KR100756457B1 - Block copolymers containing perfluorocyclobutane rings and electrolyte membranes using the same - Google Patents

Abstract

The present invention relates to a block copolymer comprising a perfluorocyclobutane group, a preparation method thereof and an electrolyte membrane including the same. The block copolymer comprising a perfluorocyclobutane group according to the present invention is easy to manufacture, and the electrolyte membrane including the same has excellent hydrogen ion conductivity and mechanical properties, as well as distribution of acid groups (sulfonic acid groups, etc.) in the polymer skeleton, It is possible to control the position, number, etc., there is no deterioration of the membrane properties due to the increase in acid groups can be used as a material of a variety of membranes, in particular there is an advantage that can be preferably used in the electrolyte membrane of the fuel cell.

Perfluorocyclobutane groups, fonned later, multiblock copolymers, electrolyte membranes, fuel cells, hydrogen ion conductivity

Description

Block copolymer containing perfluorocyclobutane group and electrolyte membrane using the same {Block copolymers containing perfluorocyclobutane rings and electrolyte membranes using the same}

1 and 2 are graphs showing the results of measuring the hydrogen ion conductivity of a fonated multiblock copolymer described below including a perfluorocyclobutane group prepared according to an embodiment of the present invention.

The present invention relates to a block copolymer comprising a perfluorocyclobutane group, a preparation method thereof and an electrolyte membrane including the same. More specifically, it is easy to manufacture, and the electrolyte membrane including the same not only has excellent hydrogen ion conductivity and mechanical properties, but also controls distribution, position, and number of acid groups such as sulfonic acid group in the polymer skeleton, The present invention relates to a multiblock copolymer comprising a perfluorocyclobutane group capable of effectively producing a membrane without deterioration of membrane properties due to an increase thereof, and a method of manufacturing the same, and an electrolyte membrane and a fuel cell including the same.

Fuel cell is an energy conversion system that converts chemical energy into electrical energy, and is actively researched due to its environmentally friendly features, which require the development of alternative energy due to the explosive increase in electric demand, high energy efficiency and low pollutant emission. Fuel cells are classified according to the electrolyte material or operating temperature used. Among them, polymer electrolyte membrane fuel cells (PEMFCs) can be used for small combined cycle power generation that supplies power and heat simultaneously. Compared to the battery, it has excellent energy conversion characteristics and power density characteristics, can operate at low temperature, and has many advantages such as stability against mechanical shock, and thus, has been in the spotlight as a power source for automobiles and electronic components.

Such polymer electrolyte membranes require high ionic conductivity, redox safety, and high mechanical strength.Nafion ^TM (Afionx, Asahi Chemical) of Dupont, an all-fluorine ion exchange membrane, is presently required. Fuel cell membranes such as (Aciplex ^™ ) are commercially available, but these all-fluorine polymer electrolyte membranes are expensive in terms of their excellent performance and have a disadvantage in that the efficiency is reduced above 80 ° C. When used in methanol fuel cell (DMFC), in addition to the drawbacks listed above, methanol has a disadvantage of being methanol crossover from the anode through the membrane. Various studies have been made to replace fluorine-based or partial fluorine-based films.

U. S. Patent No. 6,559, 237 discloses a post-treatment sulfonation process of a perfluorocyclobutane membrane which is a partially fluorine based polymer electrolyte membrane. However, the post-treatment sulfonation method is difficult to control the distribution, position, and number of sulfonic acid groups in the polymer skeleton, and as the sulfonic acid group increases, the water content of the membrane increases, thereby deteriorating the properties of the electrolyte membrane.

U.S. Patent No. 5,602,185 discloses a process for preparing a polymer electrolyte membrane by random copolymerization of a trifluorostyrene derivative which is partially fluorine. However, the above method uses a palladium catalyst in the manufacturing process, so the production cost of the monomer is too expensive. Due to the rigid structure of the polystyrene itself, the mechanical properties are poor, and it is difficult to control the distribution, position, and number of sulfonic acid groups in the polymer skeleton. As the sulfonic acid group increases, the water content of the membrane increases, thereby deteriorating the physical properties of the electrolyte membrane.

U.S. Patent No. 6,090,895 also discloses a crosslinking process of sulfonated polymers such as sulfonated polyetherketones, sulfonated polyethersulfones, and sulfonic acid polystyrenes. However, when preparing a thin film in a large amount from the cross-linked sulfonic acid polymer, it did not suggest an effective method for properly processing.

On the other hand, EP 1,113,517 A2 discloses a block copolymer polymer electrolyte membrane having no sulfonic acid group and a block having sulfonic acid group. The sulfonated aromatic block using sulfuric acid is a block copolymer composed of an aliphatic block and an aromatic block, but there is a problem in that the aliphatic polymer bond is chemically decomposed during the sulfonation process.

In addition, US Patent Publication No. 2004-186262 discloses a method for producing a multiblock copolymer polymer electrolyte membrane in which hydrophobic blocks made of hydrocarbons and hydrophilic blocks are alternately made. The method converts the -SO ₃ K type copolymer into -SO ₂ Cl using cionyl chloride to give hydrogen ion conductivity to the polymer membrane due to the low solubility of the multiblock copolymer. However, the method has a problem in that the manufacturing process is complicated, there is a problem of toxicity during the manufacturing process, and the mechanical integrity of the polymer thin film does not reach the level required for driving the fuel cell.

The present inventors have made efforts to improve the disadvantages of the conventional polymer as described above, using a hydrophilic monomer and an unsulfonated hydrophobic monomer containing a perfluorovinyloxy group in the sock end can easily prepare a hydrophilic and hydrophobic oligomer In particular, a block oligomer may be synthesized from a monomer having a high sulfonation activity and a monomer having a low sulfonation activity, in which a perfluorovinyloxy group is included in a sock end, to synthesize a block copolymer. The present invention has been accomplished by knowing that multiblock copolymers can be prepared.

Accordingly, it is an object of the present invention to provide a block copolymer which is easy to manufacture, has excellent hydrogen ion conductivity and mechanical properties, and is chemically stable, in particular, a fonned block copolymer described below and a method for producing the same.

Another object of the present invention is to control the distribution, position, and number of sulfonic acid groups in the polymer skeleton, have excellent hydrogen ion conductivity, excellent mechanical properties and chemical stability, and membrane properties with the increase of sulfonic acid groups It is to provide an electrolyte membrane comprising the block copolymer without deterioration and a method of manufacturing the same.

Still another object of the present invention is to provide a fuel cell including the electrolyte membrane.

The present invention provides a block copolymer (I) comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (4).

(-R-P-Q-P-)

(-R "-P-Q-P-)

Where

Each -P- is independently selected from the group consisting of -O-, -S-, -SO-, SO _2- , -CO-, -NH-, -NR _1- , and -R _2- , wherein R ₁ represents alkyl or aryl having 1 to 25 carbon atoms, R ₂ represents alkylene or arylene having 1 to 25 carbon atoms,

-Q- each independently represent 1,2-perfluorocyclobutylene (C ₄ F ₆ ),

R is an aromatic group substituted with an unsubstituted or inert group that does not induce other chemical reactions in forming the group -Q-,

R ″ is an aromatic group comprising one or more benzene rings substituted with one or more —PO ₃ H ₂ or —SO ₃ H.

In the formula, -P- preferably represents -O- or -S-, R ₁ preferably represents alkyl of 1 to 3 carbon atoms, and R ₂ preferably represents alkylene of 1 to 3 carbon atoms. .

In addition, when R or R "includes two or more benzene rings, these benzene rings are each directly connected, or -O-, -S-,-(CH ₂ )-,-(C (O))-, -(S (O) ₂ )-,-(-P (O))-,-(Si (CH ₃ ) ₂ )-,-(C (CH ₃ ) ₂ )-,-(C (CF ₃ ) ₂ It is preferred to be connected by)-or-(Si (C ₆ H ₅ ) ₂ )-.

In the block copolymer (I) according to the present invention, after the hydrophobic block (Formula 1) containing no acid substituents and the hydrophilic block (Formula 4) containing an acid substituent are polymerized, the acid substituent moiety is acid. The hydrophobic block that maintains the mechanical integrity of the thin film and the hydrophilic block that imparts ion conductivity to the thin film alternately lead to chemical bonding.

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로 이루어진 그룹으로부터 선택된 하나 이상의 방향족 화합물 등을 들 수 있으나 이에 제한되지 않는다. 보다 바람직한 치환체 R은

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로 이루어진 그룹으로부터 선택된 방향족 화합물이다. Specific examples of the substituent R of the hydrophobic block

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One or more aromatic compounds selected from the group consisting of, but is not limited thereto. More preferred substituent R is

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Aromatic compounds selected from the group consisting of:

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로 이루어진 그룹으로부터 선택된 하나 이상의 방향족 화합물 R'의 하나 이상의 벤젠환이 하나 이상의 -PO₃H₂ 또는 -SO₃H로 치환된 방향족 화합물을 들 수 있으나, 이에 제한되지 않는다. 상기 식에서 A는 -NO₂, 또는 -CF₃을 나타낸다. 보다 바람직한 치환체 R"는

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로 이루어진 그룹으로부터 선택된 하나 이상의 방향족 화합물 R'의 벤젠환이 하나 이상의 -PO₃H₂ 또는 -SO₃H로 치환된 방향족 화합물이다.Specific examples of the substituent R ″ of the hydrophilic block

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An aromatic compound in which at least one benzene ring of at least one aromatic compound R 'selected from the group consisting of is substituted with at least one -PO ₃ H ₂ or -SO ₃ H, but is not limited thereto. In the formula, A represents -NO ₂ , or -CF ₃ . More preferred substituent R ″

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And

The benzene ring of at least one aromatic compound R 'selected from the group consisting of is an aromatic compound substituted with at least one -PO ₃ H ₂ or -SO ₃ H.

In particular, the block copolymer according to the present invention preferably includes a repeating unit represented by the following Chemical Formula 5.

Wherein R and R "are each as defined above,

n and m are each an integer of 1 to 10,000.

The present invention also provides a block copolymer (II) comprising a block containing an aromatic compound having a high sulfonating activity and a block containing an aromatic compound having a low sulfonating activity.

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로 이루어진 그룹으로부터 선택된 하나 이상의 술폰화 활성이 낮은 방향족 화합물을 나타내는 것이 바람직하고, 보다 바람직하게는

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또는

로부터 선택되는 방향족 화합물을 나타내는 것이다. In this case, the substituent R of the repeating unit represented by Formula 1 is

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It is preferable to represent one or more sulfonated low aromatic compounds selected from the group consisting of, more preferably

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It represents an aromatic compound selected from.

