CN116874784A - Transparent flexible aerogel for curved glass and preparation method thereof - Google Patents
Transparent flexible aerogel for curved glass and preparation method thereof Download PDFInfo
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- CN116874784A CN116874784A CN202310893337.9A CN202310893337A CN116874784A CN 116874784 A CN116874784 A CN 116874784A CN 202310893337 A CN202310893337 A CN 202310893337A CN 116874784 A CN116874784 A CN 116874784A
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- aerogel
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- alkyl
- transparent flexible
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- 239000004964 aerogel Substances 0.000 title claims abstract description 139
- 239000011521 glass Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 22
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims description 47
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000470 constituent Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 125000004946 alkenylalkyl group Chemical group 0.000 claims description 7
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- ZYSDERHSJJEJDS-UHFFFAOYSA-M tetrakis-decylazanium;hydroxide Chemical compound [OH-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC ZYSDERHSJJEJDS-UHFFFAOYSA-M 0.000 claims description 3
- OQZAQBGJENJMHT-UHFFFAOYSA-N 1,3-dibromo-5-methoxybenzene Chemical compound COC1=CC(Br)=CC(Br)=C1 OQZAQBGJENJMHT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005452 bending Methods 0.000 claims description 2
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001231 choline Drugs 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- DCFYRBLFVWYBIJ-UHFFFAOYSA-M tetraoctylazanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC DCFYRBLFVWYBIJ-UHFFFAOYSA-M 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 22
- 239000002245 particle Substances 0.000 abstract description 20
- 230000006835 compression Effects 0.000 abstract description 8
- 238000007906 compression Methods 0.000 abstract description 8
- 238000009413 insulation Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 23
- -1 polysiloxane Polymers 0.000 description 19
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- 238000006068 polycondensation reaction Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 13
- 239000002585 base Substances 0.000 description 12
- 239000000499 gel Substances 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000000352 supercritical drying Methods 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000003586 protic polar solvent Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical group CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical group CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The application provides a transparent flexible aerogel for curved glass, which is prepared by using a nitrogen-containing aprotic solvent, weak base and organic strong base to perform two-step catalytic reaction, so that the size of aerogel particles is better controlled, a more uniform network structure is formed, and the visible light transmittance and the compression strength of the aerogel are improved; further optimizing the network skeleton of the aerogel, and improving the flexibility and hydrophobicity of the aerogel; the prepared aerogel has the characteristics of high transparency, strong flexibility, good heat insulation and the like, and can be used in the manufacturing process of curved glass.
Description
Technical Field
The application relates to the technical field of aerogel manufacturing, in particular to a transparent flexible aerogel for curved glass and a preparation method thereof, and C08G 77/14.
Background
Aerogel is a porous material with a typical three-dimensional continuous nano structure, has the advantages of low heat conductivity coefficient, low density, high porosity, low refraction, high echo impedance and the like, and has very broad prospects in the fields of energy-saving buildings, electronics, communication, aerospace and the like.
The conventional method for preparing the polysiloxane aerogel generally adopts an acidic environment to hydrolyze polysiloxane, then utilizes an alkaline environment to perform polycondensation, and finally prepares the aerogel through normal pressure drying or supercritical drying; however, the light transmittance and flexibility of the aerogel prepared by the methods are very poor, which severely limits the application of the aerogel. At present, some reports on the preparation of flexible light-transmitting aerogel by using bridging siloxane as a raw material are provided, but the preparation process is complex, the required bridging siloxane has high cost, and industrialization is difficult. In addition, the problem that the aerogel has poor flexibility, low mechanical strength and the like is aggravated by the collapse phenomenon of the aerogel structure caused by capillary force in the later drying process. The aerogel prepared by the conventional method has insufficient hydrophobic property, complex and complicated surface hydrophobic modification operation is needed, and the production efficiency is low.
