KR20120009789A - Proton-conducting polymer, polymer electrolyte membrane comprising polymer, cation-exchange resin comprising polymer, cation-exchange membrane comprising polymer, method for preparing polymer - Google Patents

Abstract

PURPOSE: A proton-conducting polymer is provided to reduce the use amount of a monomer for introducing a cation exchanger through a process after condensation polymerization, thereby variously using for a polymer electrolyte membrane, a cation exchange resin, or a cation exchange membrane. CONSTITUTION: A proton-conducting polymer is in chemical formula 1. In the chemical formula 1, Ar1 is a single bond, or substituted or unsubstituted C6-20 arylene group, E1 and E2 are selected from a sulfonic acid group, a sulfonated group, and a phosphate group, and R1, R2, R3, R4, R5 and R6 is hydrogen, a sulfonic acid group, a sulfonate group, a phosphate group, a substituted or unsubstituted C1-20 alkyl group, a substituted or unsubstituted C2-20 alkynyl group, a substituted or unsubstituted C5-20 cycloalkyl group, a substituted or unsubstituted C6-20 aryl, a substituted or unsubstituted C2-20 heteroaryl group, a substituted or unsubstituted C7-20 alkylaryl group, or a substituted or unsubstituted alkoxy group.

Description

Proton-conducting polymer, cation exchange resin, cation exchange membrane, and method for producing the polymer, including proton conductive polymer, cation-exchange resin comprising polymer, cation-exchange membrane comprising polymer, method for preparing polymer}

The present invention, by introducing a cation exchanger through a post-process, can reduce the amount of the monomer having a cation exchanger, as well as a proton conductive polymer that can be used as a polymer electrolyte membrane, a cation exchange resin or a cation exchange membrane, a method for producing the same, and To its use.

In order to prevent the pollution of industrial water and river water according to the industrial development of the modern society, and to secure valuable metal resources, much attention has been focused. Physical and chemical methods are known as a method for this purpose, and ion exchange methods are most commonly used as a dual chemical method.

Ion exchange is a method of recovering ions in a solution by contacting a solution with an ion exchange resin to exchange ions to be extracted from the solution with a functional group of a resin. It can be described as an extraction step for recovering from the resin to the acid or alkaline solution and a regeneration step for reusing the resin.

Ion exchange resins may be classified according to the type of ion exchange groups introduced into the base resin and the type of ion exchange resin. The functional groups are classified into cation exchange resins for removing cations in a solution by replacing cations in the solution with their own cations and anion exchange resins for removing anions in a solution by replacing anions in the solutions with their anions. In addition, the classification according to the form can be divided into granular ion exchanger and fibrous ion exchanger.

Currently, styrene-based resins incorporating ion exchangers into resins having a three-dimensional network structure made by using divinylbenzene as a crosslinking agent in styrene as a cation exchange resin are commercially available. It is chemically stable to strong acids and strong bases, and has the advantage of being capable of ion exchange in the entire pH range since sulfonic acid groups are exchangers, but when heated to 150 ° C. or higher, they are decomposed and the exchange capacity, density, and water adsorption are reduced. When heated at ℃ for 24 hours, the exchange capacity is reduced by 15 to 40%, there is a disadvantage that can not be used.

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.

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 membrane is 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 electrolyte membranes in order to impart hydrogen ion conductivity of fluorine-based membranes. Accordingly, the mechanical properties are degraded due to excessive swelling by water, 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 suppress 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 for improving the conductivity of ions has been 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 due to the increase in glass transition temperature (Tg), the polymer fluidity of the membrane is insufficient due to insufficient fluidity of the membrane. have.

One aspect of the present invention is to provide a proton conductive polymer having a novel structure with excellent processability and physical properties.

Another aspect of the invention to provide a polymer electrolyte membrane comprising the polymer.

Yet another aspect of the present invention is to provide a membrane-electrode assembly including the polymer electrolyte membrane.

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

Another aspect of the invention is to provide a cation exchange resin comprising the polymer.

Another aspect of the invention is to provide a cation exchange membrane comprising the polymer.

Another aspect of the present invention is to provide a method for producing the proton conductive polymer.

In order to achieve the above object, the present invention provides a proton conductive polymer represented by the following formula (1).

[Formula 1]

Where

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

E ₁ and E ₂ are each independently selected from hydrogen, sulfonic acid group, sulfonate group, and phosphoric acid group,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, sulfonic acid group, sulfonate group, phosphoric acid group, substituted or unsubstituted straight or branched alkyl group of 1 to 20 carbon atoms, substituted Or an unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C5-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group , A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,

Provided that at least one of E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ is a sulfonic acid group, a sulfonate group, or a phosphoric acid group, or a sulfonic acid group, a sulfonate group, or a phosphoric acid group Substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkylaryl, or alkoxy groups,

a + b = 4, c + d = 4 and a and c are each independently an integer of 1 to 4;

n is 10 to 10,000 as polymerization degree.

