CN115109492B - Preparation method of hydrophilic anti-icing coating - Google Patents
Preparation method of hydrophilic anti-icing coating Download PDFInfo
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- CN115109492B CN115109492B CN202210890116.1A CN202210890116A CN115109492B CN 115109492 B CN115109492 B CN 115109492B CN 202210890116 A CN202210890116 A CN 202210890116A CN 115109492 B CN115109492 B CN 115109492B
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides a preparation method of a hydrophilic anti-icing coating, and belongs to the technical field of coating preparation. Firstly, adding polyethylene glycol diglycidyl ether, diamine monomer and diluent into a solvent, and stirring to obtain a mixed solution A; the diamine monomer comprises aliphatic diamine or aromatic diamine; stirring the mixed solution A at 0-100 ℃ for reaction for 0.5-6 hours to obtain sol B to be coated; preparing the sol B to be coated into an anti-icing coating, and gelling at 0-50 ℃ for 2-48 hours to obtain the 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 ice adhesion can be as low as 11.3kPa, and the light transmittance can be as high as 98.6%.
Description
Technical Field
The invention belongs to the technical field of coating preparation, and particularly relates to a preparation method of a hydrophilic anti-icing coating.
Background
The unavoidable icing phenomenon in nature has a great influence on the fields of daily life, industrial production, road traffic and the like. The cable is covered with ice caused by the snow disaster, so that large-area power failure is caused, and huge property loss is caused; the aircraft surface is coated with ice, so that the aerodynamic shape is changed, the flight resistance is increased, the lift loss is caused, the safety performances such as the maneuverability and the stability of the aircraft are reduced, and the flight safety is influenced; the surface of the automobile is covered with ice, and the travel is affected. In order to reduce the loss caused by icing, various anti-icing and deicing methods have been developed, such as a chemical deicing method of spraying anti-icing liquid before aircraft take-off, an electric heating deicing method of erecting direct current deicing devices at two ends of a cable, a mechanical deicing method of knocking deicing on the surface of an automobile, and other traditional active deicing methods. However, these methods often have problems of high energy consumption, high cost, environmental pollution, and the like.
In order to avoid the adverse effects of the above conventional active deicing methods, in recent years, researchers have developed a series of anti-icing coatings around passive coating deicing methods. At present, the main preparation method of the anti-icing coating comprises the following steps: 1) The super-hydrophobic ice-resistant coating inspired by the micro/nano structure of the lotus leaf surface; 2) A smooth lubricating fluid initiated by nepenthes "smooth lips" is infused into the porous surface (SLIPS) anti-icing coating; 3) Hydrophilic anti-icing coatings. 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 subsequently Kimura et al prepared polyurethane-PTFE superhydrophobic anti-ice coatings by organic-inorganic hybridization (No. 2007-01-3315.SAE Technical Paper,2007.). Chinese patent CN111303738A provides a superhydrophobic anti-ice coating by spraying micro/nano particles on a substrate surface and then performing a heat treatment and a fluorination treatment. However, it was subsequently found that the viscosity of the rainwater at low temperature became large, and the rainwater was difficult to pop open after contacting the micro/nano structure of the superhydrophobic coating, and lost the ice resistance. Due to the above drawbacks of superhydrophobic anti-icing coatings and the emergence of novel passive anti-icing methods, superhydrophobic surface anti-icing methods are gradually replaced. In 2011, joanna Aizenberg was inspired by nepenthes smooth surface (Nature 477.7365 (2011): 443-447.) by infiltration of functionalized porous/textured solids with low surface energy, chemically inert liquids to form a physically smooth and chemically uniform porous smooth surface (SLIPS) anti-ice coating of infused lubricating liquid on the substrate surface. However, the porous smooth surface (SLIPS) injected with the lubricating liquid has the defect of easy loss of the lubricating liquid because the lubricating liquid is difficult to stably exist in the coating due to the injection mode of porous adsorption, and the application of the porous smooth surface (SLIPS) is limited. In addition, in 2014, jianjun Wang prepared hydrophilic anti-ice coatings with quaternary ammonium salts on the surface, showing lower ice adhesion (ACS applied materials & interfaces 6.10 (2014): 6998-7003.). However, the preparation condition of the hydrophilic anti-icing coating containing the quaternary ammonium salt is harsh, relates to various isocyanates and high-temperature reactions, and is not favorable for wide application.
