WO2009038268A1

WO2009038268A1 - Sulfonated poly(arylene ether), method of manufacturing the same, and crosslinked polymer electrolyte membrane using the same

Info

Publication number: WO2009038268A1
Application number: PCT/KR2008/002712
Authority: WO
Inventors: Jae-Suk Lee; Kwan-Soo Lee; Myung-Hwan Jeong
Original assignee: Gwangju Institute Of Science And Technology
Priority date: 2007-09-21
Filing date: 2008-05-15
Publication date: 2009-03-26
Also published as: KR20090031107A; KR100954060B1

Abstract

A crosslinked sulfonated polyCarylene ether) copolymer, a method of preparing the same and a polymer electrolyte membrane using the same are provided. The sulfonated polyCarylene ether) copolymer is synthesized by polycondensation of a dihalide monomer and a dihydroxy monomer having a sulfonate group or a dihydroxy monomer and a dihalide monomer having a sulfonate group. In addition, polymers are crosslinked by polycondensation between crossl inkable monohydroxy monomers. Thus, the copolymer and membrane have thermal stability, mechanical stability, chemical stability and film- forming capacity equal to or higher than a conventional sulfonated ρoly(arylene ether) copolymer or a commercially available polymer electrolyte membrane, i.e., a nafion film, and also have further improved proton conductivity and cell performance. Moreover, the polymer electrolyte membrane does not have any change in characteristics even though it is exposed to moisture for a long time.

Description

[DESCRIPTION] [Invention Title]

SULFONATED POLY(ARYLENE ETHER), METHOD OF MANUFACTURING THE SAME, AND CROSSLINKED POLYMER ELECTROLYTE MEMBRANE USING THE SAME [Technical Field]

<i> The present invention relates to a sulfonated poly(arylene ether) copolymer, a method of preparing the same, and a polymer electrolyte membrane using the same, and more particularly, to a sulfonated polyCarylene ether) copolymer having a crossl inked structure, a method of preparing the same, and a crossl inked polymer electrolyte membrane using the same. [Background Art]

<2> A fuel cell is an electrical energy conversion system that converts chemical energy into electrical energy through an electrochemical reaction. While the fuel cell had only limited applications in the 1960s, such as in Gemini aircraft, it is currently considered as an alternative energy source and answer to increased demand for electricity, and thus is being actively researched all over the world.

<3> Particularly, on the verge of new regulations of carbon-dioxide emissions required by Green Round (Climate Change Agreement), and new regulations of automobile emissions in the form of low pollution requirements for all new automobile sales, automobile companies around the world are hurrying to develop pollution-free automobiles such as fuel cell cars. Also, the fuel cell can be readily applied as a power source in remote locations and in certain military applications such as submarines and mobile communications. The fuel cell does not store electricity, but is a more efficient power generating device than a conventional internal-combust ion engine. Also, the fuel cell, a clean, efficient power generating device, has nearly no emission of environmentally harmful materials such as sulfur oxide (SOx) and nitrogen oxide (NOx), and thus is expected to help solve recent environmental problems caused by use of fossil-based fuel.

<4> A polymer electrolyte has been studied and used as a proton exchange resin or proton exchange membrane in a fuel cell for several decades. Recent studies have focused on using the proton exchange membrane as a mediator delivering protons used for a direct methanol fuel cell (DMFC) or a polymer electrolyte membrane fuel cell (PEMFC; a polymer electrolyte membrane fuel cell, a solid polymer electrolyte fuel cell, a solid polymer fuel cell or a proton exchange membrane fuel cell). <5> One of the widely used proton exchange membranes in the current fuel

TM cell industry is a Nafion film, which is formed of a polymer containing a perflourinated sulfonic acid group developed by DuPont (USA). When water

TM saturated, the Nafion film has an ionic conductivity of 0.1 S/cm, excellent mechanical strength and chemical resistance, and stable performance as an electrolyte membrane enough to be applied to an automobile fuel cell. Similar types of commercially-available membranes include the Acipleχ-S membrane (Asahi Chemicals), the Dow membrane (Dow Chemicals), the Flemion membrane (Asahi Glass), and the GoreSelect membrane (Gore & Associate), and an α- or J3 -polyunsaturated polymer is being developed by BaI lard Power Systems (Canada).

<6> However, these membranes are difficult to mass-produce because of high costs and complicated synthesis methods. And, they have limited applications due to less efficient characteristics when used as a proton exchange membrane, such as methanol crossover occurring in an electrical energy system like the direct methanol fuel cell, and low proton conductivity at both high and low temperatures.

<7> To make up for these shortcomings, a great deal of research has focused on non-fluorinated and partial ly-fluorinated proton exchange membranes, which include sulfonated poly(phenylene oxides), poly(phenylene sulfides), polysulfonates, poly(para-phenylenes), polystyrenes, polyetheresterketones, and polyimides.

<8> However, when the membranes are sulfonated beyond a critical concentration since their ionic conductivities are directly proportional to their degree of sulfonation, their molecular weight unavoidably decreases, and they cannot be used over a long period of time due to deterioration of their mechanical properties during hydration. To overcome these problems, a method of preparing a polymer using a sulfonated monomer and a method of selectively sulfonating a polymer are being developed [U.S. Patent Nos. 5468574, 5679482 and 6110616], but these methods also cannot achieve high temperature stability, nor can they completely overcome potential problems caused by long-term use.

<9> Meanwhile, U.S. Patent Application No. 6245881 discloses various methods of preparing a sulfonated polyimide such as a method using a diamine monomer containing a sulfonic acid group, and directly sulfonation a polyimide main chain. The sulfonated polyimide exhibits very higher thermal stability and oxidative and reductive stabilities compared to a conventional proton conductive polymeric material.

<io> However, when a polymer is selectively sulfonated to form a sulfonated polyimide, its mechanical strength is reduced. And when a sulfonated polyimide is prepared using a sulfonic acid diamine monomer, its solubility is lowered, thus it does not have good reactivity and facilitate film formation.

<π> Therefore, there is need of a new material that exhibits excellent electrochemical characteristics, high-temperature stability, and can be formed as a thin film. [Disclosure] [Technical Problem]

<i2> The present invention is directed to a sulfonated poly(arylene ether) copolymer having a crossl inked structure.

<i3> The present invention is also directed to a crossl inked polymer electrolyte membrane formed using the sulfonated polyCarylene ether) copolymer. [Technical Solution]

<i4> One aspect of the present invention provides a sulfonated poly(arylene ether) copolymer having a crosslinkable moiety at an end, represented by the following formula.

CMl-K-O-SAr-O-Ar24-/-fO-ArI-O-Ar2-)^CM2 <15> L ^{K S}Jn

<16> In this formula, SAr is a sulfonated aromatic group, and ArI and Ar2 are unsulfonated aromatic groups. Further, CMl and CM2 are crosslinkable moieties. Herein, k has a range of 0.001 to 1, s is 1-k, and n is an integer from 10 to 500 indicating the number of a repeating units.

<i7> Another aspect of the present invention provides a sulfonated poly(arylene ether) copolymer having a crosslinkable moiety at an end, represented by another formula.

CMl^fθ-Ar2-O-SAr-)^-/-fθ-Ar2-O~Arl-)—1— CM2 <₁8> L K ^SJn

<19> In this formula, SAr is a sulfonated aromatic group, and ArI and Ar2 are unsulfonated aromatic groups. Further, CMl and CM2 are crosslinkable moieties. Herein, k has a range of 0.001 to 1, s is 1-k, and n is an integer from 10 to 500 indicating the number of a repeating units.

<20> Still another aspect of the present invention provides a crossl inked polymer electrolyte membrane, which is formed by annealing the sulfonated poly(arylene ether) copolymer obtained above. [Advantageous Effects]

<2i> According to the present invention, a polymer electrolyte membrane using a sulfonated polyCarylene ether) copolymer having a crosslinkable structure exhibits equivalent or superior thermal stability, mechanical stability, chemical stability and membrane forming capability compared to conventional polymer electrolyte membranes. In addition, the inventive membrane shows remarkably improved proton conductivity and cell performance, its characteristics are unaffected even when it is exposed to moisture for a long period of time, and it can be applied to a fuel cell or a secondary battery. [Description of Drawings] 1 19

<22> FIG. 1 shows H-NMR and F-NMR spectra of sulfonated poly(arylene ether) copolymers having crossl inked structures (E-SFQK-6Fs).

1 19

<23> FIG. 2 shows H-NMR and F-NMR spectra of sulfonated poly(arylene ether) copolymers having crossl inked structures (E-SFQK-BPs).

1 19

<24> FIG. 3 shows H-NMR and F-NMR spectra of sulfonated poly(arylene ether) copolymers having crossl inked structures (E-SFQK-HQs).

1 19

<25> FIG. 4 shows H-NMR and F-NMR spectra of sulfonated poly(arylene ether) copolymers having crosslinked structures (E-SFQK-6Hs) .

1 19

<26> FIG. 5 shows H-NMR and F-NMR spectra of sulfonated poly(arylene ether) copolymers having crosslinked structures (E-SFQK-DPEs).

