A photothermal self-healing anti-icing coating material, a preparation method and application thereof

Abstract

The application discloses a kind of photo-thermal self-healing anti-icing coating materials and its preparation method and application, the coating material is prepared by using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, triformylphloroglucin and photo-thermal nanoparticles Polymer;Wherein, the amino group on the amino-terminated polydimethylsiloxane and the isocyanate group on hexamethylene diisocyanate occur condensation polymerization, generate polymer long chain, there is hydrogen bond effect between the urea group produced by amino and isocyanate group;At the same time, amino-terminated polydimethylsiloxane and triformylphloroglucin occur condensation polymerization, form polymer network, the dynamic imine bond produced can dynamically form and break reaction.The material photo-thermal responsiveness, self-healing, substrate independence and low surface energy, especially in preventing and removing ice, frost, can extend water droplet freezing time 3 times in low temperature environment of-10 DEG C, and can realize photo-thermal anti-icing, frost by near infrared light.

Description

Technical Field

[0001] This invention relates to the field of polymer coating preparation technology, and in particular to a photothermal self-healing anti-icing coating material, its preparation method, and its application. Background Technology

[0002] Icing is a common physical phenomenon, but ice and frost adhering to surfaces adversely affect equipment operation and transportation. Currently used de-icing technologies include mechanical de-icing, chemical de-icing, and thermal de-icing, but these suffer from low efficiency, corrosion, and high energy consumption. Therefore, there is an urgent need for green and efficient solutions that can prevent ice and frost formation on equipment surfaces and quickly remove them. Ferric oxide nanoparticles (Fe3O4 NPs) have a large specific surface area and can utilize the near-infrared wavelengths of sunlight, which constitute a large proportion, to convert into heat, effectively inhibiting surface ice and frost formation and melting existing ice and frost. However, they are easily oxidized to iron oxide, making it impossible for them to maintain their photothermal properties stably over a long period.

[0003] Polydimethylsiloxane (PDMS) is renowned for its excellent optical transparency, chemical stability, and low surface energy. It ensures smooth light transmission to magnetite nanoparticles while preventing their oxidation, thus guaranteeing long-term stable photothermal properties. However, PDMS has insufficient adhesion strength to the substrate, making the prepared coating prone to detachment from the substrate surface. Furthermore, its low modulus makes the surface easily damaged, leading to mechanical interlocking that reduces anti-icing performance and further deteriorates its properties. It also easily causes large-area material detachment, compromising its long-term effectiveness. Introducing dynamic covalent and non-covalent interactions into the network promises to increase the coating's lifespan and adhesion strength to the substrate. Summary of the Invention

[0004] To address the problems existing in the prior art and reduce the performance degradation of polymer coatings caused by mechanical damage or peeling, and to achieve long-term anti-icing and de-icing effects, this invention proposes a method for preparing a photothermal self-healing polymer coating using amino-terminated polydimethylsiloxane (NH2-PDMS), hexamethylene diisocyanate (HDI), trimesoaldehyde (BA), and iron oxide nanoparticles (Fe3O4 NPs) as raw materials. This polymer coating is a multifunctional PDMS@Fe3O4 polymer composite material with various properties, including photothermal responsiveness, adhesion, self-healing, and plasticity. In a -10°C environment, it can inhibit surface ice and frost accumulation with the aid of near-infrared light (1.2W) and can melt surface ice and frost.

[0005] To achieve the above objectives, in a first aspect, the present invention provides a photothermal self-healing anti-icing coating material, wherein the coating material is a polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, trimesin, and photothermal nanoparticles; wherein, the amino groups on the amino-terminated polydimethylsiloxane and the isocyanates on the hexamethylene diisocyanate undergo a condensation reaction to generate a long polymer chain, and there are hydrogen bonds between the urea groups generated by the amino groups and the isocyanates; simultaneously, the amino-terminated polydimethylsiloxane and trimesin undergo a condensation reaction to form a polymer network, and the resulting dynamic imine bonds can dynamically form and break.

