CN112375418A - Preparation method of multistage porous radiation refrigeration film coating - Google Patents
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- CN112375418A CN112375418A CN202011082145.2A CN202011082145A CN112375418A CN 112375418 A CN112375418 A CN 112375418A CN 202011082145 A CN202011082145 A CN 202011082145A CN 112375418 A CN112375418 A CN 112375418A
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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
- C09D5/004—Reflecting paints; Signal paints
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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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
- 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
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Abstract
The invention relates to a preparation method of a multistage porous radiation refrigeration film coating, which comprises the steps of taking a high internal phase water-in-oil emulsion as a template, dissolving organosilane and a high molecular prepolymer or a monomer in an oil phase, heating and polymerizing to form an organic-inorganic composite framework, and drying to obtain the multistage porous radiation refrigeration film coating. The invention can realize large-scale production without using complex and expensive processing equipment and harsh processing conditions. The film coating prepared by the invention not only can reflect the sunlight with the wavelength range of 0.3-2.5 mu m back to the high degree due to the abundant multi-stage pore structure and the excellent optical inherent characteristic, but also can dissipate the self heat to the cold outer space through the atmospheric transparent window with the wavelength of 8-13 mu m, and the film coating can still be cooled by more than 5 ℃ even under the direct irradiation of the sunlight. As a novel refrigeration technology, the invention is expected to reduce or replace the traditional electric cooling system, realize the spontaneous cooling of the surface of the building and effectively relieve the problem of global warming.
Description
Technical Field
The invention belongs to the field of radiation refrigeration, and particularly relates to a preparation method of a multistage porous radiation refrigeration film coating.
Background
With the rapid increase of global energy consumption, more and more research efforts are put into developing energy-saving technologies. In order to deal with the rapid increase of the electricity consumption of the global air conditioner and solve the problems that the traditional refrigeration technology not only has serious electricity consumption and causes 'net' heating, but also damages the ozone layer or brings strong greenhouse effect, people provide a passive radiation cooling technology, in particular to a daytime passive radiation cooling (PDRC) technology, which has the principle of reflecting sunlight with the wavelength range of about 0.3-2.5 mu m back highly and emitting the self heat to cold outer space through an atmosphere transparent window with the wavelength of 8-13 mu m. The passive radiation cooling technology is not only beneficial to relieving the global warming problem, but also hopeful to replace a refrigeration system based on air compression, realizes the spontaneous cooling of the building surface, and has great influence on the world energy pattern.
In recent years, some advanced PDRC designs attract extensive attention, but complex and expensive processing equipment is often required in the production process, and the PDRC designs are not suitable for large-scale popularization. Therefore, it is a challenge to research and develop PDRC materials that are simple, inexpensive, efficient, environmentally friendly, and scalable.
Disclosure of Invention
The invention aims to provide a preparation method of a multistage porous radiation refrigeration film coating which is simple, efficient, low in cost and capable of being produced in a large scale. Because the film coating has rich micro-nano pore structures, the solar reflectivity is up to 0.95, the long-wave infrared emissivity is up to 0.98, and the film coating can still be cooled by about 6.5 ℃ under the direct sunlight at noon. In addition, the film coating has a series of advantages of super-hydrophobicity, low cost, easy processing and the like, and can be applied on a large scale in various climatic environments and on complex surfaces.
The invention provides a preparation method of a multistage porous radiation refrigeration film coating, which comprises the following specific steps:
(1) adding organosilane, high-molecular prepolymer or monomer and corresponding curing agent or initiator into an organic solvent in proportion, and uniformly mixing to obtain an oil phase mixture; wherein: the organic silane accounts for 10-50wt% of the oil phase, and the high molecular prepolymer or monomer accounts for 20-60wt% of the oil phase;
(2) dropwise adding deionized water into the oil phase mixture obtained in the step (1), slowly shaking and uniformly mixing, and performing homogenization, stirring or ultrasonic emulsification to obtain a water-in-oil emulsion, namely a high internal phase emulsion, wherein the internal water phase accounts for 40-80% of the total volume;
(3) pouring the high internal phase emulsion obtained in the step (2) into a mould, sealing, putting into a blast box, and heating and reacting at 50-100 ℃ for 6-12 h;
(4) and (4) removing the organic solvent from the polymeric hybrid system obtained in the step (3) and drying to obtain the multistage porous radiation refrigeration film coating.
