Ionic copolymers, methods and uses thereof

Abstract

Ionic random, statistical, linear, branched, and block copolymers and reinforced membranes thereof are described herein. Such ionic copolymers comprise both sulfonated polyphenylene monomers and non-sulfonated polyphenylene monomers. Also described herein are uses of such ionic polymer membranes. Such ionic copolymers and membranes made therefrom are useful in fuel cells, water electrolysers, water purification, and battery products.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 505,012, filed May 30, 2023, the disclosure of which is hereby incorporated in its entirety by reference.

[0003] background

[0004] Sulfonated hydrocarbon-based ionic polymers and proton exchange membranes (PEMs) made from them are gaining increasing attention in electrochemical energy conversion devices, such as fuel cells, electrolyzers, and batteries, as well as in other technological fields such as humidification and water purification devices.

[0005] In these applications, and in many others, perfluorinated materials are the primary materials used, such as perfluorosulfonic acid (PFSA) materials, like Nafion. ® .

[0006] Hydrocarbon materials offer significant advantages over conventional PFSA materials, including but not limited to improved thermomechanical stability, simplified manufacturing methods, reduced costs, and reduced environmental impact throughout the manufacturing and end-of-life process.

[0007] However, developing hydrocarbon ionic polymers suitable for such applications requires extensive iterative design and optimization of structure-property relationships. Ionic polymers should simultaneously exhibit a) high ionic conductivity; b) balanced water absorption, retention, and distribution; c) limited swelling, volume expansion, and contraction behavior in response to hydration and / or dehydration; and d) significant chemical robustness sufficient to withstand the dynamic electrochemical, thermochemical, and thermomechanical environments typically associated with ionic polymer applications.

[0008] Few ionic polymers exhibit the properties necessary for practical use in electrochemical environments. Highly functionalized polymers (e.g., those with >2 meq / g ion exchange capacity) often absorb large amounts of water (wt%) and swell significantly when introduced into moisture or liquid water. Simultaneously, reduced humidity leads to significant internal stress (i.e., large dehydration) and decreased ionic conductivity. These effects are further exacerbated during electrochemical operation (e.g., in hydrogen fuel cells), where both water flux and hydration gradient exist due to electroosmotic drag and the formation or consumption of water.

[0009] The aforementioned conditions create in-situ mechanical stress on the ionic polymer membrane without significant robustness, such as resistance to swelling and deformation, which may lead to premature failure of the ionic polymer membrane and consequently, failure of the device including the membrane.

[0010] Therefore, methods to reduce the swelling behavior of ionic polymers and membranes containing ionic polymers and / or improve their mechanical elasticity and toughness are crucial for improving the overall lifespan of ionic polymers and membranes containing ionic polymers in desired applications.

[0011] Common methods for reducing swelling of ionic polymers and membranes containing ionic polymers include reducing the ion exchange capacity (IEC) of the ionic polymer. Reducing the number of acid functional units in the ionic polymer decreases the hydrophilicity of the material and generally leads to reduced water absorption and swelling, which is desirable. However, it usually also results in a decrease in ionic (proton) conductivity and electrochemical performance, which is undesirable.

[0012] The aforementioned effects are generally linearly related, with the reduction in water absorption being proportional to the reduction in IEC, and the reduction in swelling being proportional to the decrease in proton conductivity and electrochemical performance.

[0013] Therefore, there is a need for ionic polymer membranes for electrochemical environments and applications that exhibit sufficiently low water absorption and swelling, while simultaneously exhibiting sufficient proton conductivity and electrochemical performance.

[0014] Overview

[0015] This overview is provided to introduce a set of concepts in a simplified form, which will be further described in detail below. This overview is not intended to identify key features of the claimed subject matter, nor is it intended to help determine the scope of the claimed subject matter.

[0016] In some respects, this document provides a copolymer comprising a first repeating unit (x) having formula (I) and a second repeating unit (y) having formula (II):

[0017]

[0018]

[0019] The copolymer comprises:

[0020] The molar percentage (x) is approximately 75% to approximately 99%.

[0021] Approximately 25% to approximately 1% of the molar percentage (y), and

[0022] in:

[0023] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0024] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0025] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein each R 3A R 3B R 3C R 3D R 3E and R 3F Not replaced or selected independently from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0026] R3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0027] A1 and B1 are independently arylene, heteroarylene, aralkylene, or heteroaralkylene, wherein each of the arylene, heteroarylene, aralkylene, and heteroaralkylene is either unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl.

[0028] A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0029] L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0030] L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0031] L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0032] X + It is a cation.

[0033] In other respects, this article provides a method for preparing random copolymers comprising forming a mixture of a first repeating unit (x) of formula (VI) and a second repeating unit (y) of formula (VII):

[0034]

[0035] in:

[0036] R 1A R 1B R1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0037] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0038] A1 is arylene, heteroarylene, arylene, or heteroarylene, wherein the arylene, heteroarylene, arylene, and heteroarylene are unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl.

[0039] A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0040] L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0041] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0042] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0043] X + It is a cation; and

[0044] A is the reactive first terminal group.

[0045]

[0046] in

[0047] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0048] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, nitro, and cyano groups;

[0049] B1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, or heteroarylalkyl group is unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups.

[0050] B2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0051] K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1 by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0052] K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0053] K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0054] B is the second reactive terminal group configured to react with A, and

[0055] React A and B to provide a random copolymer of formula (III):

[0056]

[0057] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0058] In other respects, this document provides films comprising the copolymers described herein. Attached Figure Description

[0059] The foregoing aspects and many accompanying advantages of this disclosure will become more readily apparent and better understood when taken in conjunction with the accompanying drawings and by referring to the following detailed description, wherein:

[0060] Figure 1 The simplified equivalent circuit is shown. (CPE) dl r- is the interfacial impedance of the electrode surface, R bIt is the impedance of the electrolyte membrane, C b It is a film capacitor.

[0061] Figure 2A and 2B The experiment demonstrates the swelling (wet) / deswelling (dry) cycle design.

[0062] Figures 3A-3D The results of membrane swelling / deswelling tests are shown for 100%-sPP, 90%-sPP, 80%-sPP and 70%-sPP unreinforced membranes.

[0063] Figure 4A This demonstrates the water absorption of reinforced membranes containing 100% functionalized sulfonated polystyrene 100%-sPP (n=15) or copolymers containing 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (90%-sPP) (n=30).

[0064] Figure 4B The thickness swelling of the reinforced film is shown to be that of 100% functionalized sulfonated polystyrene 100%-sPP (n=15) or a copolymer containing 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (90%-sPP) (n=30).

[0065] Figure 5 The dimensional swelling (longitudinal (MD) and transverse (TD)) of reinforced films containing 100% functionalized sulfonated polystyrene 100%-sPP (n=15) or copolymers containing 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (n=30) is shown.

[0066] Figure 6 The in-plane and through-plane proton conductivity of reinforced films containing 100% functionalized sulfonated polystyrene 100%-sPP (n=15) or copolymers containing 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (n=30) is displayed.

[0067] Figure 7 The results of membrane swelling / deswelling tests are shown for reinforced membranes of 100%-sPP and 90%-sPP.

[0068] Figure 8A The display showcases the sPP ionic polymer and copolymer series, as well as Nafion XL reinforced membranes for applications requiring 150 kPa. g Fuel cell performance under back pressure H2 / O2 at 80°C and 100% RH.

[0069] Figure 8B The display showcases the sPP ionic polymer and copolymer series, as well as Nafion XL reinforced membranes for applications requiring 150 kPa. gThe areal resistivity (ASR) of fuel cells with back pressure H2 / O2 at 80°C and 100% RH.

[0070] Figure 9A The display showcases the sPP ionic polymer and copolymer series, as well as Nafion XL reinforced membranes for applications requiring 150 kPa. g Fuel cell performance under back pressure H2 / air at 80°C and 100% RH.

[0071] Figure 9B The display showcases the sPP ionic polymer and copolymer series, as well as Nafion XL reinforced membranes for applications requiring 150 kPa. g The areal resistivity (ASR) of a fuel cell with back pressure H2 / air at 80°C and 100% RH.

[0072] Figure 10A The display shows the sPP ionic polymer and copolymer series and Nafion XL reinforced film at 300 kPa. g Fuel cell performance under H2 / air conditions at 80°C and 100% RH.

[0073] Figure 10B The display shows the sPP ionic polymer and copolymer series and Nafion XL reinforced film at 300 kPa. g The areal resistivity (ASR) of fuel cells at 80°C and 100% RH under H2 / air conditions.

[0074] Figure 11A The display shows the performance of sPP ionic copolymer series and Nafion XL reinforced membrane in H2 / air, 150 kPa. g Fuel cell performance at 80℃ and 30% RH.

[0075] Figure 11B The display shows the performance of sPP ionic copolymer series and Nafion XL reinforced membrane in H2 / air, 150 kPa. g The areal resistivity (ASR) of fuel cells at 80°C and 30% RH.

[0076] Figure 12 The measured maximum power density (mW / cm²) of various MEAs containing the reinforcing membrane is displayed. 2 The reinforcing membrane comprises 100% functionalized sulfonated polystyrene 100%-sPP (n=8) or a copolymer comprising 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (n=9).

[0077] Figure 13 The measured areal resistivity (mΩ / cm) of various MEAs containing reinforcing films is displayed. 2The reinforcing membrane comprises 100% functionalized sulfonated polystyrene 100%-sPP (n=8) or a copolymer comprising 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (n=9).

[0078] Detailed Explanation

[0079] This article describes copolymers comprising both anionic phenylene (ionic) and hydrophobic monomer units, as well as membranes and devices comprising such compositions. The copolymers can be prepared in a convenient and well-controlled manner by precisely controlling the position and number of anionic groups. Such copolymers can be used in cation exchange membranes.

[0080] definition

[0081] The term "substituted" means that one atom or group of atoms formally acts as a "substituent" in place of hydrogen atom attached to another group. Unless otherwise stated, the term "substituted" refers to any level of substitution, such as mono-, di-, tri-, tetra-, penta-, or more substitutions, where such substitution is permissible (e.g., producing a stable compound). Substituents are chosen independently, and substitution can occur at any chemically accessible position. It should be understood that substitution on a given atom is limited by valence. A single divalent substituent, such as an oxo, substitutes for two hydrogen atoms. In unsubstituted positions, hydrogen atoms can be present, consistent with the chemical motif, and are generally known to those skilled in the art. For example, an alkyl-substituted aryl group refers to an aryl ring in which a non-hydroalkyl substituent replaces the hydrogen atom.

[0082] When a group is not substituted, it is referred to by its group name, such as alkyl or aryl. When a group is substituted by another functional group, it can be more generally referred to as, for example, substituted alkyl or substituted aryl.

[0083] Substituents of the compounds disclosed herein are disclosed in groups or ranges. In particular, this disclosure is intended to include each and every individual subcombination of members of such groups and ranges. For example, the term "C" 1-6 The terms "alkyl" and "C1-C6 alkyl" are specifically intended to individually disclose (but are not limited to) methyl, ethyl, C3 alkyl, C4 alkyl, C5 alkyl, and C6 alkyl, whether linear or branched. For example, a C4 alkyl may be n-butyl, sec-butyl, isobutyl, or tert-butyl. For example, the term "substituted with 1, 2, 3, 4, or 5 substituents" is intended to individually disclose substitution with 1, 2, 3, or 4 substituents; substitution with 1, 2, or 3 substituents; substitution with 1 or 2 substituents; or substitution with 1 substituent.

[0084] This further implies that the compounds disclosed herein are stable. As used herein, "stable" means a compound that is robust enough to withstand separation from the reaction mixture to a useful purity.

[0085] It should also be recognized that, for clarity, certain features of this disclosure described in the context of separate embodiments may also be provided in combination in a single embodiment. Conversely, for brevity, various features of this disclosure described in the context of a single embodiment may also be provided separately or in any suitable sub-combination.

[0086] Divalent groups, such as linking groups between the first and second parts (e.g., alkylene, arylene, etc.), are intended to be oriented in both the forward and reverse directions relative to the first and second parts, unless otherwise specifically described.

[0087] As used herein, the term “about” can be understood to include values ​​up to 10% of the stated value. For example, about 2 meq / g in IEC means 2 + / - 0.2 meq / g, or 1.8–2.2 meq / g in IEC.

[0088] As used herein, the term "alkyl" refers to a straight-chain or branched hydrocarbon group. In some embodiments, the alkyl group has 1 to 12 carbon atoms, and may have 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 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), butyl (e.g., n-butyl, sec-butyl, isobutyl, and tert-butyl), pentyl (e.g., n-pentyl, tert-pentyl, neopentyl, isopentyl, pent-2-yl, pent-3-yl), and hexyl (e.g., n-hexyl, geometric isomers). Where a stereocenter is present, alkyl also refers to any stereoisomer.

[0089] As used herein, the term "alkylene" refers to the alkyl group attached to it.

[0090] As used herein, the term "cycloalkyl" refers to a non-aromatic carbide ring, including cyclic alkyl, alkenyl, and alkynyl groups. Cycloalkyl groups can comprise monocyclic or polycyclic (e.g., having 2, 3, or 4) fused ring systems or spirocyclic rings. In some embodiments, the cycloalkyl group may 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 may further have 0, 1, 2, or 3 double bonds and / or 0, 1, or 2 triple bonds. The definition of cycloalkyl also includes a portion having one or more aromatic rings fused to a cycloalkyl ring (i.e., sharing a common bond), such as benzo[a] derivatives of pentane, pentene, hexane, etc. Cycloalkyl groups having one or more fused aromatic rings are linked by a non-aromatic portion. One or more cyclic carbon atoms of the cycloalkyl group may be oxidized, for example by having oxo or thio substituents. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptanetrienyl, norbornyl, norpinyl, norcamyl, adamantyl, etc.

[0091] As used herein, the term "aryl" refers to an aromatic hydrocarbon group having 6 to 10 carbon atoms. Representative aryl groups include phenyl and naphthyl groups. In some embodiments, the term "aryl" includes monocyclic or polycyclic (e.g., having 2, 3, or 4 fused rings) aromatic hydrocarbons, such as, for example, naphthyl, anthracene, indene, and indene. The definition of aryl also includes a portion having one or more cycloalkyl rings fused to an aromatic ring (i.e., having a common bond), such as benzo[a] derivatives of pentane, pentene, hexane, etc. The aryl group having one or more fused cycloalkyl rings is linked by an aromatic moiety.

[0092] As used herein, the term "arylene" refers to a group attached to an aryl group. For example, the term "phenylene" refers to a group attached to a phenyl group, and "naphthylene" refers to a group attached to a naphthyl group.

[0093] As used herein, the term "aralkyl" refers to an alkyl or cycloalkyl group as defined herein, wherein an aryl group, as defined herein, replaces one alkyl hydrogen atom. A representative aralkyl group is the benzyl group.

[0094] As used herein, the term "aramidene" refers to the aramid group attached to the aramid group.

