CN114933731A - Polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes and preparation method thereof - Google Patents
Polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes and preparation method thereof Download PDFInfo
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Abstract
A polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes and a preparation method thereof relate to the technical field of material science, in particular to a radiation refrigeration material and a preparation method thereof. The invention aims to solve the problems that the porous material prepared by the existing template method has weak scattering ability in ultraviolet and short visible light wave bands and low reflectivity in solar spectrum wave bands. The polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes has a single-layer structure in the form of a film, a sheet or a coating, the polymer-based radiation refrigeration material takes a polymer material as a substrate, and large-particle-size microsphere materials, small-particle-size microsphere materials and micropores are uniformly distributed in the substrate. The preparation method comprises the following steps: firstly, primary mixing; secondly, final mixing; thirdly, tiling; fourthly, curing; fifthly, removing the pore-foaming agent. The advantages are that: the structure is simple, the cost is low, the preparation process is simple, the stability is good, and the radiation refrigeration effect is good. The invention is mainly used for preparing the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a radiation refrigeration material and a preparation method thereof.
Background
The building energy consumption of China accounts for a large proportion of the total energy consumption of the whole society, wherein the air conditioner energy consumption accounts for 30-60% of the total energy consumption of the building. And the global cooling energy consumption in 2050 years is expected to be 2 times of the current energy consumption, so that the research and development of a novel zero-carbon passive cooling technology for reducing the use of active cooling equipment of an air conditioner is of great importance to building energy conservation.
Radiation refrigeration is used as a novel passive refrigeration mode without energy consumption, self heat can be radiated into a huge outer space cold source through an atmospheric window (8-13 mu m), any electric energy or heat energy is not required to be consumed, and the passive refrigeration mode has important significance for reducing refrigeration energy consumption and realizing zero-carbon environmental protection. Currently, radiation refrigeration materials are mainly based on the following four design modes: the material comprises a multilayer structure, a metamaterial with a surface periodic structure, a randomly distributed particle structure and a porous structure. The radiation refrigeration material with the randomly distributed particle structure and the porous structure is distinguished by the advantages of good refrigeration effect, simple preparation method, low cost and large-scale preparation, so that the material with the composite pores and spheres is expected to become the radiation refrigeration material with the most practical and commercial potential.
At present, the preparation methods of porous materials include a phase inversion method (for example, a Chinese published patent of 'a super-hydrophobic self-cleaning radiation cooling film and a preparation method thereof', publication No. CN110483924A), a template method (for example, a Chinese published patent of 'porous polydimethylsiloxane with daytime radiation refrigeration and a preparation method thereof', publication No. CN113072737A), an electrostatic spinning method (for example, a Chinese published patent of 'a three-dimensional porous micro-nano composite material and a preparation method and application thereof', publication No. CN114232108A) and the like, but the preparation method of the phase inversion method is not environment-friendly, and the problems of difficulty in controlling the solution viscosity, difficulty in determining parameters in the preparation process and the like in the electrostatic spinning method limit the practical application of the phase inversion method. Comprehensively considered, the template method becomes the most environment-friendly and simple preparation method. However, the sizes of pores prepared by the NaCl and sugar template method (such as Chinese published patent ' porous polydimethylsiloxane with daytime radiation refrigeration and preparation method thereof ', publication No. CN 113072737A; ' preparation method of high-efficiency PDMS-based electromagnetic shielding composite film ', publication No. CN 114181427A; ' porous flexible GNP/PDMS composite material, preparation method thereof and application thereof in strain sensors ', publication No. CN113372609A ') which is commonly used at present are all above 5 μm, and because micron-sized pores have strong scattering ability for visible light and near infrared radiation, nano-sized pores have strong scattering ability in ultraviolet and visible regions, the porous material prepared by the template method at present has the problems of weak scattering ability in ultraviolet and short visible light bands and low reflectivity in solar spectrum bands.
