Low-ice-adhesion super-hydrophobic anti-icing coating as well as preparation method and application thereof

Abstract

The invention relates to a low-ice-adhesion super-hydrophobic anti-icing coating as well as a preparation method and application thereof. Single-end amino fluorosilicone oil is grafted to the surface of an aldehyde group functionalized metal organic framework material through an amino-aldehyde group condensation reaction to obtain a hydrophobically modified metal organic framework material, the hydrophobically modified metal organic framework material is compounded with a synthesized fluorinated acrylate copolymer, and the coating is prepared through ultrasonic dispersion and spraying curing processes. According to the prepared low-ice-adhesion super-hydrophobic anti-icing coating, through the synergistic effect of fluorosilane grafting modification and a micro-nano structure, the excellent performance that the static water contact angle is larger than or equal to 160 degrees, the rolling angle is smaller than or equal to 2 degrees, and the ice adhesion strength is smaller than or equal to 20 kPa is achieved. Compared with a traditional anti-icing coating, a metal organic framework material functional modification strategy is adopted, the ice adhesion force is remarkably reduced while the mechanical stability of the coating is kept, and uniform film forming on the surfaces of base materials such as aluminum wires can be achieved through the spraying technology. The coating is suitable for anti-icing protection of the aluminum conductor of the power transmission line, and has the characteristics of long-acting icing resistance and low ice adhesion.

Description

Technical Field

[0001] This invention relates to the field of superhydrophobic materials technology, and in particular to a low-ice-adhesion superhydrophobic anti-icing coating, its preparation method, and its application. Background Technology

[0002] Surface icing poses a severe challenge to modern industrial infrastructure and operations in extreme environments. Particularly in the power transmission sector, icing on aluminum conductors of transmission lines can lead to major accidents such as conductor breakage and tower collapse, seriously threatening the safe operation of the power grid. Statistics show that direct economic losses caused by icing on transmission lines in my country reach billions of yuan annually, and power outages caused by ice storms in extreme weather conditions can affect millions of users. Traditional de-icing methods, such as electric de-icing and mechanical de-icing, can alleviate the problem, but they suffer from drawbacks such as high energy consumption (electric de-icing consumes thousands of kilowatts), high operational risks (mechanical vibration can easily damage conductors), and strong environmental dependence. While chemical anti-icing agents can lower the freezing point, their durability is poor and they easily pollute the environment, making them unsuitable for long-term outdoor protection.

[0003] Superhydrophobic technology, with its self-cleaning effect and delayed icing properties, is considered a breakthrough anti-icing strategy. Superhydrophobic surfaces, by constructing micro- and nano-rough structures and modifying them with low surface energy materials, achieve water contact angles exceeding 150° and roll-off angles below 10°, significantly reducing the probability of ice nucleation and lowering ice adhesion. Theoretical studies show that when the surface ice adhesion strength is below 60 kPa, natural wind or slight vibrations can cause the ice to detach spontaneously, greatly reducing de-icing energy consumption.

[0004] However, existing superhydrophobic coatings face severe challenges in practical applications: insufficient mechanical durability: superhydrophobic coatings rely on micro-nano rough structures (such as nanoparticles, micron column arrays), which are susceptible to rain erosion, wind and sand abrasion, or freeze-thaw cycles, leading to structural collapse and failure of hydrophobicity; lack of long-term performance: hydrophobic performance is excellent in laboratory environments (contact angle >150°), but performance degrades sharply in harsh outdoor environments (such as UV aging, temperature shock), making it difficult to meet the decades-long service life requirements of power transmission lines; functional limitation: most coatings only focus on initial hydrophobicity, neglecting the synergistic design of low ice adhesion strength and wear resistance, resulting in ice adhesion force still exceeding the critical threshold (60kPa).

[0005] In recent years, metal-organic frameworks (MOFs) have been explored for enhancing the mechanical strength of coatings due to their high specific surface area, tunable pore structure, and ease of surface functionalization. Chinese patent CN116217949A discloses a superhydrophobic MOF material, its preparation method, and its applications. The crystalline surface of this MOF is chemically modified with cashew phenolic resin. The organic ligands of the MOF contain amino groups, and the molar ratio of the amino groups to the aldehyde groups in the cashew phenolic resin is 1:1 to 1:5. This approach focuses on oil-water separation and antibacterial applications. Its superhydrophobic design (contact angle 171°) only addresses liquid water repulsion and does not involve the regulation of solid-ice interface interactions.