<27> FIG. 6 shows H-NMR spectrumsspectra of sulfonated poly(arylene ether) copolymers having crosslinked structures (E^~SFQK-6Fs) . <28> FIG. 7 shows FT-IR spectrumsspectra of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH~6Fs). <29> FIG. 8 shows FT-IR spectrumsspectra of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-BPs). <30> FIG. 9 shows glass transition temperatures (Tg) and decomposition temperatures (Td) of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-6Fs). <3i> FIG. 10 shows glass transition temperatures (Tg) and decomposition temperatures (Td) of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-BPs). <32> FIG. 11 shows glass transition temperatures (Tg) and decomposition temperatures (Td) of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-HQs). <33> FIG. 12 shows glass transition temperatures (Tg) and decomposition temperatures (Td) of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-DPEs). <34> FIG. 13 shows glass transition temperatures (Tg) and decomposition temperatures (Td) of sulfonated poly(arylene ether) copolymers having crosslinked structures (CSFQH-6Hs).

<35> FIG. 14 shows a photograph of crossl inked polymer electrolyte membrane. [Mode for Invention]

<36> Hereinafter, embodiments of the present invention will be described in detai 1.

<37> Embodimerit 1 <38> A sulfonated poly(arylene ether) copolymer according to the present embodiment has a crossl inked structure. The sulfonated poly(arylene ether) copolymer is represented by Formula 1.

<39> [Formula 1]

CMl-H-O-SAr-O-Ar2-)p/-fθ-ArI-O-Ar2-)4- CM2

<40> <41> In Formula 1, SAr is a sulfonated aromatic group, which includes

SO₃ M

<42> In addition, ArI and Ar2 are unsulfonated aromatic groups, which may be the same as or different from each other.

<43> The ArI and Ar 2 are

or

<44> Y is a carbon-to-carbon single bond, -Q-, -S-,

/=V^A~

-A-

\_J \ //

, AA is a carbon-to-carbon single bond, -Q-, -S-, -s—

, and E is H, F, C1~C5 or

A-

-A-

<45> Here, in Y, denotes a benzene structure having ortho, A— meta or para-substituted connecting moieties, and ^~A V—/ denotes a fully fluorine-substituted benzene structure having ortho, meta or para-

A- substituted connecting moieties. That is, ^^~^ ^^ denotes fully

F F A F

fluorine-substituted benzene structures having ortho- ( ),

meta-(

) substituted connecting moieties. In addition, in E, H denotes hydrogen, F denotes fluorine, Cl~ C5 denote hydrogen- or fluorine-substituted alkyl structures

having 1 to 5 carbon atoms, respectively, and

denotes an L- substituted benzene structure. In the above structural formula, L is H, F or Cl to C5, H is hydrogen, F is fluorine, and Cl to C5 denote hydrogen- or fluorine-substituted alky structures having 1 to 5 carbon atoms. <46> In addition, Z denotes a bond directly attached to carbon of benzene

and - SO₃ M ,

, , or , which may be connected

at an ortho, meta or para position. In Z, Y is the same as described above.

+ <47> M is a counter ion having a positive charge, and may be a potassium

ion (K), a sodium ion (Na) or an alkyl ammonium ion (NR4), and preferably, a potassium ion or a sodium ion. <48> CMl and CM2 denotes a crossl inkable moieties, which are independently

)

or vinyl part ((R= ), which is substituted with Rl, or ^v , and may positioned at ortho, meta or para position. In R, G is a carbon-to-

carbon single bond, -Q-, -S- or

, and Rl is H, F, Cl to C5 or

In Rl, H denotes hydrogen, F denotes fluorine, Cl to C5 denote hydrogen- or fluorine-substituted alkyl structures having 1 to 5 carbon

^{^}R2 atoms, and denotes benzene ring having ortho, meta or para- substituted R2. Here, R2 is H, X or Cl ~ C5. In R2, H denotes hydrogen, Cl to C5 denote hydrogen- or fluorine-substituted alkyl structures having 1 to 5 carbon atoms, and X denotes a halogen atom (F, Cl or Br), which is a functional group enabling polymerization with a hydroxyl group of another polymer chain. Also, in Formula 1, k ranges from 0.001 to 1.000, s has a value of 1-k. And n is an integer, ranging from 10 to 500, indicating the number of repeating units in a polymer.

<49> A method of manufacturing the sulfonated poly(ethylene ether) copolymer represented by Formula 1 is prepared by the following Reaction Scheme 1, which will be described in detail.

<50> [Reaction Scheme 1]

<5i> k HO-SAr-OH + s HO-ArI-OH + m X-Ar2-X

<52> [Formul a 2]

(-O-SAr-O- Ar2-)r-/-fθ- ArI-O- Ar2-)— ]—

<53> L ^{k S J n}

<54> [Formula 3]

HO- X-

D R

<55> ^κ or

<56> [Formula 1]

CMl-H-O-SAr-O-Ar2-V-/-fO-ArI-O-Ar2-)—I— CM2

<57> ^{L k sJn}

<58> Reaction Scheme 1 shows a mechanism for preparing a polymer of Formula 1 by polycondensation, in which monomers participating in the reaction may vary. Here, a sulfonated monomer used in Reaction Scheme 1 is a dihydroxy monomer .

<59> The sulfonated poly(arylene ether) copolymer having a crossl inking moiety may be prepared by Reaction Scheme 1.

<60> In Reaction Scheme 1, k ranges from 0.001 to 1, s is 1-k, and (k+s)/m ranges from 0.800 to 1.200. Also, k, s and m independently denote mole fractions of monomers participating in the reaction.

<6i> Here, a compound of Formula 3 may be divided into a hydroxy-substituted HO-< -J X- monomer ( ^κ ) and a hal ide-subst ituted monomer ( ). In

Reaction Scheme 1, when (k+s)/m is 1.000 or less, the hydroxy1-subst ituted monomer may be used, and when (k+s)/m is more than 1.000, the halide- subst ituted monomer may be used. When R2 is X in the compound of Formula 3,

the hydroxy1-substituted monomer (

) may be used regardless of the value of (k+s)/m.

<62> In the preparation process of Reaction Scheme 1, a sulfonated dihydroxy monomer and an unsulfonated dihydroxy monomer are activated to facilitate polycondensation of the dihydroxy monomer with the dihalide monomer. Also, the unsulfonated dihalide monomer can be added together with the dihydroxy monomer in the same step of the manufacturing process.

<63> First, in the presence of a solvent mixture consisting of a base, an azeotropic solvent and an aprotic polar solvent, the polycondensation reaction is performed at 0 to 300^°C for 1 to 100 hours to give a polymer of Formula 2. Also, according to the type of manufacturing process, a protic polar solvent may be used instead of the aprotic polar solvent.

<64> Subsequently, the crosslinking moiety-substituted polymer of Formula 1 is prepared using the polymer of Formula 2, and the hydroxyl- or hal ide- subst ituted monomer of Formula 3.

<65> A preparation process for the compound of Formula 1 is the same as that for the polymer of Formula 2. That is, the crosslinkable moiety-substituted polymer of Formula 1 is prepared by activation and polycondensation. Also, removal of the azeotropic solvent may be further included after activation and before the polycondensation.

<66> Further, in the present embodiment, the sulfonated polyCarylene ether) copolymer having a crosslinkable moiety of Formula 1 is prepared by substitution of a crosslinkable moiety (CM) 1 or CM2 having a crosslinking group enabling thermal crosslinking to a polymer chain through polycondensation to give improved thermal stability, electrochemical characteristics, film-forming capacity, dimensional stability, mechanical stability, chemical characteristics, physical properties and cell performance to the polymer represented by Formula 2.

<67> In the polycondensat ion and crossl inking group introduction for preparing the sulfonated poly(arylene ether) copolymer having a crossl inkable moiety, a base is used, which includes an inorganic base selected from the group consisting of a hydroxide of alkali metal or alkali earth metal, carbonate and sulfonate, and an organic base selected from the group consisting of general amines including ammonia, may be used as a base.

<68> Also, an aprotic or protic polar solvent may be used as the reaction solvent. The aprotic polar solvent may include N-methylpyrolidone (NMP), dimethyl formamide (DMF), N,N-dimethylacetamide (DMAc) and dimethyl sulfoxide (DMSO), and the protic polar solvent may include methylene chloride (CH2CI2), chloroform (CH₃Cl) and tetrahydrofuran (THF). The azeotropic solvent may include benzene, toluene and xylene.

<69> The sulfonated poly(arylene ether) copolymer having a crossl inkable moiety prepared by the above described method exhibits equivalent or superior thermal stability, film-forming capacity, mechanical stability, chemical characteristics, physical properties and cell performance compared to the conventional sulfonated poly(arylene ether) copolymer or Nafion film that is commercially available as a polymer electrolyte membrane. It also exhibits remarkably improved electrochemical characteristics, and particularly, proton conductivity and cell performance, and also high dimensional stability. Further, its characteristics are unaffected even when the membrane is exposed to moisture over a long period of time.

<70> The present invention will now be described in more detail with reference to Preparation Examples, however its scope is not limited thereto.

