CN115109492A - Preparation method of hydrophilic anti-ice coating - Google Patents

Abstract

The invention provides a preparation method of a hydrophilic anti-icing coating, belonging to the technical field of coating preparation. In the method, polyethylene glycol diglycidyl ether, diamine monomer and diluent are firstly added to the solvent, and stirred to obtain mixed solution A; the diamine monomer includes aliphatic diamine or aromatic diamine amine; the mixed solution A is stirred and reacted at 0-100 ℃ for 0.5-6 hours to obtain the to-be-coated sol B; the to-be-coated sol B is prepared into an anti-icing coating, and gelled at 0-50 ℃ for 2-48 hours , to obtain a hydrophilic anti-icing coating. The coating prepared by the invention has a loose ice layer between the ice layer and the coating at low temperature, so that the minimum ice adhesion force can be as low as 11.3kPa, and the light transmittance can be as high as 98.6%.

Description

A kind of preparation method of hydrophilic anti-icing coating

technical field

The invention belongs to the technical field of coating preparation, and in particular relates to a preparation method of a hydrophilic anti-icing coating.

Background technique

The unavoidable icing phenomenon in nature has a huge impact on daily life, industrial production, road traffic and other fields. Snow disasters lead to icing of cables, causing large-scale power outages, and causing huge property losses; icing on the surface of aircraft, changing aerodynamic shape, increasing flight resistance, resulting in loss of lift, reducing aircraft handling, stability and other safety performance, affecting flight Safety; the surface of the car is covered with ice, which affects travel. In order to reduce the loss caused by icing, a variety of anti-icing and deicing methods have been developed, such as the chemical deicing method of spraying anti-icing liquid before the aircraft takes off, and the electric heating deicing method of installing DC ice melting devices at both ends of the cable. , traditional active deicing methods such as the mechanical removal method of knocking and deicing the car surface. However, these methods often bring problems such as high energy consumption, high cost, and environmental pollution.

In order to avoid the adverse effects of the above traditional active deicing methods, in recent years, researchers have developed a series of anti-icing coatings around the passive coating deicing method. At present, the main preparation methods for anti-icing coatings are: 1) superhydrophobic anti-icing coatings inspired by the micro/nanostructures on the lotus leaf surface; 2) smooth lubricating fluid injected into the porous surface inspired by the "smooth lips" of Nepenthes (SLIPS) anti-icing coating; 3) hydrophilic anti-icing coating. In 2002, Laforte et al. demonstrated for the first time that superhydrophobic coatings have low ice adhesion (Proceedings of the international workshop on atmospheric icing of structures (IWAIS). Vol.6.2002.), and Kimura et al. subsequently adopted the method of organic-inorganic hybridization. An acrylic polyurethane-PTFE superhydrophobic anti-icing coating was prepared (No. 2007-01-3315. SAE Technical Paper, 2007.). Chinese patent CN111303738A obtains a super-hydrophobic anti-icing coating by spraying micro/nano particles on the surface of the substrate, heat treatment and fluorination treatment. However, it was later found that the viscosity of rainwater became larger at low temperature, and it was hard to bounce off after contacting the micro/nanostructure of the superhydrophobic coating, which lost its anti-icing performance. Due to the above shortcomings of superhydrophobic anti-icing coatings and the emergence of new passive anti-icing methods, super-hydrophobic surface anti-icing methods are gradually replaced. In 2011, Joanna Aizenberg, inspired by the smooth surface of Nepenthes (Nature 477.7365(2011):443-447.), formed on the substrate surface by infiltrating functionalized porous/textured solids with low surface energy, chemically inert liquids Physically smooth and chemically uniform lubricating fluid impregnated porous smooth surface (SLIPS) anti-icing coating. However, the lubricating fluid-injected porous smooth surface (SLIPS) is mostly in the form of porous adsorption, which makes it difficult for the lubricating fluid to exist stably in the coating, so it has the disadvantage of easy loss of lubricating fluid, which limits its application. . In addition, in 2014, Jianjun Wang prepared a hydrophilic anti-icing coating containing quaternary ammonium salts on the surface, which showed lower ice adhesion (ACS applied materials & interfaces 6.10 (2014): 6998-7003.). However, the preparation conditions of this quaternary ammonium salt-containing hydrophilic anti-icing coating are harsh, involving a variety of isocyanates and high-temperature reactions, which are not conducive to wide application.

