KR20180047376A - Polymer electrolyte membrane, membrane electrode assembly comprising the same and fuel cell comprising the same - Google Patents

Abstract

The present invention relates to a polymer electrolyte membrane, to a membrane electrode assembly comprising the same and to a fuel cell comprising the same. The polymer electrolyte membrane according to one embodiment of the present invention secures mechanical properties through blending of a block copolymer and a random copolymer, and has excellent current density values under a low humidification operating condition.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer electrolyte membrane, a membrane electrode assembly including the same, and a fuel cell including the membrane electrode assembly. [0002]

TECHNICAL FIELD The present invention relates to a polymer electrolyte membrane, a membrane electrode assembly including the membrane electrode assembly, and a fuel cell including the membrane electrode assembly.

Research on the application of hydrocarbon polymer as an electrolyte membrane in polymer electrolyte fuel cell (FEA) has been carried out. Generally, in the case of the hydrocarbon-based electrolyte membrane, the unit cell performance is equivalent to that of the fluorine electrolyte membrane at a sufficient humidification condition (> 50% RH), whereas in the low humidification region (<RH 50%), Lt; RTI ID = 0.0 &gt; current density &lt; / RTI &gt;

Therefore, research is underway to improve the mechanical durability that occurs mainly in the RH cycle test through blending.

Korean Patent Publication No. 2009-0039180

The present invention provides a polymer electrolyte membrane, a membrane electrode assembly including the membrane electrode assembly, and a fuel cell including the membrane electrode assembly.

According to one embodiment of the present invention, a block copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And a random copolymer comprising a repeating unit represented by the following formula (3): &lt; EMI ID =

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

G1 to G4 are the same or different and are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; -PO ₃ ^2- 2M ^+; Hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, g1 to g4 are the same or different from each other and independently represent an integer of 0 to 4; when g1 to g4 are an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, Is a metallic element,

a and a 'are an integer of 1 or more, a: a' is 1,000: 1 to 5: 1,

b and b 'are an integer of 1 or more, b: b' is 1,000: 1 to 5: 1,

n is an integer of 1 or more and 100,000 or less,

m is an integer of 1 or more and 100,000 or less,

A1, B1, V1 and V2 are the same as or different from each other, and each independently represents one selected from the following formulas (1-1) to (1-3)

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 through 1-3,

X1 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,

S1 to S10 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, c to l are the same as or different from each other, and each independently is an integer of 0 to 4, and when c to l are an integer of 2 or more, the substituents in the parentheses are the same or different,

U1 and U2 are the same or different and are each independently selected from any one of the following formulas (1-4) to (1-7)

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

In Formulas 1-4 to 1-7,

X2 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,

T1 and T2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

T3 to T6 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

T7 and T8 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Lt; ₉ &gt; each independently represent -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

M is a metallic element,

q and v are the same or different and each independently an integer of 0 to 4, w and x are the same or different and each independently an integer of 0 to 3, y is an integer of 1 to 4, q to y Q + r? 8, 1? S + t + u + v? 16, and 1? W + x? 6, wherein the substituents in the parentheses are the same or different from each other,

A2 and B2 are the same or different from each other and each independently represents any one selected from the following formulas (1-8) to (1-10)

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

In Formulas 1-8 to 1-10,

X13 to X17 are the same or different from each other, and each independently is a direct bond, -CO-; And -SO ₂ - and any one selected from,

J1 to J8 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Y3 to Y5 are the same or different and are each independently a direct bond; Or an alkylene group having 1 to 60 carbon atoms,

j1 to j3, j6 and j8 are the same or different and each independently an integer of 0 to 4, j4, j5 and j7 are the same or different and each independently an integer of 0 to 3, j1 to j8 are 2 or more The substituents in parentheses are the same or different from each other,

W1 to W3 are the same or different from each other and each independently represents a repeating unit represented by the following formula (1a) in A2, a repeating unit represented by the following formula (1b)

[Formula 1a]

[Chemical Formula 1b]

In the above general formulas (1a) and (1b)

n 'and m' are an integer of 1 or more and 100,000 or less,

A1, B1, U1 and V1 are as defined in the above formulas (1) and (2).

According to one embodiment of the present disclosure, there is provided a membrane electrode assembly (MEA) comprising the above-described polymer electrolyte membrane.

Further, according to one embodiment of the present invention, there is provided a fuel cell including the membrane electrode assembly described above.

The polymer electrolyte membrane according to one embodiment of the present invention secures mechanical properties through blending of a block copolymer and a random copolymer, and has excellent current density values under low humidification operating conditions.

1 is a schematic view showing an electricity generation principle of a fuel cell.
2 is a schematic view showing an embodiment of a fuel cell.
FIG. 3 is a graph showing tensile strengths of the polymer electrolyte membranes prepared in Examples 1-1 to 1-3 and Comparative Examples 1 and 2 according to the present invention, and a unit using the membrane electrode assembly of the prepared polymer electrolyte membrane FIG. 5 is a graph showing the performance evaluation results of the battery. FIG.

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

Whenever a component is referred to as "comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

As used herein, the term "unit" means a structure in which a monomer is repeatedly contained in a polymer, and the monomer is bonded to the polymer by polymerization.

In this specification, the meaning of "including a unit" means that it is included in the main chain in the polymer.

As used herein, the term "electrolyte membrane" is a membrane capable of ion exchange, and includes a membrane, an ion exchange membrane, an ion transport membrane, an ion conductive membrane, an ion exchange membrane, A transfer electrolyte membrane, an ion conductive electrolyte membrane, and the like.

In the present specification, the term "block copolymer" refers to a polymer formed of two or more monomers. In addition to the copolymerization mode in which a hydrophilic block and a hydrophobic block form a main chain structure, one block forms a main chain structure And a copolymer of a graft polymerization type in which the other block forms a branched structure. On the other hand, the polymer used in the present application is not limited to the above-mentioned block copolymer, and a polymer including a fluorine-based element may also be used. At this time, the polymer including a fluorine-containing element may also include a functional group, which may be hydrophilic. For example, the functional group is -SO ₃ H, -SO ₃ ^- M a ^+, and ^{_{-PO 3 2- 2M + - M +}} , -COOH, -COO - M +, -PO 3 H 2, -PO 3 H And the like. Here, M may be a metallic element.

As used herein, "blended copolymer" means a copolymer in which a block copolymer and a random copolymer are contained at a constant weight ratio.

As used herein, the term "hydrocarbon-based" means an organic compound consisting solely of carbon and hydrogen, and includes, but is not limited to, linear, branched or cyclic hydrocarbons. It may also include, but is not limited to, a single bond, a double bond, or a triple bond.

In the present specification, the term "fluorine-based conjugate" means that part or all of the carbon-hydrogen bond in the hydrocarbon system is substituted with fluorine.

Examples of substituents in the present specification are described below, but are not limited thereto.

In the present specification, the term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the substituent is a substitutable position, When the substituent is more than two, the two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" A halogen group; A nitrile group; Sulfonic acid base; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heteroaryl group, or does not have any substituent (s).

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety bonded to another substituent or bond.

In the present specification, the sulfonic acid base can be expressed as -SO ₃ M, and M can be hydrogen or a metallic element. For example, the sulfato group may be -SO ₃ H, -SO ₃ Na, or -SO ₃ K, but is not limited thereto.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a n-propyl group, an isopropyl group, a butyl group, a n-butyl group, an isobutyl group, N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, N-octyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 50 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but may have from 6 to 50 carbon atoms, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. Examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and the like. Examples of the polycyclic aryl group include a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, A naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group,

In the present specification, the heteroaryl group includes one or more atoms other than carbon, that is, a heteroatom. Specifically, the heteroatom includes an atom selected from the group consisting of N, P, O, S, Se, 1 or more. The number of carbon atoms is not particularly limited, but is preferably 2 to 50 carbon atoms. According to one embodiment, the heteroaryl group has 2 to 30 carbon atoms. According to another embodiment, the heteroaryl group has 2 to 20 carbon atoms. The heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, A thiazolyl group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidyl group, A benzoimidazolyl group, a benzothiazolyl group, a benzothiazolyl group, a benzothiophene group, a dibenzothiophene group, a benzoimidazolyl group, a benzoimidazolyl group, a benzimidazolyl group, A furanyl group, a dibenzofuranyl group, a naphthobenzofuranyl group, a phenanthroline group, a thiadiazolyl group, a phenothiazinyl group, an acenaphthoquinoxalyl group, an indenoquinazolyl group, an indenoisoquinolyl group Group, an indenoquinolyl group, a pyridinyl group, a phenoxazinyl group, a benzoquinazolyl group, Group, benzo Perry MIDI quinolyl group, a benzo group and Perry media include, but RY Loa acridine fluorenyl group, and the like.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy and the like, no.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 50. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl and styrenyl groups. no.

In the present specification, the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group and a phenylsilyl group. It is not.

In the present specification, the boron group may be represented by the formula of -BRaRb, wherein Ra and Rb are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-alkylarylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine group, and a heteroarylamine group. The number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples of the amine group include methylamine, dimethylamine, ethylamine, diethylamine, phenylamine, naphthylamine, biphenylamine, anthracenylamine, 9- A diphenylamine group, an N-phenylnaphthylamine group, a ditolylamine group, an N-phenyltolylamine group, a triphenylamine group, an N-phenylbiphenylamine group, an N-phenylnaphthylamine group, A naphthylamine group, a naphthylamine group, an N-naphthylfluorenylamine group, an N-phenylphenanthrenylamine group, an N-biphenylphenanthrenylamine group, an N-phenylfluorenylamine group, , An N-phenanthrenyl fluorenylamine group, and an N-biphenylfluorenylamine group, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having two or more of the aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be the same as the aryl group described above.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group containing two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group can be applied to the description of the above-mentioned heteroaryl group.

In the present specification, the aryl group in the arylamine group, the aryloxy group, the aralkyl group, and the alkylaryl group may be an explanation of the aryl group described above.

In the present specification, the alkyl group in the haloalkyl group, the alkylamine group, the alkylsilyl group, the alkoxy group, the aralkyl group and the alkylaryl group is applicable to the description of the alkyl group described above.

In the present specification, examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, an m-tolyloxy group, a 3,5-dimethylphenoxy group, a 2,4,6- trimethylphenoxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1- Anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group and the like.

In the present specification, the hydrocarbon ring is a substituted or unsubstituted monocyclic or polycyclic aliphatic or aromatic ring consisting only of carbon and hydrogen.