<7i> Preparation Example 1: Synthesis of sulfonated poly(arylene ether) copolymer having a crossl inkable moiety (E-SFQK-6F)

<72> [Reaction Scheme 2] KJCOJ k F „0 *

<74> <75> Prepared was a 100ml two-necked round-bottom flask connected with a stirrer, a nitrogen gas inlet, a magnetic stir bar and a Dean-Stark (azeotropic distillation) device. Therein, hydroquinonesulfonic acid potassium salt and (4,4'-hexafluoroisopropyIidene)diphenol were mixed in a molar ratio of 19:1 mmol (k:s=0.95:0.05) , and then K₂CO₃ (equivalent ratio of

1.15), N,N-dimethylacetamide (DMAc; 60ml) and benzene (20ml) were added.

<76> Activation was performed at 135 to 140"C for 6 to 8 hours, and water generated as a byproduct in the reaction was removed by azeotropic distillation using benzene, one of the reaction solvents, which was removed from the reactor after the activation step.

<77> Then, 20mmol of decaf1uorobiphenyl was added to the reactor and maintained at 140^°C for more than 12 hours to give an intermediate compound at 140°C for at least 20 hours.

<78> 3-ethynyl phenol was added with an amount corresponding to a 0.2 to 0.5 times the molar ratio than a of decafluorobiphenyl monomer, together with benzene (10ml) and K2CO3 (equivalent ratio of 1.15), in the solution having the intermediate compound, and maintained for at least 6 hours at 140°C , and then benzene was completely removed. Also, water, the byproduct generated from the reaction, was removed by azeotropic distillation with benzene. Afterward, the resulting product was precipitated with 500ml ethanol, washed with water and ethanol several times, and vacuum-dried at 60^°C for 3 days. The final product (E-SFQK95-6F) was obtained as a light brown solid with a yield of 90% or more.

<79> Also, sulfonated polyCarylene ether) copolymers having crossl inking moiety were independently prepared using starting materials, including hydroquinonesulfonic acid potassium salt and 4,4'- (hexafluoroisopropylidiene)diphenol , in various molar ratios of lδmmo1 :2mmo1 (k:s=0.9:0.1), 17mmol:3mmol (k:s=0.85:0.15), 16mmo1 :4mmo1 (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol:8mmol (k:s=0.6:0.4), lOmmol :10mmol (k:s=0.5:0.5), 8mmol:12mmol (k:s=0.4:0.6) and 6mmo1 : 14mmo1 (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<80> The polyCarylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-6F, E-SFQK90-6F, E-SFQK85-6F, E-SFQK80- 6F, E-SFQK75-6F, E-SFQK70-6F, E-SFQK60-6F, E-SFQK50-6F, E-SFQK40-6F and E- SFQK30-6F.

<81>

<82> Preparation Example 2: Preparation of sulfonated polyCarylene ether) copolymer having a crossl inkable moiety (E-SFQK-BP) <83> [Reaction Scheme 3]

zerae

<85> Reaction Scheme 3 was performed by the same method as Preparation Example 1 using 4,4'-biphenol as a starting material instead of (4,4'- (hexaf1uoroisopropyIidene)diphenol . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'-biphenol as starting materials in various molar ratios of 19mmol:lmmol (k:s=0.95:0.05) , 18mmol:2mmol (k:s=0.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), 16mmol:4mmol (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol:8mmol (k:s=0.6:0.4), lOmmol :lOmmol (k:s=0.5:0.5), 8mmol:l2mmol (k:s=0.4:0.6) , and βmmol :l4mmol (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<86> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-BP, E-SFQK90-BP, E-SFQK85-BP, E-SFQK80- BP, E-SFQK75-BP, E-SFQK70-BP, E-SFQK60-BP, E-SFQK50-BP, E-SFQK40-BP and E- SFQK30-BP.

<87> <88> Preparation Example 3: Preparation of sulfonated poly(arylene ether) copolymer having a cross l inkable moi ety (E-SFQK-HQ)

<89> [React ion Scheme 4]

fe

<91 > Reaction Scheme 4 was performed by the same method as Preparation Example 1 using hydroquinone as a starting material instead of (4,4'- hexafluoroisopropyIidene)diphenol . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using the starting materials, that is hydroquinonesulfonic acid potassium salt and hydroquinone as initial materials in various molar ratios of 19mmo1 : lmmo1 (k:s=0.95:0.05), 18mmol:2mmol (k:s=0.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), lβmmo1 :4mmo1 (k:s=0.8:0.2), lδmmol :5mmol (k:s=0.75:0.25) , 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol:8mmol (k:s=0.6:0.4), lOmmo1 : lOmmo1 (k:s=0.5:0.5), 8mmo1 : 12mmo1 (k:s=0.4:0.6) and 6mmo1 : 14mmo1 (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<92> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-HQ, E-SFQK90- HQ, E-SFQK85-HQ, E-SFQK80- HQ, E-SFQK75-HQ, E-SFQK70-HQ, E-SFQK60-HQ, E-SFQK50-HQ, E-SFQK40-HQ and E- SFQK30-HQ. <93> <94> Preparation Example 4: Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SFQK-6H)

<9^> [Reaction Scheme 5]

It

<97> Reaction Scheme 5 was performed by the same method as Preparation Example 1 using bisphenol-A as a starting material instead of (4,4'- hexafluoroisopropylidene)diphenol . Sulfonated polyCarylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and bisphenol-A as starting materials in various molar ratios of 19mmol:lmmol (k:s=0.95:0.05), 18mmol:2mmol (k:s=0.9:0.1), 17mraol :3mmol (k:s=0.85:0.15), 16mmol:4mmol (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmol:6mmol (k:s=0.7:0.3), 12mmol:8mmol (k:s=0.6:0.4), lOmmol :lOmmol (k:s=0.5:0.5), 8mmo1 : 12mmo1 (k:s=0.4:0.6) and 6mmo1 : 14mmo1 (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<98> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-6H, E-SFQK90-6H, E-SFQK85-6H, E-SFQK80- 6H, E-SFQK75-6H, E-SFQK70-6H, E-SFQK60-6H, E-SFQK50-6H, E-SFQK40-6H and E- SFQK30-6H. <99> <10()> Preparation Example 5: Preparation of sulfonated poly(arylene ether) copolymer having a crossl inkable moiety (E-SFQK-2BP)

<101> [Reaction Scheme 6J

t Benzene

<l O3> Reaction Scheme 6 was performed by the same method as Preparation Example 1 using 2,2'-biphenol as a starting material instead of (4,4'- hexafluoroisopropyIidene)diphenol . Sulfonated poly(arylene ether) copolymers having crossl inkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 2,2'-biphenol as starting materials in various molar ratios of 19mmol:lmmol (k:s=0.95:0.05), lδmmol :2mmol (k:s=0.9:0.1), 17mmol:3mmol (k:s=0.85:0.15) , lδmmo1 :4inmo1 (k:s=0.8:0.2), lδmmol :5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol :8mmol (k:s=0.6:0.4), 10mmol:l0mmol (k:s=0.5:0.5), 8mmo1 : 12mmo1 (k:s=0.4:0.6) and ^βmmo1 : 14mmo1 (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<104> The polyCarylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-2BP, E-SFQK90-2BP, E-SFQK85-2BP, E- SFQK80-2BP, E-SFQK75-2BP, E-SFQK70-2BP, E-SFQK60-2BP, E-SFQK50-2BP, E-SFQK40- 2BP and E-SFQK30-2BP. <105> < I ()6> Preparation Example 6: Preparation of sulfonated poly(arylene ether) copolymer having a crossl inkable moiety (E-SFQK-DPE)

<107> [Reaction Scheme 7]

/ ββnzβπβ

<lO9> Reaction Scheme 7 was performed by the same method as Preparation Example 1 using 4,4'-dihydroxydiphenyl ether as a starting material instead of (4,4'-hexafluoroisopropylidene)diphenol . Sulfonated poly(arylene ether) copolymers having crossl inkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4, 4'-dihydroxydiphenyl ether as starting materials in various molar ratios of 19mmol ^lmmol (k:s=0.95:0.05), 18mmol:2mmol (k:s=0.9:0.1), 17mmol :3mmol (k:s=0.85:0.15), 16mmo1 :4mmo1 (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol:8mmol (k:s=0.6:0.4), lOmmo1 : lOmmo1 (k:s=0.5:0.5), 8mmo1 : 12mmo1 (k:s=0.4:0.6) and 6mmol:14mmol (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<l lθ> The polyCarylene ether) copolymers prepared with various ratios of k to s were independently named E-SFQK95-DPE, E-SFQK90-DPE, E-SFQK85-DPE, E- SFQK80-DPE, E-SFQK75-DPE, E-SFQK70-DPE, E-SFQK60-DPE, E-SFQK50-DPE, E-SFQK40- DPE and E-SFQK30-DPE.

<1 12> Preparation Example !^'• Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SPECN-HQ)

<1 13> [Reaction Scheme 8]

<ll5> Reaction Scheme 8 was performed by the same method as Preparation Example 1 using hydroquinone as a starting material instead of (4,4'— hexaf1uoroisopropyIidene)diphenol , and 2,6-difluorobenzonitri Ie as a dihalide material instead of decafluorobiphenyl .

