CN113387365A - Method for organically modifying nano silicon dioxide aerogel - Google Patents
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- CN113387365A CN113387365A CN202110814842.0A CN202110814842A CN113387365A CN 113387365 A CN113387365 A CN 113387365A CN 202110814842 A CN202110814842 A CN 202110814842A CN 113387365 A CN113387365 A CN 113387365A
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- 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
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- 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
- C01B33/141—Preparation of hydrosols or aqueous dispersions
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
- Y02B80/10—Insulation, e.g. vacuum or aerogel insulation
Abstract
The invention discloses a method for organically modifying nano silicon dioxide aerogel, belonging to the technical field of aerogel, and the method comprises the following steps: mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel to obtain the organic modified nano silicon dioxide aerogel; the modifier prepared in the invention contains a flame-retardant element N, and C ═ N double bonds in the molecular structure of the modifier can generate a crosslinking reaction at high temperature to form a stable carbon layer, so that the modifier plays a role in thermal protection on a polymer material. The hydroxyl on the surface of the silicon dioxide is modified by adopting the modifier to prepare the aerogel with hydrophobic property, so that the compatibility of the aerogel and a matrix is further improved, the problem of interface compatibility is solved, and the application of the aerogel in the aspect of heat insulation and flame retardation materials is improved.
Description
Technical Field
The invention belongs to the technical field of aerogel, and particularly relates to a method for organically modifying nano silicon dioxide aerogel.
Background
The nano silicon dioxide aerogel is a novel porous amorphous material with low density, low thermal conductivity and high porosity, has unique thermal, acoustic, optical and electrical properties, and has wide application in various fields such as heat insulation, sound insulation, adsorption and the like. The surface of the silica aerogel has a plurality of hydroxyl groups, so that the silica aerogel has poor compatibility with a polyester heat-insulating flame-retardant material matrix, and the practical application of the nano silica aerogel is limited.
According to the invention, the surface of the silicon dioxide aerogel is organically modified, so that the interface effect of the silicon dioxide aerogel and a polyester matrix is improved, the problem of interface compatibility is solved, and the improvement of the dispersibility of the silicon dioxide aerogel in the polyester matrix is realized.
Disclosure of Invention
The invention provides a method for organically modifying nano silicon dioxide aerogel.
The purpose of the invention can be realized by the following technical scheme:
a method for organically modifying nano-silica aerogel comprises the following steps:
mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel to obtain the organic modified nano silicon dioxide aerogel;
wherein, the modifier is prepared by the following steps:
step S11, mixing aniline, p-hydroxybenzaldehyde and 1, 4-dioxane, heating to 85 ℃ under the protection of nitrogen, reacting for 6 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: cooling the obtained reaction solution to room temperature, reducing pressure, concentrating to remove the solvent, then washing with ethanol, and after washing is finished, drying at the temperature of 75 ℃ to constant weight to obtain an intermediate 1; the dosage ratio of the aniline to the p-hydroxybenzaldehyde to the 1, 4-dioxane is 1 g: 1.2 g: 20 mL;
the reaction process is as follows:
step S12, mixing the intermediate 1, tetrahydrofuran and triethylamine, dropwise adding phosphorus oxychloride at the temperature of 20-25 ℃, keeping the temperature unchanged after dropwise adding, stirring for reacting for 10 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: concentrating the obtained reaction solution under reduced pressure to remove the solvent, and purifying by a column to obtain an intermediate 2; 2.2g of the intermediate 1, tetrahydrofuran, triethylamine and phosphorus oxychloride: 40mL of: 2.97 g: 1.5 g;
the reaction process is as follows:
step S13, mixing 2-hydroxyethyl acrylate, dichloromethane and triethylamine, stirring and cooling to 0 ℃ under the protection of nitrogen, slowly dropwise adding a dichloromethane solution of the intermediate 2, keeping the temperature unchanged after dropwise adding, continuously stirring and reacting for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: washing the obtained reaction solution with deionized water, a sodium hydroxide solution with the mass fraction of 5% and deionized water in sequence, drying the obtained organic phase with anhydrous sodium sulfate after washing, and removing the solvent by decompression concentration after drying to obtain an intermediate 3; the dosage ratio of the dichloromethane solution of the 2-hydroxyethyl acrylate, the dichloromethane, the triethylamine and the intermediate 2 is 1.2 g: 30mL of: 2.1 g: 50mL, wherein the dichloromethane solution of intermediate 2 is intermediate 2 and dichloromethane is prepared according to the following steps of 1 g: 10mL of the mixture is mixed;
the reaction process is as follows:
step S14, mixing the intermediate 3 and toluene, heating to 50 ℃ under the protection of nitrogen, adding a Kaster catalyst, continuing to stir and react for 60min, then dropwise adding triethoxysilane, heating to 70 ℃ after dropwise adding, reacting for 24h, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: filtering the obtained reaction solution while the reaction solution is hot, cooling to room temperature, and removing the solvent by vacuum concentration to obtain a modifier; the dosage ratio of the intermediate, the toluene, the Kaster catalyst and the triethoxysilane is 5.5 g: 100mL of: 0.2 mL: 1.7 g.
