KR101517011B1 - Tetrasulfonated poly(arylene biphenyl sulfone) copolymers, Manufacturing Method thereof and Proton Exchange Membrane for Fuel Cells comprising thereof - Google Patents

Abstract

...화학식(1)
상기 화학식(1)에서 Ar₁, Ar₂ 및 Ar₃은 각각 독립적으로 하기 화학식(2-1) 내지 화학식(2-6) 중에서 선택된 어느 하나인 것이며,
Y는 -S-, -O-, -N-, -C(=O)- 또는 -S(=O)₂-이며,
X는

또는

이며,
M은 -H, -Li, -Na, -K, -Rb, -Cs 또는 Fr이며,
n는 0.01∼1이고,
z는 10∼800이다.

...화학식(2-1)

...화학식(2-2)

...화학식(2-3)

...화학식(2-4)

...화학식(2-5)

...화학식(2-6)The present invention relates to a tetra sulfonated polyarylene biphenyl sulfone copolymer having the following general formula (1), a process for producing the same, and a cation exchange membrane for a fuel cell comprising the compound represented by the general formula (1).

(1)
In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)
Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and
X is

or

Lt;
M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,
n is from 0.01 to 1,
z is from 10 to 800.

(2-1)

(2-2)

(2-3)

(2-4)

(2-5)

(2-6)

Description

TECHNICAL FIELD The present invention relates to a tetra sulfonated polyarylene biphenyl sulfone copolymer, a process for producing the same, and a cation exchange membrane for fuel cells including the above compound (Tetrasulfonated poly (arylene biphenyl sulfone) copolymers, Manufacturing Method thereof and Proton Exchange Membrane for Fuel Cells,

The present invention relates to a tetra sulfonated polyarylene biphenyl sulfone copolymer having the following general formula (1), a process for producing the same, and a cation exchange membrane for a fuel cell comprising the compound represented by the general formula (1).

...화학식(1)

(1)

In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

...화학식(2-4)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

A fuel cell is a power generation system that converts chemical energy generated by the electrochemical reaction of fuel and oxygen into electrical energy.

The type of the fuel cell depends on the type of the electrolyte used. Examples of the type of the fuel cell include an alkaline fuel cell (AFC), a proton exchange membrane fuel cell (PEMFC), a phosphoric acid fuel cell phosphoric acid fuel cells (PAFC), molten carbonate fuel cells (MCFC), and solid oxide fuel cells (SOFC).

Each fuel cell operates on a fundamentally similar principle, but the type of fuel, the operating temperature, the catalyst, and the electrolyte are different.

Fuel cells, which are attracting attention as eco-friendly energy, have been actively studied for the application of cation exchange membrane fuel cells to popularization. The reason for this is that the cation exchange membrane fuel cell is superior to other fuel cells in terms of energy output characteristics through fuel and is suitable for application to power generation systems in mobile type, It has a very good advantage in terms of application.

The cation exchange membrane used as the material of the cation exchange membrane fuel cell (PEMFC) is generally composed of a main chain composed of fluorinated alkylene and a sulfonated perfluoropolymer composed of sulfonic acid group-introduced fluorinated vinyl ether (for example, Nafion, Products) have been used. This type of cation exchange membrane exhibits effective ion conductivity by absorbing a certain amount of water.

However, fluorinated cation exchange membranes are not available for industrial applications in terms of cost, unlike their excellent performance. Therefore, in order to lower the recent price, researches on hydrocarbons based ion exchange membranes are underway.

The inventors of the present invention have found that a cation exchange membrane for a fuel cell comprising a tetra-sulphonated polyarylene biphenylsulfonic copolymer having the following formula (1) has excellent ion conductivity and has a high ion conductivity of medium to long term And thus, an inexpensive cation-exchange membrane can be produced. Thus, the present invention has been completed.

