Composition for preparing self-healing anti-icing coating, self-healing anti-icing coating and preparation method thereof, anti-icing coating as well as preparation method and application of anti-icing coating
Patent Information
- Application Number
- CN202510775002.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-11
- Publication Date
- 2025-10-28
Smart Images
Figure CN120842986A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of anti-icing coating technology, specifically to compositions for preparing self-healing anti-icing coatings, self-healing anti-icing coatings and their preparation methods, anti-icing coatings and their preparation methods and applications. Background Art
[0002] In low-temperature environments, moisture freezing on mechanical parts can cause them to freeze or become stuck. In industrial equipment such as car engines and robotic arms, icing can prevent normal operation, affecting production efficiency and work progress. Icing increases the surface roughness of fan blades, alters airflow distribution, and leads to decreased aerodynamic performance, reducing fan efficiency and output. Currently, two strategies are generally used to combat the damage caused by icing: active de-icing and passive de-icing. Active de-icing is usually direct and fast, but it consumes more energy. Passive de-icing achieves anti-icing through materials and design; its effect may be slower and dependent on environmental conditions, but it consumes less energy. It mainly uses superhydrophobic coatings, surface lubricating coatings, and anti-icing coatings to cover the surface.
[0003] Various anti-icing coatings can lose their ice-repellent effect due to mechanical damage, and may even develop strong ice adhesion due to interlocking phenomena between ice surfaces. Therefore, introducing self-healing functionality into ice-repellent coatings is a feasible and effective strategy to achieve durable anti-icing performance. Currently, most reported self-healing materials require energy absorption from the external environment to achieve self-healing, which limits the application scenarios of self-healing coatings. Some existing technologies achieve coating self-healing through disulfide bonds with dynamic exchange capabilities and introduce low surface energy resins and bio-based epoxy resins to achieve good anti-icing and ice-repellent properties. For example, CN109384927A discloses the application of a polysiloxane elastomer based on aromatic disulfide bonds and imine bonds as a self-healing material. In this application, 1,3,5-triphenylmethane, polysiloxane, and diaminodiphenyl disulfide are directly crosslinked through the condensation reaction of aldehyde and amino groups under the action of a catalyst. The reaction system excludes oxygen, and both aromatic disulfide bonds and imine bonds, two types of dynamic covalent bonds, are simultaneously introduced into the polysiloxane. A polysiloxane elastomer with excellent self-healing properties and high elongation at break was prepared, which can self-heal under room temperature / low temperature conditions. However, the anti-icing performance of this self-healing material is very poor. Summary of the Invention
[0004] The purpose of this invention is to provide a self-healing anti-icing coating with low ice adhesion strength, long delayed freezing time, and good ultraviolet shielding performance.
[0005] To achieve the above objectives, a first aspect of the present invention provides a composition for preparing a self-healing anti-icing coating, the composition comprising bis(3-aminopropyl)-terminated polydimethylsiloxane, a disulfide monomer, and a ternary glycidyl ether compound, wherein the weight ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the disulfide monomer, and the ternary glycidyl ether compound is 1:0.02-1.2:0.08-0.2; The number-average molecular weight of the bis(3-aminopropyl)-terminated polydimethylsiloxane is 4000-6000.
[0006] Preferably, the water content of the bis(3-aminopropyl)-terminated polydimethylsiloxane is not higher than 2 wt%.
[0007] Preferably, the kinematic viscosity of the bis(3-aminopropyl)-terminated polydimethylsiloxane at 25°C is 13-18 mm. 2 / s.
[0008] In a preferred embodiment, the disulfide monomer is 2,2'-diaminodiphenyl disulfide and / or 4,4'-dithiodiphenylamine.
[0009] Preferably, the ternary glycidyl ether compound is selected from at least one of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and tris(4-hydroxyphenyl)methane triglycidyl ether.
[0010] A second aspect of the present invention provides a method for preparing a self-healing anti-icing coating, the method comprising: mixing and reacting the components of a composition in the presence of an organic solvent to obtain the self-healing anti-icing coating; The composition is the composition for preparing a self-healing anti-icing coating as described in the first aspect.
[0011] Preferably, the organic solvent is selected from at least one of ethanol, methanol, n-hexane, petroleum ether, dichloromethane, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide, with tetrahydrofuran being the most preferred.
[0012] Preferably, the conditions for the mixing reaction include: being carried out under an inert atmosphere, at a temperature of 50-70°C, and for a time of 36-72 hours.
[0013] A third aspect of the present invention provides a self-healing anti-icing coating prepared by the method described in the second aspect.
