group" means a constituent unit having only one bond to the polymer chain and is located at the end of the polymer. For example, the end group can be derived from a monomer unit at the end of the polymer when the monomer is polymerized. As another example, the end group can be part of a chain extender or initiator used in synthesizing the polymer.

[0060] As used herein, the term "end" of a polymer means a constituent unit located at the end of the polymer backbone. As used herein, the term "end group" means a functional group located at the end of the polymer backbone. As used herein, the term "cation" means a moiety having a positive charge or capable of ionizing to a positively charged site under physiological conditions. Examples of cationic sites include, for example, amino, ammonium, pyridinium, imino, sulfonium, quaternary phosphonium groups, and the like. As used herein, the term "anion" means a moiety having a negative charge or capable of ionizing to a negatively charged site under physiological conditions. Examples of anionic sites include, for example, carboxylate, sulfate, sulfonate, phosphate groups, and the like.

[0061] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, the appropriate methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. Further, the materials, methods, and examples are illustrative only and not intended to be limiting.

[0062] Polymer The present application particularly relates to a polymer comprising repeating units of formula (I):

[0063] [Chemical formula]

[0064] {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 (as used herein, 1, 2, 3, or 4; 1, 2, or 3; 1 or 2; or 1) substituents independently selected from C 1-6 alkyl, halo, nitro (NO2), cyano (CN), SO3 - X + 、PO3 2- X + 2, and COO - X + ; where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are independently SO3- X + 、 PO3 2- X + 2, and COO - X + aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents independently selected from R 1G and R 1H are independently H, aryl, or heteroaryl, and the aryl and heteroaryl are each optionally C 1-6 alkyl, halo, nitro, cyano, SO3 - X + 、 PO3 2- X + 2, and COO - X + substituted by 1, 2, 3, 4, or 5 substituents independently selected from, and X + is H + or a cation; A1 is arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; L1 is an optionally substituted linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by 1, 2, 3, or 4 substituents independently selected from; L2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C1-6 substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl; L3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 substituted with 1, 2, 3, or 4 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl} provided that the repeating unit of formula (I) is not the following.

[0065]

Chemical formula

[0066] In some embodiments, when the polymer comprising formula (I) is a homopolymer, the repeating unit of formula (I) is not the following.

[0067]

Chemical formula

[0068] In some embodiments, for the aforementioned polymer, R 1G and R 1H are independently H.

[0069] In some embodiments, the repeating unit represented by formula (I) is the repeating unit represented by formula (I-A):

[0070]

Chemical formula

[0071] {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1Fis independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, nitro, cyano, SO3 - X + , PO3 2- X + 2, and COO - X + substituted by 1, 2, 3, 4, or 5 substituents independently selected from + H + or a cation, and at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents independently selected from SO3 - X + , PO3 2- X + 2, and COO - X + ; R 2A , R 2B , R 2C , and R 2D are independently selected from H, halo, nitro, cyano, aryl, and heteroaryl; L1 is optionally substituted linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by 1, 2, 3, or 4 substituents independently selected from L2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by 1, 2, 3, or 4 substituents independently selected from L3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from 1, 2, 3, or 4 substituents

[0072] In some embodiments, for any of the foregoing polymers, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, nitro, cyano, SO3 - X + , and PO3 2- X + 2, independently selected from 1, 2, 3, 4, or 5 substituents, and X + is H + or a cation, and at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from SO3 - X + and PO3 2- X + 2.

[0073] In some embodiments, for any of the foregoing polymers, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, and SO3 - X +is substituted by 1, 2, 3, 4, or 5 substituents independently selected therefrom, and X + is H + or a cation, and at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 - X + .

[0074] In some embodiments, for any of the foregoing polymers, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally substituted by 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and SO3 - X + , and X + is H + or a cation, and at least two of R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 - X + .

[0075] In some embodiments, for any of the foregoing polymers, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally substituted by 1, 2, 3, 4, or 5 SO3 - X + , and X+ is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F of which at least two are, independently, aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 - X + .

[0076] In some embodiments, for any of the foregoing polymers, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are, independently, optionally C 1-6 alkyl, halo, SO3 - X + substituted aryl selected independently from 1, 2, 3, 4, or 5 substituents, and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F of which at least two are, independently, aryl substituted by 1, 2, 3, 4, or 5 SO3 - X + . For example, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are, independently, optionally C 1-6 alkyl, and SO3 - X + substituted aryl selected independently from 1, 2, 3, 4, or 5 substituents, and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R1E and R 1F At least two of which are, independently, aryl substituted with 1, 2, 3, 4, or 5 SO3 - X + For example, R 1A R 1B R 1C R 1D R 1E and R 1F are, independently, optionally aryl substituted with 1, 2, 3, 4, or 5 SO3 - X + where X + is H + or a cation, and R 1A R 1B R 1C R 1D R 1E and R 1F At least two of which are, independently, aryl substituted with 1, 2, 3, 4, or 5 SO3 - X + In some embodiments, R 1A R 1B R 1C R 1D R 1E and R 1F are, independently, optionally phenyl substituted with 1, 2, 3, 4, or 5 SO3 - X + where X + is H + or a cation, and R 1A R 1B R 1C R 1D R 1E and R 1F At least two of which are, independently, phenyl substituted with 1, 2, 3, 4, or 5 SO3 - X + In some embodiments, for any of the aforementioned polymers, X

[0077] In some embodiments, for any of the aforementioned polymers, X + is H + or [N(R 5A )(R5B )(R 5C )(R 5D )] + which is a cation selected from the group consisting of, or an alkali metal ion (e.g., Na + Li + , and / or K + ), and R 5A , R 5B , R 5C , R 5D are, independently, H, C 1-6 alkyl, aryl, or heteroaryl. For example, X + may be H + . In some embodiments, X + is [N(R 5A )(R 5B )(R 5C )(R 5D )] + , and R 5A , R 5B , R 5C , R 5D are, independently, H, C 1-6 alkyl, aryl, or heteroaryl. For example, X + may be [NH(ethyl)3] + such as [NH(C 1-6 alkyl)3] + .

[0078] In some embodiments, for any of the foregoing polymers, A1 is arylene, heteroarylene, or aralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A1 is arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A1 is arylene (e.g., phenylene) optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

[0079] In some embodiments, for any of the foregoing polymers, A2 is absent or is arylene, which arylene is optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A2 is absent. In some embodiments, A2 is arylene (e.g., phenylene) optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

[0080] In some embodiments, for any of the foregoing polymers, R 2A , R 2B , R 2C , and R 2D are independently H, halo, nitro, or cyano. For example, R 2A , R 2B , R 2C , and R 2D can be independently H, halo, or nitro. In certain embodiments, R 2A , R 2B , R 2C , and R 2D are independently H or halo. For example, R 2A , R 2B , R 2C , and R 2D can each be H.

[0081] In some embodiments, for any of the foregoing polymers, L1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each of which is optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, aryl, and heteroaryl. For example, L1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each of which is optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, and aryl. In certain embodiments, L1 is arylene, heteroarylene, aralkylen, or heteroaralkylen (each of which is optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo). In some embodiments, L1 is arylene, heteroarylene, aralkylen, or heteroaralkylen, each of which is optionally 1, 2, 3, or 4 C 1-6 substituted by alkyl. In certain embodiments, L1 is arylene, heteroarylene, or aralkylen. For example, L1 can be arylene or heteroarylene, each of which is optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, aryl, and heteroaryl. By way of example, L1 is arylene or heteroarylene, each of which is optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, and aryl. In some embodiments, L1 is arylene or heteroarylene, each of which is optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In certain embodiments, L1 is arylene or heteroarylene, each of which is optionally 1, 2, 3, or 4 C 1-6 substituted by alkyl. For example, L1 can be arylene or heteroarylene. In some embodiments, L1 is arylene optionally substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, L1 is arylene optionally substituted by 1, 2, 3, or 4 C 1-6 alkyl. In some embodiments, L1 is arylene. In some embodiments, L1 is naphthalenylene, phenylene, or C 1-6 alkyl. In some embodiments, L1 is arylene. In some embodiments, L1 is naphthalenylene, phenylene, or C 1-6A phenylene substituted by an alkyl, provided that the phenylene is not p-phenylene. In some embodiments, L1 is a phenylene, provided that the phenylene is not p-phenylene.

[0082] In some embodiments, for any of the aforementioned polymers, L2 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 Substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In certain embodiments, L2 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally 1, 2, 3, or 4 C 1-6 Substituted by an alkyl. For example, L2 can be absent, an arylene, or a heteroarylene. In some embodiments, L2 is absent or an arylene, and the arylene is optionally C 1-6 Substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, L2 is absent or an arylene, and the arylene is optionally 1, 2, 3, or 4 C 1-6 Substituted by an alkyl. In certain embodiments, L2 is absent or an arylene. In some embodiments, L2 is absent or a phenylene. In some embodiments, L2 is absent. In some embodiments, L2 is a phenylene.

[0083] In certain embodiments, for any of the aforementioned polymers, L3 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 Substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, L3 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally 1, 2, 3, or 4 C1-6 It is substituted by alkyl. In certain embodiments, L3 is absent, or is arylene or heteroarylene. In some embodiments, L3 is absent or is arylene, and the arylene is optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In certain embodiments, L3 is absent or is arylene, and the arylene is optionally substituted by 1, 2, 3, or 4 C 1-6 alkyl. In some embodiments, L3 is absent or is arylene. In some embodiments, L3 is absent or is phenylene. In some embodiments, L3 is absent. In some embodiments, L3 is phenylene.

[0084] In some embodiments, for any of the aforementioned polymers, -L3-L2-L1- is independently selected from the following:

[0085]

Chemical formula

[0086] In some embodiments, any of the aforementioned polymers comprises a repeating unit selected from the following:

[0087]

Chemical formula

[0088] {wherein X + is as defined above.}

[0089] In some embodiments, any of the aforementioned polymers comprises a repeating unit selected from the following:

[0090]

Chemical formula

[0091] {wherein X + is as defined above.}

[0092] In some embodiments, the aforementioned polymer is a random copolymer. The random copolymer may further include more hydrophobic repeating units. The hydrophobic repeating unit may have the formula (II):

[0093]

Chemical formula

[0094] {wherein R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; R 3G and R 3H are each independently H, aryl, or heteroaryl, and the aryl and heteroaryl are each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; B1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl: K1 is a linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-) optionally substituted, arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from C alkyl, halo, nitro, cyano, aryl, and heteroaryl; 1-6 K2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C substituted by 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, and heteroaryl;}

[0095] In some embodiments, in any of the hydrophobic repeating units having the foregoing formula (II), R 3G and R 3H are independently H.

[0096] In some embodiments, any of the hydrophobic repeating units having the foregoing formula (II) is a repeating unit of formula (II-A).

[0097]

Chemical formula

[0098] {Wherein, R 3A , R 3B , R 3C , R 3D , R 3E , and R 3Fis independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; R 4A R 4B R 4C and R 4D are independently halo, nitro, cyano, aryl, or heteroaryl; K1 is an optionally substituted linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, where the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; K2 is absent, arylene, or heteroarylene, where the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; K3 is absent, arylene, or heteroarylene, where the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl.}

[0099] In some embodiments, in any of the hydrophobic repeating units having the foregoing formula (II), R 3A R 3B R 3C R 3D R 3E and R 3F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 C 1-6It is substituted by alkyl, nitro, or cyano. In some embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, aryl optionally substituted by 1, 2, 3, 4, or 5 halos. In certain embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, aryl substituted by a substituent selected from optionally 1, 2, 3, 4, or 5 C 1-6 alkyl and halo. In certain embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, aryl substituted by optionally 1, 2, 3, 4, or 5 C 1-6 alkyl. In certain embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, aryl optionally substituted by 1, 2, 3, 4, or 5 halos. In some embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, phenyl substituted by a substituent selected from optionally 1, 2, 3, 4, or 5 C 1-6 alkyl and halo. In some embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, optionally substituted by 1, 2, 3, 4, or 5 C 1-6It is phenyl substituted by alkyl. In some embodiments, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently phenyl optionally substituted by 1, 2, 3, 4, or 5 halos.

[0100] In certain embodiments, in any of the hydrophobic repeating units having the foregoing formula (II), B1 is arylene, heteroarylene, or aralkylene, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, B1 is arylene or heteroarylene, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In specific embodiments, B1 is arylene (e.g., phenylene), optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, B1 is phenyl.

[0101] In some embodiments, B2 is absent or is arylene, and the arylene is optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. For example, B2 may be absent. As another example, B2 is arylene (e.g., phenylene) optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, B2 is phenylene.

[0102] In some embodiments, in any of the hydrophobic repeating units having the foregoing formula (II), R 4A 、R 4B 、R 4C, and R 4D is independently H, halo, nitro, or cyano. In certain embodiments, R 4A , R 4B , R 4C , and R 4D is independently H, halo, or nitro. In some embodiments, R 4A , R 4B , R 4C , and R 4D is independently H or halo. For example, R 4A , R 4B , R 4C , and R 4D can each be H.

[0103] In some embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), K1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, aryl, and heteroaryl. In some embodiments, K1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, and aryl. In certain embodiments, K1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl and halo. In some embodiments, K1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl. For example, K1 can be arylene, heteroarylene, or aralkylene. By way of example, K1 is arylene or heteroarylene, each optionally C 1-6It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, aryl, and heteroaryl. In certain embodiments, K1 is arylene or heteroarylene, each optionally C 1-6 It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, and aryl. In some embodiments, K1 is arylene or heteroarylene, each optionally C 1-6 It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, K1 is arylene or heteroarylene, each optionally 1, 2, 3, or 4 C 1-6 It is substituted by alkyl. For example, K1 can be arylene or heteroarylene. In some embodiments, K1 is optionally C 1-6 It is arylene substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. For example, K1 is optionally 1, 2, 3, or 4 C 1-6 It is arylene substituted by alkyl. By way of example, K1 can be naphthalenylene, phenylene, or C 1-6 It can be phenylene substituted by alkyl. For example, K1 can be phenylene.

[0104] In some embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), K2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, K2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally 1, 2, 3, or 4 C 1-6 It is substituted by alkyl. For example, K2 can be absent, arylene, or heteroarylene. By way of example, K2 is absent or arylene, and the arylene is optionally C1-6 It is substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In some embodiments, K2 is absent or is arylene, and the arylene is optionally 1, 2, 3, or 4 C 1-6 Substituted by alkyl. In some embodiments, K2 is absent or is arylene. For example, K2 is absent or is phenylene. In some embodiments, K2 is absent. In some embodiments, K2 is phenylene.

[0105] In some embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), K3 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 Substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. In certain embodiments, K3 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally 1, 2, 3, or 4 C 1-6 Substituted by alkyl. In some embodiments, K3 is absent, arylene, or heteroarylene. For example, K3 may be absent or arylene, and the arylene is optionally C 1-6 Substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo. As an example, K3 may be absent or arylene, and the arylene is optionally 1, 2, 3, or 4 C 1-6 Substituted by alkyl. In some embodiments, K3 is absent or arylene. For example, K3 may be absent or phenylene. As an example, K3 may be absent. As another example, K3 may be phenylene.

[0106] In certain embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), K3-K2-K1- is independently selected from the following.

[0107]

Chem.

[0108] In some embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), the hydrophobic repeating unit is selected from the following.

[0109]

Chem.

[0110] In some embodiments, in any of the hydrophobic repeating units having the aforementioned formula (II), the hydrophobic repeating unit is selected from the following.

[0111]

Chem.

[0112] The disclosure of the present application particularly includes a first repeating unit selected from the following and any combination thereof

[0113]

Chem.

[0114] {wherein X + is as defined above} and a second repeating unit selected from the following and any combination thereof

[0115]

Chem.

[0116] Disclosed is a polymer containing the same, wherein the molar ratio of the first repeating unit to the second repeating unit is in the range of 1:99 to 99:1.

[0117] The disclosure of the present application particularly includes a first block selected from the following and any combination thereof

[0118]

Chemical formula

[0119] {wherein X + is as defined above, and n is an integer from 3 to 100} and a second block selected from the following and any combination thereof

[0120]

Chemical formula

[0121] {wherein m is an integer from 3 to 100} Disclosed is a random block polymer containing the same, wherein the molar ratio of the first block to the second block is in the range of 1:99 to 99:1.

[0122] The disclosure of the present application particularly discloses a compound represented by formula (III).

[0123]

Chemical formula

[0124] {wherein R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F are independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, SO3 - X+ , PO3 2- X + 2, and COO - X + is substituted by 1, 2, 3, or 4 substituents independently selected from, and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F at least two of which are independently substituted by 1, 2, 3, 4, or 5 substituents selected from SO3 - X + , PO3 2- X + 2, and COO - X + is aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents selected from; A1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl}{ However, the compound represented by formula (III) is not the following.

[0125]

Chemical formula

[0126] In some embodiments, any compound represented by formula (III) includes a compound represented by formula (III-A).

[0127]

Chemical formula

[0128] wherein R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, SO3 - X + 、PO3 2- X + 2, and COO - X + ; X + is H + or a cation; and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents selected from SO3 - X + 、PO3 2- X + 2, and COO - X + ; R 2A 、R 2B 、R 2C 、and R 2D are each independently selected from H, halo, nitro, cyano, aryl, and heteroaryl}{ provided that the compound represented by formula (III-A) is not the following.

[0129]

Chemical formula

[0130] In some embodiments, for any compound represented by formula (III), R 1A 、R 1B 、R 1C 、R 1D 、R1E and R 1F is independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, SO3 - X + and PO3 2- X + is substituted by 1, 2, 3, 4, or 5 substituents independently selected from 2 to, X + is H + or a cation, R 1A R 1B R 1C R 1D R 1E and R 1F at least two of are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents independently selected from SO3 - X + and PO3 2- X + is substituted by 1, 2, 3, 4, or 5 substituents independently selected from 2 to. In some embodiments, R 1A R 1B R 1C R 1D R 1E and R 1F is independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, and SO3 - X + is substituted by 1, 2, 3, 4, or 5 substituents independently selected from, X + is H + or a cation, R 1A R 1B R 1C R 1D R 1E and R 1F at least two of are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 - X + is substituted by. In some embodiments, R 1A R 1B R 1C R 1D R 1E and R 1Fis independently aryl or heteroaryl, each optionally C 1-6 alkyl and SO3 - X + is substituted by 1, 2, 3, 4, or 5 substituents independently selected from + H + or a cation, and at least two of R 1A R 1B R 1C R 1D R 1E R 1F and R - X + are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 1A R 1B R 1C R 1D R 1E R 1F is independently aryl or heteroaryl, each optionally substituted by 1, 2, 3, 4, or 5 SO3 - X + where X + is H + or a cation, and at least two of R 1A R 1B R 1C R 1D R 1E R 1F and R - X + are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 SO3 1A R 1B R 1C R 1D R 1E R 1F is independently aryl, optionally substituted by 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, and SO3 - X + where X + is H + or a cation, and R1A , R 1B , R 1C , R 1D , R 1E , and R 1F At least two of them are, independently, aryl substituted by SO3 - X + . For example, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F can be independently aryl, optionally substituted by 1, 2, 3, 4, or 5 substituents selected independently from C 1-6 alkyl and SO3 - X + , and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F At least two of them are, independently, aryl substituted by 1, 2, 3, 4, or 5 SO3 - X + . In a particular embodiment, R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F can be independently aryl, optionally substituted by 1, 2, 3, 4, or 5 SO3 - X + , and X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F At least two of them are, independently, aryl substituted by 1, 2, 3, 4, or 5 SO3 - X + . For example, R 1A , R 1B , R 1C , R1D , R 1E , and R 1F is, independently, optionally 1, 2, 3, 4, or 5 SO3 - X + -substituted phenyl, where X + is H + or a cation, and R 1A , R 1B , R 1C , R 1D , R 1E , and R 1F at least two of which are, independently, 1, 2, 3, 4, or 5 SO3 - X + -substituted phenyl.

[0131] In some embodiments, for any compound represented by formula (III), X + is H + , or [N(R 5A )(R 5B )(R 5C )(R 5D )] + , a cation selected from the group consisting of alkali metal ions (e.g., Na + , Li + , and / or K + ), and R 5A , R 5B , R 5C , R 5D are, independently, H, C 1-6 alkyl, aryl, or heteroaryl. In certain embodiments, X + is H + . In some embodiments, X + is [N(R 5A )(R 5B )(R 5C )(R 5D )] + , and R 5A , R 5B , R 5C , R 5D are, independently, H, C 1-6 alkyl, aryl, or heteroaryl. For example, X + is [NH(C 1-6(Alkyl)3 + can be.

[0132] In some embodiments, for any compound represented by formula (III), A1 is arylene, heteroarylene, or aralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A1 is arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In certain embodiments, A1 is arylene (e.g., phenylene), optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A1 is phenylene.

[0133] In some embodiments, for any compound represented by formula (III), A2 is absent or is arylene, which arylene is optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In certain embodiments, A2 is absent. In some embodiments, A2 is arylene (e.g., phenylene), optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, A2 is phenylene.

[0134] In some embodiments, for any compound represented by formula (III), R 2A , R 2B , R 2C , and R 2D are independently H, halo, nitro, or cyano. In certain embodiments, R 2A , R 2B , R 2C , and R 2D are independently H, halo, or nitro. For example, R2A , R 2B , R 2C , and R 2D may independently be H or halo. By way of example, R 2A , R 2B , R 2C , and R 2D may each be H.

[0135] The disclosure of the present application further includes a method for manufacturing any of the aforementioned polymers, which comprises preparing a mixture containing a compound represented by formula (III) and at least one compound represented by formula (IV)

[0136] [Chemical formula]

[0137] {wherein, L1 is an optionally substituted linking heteroatom (e.g., -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L3 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted by 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; D1 and D2 are independently H, R 1G , R 1H , R3G , R 3H , or a protecting group (e.g., a silyl protecting group, a substituted silyl protecting group, a trialkylsilyl protecting group, a silyl ether protecting group, a trialkylsilyl ether protecting group, a trimethylsilyl ether), where R 1G and R 1H are as defined above, and R 3G and R 3H are as defined above}; and reacting a compound represented by formula (III) or formula (III-A) with at least one compound represented by formula (IV) by a Diels Alder reaction to obtain the aforementioned polymer: comprising.

[0138] In some embodiments, the method for producing the aforementioned polymer comprises reacting a compound represented by formula (III) with a compound represented by formula (IV) by a Diels Alder reaction, and the Diels Alder reaction comprises heating the mixture at a temperature of 150 °C to 300 °C (e.g., 180 °C to 230 °C) for 5 minutes to 30 days (e.g., 60 minutes to 7 days). This method further comprises deprotecting the compound represented by formula (IV) before or during the Diels Alder reaction when at least one of D1 and D2 is a protecting group.

[0139] In certain embodiments, the aforementioned mixture in the method further comprises a compound represented by formula (V).

[0140]

Chemical formula

[0141] {wherein, R 3A , R 3B , R 3C , R 3D , R 3E , and R 3F are independently aryl or heteroaryl, each optionally C 1-6Substituted with 1, 2, 3, 4, or 5 substituents independently selected from alkyl and halo, X + is H + or a cation; B1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl}

[0142] In some embodiments, the aforementioned mixture in the method further comprises a compound represented by formula (V-A).

