CN113174245A - Polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and preparation method thereof - Google Patents

Polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and preparation method thereof Download PDF

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CN113174245A
CN113174245A CN202110454791.5A CN202110454791A CN113174245A CN 113174245 A CN113174245 A CN 113174245A CN 202110454791 A CN202110454791 A CN 202110454791A CN 113174245 A CN113174245 A CN 113174245A
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water
phase
preparation
vanadium dioxide
polyvinyl alcohol
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CN113174245B (en
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蒋绪川
赵修贤
姚伟
聂永
游淇
郭泽艺
徐记岐
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Shandong Xinna Intelligent New Material Co ltd
University of Jinan
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Shandong Xinna Intelligent New Material Co ltd
University of Jinan
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    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
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Abstract

The invention provides a polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule and a preparation method thereof, belonging to the technical field of synthesis of nano polymer composite materials. The preparation method comprises the following steps: (1) vanadium dioxide (VO)2) Modifying the surface of the nano particles; (2) preparing an internal water phase; (3) preparing an oil phase; (4) preparing the product of the step (2)Slowly adding the prepared internal water phase into the oil phase prepared in the step (3), and heating and stirring to obtain water-in-oil type primary emulsion; (5) preparing an external water phase; (6) and (4) dropwise adding the water-in-oil type primary emulsion prepared in the step (4) into the external water phase prepared in the step (5), heating and stirring, and performing post-treatment to obtain the polyvinyl alcohol-coated nano vanadium dioxide photo-thermal response microcapsule. The preparation method provided by the invention is simple, and VO is prepared by2Microencapsulation, enhances the weather resistance, and VO2The compatibility with the organic matrix is also improved; the addition of the photo-responsive organic molecules changes the color of the vanadium dioxide film.

Description

Polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and preparation method thereof
Technical Field
The invention belongs to the technical field of synthesis of nano polymer composite materials, and particularly relates to a polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule polymer composite material and a preparation method thereof.
Background
Vanadium dioxide (VO)2) Is a very typical thermochromic material and is at a critical temperature (T)c) At 68 ℃ VO2Has a reversible metal-insulator transition (MIT) that exhibits a monoclinic (M) phase to rutile (R) phase transition in crystal structure. And VO changes with phase state2Has obvious near infrared transmittance difference. Is embodied as being below T at the phase transition temperaturecThen, VO2Is in an insulator state of M phase, VO2The transmission of infrared rays is not blocked; and above T at the phase transition temperaturecThen, VO2The material is converted into a metallic R phase, and has obvious infrared blocking effect, so that the material is particularly suitable for application of energy-saving intelligent windows. VO is introduced into a reactor2Coated on the surface of the glass, the energy-saving mode of keeping the indoor warm in winter and keeping the indoor cool in summer is realized, but VO2In practical application, the following disadvantages existPoint:
1)VO2the film can not realize the adjustment of visible light, and the coating film is brownish yellow and is not popular in the market;
2)VO2the nano particles are easy to agglomerate due to small particle size and large specific surface area, resulting in VO2The optical properties of the film are degraded;
3)VO2is poor in weather resistance and is easily oxidized to V in the air2O5Loss of the ability to modulate sunlight;
4)VO2the poor compatibility of the nano-particles and the organic matrix during compounding leads to the generation of voids on an inorganic-organic interface, which causes the degradation and embrittlement of the resin at the interface and the organic matrix, and leads to the reduction of the external stress resistance of the resin.
In order to solve the above problems, researchers have made many efforts to prepare VO2The core-shell structure is a well-established method. In the literature, VO is prepared2@SiO2、VO2@TiO2、VO2@ZrO2The inorganic composite core-shell structure solves VO2Poor weather resistance and easy agglomeration, but the problem of compatibility with organic matrix cannot be improved. And the inorganic shell layer is mostly a rigid structure, and VO2The phase change process is accompanied by volume change, so that the inorganic material as a shell layer is easy to crack and break. Furthermore, SiO is prepared2、TiO2And the inorganic shell layer needs high-temperature annealing and other processes, the preparation process is complex, the energy consumption is high, a large amount of waste water is generated, and the method is not suitable for industrial production.