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로 이루어진 그룹으로부터 선택된 하나 이상의 술폰화 활성이 높은 방향족 화합물 R'의 벤젠환이 하나 이상의 -SO₃H로 치환된 방향족 화합물을 나타내는 것이 바람직하고, 보다 바람직하게는

또는

로부터 선택된 방향족 화합물 R'의 벤젠환이 하나 이상의 -SO₃H로 치환된 방향족 화합물을 나타내는 것이다. In addition, the substituent R ″ of the repeating unit represented by Formula 4 is

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It is preferable that the benzene ring of one or more sulfonated highly active aromatic compounds R 'selected from the group consisting of represents an aromatic compound substituted with one or more -SO ₃ H, more preferably.

or

The benzene ring of the aromatic compound R 'selected from represents an aromatic compound substituted with at least one -SO ₃ H.

The later-fonned block copolymer (II) according to the present invention is polymerized using a monomer or a block oligomer having a high sulfonation activity and a monomer or a block oligomer having a low sulfonation activity and then fonned later, thereby increasing the mechanical density of the thin film. Blocks with low sulfonation activity to maintain and sulfonated block oligomers that impart ionic conductivity to the thin film alternately lead to chemical bonding.

Meanwhile, the block copolymer according to the present invention has a weight average molecular weight of 500 to 500,000 (g / mol) of a block including a repeating unit represented by Formula 1, and a weight average of a block including a repeating unit represented by Formula 4 It is preferable that the molecular weight is 500-500,000 (g / mol). When the weight average molecular weight of each is less than 500 (g / mol), the block size is difficult to form a small block copolymer, the mechanical density of the prepared film is reduced, or if the exceeds 500,000 (g / mol) block size is too large Resizing blocks is not easy.

In addition, the present invention provides a method for producing the block copolymer (I), wherein the preparation method comprises: (i) a method of preparing from a hydrophobic block and a hydrophilic block, and (ii) a method of preparing from a hydrophobic block and a hydrophilic monomer. And (iii) a method for preparing from hydrophobic monomers and hydrophilic blocks.

More specifically, the method (i) prepared from the hydrophobic block and the hydrophilic block,

a) preparing a hydrophobic block oligomer of Chemical Formula 7 by polymerizing an aromatic monomer of Chemical Formula 6 including a perfluorovinyl oxy group in a sock end;

b) preparing an hydrophilic block oligomer represented by the following Chemical Formula 9 by polymerizing an aromatic monomer represented by the following Chemical Formula 8 having an acid-substituted group and including a perfluorovinyl oxy group in a sock end;

c) reacting the hydrophobic block oligomer prepared in step a) and the hydrophilic block oligomer prepared in step b) to prepare an acid-substituted block copolymer represented by Chemical Formula 10; And

d) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step c) to an acid group (R ″).

It includes.

F ₂ C = FC-PRP-CF = CF ₂

F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂

F ₂ C = FC-P-R '"-P-CF = CF ₂

F ₂ C = FC-P-(-R '"-PQP-) _m' -R '"-P-CF = CF ₂

-(-RPQP-) _n -(-R '"-PQP-) _m-

In the above, P, Q, R, and R "are as defined in Formula 1 and 4, respectively,

R '"is _{-SO 2 Cl, -SO 2 F,} -SO 3 - M +, -P (O) (OA) 2, -PO 3 H - M + and -PO ₃ ^{2 -} 2M ⁺ (wherein, A Is alkyl having 1 to 4 carbon atoms, more preferably methyl or ethyl, and M is an alkali metal, more preferably Na or K) at least one benzene ring substituted with at least one acid substituent group selected from the group consisting of An aromatic group containing

n, m, n 'and m' are each an integer of 1 to 10,000.

Also, the process (ii) prepared from hydrophobic blocks and hydrophilic monomers

a) preparing a hydrophobic block oligomer of Chemical Formula 7 by polymerizing an aromatic monomer of Chemical Formula 6 including a perfluorovinyl oxy group in a sock end;

b) an acid-substituted block copolymer represented by the following Chemical Formula 10 by polymerizing an aromatic monomer of the following Chemical Formula 8 having an acid-substituted group and including a perfluorovinyl oxy group in the sock end with the hydrophobic block oligomer prepared in step a) Preparing a; And

c) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step b) to an acid group (R ″).

[Formula 6]

F ₂ C = FC-PRP-CF = CF ₂

[Formula 7]

F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂

[Formula 8]

F ₂ C = FC-P-R '"-P-CF = CF ₂

[Formula 10]

-(-RPQP-) _n -(-R '"-PQP-) _m-

In the above, P, Q, R, R ", R '", n', n and m are as defined in the above method i), respectively.

On the other hand, the method (iii) prepared from the hydrophobic monomer and the hydrophilic block

a) preparing an hydrophilic block oligomer represented by the following Chemical Formula 9 by polymerizing an aromatic monomer of Chemical Formula 8 having an acid substituent group and including a perfluorovinyl oxy group in a sock end;

b) preparing an acid-substituted block copolymer represented by the following Chemical Formula 10 by polymerizing an aromatic monomer of the following Chemical Formula 6 containing a perfluorovinyl oxy group in a sock end with the hydrophilic block oligomer prepared in step a); And

c) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step b) to an acid group (R ″).

[Formula 6]

F ₂ C = FC-PRP-CF = CF ₂

[Formula 8]

F ₂ C = FC-P-R '"-P-CF = CF ₂

[Formula 9]

F ₂ C = FC-P-(-R '"-PQP-) _m' -R '"-P-CF = CF ₂

[Formula 10]

-(-RPQP-) _n -(-R '"-PQP-) _m-

In the above, P, Q, R, R '", m', n and m are as defined in the above method i), respectively.

"In the step of conversion (the" acid group (R), the acid substituent group R R) "" of the method "are ^{_{-SO 3 - M +, -PO 3}} H - M + or -PO ₃ ^{2 -} 2M ^In the case of containing an acid substituent group of ⁺ , an acid solution is added to the acid substituent multiblock copolymer to convert into an acid group, and an acid substituent of -SO ₂ Cl, -SO ₂ F or -P (O) (OA) ₂ . In the case of containing a group, the acid-substituted multiblock copolymer may be converted into an acid group by hydrolysis in an acidic solution, or hydrolyzed in a basic solution, and then treated with an acidic solution.

The method for preparing the block copolymer (I) according to the present invention will be described in more detail with reference to Scheme 1 below.

As shown in the above scheme, in the case of the block oligomer compound (7) and the compound (9), respectively, the monomer compound (6) and the compound (8) are prepared, and the multiblock copolymer (10) having an acid substituent is a hydrophobic block oligomer. A phosphorus compound (7) and a hydrophilic block oligomer compound (9) are mixed, or a compound (7) and a hydrophilic monomer compound (8) which are hydrophobic block oligomers are mixed, or a hydrophobic monomer compound (6) and a hydrophilic block oligomer compound (9) It can be prepared by mixing. At this time, heat is applied for 30 minutes to 48 hours under nitrogen or argon atmosphere, which is an inert gas, to form a perfluorocyclobutane ring in a molten state or a solution state, thereby causing a polymerization reaction. The temperature of the reaction is suitably made at 80 ° C. or higher, preferably 130 ° C. or higher, because at 80 ° C. or lower, the cyclization reaction does not occur or occurs too slowly.

When prepared in solution, the reaction organic solvent is not particularly limited as long as it can properly dissolve the reactants and the product. However, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF) Aprotic polar solvent such as dimethylacetamide (DMAC) or a solvent having a boiling point of 130 ° C. or higher, such as diphenyl ether (DPE), 1,3,5-trimethylbenzene, or the like.

In the above methods, when the copolymer is formed of the hydrophobic monomer compound (6) and the hydrophilic block compound (9), m 'is 2 or more, and the copolymer is formed of the hydrophobic block compound (7) and the hydrophilic monomer compound (8). N 'is 2 or more when formed, and n' and m 'are 2 or more when a copolymer is formed from a hydrophobic block compound (7) and a hydrophilic block compound (9).

The multiblock copolymer prepared as described above has excellent mechanical properties compared to conventional homopolymers or random copolymers containing perfluorocyclobutane, and the distribution, position and number of acid groups such as sulfonic acid groups in the polymer skeleton. Control is possible, and there is no deterioration of the film properties due to the increase of the acid groups, thus enabling effective membrane production.

The present invention relates to a block copolymer (III) comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[Formula 1]

(-R-P-Q-P-)

(-R'-P-Q-P-)

Where

Each -P- is independently selected from the group consisting of -O-, -S-, -SO-, SO _2- , -CO-, -NH-, -NR _1- , and -R _2- , wherein R ₁ represents alkyl or aryl having 1 to 25 carbon atoms, R ₂ represents alkylene or arylene having 1 to 25 carbon atoms,

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로 이루어진 그룹으로부터 선택된 하나 이상의 술폰화 활성이 낮은 방향족 화합물을 나타내고, -Q- each independently represent 1,2-perfluorocyclobutylene (C ₄ F ₆ ), and R is

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At least one sulfonated low aromatic compound selected from the group consisting of

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로 이루어진 그룹으로부터 선택된 하나 이상의 술폰화 활성이 높은 방향족 화합물을 나타내며, R 'is

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At least one sulfonated high aromatic compound selected from the group consisting of

Where A represents -NO ₂ , or -CF ₃ .

More preferred block copolymer (III) includes a repeating unit represented by the following formula (3).

Wherein R and R 'are the same as defined in the above block copolymer (III),

n and m are each an integer of 1 to 10,000.

The block copolymer according to the present invention is characterized in that the block oligomer having a low sulfonation activity represented by the formula (1) and the block oligomer having a high sulfonation activity represented by the formula (2) are alternately bonded. Therefore, by adjusting the n and m values of the formula (3) it is possible to easily control the distribution, position, number and the like of the sulfonic acid group in the polymer skeleton.

The present invention also provides A) polymerization of a block oligomer having a high sulfonation activity and a block oligomer having a low sulfonation activity, or B) a block oligomer having a low sulfonation activity and a perfluorovinyl oxy group at the end thereof. To prepare a block copolymer (III) by polymerizing a monomer having a high sulfonation activity or polymerizing a block oligomer having a high sulfonation activity and a monomer having a low sulfonation activity including a perfluorovinyl oxy group at the end thereof. It is about a method.

More specifically, the preparation method A) of the block copolymer (III) according to the present invention is

a) preparing a block oligomer of the general formula (7) having a low sulfonation activity by polymerizing an aromatic monomer of the general formula (6) having a low sulfonation activity and including a perfluorovinyl oxy group in a sock end;

b) preparing a block oligomer of Formula 12 having high sulfonation activity by polymerizing an aromatic monomer of Formula 11 having a high sulfonation activity and a perfluorovinyl oxy group in a sock end; And

c) polymerizing the low sulfonation activity block oligomer prepared in step a) and the high sulfonation activity block oligomer prepared in step b).

