Quaternary ammonium salt modified silica nanospheres, method for preparing the same, and anti-icing coating

Abstract

The application discloses a kind of quaternary ammonium salt modified silica nanospheres and its preparation method and anti-icing coating, quaternary ammonium salt modified silica nanospheres, chemical formula as shown in formula (I): chemical formula (I) R2It represents;R1It represents;N=2-6.Quaternary ammonium salt modified silica nanospheres are used as raw material to prepare hydrophilic metal-based coating, and the super-hydrophilic performance of material is improved by modified silica nanospheres with quaternary ammonium salt group, so that quaternary ammonium salt group is combined with water molecules to destroy hydrogen bond between water molecules, and non-freezing water is formed between media, to achieve the purpose of reducing freezing point, and the non-freezing water formed as lubricating layer is beneficial to reduce the adhesion between media, to promote ice layer to be removed by its own gravity, so as to realize the effect of anti-icing.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a quaternary ammonium salt modified silica nanosphere, its preparation method, and an anti-icing coating. Background Technology

[0002] In winter, icing is inevitable, affecting people's work, lives, and safety. Ice on roads and car windshields is difficult to remove completely, directly impacting traffic safety. At low temperatures, atmospheric moisture condenses on equipment, severely affecting its normal operation and potentially causing economic losses or safety accidents. Icing on long-distance power transmission lines increases their load, leading to line breaks or tower collapses, causing large-scale power outages and disrupting people's work and lives. Therefore, anti-icing projects are extremely important.

[0003] With the development of atmospheric icing physics, nanotechnology, and chemical synthesis technology, anti-icing coatings have become an important measure in anti-icing engineering. Anti-icing coatings include superhydrophobic coatings, photothermal coatings, hydrophilic coatings, and electrothermal composite coatings, all of which offer some anti-icing effect. Superhydrophobic coatings have low ice adhesion, but their surface micro-nano structures are easily damaged, leading to unstable performance. The delayed icing effect of photothermal coatings depends on light intensity; their performance significantly decreases under no-light or low-light conditions. Electrothermal composite coatings can rapidly reduce ice adhesion when energized, but the ice adhesion returns to a high level after power is cut off. Only hydrophilic coatings achieve passive anti-icing primarily through physical adsorption and reduction of ice adhesion, requiring no additional energy input (such as the light or electrical energy required for photothermal or electrothermal coatings), thus offering advantages in scenarios without energy supply. However, hydrophilic anti-icing coatings have weak abilities to delay icing time and reduce ice adhesion, resulting in poor anti-icing effects.

[0004] Therefore, it is necessary to provide a hydrophilic anti-icing coating with good anti-icing effect. Summary of the Invention

[0005] In view of this, this application provides a quaternary ammonium salt modified silica nanosphere, its preparation method, and an anti-icing coating to solve the problem of how to improve the anti-icing effect of hydrophilic anti-icing coatings.

[0006] To achieve the above technical objectives, this application adopts the following technical solution:

[0007] In a first aspect, this application provides a quaternary ammonium salt modified silica nanosphere, the chemical formula of which is shown in formula (I):

[0008]

[0009] Chemical formula (I)

[0010] R2 represents ;

[0011] R1 represents n = 2-6.

[0012] Secondly, this application provides a method for preparing quaternary ammonium salt modified silica nanospheres, comprising the following steps:

[0013] Silicon ester, alcohol, ammonia, and water are mixed and subjected to a single heating reaction to obtain nano-silica.

[0014] Using nano-silica and γ-(2,3-epoxypropoxy)propyltrimethoxysilane as raw materials, a second heating reaction was carried out to obtain the first intermediate product;

[0015] Using the first intermediate product and polyethylene polyamine as raw materials, a second intermediate product was obtained by three heating reactions.

[0016] Using the second intermediate product and 2,3-epoxypropyltrimethylammonium chloride as raw materials, four heating reactions were carried out to obtain quaternary ammonium salt modified silica nanospheres.

[0017] Preferably, the silicone ester includes one or more of tetrabutyl orthosilicate and tetrabutyl titanate; the alcohol includes ethanol; and the polyethylene polyamine includes one or more of tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and pentaethylenehexamine.

