KR100954060B1 - Sulfonated PolyArylene Ether, Method of manufacturing the same, and Crosslinked Polymer Electrolyte Membrane using the same - Google Patents

Abstract

A sulfonated poly (arylene ether) copolymer having a crosslinked structure, a preparation method thereof, and a polymer electrolyte membrane using the same are disclosed. A poly (arylene ether) copolymer containing sulfonic acid is synthesized by condensation polymerization of a dihydroxy monomer having a sulfonate group with a dihalide monomer or a dihydroxy monomer having a sulfonate group and a dihydroxy monomer. In addition, polycondensation reaction of the crosslinkable monohydroxy monomer or crosslinkable monohydroxy monomer enables the crosslinking of the polymer. In this way, thermal stability, mechanical stability, chemical stability, and film formation ability are maintained at the same level or higher than those of conventional sulfonated poly (arylene ether) copolymers or Nafion membranes currently used as commercially available polymer electrolyte membranes. The effect is significantly improved in terms of cation conductivity and cell performance. Moreover, even if it is exposed to moisture for a long time, there is no change in the characteristics of the electrolyte membrane, which shows high dimensional stability.

Fuel cell, sulfonate group, poly (arylene ether) copolymer, crosslinking, polymer electrolyte membrane, aromatic nucleophilic substitution reaction

Description

Sulfonated Poly (Arylene Ether), Method of manufacturing the same, and Crosslinked Polymer Electrolyte Membrane using the same

The present invention relates to a sulfonated poly (arylene ether) copolymer, a method for preparing the same, and a polymer electrolyte membrane using the same, and more particularly, to a sulfonated poly (arylene ether) copolymer having a crosslinked structure, and a preparation thereof. It relates to a method and a crosslinked polymer electrolyte membrane using the same.

A fuel cell is an electrical energy conversion system that converts chemical energy into electrical energy by an electrochemical reaction invented by 19th century Grove. The fuel cell was used for a special purpose like the Gemini spacecraft in the 1960s, but is currently a product that is actively researched and developed worldwide as an alternative energy corresponding to the increase in electric demand.

In particular, due to the imminent regulation of the total amount of carbon dioxide through the Green Round (Climate Change Convention) and the regulation of automobile exhaust gas through the obligatory sale of low-emission cars, automobile companies in each country are in a hurry to develop pollution-free automobiles such as fuel cell vehicles. It is true. In addition, fuel cells can be used directly for military power generation, such as small buildings, submarines and mobile communications on site and in some areas. These fuel cells do not accumulate electricity, but they are more efficient than conventional internal combustion engines, use less fuel, and emit little environmentally damaging substances such as sulfur oxides (SOx) and nitrogen oxides (NOx). It is expected to be a solution to environmental problems emerging from the use of fossil fuels as a clean high efficiency power generation device.

Polymer electrolytes, which are used as cation exchange resins or cation exchange membranes in fuel cells, have been used for decades and are constantly being studied. Recently used in direct methanol fuel cell (DMFC) or polymer electrolyte membrane fuel cell (PEMFC) polymer electrolyte membrane fuel cell, solid polymer electrolyte fuel cell, solid polymer fuel cell, or proton exchange membrane fuel cell Numerous studies have been conducted on cation exchange membranes as carriers of cations.

Currently, cation exchange membranes that are widely commercialized in the fuel cell field include the Nafion ™ series membrane, a polymer containing perfluorinated sulfonic acid group, DuPont, USA. The membrane has an ion conductivity of 0.1 S / cm, excellent mechanical strength and chemical resistance when saturated water content is present, and has stable performance as an electrolyte membrane for use in automotive fuel cells. Similar types of commercial membranes include Asahi Chemicals' Aciplex-S membrane, Dow Chemical's Dow membrane and Asahi Glass's flare. Flemion membrane, Gore & Associate's GoreSelcet membrane, and Canada's Ballard Power System Co., Ltd. developed alpha and beta perfluorinated polymers. It is under study.

However, the membranes are expensive and have difficulty in mass production due to the complexity of the synthesis methods, as well as methanol crossover in electrical energy systems such as direct methanol fuel cells, and low cationic conductivity at high or low temperatures. As a cation exchange membrane such as the like, it is used in a limited form because it has a characteristic that efficiency is greatly reduced.

Due to these drawbacks, many studies are being conducted on non-fluorine-based and partially fluorine-substituted cation exchange membranes, and representative examples thereof include sulfonated poly (phenylene oxide), poly (phenylene sulfide), and polysulfide. And the like, poly (para-phenylene), polystyrene, polyether ether ketone, polyimide and the like.

However, since their ion conductivity is proportional to the degree of sulfonation, when sulfonated above a critical concentration, the molecular weight decrease cannot be avoided, and there is a disadvantage that it cannot be used for a long time due to the reduction of mechanical properties during hydration. Methods for producing polymers using sulfonated monomers and methods for selective sulfonation of polymers have also been researched and developed (US Pat. Nos. 5,585,74, 5679482, 6110616). The situation may not be completely solved.

On the other hand, US Patent No. 6245881 discloses various forms of sulfonated polyimide using a form inducing a sulfonation reaction directly to the main chain of polyimide and a diamine monomer containing a sulfonic acid group. Compared with the conductive polymer material, it showed very high thermal stability and oxidation and reduction stability.

However, in the case of selectively sulfonating the polymer, there is a disadvantage in that the mechanical strength is reduced according to the sulfonation, and when using a sulfonic acid diamine monomer, there is a problem that the reactivity and film formation is not smooth due to poor solubility in the solvent. have.

Therefore, there is an urgent need for research on the development of a new type of material having excellent electrochemical properties, excellent high temperature stability, and easy manufacturing into a thin film.

The first object of the present invention for solving the above problems is to provide a sulfonated poly (arylene ether) copolymer having a crosslinked structure.

In addition, a second object of the present invention is to provide a crosslinked polymer electrolyte membrane using a sulfonated poly (arylene ether) copolymer obtained through the achievement of the first object.

The present invention for achieving the first object provides a sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal represented by the following formula.

In the above formula, SAr represents sulfonated aromatics, and Ar1 and Ar2 represent unsulfonated aromatics. In addition, CM1 and CM2 represent the part which can be bridge | crosslinked.

In the above formula k has a range of 0.001 to 1, s has a value of 1-k, n represents a repeating unit of the polymer polymer, n is an integer of 10 to 500.

In addition, the first object of the present invention can also be achieved through the provision of a sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal represented by the following formula.

In the above formula, SAr represents sulfonated aromatics, and Ar1 and Ar2 represent unsulfonated aromatics. In addition, CM1 and CM2 represent the part which can be bridge | crosslinked.

In the above formula k has a range of 0.001 to 1, s has a value of 1-k, n represents a repeating unit of the polymer polymer, n is an integer of 10 to 500.

The present invention for achieving the second object is achieved by providing a crosslinked polymer electrolyte membrane by heat-treating the sulfonated poly (arylene ether) copolymer obtained through the achievement of the first object.

According to the present invention as described above, the polymer electrolyte membrane using a sulfonated poly (arylene ether) copolymer having a crosslinked structure is equivalent to the conventional commercialized polymer electrolyte membrane in thermal stability, mechanical stability, chemical stability, membrane formation ability, etc. Or at a higher level. In addition, it exhibits a significantly improved effect on the cation conductivity and the cell performance compared to the conventional polymer electrolyte membrane, and exhibits high dimensional stability even when exposed to moisture for a long time without changing the characteristics of the electrolyte membrane, and can be used in fuel cells or secondary batteries. .

First Example

The sulfonated poly (arylene ether) copolymer according to the first embodiment of the present invention has a crosslinked structure. The sulfonated poly (arylene ether) copolymer is according to the following formula (1).

[Formula 1]

,

,

,

또는

이다.In Formula 1, SAr represents sulfonated aromatics. SAr in Formula 1 is

,

,

,

or

to be.

In addition, Ar1 and Ar2 represent unsulfonated aromatics and may be the same or different from each other.

또는

이다. Ar1 or Ar2 is

or

to be.

,

,

,

,

,

,

,

,

또는

이며, A는 탄소와 탄소가 직접 연결되어 있는 단일결합, -O-, -S-,

,

,

,

,

또는

이며, E는 H, F, C1 ~ C5 또는

이다.Y is a single bond, -O-, -S-,

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

to be.