According to another aspect of the invention there is provided a polymer electrolyte membrane comprising the polymer.

According to another aspect of the invention there is provided a membrane-electrode assembly comprising the polymer electrolyte membrane.

According to another aspect of the invention there is provided a fuel cell comprising the polymer electrolyte membrane.

According to another aspect of the invention there is provided a cation exchange resin comprising the polymer.

According to another aspect of the invention there is provided a cation exchange membrane comprising the polymer.

According to another aspect of the invention,

Preparing a compound represented by Chemical Formula 10 by reacting a compound represented by Chemical Formula 6 to 9; And

A method of preparing a proton conductive polymer comprising: introducing a cation exchange group into a compound represented by Formula 10 to prepare a compound represented by Formula 3 below:

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

<Formula 10>

<Formula 3>

,

,

Where

R ' ₁ , R' ₂ , R ' ₃ , R' ₄ , R ' ₅ , and R' ₆ are hydrogen, a substituted or unsubstituted carbohydrate having 1 to 20 alkyl groups, or a substituted or unsubstituted carbon having 2 to 20 carbon atoms. Alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C2-C20 A heteroaryl group of 20, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,

E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, and d are as defined in claim 1,

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

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

X is Cl, Br, I, or F,

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

r is 10-10000 as a degree of polymerization.

The proton conductive polymer according to the present invention can introduce two or more, preferably four or more, up to eight cation exchangers through a post-process, thereby reducing the amount of monomer used for the introduction of the cation exchanger.

In addition, the proton-conducting polymer is not only excellent in physical properties, hydrogen ion conductivity ion exchange capacity and metal ion adsorption capacity, but also easily processed and molded into various forms, and is applicable to a wide range of applications such as polymer electrolyte membrane, cation exchange resin, and cation exchange membrane. Can be.

1 is a schematic diagram of a direct methanol fuel cell according to one embodiment of the invention.
2 is a graph showing the value of the battery voltage according to the current density of the unit cells manufactured in Examples 10 to 12 and Comparative Example 3.

Hereinafter, a proton conductive polymer according to an embodiment of the present invention, a polymer electrolyte membrane including the same, a membrane-electrode assembly including the same, a fuel cell employing the same, and a manufacturing method of the polymer will be described in more detail.

Proton conductive polymer according to an embodiment of the present invention includes a repeating unit represented by the following formula (1):

<Formula 1>

Where

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

E ₁ and E ₂ are each independently selected from hydrogen, sulfonic acid group, sulfonate group, and phosphoric acid group,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently hydrogen, sulfonic acid group, sulfonate group, phosphoric acid group, substituted or unsubstituted straight or branched alkyl group of 1 to 20 carbon atoms, substituted Or an unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C5-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group , A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,

Provided that at least one of E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ is a sulfonic acid group, a sulfonate group, or a phosphoric acid group, or a sulfonic acid group, a sulfonate group, or a phosphoric acid group Substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkylaryl, or alkoxy groups,

a + b = 4, c + d = 4 and a and c are each independently an integer of 1 to 4;

n is 10 to 10,000 as polymerization degree.

The probable ground in which the proton conductive polymer according to an embodiment of the present invention may have excellent physical properties will be described in more detail below, which is intended to help the understanding of the present invention, and thus, limits the scope of the present invention in any way. It is not intended to be.

The cation exchange group included in the polymer is preferably connected to one end of the side chain. The cation exchange group is linked to one end of the polymer side chain and can move relatively freely away from the main chain. The cation exchanger linked to the side chain may serve as a surfactant in the polymer. Therefore, the cation exchanger at the side chain end is easy to form an ion channel such as a micelle, and the size of the ion channel can be controlled by controlling the position where the cation exchanger is connected to the side chain. As a result, the proton conductive polymer can easily control the amount of water contained in the ion channel and can 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 easily permeable 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.

In the cation exchange group is capable of such a sulfonic acid group (-SO ₃ H) or a sulfonic acid base (-SO ₃ M, where M is lithium, being sodium or potassium), phosphoric acid group represented by -OPO ₃ H. In particular, the sulfonic acid group or sulfonate group is advantageous because the CS bond has a strong resistance to oxidation conditions.

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

The alkyl group, which is a substituent used in the present invention, refers to 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''),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, C1- C20 alkyl group, C1-C20 halogenated alkyl group, C1-C20 alkenyl group, C1-C20 alkynyl group, C1-C20 heteroalkyl group, C6-C20 aryl group, C6-C20 arylalkyl group, C6-C20 It may be substituted with a heteroaryl group, or a C6-C20 heteroarylalkyl group.

