KR20110032257A - Polysufone based polymer, polymer electrolyte membrane comprising polymer, membranes-electrode assembly comprising membrane and fuel cell comprising membrane, and preparing method thereof - Google Patents

Abstract

PURPOSE: A polysufone-based polymer is provided to obtain a polymer electrolyte membrane with high hydrogen ion conductivity, low methanol permeability, and excellent moisture content. CONSTITUTION: A polysufone-based polymer comprises a repeating unit represented by chemical formula 1. In chemical formula 1, X is a single bond or Ar1; R1, R2, R3, R4, R5 and R6 are hydrogen, -SO3M, -SO3M substituent-(non)containing C1~50 alkyl group, C2~50 alkenyl group, C2~50 alkynyl group, C5~50 cycloalkyl group, C6~50 aryl group, C2~50 heteroaryl group, C7~50 alkylaryl group, or C1~50 alkoxy group; M is hydrogen, lithium, sodium or potassium; a, b, c, and d are an integer of 0-5; e and f are an integer of 0-2; and n is 2-10,000 as the degree of polymerization.

Description

Polysulfone polymer, a polymer electrolyte membrane comprising the same, a membrane-electrode assembly comprising the same, a fuel cell employing the same and a method for producing the polymer {Polysufone based polymer, polymer electrolyte membrane comprising polymer, membranes-electrode assembly comprising membrane and fuel cell comprising membrane, and preparing method

Polysulfone polymer, a polymer electrolyte membrane comprising the same, a membrane-electrode assembly comprising the same, a fuel cell employing the same and a method for producing the polymer, and more particularly, a polysulfone polymer having a new structure, comprising the The present invention relates to a polymer electrolyte membrane, a membrane-electrode assembly including the same, a fuel cell employing the same, and a manufacturing method of the polymer.

The fuel cells are polymer electrolyte membrane fuel cells (PEMFC), phosphoric acid fuel cells (PAFC), molten carbonate fuel cells (MCFC), and solid oxides depending on the type of electrolyte. It is classified into a solid oxide fuel cell (SOFC), and the operating temperature of the fuel cell and the material of components vary according to the type of electrolyte used.

Polymer Electrolyte Membrane Fuel Cell (PEMFC) has better output, lower operating temperature and faster response than other fuel cells.

The fuel cell is composed of a power generation unit for generating electricity, a reformer, a fuel tank and a fuel pump. The power generation unit forms a main body of the fuel cell, and the fuel pump supplies the fuel in the fuel tank to the reformer. Hydrogen gas is generated through the reformer and fuel is supplied to the power generation unit by a pump to generate electrical energy by an electrochemical reaction. The power generation unit may be composed of a membrane electrode assembly (MEA) consisting of an anode, a cathode, and a polymer electrolyte membrane.

In addition, a fuel cell is classified into a fuel direct supply type or an internal reforming type according to a method of supplying fuel to an anode, and a direct methanol fuel cell (DMFC: direc methnol fuel cell) is a typical fuel direct supply type.

Since the direct methanol fuel cell uses a polymer electrolyte membrane as an electrolyte, the direct methanol fuel cell belongs to the polymer electrolyte fuel cell.

Direct methanol fuel cells do not use hydrogen reformers because they use methanol as fuel, and operate at low temperatures, making the system simple and compact, making them suitable for powering small and portable devices.

The principle of generating electricity in a direct methanol fuel cell is that methanol is supplied to the anode electrode, and methanol is decomposed into hydrogen ions, electrons, and carbon dioxide (CO ₂ ) by the oxidation reaction of the electrode catalyst, and the hydrogen ions decompose the polymer electrolyte membrane. The electrons move to the cathode through an external circuit. In the cathode, water is generated by reaction of oxygen introduced into the air, electrons moved through an external circuit, and hydrogen ions moved through a membrane. The electrochemical reaction is represented by Scheme 1 below.

<Scheme 1>

_{Anode: CH 3 OH + H 2 O} → CO 2 + 6H + + 6e -

^{_{Cathode: 3/2 O 2 + 6H + +}} 6e - → 3H 2 O

Total reaction: CH ₃ OH + 3 / 2O ₂ → CO ₂ + 2H ₂ O

As the electrolyte membrane of the polymer electrolyte fuel cell, a functional hydrogen ion exchange membrane having a cation exchange capacity is used. Commercially, hydrophobic exchange membranes containing sulfonic acid groups are mainly used. This is because sulfonic acid groups have very high acidity and C-S bonds are stable even under oxidizing conditions. In the hydrogen ion exchange membrane where sulfonic acid group is present, water molecules must be present together to maintain high hydrogen ion conductivity. In the presence of water molecules, the sulfonic acid groups present in the electrolyte membrane are dissociated into sulfonate anions and hydrogen ions, and the hydrogen ions move by the gradient of hydrogen ions concentration or by an electric field as in the sulfuric acid solution electrolyte. Hydrogen ion conductivity is affected by the number of sulfonic acid groups included in the polymer electrolyte membrane, the structure of the polymer electrolyte membrane, the amount of water contained in the polymer electrolyte membrane, and the like.

An electrolyte membrane of a typical polymer electrolyte fuel cell is a fluorine-based polymer electrolyte membrane such as a Nafion membrane, an Aciplex membrane, a Flemion membrane, or a Dow membrane. The fluorine-based polymer electrolyte membranes have a low hydrogen ion conductivity at a high temperature of 100 ° C. or higher, high permeability of fuel gas, and high price. In addition, as the hydrogen ion conductivity is increased, the water permeability of the polymer electrolyte membrane is increased, thereby increasing the permeability of the fuel (for example, methanol). Therefore, it is difficult to secure high ion conductivity and low fuel permeability at the same time.

Therefore, there is still a need for a polymer electrolyte membrane having low production cost and high hydrogen ion conductivity and low permeability to fuel.

One aspect is to provide a polysulfone-based polymer having a new structure.

Another aspect is to provide a polymer electrolyte membrane comprising the polymer.

