Degradable insulating paint, and preparation and use methods thereof

Abstract

The invention discloses a degradable insulating coating and a preparation and use method thereof. The degradable insulating coating contains (a) a cyclic carbonate monomer and / or a cyclic ester monomer; (b) an acrylate monomer; and (c) an organosilicon polymer, an acrylate monomer, a dispersion medium and a cross-linking agent, mixing the three components for reaction, and performing ultraviolet curing to obtain the degradable insulating coating. After the coating is degraded for 45 days in a simulated natural environment, the biological decomposition rate exceeds 89%, and the coating is an excellent environment-friendly material; the dielectric strength is greater than 21kV / mm, and the insulating property is superior to the national standard; the contact angle is larger than 150 degrees, and the rolling angle is smaller than 5.5 degrees, so that the super-hydrophobicity is achieved, and meanwhile, the removal of liquid attached to the surface is facilitated; the coating has good self-cleaning performance in a heavy pollution environment, dirt is difficult to adhere to the surface of the coating, and the coating has high surface pollution flashover resistance and is a degradable anti-pollution-flashover and anti-icing-flashover material with great application potential.

Description

Technical Field

[0001] The present invention relates to an insulating coating, and in particular to a degradable insulating coating, a preparation method and a use method thereof. Background Art

[0002] Insulators of transmission lines face severe challenges in complex environments. Conductive dirt accumulated under polluted conditions is likely to cause flashover, while ice flash caused by icing in low-temperature and humid environments also threatens the stable operation of the power grid. These two types of flashover phenomena not only cause large-scale power outages, but also result in direct economic losses of up to tens of billions of yuan every year, posing a continuous pressure on the safety of the power system.

[0003] Although the currently mainstream room temperature vulcanized silicone rubber (RTV) anti-fouling flashover coating can inhibit leakage current through surface hydrophobicity, its static contact angle is generally lower than 120°, and its dynamic hydrophobic recovery ability is insufficient, making it difficult to effectively block the formation of melting ice water film, resulting in weak anti-ice flash performance. In recent years, superhydrophobic coatings have attracted attention due to their characteristics of contact angle exceeding 150° and rolling angle less than 10°. The "air cushion effect" formed by their micro-nano composite structure can theoretically block both dirt adsorption and ice crystal anchoring at the same time. However, the structural vulnerability problems exposed in practical applications have become a bottleneck: mechanical wear caused by rainfall scouring, fracture of nano-protrusions caused by impact of sand and dust particles, and structural stress caused by ice-icing and melting cycles will all damage the surface roughness, resulting in the contact angle dropping suddenly below 120°, and the ice-repellent performance declining synchronously. More seriously, traditional fluorosilicon-based superhydrophobic materials are difficult to degrade, and their shed fragments may cause soil heavy metal pollution, conflicting with increasingly strict environmental protection regulations.

[0004] At present, there is no protective coating that can break through the dual limitations of the material system and structural design to form a comprehensive solution with the characteristics of anti-fouling flashover, anti-icing and ecological safety. Summary of the Invention

[0005] Object of the Invention: The object of the present invention is to provide a degradable insulating coating with superhydrophobic dust-proof performance, and the second object is to provide a preparation method and a use method of the coating.

[0006] Technical Solution: The degradable insulating coating described in the present invention contains:

[0007] (a) cyclic carbonate monomer and / or cyclic ester monomer;

[0008] (b) acrylate monomer;

[0009] (c) organosilicon polymer, acrylate monomer, dispersion medium, crosslinking agent;

[0010] Among them, the mass ratio of the silicone polymers in component (a), component (b) and component (c) is 0.5-1:0.5-1:0.5-1; the mass ratio of the silicone polymer, acrylate monomer, dispersion medium and crosslinking agent in (c) is 0.5-1:0.0005-0.001:0.5-1:0.1-0.2.

[0011] Preferably, the component (a) is selected from caprolactone, lactide, trimethylene carbonate.

