CN114763412A - High-efficiency preparation method of phosphonate polymer and application of phosphonate polymer in high-temperature fuel cell - Google Patents
High-efficiency preparation method of phosphonate polymer and application of phosphonate polymer in high-temperature fuel cell Download PDFInfo
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- CN114763412A CN114763412A CN202110000812.6A CN202110000812A CN114763412A CN 114763412 A CN114763412 A CN 114763412A CN 202110000812 A CN202110000812 A CN 202110000812A CN 114763412 A CN114763412 A CN 114763412A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 110
- 239000000446 fuel Substances 0.000 title claims abstract description 41
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 7
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 230000001699 photocatalysis Effects 0.000 claims abstract description 3
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000002904 solvent Substances 0.000 claims description 57
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- 238000001035 drying Methods 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 49
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 37
- 210000004027 cell Anatomy 0.000 claims description 35
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 23
- 238000001704 evaporation Methods 0.000 claims description 23
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 22
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 16
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000004693 Polybenzimidazole Substances 0.000 claims description 10
- 229920002480 polybenzimidazole Polymers 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 210000000170 cell membrane Anatomy 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- 125000004424 polypyridyl Polymers 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052717 sulfur Chemical group 0.000 claims description 2
- 239000011593 sulfur Chemical group 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims 2
- 229920006380 polyphenylene oxide Polymers 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 238000007385 chemical modification Methods 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000026731 phosphorylation Effects 0.000 abstract description 2
- 238000006366 phosphorylation reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229920000554 ionomer Polymers 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 108
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 42
- 229910000027 potassium carbonate Inorganic materials 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 17
- 239000012467 final product Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 229920002492 poly(sulfone) Polymers 0.000 description 10
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000005286 illumination Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 Polytetrafluoroethylene Polymers 0.000 description 6
- 125000001246 bromo group Chemical group Br* 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 238000005954 phosphonylation reaction Methods 0.000 description 5
- 229920006393 polyether sulfone Polymers 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- XHWWJYJRLKMVDZ-UHFFFAOYSA-N 3-(2-phenylphenyl)benzene-1,2-diol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)C=2C=CC=CC=2)=C1O XHWWJYJRLKMVDZ-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
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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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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]
-
- 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
- H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
-
- 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
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Medicinal Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to a method for simply, mildly and efficiently synthesizing a phosphonated polymer by surface light source catalysis, and application of the phosphonated polymer in a high-temperature fuel cell, belonging to the technical fields of ion exchange membrane material preparation processes and fuel cells. The invention modifies polyaryl ether sulfone polymers by an Arbuzov reaction initiated by mild surface light source photocatalysis, solves the problems of low molecular weight, low ion exchange capacity and difficult film formation in the synthesis process of the existing phosphonated polymers, and uses the obtained phosphonated polymers as proton exchange membranes and ionomers in catalyst layers in high-temperature fuel cells. The method for initiating the phosphorylation by the surface light source has the advantages of mild and simple preparation conditions, high polymer molecular weight, good film forming property, and stable conductivity and output power of corresponding film materials and ionomers in a high-temperature fuel cell.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, relates to the field of preparation of fuel cell application materials, and particularly relates to a synthetic phosphorylated high polymer and an efficient preparation method thereof.
Technical Field
With the increasing tension of fossil energy and the problem of emission of various pollutants, hydrogen energy has received worldwide attention as a final solution to energy and environmental problems. The global hydrogen energy ratio reaches 10 percent, and the output value reaches 12 trillion yuan. The key point of hydrogen energy utilization depends on fuel cell technology, and the fuel cell as an energy technology has the advantages of energy safety, safe supply, environmental friendliness and the like.
The proton exchange membrane is a core component of the fuel cell, and the proton exchange membrane in the high-efficiency fuel cell has the following characteristics: high proton conductivity, low electron conductivity, low fuel and oxidant permeability, low water conductivity, oxidation and hydrolytic stability, good mechanical properties in dry/wet state, can be used to make membrane cell assembled devices, and is low cost. The Nafion membrane produced by DuPont in the united states is a mainstream proton exchange membrane product at present, has the advantages of good chemical stability, high proton conductivity under high humidity and the like, and has the fatal defects of high price, low proton conductivity under low humidity, low mechanical strength under high temperature and the like. The operating temperature of the current commercialized perfluorinated sulfonic acid proton exchange membrane (such as Nafion) battery is lower (less than or equal to 80 ℃), so that the PEMFC catalyst is easy to be poisoned by CO, the requirement on the purity of hydrogen is extremely high (the requirement on the purity is 99.9999%), the use cost is high, and simultaneously, the water management of a fuel cell stack is complex, and the efficiency of the fuel cell is reduced. Compared with a medium-low temperature fuel cell, the high-temperature fuel cell (HT-PEMFC) has higher electrochemical reaction activity and higher CO tolerance (the concentration can reach 3 percent), so that methanol, natural gas and other reformed hydrogen or coal chemical byproduct hydrogen and the like can be used as fuels, and the hydrogen purification cost is greatly reduced. In addition, simple water thermal management fundamentally simplifies the operation and management of the fuel cell system. Therefore, HT-PEMFCs are considered to be the next generation of revolutionary fuel cell technology. The high-temperature proton exchange membrane electrode is a key material of the high-temperature fuel cell technology. The currently used membrane and catalyst layer binders are Polybenzimidazole (PBI) materials, and the proton conductivity is obtained by doping phosphoric acid, and good initial performance and stability are obtained, for example, the leiqing peak topic group (Fuel Cells (2014)14 (1): 7-15) compares the single cell stability of PBI with different molecular weights, and the stable operation exceeds 1600 h. However, in the practical application process, the PBI doped phosphoric acid as the binder of the ionic membrane and the catalytic layer faces the problem that the phosphoric acid loses with the water generated by the cathode and the start-stop condensed water (j. mater.chem. a (2013) 1: 2578), because the calculated value of the intermolecular interaction energy of the weak base group imidazole and the phosphoric acid in the PBI is 17.4 kcal/mol, and only phosphoric acid is compared with H2The functional energy of O (12.6kcal/mol) is greater than 4.8kcal/mol, and the free phosphoric acid has weaker interaction with the membrane, which causes the proton conductivity of the membrane electrode to be reduced and the performance of the cell to be degraded. Another commonly used high temperature fuel cell binder material is Polytetrafluoroethylene (PTFE), which has hydrophobic properties that reduce The potential for flooding of The catalytic layer, but with increasing PTFE content of The catalytic layer, leads to increased internal resistance and reduced Electrochemical performance of The overall fuel cell (Journal of The Electrochemical Society (2011)158 (6): B675-B681). Therefore, how to reduce phosphoric acid loss from the catalytic layer perspective and maintain ion transport properties is critical to the improvement of high temperature fuel cell stability. Based on the above problems, the most powerful method for overcoming this drawback is to introduce phosphate groups into the polymer compound by covalent bonds. Macromolecules containing phosphonic acid groups have attracted interest to researchers (Journal of Membrane Science (2006) 285: 206- & 213; Journal of Membrane Science (2020) 605: 11807). The polymer has high temperature resistance and good oxidation resistance, has good proton conductivity under high temperature and dry/wet states, and has certain effect when being used as a proton exchange membrane and catalyst layer binder in the field of high-temperature proton exchange membrane fuel cells.
