WO2017052226A1 - Block polymer and polymer electrolyte membrane including same - Google Patents

Block polymer and polymer electrolyte membrane including same Download PDF

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Publication number
WO2017052226A1
WO2017052226A1 PCT/KR2016/010582 KR2016010582W WO2017052226A1 WO 2017052226 A1 WO2017052226 A1 WO 2017052226A1 KR 2016010582 W KR2016010582 W KR 2016010582W WO 2017052226 A1 WO2017052226 A1 WO 2017052226A1
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formula
group
substituted
unsubstituted
polymer
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PCT/KR2016/010582
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French (fr)
Korean (ko)
Inventor
장용진
한중진
강에스더
유윤아
김영제
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주식회사 엘지화학
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Priority claimed from KR1020160116613A external-priority patent/KR102068872B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2018530467A priority Critical patent/JP6642881B2/en
Priority to CN201680050754.5A priority patent/CN107922596B/en
Priority to US15/753,095 priority patent/US10899874B2/en
Priority to EP16848951.6A priority patent/EP3327059B1/en
Publication of WO2017052226A1 publication Critical patent/WO2017052226A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present specification relates to a block polymer and a polymer electrolyte membrane including the same.
  • a fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy.
  • a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.
  • the membrane electrode assembly (MEA) of a fuel cell is a portion in which an electrochemical reaction between hydrogen and oxygen occurs and is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane.
  • a redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy by charging and discharging the active material contained in the electrolyte. to be.
  • the unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).
  • Fuel cells and redox flow cells are being researched and developed as next generation energy sources due to their high energy efficiency and eco-friendly features with low emissions.
  • the key components of fuel cell and redox flow cell are polymer electrolyte membranes capable of cation exchange, including 1) excellent proton conductivity 2) prevention of crossover of electrolyte, 3) strong chemical resistance, 4) mechanical It is desirable to have properties of enhanced physical properties and / or 4) low swelling ratio.
  • the polymer electrolyte membrane is classified into fluorine-based, partially fluorine-based, hydrocarbon-based, and the like, and the partial fluorine-based polymer electrolyte membrane has a fluorine-based main chain, which has advantages of excellent physical and chemical stability and high thermal stability.
  • the partial fluorine-based polymer electrolyte membrane has a cation transfer functional group attached to the end of the fluorine-based chain, and thus has the advantages of a hydrocarbon-based polymer electrolyte membrane and a fluorine-based polymer electrolyte membrane.
  • the partial fluorine-based polymer electrolyte membrane has a problem that the cation conductivity is relatively low because the fine phase separation of the cation transport functional group and the control of the aggregation phenomenon are not effectively performed. Therefore, research has been conducted toward securing high cationic conductivity through the control of the distribution of sulfonic acid groups and microphase separation.
  • the present specification is to provide a polymer and a polymer electrolyte membrane including the same.
  • the present specification is a hydrophobic block; And hydrophilic blocks,
  • the hydrophobic block comprises at least one cationic side chain
  • the hydrophilic block provides a block polymer comprising a unit derived from a compound represented by the following formula (1).
  • A 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 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 ) m PO 3 H 2, -O (CF 2) m PO 3 H - M + , or -O (CF 2) m PO 3 2- 2M + , and
  • n 2 to 6
  • M is a group 1 element
  • R1 to R5 are the same as or different from each other, and each independently hydrogen; Halogen group; Or a hydroxyl group,
  • At least two of R1 to R5 are halogen groups; Or a hydroxyl group,
  • R6 and R7 are the same as or different from each other, and each independently a halogen group
  • La is a direct bond; S; O; NRa; SO 2 ; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • Ra is hydrogen; Or a substituted or unsubstituted alkyl group,
  • n is an integer from 2 to 10, and the structures in the 2 to 10 parentheses are the same or different from each other.
  • the present specification provides a polymer electrolyte membrane including the block polymer.
  • the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
  • the present specification includes two or more of the aforementioned membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
  • the present specification is a positive electrode cell comprising a positive electrode and a positive electrode electrolyte;
  • a cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising the above-described polymer electrolyte membrane provided between the cathode cell and the anode cell.
  • the polymer electrolyte membrane including the block polymer according to one embodiment of the present specification easily forms a hydrophilic-hydrophobic phase separation structure.
  • the polymer electrolyte membrane effectively forms a hydrophilic channel in the polymer electrolyte membrane by controlling the phase separation structure.
  • polymer electrolyte membrane including the block polymer according to the exemplary embodiment of the present specification may simultaneously realize the advantages of the cationic polymer electrolyte membrane and the anionic polymer electrolyte membrane.
  • the polymer electrolyte membrane according to one embodiment of the present specification has excellent proton conductivity.
  • the result is a high performance of fuel cells and / or redox flow cells comprising the same.
  • gas crossover may be prevented and ion conductivity may be improved even under low humidity conditions.
  • the redox flow battery including the polymer electrolyte membrane according to one embodiment of the present specification may reduce crossover of vanadium ions.
  • FIG. 1 is a schematic diagram illustrating a principle of electricity generation of a fuel cell.
  • FIG. 2 is a view schematically showing an embodiment of a redox flow battery.
  • FIG 3 is a view schematically showing an embodiment of a fuel cell.
  • FIG. 5 is a diagram showing an H-NMR spectrum of Intermediate 1.
  • 'unit' is a repeating structure in which the monomer is included in the polymer, and means a structure in which the monomer is bonded into the polymer by polymerization.
  • the block polymer refers to a polymer in which one block and one or more blocks different from the block are connected to each other by a main chain of the polymer.
  • the block polymer may include a hydrophilic block and a hydrophobic block.
  • the block polymer may include a hydrophilic block having a unit represented by Chemical Formula 1 and a hydrophobic block having a cationic side chain.
  • hydrophilic block herein is meant a block having an ion exchange group as a functional group.
  • the functional groups are -SO 3 H, -SO 3 - M +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, -O (CF 2 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 may be at least one selected from the group consisting of 2M + -) m PO 3 H 2, -O (CF 2) m PO 3 H - M + , and -O (CF 2) m PO 3 2.
  • M may be a metallic element. That is, the functional group may be hydrophilic.
  • the first unit represented by Formula 1 may exhibit hydrophilicity by including a functional group of A.
  • block having an ion exchange group in the present specification means a block containing an average of 0.5 or more represented by the number of ion exchange groups per structural unit constituting the block, and an average of 1.0 or more ions per structural unit It is more preferable to have an exchanger.
  • the cationic side chain is-(L) oN + RR'R ";-(L) oP + RR'R”; Or in the following Chemical Formula 1-A,
  • L is a direct bond; O; NR ′′ ′; S; SO 2 ; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • o is an integer from 1 to 10
  • R, R ', R ", R'” and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
  • the hydrophobic block includes a unit represented by the following Chemical Formula 2 or Chemical Formula 3.
  • S1 to S4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or in the following Chemical Formula 1-A,
  • L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • o is an integer from 1 to 10
  • R, R ', R ", R'” and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
  • a, a ', b and b' are each an integer of 1 to 4,
  • the hydrophobic block includes at least one cationic side chain.
  • the block polymer according to one embodiment of the present specification includes at least one cationic side chain in the hydrophobic block, thereby preventing crossover through the membrane of vanadium ions, thereby improving current efficiency.
  • the block polymer may be easily partitioned and separated from the hydrophilic block and the hydrophobic block to facilitate phase separation, thereby facilitating ion transfer.
  • the hydrophilic block and the hydrophobic block are more clearly distinguished, and the ion transfer effect may be superior to that of the conventional polymer.
  • block polymer according to the exemplary embodiment of the present specification may simultaneously realize the advantages of the cationic polymer electrolyte membrane of the unit represented by Formula 1 included in the hydrophilic block and the anion polymer electrolyte membrane included in the hydrophobic block.
  • the hydrophobic block or the hydrophilic block further includes a unit derived from a compound represented by the following formula (4).
  • E1 and E2 are hydroxy or thiol groups
  • S5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
  • L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • o is an integer from 1 to 10
  • R, R ', R ", R'” and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
  • c is an integer from 1 to 4,
  • c ' is an integer of 1 to 3
  • the hydrophobic block is a unit represented by Formula 2 or Formula 3; And units derived from the compound represented by the formula (4).
  • E1 and E2 are hydroxy or thiol groups
  • S1 to S5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
  • L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
  • o is an integer from 1 to 10
  • R, R ', R ", R'” and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
  • a, a ', b, b' and c are each an integer of 1 to 4,
  • c ' is an integer of 1 to 3
  • R, R 'and R are the same as or different from each other, and each independently an alkyl group having 1 to 10 carbon atoms.
  • R, R 'and R " are methyl groups.
  • the unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1.
  • the unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-1.
  • E1 and E2 are a hydroxyl group or a thiol group.
  • E1 is a hydroxy group.
  • E1 is a thiol group.
  • E2 is a hydroxy group.
  • E2 is a thiol group.
  • c ' is 1.
  • c ' is two.
  • the compound represented by Chemical Formula 4 is represented by any one of the following Chemical Formulas 4-1 to 4-4.
  • S5 ' is the same as or different from S5, and each independently the same as S5.
  • an S atom is used as a linker of the-[CR6R7] n- A structure and the benzene ring in Chemical Formula 1.
  • S atoms due to the electron withdrawing character of-[CR6R7] n -A linked by S atoms, it is possible to provide a polymer which is easy to form and stable.
  • R6 and R7 are the same as or different from each other, and are each independently a halogen group. Specifically R 6 and R 7 are each independently F; Cl; Br; And I can be selected from the group consisting of.
  • n is an integer of 2 to 10. In another embodiment of the present specification, n is an integer of 2 to 6.
  • a monomer including a unit of Formula 1 may control the number of n.
  • the monomer including the unit of formula (1) can be adjusted as necessary according to the difference in reactivity and the physical properties of the final polymer according to the length control of the structure in parentheses.
  • R3 and R5 are fluorine.
  • a unit derived from the compound represented by Formula 1 may be included in the polymer.
  • n is 2.
  • n 3.
  • n 4.
  • n is 5.
  • n is 6.
  • n 7.
  • n 8.
  • n 9.
  • n 10
  • A is -SO 3 H or -SO 3 - M + .
  • A is —SO 3 H.
  • any of formulas A 1 -SO 3 H or -SO 3 - M + may be the case, form a stable polymer chemically.
  • M is a Group 1 element.
  • the Group 1 element may be Li, Na, or K.
  • the unit derived from the fused fire represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 7 to 9.
  • the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-18.
  • the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-19 to 1-36.
  • the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-37 to 1-54.
  • the hydrophilic block is a unit represented by Formula 1; And a unit derived from the compound represented by Formula 4 above.
  • S1 is-(L) oN + RR'R ".
  • S2 is-(L) oN + RR'R ".
  • S3 is-(L) oN + RR'R ".
  • the hydrophobic block includes a cationic side chain, and the position thereof is not limited.
  • the block polymer includes a unit represented by any one of the following Formulas A to J and A-1 to J-1.
  • x and y are each independently a molar ratio of the block polymer, an integer greater than 0 and less than 1,
  • the hydrophilic block and the hydrophobic block are included in the mole ratio of 1: 0.001 to 1: 100 in the block polymer. In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the block polymer in a ratio of 1: 1 to 1: 0.001. In another embodiment, the hydrophilic block and hydrophobic block in the block polymer is included in a molar ratio of 1: 0.1 to 1: 0.01.
  • the hydrophobic block is preferably included in an amount of 0.1 mol% to 50 mol%, more preferably 1 mol% to 10 mol% based on the entire polymer of the block polymer.
  • the ion transport ability of the block polymer can be raised.
  • the unit represented by Chemical Formula 1 in the hydrophilic block is included from 0.01 mol% to 100 mol% based on the hydrophilic block.
  • the number average molecular weight of the hydrophilic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
  • the number average molecular weight of the hydrophobic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
  • the block polymer may further include a brancher.
  • a brancher serves to link or crosslink a polymer chain.
  • the brancher may directly constitute the main chain of the polymer, and may improve the mechanical density of the thin film.
  • the branched block polymers of the present invention are polymerized by post-treatment by polymerizing branched hydrophobic blocks that do not contain acid substituents and branched hydrophilic blocks that include acid substituents. Without the post-sulfonation or cross-linking of the sulfonated polymer, the brancher directly forms the main chain of the polymer and maintains the mechanical density of the thin film. In the main, a small number of blocks and a hydrophilic block that imparts ion conductivity to the thin film are alternately connected to the chemical bond.
  • the block polymer is a brancher derived from a compound represented by the following formula (5); Or a brancher represented by the following formula (6).
  • X is S; O; CO; SO; SO 2 ; NR ""; Hydrocarbon-based or fluorine-based conjugates,
  • R ′′ ′′ is hydrogen; Aromatic rings substituted with halogen groups; Or an aliphatic ring substituted with a halogen group,
  • l is an integer from 0 to 10
  • Y1 and Y2 are the same as or different from each other, and each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,
  • Z is a trivalent organic group.
  • the unit derived from the compound may mean a unit connected to the main chain of the polymer.
  • the unit may be included in the main chain in the polymer to constitute the polymer.
  • the unit derived from the compound represented by Chemical Formula 1 may mean that when at least two of R1 to R5 are halogen groups, the halogen groups are separated and connected to the main chain of the polymer. .
  • the unit derived from the compound represented by Chemical Formula 1 is a hydroxy group, and when at least two of R1 to R5 are hydroxy groups, a halogen group of a comonomer having a halogen group is dropped to connect with the main chain of the polymer. Can mean being.
  • the unit derived from the compound represented by Chemical Formula 4 may mean that E1 and E2 are thiol groups or hydroxy groups, and are connected to the polymer main chain while dehydrogenating the thiol groups or hydroxy groups. have.
  • the derived unit may include being connected to the main chain of the polymer while being carbohydrated, and may also include modifying a site connected to the main chain through post-treatment such as acid treatment and heat treatment.
  • a linking group of -O- may be provided in the polymer main chain
  • E1 and E2 are thiol groups
  • the linking group of -S- in the polymer main chain may be provided. It may be provided.
  • the linking group of -S- of the polymer backbone can be converted to -SO 2- .
  • the brancher derived from the compound of Formula 5 in the present specification is an aromatic ring substituted with a halogen group of each of the Y1 and Y2; Or a halogen group in the aliphatic ring substituted with a halogen group may act as a brancher while being separated from the aromatic ring or aliphatic ring. Specifically, two or more halogen groups may fall off and act as a brancher in the polymer.
  • substituted means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
  • the hydrocarbon-based means an organic compound consisting of only carbon and hydrogen, and includes a straight chain, branched chain, cyclic hydrocarbon, and the like, but is not limited thereto. In addition, it may include a single bond, a double bond or a triple bond, but is not limited thereto.
  • the fluorine-based conjugate means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.
  • the aromatic ring may be an aromatic hydrocarbon ring or an aromatic hetero ring, and may be monocyclic or polycyclic.
  • aromatic hydrocarbon ring monocyclic aromatic and naphthyl groups, binaphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, peryllenyl groups, tetrasenyl groups, chrysenyl groups such as phenyl groups, biphenyl groups and terphenyl groups
  • polycyclic aromatics such as fluorenyl group, acenaphthasenyl group, triphenylene group, and fluoranthene group, and the like.
  • the aromatic heterocycle means a structure including one or more hetero atoms such as O, S, N, Se, or the like instead of a carbon atom in the aromatic hydrocarbon ring.
  • thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group, pyridazine group , Pyrazinyl, quinolinyl, quinazolin, quinoxalinyl, phthalazinyl, pyrido pyrimidinyl, pyrido pyrazinyl, pyrazino pyrazinyl, isoquinoline, indole, carbazole, Benzoxazole group, benzoimidazole group, benzothiazole group, benzo
  • the aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic hetero ring, and may be monocyclic or polycyclic.
  • Examples of the aliphatic ring include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.
  • an organic group an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned.
  • This organic group may contain the bond and substituents other than hydrocarbon groups, such as a hetero atom, in the said organic group.
  • the organic group may be any of linear, branched and cyclic.
  • the trivalent organic group means a trivalent group having three bonding positions in an organic compound.
  • the organic group may form a cyclic structure, may form a cyclic structure, and may include a hetero atom to form a bond as long as the effects of the invention are not impaired.
  • the bond containing hetero atoms such as an oxygen atom, a nitrogen atom, and a silicon atom
  • hetero atoms such as an oxygen atom, a nitrogen atom, and a silicon atom
  • the cyclic structure may include the aforementioned aromatic ring, aliphatic ring, and the like, and may be monocyclic or polycyclic.
  • the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl groups.
  • the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40.
  • Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
  • the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and especially cyclopentyl group, cyclohexyl group, and the like, but is not limited thereto.
  • l is 3 or more.
  • X is S.
  • X is a haloalkyl group.
  • X is CH 2 .
  • X is NR '".
  • Y1 and Y2 are the same as or different from each other, and are each independently a halogen substituted aromatic ring.
  • Y1 and Y2 are the same as or different from each other, and are each independently a fluorine-substituted aromatic hydrocarbon ring.
  • Y1 and Y2 are each a fluorine substituted phenyl group.
  • 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl and the like are not limited thereto.
  • the compound represented by Formula 5 may be represented by any one of the following structures.
  • Z in Chemical Formula 6 may be represented by any one of the following Chemical Formulas 6-1 to 6-4.
  • L1 To L7 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -CO-; Or -SO 2- ,
  • R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
  • e, e ', e ", f', h, i and j are each an integer of 1 to 4,
  • d, f, g and k are each an integer of 1 to 3,
  • L1 is CO
  • L1 is SO 2 .
  • L1 is S.
  • L2 is CO
  • L2 is SO 2 .
  • L2 is S.
  • L3 is CO.
  • L3 is SO 2 .
  • L3 is S.
  • L4 is CO
  • L4 is SO 2 .
  • L5 is a direct bond
  • L6 is a direct bond
  • L7 is a direct bond.
  • R10 to R20 are hydrogen.
  • R16 is a halogen group.
  • R16 is fluorine
  • brancher represented by Chemical Formula 6 may be represented by any one of the following structures.
  • the weight average molecular weight of the polymer is 500 g / mol to 5,000,000 g / mol. In another embodiment of the present specification, the weight average molecular weight of the polymer is 10,000 g / mol to 3,000,000 g / mol.
  • the weight average molecular weight of the polymer is in the above range, the mechanical properties of the electrolyte membrane including the polymer are not lowered, and the solubility of the polymer may be maintained to facilitate the preparation of the electrolyte membrane.
  • the present disclosure provides a polymer electrolyte membrane including the block polymer described above.
  • a block polymer including a unit represented by Formula 1 In the case of including a block polymer including a unit represented by Formula 1 according to an exemplary embodiment of the present specification, it has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the electrolyte membrane.
  • electrolyte membrane is a membrane capable of exchanging ions, such as membrane, ion exchange membrane, ion transfer membrane, ion conductive membrane, separator, ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion And a transfer electrolyte membrane or an ion conductive electrolyte membrane.