Chinese patent CN 110511425a discloses a flexible polysiloxane aerogel and a preparation method thereof, wherein the aerogel skeleton contains a large number of non-hydrolytic alkyl groups, and the alkyl groups generate repulsive force during compression to endow the aerogel with excellent flexibility; however, the prepared aerogel is opaque, and limits the application range. Chinese patent CN 114655960a discloses a method for preparing aerogel, which comprises polymerizing different siloxane precursors to form sol, condensing with reinforcing agent to form oligomer or siloxane chain with specific structure such as chain, trapezoid, cage or semi-cage, and endowing wet gel skeleton with high mechanical strength and special pore surface chemical property, and strictly controlling surface drying process to avoid collapse of aerogel structure; however, the prepared aerogel is still low in light transmittance, heat insulation and flexibility.
Therefore, the polysiloxane aerogel with high light transmittance, good heat insulation property, strong flexibility, excellent hydrophobicity and stable structure and performance is very important to prepare, and the application range of the aerogel can be greatly widened.
Disclosure of Invention
In order to solve the technical problems, the application firstly provides a transparent flexible aerogel for curved glass, wherein the aerogel comprises the following component unit structures:
wherein R is 1 、R 2 、R 3 、R 4 Independently selected from any of C1-C6 alkyl, C3-C8 alkenyl alkyl, C3-C8 cycloalkyl, phenyl, C1-C6 alkoxy, polymer chains comprising the above constituent units.
Further, the C3-C8 alkenyl group includes, but is not limited to, any one of propenyl, butenyl, 2-methylpropenyl, pentenyl, hexenyl, heptenyl, octenyl.
Further, the C3-C8 alkenyl alkyl group includes, but is not limited to, any one of allyl, allyl hexyl, 3-allyl.
Further, the meaning of the polymer chain comprising the above constituent units means R 4 The term "constituent unit structure" means that two constituent unit structures are connected.
Further, the ratio of (x+y)/2 is 1.1 to 1.45.
Further, the R 1 And R is 2 Alkyl groups, which may be the same or different, preferably C1-C6, including but not limited to any of methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, tert-butyl.
Further, the R 3 And R is 4 May be the same or different, preferably R 3 And R is 4 At least one of the polymer chains is a polymer chain comprising the above constituent units.
In a preferred embodiment, in the constituent unit structure of the aerogel, the R 1 、R 2 And R is 3 Independently selected from any of the C1-C6 alkyl groups, more preferably from any of the methyl, ethyl, propyl groups.
Further, the R 4 Is a polymer chain comprising the above constituent units.
Preferably, the (x+y)/2 is 1.375.
Further, the aerogel has a visible light transmittance of > 70%; aerogel density of 0.08-0.20g/cm 3 。
Further, the aerogel has a thermal conductivity of < 0.018W/(m.k); the contact angle with water is > 150 deg..
Further, the aerogel has a compressive strength > 0.2MPa; the aerogel can rebound to the initial size after releasing pressure when the compression deformation of the aerogel is less than or equal to 80 percent.
Further, the aerogel has a flexural strength > 90 °.
Secondly, the application also provides a preparation method of the aerogel, which comprises the following steps: mixing the substance A and the substance B in a mixed solution of a nitrogen-containing aprotic solvent and water, adding weak base to adjust the pH value to 8.0-10.0, catalyzing for 6-14h, and adding organic strong base to adjust the pH value to 11-14, catalyzing for 5-40min; and finally, drying to obtain the aerogel.
Further, the structure of the substance A is as follows:
wherein the R is 1 And R is 3 Independently selected from any one of C1-C6 alkyl, C3-C8 alkenyl alkyl, C3-C8 cycloalkyl, phenyl, C1-C6 alkoxy, preferably C1-C6 alkyl. R of substance A 1 And R is 3 R in the constituent unit structure corresponding to aerogel 1 And R is 3 。
Preferably, said R 1 And R is 3 Independently selected from any one of methyl, ethyl and propyl. More preferably, the R 1 And R is 3 Is methyl.
Preferably, said R 5 And R is 6 And is independently selected from any one of C1-C12 alkyl, wherein the C1-C12 alkyl comprises any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, amyl, neopentyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, n-undecyl and n-dodecyl.
