KR101543359B1 - Ion-conducting polymer based on polyphenylene structure and use thereof - Google Patents

Abstract

The present invention relates to an ion conductive polymer comprising a hydrophilic moiety having a polyphenylene structure as a basic skeleton and having hydrophilic substituents introduced into the side chain by post treatment and a hydrophobic moiety having one or more phenylene groups connected to the side chain, An ion conductor including the polymer, a molded article formed from the resin composition containing the polymer, and an electrolyte membrane formed from the resin composition containing the polymer.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ion conductive polymer based on a polyphenylene structure,

The present invention relates to an ion conductive polymer comprising a hydrophilic moiety having a polyphenylene structure as a basic skeleton and having hydrophilic substituents introduced into the side chain by post treatment and a hydrophobic moiety having one or more phenylene groups connected to the side chain, An ion conductor including the polymer, a molded article formed from the resin composition containing the polymer, and an electrolyte membrane formed from the resin composition containing the polymer.

Fuel cells are energy conversion devices that convert the chemical energy of fuels directly into electric energy, and have been developed as a next generation energy source with high energy efficiency and eco-friendly characteristics with less pollutant emissions. Proton exchange membrane fuel cells (PEMFCs) containing polymer electrolyte membranes have advantages such as low operating temperature, elimination of leakage problems due to the use of solid electrolytes, and fast operation, Devices.

In general, an electrolyte membrane used in a polymer electrolyte fuel cell can be divided into a perfluorinated polymer electrolyte and a hydrocarbon polymer electrolyte. The fluorinated polymer electrolyte is chemically stable due to a strong binding force between carbon-fluorine (CF) and a shielding effect which is a characteristic of a fluorine atom, and has excellent mechanical properties. Particularly, And has been commercialized as a polymer membrane of an electrolyte type fuel cell. Nafion (perfluorinated sulfonic acid polymer), a product of Du Pont, USA, is a typical example of a commercially available hydrogen ion exchange membrane, and has been most commercially used since it has excellent ionic conductivity, chemical stability and ion selectivity. However, the fluorinated polymer electrolyte membrane has a low utilization rate for industrial use due to its high price compared to the excellent performance, a disadvantage that the methanol permeability (methanol crossover) of methanol through the polymer membrane is high and the efficiency of the polymer membrane is decreased And therefore, researches on hydrocarbon ion exchange membranes that can be competitive in terms of price have been actively conducted.

Since the polymer electrolyte membrane used in the fuel cell must be stable under the conditions required for driving the fuel cell, the usable polymer is very limited by aromatic polyether (APE) and the like. Hydrolysis, oxidation, and reduction reactions during the operation of a fuel cell cause degradation of the polymer membrane, thereby deteriorating the performance of the fuel cell. Therefore, polyetherketone and polyethersulfone-based polyaryleneether polymers have been studied for application to fuel cells due to their excellent chemical stability and mechanical properties.

U.S. Patent No. 4,625,000 discloses a post-sulfonation process of a polyethersufone with a polymer electrolyte membrane. The post-treatment sulfonation method disclosed in the above document uses a strong acid such as sulfuric acid as a sulfonating agent and randomly introduces a sulfonic acid group (-SO ₃ H) into the polymer skeleton, so that the distribution of sulfonic acid groups, It is difficult to control the position, number, and the like.

In addition, European Patent No. 1,113,517 A2 discloses a block copolymer polyelectrolyte membrane composed of a block having a sulfonic acid group and a block having no sulfonic acid group. There is a problem such that the chemical bond of the aliphatic polymer is decomposed during the sulfonation process because the block copolymer composed of the aliphatic block and the aromatic block is sulfonated using sulfuric acid which is a strong acid, It is difficult to control the position and number of sulfonic acid groups in the polymer skeleton.

On the other hand, Japanese Patent Application Laid-Open No. 2003-147074 discloses a method of introducing a sulfonic acid group into a fluorene of a polymer by using a chlorosulfonic acid (HSO ₃ Cl) or a sulfuric acid as a copolymer containing a fluorene compound Method. In this method, a sulfone group is randomly introduced into a ring constituting a fluorene compound.

The polymer sulfonation methods proposed in the above-mentioned prior arts have the disadvantages that when the sulfonate group content (sulfonation degree: DS, degree of sulfonation) is increased in order to realize hydrogen ion conductivity similar to that of commercialized Nafion, Dupont, The water content and the methanol content are excessively increased to dissolve the electrolyte membrane in methanol, and the mechanical densities of the electrolyte membranes are remarkably decreased, failing to satisfy the physical properties of the electrolyte membrane required for fuel cell operation.

On the other hand, Fujimoto et al. (Macromolecules, 2005, 38: 5010-5016) disclosed in Macromolecules can reduce the cost and thermal stability of conventional thermoplastic sulphonation, In order to improve the stability lower than Nafion, a complete aromatic polymer was prepared and then sulfonated to produce an ion conductive polymer. However, the thermo-chemical stability of the polymer is improved, but the polymer is difficult to be formed into a membrane due to its rigid chemical structure.

In order to provide an electrolyte membrane for a fuel cell which exhibits a high ionic conductivity and an excellent chemical stability at the same time, the present inventors have found that by introducing a hydrophilic functional group such as a sulfonic acid group selectively to the pendant phenyl group substituted on the side chain, and densely and locally sulfonated Polymer structure capable of inducing effective phase separation between a hydrophilic domain and a hydrophobic domain by forming a polymer structure and further constituting a polymer skeleton as a carbon-carbon bond without a highly reactive ether bond (-O-), thereby achieving chemical stability against various radicals The polymer was designed.

The present invention provides an ion conductive polymer comprising a hydrophilic phenylene repeating unit represented by the following formula (1) and a hydrophobic phenylene repeating unit represented by the following formula (2) in a polymer backbone:

[Chemical Formula 1]

(2)

In the above formulas,

R ₁ to R ₃ are each independently a hydrogen atom (-H); An aryl group substituted with at least one sulfonic acid group (-SO ₃ H), a phosphonic acid group (-PO ₃ H ₂ ), or a carboxylic acid group (-CO ₂ H) or an alkali metal salt thereof; Or a perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group, and the perfluoro compound includes at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof,

R ₄ each independently represents a hydrogen atom, a fluorine atom, an aryl group, a perfluoroalkyl group, or a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in its chain, a perfluoroaryl group or a -O-purple Lt; / RTI >

Provided that at least one of R ₁ to R ₃ is an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof;

,

,

또는

이고,Ar ₁ is selected from the group consisting of phenylene, phenylene substituted with one or more fluorine, pyridinylene, pyridazinylene, pyrimidinylene, biphenylene, But are not limited to, bipyridinylene, naphthylene, anthracenylene, pyrenylene,

