CN107082996B - 氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 - Google Patents
氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 Download PDFInfo
- Publication number
- CN107082996B CN107082996B CN201710264556.5A CN201710264556A CN107082996B CN 107082996 B CN107082996 B CN 107082996B CN 201710264556 A CN201710264556 A CN 201710264556A CN 107082996 B CN107082996 B CN 107082996B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- parts
- interpenetrating network
- organic solvent
- polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000004642 Polyimide Substances 0.000 title claims abstract description 86
- 229920001721 polyimide Polymers 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 75
- 239000011347 resin Substances 0.000 claims abstract description 75
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 62
- 239000003960 organic solvent Substances 0.000 claims abstract description 61
- 150000004985 diamines Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 74
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000002791 soaking Methods 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 28
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 238000000944 Soxhlet extraction Methods 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000013557 residual solvent Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 229920000557 Nafion® Polymers 0.000 claims description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 claims description 4
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- ZBOLYDUBEGGDKS-UHFFFAOYSA-N 1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=C(Cl)C=C(C(O)=O)C2=C(C(O)=O)C=C(Cl)C=1C1=C(Cl)C=C(C(O)=O)C2=C1C3=C(Cl)C=C2C(=O)O ZBOLYDUBEGGDKS-UHFFFAOYSA-N 0.000 claims description 3
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- DSCIZKMHZPGBNI-UHFFFAOYSA-N naphthalene-1,3,5,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C2=CC(C(=O)O)=CC(C(O)=O)=C21 DSCIZKMHZPGBNI-UHFFFAOYSA-N 0.000 claims description 3
- OAXARSVKYJPDPA-UHFFFAOYSA-N tert-butyl 4-prop-2-ynylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(CC#C)CC1 OAXARSVKYJPDPA-UHFFFAOYSA-N 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- BTFWJAUZPQUVNZ-UHFFFAOYSA-N 1-methyl-3-[(3-methylphenyl)methyl]benzene Chemical compound CC1=CC=CC(CC=2C=C(C)C=CC=2)=C1 BTFWJAUZPQUVNZ-UHFFFAOYSA-N 0.000 claims description 2
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 2
- POLIXZIAIMAECK-UHFFFAOYSA-N 4-[2-(2,6-dioxomorpholin-4-yl)ethyl]morpholine-2,6-dione Chemical compound C1C(=O)OC(=O)CN1CCN1CC(=O)OC(=O)C1 POLIXZIAIMAECK-UHFFFAOYSA-N 0.000 claims description 2
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 claims description 2
