Method for sulfonating precursor monomers in the synthesis of advanced anionic sulfonated polyphenylene polymers

Abstract

Disclosed herein are new and improved sulfonation processes for generating sulfonated polyphenylenes using acetic anhydride and sulfuric acid as the sulfonating agent. Sulfonated polyphenylene polymers are generated from the sulfonated polyphenylenes. This improved process offers higher yields, easier handling, and a reduced environmental footprint compared to existing methods of generating sulfonated polyphenylene polymers. Sulfonated polyphenylene polymers can be used in proton exchange membranes for electrochemical devices such as fuel cells, electrolyzers, dialyzers, hydrogen pumps, thermoelectrochemical hydrogen pumps, electrochemical hydrogen compressors, redox flow batteries, and other electrochemical devices.

Description

METHOD FOR SULFONATING PRECURSOR MONOMERS IN THE SYNTHESIS OF ADVANCED ANIONIC SULFONATED POLYPHENYLENE POLYMERSCROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U. S. Application No. 63 / 717,449, filed on November 7, 2024, the disclosure of which is hereby incorporated by reference in its entirety.FIELD OF THE INVENTION

[0002] The present invention relates to the field of polymer chemistry, specifically to an improved method for sulfonating polyphenylenes used in the synthesis of high-performance anionic sulfonated polyphenylene polymers.BACKGROUND

[0003] Hydrocarbon-based proton exchange membranes (PEMs) and ionomers are alternatives to traditional perfluorosulfonic acid (PFSA) ionomers for electrochemical applications. These hydrocarbon-based materials offer ease of synthesis, low cost, low gas crossover, high glass transition temperature (Tg), and fewer environmental concerns. Many different ion-containing polymers have been investigated, such as sulfonated derivatives of poly(arylene ether)s, poly(arylene ether ketone)s, poly(arylene sulfone)s, poly(imide)s, and poly(benzimidazole)s. However, hydrocarbon-based ionomers often suffer from sensitivity to oxidative degradation, both ex situ and in situ.

[0004] Recent attention has focused on the rational design of hydrocarbon ionomers for use in electrochemical membranes.

[0005] Recently, these polymers have been examined for use in proton exchange membrane fuel cells (PEMFCs), and post-quaternized ammonium derivatives have been examined in anionic exchange membrane fuel cells (AEMFCs).

[0006] Traditional sulfonated polyphenylene polymer synthesis requires post sulfonation of polyphenylenes, resulting in polymers having sulfonation in varying positions and which have inconsistent degrees of sulfonation.

[0007] Other sulfonated polyphenylene polymer syntheses focus on controlled synthesis of anionic phenylene monomers having precisely positioned anionic groups. A key to such sulfonated polyphenylene polymers lies in their synthesis method, which involves Diels-Alder condensation of a sulfonated bis-tetracyclone with a bis-alkyne. The properties crucial for the resulting polymers, such as high ion exchange capacity (IEC), conductivity, and water absorption, depend significantly on controlling the degree of sulfonation in the polymer. Membranes cast from these polymers exhibited good conductivity and ex situ stability.

[0008] Achieving precise control over the number and location of anionic groups in the synthesis of these polymers is critical. This precision is attained through the sulfonation of the monomer, using trimethyl silyl chlorosulfonate as the sulfonating agent. However, the process requires an excess of trimethyl silyl chlorosulfonate, which is highly hygroscopic and unstable in the presence of water. Consequently, the use of trimethyl silyl chlorosulfonate poses significant challenges related to handling, yield, cost-effectiveness, and scalability.

[0009] Therefore, there is an urgent need for a more efficient and effective sulfonation method that can address these limitations while maintaining precise control over polymer properties. Specifically, there is a need in the art for improved sulfonation processes that offer higher yields, easier handling, and a reduced environmental footprint.SUMMARY

[0010] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This summary is not intended to identify 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.

[0011] In one aspect of the disclosure, provided herein is a method for sulfonation of a polyphenylene, comprising:a) dissolving a polyphenylene in dichloromethane;b) reacting acetic anhydride with concentrated sulfuric acid in dichloromethane to form acetyl sulfate; andc) reacting the dissolved polyphenylene with the acetyl sulfate to form a sulfonated tetracyclone.

[0012] In another aspect of the disclosure, provided herein is another method for sulfonation of a polyphenylene, comprising:a) dissolving a polyphenylene in a mixture of dichloromethane and acetic anhydride; andb) reacting the dissolved polyphenylene with concentrated sulfuric acid to produce a sulfonated tetracyclone.DESCRIPTION OF THE DRAWINGS

[0013] The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same become better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein:

[0014] FIG. 1 shows a synthetic scheme for sulfonation of polyphenylenes, in accordance with embodiments described;

[0015] FIG. 2 shows nuclear magnetic resonance spectroscopy (NMR) data of seven individual tetra(para-sulfonated) bistetracyclone (TPSB)-H+batches, in accordance with embodiments described; and

[0016] FIG. 3 shows NMR data at the aromatic region of seven individual TPSB-H+batches, in accordance with embodiments described.DETAILED DESCRIPTION

[0017] The present disclosure addresses the deficiencies of present polymer synthesis methods by providing an improved process for producing sulfonated polyphenylene monomer units using acetic anhydride and sulfuric acid as the sulfonating agent. This new approach offers a cheaper, safer, and more scalable method for synthesizing sulfonated polyphenylene polymers, while providing tailored polymer characteristics. By addressing the key challenges of existing synthetic methods, this disclosure provides a significant advancement in the efficient and effective synthesis of sulfonated polyphenylene monomers and the anionic phenylene oligomers, polymers, and copolymers that can be produced from the monomers.