SUMMARY OF THE INVENTION

The purpose of the present invention is to solve the shortcomings of the unsatisfactory anti-icing effect of the super-hydrophobic anti-icing coating, the poor wear resistance and the easy loss of the lubricating fluid of the anti-icing coating on the porous surface (SLIPS) in the prior art, and A preparation method of a hydrophilic anti-icing coating is provided.

The invention provides a preparation method of a hydrophilic anti-icing coating, the steps of which are as follows:

Step 1: add polyethylene glycol diglycidyl ether, diamine monomer and diluent to the solvent, stir to obtain mixed solution A; the diamine monomer includes aliphatic diamine or aromatic diamine ;

Step 2: The mixed solution A of step 1 is stirred and reacted at 0-100 ° C for 0.5-6 hours to obtain the sol B to be coated;

Step 3: Prepare the sol B to be coated obtained in Step 2 into an anti-icing coating, and gel at 0-50° C. for 2-48 hours to obtain a hydrophilic anti-icing coating.

Preferably, in the first step, other glycidyl ether monomers and reinforcing agents are also added.

Preferably, the other glycidyl ether monomers are selected from one or both of polyethylene glycol monoglycidyl ether or aromatic glycidyl ether.

Preferably, described aromatic glycidyl ether has the following structure:

where R1 includes the following structures _:

Preferably, the aliphatic diamine includes the following structure:

n＝2、3、4、6、8、10、12、14、16、18、20、24、30

n=2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, 24, 30

R ₂ , R ₄ , R ₇ , R ₁₀ are independently selected from -CH ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O( CH ₂ ) ₂ - or -(CH ₂ ) ₂ O(CH ₂ ) ₂ O(CH ₂ ) ₂ -;

R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₁ , R ₁₂ are independently selected from -CH ₃ , -C ₂ H ₅ , ^-tBu , -CH ₂ OCH ₃ or -CH(CH ₃ ) ₂ .

Preferably, the aromatic diamine includes the following structure:

Preferably, in the described step 1, the mass ratio of polyethylene glycol diglycidyl ether, other glycidyl ether monomers, diamine monomers, reinforcing agent and diluent is (1-10): ( 0-1): (0.1-10): (0-0.5): (5-20).

Preferably, the reinforcing agent in step 1 is silica nanoparticles, light calcium carbonate, talc, titanium dioxide or a combination thereof.

Preferably, a leveling agent, a defoaming agent, an antioxidant and an anti-ultraviolet absorbent are also added in the step 1, and the weight ratio of the leveling agent, the anti-foaming agent, the antioxidant and the anti-ultraviolet absorbent is 1: (0.1-10): (0.1-10): (0.1-10), and the addition amount of the above substances accounts for 0.1%-10% of the total weight.

Preferably, the leveling agent includes BYK-300, 301, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340 from BYK , 341, 344, 345, 346, 347, 348, 349, 350, 352, 353, 354, 355 or 356 one or more.

Preferably, the defoamer includes BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033 from BYK, Germany , 034, 035, 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085 or several.

Preferably, the antioxidant includes one or more of phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 or antioxidant B215.

Preferably, the anti-ultraviolet absorber comprises phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxydiphenylmethane ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, resorcinol monobenzoate or 2,2'-thiobis(4 - One or more of tert-octylphenoxy) nickel.

Principles of the invention

The invention mainly uses the hydrophilicity of polyethylene glycol in polyethylene glycol diglycidyl ether, the prepared coating has good hydrophilicity, the surface of the coating swells with water, and there is a layer between the coating and the ice layer The thin loose ice layer (see Fig. 3a) makes it difficult for the ice layer to adhere to the coating, and it is released from the coating after wind blowing (see Fig. 3b). Because the existence of the coating reduces the ice adhesion strength, it has a good anti-icing effect.

The beneficial effects of the present invention

(1) The present invention uses polyethylene glycol diglycidyl ether to react with diamines for the first time, and utilizes the sol-gel method to prepare the sol mother liquor of the hydrophilic anti-icing coating. There is a loose ice layer between the coatings, so that the minimum ice adhesion can be as low as 11.3kPa; (2) The anti-ice coating prepared by the sol-gel method of the present invention has good light transmittance and the highest light transmittance up to 98.6%;

(3) the present invention improves the mechanical strength and water resistance of coating by adding reinforcing agents such as silica nanoparticles;

(4) The reaction conditions of the present invention are mild, the preparation is simple, the coating has excellent anti-icing performance, there is no risk of loss of lubricating fluid, and at the same time, it has high transparency and good engineering application prospects.

