阅读说明：本技术 超疏水性二氧化硅气凝胶微球的制备方法 (Preparation method of super-hydrophobic silica aerogel microspheres ) 是由 施翌 葛金龙 王传虎 刘超 田辰睿 于 2021-08-16 设计创作，主要内容包括：本发明公开超疏水性二氧化硅气凝胶微球的制备方法,包括以下步骤：S1：将甲基三乙氧基硅烷、五氟苯基三乙氧基硅烷、十六烷基三甲基溴化铵加入去离子水中,强力搅拌10min,调节pH至2-3,25℃水解反应20-30min,得到混合溶液；S2：向混合溶液中加入甲醇钠、双环氧化合物,调节pH至9.5-10.5,25℃充分搅拌5min得透明状溶液；S3：将透明状溶液缓慢倒入正己烷,以25℃的温度、1000r/min的转速恒温磁力搅拌5-10min,再静置20-30min,再转移至反应釜中,于100-150℃缩合反应30-60min,冷却、无水乙醇洗涤、过滤后,得到湿凝胶；S4：真空干燥箱、研磨。本发明方法制备时间短,反应活性高,制备出的二氧化硅气凝胶微球的疏水性、力学性能优异,比表面积高,其接触角高达164°。(The invention discloses a preparation method of super-hydrophobic silica aerogel microspheres, which comprises the following steps: s1: adding methyltriethoxysilane, pentafluorophenyl triethoxysilane, and hexadecyl trimethyl ammonium bromide into deionized water, strongly stirring for 10min, adjusting pH to 2-3, and performing hydrolysis reaction at 25 deg.C for 20-30min to obtain mixed solution; s2: adding sodium methoxide and diepoxide into the mixed solution, adjusting pH to 9.5-10.5, and fully stirring at 25 ℃ for 5min to obtain a transparent solution; s3: slowly pouring the transparent solution into n-hexane, magnetically stirring at a constant temperature of 25 ℃ and a rotation speed of 1000r/min for 5-10min, standing for 20-30min, transferring to a reaction kettle, performing condensation reaction at 100-150 ℃ for 30-60min, cooling, washing with absolute ethyl alcohol, and filtering to obtain wet gel; s4: vacuum drying oven, grinding. The method has the advantages of short preparation time and high reaction activity, and the prepared silica aerogel microspheres have excellent hydrophobicity and mechanical properties, high specific surface area and contact angles as high as 164 degrees.)

1. A preparation method of super-hydrophobic silica aerogel microspheres is characterized in that methyl triethoxysilane is used as a precursor, pentafluorophenyl triethoxysilane is used as a modified silicon source, hexadecyl trimethyl ammonium bromide is used as a surfactant, hydrolysis reaction is carried out, and then a diepoxy compound is used as a cross-linking agent to carry out condensation reaction to form SiO with a C-F hydrophobic structure and a benzene ring rigid structure₂Aerogel microspheres; the method specifically comprises the following steps:

s1: uniformly mixing methyltriethoxysilane and pentafluorophenyl triethoxysilane, adding into deionized water, adding hexadecyl trimethyl ammonium bromide, strongly stirring for 10min, adding dilute hydrochloric acid solution to adjust pH to 2-3, and performing hydrolysis reaction at 25 ℃ for 20-30min to obtain a mixed solution;

s2: adding sodium methoxide and a diepoxide into the mixed solution, adding sodium hydroxide solution to adjust the pH to 9.5-10.5, and fully stirring for 5min at 25 ℃ to obtain a transparent solution;

s3: slowly pouring the transparent solution into n-hexane, magnetically stirring at a constant temperature of 25 ℃ and a rotation speed of 1000r/min for 20-30min to obtain a water-in-oil emulsion, transferring the water-in-oil emulsion into a reaction kettle, carrying out condensation reaction at 100-150 ℃ for 30-60min, cooling, washing with absolute ethyl alcohol, and filtering to obtain wet gel;

s4: and (3) putting the wet gel into a vacuum drying oven for drying for 6h at the temperature of 80 ℃, and grinding into powder to obtain the super-hydrophobic silica aerogel microspheres.

2. The method for preparing superhydrophobic silica aerogel microspheres of claim 1, wherein the diepoxide is ethylene glycol diglycidyl ether.