...화학식(1)

(1)

In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

...화학식(2-4)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

As a prior art related to the present invention, in Polymer 2006, 47, 4132, and 4139, a multi-block copolymer (multi-block copolymer) composed of a hydrophilic block and a hydrophobic block alternately as a cation- block copolymer cation exchange membrane.

Korean Patent No. 10-0823503 discloses an ion exchange resin membrane; And self-humidifying particles dispersed in the ion exchange resin membrane, wherein the self-humidifying particles represent a cation exchange membrane for a fuel cell having an average particle diameter of 1 to 30 nm.

Korean Patent Publication No. 2011-0126033 discloses a compound which is a product obtained by polymerizing a composition for forming a polyurethane compound containing a diisocyanate compound and an aromatic polyol, a composition comprising the compound and the interpenetrating polymer, an electrode for a fuel cell comprising the same, An electrolyte membrane for a fuel cell, and a fuel cell having the same.

However, the present invention and the prior arts are different from each other in the technical features of the invention, and thus the inventions have different configurations.

It is an object of the present invention to provide a cation exchange membrane for fuel cells having excellent ion conductivity and a method for producing the same.

Another object of the present invention is to develop an inexpensive cation exchange membrane by exhibiting a high ion conductivity performance over the medium to long term under moderate to low temperature and high humidity.

Another object of the present invention is to provide a cation exchange membrane for a fuel cell which is superior to a Nafion membrane by exhibiting higher ion conductivity at a temperature range similar to Nafion which is a common membrane of a cation exchange membrane for a fuel cell, And a fuel cell including the cation exchange membrane for the fuel cell.

The present invention relates to a tetrasulfonated polyarylene biphenylsulfonic copolymer having the following formula (1), a process for producing the same, a method for producing a cation exchange membrane for a fuel cell and a method for producing a cation exchange membrane for a fuel cell, .

The present invention can provide a conjugate of an electrode and a cation exchange membrane for a fuel cell comprising a tetrasulfonated polyarylene biphenylsulfonic copolymer having the following formula (1).

The present invention can provide a fuel cell containing a cation exchange membrane for a fuel cell comprising a tetrasulfonated polyarylene biphenylsulfonic copolymer having the following formula (1).

...화학식(1)

(1)

In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

...화학식(2-4)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

The tetra sulfonated polyarylene biphenyl sulfone copolymer of the present invention can be used to produce a cation exchange membrane for a fuel cell without additional apparatus and process steps requiring additional high pressure or reduced pressure.

Further, the present invention is advantageous in that a cation exchange membrane for a fuel cell can be easily provided through the advantage that a tetra sulfonated polyarylene biphenyl sulfonic copolymer can be easily used to obtain a cation exchange membrane for a fuel cell.

1 is a graph showing the results of measurement of a polymer prepared in Preparation Example 1, a polymer prepared in Preparation Example 2, a polymer prepared in Example 1, a polymer prepared in Example 2, a polymer prepared in Example 3, ^& Lt; ¹ > H NMR.
FIG. 2 shows FT-IR measurement results of the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, and the copolymers prepared in Comparative Examples.
FIG. 3 is a graph showing the relationship between the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, the copolymer prepared in Comparative Example, and Taf (117) And the transition temperature (right side in Fig. 3).
4 shows the water content of the copolymer prepared in Example 1, the copolymer prepared in Example 2 and the copolymer prepared in Example 3 according to the temperature.
5 shows ionic conductivity values according to the temperature of the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, the copolymer prepared in Comparative Example, and Nafion 117 will be.

The present invention relates to a tetra-sulphonated polyarylene biphenyl sulfone copolymer having the following formula (1).

...화학식(1)

(1)

In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

The present invention relates to a process for preparing a tetrasulfonated polyarylene biphenylsulfonic copolymer of the following formula (1) by reacting a compound of the formula (3), a compound of the formula (4) and a compound of the formula (5) .

