CN105367782B - 一种2‑甲基‑3‑烷基咪唑鎓盐聚芳醚梳型聚合物及其制备与应用 - Google Patents
一种2‑甲基‑3‑烷基咪唑鎓盐聚芳醚梳型聚合物及其制备与应用 Download PDFInfo
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- CN105367782B CN105367782B CN201510731037.6A CN201510731037A CN105367782B CN 105367782 B CN105367782 B CN 105367782B CN 201510731037 A CN201510731037 A CN 201510731037A CN 105367782 B CN105367782 B CN 105367782B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- -1 alkyl imidazole salt Chemical class 0.000 title claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 title abstract description 6
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 32
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- 230000004044 response Effects 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002253 acid Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000003513 alkali Substances 0.000 abstract description 13
- 238000005191 phase separation Methods 0.000 abstract description 9
- 230000008961 swelling Effects 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000005342 ion exchange Methods 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 125000003010 ionic group Chemical group 0.000 abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 239000004721 Polyphenylene oxide Substances 0.000 description 19
- 229920000570 polyether Polymers 0.000 description 18
- 125000001174 sulfone group Chemical group 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000005266 casting Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical class CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 238000000235 small-angle X-ray scattering Methods 0.000 description 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 3
- BKFRZOZNMWIFLH-UHFFFAOYSA-N 1-decyl-2-methylimidazole Chemical class CCCCCCCCCCN1C=CN=C1C BKFRZOZNMWIFLH-UHFFFAOYSA-N 0.000 description 3
- 150000008614 2-methylimidazoles Chemical class 0.000 description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 2
