CN112980007B - Phosphonic acid modified graphene oxide cross-linked polyolefin grafted benzimidazole polymer composite material - Google Patents
Phosphonic acid modified graphene oxide cross-linked polyolefin grafted benzimidazole polymer composite material Download PDFInfo
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- CN112980007B CN112980007B CN202110163545.4A CN202110163545A CN112980007B CN 112980007 B CN112980007 B CN 112980007B CN 202110163545 A CN202110163545 A CN 202110163545A CN 112980007 B CN112980007 B CN 112980007B
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- phosphonic acid
- graphene oxide
- composite material
- polymer
- modified graphene
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- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 82
- -1 Phosphonic acid modified graphene Chemical class 0.000 title claims abstract description 75
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000012528 membrane Substances 0.000 claims description 62
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 46
- 125000003277 amino group Chemical group 0.000 claims description 42
- 229910021389 graphene Inorganic materials 0.000 claims description 37
- 229920002125 Sokalan® Polymers 0.000 claims description 34
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 125000000732 arylene group Chemical group 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 102
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 51
- 230000008961 swelling Effects 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000007654 immersion Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 50
- 239000004693 Polybenzimidazole Substances 0.000 description 46
- 229920002480 polybenzimidazole Polymers 0.000 description 46
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 44
- 239000006185 dispersion Substances 0.000 description 31
- 239000004584 polyacrylic acid Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- 150000002500 ions Chemical class 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 description 10
- GSZQTIFGANBTNF-UHFFFAOYSA-N (3-aminopropyl)phosphonic acid Chemical compound NCCCP(O)(O)=O GSZQTIFGANBTNF-UHFFFAOYSA-N 0.000 description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 10
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000000034 method Methods 0.000 description 7
- 238000002791 soaking Methods 0.000 description 7
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 description 6
- 229960004343 alendronic acid Drugs 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HMTLHFRZUBBPBS-UHFFFAOYSA-N 2-[2-(2-hydroxyethyl)hydrazinyl]ethanol Chemical compound OCCNNCCO HMTLHFRZUBBPBS-UHFFFAOYSA-N 0.000 description 4
- MJINPOMKSVZKFL-UHFFFAOYSA-N 3-aminobutylphosphonic acid Chemical compound CC(N)CCP(O)(O)=O MJINPOMKSVZKFL-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
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- BMYBKYQDGKGCSU-UHFFFAOYSA-N (2-aminophenyl)phosphonic acid Chemical compound NC1=CC=CC=C1P(O)(O)=O BMYBKYQDGKGCSU-UHFFFAOYSA-N 0.000 description 2
- MZZQBSHNCYWSTL-UHFFFAOYSA-N (3-aminophenyl)phosphonic acid Chemical compound NC1=CC=CC(P(O)(O)=O)=C1 MZZQBSHNCYWSTL-UHFFFAOYSA-N 0.000 description 2
- OAOBMEMWHJWPNA-UHFFFAOYSA-N (4-aminophenyl)phosphonic acid Chemical compound NC1=CC=C(P(O)(O)=O)C=C1 OAOBMEMWHJWPNA-UHFFFAOYSA-N 0.000 description 2
- UIQSKEDQPSEGAU-UHFFFAOYSA-N 1-Aminoethylphosphonic Acid Chemical compound CC(N)P(O)(O)=O UIQSKEDQPSEGAU-UHFFFAOYSA-N 0.000 description 2
- UAEPDDGDPAPPHZ-UHFFFAOYSA-N 1-aminobutylphosphonic acid Chemical compound CCCC(N)P(O)(O)=O UAEPDDGDPAPPHZ-UHFFFAOYSA-N 0.000 description 2
- DELJNDWGTWHHFA-UHFFFAOYSA-N 1-azaniumylpropyl(hydroxy)phosphinate Chemical compound CCC(N)P(O)(O)=O DELJNDWGTWHHFA-UHFFFAOYSA-N 0.000 description 2
- YKTGHPUVQJCWHB-UHFFFAOYSA-N 3-aminopentylphosphonic acid Chemical compound CCC(N)CCP(O)(O)=O YKTGHPUVQJCWHB-UHFFFAOYSA-N 0.000 description 2
- RCUUZWBKMBNAIA-UHFFFAOYSA-N 4-aminopentylphosphonic acid Chemical compound CC(N)CCCP(O)(O)=O RCUUZWBKMBNAIA-UHFFFAOYSA-N 0.000 description 2
- VOROEQBFPPIACJ-UHFFFAOYSA-N 5-Phosphononorvaline Chemical compound OC(=O)C(N)CCCP(O)(O)=O VOROEQBFPPIACJ-UHFFFAOYSA-N 0.000 description 2
- CTJLHQOKWJEKHY-UHFFFAOYSA-N 5-aminopentylphosphonic acid Chemical compound NCCCCCP(O)(O)=O CTJLHQOKWJEKHY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 229920005597 polymer membrane Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N trifluoroacetic acid Substances OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- 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
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- 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
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
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- 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
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- 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
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- Medicinal Chemistry (AREA)
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- Materials Engineering (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention also provides a polyolefin grafted benzimidazole polymer grafted modified graphene oxide composite material and a preparation method and application thereof. The phosphonic acid modified graphene oxide in the composite material is introduced into the polyolefin grafted benzimidazole polymer in a covalent bond mode, and the introduction of a small amount of phosphonic acid modified graphene oxide further reduces the doping level of phosphoric acid to below 9, so that the proton conductivity is obviously improved and can reach 10 multiplied by 10‑2S/cm, transverse swelling rate after phosphoric acid immersion is as low as 6.9%, and tensile strength is more than 8 MPa.
Description
Technical Field
The invention relates to a phosphonic acid modified graphene oxide cross-linked polyolefin grafted benzimidazole polymer composite material, and a preparation method and application thereof, and belongs to the technical field of proton exchange membranes.
Background
Benzimidazole Polymers (PBIs) are polymers containing benzimidazole rings in a main chain structure, have excellent physicochemical properties such as chemical stability, thermal stability, flame retardance, mechanical property and the like, and are widely applied to high-temperature-resistant fabrics, fireproof flame-retardant materials, industrial product filter materials and the like. With the development of fuel cell research, the conventional perfluorosulfonic acid proton exchange membrane cannot meet the operation of the fuel cell under the conditions of high temperature and low humidity due to the defects of proton conductivity, mechanical property reduction and the like under the conditions of high temperature and low humidity, and researchers begin to search and research novel proton exchange membrane materials. PBIs are favored because of their excellent chemical and thermal stability, and researchers have found that although PBIs do not conduct protons, PBIs exhibit basicity due to their specific imidazole ring structure, and undergo protonation with inorganic acids, particularly Phosphoric Acid (PA), to form ion pairs, resulting in certain proton conductivity.