...화학식(1)

(1)

...화학식(3)

(3)

...화학식(4)

(4)

X ????? (5)

Ar ₁ , Ar ₂ and Ar ₃ in the compound of the formula (1), the compound of the formula (3), the compound of the formula (4) and the compound of the formula (5) (2-6). In this case,

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

...화학식(2-4)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

In the preparation of the tetrasulfonated polyarylene biphenyl sulfone copolymer of the above formula (1), the reaction is carried out by mixing the compound of the formula (3), the compound of the formula (4) and the compound of the formula (5) The solvent and toluene were added and the dehydration reaction was carried out at 130 to 150 ° C for 3 to 8 hours to remove the toluene and then the reaction was maintained at 180 to 200 ° C for 24 to 48 hours to obtain a reaction product having viscosity, A sulfonated polyarylene biphenyl sulfone copolymer can be prepared.

In the preparation of the compound of formula (1), the compound of formula (3) and the compound of formula (4) may be mixed in a molar ratio of 1: 9 to 9: 1.

In the preparation of the compound of formula (1), the compound of formula (3) and the compound of formula (4) may be mixed in a molar ratio of 1: 9 to 5: 5.

In the preparation of the compound of formula (1), the reaction can be carried out after mixing the compound of formula (3): the compound of formula (4) in a molar ratio of 1: 9.

In the preparation of the compound of formula (1), the reaction may be carried out after the compound of formula (3): the compound of formula (4) is mixed at a molar ratio of 3: 7.

In the preparation of the compound of formula (1), the reaction can be carried out after mixing the compound of formula (3): the compound of formula (4) in a molar ratio of 5: 5.

In the preparation of the compound of formula (1), the compound of formula (3): the compound of formula (5) may be reacted in a molar ratio of 1: 9 to 9: 1.

In the preparation of the compound of formula (1), the reaction may be carried out after mixing the compound of formula (3): the compound of formula (5) in a molar ratio of 1: 1.

In the preparation of the compound of formula (1), the reaction is carried out in a solvent in which the solvent is selected from dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methylpyrrolidone (NMP), dimethylformamide (DMF), and tetrahydrofuran You can use one.

The potassium carbonate used in preparing the compound of formula (1) may be used in an amount of 1 to 5 moles per mole of the compound of formula (3), and the solvent may be 5 to 50 ml per 1 mole of the compound of formula (3) And toluene may be used in an amount of 5 to 50 ml per 1 mole of the compound of the formula (3).

The compound of formula (3) may have a weight average molecular weight (Mw) of 3000 g / mol to 500,000 g / mol.

The compound of formula (4) may have a weight average molecular weight (Mw) of 3000 g / mol to 500,000 g / mol.

The present invention relates to a cation exchange membrane for a fuel cell comprising a tetra-sulphonated polyarylene biphenyl sulfone copolymer having the following general formula (1) and a process for producing the same.

...화학식(1)

(1)

In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)

Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and

또는

이며, X is

or

Lt;

M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,

n is from 0.01 to 1,

z is from 10 to 800.

...화학식(2-1)

(2-1)

...화학식(2-2)

(2-2)

...화학식(2-3)

(2-3)

...화학식(2-4)

(2-4)

...화학식(2-5)

(2-5)

...화학식(2-6)

(2-6)

The cation exchange membrane for a fuel cell comprising the tetra sulfonated polyarylene biphenyl sulfone copolymer of formula (1) can be prepared using the following steps (a) to (c).

(A) adding a tetrasulfonated polyarylenebiphenylsulfonic copolymer represented by the formula (1) to a solvent, agitating and then allowing to stand to obtain a precipitate and drying the precipitate;

(B) dissolving the dried precipitate in a solvent and stirring to obtain a solution;

(C) pouring the above solution onto a substrate and drying

The above step (a) may be carried out by adding the compound of formula (1) to a solvent at a ratio of 200 to 500 parts by weight based on 100 parts by weight of the compound of formula (1), stirring the mixture at 100 to 500 rpm for 10 to 15 hours It is allowed to stand for 1 to 6 hours to obtain a precipitate, and the precipitate can be dried at 80 to 100 ° C for 1 to 3 hours.

