CN113999585A - Thermochromic radiation refrigeration coating, thermochromic radiation refrigeration film and preparation method thereof - Google Patents

Thermochromic radiation refrigeration coating, thermochromic radiation refrigeration film and preparation method thereof Download PDF

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CN113999585A
CN113999585A CN202111439840.4A CN202111439840A CN113999585A CN 113999585 A CN113999585 A CN 113999585A CN 202111439840 A CN202111439840 A CN 202111439840A CN 113999585 A CN113999585 A CN 113999585A
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film
thermochromic
radiation
agent
temperature
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夏欣瑶
王赛
季浩卿
陆洪彬
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Nantong Juren New Material Technology Co ltd
Suzhou University
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Nantong Juren New Material Technology Co ltd
Suzhou University
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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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Abstract

A thermochromic radiation refrigeration coating is prepared from the following raw materials in parts by weight: 50-150 parts of temperature-sensitive resin; 5-10 parts of a film forming agent; 0.1-5 parts of a dispersing agent; 0.1-4 parts of a defoaming agent; 0.1-4 parts of a thickening agent; 4-7 parts of a radiation agent; 1-7 parts of a reflecting agent; 100-500 parts of a solvent. The thermochromic radiation refrigerating film disclosed by the invention has the advantages that the color change mechanism is temperature-controlled color change, the color change temperature range is in the natural environment temperature range, and when the environment temperature is higher, the color of the film is white, so that the solar radiation reflection is enhanced; when the ambient temperature is lower, the color of the film becomes transparent, and the radiation refrigerating capacity of the film is reduced; thereby achieving the effects of saving energy for buildings all the year round, keeping indoor comfortable temperature, reducing the use of air conditioners and heating equipment and reducing carbon emission. In addition, the thermochromic temperature can be adjusted through simple formula adjustment; the film has sensitive color change, strong temperature sensitivity and rapid color change; the raw material cost is low, the preparation method is simple, and the method can be widely applied to industries such as buildings, automobiles and the like.

Description

Thermochromic radiation refrigeration coating, thermochromic radiation refrigeration film and preparation method thereof
Technical Field
The invention relates to the field of composite films, in particular to a thermochromic radiation refrigeration coating, a thermochromic radiation refrigeration film and a preparation method thereof.
Background
With the continuous growth of global economy, population and the like, the rapid advance of industrialization and urbanization processes, the world energy consumption is increasing day by day. According to the investigation, in developed countries, up to 40% of the total energy consumption is used for building energy consumption, and the building energy consumption rate in China is also up to one third. According to the prediction of the energy information administration of the United states, China will become the largest building energy consumption country by 2040 years, and the energy consumption of China is twice that of the United states and accounts for 24% of the total building energy consumption of the world. At present, about 50% of building energy consumption in China is used for heating, cooling, ventilating and other systems. Therefore, the reduction of the energy consumption of the building and the development of a new method and a new technology for refrigeration and cooling to save the energy consumption of the building are very slow tasks and are significant challenges in the strategy of sustainable development.
In reducing the energy consumption of buildings, the radiation refrigeration is a novel refrigeration mode without energy consumption and pollution. The radiation refrigeration is a cooling technology for radiating heat of objects on the earth to outer space by reflecting solar radiation and utilizing thermal radiation. Thermal radiation is one type of energy transfer, and any object with a temperature higher than 0K radiates energy to the surrounding environment due to its temperature. However, the earth has a thick layer of atmosphere on the surface, so that the heat radiation of the objects on the earth cannot easily pass through the earth. Through analysis of atmospheric spectral transmission characteristics, researchers find that electromagnetic waves with the wavelength of 8-14 μm can efficiently penetrate through the atmosphere on the earth surface. Therefore, these regions are referred to as "atmospheric windows". If the heat radiation of the object on the earth surface is heat exchanged with the outer space through the atmospheric window, the refrigeration effect without energy consumption can be achieved.
Most of the research on the traditional radiation refrigeration coating focuses on the solar radiation modulation capability, and relatively few researches on other functions are carried out. Conventional radiation refrigeration coatings have good refrigeration capacity when the temperature is higher in the summer and increased heating energy consumption when the temperature is lower in the winter.
In view of the above problems, it is highly desirable to develop a novel refrigeration film.