는 연결부분이 오르소, 메타, 파라 위치에 올 수 있는 벤젠구조를 나타내며,

는 불소(F)가 완전히 치환되어 있으며 연결부분이 오르소, 메타, 파라 위치에 올수 있는 벤젠구조를 의미한다. 즉

라 함은 연결부분이 오르소 (

), 메타 (

), 파라 (

) 위치에 올수 있는 불소가 완전히 치환된 벤젠구조들을 의미한다. 또한 E에서 H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬 구조를

는 L이 벤젠에 치환되어 있는 벤젠구조를 의미한다. 상기 구조식에서 L은 H, F, C1 ~ C5 를 나타내며, H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조를 의미한다.Also, in Y

Represents a benzene structure in which the linking moiety can be in the ortho, meta, or para position,

Refers to a benzene structure in which fluorine (F) is completely substituted and the linking portion can be at ortho, meta and para positions. In other words

Means the connection is ortho (

), Meta (

), Para (

Benzene structure that is completely substituted with fluorine which may be at position). In E, H represents hydrogen, F represents fluorine, and C1 to C5 represent an alkyl structure with hydrogen or fluorine substituted with 1 to 5 carbon atoms.

Means a benzene structure in which L is substituted for benzene. In the above structural formula, L represents H, F, C1 ~ C5, H means hydrogen, F is fluorine, C1 ~ C5 means an alkyl structure substituted with hydrogen or fluorine having 1 to 5 carbon atoms.

,

또는

이며 오르소, 메타, 파라 구조의 위치에 올 수 있다. Z에서 Y는 앞서 설명한 Y와 의미가 같다.In addition, Z is a bond in which carbon of benzene and -SO ₃ ^- M ⁺ are directly connected,

,

or

And can come in positions of ortho, meta, and para structures. Y in Z has the same meaning as Y described above.

M ⁺ is a counterion with a cationic charge and represents potassium ions (K ⁺ ), sodium ions (Na ⁺ ), alkyl amines ( ⁺ NR 4), and the like, and preferably potassium ions or sodium ions.

또는

이다. CM1 또는 CM2에서 R은 R1이 치환되어있는 삼중결합(ethynyl part)(R=

), 이중결합(vinyl part)(R=

) 또는

이며 오르소, 메타, 파라 구조의 위치에 올 수 있다. 상기 R에서 G는 탄소와 탄소가 직접 연결되어 있는 단일 결합, -O-, -S- 또는

를 의미한다. 또한 R1은 H, F, C1 ~ C5 또는

이다. 상기 R1에서 H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조, R2가 오르소, 메타, 파라 위치에 치환되어 있을 수 있는 벤젠구조(

)들을 갖는 치환체임을 나타낸다. R2는 H, X 또는 C1~C5이다. 상기 R2에서 H는 수소, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조, X는 할로겐 원자(F, Cl, Br)에 해당되며, X의 경우는 다른 고분자 사슬의 하이드록시 그룹과의 중합을 이룰 수 있는 기능성 그룹이기도 하다. 또한 상기 화학식 1에서 k는 0.001 - 1.000 의 범위를 지니며, s = 1 - k 값을 가지며, n은 고분자 중합체의 반복단위(repeating unit)를 나타내며, n은 정수로서 10~500을 나타낸다.CM1 or CM2 represents a crosslinkable moiety,

or

to be. In CM1 or CM2, R is an ethynyl part in which R1 is substituted (R =

), The double part (R =

) or

And can come in positions of ortho, meta, and para structures. G in R is a single bond, -O-, -S- or directly connected to carbon and carbon

Means. R1 is also H, F, C1 to C5 or

to be. In R1, H is hydrogen, F is fluorine, and C1 to C5 are hydrogen or fluorine-substituted alkyl structures having 1 to 5 carbon atoms, R2 may be substituted at ortho, meta and para positions. Benzene Structure

It is a substituent having a). R2 is H, X or C1-C5. In R2, H is hydrogen, C1 to C5 is an alkyl structure substituted with hydrogen or fluorine having 1 to 5 carbon atoms, X is a halogen atom (F, Cl, Br), and in case of X another polymer It is also a functional group capable of polymerizing with the hydroxy group of the chain. In addition, in Chemical Formula 1, k has a range of 0.001-1.000, has a value of s = 1-k, n represents a repeating unit of the polymer, and n represents 10 to 500 as an integer.

The sulfonated poly (arylene ether) copolymer containing the crosslinked structure of Chemical Formula 1 according to the first embodiment of the present invention is described in more detail according to the preparation method of Scheme 1 below.

Scheme 1

  k HO-SAr-OH + s HO-Ar1-OH + m X-Ar2-X

(2)

[Formula 3]

[Formula 1]

Reaction Scheme 1 is a reaction process for preparing Chemical Formula 1, and a method for preparing a polymer corresponding to Chemical Formula 1 is a condensation polymerization method, and monomers participating in the reaction may be different. In addition, the sulfonated monomer used in Scheme 1 uses a dihydroxy monomer.

Through the Scheme 1, a sulfonated poly (arylene ether) copolymer containing a crosslinked structure may be prepared.

In addition, in Reaction Scheme 1, k has a range of 0.001 to 1, s = 1-k, and (k + s) / m represents a range of 0.800 to 1.200. In addition, k, s, m correspond to the molar ratio of the monomer which participates in reaction.

)와 할라이드가 치환된 단량체(

)로 나뉠 수 있는데, 반응식 1에서의 (k+s)/m이 1.000 이하의 값을 가질 경우는 하이드록시가 치환된 단량체를 사용하고, (k+s)/m이 1.000 이상의 값을 가질 경우는 할라이드가 치환된 단량체를 사용한다. 화학식 3의 R2가 X일 경우에는 화학식 3에서 (k+s)/m의 값에 상관없이 하이드록시가 치환된 단량 체(

)를 사용할 수 있다.Where formula (3) is a hydroxy substituted monomer (

) And halide substituted monomers (

When (k + s) / m in Scheme 1 has a value of 1.000 or less, a hydroxy substituted monomer is used, and (k + s) / m has a value of 1.000 or more. Uses a monomer substituted with a halide. When R 2 in Formula 3 is X, hydroxy-substituted monomer regardless of the value of (k + s) / m in Formula 3 (

) Can be used.

Looking at the preparation process of Scheme 1, the sulfonated dihydroxy monomer and unsulfonated dihydroxy monomer are activated. The activation process is a process in which the dihydroxy monomer is activated to facilitate the polycondensation reaction with the dihalide monomer. In addition, the unsulfonated dihalide monomer may be added to the manufacturing process in the same step as the dihydroxy monomer.

First, a polycondensation reaction is carried out for 1 to 100 hours in a temperature range of 0 ° C. to 300 ° C. in the presence of a solvent consisting of a base, an azeotropic solvent, and an aprotic polar solvent to prepare a polymer according to Chemical Formula 2. In addition, a protic polar solvent may be used instead of the aprotic polar solvent depending on the type of preparation.

Subsequently, a crosslinked polymer of Formula 1 is formed by using the polymer of Formula 2 and the monomer substituted by hydroxy of Formula 3 or the monomer substituted by halide.

The formation reaction of Chemical Formula 1 uses the same method as the method of making the polymer polymer of Chemical Formula 2. That is, using the activation step and the polycondensation step to prepare a high-molecular polymer substituted with the cross-linking structure of the formula (1). In addition, the step of removing the azeotropic solvent may be further interposed before the condensation polymerization step after the activation step.

In addition, in the present embodiment, in order to improve the thermal stability, electrochemical properties, film forming ability, dimensional stability, mechanical stability, chemical properties, physical properties, cell performance, etc. of the polymer represented by the formula (2), Crosslinkable Moiety (CM1) or CM2 containing a crosslinkable crosslinkable group is substituted by a polycondensation reaction to obtain a sulfonated poly (arylene ether) copolymer containing a crosslinked structure of Formula 1 as a target of the present invention. Manufacture.

The polycondensation reaction and crosslinkable group introduction reaction for the synthesis of sulfonated poly (arylene ether) copolymer containing a crosslinked structure of the present invention include inorganic, selected from alkali metal, alkaline earth metal hydroxides, carbonates and sulfates as bases. It is also possible to use a base or an organic base selected from common amines including ammonia.