[0012] Preferably, the component (b) is selected from methyl methacrylate, isothiazolinone acrylate, isothiazolinone methacrylate, indole acrylate, indole methacrylate, isothiazolinone-indole acrylate.

[0013] Preferably, the silicone polymer in the component (c) is selected from perhydropolysilazane, dihydroxyhydrocarbyl polydimethylsiloxane; the dispersion medium is selected from dichloromethane, n-butyl ether, n-hexane, ethyl acetate, perfluorocyclohexane, perfluorotoluene, perfluoroheptane; the crosslinking agent is polyethylene glycol.

[0014] The preparation method of the degradable insulating coating of the present invention is characterized in that the steps include:

[0015] (1) Purify the cyclic carbonate monomer and / or cyclic ester monomer to obtain component (a);

[0016] (2) Purify the acrylate monomer to obtain component (b);

[0017] (3) Mix the silicone polymer and the dispersion medium in a mass ratio of 0.5-1:0.5-1, add a crosslinking agent of 10-20% of the mass of the dispersion medium and an acrylate monomer of 1-5% of the mass of the dispersion medium, and react to obtain component (c).

[0018] Preferably, in step 1, the purification step includes:

[0019] (11) Mix ethylene glycol, methanol, sodium, and the substance to be purified in a mass ratio of 0.5-1:0.5-1:0.2-0.6:0.2-0.6, heat to reflux under a nitrogen protective atmosphere and then perform vacuum distillation;

[0020] (12) Rinse the product of step 11 with an aqueous sodium carbonate solution, dry with potassium carbonate, and distill with calcium hydride,

[0021] Among them, the concentration of the aqueous sodium carbonate solution is 5%, the mass of potassium carbonate is the same as that of the substance to be purified, the mass of calcium hydride is 50% of the substance to be purified, and the distillation temperature is 65-75°C.

[0022] Preferably, in step 2, the purification step includes mixing calcium hydride and the substance to be purified at a mass ratio of 0.5-1:0.5-1, drying and then performing vacuum distillation, wherein the distillation temperature is 65-75°C and the pressure is 0.8-0.9 times the standard atmospheric pressure.

[0023] Preferably, in step 3, the reaction temperature is 20-30°C, the reaction time is 2-5 h, and nitrogen is used as the protective atmosphere for the reaction.

[0024] The method for using the degradable insulating coating according to the present invention is characterized in that the steps include:

[0025] (1) Mix components a, b, and c in the degradable insulating coating, and react for at least 0.5 h after coating;

[0026] (2) Irradiate and cure with ultraviolet light having a wavelength of 100-200 nm to obtain a degradable insulating coating.

[0027] Preferably, in step 2, the irradiation intensity is 0.05-0.2 kW / cm 2 , and the curing time is not less than 0.5 h.

[0028] Beneficial effects: Compared with the prior art, the present invention has the following remarkable advantages:

[0029] 1. After the coating prepared from the degradable insulating coating is simulated to degrade in a natural environment for 45 days, the biodegradation rate exceeds 89%, and it is an excellent environmentally friendly material;

[0030] 2. The dielectric strength of the coating prepared from the degradable insulating coating is greater than 21 kV / mm, and the insulation performance is better than the national standard;

[0031] 3. The contact angle of the coating prepared from the degradable insulating coating is greater than 150°, and the rolling angle is less than 5.5°. While having superhydrophobicity, it is beneficial to the exclusion of the liquid attached to the surface;

[0032] 4. The coating prepared from the degradable insulating coating exhibits good self-cleaning performance in a heavily polluted environment, and it is difficult for dirt to adhere to the surface of the coating, and it has strong resistance to surface flashover;

[0033] 5. Based on the above advantages, the coating prepared from the degradable insulating coating is a degradable anti-flashover and anti-ice flashover material with great application potential. Description of the Drawings

[0034] Figure 1 It is a graph showing the relationship between the equivalent salt deposit density and the test time of the degradable insulating coatings obtained in Examples 1-3;

[0035] Figure 2Graph showing the test results of the hydrophobic properties of the degradable insulating coatings obtained in Examples 1-3;

[0036] Figure 3 Graph showing the test results of the insulating properties of the degradable insulating coatings obtained in Examples 1-3;

[0037] Figure 4 Graph showing the test results of the degradable properties of the degradable insulating coatings obtained in Examples 1-3. Detailed implementation mode

[0038] The technical solution of the present invention will be further described below.