  • a polymer electrolyte membrane according to one embodiment of the present specification includes a hydrophilic block including a unit represented by Chemical Formula 1; And block polymers including hydrophobic blocks comprising at least one cationic side chain, using materials and / or methods known in the art.
  • the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less. In another exemplary embodiment, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.3 S / cm or less.
  • the ionic conductivity of the polymer electrolyte membrane may be measured under humidification conditions.
  • the humidification condition may mean 10% to 100% relative humidity (RH).
  • the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g.
  • IEC ion exchange capacity
  • the thickness of the polymer electrolyte membrane is 1 ⁇ m to 500 ⁇ m.
  • the polymer electrolyte membrane having the above range thickness lowers an electrical short and a cross over of an electrolyte material, and may exhibit excellent cation conductivity characteristics.
  • the present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
  • Membrane-electrode assembly is an electrode (cathode and anode) in which the electrochemical catalysis of fuel and air occurs and a polymer membrane in which hydrogen ions are transferred.
  • the electrode (cathode and anode) and the electrolyte membrane are bonded together. It is a single unitary unit.
  • the membrane-electrode assembly of the present specification is a form in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane, and may be prepared according to conventional methods known in the art.
  • 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.
  • the cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer.
  • the cathode gas diffusion layer may further include a cathode microporous layer and a cathode electrode substrate.
  • FIG. 1 schematically illustrates the principle of electricity generation of a fuel cell.
  • the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is an electrolyte membrane 100 and the electrolyte membrane 100. It consists of an anode (200a) and a cathode (200b) electrode formed on both sides of the.
  • MEA membrane electrode assembly
  • an anode 200a generates an oxidation reaction of a fuel such as hydrogen or a hydrocarbon such as methanol and butane to generate hydrogen ions (H +) and electrons (e ⁇ ). Hydrogen ions move to the cathode 200b through the electrolyte membrane 100.
  • water is generated by reacting hydrogen ions transferred through the electrolyte membrane 100 with an oxidant such as oxygen and electrons. This reaction causes the movement of electrons in the external circuit.
  • the catalyst layer of the anode electrode is where the oxidation reaction of the fuel occurs, the catalyst is selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-transition metal alloy. Can be used.
  • the catalyst layer of the cathode electrode is where the reduction reaction of the oxidant occurs, platinum or platinum-transition metal alloy may be preferably used as a catalyst.
  • the catalysts can be used on their own as well as supported on a carbon-based carrier.
  • the introduction of the catalyst layer may be carried out by conventional methods 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 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.
  • Catalytic inks can typically consist of a catalyst, a polymer ionomer, and a solvent.
  • the gas diffusion layer serves as a passage for the reaction gas and water together with a role as a current conductor, 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 may be used to improve the performance of the fuel cell in low-humidity conditions, and serves to reduce the amount of water flowing out of the gas diffusion layer so that the electrolyte membrane is in a sufficient wet state.
  • One embodiment of the present specification includes two or more membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
  • a fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy.
  • a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.
  • the fuel cell can be manufactured according to conventional methods known in the art using the membrane-electrode assembly (MEA) described above.
  • MEA membrane-electrode assembly
  • it may be prepared by configuring a membrane electrode assembly (MEA) and a bipolar plate (bipolar plate) prepared above.
  • the fuel cell of the present specification includes a stack, a fuel supply unit and an oxidant supply unit.
  • FIG. 3 schematically illustrates the structure of a fuel cell, in which the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.
  • the stack 60 includes one or two or more membrane electrode assemblies as described above, and includes two or more separators 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 fuel and oxidant supplied from the outside to the membrane electrode assembly.
  • the oxidant supply unit 70 serves to supply the oxidant to the stack 60.
  • Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into the pump 70.
  • the fuel supply unit 80 serves to supply fuel to the stack 60, and to the fuel tank 81 storing fuel and the pump 82 supplying fuel stored in the fuel tank 81 to the stack 60.
  • fuel hydrogen or hydrocarbon fuel in gas or liquid state may be used.
  • 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.
  • the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a fuel cell, the above-described effects can be obtained.
  • an exemplary embodiment of the present specification includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising a polymer electrolyte membrane according to one embodiment of the present specification provided between the cathode cell and the anode cell.
  • the redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy. It is a system in which the active material contained in the electrolyte is oxidized, reduced, and charged and discharged. to be.
  • the redox flow battery uses a principle that charges and discharges are exchanged when electrons containing active materials having different oxidation states meet with an ion exchange membrane interposed therebetween.
  • a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte solution between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, an electrolyte, and an ion. Exchange membrane.
  • the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a redox flow battery, the above-described effects may be exhibited.
  • the redox flow battery of the present specification may be manufactured according to conventional methods known in the art, except for including the polymer electrolyte membrane according to one embodiment of the present specification.
  • the redox flow battery is divided into the positive electrode cell 32 and the negative electrode cell 33 by the electrolyte membrane 31.
  • the anode cell 32 and the cathode cell 33 include an anode and a cathode, respectively.
  • the anode cell 32 is connected to the anode tank 10 for supplying and discharging the anode electrolyte 41 through a pipe.
  • the cathode cell 33 is also connected to the cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe.
  • the electrolyte is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions changes occurs, thereby causing charge and discharge at the anode and the cathode.
  • an oxidation / reduction reaction that is, a redox reaction
  • Each of the monomers and potassium carbonate (K 2 CO 3 : molar ratio 4) were mixed in an NMP 30 wt% ratio and a benzene 20 wt% ratio, and polymerized at 140 ° C. for 4 hours and at 180 ° C. for 16 hours to prepare the polymer. It was. H-NMR of the polymer is shown in Figure 5, after dissolving Polymer 1 in DMAC was carried out H-NMR experiment in CDCl 3 solvent.
  • the vanadium permeability of the electrolyte membrane using the compound 1 was measured and shown in Table 1 below.
  • the vanadium permeability of the electrolyte membrane using Nafion 115 was measured and shown in Table 1 below.
  • the vanadium ion permeability is 1M VOSO 4 in 2M H 2 SO 4 solution on one side and 1M MgSO 4 in 2M H 2 SO 4 solution on the other side, the electrolyte membrane is installed between the two solutions over time VO 2+ concentration in 1M MgSO 4 in 2M H 2 SO 4 solution was measured.
  • the active area was measured at 7.69 cm 2 , the volume was 200 ml, and room temperature.
  • the permeability of vanadium ions is significantly lower than that of the conventional Nafion electrolyte membrane due to the presence of cationic functional groups in the electrolyte membrane main chain as compared to the Nafion 115 electrolyte membrane.
  • the efficiency of the battery can be improved.

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Abstract

The present specification relates to: a block polymer and a polymer electrolyte membrane including same; a membrane-electrode assembly including the polymer electrolyte membrane; and a redox flow battery including a fuel cell including the membrane-electrode assembly, and the polymer electrolyte membrane.

Description

블록 중합체 및 이를 포함하는 고분자 전해질막Block polymer and polymer electrolyte membrane comprising the same
본 명세서는 2015년 09월 22일 한국 특허청에 제출된 한국 특허 출원 제10-2015-0133845호 및 2016년 09월 09일 한국 특허청에 제출된 한국 특허 출원 제10-2016-0116613호의 출원일 이익을 주장하며, 그 내용 전부는 본 명세서에 포함된다.This specification claims the benefit date of Korean Patent Application No. 10-2015-0133845 filed with the Korean Intellectual Property Office on September 22, 2015 and Korean Patent Application No. 10-2016-0116613 filed with the Korean Patent Office on September 09, 2016. All of the content is included in this specification.
본 명세서는 블록 중합체 및 이를 포함하는 고분자 전해질막에 관한 것이다.The present specification relates to a block polymer and a polymer electrolyte membrane including the same.
연료전지는 연료의 화학적 에너지를 직접 전기적 에너지로 변환시키는 에너지 변환 장치이다. 즉 연료전지는 연료가스와 산화제를 사용하고, 이들의 산화환원 반응 중에 발생하는 전자를 이용하여 전력을 생산하는 발전 방식이다. 연료전지의 막 전극 접합체(MEA)는 수소와 산소의 전기화학적 반응이 일어나는 부분으로서 캐소드와 애노드 그리고 전해질막, 즉 이온 전도성 전해질막으로 구성되어 있다.A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy. In other words, a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction. The membrane electrode assembly (MEA) of a fuel cell is a portion in which an electrochemical reaction between hydrogen and oxygen occurs and is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane.
레독스 플로우 전지(산화-환원 흐름 전지, Redox Flow Battery)란 전해액에 포함되어 있는 활성물질이 산화·환원되어 충전·방전되는 시스템으로 활성물질의 화학적 에너지를 직접 전기에너지로 저장시키는 전기화학적 축전 장치이다. 레독스 플로우 전지의 단위셀은 전극, 전해질 및 이온교환막(전해질막)을 포함한다.A redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy by charging and discharging the active material contained in the electrolyte. to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).
연료전지 및 레독스 플로우 전지는 높은 에너지 효율성과 오염물의 배출이 적은 친환경적인 특징으로 인하여 차세대 에너지원으로 연구 개발되고 있다. Fuel cells and redox flow cells are being researched and developed as next generation energy sources due to their high energy efficiency and eco-friendly features with low emissions.
연료전지 및 레독스 플로우 전지에서 가장 핵심이 되는 구성요소는 양이온 교환이 가능한 고분자 전해질막으로서, 1) 우수한 양성자 전도도 2) 전해질의 크로스오버(Cross Over) 방지, 3) 강한 내화학성, 4) 기계적 물성 강화 및/또는 4) 낮은 스웰링 비(Swelling Ratio)의 특성을 갖는 것이 좋다. 고분자 전해질막은 불소계, 부분불소계, 탄화수소계 등으로 구분이 되며, 부분불소계 고분자 전해질막의 경우, 불소계 주 사슬을 가지고 있어 물리적, 화학적 안정성이 우수하며, 열적 안정성 높다는 장점이 있다. 또한, 부분불소계 고분자 전해질막은 불소계 고분자 전해질막과 마찬가지로 양이온 전달 관능기가 불소계 사슬의 말단에 붙어있어, 탄화수소계 고분자 전해질막과 불소계 고분자 전해질막의 장점을 동시에 가지고 있다.The key components of fuel cell and redox flow cell are polymer electrolyte membranes capable of cation exchange, including 1) excellent proton conductivity 2) prevention of crossover of electrolyte, 3) strong chemical resistance, 4) mechanical It is desirable to have properties of enhanced physical properties and / or 4) low swelling ratio. The polymer electrolyte membrane is classified into fluorine-based, partially fluorine-based, hydrocarbon-based, and the like, and the partial fluorine-based polymer electrolyte membrane has a fluorine-based main chain, which has advantages of excellent physical and chemical stability and high thermal stability. In addition, as in the fluorine-based polymer electrolyte membrane, the partial fluorine-based polymer electrolyte membrane has a cation transfer functional group attached to the end of the fluorine-based chain, and thus has the advantages of a hydrocarbon-based polymer electrolyte membrane and a fluorine-based polymer electrolyte membrane.
그러나, 부분불소계 고분자 전해질막은 양이온 전달 관능기의 미세 상 분리와 응집현상의 제어가 효과적으로 이루어지지 않아 양이온 전도도가 비교적 낮은 문제점이 있다. 따라서, 술폰산기의 분포 및 미세 상 분리의 제어를 통해 높은 양이온 전도도를 확보하는 방향으로 연구가 진행되어오고 있다.However, the partial fluorine-based polymer electrolyte membrane has a problem that the cation conductivity is relatively low because the fine phase separation of the cation transport functional group and the control of the aggregation phenomenon are not effectively performed. Therefore, research has been conducted toward securing high cationic conductivity through the control of the distribution of sulfonic acid groups and microphase separation.
본 명세서는 중합체 및 이를 포함하는 고분자 전해질막을 제공하고자 한다. The present specification is to provide a polymer and a polymer electrolyte membrane including the same.
본 명세서는 소수성 블록; 및 친수성 블록을 포함하고, The present specification is a hydrophobic block; And hydrophilic blocks,
상기 소수성 블록은 적어도 하나의 양이온성 측쇄를 포함하며, The hydrophobic block comprises at least one cationic side chain,
상기 친수성 블록은 하기 화학식 1로 표시되는 화합물로부터 유래된 단위를 포함하는 것인 블록 중합체를 제공한다. The hydrophilic block provides a block polymer comprising a unit derived from a compound represented by the following formula (1).
[화학식 1][Formula 1]
Figure PCTKR2016010582-appb-I000001
Figure PCTKR2016010582-appb-I000001
화학식 1에 있어서, In Chemical Formula 1,
A는 -SO3H, -SO3 -M+, -COOH, -COO-M+, -PO3H2, -PO3H-M+, -PO3 2-2M+, -O(CF2)mSO3H, -O(CF2)mSO3 -M+, -O(CF2)mCOOH, -O(CF2)mCOO-M+, -O(CF2)mPO3H2, -O(CF2)mPO3H-M+ 또는 -O(CF2)mPO3 2-2M+이고,A 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 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 ) m PO 3 H 2, -O (CF 2) m PO 3 H - M + , or -O (CF 2) m PO 3 2- 2M + , and
m은 2 내지 6의 정수이며, m is an integer from 2 to 6,
M은 1족 원소이고,M is a group 1 element,
R1 내지 R5는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 할로겐기; 또는 히드록시기이며, R1 to R5 are the same as or different from each other, and each independently hydrogen; Halogen group; Or a hydroxyl group,
R1 내지 R5 중 적어도 두 개는 할로겐기; 또는 히드록시기이고, At least two of R1 to R5 are halogen groups; Or a hydroxyl group,
R6 및 R7은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐기이며,R6 and R7 are the same as or different from each other, and each independently a halogen group,
La는 직접결합; S; O; NRa; SO2; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, La is a direct bond; S; O; NRa; SO 2 ; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
Ra는 수소; 또는 치환 또는 비치환된 알킬기이며, Ra is hydrogen; Or a substituted or unsubstituted alkyl group,
n은 2 내지 10의 정수이며, 2 내지 10 개의 괄호 내의 구조는 서로 동일하거나 상이하다. n is an integer from 2 to 10, and the structures in the 2 to 10 parentheses are the same or different from each other.
본 명세서는 상기 블록 중합체를 포함하는 고분자 전해질막을 제공한다. The present specification provides a polymer electrolyte membrane including the block polymer.
또한, 본 명세서는 애노드; 캐소드; 및 상기 애노드와 상기 캐소드 사이에 구비된 전술한 고분자 전해질막을 포함하는 막-전극 접합체를 제공한다.In addition, the present specification is an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
본 명세서는 2 이상의 전술한 막-전극 접합체; 상기 막-전극 접합체들 사이에 구비되는 바이폴라 플레이트를 포함하는 스택; 상기 스택으로 연료를 공급하는 연료공급부; 및 상기 스택으로 산화제를 공급하는 산화제공급부를 포함하는 고분자 전해질형 연료전지를 제공한다. The present specification includes two or more of the aforementioned membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
마지막으로, 본 명세서는 양극 및 양극 전해액을 포함하는 양극 셀; 음극 및 음극 전해액을 포함하는 음극 셀; 및 상기 양극 셀과 상기 음극 셀 사이에 구비되는 전술한 고분자 전해질막을 포함하는 레독스 플로우 전지를 제공한다. Finally, the present specification is a positive electrode cell comprising a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising the above-described polymer electrolyte membrane provided between the cathode cell and the anode cell.
본 명세서의 일 실시상태에 따른 블록 중합체를 포함하는 고분자 전해질막은 친수성-소수성 상분리 구조를 용이하게 형성한다.The polymer electrolyte membrane including the block polymer according to one embodiment of the present specification easily forms a hydrophilic-hydrophobic phase separation structure.
또한, 상기 고분자 전해질막은 상분리 구조를 제어함으로써 친수성 채널을 효율적으로 고분자 전해질막 중에 형성한다.In addition, the polymer electrolyte membrane effectively forms a hydrophilic channel in the polymer electrolyte membrane by controlling the phase separation structure.
추가로, 본 명세서의 일 실시상태에 따른 블록 중합체를 포함하는 고분자 전해질막은 양이온 고분자 전해질막 및 음이온 고분자 전해질막의 장점을 동시에 구현할 수 있다. In addition, the polymer electrolyte membrane including the block polymer according to the exemplary embodiment of the present specification may simultaneously realize the advantages of the cationic polymer electrolyte membrane and the anionic polymer electrolyte membrane.
본 명세서의 일 실시상태에 따른 상기 고분자 전해질막은 양성자 전도도가 우수하다. 결과적으로 이를 포함하는 연료전지 및/또는 레독스 플로우 전지의 고성능화를 가져온다.The polymer electrolyte membrane according to one embodiment of the present specification has excellent proton conductivity. The result is a high performance of fuel cells and / or redox flow cells comprising the same.
또한, 본 명세서의 일 실시상태에 따른 고분자 전해질막을 포함하는 고분자 전해질형 연료전지의 경우에는 가스 크로스오버(gas crossover)를 방지할 수 있으며, 저가습 조건에서도 이온 전도도를 향상시킬 수 있다. In addition, in the case of the polymer electrolyte fuel cell including the polymer electrolyte membrane according to one embodiment of the present specification, gas crossover may be prevented and ion conductivity may be improved even under low humidity conditions.
추가로, 본 명세서의 일 실시상태에 따른 고분자 전해질막을 포함하는 레독스 플로우 전지는 바나듐 이온의 크로스 오버(crossover)를 감소시킬 수 있다.In addition, the redox flow battery including the polymer electrolyte membrane according to one embodiment of the present specification may reduce crossover of vanadium ions.
도 1은 연료전지의 전기 발생 원리를 나타내는 개략적인 도면이다.1 is a schematic diagram illustrating a principle of electricity generation of a fuel cell.
도 2는 레독스 플로우 전지의 일 실시예를 개략적으로 나타낸 도면이다. 2 is a view schematically showing an embodiment of a redox flow battery.
도 3은 연료전지의 일 실시예를 개략적으로 나타낸 도면이다.3 is a view schematically showing an embodiment of a fuel cell.
도 4는 화합물 B의 H-NMR 스펙트럼을 나타낸 도이다.4 is a diagram showing an H-NMR spectrum of Compound B.
도 5는 중간체 1의 H-NMR 스펙트럼을 나타낸 도이다.5 is a diagram showing an H-NMR spectrum of Intermediate 1. FIG.
100: 전해질 막100: electrolyte membrane
200a: 애노드200a: anode
200b: 캐소드200b: cathode
10, 20: 탱크10, 20: tank
11, 21: 펌프11, 21: pump
31: 전해질막31: electrolyte membrane
32: 양극 셀32: anode cell
33: 음극 셀33: cathode cell
41: 양극 전해액41: anode electrolyte
42: 음극 전해액42: cathodic electrolyte
60: 스택60: stack
70: 산화제 공급부70: oxidant supply
80: 연료 공급부80: fuel supply
81: 연료 탱크81: fuel tank
82: 펌프82: pump
이하, 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, this specification is demonstrated in detail.
