KR20150060159A - Electrolyte membranes of partially fluorinated and tetrasulfonated block coploymers for fuel cells and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a tetrasulfonated poly arylene biphenyl sulfone copolymer represented as chemical formula (1), a manufacturing method thereof, and a cation exchange membrane for a fuel cell, comprising the tetrasulfonated poly arylene biphenyl sulfone copolymer in the chemical formula (1).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a block copolymer electrolyte membrane for partially fluorinated and tetrasulfonated fuel cells and a method for producing the same.

The present invention relates to a block copolymer electrolyte membrane for a partially fluorinated and tetra-sulphonated fuel cell and a method for preparing the same, and more particularly to a tetrasulfonated polyarylene biphenyl sulfone copolymer having the following formula (1) And a tetra sulfonated polyarylene biphenyl sulfone copolymer of formula (1).

...화학식(1)

(1)

(1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-4)

Y is -S-, -O-, -N- or -S (= O) ₂ -

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

n is from 0.01 to 1,

z is 10 to 800.)

... 화학식(2-1),

(2-1),

..화학식(2-2),

(2-2),

... 화학식(2-3),

(2-3),

... 화학식(2-4)

(2-4)

(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -.

Fuel cells produce electricity, water, and heat with electrochemical energy conversion devices that convert chemical energy directly into electrical energy by utilizing a variety of fuels that react with oxygen in the presence of an electrolyte.

Because it is not a carnot cycle (conventional heat energy) engine, fuel cells operate with much higher efficiency than traditional energy systems for converting chemical energy directly into electrical energy. It also has a wide range of applications, ranging from a few mW to hundreds of kW.

Generally, the fuel cell varies depending on the type of the electrolyte. Examples of the fuel cell include an alkaline fuel cell (AFC), a proton exchange membrane fuel cell (PEMFC), a phosphoric acid fuel cell fuel cells, PAFCs, molten carbonate fuel cells (MCFCs), and solid oxide fuel cells (SOFCs).

Each of these fuel cells operates on a similar principle, but there are differences in operating temperature, catalyst, electrolyte and fuel for each fuel cell.

Researches on cation exchange membrane fuel cells have been actively conducted to popularize such fuel cells. This is because the operating temperature of several fuel cells is low and suitable for power generation applications in mobile, household generators, and public facilities such as automobiles.

A cation exchange membrane fuel cell (PEMFC) consists of an anode, a cathode, and an electrolyte. The electrolyte used here is a polymer such as a sulfonated perfluoropolymer (for example, Nafion, manufactured by DuPont) composed of a main chain composed of fluorinated alkylene and a fluorinated vinyl ether having a sulfonic acid group introduced into a functional group. Such a polymer electrolyte exhibits effective ion conductivity by absorbing a certain amount of water.

However, fluorinated cation exchange membranes have poor performance, flexible membrane characteristics, good mechanical and chemical stability, but are also unavailable for industrial applications. This is due to limited operating temperatures, too high production costs and complex manufacturing processes.

Therefore, in order to improve various disadvantages, researches are being conducted on aromatic-based ion exchange membranes.

As a prior art related to the present invention, Polymer 2006, 47, 41324139 discloses a multi-block copolymer in which a hydrophilic block and a hydrophobic block are alternately made of a hydrocarbon-based cation exchange membrane, And a method for producing the same as a 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.

The present inventors have succeeded in producing an inexpensive cation-exchange membrane through direct block copolymers without using a linker, having excellent ion conductivity, and exhibiting high ionic conductivity in the mid- and long-term under low- and high-humidity conditions And completed the present invention.

Accordingly, an object of the present invention is 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 provide a low-cost cation exchange membrane by exhibiting high ion conductivity performance over the medium to long term under the conditions of medium-low temperature and high humidity.