In the field of high-temperature proton exchange membranes, the proton conductivity of the PBIs-based proton exchange membranes depends heavily on the phosphoric acid doping level (ADL, the number of moles of phosphoric acid bound per mole of polymer repeating unit), and a large amount of phosphoric acid needs to be doped to ensure that the membranes have high proton conductivity, which causes the mechanical properties of the membranes to be obviously reduced, so that the balance between the proton conductivity and the mechanical properties needs to be considered; in addition, more phosphoric acid is easy to run off along with water generated by the cathode in the using process, and the proton conductivity of the membrane is reduced. The conventional solution to the above problems is crosslinking, incorporation of proton carriers such as zirconium phosphate, heteropoly acid, ionic liquid, etc., or introduction of SiO2、TiO2Clay, zeolite, and montmorillonite. In the prior art, a cross-linking type high-temperature proton exchange membrane is formed by self-crosslinking by taking polybenzimidazole as a polymer framework and triazole ionic liquid-based polyethylene as a cross-linking agent; in the prior art, it has also been reported that 0.1-30% of acid modified ordered mesoporous SiO is doped into the composite high-temperature proton exchange membrane2The proton transfer is promoted, and the proton conductivity is improved; or doping inorganic porous materials in the PBIs membrane to prepare the composite membrane.
The graphene is formed by sp from carbon atoms2The hybrid tracks form a hexagonal honeycomb-lattice two-dimensional structure material, have high specific surface area, high thermal conductivity and excellent mechanical properties, and can be applied to electrode materials of super capacitors, lithium ion batteries and the like. The graphene oxide has rich functional groups, so that the graphene oxide is favorable for the dispersion of the graphene oxide in an organic solvent and a polymer, and simultaneously provides a large number of modification sites, and can be modified according to needs, so that the graphene oxide has higher compatibility in the polymer, and the application of the graphene oxide in a polymer material is expanded. The dispersion of graphene in the matrix may be achieved by pi-pi non-covalent bonding forces.
In the prior art, graphene oxide is directly mixed and doped with a polybenzimidazole matrix to prepare a composite material, so that the compatibility problem of the graphene oxide and the polymer matrix exists, and the problems that the graphene oxide is easy to aggregate in the polybenzimidazole matrix and has poor binding force with the polybenzimidazole matrix exist.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a phosphonic acid modified graphene oxide crosslinked polyolefin grafted benzimidazole polymer composite material, and a preparation method and application thereof. In the composite material, the phosphonic acid modified graphene oxide is used as a cross-linking agent, and the polyolefin grafted benzimidazole polymer is cross-linked, so that the compatibility of the phosphonic acid modified graphene oxide and the polyolefin grafted benzimidazole polymer matrix can be improved, the swelling of the polyolefin grafted benzimidazole polymer matrix can be limited, phosphonic acid (amino-containing phosphonic acid compound molecules) in the phosphonic acid modified graphene oxide is beneficial to proton conduction, and the problems of swelling and high phosphoric acid doping level of the polyolefin grafted benzimidazole polymer are solved. In the composite material, due to the introduction of a small amount of phosphonic acid modified graphene oxide, the doping level of phosphoric acid is further reduced to below 9, and the proton conductivity is obviously improved to 10 multiplied by 10 -2S/cm, the transverse swelling ratio after being soaked in phosphoric acid is as low as 6.9 percent, and the tensile strength is more than 8 MPa. Therefore, the phosphonic acid modified graphene oxide is introduced into the polyolefin grafted benzimidazole polymer, so that the doping level of phosphoric acid in the polyolefin grafted benzimidazole polymer-based proton exchange membrane can be reduced, and high proton conductivity retention rate under a high-temperature anhydrous condition can be obtained, and the research and application prospects are extremely good.
Specifically, the invention provides the following technical scheme:
< composite Material >
The invention provides a phosphonic acid modified graphene oxide cross-linked polyolefin grafted benzimidazole polymer composite material which comprises a polyolefin grafted benzimidazole polymer and phosphonic acid modified graphene oxide, wherein phosphonic acid in the phosphonic acid modified graphene oxide is selected from phosphonic acid compounds containing amino groups.
In one embodiment, the phosphonic acid-modified graphene oxide is grafted to the polyolefin-grafted benzimidazole polymer through an amide bond (-CO-NH-) and/or the phosphonic acid-modified graphene oxide is grafted to the polyolefin-grafted benzimidazole polymer through a secondary amine bond (-NH-).
In one embodiment, the composite material is prepared by chemically reacting polyolefin grafted benzimidazole polymer and phosphonic acid modified graphene oxide.
In one embodiment, the composite material is obtained by reacting terminal amino groups in a polyolefin grafted benzimidazole polymer with carboxyl and/or epoxy groups in phosphonic acid modified graphene oxide, and the molecular structure of the composite material is as shown in the following:
wherein-NH-R1-H2PO3The meaning of which is represented by the phosphonic acid compound molecule containing amino, R1Selected from substituted or unsubstituted arylene, substituted or unsubstituted alkylene, the substituent being selected from phosphonic acid group (-H)2PO3)； R2Through two terminal amino groups (-NH)2) A benzimidazole polymer side chain connected to the olefin polymer main chain containing carboxyl on the side chain after condensation reaction with-COOH on R'.
Wherein the amount of the phosphonic acid modified graphene oxide added is 1 to 5 wt%, preferably 1 to 4 wt%, more preferably 1 to 3 wt%, for example, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.5 wt%, or 5 wt% of the total mass of the composite.
Wherein the amount of the polyolefin grafted benzimidazole polymer added is 95-99 wt%, preferably 96-99 wt%, more preferably 97-99 wt%, for example, 95 wt%, 95.5 wt%, 96 wt%, 96.2 wt%, 96.5 wt%, 96.8 wt%, 97 wt%, 97.2 wt%, 97.5 wt%, 97.8 wt%, 98 wt%, 98.2 wt%, 98.5 wt%, 98.8 wt% or 99 wt% of the total mass of the composite material.
In one embodiment, the composite material is prepared by a chemical reaction of an amino-terminated benzimidazole polymer, an olefin polymer with a side chain containing carboxyl, and phosphonic acid modified graphene oxide.
Wherein the amount of the phosphonic acid modified graphene oxide added is 1 to 5 wt%, preferably 1 to 4 wt%, more preferably 1 to 3 wt%, for example, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.2 wt%, 3.5 wt%, 3.8 wt%, 4 wt%, 4.5 wt%, or 5 wt% of the total mass of the composite.
Wherein the amount of the olefin-based polymer having carboxyl groups in side chains added is 5 to 40 wt%, preferably 5 to 30 wt%, more preferably 10 to 20 wt%, for example, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%, 32 wt%, 35 wt%, 38 wt% or 40 wt% of the total mass of the composite.
< phosphonic acid-modified graphene oxide >
In one embodiment, the phosphonic acid modified graphene oxide is prepared by reacting graphene oxide with phosphonic acid containing an amino group.