[0006] Therefore, developing a coating that combines superhydrophobicity, low ice adhesion, and high mechanical durability is a key breakthrough for solving the problem of ice prevention in power transmission aluminum conductors. Summary of the Invention

[0007] The purpose of this invention is to provide a low-ice-adhesion superhydrophobic anti-icing coating, its preparation method, and its application. This invention involves grafting single-terminated amino fluorosilicone oil onto the surface of an aldehyde-functionalized metal-organic framework material via an amino-aldehyde condensation reaction to obtain a hydrophobically modified metal-organic framework material. This material is then composited with a synthesized fluorinated acrylate copolymer, and the coating is prepared through ultrasonic dispersion and spray curing processes.

[0008] The objective of this invention can be achieved through the following technical solutions:

[0009] A low-ice-adhesion superhydrophobic anti-icing coating, comprising, by weight, 20-40 parts of a fluorinated acrylate copolymer and 8-40 parts of a modified metal-organic framework material.

[0010] The modified metal-organic framework material is obtained by grafting single-ended amino fluorosilicone oil onto the surface of an aldehyde-functionalized metal-organic framework material.

[0011] Furthermore, the fluorinated acrylate copolymer is a copolymer of perfluorooctyl ethyl methacrylate, hexafluorobutyl methacrylate, and methyl methacrylate.

[0012] Furthermore, the static water contact angle of the low-ice-adhesion superhydrophobic anti-icing coating is ≥160°, the roll-off angle is ≤2°, and the ice adhesion strength is ≤20kPa.

[0013] This invention also provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating, the specific steps of which are as follows:

[0014] S1. A single-terminal amino fluorosilicone oil is grafted onto the surface of an aldehyde-functionalized metal-organic framework material by a condensation reaction of amino and aldehyde groups to obtain a modified metal-organic framework material.

[0015] S2. Disperse the modified metal-organic framework material obtained in step S1 in an organic solvent to obtain suspension A;

[0016] S3. Perfluorooctyl ethyl methacrylate, hexafluorobutyl methacrylate, and methyl methacrylate are added as comonomers to a solvent, and a chain transfer agent and an initiator are added to carry out a solution polymerization reaction to obtain a fluorinated acrylate copolymer.

[0017] S4. Dissolve the fluorinated acrylate copolymer obtained in step S3 in an organic solvent to obtain a mixed solution;

[0018] S5. The mixed solution obtained in step S4 and the suspension A obtained in step S2 are mixed and then ultrasonically dispersed to form a uniformly dispersed suspension B.

[0019] S6. Spray the suspension B obtained in step S5 onto the surface of the substrate, and after curing, obtain a low-ice adhesion superhydrophobic anti-icing coating.

[0020] Further, in step S1, the aldehyde-functionalized metal-organic framework material is selected from any one of ZIF-90, ZIF-93, or ZIF-94.

[0021] Furthermore, in step S1, the weight-average molecular weight of the single-terminated amino fluorosilicone oil is 1000-4000.

[0022] Further, in step S1, the mass ratio of the single-terminal amino fluorosilicone oil to the aldehyde-functionalized metal-organic framework material is 0.4 to 1:1.

[0023] Further, in step S1, the solvent for the condensation reaction is selected from tetrahydrofuran or N,N-dimethylformamide, the temperature of the condensation reaction is 15-40°C, and the time of the condensation reaction is 2-10 h.

[0024] Further, in step S2, the mass ratio of the modified metal-organic framework material to the organic solvent is 8-40 parts: 100 parts.

[0025] Further, in step S3, the mass ratio of perfluorooctyl ethyl methacrylate, hexafluorobutyl methacrylate, and methyl methacrylate is 1:1 to 20:1 to 20.

[0026] Further, in step S3, the chain transfer agent is dodecyl mercaptan, and the mass of the chain transfer agent is 2-5% of the total mass of the three comonomers.