,

,

or

ego,

In this case, J is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - (C (CF _{3) 2} ) -;

또는

이고,Ar ₂ is

or

ego,

Here, R ₁₀ to R ₁₇ are each independently a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group,

T represents a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -ego;

W is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -;

R ₅ to R ₉ each independently represent a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group;

a is an integer of 0 to 10;

The present invention also provides a compound comprising a repeating unit represented by the following Formula 3:

(3)

In the above formulas,

R ₁ to R ₃ are each independently a hydrogen atom; An aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof; Or a perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group, and the perfluoro compound includes at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof,

R ₄ each independently represents a hydrogen atom, a fluorine atom, an aryl group, a perfluoroalkyl group, or a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in its chain, a perfluoroaryl group or a -O-purple Lt; / RTI >

Provided that at least one of R ₁ to R ₃ is an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof;

,

,

또는

이고,Ar ₁ is selected from the group consisting of phenylene, phenylene substituted with one or more fluorine, pyridinylene, pyridazinylene, pyrimidinylene, biphenylene, bipyridinylene, naphthylene, anthracenylene, pyrenylene,

,

,

or

ego,

In this case, J is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - (C (CF _{3) 2} ) -;

또는

이고,Ar ₂ is

or

ego,

Here, R ₁₀ to R ₁₇ are each independently a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group,

T represents a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -ego;

W is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -;

R ₅ to R ₉ each independently represent a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group;

a is an integer of 0 to 10,

x is an integer of 1 to 1,000,

y is an integer from 1 to 10,000,

and n is an integer of 1 to 1,000.

Further, the present invention provides a process for preparing the ion conductive polymer or compound, comprising the steps of: preparing a first compound containing at least one aromatic ring and containing cyclopendienes at both ends; A second step of preparing, as dienophiles, a second compound comprising at least one aromatic ring and an alkyne group; A third step of mixing the first compound and the second compound to prepare a hydrophilic precursor having reactive functional groups at both terminals by the Diels-Alder reaction represented by the following Reaction Scheme 1; A fourth step of mixing a hydrophilic precursor prepared from the third step with a hydrophobic monomer of formula (2) to form a copolymer; And a fourth step of post-treating the copolymer to introduce a sulfonic acid group, a phosphonic acid group, a nitric acid group, a halogen atom or a carboxylic acid group as a substituent.

[Reaction Scheme 1]

The present invention also provides an ion conductor comprising the polymer.

Further, the present invention provides a molded article formed from the resin composition containing the polymer.

Still further, the present invention provides a battery having an electrolyte membrane formed from a resin composition containing a polymer.

Hereinafter, the present invention will be described in detail.

The ion conductive polymer according to the present invention comprises a hydrophilic portion having a polyphenylene structure as a basic skeleton and having hydrophilic substituents introduced into the side chain by post treatment and a hydrophobic portion having at least one phenylene group connected to the side chain, Is bonded to the backbone of the polymer through an electron-withdrawing group to maintain hydrophobicity because a substituent is not introduced into the side chain even if a post-treatment for introducing a hydrophilic substituent is carried out. The polymer according to the present invention has a rigid backbone structure in which an aromatic ring compound such as a phenylene group or an arylene group is directly bonded. The hydrophilic substituents introduced by post-treatment are selectively added to only the so-called pendant phenyl group It is characterized by the fact that it combines to form a dense, localized sulfonated structure. Accordingly, since the polymer according to the present invention is formed into a carbon-carbon bond without an ether bond having a high chemical reactivity in the main chain, the chemical stability against various radicals is improved and effective phase separation of the hydrophilic part and the hydrophobic part can be induced.

The "pendant" broadly refers to a functional group bonded to a side chain other than an element constituting the main chain skeleton, particularly an aromatic ring substituent such as a phenyl group. These substituents may have substituents because they have more or less reactivity. The pendant is capable of introducing a substituent capable of imparting hydrophilicity to the aromatic ring substituent while protecting the arylene group forming the main chain skeleton by a three-dimensional effect in the post-treatment process, thereby controlling the degree of introduction of the substituent.

As described above, by introducing a pendant aryl group into the side chain and introducing a hydrophilic substituent such as a sulfonic acid group through a post-treatment, the hydrophilic part can be more fluidized to form a more hydrophilic channel, and more effective nano-phase separation can be induced. In addition, the degree of sulfonation may be controlled by controlling the number of pendant substituents introduced. On the other hand, since the polymer backbone skeleton is prevented from being directly sulfonated and the sulfonic acid group is located at a distance therefrom, the decomposition possibility of the polymer backbone structure that can be induced by the introduced substituent can be reduced.

A sulfonic acid group (-SO ₃ H), a phosphonic acid group (-PO ₃ H ₂ ), or a carboxylic acid group (-CO ₂ H), which are hydrophilic functional groups introduced by the post- Is introduced to impart hydrogen ion (proton, H ⁺ ) conductivity to the polymer electrolyte membrane. For the same purpose, alkali metal salts of the above acid functional groups can be used. The "alkali metal salt" may be that a cation of an alkali metal such as Na, K, Li, Rb, Cs or Fr replaces a proton of hydrophilic functional groups. Preferably, the hydrophilic functional group may be a sulfonic acid group. The sulfonic acid group may be a sodium salt, a potassium salt, or a lithium salt, and more preferably, it may be in the form of a sodium salt, but is not limited thereto.

On the other hand, the sulfonic acid group, the phosphonic acid group, or the carboxylic acid group and the alkali metal salt thereof are hydrophilic. Therefore, when a large amount of such a substituent is introduced, the water resistance of the polymer electrolyte membrane deteriorates and the mechanical strength and density of the polymer electrolyte membrane deteriorate due to swelling It may be difficult to satisfy the physical properties of the polymer electrolyte membrane required for driving the fuel cell. Accordingly, since the polymer of the present invention contains the hydrophobic monomer represented by the above formula (2) in the skeleton, it can provide an increased mechanical strength and can effectively control the ion exchange rate.

Preferably, the molecular weight of the polymer according to the present invention may be Mn (number-average molecular weight) of 10,000 to 1,000,000 or molecular weight of Mw (weight-average molecular weight) of 10,000 to 10,000,000 . More preferably from 10,000 to 300,000, or from 10,000 to 2,000,000. When the molecular weight is low, for example, when the molecular weight is less than 10,000, film formation is difficult, the moisture content is increased, and the polymer is easily decomposed by the attack of radicals, thereby decreasing the conductivity and durability. On the other hand, when the molecular weight is high, for example, when the number average molecular weight exceeds 1,000,000 or the weight average molecular weight exceeds 10,000,000, the production of the polymer solution and formation into a film become difficult due to the rapidly increased viscosity, .

