CN110817889A - Preparation method of toughened silica aerogel, toughened silica aerogel and application of toughened silica aerogel - Google Patents
Preparation method of toughened silica aerogel, toughened silica aerogel and application of toughened silica aerogel Download PDFInfo
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- CN110817889A CN110817889A CN201911195855.3A CN201911195855A CN110817889A CN 110817889 A CN110817889 A CN 110817889A CN 201911195855 A CN201911195855 A CN 201911195855A CN 110817889 A CN110817889 A CN 110817889A
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- silica aerogel
- toughened
- wet gel
- surface modifier
- toughened silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011240 wet gel Substances 0.000 claims abstract description 47
- 238000001035 drying Methods 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKQXCDUCLYWRHA-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[Si](C)(C)Cl OKQXCDUCLYWRHA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- CSBJCQMIXISILC-UHFFFAOYSA-N 3-[chloro(dimethyl)silyl]propyl prop-2-enoate Chemical compound C[Si](C)(Cl)CCCOC(=O)C=C CSBJCQMIXISILC-UHFFFAOYSA-N 0.000 claims abstract description 6
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000499 gel Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000012774 insulation material Substances 0.000 claims abstract description 5
- 239000002912 waste gas Substances 0.000 claims abstract description 4
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 4
- ZCRUJAKCJLCJCP-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C=C ZCRUJAKCJLCJCP-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 239000003937 drug carrier Substances 0.000 claims description 3
- -1 polysiloxane Polymers 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 16
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 239000004964 aerogel Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- 238000002791 soaking Methods 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000007605 air drying Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000004438 BET method Methods 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 238000007906 compression Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000004108 freeze drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- ZUKORJOFWRTPBM-UHFFFAOYSA-N (chloro-methyl-propylsilyl)methyl prop-2-enoate Chemical compound C(C=C)(=O)OC[Si](Cl)(C)CCC ZUKORJOFWRTPBM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SHTFMSFIGYPTIX-UHFFFAOYSA-M dodecyl-dimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCOC(=O)C(C)=C SHTFMSFIGYPTIX-UHFFFAOYSA-M 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/158—Purification; Drying; Dehydrating
- C01B33/1585—Dehydration into aerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to the technical field of aerogel, in particular to a preparation method of toughened silica aerogel, the toughened silica aerogel and application thereof. Uniformly mixing a silicon source, an organic solvent and water, preparing wet gel through a sol-gel step, and then performing aging, solvent replacement, surface modifier modification, crosslinking and drying to obtain the toughened silica aerogel; the surface modifier is selected from one or more of 3-methacryloxypropyldimethylchlorosilane, acryloxypropyldimethylchlorosilane, 3-methacryloxypropyldimethylmethoxysilane and acryloxypropyldimethylmethoxysilane. The silicon dioxide aerogel disclosed by the invention has better toughness, wet gel can be dried under normal pressure without being damaged, the equipment investment is saved, the production efficiency is improved, the production cost is reduced, and the silicon dioxide aerogel can be applied to the fields of heat insulation materials, waste gas treatment materials, waste water treatment materials, catalysts and the like.
Description
Technical Field
The invention relates to the technical field of aerogel, in particular to a preparation method of toughened silica aerogel, the toughened silica aerogel and application thereof.
Background
The silica aerogel is a novel light nano porous amorphous solid material, has a continuous irregular network structure, has unique properties including high specific surface, low refractive index, low conductivity, low thermal conductivity, low sound propagation speed, low density and the like, can be applied to insulating layers, refractive coatings and reflective coatings of ultralow conductivity, sound insulation plates, acoustic impedance coupling materials, catalyst carriers, efficient heat insulation materials, rechargeable batteries, drug carriers and the like, and is valued by researchers in the industry.
Silica aerogel has been taken out of laboratories and entered the field of industrial application at present, but since it generally requires freeze drying or supercritical drying when dried, the equipment is expensive, the cost is high, it is not suitable for mass production, and it is easy to be broken, so that its production and application are severely limited.
