KR102481620B1 - Block copolymer and preparation method thereof - Google Patents

Abstract

The present specification includes a hydrophilic unit, a hydrophobic unit, and a fluorine-containing compound, wherein the hydrophilic unit includes a unit derived from a compound represented by Formula 1, and the hydrophobic unit includes a unit derived from a compound represented by Formula 3 It relates to a block copolymer that includes.

Description

Block copolymer and its preparation method {BLOCK COPOLYMER AND PREPARATION METHOD THEREOF}

The present specification relates to a block copolymer and a method for preparing the same.

Separator materials for fuel cells have high ionic conductivity, and at the same time, to prevent cell efficiency deterioration during operation, 1) prevention of crossover of electrolyte materials, 2) strong chemical resistance during cell operation, 3) enhanced mechanical properties, 4 ) Must have characteristics such as low swelling ratio. Currently, most fuel cell separator materials use Nafion. Nafion has high ionic conductivity and good thermal and mechanical properties, but has the disadvantage of increasing membrane resistance with increasing thickness to secure high price, methanol crossover, and mechanical properties. Therefore, it is required to develop a material that has both the high ionic conductivity of Nafion and the mechanical properties of hydrocarbons.

US Patent Application Publication No. 2008-0241626

The present specification provides a block copolymer and a method for preparing the same.

An exemplary embodiment of the present specification includes a hydrophilic unit, a hydrophobic unit, and a fluorine-containing compound, wherein the hydrophilic unit includes a unit derived from a compound represented by Formula 1 below, and the hydrophobic unit is represented by Formula 3 below It provides a block copolymer comprising units derived from the compound:

[Formula 1]

In Formula 1,

L1 and L2 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRa-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

A is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , or -PO ₃ ^{2-2M +} ;

R1 to R5 are the same as or different from each other, and each independently hydrogen; halogen group; Or a hydroxy group, at least two of R1 to R5 are halogen groups or hydroxy groups,

R6 to R9 are the same as or different from each other, and each independently represents a halogen group;

Ra is hydrogen; Or a substituted or unsubstituted alkyl group,

n is an integer from 2 to 10, m is an integer from 2 to 10, and when n and m are integers greater than or equal to 2, the structures in parentheses are the same as or different from each other,

M is a group 1 element.

[Formula 3]

In Formula 3,

X2 is a direct bond; -C(Z3)(Z4)-; -O-; -S-; —SO ₂ —; -CO-; or -Si(Z3)(Z4)-;

Y1 and Y2 are the same as or different from each other, and each independently a halogen group; Or a hydroxy group,

Z3 and Z4 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

S1 and S2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, s1 and s2 are integers from 0 to 4, and when s1 and s2 are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, an exemplary embodiment of the present specification includes (A) synthesizing a hydrophilic unit including a unit derived from the compound represented by Formula 1; (B) synthesizing a hydrophobic unit including a unit derived from the compound represented by Formula 3; and (C) reacting the hydrophilic unit, the hydrophobic unit, and a fluorine-containing compound.

The block copolymer according to an exemplary embodiment of the present specification can secure a high level of molecular weight without difficulty in adjusting the polymer equivalent, and the ion exchange capacity (IEC) value can be adjusted by adjusting the reaction ratio between the hydrophilic unit and the hydrophobic unit. Do.

In addition, the block copolymer according to an exemplary embodiment of the present specification can achieve high ion conductivity through perfluorosulfonic acid of the hydrophilic unit and high mechanical stability even under humidification conditions through the hydrophobic unit.

In addition, in the method for producing a block copolymer according to an exemplary embodiment of the present specification, a coupling reaction is possible even at a low temperature by using decafluorobiphenyl showing high reactivity between a hydrophilic unit and a hydrophobic unit.

1 is a schematic diagram showing the principle of generating electricity in a fuel cell.
2 is a diagram schematically illustrating an embodiment of a fuel cell.
3 is a diagram showing an NMR spectrum of a hydrophilic unit A according to an exemplary embodiment of the present specification.
4 is a diagram showing an NMR spectrum of a hydrophilic unit B according to an exemplary embodiment of the present specification.
5 is a diagram showing an NMR spectrum of a hydrophilic unit C according to an exemplary embodiment of the present specification.
6 is a diagram showing an NMR spectrum of a hydrophobic unit according to an exemplary embodiment of the present specification.
7 is a diagram showing an NMR spectrum of a random multi-block copolymer I according to an exemplary embodiment of the present specification.
8 is a diagram showing an NMR spectrum of a random multi-block copolymer II according to an exemplary embodiment of the present specification.
9 is a diagram showing an NMR spectrum of a random multi-block copolymer III according to an exemplary embodiment of the present specification.

Hereinafter, this specification will be described in more detail.

According to an exemplary embodiment of the present specification, a hydrophilic unit, a hydrophobic unit, and a fluorine-containing compound are included, wherein the hydrophilic unit includes a unit derived from a compound represented by Formula 1 below, and the hydrophobic unit is represented by Formula 3 below A block copolymer containing units derived from the compounds shown is provided.

[Formula 1]

In Formula 1,

L1 and L2 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRa-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

A is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , or -PO ₃ ^{2-2M +} ;

R1 to R5 are the same as or different from each other, and each independently hydrogen; halogen group; Or a hydroxy group, at least two of R1 to R5 are halogen groups or hydroxy groups,

R6 to R9 are the same as or different from each other, and each independently represents a halogen group;

Ra is hydrogen; Or a substituted or unsubstituted alkyl group,

n is an integer from 2 to 10, m is an integer from 2 to 10, and when n and m are integers greater than or equal to 2, the structures in parentheses are the same as or different from each other,

M is a group 1 element.

[Formula 3]

In Formula 3,

X2 is a direct bond; -C(Z3)(Z4)-; -O-; -S-; —SO ₂ —; -CO-; or -Si(Z3)(Z4)-;

Y1 and Y2 are the same as or different from each other, and each independently a halogen group; Or a hydroxy group,

Z3 and Z4 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

S1 and S2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, s1 and s2 are integers from 0 to 4, and when s1 and s2 are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

The block copolymer according to an exemplary embodiment of the present specification can secure a high level of molecular weight without difficulty in adjusting the polymer equivalent, and the ion exchange capacity (IEC) value can be adjusted by adjusting the reaction ratio between the hydrophilic unit and the hydrophobic unit. Do.

In addition, the block copolymer according to an exemplary embodiment of the present specification can achieve high ion conductivity through perfluorosulfonic acid of the hydrophilic unit and high mechanical stability even under humidification conditions through the hydrophobic unit.

In addition, in the method for producing a block copolymer according to an exemplary embodiment of the present specification, a coupling reaction is possible even at a low temperature by using decafluorobiphenyl showing high reactivity between a hydrophilic unit and a hydrophobic unit.

As a result, a hydrophilic domain of a continuous structure can be obtained by phase separation of a copolymer of a hydrophilic block and a hydrophobic block, and through this, an interconnected channel can be formed.

