CN111187570A - High-transparency rare earth nano composite heat-insulating coating and preparation method and application thereof - Google Patents
High-transparency rare earth nano composite heat-insulating coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-transparency rare earth nano composite heat insulation coating and a preparation method and application thereof, wherein the high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight: 15-30 parts of rare earth nano composite heat insulation slurry, 20-30 parts of organic silicon resin, 10-20 parts of polyurethane modified epoxy resin, 3-15 parts of transparent hollow glass beads, 30-50 parts of diluent and 0.3-1.1 parts of film forming auxiliary agent. The high-transmittance rare earth nano composite heat-insulating coating disclosed by the invention is stable in property, strong in weather resistance, good in heat-insulating effect, low in cost and convenient and fast to apply.
Description
Technical Field
The invention belongs to the field of energy-saving and environment-friendly materials, and particularly relates to a high-transparency rare earth nano composite heat-insulating coating as well as a preparation method and application thereof.
Background
In recent years, the problem of energy shortage is more and more emphasized, and energy conservation and emission reduction become the main melody of the times. The global greenhouse gas emission is related to the building energy consumption by statistics of about 1/3. In the case of using a large amount of glass for windows of buildings, ceilings, automobile windows, etc., the heat radiation of light will cause a large increase in energy consumption. Heat insulation products in the market such as hollow glass, Low-e glass and the like are expensive in manufacturing cost, poor in heat insulation effect, high in glass replacement difficulty and difficult to popularize in the market. The existing solution mainly comprises a heat insulation coating using inorganic functional materials such as ITO (indium tin oxide), ATO (antimony tin oxide) and the like as additives, but the heat insulation effect and the weather resistance of the heat insulation material are both required to be improved.
At present, some research achievements are made on transparent heat-insulating coatings at home and abroad. Through patent retrieval, PCT international application WO2018103063 (a manufacturing process of a nano ATO transparent heat-insulating energy-saving glass coating) disperses nano ATO in a water-based resin to form a heat-insulating coating, but the coating has high requirements on nano material dispersibility and compatibility, and has a limited heat-insulating effect. Chinese patent with application number CN201710243083.0, "a glass transparent heat insulation nano coating and a preparation method thereof" uses nano ATO-rare earth-polycrystalline silicon as a heat insulation auxiliary agent, but the heat insulation effect is very limited; the Chinese patent with the application number of CN201610979211.3, namely the water-based strippable transparent heat-insulating glass paint and the preparation method thereof, adopts water-based nano ATO and ITO composite heat-insulating slurry, so that the cost is high, and the mixed slurry is easy to agglomerate. Chinese patent CN201710709405.6, a transparent nano heat-insulating coating, uses nano ATO and tungsten oxide as heat-insulating additives, which is too high in cost and poor in weather resistance. Chinese patent CN201721118368.3 application number "a heat-insulating energy-saving glass", which comprises an outer layer glass and an inner layer glass, wherein the two layers of glass are separated by a distance and a heat-insulating cavity is formed between the two layers of glass, the outer layer glass comprises a heat-insulating layer containing nano tungsten oxide and/or nano tin antimony oxide heat-insulating powder, and the process is complex and the requirements are strict. Therefore, the invention of the novel heat-insulating coating which has the advantages of obvious effect, stable performance, low cost, high transmittance and convenient coating application and popularization is necessary.
Disclosure of Invention
In view of the above, the invention aims to provide a high-transmittance rare earth nanocomposite heat insulation coating to overcome the defects of the prior art, and the coating has the advantages of stable property, strong weather resistance, good heat insulation effect, low cost and convenient application.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight: 15-30 parts of rare earth nano composite heat insulation slurry, 20-30 parts of organic silicon resin, 10-20 parts of polyurethane modified epoxy resin, 3-15 parts of transparent hollow glass beads, 30-50 parts of diluent and 0.3-1.1 parts of film forming auxiliary agent.
Preferably, the rare earth nano composite heat insulation slurry comprises the following components in parts by weight: 5-30 parts of rare earth boride, 1-15 parts of cesium tungsten bronze powder, 0.06-2.25 parts of a dispersing agent and 100 parts of a dispersing medium.
Preferably, the rare earth boride is one of praseodymium hexaboride, dysprosium hexaboride, lanthanum hexaboride, cerium hexaboride, rubidium hexaboride, ytterbium hexaboride, europium hexaboride and yttrium hexaboride.
Preferably, the average particle size of the rare earth nano composite heat insulation slurry is between 10 and 100nm
Preferably, the dispersing agent is one or more than two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyl trimethyl ammonium bromide, ethylenediamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate, polyether modified silicone oil, modified acrylate copolymer, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 and silane coupling agent KH 792.
