CN111471392B

CN111471392B - Amphiphilic ice-resistant coating based on PVP and preparation method thereof

Info

Publication number: CN111471392B
Application number: CN202010096180.3A
Authority: CN
Inventors: 张雷; 杨静; 陈鹏光; 郭洪爽
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 2020-02-17
Filing date: 2020-02-17
Publication date: 2021-09-17
Anticipated expiration: 2040-02-17
Also published as: CN111471392A

Abstract

The invention belongs to the field of organic materials, and particularly relates to an amphipathic ice-resistant coating based on PVP and a preparation method thereof. The amphipathic ice-resistant coating based on PVP comprises the following components in parts by mass: 100 parts of PDMS; 5-15 parts of amphiphilic polymer based on PVP; 0-15 parts of photo-thermal material; 2-5 parts of a cross-linking agent; 1-2 parts of a catalyst; in the invention, PDMS is a hydrophobic chain segment and PVP is a hydrophilic chain segment in the amphiphilic polymer, after the coating is formed by crosslinking with a PDMS matrix, a microphase separation structure can be generated on the surface, and meanwhile, the fluorine-containing FA chain segment has the characteristic of low surface energy, so that the ice shear strength is greatly reduced; most preferably, the photo-thermal material can efficiently absorb sunlight and convert the sunlight into heat energy, so that the photo-thermal material is introduced into the amphiphilic polymer coating, the photo-thermal effect of the amphiphilic polymer coating can be utilized, the temperature is rapidly increased under illumination, and the anti-icing effect of the coating is further improved.

Description

Amphiphilic ice-resistant coating based on PVP and preparation method thereof

Technical Field

The invention belongs to the field of organic materials, and particularly relates to an amphipathic ice-resistant coating based on PVP and a preparation method thereof.

Background

The occurrence of ice formation on the equipment operating in the air can seriously affect the operation safety of the equipment, thereby causing great economic loss. For example, ice coating on the transmission line can pose a serious threat to the normal operation of electric power, railways and network communication systems; icing on aircraft surfaces can increase drag and fuel consumption, reducing performance by up to 50% and even causing catastrophic air crashes. In order to prevent damage due to ice coating, a variety of methods for preventing or removing ice have been developed, and conventional methods for removing ice include a chemical method, a mechanical removal method, a surface electrical heating method, etc., which have disadvantages such as high economic cost, large energy consumption, damage to equipment surfaces, and environmental pollution. In recent years, coating deicing has begun to be applied to anti-icing protection of equipment surfaces as a new active protection type technology with good effect and low energy consumption. The excellent ice-resistant coating can not only reduce the adhesion of ice to the surface of the equipment, but also delay the freezing of water on the surface, thereby achieving the effect of ice prevention and removal.

Currently, the most studied anti-icing coatings mainly include super-hydrophobic coatings inspired by the surface of lotus leaves and smooth coatings inspired by the 'smooth lips' of pitcher plant. The presence of micro/nanostructures on the surface of the superhydrophobic coating can reduce the contact area of ice with the substrate, thereby facilitating the reduction of ice adhesion. In addition, the presence of air between the ice and the coating surface reduces heat transfer while providing stress sites that initiate cracks between the matrix and the ice during de-icing. While superhydrophobic surfaces can be effective at reducing ice formation temperatures, at high humidity, superhydrophobic surfaces have a higher ice freezing rate than smooth surfaces, and tiny water droplets can penetrate into the nano-texture, resulting in destruction of the surface micro/nano structure after a deicing cycle, reduced mechanical durability, and increased ice adhesion strength on solid surfaces. Thus, an efficient anti-icing coating cannot be limited to using a single hydrophobic material. The porous surface impregnated with lubricating liquid (SLIPS) is an anti-icing lubricious coating material, can delay frosting and reduce ice adhesion strength, has excellent anti-fouling, anti-icing and self-healing properties, and its high stability and moisture resistance make SLIPS a promising alternative to superhydrophobic surfaces. In the preparation of SLIPS, the surface should have a good nano-microstructure to provide space for absorbing the lubricant, which is not miscible with water, while the chemical affinity of the lubricant to the solid surface should be greater than the affinity of water to the surface. However, the lubricant layer in SLIPS is easily carried away by water droplets or replaced by ice, resulting in a significant reduction in anti-icing performance and poor durability after several icing/de-icing cycles. In addition, the preparation process of the anti-ice coating is complex, the cost is high, and the large-scale application of the anti-ice coating is restricted.