On the other hand, the multi-polymer polymer having a structure of hydrophilic and hydrophobic units forms a hydrophilic domain and a hydrophobic domain structure, and through the formation of a continuous ion channel structure through the hydrophilic domain, not only can the hydrogen ion conductivity be clearly increased, but also , mechanical properties can also be increased through the hydrophobic domain. Therefore, the concept of a polymer having a hydrophilic unit-hydrophobic unit structure is essential to the application of a fuel cell separator using a hydrocarbon-based polymer.

Accordingly, the polymer according to one embodiment of the present specification introduces the concept of a random multi-block copolymer to increase ionic conductivity and maintain mechanical properties, transfer ions through hydrophilic units, and improve mechanical properties through hydrophobic units. On the other hand, high ion conductivity can be imparted by introducing -CF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ K instead of -OCF ₂ CF ₂ SO ₃ K generally introduced into hydrocarbon-based polymers. According to references, -OCF ₂ CF ₂ SO ₃ K has a rigid structure and is disadvantageous in forming an ion conducting channel, resulting in lower performance. Therefore, it can be seen that -CF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ K having a longer length shows higher performance. (See References Jounal of Fluorine Chemistry 2016, 189, 43-50, doi: 10.1016/j.fluchem.2016.07.017, 44p line 17)

In JP2005-314452A (Sumitomo Chemical) for polyarylene-based polymers, the main chain of the polymer is a polymer composed of carbon-carbon (C-C) bonds by polymerization using a Yamamoto coupling reaction, and in one embodiment of the present specification The hydrophilic unit is a polymer formed by polymerization using a nucleophilic aromatic substitution reaction (SNAr). Therefore, oxygen (O), which is a hetero element, is included in the main chain, and a C-O bond is included.) In addition, monomers containing perfluorinated sulfonic acid are not randomly located, but are selectively located in hydrophilic blocks. , the polymer in the form of a random multi-block copolymer exhibits better performance as a separator material for fuel cells.

JP2005-314452A (Sumitomo Chemical) synthesizes the main chain by Yamamoto coupling a monomer having two chlorine functional groups, and then post-modification (reaction to introduce Br) Through the introduction of a bromine (Br) functional group to the side branch, the introduction of perfluorinated sulfonic acid by Ullmann coupling. It can be seen that the position at which the bromine (Br) functional group can be introduced by post modification of the polymer is the para or ortho position, which is relatively electron-rich, and the meta position is not possible.

Specifically, in this case, Br and I of ICF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ H at the para position of the benzene ring are desorbed under the Cu catalyst, and the -CF ₂ CF ₂ OCF ₂ CF ₂ SO ₃ H functional group is formed on the benzene ring. introduced At this time, it is difficult to obtain a yield of 100% of this reaction, and a process for removing Cu is additionally required. In addition, there is a disadvantage in that it is difficult to accurately introduce a selective position and a target amount.

However, according to an exemplary embodiment of the present specification, in the compound represented by Chemical Formula 1, perfluorinated sulfonic acid may be introduced at positions such as meta and para based on the main chain of the polymer, and a polymer is formed and the polymer is formed. It is characterized in that a step of introducing additional perfluorinated sulfonic acid is not required by introducing it from the monomer step rather than introducing it later. In addition, it is judged that the introduction of perfluorinated sulfonic acid into the phenyl group will be stable from hydroxyl radical (˚OH), which is known to degrade membrane performance during fuel cell operation, and thioether ( Since -S-) can act as an internal scavenger, it can provide sufficient stability. (See reference Macromolecules 2016, 49, 4164-4177, doi: 10.1021/acs.macromol.6b00629, 4165p line 16).

In addition, according to an exemplary embodiment of the present specification, the compound represented by Formula 1 has acid resistance due to a sulfur (S) linking group, and in particular forms a polymer using the compound represented by Formula 1 or a unit derived therefrom. In the case of doing so, excellent acid resistance properties can be exhibited.

In addition, the unit derived from the compound represented by Chemical Formula 1 according to an exemplary embodiment of the present specification has high reactivity in the polymerization process, thereby increasing process efficiency.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

In the present specification, "derived" means that a bond of a compound is broken or a new bond is generated while a substituent is removed, and a unit derived from the compound may refer to a unit connected to the main chain of the polymer. The unit may constitute a polymer by being included in a main chain in a polymer.

In the present specification, a "unit" is a structure in which a monomer is included in a polymer and is repeated, and means a structure in which the monomer is bonded to the polymer by polymerization.

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

In this specification, "separation membrane" is a membrane capable of exchanging ions, and includes a membrane, an ion exchange membrane, an ion transfer membrane, an ion conductive membrane, an ion exchange separator, an ion transfer separator, an ion conductive separator, an ion exchange electrolyte membrane, and an ion transfer membrane. and an electrolyte membrane or an ion conductive electrolyte membrane.

In the present specification, the term "substituted or unsubstituted" means deuterium; halogen group; cyano group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; And substituted with one or more substituents selected from the group consisting of substituted or unsubstituted heteroaryl groups, substituted with substituents in which two or more substituents among the above-exemplified substituents are linked, or without any substituents. For example, “a substituent having two or more substituents connected” includes an alkyl group substituted with a halogen group, an aryl group substituted with an alkyl group, an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, an aryl group substituted with a silyl group, and an aryl group substituted with an alkyl group. A silyl group, a heteroaryl group substituted with an alkyl group, a heteroaryl group substituted with an aryl group, and a heteroaryl group substituted with a heteroaryl group, but are not limited thereto.

In the present specification, the term "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is changed to another substituent, and the position to be substituted is not limited to a position where a hydrogen atom is substituted, that is, a position where the substituent is substituted, 2 In the case of over-substitution, two or more substituents may be the same as or different from each other.

In the present specification, "hydrocarbon" refers to an organic compound composed of only carbon and hydrogen, and includes straight-chain, branched-chain, and cyclic hydrocarbons, but is not limited thereto. In addition, it may include a single bond, double bond or triple bond, but is not limited thereto.

In the present specification, "fluorine-based compound" means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.

In the present specification, "hydrophilic unit" means a polymer having an ion exchange group as a functional group. Here, the functional group is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , -PO ₃ ^2- 2M ⁺ , -O(CF ₂ ) _w SO ₃ H, -O(CF ₂ ) _w SO ₃ ^- M ⁺ , -O(CF ₂ ) _w COOH, -O(CF ₂ ) _w COO ^- M ⁺ , -O(CF ₂ ) _w PO ₃ H ₂ , -O(CF ₂ ) _w PO ₃ H ^- M ⁺ and -O(CF ₂ ) _w PO ₃ ^{2 -} may be at least one selected from the group consisting of 2M ⁺ . Here, M is a metallic element, and w may have a range of 1<w<10. That is, the functional group may be hydrophilic.

In the present specification, "polymer having an ion exchange group" means a polymer containing an average of 0.5 or more, expressed as the number of ion exchange groups per structural monomer constituting the polymer, and an average of 1.0 or more per structural monomer. It is more preferable if it has an ion exchanger.