Preferably, the polymer according to the present invention may incorporate an arylene group linked to both ends of a polyphenylene moiety having a pendant aryl group in its side chain, which is capable of introducing a hydrophilic substituent into the hydrophilic moiety, via an electron withdrawing group. As described above, the present invention provides a polymer having a large molecular weight by introducing an arylene group at both ends of a polyphenylene moiety, and the arylene group is linked to the arylene group through an electron withdrawing group to form an arylene group The group is characterized by providing a non-sulfonated polymer. In addition, introduction of an arylene group connected to the electron withdrawing group can impart flexibility, so that it is easy to form during the formation of a film which may appear in a polyphenylene moiety formed only of a carbon-carbon bond in order to improve physical strength, Can be overcome.

Non-limiting examples of the electron withdrawing group include -O-, -S-, - (C = O) -, - (P = O) -, - (SO ₂ ) -, -CF ₂ - and - CF ₃ ) ₂ ) - and the like. Preferably - (C = O) -, but is not limited thereto.

In the polymer according to the present invention, the repeating units may be random, alternating, or sequential. The repeating units may be block copolymers. When sufficiently limited, the molar ratio of each repeating unit can be varied variously.

The polymer according to the present invention may be a polymer formed by using a polymer represented by the general formula (3) in which the repeating units are bonded at a certain ratio as repeating units.

(3)

In Formula 3, R ₁ to R ₃ are each independently a hydrogen atom; An aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof; Or a perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group, and the perfluoro compound includes at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof,

R ₄ each independently represents a hydrogen atom, a fluorine atom, an aryl group, a perfluoroalkyl group, or a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in its chain, a perfluoroaryl group or a -O-purple Lt; / RTI >

Provided that at least one of R ₁ to R ₃ is an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof;

,

,

또는

이고,Ar ₁ is selected from the group consisting of phenylene, phenylene substituted with one or more fluorine, pyridinylene, pyridazinylene, pyrimidinylene, biphenylene, bipyridinylene, naphthylene, anthracenylene, pyrenylene,

,

,

or

ego,

In this case, J is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - (C (CF _{3) 2} ) -;

또는

이고,Ar ₂ is

or

ego,

Here, R ₁₀ to R ₁₇ are each independently a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group,

T represents a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -ego;

W is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -;

R ₅ to R ₉ each independently represent a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group;

x is an integer of 1 to 1,000,

y is an integer from 1 to 10,000,

and n is an integer of 1 to 1,000.

The "aryl" means a functional group or substituent derived from an aromatic ring compound. The cyclic compound may be composed of only carbon atoms and may include one or more hetero atoms selected from oxygen, sulfur and / or nitrogen. For example, the carbon-only aryl group includes phenyl, naphthyl, anthracenyl and the like. Examples of the aryl group containing a hetero atom include thienyl, indolyl, Pyridinyl, and the like. The heteroatom-containing aryl may be heteroaryl, but in the present invention, it is aryl.

"Alkyl" is a saturated linear or branched structure of from 1 to 20 carbon atoms, or a saturated cyclic structure consisting of from 3 to 20 carbon atoms. For example, methyl, ethyl, n-propyl, i-propyl (isopropyl), n-butyl, i-butyl, t-butyl, n-dodecyl, cyclopropyl or cyclohexyl groups do. And may contain one or more heteroatoms selected from oxygen, sulfur and / or nitrogen in the cyclic structure.

The term "perfluoroalkyl", "perfluoroaryl", "-O-perfluoroaryl", and "perfluoroalkylaryl" Means alkyl, aryl and -O-aryl in which all of the hydrogen atoms thereof are all substituted with fluorine atoms (F).

Preferably, the ratio of x to y in Formula 3 may be 1: 1 to 1:50, more preferably 1: 3 to 1:20, but is not limited thereto. For example, in the polymer of the present invention, the hydrophilic repeating unit having an aryl group substituted with a sulfonic acid group in the side chain represented by the general formula (1) has 1 to 50, preferably 3 to 20, hydrophobic repeating units represented by the general formula Or may be a polymer formed by using a bonded polymer as a repeating unit.

이고, 이때, R₁₀ 내지 R₁₃은 모두 수소원자, T는 -(C=O)-이고; W는 -(C=O)-이며; R₅ 내지 R₉는 모두 수소원자이고; a는 0 내지 10의 정수인 것일 수 있다.Preferably, the polymer of the present invention is a compound represented by the general formula (3), wherein each of R ₁ to R ₄ is independently a hydrogen atom or an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group, , The phosphonic acid group and the carboxylic acid group may be in the form of an alkali metal salt, at least one of R ₁ to R ₄ is a hydrogen atom; Ar ₁ is phenylene; Ar ₂ is

, Wherein R ₁₀ to R ₁₃ are all hydrogen atoms and T is - (C = O) -; W is - (C = O) -; R ₅ to R ₉ are both hydrogen atoms; and a may be an integer of 0 to 10.

More preferably, R ₁ to R ₄ are each independently a hydrogen atom or an aryl group substituted with at least one sulfonic acid group, and the sulfonic acid group may be in the form of an alkali metal salt, and one of R ₁ to R ₄ is a hydrogen atom It can be a polymer.

In a specific example of the present invention, a compound represented by the following general formula (4) was prepared. At this time, three kinds of ion conductive polymers are synthesized by varying the ratio of x and y, and the molecular weight, polydispersity index, ion exchange capacity (ICE), water absorption rate, dimensional change degree and ionic conductivity (Table 1). Therefore, the polymer according to the present invention has an electrolyte membrane which satisfies physical properties required for driving a battery because it has high hydrogen ion conductivity and mechanical strength provided by a main chain skeleton connected by a carbon-carbon bond provided by a hydrophilic repeating unit .

[Chemical Formula 4]

A method for preparing a polymer according to the present invention comprises: a first step of preparing a first compound containing at least one aromatic ring and cyclopendienes at both ends; A second step of preparing, as dienophiles, a second compound comprising at least one aromatic ring and an alkyne group; A third step of mixing the first compound and the second compound to prepare a hydrophilic precursor having reactive functional groups at both terminals by the Diels-Alder reaction represented by the following Reaction Scheme 1; A fourth step of mixing a hydrophilic precursor prepared from the third step with a hydrophobic monomer of formula (2) to form a copolymer; And a fifth step of post-treating the copolymer of the fourth step to introduce a sulfonic acid group, a phosphoric acid group, a nitric acid group, a halogen atom or an acetic acid group as a substituent.