Disclosure of Invention
In view of the above, the invention provides a thermochromic radiation refrigeration coating, a thermochromic radiation refrigeration film and a preparation method thereof, wherein the thermochromic radiation refrigeration coating and the thermochromic radiation refrigeration film can save energy sources and reduce carbon emission for buildings, automobiles and the like.
The invention aims to provide a thermochromic radiation refrigeration coating, which is prepared from the following raw materials in parts by weight:
Figure BDA0003382559070000021
specifically, the temperature-sensitive resin is polyacrylamide resin, and the relative molecular mass of the polyacrylamide resin is 103、104、105、106g·mol-1One or more of;
preferably, the polyacrylamide resin is poly-N-isopropylacrylamide.
Specifically, the film forming agent is one or more of a protein film forming agent, an acrylic resin film forming agent, a polyurethane film forming agent, a butadiene resin film forming agent and a nitrocellulose film forming agent; the dispersant is one or more of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum and fatty acid polyglycol ester
Specifically, the defoaming agent is one or a mixture of more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene; the thickening agent is one or a mixture of more of sodium carboxymethylcellulose, agar, xanthan gum, carrageenan and pectin; the solvent is water.
Specifically, the radiation agent is silica particles, and the particle size of the silica particles is 5.0 μm; the reflecting agent is titanium dioxide particles, and the particle size of the titanium dioxide particles is 0.4 mu m.
The second purpose of the invention is to provide a thermochromic radiation refrigerating film prepared from the thermochromic radiation refrigerating coating.
Specifically, before thermochromic change, the film is a transparent film, the initial transmittance of the film is 79.5% -91.8%, the initial average reflectivity in a solar spectrum waveband is 37.5% -46.7%, and the initial average emissivity in an atmospheric window waveband is 43.2% -49.8%.
Specifically, the thermochromic temperature of the film is 28.7-37.4 ℃, after the film is thermally changed into white, the light transmittance of the film is 10.5-36.2%, the average reflectivity of the film is 90.3-95.5% when the film is flattened in a solar spectrum waveband, and the average radiance of the film is up to 89.8-94.1% when the film is flattened in an atmospheric window waveband.
Specifically, the thickness of the film is 200-600 μm, and the film can be recycled for at least 1000 times.
The third purpose of the invention is to provide a preparation method of the film, which comprises the following steps:
respectively weighing the temperature-sensitive resin, the film forming agent, the dispersing agent, the defoaming agent, the thickening agent, the radiant agent, the reflecting agent and the solvent, mixing and stirring to form the thermochromic radiation refrigeration coating, and coating the thermochromic radiation refrigeration coating to prepare the film.
The invention creatively provides that compared with the prior art, the invention has the following advantages:
1. the thermochromic radiation refrigerating film disclosed by the invention has the advantages that the color change mechanism is temperature-controlled color change, the color change temperature range is in the natural environment temperature range, and when the environment temperature is higher, the color of the film is white, so that the solar radiation reflection is enhanced; when the ambient temperature is lower, the color of the film becomes transparent, and the radiation refrigerating capacity of the film is reduced; thereby achieving the effects of saving energy for buildings all the year round, keeping indoor comfortable temperature, reducing the use of air conditioners and heating equipment and reducing carbon emission.
2. The selection of the temperature-sensitive resin can promote the enhancement of the radiation refrigeration effect, so that the film is a reversible color-changing film, the service life is long, and the color-changing performance and the radiation refrigeration performance are still stable after long-term use;
3. in addition, the thermochromic temperature can be adjusted through simple formula adjustment; the film has sensitive color change, strong temperature sensitivity and rapid color change; the raw material cost is low, the preparation method is simple, and the method can be widely applied to industries such as buildings, automobiles and the like.
Detailed Description
Reducing the energy consumption of buildings, and developing new methods and new technologies for refrigeration and cooling to save the energy consumption of the buildings are irresistible tasks and are significant challenges in the strategy of sustainable development. In order to solve the problems that in the prior art, most researches on the traditional radiation refrigeration coating focus on solar radiation modulation capability, and researches on other functions are relatively few; the application provides a thermochromic radiation refrigeration coating, a thermochromic radiation refrigeration film and a preparation method thereof, which can save energy and reduce carbon emission for buildings, automobiles and the like.