In the present specification, "hydrophobic unit" means the above-described polymeric polymer having substantially no ion exchange group.

In the present specification, "a polymer having substantially no ion exchange groups" means a polymer having an average number of ion exchange groups per structural monomer constituting the polymer, which is less than 0.1, and an average of 0.05 or less is more preferable. , it is more preferable if it is a polymer having no ion exchange groups at all.

In the present specification, the halogen group may be F, Cl, Br, I or the like.

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. According to one embodiment, the number of carbon atoms of the alkyl group is 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is 1 to 10. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl heptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 50 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 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 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 number of carbon atoms of the aryl group is 6 to 30. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 20. The monocyclic aryl group may include, but is not limited to, a phenyl group, a biphenyl group, and a terphenyl group. Examples of the polycyclic aryl group include a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenalenyl group, chrysenyl group, fluorenyl group, and benzofluorene. It may be a yl group, a spirobifluorenyl group, a triphenylene group, and a spirobenzoanthracene fluorenyl group, but is not limited thereto.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, that is, heteroatoms, specifically, the heteroatoms are atoms selected from the group consisting of N, P, O, S, Se, Ge, and Si. Can contain 1 or more. The carbon number is not particularly limited, but preferably has 2 to 50 carbon atoms, and according to an exemplary 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 pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, Triazinyl group, triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyra Ginopyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzo Furanyl group, dibenzofuranyl group, naphthobenzofuranyl group, phenanthroline group, thiadiazolyl group, phenothiazinyl group, acenaphthoquinoxalyl group, indenoquinazolyl group, indenoisoquinolyl group group, an indenoquinolyl group, a pteridinyl group, a phenoxazinyl group, a benzoquinazolyl group, an indazolyl group, a benzoperimidinolyl group, a benzoperimidinyl group, and a spiroacridine fluorenyl group, but are limited thereto it is not going to be

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 50 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, etc., but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 9-methylanthracenylamine group, Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-biphenyl Naphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group , N- phenanthrenyl fluorenyl amine group, N- biphenyl fluorenyl amine group, etc., but is not limited thereto.

는 인접한 치환기 또는 중합체의 주쇄와 결합할 수 있는 것을 의미한다.According to one embodiment of the present specification,

means capable of bonding with an adjacent substituent or the main chain of a polymer.

According to an exemplary embodiment of the present specification, the hydrophilic unit in the block copolymer includes a unit derived from the compound represented by Formula 1.

According to an exemplary embodiment of the present specification, R1 to R5 are the same as or different from each other, and each independently hydrogen; F; or a hydroxy group, and at least two of R1 to R5 are F or hydroxy groups.

According to an exemplary embodiment of the present specification, at least two of R1 to R5 are sites binding to the main chain of the polymer.

According to an exemplary embodiment of the present specification, R2 and R4 are sites binding to the main chain of the polymer.

According to an exemplary embodiment of the present specification, R2 and R4 are F.

According to an exemplary embodiment of the present specification, R2 and R4 are hydroxyl groups.

According to an exemplary embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRa-; -SO ₂ -; or an alkylene group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRa-; or -SO ₂ -.

According to an exemplary embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; -S-; or -O-.

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

According to one embodiment of the present specification, L2 is -O-.

According to an exemplary embodiment of the present specification, A is -SO ₃ H or -SO ₃ ^- M ⁺ .

According to an exemplary embodiment of the present specification, when A is -SO ₃ H, or -SO ₃ -M ⁺ , a polymer including a unit derived from the compound represented by Formula ¹ may be chemically stably formed there is.

According to an exemplary embodiment of the present specification, M is a group 1 element.

According to one embodiment of the present specification, the group 1 element is Li, Na or K.

According to an exemplary embodiment of the present specification, R6 to R9 are the same as or different from each other, and each independently represents a halogen group.

According to an exemplary embodiment of the present specification, R6 to R9 are F.

According to an exemplary embodiment of the present specification, n is an integer of 2 to 6, and m is an integer of 2 to 6.

According to an exemplary embodiment of the present specification, n is an integer of 2.

According to an exemplary embodiment of the present specification, m is an integer of 2.

According to an exemplary embodiment of the present specification, Formula 1 may be represented by Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2, substituents are defined as defined in Chemical Formula 1.

According to an exemplary embodiment of the present specification, Chemical Formula 1 may be represented by one selected from Chemical Formulas 1-1-1 to 1-1-5.

[Formula 1-1-1]

[Formula 1-1-2]

[Formula 1-1-3]

[Formula 1-1-4]

[Formula 1-1-5]

In Chemical Formulas 1-1-1 to 1-1-5, substituents are defined as defined in Chemical Formula 1.

According to an exemplary embodiment of the present specification, the hydrophilic unit in the block copolymer may further include a unit derived from a compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

X1 is a direct bond; -C(Z1)(Z2)-; -O-; -S-; —SO ₂ —; -CO-; or -Si(Z1)(Z2)-;

Z1 and Z2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

T1 and T2 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, t1 and t2 are integers from 0 to 4, and when t1 and t2 are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, X1 is a direct bond.

According to an exemplary embodiment of the present specification, the X1 is -C(Z1)(Z2)-.

According to an exemplary embodiment of the present specification, X1 is -O-.

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

According to an exemplary embodiment of the present specification, X1 is —SO ₂ —.

According to an exemplary embodiment of the present specification, X1 is —CO—.

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

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; 1 to 10 substituted or unsubstituted alkyl groups; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently a halogen group; or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z1 and Z2 are the same as or different from each other, and each independently represents a methyl group unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z1 and Z2 are -CF ₃ .

According to an exemplary embodiment of the present specification, T1 and T2 are the same as or different from each other, and each independently hydrogen; or a halogen group.

According to an exemplary embodiment of the present specification, T1 and T2 are hydrogen.

According to an exemplary embodiment of the present specification, the hydrophilic unit may include a repeating unit represented by Formula 4 below.

[Formula 4]

In Formula 4,

p1, a and a' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, a: a' is 1,000: 1 to 1: 1,000,

R10 is a halogen group, k is an integer from 0 to 3,

L11 and L12 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRb-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

A' is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , or -PO ₃ ^2- 2M ⁺ , and M is is a group 1 element,

R16 to R19 are the same as or different from each other, and each independently represents a halogen group;

Rb is hydrogen; Or a substituted or unsubstituted alkyl group,

n' is an integer from 2 to 10, m' is an integer from 2 to 10, the structures in parentheses are the same as or different from each other,

X11 is a direct bond; -C(Z11)(Z12)-; -O-; -S-; —SO ₂ —; -CO-; or -Si(Z11)(Z12)-;

Z11 and Z12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

T11 and T12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, t11 and t12 are integers from 0 to 4, and when t11 and t12 are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, the L11 and L12 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -NRa-; or -SO ₂ -.