Preferably, the dispersion medium is one or two of deionized water, ethanol, tert-butyl alcohol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, propylene glycol methyl ether acetate, cyclohexane and toluene.
Preferably, the organic silicon resin is one or more than two of SI-100, SI-400, PSI-050, PSI-060, ACR902, ACR-903 and ACR-904A.
Preferably, the diluent is one or more than two of propylene glycol methyl ether, isopropanol, ethanol, butanol, sec-butanol, acetone, butyl acetate and ethyl acetate.
Preferably, the film forming aid comprises a defoaming agent, a leveling agent and a drier.
Preferably, the weight ratio of the defoaming agent to the leveling agent to the drier is (1-3): (1-4): (1-4).
Further preferably, the defoaming agent is a silicone defoaming agent.
Preferably, the leveling agent is one or more than two of BYK-323, BYK-331, BYK-333, BYK310 and BYK-361N.
Preferably, the drier is one or more of dibutyltin dilaurate, cobalt naphthenate, zirconium isooctanoate and cobalt isooctanoate.
The invention also aims to provide a preparation method of the high-transparency rare earth nano composite heat-insulating coating, so as to prepare the high-transparency rare earth nano composite heat-insulating coating.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a high-transparency rare earth nano-composite heat insulation coating comprises the steps of preparing rare earth nano-composite heat insulation slurry and adding organic silicon resin, polyurethane modified epoxy resin, transparent hollow glass microspheres, a diluent and a film forming aid into the nano-composite heat insulation slurry, uniformly stirring and ultrasonically dispersing to obtain the high-transparency rare earth nano-composite heat insulation coating.
Preferably, the preparation method of the rare earth nano composite heat insulation slurry comprises the following steps: the rare earth boride is used as a base material, the rare earth boride and cesium tungsten bronze powder are stirred and mixed, then the mixture is fully mixed with a dispersing agent in a dispersing medium to obtain a dispersion liquid, and then the dispersion liquid is subjected to sand grinding and ultrasonic treatment to prepare the uniformly dispersed high-permeability rare earth nano composite heat insulation slurry.
Preferably, the dispersion is dispersed in a sand mill under high shear for 0.5 to 24 hours.
Preferably, the ultrasonic time after the dispersion is sanded is 2-60 min.
The invention also relates to the application of the high-permeability rare earth nano composite heat insulation coating in the field of heat preservation and heat insulation.
The invention also relates to a preparation method of a coating containing the high-permeability rare earth nano composite heat insulation coating, which comprises the following steps: and uniformly coating the high-permeability rare earth nano composite heat insulation coating on a glass substrate by a spin coating method or a wire rod method, and drying at 150-250 ℃ for 20-60 min to solidify the coating to obtain the coating.
Preferably, the coating thickness of the high-permeability rare earth nano composite heat insulation coating is 1-60 mu m.
Compared with the prior art, the high-transmittance rare earth nano composite heat insulation coating has the following advantages:
(1) the rare earth boride is used as a raw material, has stable property and a CsCl structure, has stronger absorption and scattering on thermal radiation in a near infrared light region of 750-1100 nm due to the local surface plasma resonance effect of free electrons, and has stronger shielding effect on near infrared light with the wavelength of more than 1100nm due to the cesium tungsten bronze, so that the cesium tungsten bronze and the CsW bronze are combined to form composite slurry, the advantages of the composite slurry are complementary, and the composite slurry has better performance than traditional transparent heat-insulating materials such as ATO, ITO and the like. The coating film made of the material can absorb more than 97% of ultraviolet light and more than 90% of infrared light, and meanwhile, the visible light transmittance reaches more than 75%.
(2) Compared with the coating taking ATO, ITO and the like as raw materials, the coating has more excellent ultraviolet and near infrared shielding effects and low production cost.
(3) Compared with the prior art, the production process is simple and easy to control and operate.
(4) The polyurethane has better hardness, abrasion resistance and solvent resistance, but the heat resistance and the water resistance of the polyurethane are poorer, the organic silicon has better high-temperature resistance and low-temperature resistance, and the epoxy resin has good adhesion and insulativity. The paint prepared by the formula has stable performance, high hardness, good weather resistance and convenient brushing.
The preparation method of the high-transparency rare earth nano-composite heat-insulating coating and the preparation method of the high-transparency rare earth nano-composite heat-insulating coating have the same advantages as the high-transparency rare earth nano-composite heat-insulating coating compared with the prior art, and are not repeated herein.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a coating containing a high-permeability rare earth nanocomposite thermal insulating coating according to the present invention;
fig. 2 is an optical transmittance detection diagram of the high-transmittance rare earth nanocomposite thermal insulation coating and a commercially available ATO coating in example 1 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail below with reference to examples and drawings, but the examples of the present invention are not limited thereto.