- IOCXBXZBNOYTLQ-UHFFFAOYSA-N 3-nitrobenzene-1,2-diamine Chemical compound NC1=CC=CC([N+]([O-])=O)=C1N IOCXBXZBNOYTLQ-UHFFFAOYSA-N 0.000 claims 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007789 gas Substances 0.000 description 13
- 239000000446 fuel Substances 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 9
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- XAFOTXWPFVZQAZ-UHFFFAOYSA-N 2-(4-aminophenyl)-3h-benzimidazol-5-amine Chemical compound C1=CC(N)=CC=C1C1=NC2=CC=C(N)C=C2N1 XAFOTXWPFVZQAZ-UHFFFAOYSA-N 0.000 description 6
- -1 hexafluoro dianhydride Chemical compound 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; 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
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
-
- 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
- H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- 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
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Fuel Cell (AREA)
Abstract
本发明涉及氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备,所述的复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2‑9份、氧化石墨烯0.005‑0.05份以及有机溶剂20‑100份;所述的氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1‑1.3份以及催化剂0.8‑1.2份。与现有技术相比,本发明氧化石墨烯交联聚酰亚胺半互穿网络型复合膜较传统的全氟磺酸膜相比,力学强度高,尺寸稳定性好,制备工艺可控性好,原料来源广泛,工艺条件温和,可有效节约生产成本,具有很好的应用前景。
Description
技术领域
本发明属于功能高分子材料和电化学技术领域,涉及一种氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备。
背景技术
质子交换膜燃料电池(PEMFCs)是以质子交换膜为电解质的燃料电池,是五种燃料电池中的一种。它是目前世界上最成熟的一种能使氢气与空气中的氧气发生化学反应,生成水并能释放出电能的技术,具有能量效率高、排放低、环境友好等优点。作为燃料电池的核心,电解质的性质直接关系到燃料电池的发电效率、使用寿命等关键性能。而质子交换膜(PEM)的质子传导率、力学性能、尺寸稳定性对PEMFC的性能则有直接的影响。目前,全氟型质子交换膜(如)是市场上质子交换膜的主体,但是其价格的昂贵、机械强度和尺寸稳定性差以及燃料渗透率高等缺点限制了它的广泛应用。
聚酰亚胺具有优越的热、化学和机械稳定性以及低的气体渗透性,在微电子、膜分离等许多工业领域已经得到了广泛的关注,而这些优点也是在质子交换膜燃料电池中期待得到的。与无机掺杂材料不同,氧化石墨烯(GO)具有两亲性,与有机膜具有较好的相容性;同时,其还具有超高的比表面积、良好的电子绝缘性以及柔韧性,可有效地提高质子膜的化学、热及机械稳定性;而且由于氧化石墨烯中—O—,—OH及—COOH等亲水基团能吸引质子,它对质子传输显示出超导性,对质子传输有促进作用。因此,在质子交换膜中引入氧化石墨烯,不仅能提高质子膜的耐化学分解、耐热性,降低膜的燃料渗透性外,还能大幅提高质子膜的质子传导率。
申请号为201610053388.0的中国专利公开了一种低介电常数增强氧化石墨烯/聚酰亚胺复合膜的制备方法,该制备方法是在湿度低于50%、室温、机械搅拌和氮气气氛中,将芳香族二胺溶于极性有机溶剂中,加入由同一种极性有机溶剂配制的超支化聚酯‐氧化石墨烯溶液,得到超支化聚酯‐氧化石墨烯/二胺溶液;加入芳香族二酐,搅拌得到氧化石墨烯/聚酰胺酸溶液;均匀涂抹于洁净玻璃片上,放置于真空干燥箱中,消除气泡,程序升温和保温,冷却至室温,脱膜,真空干燥。上述专利技术中聚酰亚胺是通过两步法合成,且与氧化石墨烯原位制备复合膜。不同于上述专利,本发明中的聚酰亚胺是通过一步法预先合成,在成膜过程中加入氧化石墨烯为交联剂,氧化石墨烯中的活性基团可以与聚酰亚胺中的氨基以及咪唑基发生反应,并与全氟磺酸树脂形成含半互穿网络结构的增强型复合质子交换膜材料。制得的膜材料具有优异的力学性能、热稳定性和质子传导率,有望应用到质子交换膜燃料电池中。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种力学强度高,尺寸稳定性好,质子传导率高的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
本发明的另一个目的就是提供上述氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法。
本发明的目的可以通过以下技术方案来实现:
氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,该复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2-9份、氧化石墨烯0.005-0.05份以及有机溶剂20-100份。