In one embodiment, the phosphonic acid is linked to graphene oxide through an amide linkage (-CO-NH-) and/or the phosphonic acid is linked to graphene oxide through a secondary amine linkage (-NH-).
In one embodiment, the phosphonic acid is grafted to the graphene oxide through amidation reaction of an amino group in the amino group-containing phosphonic acid compound with a carboxyl group on the graphene oxide and/or nucleophilic substitution reaction of an epoxy group.
In one embodiment, a carboxyl group in the graphene oxide undergoes an amidation reaction with an amino group in the amino group-containing phosphonic acid compound, and/or an epoxy group in the graphene oxide undergoes a nucleophilic substitution reaction with an amino group in the amino group-containing phosphonic acid compound.
In one embodiment, the mass ratio of the graphene oxide to the amino group-containing phosphonic acid compound is 2:1 to 2:3, for example, 2:1, 2:1.5, 2:2, 2:2.5, or 2: 3.
In one embodiment, the molar ratio of the carboxyl group in the graphene oxide and/or the epoxy group in the graphene oxide to the amino group in the amino group-containing phosphonic acid compound is 9:1 to 1.5:1, for example, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, or 1.5: 1.
In one embodiment, the graphene oxide is graphene oxide conventional in the art, which is commercially available or may be prepared by methods known in the art, such as the Hummer method.
In one embodiment, the amino group-containing phosphonic acid compound has the formula, for example, NH2-R1-H2PO3(ii) a Wherein R is1Selected from substituted or unsubstituted arylene, substituted or unsubstituted alkylene, the substituent being selected from phosphonic acid group (-H)2PO3)。
More specifically, the amino group-containing phosphonic acid compound is at least one selected from the group consisting of 4-amino-1-hydroxybutylidene-1, 1-diphosphonic acid (alendronic acid), 4-aminobutylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminobutylphosphonic acid, 3-aminopropylphosphonic acid, (1-aminoethyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (1-aminobutyl) phosphonic acid, 2-amino-5-phosphonovaleric acid, 5-aminopentylphosphonic acid, 4-aminopentylphosphonic acid, 3-aminopentylphosphonic acid, (4-aminophenyl) phosphonic acid, (3-aminophenyl) phosphonic acid, and (2-aminophenyl) phosphonic acid; preferably, it is selected from at least one of 4-amino-1-hydroxybutylidene-1, 1-diphosphonic acid (alendronic acid), 4-aminobutylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminobutylphosphonic acid.
In one embodiment, the phosphonic acid-modified graphene oxide contains a phosphonic acid compound molecule containing an amino group, a carboxyl group and/or an epoxy group, a hydroxyl group, and the like on the surface thereof.
In one embodiment, in the phosphonic acid-modified graphene oxide, the content of the amino group-containing phosphonic acid compound molecules grafted to the surface of the graphene oxide (the mass percentage of the amino group-containing phosphonic acid compound molecules grafted to the surface of the graphene oxide to the total mass of the phosphonic acid-modified graphene oxide) is 5 to 30 wt%, for example, 5 wt%, 8 wt%, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, or 30 wt%.
In one embodiment, the content of carboxyl groups and/or epoxy groups (mass percentage of carboxyl groups and/or epoxy groups to the total mass of the phosphonic acid-modified graphene oxide) in the phosphonic acid-modified graphene oxide is 10 to 30 wt%, for example, 10 wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, 30 wt%.
In one embodiment, the molecular structure of the phosphonic acid modified graphene oxide is schematically shown as follows:
wherein-NH-R1-H2PO3The meaning of which is represented by the phosphonic acid compound molecule containing amino, R1The definition of (1) is as before; still specifically, the amino group-containing phosphonic acid compound is at least one selected from the group consisting of 4-amino-1-hydroxybutylidene-1, 1-diphosphonic acid (alendronic acid), 4-aminobutylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminobutylphosphonic acid, 3-aminopropylphosphonic acid, (1-aminoethyl) phosphonic acid, (1-aminopropyl) phosphonic acid, (1-aminobutyl) phosphonic acid, 2-amino-5-phosphonovaleric acid, 5-aminopentylphosphonic acid, 4-aminopentylphosphonic acid, 3-aminopentylphosphonic acid, (4-aminophenyl) phosphonic acid, (3-aminophenyl) phosphonic acid, and (2-aminophenyl) phosphonic acid; preferably, it is selected from at least one of 4-amino-1-hydroxybutylidene-1, 1-diphosphonic acid (alendronic acid), 4-aminobutylphosphonic acid, 2-aminoethylphosphonic acid, 3-aminobutylphosphonic acid.
The invention also provides a preparation method of the phosphonic acid modified graphene oxide, which comprises the following steps:
(1) dispersing graphene oxide in a solvent to obtain a graphene oxide dispersion liquid;
(2) and (2) adding an amino-containing phosphonic acid compound into the graphene oxide dispersion liquid obtained in the step (1) for reaction to prepare the phosphonic acid modified graphene oxide.
In one embodiment, in the step (1), the concentration of the graphene oxide dispersion liquid is 0.5-5 mg/mL.
In one embodiment, in step (1), the solvent is selected from water.
In one embodiment, in the step (2), the reaction temperature is 90-110 ℃, and the reaction time is 8-24 h.
In one embodiment, in the step (2), the mass ratio of the graphene oxide to the amino group-containing phosphonic acid compound is 2:1 to 2:3, for example, 2:1, 2:1.5, 2:2, 2:2.5, or 2: 3.
In one embodiment, the reaction further comprises a post-treatment step after the reaction, wherein the post-treatment step is, for example, suction filtration, washing, dispersion in a solvent for use, and the like.
< polyolefin graft benzimidazole polymers >
In one embodiment, the polyolefin graft benzimidazole polymer is a graft copolymer in which a benzimidazole polymer obtained by a condensation reaction of a terminal amino group in a benzimidazole polymer containing a terminal amino group and a carboxyl group in an olefin polymer having a carboxyl group in a side chain is grafted to an olefin polymer main chain having a carboxyl group in a side chain.
In one embodiment, the polyolefin grafted benzimidazole polymer is a graft copolymer in which a benzimidazole polymer containing terminal amino groups is grafted to an olefin-based polymer backbone having carboxyl groups in the side chains through imidazole rings.
In one embodiment, the polyolefin grafted benzimidazole polymer is a graft copolymer obtained by grafting an amino-terminated benzimidazole polymer to a side-chain carboxyl-containing olefin polymer backbone through an imidazole condensation reaction between carboxyl and two adjacent amino-terminated groups on a backbone structure of the benzimidazole polymer.