The reaction process is as follows:
further, when the gel is dried, a fractional drying method is adopted, and the gel is dried for 24 hours, 2 hours, 1.5 hours and 1 hour at 60 ℃, 80 ℃, 100 ℃ and 120 ℃.
Further, the concentration of the oxalic acid aqueous solution is 1 mol/L; the mass fraction of the ammonia water is 25 percent; the dosage mass ratio of the ethyl orthosilicate to the modifier is 1: 0.5-0.7; the dosage ratio of the ethyl orthosilicate, the ethanol, the oxalic acid aqueous solution and the ammonia water is 1 g: 20mL of: 0.6 g: 0.5 g.
The invention has the beneficial effects that:
the modifier prepared in the invention contains a flame-retardant element N, and C ═ N double bonds in the molecular structure of the modifier can generate a crosslinking reaction at high temperature to form a stable carbon layer, so that the modifier plays a role in thermal protection on a polymer material. The modified silicon dioxide aerogel contains flexible Si-C bonds, rigid benzene rings and C-N bonds, so that the nano-pore structure can be maintained in normal-pressure drying, and the modified silicon dioxide aerogel has good mechanical properties. The surface of the silicon dioxide aerogel is rich in hydroxyl groups, and the hygroscopicity is strong, so that the structure of the aerogel collapses. The hydroxyl on the surface of the silicon dioxide is modified by adopting the modifier to prepare the aerogel with hydrophobic property, the compatibility of the modified silicon dioxide aerogel and other flame-retardant matrixes is further improved, the problem of interface compatibility is solved, and the application of the modified silicon dioxide aerogel in the aspect of heat-insulating flame-retardant materials is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a modifier:
step S11, mixing aniline, p-hydroxybenzaldehyde and 1, 4-dioxane, heating to 85 ℃ under the protection of nitrogen, reacting for 6 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: cooling the obtained reaction solution to room temperature, reducing pressure, concentrating to remove the solvent, then washing with ethanol, and after washing is finished, drying at the temperature of 75 ℃ to constant weight to obtain an intermediate 1;
step S12, mixing the intermediate 1, tetrahydrofuran and triethylamine, dropwise adding phosphorus oxychloride at the temperature of 20 ℃, keeping the temperature unchanged after the dropwise adding is finished, stirring for reacting for 10 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: concentrating the obtained reaction solution under reduced pressure to remove the solvent, and purifying by a column to obtain an intermediate 2;
step S13, mixing 2-hydroxyethyl acrylate, dichloromethane and triethylamine, stirring and cooling to 0 ℃ under the protection of nitrogen, slowly dropwise adding a dichloromethane solution of the intermediate 2, keeping the temperature unchanged after dropwise adding, continuously stirring and reacting for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: washing the obtained reaction solution with deionized water, a sodium hydroxide solution with the mass fraction of 5% and deionized water in sequence, drying the obtained organic phase with anhydrous sodium sulfate after washing, and removing the solvent by decompression concentration after drying to obtain an intermediate 3;
step S14, mixing the intermediate 3 and toluene, heating to 50 ℃ under the protection of nitrogen, adding a Kaster catalyst, continuing to stir and react for 60min, then dropwise adding triethoxysilane, heating to 70 ℃ after dropwise adding, reacting for 24h, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: and filtering the obtained reaction solution while the reaction solution is hot, cooling to room temperature, and concentrating under reduced pressure to remove the solvent to obtain the modifier.
Wherein the dosage ratio of the aniline, the p-hydroxybenzaldehyde and the 1, 4-dioxane in the step S11 is 1 g: 1.2 g: 20 mL; in step S12, 2.2g of intermediate 1, tetrahydrofuran, triethylamine, and phosphorus oxychloride: 40mL of: 2.97 g: 1.5 g; the amount ratio of the 2-hydroxyethyl acrylate, dichloromethane, triethylamine and the dichloromethane solution of intermediate 2 in step S13 was 1.2 g: 30mL of: 2.1 g: 50mL, wherein the dichloromethane solution of intermediate 2 is intermediate 2 and dichloromethane is prepared according to the following steps of 1 g: 10mL of the mixture is mixed; in the step S14, the using amount ratio of the intermediate, the toluene, the Kaster catalyst and the triethoxysilane is 5.5 g: 100mL of: 0.2 mL: 1.7 g.