The organic polymer material such as polyvinyl alcohol has excellent transparency and performances such as heat resistance, wear resistance, acid and alkali resistance and the like, and is an ideal shell material. VO is introduced into a reactor2The surface is coated with a layer of organic polymer materials such as polyvinyl alcohol and the like, so that the material has the advantages of an inorganic shell layer and can also improve the stress resistance and the strain resistance. In addition, the problem of compatibility of inorganic materials with organic matrices is also solved. Active groups on the surface of the organic polymer material can be combined with photoresponsive molecules such as organic photoluminescence and the like in a chemical bond form, so that VO is changed2Color of the film, increase VO2The film has the capability of modulating sunlight, and the diversity of products is increased.
Disclosure of Invention
The invention aims to provide a polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule and a preparation method thereof, and the method can effectively improve VO (volatile organic compounds)2Easy agglomeration and poor weather resistance. VO can also be changed by introducing photoluminescent organic molecules2The color of the film. In addition, the compatibility problem of inorganic material and organic matrix is improved, and VO is obtained2The application range of the film is improved.
In order to achieve the above object or other objects, the present invention is achieved by the following aspects.
A preparation method of polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules comprises the following steps:
(1) VO is introduced into a reactor2Dispersing in solvent, ultrasonic treating, adding modifier, heating while stirring, centrifugal collecting, washing, vacuum drying to obtain modified VO2；
(2) Preparation of the internal aqueous phase: the modified VO2Adding a cross-linking agent, a catalyst and a water-soluble emulsifier into deionized water, and performing ultrasonic dispersion;
(3) preparation of oil phase: adding photoluminescent organic molecules and an oil-soluble emulsifier into the organic phase to form an oil phase;
(4) slowly adding the internal water phase prepared in the step (2) into the oil phase, heating and stirring to obtain a water-in-oil type primary emulsion;
(5) preparation of external water phase: dissolving wall materials and a water-soluble emulsifier in deionized water to form an external water phase;
(6) and (4) dropwise adding the water-in-oil type primary emulsion prepared in the step (4) into the external water phase prepared in the step (5), heating and stirring, and performing post-treatment to obtain the polyvinyl alcohol-coated nano vanadium dioxide photo-thermal response microcapsule.
Further, the VO2Monoclinic (M) phase.
Further, the modifier is selected from one or more of catechol, ascorbic acid and a silane coupling agent KH-550. Preferably, the modifying agent is ascorbic acid.
Further, the solvent is selected from one or two of ethanol, methanol, deionized water and toluene. Preferably, the solvent is deionized water.
Further, the cross-linking agent is selected from one or more of terephthalaldehyde, succinaldehyde, glutaraldehyde and adipaldehyde. Preferably, the cross-linking agent is glutaraldehyde.
Further, the catalyst is selected from one or more of sulfuric acid, hydrochloric acid and acetic acid. Preferably, the catalyst is hydrochloric acid.
Further, the water-soluble emulsifier is selected from one or two of cetyl trimethyl ammonium bromide, sodium dodecyl benzene sulfonate, Tween80 and PVA. Preferably, the water-soluble emulsifier is Tween 80.
Further, the photoluminescent organic molecule is selected from pyrenecarboxaldehyde, tris (8-hydroxyquinoline) aluminum derivative (Alq)3) Bis (8-hydroxyquinoline) zinc derivative (Znq)2) One or more of (a). Wherein the tris (8-hydroxyquinoline) aluminum derivative can be one or more selected from tris (8-hydroxyquinoline-2-carbaldehyde) aluminum, bis (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde) aluminum and (8-hydroxyquinoline) bis (8-hydroxyquinoline-2-carbaldehyde) aluminum; the bis (8-hydroxyquinoline) zinc derivative is as follows: one or more of bis (8-hydroxyquinoline-2-carbaldehyde) zinc and (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde) zinc.
Further, the oil-soluble emulsifier is selected from one or two of Span60, Span65, Span80 and Span 85. Preferably, the oil soluble emulsifier is Span 80.
Further, the organic phase is selected from one or more of toluene, n-hexane, n-heptane and n-octane. Preferably, the organic phase is toluene.
Further, the wall material is selected from one or more of PVA-0588 type, PVA-1788 type, PVA-1799 type, PVA-2088 type, PVA-2099 type, PVA-2488 type and PVA-2499 type. Preferably, the wall material is of the PVA-1788 type.
Further, the addition amount of the modifier in the step (1) is VO21 to 10 percent of the mass. Preferably, the addition amount of the modifier in the step (1) is VO22.5% of the mass.
Further, the pH value of the inner water phase in the step (2) is between 1 and 4. Preferably, in step (1), the pH of the internal aqueous phase is 2.