[0018] The improved sulfonation process using acetic anhydride and sulfuric acid presents several advantages over traditional methods. While acetic anhydride and sulfuric acid typically yield sulfonated products comparable to those of existing techniques, the process disclosed herein enhances efficiency by reducing the number of steps and simplifying reagent handling. This process makes it better suited for industrial-scale production. By eliminating trimethyl silyl chlorosulfonate — a highly hygroscopic and challenging chemical to manage — the process not only lowers the environmental impact associated with its synthesis and disposal, but also improves overall safety. The method is easily scalable to industrial levels without significant modifications and utilizes readily available, less expensive reagents, making it more cost-effective compared to methods involving trimethyl silyl chlorosulfonate.

[0019] By addressing these key areas, the methods disclosed herein represent a significant advancement in the field of sulfonated polyphenylene synthesis, opening new possibilities for material design and application. The sulfonated polyphenylene monomers produced by the methods disclosed herein are characterized by precise control over the degree and position of sulfonation, enabling the synthesis of high-performance anionic phenylene polymers with tailored properties. Materials comprising such polymers show great promise inapplications such as fuel cells and water purification membranes, where their high ion exchange capacity (IEC), conductivity, and water absorption are crucial.Definitions

[0020] The terminology used in the description of the invention herein is for the purpose of describing particular embodiments and is not intended to be limiting for the invention.

[0021] It is further appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, can also be provided separately or in any suitable subcombination.

[0022] The term “substituted” means that an atom or group of atoms formally replaces hydrogen as a “substituent” attached to another group. The term “substituted,” unless otherwise indicated, refers to any level of substitution, e.g., mono-, di-, tri-, tetra-, penta-, or higher substitution, where such substitution is permitted (e.g., results in a stable compound). The substituents are independently selected, and substitution may be at any chemically accessible position. It is to be understood that substitution at a given atom is limited by valency.

[0023] When a group is unsubstituted, it can be referred to as the group name, for example, alkyl or aryl.

[0024] Substituents of polymers of the disclosure are disclosed herein in groups or in ranges. It is specifically intended that the disclosure includes each and every individual subcombination of the members of such groups and ranges. For example, the term “Ci-6 alkyl” is specifically intended to individually disclose (without limitation) methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and Ce alkyl, and to include linear or branched geometric isomers when such geometric isomers are possible. For example, C4alkyl can be n-butyl, sec-butyl, isobutyl, or tert-butyl.

[0025] As used herein, the term “alkyl” refers to straight, branched, or cyclic hydrocarbon groups. In some embodiments, alkyl has 1 to 6 carbon atoms, 1 to 5 carbonatoms, 1 to 4 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, cyclopropyl), butyl (e.g., n-butyl, sec-butyl, isobutyl, tert-butyl, cyclobutyl), pentyl (e.g., n-pentyl, tert-pentyl, neopentyl, isopentyl, pentan-2-yl, pentan-3-yl, cyclopentyl), and hexyl (e.g., n-hexyl, geometric isomers, cyclohexyl) groups.

[0026] As used herein, the term “alkylene” refers to a linking alkyl group.

[0027] As used herein, the term “aryl” refers to an aromatic hydrocarbon group having 6 to 14 carbon atoms. Representative aryl groups include phenyl groups and naphthyl groups. In some embodiments, the term “aryl” includes monocyclic or polycyclic (e.g., having 2 or 3 fused rings) aromatic hydrocarbons such as, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, and indenyl.

[0028] As used herein, the term “arylene” refers to a linking aryl group. For example, the term “phenylene” refers to a linking phenyl group.

[0029] As used herein, the term “aralkyl” refers to an alkyl group as defined herein, with an aryl group as defined herein, substituted for one of the alkyl hydrogen atoms. A representative aralkyl group is a benzyl group.

[0030] As used herein, the term “aralkylene” refers to a linking aralkyl group.

[0031] As used herein, the term “heteroaryl” refers to a 5- to 10-membered aromatic monocyclic or bicyclic ring containing 1-4 heteroatoms selected from O, S, and N. Representative 5- or 6-membered aromatic monocyclic ring groups include pyridine, pyrimidine, pyridazine, furan, thiophene, thiazole, oxazole, and isooxazole. Representative 9-or 10-membered aromatic bicyclic ring groups include benzofuran, benzothiophene, indole, pyranopyrrole, benzopyran, quinoline, benzocyclohexyl, and naphthyridine.

[0032] As used herein, the term “heteroarylene” refers to a linking heteroaryl group.

[0033] As used herein, the term “heteroaralkyl” refers to an alkyl group as defined herein with a heteroaryl group as defined herein substituted for one of the alkyl hydrogen atoms. For example, a representative heteroaralkyl group is an alkylpyridyl group.

[0034] As used herein, the term “ heteroaralkyl ene” refers to a linking heteroaralkyl group.