Preferably, said R 5 And R is 6 Independently selected from any one of methyl, ethyl and propyl.
Further, the structure of the substance B is:
wherein the R is 7 、R 8 And R is 2 Independently selected from any one of C1-C6 alkyl, C3-C8 alkenyl alkyl and C3-C8 cycloalkyl; the R is 9 Is C1-C10 alkoxy. The R is 2 R in the constituent unit structure corresponding to aerogel 2 。
Preferably, said R 7 、R 8 And R is 2 Independently selected from any one of C1-C6 alkyl groups, more preferably any one of methyl, ethyl, propyl and butyl.
Further, R in the aerogel structures of the present application 4 R produced in substance B 9 When R is 4 In the case of alkoxy, the corresponding R 9 Without hydrolysis, i.e. R 4 And R is R 9 Consistent; when R is 4 R in the case of a polymer chain comprising the above aerogel constituent units 9 Adapted to be alkoxy, in which case R on substance B 9 As reaction sites for hydrolysis and polycondensation, aerogels can be promoted to create larger network structures. When R is 9 In the case of C1-C10 alkoxy, the hydrolysis rate and the hydrolysis degree are more suitable, and the prepared air-setThe glue structure is more uniform.
Preferably, said R 9 Methoxy or ethoxy.
Further, the molar ratio of the substance A to the substance B is (0.3-1.5): 1.
according to the application, the alkali-catalyzed siloxane is adopted to carry out hydrolysis and polycondensation reaction, silicon hydroxyl groups generated after the hydrolysis of adjacent siloxane are bonded with each other and extend to a three-dimensional direction to form a larger network crosslinking structure, but the flexibility of the crosslinking structure is not ideal, based on the alkali-catalyzed siloxane, substances A and B with different functionalities are further compounded to participate in the skeleton structure of the aerogel together, and the proper crosslinking strength and density are generated by controlling the silicon-oxygen bond in polysiloxane, so that the flexibility of the aerogel is improved, and most importantly, the excellent stability of the network structure of the aerogel is ensured, and pore collapse cannot be generated in the drying process; therefore, the amount of siloxane needs to be strictly controlled, when the amount of the substance A is too high, the crosslinking effect is too weak, even gel is not formed, when the amount of the substance B is too high, the flexibility of the gel is obviously insufficient, and only the flexibility and the stability of the framework structure of the substance A and the substance B can be considered under a specific molar ratio.
Preferably, the molar ratio of substance a to substance B is (0.33-1.33): 1.
further, the nitrogen-containing aprotic solvent is selected from any one or a combination of a plurality of N, N-dimethylformamide, N-dimethylacetamide, N-dimethylacrylamide, N-methylpyrrolidone and hexamethylphosphoric triamide.
The application emphasizes that the nitrogen-containing aprotic solvent participates in the sol-gel process of the siloxane, the nitrogen-containing aprotic solvent can be used as a receptor or an implementation body of a hydrogen bond due to the existence of a strong electronegative N atom of the nitrogen-containing aprotic solvent, and has a hydrogen bond effect with silicon hydroxyl on the surface of the sol of the siloxane, so that the nitrogen-containing aprotic solvent covers the surface of sol particles to generate a space shielding effect, prevent further collision and combination among the sol particles, ensure that the particle size of the gel particles is smaller, and promote the transparency of the aerogel; in addition, the addition of the nitrogen-containing aprotic solvent increases the gel network, improves the distribution uniformity of the gel network, inhibits the phenomenon that the structure is damaged due to stress in the gel structure, and increases the flexibility of the aerogel; however, the nitrogen-containing aprotic solvent occupying the gel pore canal is removed in the later drying process, and then larger pores remain, if the dosage is too high, more macroporous pores exist in the aerogel network structure and the non-uniformity of the pore diameter distribution of the aerogel network is increased, which in turn leads to the reduction of light transmittance.
Preferably, the nitrogen-containing aprotic solvent is selected from any one of N, N-dimethylformamide, N-dimethylacetamide and hexamethylphosphoric triamide.