Further, the mass fraction of the water-soluble emulsifier in the step (2) is 1-10%. Preferably, the mass fraction of the water-soluble emulsifier in the step (2) is 5%.
Further, the mass fraction of the oil-soluble emulsifier in the step (3) is 1-30%. Preferably, the mass fraction of the oil-soluble emulsifier in the step (3) is 10%.
Further, the volume ratio of the internal water phase to the oil phase in the step (4) is 1 (1-10). Preferably, the volume ratio of the internal water phase to the oil phase in step (4) is 1: 3.
Further, the mass fraction of the water-soluble emulsifier in the step (5) is 1-10%. Preferably, the mass fraction of the water-soluble emulsifier in the step (5) is 5%.
Furthermore, the mass ratio of the wall material to the deionized water in the step (5) is (0.002-0.01): 1. Preferably, the mass ratio of the wall material to the deionized water in the step (5) is 0.004: 1.
further, the volume ratio of the primary emulsion to the external water phase in the step (6) is 1: (10-40). Preferably, the volume ratio of the primary emulsion to the external aqueous phase is 1: 10.
further, the modified VO2The mass ratio of the wall material to the wall material is (0.01-1): 1. Preferably, VO after modification2The mass ratio of the wall material to the wall material is 0.5: 1.
Furthermore, the mass ratio of the photoluminescent organic molecules to the wall material is (0.01-1): 1. Preferably, the mass ratio of photoluminescent organic molecules to wall material is 0.2: 1.
Further, the mass ratio of the cross-linking agent to the wall material is (0.1-2.5): 1. Preferably, the mass ratio of the cross-linking agent to the wall material is 0.5: 1.
Further, the ultrasonic time is 10-60 min. Preferably, the sonication time is 30 min.
Further, the reaction temperature in the step (1) is 30-80 ℃. Preferably, the reaction temperature in step (1) is 60 ℃.
Further, the reaction time in the step (1) is 3-12 h. Preferably, the reaction time in step (1) is 4 h.
Further, the emulsifying temperature in the step (4) is 40-80 ℃. Preferably, the emulsification temperature in step (4) is 70 ℃.
Further, the dissolving temperature of the wall material in the step (5) is 60-90 ℃. Preferably, the wall material dissolution temperature in step (5) is 60 ℃.
Further, the reaction temperature in the step (6) is 40-80 ℃. Preferably, the reaction temperature in step (6) is 70 ℃.
Further, in the step (6), the stirring speed is 200-2000 rpm, and the stirring time is 1-6 h. Preferably, the stirring speed in step (6) is 1000rpm, and the stirring time is 2 h.
Further, after the heating reaction in the step (6) is finished, post-treatment is carried out, wherein the post-treatment comprises centrifugation, washing and vacuum drying. Wherein, the washing is carried out by sequentially adopting deionized water and ethanol. The vacuum drying temperature was 35 ℃.
The preparation method of the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule provided by the invention is simple and feasible, and the prepared VO2The core-shell structure not only has the advantages of an inorganic shell layer, but also has strong stress resistance and strain resistance of a flexible shell layer. VO can be changed by introducing organic molecules such as photoluminescence and the like into a polymer shell layer2Color of film, VO2The film has enhanced solar light modulation capability and VO2The application range of the coated glass is improved.
Drawings
FIG. 1 is an SEM image of polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules of example 1;
FIG. 2 is a TEM image of polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule of example 1;
FIG. 3 is a steady-state fluorescence emission spectrum of the polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule in example 1;
FIG. 4 is VO2XRD pattern of nanoparticles;
FIG. 5 is an XRD pattern of the polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule of example 1.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention. Test methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the respective manufacturers.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
In the embodiment of the invention, a scanning electron microscope (SEM, Regulus 8100, Hitachi, Japan) is used for observing the appearance of the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule; observing the coating condition of the polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule by using a transmission electron microscope (TEM, JEM 2100, Japan); measurement Using Combined Steady-State fluorescence Spectroscopy (FLS920, Edinburgh Instruments, Britain)Measuring the fluorescence emission spectrum of the polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule, wherein the excitation wavelength is 365 nm; observation of VO Using X-ray diffraction (XRD, Model SmartLabSE, Rigaku, Japan)2And the phase state of the nanometer vanadium dioxide particles coated by the polyvinyl alcohol.