In the present specification, the heterocyclic ring may be an aliphatic heterocyclic ring or an aromatic heterocyclic ring and may be selected from the group consisting of heteroatoms such as N, P, O, S, Se, Ge and Si in place of carbon atoms in the hydrocarbon ring Quot; refers to a structure containing at least one atom to be bonded.

In the present specification, the aromatic ring may be a substituted or unsubstituted aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may be monocyclic or polycyclic.

In the present specification, the description of the aryl group for the aromatic hydrocarbon ring can be applied.

In this specification, the aromatic heterocycle includes a structure containing at least one atom selected from the group consisting of heteroatoms such as N, P, O, S, Se, Ge and Si in place of carbon atoms in the aromatic hydrocarbon ring And the description of the heteroaryl group can be applied.

In the present specification, the aliphatic ring may be a substituted or unsubstituted aliphatic hydrocarbon ring or an aliphatic heterocyclic ring, and may be monocyclic or polycyclic.

In the present specification, the description of the aliphatic hydrocarbon ring for the cycloalkyl group can be applied.

In the present specification, the aliphatic heterocycle includes a structure containing at least one atom selected from the group consisting of heteroatoms such as N, P, O, S, Se, Ge and Si in place of carbon atoms in the aliphatic hydrocarbon ring it means.

In the present specification, examples of the "organic group" include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, and a heteroaryl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom. The organic group may be linear, branched or cyclic.

In the present specification, "trivalent organic group" means a trivalent group having three bonding positions to an organic compound.

Also, in the present specification, the organic group may form a cyclic structure and may form a bond including a heteroatom unless the effect of the invention is impaired. Specifically, a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═C (-B) -: B represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like, but is not limited thereto.

In the present specification, the cyclic structure may include the above-mentioned aromatic ring, aliphatic ring, and the like, and may be monocyclic or polycyclic.

In the present specification, a fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

According to one embodiment of the present invention, the block copolymer may be a copolymer including, for example, a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), but is not limited thereto.

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

a and a 'are an integer of 1 or more, a: a' is 1,000: 1 to 5: 1,

b and b 'are an integer of 1 or more, b: b' is 1,000: 1 to 5: 1,

n is an integer of 1 or more and 100,000 or less,

m is an integer of 1 or more and 100,000 or less.

According to one embodiment of the present disclosure, a is an integer greater than or equal to 2.

According to one embodiment of the present disclosure, a 'is an integer greater than or equal to 2.

According to one embodiment of the present disclosure, n is an integer greater than or equal to 2.

According to one embodiment of the present disclosure, b is an integer greater than or equal to 2.

According to one embodiment of the present disclosure, b 'is an integer greater than or equal to 2.

According to one embodiment of the present disclosure, m is an integer greater than or equal to 2.

According to one embodiment of the present invention, A1, B1, V1 and V2 may be the same or different from each other, and each independently may be represented by any one of the following formulas (1-1) to (1-3).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 through 1-3,

X1 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,

S1 to S10 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, and c to l are the same as or different from each other and each independently an integer of 0 to 4, and when c to l are an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present specification, U1 and U2 may be the same or different from each other, and each independently may be represented by any one of the following formulas 1-4 to 1-7.

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

In Formulas 1-4 to 1-7,

X2 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,

T1 and T2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

T3 to T6 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

T7 and T8 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Lt; ₉ &gt; each independently represent -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

M is a metallic element,

q and v are the same or different and each independently an integer of 0 to 4, w and x are the same or different and each independently an integer of 0 to 3, y is an integer of 1 to 4, q to y The substituents in the parentheses are the same or different from each other and 1? Q + r? 8, 1? S + t + u + v? 16, and 1? W + x?

According to one embodiment of the present invention, each of A2 and B2 may independently be represented by any one selected from the following formulas (1-8) to (1-10).

[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

In Formulas 1-8 to 1-10,

X13 to X17 are the same or different from each other, and each independently is a direct bond, -CO-; And -SO ₂ - and any one selected from,

J1 to J8 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Y3 to Y5 are the same or different and are each independently a direct bond; Or an alkylene group having 1 to 60 carbon atoms,

j1 to j3, j6 and j8 are the same or different and each independently an integer of 0 to 4, j4, j5 and j7 are the same or different and each independently an integer of 0 to 3, j1 to j8 are 2 or more The substituents in parentheses are the same or different from each other,

W1 to W3 are the same or different from each other and each independently represents a repeating unit represented by the following formula (1a) in A2, a repeating unit represented by the following formula (1b)

[Formula 1a]

[Chemical Formula 1b]

In the above formulas (1a) and (1b)

n 'and m' are an integer of 1 or more and 100,000 or less,

A1, B1, U1 and V1 are as defined in the above formulas (1) and (2).

According to one embodiment of the present invention, the formula 1-1 may be represented by the following formula 1-1-1.

[Formula 1-1-1]

In Formula 1-1-1, X1, S1, S2, c, and d are as defined in Formula 1-1.

According to one embodiment of the present disclosure, X1 is -C (Z1) (Z2) -.

According to one embodiment of the present disclosure, X1 is -CO-.

According to one embodiment of the present disclosure, X1 is -O-.

According to one embodiment of the present disclosure, X1 is -S-.

According to an exemplary embodiment of the present disclosure, wherein X1 is -SO ₂ - it is a.

According to one embodiment of the present disclosure, X1 is -Si (Z1) (Z2) -.

According to one embodiment of the present disclosure, Z1 and Z2 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

According to one embodiment of the present disclosure, Z1 and Z2 are each hydrogen.

According to one embodiment of the present invention, Z1 and Z2 are the same or different and each independently substituted or unsubstituted alkyl group.

According to one embodiment of the present invention, Z1 and Z2 are the same or different and each independently an alkyl group substituted or unsubstituted with a fluoro group.

According to one embodiment of the present invention, Z1 and Z2 are the same or different from each other and each independently is a trifluoromethyl group.

According to one embodiment of the present invention, the formula 1-2 may be represented by the following formula 1-2-1.

[Formula 1-2-1]

In Formula 1-2-1, S3 to S6 and e to h are as defined in Formula 1-2.

According to one embodiment of the present invention, the formula 1-3 may be represented by the following formula 1-3-1.

[Formula 1-3-1]

In the formula 1-3-1, S7 to S10 and i to 1 are the same as defined in the formula 1-3.

According to one embodiment of the present invention, the formula 1-1 may be represented by any one of the following formulas.

In the above structural formulas, R61 and R62 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o21 and o22 are the same as or different from each other, and each independently an integer of 0 to 4, and when o21 and o22 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the formula 1-2 may be represented by any one of the following formulas.

In the above structural formulas, R61 and R62 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o21 and o22 are the same as or different from each other, and each independently an integer of 0 to 4, and when o21 and o22 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the formula 1-3 may be represented by any one of the following formulas.

In the above structural formulas, R61 and R62 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o21 and o22 are the same as or different from each other, and each independently an integer of 0 to 4, and when o21 and o22 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, A1, B1, V1 and V2 are the same as or different from each other and can be represented by any one of the following structural formulas.

In the above structural formulas, R61 and R62 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o21 and o22 are the same as or different from each other, and each independently an integer of 0 to 4, and when o21 and o22 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, A1, B1, V1 and V2 may be the same or different from each other, and each independently may be represented by any one of the following structural formulas.

According to one embodiment of the present invention, the formula 1-4 may be represented by the following formula 1-4-1.

[Formula 1-4-1]

In Formula 1-4-1, X2, T1, T2, q and r are as defined in Formula 1-4.

According to one embodiment of the present disclosure, X2 is -C (Z1) (Z2) -.

According to one embodiment of the present disclosure, X2 is -CO-.

According to one embodiment of the present disclosure, X2 is -O-.

According to one embodiment of the present disclosure, X2 is -S-.

According to an exemplary embodiment of the present disclosure, wherein X2 is -SO ₂ - it is a.

According to one embodiment of the present disclosure, X2 is -Si (Z1) (Z2) -.

According to one embodiment of the present disclosure, Z1 and Z2 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

According to one embodiment of the present disclosure, Z1 and Z2 are each hydrogen.

According to one embodiment of the present invention, Z1 and Z2 are the same or different and each independently substituted or unsubstituted alkyl group.

According to one embodiment of the present invention, Z1 and Z2 are the same or different and each independently an alkyl group substituted or unsubstituted with a fluoro group.

According to one embodiment of the present invention, Z1 and Z2 are the same or different from each other and each independently is a trifluoromethyl group.

According to one embodiment of the present disclosure. The T1 and T2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO ₃ ^2- 2M ⁺ .

According to one embodiment of the present disclosure. The T1 and T2 are the same or different from each other, at least one is independently -SO ₃ H; Or -SO ₃ ^- M a ^+.

According to one embodiment of the present disclosure. The T1 and T2 are the same or different from each other, at least one each independently is -SO ₃ H.

According to one embodiment of the present disclosure. The T1 and T2 are the same or different and at least one another are each independently a -SO ₃ ^- M a ^+.

According to one embodiment of the present invention, the formula 1-5 may be represented by the following formula 1-5-1.

[Formula 1-5-1]

In the above formula (1-5-1), T3 to T6, s to v are as defined in formula (1-5).

According to one embodiment of the present disclosure. The T3 to T6 is the same as or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO ₃ ^2- 2M ⁺ .

According to one embodiment of the present disclosure. The T3 to T6 is the same as or different from each other, at least one is independently -SO ₃ H; Or -SO ₃ ^- M a ^+.

According to one embodiment of the present disclosure. The T3 to T6 are the same or different from each other, at least one each independently is -SO ₃ H.

According to one embodiment of the present disclosure. The T3 to T6 is the same as or different from each other, at least one is independently -SO ₃ ^- M a ^+.

According to one embodiment of the present invention, the formula 1-6 may be represented by any one of the following formulas 1-6-1 to 1-6-3.

[Chemical Formula 1-6-1]

[Chemical Formula 1-6-2]

[Chemical Formula 1-6-3]

In Formulas 1-6-1 to 1-6-3, T7, T8, w and x are as defined in Formula 1-6.

According to one embodiment of the present disclosure. The T7 and T8 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO ₃ ^2- 2M ⁺ .

According to one embodiment of the present disclosure. The T7 and T8 are the same or different from each other, at least one is independently -SO ₃ H; Or -SO ₃ ^- M a ^+.

According to one embodiment of the present disclosure. The T7 and T8 are the same or different and at least one another are each independently a -SO ₃ H.

According to one embodiment of the present disclosure. The T7 and T8 are the same or different and at least one another are each independently a -SO ₃ ^- M a ^+.

According to one embodiment of the present invention, the formula 1-7 may be represented by the following formula 1-7-1.

