Sulfonated polyphenylene (phenylene) ether random copolymer, preparation method and application thereof

Abstract

The present invention discloses sulfonated polyphenylene (phenylene) ether random copolymer, preparation method and application thereof, which has a general chemical formula:

##STR00001## wherein, X is 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is 2 to 5 arylene groups or nitrogen-containing heteroarylene groups, C(CF.sub.3)Ph, C(Ph).sub.2; Z is direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph, C(Ph).sub.2, 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; R.sub.1 is 0 or more of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 or SO.sub.3H; R.sub.2 is 1 to 8 aryl groups or nitrogen-containing heteroaryl groups optionally substituted with 0 to 8 substituents of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 or SO.sub.3H; R.sub.3 is 0 to 4 substituents of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, aryl or nitrogen-containing heteroaryl; R.sub.4 is 0 or more of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 is 0 or more of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, or 0 to 8 aryl or nitrogen-containing heteroaryl substituted with 0 to 8 substituents of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3.

Whereby, the polyphenyl polymer has hydrophilic part and dense sulfonic acid side chains, membrane made by the polymer with polyphenyl structure does have strong mechanical properties and maintains good dimensional stability when in contact with water for a long time. Through controlling the polymerization equivalent ratio of Z, the ratio between the hydrophilic and hydrophobic segments can be precisely adjusted.

Claims

1. A sulfonated polyphenylene (phenylene) ether random copolymer having a general chemical structure of the following formula: ##STR00007## wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF.sub.3)Ph groups or C(Ph).sub.2 groups; R.sub.1 represents 0 or an integer number greater than 0 of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 or SO.sub.3H; R.sub.2 represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; R.sub.3 is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph, C(Ph.sub.2), 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph or C(Ph).sub.2, R.sub.4 is 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 is 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3; wherein, when Z is 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R.sub.4 is 1 or an integer number greater than 1 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 is 0 to 8 aryl groups or nitrogen-containing heteroarylene groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH.sub.3, NO.sub.2, CN and CF.sub.3; the repeating unit with the repeating number of n greater than 0 in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment.

2. The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 1, wherein R.sub.1 and R.sub.4 further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R.sub.2, R.sub.3 and R.sub.5 are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups.

3. The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 2, wherein the aromatic groups of R.sub.1, R.sub.2 and R.sub.3 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; wherein the aromatic groups of R.sub.4 and R.sub.5 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3 and CH.sub.3.

4. The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 1, wherein through a nucleophilic polycondensation reaction, X, Y and Z are formed by polyphenyl ring monomers x, y and z correspondingly; wherein, when x is a dihalogen or diol monomer having an equivalent ratio of 1, y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when y is a dihalogen or diol monomer having an equivalent ratio of 1, x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1; the equivalent ratios of x, y and z are respectively not equal to 0.

5. The sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 4, wherein a weight ratio between the hydrophilic and hydrophobic segments is adjustable by controlling the equivalent ratio of z.

6. A method for preparing the sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 1 comprised the steps of: treating three polyphenyl ring monomers x, y and z by a nucleophilic polycondensation reaction to obtain polyphenyl ring segments of X, Y and Z correspondingly; wherein, when the polyphenyl ring monomer x is a dihalogen or diol monomer having an equivalent ratio of 1, the polyphenyl ring monomers y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when the polyphenyl ring monomer y is a dihalogen or diol monomer having an equivalent ratio of 1, the polyphenyl ring monomers x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1, and then through a post-sulfonation reaction to obtain the sulfonated polyphenylene (phenylene) ether random copolymer having a general chemical structure of the following formula: ##STR00008## wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF.sub.3)Ph groups or C(Ph).sub.2 groups; R.sub.1 represents 0 or an integer number greater than 0 of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 or SO.sub.3H; R.sub.2 represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; R.sub.3 is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph, C(Ph.sub.2), or a third linker group optionally substituted with 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph or C(Ph).sub.2, R.sub.4 is 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 is 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3; wherein, when Z is the third linker group of 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R.sub.4 is 1 or an integer number greater than 1 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 is 0 to 8 aryl groups or nitrogen-containing heteroarylene groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH.sub.3, NO.sub.2, CN and CF.sub.3; the repeating unit with the repeating number of n greater than 0 in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment.

7. The method as claimed in claim 6, wherein R.sub.1 and R.sub.4 further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R.sub.2, R.sub.3 and R.sub.5 are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups.