Another aspect is to provide a membrane-electrode assembly comprising the polymer electrolyte membrane.

Another aspect is to provide a fuel cell comprising the polymer electrolyte membrane.

It is to provide a method for producing the polysulfone polymer.

According to one aspect, there is provided a polysulfone polymer comprising a repeating unit represented by Formula 1 below:

<Formula 1>

Where

X is a single bond or Ar ₁ , and Ar ₁ is a substituted or unsubstituted C 6 -C 20 arylene group;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium;

a, b, c, and d are each independently an integer from 0 to 5;

e and f are each independently an integer of 0 to 2,

n is 2 to 10,000 as the degree of polymerization,

Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ contain one or more sulfonate groups.

According to another aspect, a polymer electrolyte membrane including the polymer is provided.

According to another aspect, a membrane-electrode assembly including the polymer electrolyte membrane is provided.

According to another aspect, a fuel cell including the polymer electrolyte membrane is provided.

According to another aspect, a method for preparing the polysulfone polymer,

Preparing a polymer by reacting a compound represented by Chemical Formulas 5 to 7; And

Preparing a sulfonated polymer represented by the following Chemical Formula 3 by sulfonating the polymer; a polysulfone copolymer manufacturing method comprising:

<Formula 3>

In Chemical Formula 3,

X is a single bond or Ar ₁ , and Ar ₁ , Ar _2, and Ar ₃ are each independently a substituted or unsubstituted C6 to C20 arylene group;

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium;

a, b, c, and d are each independently an integer from 0 to 5;

e and f are each independently an integer of 0 to 2,

p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1,

r is 2 to 10000 as the degree of polymerization,

Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ include one or more sulfonate groups,

<Formula 5>

In Formula 5,

R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are independently hydrogen, C 1 -C 50 alkyl group, C 2 -C 50 alkenyl group, C 2 -C 50 alkynyl group, C 5 -C 50 cycloalkyl group, C 6 C50-C50 aryl group, C2-C50 heteroaryl group, C7-C50 alkylaryl group, or C1-C50 alkoxy group;

<Formula 6> <Formula 7>

R ₃₁ -Ar ₂ -R ₃₂ R ₃₃ -Ar ₃ -R ₃₄

In Chemical Formulas 6 and 7,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group;

R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are independently of each other -F, -Cl, -Br, -I, or -OH.

According to one aspect, the fuel cell employing the polymer electrolyte membrane including the polysulfone polymer having the new structure has improved characteristics such as hydrogen ion conductivity and gas permeability.

Hereinafter, a polysulfone polymer according to at least one exemplary embodiment, a polymer electrolyte membrane including the same, a membrane-electrode assembly including the same, a fuel cell employing the same, and a method of preparing the polymer will be described in more detail.

Polysulfone polymer according to one embodiment includes a repeating unit represented by the following formula (1):

<Formula 1>

Wherein X is a single bond or Ar ₁ , and Ar ₁ is a substituted or unsubstituted C 6 -C 20 arylene group; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium; a, b, c, and d are each independently an integer from 0 to 5; e and f are each independently an integer of 0 to 2, n is 2 to 10,000 as the degree of polymerization; Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ contain one or more sulfonate groups.

A possible basis for the polysulfone polymer according to one embodiment may have excellent physical properties will be described in more detail below, which is intended to limit the scope of the present invention in any way as to aid the understanding of the present invention. Is not.

The sulfonic acid group contained in the polymer is preferably connected to one end of the phenyl group constituting the side chain. The sulfonic acid group can be relatively freely moved away from the main chain by being connected to one end of the polymer side chain. The sulfonic acid group linked to the side chain may serve as a surfactant in the polymer. Therefore, the sulfonic acid group at the side chain terminal is easy to form an ion channel such as a micelle, and the ion is controlled by controlling the position of the sulfonic acid group connected to the side chain and / or the structure of the substituent connected to the phenyl group constituting the side chain. You can also adjust the size of the channel. As a result, the polysulfone-based polymer can easily control the amount of water contained in the ion channel and have a high hydrogen ion conductivity.

In the conventional general polysulfone-based polymer, when the sulfonic acid group is directly connected to the main chain, when the sulfonic acid group content is high in the polymer, the polymer itself is dissolved in water and thus the function of the electrolyte membrane may be lost, thereby limiting the content of the sulfonic acid group. Therefore, conventional polysulfone-based copolymers in which sulfonic acid groups are linked only to the main chain may not have high hydrogen ion conductivity and may be easily permeable through the main chain of methanol.

In addition, since the hydrophilic part and the hydrophobic part are separated from the copolymer by the presence of sulfonic acid groups separated from the main chain in the polymer, permeation of methanol through the main chain which is a hydrophobic part can be further suppressed. In addition, the sulfonic acid group is not present in the main chain, but is present in the side chain, thereby improving the flexibility of the polysulfone polymer itself, and may also improve thermal stability and stability against oxidation / reduction reactions.

In addition, four or more sulfonic acid groups may be bonded to one repeating unit skeleton in the polymer. For example, 4 to 8 sulfonic acid groups may be bonded to one repeating unit. For example, one or more sulfonic acid groups may be linked to each phenyl group of the side chain in the repeating unit of Formula 1.

Since the polymer has a high content of sulfonic acid groups, it may have high conductivity even at a low moisture content. In addition, the polymer may be exposed to moisture for a long time to provide high dimensional stability without changing the characteristics of the electrolyte membrane.

The arylene group is a divalent functional group having an aromatic ring system, and may include two or more ring systems, and the two or more ring systems may exist in a bonded or fused form with each other. For example, the two or more ring systems may be in a form joined by a single bond or in a form including an additional linking group inserted between the two or more ring systems. The additional linking group may be a substituted or unsubstituted alkylene group, S, S (= 0) ₂ , C (= 0), and the like.

