CN110862709A - Reversible thermochromic metal complex microcapsule and preparation method and application thereof - Google Patents
Reversible thermochromic metal complex microcapsule and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/26—Thermosensitive paints
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/02—Homopolymers or copolymers of unsaturated alcohols
- C09D129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention provides a reversible thermochromic metal complex microcapsule and a preparation method and application thereof, belonging to the field of metal complex microcapsules. The preparation method comprises the following steps: (1) preparing an internal water phase, (2) preparing an oil phase, (3) dropwise adding the internal water phase prepared in the step (1) into the oil phase prepared in the step (2), stirring and shearing to obtain water-in-oil type colostrum, (4) preparing an external water phase, (5) dropwise adding the water-in-oil type colostrum prepared in the step (3) into the external water phase prepared in the step (4), heating and stirring, and performing post-treatment to obtain the reversible thermochromic metal complex microcapsule. The preparation method of the reversible thermochromic metal complex microcapsule provided by the invention is simple to operate, the prepared reversible thermochromic metal complex microcapsule has high encapsulation, the stability and the weather resistance of the metal complex can be well improved, the dispersibility of the metal complex is improved, and the film forming property of the metal complex after microcapsule encapsulation is high.
Description
Technical Field
The invention belongs to the field of metal complex microcapsules, and particularly relates to a reversible thermochromic metal complex microcapsule and a preparation method thereof.
Background
The water-soluble reversible thermochromic metal complex has high application value in the fields of temperature alarm, thermal display, note anti-counterfeiting labels and the like, and particularly in recent years, the reversible thermochromic intelligent coating becomes a research hotspot of people along with the development of intelligent windows. The reversible thermochromic metal complex has different color changes before and after phase change, can intelligently adjust visible light, and meets the market requirements of people, so that the metal complex coating has good application prospect. However, the water-soluble reversible thermochromic metal complex is easy to deliquesce in air, poor in weather resistance and poor in dispersibility in a film due to easy crystallization, and further application of the metal complex is restricted due to the problems. The encapsulation of the water-soluble reversible thermochromic metal complex is an effective way for solving the problem, the stability and the weather resistance of the encapsulated metal complex are improved, the problem that the metal complex is easy to crystallize is solved, the dispersibility of the metal complex is improved, and the film-forming property of the metal complex is high.
Disclosure of Invention
The invention aims to provide a reversible thermochromic metal complex microcapsule and a preparation method thereof, which can effectively solve the problem of poor stability of a reversible thermochromic metal complex, can improve the stability and weather resistance of the thermochromic metal complex, solve the problem of easy crystallization of the complex and improve the film forming property of the metal complex.
In order to achieve the above object or other objects, the present invention is achieved by the following aspects.
A preparation method of reversible thermochromic metal complex microcapsules comprises the following steps:
(1) preparation of the internal aqueous phase: adding a metal complex, a cross-linking agent, a catalyst and a water-soluble emulsifier into deionized water, and stirring for dissolving;
(2) preparation of oil phase: adding an oil-soluble emulsifier into the organic phase to form an oil phase;
(3) dropwise adding the internal water phase prepared in the step (1) into the oil phase prepared in the step (2), and stirring and shearing to obtain water-in-oil type colostrum;
(4) preparation of external water phase: dissolving wall materials and a water-soluble emulsifier in deionized water to form an external water phase;
(5) and (4) dropwise adding the water-in-oil type colostrum prepared in the step (3) into the external water phase prepared in the step (4), heating and stirring, and performing post-treatment to obtain the reversible thermochromic metal complex microcapsule.
Further, the metal complex is selected from [ (C)2H5)2NH2]2NiCl4、[(C2H5)2NH2]2NiBr4、[(C2H5)2NH2]2CuCl4、[(C2H5)2NH2]2CuBr4、[(C2H5)2NH2]2NiBr2I2、[(C2H5)2NH2]2NiBr3I、[(C2H5)2NH2]2NiBr3.5I0.5、[(C2H5)2NH2]2NiCl2I2、[(C2H5)2NH2]2NiCl3I、[(C2H5)2NH2]2NiCl3.5I0.5One or more of (a).