[0095] As used herein, the term "heteroaryl" refers to a 5- to 10-membered aromatic monocyclic or bicyclic group containing 1 to 4 heteroatoms selected from O, S, and N. Representative 5- or 6-membered aromatic monocyclic groups include pyridine, pyrimidine, pyridazine, furan, thiophene, thiazole, oxazole, and isoxazole. Representative 9- or 10-membered bicyclic aromatic groups include benzofuran, benzothiophene, indole, pyranopyrrole, benzopyran, quinoline, benzocyclohexyl, and naphthidine.

[0096] As used herein, the term "heteroaryl" refers to the linking heteroaryl group.

[0097] As used herein, the term “heteroaryl” means an alkyl or cycloalkyl group as defined herein, wherein the heteroaryl group as defined herein replaces one alkyl hydrogen atom.

[0098] As used herein, the term "heteroarylene" refers to the term attached to a heteroarylene alkyl group.

[0099] As used herein, the term “halogen” or “halogenated” refers to a fluorine, chlorine, bromine, or iodine group. “Halogen” or “halogenated” may refer to the entire set of fluorine, chlorine, bromine, and iodine groups, or a subset of halogens, such as fluorine, chlorine, and bromine; chlorine, bromine, and iodine; and any other combination or subcombination of halogen atoms.

[0100] As used herein, the term "copolymer" refers to a polymer composed of two or more different monomer units. A copolymer comprises at least one ionic monomer unit and at least one hydrophobic monomer unit. The ionic monomers in a copolymer may be the same or different. The hydrophobic monomers in a copolymer may be the same or different. The quantity and properties of each monomer unit in a copolymer can be controlled individually.

[0101] Unless otherwise explicitly stated, monomer units may be arranged in completely random, alternating random, regular alternating, statistical, regular block, or random block configurations. For example, a completely random configuration may be: xxyzxyyzyzzz… or y zx yzyzxx…. An alternating random configuration may be: xyxzyxyzyxz…, and a regular alternating configuration may be: xyzxyzxyz…. When containing three different block monomer units (x, y, and z), the regular block configuration (i.e., the block copolymer) has the following example configuration: …xxxyyyzzzxxx…, while the random block configuration has the following example configurations: …xxxzzzxxxyyyyzzzxxxzz zz…, or …xxxyyyyxxxyyyxxxxyyy…. Block copolymers contain blocks of three or more identical monomer units.

[0102] As used herein, the polymer term "monomer unit" refers to an atom or group of atoms in a polymer, including a portion of the chain and its side chain atoms or groups of atoms, if any, and includes "structural units." A monomer unit can be a repeating unit in the chain. A monomer unit can also refer to an end group on the polymer chain. For example, the monomer unit of polyethylene glycol can be –CH2CH2O– corresponding to a repeating unit, or –CH2CH2OH corresponding to an end group.

[0103] As used herein, the term “repeating unit” corresponds to the smallest monomeric unit or structural unit, which repeats to form macromolecules (or oligomers or blocks).

[0104] As used herein, the term "terminal group" refers to a monomeric or structural unit located at the end of a polymer chain that has only one connection to the polymer chain. For example, a terminal group can originate from a monomeric unit and be present at the end of the polymer chain. As another example, a terminal group can be part of a chain transfer agent or initiator used to synthesize the polymer.

[0105] As used herein, the term “end” of a polymer refers to a monomeric or structural unit of the polymer located at the end of the polymer backbone.

[0106] As used herein, the term "terminal group" refers to a functional group located at the end of the polymer backbone.

[0107] As used herein, the term "cation" refers to a positively charged moiety, or a moiety that can be ionized into a positively charged moiety under chemical conditions, such as by passing through a pH below the pKa of that moiety. Examples of cation moieties include, for example, ammonium, pyridinium, imino, sulfonium, quaternary phosphonium, etc.

[0108] As used herein, the term "anion" refers to a negatively charged functional group, or a functional group that can ionize into a negatively charged portion under chemical conditions, such as by passing through a pH above the pKa of that portion. Examples of anionic groups include carboxylates, sulfates, sulfonates, phosphates, phosphonates, etc.

[0109] As used herein, the term "linear" refers to a polymer having a main chain that extends unidirectionally or comprises main chain atoms, functional groups, and some and / or monomer units that are connected end-to-end without branching. A linear polymer itself may not be straight, but may be curved due to the bonding configuration of the main chain atoms, functional groups, and some and / or monomer units (e.g., ortho or meta substitution of the benzene ring), or due to rotation around bonds (e.g., C-C bonds) that cause the linear chain to bend or fold. Linear polymers include polymers containing monomer units having substituents or side groups that can extend away from the polymer main chain.

[0110] As used herein, the term "branched" refers to a polymer that includes side chains or "branches" growing from a main polymer segment (e.g., the polymer backbone). Branches consist of repeating units similar to the main segment. Branched copolymers contain branched monomers in relatively low abundance within the copolymer. Branched copolymers can comprise a mixture of linear and branched segments.

[0111] The difference between branched ionic polymers and cross-linked polymers is that branched ionic polymers do not include (multiple) polymer chains or pre-existing connections between (multiple) polymer chains.

[0112] As used herein, the term "random copolymer" is a copolymer having an irregular sequence or combination of two or more monomer units. In a completely random configuration, the monomer units may be arranged irregularly, for example, as shown below: ...xxyzxyyzyzzz... or ...yzxyzyzxx...

[0113] As used herein, the term "statistical copolymer" is a copolymer having monomer units that are determined by the molar percentage of monomer units used to generate the polymer. For example, in a statistical copolymer containing 90% ionic monomers and 10% hydrophobic monomers, the resulting polymer is expected to consist of approximately 90% ionic monomer units and approximately 10% hydrophobic monomer units.

[0114] 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 suitable methods and materials are described below, similar or equivalent methods and materials may be used in practice or testing of this disclosure. All publications, patent applications, patents, and other references mentioned herein are incorporated herein by reference in their entirety. In case of conflict, this specification (including definitions) shall prevail. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting.

[0115] copolymer

[0116] The present disclosure is particularly characterized by copolymers comprising a first repeating unit (x) having formula (I) and a second repeating unit (y) having formula (II):

[0117]

[0118]

[0119] The copolymer comprises:

[0120] The molar percentage (x) is approximately 75% to approximately 99%.

[0121] The molar percentage (y) of approximately 25% to approximately 1%, and

[0122] in:

[0123] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0124] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0125] R 3A R 3B R 3C R 3D R 3E and R 3FIndependently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0126] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0127] A1 and B1 are independently arylene, heteroarylene, arylene, or heteroarylene, each unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl;

[0128] A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0129] L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0130] L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0131] L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0132] X + It is a cation.

[0133] In one embodiment, the copolymer comprises a first repeating unit (x) having formula (I) and a second repeating unit (y) having formula (II):

[0134]

[0135] The copolymer comprises:

[0136] The molar percentage (x) is approximately 75% to approximately 99%.

[0137] Approximately 25% to approximately 1% of the molar percentage (y), and

[0138] in:

[0139] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0140] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X+ Substituents of the substituents;

[0141] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0142] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0143] A1 and B1 are independently arylene, heteroarylene, arylene, or heteroarylene, each unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl;

[0144] A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0145] L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0146] L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0147] L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0148] X + It is a cation; and

[0149] The condition is that the repeating unit in equation (I) is not:

[0150] .

[0151] In some embodiments, the copolymer comprises a first repeating unit (x) having formula (I), wherein the composition of the monomeric unit of (x) is the same as that of another monomeric unit of (x), or the composition of the monomeric unit of (x) is different from that of another monomeric unit of (x). For all monomeric units of formula (I) in the copolymer, the repeating unit (x) may be the same, or the repeating unit (x) may comprise monomeric units of different (x). For example, (x) may differ due to the number of substituents (e.g., sulfonate) or due to the nature of the substituents (e.g., sulfonate versus phosphonate or carbonate).

[0152] In some embodiments, the copolymer comprises a second repeating unit (y) having formula (II), wherein the composition of the monomer unit (y) is the same as that of another monomer unit of (y), or the composition of the monomer unit (y) is different from that of another monomer unit of (y). For all monomer units of formula (II) in the copolymer, the repeating unit (y) may be the same, or the repeating unit (y) may comprise monomer units of different y.

[0153] In some embodiments, the copolymer comprises about 75% to about 99% molar percentage (x). In some embodiments, the copolymer comprises about 80% to about 99% molar percentage (x). In some embodiments, the copolymer comprises about 85% to about 99% molar percentage (x). In some embodiments, the copolymer comprises about 90% to about 99% molar percentage (x). In some embodiments, the copolymer comprises about 75% to about 95% molar percentage (x). In some embodiments, the copolymer comprises about 80% to about 95% molar percentage (x). In some embodiments, the copolymer comprises about 85% to about 95% molar percentage (x). In some embodiments, the copolymer comprises about 88% to about 92% molar percentage (x). In some embodiments, the copolymer comprises about 90% molar percentage (x). In some embodiments, the copolymer comprises at least about 75% molar percentage (x). In some embodiments, the copolymer comprises at least about 80% molar percentage (x). In some embodiments, the copolymer comprises at least about 85% molar percentage (x). In some embodiments, the copolymer contains at least about 88% molar percentage of (x). In some embodiments, the copolymer contains no more than about 95% molar percentage of (x). In some embodiments, the copolymer contains no more than about 92% molar percentage of (x).

[0154] In some embodiments, the copolymer comprises about 25% to about 1% molar percentage (y). In some embodiments, the copolymer comprises about 20% to about 1% molar percentage (y). In some embodiments, the copolymer comprises about 15% to about 1% molar percentage (y). In some embodiments, the copolymer comprises about 10% to about 1% molar percentage (y). In some embodiments, the copolymer comprises about 25% to about 5% molar percentage (y). In some embodiments, the copolymer comprises about 20% to about 5% molar percentage (y). In some embodiments, the copolymer comprises about 15% to about 5% molar percentage (y). In some embodiments, the copolymer comprises about 12% to about 8% molar percentage (y). In some embodiments, the copolymer comprises about 10% molar percentage (y). In some embodiments, the copolymer comprises about 25% or less molar percentage (y). In some embodiments, the copolymer comprises about 20% or less molar percentage (y). In some embodiments, the copolymer comprises about 15% or less molar percentage (y). In some embodiments, the copolymer contains about 12% or less molar percentage (y). In some embodiments, the copolymer contains at least about 5% molar percentage (y). In some embodiments, the copolymer contains at least about 8% molar percentage (y).

[0155] In some implementations, the sum of the mole percentage of the first repeating unit (x) and the mole percentage of the second repeating unit (y) is approximately 100 mole percentages.

[0156] In some implementations, the sum of the mole percentage of the first repeating unit (x) and the mole percentage of the second repeating unit (y) is less than about 100 mole percentages.

[0157] In some embodiments, the copolymer comprises about 75% to about 99% molar percentage of (x) and about 25% to about 1% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 75% to about 99% molar percentage of (x) and about 25% to about 1% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 75% to about 99% molar percentage of (x) and about 25% to about 1% molar percentage of (y), wherein the molar percentage of x+y is less than about 100%. In some embodiments, the copolymer comprises about 75% molar percentage of (x) and about 25% molar percentage of (y). In some embodiments, the copolymer comprises about 75% molar percentage of (x) and about 25% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 75% molar percentage of (x) and about 25% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 75% molar percentage of (x) and about 25% molar percentage of (y), wherein the molar percentage of x+y is less than 100%.

[0158] In some embodiments, the copolymer comprises about 80% to about 99% molar percentage of (x) and about 20% to about 1% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 80% to about 99% molar percentage of (x) and about 20% to about 1% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 80% to about 99% molar percentage of (x) and about 20% to about 1% molar percentage of (y), wherein the molar percentage of x+y is less than about 100%. In some embodiments, the copolymer comprises about 80% molar percentage of (x) and about 20% molar percentage of (y). In some embodiments, the copolymer comprises about 80% molar percentage of (x) and about 20% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 80% molar percentage of (x) and about 20% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 80% molar percentage of (x) and about 20% molar percentage of (y), wherein the molar percentage of x+y is less than 100%.

[0159] In some embodiments, the copolymer comprises about 85% to about 99% molar percentage of (x) and about 15% to about 1% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 85% to about 99% molar percentage of (x) and about 15% to about 1% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 85% to about 99% molar percentage of (x) and about 15% to about 1% molar percentage of (y), wherein the molar percentage of x+y is less than about 100%. In some embodiments, the copolymer comprises about 85% molar percentage of (x) and about 15% molar percentage of (y). In some embodiments, the copolymer comprises about 85% molar percentage of (x) and about 15% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 85% molar percentage of (x) and about 15% molar percentage of (y), wherein the molar percentage of x+y is 100%. In some embodiments, the copolymer comprises about 85% molar percentage of (x) and about 15% molar percentage of (y), wherein the molar percentage of x+y is less than 100%.

[0160] In some embodiments, the copolymer comprises about 90% to about 99% molar percentage of (x) and about 10% to about 1% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 90% to about 99% molar percentage of (x) and about 10% to about 1% molar percentage of (y), wherein the molar percentage of x+y is less than about 100%.

[0161] In some embodiments, the copolymer comprises about 88% to about 92% molar percentage of (x) and about 12% to about 8% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 88% to about 92% molar percentage of (x) and about 12% to about 8% molar percentage of (y), wherein the molar percentage of x+y is less than about 100%.

[0162] In some embodiments, the copolymer comprises about 90% molar percentage of (x) and about 10% molar percentage of (y). In some embodiments, the copolymer comprises about 90% molar percentage of (x) and about 10% molar percentage of (y), wherein the molar percentage of x+y is about 100%. In some embodiments, the copolymer comprises about 90% molar percentage of (x) and about 10% molar percentage of (y), wherein the molar percentage of x+y is less than 100%.

[0163] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present.1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are aryl or heteroaryl groups.

[0164] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F The four independent elements are selected from SO3 by 1, 2, 3, 4 or 5 independently. - X + PO3 2- X + 2 and COO - X + The substituents are aryl or heteroaryl groups.

[0165] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + and PO3 2- X + Substitution of 2, condition R 1AR 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + and PO3 2- X + 2. Substituents of aryl or heteroaryl groups.

[0166] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl and SO3 - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted aryl or heteroaryl groups.

[0167] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or surrounded by 1, 2, 3, 4 or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted aryl or heteroaryl groups.

[0168] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R1F Independently aryl or heteroaryl, each unsubstituted or surrounded by 1, 2, 3, 4 or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F The four in the text are independently controlled by 1, 2, 3, 4, or 5 SO3 groups. - X + Substituted aryl or heteroaryl groups.

[0169] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from SO3. - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are aryl or heteroaryl groups.

[0170] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F It is a heteroaryl group on its own.

[0171] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently, they are heteroaryl groups, each unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C.1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + Substituents of heteroaryl groups.

[0172] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently, they are heteroaryl groups, each unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Alkyl, halogen, phenyl and SO3 - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted heteroaryl groups.