Disclosure of Invention
The invention aims to solve the problems that the porous material prepared by the existing template method has weak scattering ability in ultraviolet and short visible light wave bands and low reflectivity in solar spectrum wave bands, and provides a polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes and a preparation method thereof.
The polymer-based radiation refrigeration material compounded by the microspheres with the graded particle size and the holes has a single-layer structure in the form of a film, a sheet or a coating, and the thickness is 400 mu m-3 mm; the method takes a polymer material as a substrate, and uniformly distributes a large-particle-size microsphere material, a small-particle-size microsphere material and micropores in the substrate, wherein the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the microsphere material with small particle size is 0.4-2 μm, and the average diameter of micropores is 1-8 μm.
The preparation method of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes comprises the following steps:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, a pore-forming agent and a surface modifier into an organic solvent, ultrasonically dispersing for 30 min-2 h, and stirring for 0.5-2 h by adopting magnetic stirring to obtain a primary mixed solution; the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the small-particle-size microsphere material is 0.4-2 mu m;
secondly, final mixing: adding a polymer material into the primary mixed liquid, and then continuously stirring for 1-3 hours by using a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank according to the requirement of actual size, and controlling the size and thickness of a single-layer structure in the form of a membrane, a sheet or a coating by using the vessel tank to obtain the vessel tank containing the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80-120 ℃ for 5-12 h to obtain a crude product of the single-layer structure material;
fifthly, removing the pore-foaming agent: soaking the crude product of the single-layer structure material into deionized water, soaking for 1-2 d at the temperature of 40-80 ℃, then placing the soaked crude product into a drying oven, and drying for 6-12 h at the temperature of 40-80 ℃ to obtain the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 400-3 mm, and the average diameter of the micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 1-8 μm.
The invention has the advantages that:
the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes takes a polymer material as a substrate, and a large-particle-size microsphere material, a small-particle-size microsphere material and micropores are uniformly distributed in the substrate; the large-particle-size microsphere material can be used as an emitter to strongly emit light in an atmospheric window waveband through a surface phonon polarization resonance effect. The microsphere material with small particle size can strongly scatter light in ultraviolet and short visible light wave bands by using the Mie scattering effect as a scattering body, makes up the deficiency of micropore scattering capability, and can further enhance the light of the material in the atmospheric window wave band as an emitter.
Secondly, the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes has a single-layer film structure, is simple in structure, low in cost, simple in preparation process and good in stability, the reflectivity R of a solar spectrum (0.3-2.5 microns) is larger than 90%, the emissivity of a thermal infrared band (2.5-20 microns) is larger than 70%, 5.6 ℃ can be reduced in daytime, and the radiation refrigeration effect is good.
Drawings
FIG. 1 is a schematic structural diagram of a polymer-based radiation refrigeration material with microspheres of graded particle size and pores in accordance with the present invention;
FIG. 2 is a spectrum of atmospheric window band emissivity of a polymer-based radiation refrigeration material with microspheres of graded particle size and holes prepared in example 1;
FIG. 3 is a spectrum of the reflectivity of the polymer-based radiant cooling material with graded-particle size microspheres and holes prepared in example 1 in the solar spectral band;
FIG. 4 is a spectrum of the reflectivity of the polymer-based radiant cooling material with graded-particle size microspheres and holes prepared in example 2 in the solar spectral band;
FIG. 5 is a spectrum of the reflectivity of the polymer-based radiant cooling material with graded-particle size microspheres and holes prepared in example 3 in the solar spectral band;
fig. 6 is a graph showing the cooling effect of the polymer-based radiation refrigeration material with the microspheres with the graded particle size and the holes, which is prepared in example 1.
Detailed Description
The first embodiment is as follows: the embodiment is a polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes, which is a single-layer structure in the form of a film, a sheet or a coating, and has the thickness of 400 mu m-3 mm; the method takes a polymer material as a substrate, and uniformly distributes a large-particle-size microsphere material, a small-particle-size microsphere material and micropores in the substrate, wherein the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the microsphere material with small particle size is 0.4-2 μm, and the average diameter of micropores is 1-8 μm.
