Anti-icing coating formula, anti-icing coating based on star-shaped long branched chain network structure and preparation method of anti-icing coating

Abstract

The invention belongs to the technical field of anti-icing, and relates to an anti-icing coating formula, an anti-icing coating based on a star-shaped long branch chain network structure and a preparation method of the anti-icing coating. The anti-icing coating disclosed by the invention is obtained by carrying out hydrosilylation reaction on octavinyl polyhedral oligomeric silsesquioxane and monohydrogen-terminated polysiloxane, mixing with hydrogen-containing polysiloxane and a lubricant, and curing. The prepared anti-icing coating cooperates with two anti-icing mechanisms of an external lubricating liquid layer and an intrinsic elastomer, the ice shear strength is effectively reduced, the robustness of low ice shear force is greatly improved, the anti-icing performance can still be kept through the intrinsic coating after the lubricating liquid is used up for a long time, and long-acting anti-icing is achieved.

Description

Technical Field

[0001] The present invention relates to the field of anti-icing technology, and relates to an anti-icing coating formula, an anti-icing coating based on a star-shaped long-branched chain network structure, and a preparation method thereof. Background Art

[0002] The polar regions are rich in resources, which are of great strategic significance in global trade, military strategy, and scientific research. However, the extreme environment in the polar regions has seriously delayed the development of the polar regions. Among them, the low temperature and ice formation in the polar regions have seriously affected the service of polar equipment. In order to overcome these challenges, scientists have conducted a lot of research on anti-icing technology. At present, there are two main methods of deicing and anti-icing: the first is active deicing, including thermodynamic deicing, chemical deicing, mechanical deicing, etc. Active deicing has problems such as high cost, huge energy consumption, complex operation, and environmental pollution, which can hardly meet social needs; the second method is passive deicing, which reduces the amount of ice by coating or constructing an anti-icing coating on the surface of the substrate, delaying the ice formation time, increasing the ice nucleation barrier, and reducing the ice adhesion strength. At present, the passive anti-icing method of constructing a low surface energy coating material with a surface micro-nano structure has become a research hotspot.

[0003] Existing anti-icing coatings are mainly based on super-hydrophobic interfaces and lubricant-injected porous interfaces (i.e., SLIPs surfaces). Among them, the super-hydrophobic interface based on the "lotus effect" has a micron / nano hierarchical structure, so water droplets have a high contact angle and an extremely low rolling angle on the surface, making it difficult for them to stay and very easy to slide off, achieving the effect of making it difficult for the coating surface to freeze. However, the super-hydrophobic interface will still freeze in environments such as high humidity, and due to the characteristics of its surface structure, it will form a mechanical interlock after freezing, making it more difficult to de-ice. At the same time, after multiple freezing / de-icing cycles, the surface structure is easily damaged and fails, and long-term anti-icing cannot be achieved. Inspired by the surface of pitcher plant leaves, the lubricant-injected porous interface is based on the high slip characteristics of the ice layer on the liquid surface, giving it an extremely low ice adhesion strength. At the same time, the porous structure inside the coating can store lubricating fluid to replenish the loss of surface lubricating fluid, making it effective for a certain period of time. However, the lubricating fluid will be lost and easily volatilize during the de-icing process. After the lubricating fluid is exhausted, the coating will fail, and its long-term effectiveness needs to be improved.

[0004] Chinese Patent Publication No. CN116040962A discloses a high-solid composite anti-icing and anti-slip coating for lubricants, its preparation method and application. In this method, solid lubricants are added after liquid lubricants are added to the interpenetrating network skeleton substrate to improve the loss of lubricating fluid. However, the anti-icing effect of the solid lubricant is not good, and the synergistic effect between the solid lubricant and the liquid lubricant in this method is not obvious, and the retention effect on the liquid lubricant remains to be verified. In recent years, elastomeric materials based on the principle of pulsed separation have been widely used in the research of anti-icing coatings. The low elastic modulus surface makes the coating have a low ice adhesion strength. A common example is PDMS. However, simply pursuing a low elastic modulus to reduce the ice adhesion strength will deteriorate the mechanical properties of the coating and affect its long-term use.

[0005] Therefore, the task of designing a special functional coating with low temperature resistance, anti-icing, and easy ice shedding is extremely urgent. Summary of the Invention

[0006] To solve the above problems existing in the prior art, the purpose of the present invention is to provide an anti-icing coating formulation, an anti-icing coating based on a star-shaped long-chain network structure, and its preparation method to overcome the deficiencies of the prior art.