[0173] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently, they are heteroaryl groups, each unsubstituted or occupied by 1, 2, 3, 4, or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1FAt least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted heteroaryl groups.

[0174] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently, they are heteroaryl groups, each unsubstituted or selected independently from SO3 by 1, 2, 3, 4, or 5 groups. - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + Substituents of heteroaryl groups.

[0175] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F It is an aryl group on its own.

[0176] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The aryl group is substituted by a substituent.

[0177] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F The four independent elements are selected from SO3 by 1, 2, 3, 4 or 5 independently. - X + PO3 2- X + 2 and COO - X + The aryl group is substituted by a substituent.

[0178] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Alkyl, halogen, phenyl and SO3 - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1FAt least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted aryl groups.

[0179] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl, each unsubstituted or occupied by 1, 2, 3, 4 or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted aryl groups.

[0180] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl, each unsubstituted or occupied by 1, 2, 3, 4 or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F The four in the text are independently controlled by 1, 2, 3, 4, or 5 SO3 groups. - X + Substituted aryl groups.

[0181] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is an aryl group, independently unsubstituted or selected from SO3 by 1, 2, 3, 4 or 5 independently. - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1BR 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The aryl group is substituted by a substituent.

[0182] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F No more than four of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The aryl group is substituted by a substituent.

[0183] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F It is independently phenyl.

[0184] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is independently a phenyl group, and each is unsubstituted or composed of 1, 2, 3, 4, or 5 molecules independently selected from C1. 1-6Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The phenyl group is substituted with a substituent.

[0185] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is independently a phenyl group, and each is unsubstituted or composed of 1, 2, 3, 4, or 5 molecules independently selected from C1. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F The four independent elements are selected from SO3 by 1, 2, 3, 4 or 5 independently. - X + PO3 2- X + 2 and COO - X + The phenyl group is substituted with a substituent.

[0186] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is independently a phenyl group, and each is unsubstituted or composed of 1, 2, 3, 4, or 5 molecules independently selected from C1.1-6 Alkyl, halogen, phenyl and SO3 - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X + Substituted phenyl groups.

[0187] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is independently a phenyl group, and each is either unsubstituted or selected independently by 1, 2, 3, 4, or 5 molecules from SO3. - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The phenyl group is substituted with a substituent.

[0188] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Individually, each is a phenyl group, either unsubstituted or surrounded by 1, 2, 3, 4, or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently controlled by 1, 2, 3, 4 or 5 SO3 groups. - X+ Substituted phenyl groups.

[0189] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Individually, each is a phenyl group, either unsubstituted or surrounded by 1, 2, 3, 4, or 5 SO3 groups. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F The four in the text are independently controlled by 1, 2, 3, 4, or 5 SO3 groups. - X + Substituted phenyl groups.

[0190] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is a phenyl group, and none of them are substituted or converted to SO3. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently SO3 - X + Substituted phenyl groups.

[0191] In some implementation schemes, R 1A R 1B R 1C R 1D R 1E and R 1F Each is a phenyl group, and none of them are substituted or converted to SO3. - X + Replacement, condition is R 1A R 1B R 1C R 1D R 1E and R 1F The four independent ones in the SO3 - X + Substituted phenyl groups.

[0192] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0193] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F It is a heteroaryl group on its own.

[0194] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Independently, they are heteroaryl groups, each unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-12 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0195] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F It is an aryl group on its own.

[0196] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-12 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0197] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Each is an aryl group, independently unsubstituted or composed of 1, 2, 3, 4, or 5 independently selected from C. 1-6 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0198] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F It is independently phenyl.

[0199] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Each is independently a phenyl group, and each is unsubstituted or composed of 1, 2, 3, 4, or 5 molecules independently selected from C1. 1-12 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0200] In some implementation schemes, R 3A R 3B R 3C R 3D R 3E and R 3F Each is independently a phenyl group, and each is unsubstituted or composed of 1, 2, 3, 4, or 5 molecules independently selected from C1. 1-6 Alkyl, halogen and phenyl substituents.

[0201] In some implementation schemes, R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted.

[0202] In some implementation schemes, R 1G and R 1H Independently aryl, wherein each aryl group is unsubstituted or surrounded by 1, 2, 3, 4 or 5 SO3 groups. - X + replace.

[0203] In some implementation schemes, R 1G and R 1H Independently, it is phenyl, wherein each phenyl group is unsubstituted or surrounded by 1, 2, 3, 4, or 5 SO3 groups. - X + replace.

[0204] In some implementation schemes, R 1G and R 1H H stands for H independently.

[0205] In some implementation schemes, R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution with alkyl, halogen, phenyl, nitro and cyano groups.

[0206] In some implementation schemes, R 3G and R 3H It is an aryl group on its own.

[0207] In some implementation schemes, R 3G and R 3H It is independently phenyl.

[0208] In some implementation schemes, R 3G and R 3H H stands for H independently.

[0209] In some embodiments, A1 is an arylene, heteroarylene, arylene, or heteroarylene that is unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro, cyano, aryl, and heteroaryl.

[0210] In some implementations, A1 is an aryl group.

[0211] In some embodiments, A1 is an arylene group that is either unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro groups, cyano groups, aryl groups, and heteroaryl groups.

[0212] In some implementations, A1 is phenylene.

[0213] In some embodiments, A1 is a phenylene group that is either unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro groups, cyano groups, aryl groups, and heteroaryl groups.

[0214] In some implementations, A1 is not present.

[0215] In some embodiments, B1 is an arylene, heteroarylene, arylene, or heteroarylene that is unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro, cyano, aryl, and heteroaryl.

[0216] In some implementations, B1 is an aryl group.

[0217] In some embodiments, B1 is an arylene group that is either unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro groups, cyano groups, aryl groups, and heteroaryl groups.

[0218] In some implementations, B1 is phenylene.

[0219] In some embodiments, B1 is a phenylene group that is either unsubstituted or substituted by one, two, three, or four substituents independently selected from halogens, nitro groups, cyano groups, aryl groups, and heteroaryl groups.

[0220] In some implementations, B1 is not present.

[0221] In some embodiments, A1 is a phenylene group that is unsubstituted or substituted by one, two, three or four substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl groups, and A2 is absent.

[0222] In some embodiments, B1 is a phenylene group that is unsubstituted or substituted by one, two, three or four substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl groups, and B2 is absent.

[0223] In some embodiments, A1 and B1 are independently arylene groups that are either unsubstituted or substituted by one, two, three, or four substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl groups, and A2 and B2 are absent.

[0224] In some embodiments, L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0225] In some implementations, L1 is the linker aryl group.

[0226] In some embodiments, L1 is a linking arylene group that is not substituted or is composed of 1, 2, 3, or 4 independently selected from C. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0227] In some implementations, L1 is a phenylene chain.

[0228] In some embodiments, L1 is a linked phenylene group that is unsubstituted or is selected independently by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0229] In some implementations, L1 is a linker for naphthylene.

[0230] In some embodiments, L1 is a linking naphthyl group that is unsubstituted or composed of 1, 2, 3, or 4 independently selected C1 groups. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0231] In some embodiments, L1 is phenylene or naphthylene. In some embodiments, L1 is phenylene or naphthylene, which is unsubstituted or is composed of 1, 2, 3, or 4 independently selected from C1. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0232] In some implementations, L1 is phenylene, provided that the phenylene is not para-phenylene.

[0233] In some embodiments, L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0234] In some implementations, L2 is not present.

[0235] In some implementations, L2 is the linker aryl group.

[0236] In some embodiments, L2 is a linking arylene group that is not substituted or is composed of 1, 2, 3, or 4 independently selected from C. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0237] In some implementations, L2 is a phenylene oxide.

[0238] In some embodiments, L2 is a linked phenylene group that is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0239] In some embodiments, L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0240] In some implementations, L3 is not present.

[0241] In some implementations, L3 is the linker aryl group.

[0242] In some embodiments, L3 is a linking arylene group that is not substituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0243] In some implementations, L3 is a phenylene chain.

[0244] In some embodiments, L3 is a linked phenylene group that is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0245] In some embodiments, K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0246] In some implementations, K1 is a linker aryl group.

[0247] In some embodiments, K1 is a linking arylene group that is not substituted or is composed of 1, 2, 3, or 4 independently selected from C. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0248] In some implementations, K1 is a phenylene chain.

[0249] In some embodiments, K1 is a linked phenylene group that is unsubstituted or is selected independently from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0250] In some implementations, K1 is a linker for naphthylene.

[0251] In some embodiments, K1 is a linking naphthyl group that is unsubstituted or composed of 1, 2, 3, or 4 independently selected C1 groups. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0252] In some embodiments, K1 is phenylene or naphthylene. In some embodiments, K1 is phenylene or naphthylene, which is unsubstituted or is composed of 1, 2, 3, or 4 independently selected from C1. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0253] In some implementations, K1 is phenylene, provided that the phenylene is not para-phenylene.

[0254] In some embodiments, K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0255] In some implementations, K2 is not present.

[0256] In some implementations, K2 is a linker for the aryl group.

[0257] In some embodiments, K2 is a linking arylene group that is not substituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0258] In some implementations, K2 is a phenylene oxide.

[0259] In some embodiments, K2 is a linked phenylene group that is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0260] In some embodiments, K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0261] In some implementations, K3 is not present.

[0262] In some implementations, K3 is a linker for the aryl group.

[0263] In some embodiments, K3 is a linking arylene group that is not substituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0264] In some implementations, K3 is a phenylene oxide.

[0265] In some embodiments, K3 is a linked phenylene group that is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0266] In some embodiments, L1 and K1 are independently naphthylene or phenylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene, wherein each phenylene group is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents.

[0267] In some embodiments, L1 and K1 are independently naphthylene or phenylene, provided that the phenylene is not p-phenylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene, wherein each phenylene is not substituted or is independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents.

[0268] In some implementations, the first repeating unit (x) of equation (I) is the repeating unit of equation (IA):

[0269]

[0270] in:

[0271] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0272] R 2A R 2B R 2C and R 2DIt can be independently H, halogen, nitro, cyano, aryl, or heteroaryl;

[0273] L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0274] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0275] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0276] In some implementation schemes, R 2A R 2B R 2C and R 2D Independently, it can be H or halogen. In some implementations, R 2A R 2B R 2C and R 2D For H.

[0277] In some implementations, the second repeating unit (y) of equation (II) is the repeating unit of equation (II-A):

[0278]

[0279] in:

[0280] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0281] R 4A R 4B R 4C and R 4D It can be independently H, halogen, nitro, cyano, aryl, or heteroaryl;

[0282] K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0283] K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0284] K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0285] In some implementations, R4 2A R 4B R 4C and R 4D Independently, it can be H or halogen. In some implementations, R 4A R 4B R 4C and R 4D For H.

[0286] In some embodiments, the copolymer has the structure of formula (III):

[0287]

[0288] in:

[0289] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1Eand R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0290] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0291] A1 and B1 are independently arylene, heteroarylene, arylene, or heteroarylene, each unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl;

[0292] A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0293] L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0294] L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0295] L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0296] X + It is a cation.

[0297] In some embodiments, the molar percentages of the first repeating unit (x) and the second repeating unit (y) of the formula (III) copolymer are as described herein.

[0298] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (III) copolymer is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0299] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (III) copolymer is about 85% to about 99%, and the molar percentage of the second repeating unit (y) is about 15% to about 1%.

[0300] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (III) copolymer is about 88% to about 92%, and the molar percentage of the second repeating unit (y) is about 12% to about 8%.

[0301] In some embodiments, the first repeating unit (x) of the copolymer of formula (III) has a molar percentage of about 75%, and the second repeating unit (y) has a molar percentage of about 25%.

[0302] In some embodiments, the first repeating unit (x) of the copolymer of formula (III) has a molar percentage of about 85%, and the second repeating unit (y) has a molar percentage of about 15%.

[0303] In some embodiments, the first repeating unit (x) of the copolymer of formula (III) has a molar percentage of about 90%, and the second repeating unit (y) has a molar percentage of about 10%.

[0304] In some embodiments, the copolymer has the structure of formula (IV):

[0305]

[0306] in:

[0307] R 1a R 1b R 1e and R 1f SO3 independently - X + Or hydrogen, provided that R 1a R 1b R 1e and R 1f At least two of them are SO3 - X + ;

[0308] R 3a R3b R 3e and R 3f Independently selected from hydrogen, C 1-12 Alkyl, halogen, phenyl, nitro, and cyano groups;

[0309] L1 and K1 are independently linked arylene groups, which are either unsubstituted or composed of 1, 2, 3, or 4 independently selected from C. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0310] L2, K2, L3, and K3 are independently absent or aryl, wherein each aryl group is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0311] In some embodiments, the molar percentages of the first repeating unit (x) and the second repeating unit (y) of the formula (IV) copolymer are as described herein.

[0312] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is from about 75% to about 99%, and the molar percentage of the second repeating unit (y) is from about 25% to about 1%.

[0313] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is about 85% to about 99%, and the molar percentage of the second repeating unit (y) is about 15% to about 1%.

[0314] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is about 88% to about 92%, and the molar percentage of the second repeating unit (y) is about 12% to about 8%.

[0315] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is about 75%, and the molar percentage of the second repeating unit (y) is about 25%.

[0316] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is about 85%, and the molar percentage of the second repeating unit (y) is about 15%.

[0317] In some embodiments, the molar percentage of the first repeating unit (x) of the formula (IV) copolymer is about 90%, and the molar percentage of the second repeating unit (y) is about 10%.

[0318] In some implementation schemes, X + Selected from H + Alkali metal ions (e.g., Na+)+ Li + and / or K + ), transition metal ions (e.g., Fe), 2+ Co 2+ Ni 2+ Pd 2+ Ir 2+ ) and [N(R 5A (R) 5B (R) 5C (R) 5D )] + The cation, wherein R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl.

[0319] In some implementation schemes, X + Selected from H + Alkali metal ions (e.g., Na+) + Li + and / or K + ) and [N(R 5A (R) 5B (R) 5C (R) 5D )] + The cation, wherein R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl.

[0320] In some implementation schemes, X + For H + .

[0321] In some implementation schemes, X + Alkali metal ions (e.g., Na+) + Li + and / or K + ).

[0322] In some implementation schemes, X + Transition metal ions (e.g., Fe) 2+ Co 2+ Ni 2+ Pd 2+ Ir 2+ ).

[0323] In some implementation schemes, X + For [N(R) 5A (R)5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl. In some embodiments, X + It is [N(R)] 5A (R) 5B (R) 5C (R) 5D )] + Its R 5A R 5B R 5C R 5D Independently H or C 1-6 Alkyl group. For example, X + It can be [NH(C)] 1-6 [alkyl)3] + In some implementations, X + [NH(ethyl)3] + .