In addition, an aprotic polar solvent or a protic polar solvent may be used as the reaction solvent. As the aprotic polar solvent, N -methylpyrrolidone (NMP), dimethylformamide (DMF), N, N -dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and the like are used. Methylene chloride (CH ₂ Cl ₂ ), chloroform (CH ₃ Cl), tetrahydrofuran (THF) and the like may be used as the solvent, and benzene, toluene or xylene may be used as the non-solvent.

The sulfonated poly (arylene ether) copolymer containing the crosslinked structure of the present invention prepared by the method as described above is conventional in thermal stability, film forming ability, mechanical stability, chemical properties, physical properties, cell performance, etc. Maintains the same or better levels of sulfonated poly (arylene ether) copolymers or the Nafion membranes currently used as commercially available polymer electrolyte membranes, while providing significantly improved effects on electrochemical properties, particularly cationic conductivity and cell performance. In addition, even after prolonged exposure to moisture, electrolyte membrane properties did not change, resulting in high dimensional stability.

Such the present invention will be described in more detail based on the following production examples, but the present invention is not limited thereto.

Production Example  One : Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK -6F)

Scheme 2

Hydroquinonesulfonic acid potassium salt and 4, in a 100 ml two-necked flask equipped with a stirrer, nitrogen introduction tube, magnetic stub, Dean-Stark (azeotropic distillation) The molar ratio of 4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol) was set to 19 mmol: 1 mmol (k: s = 0.95: 0.05), K2CO3 (1.15 equivalence ratio), N, N -Dimethylacetamide (DMAc) (60 ml) and benzene (20 ml) were added.

The activation step was carried out at a temperature ranging from 135 ° C. to 140 ° C. for 6 to 8 hours, and water produced as a by-product during the reaction was removed by azeotropic distillation with benzene, one of the reaction solvents. Benzene was then removed from the reactor.

Thereafter, 20 mmol of decafluorobiphenyl is added to the reactor, and the reaction temperature is maintained at 140 ° C. for at least 12 hours to produce an intermediate compound.

To the solution containing the resulting intermediate compound, 3-ethynylphenol, benzene (10 ml) and K ₂ CO ₃ (1.15 equiv. Ratio) were added to the solution containing 0.2-0.5-fold molar ratio of the decafluorobiphenyl monomer. After further reacting at 140 ° C. for more than an hour, benzene was completely removed. In addition, water was removed by azeotropic distillation with benzene in order to remove the by-product water during the reaction. After the reaction was completed, precipitated in 500 mL of ethanol, washed several times with water and ethanol, and vacuum dried at 60 ℃ for 3 days. The final product (E-SFQK95-6F) was obtained as a pale brown solid, yielding over 90%.

In addition, the molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol) was 18 mmol. : 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k : s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to form sulfonated poly (arylene ether) copolymers having a crosslinked structure. Prepared. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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.

Production Example  2 : Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK - BP )

Scheme 3

In the same manner as in Preparation Example 1, the starting material was 4,4'-biphenol (4, instead of 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol) 4'-biphenol). 19 mmol: 1 mmol (k: s = 0.95: 0.05) of the molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4'-biphenol (4: 4'-biphenol), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7) sulfonated poly (arylene ether) aerial with crosslinked structure The coalescence was prepared. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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, E-SFQK30-BP.

Production Example  3: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK - HQ )

Scheme 4

The same procedure as in Preparation Example 1, except that 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisoprpylidene) diphenol) was used as a starting material, and hydroquinone was used. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and hydroquinone was 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1 ), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: A sulfonated poly (arylene ether) copolymer having a crosslinked structure was prepared using s = 0.4: 0.6) and 6 mmol: 14 mmol (k: s = 0.3: 0.7). Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SFQK95-HQ, E-SFQK90-HQ, E-SFQK85-HQ, E-SFQK80-HQ, E-SFQK75- Referred to as HQ, E-SFQK70-HQ, E-SFQK60-HQ, E-SFQK50-HQ, E-SFQK40-HQ, E-SFQK30-HQ.

Production Example  4 : Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK -6H)

Scheme 5

In the same manner as in Preparation Example 1, instead of 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol), the starting material was replaced with bisphenol-A (bisphenol-A). The molar ratio of hydroquinonesulfonic acid potassium salt and bisphenol-A was 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25) , 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 A sulfonated poly (arylene ether) copolymer having a crosslinked structure was prepared using mmol (k: s = 0.4: 0.6) and 6 mmol: 14 mmol (k: s = 0.3: 0.7). Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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, E-SFQK30-6H.

Production Example  5: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK -2 BP )

Scheme 6

2,2'-biphenol (2) instead of 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol , 2'-biphenol) was used, and the molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 2,2'-biphenol was 19 mmol: 1 mmol (k: s = 0.95: 0.05 ), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7) ) Copolymers were prepared. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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, E-SFQK30-2BP.

Production Example  6: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SFQK - DPE )

Scheme 7

In the same manner as in Preparation Example 1, the starting material was 4,4'-dihydroxydiamine instead of 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol) Phenyl ether (4,4'-dihydroxydiphenyl ether) was used, and the molar ratio of hydroquinonesulfonic acid potassium salt and 4,4'-dihydroxydiphenyl ether as starting materials was 19 mmol: 1. mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4) , 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7) Eggplants made sulfonated poly (arylene ether) copolymers. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SFQK95-DPE, E-SFQK90-DPE, E-SFQK85-DPE, E-SFQK80-DPE, E-SFQK75- It is referred to as DPE, E-SFQK70-DPE, E-SFQK60-DPE, E-SFQK50-DPE, E-SFQK40-DPE, E-SFQK30-DPE.

Production Example  7: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPECN - HQ )

Scheme 8

In the same manner as in Preparation Example 1, a starting material was used instead of 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol, hydroquinone (hydroquinone), 2,6-difluorobenzonitrile was used in place of decafluoro biphenyl as the dihalide material.

In addition, dimethyl sulfoxide (DMSO) (60 mL) and toluene (20 mL) were added as a reaction solvent instead of DMAc and benzene. The activation step was a temperature in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and hydroquinone was 20 mmol: 0 mmol (k: s = 1.00: 0), 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol Sulfonated poly (arylene ether) copolymers having a crosslinked structure were prepared using (k: s = 0.5: 0.5) and 8 mmol: 12 mmol (k: s = 0.4: 0.6). Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPECN100-HQ, E-SPECN95-HQ, E-SPECN90-HQ, E-SPECN85-HQ, E-SPECN80- It is called HQ, E-SPECN75-HQ, E-SPECN70-HQ, E-SPECN60-HQ, E-SPECN50-HQ, E-SPECN40-HQ.

Production Example  8 : Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPEK -6F)

Scheme 9

A 2,3-dihydroxynaphthalene-6-sulfonic acid monosoy in a 100 ml two-necked round flask equipped with a stirrer, nitrogen introduction tube, magnetic stub, and Dean-Stark (azeotropic distillation) Molar ratio of 2,3-dihydroxynaphthalene-6-sulfonic acid monosodium salt) and 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol K ₂ CO ₃ (1.15 equivalent ratio), N, N -dimethylsulfoxide (DMSO) (60 mL) and toluene (20 mL) were added as (k: s = 0.6: 0.4).

The activation step was carried out at a temperature ranging from 135 ° C to 140 ° C for 6-8 hours. The water produced as a by-product during the reaction was removed by azeotropic distillation with toluene, one of the reaction solvents. Removed from the reactor.

Thereafter, 20 mmol of 4,4'-difluorobenzophenone was added to the reactor, and the reaction temperature was maintained at 180 ° C. to form an intermediate compound reacted for 12 hours or more.

3-ethynylphenol, benzene (10 mL) and K ₂ CO ₃ (1.15 equivalents) in an amount corresponding to a 0.2 to 0.5-fold molar ratio of the 4,4'-difluorobenzophenone monomer in the polymer solution containing the intermediate compound formed. ) Was further reacted at 140 DEG C for at least 6 hours, and then toluene was completely removed. In addition, water was removed by azeotropic distillation with toluene in order to remove the by-product water during the reaction. After the reaction was completed, precipitated in 500 ml of ethanol, washed several times with water and ethanol, and vacuum dried at 60 ℃ for 3 days. The final product (E-SPEK60-6F) was obtained as a pale brown solid, yielding at least 90%.