There are generally two methods for preparing phosphorylated polymers, one is direct nucleophilic polycondensation of a phosphorylated dihalo monomer with a non-phosphorylated diphenol monomer to obtain (J.Mater.chem. (2013) 1: 1457-1464, chem.Mater. (2011) 24: 115-122, Asia Pac.J.chem.Eng. (2010) 5: 249-255), but the phosphorylated polymers synthesized by the method have low molecular weight and poor mechanical and film-forming properties due to solubility problems. The second method is to bromize or lithiate the existing polymer, and then to perform phosphonylation by a mercury lamp or heating method, etc., the molecular weight of the obtained post-phosphonylation polymer is reduced rapidly, the polymer is degraded due to severe reaction conditions (Macromolecules (2010) 43: 3634-3651), and the molecular weight of Macromolecules (2002) 35: 3484-3489).
Disclosure of Invention
Based on the above difficulties in synthesis of the phosphonylation polymer and the key problems existing in the field of high-temperature proton exchange membrane fuel cells, the invention aims to use a high-efficiency and mild surface light source (250-455nm) to catalyze the Arbuzov reaction of the halogenated polymer to efficiently synthesize a series of polymers with high molecular weight and high phosphonylation degree containing phosphonic acid groups, and the polymers are used as a catalyst layer binder to be applied in the field of high-temperature proton exchange membrane fuel cells.
In order to achieve the purpose, the invention discloses the following technical contents:
a novel polymer containing phosphonic acid groups and salts thereof has a structure shown in formula (I) or (II):
wherein, (I) (II) X ═ oxygen or sulfur; m is more than 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m + n is equal to 1;
the invention further discloses a method for efficiently preparing polymers (I) and (II) containing phosphonic acid groups by surface light source catalysis, which is characterized by comprising the following steps:
(1) photocatalytic Arbuzov reaction: under the atmosphere of nitrogen (99.999 percent, the flow rate: 10-15mL/min), adding brominated high molecular polymer into a quartz four-mouth bottle with magnetic stirring, then adding 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 50-100 ℃ to completely dissolve the raw materials, adding triethyl phosphite by using a constant pressure dropping funnel, carrying out photocatalytic reaction by using an LED surface light source irradiator with 200-455nm when the triethyl phosphite is completely dissolved into a clear transparent solution, distilling a sample under reduced pressure to remove the solvent after the reaction is carried out for 0-10h, and then using chloroform (CHCl)3) Dissolving, dripping the mixture into isopropanol to separate out a product, washing the product for multiple times by using the isopropanol to remove low molecular organic matters in the reaction, filtering the product, and drying the product at 120 ℃ to obtain a phosphonate polymer;
(2) acidifying: the phosphonate polymer was dissolved in CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the mixture is completely dissolved into clear and transparent solution, under the condition of ice water bath at 0 ℃,slowly dripping trimethyl bromosilane by using a constant-pressure dropping funnel, heating and stirring at 20-80 ℃ for 10-30h when dripping is carried out till no precipitate is separated out, after the reaction is finished, decompressing and evaporating the solvent by using a water pump to obtain a solid residue, adding methanol into the solid residue, stirring and washing at room temperature for 24h, evaporating the methanol, soaking and washing the obtained product by using deionized water for multiple times so as to remove the solvent and inorganic salt contained in the polymer, and drying to obtain a gray block solid, namely the phosphonated polymer;
the invention further discloses an application of the phosphonic acid group polymer as a high-temperature proton exchange membrane and a catalyst layer binder in a high-temperature fuel cell, wherein the phosphonic acid group polymer comprises the following components in percentage by weight:
(1) high temperature proton exchange membrane: dissolving a phosphonated polymer in a common organic solvent, such as chloroform, dimethyl sulfoxide, dimethylacetamide, N-methyl pyrrolidone, dimethylformamide and the like to obtain a casting solution with the solid content of 2-25%, then scraping or brushing the casting solution on a glass plate, and completely drying the solvent to obtain an ion exchange membrane;
(2) step 1, mixing and dissolving a phosphonated polymer and a commercial fuel cell Pt/C catalyst in a mixed solution of isopropanol, N-propanol, N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide and water, and stirring and ultrasonically to completely dissolve the phosphonated polymer and uniformly disperse the catalyst to obtain uniform and non-precipitated slurry, wherein the mass ratio of the phosphonated polymer to the catalyst is 1: 1-1: 10;
the experimental result shows that the concentration is 200sccm H2/O2At 160 ℃, phosphonic acid polymer is used as a bonding agent, a commercial PBI ionic membrane is soaked in 85% phosphoric acid to be used as a proton exchange membrane, and good initial performance is realized in a high-temperature fuel cellCan, and can stably operate for a long time.
