KR20230168096A - Novel poly(aryl piperidinium) ionomer containing branched moeity, an anion exchange membrane and method for preparing the same - Google Patents
Novel poly(aryl piperidinium) ionomer containing branched moeity, an anion exchange membrane and method for preparing the same Download PDFInfo
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- KR20230168096A KR20230168096A KR1020220126048A KR20220126048A KR20230168096A KR 20230168096 A KR20230168096 A KR 20230168096A KR 1020220126048 A KR1020220126048 A KR 1020220126048A KR 20220126048 A KR20220126048 A KR 20220126048A KR 20230168096 A KR20230168096 A KR 20230168096A
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- Prior art keywords
- anion exchange
- branch
- exchange membrane
- piperidinium
- aryl
- Prior art date
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- 229920000554 ionomer Polymers 0.000 title claims abstract description 68
- 239000003011 anion exchange membrane Substances 0.000 title claims abstract description 63
- -1 poly(aryl piperidinium Chemical compound 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 66
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000000446 fuel Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006085 branching agent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 claims description 2
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 30
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 description 9
- 239000011884 anode binding agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003013 cathode binding agent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- NNCAWEWCFVZOGF-UHFFFAOYSA-N mepiquat Chemical compound C[N+]1(C)CCCCC1 NNCAWEWCFVZOGF-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 150000008378 aryl ethers Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229930184652 p-Terphenyl Natural products 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical group C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- PFWWZGINJSDVGU-UHFFFAOYSA-N piperidine Chemical group C1CCNCC1.C1CCNCC1 PFWWZGINJSDVGU-UHFFFAOYSA-N 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- 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
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
-
- 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
-
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
Abstract
본 발명은 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 가지부 함유 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 공중합체 이오노머에 관한 것으로, 화학적 안정성이 뛰어나고, 분자량이 높으면서 기계적 물성이 우수하며, 낮은 팽창률과 높은 치수안정성 및 이온전도도, 및 제한된 페닐 흡착 효과를 갖는다.
또한, 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 제조되는 음이온교환막은 저습도 조건에서도 작동 가능하고 물 관리 능력이 우수하여 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 바나듐 레독스 플로우 배터리 또는 금속-공기 전지 등에 응용할 수 있다.The present invention relates to a poly(aryl piperidinium) copolymer ionomer with no aryl ether bond in the polymer backbone and introduced with branch-containing piperidinium groups in the repeating unit. It has excellent chemical stability, high molecular weight, and excellent mechanical properties. It has a low expansion rate, high dimensional stability and ionic conductivity, and limited phenyl adsorption effect.
In addition, the anion exchange membrane manufactured from the branch-containing poly(aryl piperidinium) copolymer ionomer can operate even in low humidity conditions and has excellent water management ability, so it is used as a membrane and binder for alkaline fuel cells, water electrolysis devices, carbon dioxide reduction, and vanadium. It can be applied to redox flow batteries or metal-air batteries.
Description
본 발명은 신규한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머, 음이온교환막 및 그 제조방법에 관한 것으로, 보다 상세하게는 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 가지부 함유 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 공중합체 이오노머를 합성하고, 이로부터 음이온교환막을 제조하여 알칼리 연료전지 및 수전해 장치에 응용하는 기술에 관한 것이다. The present invention relates to a novel branch-containing poly(aryl piperidinium) copolymer ionomer, anion exchange membrane, and method for manufacturing the same. More specifically, the present invention relates to a novel branch-containing poly(aryl piperidinium) copolymer ionomer, an anion exchange membrane, and a method for manufacturing the same. More specifically, the present invention relates to a branch-containing piperidinium piperidinium repeating unit without an aryl ether bond in the polymer backbone. This relates to a technology for synthesizing a poly(aryl piperidinium) copolymer ionomer into which a group is introduced, manufacturing an anion exchange membrane therefrom, and applying it to alkaline fuel cells and water electrolysis devices.
지금까지 고분자 전해질막 연료전지(polymer electrolyte membrane fuel cell, PEMFC)는 비교적 높은 전류밀도를 갖고 친환경성이라는 장점 때문에 많은 연구가 진행되어 왔다. 특히, 나피온으로 대표되는 과불소화탄소 계열의 프로톤 교환막이 고분자 전해질막으로 주로 사용되었다. 그런데 나피온막은 낮은 산소환원반응(oxygen reduction reaction, ORR)으로 인하여 백금 기반의 귀금속 촉매 사용이 필수불가결 하므로 가격이 매우 높고 유리전이온도가 낮아 방향족 탄화수소계 고분자 전해질막 등의 개발을 비롯하여 나피온을 대체할 수 있는 연구가 활발하게 수행되고 있다.To date, much research has been conducted on polymer electrolyte membrane fuel cells (PEMFC) due to their relatively high current density and environmental friendliness. In particular, perfluorocarbon-based proton exchange membranes, represented by Nafion, were mainly used as polymer electrolyte membranes. However, due to the low oxygen reduction reaction (ORR) of the Nafion membrane, the use of a platinum-based noble metal catalyst is essential, so the price is very high and the glass transition temperature is low, leading to the development of aromatic hydrocarbon-based polymer electrolyte membranes, etc. Research on alternatives is being actively conducted.
이러한 연구들 중 음이온교환막을 이용하는 알칼리막 연료전지(alkaline membrane fuel cell, AMFC) 및 수전해는 백금 대신에 니켈, 망간 등 저가의 비귀금속을 전극촉매로 사용할 수 있고, 우수한 성능과 더불어 가격 경쟁력 또한 월등히 높은 것으로 알려져 지속적인 연구가 이루어지고 있다. 그러나 운전 시 하이드록실라디칼 및 이온의 분해 거동으로 인한 낮은 장기안정성 문제 때문에 알칼리막 연료전지의 내구성을 향상시키기 위한 연구가 필요한 실정이다. Among these studies, alkaline membrane fuel cell (AMFC) and water electrolysis using an anion exchange membrane can use low-cost non-precious metals such as nickel and manganese as electrode catalysts instead of platinum, and have excellent performance and price competitiveness. It is known to be significantly higher and ongoing research is being conducted. However, research is needed to improve the durability of alkaline membrane fuel cells due to low long-term stability problems due to the decomposition behavior of hydroxyl radicals and ions during operation.
알칼리막 연료전지에 적용하기 위한 음이온교환막으로서 폴리술폰(PSF), 폴리페닐에테르(PPO) 또는 폴리에테르에테르케톤(PEEK) 등과 같은 아릴 에테르 계열의 방향족 고분자 구조에 벤질 트리메틸암모늄기를 도입한 합성방법이 알려지게 되고, 고분자 주사슬을 따라 아릴 에테르(C-O) 결합을 갖는 반복단위를 형성하게 됨으로써 고분자의 용해도가 향상되는 등의 장점이 있었다. 그러나 한편으로는 고분자 주사슬의 아릴 에테르 결합으로 인하여 연료전지의 작동 시 전해질막의 하이드록실 라디칼 분해 거동을 수반하여 장기 안정성이 떨어지는 문제점이 발생하였으므로, 고분자 주사슬의 분해를 방지하는 것이 알칼리막 연료전지의 내구성을 향상시키기 위한 해결과제가 되었다.As an anion exchange membrane for application to alkaline membrane fuel cells, a synthesis method is used to introduce a benzyl trimethylammonium group into an aryl ether-based aromatic polymer structure such as polysulfone (PSF), polyphenyl ether (PPO), or polyetheretherketone (PEEK). It became known, and there were advantages such as improved solubility of the polymer by forming repeating units with aryl ether (C-O) bonds along the polymer main chain. However, on the other hand, due to the aryl ether bond in the polymer main chain, there is a problem of low long-term stability due to hydroxyl radical decomposition behavior of the electrolyte membrane during operation of the fuel cell, so it is important to prevent decomposition of the polymer main chain by using an alkaline membrane fuel cell. It became a problem to be solved to improve the durability of
또한, 통상의 음이온교환막은 제한된 화학적 안정성(80℃, 1M NaOH 용액에서 500시간 미만) 및 기계적 물성(인장강도 30Mpa 미만)을 가지므로 이를 적용한 연료전지의 경우에는 전력밀도가 낮고(0.1~0.5 W cm-2) 내구성도 낮은 단점이 있다. 또한, 높은 페닐 구조의 흡착효과로 인하여 바인더로 사용되었을 시, 삼상 계면형성이 제한되며 연료 효율성이 떨어진다는 문제점이 있다. In addition, typical anion exchange membranes have limited chemical stability (80°C, less than 500 hours in 1M NaOH solution) and mechanical properties (tensile strength less than 30Mpa), so fuel cells using them have low power density (0.1 to 0.5 W). cm -2 ) It has the disadvantage of low durability. In addition, due to the high adsorption effect of the phenyl structure, there is a problem that when used as a binder, the formation of a three-phase interface is limited and fuel efficiency is reduced.