[0018] Preferably, the molar ratio of silicone ester, alcohol, and ammonia is (1-3):(26-39):(0.13-0.19); the molar ratio of water to silicone ester is (0.39-0.57):(1-3); and the heating temperature is 50-60℃.

[0019] Preferably, the molar ratio of nano-silica to γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:(0.5-2); the temperature of the secondary heating reaction is 50-60℃, and the time is 4-6h.

[0020] Preferably, the molar ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane to polyvinyl polyamine is 1:(1-1.2); the temperature of the three heating reactions is 50-60℃ and the time is 4-6h.

[0021] Preferably, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to polyethylene polyamine is (5-7):1; the temperature of the four heating reactions is 70-80℃ and the time is 4-6h.

[0022] Thirdly, this application provides a hydrophilic metal-based anti-icing coating containing quaternary ammonium salt modified silica nanospheres, comprising, by weight, 1-3 parts of the quaternary ammonium salt modified silica nanospheres, 8-12 parts of epoxy resin, and 5-8 parts of curing agent.

[0023] Fourthly, this application provides an anti-icing composite coating prepared from a hydrophilic metal-based anti-icing coating.

[0024] Fifthly, this application provides a method for preparing an anti-icing composite coating, comprising the following steps: mixing 1-3 parts of the quaternary ammonium salt modified silica nanospheres, 8-12 parts of epoxy resin, and 5-8 parts of curing agent evenly, coating the mixture onto a metal surface, and curing it at room temperature to obtain a hydrophilic metal-based coating.

[0025] The beneficial effects of this application are as follows: This application improves the superhydrophilic properties of materials by using modified silica nanospheres with quaternary ammonium salt groups, which allows the quaternary ammonium salt groups to combine with water molecules and break the hydrogen bonds between water molecules, forming non-freezing water between the media, thereby lowering the freezing point. At the same time, the formed non-freezing water acts as a lubricating layer, which helps to reduce the adhesion between the media and promotes the ice layer to fall off under its own gravity, thereby achieving the anti-icing effect. Attached Figure Description

[0026] Figure 1 A schematic diagram of the structure of quaternary ammonium salt modified silica nanospheres;

[0027] Figure 2 Infrared spectrum of quaternary ammonium salt modified silica nanospheres;

[0028] Figure 3 This is a particle size distribution diagram of quaternary ammonium salt modified silica nanospheres;

[0029] Figure 4 XPS image of the anti-icing coating. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0031] This application provides a quaternary ammonium salt modified silica nanosphere, the chemical formula of which is shown in formula (I):

[0032]

[0033] Chemical formula (I)

[0034] R2 represents ;

[0035] R1 represents n = 2-6.

[0036] In this application, the quaternary ammonium salt modified silica nanospheres are grafted with quaternary ammonium salts. Quaternary ammonium salts, as organometallic salts, are white solids at room temperature, readily soluble in water, hygroscopic, and can directly absorb water and melt upon contact with air. The modified silica nanospheres with quaternary ammonium salt groups have superhydrophilic properties, which allow the quaternary ammonium salt groups to combine with water molecules, breaking the hydrogen bonds between water molecules and forming non-freezing water between the media, thereby lowering the freezing point. At the same time, the formed non-freezing water acts as a lubricating layer, which helps to reduce the adhesion between the media and promotes the ice layer to fall off under its own gravity, thus achieving the anti-icing effect.

[0037] This application provides a method for preparing quaternary ammonium salt modified silica nanospheres, comprising the following steps:

[0038] S1. Mix silicone ester, alcohol, ammonia, and water, and carry out a heating reaction to obtain nano-silica;

[0039] S2. Using nano-silica and γ-(2,3-epoxypropoxy)propyltrimethoxysilane as raw materials, a second heating reaction is carried out to obtain the first intermediate product;

[0040] S3. Using the first intermediate product and polyethylene polyamine as raw materials, a second intermediate product is obtained by three heating reactions.

[0041] S4. Using the second intermediate product and 2,3-epoxypropyltrimethylammonium chloride as raw materials, four heating reactions were carried out to obtain quaternary ammonium salt modified silica nanospheres.

[0042] This application modifies nano-silica through a stepwise reaction, successfully grafting quaternary ammonium salts onto nano-silica.