Drawings
FIG. 1 is a graph of proton conductivity change in various phosphonylated polymer membranes at 100% humidity and temperatures ranging from 20 ℃ to 80 ℃;
FIG. 2 is a graph of proton conductivity for various phosphonated phosphorylated polymers at a temperature in the range of from 20 to 180 ℃ with humidity of 0;
FIG. 3 is a schematic diagram of a high-temperature fuel cell and stack;
FIG. 4 shows the result of a binder high temperature fuel cell durability test using the phosphonated polymer P-PPSU.
Detailed Description
For the sake of simplicity and clarity, descriptions of well-known techniques are omitted below where appropriate so as not to obscure the description of the present solution with unnecessary detail. The present invention is further illustrated by the following examples, which are only used as representative examples to clearly and completely explain the present invention, but the scope of the present invention is not limited by these examples. Wherein the difluorodiphenol, the N-bromosuccinimide, the chloroform and the Na2CO3Anhydrous MgSO (MgSO)4Materials such as methylene chloride, biphenol, triethyl phosphite, bisphenol A, toluene, and the like are commercially available.
Example 1:
preparation of phosphonated Polytriphenylsulfone (P-PTPSU):
(1) preparation of bromodifluorodiphenyl sulfone (DBDFDPS) monomer:
25.41g of 4, 4' -difluorodiphenyl sulfone (DFDPS) were mixed with 150mL of concentrated H at room temperature under a nitrogen atmosphere2SO4Mix and stir to homogeneous and add 14.13g N-bromosuccinimide (NBS) slowly to the reaction in three portions (within 15 min). The mixture is stirred at room temperature for 8h, after completion of the reaction mixture is poured slowly and under stirring into ice-water (about 500g), allowed to settle overnight and filtered, the filter cake is washed three times with water and then with waterDissolving in chloroform, sequentially adding water and saturated Na2CO3Washing the solution and saturated NaCl solution 3-4 times respectively, and finally using anhydrous MgSO4Drying overnight, filtering off MgSO4Then removing the solvent in vacuum to obtain a white solid crude product, and recrystallizing with dichloromethane to obtain 38.09g of white crystals with m.p.158-160 ℃ and the yield of 92%.
(2) Preparation of bromo PTPSU (BrPTPSU):
pretreating the raw materials before the reaction, drying DBDFDPS and tribP in a vacuum oven at 55 ℃ for 12h, and K2CO3Drying in a vacuum oven at 120 deg.C for 12 hr. 4.14g (10mmol) of DBDFDPS and 2.62g (10mmol) of terphenyl-diol (tribP) were charged in equimolar ratio under nitrogen (99.999%, flow rate: 10-15mL/min) into a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air-guide tube, and then 36.5mL of dimethylacetamide (DMAc), 17.5mL of toluene (Tol), 4.69g (11.5mmol) of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the oil bath temperature) for continuous reaction, the reaction is continued for 4 hours at the temperature to obtain a dark brown viscous solution, the reaction is stopped, and the final product is slowly poured into 1L of distilled water to obtain a white strip-shaped polymer. The polymer was boiled in water at 105 c (hot plate temperature) for 12h 3-4 times to remove the solvent and inorganic salts contained in the polymer and to obtain pure white polymer in the form of a strand 6.3g with a Y of 94%. Intrinsic viscosity: 1.45 dL/g.
(3) Preparation of phosphorylated PTPSU:
under nitrogen (99.999%, flow rate): 10-15mL/min) is added into a quartz four-mouth bottle with magnetic stirring, then 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI) is added, and 80 ℃ (heating plate) is heated and stirred to completely dissolve the raw materials, 80mL of triethyl phosphite is added by a constant pressure dropping funnel, when the triethyl phosphite is completely dissolved into a clear transparent solution, a 365nm UVLED surface light source irradiator is used for carrying out illumination reaction, the sample is decompressed and distilled to remove the solvent, CHCl is used for removing the solvent3Dissolving, dripping into 20mL isopropanol, precipitating the product, washing with isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking the filter cake, drying in a common oven at 120 ℃ for 12h, and drying in a vacuum oven at 120 ℃ for 12 h.
(4) Preparation of P-PTPSU (acidification):
0.5g of the polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dripping 1mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when the bromotrimethylsilane is dripped till no precipitate is separated out, evaporating the solvent to dryness under reduced pressure by using a water pump after the reaction is finished to obtain solid residues, adding 5mL of methanol into the solid residues, stirring for 18 hours at room temperature, and evaporating the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvents and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.43g of a gray lumpy solid with Y86%. Intrinsic viscosity: 0.55 dL/g.
Example 2:
preparation of phosphonated polysulfone (P-PSU)
(1) Preparation of brominated PSU:
bromo difluoro diphenyl sulfone (DBDFDPS) monomer was prepared as in example 1. Pretreating the raw materials before the reaction, drying DBDFDPS and bisphenol A in a vacuum oven at 55 ℃ for 12h, and drying the dried product with the temperature of K2CO3Drying in a vacuum oven at 120 deg.C for 12 hr. 2.07g (5mmol) of DBDFDPS and 1.14g (5mmol) of bisphenol A (BPA) were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air duct under nitrogen (99.999%, flow rate: 10-15mL/min), to which 10.5mL of N, N-dimethylacetamide (DMAc), 5mL of toluene (Tol), 0.79g (5.75 mmol) of anhydrous potassium carbonate was then added. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the oil bath temperature) for continuous reaction, the reaction is continued for 6 hours at the temperature to obtain a dark brown viscous solution, the reaction is stopped, and the final product is slowly poured into 1L of distilled water to obtain a white strip-shaped polymer. The polymer was boiled in water for 12h at 105 c (heating plate temperature) 3-4 times to remove the solvent and inorganic salts contained in the polymer and finally to obtain pure white polymer in the form of strands 2.91g with Y97%. Intrinsic viscosity: 1.01 dL/g.