[0007] One object of the present invention is achieved through the following technical solutions:

[0008] An anti-icing coating formulation is obtained by subjecting octavinylcage polyhedral oligomeric silsesquioxane and mono-hydrogen-terminated polysiloxane to a hydrosilylation reaction, and then mixing with a crosslinking agent and a lubricant.

[0009] The crosslinking agent is one or more of di-hydrogen-terminated polysiloxane, side-hydrogen-containing polysiloxane, and end-side-hydrogen-containing polysiloxane.

[0010] The raw materials for preparing the anti-icing coating include: octavinylcage polyhedral oligomeric silsesquioxane, mono-hydrogen-terminated polysiloxane, crosslinking agent, catalyst, solvent, and lubricant.

[0011] The hydrosilylation reaction of octavinylcage polyhedral oligomeric silsesquioxane and mono-hydrogen-terminated polysiloxane is carried out in a solvent in the presence of a catalyst. After removing the solvent from the product prepared by the hydrosilylation reaction, it is then mixed with a crosslinking agent and a lubricant to obtain the anti-icing coating formulation.

[0012] Preferably, the mono-hydrogen-terminated polysiloxane is preferably mono-hydrogen-terminated polydimethylsiloxane.

[0013] Preferably, the crosslinking agent is one or more of di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane, and end-side-hydrogen-containing polydimethylsiloxane.

[0014] Preferably, the viscosity of mono-hydrogen-terminated polydimethylsiloxane, di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane and end-side-hydrogen-containing polydimethylsiloxane at room temperature (25 °C) is 50 to 2000 mPa·s.

[0015] Preferably, in mono-hydrogen-terminated polydimethylsiloxane, di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane and end-side-hydrogen-containing polydimethylsiloxane, the hydrogen content is 0.005% to 0.25 wt%.

[0016] Preferably, the lubricant is one or more of silicone oil, fluorosilicone oil and perfluoropolyether.

[0017] Preferably, the viscosity of the lubricant at room temperature (25 °C) is 50 to 3000 mPa·s.

[0018] The second object of the present invention is achieved by the following technical solutions:

[0019] A preparation method of an anti-icing coating formulation, comprising the following steps:

[0020] S1. Dissolve octavinylcage polyhedral oligomeric silsesquioxane, mono-hydrogen-terminated polysiloxane and a catalyst in a solvent, carry out a hydrosilylation reaction, and remove the solvent to obtain a precursor;

[0021] S2. Mix the precursor, a crosslinking agent and a lubricant to obtain the anti-icing coating formulation.

[0022] Preferably, in step S1, the molar ratio of the silicon-hydrogen bond on the octavinylcage polyhedral oligomeric silsesquioxane to the silicon-hydrogen bond on the mono-hydrogen-terminated polysiloxane is 1:1 to 10.

[0023] Preferably, in step S1, the mass ratio of the catalyst to the octavinylcage polyhedral oligomeric silsesquioxane is 0.1 to 5:1.

[0024] Preferably, the mass ratio of the mono-hydrogen-terminated polysiloxane to the solvent is 1:1 to 10.

[0025] Preferably, in step S1, the temperature of the hydrosilylation reaction is 40 to 130 °C, and the reaction time is 3 to 30 hours. The hydrosilylation reaction is carried out under stirring conditions, and the stirring speed is 200 to 1000 rpm.

[0026] Preferably, in step S2, the molar ratio of the silicon-hydrogen bond on the octavinylcage polyhedral oligomeric silsesquioxane in the precursor to the silicon-hydrogen bond on the crosslinking agent is 1:1 to 15.

[0027] Preferably, in step S2, the weight ratio of the precursor to the lubricant is 1:1 to 10.

[0028] Preferably, in step S2, the mixing method is mechanical stirring, the stirring speed is 200-1000 rpm, and the mixing time is 1-10 min.

[0029] The third object of the present invention is achieved by the following technical solutions:

[0030] An anti-icing coating based on a star-shaped long-chain network structure is obtained by coating the above anti-icing coating formulation on a substrate and curing it. The curing temperature is 50-130 °C, and the curing time is 1-10 hours.

[0031] Preferably, the contact angle of the anti-icing coating with a static liquid droplet is greater than 90°, and the ice shear strength of the anti-icing coating is ≤10 kPa.