[0143]

Chemical formula

[0144] {In the formula, R 3A , R 3B , R 3C , R 3D , R 3E and R 3F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo, X + is H + or a cation; R 4A , R 4B , R 4C and R 4D are independently halo, nitro, cyano, aryl, or heteroaryl}

[0145] This application discloses, inter alia, a method for producing a random block copolymer, the method comprising a first polymer represented by formula (VI):

[0146]

Chemical formula

[0147] {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、R 1F 、R 1G 、R 1H 、R 2A 、R 2B 、R 2C 、and R 2D 、A1, A2, L1, L2, and L3 are as defined above; n is an integer from 3 to 100; A is a reactive first terminal group}, and a second polymer represented by formula (VII):

[0148]

Chemical formula

[0149] {wherein, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、R 3F 、R 3G 、R 3H 、R 4A 、R 4B 、R 4C 、R 4D 、B1, B2, K1, K2, and K3 are as defined above; m is an integer from 3 to 100; B is a second reactive terminal group configured to react with A} preparing a mixture of; and Reacting A (for example, an alkyne having reactivity with respect to tetracyclone) or tetracyclone (having reactivity with respect to an alkyne) and B (for example, tetracyclone or an alkyne) to obtain a random block copolymer represented by formula (VIII); comprising.

[0150]

Chemical formula

[0151] However, the molar ratio of the first block to the second block is in the range of 1:99 to 99:1.

[0152] The disclosure of the present application discloses, among other things, a method for producing the aforementioned polymer. The production method involves preparing a mixture of a compound represented by formula (III) and at least one compound represented by formula (IX):

[0153]

Chemical formula

[0154] {wherein, L1 is an optionally substituted linking heteroatom (for example, -N-, -O-, -S-, -C(O)-, or -SO2-), arylene, heteroarylene, aralkylen, or heteroaralkylen, and the arylene, heteroarylene, aralkylen, and heteroaralkylen are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, and is substituted by 1, 2, 3, or 4 substituents independently selected therefrom; L2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, and is substituted by 1, 2, 3, or 4 substituents independently selected therefrom; L3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently substituted by 1, 2, 3, or 4 substituents selected therefrom; D3 is H, R 1G 、R 1H 、R 3G 、R 3H 、or a protecting group (e.g., silyl protecting group, substituted silyl protecting group, trialkylsilyl protecting group, silyl ether protecting group, trialkylsilyl ether protecting group, trimethylsilyl ether), and R 1G and R 1H are as defined above, and R 3G and R 3H are as defined above; D4 is halo}; Reacting a compound represented by formula (III) or formula (III-A) with at least one compound represented by formula (IX) by a Diels Alder reaction to obtain a halogenated intermediate compound; Coupling the halogenated intermediate compound in the presence of an organopalladium catalyst, an organocopper catalyst, an organonickel catalyst, an organomanganese catalyst, an organoplatinum catalyst, an organoruthenium catalyst, or a combination thereof to obtain the polymer of the present application; Including. The method further includes deprotecting the compound represented by formula (IV) before or during the Diels Alder reaction when at least one of D1 and D2 is a protecting group. The mixture may further include a compound represented by formula (V).

[0155]

Chemical formula

[0156] {In the formula, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R3F is independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo, and X + is H + or a cation; B1 is arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B2 is absent, arylene, or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl} In some embodiments, the mixture further comprises a compound represented by formula (V-A).

[0157]

Chemical formula

[0158] {wherein, R 3A , R 3B , R 3C , R 3D , R 3E , and R 3F are independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo, and X + is H + or a cation; R 4A , R 4B , R 4C , and R 4D are independently halo, nitro, cyano, aryl, or heteroaryl.}

[0159] For any compound / polymer represented by the foregoing formulas (V), (V-A), (VII), and (VIII), R 3A R 3B R 3C R 3D R 3E R 3F R 3G R 3H R 4A R 4B R 4C R 4D B1, B2, K 1、 K2, K3 can be as per any of the foregoing arbitrary stipulations.

[0160] For any compound / polymer represented by the foregoing formulas (IV), (VI), (VIII), and (IX), R 1A R 1B R 1C R 1D R 1E R 1F R 1G R 1H R 2A R 2B R 2C and R 2D A1, A2, L1, L2, and L3 can be as per any of the foregoing arbitrary stipulations.

[0161] Polyvalent linking group In some embodiments, the polymers of the present application are linear. In certain embodiments, the polymers of the present application are branched. When the polymer is branched, the polymer includes a polyvalent linking group M1 that is directly bonded via a covalent bond to at least three repeating units (e.g., an anionic repeating unit disclosed herein, a hydrophobic repeating unit disclosed herein, or any combination thereof). As used herein, the term polyvalent means a site that is trivalent or higher (e.g., tetravalent, pentavalent, hexavalent, etc.). For example, M1 can be a trivalent, tetravalent, pentavalent, or hexavalent linking group. By way of example, the polyvalent linking group M1 can be a carbon atom, a heteroatom (e.g., N, P, or B), a polyvalent aryl, a polyvalent heteroaryl, a polyvalent aralkyl, or a polyvalent heteroaralkyl, each of which is bonded to at least three repeating units. The carbon atom, heteroatom (e.g., P), polyvalent aryl, polyvalent heteroaryl, polyvalent aralkyl, or polyvalent heteroaralkyl is each optionally C 1-6 substituted with 1, 2, or 3 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl. In some embodiments, the polyvalent linking group is selected from trivalent nitrogen, tetravalent carbon, trivalent phenyl, trivalent pyridyl, trivalent pyrazyl, tetravalent phenyl, tetravalent pyridyl, tetravalent pyrazyl, pentavalent phenyl, pentavalent pyridyl, and hexavalent phenyl. The trivalent phenyl and trivalent pyridyl are each optionally C 1-6 substituted with 1, 2, or 3 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl. The tetravalent phenyl, tetravalent pyridyl, and trivalent pyrazyl are each optionally C 1-6 substituted with 1 or 2 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl. The pentavalent phenyl is optionally C 1-6 substituted with a substituent independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl.

[0162] For example, the polyvalent linking group can be the following.

[0163]

Chem.

[0164] In some embodiments, the polyvalent linking group is as follows.

[0165]

Chem.

[0166] Membrane The disclosure of the present application further discloses, inter alia, an ionic membrane comprising any of the aforementioned polymers. The ionic membrane can have proton conductivity (e.g., ex situ conductivity, in-plane), and when measured at a temperature of 20 °C to 90 °C using AC impedance spectroscopy (electrochemical impedance spectroscopy) at a relative humidity of 30% to 100%, it has a conductivity of 0.001 mS cm -1 ~1000 mS cm -1 (e.g., 0.001 mS cm -1 ~450 mS cm -1 ), or when measured using AC impedance spectroscopy (electrochemical impedance spectroscopy) in water at 80 °C, it can have a conductivity of 1 mS cm -1 ~1000 mS cm -1 (e.g., 50 mS cm -1 ~450 mS cm -1 ).

[0167] The disclosure of the present application further discloses, inter alia, an ionomer comprising any of the aforementioned polymers. The ionomer can be incorporated into the catalyst layer of a fuel cell, an electrolyzer, or other electrochemical devices. For example, the ionomer can be incorporated into the catalyst layer at a solid content of 5 wt% to 45 wt% (e.g., 10 wt% to 45 wt%, 15 wt% to 45 wt%, 30 wt% to 45 wt%, 5 wt% to 30 wt%, 15 wt% to 45 wt%, 30 wt% to 45 wt%, 10 wt% to 30 wt%, 10 wt% to 20 wt%, or 15 wt% to 30 wt%).

[0168] In some embodiments, the ionomers disclosed herein are incorporated into a cation exchange resin.

[0169] The polymers disclosed herein may exhibit less than 20% (e.g., less than 10%) mass loss when exposed to a Fenton's reagent at a temperature of 80 °C and a pressure of 1 atmosphere for 0 to 180 minutes (e.g., 0 to 90 minutes, or 0 to 60 minutes). The polymers disclosed herein may have an ion exchange capacity of 2 to 4.5 (e.g., 3.2 to 3.8) as evaluated by acid-base titration. The evaluation by acid-base titration is performed, for example, by immersing a sample in a pH 7, 1 M NaCl solution for 48 hours to convert the membrane in the acid form (-SO3 - H + ) to the corresponding sodium salt (-SO3 - Na + ), and then returning the resulting acidic solution to pH 7 by titration using a standard titration solution (e.g., 0.01 M NaOH solution, Sigma Aldrich). The IEC can be calculated from the volume and molar concentration of the standard titration solution used and the dry mass of the sample being titrated. Those skilled in the art will understand that the titration can be performed using other cations, such as KCl. In this case, the polymer is converted to (-SO3 - K + ), and then the titration is performed. The titration solution can also be changed.

[0170] Synthesis In some embodiments, the polyphenylene precursors disclosed herein can be produced according to Scheme 1.

[0171] Scheme 1: General scheme for synthesizing a precursor compound into the polyphenylene disclosed herein ([HN(CH2CH3)3] + is shown as an example of a non-limiting cation)

[0172]

Chemical formula

[0173] {In the scheme, (i) KOH, EtOH, reflux; (ii) Me3SiOSO2Cl, 1,2-dichloroethane; (iii) Et3N, n-BuOH; Ar is arylene, heteroarylene, aralkylene, or heteroaralkylene or a linking site where two of these linking sites are linked to each other to form two linked aromatic groups, and Ar is arylene.}

[0174] The tetraketone of Scheme 1 can be synthesized by the following synthetic steps.

[0175] Scheme 2: General synthetic scheme of tetraketone

[0176]

Chemical formula

[0177] {In the scheme, (iv) Pd(PPh3)2Cl2, CuI, HNEt2; (v) I2, DMSO, reflux; Ar is as defined in Scheme 1.}

[0178] Examples of the X-Ar-X compound include the following.

[0179]

Chemical formula

[0180] Compounds 1, 2, 4, 5, and 6 are available for purchase from, for example, Sigma-Aldrich Co. LLC., compounds 3, 7, and 9 are available for purchase from, for example, TCI Chemicals Industry Co., Ltd., and compound 9 is available for purchase from, for example, Oakwood Products, Inc.

[0181] As an example, when used as starting materials for Schemes 2 and 1, the resulting precursor compounds can be as follows when Compound 2A is used as X-Ar-X.

[0182] [Chemical formula]

[0183] As another example, when used as starting materials for Schemes 2 and 1, the resulting precursor compounds can be as follows when Compound 6 is used as X-Ar-X.

[0184] [Chemical formula]

[0185] In some embodiments, the polymers disclosed in the present application can be synthesized via Scheme 3 (for example, showing naphthyl-linked polyphenylene), where a protecting group such as TMS (trimethylsilyl ether) is first removed from the dialkyne compound, and then the resulting dialkyne is reacted with a precursor compound by a Diels-Alder reaction to obtain a polymer.

[0186] Scheme 3: Synthesis of Naphthyl-Linked Polyphenylene

[0187] [Chemical formula]

[0188] In some embodiments, instead of first deprotecting the dialkyne compound, deprotection can occur in situ during polymerization (for example, Scheme 4).

[0189] Scheme 4: In Situ Deprotection of Protected Dialkyne Compounds

[0190] [Chemical formula]

[0191] In some embodiments, the polymers disclosed in the present application can be synthesized by the following synthetic schemes.

[0192] Scheme 5: Synthesis of exemplary polymers disclosed in the present application by coupling via organometallic catalysts. One embodiment of the polymer is shown below, and those skilled in the art will understand that other linking groups mentioned can also be synthesized by synthetic methods similar to this scheme.

[0193]

Chemical formula

[0194] Some exemplary linking groups useful for coupling via organometallic catalysts shown in Scheme 5 include the following.

[0195]

Chemical formula

[0196] Polyfunctional monomer As described above, in some embodiments, the polymers disclosed in the present application are branched. Without wishing to be bound by theory, in some embodiments, the branched polymers may have physical properties superior to those of their linear polymer analogs. The branched polymers can have a polyvalent linking group directly covalently bonded to at least three repeating units (e.g., anionic, hydrophobic, or combinations thereof). The branched polymers can be synthesized via the addition of a polyfunctional linking group (e.g., dienophile) having three or more reactive functional groups. For example, the outline of the case of a trifunctional monomer is shown in Scheme 6(b) below. Scheme 6(a) shows the synthesis of a linear sulfonated polymer.

[0197] Schemes 6(a) and 6(b): Sulfonated and phenylated polyphenylene using trifunctional monomers to introduce branches.

[0198]

Chem.

[0199] Representative functional monomers are shown below.

[0200]

Chem.

[0201] {wherein, L3' is each an optionally substituted heteroatom (e.g., N, P, B), polyvalent aryl, polyvalent heteroaryl, polyvalent aralkyl, or polyvalent heteroaralkyl, and the polyvalent aryl, polyvalent heteroaryl, polyvalent aralkyl, and polyvalent heteroaralkyl are each optionally substituted with 1, 2, or 3 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L2' is absent or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L1' is absent or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; D1', D2', and D3' are independently H, R 1G 、R 1H 、R 3G 、R 3H, or a protecting group (e.g., a silyl protecting group, a substituted silyl protecting group, a trialkylsilyl protecting group, a silyl ether protecting group, a trialkylsilyl ether protecting group, a trimethylsilyl ether), and R 1G and R 1H are as defined above, and R 3G and R 3H are as defined above.}

[0202] As shown in Scheme 6, the polyvalent linking group can be introduced into the polymer using a hetero-functional aromatic system terminated with an alkyne or a protected alkyne, which can later be used in combination with a dienophile monomer such as anionic 1c to generate a branching point. The dienophile monomer can be a mixture of an anionic monomer and a hydrophobic uncharged monomer. The hetero-functional aromatic system can be small, such as 1,3,5-triethynylbenzene, or larger with more than one aromatic group. The hetero-functional aromatic system can include a heteroaromatic ring such as pyridine (shown below) or a pyrazine-containing linking group.

[0203]

Chemical Structure

[0204] In some embodiments, the hetero-functional aromatic system can contain a heteroatom such as nitrogen or be centered around carbon as shown below.

[0205]

Chemical Structure

[0206] In some embodiments, the terminal acetylene group is replaced by H.

[0207] Further examples of hetero-functional aromatic systems based on hexa- or penta-phenylbenzene compounds are shown below. This gives a 5- or 6-functional linking group.

[0208]

Chem.

[0209] In some embodiments, the branched polymers disclosed in the present application can be synthesized using monomers having three or more ketone sites, and examples of the monomers include compounds represented by the following formula (V-B).

[0210]

Chem.

[0211] {In the formula, R 1A and R 1B are as defined above respectively, and at least one (for example, at least two) of R 1A and R 1B is independently an aryl or heteroaryl substituted with one, two, three, four, or five substituents selected independently from SO3 - X + 、PO3 2- X + 2, and COO - X + , and X + is as defined above.} In some embodiments, R 1A and R 1B do not exist, and the monomer represented by the formula (V-B) is hydrophobic and uncharged.

[0212] The aforementioned polyfunctional linking groups or monomers can be used as one of the starting materials in the reaction mixture to obtain branched polymers. The polyfunctional linking groups can be present in an amount of 0.001 to 20 mol% based on Compound III. In some embodiments, the aforementioned polyfunctional linking groups or monomers can be present in an amount of 0.001 to 20 mol% based on Compound III-A.

[0213] In some embodiments, any of the foregoing polymers can be incorporated into an ionic membrane and / or an ionomer. The ionomer can be incorporated, for example, into the catalyst layer of a fuel cell, an electrolytic cell, or other electrochemical devices.

[0214] Examples of anionic polyphenylene monomers, oligomers, and polymers are shown below. Example 1 shows the controlled synthesis of sulfonated monomers and their utilization in the synthesis of sulfonated, branched oligophenylene and homopolymers (sPPP-H + ). The position and number of sulfonic acid groups are precisely controlled. Example 2 shows two novel sulfonated phenylated polyphenylene ionomers, which can be used in polyaromatic proton exchange membranes. Both types of ionomers exhibited high ion exchange capacity and were insoluble in water even when heated. Also, the ionomers exhibited high proton conductivity in both fully hydrated and reduced relative humidity states. Furthermore, they showed remarkable recoverability against attack by free radicals. Example 3 shows the improvement in the stability and efficiency of sulfonated poly(para-phenylene).

[0215] Examples Example 1: Synthesis and Characterization of Sulfonated Monomers, Oligomers, and Polymers The synthesis and property evaluation of oligo- and poly-phenylene that are structurally defined, sulfonated-phenylated, and incorporated with bis-tetracyclone monomer of tetrasulfonic acid are disclosed. The monomer can be used in [4+2] Diels-Alder addition cyclization to obtain well-defined sulfonated oligophenylene and pre-functionalized polyphenylene homopolymers. The property evaluation of oligophenylene suggests that meta-meta adduct and para-para adduct can be obtained in a 1:1 ratio. These functionalized monomers and subsequent coupling provide a route to synthesize novel, sterically hindered sulfonated polyphenylene with unprecedented structural control.

[0216] Strategies leading to the controlled synthesis of novel sulfonated monomers (Scheme 1-1) are shown below. Sulfonated branched oligophenylene and homopolymers ((sPPP-H + , Figure 1) are presented in terms of the utility of the monomers in the synthesis with precise control of the position and number of sulfonic acids (Figure 2).

[0217] Scheme 1-1: Synthesis of sulfo-phenylated dienes and polyphenylene homopolymers

[0218]

Chemical formula

[0219] i) KOH / EtOH, reflux; ii) Me3SiOSO2Cl, 1,2-C2H4Cl2; iii) NEt3, n-BuOH; iv) PhNO2: sand bath (180 °C, 12 h) or microwave synthesizer (195 °C, 2 h); v) 2M KOH; vi) 0.5M H2SO4 The sulfonated diene was prepared as shown in Scheme 1-1. Tetracyclone 3 was sulfonated using trimethylsilyl chlorosulfonate to obtain novel disulfonic acid tetracyclone 4. The 1In the 1H NMR spectrum, a doublet (integral value 4H) appears at 7.46 ppm, suggesting a symmetric structure. By using COSY, it is found that this doublet correlates with a doublet at 7.11 ppm (4H). These two doublets suggest disulfonation at the p-positions of the two phenylene rings parallel to the ketone in 3. Due to the delocalization of the charge by the ketone, sulfonation proceeds at this position. The remaining 10 protons are observed as doublets at 6.95 ppm and 7.22 - 7.29 ppm for the unsulfonated phenylene, and as multiplets at 7.22 ppm - 7.29 ppm and 6.95 ppm for the unsulfonated phenylene. The acidic proton in 4 was replaced by a triethylammonium cation by treatment with triethylamine to obtain 5.

[0220] The symmetric tetrasulfonated monomer 8 was synthesized in the same manner as 4. 8 was 1 analyzed by 1H NMR, and two doublets were observed at low magnetic fields (7.55 and 7.50 ppm). By using COSY, these protons correlate with doublets at 7.10 ppm and 7.16 ppm, which is consistent with the p-substitution of the phenyl ring adjacent to the ketone. The signal of the acidic proton appears at 7.57 ppm. 1 By 1H NMR analysis, since H core appears as a singlet peak at 6.87 ppm, it is suggested that 8 is symmetric. Using COSY and 1D NOE analysis, it was determined whether all four sulfonic acid groups are separated from each other ("H" conformation) or two are close to each other ("A" conformation). The Hα1 and Hβ1 protons (7.55 and 7.10 ppm, respectively) do not show spatial correlation with the protons (H o , H m and H p ) on the unsulfonated phenyl ring, while the Hα2 and Hβ2 (7.51 and 7.17 ppm, respectively) do. From this, it is suggested that 8 exclusively has the "A" conformation in solution.

[0221] Compound 8 is converted to ammonium derivative 9 prior to Diels - Alder (D - A) coupling in order to improve its thermal stability. By 1 1H NMR analysis, Et3NH + : HN + (8.88 ppm); additional signals from - CH2 - (two overlapping quartets at 3.09 and 3.10 ppm); and - CH3 (1.16 ppm) were observed.

[0222] The synthesis of bis - dienophile 13 is disclosed below. Oligomers 14 and 16 were synthesized (Scheme 1 - S1), and the D - A coupling of comonomers 9 and 13 was investigated. Compound 14 was obtained by the D - A addition cyclization of 2 molar equivalents of dienophile 13 to 5. The D - A proton (H DA ) is derived from the terminal alkyne of 13, Hα1 and Hβ1 are the ortho and meta protons of the sulfonic acid group of the phenyl ring adjacent to H DA respectively, and Hα2 and Hβ2 are analogous protons located on the other sulfonated phenyl ring. From the 1 1H NMR spectrum of 14, it is revealed that H DA is at 7.38 ppm and H core of the central phenyl ring is at 6.93 ppm. For the peripheral phenyl rings, signals at 7.36 ppm (Hα1) and 7.23 ppm (Hα2) corresponding to protons on the sulfonated rings correlate to peaks at 7.14 (Hβ1) and 6.77 (Hβ2) ppm respectively, reflecting different chemical environments. Signals corresponding to the non - sulfonated phenyl ring are observed at 6.96 - 6.83 ppm. The possibility of conformational isomers was investigated using 1D NOE. Irradiation of H DA at 7.38 ppm reveals the vicinity of H core at 6.88 ppm (singlet peak) and Hβ1 at 7.11 ppm. Irradiation of Hβ1 at 7.11 ppm confirms the vicinity of H core and H DA . Irradiation of Hβ1 reveals the corresponding H DAAlthough it does not imply the vicinity of, there is a correlation between unsulfonated phenylene (6.88 ppm, 1 peak) and H core (two peaks). This suggests that compound 14 also has the "A" conformation in solution.

[0223] Compound 16 was synthesized by the D-A cycloaddition of 9 and 15. The protons of 16 derived from the phenyl ring of 15 are observed at 7.00, 6.68, and 6.62 ppm. According to the literature, in this reaction, as shown in Scheme 1-S10, both m- and p-additions can occur, so a pure isomer cannot be obtained. As a result, three positional isomers of 16 are observed, which are core For H, three main NMR signals are observed at 6.41, 6.31, and 6.14 ppm, corresponding to the p-p, m-m, and m-p isomers, respectively. The signal at 7.28 ppm is due to the H DA proton, which can be seen from the lack of correlation with other protons in the molecule in COSY. The spectrum of compound 16 shows signals at 7.23 and 7.11 ppm due to Hα1, signals at 6.57 and 6.77 ppm due to Hβ1, signals at 7.55 and 7.46 ppm due to Hα2, and signals at 6.93 and 6.85 ppm due to Hβ2. Using COSY, the pairing of Hα1 and Hβ1, as well as the pairing of Hα2 and Hβ2, is established. The downfield shift of the Hα proton is correlated with the upfield shift of the Hβ proton (for example, the peaks at 7.23 and 6.57 are correlated), and a similar situation is also seen in the downfield pair (for example, the peaks at 7.46 and 6.85 ppm are correlated). This is interpreted to mean that while 14 has the "A" conformation exclusively, 16 consists of a mixture of the "H" and "A" conformations. For each conformation, a set of three positional isomers can occur, resulting in a total of six peaks, and the peaks corresponding to the H core protons of the three positional isomers of each conformation are observed between 6.00 ppm and 6.50 ppm.

[0224] Protected sulfonated poly(phenylene), sPPP-NHEt3 + (Scheme 1-S12) was synthesized by [4+2] D-A cycloaddition of comonomers 9 and 13. GPC analysis suggested a Mn of 186,000 Da and a polydispersity index (PDI) of 1.44. sPPP-NHEt3 + of 1 The methyl groups of NHEt3 + appeared at 1.12 ppm (36H) by 1H NMR analysis and were later used as an internal standard in the quantification of residual protons. The methylene protons (24H) appeared as two overlapping quartets at 3.05 ppm, and the ammonium protons (4H) were found at 8.92 ppm. The signals of the protons of the polymer backbone were observed in the region of 5.90 ppm ~7.60 ppm. The integration ratio of the methyl group of NHEt3 + salt to the polymer backbone was 1:1, demonstrating that the sulfonic acid groups in the salt form were maintained in the D-A reaction. In the model compound, the polymer showed evidence of positional isomers: the signal of H core was found for the m-m (6.32 ppm), p-p (6.17 ppm), and m-p (5.98 ppm) isomers. Integration of these peaks resulted in an isomer composition containing 42%, 40%, and 18%, respectively.