Further, the cross-linking agent is selected from one or more of malondialdehyde, succindialdehyde, glutaraldehyde and adipaldehyde. Preferably, the cross-linking agent is glutaraldehyde.
Further, the catalyst is selected from one or more of hydrochloric acid, sulfuric acid and acetic acid. Preferably, the catalyst is hydrochloric acid.
Further, the water-soluble emulsifier is selected from one or more of Tween80, sodium dodecyl benzene sulfonate and polyvinyl alcohol. Preferably, the water-soluble emulsifier is selected from Tween 80.
Further, the oil-soluble emulsifier is selected from one or two of Span80 and polylactic acid. Preferably, the oil soluble emulsifier is selected from Span 80.
Further, the organic phase is selected from one or more of cyclohexane, normal hexane, normal heptane and normal octane. Preferably, the organic phase is selected from cyclohexane.
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.
Further, the mass ratio of the metal complex to the deionized water in the step (1) is (0.01-0.5): 1. Preferably, the mass ratio of the metal complex to the deionized water in the step (1) is 0.1: 1.
preferably, the amount of catalyst is 0.5-5mL and the amount of cross-linking agent is 0.3-3 mL.
Further, the mass ratio of the water-soluble emulsifier to the oil-soluble emulsifier in the step (1) is 1: (1-10); preferably 1: 6.
in the step (3), the volume ratio of the internal water phase to the oil phase is 1 (1-10).
Further, the volume ratio of the internal water phase to the oil phase in the step (3) is 1 (1-10). Preferably, the volume ratio of the internal water phase to the oil phase in step (3) is 1: 3.
Further, the mass ratio of the water-soluble emulsifier to the oil-soluble emulsifier in the step (4) is 1: (1-10).
Preferably, the mass ratio of the water-soluble emulsifier to the oil-soluble emulsifier in the step (4) is 1: 6.
further, the mass ratio of the wall material to the deionized water in the step (4) is (0.01-0.5): 1. Preferably, the mass ratio of the wall material to the deionized water in the step (4) is 0.05: 1.
furthermore, the mass ratio of the metal complex to the wall material is (0.01-1): 1. Preferably, the mass ratio of the metal complex to the wall material is 0.4: 1.
further, the shearing time in the step (3) is 20-60min, and the shearing rate is 1000-. Preferably, the shear time in step (3) is 40min and the shear rate is 3000 rpm.
Further, the stirring speed in the step (5) is 200-800rpm, and the stirring time is 2-6 h. Preferably, the stirring speed in step (5) is 600rpm, and the stirring time is 5 h.
Further, the stirring temperature in the step (5) is 20-80 ℃. Preferably, the stirring temperature in step (5) is 60 ℃.
Further, after the heating reaction in the step (5) is finished, further performing post-treatment, wherein the post-treatment comprises centrifugation, washing and vacuum drying. Wherein, the washing is carried out by sequentially adopting deionized water and petroleum ether. The vacuum drying temperature was 45 ℃.
The invention also discloses the reversible thermochromic metal complex microcapsule prepared by the preparation method.
The reversible thermochromic metal complex microcapsule is of a capsule structure, the capsule core is a metal complex, and the capsule wall is PVA.
The third aspect of the invention also provides application of the reversible thermochromic metal complex microcapsule in the field of reversible thermochromic intelligent coatings.
Specifically, 0.5g of the reversible thermochromic metal complex microcapsule is taken and ultrasonically dispersed in 10mL of deionized water, 1.75g of PVA-1788 is added, the mixture is heated and stirred for 1h to stabilize the suspension, then the mixture is rolled on a quartz glass sheet and dried for 1h at the temperature of 80 ℃ to prepare [ (C)2H5)2NH2]2NiCl4A microcapsule film. The microcapsule film has reversible thermochromic properties.