[0032] The fourth object of the present invention is achieved by the following technical solutions:

[0033] A preparation method of an anti-icing coating based on a star-shaped long-chain network structure includes the following steps:

[0034] S1. Octavinylcage polyhedral oligomeric silsesquioxane, monohydride-terminated polysiloxane, and a catalyst are dissolved in a solvent, and a hydrosilylation reaction is carried out. After removing the solvent, a precursor is obtained;

[0035] S2. The precursor, a cross-linking agent, and a lubricant are mixed to obtain an anti-icing coating formulation;

[0036] S3. The anti-icing coating formulation is coated on a substrate, and then cured at 50-130 °C for 1-10 hours. After curing, an anti-icing coating based on a star-shaped long-chain network structure is obtained.

[0037] Preferably, the substrate is one of glass, an aluminum plate, and an iron plate.

[0038] Preferably, the thickness of the anti-icing coating is 5-1000 μm.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] (1) The anti-icing coating of the present invention utilizes the star-shaped sites of vinyl POSS. PDMS long chains capped with methyl groups are grafted onto some sites of POSS, and cross-linkable polyorganosiloxane chains are grafted onto some sites to form a network. When an external force acts on the surface ice layer, a shear force is applied to the coating. The coating is deformed partially under pressure, and the potential energy between the long chains in the coating increases, generating an additional rebound driving force, making the surface ice layer more likely to break away from the coating. Utilizing the characteristics of the star-shaped long-chain network structure, the de-icing effect of the coating is improved while maintaining certain mechanical properties.

[0041] (2) Before curing, the lubricant is filled. The long chains of the lubricant are entangled with the subsequently formed network. Compared with the penetration and entanglement of the long chains of the lubricant in the network structure in SLIPs, the entanglement between the end chains of the long chains of the lubricant and the end chains of the long branched chains in the star-shaped long branched chain network structure is more firm, achieving long-term slow release. The lubricant is not easily lost, improving the durability of the anti-icing coating. Moreover, the lubricating fluid is added in the second reaction, and there is no solvent involved in the second reaction, so the lubricating fluid is filled more evenly and in a larger amount.

[0042] (3) The one-pot preparation process of mixing the precursor, cross-linking agent, and lubricating fluid is adopted, enabling the lubricating fluid to be directly filled into the interior of the network structure during the reaction process. Compared with the current method of injecting the lubricating fluid by subsequent soaking and dropping, this process can greatly increase the storage amount of the lubricating fluid in the coating, ensure the continuous release of the lubricating fluid, and enhance the long-term effectiveness of the anti-icing coating.

[0043] (4) The anti-icing coating of the present invention combines the intrinsic anti-icing of the elastomer and the external anti-icing of the lubricating fluid. Even after the lubricating fluid is exhausted, the ice shear strength can still be reduced through the deformation of the elastomer network, breaking through the limitations of the traditional single anti-icing mechanism and significantly extending the service life of the anti-icing coating.

[0044] (5) The anti-icing coating with a star-shaped long branched chain network structure of the present invention has excellent anti-icing performance, can achieve long-term anti-icing, and at the same time, the preparation method is simple and convenient, and the cost is low. Description of the Drawings

[0045] Figure 1 It is the reaction flow chart for preparing the precursor in the present invention;

[0046] Figure 2 It is the reaction flow chart for forming the network structure during the curing process of the present invention;

[0047] Figure 3 It is the structural schematic diagram of the anti-icing coating with a star-shaped long branched chain network structure in the present invention;

[0048] Figure 4 It is the schematic diagram of the ice shear strength test device of the present invention;

[0049] Figure 5 It is the test result chart of the ice shear strength after the icing / de-icing cycle of the anti-icing coatings prepared in Examples 1 to 3 and the comparative example of the present invention. Detailed Embodiments

[0050] Hereinafter, the embodiments of the preparation method of the anti-icing coating based on the star-shaped long branched chain network structure of the present invention will be described in detail. However, these embodiments are exemplary, and the disclosure of the present invention is not limited thereto. Moreover, the drawings used herein are only for better illustrating the content disclosed by the present invention and do not limit the protection scope.

[0051] In some embodiments of the present invention, a method for preparing an anti-icing coating based on a star-shaped long-chain branched network structure is provided, including the following steps:

[0052] S1. Octavinylcage polyhedral oligomeric silsesquioxane, mono-hydrogen-terminated polysiloxane, and a catalyst are dissolved in a solvent, and a hydrosilylation reaction is carried out. After removing the solvent, a precursor is obtained;

[0053] S2. The precursor, a crosslinking agent, and a lubricant are mixed to obtain an anti-icing coating formulation;

[0054] S3. The anti-icing coating formulation is coated on a substrate, and then cured at 50-130 °C for 1-30 hours. After curing, an anti-icing coating based on a star-shaped long-chain branched network structure is obtained.