According to an exemplary embodiment of the present specification, the L11 and L12 are the same as or different from each other, and each independently a direct bond; -S-; or -O-.

According to one embodiment of the present specification, L11 is -S-.

According to one embodiment of the present specification, L12 is -O-.

According to an exemplary embodiment of the present specification, A' is -SO ₃ H or -SO ₃ ^- M ⁺ .

According to an exemplary embodiment of the present specification, when A' is -SO ₃ H or -SO ₃ -M ⁺ , a polymer including a unit derived from the compound represented by Formula ¹ is chemically stably formed can

According to an exemplary embodiment of the present specification, R16 to R19 are the same as or different from each other, and each independently represents a halogen group.

According to an exemplary embodiment of the present specification, R16 to R19 are F.

According to an exemplary embodiment of the present specification, n' is an integer of 2 to 6, and m' is an integer of 2 to 6.

According to an exemplary embodiment of the present specification, n' is an integer of 2.

According to an exemplary embodiment of the present specification, m' is an integer of 2.

According to one embodiment of the present specification, X11 is a direct bond.

According to one embodiment of the present specification, the X11 is -C(Z11)(Z12)-.

According to one embodiment of the present specification, the X11 is —O—.

According to one embodiment of the present specification, the X11 is -S-.

According to one embodiment of the present specification, the X11 is —SO ₂ —.

According to one embodiment of the present specification, the X11 is —CO—.

According to one embodiment of the present specification, X11 is -Si(Z11)(Z12)-.

According to an exemplary embodiment of the present specification, Z11 and Z12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; 1 to 10 substituted or unsubstituted alkyl groups; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Z11 and Z12 are the same as or different from each other, and each independently a halogen group; or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z11 and Z12 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z11 and Z12 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z11 and Z12 are the same as or different from each other, and each independently represents a methyl group substituted with F.

According to an exemplary embodiment of the present specification, Z11 and Z12 are -CF ₃ .

According to an exemplary embodiment of the present specification, T11 and T12 are the same as or different from each other, and each independently hydrogen; or a halogen group.

According to an exemplary embodiment of the present specification, T11 and T12 are hydrogen.

According to an exemplary embodiment of the present specification, R10 is hydrogen.

According to an exemplary embodiment of the present specification, Chemical Formula 4 may be represented by Chemical Formula 4-1 below.

[Formula 4-1]

In Formula 4-1, substituents are defined as defined in Formula 4.

According to an exemplary embodiment of the present specification, Chemical Formula 4 may be represented by one selected from Chemical Formulas 4-1-1 to 4-1-3.

[Formula 4-1-1]

[Formula 4-1-2]

[Formula 4-1-3]

In Chemical Formulas 4-1-1 to 4-1-3, substituents are defined as defined in Chemical Formula 4.

According to one embodiment of the present specification, the hydrophobic unit in the block copolymer may include a unit derived from the compound represented by Chemical Formula 3.

According to one embodiment of the present specification, the X2 is a direct bond.

According to one embodiment of the present specification, the X2 is -C(Z3)(Z4)-.

According to one embodiment of the present specification, the X2 is —O—.

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

According to an exemplary embodiment of the present specification, the X2 is -SO ₂ -.

According to one embodiment of the present specification, the X2 is —CO—.

According to one embodiment of the present specification, X2 is -Si(Z3)(Z4)-.

According to an exemplary embodiment of the present specification, Z3 and Z4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; 1 to 10 substituted or unsubstituted alkyl groups; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Z3 and Z4 are the same as or different from each other, and each independently a halogen group; or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z3 and Z4 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z3 and Z4 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z3 and Z4 are the same as or different from each other, and each independently represents a methyl group unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z3 and Z4 are -CF ₃ .

According to an exemplary embodiment of the present specification, S1 and S2 are the same as or different from each other, and each independently hydrogen; or a halogen group.

According to an exemplary embodiment of the present specification, S1 and S2 are hydrogen.

According to an exemplary embodiment of the present specification, Chemical Formula 3 may be represented by one selected from Chemical Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

According to an exemplary embodiment of the present specification, the hydrophobic block may include two or more different units derived from the compound represented by Chemical Formula 3.

According to an exemplary embodiment of the present specification, the hydrophobic block may include units derived from compounds represented by the following Chemical Formulas 3A and 3B.

[Formula 3A]

[Formula 3B]

In Formulas 3A and 3B,

X20 and X30 are the same as or different from each other and are each independently a direct bond; -C(Z21)(Z22)-; -O-; -S-; —SO ₂ —; -CO-; or —Si(Z21)(Z22)—, Z21 and Z22 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

Y20, Y21, Y30, and Y31 are the same as or different from each other, and each independently a halogen group; Or a hydroxy group,

S20, S21, S30, and S31 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, s20, s21, s30 and s31 are integers from 0 to 4, and when s20, s21, s30 and s31 are an integer of 2 or more, the substituents in parentheses are the same as or different from each other,

However, at least 2 of Y20, Y21, Y30 and Y31 is a hydroxyl group.

According to one embodiment of the present specification, the X20 is a direct bond.

According to one embodiment of the present specification, the X20 is -C(Z21)(Z22)-.

According to one embodiment of the present specification, the X20 is —O—.

According to one embodiment of the present specification, the X20 is -S-.

According to one embodiment of the present specification, the X20 is -SO ₂ -.

According to one embodiment of the present specification, the X20 is —CO—.

According to one embodiment of the present specification, X20 is -Si(Z21)(Z22)-.

According to one embodiment of the present specification, the X30 is a direct bond.

According to one embodiment of the present specification, the X30 is -C(Z21)(Z22)-.

According to one embodiment of the present specification, the X30 is —O—.

According to one embodiment of the present specification, the X30 is -S-.

According to one embodiment of the present specification, the X30 is —SO ₂ —.

According to one embodiment of the present specification, the X30 is —CO—.

According to one embodiment of the present specification, the X30 is -Si(Z21)(Z22)-.

According to an exemplary embodiment of the present specification, Z21 and Z22 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; 1 to 10 substituted or unsubstituted alkyl groups; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, Z21 and Z22 are the same as or different from each other, and each independently a halogen group; or an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z21 and Z22 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, Z21 and Z22 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms unsubstituted or substituted with F.

According to an exemplary embodiment of the present specification, Z21 and Z22 are the same as or different from each other, and each independently represents a methyl group substituted with F.

According to an exemplary embodiment of the present specification, Z21 and Z22 are -CF ₃ .

According to an exemplary embodiment of the present specification, S20, S21, S30 and S31 are the same as or different from each other, and each independently hydrogen; or a halogen group.

According to an exemplary embodiment of the present specification, S20, S21, S30 and S31 are hydrogen.

According to an exemplary embodiment of the present specification, Y20 and Y21 are identical to each other.

According to an exemplary embodiment of the present specification, Y30 and Y31 are identical to each other.

According to an exemplary embodiment of the present specification, Y20 and Y21 are halogen groups, and Y30 and Y31 are hydroxy groups.