<116> Further, instead of DMAc and benzene, dimethylsulfoxide (DMSO; 60ml) and toluene (20ml) was added as a reaction solvent. Activation was performed at 150 to 160^°C and maintained at 170"C . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and hydroquinone as starting materials in various molar ratios of 20mmol:0mmol (k:s=1.00:0), 19mmol:lmmol (k:s=0.95:0.05), 18mmo1 :2mmo1 (k:s=O.9:0.1), 17mmol :3mmol (k:s=0.85:0.15), 16mmol:4mmol (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol :8mmol (k:s=0.6:0.4), lOmmol :10mmol (k:s=0.4:0.5) and 8mmo1 : 12mmo1 (k:s=0.3^'0.7) . Each product was obtained with a yield of at least 90%.

<I17> The poly(arylene ether) copolymers prepared with various rations of k to s were independently named E-SPECN100-HQ, E-SPECN95-HQ, E-SPECN90-HQ, E- SPECN85-HQ, E-SPECN80-HQ, E-SPECN75-HQ, E-SPECN70-HQ, E-SPECN60-HQ, E- SPECN50-HQ and E-SPECN40-HQ.

<I18> <119> Preparation Example 8: Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SPEK-6F)

<120> [Reaction Scheme 9]

_ O 14D C₁ 6 hrs , i aθ X 24 hre k + S HO— ~OH ^_

CF^ K_jCO₅ DMSO . Toluene

HO OH

S O, Na

HO

O CF₅

O ' C I O O

140 X, 6 hre k KyCO_' DMSO , Toluene

SO₄Kb

O

, Q C O k ^*

<121> <122> Prepared was a 100ml two-necked round-bottom flask connected with a stirrer, a nitrogen gas inlet, a magnetic stir bar and a Dean-Stark (azeotropic distillation) device. Therein, 2,3-dihydroxynaphthalene-6- sulfonic acid monosodium salt and 4,4'-hexafluoroisopropylidene)diphenol were mixed in a molar ratio of 12:8 mmol Ck^s=O.6:0.4) , and added together with K₂CO₃ (equivalent ratio of 1.15), N,N-dimethylsulfoxide (DMSO; 60ml) and toluene (20ml). <123> Activation was performed at 135 to 140⁰C for 6 to 8 hours, and water generated as a byproduct in the reaction was removed by azeotropic distillation with toluene, one of the reaction solvents, which was removed from a reaction after the reactor.

<124> Then, 20 mmol of 4,4' —di fluorobenzophenone was added to the reactor and maintained at 180^°C for at least 12 hours to produce an intermediate compound.

<125> 3-ethynyl phenol was added with an amount corresponding to 0.2 to 0.5 times the mole ratio of 4,4' —di fluorobenzophenone monomer in the polymer solution including the intermediate compound, together with benzene (10ml) and K₂CO₃ (equivalent ratio of 1.15) for at least 6 hours at 140^°C, and then toluene was completely removed. Also, water, the byproduct, was removed by azeotropic distillation with toluene. Afterward, the resulting product was precipitated with 500ml ethanol, washed with water and ethanol several times, and vacuum-dried at 60^°C for 3 days. The final product (E-SPEK60-6F) was obtained as a light brown solid with a yield of at least 90% or more.

<126> Also, sulfonated poly(arylene ether) copolymers having crossl inked structures were prepared using 2,3-dihydroxynaphthalene-6-sulfonic acid monosodium salt and 4,4'-(hexafluoroisopropylidene)diphenol as starting materials in various molar ratios of 19mmo1 : lmmo1 (k:s=0.95:0.05), 18mmol:2mmol (k:s=0.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), lβramol :4mmol (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), lOmmoiαOmmol (k:s=0.5:0.5), 8mmol:l2mmol (k: s=0.4:0.6) and 6mmol :14mmol (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<127> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPEK95-6F, E-SPEK90-6F, E-SPEK85-6F, E-SPEK80- 6F, E-SPEK75-6F, E-SPEK70-6F, E-SPEK60-6F, E-SPEK50-6F, E-SPEK40-6F and E- SPEK30-6F.

<128>

<129> Preparation Example 9: Preparation of sulfonated poly(arylene ether) copolymer having a crossl inkable moiety (E-SPEK-BP) < 130> [Reaction Scheme 10]

24 hre

hre

, Toluene

<13 1 > <132> Reaction Scheme 10 was performed by the same method as Preparation Example 1 using 4,4'-biphenol as a starting material instead of (4,4'- hexafluoroisopropylidene)diphenol . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using 2,3-dihydroxynaphthalene-6- sulfonic acid monosodium salt and 4,4'-biphenol as starting materials in various molar ratios of 19mmol :lmmol(k:s=0.95:0.05), lδmmol :2mmol (k:s=O.9:0.1), 17mmol :3mmol (k:s=0.85:0.15), 16mmol:4mmol (k:s=0.8:0.2), lδmmol :5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmo1 :8mmo1 (k:s=0.6:0.4), lOmmol :lOmmol (k:s=0.5:0.5), 8mmol:l2mmol (k:s=0.4:0.6) and 6mmo1 : 14mmo1 (k:s=0.3:0.7). Each product was obtained with a yield of at least 90%.

<133> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPEK95-BP, E-SPEK90-BP, E-SPEK85-BP, E-SPEK80- BP, E-SPEK75-BP, E-SPEK70-BP, E-SPEK60-BP, E-SPEK50-BP, E-SPEK40-BP and E- SPEK30-BP.

<134> <135> Preparat ion Example 10 : Preparat i on of sul fonated poly(arylene ether ) copolymer having a cross l inkabl e moi ety (E-SPAEK-BP) <I 36> [React i on Scheme 11 ]

K₂CO₅ o k HO i OH + S HO- /-OH F-i ,HM /)-F 17O tJ

<137> <138> Reaction Scheme 11 was performed by the same method as Preparation Example 1 using 4,4'-biphenol as a starting material instead of (4,4'- hexafluoroisopropylidene)diphenol , and 4,4'—di fluorobenzophenone as a dihalide material instead of decafluoro biphenyl.

<139> Further, activation was performed at 150 to 160^°C , and maintained at 170^°C. Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'-biphenol as starting materials in various molar ratios of 20mmo1 :Ommo1 (k:s=1.00:0), 19mmol :lmmol (k:s=0.95:0.05), 18mmo1 :2mmo1 (k:s=0.9:0.1), 17mmo1 :3mmo1 Ck^s=O.85:0.15), lβmmol ^mmol (k:s=0.8:0.2), 15mmo1 :5mmo1 (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 12mmol :8mmol (k:s=0.6:0.4), lOmmo1 : lOmmo1 (k:s=0.5:0.5) and 8mmo1 : 12mmo1 (k:s=0.4:0.6). Each product was obtained with a yield of at least 90%.

<140> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPAEKlOO, E-SPAEK95-BP, E-SPAEK90-BP, E-SPAEK85- BP, E-SPAEK80-BP, E-SPAEK75-BP, E-SPAEK70-BP, E-SPAEK60-BP, E-SPAEK50-BP and E-SPAEK40-BP.

<141> <!42> Preparation Example 11: Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SPAEK-6F)

<143> [Reaction Scheme 12]

SOi K⁺ K₂CO₃

CF_j DMAc I Benzene k HO OH + s HO- -^ >-i OH F i, ,r~ C -χ ,) -F 170 ¹Q

CFs

<

< 145> Reaction Scheme 12 was performed by the same method as Preparation Example 1 using 4,4'-di fluorobenzophenone as a starting material instead of decafluorobiphenyl . Further, activation was performed in the range of 150 to 160^°C , and then maintained at 170°C . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'- (hexafluoroisopropylidene)diphenol as starting materials in various molar ratios of 19mmol:lmmol (k:s=0.95:0.05) , 18mmol :2mmol (k:s=O.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), 16mmo1 :4mmo1 (k:s=0.8:0.2), lδmmol :5mmol (k:s=0.75:0.25), 14mmo1 :6mmo1 (k:s=0.7:0.3), 13mmo1 :7ramo1 (k:s=0.65:0.35), 12mmol:8mmol

lOmmol :10mmol (k:s=0.5:0.5) and 8mmo1 : 12mmo1 (k:s=0.4:0.6). Each product was obtained with a yield of at least 90%.

<146> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPAEK95-6F, E-SPAEK90-6F, E-SPAEK85-6F, E- SPAEK80-6F, E-SPAEK75-6F, E-SPAEK70-6F, E-SPAEK65-6F, E-SPAEK60-6F, E- SPAEK50-6F and E-SPAEK40-6F.