Disclosure of Invention
The invention aims to solve the defects of the prior art that the super-hydrophobic anti-icing coating has unsatisfactory anti-icing effect and poor wear resistance, and the smooth lubricating liquid is easy to run off when being injected into a porous surface (SLIPS) anti-icing coating, and provides a preparation method of a hydrophilic anti-icing coating.
The invention provides a preparation method of a hydrophilic anti-icing coating, which comprises the following steps:
step one: adding polyethylene glycol diglycidyl ether, diamine monomer and diluent into a solvent, and stirring to obtain a mixed solution A; the diamine monomer comprises aliphatic diamine or aromatic diamine;
step two: stirring the mixed solution A in the step one at 0-100 ℃ for reaction for 0.5-6 hours to obtain sol B to be coated;
step three: preparing the sol B to be coated obtained in the step two into an anti-icing coating, and gelling at 0-50 ℃ for 2-48 hours to obtain the 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 two of polyethylene glycol monoglycidyl ether or aromatic glycidyl ether.
Preferably, the aromatic glycidyl ether has the following structure:
wherein R is 1 The structure comprises the following steps:
preferably, the aliphatic diamine comprises the following structure:
n＝2、3、4、6、8、10、12、14、16、18、20、24、30
R 2 、R 4 、R 7 、R 10 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 Independently selected from-CH 3 、-C 2 H 5 、- t Bu、-CH 2 OCH 3 or-CH (CH) 3 ) 2 。
Preferably, the aromatic diamine comprises the following structure:
preferably, in the first step, the mass ratio of the polyethylene glycol diglycidyl ether, other glycidyl ether monomers, diamine monomers, reinforcing agents and diluents is (1-10): (0-1): (0.1-10): (0-0.5): (5-20).
Preferably, the reinforcing agent in the first step is silica nanoparticles, light calcium carbonate, talcum powder, titanium dioxide or a combination thereof.
Preferably, in the first step, a leveling agent, a defoaming agent, an antioxidant and an anti-ultraviolet absorber are further added, wherein the weight ratio of the leveling agent to the defoaming agent to the antioxidant to the anti-ultraviolet absorber is (1) (0.1-10): (0.1-10): (0.1-10), and the addition amount of the substances accounts for 0.1-10% of the total weight.
Preferably, the leveling agent comprises one or more of BYK-300, 301, 302, 306, 307, 310, 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 of Pick, germany.
Preferably, the defoamer comprises one or more of BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033, 034, 035, 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085 of Pick.
Preferably, the antioxidant comprises one or more of phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 and antioxidant B215.
Preferably, the anti-ultraviolet absorbent comprises one or more of phenyl o-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate or 2,2' -thiobis (4-tert-octylphenol oxy) 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 absorbs water and swells, a thin loose ice layer exists between the coating and the ice layer (see figure 3 a), so that the ice layer is difficult to adhere on the coating, and the ice layer is separated from the coating after blowing (see figure 3 b). The presence of the coating reduces ice adhesion strength and has good anti-icing effect.
The beneficial effects of the invention are that
(1) According to the invention, polyethylene glycol diglycidyl ether is reacted with diamine for the first time, a sol-gel method is utilized to prepare a sol mother solution of a hydrophilic anti-icing coating, and a loose ice layer exists between the ice layer and the coating at low temperature of the prepared coating, so that the ice adhesion force can be as low as 11.3kPa; (2) The anti-icing coating prepared by the sol-gel method has good light transmittance, and the highest light transmittance can reach 98.6%;
(3) According to the invention, the mechanical strength and the water resistance of the coating are improved by adding reinforcing agents such as silica nanoparticles;
(4) The invention has mild reaction condition, simple preparation, excellent anti-icing performance of the coating, no risk of lubricating liquid loss, high transparency and good engineering application prospect.
Drawings
FIG. 1 is a graph of contact angles for coatings prepared in examples 1-5.
FIG. 2 is a graph showing the comparison of the adhesion strength of ice to various substrates.
