CN117362743B - Preparation method of heat-shock-resistant aramid aerogel and aramid aerogel - Google Patents
Preparation method of heat-shock-resistant aramid aerogel and aramid aerogel Download PDFInfo
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- CN117362743B CN117362743B CN202311682502.2A CN202311682502A CN117362743B CN 117362743 B CN117362743 B CN 117362743B CN 202311682502 A CN202311682502 A CN 202311682502A CN 117362743 B CN117362743 B CN 117362743B
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- aramid
- aerogel
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- preparation
- hydrogel
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- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 194
- 239000004760 aramid Substances 0.000 title claims abstract description 188
- 239000004964 aerogel Substances 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000017 hydrogel Substances 0.000 claims abstract description 61
- 239000002121 nanofiber Substances 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 46
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 230000035939 shock Effects 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 229920006231 aramid fiber Polymers 0.000 claims description 70
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 53
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 23
- 230000001112 coagulating effect Effects 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- 238000007790 scraping Methods 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229940001584 sodium metabisulfite Drugs 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 238000009413 insulation Methods 0.000 abstract description 10
- 239000012774 insulation material Substances 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 62
- 239000007864 aqueous solution Substances 0.000 description 31
- 239000000835 fiber Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052582 BN Inorganic materials 0.000 description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 12
- 238000007710 freezing Methods 0.000 description 11
- 230000008014 freezing Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000013557 residual solvent Substances 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000004965 Silica aerogel Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000002981 blocking agent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 1
- PWTIWIZYPHOOGL-UHFFFAOYSA-N B(O)OBO.N1=C(N)N=C(N)N=C1N Chemical compound B(O)OBO.N1=C(N)N=C(N)N=C1N PWTIWIZYPHOOGL-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- 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
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention provides a preparation method of heat shock resistant aramid aerogel and the aramid aerogel, and belongs to the field of heat insulation materials. According to the preparation method, the aerogel composite material is obtained through the steps of preparing the aramid nanofiber dispersion liquid, organic-inorganic composite aramid nanofiber dispersion liquid, replacing an aramid hydrogel with a solvent, dipping a cross-linking agent solution and the like, and the high toughness and the high specific surface area of the aramid nanofiber and the excellent heat insulation property and environmental stability of the inorganic aerogel are integrated together, so that the decomposition temperature is 544.2 ℃, the thermal shock at 650 ℃ can be borne, and the defects of poor mechanical property, low thermal stability and the like of the existing aramid aerogel are overcome.
Description
Technical Field
The invention belongs to the field of heat insulation materials, and particularly relates to a preparation method of heat shock resistant aramid aerogel and the aramid aerogel.
Background
With the development of socioeconomic performance, the need for energy has become an important issue in the world today. The heat insulating material is used as the heat insulating layer, so that the energy cost can be greatly reduced, and the heat insulating layer is an important energy saving measure in the fields of construction, industry, national defense, aerospace and the like. Although the traditional heat insulation materials are widely applied, the heat conductivity coefficient is relatively high, and the heat insulation capability is relatively general. Aerogel is used as an emerging heat insulation material and has a three-dimensional porous structure, and the porous structure can keep a large amount of air in the material, so that the heat conductivity coefficient of the aerogel is greatly reduced, and the heat insulation material is the solid with the best heat insulation effect at presentA bulk material. In addition, the special structural characteristics of the aerogel endow the aerogel with the performance advantages of high specific surface area, low density and high porosity, so that the aerogel has wide application prospects in the fields of new energy sources, fire protection, construction, catalysis, adsorption and the like. The most common SiO at present 2 Aerogel, because the matrix material is inorganic matter, has low mechanical strength and brittleness, is difficult to form into a whole material, and limits SiO 2 Aerogel is practically used.
The aramid aerogel prepared from the aramid nano fiber has unique application prospect in the fields of heat insulation, adsorption, catalysis, electromagnetic shielding and the like because the aramid has excellent properties of light weight, flame retardance, temperature resistance, high strength, high modulus and the like. The toughness of the prepared aramid aerogel is greatly increased compared with that of inorganic aerogel, but the mechanical property of the prepared aramid aerogel is still relatively poor. In addition, because the thermal decomposition temperature of the aramid fiber is about 560 ℃, the aramid aerogel is difficult to use at extremely high temperature, and the application of the aramid aerogel in special scenes is limited, so that the aramid aerogel is modified, good toughness is reserved, mechanical properties can be improved, and the aramid aerogel has important significance for popularization and application.