The first embodiment is as follows: the present embodiment differs from the first embodiment in that: the volume fraction of the large-particle-size microsphere material in the polymer-based radiation refrigeration material compounded by the graded-particle-size microspheres and the holes is 6-15%, the volume fraction of the small-particle-size microsphere material is 0.1-59%, the volume fraction of the micropores is 0.1-59%, and the total volume fraction of the small-particle-size microsphere material and the micropores is 1-60%. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the polymer material is one or more of epoxy resin, polyester resin, polyacrylate resin, polyamide resin, polyurethane resin, polyolefin resin and fluororesin. The rest is the same as the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is as follows: the large-particle-size microsphere material is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder; the small-particle-size microsphere material is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder. The others are the same as in the first to third embodiments.
The fifth concrete implementation mode: the embodiment is a preparation method of a polymer-based radiation refrigeration material compounded by microspheres with graded particle sizes and holes, which is specifically completed according to the following steps:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, a pore-forming agent and a surface modifier into an organic solvent, ultrasonically dispersing for 30 min-2 h, and stirring for 0.5-2 h by adopting magnetic stirring to obtain a primary mixed solution; the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the microsphere material with small particle size is 0.4-2 μm;
secondly, final mixing: adding a polymer material into the primary mixed liquid, and then continuously stirring for 1-3 h by using a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank according to the requirement of actual size, and controlling the size and thickness of a single-layer structure in the form of a membrane, a sheet or a coating by using the vessel tank to obtain the vessel tank containing the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80-120 ℃ for 5-12 h to obtain a crude product of the single-layer structure material;
fifthly, removing the pore-foaming agent: soaking the crude product of the single-layer structure material into deionized water, soaking for 1-2 d at the temperature of 40-80 ℃, then placing the soaked crude product into a drying oven, and drying for 6-12 h at the temperature of 40-80 ℃ to obtain the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 400-3 mm, and the average diameter of the micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 1-8 μm.
The sixth specific implementation mode: the present embodiment is different from the fifth embodiment in that: in the first step, the polymer material is one or more of epoxy resin, polyester resin, polyacrylate resin, polyamide resin, polyurethane resin, polyolefin resin and fluororesin. The rest is the same as the fifth embodiment.
The seventh concrete implementation mode: the present embodiment is different from the fifth or sixth embodiment in that: in the step one, the large-particle-size microsphere material is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder; in the step one, the microsphere material with small particle size is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder. The other is the same as the fifth or sixth embodiment.
The specific implementation mode is eight: the fifth to seventh embodiments are different from the first to seventh embodiments in that: in the first step, the surface modifier is one or more of fluorosilane, methylsilane, octadecanoic acid and silane coupling agent. The rest is the same as the fifth to seventh embodiments.
The specific implementation method nine: the fifth to eighth differences from the present embodiment are: in the first step, the pore-forming agent is NaCl powder. The rest is the same as the fifth to eighth embodiments.
The detailed implementation mode is ten: the fifth to ninth embodiments are different from the fifth to ninth embodiments in that: and fifthly, the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, acetone, tetrahydrofuran, dichloromethane or benzene. The rest is the same as the fifth to ninth embodiments.