본 명세서에서 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다. In the present specification, when a part "contains" a certain component, this means that the component may further include other components, except for the case where there is no contrary description.
본 명세서에 있어서 '단위'란 단량체가 중합체에 포함되는 반복되는 구조로서, 단량체가 중합에 의하여 중합체 내에 결합된 구조를 의미한다.In the present specification, 'unit' is a repeating structure in which the monomer is included in the polymer, and means a structure in which the monomer is bonded into the polymer by polymerization.
본 명세서에 있어서 '단위를 포함'의 의미는 중합체 내의 주쇄에 포함된다는 의미이다.In the present specification, the term "including units" means being included in the main chain in the polymer.
본 명세서에 있어서,
Figure PCTKR2016010582-appb-I000002
는 인접한 치환기 또는 중합체의 주쇄와 결합함을 의미한다.In the present specification,
Figure PCTKR2016010582-appb-I000002
Means bonding with the backbone of an adjacent substituent or polymer.
본 명세서에서 상기 블록 중합체란 하나의 블록과 상기 블록과 상이한 1 또는 2 이상의 블록이 서로 고분자의 주쇄로 연결되어 구성된 고분자를 의미한다. In the present specification, the block polymer refers to a polymer in which one block and one or more blocks different from the block are connected to each other by a main chain of the polymer.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체는 친수성 블록 및 소수성 블록을 포함할 수 있다. 구체적으로 하나의 실시상태에 있어서, 상기 블록 중합체는 상기 화학식 1로 표시되는 단위를 포함하는 친수성 블록 및 양이온성 측쇄를 갖는 소수성 블록을 포함할 수 있다. In one embodiment of the present specification, the block polymer may include a hydrophilic block and a hydrophobic block. Specifically, in one exemplary embodiment, the block polymer may include a hydrophilic block having a unit represented by Chemical Formula 1 and a hydrophobic block having a cationic side chain.
본 명세서의 "친수성 블록"은 작용기로 이온 교환기를 갖는 블록을 의미한다. 여기서, 상기 작용기는 -SO3H, -SO3 -M+, -COOH, -COO-M+, -PO3H2, -PO3H-M+, -PO3 2-2M+, -O(CF2)mSO3H, -O(CF2)mSO3 -M+, -O(CF2)mCOOH, -O(CF2)mCOO-M+, -O(CF2)mPO3H2, -O(CF2)mPO3H-M+ 및 -O(CF2)mPO3 2 -2M+로 이루어지는 그룹에서 선택된 적어도 어느 하나일 수 있다. 여기서, M은 금속성 원소일 수 있다. 즉, 작용기는 친수성일 수 있다.By “hydrophilic block” herein is meant 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 +, -PO 3 2- 2M +, -O (CF 2 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 may be at least one selected from the group consisting of 2M + -) m PO 3 H 2, -O (CF 2) m PO 3 H - M + , and -O (CF 2) m PO 3 2. Here, M may be a metallic element. That is, the functional group may be hydrophilic.
본 명세서의 일 실시상태에 따른 화학식 1로 표시되는 제1 단위는 A 의 작용기를 포함함으로써, 친수성을 나타낼 수 있다. The first unit represented by Formula 1 according to an exemplary embodiment of the present specification may exhibit hydrophilicity by including a functional group of A.
본 명세서의 상기 "이온 교환기를 갖는 블록"이란, 해당 블록을 구성하는 구조 단위 1개당 있는 이온 교환기수로 나타내어 평균 0.5개 이상 포함되어 있는 블록인 것을 의미하고, 구조 단위 1개당 평균 1.0개 이상의 이온 교환기를 갖고 있으면 더 바람직하다.The term "block having an ion exchange group" in the present specification means a block containing an average of 0.5 or more represented by the number of ion exchange groups per structural unit constituting the block, and an average of 1.0 or more ions per structural unit It is more preferable to have an exchanger.
본 명세서의 일 실시상태에 있어서, 상기 소수성 블록은 주쇄에 -(C=O)-; 또는 -(SO2)- 를 포함한다. In one embodiment of the present specification, the hydrophobic block is-(C = O)-in the main chain; Or-(SO 2 )-.
본 명세서의 일 실시상태에 있어서, 상기 양이온성 측쇄는 -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이고, In one embodiment of the present specification, the cationic side chain is-(L) oN + RR'R ";-(L) oP + RR'R"; Or in the following Chemical Formula 1-A,
[화학식 1-A] [Formula 1-A]
Figure PCTKR2016010582-appb-I000003
Figure PCTKR2016010582-appb-I000003
L은 직접결합; O; NR"'; S; SO2; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이며, L is a direct bond; O; NR ″ ′; S; SO 2 ; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
o는 1 내지 10의 정수이고, o is an integer from 1 to 10,
o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하며, when o is 2 or more, two or more L are the same as or different from each other,
R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이다. R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
또 하나의 실시상태에 있어서, 상기 소수성 블록은 하기 화학식 2 또는 화학식 3으로 표시되는 단위를 포함한다. In another exemplary embodiment, the hydrophobic block includes a unit represented by the following Chemical Formula 2 or Chemical Formula 3.
[화학식 2][Formula 2]
Figure PCTKR2016010582-appb-I000004
Figure PCTKR2016010582-appb-I000004
[화학식 3][Formula 3]
Figure PCTKR2016010582-appb-I000005
Figure PCTKR2016010582-appb-I000005
화학식 2 및 화학식 3에 있어서, In Chemical Formula 2 and Chemical Formula 3,
S1 내지 S4는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이고, S1 to S4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or in the following Chemical Formula 1-A,
[화학식 1-A] [Formula 1-A]
Figure PCTKR2016010582-appb-I000006
Figure PCTKR2016010582-appb-I000006
L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이며, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
o는 1 내지 10의 정수이고, o is an integer from 1 to 10,
o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하며, when o is 2 or more, two or more L are the same as or different from each other,
R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이고, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
a, a', b 및 b'는 각각 1 내지 4의 정수이며, a, a ', b and b' are each an integer of 1 to 4,
a, a', b 및 b'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When a, a ', b and b' are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 있어서, 상기 소수성 블록은 적어도 하나의 양이온성 측쇄를 포함한다.In one embodiment of the present specification, the hydrophobic block includes at least one cationic side chain.
종래의 이온 교환기를 갖는 블록을 포함하는 양이온성 고분자 전해질막의 경우에는 내구성 및 내구성이 낮고, 바나듐 이온의 막을 통한 크로스 오버로 인한 전지의 효율 저하가 문제되었다. In the case of a cationic polymer electrolyte membrane including a block having a conventional ion exchanger, durability and durability are low, and a decrease in efficiency of a battery due to crossover through a membrane of vanadium ions has been a problem.
본 명세서의 일 실시상태에 따른 블록 중합체는 소수성 블록에 적어도 하나의 양이온성 측쇄를 포함함으로써, 바나듐 이온의 막을 통한 크로스 오버를 방지할 수 있어, 전류의 효율을 개선시킬 수 있다.The block polymer according to one embodiment of the present specification includes at least one cationic side chain in the hydrophobic block, thereby preventing crossover through the membrane of vanadium ions, thereby improving current efficiency.
본 명세서의 실시상태에 따라, 블록 중합체는 친수성 블록과 소수성 블록의 구획, 구분이 명확하여 상분리(phase separation)가 용이하여, 이온 전달이 용이할 수 있다. 본 명세서의 일 실시상태에 따라서, 상기 화학식 1로 표시되는 단위를 포함하는 경우에는 친수성 블록과 소수성 블록의 구분이 더욱 명확하게 되어, 종래의 고분자보다 이온 전달 효과가 우수할 수 있다. According to the exemplary embodiment of the present specification, the block polymer may be easily partitioned and separated from the hydrophilic block and the hydrophobic block to facilitate phase separation, thereby facilitating ion transfer. According to the exemplary embodiment of the present specification, when the unit represented by Chemical Formula 1 is included, the hydrophilic block and the hydrophobic block are more clearly distinguished, and the ion transfer effect may be superior to that of the conventional polymer.
또한, 본 명세서의 일 실시상태에 따른 블록 중합체는 친수성 블록에 포함되는 화학식 1로 표시되는 단위의 양이온 고분자 전해질막의 장점과 소수성 블록에 포함되는 음이온 고분자 전해질막의 장점을 동시에 구현할 수 있다. In addition, the block polymer according to the exemplary embodiment of the present specification may simultaneously realize the advantages of the cationic polymer electrolyte membrane of the unit represented by Formula 1 included in the hydrophilic block and the anion polymer electrolyte membrane included in the hydrophobic block.
본 명세서의 일 실시상태에 있어서, 상기 소수성 블록 또는 친수성 블록은 하기 화학식 4로 표시되는 화합물로부터 유래되는 단위를 더 포함한다. In one embodiment of the present specification, the hydrophobic block or the hydrophilic block further includes a unit derived from a compound represented by the following formula (4).
[화학식 4][Formula 4]
Figure PCTKR2016010582-appb-I000007
Figure PCTKR2016010582-appb-I000007
화학식 4에 있어서, In Chemical Formula 4,
E1 및 E2는 히드록시기 또는 티올기이고, E1 and E2 are hydroxy or thiol groups,
S5는 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이며, S5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
[화학식 1-A] [Formula 1-A]
Figure PCTKR2016010582-appb-I000008
Figure PCTKR2016010582-appb-I000008
L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
o는 1 내지 10의 정수이며, o is an integer from 1 to 10,
o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하고, when o is 2 or more, two or more L are the same as or different from each other,
R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이며, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
c는 1 내지 4의 정수이고, c is an integer from 1 to 4,
c'는 1 내지 3의 정수이며, c 'is an integer of 1 to 3,
c 및 c'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When c and c 'are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 있어서, 상기 소수성 블록은 하기 화학식 2 또는 화학식 3으로 표시되는 단위; 및 화학식 4로 표시되는 화합물로부터 유래되는 단위를 포함한다. In one embodiment of the present specification, the hydrophobic block is a unit represented by Formula 2 or Formula 3; And units derived from the compound represented by the formula (4).
[화학식 2][Formula 2]
Figure PCTKR2016010582-appb-I000009
Figure PCTKR2016010582-appb-I000009
[화학식 3][Formula 3]
Figure PCTKR2016010582-appb-I000010
Figure PCTKR2016010582-appb-I000010
[화학식 4][Formula 4]
Figure PCTKR2016010582-appb-I000011
Figure PCTKR2016010582-appb-I000011
화학식 2 내지 4에 있어서, In Chemical Formulas 2 to 4,
E1 및 E2는 히드록시기 또는 티올기이고, E1 and E2 are hydroxy or thiol groups,
S1 내지 S5는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이며, S1 to S5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
[화학식 1-A] [Formula 1-A]
Figure PCTKR2016010582-appb-I000012
Figure PCTKR2016010582-appb-I000012
L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
o는 1 내지 10의 정수이며, o is an integer from 1 to 10,
o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하고, when o is 2 or more, two or more L are the same as or different from each other,
R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이며, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
a, a', b, b' 및 c는 각각 1 내지 4의 정수이고,a, a ', b, b' and c are each an integer of 1 to 4,
c'는 1 내지 3의 정수이며, c 'is an integer of 1 to 3,
a, a', b, b', c 및 c'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When a, a ', b, b', c and c 'are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 있어서, 상기 R, R' 및 R"는 서로 동일하거나 상이하고, 각각 독립적으로 탄소수 1 내지 10의 알킬기이다.In one embodiment of the present specification, R, R 'and R "are the same as or different from each other, and each independently an alkyl group having 1 to 10 carbon atoms.
하나의 실시상태에 있어서, R, R' 및 R"는 메틸기이다. In one embodiment, R, R 'and R "are methyl groups.
본 명세서의 일 실시상태에 있어서, 상기 화학식 2로 표시되는 단위는 하기 화학식 2-1로 표시된다. In one embodiment of the present specification, the unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1.
[화학식 2-1][Formula 2-1]
Figure PCTKR2016010582-appb-I000013
Figure PCTKR2016010582-appb-I000013
화학식 2-1에 있어서, S1, S2, a 및 a'는 전술한 바와 동일하다.In the formula (2-1), S1, S2, a and a 'are the same as described above.
본 명세서의 일 실시상태에 있어서, 상기 화학식 3으로 표시되는 단위는 하기 화학식 3-1으로 표시된다. In one embodiment of the present specification, the unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-1.
[화학식 3-1][Formula 3-1]
Figure PCTKR2016010582-appb-I000014
Figure PCTKR2016010582-appb-I000014
화학식 3-1에 있어서, S3, S4, b 및 b'는 전술한 바와 동일하다. In the formula (3-1), S3, S4, b and b 'are the same as described above.
본 명세서의 일 실시상태에 있어서, 상기 E1 및 E2는 히드록시기 또는 티올기이다. In one embodiment of the present specification, E1 and E2 are a hydroxyl group or a thiol group.
또 하나의 실시상태에 있어서, 상기 E1은 히드록시기이다. In another exemplary embodiment, E1 is a hydroxy group.
또 다른 실시상태에 있어서, 상기 E1은 티올기이다. In another embodiment, E1 is a thiol group.
본 명세서의 일 실시상태에 있어서, 상기 E2는 히드록시기이다. In one embodiment of the present specification, E2 is a hydroxy group.
또 다른 실시상태에 있어서, 상기 E2는 티올기이다. In another embodiment, E2 is a thiol group.
본 명세서의 일 실시상태에 있어서, 상기 c'는 1이다. In one embodiment of the present specification, c 'is 1.
또 다른 실시상태에 있어서, 상기 c'는 2이다. In another embodiment, c 'is two.
본 명세서의 일 실시상태에 있어서, 상기 화학식 4로 표시되는 화합물은 하기 화학식 4-1 내지 4-4 중 어느 하나로 표시된다. In one embodiment of the present specification, the compound represented by Chemical Formula 4 is represented by any one of the following Chemical Formulas 4-1 to 4-4.
[화학식 4-1][Formula 4-1]
Figure PCTKR2016010582-appb-I000015
Figure PCTKR2016010582-appb-I000015
[화학식 4-2][Formula 4-2]
Figure PCTKR2016010582-appb-I000016
Figure PCTKR2016010582-appb-I000016
[화학식 4-3][Formula 4-3]
Figure PCTKR2016010582-appb-I000017
Figure PCTKR2016010582-appb-I000017
[화학식 4-4][Formula 4-4]
Figure PCTKR2016010582-appb-I000018
Figure PCTKR2016010582-appb-I000018
화학식 4-1 내지 4-4에 있어서, In Chemical Formulas 4-1 to 4-4,
S5 및 c의 정의는 전술한 바와 동일하고, The definitions of S5 and c are as described above,
S5'는 S5와 서로 동일하거나 상이하고, 각각 독립적으로 S5의 정의와 동일하다. S5 'is the same as or different from S5, and each independently the same as S5.
본 명세서에서 상기 화학식 1 중 -[CR6R7]n-A 구조와 벤젠고리의 링커로서 S 원자를 사용한다. 이 경우, S 원자로 연결된 -[CR6R7]n-A의 전자끌개 성질 (electron withdrawing character)로 인하여, 중합체의 형성에 용이하고, 안정한 중합체를 제공할 수 있다. In the present specification, an S atom is used as a linker of the-[CR6R7] n- A structure and the benzene ring in Chemical Formula 1. In this case, due to the electron withdrawing character of-[CR6R7] n -A linked by S atoms, it is possible to provide a polymer which is easy to form and stable.
본 명세서의 일 실시상태에 있어서, 상기 R6 및 R7은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐기이다. 구체적으로 상기 R6 및 R7은 각각 독립적으로, F; Cl; Br; 및 I로 이루어진 군으로부터 선택될 수 있다. In one embodiment of the present specification, R6 and R7 are the same as or different from each other, and are each independently a halogen group. Specifically R 6 and R 7 are each independently F; Cl; Br; And I can be selected from the group consisting of.
본 명세서의 상기 화학식 1로 표시되는 단위를 포함하는 중합체가 고분자 전해질막에 포함되는 경우, 화학식 1의 R6 및 R7이 할로겐기이면 전자를 잘 끌어 수소이온의 이동을 용이하게 할 수 있으며, 고분자 전해질막의 구조를 강하게 할 수 있는 장점이 있다. 구체적으로, 본 명세서의 일 실시상태에 따르면, 상기 R6 및 R7이 불소인 경우, 상기 장점이 극대화될 수 있다. When the polymer including the unit represented by Chemical Formula 1 of the present specification is included in the polymer electrolyte membrane, when R6 and R7 of Chemical Formula 1 are halogen groups, electrons may be well attracted to facilitate the movement of hydrogen ions, and the polymer electrolyte There is an advantage that the structure of the membrane can be strengthened. Specifically, according to one embodiment of the present specification, when R6 and R7 are fluorine, the advantages can be maximized.
본 명세서의 일 실시상태에 있어서, 상기 n은 2 내지 10의 정수이다. 본 명세서의 다른 실시상태에 있어서, 상기 n은 2 내지 6의 정수이다. In one embodiment of the present specification, n is an integer of 2 to 10. In another embodiment of the present specification, n is an integer of 2 to 6.
본 명세서의 일 실시상태에 따른 화학식 1의 단위를 포함하는 단량체는 n의 개수를 조절할 수 있다. 이 경우, 상기 괄호내의 구조의 길이를 조절하여, 고분자 전해질막의 상분리 현상을 용이하게 할 수 있는 역할을 할 수 있으며, 고분자 전해질막의 수소 이온의 이동을 용이하게 할 수 있다. 또한, 화학식 1의 단위를 포함하는 단량체는 괄호 내의 구조의 길이 조절에 따라서 반응성의 차이 및 최종 중합체의 물성을 필요에 따라서 조절할 수 있다. A monomer including a unit of Formula 1 according to an exemplary embodiment of the present specification may control the number of n. In this case, by controlling the length of the structure in the parentheses, it may serve to facilitate the phase separation phenomenon of the polymer electrolyte membrane, it is possible to facilitate the movement of hydrogen ions in the polymer electrolyte membrane. In addition, the monomer including the unit of formula (1) can be adjusted as necessary according to the difference in reactivity and the physical properties of the final polymer according to the length control of the structure in parentheses.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R5가 불소이다. In one embodiment of the present specification, R3 and R5 are fluorine.
본 명세서의 일 실시상태에 있어서, 상기 R3 및 R5의 불소가 떨어져 나가면서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 단위가 중합체 내에 포함될 수 있다. In one embodiment of the present specification, while the fluorine of the R3 and R5 is separated, a unit derived from the compound represented by Formula 1 may be included in the polymer.
본 명세서의 일 실시상태에 있어서, 상기 n은 2이다.In one embodiment of the present specification, n is 2.
다른 실시상태에 있어서, 상기 n은 3이다. In another embodiment, n is 3.
또 다른 실시상태에 있어서, 상기 n은 4이다. In another embodiment, n is 4.