8. The method as claimed in claim 7, wherein the aromatic groups of R.sub.1, R.sub.2 and R.sub.3 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; wherein the aromatic groups of R.sub.4 and R.sub.5 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3 and CH.sub.3.

9. The method as claimed in claim 6, wherein the polyphenyl ring segments of X, Y, and Z are randomly copolymerized through the nucleophilic polycondensation reaction to control the post-sulfonation reaction so that the polyphenyl ring segments X and Y are sulfonated to form the hydrophilic segment, the substituents of R.sub.4 and R.sub.5 on the polyphenyl ring segment Z cannot be sulfonated so as to form the hydrophobic segment; wherein, by controlling the equivalent ratio of the polyphenyl ring monomer z, an weight ratio between the hydrophilic and hydrophobic segments is adjusted.

10. The method as claimed in claim 6, wherein a weight ratio between the hydrophilic and hydrophobic segments is adjustable by controlling the equivalent ratio of the polyphenyl ring monomer z; and the equivalent ratios of x, y and z are respectively not equal to 0.

11. A product made by the sulfonated polyphenylene (phenylene) ether random copolymer as claimed in claim 1, the product is formed by the sulfonated polyphenylene (phenylene) ether random copolymer to be proton exchange membranes, coating solutions or electrodes to be applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

12. The product as claimed in claim 11, wherein, in the general chemical structure of the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, wherein R.sub.1 and R.sub.4 further respectively represent 0 or an integer number greater than 0 of alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; the substituents of R.sub.2, R.sub.3 and R.sub.5 are further independently selected from the groups consisting of alkyl groups, per-polyfluoroalkyl substance (PFAS) groups and aromatic groups.

13. The product as claimed in claim 12, wherein the aromatic groups of R.sub.1, R.sub.2 and R.sub.3 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; wherein the aromatic groups of R.sub.4 and R.sub.5 respectively contain 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3 and CH.sub.3.

14. The product as claimed in claim 11, wherein, in the general chemical structure of the formula of the sulfonated polyphenylene (phenylene) ether random copolymer, through a nucleophilic polycondensation reaction, X, Y and Z are formed by polyphenyl ring monomers x, y and z correspondingly; wherein, when x is a dihalogen or diol monomer having an equivalent ratio of 1, y and z are diol or dihalogen monomers and a sum of equivalent ratios of y and z is 1; wherein, when y is a dihalogen or diol monomer having an equivalent ratio of 1, x and z are diol or dihalogen monomers and a sum of equivalent ratios of x and z is 1; the equivalent ratios of x, y and z are respectively not equal to 0.

15. The product as claimed in claim 14, wherein a weight ratio between the hydrophilic and hydrophobic segments of the sulfonated polyphenylene (phenylene) ether random copolymer is adjustable by controlling the equivalent ratio of the polyphenyl ring monomer z.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is a schematic diagram of the sulfonation process for preparing sulfonated polyphenylene (phenylene) ether random copolymers according with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0013] Referring to FIG. 1, One embodiment of the sulfonated poly(phenylene) ether random copolymer structure to achieve the main purpose of the present invention has the following general chemical structure of the following formula:

##STR00005## [0014] wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF.sub.3)Ph groups or C(Ph).sub.2 groups; R.sub.1 represents 0 or an integer number greater than 0 of halogen, NO.sub.2, CN, CF.sub.3, SO.sub.3H, CH.sub.3, alkyl group, per-polyfluoroalkyl substance (PFAS) group or aromatic group, and in one preferable embodiment, wherein the aromatic group contains 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, alkyl group, per-polyfluoroalkyl substance (PFAS) group and aromatic group; R.sub.2 represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, alkyl group, per-poly fluoroalkyl group (PFAS) and aromatic group, and in one preferable embodiment, wherein the aromatic group contains 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; R.sub.3 is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph, C(Ph.sub.2), or a third linker group optionally substituted with 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph or C(Ph).sub.2, R.sub.4 represents 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN, CF.sub.3, alkyl group, per-poly fluoroalkyl group (PFAS) or aromatic group, wherein the aromatic group contains 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3 and CH.sub.3, and R.sub.5 represents 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3; wherein, when Z is the third linker group having 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R.sub.4 represents 1 or an integer number greater than 1 of halogen, CH.sub.3, NO.sub.2, CN, CF.sub.3, alkyl group, per-polyfluoroalkyl substance (PFAS) group or aromatic group, wherein the aromatic group contains 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3 and CH.sub.3, and R.sub.5 represents 0 to 8 aryl groups or nitrogen-containing heteroarylene groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH.sub.3, NO.sub.2, CN and CF.sub.3, alkyl group and per-polyfluoroalkyl substance (PFAS) group; wherein, the repeating unit with the repeating number of n greater than 0 in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment.

