CN111635527A - Benzimidazole polymer cross-linking agent, and preparation method and application thereof - Google Patents
Benzimidazole polymer cross-linking agent, and preparation method and application thereof Download PDFInfo
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- CN111635527A CN111635527A CN202010448571.7A CN202010448571A CN111635527A CN 111635527 A CN111635527 A CN 111635527A CN 202010448571 A CN202010448571 A CN 202010448571A CN 111635527 A CN111635527 A CN 111635527A
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- benzimidazole
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- 239000003431 cross linking reagent Substances 0.000 title claims abstract description 57
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229920000642 polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012528 membrane Substances 0.000 claims abstract description 16
- 239000000446 fuel Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 20
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000944 Soxhlet extraction Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 12
- -1 dicarboxylic acid compound Chemical class 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- KSFAWAYSJUPRED-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetramine Chemical group NC1=C(N)C(N)=CC(C=2C=CC=CC=2)=C1N KSFAWAYSJUPRED-UHFFFAOYSA-N 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 7
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- XXXRZGXFFMAJKQ-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 XXXRZGXFFMAJKQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000004132 cross linking Methods 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 9
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 abstract description 2
- 239000004693 Polybenzimidazole Substances 0.000 description 97
- 229920002480 polybenzimidazole Polymers 0.000 description 97
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 4
- BYOBCYXURWDEDS-IUCAKERBSA-N (2s,3s)-2-amino-3-phenylmethoxybutanedioic acid Chemical compound OC(=O)[C@@H](N)[C@@H](C(O)=O)OCC1=CC=CC=C1 BYOBCYXURWDEDS-IUCAKERBSA-N 0.000 description 3
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- AGYSXPVGOQBEKA-UHFFFAOYSA-N 1h-benzimidazole;1,1'-biphenyl Chemical compound C1=CC=C2NC=NC2=C1.C1=CC=CC=C1C1=CC=CC=C1 AGYSXPVGOQBEKA-UHFFFAOYSA-N 0.000 description 2
- KLSIDTZOUQLHHU-UHFFFAOYSA-N 2h-1,3-oxazin-6-amine Chemical compound NC1=CC=NCO1 KLSIDTZOUQLHHU-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- JCUQWSIALJCIEE-UHFFFAOYSA-N 3,4-dichlorothiolane 1,1-dioxide Chemical compound ClC1CS(=O)(=O)CC1Cl JCUQWSIALJCIEE-UHFFFAOYSA-N 0.000 description 1
- HKGUGNAOSOYEJA-UHFFFAOYSA-N 3,5,5-trimethyl-1-(3-methylphenyl)cyclohexa-1,3-diene Chemical group CC1(CC(=CC(=C1)C)C1=CC=CC(=C1)C)C HKGUGNAOSOYEJA-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- PHQYMDAUTAXXFZ-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C=C1 PHQYMDAUTAXXFZ-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IXTGXVWLIBNABC-UHFFFAOYSA-N dichloromethylphosphonic acid Chemical compound OP(O)(=O)C(Cl)Cl IXTGXVWLIBNABC-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011345 viscous material Substances 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- Y02E60/30—Hydrogen technology
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Abstract
The invention belongs to the field of high-temperature proton exchange membranes for fuel cells, and discloses a benzimidazole polymer cross-linking agent and a preparation method thereof, wherein a benzimidazole structure is used as a framework, and benzoxazine in PBOA is used for end capping, so that the obtained benzimidazole polymer cross-linking agent can be cross-linked with PBI only by simple heating, and the mechanical strength and the chemical stability of the PBI can be greatly improved; meanwhile, the main chain structure of the cross-linking agent is consistent with that of PBI, so that sufficient thermal stability can be ensured; in addition, the molecular chain of the cross-linking agent is longer, the molecular chain movement is less hindered after cross-linking, and the content of imidazole units is not reduced, so that the acid doping amount of the cross-linked PBI film is not reduced, and the comprehensive performance of the cross-linked PBI film can be comprehensively improved. The invention also provides a cross-linked PBI film prepared by adopting the cross-linking agent and a preparation method thereof, and the prepared cross-linked PBI film has excellent comprehensive performance and can be applied to fuel cells as a high-temperature proton exchange membrane.