다른 실시상태에 있어서, 상기 n은 5이다. In another embodiment, n is 5.
또 하나의 실시상태에 있어서, 상기 n은 6이다. In another exemplary embodiment, n is 6.
다른 실시상태에 있어서, 상기 n은 7이다. In another embodiment, n is 7.
본 명세서의 일 실시상태에 있어서, 상기 n은 8이다. In one embodiment of the present specification, n is 8.
다른 실시상태에 있어서, 상기 n은 9이다. In another embodiment, n is 9.
본 명세서의 일 실시상태에 있어서, 상기 n은 10이다. In one embodiment of the present specification, n is 10.
본 명세서의 일 실시상태에 있어서, 상기 A는 ―SO3H 또는 ―SO3 -M+ 이다.In one embodiment of the present specification, A is -SO 3 H or -SO 3 - M + .
또 하나의 실시상태에 있어서, 상기 A는 ―SO3H이다. In another embodiment, A is —SO 3 H.
상기와 같이, 화학식 1 중 A가 ―SO3H 또는 ―SO3 -M+인 경우, 화학적으로 안정한 중합체를 형성할 수 있다. As described above, is any of formulas A 1 -SO 3 H or -SO 3 - M + may be the case, form a stable polymer chemically.
본 명세서의 일 실시상태에 있어서, 상기 M은 1족 원소이다.In one embodiment of the present specification, M is a Group 1 element.
본 명세서에서 1족 원소는 Li, Na 또는 K일 수 있다.In the present specification, the Group 1 element may be Li, Na, or K.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합불로부터 유래된 단위는 하기 화학식 7 내지 9 중 어느 하나로 표시된다.In an exemplary embodiment of the present specification, the unit derived from the fused fire represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 7 to 9.
[화학식 7][Formula 7]
Figure PCTKR2016010582-appb-I000019
Figure PCTKR2016010582-appb-I000019
[화학식 8][Formula 8]
Figure PCTKR2016010582-appb-I000020
Figure PCTKR2016010582-appb-I000020
[화학식 9][Formula 9]
Figure PCTKR2016010582-appb-I000021
Figure PCTKR2016010582-appb-I000021
상기 화학식 7 내지 9에 있어서, La, R6, R7, n 및 A의 정의는 상기 화학식 1에서의 정의와 같다.In Formulas 7 to 9, La, R6, R7, n and A are the same as defined in the formula (1).
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 제1 단위는 하기 화학식 1-1 내지 1-18 중 어느 하나로 표시된다. In one embodiment of the present specification, the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-18.
[화학식 1-1][Formula 1-1]
Figure PCTKR2016010582-appb-I000022
Figure PCTKR2016010582-appb-I000022
[화학식 1-2][Formula 1-2]
Figure PCTKR2016010582-appb-I000023
Figure PCTKR2016010582-appb-I000023
[화학식 1-3][Formula 1-3]
Figure PCTKR2016010582-appb-I000024
Figure PCTKR2016010582-appb-I000024
[화학식 1-4][Formula 1-4]
Figure PCTKR2016010582-appb-I000025
Figure PCTKR2016010582-appb-I000025
[화학식 1-5][Formula 1-5]
Figure PCTKR2016010582-appb-I000026
Figure PCTKR2016010582-appb-I000026
[화학식 1-6][Formula 1-6]
Figure PCTKR2016010582-appb-I000027
Figure PCTKR2016010582-appb-I000027
[화학식 1-7][Formula 1-7]
Figure PCTKR2016010582-appb-I000028
Figure PCTKR2016010582-appb-I000028
[화학식 1-8][Formula 1-8]
Figure PCTKR2016010582-appb-I000029
Figure PCTKR2016010582-appb-I000029
[화학식 1-9][Formula 1-9]
Figure PCTKR2016010582-appb-I000030
Figure PCTKR2016010582-appb-I000030
[화학식 1-10][Formula 1-10]
Figure PCTKR2016010582-appb-I000031
Figure PCTKR2016010582-appb-I000031
[화학식 1-11][Formula 1-11]
Figure PCTKR2016010582-appb-I000032
Figure PCTKR2016010582-appb-I000032
[화학식 1-12][Formula 1-12]
Figure PCTKR2016010582-appb-I000033
Figure PCTKR2016010582-appb-I000033
[화학식 1-13][Formula 1-13]
Figure PCTKR2016010582-appb-I000034
Figure PCTKR2016010582-appb-I000034
[화학식 1-14][Formula 1-14]
Figure PCTKR2016010582-appb-I000035
Figure PCTKR2016010582-appb-I000035
[화학식 1-15][Formula 1-15]
Figure PCTKR2016010582-appb-I000036
Figure PCTKR2016010582-appb-I000036
[화학식 1-16][Formula 1-16]
Figure PCTKR2016010582-appb-I000037
Figure PCTKR2016010582-appb-I000037
[화학식 1-17][Formula 1-17]
Figure PCTKR2016010582-appb-I000038
Figure PCTKR2016010582-appb-I000038
[화학식 1-18][Formula 1-18]
Figure PCTKR2016010582-appb-I000039
Figure PCTKR2016010582-appb-I000039
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 제1 단위는 하기 화학식 1-19 내지 1-36 중 어느 하나로 표시된다. In one embodiment of the present specification, the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-19 to 1-36.
[화학식 1-19][Formula 1-19]
Figure PCTKR2016010582-appb-I000040
Figure PCTKR2016010582-appb-I000040
[화학식 1-20][Formula 1-20]
Figure PCTKR2016010582-appb-I000041
Figure PCTKR2016010582-appb-I000041
[화학식 1-21][Formula 1-21]
Figure PCTKR2016010582-appb-I000042
Figure PCTKR2016010582-appb-I000042
[화학식 1-22][Formula 1-22]
Figure PCTKR2016010582-appb-I000043
Figure PCTKR2016010582-appb-I000043
[화학식 1-23][Formula 1-23]
Figure PCTKR2016010582-appb-I000044
Figure PCTKR2016010582-appb-I000044
[화학식 1-24][Formula 1-24]
Figure PCTKR2016010582-appb-I000045
Figure PCTKR2016010582-appb-I000045
[화학식 1-25][Formula 1-25]
Figure PCTKR2016010582-appb-I000046
Figure PCTKR2016010582-appb-I000046
[화학식 1-26][Formula 1-26]
Figure PCTKR2016010582-appb-I000047
Figure PCTKR2016010582-appb-I000047
[화학식 1-27][Formula 1-27]
Figure PCTKR2016010582-appb-I000048
Figure PCTKR2016010582-appb-I000048
[화학식 1-28][Formula 1-28]
Figure PCTKR2016010582-appb-I000049
Figure PCTKR2016010582-appb-I000049
[화학식 1-29][Formula 1-29]
Figure PCTKR2016010582-appb-I000050
Figure PCTKR2016010582-appb-I000050
[화학식 1-30][Formula 1-30]
Figure PCTKR2016010582-appb-I000051
Figure PCTKR2016010582-appb-I000051
[화학식 1-31][Formula 1-31]
Figure PCTKR2016010582-appb-I000052
Figure PCTKR2016010582-appb-I000052
[화학식 1-32][Formula 1-32]
Figure PCTKR2016010582-appb-I000053
Figure PCTKR2016010582-appb-I000053
[화학식 1-33][Formula 1-33]
Figure PCTKR2016010582-appb-I000054
Figure PCTKR2016010582-appb-I000054
[화학식 1-34][Formula 1-34]
Figure PCTKR2016010582-appb-I000055
Figure PCTKR2016010582-appb-I000055
[화학식 1-35][Formula 1-35]
Figure PCTKR2016010582-appb-I000056
Figure PCTKR2016010582-appb-I000056
[화학식 1-36][Formula 1-36]
Figure PCTKR2016010582-appb-I000057
Figure PCTKR2016010582-appb-I000057
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 제1 단위는 하기 화학식 1-37 내지 1-54 중 어느 하나로 표시된다. In one embodiment of the present specification, the first unit derived from the compound represented by Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-37 to 1-54.
[화학식 1-37][Formula 1-37]
Figure PCTKR2016010582-appb-I000058
Figure PCTKR2016010582-appb-I000058
[화학식 1-38][Formula 1-38]
Figure PCTKR2016010582-appb-I000059
Figure PCTKR2016010582-appb-I000059
[화학식 1-39][Formula 1-39]
Figure PCTKR2016010582-appb-I000060
Figure PCTKR2016010582-appb-I000060
[화학식 1-40][Formula 1-40]
Figure PCTKR2016010582-appb-I000061
Figure PCTKR2016010582-appb-I000061
[화학식 1-41][Formula 1-41]
Figure PCTKR2016010582-appb-I000062
Figure PCTKR2016010582-appb-I000062
[화학식 1-42][Formula 1-42]
Figure PCTKR2016010582-appb-I000063
Figure PCTKR2016010582-appb-I000063
[화학식 1-43][Formula 1-43]
Figure PCTKR2016010582-appb-I000064
Figure PCTKR2016010582-appb-I000064
[화학식 1-44][Formula 1-44]
Figure PCTKR2016010582-appb-I000065
Figure PCTKR2016010582-appb-I000065
[화학식 1-45][Formula 1-45]
Figure PCTKR2016010582-appb-I000066
Figure PCTKR2016010582-appb-I000066
[화학식 1-46][Formula 1-46]
Figure PCTKR2016010582-appb-I000067
Figure PCTKR2016010582-appb-I000067
[화학식 1-47][Formula 1-47]
Figure PCTKR2016010582-appb-I000068
Figure PCTKR2016010582-appb-I000068
[화학식 1-48][Formula 1-48]
Figure PCTKR2016010582-appb-I000069
Figure PCTKR2016010582-appb-I000069
[화학식 1-49][Formula 1-49]
Figure PCTKR2016010582-appb-I000070
Figure PCTKR2016010582-appb-I000070
[화학식 1-50][Formula 1-50]
Figure PCTKR2016010582-appb-I000071
Figure PCTKR2016010582-appb-I000071
[화학식 1-51][Formula 1-51]
Figure PCTKR2016010582-appb-I000072
Figure PCTKR2016010582-appb-I000072
[화학식 1-52][Formula 1-52]
Figure PCTKR2016010582-appb-I000073
Figure PCTKR2016010582-appb-I000073
[화학식 1-53][Formula 1-53]
Figure PCTKR2016010582-appb-I000074
Figure PCTKR2016010582-appb-I000074
[화학식 1-54][Formula 1-54]
Figure PCTKR2016010582-appb-I000075
Figure PCTKR2016010582-appb-I000075
본 명세서의 일 실시상태에 있어서, 상기 친수성 블록은 상기 화학식 1로 표시되는 단위; 및 상기 화학식 4로 표시되는 화합물로부터 유래되는 단위를 포함한다. In one embodiment of the present specification, the hydrophilic block is a unit represented by Formula 1; And a unit derived from the compound represented by Formula 4 above.
본 명세서의 일 실시상태에 있어서, 상기 S1은 -(L)o-N+RR'R"이다. In one embodiment of the present specification, S1 is-(L) oN + RR'R ".
또 하나의 실시상태에 있어서, 상기 S2는-(L)o-N+RR'R"이다. In another exemplary embodiment, S2 is-(L) oN + RR'R ".
본 명세서의 일 실시상태에 있어서, 상기 S3는 -(L)o-N+RR'R"이다. In one embodiment of the present specification, S3 is-(L) oN + RR'R ".
본 명세서의 일 실시상태에 있어서, 상기 소수성 블록은 양이온 측쇄를 포함하면, 족하며 그의 위치는 한정하지 않는다.In one embodiment of the present specification, the hydrophobic block includes a cationic side chain, and the position thereof is not limited.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체는 하기 화학식 A 내지 J 및 A-1 내지 J-1 중 어느 하나로 표시되는 단위를 포함한다. In one embodiment of the present specification, the block polymer includes a unit represented by any one of the following Formulas A to J and A-1 to J-1.
[화학식 A][Formula A]
Figure PCTKR2016010582-appb-I000076
Figure PCTKR2016010582-appb-I000076
[화학식 A-1][Formula A-1]
Figure PCTKR2016010582-appb-I000077
Figure PCTKR2016010582-appb-I000077
[화학식 B][Formula B]
Figure PCTKR2016010582-appb-I000078
Figure PCTKR2016010582-appb-I000078
[화학식 B-1][Formula B-1]
Figure PCTKR2016010582-appb-I000079
Figure PCTKR2016010582-appb-I000079
[화학식 C][Formula C]
Figure PCTKR2016010582-appb-I000080
Figure PCTKR2016010582-appb-I000080
[화학식 C-1][Formula C-1]
Figure PCTKR2016010582-appb-I000081
Figure PCTKR2016010582-appb-I000081
[화학식 D][Formula D]
Figure PCTKR2016010582-appb-I000082
Figure PCTKR2016010582-appb-I000082
[화학식 D-1][Formula D-1]
Figure PCTKR2016010582-appb-I000083
Figure PCTKR2016010582-appb-I000083
[화학식 E][Formula E]
Figure PCTKR2016010582-appb-I000084
Figure PCTKR2016010582-appb-I000084
[화학식 E-1][Formula E-1]
Figure PCTKR2016010582-appb-I000085
Figure PCTKR2016010582-appb-I000085
[화학식 F]Formula F]
Figure PCTKR2016010582-appb-I000086
Figure PCTKR2016010582-appb-I000086
[화학식 F-1][Formula F-1]
Figure PCTKR2016010582-appb-I000087
Figure PCTKR2016010582-appb-I000087
[화학식 G][Formula G]
Figure PCTKR2016010582-appb-I000088
Figure PCTKR2016010582-appb-I000088
[화학식 G-1][Formula G-1]
Figure PCTKR2016010582-appb-I000089
Figure PCTKR2016010582-appb-I000089
[화학식 H][Formula H]
Figure PCTKR2016010582-appb-I000090
Figure PCTKR2016010582-appb-I000090
[화학식 H-1][Formula H-1]
Figure PCTKR2016010582-appb-I000091
Figure PCTKR2016010582-appb-I000091
[화학식 I][Formula I]
Figure PCTKR2016010582-appb-I000092
Figure PCTKR2016010582-appb-I000092
[화학식 I-1][Formula I-1]
Figure PCTKR2016010582-appb-I000093
Figure PCTKR2016010582-appb-I000093
[화학식 J][Formula J]
Figure PCTKR2016010582-appb-I000094
Figure PCTKR2016010582-appb-I000094
[화학식 J-1][Formula J-1]
Figure PCTKR2016010582-appb-I000095
Figure PCTKR2016010582-appb-I000095
화학식 A 내지 J 및 A-1 내지 J-1에 있어서, In Chemical Formulas A to J and A-1 to J-1,
L 및 o는 전술한 바와 동일하고, L and o are the same as described above,
x 및 y는 각각 독립적으로 블록 중합체의 몰비율로서, 0 초과 1 미만의 정수이고, x and y are each independently a molar ratio of the block polymer, an integer greater than 0 and less than 1,
x+y = 1이다. x + y = 1.
또 하나의 실시상태에 있어서, 상기 화학식 A 내지 H 중
Figure PCTKR2016010582-appb-I000096
는
Figure PCTKR2016010582-appb-I000097
또는
Figure PCTKR2016010582-appb-I000098
로 치환될 수 있다. In another exemplary embodiment, the chemical formulas A to H
Figure PCTKR2016010582-appb-I000096
Is
Figure PCTKR2016010582-appb-I000097
or
Figure PCTKR2016010582-appb-I000098
It may be substituted by.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체 내에서 상기 친수성 블록과 소수성 블록은 1:0.001 내지 1:100 의 몰 비율로 포함된다. 본 명세서의 일 실시상태에 있어서, 상기 블록 중합체 내에서 상기 친수성 블록과 소수성 블록은 1: 1 내지 1:0.001 몰 비율로 포함된다. 또 다른 실시상태에 있어서, 상기 블록 중합체 내에서 상기 친수성 블록과 소수성 블록은 1:0.1 내지 1:0.01의 몰 비율로 포함된다.In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the mole ratio of 1: 0.001 to 1: 100 in the block polymer. In one embodiment of the present specification, the hydrophilic block and the hydrophobic block are included in the block polymer in a ratio of 1: 1 to 1: 0.001. In another embodiment, the hydrophilic block and hydrophobic block in the block polymer is included in a molar ratio of 1: 0.1 to 1: 0.01.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체의 전체 중합체를 기준으로 소수성 블록이 0.1 몰% 내지 50 몰%로 포함되는 것이 바람직하며, 1 몰% 내지 10몰% 로 포함되는 것이 더욱 바람직하다. In one embodiment of the present specification, the hydrophobic block is preferably included in an amount of 0.1 mol% to 50 mol%, more preferably 1 mol% to 10 mol% based on the entire polymer of the block polymer.
이 경우, 블록 중합체의 이온 전달 능력을 상승시킬 수 있다.In this case, the ion transport ability of the block polymer can be raised.
본 명세서의 일 실시상태에 있어서, 상기 친수성 블록 내에서 상기 화학식 1로 표시되는 단위는 상기 친수성 블록을 기준으로 0.01 몰% 내지 100몰% 포함된다. In one embodiment of the present specification, the unit represented by Chemical Formula 1 in the hydrophilic block is included from 0.01 mol% to 100 mol% based on the hydrophilic block.
본 명세서의 하나의 실시상태에 있어서, 상기 친수성 블록의 수평균 분자량은 1,000 g/mol 내지 300,000 g/mol 이다. 구체적인 실시상태에 있어서, 2,000 g/mol 내지 100,000 g/mol 이다. 또 다른 실시상태에 있어서, 2,500 g/mol 내지 50,000 g/mol 이다. In one embodiment of the present specification, the number average molecular weight of the hydrophilic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
본 명세서의 하나의 실시상태에 있어서, 상기 소수성 블록의 수평균 분자량은 1,000 g/mol 내지 300,000 g/mol 이다. 구체적인 실시상태에 있어서, 2,000 g/mol 내지 100,000 g/mol 이다. 또 다른 실시상태에 있어서, 2,500 g/mol 내지 50,000 g/mol 이다. In one embodiment of the present specification, the number average molecular weight of the hydrophobic block is 1,000 g / mol to 300,000 g / mol. In a specific embodiment, 2,000 g / mol to 100,000 g / mol. In another embodiment, it is from 2,500 g / mol to 50,000 g / mol.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체는 브랜처(brancher)를 더 포함할 수 있다. 본 명세서에서 브랜처란 중합체 사슬을 연결 또는 가교하는 역할을 한다. In one embodiment of the present specification, the block polymer may further include a brancher. In the present specification, a brancher serves to link or crosslink a polymer chain.