3. The method for preparing superhydrophobic silica aerogel microspheres of claim 1, wherein the concentration of the dilute hydrochloric acid solution is 1-2 mol/L.

4. The method for preparing superhydrophobic silica aerogel microspheres of claim 1, wherein the concentration of the sodium hydroxide solution is 1-2 mol/L.

5. The method for preparing superhydrophobic silica aerogel microspheres of claim 1, wherein in S1-S2, the ratio of the methyl triethoxysilane, the pentafluorophenyl triethoxysilane, the cetyl trimethylammonium bromide, the deionized water, the sodium methoxide, and the diepoxide is 20 mL: 2mL of: 0.2 g: 60mL of: 0.2 g: 2.5 g.

6. The method for preparing superhydrophobic silica aerogel microspheres of claim 1, wherein in S3, the volume ratio of the transparent solution to n-hexane is (3-4): 10.

Technical Field

The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a preparation method of super-hydrophobic silica aerogel microspheres.

Background

SiO₂Aerogels are nanostructured solids with an open pore structure. It has many excellent properties, including a high surface area (500- & lt1000 m. & gt)²Per g), high porosity (80-99.8%), low volume weight (0.003-0.8 g/cm)³) Low thermal conductivity (-0.02W/m K). The microstructure is shown in FIG. 1, and these properties are such that SiO is present₂The aerogel has potential application value. In the field of sound-insulating materials, SiO₂Aerogel is a nanoporous material. As the sound propagates through the aerogel, it first enters its nanopores. SiO2₂The three-dimensional network structure of the aerogel can cause multiple back-transmissions, collisions, and reflections of sound waves. In addition, the sound wave in the nanopore can rub with air and the wall of the nanopore, so that the propagation of the sound wave is delayed, and huge sound loss is caused. Thus, SiO₂Aerogel can be used as a good sound insulation material. In the field of catalysis, SiO₂The high porosity of aerogels can serve as an excellent catalyst support. And secondly, the catalyst has good application value in a novel catalyst or a catalyst as a carrier due to good catalytic performance. In the field of adsorption, SiO₂The aerogel has the characteristics of extremely low density, ultrahigh porosity and large specific surface area, and is an excellent adsorbent carrier. SiO2₂The excellent adsorption capacity and recyclability of aerogels for organic liquids and oils has greatly expanded the commercial use of silica aerogels. In addition to this, SiO₂The concave-convex porous rough structure of the aerogel can well construct a super-hydrophobic surface.

In recent years, research in the field of functional silica aerogel at home and abroad is popular, in 2005, Rao and the like prepare hydrophobic silica aerogel by using tetraethyl orthosilicate (TEOS) precursor, tetraethylpentasilicate, hexamethyldisilazane silylating agent, n-hexane, cyclohexane, heptane, benzene, toluene and xylene as solvents and drying at normal pressure by a two-step catalysis method, and research finds that in an n-heptane solvent, compared with other solvents, the silica aerogel has lower hydrophobicity, high porosity (97%), hydrophobicity (θ ═ 160 °), uniform porosity and high transparency (90%). In 2006, Bhagat and the like adopt a co-precursor method to synthesize silica aerogel microspheres taking water glass as a precursor, and the hydrogel is subjected to surface modification, so that the processing time of the microspheres can be greatly shortened. The route of synthesizing aerogel microspheres by using the water glass precursor completely avoids the use of a solvent, and exchanges water from the hydrogel, thereby further reducing the cost. In 2010, Sarawade and the like prepare hydrophobic mesoporous sodium silicate-based silica aerogel microspheres, prepare silica sol by a silica sol rapid gel method, determine that the% V of a surface modifier TMCS has a great influence on the performance of a final product, have more ideal performance than unmodified silica beads, utilize a low-cost silica source (sodium silicate) and simultaneously perform a surface modification process, and are suitable for economic and large-scale industrial production of silica aerogel beads. In 2011 Hong et al successfully prepared spherical silica aerogel particles using surfactant Span 80 and separated from water glass using an atmospheric drying process. The preparation of stable silicic acid droplets in n-hexane is a key step in the preparation of silica aerogel particles of uniform size and microstructure. In addition, the mixing speed of the droplet/n-hexane mixture may affect the gelation of silicic acid droplets, which is also an important factor, and the prepared aerogel particles exhibit large specific pore volume and large specific surface area.