[0027] Further, in step S3, the initiator is azobisisobutyronitrile, and the mass of the initiator is 0.3 to 1% of the total mass of the three comonomers.

[0028] Further, in step S3, the solvent is acetone, the temperature of the solution polymerization reaction is 45–75°C, and the time of the solution polymerization reaction is 6–8 hours.

[0029] Further, in step S4, the mass ratio of the fluorinated acrylate copolymer to the organic solvent is 20-40 parts: 100 parts.

[0030] Furthermore, the organic solvents used in steps S2 and S4 are the same, both selected from butyl acetate or tetrahydrofuran.

[0031] Further, in step S5, the mass ratio of the mixed solution obtained in step S4 to the suspension A obtained in step S2 is 1:1, preferably 100 parts: 100 parts.

[0032] Furthermore, in step S5, the ultrasonic dispersion treatment time is 30 to 50 minutes.

[0033] Further, in step S6, the amount of spraying is 100-300 ml / m. 2 Preferably 200ml / m 2 .

[0034] Furthermore, in step S6, the substrate is aluminum.

[0035] Furthermore, in step S6, the curing temperature is 50–100°C, and the curing time is 2–6 hours.

[0036] In addition, the present invention also provides an application of a low-ice adhesion superhydrophobic anti-icing coating in aluminum conductors of power transmission lines, wherein the low-ice adhesion superhydrophobic anti-icing coating is used for long-term anti-icing in aluminum conductors of power transmission lines.

[0037] The principle of this invention is as follows:

[0038] This invention constructs a modified MOF filler with a flexible fluorocarbon chain shell by grafting aldehyde-functionalized MOFs with single-terminated amino fluorosilicone oil through a directional condensation reaction. This design not only enhances the mechanical strength of the coating through the rigid skeleton of the MOFs, but also alleviates stress concentration by utilizing the molecular chain flexibility of the fluorosilicone oil. Further dispersion in a fluorinated acrylate copolymer matrix and formation of a multi-layered micro / nano structure through a spraying process results in a coating that exhibits superhydrophobicity (contact angle ≥160°), low ice adhesion (≤20kPa), and excellent wear resistance. Experiments show that after 200 cycles of sandpaper rubbing, the coating still maintains a contact angle greater than 158° and an ice adhesion strength below 20kPa, making it particularly suitable for long-term anti-icing protection under harsh conditions such as aluminum conductors in power transmission lines.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] (1) The low-ice adhesion superhydrophobic anti-icing coating and its preparation method of the present invention use fewer types of raw materials that are inexpensive and have a simple formulation. They eliminate the expensive nanomaterials and complex additive systems relied upon in traditional methods, thus significantly reducing the cost of raw materials. At the same time, the raw material processing technology of the present invention is simple and the production difficulty is low. The preparation process does not require complex equipment or process control, which further reduces equipment investment and energy consumption costs, and facilitates large-scale production.

[0041] (2) The low-ice adhesion superhydrophobic anti-icing coating of the present invention grafts single-ended amino fluorosilicone oil onto the surface of aldehyde-functionalized metal-organic framework material through the condensation reaction of amino and aldehyde groups, giving the coating excellent micro / nano structure and low surface energy characteristics, with a static water contact angle ≥160° and a roll-off angle ≤2°, exhibiting excellent superhydrophobic performance.

[0042] (3) The low-ice-adhesion superhydrophobic anti-icing coating of the present invention has extremely low ice adhesion strength (≤20kPa), which can effectively reduce the adhesion force between the ice layer and the coating, thereby reducing ice accumulation and preventing ice damage to the substrate. This characteristic is particularly suitable for the anti-icing requirements of aluminum conductors in power transmission lines, and can significantly extend the service life of power transmission lines and improve their operational stability.

[0043] (4) Compared with the prior art, the present invention achieves multi-functional integration of low ice adhesion, superhydrophobicity, and wear resistance by optimizing the coating composition and structure. The modified metal-organic framework material accounts for 16.7% to 66.7% of the coating mass, ensuring the mechanical strength and durability of the coating. At the same time, the introduction of fluorinated acrylate copolymer further enhances the hydrophobicity and anti-icing properties of the coating.