[0225] The effect of positional isomerization was also observed for the H DA protons and can be para (H core ) or meta (H DA1 ) with respect to the central phenyl ring (i.e., H DA2 ). However, the H DA protons were observed as a broad peak near 7.23 ppm, which was due to partial shielding by its low intensity and Hα1 located at 7.43 ppm (assigned by COSY analysis of 14 and 16). The model compound 16 presented the signal of Hα1 at 7.43 ppm by COSY analysis, while sPPP-NHEt3 +According to the COSY analysis, the peak at 7.22 ppm has no correlation with any other peaks. Therefore, we assign this signal to the H of the polymer. DA Protons on the sulfonated phenyl ring that are meta or para to the central phenyl ring appear at 7.43 (Hα2) and 7.18 (Hα1) ppm. According to the COSY analysis, these correlate with 6.82 (Hβ2) and 6.64 (Hβ1) ppm respectively. Protons on the unsulfonated outer phenyl ring, namely H o , H m and H p have signals at 7.34, 6.53, and 7.02 ppm respectively.

[0226] sPPP-NHEt3 + After the conversion from sPPP-NHEt3 to sPPP-H + , a film was cast using DMSO. The ion exchange capacity (IEC) was determined to be 3.47 meq g -1 , which was close to the theoretical value of 3.70 meq g -1 . This is a very high IEC value for an aromatic polymer, and it was found that the polymer is insoluble and independent in water at room temperature (water content, 85 wt%). For comparison, as previously reported, postsulfonated polyphenylene (see, for example, Fujimoto, C. H.; Hickner, M. A.; Cornelius, C. J.; Loy, D. A. Macromolecules 2005, 38, 5010) has an average of four sulfonic acid groups per repeating unit and an IEC of 2.2 meq g -1 , but forms a hydrogel in water. The sPPP-H + film dissolved when placed in the Fenton's reagent, but subsequent 1 1H NMR analysis revealed no change in the chemical structure, suggesting that it has very high oxidative stability.

[0227] sPPP-H +(Figure 3) The proton conductivity was investigated using samples saturated with water and partially hydrated (30 - 95% RH) membranes at 30 °C. As is commonly seen in aromatic membranes, the proton conductivity, as a function of RH, increases from a low value of 8.65 mS cm at 40% RH -1 to 106 mS cm at 95% RH -1 . In contrast to most aromatic membranes, sPPP-H + shows conductivity comparable to that of NR211 at low RH. The conductivity of sPPP-H + decreases when hydrated (from 106 mS cm at 95% RH -1 to 77 mS cm -1 ), which reflects the high water uptake ability of sPPP-H + when in contact with liquid water and the resulting decrease in the acid concentration [-SO3H] by analysis (0.92 M for sPPP-H + and 1.55 M for N211).

[0228] Preliminary studies were conducted on sPPP-H + incorporated into the cathode catalyst layer (CCL) of a PEMFC. The performance of the sPPP-H + -based CCL (90% RH) was compared with that when Nafion® D520 was used in the CCL (Figure 4, in both cases, N211 was used as the membrane), and reasonable performance was found in the aromatic ionomer. However, when the cathode inlet was reduced to 0% RH, the sPPP-H + -based CCL not only exhibited better performance than at 90% RH but also significantly higher performance compared to the Nafion®-based CCL. For example, a current density of 3000 mA cm + was obtained with the sPPP-H -2 -based CCL, while only 800 mA cm -2 was obtained with the Nafion®-based CCL. By in-situ calculation of the membrane conductivity (using Equation 1 - S6 and iR drop in the ohmic region) (Figure 5), sPPP-H +It is revealed that the in-situ conductivity of the membrane is increased by 4 to 6 times.

[0229] The membrane and sPPP-H as an ionomer + According to the preliminary FC analysis (Figure 6), compared with N212, sPPP-H + was suggested to have low performance, which was due to its three times thickness. This is clear from the in-situ membrane conductivity calculation (Figure 7) that under FC conditions, sPPP-H + was six times higher than NR212. This result is unprecedented in aromatic membranes, especially in the case of integrating a complete aromatic-based MEA into an operating fuel cell. Therefore, the thinner sPPP-H + membrane can achieve competitive performance, if not higher than Nafion (registered trademark).

[0230] In summary, through the synthesis of a novel sulfonated self-play 9, well-defined sulfonated oligophenylene and polyphenylene homopolymers were obtained. For the homopolymer, the stereochemistry of the formed phenyl-phenyl bond was clarified by using it as a model compound to be a 42:40:18 mixture of m-m, p-p, and m-p. sPPP-H + was found to be relatively stable to the Fenton reagent. The membrane had a high IEC, maintained insolubility in water, and showed high proton conductivity. sPPP-H + The results of the preliminary study of the fuel cell incorporating it were promising. In the investigation of the copolymer derivative, the control of the polymer morphology, the limitation of water adsorption, the improvement of proton conductivity, and the increase in the mechanical strength of the thin film were guaranteed.

[0231] Experimental Procedures Apparatus and Raw Materials 1 H and 1313C NMR spectra were measured on a Bruker AVANCE III 500 MHz equipped with a 5 mm TXI inverse probe at room temperature (T = 298 K). 2D (COSY) and 1D NOE were measured on a Bruker AVANCE II 600 MHz "TCI 600" spectrometer equipped with a 5 mm TCI cryoprobe.

[0232] Mass spectra were measured for all molecules on an AB Sciex 4000 Q TRAP spectrometer (ESI mode).

[0233] Size exclusion chromatography analysis was performed using Water HPLC HR 5, HR 4, and HR 3 columns, with HPLC grade DMF (containing 0.10 M LiBr) as the eluent. A polystyrene sample purchased from Waters Associates Inc. was used as the calibration standard.

[0234] Reactions promoted by microwave were carried out using a Biotage® Initiator, a 20 mL sized microwave synthesizer equipped with a stirring bar.

[0235] Triethylamine (99%, Anachemia Science), and 1,4-diiodobenzene (98%) were purchased from Combi-Blocks, Inc. Acetone, dichloromethane (DCM), diethyl ether (reagent grade), methanol (MeOH), petroleum ether (PE), potassium carbonate (reagent grade), and toluene (ACS reagent) were purchased from Thermo Fisher Scientific. n-Butanol, dichloroethane (DCE), dimethyl sulfoxide (DMSO), ethyl acetate (AcOEt), and potassium hydroxide (KOH, reagent grade) were purchased from Caledon Laboratories Ltd. Nitrobenzene (ACS reagent, >99%) and trimethylsilyl chlorosulfonate (99%) were purchased from Sigma Aldrich Canada Co. Dimethylformamide (DMF, anhydrous HPLC grade) was purchased from J&K Scientific. Anhydrous ethanol was purchased from Commercial Alcohols. Diphenylphosphine ferrocene dichloride (97%) was purchased from Strem Chemicals, Inc. 1,3-(Diphenyl)propan-2-one (98%), bisbenzyl (98%), and trimethylsilyl ethynyl (98%) were purchased from Tokyo Chemical Industry Co., Ltd America. Diphenylphosphine palladium dichloride (98%) was purchased from Strem Chemicals, Inc. Copper iodide (99.9%) was purchased from Santa Cruz Biotechnology, Inc. All of the aforementioned reagents were used without further purification. Toluene was degassed with argon for 30 minutes with molecular sieves before use.

[0236] Synthesis Scheme 1-S1: Synthesis of polyphenylene monomers, oligomers, and homopolymers

[0237] [Chemical formula]

[0238] Synthesis of Tetracyclone 3 Scheme 1-S2: Synthesis of Tetracyclone 3

[0239]

Chem.

[0240] Compound 3 was synthesized according to the literature procedure. 175 mL of anhydrous ethanol was charged into a 250 mL two-necked round-bottom flask, which was equipped with a condenser, a septum, and a stir bar. 1,3-(Diphenyl)propan-2-one 1 (4.00 g, 19.0 mmol, 1.02 equiv) and benzyl 2 (3.92 g, 18.7 mmol, 1.00 equiv) were added. The solution was refluxed for 1 h. To the warm solution, KOH (1.04 g, 18.7 mmol, 1.0 equiv, dissolved in 5 mL of ethanol) was added dropwise via syringe through the septum. The solution was refluxed for an additional 45 min and cooled to 0 °C using an ice bath. After 2 h, the solution was filtered and the precipitate was washed twice with cold methanol to afford 3 (7.17 g, 15.0 mmol, 86.0%) as a purple crystalline powder. FTIR-ATR (cm -1 ): 3060, 1709, 1494, 1444. 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 6.95 (d, J = 7.01 Hz, 4 H), 7.18 (t, J = 7.47 Hz, 4 H), 7.21 - 7.27 (m, 12 H). 13 C NMR (125 MHz, CD2Cl2) δ (ppm): 200.86, 155.33, 133.77, 131.54, 130.68, 129.80, 129.00, 128.51, 128.00, 126.01. HRMS [M+H] + : calcd for C 29 H 20 O 385.1583, found 385.1587.

[0241] Synthesis of 4,4'-(2-Oxo-4,5-diphenylcyclopenta-3,5-diene-1,3-diyl)dibenzene Sulfonic Acid, 4 Scheme 1-S3: Synthesis of Cyclone Disulfonic Acid 4

[0242]

Chem.

[0243] Into a 500 mL round-bottom flask equipped with a stir bar, 300 mL of dichloroethane degassed with argon was charged, and 3 (3.00 g, 7.81 mmol, 1 equiv) was dissolved. Trimethylsilyl chlorosulfonate (5.57 mL, 31.24 mmol, 4 equiv) was diluted with 8 mL of degassed dichloroethane and added dropwise to the flask. The solution was stirred for 12 h. Ethanol (3 mL) was added to initiate precipitation and stop the reaction. The reaction mixture was stirred for an additional 2 h, poured into 1.0 L of dry ether, filtered, and washed several times with cold diethyl ether. The precipitate was collected and dried under vacuum at 60 °C for 8 h to quantitatively obtain 4 (4.25 g, 7.81 mol) as a bright purple powder. FTIR-ATR (cm -1 ): 3404, 1711, 1133, 1032, 1000. 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 3.86 (s, H20 / H3O + ), 6.95 (d, J = 7.24 Hz, 4 H), 7.11 (d, J = 8.38 Hz, 4 H), 7.22 - 7.29 (m, 6 H), 7.46 (d, J = 8.38 Hz, 4 H). 13 C NMR (125 MHz, CD2Cl2) δ (ppm): 199.48, 155.08, 147.05, 132.63, 130.68, 129.25, 128.90, 128.72, 128.16, 125.23, 124.60. HRMS [M-e] - : calcd for C 29 H 20O7S2543.0577, found 543.0564, [M-e] 2- 271.0231.

[0244] Synthesis of Bistriethylammonium Cyclodisulfonate 5 Scheme 1-S4: Synthesis of Triethylammonium Cyclodisulfonate 5

[0245]

Chemical Structure

[0246] 150 mL of n-butanol was added to a 500 mL round-bottom flask equipped with a stir bar, 4 (4.00 g, 3.52 mmol, 1 equiv) was dissolved, and then 100 mL of triethylamine was added. The solution was stirred for 12 hours and then filtered and washed several times with cold ethyl acetate or diethyl ether. The precipitate was collected and dried overnight under vacuum at 100 °C to give 5 (4.56 g, 6.12 mol, 83.1%). 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 1.17 (t, J = 7.10 Hz, 36 H), 3.09 (m, two overlapped quartets, 12 H), 6.97 (d, J = 6.93 Hz, 4 H), 7.11 (d, J = 8.29 Hz, 4 H), 7.22 - 7.29 (m, 6 H), 7.46 (d, J = 8.29Hz, 4 H), 8.85 (s, 4 H). 13 C NMR (125 MHz, CD2Cl2) δ (ppm): 199.46, 155.00, 147.19, 132.61, 130.55, 129.17, 128.86, 128.66, 128.11, 125.18, 124.57, 45.78, 8.65. HRMS [M-e] - : calcd for C 29 H 20 O7S2543.0578, found 543.0595, [M-e]2- 271.0231. [M+H] + : calculated for C6H16N 102.1277, found 102.1278.

[0247] Synthesis of Bis-Tetracyclone 7 Scheme 1-S5: Synthesis of bis-tetracyclone 7

[0248]

Chemical formula

[0249] 275 mL of anhydrous ethanol was added to a 250 mL two-necked round-bottom flask equipped with a condenser, a stir bar, and a septum. 1,3-(Diphenyl)propan-2-one 1 (4.00 g, 19.0 mmol, 2.1 equiv) and bisbenzyl 6 (3.10 g, 9.07 mmol, 1 equiv) were added and the solution was refluxed. After 1 h, KOH (1.02 g, 18.1 mmol, 2.0 equiv, dissolved in 5 mL of ethanol) was added dropwise to the refluxing solution. The solution was refluxed for an additional 45 min and cooled to 0 °C for 2 h using an ice bath. The solution was filtered and the precipitate was dissolved in boiling DCM and recrystallized at 4 °C to give purple needle crystals (5.5 g, 7.97 mmol, 88%). 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 6.78 (s), 6.92 (d, J d = 7.06 Hz, 4 H), 7.19 - 7.30 (m, 26 H). 13 C NMR (126 MHz, CD2Cl2) δ 200.60, 154.93, 154.66, 134.11, 133.50, 130.65, 130.59, 129.77, 129.51, 129.05, 128.53, 128.12, 128.07. HRMS [M+H]+: calculated for C 52 H 34 O2: 690.2559 found 691.2619

[0250] Synthesis of Tetra(para-sulfonated)bis-tetracyclone 8 Scheme 1-S6: Synthesis of tetra(para-sulfonated) bis-tetracyclone 8

[0251] [Chemical formula]

[0252] 300 mL of dichloroethane degassed with argon was charged into a 500 mL round-bottom flask equipped with a stir bar, and 7 (4.00 g, 5.8 mmol, 1 equivalent) was dissolved therein. Trimethylsilyl chlorosulfonate (6.74 mL, 46.4 mmol, 8 equivalents) in 8 mL of degassed dichloroethane was added dropwise to the round-bottom flask. The solution was stirred for 12 hours. Ethanol (5 mL) was added to initiate precipitation and stop the reaction. Stirring was continued for an additional 2 hours, and the reaction mixture was poured into 1.5 L of diethyl ether, filtered, and washed several times with cold diethyl ether. The precipitate was collected and dried under vacuum at 60 °C for 8 hours to obtain 8 (4.74 g, 4.69 mol, 80.9%). 1 H NMR (500 MHz, DMSO-d6) δ (ppm): 6.87 (s, 4 H core ), 6.92 (d, J d = 7.40 Hz, 4 H o ), 7.10 (d, J d = 8.16 Hz 4 Hβ1), 7.16 (d, J = 8.50 Hz, 4 Hβ2), 7.25 (t, J t = 7.74 Hz, 4 H m ), 7.33 (m, 2H p ), 7.50 (D, J D = 8.32 Hz, 4 Hα2), 7.55 (D, J D = 8.54 Hz, 4 Hα1) 7.57 (s, 4H, H20 / H3O + ) 1313C NMR (151 MHz, DMSO-d6) δ 199.45, 155.13, 155.00, 146.56, 146.46, 133.35, 132.22, 131.15, 130.84, 129.53, 129.30, 128.98, 128.84, 128.36, 125.48, 125.45, 124.63, 124.35. HRMS [M-e] - : calcd for C 52 H 34 O 14 S41010.0831, found 1009.0768, [M-e] 2- 504.0358, [M-e] 3- 335.6890. [M+H] + : calcd for C6H16N 102.1277, found 102.1278.

[0253] Synthesis of Tetratriethylammonium Tetra(para-sulfonated)bis-tetracyclone 9 Scheme 1-S7: Synthesis of Tetratriethylammonium Tetra(para-sulfonated) Bistetracyclone 9

[0254]

Chem.

[0255] 200 mL of n-butanol was added to a 500 mL round-bottom flask, 8 (4.41 g, 4.37 mmol, 1 equiv) was dissolved, and then 100 mL of triethylamine was added. The solution was stirred for 12 h and then filtered and washed several times with cold ethyl acetate or diethyl ether. The precipitate was collected and dried overnight under vacuum at 100 °C to give 9 (6.08 g, 4.30 mol, 98.3%). 1 1H NMR (600 MHz, DMSO-d6) δ (ppm): 1.16 (t, J t = 7.20 Hz, 36H, 1 or CH3), 3.09 and 3.10 (2 d, J d= 4.71 Hz, 24H, 2 or -CH2-), 6.86 (s, 4 H, Hcore), 6.93 (d, J d = 7.35 Hz, 4 H, Ho), 7.08 (d, J d = 8.42 Hz 4 H, Hβ1), 7.14 (D, J D = 8.54 Hz, 4 H, Hβ2), 7.26 (t, J t = 7.15 Hz, 4 H, Hm), 7.34 (m, 2H, Hp), 7.48 (D, J D = 8.42 Hz, 4 H, Hα2) 7.52 (D, J D = 8.54 Hz, 4 H, Hα1), 8.88 (s, 4H, 3 or NH+). 13 C NMR (151 MHz, DMSO-d6) δ 199.37, 154.81, 154.64, 147.06, 147.05, 133.18, 132.08, 130.61, 130.24, 129.20, 129.04, 128.95, 128.81, 128.78, 128.74, 128.61, 128.11, 128.04, 125.24, 125.20, 124.43, 124.16, 45.78, 8.61. HRMS [M-e] - : calcd for C 52 H 34 O 14 S41010.0831, wasn't observed, [M-e] 2- 504.0358, [M-e] 3- 335.6884, [M-e] 4- 251.5147.

[0256] Compounds 12 and 13 were synthesized according to the methods described in the literature. Synthesis of 1,4-Bis(trimethylsilylethynyl)-benzene 12 Scheme S8: Synthesis of 1,4-bis(trimethylsilylethynyl)-benzene 12

[0257]

Chem.

[0258] A 100 mL Schlenk flask equipped with a stir bar was degassed three times in advance by argon / vacuum, and 1,4-diiodobenzene 10 (14.54 g, 44.1 mmol, 1 equiv), 45 mL of anhydrous toluene, diphenylphosphine ferrocene palladium dichloride (0.180 g, 0.22 mmol, 0.5 mol %), and trimethylsilylacetylene 11 (1.28 mL, 92.6 mmol, 2.1 equiv) were added. The solution was stirred for 10 minutes. A second Schlenk tube equipped with a stir bar was degassed as described above, CuI (0.042 g, 0.22 mmol, 0.5 mol %), and triethylamine (6 mL, containing 1 mL / 0.007 g of CuI) were added, and the solution was stirred for 20 minutes. The content of the second Schlenk tube was transferred to the first Schlenk tube using a PEEK cannula. The combined reaction mixture was vigorously stirred at room temperature for 15 minutes, during which time the mixture turned black. Next, the mixture was heated at 91 °C for 1 hour and then allowed to cool to room temperature. The solution was filtered and washed several times with diethyl ether. The filtrate was washed successively with saturated ammonium chloride, 5.0 M hydrochloric acid, and saturated brine, dried over MgSO4, and filtered. The filtrate was concentrated using a rotary evaporator to obtain yellow crystals. The product was purified by sublimation or recrystallization from cold petroleum ether to obtain 12 (11.62 g, 97.6% by recrystallization, 89.0% by sublimation). 1 H NMR (500 MHz, acetone-d6) δ (ppm): 0.23 (s, 18H), 7.45 (s, 4H). 13 C NMR (125 MHz, acetone-d6) δ (ppm): δ 132.66, 124.18, 105.20, 96.89, -0.11.

[0259] Synthesis of 1,4-Bisethynylbenzene 13 Scheme S9: Synthesis of 1,4-bisethynylbenzene 13

[0260] [Chemical]

[0261] A 250 mL round-bottom flask equipped with a stir bar was degassed with argon for 20 minutes in advance and shielded from light with aluminum foil. To this, 140 mL of tetrahydrofuran, 70 mL of methanol, and 12 (1.92 g, 7.11 mmol, 1 equivalent) were added. K2CO3 (4.48 g, 35.5 mmol, 5 equivalents) was quickly added, and the reaction mixture was stirred for 3 hours. The solution was opened and poured into 200 mL of DCM, and washed three times with water. The aqueous phase was washed once with DCM, the combined organic phases were dried over MgSO4, filtered, and concentrated using a rotary evaporator to obtain white-yellow crystals. The final product was purified by sublimation to obtain 13 (0.66 g, 68.3%). 1 H NMR (500 MHz, acetone-d6) δ (ppm): 3.81 (s, 2 H), 7.50 (s, 4 H). 13 C NMR (125 MHz, acetone-d6) δ (ppm): 132.88, 123.64, 83.49, 81.21.

[0262] Synthesis of Compound 14 Scheme S10: Synthesis of Compound 14

[0263] [Chemical]

[0264] Into a 60 mL Schlenk tube equipped with a stir bar, 13 (0.150 g, 1.19 mmol, 1.0 equiv), 5 (1.76 g, 2.36 mmol, 2.0 equiv), and 5 mL of nitrobenzene were added. The Schlenk tube was sealed with a septum, stirred for 10 minutes, and inserted into a sand bath at 190 - 200 °C. After 8 hours, the solution turned black. The tube was allowed to cool to room temperature, and the contents were transferred to a 250 mL round-bottom flask containing 200 mL of ethyl acetate. The solution turned white, refluxed for 4 hours, and the solution was filtered using a Buchner funnel and washed once with boiling ethyl acetate and twice with boiling acetone to obtain 14 (1.76 g, 94.7%). 1 H NMR (500 MHz, DMSO-d6) δ (ppm): 1.14(t, J tzz = 7.26 Hz, 36 H), 3.08 (two overlapped quadruplet, 24 H), 6.73 (d, J d = 8.21 Hz, H), 6.83 - 6.96 (m, 24 H), 7.13 (D, J D = 8.38 Hz, 4 H), 7.23 (d, J d = 8.27 Hz, 4 H), 7.36 - 7.38 (m, 6H), 8.90 (s, 4H) 13 C NMR (151 MHz, DMSO-d6) δ 145.89, 145.25, 141.74, 141.33, 139.94, 139.77, 139.71, 139.61, 139.45, 139.21, 138.83, 138.43, 131.02, 130.96, 130.47, 130.41, 129.01, 128.94, 126.89, 126.59, 125.81, 125.63, 124.82, 124.17, 45.78, 8.60. HRMS [M-e] - : calcd for C 66 H 46 O 12 S41158,1872, found 1157.1811, [M-e] 2- 578.0868, [M-e]3- 385.0559 [M-e] 4- 288.5403 [M+H] + : calculated for C6H 16 N 102.1277, found 102.1278

[0265] Synthesis of Compound 16 Scheme S11: Synthesis of Compound 16. The states of the intermediates in parentheses indicate two possible adducts from 15 to 19, giving a mixture of isomers.

[0266]

Chemical formula

[0267] To a 60 mL Schlenk tube equipped with a stir bar, 9 (1.000 g, 0.707 mmol, 1.0 equiv), 15 (0.163 mL, 1.485 mmol, 2.1 equiv), and 6 mL of nitrobenzene were added. The solution was stirred for 10 minutes. The Schlenk tube was sealed with a septum, and the contents were stirred at room temperature for 10 minutes and then inserted into a sand bath at 190 - 200 °C. After 8 hours, the solution turned orange, and the tube was allowed to cool to room temperature. The contents were transferred to a 100 mL round-bottom flask containing 50 mL of ethyl acetate. At this time, the solution turned white. After refluxing for 4 hours, the product was filtered and washed twice with boiling ethyl acetate and twice with acetone. After drying overnight at 100 °C, Compound 16 was recovered as a bright yellow powder (0.855 g, 77.3%). 1 H NMR (500 MHz, DMSO-d6)) δ (ppm): 1.16 (t, Jt = 7.24Hz, 36H), 3.09 (two overlapped quadruplet, Jq = 7.37 Hz, 24 H), 13 C NMR (151 MHz, DMSO-d6) δ HRMS [M-e] - : calculated for C 126 H 86 O 12 S4 Calculated for C6H 16 N 102.1277, found 102.1278.