In the present specification, "substituted", unless otherwise defined, hydroxyl group, halogen group, C1-C20 alkyl group, C2-C20 alkenyl group, C2-C20 alkynyl group, C5-C20 cycloalkyl group, C6 ~ It means substituted with an aryl group of C20, a heteroaryl group of C2 ~ C20 or a functional group combined.

The alkyl group is composed of only carbon and hydrogen, and is a monovalent hydrocarbon functional group in which carbon is connected only by a single bond. For example, they are a methyl group, an ethyl group, a butyl group, an isobutyl group, a tert- butyl group, a pentyl group, and a hexyl group.

The alkenyl group is a monovalent hydrocarbon functional group containing at least one carbon-carbon double bond in the chain. For example, it is a vinyl group, an allyl group, etc.

The alkynyl group is a monovalent hydrocarbon functional group containing at least one carbon-carbon triple bond in the carbon chain.

Cycloalkyl groups are monovalent alkyl groups in which the carbon chain forms a ring. For example, it is a cyclopentyl group, a cyclohexyl group, etc.

The heteroaryl group is a monovalent functional group in which one or more carbons of the aryl groups are substituted with one or more selected from the group consisting of N, O, S and P.

According to another embodiment it is preferred that the polymer is a copolymer further comprising a repeating unit represented by the following formula (2):

<Formula 2>

Wherein Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group; m is 2 to 10,000 as polymerization degree.

According to another embodiment it is preferable that the polymer is a copolymer comprising a repeating unit represented by the following formula (3):

<Formula 3>

Wherein X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, d, e, and f are as defined above, and Ar ₂ and Ar ₃ are mutually Independently a substituted or unsubstituted C6 ~ C20 arylene group; p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, provided that a + b + c + d + e + f is At least one, and R ₁ to R _{6 include} at least one sulfonate group and / or sulfonic acid group.

According to another embodiment it is preferred that the substituted or unsubstituted C6 to C20 arylene group in the polymer is represented by one of the following formulas:

<Formula 1a> <Formula 1b>

In the above equations,

R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently hydrogen, halogen atom, -SO ₃ M, C1 C50-C50 alkyl group, C2-C50 alkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkyl group, C6-C50 aryl group, C2-C50 heteroaryl group, C7-C50 alkylaryl group, or A C1-C50 alkoxy group;

Y is a single bond, S, S (= 0) ₂ , C (= 0), P (= 0) (R ₁₇ ) or C (R ₁₈ ) (R ₁₉ ), wherein R ₁₇ , R ₁₈ , and R ₁₉ independently of each other is a C1-C20 alkyl group unsubstituted or substituted with halogen, or a C6-C20 aryl group unsubstituted or substituted with halogen.

According to another embodiment, the arylene group represented by Formulas 1a and 1b in the polymer may further include -SO ₃ M (M is hydrogen or an alkali metal) as a substituent. In general, the arylene group does not include a sulfonate group, but if necessary, one or more of the sulfonate groups may be substituted with the arylene group.

According to another embodiment, it is preferable that the polymer is a copolymer including a repeating unit represented by Formula 4 below:

<Formula 4>

In the above formula, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently a C 6 to C 50 aryl group unsubstituted or substituted with —SO ₃ M, or —SO ₃ M, and R ₂₅ and R ₂₆ are each other. independently is hydrogen, -SO ₃ M, -SO ₃ M by a substituted or unsubstituted C1 ~ C10 with C6 ~ C20 substituted or unsubstituted alkyl group, or -SO ₃ M in unsubstituted aryl group, Ar ₄ and Ar ₅ is Independently a substituted or unsubstituted C6 ~ C20 arylene group; p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, provided that R ₂₁ to R ₂₆ are at least one sulfonate group and And / or sulfonic acid groups.

According to another embodiment, in the polymer, R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ may be represented independently of one another by one of the following substituents:

In the substituents, M is independently of each other hydrogen, lithium, sodium or potassium, aa, ac, af, aj and ao are each independently an integer from 1 to 5, ab, ad, ae, ag, ah, ai , ak, al, am and an are each independently an integer from 0 to 4.

According to another embodiment, Ar ₄ or Ar ₅ may be represented by one of the following structures:

Wherein A is a single bond, S, S (= 0) ₂ , or C (= 0); B is a single bond, S, S (= O) ₂ , C (= O), P (= O) (C ₆ H ₅ ), C (CF ₃ ) (C ₆ H ₅ ), C (CH ₃ ) ₂ Or C (CF ₃ ) ₂ .

According to another embodiment, the ratio of p and q in the copolymer represented by Formula 3 or 4 is preferably 1: 9 to 9.9: 0.1. The ratio of p and q is suitable for achieving the object of the present invention.

According to another embodiment, the weight average molecular weight of the polymer represented by Formulas 1 to 4 is preferably from 1,000 to 500,000, more preferably from 1,000 to 100,000. The weight average molecular weight range is suitable for achieving the object of the present invention.

According to another embodiment, the dispersion degree (PDI, polydispersion index) of the polymer represented by Formula 1 to 4 may be 1 to 10. For example, the dispersion degree may be 1 to 5. For example, the dispersion degree may be 1 to 3.

According to another embodiment, the copolymer represented by Formulas 2 to 4 may be a random copolymer or a block copolymer. Preferably the copolymer is a block copolymer. The block copolymer is more suitable for use as an electrolyte membrane.

According to another embodiment, a polymer electrolyte membrane including the polysulfone polymer is provided. The polymer electrolyte membrane has a low methanol permeability and high hydrogen ion conductivity by including the polysulfone polymer of any one of Formulas 1 to 4. And moisture content characteristics are also excellent.

In addition, the polymer electrolyte membrane including the polymer may generally have thermal and chemical stability of the poly (arylene ether) polymer, and may be used as a thermoplastic polymer, a membrane elastomer, and the like because it is easy to process and has a low moisture absorption rate. It contains sulfonic acid group, which can have high hydrogen ion conductivity even at low moisture content, and can show high dimensional stability even if it is exposed to moisture for a long time. Suitable for use in batteries, etc.

