CN111876073B - Weather-resistant organic silicon transparent temperature control coating and preparation method thereof - Google Patents
Weather-resistant organic silicon transparent temperature control coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of coatings, and discloses a weather-resistant organic silicon transparent temperature control coating and a preparation method thereofThe raw materials in parts by weight include: 30-60 parts of high-boiling silicone oil, 30-60 parts of a cross-linking agent, 5-20 parts of a chain extender, 3-15 parts of a modified filler, 0.01-1 part of dodecyl diamine hydrochloride, 0.1-1 part of a catalyst, 0.01-1 part of a thickening agent and 100-500 parts of a solvent. The invention adopts high boiling silicone oil to prepare transparent coating, and LaCrO is added into the coating3Coated VO2As the modified filler, the prepared transparent coating has good weather resistance and an automatic temperature regulation function, so that the energy consumption of the coating can be effectively reduced in summer and winter.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a weather-resistant organic silicon transparent temperature control coating and a preparation method thereof.
Background
The "energy crisis" is the focus of attention of people in China and even worldwide in the present generation. With the high-speed development of Chinese economy, how to reduce energy consumption and improve energy utilization rate becomes a crucial problem for ensuring sustainable development of Chinese economy. The nano transparent heat-insulating coating is an energy-saving product, has quite wide application field, is particularly suitable for places such as high-rise houses, commercial office buildings, schools, automobile glass and the like which require heat insulation, heat preservation and ultraviolet ray blocking and have special requirements on light transmission performance and sight line, and has very great energy-saving potential.
Transparent thermal insulation coatings have been developed in China for many years and have been widely used. Chinese patent CN201810144270.8 discloses a transparent heat-insulating coating and a preparation and coating process thereof, and the product has excellent heat preservation and heat insulation effects and has the characteristics of strong decoration and the like; chinese patent CN201811523336.0 discloses a PS microsphere modified waterborne polyurethane transparent heat-insulating coating, which has the characteristics of good wear resistance, high visible light transmittance, remarkable heat-insulating new performance and the like. Chinese patent CN201610128805.3 discloses a nano transparent heat-insulating coating and a preparation method thereof, the product takes water-based acrylic resin as a film-forming substance, and the product has the characteristics of good heat-insulating property, high transparency of a coating, low cost and the like.
Although various transparent heat-insulating coatings have many product achievements, most of the film-forming substances of the current products are acrylic resin coatings or polyurethane coatings, and the products have certain defects in the aspects of weather resistance, high temperature resistance and the like. In addition, the transparent heat insulation coating in the prior art can block most of near infrared and part of visible light in sunlight in summer, can reduce the energy consumption of an air conditioner in summer, but can also block heat in winter, cannot enter a room, and can increase heating energy consumption.
Disclosure of Invention
The invention provides a weather-proof type organic silicon transparent temperature control coating and a preparation method thereof, aiming at overcoming the defects of weather resistance, high temperature resistance and the like of a transparent heat insulation coating in the prior art, and solving the problems that the transparent heat insulation coating can block most of near infrared and partial visible light in sunlight in summer and can reduce the energy consumption of an air conditioner in summer, but the heat in winter can be blocked, cannot enter a room and can increase the heating energy consumption, the transparent heat insulation coating is prepared by adopting high-boiling silicone oil, and LaCrO is added into the coating3Coated VO2As the modified filler, the prepared transparent coating has good weather resistance and an automatic temperature regulation function, so that the energy consumption of the coating can be effectively reduced in summer and winter.
In order to achieve the purpose, the invention adopts the following technical scheme:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight:
preferably, the preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, and stirring for 20-30 min to obtain a mixed solutionLiquid, VOSO in said mixed solution4·xH2The concentration of O is 0.2-0.3 g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: (0.8 to 1);
B) dropwise adding NaHCO with mass concentration of 5-8% into the mixed solution3The pH value of the solution is 6-7, stirring and reacting for 30-40 min, filtering, washing the product with deionized water and ethanol, and drying;
C) calcining the dried product in a nitrogen atmosphere at 800-850 ℃ for 3-4 h, and cooling to obtain VO2Powder;
D) the molar ratio is (0.7-0.9): 1 La (NO)3)3·6H2O and Cr (NO)3)3·9H2Dissolving O in deionized water to obtain La (NO)3)3·6H2Adding a nitrate solution with the mass fraction of O being 20-40% and La (NO) into the nitrate solution3)3·6H2The molar ratio of O is (2-4): VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) dropwise adding 1-2 mol/L ammonia water into the dispersion liquid under a stirring state to adjust the pH of the system to 4-5, and cleaning a product with deionized water after filtering;
F) adding Cr (NO) to the cleaned product3)3·9H2The molar ratio of O is (0.1-0.3): ca (NO) of 13)2·4H2And O, stirring for 20-30 min, drying at 80-90 ℃, and calcining at 800-850 ℃ for 2-3 h to obtain the modified filler.