The solvent in step (a) may be distilled water, methanol, ethanol, or acetone. Examples of the solvent include a mixed solvent of a mixture of tertiary distilled water 1, methanol 6, and acetone 1 in a volume ratio Can be used.

In the step (b), 1 to 50 parts by weight of a dried precipitate is added to 100 parts by weight of the solvent, and the mixture is stirred at 100 to 500 rpm for 12 to 24 hours to obtain a solution.

In step (b), any one selected from dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methylpyrrolidone (NMP), dimethylformamide (DMF), and tetrahydrofuran (THF) may be used. Examples of the solvent include dimethylacetamide DMAc) can be used.

In the step (c), a glass substrate may be used as the substrate, and drying may be performed at 80 to 100 ° C for 1 to 3 hours.

In the above, the cation exchange membrane for a fuel cell may be manufactured to have a thickness of 10 to 200 mu m.

The cation exchange membrane for a fuel cell may be manufactured to have a thickness of 50 to 150 mu m.

In the above, the cation exchange membrane for a fuel cell can be manufactured to have a thickness of 75 to 125 mu m.

The tetrasulfonated polyarylene biphenyl sulfone copolymer of the present invention, a process for producing the same, a cation exchange membrane for a fuel cell comprising the compound, and a method for producing a cation exchange membrane for a fuel cell comprising the compound are provided under various conditions In order to achieve the object of the present invention, there is provided a tetra-sulphonated polyarylene biphenyl sulfone copolymer according to the above-mentioned conditions, a process for producing the same, a cation exchange membrane for a fuel cell comprising the compound, It is desirable to provide a method for producing a cation exchange membrane for a battery.

The present invention relates to a cation exchange membrane / electrode assembly for a fuel cell in which an electrode is bonded to a cation exchange membrane for a fuel cell comprising the above-mentioned tetra sulfonated polyarylene biphenylsulfonic copolymer.

The present invention relates to a cation exchange membrane for a fuel cell comprising the above-mentioned tetra-sulphonated polyarylene biphenylsulfonic copolymer and to a cation exchange membrane for a fuel cell comprising an electrode bonded to a cation exchange membrane for a fuel cell, Exchange membrane / electrode assembly.

The present invention relates to a fuel cell containing a cation exchange membrane for a fuel cell comprising the above-mentioned tetra-sulphonated polyarylene biphenylsulfonic copolymer.

Hereinafter, the content of the present invention will be described in detail through Production Examples, Examples and Test Examples. However, these are for the purpose of illustrating the present invention in more detail, and the scope of the present invention is not limited thereto.

Preparation Example 1 Preparation of Hydrophilic Polymer

A sulfonated arylene biphenyl sulfone polymer, which is a hydrophilic polymer, was prepared using the following Reaction Scheme 1.

[Reaction Scheme 1]

Bis (4-chloro-3-sulfonatophenylsulfonyl) biphenyl-2,2'-disulfonate (8.78 mmol), 3.25 g of 4,4'- Hexafluoroisopropyl laden diphenol (9.65 mmol), 2.67 g potassium carbonate (19.3 mmol), 35 mL DMAc and 30 mL toluene were placed in a 2-neck round bottom flask equipped with magnetic stirrer and Dean-stark trap.

Then, dehydration reaction was carried out at 135 ° C for 6 hours while maintaining the stirring speed at 300 rpm, toluene was removed and the temperature was maintained at 190 ° C for 24 hours to prepare a sulfonated biphenylsulfone polymer as a viscous material.

The sulfonated arylene biphenylsulfone prepared above was subjected to structural analysis through infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy ( ¹ H NMR), and the results are shown below.