Description of drawings

Figure 1 is a graph of the contact angle of the coatings prepared in Examples 1-5.

Figure 2 is a schematic diagram showing the comparison of the adhesion strength of ice on different substrates.

3 is a photo of the ice adhesion test of the coatings prepared in Examples 1-5.

Detailed ways

The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited thereto.

The invention provides a preparation method of a hydrophilic anti-icing coating, the steps of which are as follows:

Step 1: add polyethylene glycol diglycidyl ether, diamine monomer and diluent in the solvent, stir, the stirring temperature is preferably 0-80 ° C, and the reaction time is preferably 5-30 minutes, and the mixture is obtained. Solution A; the diamine monomers include aliphatic diamine or aromatic diamine;

Step 2: The mixed solution A of step 1 is stirred and reacted at 0-100 ° C for 0.5-6 hours to obtain the sol B to be coated; the reaction temperature varies according to the types of diamine monomers in the mixed solution A, When the diamine monomer is an aliphatic diamine, the reaction temperature is preferably 0-80 °C, more preferably 20-60 °C; when the diamine monomer is an aromatic diamine, the reaction temperature is preferably 0-100 °C °C, more preferably 30-80 °C;

Step 3: Prepare the sol B to be coated obtained in Step 2 into an anti-icing coating, and gel at 0-50° C. for 2-48 hours, preferably 4-24 hours, to obtain a hydrophilic anti-icing coating. The method for preparing the anti-icing coating with the sol B to be coated is not particularly limited, and can be prepared by casting, brushing or spraying methods well known in the art, and the solid content of the sol B to be coated is preferably 5%. -100%, more preferably 10-60%.

According to the present invention, other glycidyl ether monomers and reinforcing agents are also added in the first step. Described other glycidyl ether monomers are selected from one or both of polyethylene glycol monoglycidyl ether or aromatic glycidyl ether, wherein said aromatic glycidyl ether preferably has the following structure:

where R1 includes the following structures _:

n的取值范围为2-20；

The value range of n is 2-20;

According to the present invention, the number average molecular weight of polyethylene glycol diglycidyl ether in the step 1 is preferably 300, 500, 600, 800, 1000, 1500, 2000, 3000, 4000, 6000, 8000, 10000, 15000, 20000; the number average molecular weight of polyethylene glycol monoglycidyl ether is preferably 300, 450, 750, 1000, 1500, 2000, 3000, 4000, 6000, 8000, 10000, 20000.

According to the present invention, the diamine monomer includes aliphatic diamine or aromatic diamine, and the aliphatic diamine preferably includes the following structure:

n＝2、3、4、6、8、10、12、14、16、18、20、24、30

n=2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, 24, 30

R ₂ , R ₄ , R ₇ , R ₁₀ are independently selected from -CH ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O( CH ₂ ) ₂ - or -(CH ₂ ) ₂ O(CH ₂ ) ₂ O(CH ₂ ) ₂ -;

R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₁ , R ₁₂ are independently selected from -CH ₃ , -C ₂ H ₅ , ^-tBu , -CH ₂ OCH ₃ or -CH(CH ₃ ) ₂ .

More preferably, the aliphatic diamine includes the following structure:

Described aromatic diamine includes following structure:

According to the present invention, the stirring reaction described in step 1 is preferably carried out under the atmosphere of air or N ₂ .

According to the present invention, the reinforcing agent in step 1 is preferably silica nanoparticles (7-100 nanometers), light calcium carbonate (20-100 nanometers), talc (3.5-75 micrometers) or titanium dioxide (20-100 nanometers) ) one or more of.

According to the present invention, the diluent in step 1 preferably comprises water, methanol, ethanol, isopropanol, ethylene glycol, n-butanol, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethy Methylacetamide, N-methyl-2-pyrrolidone, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, ethyl acetate, methyl acetate, acetone, butanone, ether, alkane One or more of , anisole or benzyl alcohol.

According to the present invention, a leveling agent, a defoaming agent, an antioxidant and an anti-ultraviolet absorber are also added in the first step. The weight ratio of the leveling agent, defoaming agent, antioxidant and anti-ultraviolet absorber is preferably 1: (0.1-10): (0.1-10): (0.1-10), and the addition amount of the above substances accounts for 0.1%-10% of the total weight.