The concrete implementation mode eleven: the fifth to tenth embodiments are different from the first to tenth embodiments in that: in the fifth step, the volume fraction of the large-particle-size microsphere material in the polymer-based radiation refrigeration material compounded by the graded-particle-size microspheres and the pores is 6-15%, the volume fraction of the small-particle-size microsphere material is 0.1-59%, the volume fraction of the micropores is 0.1-59%, and the total volume fraction of the small-particle-size microsphere material and the micropores is 1-60%. The rest is the same as the fifth to tenth embodiments.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests are adopted to verify the effect of the invention:
example 1: the preparation method of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes comprises the following steps:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, NaCl powder and a silane coupling agent KH570 into an organic solvent, performing ultrasonic dispersion for 30min, and stirring for 1h by adopting magnetic stirring to obtain a primary mixed solution; the average particle size of the large-particle-size microsphere material is 8 mu m; the average grain diameter of the small-grain-diameter microsphere material is 1 mu m; the large-particle-size microsphere material is SiO 2 (ii) a In the step one, the microsphere material with small particle size is SiO 2 ；
Secondly, final mixing: adding polymethyl methacrylate resin into the primary mixed liquid, and then continuously stirring for 1h by adopting a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank, and controlling the size and the thickness of a membrane single-layer structure by adopting the vessel tank to obtain the vessel tank filled with the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80 ℃ for 8h to obtain a crude product of the membrane single-layer structure material;
fifthly, removing the pore-foaming agent: soaking the crude product of the membrane single-layer structure material into deionized water at the temperature of 80 ℃ for 1d, then placing the soaked crude product into a drying oven, and drying the soaked crude product at the temperature of 80 ℃ for 6h to obtain the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 750 mu m, and the average diameter of the micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 6 mu m.
Example 1 step five the organic solvent was N, N-dimethylacetamide.
In the polymer-based radiation refrigeration material in which the graded-particle-size microspheres and the pores are compounded in the step five of example 1, the volume fraction of the large-particle-size microsphere material is 10%, the volume fraction of the small-particle-size microsphere material is 20%, and the volume fraction of the micropores is 30%.
Fig. 1 is a schematic structural diagram of a polymer-based radiation refrigeration material formed by compounding graded-particle-size microspheres and pores. The polymer material comprises large-particle-size microspheres, small-particle-size microspheres and micropores, the large-particle-size microspheres have high emission characteristics in an atmospheric window waveband due to a strong surface phonon polarization resonance phenomenon, and the coupling action of the small-particle-size microspheres and the pores strengthens a scattering action and has high reflection characteristics in a solar spectrum waveband.
Fig. 2 is a spectrum diagram of atmospheric window waveband emissivity of the polymer-based radiation refrigeration material with the microspheres with the graded particle size and the holes, which is prepared in example 1, and it can be known from fig. 2 that the polymer-based radiation refrigeration material with the microspheres with the graded particle size and the holes, which is prepared in example 1, has higher emissivity in an atmospheric window area, and meets the spectral requirement of the daytime radiation refrigeration material.
Fig. 3 is a spectrum diagram of the reflectivity of the polymer-based radiation refrigeration material with the microspheres and pores in the graded particle size, which is prepared in example 1, in a solar spectrum band, as can be seen from fig. 3, the polymer-based radiation refrigeration material with the microspheres and pores in the graded particle size, which is prepared in example 1, has a high reflectivity (reflectivity of 90.6%) in the solar spectrum band, and meets the spectrum requirement of the daytime radiation refrigeration material.
Fig. 6 is a graph showing the cooling effect of the polymer-based radiation refrigeration material with the microspheres with the graded particle size and the holes, which is prepared in example 1. As can be seen from FIG. 6, the polymer-based radiation refrigeration material with composite microspheres with graded particle sizes and pores prepared in example 1 can reduce the temperature by 5.6 ℃ in the daytime, and has a good radiation refrigeration effect.
Example 2: the preparation method of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes comprises the following steps:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, NaCl powder and a silane coupling agent KH570 into an organic solvent, performing ultrasonic dispersion for 30min, and stirring for 1h by adopting magnetic stirring to obtain a primary mixed solution; the average particle size of the large-particle-size microsphere material is 8 mu m; the average grain diameter of the small-grain-diameter microsphere material is 1 mu m; the large-particle-size microsphere material is SiO 2 (ii) a In the step one, the microsphere material with small particle size is SiO 2 ；
Secondly, final mixing: adding polymethyl methacrylate resin into the primary mixed liquid, and then continuously stirring for 1h by adopting a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank, and controlling the size and the thickness of a membrane single-layer structure by adopting the vessel tank to obtain the vessel tank containing the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80 ℃ for 8h to obtain a crude product of the membrane single-layer structure material;
fifthly, removing the pore-foaming agent: soaking the crude product of the membrane single-layer structure material into deionized water at the temperature of 80 ℃ for 1d, then placing the soaked crude product into a drying oven, and drying the soaked crude product at the temperature of 80 ℃ for 6h to obtain the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle size and the holes is 1mm, and the average diameter of micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle size and the holes is 6 mu m.