It is another object of the present invention to provide a cation exchange membrane for a fuel cell, which is superior to a Nafion membrane by exhibiting a 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 biphenyl sulfone copolymer having the following general formula (1), a process for producing the same, a cations for fuel cells comprising a tarsulfonated polyarylene biphenyl sulfone copolymer represented by the following general formula (1) A cation exchange membrane / electrode assembly for a fuel cell in which an electrode is bonded to the cation exchange membrane for the fuel cell, a fuel cell including the cation exchange membrane for the fuel cell, and a polymer electrolyte fuel cell comprising the cation exchange membrane / electrode assembly.

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

...화학식(1)

(1)

(1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-4)

Y is -S-, -O-, -N- or -S (= O) ₂ -

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

n is from 0.01 to 1,

z is 10 to 800.)

... 화학식(2-1),

(2-1),

..화학식(2-2),

(2-2),

... 화학식(2-3),

(2-3),

... 화학식(2-4)

(2-4)

(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -.

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, the copolymer prepared in Example 3 and Nafion 117 according to the temperature.
5 shows hydrogen ion conductivity values at 100% humidification of the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, and Nafion 117. FIG.
Fig. 6 shows the percentages of the swelling of the water content according to the temperature of the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, and Nafion 117. Fig.
7 shows the hydrogen ion conductivity values of the copolymer prepared in Example 1, the copolymer prepared in Example 2, the copolymer prepared in Example 3, and Nafion 117 according to the humidification at a temperature of 80 ° C.
8 shows the single cell performance of the copolymer prepared in Example 3 at 70 캜.

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

...화학식(1)

(1)

(1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-4)

Y is -S-, -O-, -N- or -S (= O) ₂ -

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

n is from 0.01 to 1,

z is 10 to 800.)

... 화학식(2-1),

(2-1),

..화학식(2-2),

(2-2),

... 화학식(2-3),

(2-3),

... 화학식(2-4)

(2-4)

(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -.

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

...화학식(1)

(1)

...화학식(3)

(3)

...화학식(4)

(4)

(Formula (1), the formula 3 and in formula (4), Ar _1, Ar ₂ and Ar ₃ is Ar _1, Ar ₂ and Ar ₃ in the formula (1) each independently are to independently formula (2-1) to (2-4), < / RTI >

Y is -S-, -O-, -N- or -S (= O) ₂ -

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

n is from 0.01 to 1,

z is 10 to 800.)

... 화학식(2-1),

(2-1),

..화학식(2-2),

(2-2),

... 화학식(2-3),

(2-3),

... 화학식(2-4)

(2-4)

(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -.

In the preparation of the tetrasulfonated polyarylene biphenyl sulfone copolymer of formula (1), the compound of formula (3) and the compound of formula (4) are mixed, potassium carbonate, a solvent and toluene are added, The reaction mixture was dissolved at -150 ° C. for 3 to 12 hours, dehydrated at 160 ° C. for 2 to 6 hours to remove toluene, and maintained at 180 to 200 ° C. for 12 to 36 hours to obtain a reaction product having viscosity 1) tetrasulfonated 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.

When the compound of formula (1) is prepared, the reaction is carried out in a solvent, and the solvent may be selected from the group consisting of dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), methylpyrrolidone (NMP) , Dimethylformamide (DMF), and tetrahydrofuran (THF) may be used.

The potassium carbonate used in the preparation of the compound of formula (1) may be used in an amount of 5 to 10 moles per 1 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 represents a cation exchange membrane for a fuel cell comprising a tetra sulfonated polyarylene biphenyl sulfone copolymer of the above formula (1).

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 8, and acetone 1 in a volume ratio Can be used.

In the step (b), 1 to 50 parts by weight of the dried precipitate is added to 100 parts by weight of the solvent and dissolved, and the mixture is stirred at 100 to 500 rpm for 12 to 48 hours to obtain a solution.

In the step (b), the solvent may be any one selected from the group consisting of dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), methylpyrrolidone (NMP), dimethylformamide (DMF) and tetrahydrofuran And dimethylacetamide (DMAc) can be used as an example of such a solvent.