The alkenyl group which is a substituent used in the present invention is a straight or branched chain 1 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 moiety. Alkenyl groups may be bonded through a carbon atom comprising 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, dodecenyl, and the like. 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 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 moiety. 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 18 ring atoms, and at least one halogen substituent May be optionally substituted by. 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.

According to another embodiment of the present invention, the polymer may be a polymer additionally including a repeating unit represented by Formula 2 below:

<Formula 2>

Where

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

According to another embodiment of the present invention, the polymer may be a copolymer including a repeating unit represented by Formula 3 below:

<Formula 3>

Where

E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, and d are as defined in claim 1,

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

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, 15 to 500, 20 to 100 as the degree of polymerization, for example.

When the degree of polymerization r is less than 10, the electrolyte membrane film forming ability may decrease, and when the degree of polymerization r is greater than 10,000, problems may occur in the solubility of the electrolyte membrane.

According to another embodiment of the present invention, the substituted or unsubstituted arylene group having 6 to 20 carbon atoms in the polymer is preferably represented by one of the following formulas:

In the above equations,

R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ are each independently a straight chain of hydrogen, halogen atom, carbohydrate 1-20 Or a branched alkyl group, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, or 7 to 7 carbon atoms An alkylaryl group of 20 or an alkoxy group having 1 to 20 carbon atoms;

Y ₁ , Y ₂ , and Y ₃ are a single bond, O, S, S (= 0) ₂ , C (= 0), P (= 0) (R ₃₅ ), C (R ₃₆ ) (R ₃₇ ) , Si (R ₃₈ ) (R ₃₉ ) or C (═O) NH, wherein R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ are each independently substituted or unsubstituted with halogen having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group unsubstituted or substituted by halogen.

In addition, the R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ are each independently hydrogen, or a straight chain having 1 to 5 carbon atoms. And a chain alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), wherein Y ₁ , Y ₂ , and Y ₃ may be S or S (═O) ₂ .

In addition, R ₁ , R ₂ , R ₃ and R ₄ may be a phenyl group substituted with at least one sulfonic acid group, sulfonate group or phosphoric acid group.

According to another embodiment of the present invention, the arylene group represented by the formula in the polymer may further include a sulfonic acid group, sulfonate group or phosphoric acid group as a substituent. That is, 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 of the present invention, the polymer may be a copolymer including a repeating unit represented by Formula 4 below:

<Formula 4>

Where

E ₃ , E ₄ , E ₅ , E ₆ , E ₇ , and E ₈ are sulfonic acid groups, sulfonate groups or phosphoric acid groups,

e and f are integers from 1 to 4, g, h, i, and j are integers from 1 to 5,

Ar ₄ and Ar ₅ 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 10-10000 as a degree of polymerization.

According to another embodiment of the present invention, the ratio of p and q in the copolymer represented by Formula 3 or 4 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 problem of deterioration in physical properties or dissolution in water may be improved.

Further, according to another embodiment of the present invention, a specific example of the polymer may be a copolymer including a repeating unit represented by one of the following Chemical Formulas 5a, 5b, and 5c, but is not limited thereto:

<Formula 5a>

<Formula 5b>

<Formula 5c>

Where

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

r is 10-10000 as a degree of polymerization.

The weight average molecular weight of the polymer according to another embodiment of the present invention is, for example, 1,000 to 1,000,000, 5,000 to 500,000, 1,000 to 100,000. When the weight average molecular weight range is satisfied, the mechanical properties and chemical stability of the polymer may be improved, and the viscosity may be appropriately controlled to facilitate handling.

According to another embodiment of the present invention, the polymers represented by Formulas 3, 4, 5a, 5b, and 5c may be random copolymers or block copolymers. Preferably the polymer is a block copolymer. The block copolymer is more suitable for use as an electrolyte membrane.

The proton conductive polymer is capable of introducing two cation exchange groups into one aromatic group, so that at least two, preferably four or more, up to eight cations in R ₁ to R ₄ of Formulas 1, 3, and 4 The introduction of an exchanger is possible, for example when the cation exchanger is a sulfonic acid group, the degree of sulfonation may be about 20-40%. That is, the sulfonation degree can be achieved by controlling the molar ratio of the compound for introducing the sulfonic acid group without excessively using a monomer having a sulfonic acid group.