Further, the molar ratio of the total amount of the substance A and the substance B, the nitrogen-containing aprotic solvent and water is (1 to 2.5): (6-12): (3-8).
Preferably, the molar ratio of the total amount of substance a and substance B, the nitrogen-containing aprotic solvent and water is (1-1.83): (9-11): (3-5).
In a preferred embodiment, the molar ratio of the total amount of substance a and substance B, the nitrogen-containing aprotic solvent and water is 1.33:10:4.
preferably, in the preparation method, weak base is added to adjust the pH value to 8.5-9.5 for catalysis for 8-12h, and organic strong base is added to adjust the pH value to 12.5-14 for catalysis for 20-30min.
Under alkaline conditions, siloxane is hydrolyzed and then rapidly condensed to generate compact colloid particles, and the particles are mutually connected to form a reticular gel; the different alkaline environments have a significant effect on the light transmission and flexibility of the aerogel of the present application: when the alkalinity is too strong, the polycondensation speed of the siloxane is very high in a short time, the particle size of the produced aerogel particles is large and the distribution is uneven, the disordered growth of the siloxane bonds in the three-dimensional space greatly reduces or even disappears the holes of the aerogel, the prepared aerogel is basically opaque, and more cracks exist on the surface of the aerogel after drying; when the alkalinity is too low, the aerogel preparation efficiency is low, and the surface of the aerogel contains a plurality of silicon hydroxyl groups, so that the aerogel is subjected to polycondensation again in the drying process, and dry shrinkage and large cracks are generated; therefore, there is also a need to provide sufficient crosslinking time for the hydrolyzed silicone to undergo hydrolysis and polycondensation reactions to a suitable degree to increase hydrogel flexibility and light transmittance. The application strictly limits the alkaline catalytic environment, and can control the aerogel particles to be finer and the pore size distribution to be denser only by comprehensively using two-stage alkali reaction and under the specific catalytic time, so that the light transmittance and the flexibility of the aerogel can be optimized.
Further, the weak base is at least one selected from ammonia water, urea, pyridine, triethanolamine, ethanolamine and diethanolamine.
Preferably, the weak base is selected from any one of ammonia water, urea and pyridine, and more preferably ammonia water.
Further, the organic strong base adopts quaternary ammonium base and derivatives thereof, including but not limited to one or a combination of a plurality of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetrahexyl ammonium hydroxide, tetraoctyl ammonium hydroxide, tetradecyl ammonium hydroxide, bisdodecyl dimethyl ammonium hydroxide and hexadecyl trimethyl ammonium hydroxide choline.
Further, the organic strong base is at least one selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrapropylammonium hydroxide.
Further, the drying mode adopts normal pressure drying or supercritical drying.
Preferably, the drying mode is supercritical drying.
Further, supercritical carbon dioxide is adopted for supercritical drying, the drying reaction temperature is 45-55 ℃, the pressure is 10-15MPa, and the heat preservation and pressure maintaining time is 5-8h.
Advantageous effects
1. According to the application, through controlling the component unit structure of the prepared aerogel, the aerogel with high light transmittance, low heat conductivity, good hydrophobicity and good flexibility can be obtained.
2. According to the application, the types and the relative contents of the substance A and the substance B are controlled, so that the aerogel skeleton generated after hydrolysis and polycondensation of the substance A and the substance B has a specific crosslinking state, excellent flexibility and superhydrophobicity are endowed to the aerogel, and a complex and complicated modification treatment process of the aerogel in the later period is avoided;
3. according to the application, the hydrolysis and polycondensation reaction and the sol-gel process of siloxane are better controlled by adopting environments with different alkalinity, so that the aerogel is grown into a more uniform network structure, the particle size and the pore space of the aerogel are finer, the visible light transmittance and the compressive strength of the aerogel are improved, the flexibility is improved, and the application range of the aerogel is widened;
4. according to the application, the nitrogen-containing aprotic solvent is used for participating in the sol-gel process of aerogel formation, the combination of the nitrogen-containing aprotic solvent and the polysiloxane precursor is increased due to the existence of the strong polar group, the excessive increase of the particle size of the polysiloxane is prevented, in addition, the capillary tension of the nitrogen-containing aprotic solvent and the aerogel framework structure is lower, the stability of the pore structure of the aerogel in the drying process is facilitated, the cracking caused by the collapse of the pores generated by the latter is avoided, and the comprehensive performance of the aerogel is further improved.