The leveling agent preferably includes BYK-300, 301, 302, 306, 307, 310, 313, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 341, One or more of 344, 345, 346, 347, 348, 349, 350, 352, 353, 354, 355 or 356.

The defoamer preferably includes BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033, 034, One or more of 035, 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085 .

Described antioxidant preferably comprises one or more in phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 or antioxidant B215.

The anti-ultraviolet absorber preferably includes phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2,4-dihydroxybenzophenone, 2 -Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, resorcinol monobenzoate or 2,2'-thiobis(4-tert-octane) One or more of nickel phenoloxy) and nickel.

According to the present invention, in the described step 1, the mass ratio of polyethylene glycol diglycidyl ether, other glycidyl ether monomers, diamine monomers, reinforcing agent and diluent is preferably (1-10): (0-1): (0.1-10): (0-0.5): (5-20). The molar ratio of the total amount of glycidyl ether to the total amount of diamine is preferably (1-10):1, more preferably (2-8):1. The molar ratio of the total molar amount of the other glycidyl ether monomers to polyethylene glycol diglycidyl ether is preferably 1:(2-15), more preferably 1:(5-10).

The hydrophilic anti-icing coating provided by the invention is mainly prepared by the sol-gel method by reacting polyethylene glycol diglycidyl ether with diamine, adding a certain amount of reinforcing agent, and the coating has excellent anti-icing properties. Ice performance, can significantly reduce ice adhesion.

The present invention is described in further detail below in conjunction with the examples, and the raw materials involved in the examples are all commercially available.

Example 1

Select polyethylene glycol diglycidyl ether (molecular weight=500) and hexamethylene diamine as the main raw material (PEGDE-1) of anti-icing coating, concrete implementation method is as follows:

Take 5.00 grams of polyethylene glycol diglycidyl ether (molecular weight = 500), 0.52 grams of hexamethylene diamine, 0.05 grams of defoamer BYK-011, 0.08 grams of leveling agent BYK-300, 0.1 grams of antioxidant antioxidant S9228, 0.05 grams 2,4-dihydroxybenzophenone, an anti-ultraviolet absorber, and 8.00 grams of absolute ethanol were added to a single-necked bottle, and the mixture was stirred evenly at room temperature to obtain a mixed solution.

The above mixed solution was magnetically stirred at room temperature for 4 hours to obtain the anti-icing coating mother liquor.

The anti-icing coating mother solution prepared above was prepared by the casting method to prepare the anti-icing coating, and gelatinized at room temperature for 12 h to obtain the hydrophilic anti-icing coating;

The anti-ice coating PEGDE-1 prepared in Example 1 is a colorless and transparent film, the contact angle of the coating is shown in Figure 1, and its ice adhesion strength at -18 degrees Celsius is 11.3kPa, as shown in Figure 1. As shown in Fig. 2, the light transmittance is characterized by ultraviolet absorption spectrometer, and the result shows that the light transmittance of the prepared anti-icing layer is above 98.6%, and the test range is 400-800 nanometers. The results are shown in Table 1.

Example 2

Select polyethylene glycol diglycidyl ether (molecular weight=500) and 1,12-diaminododecane as the main raw material (PEGDE-2) of anti-icing coating, concrete implementation method is as follows:

Take 5.00 g of polyethylene glycol diglycidyl ether (molecular weight = 500), 0.87 g of 1,12-diaminododecane, 0.05 g of defoamer BYK-021, 0.08 g of leveling agent BYK-310, 0.1 g of antifoam Oxidant antioxidant S9228, 0.05 g of anti-ultraviolet absorber 2,4-dihydroxybenzophenone, and 8.00 g of absolute ethanol were added to a single-neck bottle, and stirred evenly at room temperature to obtain a mixed solution.

The above mixed solution was magnetically stirred at 50 degrees Celsius for 1 hour to obtain an anti-icing coating mother solution.

The anti-icing coating mother solution prepared above was used to prepare an anti-icing coating by a casting method, and gelling at room temperature for 12 hours to obtain a hydrophilic anti-icing coating.