At present, a plurality of domestic patents are researching aerogel. For example, CN115710117 discloses an aerogel composite material, a preparation method and application thereof, and relates to the technical field of aerogel. Specifically, polymer aerogels and inorganic nano aerogels are included; the polymer aerogel is prepared from at least one of aramid fiber, poly-p-phenylene benzobisoxazole and polyimide; inorganic nano-aerogels include silica aerogels. (1) Preparing polymer wet gel from the polymer dispersion liquid through a phase inversion method, and preparing polymer aerogel from the polymer wet gel through a freeze drying method and/or a carbon dioxide supercritical drying method; (2) adding a silica sol to the polymer aerogel; (3) Vacuumizing the mixed gel obtained in the step (3) to enable the silica sol to completely permeate into the polymer wet gel, standing until the silica sol is completely gelled, and sequentially carrying out ageing treatment and surface hydrophobicity treatment to obtain the aerogel composite material. However, this preparation process is too long, and it usually takes more than one week to prepare the organic aerogel, and it takes a significant time and cost to complete the preparation through the process of compounding with the silica aerogel. In addition, the prepared sample is hardened and embrittled due to the silica aerogel filled in the organic aerogel, which seriously affects the practicability of the invention.
CN116284973 discloses a boron nitride/aramid nanofiber aerogel and a preparation method thereof. The method comprises the following steps: dispersing chopped aramid fiber and boron nitride nanobelt powder in an organic solvent for reaction to obtain aramid nanofiber/boron nitride hydrogel; performing liquid nitrogen directional freezing and freeze drying treatment on the aramid nanofiber/boron nitride hydrogel to obtain boron nitride/aramid nanofiber aerogel; according to the technology, the characteristics of boron nitride aerogel (inorganic aerogel) and aramid nanofiber aerogel (organic aerogel) are effectively integrated, due to the action of hydrogen bonds, the high-aspect-ratio flexible boron nitride nanobelt is firmly locked by aramid fibers, and after suction filtration and liquid nitrogen directional freezing operation, the inside of the boron nitride/aramid nanofiber aerogel is assembled into a lamellar structure, so that the multifunctional integrated aerogel with the functions of heat insulation, heat preservation, elasticity, flexibility, flame retardance and thermal stability is obtained. However, in the sol-gel stage, the hydrogel is prepared by adding a coagulating bath into the nano dispersion and stirring, and is shaped by suction filtration after being molded, so that the porosity of the prepared composite aerogel is low, the heat conductivity coefficient of the composite aerogel is influenced, and the practical application of the composite aerogel in the field of heat insulation is hindered.
Therefore, how to overcome the defects of the prior aramid aerogel and further optimize the preparation process of the aramid aerogel on the basis of maintaining the high toughness characteristic of the aramid, so that the obtained product has excellent mechanical properties and thermal stability, which is a problem to be solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of heat shock resistant aramid aerogel. According to the invention, the aramid nanofiber and the inorganic nanoparticle are prepared into the aerogel composite material through sol-gel process, dipping cross-linking agent and other processes, and the high toughness and the high specific surface area of the aramid nanofiber and the excellent heat insulation property and environmental stability of the inorganic aerogel are integrated, so that the defects of poor mechanical property, low heat stability and the like of the existing aramid aerogel are overcome.
The technical scheme of the invention is as follows:
the invention provides a preparation method of heat shock resistant aramid aerogel, which comprises the following steps:
step (1): preparation of an aramid nano dispersion liquid:
heating and stirring the pretreated aramid fiber in an alkali-containing solution, removing protons on amide bonds of the aramid fiber in a solution system, and then dispersing to form nanofibers to obtain an aramid nanofiber dispersion;
step (2): organic-inorganic composite aramid nanofiber dispersion:
adding inorganic nano particles into the aramid nanofiber dispersion liquid obtained in the step (1), and uniformly stirring and dispersing to obtain the organic-inorganic composite aramid nanofiber dispersion liquid;
step (3): preparation of aramid hydrogel:
scraping or injecting the organic-inorganic composite aramid nanofiber dispersion liquid obtained in the step (2) to form a liquid film, soaking the liquid film in a coagulating bath, and standing to obtain the aramid hydrogel;
step (4): and (3) carrying out solvent replacement, dipping the cross-linking agent solution and drying on the aramid fiber hydrogel obtained in the step (3), and finally carrying out heat treatment to obtain the heat-shock-resistant aramid fiber aerogel which can bear the heat shock at the temperature of more than 650 ℃.
In the step (1), at least one of acetone, ethanol and fatty alcohol polyoxyethylene ether sodium sulfate solution is adopted for pretreatment of the aramid fiber, and cleaning and drying treatment is carried out under the ultrasonic action so as to remove fiber oiling agent and impurities.
Further, in step (1), the base includes at least one of potassium hydroxide, sodium hydride, potassium hydride, butyllithium, sodium ethoxide, potassium ethoxide, and potassium tert-butoxide.
Further, in the step (1), the solution is prepared by mixing water and at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or acetonitrile, wherein the mass ratio of the preparation is 25:1.
further, in the step (1), the temperature of heating and stirring is 40-75 ℃, preferably 60 ℃, the heating time is 3-10 h, and the stirring speed is 50-500 RPM.
In the step (1), the aramid fiber is firstly deprotonated through alkali treatment, so that intermolecular hydrogen bonding is weakened, and the nanofibers are mutually peeled off, so that an aramid nanofiber dispersion liquid is formed.