According to another embodiment of the present invention

Preparing a compound represented by Chemical Formula 10 by reacting a compound represented by Chemical Formula 6 to 9; And

A method of preparing a proton conductive polymer is provided, including: preparing a compound represented by the following Chemical Formula 3 by introducing a cation exchange group into a compound represented by the following Chemical Formula 10:

<Formula 6>

<Formula 7>

<Formula 8>

<Formula 9>

<Formula 10>

<Formula 3>

,

,

Where

R ' ₁ , R' ₂ , R ' ₃ , R' ₄ , R ' ₅ , and R' ₆ are hydrogen, a substituted or unsubstituted carbohydrate having 1 to 20 alkyl groups, or a substituted or unsubstituted carbon having 2 to 20 carbon atoms. Alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C2-C20 A heteroaryl group of 20, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,

E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, and d are as defined above,

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

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

X is Cl, Br, I, or F,

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

r is 10-10000 as a degree of polymerization.

In this case, for example, X is F, R ₁ to R ₄ are the same as or different from each other, H or a phenyl group, or both are phenyl groups.

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.

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

First, the copolymer represented by Formula 10 is synthesized by performing a condensation polymerization reaction of the dihydroxy monomers of Formulas 6, 7, and 9 and the dihalide 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.

In this case, with respect to 1 mol of the dihalide monomer of Formula 8, 0.1 to 0.4 mol of the dihydroxy monomer of Formula 6, the dihydroxy monomer of Formula 7 and 9 may be reacted in a molar ratio of 0.6 to 0.9 mol. When the molar ratio range of the reaction monomer is satisfied, an appropriate level of hydration can be maintained.

In this case, as a specific example of the dihydroxy monomer of Chemical Formula 6, a compound represented by the following Chemical Formula may be used, but is not limited thereto.

The dihalide monomer of Formula 8 may be a compound represented by the following Formula, but is not limited thereto:

The dihydroxy monomers of Formulas 7 and 9 may be a compound represented by the following Formula, but are not limited thereto:

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.

Next, a cation exchange group is introduced into the side chain of the compound represented by the formula (10).

Compounds for introducing the cation exchange group 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 At least one selected from the group consisting of phosphoric acid can be used.

The content of the compound for introducing the cation exchange group is added in 4 to 6 moles per mole of the compound represented by the formula (10).

If the amount of the compound for introducing the cation exchange group is less than 4 moles, the introduction ratio of the cation exchange group is low, on the contrary, if the amount of the compound for more than 6 moles, the final product is crosslinked or decomposed.

The cation exchange group introduction reaction (if the cation exchange group is sulfonic acid, the sulfonation reaction) is a compound represented by the formula (10) and a compound for introducing a cation exchange group, for example from 0 to 100 ℃, or 25 to 50 ℃ 0.1? The reaction is carried out for 2 hours.

At this time, if the reaction temperature is less than 0 ℃ can not obtain a polymer sufficiently introduced with a cationic inductor, 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 Formula 3 has a sulfone functional group, the sulfone functional group is a result of oxidation reaction of a sulfane functional group as shown in Scheme 1 below. Can be obtained as

Scheme 1

Z ₁ and Z ₂ in the scheme are independently hydrogen, a halogen atom, a straight or branched alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl of 5 to 20 carbon atoms. An alkyl group, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

The oxidation reaction is not particularly limited in the present invention, a method commonly used in this field is possible.

For example, the oxidation reaction is carried out by mixing the compound represented by the formula (3) and the oxidizing agent in a constant equivalent ratio in the presence of a solvent. 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.

Proton-conducting polymer of the present invention prepared as described above is capable of introducing two or more, preferably 4 to 8 cation exchangers through a post-process, thereby obtaining an effect of reducing the amount of monomer used for introduction of a cation exchanger.

The proton conductive polymer has excellent physical properties, ion exchange capacity, and metal ion adsorption capacity, and thus can be applied to various fields.

According to another embodiment of the present invention, a polymer electrolyte membrane including the proton conductive polymer is provided. The polymer electrolyte membrane has a low methanol permeability and high hydrogen ion conductivity by including the aforementioned proton conductive polymer. The moisture content characteristics are also excellent.

In addition, the polymer electrolyte membrane including the polymer may generally have thermal stability 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. Since it contains sulfonic acid group, it can have high hydrogen ion conductivity even at low moisture content, and it can show high dimensional stability even if it is exposed to moisture for a long time, so it can show high dimensional stability. Suitable for use in batteries, etc.

The polymer electrolyte membrane may be prepared by a conventional method in the art, except for using the proton conductive polymer according to the present invention.

That is, the proton conductive polymer is dissolved in an organic solvent such as dimethylacrylic acid (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and then cast on a glass plate, and then cast at 80 to 160 ° C. It can be prepared by the method of drying in.

At this time, in addition to the proton conductive polymer according to the present invention in the production of the polymer electrolyte membrane, the components usable in the production of the polymer electrolyte membrane in the art to which the present invention belongs may be further added.