[0035] As used herein, the term “halogen” or “halo” refers to fluoro, chloro, bromo, and iodo groups. “Halogen” or “halo” can refer to the entire set of fluoro, chloro, bromo, and iodo groups, or to a subset of halogen atoms, e.g., fluoro, chloro, and bromo; chloro, bromo, and iodo; and any other combination or subcombination of halogen atoms.

[0036] As used herein, the term “heteroatomic” or “heteroatomic groups” refers to one or more heteroatoms, wherein the one or more heteroatoms is selected from N, O, and S.

[0037] As used herein, the term “copolymer” refers to a polymer that is the result of polymerization of two or more different monomeric units. The number and the nature of each monomeric unit can be separately controlled in a copolymer. The copolymer comprises at least one monomeric unit that is ionomeric, and at least one monomeric unit that is not ionomeric, or is uncharged. The ionomeric monomers in the copolymer can be the same or can be different. The uncharged monomers in the copolymer can be the same or can be different.

[0038] As used herein, the term “repeat unit” or “repeating unit” corresponds to the smallest monomeric unit, the repetition of which constitutes a macromolecule, or a polymer chain. The monomeric unit is a repeat unit within the polymer chain. As used herein, monomeric unit and repeat unit are used interchangeably. The monomeric unit of a polymer chain refers to a group of atoms in the monomer which comprise the backbone, together with its pendant atoms or groups of atoms. The monomeric units in a polymer chain may be the same, or may be different. For example, any monomeric unit can comprise one, two, three, or four sulfonate groups, or any monomeric unit can lack any sulfonate groups. The monomeric unit can also refer to an end group on the polymer chain. For example, the monomeric unit of polyethylene glycol can be -CH2CH2O- corresponding to a repeating unit, or -CH2CH2OH corresponding to an end group. As used herein, the term “end group” refers to a repeating unit, or monomeric unit, with only one attachment to the polymer chain, located at an end of the polymer chain.

[0039] The repeat units can be disposed in a purely random, an alternating random, a regular alternating, a statistical, a regular block, or a random block configuration unless expressly stated to be otherwise. The repeat units can be connected end-on-end to form apolymer that is linear in its primary structure, or the repeat units can be connected in a polymer that is branched.

[0040] As used herein, the term “random copolymer” is a copolymer having an irregular mixture of two or more monomeric units. The distribution of the monomeric units throughout the polymer can be a statistical distribution, or approach a statistical distribution, of the repeat units. In some embodiments, the distribution of one or more of the monomeric units is favored. A purely random configuration can, for example, be: x x y z x y y z y z z z... oryzxyzy zxx.... An alternating random configuration can be: xyx zyxy zyxz..., and a regular alternating configuration can be: xy z xy zx y z....

[0041] As used herein, the term “statistical copolymer” is a copolymer having a composition of monomeric units as determined by the mole percent of monomeric units used to generate the polymer. For example, in a statistical copolymer comprising 90% ionomeric monomer and 10% uncharged monomer, the resulting polymer is expected to consist of about 90% ionomeric monomer units and about 10% uncharged monomer units. A statistical polymer comprises an average composition ratio of x and y monomer units.

[0042] A regular block configuration (z.e., a block copolymer) has the following example configuration when comprising three different monomeric units (x, y, and z) for the block:...x x x y y y z z z x x x..., while a random block configuration has the following general example configuration of, for example:...x x x z z z x x x y y y y z z z x x x z z z z...., or for example,...x-x-x-y-y-y-y-x-x-x-y-y-y-x-x-x-x-y-y-y.... A block copolymer comprises blocks of 3 or more of the same monomeric unit.

[0043] As used herein, the term “cationic” refers to a moiety that is positively charged, or ionizable to a positively charged moiety under chemical or acidic conditions relative to the pKa of an atom. Examples of cationic moieties include, for example, ammonium, iminium, imidazolium, oxazolium, thiazolium groups, etc.

[0044] As used herein, “eq” means equivalents. For example, as used herein, equivalents means molar equivalents, unless otherwise stated.

[0045] As used in the description and the appended claims of the disclosure, the singular forms “a”, “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0046] As used herein, the term “about” can be understood to include values within 10% of the stated value. For example, a temperature of “about 50°C” means the temperature is 50 ± 5 °C. Otherwise stated, the temperature is 45°C to 55°C.

[0047] It is further intended that the polymers of the disclosure are stable. In the context of the present disclosure, “stable” refers to a polymer that can withstand heating as a polymer film and at 100°C to 120°C for at least 24 hours without appreciable chemical degradation. The “stability” of the polymer can be verified by analyzing its1H NMR spectrum after heating at these conditions and comparing it to that of the pristine polymer.

[0048] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the present disclosure and relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.Polyphenylene Polymer Compositions

[0049] In some aspects, disclosed herein is a method for sulfonation of a polyphenylene of Formula (I) as described herein, the method comprising:a) dissolving a polyphenylene of Formula (I) in dichloromethane;b) reacting acetic anhydride with concentrated sulfuric acid in dichloromethane to form acetyl sulfate; andc) reacting the dissolved polyphenylene of Formula (I) with the acetyl sulfate to form a sulfonated tetracyclone of Formula (II), as described herein.