[0055] Figure 1 FIG. is a reaction flow chart for preparing the precursor in step S1 of the present invention. Step S1 is described in detail below:

[0056] The structural formula of octavinylcage polyhedral oligomeric silsesquioxane is shown in formula (I):

[0057]

[0058] The mono-hydrogen-terminated polysiloxane is preferably mono-hydrogen-terminated polydimethylsiloxane, and its structural formula is shown in formula (II):

[0059]

[0060] Preferably, the viscosity of mono-hydrogen-terminated polydimethylsiloxane at room temperature (25 °C) is 50-2000 mPa·s. More preferably, it is 80-1000 mPa·s.

[0061] Preferably, in the mono-hydrogen-terminated polydimethylsiloxane, the hydrogen content is 0.005%-0.25 wt%, and more preferably, it is 0.01%-0.2 wt%.

[0062] The catalyst is not particularly limited, and any catalyst that can catalyze the hydrosilylation reaction can be used. Examples include platinum-based catalysts and palladium-based catalysts. Preferably, it is a platinum-containing catalyst, and examples of the platinum-containing catalyst include one or more of Karstedt and chloroplatinic acid catalysts.

[0063] The solvent is also not particularly limited, and any organic solvent that can dissolve octavinylcage polyhedral oligomeric silsesquioxane, mono-hydrogen-terminated polysiloxane, and the catalyst can be used. Examples include at least one of benzene, toluene, ethylbenzene, xylene, dichloromethane, chloroform, acetone, ethyl acetate, butyl acetate, ethanol, and tetrahydrofuran.

[0064] Preferably, the molar ratio of the octavinylcage silsesquioxane to the silicon-hydrogen bond on the mono-hydrogen-terminated polysiloxane is 1:1 to 10, preferably 1:1 to 7.

[0065] Preferably, the mass ratio of the catalyst to the octavinylcage silsesquioxane is 0.1 to 5:1.

[0066] Preferably, the mass ratio of the mono-hydrogen-terminated polysiloxane to the solvent is 1:1 to 10.

[0067] Preferably, the hydrosilylation reaction temperature is 40 to 130 °C, and the reaction time is 3 to 30 hours. More preferably, the hydrosilylation reaction temperature is 50 to 120 °C, and the reaction time is 5 to 25 hours. The hydrosilylation reaction is carried out under stirring conditions, and the stirring speed is 200 to 1000 rpm.

[0068] The solvent is removed by drying or rotary evaporation. The heating temperature of the drying process is 80 to 120 °C, and the time is 2 to 10 hours.

[0069] The following details step S2:

[0070] In step 2, the crosslinking agent is one or more of di-hydrogen-terminated polysiloxane, side-hydrogen-containing polysiloxane, and end-side-hydrogen-containing polysiloxane. Preferably, the crosslinking agent is one or more of di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane, and end-side-hydrogen-containing polydimethylsiloxane. The structural formulas of di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane, and end-side-hydrogen-containing polydimethylsiloxane are shown in Formula (III), Formula (IV), and Formula (V) respectively:

[0071]

[0072] Preferably, the viscosities of di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane, and end-side-hydrogen-containing polydimethylsiloxane at room temperature (25 °C) are 50 to 2000 mPa·s. More preferably, they are 80 to 1000 mPa·s.

[0073] Preferably, in di-hydrogen-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane, and end-side-hydrogen-containing polydimethylsiloxane, the hydrogen content is 0.005% to 0.25 wt%. More preferably, it is 0.01% to 0.2 wt%.

[0074] Preferably, the lubricant is one or more of silicone oil, fluorosilicone oil, and perfluoropolyether.

[0075] Preferably, the viscosity of the lubricant at room temperature (25 °C) is 50 to 3000 mPa·s. More preferably, it is 100 to 2000 mPa·s.

[0076] Preferably, in step S2, the molar ratio of octavinyl silsesquioxane in the precursor to the silicon-hydrogen bond on the crosslinking agent is 1:1 to 15, preferably 1:1 to 10.

[0077] Preferably, the molar ratio of octavinyl silsesquioxane to the total silicon-hydrogen bonds on the mono-hydrogen-terminated polysiloxane and the crosslinking agent is 1:2 to 20, preferably 1:3 to 16.

[0078] Preferably, in step S2, the weight ratio of the precursor to the lubricant is 1:1 to 10.

[0079] Preferably, in step S2, the mixing method is mechanical stirring, the stirring speed is 200 to 1000 rpm, and the mixing time is 1 to 10 min.