The preparation method of the reversible thermochromic metal complex microcapsule provided by the invention is simple to operate, the prepared reversible thermochromic metal complex microcapsule has high encapsulation, the stability and the weather resistance of the metal complex can be well improved, the dispersibility of the metal complex is improved, and the film forming property of the metal complex after microcapsule encapsulation is high.
Drawings
FIG. 1 is a DSC of the reversible thermochromic metal complex microcapsules obtained in example 1;
FIG. 2 is an SEM photograph of reversible thermochromic metal complex microcapsules obtained in example 1;
FIG. 3 is a graph showing a distribution of particle sizes of reversible thermochromic metal complex microcapsules obtained in example 1;
FIG. 4 is a UV-VIS absorption spectrum of the reversible thermochromic metal complex microcapsule film obtained in example 7.
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.
Regulus 8100 was used in the present examples to test microcapsule Scanning Electron Microscope (SEM) images; the microcapsules mean particle size was measured using a Malvern Instrument Zetasizer Nano; measuring the microcapsule phase transition temperature using DSC 25; measuring the absorption spectrum of the microcapsule film using UV-3600 Plus; the loading rate and the encapsulation rate of the reversible thermochromic metal complex microcapsules are measured by ICP. Specifically, the method comprises the following steps: and (3) placing 10mg of microcapsules in a centrifugal tube, digesting by microwave, and then carrying out ICP detection to obtain the total mass of the metal complex.
The invention is further illustrated by the following specific examples, which are not intended to be limiting and whose scope is indicated in the claims.
Example 1
0.4g of [ (C)2H5)2NH2]2NiCl40.2mL of Tween80, 2mL of glutaraldehyde aqueous solution and 1mL of hydrochloric acid are dissolved in 4mL of deionized water to form an internal water phase; dissolving 1.2mL of Span80 in 20mL of cyclohexane to form an oil phase; 0.2mL of Tween80, 1g of wall material PVA-1799 was dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 3000rpm for 40min to obtain water-in-oil type colostrum, dropwise adding the colostrum into the outer water phase, heating to 60 ℃, continuously stirring at 600rpm for 5h, centrifugally separating a product after the reaction is finished, washing with deionized water and petroleum ether for three times, and then drying in vacuum at 45 ℃ to obtain the microcapsule, wherein the encapsulation rate is 85.2%, and the load rate is 16.7%.
FIG. 1 is a DSC of the reversible thermochromic metal complex microcapsule of example 1, from which it can be seen that the temperature of the endothermic peak is 75 ℃ and the temperature of the exothermic peak is 38.5 ℃. Fig. 2 and 3 are SEM images and particle size distribution diagrams of the reversible thermochromic metal complex microcapsules of example 1, respectively, and it can be seen from fig. 2 that the prepared microcapsules are approximately spherical particles, and have a wide particle size distribution in the range of 0.2 to 0.5 μm. The nano laser particle size instrument shows that the particle size of the prepared microcapsule is normally distributed, the average particle size is about 396.5nm, and the particle size is basically consistent with an SEM picture.
Example 2
0.4g of [ (C)2H5)2NH2]2NiBr40.2mL of Tween80, 2mL of succinaldehyde aqueous solution and 1mL of acetic acid are dissolved in 4mL of deionized water to form an internal water phase; dissolving 1.2mL of Span80 in 20mL of n-octane to form an oil phase; 0.2mL of Tween80, 1g of wall material PVA-1788 was dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 3000rpm for 40min to obtain water-in-oil type colostrum, dropwise adding the colostrum into the outer water phase, heating to 60 ℃, continuously stirring at 600rpm for 5h, centrifugally separating a product after the reaction is finished, washing with deionized water and petroleum ether for three times, and drying in vacuum at 45 ℃ to obtain the microcapsule, wherein the encapsulation rate is 80.4%, and the load rate is 15.9%.
