WO2011087344A2 - Porous support, and polymer electrolyte membrane for a fuel cell comprising same - Google Patents

Porous support, and polymer electrolyte membrane for a fuel cell comprising same Download PDF

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Publication number
WO2011087344A2
WO2011087344A2 PCT/KR2011/000368 KR2011000368W WO2011087344A2 WO 2011087344 A2 WO2011087344 A2 WO 2011087344A2 KR 2011000368 W KR2011000368 W KR 2011000368W WO 2011087344 A2 WO2011087344 A2 WO 2011087344A2
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formula
porous support
group
polyimide
polymer
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PCT/KR2011/000368
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French (fr)
Korean (ko)
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WO2011087344A3 (en
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이영무
박치훈
이소영
한상훈
황두성
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한양대학교 산학협력단
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Publication of WO2011087344A2 publication Critical patent/WO2011087344A2/en
Publication of WO2011087344A3 publication Critical patent/WO2011087344A3/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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/18—Polybenzimidazoles
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • Porous support and polymer electrolyte membrane for fuel cell comprising same
  • the present invention relates to a porous support and a polymer electrolyte membrane for a fuel cell comprising the same.
  • a fuel cell is a power generation system that directly converts the chemical reaction energy of hydrogen and oxygen contained in hydrocarbon-based materials such as methanol, ethanol and natural gas into electrical energy. Such fuel cells are drawing attention as a clean energy source that can replace fossil energy.
  • Typical examples of fuel cells include a polymer, electrolyte fuel cells (polymer electrolyte membrane fuel cell, PEMFC ), direct oxidation fuel cell (direct oxidation fuel cell).
  • PEMFC polymer electrolyte membrane fuel cell
  • direct oxidation fuel cell direct oxidation fuel cell
  • methane methane is used as the fuel in the direct oxidation fuel cell, it is called a direct methanol fuel cell (DMFC).
  • the stack that substantially generates electricity has a structure in which several to tens of unit cells including a membrane-electrode assembly (MEA) and a separator are stacked.
  • the membrane-electrode assembly includes an anode and a cathode interposed between a polymer electrolyte membrane including a cation exchange resin having hydrogen ion conductivity. It has a structure that is located opposite.
  • the principle of generating electricity in a fuel cell is that fuel is supplied to an anode, which is a fuel electrode, adsorbed to a catalyst of the anode, and fuel is ionized by an oxidation reaction to generate electrons.
  • an oxidation reaction to generate electrons.
  • hydrogen ions pass through the polymer electrolyte membrane and are delivered to the cathode.
  • An oxidant is supplied to the cathode, and the oxidant, hydrogen ions and electrons react on the catalyst of the cathode to generate electricity while producing water.
  • a membrane is provided, and a method of manufacturing the porous support and the polymer electrolyte membrane for the fuel cell is provided.
  • It provides a membrane-electrode assembly comprising the porous support and the polymer electrolyte membrane for the fuel cell, and provides a fuel cell system comprising the membrane-electrode assembly.
  • the porous support comprises a polymer derived from polyamic acid or a polymer derived from polyimide.
  • the porous support has micropores and picopores present in the polymer derived from the polyamic acid or picopores present in the polymer derived from the polyimide, wherein the polyamic acid and the polyimide have an ortho position relative to an amine group.
  • the functional group may comprise OH, SH or N3 ⁇ 4.
  • the polymer is induced by thermal conversion from the polyamic acid or the polyimide, and the ratio (thermal conversion rate) of the thermally converted unit with respect to the total amount (100 mol 3 ⁇ 4;) of the repeating units included in the polyamic acid or the polyimide ) May be about 10 mol% to about 100 mol%.
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume degree (FFV) of about 0.18 to about 0.40.
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may have an interplanar distance by XRD measurement in the range of about 550 pm to about 800 pm.
  • Two or more picopores may be connected to each other to form an hourglass shape.
  • the picopores are positron decay time spectroscopy (positron Full width at half maximum (FWHM) by annihilation lifetime spectroscopy (PALS) measurement may range from about 10 pm to about 40 pm.
  • the porous support may have a porosity of about 10% by volume to about 95% by volume relative to the total volume of the support.
  • the porous support may be formed to a thickness of about 10 iM to about 200.
  • the polyamic acid is a polyamic acid including a repeating unit represented by the following Chemical Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by the following Chemical Formulas 5 to 8, copolymers thereof, and blends thereof
  • the polyimide is a polyimide comprising a repeating unit represented by the following formula 19 to 22, a polyimide copolymer comprising a repeating unit represented by the following formula 23 to 26, copolymers thereof and their It can be selected from the group consisting of blends.
  • the ylene group is substituted with a C1 to C6 alkyl group or a C1 to C6 haloalkyl group, wherein Q is connected to both aromatic rings with the mm, mp, pm, or pp position, and ⁇ is the same or different from each other at each repeating unit.
  • Each independently OH, SH or NH 2
  • n is an integer satisfying 20 ⁇ n ⁇ 200,
  • n is an integer satisfying 10 ⁇ m ⁇ 400
  • 1 is an integer satisfying 10 ⁇ 1 ⁇ 400.
  • the molar ratio between each repeating unit in the copolymer of the polyimide including or the molar ratio of m: l in the above formulas 23 to 26 may be about 0.1: 9.9 to about 9.9: 0.1.
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may include a polymer including a repeating unit represented by any one of Formulas 37 to 50 or a copolymer thereof.
  • X 2 , 3 ⁇ 4 and X 4 are the same or different from each other and each independently 0, S,
  • 3 ⁇ 4 and 3 ⁇ 4 are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time is not CR 103 ;
  • Ri to 2 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
  • kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
  • k4, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers of 0 to 3,
  • k30, k37, k40 and k41 are integers from 0 to 4,
  • k32 and k33 are integers of 0-5.
  • R 100 , R 101 and R 102 are the same or different from each other and are each independently hydrogen or a C1 to C5 alkyl group,
  • Z 2 and 3 ⁇ 4 are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time is not CR 103 ;
  • R 43 to R 89 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group,
  • k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
  • k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
  • k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are integers from 0 to 2
  • k50 is an integer of 0 or 1
  • k69, k71, k77 and k79 are integers of 0-5.
  • specific examples of Ar 2 may be selected from those represented by the following formulas.
  • M is a metal
  • the metal may be sodium, potassium, lithium, alloys thereof, or a combination thereof.
  • examples and specific examples of AiV are the same as those mentioned for the examples and specific examples of Ar 2 of Formulas 1 to 8, 19 to 26, and 37 to 50.
  • A represents the following formula It may be a functional group represented by any one of Al to A8, Ar 2 is represented by the following formula
  • Q may be C (CF 3 ) 2 .
  • Arr ⁇ may be a functional group represented by any one of Formulas A1 to A8, An 'may be a functional group represented by any one of Formulas C1 to C8, and Ar 2 may be represented by Formulas B1 to B11 It may be a functional group represented by any one of, Q may be C (CF 3 ) 2 .
  • the porous support may include a fiber including a polymer having the picopores, and the fibers may be randomly arranged.
  • the porous support may comprise a fiber comprising a polymer having the picopores, the fibers may be arranged in one direction.
  • the porous support provides a polymer electrolyte membrane for a fuel cell comprising a cation exchange resin formed on the inside, the surface, or the inside and the surface of the porous support.
  • the cation exchange resin may be a polymer including a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups and phosphoric acid groups, phosphonic acid groups, and derivatives thereof.
  • the porous support and the Cation exchange resins may be included in a weight ratio of about 99: 1 to about 10:90.
  • a polymer electrolyte membrane for a fuel cell including the porous support and formed by acid doping on the inside, the surface, or the inside and the surface of the porous support.
  • the doped acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof.
  • a polymer electrolyte membrane for a fuel cell including a porous support and a fluorine group on the surface of the porous support.
  • the fuel cell polymer electrolyte membrane may be formed to a thickness of about 20 ⁇ to about 300.
  • a polyamic acid or polyimide having a repeating unit prepared from aromatic diamine and dianhydride comprising at least one functional group present in the ortho position relative to the amine group; And it provides a composition for forming a porous support comprising an organic solvent.
  • the organic solvent is dimethyl sulfoxide; ⁇ -methyl-2—pyrrolidone; ⁇ -methylpyridone; ⁇ , ⁇ -dimethylformamide; ⁇ , ⁇ -dimethylacetamide;
  • Ketones selected from the group consisting of butyrolactone, cyclonucleanone, 3 ′ nucleosanone, 3-heptanone and 3-octanone; And it is selected from the group consisting of a combination thereof.
  • the composition for forming a porous support is a composition for forming a porous support
  • the polyamic acid or the polyimide may include about 1 wt% to about 40 wt% of the total amount, and about 60 wt% to about 99 wt% of the organic solvent.
  • the composition for forming the porous support is water; Methane, ethane, alcohol selected from the group consisting of 2-methyl-1-butanol, 2-methyl-2-butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; Ketones selected from the group consisting of acetone and methylethyl ketone; A polymer compound selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polypropylene glycol, chitosan, chitin, dextran, and polyvinylpyridone; Tetrahydrofuran; Trichloroethane; And it may further comprise an adjuvant selected from the group consisting of a combination thereof.
  • the composition for forming the porous support is about 1% by weight to about 40% by weight of the polyamic acid or the polyimide and about 10% by weight of the organic solvent based on the total amount of the composition for forming the porous support including the auxiliary agent. About 95% by weight, and about 4% to about 70% by weight of the adjuvant.
  • the polyamic acid and the polyimide may each have a weight average molecular weight (Mw) of about 10,000 g / mol to about 500,000 g / m.
  • the composition for forming the porous support may have a viscosity of about 0.01 Pa-s to about 100 Pa ⁇ s.
  • the heat-treated to induce from a polymer or a polyimide derived from the polyamic acid polymers provides a method for producing the porous support, comprising the step of forming a porous support comprising.
  • the step of electrospinning the composition for forming the porous support to form a nonwoven fabric Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of forming a cation exchange resin on the inside, surface, or the inside and the surface of the porous support.
  • the step of electrospinning the composition for forming the porous support to form a nonwoven fabric Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of doping the acid inside, the surface, or the inside and the surface of the porous support.
  • the acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof.
  • the step of forming a nonwoven fabric by electrospinning the composition for forming a porous support Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And on the surface of the porous support It provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of introducing a fluorine group.
  • the electrospinning may be performed by applying a voltage of about 1 kV to about 1,000 kV.
  • the nonwoven fabric formed by the electrospinning may be randomly arranged fibers including the composition for forming a porous support.
  • the non-woven fabric formed by the electrospinning may be a fiber comprising a composition for forming a porous support may be arranged in one direction.
  • the polymer is induced by thermal conversion from the polyamic acid or the polyimide, and with respect to the total amount (100 mol%) of the repeating units included in the polyamic acid or the polyimide, the ratio of the thermally converted units (thermal conversion rate) ) May be about 10 mole% to about 100 mole>.
  • the heat treatment may be carried out at a temperature of about 250 ° C to about 550 ° C, may be carried out for about 10 minutes to about 5 hours.
  • the temperature increase rate during the heat treatment may be about 1 ° C / min to about 20 ° C / min.
  • the anode and the cathode located opposite each other; And a membrane-electrode assembly positioned between the anode and the cathode, the membrane comprising an electrolyte membrane for the fuel cell.
  • the membrane electrode assembly and at least one separator including the electrochemical reaction of fuel and oxidant
  • the porous support has excellent mechanical properties, dimensional stability, and chemical resistance
  • the polymer electrolyte membrane for fuel cells has excellent hydrogen ion conductivity, mechanical properties, dimensional stability, and chemical resistance, and excellent fuel barrier property.
  • the output density can be improved.
  • FIG. 1 is a view schematically showing a membrane-electrode assembly for a fuel cell according to an embodiment of the present invention.
  • FIG. 2 is a view schematically showing the structure of a fuel cell system according to another embodiment of the present invention.
  • Example 3 is a photograph of the porous support prepared in Example 4.
  • FIG. 4 is a photograph of a polymer electrolyte membrane for a fuel cell prepared in Example 4.
  • picopores refers to pores having an average diameter of pores of several hundred picometers, specifically, about 100 pm to about 1,000 pm, and "microporous pores” means the average diameter of pores. It means pores that are about 2 nm to about 50 im, specifically about 10 nm to about 10.
  • substituted or “substituted” means that the hydrogen atom in the compound or functional group consists of a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 haloalkyl group, and a C1 to C10 haloalkoxy group It means substituted by one or more substituents selected from the group, "hetero ring group” means a hetero atom selected from the group consisting of 0, S, N, P, Si and combinations thereof in one ring from 1 to 3 substituted or unsubstituted C2 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 cycloalkynyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 cycloal
  • aliphatic organic group is a C1 to C30 alkyl group, C2 to C30 alkenyl group, or C2 to C30 alkynyl group, specifically, C1 to C15 alkyl group, C2 to C15 alkenyl group, Or a C2 to C15 alkynyl group, more specifically a C1 to C10 alkyl group, a C2 to C10 alkenyl group, or a C2 to C10 alkynyl group.
  • FIG. 1 is a schematic diagram of a membrane-electrode assembly for a fuel cell according to an embodiment of the present invention It is a figure shown.
  • the membrane-electrode assembly 20 for a fuel cell includes an anode 22, a polymer electrolyte membrane 24, and a cathode 26.
  • the anode 22 and cathode 26 comprise an electrode substrate and a catalyst layer formed on the electrode substrate.
  • the reaction of the fuel can be promoted at the anode, and the reaction of the oxidant, hydrogen ions and electrons supplied to the cathode can be promoted at the cathode, thereby improving the efficiency of the fuel cell.
  • Examples of the catalyst included in the catalyst layer include platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-M alloy, where M is gallium (Ga), titanium (Ti), vanadium (V), crumb (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), molybdenum (Mo), Tungsten (W), rhodium (Rh), ruthenium (Ru) and combinations thereof, and combinations thereof, but is not limited thereto. More specific examples of the catalyst include Pt, Pt / Ru, Pt / W, Pt / Ni,
  • Pt / Sn Pt / Mo, Pt / Pd, Pt / Fe, Pt / Cr, Pt / Co, Pt / Ru / W, Pt / Ru / Mo, Pt / Ru / V, Pt / Fe / Co, Pt / And at least one selected from the group consisting of Ru / Rh / Ni and Pt / Ru / Sn / W.
  • the catalyst may be used as the catalyst itself (black) or may be supported on a carrier.
  • a carrier carbonaceous materials such as graphite, denka black, ketjen black, acetylene black, carbon nanotube, carbon nanofiber, carbon nanowire, carbon nanoball, or activated carbon may be used, or alumina, silica, zirconia, Inorganic fine particles such as titania may also be used, but are not limited thereto.
  • the polymer electrolyte membrane 24 for the fuel cell is positioned between the anode 22 and the cathode 26 and has a porous support 244 and a cation exchange resin present inside, on the surface, or within and inside the porous support ( 242).
  • the cation exchange resin 242 may be one having a cation conductivity, for example, hydrogen ion conductivity.
  • the polymer electrolyte membrane 24 is an insulator that electrically separates the anode 22 and the cathode 26, but acts as a medium for transferring hydrogen ions from the anode 22 to the cathode 26 during battery operation. It serves to separate gas or liquid.
  • the membrane 24 may include the porous support 244 to electrically separate the anode 22 and the cathode 26, and may have excellent mechanical properties and dimensional stability. This allows the membrane-electrode assembly comprising it to facilitate the stack construction.
  • the porous support 244 includes a polymer derived from polyamic acid or a polymer derived from polyimide.
  • the polyamic acid, the polyimide, and the polymer derived therefrom will be described later.
  • the porous support 244 has micropores and picopores present in the polymer derived from the polyamic acid or picopores present in the polymer derived from the polyimide, wherein the polyamic acid and the polyimide have an amine group. Repeat units made from aromatic diamines and dianhydrides comprising at least one functional group present at the ortho position.
  • the porous support 244 may have a high porosity and thus efficiently include a cation exchange resin in the pores, thereby allowing a cation such as hydrogen ions to be easily transferred from the anode 22 to the cathode 26 so as to provide fuel.
  • the efficiency of the battery can be improved.
  • the cation exchange resin is adsorbed to the picopores of the porous support 244 or the acid is doped, the adsorbed cation exchange resin and the doped acid are hardly separated from the porous support body. This makes it possible to transfer cations such as hydrogen ions from the anode 22 to the cathode 26 more stably, thereby improving the efficiency and life characteristics of the fuel cell.
  • the functional group present in the ortho position relative to the amine group may comprise OH, SH or NH 2 .
  • the polyamic acid and the polyimide can be prepared according to a general method.
  • the polyamic acid may be prepared by reacting an aromatic diamine and tetracarboxylic anhydride including OH, SH, or NH 2 groups present at an ortho position with respect to an amine group, and the polyimide may have already formed the polyamic acid. It can be prepared by hydration, such as thermal solution imidization or chemical imidization.
  • the thermal solution imidization further comprises an organic solvent such as N-methylpyrrolidone (NMP), an aliphatic organic solvent such as benzene, toluene, xylene, cresol, etc., nucleic acid, cyclonucleic acid, or the like. It can be made using an azeotrope made by addition.
  • NMP N-methylpyrrolidone
  • an aliphatic organic solvent such as benzene, toluene, xylene, cresol, etc.
  • nucleic acid cyclonucleic acid, or the like.
  • the polyamic acid and the polyimide are thermally converted by a predetermined heat treatment to polymers such as polybenzoxazole, polybenzothiazole and polypyrrole having picopores and excellent mechanical strength and high free volume. Can be switched.
  • the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 10 mol% to about 100 mol3 ⁇ 4>.
  • the heat resistance and mechanical strength of the porous support can be effectively improved, and for cation exchange resins
  • the wettability is improved so that the compatibility between the porous support and the cation exchange resin can be improved.
  • delamination between the porous support and the cation exchange resin can be prevented, and durability of the polymer electrolyte membrane for a fuel cell including the porous support can be effectively improved.
  • the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 40 mol% to about 100 mol%.
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume (FFV) of about 0.18 to about 0.40, and the d-spacing by XRD is about 550 pm to about It can be in the range of 800 pm.
  • FMV free volume
  • XRD XRD-d-spacing by XRD
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may include picopores, and two or more picopores may be connected to each other to form an hourglass shape. As a result, the polymer may have high porosity, so that low molecules may be efficiently permeated or selectively separated.
  • the average diameter of the picopores may be about 600 pm to about 800 pm, but is not limited thereto.
  • the picopores were immediately determined by positron annihilat ion lifetime spectroscopy (PALS). Full width at half maximum (FWHM) may range from about 10 pm to about 40 pm. This indicates that the size of the generated picopores is fairly uniform.
  • PALS data or the like 22 of 0.511MeV generated at the time of 1.27MeV Na is generated at the time of generating by irradiating the positron emitted from the isotopes decay ⁇ ⁇ , time difference ⁇ 2 " ⁇ , ⁇ 2> ⁇ 3 You can get it by using.
  • the porous support 244 may uniformly include micropores and picopores as a whole, and may have a porosity of about 10% by volume to about 95% by volume with respect to the total volume of the support, and may include a cation exchange resin in the pores. As such, it is possible to effectively improve the efficiency of the fuel cell by improving the cation conductivity, such as hydrogen ion conductivity.
  • the porous support 244 may be formed through electrospinning, and by adjusting the method or process conditions of the electrospinning, such that the fibers including the polymer having the picopores are randomly arranged in the porous support 244. Can be formed.
  • the fiber containing the polymer having the picopores may be formed to be arranged in one direction on the porous support 244. have.
  • the strength in the direction in which the fibers are arranged can be effectively improved.
  • hydrogen ions are rapidly formed along the direction in which the fibers are arranged. Can be delivered to effectively improve hydrogen ion conductivity.
  • the porous support 244 may be formed to have a thickness of about 10 1 to about 200.
  • the porous support 244 When the thickness of the porous support 244 is in the above range, it is possible to improve the mechanical properties, chemical resistance and dimensional stability of the polymer electrolyte membrane 24 including the same. Specifically, the porous support 244 may be formed to have a thickness of about 20 to about 180.
  • the fuel cell polymer electrolyte membrane 24 includes a cation exchange resin 242, thereby improving cation conductivity, for example, hydrogen ion conductivity, and suppressing fuel crossover.
  • the cation exchange resin 242 is present inside, on the surface, or inside and on the surface of the porous support 244. When the cation exchange resin is present in the porous support, it may be present in the micropores and picopores of the porous support.
  • the polymer electrolyte membrane 24 for fuel cell excellent in mechanical strength and dimensional stability and also excellent in cation conductivity, such as hydrogen ion conductivity, can be provided.
  • the cation exchange resin can improve the cation conductivity, such as hydrogen ion conductivity, of the polymer electrolyte membrane 24 for fuel cells, and can improve the efficiency of the fuel cell.
  • the cation exchange resin is a cation selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof
  • a polymer containing an exchange group for example, a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a poly Ether ketone polymers, polyether ether ketone polymers, polyphenylquinoxaline polymers, or combinations thereof, but is not limited thereto.
  • the cation exchange resin may include a polymer having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the polymer.
  • the cation exchange resin may include a polymer in which the functional group is substituted with a polymer which does not have the functional group, and has an acid having the functional group as described above in the polymer which does not have the functional group. It may also comprise a doped polymer.
  • Examples of the polymer having a functional group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof in the original polymer include Nafion (Nafion, Dupont), sulfonated poly (phenylene Sulfonated_poly (phenylene sulfide sul f one nitrile: s-PSSN), sulfonated poly (arylene ether sul f one: s-PAES), sulfonated Sulfonated-poly (ether ether ketone: s-PEEK) and the like, but are not limited thereto.
  • polymers capable of forming a cation exchange resin by substituting a functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group and derivatives thereof, or by doping an acid having the functional group as described above.
  • a functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group and derivatives thereof, or by doping an acid having the functional group as described above.
  • the polybenzimidazole, polyimide, polyphenylene sulfide, polysulfone, polysulfone derivative, polyphenylene oxide, polyphenylene sulfide, polyphosphazene and the like but is not limited thereto.
  • the polymer electrolyte membrane 24 for the fuel cell may include the porous support and the cation exchange resin in a weight ratio of about 99: 1 to about 10:90.
  • the polymer electrolyte membrane for a fuel cell including the same may have excellent mechanical strength and dimensional stability.
  • the porous support and the cation exchange resin may be included in a weight ratio of about 95: 5 to about 30:70.
  • the fuel cell polymer electrolyte membrane 24 is formed by acid doping therein, on the surface, or inside and the surface thereof.
  • the acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof, but is not limited thereto.
  • the acid doped in the porous support 244 plays a role similar to that of the cation exchange resin 242. Therefore, the acid doped in the porous support 244 is The cation conductivity, such as hydrogen ion conductivity, of the polymer electrolyte membrane 24 for fuel cells can be improved, and the efficiency of the fuel cell can be improved.
  • the fuel cell polymer electrolyte membrane 24 may have a thickness of about 20 IM to about 300.
  • excellent cation conductivity such as hydrogen ion conductivity
  • fuel crossover can be suppressed, and also excellent mechanical strength, dimensional stability, heat resistance and resistance to heat. Chemicality can be effectively achieved.
  • the fuel cell polymer electrolyte membrane 24 may have a thickness of about 20 to about 250.
  • the polyamic acid used to form the porous support may be a polyamic acid including a repeating unit represented by the following Chemical Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by the following Chemical Formulas 5 to 8, a copolymer thereof, and It can be selected from the group consisting of these blends.
  • ⁇ is an integer satisfying 20 ⁇ 200
  • n is an integer satisfying 10 ⁇ m ⁇ 400
  • 1 is an integer satisfying 10 ⁇ 1 ⁇ 400.
  • Examples of the copolymer of the polyamic acid including the repeating units represented by Formulas 1 to 4 include polyamic acid copolymers including the repeating units represented by the following Formulas 9 to 18.
  • the polyimide used to form the porous support is a polyimide comprising a repeating unit represented by the following formulas 19 to 22, a polyimide copolymer comprising a repeating unit represented by the following formulas 23 to 26, a copolymer thereof, and It may be selected from the group consisting of blends, but is not limited thereto.
  • Examples of the copolymer of the polyimide including the repeating units represented by the formulas (19) to (22) include polyimide copolymers including the repeating units represented by the following formulas (27) to (36).
  • Y and Y ' are the same or different from each other and are each independently OH, SH or N3 ⁇ 4.
  • examples of A may be selected from those represented by the following formulas, but are not limited thereto.
  • Wi and are the same or different and are each independently 0, S, or C ( 0),
  • Z 2 and 3 ⁇ 4 are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time not CR 103;
  • Ri to R 42 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
  • kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
  • k4, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers of 0 to 3,
  • k30, k37, k40 and k41 are integers from 0 to 4,
  • k32 and k33 are integers of 0-5.
  • R 100 , R 101 and R 102 are the same or different and are each independently hydrogen or a C1 to C5 alkyl group,
  • Z 3 ⁇ 4 and Z 3 are the same or different from each other and independently from each other N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group), but not 01 ⁇ 2 3 ;
  • 3 to 3 ⁇ 49 are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group, wherein the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof
  • the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof
  • k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
  • k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
  • k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are numbers from 0 to 2
  • k50 is an integer of 0 or 1
  • k69, k71, k77 and k79 are integers of 0-5.
  • Ar 2 may be selected from the following, but are not limited thereto.
  • M is a metal, and the metal may be sodium, potassium, lithium, alloys thereof, or a combination thereof, but is not limited thereto.
  • A may be a functional group represented by any one of Formulas A1 to A8, Ar 2 may be a functional group represented by any one of Formulas B1 to B11, and Q is C (CF 3 ) 2 May be, but It is not limited.
  • the polyamic acid including the repeating unit represented by Formula 1 to Formula 4 and the polyimide including the repeating unit represented by Formula 19 to Formula 22 may be manufactured by a general manufacturing method. For example, it is prepared by reacting tetracarboxylic anhydride with an aromatic diamine containing a subgroup I, SH or NH 2 as a monomer.
  • the polyamic acid including the repeating unit represented by Formula 1 to Formula 4 is imidized and thermally converted by a predetermined heat treatment, and the polyimide including the repeating unit represented by Formula 19 to Formula 22 is subjected to a predetermined heat treatment. It is thermally converted to a polymer such as polybenzoxazole, polybenzothiazole, polypylon, which has picopores and has excellent mechanical properties and high free volume.
  • Y in Formula 1 to Formula 4 is 0H
  • a porous support is prepared comprising polypylons derived from polyaminoamic acid or polyaminoimide wherein Y is NH 2 .
  • the molar ratio between the repeating units in the copolymer of the polyimide including the repeating units represented by Formulas 19 to 22 it is possible to control the physical properties of the prepared porous support.
  • the polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 may be imidized and thermally converted by a predetermined heat treatment.
  • the polyimide comprising the repeating unit represented by Formula 23 to Formula 26 The copolymer can be thermally converted by a predetermined heat treatment.
  • the polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 and the polyimide copolymer including the repeating unit represented by Formula 23 to Formula 26 have picopores and have excellent mechanical properties and high freedom.
  • a porous support comprising coalescing can be formed.
  • a porous support comprising coalescing can be formed.
  • the copolymerization ratio molar ratio
  • the copolymer of the polyamic acid including the repeating unit represented by Formula 9 to Formula 18 may be imidized and thermally converted by a predetermined heat treatment.
  • the copolymer of polyimide can be thermally converted by a predetermined heat treatment.
  • the copolymer of the polyamic acid including the repeating unit represented by the formula (9) to the formula (18) and the copolymer of the polyimide including the repeating unit represented by the formula (27) to (36) has picopores and excellent mechanical properties and It is converted into a copolymer of polybenzoxazole, polybenzothiazole and polypyrrolone having a high degree of free volume, which can be used to form a porous support comprising such a copolymer.
  • the copolymerization ratio molar ratio
  • Molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating unit represented by Formula 1 to Formula 4; Or the inter-block copolymerization ratio (molar ratio) m: l of the polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: 2, more specifically about 5: 5.
  • the molar ratio between each repeating unit in the co-polymer of a polyimide containing a repeating unit represented by the formula (19) to formula (22); Or the interblock copolymerization ratio (molar ratio) m: l of the polyimide copolymer including the repeating unit represented by Formula 23 to Formula 26 is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: 2, more specifically about 5: 5.
  • the molar ratio to the copolymerization ratio affects the morphology of the porous support to be produced, which is related to pore properties, heat resistance, surface hardness, and the like.
  • the porous support to be prepared may have excellent mechanical properties and dimensional stability, may have excellent 'porosity, and also have excellent workability to reduce the process time and cost reduction effect have.
  • the polymer derived from the polyamic acid and the polymer derived from the polyimide may include a polymer including a repeating unit represented by any one of the following Formulas 37 to 50 or a copolymer thereof: Or not limited thereto.
  • examples and specific examples of ArV are the same as those mentioned for the examples and specific examples of Ar 2 of Formulas 1 to 36.
  • A may be a functional group represented by any one of Formulas A1 to A8,
  • Ar may be a functional group represented by any one of Formulas C1 to C8, and
  • Ar 2 is represented by Formulas B1 to B11 It may be a functional group represented by any one, and Q may be C (CF 3 ) 2 , but is not limited thereto.
  • the porous support may include a fluorine group on the surface.
  • the adhesion with the ion conductor can be improved, and the wettability, permeat ion, electrical conductivity, grafting property and mechanical behavior of the porous support can be improved. ) Can be improved.
  • the fluorine group may be introduced by, for example, direct fluorination or plasma deposition using fluorine or fluoride, but is not limited thereto.
  • the porous support has excellent dimensional stability with shrinkage of less than about 10% even after heat treatment.
  • a polyamic acid or polyimide having a repeating unit prepared from an aromatic diamine and a dianhydride including at least one functional group present at an ortho position relative to an amine group; And it provides a composition for forming a porous support comprising an organic solvent.
  • the organic solvent is dimethyl sulfoxide; N-methyl-2-pyridone; N-methylpyridone; ⁇ , ⁇ ⁇ dimethylformamide; ⁇ , ⁇ —dimethylacetamide;
  • Ketones selected from the group consisting of butyrolactone, cyclonucleanone, 3-nuxanone, 3-heptanone and 3-octanone; And combinations thereof It is chosen.
  • the organic solvent can easily dissolve a polymer such as the polyamic acid or the polyimide.
  • a polymer such as the polyamic acid or the polyimide.
  • the adjuvant to be described later it is possible to form the composition for forming a porous support in a stable (met a-stable) state, thereby making it possible to easily form a porous support.
  • the composition for forming a porous support includes about 1 wt% to about 40 wt% of the polyamic acid or the polyimide and about 60 wt% to about 99 wt% of the organic solvent, based on the total amount of the composition for forming the porous support. can do.
  • the viscosity of the composition for forming a porous support may be properly maintained to facilitate the preparation of the porous support, and the size of the surface and internal pores of the formed porous support may be adjusted. It can be adjusted appropriately.
  • the strength of the porous support can be maintained excellent, thereby easily forming a porous support having excellent mechanical strength and dimensional stability and a polymer electrolyte membrane for a fuel cell including the same.
  • composition for forming the porous support ' water Alcohols selected from the group consisting of methanol, ethanol, 2-methyl-l-butanol, 2-methyl-2'butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; Ketones selected from the group consisting of acetone and methylethyl ketone; A polymer compound selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polypropylene glycol, chitosan, chitin, dextran, and polyvinylpyridone; Tetrahydrofuran; Trichloroethane; And it may further comprise an adjuvant selected from the group consisting of a combination thereof.
  • Alcohols selected from the group consisting of methanol, ethanol, 2-methyl-l-butanol, 2-methyl-2'butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol
  • Ketones
  • the auxiliary agent may not be used alone because it is not excellent in solubility with polyamic acid or polyimide, but when properly mixed with an organic solvent, a composition for forming a meta-stable porous support may be prepared. When electrospinning, it is possible to effectively form a nonwoven fabric having an appropriate pore size, pore distribution and porosity.
  • the auxiliary agent may be removed by diffusion, evaporation, etc. during formation of the porous support to form micropores in the porous support, thereby increasing the porosity of the porous support.
  • the polymer compound can be used as a pore control agent.
  • the adjuvant may be used for controlling the viscosity of the composition for forming a phase separation temperature or the porous support.