[0080] Figure 2 This is the reaction flow chart for forming a network structure during the curing process of the present invention. The following details step S3:

[0081] Coat the anti-icing coating formulation on the substrate, and then cure it at 50 to 130 °C for 1 to 30 hours. After curing, an anti-icing coating based on a star-shaped long-chain network structure is obtained.

[0082] The curing is further preferably: the curing temperature is 50 to 120 °C, and the time is 2 to 25 hours.

[0083] Preferably, the substrate is one of glass, aluminum plate, and iron plate.

[0084] Preferably, the thickness of the anti-icing coating is 5 to 1000 μm, and further preferably 50 to 1000 μm.

[0085] Figure 3 This is the structural schematic diagram of the anti-icing coating with a star-shaped long-chain network structure prepared by the present invention; it can be seen from the figure that the anti-icing coating of the present invention utilizes the star-shaped sites of vinyl POSS, grafts PDMS long chains capped with methyl groups at some sites of POSS, and grafts crosslinkable polyorganosiloxane chains at some sites to form a network, and fills the lubricant before curing. The long chains of the lubricant are entangled with the subsequently formed network, forming a unique lubricating liquid injected into the star-shaped long-chain network structure.

[0086] POSS has tentacles like an "octopus" and spreads out in eight directions. When shear force is applied between the tentacles of one POSS center and the tentacles of another POSS center, repulsion will occur due to steric hindrance effect, forming a rebound and generating a reverse driving force, thus making the ice layer easily detached. In addition, the lubricant is filled before curing. The long chains in the star-shaped long-chain network structure and the lubricant with a chain-like structure are more firmly linked through entanglement, realizing long-term slow release, the lubricant is not easily lost, and the durability of the anti-icing coating is improved.

[0087] The technical solution of the present invention will be further described and illustrated below through specific embodiments and drawings. It should be understood that the specific embodiments described herein are only used to assist in understanding the present invention and are not used for specific limitations of the present invention. Moreover, the drawings used herein are only for better illustrating the disclosed content of the present invention and do not have a limiting effect on the protection scope. If there is no special description, the raw materials used in the embodiments of the present invention are all common raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.

[0088] In the following examples and comparative examples, the raw materials used are as follows:

[0089] Octavinylcage polyhedral oligomeric silsesquioxane: Shanghai Aladdin Biochemical Technology Co., Ltd.

[0090] Mono-hydrogen-terminated polydimethylsiloxane 1: The viscosity is 100 mPa·s at room temperature (25°C), and the hydrogen content is 0.03%.

[0091] Mono-hydrogen-terminated polydimethylsiloxane 2: The viscosity is 150 mPa·s at room temperature (25°C), and the hydrogen content is 0.02%.

[0092] Di-hydrogen-terminated polydimethylsiloxane 1: The viscosity is 500 mPa·s at room temperature (25°C), and the hydrogen content is 0.015%.

[0093] Di-hydrogen-terminated polydimethylsiloxane 2: The viscosity is 1000 mPa·s at room temperature (25°C), and the hydrogen content is 0.012%.

[0094] Hydrogen-containing polydimethylsiloxane 1 with hydrogen at the end side: The viscosity is 100 mPa·s at room temperature (25°C), and the hydrogen content is 0.15%.

[0095] The viscosity in this article is measured according to the GB / T 265-1988 standard.

[0096] Example 1

[0097] The preparation method of the anti-icing coating based on the star-shaped long-branched chain network structure in this example is as follows:

[0098] (1) Preparation of the precursor:

[0099] Put 0.6 parts by weight of octavinylcage polyhedral oligomeric silsesquioxane, 12 parts by weight of mono-hydrogen-terminated polydimethylsiloxane 1, 0.4 parts by weight of Karstedt catalyst, and 40 parts by weight of toluene into a flask, and react for 12 hours under the reaction conditions of magnetic stirring at 400 rpm and heating at 70°C; remove the solvent from the reacted solution by rotary evaporation to obtain the precursor.

[0100] (2) Preparation of the mixed solution:

[0101] Put the prepared precursor, 12 parts by weight of the crosslinking agent dihydroxy-terminated polydimethylsiloxane 1, and 35 parts by weight of silicone oil (viscosity of 500 mPa·s at room temperature of 25°C) into a beaker, and stir at a stirring rate of 300 rpm for 5 minutes to obtain the anti-icing coating formulation.

[0102] (3) Preparation of the anti-icing coating with a star-shaped long-chain branched network structure:

[0103] Uniformly coat the above anti-icing coating formulation on a glass substrate through an automatic film applicator, put it into an oven, set the temperature to 80°C, and cure for 6 hours. After curing, an anti-icing coating based on a star-shaped long-chain branched network structure is obtained.