[0268] Synthesis of sPPP-NHEt 3 + Synthesis of sPPP-H Scheme S12: Synthesis of polymer sPPP-NHEt3 + of

[0269] [Chemical Structure]

[0270] 9 (1.2 g, 0.848 mmol, 1 equiv), 13 (0.108 g, 0.859 mmol, 1.02 equiv), and 10.0 mL of nitrobenzene were charged into a 20 mL Biotage® microwave synthesizer, and the synthesizer was sealed. After stirring for 10 minutes, the reaction was allowed to proceed by activating with microwave at 195 °C for 2 hours. The solution changed color from purple to orange. After cooling, the synthesizer was opened, and ethyl acetate was added to precipitate the polymer. The polymer was refluxed in ethyl acetate for 4 hours and washed twice with boiling ethyl acetate and once with diethyl ether. After drying in vacuo at 120 °C, polymer sPPP-NHEt3+ was obtained as a white powder (1.042 g, 82.8%). GPC analysis: M n = 186,000 g mol -1 , M w = 269,000 g mol- 1 , M w / M n = 1.44. 1 H NMR (500 MHz, DMSO-d6)) δ (ppm): 1.12 (t, Jt = 7.29Hz, 36H), 3.05 (two overlapped quadruplet, Jq = 7.26 Hz, 24H), 6.16 - 7.54 (m, 36H), 8.92 (s, 4H)

[0271] Membrane Formation + Procedure of Fenton Test Scheme S13: sPPP-K as an intermediate + sPPP-H via + Synthesis route

[0272] [Chemical formula]

[0273] In a 200 mL round-bottom flask, polymer sPPP-NHEt3 + was dissolved in 100 mL of methanol at room temperature with vigorous stirring. After complete dissolution, 75 mL of 2.0 M KOH in methanol was added to precipitate polymer sPPP-K + . The solution was stirred for an additional 2 hours. The solution was filtered, and the polymer was washed twice with methanol and diethyl ether. The polymer was dried under vacuum at 80 °C overnight. sPPP-K + was dissolved in 75 mL of DI H2O. After complete dissolution by vigorous stirring, 75 mL of 2.0 M H2SO4 was added. The solution was stirred for an additional 2 hours, filtered, washed several times with water and twice with ether. It was dried under vacuum at 120 °C overnight to recover sPPP-H + . GPC analysis: M n = 135,000 g mol -1 , M w = 262,000 g mol- 1 , M w / M n = 1.49. 1 H NMR (500 MHz, DMSO-d6)) δ (ppm): 4.93 (s, H + / H2O), 6.16 - 7.54 (m, 36H), 8.92 (s, 4H)

[0274] Ex-situ Performance Evaluation of Membrane sPPP-H +The membrane was formed from a 7 w% DMSO solution. For example: 0.350 g of sPPP-H+ was dissolved in 5.0 mL of DMSO at 80 °C. The solution was filtered through a glass fiber filter into a flat 65 mm diameter Petri dish. The solution was slowly evaporated in a sealed vacuum oven at 80 °C under atmospheric pressure for 2 days. After 2 days, the membrane was immersed in 0.5 M H2SO4 in water for 12 hours. The membrane was immersed / washed 4 times with DI H2O and dried overnight under vacuum at 100 °C.

[0275] Fuel Cell Tests as Membrane and in Catalyst Layer A piece of the membrane dried overnight at 80 °C under vacuum and 0.104 g of sPPP-H + were placed with stirring at 80 °C into a vial containing 20 mL of a 3.0% H2O2 solution in DI H2O. 1.54 mL of 3.0 ppm FeSO4 was added. The resulting solution was stirred for an additional 1 hour. After cooling to room temperature, sodium sulfite was added to the solution until bubbling ceased to stop the reaction. The polymer precipitated and was collected by filtration and washed several times with ion-exchanged water. Next, the polymer was immersed in 1.0 M HCl in water and washed 6 times with DI H2O. The resulting polymer was dried overnight at 120 °C. The polymer was 1 analyzed by an H NMR spectrometer.

[0276] Example 2: Phenylated Polyphenylene with High Stability, Low Gas Crossover, and Proton Conductivity sPPP-H + small pieces (2 cm × 2 cm) were equilibrated overnight in 2 M NaCl to release protons and titrated with 0.001 M NaOH to the phenolphthalein endpoint. An acid-base control titration was performed with 2 M NaCl without the membrane to obtain the blank titration volume. After titration, the membrane was immersed in 2 M HCl for at least 4 hours to reprotonate the sulfone sites. After drying overnight at 120 °C under vacuum, the "dry" weight of the membrane was measured. The ion exchange capacity (IEC, mmol / g) of the membrane was calculated using Equation 1-S1.

[0277]

Number

[0278] {wherein, V NaOH and M NaOH are the volume (mL) and molar concentration (mol / L), respectively, adjusted with a blank of the NaOH solution. W dry is the dry weight of the membrane.}

[0279] The membrane was equilibrated overnight in ion-exchanged water at room temperature, and the surface moisture was removed with Kimwipes and dried to measure the "wet" weight. The water absorption was calculated as the mass increase rate with respect to the "dry" weight according to the following formula. The water absorption was reported as the average of the measured values of three similar samples.

[0280]

Equation

[0281] {wherein, W wet and W dry are the weights of the membrane in the wet and dry states, respectively.}

[0282] The proton conductivity was measured by the following procedure. The membrane (10 mm × 5 mm) was placed between two platinum electrodes of a conductivity cell, and a 100 mV sinusoidal AC voltage was applied in the frequency range of 10 MHz to 100 Hz using an AC impedance spectrometer with a Solartron 1260 frequency response analyzer (FRA). The obtained Nyquist diagram was fitted to a standard Randles equivalent circuit to determine the membrane resistance. The proton conductivity (σ) was calculated using Equation 1-S3.

[0283]

Equation

[0284] {wherein, L (cm) is the distance between the electrodes, and R H+ (Ω) is the ionic resistance of the membrane, and A (cm 2 ) is the cross-sectional area of the membrane.}

[0285] Measurements with controlled temperature and humidity were carried out in an Espec model SH-241 humidity chamber maintained at 30 °C.

[0286] The acid concentration (as an approximation of the dissociated proton concentration of the membrane) was calculated according to Equation 1-S4.

[0287]

Number

[0288] The effective proton mobility (μ H+ ) was calculated from Equation 1-S5.

[0289]

Number

[0290] {In the formula, F is the Faraday constant.}

[0291] The in-plane proton conductivity was measured by an impedance spectrometer using a Solartron 1260 frequency response analyzer (FRA) having a configuration including two electrodes. The proton conductivity at various RHs was measured by placing the conductivity cell in an Espec model SH-241 humidity chamber maintained at 30 °C.

[0292] Experiments and Raw Materials The optimized Nafion catalyst ink was prepared by a conventional method. Water was added to the Pt / C powder, methanol was added to make the final ratio 1:1 (MeOH:H2O), and the ionomer solution (Nafion® D520) was added dropwise with stirring. Finally, 1 wt% solids in the solution contained 30 wt% ionomer and 70 wt% Pt / C (TKK TEC-10E50E, Pt on 46.4 wt% graphite C). The catalyst ink was applied onto the electrode at 80 °C for 5 cm 2The area was applied onto the membrane via a spray coater (Sono-Tek ExactaCoat SC). To fabricate the hydrocarbon ionomer electrode, the catalyst ink was similarly prepared with 20 wt% ionomer and the final solvent ratio was 3:1 (MeOH:H2O), and it was similarly coated using a spray coater.

[0293] To investigate sPPPH+ as the cathode, the hydrocarbon ionomer electrode was loaded with 0.4 mg Pt / cm 2 on Nafion® NR211, and the reference electrode was loaded with 0.2 mg Pt / cm 2 on Nafion® D520. For sPPPH+ as the membrane, the Nafion® D520 electrode was placed on a 113 μm sPPP-H + membrane. For the complete sPPPH+, the hydrocarbon ionomer electrode was placed on a 150 μm sPPP-H + membrane.

[0294] The obtained MEA was mounted on a fuel cell hardware. MEAs with hydrocarbon membranes were stacked, and the final active area was 4 cm 2 using a standard 3-mil laminate sheet. Using a conventional GDL (Sigracet 24BC), the gasket at this time was sufficient to compress the GDL by 20 - 30% using 30 inch-pound torque.

[0295] The performance of the fuel cell was evaluated using a fuel cell test station (Teledyne Medusa RD 890CL, Scribner Associates Inc.). The adjustment of the MEA was performed by slowly increasing the current at a rate of 25 mA / cm 2 and then passing through the ohmic region polarization curve within 6 hours until a certain function was achieved. The polarization curve was measured at 80 °C, relative humidity (RH) 100%, 0.5 / 1.0 slpm H2 / O2, from 0 to high current density, with 5 min / pt at OCV and up to 200 mA / cm 2 at a rising rate of (1 min / pt, 2 mA / cm 2 rising rate of 2 - 20 mA / cm2 and 50, 100, and 150 mA / cm for 5 min / pt 2 were employed and determined in the case where the dynamic region was eliminated). The membrane conductivity was determined from the iR drop in the ohmic region using Equation 1-S6 (current interruption method).

[0296]

Equation

[0297] {In the equation, σ H+ is the proton conductivity, l is the membrane thickness, R total is the measured total resistance, R cell is a constant value of the cell offset (due to the potentiostat, flow field, hardware, and GDL), and A is the area.}

[0298] In the cathode and the complete hydrocarbon MEA, all electrochemical data were obtained after equilibration of the CCM adjusted to a low potential of less than 0.25 / 0.5 slpm H2 / N2 by a combination of a potentiostat / gain phase analyzer (PAR VersaStat). Chronoamperometry (CA), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) were performed at 0.25 / 0.5 slpm H2 / N2.

[0299] CA was performed with a potential hold at 0 V, and then 0.1 to 0.5 V at 0.1 V intervals, each step held for 30 s. The fuel crossover was calculated as the ± sample standard deviation from the average current at 0.5 V after the pseudo-capacitive region. The low potential steps below 0.5 V confirm that the electrodes are fully activated and no electrical short circuit occurs. LSV was performed as a potential sweep of 2 mV·s -1 from the open circuit potential to 0.6 V, confirming no electrical short circuit and confirming the fuel crossover.

[0300] EIS was performed at a bias of 0.45 V with 10 V AC from 1 to 10 5It was swept up to Hz. The proton conductivity in the catalyst layer was calculated by a standard method, for example, the method is disclosed in Strong et al., J. Electrochem. Soc. 2015, 162, F513.

[0301] CV was 50 mV·s -1 and was carried out. At this time, the initial potential was 0.4 V, and the peak potentials were 0.04 and 0.8 V. The ECSA was calculated from the integrated H2 adsorption and desorption peaks. C dl was calculated from the minimum distance between the forward scan and the reverse scan in the region of 0.35 to 0.55 V.

[0302] Synthesis Route In this example, two types of novel sulfonated phenylated polyphenylene ionomers were investigated as polyaromatic proton exchange membranes. Both types of ionomers had a high ion exchange capacity and were insoluble in water even at elevated temperatures. They showed high proton conductivity in both the fully hydrated state and the state with reduced relative humidity and had remarkable resistance to free radical attack. The fuel cell constructed with the membrane - electrode - assembly containing each ionomer membrane achieved higher in situ proton conductivity and peak power density than when using a Nafion® control membrane. Through in situ chemical / mechanical accelerated stress tests, this type of polyaromatic membrane achieved significantly lower gas crossover and lower degradation rate compared to the Nafion benchmark system. Sulfonated phenylated polyphenylene by molecular design can be used as a proton conductive medium.

[0303] The synthesis of sulfonated phenylated polyphenylene using the Diels - Alder (D - A) polymerization reaction is disclosed. sPPP - H +Molecular design for improving the preferred contribution is emphasized. This is achieved by incorporating biphenyl and naphthyl, which are spacer units, into the polymer backbone. Optimization of the polymerization conditions is promoted by the synthetic study of oligophenylene model compounds. The model compounds have structural similarities with the related polymers but are easier to evaluate for their properties. Small molecules SM-B and SM-N linked with biphenyl and naphthyl were obtained via [4+2] D-A cycloaddition reactions between 3c and 2b or 2c respectively (Scheme 2-1a). The reactions were carried out under the same reaction conditions as the intended polymerization conditions to confirm the stability of the desired spacer unit at the temperature required for the D-A reaction.

[0304] Scheme 2-1a and 2-1b Sulfonated branched oligophenylene (2-1a) and polyphenylene (2-1b)

[0305]

Chemical Structure

[0306] Using a pre-sulfonated monomer, a polymer containing four sulfonic acid groups per repeating unit can be synthesized, and their positions can also be accurately controlled. The synthesis was achieved by [4+2] D-A cycloaddition between monomer 1c and linking group 2b or 2c to obtain sPPB-HNEt3 + and sPPN-HNEt3 + respectively (Scheme 2-1b). The details of the synthesis of each compound are described below. Gel permeation chromatography (GPC) analysis suggested that sPPB-HNEt3 + had an Mw of 175,000 Da (M w / M n = 1.56), and sPPN-HNEt3 + had an Mw of 329,000 Da (M w / M n = 2.33). It was suggested that the polymerization was successful. 1It was confirmed by 1H NMR spectrometer analysis. At this time, triethylammonium cation was used as the internal probe. Methyl protons (36H), methylene protons (24H), and aromatic backbone protons of the polymer (40H for sPPB-HNEt3 + and 38H for sPPN-HNEt3 + ) were observed with the expected integration ratios among them.

[0307] sPPB-H in the acid form of the polymer + and sPPN-H + were formed into films with a DMSO solution (5% w / w) and dried overnight at 85 °C. The water absorption and impregnation rates are shown in Table 2-1. Both polymers were insoluble in DI H2O at 80 °C. sPPB-H + showed significantly lower water absorption and impregnation rates compared to sPPN-H + , but higher than Nafion® NR-211.

[0308] The Fenton reagent is commonly used in preliminary ex-situ accelerated degradation tests, and the oxidative stability of PEMs is studied by the ability to generate oxygen-containing free radicals in solution. After exposure to the Fenton reagent (1 hour, 80 °C), no mass loss was observed in the films (0.69 ± 0.71% and 0.09 ± 0.62% for sPPB-H + and sPPN-H + respectively), and no changes were observed in the chemical structure ( 1 1H NMR), suggesting a significantly high chemical resistance to free radical attack.

[0309] By titration experiments, it was shown that sPPB-H + and sPPN-H + had IECs of 3.19 ± 0.05 meq. g -1 and 3.28 ± 0.06 meq. g -1 respectively, and the theoretical values compared with these were 3.46 meq. g -1 and 3.54 meq. g -1 respectively. These IECs were for sPPP-H+ membrane (experimental value: 3.47 meq. g -1 , theoretical value: 3.70 meq. g -1 ) is slightly lower than that measured in, which is due to the increase in equivalent weight caused by incorporating biphenyl and naphthyl moieties.

[0310] Proton conductivity measurements were carried out using electrochemical impedance spectroscopy (EIS) at both 30 °C and 80 °C in the range of relative humidity (RH) 30% - 95% (Figures 8A and 8B). The maximum values of 222 mS cm -1 and 268 mS cm -1 were observed at 95% RH in sPPN-H at 30 °C and 80 °C, respectively. These values are significantly higher than those previously reported for sulfonated polyphenylene and those obtained for Nafion® NR-211, which are 79 mS cm + (30 °C) and 113 mS cm -1 (80 °C). sPPB-H -1 showed proton conductivities of 129 mS cm + and 172 mS cm -1 at 30 °C and 80 °C, respectively, which are higher than those previously reported for sPPP-H -1 and NR-211. As expected, the conductivity decreases with the decrease in the water content of the membrane. The high proton conductivity of sPPN-H + is due to its significantly high water absorption rate, which is considered to improve the connectivity of the aqueous domains across the material. The comparison of acid concentrations ([SO3H]) for sPPN-H + , sPPB-H + , and NR-211 at 30 °C: 1.17, 1.43, and 1.55 mmol + / cm SO3H and their proton mobility values (μ 3 membrane +): 2.0, 0.9, and 0.5 × 10 H cm -3 V 2 s -1 s -1Further supporting this assumption (Tables 2-3), even though the membranes have lower acid concentrations than NR-211, their proton mobilities are much higher (especially sPPN-H + in the case of).

[0311] 33±2μm sPPB-H + and sPPN-H of 80±4μm + On the membrane, PFSA ionomer and 0.4 mg Pt cm -2 A catalyst layer containing sPPB-H was applied by ultrasonic spray coating. These were installed in fuel cells, tuned in situ, and showed highly repeatable operation over a 25-hour RH cycle (Figure 12). At 80°C and zero backpressure, the sPPB-H + and sPPN-H + The membrane electrode assemblies (MEAs) of -2 These MEAs showed peak power densities of 587 and 445 mW cm, respectively, which were 56% and 17% higher than those obtained using the N212 reference MEA (Figure 9). With H2 / air, these MEAs achieved peak power densities of 587 and 445 mW cm -2 The peak power densities of sPPB-H211 and sPPB-H2212 were 29% higher or comparable to N212, respectively (Figure 14). Using H2 / O2 and H2 / air gave better results compared to N211, which was due to the optimization of the membrane thickness and gas diffusion layer (GDL) (Figures 14 and 15). In both cases, the in situ membrane resistance (insets), measured during operation by the iR-drop method and verified by high frequency resistance measurements, was significantly lower than the N212 reference MEA and atypical for hydrocarbon membranes. The in situ conductivity taking into account the difference in membrane thickness was significantly lower than the N212 reference MEA and atypical for hydrocarbon membranes. + or sPPN-H + 170±21 and 261±22 mS cm for the base MEA -1 which are 111 and 223% greater than N212 at 80° C., respectively (FIGS. 13A and 13B).

[0312] An in situ chemical / mechanical accelerated stress test (AST) was performed on sPPB-H under the conditions of potential holding at high temperature and low RH open circuit voltage (OCV). + was compared with the N211 reference (Figure 10). When using H2 / air, the initial OCV of sPPB-H + / N211 was 0.965 / 0.942 V. The losses at 1, 10, 50, and 100 hours were 2 / 66, 29 / 181, 55 / 231, 111 / 271 mV, respectively (Table 2-4). Furthermore, the H2 gas crossover of sPPB-H + was substantially lower than that of N211, for example, 0.5 vs 3.8 mA / cm 2 at 42 hours (Figure 2-S45). As shown in Figure 10, the N211 cell showed signs of failure after 100 hours, and the H2 crossover current approached 100 mA / cm 2 , but the sPPB-H + cell showed a crossover current of 12 mA / cm 2 after 100 hours of accelerated degradation. The sPPB-H + cell maintained an OCV of 0.71 after 400 hours, while the N211 cell dropped below 0.7 V after 100 hours of accelerated degradation. It was suggested that the sPPB-H + membrane cell had a four-fold longer lifespan compared to N211. The Nafion® 211 cell completely degraded in 153 hours, and the sPPB-H + cell still gave a polarization curve after 400 hours (Figure 17), showing a final OCV of 0.71 V, and the in situ conductivity decreased by only 31%, still 21% higher than the initial value of the fully conditioned N211 cell (Figure 18).

[0313] Therefore, two new sulfonated oligophenylene SM-N and SM-B are presented, leading to the synthesis of the corresponding sulfonated polyphenylene sPPB-HNEt3 + and sPPN-HNEt3 + . The pre-sulfonation technique enables the complete retention of sulfonic acid sites in the subsequent D-A polymerization, and the resulting polymers have high molecular weights. Conversion to the active acid form results in sPPB-H +and sPPN-H + were obtained, and membranes were formed from these for further property evaluation. EIS analysis revealed that exceptional proton conductivity was achieved even when RH decreased. All polymers showed remarkable fuel cell performance under unoptimized conditions, and sPPB-H + maintained high conductivity even after 400 hours of accelerated stress testing.

[0314] Tetraphenylcyclopentadienone (3a) 1 H and 13 13C NMR spectra were measured on a Bruker AVANCE III 500 MHz equipped with a 5 mm TXI inverse probe at room temperature (T = 298 K).

[0315] Size exclusion chromatography analysis was performed using Waters HPLC HR 5, HR 4, and HR 3 columns, with HPLC grade DMF (containing 0.10 M LiBr) as the eluent. Polystyrene samples purchased from Waters Associates Inc. were used as calibration standards.

[0316] Thermogravimetric analysis (TGA) measurements were carried out on a PerkinElmer STA6000 to evaluate the thermal stability of the polymers, with the temperature increased at a rate of 10 °C per minute from 30 °C to 600 °C under a nitrogen atmosphere.

[0317] Triethylamine (99%, Anachemia Science) and 1,4-dibromonaphthalene (98%) were purchased from Combi-Blocks, Inc. Acetone, dichloromethane (DCM), diethyl ether (reagent grade), methanol (MeOH), petroleum ether (PE), potassium carbonate (K2CO3, reagent grade) were purchased from Thermo Fisher Scientific. n-Butanol, dichloroethane (DCE), dimethyl sulfoxide (DMSO), ethyl acetate (EtOAc), and potassium hydroxide (KOH, reagent grade) were purchased from Caledon Laboratories Ltd. Nitrobenzene (ACS reagent, >99%), trimethylsilyl chlorosulfonate (99%), and 4,4'-diiodobiphenyl (technical grade, 90%) were purchased from Sigma Aldrich Canada Co. Dimethylformamide (DMF, anhydrous HPLC grade) was purchased from J&K Scientific. Anhydrous ethanol was purchased from Commercial Alcohols.

[0318] Diphenylphosphine ferrocene palladium dichloride (97%) was purchased from Strem Chemicals, Inc. 1,3-(Diphenyl)propan-2-one (98%), bisbenzyl (98%), and trimethylsilyl ethynyl (98%) were purchased from Tokyo Chemical Industry Co., Ltd. America. Diphenylphosphine palladium dichloride (98%) was purchased from Strem Chemicals, Inc. Copper iodide (99.9%) was purchased from Santa Cruz Biotechnology, Inc. All of the above-mentioned reagents were used without further purification.

[0319] 4,4'-(2-Oxo-4,5-diphenylcyclopenta-3,5-diene-1,3-diyl)dibenzene Sulfonic Acid (3b) Scheme 2-S1 Synthesis of Compound 3c

[0320] [Chemical Structure]

[0321] Scheme 2 - S2 Compound sPPB - H + Synthesis

[0322]

Chem.

[0323] 4,4'-(2-Oxo-4,5-diphenylcyclopenta-3,5-diene-1,3-diyl)dibenzene Sulfonic Acid Triethylammonium Salt (3c) A mixture of absolute ethanol (40 mL), benzyl (4.21 g, 20 mmol), and 1,3 - (diphenyl)propan - 2 - one (4.21 g, 20 mmol) was placed in a 100 mL two - necked round - bottom flask equipped with a stir bar. The flask was equipped with a condenser and an addition funnel with a cap and stirred under reflux for 30 minutes to dissolve completely. Next, a solution of KOH (1.12 g, 20 mmol, dissolved in 6 mL of absolute ethanol) was added dropwise to the yellow solution using a dropping funnel. The resulting black solution was stirred under reflux for an additional 30 minutes and cooled to 0 °C in an ice bath. The solution was filtered, and the precipitate was washed several times with ice - cold ethanol and dried under blowing air for 20 minutes, followed by overnight drying at 50 °C in a vacuum oven. The product was obtained as a shiny black crystalline powder (6.55 g, 17.04 mmol, 85.2%). 1H NMR (500 MHz, CDCl3) δ (ppm): 7.25 ‐ 7.21 (m, 12H), 7.17 (t, J = 7.4 Hz, 4H), 6.93 (d, J = 7.0 Hz, 4H). 13C NMR (125 MHz, CDCl3) δ (ppm): 200.5, 154.6, 133.2, 130.9, 130.3, 129.5, 128.6, 128.2, 128.1, 127.6, 125.5. LRMS [M+H]+: Calculated for C29H20O 385.1592, found 385.1572.