In addition, 2,3-dihydroxynaphthalene-6-sulphonic acid monosodium salt (2,3-dihydroxynaphthalene-6-sulfonic acid monosodium salt) and 4,4 '-(hexafluoroisopropylidene) as starting materials The molar ratio of diphenol ((4,4'-hexafluoroisopropylidene) diphenol) was 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7 Sulfonated poly (arylene ether) copolymers having a crosslinked structure were prepared. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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-SPAEK40-6F, E-SPEK30-6F.

Production Example  9: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPEK - BP )

Scheme 10

4,4'-biphenol (4 instead of 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol) , 4'-biphenol) and 2,3-dihydroxynaphthalene-6-sulphonic acid monosodium salt and 4,4 'as starting materials The molar ratio of biphenols is 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15) , 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to prepare sulfonated poly (arylene ether) copolymers having a crosslinked structure. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPEK95-BP, E-SPEK90-BP, E-SPEK85-BP, E-SPEK80-BP, E-SPEK75- Referred to as BP, E-SPEK70-BP, E-SPEK60-BP, E-SPEK50-BP, E-SPAEK40-BP, E-SPEK30-BP.

Production Example  10: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPAEK - BP )

Scheme 11

The same process as in Preparation Example 1, except that the starting material was 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol instead of 4,4'-biphenol ( 4,4'-biphenol) was used, and 4,4'-difluorobenzophenone (4,4'-difluorobenzophenone) was used instead of decafluoro biphenyl as the dihalide material.

In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. 20 mmol: 0 mmol (k: s = 1.00: 0), 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2 ), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: Sulfonated poly (arylene ether) copolymers having a crosslinked structure were prepared using 10 mmol (k: s = 0.5: 0.5) and 8 mmol: 12 mmol (k: s = 0.4: 0.6). Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPAEK100, E-SPAEK95-BP, E-SPAEK90-BP, E-SPAEK85-BP, E-SPAEK80-BP, E-SPAEK75-BP, E-SPAEK70-BP, E-SPAEK60-BP, E-SPAEK50-BP, E-SPAEK40-BP.

Production Example  11: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPAEK -6F)

Scheme 12

In the same manner as in Preparation Example 1, 4,4'-difluorobenzophenone (4,4'-difluorobenzophenone) was used instead of decafluoro biphenyl as the starting material as the dihalide material. In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4 '-(hexafluoroisopropylidene) diphenol (19,4 mmol: 1) mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 13 mmol: 7 mmol (k: s = 0.65: 0.35) , 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6) Eggplants made sulfonated poly (arylene ether) copolymers. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were 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, E-SPAEK40-6F.

Production Example  12: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPAESO - BP )

Scheme 13

In the same manner as in Preparation Example 1, the starting material was 4,4-biphenol (4, instead of 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol) 4'-biphenol) was used and 4,4'-difluorodiphenyl sulfone was used instead of decafluoro biphenyl as the dihalide material. In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4'-biphenol was 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 13 mmol: 7 mmol (k: s = 0.65: 0.35), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6) sulfonated poly (arylene ether) aerial with crosslinked structure The coalesces were prepared. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPAESO95-BP, E-SPAESO90-BP, E-SPAESO85-BP, E-SPAESO80-BP, E-SPAESO75- It is referred to as BP, E-SPAESO70-BP, E-SPAESO65-BP, E-SPAESO60-BP, E-SPAESO50-BP, E-SPAESO40-BP.

Production Example  13: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPAESO -6F)

Scheme 14

In the same manner as in Preparation Example 1, 4,4'-difluorodiphenyl sulfone (4,4'-difluorodiphenyl sulfone) was used instead of decafluoro biphenyl as the starting material as a dihalide material. In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4 '-(hexafluoroisopropylidene) diphenol (19,4 mmol: 1) mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 13 mmol: 7 mmol (k: s = 0.65: 0.35) , 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6) Eggplants made sulfonated poly (arylene ether) copolymers. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPAESO95-6F, E-SPAESO90-6F, E-SPAESO85-6F, E-SPAESO80-6F, E-SPAESO75- 6F, E-SPAESO70-6F, E-SPAESOK65-6F, E-SPAESO60-6F, E-SPAESO50-6F, E-SPAESO40-6F.

Production Example  14: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPEKK - BP )

Scheme 15

4,4'-biphenol (4 instead of 4,4 '-(hexafluoroisopropylidene) diphenol (4,4'-hexafluoroisopropylidene) diphenol) , 4'-biphenol), and 1,3-bis (4-fluorobenzoyl) -benzene (1,3-bis (4-flurobenzoyl) -benzene) was used instead of decafluoro biphenyl as a dihalide material. Used. In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. 20 mmol: 0 mmol (k: s = 1.00: 0), 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2 ), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: Sulfonated poly (arylene ether) copolymers having a crosslinked structure were prepared using 10 mmol (k: s = 0.5: 0.5) and 8 mmol: 12 mmol (k: s = 0.4: 0.6). Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPEKK100, E-SPEKK95-BP, E-SPEKK90-BP, E-SPEKK85-BP, E-SPEKK80-BP, It is referred to as E-SPEKK75-BP, E-SPEKK70-BP, E-SPEKK60-BP, E-SPEKK50-BP, E-SPEKK40-BP.

Production Example  15: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- SPEKK -6F)

Scheme 16

1,3-bis (4-fluorobenzoyl) -benzene (1,3-bis (4-flurobenzoyl)-instead of decafluoro biphenyl as starting material was used as the dihalide material. benzene) was used. In addition, the activation step (activation step) the temperature was in the range of 150 ℃ ~ 160 ℃, the reaction temperature was also maintained by maintaining the 170 ℃. The molar ratio of the starting material hydroquinonesulfonic acid potassium salt and 4,4 '-(hexafluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol) was 19 mmol: 1 mmol (k: s = 0.95: 0.05), 18 mmol: 2 mmol (k: s = 0.9: 0.1), 17 mmol: 3 mmol (k: s = 0.85: 0.15), 16 mmol: 4 mmol (k: s = 0.8: 0.2), 15 mmol: 5 mmol (k: s = 0.75: 0.25), 14 mmol: 6 mmol (k: s = 0.7: 0.3), 13 mmol: 7 mmol (k: s = 0.65: 0.35) , 12 mmol: 8 mmol (k: s = 0.6: 0.4), 10 mmol: 10 mmol (k: s = 0.5: 0.5), 8 mmol: 12 mmol (k: s = 0.4: 0.6) Eggplants made sulfonated poly (arylene ether) copolymers. Each yield was at least 90%.

The poly (arylene ether) copolymers prepared by varying the ratio of k: s described above were E-SPEKK95-6F, E-SPEKK90-6F, E-SPEKK85-6F, E-SPEKK80-6F, E-SPEKK75- Refer to 6F, E-SPEKK70-6F, E-SPEKK65-6F, E-SPEKK60-6F, E-SPEKK50-6F, E-SPEKK40-6F.

The structures of the polymers of sulfonated poly (arylene ether) copolymers having a crosslinked structure synthesized by Preparation Examples 1 to 15 were analyzed by 1 H-NMR, 19 F-NMR, and FT-IR.

In the 1H-NMR analysis results in Figures 1 to 6, for comparison, E-SFQK polymer incorporating ethynyl group by polymerization with hydroquinonesulfonic acid potassium salt and decafluorobiphenyl. Compared with, it was confirmed that there is no hydroxy group peak of the monomer, proton peak corresponding to the ethynyl group can also be confirmed that the crosslinkable ethynyl group is substituted.

It can also be seen that the peaks corresponding to the peaks of the polymer appear. In addition, as a result of 19F-NMR analysis, only two peaks appeared, indicating that F dropped in the para position of the decafluorobiphenyl group by participating in the polymerization reaction.

Production Example  16: polymer Electrolyte membrane  Produce

Sulfonated poly (arylene ether) copolymers having a crosslinked structure synthesized in Preparation Examples 1 to 15 were dissolved in a solvent, and then filtered using a 0.45 µm to 1 µm PTFE membrane filter. Thereafter, the polymer solvent is poured onto the glass plate by a casting method on a clean glass plate support, and then left in a 40 ° C. oven for 24 hours.

Subsequently, heat treatment is performed for 30 minutes or more at a temperature of 80 ° C to 350 ° C for crosslinking of the polymer terminal. Also, preferably, the heat treatment is performed at 250 ° C. to 260 ° C. for at least 2 hours.

At this time, the solvent used may be a dipolar solvent, specifically N, N' -dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP) can be used.