[0006] Furthermore, the photothermal nanoparticles are iron oxide nanoparticles; the polymer is a modified polydimethylsiloxane composite iron oxide multifunctional polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, pyromellitic methyl ether and iron oxide nanoparticles.

[0007] Furthermore, the amino-terminated polydimethylsiloxane is a chain polymer with an average molecular weight of 3000 g / mol.

[0008] In an alternative embodiment, the present invention provides a photothermal self-healing anti-icing coating material, wherein the coating material is a polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, and photothermal nanoparticles; wherein the amino groups on the amino-terminated polydimethylsiloxane and the isocyanates on the hexamethylene diisocyanate undergo a condensation reaction to generate a long polymer chain, and there are hydrogen bonds between the urea groups generated by the amino groups and the isocyanates; the photothermal nanoparticles are iron oxide nanoparticles; and the polymer is a modified polydimethylsiloxane composite iron oxide multifunctional polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, and iron oxide nanoparticles.

[0009] In another alternative, the present invention provides a photothermal self-healing anti-icing coating material, wherein the coating material is a polymer prepared using amino-terminated polydimethylsiloxane, trimesin, and photothermal nanoparticles; wherein the amino-terminated polydimethylsiloxane undergoes a condensation reaction with trimesin to form a polymer network, and the resulting dynamic imine bonds can dynamically form and break; the photothermal nanoparticles are iron oxide nanoparticles; and the polymer is a modified polydimethylsiloxane composite iron oxide multifunctional polymer prepared using amino-terminated polydimethylsiloxane, trimesin, and iron oxide nanoparticles.

[0010] Secondly, the present invention provides a method for preparing the above-mentioned photothermal self-healing anti-icing coating material, the method comprising the following steps:

[0011] S1. Dissolve hexamethylene diisocyanate and / or trimesaldehyde in tetrahydrofuran to obtain a mixed solution;

[0012] S2. Sonicate the mixed solution until it is completely dissolved to obtain a hexamethylene diisocyanate mixed solution, a pyromellitic trioxide mixed solution, or a pyromellitic trioxide-hexamethylene diisocyanate-pyromellitic trioxide mixed solution.

[0013] S3. Add amino-terminated polydimethylsiloxane to the mixed solution to obtain a PDMS precursor solution, and obtain a uniform PDMS prepolymer solution after magnetic stirring and heating.

[0014] S4. Add Fe3O4 nanoparticles to PDMS prepolymer solution, and obtain a uniform PDMS@Fe3O4 prepolymer solution after oscillation and sonication.

[0015] S5. The PDMS@Fe3O4 prepolymer liquid is coated onto the material surface and cured at room temperature and normal pressure to obtain a photothermal self-healing anti-icing coating.

[0016] Furthermore, in step S1, the ratio of hexamethylene diisocyanate to pyromellitic aldehyde is 1:0-0:1.

[0017] Furthermore, in step S2, the ultrasonic treatment parameters are as follows: the mixed solution is treated in an ultrasonic device with a power of 60W for 5 minutes to dissolve hexamethylene diisocyanate and / or pyromellitic aldehyde.

[0018] Furthermore, the amino-terminated polydimethylsiloxane is a chain polymer with an average molecular weight of 3000 g / mol.

[0019] Furthermore, in step S3, the mass ratio of amino-terminated polydimethylsiloxane to tetrahydrofuran in the PDMS precursor solution is 1:3.

[0020] Furthermore, the stirring and heating parameters in step S3 are as follows: the PDMS precursor solution is magnetically stirred for 30 minutes, and the heating temperature is set to 50°C to obtain a uniform PDMS prepolymer solution.

[0021] Furthermore, the diameter of the iron oxide nanoparticles is 20 nm.