According to another embodiment, the hydrogen ion conductivity of the polymer electrolyte membrane is preferably 0.5 × 10 ^-3 S / cm or more at 100% relative humidity and 25 ℃, more preferably 1 × 10 ^-3 S / cm The above is most preferably 1.5 × 10 ⁻³ S / cm to 200 × 10 ⁻³ S / cm.

According to another embodiment, the methanol permeability of the polymer electrolyte membrane is preferably 20 × 10 ^-7 cm ² / s or less at 100% relative humidity and 25 ℃, more preferably 16 × 10 ^-7 cm ² / s It is below, Most preferably, it is 15.8x10 <^-7> cm <^2> / s-0.01x10 <^-7> cm <^2> / s.

According to another embodiment, the polymer electrolyte membrane is polyimide, polyetherketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, except the polymer of Formula 1 to 4, Polyphenylenesulfide, polystyrene, polytrifluorourostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, branched sulfonated polysulfone ketone copolymers or mixtures thereof.

According to another embodiment, the polymer electrolyte membrane is an inorganic material, such as silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), inorganic phosphoric acid, sulfonated SiO ₂ , sulfonated zirconium oxide (sufonated ZrO) ), Sulfonated zirconium phosphate (sulfonated ZrP) or mixtures thereof. By including such an inorganic material, the inorganic material may act as a barrier of a channel through which hydrogen ions and methanol are permeated, thereby reducing fuel permeability of the polymer electrolyte membrane.

According to another embodiment, the polymer electrolyte membrane may further include a porous support. By including the porous support, it is possible to improve the tensile strength of the polymer electrolyte membrane. The porous support is, for example, a porous polyolefin such as porous polyethylene, porous teflon, porous polyimide and the like.

According to another embodiment, a membrane-electrode assembly and a fuel cell including the polymer electrolyte membrane are provided. The membrane-electrode adhesive includes a cathode, an anode, and a polymer electrolyte membrane according to an embodiment of the present invention interposed therebetween. In addition, the fuel cell further includes a separator plate attached to both surfaces of the membrane-electrode assembly including the polymer electrolyte membrane according to one embodiment of the present invention. A reformer, a fuel tank, a fuel pump, etc. may be selectively added to the separator as needed. In addition, the fuel cell may include a plurality of membrane electrode assemblies.

The cathode and anode consist of a gas diffusion layer and a catalyst layer. The catalyst layer includes a metal catalyst for promoting oxidation of hydrogen and reduction of oxygen. The catalyst layer is made of platinum, ruthenium, osmium, platinum-osmium alloy, platinum-palladium alloy, and platinum-M alloy (M is Ga, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, or Zn). It is preferable to include at least one selected from the group. In particular, it is preferable to include platinum, ruthenium, osmium, platinum-ruthenium alloys, platinum-osmium alloys, platinum-palladium alloys, platinum-cobalt alloys, platinum-nickel alloys or mixtures thereof.

The metal catalyst is generally used while supported on a carrier. The carrier may be a carbon-based material such as acetylene black or black salt; Or inorganic fine particles such as alumina and silica; For example, the carrier supporting the catalyst may have a porosity and a surface area of 150 m 2 / g or more, particularly 500 to 1200 m 2 / g, and an average particle diameter of 10 to 300 nm, particularly 20 to 100 nm.

The gas diffusion layer may be carbon paper or carbon cloth, but is not limited thereto. The gas diffusion layer serves to support the fuel cell electrode and serves to make the reaction gas easily accessible to the catalyst layer by diffusing the reaction gas into the catalyst layer. As the gas diffusion layer, it is preferable to use a water repellent treatment of carbon paper or carbon cloth with a fluorine resin such as polytetrafluoroethylene. The water repellent treated carbon paper or carbon cloth may prevent the gas diffusion efficiency from being lowered by water generated when the fuel cell is driven.

The electrode may further include a microporous layer to further enhance the gas diffusion effect between the gas diffusion layer and the catalyst layer. The microporous layer may be prepared by applying a composition including an ionomer according to a filler and a filler such as carbon powder, carbon black, activated carbon, acetylene black, a conductive material such as polytetrafluoroethylene, and the like.

The cathode and / or anode can be prepared, for example, as follows. First, a catalyst slurry is prepared by mixing the catalyst powder, the binder, and the mixed solvent. The catalyst powder is as described above, may be a metal particle supported on the carbon-based support, or a metal particle state not supported on the carbon-based support, and platinum is particularly preferable. The mixed solvent and binder are not particularly limited as long as they can be generally used in the art. Next, the catalyst slurry is coated on a gas diffusion layer using a coater and dried to prepare a cathode and / or an anode composed of a catalyst layer and a gas diffusion layer.

When the polymer electrolyte membrane according to the embodiment of the present invention is inserted between the cathode and the anode and pressed by a hot pressing method, a membrane-electrode assembly is obtained. The conditions used in the hot pressing method are, for example, a pressure of 500 to 2000 psi, a temperature of 50 to 300 ° C, and a pressurization time of 1 to 60 minutes.

A separator is added to the membrane / electrode assembly to obtain a power generation section. The separator is attached to both sides of the membrane / electrode assembly, and the separator attached to the anode is an anode separator and a separator attached to the cathode is a cathode separator. The anode separator has a flow path for supplying fuel to the anode, and serves as an electron conductor for transferring electrons generated from the anode to an external circuit or an adjacent unit cell. The cathode separator has a flow path for supplying an oxidant to the cathode, and serves as an electron conductor for transferring electrons supplied from an auxiliary circuit or an adjacent unit cell to the cathode. Next, the fuel cell is completed by selectively adding at least one reformer, a fuel tank, a fuel pump, and the like to the power generation unit.

According to another embodiment the fuel cell may be a direct methanol fuel cell. A schematic of the direct methanol fuel cell is shown in FIG. 1.

