Preparation method and application of water-based anti-pollution coating
The water-based anti-pollution coating technology, which combines organosilicon triazine polymer with nano-silica, solves the problem of insufficient waterproof, dustproof and pollution-proof performance of epoxy resin coatings, and improves superhydrophobic properties and heat resistance, thereby improving the efficiency and reliability of solar photovoltaic modules.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHANGZHOU HUAMEI PHOTOVOLTAIC MATERIALS
- Filing Date
- 2025-07-30
- Publication Date
- 2026-06-09
Smart Images
Figure BDA0005525861760000021 
Figure BDA0005525861760000031 
Figure BDA0005525861760000042
Abstract
Description
Technical Field
[0001] This invention relates to the field of superhydrophobic coating technology, specifically to a method for preparing and applying a water-based anti-pollution coating. Background Technology
[0002] Currently, solar photovoltaic (PV) power plants are mainly installed in relatively open, sparsely populated areas. These areas often experience strong winds and sandstorms, which can form a layer of sand on the surface of the solar panels, affecting their light transmittance and even heat dissipation performance, potentially damaging the panels or cells and impacting overall PV efficiency. Applying a coating to the surface of solar panels can improve their anti-fouling properties and reduce reflectivity, thus enhancing PV efficiency. Superhydrophobic coatings possess excellent waterproof, dustproof, and anti-fouling properties, and have broad application prospects in fields such as construction, transportation, energy, and electronic communications.
[0003] Epoxy resins are widely used due to their high transparency, excellent corrosion resistance, and good mechanical strength. However, ordinary epoxy resin coatings lack superhydrophobic properties and have poor waterproof, dustproof, and pollution-proof performance, limiting their practical application in areas such as pollution prevention for solar panel modules. Nano-silica, with its small particle size and large specific surface area, can construct a rough structure on the resin coating surface, imparting superhydrophobic properties. Furthermore, nano-silica has a low refractive index, making it important for antireflective coatings in solar panel modules. Polysiloxanes, polymers with strong hydrophobicity, good heat resistance, and chemical stability, can be combined with inorganic nanomaterials to enable epoxy resin and other coatings to exhibit superhydrophobic properties. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention provides a method for preparing and applying a water-based anti-fouling coating, which solves the problem of epoxy resin's superhydrophobicity and poor anti-fouling performance.
[0005] The technical solution of this invention is as follows: A method for preparing a water-based anti-pollution coating: 40-70 parts by weight of organosilicon triazine polymer are added to acetone, and after stirring, 100 parts by weight of water-based epoxy resin emulsion, 10-30 parts by weight of nano-silica, 0.3-0.5 parts by weight of dispersant, 0.6-1 parts by weight of emulsifier, and 0.4-0.7 parts by weight of defoamer are added. The mixture is sheared and dispersed, and then 0.8-1.3 parts by weight of curing accelerator and 32-40 parts by weight of curing agent are added. After stirring, the emulsion is coated onto the surface of the substrate and heat-cured to obtain a water-based anti-pollution coating.
[0006] Furthermore, the curing accelerator includes DMP-30.
[0007] Furthermore, the curing agents include methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.
[0008] Furthermore, the thermosetting method involves first curing at 100-120℃ for 3-4 hours, and then curing at 140-150℃ for 6-8 hours.
[0009] Further, the preparation method of organosilicon triazine polymer includes: adding 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and triethylamine to xylene under a nitrogen atmosphere, adding dimethyldichlorosilane dropwise at 15-30℃, then heating to 60-80℃ and stirring for 12-18h, finally adding 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine, stirring for 40-60min, extracting and washing with water, distilling the organic layer under reduced pressure, washing the product with petroleum ether and ethanol, and drying to obtain organosilicon triazine polymer.
[0010] The preparation reaction formula is:
[0011]
[0012] Furthermore, the molar ratio of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine, triethylamine, and dimethyldichlorosilane is (1.04-1.1):(2-2.2):1.
[0013] Further, the preparation method of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine includes: adding an aliphatic amine, potassium hydroxide, and 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to tetrahydrofuran, stirring the reaction at 20-40℃ for 12-18 h, distilling under reduced pressure, washing the product sequentially with water and petroleum ether, and then recrystallizing in ethanol to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine. The preparation reaction formula is:
[0014]
[0015] Furthermore, the molar ratio of fatty amine, potassium hydroxide, and 3-(2,4-dihydroxyphenyl)-1,3,5-triazine is (2-2.2):(2-2.1):1.
[0016] Furthermore, the molecular formula of aliphatic amines is NH2-C. a H 2a+1 , where a is any integer from 12 to 18.
[0017] Furthermore, water-based anti-fouling coatings are applied to anti-reflective coatings for solar modules.