In one embodiment, the polyolefin grafted benzimidazole polymer contains a structural unit represented by the following formula (1):
in the formula (1), R' is selected from H and alkyl; r' is selected from the group consisting of absent, substituted or unsubstituted arylene, substituted or unsubstituted alkylene, wherein the substituents may be selected from the group consisting of alkyl, carboxyl, halogen; r2Through two terminal amino groups (-NH)2) Benzimidazole polymer side chains connected to the olefin polymer main chains with side chains containing carboxyl after undergoing a condensation reaction with-COOH on R';
m is an integer between 100 and 50000;
when R' is not existed, z is 0, 1 is more than or equal to x1+ x2>0, and y is 1-x1-x 2; when R' is arylene or alkylene, 1> z ≧ 0, 1 ≧ x1+ x2>0, y ═ 1-z-x1-x 2.
Specifically, x1+ x2 is preferably 0.001 to 0.2, more preferably 0.005 to 0.1, and still more preferably 0.01 to 0.1.
Specifically, the meaning of the repeating unit with the polymerization degree of x1 is a polymer chain segment which is subjected to a cross-linking reaction with the phosphonic acid modified graphene oxide; the repeating unit with the polymerization degree of x2 represents a high-molecular chain segment which is not subjected to crosslinking reaction with the phosphonic acid modified graphene oxide.
Specifically, the R' is selected from H, C1-6An alkyl group; still more particularly, said R "is selected from H, methyl or ethyl.
Specifically, R' is selected from the group consisting of absent, substituted or unsubstituted alkylene, substituted or unsubstituted phenylene, wherein the substituent may be selected from the group consisting of alkyl, carboxyl. For example, the R' is selected from absent, or one or more of the following:
wherein denotes the connection point.
More specifically, the molecular structural formula of the polyolefin grafted benzimidazole polymer is one of the following:
wherein, x1, x2, y, m and R2The definition of (1) is as before; p represents the degree of carboxylation, 1. gtoreq.p>0, and p + q ═ 1; ar is selected from one or more of the following groups:
denotes the connection point.
According to the invention, benzimidazole Polymers (PBIs) containing terminal amino groups are grafted to olefin polymers with side chains containing carboxyl groups to obtain a graft copolymer with soft-hard chain segments, and the specific reaction principle is that the side groups-carboxyl groups in the olefin polymers with side chains containing carboxyl groups, such as poly (methyl) acrylic acid, and two adjacent terminal amino groups on the main chain structure of the benzimidazole polymers undergo an imidazole condensation reaction to obtain the graft copolymer of the olefin polymers with side chains containing carboxyl groups grafted by PBIs. Researches find that the proton exchange membrane containing the graft copolymer is suitable for being used as a high-temperature proton exchange membrane, and has higher proton conductivity under the condition of lower phosphoric acid doping level.
The polyolefin grafted benzimidazole polymer is prepared by the following method:
dissolving benzimidazole polymer containing terminal amino in an organic solvent to obtain a solution of the polymer;
adding an olefin polymer with a side chain containing carboxyl into the solution, and reacting under heating; and preparing the polyolefin grafted benzimidazole polymer.
Wherein the organic solvent is one or more of the following in combination: DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), NMP (N, N-dimethylpyrrolidone), polyphosphoric acid, methanesulfonic acid, TFA (trifluoroformic acid sulfonic acid), preferably DMF.
Wherein, the benzimidazole polymer containing the terminal amino group can be purchased from commercial sources or prepared by the method known in the field.
Wherein, the olefin polymer containing carboxyl on the side chain is selected from at least one of polyacrylic acid (PAA), polymethacrylic acid (PMAA) and carboxylated polystyrene, wherein, the preparation method of the carboxylated polystyrene is described in Novel strategies for the synthesis of hydroxylated and carboxylated polystyrenes.
Wherein, the olefin polymer with side chain containing carboxyl is added into the solution, and the total solid content is controlled to be 1-25 percent.
Wherein the molar ratio of the carboxyl in the benzimidazole polymer containing the terminal amino group to the olefin polymer containing the carboxyl on the side chain is 1: 5-1: 1000, for example, 1: 8-1: 1000, specifically, 1:8, 1:10, 1:100, 1:200, 1:300, 1:400, 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000 and the like.
Wherein the reaction is carried out under the conditions of heating at 150-200 ℃ and protection of inert gas; specifically, the reaction time is 10-24 h.
< benzimidazole polymers containing terminal amino groups >
Specifically, the benzimidazole polymer containing the terminal amino is a polymer containing benzimidazole rings in a main chain structure; specifically, the main chain structure of the benzimidazole polymer containing the terminal amino contains a benzimidazole ring, one end of the main chain structure also contains a benzene ring, and two adjacent terminal amino (-NH) are connected to the benzene ring2) The polymer of (a); according to the requirement, the benzimidazole polymer is a polymer with amino groups at both ends, and the polymerization degree n of the benzimidazole polymer containing amino groups at the ends can be 10-5000, preferably 50-1000, and more preferably 100-500.
Specifically, the benzimidazole polymer containing the terminal amino is selected from at least one of the following structures of formula (2) or formula (3):
in the formulae (2) to (3), X is selected from,
-S-, -O-, halogen substituted or unsubstituted C1-6An alkyl group; r is selected from halogen substituted or unsubstituted C1-8Alkylene, halogen substituted or unsubstituted C6-20An arylene group; n is an integer between 10 and 5000.
In one embodiment of the invention, X is selected from absent,
-S-、-O-、 -C(CH3)2-、-C(CF3)2-、-CH2-。
In one embodiment of the present invention, R is selected from halogen substituted or unsubstituted C3-8Alkylene, halogen substituted or unsubstituted C6-16Arylene radicals, e.g. selected from-C6H4-、-C6H4-C6H4-、-C6H4-O-C6H4-、 -C6H4-C(CH3)2-C6H4-、-C6H4-C(CF3)2-C6H4-、-C6H4-CH2-C6H4-、-CH2-C6H4-CH2-、 -(CH2)4-8-、-(CF2)3-6-。
Illustratively, the benzimidazole polymer containing terminal amino groups is selected from at least one of the following structures:
wherein n is an integer between 10 and 5000; r is selected from one of the following structures:
denotes the connection point.
< olefin-based Polymer having carboxyl group in side chain >
Specifically, the olefin polymer having carboxyl groups in the side chains is, for example, at least one selected from polyacrylic acid (PAA), polymethacrylic acid (PMAA), and carboxylated polystyrene, wherein the preparation method of the carboxylated polystyrene is described in Novel copolymers for the synthesis of hydroxylated and carboxylated polystyrenes.
< definition of terms >
The "halogen" in the invention refers to fluorine, chlorine, bromine or iodine.
"alkyl" used herein alone or as suffix or prefix, is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having from 1 to 20, preferably from 1 to 6, carbon atoms. For example, "C1-6 alkyl" denotes straight and branched chain alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
"aryl" used herein alone or as a suffix or prefix, refers to an aromatic ring structure made up of 5 to 20 carbon atoms. For example: the aromatic ring structure containing 5, 6, 7 and 8 carbon atoms may be a monocyclic aromatic group such as phenyl; the ring structure containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms may be polycyclic, for example naphthyl. The aromatic ring may be substituted at one or more ring positions with substituents such as alkyl, carboxyl and the like, for example, tolyl.