[0015] Referring to FIG. 1, the method for preparing a sulfonated poly(phenylene) ether random copolymer is reacting three different polyphenyl ring monomers x, y and z (such as dihalogen monomer and diol monomer) through a nucleophilic polycondensation reaction and a post-sulfonation reaction to prepare the sulfonated polyphenylene (phenylene) ether random copolymer, so that the sulfonated polyphenylene (phenylene) ether random copolymer has the following general chemical formula structure:

##STR00006## [0016] wherein, X is a first linker group optionally substituted with 2 to 5 arylene groups or nitrogen-containing heteroarylene groups; Y is a second linker group optionally substituted with 2 to 5 arylene groups, nitrogen-containing heteroarylene groups, C(CF.sub.3)Ph groups or C(Ph).sub.2 groups; R.sub.1 represents 0 or an integer number greater than 0 of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 or SO.sub.3H; R.sub.2 represents 1 to 8 aryl groups or nitrogen-containing heteroaryl groups which optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3 and SO.sub.3H; R.sub.3 is optionally substituted with 0 to 4 substituents which are independently selected from halogen, NO.sub.2, CN, CF.sub.3, CH.sub.3, SO.sub.3H, aryl and nitrogen-containing heteroaryl; Z is a direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph, C(Ph.sub.2), or a third linker group optionally substituted with 0 to 5 arylene groups or nitrogen-containing heteroarylene groups; wherein, when Z is the direct bond, S, C(CF.sub.3).sub.2, C.sub.3H.sub.6, SO.sub.2, CO.sub.2, C(CF.sub.3)Ph or C(Ph).sub.2, R.sub.4 represents 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 represents 0 or an integer number greater than 0 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3; wherein, when Z is the third linker group of 0 to 5 arylene groups or nitrogen-containing heteroarylene groups, R.sub.4 represents 1 or an integer number greater than 1 of halogen, CH.sub.3, NO.sub.2, CN or CF.sub.3, and R.sub.5 represents 0 to 8 aryl groups or nitrogen-containing heteroarylene groups and is optionally substituted with 0 to 8 substituents which are independently selected from the groups consisting of halogen, CH.sub.3, NO.sub.2, CN and CF.sub.3; the repeating unit with the repeating number of n greater than 0 (n>0) in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophilic segment, and the repeating unit with the repeating number of 1-n in the formula of the sulfonated polyphenylene (phenylene) ether random copolymer is acting as a hydrophobic segment.

[0017] Specifically, as shown in FIG. 1, three different polyphenyl ring segments X, Y, and Z are randomly copolymerized by three polyphenyl ring monomers x, y and z correspondingly to control the position of sulfonation so that the polyphenyl ring segments X and Y can be sulfonated to obtain a hydrophilic segment, and the substituents of R.sub.4 and R.sub.5 on the polyphenyl ring segment Z are unable to be sulfonated or the number of sulfonate groups is reduced so as to form the hydrophobic segments. The weight ratio of the hydrophilic and hydrophobic segments can be finely adjusted by controlling the polymerization equivalent ratio of the polyphenyl ring monomers z.

[0018] One application of the present invention is to make products of proton exchange membranes, wherein the sulfonated polyphenylene (phenylene) ether random copolymer is coated to form thin films to be proton exchange membranes, and the proton exchange membranes are applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

[0019] Another application of the present invention is to make products of solution for coating, wherein the sulfonated polyphenylene (phenylene) ether random copolymer is prepared to be coating solution, and the coating solution is applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

[0020] Another application of the present invention is to make products of electrodes, wherein the sulfonated polyphenylene (phenylene) ether random copolymer is formed as electrodes, and the electrodes are applied to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells or membrane electrodes.

