CN115873490B - Self-regulating photo-thermal anti-icing deicing coating and coating - Google Patents
Self-regulating photo-thermal anti-icing deicing coating and coating Download PDFInfo
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- CN115873490B CN115873490B CN202310000344.1A CN202310000344A CN115873490B CN 115873490 B CN115873490 B CN 115873490B CN 202310000344 A CN202310000344 A CN 202310000344A CN 115873490 B CN115873490 B CN 115873490B
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a self-regulating photo-thermal anti-icing deicing coating and a coating, and belongs to the technical field of anti-icing deicing. The self-regulating photo-thermal anti-icing deicing coating provided by the invention comprises the following components in percentage by mass: 60-90% of resin prepolymer; 10-40% of thermosensitive color-changing dye microcapsule; the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers. In the invention, the heat-sensitive color-changing dye makes the paint have dark color under the low temperature condition below 0 ℃ in winter, has high photo-thermal conversion efficiency and plays roles in preventing and removing ice; the light-colored solar energy collector has light color under the high temperature condition in summer, has low light-heat conversion efficiency and avoids the condition of overheating. The thermochromic dye microcapsule contains higher fatty alcohol, has phase change in the photo-thermal conversion process, and can effectively absorb heat and release heat through the phase change, so that the effect of delaying surface cooling and icing is achieved.
Description
Technical Field
The invention relates to the technical field of anti-icing and deicing, in particular to a self-control photo-thermal anti-icing and deicing coating and a coating.
Background
Icing is a common phenomenon in nature, brings potential safety hazards to industries such as transportation, energy transmission, wind power generation and the like, influences the original performance of equipment, and can bring economic loss or casualties when serious. Therefore, development of anti-icing and deicing techniques is imperative. Conventional deicing methods include mechanical deicing, deicing with snow-melting agents, electrical heating deicing, and the like. Thermal deicing is a common method of deicing. The conventional thermal deicing method melts accumulated ice using the joule heating effect or the thermal blowing method, and consumes a large amount of electric energy.
In recent years, the application of photo-thermal coatings capable of converting light energy into heat energy has received a great deal of attention in the field of anti-icing and deicing. The photo-thermal anti-icing deicing coating only consumes solar energy in the deicing process, does not need additional power supply, and is an economic, applicable and environment-friendly anti-icing deicing method. However, most of the photo-thermal materials are black or dark coatings with high photo-thermal conversion efficiency, the chemical compositions of the photo-thermal materials comprise carbon materials, siC, ferroferric oxide and the like, and under the condition of overheating in high-temperature and high-light-intensity climates in summer, the service life of the coatings can be shortened, and the urban heat island effect is aggravated.
Disclosure of Invention
In view of the above, the present invention aims to provide a self-regulating photo-thermal anti-icing and deicing coating and a coating, wherein the self-regulating photo-thermal anti-icing and deicing coating provided by the present invention can self-regulate photo-thermal conversion performance according to use temperature, has high photo-thermal conversion performance at low temperature, plays an anti-icing and deicing function, has low photo-thermal conversion performance at high temperature, and avoids overheating phenomenon.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a self-regulating photo-thermal anti-icing deicing coating which comprises the following components in percentage by mass:
60-90% of resin prepolymer;
10-40% of thermosensitive color-changing dye microcapsule;
the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers.
Preferably, the thermochromic dye comprises one or more of crystal violet lactone, 2-phenylamino-3-methyl-6-dibutyl fluorane, bisphenol A and alpha-naphthol.
Preferably, stearic acid is also included in the thermochromic dye.
Preferably, the higher fatty alcohol comprises one or more of dodecanol, tetradecanol and hexadecanol;
the mass ratio of the thermochromic dye to the higher fatty alcohol is 2-6:300.
Preferably, the grain diameter of the thermosensitive color-changing dye microcapsule is 500 nm-10 mu m, and the thickness of the capsule wall is 10-200 nm.
Preferably, the resin prepolymer is one or more of a water-based epoxy resin prepolymer, a water-based polyurethane prepolymer, a solvent-free epoxy resin prepolymer and an organic silicon resin prepolymer;
the polymer is one or more of polystyrene, polymethyl methacrylate and polyvinyl acetate.
Preferably, the preparation method of the thermochromic dye microcapsule comprises the following steps:
mixing the capsule core component, the capsule wall component and the organic solvent to obtain an oil phase;
mixing a surfactant with water to obtain a water phase;
and adding the oil phase into the water phase, and stirring and mixing to obtain the thermochromic dye microcapsule.
Preferably, the surfactant is one or more of sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, polyvinyl alcohol, gum arabic, tween 80 and span 20;
the mass concentration of the surfactant in the water phase is 0.1-5%.