According to an exemplary embodiment of the present specification, Y20 and Y21 are hydroxy groups, and Y30 and Y31 are halogen groups.

According to an exemplary embodiment of the present specification, Y20 and Y21 are hydroxyl groups, and Y30 and Y31 are hydroxyl groups.

According to an exemplary embodiment of the present specification, the hydrophobic unit may include a repeating unit represented by Formula 5 below.

[Formula 5]

In Formula 5,

p2, b and b' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, b: b' is 1,000: 1 to 1: 1,000,

X3 and X4 are the same as or different from each other, and are each independently a direct bond; -C(Z3)(Z4)-; -O-; -S-; —SO ₂ —; -CO-; or -Si(Z3)(Z4)-;

Z3 and Z4 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

S3 to S6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, s3 to s6 are integers from 0 to 4, and when s3 to s6 are an integer of 2 or more, the substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, Formula 5 may be represented by Formula 5-1 below.

[Formula 5-1]

In Formula 5-1, substituents are defined as defined in Formula 5.

According to an exemplary embodiment of the present specification, the fluorine-containing compound may be decafluorobiphenyl. However, it is not limited thereto. Decafluorobiphenyl is represented by the following structural formula.

According to one embodiment of the present specification, the block copolymer may further include a brancher.

In the present specification, "Brancher" serves to connect or bridge polymer chains.

According to an exemplary embodiment of the present specification, the branch may serve to connect or bridge the polymer chain.

According to an exemplary embodiment of the present specification, in the case of a block copolymer further comprising the branch office, the branch office may directly constitute the main chain of the copolymer, and improve the mechanical integration of the thin film. For example, the branched block copolymer according to one embodiment of the present specification includes a branched hydrophobic block containing no acid substituents and a branched hydrophilic block containing acid substituents. By polymerization, the brancher directly constitutes the main chain of the polymer without performing post-sulfonation or cross-linking of the sulfonated polymer, and the thin film The hydrophobic block that maintains the mechanical density of the film and the hydrophilic block that imparts ionic conductivity to the thin film can alternately lead to chemical bonding.

According to an exemplary embodiment of the present specification, the block copolymer may further include a branch derived from a compound represented by Formula 6 or a branch represented by Formula 7 below.

[Formula 6]

[Formula 7]

In Formulas 6 and 7,

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

l is an integer from 0 to 100, and when l is 2 or more, 2 or more X's are the same as or different from each other;

Q1 and Q2 are the same as or different from each other, and are each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxyl group and a halogen group; an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an amine group represented by NR'R",

R, R' and R" are an aromatic ring substituted with a halogen group; or an aliphatic ring substituted with a halogen group,

Z is a trivalent organic group.

In the present specification, the "organic group" includes an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and the like. Bonds other than hydrocarbon groups such as heteroatoms or substituents may be included in the organic groups. Moreover, any of linear, branched chain, and cyclic may be sufficient as the said organic group.

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

In addition, according to one embodiment of the present specification, the organic group may form a cyclic structure, and may include a heteroatom to form a bond as long as the effects of the invention are not impaired. Specifically, a bond containing a heteroatom such as an oxygen atom, a nitrogen atom, or a silicon atom is exemplified. Specific examples include ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond (-N=C(-W)-, -C(=NW) -; W represents a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like, but are not limited thereto.

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

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

In the present specification, the aromatic hydrocarbon ring includes a monocyclic aromatic ring such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a binaphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a perylenyl group, and a tetracenyl group. , polycyclic aromatic rings such as a chrysenyl group, a fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthene group, and the like, but are not limited thereto. In the present specification, the description of the aryl group may be applied to the aromatic hydrocarbon ring.

In the present specification, the aromatic heterocycle is a structure containing one or more atoms selected from the group consisting of heteroatoms such as N, P, O, S, Se, Ge, and Si instead of carbon atoms in the aromatic hydrocarbon ring. Meaning, the description of the heteroaryl group may be applied. Specifically, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, a triazole group, an acridyl group, Pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group, Carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group , a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

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 cycloalkyl group may be applied to the aliphatic hydrocarbon ring.

In the present specification, the aliphatic heterocycle is a heteroatom instead of a carbon atom in the aliphatic hydrocarbon ring, such as a structure containing one or more atoms selected from the group consisting of N, P, O, S, Se, Ge, and Si. it means.

In the present specification, the heterocyclic group may be applied to the description of the aromatic heterocyclic ring and aliphatic heterocyclic ring.

According to an exemplary embodiment of the present specification, Z is a trivalent substituted or unsubstituted alkyl group.

According to an exemplary embodiment of the present specification, Z is a trivalent alkyl group.

According to an exemplary embodiment of the present specification, the branch derived from the compound of Formula 6 is an aromatic ring substituted with a halogen group of each of Q1 and Q2; an aliphatic ring substituted with a halogen group; Alternatively, the halogen group of the amine group represented by NR'R" may act as a brancher while being separated from the aromatic ring or the aliphatic ring.

According to an exemplary embodiment of the present specification, l is an integer of 3 or greater.

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

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

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

According to an exemplary embodiment of the present specification, Q1 and Q2 are the same as or different from each other, and each independently represents an aromatic ring substituted with a halogen group.

According to an exemplary embodiment of the present specification, Q1 and Q2 are the same as or different from each other, and are each independently an aromatic hydrocarbon ring substituted with F.

According to an exemplary embodiment of the present specification, Q1 and Q2 are the same as or different from each other, and are each independently an amine group represented by NR'R".

According to another exemplary embodiment of the present specification, each of Q1 and Q2 is a phenyl group substituted with fluorine. Specifically, 2,4-difluorophenyl, 2,6-difluorophenyl, 2,3-difluorophenyl, 3,4-difluorophenyl and the like, but are not limited thereto.

According to an exemplary embodiment of the present specification, the compound of Formula 6 may be represented by any one selected from the following structures.

In the above structures, the definitions of X, l, R' and R" are as defined in Formula 6.

According to an exemplary embodiment of the present specification, Z in Formula 7 may be represented by one selected from Formulas 7-1 to 7-4.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Formula 7-4]

In Chemical Formulas 7-1 to 7-4,

L21 to L27 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -CO-; or -SO ₂ -;

W11 to W21 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

w1, w2, w3, w6, w8, w9 and w10 are each an integer of 1 to 4, w4, w5 and w7 are each an integer of 1 to 3, w11 is an integer of 1 to 6, and w1 to w11 are each an integer of 1 to 3 In the case of an integer of 2 or more, structures in parentheses of 2 or more are the same as or different from each other.

According to an exemplary embodiment of the present specification, L21 is CO.

According to an exemplary embodiment of the present specification, L21 is SO ₂ .

According to one embodiment of the present specification, L21 is S.

According to an exemplary embodiment of the present specification, L22 is CO.

According to an exemplary embodiment of the present specification, L22 is SO ₂ .

According to one embodiment of the present specification, L22 is S.

According to one embodiment of the present specification, L23 is CO.

