KR101272661B1 - Sulfonated poly(arylene ether) copolymer, method for preparing the saem and use thereof - Google Patents

Abstract

The present invention relates to sulfonated poly (arylene ether) copolymers and processes for their preparation. The sulfonated poly (arylene ether) copolymer according to the present invention is capable of introducing 2 to 10 sulfonic acid groups through the phonation process described below, thereby reducing the amount of monomer used for introducing sulfonic acid groups, as well as a polymer electrolyte membrane and a cation. Various applications are possible with exchange resins or cation exchange membranes.

Description

Sulfonated poly (arylene ether) copolymers, preparation method thereof and use thereof {SULFONATED POLY (ARYLENE ETHER) COPOLYMER, METHOD FOR PREPARING THE SAEM AND USE THEREOF}

The present invention relates to sulfonated poly (arylene ether) copolymers having excellent processability and physical properties as well as reducing the amount of monomers having sulfonic acid groups by introducing sulfonic acid groups through a post-process, and methods for preparing the same. will be.

In order to prevent pollution of river water caused by industrial water due to industrial development in modern society and to secure valuable metal resources, much attention has been focused. Many physical or chemical methods are known for this purpose, and among these, ion exchange methods are most commonly used.

The ion exchange method is a method of recovering ions in a solution by exchanging ions to be extracted in a solution with a functional group of a resin, and an adsorption step for separating desired ions from a solution into a solid resin. It can be described as an extraction step for recovering and a regenerating step for reusing the resin.

Ion exchange resins can be classified according to the type of ion exchange groups introduced into the base resin and the type of ion exchange resin. When classified according to the type of ion exchange resin, it can be divided into granular ion exchanger and fibrous ion exchanger. In addition, according to the type of the ion exchange group, the cation exchange resin to remove the cation in the solution by replacing the cation in the solution with its own cation, and the anion exchange resin to remove the anion in the solution by replacing the anion in the solution with its own anion. There is.

What is currently used as a cation exchange resin is a styrene-based resin in which an ion exchange group is introduced into a resin having a three-dimensional network structure manufactured by using divinylbenzene as a crosslinking agent in styrene. It is chemically stable to strong acid and strong base and has the advantage that ion exchange is possible in all pH range because sulfonic acid group is exchanger. If it is heated for 24 hours at, the exchange capacity is reduced by 15 to 40%. Such ion exchange resins are used for various purposes such as recovery of valuable metals, air purification, catalysts, water treatment, pharmaceuticals and protein separation. However, currently used ion exchange resins have a limit in ion exchange capacity, and most of them are crosslinked, and thus have disadvantages of poor workability. Therefore, there is an urgent need for the development of new ion exchange resins that have alleviated these shortcomings.

In addition, the ion exchange resin can be applied as a polymer electrolyte membrane of a fuel cell due to the ion exchange capacity. Polymer electrolyte membranes are classified into fluorinated PEM and hydrocarbon-based PEM. Among them, hydrocarbon electrolyte membranes are polyimide (PI), polysulfone (PSU), polyether ketone (PEK), poly It is manufactured using a polymer such as arylene ether sulfone (PAES), and generally has a low manufacturing cost and excellent thermal stability as compared to a fluorine-based electrolyte membrane.

However, hydrophilic ionic groups such as sulfonic acid groups are introduced to hydrocarbon-based electrolyte membranes to impart hydrogen ion conductivity at the level of fluorine-based membranes. Thus, mechanical properties are degraded due to excessive swelling by moisture, resulting in poor membrane stability, There is a problem that some are eluted. In order to solve the above problems, a crosslinked structure by covalent bonding is introduced into the raw material resin to lower the water solubility of the electrolyte membrane to inhibit elution of the resin, or by introducing sulfonic acid groups into the side chain rather than the main chain of the polymer to increase the fluidity of the polymer chain. A method of improving the conductivity of the is proposed. However, the hydrogen ion conductivity is still low, the macromolecule by crosslinking is difficult in the synthesis process and the membrane manufacturing process using the same, and the mechanical properties of the membrane is insufficient due to the fluidity of the polymer due to the increase in glass transition temperature (T _g ) There is this.

It is an object of the present invention to provide sulfonated poly (arylene ether) copolymers having good processability and physical properties.

Another object of the present invention is to provide a method for preparing the sulfonated poly (arylene ether) copolymer.

Another object of the present invention is to provide a polymer electrolyte membrane including the sulfonated poly (arylene ether) copolymer having improved ion exchange capacity and metal ion adsorption capacity, a membrane-electrode assembly and a fuel cell employing the same.

In order to achieve the above object, the present invention provides a sulfonated poly (arylene ether) copolymer comprising a repeating unit represented by the following formula (1) or (2).

 [Formula 1]

[Formula 2]

Where

X is a single bond or Ar ₁ , Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ and M ₈ are independently of each other hydrogen, lithium, sodium or potassium,

a + b = 5, c + d = 5,

a and c are each independently an integer of 1 to 5,

b, c, e and f are each independently an integer from 0 to 4,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, straight or branched alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, alkynyl group of 2 to 20 carbon atoms, 5 carbon atoms A cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an alkoxy group of 1 to 20 carbon atoms,

n is 10 to 10,000 as polymerization degree.

In addition, the present invention as shown in Scheme 1,

(S1) synthesizing a copolymer represented by Formula 9 by polymerizing a monomer of Formula 5, a monomer of Formula 7 and a monomer of Formula 8; And (S2) provides a method for producing a sulfonated poly (arylene ether) copolymer represented by the formula (3) comprising the step of introducing a sulfonic acid group to the phenyl ring portion of the copolymer of formula (9).

[Reaction Scheme 1]

Where

X, M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , a, b, c, d, e, f are As defined above,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

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

r is 10 to 10,000 as the degree of polymerization,

_{R '1, R' 2,} R '3 and R' ₄ is hydrogen, a substituted or unsubstituted C _{1 -20} alkyl, substituted or unsubstituted C _{2 -20} alkenyl group, a substituted or unsubstituted C _{2 -20} Exchange alkynyl group, a substituted or unsubstituted C _{5 -20} cycloalkyl group, a substituted or unsubstituted C _{6 -20} aryl group, a substituted or unsubstituted C _{2 -20} heteroaryl group, a substituted or unsubstituted C _{7 -20} alkyl an aryl group, or a substituted or unsubstituted C _{1 -20} alkoxy group,

X ₁ and X ₂ are Cl, Br, I, or F.