Preferably, the preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain the dodecyl diamine hydrochloride.
Preferably, the cross-linking agent is one or a mixture of more of ethyl orthosilicate, methyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.
Preferably, the chain extender is one or a mixture of two of dimethyldimethoxysilane and dimethyldiethoxysilane.
Preferably, the catalyst is one or a mixture of two of hydrochloric acid and glacial acetic acid.
Preferably, the solvent is one or more of ethanol, isopropanol, n-butanol, ethyl acetate, xylene and toluene.
The invention also provides a preparation method of the weather-resistant organic silicon transparent temperature control coating, which comprises the following steps:
(1) adding dodecyl diamine hydrochloride into 10-50 parts of solvent, stirring until the dodecyl diamine hydrochloride is dissolved, adding modified filler, stirring for reacting for 1-2 hours after ultrasonic dispersion, and cooling to obtain modified filler dispersion liquid;
(2) mixing high-boiling silicone oil, a cross-linking agent and a chain extender in proportion to obtain a mixed solution, mixing a catalyst with the rest solvent to obtain a catalyst solution, dropwise adding the catalyst solution into the mixed solution while stirring, and stirring for reaction for 3-5 hours;
(3) dropwise adding the modified filler dispersion liquid and the thickening agent into the mixed liquid after reaction, and stirring for 20-30 min to obtain the organic silicon transparent temperature-control coating.
Preferably, the ultrasonic dispersion time in the step (1) is 40-60 min, and the reaction temperature is 40-50 ℃.
Preferably, the reaction temperature in the step (2) is 40-60 ℃.
The invention adopts high-boiling silicone oil as a raw material to produce the transparent coating, the high boiling of the organosilicon is a common organosilicon byproduct, and with the rapid development of the world, particularly the organosilicon industry in China, the yield of the methyl chlorosilane is more and more large, so that a large amount of organosilicon high-boiling substances are produced. In the process of synthesizing methyl chlorosilane by adopting a direct method, 5-10% of high-boiling residues are generated when one ton of crude monomers are synthesized. At present, organic silicon high-boiling substances are mainly treated by being converted into high-boiling silicon oil, but the market amount of the high-boiling silicon oil is limited, and the high-boiling products are completely cupped waterwheel salaries relative to huge amount of high-boiling products, so that the problem that the reasonable utilization of the high-boiling silicon oil to obtain products with higher added values is urgently needed to be solved by organic monomer factories is solved.
The high-boiling silicone oil is a primary condensed ring body prepared by adding water into dimethyldichlorosilane for hydrolysis, the high-boiling silicone oil, a chain extender and a cross-linking agent react under the action of a catalyst to prepare the organic silicon transparent coating, and because the organic silicon product takes a silicon-oxygen bond as a main chain structure, the bond energy of the silicon-oxygen bond is 121 kilocalories/gram molecule, and the bond energy of a carbon-carbon bond is 82.6 kilocalories/gram molecule, the obtained organic silicon transparent coating has high thermal stability, and chemical bonds of the molecules are not cracked or decomposed under high temperature or radiation irradiation, so that the organic silicon transparent coating has good high temperature resistance; in addition, the silicon-oxygen bond is not easy to be decomposed by ultraviolet light and ozone, so that the prepared organic silicon transparent coating has good thermal stability, irradiation resistance and weather resistance.