[Formula 6]

F ₂ C = FC-PRP-CF = CF ₂

[Formula 7]

F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂

F ₂ C = FC-P-R'-P-CF = CF ₂

F ₂ C = FC-P-(-R'-PQP-) _{m '} -R'-P-CF = CF ₂

Wherein P, Q, R, and R 'are as defined for each block copolymer (III),

n 'and m' are each an integer of 2 to 10,000.

Process B) for preparing block copolymer (III) according to the present invention

a) preparing a block oligomer of the general formula (7) having a low sulfonation activity by polymerizing an aromatic monomer of the general formula (6) having a low sulfonation activity and including a perfluorovinyl oxy group in a sock end; And

b) polymerizing the block oligomer having a low sulfonation activity prepared in step a) and an aromatic monomer of Formula 11 having a high sulfonation activity and a perfluorovinyl oxy group in the sock end.

[Formula 6]

F ₂ C = FC-PRP-CF = CF ₂

[Formula 7]

F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂

[Formula 11]

F ₂ C = FC-P-R'-P-CF = CF ₂

Wherein P, Q, R, and R 'are as defined for each block copolymer (III),

n 'is an integer from 2 to 10,000.

In addition, the preparation method C) of the block copolymer (III) according to the present invention is

a) preparing a block oligomer of formula 12 having a high sulfonation activity by polymerizing an aromatic monomer of formula 11 having a high sulfonation activity and a perfluorovinyl oxy group in a sock end; And

b) polymerizing an aromatic monomer of Formula 6 having a high sulfonation activity block oligomer prepared in step a) and a low sulfonation activity and a perfluorovinyl oxy group in the sock end.

[Formula 6]

F ₂ C = FC-PRP-CF = CF ₂

[Formula 11]

F ₂ C = FC-P-R'-P-CF = CF ₂

[Formula 12]

F ₂ C = FC-P-(-R'-PQP-) _{m '} -R'-P-CF = CF ₂

Wherein P, Q, R, and R 'are as defined for each block copolymer (III),

m 'is an integer from 2 to 10,000.

A method for preparing block copolymer (III) according to the present invention will be described in more detail with reference to Scheme 2 below.

As shown in Scheme 2, the block oligomer compounds (7) and (12) are prepared from the monomer compounds (6) and (11), respectively, and the compound is a monomer in the case of (III) which is a block copolymer before the sulfonic acid group is introduced. ) And a block oligomer compound (12), a block oligomer compound (7) and a monomer compound (11), or a block oligomer compound (7) and (12) is prepared by mixing under an inert gas nitrogen or argon atmosphere Heating from 30 minutes to 72 hours results in the formation of perfluorocyclobutane rings in the molten or solution state, and polymerization occurs. It is preferable that the temperature of reaction is 80 degreeC-300 degreeC, More preferably, it is 130 degreeC or more. Below 80 ° C., no cyclization occurs or occurs too slowly, and above 300 ° C. decomposition may occur.

When prepared in solution, the reaction organic solvent is not particularly limited as long as it can dissolve the reactants and products properly. However, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), and dimethylformamide (DMF) And an aprotic polar solvent such as dimethylacetamide (DMAc) or a solvent having a boiling point of 130 ° C. or higher, such as diphenyl ether, 1,3,5-trimethylbenzene, or the like.

The present invention also relates to a process for the preparation of the fonned block copolymer (II) described below which comprises the step of sulfonating the block copolymers prepared by the above production methods A) to C).

The sulfonation step may use a well-known method, and the fonning agent to be used includes all materials capable of introducing -SO ₃ H into the polymer, in particular chlorosulphonic acid, sulfur trioxide, sulfuric acid, fuming sulfuric acid, Preference is given to using, but not limited to, additive compounds comprising acyl sulfate and sulfur trioxide.

The invention also relates to an electrolyte membrane comprising the block copolymer according to the invention. The electrolyte membrane may be prepared in all known membrane forms and may have, for example, a flat membrane, a hollow fiber membrane, a composite membrane, or a tube membrane. The electrolyte membrane prepared according to the present invention has excellent mechanical properties compared to conventional homopolymers or random copolymers containing perfluorocyclobutane, and can control the distribution, position, number, and the like of sulfonic acid groups in the polymer skeleton. There is no deterioration of the film properties due to the increase of the group.

The present invention also provides a method for preparing the electrolyte membrane, wherein the preparation method comprises the use of an acid-substituted block copolymer of formula (10) and a block copolymer (I) or (III) according to the present invention. (B) is an example.

The method (A) comprises the step of dissolving the acid-substituted block copolymer of the formula (10) in a molten or organic solvent to prepare a polymer film having a predetermined thickness and then substituted with an acid.

[Formula 10]

-(-RPQP-) _n -(-R '"-PQP-) _m-

In the above, P, Q, R, R '", n' and m 'are as defined in the formula (10), respectively.

The method (B) comprises the steps of dissolving the block copolymer (I) or (III) according to the present invention in an organic solvent;

Coating the polymer solution on a support to form a film; And

It relates to a method for producing an electrolyte membrane comprising the step of drying the formed film.

Looking at the manufacturing method in detail as follows.

First, referring to the method (A), a polymer solution is prepared by dissolving a polymeric acid substituent agent represented by Chemical Formula 10 in an organic solvent. The prepared polymer solution is film-coated on a porous polymer support or solid surface such as glass plate, metal, ceramic and polysulfone or polyisamide, which are used for known membrane coating, to form a film. The formed film is dried for 10 minutes to 24 hours at atmospheric pressure or vacuum in the temperature range of 50 ℃ to 250 ℃ to prepare a polymer film. In the polymer membrane thus prepared, when the acid substituent is -SO ₂ Cl, -SO ₂ F or -P (O) (OA) ₂ , the membrane is hydrolyzed in an acidic solution or hydrolyzed in a basic solution and then acidic again. It can be prepared by treating with a solution. The acidic or basic solution used at this time is a solution which does not dissolve the membrane, and an aqueous solution containing an acid or a base is preferable. The acid substituent ^{_{-SO 3 - M +, -PO 3}} H - M + or -PO ₃ ^{2 -} If the 2M ^+, can be prepared by treating a film with an acidic solution.

In addition, looking at the method (B), a polymer solution is prepared by dissolving the fonned block copolymer according to the present invention in an organic solvent. The organic solvent does not induce a chemical reaction and is not particularly limited as long as it can dissolve the polymer appropriately. Specific examples thereof include dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), Dimethylformamide (DMF) or dimethylacetamide (DMAc) and the like can be used. The prepared polymer solution is coated on a support used for known membrane coating to form a film. The support is not particularly limited and includes, for example, a solid support such as a glass plate, a metal, or a ceramic, and a porous polymer support such as polysulfone or polyisamide. The film formed on the support is dried for 10 minutes to 48 hours at atmospheric pressure or vacuum in the temperature range of 50 ℃ to 250 ℃ to prepare an electrolyte membrane.

The invention also relates to a fuel cell comprising the electrolyte membrane according to the invention. The fuel cell is preferably a polymer electrolyte fuel cell or a direct methanol fuel cell. In addition, the electrolyte membrane according to the present invention may be used in various applications such as an ion exchange membrane, a dehumidification membrane, or a humidification membrane in addition to the fuel cell membrane.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Example 1

1) Biphenyl Hydrophobic Block Oligomer  Preparation (Compound 6-1)

end. Preparation of 4,4'-Bis (2-bromotetrafluoroethoxy) biphenyl

700 ml of anhydrous DMSO and 10.56 g (0.44 mol) of NaH were added to a 2000 ml round flask under nitrogen atmosphere, and 37.20 g (0.20 mol) of 4,4'-Biphenol was slowly injected four times while stirring. After the completion of the hydrogen gas generation, 114.40 g (0.44 mol) of 1,2-dibromotetra fluoroethane was slowly added dropwise, and the reaction temperature was stirred for one day so as not to exceed 35 ° C. The reaction mixture was mixed with water, extracted with diethyl ether, and the dried product was separated and purified through normal column with hexane through a column containing silica gel.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.31 (d), 7.58 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.5 (s), -86.4 (s).

I. Preparation of 4,4'-Bis (trifluorovinyloxy) biphenyl (Compound 6-1)

In a nitrogen atmosphere, 4,4'-Bis (2-bromotetrafluoroethoxy) biphenyl 54.40 g (0.10 mol) and Zinc powder 19.60 g (0.30 mol) were added to 300 mL of anhydrous CH ₃ CN and heated to reflux with stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane through a column containing silica gel.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.18 (d), 7.54 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -119.9 (dd), -126.7 (dd), -134.9 (dd).

All. Preparation of Hydrophobic Block Oligomer Compound (7-1)

In a nitrogen atmosphere, 4,4'-Bis (trifluorovinyloxy) biphenyl was heated at 170 ℃ for 4 hours and then slowly cooled to room temperature.

Polystyrene column (GPC) Mn 3,000 (g / mol).

2) Biphenyl Hydrophilic Block Oligomer  Preparation (Compound 9-1)

end. Preparation of 4,4'-Bis (2-bromotetrafluoroethoxy) -biphenyl-3,3'-disulfonyl chloride

Place a 1000 mL round flask in an ice bath, mix 54.40 g (0.10 mol) of 4,4'-Bis (2-bromotetra fluoroethoxy) biphenyl with 200 mL of CHCl ₃ , and add 400 g of chlorosulfonic acid under a nitrogen atmosphere. Slowly added dropwise. After 12 hours, the reaction solution was added to 2000 mL ice water, and the organic layer was separated and washed several times with ice water. The dried product was separated and purified using normal hexane and ethyl acetate through a column containing silica gel.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.76 (d), 7.97 (d), 8.29 (s), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.4 (s), -85.9 ( s).

I. Preparation of 4,4'-Bis (2-bromotetrafluoroethoxy) -biphenyl-3,3'-disulfonyl fluoride

200 mL of CH ₃ CN dried in a 500 mL round flask under nitrogen atmosphere, 37.10 g (0.05 mol) of 4,4'-Bis (2-bromotetrafluoroethoxy) -biphenyl-3,3'-disulfonyl chloride, 21.80 g (0.38 mol) of NaF ) And refluxed. After two days, the reaction was filtered through a filter paper, and the filtrate was washed with water and dried in vacuo. The dried product was separated and purified through a column containing silica gel using ethyl acetate and normal hexane.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.76 (d), 7.99 (d), 8.27 (s), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): 62.0 (s), -68.8 (s ), -86.1 (s).

All. Preparation of 4,4'-Bis (trifluorovinyloxy) -biphenyl-3,3'-disulfonyl fluoride (Compound 8-1)

4,4'-Bis (2-bromotetrafluoroethoxy) -biphenyl-3,3'-disulfonyl fluoride 20.00 g (28.00 mmol), copper (I) chloride 5.60 g (0.05 mol) Zinc powder 5.90 g (0.09 mol) _It was added to 150 mL of ₃ CN and heated to reflux with stirring. After 3 days the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane and ethyl acetate through a column containing silica gel.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.76 (d), 7.98 (d), 8.23 (s), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): 62.6 (s), -115.5 (dd ), -122.1 (dd), -135.1 (dd).

la. Preparation of Hydrophilic Block Oligomer Compound (Compound 9-1)

In a nitrogen atmosphere, 4,4'-Bis (trifluorovinyloxy) -biphenyl-3,3'-disulfonyl fluoride was heated at 160 ℃ for 4 hours, and then slowly cooled to room temperature.