[0022] Furthermore, the mass of the iron oxide nanoparticles in the PDMS@Fe3O4 prepolymer solution is 0g-3g.

[0023] Furthermore, the oscillation and ultrasonic parameters in step S4 are as follows: after oscillating the PDMS@Fe3O4 prepolymer liquid for 1 minute, it is treated in a 200W ultrasonic device for 15 minutes, and the above process is repeated 3 times.

[0024] Thirdly, the present invention provides an application of a photothermal self-healing anti-icing coating material, which can be applied to electronic components and / or structural parts that need to work in cold environments in the fields of aviation, marine engineering, power industry and / or aerospace.

[0025] Furthermore, the coating material is applied to electronic components and / or structural parts of aircraft, wind turbines, power transmission lines, outdoor electronic products used in cold regions, ships at sea, and offshore platforms.

[0026] According to the photothermal self-healing anti-icing coating material of the present invention, in order to achieve long-lasting anti-icing and de-frost performance, self-healing and photothermal properties are introduced into a polydimethylsiloxane material system with low surface energy. By crosslinking amino-terminated polydimethylsiloxane (NH2-PDMS), hexamethylene diisocyanate (HDI), and pyromellitic trioxide (BA), dynamic imine bonds and hydrogen bonds containing self-healing properties are introduced into the polymer network. The mechanical strength, thermal stability, and self-healing properties of the coating are controlled by controlling the ratio of hexamethylene diisocyanate to pyromellitic trioxide in the polymer network. Utilizing the excellent photothermal properties of iron oxide nanoparticles in the near-infrared region, the coating can rapidly self-heal to restore its performance, while simultaneously endowing the coating with photothermal anti-icing and de-frost capabilities.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] (1) Introducing urea groups and dynamic imine bonds into the polymer network gives it excellent self-healing properties.

[0029] (2) The polymer coating has adjustable properties. The mechanical properties, self-healing properties and thermal stability can be adjusted by adjusting the ratio of hexamethylene diisocyanate and pyromellitic aldehyde to adapt to more complex application scenarios.

[0030] (3) The polymer coating has photothermal response. Under near-infrared light, the polymer coating can achieve rapid heating and temperature control by controlling the light power.

[0031] (4) The polymer coating has anti-icing properties and can quickly remove surface ice and inhibit icing in low-temperature environments (such as -10℃).

[0032] (5) The polymer coating has anti-frost properties and can quickly remove frost and inhibit frost formation in low-temperature environments (such as -10℃).

[0033] (6) The operation method of this application is simple, low-cost, universal, and easy to scale up production. Attached Figure Description

[0034] Figure 1This is a synthesis route diagram of the photothermal self-healing anti-icing and anti-frost polymer coating described in this invention;

[0035] Figure 2 The graph shows the photothermal response performance of the photothermal self-healing anti-icing and anti-frost polymer coating in Example 1.

[0036] Figure 3 The graph shows the photothermal response performance of the photothermal self-healing anti-icing and defrost polymer coating in Example 1 under different near-infrared light powers.

[0037] Figure 4 A demonstration image of a photothermal self-healing anti-icing and de-icing polymer coating;

[0038] Figure 5 A demonstration image of a photothermal self-healing anti-icing and de-icing polymer coating for de-icing;

[0039] Figure 6 This is a frost-prevention illustration of the photothermal self-healing anti-icing and anti-frost polymer coating in this invention;

[0040] Figure 7 The graph shows the self-healing performance of the photothermal self-healing anti-icing and defrost polymer coating described in Example 1 at 80°C. Detailed Implementation

[0041] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0043] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0044] The following combination Figures 1-7 Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the present invention.