Description
Technical Field
The invention belongs to the technical field of high-temperature proton exchange membranes for fuel cells, and particularly relates to a benzimidazole polymer cross-linking agent, and a preparation method and application thereof.
Background
Polybenzimidazole (PBI) is a heterocyclic polymer containing benzimidazole repeating units on a main chain, and the main chain of a molecule of the Polybenzimidazole (PBI) has a trapezoidal structure and has good high-temperature resistance and mechanical properties, so that the PBI is one of the main materials of a proton exchange membrane for a high-temperature proton exchange membrane fuel cell at present, but because the PBI does not have proton conductivity, proton conductivity can be realized only after doping protonic acid (usually using phosphoric acid), and the higher the doping amount of the acid is, the higher the proton conductivity of the PBI/acid composite membrane is. However, the incorporation of acid greatly reduces the mechanical strength and thermal stability of the membrane, thereby limiting the application of PBI proton exchange membranes. Therefore, the PBI proton exchange membrane generally needs to be cross-linked to improve its mechanical strength, thermal stability and chemical stability, so as to improve its comprehensive performance after being doped with acid.
Because the nitrogen-hydrogen bond on the imidazole ring in the PBI is the position with the highest activity, the reaction of the nitrogen-hydrogen bond is commonly used in the prior art to realize crosslinking, and the commonly used crosslinking agent mainly comprises organic acid with bifunctional group or polyfunctional group or halide thereof, or other compounds capable of reacting with imidazole can be used as the crosslinking agent of the PBI, such as: p-dibromide benzyl, p-dichlorobenzyl, dichloromethylphosphonic acid, ethylene glycol diglycidyl ether, 4 '-diepoxy- (3,3,5, 5' -tetramethylbiphenyl), neopentyl glycol diglycidyl ether, bisphenol a type diepoxy ether resin, divinylsulfone, 3, 4-dichloro-1, 1-dioxo-tetrahydro-thiophene. The crosslinking agent of the above category can improve the mechanical strength and chemical stability of the PBI to a certain extent, but because the heat resistance and chemical resistance of the crosslinking agent are inferior to those of the PBI, the thermal stability of the PBI is greatly reduced after the crosslinking agent is crosslinked with the PBI. Meanwhile, due to the decrease of the content of the acidphilic structure (imidazole structure) and the limitation of the molecular chain movement, the acid doping amount of the PBI after the crosslinking is generally decreased, so that the comprehensive performances of the PBI after the acid doping, such as mechanical strength, thermal stability, chemical stability, proton conductivity and the like, still cannot be improved at the same time.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a benzimidazole polymer cross-linking agent, and a preparation method and application thereof.
In order to overcome the technical problems, the technical scheme adopted by the invention is as follows:
a benzimidazole-type polymer crosslinking agent having the structural formula:
wherein R is selected from one of an aliphatic chain structure or an aromatic chain structure, and n is an integer of 10-1000;
the fatty chain structure is
Wherein m is an integer of 2 to 12;
the aromatic chain structure is selected from any one of the following structures;
a method for preparing a benzimidazole-type polymer crosslinking agent as described above, comprising the steps of:
a. synthesis of carboxyl terminated benzimidazole oligomers: dissolving a tetra-aminobiphenyl and a dicarboxylic acid compound in polyphosphoric acid, carrying out heat preservation reaction at 160 ℃ under the protection of inert gas, heating to 210 ℃ under the protection of 190 ℃, adding phosphorus pentoxide and triphenyl phosphite, continuing the reaction for more than 10 hours, adding the obtained product into a precipitator to obtain a first precipitate, washing with an alkali solution and water in sequence, carrying out Soxhlet extraction, and drying to obtain a carboxyl-terminated benzimidazole oligomer;
b. synthesis of benzimidazole-type polymer cross-linking agent: and c, dissolving the carboxyl-terminated benzimidazole oligomer obtained in the step a in an organic solvent, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring, adding PBOA for reaction, adding the obtained product into a precipitator to obtain a second precipitate, and performing Soxhlet extraction and drying to obtain the benzimidazole polymer crosslinking agent.