  • the composition for forming a porous support may include about 1 wt% to about 40 wt% of the polyamic acid or polyimide, and about 10 wt% to about 95 of the organic solvent, based on the total amount of the composition for forming a porous support including the auxiliary agent. Weight percent, and from about 4 weight percent to about 70 weight percent of the adjuvant.
  • the viscosity of the composition for forming a porous support may be properly maintained to facilitate the preparation of the porous support, and the size of the surface and internal pores of the formed porous support may be adjusted. It can be adjusted appropriately.
  • porous The strength of the support can be maintained excellent, thereby easily forming a porous support excellent in mechanical strength and dimensional stability and a polymer electrolyte membrane for a fuel cell including the same.
  • the composition for forming the porous support may have a viscosity of about 0.01 Pa-s to about 100 Pa-s.
  • the viscosity of the composition for forming a porous support is within the above range, the composition for forming a porous support can be easily electrospun, and the porous support can be easily solidified through a phase transition phenomenon.
  • the polyamic acid and the polyimide may each have a weight average molecular weight (Mw) of about 10,000 g / mol to about 500,000 g / nrol.
  • Mw weight average molecular weight
  • the synthesis thereof is easy, and the viscosity of the composition for forming a porous support including the same is appropriately maintained so as to be excellent in processability, and the polymer and poly is derived from the polyamic acid.
  • Polymers derived from meads can be maintained with good mechanical strength and dimensional stability.
  • the polyamic acid is a polyamic acid comprising a repeating unit represented by Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by Formulas 5 to 8, copolymers thereof And blends thereof.
  • the polyimide is a polyimide containing a repeating unit represented by the formula (19) to 22, the repeating unit represented by the formula (23 to 26) It can be selected from the group consisting of polyimide copolymers, copolymers thereof and blends thereof.
  • forming a nonwoven fabric by electrospinning the composition for forming the porous support; And heat treating the nonwoven fabric to form a porous support including a polymer derived from a polyamic acid or a polymer derived from polyimide.
  • forming a nonwoven fabric by electrospinning the composition for forming the porous support; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of forming a cation exchange resin on the inside, surface, or the inside and the surface of the porous support.
  • a nonwoven fabric including fibers having a diameter of several nm to several tens can be formed.
  • Nonwovens comprising such fibers can have a large specific surface area and can have significant surface roughness.
  • the nonwoven fabric formed at this time includes micropores.
  • the nonwoven fabric may be formed by randomly arranging fibers including the composition for forming the porous support by controlling the method and process conditions of the electrospinning process.
  • the nonwoven fabric may be formed by adjusting the method and the process conditions of the electrospinning, the fiber containing the composition for forming the porous support is arranged in one direction.
  • the electrospinning may be performed by applying a high voltage of about 1 kV to about 1,000 kV. Since electrospinning can be performed according to a general method, details thereof will be omitted.
  • the nonwoven fabric is heat treated.
  • the polyamic acid or polyimide included in the nonwoven fabric by the heat treatment is excellent in mechanical strength and dimensional stability by thermal conversion, and has a high free volume polymer such as polybenzoxazole, polybanzothiazole, polypylon Is converted to a polymer such as As a result, a porous support having excellent physical properties such as mechanical strength and dimensional stability can be formed.
  • the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 10 mol% to about 100 mol%, specifically about 40 Mole% to about 100 mole%. Advantages that the thermal conversion rate may be in the above range is as described above.
  • the heat treatment may be performed at a temperature of about 250 ° C to about 550 ° C, may be performed for about 10 minutes to about 5 hours, the temperature increase rate during the heat treatment is from about 1 ° C / min to about 20 ° C / It may be minutes.
  • the thermal conversion of the polyamic acid and the polyimide is effectively Can be done. That is, the physical properties of the polyamic acid and the polyimide are easily converted into polymers such as polybenzoxazole, polybenzothiazole, and polypylon, which have picopores and have excellent mechanical properties and high free volume. It is excellent in dimensional stability, chemical resistance and heat resistance, can effectively contain a cation exchange resin, and can form a porous support.
  • the heat treatment may be performed with a silver of about 35 CTC to about 450 ° C, may be performed for about 1 hour to about 3 hours, the temperature increase rate during the heat treatment is from about 5 ° C / min to about 10 ° C It can be / minute.
  • a cation exchange resin is formed on the inside, the surface, or the inside and the surface of the porous support.
  • the method of forming a cation exchange resin in the interior, the surface, or the interior and the surface of the porous support has a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups and derivatives thereof in the polymer.
  • the solution containing the polymer for forming the cation exchange resin is the polymer ⁇ , ⁇ -dimethylacetamide ( ⁇ , ⁇ -dimethylacetamide, DMAc), N- methylpyrrolidone (N— Methyl pyrrol i done, NMP) Dissolved in organic solvents, It can manufacture.
  • the solution containing the polymer may be prepared by dissolving in an organic solvent such as ⁇ , ⁇ -dimethylacetamide, ⁇ -methylpyrrolidone such that the polymer is about 1% by weight to about 40% by weight. .
  • the porous support when the porous support is immersed in a solution containing a polymer having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof, in the original polymer, By drying in an oven, a polymer electrolyte membrane for a fuel cell can be formed.
  • the present invention is not limited thereto, and the polymer electrolyte membrane for a fuel cell may be formed by immersion and drying again in an acid aqueous solution having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof after the drying. have.
  • the porous support When the porous support is immersed in a solution containing a polymer which does not have a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the polymer, it is dried in a vacuum Aubon. And then immersed in an aqueous solution containing an acid selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof, and then left out, washed and dried with distilled water to form a polymer electrolyte membrane for fuel cells. can do.
  • forming a nonwoven fabric by electrospinning the composition for forming the porous support; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from the polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of doping the acid on the inside, the surface, or the inside and the surface of the porous support.
  • the acid may be selected from the group consisting of sulfonic acid carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof, but is not limited thereto.
  • a polymer electrolyte membrane for a fuel cell is formed by directly doping an acid into the inside, the surface, or the inside and the surface of the porous support without forming a separate cation exchange resin inside, the surface, or the inside and the surface of the porous support. That's how.
  • the porous support is immersed in an aqueous solution containing an acid selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof, while maintaining about 25 ° C to about 200 ° C, After being left for about 1 hour to about 24 hours, the polymer electrolyte membrane for fuel cells can be formed by drying.
  • an acid aqueous solution having a concentration of about 1 M to about 30 M may be used.
  • the description of the electrospinning and heat treatment is as described above. .
  • forming a nonwoven fabric by electrospinning the composition for forming the porous support;
  • the nonwoven fabric Heat treating to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide;
  • it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of introducing a fluorine group on the surface of the porous support.
  • the adhesion between the porous support and the cation exchange resin for example, can be improved, and the wettability of the porous support to the cation exchange resin can be improved.
  • the permeation, electrical conductivity, grafting characteristics and mechanical behavior of the polymer electrolyte membrane for a fuel cell including the porous support may be improved.
  • the fluorine group may be introduced into the porous support by using fluorine and fluoride, for example, by direct fluorination or plasma deposition, thereby preparing a surface fluorinated porous support.
  • the porous support may be impregnated with a cation exchange resin to prepare a polymer electrolyte membrane for a fuel cell.
  • FIG. 2 shows a schematic structure of a fuel cell system according to an embodiment of the present invention.
  • a system for supplying fuel and an oxidant to an electric generator using a pump is illustrated.
  • the present invention is not limited thereto and may be used in a fuel cell system structure using a diffusion method without using a pump. .
  • Fuel cell system 1 is characterized in that the oxidation of the fuel At least one electricity generator 3 for generating electrical energy through reaction and reduction of oxidant, a fuel supply unit 5 for supplying fuel to the electricity generator 3, and an oxidant for the electricity generator 3 And an oxidant supply portion 7 to be supplied to the furnace.
  • the fuel supply unit 5 for supplying the fuel may include a fuel tank 9 storing fuel and a fuel pump 11 connected to the fuel tank 9.
  • the fuel pump 11 functions to discharge fuel stored in the fuel tank 9 by a predetermined pumping force.
  • the oxidant supply unit 7 for supplying the oxidant to the electricity generating unit 3 is provided with at least one oxidant pump 13 which sucks the oxidant with a predetermined pumping force.
  • the electric generator 3 is composed of a membrane-electrode assembly 17 for oxidizing and reducing a fuel and an oxidant and a separator 19, 19 'for supplying fuel and an oxidant to both sides of the membrane-electrode assembly. At least one of these electricity generating units 17 constitutes a stack 15.
  • DMF Dimethylformamide
  • the composition for forming the porous support was + 10kV to the cylinder part and _4kV to the drum part using a drum-type electrospinning equipment ESR200RD NanoNC (manufactured by NanoNC)), radiating interval 15 cm, flow rate 0.1 ⁇ / min, and electrospinning under the condition of a drum speed of 50 rpm to prepare a nonwoven fabric comprising fibers.
  • ESR200RD NanoNC manufactured by NanoNC
  • the nonwoven fabric prepared above was heat-treated at 300 ° C. for 1 hour, and then heat-treated at 40 CTC for 1 hour, and then slowly cooled to room temperature to prepare a porous support including polybenzoxazole.
  • the temperature increase rate at the time of the said heat processing was 5 degrees C / min.
  • '' capillary flow porometer equipment CFP-1500-AE (Po r ou s
  • the porosity of the porous support measured using Materials Corp. was 91%.
  • the porous support had a thickness of 40 ⁇ .
  • porous support was dissolved in 10 g of sulfonated-poly (arylene ether sulfone: s-PAES) in 90 g of ⁇ , ⁇ -dimethylacetamide (DMAc) for 1 hour. After immersion, the polymer electrolyte membrane for a fuel cell containing polybenzoxazole was prepared by slowly drying in an oven. The thermal conversion was 46 mol3 ⁇ 4>.
  • the prepared polymer had a free volume of 0.193 and an interplanar distance of 558 pm.
  • the density of the polymer is related to the free volume.
  • the film density was measured by a buoyancy method using a Sartorius LA 310S analytical balance according to Equation 1 below.
  • V is the specific volume of the polymer
  • Vw is the specific Van der Waals volume.
  • the interplanar distance was calculated according to the Bragg's equation from the X-ray diffraction pattern results.
  • the full width at half maximum (FWHM) by positron annihilation lifetime spectroscopy (PALS) was 16.1 pm.
  • PALS measurements were performed on nitrogen at ambient temperature using an automated EG & G Ortec fast-fast coincidence spectrometer.
  • the time resolution of the system was 240 ps.
  • the polymer film on either side of the 22 Na-Ti foil source (22 Na_Ti foil source) 1 ⁇ Installed in thickness. There was no source correction for Ti foil (thickness 2. mi).
  • Each spectrum consists of about 10 million integrated counts and is made up of a sum of three decaying exponent ials or a continuous distribution.
  • the PALS data were obtained by investigating positrons generated from 22 Na isotopes using the time difference between 1.27 MeV generated at the time of generation and Y l , 0.511MeV generated at the time of extinction, ⁇ 2 , ⁇ 3 , and the like.
  • ⁇ 2 , ⁇ 3 0.511MeV generated at the time of extinction
  • the pore size was calculated using Equation 3 below using the extinction time of two ⁇ signals of 0.511 MeV.
  • T 0 - Ps is the extinction time of the positron
  • R is the pore size
  • a polymer electrolyte membrane for a fuel cell comprising a polybenzoxazole including a repeating unit represented by Chemical Formula 51 in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 400 ° C. for 2 hours. Prepared. The thermal conversion was 61%.
  • the FT-IR analysis confirmed the bands of 1,553 ⁇ 1 , 1,480 cnf ON) and 1,058 cm _1 (C-0), which were characteristic bands of polybanozoxazole, which did not exist in polyhydroxyimide.
  • the prepared polymer had a free volume of 0.200 and an interplanar distance of 564.4 pm.
  • FWHM full width at half maximum
  • a polymer electrolyte membrane for a fuel cell including a polybenzoxazolol including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 400 ° C. for 3 hours. Thermal conversion was 69%.
  • the FT-IR analysis revealed a band of 1,553 cm “1 , 1,480 cm-ON) and 1,058 cm ' HC-0), a polybenzoxazole characteristic band that did not exist in polyhydroxyimide.
  • the free volume of was 0.204 and the distance between planes was 567.6 pm.
  • FWHM full width at half maximum
  • Example 4 Preparation of Polymer Electrolyte Membrane for Fuel Cell
  • a polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 425 ° C. for 1 hour. The thermal conversion was 80%.
  • FWHM full width at half maximum
  • a polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 425 ° C. for 2 hours. Thermal conversion was 88%.
  • the free volume of the polymer was 0.214 and the interplanar distance was 575.2 pm.
  • a polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat-treated at 425 ° C. for 3 hours. Thermal conversion was 91%.
  • the free volume of the polymer was 0.215 and the interplanar distance was 576.4 pm.
  • FWHM full width at half maximum
  • a polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 450 ° C. for 1 hour. Thermal conversion was 95%.
  • the prepared polymer had a free volume of 0.217 and an interplanar distance of 578 pm.
  • FWHM full width at half maximum
  • a polymer electrolyte membrane for a fuel cell including a polymer including a polyimide including a repeating unit represented by the following Chemical Formula 52 was prepared from a polyamic acid as represented by the following formula (2).
  • the nonwoven fabric prepared above was heat-treated at 350 ° C. for 1 hour, and then slowly reacted to room temperature to prepare a porous support including polyimide.
  • the temperature increase rate during the heat treatment was 5 ° C / min.
  • the porosity of the porous support measured using a capillary flow porometer device was 653 ⁇ 4>.
  • the porous support had a thickness of 43 / m.
  • the porous support prepared in Examples 1 to 7 and Comparative Example 1 was photographed using a general camera. Among them, a photo of the porous support prepared in Example 4 is shown in FIG.
  • the fuel cell polymer electrolyte membranes prepared in Examples 1 to 7 and Comparative Example 1 were photographed using a general camera. Among these, the photo of the fuel cell polymer electrolyte membrane prepared in Example 4 is shown in FIG.
  • the porous support prepared in Example 4 is effectively wetted with bivalent silver exchange resin to change transparent.
  • the porous support prepared in Example 4 can be confirmed that the cation exchange resin is well impregnated with excellent wettability to the cation exchange resin.
  • Example 4 After cutting the polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 to 1 cm X 4 cm size, i mpedance / ga i n phase analyzer (Solartron 1260) and electrochemical interace (Solartron 1287, Farnborough, Hampshire, UK) was fixed to each of the polymer electrolyte membrane for the fuel cell, the R value was measured, the proton conductivity was calculated through the following equation (4). Among them, the results for Example 4 are shown in Table 1 below. Indicated.
  • W s width of polymer electrolyte membrane for fuel cell (1 cm)
  • the polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 was cut to a size of 4 cm X 4 cm.
  • each of the fuel cell polymer electrolyte membranes was immersed in distilled water at 8 ( rc for 24 hours. Then, each of the fuel cell polymer electrolyte membranes was taken out to measure the weight (W w ) of the fuel cell polymer electrolyte membranes.
  • the moisture absorption rate was calculated by substituting the measured weight value into the following Equation 5.
  • W d dry weight of the polymer electrolyte membrane for a fuel cell
  • W w Weight after hydration of the polymer electrolyte membrane for fuel cell
  • the polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 was cut to a size of 4 cm X 4 cm. Each polymer electrolyte membrane for fuel cells was then dried in a vacuum oven of lOCrC for 24 hours. In the dry state, the length and width of each of the polymer electrolyte membranes for fuel cells were measured.
  • each of the fuel cell polymer electrolyte membranes was immersed in 8 ( rc distilled water and left for one day. Each of the hydrated fuel cell polymer electrolyte membranes was taken out to measure the length and width of the fuel cell polymer electrolyte membranes.
  • the length and width of the polymer electrolyte membrane for fuel cells may be reduced by using a video microscope system ICS-305B (manufactured by Sometech) to reduce errors due to rapid desorption of water molecules from the hydrated fuel cell polymer electrolyte membrane. Measured.
  • the dimensional stability was evaluated by substituting the measured length and width of the fuel cell polymer electrolyte membrane into the following equation (6). Dimensional stability was evaluated here using the length of the polymer electrolyte membrane for fuel cells.
  • D dry Dimension (length or width) of polymer electrolyte membrane for dry fuel cell
  • D wet Dimension (length or width) of polymer electrolyte membrane for hydrated fuel cell [Table 1]
  • the fuel cell polymer electrolyte membrane prepared in Example 4 has a superior proton conductivity than the fuel cell polymer electrolyte membrane prepared in Comparative Example 1, and at the same time exhibits low water absorption and high dimensional stability. have.
  • 244 porous support
  • 242 cation exchange water 1: fuel cell system
  • 3 electricity generator
  • 5 fuel supply
  • 7 oxidant supply
  • 9 fuel tank
  • 11 fuel pump
  • 17 Membrane-electrode assembly
  • 19 ′ Separator 15 : Stack

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Abstract

Provided is a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide. The porous support has micro-pores as well as pico-pores present in the polymer derived from the polyamic acid, or pico-pores present in the polymer derived from the polyimide. The polyamic acid and the polyimide comprise repeating units produced from an aromatic diamine and dianhydride containing at least one functional group which is present at the ortho position with respect to an amine group.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
다공성 지지체 및 이를 포함하는 연료 전지용 고분자 전해질 막 【기술분야】  Porous support and polymer electrolyte membrane for fuel cell comprising same
본 기재는 다공성 지지체 및 이를 포함하는 연료 전지용 고분자 전해질 막에 관한 것이다.  The present invention relates to a porous support and a polymer electrolyte membrane for a fuel cell comprising the same.
【배경기술】  Background Art
연료 전지 (fuel cell)는 메탄올, 에탄올， 천연기체와 같은 탄화수소 계열의 물질 내에 함유되어 있는 수소와 산소의 화학 반웅 에너지를 직접 전기 에너지로 변환시키는 발전 시스템이다. 이러한 연료 전지는 화석 에너지를 대체할 수 있는 청정 에너지원으로 주목받고 있다.  A fuel cell is a power generation system that directly converts the chemical reaction energy of hydrogen and oxygen contained in hydrocarbon-based materials such as methanol, ethanol and natural gas into electrical energy. Such fuel cells are drawing attention as a clean energy source that can replace fossil energy.
연료 전지의 대표적인 예로는 고분자 '전해질형 연료 전지 (polymer electrolyte membrane fuel cell , PEMFC) , 직접 산화형 연료 전지 (direct oxidation fuel cell)를 들 수 있다. 상기 직접 산화형 연료 전지에서 연료로 메탄을을 사용하는 경우는 직접 메탄올 연료 전지 (direct methanol fuel cell, DMFC)라 한다. Typical examples of fuel cells include a polymer, electrolyte fuel cells (polymer electrolyte membrane fuel cell, PEMFC ), direct oxidation fuel cell (direct oxidation fuel cell). When methane is used as the fuel in the direct oxidation fuel cell, it is called a direct methanol fuel cell (DMFC).
이러한 연료 전지 시스템에 있어서, 전기를 실질적으로 발생시키는 스택은 막—전극 어셈브리 (membrane— electrode assembly, MEA)와 세퍼레이터 (separator)로 이루어진 단위 셀이 수 개 내지 수 십개로 적층된 구조를 가진다. 상기 막 -전극 어셈블리는 수소 이온 전도성을 갖는 양이온 교환수지를 포함하는 고분자 전해질 막을 사이에 두고 애노드와 캐소드가 대향하여 위치하는 구조를 가진다 . In such a fuel cell system, the stack that substantially generates electricity has a structure in which several to tens of unit cells including a membrane-electrode assembly (MEA) and a separator are stacked. The membrane-electrode assembly includes an anode and a cathode interposed between a polymer electrolyte membrane including a cation exchange resin having hydrogen ion conductivity. It has a structure that is located opposite.
연료 전지에서 전기를 발생시키는 원리는 연료가 연료극인 애노드로 공급되어 애노드의 촉매에 흡착되고， 산화 반응에 의하여 연료가 이온화되어 전자가 발생하며， 이때 발생된 전자는 외부 회로에 따라 산화극인 캐소드에 도달하며， 수소 이온은 고분자 전해질 막을 통과하여 캐소드로 전달된다. 캐소드로 산화제가 공급되고, 이 산화제, 수소 이온 및 전자가 캐소드의 촉매 상에서 반웅하여 물을 생성하면서 전기를 발생시키게 된다.  The principle of generating electricity in a fuel cell is that fuel is supplied to an anode, which is a fuel electrode, adsorbed to a catalyst of the anode, and fuel is ionized by an oxidation reaction to generate electrons. In turn, hydrogen ions pass through the polymer electrolyte membrane and are delivered to the cathode. An oxidant is supplied to the cathode, and the oxidant, hydrogen ions and electrons react on the catalyst of the cathode to generate electricity while producing water.
현재 상기 고분자 전해질 막의 수소 이온 전도성， 기계적 물성， 치수 안정성 및 내화학성을 개선하기 위한 연구가 활발히 이루어지고 있다.  Currently, researches are being actively conducted to improve the hydrogen ion conductivity, mechanical properties, dimensional stability, and chemical resistance of the polymer electrolyte membrane.
【발명의 상세한 설명】  [Detailed Description of the Invention]
【기술적 과제】  [Technical problem]
기계적 물성， 치수 안정성 및 내화학성이 우수한 다공성 지지체， 그리고 상기 다공성 지지체를 포함하며， 수소 이온 전도성, 기계적 물성， 치수 안정성 및 내화학성이 우수하고 연료 전지의 출력 밀도를 향상시킬 수 있는 연료 전지용 고분자 전해질 막을 제공하며， 상기 다공성 지지체 및 상기 연료 전지용 고분자 전해질 막의 제조방법을 제공한다.  A porous support having excellent mechanical properties, dimensional stability, and chemical resistance, and a porous electrolyte including the porous support, and having excellent hydrogen ion conductivity, mechanical properties, dimensional stability, and chemical resistance, and capable of improving output density of a fuel cell. A membrane is provided, and a method of manufacturing the porous support and the polymer electrolyte membrane for the fuel cell is provided.
상기 다공성 지지체 및 상기 연료 전지용 고분자 전해질 막을 포함하는 막 -전극 어셈블리를 제공하고， 상기 막 -전극 어셈블리를 포함하는 연료전지 시스템을 제공한다.  It provides a membrane-electrode assembly comprising the porous support and the polymer electrolyte membrane for the fuel cell, and provides a fuel cell system comprising the membrane-electrode assembly.
【기술적 해결방법】 본 발명의 일 측면에 따르면， 다공성 지지체는 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함한다 . 상기 다공성 지지체는 미세기공， 그리고 상기 폴리아믹산으로부터 유도된 고분자에 존재하는 피코기공 또는 상기 폴리이미드로부터 유도된 고분자에 존재하는 피코기공을 가지며， 상기 폴리아믹산 및 상기 폴리이미드는 아민기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 포함한다. 상기 작용기는 OH, SH 또는 N¾를 포함할 수 있다. Technical Solution According to one aspect of the invention, the porous support comprises a polymer derived from polyamic acid or a polymer derived from polyimide. The porous support has micropores and picopores present in the polymer derived from the polyamic acid or picopores present in the polymer derived from the polyimide, wherein the polyamic acid and the polyimide have an ortho position relative to an amine group. Repeating units prepared from aromatic diamines and dianhydrides comprising at least one functional group present in. The functional group may comprise OH, SH or N¾.
상기 고분자는 상기 폴리아믹산 또는 상기 폴리이미드로부터 열전환되어 유도되는 것이고， 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량 (100몰 ¾；)에 대하여 열전환되는 반복단위의 비율 (열전환율)은 약 10몰% 내지 약 100몰%일 수 있다.  The polymer is induced by thermal conversion from the polyamic acid or the polyimide, and the ratio (thermal conversion rate) of the thermally converted unit with respect to the total amount (100 mol ¾;) of the repeating units included in the polyamic acid or the polyimide ) May be about 10 mol% to about 100 mol%.
상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 약 0.18 내지 약 0.40의 자유 체적도 (FFV)를 가질 수 있다.  The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume degree (FFV) of about 0.18 to about 0.40.
또한 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 XRD 측정에 의한 면간 거리가 약 550 pm 내지 약 800 pm의 범위일 수 있다.  In addition, the polymer derived from the polyamic acid and the polymer derived from the polyimide may have an interplanar distance by XRD measurement in the range of about 550 pm to about 800 pm.
상기 피코기공은 2개 이상이 서로 연결되어 모래시계 모양 (hourglass shaped)을 형성할 수 있다.  Two or more picopores may be connected to each other to form an hourglass shape.
또한 상기 피코기공은 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)이 약 10 pm 내지 약 40 pm의 범위일 수 있다. 상기 다공성 지지체는 지지체 총 부피에 대하여 약 10 부피 % 내지 약 95 부피 %의 기공도를 가질 수 있다. 또한 상기 다공성 지지체는 약 10 iM 내지 약 200 의 두께로 형성될 수 있다. In addition, the picopores are positron decay time spectroscopy (positron Full width at half maximum (FWHM) by annihilation lifetime spectroscopy (PALS) measurement may range from about 10 pm to about 40 pm. The porous support may have a porosity of about 10% by volume to about 95% by volume relative to the total volume of the support. In addition, the porous support may be formed to a thickness of about 10 iM to about 200.
상기 폴리아믹산은 하기 화학식 1 내지 4로 표시되는 반복단위를 포함하는 폴리아믹산, 하기 화학식 5 내지 8로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있고， 상기 폴리이미드는 하기 화학식 19 내지 22로 표시되는 반복단위를 포함하는 폴리이미드， 하기 화학식 23 내지 26으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있다.  The polyamic acid is a polyamic acid including a repeating unit represented by the following Chemical Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by the following Chemical Formulas 5 to 8, copolymers thereof, and blends thereof It may be selected, the polyimide is a polyimide comprising a repeating unit represented by the following formula 19 to 22, a polyimide copolymer comprising a repeating unit represented by the following formula 23 to 26, copolymers thereof and their It can be selected from the group consisting of blends.
[화학식 1]
Figure imgf000006_0001
[Formula 1]
Figure imgf000006_0001
[화학식 2]
Figure imgf000006_0002
[화학식 3]
Figure imgf000007_0001
[Formula 2]
Figure imgf000006_0002
[Formula 3]
Figure imgf000007_0001
[화학식 4]
Figure imgf000007_0002
[Formula 4]
Figure imgf000007_0002
[화학식 5]
Figure imgf000007_0003
[Formula 5]
Figure imgf000007_0003
[화학식 6]
Figure imgf000007_0004
[Formula 6]
Figure imgf000007_0004
[화학식 7]
Figure imgf000007_0005
[Formula 7]
Figure imgf000007_0005
[화학식 8]
Figure imgf000007_0006
[화학식 19]
Figure imgf000008_0001
[Formula 8]
Figure imgf000007_0006
[Formula 19]
Figure imgf000008_0001
[화학식 20]
Figure imgf000008_0002
[Formula 20]
Figure imgf000008_0002
[화학식 21]
Figure imgf000008_0003
[Formula 21]
Figure imgf000008_0003
[화학식 22]
Figure imgf000008_0004
[Formula 22]
Figure imgf000008_0004
[화학식 23]
Figure imgf000008_0005
[화학식 24]
Figure imgf000009_0001
[Formula 23]
Figure imgf000008_0005
[Formula 24]
Figure imgf000009_0001
[화학식 25]
Figure imgf000009_0002
[Formula 25]
Figure imgf000009_0002
[화학식 26]
Figure imgf000009_0003
[Formula 26]
Figure imgf000009_0003
상기 화학식 1 내지 8 및 화학식 19 내지 26에서,  In Chemical Formulas 1 to 8 and 19 to 26,
A 은 치환 또는 비치환된 4가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 4가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0， S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (CH2)P (여기서, l≤p≤10), (CF2)q (여기서， l≤q≤10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고,A is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6 to C24 arylene group and a substituted or unsubstituted tetravalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more are joined to each other to form a condensed ring; Two or more single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P (where l≤p≤10) , (CF 2 ) q (wherein l ≦ q ≦ 10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH,
Ar2는 치환 또는 비치환된 2가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 2가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고， 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0， S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (C¾)p (여기서， 1<ρ<10), (CF2)q (여기서, l<q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고，Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more Joined to form a condensed ring; At least two single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (C¾) p (where 1 <ρ <10), (CF 2 ) q where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH,
Q는 0， S, C(=0), CH(OH) , S(=0)2, Si(CH3)2> (C¾)p (여기서， 1<ρ<10), (CF2)q (여기서， l<q<10), C(C¾)2, C(CF3)2, CO0)NH, C(CH3)(CF3), 또는 치환 또는 비치환된 페닐렌기 (여기서 치환된 페닐렌기는 C1 내지 C6 알킬기 또는 C1 내지 C6 할로알킬기로 치환된다)이고， 이때 상기 Q는 양쪽 방향족 고리와 m-m, m-p, p-m, 또는 p-p 위치로 연결되고， γ는 각각의 반복단위에서 동일하거나 서로 상이하며， 각각 독립적으로 OH, SH또는 NH2이고， Q is 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2> (C¾) p (where 1 <ρ <10), (CF 2 ) q Wherein l <q <10), C (C¾) 2 , C (CF 3 ) 2 , CO0) NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group (where substituted phenyl The ylene group is substituted with a C1 to C6 alkyl group or a C1 to C6 haloalkyl group, wherein Q is connected to both aromatic rings with the mm, mp, pm, or pp position, and γ is the same or different from each other at each repeating unit. Each independently OH, SH or NH 2 ,
n은 20≤n≤200을 만족하는 정수이고，  n is an integer satisfying 20≤n≤200,
m은 10≤m≤400을 만족하는 정수이고，  m is an integer satisfying 10≤m≤400,
1은 10≤1≤400을 만족하는 정수이다.  1 is an integer satisfying 10≤1≤400.
상기 화학식 1 내지 4로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체에서의 각 반복단위 사이의 몰비， 상기 화학식 5 내지 8에서 m:l의 몰비， 상기 화학식 19 내지 22로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체에서의 각 반복단위 사이의 몰비 또는 상기 화학식 23 내지 26에서 m:l의 몰비는 약 0.1:9.9 내지 약 9.9:0.1일 수 있다.  The molar ratio between each repeating unit in the copolymer of the polyamic acid containing a repeating unit represented by the formula 1 to 4, the molar ratio of m: l in the formula 5 to 8, the repeating unit represented by the formula 19 to 22 The molar ratio between each repeating unit in the copolymer of the polyimide including or the molar ratio of m: l in the above formulas 23 to 26 may be about 0.1: 9.9 to about 9.9: 0.1.
상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 하기 화학식 37 내지 50 중 어느 하나로 표시되는 반복단위를 포함하는 고분자 또는 이들의 공중합체를 포함할 수 있다. [화학식 37]
Figure imgf000011_0001
The polymer derived from the polyamic acid and the polymer derived from the polyimide may include a polymer including a repeating unit represented by any one of Formulas 37 to 50 or a copolymer thereof. [Formula 37]
Figure imgf000011_0001
[화학식 38]
Figure imgf000011_0002
[Formula 38]
Figure imgf000011_0002
[화학식 39]
Figure imgf000011_0003
[Formula 39]
Figure imgf000011_0003
[화학식 40]
Figure imgf000011_0004
[Formula 40]
Figure imgf000011_0004
[화학식 41]
Figure imgf000011_0005
[Formula 41]
Figure imgf000011_0005
[화학식 42]
Figure imgf000011_0006
[화학식 43]
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000012_0004
Figure imgf000012_0005
[Formula 42]
Figure imgf000011_0006
[Formula 43]
Figure imgf000012_0001
Figure imgf000012_0002
Figure imgf000012_0003
Figure imgf000012_0004
Figure imgf000012_0005
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0003
Figure imgf000013_0003
상기 화학식 37 내지 50에서，  In Chemical Formulas 37 to 50,
An, Ar2l Q, n, m 및 1은 각각 상기 화학식 1 내지 8 및 화학식 19 내지 26의 An, Ar2, Q, n, m 및 1에서 설명된 바와 같고， An, Ar 2l Q, n, m and 1 are as described in An, Ar 2 , Q, n, m and 1 of Formulas 1 to 8 and 19 to 26, respectively,
Ai 는 치환 또는 비치환된 2가의 C6 내지 C24 아릴렌기 및 치환 또는 비치환된 2가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0， S, C(=0), CH(OH), S(=0)2, Si(C¾)2, (C¾)p (여기서， 1<ρ≤10), (CF2)q (여기서, l≤q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고， Y' '는 0또는 S 이다. Ai is an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more are joined to each other to form a condensed ring; At least two single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (C¾) 2 , (C¾) p (where 1 <ρ≤10), ( CF 2 ) q (where connected by a functional group of l ≦ q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH, and Y ′ ′ is 0 or S.