In the prior art, the mechanical strength of silica aerogel is mainly improved by adding a supporting material before preparing wet gel, wherein a method of adding hydroxyl-terminated dimethyl siloxane after hydrolysis (CN105036142B), a method of adding melamine after hydrolysis (CN106477588B), a method of adding chopped carbon fiber after hydrolysis (CN109650843A) and a method of forming calcium silicate fiber in situ in silica wet gel (CN106565198B) are provided.
Other methods are disclosed in CN103708476B using methyltrimethoxysilane or methyltriethoxysilane as the silicon source; CN107513140A, namely a method for preparing silica aerogel by adding methacryloyloxyethyl dodecyl trimethyl ammonium chloride into wet gel and then adding the silica aerogel into methyl methacrylate for copolymerization reaction; CN105621420B discloses a method for obtaining silica aerogel by adding polyvinyl alcohol in hydrolysis, drying the sol-gel under normal pressure to obtain a semi-dry gel, and adding into a foaming composition for foaming.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of toughened silica aerogel, the prepared toughened silica aerogel can be dried under normal pressure, the equipment investment is saved, the production efficiency is improved, the production cost is reduced, and the large-scale production of the silica aerogel can be realized.
The invention also aims to provide the toughened silica aerogel which has better mechanical strength.
The invention also aims to provide application of the toughened silica aerogel.
The invention adopts the following technical scheme:
a preparation method of toughened silica aerogel comprises the following steps of uniformly mixing a silicon source, an organic solvent and water, preparing wet gel through a sol-gel step, aging, absolute ethyl alcohol replacement, surface modifier modification, crosslinking and drying to obtain the toughened silica aerogel; the surface modifier is selected from one or more of 3-methacryloxypropyldimethylchlorosilane, acryloxypropyldimethylchlorosilane, 3-methacryloxypropyldimethylmethoxysilane and acryloxypropyldimethylmethoxysilane.
Preferably, the step of replacing with absolute ethyl alcohol is further included between the modification and the crosslinking of the surface modifier. Through the step of absolute ethyl alcohol replacement, part of the surface modifier which does not participate in the reaction can be removed.
Preferably, the silicon source is selected from one or more of methyl orthosilicate, ethyl orthosilicate, sodium silicate, methyltrimethoxysilane, methyltriethoxysilane and polysiloxane. In a more preferred embodiment, the silicon source is selected from a single silicon source, such as methyl orthosilicate, ethyl orthosilicate or sodium silicate, and may also be selected from a composite silicon source, such as a mixture of methyl orthosilicate and methyltrimethoxysilane, a mixture of ethyl orthosilicate and methyltrimethoxysilane, and a mixture of sodium silicate and methyltrimethoxysilane.
Preferably, the organic solvent is selected from one or more of methanol, ethanol, isopropanol, acetone and tetrahydrofuran.
Preferably, the molar ratio of the silicon source, the organic solvent and the water is 1:8-15: 4-8. In a more preferable embodiment, the molar ratio of the silicon source, the organic solvent and the water is 1:8-13: 4-6.
The sol-gel step is that firstly, the pH value of a reaction system is adjusted to 2-4 by using an acidic substance for hydrolysis, and then, the pH value of the reaction system is adjusted to 8-12 by using an alkaline substance for condensation, wherein the acidic substance can be at least one of sulfuric acid, hydrochloric acid, nitric acid, formic acid, acetic acid and oxalic acid, and the alkaline substance can be at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tetramethylammonium hydroxide, ammonia water and barium hydroxide.
The aging may be by placing the wet gel in a water bath at 30-90 ℃ for 1-3 hours.
And replacing the absolute ethyl alcohol with the aged absolute ethyl alcohol, adding the absolute ethyl alcohol into the wet gel, soaking the wet gel for 1-2 hours, and filtering to remove the redundant solvent.
Preferably, the molar ratio of the silicon source to the surface modifier is 1: 0.1-0.5.
Preferably, the molar ratio of the silicon source to the surface modifier is 1: 0.15-0.4.
The surface modifier modification is to dissolve the modifier in n-hexane according to the volume ratio of the modifier to the n-hexane of 1:5-10, and soak the wet gel for 1-5 hours at normal temperature.