[0044] (5) The low-ice-adhesion superhydrophobic anti-icing coating prepared in this invention achieves excellent performance with a static water contact angle ≥160°, a roll-off angle ≤2°, and an ice adhesion strength ≤20kPa through the synergistic effect of fluorosilane grafting modification and micro / nano structure. Compared with traditional anti-icing coatings, this invention adopts a functional modification strategy using metal-organic framework materials, which significantly reduces ice adhesion while maintaining the mechanical stability of the coating. The spraying process can achieve uniform film formation on the surface of substrates such as aluminum conductors. This coating is particularly suitable for anti-icing protection of aluminum conductors in power transmission lines, and has long-lasting anti-icing and low-ice-adhesion characteristics. Attached Figure Description

[0045] Figure 1 This is a SEM image of the surface of the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 of the present invention;

[0046] Figure 2 These are contact angle test images of the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 of the present invention;

[0047] Figure 3These are contact angle test images of the coating prepared in Comparative Example 1 of this invention.

[0048] Figure 4 These are contact angle test images of the coating prepared in Comparative Example 2 of this invention.

[0049] Figure 5 These are contact angle test images of the coating prepared in Comparative Example 3 of this invention. Detailed Implementation

[0050] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0051] In the following embodiments, unless otherwise specified, the raw materials or processing techniques are conventional commercially available raw materials or conventional processing techniques in the art.

[0052] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0053] Example 1

[0054] This embodiment provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating, the specific steps of which are as follows:

[0055] S1. Dissolve 4g of single-terminated amino fluorosilicone oil (weight average molecular weight of 1000) and 10g of ZIF-90 in 40g of tetrahydrofuran solution, stir and react at 25℃ for 5h, centrifuge and dry to obtain modified metal-organic framework material.

[0056] S2. Disperse 8g of the modified metal-organic framework material obtained in step S1 in 100g of tetrahydrofuran to obtain suspension A;

[0057] S3. Add 1g of perfluorooctyl ethyl methacrylate, 1g of hexafluorobutyl methacrylate, and 20g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.11g of azobisisobutyronitrile and 0.44g of dodecanethiol dropwise. React at 75℃ for 6h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0058] S4. Dissolve 20g of the fluorinated acrylate copolymer obtained in step S3 in 100g of tetrahydrofuran to obtain a mixed solution;

[0059] S5. Mix all the mixed solutions obtained in step S4 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 30 minutes to form a uniformly dispersed suspension B.

[0060] S6. Apply the suspension B obtained in step S5 using a spraying process at a concentration of 200 ml / m 2 The coating is sprayed onto the surface of aluminum material and then heated and cured in an 80℃ oven for 4 hours to obtain a low-icing, superhydrophobic, and anti-icing coating.

[0061] Example 2

[0062] This embodiment provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating, the specific steps of which are as follows:

[0063] S1. Dissolve 10g of single-terminated amino fluorosilicone oil (weight average molecular weight of 4000) and 10g of ZIF-90 in 50g of N,N-dimethylformamide solution, stir and react at 40℃ for 4h, centrifuge and dry to obtain modified metal-organic framework material.

[0064] S2. Disperse 35g of the modified metal-organic framework material obtained in step S1 in 100g of butyl acetate to obtain suspension A;

[0065] S3. Add 1g of perfluorooctyl ethyl methacrylate, 20g of hexafluorobutyl methacrylate, and 1g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.22g of azobisisobutyronitrile and 1.1g of dodecanethiol dropwise. React at 45℃ for 8h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0066] S4. Dissolve 40g of the fluorinated acrylate copolymer obtained in step S3 in 100g of butyl acetate to obtain a mixed solution;

[0067] S5. Mix all the mixed solutions obtained in step S4 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 40 minutes to form a uniformly dispersed suspension B.

[0068] S6. Apply the suspension B obtained in step S5 using a spraying process at a concentration of 200 ml / m 2 The coating is sprayed onto the surface of aluminum material and then heated and cured in a 90℃ oven for 2 hours to obtain a low-icing, superhydrophobic, and anti-icing coating.