[0324] In some embodiments, L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0325] In some embodiments, L1 is an unsubstituted heteroaryl group. In some embodiments, L1 is composed of 1, 2, 3, or 4 independently selected C14 groups. 1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0326] In some embodiments, L1 is an unsubstituted aryl group. In some embodiments, L1 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 The arylethemate is substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L1 is substituted with 1, 2, 3, or 4 groups independently selected from C1. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0327] In some embodiments, L1 is an unsubstituted phenylene oxide. In some embodiments, L1 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L1 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0328] In some implementations, L1 is a naphthylene group.

[0329] In some implementations, L1 is not p-phenylene.

[0330] In some embodiments, L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0331] In some implementations, L2 is not present.

[0332] In some embodiments, L2 is an unsubstituted heteroaryl group. In some embodiments, L2 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0333] In some embodiments, L2 is an unsubstituted aryl group. In some embodiments, L2 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 A arylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L2 is a group independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0334] In some embodiments, L2 is an unsubstituted phenylene oxide. In some embodiments, L2 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6 A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L2 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0335] In some embodiments, L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0336] In some implementations, L3 is not present.

[0337] In some embodiments, L3 is an unsubstituted heteroaryl group. In some embodiments, L3 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0338] In some embodiments, L3 is an unsubstituted aryl group. In some embodiments, L3 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 Aromaticyl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L3 is a group independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0339] In some embodiments, L3 is an unsubstituted phenylene oxide. In some embodiments, L3 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6 A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, L3 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0340] In some embodiments, K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0341] In some embodiments, K1 is an unsubstituted heteroaryl group. In some embodiments, K1 is composed of 1, 2, 3, or 4 independently selected C1 groups. 1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0342] In some embodiments, K1 is an unsubstituted aryl group. In some embodiments, K1 is composed of 1, 2, 3, or 4 independently selected C1 groups. 1-6 Aromatic groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K1 is a group independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0343] In some embodiments, K1 is an unsubstituted phenylene oxide. In some embodiments, K1 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K1 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0344] In some implementations, K1 is not p-phenylene.

[0345] In some embodiments, K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0346] In some implementations, K2 is not present.

[0347] In some embodiments, K2 is a heteroarylene. In some embodiments, K2 is unsubstituted or composed of 1, 2, 3, or 4 independently selected C. 1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0348] In some embodiments, K2 is an unsubstituted aryl group. In some embodiments, K2 is composed of 1, 2, 3, or 4 independently selected C... 1-6 Aromatic groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K2 is a group independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0349] In some embodiments, K2 is an unsubstituted phenylene oxide. In some embodiments, K2 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6 A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K2 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0350] In some embodiments, K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0351] In some implementations, K3 is not present.

[0352] In some embodiments, K3 is a heteroarylene. In some embodiments, K3 is unsubstituted or composed of 1, 2, 3, or 4 independently selected C3 groups.1-6 Heteroaryl groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0353] In some embodiments, K3 is an unsubstituted aryl group. In some embodiments, K3 is composed of 1, 2, 3, or 4 independently selected C64 groups. 1-6 Aromatic groups substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K3 is a group independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents substituted with aryl groups.

[0354] In some embodiments, K3 is an unsubstituted phenylene oxide. In some embodiments, K3 is a phenylene oxide selected independently by 1, 2, 3, or 4 C atoms. 1-6 A phenylene group substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In some embodiments, K3 is a phenylene group independently selected from C1, C2, C3, or C4. 1-6 Phenylidene substituted with alkyl or halogen substituents.

[0355] In some embodiments, L1 and K1 are independently aryl groups; L2 and K2 are independently absent or aryl groups; L3 and K3 are independently absent or aryl groups, wherein each aryl group is not substituted or is independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents.

[0356] In some embodiments, L1 and K1 are independently phenylene or naphthylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene, wherein each phenylene group is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents.

[0357] In some embodiments, L1 and K1 are independently phenylene or naphthylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene.

[0358] In some implementations, L3, L2, and L1 in –L3–L2–L1– and K3, K2, and K1 in –K3–K2–K1– are each independently selected from:

[0359] , , , , , , , , , , , , , , , , , , , , , , , , , , ,and .

[0360] In some implementations, the first repeating unit (x) is selected from:

[0361] , , , and any combination thereof.

[0362] In some implementations, the first repeating unit (x) is selected from:

[0363] , , , and any combination thereof.

[0364] In some implementations, the second repeating unit (y) is selected from:

[0365] , , , and any combination thereof.

[0366] In some implementations, the second repeating unit (y) is selected from:

[0367] , ,

[0368] , and any combination thereof,

[0369] In some implementations, the first repeating unit (x) is selected from:

[0370] , , , and any combination thereof, where X + For H + Alkali metal ions, transition metal ions, or [N(R5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl or heteroaryl; and

[0371] The second repeating unit (y) is selected from:

[0372] , , , and any combination thereof,

[0373] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0374] In some embodiments, the copolymers described herein are random copolymers having random distributions of (x) and (y).

[0375] In some embodiments, the copolymers described herein are statistical copolymers having average compositional ratios of (x) and (y).

[0376] In some embodiments, the copolymers described herein are linear.

[0377] In some embodiments, the copolymers described herein are branched.

[0378] As described herein, the branched copolymer comprises a multivalent linker M1 directly bonded to at least three repeating units via covalent bonds.

[0379] In some embodiments, linker M1 is covalently bonded directly to at least three repeating units (x) of sulfonated polyphenylene of formula (I). In some embodiments, linker M1 is covalently bonded directly to three repeating units (x) of sulfonated polyphenylene of formula (I). In some embodiments, linker M1 is covalently bonded directly to four repeating units (x) of sulfonated polyphenylene of formula (I). In some embodiments, linker M1 is covalently bonded directly to five repeating units (x) of sulfonated polyphenylene of formula (I). In some embodiments, linker M1 is covalently bonded directly to six repeating units (x) of sulfonated polyphenylene of formula (I). In some embodiments, linker M1 is covalently bonded directly to 3-6 repeating units (x) of sulfonated polyphenylene of formula (I).

[0380] In some embodiments, linker M1 is directly covalently bonded to at least three hydrophobic polyphenylene repeating units (y) of formula (II). In some embodiments, linker M1 is directly covalently bonded to three hydrophobic polyphenylene repeating units (y) of formula (II). In some embodiments, linker M1 is directly covalently bonded to four hydrophobic polyphenylene repeating units (y) of formula (II). In some embodiments, linker M1 is directly covalently bonded to five hydrophobic polyphenylene repeating units (y) of formula (II). In some embodiments, linker M1 is directly covalently bonded to six hydrophobic polyphenylene repeating units (y) of formula (II). In some embodiments, linker M1 is directly covalently bonded to 3-6 hydrophobic polyphenylene repeating units (y) of formula (II).

[0381] In some embodiments, the linker M1 is directly covalently bonded to at least three repeating units, the repeating units comprising a combination of sulfonated polyphenylene repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II).

[0382] In some embodiments, the linker M1 is directly covalently bonded to three repeating units, which include a combination of a sulfonated polyphenylene repeating unit (x) of formula (I) and a hydrophobic polyphenylene repeating unit (y) of formula (II). For example, M1 can be directly covalently bonded to one repeating unit (x) of formula (I) and two repeating units (y) of formula (II). In another example, M1 can be directly covalently bonded to two repeating units (x) of formula (I) and one repeating unit (y) of formula (II).

[0383] In some embodiments, the linker M1 is directly covalently bonded to four repeating units, which include a combination of sulfonated polyphenylene repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II). For example, M1 is directly covalently bonded to one repeating unit (x) of formula (I) and three repeating units (y) of formula (II). In another example, M1 is directly covalently bonded to two repeating units (x) of formula (I) and two repeating units (y) of formula (II). In yet another example, M1 is directly covalently bonded to three repeating units (x) of formula (I) and one repeating unit (y) of formula (II).

[0384] In some embodiments, the linker M1 is directly covalently bonded to five repeating units, which include combinations of sulfonated polyphenylene repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II). For example, in any possible combination of repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II), the linker M1 is directly covalently bonded to the five repeating units.

[0385] In some embodiments, the linker M1 is directly covalently bonded to six repeating units, which include combinations of sulfonated polyphenylene repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II). For example, in any possible combination of repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II), the linker M1 is directly covalently bonded to the six repeating units.

[0386] In some embodiments, the linker M1 is directly covalently bonded to 3-6 repeating units, which include combinations of sulfonated polyphenylene repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II). For example, in any possible combination of repeating units (x) of formula (I) and hydrophobic polyphenylene repeating units (y) of formula (II), the linker M1 is directly covalently bonded to 3-6 repeating units.

[0387] In some implementations, the multivalent linker M1 is selected from:

[0388] , , , , , and .

[0389] In some implementations, the multivalent linker M1 is .

[0390] As used herein, polyvalent refers to a trivalent moiety and higher valence moieties (e.g., tetravalent, pentavalent, hexavalent, etc.). For example, M1 can be a trivalent, tetravalent, pentavalent, or hexavalent linker. For example, a polyvalent linker M1 can be a carbon atom, a heteroatom (e.g., N, P, or B), a polyaryl group, a polyheteroaryl group, a polyaralkyl group, or a polyheteroaryl group, each of which is bonded to at least three repeating units; wherein the carbon atom, heteroatom (e.g., P), polyaryl group, polyheteroaryl group, polyaralkyl group, or polyheteroaryl group is not substituted or is composed of one, two, or three independently selected C atoms. 1-6The multivalent linker is substituted with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents. In some embodiments, the multivalent linker is selected from trivalent nitrogen and tetravalent carbon. In some embodiments, the multivalent linker is a trivalent phenyl. In some embodiments, the multivalent linker is a trivalent pyridyl. In some embodiments, the multivalent linker is a trivalent pyrazyl. In some embodiments, the multivalent linker is a tetravalent phenyl. In some embodiments, the multivalent linker is a tetravalent pyridyl. In some embodiments, the multivalent linker is a tetravalent pyrazyl. In some embodiments, the multivalent linker is a pentavalent phenyl. In some embodiments, the multivalent linker is a pentavalent pyridyl. In some embodiments, the multivalent linker is a hexavalent phenyl. In embodiments containing a trivalent phenyl or a trivalent pyridyl group, the trivalent phenyl and the trivalent pyridyl group are each unsubstituted or substituted by one, two, or three independently selected C1, C2, or C3 groups. 1-6 Substituents of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In embodiments comprising tetravalent phenyl, tetravalent pyridyl, or trivalent pyrazinyl groups, the tetravalent phenyl, tetravalent pyridyl, and trivalent pyrazinyl groups are either unsubstituted or substituted by one or two independently selected from C10. 1-6 Substituents of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups. In embodiments containing a pentavalent phenyl group, the pentavalent phenyl group is unsubstituted or selected from C10. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0391] According to scheme 6, a multivalent linker can be introduced into the polymer using a multifunctional aromatic system terminated by an alkyne or a protected alkyne, and then combined with a dienophilic monomer to generate branching points. The dienophilic monomer can be a mixture of anionic and hydrophobic uncharged monomers. The multifunctional aromatic system can be small, such as 1,3,5-triethynylbenzene, or large, having more than one aromatic group. The multifunctional aromatic system can include heteroaromatic rings, such as pyridine (as shown below) or pyrazine-containing linkers.

[0392]

[0393] In some implementations, the multifunctional aromatic system may include a central heteroatom, such as nitrogen or carbon, as shown below.

[0394]

[0395] In some implementations, the terminal acetylene group is replaced by H.

[0396] Other examples of multifunctional aromatic systems based on hexaphenylbenzene or pentaphenylbenzene compounds are shown below, which produce linkers with up to five or six functionalities.

[0397]

[0398] In some embodiments, the branched polymers of this disclosure can be prepared using monomers having three or more ketone moieties, such as compounds of formula (XI) as shown below:

[0399]

[0400] Where R 1A and R 1B As defined above, each occurrence is given, and the condition is R. 1A and R 1B At least one (e.g., at least two) of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently. - X + PO3 2- X + 2 and COO - X + The substituents of the aryl or heteroaryl groups, wherein X + As defined above. In some implementations, such as in a single-unit (y) having formula (II), R 1A and R 1B There is no such condition that makes the monomer of equation (XI) hydrophobic and uncharged.

[0401] The multifunctional linkers or monomers described herein can be used as one of the starting materials in the reaction mixture to provide branched polymers. The multifunctional linkers may be present in amounts from 0.001 to 20 mol percent relative to the compounds of formula (I) or (II).

[0402] In some embodiments, the copolymer has a branched structure of formula (V):

[0403]

[0404] P1 and P2 are independently selected from repeating units (x) of equation (I) and repeating units (y) of equation (II), and the repeating units (x) of equation (I) and repeating units (y) of equation (II) are as described herein.

[0405] In some implementations of equation (V), the ratio of z / (x+P1+P2) is less than 0.2.

[0406] In some embodiments, the copolymer is a random block copolymer, comprising:

[0407] The first segment selected from the first repeating unit (x):

[0408] , , , and any combination thereof; and

[0409] The second segment selected from the second repeating unit (y):

[0410] , , , and any combination thereof, wherein:

[0411] n is an integer from 3 to 100.

[0412] m is an integer from 3 to 100; and

[0413] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0414] This disclosure is characterized by a method for preparing a random copolymer comprising forming a mixture of a first repeating unit (x) of formula (VI) and a second repeating unit (y) of formula (VII):

[0415]

[0416] in:

[0417] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0418] R1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0419] A1 is arylene, heteroarylene, arylene, or heteroarylene, wherein the arylene, heteroarylene, arylene, or heteroarylene is unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl.

[0420] A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0421] L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0422] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0423] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0424] X + It is a cation; and

[0425] A is the reactive first terminal group.

[0426]

[0427] in

[0428] R 3A R 3B R 3C R 3D R3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0429] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, nitro, and cyano groups;

[0430] B1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, or heteroarylalkyl group is unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups.

[0431] B2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0432] K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1 by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0433] K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0434] K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0435] B is the second reactive terminal group configured to react with A, and

[0436] React A and B to provide a random copolymer of formula (III):

[0437]

[0438] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0439] This disclosure is characterized by a method for preparing a random copolymer comprising forming a mixture of a first repeating unit (x) of formula (VI) and a second repeating unit (y) of formula (VII):

[0440]

[0441] in:

[0442] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0443] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0444] A1 is arylene, heteroarylene, arylene, or heteroarylene, wherein the arylene, heteroarylene, arylene, or heteroarylene is unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl.

[0445] A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0446] L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0447] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0448] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0449] X + It is a cation; and

[0450] A is the reactive first terminal group.

[0451]

[0452] in

[0453] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0454] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6Substitution of alkyl, halogen, nitro, and cyano groups;

[0455] B1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, or heteroarylalkyl group is unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups.

[0456] B2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0457] K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1 by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0458] K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0459] K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0460] B is the second reactive terminal group configured to react with A, and

[0461] React A and B to provide a random copolymer of formula (III):

[0462]

[0463] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0464] The condition is that the repeating unit (x) in equation (I) is not:

[0465] .