Simultaneously, VO is added into the organic silicon transparent coating2As a nucleus, LaCrO3The core-shell structure of the shell is used for modifying the filler, so that the coating has temperature control performance and can effectively save energy. VO (vacuum vapor volume)2Is an oxide with phase change function, and VO is generated when the temperature is higher than the phase change point2The solar energy collector is in a metal state, a visible light area is transparent, an infrared light area is highly reflective, the infrared light part of solar radiation is shielded outdoors, and the transmittance of the infrared light is low; VO at a temperature lower than the phase transition point2In a semi-conducting state, is transparent to a medium degree from visible light to infrared light, allows most of the solar radiation (including visible light and infrared light) to enter the room, has high transmittance, and is reversible. VO is therefore added to the coating2VO coated on glass door and window at high temperature in summer2Infrared light can be reflected, so that the indoor temperature is reduced, and the refrigeration energy consumption is reduced; when the temperature is low in winter, VO2The phase change occurs, infrared light can penetrate through the coating to keep the indoor temperature, heating energy consumption is reduced, and the coating has an intelligent temperature control effect, so that energy is saved.
But VO2The phase transition temperature of the VO is 68 ℃ and far higher than the room temperature, and the VO needs to be regulated and controlled intelligently2The phase transition temperature of (a) falls below room temperature. Therefore, the invention uses W to VO through steps A) to C)2After doping and replacing V with W atom with larger radius, VO is stabilized2Is effective in making VO2The phase transition temperature is reduced to be lower than the room temperature, so that the transparent coating can intelligently regulate and control the room temperature in different seasons.
And because of VO2The coating has strong in-band and inter-band absorption in a short wavelength range, so that the coating is yellow gray, the visible light transmittance is low, and the application of the transparent coating is influenced. Therefore, the invention passes through steps D) to F) at VO2Ca-doped LaCrO coated on the surface3To prepare VO2As a nucleus, LaCrO3Is a core-shell structure modified filler of a shell. LaCrO3The material is a perovskite structure material, has a wider energy band gap and high visible light transmittance, and has good infrared radiation performance in an infrared band after being doped with Ca; adopting coprecipitation method to mix LaCrO3Coating VO2At the surface of (A), VO2The crystal can be recrystallized, the visible light transmittance of the coating can be effectively improved after coating, and VO (volatile organic compounds) can not be influenced2Intelligent temperature control performance.
Because the prepared modified filler powder has small particles, large specific surface area and high surface energy, and the agglomeration phenomenon is easy to occur, the invention uses dodecyl diamine hydrochloride to carry out surface modification on the modified filler powder, and-NH formed after protonation of amino in the dodecyl diamine hydrochloride3+LaCrO capable of being combined with modified filler shell3Hydrogen bonding is formed, so that adjacent LaCrO is formed3The crystal grains are crosslinked through the dodecyl long chain, so that the dispersion performance of the modified filler is effectively improved.
Therefore, the invention has the following beneficial effects:
(1) the transparent coating is produced by using high-boiling silicone oil as a raw material, so that organic silicon industrial byproducts can be effectively utilized, the waste is recycled, and the energy is saved and the environment is protected;
(2) VO is added into the transparent coating2As a nucleus, LaCrO3The core-shell structure of the shell is used as the modified filler, so that the coating has temperature control performance and good visible light transmittance, and can effectively save energy in winter and summer;
(3) the dodecyl diamine hydrochloride is used for carrying out surface modification on the modified filler, so that the modified filler has good dispersing performance, and the influence of filler agglomeration on the coating performance is avoided.
Detailed Description
The invention is further described with reference to specific embodiments.
Example 1:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 50 parts of high-boiling silicone oil, 50 parts of ethyl orthosilicate, 10 parts of dimethyl dimethoxy silane, 10 parts of modified filler, 0.05 part of dodecyl diamine hydrochloride, 0.7 part of glacial acetic acid, 0.07 part of acrylic acid alkali swelling thickener and 300 parts of ethanol.
The preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid with the mass fraction of 36% into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain dodecyl diamine hydrochloride.
The preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, stirring for 25min to obtain mixed solution, and adding VOSO in the mixed solution4·xH2O concentration of 0.25g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: 0.9; B) dropwise adding NaHCO with mass concentration of 6% into the mixed solution3The solution is stirred to react for 35min until the pH value of the system is 6.5, and the product is washed by deionized water and ethanol and then dried after being filtered;
C) calcining the dried product in nitrogen atmosphere at 820 ℃ for 3.5h, and cooling to obtain VO2Powder;
D) mixing the components in a molar ratio of 0.8: 1 La (NO)3)3·6H2O and Cr (NO)3)3·9H2Dissolving O in deionized water to obtain La (NO)3)3·6H2Adding 30 wt% of nitrate solution of O into the nitrate solutionAdding La (NO)3)3·6H2The molar ratio of O is 3: VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) dropwise adding 1.5mol/L ammonia water into the dispersion liquid under the stirring state to adjust the pH of the system to 4.5, and cleaning a product by using deionized water after filtering;
F) adding Cr (NO) to the cleaned product3)3·9H2The molar ratio of O is 0.2: ca (NO) of 13)2·4H2And O, stirring for 25min, drying at 85 ℃, and calcining at 820 ℃ for 2.5h to obtain the modified filler.