At present, SiO₂The preparation method of the aerogel mainly comprises a sol-gel method which is a main method for preparing a silica aerogel wet gel precursor, wherein the precursor is dispersed in a solvent and hydrolyzed to form tiny spherical particles with small particle size and high surface energy, so that the tiny spherical particles are spontaneously condensed into gel, but the traditional sol-gel method has the defects of long preparation period, long time and generally requiring several days or even one week (for example, a patent with the application number of CN201010515083.X discloses a glass fiber reinforced silica aerogel composite material and a preparation method thereof, the aging time of the preparation method is 1-3 days, and the modification time is 1-2 days)Amplitude shrinkage and agglomeration. Therefore, how to rapidly prepare the SiO with high strength, high crosslinking degree and super-hydrophobicity₂Aerogels are of great significance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of super-hydrophobic silica aerogel microspheres.

The technical scheme of the invention is summarized as follows:

a preparation method of super-hydrophobic silica aerogel microspheres comprises the steps of carrying out hydrolysis reaction by taking methyl triethoxysilane as a precursor, taking pentafluorophenyl triethoxysilane as a modified silicon source and taking hexadecyl trimethyl ammonium bromide as a surfactant, and carrying out condensation reaction by taking a diepoxide as a cross-linking agent to form SiO with a C-F hydrophobic structure and a benzene ring rigid structure₂Aerogel microspheres; the method specifically comprises the following steps:

s1: uniformly mixing methyltriethoxysilane and pentafluorophenyl triethoxysilane, adding into deionized water, adding hexadecyl trimethyl ammonium bromide, strongly stirring for 10min, adding dilute hydrochloric acid solution to adjust pH to 2-3, and performing hydrolysis reaction at 25 ℃ for 20-30min to obtain a mixed solution;

s2: adding sodium methoxide and a diepoxide into the mixed solution, adding sodium hydroxide solution to adjust the pH to 9.5-10.5, and fully stirring for 5min at 25 ℃ to obtain a transparent solution;

s3: slowly pouring the transparent solution into n-hexane, magnetically stirring at a constant temperature of 25 ℃ and a rotation speed of 1000r/min for 20-30min to obtain a water-in-oil emulsion, transferring the water-in-oil emulsion into a reaction kettle, carrying out condensation reaction at 100-150 ℃ for 30-60min, cooling, washing with absolute ethyl alcohol, and filtering to obtain wet gel;

s4: and (3) putting the wet gel into a vacuum drying oven for drying for 6h at the temperature of 80 ℃, and grinding into powder to obtain the super-hydrophobic silica aerogel microspheres.

Preferably, the diepoxide is ethylene glycol diglycidyl ether.

Preferably, the concentration of the dilute hydrochloric acid solution is 1-2 mol/L.

Preferably, the concentration of the sodium hydroxide solution is 1-2 mol/L.

Preferably, in S1-S2, the dosage ratio of the methyl triethoxysilane, the pentafluorophenyl triethoxysilane, the hexadecyl trimethyl ammonium bromide, the deionized water, the sodium methoxide and the diepoxide is 20 mL: 2mL of: 0.2 g: 60mL of: 0.2 g: 2.5 g.

Preferably, in S3, the volume ratio of the transparent solution to n-hexane is (3-4): 10.

the invention has the beneficial effects that:

1. the methyl triethoxysilane is used as a precursor, the pentafluorophenyl triethoxysilane is used as a modified silicon source, hexadecyl trimethyl ammonium bromide is used as a surfactant for hydrolysis reaction, then a diepoxy compound is used as a cross-linking agent, a microemulsion method is adopted, and a benzene ring rigid structure and a C-F hydrophobic structure are grafted to SiO by utilizing nucleophilic addition reaction between silanol groups and epoxy groups or intermolecular dehydration etherification action between hydroxyl groups₂The mechanical property and the hydrophobic property of the wet gel are improved on the surface of the particles, and meanwhile, the gel system forms a stable whole with three-dimensional network interpenetrating of mutual entanglement, high strength and high crosslinking density under the action of high crosslinking association between the diepoxide and the silane hydrolysate, so that the problems of collapse and shrinkage of a gel framework structure caused by evaporation or escape of water and organic gas in the drying process of the wet gel are solved.