Polystyrene column (GPC) Mn 2,100 (g / mol).

3): Biphenyl-based multiblock copolymer (Compound 10-1) and Electrolyte membrane  Produce

Under a nitrogen atmosphere, the hydrophobic block oligomer of Compound 6-1 and the hydrophilic block oligomer of Compound 9-1 were mixed at a weight ratio of 5: 1, 10: 1, and 20: 1, respectively, heated at 250 ° C. for 5 hours, and then slowly cooled to room temperature. Cooled to. Each of the obtained polymers was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a polymeric acid substituent corresponding to compound (10-1). The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze, followed by conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. As a result of measuring the Cannon-Fenske viscometer, the weight ratio is 1.5 (g / dl) ^-1 for 5: 1, 1.2 (g / dl) ^-1 for 10: 1 and 1.3 (for 20: 1) g / dl) ^-1 .

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 2

After melting the three kinds of the polymeric acid substituent (Compound 10-1) prepared in Example 1 on the glass plate, after adjusting the thickness of the copolymer solution on the glass plate with a film applicator, dried in an oven at 80 ℃ for one day, Vacuum drying at 140 ℃ oven for 10 hours to prepare a polymer film of 50 ~ 120 ㎛ thickness. The polymer membrane was hydrolyzed in K ₂ CO ₃ aqueous solution (10 wt%) for one day, and then conc. A multiblock copolymer electrolyte membrane was prepared by treating with aqueous HCl solution and distilled water.

Example 3

One) Fluorene Hydrophobic block Oligomer  Preparation (Compound 7-2)

end. Preparation of 9,9-Bis- {4- (2-bromotetrafluoroethoxy) -phenyl} fluorene

In a 2000 mL round flask, 1000 mL of anhydrous DMSO and 10.56 g (0.44 mol) of NaH were added and stirred under nitrogen atmosphere, and 70.10 g (0.20 mol) of 9,9-bis (4'-hydroxyphenyl) fluorene was slowly injected four times. And stirred. After the hydrogen gas production was completed, 114.40 g (0.44 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise, and the reaction temperature was stirred for one day while not exceeding 35 ° C. The reaction mixture was mixed with water, extracted with diethyl ether, and the dried product was separated and purified through normal column with hexane through a column containing silica gel.

I. Preparation of 9,9-Bis (4-trifluorovinyloxyphenyl) fluorine (Compound 6-2)

In a nitrogen atmosphere, 70.80 g (0.10 mol) of 9,9-bis- [4- (2-bromotetrafluoroethoxy) -phenyl] fluorene and 19.60 g (0.30 mol) of zinc powder were added to 500 mL of anhydrous diglyme, and heated to reflux. . After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane through a column containing silica gel.

All. Preparation of Hydrophobic Block Oligomer Compound (7-2)

In a nitrogen atmosphere, 10.00 g of 9,9-bis (4-trifluorovinyloxyphenyl) fluorene was dissolved in 50.00 g of diphenyloxide, heated at 170 ° C. for 4 hours, and then slowly cooled to room temperature.

Polystyrene column (GPC) Mn 3,100 (g / mol).

2): Preparation of Fluorene Hydrophilic Block Oligomer (Compound 9-2 )

end. Preparation of 9,9-bis- {4- (2-bromotetrafluoroethoxy) phenyl} fluorene-2,7-disulfonic acid, sodium salt

Place a 1000 mL round flask in an ice bath, mix 70.80 g (0.10 mol) of 9,9-bis- [4- (2-bromotetrafluoroethoxy) -phenyl] fluorene with 200 mL of CHCl ₃ , then add chlorosulfonic acid 400.00 g was slowly added dropwise under a nitrogen atmosphere. After 12 hours, the reaction solution was added to 2000 mL ice water, and the organic layer was separated, washed with ice water, and stirred for 10 days by adding 10 wt% Na ₂ CO ₃ aqueous solution, and the dried product was recrystallized with acetone.

I. Preparation of 9,9-bis- (4-trifluorovinyloxyphenyl) fluorene-2,7-disulfonic acid, sodium salt (Compound 8-2)

9,9-bis- [4- (2-bromotetrafluoroethoxy) phenyl] fluorene-2,7-disulfonic acid, sodium salt 27.40 g (0.03 mol), copper (I) chloride 5.60 g (0.05 mol), Zinc powder 5.90 g (0.09 mol) was added to 150 mL of anhydrous CH ₃ CN and heated to reflux with stirring. After 3 days the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was recrystallized using acetone.

All. Preparation of the hydrophilic block oligomeric compound (9-2)

10.00 g of 9,9-bis- [4- (2-bromotetrafluoroethoxy) phenyl] fluorene-2,7-disulfonic acid and sodium salt were added to 50 mL of NMP, and heated at 160 ° C. for 4 hours under nitrogen atmosphere. Cooled to.

Polystyrene column (GPC) Mn 3,400 (g / mol).

3): Fluorene Multi-block copolymers and Electrolyte membrane  Produce

The hydrophobic block oligomer (compound 7-2) and the hydrophilic block oligomer (compound 9-2) were mixed at a weight ratio of 5: 1, 10: 1, and 20: 1, respectively, and added to 20 wt% in NMP, followed by nitrogen atmosphere. Under heating at 200 ° C. for one day and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise to excess methanol to precipitate, followed by filtration and drying to obtain a polymer acid substituent corresponding to compound (10-2). The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze, followed by conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. As a result of measuring the Cannon-Fenske viscometer, the weight ratio is 0.9 (g / dl) ^-1 for 5: 1, 1.0 (g / dl) ^-1 for 10: 1 and 1.1 (for 20: 1) g / dl) ^-1 .

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 4

One): Phosphine  oxide hydrophobic block Oligomer  Preparation (Compound 7-3)

end. Preparation of Bis {4- (2-bromotetrafluoroethoxy) phenyl} phenylphosphine oxide

In a 2000 mL round flask, 700 mL of anhydrous DMSO and 10.56 g (0.44 mol) of NaH were added and stirred under a nitrogen atmosphere, and 62.00 g (0.20 mol) of bis (4-hydroxyphenyl) phenylphosphine oxide was slowly injected and stirred four times. After the completion of the hydrogen gas generation, 114.40 g (0.44 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise and the reaction temperature was stirred for one day while not exceeding 35 ° C. The reaction mixture was mixed with water, extracted with ethyl acetate, and the dried product was separated and purified through normal column with silica gel using normal hexane and ethyl acetate.

I. Preparation of Bis (4-trifluorovinyloxyphenyl) phenylphosphine oxide (Compound 6-3)

In a nitrogen atmosphere, 66.80 g (0.10 mol) of bis [4- (2-bromotetrafluoroethoxy) phenyl] phenylphosphine oxide and 19.60 g (0.30 mol) of zinc powder were added to 500 mL of anhydrous CH ₃ CN, and the mixture was heated to reflux. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane and ethyl acetate through a column containing silica gel.

All. Preparation of Hydrophobic Block Oligomer Compound (7-3)

In a nitrogen atmosphere, 10.00 g of bis (4-trifluorovinyloxyphenyl) phenylphosphine oxide was dissolved in 50.00 g of diphenyloxide, heated at 170 ° C. for 4 hours, and then slowly cooled to room temperature.

Polystyrene column (GPC) Mn 2,800 (g / mol).

(2): Phosphine  oxide hydrophilic block Oligomer  Preparation (Compound 9-3)

end. Preparation of Bis {4- (2-bromotetrafluoroethoxy) -3-chlorosulfonylphenyl} -3-chlorosulfonyl phenylphosphine oxide

Place a 1000 mL round flask in an ice bath, mix 66.80 g (0.10 mol) of bis [4- (2-bromo tetrafluoroethoxy) phenyl] phenylphosphine oxide with 300 mL of CHCl ₃ , and add 400.00 g of chlorosulfonic acid to a nitrogen atmosphere. It was dripped slowly under. After 12 hours, the reaction solution was added to 2000 mL ice water, and the organic layer was separated and washed several times with ice water. The dried product was separated and purified using normal hexane and ethyl acetate through a column containing silica gel.

I. Preparation of Bis {4- (2-bromotetrafluoroethoxy) -3-chlorosulfonylphenyl} -3-fluorosulfonyl phenyl phosphine oxide

200 mL of CH ₃ CN dried in a 500 mL round flask under nitrogen atmosphere, 48.20 g (0.05 mol) of bis [4- (2-bromo tetrafluoroethoxy) -3-chlorosulfonylphenyl] -3-chlorosulfonyl phenyl phosphine oxide, 21.80 g NaF (0.38) mol) was added and refluxed. After two days, the reaction was filtered through a filter paper, and the filtrate was washed with water and dried in vacuo. The dried product was separated and purified through a column containing silica gel using ethyl acetate and normal hexane.

All. Preparation of Bis (4-trifluorovinyloxy-3-chlorosulfonylphenyl) -3-fluorosulfonyl phenyl phosphine oxide (Compound 8-3)

Bis [4- (2-bromotetrafluoroethoxy) -3-chlorosulfonylphenyl] -3-fluorosulfonyl phenyl phosphine oxide 27.40 g (0.03 mol), copper (I) chloride 5.60 g (0.05 mol), Zinc powder 5.90 g (0.09 mol) It was added to 150 mL of CH ₃ CN and heated to reflux with stirring. After 3 days the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane and ethyl acetate through a column containing silica gel.

la. Preparation of the hydrophilic block oligomeric compound (9-3)

10.00 g of Bis (4-trifluorovinyloxy-3-chlorosulfonylphenyl) -3-fluorosulfonyl phenyl phosphine oxide was added to 50 mL of NMP, and then heated at 160 ° C. for 4 hours under a nitrogen atmosphere, and then slowly cooled to room temperature.

Polystyrene column (GPC) Mn 3,500 (g / mol).