As shown in FIG. 1, the direct methanol fuel cell includes an anode 32 supplied with fuel, a cathode 30 supplied with an oxidant, and an electrolyte membrane 41 positioned between the anode 32 and the cathode 30. It includes. The anode 32 is composed of an anode diffusion layer 22 and an anode catalyst layer 33, and the cathode 30 is composed of a cathode diffusion layer 32 and a cathode catalyst layer 31.

The aqueous methanol solution transferred to the anode catalyst layer 33 through the anode diffusion layer 22 is decomposed into electrons, hydrogen ions, carbon dioxide, and the like by the catalyst. Hydrogen ions are transferred to the cathode catalyst layer 31 through the electrolyte membrane 41, electrons are transferred to an external circuit, and idealized carbon is discharged to the outside. In the cathode catalyst layer 31, water is generated by reaction of hydrogen ions transferred through the electrolyte membrane, electrons supplied from an external circuit, and oxygen in the air supplied through the cathode diffusion layer 32. However, it is apparent that the polymer electrolyte membrane including the polymer according to one embodiment of the present invention can be used for all other types of fuel cells.

According to yet another embodiment the fuel cell may be a vehicle fuel cell (vehicle). Accordingly, the vehicle includes all kinds of vehicles, such as vehicles for transportation, such as automobiles and trucks, and vehicles for other purposes such as excavators and forklifts. The configuration and output of the fuel cell may be appropriately modified according to the use. For example, a large amount of current is required in a short time for starting, sudden start and the like of a vehicle, so a fuel cell having a high output density is suitable.

According to another embodiment the (co) polymer represented by the formula (1) to 4 can be used in various technical fields, and the field is not limited. For example, the (co) polymer can be used in all energy storage and production devices such as solar cells, secondary cells, supercapacitors and the like. It can also be used in organic electroluminescent devices. It can also be used in any technical field utilizing the proton conductivity of the copolymer.

According to another embodiment of the present invention, a method for preparing a polysulfone copolymer may include preparing a polymer by reacting a compound represented by the following Chemical Formulas 5 to 7; And sulfonating the polymer to prepare a sulfonated polymer represented by Formula 3 below:

<Formula 3>

In Formula 4, X is a single bond or Ar ₁ , wherein Ar ₁ , Ar ₂ and Ar ₃ are independently substituted or unsubstituted C6 to C20 arylene groups; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium; a, b, c, and d are each independently an integer from 0 to 4; e and f are each independently an integer of 0 to 2, p and q are mole fraction, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ include one or more sulfonate groups,

<Formula 5>

In Formula 5, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are independently hydrogen, an alkyl group of C1 ~ C50, an alkenyl group of C2 ~ C50, an alkynyl group of C2 ~ C50, C5 ~ C50 A cycloalkyl group, a C6 ~ C50 aryl group, a C2 ~ C50 heteroaryl group, a C7 ~ C50 alkylaryl group, or a C1 ~ C50 alkoxy group;

<Formula 6> <Formula 7>

R ₃₁ -Ar ₂ -R ₃₂ R ₃₃ -Ar ₃ -R ₃₄

In Formulas 6 and 7, Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group; R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are independently of each other -F, -Cl, -Br, -I, or -OH.

According to another embodiment, the compound of Formula 5 may be represented by one of the following structures in the preparation method:

The production method is simple to manufacture, easy to purify and high yield, so that the polymer can be produced in large quantities at a low cost, very economical. It is also easy to adjust the degree of sulfonation.

For example, the monomers represented by the formulas (5), (6) and (7) produce a copolymer by a nucleophilic substitution reaction. For example, the polymerization may be carried out at a ratio of 2 mol of the monomer represented by Formula 6 and 1 mol of the monomer represented by Formula 7 with respect to 1 mol of the monomer represented by Formula 5. For example, the monomer may be polymerized at a ratio of 0.2 to 8 mol of the monomer represented by Formula 6 and 1 mol of the monomer represented by Formula 7 with respect to 1 mol of the monomer represented by Formula 5.

Subsequently, the copolymer is sulfonated to obtain a sulfonated copolymer represented by Chemical Formula 3. The sulfonic acid compounds used in the sulfonation reaction are concentrated sulfuric acid (Conc H ₂ SO ₄ ), chlorosulfonic acid (ClSO ₃ H), fuming sulfuric acid (Fumming SO ₃ ), fuming sulfuric acid triethylphosphate salt (SO ₃ .TEP) And the like may be used, but not limited thereto, and any compound capable of sulfonation may be used. The sulfonation reaction may be carried out at a temperature of 0 ° C to 100 ° C, for example, 25 ° C to 50 ° C. The sulfonation degree of the copolymer represented by Chemical Formula 3 can be adjusted according to the conditions of the sulfonation reaction. For example, the sulfonation degree of the copolymer represented by Chemical Formula 3 may be 10 to 99. The sulfonation degree is a mole fraction of a specific repeating unit substituted with a sulfonated group included in the sulfonated polymer.

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

(Production of polysulfone polymer)

The polysulfone copolymer (Compound 500) of Examples 1 to 2 was prepared by following the route of Scheme 1 below.

<Scheme 1>

Example 1 (x = 0.2)

First step: nucleophilic substitution reaction

A 250 mL two-necked round bottom flask was equipped with a magnetic sterling bar, Dean-stark trap and condenser, and in a nitrogen atmosphere 3,3 ', 5,5'-tetraphenylbiphenyl-4,4'- Diol (3,3 ', 5,5'-Tetraphenylbiphenyl-4,4'-diol, compound 100) 4 mmol, 4,4'-(hexafluoroisopropylidine) diphenol (4,4 '-(hexafluoroiopropylidene) diphenol, Compound 300) 16 mmol, 4,4'-difluorodiphenylsulfone (Compound 200) 20 mmol and dimethylacetamide (Dimethylacetamide: DMAc, 70 mL) were added to the flask and completely dissolved. After completely dissolving the monomers, potassium carbonate (24 mmol) and toluene (50 mL) were added thereto, and water was removed while refluxing at 120 ° C. for 4 hours. After removing water, toluene was removed while raising the reactor temperature to 140 ° C. After removing toluene, the reaction temperature was raised to 165 ° C and reacted for about 24 hours. After the reaction was completed, the mixture was washed several times with a methanol / water (1: 1 v / v) mixture and then vacuum dried at 60 ° C. for 24 hours to obtain a white solid product (Compound 400). Yield 93%. The X value of the compound 400 was 0.2.