Preferably, the crosslinking is irradiation crosslinking. The irradiation crosslinking does not need to additionally use a free radical initiator, and can generate free radicals in a reaction system at room temperature to initiate and complete polymerization.
The drying may be supercritical drying or freeze drying, or atmospheric drying.
A toughened silica aerogel prepared by the preparation method of any one of the above embodiments.
The application of the toughened silica aerogel in the embodiment in the fields of heat insulation materials, waste gas and wastewater treatment materials, catalysts and drug carriers.
The invention has the beneficial effects that:
(1) according to the invention, after the silica wet gel is aged, the silicon hydroxyl on the surface of the silica particles is treated by adopting the silane coupling agent containing the carbon-carbon unsaturated double bond organic group, so that the silica particles are changed from hydrophilicity to hydrophobicity, and meanwhile, the carbon-carbon unsaturated double bond can participate in free radical polymerization and crosslinking, so that on one hand, the hydrophobicity can be continuously improved, and on the other hand, the mechanical strength of the silica wet gel can be improved by virtue of the crosslinked three-dimensional structure of the organic group, therefore, a normal-pressure drying process can be used, the cost of drying equipment is saved, the production efficiency is improved, the production.
(2) The compressive strength of the obtained toughened silica aerogel reaches over 0.58MPa, is improved by over 13 times compared with that of the conventional silica aerogel, and is not crushed when being compressed by 20 percent, while the conventional silica aerogel is crushed when being compressed by less than 3 percent.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description.
Example 1
Adding tetraethoxysilane, absolute ethyl alcohol and deionized water into a container at normal temperature according to the molar ratio of 1:8:4.2, uniformly mixing, adding 0.1mol/L dilute sulfuric acid to adjust the pH value to be 2.5 for hydrolysis, adding sodium hydroxide to adjust the pH value to be 9.5 for condensation, and obtaining wet gel; aging the wet gel in a water bath at 40 ℃ for 2 hours, soaking the wet gel in absolute ethyl alcohol for 2 hours for solvent replacement, performing solvent replacement for 3 times, taking out the wet gel, soaking the wet gel in a n-hexane solution of 3-methacryloxypropyl dimethylchlorosilane (the molar ratio of the 3-methacryloxypropyl dimethylchlorosilane to the ethyl orthosilicate is 0.12:1, and the volume ratio of the 3-methacryloxypropyl dimethylchlorosilane to the n-hexane is 1:10) for 3 hours, taking out the wet gel, performing irradiation crosslinking, and sequentially drying in a 40 ℃ forced air drying oven for 2 hours, a 70 ℃ forced air drying oven for 3 hours, and a 110 ℃ forced air drying oven for 1.5 hours to obtain the toughened silica aerogel 1. The specific surface area (BET method) of toughened silica aerogel 1 was measured to be 530m2G, density 0.115g/cm3The porosity was 91%, the thermal conductivity at room temperature (hot wire method) was 0.0155W/(m.k), the compressive strength was 0.85MPa, and no fracture occurred at 20% compression.
Example 2
Adding tetraethoxysilane, acetone and deionized water into a container at normal temperature according to the molar ratio of 1:10:4.5, uniformly mixing, adding oxalic acid to adjust the pH to 2.5 for hydrolysis, adding ammonia water to adjust the pH to 10.0 for condensation to obtain wet gel; aging the wet gel in 60 deg.C water bath for 1.5 hr, soaking in anhydrous ethanol for 2 hr for solvent replacement for 3 times, taking out the wet gel, and soaking in n-hexane solution of acryloyloxypropyl dimethylchlorosilane (acryloyloxypropyl dimethylchlorosilane and n-hexane solution of acryloyloxypropyl dimethylchlorosilane)The molar ratio of ethyl silicate is 0.2:1, the volume ratio of acryloyloxy propyl dimethylchlorosilane to n-hexane is 1:12), the wet gel is taken out, the wet gel is soaked in absolute ethyl alcohol for 2 hours and then subjected to solvent replacement for 2 times, the wet gel is taken out again, irradiation crosslinking is carried out, and the wet gel is dried in a 40 ℃ forced air drying oven for 2.5 hours, a 70 ℃ forced air drying oven for 2.5 hours and a 110 ℃ forced air drying oven for 1.5 hours in sequence to obtain the toughened silica aerogel 2. The specific surface area (BET method) of toughened silica aerogel 2 was measured to be 620m2G, density 0.109g/cm3The porosity was 93%, the thermal conductivity at room temperature (hot wire method) was 0.0145W/(m.k), the compressive strength was 0.58MPa, and no fracture occurred at 20% compression.