[0104] Example 2

[0105] The preparation method of the anti-icing coating based on a star-shaped long-chain branched network structure in this example is as follows:

[0106] (1) Preparation of the precursor:

[0107] Put 1 part by weight of octavinylcage polyhedral oligomeric silsesquioxane, 12 parts by weight of monohydroxy-terminated polydimethylsiloxane 2, 1 part by weight of Karstedt catalyst, and 35 parts by weight of xylene into a flask, and react under the reaction conditions of magnetic stirring at 500 rpm and heating at 80°C for 8 hours; remove the solvent from the reacted solution by rotary evaporation to obtain the precursor.

[0108] (2) Preparation of the mixed solution:

[0109] Put the prepared precursor, 23 parts by weight of the crosslinking agent dihydroxy-terminated polydimethylsiloxane 2, and 25 parts by weight of silicone oil (viscosity of 1000 mPa·s at room temperature of 25°C) into a beaker, and stir at a stirring rate of 500 rpm for 5 minutes to obtain the anti-icing coating formulation.

[0110] (3) Preparation of the anti-icing coating with a star-shaped long-chain branched network structure:

[0111] Uniformly coat the above anti-icing coating formulation on a glass substrate through an automatic film applicator, put it into an oven, set the temperature to 100°C, and cure for 6 hours. After curing, an anti-icing coating based on a star-shaped long-chain branched network structure is obtained.

[0112] Example 3

[0113] The preparation method of the anti-icing coating based on a star-shaped long-chain branched network structure in this example is as follows:

[0114] (1) Preparation of the precursor:

[0115] Put 1.2 parts by weight of octavinyl silsesquioxane, 24 parts by weight of monohydride-terminated polydimethylsiloxane 1, 0.8 part by weight of Karstedt catalyst, and 40 parts by weight of toluene into a flask, and react for 18 hours under the reaction conditions of magnetic stirring at 700 rpm and heating at 70 °C; remove the solvent from the reacted solution by rotary evaporation to obtain a precursor.

[0116] (2) Preparation of the mixed solution:

[0117] Put the prepared precursor, 14 parts by weight of crosslinking agent hydrogen-terminated polydimethylsiloxane, and 20 parts by weight of silicone oil (viscosity of 500 mPa·s at room temperature of 25 °C) into a beaker, and stir at a stirring rate of 500 rpm for 8 minutes to obtain an anti-icing coating formulation.

[0118] (3) Preparation of the star-shaped long-branched network structure anti-icing coating:

[0119] Uniformly coat the above anti-icing coating formulation on a glass substrate through an automatic film applicator, put it into an oven, set the temperature to 100 °C, and cure for 8 hours to obtain an anti-icing coating based on a star-shaped long-branched network structure after curing.

[0120] Comparative Example 1

[0121] Silicone oil was not filled in Comparative Example 1, and the specific steps are as follows:

[0122] (1) Preparation of the precursor: The same as in Example 1.

[0123] (2) Preparation of the mixed solution:

[0124] Put the prepared precursor and 12 parts by weight of crosslinking agent dihydrogen-terminated polydimethylsiloxane 1 into a beaker, and stir at a stirring rate of 300 rpm for 5 minutes to obtain an anti-icing coating formulation.

[0125] (3) Preparation of the star-shaped long-branched network structure anti-icing coating: The same as in Example 1.

[0126] Comparative Example 2

[0127] The preparation method of the anti-icing coating in Comparative Example 2 is as follows:

[0128] (1) Preparation of the precursor:

[0129] Put 0.5 part by weight of octavinyl silsesquioxane, 35.6 parts by weight of crosslinking agent dihydrogen-terminated polydimethylsiloxane 1, 0.3 part by weight of Karstedt catalyst, and 33.9 parts by weight of toluene into a flask, and react for 12 hours under the reaction conditions of magnetic stirring at 400 rpm and heating at 70 °C; remove part of the solvent from the reacted solution by rotary evaporation until a viscous liquid is formed to obtain a precursor.

[0130] (2) Preparation of the mixed solution:

[0131] Put the prepared precursor and 29.6 parts by weight of silicone oil (viscosity of 500 mPa·s at room temperature of 25°C) into a beaker, and stir at a stirring rate of 300 rpm for 5 minutes to obtain the anti-icing coating formulation.