상기 화학식 1 내지 8， 화학식 19 내지 26 및 화학식 37 내지 50에서 八！^의 예는 하기 식으로 표시된 것 중에서 선택될 수 있다. In Formulas 1 to 8, Formulas 19 to 26, and Formulas 37 to 50, examples of O! ^ May be selected from the following formulas.
Figure imgf000015_0001
상기 식에서，
Figure imgf000015_0001
In the above formula,
¾, X2, ¾ 및 X4는 동일하거나 서로 상이하며 각각 독립적으로 0， S,¾, X 2 , ¾ and X 4 are the same or different from each other and each independently 0, S,
C(=0), CH(OH), S(-0)2, Si(CH3)2l (C¾)p (여기서， 1<ρ<10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2, 또는 CO0)NH이고， C (= 0), CH (OH), S (-0) 2 , Si (CH 3 ) 2 l (C¾) p (where 1 <ρ <10), (CF 2 ) q (where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 , or CO 0) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는 c(=o)이고, Wi and W 2 are the same or different from each other and are each independently 0, S, or c (= o),
^은 0， S, CR100Rioi 또는 NR102이고, 여기서 Rioo, Rioi 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고， ^ Is 0, S, CR 100 Rioi or NR 102 , wherein Rioo, Rioi and R 102 are the same or different from each other and are each independently hydrogen or a C1 to C5 alkyl group,
¾ 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CR103(여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고, ¾ and ¾ are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time is not CR 103 ;
Ri 내지 2는 동일하거나 서로 상이하며 각각 독립적으로 수소， 또는 치환 또는 비치환된 C1 내지 C10 지방족 유기기이고，  Ri to 2 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
kl 내지 k3, k8 내지 kl4, k24 및 k25는 0 내지 2의 정수이고， k5, kl5, kl6, kl9, k21 및 k23은 0또는 1의 정수이고，  kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
k4, k6, k7, kl7, kl8, k20, k22, k26 내지 k29, k31, k34 내지 k36, k38, k39 및 k42는 0 내지 3의 정수이고，  k4, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers of 0 to 3,
k30, k37, k40 및 k41은 0 내지 4의 정수이고，  k30, k37, k40 and k41 are integers from 0 to 4,
k32 및 k33은 0 내지 5의 정수이다.  k32 and k33 are integers of 0-5.
상기 화학식 1 내지 8， 화학식 19 내지 26 및 화학식 37 내지 50에서 : 八！^의 구체적인 예는 하기 식으로 표시된 것 증에서 선택될 수 있다.
Figure imgf000017_0001
In the above Chemical Formulas 1 to 8 and Chemical Formulas 19 to 26) and (37 to 50:!八Specific examples of ^ may be selected from one of the following Chemical Formulas increased.
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000018_0002
Figure imgf000019_0001
Figure imgf000019_0001
상기 식에서，  In the above formula,
및 X4는 동일하거나 서로 상이하며 각각 독립적으로 0, S, C(=0), CH(OH) , S(=0)2, Si(CH3)2, (CH2)P (여기서， l<p<10), (CF2)q (여기서 , l<q<10), C(C¾)2, C(CF3)2) 또는 (XO)NH이고， And X 4 are the same or different from each other and each independently 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P (where l <p <10), (CF 2 ) q (where, l < q <10), C (C¾) 2 , C (CF 3 ) 2) or (XO) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0, S, 또는 c(=o)이고， Wi and W 2 are the same or different from each other and are each independently 0, S, or c (= o),
^은 0， S, CRiooRioi 또는 NR102이고, 여기서 R100, R101 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고, ^ Is 0, S, CRiooRioi or NR 102 , wherein R 100 , R 101 and R 102 are the same or different from each other and are each independently hydrogen or a C1 to C5 alkyl group,
Z2 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CR103(여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고, Z 2 and ¾ are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time is not CR 103 ;
R43 내지 R89는 동일하거나 서로 상이하며 각각 독립적으로 수소， 치환 또는 비치환된 C1 내지 C10 지방족 유기기， 또는 금속 술포네이트기이고, R 43 to R 89 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group,
k43, k49, k64 내지 k68, k72 내지 k76, 및 k82 내지 k89는 0 내지 4의 정수이고，  k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
k44 내지 k46, k48, k51, k54, k55, k57, k58, k61 및 k63은 0 내지 3의 정수이고,  k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 및 k81은 0 내지 2의 정수이고，  k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are integers from 0 to 2,
k50은 0 또는 1의 정수이고，  k50 is an integer of 0 or 1,
k69, k71, k77 및 k79는 0 내지 5의 정수이다. 상기 화학식 1 내지 8, 화학식 19 내지 26 및 화학식 37 내지 50에서， Ar2의 구체적인 예는 하기 식으로 표시된 것 중에서 선택될 수 있다. k69, k71, k77 and k79 are integers of 0-5. In Formulas 1 to 8, 19 to 26, and 37 to 50, specific examples of Ar 2 may be selected from those represented by the following formulas.
oz oz
Figure imgf000022_0001
Figure imgf000022_0001
89£000/llOZ¾¾/13d
Figure imgf000023_0001
89 £ 000 / llOZ¾¾ / 13d
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0001
상기 식에서， M 은 금속이고， 상기 금속은 나트륨， 칼륨， 리튬, 이들의 합금 또는 이들의 조합일 수 있다.  Wherein M is a metal, and the metal may be sodium, potassium, lithium, alloys thereof, or a combination thereof.
상기 화학식 1 내지 8, 화학식 19 내지 26 및 화학식 37 내지 50에서， Q의 예는 C(C¾)2, C(CF3)2, 0， S, S(=0)2 또는 C(=0) 중에서 선택될 수 있다. 상기 화학식 37 내지 50에서， AiV의 예 및 구체적인 예는 상기 화학식 1 내지 8， 화학식 19 내지 26 및 화학식 37 내지 50의 Ar2의 예 및 구체적인 예로 언급된 것과 동일하다. In Formulas 1 to 8, 19 to 26, and 37 to 50, examples of Q include C (C¾) 2 , C (CF 3 ) 2 , 0, S, S (= 0) 2 or C (= 0) Can be selected from. In Formulas 37 to 50, examples and specific examples of AiV are the same as those mentioned for the examples and specific examples of Ar 2 of Formulas 1 to 8, 19 to 26, and 37 to 50.
상기 화학식 1 내지 8 및 화학식 19 내지 26에서， A 은 하기 화학식 Al 내지 A8 중 어느 하나로 표시되는 작용기일 수 있고, Ar2는 하기 화학식In Formulas 1 to 8 and 19 to 26, A represents the following formula It may be a functional group represented by any one of Al to A8, Ar 2 is represented by the following formula
B1 내지 B11 중 어느 하나로 표시되는 작용기일 수 있고， Q는 C(CF3)2일 수 있다. It may be a functional group represented by any one of B1 to B11, Q may be C (CF 3 ) 2 .
[화학식 A1] [화학식 A2] [화학식 A3]  [Formula A1] [Formula A2] [Formula A3]
Figure imgf000025_0001
Figure imgf000025_0001
[화학식 A5] [화학식 A6]  Formula A5 Formula A6
Figure imgf000025_0002
Figure imgf000025_0002
[화학식 A7]
Figure imgf000025_0003
Figure imgf000025_0004
Figure imgf000025_0005
[화학식 B4] [화학식 B5] [화학식 B6] [화학식 B7] [Formula A7]
Figure imgf000025_0003
Figure imgf000025_0004
Figure imgf000025_0005
[Formula B4] [Formula B5] [Formula B6] [Formula B7]
Figure imgf000026_0001
Figure imgf000026_0001
[화학식 B8] [화학식 B9]
Figure imgf000026_0002
Formula B8 Formula B9
Figure imgf000026_0002
[화학식 BIO] [화학식 Bll] [Formula BIO] [Formula Bll]
Figure imgf000026_0003
Figure imgf000026_0003
상기 화학식 37 내지 50에서， Arr^ 상기 화학식 A1 내지 A8 중 어느 하나로 표시되는 작용기일 수 있고， An'는 하기 화학식 C1 내지 C8 중 어느 하나로 표시되는 작용기일 수 있고， Ar2는 상기 화학식 B1 내지 B11 중 어느 하나로 표시되는 작용기일 수 있고， Q는 C(CF3)2일 수 있다. In Formulas 37 to 50, Arr ^ may be a functional group represented by any one of Formulas A1 to A8, An 'may be a functional group represented by any one of Formulas C1 to C8, and Ar 2 may be represented by Formulas B1 to B11 It may be a functional group represented by any one of, Q may be C (CF 3 ) 2 .
[화학식 C1] [화학식 C2] [화학식 C3]  [Formula C1] [Formula C2] [Formula C3]
Figure imgf000026_0004
[화학식 C4] [화학식 C5] [화학식 C6]
Figure imgf000026_0004
[Formula C4] [Formula C5] [Formula C6]
Figure imgf000027_0001
Figure imgf000027_0001
상기 다공성 지지체는 상기 피코기공을 가지는 고분자를 포함하는 섬유를 포함하고, 상기 섬유는 랜덤하게 배열되어 있을 수 있다.  The porous support may include a fiber including a polymer having the picopores, and the fibers may be randomly arranged.
한편， 상기 다공성 지지체는 상기 피코기공을 가지는 고분자를 포함하는 섬유를 포함하고， 상기 섬유는 일방향으로 배열되어 있을 수 있다. 본 발명의 다른 일 측면에 따르면， 상기 다공성 지지체; 및 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 형성된 양이온 교환 수지를 포함하는 연료 전지용 고분자 전해질 막을 제공한다.  On the other hand, the porous support may comprise a fiber comprising a polymer having the picopores, the fibers may be arranged in one direction. According to another aspect of the invention, the porous support; And it provides a polymer electrolyte membrane for a fuel cell comprising a cation exchange resin formed on the inside, the surface, or the inside and the surface of the porous support.
상기 양이온 교환 수지는 술폰산기， 카르복실산기ᅳ 인산기， 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 양이온 교환기를 포함하는 고분자일 수 있다.  The cation exchange resin may be a polymer including a cation exchange group selected from the group consisting of sulfonic acid groups, carboxylic acid groups and phosphoric acid groups, phosphonic acid groups, and derivatives thereof.
상기 연료 전지용 고분자 전해질 막에서, 상기 다공성 지지체와 상기 양이온 교환 수지는 약 99:1 내지 약 10 :90의 중량비로 포함될 수 있다. 본 발명의 또 다른 일 측면에 따르면， 상기 다공성 지지체를 포함하고， 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 산이 도핑되어 형성된 연료 전지용 고분자 전해질 막을 제공한다. In the polymer electrolyte membrane for the fuel cell, the porous support and the Cation exchange resins may be included in a weight ratio of about 99: 1 to about 10:90. According to another aspect of the present invention, there is provided a polymer electrolyte membrane for a fuel cell including the porous support and formed by acid doping on the inside, the surface, or the inside and the surface of the porous support.
상기 도핑되는 산은 술폰산， 카르복실산， 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 것일 수 있다.  The doped acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof.
본 발명의 또 다른 일 측면에 따르면， 다공성 지지체를 포함하고， 상기 다공성 지지체의 표면에 불소기를 포함하는 연료 전지용 고분자 전해질 막을 제공한다.  According to another aspect of the present invention, there is provided a polymer electrolyte membrane for a fuel cell including a porous support and a fluorine group on the surface of the porous support.
상기 연료 전지용 고분자 전해질 막은 약 20 μη 내지 약 300 의 두께로 형성될 수 있다.  The fuel cell polymer electrolyte membrane may be formed to a thickness of about 20 μηι to about 300.
본 발명의 또 다른 일 측면에 따르면， 아민기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 가지는 폴리아믹산 또는 폴리이미드; 및 유기 용매를 포함하는 다공성 지지체 형성용 조성물을 제공한다. 상기 유기 용매는 디메틸설폭사이드; Ν-메틸 -2—피롤리돈; Ν- 메틸피를리돈; Ν,Ν-디메틸포름아미드; Ν,Ν-디메틸아세트아미드;  According to another aspect of the invention, a polyamic acid or polyimide having a repeating unit prepared from aromatic diamine and dianhydride comprising at least one functional group present in the ortho position relative to the amine group; And it provides a composition for forming a porous support comprising an organic solvent. The organic solvent is dimethyl sulfoxide; Ν-methyl-2—pyrrolidone; Ν-methylpyridone; Ν, Ν-dimethylformamide; Ν, Ν-dimethylacetamide;
부티로락톤， 사이클로핵사논, 3ᅳ핵사논， 3-헵타논 및 3-옥타논으로 이루어진 군에서 선택된 케톤; 및 이들의 조합으로 이루어진 군에서 선택되는 것이다. Ketones selected from the group consisting of butyrolactone, cyclonucleanone, 3 ′ nucleosanone, 3-heptanone and 3-octanone; And it is selected from the group consisting of a combination thereof.
상기 다공성 지지체 형성용 조성물은 다공성 지지체 형성용 조성물 총량에 대하예 상기 폴리아믹산 또는 상기 폴리이미드를 약 1 중량 ¾> 내지 약 40 중량 %， 그리고 상기 유기 용매를 약 60 중량 % 내지 약 99 중량 %로 포함할 수 있다. The composition for forming a porous support is a composition for forming a porous support For example, the polyamic acid or the polyimide may include about 1 wt% to about 40 wt% of the total amount, and about 60 wt% to about 99 wt% of the organic solvent.
상기 다공성 지지체 형성용 조성물은 물; 메탄을, 에탄을, 2-메틸- 1-부탄올, 2-메틸 -2ᅳ부탄올， 글리세롤, 에될렌글리콜， 디에틸렌글리콜 및 프로필렌글리콜로 이루어진 군에서 선택된 알코올; 아세톤 및 메틸에틸 케톤으로 이루어진 군에서 선택된 케톤; 폴리비닐알코올， 폴리아크릴산, 폴리아크릴아마이드， 폴리에틸렌글리콜， 폴리프로필렌글리콜， 키토산, 키틴， 덱스트란 및 폴리비닐피를리돈으로 이루어진 군에서 선택된 고분자 화합물; 테트라하이드로퓨란; 트리클로로에탄; 및 이들의 조합으로 이루어진 군에서 선택되는 보조제를 더 포함할 수 있다. 이 경우 상기 다공성 지지체 형성용 조성물은 상기 보조제를 포함하는 다공성 지지체 형성용 조성물 총량에 대하여， 상기 폴리아믹산 또는 상기 폴리이미드를 약 1 중량 % 내지 약 40 중량 %, 상기 유기 용매를 약 10 중량 % 내지 약 95 중량 %, 그리고 상기 보조제를 약 4 중량 % 내지 약 70 중량 %로 포함할 수 있다.  The composition for forming the porous support is water; Methane, ethane, alcohol selected from the group consisting of 2-methyl-1-butanol, 2-methyl-2-butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; Ketones selected from the group consisting of acetone and methylethyl ketone; A polymer compound selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polypropylene glycol, chitosan, chitin, dextran, and polyvinylpyridone; Tetrahydrofuran; Trichloroethane; And it may further comprise an adjuvant selected from the group consisting of a combination thereof. In this case, the composition for forming the porous support is about 1% by weight to about 40% by weight of the polyamic acid or the polyimide and about 10% by weight of the organic solvent based on the total amount of the composition for forming the porous support including the auxiliary agent. About 95% by weight, and about 4% to about 70% by weight of the adjuvant.
상기 폴리아믹산 및 상기 폴리이미드는 각각 약 10,000 g/mol 내지 약 500,000 g/m 의 중량평균 분자량 (Mw)을 가질 수 있다.  The polyamic acid and the polyimide may each have a weight average molecular weight (Mw) of about 10,000 g / mol to about 500,000 g / m.
상기 다공성 지지체 형성용 조성물은 약 0.01 Pa - s 내지 약 100 Pa · s의 점도를 가질 수 있다.  The composition for forming the porous support may have a viscosity of about 0.01 Pa-s to about 100 Pa · s.
본 발명의 또 다른 일 측면에 따르면, 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 및 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 '포함하는 다공성 지지체를 형성하는 단계를 포함하는 다공성 지지체의 제조 방법을 제공한다. According to another aspect of the invention, the step of electrospinning the composition for forming the porous support to form a nonwoven fabric; And the nonwoven fabric The heat-treated to induce from a polymer or a polyimide derived from the polyamic acid polymers provides a method for producing the porous support, comprising the step of forming a porous support comprising. "
본 발명의 또 다른 일 측면에 따르면， 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 내부， 표면， 또는 내부와 표면에 양이온 교환 수지를 형성하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법을 제공한다.  According to another aspect of the invention, the step of electrospinning the composition for forming the porous support to form a nonwoven fabric; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of forming a cation exchange resin on the inside, surface, or the inside and the surface of the porous support.
본 발명의 또 다른 일 측면에 따르면， 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 산을 도핑하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법을 제공한다.  According to another aspect of the invention, the step of electrospinning the composition for forming the porous support to form a nonwoven fabric; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of doping the acid inside, the surface, or the inside and the surface of the porous support.
상기 산은 술폰산， 카르복실산, 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 것일 수 있다.  The acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof.
본 발명의 또 다른 일 측면에 따르면， 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 표면에 불소기를 도입하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법을 제공한다. According to another aspect of the invention, the step of forming a nonwoven fabric by electrospinning the composition for forming a porous support; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And on the surface of the porous support It provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of introducing a fluorine group.
상기 전기방사는 약 1 kV 내지 약 1，000 kV의 전압을 인가하여 실시될 수 있다.  The electrospinning may be performed by applying a voltage of about 1 kV to about 1,000 kV.
상기 전기방사로 형성된 부직포는 다공성 지지체 형성용 조성물을 포함하는 섬유가 랜덤하게 배열되어 있을 수 있다.  The nonwoven fabric formed by the electrospinning may be randomly arranged fibers including the composition for forming a porous support.
한편， 상기 전기방사로 형성된 부직포는 다공성 지지체 형성용 조성물을 포함하는 섬유가 일방향으로 배열되어 있을 수 있다.  On the other hand, the non-woven fabric formed by the electrospinning may be a fiber comprising a composition for forming a porous support may be arranged in one direction.
상기 고분자는 상기 폴리아믹산 또는 상기 폴리이미드로부터 열전환되어 유도되는 것이고， 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량 (100몰 %)에 대하여， 열전환되는 반복단위의 비율 (열전환율)은 약 10몰% 내지 약 100몰 >일 수 있다.  The polymer is induced by thermal conversion from the polyamic acid or the polyimide, and with respect to the total amount (100 mol%) of the repeating units included in the polyamic acid or the polyimide, the ratio of the thermally converted units (thermal conversion rate) ) May be about 10 mole% to about 100 mole>.
상기 열처리는 약 250°C 내지 약 550°C의 온도에서 실시될 수 있으며, 약 10분 내지 약 5시간 동안 실시될 수 있다. 또한 상기 열처리시 승온속도는 약 1 °C/분 내지 약 20 °C/분일 수 있다. The heat treatment may be carried out at a temperature of about 250 ° C to about 550 ° C, may be carried out for about 10 minutes to about 5 hours. In addition, the temperature increase rate during the heat treatment may be about 1 ° C / min to about 20 ° C / min.
본 발명의 또 다른 일 측면에 따르면 서로 대향하여 위치한 애노드 및 캐소드; 그리고 상기 애노드와 상기 캐소드 사이에 위치하며 , 상기 연료 전지용 고분자 전해질 막을 포함하는 연료 전지용 막—전극 어셈블리를 제공한다.  According to another aspect of the invention the anode and the cathode located opposite each other; And a membrane-electrode assembly positioned between the anode and the cathode, the membrane comprising an electrolyte membrane for the fuel cell.
본 발명의 또 다른 일 측면에 따르면, 상기 막ᅳ전극 어셈블리 및 세퍼레이터를 하나 이상 포함하며， 연료와 산화제의 전기화학적 반웅을 통하여 전기를 발생시키는 전기 발생부; 연료를 상기 전기 발생부로 공급하는 연료 공급부; 및 산화제를 상기 전기 발생부로 공급하는 산화제 공급부를 포함하는 연료 전지 시스템을 제공한다. According to another aspect of the invention, the membrane electrode assembly and at least one separator, including the electrochemical reaction of fuel and oxidant An electricity generating unit for generating electricity through; A fuel supply unit supplying fuel to the electricity generation unit; And an oxidant supply unit supplying an oxidant to the electricity generation unit.
기타 본 발명의 측면들의 구체적인 사항은 이하의 상세한 설명에 포함되어 있다.  Other details of aspects of the invention are included in the following detailed description.
【유리한 효과】  Advantageous Effects
상기 다공성 지지체는 기계적 물성, 치수 안정성 및 내화학성이 우수하고, 상기 연료 전지용 고분자 전해질 막은 수소 이온 전도성， 기계적 물성， 치수 안정성 및 내화학성이 우수하고, 또한 연료에 대한 차단성이 우수하몌 연료 전지의 출력 밀도를 향상시킬 수 있다.  The porous support has excellent mechanical properties, dimensional stability, and chemical resistance, and the polymer electrolyte membrane for fuel cells has excellent hydrogen ion conductivity, mechanical properties, dimensional stability, and chemical resistance, and excellent fuel barrier property. The output density can be improved.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은 본 발명의 일 구현예에 따른 연료 전지용 막 -전극 어셈블리를 개략적으로 나타낸 도면이다.  1 is a view schematically showing a membrane-electrode assembly for a fuel cell according to an embodiment of the present invention.
도 2는 본 발명의 다른 일 구현예에 따른 연료 전지 시스템의 구조를 개략적으로 나타낸 도면이다.  2 is a view schematically showing the structure of a fuel cell system according to another embodiment of the present invention.
도 3은 실시예 4에서 제조한 다공성 지지체의 사진이다.  3 is a photograph of the porous support prepared in Example 4.
도 4는 실시예 4에서 제조한 연료 전지용 고분자 전해질 막의 사진이다.  4 is a photograph of a polymer electrolyte membrane for a fuel cell prepared in Example 4. FIG.
【발명의 실시를 위한 최선의 형태】  [Best form for implementation of the invention]
이하， 본 발명의 구현예를 상세히 설명하기로 한다. 다만， 이는 예시로서 제시되는 것으로， 이에 의해 본 발명이 제한되지는 않으며 본 발명은 후술할 청구항의 범주에 의해 정의될 뿐이다. Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited to this The invention is only defined by the scope of the claims which follow.
도면에서는 여러 층 및 영역을 명확하게 표현하기 위하여 두께를 확대하여 나타내었다. 도면을 사용하여 설명하는 경우 명세서 전체를 통하여 유사한 부분에 대해서는 동일한 도면 부호를 부여한다.  In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the description using the drawings, like reference numerals designate like parts throughout the specification.
본 명세서에서 별도의 정의가 없는 한, "피코기공"은 기공의 평균 직경이 수백 피코미터， 구체적으로는 약 100 pm 내지 약 1,000 pm인 기공을 의미하고， "미세기공' '은 기공의 평균 직경이 약 2 nm 내지 약 50 im, 구체적으로는 약 10 nm 내지 약 10 인 기공을 의미한다.  Unless otherwise defined herein, "picopores" refers to pores having an average diameter of pores of several hundred picometers, specifically, about 100 pm to about 1,000 pm, and "microporous pores" means the average diameter of pores. It means pores that are about 2 nm to about 50 im, specifically about 10 nm to about 10.
본 명세서에서 별도의 정의가 없는 한， "치환'' 또는 "치환된 "이란 화합물 또는 작용기 중의 수소 원자가 C1 내지 C10 알킬기 , C1 내지 C10 알콕시기, C1 내지 C10 할로알킬기 및 C1 내지 C10 할로알콕시기로 이루어진 군에서 선택되는 1종 이상의 치환기로 치환된 것을 의미하고, "헤테로 고리기 "란 0， S, N, P, Si 및 이들의 조합으로 ᅳ이루어진 군에서 선택되는 헤테로 원자를 하나의 고리 내에 1 내지 3 개 함유하는， 치환 또는 비치환된 C2 내지 C30의 사이클로알킬기， 치환 또는 비치환된 C2 내지 C30의 사이클로알케닐기， 치환 또는 비치환된 C2 내지 C30의 사이클로알키닐기， 치환 또는 비치환된 C2 내지 C30 헤테로아릴기， 치환 또는 비치환된 C2 내지 C30의 사이클로알킬렌기, 치환 또는 비치환된 C2 내지 C30의 사이클로알케닐렌기， 치환 또는 비치환된 C2 내지 C30의 사이클로알키닐렌기, 또는 치환 또는 비치환된 C2 내지 C30 헤테로아릴렌기를 의미한다. 본 명세서에서 별도의 정의가 없는 한， "지방족 유기기' '란 C1 내지 C30 알킬기， C2 내지 C30 알케닐기, 또는 C2 내지 C30 알키닐기이고， 구체적으로는 C1 내지 C15 알킬기， C2 내지 C15 알케닐기， 또는 C2 내지 C15 알키닐기이고， 더욱 구체적으로는 C1 내지 C10 알킬기， C2 내지 C10 알케닐기， 또는 C2 내지 C10 알키닐기이다. Unless otherwise defined herein, the term "substituted" or "substituted" means that the hydrogen atom in the compound or functional group consists of a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 haloalkyl group, and a C1 to C10 haloalkoxy group It means substituted by one or more substituents selected from the group, "hetero ring group" means a hetero atom selected from the group consisting of 0, S, N, P, Si and combinations thereof in one ring from 1 to 3 substituted or unsubstituted C2 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 cycloalkynyl group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 cycloalkylene group, substituted or unsubstituted C2 to C30 cycloalkenylene group, substituted or unsubstituted C2 C30 cycloalkyl and the alkynyl group means, or a substituted or unsubstituted C2 to C30 heteroarylene group ring. Unless otherwise defined herein, "aliphatic organic group" is a C1 to C30 alkyl group, C2 to C30 alkenyl group, or C2 to C30 alkynyl group, specifically, C1 to C15 alkyl group, C2 to C15 alkenyl group, Or a C2 to C15 alkynyl group, more specifically a C1 to C10 alkyl group, a C2 to C10 alkenyl group, or a C2 to C10 alkynyl group.
본 명세서에서 별도의 정의가 없는 한， "조합 "이란 흔합 또는 공중합을 의미한다. 또한 "공중합' '이란 블록 공중합 내지 랜덤 공중합을 의미하고， "공중합체"란 블록 공중합체 내지 랜덤 공중합체를 의미한다. 도 1은 본 발명의 일 구현예에 따른 연료 전지용 막 -전극 어셈블리를 개략적으로 나타낸 도면이다.  Unless otherwise defined herein, "combination" means compatible or copolymerized. In addition, "copolymerization" "means block copolymer to random copolymer," copolymer "means block copolymer to random copolymer Figure 1 is a schematic diagram of a membrane-electrode assembly for a fuel cell according to an embodiment of the present invention It is a figure shown.
도 1을 참조하면， 연료 전지용 막 -전극 어셈블리 (20)는 애노드 (22)， 고분자 전해질 막 (24) 및 캐소드 (26)를 포함한다.  Referring to FIG. 1, the membrane-electrode assembly 20 for a fuel cell includes an anode 22, a polymer electrolyte membrane 24, and a cathode 26.
상기 애노드 (22) 및 캐소드 (26)는 전극 기재와 상기 전극 기재에 형성된 촉매층을 포함한다.  The anode 22 and cathode 26 comprise an electrode substrate and a catalyst layer formed on the electrode substrate.
상기 촉매층이 존재함으로써, 애노드에서는 연료의 산화 반웅을 촉진시킬 수 있고, 캐소드에서는 캐소드로 공급되는 산화제, 수소 이온 및 전자의 반웅을 촉진시킬 수 있어， 연료 전지의 효율을 개선할 수 있다.  By the presence of the catalyst layer, the reaction of the fuel can be promoted at the anode, and the reaction of the oxidant, hydrogen ions and electrons supplied to the cathode can be promoted at the cathode, thereby improving the efficiency of the fuel cell.
상기 촉매층에 포함되는 촉매의 예로는 백금， 루테늄, 오스뮴， 백금- 루테늄 합금， 백금-오스뮴 합금, 백금-팔라듐 합금， 백금 -M 합금 (여기서, M은 갈륨 (Ga), 티타늄 (Ti), 바나듐 (V), 크름 (Cr), 망간 (Mn), 철 (Fe), 코발트 (Co), 니켈 (Ni), 구리 (Cu), 아연 (Zn), 주석 (Sn), 몰리브덴 (Mo), 텅스텐 (W), 로듐 (Rh), 루테늄 (Ru) 및 이들의 조합으로 이루어진 군으로부터 선택되는 전이 금속이다) 및 이들의 조합을 들 수 있으나， 이에 한정되는 것은 아니다. 상기 촉매의 더욱 구체적인 예로는 Pt, Pt/Ru, Pt/W, Pt/Ni,Examples of the catalyst included in the catalyst layer include platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy, platinum-M alloy, where M is gallium (Ga), titanium (Ti), vanadium (V), crumb (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), tin (Sn), molybdenum (Mo), Tungsten (W), rhodium (Rh), ruthenium (Ru) and combinations thereof, and combinations thereof, but is not limited thereto. More specific examples of the catalyst include Pt, Pt / Ru, Pt / W, Pt / Ni,
Pt/Sn, Pt/Mo, Pt/Pd, Pt/Fe, Pt/Cr, Pt/Co, Pt/Ru/W, Pt/Ru/Mo, Pt/Ru/V, Pt/Fe/Co, Pt/Ru/Rh/Ni 및 Pt/Ru/Sn/W으로 이루어진 군에서 선택되는 1종 이상을 들 수 있다. Pt / Sn, Pt / Mo, Pt / Pd, Pt / Fe, Pt / Cr, Pt / Co, Pt / Ru / W, Pt / Ru / Mo, Pt / Ru / V, Pt / Fe / Co, Pt / And at least one selected from the group consisting of Ru / Rh / Ni and Pt / Ru / Sn / W.
상기 촉매는 촉매 자체 (black)로 사용할 수도 있고, 담체에 담지시켜 사용할 수도 있다. 상기 담체로는 흑연， 덴카 블랙， 케첸 블랙， 아세틸렌 블랙， 카본 나노 튜브， 카본 나노 파이버， 카본 나노 와이어， 카본 나노 볼 또는 활성 탄소 등의 탄소계 물질을 사용할 수도 있고， 또는 알루미나, 실리카， 지르코니아， 티타니아 등의 무기물 미립자를 사용할 수도 있으나, 이에 한정되는 것은 아니다.  The catalyst may be used as the catalyst itself (black) or may be supported on a carrier. As the carrier, carbonaceous materials such as graphite, denka black, ketjen black, acetylene black, carbon nanotube, carbon nanofiber, carbon nanowire, carbon nanoball, or activated carbon may be used, or alumina, silica, zirconia, Inorganic fine particles such as titania may also be used, but are not limited thereto.
상기 연료 전지용 고분자 전해질 막 (24)은 상기 애노드 (22)와 상기 캐소드 (26) 사이에 위치하며, 다공성 지지체 (244) 및 상기 다공성 지지체 내부， 표면， 또는 내부와 표면에 존재하는 양이온 교환수지 (242)를 포함한다. 상기 양이온 교환수지 (242)는 양이온 전도성， 예컨대 수소 이온 전도성을 가지는 것일 수 있다.  The polymer electrolyte membrane 24 for the fuel cell is positioned between the anode 22 and the cathode 26 and has a porous support 244 and a cation exchange resin present inside, on the surface, or within and inside the porous support ( 242). The cation exchange resin 242 may be one having a cation conductivity, for example, hydrogen ion conductivity.