Further, in the step (1), the mass ratio of the aramid fiber to the alkali is 1: (0.75-5).
Further, in the step (1), the mass fraction of the aramid fiber in the aramid fiber nanofiber dispersion liquid is 1-3.5%.
Further, in the step (2), the inorganic nanoparticles include any one or two or more of silica, titania, zirconia, alumina, and zinc oxide.
Further, in the step (2), the inorganic nanoparticles are added in an amount of 25 to 500 mass% based on the mass of the aramid fiber of the step (1).
Further, in the step (2), the stirring temperature is 40-75 ℃, the stirring time is 3-10 h, and the stirring speed is 50-500 RPM.
In the step (3), the thickness of the liquid film is controlled by controlling the distance between the film scraping knife and the release paper, and the liquid film with the corresponding thickness is obtained along with the film scraping process.
Further, in the step (3), the coagulation bath contains a solvent capable of providing protons, including any one or two or more of water, sulfuric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, citric acid, tartaric acid, ethanol, or isopropanol. The concentration of the coagulation bath is 0-75% except pure water.
Further, in the step (3), the liquid film is soaked in the coagulating bath for 5 min-1 h.
In the step (3), the coagulation bath has the function of reducing protons to amide bonds, and the aramid nanofibers gradually recover intermolecular forces due to gradual permeation of the coagulation bath, so that the aramid nanofibers are lapped into a nanofiber network, and hydrogel is formed.
Further, in the step (4), the solvent replaced by the solvent adopts at least one of water, ethanol or tertiary butanol solution, and the residual solvent in the aramid hydrogel is replaced.
Further, in the step (4), the time for solvent replacement is controlled to be 12-48 hours.
In the step (4), the solvent is replaced by water or other solution in the aramid hydrogel nanofiber network formed in the step (3). The solvent replacement is performed by immersing the aramid hydrogel, and replacing the solvent at intervals (for example, 5 hours).
Further, in step (4), the impregnated crosslinker solution is a blocked aqueous polyisocyanate, i.e., a blocked polyisocyanate, wherein the polyisocyanate comprises at least one of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate; the blocking agent used includes at least one of sodium bisulphite, sodium metabisulphite, ethanol, n-propanol, n-butanol, methyl ethyl ketone oxime, acetone oxime, cyclohexanone oxime and acetophenone oxime. The molar ratio of polyisocyanate to blocking agent is 1: (2-2.5).
Further, in the step (4), the usage amount of the impregnated cross-linking agent is controlled by the concentration of the cross-linking agent solution, wherein the concentration of the cross-linking agent solution is 3-18wt% and the impregnation time is 2-5 h. The cross-linking agent solution is prepared by dissolving a cross-linking agent in ethanol or tertiary butanol aqueous solution with the concentration of 30-70%.
Further, in the step (4), after the cross-linking agent is impregnated, the adding amount of the cross-linking agent in the final aramid aerogel is 5-14wt%.
In the step (4), the polyisocyanate is extremely easy to react with other substances containing active hydrogen atoms, so that the polyisocyanate is blocked by using a blocking agent to enable the polyisocyanate to be stably in a water system, and after the polyisocyanate is dried, blocking groups of the polyisocyanate are removed by a heat treatment mode, so that the polyisocyanate reacts with amide bonds of the aramid fiber to form urea bonds, and a bonding structure is formed by using chemical bonds, so that the mechanical property of the aramid fiber aerogel is improved.
Further, in the step (4), the drying mode is freeze drying or supercritical CO 2 And (5) drying.
Further, the freeze-drying step comprises the steps of freezing for 3-5 h at the temperature of less than or equal to 0 ℃, and then drying for 6-48 h under the condition that the vacuum degree is less than 15Pa, wherein the drying temperature is-50-40 ℃.
Further, the supercritical CO 2 The pressure is more than 7.38MPa, the temperature is more than 31.1 ℃ and the drying time is 0.5-12 h.
Further, in the step (4), the heat treatment temperature is 60-185 ℃, and the heat treatment time is 5-45 min. The heat treatment temperature is dependent on the capping agent used, and the deblocking temperature is typically alcohol capping agent > oxime capping agent > sodium sulfite capping agent.
The invention also provides the thermal shock resistant aramid aerogel obtained by the preparation method, wherein the aramid aerogel has the membrane porosity of 91-97%, the breaking strength of 8.9-17.5 MPa, the tensile modulus of 230-350 MPa, the decomposition temperature of 544.2 ℃ and can bear the thermal shock of 650 ℃.
After the aramid aerogel reaches the decomposition temperature, the carbonized network of the aramid nanofiber can still well load inorganic nanoparticles, so that the whole structure can bear the thermal shock of 650 ℃, and the aramid aerogel without the inorganic nanoparticles can only bear the thermal shock of 500 ℃.