In addition, the present invention as shown in Scheme 2,

(S1) synthesizing a copolymer represented by Formula 10 by polymerizing a monomer of Formula 6, a monomer of Formula 7 and a monomer of Formula 8; And (S2) provides a method for producing a sulfonated poly (arylene ether) copolymer represented by the formula (4) comprising the step of introducing a sulfonic acid group to the phenyl ring portion of the copolymer of formula (10).

[Reaction Scheme 2]

Wherein X, X ₁ , X ₂ , M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , R ' ₁ , R ' ₂ , R' ₃ , R ' ₄ , a, b, c, d, e, f, Ar ₂ , Ar ₃ , p, q and r are as defined above.

In addition, the present invention provides a polymer electrolyte membrane including the proton conductive block copolymer.

In addition, the present invention provides a membrane-electrode assembly including the polymer electrolyte membrane.

The present invention also provides a fuel cell employing the membrane-electrode assembly.

Since the sulfonated poly (arylene ether) copolymer according to the present invention is capable of introducing two or more, most preferably ten or more sulfonic acid groups through a post-process, monomers for introducing the sulfonic acid groups The usage amount of can be reduced.

In addition, the sulfonated poly (arylene ether) copolymer of the present invention is not only excellent in physical properties, hydrogen ion conductivity ion exchange capacity and metal ion adsorption capacity, but also easy to be processed and molded into various forms to polymer electrolyte membrane and cation exchange. It can be applied to a wide range of applications such as resins.

Hereinafter, the present invention will be described in more detail.

The present invention provides sulfonated poly (arylene ether) copolymers comprising repeating units represented by Formula 1 or Formula 2:

[Formula 1]

[Formula 2]

Where

X is a single bond or Ar ₁ , Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ and M ₈ are independently of each other hydrogen, lithium, sodium or potassium,

a + b = 5, c + d = 5, a and c are each independently an integer from 1 to 5,

b, c, e and f are each independently an integer from 0 to 4,

R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, straight or branched alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, alkynyl group of 2 to 20 carbon atoms, 5 carbon atoms A cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an alkoxy group of 1 to 20 carbon atoms,

n is 10 to 10,000 as polymerization degree.

The sulfonic acid groups included in the sulfonated poly (arylene ether) copolymers of the present invention are linked to one end of the side chain. The sulfonic acid group can be relatively freely moved away from the main chain by being linked 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 size of the ion channel can be controlled by adjusting the position where the sulfonic acid group is connected to the side chain. As a result, the sulfonic acid polymer may easily control the amount of water contained in the ion channel and may have high hydrogen ion conductivity.

Conventional proton-conducting polymers have a limitation in the content of the cation exchanger because the cation exchanger is directly connected to the main chain to increase the content of the cation exchanger in the polymer, so that the polymer itself is dissolved in water and thus the function of the electrolyte membrane may be lost. Therefore, conventional general proton conducting polymers in which a cation exchanger is connected only to the main chain are difficult to have high hydrogen ion conductivity and may be easy to permeate through the main chain of methanol. In addition, since the hydrophilic part and the hydrophobic part in the polymer are separated by the presence of a cation exchange group spaced apart from the main chain in the polymer, permeation of methanol via the main chain which is a hydrophobic part can be further suppressed. In addition, since the cation exchanger is not present in the main chain but in the side chain, the flexibility of the proton conductive polymer itself may be improved, and thermal stability and stability to oxidation / reduction reaction may be improved.

The copolymer according to the present invention may further include a repeating unit represented by Formula 11 below:

[Formula 11]

Where

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and m is 10 to 10,000 as the degree of polymerization.

Looking at the definition of the above-described substituents in detail as follows.

In the sulfonated poly (arylene ether) copolymer of the present invention, the substituted or unsubstituted arylene group having 6 to 20 carbon atoms is preferably represented by the following formula (14) or (15).

[Formula 14]

[Formula 15]

Where

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 independently of one another are hydrogen, halogen atoms, carbon atoms of 1 to 20 Straight chain or branched alkyl group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl having 2 to 20 carbon atoms Group, a C7-C20 alkylaryl group, or a C1-C20 alkoxy group,

Y is a single bond, S, S (= O) ₂ , C (= O), P (= O) (R ₁₇ ) or C (R ₁₈ ) (R ₁₉ ), wherein R _{17 ,} R ₁₈ , R ₁₉ Are independently an aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with halogen.

The arylene groups represented by Formulas 14 and 15 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.

,

,

및

로 이루어진 군에서 선택되는 탄소 수 6 내지 20의 아릴렌기이다:Preferably, Ar ₁ , Ar ₂ and Ar ₃ are

,

,

And

An arylene group having 6 to 20 carbon atoms selected from the group consisting of:

Wherein 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 , R ₁₉ is an independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

An alkyl group which is a substituent used in the present invention means a straight or branched chain saturated monovalent hydrocarbon moiety of 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Specific examples of the unsubstituted alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. In addition, unless otherwise defined herein, at least one hydrogen atom included in the alkyl group may be a halogen atom, a hydroxy group, a nitro group, a cyano group, a substituted or unsubstituted amino group (-NH ₂ , -NH (R), -N (R ') (R''), wherein R' and R "are independently of each other an alkyl group having 1 to 10 carbon atoms, amidino group, hydrazine, or hydrazone group carboxyl group, sulfonic acid group, phosphoric acid group, C _{1 -20} alkyl group, a halogenated C _{1 -20} alkyl, C _{1 -20} alkenyl, C _{1 -20} alkynyl group, C _{1 -20} alkyl heteroaryl, C _{6 -20} aryl group, a C _{6 -20} aryl group, a C ₆ a heteroaryl group, a heteroarylalkyl group or a C _{6 -20 -20} may be substituted.

Alkenyl groups, which are substituents used in the present invention, are linear or branched monovalent of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon double bond. Means a hydrocarbon site. The alkenyl group may be bonded through a carbon atom containing a carbon-carbon double bond or through a saturated carbon atom. Examples of the alkenyl group include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, pentenyl, 5-hexenyl and dodecenyl. At least one hydrogen atom of the alkenyl group may be substituted with the same substituent as in the alkyl group.