Firstly, the source of raw materials
1. The organic silicon resins ACR-903, ACR-902, PSI-050, PSI-060, ACR-904A, SI-100 and SI-400 are all produced by the intelligent science and technology (China) limited company.
2. The polyurethane modified epoxy resin 120C-1 and 120C-3 are produced by Hengchuang insulation materials Co.
3. The 325-mesh transparent hollow glass beads are produced by Shijiazhuang bamboo science and technology Co.
4. Cesium tungsten bronze powder is produced by Nicoti Jialong nanometer industry Co.
5. The silicone defoamer FAG470 is a defoaming king FAG470 product produced by Haian petrochemical plants in Jiangsu province.
6. BYK-331, BYK-310, BYK-361N, BYK-323 are all available from the full company of the Shanghai province.
7. The high molecular weight silane copolymer is a WA8876 product produced by Wanjun chemical technology Co., Ltd.
Examples 1 to 4 and Performance test
Example 1
A high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight:
wherein: the organic silicon resin is a mixture of organic silicon modified acrylic resin ACR-903 and organic silicon modified acrylic resin ACR-902 in a weight ratio of 8: 2.
The rare earth nano composite heat insulation slurry comprises the following components in parts by weight:
wherein the weight ratio of the polyvinylpyrrolidone to the sodium dodecyl benzene sulfonate is 5: 8; the rare earth boride is lanthanum hexaboride.
The preparation method of the high-transparency rare earth nano composite heat-insulating coating comprises the following steps:
mixing and stirring the rare earth boride powder and cesium tungsten bronze powder, fully mixing the mixture with polyvinylpyrrolidone and sodium dodecyl benzene sulfonate in ethanol, adding the mixed solution into a sand mill, grinding and dispersing for 0.5h, taking out, and performing ultrasonic dispersion for 2min to obtain the rare earth nano composite heat insulation slurry with the average particle size of 70 nm. And then adding organic silicon resins ACR-903, ACR-902, polyurethane modified epoxy resin, transparent hollow glass microspheres, ethyl acetate, an organic silicon defoaming agent, BYK-331 and cobalt isooctanoate into the rare earth nano composite heat insulation slurry, uniformly stirring and carrying out ultrasound treatment for 15min to obtain the high-transparency rare earth nano composite heat insulation coating.
Uniformly coating the high-permeability rare earth nano composite heat insulation coating on the surface of a clean glass substrate by a wire rod method, placing the glass substrate in a drying oven, heating to 200 ℃, and drying for 20min to solidify the coating to obtain the coating. The test can obtain: the thickness of the coating is 10 mu m, the visible light transmittance is 77%, the infrared ray rejection rate is 91%, the ultraviolet rejection rate is 97.1%, and the temperature drop range of a heat insulation instrument is 12 ℃.
In addition, the optical transmittance of the high-transmittance rare earth nanocomposite thermal insulation coating of the embodiment and a commercially available ATO coating is detected, and the detection result is shown in FIG. 2. As can be seen from FIG. 2, compared with the blank glass and the commercially available ATO coating, the infrared blocking rate of the coating of the present invention at 750-2500nm is much higher than that of the commercially available coating, and the transmittance in the visible light range of 780-380 nm is also higher than that of the commercially available coating.
Example 2
A high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight:
wherein: the weight ratio of the silicone resin PSI-050 to PSI-060 is 7: 3.
The rare earth nano composite heat insulation slurry comprises the following components in parts by weight:
wherein: the mixing weight ratio of the tertiary butanol to the deionized water is 1: 2; the weight ratio of the rare earth boride to cerium hexaboride polyvinylpyrrolidone to sodium dodecyl benzene sulfonate is 4: 7.
The preparation method of the high-transparency rare earth nano composite heat-insulating coating comprises the following steps:
mixing and stirring rare earth boride powder and cesium tungsten bronze powder, fully mixing the mixture with polyvinylpyrrolidone and sodium dodecyl sulfate in a mixed solution of tert-butyl alcohol and deionized water, adding the mixed solution into a sand mill, grinding and dispersing for 1h, taking out, and performing ultrasonic dispersion for 15min to obtain the high-permeability rare earth nano composite heat insulation slurry with the average particle size of 50 nm. And then adding organic silicon resin PSI-050, PSI-060, polyurethane modified epoxy resin, transparent hollow glass microspheres, sec-butyl alcohol, an organic silicon defoamer, BYK-310 and dibutyltin dilaurate into the rare earth nano composite heat insulation slurry, uniformly stirring and carrying out ultrasonic treatment for 15min to obtain the high-transparency rare earth nano composite heat insulation coating.