The invention is further illustrated by the following specific examples, but the invention is not limited thereto, and the specific scope of protection is found in the claims.
Example 1
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of deionized water, and sonicating for 30 min. Then heated to 60 ℃ with a water bath and stirred for 10 min. 0.025g of ascorbic acid was weighed into the above system and the reaction was continued for 4 h. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparation of tris (8-hydroxyquinoline-2-carbaldehyde) aluminum:
a100 mL three-necked flask was charged with 2.04g of aluminum isopropoxide and 50mL of anhydrous ethanol, heated and stirred, and then 5.20g of 8-hydroxyquinoline-2-carbaldehyde was added thereto to continue the reaction for 2 hours. After the reaction was completed, the solvent was removed, washed with n-hexane several times, and dried under vacuum to obtain an orange solid powder.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.2g of modified VO2Adding into 3mL deionized water, and ultrasonically dispersing for 30 min. Then 0.20g of glutaraldehyde and 0.18g of Tween80 are added, the mixture is stirred until uniform, and hydrochloric acid is used for adjusting the pH value to 2 to form an internal water phase; 0.08g of tris (8-hydroxyquinoline-2-carbaldehyde) aluminum and 1.00g of Span80 were added to 10mL of toluene to form an oil phase; 0.4PVA-1788 and 5g Tween80 were dissolved in 100mL deionized water and warmed to 60 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 70 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 70 ℃ and continuously stirring for 2 hours at 1000rpm, centrifugally separating a product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
FIG. 1 is an SEM image of the polyvinyl alcohol-coated vanadium dioxide nano photo-thermal response microcapsule in example 1, and it can be seen that the prepared microcapsule is approximately spherical particles, and the particle size distribution is in the range of 150-200 nm. FIG. 2 is a TEM image of the PVA-coated nano vanadium dioxide photothermal response microcapsule in example 1, and it can be seen that PVA is coated on VO2The surface and the shell layer thickness are about 20 nm. Fig. 3 is a steady state fluorescence spectrum of the polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule in example 1, and it can be seen from the steady state fluorescence spectrum that the polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsule emits 512nm in wavelength and is green light by using 365nm ultraviolet light for excitation. FIG. 4 shows uncoated VO2XRD pattern of (1), XRD characterization VO after indoor placement for 90 days2The nanoparticles appear heterogeneous, indicating VO2Is oxidized. FIG. 5 is an XRD pattern of the polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule in example 1, and after the microcapsule is placed indoors for 90 days, the XRD represents VO2The nano particles are not obviously changed, which shows that the shell layer of the polyvinyl alcohol can effectively improve VO2Weatherability of the nanoparticles.
Example 2
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of ethanol, and performing ultrasonic treatment for 60 min. Subsequently, the mixture was heated to 30 ℃ in a water bath and stirred for 10 min. 0.01g of ascorbic acid was weighed out and added to the above system, and the reaction was continued for 6 hours. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparation of (8-hydroxyquinoline) bis (8-hydroxyquinoline-2-carbaldehyde) aluminum:
a100 mL three-necked flask was charged with 2.04g of aluminum isopropoxide and 50mL of anhydrous ethanol, heated and stirred, and then 1.45g of 8-hydroxyquinoline was added thereto to conduct a reaction for 30min, followed by addition of 3.46g of 8-hydroxyquinoline-2-carbaldehyde and continuation of the reaction for 2 hours. After the reaction was completed, the solvent was removed, washed with n-hexane several times, and dried under vacuum to obtain an orange solid powder.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.2g of modified VO2Adding into 4mL deionized water, and ultrasonically dispersing for 30 min. Then 0.20g of hexanedial and 0.2g of sodium dodecyl benzene sulfonate are added, stirred until uniform, and the pH value is adjusted to 1.5 by hydrochloric acid to form an internal water phase; 0.08g of (8-hydroxyquinoline) bis (8-hydroxyquinoline-2-carbaldehyde) and 1.00g of Span85 were added to 10mL of toluene to form an oil phase; 0.4PVA-1799 and 5g sodium dodecylbenzenesulfonate were dissolved in 100mL deionized water and warmed to 70 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 40 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 70 ℃ and continuously stirring at 800rpm for 3 hours, centrifugally separating the product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
Example 3
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of deionized water, and sonicating for 50 min. Then heated to 50 ℃ with a water bath and stirred for 10 min. 0.05g of catechol was weighed out and added to the above system, and the reaction was continued for 5 hours. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparation of bis (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde) aluminum:
a100 mL three-necked flask was charged with 2.04g of aluminum isopropoxide and 50mL of anhydrous ethanol, heated and stirred, and then 2.90g of 8-hydroxyquinoline was added thereto to conduct a reaction for 30min, followed by addition of 1.73g of 8-hydroxyquinoline-2-carbaldehyde and continuation of the reaction for 2 hours. After the reaction was completed, the solvent was removed, washed with n-hexane several times, and dried under vacuum to obtain an orange solid powder.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.1g of modified VO2Adding into 2mL deionized water, and ultrasonically dispersing for 30 min. Then adding 0.30g of succinaldehyde and 0.2g of hexadecyl trimethyl ammonium bromide, stirring until the mixture is uniform, and adjusting the pH value to be 1 by hydrochloric acid to form an inner water phase; 0.1g of bis (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde)) Aluminum, 1.00g Span65 was added to 10mL toluene to form an oil phase; 0.4PVA-2088 and 6g cetyltrimethylammonium bromide were dissolved in 200mL deionized water and warmed to 60 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 60 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 70 ℃ and continuously stirring for 2 hours at 1000rpm, centrifugally separating a product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
Example 4
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of deionized water, and sonicating for 10 min. Then heated to 80 ℃ with a water bath and stirred for 10 min. 0.025g of silane coupling agent KH-550 is weighed and added into the system, and the reaction is continued for 12 hours. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparation of bis (8-hydroxyquinoline-2-carbaldehyde) zinc:
1.86g of zinc acetate was weighed into 50mL of deionized water (No. 1) and stirred at room temperature, 3.46g of 8-hydroxyquinoline-2-carbaldehyde was weighed into 50mL of absolute ethanol (No. 2), and 4g of NaOH was weighed into 20mL of deionized water (No. 3). Adding the solution No. 2 into the solution No. 1, stirring and reacting for 1h, then dripping the solution No. 3 into the mixed solution, separating out flocculent precipitate, continuing to react for 1h, removing the solvent after the reaction is finished, washing with water and normal hexane for multiple times, and drying in vacuum to obtain solid powder.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.1g of modified VO2Put into 3mL deionized water and dispersed for 30min by ultrasonic. Then 0.20g of glyoxal and 0.18g of Tween80 are added, the mixture is stirred until the mixture is uniform, and hydrochloric acid is used for adjusting the pH value to 1 to form an internal water phase; 0.08g of zinc bis (8-hydroxyquinoline-2-carbaldehyde) and 1.00g of Span60 were added to 10mL of toluene to form an oil phase; 0.4PVA-1788 and 5g Tween80 were dissolved in 100mL deionized water and warmed to 80 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 60 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 40 ℃ and continuously stirring for 2 hours at 1000rpm, centrifugally separating a product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
Example 5
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of methanol, sonicated for 20 min. Then heated to 60 ℃ with a water bath and stirred for 10 min. 0.1g of ascorbic acid was weighed into the above system and reacted for 3 hours. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparation of (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde) zinc:
1.86g of zinc acetate is weighed and dissolved in 50mL of deionized water (No. 1), stirred at room temperature, 1.45g of 8-hydroxyquinoline is weighed and dissolved in 50mL of absolute ethyl alcohol (No. 2), 1.73g of 8-hydroxyquinoline-2-formaldehyde is weighed and dissolved in 50mL of absolute ethyl alcohol (No. 3), and 4g of NaOH is weighed and dissolved in 20mL of deionized water (No. 4). Adding the No. 2 solution into the No. 1 solution, stirring to react for 30min, adding the No. 3 solution, continuing to react for 30min, then dripping the No. 4 solution into the mixed solution, separating out flocculent precipitate, continuing to react for 1h, removing the solvent after the reaction is finished, washing with water and n-hexane for multiple times, and drying in vacuum to obtain solid powder.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.1g of modified VO2Adding into 4mL deionized water, and ultrasonically dispersing for 30 min. Then 0.20g of glutaraldehyde and 0.18g of Tween80 are added, the mixture is stirred until the mixture is uniform, and hydrochloric acid is used for adjusting the pH value to 1 to form an internal water phase; 0.06g of (8-hydroxyquinoline) (8-hydroxyquinoline-2-carbaldehyde) zinc and 1.00g of Span80 were added to 10mL of toluene to form an oil phase; 0.4PVA-1788 and 5g Tween80 were dissolved in 100mL deionized water and warmed to 60 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 60 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 80 ℃ and continuously stirring for 6 hours at 200rpm, centrifugally separating a product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
Example 6
VO2Surface treatment of nano particles:
into a 250mL three-necked flask was added 1g of VO2And 100mL of deionized water, and sonicating for 40 min. Then heated to 70 ℃ with a water bath and stirred for 10 min. 0.025g of catechol was weighed into the above system and reacted for 3.5 h. The product was collected by centrifugation, washed with deionized water and dried in vacuo.