After the heat treatment is completed, the reaction is cooled to room temperature and acid treatment to replace the salt ions (Na ⁺ , K ⁺ , alkyl amonium ion) of the sulfonate of the polymer prepared in Schemes 2 to 15 by hydrogen.

The acid treatment method is immersed in an aqueous solution of sulfuric acid (H ₂ SO ₄ ) at 2 normal concentration, an aqueous solution of nitric acid (HNO ₃ ) at 1 normal concentration, or an aqueous solution of hydrochloric acid (HCl) at 1 normal concentration for 24 hours, and then soaked in distilled water for 24 hours. It is placed in a solution of sulfuric acid (H ₂ SO ₄ ) of 0.5 molar concentration or boiling for 2 hours, but the acid treatment method is not limited thereto. The acid treated polymer electrolyte membrane was immersed in distilled water for 24 hours and then the cationic conductivity was measured.

According to the names of the sulfonated poly (arylene ether) copolymers according to Preparation Examples 1 to 15, the name of the prepared polymer membrane is also given separately. That is, when the polymer membrane was prepared using E-SFQK-6F in Preparation Example 1, the name of the polymer membrane is referred to as CSFQH-6F. Namely, the names of the 15 polymer membranes using the sulfonated poly (arylene ether) copolymers disclosed in Preparation Examples 1 to 15 were CSFQH-6F, CSFQH-BP, CSFQH-HQ, and CSFQH according to the order of Preparation Example. -6H, CSFQH-2BP, CSFQH-DPE, CSPECN-HQ, CSPEK-6F, CSPEK-BP, CSPAEK-BP, CSPAEK-6F, CSPAESO-BP, CSPAESO-6F, CSPEKK-BP, CSPEKK-6F.

Table 1 below shows the solubility of the 15 polymer membranes.

TABLE 1

Polyelectrolyte membrane NMP DMAc DMSO DMF THF Acetone CHCl3 MeOH Water CSFQH-6F I I I I I I I I I CSFQH-BP I I I I I I I I I CSFQH-HQ I I I I I I I I I CSFQH-6H I I I I I I I I I CSFQH-2BP I I I I I I I I I CSFQH-DPE I I I I I I I I I CSPECN-HQ I I I I I I I I I CSPEK-6F I I I I I I I I I CSPEK-BP I I I I I I I I I CSPAEK-BP I I I I I I I I I CSPAEK-6F I I I I I I I I I CSPAESO-BP I I I I I I I I I CSPAESO-6F I I I I I I I I I CSPEKK-BP I I I I I I I I I CSPEKK-6F I I I I I I I I I

As can be seen in Table 1, the polymer electrolyte membrane was not dissolved in any solvent, indicating that the polymer electrolyte membrane was crosslinked. In addition, it can be seen that not only is very chemically stable but also excellent in dimensional stability.

As can be seen in FIGS. 7 and 8, an electrolyte made of an E-SFQK polymer in which an ethynyl group is introduced by polymerizing with hydroquinonesulfonic acid potassium salt and decafluorobiphenyl. Compared with the membrane CSFQH, the structure of the polymer electrolyte membrane crosslinked through FT-IR is analyzed.

In addition, the glass transition temperature (Tg) of the polymer electrolyte membranes prepared in Preparation Example 16 was measured under a nitrogen atmosphere at 10 ° C./min by differential scanning calorimetry. As can be seen in Figures 9, 10, 11, 12 to 13 it can be seen that the thermal stability of Nafion which is currently commercialized at 200 ° C or more. In addition, the thermal decomposition temperature Td is also 300 ° C or higher, which is very excellent in thermal stability.

9, 10, 11, 12, and 13, the names of the polymer membranes, CSFQH90-6F, CSFQH80-6F, CSFQH70-6F, CSFQH90-BP, CSFQH80-BP, CSFQH70-BP means the following Has That is, CSFQH90-6F refers to a polymer electrolyte membrane formed using E-SFQK90-6F prepared in Preparation Example 1, and CSFQH90-BP refers to a polymer formed using E-SFQK90-BP prepared in Preparation Example 2. Refers to the electrolyte membrane, CSFQH90-HQ refers to the polymer electrolyte membrane formed using E-SFQK90-HQ prepared in Preparation Example 3, CSFQH90-6H refers to the E-SFQK90-6H prepared in Preparation Example 4 It refers to the polymer electrolyte membrane formed using, CSFQH90-DPE refers to the polymer electrolyte membrane formed using the E-SFQK90-DPE prepared in Preparation Example 6.

In addition, it can be seen that the polymer electrolyte membrane prepared as disclosed in FIG. 14 is transparent and amorphous.

The water uptake and cation conductivity of the polymer electrolyte membrane prepared in Preparation Example 16 are shown in Table 2 below in comparison with Nafion which is currently commercialized.

TABLE 2

Electrolyte membrane Ion exchange capacity (meq / g) Ion Conductivity (S / cm) c Water absorption rate (wt%) d Calculation a Experimental value b CSFQH95-6F 1.93 1.99 0.124 68 CSFQH90-6F 1.80 1.83 0.111 46 CSFQH85-6F 1.68 1.70 0.095 35 CSFQH80-6F 1.56 1.61 0.077 33 CSFQH70-6F 1.33 1.35 0.054 24 CSFQH95-BP 1.96 2.01 0.127 70 CSFQH90-BP 1.86 1.90 0.108 42 CSFQH85-BP 1.76 1.78 0.093 35 CSFQH80-BP 1.66 1.67 0.075 30 CSFQH70-BP 1.45 1.49 0.053 22 CSFQH95-HQ 1.98 1.98 0.132 74 CSFQH90-HQ 1.89 1.92 0.124 53 CSFQH85-HQ 1.80 1.87 0.109 45 CSFQH80-HQ 1.71 1.79 0.089 38 CSFQH70-HQ 1.52 1.53 0.066 27 CSFQH95-6H 1.95 1.98 0.131 80 CSFQH90-6H 1.84 1.87 0.123 60 CSFQH85-6H 1.74 1.75 0.094 36 CSFQH80-6H 1.63 1.67 0.076 31 CSFQH70-6H 1.41 1.55 0.069 27 CSFQH95-2BP 1.96 1.98 0.131 68 CSFQH90-2BP 1.86 1.87 0.100 40 CSFQH85-2BP 1.76 1.77 0.094 38 CSFQH80-2BP 1.66 1.65 0.060 30 CSFQH70-2BP 1.45 1.43 0.041 21 CSFQH95-DPE 1.96 2.02 0.138 104 CSFQH90-DPE 1.85 1.94 0.130 81 CSFQH85-DPE 1.75 1.78 0.101 55 CSFQH80-DPE 1.64 1.70 0.081 37 CSFQH70-DPE 1.44 1.50 0.055 27 E-SPEK60-6F 1.31 1.04 0.045 14 E-SPEK70-6F 1.56 1.30 0.056 21 E-SPEK80-6F 1.83 1.72 0.072 33 E-SPEK70-BP 1.74 1.65 0.060 22 Nafion 117 0.91 0.91 0.094 32   a: Calculated by monomer molar ratio {IEC = (1000 / repeated unit molecular weight) x sulfonated ratio x number of sulfonic acid groups} b: After soaking in 0.01N NaCl solution for 24 hours, titrated with 0.01N NaOH and measured. (Use phenolphthalein as indicator) c: Equivalent per sulfonic acid group d: Measured by impedance analyzer (AutoLab, PGSTAT 30, Netherlands) {σ (S / cm) / (R × S), L (cm) is between two electrodes Where R (Ω) is the membrane resistance and S (cm2) is the surface area of the membrane through which the ions pass} e: Weight calculation of the membrane {% water absorption (%) = (Wwet-Wdry) × 100 / Wdry, Wwet is wet Membrane weight, Wdry is the dry membrane weight}

As can be seen in Table 2, it can be seen that the positive ion conductivity, which is the most important property as the polymer electrolyte membrane, is much improved compared to Nafion, and the water absorption rate is lowered.

2nd Example

The sulfonated poly (arylene ether) copolymer according to the second embodiment of the present invention has a crosslinked structure at the end and is represented by the following Chemical Formula 4.

[Formula 4]

In Formula 4, SAr represents sulfonated aromatic.

,

,

,

또는

이다.SAr in Formula 4 is

,

,

,

or

to be.

In addition, Ar1 and Ar2 represent unsulfonated aromatics and may be the same or different from each other.

또는

이다. Ar1 or Ar2 is

or

to be.