Wherein the precipitating agent comprises water; the PBOA is 3-phenyl-3, 4-dihydro-2H-phenyl [ e ] [1,3] oxazine-6-amine, and the preparation process comprises the following steps:
synthesis of 2,2, 2-trifluoro-N- (4-hydroxyphenol) acetamide (THA): dissolving 1 part of p-aminophenol in a molar amount in tetrahydrofuran, stirring, placing in an ice bath for 15 minutes, dropwise adding 2 parts of trifluoroacetic anhydride within 30 minutes, continuously reacting in the ice bath for 1.5 hours, then carrying out rotary evaporation to remove a solvent, dissolving a residue in ethyl acetate, sequentially washing with a saturated sodium bicarbonate solution for 3 times, washing with water for 3 times, drying over night with anhydrous sodium sulfate, filtering, concentrating a solution by rotary evaporation, precipitating in cyclohexane, filtering, and drying a precipitate to obtain a pure product THA;
(ii) Synthesis of 2,2, 2-trifluoro-N- (3-phenyl-3, 4-dihydro-2H-phenyl [ e ] [1,3] oxazin-6-yl) acetamide (TBOA): dissolving 1 part of THA, 1 part of aniline and 3 parts of paraformaldehyde in dimethylbenzene, then reacting at 120 ℃ for 4 hours, cooling, pouring the solution into cyclohexane for precipitation, filtering, washing the cyclohexane for several times to obtain a crude product, dissolving the crude product in ethyl acetate, washing the crude product with 5 wt% of sodium carbonate solution for 3 times, washing the crude product with water for 3 times, drying the crude product with anhydrous sodium sulfate overnight, removing the solvent by rotary evaporation, and drying the product to obtain TBOA;
synthesis of 3-phenyl-3, 4-dihydro-2H-phenyl [ e ] [1,3] oxazin-6-amine (PBOA): a molar amount of 1 part of TBOA is dissolved in ethyl acetate: adding 5 parts of sodium borohydride into a 100:1 (volume) solution of methanol, stirring for 6 hours at 20 ℃ under the protection of nitrogen, washing the reaction solution with saline water for 1 time and 3 times in sequence, drying the reaction solution over anhydrous sodium sulfate overnight, filtering, and removing the solvent by rotary evaporation to obtain a colorless viscous substance PBOA.
As a further improvement of the above aspect, the dicarboxylic acid compound is at least one selected from the group consisting of isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4' -dicarboxydiphenyl ether, 2-bis (4-carboxyphenyl) hexafluoropropane, and sebacic acid.
As a further improvement of the above scheme, the organic solvent in step b is selected from one of N-methylpyrrolidone, N '-dimethylformamide and N, N' -dimethylacetamide.
As a further improvement of the above scheme, the molar ratio of the tetraaminobiphenyl to the dicarboxylic acid compound is 1 (1.001-2).
As a further improvement of the scheme, the mass ratio of the dicyclohexylcarbodiimide to the 4-dimethylaminopyridine to the PBOA is 5: 3: 14.
the cross-linked PBI is prepared by adopting the benzimidazole polymer cross-linking agent, and has a structural formula as follows:
wherein R is selected from one of an aliphatic chain structure or an aromatic chain structure, R1One selected from aliphatic chain structure or aromatic chain structure, n is an integer of 10-1000, x is an integer of 10-10000, and y is an integer of 10-10000;
the fatty chain structure is
Wherein m is an integer of 2 to 12;
the aromatic chain structure is selected from any one of the following structures;
a preparation method of a cross-linked PBI film comprises the following steps: dissolving PBI polymer powder in an organic solvent, adding the benzimidazole polymer cross-linking agent, stirring, filtering, heating the filtrate until the organic solvent is volatilized to obtain a solid film, and drying the solid film to obtain the cross-linked PBI film.