According to one embodiment of the present invention, the polymer electrolyte membrane is polyimide, polyether ketone, polysulfone, polyethersulfone, polyetherethersulfone, polybenzimidazole, polyphenylene oxide, polyphenylene sulfide in addition to the proton conductive polymer It may further comprise one or more polymers selected from the group consisting of polystyrene, 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 is silicon oxide (SiO ₂ ), titanium oxide (TiO ₂ ), inorganic phosphoric acid, sulfonated SiO ₂ , sulfonated zirconium oxide (sufonated ZrO) ) And sulfonated zirconium phosphate (sulfonated ZrP) may further comprise at least one inorganic material selected from the group consisting of. 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 of the present invention, 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.

The polymer electrolyte membrane has excellent thermal and chemical stability and processability as it is prepared using the proton conductive polymer according to the present invention, and not only has high hydrogen ion conductivity by a substituted sulfonic acid group, but also when exposed to moisture for a long time. The polymer electrolyte membrane is excellent in performance, such as a small change in the high dimensional stability is expected to be effective in the field of battery chemistry, such as fuel cells or secondary batteries.

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 an 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.

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 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.

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 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 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 of the present invention, 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 the embodiment of the present invention may be used in all other types of fuel cells.

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.

According to another embodiment of the present invention there is provided a cation exchange resin comprising the proton conductive polymer.

The proton conductive polymer may be molded in various forms because of its excellent solubility in various solvents at room temperature. For example, it may be prepared in the form of gel, porous spherical beads, granules, etc. to be applied as a cation exchange resin. The cation exchange resin according to an embodiment of the present invention thus formed may be applied as a chromatography column including a cation exchange resin, a composite material including a cation exchange resin, a filtration member including a cation exchange resin, and the like.

According to another embodiment of the present invention there is provided a cation exchange membrane comprising the proton conductive polymer.

Since the film forming method using the proton conductive polymer is well known in the art, a detailed description thereof will be omitted. For example, the proton conductive polymer may be dissolved in an organic solvent, cast on a glass substrate, and then the solvent may be removed to prepare a film. In particular, the proton conductive polymer according to an embodiment of the present invention has excellent processability and thus is convenient for film formation.

Specifically, the cation exchange membrane according to one embodiment of the present invention is applied as a desalting membrane, a concentrated membrane, a specially selected permeable membrane, and an electrolyte membrane according to the use, such as electrodialysis, diffusion dialysis, reverse osmosis process, electrodialysis, fuel cell, etc. It can be widely used in the field. It can also be used to remove metal ion contaminants in positive and negative photoresist fabrication.

Hereinafter, preferred examples and experimental examples of the present invention are described. The following examples and experimental examples are described for the purpose of more clearly expressing the present invention, but the contents of the present invention are not limited to the following examples and comparative examples.

Example 1 Preparation of Proton Conductive Polymer

(Step 1) Condensation polymerization step

Three monomers 4,4'-dihydroxyphenylsulfone, (4,4-Dihydroxyphenylsulfone: 8.8 mmol), 1, in a two-necked round bottom flask in a nitrogen atmosphere on a device equipped with a condenser, Deanstock trap and magnetic stub. 2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenyl benzene, (1,2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenylbenzene: 1.7 mmol), 4 , 4'-difluorodiphenylsulfone (4,4'-difluorodiphenylsulfone: 10 mmol) was added thereto, and potassium carbonate (24 mmol) was added thereto. Dimethyl acetamide (70 mL) and toluene (50 mL) were used as the reaction solvent.

The temperature of the reactor was raised to 140 ° C., and an activation step for polymerization was performed for 4 hours, and then the reaction temperature was gradually raised to 165 ° C. to carry out a condensation polymerization reaction for 24 hours. At this time, by-products generated during the reaction were removed, and the reaction product obtained after the completion of the reaction was washed several times with methanol / water (1: 1, v / v). Then, vacuum dried at 60 ℃ for 1 day to prepare a copolymer of a white solid, the structure was confirmed by ¹ H-NMR.

(Step 2) cation exchanger introduction step (postsulfonation step)

5 g of the obtained oxidized copolymer was injected into a 100 mL flask. In this case, the flask was equipped with a condenser magnetic bar, and 60 mL of concentrated sulfuric acid was added thereto, followed by stirring at 45 ° C. for 12 hours to proceed with sulfonation reaction.

The obtained reaction solution was poured into distilled water to obtain a precipitate, which was washed several times with distilled water to remove residual sulfuric acid. The precipitate obtained after filtration was then vacuum dried at 120 ° C. to obtain a proton conductive polymer. The yield was as high as 94%.

