CN111471392A - Amphiphilic ice-resistant coating based on PVP and preparation method thereof - Google Patents

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

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CN111471392A
CN111471392A CN202010096180.3A CN202010096180A CN111471392A CN 111471392 A CN111471392 A CN 111471392A CN 202010096180 A CN202010096180 A CN 202010096180A CN 111471392 A CN111471392 A CN 111471392A
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张雷
杨静
陈鹏光
郭洪爽
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Tianjin University
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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.
Although the superhydrophobic coating can effectively reduce the ice formation temperature, under high humidity, the superhydrophobic surface has a higher ice freezing rate than the smooth surface, and tiny water droplets can penetrate into the nano texture, thereby causing the destruction of the surface micro/nano structure after the deicing cycle, reducing the mechanical durability, and increasing the ice adhesion strength of the solid surface, therefore, the highly efficient anti-icing coating cannot be limited to using a single hydrophobic material, the porous surface injected with a lubricating liquid (S L IPS) is an anti-icing smooth coating, can delay and reduce the ice adhesion strength, has excellent anti-fouling adhesion, and self-priming properties, and is expected to be replaced by a lubricant with a high affinity to absorb water, which is expected to be used as a lubricant for a large scale, such as IPS 56, IPS, which is expected to be used for a large scale repair of ice-resistant coatings, such as a lubricant with a high affinity for water, which is more than IPS, and is expected to be used for a lubricant with a large scale.
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.
Figure BDA0002385427380000021
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.
Figure BDA0002385427380000031
Preferably, the cross-linking agent is methyl triethoxysilane METES, the catalyst is dibutyltin dilaurate DBTD L, and 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,the coating can 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) And (3) testing the ice shear strength, namely taking 3 coating samples in each group, placing the coating samples on a cold table, performing hydrophobic treatment on a hollow organic glass cylinder with the inner diameter of 10mm by using perfluorooctyl trichlorosilane, vertically placing the hollow organic glass cylinder on the surface of each sample, dropwise adding 450 mu L deionized water into the sample, cooling the cold table from room temperature to-15 ℃, keeping the temperature for 4 hours in a nitrogen atmosphere, ensuring that the liquid in the cylinder is completely frozen, using an Imada ZP-50N push-pull dynamometer, pushing the cylinder forwards at the speed of 0.1mm/s, recording the maximum shear force of the push-pull dynamometer just contacting the cylinder until the ice is completely separated from the coating surface, and taking an average value after testing each group of samples for 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 1A amphiphilic polymer PVP-PDMS-CTA (3.7 g) was taken and dissolved in 8m L1, 4-dioxane as 3.11 g of CTA-PDMS-CTA (0.625mmol), 11.11g of NVP (100mmol), 16.4mg of 2, 2-azobisisobutyronitrile AIBN (1.0mmol) was added to a dry round bottom flask and the solution was deoxygenated by bubbling nitrogen at room temperature for 30min, after which the flask was immersed in an oil bath preheated to 75 ℃ and reacted for 24h with stirring and then quenched with a mixture of ice and water, the reacted solution was concentrated in decaploid cold ether at least three times, the solid was collected after filtration and then dried under vacuum at 40 ℃ overnight to give the amphiphilic polymer PVP-PDMS-PVP.
Dissolving 5.0g PDMS (molecular weight 26000) and 0.25g PVP-PDMS-PVP in a mixed solution of 3m L dichloromethane and 5m L tetrahydrofuran, mixing, adding 0.1g cross-linking agent METES and 50mg catalyst DBTD L, 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 PP5。
The coating was measured to have a static water contact angle of 104 deg. and an ice shear strength of 43 kPa.
Example 2A amphiphilic polymer PVP-PDMS-PVP was obtained by dissolving 7.4g of CTA-PDMS-CTA (1.25mmol), 22.22g of NVP (200mmol), 32.8mg of AIBN (2.0mmol) in 16m L1, 4-dioxane, adding it to a dry round bottom flask, deoxygenating the solution by bubbling argon at room temperature for 30min, subsequently immersing the flask in an oil bath preheated to 75 deg.C, reacting for 24h with stirring, then quenching with a mixture of ice and water, concentrating the reacted solution in a decaploid cold ether at least three times, collecting the solid after filtration, then drying overnight under vacuum at 40 deg.C.
8.0g of PDMS (molecular weight 26000), 0.4g of PVP-PDMS-PVP and 0.4g of carbon fiber were dissolved in a mixed solution of 6m L dichloromethane and 8m L tetrahydrofuran, mixed well, added with 0.24g of cross-linking agent METES and 120mg of catalyst DBTD L, and the solution was uniformly coated on clean 40 × 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 an amphiphilic polymer FA-PVP-PDMS-PVP-FA was obtained by dissolving 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) in 12m L1, 4-dioxane, adding to a dry round bottom flask, deoxygenating the solution by bubbling nitrogen at room temperature for 30min, subsequently immersing the flask in an oil bath preheated to 75 deg.C, reacting for 24h with stirring, then quenching with a mixture of ice and water, precipitating the reacted solution in decaploid cold ether at least three times, collecting the solid after filtration, and drying in vacuum at 40 deg.C overnight.