Uniformly coating the high-permeability rare earth nano composite heat-insulating coating on the surface of a clean glass substrate by a wire rod method, placing the glass substrate in a drying oven, heating to 250 ℃, and drying for 40min to solidify the coating to obtain the coating. The test can obtain: the thickness of the coating is 15 mu m, the visible light transmittance is 70%, the infrared ray rejection rate is 94%, the ultraviolet rejection rate is 97.2%, and the temperature drop range of a heat insulation instrument is 13 ℃.
Example 3
A high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight:
wherein the weight ratio of the organic silicon resin ACR-903 to the ACR-904A is 7: 2.
The rare earth nano composite heat insulation slurry comprises the following components in parts by weight:
wherein the rare earth boride is lanthanum hexaboride, and the mixing weight ratio of the polyethylene glycol and the silane coupling agent KH550 is 1: 2.
The preparation method of the high-transparency rare earth nano composite heat-insulating coating comprises the following steps:
mixing and stirring the rare earth boride powder and the cesium tungsten bronze powder, fully mixing the mixture with polyethylene glycol and a silane coupling agent in ethyl acetate, adding the mixed solution into a sand mill, grinding and dispersing for 3.5h, taking out, and performing ultrasonic dispersion for 30min to obtain the high-transmittance rare earth nano composite heat insulation slurry with the average particle size of 30 nm. And then adding organic silicon resins ACR-903, ACR-904A, polyurethane modified epoxy resin, propylene glycol methyl ether, an organic silicon defoaming agent, BYK-361N and zirconium isooctanoate into the rare earth nano composite heat insulation slurry, uniformly stirring and carrying out ultrasonic treatment for 15min to obtain the high-transparency rare earth nano composite heat insulation coating.
And (3) uniformly coating the high-transparency rare earth nano composite heat insulation coating on the surface of a clean glass substrate by using a spin coating method, placing the glass substrate in an oven, heating to 250 ℃, and drying for 30min to solidify the coating to obtain the coating. The test can obtain: the thickness of the coating is 8 mu m, the visible light transmittance is 75%, the infrared ray rejection rate is 93.2%, the ultraviolet rejection rate is 98.8%, and the temperature drop range of a heat insulation instrument is 15 ℃.
Example 4
A high-transparency rare earth nano composite heat insulation coating comprises the following components in parts by weight:
wherein the weight ratio of the organic silicon resin SI-100 to the SI-400 is 8: 3.
The rare earth nano composite heat insulation slurry comprises the following components in parts by weight:
wherein the rare earth boride is europium hexaboride.
The preparation method of the high-transparency rare earth nano composite heat-insulating coating comprises the following steps:
mixing and stirring rare earth boride powder and cesium tungsten bronze powder, fully mixing the mixture with a high molecular weight silane copolymer in cyclohexane, adding the mixed solution into a sand mill, grinding and dispersing for 20 hours, taking out, and performing ultrasonic dispersion for 20min to obtain the high-transparency rare earth nano composite heat insulation slurry with the particle size of 20 nm. And then adding organic silicon resins SI-100 and SI-400, polyurethane modified epoxy resin, transparent hollow glass microspheres, butyl acetate, an organic silicon defoaming agent, BYK-323 and cobalt naphthenate into the rare earth nano composite heat insulation slurry, uniformly stirring and carrying out ultrasonic treatment for 15min to obtain the high-transparency rare earth nano composite heat insulation coating.
And (3) uniformly coating the high-transparency rare earth nano composite heat insulation coating on the surface of a clean glass substrate by using a spin coating method, placing the glass substrate in an oven, heating to 250 ℃, and drying for 60min to solidify the coating to obtain the coating. The test can obtain: the coating thickness is 20 mu m, the visible light transmittance is 75%, the infrared ray rejection rate is 90.7%, the ultraviolet rejection rate is 96.2%, and the testing temperature range of a heat insulation instrument is 13 ℃.
In conclusion, the high-transmittance rare earth nanometer heat-insulating composite coating has the advantages of strong weather resistance, low cost, obvious effect, direct coating on the surface of glass and convenient and fast application. When the high-transmittance rare earth nano heat-insulating coating is coated on glass, the high-transmittance rare earth nano heat-insulating coating not only has higher light transmittance, but also has excellent infrared barrier rate and ultraviolet barrier rate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A high-transparency rare earth nano composite heat insulation coating is characterized in that: the paint comprises the following components in parts by weight: 15-30 parts of rare earth nano composite heat insulation slurry, 20-30 parts of organic silicon resin, 10-20 parts of polyurethane modified epoxy resin, 3-15 parts of transparent hollow glass beads, 30-50 parts of diluent and 0.3-1.1 parts of film forming auxiliary agent.