Example 2
Preparing a modifier:
step S11, mixing aniline, p-hydroxybenzaldehyde and 1, 4-dioxane, heating to 85 ℃ under the protection of nitrogen, reacting for 6 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: cooling the obtained reaction solution to room temperature, reducing pressure, concentrating to remove the solvent, then washing with ethanol, and after washing is finished, drying at the temperature of 75 ℃ to constant weight to obtain an intermediate 1;
step S12, mixing the intermediate 1, tetrahydrofuran and triethylamine, dropwise adding phosphorus oxychloride at the temperature of 25 ℃, keeping the temperature unchanged after the dropwise adding is finished, stirring for reacting for 10 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: concentrating the obtained reaction solution under reduced pressure to remove the solvent, and purifying by a column to obtain an intermediate 2;
step S13, mixing 2-hydroxyethyl acrylate, dichloromethane and triethylamine, stirring and cooling to 0 ℃ under the protection of nitrogen, slowly dropwise adding a dichloromethane solution of the intermediate 2, keeping the temperature unchanged after dropwise adding, continuously stirring and reacting for 24 hours, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: washing the obtained reaction solution with deionized water, a sodium hydroxide solution with the mass fraction of 5% and deionized water in sequence, drying the obtained organic phase with anhydrous sodium sulfate after washing, and removing the solvent by decompression concentration after drying to obtain an intermediate 3;
step S14, mixing the intermediate 3 and toluene, heating to 50 ℃ under the protection of nitrogen, adding a Kaster catalyst, continuing to stir and react for 60min, then dropwise adding triethoxysilane, heating to 70 ℃ after dropwise adding, reacting for 24h, and performing post-treatment after the reaction is finished, wherein the post-treatment process comprises the following steps: and filtering the obtained reaction solution while the reaction solution is hot, cooling to room temperature, and concentrating under reduced pressure to remove the solvent to obtain the modifier.
Wherein the dosage ratio of the aniline, the p-hydroxybenzaldehyde and the 1, 4-dioxane in the step S11 is 1 g: 1.2 g: 20 mL; in step S12, 2.2g of intermediate 1, tetrahydrofuran, triethylamine, and phosphorus oxychloride: 40mL of: 2.97 g: 1.5 g; the amount ratio of the 2-hydroxyethyl acrylate, dichloromethane, triethylamine and the dichloromethane solution of intermediate 2 in step S13 was 1.2 g: 30mL of: 2.1 g: 50mL, wherein the dichloromethane solution of intermediate 2 is intermediate 2 and dichloromethane is prepared according to the following steps of 1 g: 10mL of the mixture is mixed; in the step S14, the using amount ratio of the intermediate, the toluene, the Kaster catalyst and the triethoxysilane is 5.5 g: 100mL of: 0.2 mL: 1.7 g.
Example 3
Preparing organic modified nano-silica aerogel:
mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel by a grading drying method at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ for 24h, 2h, 1.5h and 1 h; obtaining the organic modified nano silicon dioxide aerogel;
wherein the concentration of the oxalic acid aqueous solution is 1 mol/L; the mass fraction of the ammonia water is 25 percent; the dosage mass ratio of the ethyl orthosilicate to the modifier is 1: 0.5; the dosage ratio of the ethyl orthosilicate, the ethanol, the oxalic acid aqueous solution and the ammonia water is 1 g: 20mL of: 0.6 g: 0.5 g; the modifier was prepared as in example 2.
Example 4
Preparing organic modified nano-silica aerogel:
mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel by a grading drying method at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ for 24h, 2h, 1.5h and 1 h; obtaining the organic modified nano silicon dioxide aerogel;
wherein the concentration of the oxalic acid aqueous solution is 1 mol/L; the mass fraction of the ammonia water is 25 percent; the dosage mass ratio of the ethyl orthosilicate to the modifier is 1: 0.6; the dosage ratio of the ethyl orthosilicate, the ethanol, the oxalic acid aqueous solution and the ammonia water is 1 g: 20mL of: 0.6 g: 0.5 g; the modifier was prepared as in example 2.
Example 5
Preparing organic modified nano-silica aerogel:
mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel by a grading drying method at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ for 24h, 2h, 1.5h and 1 h; obtaining the organic modified nano silicon dioxide aerogel;
wherein the concentration of the oxalic acid aqueous solution is 1 mol/L; the mass fraction of the ammonia water is 25 percent; the dosage mass ratio of the ethyl orthosilicate to the modifier is 1: 0.7; the dosage ratio of the ethyl orthosilicate, the ethanol, the oxalic acid aqueous solution and the ammonia water is 1 g: 20mL of: 0.6 g: 0.5 g; the modifier was prepared as in example 2.