The "alkylene" in the present invention is a group obtained by substituting one H with the "alkyl".
The term "arylene" as used herein refers to a group formed by substituting said "aryl" for one H.
< preparation method of composite Material >
The invention also provides a preparation method of the phosphonic acid modified graphene oxide crosslinked polyolefin grafted benzimidazole polymer composite material, which comprises the following steps:
(a1) dissolving polyolefin grafted benzimidazole polymer in an organic solvent to obtain polyolefin grafted benzimidazole polymer solution;
(a2) adding phosphonic acid modified graphene oxide into the solution, and reacting under a heating condition to obtain the polyolefin grafted benzimidazole polymer grafted modified graphene oxide composite material; or,
(b1) dissolving the benzimidazole polymer containing the terminal amino group in an organic solvent to obtain benzimidazole polymer solution containing the terminal amino group;
(b2) dissolving an olefin polymer with a side chain containing carboxyl in an organic solvent to obtain an olefin polymer solution with a side chain containing carboxyl;
(b3) mixing phosphonic acid modified graphene oxide, a benzimidazole polymer solution containing terminal amino groups and an olefin polymer solution containing carboxyl on side chains, and reacting under a heating condition to prepare the polyolefin grafted benzimidazole polymer grafted modified graphene oxide composite material.
In steps (a1), (b1) and (b2), the organic solvent is one or a combination of more of the following: DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethyl sulfoxide), NMP (N, N-dimethylpyrrolidone).
In the step (a1), the concentration of the polyolefin grafted benzimidazole polymer solution is 1-20 wt%, preferably 2-15 wt%, and more preferably 5-10 wt%.
In the step (b1), the concentration of the benzimidazole polymer solution containing terminal amino groups is 1-20 wt%, preferably 2-15 wt%, and more preferably 5-10 wt%.
In the step (b2), the concentration of the olefin polymer solution having carboxyl groups in the side chains is 1 to 20 wt%, preferably 2 to 15 wt%, and more preferably 5 to 10 wt%.
In the steps (a2) and (b3), the phosphonic acid modified graphene oxide is prepared by the method.
In the step (a2), preferably, phosphonic acid modified graphene oxide is dispersed in an organic solvent to obtain a dispersion of phosphonic acid modified graphene oxide, and then the dispersion is added to the polyolefin grafted benzimidazole polymer solution.
In the step (b3), the phosphonic acid-modified graphene oxide is preferably dispersed in an organic solvent to obtain a dispersion of the phosphonic acid-modified graphene oxide, and then the dispersion is added to the benzimidazole polymer solution containing terminal amino groups and the olefin polymer solution containing carboxyl groups on side chains.
In the step (a2), the mass ratio of the polyolefin grafted benzimidazole polymer to the phosphonic acid modified graphene oxide is 95-99: 1-5, preferably 96-99: 1-4, and more preferably 97-99: 1-3.
In the steps (a2) and (b3), the reaction is carried out under the conditions of heating at 130-200 ℃ and protection of inert gas; specifically, the reaction time is 6-24 h.
< proton exchange Membrane and method for producing the same and use >
The invention also provides a proton exchange membrane which comprises the composite material.
Furthermore, the proton exchange membrane is also doped with phosphoric acid.
Further, the doping level ADL of phosphoric acid is less than 9.
The invention also provides a preparation method of the proton exchange membrane, which comprises the following steps:
(c1) dissolving polyolefin grafted benzimidazole polymer in an organic solvent to obtain polyolefin grafted benzimidazole polymer solution;
(c2) adding phosphonic acid modified graphene oxide into the solution, and reacting under a heating condition;
(c3) after the reaction is finished, pouring the solution onto the surface of a base material for tape casting, volatilizing the solvent at 60-120 ℃, and soaking the base material in phosphoric acid after the solvent is completely volatilized to obtain the proton exchange membrane; or,
(d1) dissolving the benzimidazole polymer containing the terminal amino group in an organic solvent to obtain benzimidazole polymer solution containing the terminal amino group;
(d2) dissolving an olefin polymer with a side chain containing carboxyl in an organic solvent to obtain an olefin polymer solution with a side chain containing carboxyl;
(d3) Mixing phosphonic acid modified graphene oxide, a benzimidazole polymer solution containing terminal amino and an olefin polymer solution containing carboxyl on a side chain, and reacting under a heating condition;
(d4) and after the reaction is finished, pouring the solution onto the surface of the base material for tape casting, volatilizing the solvent at 60-120 ℃, and soaking the base material in phosphoric acid after the solvent is completely volatilized to obtain the proton exchange membrane.
In the steps (c3) and (d4), the base material is one of copper foil, aluminum foil, glass plate, polypropylene, polyester, polytetrafluoroethylene and polyvinylidene fluoride.
In steps (c3) and (d4), the concentration of phosphoric acid is 60 to 90 wt%, for example 85 wt%.
In steps (c3) and (d4), the immersion time is 6 to 30 hours, for example 12 to 24 hours.
The invention also provides the application of the proton exchange membrane in the fields of fuel cells, flow batteries and the like.
It is to be understood that the above-described technical features of the present invention and the respective technical features described in detail hereinafter may be combined with each other to constitute a new or preferred technical solution.
The invention has the advantages of
The invention also provides a polyolefin grafted benzimidazole polymer grafted modified graphene oxide composite material and a preparation method and application thereof. The phosphonic acid modified graphene oxide in the composite material is introduced into the polyolefin grafted benzimidazole polymer in a covalent bond mode, and the introduction of a small amount of phosphonic acid modified graphene oxide further reduces the doping level of phosphoric acid to below 9, so that the proton conductivity is obviously improved and can reach 10 multiplied by 10 -2S/cm, transverse swelling rate after phosphoric acid immersion is as low as 6.9%, and tensile strength is more than 8 MPa.
The modification of the phosphonic acid modified graphene oxide in the composite material improves the compatibility and the bonding force of the phosphonic acid modified graphene oxide with polyolefin grafted benzimidazole polymers, improves the ionic conductivity of the composite material, further reduces the phosphoric Acid Doping Level (ADL) of the composite material, improves the swelling resistance and the mechanical property of the composite material, optimizes the comprehensive performance of the composite material, and can be suitable for manufacturing fuel cell electrolyte membrane materials.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Unless otherwise indicated, the following materials were used in the examples described below:
Graphene oxide GO, purchased from piofeng nano corporation under the designation XF 224-1.
The structural formula of the PBI containing double amino groups is as follows:
PAA has a molecular weight Mn of 45 ten thousand, purchased from alatin reagent.