- YFSQYUBYYKHCQV-UHFFFAOYSA-N 1-hexyl-2-methylimidazole Chemical class CCCCCCN1C=CN=C1C YFSQYUBYYKHCQV-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 description 1
- JKOTZBXSNOGCIF-UHFFFAOYSA-N 1-bromopentadecane Chemical compound CCCCCCCCCCCCCCCBr JKOTZBXSNOGCIF-UHFFFAOYSA-N 0.000 description 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- IKPSIIAXIDAQLG-UHFFFAOYSA-N 1-bromoundecane Chemical compound CCCCCCCCCCCBr IKPSIIAXIDAQLG-UHFFFAOYSA-N 0.000 description 1
- GMGLGUFSJCMZNT-UHFFFAOYSA-N BrCCCCCC.BrCCCCCC Chemical class BrCCCCCC.BrCCCCCC GMGLGUFSJCMZNT-UHFFFAOYSA-N 0.000 description 1
- UHIGAMJROXJLBQ-UHFFFAOYSA-N CCCCCCCCCCCCC.Br Chemical compound CCCCCCCCCCCCC.Br UHIGAMJROXJLBQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920002892 amber Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002579 anti-swelling effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BDDIUTHMWNWMRJ-UHFFFAOYSA-N octane;hydrobromide Chemical compound Br.CCCCCCCC BDDIUTHMWNWMRJ-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/126—Polyphenylene oxides modified by chemical after-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyethers (AREA)
Abstract
本发明涉及一种2‑甲基‑3‑烷基咪唑鎓盐聚芳醚梳型聚合物及其制备方法,属于梳型聚合物及其制备方法,以及由其制备的阴离子交换膜。梳型聚合物上连接的离子交换基团是C2和N3位取代的咪唑鎓盐,相比于传统的季铵盐和未取代的咪唑鎓盐,具有更好的耐碱稳定性;其次,本发明所述的连有不同长度的疏水侧链的咪唑鎓盐聚芳醚梳型聚合物,具有明显的亲水/疏水相分离结构,具有较高的离子传导率;再次,空间延展的憎水性长烷基侧链可将离子基团四周保护起来,进一步增强了阴离子交换膜的耐碱稳定性,还具有较低的吸水率,能够抑制膜的溶胀。
Description
技术领域
本发明涉及一种梳型聚合物及其制备方法,以及该梳型聚合物在阴离子交换膜技术领域的应用,其体涉及2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物及其制备方法及应用。
背景技术
高性能膜材料是解决能源、资源和环境等领域重大问题的核心材料之一,在氯碱、水处理、燃料电池和储能电池等行业有着极大的应用需求。目前以膜为代表的质子交换膜在这些行业使用最为广泛。虽然它们具有良好的热、化学和机械稳定性以及高的离子传导率,但由于要使用铂等贵金属催化剂来催化电化学反应等因素大大限制了酸性电化学器件的普及应用。不同于质子交换膜,以氢氧根离子作为离子传导载体的阴离子交换膜却具有独特的优势:由于在碱性介质中使用,催化剂的活性可大幅度提升,有望摆脱贵金属催化剂Pt的限制,使用稳定的廉价易得的镍、银等非贵金属催化剂,大幅度降低电化学器件的成本。