[0039] Example 1:

[0040] (1) Ethylene glycol, methanol, sodium, and caprolactone with a mass ratio of 1:1:0.4:0.4 were mixed, heated to reflux under a nitrogen protective atmosphere, and distilled under vacuum at 70°C for 3 h; after rinsing 5 times with 5% sodium carbonate aqueous solution, 10 g of potassium carbonate was added for drying, and after filtration, 5 g of calcium hydride was added and distilled at 70°C to obtain purified caprolactone, which is component a,

[0041] where the mass of ethylene glycol is 25.0 g, the mass of methanol is 25.0 g, the mass of sodium is 10.0 g, and the mass of caprolactone is 10 g;

[0042] (2) Calcium hydride and methyl methacrylate with a mass ratio of 1:2 were mixed, dried for 1 h, and distilled at 70°C for 2 h under 0.9 times the standard atmospheric pressure to obtain purified methyl methacrylate, which is component b,

[0043] where the mass of calcium hydride is 5 g and the mass of methyl methacrylate is 10 g;

[0044] (3) Perhydropolysilazane and dichloromethane with a mass ratio of 1:1 were mixed, and 16.667% of the mass of the dispersing medium of polyethylene glycol and 3.333% of the mass of the dispersing medium of methyl methacrylate were added dropwise, and the reaction was carried out at 25°C for 3 hours to obtain component c,

[0045] where the mass of perhydropolysilazane is 10 g, the mass of dichloromethane is 10 g, the mass of polyethylene glycol is 1.667 g, and the mass of methyl methacrylate is 0.333 g;

[0046] (4) The components a, b, and c obtained in the above steps were mixed, and the mass ratio of caprolactone, methyl methacrylate, and perhydropolysilazane contained therein was 1:1:1, and spin-coated on a silicon wafer at 5000 rpm for 30 s, and after coating, ring-opening polymerization reaction was carried out at room temperature for 0.5 h;

[0047] (5) Ultraviolet light with a wavelength of 172 nm, 0.1 kW / cm 2Irradiate and cure with power for 0.5 h to obtain a degradable insulating coating.

[0048] Example 2:

[0049] Referring to the preparation steps described in Example 1, in step 1, lactide was used to replace caprolactone, and the remaining steps were the same, to obtain a degradable insulating coating.

[0050] Example 3:

[0051] Referring to the preparation steps described in Example 1, in step 1, trimethylene carbonate was used to replace caprolactone, and the remaining steps were the same, to obtain a degradable insulating coating.

[0052] Test Example 1:

[0053] The silicon wafers with the degradable insulating coatings prepared in Examples 1-3 were used as specimens and hung in the same environment. A high-pressure mercury lamp was used to simulate sunlight. During the test, a contamination solution composed of deionized water, kaolin, and NaCl with a mass ratio of 100:10:1 was used. The test was carried out for 120 h. During this period, the contamination solution was sprayed on the specimens every 5 h. At the same time, according to the method described in Appendix C of GB / T 26218.1-2010, the change of the equivalent salt deposit density of the coatings obtained in Examples 1-3 with time was measured. The results are as Figure 1 shown. The degradable insulating coatings prepared by the present invention show good self-cleaning performance, and it is difficult for contaminants to adhere to the coating surface, and they have strong resistance to surface flashover.

[0054] Test Example 2:

[0055] According to the method described in GB / T 30693-2014, the contact angles of the coatings obtained in Examples 1-3 were measured. The results are as Figure 2 shown. The contact angles of the three coatings are all greater than 150°, and they are superhydrophobic coatings; and the rolling angles of the three coatings are all less than 5.5°, which is beneficial to the exclusion of the liquid attached to the surface.