Further, the aramid aerogel has a density of up to 290m 2 Specific surface area per g, thermal conductivity of 26-34 mW.m -1 K -1 。
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a method for preparing high-toughness aramid aerogel with heat shock resistance. The aramid fiber is used as a raw material, the aramid fiber is prepared into an aramid nanofiber dispersion liquid, inorganic nano particles are mixed, and the aramid composite aerogel with low heat conductivity coefficient, high temperature resistance and high toughness is prepared by performing solvent replacement, dipping a cross-linking agent and drying through a sol-gel process, so that the aramid fiber composite aerogel has a wide application prospect;
2. according to the invention, the characteristic of high specific surface area of the aerogel is utilized, the aramid nanofiber network is used as a good carrier of the inorganic nanoparticles, and the inorganic nanoparticles and the aramid fibers are firmly combined together due to the action of hydrogen bonds, so that the organic-inorganic composite aramid aerogel is prepared, and compared with the organic aerogel, the heat shock resistance and the flame retardant property of the organic-inorganic composite aramid aerogel are greatly improved, and the performance advantages of the organic-inorganic composite aramid aerogel are considered;
4. according to the invention, the cross-linking agent is added in the preparation process of the aerogel and is subjected to thermal cross-linking, so that the flexibility and tensile breaking strength of the aramid aerogel are improved, and the reliability and safety in the practical application process are enhanced.
5. The aerogel film prepared by the invention has the characteristics of excellent heat insulation, heat stability, flame retardance and light weight and high strength, can be used as high Wen Fangguan aerogel, and widens the application of the aramid aerogel in a high-temperature environment;
6. the invention combines the characteristics of organic matters and inorganic matters, and the flexibility and the mechanical property of the invention are greatly improved compared with those of inorganic aerogel; the thermal protection material used in the environment has wide application prospect in the fields of automobiles, fire protection, equipment protection, building heat preservation and the like.
Drawings
FIG. 1 is a scanning electron microscope image of the cross section of an aramid aerogel obtained by the preparation method of example 1 at different magnifications;
FIG. 2 is an external view of an aramid aerogel obtained by the preparation method of example 1;
FIG. 3 is a scanning electron microscope image of an aramid aerogel obtained by the preparation method of example 2;
FIG. 4 is a graph showing the tensile fracture of the aramid aerogel obtained by the preparation method of example 1;
fig. 5 is a tensile fracture graph of an aramid aerogel obtained by the preparation method of example 2.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
The test methods for all examples of the present invention and comparative examples are as follows:
(1) Thermal conductivity coefficient:
the heat conductivity coefficient is tested on the sample by adopting a transient plane heat source method, and the test standard is referred to GB/T32064-2015.
(2) Tensile breaking strength and tensile modulus:
the test was performed using an INSTRON 34TM-30 electronic tensile tester, test standard reference GB/T17911-2018.
(3) Porosity:
the porosity was calculated according to the following formula, a certain mass of aerogel was weighed, immersed in a container with a volume of 10 mL filled with absolute ethyl alcohol, and the container was put into an ultrasonic cleaner for degassing treatment, then filled with absolute ethyl alcohol, and left to stand for 30min and taken out. The porosity of the sample was calculated according to the formula.
，
Wherein: p-porosity (%);
m 1 -sample mass (g);
m 2 absolute ethanol and total mass of container without sample (g);
m 3 -total mass of container after sample addition (g);
m 4 -the total mass of absolute ethanol and container (g) after removal of the sample.
(4) Thermal deformation:
aerogel samples with the size of 80X 10mm are placed in a high-temperature oven at 650 ℃, taken out after being kept for 300 seconds, the size is measured, and the reduction amount of the area is calculated.
Example 1
A preparation method of heat shock resistant aramid aerogel comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in an acetone solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an alkali-containing dimethyl sulfoxide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is potassium hydroxide, the addition amount of the alkali is 1.5 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the dimethyl sulfoxide aqueous solution is 2 wt%;
(2) Organic-inorganic composite aramid nanofiber dispersion:
adding 25% of nano silicon dioxide by mass of aramid fiber into the dispersion liquid of the aramid fiber nano fiber and uniformly stirring;
(3) Preparation of aramid hydrogel:
preparing and molding the aramid nanofiber dispersion liquid prepared in the step (2) in a film scraping mode, adjusting the distance between a scraper of a film scraping machine and release paper to be 2mm, and controlling the thickness of an aerogel film by controlling the distance between the scraper and the release paper, so as to obtain a liquid film with corresponding thickness along with the film scraping process;
immersing the release paper into a coagulating bath, wherein the coagulating bath is deionized water, controlling the immersing time of the coagulating bath to be 30min, and waiting until the sol-gel conversion is completed, thus obtaining an aramid hydrogel film;
(4) Placing the aramid hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the aramid hydrogel;
then 100g of 4-4 diphenylmethane diisocyanate was added to 1L of 50% aqueous t-butanol solution, the solution system was placed in a heating medium at 40 ℃, 100ml of 84% by mass sodium bisulfite solution was added dropwise thereto, nitrogen was introduced and stirring was carried out for 3 hours, to obtain a cross-linking agent solution having a concentration of 8.5% by weight;
immersing the prepared aramid fiber aerogel film in the prepared cross-linking agent solution for 5 hours, then putting the aramid fiber aerogel film into a freeze dryer, freezing the aramid fiber hydrogel film for 3 hours at the temperature of 50 ℃ below zero, and then drying the aramid fiber aerogel film for 12 hours under the condition that the vacuum degree is less than 15Pa to obtain the aramid fiber aerogel film;
and placing the dried aramid aerogel in a vacuum oven at 80 ℃ for heat treatment for 45min to strengthen the bonding force between fibers, thereby obtaining the high-toughness aramid aerogel with heat shock resistance.