Drawings
Fig. 1: aerogel appearance pictures prepared in example 1;
fig. 2: SEM image of aerogel prepared in example 1 (scale: 500 nm);
fig. 3: aerogel appearance pictures prepared in comparative example 1;
fig. 4: SEM pictures of the aerogel prepared in comparative example 1 (scale: 50 μm).
Detailed Description
Examples
Example 1
The embodiment provides a transparent flexible aerogel for curved glass, the constitution unit structure of aerogel is:
R 1 、R 2 、R 3 are all methyl, R 4 Is a polymer chain comprising the above constituent units, (x+y)/2 is 1.375;
the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylformamide and water, adding ammonia water to adjust the pH value to 9.0, catalyzing for 8 hours, adding tetramethyl ammonium hydroxide to adjust the pH value to 13, and catalyzing for 30 minutes; finally, drying by supercritical carbon dioxide, wherein the drying reaction temperature is 50 ℃, the pressure is 12MPa, and the heat preservation and pressure maintaining time is 6 hours, so that the aerogel can be obtained;
the substance A is dimethyl dimethoxy silane, and the substance B is methyl trimethoxy silane; the ratio of the total molar amount of substance a and substance B, the molar amount of N, N-dimethylformamide, the molar amount of water was 1.33:10:4, a step of; the molar ratio of substance a to substance B was 0.9:1. fig. 1 is an external image of the aerogel prepared in example 1, and it can be seen from fig. 1 that the aerogel prepared in example 1 has a good light transmission effect. Fig. 2 is an SEM image of the aerogel prepared in example 1, and fig. 2 illustrates that the nitrogen-containing aprotic solvent can form hydrogen bonds with silicon hydroxyl groups generated by the hydrolysis of siloxane, so as to slow down the dehydration polycondensation between the silicon hydroxyl groups, control the further growth of polysiloxane particles to form larger particles, form a more uniform network structure, reduce the scattering of visible light, and improve the light transmittance.
Example 2
The embodiment provides a transparent flexible aerogel for curved glass, the constitution unit structure of aerogel is:
R 1 、R 2 、R 3 all are ethyl, R 4 Is a polymer chain comprising the above constituent units, (x+y)/2 is 1.1;
the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylacetamide and water, adding ammonia water to adjust the pH value to 9.5, catalyzing for 8 hours, adding tetraethylammonium hydroxide to adjust the pH value to 12.5, and catalyzing for 30 minutes; finally, drying by supercritical carbon dioxide, wherein the drying reaction temperature is 45 ℃, the pressure is 10MPa, and the heat preservation and pressure maintaining time is 8 hours, so that the aerogel can be obtained;
the substance A is diethyl diethoxy silane, and the substance B is ethyl triethoxy silane; the ratio of the total molar amount of the substance A to the substance B, the molar amount of N, N-dimethylformamide and the molar amount of water is 1:11:3, a step of; the molar ratio of substance a to substance B was 0.33:1.
example 3
The embodiment provides a transparent flexible aerogel for curved glass, the constitution unit structure of aerogel is:
R 1 、R 3 are all methyl, R 2 Is propyl, R 4 Is a polymer chain comprising the above constituent units, (x+y)/2 is 1.45;
the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylformamide and water, adding pyridine to adjust the pH value to 8.5, catalyzing for 12 hours, adding tetramethylammonium hydroxide to adjust the pH value to 14, and catalyzing for 20 minutes; finally, drying by supercritical carbon dioxide, wherein the drying reaction temperature is 55 ℃, the pressure is 15MPa, and the heat preservation and pressure maintaining time is 5 hours, so that the aerogel can be obtained;
the substance A is dimethyl dipropyloxy silane, and the substance B is propyl trimethoxy silane; the ratio of the total molar amount of substance A and substance B, the molar amount of N, N-dimethylformamide, and the molar amount of water was 1.83:9:5, a step of; the molar ratio of substance a to substance B was 1.33:1.