[0045] To address the issues of susceptibility to mechanical damage and relatively low adhesion strength of polymer coatings used in de-icing applications, this invention proposes a method for preparing a photothermal self-healing de-icing and de-frost coating using amino-terminated polydimethylsiloxane (NH2-PDMS), hexamethylene diisocyanate (HDI), trimesoaldehyde (BA), and photothermal nanoparticles as raw materials. Specifically, the photothermal nanoparticles are iron(III) oxide nanoparticles (Fe3O4 NPs), and the photothermal self-healing de-icing coating is a multifunctional polydimethylsiloxane (PDMS@Fe3O4) polymer material with various properties, including photothermal responsiveness, self-healing, substrate independence, and low surface energy. Especially in de-icing and de-frost protection, it can extend the freezing time by up to 3 times at -10℃ and inhibits freezing and frost formation and rapidly melts ice and frost upon near-infrared light excitation.

[0046] The photothermal self-healing anti-icing and defrost coating provided by this invention comprises amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, trimesin, and iron oxide nanoparticles. The iron oxide nanoparticles exhibit excellent photothermal properties in the near-infrared region and can increase the mechanical strength of the polymer coating to a certain extent. The polymer network is composed of amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, and trimesin. The amino-terminated polydimethylsiloxane reacts with hexamethylene diisocyanate to form long polymer chains. Strong hydrogen bonds exist between the urea groups generated from the amino and isocyanate groups. These dynamic hydrogen bonds can dynamically break and form, contributing to the self-healing of the coating. Furthermore, these hydrogen bonds also ensure the adhesion between the coating and the substrate. Simultaneously, the reaction of amino-terminated polydimethylsiloxane with trimesin to form a polymer network gives the coating stronger mechanical properties, and the dynamic imine bonds generated from the amino and aldehyde groups also promote the self-healing of the coating. In summary, this polymer is a multifunctional polymer with a variety of properties, including photothermal responsiveness, self-healing properties, substrate independence, and low surface energy. It can extend the freezing time by 3 times at -10℃ and inhibit freezing and frost formation and rapidly melt ice and frost when excited by near-infrared light.

[0047] In the extended scheme, hexamethylene diisocyanate and pyromellitic aldehyde can be used interchangeably. Therefore, in one embodiment of the present invention (corresponding to the preparation method of Example 2 below), the coating material is a modified polydimethylsiloxane composite iron tetroxide multifunctional polymer prepared by amino-terminated polydimethylsiloxane, hexamethylene diisocyanate and iron tetroxide nanoparticles; wherein, the amino groups on the amino-terminated polydimethylsiloxane and the isocyanates on the hexamethylene diisocyanate undergo a condensation reaction to generate a long polymer chain, and there are hydrogen bonds between the urea groups generated by the amino groups and the isocyanates.

[0048] In another embodiment (corresponding to the preparation method in Example 6 below), the coating material is a modified polydimethylsiloxane composite iron tetroxide multifunctional polymer prepared using amino-terminated polydimethylsiloxane, trimesin, and iron oxide nanoparticles; wherein, the amino-terminated polydimethylsiloxane undergoes a condensation reaction with trimesin to form a polymer network, and the resulting dynamic imine bonds can dynamically form and break.

[0049] The molar ratio of hexamethylene diisocyanate to trimesodium is 1:0 to 0:1. The mechanical strength, thermal stability, and self-healing properties of the coating are controlled by adjusting this ratio within the polymer network. Utilizing the photothermal properties of iron oxide nanoparticles in the near-infrared region, the coating can achieve photothermal self-healing to restore its properties. Increasing the proportion of hexamethylene diisocyanate in the coating significantly improves its self-healing properties and adhesion to the substrate, while trimesodium contributes significantly to the mechanical properties and thermal stability of the coating. For de-icing applications, the preferred ratio of hexamethylene diisocyanate to trimesodium is 0.9:0.1 to 0.5:0.5.

