CN110052228B - Cellulose aerogel microsphere with light stress hydrophilic-hydrophobic conversion response function and preparation method thereof - Google Patents
Cellulose aerogel microsphere with light stress hydrophilic-hydrophobic conversion response function and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose aerogel microsphere with a light stress hydrophilic-hydrophobic conversion response function and a preparation method thereof. The method takes absorbent cotton as a raw material to prepare cellulose hydrosol, obtains cellulose aerogel microspheres by utilizing reversed phase suspension and normal pressure drying, and loads titanium dioxide on the surfaces of the cellulose aerogel microspheres through the bridging action of tannic acid, thereby realizing the preparation of the cellulose aerogel microspheres with the special light stress hydrophilic-hydrophobic conversion response function. The preparation process is simple in flow and low in equipment requirement; the production raw materials are low in price, the solvent is easy to recover, the cost is low, and the yield is high; the preparation process does not need the traditional solvent replacement process of normal pressure drying of the aerogel, and is convenient for large-scale industrial production. The prepared microspheres are spherical particles, the average particle size can be regulated and controlled within the range of 1-2000 mu m, and the microspheres have the function of light stress hydrophilic-hydrophobic conversion response, and can be applied to the fields of oil-water separation, heat insulation, chromatographic separation, catalysis, biological drug loading, blood purification and the like.
Description
Technical Field
The invention relates to a preparation method of aerogel microspheres, in particular to cellulose aerogel microspheres with a light stress hydrophilic-hydrophobic switching response function and a preparation method thereof.
Background
The aerogel is a high-dispersion solid material which forms a nano porous network structure by mutually gathering nano-scale particles and is filled with gaseous dispersion media in pores, has the characteristics of a nano porous structure, low density, low dielectric constant, low thermal conductivity coefficient, high porosity, high specific surface area and the like, shows unique properties in the aspects of mechanics, acoustics, thermal property, optics and the like, has wide and huge application value in numerous fields of aerospace, military, petroleum, chemical industry, mineral products, communication, medical use, building materials, electronics, metallurgy and the like, is called as a magic material for changing the world, and develops rapidly in recent years.
Cellulose aerogels are a new class of aerogel materials that have been developed in recent years. Cellulose is a green renewable resource with abundant reserves on the earth, and cellulose aerogel has the advantages of the traditional aerogel material, and also has the incomparable characteristics of inorganic aerogel such as good toughness, easy processing, simple preparation process, controllable structure, abundant and renewable sources, good biocompatibility and degradability, and the like, so that the cellulose aerogel becomes a new material with wide application prospect and great development value. The spherical cellulose microsphere microparticles have regular shapes, and the powder aerogel material formed by the spherical cellulose microsphere microparticles has lower apparent density and better fluidity, thereby being beneficial to the application of the aerogel material in the fields of heat insulation, chromatographic separation, catalysis, oil-water separation, controllable drug release, blood purification and the like.
The wettability is one of important properties of the surface of the cellulose aerogel material, for example, the wettability of the surface of the cellulose aerogel material can be conveniently and accurately regulated through external stimulation such as light, heat, pH value and the like, so that the cellulose aerogel material is converted under a hydrophilic state and a hydrophobic state, special functional characteristics are given to the cellulose aerogel material, and the application range of the cellulose aerogel material is expanded. At present, the preparation method of aerogel materials, particularly cellulose aerogel microsphere materials has the defects of complexity, complex process, complex and expensive equipment, high energy consumption of the drying process, high danger and the like. The method has the advantages of low cost, simple process, and important practical significance for researching and developing the functional characteristics of preparing the spherical cellulose aerogel microsphere particles and endowing the cellulose aerogel microsphere materials with special responsiveness and wettability change.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a cellulose aerogel microsphere with a special light stress hydrophilic-hydrophobic switching response function and a preparation method thereof. The method comprises the steps of preparing cellulose hydrosol by using absorbent cotton as a raw material, realizing the molding of cellulose gel microspheres by using a reverse suspension and sol-gel mode, synchronously carrying out hydrophobic modification and solvent replacement of the cellulose gel microspheres under the action of a silane modifier, and drying at normal pressure to obtain the cellulose aerogel microspheres; on the basis, titanium dioxide is loaded on the surface of the cellulose aerogel microsphere through the bridging action of tannic acid, so that the preparation of the cellulose aerogel microsphere with the special light stress hydrophilic-hydrophobic conversion response function is realized.