As a further improvement of the above scheme, the mass ratio of the benzimidazole polymer cross-linking agent to the PBI polymer powder is (1-80):100, and the organic solvent is one selected from N, N' -dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The preparation of the cross-linked PBI solid material can also be carried out by adopting a powder hot-pressing cross-linking method: crushing and screening the benzimidazole polymer cross-linking agent to obtain a powder product with 400 meshes, adding PBI polymer powder with 400 meshes obtained by screening, uniformly mixing, pouring into a mould, and carrying out hot pressing at the temperature of 120-200 ℃ for 1-12h to obtain the cross-linked PBI solid material, wherein the mass ratio of the benzimidazole polymer cross-linking agent to the PBI polymer powder is (1-80): 100.
The application of the cross-linked PBI is to prepare a high-temperature proton exchange membrane for a fuel cell.
The invention has the beneficial effects that: the invention provides a benzimidazole polymer cross-linking agent and a preparation method thereof, wherein a benzimidazole structure is taken as a framework, and benzoxazine in PBOA is used for end capping, so that the obtained benzimidazole polymer cross-linking agent can be cross-linked with PBI by simple heating, and the mechanical strength and the chemical stability of the PBI can be greatly improved; meanwhile, the main chain structure of the cross-linking agent is consistent with that of PBI, so that sufficient thermal stability can be ensured; in addition, the benzimidazole polymer cross-linking agent has longer molecular chain, the movement of the molecular chain is less hindered after cross-linking, and the content of imidazole units is not reduced, so the acid doping amount of the cross-linked PBI film can not be reduced, the benzimidazole polymer cross-linking agent can be effectively applied to the preparation of the cross-linked PBI film, the comprehensive performance of PBI is comprehensively improved, and the cross-linking agent is simple to use, convenient to store and wide in applicability. The invention also provides a cross-linked PBI film prepared by the cross-linking agent and a preparation method thereof, wherein the cross-linked PBI film is formed by cross-linking by a solution method, and the prepared cross-linked PBI film has excellent comprehensive properties such as mechanical strength, thermal stability, chemical stability, proton conductivity and the like, and can be applied to fuel cells as a high-temperature proton exchange membrane.
Drawings
FIG. 1 is a thermogravimetric plot of a cross-linked PBI film finished product 1 obtained in example 1 of the present invention and a pure PBI film prepared in comparative example 1, wherein a is the thermogravimetric plot of the pure PBI film, b is the thermogravimetric plot of PBI-Ben (15), and PBI-Ben (15) represents the cross-linked PBI film finished product 1 obtained in example 1, wherein the addition amount of the benzimidazole polymer cross-linking agent is 15% of the mass of PBI.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercially available products; the process steps or extraction methods not mentioned in detail are all process steps or extraction methods known to the person skilled in the art.
Example 1
90g of polyphosphoric acid is added into a three-neck flask, nitrogen is introduced, the temperature is raised to 150 ℃, 1.605g of tetraaminobiphenyl (7.5mmol) is added and dissolved in the polyphosphoric acid, 1.370g of isophthalic acid (8.25mmol) is added, the reaction is carried out for 30 minutes at 150 ℃ under the protection of inert gas, the temperature is raised to 200 ℃, 2.5g of phosphorus pentoxide and one drop of triphenyl phosphite are added, and the reaction is continued for 20 hours. After the reaction, the product was poured into deionized water to obtain a precipitate. And washing the precipitate with sodium hydroxide solution, washing with deionized water, performing Soxhlet extraction washing, and drying to obtain the carboxyl-terminated m-benzene benzimidazole oligomer with the repeating unit of about 10.
0.2g of the above carboxyl terminated benzimidazole oligomer was dissolved in 10mL of N-methylpyrrolidone, 0.05g of dicyclohexylcarbodiimide and 0.03g of 4-dimethylaminopyridine were added at 50 ℃ and stirred for 30 minutes, 0.14g of PBOA was added and the reaction was carried out for 24 hours. Then pouring the solution into water for precipitation, carrying out Soxhlet extraction on the precipitate, and drying to obtain the m-benzene benzimidazole cross-linking agent with the repeating unit of about 10.
Dissolving 1g of PBI in 9g N, N' -Dimethylformamide (DMF) to prepare a 10 wt% solution, adding 15% of PBI by mass of an m-benzene type benzimidazole cross-linking agent with a repeating unit of about 10, dissolving, filtering, pouring the obtained solution into a mold frame, heating at 120 ℃ until the solvent is volatilized to obtain a solid film, and continuously heating the solid film at 150 ℃ for 24h to obtain a cross-linked PBI film finished product 1.