[0043] In some embodiments, the silicone ester includes one or more of tetrabutyl orthosilicate and tetrabutyl titanate; the alcohol includes ethanol; and the polyvinyl polyamine includes one or more of tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and pentaethylenehexamine.

[0044] In this embodiment, the polyvinyl polyamine of this application is used to control the n value (2-6). Tetraethylenepentamine, triethylenetetramine, diethylenetriamine, and pentaethylenehexamine are all homologues, which can control the chain length of the quaternary ammonium salt side chains grafted on the nano-silica microspheres and the number of hydrophilic groups. To expand the types of coatings, the silicone ester includes tetraethyl orthosilicate and tetrabutyl titanate. Tetrabutyl titanate can be used to prepare photothermal coatings. Taking tetraethyl orthosilicate as the silicone ester, ethanol as the alcohol, and tetraethylenepentamine as the polyvinyl polyamine as an example, the preparation process of quaternary ammonium salt modified silica nanospheres is as follows:

[0045]

[0046] n=4

[0047] In some embodiments, the molar ratio of silicone ester, alcohol, and ammonia is (1-3):(26-39):(0.13-0.19); the molar ratio of water to silicone ester is (0.39-0.57):(1-3); and the heating temperature is 50-60°C.

[0048] In this embodiment, the amount of ammonia and deionized water used will affect the synthesis rate and particle size of nano-silica. The particle size of nano-silica microspheres will affect the subsequent reaction. If the particle size is too small, it will be difficult to filter out and form quaternary ammonium salt modified silica nanospheres.

[0049] In some embodiments, the molar ratio of nano-silica to γ-(2,3-epoxypropoxy)propyltrimethoxysilane is 10:(0.5-2); the temperature of the secondary heating reaction is 50-60℃, and the time is 4-6h.

[0050] In this embodiment, the amount of γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) affects the content of hydrophilic groups, which in turn affects the hydrophilicity of the product. Therefore, too much or too little γ-(2,3-epoxypropoxy)propyltrimethoxysilane does not effectively improve the anti-icing effect.

[0051] In some embodiments, the molar ratio of γ-(2,3-epoxypropoxy)propyltrimethoxysilane to polyethylene polyamine is 1:(1-1.2); the three heating reactions are carried out at a temperature of 50-60°C for 4-6 hours.

[0052] In this embodiment, the amount of polyethylene polyamine used will affect the content of hydrophilic groups, and thus affect the hydrophilicity of the product. Therefore, too much or too little polyethylene polyamine will not improve the anti-icing effect.

[0053] In some embodiments, the molar ratio of 2,3-epoxypropyltrimethylammonium chloride to polyvinyl polyamine is (5-7):1; the temperature of the four heating reactions is 70-80°C, and the time is 4-6 hours.

[0054] In this embodiment, if the amount of γ-(2,3-epoxypropoxy)propyltrimethoxysilane is too large, the solution viscosity will increase and the anti-icing performance of the coating will decrease. If the amount of γ-(2,3-epoxypropoxy)propyltrimethoxysilane is too small, the hydrophilicity of the coating will decrease and the anti-icing performance will be reduced.

[0055] This application provides a hydrophilic metal-based anti-icing coating comprising, for example, quaternary ammonium salt modified silica nanospheres, including 1-3 parts of quaternary ammonium salt modified silica nanospheres, 8-12 parts of epoxy resin, and 5-8 parts of curing agent.

[0056] In this application, the excellent adhesion properties of epoxy resin to metal are utilized to create a film material. Quaternary ammonium salt modified silica nanospheres are added and mixed with epoxy resin, then coated onto the metal surface and cured to form an anti-icing coating, thus improving the anti-icing effect. The reason for this is that epoxy resin has excellent adhesion properties to metal, and the epoxy groups on the surface of the silica microspheres in this application are used to anchor themselves to the epoxy coating surface. The multi-quaternary ammonium salt segments grafted on the surface of the silica microspheres are used to absorb water and moisture, forming a superhydrophilic coating surface. This allows the quaternary ammonium salt groups in the coating to combine with water molecules, breaking the hydrogen bonds between water molecules and forming a non-freezing water layer between the coating and the water, thereby lowering the freezing point. At the same time, the non-freezing water acts as a lubricating layer between the condensed ice layer and the coating, reducing the adhesion between the two and promoting the ice layer to reach a certain thickness. Under the action of the ice layer's own gravity, the ice layer falls off, avoiding damage to power facilities. This improves the anti-icing effect by reducing the adhesion of ice, extending the freezing time, and improving the durability of the coating.