¹ H-NMR (400MHz DMSO-d6, ppm): δ8.1 ~ 7.84 (C ₆ H ₄ SO ₂ , 8H), δ7.28 ~ 6.62 (phenyl ring m, 35H)

Second Step: Sulfonation Reaction

A dropping funnel, a magnetic sterling bar, and a condenser were installed in a 250 mL two-neck flask, and 2.0 mmol of the product (Compound 400) obtained in the first step and 20 ml of dichloromethane were added and dissolved completely in a nitrogen atmosphere. While refluxing the solution in which Compound 400 was dissolved, a mixed solution of 20 ml of chloromethane and 4.8 mmol of chlorosulfonic acid was slowly added dropwise to the solution over 1 hour. At this time, the reaction temperature was room temperature and the reaction time was 3 hours. As the reaction proceeded, the sulfonated polymer precipitated. After the reaction was completed, the reaction solution was washed several times with distilled water to remove unreacted chlorosulfonic acid. The precipitate was then filtered and vacuum dried at 60 ° C. for 24 hours. The dried precipitate was dissolved in dimethylacetamide again to prepare a solution, and then 3% by weight aqueous solution of calcium hydroxide was added dropwise, followed by addition of hydrochloric acid to neutralize the pH of the solution. The product was then filtered and dried in vacuo to give a sulfonated copolymer (Compound 500). Yield 91%.

¹ H-NMR (400 MHz DMSO-d _6, ppm): δ8.1-7.84 (C ₆ H ₄ SO ₂ , 4H), δ7.52 (C ₆ H ₄ -SO ₃ H, 8H) δ 7.28-6.62 (phenyl ring m, 35H)

Example 2 (x = 0.4)

First step: nucleophilic substitution reaction

By varying the number of moles of the reactants, 3,3 ', 5,5'-tetraphenylbiphenyl-4,4'-diol (3,3'5,5'-Tetraphenylbiphenyl-4,4'-diol, compound 100) 8 mmol, 4,4 '-(hexafluoroisopropylidine) diphenol (4,4'-(hrxafluoroiopropylidene) diphenol, compound 300) 12 mmol, and 4,4'-difluorodiphenylsulfone (4,4'- Compound 400 was prepared in the same manner as in Example 1, except that 20 mmol of difluorodiphenylsulfone (Compound 200) was used. The value of X in the compound 400 was 0.4. Yield 90%.

¹ H-NMR (400MHz DMSO-d _6, ppm): δ8.1 ~ 7.84 (C ₆ H ₄ SO ₂ , 8H), δ7.28 ~ 6.62 (phenyl ring m, 35H)

Second Step: Sulfonation Reaction

The compound 500 was prepared in the same manner as in the second step of Example 1, except that the product obtained in the first step of Example 2 was used. Yield 90%.

¹ H-NMR (400MHz DMSO-d _6, ppm): δ8.1 ~ 7.84 (C ₆ H ₄ SO ₂ , 4H), δ7.52 (C ₆ H ₄ -SO ₃ H, 8H) δ7.28 ~ 6.62 (phenyl ring m, 35H)

The polysulfone copolymer (Compound 501) of Examples 3 to 4 was prepared by following the route of Scheme 2.

<Scheme 2>

Example 3 (x = 0.2)

First step: nucleophilic substitution reaction

3,3 ', 5,5'-tetraphenylbiphenyl-4,4'-diol (3,3'5,5'-Tetraphenylbiphenyl-4,4'-diol, compound 100) 2,2' instead of 4mmol -Dimethyl-3,3'.3.3'-tetraphenylbiphenyl-4,4'-diol (2,2'-Dimethyl-3,3'5,5'-Tetraphenylbiphenyl-4,4'-diol, compound 101 ) Compound 401 was prepared by the same method as the first step of Example 1, except that 4 mmol was used. In Compound 401, the X value was 0.2. Yield 92%.

¹ H-NMR (400 MHz DMSO-d _6, ppm): δ8.1-7.84 (C ₆ H ₄ SO ₂ , 8H), δ 7.39-6.39 (phenyl ring m, 35H), δ 1.98 (CH ₃ , 6H)

Second Step: Sulfonation Reaction

Compound 501 was prepared by the same method as the second step of Example 1, except that the product obtained in the first step of Example 3 was used. Yield 92%.

¹ H-NMR (400 MHz DMSO-d _6, ppm): δ8.1-7.84 (C ₆ H ₄ SO ₂ , 8H), δ 7.39-6.39 (phenyl ring m, 35H), δ 1.98 (CH ₃ , 6H)

Example 4 (x = 0.4)

First step: nucleophilic substitution reaction

By varying the number of moles of the reactants, 2,2'-dimethyl3,3'.3.3'-tetraphenylbiphenyl-4,4'-diol (2,2'-Dimethyl-3,3'5,5'-Tetraphenylbiphenyl -4,4'-diol, compound 101) 8 mmol, 4,4 '-(hexafluoroisopropylidine) diphenol (4,4'-(hrxafluoroiopropylidene) diphenol, compound 300) 12 mmol, and 4,4'- Compound 401 was prepared by the same method as the first step of Example 3, except that 20 mmol of difluorodiphenylsulfone (4,4'-difluorodiphenylsulfone, compound 200) was used. In Compound 401, the X value was 0.4. Yield 92%.

¹ H-NMR (400 MHz DMSO-d _6, ppm): δ8.1-7.84 (C ₆ H ₄ SO ₂ , 8H), δ 7.39-6.39 (phenyl ring m, 35H), δ 1.98 (CH ₃ , 6H)

 Second Step: Sulfonation Reaction

Compound 501 was prepared by the same method as the second step of Example 1, except that the product obtained in the first step of Example 4 was used. Yield 88%.