(2) Preparation of phosphorylated PSU:
adding 3g of brominated PSU into a quartz four-mouth bottle with magnetic stirring in the atmosphere of nitrogen (99.999 percent, flow rate: 10-15mL/min), then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, performing illumination reaction by using a 365nm LED surface light source irradiator when the triethyl phosphite is completely dissolved into a clear transparent solution, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping into 20mL isopropanol, precipitating, washing with isopropanol for 3 times to remove low molecular organic substances, filtering, and collecting filter cakeDrying in an oven at 120 ℃ for 12h, and drying in a vacuum oven at 120 ℃ for 12 h.
(3) Acidification of phosphorylated PSU (P-PSU):
0.5g of the phosphonylated PSU polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dripping 1mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when the bromotrimethylsilane is dripped till no precipitate is separated out, evaporating the solvent to dryness under reduced pressure by using a water pump after the reaction is finished to obtain solid residues, adding 5mL of methanol into the solid residues, stirring for 18 hours at room temperature, and evaporating the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvents and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.41g of a grey lumpy solid, Y ═ 82%. Intrinsic viscosity: 0.87 dL/g.
Example 3:
preparation of phosphonated polyethersulfone (P-PES):
(1) preparation of brominated PES:
pretreating the raw materials before starting the reaction, drying DBDFDPS and dihydroxy benzophenone in a vacuum oven at 55 ℃ for 12h, and drying the dried product with the temperature of K2CO3Drying in a vacuum oven at 120 deg.C for 12 h. 4.14g (10mmol) of DBDFDPS and 2.14g (10mmol) of dihydroxybenzophenone were added in equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, a bend, a stirring paddle and an air-guide tube under nitrogen (99.999%, flow rate: 10-15mL/min), to which was then added 21mL of LN, N-dimethylacetamide (DMAc), 10.5mL of toluene (Tol), 1.59g (11.5mmol) of anhydrous potassium carbonate. DMAc as solvent, anhydrous carbonPotassium is used as a catalyst, methylbenzene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (oil bath temperature), the methylbenzene is refluxed and separated for 12 hours, after water separation is finished, the methylbenzene in the system is removed through a water separator, the temperature is raised to 186 ℃ (oil bath temperature) for continuous reaction, the reaction is continued for 12 hours at the temperature to obtain a brown viscous solution, the reaction is stopped, and a final product is slowly poured into 1L of distilled water to obtain a brown strip-shaped polymer. Boiling in water at 105 deg.C (heating plate temperature) for 12h, 3-4 times to remove solvent and inorganic salts contained in the polymer, and obtaining 5.5g of brown yellow stripe polymer, wherein Y is 88%. Intrinsic viscosity: 0.75 dL/g.
(2) Preparation of phosphonated PES:
adding 3g of bromoPES into a quartz four-mouth bottle with magnetic stirring in the atmosphere of nitrogen (99.999 percent, flow rate: 10-15mL/min), then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, when the triethyl phosphite is completely dissolved into a clear transparent solution, carrying out illumination reaction by using a 365nm LED surface light source irradiator, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping the mixture into 20mL of isopropanol to separate out a product, washing the product with the isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking a filter cake, drying the filter cake in a common oven at 120 ℃ for 12 hours, and drying the filter cake in a vacuum oven at 120 ℃ for 12 hours.
(3) Acidification of phosphonated PES (P-PES):
0.5g of phosphonylated PES polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the intermediate solution is completely dissolved into clear transparent solution, under the condition of ice water bath at 0 ℃, dropwise adding trimethyl bromosilane 1 slowly by using a constant-pressure dropping funnelAnd mL, when dropwise adding till no precipitate is separated out, heating and stirring for 24h at 40 ℃ (a heating plate), after the reaction is finished, evaporating the solvent to dryness under reduced pressure by using a water pump to obtain a solid residue, adding 5mL of methanol into the solid residue, stirring for 18h at room temperature, and evaporating the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvents and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.36g of a grey lumpy solid, Y ═ 82%. Intrinsic viscosity: 0.66 dL/g.
Example 4:
preparation of phosphonated fluorination (P-6F-PSU):
(1) preparation of bromo-6F-PSU:
pretreating the raw materials before the reaction, drying DBDFDPS and hexafluorobisphenol A in a vacuum oven at 55 ℃ for 12h, and drying K2CO3Drying in a vacuum oven at 120 deg.C for 12 hr. 4.14g (10mmol) of DBDFDPS and 3.36g (10mmol) of hexafluorobisphenol A were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air guide tube under nitrogen (99.999%, flow rate: 10-15mL/min), and then 21mL of N, N-dimethylacetamide (DMAc), 10.5mL of toluene (Tol), 1.59g (11.5mmol) of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the temperature of an oil bath), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the temperature of the oil bath) for continuous reaction, the reaction is continued for 12 hours at the temperature to obtain a brown viscous solution, the reaction is stopped, and a final product is slowly poured into 1L of distilled water to obtain a light brown strip-shaped polymer. Boiling in water at 105 deg.C (heating plate temperature) for 12h, 3-4 times to remove solvent and inorganic salts contained in the polymer, and obtaining brown yellow stripe polymer 6.75g, Y being 90%. Intrinsic viscosity: 0.85 dL/g.