目前,商品化的阴离子交换膜主要应用于电渗析等电化学领域,大多通过辐射接枝制备,品种相对单一,还存在着离子传导率低、季铵基团在碱中易降解等问题,难以满足实际工况下长期稳定使用的要求。因此,寻求具有优良的传导性能兼具高的化学与机械稳定性的阴离子交换膜日益成为国内外科学家关注的热点。选用高耐热性和机械、化学稳定性的芳香族离聚物作为阴离子交换膜的骨架材料是这些研究的重点。以季铵盐为代表的阳离子基团以共价键的形式接枝到芳香族聚合物主链上,成为聚合物主链结合氢氧根等阴离子的位点。但综合来看,由于作为传导介质的OH-的离子淌度明显低于质子,阴离子交换膜的传导率不高,一般为10-3-10-2S/cm。为了提高传导率,势必需要在聚合物主链上接枝更多的离子基团,提高离子交换容量,以获得高的离子浓度。但是,随着离子化程度的提高,膜的亲水性增强,含水量和溶胀率大幅度增加,以至膜丧失了力学强度,甚至会在高温下溶解于水中。这种膜的离子传导性能与膜的力学强度相互制约、难以兼得的问题成为了芳香族离聚物型阴离子交换膜研发所面临的最大挑战。
Pan等(J.Pan,et al.,Energy Environ.Sci.,2014,7:354)在季铵化聚醚砜主链上引入疏水性柔性侧链,使聚合物内部形成微观相分离结构,有效地提高了离子传输效率和膜的抗溶胀性,其离子传导率可达10-1S/cm,接近Nafion膜中质子传导效率,并可在80℃纯水条件下长期稳定工作。Li等(N.Li,et al.,J.Am.Chem.Soc.,2013,135:10124)利用溴甲基化的聚苯醚,与带柔性烷基长侧链的叔胺反应,制备了季铵化的聚苯醚梳型共聚物。由于存在着亲水的骨架与疏水的长链之间的微相分离结构,梳型共聚物表现出了较低的吸水率(10-20%)和较高的离子传导率。特别是耐碱稳定性特别优异,在1M NaOH溶液中80℃下浸泡2000h后仍然保持较高的离子传导率。Xu等(S.Xu,et al.,J.Power Sources,2012,209:228)合成了一种含侧甲基苯基的双酚单体,并通过进一步的聚合、溴甲基化及季铵化反应,制备了侧链带有碱性侧基的聚合物膜材料。所制备的阴离子交换膜具有很好的机械性能和尺寸稳定性,在低离子交换容量(0.90mmol/g)时,氢氧根离子传导率也可达到0.031S cm-1(80℃),溶胀率仅为9.0%。可见:通过对聚合物分子结构的合理设计,实现对聚合物微观相分离结构的有效调控,是提高离子传输效率和增强膜的稳定性的有效手段。
不过,上述实例中季铵根阳离子在高温碱性条件下易受OH-的亲核进攻,发生重排或降解,使聚合物链失去阳离子基团,损失电荷。具有平面五元环结构,并存在离域π键的咪唑鎓阳离子基团成为研究者寄予厚望的季铵基团替代者。虽然早期的一些研究者认为咪唑鎓阳离子在受到OH-进攻时可以将离子有效分散,以减弱降解趋势,在NaOH或KOH里具有良好的稳定性。但近期一些报道则指出:咪唑阳离子C2位上的H具有弱酸性,容易受到OH-的进攻而开环,并失去离子交换能力。如果能够将咪唑鎓阳离子C2位上的H加以取代,则有可能实现其耐碱性的提高。再结合对聚合物链结构和微观相分离的调控,有望制备出一种兼有优良的传导性能和高的化学与机械稳定性的阴离子交换膜。
发明内容
本发明提供一种2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物及其制备与应用,以解决现有的阴离子交换膜常用季铵基团的耐碱性差和离子传导率低的问题。
本发明提供一种2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物,所述聚芳醚梳型聚合物具有式I所示的结构:
其中,n为聚合度,1≤n≤400;m为0到15的整数;R1为CH3或
Ar1选自式1~式7所示的基团中的一种或多种:
本发明还提供了一种式I所示2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物的制备方法,该方法包括以下步骤:
(1)溴甲基化:将四甲基联苯二酚型聚芳醚溶解在极性溶剂中,加入N-溴代琥珀酰亚胺和过氧化苯甲酰,加热反应,冷却后出料于丙酮中,粉碎、过滤、洗涤、干燥,得到溴甲基化聚芳醚;
(2)1-烷基-2-甲基咪唑的制备:将2-甲基咪唑、溴代烷烃与缚酸剂溶于极性溶剂中,加热反应,冷却至室温,过滤掉沉淀,旋蒸出大量溶剂,得到油状粗产品,再将其溶于二氯甲烷,水洗四次,分液,用无水硫酸镁干燥,过滤制得;
(3)将步骤(1)制得的溴甲基化聚芳醚与步骤(2)制得的1-烷基-2-甲基咪唑溶解于极性溶剂中,加热反应,冷却后出料于丙酮中,粉碎、过滤、洗涤、干燥,制得溴型2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物。
本发明所述步骤(1)中所述四甲基联苯二酚型聚芳醚具有式II所示结构:
其中,n为聚合度,1≤n≤400;
Ar2具有式8~式14所示的基团中的一种或多种:
本发明所述步骤(1)所述极性溶剂为氯仿、1,1,2,2-四氯乙烷、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、环丁砜或二甲基亚砜中的一种或两种混合溶剂,优选为氯仿和1,1,2,2-四氯乙烷。
所用四甲基联苯二酚型聚芳醚、N-溴代琥珀酰亚胺和过氧化苯甲酰的摩尔比为1:(1~4):(0.1~0.4)。所制备的溴甲基化聚芳醚的溴化度优选为1.0~2.0。
所述加热反应的优选条件是70~85℃反应12~48h。
优选地,此加热反应在惰性气氛保护下进行。
步骤(2)所述溴代烷烃可以包含一切链长的溴代烷烃,从原料易得性的角度考虑,所述溴代烷烃可以为溴代乙烷、溴代丙烷、溴代正丁烷、溴代正戊烷、溴代正己烷、溴代正庚烷、溴代正辛烷、溴代正壬烷、溴代正癸烷、溴代十一烷、溴代十二烷、溴代十三烷、溴代十四烷、溴代十五烷、溴代十六烷。
所述极性溶剂为乙腈、氯仿、1,1,2,2-四氯乙烷、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲基亚砜中的一种或两种,优选为乙腈。
所述缚酸剂没有特别地限定,可以为本领域的常规选择,本发明中优选为氢氧化钠、氢化钠或碳酸钾。
所述加热反应的优选条件是60~80℃反应6~12h。优选地,此加热反应在惰性气氛保护下进行。
步骤(3)所用溴甲基化聚芳醚与1-烷基-2-甲基咪唑的摩尔比由溴甲基化聚芳醚的溴化度确定,采用等摩尔比投料。
所述极性溶剂为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、环丁砜或二甲基亚砜中的一种或两种混合溶剂,优选为N-甲基吡咯烷酮或二甲基亚砜。
所述加热反应的优选条件是25~70℃反应8~24h。优选地,此加热反应在惰性气氛保护下进行。
本发明还提供了一种溴型阴离子交换膜,由上述式I所示溴型的2-甲基咪唑鎓盐聚芳醚梳型聚合物制备而成。本发明对阴离子交换膜的制备方法没有特别地限定,可使用含有式I所示的2-甲基咪唑鎓盐聚芳醚梳型聚合物和有机溶剂的铸膜液按照本领域技术人员所熟知的常规的流延或涂覆的方法制备。所述铸膜液中2-甲基咪唑鎓盐聚芳醚梳型聚合物的质量浓度为5~20%,优选为8~12%。所述有机溶剂可以为N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、环丁砜或二甲基亚砜中的一种或两种。
尽管采用上述方法可以制备得到阴离子交换膜,为了使离子基团完全转化为OH-,本发明还提供了一种氢氧根型阴离子交换膜,由上述溴型阴离子交换膜在浓度为0.1~1mol/L的氢氧化钠的溶液中浸泡12~48h。
上述氢氧根型阴离子交换膜用作碱性聚合物电解质燃料电池中的碱性阴离子交换膜使用。
本发明的发明人经过深入研究发现,一方面,本发明所述的,连有不同长度的疏水侧链的咪唑鎓盐聚芳醚,呈现梳型结构,可实现对聚合物亲水/疏水相分离结构的有效调控,构筑高效的离子传输通道,提高OH-传输效率,得到尽可能高的离子传导率;另一方面,空间延展的憎水性长烷基侧链和C2位上的甲基可将离子基团四周保护起来,有效降低了OH-对荷电咪唑鎓阳离子的进攻,增强了阴离子交换膜的耐碱稳定性。作为兼有良好的离子传导率和耐碱稳定性的阴离子交换膜在碱性聚合物电解质燃料电池具有广阔的应用前景。
附图说明
图1为三种2-甲基-3-烷基咪唑鎓盐聚芳醚砜聚合物的核磁谱图。
图2为三种2-甲基-3-烷基咪唑鎓盐聚芳醚砜聚合物的的小角X光散射曲线。
图3为三种2-甲基-3-烷基咪唑鎓盐聚芳醚砜阴离子交换膜的传导率随在1mol/L氢氧化钠溶液中浸泡时间的变化情况。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,并不用于限制本发明。
实施例1:2-甲基-3-己基咪唑鎓盐聚芳醚砜梳型聚合物及其制备方法
(1)溴甲基化聚芳醚砜的制备:将15g四甲基联苯二酚型聚芳醚砜溶于200mL氯仿中,加入到500mL的通入N2保护的三口烧瓶中,机械搅拌下加热到70℃。将11.75g N-溴代琥珀酰亚胺和1.6g过氧化苯甲酰分两次加入到反应体系中。持续反应24h,冷却后出料于丙酮中。将条状物用高速搅碎机粉碎,再用蒸馏水煮洗聚合物、过滤,重复6次后,真空烘箱中烘干制得。
核磁共振谱图中4.5ppm处的峰对应于苄基溴碳上的氢(Ar-CH2-Br),2.2ppm处的峰对应于未参与溴甲基化反应的残余的甲基上的氢。利用这两处峰对应的积分面积之比,可计算出溴甲基化聚芳醚砜的溴代度为1.75。