상기 고분자 전해질 막 (24)은 애노드 (22) 및 캐소드 (26)를 전기적으로 분리하는 절연체이나， 전지 작동 중에는 애노드 (22)로부터 캐소드 (26)로 수소 이온을 전달하는 매개체로 작용하며， 동시에 반웅 기체 또는 액체를 분리하는 역할을 수행한다. 상기 고분자 전해질 . 막 (24)은 상기 다공성 지지체 (244)를 포함함으로써, 애노드 (22)와 캐소드 (26)를 전기적으로 분리할 수 있으며, 우수한 기계적 물성 및 치수 안정성을 가질 수 있다. 이로써 이를 포함하는 막 -전극 어셈블리는 스택 구성을 용이하게 할 수 있다. The polymer electrolyte membrane 24 is an insulator that electrically separates the anode 22 and the cathode 26, but acts as a medium for transferring hydrogen ions from the anode 22 to the cathode 26 during battery operation. It serves to separate gas or liquid. The polymer electrolyte . The membrane 24 may include the porous support 244 to electrically separate the anode 22 and the cathode 26, and may have excellent mechanical properties and dimensional stability. This allows the membrane-electrode assembly comprising it to facilitate the stack construction.
상기 다공성 지지체 (244)는 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함한다. 상기 폴리아믹산， 상기 폴리이미드 및 이들로부터 유도된 고분자에 대하여는 후술한다. 상기 다공성 지지체 (244)는 미세기공， 그리고 상기 폴리아믹산으로부터 유도된 고분자에 존재하는 피코기공 또는 상기 폴리이미드로부터 유도된 고분자에 존재하는 피코기공을 가지며, 상기 폴리아믹산 및 상기 폴리이미드는 아민기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 포함한다. 이로 인해 상기 다공성 지지체 (244)는 공극률이 높아져 효율적으로 양이온 교환수지를 공극 내에 포함할 수 있고， 이로써 양이온， 예컨대 수소 이온이 애노드 (22)로부터 캐소드 (26)로 용이하게 전달되도록 할 수 있어 연료 전지의 효율을 개선할 수 있다. 특히 상기 다공성 지지체 (244)의 피코기공에 양이온 교환수지가 흡착되거나 산이 도핑되는 경우， 흡착된 양이온 교환수지， 그리고 도핑된 산이 상기 다공성 지제체로부터 잘 분리되지 않는다. 이로 인해 양이온， 예컨대 수소 이온을 더욱 안정적으로 애노드 (22)로부터 캐소드 (26)로 전달할 수 있어, 연료 전지의 효율 및 수명 특성을 개선할 수 있다. 상기 아민기에 대하여 오르쏘 위치에 존재하는 작용기는 OH, SH 또는 NH2를 포함할 수 있다. The porous support 244 includes a polymer derived from polyamic acid or a polymer derived from polyimide. The polyamic acid, the polyimide, and the polymer derived therefrom will be described later. The porous support 244 has micropores and picopores present in the polymer derived from the polyamic acid or picopores present in the polymer derived from the polyimide, wherein the polyamic acid and the polyimide have an amine group. Repeat units made from aromatic diamines and dianhydrides comprising at least one functional group present at the ortho position. As a result, the porous support 244 may have a high porosity and thus efficiently include a cation exchange resin in the pores, thereby allowing a cation such as hydrogen ions to be easily transferred from the anode 22 to the cathode 26 so as to provide fuel. The efficiency of the battery can be improved. In particular, when the cation exchange resin is adsorbed to the picopores of the porous support 244 or the acid is doped, the adsorbed cation exchange resin and the doped acid are hardly separated from the porous support body. This makes it possible to transfer cations such as hydrogen ions from the anode 22 to the cathode 26 more stably, thereby improving the efficiency and life characteristics of the fuel cell. The functional group present in the ortho position relative to the amine group may comprise OH, SH or NH 2 .
상기 폴리아믹산 및 상기 폴리이미드는 일반적인 방법에 따라 제조할 수 있다.  The polyamic acid and the polyimide can be prepared according to a general method.
일 예로， 상기 폴리아믹산은 아민기에 대하여 오르쏘 위치에 존재하는 OH, SH 또는 NH2기를 포함하는 방향족 디아민과 테트라카르복실산 무수물을 반웅시켜 제조할 수 있고， 상기 폴리이미드는 상기 폴리아믹산을 이미드화, 예컨대 열적 용액 이미드화 또는 화학적 이미드화함으로써 제조할 수 있다. For example, the polyamic acid may be prepared by reacting an aromatic diamine and tetracarboxylic anhydride including OH, SH, or NH 2 groups present at an ortho position with respect to an amine group, and the polyimide may have already formed the polyamic acid. It can be prepared by hydration, such as thermal solution imidization or chemical imidization.
예컨대, 상기 열적 용액 이미드화는 N—메틸피롤리돈 (NMP)과 같은 유기 용매에， 벤젠， 를루엔， 자일렌， 크레졸 등의 벤젠류， 핵산, 시클로핵산 등의 지방족 유기 용매류 등을 더 첨가하여 이루어진 공비흔합물을 이용하여 이루어질 수 있다.  For example, the thermal solution imidization further comprises an organic solvent such as N-methylpyrrolidone (NMP), an aliphatic organic solvent such as benzene, toluene, xylene, cresol, etc., nucleic acid, cyclonucleic acid, or the like. It can be made using an azeotrope made by addition.
상기 폴리아믹산 및 상기 폴리이미드는 소정의 열처리에 의해 열전환되어, 피코기공을 가지며 기계적 강도가 우수하고 높은 자유 체적도를 갖는 폴리벤조옥사졸， 폴리벤조티아졸， 폴리피를론과 같은 고분자로 전환될 수 있다.  The polyamic acid and the polyimide are thermally converted by a predetermined heat treatment to polymers such as polybenzoxazole, polybenzothiazole and polypyrrole having picopores and excellent mechanical strength and high free volume. Can be switched.
구체적으로는 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량에 대하여, 열전환되는 반복단위의 비율 (열전환율)은 약 10몰% 내지 약 100몰¾> 일 수 있다. 이 경우, 다공성 지지체의 내열성 및 기계적 강도가 효과적으로 개선될 수 있고， 양이온 교환 수지에 대한 젖음성 (wettability)이 좋아져 상기 다공성 지지체와 양이온 교환 수지와의 호환성^에 ^^ ；！이 효과적으로 개선될 수 있다. 또한, 다공성 지지체와 양이온 교환 수지 간의 박리 (delamination)를 방지할 수 있고, 상기 다공성 지지체를 포함하는 연료 전지용 고분자 전해질 막의 내구성을 효과적으로 개선할 수 있다. 구체적으로는 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량에 대하여， 열전환되는 반복단위의 비율 (열전환율)은 약 40몰%내지 약 100몰 %일 수 있다. Specifically, with respect to the total amount of the repeating units included in the polyamic acid or the polyimide, the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 10 mol% to about 100 mol¾>. In this case, the heat resistance and mechanical strength of the porous support can be effectively improved, and for cation exchange resins The wettability is improved so that the compatibility between the porous support and the cation exchange resin can be improved. In addition, delamination between the porous support and the cation exchange resin can be prevented, and durability of the polymer electrolyte membrane for a fuel cell including the porous support can be effectively improved. Specifically, with respect to the total amount of the repeating units included in the polyamic acid or the polyimide, the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 40 mol% to about 100 mol%.
상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 약 0.18 내지 약 0.40의 자유 체적도 (FFV)를 가질 수 있고， XRD 측정에 의한 면간 거리 (d-spacing)가 약 550 pm 내지 약 800 pm의 범위에 있을 수 있다. 이로써 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 저분자를 용이하게 투과 내지 분리할 수 있다.  The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume (FFV) of about 0.18 to about 0.40, and the d-spacing by XRD is about 550 pm to about It can be in the range of 800 pm. As a result, the polymer derived from the polyamic acid and the polymer derived from the polyimide can easily permeate or separate low molecules.
상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 피코기공을 포함하고, 상기 피코기공은 2개 이상이 서로 연결되어 모래시계 모양 (hourglass shaped)을 형성할 수 있다. 이로써 상기 고분자는 공극률이 높아져 저분자를 효율적으로 투과시키거나 선택적으로 분리할 수 있다.  The polymer derived from the polyamic acid and the polymer derived from the polyimide may include picopores, and two or more picopores may be connected to each other to form an hourglass shape. As a result, the polymer may have high porosity, so that low molecules may be efficiently permeated or selectively separated.
또한 상기 피코기공의 평균 직경은 약 600 pm 내지 약 800 pm일 수 있으나， 이에 한정되는 것은 아니다. 상기 피코기공은 양전자 소멸시간 분광분석 (positron annihi lat ion lifetime spectroscopy, PALS) 즉정에 의한 반가폭 (full width at half maximum, FWHM)이 약 10 pm 내지 약 40 pm의 범위에 있을 수 있다. 이는 생성되는 피코기공의 크기가 상당히 균일함을 나타내는 것이다. 상기 PALS 데이터는 22Na 동위원소로부터 발생되는 양전자를 조사하여 생성시에 발생되는 1.27MeV의 와 소멸시에 생성되는 0.511MeV의 Υ ι, γ2의 시간차이 "π, τ2> τ3 등을 이용하여 얻을 —수 있다. In addition, the average diameter of the picopores may be about 600 pm to about 800 pm, but is not limited thereto. The picopores were immediately determined by positron annihilat ion lifetime spectroscopy (PALS). Full width at half maximum (FWHM) may range from about 10 pm to about 40 pm. This indicates that the size of the generated picopores is fairly uniform. The PALS data or the like 22 of 0.511MeV generated at the time of 1.27MeV Na is generated at the time of generating by irradiating the positron emitted from the isotopes decay Υ ι, time difference γ 2 "π, τ 2> τ 3 You can get it by using.
상기 다공성 지지체 (244)는 미세기공 및 피코기공을 전체적으로 균일하게 포함함으로써， 지지체 총 부피에 대하여 약 10 부피 % 내지 약 95 부피 %의 기공도를 가질 수 있고, 상기 기공에 양이온 교환수지를 포함할 수 있으므로， 양이온 전도도, 예컨대 수소 이온 전도도를 향상시켜 연료 전지의 효율을 효과적으로 개선할 수 있다.  The porous support 244 may uniformly include micropores and picopores as a whole, and may have a porosity of about 10% by volume to about 95% by volume with respect to the total volume of the support, and may include a cation exchange resin in the pores. As such, it is possible to effectively improve the efficiency of the fuel cell by improving the cation conductivity, such as hydrogen ion conductivity.
상기 다공성 지지체 (244)는 전기방사를 통해서 형성할 수 있으며， 상기 전기방사의 방법 내지 공정 조건을 조절함으로써, 상기 피코기공을 가지는 고분자를 포함하는 섬유가 상기 다공성 지지체 (244)에서 랜덤하게 배열되도록 형성할 수 있다.  The porous support 244 may be formed through electrospinning, and by adjusting the method or process conditions of the electrospinning, such that the fibers including the polymer having the picopores are randomly arranged in the porous support 244. Can be formed.
한편， 상기 다공성 지지체 (244)를 형성할 때， 상기 전기방사의 방법 내지 공정 조건을 조절함으로써, 상기 피코기공을 가지는 고분자를 포함하는 섬유가 상기 다공성 지지체 (244)에서 일방향으로 배열되도록 형성할 수도 있다. 이 경우， 섬유가 배열된 방향으로의 강도를 효과적으로 개선할 수 있다. 또한 상기 다공성 지지체 (244)를 포함하는 연료 전지용 고분자 전해질 막에서 수소 이온이 섬유가 배열된 방향을 따라 빠르게 전달되도록 할 수 있어 수소 이온 전도도를 효과적으로 개선할 수 있다. 상기 다공성 지지체 (244)는 약 10 1 내지 약 200 의 두께를 가지도록 형성할 수 있다. 다공성 지지체 (244)의 두께가 상기 범위 내인 경우， 이를 포함하는 고분자 전해질 막 (24)의 기계적 물성， 내화학성 및 치수안정성을 개선할 수 있다. 구체적으로는 상기 다공성 지지체 (244)는 약 20 내지 약 180 의 두께를 가지도록 형성할 수 있다. On the other hand, when forming the porous support 244, by controlling the method or the process conditions of the electrospinning, the fiber containing the polymer having the picopores may be formed to be arranged in one direction on the porous support 244. have. In this case, the strength in the direction in which the fibers are arranged can be effectively improved. In addition, in the polymer electrolyte membrane for a fuel cell including the porous support 244, hydrogen ions are rapidly formed along the direction in which the fibers are arranged. Can be delivered to effectively improve hydrogen ion conductivity. The porous support 244 may be formed to have a thickness of about 10 1 to about 200. When the thickness of the porous support 244 is in the above range, it is possible to improve the mechanical properties, chemical resistance and dimensional stability of the polymer electrolyte membrane 24 including the same. Specifically, the porous support 244 may be formed to have a thickness of about 20 to about 180.
또한 상기 연료 전지용 고분자 전해질 막 (24)은 양이온 교환수지 (242)를 포함함으로써， 양이온 전도도， 예컨대 수소 이온 전도도를 향상시키고， 연료의 크로스 오버를 억제할 수 있다.  In addition, the fuel cell polymer electrolyte membrane 24 includes a cation exchange resin 242, thereby improving cation conductivity, for example, hydrogen ion conductivity, and suppressing fuel crossover.
상기 양이온 교환수지 (242)는 상기 다공성 지지체 (244)의 내부， 표면， 또는 내부와 표면에 존재한다. 상기 양이온 교환수지가 상기 다공성 지지체의 내부에 존재하는 경우, 이는 상기 다공성 지지체의 미세기공 및 피코기공에 채워져 존재할 수 있다.  The cation exchange resin 242 is present inside, on the surface, or inside and on the surface of the porous support 244. When the cation exchange resin is present in the porous support, it may be present in the micropores and picopores of the porous support.
이로써， 기계적 강도 및 치수 안정성이 우수하면서, 동시에 양이온 전도도， 예컨대 수소 이온 전도도도 우수한 연료 전지용 고분자 전해질 막 (24)을 제공할 수 있다.  Thereby, the polymer electrolyte membrane 24 for fuel cell excellent in mechanical strength and dimensional stability and also excellent in cation conductivity, such as hydrogen ion conductivity, can be provided.
상기 양이온 교환수지는 연료 전지용 고분자 전해질 막 (24)의 양이온 전도도， 예컨대 수소 이온 전도도를 향상시킬 수 있고， 연료 전지의 효율을 개선할 수 있다.  The cation exchange resin can improve the cation conductivity, such as hydrogen ion conductivity, of the polymer electrolyte membrane 24 for fuel cells, and can improve the efficiency of the fuel cell.
상기 양이온 교환수지는 술폰산기， 카르복실산기， 인산기， 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 양이온 교환기를 포함하는 고분자로서, 예를 들면 플루오르계 고분자， 벤즈이미다졸계 고분자， 폴리이미드계 고분자， 폴리에테르이미드계 고분자， 폴리페닐렌설파이드계 고분자, 폴리술폰계 고분자, 폴리에테르술폰계 고분자， 폴리에테르케톤계 고분자， 폴리에테르-에테르케톤계 고분자， 폴리페닐퀴녹살린계 고분자 또는 이들의 조합을 들 수 있으나， 이에 한정되는 것은 아니다. The cation exchange resin is a cation selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof As a polymer containing an exchange group, for example, a fluorine polymer, a benzimidazole polymer, a polyimide polymer, a polyetherimide polymer, a polyphenylene sulfide polymer, a polysulfone polymer, a polyether sulfone polymer, a poly Ether ketone polymers, polyether ether ketone polymers, polyphenylquinoxaline polymers, or combinations thereof, but is not limited thereto.
상기 양이온 교환수지는 본래 고분자 내에 술폰산기， 카르복실산기， 인산기, 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지고 있는 고분자를 포함할 수 있다. 또한 상기 양이온 교환수지는 본래 상기와 같은 작용기를 가지고 있지 않은 고분자에 상기와 같은 작용기를 치환시킨 고분자를 포함할 수도 있고， 본래 상기와 같은 작용기를 가지고 있지 않은 고분자에 상기와 같은 작용기를 가지는 산을 도핑한 고분자를 포함할 수도 있다.  The cation exchange resin may include a polymer having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the polymer. In addition, the cation exchange resin may include a polymer in which the functional group is substituted with a polymer which does not have the functional group, and has an acid having the functional group as described above in the polymer which does not have the functional group. It may also comprise a doped polymer.
상기 본래 고분자 내에 술폰산기， 카르복실산기， 인산기， 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지고 있는 고분자의 예로는 나피온 (Nafion, Dupont사)， 술폰화된 폴리 (페닐렌 설파이드 술폰 나이트릴) (sulfonated_poly(phenylene sulfide sul f one nitrile: s-PSSN)), 술폰화된 폴리 (아릴렌 에테르 술폰) (sulfonated-poly(arylene ether sul f one: s-PAES)), 술폰화된 폴리 (에테르 에테르 케톤) (sulfonated-poly(ether ether ketone: s-PEEK)) 등을 들 수 있으나, 이에 한정되는 것은 아니다. 술폰산기， 카르복실산기， 인산기， 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 치환시키거나， 또는 상기와 같은 작용기를 가지는 산을 도핑하여, 양이온 교환수지를 만들 수 있는 고분자의 예로는 폴리벤즈이미다졸, 폴리이미드, 폴리페닐렌 술파이드， 폴리술폰, 폴리술폰 유도체， 폴리페닐렌 옥사이드, 폴리페닐렌 술파이드, 폴리포스파젠 등을 들 수 있으나， 이에 한정되는 것은 아니다. Examples of the polymer having a functional group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof in the original polymer include Nafion (Nafion, Dupont), sulfonated poly (phenylene Sulfonated_poly (phenylene sulfide sul f one nitrile: s-PSSN), sulfonated poly (arylene ether sul f one: s-PAES), sulfonated Sulfonated-poly (ether ether ketone: s-PEEK) and the like, but are not limited thereto. Examples of polymers capable of forming a cation exchange resin by substituting a functional group selected from the group consisting of a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group and derivatives thereof, or by doping an acid having the functional group as described above. The polybenzimidazole, polyimide, polyphenylene sulfide, polysulfone, polysulfone derivative, polyphenylene oxide, polyphenylene sulfide, polyphosphazene and the like, but is not limited thereto.
상기 연료 전지용 고분자 전해질 막 (24)은 상기 다공성 지지체와 상기 양이온 교환수지를 약 99:1 내지 약 10 :90의 중량비로 포함할 수 있다. 다공성 지지체와 양이온 교환수지의 함량비가 상기 범위 내인 경우, 이를 포함하는 연료 전지용 고분자 전해질 막은 우수한 기계적 강도와 치수안정성을 가질 수 있다. 구체적으로는 상기 다공성 지지체와 양이온 교환수지는 약 95:5 내지 약 30 :70의 중량비로 포함될 수 있다.  The polymer electrolyte membrane 24 for the fuel cell may include the porous support and the cation exchange resin in a weight ratio of about 99: 1 to about 10:90. When the content ratio of the porous support and the cation exchange resin is within the above range, the polymer electrolyte membrane for a fuel cell including the same may have excellent mechanical strength and dimensional stability. Specifically, the porous support and the cation exchange resin may be included in a weight ratio of about 95: 5 to about 30:70.
한편， 도 1에 도시하지는 않았지만, 상기 애노드 (22)와 상기 캐소드 (26) 사이에 위치하며, 다공성 지지체 (244)를 포함하나， 별도의 양이온 교환수지 (242)를 포함하지 않는 연료 전지용 고분자 전해질 막 (24)이 사용될 수 있다. 이 경우， 상기 연료 전지용 고분자 전해질 막 (24)은 그 내부， 표면， 또는 내부와 표면에 산이 도핑되어 형성되어 있다. 상기 산은 술폰산, 카르복실산， 인산, 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 것일 수 있으나, 이에 한정되는 것은 아니다. 상기 다공성 지지체 (244)에 도핑된 산은 상기 양이온 교환수지 (242)와 유사한 역할을 수행한다. 따라서， 상기 다공성 지지체 (244)에 도핑된 산은 연료 전지용 고분자 전해질 막 (24)의 양이온 전도도, 예컨대 수소 이온 전도도를 향상시킬 수 있고, 연료 전지의 효율을 개선할 수 있다. On the other hand, although not shown in Figure 1, located between the anode 22 and the cathode 26, including a porous support 244, but does not include a separate cation exchange resin 242 for a fuel cell polymer electrolyte Membrane 24 may be used. In this case, the fuel cell polymer electrolyte membrane 24 is formed by acid doping therein, on the surface, or inside and the surface thereof. The acid may be selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof, but is not limited thereto. The acid doped in the porous support 244 plays a role similar to that of the cation exchange resin 242. Therefore, the acid doped in the porous support 244 is The cation conductivity, such as hydrogen ion conductivity, of the polymer electrolyte membrane 24 for fuel cells can be improved, and the efficiency of the fuel cell can be improved.
상기 연료 전지용 고분자 전해질 막 (24)은 약 20 IM 내지 약 300 의 두께를 가질 수 있다. 연료 전지용 고분자 전해질 막 (24)의 두께가 상기 범위 내인 경우 우수한 양이온 전도성, 예컨대 수소 이온 전도성을 달성할 수 있고， 연료의 크로스 오버를 억제할 수 있으며, 또한 우수한 기계적 강도， 치수 안정성， 내열성 및 내화학성을 효과적으로 달성할 수 있다. 구체적으로는 상기 연료 전지용 고분자 전해질 막 (24)은 약 20 내지 약 250 의 두께를 가질 수 있다.  The fuel cell polymer electrolyte membrane 24 may have a thickness of about 20 IM to about 300. When the thickness of the polymer electrolyte membrane 24 for fuel cells is within the above range, excellent cation conductivity, such as hydrogen ion conductivity, can be achieved, fuel crossover can be suppressed, and also excellent mechanical strength, dimensional stability, heat resistance and resistance to heat. Chemicality can be effectively achieved. Specifically, the fuel cell polymer electrolyte membrane 24 may have a thickness of about 20 to about 250.
이하 다공성 지지체를 형성하는 고분자에 대하여 구체적으로 설명한다.  Hereinafter, the polymer forming the porous support will be described in detail.
상기 다공성 지지체를 형성하는데 사용되는 폴리아믹산은 하기 화학식 1 내지 4로 표시되는 반복단위를 포함하는 폴리아믹산, 하기 화학식 5 내지 8로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있다.  The polyamic acid used to form the porous support may be a polyamic acid including a repeating unit represented by the following Chemical Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by the following Chemical Formulas 5 to 8, a copolymer thereof, and It can be selected from the group consisting of these blends.
[화학식 1]
Figure imgf000043_0001
[화학식 2]
Figure imgf000044_0001
[Formula 1]
Figure imgf000043_0001
[Formula 2]
Figure imgf000044_0001
[화학식 3]
Figure imgf000044_0002
[Formula 3]
Figure imgf000044_0002
[화학식 4]
Figure imgf000044_0003
[Formula 4]
Figure imgf000044_0003
[화학식 5]
Figure imgf000044_0004
[Formula 5]
Figure imgf000044_0004
[화학식 6]
Figure imgf000044_0005
[Formula 6]
Figure imgf000044_0005
[화학식 7]
Figure imgf000044_0006
[화학식 8]
Figure imgf000045_0001
[Formula 7]
Figure imgf000044_0006
[Formula 8]
Figure imgf000045_0001
상기 화학식 1 내지 8에서，  In Chemical Formulas 1 to 8,
Arr 치환 또는 비치환된 4가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 4가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고， 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합, 0， S, C(=0), CH(OH) , S(=0)2, Si(CH3)2, (C )p (여기서 , 1<ρ<10), (CF2)q (여기서 , l<q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고，An aromatic ring group selected from an Arr substituted or unsubstituted tetravalent C6 to C24 arylene group and a substituted and unsubstituted tetravalent C4 to C24 heterocyclic group, wherein the aromatic ring groups are present alone; Two or more are joined to each other to form a condensed ring; At least two single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (C) p (where 1 <ρ <10), (CF 2 ) q where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH,
Ar2는 치환 또는ᅵ비치환된 2가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 2가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0, S, C(=0), CH(OH) , SO0)2, Si(CH3)2, (C¾)p (여기서 , 1<ρ<10), (CF2)q (여기서， l<q<10), C(C¾)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고, Q는 0， S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (C¾)p (여기서， 1<P<10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2, C(=0)NH,Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more are joined to each other to form a condensed ring; 2 or more single bonds, 0, S, C (= 0), CH (OH), SO0) 2 , Si (CH 3 ) 2 , (C¾) p (where, 1 <ρ <10), (CF 2 ) q (wherein l <q <10), C (C¾) 2 , C (CF 3 ) 2 or C (= 0) NH, and Q is 0, S, C (= 0) , CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (C¾) p (where 1 <P <10), (CF 2 ) q (where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 , C (= 0) NH,
C(C¾)(CF3), 또는 치환 또는 비치환된 페닐렌기 (여기서 치환된 페닐렌 7C (C¾) (CF 3 ), or a substituted or unsubstituted phenylene group, wherein substituted phenylene 7
C1 내지 C6 알킬기 또는 C1 내지 C6 할로알킬기로 치환된다)이고， o 상기 Q는 양쪽 방향족 고리와 m-m, m-p, p-m, 또는 p-p 위치로 연결되고ᅳ γ는 각각의 반복단위에서 동일하거나 서로 상이하며， 각각 독립적으로 OH, SH 또는 Ν¾이고， C1 to C6 alkyl group or C1 to C6 haloalkyl group, and o is Q connected to both aromatic rings in mm, mp, pm, or pp position; γ is the same or different from each repeat unit, and each independently OH, SH or Ν¾,
η은 20≤η≤200을 만족하는 정수이고，  η is an integer satisfying 20≤η≤200,
m은 10≤m≤400을 만족하는 정수이고，  m is an integer satisfying 10≤m≤400,
1은 10≤1≤400을 만족하는 정수이다.  1 is an integer satisfying 10≤1≤400.
상기 화학식 1 내지 4 로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체의 예로는 하기 화학식 9 내지 18 로 표시되는 반복단위를 포함하는 폴리아믹산 공증합체를 들 수 있다.  Examples of the copolymer of the polyamic acid including the repeating units represented by Formulas 1 to 4 include polyamic acid copolymers including the repeating units represented by the following Formulas 9 to 18.
[화학식 9] [Formula 9]
Figure imgf000046_0001
[화학식 12]
Figure imgf000047_0001
Figure imgf000047_0002
Figure imgf000047_0003
Figure imgf000047_0004
Figure imgf000047_0005
[화학식 17]
Figure imgf000046_0001
[Formula 12]
Figure imgf000047_0001
Figure imgf000047_0002
Figure imgf000047_0003
Figure imgf000047_0004
Figure imgf000047_0005
[Formula 17]
Figure imgf000048_0001
상기 화학식 9 내지 화학식 18에서，
Figure imgf000048_0001
In Chemical Formulas 9 to 18,
An, Q, n, m 및 1은 상기 화학식 1 내지 화학식 8에서 정의한 바와 같고,  An, Q, n, m and 1 are the same as defined in Formula 1 to Formula 8,
Y 및 Y' 는 서로 상이하며， 각각 독립적으로 OH, SH 또는 N¾이다. 상기 다공성 지지체를 형성하는데 사용되는 폴리이미드는 하기 화학식 19 내지 22로 표시되는 반복단위를 포함하는 폴리이미드， 하기 화학식 23 내지 26으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있으나， 이에 한정되는 것은 아니다.  Y and Y 'are different from each other, and are each independently OH, SH or N¾. The polyimide used to form the porous support is a polyimide comprising a repeating unit represented by the following formulas 19 to 22, a polyimide copolymer comprising a repeating unit represented by the following formulas 23 to 26, a copolymer thereof, and It may be selected from the group consisting of blends, but is not limited thereto.
[화학식 19] ' [Formula 19] '
Figure imgf000048_0002
[화학식 20]
Figure imgf000049_0001
Figure imgf000048_0002
[Formula 20]
Figure imgf000049_0001
[화학식 21]
Figure imgf000049_0002
[Formula 21]
Figure imgf000049_0002
[화학식 22]
Figure imgf000049_0003
[Formula 22]
Figure imgf000049_0003
[화학식 23]
Figure imgf000049_0004
[화학식 25]
Figure imgf000050_0001
[Formula 23]
Figure imgf000049_0004
[Formula 25]
Figure imgf000050_0001
[화학식 26]
Figure imgf000050_0002
[Formula 26]
Figure imgf000050_0002
상기 화학식 19 내지 26에서，  In Chemical Formulas 19 to 26,
An, Ar2l Q, Y, n, m 및 1은 상기 화학식 1 내지 8에서 정의한 바와 같다 An, Ar 2l Q, Y, n, m and 1 are the same as defined in Chemical Formulas 1 to 8 above.
화학식 19 내지 22 로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체의 예로는 하기 화학식 27 내지 36 으로 표시되 반복단위를 포함하는 폴리이미드 공중합체를 들 수 있다.  Examples of the copolymer of the polyimide including the repeating units represented by the formulas (19) to (22) include polyimide copolymers including the repeating units represented by the following formulas (27) to (36).
[화학식 27][Formula 27]
Figure imgf000050_0003
Figure imgf000050_0003
[화학식 28] [Formula 28]
Figure imgf000050_0004
[화학식 29]
Figure imgf000051_0001
Figure imgf000050_0004
[Formula 29]
Figure imgf000051_0001
[화학식 30]
Figure imgf000051_0002
[Formula 30]
Figure imgf000051_0002
화학식 31]
Figure imgf000051_0003
Formula 31]
Figure imgf000051_0003
화학식 32:
Figure imgf000051_0004
Formula 32:
Figure imgf000051_0004
화학식 33
Figure imgf000051_0005
Formula 33
Figure imgf000051_0005
화학식 34
Figure imgf000051_0006
[화학식 35] Formula 34
Figure imgf000051_0006
[Formula 35]
Figure imgf000052_0001
Figure imgf000052_0001
상기 화학식 27 내지 36에서，  In Chemical Formulas 27 to 36,
An, Q, m 및 1은 상기 화학식 1 내지 8에서 정의한 바와 같고, An, Q, m and 1 are the same as defined in Chemical Formulas 1 to 8,
Ϋ 및 Y'는 각각의 반복단위에서 동일하거나 서로 상이하며 , 각각 독립적으로 OH, SH 또는 N¾이다. And Y and Y 'are the same or different from each other and are each independently OH, SH or N¾.
상기 화학식 1 내지 36에서， A 의 예는 하기 식으로 표시된 것 중에서 선택될 수 있으나， 이에 한정되는 것은 아니다. In Chemical Formulas 1 to 36, examples of A may be selected from those represented by the following formulas, but are not limited thereto.
Figure imgf000053_0001
Figure imgf000053_0001
상기 식에서，  In the above formula,
Xi, ， ¾ 및 는 동일하거나 서로 상이하며 각각 독립적으로 0, S, C(=0), CH(OH), S(=0)2, Si(CH3)2> (C¾)p (여기서， 1<P<10), (CF2)q (여기서， l<q<10), C(C¾)2, C(CF3)2) 또는 C(=0)NH이고, Xi,, ¾ and are the same or different and are each independently 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2> (C¾) p (where ， 1 < P <10), (CF 2 ) q (where l <q <10), C (C¾) 2 , C (CF 3 ) 2) or C (= 0) NH,
Wi 및 는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는 C(=0)이고，  Wi and are the same or different and are each independently 0, S, or C (= 0),
^은 0, S, CRiOoRlOl 또는 服102이고， 여기서 RlOO, RlOl 및 02는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고，  ^ Is 0, S, CRiOoRlOl or 服 102, wherein RlOO, RlOl and 02 are the same or different and are each independently hydrogen or a C1 to C5 alkyl group,
Z2 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CR103(여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고 Z 2 and ¾ are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group) but at the same time not CR 103;
Ri 내지 R42는 동일하거나 서로 상이하며 각각 독립적으로 수소， 또는 치환 또는 비치환된 C1 내지 C10 지방족 유기기이고, Ri to R 42 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
kl 내지 k3, k8 내지 kl4, k24 및 k25는 0내지 2의 정수이고， k5, kl5, kl6, kl9, k21 및 k23은 0또는 1의 정수이고，  kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
k4, k6, k7, kl7, kl8, k20, k22, k26 내지 k29, k31, k34 내지 k36, k38, k39 및 k42는 0 내지 3의 정수이고，  k4, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers of 0 to 3,
k30, k37, k40 및 k41은 0내지 4의 정수이고，  k30, k37, k40 and k41 are integers from 0 to 4,
k32 및 k33은 0내지 5의 정수이다.  k32 and k33 are integers of 0-5.