Example 3
0.4g of [ (C)2H5)2NH2]2CuCl40.2mL of Tween80, 2mL of malonaldehyde aqueous solution and 1mL of sulfuric acid are dissolved in 4mL of deionized water to form an internal water phase; dissolving 1.2mL of Span80 in 20mL of n-heptane to form an oil phase; 0.2mL of Tween80, 1g of wall material PVA-2088 was dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 3000rpm for 40min to obtain water-in-oil type colostrum, dropwise adding the colostrum into the outer water phase, heating to 60 ℃, continuously stirring at 600rpm for 5h, centrifugally separating a product after the reaction is finished, washing with deionized water and petroleum ether for three times, and drying in vacuum at 45 ℃ to obtain the microcapsule, wherein the encapsulation rate is 83.0 percent, and the load rate is 16.8 percent.
Example 4
0.4g of [ (C)2H5)2NH2]2NiBr3.5I0.50.2mL of Tween80, 2mL of an aqueous solution of hexanedial and 1mL of hydrochloric acid are dissolved in 4mL of deionized water to form an internal aqueous phase; dissolving 1.2mL of Span80 in 20mL of n-hexane to form an oil phase; 0.2mL of TWEEN80, 1g of wall material PVA-2099 was dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 3000rpm for 40min to obtain water-in-oil type colostrum, dropwise adding the colostrum into the outer water phase, heating to 60 ℃, continuously stirring at 600rpm for 5h, centrifugally separating a product after the reaction is finished, washing with deionized water and petroleum ether for three times, and drying in vacuum at 45 ℃ to obtain the microcapsule, wherein the encapsulation rate is 78.2%, and the load rate is 15.2%.
Example 5
0.6g of [ (C)2H5)2NH2]2NiCl3.5I0.50.1g of polyvinyl alcohol, 1mL of glutaraldehyde aqueous solution and 1mL of hydrochloric acid are dissolved in 3mL of deionized water to form an inner water phase; dissolving 0.5g of polylactic acid in 20mL of cyclohexane to form an oil phase; 0.3g of polyvinyl alcohol, 1g of wall material PVA-1799 was dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 2000rpm for 30min to obtain water-in-oil type colostrum, dripping the colostrum into the outer water phase, heating to 40 ℃, stirring at 800rpm for 4h, centrifugally separating the product after the reaction is finished, washing with deionized water and petroleum ether for three times, and drying at 45 ℃ in vacuum to obtain the microcapsule, wherein the encapsulation rate is 68.7%, and the load rate is 23.8%.
Example 6
0.8g of [ (C)2H5)2NH2]2CuBr40.1g of sodium dodecyl benzene sulfonate, 1mL of glutaraldehyde aqueous solution and 1mL of hydrochloric acid are dissolved in 6mL of deionized water to form an internal water phase; dissolving 0.5g of polylactic acid in 10mL of n-heptane to form an oil phase; 0.3g of sodium dodecylbenzenesulfonate and 1g of wall material PVA-1799 were dissolved in 20mL of deionized water to form an external aqueous phase.
Adding the inner water phase into the oil phase, shearing at 1500rpm for 20min to obtain water-in-oil type colostrum, adding the colostrum dropwise into the outer water phase, heating to 50 ℃, stirring at 600rpm for 6h, centrifugally separating the product after the reaction is finished, washing with deionized water and petroleum ether for three times, and drying in vacuum at 45 ℃ to obtain the microcapsule, wherein the encapsulation rate is 62.7%, and the loading rate is 28.3%.
Examples of the experiments
The [ (C) prepared in example 1 was weighed2H5)2NH2]2NiCl4Dispersing 0.5g of microcapsule in 10mL of deionized water by ultrasonic dispersion, adding 1.75g of PVA-1788, heating and stirring for 1h to stabilize the suspension, roller-coating onto quartz glass sheet, and drying at 80 deg.C for 1h to obtain [ (C)2H5)2NH2]2NiCl4A microcapsule film.