[0069] Example 3

[0070] This embodiment provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating, the specific steps of which are as follows:

[0071] S1. Dissolve 5g of single-terminated amino fluorosilicone oil (weight average molecular weight of 3000) and 10g of ZIF-90 in 50g of N,N-dimethylformamide solution, stir and react at 30℃ for 4h, centrifuge and dry to obtain modified metal-organic framework material.

[0072] S2. Disperse 25g of the modified metal-organic framework material obtained in step S1 in 100g of butyl acetate to obtain suspension A;

[0073] S3. Add 1g of perfluorooctyl ethyl methacrylate, 10g of hexafluorobutyl methacrylate, and 10g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.63g of azobisisobutyronitrile and 0.42g of dodecanethiol dropwise. React at 65℃ for 7h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0074] S4. Dissolve 30g of the fluorinated acrylate copolymer obtained in step S3 in 100g of butyl acetate to obtain a mixed solution;

[0075] S5. Mix all the mixed solutions obtained in step S4 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 40 minutes to form a uniformly dispersed suspension B.

[0076] S6. Apply the suspension B obtained in step S5 using a spraying process at a concentration of 200 ml / m 2 The coating is sprayed onto the surface of aluminum material and then heated and cured in a 70℃ oven for 5 hours to obtain a low-icing, superhydrophobic, and anti-icing coating.

[0077] Example 4

[0078] This embodiment provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating. Except for replacing ZIF-90 with ZIF-93 in step S1, the other steps are the same as in embodiment 1.

[0079] Example 5

[0080] This embodiment provides a method for preparing a low-ice-adhesion superhydrophobic anti-icing coating. Except for replacing ZIF-90 with ZIF-94 in step S1, the other steps are the same as in embodiment 1.

[0081] Comparative Example 1

[0082] This comparative example provides a method for preparing a coating, the specific steps of which are as follows:

[0083] S1. Disperse 8g of metal-organic framework material ZIF-90 in 100g of tetrahydrofuran to obtain suspension A;

[0084] S2. Add 1g of perfluorooctyl ethyl methacrylate, 1g of hexafluorobutyl methacrylate, and 20g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.11g of azobisisobutyronitrile and 0.44g of dodecanethiol dropwise. React at 75℃ for 6h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0085] S3. Dissolve 20g of the fluorinated acrylate copolymer obtained in step S2 in 100g of tetrahydrofuran to obtain a mixed solution;

[0086] S4. Mix all the mixed solutions obtained in step S3 with all the suspensions A obtained in step S1, and then perform ultrasonic dispersion treatment for 30 minutes to form a uniformly dispersed suspension B.

[0087] S5. Apply the suspension B obtained in step S4 using a spraying process at a concentration of 200 ml / m 2 The coating is obtained by spraying it onto the surface of aluminum material and then heating and curing it in an 80℃ oven for 4 hours.

[0088] Comparative Example 2

[0089] This comparative example provides a method for preparing a coating, the specific steps of which are as follows:

[0090] S1. Dissolve 4g of single-terminated amino fluorosilicone oil (weight average molecular weight of 1000) and 10g of ZIF-90 in 40g of tetrahydrofuran solution, stir and react at 25℃ for 5h, centrifuge and dry to obtain modified metal-organic framework material.

[0091] S2. Disperse 8g of the modified metal-organic framework material obtained in step S1 in 100g of tetrahydrofuran to obtain suspension A;

[0092] S3. Dissolve 20g of E51 epoxy resin in 100g of tetrahydrofuran to obtain a mixed solution;

[0093] S4. Mix all the mixed solutions obtained in step S3 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 30 minutes to form a uniformly dispersed suspension B.

[0094] S5. Apply the suspension B obtained in step S4 using a spraying process at a concentration of 200 ml / m 2 The coating is obtained by spraying it onto the surface of aluminum material and then heating and curing it in an 80℃ oven for 4 hours.

[0095] Comparative Example 3

[0096] This comparative example provides a method for preparing a coating, the specific steps of which are as follows:

[0097] S1. Dissolve 5g of single-terminated amino polydimethylsiloxane (weight average molecular weight of 2500) and 10g of ZIF-90 in 50g of N,N-dimethylformamide solution, stir and react at 30℃ for 4h, centrifuge and dry to obtain modified metal-organic framework material.