[0018] The beneficial technical effects of this invention are as follows: 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and dimethyldichlorosilane are polymerized to obtain an organosilicon triazine polymer containing terminal hydroxyl groups and long carbon chains. Then, it is mixed with nano-silica, waterborne epoxy resin, emulsifier, curing agent, etc. and thermocured to obtain a waterborne anti-pollution coating.
[0019] The organosilicon triazine polymer of the present invention contains terminal hydroxyl groups. During the high-temperature curing process, it undergoes a ring-opening curing reaction with epoxy resin, thereby bonding the heat-resistant phenylsiloxane structure and phenyltriazine ring structure into the epoxy resin molecular chain, which is beneficial to improving the heat resistance of the coating.
[0020] The organosilicon triazine polymer of the present invention contains multiple long carbon chains with strong hydrophobicity and a phenylsiloxane structure, which significantly improves the hydrophobicity of the epoxy resin coating and significantly increases the water contact angle of the coating. Combined with nano-silica, it endows the coating surface with unique superhydrophobic properties, strong anti-settling, waterproof and anti-pollution performance, and excellent resistance to damp heat. Detailed Implementation
[0021] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0022] 3-(2,4-dihydroxyphenyl)-1,3,5-homogeneous triazine was prepared according to the method described in the October 2008 issue of the journal *Journal of Beijing Institute of Fashion Technology*, Vol. 28, No. 4. The method involved adding 0.03 mol of cyanuric chloride to 120 mL of chlorobenzene, followed by the addition of 0.033 mol of aluminum trichloride and 0.036 mol of resorcinol at 5 °C. The reaction was allowed to proceed for 8 h. The solution was then poured into 120 mL of water, the pH was adjusted to 2, and the mixture was allowed to stand for 18 h. After filtration, the product was washed with ether and then added to acetone. The mixture was heated to 50 °C, filtered while hot, and dried to obtain 3-(2,4-dihydroxyphenyl)-1,3,5-homogeneous triazine, with the structural formula [not provided].
[0023] Example 1
[0024] (1) Add 1 mol tetradecylamine, 1 mol potassium hydroxide, and 0.5 mol 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to 6 L of tetrahydrofuran. Stir the reaction mixture at 20 °C for 18 h. Distill under reduced pressure, wash the product sequentially with water and petroleum ether, and then recrystallize in ethanol to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine. The structural formula is...
[0025] (2) In a nitrogen atmosphere, 1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and 2 mol of triethylamine were added to 1.5 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 15 °C. The mixture was then heated to 75 °C and stirred for 18 h. Finally, 0.04 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine was added and stirred for 60 min. The mixture was then extracted and washed with water, the organic layer was distilled under reduced pressure, and the product was washed with petroleum ether and ethanol and dried to obtain the organosilicon triazine polymer.
[0026] (3) Add 200g of organosilicon triazine polymer to 400mL of acetone, stir, and then add 500g of waterborne epoxy resin emulsion (model DER-WB3002, solid content 46%), 150g of nano silica (average particle size 200nm, the same below), 2.5g of dispersant (SN-DISPERSANT 5040, the same below), 3g of emulsifier (Huaxiang Kejie PEG-9 methyl ether polydimethylsiloxane), and 2.5g of defoamer (model DIG825, the same below). Shear and disperse, then add 5.3g of curing accelerator DMP-30 and 190g of curing agent methyl hexahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 120℃ for 3h, and then cure at 150℃ for 6h to obtain a waterborne anti-pollution coating.
[0027] Example 2
[0028] (1) Add 1.1 mol octadecylamine, 1 mol potassium hydroxide, and 0.5 mol 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to 8 L of tetrahydrofuran. Stir the reaction at 40 °C for 12 h. Distill under reduced pressure, wash the product with water and petroleum ether in turn, and then recrystallize in ethanol to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine.
[0029] (2) In a nitrogen atmosphere, 1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and 2.2 mol of triethylamine were added to 2 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 30 °C. The mixture was then heated to 60 °C and stirred for 18 h. Finally, 0.1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine was added and stirred for 40 min. The mixture was then extracted and washed with water, the organic layer was distilled under reduced pressure, and the product was washed with petroleum ether and ethanol and dried to obtain the organosilicon triazine polymer.
[0030] (3) Add 250g of organosilicon triazine polymer to 500mL of acetone, stir, then add 500g of waterborne epoxy resin emulsion, 120g of nano silica, 2.2g of dispersant, 4.3g of emulsifier, and 2g of defoamer. Shear and disperse, then add 4g of curing accelerator DMP-30 and 200g of curing agent methyl hexahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 100℃ for 4h, then cure at 150℃ for 6h to obtain a waterborne anti-pollution coating.
[0031] Example 3
[0032] (1) Add 1 mol dodecylamine, 1.05 mol potassium hydroxide and 0.5 mol 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to 7 L of tetrahydrofuran. Stir the reaction at 25 °C for 18 h. Distill under reduced pressure and wash the product with water and petroleum ether in turn. Then recrystallize in ethanol to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine.