According to an exemplary embodiment of the present specification, L23 is SO ₂ .

According to an exemplary embodiment of the present specification, L23 is S.

According to an exemplary embodiment of the present specification, L24 is CO.

According to an exemplary embodiment of the present specification, L24 is SO ₂ .

According to an exemplary embodiment of the present specification, L25 is a direct bond.

According to an exemplary embodiment of the present specification, L26 is a direct bond.

According to an exemplary embodiment of the present specification, L27 is a direct bond.

According to an exemplary embodiment of the present specification, W11 to W21 are hydrogen.

According to an exemplary embodiment of the present specification, each of W11 to W16 and W18 to W21 is hydrogen.

According to an exemplary embodiment of the present specification, W17 is a halogen group.

According to one embodiment of the present specification, the W17 is fluorine (F).

According to an exemplary embodiment of the present specification, W17 is hydrogen (H).

According to an exemplary embodiment of the present specification, the branch represented by Formula 7 may be represented by one selected from the following structures.

According to one embodiment of the present specification, the polymer may be a random multi-block copolymer including a hydrophilic unit and a hydrophobic unit.

According to one embodiment of the present specification, the block copolymer may be a random multi-block copolymer, and the random multi-block copolymer may include a hydrophilic unit, a hydrophobic unit, and a fluorine-containing compound.

According to an exemplary embodiment of the present specification, the random multi-block copolymer includes a hydrophilic unit including a unit derived from a compound represented by Formula 1, a hydrophobic unit including a unit derived from a compound represented by Formula 3, and the aforementioned fluorine-containing compounds.

According to an exemplary embodiment of the present specification, the weight average molecular weight of the block copolymer is 1,000 g/mol to 2,000,000 g/mol. When the weight average molecular weight of the block copolymer is within the above range, the mechanical properties of the polymer separator including the block copolymer are not deteriorated, and the proper solubility of the polymer is maintained, so that the separator can be easily manufactured.

According to one embodiment of the present specification, the hydrophilic unit and the hydrophobic unit may be included in a molar ratio of 1:0.1 to 1:10 in the block copolymer. According to one embodiment of the present specification, the hydrophilic unit and the hydrophobic unit may be included in a molar ratio of 1:0.1 to 1:2 in the block copolymer. According to another exemplary embodiment of the present specification, the hydrophilic unit and the hydrophobic unit may be included in a molar ratio of 1:0.8 to 1:1.2 in the block copolymer. When the molar ratio of the hydrophilic unit and the hydrophobic unit satisfies the above range, the ion transport ability of the block copolymer according to an exemplary embodiment of the present invention may be increased.

According to one embodiment of the present specification, in the block copolymer, the hydrophilic unit: the hydrophobic unit: the fluorine-containing compound may be included in a molar ratio of 1: 0.1 to 10: 0.01 to 0.1. When the molar ratio of the hydrophilic unit, the hydrophobic unit, and the fluorine-containing compound satisfies the above range, the ion transport ability of the block copolymer according to an exemplary embodiment of the present invention may be increased.

According to an exemplary embodiment of the present specification, the unit derived from the compound represented by Formula 1 in the hydrophilic unit is included in an amount of 0.01 mol% to 100 mol% based on the hydrophilic unit.

According to an exemplary embodiment of the present specification, the number average molecular weight of the hydrophilic unit is 1,000 g/mol to 300,000 g/mol. According to a specific embodiment, it is 2,000 g/mol to 100,000 g/mol. According to another embodiment, it is 2,500 g/mol to 50,000 g/mol.

According to an exemplary embodiment of the present specification, the number average molecular weight of the hydrophobic unit is 1,000 g/mol to 300,000 g/mol. According to a specific embodiment, it is 2,000 g/mol to 100,000 g/mol. According to another embodiment, it is 2,500 g/mol to 50,000 g/mol.

According to an exemplary embodiment of the present specification, in the case of a high-molecular polymer, the hydrophilic unit and the hydrophobic unit are partitioned and distinguished so that phase separation is easy, and ion transfer can be facilitated.

According to an exemplary embodiment of the present specification, when the unit derived from the compound represented by Formula 1 is included, the distinction between the hydrophilic unit and the hydrophobic unit becomes more clear, and the ion transport effect can be superior to that of conventional polymers. .

In one embodiment of the present specification, (A) synthesizing a hydrophilic unit including a unit derived from the compound represented by Formula 1; (B) synthesizing a hydrophobic unit including a unit derived from the compound represented by Formula 3; and (C) reacting the hydrophilic unit, the hydrophobic unit, and a fluorine-containing compound.

According to an exemplary embodiment of the present specification, the reaction temperature of step (C) may be 25 ° C to 50 ° C, preferably 40 ° C to 50 ° C. Specifically, the block copolymer according to an exemplary embodiment of the present specification can form a random multi-block polymer having a high molecular weight even at a low temperature due to the high reactivity of the fluorine-containing compound.

According to one embodiment of the present specification, the hydrophilic unit, the hydrophobic unit, and the fluorine-containing compound may be applied to the above-mentioned hydrophilic unit, the above-mentioned hydrophobic unit, and the above-mentioned fluorine-containing compound.

According to an exemplary embodiment of the present specification, step (C) may react by further including a branch derived from the compound of Formula 6 or a branch represented by Formula 7. The information about the brancher may be applied to the information about the brancher described above.

According to an exemplary embodiment of the present specification, the reaction solvent in step (C) is N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) , diphenylsulfone, or N,N-dimethylformamide (DMF) may be used, but is not limited thereto.

According to one embodiment of the present specification, the reaction time of step (C) is 24 hours or more depending on the viscosity of the reactant. Preferably it may be 72 hours or more.

According to one embodiment of the present specification, the method for preparing the block copolymer may further include adding an acid solution to a solution containing the copolymer. The acid solution may be hydrochloric acid (HCl).

According to an exemplary embodiment of the present specification, when an acid solution is added to a solution containing the block copolymer, the metal M of A in Formula 1 may be substituted with H (hydrogen).

The block copolymer according to an exemplary embodiment of the present specification may be used in a polymer separator of a fuel cell. A fuel cell is an energy conversion device that directly converts chemical energy of fuel into electrical energy. That is, a fuel cell is a power generation method that uses a fuel gas and an oxidizer and uses electrons generated during an oxidation-reduction reaction thereof to generate power.

1 schematically illustrates the principle of generating electricity in a fuel cell. In a fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is a separator 100 and both sides of the separator 100. It consists of an anode (200a) and a cathode (200b) electrode formed on. Referring to FIG. 1 showing the principle of electricity generation of a fuel cell, in the anode 200a, an oxidation reaction of fuel such as hydrogen or hydrocarbons such as methanol and butane occurs to generate hydrogen ions (H ⁺ ) and electrons (e ^- ), , hydrogen ions move through the separator 100 to the cathode 200b. In the cathode 200b, hydrogen ions transferred through the separator 100 react with an oxidizing agent such as oxygen and electrons to generate water. This reaction causes the movement of electrons in the external circuit.