<I47> <148> Preparation Example 12: Preparation of sulfonated polyCarylene ether) copolymer having a crossl inkable moiety (E-SPAESO-BP)

<149> [Reaction Scheme 13]

k HO-V₁ -OH + s HO .? W OH

<151 > Reaction Scheme 13 was performed by the same method as Preparation Example 1 using 4,4'-biphenol as a starting material instead of 4,4'- (hexafluoroisopropylidene)diphenol , and 4,4'-di fluorodiphenyl sulfone as a dihalide material instead of decafluorobiphenyl . Further, activation was performed in the range of 150 to 160°C , and maintained at 170°C. Sulfonated polyCarylene ether) copolymers having crossl inkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'-biphenol as starting materials in various molar ratios of 19mmo1 : lmino1 (k:s=0.95-'0.05) , 18mmol:2mmol (k:s=O.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), 16mmol:4mmol (k:s=0.8:0.2), 15mmol:5mmol (k:s=0.75:0.25), 14mmol:6mmol (k:s=0.7:0.3), 13mmol:7mmol (k:s=0.65:0.35) , 12mmol :8mmol (k:s=0.6:0.4), lOmmol :lOmmol (k:s=0.5:0.5) and 8mmol:12mmol (k:s=0.4:0.6). Each product was obtained with a yield of at least 90%. <152> The polyCarylene ether) copolymers prepared with various ratios of k to s were independently named E-SPAES095-BP, E-SPAES090-BP, E-SPAES085-BP, E- SPAES080-BP, E-SPAES075-BP, E-SPAES070-BP, E-SPAES065-BP, E-SPAES060-BP, E- SPAES050-BP and E-SPAES040-BP.

<153>

<154> Preparation Example 13: Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SPAES0-6F)

<I55> [Reaction Scheme 14] zsne

<157> Reaction Scheme 14 was performed by the same method as Preparation Example 1 using 4,4'-difluorodiphenyl sulfone as a starting material instead of decafluorobiphenyl . Further, activation was performed in the range of 150 to 160^°C, and then maintained at 170^°C . Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'- (hexafluoroisopropylidene)diphenol as starting materials in various molar ratios of 19mmol:lmmol (k:s=0.95:0.05) , 18mmo1 :2mmo1 (k:s=0.9:0.1), 17mmol:3mmol (k:s=0.85:0.15), lβmmo1 :4mmo1 (k:s=0.8:0.2), lδinmol :5mmol (k:s=0.75:0.25), 14mmol:6mmol (k:s=0.7:0.3), 13mmo1 :7mmo1 (k:s=0.65:0.35), 12mmol:8mmol (k:s=0.6:0.4), lOmmo1 : lOmmo1 (k:s=0.5:0.5) and 8mmol :l2mmol (k:s=0.4:0.6) . Each product was obtained with a yield of at least 90%.

<158> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPAES095-6F, E-SPAES090-6F, E-SPAES085-6F, E- SPAES080-6F, E-SPAES075-6F, E-SPAES070-6F, E-SPAES065-6F, E-SPAES060-6F, E- SPAES050-6F and E-SPAES040-6F.

<159> <I6O> Preparation Example 14: Preparation of sulfonated poly(arylene ether) copolymer having a crossl inkable moiety (E-SPEKK-BP)

<16I> [Reaction Scheme 15]

SO₅-K⁴ Beniβπe

<162> <163> Reaction Scheme 15 was performed by the same method as Preparation Example 1 using 4,4'-biphenol as a starting material instead of (4,4'- hexafluoroisopropyIidene)diphenol , and l,3-bis(4-fluorobenzoyD-benzene instead of decafluorobiphenyl as a dihalide material. Further, activation was performed in the range of 150 to 160^°C , and maintained at 170°C . Sulfonated poly(arylene ether) copolymers having crossl inkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'-biphenol as starting materials in various molar ratios of 20mmo1 :Ommo1 (k:s=1.00:0), 19mmol:lmmol (k:s=0.95:0.05) , 18mmo1 :2mmo1 (k:s=0.9:0.1), 17mmo1 :3mmo1 (k:s=0.85:0.15), 16mmo1 :4mmo1 (k:s=0.8:0.2), lδmmol :5mmol (k:s=0.75:0.25) , 14mmol:6mmol (k:s=0.7:0.3), 12mmo1 :8mmo1

lOmmo1 : lOmmo1 (k:s=0.5:0.5) and 8mmo1 : 12mmo1 (k:s=0.4:0.6). Each product was obtained with a yield of at least 90%.

<164> The polyCarylene ether) copolymers prepared with various ratios of k to s were independently named E-SPEKK100-BP, E-SPEKK95-BP, E-SPEKK90-BP, E- SPEKK85-BP, E-SPEKK80-BP, E-SPEKK75-BP, E-SPEKK70-BP, E-SPEKK60-BP, E- SPEKK50-BP and E-SPEKK40-BP.

<165> <166> Preparation Example 15: Preparation of sulfonated poly(arylene ether) copolymer having a crosslinkable moiety (E-SPEKK-6F)

<167> [Reaction Scheme 16]

<168> <169> Reaction Scheme 16 was performed by the same method as Preparation Example 1 using l,3-bis(4-fluorobenzoly)-benzene, a dihalide material, as a starting material instead of decafluorobiphenyl . Further, activation was performed in the range of 150 to 160°C, and then maintained at 170°C. Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared using hydroquinonesulfonic acid potassium salt and 4,4'- (hexafluoroisopropylidene)diphenol as starting materials in various molar ratios of 19mmo1 : lmmo1 (k:s=0.95:0.05) , lδmmol :2mmol (k:s=O.9:0.1), 17mmol:3mmol (k:s=0.85:0.15), lθmmol :4mmol (k:s=0.8:0.2), 15mmo1 :5mmo1 (k:s=0.75:0.25), 14mmo1 :6ramo1 (k:s=0.7:0.3), 13mmo1 :7mmo1 (k:s=0.6:0.35) , 12mmol:8mmol (k:s=0.5:0.4), lOmmol : lOmmol (k:s=0.5:0.5) and 8mmo1 : 12mmo1 (k:s=0.4:0.6) . Each product was obtained with a yield of at least 90%. <17O> The poly(arylene ether) copolymers prepared with various ratios of k to s were independently named E-SPEKK95-6F, E-SPEKK90-6F, E-SPEKK85-6F, E- SPEKK80-6F, E-SPEKK75-6F, E-SPEEK70-6F, E-SPEKK65-6F, E-SPEKK60-6F, E- SPEEK50-6F and E-SPEEK40-6F.

<171>

<i72> Structures of the sulfonated poly(arylene ether) copolymers having crosslinkable moieties synthesized by Preparation Examples 1 to 15 were analyzed using IH-NMR, 19F-NMR and FT-IR.

<173> Referring to IH-NMR results shown in FIGS. 1 to 6, the polymers were compared to an E-SFQK polymer formed by polymerization of hydroquinonesulfonic acid potassium salt with decafluorobiphenyl and introduction of an ethynyl group. The results show no peak corresponding to a hydroxyl group of a monomer and a proton peak corresponding to an ethynyl group. Thus, it could be confirmed that the polymer is substituted with a crosslinkable ethynyl group.

<174> The results also show peaks corresponding to the polymers. In 19F-NMR results, only two peaks are shown, which indicates that F, located at a para position on the decafluorobiphenyl group, participated in polymerization and then released.

<175>

<176> Preparation Example 16: Preparation of polymer electrolyte membrane <177> Sulfonated poly(arylene ether) copolymers having a crosslinkable moiety synthesized according to Preparation Examples 1 to 15 were dissolved in a solvent, followed by being filtered using a 0.45μm to lμm PTFE membrane filter. Afterward, the polymer solvent was poured over a glass plate by casting, and maintained in an oven at 40°C for 24 hours. <178> Subsequently, for crossl inking polymer ends, annealing was performed at 80 to 350^°C for 30 minutes or more, and preferably at 250 to 260^°C for at least 2 hours.

<i79> Here, the available solvents were dipolar solvent, including N,N'- dimethylformamide (DMF), diraethylacetamide (DMAc), dimethylsulfoxide (DMSO) and N-methy1pyro1 idone (NMP) .

<i80> After the annealing, the polymer membrane was cooled down to room

+ + temperature, and treated with an acid to substitute a counter ion (Na , K or alkyl ammonium ion) of a sulfone part in the polymers prepared in Reaction Schemes 2 to 15 with hydrogen.

<i8i> The acid treatment was performed by soaking the membrane in a 2N H2S04 solution, IN HNO₃ solution or IN HCl solution for 24 hours and then transferred to distilled water for another 24 hours, or boiled in 0.5M H₂SO₄ solution for 2 hours. However, the present invention is not limited thereto.

<182> According to the sulfonated poly(arylene ether) copolymers prepared by Preparation Examples 1 to 15, the polymer membranes were independently named. That is, when the polymer membrane was formed using E-SFQK-6F in Preparation Example 1, the membrane was named CSFQH-6F. Accordingly, the 15 kinds of polymer membranes formed using sulfonated poly(arylene ether) copolymers disclosed in Preparation schemes 1 to 15 were independently named CSFQH-6H, CSFQH-BP, CSFQH-HQ, CSFQH-6H, CSFQH-2BP, CSFQH-DPE, CSPECN-HQ, CSPEK-6F, CSPEK-BP, CSPAEK-BP, CSPAEK-6F, CSPAESO-BP, CSPAES0-6F, CSPEKK-BP and CSPEKK- 6F, respectively.

<183> Table 1 shows solubilities of the 15 kinds of polymer membranes.

