Sulfonated polyphenylene (phenylene) ether random copolymer, method for producing the same, and use thereof

Abstract

To provide a sulfonated polyphenylene (phenylene) ether random copolymer, a method for producing the same, and use thereof.SOLUTION: A sulfonated polyphenylene (phenylene) ether random copolymer is represented by the following chemical formula, where X represents an arylene group having 2 to 5 carbon atoms or a heteroarylene group containing nitrogen; Y represents an arylene group having 2 to 5 carbon atoms or a heteroarylene group containing nitrogen, C(CF3)Ph, or C(Ph)2; and Z represents a direct bond, S, C(CF3)2, C3H6, SO2, CO2, C(CF3)Ph, C(Ph)2, or an arylene group having 0 to 5 carbon atoms or a heteroarylene group containing nitrogen.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to sulfonated polyphenylene (phenylene) ether random copolymers, their production methods, and their uses. In particular, the present invention relates to polyphenyl polymers having hydrophilic moieties and closely packed sulfonic acid side chains, and is characterized by the ability to precisely adjust the ratio of hydrophilic to hydrophobic moieties. [ka] [Background technology]

[0002] As is well known, proton exchange membrane fuel cells primarily use hydrogen as fuel and produce only water and thermal energy after the reaction, causing no environmental pollution. As a result, they are gradually becoming a very important field in energy-related (green energy) technologies, with industry evaluating and competing for development. Generally, proton exchange membranes are classified as solid electrolytes. Unlike conventional battery electrolytes, which are aqueous solutions, proton exchange membranes, like aqueous electrolytes, are conductors that can transport positive and negative ions. The primary function of a proton exchange membrane is to transport protons. The polymer-based proton exchange membrane is the most important component of a fuel cell, and its characteristics have a significant impact on the performance and lifespan of the fuel cell.

[0003] In view of the shortcomings of the above-mentioned existing technologies, the present invention aims to overcome these incomplete points through thorough research. There are many conventional proton exchange membranes on the market, such as Nafion, manufactured by DuPont. Nafion is a perfluorosulfonated polymer with high proton conductivity and a long lifespan. However, conventional proton exchange membranes cannot effectively retain water molecules in high-temperature, low-humidity environments, resulting in reduced proton conductivity. If their glass transition temperatures are too low, they cannot operate continuously in high-temperature environments and require frequent replacement, resulting in high costs. Therefore, the development of proton exchange membrane technology that can effectively replace conventional proton exchange membranes at a low price is a challenge that industries in related technology fields must overcome.

[0004] The prior art related to the present invention is as follows: As an example of a conventional polymer, Patent Document 1 discloses a fluorine-containing sulfonated polyaromatic ether polymer having a repeating unit having the following molecular formula: [ka] wherein z is independently selected from the group -F or -CF3, n is an integer of 2 or greater, i is an integer from 0 to 10, j is an integer from 1 to 10, and k is an integer from 1 to 6. Furthermore, Patent Document 2 discloses, as a conventional polymer, a cation-containing conductive polymer containing a large number of repeating units having the following chemical formula: [ka] where i is an integer greater than or equal to 1 and j is an integer greater than or equal to 1. The above two patents disclose the use of various sulfonated alternating polyaromatic ether copolymers in proton exchange membranes. These sulfonated alternating polyaromatic ether copolymers have excellent mechanical and thermal stability, multiple sulfonation sites provide high ionic conductivity, and maintain excellent dimensional stability. However, the polymers used in proton exchange membranes are manufactured using post-sulfonation reactions, and the ion exchange capacity and ionic conductivity of the membranes, as well as the reduction of water absorption and the maintenance of membrane dimensional stability, can only be adjusted by adjusting the ratio of sulfonating agent and the number of substituents on the benzene ring. Furthermore, the IEC of each batch of polymer manufactured by post-sulfonation is often inconsistent, making it difficult to fine-tune the compound or achieve functional design, which causes inconvenience and problems in the application of proton exchange membranes. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Taiwan Publication No. I527842 Patent Publication [Patent Document 2] Taiwan Publication No. I675864 Patent Publication Summary of the Invention [Problem to be solved by the invention]