[0050] In other aspects, disclosed herein is another method for sulfonation of a polyphenylene of Formula (I), as described herein, the method comprising:a) dissolving a polyphenylene of Formula (I) in a mixture of dichloromethane and acetic anhydride; andb) reacting the dissolved polyphenylene of Formula (I) with concentrated sulfuric acid to produce a sulfonated tetracyclone of Formula (II), as described herein.

[0051] In some embodiments, the concentration of the polyphenylene of Formula (I) in dichloromethane is about 2 wt % to about 25 wt %. In some embodiments, the concentration of the polyphenylene of Formula (I) in dichloromethane is about 5 wt % to about 15 wt %.

[0052] In some embodiments, the concentration of the polyphenylene of Formula (I) in the mixture of di chloromethane and acetic anhydride is about 2 wt % to about 25 wt %. In some embodiments, the concentration of the polyphenylene of Formula (I) in the mixture of dichloromethane and acetic anhydride is about 5 wt % to about 15 wt %.

[0053] In some embodiments, the ratio of equivalents of acetic anhydride to equivalents of concentrated sulfuric acid to equivalents of the polyphenylene of Formula (I) is 30:25:1 molar equivalents.

[0054] In some embodiments, the amount of acetyl sulfate is about 10 molar equivalents to about 30 molar equivalents excess with respect to an amount of the polyphenylene of Formula (I).

[0055] In some embodiments, the reacting occurs at a temperature below about 15°C.In some embodiments, the reacting is at a temperature between about 10°C and about 15°C. In some embodiments, the reacting is at a temperature between about 20°C and about 50°C. In some embodiments, the reacting is at a temperature between about 25°C and about 50°C.

[0056] In some embodiments, the reacting is for between about 1 and about 72 hours.

[0057] In some embodiments, the sulfonated tetracyclone of Formula (II) is isolated. For example, the sulfonated tetracyclone of Formula (II) can be isolated by precipitation, filtration, extraction, distillation, or a combination thereof. In a preferred embodiment, the sulfonated tetracyclone of Formula (II) is isolated by precipitation and filtration.

[0058] In some embodiments, Formula (I) has the structure:wherein:R1A, RIB, RIG RID, RIE,an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, and cyano;A| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

[0059] In some embodiments, Formula (II) has the structure:wherein:R1A, RIB, RIG RID, RIE>an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3'X+, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, Re,an(RDareindependently H, CB6alkyl, aryl, or heteroaryl;A| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and A2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

[0060] In some embodiments, Formula (II) comprises one, two, three, or four -SO3H groups. In some embodiments, Formula (II) comprises at least two -SO3H groups. In some embodiments, Formula (II) comprises four -SO3H groups.

[0061] In some embodiments, Formula (II) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3-X+, provided that at least two of R1A, R1B, R1C, R1D, R1E, and R1Fare independently aryl or heteroaryl substituted with SO3'X+, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C3.6alkyl, aryl, or heteroaryl;A1is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andA2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

[0062] In some embodiments, the sulfonated tetracyclone of Formula (II) has the(VIII).

[0063] In some embodiments, the sulfonated tetracyclone of Formula (II) is reacted with triethylamine to form a tri ethylammonium salt of Formula (II).

[0064] In some embodiments, the sulfonated tetracyclone of Formula (II) is reacted with an alkyne of Formula (III), wherein Formula (III) has the structure:Di = L1-L2-L3- D2(III),wherein:L1is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl;L2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl;L3is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andD1and D2are independently H, R1G, R1H, or a protecting group, wherein R1Gand R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3-X+, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.In some embodiments, the reaction between the sulfonated tetracyclone of Formula (II) and the alkyne of Formula (III) forms a sulfonated polyphenylene polymer repeat unit (x) of Formula (IV), wherein Formula (IV) has the structure:(IV),wherein:R1A, R1B, R1C, R1D, R1E, and R1Fare independently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3-X+, provided that at least two of R1A, R1B, R1C, R1D, R1E, and R1Fare independently aryl or heteroaryl substituted with SO3'X+;R1Gand R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+;A| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;A2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;L| is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L2and L3are independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andwherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

[0065] In some embodiments, the reaction between the sulfonated tetracyclone of Formula (II) and the alkyne of Formula (III) forms a sulfonated polyphenylene polymer repeat unit (x) of Formula (IV), provided that the repeat unit of Formula (IV) is not:(A).

[0066] In some embodiments, A | is unsubstituted or substituted arylene, wherein the substituted arylene is substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, and A2is absent.

[0067] In some embodiments, I is naphthalenylene, phenylene, oralkylsubstituted phenylene, and L2and L3are independently absent or phenylene, and wherein when present, each phenylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl and halo.

[0068] In some embodiments, a compound of Formula (II) is mixed with a compound of Formula (V) prior to reacting with a compound of Formula (III), wherein Formula (V) has the structure:wherein:R2A, F^2B’ ^20 ^2D’ R-2E, and R-2Fareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected fromalkyl, halo, nitro, and cyano;B| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; and B2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.In some embodiments, the mixing of a compound of Formula (II) with a compound of Formula (V), prior to reacting with a compound of Formula (III), produces a sulfonated polyphenylene copolymer of Formula (VI) having a repeat unit (x) and a repeat unit (y), wherein Formula (VI) has the structure:(VI),wherein:R1A, RIB, RIO RID, R1E, and R1Fareindependently aryl or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3'X+;R2A, R2B, ^2C’, R2D, R2E,ar|d ^2Fareindependently aryl or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, and cyano;R1Gand R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+;R2Gand R2Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, and cyano;A| and B| are independently arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from CB6alkyl, halo, nitro, cyano, aryl, and heteroaryl;A2and B2are independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L| is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andL2and L3are each independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C3.6alkyl, aryl, or heteroaryl.