[0014] A fourth aspect of the present invention provides a method for preparing an anti-icing coating, the method comprising: applying a self-healing anti-icing coating onto a substrate and performing a curing treatment to obtain the anti-icing coating; The curing conditions include: a temperature of 50-70℃ and a time of 10-24h. The self-healing anti-icing coating is the self-healing anti-icing coating described in the third aspect.
[0015] The fifth aspect of the present invention provides an anti-icing coating prepared by the method described in the fourth aspect.
[0016] The sixth aspect of the present invention provides the application of the self-healing anti-icing coating described in the third aspect and / or the anti-icing coating described in the fifth aspect in the anti-icing of mechanical components.
[0017] Through the above technical solution, the present invention has at least the following advantages compared with the prior art: (1) The composition for preparing self-healing anti-icing coating provided by the present invention is used to prepare self-healing anti-icing coating. The anti-icing coating formed by the self-healing anti-icing coating can reduce the ice adhesion strength and improve the delayed freezing time, thereby achieving the overall ice-repellent performance of the coating.
[0018] (2) The self-healing anti-icing coating provided by the present invention introduces benzene rings into disulfide monomers and trihydryl ether compounds to form a cross-linked network, which plays a role in ultraviolet shielding and extends the service life of equipment in outdoor scenarios. Attached Figure Description
[0019] Figure 1 These are experimental test diagrams showing the delayed freezing time of the anti-icing coatings prepared with the self-healing anti-icing coatings of Embodiments 1, 2, and 3 of the present invention and the aluminum sheets. Figure 2 These are test diagrams showing the ice adhesion strength between the anti-icing coatings prepared by the self-healing anti-icing coatings of Embodiments 1, 2, and 3 of the present invention and aluminum sheets. Figure 3 This is a test diagram of the self-healing performance of the anti-icing coating prepared by the self-healing anti-icing coating of Embodiment 3 of the present invention. Figure 4 These are UV shielding performance test diagrams of the anti-icing coatings prepared by the self-healing anti-icing coatings of Embodiments 1, 2, and 3 of the present invention. Detailed Implementation
[0020] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0021] As previously stated, a first aspect of the present invention provides a composition for preparing a self-healing anti-icing coating, the composition comprising bis(3-aminopropyl)-terminated polydimethylsiloxane, a disulfide monomer, and a ternary glycidyl ether compound, wherein the weight ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the disulfide monomer, and the ternary glycidyl ether compound is 1:0.02-1.2:0.08-0.2; The number-average molecular weight of the bis(3-aminopropyl)-terminated polydimethylsiloxane is 4000-6000.
[0022] Preferably, the weight ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the disulfide monomer, and the ternary glycidyl ether compound is 1:0.1-0.5:0.1-0.15. The inventors have found that, under this preferred condition, the technical solution provided by the present invention can obtain an anti-icing coating with lower ice adhesion strength, stronger ultraviolet shielding performance, and longer delayed icing time.
[0023] Preferably, the water content of the bis(3-aminopropyl)-terminated polydimethylsiloxane is not higher than 2 wt%.
[0024] Preferably, the kinematic viscosity of the bis(3-aminopropyl)-terminated polydimethylsiloxane at 25°C is 13-18 mm. 2 / s.
[0025] Preferably, the disulfide monomer is 2,2'-diaminodiphenyldisulfide and / or 4,4'-dithiodiphenylamine.
[0026] Preferably, the ternary glycidyl ether compound is selected from at least one of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and tris(4-hydroxyphenyl)methane triglycidyl ether.
[0027] As mentioned above, a second aspect of the present invention provides a method for preparing a self-healing anti-icing coating, the method comprising: mixing and reacting the components of a composition in the presence of an organic solvent to obtain the self-healing anti-icing coating; The composition is the composition for preparing a self-healing anti-icing coating as described in the first aspect.
[0028] Preferably, the organic solvent is selected from at least one of ethanol, methanol, n-hexane, petroleum ether, dichloromethane, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide, with tetrahydrofuran being the most preferred.
[0029] Preferably, the water content of the organic solvent is not higher than 2 wt%.
[0030] In a preferred embodiment, the amount of organic solvent used is 3-5 mL relative to 1 g of the bis(3-aminopropyl)-terminated polydimethylsiloxane.
[0031] Preferably, the conditions for the mixing reaction include: being carried out under an inert atmosphere, at a temperature of 50-70°C, and for a time of 36-72 hours.
[0032] Preferably, the mixing reaction is carried out under an inert atmosphere; more preferably, the inert atmosphere is nitrogen.