The structural formula of poly [2,6- (p-phenylene) -phenmedibenediimidazole ] is as follows:
test example:
1. determination of ADL
The polymer films of examples and comparative examples were immersed in 85% phosphoric acid solution at 60 ℃ for 24 h; then, the membrane surface was taken out and acid-adsorbed by filter paper, and then dried at 80 ℃, and then the mass of the polymer membrane before and after the impregnation was measured, and the phosphoric Acid Doping Level (ADL) was calculated by the formula (1).
ADL＝(m2-m1/98)×(Mw/m1) (1)
Wherein the ADL is a polymer filmPhosphoric acid doping level, m1And m2Respectively the mass of the polymer film before and after impregnation with phosphoric acid, MwIs the repeat unit molecular weight of the polymer film, and 98 is the molecular weight of phosphoric acid.
2. Determination of proton conductivity
Cutting the phosphoric acid-doped proton exchange membranes prepared in the examples and the comparative examples into membranes of 5cm multiplied by 5cm, placing the membranes between two graphite plates, testing the resistance of the membranes at different temperatures by using an electrochemical workstation through alternating current impedance, and calculating the proton conductivity of the membranes at different temperatures through a formula (2);
σ＝t/R×S (2)
wherein σ is proton conductivity (S/cm), t is thickness (cm) of the proton exchange membrane, R is in-plane resistance (Ω) perpendicular to the membrane surface, and S is effective membrane area (cm) 2)。
3. Determination of proton conductivity Retention
And taking down the tested proton exchange membrane doped with phosphoric acid, soaking the proton exchange membrane in deionized water for 30s, taking out the proton exchange membrane, drying the proton exchange membrane, and then performing the conductivity test again, repeating the process for 10 times, wherein the proton conductivity after soaking the deionized water for 10 times replaces the long-time fuel cell membrane electrode test, and the proton conductivity retention rate of the proton exchange membrane is indirectly shown.
4. Tensile strength
The proton exchange membrane impregnated with phosphoric acid was cut into 5mm × 30mm strips, and the tensile strength was measured on a tensile machine.
5. Transverse swelling ratio
The proton exchange membrane was cut into disks with a diameter of 16mm, then immersed in phosphoric acid at 120 ℃ for 12h, and then the diameter change of the membrane was tested:
wherein,
in order to obtain a diameter after the phosphoric acid impregnation,
the diameter before phosphoric acid impregnation.
Example 1
(1) 0.2g of graphene oxide is dispersed in 100mL of water by ultrasonic to prepare graphene oxide/water dispersion with the concentration of 2 mg/mL. 0.2g of 3-aminopropyl phosphonic acid was dissolved in 20mL of ethanol to prepare a 10mg/mL 3-aminopropyl phosphonic acid/ethanol solution. Adding the 3-aminopropyl phosphonic acid/ethanol solution into the graphene oxide/water dispersion, and stirring and refluxing for 12h at 95 ℃. And (3) performing suction filtration, washing filter residues in ethanol, and then dispersing the filter residues in DMAc to obtain a phosphonic acid modified graphene oxide/DMAc dispersion liquid (recorded as LGO/DMAc dispersion liquid, wherein the content of 3-aminopropyl phosphonic acid in LGO is 17.2 wt%) with the concentration of 2.5 mg/mL.
(2) Mixing and stirring LGO/DMAc dispersion (59mL) and 64.8g of PBI/DMAc solution containing amino double terminals in a concentration of 10 wt% (PBI molecular weight is 3.1kDa), then reacting at 150 ℃ for 4h, adding 7.2g of PAA/DMAc solution in a concentration of 10 wt%, continuing to react for 8h, and after the reaction is finished, placing the solution in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 9.8 wt%, the PBI content is 88.2 wt%, and the LGO content is 2 wt%).
(3) And (3) soaking the composite film material in the step (2) in 85% phosphoric acid for 12 hours, and standing for phosphoric acid permeation to obtain the proton exchange film material.
The ADL of the membrane material is 8.88 by test, and the ion conductivity of the membrane material is 8.78 multiplied by 10 measured at 180 DEG C-2S/cm, 6.68X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 76.0 percent, the transverse swelling rate after phosphoric acid doping is 17.8 percent, and the tensile strength is 8.5 MPa.
Example 2
(1) The same as in example 1, except that the amount of 3-aminopropylphosphonic acid added was adjusted to 0.1g, the content of 3-aminopropylphosphonic acid in the obtained LGO was 6.4% by weight.
(2) LGO/DMAc dispersion (59mL) and 57.6g of PBI/DMAc solution containing amino double terminals in a concentration of 10 wt% (PBI molecular weight is 3.1kDa) are mixed and stirred uniformly, then the mixture is reacted for 4 hours at 150 ℃, 14.4g of PAA/DMAc solution in a concentration of 10 wt% is added, the reaction is continued for 8 hours, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 9.6 wt%, the PBI content is 88.4 wt%, and the LGO content is 2 wt%).
(3) Same as in example 1.
The ADL of the membrane material is 8.06 by test, and the ion conductivity is 9.48 multiplied by 10 at 180 DEG C-2S/cm, 7.30X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 77.0%, the transverse swelling rate after phosphoric acid doping is 21.9%, and the tensile strength is 8.8 MPa.
Example 3
(1) The same as in example 1, except that the amount of 3-aminopropylphosphonic acid added was adjusted to 0.15g, the content of 3-aminopropylphosphonic acid in the obtained LGO was 11.3% by weight.
(2) LGO/DMAc dispersion (78mL) and 81.6g of PBI/DMAc solution containing amino double terminals in concentration of 10 wt% (PBI molecular weight is 3.1kDa) are mixed and stirred uniformly, then the mixture is reacted for 4 hours at 150 ℃, 14.4g of PAA/DMAc solution containing 10 wt% is added, the reaction is continued for 8 hours, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 9.7 wt%, the PBI content is 88.3 wt%, and the LGO content is 2 wt%).
(3) Same as in example 1.
The ADL of the membrane material is 8.35 by test, and the ion conductivity is 9.76 multiplied by 10 at 180 DEG C-2S/cm, 7.69 multiplied by 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 78.8%, the transverse swelling rate after phosphoric acid doping is 19.2%, and the tensile strength is 8.6 MPa.
Example 4
(1) 0.2g of graphene oxide is dispersed in 100mL of water by ultrasonic to prepare graphene oxide/water dispersion with the concentration of 2 mg/mL. 0.2g of alendronic acid was added to the dispersion and stirred under reflux at 95 ℃ for 12 h. And (3) performing suction filtration, washing the filter residue in water, and then dispersing the filter residue in DMAc to obtain a phosphonic acid modified graphene oxide/DMAc dispersion liquid (recorded as an LGO/DMAc dispersion liquid, wherein the content of the alendronic acid in the LGO is 15.3 wt%) with the concentration of 2.5 mg/mL.