¹ H-NMR (400 MHz DMSO-d _6, ppm): δ8.1-7.84 (C ₆ H ₄ SO ₂ , 8H), δ 7.39-6.39 (phenyl ring m, 35H), δ 1.98 (CH ₃ , 6H)

(Production of Polymer Electrolyte Membrane)

Example 5

The polysulfone copolymer prepared in Example 1 was dissolved in DMSO (dimethyl sulfoxide) and cast on a glass plate using a flat glass plate and a round glass rod, respectively, and dried at 150 ° C. in a vacuum oven to have a polymer having a thickness of 50 μm. An electrolyte membrane was prepared.

Example 6

Using a polysulfone copolymer prepared in Example 2 was prepared a polymer electrolyte membrane having a thickness of 50㎛ in the same manner as in Example 5.

Example 7

Using a polysulfone copolymer prepared in Example 3 to prepare a polymer electrolyte membrane having a thickness of 50㎛ in the same manner as in Example 5.

Example 8

Using a polysulfone copolymer prepared in Example 4 to prepare a polymer electrolyte membrane having a thickness of 50㎛ in the same manner as in Example 5.

Comparative Example 1

Nafion 112 (DuPont) was used as the polymer electrolyte membrane. Nafion 112 was precipitated in a 1 M concentration sulfuric acid solution at 100 ° C. for 24 hours to exchange the cation of the sulfonate group from sodium to hydrogen ions. The hydrogenated copolymer was then washed with deionized water.

Evaluation Example 1 Hydrogen Ion Conductivity Measurement

Proton conductivity of the polymer electrolyte membranes of Examples 5 to 8 and Comparative Example 1 was measured. Hydrogen ion conductivity was measured by interposing the polymer electrolyte membrane between two platinum electrodes 2.54 cm ² wide and then initial resistance at 30 ° C. using an electrochemical impedance spectroscopy (EIS) with IM6ex (Zahner). The value was measured, and then hydrogen ion conductivity was calculated using Equation 1 below. The results are shown in Table 1 below.

&Quot; (1) &quot;

Hydrogen ion conductivity [S / cm] = (film thickness [cm] / film area [cm ² ]) x initial conductivity [S]

Evaluation Example 2: Methanol Permeability Measurement

After the polymer electrolyte membranes of Examples 5 to 8 and Comparative Example 1 were interposed between the two cells, 15 mL of 1 M aqueous methanol solution was injected into one cell, and 15 mL of distilled water was injected into the other cell, followed by distilled water. 10 µl was aliquoted per 10 minutes in the cell, and then again filled with 10 µl of distilled water. Fine pores are present on the surface of the cell adjacent to the polymer electrolyte membrane to allow the movement of the solvent. The aliquot was sampled and the methanol concentration was measured by gas chromatography. In addition, the change in methanol concentration over time was plotted and the methanol permeability was calculated from the slope using Equation 2 below. The results are shown in Table 1 below.

<Equation 2>

Methanol permeability [cm ² / S] = (Slope [ppm / s] × solution volume × electrolyte membrane thickness) / (electrolyte membrane area × methanol concentration)

In the above formula, the thickness of the film to be cut off is 0.05 μm; Methanol concentration 1 mol / L (32000 ppm); Solution volume 15 ml; Electrolytic membrane area 7.06 cm ²

Evaluation Example 3 Measurement of Molecular Weight and Dispersion

The weight average molecular weight and dispersion of the polymers prepared in Examples 1 to 4 were measured using chromatography, and the results are shown in Table 1 below. The instruments and conditions used in the measurements are as follows.

GPC unit: Waters, model 2424

Use column: Waters, model name HR3, 4, 5 column Temperature: 80 ℃

Elution solvent: dimethylformamide

Elution rate: 1 ml / min.

Reference Material: Polymethylmethacrylate (PMMA)

TABLE 1

Sulfonated Weight average
Molecular Weight Dispersion
polydispersion index, PDI Hydrogen ion conductivity
[S / cm] Methanol transmittance [cm ² / S] Example 5 20 54200 2.14 1.9 × 10 ^-3 5.4 × 10 ^-7 Example 6 40 41000 1.98 4.1 × 10 ^-3 15.8 × 10 ^-7 Example 7 20 48300 2.54 1.8 × 10 ^-3 4.2 × 10 ^-7 Example 8 40 32100 2.24 3.7 × 10 ^-3 12.8 × 10 ^-7 Comparative Example 1 3.5 × 10 ^-3 21.0 × 10 ^-7

As shown in Table 1, the polymer electrolyte membranes of Examples 5 to 8 including the polysulfone polymer of Examples 1 to 4 have a low methanol permeability compared to Comparative Example 1 while having a hydrogen ion conductivity similar to that of Comparative Example 1 Showed.

1 is a schematic diagram of a direct methanol fuel cell according to one embodiment of the invention.

Claims (20)

Polysulfone polymer comprising a repeating unit represented by the formula (1): <Formula 1>

Where X is a single bond or Ar ₁ , and Ar ₁ is a substituted or unsubstituted C 6 -C 20 arylene group; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium; a, b, c, and d are each independently an integer from 0 to 5; e and f are each independently an integer of 0 to 2, n is 2 to 10,000 as the degree of polymerization, Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ contain one or more sulfonate groups. The polymer according to claim 1, wherein the polymer is a copolymer further comprising a repeating unit represented by the following Chemical Formula 2. <Formula 2>

Where Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group; m is 2 to 10,000 as polymerization degree. The polymer according to claim 1, wherein the polymer is a copolymer including a repeating unit represented by the following Chemical Formula 3: <Formula 3>

Where X, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, d, e, and f are as defined in claim 1, Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group; p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ contain one or more sulfonate groups. The polymer according to claim 3, wherein the substituted or unsubstituted C6-C20 arylene group is represented by one of the following formulas: <Formula 1a> <Formula 1b>