[0033] As previously stated, a third aspect of the present invention provides a self-healing anti-icing coating prepared by the method described in the second aspect.
[0034] As mentioned above, a fourth aspect of the present invention provides a method for preparing an anti-icing coating, the method comprising: applying a self-healing anti-icing coating onto a substrate and performing a curing treatment to obtain the anti-icing coating; The curing conditions include: a temperature of 50-70℃ and a time of 10-24h. The self-healing anti-icing coating is the self-healing anti-icing coating described in the third aspect.
[0035] Preferably, the substrate is selected from at least one of aluminum sheet, fiberglass and polytetrafluoroethylene mold, and is preferably aluminum sheet.
[0036] Preferably, the coating density is 2-6 cm³. 2 / g.
[0037] As previously stated, the fifth aspect of the present invention provides an anti-icing coating prepared by the method described in the fourth aspect.
[0038] As previously stated, the sixth aspect of the present invention provides the application of the self-healing anti-icing coating of the third aspect and / or the anti-icing coating of the fifth aspect in the anti-icing of mechanical components.
[0039] In the following examples, unless otherwise specified, all instruments, reagents, and materials used are conventional and can be obtained through conventional commercial channels. Unless otherwise stated, all reagents used are commercially available analytical grade products.
[0040] Polypropylene glycol diglycidyl ether: purchased from Shanghai Titan Technology Co., Ltd.
[0041] Anhydrous tetrahydrofuran: purchased from Shanghai Titan Technology Co., Ltd., with a water content of 0.05 wt%.
[0042] The bis(3-aminopropyl)-terminated polydimethylsiloxanes were all purchased from Shanghai Titan Technology Co., Ltd., CAS No. 106214-84-0, grade 013748621, of which: Bis(3-aminopropyl)-terminated polydimethylsiloxane (W-1): 2wt% water content, kinematic viscosity of 15 mm at 25°C. 2 / s, with a number-average molecular weight of 5000; Bis(3-aminopropyl)-terminated polydimethylsiloxane (W-2): 2 wt% water content, kinematic viscosity of 14 mm at 25°C. 2 / s, with a number-average molecular weight of 4000; Bis(3-aminopropyl)-terminated polydimethylsiloxane (W-3): 2 wt% water content, kinematic viscosity of 18 mmHg at 25°C. 2 / s, with a number-average molecular weight of 6000; Bis(3-aminopropyl)-terminated polydimethylsiloxane (W-D1): with a water content of 2 wt% and a kinematic viscosity of 13 mm at 25°C. 2 / s, with a number-average molecular weight of 3000.
[0043] Example 1 In an organic solvent (anhydrous tetrahydrofuran solution), bis(3-aminopropyl)-terminated polydimethylsiloxane (W-1, 12.08 g), disulfide monomer (4,4'-dithiodiphenylamine), and ternary glycidyl ether compound (tris(4-hydroxyphenyl)methane triglycidyl ether) were added and stirred until completely dissolved. The mixture was then stirred under nitrogen conditions (60 °C for 48 h) to obtain a self-healing anti-icing coating. The weight ratio of bis(3-aminopropyl)-terminated polydimethylsiloxane, disulfide monomer, and ternary glycidyl ether compound is 1:0.024:0.09. The amount of organic solvent used is 4 mL relative to 1 g of bis(3-aminopropyl)-terminated polydimethylsiloxane.
[0044] Example 2 In an organic solvent (anhydrous tetrahydrofuran solution), bis(3-aminopropyl)-terminated polydimethylsiloxane (W-2, 6.04 g), disulfide monomer (2,2'-diaminodiphenyl disulfide), and ternary glycidyl ether compound (glycerol triglycidyl ether) were added and stirred until completely dissolved. The mixture was then subjected to a nitrogen reaction (stirring at 60°C for 48 h) to obtain a self-healing anti-icing coating. The weight ratio of bis(3-aminopropyl)-terminated polydimethylsiloxane, disulfide monomer and ternary glycidyl ether compound is 1:0.05:0.122. The amount of organic solvent used is 4 mL relative to 1 g of bis(3-aminopropyl)-terminated polydimethylsiloxane.
[0045] Example 3 In an organic solvent (anhydrous tetrahydrofuran solution), bis(3-aminopropyl)-terminated polydimethylsiloxane (W-3, 3.02 g), disulfide monomer (4,4'-dithiodiphenylamine), and ternary glycidyl ether compound (trimethylolpropane triglycidyl ether) were added and stirred until completely dissolved. The mixture was then subjected to a nitrogen reaction (stirring at 60°C for 48 h) to obtain a self-healing anti-icing coating. The weight ratio of bis(3-aminopropyl)-terminated polydimethylsiloxane, disulfide monomer and ternary glycidyl ether compound is 1:1:0.185. The amount of organic solvent used is 4 mL relative to 1 g of bis(3-aminopropyl)-terminated polydimethylsiloxane.