Example 2
A preparation method of heat shock resistant aramid aerogel comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in an acetone solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an alkali-containing dimethyl sulfoxide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is sodium hydroxide, the addition amount of the alkali is 0.75 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the dimethyl sulfoxide aqueous solution is 2 wt%;
(2) Organic-inorganic composite aramid nanofiber dispersion:
adding nano zirconium dioxide accounting for 100% of the mass of the aramid fiber into the dispersion liquid of the aramid fiber nano fiber, and uniformly stirring;
(3) Preparation of aramid hydrogel:
preparing and molding the aramid nanofiber dispersion liquid prepared in the step (2) in a film scraping mode, adjusting the distance between a scraper of a film scraping machine and release paper to be 2mm, and controlling the thickness of an aerogel film by controlling the distance between the scraper and the release paper, so as to obtain a liquid film with corresponding thickness along with the film scraping process;
immersing the release paper into a coagulating bath, wherein the coagulating bath is 5% sulfuric acid water solution, controlling the immersing time of the coagulating bath to be 20min, and obtaining the aramid hydrogel film after the sol-gel conversion is completed;
(4) Placing the aramid fiber hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the hydrogel;
then 50ml of N-propanol is added into 500ml of N, N-dimethylacetamide solution, then 100g of dicyclohexylmethane diisocyanate is added, the solution system is placed in a heating medium at 40 ℃, 235g of N-propanol solution is dropwise added into the solution, nitrogen is introduced into the solution and the solution is stirred for 2 hours, then solid substances are obtained after the solution is dried, and the solid substances are uniformly stirred in 550ml of 80% ethanol water solution to obtain a cross-linking agent solution with the concentration of 18 wt%;
immersing the prepared aramid hydrogel film in the prepared cross-linking agent solution for 5h, and then putting CO 2 A supercritical dryer is used for replacing with liquid carbon dioxide for 2 hours under the environment of 20Mpa, then the temperature is raised to 40 ℃, and the aramid aerogel film is obtained after drying for 4 hours;
and placing the dried aramid aerogel in a vacuum oven at 185 ℃ for heat treatment for 5min to strengthen the bonding force between fibers, thereby obtaining the high-toughness aramid aerogel with heat shock resistance.
Example 3
A preparation method of heat shock resistant aramid aerogel comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in 30% fatty alcohol polyoxyethylene ether sodium sulfate aqueous solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an alkali-containing dimethyl sulfoxide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is potassium hydroxide, the addition amount of the alkali is 5 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the dimethyl sulfoxide aqueous solution is 1 wt%;
(2) Organic-inorganic composite aramid nanofiber dispersion:
adding nano alumina accounting for 200% of the mass of the aramid fiber into the aramid fiber nano fiber dispersion liquid and uniformly stirring;
(3) Preparation of aramid hydrogel:
pouring the aramid nanofiber dispersion liquid prepared in the step (2) into a die in a film casting mode, controlling the thickness of a liquid film to be 2mm, and obtaining the liquid film with corresponding thickness after the liquid film is cast to be flat;
then slowly immersing the prepared liquid film into a coagulating bath, wherein the coagulating bath is a 60% formic acid aqueous solution, controlling the immersing time of the coagulating bath to be 5min, and obtaining the aramid hydrogel film after the sol-gel conversion is completed;
(4) Placing the hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the hydrogel;
then adding 44g of hexamethylene diisocyanate into 1L of 65% tertiary butanol aqueous solution, placing the solution system in a heating medium at 40 ℃, dropwise adding 300ml of sodium bisulfite solution with the mass fraction of 89%, introducing nitrogen and stirring for 3 hours to obtain a cross-linking agent solution with the concentration of 3 wt%;
immersing the prepared aramid fiber hydrogel film in the prepared cross-linking agent solution for 5 hours, then putting the aramid fiber hydrogel film into a freeze dryer, freezing for 3 hours at the temperature of 50 ℃ below zero, and then drying for 12 hours under the condition that the vacuum degree is less than 15Pa to obtain the high-toughness aramid fiber aerogel with heat shock resistance;
and placing the dried aramid aerogel in a vacuum oven at 60 ℃ for heat treatment for 20min to strengthen the bonding force between fibers, thereby obtaining the high-toughness aramid aerogel with heat shock resistance.