[Formula 1-7-1]

In the above formula (1-7-1), T9 and y are the same as defined in the formula (1-7).

According to one embodiment of the present disclosure. Lt; ₉ &gt; each independently represent -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to one embodiment of the present disclosure. T9 is the case where y is 1 -SO ₃ H; Or -SO ₃ ^- M ^+, and not less than 2, y is at least one of the two or more T9 are each independently a -SO ₃ H; Or -SO ₃ ^- M a ^+.

According to one embodiment of the present invention, the formula 1-4 may be represented by any one of the following formulas.

In the above formula, Q1 and Q2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; B1 and b2 are the same or different and each independently represents an integer of 0 to 4, 1? B1 + b2? 8, and b1 and b2 represent a When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula 1-5 may be represented by the following structural formula.

In the above formula, Q1 and Q2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b11 and b12 are the same or different and each independently an integer of 0 to 8, 1? B11 + b12? 8, When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula 1-6 may be represented by any one of the following formulas.

In the above formula, Q1 and Q2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; B1 'and b2' are the same or different and each independently represents an integer of 0 to 6, 1? B1 '+ b2'? 6, and m is an integer of 0 to 6, When b1 'and b2' are an integer of 2 or more, the substituents in parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula 1-7 may be represented by the following structural formula.

Wherein at least one of Q &lt; ₄ &gt; is independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b4 is an integer of 1 to 4, and b4 is an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, U1 and U2 may be the same or different from each other, and each independently may be represented by any one of the following structural formulas.

In the above formula, Q1 and Q2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of Q &lt; ₄ &gt; is each independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b1 and b2 are the same or different and each independently an integer of 0 to 4, b1 'and b2' are the same or different and independently B1 '+ b2'? 6 and 1? B11, where b11 and b12 are the same or different and each independently an integer of 0 to 8, b4 is an integer of 1 to 4, + b12 8; and when b1, b2, b4, b1 ', b2', b11 and b12 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the formula 1-8 may be represented by the following formula 1-8-1.

[Formula 1-8-1]

In the above formula (1-8-1), the definition of the substituents is as defined in the formula (1-8).

According to one embodiment of the present disclosure, X13 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X13 is -SO ₂ - it is a.

According to one embodiment of the present disclosure, X14 is-CO-.

According to an exemplary embodiment of the present disclosure, wherein X14 is -SO ₂ - it is a.

According to one embodiment of the present disclosure, X15 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X15 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula 1-9 may be represented by the following formula 1-9-1.

[Chemical Formula 1-9-1]

In the above general formula 1-9-1, the definition of the substituents is as defined in the general formulas 1-9.

According to one embodiment of the present disclosure, X16 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X16 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula 1-10 may be represented by the following formula 1-10-1.

[Chemical Formula 1-10-1]

In the above formulas 1-10-1, the definition of the substituents is as defined in formulas 1-10.

According to one embodiment of the present disclosure, X &lt; 17 &gt; is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X17 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula 1-8 may be represented by any one of the following formulas.

In the above structural formulas, J11 to J14 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, j11 to j13 are the same or different from each other and independently represent an integer of 0 to 4, j14 is an integer of 0 to 3, and when j11 to j14 are each an integer of 2 or more, the substituents in the parentheses are the same And the definitions of the remaining substituents are as defined in the general formulas 1-8.

According to one embodiment of the present invention, the formula 1-9 may be represented by any one of the following formulas.

In the above structural formulas, J15 and J16 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group; j15 is an integer of 0 to 3; j16 is an integer of 0 to 4; when j15 and j16 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, 1-9.

According to one embodiment of the present invention, the formula 1-10 may be represented by any one of the following formulas.

In the above structural formulas, J17 and J18 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group; j17 is an integer of 0 to 3; j18 is an integer of 0 to 4; when j17 and j18 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, As defined in 1-10.

According to one embodiment of the present invention, each of A2 and B2 may be represented by any one of the following structural formulas.

In the above structural formulas, J11 to J18 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group,

j11 to j13, j16 and j18 are the same or different and each independently an integer of 0 to 4, j14, j15 and j17 are the same or different and each independently an integer of 0 to 3, j11 to j18 are each 2 The substituents in the parentheses are the same as or different from each other, and the definitions of the remaining substituents are as defined in formulas 1-8 to 1-10.

According to one embodiment of the present invention, the random copolymer may include a repeating unit represented by the following formula (3).

(3)

In Formula 3,

G1 to G4 are the same or different and are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; -PO ₃ ^2- 2M ^+; Hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, g1 to g4 are the same or different from each other and independently represent an integer of 0 to 4; when g1 to g4 are an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, Is a metallic element.

According to one embodiment of the present invention, the formula (3) may be represented by the following formula (3-1).

[Formula 3-1]

In the above formula (3-1), G1 to G4 and g1 to g4 are as defined in formula (3).

According to one embodiment of the present invention, the formula (3) may be represented by any one of the following structural formulas.

In the above structural formulas, R11 to R14 are the same or different from each other and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, Q11 and Q12 are the same or different and at least one another are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, o1 to o4 are the same as or different from each other and each independently an integer of 0 to 4, q1 and q2 are the same or different and independently 0 Q1 + q2? 8, and when o1, o2, o3, o4, q1 and q2 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the random copolymer may include at least one repeating unit represented by the following formulas (4) to (10).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 4 to 10,

X3 to X7 are the same or different from each other, and each independently is a direct bond or -CO-; Or -SO ₂ - and,

E1 to E14 are the same or different and are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; -PO ₃ ^2- 2M ^+; Hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; ?,?,?,?,?,?,? And? Are the same or different from each other and each independently an integer of 0 to 4,?,?,?,?,?,?, ? and? are the same or different from each other and each independently an integer of 0 to 3, 0?? +? 7, 0?? +? 6, 0?? +? 5, The substituents in the parentheses are the same or different when?,?,?,?,?,?,?,?,?,?,? and?

According to one embodiment of the present disclosure, the random copolymer may comprise a repeating unit comprising a hydrophilic functional group.

According to one embodiment of the present disclosure, the random copolymer may include a repeating unit not containing a hydrophilic functional group.

According to one embodiment of the present disclosure, the random copolymer may be composed of a repeating unit containing a hydrophilic functional group.

According to one embodiment of the present disclosure, the random copolymer may be composed of a repeating unit not containing a hydrophilic functional group.

According to one embodiment of the present invention, the random copolymer may include both a repeating unit including a hydrophilic functional group and a repeating unit not including a hydrophilic functional group.

As used herein, "hydrophilic functional group" means a functional group having an ion-exchange group. For example, -SO ₃ H, -SO ₃ ^- M ^+, -COOH, -COO ^- M ^+, ₂ H -PO _3, -PO ₃ H ^- M ^+, and -PO ₃ ^2- 2M ⁺ selected from the group consisting at least But the present invention is not limited thereto. Here, M may be a metallic element.

According to one embodiment of the present invention, when the random copolymer includes a repeating unit containing a hydrophilic functional group, the above-mentioned formulas 4 to 10 may be represented by the following formulas 4-1 to 10-1.

[Formula 4-1]

[Formula 5-1]

[Formula 6-1]

[Formula 7-1]

[Formula 8-1]

[Formula 9-1]

[Formula 10-1]

In the general formulas (4-1) to (10-1)

X23 to X27 are the same or different from each other, and each independently is a direct bond, -CO-; Or -SO ₂ - and,

E21 to E24 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

E25 and E26 are equal to or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

E27 and E28 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

E29 and E30 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

E31 and E32 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

E33 is a case where ψ1 is 1 -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO ₃ ^2- 2M ^+, and not less than ψ1 is 2 at least one of two or more of E33 is -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M ^&

At least one of the E34 are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M ^&

? 1,? 1,? 1,? 1,? 1 and? 1 are the same or different from each other and each independently an integer of 0 to 4, and? 1 and? 1 are the same or different from each other and each independently 0 to 3侶 1 is an integer of 1 to 4, ω 1 is an integer of 1 to 3, 1 ≦ η 1 + θ 1 ≦ 7, 1 ≦ κ 1 + λ 1 ≦ 6, 1 ≦ μ 1 + π 1 ≦ 5, 1,? 1,? 1,? 1,? 1,? 1,? 1,? 1 and? 1 are integers of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, when the random copolymer includes a repeating unit that does not include a hydrophilic functional group, the above-mentioned formulas (4) to (10) may be represented by the following formulas (4-2) to (10-2).

[Formula 4-2]

[Formula 5-2]

[Formula 6-2]

[Formula 7-2]

[Formula 8-2]

[Formula 9-2]

[Formula 10-2]

In the above formulas (4-2) to (10-2)

X33 to X37 are the same or different from each other, and each independently is a direct bond, -CO-; Or -SO ₂ - and,

E41 to E54 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; 2,? 2,? 2,? 2,? 2,? 2,? 2,? 2,? 2 and? 2 are the same or different and each independently an integer of 0 to 4, and? 2,? 2,? 2, ? 2 and? 2 are the same or different from each other and each independently an integer of 0 to 3, 0?? 2 +? 2? 7, 0?? 2 +? 2? 6, 0? ? 2,? 2,? 2,? 2,? 2 and? 2 are integers of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the random copolymer may be a copolymer including a repeating unit represented by the following formula (13) and a repeating unit represented by the following formula (14), but is not limited thereto.

[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas (13) and (14)

U3 is represented by any one of the formulas (5-1), (7-1) and (9-1), A3 and B3 are the same or different and at least one is independently represented by the formula (3) Are each the same or different and each independently represents any one selected from the above-mentioned formulas (5-2), (7-2) and (9-2), and a3 and b3 are an integer of 1 or more.

According to one embodiment of the present invention, the repeating unit represented by the formula (13) may be a repeating unit containing a hydrophilic functional group.

According to one embodiment of the present invention, the repeating unit represented by the formula (14) may be a repeating unit not containing a hydrophilic functional group.

According to one embodiment of the present invention, the formula (4-1) may be represented by the following formula (4-1-1).

[Formula 4-1-1]

In the above formula (4-1-1), X23 to X25, E21 to E24,? 1,? 1,? 1 and? 1 are as defined in formula (4-1).

According to one embodiment of the present invention, X23 to X25 are the same as or different from each other, and each independently is a direct bond or -CO-; Or -SO ₂ - it is.

According to one embodiment of the present invention, each of X23 to X25 is a direct bond.

According to one embodiment of the present disclosure, X23 to X25 are each -CO-.

According to an exemplary embodiment of the present disclosure, wherein X23 to X25 are each -SO ₂ - a.