상기 화학식 1 내지 36에서, 의 구체적인 예는 하기 식으로 표시된 것 중에서 선택될 수 있으나, 이에 한정되는 것은 아니다. In Chemical Formulas 1 to 36, specific examples of may be selected from those represented by the following formula, but are not limited thereto.
Figure imgf000055_0001
Figure imgf000055_0001
53
Figure imgf000056_0001
53
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000057_0001
상기 식에서，  In the above formula,
¾, ¾, ¾ 및 X4는 동일하거나 서로 상이하며 각각 독립적으로 0, S, C(=0), CH(OH), S(=0)2, Si(C¾)2, (C¾)p (여기서， 1<ρ<10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2, 또는 C(=0)NH이고, ¾, ¾, ¾, and X4 are the same or different from each other and each independently 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (C¾) 2 , (C¾) p (where 1 <ρ <10), (CF 2 ) q (where l <q < 10), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (= 0) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는 c(=o)이고, Wi and W 2 are the same or different from each other and are each independently 0, S, or c (= o),
^은 0， S, CRiooRioi 또는 NR102이고, 여기서 R100, R101 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고， ^ Is 0, S, CRiooRioi or NR 102 , wherein R 100 , R 101 and R 102 are the same or different and are each independently hydrogen or a C1 to C5 alkyl group,
¾ 및 Z3는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CR103 (여기서, R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 0½3은 아니고，¾ and Z 3 are the same or different from each other and independently from each other N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group), but not 0½ 3 ;
3 내지 ¾9는 동일하거나 서로 상이하며 각각 독립적으로 수소, 치환 또는 비치환된 C1 내지 C10 지방족 유기기， 또는 금속 술포네이트기이고， 여기서 금속은 나트륨， 칼륨， 리튬, 이들의 합금 또는 이들의 조합일 수 있고，  3 to ¾9 are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group, wherein the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof Can
k43, k49, k64 내지 k68, k72 내지 k76, 및 k82 내지 k89는 0 내지 4의 정수이고，  k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
k44 내지 k46, k48, k51, k54, k55, k57, k58, k61 및 k63은 0 내지 3의 정수이고，  k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 및 k81은 0 내지 2의 수이고，  k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are numbers from 0 to 2,
k50은 0 또는 1의 정수이고， k69, k71, k77 및 k79는 0 내지 5의 정수이다. k50 is an integer of 0 or 1, k69, k71, k77 and k79 are integers of 0-5.
상기 화학식 1 내지 36에서， Ar2의 구체적인 예는 하기 표시된 것 중에서 선택될 수 있으나， 이에 한정되는 것은 아니다. In Chemical Formulas 1 to 36, specific examples of Ar 2 may be selected from the following, but are not limited thereto.
8S 8S
Figure imgf000060_0001
Figure imgf000060_0001
89COOO/llOZa¾/X3d
Figure imgf000061_0001
89COOO / llOZa¾ / X3d
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000062_0001
Figure imgf000062_0002
Figure imgf000062_0002
상기 식에서， M은 금속이고， 상기 금속은 나트륨， 칼륨, 리튬， 이들의 합금 또는 이들의 조합일 수 있으나， 이에 한정되는 것은 아니다. 상기 화학식 1 내지 36에서， Q의 예는 C(CH3)2, C(CF3)2, 0, S, S(=0)2 또는 C(=0) 중에서 선택될 수 있으나， 이에 한정되는 것은 아니다. 상기 화학식 1 내지 36에서, A 은 하기 화학식 A1 내지 A8 중 어느 하나로 표시되는 작용기일 수 있고, Ar2는 하기 화학식 B1 내지 B11 중 어느 하나로 표시되는 작용기일 수 있고， Q는 C(CF3)2일 수 있으나， 이에 한정되는 것은 아니다 . In the above formula, M is a metal, and the metal may be sodium, potassium, lithium, alloys thereof, or a combination thereof, but is not limited thereto. In Formulas 1 to 36, examples of Q may be selected from C (CH 3 ) 2 , C (CF 3 ) 2 , 0, S, S (= 0) 2 or C (= 0), but are not limited thereto. It is not. In Formulas 1 to 36, A may be a functional group represented by any one of Formulas A1 to A8, Ar 2 may be a functional group represented by any one of Formulas B1 to B11, and Q is C (CF 3 ) 2 May be, but It is not limited.
[화학식 A1] [화학식 A2] [화학식 A3]  [Formula A1] [Formula A2] [Formula A3]
Figure imgf000063_0001
Figure imgf000063_0001
[화학식 A8] [Formula A8]
Figure imgf000063_0002
Figure imgf000063_0002
[화학식 B1] [화학식 B2] [화학식 B3]
Figure imgf000063_0003
[화학식 B4] [화학식 B5] [화학식 B6] [화학식 B7] [Formula B1] [Formula B2] [Formula B3]
Figure imgf000063_0003
[Formula B4] [Formula B5] [Formula B6] [Formula B7]
Figure imgf000064_0001
Figure imgf000064_0001
[화학식 B10] [화학식 B11]  [Formula B10] [Formula B11]
Figure imgf000064_0002
Figure imgf000064_0002
상기 화학식 1 내지 화학식 4 로 표시되는 반복단위를 포함하 폴리아믹산 및 상기 화학식 19 내지 화학식 22 로 표시되는 반복단위를 포함하는 폴리이메는 일반적인 제조방법을 통해 제조가 가능하다. 일 예로， 단량체로 테트라카르복시산 무수물과 아 I， SH 또는 NH2기를 포함하는 방향족 디아민을 반웅시켜 제조한다. The polyamic acid including the repeating unit represented by Formula 1 to Formula 4 and the polyimide including the repeating unit represented by Formula 19 to Formula 22 may be manufactured by a general manufacturing method. For example, it is prepared by reacting tetracarboxylic anhydride with an aromatic diamine containing a subgroup I, SH or NH 2 as a monomer.
상기 화학식 1 내지 화학식 4 로 표시되는 반복단위를 포함하 폴리아믹산은 소정의 열처리에 의해 이미드화 및 열전환되고， 상기 화학식 19 내지 화학식 22 로 표시되는 반복단위를 포함하는 폴리이미드는 소정의 열처리에 의해 열전환되어， 피코기공을 가지며 우수한 기계적 물성 및 높은 자유 체적도를 갖는 폴리벤조옥사졸， 폴리벤조티아졸， 폴리피를론과 같은 고분자로 전환된다. 이때 상기 화학식 1 내지 화학식 4 의 Y 가 0H 인 폴리하이드록시아믹산 또는 상기 화학식 19 내지 화학식 22 의 Y 가 0H 인 폴리하이드록시이미드로부터 유도된 폴리벤조옥사졸， Y 가 SH 인 폴리티올아믹산 또는 폴리티올이미드로부터 유도된 폴리벤조티아졸, Y 가 NH2인 폴리아미노아믹산 또는 폴리아미노이미드로부터 유도된 폴리피를론을 포함하는 다공성 지지체가 제조된다. The polyamic acid including the repeating unit represented by Formula 1 to Formula 4 is imidized and thermally converted by a predetermined heat treatment, and the polyimide including the repeating unit represented by Formula 19 to Formula 22 is subjected to a predetermined heat treatment. It is thermally converted to a polymer such as polybenzoxazole, polybenzothiazole, polypylon, which has picopores and has excellent mechanical properties and high free volume. Wherein Y in Formula 1 to Formula 4 is 0H Polybenzoxazoles derived from polyhydroxyamic acids or polyhydroxyimides having Y of 0H of Formulas 19-22, polythiolamic acid or polythiolimide derived of Y of SH, A porous support is prepared comprising polypylons derived from polyaminoamic acid or polyaminoimide wherein Y is NH 2 .
또한 상기 화학식 1 내지 화학식 4 로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체에서의 각 반복단위 사이의 몰비; 또는 상기 화학식 19 내지 화학식 22 로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체에서의 각 반복단위 사이의 몰비를 조절하여, 제조된 다공성 지지체의 물성 제어가 가능하다.  In addition, the molar ratio between each repeating unit in the copolymer of the polyamic acid containing a repeating unit represented by the formula (1) to (4); Alternatively, by controlling the molar ratio between the repeating units in the copolymer of the polyimide including the repeating units represented by Formulas 19 to 22, it is possible to control the physical properties of the prepared porous support.
상기 화학식 5 내지 화학식 8 로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체는 소정의 열처리에 의해 이미드화 및 열전환될 수 있다ᅳ 또한 상기 화학식 23 내지 화학식 26 으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체는 소정의 열처리에 의해 열전환될 수 있다. 이로써, 상기 화학식 5 내지 화학식 8 로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체 및 상기 화학식 23 내지 화학식 26 으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체는 피코기공을 가지며 우수한 기계적 물성 및 높은 자유 체적도를 갖는 폴리 (벤조옥사졸-이미드) 공중합체, 폴리 (밴조티아졸—이미드) 공중합체 또는 폴리 (피를론-이미드) 공중합체로 전환되고， 이를 이용하면 상기와 같은 공중합체를 포함하는 다공성 지지체를 형성할 수 있다. 이때 분자내 및 분자간 재배열에 의해 폴리벤조옥사졸， 폴리벤조티아졸 또는 폴리피롤론으로 열전환되는 블럭과 폴리이미드로 되는 블럭간의 공중합비 (몰비 )를 조절하여， 제조되는 다공성 지지체의 물성 제어가 가능하다. The polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 may be imidized and thermally converted by a predetermined heat treatment. In addition, the polyimide comprising the repeating unit represented by Formula 23 to Formula 26 The copolymer can be thermally converted by a predetermined heat treatment. As a result, the polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 and the polyimide copolymer including the repeating unit represented by Formula 23 to Formula 26 have picopores and have excellent mechanical properties and high freedom. Converted to poly (benzoxazole-imide) copolymers, poly (banjothiazole-imide) copolymers, or poly (pyrrolone-imide) copolymers having a volumetric degree, A porous support comprising coalescing can be formed. In this case, by intramolecular and intermolecular rearrangement By controlling the copolymerization ratio (molar ratio) between blocks converted to polybenzoxazole, polybenzothiazole or polypyrrolone and blocks made of polyimide, it is possible to control physical properties of the prepared porous support.
-상기 화학식 9 내지 화학식 18 로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체는 소정의 열처리에 의해 이미드화 및 열전환될 수 있다ᅳ 또한 상기 화학식 27 내지 화학식 36 으로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체는 소정의 열처리에 의해 열전환될 수 있다. 이로써， 상기 화학식 9 내지 화학식 18 로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체 및 상기 화학식 27 내지 화학식 36 으로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체는 피코기공을 가지며 우수한 기계적 물성 및 높은 자유 체적도를 갖는 폴리벤조옥사졸， 폴리벤조티아졸 및 폴리피롤론의 공중합체로 전환되고， 이를 이용하면 상기와 같은 공중합체를 포함하는 다공성 지지체를 형성할 수 있다. 이때 각각 폴리벤조옥사졸， 폴리벤조티아졸 및 폴리피롤론으로 열전환되는 블럭간의 공중합비 (몰비)를 조절하여, 제조되는 다공성 지지체의 물성 제어가 가능하다.  The copolymer of the polyamic acid including the repeating unit represented by Formula 9 to Formula 18 may be imidized and thermally converted by a predetermined heat treatment. The copolymer of polyimide can be thermally converted by a predetermined heat treatment. As a result, the copolymer of the polyamic acid including the repeating unit represented by the formula (9) to the formula (18) and the copolymer of the polyimide including the repeating unit represented by the formula (27) to (36) has picopores and excellent mechanical properties and It is converted into a copolymer of polybenzoxazole, polybenzothiazole and polypyrrolone having a high degree of free volume, which can be used to form a porous support comprising such a copolymer. At this time, by controlling the copolymerization ratio (molar ratio) between the blocks thermally converted to polybenzoxazole, polybenzothiazole and polypyrrolone, it is possible to control the physical properties of the prepared porous support.
상기 화학식 1 내지 화학식 4 로 표시되는 반복단위를 포함하는 폴리아믹산의 공중합체에서의 각 반복단위 사이의 몰비; 또는 상기 화학식 5 내지 화학식 8 로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체의 블럭간 공중합비 (몰비) m:l 은 약 0.1:9.9 내지 약 9.9:0.1， 구체적으로는 약 2:8 내지 약 8:2， 더욱 구체적으로는 약 5:5로 조절할 수 있다. 또한 상기 화학식 19 내지 화학식 22 로 표시되는 반복단위를 포함하는 폴리이미드의 공증합체에서의 각 반복단위 사이의 몰비; 또는 상기 화학식 23 내지 화학식 26 으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체의 블럭간 공중합비 (몰비) m:l 은 약 0.1:9.9 내지 약 9.9:0.1, 구체적으로는 약 2:8 내지 약 8:2, 더욱 구체적으로는 약 5:5 로 조절할 수 있다. Molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating unit represented by Formula 1 to Formula 4; Or the inter-block copolymerization ratio (molar ratio) m: l of the polyamic acid copolymer including the repeating unit represented by Formula 5 to Formula 8 is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: 2, more specifically about 5: 5. In addition, the molar ratio between each repeating unit in the co-polymer of a polyimide containing a repeating unit represented by the formula (19) to formula (22); Or the interblock copolymerization ratio (molar ratio) m: l of the polyimide copolymer including the repeating unit represented by Formula 23 to Formula 26 is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: 2, more specifically about 5: 5.
이러한 몰비 내지 공중합비는 제조되는 다공성 지지체의 모폴로지에 영향을 주는데， 이러한 모폴로지 변화는 기공 특성， 내열성， 표면 경도 등과 관련되어 있다. 상기 몰비 내지 공중합비가 상기 범위 내인 경우， 제조되는 다공성 지지체는 우수한 기계적 물성 및 치수 안정성을 가질 수 있고， 우수한 '기공도를 가질 수 있으며, 또한 우수한 가공성을 가져 공정시간 단축 및 비용 절감 효과를 가질 수 있다.  The molar ratio to the copolymerization ratio affects the morphology of the porous support to be produced, which is related to pore properties, heat resistance, surface hardness, and the like. When the molar ratio to the copolymerization ratio is within the above range, the porous support to be prepared may have excellent mechanical properties and dimensional stability, may have excellent 'porosity, and also have excellent workability to reduce the process time and cost reduction effect have.
상기 다공성 지지체에서， 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부.터 유도되는 고분자는 하기 화학식 37 내지 50 중 어느 하나로 표시되는 반복단위를 포함하는 고분자 또는 이들의 공중합체를 포함할 수 있으나， 이에 한정되는 것은 아니다.  In the porous support, the polymer derived from the polyamic acid and the polymer derived from the polyimide may include a polymer including a repeating unit represented by any one of the following Formulas 37 to 50 or a copolymer thereof: Or not limited thereto.
[화학식 37]
Figure imgf000067_0001
[화학식 38] [Formula 37]
Figure imgf000067_0001
[Formula 38]
Figure imgf000068_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000069_0003
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000069_0003
[화학식 47]
Figure imgf000069_0004
[Formula 47]
Figure imgf000069_0004
[화학식 48]
Figure imgf000069_0005
P T/KR2011/000368 [Formula 48]
Figure imgf000069_0005
PT / KR2011 / 000368
[화학식 49] [Formula 49]
Figure imgf000070_0001
Figure imgf000070_0001
상기 화학식 37 내지 50에서 ,  In Chemical Formulas 37 to 50,
An, Ar2, Q, n, m 및 1 은 각각 상기 화학식 1 내지 8의 A , Ar2, Q, n, m 및 1에서 설명된 바와 같고， An, Ar 2 , Q, n, m and 1 are as described in A, Ar 2 , Q, n, m and 1 of Formulas 1 to 8, respectively,
Ar 는 치환 또는 비치환된 2 가의 C6 내지 C24 아릴렌기 및 치환 또는 비치환된 2 가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2 개 이상이 서로 접합되어 축합 고리를 형성하거나; 2 개 이상이 단일결합， 0, S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (CH2)P (여기서, 1<ρ<10), (CF2)q (여기서, l<q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고, Y' '는 0또는 S 이다. Ar is an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more are joined to each other to form a condensed ring; Two or more single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P (where 1 <ρ <10) , (CF 2 ) q (wherein l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH, and Y ′ ′ is 0 or S is.
상기 화학식 37 내지 50 에서， An, Ar2 및 Q 의 예 및 구체적인 예는 각각 상기 화학식 1 내지 36 의 A , Ar2 및 Q 의 예 및 구체적인 예로 언급된 것과 동일하다. In Formulas 37 to 50, Examples of An, Ar 2 and Q and specific examples Respective examples of A, Ar 2 and Q of Formulas 1 to 36 are the same as those mentioned in the specific examples.
또한 상기 화학식 37 내지 50에서, ArV의 예 및 구체적인 예는 상기 화학식 1 내지 36의 Ar2의 예 및 구체적인 예로 언급된 것과 동일하다. 상기 화학식 37 내지 50에서， A 은 상기 화학식 A1 내지 A8 중 어느 하나로 표시되는 작용기일 수 있고， Ar 는 하기 화학식 C1 내지 C8 중 어느 하나로 표시되는 작용기일 수 있고， Ar2는 상기 화학식 B1 내지 B11 중 어느 하나로 표시되는 작용기일 수 있고， Q는 C(CF3)2일 수 있으나， 이에 한정되는 것은 아니다. In addition, in Formulas 37 to 50, examples and specific examples of ArV are the same as those mentioned for the examples and specific examples of Ar 2 of Formulas 1 to 36. In Formulas 37 to 50, A may be a functional group represented by any one of Formulas A1 to A8, Ar may be a functional group represented by any one of Formulas C1 to C8, and Ar 2 is represented by Formulas B1 to B11 It may be a functional group represented by any one, and Q may be C (CF 3 ) 2 , but is not limited thereto.
[화학식 C1] [화학식 C2] [화학식 C3]  [Formula C1] [Formula C2] [Formula C3]
Figure imgf000071_0001
Figure imgf000071_0001
[화학식 C4] [화학식 C5] [화학식 C6]  [Formula C4] [Formula C5] [Formula C6]
Figure imgf000071_0002
Figure imgf000071_0002
[화학식 C7]
Figure imgf000071_0003
[화학식 C8]
Figure imgf000072_0001
[Formula C7]
Figure imgf000071_0003
[Formula C8]
Figure imgf000072_0001
한편， 상기 연료 전지용 고분자 전해질 막에서， 상기 다공성 지지체는 표면에 불소기를 포함하는 것일 수 있다. 이 경우， 이온 전도체와의 접착성이 향상될 수 있고， 다공성 지지체의 젖음성 (wettability), 삼투성 (permeat ion) , 전기 전도도 (electrical conductivity), 그래프팅 (graft ing) 특성 및 기계적 특성 (mechanical behavior)을 개선할 수 있다.  On the other hand, in the fuel cell polymer electrolyte membrane, the porous support may include a fluorine group on the surface. In this case, the adhesion with the ion conductor can be improved, and the wettability, permeat ion, electrical conductivity, grafting property and mechanical behavior of the porous support can be improved. ) Can be improved.
상기 불소기는 예컨대， 플루오린， 플루오르화물 (fluoride)을 사용하여 직접 불소화법， 플라즈마 증착법 등의 방법으로 도입할 수 있으나， 이에 한정되는 것은 아니다.  The fluorine group may be introduced by, for example, direct fluorination or plasma deposition using fluorine or fluoride, but is not limited thereto.
상기 다공성 지지체는 열처리 이후에도 수축율이 약 10% 미만으로 우수한 치수 안정성을 가진다.  The porous support has excellent dimensional stability with shrinkage of less than about 10% even after heat treatment.
본 발명의 다른 일 구현예에 따르면， 아민기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 가지는 폴리아믹산 또는 폴리이미드; 및 유기 용매를 포함하는 다공성 지지체 형성용 조성물을 제공한다. 상기 유기 용매는 디메틸설폭사이드; N-메틸 -2-피를리돈; N- 메틸피를리돈; Ν,Νᅳ디메틸포름아미드; Ν,Ν—디메틸아세트아미드;  According to another embodiment of the present invention, a polyamic acid or polyimide having a repeating unit prepared from an aromatic diamine and a dianhydride including at least one functional group present at an ortho position relative to an amine group; And it provides a composition for forming a porous support comprising an organic solvent. The organic solvent is dimethyl sulfoxide; N-methyl-2-pyridone; N-methylpyridone; Ν, Ν ᅳ dimethylformamide; Ν, Ν—dimethylacetamide;
부티로락톤， 사이클로핵사논， 3-핵사논， 3-헵타논 및 3-옥타논으로 이루어진 군에서 선택된 케톤; 및 이들의 조합으로 이루어진 군에서 선택되는 것이다. Ketones selected from the group consisting of butyrolactone, cyclonucleanone, 3-nuxanone, 3-heptanone and 3-octanone; And combinations thereof It is chosen.
상기 유기 용매를 사용하면 상기 폴리아믹산 또는 상기 폴리이미드와 같은 고분자를 쉽게 용해시킬 수 있다. 또한, 후술하는 보조제와 잘 섞임으로써 다공성 지지체 형성용 조성물을 불안정한 (met a— stable) 상태로 형성할 수 있고， 이로 인해 다공성 지지체를 용이하게 형성할 수 있다.  Using the organic solvent can easily dissolve a polymer such as the polyamic acid or the polyimide. In addition, by mixing well with the adjuvant to be described later it is possible to form the composition for forming a porous support in a stable (met a-stable) state, thereby making it possible to easily form a porous support.
상기 다공성 지지체 형성용 조성물은 다공성 지지체 형성용 조성물 총량에 대하여, 상기 폴리아믹산 또는 상기 폴리이미드를 약 1 중량 % 내지 약 40 중량 %， 상기 유기 용매를 약 60 중량 % 내지 약 99 중량 ¾>로 포함할 수 있다. 다공성 지지체 형성용 조성물의 각 성분의 함량이 상기 범위 내인 경우, 다공성 지지체 형성용 조성물의 점도를 적절히 유지하여 다공성 지지체의 제조를 용이하게 할 수 있고, 형성되는 다공성 지지체의 표면 및 내부 기공의 크기를 적절히 조절할 수 있다. 또한 다공성 지지체의 강도를 우수하게 유지할 수 있고， 이로써 기계적 강도 및 치수 안정성이 우수한 다공성 지지체 및 이를 포함하는 연료 전지용 고분자 전해질 막을 용이하게 형성할 수 있다.  The composition for forming a porous support includes about 1 wt% to about 40 wt% of the polyamic acid or the polyimide and about 60 wt% to about 99 wt% of the organic solvent, based on the total amount of the composition for forming the porous support. can do. When the content of each component of the composition for forming a porous support is within the above range, the viscosity of the composition for forming a porous support may be properly maintained to facilitate the preparation of the porous support, and the size of the surface and internal pores of the formed porous support may be adjusted. It can be adjusted appropriately. In addition, the strength of the porous support can be maintained excellent, thereby easily forming a porous support having excellent mechanical strength and dimensional stability and a polymer electrolyte membrane for a fuel cell including the same.
상기 다공성 지지체 '형성용 조성물은 물; 메탄올， 에탄올， 2-메틸一 1- 부탄올， 2-메틸 -2ᅳ부탄올, 글리세롤， 에틸렌글리콜， 디에틸렌글리콜 및 프로필렌글리콜로 이루어진 군에서 선택된 알코올; 아세톤 및 메틸에틸 케톤으로 이루어진 군에서 선택된 케톤; 폴리비닐알코을， 폴리아크릴산， 폴리아크릴아마이드， 폴리에틸렌글리콜， 폴리프로필렌글리콜, 키토산， 키틴， 덱스트란 및 폴리비닐피를리돈으로 이루어진 군에서 선택된 고분자 화합물; 테트라하이드로퓨란 ; 트리클로로에탄; 및 이들의 조합으로 이루.어진 군에서 선택되는 보조제를 더 포함할 수 있다. The composition for forming the porous support ' water; Alcohols selected from the group consisting of methanol, ethanol, 2-methyl-l-butanol, 2-methyl-2'butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; Ketones selected from the group consisting of acetone and methylethyl ketone; A polymer compound selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol, polypropylene glycol, chitosan, chitin, dextran, and polyvinylpyridone; Tetrahydrofuran; Trichloroethane; And it may further comprise an adjuvant selected from the group consisting of a combination thereof.
상기 보조제는 폴리아믹산 또는 폴리이미드와의 용해도가 우수한 것은 아니므로 홀로 사용될 수 없지만, 유기 용매와 적절히 흔합되면 불안정한 (meta-stable) 다공성 지지체 형성용 조성물을 제조할 수 있으며， 다공성 지지체 형성용 조성물을 전기방사할 때 적절한 기공 크기， 기공 분포 및 기공도를 가지는 부직포를 효과적으로 형성할 수 있다.  The auxiliary agent may not be used alone because it is not excellent in solubility with polyamic acid or polyimide, but when properly mixed with an organic solvent, a composition for forming a meta-stable porous support may be prepared. When electrospinning, it is possible to effectively form a nonwoven fabric having an appropriate pore size, pore distribution and porosity.
상기 보조제는 다공성 지지체 형성 시에 확산， 증발 등에 의해서 제거되면서， 상기 다공성 지지체 내부에 미세기공을 형성할 수 있으며， 이로써 상기 다공성 지지체의 기공도를 높일 수 있다. 구체적으로는 상기 고분자 화합물은 공극 조절제로 사용할 수 있다. 또한 상기 보조제는 상분리 온도 또는 다공성 지지체 형성용 조성물의 점성 조절을 위해 사용될 수도 있다.  The auxiliary agent may be removed by diffusion, evaporation, etc. during formation of the porous support to form micropores in the porous support, thereby increasing the porosity of the porous support. Specifically, the polymer compound can be used as a pore control agent. In addition, the adjuvant may be used for controlling the viscosity of the composition for forming a phase separation temperature or the porous support.
상기 다공성 지지체 형성용 조성물은 상기 보조제를 포함하는 다공성 지지체 형성용 조성물 총량에 대하여， 상기 폴리아믹산 또는 상기 폴리이미드를 약 1 중량 % 내지 약 40 중량 %， 상기 유기 용매를 약 10 중량 % 내지 약 95 중량 %, 그리고 상기 보조제를 약 4 중량 ¾> 내지 약 70 중량 %로 포함할 수 있다. 다공성 지지체 형성용 조성물의 각 성분의 함량이 상기 범위 내인 경우ᅳ 다공성 지지체 형성용 조성물의 점도를 적절히 유지하여 다공성 지지체의 제조를 용이하게 할 수 있고， 형성되는 다공성 지지체의 표면 및 내부 기공의 크기를 적절히 조절할 수 있다. 또한 다공성 지지체의 강도를 우수하게 유지할 수 있고, 이로써 기계적 강도 및 치수 안정성이 우수한 다공성 지지체 및 이를 포함하는 연료 전지용 고분자 전해질 막을 용이하게 형성할 수 있다. The composition for forming a porous support may include about 1 wt% to about 40 wt% of the polyamic acid or polyimide, and about 10 wt% to about 95 of the organic solvent, based on the total amount of the composition for forming a porous support including the auxiliary agent. Weight percent, and from about 4 weight percent to about 70 weight percent of the adjuvant. When the content of each component of the composition for forming a porous support is within the above range, the viscosity of the composition for forming a porous support may be properly maintained to facilitate the preparation of the porous support, and the size of the surface and internal pores of the formed porous support may be adjusted. It can be adjusted appropriately. Also porous The strength of the support can be maintained excellent, thereby easily forming a porous support excellent in mechanical strength and dimensional stability and a polymer electrolyte membrane for a fuel cell including the same.
상기 다공성 지지체 형성용 조성물은 약 0.01 Pa - s 내지 약 100 Pa - s 의 점도를 가질 수 있다. 다공성 지지체 형성용 조성물의 점도가 상기 범위 내이면 다공성 지지체 형성용 조성물올 용이하게 전기방사할 수 있고， 다공성 지지체를 상전이 현상을 통해 용이하게 고형으로 웅고시킬 수 있다.  The composition for forming the porous support may have a viscosity of about 0.01 Pa-s to about 100 Pa-s. When the viscosity of the composition for forming a porous support is within the above range, the composition for forming a porous support can be easily electrospun, and the porous support can be easily solidified through a phase transition phenomenon.
상기 다공성 지지체 형성용 조성물에서， 상기 폴리아믹산 및 상기 폴리이미드는 각각 약 10,000 g/mol 내지 약 500,000 g/nrol의 중량평균 분자량 (Mw)을 가질 수 있다. 폴리아믹산 및 폴리이미드의 중량평균 분자량이 상기 범위 내이면 이의 합성이 용이하고， 이를 포함하는 다공성 지지체 형성용 조성물의 점도가 적절하게 유지되어 가공성이 우수하며， 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 기계적 강도 및 치수 안정성이 우수하게 유지될 수 있다. 상기 다공성 지지체 형성용 조성물에서， 상기 폴리아믹산은 상기 화학식 1 내지 4로 표시되는 반복단위를 포함하는 폴리아믹산, 상기 화학식 5 내지 8 로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있다. 또한 상기 폴리이미드는 상기 화학식 19 내지 22 로 표시되는 반복단위를 포함하는 폴리이미드， 상기 화학식 23 내지 26 으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체, 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택될 수 있다. In the composition for forming the porous support, the polyamic acid and the polyimide may each have a weight average molecular weight (Mw) of about 10,000 g / mol to about 500,000 g / nrol. When the weight average molecular weight of the polyamic acid and the polyimide is within the above range, the synthesis thereof is easy, and the viscosity of the composition for forming a porous support including the same is appropriately maintained so as to be excellent in processability, and the polymer and poly is derived from the polyamic acid. Polymers derived from meads can be maintained with good mechanical strength and dimensional stability. In the composition for forming a porous support, the polyamic acid is a polyamic acid comprising a repeating unit represented by Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by Formulas 5 to 8, copolymers thereof And blends thereof. In addition, the polyimide is a polyimide containing a repeating unit represented by the formula (19) to 22, the repeating unit represented by the formula (23 to 26) It can be selected from the group consisting of polyimide copolymers, copolymers thereof and blends thereof.
본 발명의 또 다른 일 구현예에 따르면, 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 및 상기 부직포를 열처리하여 폴리아믹산으로부터 유도되는 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계를 포함하는 다공성 지지체의 제조 방법을 제공한다.  According to another embodiment of the present invention, forming a nonwoven fabric by electrospinning the composition for forming the porous support; And heat treating the nonwoven fabric to form a porous support including a polymer derived from a polyamic acid or a polymer derived from polyimide.
본 발명의 또 다른 일 구현예에 따르면， 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 내부， 표면， 또는 내부와 표면에 양이온 교환 수지를 형성하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법을 제공한다.  According to another embodiment of the present invention, forming a nonwoven fabric by electrospinning the composition for forming the porous support; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of forming a cation exchange resin on the inside, surface, or the inside and the surface of the porous support.
상기 다공성 지지체 형성용 조성물을 전기방사함으로써, 수 nm 내지 수십 의 직경을 가지는 섬유를 포함하는 부직포를 형성할 수 있다. 상기 섬유를 포함하는 부직포는 넓은 비표면적을 가질 수 있고， 상당한 표면 거칠기를 가질 수 있다. 또한 이때 상기 형성되는 부직포는 미세기공을 포함한다.  By electrospinning the composition for forming the porous support, a nonwoven fabric including fibers having a diameter of several nm to several tens can be formed. Nonwovens comprising such fibers can have a large specific surface area and can have significant surface roughness. In addition, the nonwoven fabric formed at this time includes micropores.
상기 부직포는 상기 전기방사의 방법 및 공정 조건을 조절함으로써, 상기 다공성 지지체 형성용 조성물을 포함하는 섬유가 랜덤하게 배열되어 형성될 수 있다. π 한편， 상기 부직포는 상기 전기방사의 방법 및 공정 조건을 조절함으로써， 다공성 지지체 형성용 조성물을 포함하는 섬유가 일방향으로 배열되어 형성될 수도 있다. 이에 따른 장점은 상술한 바와 같다. The nonwoven fabric may be formed by randomly arranging fibers including the composition for forming the porous support by controlling the method and process conditions of the electrospinning process. π On the other hand, the nonwoven fabric may be formed by adjusting the method and the process conditions of the electrospinning, the fiber containing the composition for forming the porous support is arranged in one direction. The advantages are as described above.