,

,

,

,

,

,

,

,

또는

이며, A는 탄소와 탄소가 직접 연결되어 있는 단일결합, -O-, -S-,

,

,

,

,

또는

이며, E는 H, F, C1 ~ C5 또는

이다.Y is a single bond, -O-, -S-,

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

to be.

는 연결부분이 오르소, 메타, 파라 위치에 올 수 있는 벤젠구조를 나타내며,

는 불소(F)가 완전히 치환되어 있으며 연결부분이 오르소, 메타, 파라 위치에 올수 있는 벤젠구조를 의미한다. 즉

라 함은 연결부분이 오르소 (

), 메타 (

), 파라 (

) 위치에 올수 있는 불소 가 완전히 치환된 벤젠구조들을 의미한다. 또한 E에서 H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조를

는 L이 벤젠에 치환되어 있는 벤젠구조를 의미한다. 상기 구조식에서 L은 H, F, C1 ~ C5 를 나타내며, H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조를 의미한다.Also, in Y

Represents a benzene structure in which the linking moiety can be in the ortho, meta, or para position,

Refers to a benzene structure in which fluorine (F) is completely substituted and the linking portion can be at ortho, meta and para positions. In other words

Means the connection is ortho (

), Meta (

), Para (

Benzene structure that is completely substituted with fluorine which may be at position). In E, H represents hydrogen, F represents fluorine, and C1 to C5 represent an alkyl structure having hydrogen or fluorine substituted with 1 to 5 carbon atoms.

Means a benzene structure in which L is substituted for benzene. In the above structural formula, L represents H, F, C1 ~ C5, H means hydrogen, F is fluorine, C1 ~ C5 means an alkyl structure substituted with hydrogen or fluorine having 1 to 5 carbon atoms.

,

또는

이며 오르소, 메타, 파라 구조의 위치에 올 수 있다. Z에서 Y는 앞서 설명한 Y와 의미가 같다.In addition, Z is a bond in which carbon of benzene and -SO ₃ ^- M ⁺ are directly connected,

,

or

And can come in positions of ortho, meta, and para structures. Y in Z has the same meaning as Y described above.

M ⁺ is a counterion with a cationic charge and represents potassium ions (K ⁺ ), sodium ions (Na ⁺ ), alkyl amines ( ⁺ NR 4), and the like, and preferably potassium ions or sodium ions.

또는

이다. CM1 또는 CM2에서 R은 R1이 치환되어있는 삼중결합(ethynyl part)(R=

), 이중결합(vinyl part)(R=

) 또는

이며 오르소, 메타, 파라 구조의 위치에 올 수 있다. 상기 R에서 G는 탄소와 탄소가 직접 연결되어 있는 단일 결합, -O-, -S- 또는

를 의미한다. 또한 R1은 H, F, C1 ~ C5 또는

이다. 상기 R1에서 H는 수소를, F는 불소를, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조, R2가 오르소, 메타, 파라 위치에 치환되어 있을 수 있는 벤젠구조(

)들을 갖는 치환체임을 나타낸다. R2는 H, X 또는 C1~C5이다. 상기 R2에서 H는 수소, C1 ~ C5는 탄소수가 1에서 5를 의미하는 수소 또는 플루오린이 치환되어 있는 알킬구조, X는 할로겐 원자(F, Cl, Br)에 해당되며, X의 경우는 다른 고분자 사슬의 하이드록시 그룹과의 중합을 이룰 수 있는 기능성 그룹이기도 하다. 또한 상기 화학식 1에서 k는 0.001 - 1.000 의 범위를 지니며, s = 1 - k 값을 가지며, n은 고분자 중합체의 반복단위(repeating unit)를 나타내며, n은 정수로서 10~500을 나타낸다.CM1 or CM2 represents a crosslinkable moiety,

or

to be. In CM1 or CM2, R is an ethynyl part in which R1 is substituted (R =

), The double part (R =

) or

And can come in positions of ortho, meta, and para structures. G in R is a single bond, -O-, -S- or directly connected to carbon and carbon

Means. R1 is also H, F, C1 to C5 or

to be. In R1, H is hydrogen, F is fluorine, and C1 to C5 are hydrogen or fluorine-substituted alkyl structures having 1 to 5 carbon atoms, R2 may be substituted at ortho, meta and para positions. Benzene Structure

It is a substituent having a). R2 is H, X or C1-C5. In R2, H is hydrogen, C1 to C5 is an alkyl structure substituted with hydrogen or fluorine having 1 to 5 carbon atoms, X is a halogen atom (F, Cl, Br), and in case of X another polymer It is also a functional group capable of polymerizing with the hydroxy group of the chain. In addition, in Chemical Formula 1, k has a range of 0.001-1.000, has a value of s = 1-k, n represents a repeating unit of the polymer, and n represents 10 to 500 as an integer.

The sulfonated poly (arylene ether) copolymer containing a crosslinked structure at the terminal of Chemical Formula 4 according to the present invention is described in more detail according to the method of the following Scheme 16.

Scheme 16

[Chemical Formula 5]

[Formula 6]

[Chemical Formula 4]

Scheme 16 is a reaction process for preparing Chemical Formula 4. In addition, the method of preparing the polymer of Formula 5 is a condensation polymerization method, and the monomers participating in the reaction may be different.

In addition, the sulfonated monomer (X-SAr-X) used in Scheme 4 uses a dihalide monomer. Through Scheme 16, a sulfonated poly (arylene ether) copolymer having a crosslinked structure may be prepared.

In addition, in Reaction Scheme 16, k has a range of 0.001 to 1, s = 1-k, and (k + s) / m has a range of 0.8 to 1.2. In addition, k, s, m represent the molar ratio of the monomer which participates in reaction.

)와 할라이드가 치환된 단량체(

)로 나뉠 수 있는데, 반응식 16에서의 (k+s)/m이 1 이하의 값을 가지는 경우, 할라이드가 치환된 단량체(

)를 사용하고, (k+s)/m이 1 이상의 값을 가지는 경우, 하이드록시가 치환된 단량체(

)를 사용한다. 또한, 화학식 6의 R2가 X일 경우에는 반응식 16에서 (k+s)/m의 값에 상관없이 하이드록시가 치환된 단량체(

)를 사용할 수 있다.Where Formula 6 represents a monomer in which a hydroxy group is substituted (

) And halide substituted monomers (

If (k + s) / m in Scheme 16 has a value of 1 or less, the halide substituted monomer (

) And (k + s) / m has a value of 1 or more, the hydroxyl substituted monomer (

). In addition, when R2 of Formula 6 is X, the monomer in which hydroxy is substituted regardless of the value of (k + s) / m in Scheme 16 (

) Can be used.

In the preparation of Scheme 16, the unsulfonated dihydroxy monomer is activated. The activation process is a process to facilitate the polycondensation reaction of the dihydroxy monomer with the dihalide monomer. In addition, the sulfonated dihalide monomer and the unsulfonated dihalide monomer may be added to the manufacturing process in the same step as the dihydroxy monomer.

First, a polycondensation reaction is carried out for 1 to 100 hours at a temperature range of 0 ° C. to 300 ° C. in the presence of a solvent composed of a base, an azeotropic solution, and an aprotic polar solvent, to prepare a polymer according to Chemical Formula 5. In addition, a protic polar solvent may be used instead of the aprotic polar solvent depending on the type of preparation.

Subsequently, a polymer polymer having a crosslinked structure is formed at the terminal of Formula 4 by using the polymer of Formula 5 and the hydroxy-substituted monomer or the halide-substituted monomer. The reaction of Formula 4 is substantially the same as the method of making the polymer of Formula 5.

That is, using the activation step and the condensation polymerization step to prepare a polymer substituted with the cross-linked structure of the formula (4). In addition, the step of removing the azeotropic solvent may be further interposed before the condensation polymerization step after the activation step.

In addition, in the present embodiment, to improve the thermal stability, electrochemical properties, film forming ability, dimensional stability, mechanical stability, chemical properties, physical properties, cell performance, etc. of the polymer represented by the formula (5), at the end of the polymer chain Crosslinkable Moiety (CM) 1 or CM2 including a crosslinkable group capable of thermally crosslinking is substituted by a polycondensation reaction to prepare a sulfonated poly (arylene ether) copolymer containing a crosslinking structure of formula (4).