[0069] In some embodiments, the sulfonated polyphenylene copolymer has a structure of Formula (VII):(VII),wherein:R3, R4, R5, and R6are independently selected from H and SO3⁻X+;R7, R8, R9, and R10are independently selected from H, C3.6alkyl, halo, nitro, and cyano;A1and B1are independently arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;A2and B2are independently absent, arylene, heteroarylene, aralkylene, or heteroaralkyl ene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene, are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L| is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andL2and L3are each independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from CB6alkyl, halo, nitro, cyano, aryl, and heteroaryl, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

[0070] In some embodiments, A1, B1, or both A1and B1are independently arylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl; and A2, B2, or both A2and B2are absent.

[0071] In some embodiments, the sulfonated polyphenylene polymer or sulfonated polyphenylene copolymer comprises a branching comonomer M wherein M1is selected from an unsubstituted or substituted linking atom, arylene, heteroarylene, aralkylene, heteroaralkyl ene, and combinations thereof, wherein the linking atom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted or substituted with 1, 2, or 3 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl.

[0072] In some embodiments, M1is bound through at least three covalent bonds, and M1is selected from the group consisting of:

[0073] In some embodiments, the structure of the sulfonated polyphenylene polymer or sulfonated polyphenylene copolymer is a branched structure of Formula (V’):(V’),wherein P| and P2are both a repeat unit (x) of Formula (I), or are independently selected from a repeat unit (x) of Formula (I) and a repeat unit (y) of Formula (II); and R1A,are as described for Formula (I).

[0074] In some embodiments, the ratio of a repeat unit (z) to the sum of a repeat unit (x), P and P2of Formula (V’) (i.e., z / (x+P3+P2)) is less than 0.2.

[0075] In some embodiments, each L1is independently naphthalenylene, phenylene, or C1-6alkyl-substituted phenylene, and each L2and each L3is independently absent or phenylene, wherein when present, each phenylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl and halo, and wherein each L3is the same or different, each L2is the same or different, and each L3is the same or different.

[0076] In some embodiments, each L3, L2, and L1of -L3-L2-L1-, when present, is independently selected from:

[0077] In some embodiments, the sulfonated polyphenylene polymer repeat unit (x) of Formula (IV) is selected from:wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

[0078] In some embodiments, the sulfonated polyphenylene polymer repeat unit (x) of Formula (IV) is selected from:wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

[0079] In some embodiments, the sulfonated polyphenylene polymer repeat unit (y) is selected from:

[0081] In some embodiments, the mole percent of the repeat unit (x) is about 59% to about 99%, and the mole percent of the repeat unit (y) is about 41% to about 1%. In some embodiments, the mole percent of the repeat unit (x) is about 79% to about 99%, and the mole percent of the repeat unit (y) is about 21% to about 1%. In some embodiments, the mole percent of the repeat unit (x) is about 85% to about 95%, and the mole percent of the repeat unit (y) is about 15% to about 5%.

[0082] In some embodiments, the mole percent of the repeat unit (x) is about 90%, and the mole percent of the repeat unit (y) is about 10%.

[0083] In some embodiments, the polyphenylene copolymer is a random copolymer comprising a random distribution of the repeat units (x) and (y).

[0084] In some embodiments, the polyphenylene copolymer is a statistical copolymer comprising an average composition ratio of the repeat units (x) and (y).

[0085] In some embodiments, the polyphenylene copolymer is a block copolymer, wherein:the repeat unit (x) is an integer from 3 to 100, andthe repeat unit (y) is an integer from 3 to 100; andwherein a mole ratio of the first block to the second block ranges from 1:99 to 99: 1.

[0086] In some embodiments, the cation is an alkali metal ion. In some embodiments, the cation is [N(RA)(RB)(RC)(RD)]+, wherein RA, RB, Rc, and RDareindependently H,alkyl, aryl, or heteroaryl. In some embodiments, the cation is triethylammonium.

[0087] In some embodiments, the sulfonated polyphenylene polymer is used in a membrane.

[0088] In some embodiments, the sulfonated polyphenylene polymer produced by the methods disclosed herein is used in an electrochemical device such as a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, or redox flow battery.