Alkynyl, which is a substituent used in the present invention, is a straight or branched chain monovalent of 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms containing at least one carbon-carbon triple bond. Means a hydrocarbon site. Representative straight and branched alkynyl groups include acetylenyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1-butynyl, 4-pentynyl, 1 -Hexynyl, 2-hexynyl, 5-hexynyl, 1-heptinyl, 2-heptinyl, 6-heptinyl, 1-octinyl, 2-octynyl, 7-octinyl, 1-noninyl, 2 -Noninyl, 8-noninyl, 1-decynyl, 2-decynyl, 9-decynyl and the like.

The aryl group, which is a substituent used in the present invention, means a monovalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 20 ring atoms, and by one or more halogen substituents May be optionally substituted. The aromatic portion of the aryl group contains only carbon atoms. Examples of the aryl group include phenyl, naphthalenyl and fluorenyl, and at least one hydrogen atom in the aryl group may be substituted with the same substituent as in the alkyl group.

Heteroaryl group which is a substituent used in the present invention means a ring aromatic system having 5 to 30 ring atoms containing 1, 2 or 3 hetero atoms selected from N, O, P or S, and the remaining ring atoms are C, The rings may be attached or fused together in a pendant manner. At least one hydrogen atom in the heteroaryl group may be substituted with the same substituent as in the alkyl group.

Alkylaryl group, which is a substituent used in the present invention, means that some of the hydrogen atoms in the aryl group as defined above are substituted with radicals such as lower alkyl, for example methyl, ethyl, propyl and the like. For example benzyl, phenylethyl and the like. At least one hydrogen atom of the arylalkyl group may be substituted with the same substituent as in the alkyl group.

The alkoxy group which is a substituent used in the present invention refers to the radical -O-alkyl, wherein alkyl is as defined above. Specific examples thereof include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. At least one hydrogen atom of the alkoxy group is an alkyl group. Substituents similar to the above can be substituted.

By cycloalkyl group used in the present invention is meant a monovalent monocyclic system having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. At least one hydrogen atom in the cycloalkyl group may be substituted with the same substituent as in the alkyl group.

The arylene group used in the present invention means a divalent monocyclic, bicyclic or tricyclic aromatic hydrocarbon moiety having 6 to 20, preferably 6 to 12 ring atoms. Examples of the arylene group include phenylene, biphenylene, terphenylene, naphthalene and the like, and likewise, at least one hydrogen atom in the arylene group may be substituted with the same substituent as in the alkyl group.

Halogen used in the present invention is fluorine, chlorine, bromine, iodine or asstatin, among which fluorine is particularly preferred.

Preferably, the sulfonated poly (arylene ether) copolymer of the present invention may be represented by the following formula (3) or (4):

(3)

 [Formula 4]

Where

X, M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , a, b, c, d, e and f are As defined above,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

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

r is 10 to 10,000 as polymerization degree.

Most preferably, the sulfonated poly (arylene ether) copolymer of the present invention may be represented by the following formula (12) or formula (13):

[Chemical Formula 12]

[Chemical Formula 13]

Where

M ₁ to M ₈ are independently of each other hydrogen, lithium, sodium or potassium,

a and c are each independently an integer of 1 to 5,

Ar ₁ , Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,

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

r is 10 to 10,000 as polymerization degree, Preferably it is 20-100. The said polymerization degree range is suitable for achieving the objective of this invention.

According to another embodiment of the present invention, the ratio of p and q in the copolymer represented by Chemical Formulas 3 and 4 or 12 and 13 is preferably 1: 9 to 9: 1. When the ratio of p and q satisfies 1: 9 to 9: 1, the conductivity may be lowered and the physical property may be degraded or the problem of dissolving in water may be improved.

The sulfonated poly (arylene ether) copolymers according to the present invention may be random or block copolymers.

The sulfonated poly (arylene ether) copolymer is designed to have an appropriate molecular weight in the preparation step, preferably to have a weight average molecular weight of 10,000 to 1,000,000. If it is less than the above range, the mechanical properties and chemical stability are insufficient, on the contrary, if the above range is exceeded, the viscosity becomes too high, which makes handling difficult.

In addition, the sulfonated poly (arylene ether) copolymer has a degree of sulfonation of 30 to 50%, can be introduced up to six in the side chain, so that the sulfonic acid or sulfonate without excessive use of the monomer for sulfonic acid introduction The degree of sulfonation can be achieved by controlling the molar ratio of the compound for introduction.

In addition, the present invention as shown in Scheme 1,

(S1) synthesizing a copolymer represented by Formula 9 by polymerizing a monomer of Formula 5, a monomer of Formula 7 and a monomer of Formula 8; And (S2) provides a method for producing a sulfonated poly (arylene ether) copolymer represented by the formula (3) comprising the step of introducing a sulfonic acid group to the phenyl ring portion of the copolymer of formula (9).

[Reaction Scheme 1]

Where

X, M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , a, b, c, d, e, f are As defined above,

Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

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

r is 10 to 10,000 as the degree of polymerization,

_{R '1, R' 2,} R '3 and R' ₄ is hydrogen, a substituted or unsubstituted C _{1 -20} alkyl, substituted or unsubstituted C _{2 -20} alkenyl group, a substituted or unsubstituted C _{2 -20} Exchange alkynyl group, a substituted or unsubstituted C _{5 -20} cycloalkyl group, a substituted or unsubstituted C _{6 -20} aryl group, a substituted or unsubstituted C _{2 -20} heteroaryl group, a substituted or unsubstituted C _{7 -20} alkyl an aryl group, or a substituted or unsubstituted C _{1 -20} alkoxy group,

X ₁ and X ₂ are Cl, Br, I, or F.

In addition, the present invention as shown in Scheme 2,

(S1) synthesizing a copolymer represented by Formula 10 by polymerizing a monomer of Formula 6, a monomer of Formula 7 and a monomer of Formula 8; And (S2) provides a method for producing a sulfonated poly (arylene ether) copolymer represented by the formula (4) comprising the step of introducing a sulfonic acid group to the phenyl ring portion of the copolymer of formula (10).

[Reaction Scheme 2]

Wherein X, X ₁ , X ₂ , M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , R ' ₁ , R ' ₂ , R' ₃ , R ' ₄ , a, b, c, d, e, f, Ar ₂ , Ar ₃ , p, q and r are as defined above.

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

Hereinafter, the manufacturing method will be described in more detail at each step.