[0006] To achieve these and other objectives, the present invention provides a sulfonated polyphenylene (phenylene) ether random copolymer, its preparation method, and its applications. The objective is to prepare a polyphenylene polymer with a hydrophilic portion and dense sulfonic acid side chains. A specific portion of the polymer contains two random segments, one of which has multiple sulfonic acid ester substituents on multiple benzene rings and acts as a hydrophilic segment, and the other segment acts as a hydrophobic segment. The ion exchange capacity of the copolymer of the present invention can be adjusted by adjusting the equivalence ratio between the hydrophilic and hydrophobic segments. The higher the equivalence ratio of the hydrophilic segments, the higher the ion exchange capacity, ionic conductivity, and water absorption of the membrane made from the copolymer, but the worse the dimensional stability. The higher the proportion of the hydrophobic segments, the lower the ion exchange capacity, ionic conductivity, and water absorption of the membrane made from the copolymer, but the better the dimensional stability. Furthermore, when a polymer film is produced using the polyphenyl structure of the present invention, it is endowed with strong mechanical properties and can maintain good dimensional stability even when in contact with water for a long period of time. The technical means for achieving the main object of the present invention is a copolymer represented by the following chemical structure: [ka]

[0007] wherein X is a first linking group optionally substituted with 2-5 arylene or nitrogen-containing heteroarylene groups, and Y is a second linking group optionally substituted with 2-5 arylene, nitrogen-containing heteroarylene, C(CF3)Ph, or C(Ph)2 groups, R1 is 0 or an integer greater than 0 and is halogen, NO2, CN, CF3, CH3, or SO3H, R2 is 1-8 aryl or nitrogen-containing heteroaryl groups optionally substituted with 0-8 substituents independently selected from halogen, NO2, CN, CF3, CH3, and SO3H, and R3 is 0-4 substituents independently selected from halogen, NO2, CN, CF3, CH3, and SO3H, aryl, and nitrogen-containing heteroaryl. Z is a direct bond, S, C(CF3)2, C3H6, SO2, CO2, C(CF3)Ph, C(Ph)2, or a third linking group optionally substituted with 0 to 5 arylene or nitrogen-containing heteroarylene groups, where when Z is a direct bond, S, C(CF3)2, C3H6, SO2, CO2, C(CF3)Ph, or C(Ph)2, R4 is 0 or an integer greater than 0, halogen, CH3, NO2, CN, or CF3, and R5 is 0 or an integer greater than 0, halogen, CH3, NO2, CN, or CF3. When Z is a third linking group consisting of 0-5 arylene or nitrogen-containing heteroarylene groups, R4 is 1 or an integer greater than 1, halogen, CH3, NO2, CN, or CF3, and R5 is 0-8 aryl or nitrogen-containing heteroarylene groups, optionally substituted with 0-8 substituents, independently selected from halogen, CH3, NO2, CN, and CF3. When the number of repeating units in the sulfonated polyphenylene (phenylene) ether random copolymer formula (n) is greater than 0, the unit functions as a hydrophilic segment. When the number of repeating units in the sulfonated polyphenylene (phenylene) ether random copolymer formula (n) is 1-n, the unit functions as a hydrophobic segment. Furthermore, the ratio of hydrophilic to hydrophobic segments can be precisely adjusted by controlling the polymerization equivalent ratio of Z. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram of a sulfonation process for producing sulfonated polyphenylene (phenylene) ether random copolymers according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to FIG. 1, one example of the structure of a sulfonated poly(phenylene) ether random copolymer for achieving the main objectives of the present invention has the following chemical structure: [ka] wherein X is 2-5 arylene groups or nitrogen-containing heteroarylene groups; Y is 2-5 arylene groups, nitrogen-containing heteroarylene groups, C(CF3)Ph groups, or C(Ph)2 groups; R1 is 0 or an integer greater than 0 and is a halogen, NO2, CN, CF3, SO3H, CH3, alkyl group, perfluoroalkyl substances (PFAS) group, or aromatic group; R2 is 1-8 aryl groups or nitrogen-containing heteroaryl groups, optionally substituted with 0-8 substituents, independently selected from halogen, NO2, CN, CF3, CH3, and SO3H; and R3 is 0-4 substituents, independently selected from halogen, NO2, CN, CF3, CH3, SO3H, aryl, and nitrogen-containing heteroaryl.