[0324] 4,4'-Bis(trimethylsilyl)biphenyl 300 mL of dichloromethane was added to a 500 mL two-necked round-bottom flask equipped with a stir bar. The flask was equipped with a septum and a sealed dropping funnel, and the apparatus was degassed with argon. 1a (4.47 g, 11.63 mmol) was added to dichloromethane, and the mixture was stirred for 15 minutes while degassing. Trimethylsilyl chlorosulfonate (12.54 mL, 81.38 mmol) was diluted with 15 mL of degassed dichloroethane, placed in the dropping funnel, and added dropwise to the flask. The mixture was stirred for 12 hours, ethanol (3 mL) was added, and stirring was continued for an additional 2 hours. The reaction mixture was poured into pentane, filtered, and the precipitate was washed with pentane and ethyl ether. It was dried in vacuo at 80 °C for 12 hours to obtain the final product as a bright purple powder (5.34 g, 9.81 mmol, 84.3%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 7.79 ( d, J = 8.3 Hz, 4H), 7.44 (d, J = 8.4 Hz, 4H), 7.34 (dd, J = 7.9 Hz, 2H), 7.28 (d, J = 8.3 Hz, 4H), 7.06 - 7.03 (m, 4H), 3.10 (s, H2O / H3O+). 13C NMR (125 MHz, DMSO-D6) δ (ppm): 199.48, 155.08, 147.05, 132.63, 130.68, 129.25, 128.90, 128.72, 128.16, 125.23, 124.60. LRMS [M‐e]‐: Calculated for C29H20O7S2 543.0578, found 543.3906, [M‐e]2- 271.2513.

[0325] 4,4'-Diethynylbiphenyl (2b) A 500 mL round-bottom flask equipped with a stir bar and containing butyl alcohol (150 mL) was charged with 1b (3.99 g, 7.33 mmol). While stirring vigorously at all times, a dropping funnel was attached to the flask and trimethylamine (10.21 mL, 73.30 mmol) was added dropwise to the mixture using this funnel. The reaction mixture was stirred for 2 h, filtered, and the precipitate was washed with trimethylamine and ethyl ether. It was dried in vacuo at 80 °C for 12 h to give the final product as a bright purple powder (5.20 g, 6.96 mmol, 95.0%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 8.86 (br. s, 2H), 7.46 (d, J = 8.1 Hz, 4H), 7.29 - 7.23 (m, 6H), 7.12 (d, J = 8.1 Hz, 4H), 6.99 - 6.97 (m, 4H), 3.10 (q, J = 7.3 Hz, 12H), 1.18 (t, J = 7.3 Hz, 18H). 13C NMR (125 MHz, DMSO-D6) δ (ppm): 199.46, 154.97, 147.30, 132.62, 130.47, 129.14, 128.86, 128.62, 128.09, 125.17, 124.56, 45.76, 8.64. LRMS [M‐e]‐: Calculated for C29H20O7S2 543.0578, found 543.3925, [M‐e]2- 271.2528. [M+H]+: Calculated for C6H16N 102.1277, found 102.1299.

[0326] 1,4-Bis(trimethylsilylethynyl)naphthalene A mixture of 4,4'-diiodobiphenyl (10.09 g, 24.85 mmol) in diethylamine (320 mL) was prepared in a 500 mL three-necked round-bottom flask equipped with a stir bar and filled with argon. A catalytic amount of Pd(PPh3)2Cl2 (174.4 mg, 0.249 mmol) and CuI (47.3 mg, 0.249 mmol) were added, the flask was sealed with a septum, and stirring was initiated. Ethynyltrimethylsilane (7.43 mL, 52.19 mmol) was injected via the septum, and the resulting mixture was stirred at 51 °C for 36 h. The reaction was cooled to room temperature, and the resulting white precipitate was removed by filtration. The filtrate was collected, and the solvent mixture was removed under reduced pressure. The resulting brown residue was purified by column chromatography (hexane on silica) to afford the pure product as white crystalline solids (6.06 g, 17.48 mmol, 70.4%). 1H NMR (500 MHz, Acetone-d6) δ (ppm): 7.71 (d, J = 7.9 Hz, 4H), 7.56 (d, J = 7.8 Hz, 4H), 0.25 (s, 18H). 13C NMR (125 MHz, Acetone-d6) δ (ppm): 140.90, 133.22, 127.73, 123.39, 105.66, 95.60, 0.00.

[0327] 1,4-Diethynylnaphthalene (2c) 4,4'-Bis(trimethylsilyl)biphenyl (1.80 g, 5.19 mmol) was dissolved in a mixed solvent of ethyl ether / methanol (1:1, 30 mL) in a 50 mL round-bottom flask equipped with a stir bar. Under vigorous stirring, K2CO3 (7.18 g, 51.93 mmol) was slowly added, and the reaction was stirred at room temperature for an additional 6 h. The reaction was poured into water (250 mL), and the aqueous phase was extracted with DCM (3 × 125 mL). The organic extracts were combined, dried over MgSO4, and the solvent mixture was removed under reduced pressure to afford the pure product as pale brown crystalline solids (1.04 g, 5.14 mmol, 99.0%). 1H NMR (500 MHz, Acetone-d6) δ (ppm): 7.72 (d, J = 8.2 Hz, 4H), 7.60 (d, J = 8.2 Hz, 4H), 3.74 (s, 2H). 13C NMR (125 MHz, Acetone-d6) δ (ppm): 141.10, 133.39, 127.83, 122.67, 83.90, 80.14.

[0328] Small Molecule Linked by Biphenyl (SM-B) 1,4-Dibromonaphthalene (2.002 g, 7 mmol) in diethylamine (70 mL) was prepared in a 100 mL round-bottom Schlenk flask equipped with a stir bar and filled with argon. A catalytic amount of Pd(PPh3)2Cl2 (49.1 mg, 0.070 mmol) and CuI (13.3 mg, 0.070 mmol) were added, the flask was sealed with a septum, and stirring was initiated. Ethynyltrimethylsilane (2.08 mL, 14.7 mmol) was injected via the septum, and the resulting mixture was stirred at 51 °C for 72 h. The reaction was cooled to room temperature and then to 0 °C in an ice bath and filtered. The filtrate was collected and the solvent mixture removed under reduced pressure. The resulting dark brown residue was dissolved in ethyl ether (40 mL) and washed with NH4Cl (3 × 15 mL), 10% v / v HCl (3 × 15 mL), and saturated brine (3 × 15 mL). The organic layer was dried over MgSO4, filtered, and the solvent mixture removed under reduced pressure. The product was obtained as a yellow-brown opaque powder (2.05 g, 6.4 mmol, 91.5%). 1H NMR (500 MHz, CDCl3) δ (ppm): 8.34 (dd, J = 6.4, 3.3 Hz, 2H), 7.62 (s, 2H), 7.60 (dd, J = 6.4, 3.3 Hz, 2H), 0.33 (s, 18H). 13C NMR (125 MHz, CDCl3) δ (ppm): 133.23, 130.12, 127.39, 126.70, 121.69, 102.95, 101.51, 0.20.

[0329] Small Molecule Linked by Naphthalene (SM-N) In a 250 mL round-bottom flask equipped with a stir bar and a dropping funnel, 1,4-bis(trimethylsilylethynyl)naphthalene (1.93 g, 6.02 mmol) was dissolved in a THF / methanol mixed solvent (4:1, 100 mL). A solution of K2CO3 (1.83 g, 13.24 mmol, in 2 mL of H2O) was added dropwise under vigorous stirring, and the reaction mixture was stirred at room temperature for an additional 6 hours. The solvent mixture was removed under reduced pressure, and the crude product was purified by column chromatography (3:1, hexane:chloroform, on silica). The pure product was obtained as pale tea crystalline solids (1.00 g, 5.68 mmol, 94.3%). 1H NMR (500 MHz, CDCl3) δ (ppm): 8.38 (dd, J = 6.4, 3.3 Hz, 2H), 7.68 (s, 2H), 7.63 (dd, J = 6.4, 3.3 Hz, 2H), 3.56 (s, 2H). 13C NMR (125 MHz, CDCl3) δ (ppm): 133.32, 130.45, 127.62, 126.59, 121.10, 83.78, 81.55.

[0330] 1,4-Bis(2,4,5-triphenylcyclopentadienone)benzene (1a) To a 25 mL Schlenk flask containing argon and equipped with a stir bar, molecule 3c (1.251 g, 1.675 mmol), linker 2b (0.165 g, 0.817 mmol), and nitrobenzene (13 mL) were added. The flask was sealed with a septum, and a freeze-pump-thaw cycle was performed three times using liquid nitrogen. The mixture was stirred vigorously for 10 minutes and reacted at 215 °C under moderate stirring for 48 hours. The reaction mixture was cooled to room temperature. Ethyl acetate (2 mL) was added to promote precipitation, and the reaction mixture was poured into ethyl acetate (200 mL), refluxed for 4 hours, filtered, and the precipitate was washed twice with boiling ethyl acetate and once with diethyl ether. The compound was dried overnight under vacuum at 80 °C to obtain the pure product as a light gray solid (1.227 g, 0.748 mmol, 91.6%). 1H NMR (600 MHz, Methanol-d4) δ (ppm): 7.66 (d, J = 8.0 Hz, 4H), 7.51 (s, 2H), 7.46 (d, J = 8.0 Hz, 4H), 7.44 (s, 4H), 7.28 (d, J = 8.0 Hz, 4H), 7.25 (d, J = 8.0 Hz, 4H), 7.06 (d, J = 8.1 Hz, 4H), 6.97 - 6.84 (m, 20H), 3.17 and 2.99 (two q, J = 7.3 Hz, 24H), 1.27 (two overlapping t, J = 7.1 Hz, 36H). 13C NMR (150 MHz, Methanol-d4) δ (ppm): 145.18, 144.35, 143.80, 143.74, 143.46, 141.89, 141.87, 141.66, 141.25, 141.05, 140.99, 140.12, 139.76, 132.64, 132.64, 132.62, 132.54, 132.10, 131.53, 130.91, 128.12, 127.86, 127.17, 126.94, 126.74, 126.36, 125.72, 47.92 and 43.55, 11.57 and 9.24. LRMS [M‐e]‐: Calculated for C72H50O12S4 1234.2185, wasn't observed, [M‐e]2- 616.4654, [M‐ e]3‐ 410.6887 [M‐e]4‐ 307.7937. [M+H]+: Calculated for C6H16N 102.1277, found 102.1297.

[0331] Tetratriethylammonium Tetra(parasulfonated)bis-tetracyclone (1c) To a 25 mL Schlenk flask containing argon and a stir bar, molecule 3c (1.260 g, 1.687 mmol), linker 2c (0.145 g, 0.823 mmol), and nitrobenzene (13 mL) were added. The flask was sealed with a septum, and a freeze-pump-thaw cycle was performed 3 times using liquid nitrogen. The mixture was stirred vigorously for 10 minutes and reacted at 215 °C with moderate stirring for 48 hours. The reaction product was cooled to room temperature. Ethyl acetate (2 mL) was added to promote precipitation, and the reaction product was poured into ethyl acetate (200 mL), refluxed for 4 hours, filtered, and the precipitate was washed twice with boiling ethyl acetate and once with diethyl ether. The compound was dried overnight at 80 °C under vacuum to obtain the pure product as a pale gray solid (1.240 g, 0.768 mmol, 93.3%). 1H NMR (600 MHz, Methanol-d4) δ (ppm): 7.77 (dd, J = 6.4, 3.3 Hz, 2H), 7.62 (d, J = 8.3 Hz, 5H), 7.41 (dd, J = 6.5, 3.3 Hz, 2H), 7.32 (dd, J = 8.3 Hz, 4H), 7.30 (s, 2H), 7.26 (d, J = 8.3 Hz, 4H), 7.20 (s, 2H), 7.09 (dd, J = 8.1 Hz, 2H), 6.98 - 6.79 (m, 20H), 3.11 (q, J = 7.3 Hz, 24H), 1.22 (t, J = 7.3 Hz, 36H). 13C NMR (150 MHz, Methanol-d4) δ (ppm): 144.98, 144.46, 143.60, 143.48, 141.58, 141.42, 141.21, 141.18, 141.01, 140.35, 139.59, 133.46, 132.77, 132.66, 132.59, 132.50, 131.06, 128.42, 128.14, 127.86, 127.83, 127.64, 126.97, 126.80, 126.73, 126.42, 125.23, 47.88, 9.22. LRMS [M−e]−: Calculated for C70H48O12S4 1208.2029, wasn't observed, [M−e]2− 603.1008, [M−e]3− 401.7318 [M−e]4− 301.0470. [M+H]+: Calculated for C6H16N 102.1277, found 102.1278

[0332] Sulfonated Polyphenylene (Biphenyl Linked) Triethylammonium Salt (sPPB-HNEt3 Absolute ethanol (600 mL), 1,4 - bisbenzyl (6.51 g, 19.02 mmol), and 1,3 - (diphenyl)propan - 2 - one (8.40 g, 39.94 mmol) were combined in a 1 L two - necked round - bottom flask equipped with a stir bar. The flask was equipped with a condenser and an addition funnel with a cap and stirred under reflux for 1 hour to dissolve completely. Next, a solution of KOH (2.14 g, 38.04 mmol, dissolved in 10 mL of absolute ethanol) was added dropwise to the yellow solution using a dropping funnel. The resulting black solution was stirred under reflux for an additional 1 hour and cooled to 0 °C in an ice bath. The solution was filtered, and the precipitate was washed several times with ice - cold ethanol and dried under vacuum at 80 °C for 8 hours. The resulting black powder was recrystallized from dichloromethane to obtain a dark - purple needle - shaped crystalline solid product (9.16 g, 13.26 mmol, 69.7%). 1H NMR (500 MHz, CD2Cl2) δ (ppm): 7.30 - 7.18 (m, 26H), 6.92 (d, J = 7.1 Hz, 4 H), 6.78 (s, 4H). 13C NMR (125 MHz, CD2Cl2) δ (ppm): 200.60, 154.93, 154.67, 134.12, 133.51, 131.41, 131.26, 130.66, 130.60, 129.77, 129.51, 129.05, 128.53, 128.12, 128.07, 126.19, 125.93. LRMS [M+H]+: Calculated for C52H34O2 690.2559, found 691.2411.

[0333] Tetra(para-sulfonated) bis-tetracyclone(1b) Dichloroethane (550 mL) was added to a 1 L two-necked round-bottom flask equipped with a stir bar. The flask was equipped with a septum and a sealed dropping funnel, and the apparatus was degassed with argon. Bistetracyclone 1a (6.00 g, 8.69 mmol) was added to the dichloroethane, and the mixture was stirred for 15 minutes while degassing. Trimethylsilyl chlorosulfonate (21.40 mL, 138.96 mmol) was diluted with 30 mL of degassed dichloroethane, placed in the dropping funnel, and added dropwise to the flask. The mixture was stirred for 16 hours, ethanol (3 mL) was added, and then the mixture was stirred for an additional 2 hours. The reaction product was poured into pentane (2 L), the precipitate was filtered, and washed with pentane and cold ethyl ether. Vacuum dried at 60 °C for 12 hours to obtain the final product as a purple solid powder (8.43 g, 8.34 mmol, 96.0%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 7.53 (s, 4H, H2O / H3O+), 7.50 (d, J = 8.2 Hz, 4H), 7.48 (d, J = 8.2 Hz, 4H), 7.33 (m, 2H), 7.25 (t, J = 7.5 Hz, 4H), 7.13 (d, J = 8.3 Hz, 4H), 7.08 (d, J = 8.3 Hz, 4H), 6.92 (d, J = 7.4 Hz, 4H), 6.86 (s, 4H). 13C NMR (125 MHz, DMSO-D6) δ (ppm): 199.38, 154.79, 154.63, 147.14, 147.08, 133.18, 132.08, 130.57, 130.23, 129.19, 128.96, 128.79, 128.63, 128.13, 125.26, 125.21, 124.44, 124.15. LRMS [M‐e]‐: Calculated for C52H34O14S4 1010.0831, found 1009.5466, [M‐e]2- 504.3521, [M‐ e]3‐ 335.9417 [M‐e]4‐ 251.7321.

[0334] Sulfonated Polyphenylene (Biphenyl Linked) Acid (sPPB-H A stir bar was equipped, and 1b (6.50 g, 6.43 mmol) was added to a 1 L round-bottom flask containing butyl alcohol (300 mL). A dropping funnel was connected to the flask, and trimethylamine (144 mL, 1.03 mmol) was added dropwise to the mixture with vigorous stirring. The reaction mixture was stirred for 12 h, filtered, and the precipitate was washed with trimethylamine (200 mL) and ethyl ether (500 mL). It was dried under vacuum at 120 °C for 72 h to obtain the final product as a bright purple powder (9.02 g, 6.37 mmol, 99.1%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 8.85 (s, 4H), 7.49 (d, J = 8.0 Hz, 4H), 7.47 (d, J = 8.1 Hz, 4H), 7.33 (m, 2H), 7.25 (t, J = 7.2 Hz, 4H), 7.13 (d, J = 8.2 Hz, 4H), 7.09 (d, J = 8.2 Hz, 4H), 6.92 (d, J = 7.4 Hz, 4H), 6.86 (s, 4H), 3.09 (q, J = 7.5 Hz, 24H), 1.17 (t, J = 7.3 Hz, 36H). 13C NMR (125 MHz, DMSO-D6) δ (ppm): 199.40, 154.76, 154.58, 147.26, 147.24, 132.08, 131.13, 130.50, 130.12, 129.16, 129.04, 128.92, 128.78, 128.61, 128.11, 125.24, 125.19, 124.44, 124.15, 45.76, 8.63. LRMS [M‐e]‐: Calculated for C52H34O14S4 1010.0831, found 1009.5577, [M‐e]2- 504.3578, [M‐ e]3‐ 335.9443 [M‐e]4‐ 251.7326. [M+H]+: Calculated for C6H16N 102.1277, found 102.1284.

[0335] ​ + )

[0336]

Chem.

[0337] To a 25 mL Schlenk flask containing argon and equipped with a stir bar, monomer 1c (1.249 g, 0.882 mmol), linking group 2b (0.184 g, 0.909 mmol), and nitrobenzene (13 mL) were added. The flask was sealed with a septum, and a freeze-pump-thaw cycle was carried out three times using liquid nitrogen. The mixture was reacted at 215 °C with moderate stirring for 48 h. After cooling, the reaction mixture was poured into ethyl acetate (600 mL), refluxed for 4 h, filtered, and the recovered precipitate was washed twice with boiling ethyl acetate and once with diethyl ether. The polymer was dried overnight at 80 °C under vacuum to obtain the pure product as a brown powder (1.31 g, 0.839 mmol, 95.1%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 8.89 (s, 4H), 7.56 - 6.02 (m, 40H), 3.05 (two overlapped q, J = 7.3 Hz, 24H), 1.10 (t, J = 7.3 Hz, 36H). GPC Analysis: Mn = 112,000 g mol-1, Mw = 175,000 g mol-1, Mw / Mn = 1.56.

[0338] ​ + ) sPPB-HNEt3 +(1.01 g, 0.647 mmol of repeating unit) was dissolved in methanol (50 mL) with vigorous stirring at room temperature in a 250 mL round-bottom flask. Next, 1 M NaOH (in 50 mL of methanol) was added dropwise. A precipitate formed, and the solution was stirred for an additional 2 hours, filtered, and the precipitate was washed three times with methanol and once with diethyl ether. The polymer sPPB-Na+ was vacuum dried at 80 °C overnight. This was dissolved in water (50 mL) with vigorous stirring at room temperature in a 250 mL round-bottom flask, and 1 M aqueous sulfuric acid (in 50 mL of water) was added dropwise. A precipitate formed, and the solution was stirred for an additional 2 hours, filtered, and the polymer was washed three times with water and once with diethyl ether. Vacuum drying at 80 °C overnight gave the pure product as a dark brown solid (0.64 g, 0.553 mmol of repeating unit, 85.5%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 6.02–7.60 (m, 40H), 4.19 (s, H2O / H3O+). GPC Analysis: Mn = 130,000 g mol-1, Mw = 189,000 g mol-1, Mw / Mn = 1.45.

[0339] Sulfonated polyphenylene (naphthalene-linked) triethylammonium salt (sPPN-HNEt3 + )

[0340]

Chemical Structure

[0341] Into a 25 mL Schlenk flask containing argon and a stir bar, monomer 1c (1.178 g, 0.832 mmol), linking group 2c (0.151 g, 0.857 mmol), and nitrobenzene (12 mL) were added. The flask was sealed with a septum, and three freeze-pump-thaw cycles were performed using liquid nitrogen. The mixture was reacted at 215 °C with moderate stirring for 48 h. After cooling, the reaction mixture was poured into ethyl acetate (600 mL), refluxed for 4 h, filtered, and the recovered precipitate was washed twice with boiling ethyl acetate and once with diethyl ether. The polymer was dried overnight under vacuum at 80 °C to obtain the pure product as a brown powder (1.180 g, 0.768 mmol, 92.3%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 8.89 (s, 4H), 7.81 - 6.30 (m, 38H), 3.02 (two overlapped q, J = 7.3 Hz, 24H), 1.09 (t, J = 7.3 Hz, 36H). GPC Analysis: Mn = 141,000 g mol-1, Mw = 329,000 g mol-1, Mw / Mn = 2.33.

[0342] Sulfonated polyphenylene (naphthalene-linked) acid (sPPN-H + )

[0343]

Chemical Structure

[0344] sPPN-HNEt3 +(2.80 g, 1.823 mmol of repeating unit) was dissolved in methanol (50 mL) with vigorous stirring at room temperature in a 250 mL round-bottom flask. The solution was stirred until completely dissolved. Next, 1 M NaOH (in 50 mL of methanol) was added dropwise. A precipitate formed, and the solution was stirred for an additional 2 h, filtered, and the precipitate was washed three times with methanol and once with diethyl ether. The polymer sPPN-Na+ was dried in vacuo overnight at 80 °C. This was dissolved in water (50 mL) with vigorous stirring at room temperature in a 250 mL round-bottom flask, and the solution was stirred until completely dissolved. 1 M aqueous sulfuric acid (in 50 mL of water) was added dropwise here. A precipitate formed, and the solution was stirred for an additional 2 h, filtered, and the polymer was washed three times with water and once with diethyl ether. It was dried in vacuo overnight at 80 °C to give the pure product as a dark brown solid (1.48 g, 1.308 mmol of repeating unit, 71.8%). 1H NMR (500 MHz, DMSO-D6) δ (ppm): 6.19‐7.63 (m, 38H), 4.15 (s, H2O / H3O+). GPC Analysis: Mn = 185,000 g mol-1, Mw = 341,000 g mol-1, Mw / Mn = 1.84.

[0345] Membrane preparation The membrane was formed from a 5 w% DMSO solution. A typical membrane preparation was carried out as follows. 0.290 g of sPPB-H+ was dissolved in 5.51 g of DMSO with stirring at 80 °C. The resulting polymer solution was filtered through a glass fiber filter into a flat 95 mm diameter Petri dish. It was carefully dried in a sealed vacuum oven at 85 °C under atmospheric pressure for 48 h to obtain a polymer film. This was immersed in 1 M H2SO4 for 24 h, in DI H2O for 24 h, immersed / washed three times in DI H2O, and dried overnight under vacuum at 80 °C.