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 24 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 may be manufactured to have a thickness of 75 to 125 mu m.

The tetrasulfonated polyarylene biphenyl sulfone copolymer of the present invention, a method 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-sulfonated polyarylene biphenyl sulfone copolymer, a method for producing the same, a cation exchange membrane for a fuel cell comprising the compound, a cation for a fuel cell It is desirable to provide a method for producing a replacement membrane.

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-sulphonated polyarylene biphenylsulfonic copolymer.

The present invention relates to a cation exchange membrane for a fuel cell comprising a tetra sulfonated polyarylene biphenylsulfone copolymer and a cathode prepared by the method and an electrode bonded to the cation exchange membrane for a fuel cell, 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.

The present invention also relates to a polymer electrolyte fuel cell comprising the above cation exchange membrane / electrode assembly for a fuel cell.

In the present invention, the polymer electrolyte fuel cell comprising the fuel cell containing the cation exchange membrane for fuel cells and the cation exchange membrane / electrode assembly for fuel cells may be manufactured by a conventional method.

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), 2.20 g of bisphenol ( 9.65 mmol), 2.67 g potassium carbonate (19.3 mmol), 30 mL DMAc and 25 mL toluene were placed in a 2-neck round bottom flask equipped with magnetic stirrer and Dean-stark trap.

Then, the mixture was stirred at 120 rpm for 12 hours and then dehydrated at 160 캜 for 6 hours. The toluene was then removed. The temperature was maintained at 180 캜 for 36 hours to obtain a sulphonated To prepare a biphenyl sulfone polymer.

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} ): 1480 (C = C), 1365, 1027 (S (= O) 2), 1170 (O = S = O), 1068 (Ar-O-Ar), 882 ( SO)

^{1 H NMR (600 MHz, DMSO-} d 6) d 8.54-8.01 (4H), 7.65-7.45 (1H), 7.42-7.15 (7H), 7.14-6.68 (8H), 1.65 (6H)

≪ Preparation Example 2 > Preparation of hydrophobic polymer

A fluorobiphenyl diisobisphenyl copolymer, which is a hydrophobic polymer represented by the following Reaction Scheme 2, was prepared.

      [Reaction Scheme 2]

(15.01 mmol), 5.77 g of decafluorobiphenyl (17.27 mmol), 4.84 g of potassium carbonate (35.0 mmol), 15 mL of DMAc and 20 mL of toluene were charged in a reaction vessel equipped with a magnetic stirrer and a dean- And placed in a two-neck round bottom flask.

After stirring at 120 rpm for 12 hours, dehydration was carried out at 160 ° C. for 6 hours. Then, toluene was removed and the temperature was maintained at 180 ° C. for 24 hours to obtain a viscous material, fluorobiphenyl To prepare a bisphenyl copolymer.

The fluorobiphenyl diisobiphenyl 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 ): 1649, 1481 (C = C), 1068 (Ar-O-Ar), 978

^{1 H NMR (600 MHz, DMSO-} d 6) d 7.24 (4H), 7.13 (4H), 1.63 (6H)

EXAMPLE 1 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Block Copolymer-30

3 moles of the sulfonated arylene biphenyl sulfone obtained in Preparation Example 1, 7 moles of the fluorobiphenyl diisobiphenyl copolymer obtained in Preparation Example 2, and 14 moles of potassium carbonate, 25 ml of DMAc and 20 ml of toluene were charged into a magnetic stirrer and a dean - placed in a two-necked round bottom flask equipped with a staple 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 fluorobiphenyl diisobiphenyl 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: 8: 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.

10wt% of the dried precipitate was dissolved in 90wt% of dimethylsulfoxide (DMSO) solvent and stirred at 300rmp 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 polyarylenebiphenylsulfone copolymer (sulfonated polyarylenebiphenylsulfone copolymer-30).