The preparation method of the weather-resistant organic silicon transparent temperature control coating comprises the following steps:
(1) adding dodecyl diamine hydrochloride into 30 parts of ethanol, stirring at 45 ℃ until the dodecyl diamine hydrochloride is dissolved, adding the modified filler, performing ultrasonic dispersion for 50min, then stirring at 45 ℃ for reaction for 1.5h, and cooling to obtain a modified filler dispersion liquid;
(2) mixing high-boiling silicone oil, a cross-linking agent and a chain extender in proportion to obtain a mixed solution, mixing a catalyst with the residual ethanol to obtain a catalyst solution, dropwise adding the catalyst solution into the mixed solution dropwise under the stirring state, and stirring and reacting for 4 hours at 50 ℃;
(3) dropwise adding the modified filler dispersion liquid and the thickening agent into the mixed liquid after reaction, and stirring for 25min to obtain the organic silicon transparent temperature-controlled coating.
Example 2:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 30 parts of high-boiling silicone oil, 30 parts of methyltrimethoxysilane, 5 parts of dimethyldiethoxysilane, 3 parts of modified filler, 0.01 part of dodecyl diamine hydrochloride, 0.1 part of glacial acetic acid, 0.01 part of acrylic acid alkali-soluble swelling thickener, 90 parts of ethanol and 10 parts of isopropanol.
The preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid with the mass fraction of 36% into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain dodecyl diamine hydrochloride.
The preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, stirring for 20min to obtain mixed solution, and adding VOSO in the mixed solution4·xH2O concentration of 0.2g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: 0.8; B) dropwise adding NaHCO with mass concentration of 5% into the mixed solution3The solution is stirred and reacted for 30min until the pH value of the system is 6, and the product is washed by deionized water and ethanol and dried after being filtered;
C) calcining the dried product at 800 ℃ for 3h in nitrogen atmosphere, and cooling to obtain VO2Powder;
D) mixing the components in a molar ratio of 0.7: 1 La (NO)3)3·6H2O and Cr (NO)3)3·9H2Dissolving O in deionized water to obtain La (NO)3)3·6H2Adding a nitrate solution with 20% of O by mass into the nitrate solution, and adding La (NO) into the nitrate solution3)3·6H2The molar ratio of O is 2: VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) dropwise adding 1mol/L ammonia water into the dispersion liquid under the stirring state to adjust the pH value of the system to 4, and cleaning the product with deionized water after filtering;
F) adding Cr (NO) to the cleaned product3)3·9H2The molar ratio of O is 0.1: ca (NO) of 13)2·4H2And O, stirring for 20min, drying at 80 ℃, and calcining at 800 ℃ for 3h to obtain the modified filler.
The preparation method of the weather-resistant organic silicon transparent temperature control coating comprises the following steps:
(1) adding dodecyl diamine hydrochloride into isopropanol, stirring at 40 ℃ until the dodecyl diamine hydrochloride is dissolved, adding the modified filler, performing ultrasonic dispersion for 60min, then stirring at 40 ℃ for reaction for 2h, and cooling to obtain a modified filler dispersion liquid;
(2) mixing high-boiling silicone oil, a cross-linking agent and a chain extender in proportion to obtain a mixed solution, mixing a catalyst and ethanol to obtain a catalyst solution, dropwise adding the catalyst solution into the mixed solution while stirring, and stirring for reaction at 40 ℃ for 5 hours;
(3) dropwise adding the modified filler dispersion liquid and the thickening agent into the mixed liquid after reaction, and stirring for 20min to obtain the organic silicon transparent temperature-controlled coating.
Example 3:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 60 parts of high-boiling silicone oil, 60 parts of methyl orthosilicate, 20 parts of dimethyl diethoxysilane, 15 parts of modified filler, 1 part of dodecyl diamine hydrochloride, 1 part of glacial acetic acid, 1 part of acrylic acid alkali swelling thickener and 500 parts of ethanol.
The preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid with the mass fraction of 36% into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain dodecyl diamine hydrochloride.
The preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, stirring for 30min to obtain mixed solution, and adding VOSO in the mixed solution4·xH2O concentration of 0.2g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: 1;
B) dropwise adding NaHCO with mass concentration of 8% into the mixed solution3The solution is stirred to react for 30min until the pH value of the system is 7, and the product is washed by deionized water and ethanol and then dried after being filtered;
C) calcining the dried product for 4 hours at 850 ℃ in a nitrogen atmosphere, and cooling to obtain VO2Powder;
D) mixing the components in a molar ratio of 0.9: 1 La (NO)3)3·6H2O and Cr (NO)3)3·9H2Dissolving O in deionized water to obtain La (NO)3)3·6H2Adding a nitrate solution with the mass fraction of O being 40% and La (NO) into the nitrate solution3)3·6H2The molar ratio of O is 4: VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) dropwise adding 2mol/L ammonia water into the dispersion liquid under the stirring state to adjust the pH value of the system to 5, and cleaning the product with deionized water after filtering;
F) adding Cr (NO) to the cleaned product3)3·9H2The molar ratio of O is 0.3: ca (NO) of 13)2·4H2And O, stirring for 30min, drying at 90 ℃, and calcining at 850 ℃ for 2h to obtain the modified filler.
The preparation method of the weather-resistant organic silicon transparent temperature control coating comprises the following steps:
(1) adding dodecyl diamine hydrochloride into isopropanol, stirring at 50 ℃ until the dodecyl diamine hydrochloride is dissolved, adding the modified filler, performing ultrasonic dispersion for 40min, then stirring at 50 ℃ for reaction for 1h, and cooling to obtain a modified filler dispersion liquid;
(2) mixing high-boiling silicone oil, a cross-linking agent and a chain extender in proportion to obtain a mixed solution, mixing a catalyst and ethanol to obtain a catalyst solution, dropwise adding the catalyst solution into the mixed solution while stirring, and stirring and reacting for 3 hours at 60 ℃;
(3) dropwise adding the modified filler dispersion liquid and the thickening agent into the mixed liquid after reaction, and stirring for 30min to obtain the organic silicon transparent temperature-controlled coating.
Comparative example 1:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 50 parts of high-boiling silicone oil, 50 parts of ethyl orthosilicate, 10 parts of dimethyl dimethoxy silane, 10 parts of modified filler, 0.05 part of dodecyl diamine hydrochloride, 0.7 part of glacial acetic acid, 0.07 part of acrylic acid alkali swelling thickener and 300 parts of ethanol.
The preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid with the mass fraction of 36% into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain dodecyl diamine hydrochloride.
The preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, stirring for 25min to obtain mixed solution, and adding VOSO in the mixed solution4·xH2O concentration of 0.25g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: 0.9;
B) dropwise adding NaHCO with mass concentration of 6% into the mixed solution3The solution is stirred to react for 35min until the pH value of the system is 6.5, and the product is washed by deionized water and ethanol and then dried after being filtered;
C) and calcining the dried product at 820 ℃ for 3.5h in a nitrogen atmosphere, and cooling to obtain the modified filler.
The preparation method of the weather-resistant organic silicon transparent temperature control coating is the same as that in the example 1.
Comparative example 2:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 50 parts of high-boiling silicone oil, 50 parts of ethyl orthosilicate, 10 parts of dimethyl dimethoxysilane, 10 parts of modified filler, 0.7 part of glacial acetic acid, 0.07 part of acrylic acid alkali swelling thickener and 300 parts of ethanol.
The preparation methods of the modified filler and the weather-resistant organic silicon transparent temperature control coating are the same as those in example 1.
Comparative example 3:
a weather-resistant organic silicon transparent temperature control coating comprises the following raw materials in parts by weight: 50 parts of high-boiling silicone oil, 50 parts of ethyl orthosilicate, 10 parts of dimethyl dimethoxy silane, 10 parts of modified filler, 0.05 part of dodecyl diamine hydrochloride, 0.7 part of glacial acetic acid, 0.07 part of acrylic acid alkali swelling thickener and 300 parts of ethanol.
The preparation method of the dodecyl diamine hydrochloride comprises the following steps: adding concentrated hydrochloric acid with the mass fraction of 36% into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain dodecyl diamine hydrochloride.