3): Phosphine  oxide-based multiblock copolymers and Electrolyte membrane  Produce

The hydrophobic block oligomer (Compound 7-3) and the hydrophilic block oligomer (Compound 9-3) were mixed at a weight ratio of 5: 1, 10: 1, and 20: 1, respectively, and added to NMP at 20 wt% and then under nitrogen atmosphere. After heating at 200 ° C. for one day, it was slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise to excess methanol to precipitate, filtered and dried to obtain a polymer acid substituent corresponding to compound 10-3. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution and hydrolyzed for one day, followed by conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. For a ^{1 0.9 (g / dl) -1} , 10:: intrinsic viscosity results, the weight ratio of 5 was measured (Cannon-Fenske viscometer) for ^{1 0.9 (g / dl) -1} , 20: For a 1 1.0 (g / dl) ^-1

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 5

The hydrophobic block oligomeric compound (7-1) of Example 1 and 4,4'-Bis (trifluorovinyloxy) -biphenyl-3,3'-disulfonyl fluoride (Compound 8-1), which are hydrophilic monomers, were each 5: 1 in weight ratio. , 10: 1, 20: 1 mixed and heated at 250 ℃ for 5 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to obtain a polymeric acid substituent corresponding to compound 10-4. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze, followed by conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. As a result of measuring the Cannon-Fenske viscometer, it is 1.7 (g / dl) ^{-1 for} weight ratio 5: 1, 1.4 (g / dl) ^-1 for 10: 1 and 1.5 (g for 20: 1 / dl) ^-1

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 6

The hydrophilic block oligomeric compound (9-1) obtained in Example 1 and the hydrophobic monomer 4,4'-Bis (trifluorovinyloxy) biphenyl (Compound 6-1) in a weight ratio of 5: 1, 10: 1, 20: 1, respectively The mixture was heated to 250 ° C. for 5 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol to precipitate, and the mixture was filtered and dried to obtain a polymer acid substituent corresponding to compound 10-5. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze and then conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. Measurements of the Cannon-Fenske viscometer showed 1.2 (g / dl) ^-1 for 5: 1, 1.4 (g / dl) ^-1 for 10: 1, and 1.5 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 7

A hydrophobic block oligomer (Compound 7-2) obtained in Example 3 and a hydrophilic monomer 9,9-bis- (4-trifluorovinyloxyphenyl) fluorene-2,7-disulfonic acid, sodium salt (Compound 8-2) by weight ratio The mixture was mixed at 5: 1, 10: 1, and 20: 1 to 20 wt% in NMP, and then heated at 200 ° C. under nitrogen atmosphere for one day, and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise to excess methanol to precipitate, filtered and dried to obtain a polymer acid substituent corresponding to compound 10-6. The high molecular acid substituent was added to a K ₂ CO ₃ aqueous solution (10 wt%) and a DMSO mixed solution and hydrolyzed for one day, followed by conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. As a result of measuring the intrinsic viscosity (Cannon-Fenske viscometer), 5 : For ^{1 1.1 (g / dl) -1} , 10: For a ^{1 1.2 (g / dl) -1} , 20: For a 1 1.1 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 8

The hydrophilic block oligomer (Compound 9-2) obtained in Example 3 and the hydrophobic monomer 9,9-bis (4-trifluorovinyloxyphenyl) fluorene (Compound 6-2) are 5: 1, 10: 1, 20: The mixture was mixed with 1 and added to NMP to 20 wt%, and then heated at 200 ° C. under nitrogen atmosphere for one day, and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise into excess methanol to precipitate, and the mixture was filtered and dried to obtain a polymer acid substituent corresponding to compound 10-7. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze and then conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. The measurement of the inherent viscosity (Cannon-Fenske viscometer): 1.3 (g / dl) ^-1 for 5: 1, 1.2 (g / dl) ^-1 for 10: 1, 1.4 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 9

The hydrophobic block oligomer (Compound 7-3) and the hydrophilic monomer Bis (4-trifluorovinyloxy-3-chlorosulfonylphenyl) -3-fluorosulfonyl phenyl phosphine oxide (Compound 8-3) obtained in Example 4 were each 5: 1, 10: 1 and 20: 1 were mixed and added to NMP to 20 wt%, and then heated at 200 ° C. under nitrogen atmosphere for one day, and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise to excess methanol to precipitate, followed by filtration and drying to obtain a polymer acid substituent corresponding to compound 10-8. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze and then conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. Measurements of the Cannon-Fenske viscometer showed 0.9 (g / dl) ^-1 for 5: 1, 1.2 (g / dl) ^-1 for 10: 1, and 1.0 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 10

The hydrophilic block oligomer (Compound 9-3) and hydrophobic monomer bis (4-trifluorovinyloxyphenyl) phenylphosphine oxide (Compound 6-3) prepared in Example 4 were 5: 1, 10: 1 and 20: 1, respectively. The mixture was added to NMP to 20 wt%, heated at 200 ° C. under nitrogen atmosphere for one day, and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise to excess methanol to precipitate, and the mixture was filtered and dried to obtain a polymer acid substituent corresponding to compound 10-9. The polymer acid substituent was added to K ₂ CO ₃ aqueous solution (10 wt%) and DMSO mixed solution for one day to hydrolyze and then conc. Sulfonated multiblock copolymers were prepared by treatment with aqueous HCl solution and distilled water. The measurement of the inherent viscosity (Cannon-Fenske viscometer): 1.3 (g / dl) ^-1 for 5: 1, 1.2 (g / dl) ^-1 for 10: 1, 1.4 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in 15 wt% in DMAc and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and vacuum dried in an oven at 140 ° C. for 10 hours. A multiblock copolymer electrolyte membrane having a thickness of 50 to 120 μm was prepared.

Example 11

One) Sulfone  block Oligomer  Preparation (Compound 7-4)

end. 4,4'-sulfonyl-bis (2-bromotetrafluoroethoxy) biphenyl manufacturing step

To a 500 mL round flask was added 250 mL of anhydrous DMSO and 7.2 g (0.3 mol) of NaH under nitrogen, followed by slow addition of 25 g (0.1 mol) of 4,4'-sulfonyl diphenol under stirring four times under stirring. . After the hydrogen gas production was completed, 35.8 mL (0.3 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise, and the reaction temperature was controlled to not exceed 35 ° C and stirred for 24 hours. The reaction mixture was mixed with water, extracted with ethyl acetate, and the dried product was separated and purified through normal column with silica gel using normal hexane and ethyl acetate to obtain the title compound.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.38 (d), 8.01 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.9 (s), -86.7 (s)

I. 4,4'-Sulfonyl-bis (trifluorovinyloxy) biphenyl (Compound 6-4)

, 및 P = -O-)을 수득하였다.In a nitrogen atmosphere, 30 g (49.3 mmol) of 4,4'-sulfonyl-bis (2-bromotetrafluoroethoxy) biphenyl and 9.7 g (148 mmol) of zinc powder were dissolved in anhydrous CH ₃ CN 150 It was added to mL and heated to reflux with stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified through a column containing silica gel using normal hexane and ethyl acetate to obtain the title compound (Formula 6 compound: R =

, And P = -O-).

¹ H-NMR (CDCl ₃ , δ in ppm): 7.22 (d), 7.97 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -118.3 (dd), -124.9 (dd), -135.7 (dd).

All. Sulfonated Block Oligomer (Compound 7-4) Preparation Step

, B= C₄F₆, 및 P = -O-)을 수득하였다.　 In a nitrogen atmosphere, 4,4'-sulfonyl-bis (trifluorovinyloxy) biphenyl was heated at 170 ° C. for 4 hours and then slowly cooled to room temperature to give the title compound (Formula 7 R:

, B = C ₄ F ₆ , and P = −O—).

Polystyrene column (GPC) Mn 2,500 (g / mol).

2) Fluorene  block Oligomer  Preparation (Compound 12-4)

end. 9,9-bis- {4- (2-bromotetrafluoroethoxy) -phenyl} fluorene manufacturing step

To a 2000 mL round flask, 1000 mL of anhydrous DMSO and 10.56 g (0.44 mol) of NaH were added under nitrogen and 70.10 g (0.20 mol) of 9,9-bis (4'-hydroxyphenyl) fluorene was added to the mixture under stirring at 4 times. Slowly add over and stir. After the hydrogen gas production was completed, 114.40 g (0.44 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise, and the reaction temperature was controlled to not exceed 35 ° C and stirred for 24 hours. The reaction mixture was mixed with water and extracted with diethyl ether, and then the dried product was separated and purified through a column containing silica gel using normal hexane to obtain the title compound.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.06-7.80 (various m, CH arom.), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.6 (s), -86.5 (s).

I. 9,9-bis (4-trifluorovinyloxyphenyl) fluorene (Compound 11-4)

, 및 P = -O-)을 수득하였다. Under nitrogen atmosphere, 70.80 g (0.10 mol) of 9,9-bis- [4- (2-bromotetrafluoroethoxy) -phenyl] fluorene and 19.60 g (0.30 mol) of zinc powder were dissolved in anhydrous di It was poured into 500 mL of ethylene glycol dimethyl ether (diglyme) and heated to reflux under stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane through a column containing silica gel to obtain the title compound (Formula 11 compound: R ′ =).

, And P = -O-).

¹ H-NMR (CDCl ₃ , δ in ppm): 6.93-7.78 (various m, CH arom.), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -119.9 (dd), -126.8 (dd), -134.2 (dd).

All. Steps for preparing fluorene-based block oligomer (Compound 12-4)

, B= C₄F₆, 및 P = -O-)을 수득하였다. In a nitrogen atmosphere, 10.00 g of 9,9-bis (4-trifluorovinyloxyphenyl) fluorene was dissolved in 10.00 g of diphenyl ether, heated at 170 ° C. for 7 hours, and then slowly cooled to room temperature to obtain the title compound (Formula 9 compound). R '=

, B = C ₄ F ₆ , and P = −O—).

Polystyrene column (GPC) Mn 3,100 (g / mol).

3) Sulfonated  Preparation of Multiblock Copolymer (Compound 5-4) and Preparation of Electrolyte Membrane

, R' =

, 및 P = -O-)를 얻었다.　 Under a nitrogen atmosphere, the sulfonated block oligomer having low sulfonation activity (Compound 7-4) and the fluorene block oligomer having high sulfonation activity (Compound 12-4) were 1: 1, 5: 1, and 10: 1, respectively. It was mixed at a weight ratio of and dissolved in diphenyl ether to 50 wt%, and then heated at 250 ° C. for 16 hours and slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R" =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulfonic acid was slowly added dropwise to 4 moles of fluorene repeat units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R "=

(1 ≦ x + y ≦ 2), and P = −O−).

As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-4 and compound 12-4 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.2 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 0.9 (g / dl) ^-1 was shown.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 12

One) Benzophenone series  block Oligomer  Preparation (Compound 7-5)

end. 4,4'-bis (2-bromotetrafluoroethoxy) benzophenone preparation step

To a 500 mL round flask was added 250 mL of anhydrous DMSO and 7.2 g (0.3 mol) of NaH under nitrogen, followed by slow addition of 21.4 g (0.1 mol) of 4,4'-dihydroxybenzophenone under stirring four times under stirring. I was. After the hydrogen gas production was completed, 35.8 mL (0.3 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise, and the reaction temperature was controlled to not exceed 35 ° C and stirred for 24 hours. The reaction mixture was mixed with water, extracted with ethyl acetate, and the dried product was separated and purified through normal column with silica gel using normal hexane and ethyl acetate to obtain the title compound.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.18 (d), 7.86 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.7 (s), -86.5 (s).