(2)1-己基-2-甲基咪唑的制备:将2.46g 2-甲基咪唑、4.46g 1-溴己烷和1.8g氢氧化钠溶于70mL乙腈中,在60℃机械搅拌加热反应12h,持续通入N2保护。待反应结束,冷却至室温,过滤掉沉淀。用旋转蒸发仪除掉乙腈溶剂,得到油状物粗产品。将粗产品溶解在70mL二氯甲烷中,水洗四次,分液,用无水硫酸镁干燥48h,过滤制得。
利用核磁共振谱对所制得的1-己基-2-甲基咪唑进行结构测定,得到结果:1H-NMR(500MHz,DMSO-d6):δ7.01(d,1H),6.70(d,1H),3.85-3.82(t,2H),2.26(s,3H),1.65-1.60(p,2H),1.28-1.22(m,6H),0.87-0.82(m,3H)。
(3)2-甲基-3-己基咪唑鎓盐聚芳醚砜梳型聚合物的制备:将3g溴代度为1.75的溴甲基化聚芳醚砜完全溶解在30mL N-甲基吡咯烷酮中,再将1.73g 1-己基-2-甲基咪唑加入到反应液中,N2保护,机械搅拌,在60℃加热反应12h。冷却后出料于丙酮中,粉碎、过滤、水洗5次、干燥,制得溴型2-甲基-3-己基咪唑鎓盐聚芳醚砜梳型聚合物(ImPAES-C6)。
图1所示ImPAES-C6的核磁共振谱图中,0.8~2.1ppm和3.9ppm处的峰对应于接枝的咪唑环上的烷基链上的氢,由此证明2-甲基-3-己基咪唑鎓基团的成功引入。通过计算核磁谱图中残余的苄基溴上的氢,计算出反应转化率为74%。利用扫描示差量热仪测得ImPAES-C6的玻璃化转变温度为200℃。图2中给出了ImPAES-C6的小角X射线散射曲线,在散射矢量(q)为3.8nm-1处出现散射峰,证明该聚合物存在着亲水/疏水相分离结构,利用公式d=2π/q可计算出离子簇之间的距离为1.65nm。
实施例2:2-甲基-3-癸基咪唑鎓盐聚芳醚砜梳型聚合物及其制备方法
(1)溴甲基化聚芳醚砜的制备:同实施例1。
(2)1-癸基-2-甲基咪唑的制备:将2.46g 2-甲基咪唑、5.97g 1-溴癸烷和1.8g氢氧化钠溶于70mL乙腈中,在60℃机械搅拌加热反应12h,持续通入N2保护。待反应结束,冷却至室温,过滤掉沉淀。用旋转蒸发仪除掉乙腈溶剂,得到油状物粗产品。将粗产品溶解在70mL二氯甲烷中,水洗四次,分液,用无水硫酸镁干燥48h,过滤制得。
利用核磁共振谱对所制得的1-癸基-2-甲基咪唑进行结构测定,得到结果:1H-NMR(500MHz,DMSO-d6):7.01(d,1H),6.70(d,1H),3.84-3.82(t,2H),2.26(S,3H),1.66-1.60(p,2H),1.29-1.20(m,14H),0.88-0.85(m,3H)。
(3)2-甲基-3-癸基咪唑鎓盐聚芳醚砜梳型聚合物的制备:将3g溴代度为1.75的溴甲基化聚芳醚砜完全溶解在30mL N-甲基吡咯烷酮中,再将2.33g 1-癸基-2-甲基咪唑加入到反应液中,N2保护,机械搅拌,在60℃加热反应12h。冷却后出料于丙酮中,粉碎、过滤、水洗5次、干燥,制得溴型2-甲基-3-癸基咪唑鎓盐聚芳醚砜梳型聚合物(ImPAES-C10)。
图1所示核磁共振谱图中,0.8~2.1ppm和3.9ppm处的峰对应于接枝的咪唑环上的烷基链上的氢,由此证明2-甲基-3-癸基咪唑鎓基团的成功引入。通过计算核磁谱图中残余的苄基溴位的氢,计算出反应转化率同样为74%。利用扫描示差量热仪测得ImPAES-C10的玻璃化转变温度为182℃。图2中给出了ImPAES-C10的小角X射线散射曲线,在散射矢量(q)为2.4nm-1处出现明显地散射峰,证明该聚合物存在着明显地亲水/疏水相分离结构,利用公式d=2π/q可计算出离子簇之间的距离为2.62nm。
实施例3:二甲基咪唑鎓盐聚芳醚砜聚合物的制备
将3g溴代度为1.75的溴甲基化聚芳醚砜完全溶解在30mL N-甲基吡咯烷酮中,再将1.01g 1,2-二甲基咪唑加入到反应液中,N2保护,机械搅拌,在60℃加热反应12h。冷却后出料于丙酮中,粉碎、过滤、水洗5次、干燥,制得溴型二甲基咪唑鎓盐聚芳醚砜聚合物(ImPAES-C1)。
图1所示核磁共振谱图中,0.8ppm处的峰对应于接枝的咪唑环的N3位甲基上的氢,由此证明二甲基咪唑鎓基团的成功引入。通过计算核磁谱图中残余的苄基溴位的氢,计算出反应转化率同样为74%。利用扫描示差量热仪测得ImPAES-C1的玻璃化转变温度为265℃。图2中给出了ImPAES-C1的小角X射线散射曲线,没有散射峰的存在。由于N3位烷基长度过短,该聚合物不存在明显的亲水/疏水相分离结构。