(2) Preparation of Phosphorylated 6F-PSU:
adding 3g of bromo-6F-PSU into a quartz four-mouth bottle with magnetic stirring in the atmosphere of nitrogen (99.999 percent, flow rate: 10-15mL/min), then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, performing illumination reaction by using a 365nm LED surface light source irradiator when the triethyl phosphite is completely dissolved into a clear transparent solution, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping into 20mL isopropanol, precipitating the product, washing with isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking the filter cake, drying in a common oven at 120 ℃ for 12h, and drying in a vacuum oven at 120 ℃ for 12 h.
(3) Preparation of phosphonated P-6F-PSU:
0.6g of the phosphonylated 6F-PSU polymer was dissolved in 5mL of CHCl under a nitrogen atmosphere (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dripping 1mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when the bromotrimethylsilane is dripped till no precipitate is separated out, evaporating the solvent to dryness under reduced pressure by using a water pump after the reaction is finished to obtain solid residues, adding 5mL of methanol into the solid residues, stirring for 18 hours at room temperature, and evaporating the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvents and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.42g of a grey lumpy solid with Y ═ 70%. Intrinsic viscosity: 0.57 dL/g.
Example 5:
preparation of phosphonated fluorination (P-6F-PSU-1):
(1) preparation of bromo-6F-PSU-1:
the raw materials are pretreated before the reaction is started, difluorodiphenol and bromohexafluorobisphenol A are placed in a vacuum oven at 55 ℃ for drying for 12h, K2CO3Drying in a vacuum oven at 120 deg.C for 12 h. 2.54g (10mmol) of difluorodiphenol and 4.92g (10mmol) of bromohexafluorobisphenol A were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, a bend, a stirring paddle and an air-guide tube under a nitrogen (99.999%, flow rate: 10-15mL/min), and then 21mL of N, N-dimethylacetamide (DMAc), 10.5mL of toluene (Tol), 1.59g (11.5mmol) of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the temperature of an oil bath), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the temperature of the oil bath) for continuous reaction, the reaction is continued for 12 hours at the temperature to obtain a brown viscous solution, the reaction is stopped, and a final product is slowly poured into 1L of distilled water to obtain a light brown strip-shaped polymer. Boiling in water at 105 deg.C (heating plate temperature) for 12h, 3-4 times to remove solvent and inorganic salts contained in the polymer, and obtaining brown yellow stripe polymer 6.23g with Y being 88%. Intrinsic viscosity: 0.66 dL/g.
(2) Preparation of Phosphorylated 6F-PSU-1:
adding 3g of bromo-6F-PSU-1 into a quartz four-mouth bottle with magnetic stirring under nitrogen (99.999% and flow rate of 10-15mL/min), adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 deg.C (heating plate) to completely dissolve the raw materials, adding 80mL of the solution by using a constant pressure dropping funnelTriethyl phosphite, when the triethyl phosphite is completely dissolved into clear transparent solution, performing illumination reaction by using a 365nm LED surface light source irradiator, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping into 20mL isopropanol, precipitating the product, washing with isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking the filter cake, drying in a common oven at 120 ℃ for 12h, and drying in a vacuum oven at 120 ℃ for 12 h.
(3) Preparation of phosphonated P-6F-PSU-1:
0.6g of the phosphonylated 6F-PSU-1 polymer was dissolved in 5mL of CHCl under a nitrogen atmosphere (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dripping 1.3mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice-water bath, heating and stirring for 24h at 40 ℃ (a heating plate) when the bromotrimethylsilane is dripped to just have no precipitate, evaporating the solvent to dryness under reduced pressure by using a water pump after the reaction is finished to obtain solid residue, adding 5mL of methanol into the solid residue, stirring for 18h at room temperature, and evaporating the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvent and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.35g of a lumpy solid, Y68%. Intrinsic viscosity: 0.71 dL/g.
Example 6:
preparation of phosphonated polypyridyl sulfone (P-PPySU):
(1) preparation of bromo-PPySU:
the raw materials are pretreated before the reaction is started, DBDFDPS and bipyridyl diphenol (BPyOH) are placed in a vacuum oven at 55 ℃ for drying for 12h, K2CO3Drying in a vacuum oven at 120 deg.C for 12 hr. Under the atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min), 4.14g of (A), (B), (C), (D), (E), (C), (D), (E), (D) and D)10mmol) of DBDFDPS and 1.88g (10mmol) of bipyridyldiphenol were charged in an equimolar ratio into a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air-guide, and then 21mL of N, N-dimethylacetamide (DMAc), 10.5mL of toluene (Tol), 1.59g (11.5mmol) of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the oil bath temperature) for continuous reaction, the reaction is continued for 4 hours at the temperature to obtain a dark brown viscous solution, the reaction is stopped, and the final product is slowly poured into 1L of distilled water to obtain a white strip-shaped polymer. The polymer was boiled in water for 12h at 105 c (heating plate temperature) 3-4 times to remove the solvent and inorganic salts contained in the polymer and finally to obtain 5.2g of pure white polymer in the form of a strand, Y being 87%. Intrinsic viscosity: 0.80 dL/g.
(2) Preparation of phosphorylated PPySU:
adding 3g of brominated high molecular polymer (DBDFDPS + BPyOH) into a quartz four-mouth bottle with magnetic stirring in the atmosphere of nitrogen (99.999 percent, flow rate: 10-15mL/min), then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, performing illumination reaction by using a 365nm UVLED surface light source irradiator when the triethyl phosphite is completely dissolved into a clear transparent solution, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping the mixture into 20mL of isopropanol to separate out a product, washing the product with the isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking a filter cake, drying the filter cake in a common oven at 120 ℃ for 12 hours, and drying the filter cake in a vacuum oven at 120 ℃ for 12 hours.