[Reaction Scheme 1]

A method for producing a polymer according to the present invention comprises preparing a hydrophilic precursor and a hydrophobic monomer, reacting them to form a copolymer, and then subjecting the copolymer to a post-treatment to form a sulfonic acid group, a phosphonic acid group or a carboxylic acid group, And a step of introducing the step

The hydrophilic precursor may be prepared by a third step which is carried out by the Diels-Alder reaction represented by the reaction scheme 1. The term "Diels-Alder reaction" of the present invention is one of the methods of synthesizing cyclic compounds, in which the cyclization of one or more unsaturated compounds by a single-step, concerted pathway it means. The Diels-Alder reaction can be used to cyclize unsaturated compounds with little or no ionic or free radical properties. The two reactants of the Diels-Alder reaction are each a diene (a conjugated system of four pi electrons) and a dienophile (a conjugate system of two pi electrons), which contains an unsaturated bond as described above, The bond may be a double or triple bond of a carbon-carbon or non-carbon atom.

Prior to the third step, the first step and the second step of preparing the two reactants of the Diels-Alder reaction, that is, the diene compound and the dienophile compound, may be separately performed. Preferably, the diene compound includes cyclopentadienes which are capable of reacting with dienophiles at both ends, and the first compound containing at least one aromatic ring forming the main chain skeleton of the polymer according to the present invention Can be prepared. Also preferably, the dienophyll compound includes an unsaturated bond as a functional group capable of reacting with a diene, and reacts with the cyclopentadienone of the first compound as a product of the Diels-Alder reaction of the third step to form a main chain skeleton of the polymer A second compound containing an alkyne group may be prepared as a reactor so as to form phenylene to be constituted. Meanwhile, the second compound may further include a plurality of phenyl groups linked with a phenyl group or an electron withdrawing group to produce a polymer having an increased molecular weight. At this time, it is preferable that the alkene group of the second compound and the other end thereof include a halogen group which is reactive so that polymerization reaction with the hydrophobic monomer occurs. The dienes according to the present invention include cyclopentadiene as a diene capable of reacting with dienophiles at both terminals, dienophiles having an alkene group as a dienophile capable of reacting with a diene at one end and halogen Since the element contains a substituted aryl group, the Diels-Alder reaction of the third step provides a hydrophilic precursor in the form of a product containing an aryl group substituted at both ends with a halogen element.

Next, the hydrophilic precursor prepared by the Diels-Alder reaction of the third step may be subjected to a fourth step of forming a copolymer by mixing with a separately prepared hydrophobic monomer represented by the general formula (2). The fourth step may be carried out by a colon coupling reaction.

The term "Colon coupling reaction " of the present invention is a coupling reaction which is carried out by reacting an aryl compound containing a halogen element with a reactive functional group in the presence of a reducing metal. The halogen element may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I). As the reducing metal, zinc (Zn), magnesium (Mg), manganese (Mn), aluminum (Al) or calcium (Ca) may be used. As the catalyst, 2,2'- bipyridine ) or triphenylphosphine (PPh _3, triphenylphosphine; TPP) of _{NiBr 2, NiCl 2, Ni (} PPh 3) 2 Cl 2, Br 2, (acac) 2 · H 2 O, (OOCCH 3) · 4H 2 O , I ₂揃 6H ₂ O or other halide salts (F <Cl <Br <I). (PPh ₃ ) ₂ Cl ₂ , sodium iodide (NaI), triphenylphosphine and zinc at a temperature of 60 to 100 ° C., preferably with DMAc (dimethylacetamide) as a solvent, for 0.5 to 100 hours . Further, after the formation of the block copolymer, the step of removing zinc, the step of washing, or the step of drying may be further included.

As described above, the hydrophilic precursor containing an aryl group substituted at both ends of the product, which is a product of the third step, can be bonded to the same molecule or an aryl group substituted with another halogen element by a colon coupling reaction. Therefore, when a compound having a halogen element bonded to the open end of the formula (2) is used as the hydrophobic monomer, the hydrophilic precursor and the hydrophobic monomer may form a random, cross-linked, block or sequentially bonded polymer. Preferably, the hydrophobic monomer having similar properties reacts preferentially to form a hydrophobic block, the hydrophilic precursor reacts preferentially to form a hydrophilic precursor block, and then these blocks recombine to form a block copolymer .

The first compound, the second compound, the hydrophilic precursor and the hydrophobic monomer used in the production of the polymer of the present invention may be prepared by preparing commercially available compounds or synthesizing them by methods known in the art.

The sulfonation can be carried out by reacting the product of the fourth step with SO ₃ and H ₂ SO ₄ , chlorosulfonic acid (HSO ₃ Cl) or trimethylsilylchlorosulfonic acid [(CH ₃ ) ₃ SiSO ₃ Cl]. As a result of the sulfonation, a sulfonic acid group (-SO ₃ H) can be introduced into the phenyl group substituted on the side chain.

Phosphone oxidation can be carried out by reacting the product of the fourth step with diethylchlorophosphate ((EtO) ₂ POCl), diphenylchlorophosphate.

Carboxylation can be carried out by introducing a carboxylic acid group (-CO ₂ H) by introducing a cyano group (-CN) or a hydroxymethyl group (-CH ₂ OH) into the product of the fourth step have.

The sulfonic acid group, the phosphonic acid group or the carboxylic acid group, or the hydrophilic repeating unit in which the alkali metal salt thereof is densely packed selectively introduced into the pendant aromatic ring substituted in the side chain through the post-treatment process forms an ion conduction channel, The hydrogen ion conductivity can be provided to the electrolyte membrane including the polymer of the present invention.

In a specific embodiment of the present invention, i) 1,4-dibromobenzene is reacted with ethynylbenzene to produce 1,4-bis (phenylethynyl) benzene (1,4- bis (phenylethynyl) benzene) and ii) oxidizing 2,2 '- (1,4-phenylene) bis (1-phenylethane- 4-phenylene bis (1-phenylethane-1,2-dione) is reacted with iii) 1,3-diphenylpropan-2-one to obtain a diene compound 4,4'- (1,4-phenylene) bis (2,3,5-triphenylcyclopenta-2,4-dienone) (4,4 '- (2,3,5-triphenylcyclopenta-2,4-dienone) M3) (FIG. 1). I) By reacting 4-bromobenzoyl chloride with chlorobenzene to obtain (4-bromophenyl) (4-chlorophenyl) methanone, methanone and reacting it with 2-methylbut-3-yn-2-ol to give (4-chlorophenyl) (4- (3- 3-methylbut-1-ynyl) phenyl) methanone), and (iii) chlorophenyl (4-chlorophenyl) (4-chlorophenyl) (4-ethynylphenyl) methanone as a dienophile (second compound), M6 (4-chlorophenyl) ) Were prepared (Fig. 1). These compounds (M3 and M6) were mixed to obtain a hydrophilic precursor (M7) at both terminals by performing a Diels-Alder reaction (Fig. 2) (PP-y / x) was obtained by conducting a colon coupling reaction with 2,5-dichlorophenyl (phenyl) methanone to obtain an ion conductive polymer precursor (PP-y / x) SPP-y / x) was synthesized (Fig. 3). At this time, a series of polymers having a controlled ratio of hydrophilic and hydrophobic parts were prepared by controlling the ratio of the hydrophilic precursor and the hydrophobic monomer used in the colon coupling reaction.