According to one embodiment of the present invention, the formula (5-1) may be represented by the following formula (5-1-1).

[Formula 5-1-1]

In Formula 5-1-1, X26, E25, E26,? 1 and? 1 are as defined in Formula 5-1.

According to one embodiment of the present disclosure, X26 is a direct bond.

According to one embodiment of the present disclosure, X26 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X26 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula (6-1) may be represented by the following formula (6-1-1) or (6-1-2).

[Formula 6-1-1]

[Formula 6-1-2]

In Formulas (6-1-1) and (6-1-2), X27, E27, E28,? 1 and? 1 are as defined in Formula (6-1).

According to one embodiment of the present disclosure, X27 is a direct bond.

According to one embodiment of the present disclosure, X27 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X27 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula (7-1) may be represented by any one of the following formulas (7-1-1) to (7-1-3).

[Formula 7-1-1]

[Formula 7-1-2]

[Formula 7-1-3]

In Formulas 7-1-1 to 7-1-3, E29, E30, 虜 1 and 了 1 are as defined in Formula 7-1.

According to one embodiment of the present invention, the formula (8-1) may be represented by any one of the following formulas (8-1-1) to (8-1-3).

[Formula 8-1-1]

[Formula 8-1-2]

[Formula 8-1-3]

In the general formulas (8-1-1) to (8-1-3), E31, E32, μ1 and π1 are as defined in the general formula (8-1).

According to one embodiment of the present invention, the formula (9-1) may be represented by the following formula (9-1-1).

[Formula 9-1-1]

In the above formula (9-1-1), E33 and? 1 are as defined in formula (9-1).

According to one embodiment of the present invention, the formula (10-1) may be represented by the following formula (10-1-1).

[Formula 10-1-1]

In the above formula (10-1-1-1), E34 and omega 1 are as defined in formula (10-1).

According to one embodiment of the present invention, the formula (4-2) may be represented by the following formula (4-2-1).

[Formula 4-2-1]

In the above formula (4-2-1), X33 to X35, E41 to E44,? 2,? 2,? 2 and? 2 are as defined in formula (4-2).

According to one embodiment of the present invention, X33 to X35 are the same or different and are each independently a direct bond or -CO-; Or -SO ₂ - it is.

According to one embodiment of the present invention, each of X33 to X35 is a direct bond.

According to one embodiment of the present disclosure, X33 to X35 are each -CO-.

According to an exemplary embodiment of the present disclosure, wherein X33 to X35 are each -SO ₂ - a.

According to one embodiment of the present invention, the formula (5-2) may be represented by the following formula (5-2-1).

[Formula 5-2-1]

In Formula 5-2-1, X36, E45, E46,? 2 and? 2 are as defined in Formula 5-2.

According to one embodiment of the present disclosure, X36 is a direct bond.

According to one embodiment of the present disclosure, X36 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X36 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula (6-2) may be represented by the following formula (6-2-1) or (6-2-2).

[Formula 6-2-1]

[Formula 6-2-2]

In Formulas (6-2-1) and (6-2-2), X37, E47, E48,? 2 and? 2 are as defined in Formula (6-2).

According to one embodiment of the present disclosure, X37 is a direct bond.

According to one embodiment of the present disclosure, X37 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein X37 is -SO ₂ - it is a.

According to one embodiment of the present invention, the formula (7-2) may be represented by any one of the following formulas (7-2-1) to (7-2-3).

[Formula 7-2-1]

[Formula 7-2-2]

[Formula 7-2-3]

In Formulas 7-2-1 to 7-2-3, E49, E50, 虜 2 and 了 2 are as defined in Formula 7-2.

According to one embodiment of the present invention, the formula (8-2) may be represented by any one of the following formulas (8-2-1) to (8-2-3).

[Formula 8-2-1]

[Formula 8-2-2]

[Formula 8-2-3]

In the above formulas 8-2-1 to 8-2-3, E51, E52, 占 and? 2 are as defined in the formula 8-2.

According to one embodiment of the present invention, the formula (9-2) may be represented by the following formula (9-2-1).

[Formula 9-2-1]

In the above formula (9-2-1), E53 and? 2 are as defined in formula (9-2).

According to one embodiment of the present invention, the formula (10-2) may be represented by the following formula (10-2-1).

[Chemical Formula 10-2-1]

In the above formula (10-2-1), E54 and? 2 are as defined in formula (10-2).

According to one embodiment of the present invention, the formula (5-1) may be represented by any one of the following formulas.

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b21 and b22 are the same or different and each independently an integer of 0 to 4, 1? B21 + b22? 8, b21 and b22 When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula (7-1) may be represented by any one of the following formulas.

In the above formula, Q19 and Q20 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b29 and b30 are the same or different from each other and independently an integer of 0 to 6, 1? B29 + b30? 6, When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula (9-1) may be represented by the following structural formula.

At least one of Q &lt; ₁₃ &gt; is independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b23 is an integer of 1 to 4, and b23 is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the formula (5-2) may be represented by any one of the following formulas.

In the above structural formulas, R41 and R42 are the same or different from each other and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o3 and o4 are the same or different and each independently an integer of 0 to 4, and when o3 and o4 are each 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the formula (7-2) may be represented by any one of the following formulas.

In the above structural formulas, R45 and R46 are the same or different from each other and each independently represents a halogen group; A nitro group; O7 and o8 are the same as or different from each other and each independently an integer of 0 to 6, 0? O7 + o8? 6, and o7 and o8 are each 2 or more, the substituents in the parentheses are the same It is different.

According to one embodiment of the present invention, the formula (9-2) may be represented by any one of the following formulas.

In the above structural formulas, R41 represents a halogen group; A nitro group; Or a trifluoromethyl group, o3 is an integer of 0 to 4, and when o3 is 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present disclosure, the U3 may be represented by any one of the following structural formulas.

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q19 and Q20 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of Q &lt; ₁₃ &gt; is each independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

M is a metallic element,

b21 and b22 are the same or different and each independently an integer of 0 to 4, b29 and b30 are the same or different and each independently an integer of 0 to 6, b23 is an integer of 1 to 4, 1? b21 + b22? 8, 1? b29 + b30? 6, and b21 to b23, b29 and b30 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, A3 and B3 are the same or different from each other and at least one of them is independently represented by the above formula (3), and the remaining and V3 are the same or different and independently selected from the following structural formulas Can be displayed in any one of them.

In the above structural formulas, R41, R42, R45 and R46 are the same or different from each other and each independently represents a halogen group; A nitro group; And o3 and o4 are the same or different from each other and each independently an integer of 0 to 4, o7 and o8 are the same or different and each independently an integer of 0 to 6 and 0? O7 + o8 6, and o3, o4, o7 and o8 are each 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, when A3 is represented by Formula 3, A3 may be represented by the following structural formula.

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And m is a metallic element, q1 and q2 are the same as or different from each other and each independently an integer of 0 to 8, 1? Q1 + q2? 8, and q1 and q2 are When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the random copolymer containing the hydrophilic functional group may include any one selected from the following structural formulas.

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of Q &lt; ₁₃ &gt; is each independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

At least one of Q &lt; ₁₄ &gt; is each independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q15 and Q16 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q17 and Q18 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q19 and Q20 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Q21 to Q24 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

M is a metallic element,

b21, b22, b28 and b31 to b33 are the same or different and each independently an integer of 0 to 4, b23 is an integer of 1 to 4, b24 is an integer of 1 to 3, b27 and b34 are the same And b25 and b26 are the same or different from each other, and each independently is an integer of 0 to 5, b29 and b30 are the same or different from each other and each independently an integer of 0 to 6, 1? B21 + b22? 8, 1? B25 + b26? 5, 1? B27 + b28? 7, 1? B29 + b30? 6, 1? B31 + b32 + b33 + b34? 15, b21 And b34 are each an integer of 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, when B3 is represented by Formula 3, B3 may be represented by any one of the following formulas.

In the above structural formulas, R11 to R14 are the same or different from each other and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o1 to o4 are the same or different from each other and independently represent an integer of 0 to 4, and when o1 to o4 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other.

According to one embodiment of the present invention, the random copolymer containing no hydrophilic functional group may include any one of repeating units selected from the following structural formulas.

In the above structural formulas, R41 to R50 are the same or different and each independently represents a halogen group; A nitro group; And o3 to o5 and o12 are the same as or different from each other and each independently an integer of 0 to 4, o6 and o11 are the same or different and each independently an integer of 0 to 3, o7 and o8 O 9 and o 10 are the same as or different from each other and each independently represents an integer of 0 to 5, 0 ≦ o 7 + o 8 ≦ 6, 0 ≦ o 9 + o 10 ≦ 5 and o3 to o12 are each 2 or more, the substituents in the parentheses are the same or different from each other.

According to one embodiment of the present invention, the random copolymer containing no hydrophilic functional group may include any one of repeating units selected from the following structural formulas.

According to one embodiment of the present invention, the random copolymer is selected from repeating units represented by the above formulas (4), (6), (8) and (10), in addition to the repeating unit represented by the above formula But the present invention is not limited thereto.

In the present specification, the metallic element may be an alkali metal, an alkaline earth metal, a lanthanide metal, an actinide group metal, a transition metal or a post-transition metal.

The alkali metal may be Li, Na, K, Rb, Cs or Fr.

The alkaline earth metal may be Be, Mg, Ca, Sr or Ba.

The lanthanide metal may be La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu.

The actinide metal may be Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No or Lr.

The transition metal is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Lu, Hf, W, Re, Os, Ir, Pt, Au, Hg, Lr, Rf, Db, Sg, Bh, Hs, Mt, Ds, Rg or Cn.

The metal may be Al, Si, P, S, Ga, Ge, As, Se, In, Sn, Sb, Te, Tl, Pb, Bi or Po.

According to one embodiment of the present invention, the repeating units represented by the formula (1) in the block copolymer may be alternately arranged, grafted or randomly arranged.

According to one embodiment of the present disclosure, the block polymer may be a block copolymer including a hydrophilic block and a hydrophobic block.

According to one embodiment of the present invention, n may be the sum of the number of repeating units represented by formula (1) arbitrarily arranged in the block copolymer.

According to one embodiment of the present disclosure, the hydrophilic block means a block having an ion-exchange group as a functional group. Wherein the functional groups are ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M + , and -PO ₃ ^2- 2M ⁺ the group consisting of Or the like. Here, M may be a metallic element. That is, the functional group may be hydrophilic.

Here, the term &quot; block having an ion exchanger &quot; means a block containing an average of 0.5 or more ion exchange groups represented by the number of ion exchange groups per structural unit constituting the block, and an average of 1.0 or more ion exchangers per structural unit It is more desirable to have it.