The invention provides a thermochromic radiation refrigeration coating, which is prepared from the following raw materials in parts by weight:
Figure BDA0003382559070000041
the temperature sensitive resin is polyacrylamide resin, and the relative molecular mass of the polyacrylamide resin is 103、104、105、106g·mol-1One or more of; preferably, the polyacrylamide resin is poly-N-isopropylacrylamide. Poly (N-isopropylacryloyl)Amine is a temperature-sensitive high-molecular polymer material, and can form particles with different particle sizes after being heated to a high temperature, so that the reflection and scattering effects of light are generated, and the radiation refrigeration effect in the application is enhanced.
In order to make the film have excellent coalescence property and stability, the invention also adds film-forming agent to promote the plastic flow and elastic deformation of high molecular polymer, improve coalescence property, and make the film be formed in a larger temperature range. The film forming agent comprises one or more of a protein film forming agent, an acrylic resin film forming agent, a polyurethane film forming agent, a butadiene resin film forming agent and a nitrocellulose film forming agent.
In order to ensure that each film forming component has good compatibility, the invention also adds a dispersant to promote inorganic particles such as a radiation agent, a reflecting agent and the like to have good dispersion effect in the film and prevent the inorganic particles from generating unstable phenomena such as sedimentation, agglomeration and the like. The dispersant includes but is not limited to one or more of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum and fatty acid polyglycol ester.
In order to ensure that the film has good transmittance, the defoaming agent is added in the invention to eliminate air bubbles brought in the preparation process and avoid influencing the initial transmittance of the film. The defoaming agent includes but is not limited to emulsified silicone oil, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and one or more mixtures of polyoxypropylene.
In order to improve the viscosity of the emulsion of the film and enhance the stability of the film, the invention also adds the thickening agent to keep the components in the emulsion for preparing the film in a uniform and stable suspension state and promote the stability of the film gel. Thickening agents include, but are not limited to, one or a mixture of several of sodium carboxymethylcellulose, agar, xanthan gum, carrageenan, and pectin.
In order to ensure that the film is low in preparation cost and environment-friendly, the solvent selected by the invention is water.
In order to make the film have a certain emissivity and realize the radiation refrigeration effect, the invention also adds a radiation agent to promote the film to enhance the emissivity of the atmospheric window, thereby reducing the self temperature and achieving the radiation refrigeration effect. The radiant agent is silica particles, and the particle size of the silica particles is 5.0 mu m.
In order to make the film have a certain reflectivity and realize the radiation refrigeration effect, the invention also adds a reflecting agent to promote the film to enhance the reflectivity of the atmospheric window, thereby avoiding the temperature rise per se and achieving the radiation refrigeration effect. The reflecting agent is titanium dioxide particles, and the particle size of the titanium dioxide particles is 0.4 mu m.
The invention also provides a thermochromic radiation refrigerating film prepared from the thermochromic radiation refrigerating coating.
Before thermochromism, the film is a transparent film, the initial transmittance of the film is 79.5-91.8%, the initial average reflectivity in a solar spectrum waveband is 37.5-46.7%, and the initial average radiance in an atmospheric window waveband is 43.2-49.8%. The thermochromism temperature of the film is 28.7-37.4 ℃, after the film is thermally changed into white, the thermochromism transmittance of the film is 10.5-36.2%, the flattening average reflectivity in a solar spectrum waveband is 90.3-95.5%, and the flattening average radiance in an atmospheric window waveband is up to 89.8-94.1%.
The thickness of the film is 200-600 mu m, and the film can be recycled for at least 1000 times.
The invention also provides a preparation method of the film, which comprises the following steps: respectively weighing temperature-sensitive resin, a film forming agent, a dispersing agent, a defoaming agent, a thickening agent, a radiation agent, a reflecting agent and a solvent, mixing and stirring to form the thermochromic radiation refrigeration coating, and coating the thermochromic radiation refrigeration coating to prepare the film. The coating method of the invention comprises spin coating, blade coating, printing, spray coating and the like.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry.
Example 1 this example provides a thermochromic radiation-curable coating, a thermochromic radiation-curable film, and methods for making the same,
1. the thermochromic radiation refrigeration coating is prepared from the following raw materials in parts by weight:
Figure BDA0003382559070000061
Figure BDA0003382559070000071
2. a thermochromic radiation refrigerating film is prepared by the following steps:
and mixing and stirring the weighed temperature-sensitive resin, film-forming agent, dispersing agent, defoaming agent, thickening agent, radiant agent, reflecting agent and solvent for 90min to form the thermochromic radiation refrigeration coating, and coating the thermochromic radiation refrigeration coating to prepare the film with the thickness of 400 mu m.