[0346] Characteristic evaluation Analysis of polymers and small molecules 1 H and 13 The 1H NMR spectrum was measured at room temperature (T = 298 K) on a Bruker AVANCE III 500 MHz equipped with a 5 mm TXI inverse probe, using DMSO-d6 as the solvent. Size exclusion chromatography analysis was performed using Waters HPLC HR 5, HR 4, and HR 3 columns, with HPLC grade DMF (containing 0.10 M LiBr) as the eluent. A polystyrene sample purchased from Waters Associates Inc. was used as the calibration standard. Thermogravimetric analysis (TGA) measurements were carried out on a PerkinElmer STA6000, heating at a rate of 10 °C per minute from 30 °C to 600 °C under a nitrogen atmosphere to evaluate the thermal stability of the polymer.

[0347] Measurement of water absorption rate of membrane First, the water absorption rate of the membrane was tested. It was immersed in DI H2O at 25 °C and then at 80 °C for 1 hour. To efficiently measure the water absorption rate, it is necessary to obtain the difference between the weight of the completely dried membrane and the weight of the completely hydrated membrane. The membrane sample was placed in a vacuum oven at 80 °C for 24 hours, cooled to room temperature under vacuum, taken out from the vacuum chamber, and weighed immediately. This process was repeated at least 5 times, and the average was taken as the mass (mdry) of the completely dried sample membrane. Next, the sample was immersed in DI H2O for 24 hours, wiped with a Kimwipe, and weighed immediately to obtain the hydrated mass (mwet). Using the following formula (1), the water absorption rate of a given sample can be calculated. Similarly, the swelling ratio of the sample can be calculated by comparing the surface areas of the completely dried sample membrane and the completely hydrated sample membrane using the following formula (2).

[0348]

Equation

[0349] Oxidation stability The acid stability test can be carried out by immersing the membrane in Fenton's reagent to determine its stability against hydroxyl species and oxygen radicals similar to the operating conditions of a fuel cell. In a typical trial, a dried membrane of 2×2 cm with a known dry weight was immersed with stirring in a >3.0% H2O2 solution in 50 mL of DI H2O at 80 °C. An FeSO4 solution in DI H2O was added thereto to make a total concentration of 3 ppm Fe2+ and 3.0% H2O2. The resulting solution was stirred for 1 hour. The membrane was recovered, immersed in 1 M H2SO4 for 24 hours, in DI H2O for 24 hours, immersed / washed three times with DI H2O, vacuum dried overnight at 80 °C, weighed again, and analyzed with a 1H NMR spectrometer.

[0350] Ion exchange capacity (IEC) of membrane The ion exchange capacity is used to represent the sulfonic acid capacity and can be measured by conventional titration techniques. This procedure involves converting the cations of the membrane in the acid form (-SO3-H+) to their corresponding sodium salts (-SO3-Na+) by immersing the sample in a pH 7, 1 M NaCl solution for 48 hours. Next, the resulting acidic solution is returned to pH 7 by back-titration using a standard titration solution (0.01 M NaOH solution, Sigma Aldrich) and a Metrohm 848 Titrino Plus automatic titrator. The IEC can be calculated from the volume (Vt) and molar concentration (Ct) of the standard titration solution used and the dry mass of the sample being titrated, as shown in Equation (3) below. All experimental results are the average of at least five measurements carried out for each test. The theoretical value of the IEC can be determined by comparing the molecular weight (MWn) of one repeating unit of the polymer and the number of moles of sulfonic acid (nSO3H) sites present therein, as shown in Equation (4) below.

[0351]

Number

[0352] Proton conductivity of membrane The proton conductivity was measured as follows. A conductivity cell was constructed with a membrane piece of 0.5×1.0 cm and subjected to an AC impedance spectrometer using a Solartron 1260 frequency response analyzer (FRA) incorporating the two - electrode configuration as described above. A sinusoidal AC voltage of 100 mV was used in the frequency range of 10 MHz to 100 Hz. The proton conductivity measurement with controlled temperature and humidity was carried out using an Espec model SH - 241 humidity chamber. The data was obtained as a Nyquist plot and fitted to a Randles equivalent circuit to obtain the value of the membrane ionic resistance Rp. The proton conductivity (σH+) can be calculated from the distance L (cm) between the electrodes and the cross - sectional area A (cm2) of the membrane using the following equation (5).

[0353] [Number]

[0354] The acid concentration [-SO3H] can be used as an approximation of the free proton concentration in the membrane and can be calculated from the following equation (6) using the experimental values of IEC (IECtitr), dry mass (mdry), and swollen volume (Vwet) in the membrane. Thus, the proton mobility (μH+) can be calculated according to the following equation (7).

[0355] [Number]

[0356] Thermogravimetric analysis The thermal degradation data of sulfonated polyphenylene shows the characteristics of three degradation patterns: thermal dissolution of the polyphenylene backbone, desulfonation, and decomposition (Figure 11). The first weight loss was observed between 100 and 150 °C and corresponds to the loss of residual absorbed water in the material. The second weight loss occurred between 260 and 400 °C in all samples as a result of the loss of -SO3H moieties. The third weight loss region observed at temperatures higher than 550 °C is due to the decomposition of the main polymer backbone. Overall, the reported sulfonated polyphenylene showed excellent thermal stability.

[0357] Table 2-1 Water Absorption and Swelling Ratio. Dimensional Changes of sPPX Film Compared with NR-211. The dimensional changes are those between the completely dried state (vacuum drying at 80 °C for 24 h) and the completely hydrated state (equilibrated with DI H2O at room temperature for 24 h).

[0358] [Table 1]

[0359] Table 2-2 Fenton Test. Accelerated Degradation and Oxidation Stability Obtained from the Fenton Reagent Test

[0360] [Table 2]

[0361] Table 2-3 sPPN-H + 、sPPB-H + 、and Values of IEC, Acid Concentration ([SO3H]), and Proton Mobility (μ H+ ) of NR-211

[0362] [Table 3]

[0363] Method for preparation of MEA and in-situ characteristic evaluation Catalyst inks with PFSA reference ionomers (Nafion® D520) and hydrocarbon ionomers (sPPB-H+, sPPN-H+) were prepared. Water and methanol were successively added to the catalyst powder. While the resulting mixture was rapidly stirred, the ionomer dispersion was dropped in. The catalyst powder was Pt / C (TKK TEC-10e50e), containing 46.4 wt% Pt on a graphite carbon support. The final water:methanol ratio was 1:3. The total solids in the solution was 1 wt%. For the electrodes incorporating PFSA, in the optimized state, the ink contained 30 wt% solid ionomer, and for the hydrocarbon ionomers, the ink contained 20 wt% solid ionomer.

[0364] The formation of the membrane electrode assembly was carried out by performing ultrasonic spray coating (Sono-Tek ExactaCoat SC) on the electrode substrate on a heated vacuum plate (85 °C) to form a coated catalyst membrane (CCM) with a final electrode area of 5 cm 2 The PFSA substrates were Nafion® 211, 25 ± 1 μm, or Nafion® 212, 50 ± 1 μm. For the hydrocarbon membrane data, the substrates were sPPB-H+, 33 ± 2 μm, and sPPN-H+, 80 ± 4 μm. The thickness was measured 8 times with a micrometer around the perimeter. The catalyst loading was 0.4 mg Pt·cm-2 per unit area of PFSA ionomer (cathode and anode) for the hydrocarbon membrane and N212 PFSA reference. The catalyst loading was 0.4 mg Pt·cm-2 for the hydrocarbon ionomer cathode and ND520 PFSA reference. The catalyst loading was 0.2 mg Pt·cm-2 per unit area of the ND520 PFSA ionomer anode on the N211 PFSA reference membrane.

[0365] To attach the resulting CCM to the fuel cell hardware, a commercially available gas diffusion layer (GDL) with a microporous layer was applied (Sigracet 24BC), achieving a final GDL compression of 20 - 30% and a torque of 5.6 N·m (50 in·lbs) with a gasket. The fuel cell was evaluated in situ using a fuel cell test station (Teledyne Medusa RD 890CL, Scribner Associates). The fuel cell was adjusted as follows. The fuel cell repeated a slow polarization curve from 200 mA·cm-2 to a cut-off of 0.35 V at 25 mA·cm-2 intervals over 12 - 24 hours until a constant operation was achieved. Polarization data was acquired at 5 min·pt-1 at 200 mA·cm-2 intervals from the OCV to a potential cut-off of 0.3 V. The resolution of the motion region at 1 min·pt-1 at this time was obtained at 2 mA·cm-2 intervals in the range of 2 - 20 mA·cm-2. These were repeated.

[0366] After adjustments were made for both the sPPB-H+ and sPPN-H+ membranes, a humidity cycle was performed at 90 - 100% RH for the cathode and 95 - 100% RH for the anode, and a mechanical load was applied to the membrane by reducing the humidity and losing water production while maintaining the current at a low power density for a long time. This was continuously performed for 13 back-to-back polarizations for each of the above methodologies, associated with the polarization curves obtained at 5 s·pt-1 and 3 s·pt-1 in the motion region, to explore any transient water transport effects, and a total of 25 hours of operation was carried out.

[0367] Using a combination of a potentiostat / FRA (PARSTAT, Princeton Applied Research), after equilibrating the fuel cell to a stable potential of <0.15 V with 0.25 / 0.5 slpm H2 / N2, electrochemical property evaluation was performed. To determine fuel crossover, chronoamperometry (CA) was carried out at 30 s·step-1 in 100 mV steps from 0 to 600 mV, and fuel crossover was determined as the average ± sample standard deviation of the current density at 500 mV for the last 50% of the holding potential, i.e., 15 s. To judge potential electrical short circuits, linear sweep voltammetry (LSV) was carried out, sweeping from a low equilibrium potential to 600 mV at a rate of 2 mV·s-1.

[0368] The accelerated stress test (AST) was conducted by open circuit voltage (OCV) hold. This was carried out using a fuel cell test station, as closely as possible in accordance with the protocol of the US Department of Energy. That is, it was carried out under the conditions of 90 °C, 30% RH at the anode and cathode, a gas flow rate of H2 / Air corresponding to a stoichiometric flow rate of 10 / 10 at a current density of 0.2 A·cm-2, zero backpressure, and 0.05 / 0.17 slpm in a 5 cm2 cell. The fuel crossover detected by CA was a normal electrochemical characteristic. sPPB-H+ was equilibrated to these conditions after being operated for 72 hours as described below. When the PFSA reference was equilibrated under these conditions, these gave an initial potential of <0.9 V and stopped. The PFSA reference was thus equilibrated under these conditions without prior adjustment and gave an initial potential of <0.9 V under AST conditions (Figs. 9 and 10).

[0369] In both cases, considering particularly the variation in RH employed and the sensitivity of these variations of the PFSA ionomer in the catalyst layer, the polarization data were in agreement (Fig. 12). The 95% confidence interval (μ ± 2σ) at 2 A·cm-2 was 999 - 1022 mW·cm-2 for the 33 ± 2 μm sPPB-H+ membrane and 903 - 927 mW·cm-2 for the 80 ± 4 μm sPPN-H+ membrane. The maximum and minimum values of the potential at a given current density within the data set corresponded to the high-hydration state and low-hydration state of the cathode, respectively, suggesting that there was no significant increase in mass transport loss in the fully humidified state as expected when the membrane swelled to compress the catalyst layer or insert into the catalyst layer. These results together suggest a high transportability of water through both the membrane and the electrode, which is supported by the measured high in situ conductivity.

[0370] The measured in situ conductivity of the adjusted membranes was also internally consistent between the IV at a specific RH and the oxidant gas supply. The resistance data of the MEA measured at 80 °C and nominally 100% RH were pooled and converted to conductivity using Equation (2-5). Further, considering the uncertainties in the iR and thickness measurements, it was finally determined that σsPPN > σsPPB > σN212. All membranes showed behavior consistent with the conductivity measured ex situ at 95% RH and 80 °C (Figure 13B).

[0371] Fuel crossover was very low for sPPB-H+ and low for sPPN-H+ after 74 and 72 hours of operation, respectively, compared to the adjusted N211 reference MEA after 41 hours of operation (Figure 13A).

[0372] Table 2-4: Combinations of chemical / mechanical accelerated stress tests by high temperature / low RH OCV hold. Representative OCV per AST time for sPPB-H+ relative to PFSA reference.

[0373]

Table 4

[0374] Fuel crossover was measured at intervals throughout the AST, and sPPB-H+ showed very low crossover compared to the PFSA reference throughout (Figure 15). The peak power densities were 587 and 408 mW·cm-2, and the in situ conductivities measured before and after 400 hours of OCV hold were 171 ± 17 and 117 ± 6 mS·cm-1, respectively, with the latter still exceeding 97 ± 4 mS·cm-1 of the fully adjusted pristine high-performance PFSA reference (Figure 18).

[0375] Example 3 Improvement of stability and efficiency of sulfonated poly(para-phenylene): Study on random copolymer Equipment and raw materials 1 H and 13The 13C NMR spectra were measured on a Bruker AVANCE III 500 MHz equipped with a 5 mm TXI inverse probe at room temperature (T = 298 K). The terms s means singlet, d means doublet, t means triplet, q means quartet, m means multiplet, chemical shifts are reported in ppm, and J-couplings are reported in Hz. The proton and carbon residual peaks of the deuterated solvents were set at 2.05 ppm and 29.84 ppm for d6-acetone, 2.50 ppm and 39.52 ppm for d6-DMSO, and 5.32 ppm and 54.00 ppm for CD2Cl2, respectively.

[0376] The mass spectra were measured in both positive and negative modes (ESI mode) using an AB Sciex 4000 Q TRAP spectrometer and a Bruker microOTOF.

[0377] Size exclusion chromatography analysis was performed using Waters HPLC HR 5, HR 4, and HR 3 columns with HPLC grade dimethylformamide (DMF: containing 0.10 M LiBr) as the eluent. Polystyrene samples purchased from Waters Associates Inc. and Sigma Aldrich Canada Co. were used as calibration standards, the elution rate was 1 mL min-1, the column oven was set at 80 °C, and the refractive index detector was set at 50 °C.

[0378] Ion-exchanged water (DI water) was purified to 18.2 MΩ using a Millipore Gradient Milli-Q® water purification system.

[0379] The film was formed using a horizontal glass plate with a K202 Control Coater casting table and an adjustable doctor blade (RK PrintCoat Instruments Ltd.) to obtain a film of the polymer solution with a thickness of 0.50 - 0.75 mm. The polymer film was dried in an oven at 85 °C for 24 hours, peeled from the glass plate, immersed in 5 L of distilled water for 24 hours, and dried under vacuum at 80 °C for 24 hours. A film with a thickness of 30 - 60 μm was obtained.

[0380] Titration was carried out using a Metrohm 848 Titrino plus equipped with a stir plate 801 Stirrer Metrohm and a pH meter probe Metrohm 6.0262.100.

[0381] The measurement of impedance was carried out using a Solartron Impedance SI 1260 / impedance gain-phase analyzer with Zview and Zplot as software. Two ESPEC SH-241s were used as the humidity chambers.

[0382] Triethylamine (NEt3, 99%), activated carbon (G-60), hydrochloric acid (ACS reagent, content 36.5 - 38%) were purchased from Anachemia Science. 1,4-Diiodobenzene (98%), phenylacetylene (98%) were purchased from Combi-Blocks, Inc and used without purification. Acetone (ACS guaranteed), dichloromethane (DSM, ACS stabilized guaranteed), diethylamine (97%), methanol (MeOH, reagent grade), pentane (reagent grade), ethyl acetate (ACS guaranteed), silica gel (S825-1, 230 - 400 mesh, grade 60), neutral alumina (60 - 325 mesh, Rockman active I), anhydrous magnesium sulfate (guaranteed powder), and Celite (trademark) (545 filter aid, unwashed powder) were purchased from Fisher Scientific. Nitrobenzene (98%, reagent plus grade), diethylamine (reagent plus grade, 98%), dimethylformamide (DMF, Chromatosolv® HPLC grade), trimethylsilyl chlorosulfonate (99%), lithium bromide (reagentPlus® grade, >99%) were purchased from Sigma-Aldrich Canada Co. Diethylamine and nitrobenzene were degassed with argon prior to each use, and all other compounds were used without further purification. Ethanol (99%) was purchased from Commercial Alcohols. Trimethylsilylacetylene (lot number 003013I12J) was purchased from Oakwood. Anhydrous diethyl ether (ACS reagent), sodium chloride (ACS reagent), anhydrous potassium carbonate (ACS grade), sodium thiosulfate anhydrous (reagent grade) were purchased from ACF Montreal. Chloroform (ACS grade), dimethyl sulfoxide (ACS grade), sodium hydroxide (ACS grade), and iodine (analytical reagent) were purchased from BDH. Petroleum ether (reagent grade), n-butanol (reagent grade), potassium hydroxide (reagent grade, 85% or higher), sulfuric acid (reagent grade) were purchased from Caledon. 1,3-Diphenylacetone (ACS reagent, 98%) was purchased from Tokyo Chemical Industry Co., Ltd. Argon (PP 4.8) was purchased from Praxair. Diphenylphosphine palladium dichloride (Pd(P(phi)3)2Cl2, 97%) and copper(I) iodide (>99.9%) were purchased from Strem Chemicals. Dimethyl sulfoxide-d6 (D, 99.9%), acetone-d6 (D, 99.9%), methylene chloride-d2 (D, 99.8%, CD2Cl2) were purchased from Cambridge Isotope Laboratories, Inc.

[0383] Synthesis and characteristic evaluation The overall synthetic scheme is shown in Scheme 3-S1 of Figure 19. Different sPPP(y)-(HNEt3 + ) and sPPP(y)-(H + ) were obtained by chemical routes. (i) Pd(P(Phi)3)2Cl2, CuI, HNEt2, 56 °C, 6 h: 3 (94.5%), 10 (98.0%); (ii) I2, DMSO, 150 °C, 8 h: 4 (65%); (iii) KOH, EtOH, 80 °C, 3 h: 6 (80.4%); (iv) TMSO-SO2-Cl, DCE, RT, 8 h: 7 (93%); (v) NEt3, n-BuOH, 4 h, 8 (98.3%); (vi) K2CO3, diethyl ether / methanol (3 / 1), RT, 6 h: 11 (97.0%); (vii) nitrobenzene, 195 - 220 °C, 2 - 3 days: PPP and sPPP(y)-(HNEt3 + )(73 - 93%); (viii) NaOH (MeOH) , MeOH, 4 h, RT, sPPP-(y)-(Na + )(93 - 99%); (ix) H2SO 4(aq) , H2O, 4 h, RT: sPPP-(y)-(H+)(75 - 94%).

[0384] Compounds 6, 7, 8, 10, and 11 were synthesized as already disclosed in T. J. G. Skalski, B. Britton, T. J. Peckham and S. Holdcroft, Journal of the American Chemical Society, 2015, 137, 12223 - 12226, which is incorporated herein by reference in its entirety.

[0385] Synthesis of compound 3: 1,4-di(phenylethynyl)-benzene Scheme 3-S2: Synthesis of compound 3: 1,4-di(phenylethynyl)-benzene

[0386]

Chemical formula

[0387] A 2 L three-necked round-bottom flask, previously dried in an oven at 105 °C, was equipped with a stir bar, a stopper, and two stoppers and filled with argon. Under a gentle flow of argon, 1,4-diiodobenzene (81.4 g, 242 mmol, 1 equiv), trans(triphenylphosphine)palladium(II) dichloride (0.343 g, 0.484 mmol, 0.002 equiv), diethylamine (1 mL / 0.100 g of the dihalogenated derivative), and phenylacetylene (56.9 mL, 508 mmol, 2.10 equiv) were added. The reaction mixture was stirred for 15 minutes. A 60 mL Schlenk tube was evacuated and purged with argon three times, and copper(I) iodide (0.0935 g, 0.484 mmol, 0.002 equiv) and diethylamine (2.0 mL) were added thereto. After the copper iodide had completely dissolved (a purple solution), the remaining solution was transferred to a 3 L reactor using a PEEK cannula. The reaction was slowly heated to 56 °C over 6 hours using an oil bath. After cooling to room temperature, the solution was carefully poured into a 4 L beaker containing 10% HCl (aq) solution while stirring the solution carefully. The precipitate was removed by suction filtration and subsequently washed with water (150 mL), methanol (2 × 150 mL), and hexane (until the color completely disappeared from the filtrate). Compound 3, 1,4-di-(phenylethynyl)-benzene, was obtained as a white to yellowish powder and used without further purification steps. Yield: 63.6 g (94.6%) 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 7.36 - 7.40 (m, 6H), 7.53 (s, 4H), 7.54 - 7.56 (m, 4H) 13 C NMR (125 MHz, CD2Cl2) δ (ppm): 89.47(b), 91.70(a), 123.52(e), 123.68(c), 129.02(g), 129.12(h), 132.09(f), 132.13(d).

[0388] Synthesis of compound 4: Bisbenzyl Scheme 3-S3: Synthesis of Compound 4: Bisbenzyl

[0389]

Chem.

[0390] To a 250 mL round-bottom flask equipped with a stir bar and a water condenser, 3 (7.5 g, 26.9 mmol, 1 equiv), DMSO (128 mL), and iodine (13.69 g, 53.9 mmol, 2 equiv) were added. The mixture was refluxed at 150 °C for 8 h, cooled, and poured into 1.0 L of 15 wt% aqueous Na2S2O3 solution, and stirred vigorously for 30 min (until the bright yellow persisted). The remaining solution was filtered and washed three times with water (100 mL each time). The precipitate was dissolved in chloroform and filtered through a small pad of silica gel (10 - 15 cm in height) until the elution of a bright yellow solution was observed from the silica gel. The solution was concentrated under vacuum and recrystallized twice from anhydrous methanol (70 - 130 mL) to give 5.99 g (65.0%) of 4 as bright yellow needle crystals. 1 H NMR (500 MHz, CD2Cl2) δ (ppm): 7.56 (t, J = 8.03 Hz, 4H,), 7.71 (t, J = 7.42 Hz, 2H), 7.97 (d, J = 7.29 Hz, 4H), 8.11 (s, 4H) 13 C NMR (125 MHz, CD2Cl2) δ (ppm): 129.71(f), 130.46(g), 130.76(b), 133.15(e), 135.84(h), 137.69(a), 194.01(c), 194.10(d). HRMS [M+H]: calcd for C 22 H 14 O4342.0892 found,[M+H]: 343.0962, [M+Na]: 365.0784

[0391] As an example, the synthesis method of sPPP(0.9)-(HNEt 3 +) is used for the general process of synthesis of sPPP-(y)-(HNEt 3 + ) Into a 250 mL Schlenk flask, 6 (0.217 g, 0.314 mmol, 0.1 eq), 8 (4.00 g, 2.83 mmol, 0.9 eq), and 11 (0.402 g, 3.19 mmol, 1.02 eq), and nitrobenzene (40 mL) were introduced. The mixture was stirred for 30 minutes until the compounds were completely dissolved. Then, it was heated at 205 °C for 3 hours using a sand bath. After cooling, the mixture was poured into ethyl acetate (400 mL) and refluxed for 4 hours. The solution was filtered while boiling and washed three times with boiling ethyl acetate. Finally, the powder was dissolved in the minimum amount of methanol (15 mL) and precipitated from ethyl acetate (500 mL). After filtration, the obtained sPPP(0.9)-(HNEt3 + ) was dried overnight at 120 °C under vacuum to obtain a white fibrous product (4.17 g, 84.7%).

[0392] According to the approach we propose, six hydrophilic polymers were created for the family of sPPP(m)(HNEt3 + ) and one completely hydrophobic polymer was created for sPPP(0.0)(HNEt3 + ).