[0098] S2. Disperse 25g of the modified metal-organic framework material obtained in step S1 in 100g of butyl acetate to obtain suspension A;

[0099] S3. Add 1g of perfluorooctyl ethyl methacrylate, 10g of hexafluorobutyl methacrylate, and 10g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.63g of azobisisobutyronitrile and 0.42g of dodecanethiol dropwise. React at 65℃ for 7h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0100] S4. Dissolve 30g of the fluorinated acrylate copolymer obtained in step S3 in 100g of butyl acetate to obtain a mixed solution;

[0101] S5. Mix all the mixed solutions obtained in step S4 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 40 minutes to form a uniformly dispersed suspension B.

[0102] S6. Apply the suspension B obtained in step S5 using a spraying process at a concentration of 200 ml / m 2 The coating is obtained by spraying it onto the surface of aluminum material and then heating and curing it in a 70℃ oven for 5 hours.

[0103] Comparative Example 4

[0104] This comparative example provides a method for preparing a coating, the specific steps of which are as follows:

[0105] S1. Dissolve 2g of cashew phenol and 10g of NH2-UiO-66(Zr) in 40g of tetrahydrofuran solution, stir and react at 25℃ for 5h, centrifuge and dry to obtain modified metal-organic framework material.

[0106] S2. Disperse 25g of the modified metal-organic framework material obtained in step S1 in 100g of butyl acetate to obtain suspension A;

[0107] S3. Add 1g of perfluorooctyl ethyl methacrylate, 10g of hexafluorobutyl methacrylate, and 10g of methyl methacrylate to 100ml of acetone solvent and stir for 30min. After the system is evenly dispersed, slowly add 0.63g of azobisisobutyronitrile and 0.42g of dodecanethiol dropwise. React at 65℃ for 7h. After evaporating the solvent by rotary evaporation at 60℃ for 20min, a fluorinated acrylate copolymer is obtained.

[0108] S4. Dissolve 30g of the fluorinated acrylate copolymer obtained in step S3 in 100g of butyl acetate to obtain a mixed solution;

[0109] S5. Mix all the mixed solutions obtained in step S4 and all the suspensions A obtained in step S2, and then perform ultrasonic dispersion treatment for 30 minutes to form a uniformly dispersed suspension B.

[0110] S6. Apply the suspension B obtained in step S5 using a spraying process at a concentration of 200 ml / m 2 The coating is obtained by spraying it onto the surface of aluminum material and then heating and curing it in an 80℃ oven for 4 hours.

[0111] To demonstrate the effectiveness of the low-ice-adhesion superhydrophobic anti-icing coating provided in this application, the following tests were conducted:

[0112] (1) Surface morphology test

[0113] The surface morphology of the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 was tested using a Zeiss SUPRA-55 field reflection scanning electron microscope (SEM). The resulting surface morphology images are shown below. Figure 1 As shown.

[0114] (2) Hydrophobicity test

[0115] The water contact angle and roll-off angle of the coating were measured using a DSA100 contact angle meter. The contact angle test images of the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 are shown below. Figure 2 As shown, the contact angle test images of the coatings prepared in Comparative Examples 1-3 are as follows. Figure 3-5 As shown in Table 1, the contact angle test results of the low-ice adhesion superhydrophobic anti-icing coatings prepared in Examples 1-5 and the coatings prepared in Comparative Examples 1-4 are shown in Table 1.

[0116] (3) Ice adhesion strength

[0117] Deionized water inside a hollow polytetrafluoroethylene mold was frozen at -10℃. After the ice column formed, a 0℃ deionized water film was applied to its surface. The water film interface was then bonded to a coating test plate. After freezing at -10℃ for 4 hours, the shear force separating the ice column from the test plate was measured using a shear force testing device. The ice adhesion strength was calculated based on the shear force and the cross-sectional area of ​​the ice column. The ice adhesion strength test results of the low ice adhesion superhydrophobic anti-icing coatings prepared in Examples 1-5 and the coatings prepared in Comparative Examples 1-4 are shown in Table 1.