example 4
Substantially identical to example 1, except that: the ratio of the total molar amount of substance a and substance B, the molar amount of N, N-dimethylformamide, the molar amount of water was 2.5:7.83:6.
example 5
Substantially identical to example 1, except that: the ratio of the total molar amount of substance a and substance B, the molar amount of N, N-dimethylformamide, the molar amount of water was 1.33:6:8.
example 6
Substantially identical to example 1, except that: the molar ratio of substance a to substance B was 0.3:1.
example 7
Substantially identical to example 1, except that: the molar ratio of substance a to substance B was 1.5:1.
example 8
Substantially identical to example 1, except that: the substance A is methyl vinyl dimethoxy silane.
Example 9
Substantially identical to example 1, except that: the substance B is octyl trimethoxy silane.
Example 10
Substantially identical to example 1, except that: the ammonia water is replaced by triethanolamine.
Example 11
Substantially identical to example 1, except that: the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylformamide and water, adding ammonia water to adjust the pH value to 8, catalyzing for 8 hours, adding tetramethyl ammonium hydroxide to adjust the pH value to 11, and catalyzing for 30 minutes; finally, supercritical carbon dioxide is adopted for drying, the drying reaction temperature is 50 ℃, the pressure is 12MPa, and the heat preservation and pressure maintaining time is 6 hours, so that the aerogel can be obtained.
Example 12
Substantially identical to example 1, except that: the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylformamide and water, adding ammonia water to adjust the pH value to 8, catalyzing for 12 hours, adding tetramethylammonium hydroxide to adjust the pH value to 11, and catalyzing for 40 minutes; finally, supercritical carbon dioxide is adopted for drying, the drying reaction temperature is 50 ℃, the pressure is 12MPa, and the heat preservation and pressure maintaining time is 6 hours, so that the aerogel can be obtained.
Example 13
Substantially identical to example 1, except that: the tetramethylammonium hydroxide was replaced with tetra-decylammonium hydroxide.
Example 14
Substantially identical to example 1, except that: the supercritical drying pressure was 17MPa.
Example 15
Substantially identical to example 1, except that: the N, N-dimethylformamide is replaced by N-methylpyrrolidone.
Comparative example 1
Substantially identical to example 1, except that: the N, N-dimethylformamide was replaced with methanol.
Fig. 3 is an external image of the aerogel prepared in comparative example 1, and as can be seen from fig. 3, the aerogel prepared in comparative example 1 is white and has no light transmission. Fig. 4 is an SEM image of the aerogel prepared in comparative example 1, and fig. 4 illustrates that the protic solvent such as alcohols, which itself generates hydrogen bonds, has little resistance to polycondensation between silicon hydroxyl groups, and is easy to form polysiloxane particles with large particle diameters, form a macroporous structure, and cannot transmit visible light.
Comparative example 2
Substantially identical to example 1, except that: the preparation method of the aerogel comprises the following steps: mixing the substance A and the substance B in a mixed solution of N, N-dimethylformamide and water, and then adding tetramethylammonium hydroxide to adjust the pH value to 12.5 for catalyzing for 8.5 hours; finally, supercritical carbon dioxide is adopted for drying, the drying reaction temperature is 50 ℃, the pressure is 12MPa, and the heat preservation and pressure maintaining time is 6 hours, so that the aerogel can be obtained.
Comparative example 3
Substantially identical to example 1, except that: the molar ratio of the substance A to the substance B is 2:1.
comparative example 4
Substantially identical to example 1, except that: the molar ratio of the substance A to the substance B is 0.2:1.
performance test results:
performance evaluation was performed on the aerogel prepared in the above example, and the aerogel prepared in example 1 was most excellent in light transmittance (see fig. 1); the aerogel prepared in comparative example 1 was light-non-transparent (see fig. 3), and the product prepared in comparative example 3 was not gel-forming; the gel block prepared in example 5 had cracks on its surface; the test results are shown in Table 1.