Example 4
A preparation method of heat shock resistant aramid aerogel comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in 30% fatty alcohol polyoxyethylene ether sodium sulfate aqueous solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an aqueous solution of N, N-dimethylacetamide containing alkali, wherein the ratio of the N, N-dimethylacetamide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is sodium hydride, the addition amount of the alkali is 1.3 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the N, N-dimethylacetamide aqueous solution is 2.5 weight percent;
(2) Organic-inorganic composite aramid nanofiber dispersion:
adding nano titanium dioxide accounting for 500% of the mass of the aramid fiber into the aramid fiber nanofiber dispersion liquid and uniformly stirring;
(3) Preparation of aramid hydrogel:
preparing and molding the aramid nanofiber dispersion liquid prepared in the step (2) in a film scraping mode, adjusting the distance between a scraper of a film scraping machine and release paper to be 1mm, and controlling the thickness of an aerogel film by controlling the distance between the scraper and the release paper, so as to obtain a liquid film with corresponding thickness along with the film scraping process;
immersing the release paper into a coagulating bath, wherein the coagulating bath is 10% trifluoroacetic acid aqueous solution, controlling the immersing time of the coagulating bath to be 30min, and obtaining the aramid hydrogel film after the sol-gel conversion is completed;
(4) Placing the aramid hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the aramid hydrogel;
then 100g of 4-4 diphenylmethane diisocyanate was added to 1L of 50% aqueous t-butanol solution, the solution system was placed in a heating medium at 40 ℃, 70g of methyl ethyl ketoxime was added dropwise thereto, nitrogen was introduced and stirring was carried out for 1.5 hours, to obtain a crosslinking agent solution having a concentration of 9.5% by weight;
immersing the prepared aramid fiber aerogel film in the prepared cross-linking agent solution for 5 hours, then putting the aramid fiber hydrogel film into a freeze dryer, freezing the aramid fiber hydrogel film for 3 hours at the temperature of 50 ℃ below zero, and then drying the aramid fiber hydrogel film for 12 hours under the condition that the vacuum degree is less than 15Pa to obtain the aramid fiber aerogel film;
and placing the dried aramid aerogel in a vacuum oven at 90 ℃ for heat treatment for 20min to strengthen the bonding force between fibers, thereby obtaining the high-toughness aramid aerogel with heat shock resistance.
Example 5
A preparation method of heat shock resistant aramid aerogel comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in 30% fatty alcohol polyoxyethylene ether sodium sulfate aqueous solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an N, N-dimethylacetamide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is potassium hydroxide, the addition amount of the alkali is 3.5 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the N, N-dimethylacetamide aqueous solution is 3.5 weight percent;
(2) Organic-inorganic composite aramid nanofiber dispersion:
adding nano zinc oxide accounting for 75% of the mass of the aramid fiber into the aramid fiber nanofiber dispersion liquid and uniformly stirring;
(3) Preparation of aramid hydrogel:
preparing and molding the aramid nanofiber dispersion liquid prepared in the step (2) in a film scraping mode, adjusting the distance between a scraper of a film scraping machine and release paper to be 1.5mm, and controlling the thickness of an aerogel film by controlling the distance between the scraper and the release paper, so as to obtain a liquid film with corresponding thickness along with the film scraping process;
immersing the release paper into a coagulating bath, wherein the coagulating bath is 75% isopropanol solution, controlling the immersing time of the coagulating bath to be 1h, and obtaining the aramid hydrogel film after the sol-gel conversion is completed;
(4) Placing the aramid hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the aramid hydrogel;
then adding 100g dicyclohexylmethane diisocyanate into 1L of 30% tertiary butanol aqueous solution, placing the solution system into a heating medium at 40 ℃, dropwise adding 100ml of 56% acetone oxime aqueous solution, introducing nitrogen and stirring for 1.5h to obtain a cross-linking agent solution with the concentration of 8.4 wt%;
immersing the prepared aramid fiber hydrogel film in the prepared cross-linking agent solution for 5 hours, then putting the aramid fiber hydrogel film into a freeze dryer, freezing the aramid fiber hydrogel film for 5 hours at the temperature of 50 ℃ below zero, then drying the aramid fiber hydrogel film for 24 hours at the vacuum degree of less than 15Pa and the temperature of 50 ℃ below zero, then gradually raising the temperature to 40 ℃, and drying the aramid fiber hydrogel film for 24 hours to obtain the aramid fiber hydrogel film;
and placing the dried aerogel in a vacuum oven at 170 ℃ for heat treatment for 20min to strengthen the bonding force among fibers, thereby obtaining the high-toughness aramid aerogel with heat shock resistance.