[0050] This invention also provides a method for preparing the photothermal self-healing anti-icing and anti-frost coating, such as... Figure 1 As shown, the preparation method includes the following steps:

[0051] S1. Dissolve hexamethylene diisocyanate (HDI) and / or pyromellitic benzoate (BA) in tetrahydrofuran (THF);

[0052] S2. The mixed solution is sonicated for 5 minutes until completely dissolved to obtain a homogeneous hexamethylene diisocyanate-trimethylammonium phosphate mixed solution;

[0053] S3. Add amino-terminated polydimethylsiloxane to the mixed solution to obtain a PDMS precursor solution. After magnetic stirring and heating at 50°C for 30 minutes, a uniform PDMS prepolymer solution is obtained.

[0054] S4. Add the iron(III) oxide nanoparticles to the PDMS prepolymer solution, shake for 1 minute, sonicate for 15 minutes, repeat 3 times to obtain a uniform PDMS@Fe3O4 prepolymer solution.

[0055] S5. The PDMS@Fe3O4 prepolymer liquid is coated onto the material surface and cured at room temperature and normal pressure for 1 day to obtain the photothermal self-healing anti-icing and anti-frost coating.

[0056] Specifically, in step S1, the molar ratio of the selected hexamethylene diisocyanate and trimesoaldehyde is 1:0-0:1.

[0057] In step S1, the mass of tetrahydrofuran contained in the mixed solution is 300% of the mass of amino-terminated polydimethylsiloxane added in step S3.

[0058] In step S4, the average diameter of the iron oxide nanoparticles is 20 nm.

[0059] Preferably, the amino-terminated polydimethylsiloxane is a chain polymer with an average molecular weight of 3000 g / mol.

[0060] Preferably, the mass ratio of amino-terminated polydimethylsiloxane to tetrahydrofuran in the PDMS precursor solution is 1:3.

[0061] Preferably, the ultrasonic treatment parameters are as follows: the hexamethylene diisocyanate-trimethylammonium methyl ester mixed solution is treated in an ultrasonic device with a power of 60W for 5 minutes to dissolve the hexamethylene diisocyanate and trimethylammonium methyl ester.

[0062] Preferably, the stirring and heating parameters are as follows: the PDMS precursor solution is magnetically stirred for 30 minutes, and the heating temperature is set to 50°C to obtain a uniform PDMS prepolymer solution.

[0063] Preferably, the mass of the iron oxide nanoparticles in the PDMS@Fe3O4 prepolymer solution is 0g-3g.

[0064] Figure 2 To demonstrate the photothermal properties of the aforementioned photothermal self-healing anti-icing and defrost-removing coating, the coating without added iron oxide nanoparticles showed almost no temperature change after irradiation with 0.6W near-infrared light for 5 minutes, with only a temperature increase of 5±0.2℃. When iron oxide nanoparticles were introduced into the polymer mesh, the coating exhibited a significant temperature rise under 0.6W near-infrared light. This temperature rise gradually increased and stabilized with increasing amounts of iron oxide nanoparticles, reaching 55.4±1.3℃ with 0.6g added, approximately 10 times higher than the coating without added iron oxide nanoparticles.

[0065] Figure 2 The photothermal response performance of the aforementioned photothermal self-healing anti-icing and defrost coating under different near-infrared light powers is demonstrated; for example... Figure 3 As shown, changing the near-infrared power significantly affects the photothermal effect of the coating. Under near-infrared light of 0.9W and 1.2W, the coating temperature rise reached 79.2±0.6℃ and 101.4±1.2℃, respectively, indicating that the temperature of the coating can be controlled by adjusting the near-infrared power. Furthermore, under different near-infrared light powers, the coating temperature quickly reached near a constant temperature and rapidly dropped to room temperature after the light was turned off, demonstrating the coating's rapid response to near-infrared light.