First, in step S1, a block copolymer represented by Formula 9 or Formula 10 is synthesized by performing a condensation polymerization reaction of a monomer of Formula 5 or 6 with a monomer of Formula 7 and a monomer of Formula 8. This polycondensation reaction proceeds through a nucleophilic substitution reaction through an activation step and a polymerization step. This reaction may be carried out under reaction conditions generally known in the art to which the present invention pertains, and therefore, the present invention is not particularly limited.

The polymerization reaction is carried out in an organic solvent, so long as it can dissolve the reactants and the product is not particularly limited in the present invention. As specific examples, toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, styrene, benzene, n-butyl acetate, methylcyclohexane, dimethylcyclohexane and mixed solvents thereof are possible. At this time, the reaction may proceed under an alkali metal base to facilitate the polycondensation reaction. Potassium carbonate, sodium carbonate, sodium hydroxide, calcium hydroxide, or the like may be used as the alkali metal base.

In step S2, a sulfonic acid group is introduced into the phenyl ring portion of the compound represented by the formula (9) or (10).

Compounds for introducing sulfonic acid groups include 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 phosphoric acid At least one selected from the group consisting of can be used.

The sulfonic acid group introduction reaction is performed by reacting a compound represented by Formula 9 or 10 with a compound for introducing sulfonic acid group, for example, at 0 to 100 ° C., or at 25 to 50 ° C. for 0.1 to 2 hours. At this time, if the reaction temperature is less than 0 ℃ can not obtain a sufficiently sulfonated polymer, on the contrary, if the temperature exceeds 100 ℃, the introduction ratio does not increase any more, and in some cases the main chain of the polymer may be decomposed.

At this time, if necessary, an additional reaction may be further performed between the condensation polymerization step and the cation exchanger introduction reaction step.

For example, when at least one of Ar ₁ , Ar _2, and Ar ₃ of Formulas 9 and 10 has a sulfone functional group, the sulfone functional group may be obtained by oxidation of a sulfane functional group as shown in Scheme 6 below. Can be obtained as a result.

[Reaction Scheme 6]

In the above reaction formula, Z ₁ and Z ₂ are independently hydrogen, a halogen atom, a straight-chain or branched C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{2 -20} alkynyl group, C _{5 -20} cycloalkyl group, C _{6 -20} aryl group, a C _{2 -20} heteroaryl group, C _{7 -20} alkyl, an aryl group, or C _{1 -20} alkoxy groups.

The oxidation reaction is not particularly limited in the present invention, a method commonly used in this field is possible. For example, in the presence of a solvent, an oxidation reaction is performed by mixing a compound containing a sulphate functional group with an oxidizing agent in a constant equivalent ratio. As the oxidizing agent, metachloroperoxybenzoic acid, hydrogen peroxide, potassium peroxymonosulfate (OXONE?), Magnesium monoperoxyphthalic acid, or the like can be used. The solvent may be dichloromethane, toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, xylene, benzene, n-butyl acetate, methylcyclohexane, dimethylcyclohexane and mixed solvents thereof. The reaction is carried out at 25 to 50 ° C. for 30 minutes to 10 hours.

The present invention also provides a polymer electrolyte membrane comprising the sulfonated poly (arylene ether) copolymer of the present invention. The polymer electrolyte membrane comprising the sulfonated poly (arylene ether) copolymer of the present invention has a low methanol permeability and high hydrogen ion conductivity. And the moisture content is also excellent. In addition, the polymer electrolyte membrane may have thermal stability and chemical stability, which are conventionally possessed by a poly (arylene ether) polymer, and may be used as a thermoplastic polymer, a membrane elastomer, and the like because of easy processing and low moisture absorption. In addition, because of the sulfonic acid group, it can have high hydrogen ion conductivity even at low moisture content, and can exhibit high dimensional stability even if it is exposed to moisture for a long time, thereby exhibiting high dimensional stability. It is very suitable for use in batteries or secondary batteries.

The polymer electrolyte membrane according to the present invention can be prepared by conventional methods in the art, except for using the sulfonated poly (arylene ether) copolymer according to the present invention. For example, the sulfonated poly (arylene ether) copolymer according to the present invention may be prepared by organic solvents such as dimethylacrylic acid (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and the like. After dissolving in, it can be produced by casting on a glass plate and drying at 80 to 160 ℃.

Meanwhile, in addition to the sulfonated poly (arylene ether) copolymer according to the present invention in the preparation of the polymer electrolyte membrane, components usable in the preparation of the polymer electrolyte membrane in the art to which the present invention pertains may be further added.

According to one embodiment of the invention, the polymer electrolyte membrane is polyimide, polyetherketone, polysulfonic acid, polyethersulfonic acid, polyetherethersulfonic acid, polybenzimidazole, polyphenylene oxide, polyphenylene sulfide, polystyrene It may further include one or more polymers selected from the group consisting of polytrifluorourostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane and branched sulfonated polysulfone ketone copolymer.

According to another embodiment of the present invention, the polymer electrolyte membrane includes silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), inorganic phosphoric acid, sulfonated SiO ₂ , sulfonated ZrO and It may further comprise at least one inorganic material selected from the group consisting of sulfonated zirconium phosphate (sulfonated ZrP). Including such inorganics may reduce the fuel permeability of the polymer electrolyte membrane by acting as a barrier of the channel through which the inorganic ions and methanol are permeated.

According to another embodiment of the present invention, the polymer electrolyte membrane may further include a porous support. Including the porous support may improve the tensile strength of the polymer electrolyte membrane. Examples of the porous support include porous polyolefins such as porous polyethylene, porous teflon, porous polyimide, and the like.

According to another embodiment of the present invention, a membrane-electrode assembly and a fuel cell including the polymer electrolyte membrane are provided.

The membrane-electrode assembly includes an anode (fuel anode), a cathode (oxygen cathode) and a polymer electrolyte membrane according to one embodiment of the present invention disposed between two electrodes. The anode and cathode are not particularly limited because they may be used in the art to which the present invention pertains.

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 one or more selected from. 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 be porous and have a surface area of at least 150 m 2 / g, in particular 500 to 1200 m 2 / g, and an average particle diameter of 10 to 300 nm, in particular 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 a carbon powder, a conductive material such as carbon black, activated carbon, acetylene black, a binder such as polytetrafluroethylene and, if necessary, an ionomer.