The object of the invention is achieved by:
a preparation method of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function comprises the following steps:
(1) preparation of cellulose aerogel microspheres
Mixing sodium hydroxide, urea and deionized water, precooling to 0-25 ℃, taking out, adding absorbent cotton, stirring and dissolving to obtain cellulose hydrosol; mixing cellulose hydrosol, deionized water and a cross-linking agent to obtain a water phase; uniformly stirring and mixing the low-surface-tension solvent and the surfactant to obtain an oil phase; mixing the water phase and the oil phase, stirring to form a suspension, adding a silane modifier, stirring and reacting for 3-10 h under the heating condition of 40-80 ℃, standing after the reaction is finished, filtering, washing and drying to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution with solute mass percent of 0.1-10%, taking out and airing after soaking for 1 second-24 hours; repeating the operation for at least 1 time to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution with solute mass percentage of 0.01-10%, reacting for 1-48 hours at 20-80 ℃, taking out, and drying to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
In the step (1), in the preparation of the cellulose hydrosol, the mass ratio of the sodium hydroxide, the urea, the deionized water and the absorbent cotton is 1-10: 1-20: 100: 0.2-10;
in the step (1), in the preparation of the water phase, the mass ratio of the cellulose hydrosol to the deionized water to the cross-linking agent is 100: 1-2000: 0-10;
in the step (1), in the preparation of the oil phase, the mass ratio of the low surface tension solvent to the surfactant is 100: 0.01-10;
in the step (1), in the preparation of the cellulose aerogel microspheres, the mass ratio of the oil phase to the water phase to the silane modifier is 100: 20-100: 0.01-10.
In the step (1), the cross-linking agent is at least one of 1,2,3, 4-butanetetracarboxylic acid, glyoxal, ammonium zirconium carbonate and divinyl sulfone; the low surface tension solvent is at least one of methyl isobutyl ketone, normal hexane and normal octane; the surfactant is at least one of tween-40, tween-60, tween-80, span-40, span-65 and span-80; the silane modifier is at least one of tetraethoxysilane, hexamethyldisiloxane, hexamethyldisilazane and hexamethylcyclotrisiloxane.
In the step (2), the preparation method of the tannic acid solution comprises the following steps: dissolving tannic acid in a solvent A, and adjusting the pH value to 7.1-10.0 to obtain a tannic acid solution, wherein the solvent A is at least one of water, ethanol and methanol.
In the step (2), the preparation method of the titanium dioxide solution comprises the following steps: dispersing anatase type nano titanium dioxide with the particle size of 0.5-300 nm in a solvent A to obtain a titanium dioxide solution, wherein the solvent A is at least one of water, ethanol and methanol.
In the step (1), drying is carried out for 1-15 h at 70-120 ℃ under normal pressure; in the step (2), the drying is carried out in a drying oven at the temperature of 40-90 ℃ for 2-24 hours.
The cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function are spherical particles, the particle size is 1-2000 mu m, and the specific surface area is 50-1200 m2(ii)/g, the pore diameter is 5 to 500 nm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation process of the light stress hydrophilic-hydrophobic conversion response functional cellulose aerogel microspheres adopted by the invention is simple in flow and low in equipment requirement; in addition, the production raw materials are low in price, the solvent is easy to recover, the production cost is low, and the yield is high.
2. The preparation process of the cellulose aerogel microspheres does not need the conventional normal-pressure drying and complex solvent replacement process of the aerogel, and is convenient for large-scale industrial production.
3. The hydrophobic nano porous cellulose microsphere prepared by the invention is spherical particles, the average particle size can be regulated and controlled within the range of 1-2000 mu m, and the hydrophobic nano porous cellulose microsphere has a light stress hydrophilic-hydrophobic conversion response function, and can be applied to the fields of oil-water separation, heat insulation, chromatographic separation, catalysis, biological medicine carrying, blood purification and the like.
Drawings
Fig. 1 is an SEM image of cellulose aerogel microspheres having photo-stress hydropathy/hydrophobicity-affinity transformation response function prepared in example 1 of the present invention.
Fig. 2 is an SEM image of cellulose aerogel microspheres having photo-stress hydropathic-hydrophobic transition response function prepared in example 1 of the present invention.
Fig. 3 is an XPS spectrum of cellulose aerogel microspheres with photo-stress hydropathy/hydrophobicity conversion response function prepared in example 1 of the present invention.