(2) LGO/DMAc dispersion (39mL) and 81.6g of PBI/DMAc solution containing amino-terminated groups with concentration of 10 wt% (PBI molecular weight is 70kDa) are mixed and stirred uniformly, then the mixture is reacted for 4 hours at 150 ℃, 14.4g of PAA/DMAc solution with concentration of 10 wt% is added, the reaction is continued for 8 hours, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 14.85 wt%, the PBI content is 84.15 wt%, and the LGO content is 1 wt%).
(3) Same as in example 1.
The ADL of the membrane material is 8.70 by test, and the ion conductivity is 9.26 multiplied by 10 at 180 DEG C-2S/cm, 7.20X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 77.8%, the transverse swelling rate after phosphoric acid doping is 22.4%, and the tensile strength is 8.0 MPa.
Example 5
(1) Same as in example 4.
(2) Similar to example 4, except that the addition amount of LGO/DMAc dispersion was adjusted to 78mL, a phosphonic acid-modified graphite oxide crosslinked PAA-grafted PBI composite film material was obtained, in which the PAA content was 14.7 wt%, the amino group-terminated PBI content was 83.3 wt%, and the LGO content was 2 wt%.
(3) Same as in example 1.
The ADL of the membrane material is 8.31, and the ion conductivity is 10.25 multiplied by 10 measured at 180 DEG C-2S/cm, 8.22X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 80.2%, the transverse swelling rate after phosphoric acid doping is 19.8%, and the tensile strength is 8.4 MPa.
Example 6
(1) Same as in example 4.
(2) Similar to example 4, except that the addition amount of LGO/DMAc dispersion was adjusted to 119mL, a phosphonic acid-modified graphite oxide crosslinked PAA-grafted PBI composite film material was obtained, in which the PAA content was 14.55 wt%, the amino group-terminated PBI content was 82.45 wt%, and the LGO content was 3 wt%.
(3) Same as in example 1.
The ADL of the membrane material is 8.01 by testing, and the ion conductivity is 9.44 multiplied by 10 at 180 DEG C-2S/cm, 8.21X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 86.9 percent, the transverse swelling rate after phosphoric acid doping is 14.7 percent, and the tensile strength is 9.1 MPa.
Example 7
(1) Same as in example 4.
(2) Similar to example 4, except that the addition amount of LGO/DMAc dispersion was adjusted to 160mL, a phosphonic acid-modified graphite oxide crosslinked PAA-grafted PBI composite film material was obtained, in which the PAA content was 14.4 wt%, the amino group-terminated PBI content was 81.6 wt%, and the LGO content was 4 wt%.
(3) Same as in example 4.
The ADL of the membrane material is 7.70 by testing, and the ion conductivity is 8.51 multiplied by 10 at 180 DEG C-2S/cm, after 10 times of deionized water immersion, 7.56 is multiplied by 10-2S/cm, the conductivity retention rate is 88.9 percent, the transverse swelling rate after phosphoric acid doping is 10.3 percent, and the tensile strength is 10.0 MPa.
Example 8
(1) Same as in example 4.
(2) Similar to example 4, except that the addition amount of LGO/DMAc dispersion was adjusted to 202mL, a phosphonic acid-modified graphite oxide crosslinked PAA-grafted PBI composite film material was obtained, in which the PAA content was 14.25 wt%, the amino group-terminated PBI content was 80.75 wt%, and the LGO content was 5 wt%.
(3) Same as in example 4.
The ADL of the membrane material is 7.40, and the ion conductivity is 7.82 multiplied by 10 at 180 DEG C-2S/cm, 7.16X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 91.6 percent, the transverse swelling rate after phosphoric acid doping is 6.9 percent, and the tensile strength is 11.4 MPa.
Example 9
(1) Same as in example 4.
(2) LGO/DMAc dispersion (29mL) and 57.6g of 10 wt% double-end amino-containing poly [2,6- (p-phenylene) -phenybiimidazole ] (molecular weight of 250kDa)/DMAc solution are mixed and stirred uniformly, then the mixture is reacted for 4h at 150 ℃, 14.4g of 10 wt% PAA/DMAc solution is added, the reaction is continued for 8h, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 14.85 wt%, the poly [2,6- (p-phenylene) -phenybiimidazole ] content is 84.15 wt%, and the LGO content is 1 wt%).
(3) Same as in example 4.
The ADL of the membrane material is 8.89, and the ion conductivity is 9.07 x 10 at 180 DEG C-2S/cm, 7.24X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 79.9 percent, the transverse swelling rate after phosphoric acid doping is 24.6 percent, and the tensile strength is 8.3 MPa.
Example 10
(1) Same as in example 4.
(2) LGO/DMAc dispersion (59mL) and 57.6g of 10 wt% double-end amino-containing poly [2,6- (p-phenylene) -phenybiimidazole ] (molecular weight of 250kDa)/DMAc solution are mixed and stirred uniformly, then the mixture is reacted for 4h at 150 ℃, 14.4g of 10 wt% PAA/DMAc solution is added, the reaction is continued for 8h, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at 80 ℃ to obtain the phosphonic acid modified graphite oxide crosslinked PAA grafted PBI composite film material (wherein the PAA content is 14.7 wt%, the poly [2,6- (p-phenylene) -phenybiimidazole ] content is 83.3 wt%, and the LGO content is 2 wt%).
(3) Same as in example 4.
The ADL of the membrane material is 8.59, and the ion conductivity is 9.70 multiplied by 10 at 180 DEG C-2S/cm, 7.92 multiplied by 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 71.7%, the transverse swelling rate after phosphoric acid doping is 23.8%, and the tensile strength is 8.8 MPa.
Comparative example 1
And (2) uniformly mixing and stirring 5 wt% of PBI/DMAc solution containing double-ended amino, and then introducing the mixture into a glass culture dish to volatilize the solvent at 80 ℃ to obtain the PBI film material. And (3) soaking the PBI film material in 85% phosphoric acid for 12h, standing, and permeating the phosphoric acid to obtain the PBI proton exchange membrane material.
The ADL of the membrane material is 11.53, and the ion conductivity of the membrane material is 7.200 multiplied by 10 measured at 180 DEG C-2S/cm, 5.02X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 69.7%, the transverse swelling rate after phosphoric acid doping is 25.6%, and the tensile strength is 8.1 MPa.
Comparative example 2
Uniformly mixing and stirring a 5 wt% poly [2,6- (p-phenylene) -phenmedic imidazole ]/DMAc solution, and then introducing the solution into a glass culture dish to volatilize a solvent at 80 ℃ to obtain the poly [2,6- (p-phenylene) -phenmedic imidazole ] film material. And (3) soaking the poly [2,6- (p-phenylene) -phenmedic benzimidazole ] membrane material in 85% phosphoric acid for 12h, standing, and permeating the phosphoric acid to obtain the poly [2,6- (p-phenylene) -phenmedic benzimidazole ] proton exchange membrane material.
The ADL of the membrane material is 11.87 by testing, and the ion conductivity is 7.313 multiplied by 10 at 180 DEG C-2S/cm, 5.031 multiplied by 10 times of deionized water immersion after 10 times of deionized water immersion-2S/cm, conductivity retention rate of 68.8%, transverse swelling rate of 26.1% after phosphoric acid doping, and tensile strength of 8.5 MPa.