The polycondensation reaction and the crosslinkable group introduction reaction for the synthesis of sulfonated poly (arylene ether) copolymer containing a crosslinked structure of the present invention include inorganic, selected from hydroxides, carbonates and sulfates of alkali or alkaline earth metals as bases. It is possible to use a base or an inorganic base selected from common amines including ammonia.

As the reaction solvent, aprotic polar solvents or methylene chlorides such as N -methylpyrrolidone (NMP), dimethylformamide (DMF), N, N -dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO) Protic polar solvents such as (CH ₂ Cl ₂ ), chloroform (CH ₃ Cl) and tetrahydrofuran (THF) may be used, and benzene, toluene, xylene or the like may be used as a non-solvent.

The sulfonated poly (arylene ether) copolymer containing the crosslinked structure of the present invention prepared by the method as described above is conventional in thermal stability, film forming ability, mechanical stability, chemical properties, physical properties, cell performance, etc. Maintains the same or better levels of sulfonated poly (arylene ether) copolymers or the Nafion membranes currently used as commercially available polymer electrolyte membranes, while providing significantly improved effects on electrochemical properties, particularly cationic conductivity and cell performance. In addition, even after prolonged exposure to moisture, electrolyte membrane properties did not change, resulting in high dimensional stability.

Such the present invention will be described in more detail based on the following production examples, but the present invention is not limited thereto.

Production Example  17: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- DSPESO -6F)

Scheme 17

E-DSPESO-6F was synthesized in the same manner as in Preparation Example 1 except that 3,3'-disulfonated-4,4'-difluorodiphenyl sulfone (3,3'-disulfonated) was used as a sulfonated monomer. -4,4'-difluorodiphenyl sulfone), 4,4'-difluorodiphenyl sulfone as an unsulfonated dihalide monomer, 4,4 '-(hexa as dihydroxy monomer The polymerization was carried out using fluoroisopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol).

The temperature of the activation step was performed for 6 to 8 hours in the range of 150 ° C to 170 ° C, and the polymerization was carried out by changing the reaction temperature to 170 ° C to 180 ° C.

3,3'-disulfonated-4,4'-difluorodiphenyl sulfone (3,3'-disulfonated-4,4'-difluorodiphenyl sulfone) and 4,4'-difluorodiphenyl sulfone (4, The molar ratio of 4'-difluorodiphenyl sulfone) is 10 mmol: 10 mmol (k: s = 0.5: 0.5), 9 mmol: 11 mmol (k: s = 0.45: 0.55), 8 mmol: 12 mmol (k: s = 0.4 : 0.6), 7 mmol: 13 mmol (k: s = 0.35: 0.65), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to form sulfonated poly (arylene ether) copolymers having a crosslinked structure. Manufacture.

The sulfonated poly (arylene ether copolymers) prepared according to the above-described change in the ratio of k: s, in order, E-DSPESO50-6F, E-DSPESO45-6F, E-DSPESO40-6F, and E-DSPESO35, respectively. -6F, E-DSPESO30-6F The yield of each product was at least 90%.

Production Example  18: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- DSPESO - BP )

Scheme 18

E-DSPESO-BP was synthesized in the same manner as in Preparation Example 1 except that 3,3'-disulfonated-4,4'-difluorodiphenyl sulfone (3,3'-disulfonated) was used as a sulfonated monomer. -4,4'-difluorodiphenyl sulfone), 4,4'-difluorodiphenyl sulfone as an unsulfonated dihalide monomer, 4,4'-biphenol as a dihydroxy monomer Polymerization was carried out using (4,4'-biphenol).

The temperature of the activation step was performed for 6 to 8 hours in the range of 150 ° C to 170 ° C, and the polymerization was performed by changing the reaction temperature to 170 ° C to 180 ° C.

3,3'-disulfonated-4,4'-difluorodiphenyl sulfone (3,3'-disulfonated-4,4'-difluorodiphenyl sulfone) and 4,4'-difluorodiphenyl sulfone (4, The molar ratio of 4'-difluorodiphenyl sulfone) is 10 mmol: 10 mmol (k: s = 0.5: 0.5), 9 mmol: 11 mmol (k: s = 0.45: 0.55), 8 mmol: 12 mmol (k: s = 0.4 : 0.6), 7 mmol: 13 mmol (k: s = 0.35: 0.65), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to form sulfonated poly (arylene ether) copolymers having a crosslinked structure. Prepared.

The sulfonated poly (arylene ether copolymers) prepared according to the above-described change in the ratio of k: s, respectively, in order, E-DSPESO50-BP, E-DSPESO45-BP, E-DSPESO40-BP, E-DSPESO35 -BP, E-DSPESO30-BP The yield of each product was at least 90%.

Production Example  19: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- DSPEK -6F)

Scheme 19

E-DSPEK-6F was synthesized in the same manner as in Preparation Example 1 except that 3,3'-disulfonated-4,4'-difluorobenzophenone (3,3'-disulfonated) was used as a sulfonated monomer. -4,4'-difluorobenzophenone), 4,4'-difluorobenzophenone as an unsulfonated dihalide monomer, 4,4 '-(hexafluoro as a dihydroxy monomer The polymerization was carried out using leusopropylidene) diphenol ((4,4'-hexafluoroisopropylidene) diphenol).

The temperature of the activation step was performed for 6 to 8 hours in the range of 150 ° C to 170 ° C, and the polymerization was carried out by changing the reaction temperature to 170 ° C to 180 ° C.

3,3'-disulfonated-4,4'-difluorobenzophenone (3,3'-disulfonated-4,4'-difluorobenzophenone) and 4,4'-difluorobenzophenone (4,4 The molar ratio of '-difluorobenzophenone) is 10 mmol: 10 mmol (k: s = 0.5: 0.5), 9 mmol: 11 mmol (k: s = 0.45: 0.55), 8 mmol: 12 mmol (k: s = 0.4: 0.6 ), 7 mmol: 13 mmol (k: s = 0.35: 0.65), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to prepare a sulfonated poly (arylene ether) having a cross-linked structure.

The sulfonated poly (arylene ether copolymers) prepared according to the above-described change in the ratio of k: s, in order, E-DSPEK50-6F, E-DSPEK45-6F, E-DSPEK40-6F, and E-DSPEK35, respectively. -6F, E-DSPEK30-6F The yield of each product was at least 90%.

Production Example  20: Crosslinked structure  Branch Sulfonated Poly ( Arylene  Ether) Preparation of Copolymers (E- DSPEK - BP )

Scheme 20

E-DSPEK-BP was synthesized in the same manner as in Preparation Example 1 except that 3,3'-disulfonated-4,4'-difluorobenzophenone (3,3'-disulfonated) was used as a sulfonated monomer. -4,4'-difluorobenzophenone), 4,4'-difluorobenzophenone as unsulfonated dihalide monomer, 4,4'-biphenol as dihydroxy monomer (4 , 4'-biphenol) was used for polymerization. The temperature of the activation step was performed for 6 to 8 hours in the range of 150 ° C to 170 ° C, and the polymerization was carried out by changing the reaction temperature to 170 ° C to 180 ° C.

3,3'-disulfonated-4,4'-difluorobenzophenone (3,3'-disulfonated-4,4'-difluorobenzophenone) and 4,4'-difluorobenzophenone (4,4 The molar ratio of '-difluorobenzophenone) is 10 mmol: 10 mmol (k: s = 0.5: 0.5), 9 mmol: 11 mmol (k: s = 0.45: 0.55), 8 mmol: 12 mmol (k: s = 0.4: 0.6 ), 7 mmol: 13 mmol (k: s = 0.35: 0.65), 6 mmol: 14 mmol (k: s = 0.3: 0.7) to prepare sulfonated poly (arylene ether) copolymers having a crosslinked structure. .

The sulfonated poly (arylene ether copolymers) prepared according to the above-described change in the ratio of k: s, in order, E-DSPEK50-BP, E-DSPEK45-BP, E-DSPEK40-BP, E-DSPEK35, respectively. -BP, E-DSPEK30-BP The yield of each product was at least 90%.

Production Example  21: polymer Electrolyte membrane  Produce( CDSPESO -6F, CDSPESO - BP , CDSPEK -6F, CDSPEK - BP )

E-DSPESO-6F, E-DSPESO-BP, E-DSPEK-6F, and E-DSPEK-BP which are sulfonated poly (arylene ether) copolymers having a crosslinked structure prepared in Preparation Examples 17-20. The polymer electrolyte membranes CDSPESO-6F, CDSPESO-BP, CDSPEK-6F, and CDSPEK-BP are prepared by using the same. The polymer electrolyte membrane is named after sulfonated poly (arylene ether) copolymers in the order listed. That is, the polymer electrolyte membrane using E-DSPESO-6F is referred to as CDSPESO-6F, and the polymer electrolyte membrane using E-DSPEK-BP is referred to as CDSPEK-BP.