[0393] sPPP(m)(HNEt 3 +) Conversion of sPPP(m)(HNEt sPPP(m)(HNEt3 + )(2.4 g) was dissolved in methanol (25 mL) in a 100 mL round-bottom flask equipped with a stir bar and a 50 mL dropping funnel. After complete dissolution, a 2 M NaOH solution in methanol (10 mL) was added dropwise. After stirring for an additional 2.5 hours, the resulting slurry was carefully vacuum filtered through a Buchner funnel equipped with a glass fiber filter paper, and the isolated solid was washed with methanol (10 mL each time) and diethyl ether (20 mL each time). It was dried overnight at 80 °C under vacuum to quantitatively obtain sPPP(m)(Na + ) without further purification.

[0394] In a 250 mL round-bottom flask equipped with a stir bar and a 50 mL dropping funnel, sPPP(m)(Na+ ) was dissolved in water (30 mL). After complete dissolution, 2 M H2SO4 solution (15 mL) was added dropwise to the aqueous solution, and the mixture was further stirred for 4 h. The precipitate was collected using a Buchner funnel equipped with a glass fiber filter paper, washed three times with 10 mL of water, and washed with 35 mL of diethyl ether. It was dried overnight at 80 °C under vacuum to obtain polymer sPPP(m)(H + ) as a white-gray powder.

[0395] sPPP(0.5)(HNEt3 + ) was used as an example, and 1.97 g of sPPP(0.5)(Na + ) (yield > 99%) was obtained from 2.4 g, and then 1.95 g of sPPP(0.5)(H + ) (yield > 99%) was obtained.

[0396] ) to sPPP(m)(Na+), sPPP(m)(H+): General process Solutions of sPPP(m)(H + ) for forming films were all prepared at 10% w / w in hot DMSO (50 - 80 °C). After complete dissolution, each solution was filtered through a Buchner funnel equipped with a glass fiber filter paper (G8 from Fisher Scientific). The remaining solution was coated onto a glass plate supported on a K202 Control Coater casting table equipped with an adjustable doctor blade (RK PrintCoat Instrument Ltd.) pre-equilibrated at room temperature. Using a doctor blade set at 500 μm and moving the blade using the gear set at #2, the solution was spread on the glass plate. Next, the glass plate was transferred to an oven pre-equilibrated using a level and heated at 86 °C for 48 h. The film was cooled to room temperature, and the film was treated with 1.6 M HCl (aq)It was removed from the glass plate by immersing it in a bath. The film was immersed in 1.8 M H2SO4 for 1 hour, then in Milli-Q water for 1.5 hours, and dried on Kimtech (registered trademark) paper at room temperature. Finally, the film was compressed between two glass plates protected by Kimtech (registered trademark), dried overnight at 80 °C under vacuum, and cooled to room temperature under vacuum.

[0397] Formation of polymer membrane in acid form The molecular weight of the polymer was 1 calculated using 1H NMR and DMF SEC. 1 For 1H NMR, the molecular weight of the polymer was determined by using the triethylammonium cation as an internal standard. For DMF SEC, the molecular weights of polymers sPPP(m)(H + ) and sPPP(m)(H + ) were determined by correlating them to polystyrene standards. The results are reported in Table 3-S1.

[0398] Table 3-S1: Summary of the properties of the synthesized polymers sPPP(m)(X)

[0399]

Table 5

[0400] 1 The molecular weight by 1H NMR was determined by theoretical calculation. This molecular weight calculation was made possible by using a slight excess of compound 11 during polymerization.

[0401] Investigation of molecular weight The value of the ion exchange capacity of the film was 0.01 M NaOH (aq)It was obtained by automatic titration using the titrant. The titrant solution was calibrated using 0.01 M potassium hydrogen phthalate obtained by dissolving dried (80 °C, overnight, under vacuum) potassium hydrogen phthalate in water. Prior to titration, the membrane was immersed in 0.5 M HCl for 1 hour, then in Milli-Q water for the same time, dried at room temperature for 10 minutes, and then dried overnight at 80 °C under vacuum. The oven was cooled to room temperature before releasing the vacuum. For accuracy, the weight of the membrane was recorded twice. Finally, each piece of membrane was immersed overnight in 2 M NaCl (20 mL) (pH adjusted to 7.00 - 7.05 in advance). After removing the membrane, the remaining solution was titrated with the calibrated NaOH solution.

[0402] Equation 3 - S1: Determination of the actual concentration of sodium hydroxide for IEC calculation

[0403]

Number

[0404] {where [NaOH] aq represents the concentration of the actual sodium hydroxide solution in mol / L, [KHP] aq represents the concentration of the potassium hydrogen phthalate solution immediately after preparation in mol / L, V (KHP) represents the volume of the KHP solution used in L, V (NaOH) represents the titration volume obtained during titration in L.}

[0405] IEC is obtained according to Equation 3 - S2 below. Equation 3 - S2: IEC calculation of polymer sPPP(m)(H + )

[0406]

Number

[0407] {where IEC represents the ion exchange capacity in mequiv. / g, [NaOH] aqrepresents the concentration of the aqueous sodium hydroxide solution determined as described above in mol / L, and V eq represents the titration volume obtained during titration in L, and m (polymer) or m (sPPP(m)(H + ) represents the weight of the dry film in g.}

[0408] The theoretical IEC can be calculated using the molecular weight of the units in the polymer according to Figure 20.

[0409] According to the theoretical composition of the polymer, for example, 100 or 90%, the polymer weight can be calculated for 100 units (Table 3-S2, column 4). The number of sulfonic acids is obtained by multiplying the % ratio of the hydrophilic composition by 4 (the number of acidic functional groups per hydrophilic block, see Figure 20), which gives the number of sulfonic acid groups per 100 units of the polymer.

[0410] Table 3-S2: Determination of the theoretical calculation of sPPP(m)(H+) according to Figure 20 (see Figure 21)

[0411]

Table 6

[0412] Finally, the theoretical IEC, IEC th is obtained using the following equation.

[0413] Equation 3-S3: Determination of IEC th

[0414]

Number

[0415] {Wherein, IEC th is expressed in mequiv. / g, and nbSO3H 100u ​represents the number of sulfonic acids per 100 units of the polymer in moles (Table 3-S2, column 5), and Mn100u represents the molecular weight of 100 units of the polymer in g / mol (Table 3-S2, column 4).}

[0416] Ion exchange capacity (IEC) Prior to each measurement, the membrane was immersed in 1.6 M H2SO4 for 1 hour and then in Milli-Q water for 3 × 1 hour. The weight (w wet ) in the wet state, the thickness (T wet ) in the wet state, the dimensions (length (L wet ) and width (W wet )) were calculated. After drying at room temperature for 1 hour, the polymer piece was dried overnight in an 80 °C oven under vacuum. Before releasing the vacuum, the temperature was cooled to room temperature. After equilibration to the ambient environment for 10 minutes, the dry weight (w dry ), the dry thickness (T dry ), the length of the dimension (L dry ) and the width (W dry ) were determined.

[0417] Physical properties of polymer A hot water test was conducted to confirm whether the polymer can maintain its performance even in hot water (e.g., whether the polymer does not dissolve due to temperature increase).

[0418] The polymer piece was immersed in water at room temperature and the temperature was raised to 80 °C.

[0419] Table 3-S3: Hot water test of polymer sPPP(m)(H+)

[0420]

Table 7

[0421] Warm water resistance The water uptake (WU) is obtained according to the following formula. Equation 3-S4: Formula for water uptake, where WU(%) in the formula is a percentage, w wet and w dryIt is represented by g.

[0422]

Number

[0423] Table 3 - S4: Water absorption of polymer sPPP(m)(H+)

[0424]

Table 8

[0425] Water content (WC) The water content (WC) is obtained according to the following formula.

[0426]

Number

[0427] Formula 3 - S5: Formula for water content, where WC(%) is in percentage and w wet and w dry are represented by g.

[0428] Table 3 - S5: Water content of polymer sPPP(m)(H+)

[0429]

Table 9

[0430] Water uptake WU The volume uptake is determined by V = L x W x T (where L represents length, W represents width, and T represents thickness in the same dimension (mm)), and V dry and V wet can be expressed by the following formula. Formula 3 - S6: Formula for volume uptake

[0431]

Number

[0432] {wherein VU(%) represents the volume uptake as a percentage, L dry and L wet represent the lengths of the film pieces in the dry and wet states, respectively, in mm, W dry and W wet represent the widths of the film pieces in the dry and wet states, respectively, in mm, T dry and T wet represent the thicknesses of the films in the dry and wet states, respectively, in mm, and Vdry and Vwet represent the volumes of the films in the dry and wet states, respectively, in mm 3 .}

[0433] Table 3 - S6: Volume Uptake of Polymer sPPP(m)(H+)

[0434]

Table 10

[0435] Volume uptake (VU) Water sorption, λ (number of water molecules per sulfonic group), can be expressed according to the following equation. Equation 3 - S7: Equation for Water Sorption λ

[0436]

Number

[0437] {wherein lambda, λ, is the water sorption (mol H2O mol -1 -SO3H)10 excluding the percentage unit of WU(%), M H2O is the molecular weight of water in g mol -1 , and IEC represents the ion exchange capacity in mequiv. g -1 or mmol g -1 .}

[0438] Table 3 - S7: Water Sorption of Polymer sPPP(m)(H+)

[0439]

Table 11

[0440] Acid concentration of the membrane in the wet state [SO3H]: The acid concentration or [SO3H] is obtained using the following formula: Formula 3-S8: Formula for acid concentration

[0441]

Number

[0442] {Wherein, W dry represents the dry weight of the polymer in g, and V wet represents the volume of the wet polymer in cm 3 and IEC is expressed in mmol / g.}

[0443]

Table 12

[0444] Water adsorption λ eff The effective proton mobility is obtained according to the following formula. Formula 3-S9: Formula for proton mobility

[0445]

Number

[0446] {Wherein, σ represents the proton conductivity of the polymer in water in S cm -1 and F is the Faraday constant 96485 C mol -1 and [SO3H] represents the acid concentration of the membrane in the wet state in mol L -1}

[0447] Effective proton mobility μ In-plane proton conductivity was measured by an ac impedance spectrometer using a Solartron 1260 Frequency Response Analyzer (FRA) having a configuration including two electrodes. The proton conductivity at various RHs was measured by placing the conductivity cell in an Espec model SH-241 humidity chamber maintained at 30 °C.

[0448] Pretreatment of the membrane: The membrane pieces were impregnated in 1.6 M H2SO4 for 1 hour and then immersed three times in Milli-Q (registered trademark). The dimensions (thickness and width) of the membrane were measured before measuring the resistance.

[0449] Proton conductivity was measured at 30 °C (Figure 23) and 80 °C (Figure 24) at different relative humidities (RH): 95% RH, 90% RH, 70% RH, 50% RH (Figures 23 - 27).

[0450] The calculation of proton conductivity is based on the Randles circuit and Equation (Figure 22).

[0451] {where R s represents the resistance of water and the equipment part in ohms, C represents the capacitance of the membrane in farads, and R p represents the resistance of the membrane in ohms. In the equation, σ represents the proton conductivity of the polymer membrane in S cm -1 , L represents the distance between the aforementioned electrodes in cm, R p represents the resistance of the membrane in ohms, T represents the thickness in cm, and w represents the width in cm.}

[0452] Proton conductivity σ Chemical stability: Fenton test Before the test, the membrane pieces were pretreated in 1.6 M HCl for 1 hour, then immersed in Milli-Q (registered trademark) for 1 hour, dried at room temperature, and dried overnight at 80 °C under vacuum. Before releasing the vacuum, the temperature of the oven was cooled to room temperature. The weight of the membrane was measured and recorded twice. sPPP(m)(H +) The membrane pieces were placed in a vial containing H2O2 (20 mL) in 3.0% (w / w) DI H2O while stirring at 80 °C. Then, 1.54 mL of a 3.0 ppm FeSO4 solution was added. The resulting solution was stirred at 80 °C for 1 hour. After cooling to room temperature, Na2SO3 was added to stop the reaction until the generation of bubbles in the solution ceased. During this process, the polymer precipitated, was collected by filtration, and washed several times with ion-exchanged water. Next, the polymer was immersed in 1.0 M HCl and subsequently washed 6 times with DI H2O. The obtained polymer was dried overnight at 120 °C under vacuum. The remaining polymer was recovered, weighed, 1 and analyzed by 1H NMR spectrometer and DMF SEC.

[0453] Although exemplary embodiments have been illustrated and described, it is understood that various changes can be made without departing from the spirit and scope of the present invention. The embodiments of the present invention for which exclusive ownership or privilege is claimed are defined in the claims.

Claims

1. A polymer comprising a repeating unit represented by formula (I): 【Chemical 81】 {wherein: R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, nitro, cyano, SO 3 - X + 、PO 3 2- X + 2 、and COO - X + substituted by 1, 2, 3, 4, or 5 substituents independently selected from + H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents independently selected from SO 3 - X + 、PO 3 2- X + 2 、and COO - X + ; R 1G and R 1H are each independently H, aryl, or heteroaryl, and the aryl and heteroaryl are each optionally C 1-6 alkyl, halo, nitro, cyano, SO 3 - X + 、PO 3 2- X + 2 、and COO - X + substituted by 1, 2, 3, 4, or 5 substituents independently selected from + H + or a cation; A 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A 2 is absent, or is arylene or heteroarylene, which arylene and heteroarylene are each optionally substituted by 1, 2, 3 or 4 substituents independently selected from halo, nitro, cyano, aryl and heteroaryl; L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, and is substituted with one, two, three, or four substituents independently selected therefrom; L 2 is absent, or is an arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently substituted by 1, 2, 3, or 4 substituents selected therefrom; L 3 is absent, or is an arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, and heteroaryl, independently selected from 1, 2, 3, or 4 substituents which are substituted} However, the repeating unit of formula (I) is not the following. 【Chemical 82】

2. The polymer according to claim 1, wherein R 1G and R 1H are each independently H.

3. The polymer according to claim 1 or 2, wherein the repeating unit represented by formula (I) is a repeating unit represented by formula (I-A). 【Chemical 83】 {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, nitro, cyano, SO 3 - X + 、PO 3 2- X + 2 、and COO - X + substituted by one, two, three, four, or five substituents independently selected from + H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted by one, two, three, four, or five substituents independently selected from SO 3 - X + 、PO 3 2- X + 2 、and COO - X + ; R 2A 、R 2B 、R 2C 、and R 2D are each independently H, halo, nitro, cyano, aryl, or heteroaryl; L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L 2 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from 1, 2, 3, or 4 substituents; L 3 is absent, or is an arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from 1, 2, 3, or 4 substituents.}

4. The polymer according to any one of claims 1 to 3, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, nitro, cyano, SO 3 - X + 、and PO 3 2- X + 2 substituted by 1, 2, 3, 4, or 5 substituents independently selected from + where X + is H 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F of which at least two are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents independently selected from SO 3 - X + and PO 3 2- X + 2 a polymer.

5. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, and SO 3 - X + substituted with 1, 2, 3, 4, or 5 substituents independently selected from, X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 SO 3 - X + : a polymer.

6. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl and SO 3 - X + substituted with 1, 2, 3, 4, or 5 substituents independently selected from, X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 SO 3 - X + a polymer.

7. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally having 1, 2, 3, 4, or 5 SO 3 - X + substitutions, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl having 1, 2, 3, 4, or 5 SO 3 - X + substitutions. Polymer

8. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently optionally C 1-6 alkyl, halo, and SO 3 - X + substituted aryl selected independently from 1, 2, 3, 4, or 5 substituents, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl substituted by 1, 2, 3, 4, or 5 SO 3 - X + : a polymer.

9. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently optionally, aryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and SO 3 - X + wherein X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, aryl substituted with 1, 2, 3, 4, or 5 SO 3 - X + ; a polymer.

10. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently optionally 1, 2, 3, 4, or 5 SO 3 - X + -substituted aryls, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently 1, 2, 3, 4, or 5 SO 3 - X + -substituted aryls, a polymer.

11. The polymer according to any one of claims 1 to 4, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently optionally 1, 2, 3, 4, or 5 SO 3 - X + -substituted phenyl, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently 1, 2, 3, 4, or 5 SO 3 - X + -substituted phenyl. Polymer

12. The polymer according to any one of claims 1 to 11, X + is a cation selected from H + or [N(R 5A )(R 5B )(R 5C )(R 5D )], + and alkali metal ions, and R 5A , R 5B , R 5C , and R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl, a polymer.

13. The polymer according to any one of claims 1 to 11, wherein X + is H + is a polymer.

14. The polymer according to any one of claims 1 to 11, wherein X + is [N(R 5A )(R 5B )(R 5C )(R 5D )] + and R 5A , R 5B , R 5C , and R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl, a polymer.

15. The polymer according to any one of claims 1 to 11, wherein X + is [NH(C 1-6 alkyl) 3 + and is a polymer.​

16. The polymer according to any one of claims 1, 2, 4 to 15, A 1 is a polymer which is an arylene, heteroarylene, or aralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

17. The polymer according to any one of claims 1, 2, 4 to 15, A 1 is a polymer that is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

18. The polymer according to any one of claims 1, 2, 4 to 15, A 1 is a polymer that is an arylene substituted with 1, 2, 3, or 4 substituents independently selected from optionally halo, nitro, cyano, aryl, and heteroaryl.

19. The polymer according to any one of claims 1, 2, 4 to 18, A 2 is a polymer which does not exist or is an arylene, and the arylene is optionally substituted by one, two, three or four substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

20. The polymer according to any one of claims 1, 2, 4 to 18, A 2 There is no polymer.

21. The polymer according to any one of claims 1, 2, 4 to 18, A 2 is a polymer that is an arylene substituted with 1, 2, 3, or 4 substituents independently and optionally selected from halo, nitro, cyano, aryl, and heteroaryl.

22. The polymer according to any one of claims 3 to 15, wherein R 2A , R 2B , R 2C , and R 2D are independently H, halo, nitro, or cyano.

23. The polymer according to any one of claims 3 to 15, wherein R 2A , R 2B , R 2C , and R 2D are independently H, halo, or nitro.

24. The polymer according to any one of claims 3 to 15, wherein R 2A , R 2B , R 2C , and R 2D are independently H or halo.

25. The polymer according to any one of claims 3 to 15, wherein R 2A , R 2B , R 2C , and R 2D are each H, the polymer.

26. The polymer according to any one of claims 1 to 25, L 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, aryl, and heteroaryl, a polymer.

27. The polymer according to any one of claims 1 to 25, L 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, and aryl, a polymer.

28. The polymer according to any one of claims 1 to 25, L 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with one, two, three, or four substituents independently selected from C 1-6 alkyl and halo, a polymer.

29. The polymer according to any one of claims 1 to 25, L 1 is an arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer.

30. The polymer according to any one of claims 1 to 25, L 1 is a polymer that is an arylene, heteroarylene or aralkylene.

31. The polymer according to any one of claims 1 to 25, L 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, aryl, and heteroaryl, a polymer.

32. The polymer according to any one of claims 1 to 25, L 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, and aryl, a polymer.

33. The polymer according to any one of claims 1 to 25, L 1 is an arylene or heteroarylene, each optionally C 1-6 a polymer substituted by 1, 2, 3, or 4 substituents independently selected from alkyl and halo.

34. The polymer according to any one of claims 1 to 25, L 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl, polymer.

35. The polymer according to any one of claims 1 to 25, wherein L 1 is arylene or heteroarylene.

36. The polymer according to any one of claims 1 to 25, L 1 is an arylene optionally substituted with one, two, three, or four substituents independently selected from C 1-6 alkyl and halo, a polymer.

37. The polymer according to any one of claims 1 to 25, L 1 is an arylene optionally substituted by one, two, three, or four C 1-6 alkyl-substituted polymer.

38. The polymer according to any one of claims 1 to 25, wherein L 1 is an arylene, the polymer.

39. The polymer according to any one of claims 1 to 25, wherein L 1 is naphthylenylene, phenylene, or C 1-6 phenylene substituted by alkyl, provided that the phenylene is not p-phenylene.

40. The polymer according to any one of claims 1 to 25, wherein L 1 is phenylene, provided that the phenylene is not p-phenylene.

41. The polymer according to any one of claims 1 to 40, L 2 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl and halo, independently selected from 1, 2, 3, or 4 substituents, a polymer.

42. The polymer according to any one of claims 1 to 40, L 2 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer.

43. The polymer according to any one of claims 1 to 40, L 2 is a polymer that is absent, or is an arylene or heteroarylene.

44. The polymer according to any one of claims 1 to 40, L 2 is absent or is an arylene which is optionally substituted by one, two, three or four substituents independently selected from C 1-6 alkyl and halo, a polymer.

45. The polymer according to any one of claims 1 to 40, L 2 is absent or is an arylene, which is optionally a polymer substituted with 1, 2, 3, or 4 C 1-6 alkyl.

46. The polymer according to any one of claims 1 to 40, L 2 is a polymer that does not exist or is an arylene.

47. The polymer according to any one of claims 1 to 40, L 2 is a polymer that does not exist or is phenylene.

48. The polymer according to any one of claims 1 to 40, L 2 There is no polymer.

49. The polymer according to any one of claims 1 to 40, L 2 is a polymer that is phenylene.

50. The polymer according to any one of claims 1 to 49, L 3 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 a polymer substituted by one, two, three, or four substituents independently selected from alkyl and halo.

51. The polymer according to any one of claims 1 to 49, L 3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymers.

52. The polymer according to any one of claims 1 to 49, L 3 is a polymer that does not exist, is an arylene, or is a heteroarylene.

53. The polymer according to any one of claims 1 to 49, L 3 is absent or is an arylene, said arylene optionally being substituted by one, two, three or four substituents independently selected from C 1-6 alkyl and halo, polymer.

54. The polymer according to any one of claims 1 to 49, L 3 is absent or is an arylene, which is optionally a polymer substituted by 1, 2, 3, or 4 C 1-6 alkyl.