I. 4,4'-bis (trifluorovinyloxy) benzophenone (Compound 6-5)

, 및 P = -O-)을 수득하였다.　　 Under nitrogen atmosphere, 28.2 g (49.3 mmol) of 4,4'-bis (2-bromotetrafluoroethoxy) benzophenone and 9.7 g (148 mmol) of zinc powder were added to 150 mL of anhydrous CH ₃ CN. Heat was added to reflux under stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified through a column containing silica gel using normal hexane and ethyl acetate to obtain the title compound (Formula 6 compound: R =

, And P = -O-).

¹ H-NMR (CDCl ₃ , δ in ppm): 7.22 (d), 7.97 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -117.5 (dd), -123.8 (dd), -136.5 (dd).

All. Preparation of benzophenone block oligomer (Compound 7-5)

, B= C₄F₆, 및 P = -O-)을 수득하였다.　　 In a nitrogen atmosphere, the 4,4'-bis (trifluorovinyloxy) benzophenone was heated at 170 ° C. for 4 hours, and then slowly cooled to room temperature to give the title compound (Formula 7 compound: R =).

, B = C ₄ F ₆ , and P = −O—).

Polystyrene column (GPC) Mn 2,800 (g / mol).

2) biphenyl block Oligomer  Preparation (Compound 12-5)

end. 4,4'-bis (2-bromotetrafluoroethoxy) biphenyl manufacturing step

700 mL of anhydrous DMSO and 10.56 g (0.44 mol) of NaH were added to a 2000 mL round flask under nitrogen, and 37.20 g (0.20 mol) of 4,4'-biphenol was added slowly and stirred four times under stirring. After the hydrogen gas production was completed, 114.40 g (0.44 mol) of 1,2-dibromotetrafluoroethane was slowly added dropwise, and the reaction temperature was controlled to not exceed 35 ° C and stirred for 24 hours. The reaction mixture was mixed with water and extracted with diethyl ether, and then the dried product was separated and purified through a column containing silica gel using normal hexane to obtain the title compound.

¹ H-NMR (CDCl ₃ , δ in ppm): 7.31 (d), 7.58 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -68.5 (s), -86.4 (s).

I. 4,4'-bis (trifluorovinyloxy) biphenyl (Compound 11-5) Preparation Step

, 및 P = -O-)을 수득하였다. In a nitrogen atmosphere, 54.40 g (0.10 mol) of 4,4'-bis (2-bromotetrafluoroethoxy) biphenyl and 19.60 g (0.30 mol) of zinc powder are added to 300 mL of anhydrous CH ₃ CN. Heat was added to reflux under stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified using normal hexane through a column containing silica gel to obtain the title compound (Compound 8: R '=

, And P = -O-).

¹ H-NMR (CDCl ₃ , δ in ppm): 7.18 (d), 7.54 (d), ¹⁹ F-NMR (CDCl ₃ , δ in ppm): -119.9 (dd), -126.7 (dd), -134.9 (dd).

All. Preparation of Biphenyl Block Oligomer (Compound 12-5)

, B= C₄F₆, 및 P = -O-)을 수득하였다. In a nitrogen atmosphere, 4,4'-bis (trifluorovinyloxy) biphenyl was heated at 170 ° C. for 4 hours, and then slowly cooled to room temperature to give the title compound (Formula 9 compound: R ′ =).

, B = C ₄ F ₆ , and P = −O—).

Polystyrene column (GPC) Mn 3,000 (g / mol).

3) Sulfonated  Preparation of Multiblock Copolymer (Formula 5-5) and Preparation of Electrolyte Membrane

, R' =

, 및 P = -O-)를 얻었다.　 Under the nitrogen atmosphere, the benzophenone block oligomer having low sulfonation activity (Compound 7-5) and the biphenyl block oligomer having high sulfonation activity (Compound 12-5) were 1: 1, 5: 1, and 10 :, respectively. The mixture was mixed at a weight ratio of 1, heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R" =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 7-5과 화합물 12-5의 중량비가 1:1의 경우 1.0 (g/dl)^-1, 5:1의 경우 0.8 (g/dl)^-1, 10:1의 경우 0.9 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R "=

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-5 and compound 12-5 is 1.0 (g / dl) ^{-1 for} 1: 1 and 0.8 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 0.9 (g / dl) ^-1 was shown.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 13

One) Fluorophenyl  block Oligomer (Compound 7-6) Preparation

end. 1,4-bis (2-bromotetrafluoroethoxy) tetrafluorobenzene manufacturing step

To a 500 mL round flask, 250 mL of anhydrous DMSO and 7.2 g (0.3 mol) of NaH were added under nitrogen, and 18.2 g (0.1 mol) of tetrafluorohydroquinone was slowly added and stirred under stirring under stirring. After the hydrogen gas production was completed, 35.8 mL (0.3 mol) of 1,2-dibromotetra fluoroethane was slowly added dropwise to adjust the reaction temperature so as not to exceed 35 ° C, and stirred for 24 hours. The reaction was mixed with water, extracted with ethyl acetate, and the dried product was separated and purified through normal column with hexane through a column containing silica gel to obtain the title compound.

I. Preparation of 1,4-bis (trifluorovinyloxy) tetrafluorobenzene (Compound 6-6)

, 및 P = -O-)을 수득하였다. In a nitrogen atmosphere, 26.6 g (49.3 mmol) of 1,4-bis (2-bromotetrafluoroethoxy) tetrafluorobenzen and 9.7 g (148 mmol) of zinc powder were added to 150 mL of anhydrous CH ₃ CN. Added and heated to reflux under stirring. After 16 hours the reaction was filtered through filter paper and the filtrate was dried in vacuo. The dried product was separated and purified through a column containing silica gel using normal hexane and ethyl acetate to obtain the title compound (Formula 6 compound: R =

, And P = -O-).

All. Steps to prepare fluorophenyl block oligomer (Compound 7-6)

, B= C₄F₆, 및 P = -O-)을 수득하였다. In a nitrogen atmosphere, the 1,4-bis (trifluorovinyloxy) tetrafluorobenzene was heated at 170 ° C. for 5 hours and then slowly cooled to room temperature to give the title compound (Formula 7 R:

, B = C ₄ F ₆ , and P = −O—).

Polystyrene column (GPC) Mn 4,000 (g / mol).

2) Sulfonated  Preparation of Multiblock Copolymer (Compound 5-6) and Preparation of Electrolyte Membrane

, R' =

, 및 P = -O-)를 얻었다. Under a nitrogen atmosphere, the sulfonated low fluorophenyl block oligomer (Compound 7-6) and the high sulfonated high fluorene block oligomer (Compound 12-4) prepared in Example 11 were each 1: 1. , 5: 1, and 10: 1 were mixed in a weight ratio, dissolved in diphenyl ether to 50 wt%, heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 7-6과 화합물 12-4의 중량비가 1:1의 경우 1.3 (g/dl)^-1, 5:1의 경우 1.7 (g/dl)^-1, 10:1의 경우 1.8 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of fluorene repeating units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-6 and compound 12-4 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.7 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 1.8 (g / dl) ^-1 was shown.

The polymer thus obtained was dissolved in DMAc at 15 wt% and cast on a glass plate. Then, the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, dried in an oven at 80 ° C. for one day, and then in a 140 ° C. oven for 10 hours. While vacuum dried to prepare a sulfonated multiblock copolymer electrolyte membrane having a thickness of 50 ~ 120 ㎛.

Example 14

, R' =

, 및 P = -O-)를 얻었다. Sulfonated block oligomer (Compound 7-4) and fluorene monomer 9,9-bis (4-trifluorovinyloxyphenyl) fluorene (Compound 11-4) prepared in Example 11, respectively 1: 1 , 5: 1, and 10: 1 were mixed in a weight ratio of 50 wt% in diphenyl ether, and then heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점 도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 7-4과 화합물 11-4의 중량비가 1:1의 경우 1.3 (g/dl)^-1, 5:1의 경우 1.5 (g/dl)^-1, 10:1의 경우 1.5 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of fluorene repeating units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-4 and compound 11-4 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.5 (g / dl for 5: 1) ) ^-1 and 10: 1 showed 1.5 (g / dl) ^-1 .

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 15

, R' =

, 및 P = -O-)를 얻었다. The fluorene-based block oligomer (Compound 12-4) and sulfone monomer 4,4'-sulfonyl-bis (trifluorovinyloxy) biphenyl (Compound 6-4) prepared in Example 11 were each 1: 1, 5: 1, and 10: 1 were mixed in a weight ratio of 50 wt% in diphenyl ether, and then heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 12-4와 화합물 6-4의 중량비가 1:1의 경우 1.3 (g/dl)^-1, 5:1의 경우 1.4 (g/dl)^-1, 10:1의 경우 1.5 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chloro sulfonic acid was slowly added dropwise to 4 moles of fluorene repeat units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 12-4 and compound 6-4 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.4 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 1.5 (g / dl) ^-1 was shown.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 16

, R' =

, 및 P = -O-)를 얻었다. The benzophenone-based block oligomer (Compound 7-5) and biphenyl monomer 4,4'-bis (trifluorovinyloxy) biphenyl (Compound 11-5) prepared in Example 12 were 1: 1, respectively. It was mixed at a weight ratio of 5: 1, and 10: 1, and added to diphenyl ether at 50 wt%, heated at 250 ° C. for 24 hours under nitrogen, and then slowly cooled to room temperature. The obtained polymer was dissolved in tetrahydrofuran, slowly added dropwise into excess methanol, precipitated, filtered, and dried to form a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 7-5와 화합물 11-5의 중량비가 1:1의 경우 1.1 (g/dl)^-1, 5:1의 경우 1.1 (g/dl)^-1, 10:1의 경우 1.2 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 5 moles of the biphenyl repeating unit and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-5 and compound 11-5 is 1.1 (g / dl) ^-1 for 1: 1 and 1.1 (g / dl) for 5: 1 1.2 (g / dl) ^-1 for ^-1 and 10: 1.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 17

, R' =

, 및 P = -O-)를 얻었다. The biphenyl block oligomer (Compound 12-5) and the benzophenone monomer 4,4'-bis (trifluorovinyloxy) benzophenone (Compound 6-5) prepared in Example 12 were 1: 1, respectively. The mixture was mixed at a weight ratio of 5: 1, and 10: 1, dissolved in NMP to 20 wt%, refluxed under nitrogen for 24 hours, and then slowly cooled to room temperature. The obtained polymer solution was slowly added dropwise into excess methanol, precipitated, filtered, and dried to give a block copolymer (Compound 3: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 12-5와 화합물 6-5의 중량비가 1:1의 경우 0.7 (g/dl)^-1, 5:1의 경우 0.8 (g/dl)^-1, 10:1의 경우 0.8 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of the biphenyl repeating unit and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring the Canon-Fenske viscometer, when the weight ratio of compound 12-5 and compound 6-5 is 1: 1, 0.7 (g / dl) ^-1 and 0.8 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 0.8 (g / dl) ^-1 was shown.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 18

, R' =

, 및 P = -O-)를 얻었다. Fluorophenyl block oligomer (Compound 7-6) prepared in Example 13 and the fluorene monomer 9,9-bis (4-trifluorovinyloxyphenyl) fluorene (compound prepared in Example 11) 11-4) were mixed at 1: 1, 5: 1, and 10: 1, respectively, and dissolved in diphenyl ether to 40 wt%, heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to give a multiblock copolymer (Formula 3 compound: R =

, R '=

, And P = -O-).