상기 전기방사는 약 1 kV 내지 약 1,000 kV의 고전압을 인가하여 실시될 수 있다. 전기방사는 일반적인 방법에 따라 수행될 수 있으므로， 자세한 내용은 생략하기로 한다.  The electrospinning may be performed by applying a high voltage of about 1 kV to about 1,000 kV. Since electrospinning can be performed according to a general method, details thereof will be omitted.
이어서， 상기 부직포를 열처리한다. 상기 열처리에 의해 상기 부직포에 포함된 폴리아믹산 또는 폴리이미드가 열전환에 의해 기계적 강도 및 치수 안정성이 우수하고 높은 자유 체적도를 갖는 고분자， 예컨대 폴리벤조옥사졸， 폴리밴조티아졸， 폴리피를론과 같은 고분자로 전환된다. 이로써 기계적 강도, 치수 안정성 등 물성이 우수한 다공성 지지체를 형성할 수 있다.  Subsequently, the nonwoven fabric is heat treated. The polyamic acid or polyimide included in the nonwoven fabric by the heat treatment is excellent in mechanical strength and dimensional stability by thermal conversion, and has a high free volume polymer such as polybenzoxazole, polybanzothiazole, polypylon Is converted to a polymer such as As a result, a porous support having excellent physical properties such as mechanical strength and dimensional stability can be formed.
구체적으로는 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량에 대하여, 열전환되는 반복단위의 비율 (열전환율)은 약 10몰% 내지 약 100몰%일 수 있으며， 구체적으로는 약 40몰% 내지 약 100몰%일 수 있다. 열전환율이 상기 범위 내인 경우 가질 수 있는 장점은 상술한 바와 같다. Specifically, with respect to the total amount of the repeating units included in the polyamic acid or the polyimide, the ratio (heat conversion rate) of the repeating units to be thermally converted may be about 10 mol% to about 100 mol%, specifically about 40 Mole% to about 100 mole%. Advantages that the thermal conversion rate may be in the above range is as described above.
상기 열처리는 약 250 °C 내지 약 550 °C의 온도로 수행될 수 있고， 약 10분 내지 약 5시간 동안 수행될 수 있으며, 열처리시 승온 속도는 약 1 °C/분 내지 약 20 °C/분일 수 있다. 열처리가 상기 조건 하에서 이루어지는 경우， 상기 폴리아믹산 및 폴리이미드의 열전환을 효과적으로 이루어지게 할 수 있다. 즉， 상기 폴리아믹산 및 상기 폴리이미드를 피코기공을 가지며 우수한 기계적 물성 및 높은 자유 체적도를 가지는 폴리벤조옥사졸， 폴리벤조티아졸， 폴리피를론과 같은 고분자로 용이하게 전환시킴으로써, 기계적 물성， 치수안정성, 내화학성 및 내열성이 우수하고 양이온 교환수지를 효과적으로 함유할 수 있으며 다공성 지지체를 형성할 수 있다. 구체적으로는 상기 열처리는 약 35CTC 내지 약 450°C의 은도로 수행될 수 있고, 약 1시간 내지 약 3시간 동안 수행될 수 있으며， 열처리시 승온 속도는 약 5 °C/분 내지 약 10 °C/분일 수 있다. The heat treatment may be performed at a temperature of about 250 ° C to about 550 ° C, may be performed for about 10 minutes to about 5 hours, the temperature increase rate during the heat treatment is from about 1 ° C / min to about 20 ° C / It may be minutes. When the heat treatment is performed under the above conditions, the thermal conversion of the polyamic acid and the polyimide is effectively Can be done. That is, the physical properties of the polyamic acid and the polyimide are easily converted into polymers such as polybenzoxazole, polybenzothiazole, and polypylon, which have picopores and have excellent mechanical properties and high free volume. It is excellent in dimensional stability, chemical resistance and heat resistance, can effectively contain a cation exchange resin, and can form a porous support. Specifically, the heat treatment may be performed with a silver of about 35 CTC to about 450 ° C, may be performed for about 1 hour to about 3 hours, the temperature increase rate during the heat treatment is from about 5 ° C / min to about 10 ° C It can be / minute.
이어서， 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 양이온 교환수지를 형성한다. 상기 다공성 지지체의 내부， 표면, 또는 내부와 표면에 양이온 교환수지를 형성하는 방법으로는 본래 고분자 내에 술폰산기， 카르복실산기, 인산기, 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지고 있는 고분자를 포함하는 용액에 상기 다공성 지지체를 침지시키는 방법; 및 본래 상기와 같은 작용기를 가지고 있지 않은 고분자를 포함하는 용액에 상기 다공성 지지체를 침지시키고 건조한 후， 상기와 같은 작용기를 포함하는 산 수용액에 다시 침지시켜 상기와 같은 작용기로 치환시키거나 또는 상기와 같은 작용기를 가지는 산으로 도핑하는 방법을 들 수 있으나， 이에 한정되는 것은 아니다. 상기 양이온 교환수지를 형성하기 위한 고분자를 포함하는 용액은 상기 고분자를 Ν,Ν-디메틸아세트아미드 (Ν,Ν-dimethylacetamide, DMAc), N- 메틸피를리돈 (N— Methyl pyrrol i done, NMP) 등의 유기 용매에 용해시켜 제조할 수 있다. 구체적으로는 상기 고분자를 포함하는 용액은 상기 고분자가 약 1 중량 %_내지 약 40 중량 %가 되도록 Ν,Ν-디메틸아세트아미드, Ν-메틸피롤리돈 등의 유기 용매에 용해시켜 제조할 수 있다. Subsequently, a cation exchange resin is formed on the inside, the surface, or the inside and the surface of the porous support. The method of forming a cation exchange resin in the interior, the surface, or the interior and the surface of the porous support has a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups and derivatives thereof in the polymer. Dipping the porous support in a solution containing a polymer; And immersing the porous support in a solution containing a polymer that does not have the functional group, and drying it, and then immersing it again in an aqueous acid solution containing the functional group to substitute the functional group as described above or And a method of doping with an acid having a functional group, but is not limited thereto. The solution containing the polymer for forming the cation exchange resin is the polymer Ν, Ν-dimethylacetamide (Ν, Ν-dimethylacetamide, DMAc), N- methylpyrrolidone (N— Methyl pyrrol i done, NMP) Dissolved in organic solvents, It can manufacture. Specifically, the solution containing the polymer may be prepared by dissolving in an organic solvent such as Ν, Ν-dimethylacetamide, Ν-methylpyrrolidone such that the polymer is about 1% by weight to about 40% by weight. .
상온 내지 약 200°C의 온도, 구체적으로는 약 80°C 내지 약 200°C의 온도에서， 상기 제조한 고분자를 포함하는 용액에 상기 다공성 지지체를 침지시킨 후， 약 1시간 내지 약 20시간 동안 방치한다. After immersing the porous support in a solution containing the prepared polymer at a temperature of room temperature to about 200 ° C, specifically about 80 ° C to about 200 ° C, for about 1 hour to about 20 hours Leave it.
예를 들어， 본래 고분자 내에 술폰산기, 카르복실산기， 인산기， 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지고 있는 고분자를 포함하는 용액에 상기 다공성 지지체를 침지시킨 경우는, 이를 진공 오븐에서 건조함으로써 연료 전지용 고분자 전해질 막을 형성할 수 있다. 그러나 이에 한정되지 않고， 상기 건조 후에 술폰산기， 카르복실산기, 인산기, 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지는 산 수용액에 다시 침지하고 건조함으로써 연료 전지용 고분자 전해질 막을 형성할 수도 있다.  For example, when the porous support is immersed in a solution containing a polymer having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof, in the original polymer, By drying in an oven, a polymer electrolyte membrane for a fuel cell can be formed. However, the present invention is not limited thereto, and the polymer electrolyte membrane for a fuel cell may be formed by immersion and drying again in an acid aqueous solution having a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof after the drying. have.
본래 고분자 내에 술폰산기， 카르복실산기， 인산기 , 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 작용기를 가지고 있지 않은 고분자를 포함하는 용액에 상기 다공성 지지체를 침지시킨 경우는， 이를 진공 오본에서 건조하고, 이어서 상기 술폰산， 카르복실산， 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 산을 포함하는 수용액에 침지하고 방치한 후, 꺼내어 증류수로 세척 및 건조함으로써 연료 전지용 고분자 전해질 막을 형성할 수 있다. 본 발명의 또 다른 일 구현예에 따르면, 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 상기 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 내부, 표면, 또는 내부와 표면에 산을 도핑하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법을 제공한다. When the porous support is immersed in a solution containing a polymer which does not have a functional group selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, phosphonic acid groups, and derivatives thereof in the polymer, it is dried in a vacuum Aubon. And then immersed in an aqueous solution containing an acid selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof, and then left out, washed and dried with distilled water to form a polymer electrolyte membrane for fuel cells. can do. According to another embodiment of the present invention, forming a nonwoven fabric by electrospinning the composition for forming the porous support; Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from the polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of doping the acid on the inside, the surface, or the inside and the surface of the porous support.
상기 산은 술폰산 카르복실산， 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택될 수 있으나， 이에 한정되는 것은 아니다. 이 경우는 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 별도의 양이온 교환수지를 형성하지 않고， 직접 상기 다공성 지지체의 내부, 표면, 또는 내부와 표면에 산을 도핑함으로써 연료 전지용 고분자 전해질 막을 형성하는 방법이다.  The acid may be selected from the group consisting of sulfonic acid carboxylic acid, phosphoric acid, phosphonic acid, and derivatives thereof, but is not limited thereto. In this case, a polymer electrolyte membrane for a fuel cell is formed by directly doping an acid into the inside, the surface, or the inside and the surface of the porous support without forming a separate cation exchange resin inside, the surface, or the inside and the surface of the porous support. That's how.
구체적으로는 상기 다공성 지지체를 술폰산， 카르복실산, 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 산을 포함하는 수용액에 침지시키고, 약 25°C 내지 약 200°C를 유지하면서， 약 1시간 내지 약 24시간 정도 방치한 후, 건조함으로써 연료 전지용 고분자 전해질 막올 형성할 수 있다. 상기 산 수용액으로는 약 1 M 내지 약 30 M의 농도를 가지는 산 수용액을 사용할 수 있다. 전기방사 및 열처리에 대한 설명은 상술한 바와 같다. . 또한 본 발명의 또 다른 일 구현예에 따르면, 상기 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및 상기 다공성 지지체의 표면에 불소기를 도입하는 단계를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법올 제공한다. 이 경우, 다공성 지지체와 예컨대 양이온 교환 수지와의 접착성이 향상될 수 있고， 다공성 지지체의 양이온 교환 수지에 대한 젖음성 (wettability)이 향상될 수 있다. 또한， 상기 다공성 지지체를 포함하는 연료 전지용 고분자 전해질 막의 삼투성 (permeation) , 전기 전도도 (electrical conductivity) , 그래프팅 (grafting) 특성 및 기계적 특성 (mechanical behavior)을 개선할 수 있다. 상기 불소기는 예컨대， 풀루오린, 플루오르화물을 사용하여 다공성 지지체에 직접 불소화법， 플라즈마 증착법 등의 방법으로 도입할 수 있고， 이로써 표면 불소화된 다공성 지지체를 제조할 수 있다. Specifically, the porous support is immersed in an aqueous solution containing an acid selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof, while maintaining about 25 ° C to about 200 ° C, After being left for about 1 hour to about 24 hours, the polymer electrolyte membrane for fuel cells can be formed by drying. As the acid aqueous solution, an acid aqueous solution having a concentration of about 1 M to about 30 M may be used. The description of the electrospinning and heat treatment is as described above. . In addition, according to another embodiment of the present invention, forming a nonwoven fabric by electrospinning the composition for forming the porous support; The nonwoven fabric Heat treating to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And it provides a method for producing a polymer electrolyte membrane for a fuel cell comprising the step of introducing a fluorine group on the surface of the porous support. In this case, the adhesion between the porous support and the cation exchange resin, for example, can be improved, and the wettability of the porous support to the cation exchange resin can be improved. In addition, the permeation, electrical conductivity, grafting characteristics and mechanical behavior of the polymer electrolyte membrane for a fuel cell including the porous support may be improved. For example, the fluorine group may be introduced into the porous support by using fluorine and fluoride, for example, by direct fluorination or plasma deposition, thereby preparing a surface fluorinated porous support.
이어서, 상술한 바에 따라 상기 다공성 지지체를 양이온 교환 수지에 함침하여 연료 전지용 고분자 전해질 막을 제조할 수 있다.  Subsequently, as described above, the porous support may be impregnated with a cation exchange resin to prepare a polymer electrolyte membrane for a fuel cell.
전기방사 및 열처리에 대한 설명은 상술한 바와 같다.  The description of the electrospinning and heat treatment is as described above.
본 발명의 일 구현예에 따른 연료 전지 시스템의 개략적인 구조를 도 2에 나타낸다. 도 2를 참조하면， 연료 및 산화제를 펌프를 사용하여 전기 발생부로 공급하는 시스템을 나타내었으나, 본 발명이 이에 한정되는 것은 아니며， 펌프를 사용하지 않는 확산 방식을 이용하는 연료 전지 시스템 구조에 사용할 수도 있다.  2 shows a schematic structure of a fuel cell system according to an embodiment of the present invention. Referring to FIG. 2, a system for supplying fuel and an oxidant to an electric generator using a pump is illustrated. However, the present invention is not limited thereto and may be used in a fuel cell system structure using a diffusion method without using a pump. .
본 발명의 일 구현예에 따른 연료 전지 시스템 (1)은 연료의 산화 반응과 산화제의 환원 반웅을 통해 전기 에너지를 발생시키는 적어도 하나의 전기 발생부 (3)， 연료를 상기 전기 발생부 (3)로 공급하는 연료 공급부 (5)， 산화제를 상기 전기 발생부 (3)로 공급하는 산화제 공급부 (7)를 포함한다. Fuel cell system 1 according to an embodiment of the present invention is characterized in that the oxidation of the fuel At least one electricity generator 3 for generating electrical energy through reaction and reduction of oxidant, a fuel supply unit 5 for supplying fuel to the electricity generator 3, and an oxidant for the electricity generator 3 And an oxidant supply portion 7 to be supplied to the furnace.
상기 연료를 공급하는 연료 공급부 (5)는 연료를 저장하는 연료 탱크 (9)， 연료 탱크 (9)에 연결 설치되는 연료 펌프 (11)를 구비할 수 있다. 상기 연료 펌프 (11)는 소정의 펌핑력에 의해 연료 탱크 (9)에 저장된 연료를 배출시키는 기능을 한다.  The fuel supply unit 5 for supplying the fuel may include a fuel tank 9 storing fuel and a fuel pump 11 connected to the fuel tank 9. The fuel pump 11 functions to discharge fuel stored in the fuel tank 9 by a predetermined pumping force.
상기 전기 발생부 (3)로 산화제를 공급하는 산화제 공급부 (7)는 소정의 펌핑력으로 산화제를 흡입하는 적어도 하나의 산화제 펌프 (13)를 구비한다.  The oxidant supply unit 7 for supplying the oxidant to the electricity generating unit 3 is provided with at least one oxidant pump 13 which sucks the oxidant with a predetermined pumping force.
상기 전기 발생부 (3)는 연료와 산화제를 산화 및 환원 반응시키는 막 -전극 어셈블리 (17)와 이 막 -전극 어셈블리의 양측에 연료와 산화제를 공급하기 위한 세퍼레이터 (19， 19')로 구성되며， 이러한 전기 발생부 (17)가 적어도 하나 모여 스택 (15)을 구성한다.  The electric generator 3 is composed of a membrane-electrode assembly 17 for oxidizing and reducing a fuel and an oxidant and a separator 19, 19 'for supplying fuel and an oxidant to both sides of the membrane-electrode assembly. At least one of these electricity generating units 17 constitutes a stack 15.
【발명의 실시를 위한 형태】  [Form for implementation of invention]
이하에서 본 발명을 실시예 및 비교예를 통하여 보다 상세하게 설명하고자 하나, 하기의 실시예 및 비교예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것은 아니다.  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.
실시예 1: 연료 전지용 고분자 전해질 막의 제조  Example 1 Preparation of Polymer Electrolyte Membrane for Fuel Cell
하기 반웅식 1로 표시되는 바에 따라 폴리하이드록시이미드로부터 하기 화학식 51로 표시되는 반복단위를 포함하는 폴리 벤조옥사졸을 포함하는 고분자를 포함하는 연료 전지용 고분자 전해질 막을 제조하였다 . From polyhydroxyimide as represented by the following reaction formula 1 A polymer electrolyte membrane for a fuel cell including a polymer including polybenzoxazole including a repeating unit represented by Formula 51 was prepared.
[반응식 1]  Scheme 1
Figure imgf000083_0001
Figure imgf000083_0001
(1) 폴리하이드록시이미드의 제조 (1) Preparation of Polyhydroxyimide
2 ,2-비스 (3-아미노 -4-하이드록시페닐)핵사플루오로프로판 3.66 g(10 誦 ol)과 4，4'— (핵사플루오로이소프로필리덴)디프탈릭 안하이드라이드 4.44 g(10 誦 ol)을 N-메틸피롤리돈 (NMP) 32.4 g에 넣고， 4시간 동안 격렬하게 교반하였다. 이어서， 공비흔합물로써 자일렌 32 ml를 첨가하고, 180°C에서 12시간 동안 열적 용액 이미드화하면서 물과 자일렌의 흔합물을 제거함으로써 폴리하이드록시이미드를 제조하였다. 3.66 g (10 μl) of 2,2-bis (3-amino-4-hydroxyphenyl) nucleofluoropropane and 4,4 ′ — (nucleofluoroisopropylidene) diphthalic anhydride Xol) was added to 32.4 g of N-methylpyrrolidone (NMP) and stirred vigorously for 4 hours. Then, polyhydroxyimide was prepared by adding 32 ml of xylene as an azeotrope and removing the mixture of water and xylene while thermal solution imidization at 180 ° C. for 12 hours.
(2) 폴리벤조옥사졸을 포함하는 다공성 지지체의 제조  (2) Preparation of Porous Support Containing Polybenzoxazole
상기 제조된 폴리하이드록시이미드를 포함하는 용액에 디메틸포름아미드 (DMF)를 첨가하여， 상기 폴리하이드록시이미드가 25 중량 %로 포함된 다공성 지지체 형성용 조성물을 제조하였다.  Dimethylformamide (DMF) was added to the prepared solution containing polyhydroxyimide to prepare a composition for forming a porous support including 25 wt% of the polyhydroxyimide.
상기 다공성 지지체 형성용 조성물을 드럼타입의 전기방사 장비 ESR200RD 나노엔씨 (NanoNC)사제)를 사용하여 실린더 부분에 +10kV, 드럼부분에 _4kV의 전기를 걸어주고， 방사간격 15 cm, flow rate 0.1^/min, 및 드럼 속도 50rpm의 조건으로 전기방사하여 섬유를 포함하는 부직포를 제조하였다.  The composition for forming the porous support was + 10kV to the cylinder part and _4kV to the drum part using a drum-type electrospinning equipment ESR200RD NanoNC (manufactured by NanoNC)), radiating interval 15 cm, flow rate 0.1 ^ / min, and electrospinning under the condition of a drum speed of 50 rpm to prepare a nonwoven fabric comprising fibers.
이어서, 상기 제조한 부직포를 300°C에서 1시간 동안 열처리한 후， 다시 40CTC에서 1시간 열처리 후에, 서서히 상온으로 넁각시켜 폴리벤조옥사졸을 포함하는 다공성 지지체를 제조하였다. 상기 열처리시의 승온 속도는 5 °C/분이었다. ' capillary flow porometer 장비 CFP- 1500-AE ( Po r ou s Materials사제)를 이용하여 측정한 상기 다공성 지지체의 기공도는 91%이었다. 또한 상기 다공성 지지체의 두께는 40 μιη이었다. Subsequently, the nonwoven fabric prepared above was heat-treated at 300 ° C. for 1 hour, and then heat-treated at 40 CTC for 1 hour, and then slowly cooled to room temperature to prepare a porous support including polybenzoxazole. The temperature increase rate at the time of the said heat processing was 5 degrees C / min. '' capillary flow porometer equipment CFP-1500-AE (Po r ou s The porosity of the porous support measured using Materials Corp. was 91%. In addition, the porous support had a thickness of 40 μιη.
(3) 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막의 제조  (3) Preparation of Polymer Electrolyte Membrane for Fuel Cell Containing Polybenzoxazole
상기 다공성 지지체를 술폰화된 폴리 (아릴렌 에테르 술폰) (sulfonated-poly(arylene ether sulfone: s-PAES)) 10 g을 Ν,Ν- 디메틸아세트아미드 (DMAc) 90 g에 용해한 용액에 1 시간 동안 침지한 후， 오븐에서 천천히 건조함으로써， 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 46몰¾>였다.  The porous support was dissolved in 10 g of sulfonated-poly (arylene ether sulfone: s-PAES) in 90 g of Ν, Ν-dimethylacetamide (DMAc) for 1 hour. After immersion, the polymer electrolyte membrane for a fuel cell containing polybenzoxazole was prepared by slowly drying in an oven. The thermal conversion was 46 mol¾>.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1,553 cm—1, 1,480 cm_1(C=N) 및 1，058 cm— O 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.193， 면간 거리는 558 pm였다. FT-IR analysis showed a band of 1,553 cm- 1 , 1,480 cm _1 (C = N) and 1,058 cm-0, which are polybenzoxazole characteristic bands that did not exist in polyhydroxyimide. In addition, the prepared polymer had a free volume of 0.193 and an interplanar distance of 558 pm.
고분자의 밀도는 자유 체적도와 관련이 있다.  The density of the polymer is related to the free volume.
먼저 막의 밀도를 하기 수학식 1에 따라 사르토리우스 LA 310S 정밀저을 (Sartorius LA 310S analytical balance)을 이용하여 부력법 (buoyancy method)으로 측정하였다.  First, the film density was measured by a buoyancy method using a Sartorius LA 310S analytical balance according to Equation 1 below.
[수학식 1]  [Equation 1]
_ W .. , . _ W ..,.
·"""■ ., 상기 수학식 1에서， Pp는 고분자의 밀도이고， ¬는 탈이온수의 밀도이고, · &Quot; " Pp is the density of the polymer, ¬ is the density of deionized water,
^는 공기 중에서 측정한 고분자의 무게이고，  ^ Is the weight of the polymer in air
^는 탈이온수에서 측정한 고분자의 무게이다.  ^ Is the weight of the polymer measured in deionized water.
자유 체적도 (FFV, V/)는 상기 데이터로부터 하기 수학식 2에 따라 계산했다. Free volume (FFV, V / ) was calculated from the data according to the following equation (2).
[수학식 2]
Figure imgf000086_0001
[Equation 2]
Figure imgf000086_0001
상기 수학식 2에서，  In Equation 2,
V는 고분자의 비부피 (specific volume)이고,  V is the specific volume of the polymer,
Vw는 반데르발스 비부피 (specific Van der Waals volume)이다.  Vw is the specific Van der Waals volume.
면간 거리는 Xᅳ선 회절 패턴 결과로부터 브래그 식 (Bragg's equation)에 따라 계산하였다.  The interplanar distance was calculated according to the Bragg's equation from the X-ray diffraction pattern results.
또한 상기 폴리벤조옥사졸을 포함하는 다공성 지지체에서， 양전자 소멸시간 분광분석 (positron annihi lation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 16.1 pm였다.  In addition, in the porous support including the polybenzoxazole, the full width at half maximum (FWHM) by positron annihilation lifetime spectroscopy (PALS) was 16.1 pm.
PALS 측정은 automated EG&G Ortec fast-fast coincidence spectrometer를 이용하여 대기 온도에서 질소에 대하여 실시하였다. 상기 시스템의 시간 해상도는 240 ps이었다.  PALS measurements were performed on nitrogen at ambient temperature using an automated EG & G Ortec fast-fast coincidence spectrometer. The time resolution of the system was 240 ps.
고분자막을 22Na-Ti 포일 소스 (22Na_Ti foil source)의 양쪽에 1 關 두께로 설치하였다. Ti 포일 (두께 2. mi)에 대한 소스 보정은 없었다. 각각의 스펙트럼은 약 工천만 통합 카운트로 이루어졌고， 세 개의 감쇠지수 (decaying exponent ial )의 합으로 또는 연속분포 (continuous distribution)로 만들어졌다. 상기 PALS 데이터는 22Na 동위원소로부터 발생되는 양전자를 조사하여 생성시에 발생되는 1.27MeV의 와 소멸시에 발생되는 0.511MeV의 Y l, 의 시간차이 " , τ2, τ3등을 이용하여 얻을 수 있었다. The polymer film on either side of the 22 Na-Ti foil source (22 Na_Ti foil source) 1關 Installed in thickness. There was no source correction for Ti foil (thickness 2. mi). Each spectrum consists of about 10 million integrated counts and is made up of a sum of three decaying exponent ials or a continuous distribution. The PALS data were obtained by investigating positrons generated from 22 Na isotopes using the time difference between 1.27 MeV generated at the time of generation and Y l , 0.511MeV generated at the time of extinction, τ 2 , τ 3 , and the like. Could.
기공의 크기는 0.511MeV의 두 개의 γ 신호의 소멸시간을 사용하여 하기 수학식 3을 통해 계산하였다.  The pore size was calculated using Equation 3 below using the extinction time of two γ signals of 0.511 MeV.
[수학식 3] -  [Equation 3]-
R 1 . 2nR R 1. 2nR
To-Ps ~ •sin T o-Ps ~ • sin
2 R + AR 2π 상기 수학식 3에서，  2 R + AR 2π In Equation 3,
T0-Ps는 양전자의 소멸시간이고, T 0 - Ps is the extinction time of the positron,
R은 기공 크기이고，  R is the pore size
은 기공이 구형이라는 가정의 실험 파라미터 (emipirical parameter)이다.  Is an experimental parameter on the assumption that the pores are spherical.
실시예 2: 연료 전지용 고분자 전해질 막의 제조  Example 2: Preparation of Polymer Electrolyte Membrane for Fuel Cell
부직포를 400°C에서 2시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 61%였다. A polymer electrolyte membrane for a fuel cell comprising a polybenzoxazole including a repeating unit represented by Chemical Formula 51 in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 400 ° C. for 2 hours. Prepared. The thermal conversion was 61%.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리밴조옥사졸 특성밴드인 1,553 ατΓ1, 1,480 cnf ON) 및 1,058 cm_1(C- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.200, 면간 거리는 564.4 pm였다. The FT-IR analysis confirmed the bands of 1,553 ατΓ 1 , 1,480 cnf ON) and 1,058 cm _1 (C-0), which were characteristic bands of polybanozoxazole, which did not exist in polyhydroxyimide. In addition, the prepared polymer had a free volume of 0.200 and an interplanar distance of 564.4 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 19.4 pm였다.  In addition, the full width at half maximum (FWHM) measured by positron annihilation lifetime spectroscopy (PALS) was 19.4 pm.
실시예 3: 연료 전지용 고분자 전해질 막의 제조  Example 3: Preparation of Polymer Electrolyte Membrane for Fuel Cell
부직포를 400°C에서 3시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸올 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 69%였다. A polymer electrolyte membrane for a fuel cell including a polybenzoxazolol including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 400 ° C. for 3 hours. Thermal conversion was 69%.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1，553 cm"1, 1,480 cm— ON) 및 1,058 cm'HC- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.204， 면간 거리는 567.6 pm였다. The FT-IR analysis revealed a band of 1,553 cm "1 , 1,480 cm-ON) and 1,058 cm ' HC-0), a polybenzoxazole characteristic band that did not exist in polyhydroxyimide. The free volume of was 0.204 and the distance between planes was 567.6 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 21.1 pm였다.  In addition, the full width at half maximum (FWHM) measured by positron annihilation lifetime spectroscopy (PALS) was 21.1 pm.
실시예 4: 연료 전지용 고분자 전해질 막의 제조 부직포를 425°C에서 1시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 80%였다. Example 4 Preparation of Polymer Electrolyte Membrane for Fuel Cell A polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 425 ° C. for 1 hour. The thermal conversion was 80%.
FT-IR 분석결과 폴라하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1,553 cm"1, 1,480 cm-1(C=N) 및 1,058 cm—1(C- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.210， 면간 거리는 572 pm였다. As a result of FT-IR analysis in the mid-polar hydroxyimino polybenzoxazole characteristic band of 1,553 cm "1, 1,480 cm -1 were not present (C = N), and it was confirmed that bands of 1,058 cm- 1 (C- 0). In addition, the prepared polymer had a free volume of 0.210 and an interplanar distance of 572 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 23.6 pm였다.  In addition, the full width at half maximum (FWHM) by positron annihilation lifetime spectroscopy (PALS) was 23.6 pm.
실시예 5: 연료 전지용 고분자 전해질 막의 제조  Example 5 Preparation of Polymer Electrolyte Membrane for Fuel Cell
부직포를 425°C에서 2시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 88%였다. A polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 425 ° C. for 2 hours. Thermal conversion was 88%.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1,553 cm"1, 1,480 cm_1(C=N) 및 1,058 cm_1(C- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.214， 면간 거리는 575.2 pm였다. The FT-IR analysis revealed bands of 1,553 cm "1 , 1,480 cm _1 (C = N) and 1,058 cm _1 (C-0), polybenzoxazole characteristic bands that were not present in the polyhydroxyimide. The free volume of the polymer was 0.214 and the interplanar distance was 575.2 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, F觀)은 25.3 pm였다. Positron annihilation lifetime The full width at half maximum (FV) by spectroscopy (PALS) measurement was 25.3 pm.
실시예 6: 연료 전지용 고분자 전해질 막의 제조  Example 6: Preparation of Polymer Electrolyte Membrane for Fuel Cell
부직포를 425°C에서 3시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 91%였다. A polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat-treated at 425 ° C. for 3 hours. Thermal conversion was 91%.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1,553 cm"1, 1,480 cm_1(C=N) 및 1,058 cm'HC- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.215， 면간 거리는 576.4 pm였다. FT-IR analysis showed a band of 1,553 cm "1 , 1,480 cm _1 (C = N) and 1,058 cm ' HC-0), polybenzoxazole characteristic bands, which were not present in polyhydroxyimide. The free volume of the polymer was 0.215 and the interplanar distance was 576.4 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 26.2 pm였다.  In addition, the full width at half maximum (FWHM) measured by positron annihilation lifetime spectroscopy (PALS) was 26.2 pm.
실시예 7: 연료 전지용 고분자 전해질 막의 제조  Example 7: Preparation of Polymer Electrolyte Membrane for Fuel Cell
부직포를 450°C에서 1시간 동안 열처리한 것을 제외하고는 상기 실시예 1과 동일한 방법으로 상기 화학식 51로 표시되는 반복단위를 포함하는 폴리벤조옥사졸을 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. 열전환율은 95%였다. A polymer electrolyte membrane for a fuel cell including a polybenzoxazole including a repeating unit represented by Chemical Formula 51 was prepared in the same manner as in Example 1 except that the nonwoven fabric was heat treated at 450 ° C. for 1 hour. Thermal conversion was 95%.
FT-IR 분석결과 폴리하이드록시이미드에서는 존재하지 않았던 폴리벤조옥사졸 특성밴드인 1，553 cm-1, 1,480 cm_1(C=N) 및 1，058 cm_1(C- 0)의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.217, 면간 거리는 578 pm였다. FT-IR analysis showed that polybenzoxazole characteristic bands 1,553 cm -1 , 1,480 cm _1 (C = N) and 1,058 cm _1 (C- A band of 0) was identified. In addition, the prepared polymer had a free volume of 0.217 and an interplanar distance of 578 pm.
또한 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)은 26.9 pm였다.  In addition, the full width at half maximum (FWHM) measured by positron annihilation lifetime spectroscopy (PALS) was 26.9 pm.
비교예 1: 연료 전지용 고분자 전해질 막의 제조  Comparative Example 1: Preparation of Polymer Electrolyte Membrane for Fuel Cell
하기 반웅식 2로 표시되는 바에 따라 폴리아믹산으로부터 하기 화학식 52로 표시되는 반복단위를 포함하는 폴리이미드를 포함하는 고분자를 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. A polymer electrolyte membrane for a fuel cell including a polymer including a polyimide including a repeating unit represented by the following Chemical Formula 52 was prepared from a polyamic acid as represented by the following formula (2).