The catalyst layer of the anode electrode is a place where the oxidation reaction of fuel occurs, and a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, and platinum-transition metal alloy is preferred. can be used

The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and platinum or a platinum-transition metal alloy may be preferably used as a catalyst. The catalysts may be used by themselves or supported on a carbon-based carrier.

The process of introducing the catalyst layer may be performed by a conventional method known in the art. For example, the catalyst ink may be directly coated on a separator or coated on a gas diffusion layer to form a catalyst layer. At this time, the coating method of the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating, or spin coating may be used. 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 reaction gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive substrate. As the conductive substrate, carbon paper, carbon cloth, or carbon felt may be preferably used.

The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive substrate. The microporous layer can be used to improve the performance of a fuel cell under low humidity conditions, and serves to keep the polymer separator in a sufficiently wet state by reducing the amount of water escaping out of the gas diffusion layer.

In the present specification, "membrane electrode assembly (MEA)" refers to an assembly of an electrode (cathode and anode) in which an electrochemical catalytic reaction of fuel and air occurs and a polymer separator in which hydrogen ion transfer occurs, and the electrode (cathode and anode) It is a single integrated unit in which the anode) and the separator are attached.

FIG. 2 schematically illustrates the structure of a fuel cell, and the fuel cell includes a stack 60, an oxidizer supply unit 70, and a fuel supply unit 80.

The stack 60 includes one or two or more membrane electrode assemblies described above, and when two or more membrane electrode assemblies are included, a separator interposed therebetween. The separator prevents the membrane electrode assemblies from being electrically connected and serves to transfer fuel and oxidant supplied from the outside to the membrane electrode assembly. The oxidizing agent supply unit 70 serves to supply the oxidizing agent to the stack 60 . Oxygen is typically used as an oxidizing agent, and oxygen or air may be injected by a pump. The fuel supply unit 80 serves to supply fuel to the stack 60, and includes a fuel tank 81 for storing fuel and a pump 82 for supplying fuel stored in the fuel tank 81 to the stack 60. can be configured. As fuel, gaseous or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The fuel cell may be a polymer electrolyte fuel cell, 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, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

< manufacturing example 1> Preparation of hydrophilic unit A

(z1 = 1 to 1,000)

Perfluorinated 3,5 was added to a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, nitrogen inlet and mechanical stirrer. -Difluorobenzene (Perfluorinated 3,5-Difluorobenzene) monomer 30 g (62.46 mmol) and 4,4'-dihydroxydiphenyl ether (4,4'-Dihydroxydiphenyl ether) 13.892 g (68.70 mmol) were added and N -Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP) was reacted with 110 mL of toluene and 50 mL of toluene in a nitrogen atmosphere using 37.979 g (274.80 mmol) of potassium carbonate as a catalyst.

The reaction mixture was stirred for 2 hours in an oil bath at 140° C., and water and toluene were removed by reflux distillation. Thereafter, the temperature was raised to 185° C. and the reaction was performed for 6 hours.

After the reaction, the temperature was lowered to room temperature, and the synthesized hydrophilic unit solution was slowly dropped into 2,000 mL of isopropyl alcohol (IPA) to obtain a precipitate. Only the precipitate was obtained through a glass filter and washed with 200 mL IPA. The obtained hydrophilic unit was dried in a vacuum oven at 60° C. for 12 hours to prepare a hydrophilic unit A.

The NMR spectrum ( ¹ H DMSO- d ₆ ) of the hydrophilic unit A is shown in FIG. 3 .

< manufacturing example 2> Preparation of hydrophilic unit B

(z2 = 1 to 1,000)

In Preparation Example 1, 1,1'-biphenyl-4,4'-diol ([1,1'-biphenyl Hydrophilic unit B was prepared in the same manner as in Preparation Example 1, except that 12.793 g (68.70 mmol) of ]-4,4'-diol) was used.

The NMR spectrum of the hydrophilic unit B is shown in FIG. 4 .

< manufacturing example 3> Preparation of hydrophilic unit C

(z3 = 1 to 1,000)

In Preparation Example 1, instead of 4,4'-dihydroxydiphenyl ether (4,4'-Dihydroxydiphenyl ether), 4,4'-(perfluoropropane-2,2-diyl)diphenol (4, Hydrophilic unit C was prepared in the same manner as in Preparation Example 1, except that 23.099 g (68.70 mmol) of 4'-(perfluoropropane-2,2-diyl)diphenol) was used.

The NMR spectrum of the hydrophilic unit C is shown in FIG. 5 .

< manufacturing example 4> Preparation of hydrophobic unit

(z = 1 to 1,000)

In a 500 mL three-necked round bottomed flask equipped with a dean-stark trap, a nitrogen inlet, and a mechanical stirrer, 4,4′-bisfluoro 15.000 g (59 mmol) of 4,4'-Bisfluorophenyl sulfone and 23.805 g (70.80 mmol) of 6-fluoro bisphenol A were added and N,N-dimethylacetamide (N, 155 mL of N-Dimethylacetamide) (DMAc) and 50 mL of benzene were reacted in a nitrogen atmosphere using 39.140 g (283.20 mmol) of potassium carbonate as a catalyst. The reaction mixture was stirred for 2 hours in an oil bath at 120° C., and water and benzene were removed by reflux distillation. Thereafter, the temperature was raised to 140° C., and the reaction was performed for 4 hours. After the reaction, the temperature was lowered to room temperature, and the synthesized hydrophobic unit solution was slowly dropped into a 1M HCl solution (Ethanol/H ₂ O, 3/1) to obtain a precipitate. Only the precipitate was obtained through a glass filter and washed with 200 mL of ethanol. The obtained hydrophobic unit was dried in a vacuum oven at 60 °C for 12 hours.

The NMR spectrum of the hydrophobic unit is shown in FIG. 6 .

< Example 1> Synthesis of Random Multiblock Copolymer I

(z = 1 to 1,000, z1 = 1 to 1,000)

Hydrophilic prepared in Preparation Example 1 in a 250 mL three-necked round bottomed flask equipped with a dean-stark trap, a nitrogen inlet, and a mechanical stirrer Unit A 3.745 g, hydrophobic unit 2.000 g prepared in Preparation Example 4, decafluorobiphenyl 0.058 g (0.175 mmol), 4,4 ', 4 "-trihydroxytriphenyl methane (4,4 ', Add 0.004 g (0.015 mmol) of 4"-Trihydroxytriphenyl methane) and use 14 mL (40 wt/v %) of N-methylpyrrolidone (NMP) and 0.404 g (2.92 mmol) of potassium carbonate as a catalyst in a nitrogen atmosphere. and reacted. The reaction was carried out while stirring the reaction mixture in an oil bath at 50 °C for 3 days.

After the reaction, it was dropped into 1M HCl aqueous solution and stirred for 24 hours, and only the precipitate was obtained through a glass filter and washed with distilled water until the filtrate was neutral. The obtained random multi-block copolymer I was dried in a vacuum oven at 60 °C for 1 day.