(3) Acidification, preparation of P-PPySU:
0.5g of polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the intermediate solution is completely dissolved into a clear transparent solution, slowly dropwise adding 1mL of trimethylbromosilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice-water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when dropwise adding is carried out until no precipitate is separated out, after the reaction is finished, evaporating the solvent by using a water pump under reduced pressure to obtain a solid residue, then adding 5mL of methanol into the solid residue, stirring for 18 hours at room temperature, and evaporating away the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvents and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.44g of a grey lumpy solid with Y88%. Intrinsic viscosity: 0.59 dL/g.
Example 7:
preparation of phosphonated polyaryl ether sulfones (P-PTBSU)
(1) Preparation of bromo PTBSU:
bromo difluoro diphenyl sulfone (DBDFDPS) monomer was prepared as in example 1. Pretreating the raw materials before the reaction, drying DBDFDPS and triphenyl ethane diphenol (PED) in a vacuum oven at 55 ℃ for 12h, and drying the dried product2CO3Drying in a vacuum oven at 120 deg.C for 12 h. 4.10g (10mmol) of DBDFDPS and 2.90g (10mmol) of PED were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a paddle and an air duct under nitrogen (99.999%, flow rate: 10-15mL/min), and then 20.5mL of N, N-dimethylacetamide (DMAc), 5mL of toluene (Tol), 1.0g of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after water separation is finished, the toluene in the system is removed through a water separator, and then the temperature is raised to 186 ℃ (the oil bath temperature is increasedTemperature) and continuously reacting for 6h at the temperature to obtain a dark brown viscous solution, stopping the reaction, and slowly pouring the final product into 1L of distilled water to obtain a white strip-shaped polymer. The polymer was boiled in water for 12h at 105 c (heating plate temperature) 3-4 times to remove the solvent and inorganic salts contained in the polymer and finally to obtain 5.2g of pure white polymer in the form of a strand, Y being 78%. Intrinsic viscosity: 0.80 dL/g.
(2) Preparation of phosphorylated PTBSU:
adding 3g of bromo-PASU into a quartz four-mouth bottle with magnetic stirring in the atmosphere of nitrogen (99.999 percent, flow rate: 10-15mL/min), then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, performing illumination reaction by using a 365nm LED surface light source irradiator when the triethyl phosphite is completely dissolved to be a clear transparent solution, decompressing and distilling a sample to remove the solvent, and using CHCl3Dissolving, dripping the mixture into 20mL of isopropanol to separate out a product, washing the product with the isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking a filter cake, drying the filter cake in a common oven at 120 ℃ for 12 hours, and drying the filter cake in a vacuum oven at 120 ℃ for 12 hours.
(3) Preparation of phosphorylated P-PTBSU:
0.5g of phosphorylated PASU polymer was dissolved in 5mL of CHCl under a nitrogen atmosphere (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dropwise adding 1mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice-water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when dropwise adding is carried out till no precipitate is separated out, after the reaction is finished, evaporating the solvent by using a water pump under reduced pressure to obtain solid residues, adding 5mL of methanol into the solid residues, stirring for 18 hours at room temperature, evaporating the methanol to obtain the solid residuesAnd (5) finishing the product. The resulting product was washed in 50mL of deionized water, heated (hotplate temperature) at 80 ℃ for 12h, boiled 3-4 times to remove the solvent and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to give 0.39g of a white lumpy solid with Y ═ 78%. Intrinsic viscosity: 0.68 dL/g.
Example 8
Preparation of phosphonated 8-fluorophenylsulfone (P-POFPSU)
(1) Preparation of bromo-POFPSU:
bromo difluoro diphenyl sulfone (DBDFDPS) monomer was prepared as in example 1. The raw materials are pretreated before the reaction is started, DBDFDPS and octafluorobiphenyl diphenol (OFBP) are placed in a vacuum oven at 55 ℃ for drying for 12h, K2CO3Drying in a vacuum oven at 120 deg.C for 12 hr. 4.10g (10mmol) of DBDFDPS and 3.30g (10mmol) of OFBP were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air guide tube under a nitrogen (99.999%, flow rate: 10-15mL/min) atmosphere, and then 20.5mL of N, N-dimethylacetamide (DMAc), 5mL of toluene (Tol), 1.0g of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the oil bath temperature) for continuous reaction, the reaction is continued for 6 hours at the temperature to obtain a dark brown viscous solution, the reaction is stopped, and the final product is slowly poured into 1L of distilled water to obtain a light yellow strip-shaped polymer. And heating at 105 ℃ for 12 hours (heating plate temperature), boiling in water for 3-4 times to remove the solvent and inorganic salts contained in the polymer, and finally obtaining 4.8g of light yellow stripe polymer, wherein Y is 69%. Characteristics ofViscosity: 0.97 dL/g.
(2) Preparation of phosphonated POFPSU:
under the atmosphere of nitrogen (99.999 percent, the flow rate: 10-15mL/min), adding 3g of bromo-POFS into a quartz four-mouth bottle with magnetic stirring, then adding 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 80 ℃ (heating plate) to completely dissolve the raw materials, adding 80mL of triethyl phosphite by using a constant-pressure dropping funnel, when the triethyl phosphite is completely dissolved into a clear transparent solution, carrying out illumination reaction by using a 365nm LED surface light source irradiator, distilling the sample under reduced pressure to remove the solvent, and using CHCl3Dissolving, dripping the mixture into 20mL of isopropanol to separate out a product, washing the product with the isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking a filter cake, drying the filter cake in a common oven at 120 ℃ for 12 hours, and drying the filter cake in a vacuum oven at 120 ℃ for 12 hours.