The FT-IR analysis of the sulfonated polyarylene biphenylsulfone block copolymer-30 prepared above showed an increase in the bend of 1068 cm ^-1 as a characteristic bend of the sulfuric acid. ^{As a} result of ¹ H NMR analysis, it was confirmed that the peak of 8.6 to 7.5 ppm, which is expected as a characteristic peak of the tetrasulfonated aromatic hydrogen, was increased.

Example 2 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Block Copolymer-50

Except that 5 moles of the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 and 5 moles of the fluorobiphenyl diisobiphenyl powder obtained in Preparation Example 2 were used, To prepare a sulfonated polyarylenebiphenylsulfone copolymer (sulfonated polyarylenebiphenylsulfone block copolymer-50).

FT-IR analysis of the sulfonated polyarylene biphenylsulfone block copolymer-50 prepared above showed that the bend of 1068 cm ^-1 , which is expected to be a characteristic bend of the sulfuric acid, was increased. ^{As a} result of ¹ H NMR analysis, it was confirmed that the peak of 8.6 to 7.5 ppm, which is expected as a characteristic peak of the tetrasulfonated aromatic hydrogen, was increased.

Example 3 Preparation of Sulfonated Polyarylene Biphenyl Sulfone Block Copolymer 70

Except that 7 moles of the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 and 3 moles of the fluorobiphenyl diisopropylphenoxide powder obtained in Preparation Example 2 were used instead of the tetra-sulfonated arylene biphenylsulfone obtained in Preparation Example 1 A sulfonated polyarylene biphenyl sulfone copolymer (sulfonated polyarylene biphenyl sulfone block copolymer-70) was prepared.

As a result of the FT-IR analysis of the sulfonated polyarylene biphenylsulfone copolymer-70 prepared above, it was confirmed that the bend of 1068 cm ^-1 , which is a characteristic bend of the sulfuric acid, was increased. ^{As a} result of ¹ H NMR analysis, it was confirmed that the peak of 8.6 to 7.5 ppm, which is expected as a characteristic peak of tetrasulfonated aromatic hydrogen, was increased.

<Comparative Example>

The procedure of Example 1 was repeated except that the tetrasulfonated arylene biphenylsulfone obtained in Preparation Example 1 was not used and 1 mol of the fluorobiphenyl diisopropylphenyl 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 block copolymer.

&Lt; Test Example 1 >

The polymer (sulfonated arylene biphenylsulfone) copolymer prepared in Preparation Example 1, the polymer [fluorobiphenyl diisobiphenyl] copolymer prepared in Preparation Example 2, the block copolymer prepared in Example 1, and the polymer The ¹ H NMR of the block copolymers prepared in Example 2, the block copolymers prepared in Example 3 and the copolymers prepared in Comparative Example were measured 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
(Mn, g mol-1) Weight average
Molecular Weight
(Mw, g mol-1) Maximum average
Molecular Weight
(Mmax, g mol-1) Polydispersity index
(PDI) Polyarylene biphenyl sulfone copolymer 0: 1 0 9500 57400 256000 8.2 Sulfonated polyarylene biphenyl sulfone copolymer 30 3: 7 32 6100 34000 168000 5.4 The sulfonated polyarylene biphenyl sulfone copolymer 50 5: 5 49 7100 56000 343000 7.0 The sulfonated polyarylene biphenyl sulfone copolymer 70 7: 3 68 14000 66000 315000 4.6

<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. In the above, "-" means that measurement is impossible because it is not dissolved.

menstruum Example 1
(Sulfonated polyarylene biphenyl sulfone copolymer-30) Example 2
(Sulfonated polyarylene biphenyl sulfone copolymer-50) Example 3
(Sulfonated polyarylene biphenyl sulfone copolymer-70) DMAc ++ ++ ++ DMF ++ ++ ++ NMP ++ + + DMSO ++ + + MC + - - - THF - - + - chloroform - - - Acetone - - - Methanol - - - water - - -

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

&Lt; Test Example 5 >

The sulfonated polyarylene biphenylsulfonic copolymers prepared in Examples 1 to 3 were measured for their chemical properties such as glass transition temperature, ion exchange capacity, water content, dimensional swelling ratio and ionic conductivity, and the results Are shown in Table 3 below.