所述的氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1-1.3份以及催化剂0.8-1.2份。
作为优选的技术方案,所述的氨基封端的聚酰亚胺中氨基的摩尔含量为5%-60%。
所述的二酐包括1,3,5,8-萘四甲酸二酐、均苯四甲酸二酐、3,4,9,10-苝四羧酸酐、4,4'-(六氟异丙烯)二酞酸酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、环丁烷四甲酸二酐、1,6,7,12-四氯-3,4,9,10-苝四甲酸二酐、双酚A型二醚二酐、1,2,3,4-环戊四羧酸二酐、乙二胺四乙酸二酐、2,3,3',4'-联苯四甲酸二酐、1,2,3,4-丁烷四羧酸二酐或2,3,3',4'-二苯醚四甲酸二酐中的一种或多种。
所述的二胺包括4,4'-二氨基二苯甲烷、4,4'-二氨基-3,3'-二甲基二苯甲烷、4,4'-二氨基-2,2',3,3'-二甲基二苯甲烷、4,4'-二氨基-2,2'-二甲基联苯、4,4'-二氨基-3,3'-二甲基联苯、4,4'-二氨基-2,2'-双三氟甲基联苯、2,6-二氨基-1,3,5-三甲苯、间苯二胺、4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、4,4'-二氨基-1”,3”-二苯氧基苯、3,3'-二氨基-1”,3”-二苯氧基苯、9,9'-双(4-氨基苯基)芴、4,4'-二氨基-4”,4”'-二苯氧基联苯、4,4'-二氨基-4”,4”'-二苯氧基-二苯基异丙烷或4,4'-二氨基-1”,4”-二苯氧基苯中的一种或多种。
所述的催化剂包括三乙胺、乙酸酐或苯甲酸中的一种或几种。
所述的全氟磺酸树脂膜选自市售的Nafion膜。
所述的氧化石墨烯为1-3层的氧化石墨烯。
所述的有机溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮中的一种或多种。
氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,该方法具体包括以下步骤:
步骤(1):按以下组分及摩尔份含量进行备料:二酐1份、二胺1-1.3份以及催化剂0.8-1.2份;
步骤(2):于反应容器中加入有机溶剂和二胺,通入惰性气体,搅拌,待二胺完全溶解后,再加入二酐和催化剂,进行聚合反应,待反应结束后,将产物缓慢加入到丙酮中沉淀,并将沉淀用丙酮进行索式提取,除去残余溶剂、催化剂及小分子量物质,再将产物进行真空干燥,即制得氨基封端的聚酰亚胺;
步骤(3):将步骤(2)制得的氨基封端的聚酰亚胺与全氟磺酸树脂膜、氧化石墨烯、有机溶剂按以下重量份含量进行备料:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2-9份、氧化石墨烯0.005-0.05份以及有机溶剂20-100份;
步骤(4):将全氟磺酸树脂膜浸泡于碱性溶液中,22-26小时后取出,烘干至恒重,再于140-180℃下溶解在一部分有机溶剂中,制得全氟磺酸树脂有机溶液;
步骤(5):将氨基封端的聚酰亚胺溶解在剩余的有机溶剂中,于室温下与步骤(4)制得的全氟磺酸树脂有机溶液混合,再加入氧化石墨烯,搅拌均匀,制得成膜溶液;
步骤(6):将成膜溶液于75-90℃下浇铸在膜框中,保温4-8小时,再升温至140-180℃,使得交联反应进行完全,冷却后,将成膜依次浸泡于去离子水、醇中,再于50-70℃下烘干,即制得含半互穿网络结构的复合膜;
步骤(7):将步骤(6)制得的含半互穿网络结构的复合膜于稀盐酸溶液中浸泡12-48小时,取出水洗,烘干至恒重,即制得所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
步骤(2)中所述的聚合反应的条件为:升温至75-85℃,反应3-5小时,之后升温使溶剂回流,反应12-20小时,反应结束后,降温至95-105℃;
步骤(4)中全氟磺酸树脂膜与有机溶剂的用量关系为:每50ml有机溶剂中全氟磺酸树脂膜的加入量为0.5-5g;
步骤(5)中氨基封端的聚酰亚胺在有机溶剂中的质量百分含量为2-5%;
步骤(4)中有机溶剂与步骤(5)中有机溶剂的质量比为1-5:5-9;
步骤(7)中稀盐酸溶液为质量百分含量为8-10%的稀盐酸溶液。
本发明技术方案的设计思路是在全氟磺酸树脂溶液中,加入氨基封端的聚酰亚胺、氧化石墨烯,在成膜过程中,利用端基氨基与氧化石墨烯中活泼基团(羧酸基团、羟基等)发生反应,使其在成膜过程中交联,并与全氟磺酸树脂的分子主链形成半互穿网络结构,进而制得氧化石墨烯交联聚酰亚胺的半互穿网络型复合膜。
在实际制备过程中,首先合成不同端氨基含量的聚酰亚胺,将其配制成溶液,在其溶液中加入全氟磺酸树脂和氧化石墨烯,溶解分散均匀后,在成膜过程中聚酰亚胺的端氨基与氧化石墨烯中的活性基团发生交联反应,并与全氟磺酸树脂的分子主链形成半互穿网络结构,即制得所述的复合膜。
与现有技术相比,本发明具有以下特点:
1)本发明在聚酰亚胺聚合物主链上引入氨基端基,然后与全氟磺酸树脂的溶液共混,再使用氧化石墨烯作为交联剂使其与聚酰亚胺交联,可以显著提高全氟磺酸膜的力学性能并仍具有较高的质子传导率;
2)本发明制得的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜较传统的全氟磺酸膜相比,力学强度高,尺寸稳定性好,在聚合物电解质膜燃料电池中具有广阔的应用前景;
3)制备工艺可控性好,原料来源广泛,工艺条件温和,可有效节约生产成本,具有很好的应用前景。
附图说明
图1是基于半互穿网络结构的氧化石墨烯交联聚酰亚胺增强Nafion质子交换膜的拉伸强度,其中Nafion-PI-20-1是Nafion:PI-X质量比为9:1,PI中氨基的摩尔含量为20%,氧化石墨烯的含量分别为1.0%;Nafion-PI-40-1是Nafion:PI-X质量比为9:1,PI中氨基的摩尔含量为40%,氧化石墨烯的含量分别为1.0%;Nafion-PI-60-1是Nafion:PI-X质量比为9:1,PI中氨基的摩尔含量为60%,氧化石墨烯的含量分别为1.0%
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1:
本实施例所用原料的配比如下:
PI-60 1份(质量数)