, R" =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 7-6과 화합물 11-4의 중량비 가 1:1의 경우 1.0 (g/dl)^-1, 5:1의 경우 1.5 (g/dl)^-1, 10:1의 경우 1.3 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of fluorene repeating units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R "=

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 7-6 and compound 11-4 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.5 (g / dl) for 5: 1 ^-1 and 10: 1 showed 1.3 (g / dl) ^-1 .

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Example 19

, R' =

, 및 P = -O-)를 얻었다.　 The fluorene-based block oligomer (Compound 12-4) prepared in Example 11 and the fluorophenyl monomer 1,4-bis (trifluorovinyloxy) tetrafluorobenzene (Compound 6- 6) were mixed at a weight ratio of 1: 1, 5: 1, and 10: 1, respectively, and dissolved in diphenyl ether to 50 wt%, and then heated at 250 ° C. for 16 hours, and then slowly cooled to room temperature. The obtained polymer was dissolved in DMAc, slowly added dropwise into excess methanol, precipitated, filtered, and dried to give a multiblock copolymer (Formula 3 compound: R =

, R '=

, And P = -O-).

, R″ =

(1≤x+y≤2), 및 P = -O-)를 제조하였다. 고유점도(Cannon-Fenske viscometer)를 측정한 결과, 화합물 12-4와 화합물 6-6의 중량비가 1:1의 경우 1.1 (g/dl)^-1, 5:1의 경우 1.6 (g/dl)^-1, 10:1의 경우 1.7 (g/dl)^-1을 보였다. The copolymer was dissolved in dichloroethane at 1 wt% under a nitrogen atmosphere, and then chlorosulphonic acid was slowly added dropwise to 4 moles of fluorene repeating units and sulfonated for 7 hours. The solvent of the mixture was removed and washed several times with distilled water to give a sulfonated multiblock copolymer (Compound 5: R =

, R ″ =

(1 ≦ x + y ≦ 2), and P = −O−). As a result of measuring Cannon-Fenske viscometer, the weight ratio of compound 12-4 and compound 6-6 is 1: 1 (g / dl) ^{-1 for} 1: 1 and 1.6 (g / dl) for 5: 1 ^{In the case of -1} and 10: 1, 1.7 (g / dl) ^-1 was shown.

The obtained polymer was dissolved in DMAc at 15 wt%, cast on a glass plate, and then the thickness of the copolymer solution on the glass plate was adjusted with a film applicator, and then dried in an oven at 80 ° C. for 1 day, and then in a 10 ° C. oven at 140 ° C. Vacuum drying for a time to prepare a sulfonated multiblock copolymer electrolyte membrane of 50 ~ 120 ㎛ thickness.

Test Example  One: Hydrogen ion  Conductivity measurement

In the multiblock copolymer electrolyte membranes obtained in Examples 1, 3 and 4, the hydrophobic block oligomer and the hydrophilic block oligomer were prepared in a weight ratio of 10: 1, and in the multiblock copolymer electrolyte membranes obtained in Examples 11 to 13. The hydrogen ion conductivity of the electrolyte membrane having a low sulfonation activity block oligomer and a high sulfonation activity block 5: 5 by weight ratio was measured by the potentio-static two-probe method, respectively. Area 2 × 2 cm ² 1 × 1 cm ² and 1.5 × 1.5 cm ² carbon paper electrodes are placed on each side of the phosphorus specimen at a constant pressure, and ultrapure water is flowed to the outside. A 5 mV AC voltage is applied across the electrodes at a frequency of 1 MHz-100 Hz. Authorized. At this time, the impedance was obtained through an alternating current applied to both ends of the electrode, and the hydrogen ion conductivity of each of the multiblock copolymer electrolyte membranes was obtained using this.

Hydrogen ion conductivity of the electrolyte membranes of Examples 1, 3 and 4 and Nafion 115 ™ were measured, and the results are shown in FIG. 1. In addition, the results of measuring the hydrogen ion conductivity of the electrolyte membrane and Nafion 115 ™ of the Examples 11 to 13 are shown in FIG. 2. As shown in FIGS. 1 and 2, the electrolyte membranes of Examples 1, 3, 4, and 11 to 13 prepared according to the present invention showed an equivalent or improved hydrogen ion conductivity as compared to Nafion used in the conventional polymer membrane. Could.

Test Example  2: polymer electrolyte fuel cell ( PEMFC Performance evaluation

In order to examine the performance of the polymer electrolyte fuel cell, the electrolyte membrane prepared in Example 4 had a hydrophobic block oligomer and a hydrophilic block oligomer in a weight ratio of 10: 1, and sulfonation activity was observed in the electrolyte membrane prepared in Example 11. An electrolyte membrane having a weight ratio of 5: 1 having a low sulfon-based block oligomer and a high sulfonating activity fluorene-based block oligomer was prepared to have a thickness of 100 μm. At this time, the MEA (membrane electrode assembly) was made of 5 layers, both the positive electrode and the negative electrode 0.5 mg Pt / cm ² The size of the electrode is 5 × 5 cm ² , the size of the electrolyte membrane is 10 × 10 cm ² It was. In addition, in order to make a well dispersed catalyst slurry without aggregation, IPA (isopropyl alcohol), the electrolyte membrane and the same fonned multiblock copolymer solution described below, and water are mixed and dispersed in an appropriate amount (10 wt% of the catalyst ink solvent). After preparing a mixed solvent, the mixture was stirred with the catalyst, and then subjected to ultrasonic grinding for 5 minutes, and subjected to ball milling to crush the catalyst cluster (cluster) to produce smaller particles.

The high temperature compression conditions of the electrolyte membrane and the gas diffusion electrode (GDE) are as follows. The temperature of the high temperature presser was raised to 140 ° C. and maintained at 0.1 ton for 5 minutes to allow sufficient heat transfer. It was then held at 1.0 ton for 2 minutes to ensure sufficient adhesion between the electrolyte membrane and GDE.

The MEA prepared as described above was assembled into a single cell, and the unit cell temperature was 70 ° C., and the flow rates of hydrogen and air were 300 sccm and 1200 cscm, respectively. The polymer electrolyte fuel cell performance was evaluated at 80 ° C. and 85 ° C. at 100% humidification conditions. The open circuit voltage (OCV) has a high value of 1.0 V or higher and pulsed in the constant voltage mode. As a result, the electrolyte membranes of Examples 4 and 11 were 0.8 A / cm ² at 0.6 V, respectively. And 0.9 A / cm ² .

Test Example  3: direct methanol fuel cell ( DMFC Performance evaluation

Direct electrolyte fuel cell performance evaluation was performed using the electrolyte membranes of Examples 4 and 11 having a thickness of 100 μm. Pt-Ru black was used as the anode catalyst and Pt black was used as the cathode catalyst. At this time, in order to make a well-dispersed catalyst slurry without aggregation, IPA, the same solution as the below-mentioned fonned multiblock copolymer solution, and water are mixed with an appropriate amount (10 wt% of the catalyst ink solvent), and the well-dispersed mixed solvent After the preparation, the mixture was stirred with the catalyst, subjected to ultrasonic grinding for 5 minutes, and subjected to ball milling to crush the catalyst cluster (cluster) to prepare smaller particles.

The electrolyte membrane was inserted into the fixing device and heated at a rear side for about 20 minutes with a heat dryer (80 ° C.) to completely remove moisture. The catalyst ink prepared as described above was taken at about 0.1 to 20 cc / cm ² and sprayed onto the front surface of the grid with a spray gun to prepare an active layer (2 mg / cm ² ) of 30 μm or less. At this time, the pressure of the carrier gas was 0.01 to 2 atm, and the catalyst slurry solvent was continuously evaporated during the spray coating by heating the electrolyte membrane with a heat dryer at the rear of the grid.

The electrode prepared as described above was finally produced MEA by pressing the electrolyte membrane including the active layer in the middle at a high temperature of 5 to 100 kg / cm ² at 140 ° C. for 3 to 10 minutes. At this time, the electrolyte membrane was slightly larger than the electrode, and the size of the electrode was 3 × 3 cm ² , and the size of the electrolyte membrane was 6 × 6 cm ^2. It was. The prepared MEA was measured at an operating temperature of 80 ° C., a catalyst usage of 2 mg / cm ² , 2 M methanol as fuel, and an oxygen flow rate of 1000 sccm. As a result, the electrolyte membranes of Examples 4 and 11 prepared according to the present invention exhibited the performance of 0.64 A / cm ² and 0.62 A / cm ² at 0.4 V, respectively.

Although only described in detail with respect to the described embodiments of the present invention, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such variations and modifications belong to the appended claims.

As described above, the electrolyte membrane membrane using the multiblock copolymer including the perfluorocyclobutane group according to the present invention has not only high hydrogen ion conductivity but also excellent mechanical properties and chemical stability, and also within the polymer skeleton. The distribution, position, number, and the like of the sulfonic acid group can be controlled, and there is no deterioration in the physical properties due to the increase in the sulfonic acid group, thereby effectively producing the membrane.