<i84> [Table 1]

< 186>

<187> As shown in Table 1, the polymer electrolyte membrane was not dissolved in any solvent, which indicates that it is crosslinked. Thus, the membrane has very high chemical stability and good dimensional stability.

< I 88> In FIGS. 7 and 8, a structure of the crosslinked polymer electrolyte membrane was analyzed by FT-IR, compared to an electrolyte membrane CSFQH prepared of an E-SFQK polymer by polymerization of hydroquinonesulfonic acid potassium salt with decafluorobiphenyl and then introduction of an ethynyl group.

<189> Further, glass transition temperatures (Tg) of the polymer electrolyte membranes formed in Preparation Example 16 were taken under a nitrogen gas atmosphere at 10^°C/inin by differential scanning calorimetry (DSC). As shown in FIGS. 9 to 13, the Tgs are at least 200^°C, which indicates that the membranes have significantly-higher thermal stabilities than that of the Nafion film, which is commercially available, and a decomposition temperatures (Tds) are 300^°C, which indicates the membranes have a very high thermal stability.

<i90> In FIGS. 9 to 13, CSFQH90-6F, CSFQH80-6F, CSFQH70-6F, CSFQH90-BP, CSFQH80-BP and CSFQH70-BP, which are the names of the polymer electrolyte membranes, have meanings as follows. For examples, CSFQH90-6F denotes a polymer electrolyte membrane formed using E-SFQK90-6F prepared in Preparation Example 1, and CSFQH90-BP denotes a polymer electrolyte membrane formed using E-SFQK90-BP prepared in Preparation Example 2, CSFQH90-HQ denotes a polymer electrolyte membrane formed using E-SFQK90-HQ prepared in Preparation Example 3, CSFQH90-6H denotes a polymer electrolyte membrane formed using E-SFQK90-6H prepared in Preparation Example 4, and CSFQH90-DPE denotes a polymer electrolyte membrane formed using E-SFQK90-DPE prepared in Preparation Example 6.

<i9i> Also, as shown in FIG. 14, it can be noted that the polymer electrolyte membranes are transparent and amorphous.

<192> Table 2 shows water uptakes and proton conductivities of the polymer electrolyte membranes formed in Preparation Example 16 compared to the currently used Nafion film, which are commercially available.

<i93> [Table 2]

<194> <195> <196>

<197>

<198>

<199>

<200>

<201>

<202>

<203>

<204>

<205>

<206>

<207>

<208>

<209>

<210>

<211>

<212>

<213>

<214>

<215>

<2!6>

<217>

<218>

<219>

<220>

<221>

<222>

<223>

<224>

<225>

<226>

<227>

<228>

<229>

<230>

<231>

a : Calculated as a monomer molar ratio! IEC = (1000/molecular weight of repeating unit)x sulfonation ratioX the number of sulfonic acid groups}

<232> b : For titration, the membrane was soaked in 0.01N NaCl solution for

24 hours, and then titrated using 0.01N NaOH. (The indicator used in the test was phenolphthalein)

<233> c : Equivalent weight per sulfonic acid group

<234> d ^'• Analyzed by an impedance analyzer (AutoLab, PGSTAT 30,

Netherlands)! σ (S/cm)/(Rx S), L(cm) is a distance between both electrodes, R(Ω) is membrane resistance, S(cni2) is surface area of an ion transporting membrane}

<235> e • Estimated weight of a membrane {Water Uptake(%) = (Wwet - Wdry) x

100/Wdry, Wwet is a weight of a wet membrane, Wdry is a weight of a dry membrane}

<236>

It can be noted from Table 2 that the polymer electrolyte membrane has much a higher ion conductivity, which is its most import characteristic, and a lower water uptakes than the Nafion film.

<237> <238> Embodiment 1 <239> A sulfonated poly(arylene ether) copolymer according to Embodiment 2 has a crosslinkable moiety, which is represented by Formula 4.

<240> [Formula 4]

CMl -H-O-Atf-O-SAr-V-/-fθ-Ar2-O-Arl-)—I— CM2

<241> L ^λ <242> In Formula 4, SAr indicates a sulfonated aromatic group.

<243> In Formula 4, SAr includes

SO₃ M

O₃S SO₃ ^" M

<244> Also, both ArI and Ar2 are unsulfonated aromatic groups, which may be the same as or different from each other.

<245> The ArI and Ar2 are independently

<246>

Y is a carbon-carbon single bond, -Q-, -S-, —

O — S — o Il

<247> A is a carbon-carbon single bond, -Q-, -S-,^~s~~, ° —c—

/=_v A-

-A

<248> Further , in Y , denotes a benzene structure having ortho,

_/=_v A-

-A- F' meta or para-substituted connecting moieties, and — denotes a fully fluorine-substituted benzene structure, which has ortho, meta or para-

substituted connecting moieties. That is,

denotes fully fluorine-substituted benzene structures having connecting moieties at ortho (

e, Cl to C5 are hydrogen- or fluorine-substituted alkyl structures having 1 to 5

carbon atoms, and

is an L-substituted benzene structure.

<249> In the above structural formula, L is H, F or Cl to C5, H is hydrogen, F is fluorine, and Cl to C5 are hydrogen- or fluorine-substituted alkyl structures having 1 to 5 carbon atoms.

- +

<250> Z denotes a bond directly attached to carbon of benzene and - SO3 M ,

or , which may be connected at an ortho, meta or para position. Y in Z is the same as described above. +

<25i> M is a counter ion having a positive charge and may be a potassium ion

(K ), a sodium ion (Na ) or an alkyl ammonium ion ( NR4), and preferably, an K

+ or Na ion.

<252> CMl or CM2 is a moiety, which includes

. In

CMl or CM2, R is a Rl-substitued ethynyl part (R= ^^R1 ), vinyl part (R= Rl

RI \ /

) or ^v which may be an ortho, meta or para-substituted radical on a benzene ring. In R, G is a carbon-carbon single bond, -O- , -S-

O or —OC- _{Also> R1 is H; F> C1 t0 C5; or} ^XR2 _ _{In R1) H is} hydrogen, F is fluorine, Cl to C5 are hydrogen- or fluorine-substituted alky

—^^R2 structures having 1 to 5 carbon atoms, denotes benzene ring having ortho, meta or para-substituted R2. R2 is H, X or Cl to C5. In R2, H is hydrogen, Cl to C5 are hydrogen- or fluorine-substituted alky structures having 1 to 5 carbon atoms, and X is a halogen atom (F, Cl or Br). Here, X is a functional group enabling polymerization with a hydroxy group in another polymer chain. Also, in Formula 1, k ranges from 0.001 to 1.000, s has 1-k, and n is an integer indicating the number of a repeating unit in a macromolecular polymer. Here, n is a natural number ranging from 10 to 500.

<253> The sulfonated poly(arylene ether) copolymer having a crosslinkable moiety at an end of Formula 4 is prepared by the method shown in Reaction Scheme 16, which will now be described in detail.

<254> [Reaction Scheme 16]

<255> k X - Sar-X + s X-ArI-X + m H0-Ar2-0H

<256> [Formul a 5] -O-Ar2-O—SAr-)r-/-fθ-Ar2-O—ArI

<257> 's Jn

<258> [Formula 6]

<260> [Formula 4]

CMl- O -Ar2-O-SAr-)—/-fθ-Ar2-O-Arl^—I— CM2

<261> ^;k ^{v ;}s Jn

<262> Reaction Scheme 16 shows a reaction process for preparing a compound of Formula 4. Also, a polymer of Formula 5 is prepared by polycondensation, and a monomer participating in the reaction can be changed.

<263> A sulfonated monomer (X-SAr-X) used for the compound of Formula 4 is a dihalide monomer. The sulfonated poly(arylene ether) copolymer having a crosslinkable moiety may be prepared according to Reaction Scheme 16.

<264> In Reaction Scheme 16, k has a range of 0.001 to 1, s is 1-k, and (k+s)/m has a range of 0.8 to 1.2. Further, k, s and m denote molar ratios of monomers participating in the reaction.

<265> Here, compounds of Formula 6 may include a hydroxy-substituted monomer

HO—{ Λ ^^~ _\ x

( ° ) and a halide-substituted monomer ( ). In Reaction

Scheme 16, when (k+s)/m is 1 or less, the halide-substituted monomer

( ) participates in the reaction, and when (k+s)/m is more than 1,

HO- _^^ the hydroxy group-substituted monomer ( ^) participates in the reaction. Further, when R2 in Formula 6 is X, the hydroxy group-substituted

monomer (

) may participate in the reaction regardless of the value of (k+S)/m. <266> In the preparation process of Reaction Scheme 16, an unsulfonated dihydroxy monomer is activated to facilitate the polycondensation facilitates the polycondensation of the dihydroxy monomer with the dihalide monomer. Also, the sulfonated and unsulfonated dihalide monomers may be added to in the same step of the preparation process, together with the dihydroxy monomer .

<267> First, in the presence of a solvent consisting of a base, an azeotropic solution and an aprotic polar solvent, polycondensation is performed at 0 to 300^°C for 1 to 100 hours to give a macromolecular polymer represented by Formula 5. Also, depending on the type of the preparation process, a protic polar solvent can be used instead of the aprotic polar solvent.