The polymer or compound according to the present invention can be used as an ion conductor by a sulfonic acid group, a phosphonic acid group or a carboxylic acid group, or an alkali metal salt thereof.

A molded article can be formed from a resin composition containing a polymer or a compound according to the present invention. Non-limiting examples of the molded body include an electrolyte membrane, a separator membrane, or a water treatment membrane.

The resin composition of the present invention may further contain various additives such as an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a defoaming agent, and a dispersant.

The resin composition comprising the polymer according to the present invention can be extruded and formed into a molded article in the form of fiber or film by any method such as spinning, rolling or casting.

For example, an electrolyte membrane can be produced by molding a resin composition containing the polymer of the present invention. Specifically, the polymer is dissolved in a solvent such as N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide or dimethylacetamide, the solution is poured into a plate such as a glass plate, and the polymer attached is dried, , Preferably 10 to 120 탆, more preferably 20 to 50 탆 thick, and then desorbed from the plate. The above-mentioned solvent is only illustrative, and the scope of the present invention is not limited thereto. Conventional organic solvents may be used as long as they dissolve the polymer and can be evaporated under the drying condition. Specifically, the same organic solvent as that used in the preparation of the polymer may be used.

The present invention provides a battery having an electrolyte membrane or a separation membrane formed from the resin composition containing the polymer or the compound.

The electrolyte membrane or separation membrane formed from the resin composition containing the polymer or compound according to the present invention has high hydrogen ion conductivity, mechanical strength and excellent chemical stability, and thus can be used as a hydrogen ion electrolyte membrane, The present invention can be used as an ion exchange membrane in a fuel cell (proton exchange membrane fuel cell aka polymer electrolyte membrane fuel cell (PEMFC), direct methanol fuel cell (DMFC), or redox flow battery.

The ion conductive polymer of the present invention comprising a hydrophilic moiety including a polyphenylene structure as a basic skeleton and having hydrophilic substituents introduced into the side chain by post-treatment and at least one phenylene group connected to the side chain is a densely packed hydrophilic sulfonic acid group Resulting in increased hydrogen ion conductivity and increased mechanical strength due to the polyphenylene skeleton. Unlike the case where the conventional repeating units are linked by an ester bond or the like, the polymer of the present invention is connected with a carbon-carbon bond and is excellent in chemical stability. Therefore, the electrolyte membrane produced by molding the resin composition containing the polymer of the present invention has high hydrogen ion conductivity, mechanical strength, and chemical stability, and thus can be utilized as an ion exchange membrane for a fuel cell driven at a high temperature.

1 is a view illustrating a process of synthesizing hydrophilic intermediates (M1 to M6) according to a specific embodiment of the present invention.
2 is a view illustrating a process of synthesizing a hydrophilic precursor (M7) according to a specific embodiment of the present invention.
3 is a view showing a process of synthesizing a polyphenylene copolymer (PP-y / x) as an intermediate and an ion conductive polyphenylene copolymer (SPP-y / x) containing a sulfonic acid group according to a specific embodiment of the present invention to be.
4 is a graph showing a typical ¹ H-NMR spectrum of an ion conductive polymer (SPP-8) according to a specific embodiment of the present invention.
5 is a graph illustrating performance of a fuel cell having an electrolyte membrane including an ion conductive polymer according to a specific embodiment of the present invention.

Hereinafter, the constitution and effects of the present invention will be described in more detail through examples. These examples are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.

Manufacturing example  1: Synthesis of hydrophilic precursor

1.1. 1,4- Bis (phenylethynyl) benz Xen (1,4- bis ( phenylethynyl ) benzene; M1 ) Synthesis of

Dibromobenzene (23.6 g, 0.1 mol), palladium acetate (0.448 g, 2 mmol) and copper (I) iodide (0.762 g, 4 mmol) were added to a 500 ml flask, , And triphenylphosphine (1.574 g, 6 mmol) were mixed in 200 ml of triethylamine and stirred for 30 minutes. Ethynylbenzene (10.4 g, 0.2 mol) was then added, and the temperature was raised to 90 ° C and reacted for 2 hours. The mixture was cooled to room temperature, washed with dichloromethane, and filtered. The filtrate was washed three times with distilled water, dried over MgSO ₄ , dried and reduced in pressure to remove the solvent to obtain a solid. The obtained product was recrystallized twice with toluene to obtain 12 g of 1,4-bis (phenylethynyl) benzene (M1).

1 H-NMR (300 MHz, CDCl ₃ ):? 7.56 (m, 8H), 7.38 (m, 6H)

1.2. 2,2 '- (1,4- Phenylene ) Bis (One- Petroleum ethane -1,2- Dion ) (2,2 '- (1,4-phenylene) bis (1-phenylethane-1,2-dione); M2 ) Synthesis of

(12 g, 0.043 mol) synthesized in Preparation 1.1 and 0.31 g (0.862 mmol) of Pd (II) iodide were mixed in 250 ml of DMSO (dimethyl sulfoxide) Lt; / RTI &gt; After cooling to room temperature, it was extracted with water and MC (methylene chloride). The organic layer was washed with NaCl solution, and water was removed with MgSO ₄ , and the solvent was removed by decompression. The obtained product was separated by flash chromatography in MC and then recrystallized with ethanol to obtain 2,2 '- (1,4-phenylene) bis (1-pentylethan-1,2-dione) 2 '- (1,4-phenylene) bis (1-phenylethane-1,2-dione); M2).

H-NMR (300 MHz, CDCl 3): δ 8.10 (s, 4H), 7.96 (d, J = 7.5 Hz, 4H), 7.68 (t, J = 7.5 Hz, 2H), 7.52 (t, J = 7.8 Hz, 4H)

1.3. 4,4 '- (1,4- Phenylene ) Bis (2,3,5- Triphenylcyclopenta -2,4- Dienon ) (4,4 '- (1,4-phenylene) bis (2,3,5-triphenylcyclopenta-2,4-diene); M3 ) Synthesis of

In a 500 ml flask, M2 (12 g, 0.035 mol) and 1,3-diphenyl-4-propanone (16.1 g, 0.076 mol) synthesized in Preparation Example 1.2 were dissolved in 300 ml ethanol and stirred at 70 ° C. When the reaction was completely dissolved, KOH aqueous solution (4.32 g / 24 mL H ₂ O) was slowly added dropwise at 78 ° C., and the temperature was raised to 85 ° C. and reacted for 3 hours.