(3) Acidification of phosphorylated P-POFPSU:
0.5g of the phosphonylated POFS polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the intermediate solution is completely dissolved into a clear transparent solution, slowly dropwise adding 1mL of trimethylbromosilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice-water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when dropwise adding is carried out until no precipitate is separated out, after the reaction is finished, evaporating the solvent by using a water pump under reduced pressure to obtain a solid residue, then adding 5mL of methanol into the solid residue, stirring for 18 hours at room temperature, and evaporating away the methanol to obtain a final product. The resulting product was washed in 50mL of deionized water, heated (heat plate temperature) for 12h, boiled 3-4 times to remove the solvent and inorganic salts contained in the polymer, and dried under vacuum at 50 ℃ for 24h to yield a white, lumpy solid of 0.42g with Y being 84%. Intrinsic viscosity: 0.88 dL/g.
Example 9
Preparation of phosphonated polyphosphonoaryl ether sulfones (P-PPOPSU)
(1) Preparation of brominated PPOPSU:
bromo difluoro diphenyl sulfone (DBDFDPS) monomer was prepared as in example 1. Pretreating raw materials before reaction, drying DBDFDPS and triphenyl phosphono diphenol (TPO) in a vacuum oven at 55 ℃ for 12h, K2CO3Drying in a vacuum oven at 120 deg.C for 12 h. 4.10g (10mmol) of DBDFDPS and 3.10g (10mmol) of OFBP were charged in an equimolar ratio to a 100mL straight three-necked flask equipped with a water separator, a serpentine condenser, an elbow, a stirring paddle and an air guide tube under a nitrogen (99.999%, flow rate: 10-15mL/min) atmosphere, and then 20.5mL of N, N-dimethylacetamide (DMAc), 5mL of toluene (Tol), 1.0g of anhydrous potassium carbonate were added thereto. DMAc is used as a solvent, anhydrous potassium carbonate is used as a catalyst, toluene is used as a water separating agent, after the mixture is completely dissolved, the temperature is raised to 165 ℃ (the oil bath temperature), the toluene is refluxed and separated for 12 hours, after the water separation is finished, the toluene in the system is removed through a water separator, the temperature is raised to 186 ℃ (the oil bath temperature) for continuous reaction, the reaction is continued for 6 hours at the temperature to obtain a dark brown viscous solution, the reaction is stopped, and the final product is slowly poured into 1L of distilled water to obtain a white strip-shaped polymer. The polymer was boiled in water at 105 c (hot plate temperature) for 12h 3-4 times to remove the solvent and inorganic salts contained in the polymer and to obtain 3.5g of white polymer in the form of a strand, Y69%. Intrinsic viscosity: 0.51 dL/g.
(2) Preparation of phosphorylated PPOPSU:
under nitrogen (99.999%, flow rate: 10-15mL/min), 3g of bromo-PTPO was added to a quartz four-necked flask equipped with magnetic stirring, and then 120mL of 1, 3-dimethyl-2-imidazolidinone (DMI) was added thereto, and the mixture was heated and stirred at 80 ℃ (heating plate) to stir the originalDissolving the materials completely, adding 80mL triethyl phosphite with constant pressure dropping funnel, performing illumination reaction with (365nm) LED area light source irradiator when the materials are completely dissolved to be clear transparent solution, distilling the sample under reduced pressure to remove solvent, and using CHCl3Dissolving, dripping into 20mL isopropanol, precipitating the product, washing with isopropanol for 3 times to remove low molecular organic matters in the reaction, filtering, taking the filter cake, drying in a common oven at 120 ℃ for 12h, and drying in a vacuum oven at 120 ℃ for 12 h.
(3) Preparation of phosphorylated P-PPOPSU:
0.5g of phosphonylated PTPO polymer was dissolved in 5mL of CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the bromotrimethylsilane is completely dissolved into a clear transparent solution, slowly dripping 1mL of bromotrimethylsilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice water bath, heating and stirring for 24 hours at 40 ℃ (a heating plate) when the bromotrimethylsilane is dripped till no precipitate is separated out, evaporating the solvent to dryness under reduced pressure by using a water pump after the reaction is finished to obtain solid residues, adding 5mL of methanol into the solid residues, stirring for 18 hours at room temperature, and evaporating the methanol to obtain a final product. The product obtained is washed in 50mL of deionized water, heated (heating plate temperature) at 80 ℃ and boiled in water for 12h, 3-4 times in order to remove the solvent and the inorganic salts contained in the polymer, dried under vacuum at 50 ℃ for 24h, and finally obtained as a white massive solid with intrinsic viscosity: 0.40 dL/g.
Example 10:
preparing a phosphonated proton exchange membrane, weighing 5g of the phosphonated polymer prepared in example 14 respectively, dissolving in 50ml of dimethylacetamide under magnetic stirring to form a uniform and transparent solution, casting the casting mold solution on a flat and clean glass plate, placing the glass plate in an air-blowing drying oven at 80 ℃, drying for 3-10h, taking out the glass plate, stripping the membrane from the glass plate, and drying in a vacuum oven at 120 ℃ for 4h to obtain the phosphonated proton exchange membrane. The proton conductivity of these polymer membranes of different degrees of phosphonylation was tested and calculated by electrochemical workstation at 20-80 ℃ under 100% full humidity conditions.
Example 11:
preparing a phosphonated proton exchange membrane, weighing 5g of phosphonated polymers P-PTPSU, P-6F-PSU-1, P-PPySU and P-PTBSU prepared in examples 5 to 7, respectively, dissolving in 50mL of N-methylpyrrolidone solution under magnetic stirring to form a uniform and transparent solution, casting the casting mold solution on a flat and clean glass plate, placing in a forced air drying box at 100 ℃, drying for 6h, taking out, peeling the membrane from the glass plate, then drying in a vacuum oven at 120 ℃ for 6h, and completely removing the residual solvent to obtain the phosphonated proton exchange membrane. Cutting the membrane into samples of 1cm multiplied by 4cm, clamping the samples in a conductivity testing pool, placing the assembled testing pool in a temperature and humidity control box, adjusting the humidity, testing the temperature rise conductivity of the polymer membranes with different degrees of phosphorylation through an electrochemical workstation, gradually raising the temperature from 20 ℃ to 180 ℃ at room temperature, calculating the conductivity, and raising the conductivity of all prepared phosphonated ion exchange membranes along with the temperature rise.