2. The invention adopts a microemulsion method to prepare SiO₂Aerogel microspheres, hydrophobic/hydrophilic molecular groups in cetyl trimethyl ammonium bromide in microemulsion separate oil phase and water phase into tiny spherical spaces to form a dispersion system with nano-scale particle structure, thermodynamic stability and isotropy, compared with sol-gel method, SiO₂Good dispersibility of aerogel, SiO₂The particles are uniformly distributed, the particle size is controllable, the particle size distribution range is narrow, the formed wet gel space framework is more stable and is not easy to agglomerate, the collapse and the shrinkage are more difficult to occur during drying, and the SiO is further improved₂Mechanical properties of aerogel microspheres.

3. The method has the advantages of short preparation time and high reaction activity, and the prepared silica aerogel microspheres have excellent hydrophobicity and mechanical properties, high specific surface area, contact angles up to 164 degrees, compressive strength up to 4.8MPa and high mechanical stability.

Drawings

FIG. 1 is SiO₂Microstructure of aerogel;

FIG. 2 shows SiO produced in example 1₂The form of the aerogel microsphere powder (left) and the form of water drops on the aerogel microsphere powder (right);

FIG. 3 shows the super-hydrophobic SiO of the present invention₂A flow chart of a preparation method of the aerogel microspheres;

FIG. 4 shows SiO produced in example 1₂Drawing aerogel microspheres TG;

FIG. 5 shows SiO produced in comparative example 1₂Drawing aerogel microspheres TG;

FIG. 6 is a SiO solid prepared in comparative example 2₂Drawing aerogel microspheres TG;

FIG. 7 shows SiO produced in comparative example 3₂Drawing aerogel microspheres TG;

FIG. 8 shows SiO produced in example 1 and comparative examples 1 to 3₂Differential thermogram of aerogel microspheres;

FIG. 9 shows SiO produced in example 1₂N of aerogel microspheres₂Adsorption-desorption curve chart;

FIG. 10 shows SiO produced in comparative example 2₂N of aerogel microspheres₂Adsorption-desorption curve chart;

FIG. 11 shows SiO produced in comparative example 3₂N of aerogel microspheres₂Adsorption-desorption curve chart;

FIG. 12 shows SiO solid formed in example 1₂A polarization diagram of the aerogel microspheres;

FIG. 13 shows SiO produced in comparative example 1₂A polarization diagram of the aerogel microspheres;

FIG. 14 shows SiO produced in comparative example 2₂A polarization diagram of the aerogel microspheres;

FIG. 15 is a polarization diagram of SiO2 aerogel microspheres prepared in comparative example 3;

FIG. 16 shows the water dropping on the SiO film produced in example 1₂A full process schematic on aerogel microspheres;

FIG. 17 shows a water droplet and SiO prepared in example 1₂Schematic diagram of the whole process of aerogel microsphere contact;

FIG. 18 shows SiO produced in example 1₂Schematic diagram of contact angle test of aerogel microspheres at different time periods.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

The invention provides a preparation method of a super-hydrophobic silica aerogel microsphere, which is implemented by taking methyltriethoxysilane as a precursor, taking pentafluorophenyl triethoxysilane as a modified silicon source, taking hexadecyl trimethyl ammonium bromide as a surfactant, carrying out hydrolysis reaction, and then taking a diepoxide ethylene glycol diglycidyl ether as a cross-linking agent to carry out condensation reaction to form SiO with a C-F hydrophobic structure and a benzene ring rigid structure₂Aerogel microspheres; the method specifically comprises the following steps:

s1: uniformly mixing methyltriethoxysilane and pentafluorophenyl triethoxysilane, adding into deionized water, adding hexadecyl trimethyl ammonium bromide, strongly stirring for 10min, adding 1-2mol/L dilute hydrochloric acid solution to adjust pH to 2-3, and performing hydrolysis reaction at 25 ℃ for 20-30min to obtain a mixed solution;