5.0g PDMS (molecular weight 320000), 0.5g FA-PVP-PDMS-PVP-FA are dissolved in a mixed solution of 3m L dichloromethane and 5m L tetrahydrofuran, after mixing uniformly, 0.125g cross-linking agent METES and 50mg catalyst DBTD L are added, and the solution is evenly coated 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 4A amphiphilic polymer FA-PVP-PDMS-CTA (8.425 mmol), prepared by dissolving 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) in 18m L1, 4-dioxane, was added to a dry round bottom flask, deoxygenated by bubbling argon at room temperature for 30min, followed by immersing the flask in an oil bath preheated to 75 deg.C, reacted for 24h with stirring, then quenched with a mixture of ice and water, after the reaction, the solution was concentrated in decaploid cold ether at least three times, the solid was collected after filtration, and then dried under vacuum at 40 deg.C overnight to give 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 4m L dichloromethane and 3m L tetrahydrofuran, after mixing, 0.12g cross-linking agent METES and 60mg catalyst DBTD L are added, and the solution is evenly coated on clean 30 × 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 12m L1, 4-dioxane, which was added to a dry round bottom flask, the solution was deoxygenated by bubbling nitrogen 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, the post-reaction solution was concentrated in decaploid cold ether at least three times, the solid was collected after filtration and then dried under vacuum at 40 ℃ overnight to give the amphiphilic polymer FA-PVP-PDMS-PVP-FA.
2.0g of PDMS (molecular weight: 360000), 0.2g of FA-PVP-PDMS-PVP-FA and 0.1g of carbon fiber are dissolved in a mixed solution of 1.5m L dichloromethane and 2m L tetrahydrofuran, after mixing uniformly, 60mg of cross-linking agent METES and 30mg of catalyst DBTD L are added, and the solution is evenly coated on clean 20 × 20mm and 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 6A amphiphilic polymer FA-PVP-PDMS-CTA (8.425 mmol), prepared by dissolving 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) in 18m L1, 4-dioxane, charging to a dry round bottom flask, deoxygenating the solution by bubbling argon at room temperature for 30min, subsequently immersing the flask in an oil bath preheated to 75 deg.C, reacting for 24h with stirring, then quenching with a mixture of ice and water, precipitating the reacted solution at least three times in a decaploid cold ether, collecting the solid after filtration, and drying in vacuo at 40 deg.C overnight to give 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 6m L dichloromethane and 6m L tetrahydrofuran, mixed uniformly, added with 0.24g of cross-linking agent METES and 120mg of catalyst DBTD L, and the solution was uniformly coated on clean 40 × 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 7A amphiphilic polymer FA-PVP-PDMS-CTA (8.425 mmol), prepared by dissolving 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) in 18m L1, 4-dioxane, charging to a dry round bottom flask, deoxygenating the solution by bubbling nitrogen at room temperature for 30min, subsequently immersing the flask in an oil bath preheated to 75 deg.C, reacting for 24h with stirring, then quenching with a mixture of ice and water, precipitating the reacted solution at least three times in a decaploid cold ether, collecting the solid after filtration, and drying in vacuo at 40 deg.C overnight to give the amphiphilic polymer FA-PVP-PDMS-PVP-FA.
5.0g of PDMS (molecular weight 400000), 0.5g of FA-PVP-PDMS-PVP-FA and 0.75g of carbon fiber were dissolved in a mixed solution of 5m L dichloromethane and 5m L tetrahydrofuran, mixed uniformly, added with 0.25g of cross-linking agent METES and 100mg of catalyst DBTD L, and the solution was uniformly coated on a clean 40 × 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 an amphiphilic polymer FA-PVP-PDMS-CTA (1.9mmol), 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 24m L1, 4-dioxane, added to a dry round bottom flask, deoxygenated by bubbling nitrogen at room temperature for 30min, followed by immersing the flask in an oil bath preheated to 75 deg.C, reacted for 24h with stirring, then quenched with a mixture of ice and water, after the reaction, the solution was concentrated in decaploid cold ether at least three times, the solid was collected after filtration, and then dried under vacuum at 40 deg.C overnight to give the amphiphilic polymer FA-PVP-PDMS-PVP-FA.
Dissolving 6.0g PDMS (molecular weight 300000) and 0.6g FA-PVP-PDMS-PVP-FA in a mixed solution of 3m L dichloromethane and 6m L tetrahydrofuran, mixing, adding 0.3g cross-linking agent METES and 120mg catalyst DBTD L, and mixingThe solution was applied uniformly to a clean 20 × 50mm2Drying the surface of the glass slide for 12 hours at room temperature to obtain the amphiphilic polymer anti-ice coating PPF10G。
The static water contact angle and ice shear strength of the coating were similar to the results in example 3.
Example 9A amphiphilic polymer FA-PVP-PDMS-CTA (11.9 mmol), 11.44 g 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 24m L1, 4-dioxane, added to a dry round bottom flask, deoxygenated by bubbling nitrogen at room temperature for 30min, followed by immersing the flask in an oil bath preheated to 75 deg.C, reacted for 24h with stirring, then quenched with a mixture of ice and water, after the reaction, the solution was concentrated in decaploid cold ether at least three times, the solid was collected after filtration, and then dried under vacuum at 40 deg.C overnight to give the amphiphilic polymer FA-PVP-PDMS-PVP-FA.
8.0g of PDMS (molecular weight of 360000), 0.8g of FA-PVP-PDMS-PVP-FA and 0.4g of carbon nanotubes are dissolved in a mixed solution of 8m L dichloromethane and 4m L tetrahydrofuran, 0.28g of cross-linking agent METES and 150mg of catalyst DBTD L are added after uniform mixing, and the solution is uniformly coated on clean 20 × 50mm and 50mm2Drying the surface of the glass slide for 12 hours at room temperature to obtain the amphiphilic polymer anti-ice coating PPF10C5G。
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 maximum temperature of the coating can reach 38.0 ℃,so that the anti-icing properties of the coating can be further enhanced by means of a photothermal 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 (9)