[0010] Z is a direct bond, S, C(CF3)2, C3H6, SO2, CO2, C(CF3)Ph, C(Ph)2, or an arylene group having 0 to 5 carbon atoms or a nitrogen-containing heteroarylene group having 0 to 5 carbon atoms, wherein when Z is a direct bond, S, C(CF3)2, C3H6, SO2, CO2, C(CF3)Ph, or C(Ph)2, R4 represents 0 or an integer greater than 0, a halogen, CH3, NO2, CN, or CF3, R5 represents 0 or an integer greater than 0, a halogen, CH3, NO2, CN, or CF3, and when Z is an arylene group or a nitrogen-containing heteroarylene group having 0 to 5 carbon atoms, R4 represents 1 or an integer greater than 1, a halogen, , CH3, NO2, CN, CF3, and R5 is 0 to 8 aryl groups or nitrogen-containing heteroarylene groups, which may be substituted with 0 to 8 substituents, which are independently selected from halogen, CH3, NO2, CN, and CF3, where, when the number of repeating units in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, n, is greater than 0, the unit acts as a hydrophilic segment, and when the number of repeating units in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, n, is 1-n, the unit acts as a hydrophobic segment. In one embodiment, R1 and R4 are further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups, and the substituents of R2, R3, and R5 are further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups. The aromatic groups of R1, R2, and R3 include 1-8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0-8 substituents, which are independently selected from halogen, NO2, CN, CF3, CH3, and SO3H. The aromatic groups of R4 and R5 include 1-8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0-8 substituents, which are independently selected from halogen, NO2, CN, CF3, and CH3.

[0011] Referring to FIG. 1, the method for producing a sulfonated poly(phenylene) ether random copolymer involves reacting three different polyphenylene ring monomers x, y, and z (e.g., a dihalogen monomer and a diol monomer) through a nucleophilic polymerization reaction followed by a sulfonation reaction to produce a sulfonated polyphenylene(phenylene) ether random copolymer, and the sulfonated polyphenylene(phenylene) ether random copolymer obtained by this method has the following chemical formula structure: [ka]

[0012] In the above chemical formula, specific and feasible embodiments of X, Y, Z, R1, R2, R3, Z, R4, and R5 are as described in the preceding two paragraphs. When the repeating number n of the repeating unit in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is greater than 0 (n>0), this unit acts as a hydrophilic segment, and when the repeating number n of the repeating unit in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is 1-n, this unit acts as a hydrophobic segment.

[0013] As shown in Figure 1, three different polyphenylene ring segments X, Y, and Z are randomly copolymerized with their respective polyphenylene ring monomers x, y, and z. By controlling the sulfonation positions, polyphenylene ring segments X and Y are sulfonated to form hydrophilic segments, while the R4 and R5 substituents of polyphenylene ring segment Z are not sulfonated or the number of sulfonic acid groups is reduced to form hydrophobic segments, which become hydrophobic segments. The equivalent ratio of the hydrophilic and hydrophobic segments can be precisely adjusted by controlling the polymerization equivalent ratio of polyphenylene ring monomer z and polyphenylene ring segment Z.

[0014] The first application example of the present invention is to coat a sulfonated polyphenylene (phenylene) ether random copolymer to form a thin film and use it as a proton exchange membrane, which is applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow batteries, or membrane electrodes. The second application example is to prepare the sulfonated polyphenylene (phenylene) ether random copolymer as a coating solution and apply the coating solution to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow batteries, or membrane electrodes. The third application example is to form the sulfonated polyphenylene (phenylene) ether random copolymer into an electrode and apply the electrode to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow batteries, or membrane electrodes.

[0015] The present invention discloses novel sulfonated polyphenylene(phenylene) ether random copolymers and methods for their preparation. These novel sulfonated polyphenylene(phenylene) ether random copolymers can be used as proton exchange membranes (PEMs), coating solutions, and electrodes in hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow batteries, and membrane electrodes. The present invention is suitable for the production of sulfonated polymer compositions and synthetic polymer compositions for use in fuel cells, electrolysis cells, energy storage, dialysis devices, and ultrafiltration, as well as electrodes and membrane electrode assemblies. The sulfonated polyphenylene(phenylene) ether random copolymers of the present invention are designed as polyphenylene polymers with hydrophilic moieties and dense sulfonic acid side chains, with certain portions of the polymer substituted with multiple sulfonic acid groups. When fabricated into polymer membranes, the polyphenylene structure imparts strong mechanical properties and maintains good dimensional stability, especially when in contact with water for extended periods of time. This method uses three polyphenylene ring monomers, x, y, and z, to control the location of sulfonation through random copolymerization. The polyphenylene ring segments X and Y can be sulfonated to provide hydrophilic segments.