s2: adding sodium methoxide and ethylene glycol diglycidyl ether into the mixed solution, adding 1-2mol/L sodium hydroxide solution to adjust the pH to 9.5-10.5, and fully stirring for 5min at 25 ℃ to obtain transparent solution;

the dosage ratio of the methyl triethoxysilane, the pentafluorophenyl triethoxysilane, the hexadecyl trimethyl ammonium bromide, the deionized water, the sodium methoxide and the diepoxide is 20 mL: 2mL of: 0.2 g: 60mL of: 0.2 g: 2.5 g;

s3: slowly pouring the transparent solution into n-hexane, and controlling the volume ratio of the transparent solution to the n-hexane to be (3-4): 10, stirring magnetically at a constant temperature of 25 ℃ and a rotation speed of 1000r/min for 20-30min to obtain a water-in-oil emulsion, transferring the water-in-oil emulsion into a reaction kettle, carrying out condensation reaction at 100-150 ℃ for 30-60min, cooling, washing with absolute ethyl alcohol, and filtering to obtain wet gel;

s4: and (3) putting the wet gel into a vacuum drying oven for drying for 6h at the temperature of 80 ℃, and grinding into powder to obtain the super-hydrophobic silica aerogel microspheres.

Example 1

S1: uniformly mixing 20mL of methyltriethoxysilane and 2mL of pentafluorophenyl triethoxysilane, adding into 60mL of deionized water, adding 0.2g of hexadecyl trimethyl ammonium bromide, strongly stirring for 10min, adding 1.5mol/L of dilute hydrochloric acid solution to adjust the pH value to 2.5, and carrying out hydrolysis reaction at 25 ℃ for 30min to obtain a mixed solution;

s2: adding 0.2g of sodium methoxide and 2.5g of ethylene glycol diglycidyl ether into the mixed solution obtained in the step S1, adding 1.5mol/L of sodium hydroxide solution, adjusting the pH to 10, and fully stirring at 25 ℃ for 5min to obtain a transparent solution;

s3: slowly pouring 40mL of transparent solution into 100mL of n-hexane, magnetically stirring at a constant temperature of 25 ℃ and a rotation speed of 1000r/min for 20min to obtain a water-in-oil emulsion, transferring the water-in-oil emulsion into a reaction kettle, carrying out condensation reaction at 130 ℃ for 45min, cooling, washing with absolute ethyl alcohol, and filtering to obtain wet gel;

s4: and (3) putting the wet gel into a vacuum drying oven for drying for 6h at the temperature of 80 ℃, and grinding into powder to obtain the super-hydrophobic silica aerogel microspheres.

Comparative example 1 is the same as example 1 except that ethylene glycol diglycidyl ether was not added during the preparation of comparative example 2.

Comparative example 2 is the same as example 1 except that no pentafluorophenyl triethoxysilane was added during the preparation of comparative example 1.

Comparative example 3 is the same as example 1 except that methyltriethoxysilane in example 1 was replaced with ethyl orthosilicate and no pentafluorophenyl triethoxysilane was added during the preparation.

Test one: thermogravimetric analysis was carried out on the products prepared in example 1 and comparative examples 1 to 3:

thermogravimetry (TG) is mainly to analyze the change in mass of a sample during a reaction, and there is a step on the TG curve as long as there is a change accompanied by the change in mass. The samples obtained in the example 1 and the comparative examples 1 to 4 are subjected to thermal weight loss analysis by adopting an STA2500 type thermogravimetric analyzer at the test temperature of 30-900 ℃ and the temperature rise speed of 20 ℃/min, and the mass change of the samples along with the temperature rise is observed.

As can be seen from FIGS. 4-7, the sample of example 1 has a slightly gradual change in mass between 250 ℃ and 650 ℃; the mass rate change is the largest at 650-800 ℃, the sample of comparative example 1 has obvious mass rate changes at 200-250 ℃ and 500-650 ℃, the sample of comparative example 2 has obvious mass rate changes at 150-200 ℃ and 500-700 ℃, and the sample of comparative example 3 has the largest mass rate change at 400-600 ℃. Overall, the aerogel microspheres prepared in example 1 were more thermally stable.