The invention provides a self-regulating photo-thermal anti-icing deicing coating, which is obtained by solidifying the self-regulating photo-thermal anti-icing deicing coating.
Preferably, the curing temperature is 40-80 ℃ and the curing time is 4-24 h.
The invention provides a self-regulating photo-thermal anti-icing deicing coating which comprises the following components in percentage by mass: 60-90% of resin prepolymer; 10-40% of thermosensitive color-changing dye microcapsule; the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers. According to the invention, the thermochromic dye microcapsule is added into the resin prepolymer, the thermochromic dye microcapsule contains the thermochromic dye, and the addition of the thermochromic dye enables the coating to be dark under the low temperature condition below 0 ℃ in winter, so that the coating has high photo-thermal conversion efficiency and plays a role in preventing ice and removing ice; the light-colored light-heat conversion efficiency is low under the high-temperature condition in summer, and the condition of overheating and accelerated aging is avoided. The thermochromic dye microcapsule contains higher fatty alcohol, has phase change in the photo-thermal conversion process, and can effectively absorb heat and release heat through the phase change, so that the effect of delaying surface cooling and icing is achieved.
Drawings
FIG. 1 is an SEM photograph of thermochromic dye microcapsules obtained in example 1;
FIG. 2 is a picture of the wall thickness of the thermochromic dye microcapsules obtained in example 2;
FIG. 3 is a photograph showing the regulated photothermal anti-icing and deicing coating obtained in example 1 at-20deg.C, 30deg.C
FIG. 4 is a graph showing the temperature change with time under irradiation of different coating simulated solar light sources;
FIG. 5 shows the melting of the regulated photothermal anti-icing deicing coating obtained in example 1 at different times;
FIG. 6 is a graphical representation of the cured self-regulating photo-thermal anti-icing deicing coating obtained in examples 2-6.
Detailed Description
The invention provides a self-regulating photo-thermal anti-icing deicing coating which comprises the following components in percentage by mass:
60-90% of resin prepolymer;
10-40% of thermosensitive color-changing dye microcapsule;
the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers.
The self-regulating photo-thermal anti-icing deicing coating provided by the invention comprises 60-90% of resin prepolymer, preferably 70-80% by mass. In the present invention, the resin prepolymer is preferably one or more of an aqueous epoxy resin prepolymer, an aqueous polyurethane prepolymer, a solvent-free epoxy resin prepolymer and a silicone resin prepolymer. The specific composition and preparation method of the resin prepolymer are not particularly limited, and those known to those skilled in the art can be used.
The self-regulating photo-thermal anti-icing deicing coating provided by the invention comprises 10-40% of thermochromic dye microcapsules, preferably 20-30% by mass. In the invention, the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers.
In the present invention, the thermochromic dye preferably includes one or more of crystal violet lactone, 2-phenylamino-3-methyl-6-dibutyl fluorane, bisphenol a, and α -naphthol.
In the present invention, stearic acid is also preferably included in the thermochromic dye. In the invention, the stearic acid participates in the electron loss of a dye system in the temperature change process, and the color change of the dye is regulated and controlled. In the present invention, the mass percentage of the stearic acid in the thermochromic dye is preferably 0.33 to 1.63%, more preferably 0.45 to 0.95%.
In the present invention, the higher fatty alcohol includes one or more of dodecanol, tetradecanol and hexadecanol. In the present invention, the mass ratio of the thermochromic dye to the higher fatty alcohol is preferably 2 to 6:300, more preferably 3 to 5:300. In the invention, the composition of the capsule core is preferably 2-phenylamino-3-methyl-6-dibutyl fluorane, bisphenol A and dodecanol, and the mass ratio of the 2-phenylamino-3-methyl-6-dibutyl fluorane, bisphenol A and dodecanol is preferably 1:1:300.
In the present invention, the polymer is preferably one or more of polystyrene, polymethyl methacrylate and polyvinyl acetate.
In the present invention, the particle diameter of the thermochromic dye microcapsules is preferably 500nm to 10. Mu.m, more preferably 800nm to 5. Mu.m, still more preferably 1 to 2. Mu.m. In the present invention, the thickness of the capsule wall is preferably 10 to 200nm, more preferably 50 to 150nm.
In the invention, the preparation method of the thermochromic dye microcapsule comprises the following steps:
mixing the capsule core component, the capsule wall component and the organic solvent to obtain an oil phase;
mixing a surfactant with water to obtain a water phase;
and adding the oil phase into the water phase, and stirring and mixing to obtain the thermochromic dye microcapsule.
In the present invention, the core component, the wall component and the organic solvent are preferably mixed to obtain an oil phase. In the present invention, the organic solvent is preferably one or more of dichloromethane, chloroform and ethyl acetate.