FT-IR (KBr, cm ^-1 ): 930 (C (-F) ₃ ), 1004 (Ar-O-Ar), 1015, 1065 (S (= O) ₂ ), 1508 (C = C).

^{1 H NMR (600 MHz, DMSO-} d 6) d 8.58-7.89 (4H) 7.79-7.7 (1H) 7.61-7.45 (3H) 7.45-7.38 (4H) 7.32-7.12 (7H) 7.0-6.86 (1H).

PREPARATION EXAMPLE 2 Preparation of Hexafluoro Isocyanate Ketone Copolymer

A hexafluorosulfuric ketone copolymer represented by the following Reaction Scheme 2 was prepared.

[Reaction Scheme 2]

(9.65 mmol), 4.0 g of 4-chlorobenzophenone (15.93 mmol), 2.67 g of potassium carbonate (19.3 mmol), 20 mL of DMAc and 15 mL Toluene was placed in a two-neck round bottom flask equipped with a magnetic stirrer and Dean-Stark trap.

After the dehydration reaction was carried out at 135 ° C for 6 hours, the toluene was removed and the temperature was maintained at 190 ° C for 24 hours to obtain a hexafluorosulfur ketone copolymer having a viscosity.

Structural analysis of the hexafluoroarsenetone prepared above was carried out by means of infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy ( ¹ H NMR), and the results are shown below.

FT-IR (KBr, cm ^-1 ): 930 (C (-F) ₃ ), 1004 (Ar-O-Ar), 1508

^{1 H NMR (600 MHz, DMSO-} d 6) d 7.8 (4H), 7.4 (4H), 7.2 (8H).

EXAMPLE 1 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Ketone Block Copolymer-10

1몰과 3몰의 탄산칼륨, 25mL DMAc 및 20mL 톨루엔을 마그네틱 교반기 및 딘-스탁 트랩이 구비된 2구 둥근바닥 플라스크에 넣었다. 이후 135℃에서 6시간 탈수반응을 수행 후 톨루엔을 제거하고 190℃에서 24시간 동안 온도를 유지하여 점도가 생긴 물질을 제조하였다(하기 [반응식 3] 참조). 1 mol of the sulfonated biphenylsulfone obtained in Preparation Example 1, 9 mol of the hexafluorobiphenyl ketone copolymer obtained in Preparation Example 2,

1 mol and 3 mol of potassium carbonate, 25 mL of DMAc and 20 mL of toluene were placed in a 2-neck round bottom flask equipped with magnetic stirrer and Dean-Stark trap. After dehydration at 135 ° C for 6 hours, toluene was removed and the temperature was maintained at 190 ° C for 24 hours to obtain a viscous material (see Reaction Scheme 3 below).

The tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 and the hexafluoroarsenetone powder obtained in Preparation Example 2 were respectively dried at 100 ° C for 24 hours before the reaction.

[Reaction Scheme 3]

100 parts by weight of the material prepared in the above reaction scheme 3 was added to 300 parts by weight of a mixed solvent of tertiary distilled water, methanol and acetone in a volume ratio of 1: 6: 1, stirred for 12 hours at 300 rpm, The precipitate was allowed to stand and the precipitate was dried at 80 DEG C for 2 hours.

10 wt% of the above dried precipitate was dissolved in Dimethylacetamide (DMAc) solvent in 90 wt% and stirred at 300 rpm for 24 hours to obtain a solution.

The solution was poured onto a glass substrate and dried in an oven at 80 DEG C for 24 hours to form a film of a sulfonated polyarylene biphenylsulfone ketone copolymer (sulfonated polyarylene biphenylsulfone ketone copolymer-10).

The FT-IR analysis of the sulfonated polyarylene biphenylsulfone ketone block copolymer-10 prepared above showed that the bend of 1065 cm ^-1 , which is expected to be a characteristic bend of the sulfuric acid, was increased.