[0466] The present disclosure is particularly characterized by compounds of formula (VII).

[0467]

[0468] in:

[0469] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3 or 4 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0470] A1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, and heteroarylalkyl groups are unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0471] A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0472] The present disclosure is particularly characterized by compounds of formula (VII).

[0473]

[0474] in:

[0475] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3 or 4 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3- X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0476] A1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, and heteroarylalkyl groups are unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0477] A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0478] In some implementations, the compound of formula (VII) is not

[0479] .

[0480] The compounds of formula (VII) described herein include compounds of formula (VII-A).

[0481]

[0482] in:

[0483] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X+ Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + Substituents of aryl or heteroaryl groups; and

[0484] R 2A R 2B R 2C and R 2D It is independently selected from H, halogen, nitro, cyano, aryl and heteroaryl.

[0485] The compounds of formula (VII) described herein include compounds of formula (VII-A).

[0486]

[0487] in:

[0488] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + Substituents of aryl or heteroaryl groups; and

[0489] R 2A R 2B R 2C and R 2D Independently selected from H, halogen, nitro, cyano, aryl, and heteroaryl.

[0490] The condition is that the compound of formula (VII-A) is not

[0491] .

[0492] This disclosure further describes methods for preparing any of the polymers disclosed herein, comprising forming a mixture of a compound of formula (VII) and at least one compound of formula (VIII).

[0493]

[0494] in

[0495] L1 is an unsubstituted or substituted linked heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatom, arylene, heteroarylene, arylene, and heteroarylene are unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0496] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0497] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0498] D1 and D2 are independently H and 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), wherein R 1G and R 1H As defined in this paper, and where R 3G and R 3H As defined in this article; and

[0499] The polymer described herein is provided by reacting a compound of formula (VII) or (VII-A) with at least one compound of formula (VIII) via the Diels Alder reaction.

[0500] In some embodiments, the method for preparing any of the above polymers includes reacting the compound of formula (VII) and the compound of formula (VIII) by a Diels Alder reaction, including heating the mixture to a temperature of 150°C to 300°C (e.g., 180°C to 230°C) for a duration of 5 minutes to 30 days (e.g., 60 minutes to 7 days). The method may further include deprotecting the compound of formula (VIII) before or during the Diels Alder reaction, when at least one of D1 and D2 is a protecting group.

[0501] In some embodiments, the mixture in the above method further comprises a compound of formula (IX):

[0502]

[0503] in

[0504] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Alkyl and halogen substituents;

[0505] B1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, and heteroarylalkyl groups are unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogens, nitro, cyano, aryl, and heteroaryl groups; and

[0506] B2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0507] In some embodiments, the mixture in the above method further includes a compound of formula (IX-A):

[0508]

[0509] in:

[0510] R 3A R 3B R 3C R 3D R3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl and halogen groups; and

[0511] R 4A R 4B R 4C and R 4D It is independently selected from H, halogen, nitro, cyano, aryl or heteroaryl.

[0512] This disclosure further describes, in particular, a method for preparing random block copolymers comprising forming a mixture of a first repeating unit (x) of formula (VI) and a second repeating unit (y) of formula (VII).

[0513]

[0514] Where R 1A R 1B R 1C R 1D R 1E R 1F R 1G R 1H A1, A2, L1, L2, and L3 are as defined in this paper.

[0515] n is an integer from 3 to 100, and

[0516] A is the reactive first terminal group;

[0517]

[0518] in

[0519] R 3A R 3B R 3C R 3D R 3E R 3F R 3G R 3H B1, B2, K1, K2, and K3 are as defined in this document.

[0520] m is an integer from 3 to 100, and

[0521] B is the second reactive terminal group configured to react with A, and

[0522] Reacting A (e.g., an alkyne (reacting with a tetracyclic ketone) or a tetracyclic ketone (reacting with an alkyne)) with B (e.g., a tetracyclic ketone or an alkyne) to provide a random block copolymer of formula (X):

[0523]

[0524] The molar percentage of the first repeating unit (x) of the first block is about 75% to about 99%, and the molar percentage of the second repeating unit (y) of the second block is about 25% to about 1%.

[0525] membrane

[0526] As disclosed herein, ionic copolymer films comprising ionic copolymers having repeating units of both hydrophilic and hydrophobic monomers exhibit reduced water absorption and swelling, compared to ionic polymer films containing only hydrophilic ionic monomers, or ionic copolymers having compositions outside the range of 75%–99% monomers (x) of formula (I) and 25%–1% monomers (y) of formula (II), and also exhibit minimal impact on proton conductivity and electrochemical performance. The reduced proton conductivity and electrochemical performance of molecular compositions exhibiting reduced water absorption and swelling are expected and previously observed to be proportionally reduced, with compositions containing 75%–99% monomers (x) of formula (I) and 25%–1% monomers (y) of formula (II) representing a contrasting property relationship.

[0527] The present disclosure is particularly characterized by films comprising any copolymers disclosed herein. The present disclosure is particularly characterized by ionomers comprising any copolymers disclosed herein.

[0528] In some embodiments, the copolymers disclosed herein are incorporated into a membrane to form an ionic copolymer membrane. In some embodiments, the ionic copolymer membrane comprises individual ionic copolymers formed by solvent casting or another method. In some embodiments, the ionic copolymer membrane comprises multiple ionic copolymers (e.g., ionic copolymers of different compositions) formed by solvent casting or another method. In some embodiments, the ionic copolymer membrane is an ionic binder. In some embodiments, the ionic copolymer membrane is a substrate. In some embodiments, the ionic copolymer membrane is a mechanical reinforcement. In some embodiments, the ionic copolymer membrane is a combination of the foregoing.

[0529] In some embodiments, ionic adhesives are bonded directly or indirectly to the substrate via physical contact and / or interconnection, covalent bonding, ionic bonding, hydrogen bonding, van der Waals forces, and / or metallic bonding. In some embodiments, ionic adhesives are bonded directly or indirectly to the mechanical reinforcement via physical contact and / or interconnection, covalent bonding, ionic bonding, hydrogen bonding, van der Waals forces, and / or metallic bonding.

[0530] Mechanical reinforcements or substrates may include porous polymer materials. Porous polymer materials can be any polymer material containing pores. Porous polymer materials can be, for example, linear sulfonated phenylenediamine poly(phenylene) ionomers, such as linear sulfonated phenylenediamine poly(phenylene)biphenyl (sPPB-H). + Ionic polymers, ionic copolymers disclosed herein, expanded polyethylene (ePE), and / or expanded polytetrafluoroethylene (ePTFE).

[0531] Ionic adhesives may contain ionic copolymers as described herein, such as ionic copolymers of formula (III) or formula (IV). The ionic copolymers of ionic adhesives may contain solids in amounts of about 0.5 wt% to about 99 wt%, about 0.5 wt% to about 50 wt%, about 0.5 wt% to about 25 wt%, or about 0.5 wt% to about 15 wt%.

[0532] In some embodiments, the ionic copolymer membrane further includes a catalyst layer. The catalyst layer may be applied to the ionic copolymer membrane to form a catalyst-coated ionic copolymer membrane, wherein the catalyst layer is in contact with the ionic copolymer membrane, an ionic binder of the ionic copolymer membrane, or a mechanical reinforcement of the ionic copolymer membrane.

[0533] In some embodiments, the catalyst layer comprises a combination of a catalyst (e.g., Pt / C, PtCo / C, MNC catalyst) and an ionic copolymer. In some embodiments, the catalyst layer also includes additives.

[0534] In some embodiments, the catalyst layer is formed of catalyst ink. In some embodiments, the catalyst layer is formed of a catalyst ink formulation comprising the ionic copolymers disclosed herein and a catalyst (e.g., Pt / C, PtCo / C, MNC catalyst).

[0535] In some embodiments, the catalyst in the catalyst slurry formulation comprises platinum (i.e., Pt / C) on a carbon support of various Pt particle sizes, and a combination of carbon materials of various surface areas and sizes. In some embodiments, the catalyst in the catalyst slurry formulation comprises Pt alloys (e.g., PtCo / C) on a carbon support of various noble metal alloy particle sizes and alloy ratios, and a combination of carbon materials of various surface areas and sizes. In some embodiments, the catalyst in the catalyst slurry formulation comprises an MNC catalyst, wherein the MNC catalyst incorporates non-noble metal ions (e.g., where M is iron or cobalt) within a nitrogen-doped carbon support.

[0536] As used herein, the weight % of Pt / C catalyst refers to the total amount of solid Pt / C used, including both Pt and carbon. For example, regardless of whether the Pt / C is 40 wt% Pt and 60 wt% carbon, or any different relative composition, the weight % of Pt / C remains the same with respect to the total mass used.

[0537] In some embodiments, the amount of catalyst used is from about 0.1 wt% to about 2.0 wt%, based on the solids content. In some embodiments, the amount of catalyst used is from about 0.1 wt% to about 25 wt% of catalyst (e.g., Pt / C, PtCo / C, and MNC catalysts) relative to the catalyst slurry solvent volume.

[0538] In some embodiments, the catalyst slurry composition comprises about 1% to about 30% by weight of an ionic copolymer and about 70% to about 99% by weight of a supported catalyst. In some embodiments, the catalyst slurry composition comprises about 10% to about 30% by weight of an ionic copolymer and about 70% to about 90% by weight of a supported catalyst.

[0539] In some embodiments, the catalyst layer comprises about 1% to about 30% by weight of an ionic polymer and about 70% to about 99% by weight of a supported catalyst or solid content.

[0540] In some embodiments, the ionic copolymers described herein are incorporated into a catalyst layer of a fuel cell, electrolyzer, or other electrochemical device. The fuel cell, electrolyzer, or other electrochemical device may include a catalyst layer comprising the ionic copolymers described herein.

[0541] For example, in some embodiments, the copolymer is incorporated into the catalyst layer of a fuel cell, electrolyzer, or other electrochemical device in amounts of about 5% to about 45% by weight solids, about 10% to about 45% by weight, about 15% to about 45% by weight, about 30% to about 45% by weight, about 5% to about 30% by weight, about 15% to about 45% by weight, about 30% to about 45% by weight, about 10% to about 30% by weight, about 10% to about 20% by weight, or about 15% to about 30% by weight.

[0542] Ionopolymer membranes can have a top surface and a bottom surface, such as a top surface and a bottom surface existing in the form of a sheet, including rolled, folded or otherwise twisted sheets.

[0543] In some implementations, the catalyst layer is in contact with only the top surface of the ionic polymer membrane, only the bottom surface of the ionic polymer membrane, or both the top and bottom surfaces of the ionic polymer membrane.

[0544] A bilayer is formed when the catalyst layer is in contact only with the top surface or only with the bottom surface of the ionomer membrane. The bilayer can be used as a bilayer membrane electrode assembly.

[0545] When the catalyst layer is in contact with both the top and bottom surfaces of the ionotropic polymer membrane, a three-layer structure is formed. This three-layer structure can be used as a three-layer membrane electrode assembly.

[0546] The catalyst-coated ionic copolymer film can be in planar form, such as a sheet. The sheet can be planar, rolled up, folded, or twisted in another way. For example, the catalyst-coated ionic copolymer film can be a sheet rolled up to form a roll, which can have dimensions such as 30 cm wide, 1 to 1000 meters long, or 10 to 100 meters long.

[0547] In one embodiment, the catalyst layer of the catalyst-coated ionic copolymer membrane acts as either an anode or a cathode. When only one surface of the ionic copolymer membrane is in contact with the catalyst layer, the catalyst layer is either an anode or a cathode. When both surfaces of the ionic copolymer membrane are in contact with the catalyst layer, one catalyst layer is an anode and the other is a cathode.

[0548] Typically, the anode is the electrode where oxidation occurs during an electrochemical reaction. The cathode is the electrode where reduction occurs during an electrochemical reaction.

[0549] Whether a catalyst layer is the anode or cathode can be determined by the orientation of the catalyst layer in a product such as a fuel cell. The orientation of the catalyst layer and the amount of catalyst present in the fuel cell can be combined to determine whether it is the anode or cathode. In a fuel cell, the anode is where fuel such as hydrogen (H2) is oxidized, releasing electrons and protons (H+). + The electrodes are then used to conduct useful work through an external circuit, while protons (H) are attracted to the electrodes. + The oxygen (O2) migrates to the cathode via the electrolyte. In a fuel cell, the cathode is where oxygen (O2) is reduced and reacts with protons (H+) from the electrolyte. + The electrodes combine to form water (H2O).

[0550] In an electrolytic cell, the anode is where water (H2O) is oxidized through an electrochemical reaction to produce oxygen (O2) and protons (H+). + ) and electrons (e - ) electrodes.

[0551] In an electrolytic cell, the cathode is where protons (H) are emitted. +An electrode that is reduced via an electrochemical reaction to produce hydrogen (H2).

[0552] In some embodiments, when measured using electrochemical impedance spectroscopy (EIS), at temperatures of about 20°C to about 90°C or about 50°C to about 90°C, the ionic copolymer film exhibits a temperature of approximately 0.001 mS / cm at a relative humidity of 30% to 100%. -1 Approximately 1000 mS cm -1 Approximately 0.001 mS cm -1 Approximately 750 mS cm -1 Approximately 0.001 mS cm -1 Approximately 450 mS cm -1 Approximately 1 mS cm -1 Approximately 1000 mS cm -1 Greater than approximately 0.001 mS cm -1 Greater than approximately 1 mS cm -1 or less than approximately 1000 mS cm -1 The proton conductivity (e.g., in-situ conductivity, in-plane conductivity). When measured using AC impedance spectroscopy (electrochemical impedance spectroscopy), in water at approximately 80 °C, the ionotropic polymer membrane can exhibit approximately 1 mS / cm. -1 Approximately 1000 mS cm -1 Or approximately 50 mS cm -1 Approximately 450 mS cm -1 The proton conductivity (e.g., non-in-situ conductivity, in-plane conductivity).

[0553] In some embodiments, the ionic copolymer film described herein has a density of about 2.4 to about 3.5 meq g. -1 The ion exchange capacity (IEC). In some embodiments, the ion-exchange capacity of the ion-exchange copolymer membrane described herein is approximately 2.4 to approximately 2.9 meq g when evaluated by acid-base titration. -1 The ion exchange capacity (IEC). For example, the acidic or protonated form (e.g., -SO3) of the copolymer can be evaluated by immersing the sample in a 1 M NaCl solution at pH 7 for 48 hours, followed by titrating the resulting acidic solution to pH 7 using a standard titrant (e.g., 0.01 M NaOH solution). - H + ) and conjugate sodium base counterparts (e.g., -SO3) - Na +The cation exchange of the sample. The IEC can be calculated using the volume and molar concentration of the titrant used and the dry mass of the sample being titrated. Those skilled in the art will understand that titration can also be performed with other bases (e.g., KOH solution) and can be achieved, for example, by exposing the sodium sulfonate to, for example, KCl to result in complete or partial potassium salt (e.g., -SO3). - K + They form counterions to cations.