The mixture was cooled to room temperature, washed with distilled water, filtered and washed with ethanol to obtain 4,4 '- (1,4-phenylene) bis (2,3,5-triphenylcyclopenta-2,4-dienone) 4,4 '- (1,4-phenylene) bis (2,3,5-triphenylcyclopenta-2,4-dienone); M3).

H-NMR (300 MHz, CDCl 3): δ 7.26-7.16 (m, 28H, aromatic), 6.92 (m, 4H), 6.77 (s, 4H)

1.4. (4- Bromophenyl )(4- Chlorophenyl ) Methanone ((4- bromophenyl ) (4-chlorophenyl) methanone; M4 ) Synthesis of

4-bromobenzoylchloride (20 g, 0.091 mol) and aluminum chloride (14.58 g, 0.0109 mol) were mixed in 40 mL of chlorobenzene, and the temperature was raised to 90 ° C And reacted for 3 hours. After cooling to room temperature, the mixture was precipitated in ice water and stirred to obtain a solid. The white solid was filtered and the obtained solid was recrystallized from a mixed solvent of MC and hexane (4: 1) to obtain (4-bromophenyl) (4-chlorophenyl) methanone ((4-chlorophenyl) methanone; M4).

H-NMR (300 MHz, CDCl 3): δ 7.73 (d, J = 8.5, 2H), 7.64 (s, 4H), 7.47 (d, J = 8.5, 2H), EI / MS (m / z = 294 [M])

1.5. (4- Chlorophenyl ) (4- (3-hydroxy-3- Methyl butyrate 1-yl) Phenyl ) Methanone ((4-chlorophenyl) (4- (3-hydroxy-3-methylbut-1-yl) phenyl) methanone; M5 ) Synthesis of

(17.736 g, 0.06 mol) and bis (triphenylphosphine) palladium (II) dichloride (0.066 g, 0.09 mol) synthesized in Preparation Example 1.4 were added to a 500 ml flask, (0.133 g, 0.066 mmol) and copper iodide (0.133 g, 0.66 mmol) were mixed in 300 ml of triethylamine and stirred for 30 minutes. 2-Methyl-3-butyn- -3-butyn-2-ol; 8.04 g, 0.0972 mol). After the temperature was raised to 90 ° C, the reaction was allowed to proceed for 16 hours. After cooling to room temperature, it was washed with 10% HCl solution. (4-chlorophenyl) (4- (3-hydroxy-3-methylbutyl) 1-ynyl) phenyl) methanone (M5) was washed with distilled water, filtered and used without further purification.

_{H-NMR (CDCl 3):} δ 7.04-7.9 (m, 8H, aromatic), 1.63 (s, 6H, CH 3)

1.6. (4- Chlorophenyl )(4- Ethynyl phenyl ) Methanone ((4- klorophenyl ) (4-ethynylphenyl) methanone; M6 ) Synthesis of

Dean-Stark was placed in a 1000 ml flask, and NaOH (10.17 g, 0.25 mol) was added to 100 ml of chlorobenzene and stirred. A solution of M5 dissolved in 300 ml of chlorobenzene was slowly added dropwise. The temperature was gradually raised to 130 DEG C and the reaction was carried out for 2 hours. After cooling to room temperature, it was diluted with MC and distilled water. Only the organic layer was extracted, dried with MgSO ₄ , and condensed under reduced pressure to remove the solvent. The resulting solid was recrystallized from hexane to obtain 8.5 g of (4-chlorophenyl) (4-ethynylphenyl) methanone (M6).

_{H-NMR (CDCl 3):} δ 7.76 (d, J = 7.8, 4H), 7.64 (t, J = 8.5, 2H), 7.48 (d, J = 8.5, 2H), 3.28 (s, 1H)

1.7. Diels - Alder  Hydrophilic precursor by reaction ( M7 ) Synthesis of

In a 250 ml flask, M6 (11.34 g, 0.0471 mol) synthesized in Preparation Example 1.6 and M3 (16.29 g, 0.0236 mol) synthesized in Preparation Example 1.3 were mixed in 120 ml of diphenylether and stirred. After raising the temperature to 300 DEG C, the reaction was carried out for 2 hours. The mixture was cooled to room temperature, precipitated in methanol and filtered to obtain a solid. The obtained solid was separated by MC to obtain 12 g of hydrophilic precursor M7.

1 H-NMR (300 Hz, CDCl ₃ ):? 6.30-7.71 (m, 44H, aromatic)

Manufacturing example  2: Polyphenylene Copolymer by Colon Coupling Reaction ( PP -y / x)

2,5-dichlorobenzophenone (3.5 g, 0.0139 mol) and M7 (1.94 g, 0.00174 mol) were mixed in a molar ratio of 8: 1 after removal of water on the surface of the 50-ml flask, (Triphenylphosphine) nickel (II) dichloride (0.3 g, 0.00047 mol), sodium iodide (0.28 g, 0.00188 mol), triphenylphosphine (1.48 g, 0.00564 mol ) And zinc fine powder (1.23 g, 0.0188 mol) in 20 ml of dimethylacetamide, followed by stirring. After reacting at 80 ° C for 3 hours, it was cooled to room temperature and precipitated in a 5% HCl methanol solution. The precipitated solid was filtered, washed again with methanol and dried to obtain 4 g of a polymer substance (PP-8).

3 g (0.0119 mol) of 2,5-dichlorobenzophenone and 2.22 g (0.00199 mol) of M7 were mixed in a molar ratio of 6: 1 and bis (triphenylphosphine) nickel (II) dichloride (0.27 g, 0.00042 mol ), Sodium iodide (0.25 g, 0.00167 mol), triphenylphosphine (1.31 g, 0.00502 mol) and zinc fine powder (1.09 g, 0.0167 mol) were stirred in 20 ml of dimethylacetamide. The reaction was carried out as described above to obtain 4 g of the polymer substance (PP-6).

1 H-NMR (500 MHz, DMSO):? 7.93 - 6.38 (m, aromatic)

Manufacturing example  3: After Sulfonation  By reaction The sulfonic acid group  Containing polyphenylene copolymer ( SPP -y / x)

In a 300 ml flask, 4 g of the polymer substance prepared in Preparation Example 2 was dissolved in 80 ml of MC and stirred. After the polymer material was completely dissolved, the temperature around the flask was kept at -50 캜. Dissolved in chlrosulfonic acid (3.5 mL) and 40 mL of MC solution, and then slowly added dropwise. The mixture was stirred for 1 hour while maintaining the temperature at -50 ° C, and the temperature was slowly raised to -20 ° C. After the temperature was raised again, the mixture was stirred at room temperature for 30 minutes. The organic layer was washed with water and the residual chlorosulfonic acid was removed. The polymer washed with water was stirred in a 3% by weight K ₂ CO ₃ solution for 3 hours, filtered, and then washed with water to obtain a polymer containing sulfonic acid groups. The synthesized polymer was identified by ¹ H-NMR measurement, and the results are shown in FIG.