Example 2
90g of polyphosphoric acid is added into a three-neck flask, nitrogen is introduced, the temperature is raised to 150 ℃, 1.605g of tetraaminobiphenyl (7.5mmol) is added and dissolved in the polyphosphoric acid, 1.257g of terephthalic acid (7.58mmol) is added, the reaction is carried out for 30 minutes at 150 ℃ under the protection of inert gas, the temperature is raised to 200 ℃, 2.5g of phosphorus pentoxide and one drop of triphenyl phosphite are added, and the reaction is continued for 20 hours. After the reaction, the product was poured into deionized water to obtain a precipitate. And washing the precipitate with sodium hydroxide solution, washing with deionized water, performing Soxhlet extraction washing, and drying to obtain the carboxyl-terminated p-benzene benzimidazole oligomer with the repeating unit of about 100.
2g of the above carboxyl-terminated benzimidazole oligomer was dissolved in 100mL of N-methylpyrrolidone, 0.05g of dicyclohexylcarbodiimide and 0.03g of 4-dimethylaminopyridine were added thereto at 50 ℃, and the mixture was stirred for 30 minutes, followed by addition of 0.14g of PBOA and reaction for 24 hours. Then pouring the solution into water for precipitation, carrying out Soxhlet extraction on the precipitate, and drying to obtain the p-benzene benzimidazole cross-linking agent with the repeating unit of about 100.
Dissolving 1.5g of PBI in 13.5g N-methyl pyrrolidone (NMP) to prepare a 15 wt% solution, adding a p-benzene benzimidazole cross-linking agent with a repeating unit of about 100 accounting for 15% of the weight of the PBI, dissolving, filtering, pouring the obtained solution into a mold frame, heating at 120 ℃ until the solvent is volatilized to obtain a solid film, and continuously heating the solid film at 150 ℃ for 24 hours to obtain a cross-linked PBI film finished product 2.
Example 3
90g of polyphosphoric acid is added into a three-neck flask, nitrogen is introduced, the temperature is raised to 150 ℃, 1.605g of tetraaminobiphenyl (7.5mmol) is added and dissolved in the polyphosphoric acid, 1.907g of 4,4' -biphenyldicarboxylic acid (7.875mmol) is added, the reaction is carried out for 30 minutes at 150 ℃ under the protection of inert gas, the temperature is raised to 200 ℃, 2.5g of phosphorus pentoxide and one drop of triphenyl phosphite are added, and the reaction is continued for 20 hours. After the reaction, the product was poured into deionized water to obtain a precipitate. And washing the precipitate with sodium hydroxide solution, washing with deionized water, performing Soxhlet extraction washing, and drying to obtain the carboxyl-terminated biphenyl benzimidazole oligomer with the repeating unit of about 20.
2g of the above carboxyl-terminated benzimidazole oligomer was dissolved in 100mL of N-methylpyrrolidone, 0.25g of dicyclohexylcarbodiimide and 0.15g of 4-dimethylaminopyridine were added thereto at 50 ℃, and the mixture was stirred for 30 minutes, followed by addition of 0.70g of PBOA and reaction for 24 hours. Then the solution is poured into water for precipitation, the precipitate is subjected to Soxhlet extraction, and the biphenyl benzimidazole cross-linking agent with the repeating unit of about 20 is obtained after drying.
Dissolving 1g of PBI in 19g N, N' -dimethylacetamide (DMAc) to prepare a 5 wt% solution, adding 15% of PBI by mass of a biphenyl type benzimidazole crosslinking agent with a repeating unit of about 20, dissolving, filtering, pouring the obtained solution into a mold, heating at 120 ℃ until the solvent is volatilized to obtain a solid film, and continuously heating the solid film at 150 ℃ for 24h to obtain a crosslinking type PBI film finished product 3.