Example 2 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Ketone Block Copolymer-30

Except that 3 moles of the tetrasulfonated arylene biphenyl sulfone obtained in Preparation Example 1 and 7 moles of the hexafluoroisocyanate powder obtained in Preparation Example 2 were used, To prepare a polyarylene biphenyl sulfone ketone copolymer (sulfonated polyarylene biphenyl sulfone ketone block copolymer-30).

The FT-IR analysis of the sulfonated polyarylene biphenylsulfone ketone block copolymer-30 prepared above showed an increase in the bend of 1065 cm ^-1 as a characteristic bend of the sulfuric acid.

Example 3 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Ketone Block Copolymer 50

Except that 5 moles of the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 and 5 moles of the hexafluorobiphenyl diisocyanate obtained in Preparation Example 2 were used, A sulfonated polyarylene biphenyl sulfone ketone copolymer (sulfonated polyarylene biphenyl sulfone ketone block copolymer-50) was prepared.

FT-IR analysis of the sulfonated polyarylene biphenylsulfone ketone copolymer 50 prepared above showed that the bend of 1065 cm ^-1 , which is expected to be a characteristic bend of the sulfuric acid, was increased.

<Comparative Example>

Except that the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 was not used and 1 mole of the hexafluoroisocyanate powder obtained in Preparation Example 2 was used instead of the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 To prepare a polyarylene biphenyl sulfone ketone block copolymer.

&Lt; Test Example 1 >

The polymer (sulfonated biphenylsulfone) copolymer prepared in Preparation Example 1, the polymer [hexafluorobiphenylketone] copolymer prepared in Preparation Example 2, the block copolymer prepared in Example 1, and the polymer The prepared block copolymers, the block copolymers prepared in Example 3, and the copolymers prepared in the comparative examples were analyzed by ¹ H NMR and the results are shown in FIG.

Referring to FIG. 1, the copolymer prepared in Example 1, the copolymer prepared in Example 2, and the copolymer prepared in Example 3 were confirmed to have an area ratio and a change in characteristic bend by ¹ H NMR peak change due to sulfonation I could.

&Lt; Test Example 2 &

FT-IR was measured on the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3 and the copolymers prepared in Comparative Example to confirm the functional groups in the polymer. The results are shown in Fig.

&Lt; Test Example 3 > Physical property analysis

The degree of sulfonation (DS), the number average molecular weight (Mn), the weight average molecular weight (Mw), the polydispersity index (Mw) of the copolymer prepared in Examples 1 to 3 and the copolymer prepared in Comparative Examples (PDI), and the results are shown in Table 1 below.

The average molecular weight (Mn) and weight average molecular weight (Mw) of the respective copolymers were determined by dissolving 40 mg of each copolymer in 2 mL of DMF to which 0.025 M LiBr had been added and measuring the gel permeation chromatography .

In the above, DS for each copolymer was measured by ¹ H area ratio of NMR.

The polydispersity index (PDI) for each copolymer was calculated as Mn / Mw obtained by gel permeation chromatography.

Copolymer Molar ratio DS Number average molecular weight
(M _n, g mol ^-1 ) Weight average
Molecular Weight
(M _w , g mol ^-1 ) Maximum average
Molecular Weight
(M _max, g mol ^-1 ) The polydispersity index (PDI) Polyarylene biphenylsulfone ketone copolymer 0: 10 0 15100 65800 218400 4.35 Sulfonated polyarylene biphenyl sulfone ketone copolymer 10 1: 9 7 - ^c) Sulfonated polyarylene biphenylsulfone ketone copolymer 30 3: 7 31 - The sulfonated polyarylene biphenylsulfone ketone copolymer 50 5: 5 47 90400 117400 165100 1.30

^{c) Can} not be measured because it is not dissolved

<Test Example 4> Analysis of solubility characteristics

The solubilities of the respective copolymers prepared in Examples 1 to 3 were measured in solvents such as DMAc, NMP, DMSO, DMF, chloroform, THF, acetone, methanol and water. Respectively.