(1) Measurement of ion exchange capacity

Each of the sulfonated polyarylene biphenylsulfonic 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 then titrated with 0.01 N NaOH to determine the ion exchange capacity IEC) were calculated.

IEC (meqg ^-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 Means the weight (g) of the dried film.)

(2) Moisture content measurement

The sulfonated polyarylene biphenylsulfonic copolymers prepared in Examples 1 to 3 were dried and then dried in water for 24 hours, and the weight change rates were calculated.

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

(Where W _wet represents the weight of the wet film, and W _dry represents the weight of the dried film).

(3) Measurement of dimensional swelling ratio

The sulfonated polyarylene biphenylsulfonic copolymers prepared in Examples 1 to 3 were dried and then dried in water for 24 hours, and the rate of change in length was calculated.

Water content (%) = [( _wet -l _dry ) / l _dry ] x 100 [

(Where, l _wet is the wet film length and l _dry is the dried film length in the above equation (3)).

(4) Measurement of ion conductivity

Each of the sulfonated polyarylene biphenylsulfonic 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
(meqg ^-1 ) Ion conductivity
(S cm ^-1 ) Example 1
(Sulfonated polyarylene
Biphenyl sulfone copolymer-30) 146 20 0.5 0.030 Example 2
(Sulfonated polyarylene
Biphenyl sulfone copolymer-50) 162 33 1.0 0.068 Example 3
(Sulfonated polyarylene
Biphenyl sulfone copolymer-70) 182 52 1.3 0.110

In Table 3, the water content and the ion exchange capacity were measured at room temperature, and the ion conductivity was measured at 100% relative humidity and 90 ° 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

Differential scanning calorimetry (TGA) and differential scanning calorimetry (TGA) were performed on each of the sulfonated polyarylenebiphenylsulfonic copolymers prepared in Examples 1 to 3, the polyarylenebiphenylsulfonic copolymers prepared in Comparative Examples and Nafion 117 Thermogravimetry analysis was performed to confirm the thermal stability of the 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 shows the TGA measurement result, and the right graph in FIG. 3 shows the measurement results of the glass transition temperature.

&Lt; Test Example 7 >

The water uptake of each of the sulfonated polyarylene biphenylsulfonic 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 biphenyl sulfonic 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 And the physical stability of the membrane was confirmed.

&Lt; Test Example 8 > Measurement of ion conductivity according to temperature

Each of the sulfonated polyarylenebiphenylsulfonic copolymers prepared in Examples 1 to 3, the polyarylenebiphenylsulfonic copolymers prepared in Comparative Examples and Nafion 117 were mixed at a relative humidity of 1100% The proton conductivity according to the temperature was measured and shown in FIG.

The ion conductivity measurement was carried out using the "(4) ion conductivity measurement" method described in Test Example 5.

5, the resistances measured by measuring the resistance of each sulfonated polyarylene biphenyl sulfone copolymer prepared in Examples 1 to 3 under a temperature of 100% relative humidity (RH) were measured as shown in Test Example 5 The ion conductivity was calculated using Equation (4), and the performance of the cation exchange membrane for a fuel cell manufactured using each of the respective copolymers was confirmed.

&Lt; Test Example 9 > Measurement of dimensional swelling ratio

The swelling ratios of the respective sulfonated polyarylene biphenyl sulfone copolymers prepared in Examples 1 to 3 were measured according to the temperature and are shown in FIG.

The swelling amount was measured by measuring the length of each of the sulfonated polyarylene biphenylsulfone ketone copolymers prepared in Examples 1 to 3 at the respective temperatures for 24 hours in water, Was calculated using Equation (3) described in Test Example 5.