[0554] In some embodiments, when exposed to Fenton's reagent at 80°C and 1 atm for a duration greater than 0 to 180 minutes, or for a duration greater than 0 to 90 minutes, or for a duration greater than 0 to 60 minutes, the ionic copolymer films described herein exhibit a mass loss of less than about 20% or less than about 10%.

[0555] In some embodiments, the ionic copolymer membranes described herein exhibit 60-120% by weight water absorption at room temperature.

[0556] In some embodiments, the copolymers of this disclosure are incorporated into a cation exchange resin.

[0557] In some embodiments, the copolymers disclosed herein or ionomer membranes containing copolymers are used in electrochemical devices, wherein the electrochemical devices are fuel cells, electrolyzers, hydrogen pumps, thermoelectrochemical hydrogen pumps, electrochemical hydrogen compressors, redox flow batteries or other electrochemical devices. Example

[0558] Example 1

[0559] Properties of copolymer films

[0560] Four different ionic polymers with varying acid functionalizations were prepared via Diels-Alder polymerization: 100% functionalized sulfonated polystyrene (“100%-sPP”), a copolymer comprising 90% functionalized sulfonated polystyrene and 10% non-sulfonated polystyrene (“90%-sPP”), a copolymer comprising 80% functionalized sulfonated polystyrene and 20% non-sulfonated polystyrene (“80%-sPP”), and a copolymer comprising 70% functionalized sulfonated polystyrene and 30% non-sulfonated polystyrene (“70%-sPP”). Films of each ionic polymer were formed using a solvent casting method, and the ion exchange capacity (IEC), mechanical properties, water absorption, dimensional stability, and proton conductivity of each film were evaluated.

[0561] The properties of the unreinforced ex-situ membrane were measured under both room temperature (22±1℃) and thermal conditions (80℃), under dry (drying at 80℃ for at least 2 hours), ambient (equilibration under environmental laboratory conditions for at least 2 hours), and / or humid (immersion in deionized water for at least 30 minutes) conditions, as shown. Water absorption samples were cut to specific dimensions (MD 5cm × TD 4cm) using a die-cutting machine. The testing procedure followed ASTM standard D570. Water absorption is expressed as a percentage increase in weight during immersion, calculated to an accuracy of 0.01% according to Formula 1, where W... w It is the weight of the hydration film, W d It is the weight of the dry film.

[0562]

[0563] The dimensional change relative to the dry state is given by Equation 2, where S x,y,z This refers to the dimensional changes in machine orientation, lateral direction, and film thickness. (D) w These are the specific dimensions after immersion (MD and TD are generally measured in cm, and thickness in μm), D d These are the specific dimensions in the dry state.

[0564]

[0565] Mass is measured using an analytical balance with a reading accuracy of at least 0.1 mg. Thickness (defined in the z-direction) is measured using a precision micrometer with a resolution of ± 1 µm, while width and length (in the x and y directions) are measured using a ruler with an accuracy of 0.5 mm or, alternatively, using a digital flatbed scanner and image analysis software (ImageJ or equivalent).

[0566] Using an impedance / gain phase analyzer (Solartron SI 1260 or equivalent), on a fully hydrated membrane immersed in liquid water, or under specific temperature and relative humidity controlled by suitable equipment (typically an environmental chamber), the impedance / gain phase was measured at 10... 7 -10 4 An AC potential scan was applied over a range of Hz, and the ionic resistance of the film in the in-plane direction was measured using a two-point probe. The analyzer recorded the electrochemical impedance, which could be input into a simplified Randle equivalent circuit. The ionic conductivity was calculated using Equation 3, where σ is the ionic conductivity (in Ω). -1 ∙cm -1 (l is the distance between probes in cm), and A is the cross-sectional area of ​​the membrane in cm². 2 R is the film resistance determined by fitting it to a standard Randle circuit model.

[0567]

[0568] Using a dual-probe configuration, the ionic resistance of the membrane in the transplanar direction was measured with an amplitude of 100 mV over a frequency range of 10 MHz to 100 Hz. The electrode area was 5 x 5 mm. The membrane resistance was obtained by fitting the electrochemical impedance to a suitable simplified equivalent circuit. Figure 1 The conductivity is calculated using formula (3), where σ is the calculated conductivity of the membrane, l is the thickness of the test membrane, R is the measured membrane resistance, and A is the active area.

[0569] Mechanical properties are measured using material samples cut by a roll die via a tensile stress-strain pull-out test. Tensile stress is defined as the ratio between the applied load (elongation) and a given cross-sectional area. The formula for tensile stress (σ, Equation 4) is the applied load (in Newtons) divided by the original cross-sectional area (A) of the sample. Tensile strain (represented by ϵ in Equation 5) is the change in length during stretching divided by the original length, and is generally expressed as a percentage of elongation. The mechanical properties of the material are characterized by plotting a curve of tensile stress versus strain. The slope of the elastic region is the elastic (or Young's) modulus, calculated according to Equation 6.

[0570]

[0571]

[0572]

[0573] Ion exchange capacity was measured by titration. A sample of the ion-exchange polymer membrane (3 x 3 cm) in its natural acidic form was immersed in 1 M NaCl solution for 24 hours. The resulting acidic solution was titrated with 0.01 M NaOH solution using phenolphthalein (1% by weight in ethanol) as an indicator. At least three replicates were performed to obtain the standard deviation. IEC was calculated according to Formula 7 below, where V NaOH Equal to the volume at the titration endpoint, M NaOH W is the concentration of the NaOH solution. 干燥 It refers to the quality of the dry film.

[0574]

[0575] The properties of unreinforced films formed from four acid-functionalized ionic polymers, 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP, are summarized in Table 1 below.

[0576] Table 1. Summary of the properties of unreinforced membranes of 100%-sPP, 90%-sPP, 80%-sPP and 70%-sPP.

[0577]

[0578] Membranes containing copolymers of sulfonated and non-sulfonated polystyrene (e.g., 90%-sPP, 80%-sPP, and 70%-sPP) exhibit significantly reduced hydrophilicity compared to membranes containing sulfonated polymers but lacking any hydrophobic monomers (e.g., 100%-sPP). This results in improved dimensional stability and reduced water absorption. However, electrochemical properties, specifically out-of-situ proton conductivity, are reduced. For example, at room temperature, 80%-sPP membranes exhibit a 28.3% reduction in proton conductivity, a 52.0% reduction in volume swelling, and a 28.1% reduction in water absorption compared to 100%-sPP.

[0579] In contrast, compared to 100%-sPP membranes, 90%-sPP membranes exhibited an average decrease of only 11.0% in proton conductivity, while water absorption and volume swelling decreased by 43.5% by weight and 43.0% by volume, respectively. This indicates that the decrease in proton conductivity is a more favorable and significantly disproportionate trade-off relative to the decrease in water absorption parameters, and deviates from the expected linear relationship.

[0580] These findings were further confirmed by cyclic swelling / deswelling tests, in which membranes of each polymer were repeatedly immersed in water at 80°C for 4 hours to swell, and changes in their dimensions (thickness and membrane area) and water absorption were measured, followed by drying in an oven at 80°C for 4 hours to deswell (Figure 2). Data are provided in Figure 3. Compared to any copolymer of sulfonated and non-sulfonated polystyrene disclosed herein, the sulfonated polystyrene (100%-sPP) membranes showed a thickness (SL) increase in each swelling / deswelling cycle. z Up to 165%), length (S) x Up to 64% of length), width (S) y Large variations in thickness swelling (up to 57% width) and water absorption (up to 475% by weight) indicate measurable dimensional instability. In contrast, 90%-sPP membranes show a reduction of nearly 50% in thickness swelling (i.e., S... z Up to 92%), and the length and width swelling decreased by approximately 40% (i.e., S). x and S y Up to 40% and 37% respectively) and water absorption reduced by 47% (i.e., up to 250% by weight). 80%-sPP and 70%-sPP membranes exhibited membrane water absorption (175% and 120% by weight, respectively) and dimensional swelling (S... z Up to 83%, S x Up to 28%, S y Up to 29.5%, and S z Up to 79%, S x Up to 14%, S yThe decline was further gradual (up to 16.5%), but the magnitude of the decline was smaller compared to the step change from 100%-sPP to 90%-sPP.

[0581] Example 2

[0582] Enhance membrane properties

[0583] The properties of the reinforced (composite) in-situ membranes were evaluated using the methods described above. As observed in the case of the unreinforced membrane, the overall water absorption and swelling behavior (Figures 4 and 5) of the reinforced membrane, composed of a copolymer of 90% functionalized sulfonated polystyrene and non-sulfonated polystyrene, was significantly reduced compared to the membrane containing 100% functionalized sulfonated polystyrene (100%-sPP), although the swelling behavior was mainly observed in the thickness (z) direction. This is due to the reinforcing and mitigating effects of the mechanical reinforcing materials used in both. For example, at room temperature (22 ± 2 °C), the 90%-sPP reinforced membrane exhibited 109.7 ± 18.6 wt% water absorption and 127.6 ± 11.2% thickness swelling, while the 100%-sPP reinforced membrane exhibited 139.7 ± 6.5 wt% water absorption and 149.9 ± 4.7% thickness swelling. Similarly, at 80 °C, the 90%-sPP reinforced membrane exhibited 156.9 ± 18.9 wt% water absorption and 170.8 ± 11.6% thickness swelling, while the 100%-sPP reinforced membrane exhibited 217.6 ± 7.1 wt% water absorption and 225.1 ± 3.9% thickness swelling. Therefore, compared to the 100%-sPP reinforced membrane, the 90%-sPP reinforced membrane showed significantly lower water absorption (21.5% and 27.9%, respectively) and thickness swelling (14.8% and 24.1%, respectively) at both room temperature and 80 °C. However, although the acid functionalization in 90%-sPP is reduced compared to 100%-sPP, and therefore the electrochemical performance is expected to be lower, no statistically significant differences were found in either the in-plane conductivity (90%-sPP = 122±7 mS / cm, 100%-sPP = 113±7 mS / cm) or the trans-plane conductivity (90%-sPP = 114±9 mS / cm, 100%-sPP = 129±11 mS / cm) for the evaluated composite membranes. Figure 6 ).

[0584] As observed in the unreinforced membrane analogue described in Example 1, the water absorption and swelling data were further confirmed by cyclic swelling / deswelling tests. Mechanically reinforced membranes of 100%-sPP and 90%-sPP were subjected to the swelling / deswelling tests outlined in Figure 2, and the data showed that… Figure 7Significant differences were observed between the 100%-sPP ionic polymer and the 90%-sPP ionic copolymer, with the 90%-sPP copolymer exhibiting significantly reduced thickness swelling and improved dimensional stability during the experiments. For example, during the experiments, 100%-sPP showed a maximum thickness swelling of 324% (S0.05). z ), while 90%-sPP exhibited a maximum thickness swelling of 248% (S z During the experiment, the difference in thickness swelling between 100%-sPP and 90%-sPP was 23.6 ± 7.9%. That is, at any given point during the experiment, the thickness swelling of 100%-sPP was approximately 1.25 times that of 90%-sPP. This further highlights the unexpected and emerging property of the functionalization reduction in the 90% sulfonated polyphenylene and 10% non-sulfonated polyphenylene copolymer (90%-sPP).

[0585] Example 3

[0586] Non-enhanced in-situ membrane properties

[0587] As described below, the properties of the unreinforced in-situ membrane were evaluated through fuel cell testing according to a standardized protocol. A catalyst slurry was prepared using Pt / C catalyst powder (TKK TEC-10e40e, 36.9 wt% Pt on graphitized carbon), a 2:1 IPA:H2O solvent, and an ionomer solution (Nafion D520). The final catalyst slurry mixture contained 1 wt% solids in a 2:1 IPA:H2O solution (0.70 wt% Pt / C catalyst powder and 0.30 wt% ionomer). A 5 cm⁻¹ membrane was then prepared on a specific membrane using ultrasonic spraying (Sono-Tek ExactaCoat SC). 2 The catalyst-coated film covers the electrode area, with a target Pt loading of 0.4 mg cm⁻¹ at each of the cathode and anode. -2 The catalyst-coated membrane was integrated into the fuel cell hardware using a commercial gas diffusion layer with a microporous layer (Freudenberg H14C15) and polyimide gaskets (100 μm in total). Testing was conducted using TP5eV2 hardware from Tandem Technologies, utilizing a bladder pressure system optimized for 160 psi compression. Compression was determined by monitoring the areal resistivity as a function of compression until no further decrease was measured. A Teledyne Medusa RD, 890CL fuel cell test station (Scribner Assoc. Inc.) was used for in-situ fuel cell characterization.

[0588] After assembling the fuel cell, the humidifier and battery temperature were set to 80°C, and nitrogen purging was performed for 5 minutes. The gas feed was then switched to H2 / air at a flow rate of 0.25 / 0.5 SLPM, and both gases were pressurized to 150 kPa. g The battery open-circuit voltage (OCV) was monitored, and once stable, the current was slowly increased in increments of 5 mA / s until a potential of 0.65 V was reached. Subsequently, 30 cycles of 0.6 V, 0.3 V, and 0.05 A (1 minute per cycle, totaling 1.5 hours) were performed for battery activation. The battery was maintained at 80°C and 150 kPa. g Polarization data were measured under pure H2 / air (0.25 / 0.5 slpm flow rate) at back pressure, and at relative humidity (RH) of 100 / 100%, 100 / 30%, or 30 / 30% (anode|cathode), as shown, with the cell ramped up from 0 A to 15 A at rates of 3 min / pt and 1 pt / step. In each case, the average current over three minutes was recorded.

[0589] Electrochemical measurements were performed using a VersaStat potentiostat, with the battery and humidifier maintained at 80 °C (100 / 100% RH) and each input gas (H2 / N2, anode | cathode) at 0.5 SLPM and 150 kPa. g Operation. Once the battery potential stabilizes below 0.150 V, linear sweep voltammetry measurements are performed. Voltage scans from 0.1 to 0.6 V are performed at a scan rate of 0.005 V / s to ensure there are no short circuits in the battery. The hydrogen permeation current of the battery is measured using chronoamperometry by increasing the voltage to 0.1 to 0.6 V, holding for 60 seconds at each step except for an extended 120-second hold at 0.5 V. The average current recorded during the final 60-second hold at 0.5 V is used as the final hydrogen permeation current. The current density is obtained by dividing by the active area of ​​the battery, with the result in mA / cm². 2 .

[0590] The evaluated performance of specific membrane electrode assemblies (MEAs) including the aforementioned gas diffusion layer, microporous layer, and electrode configuration, but with different membranes, was measured at maximum power density (mW / cm²). 2 ) and area resistivity (mΩ / cm 2 Report in ) format. Membranes of 100%-sPP (44.0 μm), 90%-sPP (45.5 μm), 80%-sPP (39.5 μm), and 70%-sPP (45.0 μm) were compared with Nafion membranes. ®The XL baseline reference was used for comparison. Performance (IV) curves are shown in Figure 8. Two different gas diffusion layers (GDLs), H15C14 (11% compression) and AvCarb 3250 (29% compression), were used in the polymer series and Nafion, respectively. ® XL.