3. The thermochromic temperature of the film prepared above was measured to be 37.4 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000072
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 2 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a preparation method thereof, which are substantially the same as those in embodiment 1, except that some of the preparation raw materials are different, specifically, the following differences are provided: Poly-N-isopropylacrylamide with a molecular weight of 104g·mol-1。
The thermochromic temperature of the film prepared above was measured to be 34.8 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000073
Figure BDA0003382559070000081
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 3 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a preparation method thereof, which are substantially the same as those in embodiment 1, except that some of the preparation raw materials are different, specifically, the following differences are provided: Poly-N-isopropylacrylamide with a molecular weight of 105g·mol-1。
The thermochromic temperature of the film prepared above was measured to be 33.6 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000082
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 4 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 1, except that some of the preparation raw materials are different, specifically, the following differences are provided: Poly-N-isopropylacrylamide with a molecular weight of 106g·mol-1。
The thermochromic temperature of the film prepared above was measured to be 32.2 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000083
Figure BDA0003382559070000091
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 5 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: the addition amount of the silicon dioxide radiation agent is 4 parts.
The thermochromic temperature of the film prepared above was measured to be 33.4 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000092
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 6 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: the addition amount of the silicon dioxide radiation agent is 6 parts.
The thermochromic temperature of the film prepared above was measured to be 33.7 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000093
Figure BDA0003382559070000101
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 7 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: the addition amount of the silicon dioxide radiation agent is 7 parts.
The thermochromic temperature of the film prepared above was measured to be 33.9 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000102
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 8 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: and 1 part of titanium dioxide reflecting agent.
The thermochromic temperature of the film prepared above was measured to be 35.2 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000103
Figure BDA0003382559070000111
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 9 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: 5 parts of titanium dioxide reflecting agent.
The thermochromic temperature of the film prepared above was measured to be 31.7 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000112
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 10 this example provides a thermochromic radiation-refrigerating coating, a thermochromic radiation-refrigerating thin film, and a method for producing the same, which are substantially the same as those in embodiment 3, except that some of the preparation raw materials are different, specifically, the following differences are provided: 7 parts of titanium dioxide reflecting agent.
The thermochromic temperature of the film prepared above was measured to be 29.8 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000113
Figure BDA0003382559070000121
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Example 11 this example provides a thermochromic radiation-curable coating, a thermochromic radiation-curable thin film, and a method for making the same, which are substantially the same as example 3, except that the thin film has a thickness of 400 μm.
The thermochromic temperature of the film prepared above was measured to be 36.8 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000122
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Example 12 this example provides a thermochromic radiation-curable coating, a thermochromic radiation-curable film, and a method for making the same, which are substantially the same as example 3, except that the film has a thickness of 600 μm.
The thermochromic temperature of the film prepared above was measured to be 28.7 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000123
Figure BDA0003382559070000131
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Embodiment 13 this example provides a thermochromic radiation-curable coating material, a thermochromic radiation-curable film, and a method for producing the same, which are substantially the same as in embodiment 3, except that 50 parts of a temperature-sensitive resin, poly (N-isopropylacrylamide).
The thermochromic temperature of the film prepared above was measured to be 41.6 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000132
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Example 14 this example provides a thermochromic radiation-curable coating material, a thermochromic radiation-curable film, and a method for producing the same, which are substantially the same as in example 3 except that the temperature-sensitive resin poly N-isopropylacrylamide is 150 parts.
The thermochromic temperature of the film prepared above was measured to be 30.3 ℃ using an ultraviolet spectrophotometer.
Figure BDA0003382559070000133
Figure BDA0003382559070000141
After the film of the invention is repeatedly discolored for 1000 times, the discoloring performance and the radiation refrigeration performance are still stable.
Comparative example 1 this comparative example provides a method for producing a thin film, which is substantially the same as in example 3 except that a part of the raw materials for production are different as follows: the temperature sensitive resin poly N-isopropyl acrylamide is changed into polyacrylamide.
The film prepared by the method is tested by an ultraviolet spectrophotometer to have no thermochromic effect, and has no enhancement effect on the radiation refrigeration effect.
Figure BDA0003382559070000142
Comparative example 2 this comparative example provides a method of producing a thin film, which is substantially the same as in example 3 except that a part of the raw materials for production are different as follows: does not contain silicon dioxide radiant agent and titanium dioxide reflecting agent.