[0118] (4) Icing volume test

[0119] Under the same icing conditions at -10℃, the amount of ice formation was compared with that of a blank aluminum plate. The ice adhesion strength test results of the low ice adhesion superhydrophobic anti-icing coatings prepared in Examples 1-5 and the coatings prepared in Comparative Examples 1-4 are shown in Table 1.

[0120] (5) Mechanical performance testing

[0121] The adhesion of the coatings was measured according to GB / T 9286-1998 "Cross-cut test of paint and varnish films". The adhesion test results of the low-ice adhesion superhydrophobic anti-icing coatings prepared in Examples 1-5 and the coatings prepared in Comparative Examples 1-4 are shown in Table 1.

[0122] The coated side of the aluminum plate is placed on 1000-grit sandpaper, and a 100g weight is placed on the test plate. The test plate is moved 20cm at a speed of 10cm / s as one sanding cycle. After 200 sanding cycles, the mechanical stability of the coating is evaluated by measuring the attenuation of the water contact angle, roll-off angle and ice adhesion strength.

[0123] (6) Freeze-thaw cycle ice adhesion strength test

[0124] Deionized water inside a hollow polytetrafluoroethylene mold was frozen. After ice column formation, a 0°C deionized water film was applied to its surface. The water film interface was then bonded to a coated test plate. After freezing at -10°C for 4 hours, the shear force separating the ice column from the test plate was measured using a shear force testing device. The ice adhesion strength was calculated based on the shear force and the cross-sectional area of ​​the ice column. The ice adhesion strength value was recorded after 100 freeze-thaw cycles.

[0125] (7) Outdoor weather resistance test

[0126] The coating was tilted at 45° south and hung in an outdoor environment in Beijing to test its long-term outdoor weather resistance. The contact angle of the coating was measured after 1000 hours.

[0127] Table 1. Performance data of the low-ice-adhesion superhydrophobic anti-icing coatings prepared in Examples 1-5 and the coatings prepared in Comparative Examples 1-3.

[0128]

[0129]

[0130] according to Figure 1 It can be seen that the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 has a significant micro-nano secondary rough structure, which is the key to the coating's superhydrophobic properties. (Comparison) Figure 3-5 It can be seen that the contact angle of the coatings prepared in Comparative Examples 1-3 is smaller than that of the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1. Therefore, the low-ice-adhesion superhydrophobic anti-icing coating prepared in Example 1 exhibits obvious superhydrophobicity.

[0131] As shown in Table 1, the superhydrophobic coatings for anti-icing aluminum wires prepared in Examples 1-5 have a water contact angle greater than 160°, a roll-off angle less than 3°, and an adhesion grade of 1. They also maintain very low ice adhesion strength (<15 kMa) and still exhibit very low ice adhesion strength (<20 kMa) after 200 polishing cycles. After 100 freeze-thaw cycles, the ice adhesion strength is still less than 30 kMa, and the contact angle is still greater than 155° after 1000 hours of outdoor irradiation. In contrast, the coatings prepared in Comparative Examples 1-4 have a water contact angle less than 156°, a roll-off angle greater than 5°, and high ice adhesion strength (>75 kPa). After 200 polishing cycles, the ice adhesion strength is >100 kPa, and after 100 freeze-thaw cycles, the ice adhesion strength is greater than 120 kMa. After 1000 hours of outdoor irradiation, the contact angle is less than 120°. Therefore, the superhydrophobic coating for anti-icing of aluminum conductors obtained by the present invention has the characteristics of superhydrophobicity, rapid ice melting, wear resistance, reduced ice adhesion strength, and reduced ice accumulation. Thus, the superhydrophobic coatings for anti-icing of aluminum conductors prepared in Examples 1 to 5 have good anti-icing function, so that aluminum conductors using the coating of the present invention have anti-icing function.

[0132] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A low-ice-adhesion superhydrophobic anti-icing coating, characterized by, comprise 20-40 parts by mass of a fluorine-containing acrylic ester copolymer and 8-40 parts by mass of a modified metal organic framework material, The modified metal organic framework material is obtained by grafting a single-end amino fluorosilicone oil onto the surface of an aldehyde group functionalized metal organic framework material.