Thus, many challenges remain in the coating anti-icing field, such as: (1) in the process of forming ice on the surface of a solid, the physical process of ice nucleation and thermodynamics of phase change are complex and need further research; (2) the passive anti-icing method cannot achieve the optimal anti-icing performance; (3) the relationship between surface wettability transition and external environmental conditions requires further investigation; (4) the anti-icing material is not sufficiently durable in practical use. Therefore, the development of the coating with high-efficiency anti-icing performance and excellent stability is of great significance.

Disclosure of Invention

The invention aims to provide an amphipathic ice-resistant coating based on PVP and a preparation method thereof.

In order to achieve the purpose, the invention adopts the technical scheme that:

the amphiphilic ice-resistant coating based on PVP comprises the following components in parts by mass: 100 parts of PDMS; 5-15 parts of amphiphilic polymer based on PVP; 0-15 parts of photo-thermal material; 2-5 parts of a cross-linking agent; 1-2 parts of a catalyst; wherein the PVP-based amphiphilic polymer is PVP-PDMS-PVP or FA-PVP-PDMS-PVP-FA.

Preferably, the mass ratio of the PDMS to the PVP-based amphiphilic polymer to the photothermal material is 20:2: 1.

The preparation method of the PVP-PDMS-PVP comprises the following steps: dissolving CTA-PDMS-CTA, N-vinyl pyrrolidone NVP and an initiator in a solvent, adding the solution into a dry container, blowing nitrogen or argon at room temperature to deoxidize the solution, then immersing the container in an oil bath, heating for polymerization reaction, and quenching with an ice water mixture after the reaction is finished; concentrating the solution after reaction, precipitating, filtering, collecting solid, and drying to obtain the product.

Wherein the molar ratio of the CTA-PDMS-CTA to the N-vinyl pyrrolidone NVP is 0.625-1.25: 100-200.

The molecular formula of the PVP-PDMS-PVP is shown as (I), wherein n and m are integers.

The preparation method of the FA-PVP-PDMS-PVP-FA comprises the following steps: dissolving CTA-PDMS-CTA, N-vinyl pyrrolidone NVP, acrylic acid-1- (1H,1H,2H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecyloxy) -isopropyl alcohol ester FA and an initiator in a solvent, adding the solvent into a dry container, blowing nitrogen or argon at room temperature to deoxidize the solution, then immersing the container in an oil bath, heating for polymerization reaction, and quenching with an ice water mixture after the reaction is finished; concentrating the solution after reaction, precipitating, filtering, collecting solid, and drying to obtain the product.

Wherein the molar ratio of CTA-PDMS-CTA, N-vinyl pyrrolidone NVP, acrylic acid-1- (1H,1H,2H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecylyloxy) -isopropyl alcohol ester FA is 0.95-1.9:200-400: 5.7-11.4.

Preferably, the mole ratio of the CTA-PDMS-CTA, N-vinyl pyrrolidone NVP, acrylic acid-1- (1H,1H,2H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecyloxy) -isopropyl alcohol ester FA is 0.95: 200:5.7.

The molecular formula of the FA-PVP-PDMS-PVP-FA is shown as (II), wherein n, m and p are integers.

Preferably, the cross-linking agent is methyl triethoxysilane (METES); the catalyst is dibutyltin dilaurate DBTDL; the molecular weight of PDMS is 26000-400000.

Preferably, the initiator is 2, 2-azobisisobutyronitrile or benzoyl peroxide.

Preferably, the photo-thermal material is a carbon-based material, an organic polymer material, a semiconductor material, or a metal-based material.

Preferably, the mass ratio of the solvent volume to the PDMS is: dichloromethane: 50-100% and/or tetrahydrofuran: 50 to 100 percent.

The invention also comprises a preparation method of the amphipathic ice-resistant coating based on PVP, which comprises the following steps: and dissolving PDMS, an amphiphilic polymer based on PVP and a photo-thermal material in a mixed solution of dichloromethane and tetrahydrofuran, uniformly mixing, adding a cross-linking agent and a catalyst, uniformly coating the solution on the surface of a clean steel sheet or glass, and drying at room temperature to obtain the amphiphilic ice-resistant coating based on PVP.

Preferably, the coating method is a method such as dropping coating, spray coating, spin coating, dip coating, or the like.