Example 4
90g of polyphosphoric acid are placed in a three-necked flask, nitrogen is introduced, the temperature is raised to 150 ℃, 1.605g of tetraaminobiphenyl (7.5mmol) is added and dissolved in the polyphosphoric acid, 3.000g of 2, 2-bis (4-carboxyphenyl) hexafluoropropane (7.65mmol) are added and the reaction is carried out for 30 minutes at 150 ℃ under the protection of inert gas, the temperature is raised to 200 ℃ again, 2.5g of phosphorus pentoxide and a drop of triphenyl phosphite are added and the reaction is continued for 20 hours. After the reaction, the product was poured into deionized water to obtain a precipitate. And washing the precipitate with sodium hydroxide solution, washing with deionized water, performing Soxhlet extraction washing, and drying to obtain the carboxyl-terminated hexafluoropropane-containing benzimidazole oligomer with the repeating unit of about 50.
2g of the above carboxyl-terminated benzimidazole oligomer was dissolved in 100mL of N-methylpyrrolidone, 0.10g of dicyclohexylcarbodiimide and 0.06g of 4-dimethylaminopyridine were added thereto at 50 ℃ and stirred for 30 minutes, 0.28g of PBOA was added thereto and the reaction was carried out for 24 hours. Then the solution is poured into water for precipitation, the precipitate is subjected to Soxhlet extraction, and after drying, the benzimidazole cross-linking agent containing hexafluoropropane and with the repeating unit of about 50 is obtained.
Dissolving 1g of PBI in 24g N, N' -Dimethylformamide (DMF) to prepare a 4 wt% solution, adding 15% of PBI by mass of a hexafluoropropane-containing benzimidazole crosslinking agent with the repeating unit of about 50, dissolving, filtering, pouring the obtained solution into a mold frame, heating at 120 ℃ until the solvent is volatilized to obtain a solid film, and continuously heating the solid film at 150 ℃ for 24 hours to obtain a crosslinking type PBI film finished product 4.
Example 5
90g of polyphosphoric acid are added into a three-neck flask, nitrogen is introduced, the temperature is raised to 150 ℃, 1.605g of tetraaminobiphenyl (7.5mmol) is added and dissolved in the polyphosphoric acid, 1.985g of 4,4' -dicarboxydiphenyl ether (7.69mmol) is added, the reaction is carried out for 30 minutes at 150 ℃ under the protection of inert gas, the temperature is raised to 200 ℃, 2.5g of phosphorus pentoxide and one drop of triphenyl phosphite are added, and the reaction is continued for 20 hours. After the reaction, the product was poured into deionized water to obtain a precipitate. And washing the precipitate with sodium hydroxide solution, deionized water, Soxhlet extraction washing and drying to obtain the carboxyl-terminated phenylate type benzimidazole oligomer with the repeating unit of about 40.
2g of the above carboxyl-terminated benzimidazole oligomer was dissolved in 10mL of N-methylpyrrolidone, 0.125g of dicyclohexylcarbodiimide and 0.075g of 4-dimethylaminopyridine were added thereto at 50 ℃ and stirred for 30 minutes, and 0.35g of PBOA was added and reacted for 24 hours. The solution was then poured into water for precipitation, and the precipitate was subjected to Soxhlet extraction and dried to obtain a phenylene ether type benzimidazole crosslinking agent having a repeating unit of about 40.
Dissolving 1g of PBI in 7g N-methylpyrrolidone (NMP) to prepare a solution with the weight percent of 12.5, adding 15% of the PBI by mass of a phenylate type benzimidazole cross-linking agent with the repeating unit of about 40, dissolving, filtering, pouring the obtained solution into a mold frame, heating at 120 ℃ until the solvent is volatilized to obtain a solid film, and continuously heating the solid film at 150 ℃ for 24 hours to obtain a cross-linked PBI film finished product 5.
Comparative example 1
Comparative example 1 differs from example 1 in that comparative example 1 had no crosslinker added and gave a finished pure PBI film.
Example 6
The thermogravimetric detection of the cross-linked PBI film finished product 1 obtained in example 1 of the invention and the pure PBI film finished product prepared in comparative example 1 is carried out, the obtained thermogravimetric curves are shown in figure 1, a is the thermogravimetric curve of the pure PBI film, b is the thermogravimetric curve of PBI-Ben (15), PBI-Ben (15) represents the cross-linked PBI film finished product 1 obtained in example 1, wherein the addition amount of the benzimidazole polymer cross-linking agent is 15% of the PBI mass.