[0021] The present invention discloses a novel sulfonated polyphenylene (phenylene) ether random copolymer and a novel method for preparing the same, and the novel sulfonated polyphenylene (phenylene) ether random copolymer can be formed as proton exchange membranes, coating solutions and electrodes for applying to hydrogen fuel cells, direct methanol fuel cells, water electrolysis membranes, vanadium liquid flow cells and membrane electrodes. The present invention is suitable for producing sulfonated polymer compositions and synthetic polymer compositions for use in fuel cells, electrolytic cells, energy storages, dialysis equipment and ultrafiltration, electrodes and membrane electrode assemblies. The sulfonated polyphenylene (phenylene) ether random copolymer of the present invention is designed to be polyphenyl polymer having hydrophilic part and dense sulfonic acid side chain, wherein the specific part of the polymer is substituted with multiple sulfonic acid groups. When made as polymer membranes, the polyphenyl structure can impart strong mechanical properties, especially maintaining good dimensional stability when in contact with water for a long time. The method uses three polyphenyl ring monomers x, y and z to control the position of sulfonation by random copolymerization. The polyphenyl ring segments X and Y can be sulfonated to obtain the hydrophilic segments. The substituents of R.sub.4 and R.sub.5 on the polyphenyl ring segment Z cannot be sulfonated so as to form the hydrophobic segment. By controlling the polymerization equivalent ratio of the chain segment of Z, the ratio between the hydrophilic and hydrophobic segments can be finely adjusted, so that the ion exchange capacity of the sulfonation copolymerization can be more effectively controlled and handled for correctly building different products with different performance levels. By fine-tuning the weight ratio of the hydrophilic segments and hydrophobic segments, the values of IEC of each batch of the polymers produced by post-sulfonation can be controlled in fixed values respectively, so the copolymers have the characteristics of good mechanical properties, excellent film dimensional stabilities, good proton conductivities and controllable ion exchange capacities. For example, when the polyphenyl ring monomer x is dihalogen or diol monomer having an equivalent ratio of 1, the polyphenyl ring monomers y and z are diol or dihalogen monomers and the sum of the equivalent ratio of y and z is also 1; when the polyphenyl ring monomer y is dihalogen or diol monomer and the equivalent ratio is 1, the polyphenyl ring monomers x and z are diol or dihalogen monomers and the sum of the equivalent ratio of x and z is also 1, depending on whether the monomers are dihalogen or diol monomers to be used for the structural design. The equivalent ratios of x, y and z are respectively not equal to 0.

[0022] As shown in FIG. 1, the polyphenyl ring monomers x, y, and z can be dihalogen monomers or diol monomers, through nucleophilic polycondensation reaction and post-sulfonation reaction, the sulfonated polyphenylene (phenylene) ether random copolymer can be obtained, if the number of repeating units at the hydrophilic segment is n, then the number of repeating units at the hydrophobic segment is 1-n.

[0023] Table 1 is a comparison table of various polymers in terms of equivalent ratios of polyphenyl ring monomers x, y, z, weight average molecular weight (Mw) and dispersity index (PDI) of the polymers according with the present invention.

TABLE-US-00001 TABLE 1 Polymer (sample) x y z Mw(kDa) PDI RA6F-0.5 1 0.5 0.5 198.4 2.55 RA6F-0.4 1 0.4 0.6 214.7 2.34 RA6F-0.3 1 0.3 0.7 200.8 2.47 RA6F-0.2 1 0.2 0.8 221.1 2.15 RA6F-0.1 1 0.1 0.9 230.6 2.82

[0024] Table 2 is a comparison table of ion exchange capacities (IEC), water absorption rates (Water Uptake) and elongations (L) of various membranes respectively made by the polymers in table 1.

TABLE-US-00002 TABLE 2 Membrane Water Uptake (%) L(%) (sample) IEC.sup.a(mmol/g) 30 C. 80 C. 30 C. 80 C. SRA6F-0.5 3.46 34 88 15 50 SRA6F-0.4 3.30 31 80 13 46 SRA6F-0.3 3.13 25 64 13 37 SRA6F-0.2 2.95 23 56 11 31 SRA6F-0.1 2.76 20 40 10 26

[0025] Table 3 is a comparison table of the thermal cracking temperature (T.sub.d), Young's modulus (GPa), tensile strength (MPa) and elongation at break of various membranes according with the present invention corresponding to the samples in tables 1 and 2.