The NMR spectrum of the random multi-block copolymer I is shown in FIG. 7 .

< Example 2> Synthesis of Random Multiblock Copolymer II

(z = 1 to 1,000, z2 = 1 to 1,000)

In Example 1, a random multi-block copolymer II was synthesized in the same manner as in Example 1, except that 2.793 g of the hydrophilic unit B prepared in Preparation Example 2 was used instead of the hydrophilic unit A prepared in Preparation Example 1. .

The NMR spectrum of the random multi-block copolymer II is shown in FIG. 8 .

< Example 3> Synthesis of Random Multiblock Copolymer III

(z = 1 to 1,000, z3 = 1 to 1,000)

In Example 1, a random multi-block copolymer III was synthesized in the same manner as in Example 1, except that 4.855 g of the hydrophilic unit C prepared in Preparation Example 3 was used instead of the hydrophilic unit A prepared in Preparation Example 1. .

The NMR spectrum of the random multi-block copolymer III is shown in FIG. 9 .

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and implementations are possible within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

100: separator
200a: anode
200b: cathode
60: stack
70: oxidizing agent supply unit
80: fuel supply unit
81: fuel tank
82: pump

Claims (16)

a hydrophilic unit, a hydrophobic unit, and a fluorine-containing compound;
The hydrophilic unit includes a repeating unit represented by Formula 4 below,
A block copolymer wherein the hydrophobic unit includes a repeating unit represented by Formula 5 below:
[Formula 4]

In Formula 4,
p1, a and a' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, a: a' is 1,000: 1 to 1: 1,000,
R10 is a halogen group, k is an integer from 0 to 3,
L11 and L12 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRb-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
A' is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , or -PO ₃ ^2- 2M ⁺ , and M is is a group 1 element,
R16 to R19 are the same as or different from each other, and each independently represents a halogen group;
Rb is hydrogen; Or a substituted or unsubstituted alkyl group,
n' is an integer from 2 to 10, m' is an integer from 2 to 10, the structures in parentheses are the same as or different from each other,
X11 is -C(Z11)(Z12)-; -O-; -S-; -CO-; or -Si(Z11)(Z12)-;
Z11 and Z12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
T11 and T12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, t11 and t12 are integers from 0 to 4, and when t11 and t12 are integers of 2 or more, the substituents in parentheses are the same as or different from each other,
[Formula 5]

In Formula 5,
p2, b and b' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, b: b' is 1,000: 1 to 1: 1,000,
X3 is —SO ₂ —;
X4 is -C(Z3)(Z4)-;
Z3 and Z4 are -CF ₃ ;
S3 to S6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
s3 to s6 are integers from 0 to 4, and when s3 to s6 are integers greater than or equal to 2, the substituents in parentheses are the same as or different from each other;

means a position bonding with an adjacent substituent or the main chain of a polymer. The block copolymer of claim 1, wherein the fluorine-containing compound is decafluorobiphenyl. delete The block copolymer according to claim 1, wherein L11 is -S- and L12 is -O-. The block copolymer according to claim 1, wherein A' is -SO ₃ H, or -SO ₃ ^- M ⁺ . The block copolymer of claim 1, wherein R16 to R19 are F. delete delete delete The block copolymer of claim 1, wherein the block copolymer is a random multi-block copolymer. The block copolymer of claim 1, wherein the block copolymer further comprises a branch derived from a compound represented by Formula 6 or a branch represented by Formula 7 below:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,
X is S; O; CO; SO; SO ₂ ; NR; A hydrocarbon-based or fluorine-based compound,
l is an integer from 0 to 100, and when l is 2 or more, 2 or more X's are the same as or different from each other;
Q1 and Q2 are the same as or different from each other, and are each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxyl group and a halogen group; an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an amine group represented by NR'R",
R, R' and R" are an aromatic ring substituted with a halogen group; or an aliphatic ring substituted with a halogen group,
Z is a trivalent organic group,

means a position bonding with an adjacent substituent or the main chain of a polymer. (A) synthesizing a hydrophilic unit including a repeating unit represented by Formula 4 below;
(B) synthesizing a hydrophobic unit including a repeating unit represented by Formula 5 below; and
(C) reacting the hydrophilic unit, the hydrophobic unit, and a fluorine-containing compound
Method for producing a block copolymer comprising:
[Formula 4]

In Formula 4,
p1, a and a' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, a: a' is 1,000: 1 to 1: 1,000,
R10 is a halogen group, k is an integer from 0 to 3,
L11 and L12 are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -NRb-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
A' is -SO ₃ H, -SO ₃ ^- M ⁺ , -COOH, -COO ^- M ⁺ , -PO ₃ H ₂ , -PO ₃ H ^- M ⁺ , or -PO ₃ ^2- 2M ⁺ , and M is is a group 1 element,
R16 to R19 are the same as or different from each other, and each independently represents a halogen group;
Rb is hydrogen; Or a substituted or unsubstituted alkyl group,
n' is an integer from 2 to 10, m' is an integer from 2 to 10, the structures in parentheses are the same as or different from each other,
X11 is -C(Z11)(Z12)-; -O-; -S-; -CO-; or -Si(Z11)(Z12)-;
Z11 and Z12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
T11 and T12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, t11 and t12 are integers from 0 to 4, and when t11 and t12 are integers of 2 or more, the substituents in parentheses are the same as or different from each other,
[Formula 5]

In Formula 5,
p2, b and b' are the repeating numbers of the units in parentheses and are integers from 1 to 1,000, b: b' is 1,000: 1 to 1: 1,000,
X3 is —SO ₂ —;
X4 is -C(Z3)(Z4)-;
Z3 and Z4 are -CF ₃ ;
S3 to S6 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; nitrile group; nitro group; hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
s3 to s6 are integers from 0 to 4, and when s3 to s6 are integers greater than or equal to 2, the substituents in parentheses are the same as or different from each other;

means a position bonding with an adjacent substituent or the main chain of a polymer. The method for preparing a block copolymer according to claim 12, wherein the reaction temperature of step (C) is performed at 25 ° C to 50 ° C. The method of claim 12, wherein the fluorine-containing compound is decafluorobiphenyl. delete The method for producing a block copolymer according to claim 12, wherein step (C) further comprises a branch source derived from a compound of Formula 6 or a branch source represented by Formula 7 below:
[Formula 6]

[Formula 7]

In Formulas 6 and 7,
X is S; O; CO; SO; SO ₂ ; NR; A hydrocarbon-based or fluorine-based compound,
l is an integer from 0 to 100, and when l is 2 or more, 2 or more X's are the same as or different from each other;
Q1 and Q2 are the same as or different from each other, and are each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxyl group and a halogen group; an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an amine group represented by NR'R",
R, R' and R" are an aromatic ring substituted with a halogen group; or an aliphatic ring substituted with a halogen group,
Z is a trivalent organic group,

means a position bonding with an adjacent substituent or the main chain of a polymer.

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