Fig. 4 is a photograph showing changes in water contact angle of cellulose aerogel microspheres having a photo-stress hydrophilic-hydrophobic transition response function according to example 1 of the present invention.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
A preparation method of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function comprises the following steps:
(1) preparation of cellulose aerogel microspheres
Mixing sodium hydroxide, urea and deionized water, precooling to 0-25 ℃, taking out, adding absorbent cotton, stirring and dissolving to obtain cellulose hydrosol; mixing cellulose hydrosol, deionized water and a cross-linking agent to obtain a water phase; uniformly stirring and mixing the low-surface-tension solvent and the surfactant to obtain an oil phase; mixing the water phase and the oil phase, stirring to form a suspension, adding a silane modifier, stirring and reacting for 3-10 h under the heating condition of 40-80 ℃, standing, filtering, washing, and drying for 1-15 h at 70-120 ℃ under normal pressure to obtain cellulose aerogel microspheres;
in the preparation of cellulose hydrosol, the mass ratio of sodium hydroxide, urea, deionized water and absorbent cotton is (1-10) to (1-20) to 100 to (0.2-10);
in the water phase preparation, the mass ratio of the cellulose hydrosol to the deionized water to the cross-linking agent is 100: 1-2000: 0-10;
in the preparation of the oil phase, the mass ratio of the low surface tension solvent to the surfactant is 100 to (0.01-10);
in the preparation of the cellulose aerogel microspheres, the mass ratio of the oil phase to the water phase to the silane modifier is 100 to (20-100) to (0.01-10);
the low surface tension solvent is at least one of methyl isobutyl ketone, normal hexane and normal octane; the silane modifier is at least one of tetraethoxysilane, hexamethyldisiloxane, hexamethyldisilazane and hexamethylcyclotrisiloxane; the surfactant is at least one of tween-40, tween-60, tween-80, span-40, span-65 and span-80; the cross-linking agent is at least one of 1,2,3, 4-butanetetracarboxylic acid, glyoxal, ammonium zirconium carbonate and divinyl sulfone;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in a solvent A, and adjusting the pH value to 7.1-10.0 to obtain a tannic acid solution; in the tannic acid solution, the mass percentage of tannic acid is 0.1-10%; dispersing anatase type nano titanium dioxide in a solvent A to obtain a titanium dioxide solution; in the titanium dioxide solution, the mass percentage of the anatase type nano titanium dioxide is 0.01-10%; wherein the solvent A is at least one of water, ethanol and methanol; the particle size of the anatase type nano titanium dioxide is 0.5-300 nm;
soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 1 second to 24 hours, and taking out and drying; repeating the operation for at least 1 time to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 1-48 hours at 20-80 ℃, taking out, and drying in a drying oven at 40-90 ℃ for 2-24 hours to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
Example 1
(1) Preparation of cellulose aerogel microspheres
Mixing 2g of sodium hydroxide, 5g of urea and 100g of deionized water, precooling to-7 ℃, taking out, adding 2g of absorbent cotton, and stirring for dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol, 200 g of deionized water and 0.2 g of ammonium zirconium carbonate to obtain a water phase; uniformly stirring and mixing 100g of normal hexane and 1g of span-65 to obtain an oil phase; mixing 80g of water phase and 100g of oil phase, stirring to form a suspension, adding 1g of hexamethyldisilazane, stirring and reacting for 8 hours under the heating condition of 60 ℃, standing, filtering, washing, and drying for 10 hours under normal pressure at 100 ℃ after the reaction is finished to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in ethanol, and adjusting the pH to 8.5 to obtain a tannic acid solution with the mass percentage of 1%; dispersing anatase type nano titanium dioxide (the particle size is 5 nm) in water to obtain a titanium dioxide solution with the mass percentage of 0.2%; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 10 seconds, and taking out and airing; repeating the operation for 5 times to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 24 hours at the temperature of 60 ℃, taking out, and drying for 10 hours in a drying oven at the temperature of 80 ℃ to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
Scanning electron micrographs of the prepared cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic switching response function are shown in attached figures 1 and 2, the particles are spherical, the particle size is 10-30 mu m, and the attached figure 2 shows that the prepared cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic switching response function are porous materials with continuous network structures. The specific surface area of the microspheres is tested as follows: 300 m2(ii)/g; average pore diameter of microspheres: 80 nm.
Using XPS test analysis, as shown in FIG. 3, the sample showed two peaks around 458.85 and 464.28 eV, which correspond to TiO2(Ti4+) 2p of3/2And 2P 1/2Indicating significant loading in the sampleThere is a titanium dioxide nanomaterial.