氧化石墨烯 0.005份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.7438g 2-(4-氨基苯基)-5-氨基苯并咪唑(APBIA),连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐(6FDA),2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.9g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于18mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.1g溶解于2mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入0.25mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例2:
本实施例所用原料的配比如下:
PI-40 1份(质量数)
氧化石墨烯 0.01份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.7212g2-(4-氨基苯基)-5-氨基苯并咪唑,连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐,2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.9g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于18mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.1g溶解于2mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入0.50mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例3:
本实施例所用原料的配比如下:
PI-20 2份(质量数)
氧化石墨烯 0.02份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.6987g2-(4-氨基苯基)-5-氨基苯并咪唑,连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐,2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.8g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于16mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.2g溶解于4mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入2.0mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例4:
本实施例所用原料的配比如下:
PI-10 3份(质量数)
氧化石墨烯 0.03份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.6874g2-(4-氨基苯基)-5-氨基苯并咪唑,连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐,2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.7g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于14mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.3g溶解于6mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入4.5mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例5:
本实施例所用原料的配比如下:
PI-30 4份(质量数)
氧化石墨烯 0.04份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.7100g2-(4-氨基苯基)-5-氨基苯并咪唑,连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐,2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.6g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于12mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.4g溶解于8mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入4.5mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例6:
本实施例所用原料的配比如下:
PI-50 5份(质量数)
氧化石墨烯 0.05份(质量数)
(1)在完全干燥的三口烧瓶中加入12mLN-甲基吡咯烷酮(NMP)和0.7325g2-(4-氨基苯基)-5-氨基苯并咪唑,连接气体入口、干燥管、气体出口和机械搅拌器,通入惰性气体并开始搅拌,当二胺完全溶解后,加入1.3599g六氟二酐,2.4mL乙酸酐和3.6mL三乙胺。常温搅拌24h,反应结束后,将产物缓慢倒入丙酮中沉淀,将沉淀用丙酮进行索式提取除去残余溶剂、催化剂和小分子量物质,之后将产物在真空烘相中60℃条件下烘干备用;
(2)将0.5g全氟磺酸树脂浸泡在质量浓度为10%的氢氧化钠溶液中,24小时后取出烘干至恒重,然后在160℃下溶解于10mL N,N-二甲基乙酰胺中,形成均匀溶液。
(3)将(1)中所得的聚合物0.5g溶解于10mL N,N-二甲基乙酰胺中,室温下与步骤(2)所得全氟磺酸树脂溶液混合,加入12.5mL的2mg/mL氧化石墨烯溶液,搅拌得到均匀溶液;将膜液在80℃时浇铸在10cm×10cm的膜框中,保温6h,再升温至150℃使得交联反应进行完全,再将所得到的膜用去离子水浸泡24h,取出后再用甲醇浸泡24h,最后将膜在60℃条件下烘干,制得含半互穿网络结构的复合膜膜;