또한, 음이온교환 고분자의 수분 투과 특성은 음이온교환막 연료전지에 있어서 물 관리에 매우 중요하다. 양극은 전기화학적 물 생성으로 인하여 물이 넘칠 수 있는 반면, 음극은 물 소비로 인하여 건조하기 쉽다. 따라서 높은 함수율 및 팽창률을 가지는 고분자의 경우 물질 전달 저항이 증가하며 전기화학적 안정성이 저해되므로 내구성에 지대한 영향을 끼친다.In addition, the water permeation characteristics of anion exchange polymers are very important for water management in anion exchange membrane fuel cells. The anode can overflow with water due to electrochemical water production, while the cathode is prone to drying out due to water consumption. Therefore, in the case of polymers with high moisture content and expansion rate, mass transfer resistance increases and electrochemical stability is impaired, which has a significant impact on durability.
한편, 아직까지 고분자 골격 내 아릴 에테르 결합이 없으면서 반복단위 내 가지부(branched moeity)를 함유하는 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 공중합체 이오노머가 합성된바 없으며, 이를 알칼리 연료전지용 막 및 바인더 또는 수전해 분야에 응용하는 기술에 대해서도 구체적으로 알려진 바 없다.Meanwhile, a poly(aryl piperidinium) copolymer ionomer into which a piperidinium group containing a branched moeity in the repeating unit is introduced without an aryl ether bond in the polymer backbone has not yet been synthesized, and it has been used as an alkaline fuel. There is no specific information about technologies applied to battery membranes and binders or to the water electrolysis field.
그러므로 본 발명자 등은, 열적·화학적 안정성 및 기계적 물성이 우수한 방향족 고분자 이온교환막의 응용분야를 확대하기 위하여 연구를 거듭한 결과, 종래 음이온교환 고분자가 갖는 낮은 분자량, 이온전도도, 함수율, 기계적 물성, 전력밀도, 내구성등과 같은 문제점을 음이온교환 고분자 반복단위 내에 가지부(branched moeity)를 함유하는 피페리디늄 그룹을 포함함으로써 해결하고자 하였다. 즉, 고분자 골격 내 아릴 에테르 결합이 없으면서 가지부(branched moeity)를 함유하는 피페리디늄 그룹이 도입된 폴리(아릴 피페리디늄) 공중합체 이오노머를 합성하며, 이로부터 음이온교환막을 제조함으로써 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 바나듐 레독스 플로우 배터리, 또는 금속-공기 전지 등에 응용할 수 있음을 발견하여 본 발명을 완성하였다.Therefore, the present inventors and others have conducted repeated research to expand the application fields of aromatic polymer ion exchange membranes with excellent thermal and chemical stability and mechanical properties, and as a result, the low molecular weight, ionic conductivity, water content, mechanical properties, and power of conventional anion exchange polymers have been determined. Problems such as density and durability were attempted to be solved by including a piperidinium group containing a branched moeity within the anion exchange polymer repeating unit. In other words, a poly(aryl piperidinium) copolymer ionomer into which a piperidinium group containing a branched moeity is introduced without an aryl ether bond in the polymer skeleton is synthesized, and an anion exchange membrane is manufactured from the poly(aryl piperidinium) ionomer for use in alkaline fuel cells. The present invention was completed by discovering that it can be applied to membranes and binders, water electrolysis devices, carbon dioxide reduction, vanadium redox flow batteries, or metal-air batteries.
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 제1 목적은 화학적 안정성이 뛰어나고, 분자량이 높으면서 기계적 물성이 우수하며, 낮은 팽창률과 높은 치수안정성 및 이온전도도, 및 제한된 페닐 흡착 효과를 갖는 신규한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머 및 그 제조방법을 제공하고자 하는 것이다.The present invention was developed in consideration of the above problems, and the first object of the present invention is to provide excellent chemical stability, high molecular weight and excellent mechanical properties, low expansion rate, high dimensional stability and ionic conductivity, and limited phenyl adsorption effect. The aim is to provide a novel branch-containing poly(aryl piperidinium) copolymer ionomer and a method for producing the same.
또한, 본 발명의 제2 목적은 상기 신규한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막을 제조함으로써, 저습도 조건에서도 작동 가능하고 물 관리 능력이 우수한 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 바나듐 레독스 플로우 배터리 또는 금속-공기 전지 등에 응용하고자 하는 것이다.In addition, the second object of the present invention is to manufacture an anion exchange membrane from the novel branch-containing poly(aryl piperidinium) copolymer ionomer, thereby providing a membrane and binder for alkaline fuel cells that can operate even in low humidity conditions and have excellent water management ability. , it is intended to be applied to water electrolysis devices, carbon dioxide reduction, vanadium redox flow batteries, or metal-air batteries.
상기한 바와 같은 목적을 달성하기 위한 본 발명은, 하기 <화학식 1>로 표시되는 반복단위를 갖는 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 제공한다.In order to achieve the above-described object, the present invention provides a branch-containing poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by the following <Formula 1>.
<화학식 1><Formula 1>
(상기 화학식 1에서, Aryl monomers는 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것이고,(In Formula 1, the Aryl monomers are one or more types selected from compounds represented by the following structural formula,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),, , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
Branching agent는 하기 구조식으로 표시되는 화합물로부터 선택되는 어느 하나의 것이다.The branching agent is any one selected from compounds represented by the following structural formula.
,,,,, ,,,, , , , , , , , , ,
또한, 본 발명은 (I) 단량체로서 (a) 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것, In addition, the present invention (I) as a monomer (a) at least one selected from the compounds represented by the following structural formula,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),, , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
(b) 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것,(b) at least one selected from compounds represented by the following structural formula,
,,,,, ,,,,, 및 , , , , , , , , , , and
(c) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계;(c) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계; (III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계; (IV) 상기 고체상의 중합체를 유기용매에 용해시킨 중합체 용액에 K2CO3 및 과량의 할로메탄을 부가 및 반응시켜 4급 피페리디늄 염을 형성하는 단계; 및 (V) 중합체 용액을 침전, 세척 및 건조하는 단계;를 포함하는 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법을 제공한다.(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution; (III) precipitating, washing and drying the viscous solution to obtain a solid polymer; (IV) adding and reacting K 2 CO 3 and an excess amount of halomethane to a polymer solution in which the solid polymer is dissolved in an organic solvent to form a quaternary piperidinium salt; and (V) precipitating, washing, and drying the polymer solution. A method for producing a branch-containing poly(aryl piperidinium) copolymer ionomer is provided.