[반응식 2]
Figure imgf000092_0001
Scheme 2
Figure imgf000092_0001
Figure imgf000092_0002
Figure imgf000092_0002
(1) 폴리아믹산의 제조 (1) Preparation of Polyamic Acid
3，3'，4，4'-비페닐 테트라카프복실릭 디안하드라이드 (3, 3' ,4,4'- bi henyl tetracarboxyl ic di anhydride) 2.94 g(10 隱 ol)과 4,4'- 디아미노디페닐 에테르 (4，4'— diaminodiphenyl ether) 2.00 g(10 mmol)을 디메틸아세트아마이드 (DMAc) 20 ml에 넣고 15°C에서 4시간 반응시켜 연노란색의 점도가 있는 폴리아믹산 용액을 제조하였다.
Figure imgf000092_0003
폴리아믹산의 중량 평균 분자량은 120 ,000이었다 3,3 ', 4,4'-biphenyl tetracapoxycyclic dianhydride (2,3', 4,4'-bihenyl tetracarboxyl ic di anhydride) 2.94 g (10 隱 ol) and 4,4'- 2.00 g (10 mmol) of diaminodiphenyl ether (4,4'—diaminodiphenyl ether) was added to 20 ml of dimethylacetamide (DMAc) and reacted at 15 ° C. for 4 hours to prepare a solution of light yellow colored polyamic acid. It was.
Figure imgf000092_0003
The weight average molecular weight of the polyamic acid was 120,000
(2) 폴리이미드를 포함하는 다공성 지지체의 제조 상기 제조된 점도가 있는 폴리아믹산 용액에 디메틸포름아미드 (DMF)를 첨가하여, 상기 폴리아믹산이 25 증량 %로 포함된 다공성 지지체 형성용 조성물을 제조하였다. (2) Preparation of Porous Support Comprising Polyimide Dimethylformamide (DMF) was added to the prepared polyamic acid solution to prepare a composition for forming a porous support including 25% by weight of the polyamic acid.
상기 다공성 지지체 형성용 드럼타입의 전기방사 장비를 사용하여 실린더 부분에 +12kV, 드럼부분에 -4kV의 전기를 걸어주고， 방사간격은 15 cm, flow rate 0.1/d/min, 및 드럼 속도 50rpm의 조건으로 전기방사하여 섬유를 포함하는 부직포를 제조하였다.  Using the drum type electrospinning equipment for forming the porous support, +12 kV is applied to the cylinder part and -4 kV to the drum part, and the radial interval is 15 cm, flow rate 0.1 / d / min, and drum speed of 50 rpm. Electrospun under conditions to prepare a nonwoven fabric containing the fiber.
이어서， 상기 제조한 부직포를 350 °C.에서 1시간 동안 열처리한 후, 서서히 상온으로 넁각시켜 폴리이미드를 포함하는 다공성 지지체를 제조하였다. 상기 열처리시의 승온 속도는 5°C/분이었다.  Subsequently, the nonwoven fabric prepared above was heat-treated at 350 ° C. for 1 hour, and then slowly reacted to room temperature to prepare a porous support including polyimide. The temperature increase rate during the heat treatment was 5 ° C / min.
capillary flow porometer 장비를 이용하여 측정한 상기 다공성 지지체의 기공도는 65¾>이었다. 또한 상기 다공성 지지체의 두께는 43 /m이었다.  The porosity of the porous support measured using a capillary flow porometer device was 65¾>. In addition, the porous support had a thickness of 43 / m.
(4) 폴리이미드를 포함하는 연료 전지용 고분자 전해질 막의 제조 상기 다공성 지지체를 술폰화된 폴리 (아릴렌 에테르 술폰) (sul fonated一 poly(arylene ether sulfone: sᅳ PAES)) 10 g을 디메틸포름아미드 (DMF) 90 g에 용해한 용액에 1 시간 동안 침지한 후， 오븐에서 천천히 건조함으로써， 폴리이미드를 포함하는 연료 전지용 고분자 전해질 막을 제조하였다. ' (4) Preparation of Polymer Electrolyte Membrane for Fuel Cell Containing Polyimide 10 g of sulfonated poly (arylene ether sulfone: s PAES) was used as the porous support. DMF) was immersed in a solution dissolved in 90 g for 1 hour, and then slowly dried in an oven to prepare a polymer electrolyte membrane for a fuel cell containing polyimide. '
FT-IR 분석결과 폴리이미드 특성밴드인 1787 cm—1, 1731cm"1, 1360 cm"1 및 724 cn 1의 밴드가 확인되었다. 또한 제조된 고분자의 자유체적도는 0.12， 면간 거리는 520 pm였다. A result of FT-IR analysis, it was confirmed that a polyimide characteristic band of 1787 bands in cm- 1, 1731cm "1, 1360 cm" 1 and 724 cn 1. In addition, the free volume of the prepared polymer 0.12, face-to-face distance was 520 pm.
시험예 1: 사진  Test Example 1: Photo
상기 실시예 1 내지 7 및 상기 비교예 1에서 제조한 다공성 지지체에 대하여 일반 카메라를 사용하여 사진을 촬영하였다. 이 중， 실시예 4에서 제조한 다공성 지지체의 사진을 도 3에 나타내었다.  The porous support prepared in Examples 1 to 7 and Comparative Example 1 was photographed using a general camera. Among them, a photo of the porous support prepared in Example 4 is shown in FIG.
상기 실시예 1 내지 7 및 상기 비교예 1에서 제조한 연료 전지용 고분자 전해질 막에 대하여 일반 카메라를 사용하여 사진을 촬영하였다. 이 중， 실시예 4에서 제조한 연료 전지용 고분자 전해질 막의 사진을 도 4에 나타내었다.  The fuel cell polymer electrolyte membranes prepared in Examples 1 to 7 and Comparative Example 1 were photographed using a general camera. Among these, the photo of the fuel cell polymer electrolyte membrane prepared in Example 4 is shown in FIG.
도 3 및 도 4에 나타난 바와 같이， 실시예 4에서 제조한 다공성 지지체는 양이은 교환 수지에 효과적으로 젖어서 투명하게 변화됨을 확인할 수 있다. 결과적으로 실시예 4에서 제조한 다공성 지지체는 양이온 교환 수지에 대한 젖음성이 우수하여 양이온 교환 수지가 잘 함침됨을 확인할 수 있다.  As shown in Figures 3 and 4, it can be seen that the porous support prepared in Example 4 is effectively wetted with bivalent silver exchange resin to change transparent. As a result, the porous support prepared in Example 4 can be confirmed that the cation exchange resin is well impregnated with excellent wettability to the cation exchange resin.
시험예 2: 프로톤 전도성 평가  Test Example 2: Proton Conductivity Evaluation
상기 실시예 1 내지 7 및 상기 비교예 1에서 제조한 연료 전지용 고분자 전해질 막을 1 cm X 4 cm 크기로 자른 早， i mpedance/ ga i nphase analyzer (Solartron 1260)과 electrochemical interf ace(Solartron 1287, Farnborough, Hampshire, UK) 장비에 상기 각각의 연료 전지용 고분자 전해질 막을 고정하여, R 값을 측정하였고， 하기 수학식 4를 통해 프로톤 전도성을 계산하였다. 그 중， 실시예 4에 대한 결과를 하기 표 1에 나타내었다. After cutting the polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 to 1 cm X 4 cm size, i mpedance / ga i n phase analyzer (Solartron 1260) and electrochemical interace (Solartron 1287, Farnborough, Hampshire, UK) was fixed to each of the polymer electrolyte membrane for the fuel cell, the R value was measured, the proton conductivity was calculated through the following equation (4). Among them, the results for Example 4 are shown in Table 1 below. Indicated.
[수학식 4]  [Equation 4]
프로톤 전도성 = d/(LsxWsxR) Proton Conductivity = d / (L s xW s xR)
d: 전극 사이의 거리  d: distance between electrodes
Ls: 연료 전지용 고분자 전해질 막의 두께 L s : Thickness of polymer electrolyte membrane for fuel cell
Ws: 연료 전지용 고분자 전해질 막의 폭 (1 cm) W s : width of polymer electrolyte membrane for fuel cell (1 cm)
R: 저항  R: resistance
시험예 3: 수분 흡수율 (water uptake) 특성 평가  Test Example 3 Evaluation of Water Uptake Characteristics
상기 실시예 1 내지 7 및 상기 비교예 1에서 제조한 연료 전지용 고분자 전해질 막을 4 cm X 4 cm의 크기로 잘랐다.  The polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 was cut to a size of 4 cm X 4 cm.
이어서, 각각의 연료 전지용 고분자 전해질 막의 건조 상태의 중량 (Wd)을 측정하였다. Subsequently, the weight (W d ) of the dry state of the polymer electrolyte membrane for each fuel cell was measured.
이어서， 상기 각각의 연료 전지용 고분자 전해질 막을 8(rc에서 증류수에 24시간 동안 담가두었다. 이어서, 상기 각각의 연료 전지용 고분자 전해질 막을 꺼내어 연료 전지용 고분자 전해질 막의 중량 (Ww)을 측정하였다. Subsequently, each of the fuel cell polymer electrolyte membranes was immersed in distilled water at 8 ( rc for 24 hours. Then, each of the fuel cell polymer electrolyte membranes was taken out to measure the weight (W w ) of the fuel cell polymer electrolyte membranes.
상기 측정한 중량값을 하기 수학식 5에 대입하여 수분 흡수율을 계산하였다.  The moisture absorption rate was calculated by substituting the measured weight value into the following Equation 5.
[수학식 5]  [Equation 5]
수분흡수율 (%) = ((Ww-Wd)/Wd)xl00 Water absorption (%) = ((W w -W d ) / W d ) xl00
Wd: 연료 전지용 고분자 전해질 막의 건조 상태의 중량 Ww: 연료 전지용 고분자 전해질 막의 수화된 후의 중량 W d : dry weight of the polymer electrolyte membrane for a fuel cell W w : Weight after hydration of the polymer electrolyte membrane for fuel cell
시험예 4: 치수안정성 평가  Test Example 4 Evaluation of Dimensional Stability
상기 실시예 1 내지 7 및 상기 비교예 1에서 제조한 연료 전지용 고분자 전해질 막을 4 cm X 4 cm의 크기로 잘랐다. 이어서, 각각의 연료 전지용 고분자 전해질 막을 lOCrC의 진공 오븐에서 24 시간 동안 건조하였다. 건조한 상태에서, 상기 각각의 연료 전지용 고분자 전해질 막의 길이 및 폭을 측정하였다.  The polymer electrolyte membrane for fuel cells prepared in Examples 1 to 7 and Comparative Example 1 was cut to a size of 4 cm X 4 cm. Each polymer electrolyte membrane for fuel cells was then dried in a vacuum oven of lOCrC for 24 hours. In the dry state, the length and width of each of the polymer electrolyte membranes for fuel cells were measured.
이어서， 상기 각각의 연료 전지용 고분자 전해질 막을 8(rc의 증류수에 담근 후， 하루 동안 방치하였다. 상기 각각의 수화된 연료 전지용 고분자 전해질 막을 꺼내어 연료 전지용 고분자 전해질 막의 길이 및 폭을 측정하였다. Subsequently, each of the fuel cell polymer electrolyte membranes was immersed in 8 ( rc distilled water and left for one day. Each of the hydrated fuel cell polymer electrolyte membranes was taken out to measure the length and width of the fuel cell polymer electrolyte membranes.
상기 연료 전지용 고분자 전해질 막의 길이 및 폭은， 수화된 연료 전지용 고분자 전해질 막에서의 물 분자의 빠른 탈착으로 인한 오차를 줄이기 위해， 비디오 현미경 시스템 (video microscope system) ICS- 305B(Sometech사제)를 사용하여 측정하였다.  The length and width of the polymer electrolyte membrane for fuel cells may be reduced by using a video microscope system ICS-305B (manufactured by Sometech) to reduce errors due to rapid desorption of water molecules from the hydrated fuel cell polymer electrolyte membrane. Measured.
상기 측정한 연료 전지용 고분자 전해질 막의 길이 및 폭을 하기 수학식 6에 대입하여 치수안정성을 평가하였다. 여기서는 연료 전지용 고분자 전해질 막의 길이를 사용하여 치수안정성을 평가하였다.  The dimensional stability was evaluated by substituting the measured length and width of the fuel cell polymer electrolyte membrane into the following equation (6). Dimensional stability was evaluated here using the length of the polymer electrolyte membrane for fuel cells.
[수학식 6]  [Equation 6]
치수안정성 (dimensional change , )= ((Dwet-Ddry)/Ddry) x 100 Dimensional change () = ((D wet -D dry ) / D dry ) x 100
Ddry: 건조한 연료 전지용 고분자 전해질 막의 치수 (길이 또는 폭) Dwet: 수화된 연료 전지용 고분자 전해질 막의 치수 (길이 또는 폭) [표 1] D dry : Dimension (length or width) of polymer electrolyte membrane for dry fuel cell D wet : Dimension (length or width) of polymer electrolyte membrane for hydrated fuel cell [Table 1]
Figure imgf000097_0001
Figure imgf000097_0001
상기 표 1에 나타난 바와 같이， 실시예 4에서 제조한 연료 전지용 고분자 전해질 막이 비교예 1에서 제조한 연료 전지용 고분자 전해질 막보다 우수한 프로톤 전도성을 가지면서 동시에 낮은 수분 흡수율 및 높은 치수안정성을 나타냄을 확인할 수 있다.  As shown in Table 1, the fuel cell polymer electrolyte membrane prepared in Example 4 has a superior proton conductivity than the fuel cell polymer electrolyte membrane prepared in Comparative Example 1, and at the same time exhibits low water absorption and high dimensional stability. have.
이상을 통해 본 발명의 구체적인 실시예에 대하여 설명하였지만， 본 발명은 이에 한정되는 것이 아니고 특허청구범위와 발명의 상세한 설명 및 첨부한 도면의 범위 안에서 여러 가지로 변형하여 실시하는 것이 가능하고 이 또한 본 발명의 범위에 속하는 것은 당연하다.  Although specific embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.
【부호의 설명】  [Explanation of code]
20： 연료 전지용 막—전극 어셈블리, 22： 애노드,  20: membrane-electrode assembly for fuel cells, 22: anode,
24： 고분자 전해질 막, 26： 캐소드，  24: polymer electrolyte membrane, 26: cathode,
244： 다공성 지지체, 242： 양이온 교환 수 1： 연료 전지 시스템， 3： 전기 발생부, 5： 연료 공급부， 7： 산화제 공급부， 9： 연료 탱크, 11: 연료 펌프, ： 산화제 펌프， 17： 막 -전극 어셈블리 ， 19'： 세퍼레이터 15： 스택 244: porous support, 242: cation exchange water 1: fuel cell system; 3: electricity generator; 5: fuel supply; 7: oxidant supply; 9: fuel tank; 11: fuel pump; ： Oxidizer pump ， 17 ： Membrane-electrode assembly ， 19 ′ ： Separator 15 ： Stack

Claims

【청구의 범위】 [Range of request]
【청구항 11  [Claim 11
폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체로，  A porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide,
상기 다공성 지지체는 미세기공, 그리고 상기 폴리아믹산으로부터 유도된 고분자에 존재하는 피코기공 또는 상기 폴리이미드로부터 유도된 고분자에 존재하는 피코기공을 가지며，  The porous support has micropores and picopores present in the polymer derived from the polyamic acid or picopores present in the polymer derived from the polyimide,
상기. 폴리아믹산 및 상기 폴리이미드는 아¾기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 포함하는 것인, 다공성 지지체. remind. Wherein the polyamic acid and the polyimide comprise repeating units made from aromatic diamines and dianhydrides comprising at least one functional group present at the ortho position relative to the amino group.
【청구항 2] [Claim 2]
제 1항에 있어서,  The method of claim 1,
상기 작용기는 OH, SH 또는 NH2를 포함하는 것인 다공성 지지체. Wherein said functional group comprises OH, SH or NH 2 .
【청구항 3】 [Claim 3]
제 1항에 있어서，  The method of claim 1,
상기 고분자는 상기 폴리아믹산 또는 상기 폴리이미드로부터 열전환되어 유도되는 것이고， 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량에 대하여, 열전환되는 반복단위의 비율 (열전환율)은 10몰% 내지 100몰%인 것인 다공성 지지체.  The polymer is induced by thermal conversion from the polyamic acid or the polyimide, and the ratio (thermal conversion rate) of the thermally converted repeating unit to the total amount of the repeating units included in the polyamic acid or the polyimide is 10 mol%. To 100 mol% of the porous support.
【청구항 4】  [Claim 4]
거 U항에 있어서， 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 0.18 내지 0.40의 자유 체적도 (FFV)를 가지는 것인 다공성 지지체. In U, The polymer derived from the polyamic acid and the polymer derived from the polyimide have a free volume (FFV) of 0.18 to 0.40.
【청구항 5】  [Claim 5]
게 1항에 있어서，  According to claim 1,
상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 XRD 측정에 의한 면간 거리가 550 pm 내지 800 pm의 범위에 있는 것인 다공성 지지처 1.  The polymer derived from the polyamic acid and the polymer derived from the polyimide have a porosity range of 550 pm to 800 pm in terms of an interplanar distance by XRD measurement.
【청구항 6】  [Claim 6]
제 1항에 있어서，  The method of claim 1,
상기 피코기공은 2개 이상이 서로 연결되어 모래시계 모양 (hourglass shaped)을 형성하는 것인 다공성 지지체. .  The picopores are two or more connected to each other to form an hourglass shaped (hourglass shaped). .
【청구항 7】 [Claim 7]
제 1항에 있어서，  The method of claim 1,
상기 피코기공은 양전자 소멸시간 분광분석 (positron annihilation lifetime spectroscopy, PALS) 측정에 의한 반가폭 (full width at half maximum, FWHM)이 10 pm 내지 40 pm의 범위에 있는 것인 다공성 지지체..  The picopores are porous supports having a full width at half maximum (FWHM) in the range of 10 pm to 40 pm by positron annihilation lifetime spectroscopy (PALS) measurement.
【청구항 8] [Claim 8]
제 1항에 있어서,  The method of claim 1,
상기 다공성 지지체는 지지체 총 부피에 대하여 10 부피 % 내지 95 부피 %의 기공도를 갖는 것인 다공성 지지체. The porous support has a porosity of 10% to 95% by volume relative to the total volume of the support.
【청구항 9】 [Claim 9]
거 U항에 있어서，  In U,
상기 다공성 지지체는 10 /zm 내지 200 의 두께를 갖는 것인 다공성 지지체ᅳ  The porous support is a porous support having a thickness of 10 / zm to 200 ᅳ
【청구항 10】  [Claim 10]
제 1항에 있어서，  The method of claim 1,
상기 폴리아믹산은 하기 화학식 1 내지 4로 표시되는 반복단위를 포함하는 폴리아믹산, 하기 화학식 5 내지 8로 표시되는 반복단위를 포함하는 폴리아믹산 공중합체， 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택되고，  The polyamic acid is a polyamic acid including a repeating unit represented by the following Chemical Formulas 1 to 4, a polyamic acid copolymer comprising a repeating unit represented by the following Chemical Formulas 5 to 8, copolymers thereof, and blends thereof Selected,
상기 폴리이미드는 하기 화학식 19 내지 22로 표시되는 반복단위를 포함하는 폴리이미드, 하기 화학식 23 내지 26으로 표시되는 반복단위를 포함하는 폴리이미드 공중합체, 이들의 공중합체 및 이들의 블렌드로 이루어진 군으로부터 선택되는 것인 다공성 지지체:  The polyimide is a polyimide comprising a repeating unit represented by the following formulas 19 to 22, a polyimide copolymer comprising a repeating unit represented by the following formulas 23 to 26, copolymers thereof and blends thereof The porous support that is selected:
[화학식 1]
Figure imgf000101_0001
[Formula 1]
Figure imgf000101_0001
[화학식 2]
Figure imgf000101_0002
[화학식 3]
Figure imgf000102_0001
[Formula 2]
Figure imgf000101_0002
[Formula 3]
Figure imgf000102_0001
[화학식 4]
Figure imgf000102_0002
[Formula 4]
Figure imgf000102_0002
[화학식 5]
Figure imgf000102_0003
[Formula 5]
Figure imgf000102_0003
[화학식 6]
Figure imgf000102_0004
[Formula 6]
Figure imgf000102_0004
[화학식 7]
Figure imgf000102_0005
Figure imgf000102_0006
[Formula 7]
Figure imgf000102_0005
Figure imgf000102_0006
Figure imgf000103_0001
Figure imgf000103_0001
Figure imgf000103_0002
Figure imgf000103_0002
Figure imgf000103_0003
Figure imgf000103_0003
Figure imgf000103_0004
Figure imgf000103_0005
Figure imgf000103_0004
Figure imgf000103_0005
101 [화학식 24]
Figure imgf000104_0001
101 [Formula 24]
Figure imgf000104_0001
[화학식 25]  [Formula 25]
Figure imgf000104_0002
Figure imgf000104_0002
상기 화학식 l 내지 8 및 화학식 19 내지 26에서，  In Chemical Formulas 1 to 8 and 19 to 26,
A 은 치환 또는 비치환된 4가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 4가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고， 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0， S, C(=0), CH(OH) , S(=0)2, Si(C¾)2, (CH2)P (여기서 , 1<ρ≤10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고，A is an aromatic ring group selected from a substituted or unsubstituted tetravalent C6 to C24 arylene group and a substituted or unsubstituted tetravalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more are joined to each other to form a condensed ring; At least two single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (C¾) 2 , (CH 2 ) P (where 1 <ρ≤10), (CF 2 ) q where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH,
Ar2는 치환 또는 비치환된 2가의 C6 내지 C24 아릴렌기 및 치환 또 비치환된 2가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고, 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합, 0, S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (CH2)P (여기서， l≤p≤10), (CF2)q (여기서, l<q<10), C(CH3)2> C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고, Q는 0， S, C(=0), CH(OH), S(=0)2, Si(C¾)2, (CH2)P (여기서, l≤p<10), (CF2)q (여기서, l<q<10), C(CH3)2> C(CF3)2> C(=0)NH, C(CH3)(CF3), 또는 치환 또는 비치환된 페닐렌기 (여기서 치환된 페닐렌기는 C1 내지 C6 알킬기 또는 C1 내지 C6 할로알킬기로 치환된다)이고, 이때 상기 Q는 양쪽 방향족 고리와 ni-m, m-p, p— m, 또는 p-p 위치로 연결되고，Ar 2 is an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring group is present alone; Two or more Joined to form a condensed ring; Two or more single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P (where l≤p≤10) , (CF 2 ) q where l <q <10), C (CH 3 ) 2> C (CF 3 ) 2 or C (= 0) NH, and Q is 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (C¾) 2 , (CH 2 ) P (where l ≦ p <10), (CF 2 ) q (where l <q <10), C (CH 3 ) 2> C (CF 3 ) 2> C (= 0) NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group (where the substituted phenylene group C1 to C6 alkyl group or C1 to C6 haloalkyl group), wherein Q is linked to both aromatic rings at ni-m, mp, p-m, or pp positions,
Y는 각각의 반복단위에서 동일하거나 서로 상이하며, 각각 독립적으로 OH, SH또는 NH2이고， Y is the same or different in each repeating unit, each independently OH, SH or NH 2 ,
n은 20≤n≤200을 만족하는 정수이고，  n is an integer satisfying 20≤n≤200,
m은 10≤m≤400을 만족하는 정수이고，  m is an integer satisfying 10≤m≤400,
1은 10≤1≤400을 만족하는 정수이다.  1 is an integer satisfying 10≤1≤400.
【청구항 11】  [Claim 11]
제 10항에 있어서，  The method of claim 10,
상기 Arr& 하기 식으로 표시된 것 중에서 선택되는 것인 다공성 지지체： The porous support selected from the above-mentioned Arr & is represented by the following formula:
Figure imgf000106_0001
상기 식에서，
Figure imgf000106_0001
In the above formula,
Xi, ¾, x3 및 는 동일하거나 서로 상이하며 각각 독립적으로 0， S, C(O), CH(OH), S(=0)2, Si(CH3)2, (C¾)p (여기서， 1<ρ<10), (CF2)q (여기서， l<q<10), C(C¾)2, C(CF3)2> 또는 C(=0)NH이고， Xi, ¾, x 3 and are the same or different and are each independently 0, S, C (O), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (C¾) p (where ， 1 <ρ <10), (CF 2 ) q (where ， l <q <10), C (C¾) 2 , C (CF 3 ) 2> or C (= 0) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0, S, 또는 c(=o)이고， Wi and W 2 are the same or different from each other and are each independently 0, S, or c (= o),
^은 0, S, CRiooRioi 또는 NR102이고， 여기서 R100, R101 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고, ^ Is 0, S, CRiooRioi or NR 102 , wherein R 100 , R 101 and R 102 are the same or different from each other and are each independently hydrogen or a C1 to C5 alkyl group,
¾ 및 ¾는 동일하거나 서로 상이하며 각각 독립적 ^로 N 또는 CR103 (여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고， ¾ and ¾ are the same or different and are each independently ^ or N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group), but not CR 103 ;
Ri 내지 R42는 동일하거나 서로 상이하며 각각 독립적으로 수소, 또는 치환 또는 비치환된 C1 내지 C10지방족 유기기이고, Ri to R 42 are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
kl 내지 k3, k8 내지 kl4, k24 및 k25는 0 내지 2의 정수이고， k5, kl5, kl6, kl9, k21 및 k23은 0또는 1의 정수이고，  kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
M, k6, k7, kl7, kl8, k20, k22, k26 내지 k29, k31, k34 내지 k36, k38, k39 및 k42는 0내지 3의 정수이고,  M, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers from 0 to 3,
k30, k37, k40 및 k41은 0 내지 4의 정수이고，  k30, k37, k40 and k41 are integers from 0 to 4,
k32 및 k33은 0 내지 5의 정수이다.  k32 and k33 are integers of 0-5.
【청구항 12】  [Claim 12]
제 11항에 있어서，  The method of claim 11,
상기 Arr& 하기 식으로 표시된 것 중에서 선택되는 것인 다공성 지지체: Wherein the Arr & is a porous support selected from one of the following formulae:
Figure imgf000108_0001
Figure imgf000108_0001
106 87344 106 87344
Figure imgf000109_0001
Figure imgf000109_0001
【청구항 13】  [Claim 13]
제 10항에 있어서，  The method of claim 10,
， ^tx\s 7 중에서 선택되는 것인 다공성 상기 Ai"2는 하기 식으로 표시된 것 ^ 1 지지체 '■ ， ^ Tx \ s 7 is selected from porosity Ai ″ 2 is represented by the following formula ^ 1 support '■
Figure imgf000110_0001
식에서，
Figure imgf000110_0001
In the formula
¾， ¾ 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 0， S, C(=0), CH(OH) , S(=0)2, Si(CH3)2, (C¾)p (여기서 , 1<ρ<10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2, 또는 C(=0)NH이고， ¾, ¾ and ¾ are the same or different and each independently 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (C¾) p (where 1 <ρ <10), (CF 2 ) q (where l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (= 0) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는 c(o)이고， Wi and W 2 are the same or different from each other and are each independently 0, S, or c (o),
^은 0, S, CRiooRioi 또는 NR102이고， 여기서 R100, R101 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고， ^ Is 0, S, CRiooRioi or NR 102 , wherein R 100 , R 101 and R 102 are the same or different and are each independently hydrogen or a C1 to C5 alkyl group,
Z2 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CR103(여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고， Z 2 and ¾ are the same or different from each other and each independently N or CR 103 (wherein R 103 is hydrogen or a C1 to C5 alkyl group), but not CR 103 ;
R43 내지 ¾9는 동일하거나 서로 상이하며 각각 독립적으로 수소， 치환 또는 비치환된 C1 내지 C10 지방족 유기기， 또는 금속 술포네이트기이고,  R43 to ¾9 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group,
k43, k49, k64 내지 k68, k72 내지 k76, 및 k82 내지 k89는 0 내지 4의 정수이고,  k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
k44 내지 k46, k48, k51, k54, k55, k57, k58, k61 및 k63은 0 내지 3의 정수이고,  k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 및 k81은 0 내지 2의 정수이고，  k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are integers from 0 to 2,
k50은 0 또는 1의 정수이고，  k50 is an integer of 0 or 1,
k69, k71, k77 및 k79는 0 내지 5의 정수이다. k69, k71, k77 and k79 are integers of 0-5.
【청구항 14】 [Claim 14]
제 13항에 있어서，  The method of claim 13,
상기 Ar2는 하기 식으로 표시된 것 중에서 선택되는 것 인 다공성 지지 체： Ar 2 is a porous support which is selected from those represented by the following formula:
Ill Ill
Figure imgf000113_0001
Figure imgf000113_0001
89COOO/llOZaM/13d
Figure imgf000114_0001
89COOO / llOZaM / 13d
Figure imgf000114_0001
Figure imgf000115_0001
상기 식에서， M 은 금속이고， 상기 금속은 나트륨， 칼륨， 리튬， 이들의 합금 또는 이들의 조합이다.
Figure imgf000115_0001
Wherein M is a metal, and the metal is sodium, potassium, lithium, alloys thereof or combinations thereof.
【청구항 15】  [Claim 15]
제 10항에 있어서，  The method of claim 10,
상기 Q는 C(CH3)2, C(CF3)2, 0, S, S(=0)2 또는 C(=0) 중에서 선택된 것인 다공성 지지체. Q is C (CH 3 ) 2 , C (CF 3 ) 2 , 0, S, S (= 0) 2 or C (= 0).
【청구항 16]  [Claim 16]
제 10항에 있어서， 상기 Arr 하기 화학식 A1 내지 A8 중 어느 하나로 표시되는 작용기이고, 상기 Ar2는 하기 화학식 B1 내지 B11 중 어느 하나로 표시되는 작용기이고, 상기 Q는 C(CF3)2인 것인 다공성 지지체: The method of claim 10, Arr is a functional group represented by any one of Formulas A1 to A8, wherein Ar 2 is a functional group represented by any one of Formulas B1 to B11, and Q is C (CF 3 ) 2 .
[화학식 A1] [화학식 A2] [화학식 A3]  [Formula A1] [Formula A2] [Formula A3]
Figure imgf000116_0001
Figure imgf000116_0001
[화학식 A4] [화학식 A5] [화학식 A6]
Figure imgf000116_0002
[Formula A4] [Formula A5] [Formula A6]
Figure imgf000116_0002
[화학식 A7]
Figure imgf000116_0003
[Formula A7]
Figure imgf000116_0003
[화학식 A8]
Figure imgf000116_0004
[Formula A8]
Figure imgf000116_0004
[화학식 B1] [화학식 B2] [화학식 B3]
Figure imgf000116_0005
[화학식 B4] [화학식 B5] [화학식 B6] [화학식 B7] [Formula B1] [Formula B2] [Formula B3]
Figure imgf000116_0005
[Formula B4] [Formula B5] [Formula B6] [Formula B7]
Figure imgf000117_0001
Figure imgf000117_0001
[화학식 B8] [화학식 B9]
Figure imgf000117_0002
Formula B8 Formula B9
Figure imgf000117_0002
[화학식 B10] [화학식 B11]  [Formula B10] [Formula B11]
Figure imgf000117_0003
Figure imgf000117_0003
【청구항 17]  [Claim 17]
제 10항에 있어서,  The method of claim 10,
상기 화학식 표시되는 반복단위를 포함하 폴리아믹산의 공중합체에서의 각 반복단위 사이의 몰비， 상기 화학식 5 내지 8에서 m:l의 몰비, 상기 화학식 19 내지 22로 표시되는 반복단위를 포함하는 폴리이미드의 공중합체에서의 각 반복단위 사이의 몰비 또는 상기 화학식 23 내지 26에서 m:l의 몰비는 0.1:9.9 내지 9.9:0.1인 것인 다공성 지지체.  The molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating unit represented by the above formula, the molar ratio of m: l in the above formulas 5 to 8, and the polyimide comprising the repeating unit represented by the above formulas 19 to 22 The molar ratio between each repeating unit in the copolymer of or the molar ratio of m: l in the formula 23 to 26 is from 0.1: 9.9 to 9.9: 0.1.