And (3) carrying out wettability test on the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic switching response function by adopting a water drop contact angle. Fixing the microspheres on the surface of the glass substrate by using a double-sided adhesive tape, wherein the microspheres have super-hydrophobic characteristics under the untreated condition, and the contact angle of water drops is more than 150 degrees, as shown in figure 4; after the microspheres are subjected to ultraviolet light irradiation treatment, the microspheres show super-hydrophilic characteristics, and water drops are adsorbed by the microspheres; after the ultraviolet light treatment and standing in the dark at room temperature for 12 hours, the microsphere can reappear the super-hydrophobic characteristic.
The cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function are used for treating the oil-water mixture, and the microspheres can effectively and quickly adsorb oil (comprising trichloromethane, normal hexane, liquid paraffin and the like) in the oil-water mixture; the microspheres adsorbed with the oil are subjected to ultraviolet light irradiation treatment, so that the oil can be desorbed from the interior of the microspheres, and better oil-water separation and recycling of the oil and microsphere materials are realized.
Example 2
(1) Preparation of cellulose aerogel microspheres
Mixing 1g of sodium hydroxide, 12 g of urea and 100g of deionized water, precooling to 0 ℃, taking out, adding 10g of absorbent cotton, stirring and dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol, 2000g of deionized water and 10g of glyoxal to obtain a water phase; uniformly stirring and mixing 100g of normal hexane and 1.5 g of span-65 to obtain an oil phase; mixing 20 g of water phase and 100g of oil phase, stirring to form a suspension, adding 5g of hexamethyldisiloxane, stirring and reacting for 10 hours under the heating condition of 40 ℃, standing, filtering, washing, and drying for 1 hour under normal pressure at 120 ℃ after the reaction is finished to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in ethanol, and adjusting the pH to 7.1 to obtain a tannic acid solution with the mass percentage of 1%; dispersing anatase type nano titanium dioxide (the particle size is 10 nm) in ethanol to obtain a titanium dioxide solution with the mass percentage of 0.01 percent; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 1 hour, and taking out and airing; repeating the operation for 2 times to obtain tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 28 hours at the temperature of 60 ℃, taking out, and drying for 10 hours in a drying oven at the temperature of 80 ℃ to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
The prepared cellulose aerogel microsphere particles with the light stress hydrophilic-hydrophobic conversion response function are spherical, and the particle size is distributed between 10 and 100 mu m. The specific surface area of the microspheres is tested as follows: 500 m2(ii)/g; average pore diameter of microspheres: 100 nm. The prepared cellulose aerogel microspheres can realize the change of the wettability of the material from hydrophobicity to hydrophilicity under the condition of ultraviolet light.
Example 3
(1) Preparation of cellulose aerogel microspheres
Mixing 10g of sodium hydroxide, 5g of urea and 100g of deionized water, precooling to-25 ℃, taking out, adding 0.2 g of absorbent cotton, and stirring for dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol, 1g of deionized water and 0.1 g of divinyl sulfone to obtain an aqueous phase; uniformly stirring and mixing 100g of normal hexane and 2g of span-80 to obtain an oil phase; mixing 100g of water phase and 100g of oil phase, stirring to form a suspension, adding 0.01 g of hexamethylcyclotrisiloxane, stirring and reacting for 10 hours under the condition of heating at 80 ℃, standing after the reaction is finished, filtering, washing, and drying for 1 hour under normal pressure at 120 ℃ to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in methanol, and adjusting the pH to 10.0 to obtain a tannic acid solution with the mass percent of 5%; dispersing anatase type nano titanium dioxide (the particle size is 100 nm) in water to obtain a titanium dioxide solution with the mass percentage of 5%; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 24 hours, and taking out and airing; repeating the operation for 4 times to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 1 hour at 80 ℃, taking out, and drying for 2 hours in a drying oven at 90 ℃ to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
The prepared cellulose aerogel microsphere particles with the light stress hydrophilic-hydrophobic conversion response function are spherical, and the particle size is distributed between 50 and 100 mu m. The specific surface area of the microspheres is tested as follows: 50m2(ii)/g; average pore diameter of microspheres: 500 nm. The prepared cellulose aerogel microspheres can realize the change of the wettability of the material from hydrophobicity to hydrophilicity under the condition of ultraviolet light.