또한, 본 발명은 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 음이온교환막을 제공한다.Additionally, the present invention provides an anion exchange membrane comprising the branch-containing poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 (i) 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 유기용매에 용해시켜 고분자용액을 형성하는 단계; (ii) 상기 고분자용액을 유리판에 캐스팅 및 건조함으로써 막을 수득하는 단계; 및 (iii) 상기 수득한 막을 1M NaHCO3 또는 1M NaOH로 처리한 후, 초순수로 수회 세척 및 건조하는 단계;를 포함하는 음이온교환막의 제조방법을 제공한다.In addition, the present invention includes the steps of (i) dissolving the branch-containing poly(aryl piperidinium) copolymer ionomer in an organic solvent to form a polymer solution; (ii) obtaining a film by casting and drying the polymer solution on a glass plate; and (iii) treating the obtained membrane with 1M NaHCO 3 or 1M NaOH, followed by washing and drying several times with ultrapure water.
또한, 본 발명은 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 알칼리 연료전지용 바인더를 제공한다.Additionally, the present invention provides a binder for an alkaline fuel cell containing the branch-containing poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 상기 음이온교환막을 포함하는 알칼리 연료전지를 제공한다.Additionally, the present invention provides an alkaline fuel cell including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 수전해 장치를 제공한다.Additionally, the present invention provides a water electrolysis device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 이산화탄소 환원 장치를 제공한다.Additionally, the present invention provides a carbon dioxide reduction device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 바나듐 레독스 플로우 배터리를 제공한다.Additionally, the present invention provides a vanadium redox flow battery including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 금속-공기 전지를 제공한다.Additionally, the present invention provides a metal-air battery including the anion exchange membrane.
본 발명에 따른 신규 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머는 화학적 안정성이 뛰어나고, 분자량이 높으면서 기계적 물성이 우수하며, 낮은 팽창률과 높은 치수안정성 및 이온전도도, 및 제한된 페닐 흡착 효과를 갖는다.The novel branch-containing poly(aryl piperidinium) copolymer ionomer according to the present invention has excellent chemical stability, high molecular weight and excellent mechanical properties, low expansion rate, high dimensional stability and ionic conductivity, and limited phenyl adsorption effect. .
아울러 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 제조되는 음이온교환막은 저습도 조건에서도 작동 가능하고 물 관리 능력이 우수하여 알칼리 연료전지용 막 및 바인더, 수전해 장치, 이산화탄소 환원, 바나듐 레독스 플로우 배터리 또는 금속-공기 전지 등에 응용할 수 있다.In addition, the anion exchange membrane manufactured from the branch-containing poly(aryl piperidinium) copolymer ionomer can operate even under low humidity conditions and has excellent water management ability, so it is used as a membrane and binder for alkaline fuel cells, water electrolysis devices, carbon dioxide reduction, and vanadium ion exchange membrane. It can be applied to dox flow batteries or metal-air batteries.
도 1은 본 발명의 실시예 1 내지 4로부터 제조한 b-PDTM-Trip-x(x=3.5, 5) 및 b-PFBM-Trip-x(x=3.5, 5)의 핵자기공명(1H NMR) 스펙트럼.
도 2는 본 발명의 실시예 5로부터 제조한 b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5 및 실시예 7로부터 제조한 b-PFBM-Tpb-3.5, b-PFBP-Tpb-3.5의 핵자기공명(1H NMR) 스펙트럼.
도 3은 본 발명의 실시예 9로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 기계적 물성을 나타낸 그래프.
도 4는 본 발명의 실시예 9로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 팽창률(swelling ratio)과 함수율(water uptake)을 나타낸 그래프.
도 5는 본 발명의 실시예 9로부터 제조한 음이온교환막(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1로부터 제조한 음이온교환막의 수소 투과도를 나타낸 그래프.
도 6은 본 발명의 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-5의 음극과 양극 바인더를 달리한 경우[실시예 3에 따른 바인더 A/C b-PFBP-Trip-3.5, 실시예 4에 따른 바인더 A/C b-PFBP-Trip-5]의 연료전지 성능을 나타낸 그래프.
도 7은 본 발명의 실시예 4에 따른 음극과 양극 바인더 b-PFBP-Trip-5를 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5 및 b-PDTP-Trip-5에 적용한 경우의 연료전지 성능을 나타낸 그래프.
도 8은 저습도 조건에서 본 발명의 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5의 음극과 양극 바인더를 달리한 경우[실시예 3에 따른 바인더 A/C b-PFBP-Trip-3.5, 실시예 4에 따른 바인더 A/C b-PFBP-Trip-5]의 연료전지 성능을 나타낸 그래프.
도 9는 저습도 조건에서 본 발명의 실시예 3에 따른 음극과 양극 바인더 b-PFBP-Trip-3.5를 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5 및 b-PDTP-Trip-5에 적용한 경우의 연료전지 성능을 나타낸 그래프.
Figure 1 shows nuclear magnetic resonance ( 1H ) of b-PDTM-Trip-x (x=3.5, 5) and b-PFBM-Trip-x (x=3.5, 5) prepared from Examples 1 to 4 of the present invention. NMR) spectrum.
Figure 2 shows b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5 prepared in Example 5 of the present invention and b-PFBM-Tpb-3.5, b-PFBP-Tpb-3.5 prepared in Example 7 of the present invention. Nuclear magnetic resonance ( 1H NMR) spectrum.
Figure 3 shows some of the anion exchange membranes (I - form) prepared in Example 9 of the present invention (made from the copolymer ionomers obtained in Examples 1 to 8) and the mechanical properties of the anion exchange membranes prepared in Comparative Examples 1 and 2. Graph showing physical properties.
Figure 4 shows the expansion coefficients of some of the anion exchange membranes (OH - form) (made from the copolymer ionomers obtained in Examples 1 to 8) prepared in Example 9 of the present invention and the anion exchange membranes prepared in Comparative Examples 1 and 2. Graph showing (swelling ratio) and water uptake.
Figure 5 is a graph showing the hydrogen permeability of some of the anion exchange membranes (made from the copolymer ionomers obtained in Examples 1 to 8) prepared in Example 9 of the present invention and an anion exchange membrane prepared in Comparative Example 1.
Figure 6 shows a case where the cathode and anode binders of b-PDTP-Trip-5 among the anion exchange membranes prepared in Example 9 of the present invention were different [Binder A/C b-PFBP-Trip-3.5 according to Example 3, carried out Graph showing the fuel cell performance of [Binder A/C b-PFBP-Trip-5] according to Example 4.
Figure 7 shows the case where the cathode and anode binder b-PFBP-Trip-5 according to Example 4 of the present invention was applied to b-PDTP-Trip-3.5 and b-PDTP-Trip-5 among the anion exchange membranes prepared in Example 9. Graph showing fuel cell performance.
Figure 8 shows the case of different cathode and anode binders of b-PDTP-Trip-3.5 among the anion exchange membranes prepared in Example 9 of the present invention under low humidity conditions [Binder A/C b-PFBP-Trip according to Example 3 -3.5, a graph showing the fuel cell performance of [binder A/C b-PFBP-Trip-5] according to Example 4.
Figure 9 shows b-PDTP-Trip-3.5 and b-PDTP-Trip- among the anion exchange membranes prepared from Example 9 with the cathode and anode binder b-PFBP-Trip-3.5 according to Example 3 of the present invention under low humidity conditions. Graph showing fuel cell performance when applied to Figure 5.