Compared with the prior art, the invention has the beneficial effects that:

the amphiphilic polymer is a macromolecular compound containing a hydrophilic chain segment and a lipophilic chain segment in the same molecular chain, wherein the hydrophilic chain segment is usually polyethylene glycol (PEG), polyvinyl ether, polyvinyl alcohol, polyvinylpyrrolidone (PVP), polyacrylic acid, polyacrylamide and the like, the hydrophobic chain segment is polypropylene oxide, polystyrene, Polydimethylsiloxane (PDMS), polymethyl methacrylate and the like, and the incompatibility of the two chain segments can cause the occurrence of microphase separation. The amphiphilic polymer can be used for preparing functional coatings and is widely applied to the fields of biological materials, adhesives, additives, coatings and the like. PDMS is a common hydrophobic organic silicon material and has low surface energy (22.7mJ m)^-2) And the PVP is a water-soluble high molecular compound which is synthesized by taking monomer vinyl pyrrolidone (NVP) as a raw material through bulk polymerization, solution polymerization and other methods, has excellent solubility, film-forming property, caking property, surface activity and the like, and can obviously reduce the freezing point of water. The photo-thermal material selected by the invention can enable the coating to be heated rapidly under the irradiation of sunlight, and the fluorine-containing polymer has the characteristics of excellent thermal stability, chemical stability, low surface energy and the like. Therefore, the amphiphilic polymer based on PVP, especially the amphiphilic polymer with the fluorine-containing segment, is expected to have potential application value in the fields of anti-icing coatings and the like.

In the invention, PDMS in the amphiphilic polymers PVP-PDMS-PVP and FA-PVP-PDMS-PVP-FA is a hydrophobic chain segment, PVP is a hydrophilic chain segment, after the coating is formed by crosslinking with a PDMS matrix, a microphase separation structure can be generated on the surface, and meanwhile, the FA chain segment containing fluorine has the characteristic of low surface energy, so that the ice shear strength is greatly reduced; most preferably, the photo-thermal material can efficiently absorb sunlight and convert the sunlight into heat energy, so that the photo-thermal material is introduced into the amphiphilic polymer coating, the photo-thermal effect of the amphiphilic polymer coating can be utilized, the temperature is rapidly increased under illumination, and the anti-icing effect of the coating is further improved.

In a word, the coating of the invention has the following characteristics that (1) the anti-ice coating can be crosslinked at room temperature in the preparation process, and the process flow and the operation are simpler and more convenient; (2) the prepared anti-ice coating has very low ice shear strength which can be as low as 17.7kPa, ice on the surface can fall off under the action of gravity or wind force, the ice shear strength of the coating is still kept below 25kPa after 50 times of icing/deicing cycles, the stability is excellent, and the ice shear strength of a pure PDMS coating which does not contain amphiphilic polymer and photo-thermal material is usually about 50 kPa; (3) the prepared anti-icing coating combines the characteristic of high thermal conductivity of a photothermal material, and compared with a coating without the photothermal material, the surface temperature can be higher than 8 ℃ under simulated sunlight irradiation, so that the shedding of ice on the surface can be further effectively promoted, and the anti-icing effect is enhanced.

Drawings

FIG. 1: water contact angle test image of the coating in example 3.

FIG. 2: the ice shear strength histograms for the coatings of examples 1-6 versus a pure PDMS coating without amphiphilic polymer and photo-thermal material.

FIG. 3: the surface average temperature histograms of the coatings in examples 3-6 after 3min of simulated daylight illumination.

Detailed Description

In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the accompanying drawings and preferred embodiments.

The performance test method for PVP-based amphiphilic ice-resistant coatings in this application:

1) water contact angle test: and (3) taking deionized water as test liquid, measuring the static water contact angle of the coating at room temperature by using a static liquid drop method, adopting a three-point fitting method during contact angle calculation, and averaging after testing each coating for five times. The contact angle tester is model number JC2000D 1.

2) Testing the ice shear strength: and 3 coating samples are taken from each group, placed on a cold table, a hollow organic glass cylinder with the inner diameter of 10mm is subjected to hydrophobic treatment by using perfluorooctyl trichlorosilane, vertically placed on the surface of each sample, and 450 mu L of deionized water is dripped into the sample. And cooling the cooling platform from room temperature to-15 ℃, and keeping the cooling platform for 4 hours in a nitrogen atmosphere to ensure that the liquid in the cylinder is completely frozen. The cylinder was pushed forward at a rate of 0.1mm/s using an Imada ZP-50N push-pull dynamometer, the maximum shear force of the push-pull dynamometer just contacting the cylinder until the ice was completely detached from the coating surface was recorded, and the average value was taken after each set of samples was tested three times.