(4)将步骤(3)所得复合膜浸泡在质量浓度为10%的稀盐酸溶液中浸泡24小时后,取出水洗并烘干至恒重,即得到所需产品。
实施例7:
本实施例所用原料的配比如下:
PI-20 1份(质量数)
氧化石墨烯 0.01份(质量数)
其余同实施例2。
实施例8:
本实施例所用原料的配比如下:
PI-60 1份(质量数)
氧化石墨烯 0.01份(质量数)
其余同实施例2。
实施例9:
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2份、氧化石墨烯0.005份以及有机溶剂20份。
其中,氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1份以及催化剂0.8份。氨基封端的聚酰亚胺中氨基的摩尔含量为60%。
本实施例中,二酐由1,3,5,8-萘四甲酸二酐、环丁烷四甲酸二酐及1,6,7,12-四氯-3,4,9,10-苝四甲酸二酐按摩尔比为1:1:2混合而成;二胺由2,6-二氨基-1,3,5-三甲苯、4,4'-二氨基-2,2'-双三氟甲基联苯按质量比为1:1混合而成;催化剂为苯甲酸。
全氟磺酸树脂膜选自市售的Nafion膜;氧化石墨烯为1层的氧化石墨烯;有机溶剂由N,N-二甲基甲酰胺与二甲基亚砜按体积比为1:1混合而成。
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,具体包括以下步骤:
步骤(1):按以下组分及摩尔份含量进行备料:二酐1份、二胺1份以及催化剂0.8份;
步骤(2):于反应容器中加入有机溶剂和二胺,通入惰性气体,搅拌,待二胺完全溶解后,再加入二酐和催化剂,进行聚合反应,待反应结束后,将产物缓慢加入到丙酮中沉淀,并将沉淀用丙酮进行索式提取,除去残余溶剂、催化剂及小分子量物质,再将产物进行真空干燥,即制得氨基封端的聚酰亚胺;
步骤(3):将步骤(2)制得的氨基封端的聚酰亚胺与全氟磺酸树脂膜、氧化石墨烯、有机溶剂按以下重量份含量进行备料:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2份、氧化石墨烯0.005份以及有机溶剂20份;
步骤(4):将全氟磺酸树脂膜浸泡于碱性溶液中,22小时后取出,烘干至恒重,再于140℃下溶解在一部分有机溶剂中,制得全氟磺酸树脂有机溶液;
步骤(5):将氨基封端的聚酰亚胺溶解在剩余的有机溶剂中,于室温下与步骤(4)制得的全氟磺酸树脂有机溶液混合,再加入氧化石墨烯,搅拌均匀,制得成膜溶液;
步骤(6):将成膜溶液于75℃下浇铸在膜框中,保温8小时,再升温至140℃,使得交联反应进行完全,冷却后,将成膜依次浸泡于去离子水、醇中,再于50℃下烘干,即制得含半互穿网络结构的复合膜;
步骤(7):将步骤(6)制得的含半互穿网络结构的复合膜于稀盐酸溶液中浸泡12小时,取出水洗,烘干至恒重,即制得所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
步骤(2)中聚合反应的条件为:升温至75℃,反应5小时,之后升温使溶剂回流,反应12小时,反应结束后,降温至95℃;
步骤(4)中全氟磺酸树脂膜与有机溶剂的用量关系为:每50ml有机溶剂中全氟磺酸树脂膜的加入量为0.5g;
步骤(5)中氨基封端的聚酰亚胺在有机溶剂中的质量百分含量为2%;
步骤(4)中有机溶剂与步骤(5)中有机溶剂的质量比为1:6;
步骤(7)中稀盐酸溶液为质量百分含量为8%的稀盐酸溶液。
实施例10:
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜9份、氧化石墨烯0.05份以及有机溶剂100份。
其中,氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1.3份以及催化剂1.2份。氨基封端的聚酰亚胺中氨基的摩尔含量为5%。
本实施例中,二酐由2,3,3',4'-二苯醚四甲酸二酐、4,4'-(六氟异丙烯)二酞酸酐及2,3,3',4'-联苯四甲酸二酐按摩尔比为1:1:1混合而成;二胺由4,4'-二氨基-3,3'-二甲基二苯甲烷、3,3'-二氨基-1”,3”-二苯氧基苯按质量比为1:2混合而成;催化剂为乙酸酐。
全氟磺酸树脂膜选自市售的Nafion膜;氧化石墨烯为3层的氧化石墨烯;有机溶剂由N,N-二甲基甲酰胺、N-甲基吡咯烷酮与二甲基亚砜按体积比为1:1:3混合而成。
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,具体包括以下步骤:
步骤(1):按以下组分及摩尔份含量进行备料:二酐1份、二胺1.3份以及催化剂1.2份;
步骤(2):于反应容器中加入有机溶剂和二胺,通入惰性气体,搅拌,待二胺完全溶解后,再加入二酐和催化剂,进行聚合反应,待反应结束后,将产物缓慢加入到丙酮中沉淀,并将沉淀用丙酮进行索式提取,除去残余溶剂、催化剂及小分子量物质,再将产物进行真空干燥,即制得氨基封端的聚酰亚胺;
步骤(3):将步骤(2)制得的氨基封端的聚酰亚胺与全氟磺酸树脂膜、氧化石墨烯、有机溶剂按以下重量份含量进行备料:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜9份、氧化石墨烯0.05份以及有机溶剂100份;
步骤(4):将全氟磺酸树脂膜浸泡于碱性溶液中,26小时后取出,烘干至恒重,再于180℃下溶解在一部分有机溶剂中,制得全氟磺酸树脂有机溶液;
步骤(5):将氨基封端的聚酰亚胺溶解在剩余的有机溶剂中,于室温下与步骤(4)制得的全氟磺酸树脂有机溶液混合,再加入氧化石墨烯,搅拌均匀,制得成膜溶液;
步骤(6):将成膜溶液于90℃下浇铸在膜框中,保温4小时,再升温至180℃,使得交联反应进行完全,冷却后,将成膜依次浸泡于去离子水、醇中,再于70℃下烘干,即制得含半互穿网络结构的复合膜;
步骤(7):将步骤(6)制得的含半互穿网络结构的复合膜于稀盐酸溶液中浸泡48小时,取出水洗,烘干至恒重,即制得所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
步骤(2)中聚合反应的条件为:升温至85℃,反应3小时,之后升温使溶剂回流,反应20小时,反应结束后,降温至105℃;