<268> Subsequently, a macromolecular polymer having a crosslinked structure at an end represented in Formula 4 is prepared using the macromolecular polymer of Formula 5, and the hydroxy- or halide-substituted monomer of Formula 6. A reaction for preparing the polymer of Formula 4 is substantially the same as the method of preparing the macromolecular polymer of Formula 5.

<269> That is, the crossl inked structure-substituted macromolecular polymer of Formula 4 is prepared by activation and polycondensation, sequentially. Before the polycondensation step, the azeotropic solvent may be removed.

<270> Also, in the present embodiment, to improve thermal stability, electrochemical stability, film-forming capacity, dimensional stability, mechanical stability, chemical characteristics, physical properties and cell performance of the polymer represented by Formula 5, CMl or CM2 including a thermal crossl inkable group is substituted at the end of the polymer chain by polycondensation to give a sulfonated poly(arylene ether) copolymer having a crossl inked structure, represented by Formula 4.

<27i> For the polycondensation and introduction of crossl inkable groups to synthesize the sulfonated polyCarylene ether) copolymer having a crossl inked structure, an inorganic base selected from the group consisting of a hydroxide of alkali metal or alkali earth metal, a carbonate and a sulfate, or a group consisting of general amines including ammonia may be used as a base .

<272> Also, as a reaction solvent, the aprotic polar solvent such as N- methylpyrolidone (NMP), dimethyl formamide (DMF), N,N-dimethylacetamide (DMAc) or dimethylsLilfoxide (DMSO), or protic polar solvent such as methylene chloride (CH2CI2), chloroform (CH₃Cl) or tetrahydrofuran (THF) may be used, and benzene, toluene or xylene may be used as an azeotropic solvent.

<273> The sulfonated poly(arylene ether) copolymer having a crossl inked structure prepared by the method described above has equal or superior thermal stability, film-forming capacity, mechanical stability, chemical characteristics, physical properties and cell performance compared to the commercially available polymer electrolyte membrane, e.g., Nafion film, and further improved electrochemical characteristics such as proton conductivity and cell performance. Moreover, the copolymer has high dimensional stability, so that the electrolyte membrane has no change in characteristics even though it is exposed to moisture for a long time.

<274> <275> Preparation Example 1^'- Preparation of sulfonated poly(arylene ether) copolymer having crossl inkable moiety (E-DSPES0-6F)

<276> [Reaction Scheme 17]

/ Benzene

<277> <278> E-DSPES0-6F was synthesized by the same method as in Preparation Example 1, except that 3,3'-disulfonated-4,4'-difluorodiphenyl sulfone, 4,4'- difluorodiphenyl sulfone and (4,4'-hexafluoroisopropyIidene)diphenol were independently used as a sulfonated monomer, an unsulfonated dihalide monomer and a dihydroxy monomer.

<279> Activation was performed at 150 to 170^°C for 6 to 8 hours, and then polymerization was performed at an increased temperature of 170 to 180^°C .

<280> Sulfonated polyCarylene ether) copolymers having crosslinkable moieties were prepared with various molar ratios of 3,3'-disulfonated-4,4'- difluorodiphenyl sulfone to 4,4'-difluorodiphenyl sulfone of lOmmol :10mmol (k:s=0.5:0.5), 9mmol:llmmol (k:s=0.45:0.55), 8mmol:l2mmol (k:s=0.4:0.6), 7mmol:l3mmol (k:s=0.3:0.65) and 6mmo1 : 14mmo1 (k:s=0.3:0.7).

<28 I > The sulfonated poly(arylene ether) copolymers prepared with various ratios of k to s described above were independently named E-DSPES050-6F, E- DSPES045-6F, E-DSPES040-6F, E-DSPES035-6F and E-DSPES030-6F, respectively. Each product was obtained with a yield of 90% or more.

<282> <283> Preparation Example 18: Preparation of sulfonated poly(arylene ether) copolymer having crosslinkable moiety (E-DSPESO-BP)

<284> [Reaction Scheme 18]

*Na%S SO₃-Na*

K₂CO₃

L \ DMfte I Benzene

% f no c

<285> <286> E-DSPESO-BP was synthesized by the same method as Preparation Example 1, except that 3,3 '-disulfonated-4,4'—di fluorodiphenyl sulfone, 4,4'- difluorodiphenyl sulfone and 4,4'-biphenol were independently used as a sulfonated monomer, an unsulfonated dihalide monomer and a dihydroxy monomer.

<287> Activation was performed at 150 to 170^°C for 6 to 8 hours, and polymerization was performed at an increased temperature of 170 to 180^°C.

<288> Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared with various molar ratios of 3,3'-disulfonated-4,4'- difluorodiphenyl sulfone to 4,4'-difluorodiphenyl sulfone of lOmmol • lOmmol (k:s=0.5:0.5), 9mmol :llmmol (k:s=0.45:0.55) , 8mmo1 : 12mmo1 (k:s=0.4:0.6), 7mmol:l3mmol (k:s=0.3:0.65) and 6mmo1 : 14mmo1 (k:s=0.3:0.7).

<289> The sulfonated poly(arylene ether) copolymers prepared with various ratios of k to s described above were independently named E-DSPES050-BP, E- DSPES045-BP, E-DSPES040-BP, E-DSPES035-BP and E-DSPES030-BP. Each product was obtained with a yield of 90% or more.

<290> <291> Preparation Example 19: Preparation of sulfonated polyCarylene ether) copolymer having crosslinkable moiety (E-DSPEK-6F)

<292> [Reaction Scheme 19]

I B^βnzerte t

<293> <294> E-DSPEK-6F was synthesized by the same method as Preparation Example 1, except that 3,3'-disulfonated-4,4'-difluorobenzophenone, 4,4'- difluorobenzophenone and 4,4'-(hexaf1uoroisopropyIidene)diphenol were independently used as a sulfonated monomer, an unsulfonated dihalide monomer and a dihydroxy monomer.

<295> Activation was performed at 150 to 170^°C for 6 to 8 hours, and polymerization was performed at an increased temperature of 170 to 180^°C.

<296> Sulfonated poly(arylene ether) copolymers having crosslinkable moieties were prepared with various molar ratios of 3,3'-disuifonated-4,4'- difluorobenzophenone to 4,4' -difluorobenzophenone of lOmiiiol :lOmmol (k: s=0.5:0.5), 9mmol :llmmol (k:s=0.45:0.55) , 8mmol : 12mmol (k:s=0.4:0.6), 7mmol:13mmol (k:s=0.3:0.65) and βmmol : 14mmol (k:s=0.3:0.7).

<297> The sulfonated poly(arylene ether) copolymers prepared with various ratios of k to s described above were independently named E-DSPEK50-6F, E- DSPEK45-6F, E-DSPE40-6F, E-DSPEK35-6F and E-DSPEK30-6F. Each product was obtained with a yield of 90% or more.

<298> <299> Preparation Example 20: Preparation of sulfonated poly(arylene ether) copolymer having crosslinkable moiety (E-DSPEK-BP)

<300> [Reaction Scheme 20]

-NsO₃S SO.-Na*

^ O ^ O K*CO,

Il Dtølftc / Benzene ij^~h~U ^f XJ-^-\j F * HO¹ % 4n -OH 170 C

<301 > <302> E-DSPEK-BP was synthesized by the same method as Preparation Example 1, except that 3,3'-disulfonated-4,4'—di fluorobenzophenone, 4,4'- difluorobenzophenone and 4,4'-biphenol were independently used as a sulfonated monomer, an unsulfonated dihalide monomer and a dihydroxy monomer. Activation was performed at 150 to 170°C for 6 to 8 hours, and polymerization was performed at an increased temperature of 170 to 180^°C.

<303> Sulfonated polyCarylene ether) copolymers having crosslinkable moieties were prepared with various molar ratios of 3,3'-disulfonated-4,4'- difluorobenzophenone to 4,4'-difluorobenzophenone of lOmmol :10mmol (k:s=0.5:0.5), 9mmol:llmmol (k:s=0.45:0.55), 8mmo1 : 12mmo1 (k:s=0.4:0.6), 7mmo1 : 13mmo1 (k:s=0.3:0.65) and 6mmo1 : 14mmo1 (k:s=0.3:0.7) .

<304> The sulfonated poly(arylene ether) copolymers prepared with various ratios of k to s described above were independently named E-DSPEK50-BP, E- DSPEK45-BP, E-DSPEK40-BP, E-DSPEK35-BP and E-DSPEK30-BP. Each product was obtained with a yield of 90% or more.

<305>

<306> Preparation Example 21: Formation of polymer electrolyte membranes (CDSPES0-6F, CDSPESO-BP, CDSPEK-6F and CDSPEK-BP)

<307> Polymer electrolyte membranes (CDSPES0-6F, CDSPESO-BP, CDSPEK-6F and CDSPEK-BP) were prepared using the sulfonated poly(arylene ether) copolymers having crossl inked structures (E-DSPES0-6F, E-DSPESO-BP, E-DSPEK-6F and E- DSPEK-BP) prepared according to Preparation Examples 17 to 20, respectively. The polymer electrolyte membranes were named in the sequence of the sulfonated polyCarylene ether) copolymers described above. For example, the polymer electrolyte membrane using E-DSPES0-6F was named DSPES0-6F, and the polymer electrolyte membrane using E-DSPEK-BP was named CDSPEK-BP.