Claims (26)

A block copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (4): [Formula 1] (-R-P-Q-P-) [Formula 4] (-R "-P-Q-P-) Where Each -P- is independently selected from the group consisting of -O-, -S-, -SO-, SO _2- , -CO-, -NH-, -NR _1- , and -R _2- , wherein R ₁ represents alkyl or aryl having 1 to 25 carbon atoms, R ₂ represents alkylene or arylene having 1 to 25 carbon atoms, -Q- each independently represent 1,2-perfluorocyclobutylene (C ₄ F ₆ ), R is an aromatic group substituted or unsubstituted with an inert group that does not induce other chemical reactions in forming the group -Q-, R ″ is an aromatic group comprising one or more benzene rings substituted with one or more —PO ₃ H ₂ or —SO ₃ H. The compound of claim 1, wherein when R or R ″ includes two or more benzene rings, their benzene rings are each directly connected, or —O—, —S—, — (CH ₂ ) —, — (C ( O))-,-(S (O) ₂ )-,-(-P (O))-,-(Si (CH ₃ ) ₂ )-,-(C (CH ₃ ) ₂ )-,-(C A block copolymer characterized by being connected by (CF ₃ ) ₂ )-or-(Si (C ₆ H ₅ ) ₂ )-. The method of claim 1, R is

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

And

At least one aromatic compound selected from the group consisting of R ″

,

,

,

,

,

,

,

,

,

,

,

,

,

,

And

At least one benzene ring of at least one aromatic compound R ′ selected from the group consisting of: at least one -PO ₃ H ₂ or -SO ₃ H represents an aromatic compound, Wherein A represents -NO ₂ or -CF ₃ . The method of claim 3, wherein R is

,

,

And

An aromatic compound selected from the group consisting of R ″

,

,

And

Block copolymer characterized in that the benzene ring of at least one aromatic compound R 'selected from the group consisting of substituted with at least one -PO ₃ H ₂ or -SO ₃ H. The block copolymer according to claim 1, comprising a repeating unit represented by the following formula (5): [Formula 5]

Wherein R and R ″ are each as defined in claim 1, n and m are each an integer of 1 to 10,000. The method of claim 3, wherein R is

,

,

,

And

At least one sulfonated low aromatic compound selected from the group consisting of R ″

,

,

,

,

,

,

,

,

,

,

,

,

And

Block copolymer characterized in that the benzene ring of at least one sulfonication-high aromatic compound R 'selected from the group consisting of represents an aromatic compound substituted with at least one -SO ₃ H. The compound of claim 6, wherein R is

,

or

An aromatic compound selected from R ″

or

Block copolymer characterized in that the benzene ring of the aromatic compound R 'selected from represents an aromatic compound substituted with at least one -SO ₃ H. According to claim 1, wherein the weight average molecular weight of the block containing a repeating unit represented by the formula (1) is 500 to 500,000 (g / mol), the weight average molecular weight of the block containing the repeating unit represented by the formula (4) is 500 to Block copolymer, characterized in that 500,000 (g / mol). a) preparing a hydrophobic block oligomer of Chemical Formula 7 by polymerizing an aromatic monomer of Chemical Formula 6 including a perfluorovinyl oxy group in a sock end; b) preparing an hydrophilic block oligomer represented by the following Chemical Formula 9 by polymerizing an aromatic monomer represented by the following Chemical Formula 8 having an acid-substituted group and including a perfluorovinyl oxy group in a sock end; c) reacting the hydrophobic block oligomer prepared in step a) and the hydrophilic block oligomer prepared in step b) to prepare an acid-substituted block copolymer represented by Chemical Formula 10; And d) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step c) to an acid group (R ″). Method for producing a block copolymer according to claim 1 comprising: [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 7] F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂ [Formula 8] F ₂ C = FC-P-R '"-P-CF = CF ₂ [Formula 9] F ₂ C = FC-P-(-R '"-PQP-) _m' -R '"-P-CF = CF ₂ [Formula 10] -(-RPQP-) _n -(-R '"-PQP-) _m- In the above, P, Q, R, and R "are each as defined in claim 1, R '"is _{-SO 2 Cl, -SO 2 F,} -SO 3 - M +, -P (O) (OA) 2, -PO 3 H - M + and -PO ₃ ^{2 -} 2M ⁺ (wherein, A Is an alkyl having 1 to 4 carbon atoms, M is an alkali metal, and is an aromatic group including at least one benzene ring substituted with at least one acid substituent group selected from the group consisting of n, m, n 'and m' are each an integer of 1 to 10,000. a) preparing a hydrophobic block oligomer of Chemical Formula 7 by polymerizing an aromatic monomer of Chemical Formula 6 including a perfluorovinyl oxy group in a sock end; b) an acid-substituted block copolymer represented by the following Chemical Formula 10 by polymerizing an aromatic monomer of the following Chemical Formula 8 having an acid-substituted group and including a perfluorovinyl oxy group in the sock end with the hydrophobic block oligomer prepared in step a) Preparing a; And c) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step b) to an acid group (R ″). Method for producing a block copolymer according to claim 1 comprising: [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 7] F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂ [Formula 8] F ₂ C = FC-P-R '"-P-CF = CF ₂ [Formula 10] -(-RPQP-) _n -(-R '"-PQP-) _m- In the above, P, Q, R, R ", R '", n', n and m are as defined in claim 9, respectively. a) preparing an hydrophilic block oligomer represented by the following Chemical Formula 9 by polymerizing an aromatic monomer of Chemical Formula 8 having an acid substituent group and including a perfluorovinyl oxy group in a sock end; b) preparing an acid-substituted block copolymer represented by the following Chemical Formula 10 by polymerizing an aromatic monomer of the following Chemical Formula 6 containing a perfluorovinyl oxy group in a sock end with the hydrophilic block oligomer prepared in step a); And c) converting the acid substituent group (R ′ ″) of the acid substituent block copolymer prepared in step b) to an acid group (R ″). Method for producing a block copolymer according to claim 1 comprising: [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 8] F ₂ C = FC-P-R '"-P-CF = CF ₂ [Formula 9] F ₂ C = FC-P-(-R '"-PQP-) _m' -R '"-P-CF = CF ₂ [Formula 10] -(-RPQP-) _n -(-R '"-PQP-) _m- In the above, P, Q, R, R '", m', n and m are as defined in Claim 9, respectively. Of claim 9 to claim 11 according to any one of claims, wherein R '"is ^{_{-SO 3 - M +, -PO 3}} H - M + or -PO ₃ ^{2 -} if the substituent contains an acid group of 2M ⁺ , An acid solution is added to the acid-substituted block copolymer to be converted into an acid group, and when the acid-substituted group includes -SO ₂ Cl, -SO ₂ F or -P (O) (OA) ₂ , The polymerized method is characterized in that the copolymerized into an acidic solution or a basic solution and hydrolyzed, and then converted to an acid group by treatment with an acidic solution. A block copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): [Formula 1] (-R-P-Q-P-) [Formula 2] (-R'-P-Q-P-) Where Each -P- is independently selected from the group consisting of -O-, -S-, -SO-, SO _2- , -CO-, -NH-, -NR _1- , and -R _2- , wherein R ₁ represents alkyl or aryl having 1 to 25 carbon atoms, R ₂ represents alkylene or arylene having 1 to 25 carbon atoms, -Q- each independently represent 1,2-perfluorocyclobutylene (C ₄ F ₆ ), R is

,

,

,

And

At least one sulfonated low aromatic compound selected from the group consisting of R 'is

,

,

,

,

,

,

,

,

,

,

,

,

And

At least one sulfonated high aromatic compound selected from the group consisting of Where A represents -NO ₂ , or -CF ₃ . The block copolymer according to claim 13, comprising a repeating unit represented by the following formula (3): [Formula 3]

Wherein R and R 'are each as defined in claim 13, n and m are each an integer of 1 to 10,000. a) preparing a block oligomer of the general formula (7) having a low sulfonation activity by polymerizing an aromatic monomer of the general formula (6) having a low sulfonation activity and including a perfluorovinyl oxy group in a sock end; b) preparing a block oligomer of Formula 12 having high sulfonation activity by polymerizing an aromatic monomer of Formula 11 having a high sulfonation activity and a perfluorovinyl oxy group in a sock end; And c) polymerizing the low sulfonation activity block oligomer prepared in step a) and the high sulfonation activity block oligomer prepared in step b) Method for producing a block copolymer according to claim 13 comprising: [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 7] F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂ [Formula 11] F ₂ C = FC-P-R'-P-CF = CF ₂ [Formula 12] F ₂ C = FC-P-(-R'-PQP-) _{m '} -R'-P-CF = CF ₂ Wherein P, Q, R, and R 'are each as defined in claim 13, n 'and m' are each an integer of 1 to 10,000. a) preparing a block oligomer of the general formula (7) having a low sulfonation activity by polymerizing an aromatic monomer of the general formula (6) having a low sulfonation activity and including a perfluorovinyl oxy group in a sock end; And b) polymerizing an aromatic monomer represented by the following formula (11) comprising a block oligomer having a low sulfonation activity and a sulfonation activity and a perfluorovinyl oxy group in a sock end prepared in step a). Method for producing a block copolymer according to claim 13 comprising: [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 7] F ₂ C = FC-P-(-RPQP-) _{n '} -RP-CF = CF ₂ [Formula 11] F ₂ C = FC-P-R'-P-CF = CF ₂ Wherein P, Q, R, and R 'are each as defined in claim 13, n 'is an integer from 1 to 10,000. a) preparing a block oligomer of formula 12 having a high sulfonation activity by polymerizing an aromatic monomer of formula 11 having a high sulfonation activity and a perfluorovinyl oxy group in a sock end; And b) polymerizing an aromatic monomer of formula 6 having a high sulfonation activity block oligomer prepared in step a) and a low sulfonation activity and a perfluorovinyl oxy group in the sock end; Process for producing a block copolymer according to claim 13 comprising a. [Formula 6] F ₂ C = FC-PRP-CF = CF ₂ [Formula 11] F ₂ C = FC-P-R'-P-CF = CF ₂ [Formula 12] F ₂ C = FC-P-(-R'-PQP-) _{m '} -R'-P-CF = CF ₂ Wherein P, Q, R, and R 'are each as defined in claim 13, m 'is an integer from 1 to 10,000. 18. A process for preparing a block copolymer according to claim 6 comprising sulfonating the block copolymer prepared according to any one of claims 15 to 17. 19. The process for producing a block copolymer according to claim 18, wherein the sulfonation is carried out with at least one sulfonating agent selected from the group consisting of chlorosulphonic acid, sulfur trioxide, sulfuric acid, fuming sulfuric acid, acyl sulfate, and sulfur trioxide. . An electrolyte membrane comprising the block copolymer according to any one of claims 1 to 8. The electrolyte membrane of claim 20, wherein the electrolyte membrane is in the form of a flat membrane, a hollow fiber membrane, a composite membrane, or a tube membrane. Preparing an polymer membrane by dissolving an acid-substituted block copolymer of Formula 10 in a molten or organic solvent; And A process for preparing an electrolyte membrane comprising the step of replacing an acid substituent group (R ′ ″) with an acid group (R ″): [Formula 10] -(-RPQP-) _n -(-R '"-PQP-) _m- In the above, P, Q, R, R ", R '", n and m are as defined in claim 9, respectively. Dissolving the block copolymer according to claim 1 or 6 in an organic solvent; Coating the polymer solution on a support to form a film; And Drying the formed film Method for producing an electrolyte membrane comprising a. 24. The method of claim 23, wherein the support is a solid support comprising a glass plate, a metal, or a ceramic, and a porous polymeric support comprising polysulfone or polyisamide. A fuel cell comprising the electrolyte membrane according to claim 20. 27. The fuel cell of claim 25, wherein the fuel cell is a polymer electrolyte fuel cell or a direct methanol fuel cell.

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