2. The high-permeability rare earth nanocomposite thermal insulation coating according to claim 1, characterized in that: the rare earth nano composite heat insulation slurry comprises the following components in parts by weight: 5-30 parts of rare earth boride, 1-15 parts of cesium tungsten bronze powder, 0.06-2.25 parts of a dispersing agent and 100 parts of a dispersing medium.
3. The high-permeability rare earth nanocomposite thermal insulation coating according to claim 2, characterized in that: the rare earth boride is one of praseodymium hexaboride, dysprosium hexaboride, lanthanum hexaboride, cerium hexaboride, rubidium hexaboride, ytterbium hexaboride, europium hexaboride and yttrium hexaboride;
and/or the average grain diameter of the rare earth nano composite heat insulation slurry is between 10 and 100 nm.
4. The high-permeability rare earth nanocomposite thermal insulation coating according to claim 2 or 3, characterized in that: the dispersing agent is one or more than two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyl trimethyl ammonium bromide, ethylenediamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lignosulfonate, polyether modified silicone oil, modified acrylate copolymer, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 and silane coupling agent KH 792;
and/or the dispersion medium is one or two of deionized water, ethanol, tert-butyl alcohol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, propylene glycol methyl ether acetate, cyclohexane and toluene.
5. The high-permeability rare earth nanocomposite thermal insulation coating according to any one of claims 2 to 4, characterized in that: the organic silicon resin is one or more than two of SI-100, SI-400, PSI-050, PSI-060, ACR902, ACR-903 and ACR-904A;
and/or the diluent is one or more than two of propylene glycol methyl ether, isopropanol, ethanol, butanol, sec-butyl alcohol, acetone, butyl acetate and ethyl acetate.
6. The high-permeability rare earth nanocomposite thermal insulation coating according to any one of claims 2 to 5, characterized in that: the film forming auxiliary agent comprises a defoaming agent, a flatting agent and a drier;
preferably, the weight ratio of the defoaming agent to the leveling agent to the drier is (1-3): (1-4): (1-4);
further preferably, the defoaming agent is an organic silicon defoaming agent; and/or the flatting agent is one or more than two of BYK-323, BYK-331, BYK-333, BYK310 and BYK-361N; and/or the drier is one or more than two of dibutyltin dilaurate, cobalt naphthenate, zirconium isooctanoate and cobalt isooctanoate.
7. A method for preparing the high-permeability rare earth nanocomposite thermal insulation coating according to any one of claims 1 to 6, characterized in that: the preparation method comprises the steps of preparing rare earth nano composite heat insulation slurry and adding organic silicon resin, polyurethane modified epoxy resin, transparent hollow glass beads, diluent and film forming auxiliary agent into the nano composite heat insulation slurry, uniformly stirring and ultrasonically dispersing to obtain the high-transparency rare earth nano composite heat insulation coating.
8. The preparation method of the high-permeability rare earth nano composite heat insulation coating according to claim 7, characterized by comprising the following steps: the preparation method of the rare earth nano composite heat insulation slurry comprises the following steps: taking rare earth boride as a base material, stirring and mixing the rare earth boride with cesium tungsten bronze powder, then fully mixing the mixture with a dispersing agent in a dispersing medium to obtain a dispersion liquid, and then preparing uniformly dispersed high-permeability rare earth nano composite heat insulation slurry after sanding and ultrasonic processing the dispersion liquid;
preferably, the dispersion liquid is sheared and dispersed in a sand mill at high speed, and the dispersion time is 0.5 to 24 hours;
preferably, the ultrasonic time after the dispersion is sanded is 2-60 min.
9. The use of the high-permeability rare earth nanocomposite thermal insulation coating according to any one of claims 1 to 8 in the field of thermal insulation.
10. A method for preparing a coating layer containing the high-permeability rare earth nanocomposite thermal insulation coating material according to any one of claims 1 to 8, characterized in that: uniformly coating the high-permeability rare earth nano composite heat-insulating coating on a glass substrate by a spin-coating method or a wire-rod method, and drying at 150-250 ℃ for 20-60 min to solidify the coating to obtain a coating;
preferably, the coating thickness of the high-permeability rare earth nano composite heat insulation coating is 1-60 mu m.
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