The cathode and / or anode can be prepared, for example, as follows. First, a catalyst slurry is prepared by mixing a catalyst powder, a binder, and a 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 an embodiment of the present invention is inserted between the cathode and the anode and compressed by hot pressing, 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.

The fuel cell further includes separator plates attached to both surfaces of the membrane-electrode assembly including the polymer electrolyte membrane according to the 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.

According to another embodiment of the present invention, the fuel cell may be a direct methanol fuel cell, but is not limited thereto.

According to another embodiment of the present invention, the fuel cell may be a vehicle fuel cell. 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.

The polymer according to another embodiment of the present invention can be used in various technical fields, and the field is not limited. For example, the 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 that utilizes the proton conductivity of the polymer.

Hereinafter, preferred examples are provided to help the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it is apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It goes without saying that changes and modifications belong to the appended claims.

Example  1: Sulfonated Poly ( Arylene  Ether) copolymer synthesis (x = 0.30)

A sulfonated poly (arylene ether) copolymer was prepared through a reaction represented by Scheme 3 below.

Scheme 3

(Step 1) Condensation polymerization  step

Three monomers 4,4'-sulfonyl diphenol 10.5 mmol, 4,4 'in a three-necked round bottom flask in a nitrogen atmosphere on a device equipped with a condenser, Deanstock trap and magnetic sterling bar. -(2,2-diphenylethenylidene) bisphenol (4,4 '-(2,2-diphenylethenylidene) bisphenol) 4.5 mmol, 4,4'-difluorodiphenylsulfone 15 mmol was added and 50 mL of dimethylacetamide was added to dissolve completely. After completely dissolving the monomers, 18 mmol of potassium carbonate and 50 mL of toluene were added thereto, and the temperature of the reactor was raised to 135 ° C to reflux for 4 hours, followed by an activation step for water removal and polymerization, and then the reaction temperature was gradually increased to 165 ° C. The collected water and toluene were removed while raising. Thereafter, the polycondensation reaction was performed for 2 hours. The reaction obtained after the reaction was washed several times in a methanol / water (1: 1, v / v) mixture. Subsequently, the resultant was vacuum dried at 60 ° C. for 1 day to obtain a white solid copolymer (yield 92%, X = 0.3).

(Step 2) Sulfonation  step

A magnetic sterling bar and a condenser were installed in a three-necked flask, 1 g of the copolymer obtained in Step 1 was added in a nitrogen atmosphere, 10 ml of concentrated sulfuric acid was added thereto, the temperature was raised to 50 ° C., and the mixture was completely reacted for 24 hours. The reaction solution was then poured into distilled water and washed several times to remove unreacted concentrated sulfuric acid. The precipitate was then filtered and vacuum dried at 60 ° C. for 24 hours. The dried precipitate was dissolved in dimethyl acetamide again to prepare a solution, and then 3% by weight of aqueous potassium hydroxide solution was added dropwise, and then hydrochloric acid was added to adjust the pH of the solution to neutrality. The product was then filtered and dried in vacuo to give a sulfonated poly (arylene ether) copolymer (yield 94%, X = 0.3).

Example  2: of formula 1 Sulfonated Poly ( Arylene  Ether) Synthesis of Copolymer (x = 0.4)

(Step 1) Condensation polymerization  step

Except that 7.5 mmol of 4,4'-sulfonyldiphenol, 5 mmol of 4,4 '-(2,2-diphenylethenylidene) bisphenol, and 12.5 mmol of 4,4'-difluorodiphenylsulfone were used , The copolymer (yield 90%, X = 0.4) was prepared in the same manner as in Step 1 of Example 1.

(Step 2) Sulfonation  step

A sulfonated poly (arylene ether) copolymer (yield 93%, X = 0.4) was prepared by the same method as Step 2 of Example 1, except that the product prepared in Step 1 of Example 2 was used. .

Example  3: of formula 1 Sulfonated Poly ( Arylene  Ether) Synthesis of Copolymer (x = 0.5)

(Step 1) Condensation polymerization  step

Except that 7 mmol of 4,4'-sulfonyldiphenol, 4 mmol of 4,4 '-(2,2-diphenylethenylidene) bisphenol, and 14 mmol of 4,4'-difluorodiphenylsulfone were used. In the same manner as in Step 1 of Example 1, a copolymer (yield 93%, x = 0.5) was prepared.

(Step 2) Sulfonation  step

The compound was prepared by the same method as Step 2 of Example 1, except that the product prepared in Step 1 of Example 3 was used. The x value of the compound was 0.5. Yield 92%.

Example  4: multiple Phenyl Monomeric  synthesis

Through the reaction represented by the following Scheme 4, a multi-phenyl monomer was prepared.

[Reaction Scheme 4]

(Step 1) Friedel - Craft  Reaction step

Into a three-necked flask, a dropping funnel was added, and 10 mmol of 4,4 '-(2,2-diphenylethenylidene) bismethoxybenzene and 10 mmol of aluminum chloride were added and stirred in a nitrogen atmosphere. Made into a state. A solution of 22 mmol of benzoyl chloride in 5 ml of carbon disulfide was then added dropwise with stirring to the suspension at room temperature. The reaction was allowed to react at room temperature for 5 hours and poured carefully with stirring in distilled water at 0 ° C. The mixture was extracted with dichloromethane and then the extracted solution was washed with aqueous sodium hydroxide solution, washed several times with distilled water and dried over sodium sulfate. The water solution was then evaporated to yield a light brown powdery monomer (yield 62%).

(Step 2) Polyphenylation  step

12 mmol of a three-necked flask diphenyl methane was dissolved in 20 ml of dry tetrahydrofuran and 4 ml of 2.5M n-butyllithium hexane solution was added at 0 ° C. under nitrogen atmosphere. After the addition was complete and stirred for 20 minutes, 4.5 mmol of the monomer obtained in Step 1 of Example 4 was added at room temperature. The reaction was terminated by reaction at room temperature for 6 hours and poured into aqueous ammonium chloride solution. The organic layer was extracted with dichloromethane and the extracted organic layer was dried over sodium sulfate and then the solvent was dried to remove the light yellow viscous liquid. The mucus was dissolved completely in 80 ml of toluene in a three neck flask and 1.8 mmol of p-toluene sulfonic acid was added. Then, a Deanstock trap and a condenser were installed and refluxed for 4 hours. The reaction was cooled to room temperature, washed several times with 10% by weight aqueous sodium bicarbonate solution, dried over sodium sulfate and evaporated to give a beige powder. The obtained powder was recrystallized from dichloromethane and methanol for purity. Yielded a high product (yield 87%).