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.
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 of claim 1, wherein the PVP-PDMS-PVP is prepared by: 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.
4. The PVP-based amphiphilic ice-resistant coating according to claim 3, wherein the molar ratio of CTA-PDMS-CTA to N-vinylpyrrolidone NVP is 0.625-1.25: 100-.
5. The PVP-based amphiphilic ice-resistant coating of claim 1, wherein the FA-PVP-PDMS-PVP-FA is prepared by: 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.
6. The PVP-based amphiphilic ice-resistant coating according to claim 5, wherein the molar ratio of CTA-PDMS-CTA, N-vinylpyrrolidone NVP, acrylic acid-1- (1H,1H,2H, 2H-perfluorodecyloxy) -3- (3,6, 9-trioxadecyloxy) -isopropyl alcohol ester FA is 0.95-1.9: 200-.
7. The PVP-based amphiphilic ice-resistant coating as claimed in claim 5, 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.
8. The PVP-based amphiphilic ice-resistant coating of claim 1, wherein the crosslinker is methyltriethoxysilane METES, the catalyst is dibutyltin dilaurate DBTD L, and the molecular weight of PDMS is 26000-400000.
9. A method of preparing a PVP-based amphiphilic ice-resistant coating according to any one of claims 1 to 8, 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.
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CN102676056A (en) * 2012-06-01 2012-09-19 天津大学 Nano composite ice-covering-proof coating containing phase change silicone oil and preparation method thereof
CN109294394A (en) * 2018-09-21 2019-02-01 华东理工大学 A kind of superhydrophilic self-cleaning epoxy coating and the preparation method and application thereof

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CN101063022A (en) * 2006-04-28 2007-10-31 联合工艺公司 Erosion resistant anti-icing coatings
CN102268222A (en) * 2011-08-17 2011-12-07 天津大学 Icing-resisting paint containing alkane phase change microcapsules and preparation method thereof
CN102676056A (en) * 2012-06-01 2012-09-19 天津大学 Nano composite ice-covering-proof coating containing phase change silicone oil and preparation method thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116515388A (en) * 2023-03-30 2023-08-01 天津大学 Anti-freezing protein-like zwitterionic polymer-based anti-icing paint and preparation method and application thereof

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