Example 2 step five the organic solvent was N, N-dimethylacetamide.
In the polymer-based radiation refrigeration material in which the graded-particle-size microspheres and the holes are compounded in the fifth step of example 2, the volume fraction of the large-particle-size microsphere material is 10%, the volume fraction of the small-particle-size microsphere material is 30%, and the volume fraction of the micropores is 20%.
Fig. 4 is a spectrum diagram of the reflectivity of the polymer-based radiation refrigeration material with the microspheres and holes with the graded particle size prepared in example 2 in the solar spectral band, and it can be known from fig. 4 that the polymer-based radiation refrigeration material with the microspheres and holes with the graded particle size prepared in example 2 has a higher reflectivity (the reflectivity is 83.2%) in the solar spectral band, and meets the spectral requirements of the daytime radiation refrigeration material.
Example 3: the preparation method of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes comprises the following steps:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, NaCl powder and a silane coupling agent KH570 into an organic solvent, performing ultrasonic dispersion for 30min, and stirring for 1h by adopting magnetic stirring to obtain a primary mixed solution; the average particle size of the large-particle-size microsphere material is 8 mu m; the average grain diameter of the small-grain-diameter microsphere material is 1 mu m; the large-particle-size microsphere material is SiO 2 (ii) a In the step one, the microsphere material with small particle size is SiO 2 ；
Secondly, final mixing: adding polyvinylidene fluoride resin into the primary mixed liquid, and then continuously stirring for 1h by adopting a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank, and controlling the size and the thickness of a membrane single-layer structure by adopting the vessel tank to obtain the vessel tank containing the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80 ℃ for 8h to obtain a crude product of the membrane single-layer structure material;
fifthly, removing the pore-foaming agent: immersing the membrane single-layer structure material crude product into deionized water, immersing for 1d at the temperature of 80 ℃, then placing the membrane single-layer structure material crude product into a drying oven, and drying for 6 hours at the temperature of 80 ℃ to obtain a polymer-based radiation refrigeration material with the microspheres and holes with graded particle diameters compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 1mm, and the average diameter of the micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 6 microns.
Example 3 step five the organic solvent was N, N-dimethylacetamide.
In the polymer-based radiation refrigeration material in which the graded-particle-size microspheres and the holes are compounded in the fifth step of example 3, the volume fraction of the large-particle-size microsphere material is 10%, the volume fraction of the small-particle-size microsphere material is 20%, and the volume fraction of the micropores is 30%.
Fig. 5 is a spectrum diagram of the reflectivity of the polymer-based radiation refrigeration material with the microspheres and holes with the graded particle size, which is prepared in example 3, and as can be seen from fig. 5, the polymer-based radiation refrigeration material with the microspheres and holes with the graded particle size, which is prepared in example 3, has a higher reflectivity (reflectivity of 77.4%) in the solar spectrum band, and meets the spectrum requirement of the daytime radiation refrigeration material.
Claims (10)
1. The polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is characterized in that the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is of a single-layer structure in the form of a film, a sheet or a coating, and the thickness of the polymer-based radiation refrigeration material is 400 mu m-3 mm; the method takes a polymer material as a substrate, and uniformly distributes a large-particle-size microsphere material, a small-particle-size microsphere material and micropores in the substrate, wherein the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the microsphere material with small particle size is 0.4-2 μm, and the average diameter of micropores is 1-8 μm.