Comparative example 1
The modifier in example 4 was replaced by silane coupling agent KH-550, and the rest of the raw materials and the preparation process were kept unchanged.
Comparative example 2
The modifier in example 4 was not added, and the rest of the raw materials and the preparation process remained unchanged.
Comparative example 3
This comparative example was prepared according to the method in patent No. CN 108017062B.
The samples prepared in examples 3-5 and comparative examples 1-3 were tested to determine the water contact angle, density and thermal conductivity at 25 deg.C of the aerogel; the density is measured by a drainage method, sample blocks with corresponding sizes are prepared according to the specification of an instrument, and the porosity, the volume density, the thermal diffusion coefficient and the like are measured to calculate the thermal conductivity coefficient.
The test results are shown in table 1 below:
TABLE 1
| Item | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Contact angle (°) | 150 | 150 | 150 | 135 | 130 | 149 |
| Density (mg/m)3) | 29 | 29 | 29 | 40 | 45 | 35 |
| Coefficient of thermal conductivity (w/m. k) | 0.01 | 0.01 | 0.01 | 0.02 | 0.03 | 0.02 |
The aerogel prepared by the invention has low thermal conductivity and excellent hydrophobic property, and can improve the application of the aerogel in the aspect of heat-insulating flame-retardant materials.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (4)
1. The method for organically modifying the nano-silica aerogel is characterized by comprising the following steps of:
mixing tetraethoxysilane, a modifier and ethanol, adding an oxalic acid aqueous solution, magnetically stirring for 30min, and standing at room temperature for 24 h; then dropwise adding ammonia water, stirring for 30min, and aging at normal temperature for 2 days to obtain gel; drying the gel to obtain the organic modified nano silicon dioxide aerogel;
wherein, the modifier is prepared by the following steps:
step S11, mixing aniline, p-hydroxybenzaldehyde and 1, 4-dioxane, heating to 85 ℃ under the protection of nitrogen, reacting for 6 hours, and performing post-treatment after the reaction is finished to obtain an intermediate 1;
step S12, mixing the intermediate 1, tetrahydrofuran and triethylamine, dropwise adding phosphorus oxychloride at the temperature of 20-25 ℃, keeping the temperature unchanged after dropwise adding, stirring for reacting for 10 hours, and performing post-treatment after the reaction is finished to obtain an intermediate 2;
step S13, mixing 2-hydroxyethyl acrylate, dichloromethane and triethylamine, stirring and cooling to 0 ℃ under the protection of nitrogen, slowly dropwise adding a dichloromethane solution of the intermediate 2, keeping the temperature unchanged after dropwise adding, continuously stirring and reacting for 24 hours, and performing post-treatment after the reaction to obtain an intermediate 3;
and step S14, mixing the intermediate 3 with toluene, heating to 50 ℃ under the protection of nitrogen, adding a Karster catalyst, continuously stirring for reacting for 60min, then dropwise adding triethoxysilane, heating to 70 ℃ after dropwise adding, reacting for 24h, and performing post-treatment after the reaction is finished to obtain the modifier.
2. The method of organically modifying nano silica aerogel according to claim 1, wherein the ratio of the amounts of aniline, p-hydroxybenzaldehyde and 1, 4-dioxane used in step S11 is 1 g: 1.2 g: 20 mL; in step S12, 2.2g of intermediate 1, tetrahydrofuran, triethylamine, and phosphorus oxychloride: 40mL of: 2.97 g: 1.5 g; the amount ratio of the 2-hydroxyethyl acrylate, dichloromethane, triethylamine and the dichloromethane solution of intermediate 2 in step S13 was 1.2 g: 30mL of: 2.1 g: 50mL, wherein the dichloromethane solution of intermediate 2 is intermediate 2 and dichloromethane is prepared according to the following steps of 1 g: 10mL of the mixture is mixed; in the step S14, the using amount ratio of the intermediate, the toluene, the Kaster catalyst and the triethoxysilane is 5.5 g: 100mL of: 0.2 mL: 1.7 g.
3. The method for organically modifying nano-silica aerogel according to claim 1, wherein the gel is dried by a fractional drying method at 60 ℃, 80 ℃, 100 ℃ and 120 ℃ for 24h, 2h, 1.5h and 1 h.
4. The method for organically modifying nano silica aerogel according to claim 1, wherein the concentration of the oxalic acid aqueous solution is 1 mol/L; the mass fraction of the ammonia water is 25 percent; the dosage mass ratio of the ethyl orthosilicate to the modifier is 1: 0.5-0.7; the dosage ratio of the ethyl orthosilicate, the ethanol, the oxalic acid aqueous solution and the ammonia water is 1 g: 20mL of: 0.6 g: 0.5 g.
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