According to one embodiment of the present disclosure, the hydrophobic block means a polymer block having substantially no ion exchanger.

Here, the &quot; block having substantially no ion-exchanger &quot; means a block represented by the number of ion-exchange groups per one structural unit constituting the block, and the average block is less than 0.1, more preferably 0.05 or less, Is more preferable.

According to one embodiment of the present invention, when a block copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is contained, it has a high mechanical strength and a high ionic conductivity, The phase separation phenomenon of the film can be facilitated.

According to one embodiment of the present invention, the hydrophilic block of the block copolymer may be represented by the repeating unit represented by the formula (1).

According to one embodiment of the present invention, the hydrophobic block of the block copolymer may be represented by the repeating unit represented by the formula (2).

According to one embodiment of the present disclosure, the weight average molecular weight of the hydrophilic block may be 1,000 to 500,000 (g / mol).

According to one embodiment of the present invention, the weight average molecular weight of the hydrophobic block may be 1,000 to 500,000 (g / mol).

According to one embodiment of the present invention, the block copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) further comprises a brancer.

According to one embodiment of the present invention, the random copolymer containing the repeating unit represented by Formula 3 further includes a brancer.

As used herein, the term "brancher " has the function of connecting or crosslinking a polymer chain.

According to one embodiment of the present invention, in the case of the copolymer further comprising the brancer, the brancer can constitute the main chain of the direct copolymer, and the mechanical densification of the thin film can be improved. For example, the branched copolymer of the present invention can be produced by polymerizing a branched hydrophilic block containing an acid substituent and a branched hydrophobic block containing no acid substituents, The brancher directly configures the main chain of the copolymer without conducting post-sulfonation or cross-linking of the sulfonated polymer and maintains the mechanical integrity of the thin film Hydrophilic blocks that impart ionic conductivity to the thin film and hydrophilic blocks that impart ionic conductivity to the thin film may be alternately connected by chemical bonding.

According to one embodiment of the present invention, the block copolymer and the random copolymer further comprise a branching agent represented by the following formula (11) or (12).

(11)

[Chemical Formula 12]

In the above formulas (11) and (12)

X is -S-; -O-; -CO-; -SO-; -SO ₂ -; -NR-; A hydrocarbon-based or fluorine-

p is an integer of 0 to 100, and when p is 2 or more, 2 or more X's are the same or different,

Y1 and Y2 are the same or different from each other and each independently represents an aromatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; An aliphatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; Or an NR ' R "

R, R 'and R "are the same or different and each independently represents an aromatic ring substituted with a halogen group, or an aliphatic ring substituted with a halogen group,

Z is a trivalent organic group.

According to one embodiment of the present invention, the branche derived from the compound of formula (11) is an aromatic ring substituted with a halogen group of each of Y1 and Y2; Or an aliphatic ring substituted with a halogen group; Or NR ' R "may act as a branching agent, with the halogen group falling off from the aromatic ring or aliphatic ring.

According to one embodiment of the present disclosure, p is 3 or more.

According to one embodiment of the present disclosure, X is -S-.

According to another embodiment of the present invention, X is a haloalkylene group.

According to another embodiment of the present disclosure, X is -NR-.

According to one embodiment of the present invention, Y1 and Y2 are the same or different and each independently an aromatic ring substituted with a halogen group.

According to one embodiment of the present invention, Y1 and Y2 are the same or different and are each independently an aromatic hydrocarbon ring substituted with F.

According to one embodiment of the present disclosure, Y1 and Y2 are the same or different and each is an amine group represented by NR'R ".

According to another embodiment of the present invention, each of Y1 and Y2 is a fluorine-substituted phenyl group. Specific examples include 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl and the like, but are not limited thereto.

According to one embodiment of the present invention, the branching agent represented by Formula 11 may be represented by any one of the following structures.

In the above structure, X, p, R 'and R "are the same as defined in Formula (11).

According to one embodiment of the present invention, Z in the formula (12) may be represented by any one of the following formulas (12-1) to (12-4).

[Formula 12-1]

[Formula 12-2]

[Formula 12-3]

[Chemical Formula 12-4]

In Formulas (12-1) to (12-4)

L1 To L &lt; 7 &gt; are the same or different and are each independently a direct bond; -S-; -O-; -CO-; Or -SO ₂ - and,

R21 to R31 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r1, r2, r3, r6, r8, r9 and r10 are the same or different and each independently an integer of 0 to 4; r4, r5, r7 and r11 are the same as or different from each other, And r1 to r11 are each an integer of 2 or more, the substituents in the parentheses of 2 or more are the same or different from each other.

According to one embodiment of the present disclosure, L1 is -CO-.

According to an exemplary embodiment of the present disclosure, the L1 is -SO ₂ - is a.

According to one embodiment of the present disclosure, L1 is -S-.

According to one embodiment of the present disclosure, L2 is -CO-.

According to an exemplary embodiment of the present disclosure, wherein L2 is -SO ₂ - it is a.

According to one embodiment of the present disclosure, L2 is -S-.

According to one embodiment of the present disclosure, L3 is -CO-.

According to an exemplary embodiment of the present disclosure, the L3 is -SO ₂ - is a.

According to one embodiment of the present disclosure, L3 is -S-.

According to one embodiment of the present disclosure, L4 is -CO-.

According to an exemplary embodiment of the present disclosure, the L4 is -SO ₂ - is a.

According to one embodiment of the present disclosure, L5 is a direct bond.

According to one embodiment of the present disclosure, L6 is a direct bond.

According to one embodiment of the present disclosure, L7 is a direct bond.

According to one embodiment of the present disclosure, each of R21 to R31 is hydrogen.

According to one embodiment of the present disclosure, R21 to R26 and R28 to R31 are each hydrogen.

According to one embodiment of the present invention, R27 is a halogen group.

According to one embodiment of the present disclosure, R27 is fluorine.

According to one embodiment of the present invention, the branching agent represented by the general formula (12) may be represented by any one of the following structures.

According to one embodiment of the present invention, the random copolymer is a copolymer further comprising a branching agent represented by the formula (11) or (12), in addition to the repeating unit represented by the formula (13) But is not limited thereto.

According to one embodiment of the present disclosure, the random copolymer may include but is not limited to three different units except for a branche.

According to one embodiment of the present invention, the block copolymer comprising the repeating unit represented by Formula 1 and the repeating unit represented by Formula 2 may be a sulfonated block copolymer.

According to one embodiment of the present invention, the random copolymer containing the repeating unit represented by the above formula (3) may be a sulfonated random copolymer.

According to one embodiment of the present invention, the block copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) may be a branched sulfonated block copolymer.

According to one embodiment of the present invention, the random copolymer containing the repeating unit represented by the formula (3) may be a branched sulfonated random copolymer.

According to one embodiment of the present invention, the block copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) may be prepared in such a manner that the branched copolymer is linearly formed It is possible to obtain a polymer having a higher molecular weight than a block copolymer and have the advantage of exhibiting higher mechanical properties on the basis of the same molecular weight as that of a random polymer. Therefore, when applied to a polymer electrolyte membrane, it exhibits higher mechanical properties.

In addition, due to the characteristics of the branched block copolymer, water uptake is low in comparison with IEC (ion exchange capacity) indicating the degree of sulfonic acid group content, and the electrolyte membrane is swelled by swelling ), There is an advantage that the dimensional stability is higher.

According to one embodiment of the present disclosure, when the random copolymer comprises a 9,9-bis (4-hydroxyphenyl) fluorene monomer, water absorption Water uptake).

According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 9.9: 0.1.

According to one embodiment of the present disclosure, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 9: 1.

According to one embodiment of the present disclosure, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 8: 2.

According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 7: 3.

According to one embodiment of the present disclosure, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 6: 4.

According to another embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 5.5: 4.5.

According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 5: 5.

According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 0.1: 9.9 to 4: 6.

According to one embodiment of the present disclosure, the weight ratio of the block copolymer and the random copolymer may be from 3: 7 to 7: 3.

According to another embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 4: 6 to 6: 4.

According to one embodiment of the present disclosure, the weight ratio of the block copolymer and the random copolymer may be from 4.5: 5.5 to 5.5: 4.5.

According to another embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer may be 5: 5.

When the weight ratio of the block copolymer and the random copolymer according to one embodiment of the present invention is in the above range, the current density value is improved in a low humidification range (< RH 50%), and the unit cell performance is excellent. In addition, there is an advantage that mechanical properties are superior to those when only a random copolymer is used, and dewetting phenomenon hardly occurs even when a reinforcing film is manufactured.

According to one embodiment of the present disclosure, the ion exchange capacity value (IEC) of the block copolymer may be 1.6 meq./g to 2.0 meq./g.

According to one embodiment of the present disclosure, the ion exchange capacity value (IEC) of the random copolymer may be 1.3 meq./g to 2.2 meq./g.

According to one embodiment of the present invention, there is provided a method for producing a polymer comprising a block copolymer comprising a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2), and a random copolymer comprising a repeating unit represented by the formula A polymer electrolyte membrane is provided.

According to one embodiment of the present invention, there is provided a polymer electrolyte membrane comprising a blended copolymer obtained by blending the block copolymer and the random copolymer.

As used herein, "blended copolymer" means a copolymer in which a block copolymer and a random copolymer are contained at a constant weight ratio.

According to one embodiment of the present invention, the polymer electrolyte membrane is formed of a block copolymer comprising the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2), and a random copolymer containing the repeating unit represented by the formula But may be made using materials and / or methods known in the art, except that they include coalescing. For example, by applying a solution comprising the blended copolymer, and drying and / or curing.

According to one embodiment of the present invention, the application may be performed by a method such as solution casting, tape casting, dip coating, spray coating, spin coating, or the like Can be used.

According to one embodiment of the present invention, the solvent used in the production of the polymer electrolyte membrane is selected from the group consisting of N, N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) N, N-dimethylformamide (DMF), or the like can be used as the organic solvent, for example, N, N-dimethylpyrollidone (NMP), diphenylsulfone or N, N- no.

According to one embodiment of the present disclosure, the curing may be performed by heating.

According to one embodiment of the present disclosure, the heating means curing by heating.

According to one embodiment of the present invention, the heating temperature may be 30 ° C or more and 200 ° C or less, specifically 50 ° C or more and 150 ° C or less.

According to one embodiment of the present invention, the heating time may be 1 hour or more and 46 hours or less, specifically, 5 hours or more and 20 hours or less.