2. The low-ice-adhesion superhydrophobic anti-icing coating according to claim 1, characterized in that, The fluorine-containing acrylic ester copolymer is a copolymer of perfluoro-octyl ethyl methacrylate, hexafluorobutyl methacrylate and methyl methacrylate.

3. The low-ice-adhesion superhydrophobic anti-icing coating according to claim 1, characterized in that, The low-ice-adhesion super-hydrophobic anti-icing coating has a static water contact angle of ≥160°, a rolling angle of ≤2° and an ice adhesion strength of ≤20 kPa.

4. A method of producing a low-ice-adhesion superhydrophobic anti-icing coating according to any one of claims 1 to 3, characterized in that, The specific steps are as follows: S1. A single-end amino fluorosilicone oil is grafted onto the surface of an aldehyde group functionalized metal organic framework material by condensation reaction of amino groups and aldehyde groups to obtain a modified metal organic framework material. S2. The modified metal organic framework material obtained in step S1 is dispersed in an organic solvent to obtain a suspension A. S3. Perfluoro-octyl ethyl methacrylate, hexafluorobutyl methacrylate and methyl methacrylate are added to a solvent as comonomers, a chain transfer agent and an initiator are added, and solution polymerization is performed to obtain a fluorine-containing acrylic ester copolymer. S4. The fluorine-containing acrylic ester copolymer obtained in step S3 is dissolved in an organic solvent to obtain a mixed solution. S5. The mixed solution obtained in step S4 and the suspension A obtained in step S2 are mixed, and after ultrasonic dispersion treatment, a uniformly dispersed suspension B is formed. S6. The suspension B obtained in step S5 is sprayed on the surface of a substrate, and after curing treatment, a low-ice-adhesion super-hydrophobic anti-icing coating is obtained.

5. The method of claim 4, wherein the low-ice-adhesion superhydrophobic anti-icing coating is prepared by the steps of: In step S1, the aldehyde group functionalized metal organic framework material is selected from any one of ZIF-90, ZIF-93 or ZIF-94. The weight average molecular weight of the single-end amino fluorosilicone oil is 1000-4000. The mass ratio of the single-end amino fluorosilicone oil to the aldehyde group functionalized metal organic framework material is 0.4-1:

1. The solvent for the condensation reaction is selected from tetrahydrofuran or N,N-dimethylformamide, the temperature for the condensation reaction is 15-40℃, and the time for the condensation reaction is 2-10 h.

6. The method of claim 4, wherein the low-ice-adhesion superhydrophobic anti-icing coating is prepared by the steps of: In step S3, the mass ratio of perfluoro-octyl ethyl methacrylate, hexafluorobutyl methacrylate and methyl methacrylate is 1:1-20:1-20. The chain transfer agent is dodecanethiol, and the mass of the chain transfer agent is 2-5% of the total mass of the three comonomers. The initiator is azobisisobutyronitrile, and the mass of the initiator is 0.3-1% of the total mass of the three comonomers. The solvent is acetone, the temperature for the solution polymerization is 45-75℃, and the time for the solution polymerization is 6-8 h.

7. The method for preparing a low-ice-adhesion superhydrophobic anti-icing coating according to claim 4, characterized in that, In step S2, the mass ratio of the modified metal organic framework material to the organic solvent is 8-40 parts by mass:100 parts by mass. In step S4, the mass ratio of the fluorine-containing acrylic ester copolymer to the organic solvent is 20-40 parts by mass:100 parts by mass. The organic solvents in steps S2 and S4 are the same and are selected from butyl acetate or tetrahydrofuran.

8. The method for preparing a low-ice-adhesion superhydrophobic anti-icing coating according to claim 4, characterized in that, In step S5, the mass ratio of the mixed solution obtained in step S4 to the suspension A obtained in step S2 is 1:

1. The ultrasonic dispersion treatment time is 30-50 min.

9. The method of claim 4, wherein the low-ice-adhesion superhydrophobic anti-icing coating is prepared by the steps of: In step S6, the amount of spraying is 100 to 300 ml / m 2 ; The substrate is aluminum material. The curing temperature is 50-100 ℃, and the curing time is 2-6 h.

10. The use of the low-ice-adhesion super-hydrophobic anti-icing coating as claimed in any one of claims 1-3 in an aluminum conductor of a power transmission line.

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