[0089] In some embodiments, disclosed herein is an electrochemical device comprising the sulfonated polyphenylene polymer produced by the methods disclosed herein, wherein the electrochemical device is a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, redox flow battery, or other electrochemical device.EXAMPLESExample 1Preparation of Acetyl Sulfate Reagent and Sulfonation of L4-bis(2,4,5- triphenylcyclopentadienone) benzene (BTCB)

[0090] The first method involves the preparation of an acetyl sulfate reagent, which is then used to sulfonate the l,4-bis(2,4,5-triphenylcyclopentadienone) benzene (BTCB) polyphenylene.Preparation of acetyl sulfate:

[0091] In a dry two-neck round bottom flask, methylene chloride was introduced, followed by the addition of acetic anhydride. The solution was purged with argon for 10 minutes, and then sulfuric acid was added dropwise, ensuring the temperature did not exceed 15°C. The solution was slowly warmed to room temperature under a gentle flow of argon, resulting in a colorless, viscous acetyl sulfate reagent.Sulfonation of BTCB with acetyl sulfate:

[0092] The BTCB polyphenylene was then introduced into a separate dried two-neck round bottom flask, and methylene chloride was added. After purging with argon, the previously prepared acetyl sulfate reagent was added dropwise using an addition funnel. The reaction mixture was heated to 50°C and stirred overnight. Upon completion, the reaction was cooled to room temperature, and the methylene chloride was removed by distillation. The product, tetra(para-sulfonated) bistetracyclone (TPSB)-H+, was obtained as a bright purple plate with a yield of 90%.

[0093] FIG. 1 shows a synthetic scheme for the formation of acetyl sulfate and for the sulfonation of BTCB polyphenylene with acetyl sulfate, resulting in TPSB-H+, as described herein.

[0094] FIG. 2 shows the nuclear magnetic resonance spectroscopy (NMR) data with well-defined signals for seven individual TPSB-H+batches, demonstrating high reproducibility of the TPSB-H+synthesis.

[0095] FIG. 3 shows the NMR data of FIG. 2 at the aromatic region, again demonstrating high reproducibility of the TPSB-H+synthesis.Example 2One-Pot Sulfonation of BTCB

[0096] The second method involves a one-pot sulfonation of the BTCB polyphenylene. In a dry two-neck round bottom flask, BTCB was introduced with methylene chloride. Acetic anhydride was then added, and the solution was purged with argon for 10 minutes. Sulfuric acid was added dropwise, ensuring the temperature did not exceed 15°C. The solution was slowly warmed to room temperature under a gentle flow of argon and then heated to 50°C overnight. After the reaction was cooled to room temperature, the methylene chloride was removed by distillation to obtain TPSB-H+.Purification of TPSB-H+:

[0097] Following the sulfonation reactions, the TPSB-H+product was purified. After the removal of methylene chloride, glacial acetic acid was introduced into the solution and stirred under an inert atmosphere. The resulting precipitate was filtered, washed with glacial acetic acid, and dried in the oven at 80°C, yielding a bright red precipitate. FIGs. 2 and 3 show NMR data with well-defined signals for multiple TPSB-H+batches, demonstrating high reproducibility of the TPSB-H+synthesis.Conversion of TPSB-H+to TPSB-TES:

[0098] The TPSB-H+was then converted to the triethylammonium salt (TES) form. After the removal of methylene chloride, glacial acetic acid was introduced, and the resulting precipitate was filtered and washed. The filtered powder was then dissolved in butanol and precipitated by the addition of triethylamine. The final product, TPSB-TES, was filtered, rinsed with butanol, and dried in the oven overnight at 80°C, with a yield of 91%. FIG. 1 shows a synthetic scheme for the conversion of TPSB-H+to TPSB-TES as described herein.Conversion of TPSB-H+to TPSB-Na+:

[0099] The TPSB-H+was also converted to the sodium form (Na+). TPSB-H+was dissolved in 2-propanol or ethanol and was stirred until complete dissolution, followed by addition of sodium acetate (NaOAc). The desired product precipitated, which was then filtered and washed with 2-propanol or ethanol. The final product, TPSB-Na+, was dried in the oven overnight at 80°C, with a yield of 93%.Example 3

[0100] Table 1 outlines the impact of BTCB concentration in dichloromethane (DCM) on overall reaction time and yields, while maintaining a constant ratio of acetic anhydride to sulfuric acid relative to BTCB.

[0101] Table 1: Summary of Synthetic Batches

[0102] The data in Table 1 clearly demonstrates that BTCB concentration in dichloromethane influences both the yield of the sulfonated product and the reaction time. Therefore, according to the 2-step sulfonation protocol of Example 1, a BTCB concentration of 0.15 g / mL or lower is preferred, as it leads to higher yields and shorter reaction times. In contrast, for the l-step sulfonation protocol of Example 2, a BTCB concentration of 0.2 g / mL of DCM is optimal, as it results in higher product yields and reduced reaction times.

[0103] While illustrative embodiments have been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention.

Claims

CLAIMSThe embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method for sulfonation of a polyphenylene of Formula (I), comprising: a) dissolving a polyphenylene of Formula (I) in dichloromethane;b) reacting acetic anhydride with concentrated sulfuric acid in dichloromethane to form acetyl sulfate; andc) reacting the dissolved polyphenylene of Formula (I) with the acetyl sulfate to form a sulfonated tetracyclone of Formula (II),wherein Formula (I) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(i RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, and cyano;A| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andA2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, andwherein Formula (II) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3⁻X+, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl;A1is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andA2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

2. The method of Claim 1, wherein a concentration of the polyphenylene of Formula (I) in dichloromethane is about 2 wt % to about 25 wt %.

3. The method of Claim 1 or Claim 2, wherein a molar ratio of equivalents of acetic anhydride to equivalents of concentrated sulfuric acid to equivalents of the polyphenylene of Formula (I) is 30:25:1.