FIG. 3 is a photograph of an ice adhesion test of the coatings prepared in examples 1-5.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
The invention provides a preparation method of a hydrophilic anti-icing coating, which comprises the following steps:
step one: adding polyethylene glycol diglycidyl ether, diamine monomer and diluent into a solvent, stirring, wherein the stirring temperature is preferably 0-80 ℃, and the reaction time is preferably 5-30 minutes, so as to obtain a mixed solution A; the diamine monomer comprises aliphatic diamine or aromatic diamine;
step two: stirring the mixed solution A in the step one at 0-100 ℃ for reaction for 0.5-6 hours to obtain sol B to be coated; the reaction temperature is different according to the types of diamine monomers in the mixed solution A, and when the diamine monomers are aliphatic diamine, the reaction temperature is preferably 0-80 ℃, more preferably 20-60 ℃; when the diamine monomer is an aromatic diamine, the reaction temperature is preferably 0 to 100 ℃, more preferably 30 to 80 ℃;
step three: preparing the sol B to be coated obtained in the step two into an anti-icing coating, and gelling at 0-50 ℃ for 2-48 hours, preferably 4-24 hours, to obtain the hydrophilic anti-icing coating. The method for preparing the anti-icing coating by the sol B to be coated is not particularly limited, and the anti-icing coating can be prepared by adopting a casting, brushing or spraying method well known in the art, wherein the solid content of the sol B to be coated is preferably 5% -100%, and more preferably 10% -60%.
According to the invention, other glycidyl ether monomers and reinforcing agents are also added in the first step. The other glycidyl ether monomer is selected from one or two of polyethylene glycol monoglycidyl ether or aromatic glycidyl ether, wherein the aromatic glycidyl ether preferably has the following structure:
wherein R is 1 The structure comprises the following steps:
n has a value range of 2-20;
according to the present invention, the number average molecular weight of the polyethylene glycol diglycidyl ether in the first step is preferably 300, 500, 600, 800, 1000, 1500, 2000, 3000, 4000, 6000, 8000, 10000, 15000, 20000; the number average molecular weight of the polyethylene glycol monoglycidyl ether is preferably 300, 450, 750, 1000, 1500, 2000, 3000, 4000, 6000, 8000, 10000, 20000.
According to the invention, the diamine monomer comprises an aliphatic diamine or an aromatic diamine, and the aliphatic diamine preferably comprises the following structure:
n＝2、3、4、6、8、10、12、14、16、18、20、24、30
R 2 、R 4 、R 7 、R 10 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 Independently selected from-CH 3 、-C 2 H 5 、- t Bu、-CH 2 OCH 3 or-CH (CH) 3 ) 2 。
More preferably, the aliphatic diamine comprises the following structure:
the aromatic diamine comprises the following structures:
according to the invention, the stirred reaction described in step one is preferably carried out in air or N 2 And (3) reacting under the atmosphere.
According to the invention, the reinforcing agent in the first step is preferably one or more of silica nanoparticles (7-100 nm), light calcium carbonate (20-100 nm), talcum powder (3.5-75 μm) or titanium dioxide (20-100 nm).
According to the present invention, the diluent of the first step preferably includes one or more of water, methanol, ethanol, isopropanol, ethylene glycol, N-butanol, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, methylene chloride, chloroform, carbon tetrachloride, benzene, toluene, xylene, ethyl acetate, methyl acetate, acetone, butanone, diethyl ether, alkane, anisole or benzyl alcohol.
According to the 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 flatting agent, the defoamer, the antioxidant and the anti-ultraviolet absorber is preferably 1 (0.1-10): (0.1-10): (0.1-10), and the addition amount of the substances accounts for 0.1-10% of the total weight.
The leveling agent preferably comprises one or more of BYK-300, 301, 302, 306, 307, 310, 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 of Pick, germany.
The defoamer preferably comprises one or more of BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033, 034, 035, 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085 of bikes of germany.
The antioxidant preferably comprises one or more of phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 and antioxidant B215.
The anti-ultraviolet absorbent preferably comprises one or more of phenyl o-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate or 2,2' -thiobis (4-tert-octylphenol oxy) nickel.
According to the invention, the mass ratio of the polyethylene glycol diglycidyl ether, other glycidyl ether monomers, diamine monomers, reinforcing agents and diluents in the step one is preferably (1-10): (0-1): (0.1-10): (0-0.5): (5-20). The molar ratio of the total amount of the glycidyl ether to the total amount of the diamine is preferably (1 to 10): 1, more preferably (2 to 8): 1. The molar ratio of the total molar amount of the other glycidyl ether monomers to the polyethylene glycol diglycidyl ether is preferably 1 (2 to 15), more preferably 1 (5 to 10).
The hydrophilic anti-icing coating provided by the invention is prepared by mainly reacting polyethylene glycol diglycidyl ether with diamine, adding a certain amount of reinforcing agent and using a sol-gel method, has excellent anti-icing performance, and can obviously reduce the adhesion of ice.
The invention is described in further detail below with reference to the examples, in which the starting materials involved are all commercially available.