TABLE 1
Analysis:
the aerogels prepared in examples 1-3 all have a visible light transmittance of greater than 70%, a water contact angle of greater than 150℃and a density of 0.08-0.20g/cm 3 The thermal conductivity is less than 0.018W/(m.k), and the compressive strength is greater than 0.2MPa; the compression deformation is within 80%, the compression deformation can be released, the compression deformation can rebound to the initial size, the compression deformation can be bent, the bending angle is about 180 degrees, and the monolithic aerogel disclosed by the application has excellent light transmittance, hydrophobicity, heat insulation, softness and structural stability.
Comparative example 1 and examples 4-5 show that: the relatively low amount of nitrogen-containing aprotic solvent in example 4 and the high water content in example 5, both of which result in an aerogel having poorer light transmittance and softness performance than example 1, may be due to: the nitrogen-containing aprotic solvent is small in amount, the siloxane (the substance A and the substance B) is relatively large in amount, the nitrogen-containing aprotic solvent cannot well shield the space of sol particles generated by prepolymerization, the polymerized network structure of the sol particles is large, the pore diameter of the aerogel is increased due to the increase of the particle size of the gel particles, and finally the light transmittance of the aerogel is reduced; the increased water content in example 5 resulted in excessive capillary stress due to solution tension in the aerogel pores during post-drying, directly resulting in collapse of the aerogel structure and cracking, and reduced performance of the aerogel.
Comparative example 1 and examples 6 to 7, comparative examples 3 to 4, as follows: with the increase of the dosage of the substance A, the flexibility of the aerogel is increased, but gel is not generated even when the dosage of the substance A is too high, and the flexibility of the gel is obviously reduced when the dosage of the substance B is too high; probably because: the Si-O chain ends existing in the substance A are fewer, so that the crosslinking degree of the silica bonds in the prepared aerogel framework can be reduced, but the addition amount of the substance A and the substance B is strictly regulated within a specified range so as to realize the optimal flexibility and the optimal light transmittance of the aerogel.
Comparative example 1 and examples 8-9 show that: the vinyl groups in example 8 may participate in the cross-linked skeleton structure of the siloxane, which increases the non-uniformity of the skeleton network distribution, thus resulting in reduced light transmittance and flexibility of the aerogel, and the other part of alkenyl groups not participating in bonding increases the attraction of the gel skeleton to water, increases the difficulty of the post-drying process, and reduces the hydrophobicity of the aerogel; the steric hindrance caused by the longer octyl group of the molecular chain in example 9 may affect the polycondensation reaction of the substance a and the substance B, and the steric effect decreases the uniformity of the polycondensation reaction and the molecular arrangement state of the aerogel skeleton structure, while the hydrophobicity of the aerogel increases, but other properties decrease instead.
Comparative example 1 and example 10 show that: in example 10, the organic weak base triethanolamine was used, but all the properties of the aerogel were slightly reduced, probably because of molecular action between the triethanolamine and the substances a and B, which increased the viscosity with the aerogel network skeleton, in which case the degree of matching between the capillary stress generated when the solvent (solution) in the system volatilized and the elastic modulus of the gel skeleton was reduced, resulting in collapse of part of the pores during drying, and thus poor overall performance of the aerogel.
Comparative example 1 and examples 11 to 12, comparative example 2, as follows: only by adopting weak base and strong base to gradually react and controlling the environmental alkalinity and the reaction time, the flexibility and the light transmittance of the aerogel can be better improved, when the alkalinity is insufficient, the polysiloxane is difficult to fully extend the network skeleton, and the hydrolysis and polycondensation reaction speeds of the polysiloxane are too different. When the alkalinity is too high, the reaction rate is too high, which results in a decrease in uniformity of the produced aerogel, thereby affecting the performance.