4. The method of any one of Claims 1-3, wherein the reacting acetic anhydride with concentrated sulfuric acid in dichloromethane to form acetyl sulfate occurs at a temperature below about 15°C.

5. The method of any one of Claims 1-4, wherein an amount of acetyl sulfate is about 10 molar equivalents to about 30 molar equivalents excess with respect to an amount of the polyphenylene of Formula (I).

6. The method of any one of Claims 1-5, wherein the reacting is at a temperature between about 20°C and about 50°C.

7. The method of any one of Claims 1-6, wherein the reacting is at a temperature between about 25°C and about 50°C.

8. A method for sulfonation of a polyphenylene of Formula (I), comprising: a) dissolving a polyphenylene of Formula (I) in a mixture of dichloromethane and acetic anhydride; andb) reacting the dissolved polyphenylene of Formula (I) with concentrated sulfuric acid to produce a sulfonated tetracyclone of Formula (II),wherein Formula (I) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(i RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, and cyano;A| is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andA2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, andwherein Formula (II) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C1-6alkyl, halo, nitro, cyano, and SO3⁻X+, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl;A1is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andA2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl.

9. The method of Claim 8, wherein a concentration of the polyphenylene of Formula (I) in the mixture of dichloromethane and acetic anhydride is about 2 wt % to about 25 wt %.

10. The method of Claim 8 or 9, wherein the reacting is at a temperature between about 10°C and about 15°C.

11. The method of any one of Claims 1-10, wherein a concentration of the polyphenylene of Formula (I) is about 5 wt% to about 15 wt %.

12. The method of any one of Claims 1-11, wherein the reacting is for between about 1 and about 72 hours.

13. The method of any one of Claims 1-12, further comprising isolating the sulfonated tetracyclone of Formula (II).

14. The method of Claim 13, wherein the isolating is isolating by precipitating, isolating by filtering, isolating by extracting, isolating by distilling, or a combination thereof.

15. The method of any one of Claims 1-14, wherein Formula (II) comprises one, two, three, or four -SO3H groups.

16. The method of Claim 15, wherein Formula (II) comprises four -SO3H groups.

17. The method of any one of Claims 1-16, wherein the sulfonated tetracyclone has a structure of Formula ((VIII).

18. The method of any one of Claims 1-17, further comprising reacting the sulfonated tetracyclone of Formula (II) with tri ethylamine to form a tri ethylammonium salt of Formula (II).

19. The method of any one of Claims 1-18, further comprising reacting the sulfonated tetracyclone of Formula (II) with an alkyne of Formula (III), to form a sulfonated polyphenylene polymer repeat unit (x) of Formula (IV),wherein Formula (III) has the structure:wherein:L1is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from CG6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from Cj.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L3is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from Cj.6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andD3and D2are independently H, R1G, R1H, or a protecting group, wherein R1Gand R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from CG6alkyl, halo, nitro, cyano, and SO3'X+, and wherein X+is H+, a cation, an alkali metal ion, or[N(RA)(RB)(RC)(RD)]+wherein RA, RB, Rc, and RDare independently H, C3.6alkyl, aryl, or heteroaryl, andwherein Formula (IV) has the structure:wherein:R1A, RIB, RIG RID, RlE’an(RIFareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+, provided that at least two of R1A, RIB, R1O R1D> R1B and R1Fare independently aryl or heteroaryl substituted with SO3'X+;R3Q and R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+;A3is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;A2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl;L| is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl;L2and L3are independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl; and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, Rc, and RDare independently H, C3.6alkyl, aryl, or heteroaryl.

20. The method of Claim 19, wherein A| is unsubstituted or substituted arylene, wherein the substituted arylene is substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl, and A2is absent.

21. The method of Claim 19 or 20, wherein L3is naphthalenylene, phenylene, or C1-6alkyl-substituted phenylene, and L2and L3are independently absent or phenylene, and wherein when present, each phenylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl and halo.

22. The method of any one of Claims 1-21, further comprising mixing a compound of Formula (II) with a compound of Formula (V) prior to reacting with a compound of Formula (III), to form a sulfonated polyphenylene copolymer of Formula (VI) having a repeat unit (x) and a repeat unit (y),wherein Formula (V) has the structure:wherein:R2A, F^2B’ ^20 ^2D’ ^2E’and R-2Fareindependently aryl or heteroaryl, each unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, and cyano;B3is arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andB2is absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from halo, nitro, cyano, aryl, and heteroaryl; andwherein Formula (VI) has the structure:(VI),wherein:R1A, RIB, RIO ®4D’ R1E>an(i ®-lFareindependently aryl or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+;R2A, ®-2B’ -2C’ ®-2D’ ®-2E’an^ ^2Fareindependently aryl or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, and cyano;R3Q and R1Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, cyano, and SO3'X+;R2Gand R2Hare independently H, aryl, or heteroaryl, wherein said aryl and heteroaryl are unsubstituted or substituted with 1, 2, 3, 4, or 5 substituents independently selected from C3.6alkyl, halo, nitro, and cyano;A1and B1are independently arylene, heteroarylene, aralkylene, or heteroaralkyl ene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene areunsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl;A2and B2are independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl;L1is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl; andL2and L3are each independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C3.6alkyl, halo, nitro, cyano, aryl, and heteroaryl, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, Rc, and RDare independently H, C3.6alkyl, aryl, or heteroaryl.