이하에서는 본 발명에 따른 신규한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머, 음이온교환막 및 그 제조방법에 관하여 상세히 설명하기로 한다.Hereinafter, the novel branch-containing poly(aryl piperidinium) copolymer ionomer, anion exchange membrane, and method for manufacturing the same according to the present invention will be described in detail.
본 발명에서는 하기 <화학식 1>로 표시되는 반복단위를 갖는 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 제공한다.The present invention provides a branch-containing poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by the following <Formula 1>.
<화학식 1><Formula 1>
(상기 화학식 1에서, Aryl monomers는 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것이고,(In Formula 1, the Aryl monomers are one or more types selected from compounds represented by the following structural formula,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),, , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
Branching agent는 하기 구조식으로 표시되는 화합물로부터 선택되는 어느 하나의 것이다.The branching agent is any one selected from compounds represented by the following structural formula.
,,,,, ,,,, , , , , , , , , ,
상기 화학식 1에서 보는 바와 같이, 본 발명에 따른 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머는 가지부(branched moeity)를 포함함으로써 고분자의 자유부피를 증가시켜 알칼리 연료전지 촉매층(catalyst layer)의 물질전달 능력을 향상시킨다. 또한, 높은 수분 보유 능력(water retention capability)은 낮은 상대습도 조건에서 안정적인 운전을 가능하게 하며, 촉매 표면과의 흡착능을 감소시켜 전극의 활성화에 따른 연료전지의 성능 향상에 기여하고 전반적인 시스템의 안정성을 높인다.As shown in Chemical Formula 1, the branched moeity-containing poly(aryl piperidinium) copolymer ionomer according to the present invention increases the free volume of the polymer by including branched moeity to form an alkaline fuel cell catalyst layer. improves the material transfer ability of In addition, high water retention capability enables stable operation under low relative humidity conditions, and reduces adsorption capacity with the catalyst surface, contributing to improved fuel cell performance due to electrode activation and overall system stability. Raise it.
또한, 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머는 기본적으로 고분자 골격 내에 아릴 에테르기를 포함하지 않고, 안정한 N-헤테로고리 암모늄기를 사용함으로써 화학적 안정성이 뛰어날 뿐만 아니라, 직선형 고분자에 비하여 높은 분자량, 내구성 및 우수한 기계적 물성을 갖는다. In addition, the branch-containing poly(aryl piperidinium) copolymer ionomer basically does not contain an aryl ether group in the polymer skeleton, and not only has excellent chemical stability by using a stable N-heterocyclic ammonium group, but also has a higher chemical stability compared to straight polymers. It has good molecular weight, durability and excellent mechanical properties.
또한, 본 발명은 (I) 단량체로서 (a) 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것, In addition, the present invention (I) as a monomer (a) at least one selected from the compounds represented by the following structural formula,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),, , , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
(b) 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것,(b) at least one selected from compounds represented by the following structural formula,
,,,,, ,,,,, 및 , , , , , , , , , , and
(c) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계;(c) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계; (III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계; (IV) 상기 고체상의 중합체를 유기용매에 용해시킨 중합체 용액에 K2CO3 및 과량의 할로메탄을 부가 및 반응시켜 4급 피페리디늄 염을 형성하는 단계; 및 (V) 중합체 용액을 침전, 세척 및 건조하는 단계;를 포함하는 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법을 제공한다.(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution; (III) precipitating, washing and drying the viscous solution to obtain a solid polymer; (IV) adding and reacting K 2 CO 3 and an excess amount of halomethane to a polymer solution in which the solid polymer is dissolved in an organic solvent to form a quaternary piperidinium salt; and (V) precipitating, washing, and drying the polymer solution. A method for producing a branch-containing poly(aryl piperidinium) copolymer ionomer is provided.
이때, 상기 (I) 단계의 유기용매는 할로겐계 용매로서 디클로로메탄, 클로로포름, 디클로로에탄, 디브로모메탄 및 테트라클로로에탄으로 이루어진 군으로부터 선택된 1종 이상의 것일 수 있고, 디클로로메탄을 바람직하게 사용한다.At this time, the organic solvent in step (I) may be one or more halogen-based solvents selected from the group consisting of dichloromethane, chloroform, dichloroethane, dibromomethane, and tetrachloroethane, and dichloromethane is preferably used. .
또한, 상기 (II) 단계의 강산 촉매는 트리플루오로아세트산, 트리플루오로메탄술폰산, 펜타플루오로에탄술폰산, 헵타플루오로-1-프로판술폰산, 퍼플루오로프로피온산, 헵타플루오로부티르산, 또는 이들의 혼합물일 수 있고, 트리플루오로아세트산/트리플루오로메탄술폰산의 혼합물을 바람직하게 사용한다.In addition, the strong acid catalyst in step (II) is trifluoroacetic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoro-1-propanesulfonic acid, perfluoropropionic acid, heptafluorobutyric acid, or these. It may be a mixture, and a mixture of trifluoroacetic acid/trifluoromethanesulfonic acid is preferably used.
또한, 상기 (IV) 단계의 유기용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸술폭시드 또는 디메틸포름아미드일 수 있다.Additionally, the organic solvent in step (IV) may be N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, or dimethylformamide.
또한, 상기 (IV) 단계에서는 4급 피페리디늄 염을 형성하기 위하여 중합체를 할로메탄과 반응시키는바, 상기 할로메탄은 플루오로메탄, 클로로메탄, 브로모메탄 또는 아이오도메탄일 수 있고, 아이오도메탄을 바람직하게 사용한다.Additionally, in step (IV), the polymer is reacted with a halomethane to form a quaternary piperidinium salt, and the halomethane may be fluoromethane, chloromethane, bromomethane, or iodomethane, and io Domethane is preferably used.
또한, 본 발명은 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 음이온교환막을 제공한다.Additionally, the present invention provides an anion exchange membrane comprising the branch-containing poly(aryl piperidinium) copolymer ionomer.
본 발명에 따른 상기 음이온교환막은 고분자 골격 내 아릴 에테르 결합이 없으면서 N-헤테로 암모늄기를 갖는 공중합체 이오노머의 구조로 인하여 화학적 안정성이 뛰어나다. 게다가 가지부가 도입된 구조로 인하여 분자량이 높고, 치수안정성 및 기계적 물성이 우수할 뿐만 아니라, 이온전도도가 높으면서도 팽창률은 억제되는 특유의 작용효과를 나타낸다.The anion exchange membrane according to the present invention has excellent chemical stability due to the structure of a copolymer ionomer having an N-hetero ammonium group without an aryl ether bond in the polymer skeleton. In addition, due to the structure in which the branch parts are introduced, the molecular weight is high, dimensional stability and mechanical properties are excellent, and the ionic conductivity is high while the expansion rate is suppressed.
또한, 본 발명은 (i) 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 유기용매에 용해시켜 고분자용액을 형성하는 단계; (ii) 상기 고분자용액을 유리판에 캐스팅 및 건조함으로써 막을 수득하는 단계; 및 (iii) 상기 수득한 막을 1M NaHCO3 또는 1M NaOH로 처리한 후, 초순수로 수회 세척 및 건조하는 단계;를 포함하는 음이온교환막의 제조방법을 제공한다.In addition, the present invention includes the steps of (i) dissolving the branch-containing poly(aryl piperidinium) copolymer ionomer in an organic solvent to form a polymer solution; (ii) obtaining a film by casting and drying the polymer solution on a glass plate; and (iii) treating the obtained membrane with 1M NaHCO 3 or 1M NaOH, followed by washing and drying several times with ultrapure water.
이때, 상기 (i) 단계의 유기용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸술폭시드 또는 디메틸포름아미드일 수 있다.At this time, the organic solvent in step (i) may be N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, or dimethylformamide.