[0056] Test Example 3:

[0057] According to the method described in GB / T 1408.1-2016, the dielectric strength of the coatings obtained in Examples 1-3 was measured. The results are as Figure 3 shown. The dielectric strengths of the three coatings are all greater than 21 kV / mm, and their insulation performance is excellent, meeting the national standards.

[0058] Test Example 4:

[0059] According to the method described in GB / T 19277.2-2013, the degradation performance of the coatings obtained in Examples 1-3 was measured. The results are as Figure 4As shown, the mass remaining of the three coatings after 45 days does not exceed 11%, that is, the biodegradation rate exceeds 89%, with excellent degradability and meeting the national standards.

Claims

1. A degradable insulating coating, characterized in that, The coating contains: (a) cyclic carbonate monomer and / or cyclic ester monomer; (b) acrylate monomer; (c) silicone polymer, acrylate monomer, dispersion medium, crosslinking agent; wherein, the mass ratio of the silicone polymer in component (a), component (b) and component (c) is 0.5-1:0.5-1:0.5-1; the mass ratio of the silicone polymer, acrylate monomer, dispersion medium, and crosslinking agent in (c) is 0.5-1:0.01-0.05:0.5-1:0.1-0.

2.

2. The degradable insulating coating according to claim 1, wherein The component (a) is selected from caprolactone, lactide, trimethylene carbonate.

3. The biodegradable insulating coating according to claim 1, characterized in that, The component (b) is selected from methyl methacrylate, isothiazolinone acrylate ester, isothiazolinone methacrylate ester, indole acrylate, indole methacrylate, isothiazolinone-indole acrylate.

4. The degradable insulating coating according to claim 1, characterized in that, The silicone polymer in the component (c) is selected from perhydropolysilazane, dihydroxyhydrocarbyl polydimethylsiloxane; the dispersion medium is selected from dichloromethane, n-butyl ether, n-hexane, ethyl acetate, perfluorocyclohexane, perfluorotoluene, perfluoroheptane; the crosslinking agent is polyethylene glycol.

5. A method for preparing the degradable insulating coating according to any one of claims 1-4, characterized in that the steps It includes: (1) Purify the cyclic carbonate monomer and / or cyclic ester monomer to obtain component (a); (2) Purify the acrylate monomer to obtain component (b); (3) Mix the silicone polymer and the dispersion medium with a mass ratio of 0.5-1:0.5-1, add a crosslinking agent accounting for 10-20% of the mass of the dispersion medium and an acrylate monomer accounting for 1-5% of the mass of the dispersion medium, and react to obtain component (c).

6. The preparation method according to claim 5, characterized in that, In step 1, the purification step includes: (11) Mix ethylene glycol, methanol, sodium, and the substance to be purified with a mass ratio of 0.5-1:0.5-1:0.2-0.6:0.2-0.6, heat to reflux under a nitrogen protective atmosphere, and then perform vacuum distillation; (12) Rinse the product of step 11 with an aqueous sodium carbonate solution, dry with potassium carbonate, and distill with calcium hydride.

7. The preparation method according to claim 5, characterized in that, In step 2, the purification step includes mixing calcium hydride and the substance to be purified with a mass ratio of 0.5-1:0.5-1, drying, and then performing vacuum distillation under reduced pressure.

8. The preparation method according to claim 5, characterized in that, In step 3, the reaction temperature is 20-30 °C, the reaction time is 2-5 h, and the reaction is carried out under a nitrogen protective atmosphere.

9. A method for using the degradable insulating coating according to any one of claims 1-4, characterized in that the steps It includes: (1) Mix components a, b, and c in the degradable insulating coating, coat and react for at least 0.5 h; (2) Irradiate and cure with ultraviolet light with a wavelength of 100-200 nm to obtain a degradable insulating coating.

10. The usage method according to claim 9, wherein, In Step 2, the irradiation intensity is 0.05 - 0.2 kW / cm 2 , and the curing time is not less than 0.5 h.

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