Example 3
In the embodiment 2, the irradiated and crosslinked wet gel is dried by a supercritical carbon dioxide drying method, so as to obtain the toughened silica aerogel 3. The specific surface area (BET method) of toughened silica aerogel 3 was measured to be 660m2A density of 0.106g/cm3The porosity was 95%, the thermal conductivity at room temperature (hot wire method) was 0.0139W/(m.k), the compressive strength was 0.61MPa, and no fracture occurred at 20% compression.
Example 4
Adding methyl orthosilicate, methanol and deionized water into a container at normal temperature according to the molar ratio of 1:12:4.8, uniformly mixing, adding 0.1mol/L dilute sulfuric acid to adjust the pH to be 3.5 for hydrolysis, adding ammonia water to adjust the pH to be 9.5 for condensation, and obtaining wet gel; aging wet gel in 40 deg.C water bath for 2.5 hr, soaking in anhydrous ethanol for 2 hr for solvent replacement, performing solvent replacement for 3 times, taking out wet gel, soaking in n-hexane solution of 3-methacryloxypropyl dimethyl methoxy silane (molar ratio of 3-methacryloxypropyl dimethyl methoxy silane to ethyl orthosilicate is 0.35:1, volume ratio of 3-methacryloxypropyl dimethyl methoxy silane to n-hexane is 1:10) for 5 hr, taking out wet gel, soaking in anhydrous ethanol for 2 hr for solvent replacement, performing solvent replacement for 2 times, taking out wet gel, irradiating for crosslinking, drying in 40 deg.C blast drying oven for 3 hr, 70 deg.CAnd drying in a forced air drying oven for 2 hours and drying in a forced air drying oven at the temperature of 110 ℃ for 1.5 hours to obtain the toughened silica aerogel 4. The specific surface area (BET method) of toughened silica aerogel 4 was measured to be 610m2G, density 0.110g/cm3The porosity was 93%, the thermal conductivity at room temperature (hot wire method) was 0.0148W/(m.k), the compressive strength was 0.63MPa, and no fracture occurred at 20% compression.
Example 5
Adding tetraethoxysilane, absolute ethyl alcohol and deionized water into a container at normal temperature according to the molar ratio of 1:12:4.5, uniformly mixing, adding oxalic acid to adjust the pH to 3.0 for hydrolysis, adding ammonia water to adjust the pH to 9.5 for condensation to obtain wet gel; aging the wet gel in a water bath at 40 ℃ for 2.5 hours, soaking the wet gel in absolute ethyl alcohol for 2 hours for solvent replacement, performing solvent replacement for 3 times, taking out the wet gel, soaking the wet gel in a n-hexane solution of 3-methacryloxypropyl dimethylchlorosilane (the molar ratio of the 3-methacryloxypropyl dimethylchlorosilane to the ethyl orthosilicate is 0.45:1, and the volume ratio of the 3-methacryloxypropyl dimethylchlorosilane to the n-hexane is 1:10) for 4 hours, taking out the wet gel again, soaking the wet gel in absolute ethyl alcohol for 2 hours for solvent replacement, performing solvent replacement for 2 times, taking out the wet gel, performing irradiation crosslinking, drying the wet gel in a blast drying oven at 40 ℃ for 3 hours, and drying the wet gel in a blast drying oven at 70 ℃ for 2 hours in turn, and drying in a forced air drying oven at 110 ℃ for 1.5 hours to obtain the toughened silica aerogel 5. The specific surface area (BET method) of toughened silica aerogel 5 was measured to be 510m2G, density 0.114g/cm3The porosity was 91%, the thermal conductivity at room temperature (hot wire method) was 0.0153W/(m.k), the compressive strength was 0.72MPa, and no fracture occurred at 20% compression.