2. The polymer-based radiation refrigerating material with microspheres and pores in graded particle sizes as claimed in claim 1, wherein the volume fraction of the microsphere material with large particle sizes in the polymer-based radiation refrigerating material with microspheres and pores in graded particle sizes is 6-15%, the volume fraction of the microsphere material with small particle sizes is 0.1-59%, the volume fraction of the micropores is 0.1-59%, and the total volume fraction of the microsphere material with small particle sizes and micropores is 1-60%.
3. The polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded according to claim 1, wherein the polymer material is one or more of epoxy resin, polyester resin, polyacrylate resin, polyamide resin, polyurethane resin, polyolefin resin and fluororesin.
4. The polymer-based radiation refrigeration material with composite of microspheres and pores with graded particle size according to claim 1, wherein the material of microspheres with large particle size is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder; the small-particle-size microsphere material is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminium silicate and ceramic powder.
5. The method for preparing the polymer-based radiation refrigerating material with the microspheres and the pores in the graded particle size compounded according to claim 1 is characterized by comprising the following steps of:
firstly, primary mixing: adding a large-particle-size microsphere material, a small-particle-size microsphere material, a pore-forming agent and a surface modifier into an organic solvent, ultrasonically dispersing for 30 min-2 h, and stirring for 0.5-2 h by adopting magnetic stirring to obtain a primary mixed solution; the particle size of the large-particle-size microsphere material is 2.1-20 mu m; the particle size of the small-particle-size microsphere material is 0.4-2 mu m;
secondly, final mixing: adding a polymer material into the primary mixed liquid, and then continuously stirring for 1-3 h by using a magnetic stirrer to obtain a mixture;
thirdly, tiling: adding the mixture into a vessel tank according to the requirement of actual size, and controlling the size and thickness of a single-layer structure in the form of a membrane, a sheet or a coating by using the vessel tank to obtain the vessel tank containing the mixture;
fourthly, curing: curing the vessel containing the mixture at the temperature of 80-120 ℃ for 5-12 h to obtain a crude product of the single-layer structure material;
fifthly, removing the pore-foaming agent: soaking the crude product of the single-layer structure material into deionized water, soaking for 1-2 d at the temperature of 40-80 ℃, then placing the soaked crude product into a drying oven, and drying for 6-12 h at the temperature of 40-80 ℃ to obtain the polymer-based radiation refrigeration material with the microspheres with the graded particle sizes and the holes compounded; the thickness of the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 400-3 mm, and the average diameter of the micropores in the polymer-based radiation refrigeration material compounded by the microspheres with the graded particle sizes and the holes is 1-8 μm.
6. The method for preparing a polymer-based radiation refrigeration material with microspheres and pores in graded particle sizes according to claim 5, wherein the polymer material in the step one is one or more of epoxy resin, polyester resin, polyacrylate resin, polyamide resin, polyurethane resin, polyolefin resin and fluororesin.
7. The polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded according to claim 6, wherein the material of microspheres in large particle size in step one is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminum silicate and ceramic powder; in the step one, the microsphere material with small particle size is SiO 2 、BaSO 4 、CaCO 3 、MgO、Al 2 O 3 、Si 3 N 4 One or more of titanium dioxide, talcum powder, aluminium silicate and ceramic powder.
8. The polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded according to claim 7, wherein the surface modifier in the first step is one or more of fluorosilane, methylsilane, octadecanoic acid and silane coupling agent; in the first step, the pore-forming agent is NaCl powder.
9. The polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded according to claim 6, wherein the organic solvent in the fifth step is N, N-dimethylformamide, N-dimethylacetamide, acetone, tetrahydrofuran, dichloromethane or benzene.
10. The polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded according to claim 6, wherein in the polymer-based radiation refrigeration material with microspheres and pores in graded particle size compounded in step five, the volume fraction of the microsphere material with large particle size is 6-15%, the volume fraction of the microsphere material with small particle size is 0.1-59%, the volume fraction of the micropores is 0.1-59%, and the total volume fraction of the microsphere material with small particle size and micropores is 1-60%.
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