The degree of dissolution of the solvent in each of the above copolymers was determined by measuring 1 g of each copolymer in 10 mL of a solvent at room temperature (++), (+), (+), (??) cost solution.

menstruum Example 1
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-10) Example 2
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-30) Example 3
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-50) DMSO ++ ++ ++ NMP + + + DMAc + + + DMF ± ± + THF - - - chloroform - - - Acetone - - - Methanol - - - water - - -

* "-" means not measurable because it is not dissolved.

Table 2 shows that the respective copolymers prepared in Examples 1 to 3 exhibit high solubility in polar organic solvents such as DMAc, NMP, DMSO, and DMF.

&Lt; Test Example 5 >

The respective sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 were measured for their chemical properties such as glass transition temperature, ion exchange capacity, water content and ionic conductivity, Table 3 shows the results.

(1) Measurement of ion exchange capacity

Each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 was immersed in 1 M NaCl for 24 hours, then phenolphthalein as a standard solution was added thereto, and the solution was titrated with 0.01 N NaOH to obtain ion exchange capacity (IEC) values were calculated.

IEC (meq ?? g ^-1 ) = (V _NaOH x C _NaOH ) / W _dry. &Quot; (1) &quot;

(V _NaOH is consumption of the used NaOH standard solution, C _NaOH is the concentration of NaOH standard solution, W _dry Weight (g) of dried film)

(2) Moisture content measurement

Each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 was dried and weighed for 24 hours in water and then the weight change rate was calculated

Water content (%) = [(W _wet - W _dry ) / W _dry ] × 100 (2)

(W _wet is the weight of the wet film, W _dry is the weight of the dried film)

(3) Measurement of ion conductivity

Each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 was measured for negative ion resistance or bulk resistance by an AC diodic method to calculate ion conductivity.

Ion conductivity (?, S cm ^-1 ) = L / (R x T x W)

(Where L is the distance between two electrodes, R is the resistance of the film, T is the thickness of the film, and W is the width of the film)

Item Glass transition temperature
(° C) Moisture content
(%) Ion exchange capacity
(meq g ^-1 ) Ion conductivity
(S cm ^-1 ) Example 1
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-10) 137 9 0.56 20 Example 2
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-30) 143 16 0.79 75 Example 3
(Sulfonated polyarylene biphenyl sulfone ketone copolymer-50) 157 36 1.02 62

In Table 3, water content and ion exchange capacity were measured at room temperature, and ionic conductivity was measured at 100% relative humidity and 60 ° C. The water content, ion exchange capacity and ionic conductivity were increased with increasing hydrophilic block.

&Lt; Test Example 6 > Measurement of differential scanning calorimetry and thermogravimetry

The differential scanning calorimetry and analysis of the respective sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3, the polyarylene biphenylsulfone ketone copolymers prepared in the Comparative Examples and Nafion 117, TGA (Thermogravimetry Analysis) was measured to confirm the thermal stability of functional groups and main chains of the polymer through TGA, and the glass transition temperature was confirmed by differential scanning calorimetry. The results are shown in FIG.

The left graph in FIG. 3 is the TGA measurement result, and the right graph in FIG. 3 is the measurement result of the glass transition temperature.

&Lt; Test Example 7 >

The water uptake of each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 was measured according to the temperature and is shown in FIG.

The water content was measured by weighing each sulfonated polyarylene biphenylsulfone ketone copolymer prepared in Examples 1 to 3 for 24 hours at each temperature and then measuring the dried weight And calculated using Equation (2) described in Example 5.

4, the water content of each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 was measured. The cation exchange membranes for fuel cells prepared using these respective copolymers were measured for water To confirm the physical stability of the membrane.

&Lt; Test Example 8 > Measurement of ion conductivity

The ionic conductivity of each sulfonated polyarylene biphenyl sulfone ketone copolymer prepared in Examples 1 to 3, the polyarylene biphenyl sulfone ketone copolymer prepared in Comparative Example and Nafion 117 (proton conductivity) was measured and is shown in Fig.