In the above equations, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ are each independently hydrogen, halogen atom, -SO ₃ M, C1 C50-C50 alkyl group, C2-C50 alkenyl group, C2-C50 alkynyl group, C5-C50 cycloalkyl group, C6-C50 aryl group, C2-C50 heteroaryl group, C7-C50 alkylaryl group, or A C1-C50 alkoxy group; Y is a single bond, S, S (= 0) ₂ , C (= 0), P (= 0) (R ₁₇ ) or C (R ₁₈ ) (R ₁₉ ), wherein R ₁₇ , R ₁₈ , and R ₁₉ independently of each other is a C1-C20 alkyl group unsubstituted or substituted with halogen, or a C6-C20 aryl group unsubstituted or substituted with halogen. The polymer according to claim 1, wherein the polymer is a copolymer comprising a repeating unit represented by the following formula (4): <Formula 4>

Where R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently a C 6 -C 50 aryl group unsubstituted or substituted with -SO ₃ M, or -SO ₃ M, R ₂₅ and R ₂₆ are each independently hydrogen, a C 1 -C 10 alkyl group unsubstituted or substituted with -SO ₃ M, -SO ₃ M, or a C 6 -C 20 aryl group unsubstituted or substituted with -SO ₃ M , Ar ₄ and Ar ₅ are each independently a substituted or unsubstituted C6-C20 arylene group; p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, Provided that R ₂₁ to R ₂₆ contain one or more sulfonate groups. The polymer of claim 5 wherein R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are independently of each other represented by one of the following substituents:

In the above substituents, M is independently of each other hydrogen, lithium, sodium or potassium, aa, ac, af, aj and ao are integers from 1 to 5, independently of one another, ab, ad, ae, ag, ah, ai, ak, al, am and an are integers from 0 to 4. The polymer of claim 5 wherein Ar ₄ or Ar ₅ is represented by one of the following structures:

In the above equations, A is a single bond, S, S (= 0) ₂ , or C (= 0); B is a single bond, S, S (= O) ₂ , C (= O), P (= O) (C ₆ H ₅ ), C (CF ₃ ) (C ₆ H ₅ ), C (CH ₃ ) ₂ Or C (CF ₃ ) ₂ . 4. The polymer of claim 3 wherein the ratio of p and q is from 1: 9 to 9.9: 0.1. 4. The polymer according to claim 3, wherein the polymer has a weight average molecular weight of 1000 to 500000. 4. The polymer of claim 3 wherein the polymer is a random copolymer or a block copolymer. A polymer electrolyte membrane comprising the copolymer according to any one of claims 1 to 10. The method of claim 11, wherein the electrolyte membrane is polyimide, polyetherketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, polyphenylene sulfide, polystyrene, polytrifluoro A polymer electrolyte membrane further comprising at least one polymer selected from the group consisting of styrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and branched sulfonated polysulfone ketone copolymers. The method of claim 11, wherein the electrolyte membrane is silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), inorganic phosphoric acid, sulfonated SiO ₂ , sulfonated ZrO and sulfonated Zirconium phosphate (sulfonated ZrP) polymer electrolyte membrane, characterized in that it further comprises at least one inorganic material selected from the group consisting of. 12. The polymer electrolyte membrane of Claim 11, wherein the electrolyte membrane further comprises a porous support. A membrane-electrode assembly comprising the polymer electrolyte membrane of claim 11. A fuel cell employing the polymer electrolyte membrane of claim 11. 17. The fuel cell of claim 16, wherein the fuel cell is a direct methanol fuel cell. The fuel cell according to claim 16, wherein the fuel cell is a vehicle fuel cell. As a method for producing a polysulfone copolymer, Preparing a polymer by reacting a compound represented by Chemical Formulas 5 to 7; And Preparing a sulfonated polymer represented by the following Chemical Formula 3 by sulfonating the polymer; a polysulfone copolymer manufacturing method comprising: <Formula 3>

In Chemical Formula 4, X is a single bond or Ar ₁ , and Ar ₁ , Ar _2, and Ar ₃ are each independently a substituted or unsubstituted C6 to C20 arylene group; R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, -SO ₃ M, -SO ₃ M substituted or unsubstituted C1-C50 alkyl group, -SO ₃ M or by unsubstituted C2 ~ C50 alkenyl group, -SO ₃ M by a substituted or unsubstituted C2 ~ alkynyl group, -SO ₃ M by a substituted or unsubstituted cycloalkyl group of C5 ~ C50 of the C50, -SO ₃ M a substituted or unsubstituted C6 ~ C50 aryl group, -SO ₃ M by a substituted or unsubstituted alkyl of C2 ~ C50 heteroaryl group, a substituted or unsubstituted by -SO ₃ M C7 ~ C50 aryl group, or - C 1 -C 50 alkoxy group unsubstituted or substituted with SO ₃ M; M is independently of each other hydrogen, lithium, sodium, or potassium; a, b, c, and d are each independently an integer from 0 to 5; e and f are each independently an integer of 0 to 2, p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1, r is 2 to 10000 as the degree of polymerization, Provided that a + b + c + d + e + f is 1 or more, and R ₁ to R ₆ include one or more sulfonate groups, <Formula 5>

In Formula 5, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ are independently hydrogen, C 1 -C 50 alkyl group, C 2 -C 50 alkenyl group, C 2 -C 50 alkynyl group, C 5 -C 50 cycloalkyl group, C 6 C50-C50 aryl group, C2-C50 heteroaryl group, C7-C50 alkylaryl group, or C1-C50 alkoxy group; <Formula 6> <Formula 7> R ₃₁ -Ar ₂ -R ₃₂ R ₃₃ -Ar ₃ -R ₃₄ In Chemical Formulas 6 and 7, Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted C6-C20 arylene group; R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are independently of each other -F, -Cl, -Br, -I, or -OH. 20. The method of claim 19, wherein the compound of Formula 5 is represented by one of the following structures:

Images