본 명세서에서 상기 브랜처를 더 포함하는 블록 중합체의 경우에는 브랜처가 직접 중합체의 주쇄를 구성할 수 있으며, 박막의 기계적 집적도를 향상시킬 수 있다. 구체적으로 본 발명의 브랜치된 블록 중합체는 산 치환체(acid substituents)를 포함하지 않는 브랜치된 소수 블록(branched hydrophobic block)과 산 치환체를 포함하는 브랜치된 친수 블록(branched hydrophilic block)을 중합함으로써 후처리 술폰화 반응(post-sulfonation)이나 술폰화된 중합체(sulfonated polymer)의 가교반응(cross-linking)을 실시하지 않고 브랜처(brancher)가 중합체의 주사슬을 직접 구성하며, 박막의 기계적 집적도를 유지시켜주는 소수 블록과 박막에 이온전도성을 부여하는 친수 블록이 교대로 화학적 결합으로 이어지게 된다.In the present specification, in the case of the block polymer further comprising the brancher, the brancher may directly constitute the main chain of the polymer, and may improve the mechanical density of the thin film. Specifically, the branched block polymers of the present invention are polymerized by post-treatment by polymerizing branched hydrophobic blocks that do not contain acid substituents and branched hydrophilic blocks that include acid substituents. Without the post-sulfonation or cross-linking of the sulfonated polymer, the brancher directly forms the main chain of the polymer and maintains the mechanical density of the thin film. In the main, a small number of blocks and a hydrophilic block that imparts ion conductivity to the thin film are alternately connected to the chemical bond.
본 명세서의 일 실시상태에 있어서, 상기 블록 중합체는 하기 화학식 5로 표시되는 화합물로부터 유래되는 브랜처; 또는 하기 화학식 6으로 표시되는 브랜처를 더 포함한다. In one embodiment of the present specification, the block polymer is a brancher derived from a compound represented by the following formula (5); Or a brancher represented by the following formula (6).
[화학식 5][Formula 5]
Figure PCTKR2016010582-appb-I000099
Figure PCTKR2016010582-appb-I000099
[화학식 6][Formula 6]
Figure PCTKR2016010582-appb-I000100
Figure PCTKR2016010582-appb-I000100
화학식 5 및 6에 있어서, In Chemical Formulas 5 and 6,
X는 S; O; CO; SO; SO2; NR""; 탄화수소계 또는 불소계 결합체이며, X is S; O; CO; SO; SO 2 ; NR ""; Hydrocarbon-based or fluorine-based conjugates,
R""은 수소; 할로겐기로 치환된 방향족고리; 또는 할로겐기로 치환된 지방족 고리이고, R ″ ″ is hydrogen; Aromatic rings substituted with halogen groups; Or an aliphatic ring substituted with a halogen group,
l은 0 내지 10의 정수이며, l is an integer from 0 to 10,
l이 2 이상인 경우, 2 이상의 X는 서로 동일하거나 상이하고, when l is 2 or more, two or more X are the same as or different from each other,
Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 히드록시기 및 할로겐기로 이루어진 군에서 선택되는 치환기로 1 또는 2 이상 치환된 방향족고리; 또는 히드록시기 및 할로겐기로 이루어진 군에서 선택되는 치환기로 1 또는 2 이상 치환된 지방족 고리이며, Y1 and Y2 are the same as or different from each other, and each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,
Z는 3가의 유기기이다. Z is a trivalent organic group.
본 명세서의 상기 치환기들의 예시들은 아래에서 설명하나, 이에 한정되는 것은 아니다. Examples of the substituents herein are described below, but are not limited thereto.
본 명세서에 있어서,
Figure PCTKR2016010582-appb-I000101
는 인접한 치환기 또는 중합체의 주쇄와 결합함을 의미한다.In the present specification,
Figure PCTKR2016010582-appb-I000101
Means bonding with the backbone of an adjacent substituent or polymer.
본 명세서에서, 상기 "유래"란 화합물의 결합이 끊기거나, 치환기가 떨어져 나가면서 새로운 결합이 발생하는 것을 의미하며, 상기 화합물로부터 유래되는 단위는 중합체의 주쇄에 연결되는 단위를 의미할 수 있다. 상기 단위는 중합체 내 주쇄에 포함되어 중합체를 구성할 수 있다. In the present specification, the "derived" means that the bonding of the compound is broken, or the substituent is separated, a new bond occurs, the unit derived from the compound may mean a unit connected to the main chain of the polymer. The unit may be included in the main chain in the polymer to constitute the polymer.
본 명세서의 일 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 단위란, R1 내지 R5 중 적어도 2 개가 할로겐기인 경우, 할로겐기가 떨어져 나가면서, 중합체의 주쇄와 연결되는 것을 의미할 수 있다. 또 다른 실시상태에 있어서, 상기 화학식 1로 표시되는 화합물로부터 유래되는 단위란, R1 내지 R5 중 적어도 2 개가 히드록시기인 경우, 할로겐기를 갖고 있는 공단량체(comonomer)의 할로겐기를 떨어뜨려 중합체의 주쇄와 연결되는 것을 의미할 수 있다. In an exemplary embodiment of the present specification, the unit derived from the compound represented by Chemical Formula 1 may mean that when at least two of R1 to R5 are halogen groups, the halogen groups are separated and connected to the main chain of the polymer. . In another exemplary embodiment, the unit derived from the compound represented by Chemical Formula 1 is a hydroxy group, and when at least two of R1 to R5 are hydroxy groups, a halogen group of a comonomer having a halogen group is dropped to connect with the main chain of the polymer. Can mean being.
본 명세서의 일 실시상태에 있어서, 상기 화학식 4로 표시되는 화합물로부터 유래되는 단위란, E1 및 E2가 티올기 또는 히드록시기이고, 티올기 또는 히드록시기의 탈수소화되면서, 중합체 주쇄와 연결되는 것을 의미할 수 있다. 상기 유래되는 단위는 탄수소화 되면서 중합체의 주쇄와 연결되는 것을 의미하는 것도 포함하고, 산처리, 열처리 등의 후처리를 통하여 주쇄와 연결되는 부위를 변형시키는 것도 포함할 수 있다. In one embodiment of the present specification, the unit derived from the compound represented by Chemical Formula 4 may mean that E1 and E2 are thiol groups or hydroxy groups, and are connected to the polymer main chain while dehydrogenating the thiol groups or hydroxy groups. have. The derived unit may include being connected to the main chain of the polymer while being carbohydrated, and may also include modifying a site connected to the main chain through post-treatment such as acid treatment and heat treatment.
예컨대, 본 명세서의 일 실시상태에 있어서, E1 또는 E2가 히드록시기인 경우에는 중합체 주쇄에서 -O-의 연결기가 구비될 수 있으며, E1 및 E2가 티올기인 경우에는 중합체 주쇄에서 -S-의 연결기가 구비될 수 있다. 또한, 필요에 따라 산처리를 통하여, 중합체 주쇄의 -S-의 연결기를 -SO2-로 변환시킬 수 있다. For example, in one embodiment of the present specification, when E1 or E2 is a hydroxy group, a linking group of -O- may be provided in the polymer main chain, and when E1 and E2 are thiol groups, the linking group of -S- in the polymer main chain may be provided. It may be provided. In addition, through acid treatment, if necessary, the linking group of -S- of the polymer backbone can be converted to -SO 2- .
또한, 구체적으로 본 명세서에서 상기 화학식 5의 화합물로부터 유래되는 브랜처는 상기 Y1 및 Y2 각각의 할로겐기로 치환된 방향족 고리; 또는 할로겐기로 치환된 지방족 고리 중 할로겐기가 방향족 고리 또는 지방족 고리에서 떨어져 나가면서, 브랜처로서 작용할 수 있다. 구체적으로 2 이상의 할로겐기가 떨어져 나가면서 중합체 내에서 브랜처로 작용할 수 있다. In addition, specifically, the brancher derived from the compound of Formula 5 in the present specification is an aromatic ring substituted with a halogen group of each of the Y1 and Y2; Or a halogen group in the aliphatic ring substituted with a halogen group may act as a brancher while being separated from the aromatic ring or aliphatic ring. Specifically, two or more halogen groups may fall off and act as a brancher in the polymer.
상기 "치환"이라는 용어는 화합물의 탄소 원자에 결합된 수소 원자가 다른 치환기로 바뀌는 것을 의미하며, 치환되는 위치는 수소 원자가 치환되는 위치 즉, 치환기가 치환 가능한 위치라면 한정하지 않으며, 2 이상 치환되는 경우, 2 이상의 치환기는 서로 동일하거나 상이할 수 있다.The term "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where a substituent can be substituted, if two or more substituted , Two or more substituents may be the same or different from each other.
본 명세서에서 탄화수소계는 탄소와 수소로만 이루어진 유기 화합물을 의미하며, 직쇄, 분지쇄, 환형 탄화수소 등이 있으며, 이를 한정하지 않는다. 또한, 단일 결합, 이중결합 또는 삼중결합을 포함할 수 있으며 이를 한정하지 않는다.In the present specification, the hydrocarbon-based means an organic compound consisting of only carbon and hydrogen, and includes a straight chain, branched chain, cyclic hydrocarbon, and the like, but is not limited thereto. In addition, it may include a single bond, a double bond or a triple bond, but is not limited thereto.
본 명세서에서 불소계 결합체는 상기 탄화수소계에서 탄소-수소 결합이 일부 또는 전부가 불소로 치환된 것을 의미한다. In the present specification, the fluorine-based conjugate means that some or all of the carbon-hydrogen bonds in the hydrocarbon system are substituted with fluorine.
본 명세서에서 상기 방향족 고리는 방향족 탄화수소고리 또는 방향족 헤테로고리일 수 있으며, 단환 또는 다환일 수 있다. In the present specification, the aromatic ring may be an aromatic hydrocarbon ring or an aromatic hetero ring, and may be monocyclic or polycyclic.
구체적으로 방향족 탄화수소고리로는 페닐기, 비페닐기, 터페닐기 등의 단환식 방향족 및 나프틸기, 비나프틸기, 안트라세닐기, 페난트레닐기, 파이레닐기, 페릴레닐기, 테트라세닐기, 크라이세닐기, 플루오레닐기, 아세나프타센닐기, 트리페닐렌기, 플루오란텐(fluoranthene)기 등의 다환식 방향족 등이 있으며, 이에 한정되지 않는다. Specifically, as the aromatic hydrocarbon ring, monocyclic aromatic and naphthyl groups, binaphthyl groups, anthracenyl groups, phenanthrenyl groups, pyrenyl groups, peryllenyl groups, tetrasenyl groups, chrysenyl groups such as phenyl groups, biphenyl groups and terphenyl groups And polycyclic aromatics such as fluorenyl group, acenaphthasenyl group, triphenylene group, and fluoranthene group, and the like.
본 명세서에서 방향족 헤테로고리는 상기 방향족 탄화수소고리에서 탄소원자 대신에 헤테로 원자 예컨대, O, S, N, Se 등을 1 이상 포함하는 구조를 의미한다. 구체적으로 티오펜기, 퓨란기, 피롤기, 이미다졸기, 티아졸기, 옥사졸기, 옥사디아졸기, 트리아졸기, 피리딜기, 비피리딜기, 피리미딜기, 트리아진기, 아크리딜기, 피리다진기, 피라지닐기, 퀴놀리닐기, 퀴나졸린기, 퀴녹살리닐기, 프탈라지닐기, 피리도 피리미디닐기, 피리도 피라지닐기, 피라지노 피라지닐기, 이소퀴놀린기, 인돌기, 카바졸기, 벤조옥사졸기, 벤조이미다졸기, 벤조티아졸기, 벤조카바졸기, 벤조티오펜기, 디벤조티오펜기, 벤조퓨라닐기, 페난쓰롤린기(phenanthroline), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 페노티아지닐기 및 디벤조퓨라닐기 등이 있으나, 이들에만 한정되는 것은 아니다.In the present specification, the aromatic heterocycle means a structure including one or more hetero atoms such as O, S, N, Se, or the like instead of a carbon atom in the aromatic hydrocarbon ring. Specifically, thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, acridil group, pyridazine group , Pyrazinyl, quinolinyl, quinazolin, quinoxalinyl, phthalazinyl, pyrido pyrimidinyl, pyrido pyrazinyl, pyrazino pyrazinyl, isoquinoline, indole, carbazole, Benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group, isoxazolyl group, oxadia There may be a jolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, but is not limited thereto.
본 명세서에서 상기 지방족 고리는 지방족 탄화수소고리 또는 지방족 헤테로고리일 수 있으며, 단환 또는 다환일 수 있다. 상기 지방족 고리의 예시로는 시클로펜틸기, 시클로헥실기 등이 있으며 이를 한정하지 않는다. In the present specification, the aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic hetero ring, and may be monocyclic or polycyclic. Examples of the aliphatic ring include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.
본 명세서에서 유기기로는 알킬기, 알케닐기, 시클로알킬기, 시클로알케닐기, 아릴기, 아랄킬기 등을 들 수 있다. 이 유기기는 상기 유기기 중에 헤테로 원자 등의 탄화수소기 이외의 결합이나 치환기를 포함하고 있어도 된다. 또한, 상기 유기기는 직쇄상, 분기쇄상, 환상 중 어느 것이어도 된다.In this specification, an organic group, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, etc. are mentioned. This organic group may contain the bond and substituents other than hydrocarbon groups, such as a hetero atom, in the said organic group. The organic group may be any of linear, branched and cyclic.
본 명세서에서 3가의 유기기란 유기 화합물에 결합 위치가 3개 있는 3가기를 의미한다.In the present specification, the trivalent organic group means a trivalent group having three bonding positions in an organic compound.
또한, 상기 유기기는 환상구조를 형성할 수도 있으며, 환상 구조를 형성할 수도 있으며, 발명의 효과가 손상되지 않는 한 헤테로 원자를 포함하여 결합을 형성할 수 있다. In addition, the organic group may form a cyclic structure, may form a cyclic structure, and may include a hetero atom to form a bond as long as the effects of the invention are not impaired.
구체적으로 산소 원자, 질소 원자, 규소 원자 등의 헤테로 원자를 포함하는 결합을 들 수 있다. 구체예로는, 에테르 결합, 티오에테르 결합, 카르보닐 결합, 티오카르보닐 결합, 에스테르 결합, 아미드 결합, 우레탄 결합, 이미노 결합(-N=C(-A)-,-C(=NA)-: A은 수소 원자 또는 유기기를 나타낸다), 카보네이트 결합, 설포닐 결합, 설피닐 결합, 아조 결합 등을 들 수 있으며, 이를 한정하지 않는다. Specifically, the bond containing hetero atoms, such as an oxygen atom, a nitrogen atom, and a silicon atom, is mentioned. Specific examples include ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, amide bonds, urethane bonds, imino bonds (-N = C (-A)-,-C (= NA) -A represents a hydrogen atom or an organic group), and a carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, etc. are mentioned, It does not limit this.
상기 환상 구조로는 전술한 방향족 고리, 지방족고리 등이 있을 수 있으며, 단환 또는 다환일 수 있다. The cyclic structure may include the aforementioned aromatic ring, aliphatic ring, and the like, and may be monocyclic or polycyclic.
본 명세서에 있어서, 상기 알킬기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나 1 내지 50인 것이 바람직하다. 구체적인 예로는 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, t-부틸기, 펜틸기, 헥실기 및 헵틸기 등이 있으나, 이들에 한정되지 않는다. In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl groups.
본 명세서에 있어서, 상기 알케닐기는 직쇄 또는 분지쇄일 수 있고, 탄소수는 특별히 한정되지 않으나, 2 내지 40인 것이 바람직하다. 구체적인 예로는 비닐, 1-프로페닐, 이소프로페닐, 1-부테닐, 2-부테닐, 3-부테닐, 1-펜테닐, 2-펜테닐, 3-펜테닐, 3-메틸-1-부테닐, 1,3-부타디에닐, 알릴, 1-페닐비닐-1-일, 2-페닐비닐-1-일, 2,2-디페닐비닐-1-일, 2-페닐-2-(나프틸-1-일)비닐-1-일, 2,2-비스(디페닐-1-일)비닐-1-일, 스틸베닐기, 스티레닐기 등이 있으나 이들에 한정되지 않는다.In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.
본 명세서에 있어서, 시클로알킬기는 특별히 한정되지 않으나, 탄소수 3 내지 60인 것이 바람직하며, 특히 시클로펜틸기, 시클로헥실기 등이 있으나, 이를 한정하지 않는다. In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and especially cyclopentyl group, cyclohexyl group, and the like, but is not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 l은 3이상이다.In one embodiment of the present specification, l is 3 or more.
본 명세서의 일 실시상태에 있어서, 상기 X는 S이다. In one embodiment of the present specification, X is S.
또 하나의 실시상태에 있어서, 상기 X는 할로알킬기이다.In another exemplary embodiment, X is a haloalkyl group.
또 다른 실시상태에 있어서, 상기 X는 CH2이다. In another embodiment, X is CH 2 .
본 명세서의 다른 실시상태에 있어서, 상기 X는 NR'"이다. In another embodiment of the present specification, X is NR '".
본 명세서의 일 실시상태에 있어서, 상기 Y1 및 Y2는 서로 동일하거나 상이하며, 각각 독립적으로 할로겐 치환 방향족 고리이다. In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and are each independently a halogen substituted aromatic ring.
본 명세서의 일 실시상태에 있어서, 상기 Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 불소 치환된 방향족 탄화수소고리이다.In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and are each independently a fluorine-substituted aromatic hydrocarbon ring.
또 하나의 실시상태에 있어서, 상기 Y1 및 Y2는 각각 불소 치환된 페닐기이다. 구체적으로 2,4-페닐, 2,6-페닐, 2,3-페닐, 3,4-페닐 등이 있으며 이를 한정하지 않는다. In another exemplary embodiment, Y1 and Y2 are each a fluorine substituted phenyl group. Specifically, 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl and the like are not limited thereto.
본 명세서의 일 실시상태에 있어서, 상기 화학식 5로 표시되는 화합물은 하기 구조 중 어느 하나로 표시될 수 있다. In one embodiment of the present specification, the compound represented by Formula 5 may be represented by any one of the following structures.
Figure PCTKR2016010582-appb-I000102
Figure PCTKR2016010582-appb-I000102
상기 구조에 있어서, X, l 및 R'"은 화학식 5에서 정의한 바와 동일하다. In the above structure, X, 1 and R '"are the same as defined in the formula (5).
본 명세서의 일 실시상태에 따르면, 상기 화학식 6의 Z는 하기 화학식6-1 내지 6-4 중 어느 하나로 표시될 수 있다. According to an exemplary embodiment of the present specification, Z in Chemical Formula 6 may be represented by any one of the following Chemical Formulas 6-1 to 6-4.