Comparative example 3
64.8g of PBI/DMAc solution containing amino-terminated groups with the concentration of 10 wt% (PBI molecular weight is 3.1kDa) and 7.2g of PAA/DMAc solution with the concentration of 10 wt% are mixed and stirred uniformly, the mixture reacts for 8 hours at the temperature of 150 ℃, and after the reaction is finished, the solution is placed in a culture dish to volatilize the solvent at the temperature of 80 ℃ to obtain the PAA grafted PBI composite film material.
The ADL of the membrane material is 9.26, and the ion conductivity is 8.33 multiplied by 10 at 180 DEG C-2S/cm, 6.07 x 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 72.9 percent, the transverse swelling rate after phosphoric acid doping is 25.8 percent, and the tensile strength is 7.4 MPa.
Comparative example 4
(1) GO was dispersed in DMAc to form a GO/DMAc dispersion at a concentration of 2.5 mg/mL.
(2) Mixing and stirring GO/DMAc dispersion (59mL) and 64.8g of PBI/DMAc solution containing amino double terminals in a concentration of 10 wt% (PBI molecular weight is 3.1kDa), then reacting at 150 ℃ for 4h, adding 7.2g of PAA/DMAc solution in a concentration of 10 wt%, continuing to react for 8h, putting the solution in a culture dish after the reaction is finished, and volatilizing the solvent at 80 ℃ to obtain the graphite oxide cross-linked PAA grafted PBI composite film material (wherein the PAA content is 9.8 wt%, the PBI content is 88.2 wt%, and the GO content is 2 wt%)
(3) Same as in example 1.
The ADL of the membrane material is 9.31, and the ion conductivity is 7.43 multiplied by 10 at 180 DEG C-2S/cm, 5.57X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 75.0%, the transverse swelling rate after phosphoric acid doping is 18.8%, and the tensile strength is 9.1 MPa.
Comparative example 5
(1) Same as in example 4
(2) 81.6g of PBI/DMAc solution containing single-terminal amino at a concentration of 10 wt% (PBI molecular weight is 70kDa) and 14.4g of PAA/DMAc solution at a concentration of 10 wt% are mixed uniformly and then reacted for 8h, then LGO/DMAc dispersion liquid (78mL) is added and mixed uniformly, and then the mixture is placed in a culture dish immediately to volatilize solvent at 80 ℃, so as to obtain the phosphonic acid modified graphite oxide doped and grafted PBI composite film material PAA (wherein the PAA content is 14.7 wt%, the PBI content is 83.3 wt%, and the LGO content is 2 wt%).
(3) Same as in example 1.
The ADL of the membrane material is 8.57, and the ion conductivity is 9.83 multiplied by 10 at 180 DEG C-2S/cm, 7.59X 10 times after 10 times of deionized water immersion-2S/cm, the conductivity retention rate is 77.2%, the transverse swelling rate after phosphoric acid doping is 22.1%, and the tensile strength is 7.6 MPa.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A phosphonic acid modified graphene oxide cross-linked polyolefin grafted benzimidazole polymer composite material comprises a polyolefin grafted benzimidazole polymer and phosphonic acid modified graphene oxide, wherein phosphonic acid in the phosphonic acid modified graphene oxide is selected from phosphonic acid compounds containing amino;
the structural formula of the phosphonic acid compound containing amino is NH2-R1-H2PO3(ii) a Wherein R is1Selected from substituted or unsubstituted arylene, substituted or unsubstituted alkylene, the substituent being selected from phosphonic acid group-H2PO3；
The polyolefin grafted benzimidazole polymer contains a structural unit shown as the following formula (1):
in the formula (1), R' is selected from H and alkyl; r' is selected from the group consisting of absent, substituted or unsubstituted arylene, substituted or unsubstituted alkylene, wherein the substituents are selected from the group consisting of alkyl, carboxyl, halogen; r is2Through two terminal amino groups (-NH)2) Benzimidazole polymer side chains connected to the olefin polymer main chain with carboxyl on the side chain after condensation reaction with-COOH on R';
m is an integer between 100 and 50000;
when R' is absent, z is 0, 1 is more than or equal to x1+ x2>0, and y is 1-x1-x 2; when R' is arylene or alkylene, 1> z ≧ 0, 1 ≧ x1+ x2>0, y ═ 1-z-x1-x 2;
Wherein, the meaning represented by the repeating unit with the polymerization degree of x1 is a high molecular chain segment which is subjected to crosslinking reaction with the phosphonic acid modified graphene oxide; the repeating unit with the polymerization degree of x2 represents a high-molecular chain segment which does not have a cross-linking reaction with the phosphonic acid modified graphene oxide.
2. The composite material according to claim 1, wherein the phosphonic acid-modified graphene oxide is grafted into the polyolefin-grafted benzimidazole polymer through an amide bond, and/or the phosphonic acid-modified graphene oxide is grafted into the polyolefin-grafted benzimidazole polymer through a secondary amine bond.
3. The composite material of claim 1, wherein the phosphonic acid modified graphene oxide is added in an amount of 1-5 wt% of the total mass of the composite material; the addition amount of the polyolefin grafted benzimidazole polymer is 95-99 wt% of the total mass of the composite material.
4. The composite material according to any one of claims 1 to 3, wherein the phosphonic acid is linked to the graphene oxide through an amide bond and/or the phosphonic acid is linked to the graphene oxide through a secondary amine bond.
5. The composite material of any one of claims 1-3, wherein R 2Is prepared from benzimidazole polymer containing terminal amino through two terminal amino (-NH)2) Benzimidazole polymer side chains connected to the olefin polymer main chain with carboxyl on the side chain after condensation reaction with-COOH on R'; the benzimidazole polymer containing the terminal amino contains a benzimidazole ring in a main chain structure, one end of the main chain structure also contains a benzene ring, and two adjacent terminal amino (-NH) are connected on the benzene ring2) The polymer of (1).
6. The composite material according to claim 5, wherein the benzimidazole polymer containing the terminal amino group is selected from at least one of the following structures of formula (2) or formula (3):
in the formulae (2) to (3), X is selected from,
-S-, -O-, halogen substituted or unsubstituted C1-6An alkylene group; r is selected from halogen substituted or unsubstituted C1-8Alkylene, halogen substituted or unsubstituted C6-20An arylene group; n is an integer between 10 and 5000.
7. The composite material according to claim 1, wherein the olefin-based polymer having carboxyl groups in side chains is selected from at least one of polyacrylic acid (PAA), polymethacrylic acid (PMAA), and carboxylated polystyrene.
8. A proton exchange membrane comprising the composite material of any one of claims 1-7.
9. The use of the proton exchange membrane of claim 8 in the field of fuel cells or flow batteries.
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