[0016] The R4 and R5 substituents of the polyphenylene ring segment Z are not sulfonated, forming hydrophobic segments. By controlling the polymerization equivalent ratio of this Z chain segment, the ratio of hydrophilic to hydrophobic segments can be precisely adjusted, allowing for more effective control of the ion exchange capacity of the sulfonated copolymer and the precise construction of a variety of products with different performance levels. By fine-tuning the equivalent ratio of the hydrophilic and hydrophobic segments, the ion exchange capacity (IEC) value of each batch of polymer produced by post-sulfonation can be controlled to a fixed value, resulting in copolymers characterized by excellent mechanical properties, excellent membrane dimensional stability, good proton conductivity, and controllable ion exchange capacity.

[0017] For example, if polyphenylene ring monomer x is a dihalogen or diol monomer and has an equivalent ratio of 1, then polyphenylene ring monomers y and z are diol or dihalogen monomers, and the sum of the equivalent ratios of y and z is also 1. If polyphenylene ring monomer y is a dihalogen or diol monomer and has an equivalent ratio of 1, then polyphenylene ring monomers x and z are diol or dihalogen monomers, and the sum of the equivalent ratios of x and z is also 1. The structural design depends on whether the monomer is a dihalogen or diol monomer.

[0018] As shown in Figure 1, the polyphenylene ring monomers x, y, and z are dihalogen monomers or diol monomers, and sulfonated polyphenylene (phenylene) ether random copolymers are obtained through a nucleophilic polycondensation reaction and a post-sulfonation reaction. When the number of repeating units of the hydrophilic segment is n, the number of repeating units of the hydrophobic segment is 1-n.

[0019] Table 1 compares various polymers in terms of the ratio of polyphenylene ring monomers x, y, and z, the weight average molecular weight of the polymer, and the dispersity index. [Table 1]

[0020] Table 2 compares the ion exchange capacity (IEC), water absorption rate (moisture uptake), and elongation rate (ΔL) of various membranes made with the polymers in Table 1. [Table 2]

[0021] Table 3 is a comparison table of the thermal decomposition temperature (Td), Young's modulus (GPa), tensile strength (MPa), and breaking elongation of various films corresponding to the samples in Tables 1 and 2. [Table 3]

[0022] Table 4 is a comparison table of the proton conductivities of various sulfonated polymers corresponding to the samples in Table 2. [Table 4]

[0023] Table 5 compares the fuel cell efficiency of the five samples shown in Table 2 with that of the SP1 membrane (the technology developed by the inventors of Taiwan Patent No. I675864). [Table 5]

[0024] As shown in Table 5, the efficiencies of SRA6F-0.4 (IEC = 3.3 mmol / g, 190 mS / cm), SRA6F-0.3 (IEC = 3.13 mmol / g, 177 mS / cm), and SRA6F-0.5 (IEC = 3.46 mmol / g, 201 mS / cm) were superior to the control SP1 (IEC = 3.27 mmol / g, 172 mS / cm). SRA6F-0.2 (IEC = 2.95 mmol / g, 166 mS / cm) and SRA6F-0.1 (IEC = 2.76 mmol / g, 155 mS / cm) had slightly lower efficiencies than the control due to their lower conductivity. Based on these results, the present invention provides a sulfonated polyphenyl(aryl)ether random copolymer, which is obtained by adjusting the polymerization ratio of three different polycyclic aromatic monomers, x, y, and z, through a nucleophilic polycondensation reaction. After the sulfonation reaction, specific hydrophilic and hydrophobic terminal chains are formed, and the hydrophilic and hydrophobic terminal chains can be fine-tuned and controlled by adjusting the polymerization ratio. As a result, the polymer of this example exhibited higher conductivity even when its IEC was close to that of the control, SP1, and its fuel cell efficiency was approximately 10% higher than that of the control.