【청구항 18】  [Claim 18]
제 1항에 있어서, 상기 폴리아믹산으로부터 유도되는 고분자 및 상기 폴리이미드로부터 유도되는 고분자는 하기 화학식 37 내지 50 중 어느 하나로 표시되는 반복단위를 포함하는 고분자 또는 이들의 공중합체를 포함하는 것인 다공성 지지체: The method of claim 1, The polymer derived from the polyamic acid and the polymer derived from the polyimide is a porous support comprising a polymer or a copolymer thereof comprising a repeating unit represented by any one of the following formulas 37 to 50:
[화학식 37] [Formula 37]
Figure imgf000118_0001
Figure imgf000118_0001
[화학식 40]
Figure imgf000118_0002
[Formula 40]
Figure imgf000118_0002
[화학식 41]
Figure imgf000118_0003
[화학식 42]
Figure imgf000119_0001
[Formula 41]
Figure imgf000118_0003
[Formula 42]
Figure imgf000119_0001
[화학식 43]
Figure imgf000119_0002
[Formula 43]
Figure imgf000119_0002
[화학식 44]
Figure imgf000119_0003
Figure imgf000119_0004
Figure imgf000119_0005
[화학식 47] [Formula 44]
Figure imgf000119_0003
Figure imgf000119_0004
Figure imgf000119_0005
[Formula 47]
Figure imgf000120_0001
Figure imgf000120_0001
상기 화학식 37 내지 50에서，  In Chemical Formulas 37 to 50,
Arr^ 치환 또는 비 치환된 4가의 C6 내지 C24 아릴렌기 및 치환 또는 비 치환된 4가의 C4 내지 C24 헤테로 고리 기 에서 선택되는 방향족 고리기이고， 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0， S, C(=0), CH(OH), S(=0)2, Si(C¾)2, (CH2)P (여기서， 1<ρ<10), (CF2)q (여기서， l≤q<10), C(C¾)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고, A ' 및 Ar2는 동일하거나 서로 상이하며 각각 독립적으로 치환 또는 비치환된 2가의 C6 내지 C24 아릴렌기 및 치환 또는 비치환된 2가의 C4 내지 C24 헤테로 고리기에서 선택되는 방향족 고리기이고， 상기 방향족 고리기는 단독으로 존재하거나; 2개 이상이 서로 접합되어 축합 고리를 형성하거나; 2개 이상이 단일결합， 0, S, C(=0), CH(OH) , S(=0)2, Si(CH3)2, (CH2)P (여기서， l≤p<10), (CF2)q (여기서, l<q<10), C(CH3)2, C(CF3)2 또는 C(=0)NH의 작용기에 의해 연결되어 있고, Aromatic selected from Arr ^ substituted or unsubstituted tetravalent C6 to C24 arylene groups and substituted or unsubstituted tetravalent C4 to C24 heterocyclic groups Ring groups, wherein the aromatic ring groups are present alone; Two or more are joined to each other to form a condensed ring; At least two single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (C¾) 2 , (CH 2 ) P (where 1 <ρ <10), (CF 2 ) q where l ≦ q <10, C (C¾) 2 , C (CF 3 ) 2 or C (= 0) NH, and A ′ and Ar 2 are the same or Different from each other and each independently an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C24 arylene group and a substituted or unsubstituted divalent C4 to C24 heterocyclic group, wherein the aromatic ring groups are present alone; Two or more are joined to each other to form a condensed ring; Two or more single bonds, 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P (where l≤p <10) , (CF 2 ) q (wherein l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 or C (= 0) NH,
Q는 0, S, C(=0), CH(OH), S(=0)2, Si(CH3)2) (C¾)p (여기서， 1<P<10), (CF2)q (여기서， l<q<10), C(CH3)2, C(CF3)2, C(=0)NH, C(CH3)(CF3), 또는 치환 또는 비치환된 페닐렌기 (여기서 치환된 페닐렌기는 C1 내지 C6 알킬기 또는 C1 내지 C6 할로알킬기로 치환된다)이고， 이때 상기 Q는 양쪽 방향족 고리와 m-m, m-p, p-m, 또는 p— p 위치로 연결되고， Y1 1는 0또는 S 이고, Q is 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2) (C¾) p (where 1 <P <10), (CF 2 ) q Wherein l <q <10), C (CH 3 ) 2 , C (CF 3 ) 2 , C (= 0) NH, C (CH 3 ) (CF 3 ), or a substituted or unsubstituted phenylene group ( Wherein the substituted phenylene group is substituted with a C1 to C6 alkyl group or a C1 to C6 haloalkyl group), wherein Q is linked to both aromatic rings in the mm, mp, pm, or p—p position, and Y 1 1 is 0 Or S,
n은 20≤n≤200을 만족하는 정수이고，  n is an integer satisfying 20≤n≤200,
m은 10≤m≤400을 만족하는 정수이고，  m is an integer satisfying 10≤m≤400,
1은 10≤1≤400을 만족하는 정수이다.  1 is an integer satisfying 10≤1≤400.
【청구항 19】 제 18항에 있어서， [Claim 19] The method of claim 18,
상기 An은 하기 식으로 표시된 것 중에서 선택되는 것인 다공성
Figure imgf000122_0001
상기 식에서， An is a porous selected from those represented by the following formula
Figure imgf000122_0001
In the above formula,
， X2, X3 및 는 동일하거나 서로 상이하며 각각 독립적으로 0, S, C(=0), CH(OH), S(=0)2, Si(CH3)2, (CH2)P (여기서, 1<ρ<10), (CF2)q (여기서, l<q<10), C(C¾)2, C(CF3)2, 또는 C(=0)NH이고， , X 2 , X 3 and are the same or different and are each independently 0, S, C (= 0), CH (OH), S (= 0) 2 , Si (CH 3 ) 2 , (CH 2 ) P Where 1 <ρ <10), (CF 2 ) q (where l <q <10), C (C¾) 2 , C (CF 3 ) 2 , or C (= 0) NH,
Wj 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는Wj and W 2 are the same or different from each other and each independently 0, S, or
C(=0)이고， C (= 0),
^은 0， S, CRjooRioi 또는 NR102이고， 여기서 Rioo, ioi 및 RK)2는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고, ^ Is 0, S, CRjooRioi or NR 102 , wherein Rioo, ioi and RK) 2 are the same or different from each other and are each independently hydrogen or a C1 to C5 alkyl group,
Z2 및 는 동일하거나 서로 상이하며 각각 독립적으로 N 또는Z 2 and are the same or different from each other and each independently N or
CR103(여기서, R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니 고, CR 103 , wherein R 103 is hydrogen or a C1 to C5 alkyl group, but at the same time is not CR 103 ;
Rl 내지 2는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 치환 또는 비치환된 C1 내지 C10 지방족 유기기이고, R1 to 2 are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
kl 내지 k3, k8 내지 kl4, k24 및 k25는 0 내지 2의 정수이고, k5, kl5, kl6, kl9, k21 및 k23은 0 또는 1의 정수이고,  kl to k3, k8 to kl4, k24 and k25 are integers of 0 to 2, k5, kl5, kl6, kl9, k21 and k23 are integers of 0 or 1,
k4,,k6, k7, kl7, kl8, k20, k22, k26 내지 k29, k31, k34 내지 k36, k38, k39 및 k42는 0 내지 3의 정수이고,  k4, k6, k7, kl7, kl8, k20, k22, k26 to k29, k31, k34 to k36, k38, k39 and k42 are integers from 0 to 3,
k30, k37( k40 및 k41은 0 내지 4의 정수이고, k30, k37 ( k40 and k41 are integers from 0 to 4,
k32 및 k33은 0 내지 5의 정수이다.  k32 and k33 are integers of 0-5.
【청구항 20】 제 19항에 있어서， [Claim 20] The method of claim 19,
상기 Arr^ 하기 식으로 표시된 것 중에서 선택되는 것인 다공성 지지체： The porous support body selected from those represented by the above Arr ^ formula:
/ 89εοοοπο2Ή/:1><ίε/ O/.80ποζAV- / 89εοοοπο2Ή / : 1>< ίε / O / .80πο ζ AV-
Figure imgf000125_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000126_0001
【청구항 21】  [Claim 21]
제 18항에 았 ^서,  In accordance with claim 18,
상기 A 1 및 Ar2는 하기 식으로 표시된 것 중에서 선택되는 다공성 지지체: The A 1 and Ar 2 is a porous support selected from those represented by the following formula:
Figure imgf000127_0001
Figure imgf000127_0001
상기 식에서，  In the above formula,
Xi, X2, X3 및 는 동일하거나 서로 상이하며 각각 독립적으로 0， S, COO) , CH(OH), S(=0)2, Si(CH3)2> (CH2)P (여기서， 1<ρ<10), (CF2)q (여기서, l<q<10), C(CH3)2, C(CF3)2, 또는 C(=0)NH이고， Xi, X 2 , X 3 and are the same or different and are each independently 0, S, COO), CH (OH), S (= 0) 2 , Si (CH 3 ) 2> (CH 2 ) P (where 1 <ρ <10), (CF 2 ) q (where l <q <10 ), C (CH 3 ) 2 , C (CF 3 ) 2 , or C (= 0) NH,
Wi 및 W2는 동일하거나 서로 상이하며 각각 독립적으로 0， S, 또는 c(o)이고， Wi and W 2 are the same or different from each other and are each independently 0, S, or c (o),
^은 0， S, CRiooRioi 또는 NR102이고， 여기서 R100, R101 및 R102는 동일하거나 서로 상이하며 각각 독립적으로 수소 또는 C1 내지 C5 알킬기이고， ^ Is 0, S, CRiooRioi or NR 102 , wherein R 100 , R 101 and R 102 are the same or different and are each independently hydrogen or a C1 to C5 alkyl group,
Z2 및 ¾는 동일하거나 서로 상이하며 각각 독립적으로 N 또는 CRi03(여기서， R103은 수소 또는 C1 내지 C5 알킬기이다)이나 동시에 CR103은 아니고， Z 2 and ¾ are the same or different from each other and each independently N or CRi 03 (wherein R 103 is hydrogen or a C1 to C5 alkyl group), but at the same time is not CR 103 ;
R43 내지 R89는 동일하거나 서로 상이하며 각각 독립적으로 수소， 치환 또는 비치환된 C1 내지 C10 지방족 유기기， 또는 금속 술포네이트기이고  R43 to R89 are the same or different and are each independently hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group
k43, k49, k64 내지 k68, k72 내지 k76, 및 k82 내지 k89는 0 내지 4의 정수이고,  k43, k49, k64 to k68, k72 to k76, and k82 to k89 are integers of 0 to 4,
k44 내지 k46, k48, k51, k54, k55, k57, k58, k61 및 k63은 0 내지 3의 정수이고,  k44 to k46, k48, k51, k54, k55, k57, k58, k61 and k63 are integers from 0 to 3,
k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 및 k81은 0 내지 2의 정수이고，  k47, k52, k53, k56, k59, k60, k62, k70, k78, k80 and k81 are integers from 0 to 2,
k50은 0 또는 1의 정수이고，  k50 is an integer of 0 or 1,
k69, k71, k77 및 k79는 0 내지 5의 정수이다. k69, k71, k77 and k79 are integers of 0-5.
【청구항 22] [Claim 22]
제 21항에 있어서,  The method of claim 21,
상기 A ' 및 Ar2는 하기 식으로 표시된 것 중에서 선택되 다공성 지지체: Wherein A 'and Ar 2 are selected from the following:
SZl SZl
Figure imgf000130_0001
Figure imgf000130_0001
89C000/TT0ra¾/13d
Figure imgf000131_0001
89C000 / TT0ra¾ / 13d
Figure imgf000131_0001
Figure imgf000132_0001
상기 식에서， M 은 금속이고 상기 금속은 나트륨, 칼륨， 리튬, 이들의 합금 또는 이들의 조합이다.
Figure imgf000132_0001
Wherein M is a metal and the metal is sodium, potassium, lithium, alloys thereof or combinations thereof.
【청구항 23】  [Claim 23]
제 18항에 있어서,  The method of claim 18,
상기 Q는 C(C¾)2, C(CF3)2, 0， S, S(=0)2 또는 C(=0) 중에서 선택된 것인 다공성 지지체. Q is C (C¾) 2 , C (CF 3 ) 2 , 0, S, S (= 0) 2 or C (= 0).
【청구항 24]  [Claim 24]
제 18항에 있어서， 상기 A 은 하기 화학식 A1 내지 A8 중 어느 하나로 표시되는 작용기이고，.상기 Ai 는 하기 화학식 C1 내지 C8 중 어느 하나로 표시되는 작용기이고， 상기 Ar2는 하기 화학식 B1 내지 B11 중 어느 하나로 표시되는 작용기이고， 상기 Q는 C(CF3)2인 것인 다공성 지지체: The method of claim 18, A is a functional group represented by any one of the following Formulas A1 to A8, Ai is a functional group represented by any one of the following Formulas C1 to C8, and Ar 2 is a functional group represented by any one of the following Formulas B1 to B11, Wherein Q is C (CF 3 ) 2 ;
[화학식 M] [화학식 A2] [화학식 A3]  [Formula M] [Formula A2] [Formula A3]
Figure imgf000133_0001
Figure imgf000133_0001
[화학식 A8]
Figure imgf000133_0002
[화학식 B1] [화학식 B2] [화학식 B3]
Figure imgf000134_0001
[Formula A8]
Figure imgf000133_0002
[Formula B1] [Formula B2] [Formula B3]
Figure imgf000134_0001
[화학식 B4] [화학식 B5] [화학식 B6] [화학식 B7]
Figure imgf000134_0002
[Formula B4] [Formula B5] [Formula B6] [Formula B7]
Figure imgf000134_0002
[화학식 B10] [화학식 B11] [Formula B10] [Formula B11]
Figure imgf000134_0003
Figure imgf000134_0003
[화학식 C1] [화학식 C2] [화학식 C3]
Figure imgf000134_0004
[화학식 C4] [화학식 C5] [화학식 C6] [Formula C1] [Formula C2] [Formula C3]
Figure imgf000134_0004
[Formula C4] [Formula C5] [Formula C6]
Figure imgf000135_0001
Figure imgf000135_0001
【청구항 25】  [Claim 25]
제 1항에 있어서,  The method of claim 1,
상기 다공성 지지체는 상기 피코기공을 가지는 고분자를 포함하는 섬유를 포함하고， 상기 섬유는 랜덤하게 배열되어 있는 것인 다공성 지지체.  The porous support includes a fiber comprising a polymer having the picopores, wherein the fibers are randomly arranged.
【청구항 26】 [Claim 26]
제 1항에 있어서，  The method of claim 1,
상기 다공성 지지체는 상기 피코기공을 가지는 고분자를 포함하는 섬유를 포함하고， 상기 섬유는 일방향으로 배열되어 있는 것인 다공성 지지체 .  The porous support comprises a fiber comprising a polymer having the picopores, wherein the fibers are arranged in one direction.
【청구항 27】  [Claim 27]
거 U항 내지 제 26항 중 어느 하나의 항에 따른 다공성 지지체; 및 상기 다공성 지지체의 내부， 표면， 또는 내부와 표면에 형성된 양이온 교환 수지를 포함하는 연료 전지용 고분자 전해질 막. A porous support according to any one of claims U to 26; And Polymer electrolyte membrane for a fuel cell comprising a cation exchange resin formed on the inside, the surface, or the inside and the surface of the porous support.
【청구항 28】  [Claim 28]
제 27항에 있어서，  The method of claim 27,
상기 양이온 교환 수지는 술폰산기， 카르복실산기， 인산기, 포스포닌산기 및 이들의 유도체로 이루어진 군에서 선택되는 양이온 교환기를 포함하는 고분자인 것인 연료 전지용 고분자 전해질 막.  The cation exchange resin is a polymer electrolyte membrane for a fuel cell is a polymer comprising a cation exchange group selected from the group consisting of sulfonic acid group, carboxylic acid group, phosphoric acid group, phosphonic acid group and derivatives thereof.
【청구항 29]  [Claim 29]
제 27항에 있어서，  The method of claim 27,
상기 다공성 지지체와 상기 양이온 교환 수지는 99:1 내지 10 :90의 중량비로 포함하는 것인 연료 전지용 고분자 전해질 막.  The porous support and the cation exchange resin is a polymer electrolyte membrane for a fuel cell comprising a weight ratio of 99: 1 to 10:90.
【청구항 30】  [Claim 30]
제 27항에 있어서，  The method of claim 27,
상기 연료 전지용 고분자 전해질 막은 20 IM 내지 300 의 두께를 갖는 것인 연료 전지용 고분자 전해질 막.  The polymer electrolyte membrane for a fuel cell is a polymer electrolyte membrane for a fuel cell having a thickness of 20 IM to 300.
【청구항 31]  [Claim 31]
제 1항 내지 제 26항 중 어느 하나의 항에 따른 다공성 지지체를 포함하고,  A porous support according to any one of claims 1 to 26,
상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 산이 도핑되어 형성된 것인 연료 전지용 고분자 전해질 막.  A polymer electrolyte membrane for a fuel cell, which is formed by doping an acid into the inside, the surface, or the inside and the surface of the porous support.
【청구항 32】 제 31항에 있어서， [Claim 32] The method of claim 31,
상기 산은 술폰산， 카르복실산， 인산， 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 것인 연료 전지용 고분자 전해질 막.  The acid is selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof.
【청구항 33] [Claim 33]
게 1항 내지 제 26항 중 어느 하나의 항에 따른 다공성 지지체를 포함하고，  A porous support according to any one of claims 1 to 26,
상기 다공성 지지체는 표면에 불소기를 포함하는 것인 연료 전지용 고분자 전해질 막.  The porous support is a polymer electrolyte membrane for a fuel cell comprising a fluorine group on the surface.
【청구항 34]  [Claim 34]
아민기에 대하여 오르쏘 위치에 존재하는 적어도 하나의 작용기를 포함하는 방향족 디아민 및 디안하이드라이드로부터 제조된 반복단위를 가지는 폴리아믹산 또는 폴리이미드; 및  Polyamic acid or polyimide having repeating units prepared from aromatic diamines and dianhydrides comprising at least one functional group present at the ortho position relative to the amine group; And
유기 용매를 포함하고，  Including an organic solvent ，
상기 유기 용매는 디메틸설폭사이드; N-메틸 -2-피를리돈; N- 메틸피를리돈; Ν,Ν-디메틸포름아미드; Ν,Ν—디메틸아세트아미드;  The organic solvent is dimethyl sulfoxide; N-methyl-2-pyridone; N-methylpyridone; Ν, Ν-dimethylformamide; Ν, Ν—dimethylacetamide;
부티로락톤， 사이클로핵사논， 3-핵사논， 3-헵타논 및 3-옥타논으로 이루어진 군에서 선택된 케톤; 및 이들의 조합으로 이루어진 군에서 선택되는 것인 다공성 지지체 형성용 조성물. Ketones selected from the group consisting of butyrolactone, cyclonucleanone, 3-nuxanone, 3-heptanone and 3-octanone; And composition for forming a porous support that is selected from the group consisting of these.
【청구항 35]  [Claim 35]
제 34항에 있어서,  The method of claim 34,
상기 다공성 지지체 형성용 조성물 총량에 대하여， 상기 폴리아믹산 또는 상기 폴리이미드를 1 내지 40 중량 %， 그리고 상기 유기 용매를 60 내지 99 중량 %로 포함하는 것인 다공성 지지체 형성용 조성물. The polyamic acid based on the total amount of the composition for forming the porous support Or 1 to 40% by weight of the polyimide, and 60 to 99% by weight of the organic solvent.
【청구항 36]  [Claim 36]
제 34항에 있어서，  The method of claim 34,
상기 다공성 지지체 형성용 조성물은  The composition for forming the porous support
물; 메탄올， 에탄올， 2-메틸 -1—부탄올, 2-메틸 -2—부탄올, 글리세를， 에틸렌글리콜， 디에틸렌글리콜 및 프로필렌글리콜로 이루어진 군에서 선택된 알코올; 아세톤 및 메틸에틸 케톤으로 이루어진 군에서 선택된 케톤; 폴리비닐알코올， 폴리아크릴산， 폴리아크릴아마이드, 폴리에틸렌글리콜 폴리프로필렌글리콜， 키토산， 키틴， 덱스트란 및 폴리비닐피를리돈으로 이루어진 군에서 선택된 고분자 화합물; 테트라하이드로퓨란; 트리클로로에탄; 및 이들의 조합으로 이루어진 군에서 선택되는 보조제를 더 포함하는 것인 다공성 지지체 형성용 조성물.  water; Alcohols selected from the group consisting of methanol, ethanol, 2-methyl-1 butanol, 2-methyl-2 butanol, glycerol, ethylene glycol, diethylene glycol and propylene glycol; Ketones selected from the group consisting of acetone and methylethyl ketone; High molecular weight compounds selected from the group consisting of polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyethylene glycol polypropylene glycol, chitosan, chitin, dextran and polyvinylpyridone; Tetrahydrofuran; Trichloroethane; And a composition selected from the group consisting of a combination thereof.
【청구항 37]  [Claim 37]
제 36항에 있어서，  The method of claim 36,
상기 보조제를 포함하는 다공성 지지체 형성용 조성물 총량에 대하여， 상기 폴리아믹산 또는 상기 폴리이미드를 1 내지 40 중량 %， 상기 유기 용매를 10 내지 95 중량 % 및 상기 보조제를 4 내지 70 중량 ¾>로 포함하는 것인 다공성 지지체 형성용 조성물.  Regarding the total amount of the composition for forming a porous support including the adjuvant, the polyamic acid or the polyimide contains 1 to 40% by weight, 10 to 95% by weight of the organic solvent and 4 to 70% by weight of the auxiliary agent. The composition for forming a porous support.
【청구항 38】  [Claim 38]
제 34항에 있어서， 상기 폴리아믹산 및 상기 폴리이미드는 각각 10,000 g/mol 내지 500,000 g/mol의 중량평균 분자량 (Mw)을 가지는 것인 다공성 지지체 형성용 조성물. The method of claim 34, Wherein said polyamic acid and said polyimide each have a weight average molecular weight (Mw) of 10,000 g / mol to 500,000 g / mol.
【청구항 39]  [Claim 39]
제 34항에 있어서，  The method of claim 34,
상기 다공성 지지체 형성용 조성물은 0.01 Pa · s 내지 100 Pa · s의 점도를 가지는 것인 다공성 지지체 형성용 조성물.  The composition for forming a porous support is a composition for forming a porous support having a viscosity of 0.01 Pa · s to 100 Pa · s.
【청구항 40】  [Claim 40]
제 34항 내지 제 39항 중 어느 하나의 항에 따른 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계; 및  40. A method of forming a nonwoven fabric by electrospinning a composition for forming a porous support according to any one of claims 34 to 39; And
상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계  Heat-treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide
를 포함하는 다공성 지지체의 제조 방법.  Method for producing a porous support comprising a.
【청구항 41】  [Claim 41]
제 40항에 있어서，  The method of claim 40,
상기 전기방사는 1 kV 내지 1,000 kV의 전압을 인가하여 실시되는 것인 다공성 지지체의 제조방법.  The electrospinning method of producing a porous support that is carried out by applying a voltage of 1 kV to 1,000 kV.
【청구항 42】  [Claim 42]
제 40항에 있어서，  The method of claim 40,
상기 부직포는 다공성 지지체 형성용 조성물을 포함하는 섬유가 랜덤하게 배열되어 있는 것인 다공성 지지체의 제조 방법. The nonwoven fabric is a fiber comprising a composition for forming a porous support Method for producing a porous support that is arranged randomly.
【청구항 43】  [Claim 43]
제 40항에 있어서,  The method of claim 40,
상기 부직포는 다공성 지지체 형성용 조성물을 포함하는 섬유가 일방향으로 배열되어 있는 것인 다공성 지지체의 제조 방법.  The nonwoven fabric is a method for producing a porous support is that the fibers comprising the composition for forming the porous support is arranged in one direction.
【청구항 44】  [Claim 44]
제 40항에 있어서，  The method of claim 40,
상기 고분자는 상기 폴리아믹산 또는 상기 폴리이미드로부터 열전환되어 유도되는 것이고， 상기 폴리아믹산 또는 상기 폴리이미드에 포함되는 반복단위의 총량에 대하여， 열전환되는 반복단위의 비율 (열전환율)은 10몰% 내지 100몰%인 것인 다공성 지지체의 제조 방법.  The polymer is induced by thermal conversion from the polyamic acid or the polyimide, and with respect to the total amount of the repeating units included in the polyamic acid or the polyimide, the ratio (thermal conversion rate) of the repeating unit thermally converted is 10 mol%. Method for producing a porous support that is from 100 mol%.
【청구항 45] [Claim 45]
제 40항에 있어서，  The method of claim 40,
상기 열처리는 25CTC 내지 550°C의 온도에서 실시되는 것인 다공성 지지체의 제조방법. The heat treatment is a method of producing a porous support that is carried out at a temperature of 25CTC to 550 ° C.
【청구항 46]  [Claim 46]
제 40항에 있어서，  The method of claim 40,
상기 열처리는 10분 내지 5시간 동안 실시되는 것인 다공성 지지체의 제조방법.  The heat treatment is a method for producing a porous support that is carried out for 10 minutes to 5 hours.
【청구항 47】  [Claim 47]
제 40항에 있어서， 상기 열처리시 승온 속도는 1 °C/분 내지 20 °C/분인 것인 다공성 지지체의 제조방법. The method of claim 40, The temperature increase rate during the heat treatment is 1 ° C / min to 20 ° C / min method of producing a porous support.
【청구항 48】  [Claim 48]
제 34항 내지 제 39항 중 어느 하나의 항에 따른 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계;  40. A method of forming a nonwoven fabric by electrospinning a composition for forming a porous support according to any one of claims 34 to 39;
상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및  Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And
. 상기 다공성 지지체의 내부, 표면， 또는 내부와 표면에 양이온 교환 수지를 형성하는 단계  . Forming a cation exchange resin on the inside, the surface, or the inside and the surface of the porous support
를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법 .  Method for producing a polymer electrolyte membrane for a fuel cell comprising a.
【청구항 49]  [Claim 49]
제 34항 내지 제 39항 중.어느 하나의 항에 따른 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계;  40. The method of claim 34, wherein the non-woven fabric is formed by electrospinning the composition for forming a porous support according to any one of claims 34 to 39;
상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및  Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And
상기 다공성 지지체의 내부， 표면， 또는 내부와 표면에 산을 도핑하는 단계  Doping acid into the interior, surface, or interior and surface of the porous support
를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법 .  Method for producing a polymer electrolyte membrane for a fuel cell comprising a.
【청구항 50] 제 49항에 있어서， [Claim 50] The method of claim 49,
상기 산은 술폰산， 카르복실산， 인산, 포스포닌산 및 이들의 유도체로 이루어진 군에서 선택되는 것인 연료 전지용 고분자 전해질 막의 제조 방법 .  The acid is selected from the group consisting of sulfonic acid, carboxylic acid, phosphoric acid, phosphonic acid and derivatives thereof.
【청구항 51】  [Claim 51]
제 34항 내지 제 39항 중 어느 하나의 항에 따른 다공성 지지체 형성용 조성물을 전기방사하여 부직포를 형성하는 단계 ;  40. A method of forming a nonwoven fabric by electrospinning a composition for forming a porous support according to any one of claims 34 to 39;
상기 부직포를 열처리하여 폴리아믹산으로부터 유도된 고분자 또는 폴리이미드로부터 유도된 고분자를 포함하는 다공성 지지체를 형성하는 단계; 및  Heat treating the nonwoven fabric to form a porous support comprising a polymer derived from polyamic acid or a polymer derived from polyimide; And
상기 다공성 지지체의 표면에 블소기를 도입하는 단계  Introducing a bloso group to the surface of the porous support
를 포함하는 연료 전지용 고분자 전해질 막의 제조 방법 .  Method for producing a polymer electrolyte membrane for a fuel cell comprising a.
【청구항 52]  [Claim 52]
서로 대향하여 위치한 애노드 및 캐소드; 그리고  Anodes and cathodes positioned opposite one another; And
상기 애노드와 상기 캐소드 사이에 위치하며， 제 1항 내지 제 28항 중 어느 하나의 항에 따른 다공성 지지체 및 상기 다공성 지지체의 내부， 표면， 또는 내부와 표면에 형성된 양이온 교환 수지를 포함하는 연료 전지용 고분자 전해질 막을 포함하는 연료 전지용 막 -전극 어셈블리.  Located between the anode and the cathode, a polymer for a fuel cell comprising a porous support according to any one of claims 1 to 28 and a cation exchange resin formed on the inside, the surface, or the inside and the surface of the porous support. A membrane-electrode assembly for a fuel cell comprising an electrolyte membrane.
【청구항 53】  [Claim 53]
제 52항에 따른 막 -전극 어셈블리 및 세퍼레이터를 하나 이상 포함하며， 연료와 산화제의 전기화학적 반웅을 통하여 전기를 발생시키는 발생부; 53. A fuel cell comprising at least one membrane-electrode assembly and a separator according to claim 52 for generating electricity through electrochemical reaction of fuel and oxidant. Generator;
연료를 상기 전기 발생부로 공급하는 연료 공급부; 및 산화제를 상기 전기 발생부로 공급하는 산화제 공급부 를 포함하는 연료 전지 시스템.  A fuel supply unit supplying fuel to the electricity generation unit; And an oxidant supply unit for supplying an oxidant to the electricity generating unit.
PCT/KR2011/000368 2010-01-18 2011-01-18 Porous support, and polymer electrolyte membrane for a fuel cell comprising same WO2011087344A2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3031848A1 (en) 2014-12-09 2016-06-15 ABB Technology Ltd Dielectric material and dielectric film

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101478301B1 (en) * 2011-08-30 2014-12-31 주식회사 엘지화학 Polymer resin composition, poly-imide resin film, preparation method of the poly-imide resin film, metallic laminate, and circuit board
WO2013032211A2 (en) * 2011-08-30 2013-03-07 주식회사 엘지화학 Polymer resin composition, polyimide resin film, method for preparing the polyimide resin film, metal stacked structure, and circuit board
US9045897B2 (en) 2012-03-23 2015-06-02 Korea Institute Of Industrial Technology Infrared ray blocking multi-layered structure insulating film having thermal anisotropy
KR101357648B1 (en) * 2012-03-23 2014-02-04 한국생산기술연구원 Composition of transparent thermal resistance including clays and manufacturing method thereof
KR101379899B1 (en) * 2012-03-23 2014-04-01 한국생산기술연구원 Composition of transparent thermal resistance and manufacturing method thereof
KR101995527B1 (en) 2012-12-28 2019-07-02 코오롱인더스트리 주식회사 Reinforced composite membrane for fuel cell and membrane-electrode assembly for fuel cell comprising the same
US20210178338A1 (en) * 2016-02-26 2021-06-17 Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) Ultrathin-film composite membrane based on thermally rearranged poly(benzoxazole-imide) copolymer, and production method therefor
KR101956169B1 (en) * 2016-05-24 2019-03-08 한양대학교 산학협력단 Self-humidifying ion-exchange composite membrane and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060085846A (en) * 2005-01-25 2006-07-28 한양대학교 산학협력단 Acid or base-doped proton conducting polymer, preparation method thereof, polymer membrane using the same and fuel cell using the same
KR100655176B1 (en) * 2005-08-11 2006-12-08 한양대학교 산학협력단 Crosslinked polyimides and their applications as electrochemical materials
WO2009142434A2 (en) * 2008-05-19 2009-11-26 한양대학교 산학협력단 Hollow fiber, dope solution composition for forming a hollow fiber, and method for manufacturing a hollow fiber using the same

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2640545A1 (en) * 2008-05-19 2009-11-19 Industry-University Cooperation Foundation, Hanyang University Polyimides dope composition, preparation method of hollow fiber using the same and hollow fiber prepared therefrom

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060085846A (en) * 2005-01-25 2006-07-28 한양대학교 산학협력단 Acid or base-doped proton conducting polymer, preparation method thereof, polymer membrane using the same and fuel cell using the same
KR100655176B1 (en) * 2005-08-11 2006-12-08 한양대학교 산학협력단 Crosslinked polyimides and their applications as electrochemical materials
WO2009142434A2 (en) * 2008-05-19 2009-11-26 한양대학교 산학협력단 Hollow fiber, dope solution composition for forming a hollow fiber, and method for manufacturing a hollow fiber using the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PARK, HO BUM ET AL.: 'Polymers with Cavities Tuned for Fast Selective Transport of Small Molecules and Ions' SCIENCE vol. 318, 12 October 2007, pages 254 - 258 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3031848A1 (en) 2014-12-09 2016-06-15 ABB Technology Ltd Dielectric material and dielectric film

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