[0057] This application provides a method for preparing a hydrophilic metal-based anti-icing coating, comprising the following steps: mixing 1-3 parts of quaternary ammonium salt modified silica nanospheres, 8-12 parts of epoxy resin, and 5-8 parts of curing agent evenly, coating the mixture onto a metal surface, and curing it at room temperature to obtain the hydrophilic metal-based coating.

[0058] The method for preparing the hydrophilic metal-based anti-icing coating of this application is simple. After stirring and mixing evenly, the air bubbles are removed, and it can be directly coated on the surface of a metal substrate (such as a steel sheet) to form a hydrophilic metal-based coating.

[0059] This application provides an application of a hydrophilic metal-based anti-icing coating in environments below 0°C.

[0060] The following specific embodiments further illustrate this solution.

[0061] Example 1

[0062] A method for preparing quaternary ammonium salt modified silica nanospheres includes the following steps:

[0063] S1. Add 10g of tetraethyl orthosilicate to 100ml of ethanol, then add 1.5ml of ammonia and 2.5ml of water in sequence, heat to 60℃ and carry out a heating reaction for 4h to obtain 2.23g of nano-silica;

[0064] S2. Take 1.5g of silica and ultrasonically disperse it in 50ml of a 1:1 alcohol-water solution. Add 0.7g of KH560 and heat to 60℃ for a second heating reaction for 4h to obtain the first intermediate product.

[0065] S3. Add 0.43 g of tetraethylenepentamine to the first intermediate product, and carry out the reaction at 60 °C for three heating cycles for 4 h to obtain the second intermediate product;

[0066] S4. Add 2.07 g of 2,3-epoxypropyltrimethylammonium chloride to the second intermediate product, heat to 70 °C and react four times for 4 h, rotary evaporate, filter, wash and dry to obtain quaternary ammonium salt modified silica nanospheres.

[0067] The chemical formula of the obtained quaternary ammonium salt modified silica nanospheres is:

[0068]

[0069] R2 represents ;

[0070] R1 represents n=4.

[0071] Example 2

[0072] A method for preparing quaternary ammonium salt modified silica nanospheres includes the following steps:

[0073] S1. Add 10g of tetraethyl orthosilicate to 100ml of ethanol, then add 1.5ml of ammonia and 2.5ml of water in sequence, heat to 60℃ and carry out a heating reaction for 4h to obtain 2.23g of nano-silica;

[0074] S2. Take 1.5g of silica and ultrasonically disperse it in 50ml of a 1:1 alcohol-water solution. Add 0.7g of KH560 and heat to 60℃ for a second heating reaction for 4h to obtain the first intermediate product.

[0075] S3. Add 0.38 g of tetraethylenepentamine to the first intermediate product, and carry out the reaction at 60 °C for three heating cycles for 4 h to obtain the second intermediate product;

[0076] S4. Add 1.83 g of 2,3-epoxypropyltrimethylammonium chloride to the second intermediate product, heat to 70 °C and react four times for 4 h, rotary evaporate, filter, wash and dry to obtain quaternary ammonium salt modified silica nanospheres.

[0077] Example 3

[0078] A method for preparing a hydrophilic metal-based anti-icing coating includes the following steps: 2.0g of quaternary ammonium salt modified silica nanospheres prepared in Example 1 are mixed evenly with 10g of epoxy resin and 10g of curing agent, coated onto a steel sheet, and cured at room temperature (25°C) to obtain the hydrophilic metal-based coating.

[0079] Example 4

[0080] A method for preparing a hydrophilic metal-based anti-icing coating includes the following steps: 3.5g of quaternary ammonium salt modified silica nanospheres prepared in Example 1 are mixed evenly with 5g of epoxy resin and 5g of curing agent, coated onto a steel sheet, and cured at room temperature (25°C) to obtain the hydrophilic metal-based coating.