实施例4:2-甲基-3-己基咪唑鎓盐聚芳醚砜阴离子交换膜
将0.8g干燥的ImPAES-C6溶解于10mL N-甲基吡咯烷酮中,配置成均匀铸膜液。将上述铸膜液均匀涂敷在洁净的水平玻璃板上,在60℃放置24h以挥发尽溶剂。将玻璃板浸泡在水中脱模。并将脱下的成型膜在1mol/L的氢氧化钠溶液中浸泡12h,去离子水冲洗3次,制得氢氧根型ImPAES-C6阴离子交换膜。
ImPAES-C6膜的离子交换容量为1.95meq/g,在30℃下的吸水率为16.54%,溶胀率为9.35%,离子传导率为18.2S/cm;在60℃下的吸水率为90.52%,溶胀率为27.44%,离子传导率为32.5S/cm。在室温下将此膜浸泡在1mol/L的氢氧化钠溶液中跟踪室温传导率的变化情况,如图3所示,170h后传导率下降仅5%,表明该膜具有很好的耐碱性,在碱性聚合物电解质燃料电池中作为阴离子交换膜使用具有良好的应用前景。
实施例5:2-甲基-3-癸基咪唑鎓盐聚芳醚砜阴离子交换膜的制备
将0.8g干燥的ImPAES-C10溶解于10mL N-甲基吡咯烷酮中,配置成均匀铸膜液。将上述铸膜液均匀涂敷在洁净的水平玻璃板上,在60℃放置24h以挥发尽溶剂。将玻璃板浸泡在水中脱模。并将脱下的成型膜在1mol/L的氢氧化钠溶液中浸泡12h,去离子水冲洗3次,制得氢氧根型ImPAES-C10阴离子交换膜。
ImPAES-C10膜的离子交换容量为1.73meq/g,在30℃下的吸水率为11.96%,溶胀率为6.93%,离子传导率为7.6mS/cm;在60℃下的吸水率为15.66%,溶胀率为17.82%,离子传导率为12.0mS/cm。在室温下将此膜浸泡在1mol/L的氢氧化钠溶液中跟踪室温传导率的变化情况,如图3所示,170h后传导率下降仅4%,表明该膜具有很好的耐碱性,在碱性聚合物电解质燃料电池中作为阴离子交换膜使用具有良好的应用前景。
实施例6:二甲基咪唑鎓盐聚芳醚砜阴离子交换膜的制备
将0.8g干燥的ImPAES-C1溶解于10mL N-甲基吡咯烷酮中,配置成均匀铸膜液。将上述铸膜液均匀涂敷在洁净的水平玻璃板上,在60℃放置24h以挥发尽溶剂。将玻璃板浸泡在水中脱模。并将脱下的成型膜在1mol/L的氢氧化钠溶液中浸泡12h,去离子水冲洗3次,制得氢氧根型ImPAES-C1阴离子交换膜。
ImPAES-C1膜的离子交换容量为2.09meq/g,在30℃下的吸水率为38.20%,溶胀率为16.19%,离子传导率为12.8mS/cm;在60℃下的吸水率为231.37%,溶胀率为55.04%,离子传导率为22.4mS/cm。在室温下将此膜浸泡在1mol/L的氢氧化钠溶液中跟踪室温传导率的变化情况,如图3所示,170h后传导率下降9%,表明该膜具有很好的耐碱性,在碱性聚合物电解质燃料电池中作为阴离子交换膜使用具有良好的应用前景。
以上详细描述了本发明的优选实施方式,但是,本发明并不限于上述实施方式中的具体细节,在本发明的技术构思范围内,可以对本发明的技术方案进行多种简单变型,这些简单变型均属于本发明的保护范围。
Claims (4)
1.一种2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物,其特征在于,所述聚芳醚梳型聚合物具有式I所示的结构:
其中,n为聚合度,1≤n≤400;m为5到15的整数;R1为CH3或Ar1具有式1~式7所示的基团中的一种或多种:
2.一种2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物的制备方法,该方法具有以下步骤:
(1)溴甲基化:将四甲基联苯二酚型聚芳醚溶解在极性溶剂中,加入N-溴代琥珀酰亚胺和过氧化苯甲酰,加热反应,冷却后出料于丙酮中,粉碎、过滤、洗涤、干燥,得到溴甲基化聚芳醚;
(2)1-烷基-2-甲基咪唑的制备:将2-甲基咪唑、溴代烷烃与缚酸剂溶于极性溶剂中,加热反应,冷却至室温,过滤掉沉淀,旋蒸出大量溶剂,得到油状粗产品, 再将其溶于二氯甲烷,水洗四次,分液,用无水硫酸镁干燥,过滤制得;
(3)将步骤(1)制得的溴甲基化聚芳醚与步骤(2)制得的1-烷基-2-甲基咪唑溶解于极性溶剂中,加热反应,冷却后出料于丙酮中,粉碎、过滤、洗涤、干燥,制得溴型2-甲基-3-烷基咪唑鎓盐聚芳醚梳型聚合物。
3.一种阴离子交换膜,其特征在于,由权利要求1所述的任一种聚芳醚梳型聚合物制备而成。
4.由权利要求3所述的阴离子交换膜在制备碱性燃料电池的碱性阴离子交换膜中的应用。
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