According to an embodiment of the present invention, the method for producing a polymer electrolyte membrane may further comprise the step of adding an acid solution to a solution containing the copolymer.

According to one embodiment of the present invention, when an acid solution is added to a solution containing the polymer, the -SO ₃ ^- M ⁺ ; -COO ^- M ⁺ ; -PO ₃ H ^- M ^+; Or the metal M of the copolymer which is -PO ₃ ^2- 2M ⁺ can be replaced by H (hydrogen).

According to one embodiment of the present disclosure, the heating is preheated at 50 ° C to 70 ° C for 2 to 6 hours, at 80 ° C for at least 12 hours, and finally at 80 ° C in a vacuum oven for at least 12 hours can do.

According to an embodiment of the present invention, the polymer electrolyte membrane may be a pure polymer electrolyte membrane including the block copolymer and the random copolymer.

According to another embodiment of the present invention, the polymer electrolyte membrane may be a reinforcing film further comprising a substrate.

The disclosure includes: a substrate; The block copolymer; And a reinforcing film comprising the random copolymer.

According to one embodiment of the present disclosure, a "reinforcing film" is a separating film containing a base material as a reinforcing material, and is a membrane capable of exchanging ions, including a film containing a substrate, an ion exchange membrane, An ion exchange membrane, an ion exchange membrane, an ion exchange membrane, an ion exchange membrane, an ion exchange membrane, an ion exchange membrane, an ion exchange electrolyte membrane, an ion transfer electrolyte membrane or an ion conductive electrolyte membrane.

As used herein, the substrate may refer to a three-dimensional networked support, wherein the reinforcing membrane comprising the substrate and the blended copolymer is formed such that the blended copolymer has one surface of the substrate, Quot; is meant to be included in at least some of the surface and the pore region within the substrate. That is, the reinforcing membrane of the present specification may be provided in a form in which the blended copolymer is impregnated in the substrate.

As used herein, the term "impregnation " means that the copolymer blended into the substrate is impregnated.

According to one embodiment of the present disclosure, the impregnation may be performed by dipping the substrate into the blended copolymer solution, slot dye coating, bar casting, or the like.

In this specification, the immersion may be expressed in terms of a dip coating or a dipping method.

According to one embodiment of the present invention, there is a problem in that, in the case of a hydrocarbon-based electrolyte membrane, rapid performance reduction occurs in a low humidification region. Thus, the reinforcing membrane according to one embodiment of the present disclosure can include the block copolymer and the random copolymer to facilitate a high current density value, good mechanical properties, and phase separation of the reinforcing film even in a low humidity region.

In addition, the reinforcing film according to one embodiment of the present invention can improve the chemical resistance and durability of the device including the substrate, thereby improving the lifetime of the device.

According to one embodiment of the present disclosure, the substrate is made of one or two or more materials selected from the group consisting of polypropylene (PP), polytetrafluoroethylene (PTFE), polyethylene (PE) and polyvinylidenedifluoride Is selected.

The disclosure also relates to a method of manufacturing a substrate, comprising: preparing a substrate; And impregnating the substrate with the blended copolymer solution.

According to one embodiment of the present disclosure, the reinforcing membrane can be oriented.

Specifically, according to one embodiment of the present specification, the substrate can be produced by uniaxial stretching or biaxial stretching, and the orientation of the substrate by the stretching can determine the orientation of the reinforcing film. Therefore, the reinforcing membrane according to one embodiment of the present disclosure can have a machine direction (MD) and a directionality in the machine direction, and the reinforcing film has stress and elongation The physical properties of the polymer can be different.

The disclosure also includes an anode; Cathode; And the above-described polymer separator provided between the anode and the cathode.

As used herein, the term "membrane electrode assembly (MEA)" means a junction body of an electrode (cathode and anode) where an electrochemical catalytic reaction of fuel and air occurs and a polymer electrolyte membrane in which hydrogen ions are transferred, Anode) and an electrolyte membrane are adhered to each other.

According to one embodiment of the present disclosure, the membrane electrode assembly may be manufactured by a conventional method known in the art, such that the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the polymer electrolyte membrane. For example, the cathode; Anode; And a polymer electrolyte membrane positioned between the cathode and the anode in close contact with each other at a temperature of 100 ° C to 400 ° C.

According to one embodiment of the present disclosure, the anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may again include an anode microporous layer and an anode electrode substrate.

According to one embodiment of the present disclosure, the cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may again include a cathode microporous layer and a cathode electrode substrate.

FIG. 1 schematically shows the principle of electricity generation of a fuel cell. In a fuel cell, a basic unit for generating electricity is a membrane electrode assembly (MEA), which includes a separation membrane 100, And an anode 200a and a cathode 200b electrode formed on the substrate 200a. 1 showing the principle of electricity generation of a fuel cell, in the anode 200a, oxidation reaction of a fuel such as hydrogen or hydrocarbons such as methanol or butane occurs to generate hydrogen ions (H ⁺ ) and electrons (e ^- ) , The hydrogen ions move to the cathode 200b through the separation membrane 100. [ In the cathode 200b, hydrogen ions transferred through the separation membrane 100, an oxidizing agent such as oxygen, and electrons react to produce water. This reaction causes electrons to migrate to the external circuit.

The catalyst layer of the anode electrode is preferably a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum- Lt; / RTI &gt;

The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and a platinum or platinum-transition metal alloy can be preferably used as a catalyst. The catalysts can be used not only by themselves but also by being supported on a carbon-based carrier.

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. The method of coating the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used. The catalyst ink may typically consist of a catalyst, a polymer ionomer and a solvent.

The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material. As the conductive substrate, carbon paper, carbon cloth or carbon felt can be preferably used.

The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive base. The microporous layer can be used to improve the performance of the fuel cell under low humidification conditions and serves to reduce the amount of water flowing out of the gas diffusion layer to make the polymer electrolyte membrane sufficiently wet.

One embodiment of the present disclosure includes at least two membrane electrode assemblies (MEAs); A stack including a bipolar plate disposed between the membrane electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supplier for supplying an oxidant to the stack.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction.

The fuel cell may be manufactured according to a conventional method known in the art using the membrane electrode assembly described above. For example, the membrane electrode assembly and the bipolar plate manufactured as described above can be manufactured.

According to one embodiment of the present disclosure, a fuel cell comprises a stack, a fuel supply, and an oxidant supply.

2 schematically shows the structure of a fuel cell, which includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80. [

The stack 60 includes one or more of the membrane electrode assemblies described above and includes a separator interposed therebetween when two or more membrane electrode assemblies are included. The separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer the fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidant supply part 70 serves to supply the oxidant to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected into the pump 70 and used.

The fuel supply unit 80 serves to supply the fuel to the stack 60 and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 Lt; / RTI &gt; As the fuel, gas or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

According to one embodiment of the present invention, when the polymer electrolyte membrane is used as an ion exchange membrane of a fuel cell, the above-described effect can be obtained. The fuel cell may be a polymer electrolyte membrane fuel cell (PEMFC), a direct liquid fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, a direct ethanol fuel cell, or a direct dimethyl ether fuel cell.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

< Manufacturing example >

< Manufacturing example  1> Synthesis of Block Copolymer

Three-neck round bottom flask A 500-mL three-neck round bottom flask was charged with hydroquinonesulfonic acid potassium salt, 4,4'-difluorobenzophenone and 3,5-bis (4-fluorobenzoyl) phenyl (4-fluorobenzoyl) phenyl (4-fluorophenyl) methanone (brancher) was added to the solution, and dimethylsulfoxide (DMSO) ) In K ₂ CO ₃ as a catalyst in a nitrogen atmosphere.

Then, the reaction mixture was stirred at a temperature of 140 ° C. for 4 hours to remove the azeotropic mixture by adsorbing molecular sieves on a Dean-Stark apparatus while benzene was refluxed, Was heated to 180 DEG C and condensation polymerization was carried out for 20 hours. After the completion of the reaction, the temperature of the reactant was reduced to 60 ° C., and 4,4'-difluorobenzophenone, 9,9-bis (4-hydroxyphenyl) (4-fluorobenzoyl) phenyl (4-fluorobenzoyl) phenylenediamine was prepared by reacting 9,9-bis (4-hydroxyphenyl) fluorene with 3,5- (4-fluorophenyl) methanone), and the reaction was resumed using DMSO and benzene as a catalyst in a nitrogen atmosphere with K ₂ CO ₃ .

Then, the reaction mixture was stirred again at 140 ° C. for 4 hours to remove the azeotropic mixture by molecular sieves in a Dean-Stark apparatus while refluxing the benzene, and then the reaction temperature was adjusted to 180 ° C. Lt; 0 &gt; C and subjected to condensation polymerization for 20 hours. Then, the temperature of the reaction was reduced to room temperature, and further DMSO was added to dilute the product. The diluted product was poured into an excess amount of methanol to separate the copolymer from the solvent. Thereafter, the excess K ₂ CO ₃ was removed using water, and the resulting copolymer was dried in a vacuum oven at 80 ° C. for 12 hours or longer to obtain a branched sulfonated block having a hydrophobic block and a hydrophilic block alternately chemically bonded To prepare a copolymer.

< Manufacturing example  2> Synthesis of Random Copolymer

&Lt; Production example 2-1 >

A three-neck round bottom flask was charged with 5,5'-sulfonylbis (2-fluorobenzenesulfonate), 4'-difluoro (4'-difluorodiphenylsulfone), 9,9-bis (4-hydroxyphenyl) fluorene, 3,5-bis (4-fluorobenzoyl) phenyl placed (4-fluorophenyl) methanone (3,5-Bis (4-fluorobenzoyl ) phenyl (4-fluorophenyl) methanone) (Brancher) in DMSO (Dimethyl Sulfoxide) and benzene (benzene) solvent, K ₂ CO ₃ As a catalyst in a nitrogen atmosphere.

Then, the reaction mixture was stirred at a temperature of 140 ° C. for 4 hours to remove the azeotropic mixture by adsorbing molecular sieves on a Dean-Stark apparatus while benzene was refluxed, Was heated to 180 DEG C and condensation polymerization was carried out for 20 hours. After the completion of the reaction, the temperature of the reaction was reduced to 60 ° C, and the product diluted with DMSO or the like was poured into an excess amount of methanol to separate the copolymer from the solvent. Thereafter, the excess K ₂ CO ₃ was removed using water, and the resulting copolymer was dried in a vacuum oven at 80 ° C. for 12 hours or longer to produce a branched sulfonated random copolymer.

&Lt; Production example 2-2 >

Except that hydroquinone was used in place of 9,9-bis (4-hydroxyphenyl) fluorene in Production Example 2-1. A branched sulfonated random copolymer was prepared in the same manner as in 2-1.