[0081] Example 5

[0082] A method for preparing a hydrophilic metal-based anti-icing coating includes the following steps: 2.0g of quaternary ammonium salt modified silica nanospheres prepared in Example 2 are mixed evenly with 10g of epoxy resin and 10g of curing agent, coated onto a steel sheet, and cured at room temperature (25°C) to obtain the hydrophilic metal-based coating.

[0083] Example 6

[0084] S1. Add 10g of tetraethyl orthosilicate to 100ml of ethanol, then add 1.5ml of ammonia and 2.5ml of water in sequence, heat to 60℃ and carry out a heating reaction for 4h to obtain 2.23g of nano-silica;

[0085] S2. Take 1.5g of silica and ultrasonically disperse it in 50ml of a 1:1 alcohol-water solution. Add 0.7g of KH560 and heat to 60℃ for a second heating reaction for 4h to obtain the first intermediate product.

[0086] S3. Add 0.21 g of diethylenetriamine to the first intermediate product, and carry out the reaction at 60 °C for three heating cycles for 4 h to obtain the second intermediate product;

[0087] S4. Add 1.31 g of 2,3-epoxypropyltrimethylammonium chloride to the second intermediate product, heat to 70 °C and react four times for 4 h, rotary evaporate, filter, wash and dry to obtain quaternary ammonium salt modified silica nanospheres.

[0088] S5. Mix 2.0g of the prepared quaternary ammonium salt modified silica nanospheres with 10g of epoxy resin and 10g of curing agent evenly, coat the mixture onto a steel sheet, and cure at room temperature (25℃) to obtain a hydrophilic metal-based coating.

[0089] Comparative Example 1

[0090] A method for preparing a coating is the same as in Example 1 except that it does not include the addition of quaternary ammonium salt modified silica nanospheres.

[0091] Comparative Example 2

[0092] A method for preparing a coating is the same as in Example 1 except that 30% more KH560 is added when synthesizing quaternary ammonium salt modified silica nanospheres.

[0093] Comparative Example 3

[0094] A method for preparing a coating is the same as in Example 1 except that 30% more tetraethylenepentamine is added when synthesizing quaternary ammonium salt modified silica nanospheres.

[0095] Comparative Example 4

[0096] A method for preparing a coating is the same as in Example 1 except that 30% more ammonia water is added when synthesizing quaternary ammonium salt modified silica nanospheres.

[0097] Testing and Evaluation

[0098] The infrared spectrum of the quaternary ammonium salt modified silica nanospheres obtained in Example 1 was tested, and the results are as follows: Figure 2 As shown in Table 1, the average particle size of the quaternary ammonium salt modified silica nanospheres was tested. The particle size affects the synthesis rate; excessively small particles cannot be filtered out during the synthesis of nano-silica, hindering subsequent experiments. Conversely, excessively large particle sizes of the quaternary ammonium salt modified silica nanospheres reduce the number of hydrophilic groups on the coating surface, thus decreasing anti-icing properties. The results are shown in Table 1. The particle size distribution of the quaternary ammonium salt modified silica nanospheres in Example 1 is shown in the figure. Figure 3 As shown.

[0099] Table 1. Average particle size and dispersion index of silica nanospheres modified with different quaternary ammonium salts.

[0100]

[0101] XPS images of the hydrophilic metal-based anti-icing coating obtained in Example 3 are shown below. Figure 4 As shown in Table 2, the surface element content analysis results of the hydrophilic metal-based anti-icing coating obtained in Example 3 are shown in Table 2.

[0102] Table 2. Surface element content analysis results of the hydrophilic metal-based anti-icing coating obtained in Example 3.

[0103]

[0104] As shown in Table 1, the nitrogen content of the hydrophilic metal-based anti-icing coating obtained in Example 3 is higher than the theoretical content, indicating that the quaternary ammonium salt was successfully grafted and grown on the coating surface. The silicon content is lower than the theoretical content, indicating that some silicon dioxide is buried in the epoxy resin. The oxygen content is also lower than the theoretical value, further indicating that the silicon dioxide is buried at the bottom. Some oxygen is covered by the quaternary ammonium salt, indicating that a large amount of quaternary ammonium salt is accumulated on the coating surface. The hydrophilic metal-based anti-icing coating of Example 3 was successfully prepared.