In addition, the method of manufacturing the polymer electrolyte membrane uses the same method as described in Preparation Example 16 of the first embodiment.

The solubility measurement results of the prepared polymer electrolyte membranes are shown in Table 3 below.

[Table 3]

Polymer electrolyte membrane NMP DMAc DMSO DMF THF Acetone CHCl3 MeOH Water CDSPESO-6F I I I I I I I I I CDSPESO-BP I I I I I I I I I CDSPEK-6F I I I I I I I I I CDSPEK-BP I I I I I I I I I

As can be seen in Table 3, the polymer electrolyte membrane is not dissolved in any solvent, and thus the polymer electrolyte membrane is crosslinked. In addition, it is chemically very stable, it can be seen that the dimensional stability is excellent.

1 shows the ¹ H-NMR and ¹⁹ F-NMR spectra of the sulfonated poly (arylene ether) copolymers (E-SFQK-6Fs) containing the crosslinked structure of the present invention.

FIG. 2 shows the ¹ H-NMR and ¹⁹ F-NMR spectra of sulfonated poly (arylene ether) copolymers (E-SFQK-BPs) containing crosslinked structures.

FIG. 3 shows the ¹ H-NMR and ¹⁹ F-NMR spectra of sulfonated poly (arylene ether) copolymers (E-SFQK-HQs) containing crosslinked structures.

FIG. 4 shows the ¹ H-NMR and ¹⁹ F-NMR spectra of sulfonated poly (arylene ether) copolymers (E-SFQK-6Hs) containing crosslinked structures.

FIG. 5 shows the ¹ H-NMR and ¹⁹ F-NMR spectra of sulfonated poly (arylene ether) copolymers (E-SFQK-DPEs) containing crosslinked structures.

FIG. 6 shows the ¹ H-NMR spectrum of a sulfonated poly (arylene ether) copolymer (E-SPEK-6Fs) containing crosslinked structure.

7 shows FT-IR spectra of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-6Fs).

8 shows FT-IR spectra of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-BPs).

9 is a graph showing the glass transition temperature (Tg) and pyrolysis temperature (Td) of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-6Fs).

10 is a graph showing the glass transition temperature (Tg) and pyrolysis temperature (Td) of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-BPs).

FIG. 11 is a graph showing the glass transition temperature (Tg) and pyrolysis temperature (Td) of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-HQs).

12 is a graph showing the glass transition temperature (Tg) and pyrolysis temperature (Td) of crosslinked sulfonated poly (arylene ether) copolymers (CSFQH-DPEs).

FIG. 13 is a graph showing the glass transition temperature (Tg) and pyrolysis temperature (Td) of crosslinked sulfonated poly (arylene ether) copolymer (CSFQH-6Hs).

14 is a photograph of a crosslinked polymer electrolyte membrane.

Claims (18)

A sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal represented by the following formula (1). [Formula 1]

In Formula 1, SAr represents sulfonated aromatics, and Ar1 and Ar2 represent unsulfated aromatics. In addition, CM1 and CM2 represent the part which can be bridge | crosslinked. In Chemical Formula 1, k has a range of 0.001 to 1, s has a value of 1-k, n represents a repeating unit of a polymer, and n is an integer of 10 to 500. In addition, in Formula 1, the SAr is

,

,

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

And L is H, F, C1-C5, and M ⁺ is a salt ion having a cationic charge. The sulfonated poly (arylene ether) copolymer according to claim 1, wherein the sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal of Chemical Formula 1 is formed by the following Scheme 1. coalescence. Scheme 1

(2)

[Formula 3]

[Formula 1]

In Reaction Scheme 1, k has a range of 0.001 to 1, s = 1-k, and (k + s) / m represents a range of 0.800 to 1.200. In addition, k, s, m correspond to the molar ratio of the monomer which participates in reaction. In Schemes 1 and 3, X is a halogen atom, and R is an ethynyl part in which R 1 is substituted (R =

), The double part (R =

) or

G is a single bond, -O-, -S- or a carbon to which carbon is directly connected.

R1 is H, F, C1 to C5 or

And R2 is H, X or C1-C5. delete The method of claim 2, wherein Ar1 or Ar2 is

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

And L is H, F, C1-C5. The method of claim 2, wherein the CM1 or CM2 is

or

Sulfonated poly (arylene ether) copolymer, characterized in that The sulfonated poly (arylene ether) copolymer of claim 1, wherein the salt ion having a cationic charge is potassium ions, sodium ions or alkyl amines. A sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal represented by the following formula (4). [Formula 4]

In Formula 4, SAr represents sulfonated aromatics, and Ar1 and Ar2 represent unsulfated aromatics. In addition, CM1 and CM2 represent the part which can be bridge | crosslinked. In Formula 4, k has a range of 0.001 to 1, s has a value of 1-k, n represents a repeating unit of the polymer, and n is an integer of 10 to 500. In addition, in Formula 4, SAr is

,

,

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

And L is H, F, C1-C5, and M ⁺ is a salt ion having a cationic charge. The sulfonated poly (arylene ether) copolymer according to claim 7, wherein the sulfonated poly (arylene ether) copolymer having a crosslinked structure at the terminal of Formula 4 is formed by the following Scheme 2. coalescence. Scheme 2

[Chemical Formula 5]

[Formula 6]

[Chemical Formula 4]

In Scheme 2, k has a range of 0.001 to 1, s = 1-k, and (k + s) / m represents a range of 0.800 to 1.200. In addition, k, s, m correspond to the molar ratio of the monomer which participates in reaction. In Scheme 2 and Chemical Formula 6, X is a halogen atom, R is an ethynyl part in which R1 is substituted (R =

), The double part (R =

) or

G is a single bond, -O-, -S- or a carbon to which carbon is directly connected.

R1 is H, F, C1 to C5 or

And R2 is H, X or C1-C5. delete The method of claim 8, wherein Ar1 or Ar2 is

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

And L is H, F, C1-C5. The method of claim 8, wherein the CM1 or CM2

or

Sulfonated poly (arylene ether) copolymer, characterized in that 8. The sulfonated poly (arylene ether) copolymer of claim 7, wherein the salt ion having a cationic charge is potassium ions, sodium ions or alkyl amines. A polymer electrolyte membrane crosslinked through heat treatment using a poly (arylene ether) copolymer represented by Formula 7 or Formula 8 below. [Formula 7]

[Formula 8]

In Formulas 7 and 8, SAr represents a sulfonated aromatic, and Ar1 and Ar2 represent an unsulfonated aromatic. In addition, CM1 and CM2 represent the part which can be bridge | crosslinked. In Formulas 7 and 8, k has a range of 0.001 to 1, s has a value of 1-k, n represents a repeating unit of the polymer, and n is an integer of 10 to 500. The SAr is

,

,

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

And L is H, F, C1-C5, and M ⁺ is a salt ion having a cationic charge. delete The crosslinked polymer electrolyte membrane of claim 13, wherein the salt ion having a cationic charge is potassium ions, sodium ions, or alkyl amines. 16. The crosslinked polymer electrolyte membrane of claim 15, wherein the crosslinked polymer electrolyte membrane is substituted with hydrogen by the salt ion of the sulfonated aromatic through acid treatment. The method of claim 13, wherein Ar1 or Ar2 is

or

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

,

,

,

,

,

,

,

,

or

A is a single bond, -O-, -S-,

,

,

,

,

or

E is H, F, C1 to C5 or

L is H, F, C1-C5, CM1 or CM2 is

or

R is a triple bond in which R1 is substituted (R =

), The double part (R =

) or

G is a single bond, -O-, -S- or a carbon to which carbon is directly connected.

R1 is H, F, C1 to C5 or

Wherein R2 is H, X or C1 to C5. The solvent according to claim 13, wherein the heat treatment is performed by dissolving the sulfonated poly (arylene ether) copolymer of Formula 7 or Formula 8 in a solvent, followed by a temperature of 80 ° C to 350 ° C, and a solvent used for the heat treatment. The crosslinked polymer electrolyte membrane, characterized in that the bipolar solvent.

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