As can be seen from fig. 1, a clear degradation step appears near 510 ℃ in the finished pure PBI film, which is caused by the degradation of the PBI main chain, while a degradation step appears near 250 ℃ in the finished cross-linked PBI film 1, which is caused by the degradation of the chemical structure generated by the reaction of the benzoxazine units at the end of the cross-linking agent, and the weight loss caused by the degradation step is small because the benzoxazine units occupy a small proportion in the cross-linking agent, and the weight loss is related to the addition amount of the cross-linking agent. Meanwhile, the cross-linked PBI film finished product 1 has obvious degradation steps above 510 ℃, belongs to the degradation of a cross-linking agent and a PBI main chain, and is composed of benzimidazole repeating units, so that the thermal degradation temperature is higher, and the thermal stability of the cross-linked PBI film finished product 1 is still maintained at a higher level. The 5% and 10% weight loss temperatures for the pure PBI membranes were 555 ℃ and 587 ℃ respectively. The weight loss temperatures of 5% and 10% of the finished product 1 of the cross-linked PBI film obtained in example 1 are 526 ℃ and 570 ℃, respectively, and although the weight loss temperatures are slightly reduced compared with those of a pure PBI film, the cross-linked PBI film simultaneously has excellent mechanical strength, thermal stability, chemical stability, proton conductivity and the like, and the comprehensive performance reaches the current better level.
Example 7
Tensile property tests were performed on the cross-linked PBI film products 1 to 5 obtained in examples 1 to 5 and the pure PBI film prepared in comparative example 1, and the obtained test results of tensile strength, elongation at break, tensile modulus and the like are shown in Table 1 (the obtained test results are the average values of 6 tests).
TABLE 1 results of tensile properties and the like of the crosslinked PBI films obtained in examples 1 to 5 and the pure PBI film prepared in comparative example 1
As can be seen from Table 1, the tensile strength of the cross-linked PBI film products 1-5 obtained in examples 1-5 is greatly improved compared with that of the pure PBI film, which is beneficial to improving the resistance of the film to damage under the conditions of heating or acid doping, etc. The tensile elastic modulus of the cross-linked PBI film finished products 1-5 is improved to different degrees compared with that of a pure PBI film, and the elongation at break is increased along with the increase of the length of a cross-linking agent.
Example 8
The results of testing the tensile strength increase, the 5% weight loss temperature and the acid content increase of the cross-linked PBI film finished product 1 obtained in example 1 and the cross-linked PBI film finished products prepared in comparative examples 2 to 10 using different cross-linking agents are shown in Table 2. (the performance test values of the finished crosslinked PBI films of comparative examples 2-10 are all the best data obtained corresponding to the original text).
Wherein, the tensile strength increment and the acid doping amount increment are obtained by comparing on the basis of pure PBI film finished products; when the PBI membrane is used as a proton exchange membrane, the PBI membrane needs to be doped with acid, and the specific acid doping process comprises the following steps: soaking the PBI film in concentrated phosphoric acid for 48 hours at room temperature, taking out and drying, wherein the mass increment of the PBI film is the mass of the doped phosphoric acid; the acid doping amount and the acid doping amount increment respectively meet the following conditions:
table 2 Performance test results of the cross-linked PBI film finished products obtained by using different cross-linking agents in example 1 and comparative examples 2-10
As can be seen from Table 2, the tensile strength of the finished cross-linked PBI film 1 obtained in example 1 is increased by 74.4%, which is much higher than that of PBI films cross-linked by other cross-linking agents. The 5 percent weight loss temperature still reaches 526 ℃, is only slightly lower than 555 ℃ of a pure PBI film and is far higher than a PBI film product obtained by crosslinking other crosslinking agents. Because the molecular chain of the cross-linked PBI film finished product 1 is longer, the motion limit of the molecular chain is smaller after cross-linking, the content of the acidphilic unit (benzimidazole) in the molecular structure is higher, the increment of the acid doping amount reaches 49-65%, and the acid doping amount is at a higher level in the existing PBI film product. In conclusion, the combination property of the cross-linked PBI film finished product 1 obtained in the example 1 is obviously better than that of a PBI film obtained by cross-linking with other cross-linking agents.