[0591] When with Nafion ® Compared to XL, the hydrocarbon ion copolymer films exhibit slightly greater losses in the activation region of their respective polarization curves, but show comparable or lower losses in the ohmic and mass transport regions (see Table 2). The IR-drop method was used at 1.6 A / cm. 2 100%-sPP, 90%-sPP, 80%-sPP and 70%-sPP measured in the ohmic region and Nafion ® The areal resistivity of XL is 79.66, 52.26, 63.82, 52.97 and 51.64 mOhm / cm², respectively. 2 (Offset R not removed). The 80%-sPP film exhibits a higher areal resistivity but also demonstrates comparable performance. Measurements were taken of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP films, as well as Nafion. ® The gas permeation currents of XL were 0.76, 1.07, 1.06, 1.49, and 4.27 mA / cm², respectively. 2 Therefore, compared to the PFSA baseline, the hydrocarbon membrane reliably showed a reduction of approximately 3–4 times in gas permeation. (100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP, as well as Nafion...) ® The maximum power densities of XL under complete humidification are 1.33, 1.68, 1.64, 1.61, and 1.64 W / cm³, respectively. 2 These measurements were performed using a PFSA-optimized cell configuration, which included fully PFSA-compatible electrodes and highly PFSA-optimized catalyst and ionomer loading. See Table 2 for the data.

[0592] Table 2. Summary of MEA composition and fuel cell test conditions (H2 / oxygen).

[0593]

[0594] According to Figure 9, when there is a moderate back pressure (150 kPa) g When evaluated under H2 / air conditions, 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP films showed greater losses in the activation and ohmic regions of the polarization curves. However, when the current density exceeded 2 A / cm², the losses decreased.2 At that time, Nafion ® XL showed greater losses in the mass transfer polarization region (see Table 3). Generally, 90%-sPP performed better than 100%-sPP, 80%-sPP, and 70%-sPP in the mass transfer region, likely due to the membrane's water transport and self-humidification, as well as its higher proton conductivity. However, the IR resistance of the equal-thickness films across the ohmic region was very similar, but increased in the mass transfer region, indicating good current flow and avoiding the generation of excessive water that could flood the electrodes. 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion ® The areal resistivity of XL is also similar: 71.31, 51.75, 63.82, 51.24 and 50.41 mOhm / cm, respectively. 2 (Offset R not removed). 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion ® The maximum power densities of XL are 988, 1013, 968, 882 and 966 mW / cm³, respectively. 2 All the above data are listed in Table 3.

[0595] Table 3. Summary of MEA composition and fuel cell test conditions (H2 / air, 150 kPa) g ).

[0596]

[0597] When the battery back pressure is 150 kPa g (21.75 psi) increased to 300 kPa g At 43.51 psi, the increased water production in the cathode appeared to better wet all the ionotropic polymer membranes, resulting in lower losses in the mass transfer polarization region and thus higher performance (see Figure 10). Furthermore, compared to Nafion… ® Compared to XL, 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP showed greater activation polarization loss but lower ohmic polarization loss. 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP and Nafion... ® XL at 300 kPa g The resistivity of the area (74.4, 50.4, 61.8, 50.8 and 49 mOhm / cm) was measured. 2 (Without removing offset R) slightly below 150 kPa gThe area resistivity of H2 / air. The maximum power densities of 100%-sPP, 90%-sPP, 80%-sPP, and 70%-sPP are 1.05, 1.16, 1.07, and 1.10 W / cm², respectively. 2 , and at 150 kPa g Compared to the same membrane evaluated under back pressure, these showed increases of 6.16%, 13.46%, 9.71%, and 13.1%, respectively. In contrast, Nafion... ® XL exhibited a 1.65% performance degradation, measured at 0.95 W / cm² under the same conditions. 2 Generally, the performance of ionomer membrane series under all conditions follows the order 90%-sPP > 100%-sPP = 80%-sPP > 70%-sPP. The superior performance of 90%-sPP and the subsequent equivalence between 100%-sPP and 80%-sPP are unexpected and represent significant differences in material properties within 90%-sPP copolymers.

[0598] Finally, as shown in Figure 11, at 80℃, 30% RH, and 150 kPa... g Ionic copolymer films were evaluated under H2 / air conditions. As relative humidity decreased, the performance of copolymers of all ionic and hydrophobic monomers deteriorated, while IR resistance increased. All ionic copolymer films exhibited greater losses in the ohmic region of their respective polarization curves, and generally measured losses were lower than Nafion due to their high areal resistivity. ® XL. The 90%-sPP membrane again exhibited different power densities, in the order of 90%-sPP > 80%-sPP > 70%-sPP. 90%-sPP > 80%-sPP > 70%-sPP and Nafion ® The areal resistivity of XL is 154, 243, 188 and 95 mOhm / cm², respectively. 2 (Without removing offset R), the maximum power densities were measured to be 584, 444, 478, and 934 mW / cm², respectively. 2 Compared to those obtained at 100% relative humidity, these values ​​show a performance degradation of 53.8%, 74.2%, and 59.5%, respectively.

[0599] For 100%-sPP unreinforced membranes, consistent mechanical failure is observed below 50% RH under the conditions used in standard fuel cell testing (e.g., high stoichiometry), making it impossible to achieve the same results at 80°C, 30% RH, and 150 kPa. gData were generated under H2 / air conditions. In addition to the failure observed in 100%-sPP, the generated data further highlight the significant differences in material properties of the ionomer films.

[0600] Example 4

[0601] Enhanced in-situ membrane properties

[0602] As described in Example 3 above, the enhanced in-situ membrane properties are evaluated by performing fuel cell testing according to a standardized protocol. The performance of specific membrane electrode assemblies (MEAs) evaluated includes the same gas diffusion layer, microporous layer, and electrode configuration, but with different membranes, at maximum power density (mW / cm²). 2 ) and area resistivity (mΩ / cm 2 Report in the form of ).

[0603] In all cases, no statistically significant performance difference was observed between MEAs reinforced with 100% functionalized sulfonated polystyrene (100%-sPP, n=8) and MEAs reinforced with a copolymer of 90% functionalized sulfonated polystyrene and non-sulfonated polystyrene (90%-sPP, n=9), despite a 10% reduction in acid functionalization. Figure 12 and 13 ).

[0604] Example 5

[0605] Synthesis and properties of ionic copolymers

[0606] Ionic copolymers of sPP were prepared at a scale of 3 g. After a preliminary evaluation of polymer solubility and film properties, each copolymer was scaled up to 20 g (monomer). Scale-up synthesis was expected to yield 12–14 g of each ionic copolymer. However, the yield of 70%-sPP was significantly lower than expected due to its limited solubility in polar solvents (Table 1). The viscosity of the resulting ionic copolymers decreased with increasing hydrophobic monomer content. The viscosity of the resulting ionic copolymers was also correlated with polymer molecular weight. This result indicates that decreasing molecular weight leads to decreased polymer solubility during polymerization and ion exchange.

[0607] Table 4. Summary of yield and viscosity properties of ionic copolymers.

[0608]

[0609] Example 6

[0610] Synthesis of ionic monomer units

[0611] In some embodiments, the polystyrene precursor compound of this disclosure can be prepared according to Scheme 1.

[0612] Scheme 1. A general scheme for preparing the polystyrene precursor compound of this disclosure ([HN(CH2CH3)3]). + (Non-limiting examples shown are cations)

[0613]

[0614] in:

[0615] (i) KOH, EtOH, reflux; (ii) Me3SiOSO2Cl, 1,2-dichloroethane; (iii) Et3N, n-BuOH; and Ar is arylene, heteroarylene, arylalkyl, or heteroarylalkyl, or two of these linking motifs are linked together to form a linking motif having two linked aromatic groups. Ar is arylene.

[0616] The tetraketone of Scheme 1 can be prepared via the following synthetic process.

[0617] Scheme 2. A general synthetic scheme for tetraketones.

[0618]

[0619] in:

[0620] (iv) Pd(PPh3)2Cl2, CuI, HNEt2; (v) I2, DMSO, reflux; Ar as defined above for scheme 1.

[0621] Examples of X-Ar-X compounds include, for example,

[0622]

[0623] As an example, when used as a starting material in schemes 2 and 1, when compound 2A is used as X-Ar-X, the resulting precursor compound can be

[0624] 4X + .

[0625] As another example, when used as a starting material in schemes 2 and 1, when compound 6 is used as X-Ar-X, the resulting precursor compound can be

[0626] .

[0627] In some embodiments, the polymers of this disclosure can be prepared via scheme 3 (which shows naphthyl-linked polyphenylene as an example), wherein a protecting group, such as TMS (tetramethylsilyl ether), is first removed from a diyne compound, and the resulting diyne is then reacted with a precursor compound via a Diels-Alder reaction to provide the polymer.

[0628] Scheme 3. Synthesis of naphthyl-linked polyphenylene.

[0629]

[0630] In some implementations, instead of first deprotecting the diyne compound, deprotection occurs in situ during polymerization (e.g., implementation 4).

[0631] Option 4. In-situ deprotection of the protected diyne compound.

[0632]

[0633] In some embodiments, the polymers of this disclosure are prepared via the following synthesis scheme.

[0634] Option 5. Providing organometallic catalyst-mediated coupling of exemplary polymers of this disclosure. Although one embodiment of the polymer is shown below, those skilled in the art will understand that polymers with other claimed linkers can be readily obtained using similar synthetic methods as shown in this option.

[0635]

[0636] Some exemplary linkers illustrated in Scheme 5 that can be used for organometallic catalyst-mediated coupling include:

[0637] , , , , , .

[0638] Example 7

[0639] Branched polymer synthesis

[0640] As discussed above, in some embodiments, the polymers of this disclosure are branched. Not wishing to be bound by theory, in some embodiments, branched polymers may possess properties improved relative to their linear polymer analogs. Branched polymers may have multivalent linkers directly covalently bonded to at least three repeating units (e.g., anionic, hydrophobic, or combinations thereof). Branched polymers can be synthesized by adding multifunctional linkers (e.g., dienophiles) having three or more reactive functional groups, such as those outlined in Scheme 6(b) below for trifunctional monomers. Scheme 6(a) shows the synthesis of a linear sulfonated polymer.

[0641] Schemes 6(a) and 6(b) use sulfonated phenyl polystyrene with branching induced by trifunctional monomers.

[0642]

[0643] Representative trifunctional monomers are shown below.

[0644]

[0645] in

[0646] L3', each time appearing, is an unsubstituted or substituted polyvalent heteroatom (e.g., N, P, B), polyaryl, polyheteroaryl, polyaralkyl, or polyheteroaryl, wherein the polyaryl, polyheteroaryl, polyaralkyl, and polyheteroaryl are each unsubstituted or independently selected from C1, C2, or C3. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0647] L2' is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0648] L1' is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0649] D1', D2', and D3' are independently H and 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), wherein R 1G and R1H As defined above, and where R 3G and R 3H As defined above.

[0650] It should be understood that although specific implementations of this disclosure have been described herein for illustrative purposes, various modifications may be made without departing from the spirit and scope of this disclosure.

[0651] Implementation Scheme 1. A copolymer comprising a first repeating unit (x) having formula (I) and a second repeating unit (y) having formula (II):

[0652]

[0653] The copolymer comprises:

[0654] The molar percentage (x) is approximately 75% to approximately 99%.

[0655] Approximately 25% to approximately 1% of the molar percentage (y), and

[0656] in:

[0657] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X+ The substituents are substituted aryl or heteroaryl groups;

[0658] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0659] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein each R 3A R 3B R 3C R 3D R 3E and R 3F Not replaced or selected independently from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0660] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0661] A1 and B1 are independently arylene, heteroarylene, arylene, or heteroarylene, wherein each of the arylene, heteroarylene, arylene, and heteroarylene is either unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl.

[0662] A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl.

[0663] L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4.1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0664] L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0665] L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0666] X + It is a cation.

[0667] Implementation Scheme 2. The copolymer of Implementation Scheme 1, wherein the copolymer has the structure of Formula (III):

[0668]

[0669] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0670] Implementation Scheme 3. The copolymer of any one of the preceding embodiments, wherein A1 and B1 are independently unsubstituted arylene groups or arylene groups substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl; and A2 and B2 are absent.

[0671] Implementation Scheme 4. The copolymer of any one of the preceding embodiments, wherein the first repeating unit (x) of formula (I) is a repeating unit of formula (IA):

[0672]

[0673] in:

[0674] R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1FEach was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0675] R 2A R 2B R 2C and R 2D It can be independently H, halogen, nitro, cyano, aryl, or heteroaryl;

[0676] L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0677] L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0678] L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0679] Implementation Scheme 5. The copolymer of any one of the preceding embodiments, wherein the second repeating unit (y) of formula (II) is a repeating unit of formula (II-A):

[0680]

[0681] in:

[0682] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0683] R 4A R 4B R 4C and R 4D It can be independently H, halogen, nitro, cyano, aryl, or heteroaryl;

[0684] K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0685] K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0686] K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0687] Implementation Scheme 6. The copolymer of any one of the preceding embodiments, wherein the copolymer has the structure of formula (IV):

[0688]

[0689] The first repeating unit (x) has a molar percentage of about 75% to about 99%, and the second repeating unit (y) has a molar percentage of about 25% to about 1%, wherein:

[0690] R 1a R 1b R1e and R 1f SO3 independently - X + or H + The condition is R 1a R 1b R 1e and R 1f At least two of them are SO3 - X + , where X + Independently selected from H + Alkali metal ions, transition metal ions and [N(R 5A (R) 5B (R) 5C (R) 5D )] + And R 5A R 5B R 5C and R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl;

[0691] R 3a R 3b R 3e and R 3f Independently selected from hydrogen, C 1-12 Alkyl, halogen, phenyl, nitro, and cyano groups;

[0692] L1 and K1 are independently linked arylene groups, wherein the arylene groups are unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0693] L2, K2, L3, and K3 are independently absent or aryl, wherein each aryl group is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

[0694] Implementation Scheme 7. The copolymer of any one of the preceding implementation schemes, wherein X + The cation is selected from H + Alkali metal ions, transition metal ions and [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6Alkyl, aryl, or heteroaryl.

[0695] Implementation Scheme 8. The copolymer of any one of the preceding embodiments, wherein L1 and K1 are independently arylene; L2 and K2 are independently absent or arylene; L3 and K3 are independently absent or arylene, wherein each arylene is unsubstituted or is composed of 1, 2, 3 or 4 independently selected from C 1-6 Alkyl and halogen substituents.

[0696] Implementation Scheme 9. The copolymer of any one of the preceding embodiments, wherein L1 and K1 are independently naphthylene, phenylene, or C 1-6 Alkyl-substituted phenylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene, wherein each phenylene is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Alkyl and halogen substituents.