(Step 3) methyl group removal step

In a three-necked flask equipped with a dropping funnel, 10 mmol of the monomer synthesized in the step 2 of Example 4 was completely dissolved in 80 ml of dichloromethane. 20 ml of 1.0 M boron tribromide-dichloromethane solution was slowly added dropwise at 0 ° C. under a nitrogen atmosphere. After the addition was completed, the temperature was raised to room temperature and reacted for 12 hours. The temperature of the reaction solution was lowered to 0 ° C. and distilled water was poured to terminate the reaction. Then, the organic layer was extracted using ethyl acetate and 1M aqueous hydrochloric acid solution. The extracted organic layer was washed several times with distilled water and then dried using sodium sulfate. The solvent of the dried solution was evaporated and the obtained powder was recrystallized using acetonitrile and distilled water to obtain a light beige monomer (yield 84%).

Example  5: of formula 2 Sulfonated Poly ( Arylene  Ether) copolymers (x = 0.1)

Through the reaction represented by Scheme 5 below, a multi-sulfonated poly (arylene ether) copolymer was prepared.

Scheme 5

(Step 1) Condensation polymerization  step

The same procedure as in Step 1 of Example 1 was repeated except that 1 mmol of the monomer synthesized in Example 4, 9 mmol of 4,4'-sulfonyldiphenol, and 10 mmol of 4,4'-difluorodiphenylsulfone were used. The compound (yield 93%, x = 0.1) was prepared.

(Step 2) Phone later  step

The compound (yield 91%, x = 0.1) was prepared by the same method as Step 2 of Example 1, except that the product prepared in Step 1 of Example 5 was used.

Example  6: of formula 2 Sulfonated Poly ( Arylene  Ether) Synthesis of Copolymer (x = 0.13)

(Step 1) Condensation polymerization  step

In the same manner as in Step 1 of Example 1, except that 1.3 mmol of the monomer synthesized in Example 4, 8.7 mmol of 4,4'-sulfonyldiphenol, and 10 mmol of 4,4'-difluorodiphenylsulfone were used. The compound (yield 94%, x = 0.13) was prepared.

(Step 2) Phone later  step

The compound (yield 90%, x = 0.13) was prepared by the same method as Step 2 of Example 1, except that the product prepared in Step 1 of Example 6 was used.

Example  7: of formula 2 Sulfonated Poly ( Arylene  Ether) copolymerization (x = 0.17)

(Step 1) Condensation polymerization  step

In the same manner as in Step 1 of Example 1, except that 1.7 mmol of the monomer synthesized in Example 4, 8.3 mmol of 4,4'-sulfonyldiphenol, and 10 mmol of 4,4'-difluorodiphenylsulfone were used. The compound (yield 91%, x = 0.17) was prepared.

(Step 2) Phone later  step

The compound (yield 92%, x = 0.17) was prepared by the same method as Step 2 of Example 1, except that the product prepared in Step 1 of Example 7 was used.

< Example  8 to 13 and Comparative example  1: Preparation of Polymer Electrolyte Membrane>

Example  8

The poly (arylene ether) copolymer prepared in Example 1 was dissolved in dimethyl acetamide, cast on a glass plate using a flat glass plate and a round glass rod, and then dried at 80 ° C. in a vacuum oven to obtain a polymer having a thickness of 50 μm. An electrolyte membrane was prepared.

Example  9

Using a poly (arylene ether) copolymer prepared in Example 2 to prepare a polymer electrolyte membrane having a thickness of 50 ㎛ in the same manner as in Example 8.

Example  10

A polyelectrolyte membrane having a thickness of 50 μm was prepared in the same manner as in Example 8, using the poly (arylene ether) copolymer prepared in Example 3.

Example  11

Using a poly (arylene ether) copolymer prepared in Example 5 to prepare a polymer electrolyte membrane having a thickness of 50 ㎛ in the same manner as in Example 8.

Example  12

Using a poly (arylene ether) copolymer prepared in Example 6 to prepare a polymer electrolyte membrane having a thickness of 50 ㎛ in the same manner as in Example 8.

Example  13

Using a poly (arylene ether) copolymer prepared in Example 7 to prepare a polymer electrolyte membrane having a thickness of 50 ㎛ in the same manner as in Example 8.

Comparative example  One

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

Experimental Example  One: Sulfonated , Molecular weight and Polydispersity index  Measure

Sulfonation was predicted by hydrogen ion titration

Chromatography was used to measure the weight average molecular weight and polydispersity index (PDI) of the sulfonated poly (arylene ether) copolymers prepared in Examples 1 to 3 and 5 to 7. The results are shown in Table 1 below. The instruments and conditions used for the measurements are as follows:

GPC unit: Waters, model 2424

Column: Waters, model HR3,4,5 Column temperature: 80 ℃

Elution solvent: dimethylformamide

Elution rate: 1 ml / min.

Reference Material: Polymethylmethacrylate (PMMA)

division Sulfonation degree (%) Weight average molecular weight () Polydispersity Index (PDI) Example 1 30 156 × 10 ³ 2.38 Example 2 40 148 × 10 ³ 2.14 Example 3 50 152 × 10 ³ 2.42 Example 5 10 138 × 10 ³ 2.41 Example 6 13 141 × 10 ³ 2.17 Example 7 17 137 × 10 ³ 2.24

Experimental Example  2: Solubility Measurement in Organic Solvents

N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide at room temperature of the sulfonated poly (arylene ether) copolymers prepared in Examples 1 to 3 and Examples 5 to 7 Solubility in (DMF), dimethylsulfone (DMSO), methanol (MeOH) and water is summarized in Table 2 below.

division NMP DMAc DMF DMSO MeOH water Example 1 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 2 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 3 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 5 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 6 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble Example 7 Dissolution Dissolution Dissolution Dissolution Insoluble Insoluble

As shown in Table 2, the sulfonated poly (arylene ether) copolymer according to the present invention has a very great advantage in that it can be processed for various uses because it has excellent solubility at room temperature in various kinds of solvents.