Example 4
(1) Preparation of cellulose aerogel microspheres
Mixing 2g of sodium hydroxide, 3g of urea and 100g of deionized water, precooling to-10 ℃, taking out, adding 1g of absorbent cotton, and stirring for dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol, 50g of deionized water and 0.5g of 1,2,3, 4-butanetetracarboxylic acid to obtain a water phase; uniformly stirring and mixing 100g of methyl isobutyl ketone and 0.8 g of span-40 to obtain an oil phase; mixing 50g of water phase and 100g of oil phase, stirring to form a suspension, adding 1g of hexamethyldisilazane, stirring and reacting for 10 hours under the heating condition of 40 ℃, standing, filtering, washing, and drying for 15 hours under the normal pressure of 70 ℃ after the reaction is finished to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in ethanol, and adjusting the pH to 9.0 to obtain 0.1% tannic acid solution by mass percent; dispersing anatase type nano titanium dioxide (the particle size is 1 nm) in methanol to obtain a titanium dioxide solution with the mass percentage of 0.1%; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 24 hours, and taking out and airing; repeating the operation for 3 times to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 48 hours at 20 ℃, taking out, and drying for 24 hours in a drying oven at 40 ℃ to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
The prepared cellulose aerogel microsphere particles with the light stress hydrophilic-hydrophobic conversion response function are spherical, and the particle size is distributed between 10 and 100 mu m. The specific surface area of the microspheres is tested as follows: 1200m2(ii)/g; average pore diameter of microspheres: 5 nm. The prepared cellulose aerogel microspheres can realize the change of the wettability of the material from hydrophobicity to hydrophilicity under the condition of ultraviolet light.
Example 5
(1) Preparation of cellulose aerogel microspheres
Mixing 4 g of sodium hydroxide, 1g of urea and 100g of deionized water, precooling to-15 ℃, taking out, adding 2.5 g of absorbent cotton, and stirring for dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol and 200 g of deionized water to obtain a water phase; uniformly stirring and mixing 100g of n-octane and 10g of tween-60 to obtain an oil phase; mixing 70g of water phase and 100g of oil phase, stirring to form a suspension, adding 10g of hexamethyldisiloxane, stirring and reacting for 4 hours under the condition of heating at 70 ℃, standing, filtering, washing, and drying for 5 hours under normal pressure at 100 ℃ after the reaction is finished to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in water, and adjusting the pH to 9.0 to obtain a tannic acid solution with the mass percent of 5%; dispersing anatase type nano titanium dioxide (the particle size is 10 nm) in ethanol to obtain a titanium dioxide solution with the mass percentage of 10%; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 0.5 hour, and taking out and airing; repeating the operation for 5 times to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 8 hours at 50 ℃, taking out, and drying for 5 hours in a 70 ℃ drying oven to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
The prepared cellulose aerogel microsphere particles with the light stress hydrophilic-hydrophobic conversion response function are spherical, and the particle size is distributed between 1000-2000 mu m. The specific surface area of the microspheres is tested as follows: 200m2(ii)/g; average pore diameter of microspheres: 90 nm. The prepared cellulose aerogel microspheres can realize the change of the wettability of the material from hydrophobicity to hydrophilicity under the condition of ultraviolet light.
Example 6
(1) Preparation of cellulose aerogel microspheres
Mixing 5g of sodium hydroxide, 20 g of urea and 100g of deionized water, precooling to-10 ℃, taking out, adding 5g of absorbent cotton, stirring and dissolving to obtain cellulose hydrosol; mixing 100g of cellulose hydrosol, 1g of deionized water and 1g of ammonium zirconium carbonate to obtain a water phase; uniformly stirring and mixing 100g of n-hexane and 0.01 g of tween-40 to obtain an oil phase; mixing 60 g of water phase and 100g of oil phase, stirring to form a suspension, adding 0.5g of ethyl orthosilicate and 2.5 g of hexamethyldisilazane, stirring and reacting for 4 hours under the heating condition of 55 ℃, standing, filtering, washing, and drying for 9 hours at 90 ℃ under normal pressure to obtain cellulose aerogel microspheres;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Dissolving tannic acid in methanol, and adjusting the pH to 8.0 to obtain a tannic acid solution with the mass percentage of 1%; dispersing anatase type nano titanium dioxide (the particle size is 8 nm) in water to obtain a titanium dioxide solution with the mass percentage of 1%; soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution for 60 seconds, and taking out and drying; repeating the operation for 10 times to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution, reacting for 12 hours at 30 ℃, taking out, and drying for 12 hours in a 70 ℃ drying oven to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
The prepared cellulose aerogel microsphere particles with the light stress hydrophilic-hydrophobic conversion response function are spherical, and the particle size is divided intoThe cloth is 500-600 μm. The specific surface area of the microspheres is tested as follows: 200m2(ii)/g; average pore diameter of microspheres: 100 nm. The prepared cellulose aerogel microspheres can realize the change of the wettability of the material from hydrophobicity to hydrophilicity under the condition of ultraviolet light.