[화학식 6-1][Formula 6-1]
Figure PCTKR2016010582-appb-I000103
Figure PCTKR2016010582-appb-I000103
[화학식 6-2][Formula 6-2]
Figure PCTKR2016010582-appb-I000104
Figure PCTKR2016010582-appb-I000104
[화학식 6-3][Formula 6-3]
Figure PCTKR2016010582-appb-I000105
Figure PCTKR2016010582-appb-I000105
[화학식 6-4][Formula 6-4]
Figure PCTKR2016010582-appb-I000106
Figure PCTKR2016010582-appb-I000106
상기 화학식 6-1 내지 6-4에 있어서,In Chemical Formulas 6-1 to 6-4,
L1 내지 L7은 서로 동일하거나 상이하고, 각각 독립적으로 직접결합; -S-; -O-; -CO-; 또는 -SO2-이고, L1 To L7 are the same as or different from each other, and each independently a direct bond; -S-; -O-; -CO-; Or -SO 2- ,
R10 내지 R20은 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기이고, R10 to R20 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
e, e', e", f', h, i 및 j는 각각 1 내지 4의 정수이며, e, e ', e ", f', h, i and j are each an integer of 1 to 4,
d, f, g 및 k는 각각 1 내지 3의 정수이고, d, f, g and k are each an integer of 1 to 3,
d, e, e', e", f, f', g, h, i, j 및 k가 각각 2 이상의 정수인 경우, 2 이상의 괄호내의 구조는 서로 동일하거나 상이하다. When d, e, e ', e ", f, f', g, h, i, j and k are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
본 명세서의 일 실시상태에 있어서, 상기 L1은 CO이다. In one embodiment of the present specification, L1 is CO.
또 하나의 실시상태에 있어서, 상기 L1은 SO2이다. In another exemplary embodiment, L1 is SO 2 .
또 하나의 실시상태에 있어서, 상기 L1은 S이다. In another exemplary embodiment, L1 is S.
또 다른 실시상태에 있어서, 상기 L2는 CO이다. In another embodiment, L2 is CO.
또 하나의 실시상태에 있어서, 상기 L2는 SO2이다. In another exemplary embodiment, L2 is SO 2 .
또 다른 실시상태에 있어서, 상기 L2는 S이다. In another embodiment, L2 is S.
본 명세서의 일 실시상태에 있어서, 상기 L3는 CO이다. In one embodiment of the present specification, L3 is CO.
또 하나의 실시상태에 있어서, 상기 L3는 SO2이다. In another exemplary embodiment, L3 is SO 2 .
또 다른 실시상태에 있어서, 상기 L3는 S이다. In another embodiment, L3 is S.
본 명세서의 일 실시상태에 있어서, 상기 L4는 CO이다. In one embodiment of the present specification, L4 is CO.
또 하나의 실시상태에 있어서, 상기 L4는 SO2이다.In another exemplary embodiment, L4 is SO 2 .
본 명세서의 일 실시상태에 있어서, 상기 L5는 직접결합이다. In one embodiment of the present specification, L5 is a direct bond.
또 하나의 실시상태에 있어서, 상기 L6는 직접결합이다. In another embodiment, L6 is a direct bond.
또 하나의 실시상태에 있어서, 상기 L7은 직접결합이다. In another embodiment, L7 is a direct bond.
본 명세서의 일 실시상태에 있어서, 상기 R10 내지 R20은 수소이다.In one embodiment of the present specification, R10 to R20 are hydrogen.
본 명세서의 일 실시상태에 있어서, 상기 R16은 할로겐기이다.In one embodiment of the present specification, R16 is a halogen group.
또 하나의 실시상태에 있어서, 상기 R16은 불소이다.In another exemplary embodiment, R16 is fluorine.
또한, 본 명세서의 일 실시상태에 있어서, 상기 화학식 6으로 표시되는 브랜처는 하기 구조 중 어느 하나로 표시될 수 있다. In addition, in one embodiment of the present specification, the brancher represented by Chemical Formula 6 may be represented by any one of the following structures.
Figure PCTKR2016010582-appb-I000107
Figure PCTKR2016010582-appb-I000107
본 명세서의 일 실시상태에 있어서, 상기 중합체의 중량평균분자량은500 g/mol 내지 5,000,000 g/mol 이다. 본 명세서의 또 하나의 실시상태에 있어서, 상기 중합체의 중량평균 분자량은 10,000 g/mol 내지 3,000,000 g/mol이다. 상기 중합체의 중량평균 분자량이 상기의 범위인 경우에는 상기 중합체를 포함하는 전해질막의 기계적인 물성이 저하되지 않으며, 적절한 고분자의 용해도를 유지하여, 전해질막의 제조가 용이할 수 있다.In one embodiment of the present specification, the weight average molecular weight of the polymer is 500 g / mol to 5,000,000 g / mol. In another embodiment of the present specification, the weight average molecular weight of the polymer is 10,000 g / mol to 3,000,000 g / mol. When the weight average molecular weight of the polymer is in the above range, the mechanical properties of the electrolyte membrane including the polymer are not lowered, and the solubility of the polymer may be maintained to facilitate the preparation of the electrolyte membrane.
또한, 본 명세서는 전술한 블록 중합체를 포함하는 고분자 전해질막을 제공한다. In addition, the present disclosure provides a polymer electrolyte membrane including the block polymer described above.
본 명세서의 일 실시상태에 따른 상기 화학식 1을 표시하는 단위를 포함하는 블록 중합체를 포함하는 경우에는 높은 기계적 강도와 높은 이온 전도도를 갖으며, 전해질막의 상분리 현상을 용이하게 할 수 있다. In the case of including a block polymer including a unit represented by Formula 1 according to an exemplary embodiment of the present specification, it has high mechanical strength and high ionic conductivity, and may facilitate phase separation of the electrolyte membrane.
본 명세서에서 "전해질막"은 이온을 교환할 수 있는 막으로서, 막, 이온교환막, 이온전달막, 이온 전도성 막, 분리막, 이온교환 분리막, 이온전달 분리막, 이온 전도성 분리막, 이온 교환 전해질막, 이온전달 전해질막 또는 이온 전도성 전해질막 등을 포함한다.In the present specification, "electrolyte membrane" is a membrane capable of exchanging ions, such as membrane, ion exchange membrane, ion transfer membrane, ion conductive membrane, separator, ion exchange membrane, ion transfer membrane, ion conductive separator, ion exchange electrolyte membrane, ion And a transfer electrolyte membrane or an ion conductive electrolyte membrane.
본 명세서의 일 실시상태에 따른 고분자 전해질막은 상기 화학식 1로 표시되는 단위를 포함하는 친수성 블록; 및 적어도 하나의 양이온성 측쇄를 포함하는 소수성 블록을 포함하는 블록 중합체를 포함하는 것을 제외하고, 당 기술분야에 알려진 재료 및/또는 방법을 이용하여 제조될 수 있다. A polymer electrolyte membrane according to one embodiment of the present specification includes a hydrophilic block including a unit represented by Chemical Formula 1; And block polymers including hydrophobic blocks comprising at least one cationic side chain, using materials and / or methods known in the art.
본 명세서의 일 실시상태에 따르면, 상기 고분자 전해질막의 이온 전도도는 0.01 S/cm 이상 0.5 S/cm 이하이다. 또 하나의 실시상태에 있어서, 상기 고분자 전해질막의 이온 전도도는 0.01 S/cm 이상 0.3 S/cm 이하이다.According to an exemplary embodiment of the present specification, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less. In another exemplary embodiment, the ion conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.3 S / cm or less.
본 명세서의 일 실시상태에 있어서, 상기 고분자 전해질막의 이온 전도도는 가습 조건에서 측정될 수 있다. 본 명세서에서 가습 조건이란 상대 습도(RH) 10% 내지 100%를 의미할 수 있다. In one embodiment of the present specification, the ionic conductivity of the polymer electrolyte membrane may be measured under humidification conditions. In this specification, the humidification condition may mean 10% to 100% relative humidity (RH).
또한, 본 명세서의 일 실시상태에 있어서, 상기 고분자 전해질막의 이온교환용량(IEC) 값은 0.01 mmol/g 내지 5 mmol/g이다. 상기 이온교환용량값의 범위를 갖는 경우에는 상기 고분자 전해질막에서의 이온 채널이 형성되고, 중합체가 이온 전도도를 나타낼 수 있다. In addition, in one embodiment of the present specification, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g. When the ion exchange capacity is in the range, an ion channel in the polymer electrolyte membrane is formed, and the polymer may exhibit ion conductivity.
본 명세서의 일 실시상태에 있어서, 상기 고분자 전해질막의 두께는 1 ㎛ 내지 500 ㎛이다. 상기 범위 두께의 고분자 전해질막은 전기적 쇼트(Electric Short) 및 전해질 물질의 크로스오버(Cross Over)를 저하시키고, 우수한 양이온 전도도 특성을 나타낼 수 있다.In one embodiment of the present specification, the thickness of the polymer electrolyte membrane is 1 μm to 500 μm. The polymer electrolyte membrane having the above range thickness lowers an electrical short and a cross over of an electrolyte material, and may exhibit excellent cation conductivity characteristics.
본 명세서는 또한, 애노드; 캐소드; 및 상기 애노드와 상기 캐소드 사이에 구비된 전술한 고분자 전해질막을 포함하는 막-전극 접합체를 제공한다. The present specification also relates to an anode; Cathode; And it provides a membrane-electrode assembly comprising the above-described polymer electrolyte membrane provided between the anode and the cathode.
막-전극 접합체(MEA)는 연료와 공기의 전기화학 촉매 반응이 일어나는 전극(캐소드와 애노드)과 수소 이온의 전달이 일어나는 고분자 막의 접합체를 의미하는 것으로서, 전극(캐소드와 애노드)과 전해질막이 접착된 단일의 일체형 유니트(unit)이다.Membrane-electrode assembly (MEA) is an electrode (cathode and anode) in which the electrochemical catalysis of fuel and air occurs and a polymer membrane in which hydrogen ions are transferred. The electrode (cathode and anode) and the electrolyte membrane are bonded together. It is a single unitary unit.
본 명세서의 상기 막-전극 접합체는 애노드의 촉매층과 캐소드의 촉매층이 전해질막에 접촉하도록 하는 형태로서, 당 분야에 알려진 통상적인 방법에 따라 제조될 수 있다. 일례로, 상기 캐소드; 애노드; 및 상기 캐소드와 애노드 사이에 위치하는 전해질막을 밀착시킨 상태에서 100 내지 400℃로 열압착하여 제조될 수 있다.The membrane-electrode assembly of the present specification is a form in which the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane, and may be prepared according to conventional methods known in the art. In one example, the cathode; Anode; And it may be prepared by thermal compression at 100 to 400 ℃ in the state in which the electrolyte membrane located between the cathode and the anode in close contact.
애노드 전극은 애노드 촉매층과 애노드 기체확산층을 포함할 수 있다. 애노드 기체확산층은 다시 애노드 미세 기공층과 애노드 전극 기재를 포함할 수 있다. 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.
캐소드 전극은 캐소드 촉매층과 캐소드 기체확산층을 포함할 수 있다. 캐소드 기체확산층은 다시 캐소드 미세 기공층과 캐소드 전극 기재를 포함할 수 있다.The cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may further include a cathode microporous layer and a cathode electrode substrate.
도 1은 연료전지의 전기 발생 원리를 개략적으로 도시한 것으로, 연료전지에 있어서, 전기를 발생시키는 가장 기본적인 단위는 막 전극 접합체(MEA)인데, 이는 전해질막(100)과 이 전해질막(100)의 양면에 형성되는 애노드(200a) 및 캐소드(200b) 전극으로 구성된다. 연료전지의 전기 발생 원리를 나타낸 도 1을 참조하면, 애노드(200a)에서는 수소 또는 메탄올, 부탄과 같은 탄화수소 등의 연료의 산화 반응이 일어나 수소 이온(H+) 및 전자(e-)가 발생하고, 수소 이온은 전해질막(100)을 통해 캐소드(200b)로 이동한다. 캐소드(200b)에서는 전해질막(100)을 통해 전달된 수소 이온과, 산소와 같은 산화제 및 전자가 반응하여 물이 생성된다. 이러한 반응에 의해 외부회로에 전자의 이동이 발생하게 된다.FIG. 1 schematically illustrates the principle of electricity generation of a fuel cell. In the fuel cell, the most basic unit for generating electricity is a membrane electrode assembly (MEA), which is an electrolyte membrane 100 and the electrolyte membrane 100. It consists of an anode (200a) and a cathode (200b) electrode formed on both sides of the. Referring to FIG. 1, which illustrates a principle of electricity generation of a fuel cell, an anode 200a generates an oxidation reaction of a fuel such as hydrogen or a hydrocarbon such as methanol and butane to generate hydrogen ions (H +) and electrons (e−). Hydrogen ions move to the cathode 200b through the electrolyte membrane 100. In the cathode 200b, water is generated by reacting hydrogen ions transferred through the electrolyte membrane 100 with an oxidant such as oxygen and electrons. This reaction causes the movement of electrons in the external circuit.
상기 애노드 전극의 촉매층은 연료의 산화 반응이 일어나는 곳으로, 백금, 루테늄, 오스뮴, 백금-루테늄 합금, 백금-오스뮴 합금, 백금-팔라듐 합금 및 백금-전이금속 합금으로 이루어진 군에서 선택되는 촉매가 바람직하게 사용될 수 있다. 상기 캐소드 전극의 촉매층은 산화제의 환원 반응이 일어나는 곳으로, 백금 또는 백금-전이금속 합금이 촉매로 바람직하게 사용될 수 있다. 상기 촉매들은 그 자체로 사용될 수 있을 뿐만 아니라 탄소계 담체에 담지되어 사용될 수 있다.The catalyst layer of the anode electrode is where the oxidation reaction of the fuel occurs, the catalyst is selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum-transition metal alloy. Can be used. The catalyst layer of the cathode electrode is where the reduction reaction of the oxidant occurs, platinum or platinum-transition metal alloy may be preferably used as a catalyst. The catalysts can be used on their own as well as supported on a carbon-based carrier.
촉매층을 도입하는 과정은 당해 기술 분야에 알려져 있는 통상적인 방법으로 수행할 수 있는데, 예를 들면 촉매 잉크를 전해질막에 직접적으로 코팅하거나 기체확산층에 코팅하여 촉매층을 형성할 수 있다. 이때 촉매 잉크의 코팅 방법은 특별하게 제한되는 것은 아니지만, 스프레이 코팅, 테이프 캐스팅, 스크린 프린팅, 블레이드 코팅, 다이 코팅 또는 스핀 코팅 방법 등을 사용할 수 있다. 촉매 잉크는 대표적으로 촉매, 폴리머 이오노머(polymer ionomer) 및 용매로 이루어질 수 있다.The introduction of the catalyst layer may be carried out by conventional methods 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. 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. Catalytic inks can typically consist of a catalyst, a polymer ionomer, and a solvent.
상기 기체확산층은 전류전도체로서의 역할과 함께 반응 가스와 물의 이동 통로가 되는 것으로, 다공성의 구조를 가진다. 따라서, 상기 기체확산층은 도전성 기재를 포함하여 이루어질 수 있다. 도전성 기재로는 탄소 페이퍼(Carbon paper), 탄소 천(Carbon cloth) 또는 탄소 펠트(Carbon felt)가 바람직하게 사용될 수 있다. 상기 기체확산층은 촉매층 및 도전성 기재 사이에 미세기공층을 더 포함하여 이루어질 수 있다. 상기 미세기공층은 저가습 조건에서의 연료전지의 성능을 향상시키기 위하여 사용될 수 있으며, 기체확산층 밖으로 빠져나가는 물의 양을 적게 하여 전해질막이 충분한 습윤 상태에 있도록 하는 역할을 한다.The gas diffusion layer serves as a passage for the reaction gas and water together with a role as a current conductor, 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 may be used to improve the performance of the fuel cell in low-humidity conditions, and serves to reduce the amount of water flowing out of the gas diffusion layer so that the electrolyte membrane is in a sufficient wet state.
본 명세서의 일 실시상태는 2 이상의 막-전극 접합체; 상기 막-전극 접합체들 사이에 구비되는 바이폴라 플레이트를 포함하는 스택; 상기 스택으로 연료를 공급하는 연료공급부; 및 상기 스택으로 산화제를 공급하는 산화제공급부를 포함하는 고분자 전해질형 연료전지를 제공한다. One embodiment of the present specification includes two or more membrane-electrode assemblies; A stack comprising a bipolar plate provided between the membrane-electrode assemblies; A fuel supply unit supplying fuel to the stack; And it provides a polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
연료전지는 연료의 화학적 에너지를 직접 전기적 에너지로 변환시키는 에너지 변환 장치이다. 즉 연료전지는 연료가스와 산화제를 사용하고, 이들의 산화환원 반응 중에 발생하는 전자를 이용하여 전력을 생산하는 발전 방식이다. A fuel cell is an energy conversion device that converts chemical energy of a fuel directly into electrical energy. In other words, a fuel cell is a power generation method that uses fuel gas and an oxidant and generates electric power by using electrons generated during the redox reaction.
연료전지는 전술한 막-전극 접합체(MEA)를 사용하여 당 분야에 알려진 통상적인 방법에 따라 제조될 수 있다. 예를 들면, 상기에서 제조된 막전극 접합체(MEA)와 바이폴라 플레이트(bipolar plate)로 구성하여 제조될 수 있다.The fuel cell can be manufactured according to conventional methods known in the art using the membrane-electrode assembly (MEA) described above. For example, it may be prepared by configuring a membrane electrode assembly (MEA) and a bipolar plate (bipolar plate) prepared above.
본 명세서의 연료전지는 스택, 연료공급부 및 산화제공급부를 포함하여 이루어진다.The fuel cell of the present specification includes a stack, a fuel supply unit and an oxidant supply unit.
도 3은 연료전지의 구조를 개략적으로 도시한 것으로, 연료전지는 스택(60), 산화제 공급부(70) 및 연료 공급부(80)를 포함하여 이루어진다.3 schematically illustrates the structure of a fuel cell, in which the fuel cell includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80.
스택(60)은 상술한 막 전극 접합체를 하나 또는 둘 이상 포함하며, 막 전극 접합체가 둘 이상 포함되는 경우에는 이들 사이에 개재되는 세퍼레이터를 포함한다. 세퍼레이터는 막 전극 접합체들이 전기적으로 연결되는 것을 막고 외부에서 공급된 연료 및 산화제를 막 전극 접합체로 전달하는 역할을 한다.The stack 60 includes one or two or more membrane electrode assemblies as described above, and includes two or more separators 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 fuel and oxidant supplied from the outside to the membrane electrode assembly.
산화제 공급부(70)는 산화제를 스택(60)으로 공급하는 역할을 한다. 산화제로는 산소가 대표적으로 사용되며, 산소 또는 공기를 펌프(70)로 주입하여 사용할 수 있다.The oxidant supply unit 70 serves to supply the oxidant to the stack 60. Oxygen is typically used as the oxidizing agent, and may be used by injecting oxygen or air into the pump 70.
연료 공급부(80)는 연료를 스택(60)으로 공급하는 역할을 하며, 연료를 저장하는 연료탱크(81) 및 연료 탱크(81)에 저장된 연료를 스택(60)으로 공급하는 펌프(82)로 구성될 수 있다. 연료로는 기체 또는 액체 상태의 수소 또는 탄화수소 연료가 사용될 수 있다. 탄화수소 연료의 예로는 메탄올, 에탄올, 프로판올, 부탄올 또는 천연가스를 들 수 있다.The fuel supply unit 80 serves to supply fuel to the stack 60, and to the fuel tank 81 storing fuel and the pump 82 supplying fuel stored in the fuel tank 81 to the stack 60. Can be configured. As fuel, hydrogen or hydrocarbon fuel in gas or liquid state may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.