[0066] Figure 4 This demonstrates the anti-icing performance of a photothermal self-healing anti-icing and anti-frost polymer coating. For example... Figure 4As shown, uncoated glass, without near-infrared light, froze completely in just 80.0 ± 3.5 s, while water droplets on coated glass took 335 ± 22.9 s to freeze completely, nearly three times longer. Comparing the initial state of the water droplets, the larger surface area spread out on the glass resulted in faster heat exchange and a significantly shorter freezing time. Applying different powers (0.6 W, 0.9 W, 1.2 W) of near-infrared light to the coated glass, no freezing was observed within 10 minutes, demonstrating the excellent anti-icing performance of the coating.

[0067] Figure 5 This demonstrates the photothermal de-icing performance of the aforementioned photothermal self-healing anti-icing and de-frost polymer coating; such as... Figure 5 As shown, the coating exhibits de-icing properties for completely frozen water droplets using near-infrared light. Applying near-infrared light causes the frozen ice to melt significantly, and the melting rate is affected by the near-infrared light power. Applying near-infrared light at different powers (0.6W, 0.9W, 1.2W), the time required for complete ice melting reaches 360.6±18.0s, 165.3±20.4s, and 127.3±7.2s, respectively, indicating that the coating possesses excellent photothermal de-icing performance.

[0068] Figure 6 Demonstration of the anti-frost performance of a photothermal self-healing anti-icing and anti-frost polymer coating. For example... Figure 6 As shown, the uncoated glass was completely covered with frost under 1.2W near-infrared light. In contrast, the coated glass showed a clear area of ​​frost suppression under only 0.6W near-infrared light, and this area increased as the power was increased to 0.9W. To verify the defrosting ability of the coating, the frosted coating was exposed to near-infrared light of different powers. 0.6W near-infrared light could not melt the frost, indicating that the frost weakened the near-infrared light energy reaching the coating. Further increasing the power to 0.9W and 1.2W, the frost melted rapidly, proving the defrosting ability of the coating.

[0069] To achieve long-lasting anti-icing and anti-frost performance, self-healing and photothermal properties are incorporated into a polydimethylsiloxane material system with low surface energy. By crosslinking amino-terminated polydimethylsiloxane (NH2-PDMS), hexamethylene diisocyanate (HDI), and pyromellitic trioxide (BA), dynamic imine and hydrogen bonds with self-healing properties are introduced into the polymer network. The mechanical strength, thermal stability, and self-healing properties of the coating are controlled by adjusting the ratio of hexamethylene diisocyanate to pyromellitic trioxide in the polymer network. Utilizing the excellent photothermal properties of iron oxide nanoparticles in the near-infrared region, the coating can rapidly self-heal to restore its performance, while simultaneously endowing it with photothermal anti-icing and anti-frost capabilities.

[0070] The aforementioned photothermal self-healing polymer is a modified polydimethylsiloxane composite magnetite multifunctional polymer coating prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, trimesin, and iron oxide nanoparticles. This polymer coating exhibits excellent anti-icing and defrost-removing properties and can achieve rapid self-healing under near-infrared light excitation. Furthermore, this polymer coating demonstrates good adhesion strength to various substrates; possesses photothermal response and self-healing properties; and can be applied in the aerospace, marine engineering, power industry, and other related fields. It is particularly suitable for electronic components and structural parts that need to operate in cold environments, such as aircraft, wind turbines, power transmission lines, or outdoor electronic products used in cold regions, ships, and offshore platforms.

[0071] To enable those skilled in the art to better understand the technical solution of the present invention, the adhesion and self-healing properties of the photothermal self-healing anti-icing and de-icing coating will be described below in conjunction with specific embodiments.

[0072] Example 1

[0073] 0.0108 g of trimesin and 0.1512 g of hexamethylene diisocyanate were dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, and the mixture was shaken for 1 minute and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the surface of a substrate and cured at room temperature and atmospheric pressure for 1 day to obtain the aforementioned photothermal self-healing anti-icing and anti-frost coating.