In the invention, the organosilane in the step (1) has a hyperbranched structure, and specifically is any one of methyltriethoxysilane, dimethyldiethoxysilane or tetraethoxysilane.
In the invention, the polymer prepolymer or monomer in the step (1) is one or more of organosiloxane prepolymer, polyurethane prepolymer, epoxy resin prepolymer, styrene monomer, vinylidene fluoride monomer or (methyl) acrylate monomer.
In the invention, the organic solvent in the step (1) is any one of toluene, xylene, cyclohexane, petroleum ether or tetrahydrofuran.
In the invention, the thickness of the multistage porous radiation refrigeration film coating is 0.5-10 mm.
In the invention, the pore size of the multistage porous radiation refrigeration film coating is in multistage distribution, the nanometer pores are distributed at 10 +/-1000 nm, and the micron pores are distributed at 1 +/-50 mu m.
In the invention, the porosity of the multistage porous radiation refrigeration film coating is 40-80%.
In the invention, the heat conductivity coefficient of the multi-stage porous radiation refrigeration film coating is as low as 31 mW/mK, and the multi-stage porous radiation refrigeration film coating has excellent heat insulation performance.
In the invention, the solar reflectivity of the multistage porous radiation refrigeration film coating is up to 0.95, and the long-wave infrared emissivity is up to 0.98.
In the invention, the multi-stage porous radiation refrigeration film coating is cooled by about 5-9 ℃ in the daytime and at night, and is cooled by 4-7 ℃ at noon.
The invention has the beneficial effects that:
(1) according to the invention, abundant micro-nano pore structures are distributed in the film coating, the porosity is up to more than 70%, sunlight can be effectively reflected, and the thermal emissivity is increased;
(2) in the invention, the film coating has excellent heat insulation performance;
(3) in the invention, the preparation process of the film coating is simple, the raw materials and the production cost are low, and large-scale preparation can be carried out;
(4) in the invention, the polymerization hybrid system can form a film and can also be directly coated into a coating.
(5) In the invention, the film coating shows excellent performance in the field of all-day passive radiation cooling.
Drawings
FIG. 1 is a photograph of the appearance and a scanning electron microscope photograph of the multi-stage porous radiation refrigeration thin film coating in example 1. Wherein: (a) the macro photo of the multi-stage porous radiation refrigeration film coating, and (b) the scanning electron microscope photo of the multi-stage porous radiation refrigeration film coating.
FIG. 2 shows the reflection spectrum and the emission spectrum of the multi-stage porous radiation refrigeration thin film coating of example 1 at a wavelength of 0.3-25 μm. Wherein: (a) the reflection spectrum of the multi-stage porous radiation refrigeration film coating at the wavelength of 0.3-25 mu m, and (b) the emission spectrum of the multi-stage porous radiation refrigeration film coating at the wavelength of 0.3-25 mu m.
FIG. 3 is a graph of the thermal conductivity of the polydimethylsiloxane film coating and the multi-stage porous radiation refrigeration film coating of example 1.
Fig. 4 is a compressive stress-strain curve of the multi-stage porous radiation refrigeration thin film coating in example 1.
FIG. 5 is the water contact angle of the polydimethylsiloxane membrane coating and the multi-stage porous radiation refrigeration membrane coating of example 1 at different accelerated aging times.
FIG. 6 is a digital photograph and an infrared image of the multi-stage porous radiation chilling film coating and polydimethylsiloxane film coating of example 1. Wherein: (a) the digital photo of the multi-stage porous radiation refrigeration film coating, (b) the infrared image of the multi-stage porous radiation refrigeration film coating, (c) the digital photo of the polydimethylsiloxane film coating, and (d) the infrared image of the polydimethylsiloxane film coating.
FIG. 7 is a full day temperature test of the polydimethylsiloxane membrane coating and the multi-stage porous radiation chilling membrane coating of example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples and drawings, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1:
firstly, dissolving 2g of hyperbranched polyethoxysilane, 3g of polydimethylsiloxane prepolymer and 0.3g of curing agent in 4g of toluene, and uniformly mixing to obtain an oil phase; and (3) dropwise adding 35g of deionized water into the oil phase mixture, slowly shaking for 1 min until water drops are uniformly dispersed in the oil phase, and emulsifying by using a homogenizer to obtain the high internal phase water-in-oil emulsion, wherein the homogenizing speed is 1000 rpm, and the homogenizing time is 5 min. Transferring the high internal phase water-in-oil emulsion into a sealed Teflon mold, and putting the mold into a blast box at 80 ℃ for reaction for 12 hours to obtain polymerized PDMS/SiO2And (4) gelling. Soaking the porous PDMS/SiO composite in absolute ethyl alcohol for 6h, taking out the porous PDMS/SiO composite, and drying the porous PDMS/SiO composite in a blast box at 80 ℃ for 6h2Radiation refrigeration thin film coating (PSHF)HP）。
As shown in FIG. 1, the PSHF preparedHPThe film coating has bright white appearance, and the interior of the film coating contains abundant micro-nano hierarchical pore structures.