또한, 상기 고분자용액의 농도는 2~30 중량%인 것이 바람직하고, 그 농도가 3.0~5.0 중량%인 것이 더욱 바람직하다. 고분자용액의 농도가 2 중량% 미만이면 막의 형성능이 떨어질 수 있고, 30 중량%를 초과하면 점도가 너무 높아져 제막 후 막이 물성이 저하될 수 있다.In addition, the concentration of the polymer solution is preferably 2 to 30% by weight, and more preferably 3.0 to 5.0% by weight. If the concentration of the polymer solution is less than 2% by weight, the film forming ability may be reduced, and if it exceeds 30% by weight, the viscosity may become too high and the physical properties of the film may be deteriorated after film formation.
또한, 상기 (ii) 단계의 건조는 80~90℃ 오븐에서 24시간 동안 유기용매를 서서히 제거한 후, 120~150℃ 진공오븐에서 12시간 동안 가열함으로써 유기용매를 완전히 제거하는 것이 바람직하다.In addition, the drying in step (ii) is preferably performed by gradually removing the organic solvent in an oven at 80-90°C for 24 hours and then completely removing the organic solvent by heating in a vacuum oven at 120-150°C for 12 hours.
이어서, 상기 (i) 내지 (ii) 단계를 거쳐 수득한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머 막을 1M NaHCO3 또는 1M NaOH로 처리함으로써, 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 할라이드 형태(I- form 등)를 HCO3 - 또는 OH- 형태로 전환시킨 음이온교환막을 제조할 수 있다.Subsequently, the branch-containing poly(aryl piperidinium) copolymer ionomer film obtained through steps (i) to (ii) was treated with 1M NaHCO 3 or 1M NaOH to form a branch-containing poly(aryl piperidinium) copolymer film. An anion exchange membrane can be manufactured by converting the halide form (I - form, etc.) of the combined ionomer into HCO 3 - or OH - form.
또한, 본 발명은 상기 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머를 포함하는 알칼리 연료전지용 바인더를 제공한다.Additionally, the present invention provides a binder for an alkaline fuel cell containing the branch-containing poly(aryl piperidinium) copolymer ionomer.
또한, 본 발명은 상기 음이온교환막을 포함하는 알칼리 연료전지를 제공한다.Additionally, the present invention provides an alkaline fuel cell including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 수전해 장치를 제공한다.Additionally, the present invention provides a water electrolysis device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 이산화탄소 환원 장치를 제공한다.Additionally, the present invention provides a carbon dioxide reduction device including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 바나듐 레독스 플로우 배터리를 제공한다.Additionally, the present invention provides a vanadium redox flow battery including the anion exchange membrane.
또한, 본 발명은 상기 음이온교환막을 포함하는 금속-공기 전지를 제공한다.Additionally, the present invention provides a metal-air battery including the anion exchange membrane.
이하 본 발명에 따른 실시예 및 비교예를 첨부된 도면과 함께 구체적으로 설명한다.Hereinafter, examples and comparative examples according to the present invention will be described in detail with the accompanying drawings.
[실시예 1 내지 2] 트립티센 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 1 to 2] Preparation of tryptycene branch-containing poly(aryl piperidinium) copolymer ionomer
단량체로서 디페닐에탄[DP, 6.75 mmol(1.23 g)], p-터페닐[TP, 20.25 mmol(4.663 g)], 트립티센[Trip, 1 mmol(0.254 g)] 및 1-메틸-4-피페리돈[MP, 34.2 mmol(3.87 g)]을 100mL 반응기에 투입한 후, 디클로로메탄(DCM, 24 mL)을 부가하여 교반하면서 단량체들을 용해시켜 용액을 형성하였다. 상기 용액의 온도를 -1℃로 냉각시킨 후, 트리플루오로아세트산(TFA, 3.6 mL) 및 트리플루오로메탄술폰산(TFSA, 30 mL)의 혼합물을 상기 용액에 서서히 부가, 교반 및 2시간 반응시켜 점성 용액을 얻었다. 상기 점성 용액을 증류수에 부어 침전, 탈이온수로 수회 세척 및 80℃ 오븐에서 24시간 건조하여 고체상의 트립티센 가지부 함유 폴리(디페닐-co-터페닐 N-메틸 피페리딘) 공중합체를 제조하였으며(수율 92%), 이를 b-PDTM-Trip-3.5라고 명명하였다.As monomers, diphenylethane [DP, 6.75 mmol (1.23 g)], p-terphenyl [TP, 20.25 mmol (4.663 g)], tryptycene [Trip, 1 mmol (0.254 g)], and 1-methyl-4- After piperidone [MP, 34.2 mmol (3.87 g)] was added to a 100 mL reactor, dichloromethane (DCM, 24 mL) was added and stirred to dissolve the monomers to form a solution. After cooling the temperature of the solution to -1°C, a mixture of trifluoroacetic acid (TFA, 3.6 mL) and trifluoromethanesulfonic acid (TFSA, 30 mL) was slowly added to the solution, stirred, and reacted for 2 hours. A viscous solution was obtained. The viscous solution was poured into distilled water to precipitate, washed several times with deionized water, and dried in an oven at 80°C for 24 hours to prepare a solid tryptycene branch-containing poly(diphenyl-co-terphenyl N-methyl piperidine) copolymer. (yield 92%), and it was named b-PDTM-Trip-3.5.
다음으로, 상기 제조한 b-PDTM-Trip-3.5(20 mmol)을 디메틸술폭시드(200 mL)에 용해시켜 중합체 용액을 얻은 후, 상기 중합체 용액에 K2CO3(6.9 g, 50 mmol) 및 아이오도메탄[MeI, 60 mmol(8.46 g)]을 부가 및 상온, 암실에서 24시간 반응시켜 4급 피페리디늄 염을 형성하였다. 다음으로, 중합체 용액을 에틸아세테이트 500mL에 침전, 여과, 탈이온수로 수회 세척 및 80℃ 대류오븐에서 완전히 건조하여 고체상의 트립티센 가지부 함유 폴리(디페닐-co-터페닐 N,N-디메틸피페리디늄) 공중합체 이오노머를 제조하였고(수율 83%), 이를 b-PDTP-Trip-3.5라고 명명하였으며, 아래 scheme 1에 그 합성경로를 반응식으로 나타내었다(실시예 1).Next, the prepared b-PDTM-Trip-3.5 (20 mmol) was dissolved in dimethyl sulfoxide (200 mL) to obtain a polymer solution, and then K 2 CO 3 (6.9 g, 50 mmol) and Iodomethane [MeI, 60 mmol (8.46 g)] was added and reacted at room temperature in the dark for 24 hours to form a quaternary piperidinium salt. Next, the polymer solution was precipitated in 500 mL of ethyl acetate, filtered, washed several times with deionized water, and completely dried in a convection oven at 80°C to obtain poly(diphenyl-co-terphenyl N,N-dimethylpipe) containing trypticene branches in the solid phase. ridinium) copolymer ionomer was prepared (yield 83%), which was named b-PDTP-Trip-3.5, and the synthetic route is shown in scheme 1 below (Example 1).
scheme 1. 트립티센 가지부 함유 폴리(디페닐-co-터페닐 N,N-디메틸피페리디늄) 공중합체 이오노머의 합성 경로Scheme 1. Synthesis route of poly(diphenyl-co-terphenyl N,N-dimethylpiperidinium) copolymer ionomer containing tryptycene branches.