[0033] (2) In a nitrogen atmosphere, 1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and 2 mol of triethylamine were added to 1.5 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 20 °C. The mixture was then heated to 80 °C and stirred for 12 h. Finally, 0.06 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine was added and stirred for 60 min. The mixture was then extracted and washed with water, the organic layer was distilled under reduced pressure, and the product was washed with petroleum ether and ethanol and dried to obtain the organosilicon triazine polymer.
[0034] (3) Add 300g of organosilicon triazine polymer to 500mL of acetone, stir, then add 500g of waterborne epoxy resin emulsion, 80g of nano silica, 1.7g of dispersant, 4.2g of emulsifier, and 3g of defoamer. Shear and disperse, then add 5.8g of curing accelerator DMP-30 and 160g of curing agent methyltetrahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 110℃ for 4h, then cure at 140℃ for 8h to obtain a waterborne anti-pollution coating.
[0035] Example 4
[0036] (1) In a nitrogen atmosphere, 1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine (prepared in the same way as in Example 1) and 2 mol of triethylamine were added to 1.5 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 30 °C. The mixture was then heated to 70 °C and stirred for 18 h. Finally, 0.1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine was added and stirred for 60 min. The mixture was then extracted and washed with water, the organic layer was distilled under reduced pressure, and the product was washed with petroleum ether and ethanol and dried to obtain the organosilicon triazine polymer.
[0037] (3) Add 350g of organosilicon triazine polymer to 500mL of acetone, stir, then add 500g of waterborne epoxy resin emulsion, 50g of nano silica, 1.5g of dispersant, 5g of emulsifier, and 3.5g of defoamer. Shear and disperse, then add 6.5g of curing accelerator DMP-30 and 160g of curing agent methyltetrahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 110℃ for 4h, then cure at 140℃ for 8h to obtain a waterborne anti-pollution coating.
[0038] Comparative Example 1
[0039] (1) Add 150g of nano silica, 2.5g of dispersant, 3g of emulsifier and 2.5g of defoamer to 500g of waterborne epoxy resin emulsion, shear and disperse, then add 5.3g of curing accelerator DMP-30 and 190g of curing agent methyl hexahydrophthalic anhydride, stir and coat the emulsion onto the surface of the substrate, first cure at 120℃ for 3h, then cure at 150℃ for 6h to obtain waterborne anti-pollution coating.
[0040] Comparative Example 2
[0041] (3) Add 200g of dihydroxy-terminated polysiloxane (model Kemikel1258437) to 400mL of acetone, stir, then add 500g of waterborne epoxy resin emulsion, 150g of nano silica, 2.5g of dispersant, 3g of emulsifier, and 2.5g of defoamer. Shear and disperse, then add 5.3g of curing accelerator DMP-30 and 190g of curing agent methyl hexahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 120℃ for 3h, then cure at 150℃ for 6h to obtain a waterborne anti-pollution coating.
[0042] Comparative Example 3
[0043] (1) In a nitrogen atmosphere, 1 mol of resorcinol and 2 mol of triethylamine were added to 1.5 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 15 °C. The mixture was then heated to 75 °C and stirred for 18 h. Finally, 0.04 mol of resorcinol was added and stirred for 60 min. The mixture was then extracted and washed with water. The organic layer was distilled under reduced pressure. The product was washed with petroleum ether and ethanol and dried to obtain the organosilicon polymer.
[0044] (2) Add 200g of organosilicon polymer to 400mL of acetone, stir, then add 500g of waterborne epoxy resin emulsion, 150g of nano silica, 2.5g of dispersant, 3g of emulsifier, and 2.5g of defoamer. Shear and disperse, then add 5.3g of curing accelerator DMP-30 and 190g of curing agent methyl hexahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 120℃ for 3h, then cure at 150℃ for 6h to obtain a waterborne anti-pollution coating.
[0045] Comparative Example 4
[0046] (1) Add 1 mol of n-propylamine, 1 mol of potassium hydroxide, and 0.5 mol of 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to 6 L of tetrahydrofuran. Stir the reaction mixture at 20 °C for 18 h. Distill under reduced pressure, wash the product sequentially with water and petroleum ether, and then recrystallize in ethanol to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine. The structural formula is...
[0047] (2) In a nitrogen atmosphere, 1 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and 2 mol of triethylamine were added to 1.5 L of xylene. 1 mol of dimethyldichlorosilane was added dropwise at 15 °C. The mixture was then heated to 75 °C and stirred for 18 h. Finally, 0.04 mol of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine was added and stirred for 60 min. The mixture was then extracted and washed with water, the organic layer was distilled under reduced pressure, and the product was washed with petroleum ether and ethanol and dried to obtain the organosilicon triazine polymer.