[0074] Figure 7 The test results for the scratch self-healing coating against ice and frost described in Example 1 at 80°C and under 0.6W near-infrared light are as follows. Figure 5 As shown, at 80℃, the width of the scratches on the coating decreased significantly in just 25 seconds, and some areas of the scratches had healed by 35 seconds. After 40-60 seconds, the scratches were completely healed. Under 0.6W near-infrared light, the self-healing process of the scratches was basically the same as that under the 80℃ heating condition.

[0075] Example 2

[0076] 0.168 g of hexamethylene diisocyanate was dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, shaken for 1 minute, and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the substrate surface and cured at room temperature and atmospheric pressure for 1 day to obtain a photothermal self-healing anti-icing and anti-frost coating.

[0077] At 80°C, the self-healing test in this example required 1.2 ± 0.5 minutes for the scratch to heal.

[0078] Example 3

[0079] 0.0216 g of trimesin and 0.1344 g of hexamethylene diisocyanate were dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, and the mixture was shaken for 1 minute and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the surface of a substrate and cured at room temperature and atmospheric pressure for 1 day to obtain a photothermal self-healing anti-icing and anti-frost coating.

[0080] At 80℃, the scratch healing time in the self-healing experiment of this example was 40.0 ± 17.3 minutes. Glass was used as the test sample.

[0081] Example 4

[0082] 0.054 g of trimesin and 0.084 g of hexamethylene diisocyanate were dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, shaken for 1 minute, and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the substrate surface and cured at room temperature and atmospheric pressure for 1 day to obtain a photothermal self-healing anti-icing and anti-frost coating.

[0083] At 80°C, the self-healing test in this example required 250.0 ± 148.0 minutes for the scratch to heal.

[0084] Example 5

[0085] 0.0864 g of trimesin and 0.0336 g of hexamethylene diisocyanate were dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, and the mixture was shaken for 1 minute and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the surface of a substrate and cured at room temperature and atmospheric pressure for 1 day to obtain a photothermal self-healing anti-icing and anti-frost coating.

[0086] At 80°C, the self-healing test in this example required 330.0 ± 286.2 minutes for the scratch to heal.

[0087] Example 6

[0088] 0.108 g of trimesin was dissolved in 9 g of tetrahydrofuran and sonicated for 5 minutes to prepare a mixed solution. Then, 3 g of amino-terminated polydimethylsiloxane was added, and the mixture was magnetically stirred and heated at 50°C for 30 minutes to obtain a homogeneous PDMS prepolymer. 0.6 g of iron(III) oxide nanoparticles were added to the PDMS prepolymer, shaken for 1 minute, and sonicated for 15 minutes. This process was repeated 3 times to obtain a PDMS@Fe3O4 prepolymer. The prepolymer was uniformly coated onto the substrate surface and cured at room temperature and atmospheric pressure for 1 day to obtain a photothermal self-healing anti-icing and anti-frost coating.

[0089] At 80°C, the self-healing test in this example required 460.0 ± 210.7 minutes for the scratch to heal.

[0090] The photothermal self-healing anti-icing and defrost coating material prepared in this invention solves the problems of low adhesion strength and susceptibility to damage of traditional polydimethylsiloxane polymer anti-icing coatings. Furthermore, this photothermal self-healing anti-icing and defrost coating material possesses multiple properties, including photothermal responsiveness, self-healing ability, substrate independence, and low surface energy. Especially in terms of anti-icing and defrost protection, it can extend the freezing time of water droplets by 3 times (compared to glass substrates) at a low temperature of -10℃, and can achieve photothermal anti-icing and defrost protection using near-infrared light.

[0091] In the description of this specification, references to terms such as "embodiment," "example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, those skilled in the art can combine or combine the different embodiments or examples described in this specification and the features therein without causing contradiction.

[0092] While embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions, and alterations to the above embodiments within the scope of the present invention.