Preparing polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules:
0.2g of modified VO2Adding into 3mL deionized water, and ultrasonically dispersing for 30 min. Then 0.20g of glutaraldehyde and 0.18g of Tween80 are added, the mixture is stirred until uniform, and hydrochloric acid is used for adjusting the pH value to 2 to form an internal water phase; adding 0.08g of pyrene formaldehyde and 1.00g of Span80 into 10mL of toluene to form an oil phase; 0.4PVA-1788 and 5g Tween80 were dissolved in 100mL deionized water and warmed to 90 ℃ to form an external aqueous phase.
Slowly adding the inner water phase into the oil phase, heating to 70 ℃ to obtain water-in-oil type primary emulsion, then dropwise adding the primary emulsion into the outer water phase, heating to 50 ℃ and continuously stirring at 800rpm for 3 hours, centrifugally separating the product after the reaction is finished, washing with deionized water and ethanol for three times, and then drying in vacuum at 35 ℃ to obtain the polyvinyl alcohol-coated nano vanadium dioxide photothermal response microcapsule.
The foregoing embodiments are merely illustrative of the principles of the present invention and its efficacy, and are not to be construed as limiting the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (8)

1. A preparation method of polyvinyl alcohol coated nano vanadium dioxide photo-thermal response microcapsules is characterized by comprising the following steps:
(1) VO is introduced into a reactor2Dispersing in solvent, ultrasonic treating, adding modifier, heating while stirring, centrifugal collecting, washing, vacuum drying to obtain modified VO2；
(2) Preparation of the internal aqueous phase: the modified VO2Adding a cross-linking agent, a catalyst and a water-soluble emulsifier into deionized water, and performing ultrasonic dispersion;
(3) preparation of oil phase: adding photoluminescent organic molecules and an oil-soluble emulsifier into the organic phase to form an oil phase;
(4) slowly adding the internal water phase prepared in the step (2) into the oil phase, heating and stirring to obtain a water-in-oil type primary emulsion;
(5) preparation of external water phase: dissolving wall materials and a water-soluble emulsifier in deionized water to form an external water phase;
(6) and (4) dropwise adding the water-in-oil type primary emulsion prepared in the step (4) into the external water phase prepared in the step (5), heating and stirring, and performing post-treatment to obtain the polyvinyl alcohol-coated nano vanadium dioxide photo-thermal response microcapsule.
2. The method according to claim 1, wherein the photoluminescent organic molecule is selected from one or more of pyrenecarboxaldehyde, tris (8-hydroxyquinoline) aluminum derivatives, bis (8-hydroxyquinoline) zinc derivatives.
3. The method of claim 1, further comprising one or more of the following technical features:
the addition amount of the modifier in the step (1) is VO21-10% of the mass;
the mass fraction of the water-soluble emulsifier in the step (2) is 1-10%;
the mass fraction of the oil-soluble emulsifier in the step (3) is 1-30%;
in the step (4), the volume ratio of the internal water phase to the oil phase is 1 (1-10);
the mass fraction of the water-soluble emulsifier in the step (5) is 1-10%;
in the step (5), the mass ratio of the wall material to the deionized water is (0.002-0.01): 1.
4. The method of claim 1, wherein the modified VO is produced by2The mass ratio of the wall material to the wall material is (0.01-1): 1.
5. The preparation method according to claim 1, wherein the mass ratio of the photoluminescent organic molecule to the wall material is (0.01-1): 1.
6. The method according to claim 1, wherein the mass ratio of the crosslinking agent to the wall material is (0.1-2.5): 1.
7. The process of claim 1, wherein the volume ratio of the water-in-oil type primary emulsion to the external aqueous phase in step (6) is from 1: (10-40).
8. The polyvinyl alcohol coated nano vanadium dioxide photothermal response microcapsule prepared by the preparation method of any one of claims 1 to 7.
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