TABLE-US-00003 TABLE 3 Tensile Elongation Membrane T.sub.d 5% Young's Strength at break (sample) ( C.) Modulus (GPa) (MPa) (%) RA6F-0.5 576 1.32 85.7 15 RA6F-0.4 570 1.12 79.8 19 RA6F-0.3 555 0.84 66.3 27 RA6F-0.2 540 0.76 54.6 31 RA6F-0.1 531 0.70 44.2 35 SRA6F-0.5 245 0.75 66.2 42 SRA6F-0.4 247 0.64 57.2 57 SRA6F-0.3 249 0.48 50.4 77 SRA6F-0.2 250 0.42 43.1 88 SRA6F-0.1 252 0.38 30.5 102

[0026] Table 4 is a comparison table of the proton conductivity of Nafion 211 Membrane with respect to various sulfonated polymer Membranes according with the present invention corresponding to the samples in table 2.

TABLE-US-00004 TABLE 4 Sulfonated Polymer Proton conductivity (80 C.)(mS/cm) sample) 40% 60% 80% 95% SRA6F-0.5 27 88 170 201 SRA6F-0.4 24 83 163 190 SRA6F-0.3 22 75 154 177 SRA6F-0.2 20 67 142 166 SRA6F-0.1 17 58 130 155 Nafion 211 20 40 90 90

[0027] Table 5 is a comparison table of the proton conductivity of SP1 with respect to various sulfonated polymers according with the present invention corresponding to the samples in table 2. Table 5 shows that the efficiency of samples 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) are all better than that of the control group SP1 (IEC=3.27 mmol/g, 172 mS/cm). The efficiency of samples SRA6F-0.2 (IEC=2.95 mmol/g, 166 mS/cm) and SRA6F-0.1 (IEC=2.76 mmol/g, 155 mS/cm) is slightly lower than that of the control group SP1 due to their low conductivity. This proves that the present invention uses three polyphenyl ring monomers x, y, and z with different structures to form the sulfonated polyphenylene (phenylene) ether random copolymer through nucleophilic polycondensation reaction and regulates the polymerization ratios of the monomers. After the sulfonation reaction, a certain polymer with a specific controlled ratio of hydrophilic and hydrophobic segments is formed. By regulating the polymerization ratio, the hydrophilic and hydrophobic segments of the polymer can be effectively fine-tuned/controlled, so that the polymer of the present invention in the implementation case can have a higher conductivity when the IEC is similar to that of the control group SP1, and the efficiency of the fuel cell is about 10% higher than that of the control group.

TABLE-US-00005 TABLE 5 Power Density Sample Voltage(V) Current(mA/cm.sup.2) (mW/cm.sup.2) SRA6F-0.5 0.4256 2800 1191.8 SRA6F-0.4 0.4111 2800 1151.1 SRA6F-0.3 0.4066 2800 1138.6 SRA6F-0.2 0.4120 2600 1071.2 SRA6F-0.1 0.3830 2400 919.3 SP1 0.4042 2800 1130.2

[0028] Therefore, through the detailed description of the above specific embodiments, the present invention does have the following advantages: a) The present invention can indeed prepare a polyphenyl polymer having a hydrophilic part and dense sulfonic acid side chains, and multiple sulfonic acid groups are substituted in a specific part of the polymer, when the polyphenyl polymer is made into a polymer membrane, the polyphenyl structure can indeed impart strong mechanical properties and maintain good dimensional stability when in contact with water for a long time; b) the sulfonated polyphenylene (phenylene) ether random copolymer prepared by the present invention can indeed be used as the materials for producing proton exchange membranes, and based on the method of the present invention to prepare the above-mentioned sulfonated polyphenylene (phenylene) ether random copolymer, and according to the above-mentioned characteristics of the sulfonated polyphenylene ionomer, the proton exchange membranes have low cost and can be effectively controlled their ion exchange capacity, so it has a good application prospect in electrochemical energy conversion devices, such as fuel cells, water electrolysis membranes, and liquid flow cells; c) the novel sulfonated polyphenylene (phenylene) ether random copolymers of the present invention, and preparation method thereof, can be prepared as products as proton exchange membranes (PEMs), coating solutions and electrodes for applying to hydrogen fuel cells, direct methanol fuel cells and membrane electrodes, and d) the method of the present invention is suitable for producing sulfonated polymer compositions and synthetic polymer composition for applying to polymer electrolyte membranes, electrodes and membrane electrode assemblies of fuel cells, electrolytic cells, and electrolyte membranes for dialysis and ultrafiltration equipment.

[0029] While we have shown and described the embodiment in accordance with the present invention, it should be clear to those skilled in the art that further embodiments may be made without departing from the scope of the present invention.