또한, 상기 scheme 1에 나타낸 합성경로의 반응식 중 트립티센의 몰 분율X(%)를 5%로 조절한 트립티센 가지부 함유 폴리(디페닐-co-터페닐 N,N-디메틸피페리디늄) 공중합체 및 그 이오노머를 실시예 1과 동일한 방법으로 제조하였고, 이를 각각 b-PDTM-Trip-5, b-PDTP-Trip-5라고 명명하였다(실시예 2).In addition, poly(diphenyl-co-terphenyl N,N-dimethylpiperidinium) containing tryptycene branches in which the mole fraction The copolymer and its ionomer were prepared in the same manner as Example 1, and were named b-PDTM-Trip-5 and b-PDTP-Trip-5, respectively (Example 2).
[실시예 3 내지 4] 트립티센 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 3 to 4] Preparation of tryptycene branch-containing poly(aryl piperidinium) copolymer ionomer
단량체로서 실시예 1, 2의 디페닐에탄 및 p-터페닐 대신에 9,9'-디메틸플루오렌 및 바이페닐을 사용한 것을 제외하고는 실시예 1, 2와 동일한 방법으로 트립티센 가지부 함유 폴리(플루오렌-co-바이페닐 N,N-디메틸피페리디늄) 공중합체 및 그 이오노머를 제조하였고, 이를 각각 b-PFBM-Trip-3.5, b-PFBP-Trip-3.5(실시예 3) 및 b-PFBM-Trip-5, b-PFBP-Trip-5(실시예 4)라고 명명하였으며, 아래 scheme 2에 그 합성경로를 반응식으로 나타내었다.Tryptycene branch-containing poly is prepared in the same manner as Examples 1 and 2, except that 9,9'-dimethylfluorene and biphenyl were used as monomers instead of diphenylethane and p-terphenyl of Examples 1 and 2. (Fluorene-co-biphenyl N,N-dimethylpiperidinium) copolymer and its ionomer were prepared, and they were b-PFBM-Trip-3.5, b-PFBP-Trip-3.5 (Example 3) and b, respectively. It was named -PFBM-Trip-5, b-PFBP-Trip-5 (Example 4), and the synthetic route is shown in scheme 2 below.
scheme 2. 트립티센 가지부 함유 폴리(플루오렌-co-바이페닐 N,N-디메틸피페리디늄) 공중합체 이오노머의 합성 경로Scheme 2. Synthesis route of poly(fluorene-co-biphenyl N,N-dimethylpiperidinium) copolymer ionomer containing tryptycene branches.
[실시예 5 내지 6] 1,3,5-트리페닐벤젠 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 5 to 6] Preparation of 1,3,5-triphenylbenzene branch-containing poly(aryl piperidinium) copolymer ionomer
단량체로서 실시예 1의 트립티센 대신에 1,3,5-트리페닐벤젠을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 1,3,5-트리페닐벤젠 가지부 함유 폴리(디페닐-co-터페닐 N,N-디메틸피페리디늄) 공중합체 및 그 이오노머를 제조하였고, 이를 각각 b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5(실시예 5) 및 b-PDTM-Tpb-5, b-PDTP-Tpb-5(실시예 6)라고 명명하였으며, 아래 scheme 3에 그 합성경로를 반응식으로 나타내었다.1,3,5-triphenylbenzene branch-containing poly(diphenyl-co) was prepared in the same manner as in Example 1, except that 1,3,5-triphenylbenzene was used instead of tryptisene in Example 1 as the monomer. -Terphenyl N,N-dimethylpiperidinium) copolymer and its ionomer were prepared, and they were prepared as b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5 (Example 5) and b-PDTM-Tpb-, respectively. 5, was named b-PDTP-Tpb-5 (Example 6), and the synthetic route is shown in scheme 3 below.
scheme 3. 1,3,5-트리페닐벤젠 가지부 함유 폴리(디페닐-co-터페닐 N,N-디메틸피페리디늄) 공중합체 이오노머의 합성 경로Scheme 3. Synthesis route of 1,3,5-triphenylbenzene branched poly(diphenyl-co-terphenyl N,N-dimethylpiperidinium) copolymer ionomer
[실시예 7 내지 8] 1,3,5-트리페닐벤젠 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조[Examples 7 to 8] Preparation of 1,3,5-triphenylbenzene branch-containing poly(aryl piperidinium) copolymer ionomer
단량체로서 실시예 3의 트립티센 대신에 1,3,5-트리페닐벤젠을 사용한 것을 제외하고는 실시예 3과 동일한 방법으로 1,3,5-트리페닐벤젠 가지부 함유 폴리(플루오렌-co-바이페닐 N,N-디메틸피페리디늄) 공중합체 및 그 이오노머를 제조하였고, 이를 각각 b-PFBM-Tpb-3.5, b-PFBP-Tpb-3.5(실시예 7) 및 b-PFBM-Tpb-5, b-PFBP-Tpb-5(실시예 8)라고 명명하였으며, 아래 scheme 4에 그 합성경로를 반응식으로 나타내었다.1,3,5-triphenylbenzene branch-containing poly(fluorene-co) was prepared in the same manner as in Example 3, except that 1,3,5-triphenylbenzene was used instead of tryptisene in Example 3 as the monomer. -Biphenyl N,N-dimethylpiperidinium) copolymer and its ionomer were prepared, and they were prepared as b-PFBM-Tpb-3.5, b-PFBP-Tpb-3.5 (Example 7) and b-PFBM-Tpb-, respectively. 5, was named b-PFBP-Tpb-5 (Example 8), and the synthetic route is shown in scheme 4 below.
scheme 4. 1,3,5-트리페닐벤젠 가지부 함유 폴리(플루오렌-co-바이페닐 N,N-디메틸피페리디늄) 공중합체 이오노머의 합성 경로Scheme 4. Synthesis route of 1,3,5-triphenylbenzene branched poly(fluorene-co-biphenyl N,N-dimethylpiperidinium) copolymer ionomer
[실시예 9] 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Example 9] Preparation of anion exchange membrane from branch-containing poly(aryl piperidinium) copolymer ionomer
상기 실시예 1 내지 8로부터 제조한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머(1.7 g)를 디메틸술폭시드에 용해시켜 4 중량% 농도의 고분자용액을 형성하였다. 이어서, 상기 고분자용액을 0.45 ㎛ PTFE 필터로 여과하고, 투명한 용액을 21 x 24 cm 유리판에 캐스팅하였다. 상기 캐스팅 용액을 90℃ 오븐에서 24시간 건조하여 용매를 서서히 제거한 후, 140℃ 진공오븐에서 12시간 가열하여 용매를 완전히 제거함으로써 막(I- 형태, 두께 25±5 ㎛)을 얻었다.The branch-containing poly(aryl piperidinium) copolymer ionomer (1.7 g) prepared in Examples 1 to 8 was dissolved in dimethyl sulfoxide to form a polymer solution with a concentration of 4% by weight. Subsequently, the polymer solution was filtered through a 0.45 ㎛ PTFE filter, and the transparent solution was cast on a 21 x 24 cm glass plate. The casting solution was dried in an oven at 90°C for 24 hours to gradually remove the solvent, and then heated in a vacuum oven at 140°C for 12 hours to completely remove the solvent, thereby obtaining a film (I - form, thickness 25±5 ㎛).
상기 수득한 I- 형태의 막을 1M NaOH 수용액에 24시간 침지하여 카운터 이온을 OH-로 전환시키고 초순수로 수회 세척 및 건조함으로써 음이온교환막을 제조하였다(얻어진 음이온교환막 샘플의 명명은 실시예 1 내지 8로부터 제조한 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머에서 명명한 것과 같다).The obtained I - form membrane was immersed in 1M NaOH aqueous solution for 24 hours to convert the counter ion into OH - and washed with ultrapure water several times and dried to prepare an anion exchange membrane (the names of the obtained anion exchange membrane samples are from Examples 1 to 8. Same as the name given to the prepared branch-containing poly(aryl piperidinium) copolymer ionomer).