FIG. 2Is PSHFHPThe reflectivity and emissivity spectrum of the film coating under the wavelength of 0.3-25 μm shows that the solar reflectivity is as high as 0.95, and almost no sunlight is absorbed; the long-wave infrared emissivity is as high as 0.98, and the self heat can be greatly dissipated to the cold outer space.
FIG. 3 shows pure PDMS and PSHFHPThe heat conductivity coefficient of the film coating and the abundant hierarchical pore structure greatly reduce PSHFHPThe heat conductivity coefficient (31 mW/mK) of the film coating improves the heat insulation performance of the film coating, and is beneficial to reducing the PSHF (patterned silicon fluoride) caused by the surrounding environmentHPNon-radiative heat transfer of the thin film coating.
FIG. 4 shows a PSHFHPThe thin film coating has a compressive stress-strain curve, and can be seen to have superelasticity and good flexibility.
As shown in FIG. 5, PSHF is comparable to pure PDMS film coatingHPHas excellent super-hydrophobic performance, and the water contact angle of the product is almost unchanged after 50 days of accelerated aging, thereby showing PSHFHPGood ageing resistance.
FIG. 6 compares PDMS and PSHFHPThermographic photograph of the thin film coating, it can be seen that PSHFHPIs significantly lower than the PDMS thin film coating.
FIG. 7 compares PDMS and PSHFHPThe whole day temperature trace curve of the thin film coating, it can be seen that PSHFHPThe temperature of the air conditioner is always lower than the ambient temperature, the average temperature reduction at night (6 p.m. -6 a.m.) is about 8.4 ℃, and the average temperature reduction at noon (11 a.m. -2 p.m.) is about 6.5 ℃. While the pure PDMS film coating can reduce the temperature by about 2.9 ℃ at night, the pure PDMS film coating does not have the daytime temperature reduction performance, and the temperature is increased by about 9.3 ℃ in direct sunlight at noon.
Example 2
The experimental apparatus and operation were the same as in example 1, where 3g of polydimethylsiloxane prepolymer was replaced with 4g of polyurethane prepolymer, and 4g of toluene was replaced with 5g of tetrahydrofuran; the magnetic stirring is changed from the emulsification of the homogenizer, the stirring speed is 1500 rpm, the stirring time is 30 min, and the stirring temperature is 50 ℃. And the rest conditions are unchanged, so that the multistage porous polyurethane/silicon dioxide radiation refrigeration film coating can be obtained.
Claims (10)
1. A preparation method of a multistage porous radiation refrigeration film coating is characterized by comprising the following specific steps:
(1) adding organosilane, high-molecular prepolymer or monomer and corresponding curing agent or initiator into an organic solvent in proportion, and uniformly mixing to obtain an oil phase mixture; wherein: the organic silane accounts for 10-50wt% of the oil phase, and the high molecular prepolymer or monomer accounts for 20-60wt% of the oil phase;
(2) dropwise adding deionized water into the oil phase mixture obtained in the step (1), slowly shaking and uniformly mixing, and performing homogenization, stirring or ultrasonic emulsification to obtain a water-in-oil emulsion, namely a high internal phase emulsion, wherein the internal water phase accounts for 40-80% of the total volume;
(3) pouring the high internal phase emulsion obtained in the step (2) into a mould, sealing, putting into a blast box, and heating and reacting at 50-100 ℃ for 6-12 h;
(4) and (4) removing the organic solvent from the polymeric hybrid system obtained in the step (3) and drying to obtain the multistage porous radiation refrigeration film coating.
2. The method according to claim 1, wherein the organosilane in step (1) has a hyperbranched structure, and specifically is any one of methyltriethoxysilane, dimethyldiethoxysilane, or tetraethoxysilane.