In the present invention, the mass ratio of the core component to the wall component is preferably 1:0.1 to 2, more preferably 1:0.5 to 1.5. In the present invention, the mass content of the organic solvent in the oil phase is preferably 50 to 85%, more preferably 70 to 85%. The mixing means of the present invention is not particularly limited, and mixing means well known to those skilled in the art, such as stirring and mixing, may be used.
The present invention preferably mixes the surfactant with water to obtain an aqueous phase. In the present invention, the surfactant is preferably one or more of sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, polyvinyl alcohol, gum arabic, tween 80 and span 20; the mass concentration of the surfactant in the aqueous phase is preferably 0.1 to 5%, more preferably 1 to 3%. The mixing means of the present invention is not particularly limited, and mixing means well known to those skilled in the art, such as stirring and mixing, may be used.
The oil phase is added into the water phase, and the mixture is stirred and mixed to obtain the thermochromic dye microcapsule. In the present invention, the mass ratio of the oil phase to the water phase is preferably 1:2 to 5, more preferably 1:3 to 4.
In the present invention, the temperature of the stirring and mixing is preferably 20 to 65 ℃, more preferably 30 to 50 ℃; the time is preferably 4 to 8 hours, more preferably 5 to 6 hours. In the present invention, the stirring and mixing rate is preferably 200 to 1000rpm, more preferably 400 to 800rpm. In the invention, in the stirring and mixing process, the organic solvent volatilizes, and dissolved capsule wall components are separated out to form a shell on the interface. The invention can maintain the stability of the emulsion system and avoid the adhesion of formed microcapsules by continuous stirring.
In the present invention, after the stirring and mixing, the present invention preferably filters and washes the obtained mixed solution, and the obtained solid is dried to obtain the thermochromic dye microcapsule. In the present invention, the detergent used for the washing is preferably deionized water. The specific manner of operation of the filtration and drying is not particularly limited by the present invention, and filtration and drying methods well known to those skilled in the art may be used.
In the invention, the preparation method of the self-regulating photo-thermal anti-icing deicing coating preferably comprises the following steps:
and mixing the resin prepolymer and the thermochromic dye microcapsules to obtain the self-regulating photo-thermal anti-icing deicing coating.
In the present invention, the mixing means is preferably stirring mixing. In the present invention, the present invention preferably performs defoaming after the stirring and mixing. The present invention is not particularly limited to the above-described defoaming method, and may be performed by a defoaming method known to those skilled in the art.
The invention provides a self-regulating photo-thermal anti-icing deicing coating, which is obtained by solidifying the self-regulating photo-thermal anti-icing deicing coating.
In the invention, the preparation method of the self-regulating photo-thermal anti-icing deicing coating preferably comprises the following steps:
and coating the self-regulating photo-thermal anti-icing deicing coating on the surface of the substrate to obtain the self-regulating photo-thermal anti-icing deicing coating.
In the present invention, the curing temperature is preferably 40 to 80 ℃, more preferably 50 to 70 ℃; the time is preferably 4 to 24 hours, more preferably 6 to 18 hours, still more preferably 10 to 15 hours.
In the invention, the thickness of the self-regulating photo-thermal anti-icing and deicing coating is preferably 2-10 mm, more preferably 4-8 mm.
The self-regulating photo-thermal anti-icing deicing coating and coating provided by the invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
Example 1
(1) Preparation of thermochromic dye microcapsules
Mixing 2-phenylamino-3-methyl-6-dibutyl fluorane, bisphenol A and dodecanol according to a ratio of 1:1:300 to obtain capsule core component.
6g of the capsule core component and 4g of PMMA are added into 50g of dichloromethane solvent, and the mixture is uniformly mixed and stirred to obtain an oil phase solution. The mass fraction of methylene dichloride in the oil phase solution is 85%, and the mass ratio of the capsule core component to the polymer is 3:2.
120mL of an aqueous solution of cetyltrimethylammonium bromide and polyvinyl alcohol was prepared, wherein the mass fraction of cetyltrimethylammonium bromide was 0.5% and the mass fraction of polyvinyl alcohol was 2%. The oil phase solution was added to the aqueous phase solution in one portion with mechanical stirring at 1000rpm and stirred for 20 minutes to form a microemulsion. The mass ratio of the solution A to the solution B in the microemulsion is 1:2. Stirring the microemulsion at 45 ℃ for 8 hours to volatilize the solvent methylene dichloride completely, and filtering and washing with deionized water to obtain the thermochromic dye microcapsule.
The resulting thermochromic dye microcapsules were characterized by scanning electron microscopy and the results are shown in fig. 1. As can be seen from FIG. 1, the prepared microcapsule has a particle size of about 1-10 μm, dense capsule wall and good coating property.