[0132] (3) Preparation of the star-shaped long-chain branched network structure anti-icing coating:

[0133] Uniformly coat the above anti-icing coating formulation on a glass substrate through an automatic film applicator, put it into an oven, set the temperature to 80°C, and cure for 6 hours. After curing, an anti-icing coating is obtained.

[0134] Comparative Example 3

[0135] The preparation method of the anti-icing coating in Comparative Example 3 is as follows:

[0136] (1) Preparation of the precursor: The same as in Example 1.

[0137] (2) Preparation of the mixed solution:

[0138] Put the prepared precursor and 12 parts by weight of the cross-linking agent dihydroxy-terminated polydimethylsiloxane 1 into a beaker, and stir at a stirring rate of 300 rpm for 5 minutes to obtain the anti-icing coating formulation.

[0139] (3) Preparation of the star-shaped long-chain branched network structure anti-icing coating:

[0140] Uniformly coat the above anti-icing coating formulation on a glass substrate through an automatic film applicator, put it into an oven, set the temperature to 80°C, and cure for 6 hours. Immerse the cured coating in excessive silicone oil (viscosity of 500 mPa·s at room temperature of 25°C) for 12 hours, take it out, dry it, and then an anti-icing coating is obtained.

[0141] Performance test:

[0142] Contact angle test of the anti-icing coating: The contact angle is measured using a water contact angle meter. The results are shown in Table 1.

[0143] Ice shear strength test of the anti-icing coating: Use a shear strength test device (the schematic diagram of the shear strength test device is as Figure 4 shown), place an ice column mold on the coating surface, wait until it is completely frozen, then place it on a -25°C cooling table for 30 minutes, control the push rod to move horizontally at a speed of 0.2 mm / s until the ice column completely detaches from the coating surface, record the peak value of the thrust during this process, and divide it by the freezing area of the ice column, which is the corresponding ice shear strength. The results are shown in Table 1.

[0144] Table 1

[0145] Example Contact angle / ° Ice shear strength / kPa Example 1 103.7 3.71 Example 2 106.4 4.64 Example 3 108.1 6.56 Comparative example 1 112.0 13.12 Comparative example 2 104.5 9.89 Comparative example 3 107.8 8.42

[0146] The anti-icing coatings prepared in Examples 1 to 3 based on the star-shaped long-chain network structure have a contact angle of about 100° to 110°, showing good hydrophobicity. Among them, the anti-icing coating without loaded lubricant prepared in Comparative Example 1 exhibits a contact angle greater than 110°, and the contact angles of the anti-icing coatings loaded with lubricant prepared in Comparative Examples 2 to 3 are also about 100° to 110°.

[0147] The anti-icing coatings prepared in Examples 1 to 3 based on the star-shaped long-chain network structure exhibit extremely low ice shear strength (≤10 kPa). At the same time, the anti-icing coating without loaded lubricant prepared in Comparative Example 1 also has a relatively low ice shear strength (≤15 kPa), but it is higher than that of the examples. The anti-icing coatings without long-chain branches prepared in Comparative Example 2 and the anti-icing coatings soaked with lubricant subsequently prepared in Comparative Example 3 have higher ice shear strength than those of the examples.

[0148] The present invention also measured the ice shear strength of the anti-icing coating after 50 cycles of freezing / de-icing, and the results are shown in Figure 5 . The anti-icing coatings prepared in Examples 1 to 3 based on the star-shaped long-chain network structure can still maintain extremely low ice shear strength (≤10 kPa) after 50 cycles of freezing / de-icing, have good retention of the lubricant, and achieve long-term de-icing. The anti-icing coating without loaded lubricant prepared in Comparative Example 1 also continuously maintains a relatively low ice adhesion strength (≤15 kPa) after 50 cycles of freezing / de-icing, indicating that the coating can also achieve long-term anti-icing through its intrinsic anti-icing ability after the lubricant is exhausted, greatly improving the durability of the coating for de-icing. The coating soaked with silicone oil subsequently prepared in Comparative Example 3 has a relatively low ice adhesion strength at the initial stage of the cycle, and the ice adhesion strength increases sharply after the silicone oil is exhausted. The coating prepared in Comparative Example 2 has a low retention of the lubricant, and the ice adhesion strength will increase sharply after a certain number (≤35 times) of cycles, indicating the failure of the surface lubricant.

[0149] All aspects, embodiments, and features of the present invention should be considered illustrative in all respects and do not limit the present invention. The scope of the present invention is only defined by the claims. Without departing from the spirit and scope of the claimed invention, those skilled in the art will understand other embodiments, modifications, and uses.