Structural analysis of the final product confirmed that the synthesis was performed by ¹ H-NMR. After sulfonation, it was confirmed that alpha hydrogen of sulfonic acid group was generated near 7.3 ppm of ¹ H-NMR, and the desired sulfonation degree was synthesized by comparing area of sulfonic acid alpha hydrogen and hydrogen of other benzene.

Example 2 Preparation of Proton Conductive Polymer

4,4'-dihydroxyphenylsulfone, (4,4-Dihydroxyphenylsulfone: 8.0 mmol), 1,2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenyl benzene, (1, Example 1 except that 2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenylbenzene: 2.0 mmol) and 4,4'-difluorodiphenylsulfone (10 mmol) were used. The synthesis was carried out in the same manner. At this time, the yield was 93%.

Example 3 Preparation of Proton Conductive Polymer

4,4'-dihydroxyphenylsulfone, (4,4-Dihydroxyphenylsulfone: 7.7 mmol), 1,2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenyl benzene, (1, Example 1 except that 2-bis (4-hydroxyphenyl) -3,4,5,6-tetraphenylbenzene: 2.3 mmol) and 4,4'-difluorodiphenylsulfone (10 mmol) were used. The synthesis was carried out in the same manner. At this time, the yield was 97%.

Experimental Example 1: Measurement of sulfonation degree, molecular weight and polydispersity index

Sulfonation degree was predicted by hydrogen ion titration

The weight average molecular weight and polydispersity index (PDI) of the sulfonated poly (arylene ether) copolymers prepared in Examples 1 and 3 were measured using chromatography, and the results are shown in Table 1 below. Indicated. 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 (X 10 ³ ) Polydispersity Index (PDI) Example 1 17 193 2.27 Example 2 20 215 2.11 Example 3 23 178 2.04

Experimental Example  2: Solubility Measurement in Organic Solvents

N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylformamide (DMF), dimethyl sulfonide (DMSO), methanol (MeOH) at room temperature of the proton conductive polymers prepared in Examples 1 and 3 ) And solubility in water are 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

As shown in Table 2, the proton-conducting polymer according to the present invention has excellent solubility at room temperature in various kinds of solvents, and has a great advantage in processing for various uses.

Experimental Example 3: Measurement of Mechanical Strength

The proton conductive polymers obtained in Examples 1 to 3 and Nafion 211 from DuPont were dissolved in N-methylpyrrolidone (NMP), cast on a glass plate, and dried at 120 ° C. to prepare a cation exchange membrane. Tensile strength was measured using an Instron mechanical testing machine (model name 5540) according to ASTM D882, and the results are shown in Table 3 below.

Nafion 211 Example 1 Example 2 Example 3 Tensile Strength (Mpa) 20 42 36 27

As shown in Table 3, the proton conductive polymer of the present invention is expected to be easy to use as a cation exchange resin or a cation exchange membrane because of excellent physical and mechanical properties due to high molecular weight and excellent solubility of an organic solvent.

Example 4 Preparation of Polymer Electrolyte Membrane

5 g of the proton conductive polymer prepared in Example 1 was cast on a glass plate in 100 ml of N-methyl-2-pyrrolidone (NMP), respectively, and dried at 120 ° C. to prepare a 3 μm thick membrane.

Example 5: Preparation of Polymer Electrolyte Membrane

5 g of the proton conductive polymer prepared in Example 2 was cast on a glass plate in 100 ml of N-methyl-2-pyrrolidone (NMP), respectively, and dried at 120 ° C. to prepare a 3 μm thick membrane.

Example 6: Preparation of Polymer Electrolyte Membrane

5 g of the proton conductive polymer prepared in Example 3 was cast on a glass plate in 100 ml of N-methyl-2-pyrrolidone (NMP), respectively, and dried at 120 ° C. to prepare a 3 μm thick membrane.

Comparative Example 1: Preparation of Polymer Electrolyte Membrane

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.

Experimental Example 4: Hydrogen ion conductivity measurement

Hydrogen ion conductivity of the polymer electrolyte membranes according to Examples 4 to 6 and Comparative Example 1 was measured using impedance spectroscopy (manufactured by Solartron), and the results are shown in Table 4 below.

At this time, the impedance measurement conditions were measured by setting the frequency from 1 Hz to 1 MHz, measured in-plane (in-plane) method, all the tests were carried out while the sample is completely wet.

Experimental Example 5: Methanol Permeability Measurement

After interposing the polymer electrolyte membranes according to Examples 4 to 6 and Comparative Example 1 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, followed by distilled water. 10 μl was aliquoted per 10 minutes in a cell containing 10 μl, followed by filling 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 1 below, and the results are shown in Table 4 below.