55. The polymer according to any one of claims 1 to 49, L 3 is a polymer that does not exist or is an arylene.

56. The polymer according to any one of claims 1 to 49, L 3 is a polymer that does not exist or is phenylene.

57. The polymer according to any one of claims 1 to 49, L 3 is a polymer that does not exist.

58. The polymer according to any one of claims 1 to 49, L 3 is a polymer that is phenylene.

59. The polymer according to any one of claims 1 to 25, -L 3 -L 2 -L 1 - is a polymer independently selected from the following. 【Chemical 84】 【Chem.】 [Chemical] 【Chem.】

60. The polymer according to any one of claims 1 to 59, A polymer comprising a repeating unit selected from the following. 【Chemical 85】 {wherein X + is as defined in any one of claims 1 and 12 to 25.}

61. The polymer according to any one of claims 1 to 60, A polymer comprising a repeating unit selected from the following. 【Chemical 86】 {Wherein, X + is as defined in any one of claims 1 and 12 to 25.}

62. The polymer according to any one of claims 1 to 61, wherein the polymer is a random copolymer.

63. The polymer according to claim 62, wherein the random copolymer further comprises a hydrophobic repeating unit. **Claim 64** The polymer according to any one of claims 1 to 62, further comprising a hydrophobic repeating unit represented by formula (II). 【Chemical 87】 {In the formula, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; R 3G and R 3H are each independently H, aryl, or heteroaryl, and the aryl and heteroaryl are each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; B 1 is arylene, heteroarylene, aralkylene, or heteroaralkylene, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B 2 is absent, an arylene, or a heteroarylene, where the arylene and heteroarylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl: K 1 is a optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by one, two, three, or four substituents independently selected therefrom; K 2 is absent or is an arylene or heteroarylene, each of which is optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by one, two, three, or four substituents independently selected therefrom; K 3 is absent, or is an arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from 1, 2, 3, or 4 substituents.} **Claim 65** The polymer according to claim 64, wherein R 3G and R 3H are independently H, a polymer. **Claim 66** The polymer according to claim 64, wherein the repeating unit represented by formula (II) is a repeating unit represented by formula (II-A). 【Chemical 88】 {In the formula, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, nitro, and cyano; R 4A 、R 4B 、R 4C 、and R 4D are each independently halo, nitro, cyano, aryl, or heteroaryl; K 1 is a concatenated heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene that is optionally substituted, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by one, two, three, or four substituents independently selected from; K 2 is absent or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl substituted by 1, 2, 3, or 4 substituents independently selected therefrom; K 3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from one, two, three, or four substituents.} **Claim 67** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, nitro, and cyano, a polymer. **Claim 68** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F is a polymer that is independently an aryl optionally substituted by 1, 2, 3, 4, or 5 halos. **Claim 69** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, optionally C 1-6 aryl substituted with 1, 2, 3, 4, or 5 substituents independently selected from alkyl and halo, a polymer. **Claim 70** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, optionally aryl substituted with 1, 2, 3, 4, or 5 C 1-6 alkyl, a polymer. **Claim 71** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, polymers that are aryl optionally substituted by 1, 2, 3, 4, or 5 halos. **Claim 72** The polymer according to any one of claims 64 to 66, R 3A 、 R 3B 、 R 3C 、 R 3D 、 R 3E 、 and R 3F are, independently, polymers that are phenyl optionally substituted by 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo. **Claim 73** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are, independently, optionally phenyl substituted with 1, 2, 3, 4, or 5 C 1-6 alkyl, a polymer. **Claim 74** The polymer according to any one of claims 64 to 66, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F is a polymer that is independently phenyl optionally substituted by 1, 2, 3, 4, or 5 halos. **Claim 75** The polymer according to any one of claims 64, 65, and 67 to 74, B 1 is a polymer that is an arylene, heteroarylene, or aralkylidene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl. **Claim 76** The polymer according to any one of claims 64, 65, and 67 to 74, B 1 is a polymer which is an arylene or heteroarylene and is optionally substituted by 1, 2, 3 or 4 substituents independently selected from halo, nitro, cyano, aryl and heteroaryl. **Claim 77** The polymer according to any one of claims 64, 65, and 67 to 74, B 1 is a polymer that is an arylene substituted with 1, 2, 3, or 4 substituents independently and optionally selected from halo, nitro, cyano, aryl, and heteroaryl. **Claim 78** The polymer according to any one of claims 64, 65, and 67 to 77, B 2 is absent or is an arylene, which is optionally substituted by one, two, three or four substituents independently selected from halo, nitro, cyano, aryl and heteroaryl, a polymer. **Claim 79** The polymer according to any one of claims 64, 65, and 67 to 77, B 2 There is no polymer. **Claim 80** The polymer according to any one of claims 64, 65, and 67 to 77, B 2 is a polymer that is an arylene substituted by 1, 2, 3, or 4 substituents independently and optionally selected from halo, nitro, cyano, aryl, and heteroaryl. **Claim 81** The polymer according to any one of claims 66 to 74, wherein R 4A , R 4B , R 4C , and R 4D are independently H, halo, nitro, or cyano. **Claim 82** The polymer according to any one of claims 66 to 74, wherein R 4A , R 4B , R 4C , and R 4D are independently H, halo, or nitro. **Claim 83** A polymer according to any one of claims 66 to 74, wherein R 4A , R 4B , R 4C , and R 4D are independently H or halo. **Claim 84** The polymer according to any one of claims 66 to 74, wherein R 4A , R 4B , R 4C , and R 4D are each H, a polymer. **Claim 85** The polymer according to any one of claims 64 to 84, K 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from 1-6 alkyl, halo, aryl, and heteroaryl, a polymer. **Claim 86** The polymer according to any one of claims 64 to 84, K 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from 1-6 alkyl, halo, and aryl, a polymer. **Claim 87** The polymer according to any one of claims 64 to 84, K 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl and halo, a polymer. **Claim 88** The polymer according to any one of claims 64 to 84, K 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer. **Claim 89** The polymer according to any one of claims 64 to 84, K 1 is a polymer that is an arylene, heteroarylene, or aralkylene. **Claim 90** The polymer according to any one of claims 64 to 84, K 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, aryl, and heteroaryl, a polymer. **Claim 91** A polymer according to any one of claims 64 to 84, K 1 is an arylene or heteroarylene, each optionally C 1-6 substituted by 1, 2, 3, or 4 substituents independently selected from alkyl, halo, and aryl, a polymer.

92. A polymer according to any one of claims 64 to 84, K 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl and halo, a polymer.

93. A polymer according to any one of claims 64 to 84, K 1 is an arylene or heteroarylene, each optionally having 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer.

94. A polymer according to any one of claims 64 to 84, K 1 is a polymer that is an arylene or heteroarylene.

95. A polymer according to any one of claims 64 to 84, K 1 is optionally C 1-6 a polymer that is an arylene substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo.

96. A polymer according to any one of claims 64 to 84, K 1 is an arylene optionally substituted by one, two, three, or four C 1-6 alkyl, a polymer.

97. A polymer according to any one of claims 64 to 84, K 1 is an arylene polymer.

98. A polymer according to any one of claims 64 to 84, K 1 is a polymer that is naphthylenylene, phenylene, or phenylene substituted by C 1-6 alkyl.

99. A polymer according to any one of claims 64 to 84, K 1 is a polymer that is phenylene.

100. A polymer according to any one of claims 64 to 99, K 2 is absent, an arylene, or a heteroarylene, which arylene and heteroarylene are optionally C 1-6 a polymer substituted by one, two, three, or four substituents independently selected from alkyl and halo.

101. A polymer according to any one of claims 64 to 99, K 2 is absent, an arylene, or a heteroarylene, and the arylene and heteroarylene are optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer.

102. A polymer according to any one of claims 64 to 99, K 2 is a polymer that does not exist, is an arylene, or is a heteroarylene.

103. A polymer according to any one of claims 64 to 99, K 2 is absent or is an arylene, which is optionally C 1-6 a polymer substituted with 1, 2, 3, or 4 substituents independently selected from alkyl and halo.

104. A polymer according to any one of claims 64 to 99, K 2 is absent or is an arylene which is optionally substituted by 1, 2, 3 or 4 C 1-6 alkyl, polymer.

105. A polymer according to any one of claims 64 to 99, K 2 is a polymer that does not exist or is an arylene.

106. A polymer according to any one of claims 64 to 99, K 2 is a polymer that does not exist or is phenylene.

107. A polymer according to any one of claims 64 to 99, K 2 There is no polymer.

108. A polymer according to any one of claims 64 to 99, K 2 is a polymer that is phenylene.

109. A polymer according to any one of claims 64 to 108, K 3 is absent or is an arylene or heteroarylene, which arylene and heteroarylene are optionally C 1-6 polymer substituted by one, two, three or four substituents independently selected from alkyl and halo.

110. A polymer according to any one of claims 64 to 108, K 3 is absent, or is an arylene or heteroarylene, each of which is optionally substituted with 1, 2, 3, or 4 C 1-6 alkyl-substituted polymer.

111. A polymer according to any one of claims 64 to 108, K 3 is a polymer that is absent, or is an arylene or heteroarylene.

112. A polymer according to any one of claims 64 to 108, K 3 is absent or is an arylene, which arylene is optionally substituted with one, two, three or four substituents independently selected from C 1-6 alkyl and halo, polymer.

113. A polymer according to any one of claims 64 to 108, K 3 is absent or is an arylene, which is optionally a polymer substituted by 1, 2, 3, or 4 C 1-6 alkyl.

114. A polymer according to any one of claims 64 to 108, K 3 is a polymer that does not exist or is an arylene.

115. A polymer according to any one of claims 64 to 108, K 3 is a polymer that does not exist or is phenylene.

116. A polymer according to any one of claims 64 to 108, K 3 is a polymer that does not exist.

117. A polymer according to any one of claims 64 to 108, K 3 is a polymer that is phenylene.

118. The polymer according to any one of claims 64 to 84, -K 3 -K 2 -K 1 - is a polymer independently selected from the following. 【Chemical 89】 【Chem.】 【Chem.】 【Chem.】

119. The polymer according to any one of claims 64 to 117, wherein the hydrophobic repeating unit is a polymer selected from the following. 【Chemical Formula 90】

120. The polymer according to any one of claims 64 to 117, wherein the hydrophobic repeating unit is a polymer selected from the following. 【Chemical Formula 91】

121. A polymer, a first repeating unit selected from the following and any combination thereof: 【Chemical Formula 92】 {wherein X + is as defined in any one of claims 1 and 12 to 15}; and a second repeating unit selected from the following and any combination thereof: 【Chemical 93】 comprising, wherein the molar ratio of the first repeating unit to the second repeating unit is in the range of 1:99 to 99:1, a polymer.

122. A block copolymer, a first block selected from the following and any combination thereof: 【Chemical Formula 94】 {wherein X + is as defined in any one of claims 1, 12 to 15, and n is an integer of 3 to 100}, and a second block selected from the following and any combination thereof: 【Chemical Formula 95】 {wherein m is an integer from 3 to 100} comprising, wherein the molar ratio of the first block to the second block is in the range of 1:99 to 99:1, a random block polymer.

123. The polymer according to any one of claims 1 to 122, wherein the polymer is linear, a polymer.

124. The polymer according to any one of claims 1 to 122, wherein the polymer is branched, a polymer.

125. A polymer according to any one of claims 1 and 122 to 124, further comprising a polyvalent linking group M directly bonded to at least three repeating units via a covalent bond 1 The polymer further comprising the same

126. The polymer according to claim 125, wherein said M 1 is a trivalent, tetravalent, pentavalent, or hexavalent linking group.

127. The polymer according to claim 125 or 126, wherein the polyvalent linking group M 1 is selected from a carbon atom, a heteroatom (e.g., N, P, or B), polyvalent aryl, polyvalent heteroaryl, polyvalent aralkyl, or polyvalent heteroaralkyl, and the carbon atom, heteroatom (e.g., P), polyvalent aryl, polyvalent heteroaryl, polyvalent aralkyl, and polyvalent heteroaralkyl are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, and is substituted by one, two, or three substituents independently selected therefrom, a polymer.

128. The polymer according to any one of claims 125 to 127, wherein the polyvalent linking group is selected from trivalent nitrogen, tetravalent carbon, trivalent phenyl, trivalent pyridyl, trivalent pyrazyl, tetravalent phenyl, tetravalent pyridyl, tetravalent pyrazyl, pentavalent phenyl, pentavalent pyridyl, and hexavalent phenyl; Trivalent phenyl and trivalent pyridyl are each optionally C 1-6 substituted with 1, 2, or 3 substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl; The tetravalent phenyl, tetravalent pyridyl, and trivalent pyrazyl are each optionally substituted with one or two substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; The pentavalent phenyl is optionally C 1-6 a polymer substituted with substituents independently selected from alkyl, halo, nitro, cyano, aryl, and heteroaryl.

129. The polymer according to any one of claims 125 to 128, wherein the polyvalent linking group is a polymer selected from the following. 【Chemical Formula 96】

130. The polymer according to any one of claims 125 to 129, wherein the polyvalent linking group is as follows, a polymer. 【Chemical Formula 97】

131. A compound represented by formula (III). 【Chemical Formula 98】 {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, SO 3 - X + 、PO 3 2- X + 2 、and COO - X + and X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents selected from SO 3 - X + 、PO 3 2- X + 2 、and COO - X + ; A 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; A 2 is absent, or is an arylene or heteroarylene, where the arylene and heteroarylene are each optionally substituted by one, two, three or four substituents independently selected from halo, nitro, cyano, aryl and heteroaryl}{ provided that the compound represented by formula (III) is not the following. 【Chemical Formula 99】

132. The compound according to claim 131, a compound comprising a compound represented by formula (III-A). 【Chemical 100】 {wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, SO 3 - X + 、PO 3 2- X + 2 、and COO - X + substituted by 1, 2, 3, 4, or 5 substituents independently selected from, X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are independently aryl or heteroaryl substituted by 1, 2, 3, 4, or 5 substituents selected from SO 3 - X + 、PO 3 2- X + 2 、and COO - X + ; R 2A 、R 2B 、R 2C 、and R 2D are independently selected from H, halo, nitro, cyano, aryl, and heteroaryl} However, the compound represented by formula (III-A) is not the following. 【Chemical 101】

133. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl, halo, SO 3 - X + 、and PO 3 2- X + 2 and X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 substituents selected from SO 3 - X + and PO 3 2- X + 2 A compound.

134. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl, halo, and SO 3 - X + substituted with 1, 2, 3, 4, or 5 substituents independently selected from + H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 SO 3 - X + ; a compound.

135. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are each independently aryl or heteroaryl, each optionally C 1-6 alkyl and SO 3 - X + substituted with 1, 2, 3, 4, or 5 substituents independently selected from, X + is H + or a cation, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F wherein at least two of are each independently aryl or heteroaryl substituted with 1, 2, 3, 4, or 5 SO 3 - X + A compound.

136. The compound according to claim 131 or 132, R 1A 、 R 1B 、 R 1C 、 R 1D 、 R 1E 、 and R 1F are each independently aryl or heteroaryl, each optionally having 1, 2, 3, 4, or 5 SO 3 - X + substitutions, where X + is H + or a cation, and at least two of R 1A 、 R 1B 、 R 1C 、 R 1D 、 R 1E 、 and R 1F are each independently aryl or heteroaryl having 1, 2, 3, 4, or 5 SO 3 - X + substitutions. Compound

137. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, optionally C 1-6 alkyl, halo, and SO 3 - X + substituted aryl selected independently from one, two, three, four, or five substituents, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, aryl substituted with SO 3 - X + : a compound.

138. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, optionally aryl substituted with one, two, three, four, or five substituents independently selected from C 1-6 alkyl and SO 3 - X + wherein X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, aryl substituted with one, two, three, four, or five SO 3 - X + groups. A compound.

139. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, optionally 1, 2, 3, 4, or 5 SO 3 - X + -substituted aryls, where X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, 1, 2, 3, 4, or 5 SO 3 - X + -substituted aryls, a compound.

140. The compound according to claim 131 or 132, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, optionally phenyl substituted by 1, 2, 3, 4, or 5 SO 3 - X + wherein X + is H + or a cation, and at least two of R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、and R 1F are, independently, phenyl substituted by 1, 2, 3, 4, or 5 SO 3 - X + ; a compound.

141. The compound according to any one of claims 131 to 140, X + is a cation selected from the group consisting of H + , or [N(R 5A )(R 5B )(R 5C )(R 5D )] + , an alkali metal ion, and R 5A , R 5B , R 5C , R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl, a compound.

142. The compound according to any one of claims 131 to 140, X + is a compound that is + H

143. The compound according to any one of claims 131 to 140, X + is [N(R 5A )(R 5B )(R 5C )(R 5D )] + wherein R 5A , R 5B , R 5C , R 5D are independently H, C 1-6 alkyl, aryl, or heteroaryl, a compound.

144. The compound according to any one of claims 131 to 140, X + is a compound represented by [NH(C 1-6 alkyl) 3 + .​

145. The compound according to claim 131 and any one of claims 133 to 144, A 1 is an arylene, heteroarylene, or aralkylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, a compound.

146. The compound according to claim 131 and any one of claims 133 to 144, A 1 is an arylene or heteroarylene, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, a compound.

147. The compound according to claim 131 and any one of claims 133 to 144, A 1 is a compound which is an arylene substituted by 1, 2, 3 or 4 substituents independently and optionally selected from halo, nitro, cyano, aryl and heteroaryl.

148. The compound according to claim 131 and any one of claims 133 to 147, A 2 is a compound which does not exist or is an arylene, the arylene being optionally substituted by 1, 2, 3 or 4 substituents independently selected from halo, nitro, cyano, aryl and heteroaryl.

149. The compound according to claim 131 and any one of claims 133 to 147, A 2 There is no such compound.

150. The compound according to claim 131 and any one of claims 133 to 147, A 2 is a compound which is an arylene substituted by 1, 2, 3 or 4 substituents independently and optionally selected from halo, nitro, cyano, aryl and heteroaryl.

151. The compound according to any one of claims 132 to 144, R 2A 、R 2B 、R 2C 、and R 2D is a compound independently being H, halo, nitro, or cyano.

152. The compound according to any one of claims 132 to 144, R 2A 、 R 2B 、 R 2C 、 and R 2D is a compound that is independently H, halo, or nitro.

153. The compound according to any one of claims 132 to 144, R 2A 、 R 2B 、 R 2C 、 and R 2D is a compound that is independently H or halo.

154. The compound according to any one of claims 131 to 144, R 2A 、R 2B 、R 2C 、and R 2D is a compound in which each is H.

155. A method for producing a polymer according to any one of claims 1 to 130, preparing a mixture containing the compound according to any one of claims 131 to 154 and at least one compound represented by formula (IV); 【Chemical 102】 {wherein, L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally substituted with 1, 2, 3, or 4 substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; L 2 is absent, or is arylene or heteroarylene, where the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl independently substituted by one, two, three, or four substituents selected therefrom; L 3 is absent or is an arylene or heteroarylene, each of which is optionally substituted with one, two, three, or four substituents independently selected from C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl; D 1 and D 2 are independently H, R 1G , R 1H , R 3G , R 3H , or a protecting group, and R 1G and R 1H are as defined in claim 1 or 2, and R 3G and R 3H are as defined in claim 64 or 65}; and Reacting a compound represented by formula (III) or formula (III-A) with at least one compound represented by formula (IV) by a Diels Alder reaction to obtain the polymer according to any one of claims 1 to 130; A method comprising.

156. The method according to claim 155, wherein reacting the compound represented by formula (III) with the compound represented by formula (IV) by a Diels Alder reaction comprises heating the mixture at a temperature of 150 ° C to 300 ° C for 5 minutes to 30 days. A method.

157. The method according to claim 155 or 156, further comprising deprotecting the compound represented by formula (IV) before or during the Diels Alder reaction, wherein at least one of D 1 and D 2 is a protecting group.

158. The method according to any one of claims 157 to 157, wherein the mixture further comprises a compound represented by formula (V). 【Chemical 103】 {Wherein, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F is independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo; B 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B 2 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally substituted with 1, 2, 3 or 4 substituents independently selected from halo, nitro, cyano, aryl and heteroaryl.}

159. The method according to any one of claims 155 to 157, wherein the mixture further comprises a compound represented by formula (V-A). 【Chemical 104】 {Wherein, R 3A 、 R 3B 、 R 3C 、 R 3D 、 R 3E 、 and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo; R 4A 、R 4B 、R 4C 、and R 4D are independently halo, nitro, cyano, aryl, or heteroaryl.}

160. The method according to any one of claims 155 to 159, wherein the mixture further comprises a compound represented by formula (V-B). 【Chemical 105】 {In the formula, R 1A and R 1B are as defined in claims 1 to 11.}

161. A method for producing a random block copolymer, comprising: A first polymer represented by formula (VI): 【Chemical 106】 {Wherein, R 1A 、R 1B 、R 1C 、R 1D 、R 1E 、R 1F 、R 1G 、R 1H 、R 2A 、R 2B 、R 2C 、and R 2D 、A 1 、A 2 、L 1 、L 2 、and L 3 are as defined in any one of claims 1 to 59; n is an integer from 3 to 100; A is a first reactive end group)}; and A second polymer represented by formula (VII): 【Chemical 107】 {Wherein, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、R 3F 、R 3G 、R 3H 、R 4A 、R 4B 、R 4C 、R 4D 、B 1 、B 2 、K 1 、K 2 、and K 3 are as defined in any one of claims 64 to 118; m is an integer from 3 to 100; B is a second reactive end group configured to react with A} Preparing a mixture of; Reacting A and B to obtain a random block copolymer represented by formula (VIII): 【Chemical 108】 {The molar ratio of the second block to the first block is in the range of 1:99 to 99:1} A method comprising obtaining.

162. A method for producing a polymer according to any one of claims 1 to 130, comprising: Preparing a mixture comprising a compound according to any one of claims 131 to 154 and at least one compound represented by formula (IX); 【Chemical 109】 {Wherein, L 1 is an optionally substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, and the arylene, heteroarylene, aralkylene, and heteroaralkylene are each optionally substituted with one, two, three, or four substituents independently selected from 1-6 C alkyl, halo, nitro, cyano, aryl, and heteroaryl; L 2 is absent or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently selected from one, two, three, or four substituents; L 3 is absent, or is arylene or heteroarylene, and the arylene and heteroarylene are each optionally C 1-6 alkyl, halo, nitro, cyano, aryl, and heteroaryl, independently substituted by 1, 2, 3, or 4 substituents selected therefrom; D 3 is H, R 1G , R 1H , R 3G , R 3H , or a protecting group, and R 1G and R 1H are as defined in claim 1 or 2, and R 3G and R 3H are as defined in claim 64 or 65; D 4 is a halo; Reacting a compound represented by formula (III) or formula (III-A) with at least one compound represented by formula (IX) by a Diels Alder reaction to obtain a halogenated intermediate compound; The halogenated intermediate compound is coupled in the presence of an organopalladium catalyst, an organocopper catalyst, an organonickel catalyst, an organomanganese catalyst, an organoplatinum catalyst, an organoruthenium catalyst, or a combination thereof to obtain the polymer according to any one of claims 1 to 130; A method comprising this.

163. The method according to claim 162, comprising deprotecting the compound represented by formula (IV) before or during the Diels Alder reaction, wherein D 1 and D 2 at least one of which is a protecting group.

164. The method according to claim 162 or 163, wherein the mixture further comprises a compound represented by formula (V). 【Chemical 110】 {In the formula, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo, and X + is H + or a cation; B 1 is an arylene, heteroarylene, aralkylen, or heteroaralkylen, each optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; B 2 is absent, an arylene, or a heteroarylene, each of which is optionally substituted by 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.}

165. The method according to claim 162 or 163, wherein the mixture further comprises a compound represented by formula (V-A). 【Chemical 111】 {In the formula, R 3A 、R 3B 、R 3C 、R 3D 、R 3E 、and R 3F are each independently aryl or heteroaryl, each optionally substituted with 1, 2, 3, 4, or 5 substituents independently selected from C 1-6 alkyl and halo, and X + is H + or a cation; R 4A 、R 4B 、R 4C 、and R 4D are each independently halo, nitro, cyano, aryl, or heteroaryl.}

166. The method according to any one of claims 162 to 165, wherein the mixture further comprises a compound represented by formula (V-B). 【Chemical 112】 {wherein R 1A and R 1B are as defined in any one of claims 1 to 11.}

167. An ion exchange membrane comprising the polymer according to any one of claims 1 to 130.

168. The ionic membrane according to claim 167, having a proton conductivity of 0.001 mS cm -1 to 1000 mS cm -1 when measured at a temperature of 20°C to 90°C using AC impedance spectroscopy at a relative humidity of 30% to 100%, or having a conductivity of 1 mS cm -1 to 1000 mS cm -1 when measured using AC impedance spectroscopy in water at 80°C, the ionic membrane.

169. An ionomer comprising the polymer according to any one of claims 1 to 130.

170. The ionomer according to claim 169, which is incorporated into the catalyst layer of a fuel cell, an electrolytic cell, or other electrochemical device.

171. The ionomer according to claim 170, which is incorporated into the catalyst layer of a fuel cell, an electrolytic cell, or other electrochemical device at a solid content of 5 wt% to 45 wt% in the catalyst layer.

172. The ionomer according to claim 169, which is incorporated into a cation exchange resin.

173. The polymer according to any one of claims 1 to 154, which shows a mass loss of less than 20% when exposed to Fenton's reagent at a temperature of 80 °C and a pressure of 1 atm for a period longer than 0 and up to 180 minutes.

174. The polymer according to any one of claims 1 to 154, which has an ion exchange capacity of 2 to 4.5 when evaluated by acid-base titration.

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