Example 1
Polyethylene glycol diglycidyl ether (molecular weight=500) and hexamethylenediamine are selected as main raw materials (PEGDE-1) of the anti-icing coating, and the specific implementation method is as follows:
5.00 g of polyethylene glycol diglycidyl ether (molecular weight=500), 0.52 g of hexamethylenediamine, 0.05 g of defoamer BYK-011,0.08 g of flatting agent BYK-300,0.1 g of antioxidant S9228,0.05 g of anti-ultraviolet absorber 2, 4-dihydroxybenzophenone and 8.00 g of absolute ethyl alcohol are added into a single-mouth bottle, and stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution for 4 hours at room temperature to obtain the anti-icing coating mother solution.
Preparing an anti-ice coating from the prepared anti-ice coating mother solution by a tape casting method, and gelling for 12 hours at room temperature to obtain a hydrophilic anti-ice coating;
the anti-ice coating PEGDE-1 prepared in example 1 is a colorless transparent film, the contact angle graph of the coating is shown in figure 1, the ice adhesion strength of the coating at-18 ℃ is 11.3kPa, the light transmittance of the coating is shown in figure 2 by an ultraviolet absorption spectrometer, the result shows that the light transmittance of the prepared anti-ice coating is above 98.6%, and the test range is 400-800 nanometers. The results are shown in Table 1.
Example 2
Polyethylene glycol diglycidyl ether (molecular weight=500) and 1, 12-diaminododecane were selected as main raw materials (PEGDE-2) for the anti-icing coating, and the specific implementation method is as follows:
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 flatting agent BYK-310,0.1 g of antioxidant S9228,0.05 g of anti-ultraviolet absorber 2, 4-dihydroxybenzophenone and 8.00 g of absolute ethyl alcohol are taken, added into a single-mouth bottle, and stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution at 50 ℃ for 1 hour to obtain the anti-icing coating mother solution.
And (3) preparing the ice-resistant coating mother solution by a tape casting method, and gelling at room temperature for 12 hours to obtain the hydrophilic ice-resistant coating.
The anti-ice coating PEGDE-2 prepared in example 2 is a colorless transparent film, the contact angle diagram of the coating is shown in figure 1, the ice adhesion strength is 17.2kPa at the temperature of minus 18 ℃, the light transmittance is shown in figure 2, the result shows that the light transmittance of the prepared anti-ice coating is above 97% by an ultraviolet absorption spectrometer, 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 (PEGDE-3) of the anti-icing coating, and the specific implementation method is as follows:
5.00 g of polyethylene glycol diglycidyl ether (molecular weight=500), 0.87 g of 1, 12-diaminododecane, 0.32 g of hydrophilic silica nanoparticles (7-20 nanometers), 0.05 g of defoamer BYK-044,0.08 g of flatting agent BYK-315,0.1 g of antioxidant SH120,0.05 g of anti-ultraviolet absorber phenyl o-hydroxybenzoate and 8.00 g of absolute ethyl alcohol are added into a single-mouth bottle, and the mixture is stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution at 50 ℃ for 1 hour to obtain the anti-icing coating mother solution.
And (3) preparing the ice-resistant coating mother solution by a tape casting method, and gelling at room temperature for 12 hours to obtain the hydrophilic ice-resistant coating.
The anti-ice coating PEGDE-3 prepared in example 3 was a colorless transparent film, the contact angle of the coating was shown in FIG. 1, and the ice adhesion strength at-18℃was 16.5kPa, as shown in FIG. 2. The transmittance of the anti-ice layer is characterized by an ultraviolet absorption spectrometer, and the result shows that the transmittance of the prepared anti-ice layer is more than 95.2%, and the testing range is 400-800 nanometers. The results are shown in Table 1.
Example 4
Polyethylene glycol diglycidyl ether (molecular weight=500), 1, 12-diaminododecane, bisphenol a diglycidyl ether, and hydrophilic silica nanoparticles (7-20 nm) were selected as the main raw materials (PEGDE-4) of the anti-icing coating, and the specific implementation method is as follows:
5.00 g of polyethylene glycol diglycidyl ether (molecular weight=500), 0.87 g of 1, 12-diaminododecane, 0.64 g of bisphenol a diglycidyl ether, 0.32 g of hydrophilic silica nanoparticles (7-20 nm), 0.05 g of defoamer BYK-044,0.08 g of flatting agent BYK-315,0.1 g of antioxidant SH120,0.05 g of anti-ultraviolet absorber phenyl o-hydroxybenzoate and 8.00 g of absolute ethyl alcohol are taken, and the mixture is stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution at 50 ℃ for 1 hour to obtain the anti-icing coating mother solution.