[0048] (3) Add 200g of organosilicon triazine polymer to 400mL of acetone, stir, and then add 500g of waterborne epoxy resin emulsion (model DER-WB3002, solid content 46%), 150g of nano silica (average particle size 200nm, the same below), 2.5g of dispersant (SN-DISPERSANT 5040, the same below), 3g of emulsifier (Huaxiang Kejie PEG-9 methyl ether polydimethylsiloxane), and 2.5g of defoamer (model DIG825, the same below). Shear and disperse, then add 5.3g of curing accelerator DMP-30 and 190g of curing agent methyl hexahydrophthalic anhydride. After stirring, coat the emulsion onto the substrate surface, first cure at 120℃ for 3h, and then cure at 150℃ for 6h to obtain a waterborne anti-pollution coating.
[0049] The water contact angle of the coating was tested according to GB / T 30447-2013 standard. The resistance to damp heat was tested according to GB / T1740-2007 standard, with a relative humidity of 96±2%, a temperature of 80℃, and a time of 360h.
[0050] Table 1 Performance Tests of Coatings
[0051] Water contact angle (°) Moist heat resistance rating Example 1 151.7 2 Example 2 153.3 1 Example 3 154.6 1 Example 4 151.0 1 Comparative Example 1 96.4 5 Comparative Example 2 120.5 4 Comparative Example 3 131.8 3 Comparative Example 4 136.6 3
[0052] Compared to Comparative Examples 1-4, the epoxy resin-nano silica coating systems of Examples 1-4 incorporated an organosilicon triazine polymer containing terminal hydroxyl groups. During high-temperature curing, this polymer undergoes a ring-opening curing reaction with the epoxy resin, thereby transforming the heat-resistant phenylsiloxane structure... and phenyltriazine ring The structure is bonded to the epoxy resin molecular chain, which helps to improve the heat resistance of the coating. In addition, the organosilicon triazine polymer contains multiple long carbon chains with strong hydrophobicity and phenylsiloxane structure, which significantly improves the hydrophobicity of the epoxy resin coating and significantly increases the water contact angle of the coating, giving the coating unique superhydrophobic properties, strong anti-settling, waterproof and anti-pollution performance, and excellent resistance to damp heat.
[0053] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.
Claims
1. A method for preparing a water-based anti-fouling coating, characterized in that, The preparation method includes: adding 40-70 parts by weight of organosilicon triazine polymer to acetone, stirring, then adding 100 parts by weight of waterborne epoxy resin emulsion, 10-30 parts by weight of nano-silica, 0.3-0.5 parts by weight of dispersant, 0.6-1 parts by weight of emulsifier and 0.4-0.7 parts by weight of defoamer, shearing and dispersing, then adding 0.8-1.3 parts by weight of curing accelerator and 32-40 parts by weight of curing agent, stirring, coating the emulsion onto the substrate surface, and heat curing to obtain a waterborne anti-pollution coating; The preparation method of the organosilicon triazine polymer includes: adding 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and triethylamine to xylene under a nitrogen atmosphere, adding dimethyldichlorosilane dropwise at 15-30°C, then heating to 60-80°C and stirring for 12-18 hours, finally adding 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine and stirring for 40-60 minutes, extracting the organic layer by vacuum distillation, washing the product, and drying to obtain the organosilicon triazine polymer; The molar ratio of 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine, triethylamine, and dimethyldichlorosilane is (1.04-1.1):(2-2.2):1; The preparation method of the 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine includes: adding aliphatic amine, potassium hydroxide, and 3-(2,4-dihydroxyphenyl)-1,3,5-triazine to tetrahydrofuran, stirring the reaction at 20-40℃ for 12-18 h, distilling under reduced pressure, washing the product, and recrystallizing to obtain 2-(2,4-dihydroxyphenyl)-4,6-dialiphatic aminotriazine.
2. The method for preparing the water-based anti-fouling coating according to claim 1, characterized in that, The curing accelerator includes DMP-30, and the curing agent includes methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.
3. The method for preparing the water-based anti-fouling coating according to claim 1, characterized in that, The thermosetting method involves first curing at 100-120℃ for 3-4 hours, and then curing at 140-150℃ for 6-8 hours.
4. The method for preparing the water-based anti-fouling coating according to claim 1, characterized in that, The molar ratio of the fatty amine, potassium hydroxide, and 3-(2,4-dihydroxyphenyl)-1,3,5-triazine is (2-2.2):(2-2.1):
1.
5. The method for preparing the water-based anti-fouling coating according to claim 4, characterized in that, The molecular formula of the fatty amine is NH2-C a H 2a+1 , where a is any integer from 12 to 18.
6. The application of an aqueous anti-fouling coating obtained by the preparation method according to any one of claims 1-5 in an anti-reflection coating for solar modules.