Claims

1. A photothermal self-healing anti-icing coating material, characterized in that, The coating material is a polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, pyromellitic trioxide, and photothermal nanoparticles. In this process, the amino groups on the amino-terminated polydimethylsiloxane and the isocyanates on the hexamethylene diisocyanate undergo a polycondensation reaction to generate long polymer chains. Hydrogen bonds exist between the urea groups generated by the amino and isocyanate groups, and these dynamic hydrogen bonds can be dynamically broken and formed, enabling the coating to self-heal. Simultaneously, the amino-terminated polydimethylsiloxane undergoes a polycondensation reaction with trimesin to form a polymer network. The dynamic imine bonds generated by the amino and aldehyde groups can be dynamically formed and broken, promoting the self-healing of the coating. The photothermal nanoparticles are iron oxide nanoparticles. The iron oxide nanoparticles generate a photothermal effect under near-infrared light excitation, enabling the coating to rapidly self-heal. Based on 3g of amino-terminated polydimethylsiloxane, the amount of iron oxide nanoparticles added was 0.6g; the amount of pyromellitic methyl ester added was 0.0108g; the amount of hexamethylene diisocyanate added was 0.1512g; the amino-terminated polydimethylsiloxane is a chain polymer with an average molecular weight of 3000g / mol. The coating material self-heals within 40-60 seconds at 80°C or under 0.6W near-infrared light.

2. The photothermal self-healing anti-icing coating material according to claim 1, characterized in that, The polymer is a modified polydimethylsiloxane composite iron oxide multifunctional polymer prepared using amino-terminated polydimethylsiloxane, hexamethylene diisocyanate, pyromellitic methyl ether and iron oxide nanoparticles.

3. A method for preparing a photothermal self-healing anti-icing coating material, used to prepare the photothermal self-healing anti-icing coating material according to any one of claims 1-2, characterized in that, The preparation method includes the following steps: S1. Dissolve hexamethylene diisocyanate and pyromellitic aldehyde in tetrahydrofuran to obtain a mixed solution; S2. Sonicate the mixed solution until it is completely dissolved to obtain a mixed solution of hexamethylene diisocyanate and pyromellitic aldehyde; S3. Add amino-terminated polydimethylsiloxane to the mixed solution to obtain a PDMS precursor solution, and obtain a uniform PDMS prepolymer solution after magnetic stirring and heating. S4. Add Fe3O4 nanoparticles to PDMS prepolymer solution, and obtain a uniform PDMS@Fe3O4 prepolymer solution after oscillation and sonication. S5. The PDMS@Fe3O4 prepolymer liquid is coated onto the material surface and cured at room temperature and normal pressure to obtain a photothermal self-healing anti-icing coating.

4. The method for preparing the photothermal self-healing anti-icing coating material according to claim 3, characterized in that, In step S3, the mass ratio of amino-terminated polydimethylsiloxane to tetrahydrofuran in the PDMS precursor solution is 1:

3.

5. The method for preparing the photothermal self-healing anti-icing coating material according to claim 3, characterized in that, In step S2, the ultrasonic treatment parameters are as follows: the mixed solution is treated in an ultrasonic device with a power of 60W for 5 minutes to dissolve hexamethylene diisocyanate and trimesin; the stirring and heating parameters in step S3 are as follows: the PDMS precursor solution is magnetically stirred for 30 minutes and the heating temperature is set to 50℃ to obtain a uniform PDMS prepolymer solution; the oscillation and ultrasonic parameters in step S4 are as follows: after oscillation for 1 minute, it is treated in an ultrasonic device with a power of 200W for 15 minutes, and the above process is repeated 3 times.

6. The method for preparing the photothermal self-healing anti-icing coating material according to claim 3, characterized in that, The diameter of the iron oxide nanoparticles is 20 nm.

7. The application of the photothermal self-healing anti-icing coating material according to any one of claims 1-2, characterized in that, The coating material is used in electronic components and / or structural parts that need to operate in cold environments in the aerospace, marine engineering, and power industries.

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