Comparative example 1
The preparation of the conventional aramid aerogel, namely aramid aerogel (without inorganic nano particles and without impregnated cross-linking agent), comprises the following specific steps:
(1) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in 30% fatty alcohol polyoxyethylene ether sodium sulfate aqueous solution for ultrasonic cleaning, then using ethanol to clean the fiber, and drying for later use;
putting the dried para-aramid fiber into an alkali-containing dimethyl sulfoxide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is potassium hydroxide, the addition amount of the alkali is 1.5 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the dimethyl sulfoxide aqueous solution is 2 wt%;
(2) Preparing and molding the aramid nanofiber dispersion liquid prepared in the step (2) by adopting a film scraping mode, and adjusting the distance between a scraper of a film scraping machine and release paper to be 1.5mm;
immersing the release paper into a coagulating bath, wherein the coagulating bath is deionized water, controlling the immersing time of the coagulating bath to be 1h, and waiting until the sol-gel conversion is completed, thus obtaining an aramid hydrogel film;
(3) Placing the aramid fiber hydrogel film in a tertiary butanol aqueous solution (the volume ratio of tertiary butanol to water is 1:1), soaking for 30 hours, wherein the solution is replaced every 5 hours, and completely removing the residual solvent in the aramid fiber hydrogel film;
and then putting the prepared aramid fiber hydrogel film into a freeze dryer, freezing for 3 hours at the temperature of 50 ℃ below zero, and then drying for 12 hours under the condition that the vacuum degree is less than 15Pa to obtain the aramid fiber aerogel.
Comparative example 2
The preparation of the conventional aramid aerogel-aramid/boron nitride composite aerogel comprises the following specific steps:
(1) Preparation of melamine diboronic aerogel:
0.4838g of melamine and 0.4762g of boric acid are weighed and sequentially added into 48ml of tertiary butanol/distilled water cosolvent, wherein the proportion of tertiary butanol to distilled water is 7:5, and a melamine diboronic acid solution with the concentration of 20mg/ml is obtained; transferring the mixture to a vacuum freeze dryer for treatment for 3 hours to obtain melamine diboronic aerogel;
(2) Preparation of an aramid nano dispersion liquid:
placing para-aramid fiber in 30% fatty alcohol polyoxyethylene ether sodium sulfate aqueous solution for ultrasonic cleaning, then using ethanol to clean the para-aramid fiber, and drying for later use;
putting the dried para-aramid fiber into an alkali-containing dimethyl sulfoxide aqueous solution, wherein the ratio of dimethyl sulfoxide to water is 25:1, continuously stirring the prepared solution under the heating condition of 60 ℃ until the aramid fibers in the solution are completely dispersed, wherein the alkali is potassium hydroxide, the addition amount of the alkali is 1.5 times of the mass of the para-aramid fibers, and the content of the para-aramid fibers in the dimethyl sulfoxide aqueous solution is 0.5 weight percent;
(3) Aramid nanofiber dispersion:
adding melamine diboronic aerogel with the same mass as para-aramid fiber into the aramid nanofiber dispersion liquid, and stirring the mixture until the mixture is completely and uniformly dispersed;
(4) Preparation of aramid nanofiber/boron nitride hydrogel:
taking 50ml of the aramid nanofiber dispersion liquid obtained in the step (3), adding 150ml of deionized water into the dispersion liquid, and fully stirring for 4 hours at a rotating speed of 150r/min to obtain an aramid nanofiber/boron nitride hydrogel;
(5) Introducing the prepared hydrogel into a Buchner funnel, adopting suction filtration operation, respectively cleaning 3 the hydrogel by using ethanol and deionized water, and cleaning the hydrogel to be neutral, wherein the volume of the cleaned hydrogel is 80ml;
transferring the washed hydrogel into a directional freezing mold, and placing the hydrogel on the surface of a specific device filled with liquid nitrogen for 30min, so as to directionally freeze the hydrogel from bottom to top;
transferring the frozen hydrogel to a freeze dryer, freezing for 3 hours at the temperature of 50 ℃ below zero, and drying for 12 hours under the condition that the vacuum degree is less than 15Pa to obtain the aramid fiber/boron nitride composite aerogel.
FIG. 1 is a scanning electron microscope image of the cross section of the aramid aerogel obtained by the preparation method of example 1 at different magnifications,
the prepared aramid aerogel has a three-dimensional network structure formed by assembling and lapping nano fibers, and provides good structural guarantee for the heat insulation performance of the aramid aerogel.
Fig. 2 is an external view of the aramid aerogel obtained by the preparation method of example 1, and it can be seen from fig. 2 that the addition of the inorganic nanoparticles and the thermal crosslinking did not have a significant effect on the external appearance of the aramid aerogel.
Fig. 3 is a scanning electron microscope image of the aramid aerogel obtained by the preparation method of example 2, and it can be seen from fig. 3 that inorganic nanoparticles are supported on a network of aramid nanofibers, and after a crosslinking agent is added, crosslinking points appear between the nanofibers, thereby providing good mechanical properties for the aramid aerogel.
Fig. 4 is a tensile fracture graph of the aramid aerogel obtained by the preparation method of example 1, and it can be seen from fig. 4 that the aramid aerogel has good mechanical properties.