Polymer electrolyte membrane Hydrogen ion conductivity (x10 ^-3 S / cm) Methanol permeability (x10 ^-6 cm ² / sec) Example 4 2.74 0.59 Example 5 3.75 0.79 Example 6 3.95 1.04 Comparative Example 1 3.37 2.1

As shown in Table 4, the polymer electrolyte membrane (Examples 4 to 6) made of a proton conductive polymer having a sulfonic acid group as a cation exchanger prepared according to the present invention has a high sulfonation degree and a high weight average molecular weight of a conventional polymer. Compared with the polymer electrolyte membrane of Comparative Example 1 prepared using Nafion 112, which is an electrolyte membrane, hydrogen ionic conductivity and low methanol permeability were shown to be equivalent to that of the polymer electrolyte membrane for fuel cells.

Example 7: Preparation of membrane-electrode assembly

To prepare a composition for forming the anode and the cathode, in 50 g of a mixed solvent of water, 1-propanol, and isopropyl alcohol (IPA), 19 g of Nafion 10 wt% solution (Dupont, Nafion Dispersion), Tanaka catalyst (45 wt% Pt / C) 5 g was added and uniformly dispersed using an ultrasonicator and mixer.

Using a coater to coat the prepared anode forming composition on the transfer paper at 0.2 mgPt / cm 2 based on the platinum catalyst, and the prepared cathode forming composition on the transfer paper at 0.4 mgPt / cm 2, thereby transferring the first and second transfers. A film was obtained.

Subsequently, the first and second transfer films prepared above were simultaneously disposed adjacent to one side and the other side of the polymer electrolyte membrane prepared in Example 4, and transferred under high temperature and high pressure to prepare a membrane electrode assembly. Transfer conditions were 130 ℃, 120kgf / ㎠, 5 minutes.

Example 8: Membrane-electrode Assembly Preparation

A membrane electrode assembly was prepared in the same manner as in Example 7, except that the polymer electrolyte membrane prepared in Example 5 was used.

Example 9: Preparation of membrane-electrode assembly

A membrane electrode assembly was prepared in the same manner as in Example 7, except that the polymer electrolyte membrane prepared in Example 6 was used.

Comparative Example 2: Preparation of the membrane-electrode assembly

A membrane electrode assembly was prepared in the same manner as in Example 7, except that an NRE 211 (Dupont, thickness 25um) membrane was used as the polymer electrolyte membrane.

Examples 10 to 12: Production of unit cell

The unit cells of Examples 10 to 12 were prepared by arranging gas diffusion layers (GDLs) (SBB 10BB) adjacent to both surfaces of the membrane electrode assemblies prepared in Examples 7 to 9, respectively.

Comparative Example 3: Fabrication of Unit Cell

A unit cell of Comparative Example 3 was prepared by arranging a gas diffusion layer (GDL) (SBB 10BB) adjacent to each of both surfaces of the membrane electrode assembly prepared in Comparative Example 2.

Experimental Example 6: unit cell performance test

In order to test the performance of the unit cells prepared in Examples 10 to 12 and Comparative Example 3, the temperature of the anode inlet / cell / air electrode inlet was maintained at 65/65/65 ° C., respectively, and the atmospheric pressure and pressure difference were (0 psig). The pressure was adjusted so that the unit cell was operated at a ratio of hydrogen: air = 1.5: 2.0 based on the chemical equivalent.

Operating the unit cells manufactured in Examples 10 to 12 and Comparative Example 3, and investigated the cell voltage according to the current density, the results are shown in Figure 2, wherein the current density value at the cell voltage of 0.6V Table 5 shows.

Unit cell Example 10 Example 11 Example 12 Comparative Example 3 Unit cell performance
(mA / cm ² ), 0.6V 1020 1050 1080 960

Referring to FIG. 2, the cell voltage characteristics of the unit cells prepared in Examples 10 to 12 were improved compared to the unit cells prepared in Comparative Example 3, and the voltage was increased as the degree of sulfonation of the proton conductive polymer (DS) increased. It can be seen that the characteristics are improved.

Claims (21)

Proton conductive polymer represented by the following formula (1):
<Formula 1>

Where
Ar ₁ is a single bond or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms;
E ₁ and E ₂ are each independently selected from hydrogen, sulfonic acid group, sulfonate group, and phosphoric acid group,
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are independently of each other hydrogen, sulfonic acid group, sulfonate group, phosphoric acid group, substituted or unsubstituted alkyl group of 1-20, substituted or unsubstituted Alkenyl group having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 20 carbon atoms, substituted or unsubstituted A substituted heteroaryl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
Provided that at least one of E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R _5, and R ₆ is a sulfonic acid group, a sulfonate group, or a phosphoric acid group, or a sulfonic acid group, a sulfonate group, or a phosphoric acid group Substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkylaryl, or alkoxy groups,
a + b = 4, c + d = 4, and a and c are each independently an integer of 1 to 4;
n is 10 to 10,000 as polymerization degree. The proton conductive polymer of claim 1, wherein the polymer further comprises a repeating unit represented by Formula 2 below:
<Formula 2>