[비교예 1] 가지부를 함유하지 않는 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Comparative Example 1] Preparation of anion exchange membrane from poly(aryl piperidinium) copolymer ionomer containing no branches
단량체로서 트립티센을 사용하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 얻어진 폴리(디페닐-co-터페닐 N, N-디메틸피페리디늄) 공중합체 이오노머를 실시예 9와 동일한 방법으로 제막함으로써 가지부를 함유하지 않는 음이온교환막을 제조하였으며, 이를 PDTP라고 명명하였다.The poly(diphenyl-co-terphenyl N, N-dimethylpiperidinium) copolymer ionomer obtained in the same manner as in Example 1, except that tryptycene was not used as a monomer, was formed into a film in the same manner as in Example 9. By doing this, an anion exchange membrane containing no branches was manufactured, and it was named PDTP.
[비교예 2] 가지부를 함유하지 않는 폴리(아릴 피페리디늄) 공중합체 이오노머로부터 음이온교환막의 제조[Comparative Example 2] Preparation of anion exchange membrane from poly(aryl piperidinium) copolymer ionomer containing no branches
단량체로서 트립티센을 사용하지 않은 것을 제외하고는 실시예 3과 동일한 방법으로 얻어진 폴리(플루오렌-co-바이페닐 N, N-디메틸피페리디늄) 공중합체 이오노머를 실시예 9와 동일한 방법으로 제막함으로써 가지부를 함유하지 않는 음이온교환막을 제조하였으며, 이를 PFBP라고 명명하였다.Poly(fluorene-co-biphenyl N, N-dimethylpiperidinium) copolymer ionomer obtained in the same manner as in Example 3, except that tryptycene was not used as a monomer, was formed into a film in the same manner as in Example 9. By doing this, an anion exchange membrane containing no branches was manufactured, and it was named PFBP.
[시험예] [Test example]
본 발명의 실시예 및 비교예로부터 제조한 음이온교환막의 기계적 물성, 함수율, 팽창률 및 연료전지 성능 등의 시험 데이터는 본 발명의 발명자 등에 의한 선출원 공개특허 제10-2021-0071810호에 기재된 방법에 의하여 측정 및 평가하였다.Test data such as mechanical properties, water content, expansion rate, and fuel cell performance of the anion exchange membrane prepared from the Examples and Comparative Examples of the present invention were obtained by the method described in Previous Patent Publication No. 10-2021-0071810 by the inventor of the present invention. Measured and evaluated.
도 1에는 본 발명의 실시예 1 내지 4로부터 제조한 b-PDTM-Trip-x(x=3.5, 5) 및 b-PFBM-Trip-x(x=3.5, 5)의 핵자기공명(1H NMR) 스펙트럼을, 도 2에는 본 발명의 실시예 5로부터 제조한 b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5 및 실시예 7로부터 제조한 b-PFBM-Tpb-3.5, b-PFBP-Tpb-3.5의 핵자기공명(1H NMR) 스펙트럼을 나타내었는바, 각각 트립티센의 특성 피크가 5.49ppm에서, 1,3,5-트리페닐벤젠의 특성 피크가 7.8ppm에서 관측되어 가지부 함유 폴리(아릴 피페리디늄) 공중합체가 합성되었음을 확인하였다.Figure 1 shows nuclear magnetic resonance ( 1H ) of b-PDTM-Trip-x (x=3.5, 5) and b-PFBM-Trip-x (x=3.5, 5) prepared from Examples 1 to 4 of the present invention. NMR) spectrum, Figure 2 shows b-PDTM-Tpb-3.5, b-PDTP-Tpb-3.5 prepared in Example 5 of the present invention, and b-PFBM-Tpb-3.5, b-PFBP prepared in Example 7. The nuclear magnetic resonance ( 1H NMR) spectrum of -Tpb-3.5 was shown, and the characteristic peak of tryptycene was observed at 5.49ppm and the characteristic peak of 1,3,5-triphenylbenzene was observed at 7.8ppm, respectively. It was confirmed that a poly(aryl piperidinium)-containing copolymer was synthesized.
또한, 도 3에는 본 발명의 실시예 9로부터 제조한 음이온교환막(I- 형태)(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 기계적 물성을 나타내었다.In addition, Figure 3 shows some of the anion exchange membranes (I - form) prepared in Example 9 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 8) and anion exchange membranes prepared in Comparative Examples 1 and 2. The mechanical properties were shown.
본 발명의 실시예에 따른 가지부를 함유하는 구조와 증가된 분자량 및 얽힌 구조로 인하여 가지부를 함유하지 않는 비교예보다 높은 인장강도 및 연신율을 나타내었으며, 증가한 기계적 강도는 셀 성능 및 내구성 향상에 기여한다.Due to the structure containing the branch portion and the increased molecular weight and entangled structure according to the embodiment of the present invention, higher tensile strength and elongation were shown than the comparative example not containing the branch portion, and the increased mechanical strength contributes to improved cell performance and durability. .
또한, 도 4에는 본 발명의 실시예 9로부터 제조한 음이온교환막(OH- 형태)(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1, 2로부터 제조한 음이온교환막의 팽창률(swelling ratio)과 함수율(water uptake)을 나타내었다.In addition, Figure 4 shows some of the anion exchange membranes (OH - form) prepared in Example 9 of the present invention (made from the copolymer ionomer obtained in Examples 1 to 8) and anion exchange membranes prepared in Comparative Examples 1 and 2. The swelling ratio and water uptake were shown.
본 발명의 실시예에 따른 가지부를 함유하는 공중합체 이오노머 막은 높은 분자량, 거대분자 사슬-스레딩(supramolecular chain-threading), 맞물림 반응(interlocking reaction), 파이 상호작용(p-stacking interaction) 및 높은 이온교환능(IEC), 향상된 자유부피로 인하여 종래 가지부를 함유하지 않는 공중합체 이오노머 막에 비하여 낮은 팽창률과 높은 함수율을 보였다.The branch-containing copolymer ionomer membrane according to an embodiment of the present invention has high molecular weight, supramolecular chain-threading, interlocking reaction, p-stacking interaction, and high ion exchange capacity. (IEC), due to the improved free volume, it showed a low expansion rate and high water content compared to a conventional copolymer ionomer membrane that does not contain branches.
일반적으로 함수율 및 이온전도성이 높으면 팽창률이 증가하는데, 본 발명에 따른 가지부를 함유하는 공중합체 이오노머 막은 함수율은 높지만, 가지 구조로 인하여 팽창률을 억제함으로써 원하는 물성을 얻을 수 있다.In general, the higher the water content and ionic conductivity, the higher the expansion rate. The copolymer ionomer membrane containing the branch portion according to the present invention has a high water content, but the desired physical properties can be obtained by suppressing the expansion rate due to the branch structure.
즉, 본 발명의 가지부를 함유하는 구조 때문에 음이온교환막의 높은 함수율, 향상된 치수안정성 및 기계적 강도로 인하여 이온전도성과 팽창률의 딜레마를 해결할 수 있었다. That is, due to the structure containing the branch portion of the present invention, the dilemma of ion conductivity and expansion rate was solved due to the high water content, improved dimensional stability, and mechanical strength of the anion exchange membrane.