<308> Further, a method of forming the polymer electrolyte membrane was the same as the methods described in Preparation Example 16.

<309> Table 3 shows solubilities of the polymer electrolyte membranes. <310> [Table 3]

<31 1 >

<312>

<313> It can be noted from Table 3 that the polymer electrolyte membrane is not dissolved in any solvent, which indicates that the polymer electrolyte membrane is crossl inked. It can be also noted that the polymer electrolyte membrane has very high chemical stability and dimensional stability.

<314> While the invention has been shown and described with reference to certain exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

[CLAIMS]

[Claim 1] <3i6> A sulfonated poly(arylene ether) copolymer having a crosslinkable moiety at an end, represented by Formula 1, <3i7> [Formula 1]

CMl . -^H^"-O^o-^~S^SA^Ar^r-^~'O^o-^~ A^Ar^r2²-7)]jr—//—^"T f O^o-^~ A^Ar^rI^l-^~O^o-^~ A^Ar^r2²TT^{~ CM2}

<318> ^{L k S J n}

<3i9> wherein SAr is a sulfonated aromatic group, ArI and Ar2 are unsulfonated aromatic groups, and CMl and CM2 are crosslinkable moieties, and <320> k has a range of 0.001 to 1, s has a value of 1-k, and n is an integer from 10 to 500 indicating the number of repeat units.

[Claim 2] <32i> The copolymer according to claim 1, wherein the sulfonated poly(arylene ether) copolymer having a crosslinkable moiety at an end, represented by

Formula 1 is prepared by Reaction scheme 1 <322> [Reaction scheme 1] <323> kOH-SAr-OH + sHC-Arl-OH + mX-Ar2-X

<324> [Formula 2]

<325>

<326> [Formul a 3]

<328> [Formul a 1]

CMl-H- 0-SAr-O- Ar2-)r-/-fθ- ArI-O- Ar2-)-^ I— CM2

<329> L ^{k S J n}

<330> wherein k has a range of 0.001 to 1, s is 1-k, (k+s)/m has a range of 0.800 to 1.200, and k, s and m are molar ratios of monomers participated in the reaction.

[Claim 3] <331> The copolymer according to claim 2, wherein SAr is

SO₃M

d

enotes a bond directly attached to carbon of benzene and - SO3 M , -

<332> wherein Y is a carbon-carbon single bond, -Q-, -S-,

<333>

wherein A is a carbon-carbon single bond, -Q-, -S-, ^s"

E E O

I I I I

O — C — —Si — P

Il I I I c— E E E <334>

wherein E is H, F, C1~C5 or <335> wherein L is H, F, or C1-C5, and

<336> wherein M is a counter ion having a positive charge.

[Claim 4] <337> The copolymer according to claim 2, wherein the counter ion having a positive charge is a potassium ion, a sodium ion or an alkyl ammonium ion.

[Claim 5]

<338> The copolymer according to claim 2, wherein ArI and Ar2 are

independently

O

—S

<340> wherein A is a carbon-carbon single bond, -Q-, -S-, —s— (3

<34I>

wherein E is H, F, C1-C5 or and <342> wherein L is H, F, Cl ~ C5.

[Claim 6] <343> The copolymer according to claim 2, wherein CMl and CM2 are

independently

or ,

<344> wherein R is a Rl-substituted ethynyl (R= ^{^}=^R1 ) or vinyl part

o

<345> wherein G is a carbon-carbon single bond, -Q-, -S- or -o-c-

<346> wherein Rl is H, F, Cl ~C5 or

, and

<347> wherein R2 is H, X or C1-C5.

[Claim 7] <348> A sulfonated poly(arylene ether) copolymer having a crosslinkable moitey at an end, represented by Formula 4. <349> [Formula 4] CM2

<35i> wherein SAr is a sulfonated aromatic group, ArI and Ar2 are unsulfonated aromatic groups, and CMl and CM2 are crosslinkable moieties, and <352> k has a range of 0.001 to 1, s is 1-k, and n is an integer from 10 to

500 indicating the number of repeating units.

[Claim 8] <353> The copolymer according to claim 7, wherein the sulfonated poly(arylene ether) copolymer having a crosslinkable moitey at an end, represented by

Formula 4, is prepared by Reaction scheme 2. <354> [Reaction scheme 2]

<355> kX-SAr-X + sX-Arl-X + mH0-Ar2-0H

<356> [Formula 5]

f O- Ar2-O-SAr-W-f O- Ar2-O- ArI -^j-

<357> <358> [Formula 6]

HO- X-

R

<359> ^■ R or <360> [Formula 4]

<362> wherein k has a range of 0.001 to 1, s is 1-k, (k+s)/m has a range of 0.800 to 1.200, and k, s and m are molar ratios of monomers participated in the reaction.

[Claim 9]

<363> The copolymer according to claim 8, wherein SAr is

<364> wherein Z denotes a bond directly attached to carbon of benzene and -

—

<365>

wherein Y is a carbon-carbon single bond, -Q-, -S-, —s—

O

O —S

<366> wherein A is a carbon-carbon single bond, -Q-, -S-, -s Il— O

<367>

wherein E is H, F, C1~C5 or <368> wherein L is H, F, C1~C5, and

+

<369> wherein M is a counter ion having a positive charge.

[Claim 10]

<370> The copolymer according to claim 8, wherein the counter ion having a positive charge is a potassium ion, a sodium ion or an alkyl ammonium ion.

[Claim 11]

<371> The copolymer according to claim 8, wherein the ArI and Ar2 are

independent Iy

, or

O

Il

O — S

<372> wherein Y is a carbon-carbon single bond, -0-, -S-, ^s , °

<373> wherein A is a carbon-carbon single bond, -Q-, -S-,

<374>

wherein E is H, F, C1~C5 or , and

<375> wherein L is H, F or Cl ~ C5.

[Claim 12]

<376> The copolymer according to claim 8, wherein CMl and CM2 are

independently

or ,

<377> wherein R is a Rl-subst ituted ethynyl (R= ^{~^R1} ) or vinyl

Rl

(R= ^R1 ) part or ^~^ ,

O

<378> wherein G is a carbon-carbon single bond, -Q-, -S- or ^~~ O-C—

<379> wherein Rl is H, F, Cl ~C5 or

, and

<380> wherein R2 is H, X or C1~C5.

[Claim 13] <38i> A polymer electrolyte membrane crossl inked by annealing using a poly(arylene ether ) copolymer represented by Formula 7 or 8. <382> [Formula 7]

CMl -f-f O-SAr- O-Ar24-/-f O- ArI-O- Ar2 -)-4- i <383> L ^{k sJn}

<384> [Formula 8]

CMl- -O-Ar2-O-SAr4— /-f O-Ar2-O-Arl4— 1— CM2

<385> <386> wherein SAr is a sulfonate aromatic group, ArI and Ar2 are unsulfonated aromatic groups, and CMl and CM2 are crosslinkable moieties, and

<387> k has a range of 0.001 to 1, s is 1-k, and n is an integer from 10 to 500 indicating the number of a repeating units.

[Claim 14] 'M

<388> The membrane according to claim 13, wherein SAr is

M

<389> wherein Z denotes a bond directly attached to carbon of benzene and -

<390>

wherein Y is a carbon-carbon single bond, -Q-, -S-,

/=\

-A- F' -A -i FΛ or

—

<391 > wherein A is a carbon-carbon single bond, -Q-, -S-, —s-

O

I I

O — C — — S i -P

I

— c— or E

<392> wherein E is H, F, Cl to C5 or

<393> wherein L is H, F or C1~C5, and

+

<394> wherein M is a counter ion having a positive charge.

[Claim 15] <395> The membrane according to claim 14, wherein the counter ion having a positive charge is a potassium ion, a sodium ion or an alkyl ammonium ion. [Claim 16]

<396> The membrane according to claim 15, wherein the crosslinked polymer electrolyte membrane has hydrogen substituting for the counter ion on the sulfonated aromatic ring by acid treatment. [Claim 17]

<397> The membrane according to claim 13, wherein ArI and Ar2 are

independently

or

<398>

wherein Y is a carbon-carbon single bond, -O-, -S-,

<399> wherein A is a carbon-carbon single bond, -Q-, -S-, -

<400>

wherein E is H, F, Cl~C5 or <401 > wherein L is H, F, Cl ~ C5,

<402> wherein CMl and CM2 are independently

<403> wherein R is a Rl-substituted ethynyl (R= ^{^^}^¹ ) or vinyl (R^z

Rl

-G

Rl .0

Rl ) part , or

<404> wherein G is a carbon-carbon single bond, -Q-, -S-, or

<405> wherein Rl is H, F, Cl ~C5 or "R2 , and <406> wherein R2 is H, X or C1~C5. [Claim 18]

<407> The membrane according to claim 13, wherein the annealing is performed at 80 to 350^°C using a dipolar solvent after melting the sulfonated poly(arylene ether) copolymer of Formula 7 or 8.

<408> <409>