FIG. 4 is an absorption spectrum of a reversible thermochromic metal complex microcapsule film of example 7. At 25 ℃, the film does not absorb in a visible light region (380-780nm), and the film is colorless and transparent; when the temperature is raised to 80 ℃, the film absorbs in the yellow to red region (570-770nm), and then the film turns into sky blue.
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 (10)
1. A preparation method of reversible thermochromic metal complex microcapsules is characterized by comprising the following steps:
(1) preparation of the internal aqueous phase: adding a metal complex, a cross-linking agent, a catalyst and a water-soluble emulsifier into deionized water, and stirring for dissolving;
(2) preparation of oil phase: adding an oil-soluble emulsifier into the organic phase to form an oil phase;
(3) dropwise adding the internal water phase prepared in the step (1) into the oil phase prepared in the step (2), and stirring and shearing to obtain water-in-oil type colostrum;
(4) preparation of external water phase: dissolving wall materials and a water-soluble emulsifier in deionized water to form an external water phase;
(5) and (4) dropwise adding the water-in-oil type colostrum prepared in the step (3) into the external water phase prepared in the step (4), heating and stirring, and performing post-treatment to obtain the reversible thermochromic metal complex microcapsule.
2. The method of claim 1, wherein the metal complex is selected from the group consisting of [ (C)2H5)2NH2]2NiCl4、[(C2H5)2NH2]2NiBr4、[(C2H5)2NH2]2CuCl4、[(C2H5)2NH2]2CuBr4、[(C2H5)2NH2]2NiBr2I2、[(C2H5)2NH2]2NiBr3I、[(C2H5)2NH2]2NiBr3.5I0.5、[(C2H5)2NH2]2NiCl2I2、[(C2H5)2NH2]2NiCl3I、[(C2H5)2NH2]2NiCl3.5I0.5One or more of (a).
3. The method of claim 1, further comprising one or more of the following technical features:
the cross-linking agent is selected from one or more of malondialdehyde, succindialdehyde, glutaraldehyde and adipaldehyde;
the catalyst is selected from one or more of hydrochloric acid, sulfuric acid and acetic acid;
the water-soluble emulsifier is selected from one or more of Tween80, sodium dodecyl benzene sulfonate and polyvinyl alcohol;
the oil-soluble emulsifier is selected from one or two of Span80 and polylactic acid;
the organic phase is selected from one or more of cyclohexane, n-hexane, n-heptane and n-octane;
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.
4. The preparation method according to claim 1, wherein the mass ratio of the metal complex to the deionized water in the step (1) is (0.01-0.5): 1.
5. The method of claim 1, further comprising one or more of the following technical features:
the mass ratio of the water-soluble emulsifier to the oil-soluble emulsifier in the step (1) is 1: (1-10);
in the step (3), the volume ratio of the internal water phase to the oil phase is 1 (1-10);
the mass ratio of the water-soluble emulsifier to the oil-soluble emulsifier in the step (4) is 1: (1-10).
6. The preparation method of claim 1, wherein the mass ratio of the wall material to the deionized water in the step (4) is (0.01-0.5): 1.
7. The preparation method according to claim 1, wherein the mass ratio of the metal complex to the wall material is (0.01-1): 1.
8. The process according to claim 1, wherein the shearing time in step (3) is 20-60min and the shearing rate is 1000-3000 rpm.
9. A reversible thermochromic metal complex microcapsule prepared by the preparation method of any one of claims 1 to 8.
10. Use of the reversible thermochromic metal complex microcapsules of claim 9 in the field of reversible thermochromic smart coatings.
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| CN114478651A (en) * | 2020-11-11 | 2022-05-13 | 中国科学院化学研究所 | Color-changing perovskite material and preparation method and application thereof |
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