Where
Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms;
m is 10 to 10,000 as polymerization degree. The proton conductive polymer of claim 1, wherein the polymer comprises a repeating unit represented by Formula 3 below:
<Formula 3>

Where
E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, and d are as defined in claim 1,
Ar ₁ is a single bond or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms;
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 10-10000 as a degree of polymerization. The proton conductive polymer of claim 3, wherein the substituted or unsubstituted arylene group having 6 to 20 carbon atoms is represented by one of the following formulas:

In the above equations,
R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ are each independently a straight chain of hydrogen, halogen atom, carbohydrate 1-20 Or a branched alkyl group, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, a heteroaryl group of 2 to 20 carbon atoms, or 7 to 7 carbon atoms An alkylaryl group of 20 or an alkoxy group having 1 to 20 carbon atoms;
Y ₁ , Y ₂ , and Y ₃ are a single bond, O, S, S (= 0) ₂ , C (= 0), P (= 0) (R ₃₅ ), C (R ₃₆ ) (R ₃₇ ) , Si (R ₃₈ ) (R ₃₉ ) or C (═O) NH, wherein R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ are each independently substituted or unsubstituted with halogen having 1 to 20 carbon atoms. It is an alkyl group or a C6-C20 aryl group unsubstituted or substituted by halogen. The method according to claim 4, wherein R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , and R ₃₄ are independently of each other hydrogen or carbohydrate A proton conductive polymer of 1 to 5 straight alkyl groups, wherein Y ₁ , Y ₂ , and Y ₃ are S or S (═O) ₂ . The proton conductive polymer of claim 3, wherein R ₁ , R ₂ , R _3, and R ₄ are phenyl groups substituted with at least one sulfonic acid group, sulfonate group, or phosphoric acid group. The proton conductive polymer of claim 3, wherein the polymer comprises a repeating unit represented by Formula 4 below:
<Formula 4>

Where
E ₃ , E ₄ , E ₅ , E ₆ , E ₇ , and E ₈ are sulfonic acid groups, sulfonate groups or phosphoric acid groups,
e and f are integers from 1 to 4, g, h, i, and j are integers from 1 to 5,
Ar ₄ and Ar ₅ 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 10-10000 as a degree of polymerization. The proton conductive polymer of claim 3, wherein the polymer is a copolymer including a repeating unit represented by one of Formulas 5a, 5b, and 5c:
<Formula 5a>

<Formula 5b>

<Formula 5c>

Where
p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1,
r is 10-10000 as a degree of polymerization. The proton conductive polymer of claim 3, wherein the polymer is a random copolymer or a block copolymer. The proton conductive polymer of claim 1, wherein the polymer has a weight average molecular weight of 10,000 to 1,000,000. A polymer electrolyte membrane comprising the proton conductive polymer according to any one of claims 1 to 10. The method according to claim 11, 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. 12. The method of claim 11, 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 comprising one inorganic material selected from the group consisting of. 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. 17. The fuel cell of claim 16, wherein the fuel cell is a vehicle fuel cell. A cation exchange resin comprising the proton conductive polymer according to any one of claims 1 to 10. A cation exchange membrane comprising the polymer according to any one of claims 1 to 10. Preparing a compound represented by Chemical Formula 10 by reacting a compound represented by Chemical Formula 6 to 9; And
A method of preparing a proton conductive polymer comprising: introducing a cation exchange group into a compound represented by Formula 10 to prepare a compound represented by Formula 3 below:
<Formula 6>

<Formula 7>

(8)

&Lt; Formula 9 >

<Formula 10>

<Formula 3>

,
Where
R ' ₁ , R' ₂ , R ' ₃ , R' ₄ , R ' ₅ , and R' ₆ are hydrogen, a substituted or unsubstituted carbohydrate having 1 to 20 alkyl groups, or a substituted or unsubstituted carbon having 2 to 20 carbon atoms. Alkenyl group, substituted or unsubstituted C2-C20 alkynyl group, substituted or unsubstituted C5-C20 cycloalkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C2-C20 A heteroaryl group of 20, a substituted or unsubstituted alkylaryl group having 7 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms,
E ₁ , E ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, and d are as defined in claim 1,
Ar ₁ is a single bond or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
Ar ₂ and Ar ₃ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
X is Cl, Br, I, or F,
p and q are mole fractions, p + q = 1, 0 <p <1, 0 <q <1,
r is 10-10000 as a degree of polymerization.

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