步骤(4)中全氟磺酸树脂膜与有机溶剂的用量关系为:每50ml有机溶剂中全氟磺酸树脂膜的加入量为5g;
步骤(5)中氨基封端的聚酰亚胺在有机溶剂中的质量百分含量为5%;
步骤(4)中有机溶剂与步骤(5)中有机溶剂的质量比为3:7;
步骤(7)中稀盐酸溶液为质量百分含量为10%的稀盐酸溶液。
实施例11:
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜6份、氧化石墨烯0.02份以及有机溶剂35份。
其中,氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1.2份以及催化剂1.0份。氨基封端的聚酰亚胺中氨基的摩尔含量为20%。
本实施例中,二酐由环丁烷四甲酸二酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐及2,3,3',4'-联苯四甲酸二酐按摩尔比为1:1:1混合而成;二胺由4,4'-二氨基-3,3'-二甲基联苯、3,3'-二氨基-1”,3”-二苯氧基苯按质量比为1:2混合而成;催化剂为苯甲酸。
全氟磺酸树脂膜选自市售的Nafion膜;氧化石墨烯为2层的氧化石墨烯;有机溶剂由N,N-二甲基甲酰胺、N-甲基吡咯烷酮与二甲基亚砜按体积比为1:1:3混合而成。
本实施例氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,具体包括以下步骤:
步骤(1):按以下组分及摩尔份含量进行备料:二酐1份、二胺1.2份以及催化剂1.0份;
步骤(2):于反应容器中加入有机溶剂和二胺,通入惰性气体,搅拌,待二胺完全溶解后,再加入二酐和催化剂,进行聚合反应,待反应结束后,将产物缓慢加入到丙酮中沉淀,并将沉淀用丙酮进行索式提取,除去残余溶剂、催化剂及小分子量物质,再将产物进行真空干燥,即制得氨基封端的聚酰亚胺;
步骤(3):将步骤(2)制得的氨基封端的聚酰亚胺与全氟磺酸树脂膜、氧化石墨烯、有机溶剂按以下重量份含量进行备料:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜6份、氧化石墨烯0.02份以及有机溶剂35份;
步骤(4):将全氟磺酸树脂膜浸泡于碱性溶液中,24小时后取出,烘干至恒重,再于150℃下溶解在一部分有机溶剂中,制得全氟磺酸树脂有机溶液;
步骤(5):将氨基封端的聚酰亚胺溶解在剩余的有机溶剂中,于室温下与步骤(4)制得的全氟磺酸树脂有机溶液混合,再加入氧化石墨烯,搅拌均匀,制得成膜溶液;
步骤(6):将成膜溶液于82℃下浇铸在膜框中,保温5小时,再升温至150℃,使得交联反应进行完全,冷却后,将成膜依次浸泡于去离子水、醇中,再于60℃下烘干,即制得含半互穿网络结构的复合膜;
步骤(7):将步骤(6)制得的含半互穿网络结构的复合膜于稀盐酸溶液中浸泡48小时,取出水洗,烘干至恒重,即制得所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
步骤(2)中聚合反应的条件为:升温至85℃,反应3小时,之后升温使溶剂回流,反应20小时,反应结束后,降温至105℃;
步骤(4)中全氟磺酸树脂膜与有机溶剂的用量关系为:每50ml有机溶剂中全氟磺酸树脂膜的加入量为5g;
步骤(5)中氨基封端的聚酰亚胺在有机溶剂中的质量百分含量为5%;
步骤(4)中有机溶剂与步骤(5)中有机溶剂的质量比为4:9;
步骤(7)中稀盐酸溶液为质量百分含量为9%的稀盐酸溶液。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (10)
1.氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,该复合膜由包括以下重量份含量的组分制备而成:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜9份、氧化石墨烯0.01份以及有机溶剂20-100份,其中,所述的氨基封端的聚酰亚胺的氨基摩尔含量为40%。
2.根据权利要求1所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的氨基封端的聚酰亚胺包括以下组分及摩尔份含量:二酐1份、二胺1-1.3份以及催化剂0.8-1.2份。
3.根据权利要求2所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的二酐包括1,3,5,8-萘四甲酸二酐、均苯四甲酸二酐、3,4,9,10-苝四羧酸酐、4,4'-(六氟异丙烯)二酞酸酐、双环[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、3,3',4,4'-联苯四羧酸二酐、3,3',4,4'-二苯甲酮四甲酸二酐、环丁烷四甲酸二酐、1,6,7,12-四氯-3,4,9,10-苝四甲酸二酐、双酚A型二醚二酐、1,2,3,4-环戊四羧酸二酐、乙二胺四乙酸二酐、2,3,3',4'-联苯四甲酸二酐、1,2,3,4-丁烷四羧酸二酐或2,3,3',4'-二苯醚四甲酸二酐中的一种或多种。
4.根据权利要求2所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的二胺包括4,4'-二氨基二苯甲烷、4,4'-二氨基-3,3'-二甲基二苯甲烷、4,4'-二氨基-2,2',3,3'-二甲基二苯甲烷、4,4'-二氨基-2,2'-二甲基联苯、4,4'-二氨基-3,3'-二甲基联苯、4,4'-二氨基-2,2'-双三氟甲基联苯、2,6-二氨基-1,3,5-三甲苯、间苯二胺、4,4'-二氨基二苯醚、3,4'-二氨基二苯醚、4,4'-二氨基-1”,3”-二苯氧基苯、3,3'-二氨基-1”,3”-二苯氧基苯、9,9'-双(4-氨基苯基)芴、4,4'-二氨基-4”,4”'-二苯氧基联苯、4,4'-二氨基-4”,4”'-二苯氧基-二苯基异丙烷或4,4'-二氨基-1”,4”-二苯氧基苯中的一种或多种。
5.根据权利要求2所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的催化剂包括三乙胺、乙酸酐或苯甲酸中的一种或几种。
6.根据权利要求1所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的全氟磺酸树脂膜选自市售的Nafion膜。