The anti-icing coating PEGDE-2 prepared in Example 2 is also a colorless and transparent film. The contact angle of the coating is shown in Figure 1, and its ice adhesion strength at -18 degrees Celsius is 17.2kPa, as shown in Figure 1. As shown in Fig. 2, the light transmittance is characterized by ultraviolet absorption spectrometer, and the result shows that the light transmittance of the prepared anti-icing layer is above 97%, and the test range is 400-800 nanometers. The results are shown in Table 1.

Example 3

Polyethylene glycol diglycidyl ether (molecular weight = 500), 1,12-diaminododecane and hydrophilic silica nanoparticles (7-20 nm) were selected as the main raw materials of the anti-icing coating (PEGDE- 3), the specific implementation method is as follows:

Take 5.00 g polyethylene glycol diglycidyl ether (molecular weight = 500), 0.87 g 1,12-diaminododecane, 0.32 g hydrophilic silica nanoparticles (7-20 nm), 0.05 g defoaming Agent BYK-044, 0.08 g leveling agent BYK-315, 0.1 g antioxidant SH120, 0.05 g anti-ultraviolet absorber phenyl o-hydroxybenzoate, 8.00 g absolute ethanol were added to a single-neck bottle, at room temperature Stir well to obtain a mixed solution.

The above mixed solution was magnetically stirred at 50 degrees Celsius for 1 hour to obtain an anti-icing coating mother solution.

The anti-icing coating mother solution prepared above was used to prepare an anti-icing coating by a casting method, and gelling at room temperature for 12 hours to obtain a hydrophilic anti-icing coating.

The anti-ice coating PEGDE-3 prepared in Example 3 is a colorless and transparent film, the contact angle of the coating is shown in Figure 1, and its ice adhesion strength at -18 degrees Celsius is 16.5kPa, as shown in Figure 1. 2 shown. The transmittance was characterized by ultraviolet absorption spectrometer, and the results showed that the transmittance of the prepared anti-icing layer was above 95.2%, and the test range was 400-800 nanometers. The results are shown in Table 1.

Example 4

Select polyethylene glycol diglycidyl ether (molecular weight = 500), 1,12-diaminododecane, bisphenol A diglycidyl ether and hydrophilic silica nanoparticles (7-20 nm) as anti-icing The main raw material of the coating (PEGDE-4), the specific implementation method is as follows:

Take 5.00 g polyethylene glycol diglycidyl ether (molecular weight = 500), 0.87 g 1,12-diaminododecane, 0.64 g bisphenol A diglycidyl ether, 0.32 g hydrophilic silica nanoparticles ( 7-20 nm), 0.05 g defoamer BYK-044, 0.08 g leveling agent BYK-315, 0.1 g antioxidant SH120, 0.05 g UV absorber phenyl phthalate, 8.00 g anhydrous Ethanol was added to a single-necked bottle, and stirred uniformly at room temperature to obtain a mixed solution.

The above mixed solution was magnetically stirred at 50 degrees Celsius for 1 hour to obtain an anti-icing coating mother solution.

The anti-icing coating mother solution prepared above was sprayed to prepare the anti-icing coating, and gelatinized at room temperature for 24 hours to obtain the hydrophilic anti-icing coating.

The anti-ice coating PEGDE-4 prepared in Example 4 is a colorless and transparent film, the contact angle of the coating is shown in Figure 1, and its ice adhesion strength at -18 degrees Celsius is 18.3kPa, as shown in Figure 1. 2 shown. The transmittance was characterized by ultraviolet absorption spectrometer, and the results showed that the transmittance of the prepared anti-icing layer was above 91.5%, and the test range was 400-800 nanometers. The results are shown in Table 1.

Example 5

Select for use polyethylene glycol diglycidyl ether (molecular weight=500), 2,2'-bissulfonic acid benzidine as the main raw material (PEGDE-5) of anti-icing coating, the specific implementation method is as follows:

Take 2.29 g of 2,2'-bissulfonic acid benzidine, disperse it in 40 g of water, heat to 80 °C under N atmosphere and add ₂ g of 10M NaOH to it to dissolve the undissolved 2,2'-bissulfonic acid Benzidine dissolves. Subsequently, 10 g polyethylene glycol diglycidyl ether (molecular weight = 500), 0.05 g defoamer BYK-044, 0.08 g leveling agent BYK-315, 0.1 _g antioxidant SH120 were added under N atmosphere , 0.05 g of phenyl o-hydroxybenzoate, an anti-ultraviolet absorber, was stirred evenly at 80 degrees Celsius to obtain a mixed solution.