The preparation method of the modified filler comprises the following steps:
A) adding VOSO4·xH2O and Na2WO4·2H2Dissolving O in deionized water, stirring for 25min to obtain mixed solution, and adding VOSO in the mixed solution4·xH2O concentration of 0.25g/mL, VOSO4·xH2O and Na2WO4·2H2The molar ratio of O is 100: 0.9;
B) dropwise adding NaHCO with mass concentration of 6% into the mixed solution3The solution is stirred to react for 35min until the pH value of the system is 6.5, and the product is washed by deionized water and ethanol and then dried after being filtered;
C) calcining the dried product in nitrogen atmosphere at 820 ℃ for 3.5h, and cooling to obtain VO2Powder;
D) mixing the components in a molar ratio of 0.8: 1 La (NO)3)3·6H2O and Cr (NO)3)3·9H2Dissolving O in deionized water to obtain La (NO)3)3·6H2Adding a nitrate solution with 30% of O by mass into the nitrate solution, and adding La (NO) into the nitrate solution3)3·6H2The molar ratio of O is 3: VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) and dropwise adding 1.5mol/L ammonia water into the dispersion liquid under the stirring state to adjust the pH of the system to 4.5, filtering, washing the product with deionized water, drying at 85 ℃, and calcining at 820 ℃ for 2.5 hours to obtain the modified filler.
The preparation method of the weather-resistant organic silicon transparent temperature control coating is the same as that in the example 1.
The organic silicon transparent temperature control coatings prepared in the above examples and comparative examples were coated on a blank glass sample to prepare a sample plate, the thickness of the coating layer was 4mm, the basic performance of the coating layer was tested and compared with the blank glass sample, and the results are shown in table 1.
Wherein the visible light transmittance of the coating is tested by using an Shimadzu ultraviolet-visible light-near infrared spectrophotometer;
adhesion test method reference: GB 1720-1979(1989) paint film adhesion assay;
water resistance test method reference: GB/T1733-93 water resistance determination method of paint film;
heat resistance test methods refer to: GB1735-89(79) method for measuring heat resistance of paint films;
hardness test method reference: GB/T6739-1996 pencil method for film hardness;
reference of the water ultraviolet aging test method: ISO11507:2007 color paints and varnishes-Artificial weather aging Exposure of coatings-Exposure to fluorescent UV light and water.
The insulation performance of the test panels made in the above examples and comparative examples was tested by the following methods: a sample plate which is placed on a foam insulation box body with the thickness of 10cm and is irradiated by a 300W infrared light source with the distance of 30cm at the room temperature of 40 ℃ and 15 ℃ respectively, one side of the sample plate coated with the coating faces upwards, and the temperature rise value in the insulation box after 30min of irradiation is recorded by a temperature probe in the insulation box, and the result is shown in Table 2.
Table 2: and (5) testing the heat insulation performance.
| Item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Temperature rise (. degree. C.) at 40 ℃ C | 8 | 10 | 7 | 10 | 11 | 10 |
| Temperature rise (. degree.C.) at 15 ℃ C | 15 | 16 | 14 | 17 | 16 | 16 |
As can be seen from tables 1 and 2, the coatings prepared in examples 1 to 3 by using the raw materials and the method of the present invention have good adhesion, good weather resistance, high visible light transmittance, and good heat insulation performance at high temperature, and can allow infrared light to transmit at lower temperature to raise indoor temperature, thereby having good intelligent temperature control function.
In contrast, in comparative example 1, uncoated LaCrO was used3VO (a) of2As a filler, the visible light transmittance of the coating layer is significantly reduced compared to that in the examples, and the heat insulation performance at high temperature is also slightly reduced; the paint in the comparative example 2 does not add dodecyl diamine hydrochloride, the dispersibility of the modified filler is reduced, and the visible light transmittance and the heat-insulating property of the coating are reduced to some extent; VO in comparative example 32Surface-coated LaCrO3The thermal insulation performance of the coating at high temperature is also reduced without doping with Ca.