In FIG. 6, the swelling of each sulfonated polyarylene biphenyl sulfonic copolymer prepared in Examples 1 to 3 was measured, and the cation exchange membrane for a fuel cell prepared using each of these copolymers was measured to the extent of water And the physical stability of the membrane was confirmed.

Test Example 10 Measurement of Ionic Conductivity by Humidification

Each of the sulfonated polyarylenebiphenylsulfonic copolymers prepared in Examples 1 to 3, the polyarylenebiphenylsulfonic copolymers prepared in the Comparative Examples and Nafion 117 were subjected to a humidification The proton conductivity was measured and is shown in Fig.

The ion conductivity measurement was carried out using the "(4) ion conductivity measurement" method described in Test Example 5.

5, the resistances measured by measuring the resistance of each sulfonated polyarylene biphenyl sulfone copolymer prepared in Examples 1 to 3 under a temperature of 100% relative humidity (RH) were measured as shown in Test Example 5 The ion conductivity was calculated using Equation (4), and the performance of the cation exchange membrane for a fuel cell manufactured using each of the respective copolymers was confirmed.

&Lt; Test Example 11 > Measurement of fuel performance

The sulfonated polyarylene biphenylsulfonic copolymer 70 prepared in Example 3 was measured for fuel cell performance at 70 ° C. The results are shown in FIG.

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 of the formula (1)

(1)
(1), Ar ₁ , Ar ₂ and Ar ₃ are each independently any one selected from the following formulas (2-1) to (2-4)
Y is -S-, -O-, -N- or -S (= O) ₂ -
M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,
n is from 0.01 to 1,
z is 10 to 800.)

(2-1),

(2-2),

(2-3),

(2-4)
(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -. A process for preparing a tetrasulfonated polyarylene biphenyl sulfone copolymer of the following formula (1) by reacting a compound of the formula (3) and a compound of the formula (4)

(1)

(3)

(4)
(Formula (1), the formula 3 and in formula (4), Ar _1, Ar ₂ and Ar ₃ is Ar _1, Ar ₂ and Ar ₃ in the formula (1) each independently are to independently formula (2-1) to (2-4), &lt; / RTI &gt;
Y is -S-, -O-, -N- or -S (= O) ₂ -
M is -H, -Li, -Na, -K, -Rb, -Cs or Fr,
n is from 0.01 to 1,
z is 10 to 800.)

(2-1),

(2-2),

(2-3),

(2-4)
(In the formulas (2-1) and (2-2), Y is -S-, -O-, -N- or -S (= O) ₂ -. 3. The method of claim 2,
The reaction is carried out by mixing the compound of the formula (3) and the compound of the formula (4), adding potassium carbonate, a solvent and toluene, dissolving at 130 to 150 캜 for 3 to 12 hours, Deg.] C to remove the toluene, and then the mixture is held at 180 to 200 [deg.] C for 12 to 36 hours to obtain a reaction product having a viscosity. 3. The method of claim 2,
Wherein the reaction is carried out by reacting the compound of formula (3) with the compound of formula (4) in a molar ratio of 1: 9 to 9: 1. The method of claim 3,
The solvent is any one selected from the group consisting of dimethylacetamide, dimethyl sulfoxide, methylpyrrolidone, dimethylformamide and tetrahydrofuran. Lt; / RTI &gt; A cation exchange membrane for a fuel cell comprising the tetrasulfonated polyarylene biphenyl sulfone copolymer of claim 1 or a tetrasulfonated polyarylene biphenyl sulfone copolymer prepared by the method of claim 2. The method according to claim 6,
Wherein the cation exchange membrane has a thickness of 10 to 200 占 퐉. A cation exchange membrane / electrode assembly for a fuel cell, wherein the electrode is bonded to the cation exchange membrane for a fuel cell according to claim 6. A fuel cell comprising the cation exchange membrane for a fuel cell according to claim 6. A polymer electrolyte fuel cell comprising the cation exchange membrane / electrode assembly for a fuel cell according to claim 8.

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