And (2) test II: the adsorption-desorption curves of the products prepared in example 1 and comparative examples 2 to 3 were carried out

The samples obtained in example 1 and comparative examples 2-3 were tested for N using TriStar II 3020 model multi-channel full-automatic specific surface area and void analyzer₂Adsorption-desorption curve.

As can be seen from FIGS. 9-12, the samples prepared in example 1 were in the P/P range₀The highest adsorption capacity is obtained in the range of 0.8-1.0, which indicates that the product of example 1 has a high specific surface area and excellent desorption performance.

And (3) test III: the polarization test was performed on the products manufactured in example 1 and comparative examples 1 to 3

The obtained sample is characterized by adopting an Axio.LabA1 type polarizing microscope to observe SiO₂The surface structure of the aerogel microspheres and the coating condition of the surface.

As can be seen from FIGS. 13-16, the samples of example 1 and comparative examples 1-3 all had bright microspheres in the polarization test, which indicates that the preparation methods of example 1 and comparative examples 1-3 both successfully prepared SiO₂Aerogel microspheres, but the aerogel microspheres produced by the method of example 1 have a more uniform particle size and a most uniform distribution.

And (4) testing: physicochemical characterization of the products prepared in example 1 and comparative examples 1 to 3

The contact angle of the obtained sample is measured and characterized by adopting a DY-100 type contact angle measuring instrument, the surface hydrophobic property of the measured sample is explored, the mechanical property of the sample is measured, and the test result is shown in the following table:

test items	Example 1	Comparative example 1	Comparative example 2	Comparative example 3
					Contact Angle/°	164	152	141	86
Compressive strength/MPa	4.8	3.1	2.4	2.2

As can be seen from the above table, SiO of comparative example 3₂The hydrophilicity of the aerogel microspheres demonstrated that methyltriethoxysilane and pentafluorophenyltriethoxysilane had a significant effect on whether the aerogel was hydrophobic, while comparative example 2 was not superhydrophobic, demonstrating that pentafluorophenyltriethoxysilane had a significant effect on the superhydrophobicity of the aerogel.

FIG. 17 shows a water droplet and SiO produced in example 1₂Aerogel microsphere contact dynamics as shown in FIG. 17It is known that the contact angle of the sample of example 1 is substantially uniform at each time period, indicating its excellent superhydrophobicity in a dynamic manner.

The methyl triethoxysilane is used as a precursor, the pentafluorophenyl triethoxysilane is used as a modified silicon source, hexadecyl trimethyl ammonium bromide is used as a surfactant for hydrolysis reaction, then a diepoxy compound is used as a cross-linking agent, a microemulsion method is adopted, and a benzene ring rigid structure and a C-F hydrophobic structure are grafted to SiO by utilizing nucleophilic addition reaction between silanol groups and epoxy groups or intermolecular dehydration etherification action between hydroxyl groups₂The mechanical property and the hydrophobic property of the wet gel are improved on the surface of the particles, and meanwhile, the gel system forms a stable whole with three-dimensional network interpenetrating of mutual entanglement, high strength and high crosslinking density under the action of high crosslinking association between the diepoxide and the silane hydrolysate, so that the problems of collapse and shrinkage of a gel framework structure caused by evaporation or escape of water and organic gas in the drying process of the wet gel are solved.

The invention adopts a microemulsion method to prepare SiO₂Aerogel microspheres, hydrophobic/hydrophilic molecular groups in cetyl trimethyl ammonium bromide in microemulsion separate oil phase and water phase into tiny spherical spaces to form a dispersion system with nano-scale particle structure, thermodynamic stability and isotropy, compared with sol-gel method, SiO₂Good dispersibility of aerogel, SiO₂The particles are uniformly distributed, the particle size is controllable, the particle size distribution range is narrow, the formed wet gel space framework is more stable and is not easy to agglomerate, the collapse and the shrinkage are more difficult to occur during drying, and the SiO is further improved₂Mechanical properties of the aerogel.

The method has the advantages of short preparation time and high reaction activity, and the prepared silica aerogel microspheres have excellent hydrophobicity and mechanical properties, high specific surface area, contact angles up to 164 degrees, compressive strength up to 4.8MPa and high mechanical stability.

While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.