Experimental Example  3: ion exchange capacity ( Ion Exchange Capacity ) Measure

The sulfonated poly (arylene ether) copolymer membranes obtained in Examples 1 to 3 and Examples 5 to 7 were respectively immersed in 0.1 M NaCl solution for at least 48 hours to hydrogen ions (H ⁺ ) to sodium ions (Na ⁺ ). Substituted by The substituted hydrogen ion (H ⁺ ) is titrated with 0.01 N NaOH standard solution, and the ion exchange capacity (Ion Exchange Capacity, IEC) value of the polymer membrane is calculated according to Equation 2 as the amount of NaOH used in the titration, The results are shown in Table 5 below.

[Equation 1]

IEC (meq / g) = (V _NaOH C _NaOH ) / W _dry

(Equation 1, W _dry : weight of dried thin film (g), V _NaOH : consumed NaOH standard solution (mL), C _NaOH : NaOH standard solution (M))

division Ion exchange capacity (meq / g) Example 1 1.14 Example 2 1.47 Example 3 1.72 Example 5 1.04 Example 6 1.32 Example 7 1.61

Experimental Example  4: Hydrogen ion  Conductivity measurement

Proton conductivity of the polymer electrolyte membranes of Examples 8 to 13 and Comparative Example 1 was measured. Hydrogen ion conductivity was measured by interposing the polymer electrolyte membrane between two platinum electrodes having a width of 2.54 cm ² , and then measuring the initial resistance value at 25 ° C. using a potentiometer (Impedance Spectroscopy, manufacturer: Solartron). Subsequently, hydrogen ion conductivity was calculated using Equation 2 below. The results are shown in Table 4 below.

&Quot; (2) &quot;

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

Experimental Example  5: methanol permeability measurement

After interposing the polymer electrolyte membranes according to Examples 8 to 13 between the two cells, 15 ml of 1M aqueous methanol solution was injected into one cell, and 15 ml of distilled water was injected into the other cell. 10 μl was aliquoted per 10 minutes and then again filled with 10 μl of distilled water. The methanol concentration was measured by gas chromatography on the sample collected. The change in methanol concentration over time was plotted and the methanol permeability was calculated from the slope according to Equation 3 below, and the results are shown in Table 4 below.

&Quot; (3) &quot;

Methanol Permeability [cm2 / s] = (Slope [ppm / s] × Solution Volume × Electrolyte Membrane Thickness) / (Electrolyte Membrane Area × Methanol Concentration)

Wherein the membrane thickness is 0.05 cm, methanol concentration 1 mol / L (32000 ppm), solution volume 15 ml, membrane area 7.06 cm 2 )

division Hydrogen ion conductivity [S / cm] Methanol transmittance [cm2 / s] Example 8 1.24 × 10 ^-3 4.1 × 10 ^-7 Example 9 1.85 × 10 ^-3 4.4 × 10 ^-7 Example 10 2.32 x 10 ^-3 4.9 × 10 ^-7 Example 11 1.23 × 10 ^-3 3.7 × 10 ^-7 Example 12 1.79 × 10 ^-3 3.9 × 10 ^-7 Example 13 2.28 × 10 ^-3 4.2 × 10 ^-7 Comparative Example 1 3.5 × 10 ^-3 21.0 × 10 ^-7

As confirmed from Table 4 above, the polymer electrolyte membranes of Examples 8 to 13 including the sulfonated poly (arylene ether) copolymer of the present invention had a hydrogen ion conductivity similar to that of Comparative Example 1, It showed significantly lower methanol permeability.

Claims (23)

Sulfonated poly (arylene ether) copolymers comprising repeating units represented by Formula 1 or Formula 2 below:
[Formula 1]

(2)

In this formula,
X is a single bond or Ar ₁ , Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ and M ₈ are independently of each other hydrogen, lithium, sodium or potassium,
a + b = 5, c + d = 5,
a and c are each independently an integer of 1 to 5,
b, c, e and f are each independently an integer from 0 to 4,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, straight or branched alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, alkynyl group of 2 to 20 carbon atoms, 5 carbon atoms A cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an alkoxy group of 1 to 20 carbon atoms,
n is 10 to 10,000 as polymerization degree. The sulfonated poly (arylene ether) copolymer according to claim 1, further comprising a repeating unit represented by the following formula (11):
(11)

In this formula,
Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and m is 10 to 10,000 as the degree of polymerization. The sulfonated poly (arylene ether) copolymer according to claim 1, wherein the copolymer is represented by the following Chemical Formula 3 or Chemical Formula:
(3)

[Chemical Formula 4]

In this formula,
X, M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ , M ₈ , R ₁ , R ₂ , R ₃ , R ₄ , a, b, c, d, e, f, Ar ₂ and Ar ₃ are as defined above,
p and q are molar fractions p + q = 1, 0 <p <1, 0 <q <1,
r is 10 to 10,000 as polymerization degree. The sulfonated poly (arylene ether) according to any one of claims 1 to 3, wherein the substituted or unsubstituted arylene group having 6 to 20 carbon atoms is represented by the following formula (14) or (15). Copolymer:
[Chemical Formula 14]

[Chemical Formula 15]

In this formula,
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 independently of one another are hydrogen, halogen atoms, carbon atoms of 1 to 20 Straight chain or branched alkyl group, alkenyl group having 2 to 20 carbon atoms, alkynyl group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl having 2 to 20 carbon atoms Group, a C7-C20 alkylaryl group, or a C1-C20 alkoxy group,
Y is a single bond, S, S (= O) ₂ , C (= O), P (= O) (R ₁₇ ) or C (R ₁₈ ) (R ₁₉ ), wherein R _17, R ₁₈ , R ₁₉ Are independently an aryl group having 6 to 20 carbon atoms which is unsubstituted or substituted with halogen. The sulfonated poly (arylene ether) copolymer according to claim 1, wherein the copolymer is represented by the following Chemical Formula 12 or Chemical Formula 13.
[Chemical Formula 12]

[Chemical Formula 13]

In this formula,
M ₁ to M ₈ are independently of each other hydrogen, lithium, sodium or potassium,
a and c are each independently an integer of 1 to 5,
Ar ₁ , Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
p and q are mole fractions p + q = 1, 0 <p <1, 0 <q <1,
r is 10 to 10,000 as polymerization degree. The method of claim 5, wherein Ar ₁ , Ar ₂ and Ar ₃ are