It will be obvious to those skilled in the art that many simple derivations or substitutions can be made without inventive effort without departing from the inventive concept. Therefore, simple modifications to the present invention by those skilled in the art according to the present disclosure should be within the scope of the present invention. The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.
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Claims (10)
1. a benzimidazole-type polymer crosslinking agent, characterized in that the structural formula is:
the fatty chain structure is
Wherein m is an integer of 2 to 12;
the aromatic chain structure is selected from any one of the following structures;
2. a method of preparing the benzimidazole-based polymer crosslinker of claim 1, comprising the steps of:
a. synthesis of carboxyl terminated benzimidazole oligomers: dissolving a tetra-aminobiphenyl and a dicarboxylic acid compound in polyphosphoric acid, performing heat preservation reaction at 160 ℃ under the protection of inert gas, heating to 210 ℃ under the protection of inert gas, adding phosphorus pentoxide and triphenyl phosphite for continuous reaction, adding the obtained product into a precipitator to obtain a first precipitate, washing with an alkali solution and water in sequence, performing Soxhlet extraction, and drying to obtain a carboxyl-terminated benzimidazole oligomer;
b. synthesis of benzimidazole-type polymer cross-linking agent: and c, dissolving the carboxyl-terminated benzimidazole oligomer obtained in the step a in an organic solvent, adding dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stirring, adding PBOA for reaction, adding the obtained product into a precipitator to obtain a second precipitate, and performing Soxhlet extraction and drying to obtain the benzimidazole polymer crosslinking agent.
3. The production method according to claim 2, wherein the dicarboxylic acid compound is at least one selected from the group consisting of isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 4' -dicarboxydiphenyl ether, 2-bis (4-carboxyphenyl) hexafluoropropane, and sebacic acid.
4. The method according to claim 2, wherein the organic solvent in step b is one selected from the group consisting of N-methylpyrrolidone, N '-dimethylformamide and N, N' -dimethylacetamide.
5. The production method according to claim 2, wherein the molar ratio of tetraaminobiphenyl to the dicarboxylic acid compound is 1 (1.001-2).
6. The method according to claim 2, wherein the mass ratio of dicyclohexylcarbodiimide to 4-dimethylaminopyridine to PBOA is 5: 3: 14.
7. a cross-linked PBI characterized by the structural formula:
the fatty chain structure is
Wherein m is an integer of 2 to 12;
the aromatic chain structure is selected from any one of the following structures;
8. a preparation method of a cross-linked PBI film is characterized by comprising the following steps: dissolving PBI polymer powder in an organic solvent, adding the benzimidazole polymer cross-linking agent of claim 1, stirring, filtering, heating the filtrate until the organic solvent is volatilized to obtain a solid film, and drying the solid film to obtain the cross-linked PBI film.
9. The method according to claim 8, wherein the mass ratio of the benzimidazole-type polymer crosslinking agent to the PBI polymer powder is (1-80):100, and the organic solvent is one selected from N, N '-dimethylformamide, N' -dimethylacetamide, and N-methylpyrrolidone.
10. Use of the cross-linked PBI according to claim 7 for the preparation of a high temperature proton exchange membrane for a fuel cell.
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| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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| CN102585224A (en) * | 2012-03-16 | 2012-07-18 | 华中师范大学 | Polybenzimidazole high temperature resistant material and preparation method thereof |
| CN107556247A (en) * | 2017-08-28 | 2018-01-09 | 吉林大学 | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom |
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| CN102585224A (en) * | 2012-03-16 | 2012-07-18 | 华中师范大学 | Polybenzimidazole high temperature resistant material and preparation method thereof |
| CN107556247A (en) * | 2017-08-28 | 2018-01-09 | 吉林大学 | A kind of functional form crosslinking agent, preparation method and the phosphate-doped cross-linking type polybenzimidazoles film of height prepared therefrom |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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