[0025] Therefore, through the detailed description of the above specific examples, it is clear that the present invention has the following advantages: The invention can reliably produce polyphenyl polymers with hydrophilic moieties and dense sulfonic acid side chains, with multiple sulfonic acid groups substituted on specific parts of the polymer. When the polyphenyl polymer is produced as a polymer membrane, the polyphenyl structure provides strong mechanical properties and maintains good dimensional stability even when in contact with water for a long period of time.

[0026] The sulfonated polyphenylene (phenylene) ether random copolymer prepared according to the present invention can be reliably used as a material for producing proton exchange membranes. Based on the above-mentioned method for preparing sulfonated polyphenylene (phenylene) ether random copolymers and the properties of the above-mentioned sulfonated polyphenylene ionomers, proton exchange membranes can be produced at low cost and with effectively controlled ion exchange capacity, which makes them suitable for use in electrochemical energy conversion devices such as fuel cells, water electrolysis membranes, and liquid flow batteries.

[0027] The novel sulfonated polyphenylene(phenylene) ether random copolymers of the present invention and their production methods can be commercialized as proton exchange membranes (PEMs), coating solutions, and electrodes for use in hydrogen fuel cells, direct methanol fuel cells, and membrane electrodes.

[0028] The method of the present invention is suitable for producing sulfonated polymer compositions and synthetic polymer compositions for application in polymer electrolyte membranes, electrodes, membrane electrode assemblies in fuel cells, electrolysis cells, electrolyte membranes in dialysis and ultrafiltration devices.

Claims

1. In the following, X represents an aryl group having 2 to 5 carbon atoms or a heteroaryl group containing nitrogen, and Y represents an aryl group having 2 to 5 carbon atoms, a heteroaryl group containing nitrogen, or C(CF ３ )Ph group or C(Ph) ２ represents a group, and R １ is 0 or an integer greater than 0, halogen, NO ２ , C.N., C.F. ３ , C.H. ３ or SO ３ H represents R ２ is 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0 to 8 first substituents, which may be halogen, NO ２ , C.N., C.F. ３ , C.H. ３ and SO ３ H, and R ３ are 0 to 4 substituents, which are independently halogen, NO ２ , C.N., C.F. ３ , C.H. ３ , SO ３ selected from H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF ３ ) ２ , C ３ H ６ , SO ２ , CO ２ , C(CF ３ )Ph, C(Ph ２ ), 0-5 aryl groups or 0-5 nitrogen-containing heteroaryl groups, and Z is a direct bond, S, C(CF ３ ) ２ , C ３ H ６ , SO ２ , CO ２ , C(CF ３ )Ph or C(Ph) ２ If R ４ is 0 or an integer greater than 0, halogen, CH ３ , NO ２ , CN or CF ３ represents R ５ is 0 or an integer greater than 0, halogen, CH ３ , NO ２ , CN or CF ３ and when Z is 0-5 aryl groups or nitrogen-containing heteroaryl groups, R ４ is 1 or an integer greater than 1, halogen, CH ３ , NO ２ , CN or CF ３ represents R ５ is 0 to 8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0 to 8 substituents, which may include halogen, CH ３ , NO ２ , CN and CF ３ wherein a portion of the formula where the number of repeating units is n (n>0) acts as a hydrophilic segment, and a portion of the formula where the number of repeating units is 1-n acts as a hydrophobic segment. A sulfonated polyphenylene (phenylene) ether random copolymer having the chemical structure shown below. 【Chemical 1】

2. R １ and R ４ is further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups; R ２ , R ３ and R ５ The sulfonated polyphenylene (phenylene) ether random copolymer of claim 1, wherein the substituents are further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups.

3. R １ , R ２ and R ３ The aromatic group contains 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may be halogen, NO ２ , C.N., C.F. ３ , C.H. ３ and SO ３ and R ４ and R ５ The aromatic group contains 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may be halogen, NO ２ , C.N., C.F. ３ and C.H. ３ 3. The sulfonated polyphenylene (phenylene) ether random copolymer of claim 2, which can be substituted with 0 to 8 substituents independently selected from:

4. treating the three polyphenyl ring monomers x, y, and z by a nucleophilic polycondensation reaction to obtain the corresponding polyphenyl ring segments X, Y, and Z; Wherein, when polyphenyl ring monomer x is a dihalogen or diol monomer with an equivalent ratio of 1, polyphenyl ring monomers y and z are diol or dihalogen monomers, and the sum of the equivalent ratios of y and z is 1; when polyphenyl ring monomer y is a dihalogen or diol monomer with an equivalent ratio of 1, polyphenyl ring monomers x and z are diol or dihalogen monomers, and the sum of the equivalent ratios of x and z is 1; then, a post-treatment sulfonation reaction is carried out to obtain a sulfonated polyphenylene (phenylene) ether random copolymer having the following chemical structure: X represents an arylene group having 2 to 5 carbon atoms or a heteroarylene group containing nitrogen; Y represents an arylene group having 2 to 5 carbon atoms, a heteroarylene group containing nitrogen, or C(CF ３ )Ph group or C(Ph) ２ represents a group, and R １ is 0 or halogen, NO ２ , C.N., C.F. ３ , C.H. ３ or SO ３ H represents any integer, and R ２ is 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0 to 8 substituents, including halogen, NO ２ , C.N., C.F. ３ , C.H. ３ , SO ３ is chosen independently of H, R ３ are 0 to 4 substituents, which are halogen, NO ２ , C.N., C.F. ３ , C.H. ３ , SO ３ independently selected from H, an aryl group, or a nitrogen-containing heteroaryl group; Z is direct connection, S, C (CF ３ ) ２ , C ３ H ６ , SO ２ , CO ２ , C(CF ３ )Ph, C(Ph) ２ , 0 to 5 arylene groups, or 0 to 5 heteroarylene groups containing nitrogen, and Z is a direct bond, S, C(CF ３ ) ２ , C ３ H ６ , SO ２ , CO ２ , C(CF ３ )Ph, C(Ph) ２ If R ４ is 0 or halogen, CH ３ , NO ２ , C.N., C.F. ３ represents any integer, and R ５ is 0 or halogen, CH ３ , NO ２ , C.N., C.F. ３ represents any integer of When Z is an arylene group having 0 to 5 carbon atoms or a heteroarylene group having 0 to 5 nitrogen atoms, R ４ is 1 or halogen, CH ３ , NO ２ , C.N., C.F. ３ represents any integer, and R ５ is 0 to 8 aryl or nitrogen-containing heteroaryl groups, which may be substituted with 0 to 8 substituents, including halogen, CH ３ , NO ２ , C.N., C.F. ３ wherein the repeating units where n is greater than 0 function as hydrophilic segments, and the repeating units 1-n function as hydrophobic segments. 【Chemical 1】

5. R １ and R ４ is further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups; R ２ , R ３ and R ５ The method for producing a sulfonated polyphenylene (phenylene) ether random copolymer according to claim 4, wherein the substituents are further independently selected from alkyl groups, perfluoroalkyl groups, and aromatic groups.

6. R １ , R ２ and R ３ The aromatic group contains 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may have 0 to 8 substituents, which may include halogen, NO ２ , C.N., C.F. ３ , C.H. ３ and SO ３ independently selected from H and R ４ and R ５ The aromatic group contains 1 to 8 aryl or nitrogen-containing heteroaryl groups, which may have 0 to 8 substituents, which may include halogen, NO ２ , C.N., C.F. ３ and C.H. ３ The method for producing a sulfonated polyphenylene (phenylene) ether random copolymer according to claim 5, characterized in that the sulfonated polyphenylene (phenylene) ether random copolymers are independently selected from the following:

7. The polyphenyl ring segments X, Y, and Z are randomly copolymerized, and the sulfonation is controlled so that the polyphenyl ring segments X and Y are sulfonated to form hydrophilic segments, and the R of the polyphenyl ring segment Z is sulfonated to form hydrophilic segments. ４ and R ５ The method for producing a sulfonated polyphenylene (phenylene) ether random copolymer according to claim 6, characterized in that the substituents of are not sulfonated, and the hydrophobic segments are formed by controlling the polymerization equivalent ratio of the polyphenyl ring segment Z, thereby making it possible to adjust the equivalent ratio of the hydrophilic and hydrophobic segments.

8. A proton exchange membrane made of the sulfonated polyphenylene (phenylene) ether random copolymer according to claim 1, characterized in that it is formed as a coating solution or as an electrode and applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

9. The coating solution made of the sulfonated polyphenylene (phenylene) ether random copolymer according to claim 1, characterized in that the coating solution is applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

10. The electrode made of the sulfonated polyphenylene (phenylene) ether random copolymer according to claim 1, characterized in that the electrode is applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

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