The thermochromic temperature of the prepared film is tested to be 36.9 ℃ by an ultraviolet spectrophotometer, and the film has no radiation refrigeration effect.
Figure BDA0003382559070000143
Figure BDA0003382559070000151
From the comparison of the data on the thermochromic and radiative cooling tests of the above examples and comparative examples, it can be seen that comparative example 1 has no thermochromic effect and no enhancement effect on the radiative cooling effect. Comparative example 2 has thermochromic effect and no radiation refrigeration. The embodiment has good thermochromic effect, and when the thermochromic temperature is higher than the set temperature, the radiation refrigeration effect can be enhanced.
In addition, the invention also makes many experiments on the influence of the contents of the dispersing agent, the defoaming agent, the thickening agent and the solvent water and the selected materials of the substances on the film, but the invention does not make the invention exhaustive as long as the selected materials and the content of the auxiliary agent are within the range defined by the application, and the requirements of the market on the color change performance and the refrigeration performance of the film can be met.
When the temperature is higher than the temperature-induced temperature, the temperature-sensitive resin poly N-isopropylacrylamide in the embodiment of the invention generates phase change, and stably forms nano-scale emulsion with the assistance of other components of the film, and the whole display is white. Doped reflector TiO2Reflecting solar radiation, radiant agent SiO2The heat is radiated to the outer space in the frequency range of the atmospheric window to realize refrigeration.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The thermochromic radiation refrigeration coating is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003382559060000011
2. the thermochromic radiation-cooling coating of claim 1, wherein: the temperature-sensitive resin is polyacrylamide resin, and the relative molecular mass of the polyacrylamide resin is 103、104、105、106g·mol-1One or more of;
preferably, the polyacrylamide resin is poly-N-isopropylacrylamide.
3. The thermochromic radiation-cooling coating of claim 1, wherein: the film forming agent is one or more of a protein film forming agent, an acrylic resin film forming agent, a polyurethane film forming agent, a butadiene resin film forming agent and a nitrocellulose film forming agent; the dispersing agent is one or more of triethyl hexyl phosphoric acid, sodium dodecyl sulfate, methyl amyl alcohol, cellulose derivatives, polyacrylamide, guar gum and fatty acid polyglycol ester.
4. The thermochromic radiation-cooling coating of claim 1, wherein: the defoaming agent is one or a mixture of more of emulsified silicone oil, a high-alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene; the thickening agent is one or a mixture of more of sodium carboxymethylcellulose, agar, xanthan gum, carrageenan and pectin; the solvent is water.
5. The thermochromic radiation-cooling coating of claim 1, wherein: the radiant agent is silicon dioxide particles, and the particle size of the silicon dioxide particles is 5.0 mu m; the reflecting agent is titanium dioxide particles, and the particle size of the titanium dioxide particles is 0.4 mu m.
6. A thermochromic radiation-curable film, comprising: prepared from the thermochromic radiation-cooling coating material of any of claims 1 to 5.
7. The film of claim 6, wherein: before thermochromism, the film is a transparent film, the initial transmittance of the film is 79.5-91.8%, the initial average reflectivity in a solar spectrum waveband is 37.5-46.7%, and the initial average radiance in an atmospheric window waveband is 43.2-49.8%.
8. The film of claim 6, wherein: the thermochromic temperature of the film is 28.7-37.4 ℃, after the film is thermally changed into white, the photochromic transmittance of the film is 10.5-36.2%, the flattening average reflectivity in a solar spectrum waveband is 90.3-95.5%, and the flattening average radiance in an atmospheric window waveband is up to 89.8-94.1%.
9. The film of claim 6, wherein: the thickness of the film is 200-600 mu m, and the film can be recycled for at least 1000 times.
10. A method of making a film as claimed in any one of claims 6 to 9, comprising the steps of:
respectively weighing the temperature-sensitive resin, the film forming agent, the dispersing agent, the defoaming agent, the thickening agent, the radiant agent, the reflecting agent and the solvent, mixing and stirring to form the thermochromic radiation refrigeration coating, and coating the thermochromic radiation refrigeration coating to prepare the film.
CN202111439840.4A 2021-11-30 2021-11-30 Thermochromic radiation refrigeration coating, thermochromic radiation refrigeration film and preparation method thereof Pending CN113999585A (en)

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