The ion conductivity measurement was carried out using the "(3) ion conductivity measurement" method described in Test Example 5.

In FIG. 5, the resistances measured by measuring the resistance of each sulfonated polyarylene biphenyl sulfone ketone copolymer prepared in Examples 1 to 3 under a temperature of 100% relative humidity (RH) were measured in Test Example 5 The ion conductivity was calculated by using Equation (3) described above, and the performance of the cation exchange membrane for a fuel cell manufactured using each of the copolymers was confirmed.

Although the present invention has been described with reference to the preferred embodiments, examples and experimental examples, it should 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 in the appended claims. It will be understood that the invention may be variously modified and changed.

The tetra sulfonated polyarylene biphenyl sulfone copolymer of the present invention can be used to produce a cation exchange membrane for a fuel cell without additional apparatus and process steps requiring additional high pressure or reduced pressure.

The present invention can easily provide a cation exchange membrane for a fuel cell through the advantage of easily obtaining a cation exchange membrane for a fuel cell by using a tetra sulfonated polyarylene biphenylsulfonic copolymer, There is a possibility of award.

Claims (10)

A tetrasulfonated polyarylene biphenyl sulfone copolymer having the formula (1):

(1)
In the above formula (1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-6)
Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and
X is

or

Lt;
M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,
n is from 0.01 to 1,
z is from 10 to 800.

(2-1)

(2-2)

(2-3)

(2-4)

(2-5)

(2-6) A process for preparing a tetrasulfonated polyarylene biphenyl sulfone copolymer of the following formula (1) by reacting a compound of the formula (3), a compound of the formula (4) and a compound of the formula (5)

(1)

(3)

(4)
X ????? (5)
Ar ₁ , Ar ₂ and Ar ₃ in the compounds of the above formula (1), the compound of the formula (3), the compound of the formula (4) and the compound of the formula (5) (2-6). In this case,
Y is -S-, -O-, -N-, -C ( = O) - or -S (= O) ₂ -, and
X is

or

Lt;
M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,
n is from 0.01 to 1,
z is from 10 to 800.

(2-1)

(2-2)

(2-3)

(2-4)

(2-5)

(2-6) 3. The method of claim 2,
The reaction is carried out by mixing the compound of the formula (3), the compound of the formula (4) and the compound of the formula (5), adding potassium carbonate, a solvent and toluene and conducting a dehydration reaction at 130 to 150 캜 for 3 to 8 hours Removing the toluene and then maintaining the temperature at 180 to 200 ° C for 24 to 48 hours to obtain a reactant having a viscosity. 3. The method of claim 2,
Wherein the reaction is carried out at a molar ratio of the compound of the formula (3) and the compound of the formula (4) in a molar ratio of 1: 9 to 9: 1. 3. The method of claim 2,
The reaction is carried out by reacting the compound of the formula (3) and the compound of the formula (5) in a molar ratio of 1: 9 to 9: 1. The method of claim 3,
Wherein the solvent is any one selected from the group consisting of Dimethylacetamide (DMAc), Dimethyl sulfoxide (DMSO), Methylpyrrolidone (NMP), Dimethylformamide (DMF) and Tetrahydrofuran (THF). A cation exchange membrane for a fuel cell comprising the tetrasulfonated polyarylene biphenyl sulfone copolymer of claim 1. 8. The method of claim 7,
Wherein the cation exchange membrane for a fuel cell has a thickness of 10 to 200 mu m. A cation exchange membrane / electrode assembly for a fuel cell in which an electrode is bonded to a cation exchange membrane comprising the tetrasulfonated polyarylene biphenyl sulfone copolymer of claim 1. In a fuel cell,
A fuel cell containing a cation exchange membrane for a fuel cell comprising the tetrasulfonated polyarylene biphenyl sulfone copolymer of claim 1.

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