Fig. 5 is a drawing breaking chart of the aramid aerogel obtained by the preparation method of example 2, and it can be seen from fig. 5 that in comparative example 1, the mechanical properties of the aramid aerogel are improved as the amount of the crosslinking agent added is increased.
Table 1 Performance parameters of the aramid aerogels prepared in examples 1 to 5 and comparative examples 1 to 2
As can be seen from Table 1, the composite aramid aerogel prepared by the preparation method of the invention improves the mechanical properties and the thermal shock resistance of the aramid aerogel by the combination of the crosslinking agent and the inorganic nano particles. Among them, it can be found that the amount of nano particles added has a certain influence on the thermal conductivity and thermal deformation of the prepared aerogel by comparing the examples of the present invention with comparative example 1. With the addition of the cross-linking agent, the mechanical property of the aerogel is also improved to a greater extent. Comparative example 2 adopts a process route of suction filtration molding and directional freezing, although the process is compounded with inorganic matters, and the heat insulation capability and mechanical property of the composite material are reduced due to lower porosity. The above examples and the comparative examples illustrate that the technical scheme of the invention makes the aramid aerogel have wider application prospects in the field of thermal protection.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any other way, but is intended to cover any modifications or equivalent variations according to the technical spirit of the present invention, which fall within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A method for preparing an aramid aerogel resistant to thermal shock, which is characterized by comprising the following steps:
step (1): preparation of an aramid nanofiber dispersion:
heating and stirring the pretreated aramid fiber in an alkali-containing solution, removing protons on amide bonds of the aramid fiber in a solution system, and then dispersing to form nanofibers to obtain an aramid nanofiber dispersion; in the aramid nanofiber dispersion liquid, the mass fraction of the aramid fibers is 1-3.5%;
step (2): organic-inorganic composite aramid nanofiber dispersion:
adding inorganic nano particles into the aramid nanofiber dispersion liquid obtained in the step (1), and uniformly stirring and dispersing to obtain the organic-inorganic composite aramid nanofiber dispersion liquid;
wherein the inorganic nano particles comprise any one or more than two of silicon dioxide, titanium dioxide, zirconium oxide, aluminum oxide and zinc oxide; based on the mass of the aramid fiber in the step (1), the adding amount of the inorganic nano particles is 25-500% by mass;
step (3): preparation of aramid hydrogel:
scraping or injecting the organic-inorganic composite aramid nanofiber dispersion liquid obtained in the step (2) to form a liquid film, soaking the liquid film in a coagulating bath, and standing to obtain the aramid hydrogel;
step (4): the aramid fiber hydrogel obtained in the step (3) is subjected to solvent replacement, dipping and drying of a cross-linking agent solution, and finally heat treatment is carried out to obtain the aramid fiber aerogel with thermal shock resistance, wherein the aramid fiber aerogel can bear thermal shock at the temperature of more than 650 ℃;
wherein the impregnated crosslinker solution is a blocked aqueous polyisocyanate solution, wherein the polyisocyanate comprises at least one of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate; the end-capping agent comprises at least one of sodium bisulphite, sodium metabisulfite, ethanol, n-propanol, n-butanol, methyl ethyl ketone oxime, acetone oxime, cyclohexanone oxime and acetophenone oxime;
the usage amount of the impregnated cross-linking agent is controlled by the concentration of a cross-linking agent solution, the concentration of the cross-linking agent solution is 3-18wt%, and the cross-linking agent solution is prepared by dissolving the cross-linking agent in ethanol or tertiary butanol water solution with the concentration of 30-70%.
2. The method of preparing an aramid aerogel according to claim 1, wherein in step (1), the base comprises at least one of potassium hydroxide, sodium hydride, potassium hydride, butyllithium, sodium ethoxide, potassium ethoxide, and potassium tert-butoxide.
3. The method for preparing an aramid aerogel according to claim 1 or 2, wherein in the step (1), the solution is prepared by mixing water and at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or acetonitrile, wherein the mass ratio of the preparation is 25:1.
4. the method for preparing an aramid aerogel according to claim 3, wherein in the step (1), the mass ratio of the aramid fiber to the alkali is 1: (0.75-5).
5. The method of producing an aramid aerogel according to claim 1 or 2, wherein in the step (3), the coagulation bath comprises any one or two or more of water, sulfuric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, oxalic acid, citric acid, tartaric acid, ethanol or isopropanol.
6. The method of claim 5, wherein in the step (3), the liquid film is immersed in the coagulating bath for 5min to 1h.
7. The method of claim 6, wherein in step (4), the drying is performed by freeze-drying or supercritical CO 2 And (5) drying.
8. The method for preparing an aramid aerogel according to claim 7, wherein in the step (4), the heat treatment temperature is 60-185 ℃.
9. An aramid aerogel having thermal shock resistance obtained by the method of any one of claims 1 to 8, characterized in that the aramid aerogel has a film porosity of 91 to 97%, a breaking strength of 8.9 to 17.5mpa, and a tensile modulus of 230 to 350mpa.
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