3. The preparation method according to claim 1, wherein the polymer prepolymer or monomer in step (1) is one or more of organosiloxane prepolymer, polyurethane prepolymer, epoxy resin prepolymer, styrene monomer, vinylidene fluoride monomer, and (meth) acrylate monomer.
4. The method according to claim 1, wherein the organic solvent in step (1) is any one of toluene, xylene, cyclohexane, petroleum ether, and tetrahydrofuran.
5. The preparation method of claim 1, wherein the thickness of the multistage porous radiation refrigeration thin film coating is 0.5-10 mm.
6. The preparation method of claim 1, wherein the pore size of the multistage porous radiation refrigeration thin film coating is in multistage distribution, the nanometer-scale pores are distributed in 10 +/-1000 nm, and the micrometer-scale pores are distributed in 1 +/-50 μm.
7. The preparation method of claim 1, wherein the porosity of the multistage porous radiation refrigeration thin film coating is 40-80%.
8. The method of claim 1, wherein the multistage porous radiant refrigeration film coating has a thermal conductivity as low as 31 mW/mK and excellent thermal insulation properties.
9. The method of claim 1, wherein the multistage porous radiation refrigeration thin film coating has a solar reflectance of up to 0.95 and a long-wave infrared emissivity of up to 0.98.
10. The preparation method of claim 1, wherein the average temperature of the multi-stage porous radiation refrigeration film coating is reduced by about 5-9 ℃ in the daytime and at night, and the temperature is reduced by 4-7 ℃ in the noon.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114016300A (en) * | 2021-11-24 | 2022-02-08 | 浙江理工大学 | Coated textile with passive radiation cooling function and preparation method thereof |
| CN115260740A (en) * | 2022-08-26 | 2022-11-01 | 电子科技大学长三角研究院(湖州) | High-mechanical-property radiation refrigeration film with composite aperture, preparation method and application thereof |
| CN115304953A (en) * | 2021-05-10 | 2022-11-08 | 上海交通大学 | Radiant heat photon control material and preparation method thereof |
| CN116574419A (en) * | 2023-04-24 | 2023-08-11 | 武汉科技大学 | Infrared radiation coating based on copper slag powder, preparation method thereof and hierarchical pore infrared radiation coating |
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| CN107778408A (en) * | 2017-11-23 | 2018-03-09 | 福州大学 | A kind of method that High Internal Phase Emulsion template prepares porous polymer materials |
| CN110182816A (en) * | 2019-04-02 | 2019-08-30 | 复旦大学 | The method of flexible aerosil is prepared under a kind of normal pressure |
| CN110452668A (en) * | 2019-08-30 | 2019-11-15 | 哈尔滨工业大学 | A kind of transmission-type radiation refrigeration material, film, preparation method and application |
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| CN107311185A (en) * | 2017-06-23 | 2017-11-03 | 复旦大学 | A kind of preparation method of superelevation porosity porous silica |
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| CN110182816A (en) * | 2019-04-02 | 2019-08-30 | 复旦大学 | The method of flexible aerosil is prepared under a kind of normal pressure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115304953A (en) * | 2021-05-10 | 2022-11-08 | 上海交通大学 | Radiant heat photon control material and preparation method thereof |
| CN115304953B (en) * | 2021-05-10 | 2023-10-20 | 上海交通大学 | Radiant heat photon control material and preparation method thereof |
| CN114016300A (en) * | 2021-11-24 | 2022-02-08 | 浙江理工大学 | Coated textile with passive radiation cooling function and preparation method thereof |
| CN114016300B (en) * | 2021-11-24 | 2024-02-02 | 浙江理工大学 | Coated textile with passive radiation cooling function and preparation method thereof |
| CN115260740A (en) * | 2022-08-26 | 2022-11-01 | 电子科技大学长三角研究院(湖州) | High-mechanical-property radiation refrigeration film with composite aperture, preparation method and application thereof |
| CN115260740B (en) * | 2022-08-26 | 2023-04-28 | 电子科技大学长三角研究院(湖州) | High mechanical property radiation refrigeration film with composite aperture, preparation method and application thereof |
| CN116574419A (en) * | 2023-04-24 | 2023-08-11 | 武汉科技大学 | Infrared radiation coating based on copper slag powder, preparation method thereof and hierarchical pore infrared radiation coating |
| CN116574419B (en) * | 2023-04-24 | 2024-06-07 | 武汉科技大学 | Infrared radiation coating based on copper slag powder, preparation method thereof and hierarchical pore infrared radiation coating |
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Application publication date: 20210219 |