Example  1: Preparation of polymer membrane

0.5 g of the polymer prepared in the above Preparation Example was dissolved in 10 ml of DMSO, and then the insoluble polymer was removed using a 5 μm syringe filter. The filtered polymer solution was poured into a 8 cm x 8 cm silicon mold provided on a glass plate and dried at 80 ° C for 24 hours. The dried polymer film was further dried in a 160 [deg.] C vacuum oven for 24 hours to completely remove the inner, unremoved solvent. After drying, it was treated with 1.5 M sulfuric acid aqueous solution for 24 hours and immersed in distilled water for at least 24 hours to remove residual acid.

Example  2: Confirmation of physical properties of polymer membrane

The physical properties of the polymers prepared by the methods described in the above examples were measured and compared.

First, the proton conductivity was measured at 100% relative humidity at 25 ° C and 80 ° C using an AC impedance analyzer (Solatron 1280, Impedance / gain phase analyzer). Four prove conductivity cells were measured in the in-phase direction in the range of 0.1 to 20 kHz. The temperature was maintained for 30 minutes in the thermo-hygrostat chamber before measurement, and the conductivity was calculated by the following equation.

Where I is the distance between the electrodes, R is the impedance of the film, and S is the surface area over which the protons move.

Next, the degree of dimensional change was measured. The volume of the wet film (V _wet ) was measured after immersing the membrane in distilled water for 24 hours to measure the degree of dimensional change, and the wet film was vacuum dried again at 120 ° C for 24 hours to measure the volume (V _dry ). These measured values were substituted into the following equations to calculate the degree of dimensional change.

Finally, water uptake (WU) was measured. The water absorption rate was calculated by measuring the mass (Wwet) of the wet film and the mass (Wdry) of the dried film using the following equation.

The molecular weight was measured by measuring intrinsic viscosity. In order to measure the intrinsic viscosity, the prepared polymer was dissolved in NMP and the viscosity of the solution prepared at a concentration of 0.5 g / dl was measured in a 25 ° C. thermostat using a Ube load viscometer.

The results thus obtained are summarized in Table 1 below.

Example  3: The sulfonic acid group  Containing polyphenylene copolymer ( SPP Preparation of Membrane-Electrode Assembly for Fuel Cell Using Polymer Membrane Prepared with -y / x

Membrane-electrode assemblies for fuel cells were prepared using the polymer membranes (SPP-8 and SPP-6) according to the present invention. Specifically, each electrolyte membrane prepared in Example 1 having a size of 6 cm x 6 cm and a catalyst slurry for electrode production were prepared. At this time, the catalyst slurry was prepared by the following method. 170 mg of a 40 wt% Pt / C catalyst commercially available from E-tek, USA, 600 mg of a 5 wt% Nafion dispersion solution (DuPont Inc., USA), 870 mg of water, isopropyl alcohol ) Were mixed and stirred with ultrasonic wave for 30 minutes to uniformly mix the catalyst and Nafion. The catalyst slurry obtained by the above method was coated on a polyimide film using a Doctor Blade. At this time, the catalyst layer was formed so as to have a thickness of 200 m in a wet state after coating. The catalyst slurry was dried in an oven of nitrogen gas atmosphere at 120 DEG C for 10 hours.

Thereafter, the catalyst layer coated on the polyimide film was cut to a size of 25 cm ² , and laminated on the electrolyte membrane (about 60 μm) prepared and synthesized in Example 5 in advance. The electrolyte membrane was synthesized, synthesized and formed into a film, and then coated with a solution of 1,2-propanediol (boiling point 188 ° C) by a brushing method. The amount of the applied hydrophilic solvent was 200 mg solvent / cm ³ electrolyte membrane. A polyimide film coated with a catalyst layer on one side of the electrolyte membrane including 1,2-propanediol is aligned so that the catalyst layer faces the electrolyte membrane, and then a polyimide film is additionally attached to the outer side of the electrolyte membrane, Thereby forming a laminate.

Finally, the laminate was sandwiched between silicone rubbers, inserted between stainless steel plates, and then pressed at 120 MPa for 3 minutes at a pressure of 2 MPa using a flat plate press (Carver Inc., USA) (MEA) was prepared. The polyimide film was removed from the prepared membrane-electrode assembly and the transfer rate was calculated from the weight of the remaining catalyst layer. The calculated transfer rate was 100%.

Example  4: The sulfonic acid group  Containing polyphenylene copolymer ( SPP -y / x) using a polymer membrane prepared by using a membrane-electrode assembly for a fuel cell

In order to verify the utilization of polyphenylene copolymers (SPP-8 and SPP-6) containing sulfonic acid groups as ion-conducting polymers according to the present invention as membrane-electrode assemblies for fuel cells, membrane-electrode assemblies (Fuel Cell Technologies Inc., USA), which is a unit cell measuring device, was used to fabricate a unit cell. The unit cell was fabricated by combining a bipolar plate-membrane electrode assembly, an electron collector-bipolar plate-membrane electrode assembly-bipolar plate- Voltage curve.

Specifically, for activation of the fuel cell, it took 48 hours at 0.6 V and the humidification amount was 100 RH%. When the unit cell is driven, the ratio of the flow rate of hydrogen as an anode fuel to the air as a cathode fuel is adjusted to 1.2: 2. The current-voltage curve was measured from 0.5 V to 1.0 V in steps of 50 mV for 25 seconds. The current-voltage curve shows the current density on the X-axis and the voltage on the Y-axis, and is a representative fuel cell performance evaluation method showing the change in the current density according to the change in the voltage applied by the measuring apparatus. The results are shown in Fig. As shown in FIG. 5, the fuel cell in which the polymer membrane prepared using the polyphenylene copolymer (SPP-8 and SPP-6) containing the sulfonic acid group of the present invention was introduced, And showed a current density of 900 mA / cm ² or more. From these results, it was confirmed that when the polyphenylene copolymer containing sulfonic acid group was molded into a polymer membrane and introduced into a fuel cell as a membrane-electrode assembly, excellent performance could be obtained.