Claims (8)
1. A preparation method of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of cellulose aerogel microspheres
Mixing sodium hydroxide, urea and deionized water, precooling to 0-25 ℃, taking out, adding absorbent cotton, stirring and dissolving to obtain cellulose hydrosol, wherein the mass ratio of the sodium hydroxide to the urea to the deionized water to the absorbent cotton is 1-10: 1-20: 100: 0.2-10;
mixing cellulose hydrosol, deionized water and a cross-linking agent according to the mass ratio of 100: 1-2000: 0-10 to obtain a water phase;
uniformly stirring and mixing the low-surface-tension solvent and the surfactant according to the mass ratio of 100: 0.01-1 to obtain an oil phase;
mixing the water phase and the oil phase, stirring to form a suspension, adding a silane modifier, stirring and reacting for 3-10 h under the heating condition of 40-80 ℃, standing after the reaction is finished, filtering, washing and drying to obtain cellulose aerogel microspheres; the mass ratio of the oil phase to the water phase to the silane modifier is 100: 20-100: 0.01-10;
(2) preparation of cellulose aerogel microspheres with light stress hydrophilic-hydrophobic conversion response function
Soaking the cellulose aerogel microspheres prepared in the step (1) in a tannic acid solution with solute mass percent of 0.1-10%, taking out and airing after soaking for 1 second-24 hours; repeating the operation for at least 1 time to obtain the tannin modified cellulose aerogel microspheres; soaking the tannic acid modified cellulose aerogel microspheres in a titanium dioxide solution with solute mass percentage of 0.01-10%, reacting for 1-48 hours at 20-80 ℃, taking out, and drying to obtain the cellulose aerogel microspheres with the light stress hydrophilic-hydrophobic conversion response function.
2. The preparation method of the cellulose aerogel microspheres with the light stress hydropathic-hydrophobic switching response function according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the cross-linking agent is at least one of 1,2,3, 4-butanetetracarboxylic acid, glyoxal, ammonium zirconium carbonate and divinyl sulfone; the low surface tension solvent is at least one of methyl isobutyl ketone, normal hexane and normal octane; the surfactant is at least one of tween-40, tween-60, tween-80, span-40, span-65 and span-80; the silane modifier is at least one of tetraethoxysilane, hexamethyldisiloxane, hexamethyldisilazane and hexamethylcyclotrisiloxane.
3. The preparation method of the cellulose aerogel microspheres with the light stress hydropathic-hydrophobic switching response function according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the preparation method of the tannic acid solution comprises the following steps: dissolving tannic acid in a solvent A, and adjusting the pH value to 7.1-10.0 to obtain a tannic acid solution.
4. The preparation method of the cellulose aerogel microspheres with the light stress hydropathic-hydrophobic switching response function according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the preparation method of the titanium dioxide solution comprises the following steps: dispersing anatase type nano titanium dioxide with the particle size of 0.5-300 nm in a solvent A to obtain a titanium dioxide solution.
5. The preparation method of cellulose aerogel microspheres with light stress hydropathic and hydrophobic switching response function according to claim 3 or 4, wherein the preparation method comprises the following steps: the solvent A is at least one of water, ethanol and methanol.
6. The preparation method of the cellulose aerogel microspheres with the light stress hydropathic-hydrophobic switching response function according to claim 1, wherein the preparation method comprises the following steps: in the step (1), drying is carried out for 1-15 h at 70-120 ℃ under normal pressure; in the step (2), the drying is carried out in a drying oven at the temperature of 40-90 ℃ for 2-24 hours.
7. Cellulose aerogel microspheres with light stress hydropathic and hydrophobic switching response function obtained by the preparation method according to any one of claims 1 to 6.
8. The cellulose aerogel microspheres having a light-stress hydropathic-hydrophobic switching response function according to claim 7, wherein: the microspheres are spherical particles, the particle size is 1-2000 mu m, and the specific surface area is 50-1200 m2(ii)/g, the pore diameter is 5 to 500 nm.
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