[0046] Example 4 The procedure was carried out using a method similar to that in Example 1, except that the amount of bis(3-aminopropyl)-terminated polydimethylsiloxane (W-1) was kept constant, and the weight ratio of bis(3-aminopropyl)-terminated polydimethylsiloxane, disulfide monomer and ternary glycidyl ether compound was adjusted to 1:0.08:0.18. Everything else is the same, resulting in a self-healing anti-icing coating.
[0047] Comparative Example 1 The procedure was carried out using a method similar to that in Example 1, except that the amount of bis(3-aminopropyl)-terminated polydimethylsiloxane (W-1) was kept constant, and the weight ratio of bis(3-aminopropyl)-terminated polydimethylsiloxane, disulfide monomer and ternary glycidyl ether compound was adjusted to 1:1.8:0.4. Everything else is the same, resulting in a self-healing anti-icing coating.
[0048] Comparative Example 2 The procedure was carried out in a similar manner to that of Example 1, except that W-D1 of equal mass was used to replace W-1. Everything else is the same, resulting in a self-healing anti-icing coating.
[0049] Comparative Example 3 The procedure was carried out using a method similar to that in Example 1, except that an equal mass of polypropylene glycol diglycidyl ether was used instead of the triglycidyl ether compound (tris(4-hydroxyphenyl)methane triglycidyl ether). Everything else is the same, resulting in a self-healing anti-icing coating.
[0050] Test case According to a coating density of 4cm2 / g The self-healing anti-icing coating prepared in the example was coated onto the substrate (aluminum sheet) and vacuum dried at 60°C for 10 h to obtain the anti-icing coating.
[0051] The delayed icing performance, ice adhesion strength, self-healing performance and ultraviolet shielding performance of the above-mentioned anti-icing coating were tested. The test results of delayed icing performance and ice adhesion strength are shown in Table 1.
[0052] The relevant testing methods are as follows: Delayed freezing performance: The cold stage was pre-cooled from room temperature to -15°C, and nitrogen gas was pumped into the sample chamber to maintain a dry environment; the anti-icing coating sample was placed on the cooling stage for 10 min, and 4 μL of deionized water was dropped onto the sample surface using a microsyringe. The time for the droplet to contact the sample surface was recorded as 0 s; the changes in the droplet were recorded using a high-speed camera in continuous shooting mode until it was completely frozen. The time for the droplet to change from transparent to opaque was the freezing delay time.
[0053] Ice adhesion strength: The anti-icing coating was placed on a cold stage, and a hollow glass cube with an inner diameter of 1 cm was placed vertically on the coating surface. 450 μL of deionized water was added, and a glass cover was placed on top. The temperature inside the glass cover was controlled at -15℃ and the glass was frozen in a nitrogen atmosphere for 4 hours to ensure that the water was completely frozen. During the test, the push-pull force gauge was used to push the hollow glass tube on the coating surface at a speed of 0.1 mm / s, and the maximum shear force was recorded from the start until the hollow glass tube completely detached from the coating surface. Each coating was tested in three parallel tests.
[0054] Self-healing performance: After scratching the anti-icing coating with a knife, the scratch disappearance time of the anti-icing coating within 300 minutes was recorded at 60℃.
[0055] Ultraviolet shielding performance: The ultraviolet shielding performance of the anti-icing coating samples was studied using a UV-3600 Plus UV-Vis spectrophotometer, with test wavelengths ranging from 200 nm to 800 nm.
[0056] Table 1
[0057] This invention is in Figure 1 The example provides test graphs of the delayed icing time of the anti-icing coatings prepared with self-healing anti-icing coatings from Examples 1, 2, and 3, and aluminum sheets. Figure 1It can be seen that the freezing delay times of Examples 1, 2 and 3 are 875s, 1443s and 1653s respectively, while the freezing delay time of aluminum sheet is only 34s. This indicates that the self-healing anti-icing coating provided by the present invention has a low molecular chain length and a high crosslinking density, resulting in a high concentration of hydroxyl groups. Hydrophilic groups such as hydroxyl groups can interact with water molecules by forming hydrogen bonds, thereby effectively prolonging the freezing time and reducing the freezing temperature.