3) Icing/deicing cycle testing: and 3 coating samples are taken from each group, placed on a cold table, and subjected to ice shear strength test circularly by the method, and the circulating times and the average value of the ice shear strength of 3 samples at each time are recorded.

4) Simulation of sunlight irradiation temperature rise test: recording the initial temperature of the coating sample at room temperature, placing the coating sample at a position 10-50 cm below a light source of a simulated fluorescent lamp, wherein the power of the simulated fluorescent lamp is 150W, recording the temperature rise curve of the surface and the average temperature of the surface after 3min, and taking an average value after testing each group of three samples.

Example 1 3.7g of CTA-PDMS-CTA (0.625mmol), 11.11g of NVP (100mmol), 16.4mg of 2, 2-azobisisobutyronitrile AIBN (1.0mmol) were dissolved in 8mL of 1, 4-dioxane, added to a dry round bottom flask, deoxygenated by bubbling nitrogen gas for 30min at room temperature, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with an ice-water mixture. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer PVP-PDMS-PVP.

Dissolving 5.0g PDMS (molecular weight 26000) and 0.25g PVP-PDMS-PVP in a mixed solution of 3mL dichloromethane and 5mL tetrahydrofuran, mixing, adding 0.1g cross-linking agent METES and 50mg catalyst DBTDL, and uniformly coating the solution on a clean 20 × 20mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PP₅。

The coating was measured to have a static water contact angle of 104 deg. and an ice shear strength of 43 kPa.

Example 2 7.4g of CTA-PDMS-CTA (1.25mmol), 22.22g of NVP (200mmol), 32.8mg of AIBN (2.0mmol) were dissolved in 16mL of 1, 4-dioxane, added to a dry round bottom flask, the solution was deoxygenated by bubbling argon at room temperature for 30min, the flask was then immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer PVP-PDMS-PVP.

8.0g PDMS (molecular weight 26000), 0.4g PVP-PDMS-PVP and 0.4g carbon fiber were dissolved in a mixed solution of 6mL dichloromethane and 8mL tetrahydrofuran, mixed well, added with 0.24g cross-linker METES and 120mg catalyst DBTDL, and the solution was uniformly coated on a clean 40X 40mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PP₅C₅。

The coating was measured to have a static water contact angle of 103 deg. and an ice shear strength of 18 kPa.

Example 3 5.62g of CTA-PDMS-CTA (0.95mmol), 22.22g of NVP (200mmol), 4.21g of FA (5.7mmol), 8.2mg of AIBN (0.5mmol) were dissolved in 12mL of 1, 4-dioxane, added to a dry round bottom flask, the solution was deoxygenated by bubbling nitrogen at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

Dissolving 5.0g PDMS (molecular weight is 320000) and 0.5g FA-PVP-PDMS-PVP-FA in a mixed solution of 3mL dichloromethane and 5mL tetrahydrofuran, mixing, adding 0.125g cross-linking agent METES and 50mg catalyst DBTDL, and uniformly coating the solution on clean 20 × 20mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PPF₁₀。

The coating was measured to have a static water contact angle of 87.5 deg. (shown in FIG. 1), an ice shear strength of 26.3kPa, and an average surface temperature of 30.9 deg.C after 3min of irradiation at 50cm from a simulated daylight lamp.

Example 4: 8.43g of CTA-PDMS-CTA (1.425mmol), 33.33g of NVP (300mmol), 6.315g of FA (8.55mmol), 12.3mg of AIBN (0.75mmol) were dissolved in 18mL of 1, 4-dioxane, which was added to a dry round-bottomed flask, the solution was deoxygenated by bubbling argon at room temperature for 30min, and then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

4.0g PDMS (molecular weight 320000), 0.6g FA-PVP-PDMS-PVP-FA are dissolved in a mixed solution of 4mL dichloromethane and 3mL tetrahydrofuran, after mixing, 0.12g cross-linking agent METES and 60mg catalyst DBTDL are added, and the solution is evenly coated on clean 30X 30mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PPF₁₅。

The coating was found to have a static water contact angle of 82.8 deg.C, an ice shear strength of 19.5kPa, and an average surface temperature of 30.7 deg.C after irradiation for 3min at a distance of 50cm from the simulated daylight lamp.