Comparative example 1 and example 13 show that: when the molecular chain of the alkyl group in the organic base is too long, although the polycondensation of the silicon hydroxyl group can be more effectively inhibited, the polymerization reaction of the siloxane is also influenced, so that the polymerization reaction is not uniformly carried out in the three-dimensional direction, and the aerogel has relatively weak performance.
Comparative example 1 and example 14 show that: excessive drying pressure can produce some compression on the pores of the aerogel, possibly resulting in breaking the originally intended uniform pore size distribution, resulting in a decrease in the flexibility and light transmittance of the aerogel.
Comparative example 1 and example 15 show that: n-methylpyrrolidone is relatively weak in polarity, and shows a slightly lower protective effect on the siloxane prepolymer, and a slight increase in the aerogel particle size results in a decrease in light transmittance.
Comparative example 1 and comparative example 1 show that: the protic solvent inhibits the hydrolysis of the polysiloxane, but hydrogen bonds generated by the protic solvent cannot better inhibit the polycondensation of the silicon hydroxyl groups, and the aerogel particle size is increased, and the light transmittance, the flexibility and the like are reduced.
Claims (10)
1. A transparent flexible aerogel for curved glass, characterized in that the aerogel comprises the following constituent unit structures:
wherein R is 1 、R 2 、R 3 、R 4 Independently selected from any of C1-C6 alkyl, C3-C8 alkenyl alkyl, C3-C8 cycloalkyl, phenyl, C1-C6 alkoxy, polymer chains comprising the above constituent units; (x+y)/2 is 1.1 to 1.45.
2. The transparent flexible aerogel of claim 1, wherein R 1 And R is 2 Alkyl groups which may be the same or different, preferably C1-C6; the R is 3 And R is 4 At least one of the polymer chains is a polymer chain comprising the above constituent units.
3. The transparent flexible aerogel of claim 1, wherein the aerogel has a visible light transmission > 70%; the thermal conductivity of the aerogel is less than 0.018W/(m.k); contact angle to water > 150 °; the bending strength is > 90 degrees.
4. A method for the preparation of a transparent flexible aerogel according to any one of claims 1 to 3, characterized in that it comprises in particular: mixing the substance A and the substance B in a mixed solution of a nitrogen-containing aprotic solvent and water, adding weak base to adjust the pH value to 8.0-10.0, catalyzing for 6-14h, and adding organic strong base to adjust the pH value to 11-14, catalyzing for 5-40min; finally, drying to obtain aerogel;
the structure of the substance A is as follows:
the R is 1 And R is 3 Independently selected from any one of C1-C6 alkyl, C3-C8 alkenyl alkyl, C3-C8 cycloalkyl, phenyl, C1-C6 alkoxy;
the structure of the substance B is as follows:
wherein the R is 7 、R 8 And R is 2 Independently selected from any one of C1-C6 alkyl, C3-C8 alkenyl alkyl and C3-C8 cycloalkyl.
5. The method of claim 4, wherein R is 1 And R is 3 Independently selected from any one of methyl, ethyl and propyl.
6. The method of claim 4, wherein R is 7 、R 8 And R is 2 Independently selected from any one of C1-C6 alkyl, more preferably any one of methyl, ethyl, propyl and butyl; r is R 9 Alkoxy of C1-C10 is preferably methoxy or ethoxy.
7. The method according to claim 4, wherein the molar ratio of the substance A to the substance B is (0.3 to 1.5): 1, a step of; preferably (0.33-1.33): 1.
8. the process according to claim 4, wherein the molar ratio of the total amount of the substance A and the substance B, the nitrogen-containing aprotic solvent and water is (1 to 2.5): (6-12): (3-8); preferably (1-1.83): (9-11): (3-5).
9. The preparation method according to claim 4, wherein in the preparation method, weak base is added to adjust the pH value to 8.5-9.5 for catalyzing for 8-12 hours, and organic strong base is added to adjust the pH value to 12.5-14 for catalyzing for 20-30 minutes.
10. The method according to claim 4, wherein the organic strong base is quaternary ammonium base or its derivative, including one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, bisdecyldimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide choline; preferably at least one of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide.
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