Claims (17)

An ion conductive polymer comprising a hydrophilic phenylene repeating unit represented by the following formula (1) and a hydrophobic phenylene repeating unit represented by the following formula (2) in a polymer backbone:
[Chemical Formula 1]

(2)

In the above formulas,
R ₁ to R ₃ are each independently a hydrogen atom (-H); The _{as; (-CO 2 H carboxylic acid group} ) or their alkali metal salts substituted with one or more sulfonic acid group _{(sulfuric acid group;; -SO 3} H), phosphonic acid groups _{(phosphonic acid group -PO 3 H 2} ) or carboxylic acid groups Aryl; Or a perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group, and the perfluoro compound includes at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof,
R ₄ each independently represents a hydrogen atom, a fluorine atom, an aryl group, a perfluoroalkyl group, or a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in its chain, a perfluoroaryl group or a -O-purple Lt; / RTI &gt;
Provided that at least one of R ₁ to R ₃ is an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof;
Ar ₁ is selected from the group consisting of phenylene, phenylene substituted with one or more fluorine, pyridinylene, pyridazinylene, pyrimidinylene, biphenylene, But are not limited to, bipyridinylene, naphthylene, anthracenylene, pyrenylene,

,

,

or

ego,
In this case, J is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - (C (CF _{3) 2} ) -;
Ar ₂ is

or

ego,
Here, R ₁₀ to R ₁₇ are each independently a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group,
T represents a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -ego;
W is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -;
R ₅ to R ₉ each independently represent a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group;
a is an integer of 0 to 10;
The method according to claim 1,
Wherein the polymer has a number-average molecular weight (Mn) of 10,000 to 1,000,000 or a weight-average molecular weight (Mw) of 10,000 to 10,000,000.
The method according to claim 1,
The polymer is characterized in that the benzene ring contained in the main chain is not sulfonated, phosphorylated, acetated or halogenated.
The method according to claim 1,
Wherein the polymer is a random, alternating, block, or sequential polymer.
The method according to claim 1,
A polymer having a skeleton containing a repeating unit represented by the following formula (3):
(3)

In Formula 3,
R ₁ to R ₁₇ , Ar ₁ , Ar ₂ , T, W and a are each the same as defined in claim 1,
x is an integer of 1 to 1,000,
y is an integer from 1 to 10,000,
and n is an integer of 1 to 1,000.
6. The method of claim 5,
Wherein the ratio of y to x (y / x) is 1 to 50.
7. The method according to any one of claims 1 to 6,
R ₁ to R ₄ are each independently a hydrogen atom or an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group, and the sulfonic acid group, the phosphonic acid group and the carboxylic acid group may be in the form of an alkali metal salt, ₁ to R &_lt; ₄ &gt; is a hydrogen atom;
Ar ₁ is phenylene;
Ar ₂ is

, Wherein R ₁₀ to R ₁₃ are all hydrogen atoms and T is - (C = O) -;
W is - (C = O) -;
R ₅ to R ₉ are both hydrogen atoms;
a is an integer of 0 to 10,
x is an integer of 1 to 1,000,
y is an integer from 1 to 10,000,
and n is an integer of 1 to 1,000.
8. The method of claim 7,
R ₁ to R ₄ are each independently a hydrogen atom or an aryl group substituted with at least one sulfonic acid group, and the sulfonic acid group may be in the form of an alkali metal salt, and one of R ₁ to R ₄ is a hydrogen atom,
a is 0,
x is an integer of 1 to 1,000, y is an integer of 1 to 10,000, x / y is 1 to 50,
and n is an integer of 1 to 1,000.
A compound comprising a repeating unit represented by the following formula (3):
(3)

In the above formulas,
R ₁ to R ₃ are each independently a hydrogen atom; An aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof; Or a perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group, and the perfluoro compound includes at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof,
R ₄ each independently represents a hydrogen atom, a fluorine atom, an aryl group, a perfluoroalkyl group, or a perfluoroalkylaryl group containing at least one oxygen, nitrogen or sulfur atom in its chain, a perfluoroaryl group or a -O-purple Lt; / RTI &gt;
Provided that at least one of R ₁ to R ₃ is an aryl group substituted with at least one sulfonic acid group, a phosphonic acid group or a carboxylic acid group or an alkali metal salt thereof;
Ar ₁ is selected from the group consisting of phenylene, phenylene substituted with one or more fluorine, pyridinylene, pyridazinylene, pyrimidinylene, biphenylene, bipyridinylene, naphthylene, anthracenylene, pyrenylene,

,

,

or

ego,
In this case, J is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or - (C (CF _{3) 2} ) -;
Ar ₂ is

or

ego,
Here, R ₁₀ to R ₁₇ are each independently a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group,
T represents a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -ego;
W is a single bond, -O-, -S-, - (C = O) -, - (P = O) -, - (SO 2) -, -CF 2 - or _{- (C (CF 3) 2} ) -;
R ₅ to R ₉ each independently represent a hydrogen atom; Fluorine atom; An aryl group; A perfluoroalkyl group; A perfluoroalkylaryl group containing at least one oxygen, nitrogen, sulfur or combinations thereof in the chain; A perfluoroaryl group; Or an -O-perfluoroaryl group;
a is an integer of 0 to 10,
x is an integer of 1 to 1,000,
y is an integer from 1 to 10,000,
and n is an integer of 1 to 1,000.
A method for producing a polymer according to claim 1 or a compound according to claim 9,
A first step of preparing a first compound containing at least one aromatic ring and containing cyclopendienes at both ends, respectively;
A second step of preparing, as dienophiles, a second compound comprising at least one aromatic ring and an alkyne group;
A third step of mixing the first compound and the second compound to prepare a hydrophilic precursor having reactive functional groups at both terminals by the Diels-Alder reaction represented by the following Reaction Scheme 1;
A fourth step of mixing a hydrophilic precursor prepared from the third step with a hydrophobic monomer of formula (2) to form a copolymer; And
A step of post-treating the copolymer of the fourth step to introduce a sulfonic acid group, a phosphonic acid group, a nitric acid group, a halogen atom or a carboxylic acid group as a substituent.
[Reaction Scheme 1]

11. The method of claim 10,
Wherein the fourth step is carried out by a colon coupling reaction.
11. The method of claim 10,
Wherein the substituent introduced by the post-processing formula of the fifth step is selectively introduced only into the aromatic ring bonded to the side chain other than the aromatic ring constituting the main chain skeleton.
An ion conductor comprising the polymer according to claim 1 or the compound according to claim 9.
14. The method of claim 13,
Wherein the ion conductor is formed from a resin composition comprising the polymer or the compound.
15. The method of claim 14,
Wherein the molded body is an electrolyte membrane, a separation membrane, or a water treatment membrane.
A battery comprising the polymer according to claim 1 or an electrolyte membrane or separator formed from a resin composition comprising the compound according to claim 9.
17. The method of claim 16,
A proton exchange membrane fuel cell (aka polymer electrolyte membrane fuel cell), a direct methanol fuel cell (DMFC), or a redox flow battery.

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