Example 5.62g of CTA-PDMS-CTA (0.95mmol), 22.22g of NVP (200mmol), 4.21g of FA (5.7mmol), 8.2mg of AIBN (0.5mmol) were dissolved in 12mL of 1, 4-dioxane, added to a dry round bottom flask, deoxygenated by bubbling nitrogen at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

2.0g PDMS (molecular weight 360000), 0.2g FA-PVP-PDMS-PVP-FA and 0.1g carbon fiber were dissolved in a mixed solution of 1.5mL dichloromethane and 2mL tetrahydrofuran, mixed well, added with 60mg cross-linker METES and 30mg catalyst DBTDL, and the solution was uniformly coated on a clean 20X 20mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PPF₁₀C₅。

The static water contact angle of the coating is 79.7 degrees, the ice shear strength is 17.7kPa, the icing/deicing cycle test frequency can reach 50 times, and the surface average temperature is 38.0 ℃ after the coating is irradiated for 3min at a position 50cm away from a simulated fluorescent lamp.

Example 6.43 g of CTA-PDMS-CTA (1.425mmol), 33.33g of NVP (300mmol), 6.315g of FA (8.55mmol), 12.3mg of AIBN (0.75mmol) were dissolved in 18mL of 1, 4-dioxane, added to a dry round-bottomed flask, the solution was deoxygenated by bubbling argon at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

6.0g of PDMS (molecular weight 400000), 0.6g of FA-PVP-PDMS-PVP-FA and 0.6g of carbon fiber were dissolved in a mixed solution of 6mL of dichloromethane and 6mL of tetrahydrofuran, mixed well, added with 0.24g of cross-linker METES and 120mg of catalyst DBTDL, and the solution was uniformly coated on a clean 40X 40mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PPF₁₀C₁₀。

The coating was found to have a static water contact angle of 87.6 deg., an ice shear strength of 23.3kPa, and icing/deicing cycle test times similar to those in example 5, with a surface average temperature of 35.8 deg.C after irradiation for 3min at a distance of 50cm from the simulated daylight.

Example 7 8.43g of CTA-PDMS-CTA (1.425mmol), 33.33g of NVP (300mmol), 6.315g of FA (8.55mmol), 12.3mg of AIBN (0.75mmol) were dissolved in 18mL of 1, 4-dioxane, added to a dry round-bottomed flask, deoxygenated by bubbling nitrogen at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

5.0g PDMS (molecular weight 400000), 0.5g FA-PVP-PDMS-PVP-FA and 0.75g carbon fiber were dissolved in a mixed solution of 5mL dichloromethane and 5mL tetrahydrofuran, mixed well, added with 0.25g cross-linker METES and 100mg catalyst DBTDL, and the solution was uniformly coated on a clean 40X 40mm²Drying the surface of the steel sheet at room temperature for 12 hours to obtain the amphiphilic polymer anti-ice coating PPF₁₀C₁₅。

The static water contact angle of the coating is measured to be 96.2 degrees, the ice shear strength is 35.0kPa, the icing/deicing cycle test times are similar to the results in the example 5, and the surface average temperature is 35.0 ℃ after the coating is irradiated for 3min at a position 50cm away from a simulated daylight lamp.

Example 8 11.24g of CTA-PDMS-CTA (1.9mmol), 44.44g of NVP (400mmol), 8.42g of FA (11.4mmol), 16.4mg of AIBN (1.0mmol) were dissolved in 24mL of 1, 4-dioxane, added to a dry round bottom flask, the solution was deoxygenated by bubbling nitrogen at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

6.0g PDMS (molecular weight 300000), 0.6g FA-PVP-PDMS-PVP-FA are dissolved in a mixed solution of 3mL dichloromethane and 6mL tetrahydrofuran, after mixing, 0.3g cross-linking agent METES and 120mg catalyst DBTDL are added, and the solution is evenly coated on clean 20X 50mm²Drying the surface of the glass slide for 12 hours at room temperature to obtain the amphiphilic polymer anti-ice coating PPF_10G。

The static water contact angle and ice shear strength of the coating were similar to the results in example 3.

Example 9 11.24g of CTA-PDMS-CTA (1.9mmol), 44.44g of NVP (400mmol), 8.42g of FA (11.4mmol), 16.4mg of AIBN (1.0mmol) were dissolved in 24mL of 1, 4-dioxane, added to a dry round bottom flask, the solution was deoxygenated by bubbling nitrogen at room temperature for 30min, then the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring, after which it was quenched with a mixture of ice and water. And (3) concentrating and precipitating the solution after reaction in cold diethyl ether with a volume of decaploid for at least three times, filtering, collecting a solid, and then drying in vacuum at 40 ℃ overnight to obtain the amphiphilic polymer FA-PVP-PDMS-PVP-FA.