[0697] Implementation Scheme 10. The copolymer of any one of the preceding embodiments, wherein L3, L2 and L1 of –L3–L2–L1– and K3, K2 and K1 of –K3–K2–K1– are each independently selected from…

[0698] , , , , , , , , , , , , , , , , , , , , , , , , , , and .

[0699] Implementation Scheme 11. The copolymer of any one of the preceding embodiments, wherein the first repeating unit (x) is selected from:

[0700] , , , and any combination thereof,

[0701] Where X + For H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl.

[0702] Implementation Scheme 12. The copolymer of any one of the preceding embodiments, wherein the second repeating unit (y) is selected from:

[0703] , , , and any combination thereof.

[0704] Implementation Scheme 13. The copolymer described in any of the preceding implementation schemes, comprising:

[0705] Selected from the following first repeating unit (x):

[0706] , , , , and any combination thereof, where X + It is H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl or heteroaryl; and

[0707] Selected from the following second repeating unit (y):

[0708] , , , and any combination thereof;

[0709] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0710] Implementation Scheme 14. The copolymer of any one of the preceding embodiments further comprises a multivalent linker M1, wherein M1 is covalently bonded to at least three sulfonated polyphenylene repeating units (x) of formula (I), hydrophobic polyphenylene repeating units (y) of formula (II), or combinations thereof, wherein the multivalent linker M1 is selected from:

[0711] , , , , , and .

[0712] Implementation Scheme 15. The copolymer of Implementation Scheme 14, wherein the ionic polymer has a branched structure of formula (V):

[0713]

[0714] P1 and P2 are independently selected from the repeating unit (x) of equation (I) and the repeating unit (y) of equation (II).

[0715] Implementation Scheme 16. The copolymer described in Implementation Scheme 15, wherein the ratio of z / (x+P1+P2) is less than 0.2.

[0716] Implementation Scheme 17. The copolymer of any one of the preceding embodiments, wherein the molar percentage of the first repeating unit (x) is about 85% to about 99%, and the molar percentage of the second repeating unit (y) is about 15% to about 1%.

[0717] Implementation Scheme 18. The copolymer of any one of the preceding embodiments, wherein the molar percentage of the first repeating unit (x) is about 90% and the molar percentage of the second repeating unit (y) is about 10%.

[0718] Implementation Scheme 19. The copolymer described in Implementation Schemes 1-18, wherein the copolymer is linear.

[0719] Implementation Scheme 20. The copolymer described in Implementation Schemes 1-18, wherein the copolymer is branched.

[0720] Implementation Scheme 21. The copolymer of any one of the preceding embodiments, wherein the copolymer is a random copolymer comprising a random distribution of x and y.

[0721] Implementation Scheme 22. The copolymer described in Implementation Schemes 1-20, wherein the copolymer is a statistical copolymer comprising average composition ratios (x) and (y).

[0722] Implementation Scheme 23. The copolymer described in Implementation Schemes 1-20, wherein the copolymer is a random block copolymer comprising:

[0723] The first segment selected from the first repeating unit (x):

[0724] , , , and any combination thereof, where X + It is H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl or heteroaryl; and

[0725] The second segment selected from the second repeating unit (y):

[0726] , , , and any combination thereof, wherein:

[0727] n is an integer from 3 to 100.

[0728] m is an integer from 3 to 100; and

[0729] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0730] Implementation Scheme 24. A method for preparing random copolymers, comprising:

[0731] A mixture of the first repeating unit (x) of formula (VI) and the second repeating unit (y) of formula (VII):

[0732]

[0733] in:

[0734] R 1A R 1BR 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups;

[0735] R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents;

[0736] A1 is independently arylene, heteroarylene, arylene or heteroarylene, each unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroarylene;

[0737] A2 is independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0738] L1 is independently a linked heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0739] L2 is independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0740] L3 is independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0741] X + For H + or cations; and

[0742] A is the reactive first terminal group.

[0743]

[0744] in

[0745] R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, each unsubstituted or composed of 1, 2, 3, 4 or 5 independently selected from C 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups;

[0746] R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, nitro, and cyano groups;

[0747] B1 is independently an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, each unsubstituted or substituted by one, two, three, or four independently selected substituents from halogen, nitro, cyano, aryl, and heteroaryl groups.

[0748] B2 is independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl;

[0749] K1 is independently a linked heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0750] K2 is independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups;

[0751] K3 is independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C by 1, 2, 3, or 4 groups. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and

[0752] B is the second reactive terminal group configured to react with A, and

[0753] React A and B to provide a random copolymer of formula (III):

[0754]

[0755] The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

[0756] Implementation Scheme 25. A membrane or ionomer comprising a copolymer of any one of Implementation Schemes 1-23.

[0757] Implementation Scheme 26. An ionic copolymer membrane comprising the copolymer of any one of Implementation Schemes 1-23, wherein the ionic copolymer membrane has an IEC of 2.4-3.5 meq / g.

[0758] Implementation Scheme 27. An ionic copolymer membrane comprising the copolymer of any one of Implementation Schemes 1-23, wherein the ionic copolymer membrane exhibits 60-120% by weight water absorption at room temperature.

Claims

1. A copolymer comprising a first repeating unit (x) having formula (I) and a second repeating unit (y) having formula (II): The copolymer comprises: The molar percentage (x) is approximately 75% to approximately 99%. Approximately 25% to approximately 1% of the molar percentage (y), and in: R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5 others. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups; R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents; R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein each R 3A R 3B R 3C R 3D R 3E and R 3F Not replaced or selected independently from C by 1, 2, 3, 4 or 5. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups; R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups; A1 and B1 are independently arylene, heteroarylene, arylene, or heteroarylene, wherein each of the arylene, heteroarylene, arylene, and heteroarylene is either unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl. A2 and B2 are independently absent, arylene or heteroarylene, wherein the arylene and heteroarylene are either unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl. L1 and K1 are independently linked heteroatoms, arylene, heteroarylene, arylene, or heteroarylene, wherein the linked heteroatoms, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; L2 and K2 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; L3 and K3 are independently absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and X + It is a cation.

2. The copolymer of claim 1, wherein the copolymer has the structure of formula (III): The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

3. The copolymer of claim 1, wherein A1 and B1 are independently arylene groups, wherein the arylene groups are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl; and A2 and B2 are absent.

4. The copolymer of claim 1, wherein the first repeating unit (x) of formula (I) is a repeating unit of formula (IA): in: R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5 others. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, provided that R is present. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups; R 2A R 2B R 2C and R 2D It can be independently H, halogen, nitro, cyano, aryl, or heteroaryl; L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are each unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

5. The copolymer of claim 1, wherein the second repeating unit (y) of formula (II) is a repeating unit of formula (II-A): in: R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5 others. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups; R 4A R 4B R 4C and R 4D It can be independently H, halogen, nitro, cyano, aryl, or heteroaryl; K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1 by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

6. The copolymer of claim 1, wherein the copolymer has the structure of formula (IV): The first repeating unit (x) has a molar percentage of about 75% to about 99%, and the second repeating unit (y) has a molar percentage of about 25% to about 1%. in: R 1a R 1b R 1e and R 1f SO3 independently - X + or H + The condition is R 1a R 1b R 1e and R 1f At least two of them are SO3 - X + , where X + Independently selected from H + Alkali metal ions, transition metal ions and [N(R 5A (R) 5B (R) 5C (R) 5D )] + And R 5A R 5B R 5C and R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl; R 3a R 3b R 3e and R 3f Independently selected from hydrogen and C 1-12 Alkyl, halogen, phenyl, nitro, and cyano groups; L1 and K1 are independently linked arylene groups, wherein the arylene groups are unsubstituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and L2, K2, L3, and K3 are independently absent or aryl, wherein each aryl group is unsubstituted or is independently selected from C1, C2, C3, or C4. 1-6 Substitution with alkyl, halogen, nitro, cyano, aryl, and heteroaryl substituents.

7. The copolymer of claim 1, wherein X + The cation is selected from H + Alkali metal ions, transition metal ions and [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl.

8. The copolymer of claim 1, wherein L1 and K1 are independently arylene; L2 and K2 are independently absent or arylene; L3 and K3 are independently absent or arylene, wherein each arylene is unsubstituted or is composed of 1, 2, 3 or 4 independently selected from C 1-6 Alkyl and halogen substituents.

9. The copolymer of claim 1, wherein L1 and K1 are independently naphthylene or phenylene; L2 and K2 are independently absent or phenylene; L3 and K3 are independently absent or phenylene, wherein each phenylene group is unsubstituted or is substituted by 1, 2, 3 or 4 groups independently selected from C 1-6 Alkyl and halogen substituents.

10. The copolymer of claim 1, wherein L3, L2, and L1 of –L3–L2–L1– and K3, K2, and K1 of –K3–K2–K1– are each independently selected from… , , , , , , , , , , , , , , , , , , , , , , , , , , and .

11. The copolymer of claim 1, wherein the first repeating unit (x) is selected from: , , , and any combination thereof, Where X + For H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl, or heteroaryl.

12. The copolymer of claim 1, wherein the second repeating unit (y) is selected from: , , , and any combination thereof.

13. The copolymer of claim 1, comprising: Selected from the following first repeating unit (x): , , , and any combination thereof, where X + It is H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl or heteroaryl; and Selected from the following second repeating unit (y): , , , and any combination thereof, The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

14. The copolymer of claim 1, further comprising a multivalent linker M1, wherein M1 is covalently bonded to at least three sulfonated polyphenylene repeating units (x) of formula (I), hydrophobic polyphenylene repeating units (y) of formula (II), or combinations thereof, wherein the multivalent linker M1 is selected from: , , , , , and .

15. The copolymer of claim 14, wherein the ionic polymer has a branched structure of formula (V): P1 and P2 are independently selected from the repeating unit (x) of equation (I) and the repeating unit (y) of equation (II).

16. The copolymer of claim 15, wherein the ratio of z / (x+P1+P2) is less than 0.

2.

17. The copolymer of claim 1, wherein the molar percentage of the first repeating unit (x) is from about 85% to about 99%, and the molar percentage of the second repeating unit (y) is from about 15% to about 1%.

18. The copolymer of claim 1, wherein the first repeating unit (x) has a molar percentage of about 90% and the second repeating unit (y) has a molar percentage of about 10%.

19. The copolymer of claim 1, wherein the copolymer is linear.

20. The copolymer of claim 1, wherein the copolymer is branched.

21. The copolymer of claim 1, wherein the copolymer is a random copolymer having a random distribution of (x) and (y).

22. The copolymer of claim 1, wherein the copolymer is a statistical copolymer having an average composition ratio of (x) and (y).

23. The copolymer of claim 1, wherein the copolymer is a random block copolymer comprising: The first segment selected from the first repeating unit (x): , , , and any combination thereof, where X + It is H + Alkali metal ions, transition metal ions, or [N(R 5A (R) 5B (R) 5C (R) 5D )] + , where R 5A R 5B R 5C R 5D H and C independently 1-6 Alkyl, aryl or heteroaryl; and The second segment selected from the second repeating unit (y): , , , and any combination thereof, wherein: n is an integer from 3 to 100. m is an integer from 3 to 100; and The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

24. A method for preparing random copolymers, comprising: A mixture of the first repeating unit (x) of formula (VI) and the second repeating unit (y) of formula (VII): in: R 1A R 1B R 1C R 1D R 1E and R 1F Independently aryl or heteroaryl, wherein R 1A R 1B R 1C R 1D R 1E and R 1F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5 others. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents are substituted, and the condition is R. 1A R 1B R 1C R 1D R 1E and R 1F At least two of them are independently selected from SO3 by 1, 2, 3, 4 or 5 independently selected. - X + PO3 2- X + 2 and COO - X + The substituents are substituted aryl or heteroaryl groups; R 1G and R 1H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Alkyl, halogen, phenyl, nitro, cyano, SO3 - X + PO3 2- X + 2 and COO - X + Substituents of the substituents; A1 is arylene, heteroarylene, arylene, or heteroarylene, wherein the arylene, heteroarylene, arylene, and heteroarylene are unsubstituted or substituted by 1, 2, 3, or 4 substituents independently selected from halogen, nitro, cyano, aryl, and heteroaryl. A2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl; L1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; L2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; L3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; X + It is a cation; and A is the reactive first terminal group. in R 3A R 3B R 3C R 3D R 3E and R 3F Independently aryl or heteroaryl, wherein R 3A R 3B R 3C R 3D R 3E and R 3F Each was not replaced or was independently selected from C by 1, 2, 3, 4 or 5 others. 1-12 Substitution of alkyl, halogen, phenyl, nitro, and cyano groups; R 3G and R 3H Independently H, aryl, or heteroaryl, wherein the aryl and heteroaryl groups are each unsubstituted or are independently selected from C by 1, 2, 3, 4, or 5 C groups. 1-6 Substitution of alkyl, halogen, nitro, and cyano groups; B1 is an arylene, heteroarylene, arylalkyl, or heteroarylalkyl group, wherein the arylene, heteroarylene, arylalkyl, or heteroarylalkyl group is unsubstituted or substituted by 1, 2, 3, or 4 independent substituents selected from halogen, nitro, cyano, aryl, and heteroaryl groups. B2 is absent, arylene or heteroarylene, wherein the arylene and heteroarylene are unsubstituted or substituted by 1, 2, 3 or 4 substituents independently selected from halogen, nitro, cyano, aryl and heteroaryl; K1 is a linking heteroatom, arylene, heteroarylene, arylene, or heteroarylene, wherein the linking heteroatom, arylene, heteroarylene, arylene, and heteroarylene are not substituted or are independently selected from C1 by 1, 2, 3, or 4 C1 atoms. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; K2 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; K3 is absent, arylene, or heteroarylene, wherein the arylene and heteroarylene groups are not substituted or are independently selected from C1, C2, C3, or C4. 1-6 Substitution of alkyl, halogen, nitro, cyano, aryl, and heteroaryl groups; and B is the second reactive terminal group configured to react with A, and React A and B to provide a random copolymer of formula (III): The molar percentage of the first repeating unit (x) is about 75% to about 99%, and the molar percentage of the second repeating unit (y) is about 25% to about 1%.

25. A membrane or ionomer comprising a copolymer of any one of claims 1-23.

26. An ionic copolymer membrane comprising the copolymer of any one of claims 1-23, wherein the ionic copolymer membrane has an IEC of 2.4-3.5 meq / g.

27. An ionic copolymer membrane comprising the copolymer of any one of claims 1-23, wherein the ionic copolymer membrane exhibits 60-120% by weight water absorption at room temperature.

28. An electrochemical device comprising the copolymer membrane of claim 25, wherein the electrochemical device is a fuel cell, an electrolyzer, a hydrogen pump, a thermoelectrochemical hydrogen pump, an electrochemical hydrogen compressor, a redox flow battery, or other electrochemical device.

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