The wall thickness SEM photograph of the obtained thermochromic dye microcapsules is shown in FIG. 2, and it can be seen from FIG. 2 that the wall thickness of the thermochromic dye microcapsules is about 190nm.
(2) Self-regulating photo-thermal anti-icing deicing coating and preparation of coating
And adding the thermochromic dye microcapsules into the organosilicon polyurethane prepolymer, wherein the mass ratio of the thermochromic microcapsules to the organosilicon polyurethane prepolymer is 1:4. And (3) mechanically stirring and uniformly mixing, and obtaining the self-regulating photo-thermal anti-icing deicing coating after low-speed stirring and defoaming. And (3) brushing the coating on a tinplate sample plate, and curing for 8 hours at 60 ℃ to obtain the self-regulating photo-thermal anti-icing deicing coating.
The picture of the self-regulating photo-thermal anti-icing deicing coating at-20 ℃ and 30 ℃ is shown in figure 3. As can be seen from fig. 3, the self-regulating photo-thermal anti-icing and deicing coating provided by the invention has a dark color at a low temperature and a light color at a higher temperature.
Performance testing
An alumina-doped white polyurethane coating and a carbon nanotube-doped black polyurethane coating were used as comparative examples.
The temperature test was performed by an infrared camera under the conditions of simulating solar light irradiation in an environment of-5 ℃ simultaneously with the regulated photothermal anti-icing deicing coating, the alumina-doped white polyurethane coating and the carbon nanotube-doped black polyurethane coating obtained in example 1, and the obtained results are shown in fig. 4. As can be seen from fig. 4, the self-regulating photo-thermal coating temperature can be stabilized at 20 ℃ with the increase of the illumination time, the white polyurethane coating temperature is still-5 ℃, and the black polyurethane coating temperature is increased to more than 30 ℃.
And (3) in an environment of-5 ℃, placing the coating under simulated sunlight irradiation, and recording the icing and melting time of the surface. The melting conditions obtained from the regulated photo-thermal anti-icing deicing coating for example 1 at different times are shown in figure 5. The self-regulating photo-thermal coating and the black polyurethane coating can completely melt the accumulated ice on the surface within 20 minutes, and the white polyurethane coating is not melted due to the fact that the surface is free of a photo-thermal effect.
Examples 2 to 6
Examples 2 to 6 are different from example 1 in the kind and amount of raw materials, and the other operations are the same. The types and amounts of the raw materials used in examples 2 to 6 are shown in Table 1.
Table 1 raw material types and amounts of examples 2 to 6
The self-regulating photo-thermal anti-icing deicing coating obtained in examples 2-4 is shown in FIG. 6. The self-regulating photo-thermal anti-icing deicing coating disclosed by the invention is dark at low temperature and light at higher temperature.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (4)
1. The self-regulating photo-thermal anti-icing deicing coating consists of the following components in percentage by mass:
60-90% of resin;
10-40% of a thermochromic dye microcapsule;
the thermochromic dye microcapsule comprises a capsule wall and a capsule core, wherein the components of the capsule core comprise thermochromic dye and higher fatty alcohol; the components of the capsule wall are polymers;
the thermochromic dye is 2-phenylamino-3-methyl-6-dibutyl fluorane and bisphenol A;
the higher fatty alcohol is dodecanol;
the mass ratio of the 2-phenylamino-3-methyl-6-dibutyl fluorane to bisphenol A to dodecanol is 1:1:300;
the resin is one or more of water-based epoxy resin, water-based polyurethane, solvent-free epoxy resin and organic silicon resin;
the polymer is one or more of polystyrene, polymethyl methacrylate and polyvinyl acetate;
the particle size of the thermochromic dye microcapsule is 500 nm-10 mu m, and the thickness of the capsule wall is 10-200 nm;
the preparation method of the thermochromic dye microcapsule comprises the following steps:
mixing the capsule core component, the capsule wall component and the organic solvent to obtain an oil phase;
mixing a surfactant with water to obtain a water phase;
adding the oil phase into the water phase, and stirring and mixing to obtain a thermochromic dye microcapsule; the stirring and mixing speed is 200-1000 rpm.
2. The self-regulating photo-thermal anti-icing deicing coating according to claim 1, wherein said surfactant is one or more of sodium dodecyl benzene sulfonate, cetyltrimethylammonium bromide, polyvinyl alcohol, gum arabic, tween 80 and span 20;
the mass concentration of the surfactant in the water phase is 0.1-5%.
3. A self-regulating photo-thermal anti-icing deicing coating obtained by curing the self-regulating photo-thermal anti-icing deicing coating of any one of claims 1-2.
4. A self-regulating photo-thermal anti-icing and deicing coating as claimed in claim 3, wherein the curing temperature is 40-80 ℃ for 4-24 hours.
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