[0105] Using steel sheets as a blank control, the anti-icing performance of the coatings obtained in Examples 3-5 and Comparative Examples 1-4 was tested: different coatings were placed in a freezer at -5℃ for freezing experiments. The freezing time, the amount of water droplets used, and the contact area between the water droplets and the coating and steel sheet were tested. Fiber cloth was placed on the steel sheet, and a controlled amount of water was dripped onto it. After freezing, the maximum tensile force between the fiber cloth and the steel sheet was tested using a tensile tester as a reference for ice adhesion. The adhesion between the ice layer and the coating, and the adhesion between the ice layer and the steel sheet, are shown in Table 3.

[0106] Table 3 Performance test results of different coatings

[0107]

[0108] The results show that the hydrophilic metal-based anti-icing coating prepared in this application has a delayed freezing time, and the adhesion between the ice layer and the coating is significantly reduced compared with the adhesion between the ice layer and the iron sheet, indicating good anti-icing performance.

[0109] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A quaternary ammonium salt-modified silica nanomicrosphere, characterized in that, The chemical formula is shown as formula (I): Chemical formula (I) R2represents ; R1represents ; n = 2-6; The preparation method of the quaternary ammonium salt modified silica nanospheres is characterized in that it comprises the following steps: Mixing silicon ester, alcohol, ammonia water and water, and performing a first heating reaction to obtain nanosilica; Using the nanosilica and γ-(2,3-epoxypropoxy) propyl trimethoxysilane as raw materials, performing a second heating reaction to obtain a first intermediate product; Using the first intermediate product and polyethylene polyamine as raw materials, performing a third heating reaction to obtain a second intermediate product; Using the second intermediate product and 2,3-epoxypropyl trimethyl ammonium chloride as raw materials, performing a fourth heating reaction to obtain the quaternary ammonium salt modified silica nanospheres; The molar ratio of the nanosilica to the γ-(2,3-epoxypropoxy) propyl trimethoxysilane is 10:(0.5-2); the temperature of the second heating reaction is 50-60 DEG C, and the time is 4-6 h; The molar ratio of the γ-(2,3-epoxypropoxy) propyl trimethoxysilane to the polyethylene polyamine is 1:(1-1.2); the temperature of the third heating reaction is 50-60 DEG C, and the time is 4-6 h.

2. The quaternary ammonium salt-modified silica nanomicrosphere according to claim 1, characterized in that The silicon ester comprises one or more of tetraethyl orthosilicate and tetrabutyl titanate; the alcohol comprises ethanol; and the polyethylene polyamine comprises one or more of tetraethylenepentamine, triethylenetetramine, diethylenetriamine, pentaethylenehexamine and hexaethylenheptamine.

3. The quaternary ammonium salt-modified silica nanomicrosphere according to claim 1, characterized in that, The molar ratio of the silicon ester, alcohol and ammonia water is (1-3):(26-39):(0.13-0.19); the molar ratio of the water to the silicon ester is (0.39-0.57):(1-3); and the temperature of the first heating is 50-60 DEG C.

4. The quaternary ammonium salt-modified silica nanomicrosphere according to claim 1, characterized in that, The molar ratio of the 2,3-epoxypropyl trimethyl ammonium chloride to the polyethylene polyamine is (5-7):1; and the temperature of the fourth heating reaction is 70-80 DEG C, and the time is 4-6 h.

5. A hydrophilic metal-based anti-icing coating comprising the quaternary ammonium salt-modified silica nanomicrosphere according to claim 1, characterized in that, The quaternary ammonium salt modified silica nanospheres, epoxy resin and curing agent are mixed in a mass ratio of 1-3:8-12:5-8.

6. An anti-icing composite coating prepared from the hydrophilic metal-based anti-icing coating of claim 5.

7. A method of producing an anti-icing composite coating as claimed in claim 6, characterised in that, The anti-icing composite coating is prepared by mixing 1-3 parts of the quaternary ammonium salt modified silica nanospheres, 8-12 parts of epoxy resin and 5-8 parts of curing agent, and then uniformly coating the mixture on a metal surface and curing at room temperature.

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