[0150] In the preparation method of the present invention, the order of each step is not limited to the listed order. For those of ordinary skill in the art, without creative efforts, the sequence changes of each step are also within the protection scope of the present invention. In addition, two or more steps or actions can be carried out simultaneously.

[0151] Finally, it should be noted that the specific embodiments described herein are merely illustrative of the present invention and do not limit the implementation of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar ways to substitute, and it is not necessary and impossible to list all the implementation manners here. And these obvious changes or variations derived from the essence of the present invention still fall within the protection scope of the present invention, and it is contrary to the spirit of the present invention to interpret them as any additional limitations.

Claims

1. An anti-icing coating formulation, characterized in that, It is obtained by hydrosilylation reaction of octavinylcage polyhedral oligomeric silsesquioxane with monohydride-terminated polysiloxane, and then mixing with a crosslinking agent and a lubricant; The crosslinking agent is one or more of dihydride-terminated polysiloxane, side-hydrogen-containing polysiloxane and end-side-hydrogen-containing polysiloxane.

2. The anti-icing coating formulation according to claim 1, characterized in that, The monohydride-terminated polysiloxane is monohydride-terminated polydimethylsiloxane; The crosslinking agent is one or more of dihydride-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane and end-side-hydrogen-containing polydimethylsiloxane.

3. The anti-icing coating formulation according to claim 2, wherein The viscosities of monohydride-terminated polydimethylsiloxane, dihydride-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane and end-side-hydrogen-containing polydimethylsiloxane at 25 °C are 50-2000 mPa·s; And / or, among monohydride-terminated polydimethylsiloxane, dihydride-terminated polydimethylsiloxane, side-hydrogen-containing polydimethylsiloxane and end-side-hydrogen-containing polydimethylsiloxane, the hydrogen content is 0.005%-0.25 wt%.

4. The anti-icing coating formulation according to claim 1, characterized in that, The lubricant is one or more of silicone oil, fluorosilicone oil and perfluoropolyether; And / or, the viscosity of the lubricant at 25 °C is 50-3000 mPa·s.

5. The preparation method of an anti-icing coating formulation according to claim 1, characterized in that, It includes the following steps: S1. Dissolve octavinylcage polyhedral oligomeric silsesquioxane, monohydride-terminated polysiloxane and a catalyst in a solvent, carry out hydrosilylation reaction, and obtain a precursor after removing the solvent; S2. Mix the precursor, the crosslinking agent and the lubricant to obtain an anti-icing coating formulation.

6. The preparation method according to claim 5, wherein In step S1, the molar ratio of the silicon-hydrogen bonds on the octavinylcage polyhedral oligomeric silsesquioxane to those on the monohydride-terminated polysiloxane is 1:1-10; And / or, the mass ratio of the catalyst to the octavinylcage polyhedral oligomeric silsesquioxane is 0.1-5:1; And / or, the mass ratio of the monohydride-terminated polysiloxane to the solvent is 1:1-10; And / or, the temperature of the hydrosilylation reaction is 40-130 °C, and the reaction time is 3-30 hours; And / or, the hydrosilylation reaction is carried out under stirring conditions, and the stirring speed is 200-1000 rpm.

7. The preparation method according to claim 5, characterized in that, In step S2, the molar ratio of the silicon-hydrogen bonds on the octavinylcage polyhedral oligomeric silsesquioxane in the precursor to those on the crosslinking agent is 1:1-15; And / or, the weight ratio of the precursor to the lubricant is 1:1-10; And / or, the mixing method is mechanical stirring, the stirring speed is 200-1000 rpm, and the mixing time is 1-10 min.

8. An anti-icing coating based on a star-shaped long-chain branched network structure, characterized in that, It is obtained by coating the substrate with the anti-icing coating formulation described in claim 1 and then curing.

9. The anti-icing coating according to claim 8, wherein The contact angle of the anti-icing coating with a static droplet is greater than 90°, and the ice shear strength of the anti-icing coating is ≤10 kPa.

10. A preparation method of an anti-icing coating based on a star-shaped long-chain branched network structure, characterized in that, It includes the following steps: S1. Dissolve octavinylcage polyhedral oligomeric silsesquioxane, monohydride-terminated polysiloxane and a catalyst in a solvent, carry out hydrosilylation reaction, and obtain a precursor after removing the solvent; S2. Mix the precursor, the crosslinking agent and the lubricant to obtain an anti-icing coating formulation; S3. Coat the anti-icing coating formulation on the substrate, and then cure it at 50-130 °C for 1-10 hours to obtain an anti-icing coating based on a star-shaped long-chain network structure after curing.

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