&Lt; Production Example 2-3 >

Except that methylhydroquinone was used in place of 9,9-bis (4-hydroxyphenyl) fluorene in Production Example 2-1. A branched sulfonated random copolymer was prepared in the same manner as in Example 2-1.

&Lt; Preparation Example 2-4 &

The procedure of Production Example 2-1 was repeated except that methoxyhydroquinone was used in place of 9,9-bis (4-hydroxyphenyl) fluorene. A branched sulfonated random copolymer was prepared in the same manner as in Production Example 2-1.

&Lt; Preparation Example 2-5 &

In Production Example 2-1, 4,4'-dihydroxybiphenyl (4,4'-dihydroxyphenyl) fluorene was used in place of 9,9-bis (4-hydroxyphenyl) fluorene '-Dihydroxybiphenyl) was used in place of the dihydroxybiphenyl used in Synthesis Example 2-1 to prepare a branched sulfonated random copolymer.

DMSO solvent was mixed with the branched sulfonated block copolymer prepared in Preparation Example 1 and the branched sulfonated random copolymer prepared in Preparation Examples 2-1 to 2-5, respectively, and then filtered to prepare a copolymer solution composition .

Then, the pure polymer electrolyte membrane was prepared by solution casting using the prepared copolymer solution, and then the dried polymer electrolyte membrane was allowed to stand in a 1 M sulfuric acid aqueous solution at 80 ° C for one day to convert the salt form of the sulfonic acid group into -SO ₃ H To prepare a polymer electrolyte membrane.

Then, the membrane area of the Active Area of electrode assembly 25cm ² if manufacturing the protection films attached to both sides to leave polymer electrolyte membrane heat-pressing to prepare such that the Open Area is 25cm ² of the protective film polymer electrolyte to be attached to a film, and that After that, an electrode having an area of 25 cm ² or more was prepared, and a polymer electrolyte membrane having a protective film attached between the electrodes was prepared. The polymer electrolyte membrane was thermocompression-bonded using a hot press machine, The electrolyte membrane and the membrane electrode assembly were prepared, and the results of the unit cell performance evaluation are shown in Table 1 below.

Samples Current density (mA / cm ² @ 0.6V)
Cell Temp. : 75 ° C Copolymer molecular weight
(MW, g / mol) RH100% RH 50% RH32% Production Example 1 1,160 1,221 753 1,030,000 Production Example 2-1 1,108 1,243 962 1,120,000 Production example 2-2 1,122 1,136 824 982,000 Production Example 2-3 - - - 141,000 Production example 2-4 945 940 785 551,000 Production example 2-5 1,098 1,125 810 780,000

In general, the performance of the unit cell at 70 ° C did not show a significant performance difference between the polymer electrolyte membranes even when the humidification state was lowered. On the other hand, when the cell operating temperature was increased to 75 ° C, it was confirmed that there was a performance difference in the region of low humidification (RH 32%).

As a result of examining the characteristics of the polymer electrolyte membrane of the branched sulfonated random copolymer in various types of monomers having no sulfonic acid group, it was found that 9,9-bis (4-hydroxyphenyl) fluorene 9,9-Bis (4-hydroxyphenyl) fluorene) exhibited the most noticeable current density at a low humidification range of 75 ° C and 32%. This current density value is better than the current density value in the low humidification region of 75 DEG C and 32% of the branched sulfonated block copolymer prepared in Production Example 1. [ On the other hand, when methylhydroquinone of Production Example 2-3 was used, it was difficult to prepare a random copolymer having a high molecular weight.

On the other hand, in the case of the branched sulfonated random copolymer, the mechanical properties of the polymer electrolyte membrane are relatively weak even though they have molecular weights similar to those of the branched sulfonated block copolymer. These properties seem to be related to the occurrence of dewetting when making reinforced membranes using branched sulfonated random copolymers.

< Example >

< Example  1-1>

1) Preparation of copolymer solution composition

The branched sulfonated block copolymer prepared in Preparation Example 1 and the branched sulfonated random copolymer prepared in Preparation Example 2-1 were mixed in a ratio of 9: 1 in a DMSO solvent and filtered to obtain a blended copolymer solution A composition was prepared.

2) Production of polymer electrolyte membrane

A pure polymer electrolyte membrane or a reinforced membrane was prepared by solution casting using the prepared copolymer solution. The polymer electrolyte membrane thus dried was left in a 1M sulfuric acid aqueous solution at 80 ° C for one day to prepare a polymer electrolyte membrane by replacing the salt form of the sulfonic acid group with the form of -SO ₃ H.

3) Production of membrane electrode assembly (MEA)

Want to make the film a protective film on both sides to leave polymer electrolyte membrane heat-pressing area is prepared so that the 25cm ² opening area (Open Area) of a protective film to be attached if 25cm ² of the active area (Active Area) of the electrode assembly to The polymer electrolyte membrane was prepared. Thereafter, electrodes having the same area of 25 cm ² or more were prepared, and a polymer electrolyte membrane having a protective film attached therebetween was prepared. Then, thermocompression was performed using a hot press machine, and then the transfer substrate on both sides was removed. A polymer electrolyte membrane and a membrane electrode assembly were prepared.

< Example  1-2>

In Example 1-1, the branched sulfonated block copolymer prepared in Preparation Example 1 and the branched sulfonated random copolymer prepared in Preparation Example 2-1 were mixed and dissolved in a ratio of 8: 2, respectively, followed by filtration A polyelectrolyte membrane and a membrane electrode assembly were prepared in the same manner as in Example 1-1 except that the blended copolymer solution composition thus obtained was used.

< Example  1-3>

In Example 1-1, the branched sulfonated block copolymer prepared in Preparation Example 1 and the branched sulfonated random copolymer prepared in Production Example 2-1 were mixed and dissolved in a ratio of 5: 5, A polyelectrolyte membrane and a membrane electrode assembly were prepared in the same manner as in Example 1-1 except that the blended copolymer solution composition thus obtained was used.

< Comparative Example  1>

In Example 1-1, except that the block copolymer solution composition obtained by dissolving the branched sulfonated block copolymer prepared in Preparation Example 1 and then filtering was used in place of the blended copolymer solution composition, Polymer electrolyte membranes and membrane electrode assemblies were prepared.

< Comparative Example  2>

Except that the random copolymer solution composition obtained by dissolving the branched sulfonated random copolymer prepared in Preparation Example 2-1 and then filtering was used in place of the blended copolymer solution composition in Example 1-1, Polymer electrolyte membranes and membrane electrode assemblies were prepared in the same manner as in 1-1.

The tensile strengths of the polymer electrolyte membranes prepared in Examples 1-1 to 1-3 and Comparative Examples 1 and 2 were measured and the performance evaluation results of the unit cells using the membrane electrode assembly of the prepared polymer electrolyte membrane The results are shown in Table 2 and FIG.

division Random copolymer ratio Block copolymer ratio Current Density
(Current density) Relative ratio UTM
(Tensile Strength) Example 1-1 0.10 0.90 788 81.91 647 Examples 1-2 0.20 0.80 745 77.44 633 Example 1-3 0.50 0.50 936 97.30 598 Comparative Example 1 0.00 1.00 753 78.27 693 Comparative Example 2 1.00 0.00 962 100 440

In Table 2 and FIG. 3, the relative ratio is a relative value of other samples in terms of percentage, based on the current density value of 75 DEG C and RH 32% of Comparative Example 2. [ The Universal Testing Machine (UTM) is a measure of the tensile strength of each polymer electrolyte membrane.

In contrast to the improved low humidification performance at 75 DEG C and RH 32% of the polyelectrolyte membrane made of the branched sulfonated random copolymer (Comparative Example 1), the branched sulfonated block copolymer according to the present invention and the present invention It was confirmed that the blending of the branched sulfonated random copolymer according to the present invention exhibited an equivalent current density value in the above-mentioned Example 3 in which the blending ratio of the branched sulfonated random copolymer was 5: 5.

As a result, it was found that the mechanical properties of the membrane were somewhat reduced as the ratio of the random copolymer was increased as compared with the polymer electrolyte membrane composed of the block copolymer. At this time, in the case of the polymer electrolyte membrane made only of the random copolymer, the mechanical properties of the film were poor as the film thickness was thinned, whereas in Example 3 where the blending ratio of the block copolymer and the random copolymer according to the present invention was 5: 5, It was possible to form a thin film having a thickness of 10 탆 or less because of good mechanical properties, and it was confirmed that dewetting phenomenon hardly occurs even in the manufacture of a reinforced film using the thin film.

When 9,9-bis (4-hydroxyphenyl) fluorine monomer was used particularly in the sulfonated random copolymer branched from the above Preparation Example and Table 1, 75 ℃, and RH32%, respectively, compared to other random copolymers.

In addition, the polymer electrolyte membrane composed only of a random copolymer has somewhat insufficient mechanical properties in comparison with the molecular weight, which can be solved through blending with the branched sulfonated block copolymer according to the present invention.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. And will be apparent to those skilled in the art.