[0058] This invention is in Figure 2 The example provides test diagrams of the ice adhesion strength between the anti-icing coatings prepared with the self-healing anti-icing coatings of Examples 1, 2, and 3 and the aluminum sheets. Figure 2 It can be seen that the ice adhesion strengths of Examples 1, 2, and 3 are 28.5 kPa, 34.7 kPa, and 38.9 kPa, respectively. During the de-icing process, the mismatch in Young's modulus between the ice and the coating may cause incompatibility in the deformation of the ice-coating interface, leading to the formation of interfacial voids, which promotes ice removal. This indicates that the self-healing anti-icing coating provided by this invention has a large ice adhesion strength, low hydrophobicity, and a large Young's modulus.
[0059] This invention is in Figure 3 The diagram above provides, exemplarily, a test image of the self-healing performance of the anti-icing coating prepared by the self-healing anti-icing coating of Embodiment 3 of the present invention; Figure 3 In the middle, from left to right, are the anti-icing coating before scraping treatment and the anti-icing coating after scraping treatment and being placed in a 60℃ drying oven for 240 minutes. Figure 3 It can be seen that the scratches basically disappeared after heating for 240 minutes. This is because the self-healing ability of the anti-icing coating mainly relies on the disulfide monomer and the low glass transition temperature. The reversible disulfide monomer can promote the exchange reaction in the anti-icing coating, and the low glass transition temperature makes the molecular chain have better mobility.
[0060] This invention is in Figure 4 The present invention provides exemplary test diagrams of the ultraviolet shielding performance of the anti-icing coatings prepared by the self-healing anti-icing coatings of Embodiments 1, 2, and 3 of the present invention; by Figure 4 It can be seen that the anti-icing coating of Example 3 even shows 0% transmittance in the wavelength range of 400-413nm, which indicates that the benzene ring density of the anti-icing coating of the present invention is large, thus improving the ultraviolet shielding capability.
[0061] The results above show that the composition for preparing self-healing anti-icing coating provided by the present invention can produce a self-healing anti-icing coating. The anti-icing coating formed by the self-healing anti-icing coating can reduce the ice adhesion strength and improve the delay of freezing time. In addition, the anti-icing coating can also play a role in ultraviolet shielding, extending the service life of the equipment in outdoor scenarios.
[0062] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A composition for preparing a self-healing anti-icing coating, characterized in that, The composition contains bis(3-aminopropyl)-terminated polydimethylsiloxane, a disulfide monomer, and a ternary glycidyl ether compound, wherein the weight ratio of the bis(3-aminopropyl)-terminated polydimethylsiloxane, the disulfide monomer, and the ternary glycidyl ether compound is 1:0.02-1.2:0.08-0.
2. The number-average molecular weight of the bis(3-aminopropyl)-terminated polydimethylsiloxane is 4000-6000.
2. The composition according to claim 1, wherein, The water content of the bis(3-aminopropyl)-terminated polydimethylsiloxane is not higher than 2 wt%. And / or, the kinematic viscosity of the bis(3-aminopropyl)-terminated polydimethylsiloxane at 25°C is 13-18 mm. 2 / s.
3. The composition according to claim 1, wherein, The disulfide monomer is 2,2'-diaminodiphenyldisulfide and / or 4,4'-dithiodiphenylamine.
4. The composition according to any one of claims 1-3, wherein, The ternary glycidyl ether compound is selected from at least one of glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and tri(4-hydroxyphenyl)methane triglycidyl ether.
5. A method for preparing a self-healing anti-icing coating, characterized in that, The method includes: mixing and reacting the components in the composition in the presence of an organic solvent to obtain the self-healing anti-icing coating; The composition is the composition for preparing a self-healing anti-icing coating as described in any one of claims 1-4.
6. The method according to claim 5, wherein, The organic solvent is selected from at least one of ethanol, methanol, n-hexane, petroleum ether, dichloromethane, ethyl acetate, tetrahydrofuran, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the conditions for the mixed reaction include: being carried out under an inert atmosphere at a temperature of 50-70°C for 36-72 hours.
7. A self-healing anti-icing coating prepared by the method of claim 5 or 6.
8. A method for preparing an anti-icing coating, characterized in that, The method includes: applying a self-healing anti-icing coating to a substrate and then curing it to obtain the anti-icing coating; The curing conditions include: a temperature of 50-70℃ and a time of 10-24h. The self-healing anti-icing coating is the self-healing anti-icing coating as described in claim 7.
9. The anti-icing coating prepared by the method of claim 8.
10. The application of the self-healing anti-icing coating of claim 7 and / or the anti-icing coating of claim 9 in the anti-icing of mechanical parts.