23. The method of Claim 22, wherein the sulfonated polyphenylene copolymer has(VII),wherein:R3, R4, R5, and R6are independently selected from H and SO3⁻X+;R7, R8, R9, and R10are independently selected from H, Cj.^ alkyl, halo, nitro, and cyano;A| and B| are independently arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl;A2and B2are independently absent, arylene, heteroarylene, aralkylene, or heteroaralkyl ene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkylene, are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from Cj.^ alkyl, halo, nitro, cyano, aryl, and heteroaryl;L1is an unsubstituted or substituted linking heteroatom, arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein said arylene, heteroarylene, aralkylene, and heteroaralkyl ene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl; andL2and L3are each independently absent, arylene, or heteroarylene, wherein said arylene and heteroarylene are unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl, and wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

24. The method of Claim 22 or 23, wherein A B or both A3and B3are independently arylene, unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected from C1-6alkyl, halo, nitro, cyano, aryl, and heteroaryl; and A2, B2, or both A2and B2are absent.

25. The method of any one of Claims 19-24, wherein the sulfonated polyphenylene polymer or sulfonated polyphenylene copolymer comprises a branching comonomer M wherein M | is selected from an unsubstituted or substituted linking atom, arylene, heteroarylene, aralkylene, heteroaralkylene, and combinations thereof, wherein the linking atom, arylene, heteroarylene, aralkylene, and heteroaralkylene are each unsubstituted orsubstituted with 1, 2, or 3 substituents independently selected fromalkyl, halo, nitro, cyano, aryl, and heteroaryl.

26. The method of Claim 25, wherein M| is bound through at least 3 covalent bonds, and M | is selected from the group consisting of:

27. The method of Claim 25 or 26, wherein the structure of the sulfonated polyphenylene polymer or sulfonated polyphenylene copolymer is a branched structure of Formula (V’):wherein P| and P2are both a repeat unit (x) of Formula (I), or are independently selected from a repeat unit (x) of Formula (I) and a repeat unit (y) of Formula (II).

28. The method of Claim 27, wherein the ratio of a repeat unit (z) to the sum of a repeat unit (x), P and P2of Formula (V’) (i.e., z / (x+P1+P2)) is less than 0.2.

29. The method of any one of Claims 19-28, wherein each L1is independently naphthalenylene, phenylene,alkyl -substituted phenylene, and each L2and each L3isindependently absent or phenylene, wherein when present, each phenylene is unsubstituted or substituted with 1, 2, 3, or 4 substituents independently selected fromalkyl and halo, and wherein each L| is the same or different, each L2is the same or different, and each L3is the same or different.

30. The method of any one of Claims 19-29, wherein each L3, L2, and L1of –L3–L2–L1–, when present, is independently selected from:

31. The method of any one of Claims 19-30, wherein the sulfonated polyphenylene polymer repeat unit (x) of Formula (IV) is selected from:wherein X+is H+, a cation, an alkali metal ion, or [N(RA)(RB)(RC)(RD)]+wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

32. The method of any one of Claims 19-30, wherein the sulfonated polyphenylene polymer repeat unit (x) of Formula (IV) is selected from:RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

33. The method of any one of Claims 22-32, wherein the sulfonated polyphenylene polymer repeat unit (y) is selected from:

34. The method of any one of Claims 22-32, wherein the repeat unit (y) is selected from:

35. The method of any one of Claims 22-34, wherein the mole percent of the repeat unit (x) is about 59% to about 99%, and the mole percent of the repeat unit (y) is about 41% to about 1%.

36. The method of any one of Claims 22-35, wherein the mole percent of the repeat unit (x) is about 90%, and the mole percent of the repeat unit (y) is about 10%.

37. The method of any one of Claims 22-36, wherein the polyphenylene copolymer is a random copolymer comprising a random distribution of the repeat units (x) and (y).

38. The method of any one of Claims 22-36, wherein the polyphenylene copolymer is a statistical copolymer comprising an average composition ratio of the repeat units (x) and (y).

39. The method of any one of Claims 22-36, wherein the polyphenylene copolymer is a block copolymer, wherein:the repeat unit (x) is an integer from 3 to 100, andthe repeat unit (y) is an integer from 3 to 100; andwherein a mole ratio of the first block to the second block ranges from 1:99 to 99: 1.

40. The method of any one of Claims 1-39, wherein the cation is an alkali metal ion or [N(RA)(RB)(RC)(RD)]+, wherein RA, RB, RC, and RDare independently H, C1-6alkyl, aryl, or heteroaryl.

41. The method of any one of Claims 1-41, wherein the cation is triethylammonium.

42. The method of any one of Claims 19-41, wherein the sulfonated polyphenylene polymer is used in a membrane.

43. A method of using the sulfonated polyphenylene polymer produced by the method of any one of Claims 19-42 in an electrochemical device such as a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, or redox flow battery.

44. An electrochemical device comprising the sulfonated polyphenylene polymer produced by the method of any one of Claims 19-42, wherein the electrochemical device is a fuel cell, electrolyzer, hydrogen pump, thermoelectrochemical hydrogen pump, electrochemical hydrogen compressor, redox flow battery, or other electrochemical device.

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