7.根据权利要求1所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的氧化石墨烯为1-3层的氧化石墨烯。
8.根据权利要求1所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜,其特征在于,所述的有机溶剂包括N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜或N-甲基吡咯烷酮中的一种或多种。
9.如权利要求2至8任一项所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,其特征在于,该方法具体包括以下步骤:
步骤(1):按以下组分及摩尔份含量进行备料:二酐1份、二胺1-1.3份以及催化剂0.8-1.2份;
步骤(2):于反应容器中加入有机溶剂和二胺,通入惰性气体,搅拌,待二胺完全溶解后,再加入二酐和催化剂,进行聚合反应,待反应结束后,将产物缓慢加入到丙酮中沉淀,并将沉淀用丙酮进行索式提取,除去残余溶剂、催化剂及小分子量物质,再将产物进行真空干燥,即制得氨基封端的聚酰亚胺;
步骤(3):将步骤(2)制得的氨基封端的聚酰亚胺与全氟磺酸树脂膜、氧化石墨烯、有机溶剂按以下重量份含量进行备料:氨基封端的聚酰亚胺1份、全氟磺酸树脂膜0.2-9份、氧化石墨烯0.005-0.05份以及有机溶剂20-100份;
步骤(4):将全氟磺酸树脂膜浸泡于碱性溶液中,22-26小时后取出,烘干至恒重,再于140-180℃下溶解在一部分有机溶剂中,制得全氟磺酸树脂有机溶液;
步骤(5):将氨基封端的聚酰亚胺溶解在剩余的有机溶剂中,于室温下与步骤(4)制得的全氟磺酸树脂有机溶液混合,再加入氧化石墨烯,搅拌均匀,制得成膜溶液;
步骤(6):将成膜溶液于75-90℃下浇铸在膜框中,保温4-8小时,再升温至140-180℃,使得交联反应进行完全,冷却后,将成膜依次浸泡于去离子水、醇中,再于50-70℃下烘干,即制得含半互穿网络结构的复合膜;
步骤(7):将步骤(6)制得的含半互穿网络结构的复合膜于稀盐酸溶液中浸泡12-48小时,取出水洗,烘干至恒重,即制得所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜。
10.根据权利要求9所述的氧化石墨烯交联聚酰亚胺半互穿网络型复合膜的制备方法,其特征在于,
步骤(2)中所述的聚合反应的条件为:升温至75-85℃,反应3-5小时,之后升温使溶剂回流,反应12-20小时,反应结束后,降温至95-105℃;
步骤(4)中全氟磺酸树脂膜与有机溶剂的用量关系为:每50ml有机溶剂中全氟磺酸树脂膜的加入量为0.5-5g;
步骤(5)中氨基封端的聚酰亚胺在有机溶剂中的质量百分含量为2-5%;
步骤(4)中有机溶剂与步骤(5)中有机溶剂的质量比为1-5:5-9;
步骤(7)中稀盐酸溶液为质量百分含量为8-10%的稀盐酸溶液。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710264556.5A CN107082996B (zh) | 2017-04-21 | 2017-04-21 | 氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710264556.5A CN107082996B (zh) | 2017-04-21 | 2017-04-21 | 氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107082996A CN107082996A (zh) | 2017-08-22 |
CN107082996B true CN107082996B (zh) | 2020-03-24 |
Family
ID=59612151
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710264556.5A Expired - Fee Related CN107082996B (zh) | 2017-04-21 | 2017-04-21 | 氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107082996B (zh) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109280168A (zh) * | 2018-10-15 | 2019-01-29 | 桂林理工大学 | 聚酰亚胺/石墨烯/苝酐耐磨性复合材料的制备方法 |
CN109575370A (zh) * | 2019-01-15 | 2019-04-05 | 西北师范大学 | 一种氨基化β-CD/PTCA功能化石墨烯复合材料的制备方法 |
CN111499876B (zh) * | 2020-04-17 | 2021-04-20 | 东北师范大学 | 一种网状聚合物及其制备方法和一种半互穿网络聚合物电解质及聚合物锂电池 |
CN112898587B (zh) * | 2021-01-22 | 2022-11-04 | 山西穿越光电科技有限责任公司 | 一种石墨烯接枝改性超支化聚酰亚胺介电材料和制备方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101510615A (zh) * | 2009-03-26 | 2009-08-19 | 同济大学 | 一种基于可交联聚酰亚胺的半互穿网络型复合质子交换膜及其制备方法 |
CN106505232A (zh) * | 2016-10-18 | 2017-03-15 | 同济大学 | 一种氧化石墨烯交联磺化聚酰亚胺质子交换膜及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11127964B2 (en) * | 2010-07-28 | 2021-09-21 | Nanyang Technological University | Method for preparing a porous polyimide film and a composite membrane comprising the same |