Example 12:
a catalyst slurry was prepared by weighing 7.5mg of the P-PTPSU polymer obtained in example 1 and 30mg of Pt/C catalyst (Pt content 40%, commercially available) in a reagent bottle, adding 225g of water and 1.35g N, N-dimethylacetamide (DMAc) as a solvent, magnetically stirring for 1 hour, and then sonicating for 30min to uniformly disperse the catalyst and polymer to form a stable catalyst slurry. The catalyst is sprayed on hydrophobic carbon paper, the spraying process is carried out in an ultra-clean workbench at 80 ℃, the evaporation of a solvent is accelerated, the adsorption of dust on the surface of an electrode is reduced, and the obtained Pt loading amount is 0.5mg/cm2。
Example 13:
the carbon paper loaded with the two positive and negative catalysts obtained in example 12 and phosphoric acid-doped polybenzimidazole (PBI, commercially available) were pressed together by hot pressing at 120 ℃ for 5min and at 0.5MPa to prepare a high-temperature proton exchange membrane fuel cell using P-PTPSU polymer as a catalyst layer binder, and then the membrane electrode was sandwiched between graphite plates with flow fields and fixed with heating end plates to obtain a single fuel cell, and O was introduced into the cathode2Anode through H2The cell temperature was raised to 160 ℃ by means of a heating rod and its electrochemical performance was measured using an electronic load (commercially available). At constant current density of 0.3A/cm2Under the condition, the output voltage of the single battery is stable at 0.57V-0.65V and is output for more than 500 h.
The starting materials and reagents involved in the above examples were prepared by commercially available or reference methods, and the chemical reaction procedures are within the skill of the art.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (4)
1. A phosphonated polymer characterized by: carrying out chemical modification on a phosphonation functional group on brominated high-temperature resistant polymers such as polypyridyl sulfone, polyphenylene oxide (PPO), polyarylethersulfone and the like to obtain a phosphonation polymer containing crosslinkable group bromine, wherein the structural general formula is as follows:
wherein, (I) (II) X ═ oxygen or sulfur; m is more than 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and m + n is equal to 1;
2. the process for efficiently preparing the phosphonated polymer (I) or (II) by surface light source catalysis according to claim 1 is characterized by the following steps:
(1) photocatalytic Arbuzov reaction: under the atmosphere of nitrogen (99.999 percent, the flow rate is 10-15mL/min), adding brominated high molecular polymer into a quartz four-mouth bottle with magnetic stirring, then adding 1, 3-dimethyl-2-imidazolidinone (DMI), heating and stirring at 50-100 ℃ to completely dissolve the raw materials, adding triethyl phosphite into a constant pressure dropping funnel, when the triethyl phosphite is completely dissolved into a clear transparent solution, carrying out photocatalytic reaction by using an LED light source irradiation machine with the wavelength of 200-450nm, after the reaction is carried out for 0-10h, distilling the sample under reduced pressure to remove the solvent, then dissolving the sample by using chloroform (CHCl3), dropping the sample into isopropanol to separate out a product, washing the product by using isopropanol for multiple times to remove low molecular organic matters in the reaction, filtering, and drying at 120 ℃ to obtain the phosphonate polymer;
(2) acidifying: the phosphonate polymer was dissolved in CHCl under an atmosphere of nitrogen (99.999%, flow rate: 10-15mL/min)3After the polymer is completely dissolved into clear transparent solution, slowly dripping trimethyl bromosilane by using a constant-pressure dropping funnel under the condition of 0 ℃ in an ice water bath, heating and stirring at 20-80 ℃ for 10-30h when the trimethyl bromosilane is dripped till no precipitate is separated out, evaporating the solvent by using a water pump under reduced pressure after the reaction is finished to obtain solid residue, adding methanol into the solid residue, stirring and washing at room temperature for 24h, evaporating the methanol, soaking and washing the obtained product by using deionized water for multiple times so as to remove the solvent and inorganic salt contained in the polymer, and drying to obtain gray massive solid, namely the phosphonated polymer.
3. The use of the phosphonated polymer of claim 1 as an ion exchange membrane material in high temperature fuel cells:
dissolving the phosphonated polymer in common organic solvent such as chloroform, dimethyl sulfoxide, dimethylacetamide, N-methyl pyrrolidone, dimethylformamide and the like to obtain casting solution with the solid content of 2-25%, then blade-coating or brush-coating the casting solution on a glass plate, and completely drying the solvent to obtain the ion exchange membrane.
4. Use of the phosphonated polymer of claim 1 as a catalyst layer binder in high temperature fuel cells:
step 1, mixing and dissolving a phosphonated polymer and a fuel cell catalyst in a mixed solution of isopropanol, N-propanol, N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide and water, and stirring and ultrasonically to completely dissolve the phosphonated polymer and uniformly disperse the catalyst to obtain uniform and non-precipitated slurry, wherein the mass ratio of the phosphonated polymer to the catalyst is 1: 1-1: 10;
and Step 2, coating the obtained catalyst slurry on a gas diffusion layer or a commercially available phosphoric acid-doped polybenzimidazole high-temperature proton exchange membrane by a spraying, brushing or blade coating process, then carrying out hot pressing on carbon paper and an ion exchange membrane to obtain a fuel cell membrane electrode, and assembling the membrane electrode, a graphite plate, an end plate and the like into a fuel cell.
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