The mixed solution was reacted at 80 degrees Celsius for 6 hours to obtain the mother liquor of the anti-icing coating.

The anti-icing coating mother solution prepared above was sprayed to prepare an anti-icing coating, and gelled at room temperature for 48 hours to obtain a hydrophilic anti-icing coating.

The anti-ice coating PEGDE-5 prepared in Example 5 is a yellow translucent film, the contact angle of the coating is shown in Figure 1, and its ice adhesion strength at -18 degrees Celsius is 45.9kPa, as shown in Figure 1. 2 shown. The light transmittance was characterized by ultraviolet absorption spectrometer, and the results showed that the light transmittance of the prepared anti-icing layer was above 85%, and the test range was 400-800 nanometers. The results are shown in Table 1.

Comparative Example 1

Select 1,12-diaminododecane, bisphenol A diglycidyl ether and hydrophilic silica nanoparticles (7-20 nanometers) as the main raw material of anti-icing coating, and the specific implementation method is as follows:

Take 1.00 g 1,12-diaminododecane, 5.12 g bisphenol A diglycidyl ether, 0.25 g hydrophilic silica nanoparticles (7-20 nm), 0.05 g defoamer BYK-044, 0.08 g Gram leveling agent BYK-315, 0.1 g antioxidant SH120, 0.05 g anti-ultraviolet absorber phenyl o-hydroxybenzoate, 8.00 g absolute ethanol were added to a single-neck bottle, and stirred evenly at room temperature to obtain a mixed solution .

The mixed solution was magnetically stirred at 50 degrees Celsius for 1 hour to obtain an anti-icing coating mother solution.

The anti-icing coating mother solution prepared above was used to prepare the anti-icing coating by the casting method, and gelatinized at room temperature for 24 hours to obtain the hydrophilic anti-icing coating.

The anti-ice coating prepared in Comparative Example 1 is a colorless and transparent film, and its ice adhesion strength at -18 degrees Celsius is 256.3kPa. Compared with the ice adhesion force after coating treatment, it can be seen that the ice adhesion force decreased significantly after coating treatment (see Figure 2). The transmittance was characterized by ultraviolet absorption spectrometer, and the results showed that the transmittance of the prepared anti-icing layer was above 92%, and the test range was 400-800 nanometers. The results are shown in Table 1.

Comparative Example 2

Select polyethylene glycol diglycidyl ether (molecular weight = 500), 1,12-diaminododecane, bisphenol A diglycidyl ether and hydrophilic silica nanoparticles (7-20 nm) as anti-icing The main raw materials of the coating are as follows:

Take 5.00 g of polyethylene glycol diglycidyl ether (molecular weight = 500), 0.67 g of 1,12-diaminododecane, 3.42 g of bisphenol A diglycidyl ether, 0.25 g of hydrophilic silica nanoparticles ( 7-20 nm), 0.05 g defoamer BYK-024, 0.08 g leveling agent BYK-345, 0.1 g antioxidant antioxidant B215, 0.05 g anti-UV absorber 2-hydroxy-4-methoxydiphenyl Methyl ketone and 8.00 g of absolute ethanol were added to a single-necked bottle, and stirred evenly at room temperature to obtain a mixed solution.

The mixed solution was magnetically stirred at 50 degrees Celsius for 1 hour to obtain the anti-icing coating mother solution.

The anti-icing coating mother solution prepared above was used to prepare the anti-icing coating by the casting method, and gelatinized at room temperature for 24 hours to obtain the hydrophilic anti-icing coating.

The anti-icing coating prepared in Comparative Example 2 is a colorless and transparent film, and its ice adhesion strength at -18 degrees Celsius is 103.2 kPa. The light transmittance was characterized by ultraviolet absorption spectrometer, and the results showed that the light transmittance of the prepared anti-icing layer was above 91%, and the test range was 400-800 nanometers. The results are shown in Table 1.