또한, 도 5에는 본 발명의 실시예 9로부터 제조한 음이온교환막(실시예 1 내지 8에서 얻은 공중합체 이오노머로부터 제조한 것) 중 일부 및 비교예 1로부터 제조한 음이온교환막의 수소 투과도를 나타내었다.In addition, Figure 5 shows the hydrogen permeability of some of the anion exchange membranes (made from the copolymer ionomers obtained in Examples 1 to 8) prepared in Example 9 of the present invention and the anion exchange membrane prepared in Comparative Example 1.
본 발명에 따른 견고한 가지 구조의 향상된 자유부피로 인하여 촉매층에 사용되는 이오노머의 수소 투과도가 향상되었으며, 이렇게 향상된 수소 투과도는 전기화학 반응 중 반응물의 물질전달 저항을 줄일 수 있고, 촉매층의 삼상계면 형성에 도움을 준다.Due to the improved free volume of the rigid branch structure according to the present invention, the hydrogen permeability of the ionomer used in the catalyst layer is improved, and this improved hydrogen permeability can reduce the mass transfer resistance of reactants during electrochemical reactions and contribute to the formation of a three-phase interface in the catalyst layer. Helpful.
또한, 도 6에는 본 발명의 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-5의 음극과 양극 바인더를 달리한 경우[실시예 3에 따른 바인더 A/C b-PFBP-Trip-3.5, 실시예 4에 따른 바인더 A/C b-PFBP-Trip-5]의 연료전지 성능을, 도 7에는 본 발명의 실시예 4에 따른 음극과 양극 바인더 b-PFBP-Trip-5를 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5 및 b-PDTP-Trip-5에 적용한 경우의 연료전지 성능을 각각 나타내었는바, 높은 상대습도, H2-O2@80℃, 1.3 bar에서 2.5 W cm-2의 우수한 성능을 보였고, 이는 pristine 구조와 비슷한 성능을 갖는 것이다.In addition, Figure 6 shows a case where the cathode and anode binders of b-PDTP-Trip-5 among the anion exchange membranes prepared in Example 9 of the present invention were different [binder A/C b-PFBP-Trip-3.5 according to Example 3. , Binder A/C b-PFBP-Trip-5 according to Example 4], and in Figure 7, the fuel cell performance of the binder A/C b-PFBP-Trip-5 according to Example 4 of the present invention is shown in Example 9. The fuel cell performance when applied to b-PDTP-Trip-3.5 and b -PDTP-Trip-5 among the anion exchange membranes manufactured from It showed excellent performance of 2.5 W cm -2 , which is similar to the pristine structure.
또한, 도 8에는 저습도 조건에서 본 발명의 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5의 음극과 양극 바인더를 달리한 경우[실시예 3에 따른 바인더 A/C b-PFBP-Trip-3.5, 실시예 4에 따른 바인더 A/C b-PFBP-Trip-5]의 연료전지 성능을, 도 9에는 저습도 조건에서 본 발명의 실시예 3에 따른 음극과 양극 바인더 b-PFBP-Trip-3.5를 실시예 9로부터 제조한 음이온교환막 중 b-PDTP-Trip-3.5 및 b-PDTP-Trip-5에 적용한 경우의 연료전지 성능을 나타내었다.In addition, Figure 8 shows a case where the cathode and anode binders of b-PDTP-Trip-3.5 among the anion exchange membranes prepared in Example 9 of the present invention were changed under low humidity conditions [binder A/C b-PFBP according to Example 3 -Trip-3.5, the fuel cell performance of the binder A/C b-PFBP-Trip-5 according to Example 4, and Figure 9 shows the cathode and anode binder b-PFBP according to Example 3 of the present invention under low humidity conditions. The fuel cell performance was shown when -Trip-3.5 was applied to b-PDTP-Trip-3.5 and b-PDTP-Trip-5 among the anion exchange membranes prepared in Example 9.
낮은 상대습도, H2-O2@80℃, 1.3 bar에서도 1.6 W cm-2의 우수한 성능을 보였는바, 이는 본 발명에 따른 가지 구조 이오노머의 향상된 자유부피, 높은 이온전도성, 높은 함수율, 촉매층의 향상된 삼상계면 덕분에 낮은 습도 및 낮은 유량에서도 우수한 연료전지 성능을 나타내는 것으로 해석할 수 있다.Even at low relative humidity, H 2 -O 2 @80°C, 1.3 bar, excellent performance of 1.6 W cm -2 was shown, which is due to the improved free volume, high ionic conductivity, high water content, and catalyst layer of the branched ionomer according to the present invention. Thanks to the improved three-phase interface, it can be interpreted that excellent fuel cell performance is achieved even at low humidity and low flow rates.
Claims (15)
<화학식 1>
(상기 화학식 1에서, Aryl monomers는 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것이고,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),,
Branching agent는 하기 구조식으로 표시되는 화합물로부터 선택되는 어느 하나의 것이다.
,,,,, ,,,, A branch-containing poly(aryl piperidinium) copolymer ionomer having a repeating unit represented by the following <Chemical Formula 1>.
<Formula 1>
(In Formula 1, the Aryl monomers are one or more types selected from compounds represented by the following structural formula,
, , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
The branching agent is any one selected from compounds represented by the following structural formula.
, , , , , , , , ,
,,,,, (R=H 또는 CH3),(R=H, OH 또는 탄소수 1 내지 5의 알콕시),(n은 1 내지 10의 정수),,
(b) 하기 구조식으로 표시되는 화합물로부터 선택되는 1종 이상의 것,
,,,,, ,,,,, 및
(c) 1-메틸-4-피페리돈을 유기용매에 용해시켜 용액을 형성하는 단계;
(II) 상기 용액에 강산 촉매를 서서히 부가, 교반 및 반응시켜 점성 용액을 얻는 단계;
(III) 상기 점성 용액을 침전, 세척 및 건조하여 고체상의 중합체를 수득하는 단계;
(IV) 상기 고체상의 중합체를 유기용매에 용해시킨 중합체 용액에 K2CO3 및 과량의 할로메탄을 부가 및 반응시켜 4급 피페리디늄 염을 형성하는 단계; 및
(V) 중합체 용액을 침전, 세척 및 건조하는 단계;를 포함하는 가지부 함유 폴리(아릴 피페리디늄) 공중합체 이오노머의 제조방법,(I) As a monomer, (a) one or more types selected from compounds represented by the following structural formula,
, , , , , (R=H or CH 3 ), (R=H, OH or alkoxy with 1 to 5 carbon atoms), (n is an integer from 1 to 10), ,
(b) at least one selected from compounds represented by the following structural formula,
, , , , , , , , , , and
(c) dissolving 1-methyl-4-piperidone in an organic solvent to form a solution;
(II) slowly adding a strong acid catalyst to the solution, stirring and reacting to obtain a viscous solution;
(III) precipitating, washing and drying the viscous solution to obtain a solid polymer;
(IV) adding and reacting K 2 CO 3 and an excess amount of halomethane to a polymer solution in which the solid polymer is dissolved in an organic solvent to form a quaternary piperidinium salt; and
(V) precipitating, washing, and drying the polymer solution; a method for producing a branch-containing poly(aryl piperidinium) copolymer ionomer,
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| WO2019068051A2 (en) | 2017-09-28 | 2019-04-04 | Yushan Yan | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
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| US20190036143A1 (en) | 2016-03-28 | 2019-01-31 | University Of Delaware | Poly(aryl piperidinium) polymers for use as hydroxide exchange membranes and ionomers |
| WO2019068051A2 (en) | 2017-09-28 | 2019-04-04 | Yushan Yan | Poly(aryl piperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
| JP2020536165A (en) | 2017-09-28 | 2020-12-10 | ヤン，ユシャン | Poly (arylpiperidinium) polymers including those with stable cationic pendant groups for use as anion exchange membranes and ionomers |
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