8.0g of PDMS (molecular weight: 360000), 0.8g of FA-PVP-PDMS-PVP-FA and 0.4g of carbon nano-tube are dissolved in a mixed solution of 8mL of dichloromethane and 4mL of tetrahydrofuran, and after uniform mixing, 0.28g of cross-linking agent METES and 150mg of catalyst are addedReagent DBTDL, the solution is uniformly applied to a clean 20X 50mm²Drying the surface of the glass slide for 12 hours at room temperature to obtain the amphiphilic polymer anti-ice coating PPF₁₀C_5G。

The static water contact angle and ice shear strength of the coating were similar to the results in example 5.

FIG. 2 shows a bar graph of ice shear strength of the coatings of examples 1-6 with a pure PDMS coating without amphiphilic polymer and photo-thermal material; FIG. 3 shows a histogram of the surface average temperature of the coatings of examples 3-6 after 3min of simulated daylight illumination. As can be seen from the graph, the ice shear strength of the coating containing the PVP-based amphiphilic polymer was reduced compared to that of the pure PDMS coating, especially the PPF prepared in example 5 with the addition of FA-PVP-PDMS-PVP-FA and the photothermal material₁₀C₅The coating can reach 17.7kPa at least, and shows excellent anti-icing performance; after 3min of simulated daylight illumination, the surface temperature of the coating with the photo-thermal material was higher than that without the photo-thermal material, and the PPF prepared in example 5₁₀C₅The coating can reach 38.0 ℃ at most, so that the ice resistance of the coating can be further enhanced by using the photo-thermal effect.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. The amphiphilic ice-resistant coating based on PVP is characterized by comprising the following components in parts by mass: 100 parts of PDMS; 5-15 parts of amphiphilic polymer based on PVP; 0-15 parts of photo-thermal material; 2-5 parts of a cross-linking agent; 1-2 parts of a catalyst; wherein the PVP-based amphiphilic polymer is PVP-PDMS-PVP or FA-PVP-PDMS-PVP-FA;

the preparation method of the PVP-PDMS-PVP comprises the following steps: dissolving CTA-PDMS-CTA, N-vinyl pyrrolidone NVP and an initiator in a solvent, adding the solution into a dry container, blowing nitrogen or argon at room temperature to deoxidize the solution, then immersing the container in an oil bath, heating for polymerization reaction, and quenching with an ice water mixture after the reaction is finished; concentrating, precipitating and filtering the solution after reaction, collecting solid, and then drying to obtain the product;

2. The amphiphilic PVP-based ice-resistant coating according to claim 1, wherein the mass ratio of the PDMS to the amphiphilic PVP-based polymer to the photothermal material is 20:2: 1.

3. The PVP-based amphiphilic ice-resistant coating as claimed in claim 1, wherein the molar ratio of CTA-PDMS-CTA to N-vinyl pyrrolidone NVP is 0.625-1.25: 100-.

4. The PVP-based amphiphilic ice-resistant coating as claimed in claim 1, wherein the molar ratio of CTA-PDMS-CTA, N-vinylpyrrolidone NVP, acrylic acid-1- (1H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecyloxy) -isopropyl alcohol ester FA is 0.95-1.9: 200-.

5. The PVP-based amphiphilic ice-resistant coating as claimed in claim 4, wherein the molar ratio of CTA-PDMS-CTA, N-vinylpyrrolidone NVP, acrylic acid-1- (1H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecyloxy) -isopropyl alcohol ester FA is 0.95: 200:5.7.

6. The PVP-based amphiphilic ice-resistant coating as claimed in claim 1, wherein the cross-linking agent is Methyltriethoxysilane (METES); the catalyst is dibutyltin dilaurate DBTDL; the molecular weight of PDMS is 26000-400000.

7. A method of preparing a PVP-based amphiphilic ice-resistant coating according to any one of claims 1 to 6, comprising the steps of: and dissolving PDMS, an amphiphilic polymer based on PVP and a photo-thermal material in a mixed solution of dichloromethane and tetrahydrofuran, uniformly mixing, adding a cross-linking agent and a catalyst, uniformly coating the solution on the surface of a clean steel sheet or glass, and drying at room temperature to obtain the amphiphilic ice-resistant coating based on PVP.