,

,

And

Sulfonated poly (arylene ether) copolymer, characterized in that the arylene group having 6 to 20 carbon atoms selected from the group consisting of:

In this formula,
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 Are independently an aryl group having 6 to 20 carbon atoms unsubstituted or substituted with halogen. 4. The sulfonated poly (arylene ether) copolymer of claim 3 wherein the ratio of p and q is from 1: 9 to 9: 1. The sulfonated poly (arylene ether) copolymer of claim 1, wherein the copolymer has a weight average molecular weight of 10,000 to 1,000,000. The sulfonated poly (arylene ether) copolymer of claim 1, wherein the copolymer is a random copolymer or a block copolymer. A polymer electrolyte membrane comprising the copolymer according to claim 3. The method of claim 10, wherein the polymer electrolyte membrane is polyimide, polyetherketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, polyphenylene sulfide, polystyrene, polytrifluoro A polymer electrolyte membrane further comprising one polymer selected from the group consisting of rostyrene sulfonic acid, polystyrene sulfonic acid, polyurethane, and branched sulfonated polysulfone ketone copolymers. The method of claim 10, wherein the polymer 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 further comprises one selected from the group consisting of. The polymer electrolyte membrane of claim 10, wherein the polymer electrolyte membrane further comprises a porous support. A membrane-electrode assembly comprising the polymer electrolyte membrane of claim 10. A fuel cell employing the polymer electrolyte membrane of claim 10. 16. The fuel cell of claim 15, wherein the fuel cell is a direct methanol fuel cell. The fuel cell according to claim 15, wherein the fuel cell is a vehicle fuel cell. As shown in Scheme 1 below,
(S1) synthesizing a copolymer represented by Formula 9 by polymerizing a monomer of Formula 5, a monomer of Formula 7 and a monomer of Formula 8; And
(S2) A method for preparing a sulfonated poly (arylene ether) copolymer represented by Formula 3 comprising introducing a sulfonic acid group into a phenyl ring portion of a copolymer of Formula 9:
[Reaction Scheme 1]

In this formula,
X is a single bond or Ar ₁ , Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ and M ₈ are independently of each other hydrogen, lithium, sodium or potassium,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, straight or branched alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, alkynyl group of 2 to 20 carbon atoms, 5 carbon atoms A cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an alkoxy group of 1 to 20 carbon atoms,
a + b = 5, c + d = 5,
a and c are each independently an integer of 1 to 5,
b, c, e and f are each independently an integer from 0 to 4,
Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
p and q are molar fractions p + q = 1, 0 <p <1, 0 <q <1,
r is 10 to 10,000 as the degree of polymerization,
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are hydrogen, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _2-20 Alkynyl groups, substituted or unsubstituted C _5-20 cycloalkyl groups, substituted or unsubstituted C _6-20 aryl groups, substituted or unsubstituted C _2-20 heteroaryl groups, substituted or unsubstituted C _7-20 alkyl An aryl group or a substituted or unsubstituted C _1-20 alkoxy group,
X ₁ and X ₂ are Cl, Br, I, or F. As shown in Scheme 2 below,
(S1) synthesizing a copolymer represented by Formula 10 by polymerizing a monomer of Formula 6, a monomer of Formula 7 and a monomer of Formula 8; And
(S2) A method for preparing a sulfonated poly (arylene ether) copolymer represented by Formula 4 comprising introducing a sulfonic acid group into a phenyl ring portion of a copolymer of Formula 10:
[Reaction Scheme 2]

In this formula,
X is a single bond or Ar ₁ , Ar ₁ is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
X ₁ and X ₂ are Cl, Br, I, or F,
M ₁ , M ₂ , M ₃ , M ₄ , M ₅ , M ₆ , M ₇ and M ₈ are independently of each other hydrogen, lithium, sodium or potassium,
R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, straight or branched alkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 20 carbon atoms, alkynyl group of 2 to 20 carbon atoms, 5 carbon atoms A cycloalkyl group of 20 to 20, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, or an alkoxy group of 1 to 20 carbon atoms,
R ' ₁ , R' ₂ , R ' ₃ and R' ₄ are hydrogen, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _2-20 Alkynyl groups, substituted or unsubstituted C _5-20 cycloalkyl groups, substituted or unsubstituted C _6-20 aryl groups, substituted or unsubstituted C _2-20 heteroaryl groups, substituted or unsubstituted C _7-20 alkyl An aryl group or a substituted or unsubstituted C _1-20 alkoxy group,
a + b = 5, c + d = 5,
a and c are each independently an integer of 1 to 5,
b, c, e and f are each independently an integer from 0 to 4,
Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
p and q are molar fractions p + q = 1, 0 <p <1, 0 <q <1,
r is 10 to 10,000 as polymerization degree. 20. The sulfonated poly (aryl) of claim 18 or 19, wherein step (S1) is carried out under one alkali metal base selected from the group consisting of potassium carbonate, sodium carbonate, sodium hydroxide, and calcium hydroxide. Ethylene ether) copolymer. 20. The process according to claim 18 or 19, wherein step (S1) is carried out under one organic solvent selected from the group consisting of toluene, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and mixtures thereof. A process for producing a sulfonated poly (arylene ether) copolymer, characterized in that 20. The method according to claim 18 or 19, wherein step (S2) comprises one copolymer of formula 9 or 10 and one sulfonic acid compound selected from the group consisting of chlorosulfonic acid, fuming sulfuric acid, triethylphosphate salt, and concentrated sulfuric acid; A method for producing a sulfonated poly (arylene ether) copolymer, characterized in that the reaction. 20. The method of claim 18 or 19, wherein after step (S1), Ar ₁ , Ar ₂ and Ar ₃ Sulfonated poly (aryl), characterized in that if at least one of the sulfane (sulfane) functional group further performs an oxidation reaction to oxidize to a sulfone functional group through an additional oxidation reaction as shown in Scheme 6 below. Ethylene ether) copolymer:
[Reaction Scheme 6]

In the above reaction formula, Z ₁ and Z ₂ are independently hydrogen, a halogen atom, a straight-chain or branched C _{1 -20} alkyl, C _{2 -20} alkenyl, C _{2 -20} alkynyl group, C _{5 -20} cycloalkyl group, C _{6 -20} aryl group, a C _2-20 heteroaryl group, C _{7 -20} alkyl, an aryl group, or C _{1 -20} alkoxy groups.