Claims (9)
1. A weather-resistant organic silicon transparent temperature control coating is characterized by comprising the following raw materials in parts by weight:
30-60 parts of high-boiling silicone oil
30-60 parts of cross-linking agent
5-20 parts of chain extender
3-15 parts of modified filler
0.01-1 part of dodecyl diamine hydrochloride
0.1 to 1 portion of catalyst
0.01-1 part of thickening agent
100-500 parts of a solvent;
the preparation method of the modified filler comprises the following steps:
A) adding VOSO4•xH2O and Na2WO4•2H2Dissolving O in deionized water, stirring for 20-30 min to obtain a mixed solution, wherein VOSO is contained in the mixed solution4•xH2The concentration of O is 0.2-0.3 g/mL, VOSO4•xH2O and Na2WO4•2H2The molar ratio of O is 100: (0.8 to 1);
B) dropwise adding NaHCO with mass concentration of 5-8% into the mixed solution3The pH value of the solution is 6-7, stirring and reacting for 30-40 min, filtering, washing the product with deionized water and ethanol, and drying;
C) calcining the dried product in a nitrogen atmosphere at 800-850 ℃ for 3-4 h, and cooling to obtain VO2Powder;
D) the molar ratio is (0.7-0.9): 1 La (NO)3)3•6H2O and Cr (NO)3)3•9H2Dissolving O in deionized water to obtain La (NO)3)3•6H2Adding a nitrate solution with the mass fraction of O being 20-40% and La (NO) into the nitrate solution3)3•6H2The molar ratio of O is (2-4): VO of 12Uniformly stirring the powder to obtain a dispersion liquid;
E) dropwise adding 1-2 mol/L ammonia water into the dispersion liquid under a stirring state to adjust the pH of the system to 4-5, and cleaning a product with deionized water after filtering;
F) adding into the cleaned productCr(NO3)3•9H2The molar ratio of O is (0.1-0.3): ca (NO) of 13)2•4H2And O, stirring for 20-30 min, drying at 80-90 ℃, and calcining at 800-850 ℃ for 2-3 h to obtain the modified filler.
2. The weather-resistant organosilicon transparent temperature-control coating as claimed in claim 1, wherein the preparation method of the dodecyl diamine hydrochloride comprises: adding concentrated hydrochloric acid into dodecyl diamine until the dodecyl diamine is completely dissolved, adding acetone into the solution until crystals are not separated out, and filtering, washing and drying to obtain the dodecyl diamine hydrochloride.
3. The weather-resistant organic silicon transparent temperature control coating as claimed in claim 1, wherein the cross-linking agent is one or a mixture of ethyl orthosilicate, methyl orthosilicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane and vinyltriethoxysilane.
4. The weather-resistant organosilicon transparent temperature-control coating as claimed in claim 1, wherein the chain extender is one or a mixture of two of dimethyldimethoxysilane and dimethyldiethoxysilane.
5. The weather-resistant organosilicon transparent temperature-control coating as claimed in claim 1, wherein the catalyst is one or a mixture of hydrochloric acid and glacial acetic acid.
6. The weather-resistant organosilicon transparent temperature-control coating as claimed in claim 1, wherein the solvent is one or more of ethanol, isopropanol, n-butanol, ethyl acetate, xylene, and toluene.
7. A preparation method of the weather-resistant type organic silicon transparent temperature control coating as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
(1) adding dodecyl diamine hydrochloride into 10-50 parts of solvent, stirring until the dodecyl diamine hydrochloride is dissolved, adding modified filler, stirring for reacting for 1-2 hours after ultrasonic dispersion, and cooling to obtain modified filler dispersion liquid;
(2) mixing high-boiling silicone oil, a cross-linking agent and a chain extender in proportion to obtain a mixed solution, mixing a catalyst with the rest solvent to obtain a catalyst solution, dropwise adding the catalyst solution into the mixed solution while stirring, and stirring for reaction for 3-5 hours;
(3) dropwise adding the modified filler dispersion liquid and the thickening agent into the mixed liquid after reaction, and stirring for 20-30 min to obtain the organic silicon transparent temperature-control coating.
8. The preparation method of the weather-resistant organic silicon transparent temperature control coating as claimed in claim 7, wherein the ultrasonic dispersion time in the step (1) is 40-60 min, and the reaction temperature is 40-50 ℃.
9. The preparation method of the weather-resistant organosilicon transparent temperature-control coating as claimed in claim 7, wherein the reaction temperature in step (2) is 40-60 ℃.
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Address after: 324000 No. 20 Huayin North Road, Quzhou City, Zhejiang Province, China Patentee after: Zhejiang Zhongtian Dongfang fluorosilicone Material Co.,Ltd. Address before: 324000 No. 20 Huayin North Road, Quzhou City, Zhejiang Province, China Patentee before: ZHONGTIAN DONGFANG FLUORINE SILICON MATERIAL Co.,Ltd. |