상기 연료전지는 고분자 전해질 연료전지, 직접 액체 연료전지, 직접 메탄올 연료전지, 직접 개미산 연료전지, 직접 에탄올 연료전지, 또는 직접 디메틸에테르 연료전지 등이 가능하다.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.
본 명세서의 일 실시상태에 따른 전해질막을 연료전지의 이온교환막으로 사용하였을 때 전술한 효과를 나타낼 수 있다.When the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a fuel cell, the above-described effects can be obtained.
또한, 본 명세서의 일 실시상태는 양극 및 양극 전해액을 포함하는 양극 셀; 음극 및 음극 전해액을 포함하는 음극 셀; 및 상기 양극 셀과 상기 음극 셀 사이에 구비되는 본 명세서의 일 실시상태에 따른 고분자 전해질막을 포함하는 레독스 플로우 전지를 제공한다.In addition, an exemplary embodiment of the present specification includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A cathode cell comprising a cathode and a cathode electrolyte; And it provides a redox flow battery comprising a polymer electrolyte membrane according to one embodiment of the present specification provided between the cathode cell and the anode cell.
레독스 플로우 전지(산화-환원 흐름 전지, Redox Flow Battery)는 전해액에 포함되어 있는 활성물질이 산화·환원되어 충전·방전되는 시스템으로 활성물질의 화학적 에너지를 직접 전기에너지로 저장시키는 전기화학적 축전 장치이다. 레독스 플로우 전지는 산화상태가 다른 활성물질을 포함하는 전해액이 이온교환막을 사이에 두고 만날 때 전자를 주고받아 충전과 방전이 되는 원리를 이용한다. 일반적으로 레독스 플로우 전지는 전해액이 담겨있는 탱크와 충전과 방전이 일어나는 전지 셀, 그리고 전해액을 탱크와 전지 셀 사이에 순환시키기 위한 순환펌프로 구성되고, 전지 셀의 단위셀은 전극, 전해질 및 이온교환막을 포함한다.The redox flow battery (redox flow battery) is an electrochemical storage device that stores the chemical energy of an active material directly as electrical energy. It is a system in which the active material contained in the electrolyte is oxidized, reduced, and charged and discharged. to be. The redox flow battery uses a principle that charges and discharges are exchanged when electrons containing active materials having different oxidation states meet with an ion exchange membrane interposed therebetween. In general, a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occurs, and a circulation pump for circulating the electrolyte solution between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, an electrolyte, and an ion. Exchange membrane.
본 명세서의 일 실시상태에 따른 전해질막을 레독스 플로우 전지의 이온교환막으로 사용하였을 때 전술한 효과를 나타낼 수 있다.When the electrolyte membrane according to one embodiment of the present specification is used as an ion exchange membrane of a redox flow battery, the above-described effects may be exhibited.
본 명세서의 레독스 플로우 전지는 본 명세서의 일 실시상태에 따른 고분자 전해질막을 포함하는 것을 제외하고는, 당 분야에 알려진 통상적인 방법에 따라 제조될 수 있다.The redox flow battery of the present specification may be manufactured according to conventional methods known in the art, except for including the polymer electrolyte membrane according to one embodiment of the present specification.
도 2에 도시한 바와 같이, 레독스 플로우 전지는 전해질막(31)에 의해 양극 셀(32)과 음극 셀(33)로 나뉘어진다. 양극 셀(32)과 음극 셀(33)은 각각 양극과 음극을 포함한다. 양극 셀(32)은 파이프를 통해 양극 전해액(41)을 공급 및 방출하기 위한 양극 탱크(10)에 연결되어 있다. 음극 셀(33) 또한, 파이프를 통해 음극 전해액(42)을 공급 및 방출하기 위한 음극 탱크(20)에 연결되어 있다. 전해액은 펌프(11, 21)를 통해 순환되고, 이온의 산화수가 변화되는 산화/환원 반응(즉, 레독스 반응)이 일어남으로써 양극과 음극에서 충전 및 방전이 일어난다. As shown in FIG. 2, the redox flow battery is divided into the positive electrode cell 32 and the negative electrode cell 33 by the electrolyte membrane 31. The anode cell 32 and the cathode cell 33 include an anode and a cathode, respectively. The anode cell 32 is connected to the anode tank 10 for supplying and discharging the anode electrolyte 41 through a pipe. The cathode cell 33 is also connected to the cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe. The electrolyte is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions changes occurs, thereby causing charge and discharge at the anode and the cathode.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 명세서의 범위가 아래에서 기술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
<제조예><Production example>
제조예 1. 화합물 A의 합성Preparation Example 1 Synthesis of Compound A
Figure PCTKR2016010582-appb-I000108
Figure PCTKR2016010582-appb-I000108
1-플루오로-4-((4-플루오로페닐)술포닐)-2-메틸벤젠 [1-fluoro-4-((4-fluorophenyl)sulfonyl)-2-methylbenzene] 200g (0.75 mol)을 클로로포름 1500 ml에 녹이고 벤조일 퍼옥사이드 (Benzoyl peroxide) 18.1g (74.5mmol)을 첨가 하였다. N-bromosuccinimide 398g (2.24mol)을 천천히 적가한 후 반응물을 65 oC로 승온하고 같은 온도에서 5시간 교반하였다. 반응 종결 후 반응물을 실온으로 냉각하고 에틸아세테이트로 묽힌 후 포화 NaHCO3 수용액을 이용해 수 차례 세척하고 하였다. 이렇게 얻은 유기층을 황산마그네슘(MgSO4)로 건조하고 증류하여 crude 상태의 화합물 A[2-(브로모메틸)-1-플루오로-4-((4-플루오로페닐)술포닐)벤젠]을 얻었다. 이렇게 얻은 crude 화합물을 추가적인 분리 정제 과정없이 다음 반응에 사용하였다.1-fluoro-4-((4-fluorophenyl) sulfonyl) -2-methylbenzene 200 g (0.75 mol) of [1-fluoro-4-((4-fluorophenyl) sulfonyl) -2-methylbenzene] It was dissolved in 1500 ml and 18.1 g (74.5 mmol) of benzoyl peroxide was added. 398 g (2.24 mol) of N-bromosuccinimide was slowly added dropwise, and the reaction was then heated to 65 ° C. and stirred at the same temperature for 5 hours. After completion of the reaction, the reaction was cooled to room temperature, diluted with ethyl acetate, and washed several times with saturated aqueous NaHCO 3 solution. The organic layer thus obtained was dried over magnesium sulfate (MgSO 4 ) and distilled to obtain crude Compound A [2- (bromomethyl) -1-fluoro-4-((4-fluorophenyl) sulfonyl) benzene] in a crude state. Got it. The crude compound thus obtained was used in the next reaction without further separation and purification.
제조예 2. 화합물 B의 합성Preparation Example 2 Synthesis of Compound B
Figure PCTKR2016010582-appb-I000109
Figure PCTKR2016010582-appb-I000109
제조예 1에서 얻은 화합물 A [2-(bromomethyl)-1-fluoro-4-((4-fluorophenyl)sulfonyl)benzene]을 THF 1500ml에 녹인 후 반응물을 0 ℃로 냉각하고, 다이메틸아민(Dimehtylamine 40wt% in H2O) 420g (3.73mol)을 천천히 적가하였다. 반응물의 온도를 실온으로 승온한 후 실온에서 4시간 교반하였다. 용매를 감압 증류로 제거하고, 에틸아세테이드로 묽힌 후 1N HCl를 적가하였다. 이렇게 얻은 물층을 에틸아세테이트로 수 차례 세척하여 불순물을 제거하고, 산성인 물층을 감압 증류를 통해 HCl salt form의 고체 화합물을 얻었다. 이렇게 얻은 고체 화합물을 메틸렌클로라이드를 넣고 슬러리 상태로 실온에서 교반한 후 여과하고 N2 gas하에서 건조하여 고순도의 최종화합물 화합물 B[1-(2-fluoro-5-((4-fluorophenyl)sulfonyl)phenyl)-N,N-dimethylmethanamine hydrochloride]를 42% 수율(2 step yield)로 얻을 수 있었다. 화합물 B의 H-NMR 스펙트럼을 도 4에 나타냈다.Compound A [2- (bromomethyl) -1-fluoro-4-((4-fluorophenyl) sulfonyl) benzene] obtained in Preparation Example 1 was dissolved in 1500 ml of THF, and the reaction mixture was cooled to 0 ° C., and dimethylamine (40 wt% Dimethhtylamine) was used. 420 g (3.73 mol)% in H 2 O) was slowly added dropwise. The temperature of the reaction was raised to room temperature and stirred for 4 hours at room temperature. The solvent was removed by distillation under reduced pressure, diluted with ethyl acetate and 1N HCl was added dropwise. The water layer thus obtained was washed several times with ethyl acetate to remove impurities, and the acidic water layer was distilled under reduced pressure to obtain a solid compound of HCl salt form. The solid compound thus obtained was added with methylene chloride, stirred at room temperature in a slurry state, filtered, and dried under N 2 gas to obtain a high purity final compound Compound B [1- (2-fluoro-5-((4-fluorophenyl) sulfonyl) phenyl ) -N, N-dimethylmethanamine hydrochloride] was obtained in 42% yield (2 step yield). H-NMR spectrum of Compound B is shown in FIG. 4.
제조예Production Example 3. 중간체 1의 합성 3. Synthesis of Intermediate 1
Figure PCTKR2016010582-appb-I000110
Figure PCTKR2016010582-appb-I000110
상기 각각의 모노머 및 탄산칼륨 (K2CO3: 몰 비 4)를 NMP 30 wt % 비율과 벤젠 20 wt % 비율로 혼합하여, 140 ℃에서 4시간, 180 ℃에서 16시간 중합하여 상기 중합체를 제조하였다. 상기 중합체의 H-NMR은 도 5에 나타냈으며, DMAC에 중합체 1을 녹인 후 CDCl3 용매에서 H-NMR 실험을 진행 하였다.Each of the monomers and potassium carbonate (K 2 CO 3 : molar ratio 4) were mixed in an NMP 30 wt% ratio and a benzene 20 wt% ratio, and polymerized at 140 ° C. for 4 hours and at 180 ° C. for 16 hours to prepare the polymer. It was. H-NMR of the polymer is shown in Figure 5, after dissolving Polymer 1 in DMAC was carried out H-NMR experiment in CDCl 3 solvent.
제조예 4, 중간체 2의 합성Preparation Example 4, Synthesis of Intermediate 2
Figure PCTKR2016010582-appb-I000111
Figure PCTKR2016010582-appb-I000111
제조예 3에서 합성한 중합체에 각각의 모노머 및 탄산칼륨 (K2CO3: 몰 비 4)를 NMP 30 wt % 비율과 벤젠 20 wt % 비율로 혼합하여, 140 ℃에서 4시간, 180 ℃에서 16시간 중합하여 상기 중간체 2를 제조하였다.Each monomer and potassium carbonate (K 2 CO 3: molar ratio 4) were mixed with the polymer synthesized in Preparation Example 3 in an NMP 30 wt% ratio and a benzene 20 wt% ratio, followed by polymerization at 140 ° C. for 4 hours and 180 ° C. for 16 hours. Intermediate 2 was prepared.
제조예 5. 화합물 1의 합성Preparation Example 5 Synthesis of Compound 1
제조예 4에서 얻은 중간체 2를 5 wt%의 농도로 DMAC에 녹인 후 메틸아이오다이드(methyliodide) 5eq를 첨가하여 실온에서 6시간 반응하여 하기의 화합물 1을 최종적으로 제조하였다.Intermediate 2 obtained in Preparation Example 4 was dissolved in DMAC at a concentration of 5 wt%, methyliodide 5eq was added thereto, and reacted at room temperature for 6 hours to finally prepare Compound 1 below.
[화합물 1][Compound 1]
Figure PCTKR2016010582-appb-I000112
Figure PCTKR2016010582-appb-I000112
<실시예 / 비교예><Example / Comparative Example>
실시예 1. Example 1.
화합물 1을 이용한 전해질막의 바나듐 투과도(vanadium permeability)를 측정하여 하기 표 1에 나타내었다.The vanadium permeability of the electrolyte membrane using the compound 1 was measured and shown in Table 1 below.
비교예 1. Comparative Example 1.
Nafion 115를 이용한 전해질막의 바나듐 투과도(vanadium permeability)를 측정하여 하기 표 1에 나타내었다.The vanadium permeability of the electrolyte membrane using Nafion 115 was measured and shown in Table 1 below.
VO2+ 투과도 (cm2/min)x10-6 VO 2+ transmittance (cm 2 / min) x10 -6
실시예 1Example 1 0.50.5
비교예 1Comparative Example 1 5.845.84
상기의 바나듐 이온 투과도는 한쪽에 1M VOSO4 in 2M H2SO4 용액을 충전하고 다른 한쪽에 1M MgSO4 in 2M H2SO4 용액을 충전한 후, 두 용액사이에 전해질막을 설치하여 시간에 따른 1M MgSO4 in 2M H2SO4 용액에서의 VO2+ 농도를 측정한 값이다.The vanadium ion permeability is 1M VOSO 4 in 2M H 2 SO 4 solution on one side and 1M MgSO 4 in 2M H 2 SO 4 solution on the other side, the electrolyte membrane is installed between the two solutions over time VO 2+ concentration in 1M MgSO 4 in 2M H 2 SO 4 solution was measured.
활성 영역(Active area)은 7.69cm2, 부피(volume)는 200ml, 상온에서 측정하였다.The active area was measured at 7.69 cm 2 , the volume was 200 ml, and room temperature.
화합물 1을 포함하는 전해질막의 경우, Nafion 115 전해질막에 비하여 전해질막 주쇄에 양이온성 작용기가 존재 함으로 인하여 바나듐 이온의 투과도가 기존 Nafion 전해질막에 비해 크게 떨어지는 것을 알 수 있다. 이와 같은 결과로 바나듐 이온의 크로스오버(crossover)를 효과적으로 억제 할 수 있어 본원 발명의 일 실시상태에 따른 공중합체를 포함하는 전해질막의 성능이 우수한 것을 예측할 수 있다.In the case of the electrolyte membrane including the compound 1, it can be seen that the permeability of vanadium ions is significantly lower than that of the conventional Nafion electrolyte membrane due to the presence of cationic functional groups in the electrolyte membrane main chain as compared to the Nafion 115 electrolyte membrane. As a result, it is possible to effectively suppress the crossover of vanadium ions, thereby predicting the excellent performance of the electrolyte membrane including the copolymer according to the exemplary embodiment of the present invention.
따라서, 본 명세서에 따른 전해질막을 이용하여 연료전지 또는 레독스 플로우 전지를 제조하였을 때, 전지의 효율을 높일 수 있다.Therefore, when the fuel cell or the redox flow battery is manufactured using the electrolyte membrane according to the present specification, the efficiency of the battery can be improved.

Claims (19)

  1. 소수성 블록; 및 Hydrophobic blocks; And
    친수성 블록을 포함하고, Contains a hydrophilic block,
    상기 소수성 블록은 적어도 하나의 양이온성 측쇄를 포함하며, The hydrophobic block comprises at least one cationic side chain,
    상기 친수성 블록은 하기 화학식 1로 표시되는 화합물로부터 유래된 단위를 포함하는 것인 블록 중합체: The hydrophilic block is a block polymer comprising a unit derived from a compound represented by the following formula (1):
    [화학식 1][Formula 1]
    Figure PCTKR2016010582-appb-I000113
    Figure PCTKR2016010582-appb-I000113
    화학식 1에 있어서, In Chemical Formula 1,
    A는 -SO3H, -SO3 -M+, -COOH, -COO-M+, -PO3H2, -PO3H-M+, -PO3 2-2M+, -O(CF2)mSO3H, -O(CF2)mSO3 -M+, -O(CF2)mCOOH, -O(CF2)mCOO-M+, -O(CF2)mPO3H2, -O(CF2)mPO3H-M+ 또는 -O(CF2)mPO3 2-2M+이고,A 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 ) m SO 3 H, -O (CF 2 ) m SO 3 - M + , -O (CF 2 ) m COOH, -O (CF 2 ) m COO - M + , -O (CF 2 ) m PO 3 H 2, -O (CF 2) m PO 3 H - M + , or -O (CF 2) m PO 3 2- 2M + , and
    m은 2 내지 6의 정수이며, m is an integer from 2 to 6,
    M은 1족 원소이고,M is a group 1 element,
    R1 내지 R5는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 할로겐기; 또는 히드록시기이며, R1 to R5 are the same as or different from each other, and each independently hydrogen; Halogen group; Or a hydroxyl group,
    R1 내지 R5 중 적어도 두 개는 할로겐기; 또는 히드록시기이고, At least two of R1 to R5 are halogen groups; Or a hydroxyl group,
    R6 및 R7은 서로 동일하거나 상이하고, 각각 독립적으로 할로겐기이며,R6 and R7 are the same as or different from each other, and each independently a halogen group,
    La는 직접결합; S; O; NRa; SO2; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, La is a direct bond; S; O; NRa; SO 2 ; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
    Ra는 수소; 또는 치환 또는 비치환된 알킬기이며, Ra is hydrogen; Or a substituted or unsubstituted alkyl group,
    n은 2 내지 10의 정수이며, 2 내지 10 개의 괄호 내의 구조는 서로 동일하거나 상이하다. n is an integer from 2 to 10, and the structures in the 2 to 10 parentheses are the same or different from each other.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 소수성 블록은 주쇄에 -(C=O)-; 또는 -(SO2)- 를 포함하는 것인 블록 중합체. The hydrophobic block comprises:-(C═O) — in the main chain; Or-(SO 2 )-.