Example 6
The wet gel after irradiation with alternating current in example 5 was dried by freeze-drying to obtain toughened silica aerogel 6. The specific surface area (BET method) of toughened silica aerogel 6 was measured to be 540m2(ii)/g, density 0.111g/cm3The porosity was 93%, the thermal conductivity at room temperature (hot wire method) was 0.0149W/(m.k), the compressive strength was 0.74MPa, and the compression was 20% or lessBreakage occurs.
Comparative example 1
The wet gel aged in example 1 was immersed in absolute ethanol for 2 hours for solvent replacement, the solvent replacement was performed 3 times, the wet gel was taken out, immersed in an n-hexane solution of trimethylchlorosilane (the volume ratio of trimethylchlorosilane to n-hexane was 1:6) for 3 hours, the wet gel was taken out, and dried by a freeze-drying method to obtain a silica aerogel. The silica aerogel was measured to have a specific surface area (BET method) of 740m2A density of 0.107 g/cm/g3The porosity was 95%, the thermal conductivity at room temperature (hot wire method) was 0.0125W/(m.k), the compressive strength was 0.042MPa, and the fracture occurred when the compression was not more than 3%.
Comparative example 2
In comparative example 1, after the wet gel was treated with trimethylchlorosilane and dried at 30 ℃ under normal pressure, silica aerogel could not be obtained.
From the above, the preparation method of the toughened silica aerogel can be used for drying under normal pressure, and the obtained silica aerogel has better compressive strength, which is improved by more than 13 times compared with the conventional silica aerogel, and can not be crushed even if being compressed by 20%. Therefore, the toughened silica aerogel is suitable for large-scale production and can be applied to the fields of heat insulation materials, waste gas treatment materials, wastewater treatment materials, catalysts and the like.
The foregoing has shown and described the fundamental principles, major features and advantages of the invention. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, which are merely preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and that equivalent changes and modifications made within the scope of the present invention and the specification should be covered thereby. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A preparation method of toughened silica aerogel is characterized by comprising the following steps: uniformly mixing a silicon source, an organic solvent and water, preparing wet gel through a sol-gel step, and then performing aging, absolute ethyl alcohol replacement, surface modifier modification, crosslinking and drying to obtain the toughened silica aerogel; the surface modifier is selected from one or more of 3-methacryloxypropyldimethylchlorosilane, acryloxypropyldimethylchlorosilane, 3-methacryloxypropyldimethylmethoxysilane and acryloxypropyldimethylmethoxysilane.
2. The method of claim 1, wherein: the step of absolute ethyl alcohol replacement is also included between the modification and the crosslinking of the surface modifier.
3. The production method according to claim 1 or 2, characterized in that: the silicon source is selected from one or more of methyl orthosilicate, ethyl orthosilicate, sodium silicate, methyltrimethoxysilane, methyltriethoxysilane and polysiloxane.
4. The production method according to claim 1 or 2, characterized in that: the organic solvent is selected from one or more of methanol, ethanol, isopropanol, acetone and tetrahydrofuran.
5. The production method according to claim 1 or 2, characterized in that: the molar ratio of the silicon source to the organic solvent to the water is 1:8-15: 4-8.
6. The production method according to claim 1 or 2, characterized in that: the molar ratio of the silicon source to the surface modifier is 1: 0.1-0.5.
7. The production method according to claim 1 or 2, characterized in that: the molar ratio of the silicon source to the surface modifier is 1: 0.15-0.4.
8. The production method according to claim 1 or 2, characterized in that: the crosslinking is irradiation crosslinking.
9. A toughened silica aerogel produced by the production method according to any one of claims 1 to 8.
10. The application of the toughened silica aerogel of claim 9 in the fields of heat insulation materials, waste gas and wastewater treatment materials, catalysts and drug carriers.
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