CN102477162A (zh) * | 2010-11-25 | 2012-05-30 | 比亚迪股份有限公司 | 一种质子交换膜的制备方法和一种聚酰亚胺全氟磺酸树脂质子交换膜 |
CN103435828B (zh) * | 2013-07-31 | 2018-02-27 | 复旦大学 | 磺化的氧化石墨烯‑二氧化硅复合物/聚合物杂化质子交换膜及其制备方法 |
CN103724630B (zh) * | 2013-12-06 | 2015-11-25 | 同济大学 | 嵌段型磺化聚酰亚胺-聚苯并咪唑质子交换膜材料的合成方法 |
CN104817803A (zh) * | 2015-04-16 | 2015-08-05 | 安徽雄亚塑胶科技有限公司 | 一种高耐候、高强度、高耐磨的高铁垫片及其制备方法 |
CN105970605B (zh) * | 2016-05-26 | 2018-09-04 | 厦门大学 | 一种氧化石墨烯复合无纺布及其制备方法与应用 |
-
2017
- 2017-04-21 CN CN201710264556.5A patent/CN107082996B/zh not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101510615A (zh) * | 2009-03-26 | 2009-08-19 | 同济大学 | 一种基于可交联聚酰亚胺的半互穿网络型复合质子交换膜及其制备方法 |
CN106505232A (zh) * | 2016-10-18 | 2017-03-15 | 同济大学 | 一种氧化石墨烯交联磺化聚酰亚胺质子交换膜及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN107082996A (zh) | 2017-08-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110224166B (zh) | 一种磷酸掺杂交联型聚苯并咪唑高温质子交换膜及其制备方法 | |
CN107082996B (zh) | 氧化石墨烯交联聚酰亚胺半互穿网络型复合膜及其制备 | |
CN103724630B (zh) | 嵌段型磺化聚酰亚胺-聚苯并咪唑质子交换膜材料的合成方法 | |
CN101724165B (zh) | 环氧交联磺化聚芳醚酮质子交换膜材料及其制备方法 | |
CN102504310B (zh) | 一种磺化聚酰亚胺/壳聚糖复合质子导电膜的制备方法 | |
Zhong et al. | Preparation and properties of UV irradiation-induced crosslinked sulfonated poly (ether ether ketone) proton exchange membranes | |
CN104530439A (zh) | 磺化聚苯并咪唑-聚酰亚胺嵌段共聚物质子交换膜材料的合成方法 | |
Gong et al. | Solution processable octa (aminophenyl) silsesquioxane covalently cross-linked sulfonated polyimides for proton exchange membranes | |
CN106505232A (zh) | 一种氧化石墨烯交联磺化聚酰亚胺质子交换膜及其制备方法 | |
CN102842726B (zh) | 倍半硅氧烷杂化磺化聚酰亚胺质子交换膜及其制备方法 | |
CN104629081A (zh) | 一种以双醚交联型多孔聚苯并咪唑酰亚胺为基底的填孔型质子交换膜的制备方法 | |
CN112133946A (zh) | 一种含羧基磺化聚芳醚酮砜/负载磷钨酸-离子液体金属有机框架复合膜及其制备方法 | |
CN105418921A (zh) | 一种高磺化度可交联聚酰亚胺、制备方法及其在质子交换膜方面的应用 | |
Wang et al. | Cross-linked proton exchange membranes for direct methanol fuel cells: Effects of the cross-linker structure on the performances | |
CN107033358A (zh) | 磺化聚苯并咪唑‑聚酰亚胺嵌段共聚物复合膜及其制备 | |
CN101205308B (zh) | 磺化聚苯砜对苯二甲酰胺质子交换膜及其制备方法 | |
Xu et al. | High strength and stable proton exchange membrane based on perfluorosulfonic acid/polybenzimidazole | |
CN100404588C (zh) | 一种制备交联磺化聚酰亚胺膜的方法 | |
CN113801474A (zh) | 一种含羧基的磺化聚芳醚酮砜/Im-Uio-66-AS复合的质子交换膜及其制备方法 | |
CN107623138B (zh) | 一种复合质子交换膜及其制备方法 | |
Shimura et al. | Poly (arylene ether) ionomers containing sulfofluorenyl groups: Effect of electron-withdrawing groups on the properties | |
CN104966845B (zh) | 一种半超支化半交联型磺化聚酰亚胺复合质子交换膜及其制备方法 | |
Ahn et al. | Low methanol permeable crosslinked sulfonated poly (phenylene oxide) membranes with hollow glass microspheres for direct methanol fuel cells | |
CN102911494A (zh) | 有机-无机三元杂化磺化聚芳醚酮质子交换膜及其制备方法 | |
CN113675450A (zh) | 一种含羧基的磺化聚芳醚酮砜/Uio-66-AS复合的质子交换膜及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200324 |