Table 1: Summary of Ice Adhesion Strength, Transmittance and Water Contact Angle of Coatings for Examples 1-5 and Comparative Examples 1-2

Ice Adhesion Strength (kPa) Transmittance (%) Contact angle (°) PEGDE-1 11.3 98.6 38 PEGDE-2 17.2 97 36 PEGDE-3 16.5 95.2 33 PEGDE-4 18.3 91.5 twenty four PEGDE-5 45.9 85 56 Comparative Example 1 256 92 85 Comparative Example 2 103 91 78

The coatings prepared in Examples 1-5 were tested for ice adhesion, as shown in Figure 3, where a is the anti-icing coating. After freezing, it can be seen that there is a loose layer between the ice layer and the coating. ice layer, thereby reducing the strength of ice adhesion. b means that the ice on the anti-ice coating can be easily detached from the coating surface after being blown by the wind, indicating that the ice adhesion strength is very small.

Claims (10)

1. a preparation method of hydrophilic anti-icing coating, is characterized in that, its steps are as follows: Step 1: add polyethylene glycol diglycidyl ether, diamine monomer and diluent to the solvent, stir to obtain mixed solution A; the diamine monomer includes aliphatic diamine or aromatic diamine ; Step 2: The mixed solution A of step 1 is stirred and reacted at 0-100 ° C for 0.5-6 hours to obtain the sol B to be coated; Step 3: Prepare the sol B to be coated obtained in Step 2 into an anti-icing coating, and gel at 0-50° C. for 2-48 hours to obtain a hydrophilic anti-icing coating. 2. the preparation method of a kind of hydrophilic anti-icing coating according to claim 1, is characterized in that, described step 1 also adds other glycidyl ether monomers and reinforcing agent. 3. the preparation method of a kind of hydrophilic anti-icing coating according to claim 2, is characterized in that, other described glycidyl ether monomers are selected from polyethylene glycol monoglycidyl ether or aromatic glycidyl ether One or both of glycerol ethers. 4. the preparation method of a kind of hydrophilic anti-icing coating according to claim 3, is characterized in that, described aromatic glycidyl ether has following structure:

where R1 includes the following structures _:

5. the preparation method of a kind of hydrophilic anti-icing coating according to claim 1, is characterized in that, described aliphatic diamine comprises following structure:

n=2, 3, 4, 6, 8, 10, 12, 14, 16, 18, 20, 24, 30

R ₂ , R ₄ , R ₇ , R ₁₀ are independently selected from -CH ₂ -, -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -CH ₂ OCH ₂ -, -(CH ₂ ) ₂ O( CH ₂ ) ₂ - or -(CH ₂ ) ₂ O(CH ₂ ) ₂ O(CH ₂ ) ₂ -; R ₃ , R ₅ , R ₆ , R ₈ , R ₉ , R ₁₁ , R ₁₂ are independently selected from -CH ₃ , -C ₂ H ₅ , ^-tBu , -CH ₂ OCH ₃ or -CH(CH ₃ ) ₂ . 6. the preparation method of a kind of hydrophilic anti-icing coating according to claim 1, is characterized in that, described aromatic diamine comprises following structure:

7. the preparation method of a kind of hydrophilic anti-icing coating according to claim 1, is characterized in that, in described step 1, polyethylene glycol diglycidyl ether, other glycidyl ether monomers, two The mass ratio of amine monomer, reinforcing agent and diluent is (1-10):(0-1):(0.1-10):(0-0.5):(5-20). 8. the preparation method of a kind of hydrophilic anti-icing coating according to claim 2, is characterized in that, the reinforcing agent of step 1 is silicon dioxide nanoparticle, light calcium carbonate, talcum powder, titanium dioxide or their The combination. 9. the preparation method of a kind of hydrophilic anti-icing coating according to claim 1, is characterized in that, in described step 1, also add leveling agent, defoamer, antioxidant and anti-ultraviolet absorber, The weight ratio of the leveling agent, defoaming agent, antioxidant and anti-ultraviolet absorber is 1:(0.1-10):(0.1-10):(0.1-10), and the addition amount of the above substances accounts for the total 0.1%-10% by weight. 10. The preparation method of a hydrophilic anti-icing coating according to claim 9, wherein the leveling agent comprises BYK-300, 301, 302, 306, 307, 310 of BYK, Germany , 313, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 341, 344, 345, 346, 347, 348, 349, 350, 352, 353, 354, 355, or 356 one or more; The defoamer includes BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033, 034, 035 from BYK, Germany , one or more of 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085; The antioxidant includes one or more of phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 or antioxidant B215; The anti-ultraviolet absorbers include phenyl o-hydroxybenzoate, 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, resorcinol monobenzoate or 2,2'-thiobis(4-tert-octyl) One or more of phenoxy) nickel.

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