  3. 청구항 1에 있어서, The method according to claim 1,
    상기 양이온성 측쇄는 -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이고, The cationic side chain is-(L) oN + RR'R ";-(L) oP + RR'R"; Or in the following Chemical Formula 1-A,
    [화학식 1-A] [Formula 1-A]
    Figure PCTKR2016010582-appb-I000114
    Figure PCTKR2016010582-appb-I000114
    L은 직접결합; O; NR"'; S; SO2; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이며, L is a direct bond; O; NR ″ ′; S; SO 2 ; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
    o는 1 내지 10의 정수이고, o is an integer from 1 to 10,
    o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하며, when o is 2 or more, two or more L are the same as or different from each other,
    R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기인 블록 중합체.R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 소수성 블록은 하기 화학식 2 또는 화학식 3으로 표시되는 단위를 포함하는 것인 블록 중합체: The hydrophobic block is a block polymer comprising a unit represented by the following formula (2) or (3):
    [화학식 2][Formula 2]
    Figure PCTKR2016010582-appb-I000115
    Figure PCTKR2016010582-appb-I000115
    [화학식 3][Formula 3]
    Figure PCTKR2016010582-appb-I000116
    Figure PCTKR2016010582-appb-I000116
    화학식 2 및 화학식 3에 있어서, In Chemical Formula 2 and Chemical Formula 3,
    S1 내지 S4는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이고, S1 to S4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or in the following Chemical Formula 1-A,
    [화학식 1-A] [Formula 1-A]
    Figure PCTKR2016010582-appb-I000117
    Figure PCTKR2016010582-appb-I000117
    L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이며, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
    o는 1 내지 10의 정수이고, o is an integer from 1 to 10,
    o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하며, when o is 2 or more, two or more L are the same as or different from each other,
    R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이고, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
    a, a', b 및 b'는 각각 1 내지 4의 정수이며, a, a ', b and b' are each an integer of 1 to 4,
    a, a', b 및 b'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When a, a ', b and b' are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
  5. 청구항 1에 있어서, The method according to claim 1,
    상기 소수성 블록 또는 친수성 블록은 하기 화학식 4로 표시되는 화합물로부터 유래되는 단위를 더 포함하는 것인 블록 중합체: Wherein the hydrophobic block or hydrophilic block further comprises a unit derived from a compound represented by Formula 4 below:
    [화학식 4][Formula 4]
    Figure PCTKR2016010582-appb-I000118
    Figure PCTKR2016010582-appb-I000118
    화학식 4에 있어서, In Chemical Formula 4,
    E1 및 E2는 히드록시기 또는 티올기이고, E1 and E2 are hydroxy or thiol groups,
    S5는 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이며, S5 is hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
    [화학식 1-A] [Formula 1-A]
    Figure PCTKR2016010582-appb-I000119
    Figure PCTKR2016010582-appb-I000119
    L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
    o는 1 내지 10의 정수이며, o is an integer from 1 to 10,
    o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하고, when o is 2 or more, two or more L are the same as or different from each other,
    R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이며, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
    c는 1 내지 4의 정수이고, c is an integer from 1 to 4,
    c'는 1 내지 3의 정수이며, c 'is an integer of 1 to 3,
    c 및 c'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When c and c 'are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
  6. 청구항 1에 있어서, The method according to claim 1,
    상기 소수성 블록은 하기 화학식 2 또는 화학식 3으로 표시되는 단위; 및 The hydrophobic block is a unit represented by the following formula (2) or formula (3); And
    하기 화학식 4로 표시되는 화합물로부터 유래되는 단위를 포함하는 것인 블록 중합체: A block polymer comprising units derived from a compound represented by the following formula (4):
    [화학식 2][Formula 2]
    Figure PCTKR2016010582-appb-I000120
    Figure PCTKR2016010582-appb-I000120
    [화학식 3][Formula 3]
    Figure PCTKR2016010582-appb-I000121
    Figure PCTKR2016010582-appb-I000121
    [화학식 4][Formula 4]
    Figure PCTKR2016010582-appb-I000122
    Figure PCTKR2016010582-appb-I000122
    화학식 2 내지 4에 있어서, In Chemical Formulas 2 to 4,
    E1 및 E2는 히드록시기 또는 티올기이고, E1 and E2 are hydroxy or thiol groups,
    S1 내지 S5는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 중수소; 할로겐기; 시아노기; 니트릴기; 니트로기; 히드록시기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 시클로알킬기; 치환 또는 비치환된 알콕시기; 치환 또는 비치환된 알케닐기; 치환 또는 비치환된 실릴기; 치환 또는 비치환된 아릴기; 치환 또는 비치환된 헤테로고리기; -(L)o-N+RR'R"; -(L)o-P+RR'R"; 또는 하기 화학식 1-A이며, S1 to S5 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitrile group; Nitro group; Hydroxyl group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; -(L) oN + RR'R ";-(L) oP + RR'R"; Or Formula 1-A
    [화학식 1-A] [Formula 1-A]
    Figure PCTKR2016010582-appb-I000123
    Figure PCTKR2016010582-appb-I000123
    L은 직접결합; O; NR"'; S; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬렌기이고, L is a direct bond; O; NR "'; S; or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
    o는 1 내지 10의 정수이며, o is an integer from 1 to 10,
    o 가 2 이상인 경우, 2 이상의 L은 서로 동일하거나 상이하고, when o is 2 or more, two or more L are the same as or different from each other,
    R, R', R", R'" 및 Rb는 서로 동일하거나 상이하고, 각각 독립적으로 수소; 또는 치환 또는 비치환된 탄소수 1 내지 10의 알킬기이며, R, R ', R ", R'" and Rb are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
    a, a', b, b' 및 c는 각각 1 내지 4의 정수이고,a, a ', b, b' and c are each an integer of 1 to 4,
    c'는 1 내지 3의 정수이며, c 'is an integer of 1 to 3,
    a, a', b, b', c 및 c'가 각각 2 이상의 정수인 경우, 2 이상의 괄호 내의 구조는 서로 동일하거나 상이하다. When a, a ', b, b', c and c 'are each an integer of 2 or more, the structures in the two or more parentheses are the same or different from each other.
  7. 청구항 1에 있어서, The method according to claim 1,
    상기 화학식 1로 표시되는 화합물로부터 유래되는 단위는 하기 화학식 1-1 내지 1-18 중 어느 하나로 표시되는 것인 블록 중합체: The block polymer derived from the compound represented by Formula 1 is represented by any one of the following Formulas 1-1 to 1-18:
    [화학식 1-1][Formula 1-1]
    Figure PCTKR2016010582-appb-I000124
    Figure PCTKR2016010582-appb-I000124
    [화학식 1-2][Formula 1-2]
    Figure PCTKR2016010582-appb-I000125
    Figure PCTKR2016010582-appb-I000125
    [화학식 1-3][Formula 1-3]
    Figure PCTKR2016010582-appb-I000126
    Figure PCTKR2016010582-appb-I000126
    [화학식 1-4][Formula 1-4]
    Figure PCTKR2016010582-appb-I000127
    Figure PCTKR2016010582-appb-I000127
    [화학식 1-5][Formula 1-5]
    Figure PCTKR2016010582-appb-I000128
    Figure PCTKR2016010582-appb-I000128
    [화학식 1-6][Formula 1-6]
    Figure PCTKR2016010582-appb-I000129
    Figure PCTKR2016010582-appb-I000129
    [화학식 1-7][Formula 1-7]
    Figure PCTKR2016010582-appb-I000130
    Figure PCTKR2016010582-appb-I000130
    [화학식 1-8][Formula 1-8]
    Figure PCTKR2016010582-appb-I000131
    Figure PCTKR2016010582-appb-I000131
    [화학식 1-9][Formula 1-9]
    Figure PCTKR2016010582-appb-I000132
    Figure PCTKR2016010582-appb-I000132
    [화학식 1-10][Formula 1-10]
    Figure PCTKR2016010582-appb-I000133
    Figure PCTKR2016010582-appb-I000133
    [화학식 1-11][Formula 1-11]
    Figure PCTKR2016010582-appb-I000134
    Figure PCTKR2016010582-appb-I000134
    [화학식 1-12][Formula 1-12]
    Figure PCTKR2016010582-appb-I000135
    Figure PCTKR2016010582-appb-I000135
    [화학식 1-13][Formula 1-13]
    Figure PCTKR2016010582-appb-I000136
    Figure PCTKR2016010582-appb-I000136
    [화학식 1-14][Formula 1-14]
    Figure PCTKR2016010582-appb-I000137
    Figure PCTKR2016010582-appb-I000137
    [화학식 1-15][Formula 1-15]
    Figure PCTKR2016010582-appb-I000138
    Figure PCTKR2016010582-appb-I000138
    [화학식 1-16][Formula 1-16]
    Figure PCTKR2016010582-appb-I000139
    Figure PCTKR2016010582-appb-I000139
    [화학식 1-17][Formula 1-17]
    Figure PCTKR2016010582-appb-I000140
    Figure PCTKR2016010582-appb-I000140
    [화학식 1-18][Formula 1-18]
    Figure PCTKR2016010582-appb-I000141
    Figure PCTKR2016010582-appb-I000141
  8. 청구항 1에 있어서, The method according to claim 1,
    상기 화학식 1로 표시되는 화합물로부터 유래되는 단위는 하기 화학식 1-19 내지 1-36 중 어느 하나로 표시되는 것인 블록 중합체: The unit derived from the compound represented by Formula 1 is a block polymer represented by any one of the following Formulas 1-19 to 1-36:
    [화학식 1-19][Formula 1-19]
    Figure PCTKR2016010582-appb-I000142
    Figure PCTKR2016010582-appb-I000142
    [화학식 1-20][Formula 1-20]
    Figure PCTKR2016010582-appb-I000143
    Figure PCTKR2016010582-appb-I000143
    [화학식 1-21][Formula 1-21]
    Figure PCTKR2016010582-appb-I000144
    Figure PCTKR2016010582-appb-I000144
    [화학식 1-22][Formula 1-22]
    Figure PCTKR2016010582-appb-I000145
    Figure PCTKR2016010582-appb-I000145
    [화학식 1-23][Formula 1-23]
    Figure PCTKR2016010582-appb-I000146
    Figure PCTKR2016010582-appb-I000146
    [화학식 1-24][Formula 1-24]
    Figure PCTKR2016010582-appb-I000147
    Figure PCTKR2016010582-appb-I000147
    [화학식 1-25][Formula 1-25]
    Figure PCTKR2016010582-appb-I000148
    Figure PCTKR2016010582-appb-I000148
    [화학식 1-26][Formula 1-26]
    Figure PCTKR2016010582-appb-I000149
    Figure PCTKR2016010582-appb-I000149
    [화학식 1-27][Formula 1-27]
    Figure PCTKR2016010582-appb-I000150
    Figure PCTKR2016010582-appb-I000150
    [화학식 1-28][Formula 1-28]
    Figure PCTKR2016010582-appb-I000151
    Figure PCTKR2016010582-appb-I000151
    [화학식 1-29][Formula 1-29]
    Figure PCTKR2016010582-appb-I000152
    Figure PCTKR2016010582-appb-I000152
    [화학식 1-30][Formula 1-30]
    Figure PCTKR2016010582-appb-I000153
    Figure PCTKR2016010582-appb-I000153
    [화학식 1-31][Formula 1-31]
    Figure PCTKR2016010582-appb-I000154
    Figure PCTKR2016010582-appb-I000154
    [화학식 1-32][Formula 1-32]
    Figure PCTKR2016010582-appb-I000155
    Figure PCTKR2016010582-appb-I000155
    [화학식 1-33][Formula 1-33]
    Figure PCTKR2016010582-appb-I000156
    Figure PCTKR2016010582-appb-I000156
    [화학식 1-34][Formula 1-34]
    Figure PCTKR2016010582-appb-I000157
    Figure PCTKR2016010582-appb-I000157
    [화학식 1-35][Formula 1-35]
    Figure PCTKR2016010582-appb-I000158
    Figure PCTKR2016010582-appb-I000158
    [화학식 1-36][Formula 1-36]
    Figure PCTKR2016010582-appb-I000159
    Figure PCTKR2016010582-appb-I000159
  9. 청구항 1에 있어서, The method according to claim 1,
    상기 화학식 1로 표시되는 화합물로부터 유래되는 단위는 하기 화학식 1-37 내지 1-54 중 어느 하나로 표시되는 것인 블록 중합체: The unit derived from the compound represented by Formula 1 is a block polymer represented by any one of the following formulas 1-37 to 1-54:
    [화학식 1-37][Formula 1-37]
    Figure PCTKR2016010582-appb-I000160
    Figure PCTKR2016010582-appb-I000160
    [화학식 1-38][Formula 1-38]
    Figure PCTKR2016010582-appb-I000161
    Figure PCTKR2016010582-appb-I000161
    [화학식 1-39][Formula 1-39]
    Figure PCTKR2016010582-appb-I000162
    Figure PCTKR2016010582-appb-I000162
    [화학식 1-40][Formula 1-40]
    Figure PCTKR2016010582-appb-I000163
    Figure PCTKR2016010582-appb-I000163
    [화학식 1-41][Formula 1-41]
    Figure PCTKR2016010582-appb-I000164
    Figure PCTKR2016010582-appb-I000164
    [화학식 1-42][Formula 1-42]
    Figure PCTKR2016010582-appb-I000165
    Figure PCTKR2016010582-appb-I000165
    [화학식 1-43][Formula 1-43]
    Figure PCTKR2016010582-appb-I000166
    Figure PCTKR2016010582-appb-I000166
    [화학식 1-44][Formula 1-44]
    Figure PCTKR2016010582-appb-I000167
    Figure PCTKR2016010582-appb-I000167
    [화학식 1-45][Formula 1-45]
    [화학식 1-46][Formula 1-46]
    Figure PCTKR2016010582-appb-I000169
    Figure PCTKR2016010582-appb-I000169
    [화학식 1-47][Formula 1-47]
    Figure PCTKR2016010582-appb-I000170
    Figure PCTKR2016010582-appb-I000170
    [화학식 1-48][Formula 1-48]
    Figure PCTKR2016010582-appb-I000171
    Figure PCTKR2016010582-appb-I000171
    [화학식 1-49][Formula 1-49]
    Figure PCTKR2016010582-appb-I000172
    Figure PCTKR2016010582-appb-I000172
    [화학식 1-50][Formula 1-50]
    Figure PCTKR2016010582-appb-I000173
    Figure PCTKR2016010582-appb-I000173
    [화학식 1-51][Formula 1-51]
    Figure PCTKR2016010582-appb-I000174
    Figure PCTKR2016010582-appb-I000174
    [화학식 1-52][Formula 1-52]
    Figure PCTKR2016010582-appb-I000175
    Figure PCTKR2016010582-appb-I000175
    [화학식 1-53][Formula 1-53]
    Figure PCTKR2016010582-appb-I000176
    Figure PCTKR2016010582-appb-I000176
    [화학식 1-54][Formula 1-54]
    Figure PCTKR2016010582-appb-I000177
    Figure PCTKR2016010582-appb-I000177
  10. 청구항 1에 있어서, The method according to claim 1,
    상기 블록 중합체 내에서 상기 친수성 블록과 소수성 블록은 1:0.001 내지 1:100의 몰 비율로 포함되는 것인 블록 중합체.Wherein the hydrophilic block and the hydrophobic block are included in the block polymer in a molar ratio of 1: 0.001 to 1: 100.
  11. 청구항 1에 있어서, The method according to claim 1,
    상기 블록 중합체는 하기 화학식 5로 표시되는 화합물로부터 유래되는 브랜처; 또는 The block polymer is a brancher derived from a compound represented by the formula (5); or
    하기 화학식 6으로 표시되는 브랜처를 더 포함하는 것인 블록 중합체: A block polymer further comprising a brancher represented by the following formula (6):
    [화학식 5][Formula 5]
    Figure PCTKR2016010582-appb-I000178
    Figure PCTKR2016010582-appb-I000178
    [화학식 6][Formula 6]
    Figure PCTKR2016010582-appb-I000179
    Figure PCTKR2016010582-appb-I000179
    화학식 5 및 6에 있어서, In Chemical Formulas 5 and 6,
    X는 S; O; CO; SO; SO2; NR""; 탄화수소계 또는 불소계 결합체이며, X is S; O; CO; SO; SO 2 ; NR ""; Hydrocarbon-based or fluorine-based conjugates,
    R""은 수소; 할로겐기로 치환된 방향족고리; 또는 할로겐기로 치환된 지방족 고리이고, R ″ ″ is hydrogen; Aromatic rings substituted with halogen groups; Or an aliphatic ring substituted with a halogen group,
    l은 0 내지 10의 정수이며, l is an integer from 0 to 10,
    l이 2 이상인 경우, 2 이상의 X는 서로 동일하거나 상이하고, when l is 2 or more, two or more X are the same as or different from each other,
    Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 히드록시기 및 할로겐기로 이루어진 군에서 선택되는 치환기로 1 또는 2 이상 치환된 방향족고리; 또는 히드록시기 및 할로겐기로 이루어진 군에서 선택되는 치환기로 1 또는 2 이상 치환된 지방족 고리이며, Y1 and Y2 are the same as or different from each other, and each independently an aromatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group; Or an aliphatic ring substituted with one or two or more substituents selected from the group consisting of a hydroxy group and a halogen group,
    Z는 3가의 유기기이다.Z is a trivalent organic group.
  12. 청구항 1에 있어서, The method according to claim 1,
    상기 블록 중합체의 중량평균분자량은 500 g/mol 내지 5,000,000 g/mol 인 것인 중합체.The weight average molecular weight of the block polymer is from 500 g / mol to 5,000,000 g / mol.
  13. 청구항 1 내지 12 중 어느 한 항에 따른 블록 중합체를 포함하는 고분자 전해질막.A polymer electrolyte membrane comprising the block polymer according to any one of claims 1 to 12.
  14. 청구항 13에 있어서, The method according to claim 13,
    상기 고분자 전해질막의 이온 전도도는 0.01 S/cm 내지 0.5 S/cm 인 것인 고분자 전해질막.Ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm to 0.5 S / cm It is a polymer electrolyte membrane.
  15. 청구항 13에 있어서, The method according to claim 13,
    상기 고분자 전해질막의 이온교환용량(IEC) 값은 0.01 mmol/g 내지 5 mmol/g 인 것인 고분자 전해질막.The ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g polymer electrolyte membrane.
  16. 청구항 13에 있어서, The method according to claim 13,
    상기 고분자 전해질막의 두께는 1 ㎛ 내지 500 ㎛ 인 것인 고분자 전해질막. The polymer electrolyte membrane has a thickness of 1 μm to 500 μm.
  17. 애노드; 캐소드; 및 상기 애노드와 상기 캐소드 사이에 구비된 청구항 13의 고분자 전해질막을 포함하는 막-전극 접합체.Anode; Cathode; And a polymer electrolyte membrane of claim 13 provided between the anode and the cathode.
  18. 2 이상의 청구항 17에 따른 막-전극 접합체;At least two membrane-electrode assemblies according to claim 17;
    상기 막-전극 접합체들 사이에 구비되는 바이폴라 플레이트를 포함하는 스택;A stack comprising a bipolar plate provided between the membrane-electrode assemblies;
    상기 스택으로 연료를 공급하는 연료공급부; 및A fuel supply unit supplying fuel to the stack; And
    상기 스택으로 산화제를 공급하는 산화제공급부를 포함하는 고분자 전해질형 연료전지.A polymer electrolyte fuel cell comprising an oxidant supply unit for supplying an oxidant to the stack.
  19. 양극 및 양극 전해액을 포함하는 양극 셀;A cathode cell comprising an anode and an anode electrolyte solution;
    음극 및 음극 전해액을 포함하는 음극 셀; 및A cathode cell comprising a cathode and a cathode electrolyte; And
    상기 양극 셀과 상기 음극 셀 사이에 구비되는 청구항 13의 고분자 전해질막을 포함하는 레독스 플로우 전지.Redox flow battery comprising the polymer electrolyte membrane of claim 13 provided between the positive electrode and the negative electrode cell.
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