100: membrane
200a: anode
200b: cathode
60: Stack
70: oxidant supplier
80: fuel supply unit
81: Fuel tank
82: Pump

Claims (19)

A block copolymer comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2); And
1. A polymer electrolyte membrane comprising a random copolymer comprising a repeating unit represented by the following formula (3): &lt; EMI ID =
[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,
G1 to G4 are the same or different and are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; -PO ₃ ^2- 2M ^+; Hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, g1 to g4 are the same or different from each other and independently represent an integer of 0 to 4; when g1 to g4 are an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, Is a metallic element,
a and a 'are an integer of 1 or more, a: a' is 1,000: 1 to 5: 1,
b and b 'are an integer of 1 or more, b: b' is 1,000: 1 to 5: 1,
n is an integer of 1 or more and 100,000 or less,
m is an integer of 1 or more and 100,000 or less,
A1, B1, V1 and V2 are the same as or different from each other, and each independently represents one selected from the following formulas (1-1) to (1-3)
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 through 1-3,
X1 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,
S1 to S10 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, c to l are the same as or different from each other, and each independently is an integer of 0 to 4, and when c to l are an integer of 2 or more, the substituents in the parentheses are the same or different,
U1 and U2 are the same or different and are each independently selected from any one of the following formulas (1-4) to (1-7)
[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

In Formulas 1-4 to 1-7,
X2 is a direct bond or -C (Z1) (Z2) -; -CO-; -O-; -S-; -SO ₂ -; And -Si (Z1) (Z2) -, Z1 and Z2 are the same or different from each other and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; And a substituted or unsubstituted aryl group,
T1 and T2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
T3 to T6 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
T7 and T8 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Lt; ₉ &gt; each independently represent -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
M is a metallic element,
q and v are the same or different and each independently an integer of 0 to 4, w and x are the same or different and each independently an integer of 0 to 3, y is an integer of 1 to 4, q to y Q + r? 8, 1? S + t + u + v? 16, and 1? W + x? 6, wherein the substituents in the parentheses are the same or different from each other,
A2 and B2 each independently represent any one selected from the following formulas 1-8 to 1-10,
[Chemical Formula 1-8]

[Chemical Formula 1-9]

[Chemical Formula 1-10]

In Formulas 1-8 to 1-10,
X13 to X17 are the same or different from each other, and each independently is a direct bond, -CO-; And -SO ₂ - and any one selected from,
J1 to J8 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Y3 to Y5 are the same or different and are each independently a direct bond; Or an alkylene group having 1 to 60 carbon atoms,
j1 to j3, j6 and j8 are the same or different and each independently an integer of 0 to 4, j4, j5 and j7 are the same or different and each independently an integer of 0 to 3, j1 to j8 are each an integer of 2 or more The substituents in parentheses are the same or different from each other,
W1 to W3 are the same or different and each independently represents a repeating unit represented by the following formula (1a) in A2, a repeating unit represented by the following formula (1b) in B2,
[Formula 1a]

[Chemical Formula 1b]

In the above formulas (1a) and (1b)
n 'and m' are an integer of 1 or more and 100,000 or less,
A1, B1, U1 and V1 are as defined in formulas (1) and (2). The polymer electrolyte membrane according to claim 1, wherein A1, B1, V1 and V2 are the same or different from each other and are represented by any one of the following structural formulas:

In the above structural formulas, R61 and R62 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o21 and o22 are the same as or different from each other, and each independently an integer of 0 to 4, and when o21 and o22 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other. 2. The polymer electrolyte membrane according to claim 1, wherein U1 and U2 are the same or different from each other, and each independently represents one selected from the following structural formulas:

In the above formula, Q1 and Q2 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted, and a heteroaryl group ring, at least one of Q4 are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; _{3 &} ^{gt ; 2-} 2M &lt; ^{+ &} gt ;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, M is a metallic element, b1 and b2 are the same or different and each independently an integer of 0 to 4, b1 'and b2' are the same or different and independently B1 '+ b2'? 6 and 1? B11, where b11 and b12 are the same or different and each independently an integer of 0 to 8, b4 is an integer of 1 to 4, + b12 8; and when b1, b2, b4, b1 ', b2', b11 and b12 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other. The polymer electrolyte membrane according to claim 1, wherein each of A2 and B2 is represented by any one of the following structural formulas:

In the above structural formulas, J11 to J18 are the same or different and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group; j11 to j13, j16 and j18 are the same or different from each other and each independently an integer of 0 to 4; j14, j15 and j17 are the same as or different from each other, and each independently an integer of 0 to 3; , j11 to j18 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other, and the definitions of the remaining substituents are as defined in formulas 1-8 to 1-10. The polymer electrolyte membrane according to claim 1, wherein the random copolymer comprises at least one selected from the repeating units represented by the following formulas (4) to (10)
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the above formulas 4 to 10,
X3 to X7 are the same or different from each other, and each independently is a direct bond or -CO-; Or -SO ₂ - and,
E1 to E14 are the same or different and are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; -PO ₃ ^2- 2M ^+; Hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; ?,?,?,?,?,?,? And? Are the same or different from each other and each independently an integer of 0 to 4,?,?,?,?,?,?, ? and? are the same or different from each other and each independently an integer of 0 to 3, 0?? +? 7, 0?? +? 6, 0?? +? 5, The substituents in the parentheses are the same or different when?,?,?,?,?,?,?,?,?,?,? and? The polymer electrolyte membrane according to claim 5, wherein the random copolymer comprises a repeating unit represented by the following formula (13) and a repeating unit represented by the following formula (14)
[Chemical Formula 13]

[Chemical Formula 14]

In the above formulas (13) and (14)
U3 is represented by any one of the following formulas (5-1), (7-1) and (9-1)
[Formula 5-1]

[Formula 7-1]

[Formula 9-1]

In Formulas 5-1, 7-1 and 9-1,
X26 is a direct bond, -CO-; Or -SO ₂ - and,
E25 and E26 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
E29 and E30 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
At least one of the E33 are each independently a -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
? 1,? 1,? 1 and? 1 are the same or different and each independently an integer of 0 to 4,? 1 is an integer of 1 to 4, 1?? 1 +? 1? 8, 1? When? 1,? 1,? 1,? 1 and? 1 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,
A3 and B3 are the same or different and at least one is independently represented by the above-described formula (3), the remaining and V3 are the same or different from each other and independently selected from the following formulas (5-2), (7-2) and Is displayed as any one selected,
[Formula 5-2]

[Formula 7-2]

[Formula 9-2]

In the above Formulas 5-2, 7-2 and 9-2,
X36 is a direct bond, -CO-; Or -SO ₂ - and,
E45, E46, E49, E50 and E53 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, and? 2,? 2,? 2,? 2 and? 2 are the same or different from each other and independently an integer of 0 to 4, 0?? 2 +? 2? 6, ,? 2 and? 2 are integers of 2 or more, the substituents in the parentheses are the same or different from each other,
a3 and b3 are an integer of 1 or more. The polymer electrolyte membrane according to claim 6, wherein the U3 is represented by any one of the following structural formulas:

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Q19 and Q20 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
At least one of Q &lt; ₁₃ &gt; is each independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
M is a metallic element,
b21 and b22 are the same or different and each independently an integer of 0 to 4, b29 and b30 are the same or different and each independently an integer of 0 to 6, b23 is an integer of 1 to 4, 1? b21 + b22? 8, 1? b29 + b30? 6, and b21 to b23, b29 and b30 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other. [7] The compound according to claim 6, wherein A3 and B3 are the same or different and at least one is independently represented by the above-described formula (3), and the remainder and V3 are the same or different and independently represent any one selected from the following structural formulas Polymer electrolyte membrane:

In the above structural formulas, R41, R42, R45 and R46 are the same or different from each other and each independently represents a halogen group; A nitro group; And o3 and o4 are the same or different from each other and each independently an integer of 0 to 4, o7 and o8 are the same or different and each independently an integer of 0 to 6 and 0? O7 + o8 6, and o3, o4, o7 and o8 are each 2 or more, the substituents in the parentheses are the same or different from each other. The polymer electrolyte membrane according to claim 6, wherein A3 is represented by the following formula (3), wherein A3 is represented by the following formula:

In the above formula, Q11 and Q12 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; And m is a metallic element, q1 and q2 are the same as or different from each other and each independently an integer of 0 to 8, 1? Q1 + q2? 8, and q1 and q2 are When each is an integer of 2 or more, the substituents in the parentheses are the same or different from each other. 7. The polymer electrolyte membrane according to claim 6, wherein B3 is represented by any one of the following structural formulas when B3 is represented by the formula (3)

In the above structural formulas, R11 to R14 are the same or different from each other and each independently represents a halogen group; A nitro group; Or a trifluoromethyl group, o1 to o4 are the same or different from each other and independently represent an integer of 0 to 4, and when o1 to o4 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other. The polymer electrolyte membrane according to claim 6, wherein the random copolymer further comprises at least one repeating unit represented by any one of the following structural formulas:

At least one of Q &lt; ₁₄ &gt; is independently -SO3H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Q15 and Q16 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Q17 and Q18 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Q21 to Q24 are the same or different from each other, at least one is independently -SO ₃ H; -SO ₃ ^- M ^+; -COOH; -COO ^- M ⁺ ; -PO ₃ H ₂ ; -PO ₃ H ^- M ^+; Or -PO &lt; ₃ &gt; ^2- 2M &lt; ⁺ &gt;; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
M is a metallic element,
b28 and b31 to b33 are the same or different and each independently an integer of 0 to 4, b24 is an integer of 1 to 3, b27 and b34 are the same or different and each independently an integer of 0 to 3, b25 And b26 are the same or different from each other and each independently an integer of 0 to 5, 1? B25 + b26? 5, 1? B27 + b28? 7, 1? B31 + b32 + b33 + b34? To b28 and b31 to b34 are each an integer of 2 or more, the substituents in the parentheses are the same or different from each other,
R41 to R44 and R47 to R50 are the same or different and each independently represents a halogen group; A nitro group; And o3 to o5 and o12 are the same as or different from each other and each independently an integer of 0 to 4, o6 and o11 are the same as or different from each other, and each independently an integer of 0 to 3, o9 and o10 O9 + o10? 5, and when o3 to o6 and o9 to o12 are each an integer of 2 or more, the substituents in the parentheses are the same as or different from each other. The polymer electrolyte membrane according to claim 1, wherein the block copolymer and the random copolymer further comprise a branching agent represented by the following formula (11) or (12):
(11)

[Chemical Formula 12]

In the above formulas (11) and (12)
X is -S-; -O-; -CO-; -SO-; -SO ₂ -; -NR-; A hydrocarbon-based or fluorine-
p is an integer of 0 to 100, and when p is 2 or more, 2 or more X's are the same or different,
Y1 and Y2 are the same or different from each other and each independently represents an aromatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; An aliphatic ring substituted by one or more substituents selected from the group consisting of a hydroxyl group and a halogen group; Or an NR &apos; R "
R, R 'and R "are the same or different and each independently represents an aromatic ring substituted with a halogen group, or an aliphatic ring substituted with a halogen group,
Z is a trivalent organic group. The polymer electrolyte membrane according to claim 1, wherein the random copolymer is a branched sulfonated random copolymer. The polymer electrolyte membrane of claim 1, wherein the block copolymer is a branched sulfonated block copolymer. According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer is 0.1: 9.9 to 9.9: 0.1. The polymer electrolyte membrane according to claim 1, wherein the block copolymer has an ion exchange capacity (IEC) of 1.6 meq./g to 2.0 meq./g. The polymer electrolyte membrane according to claim 1, wherein the ion exchange capacity (IEC) of the random copolymer is 1.3 meq./g to 2.2 meq./g. Anode; Cathode; And a polymer electrolyte membrane according to any one of claims 1 to 17 provided between the anode and the cathode. At least two membrane electrode assemblies (MEAs) according to claim 18;
A stack including a bipolar plate disposed between the membrane electrode assemblies;
A fuel supply unit for supplying fuel to the stack; And
And an oxidant supplier for supplying the oxidant to the stack.

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