And preparing the ice-resistant coating from the prepared ice-resistant coating mother solution by a spraying method, and gelling at room temperature for 24 hours to obtain the hydrophilic ice-resistant coating.
The anti-ice coating PEGDE-4 prepared in example 4 was a colorless transparent film, the contact angle of the coating was shown in fig. 1, and the ice adhesion strength at-18 degrees celsius was 18.3kPa, as shown in fig. 2. The transmittance of the anti-ice layer is characterized by an ultraviolet absorption spectrometer, and the result shows that the transmittance of the prepared anti-ice layer is more than 91.5%, and the testing range is 400-800 nanometers. The results are shown in Table 1.
Example 5
Polyethylene glycol diglycidyl ether (molecular weight=500) and 2,2' -disulfonic acid benzidine are selected as main raw materials (PEGDE-5) of the anti-icing coating, and the specific implementation method is as follows:
2.29 g of 2,2' -disulfonic acid benzidine are taken and dispersed in 40 g of water, N 2 Undissolved 2,2' -disulfonic acid benzidine was dissolved by heating to 80℃under an atmosphere and adding 2 g of 10M NaOH thereto. Subsequently, at N 2 10 g of polyethylene glycol diglycidyl ether (molecular weight=500) is added under the atmosphere, 0.05 g of bubble eliminating agent BYK-044,0.08 g of flatting agent BYK-315,0.1 g of antioxidant SH120 and 0.05 g of anti-ultraviolet absorbent phenyl o-hydroxybenzoate are stirred uniformly at 80 ℃ to obtain mixed solutionAnd (3) liquid.
The mixed solution is reacted for 6 hours at 80 ℃ to obtain mother liquor of the anti-icing coating.
And preparing the ice-resistant coating from the prepared ice-resistant coating mother solution by a spraying method, and gelling at room temperature for 48 hours to obtain the hydrophilic ice-resistant coating.
The anti-ice coating PEGDE-5 prepared in example 5 was a yellow translucent film, the contact angle of the coating was shown in fig. 1, and the ice adhesion strength at-18 degrees celsius was 45.9kPa, as shown in fig. 2. The transmittance of the anti-ice layer is characterized by an ultraviolet absorption spectrometer, and the result shows that the transmittance of the prepared anti-ice layer is more than 85%, and the testing range is 400-800 nanometers. The results are shown in Table 1.
Comparative example 1
1, 12-diaminododecane, bisphenol A diglycidyl ether and hydrophilic silica nanoparticles (7-20 nanometers) are selected as main raw materials of the anti-icing coating, and the specific implementation method is as follows:
1.00 g of 1, 12-diaminododecane, 5.12 g of bisphenol A diglycidyl ether, 0.25 g of hydrophilic silica nanoparticles (7-20 nanometers), 0.05 g of defoamer BYK-044,0.08 g of flatting agent BYK-315,0.1 g of antioxidant SH120,0.05 g of anti-ultraviolet absorbent phenyl o-hydroxybenzoate and 8.00 g of absolute ethyl alcohol are taken, added into a single-mouth bottle, and stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution at 50 ℃ for 1 hour to obtain the anti-icing coating mother solution.
And (3) preparing the ice-resistant coating mother solution by a tape casting method, and performing gel at room temperature for 24 hours to obtain the hydrophilic ice-resistant coating.
The ice-resistant coating prepared in comparative example 1 was a colorless transparent film having an ice adhesion strength of 256.3kPa at-18 degrees celsius, and compared with the ice adhesion strength of different substrates, it was seen that the ice adhesion strength was significantly reduced after the coating treatment (see fig. 2). The transmittance of the anti-ice layer is characterized by an ultraviolet absorption spectrometer, and the result shows that the transmittance of the prepared anti-ice layer is more than 92%, and the testing range is 400-800 nanometers. The results are shown in Table 1.
Comparative example 2
Polyethylene glycol diglycidyl ether (molecular weight=500), 1, 12-diaminododecane, bisphenol a diglycidyl ether and hydrophilic silica nanoparticles (7-20 nm) are selected as main raw materials of the anti-icing coating, and the specific implementation method is as follows:
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 of defoamer BYK-024,0.08 g of flatting agent BYK-345,0.1 g of antioxidant B215,0.05 g of anti-ultraviolet absorber 2-hydroxy-4-methoxybenzophenone and 8.00 g of absolute ethyl alcohol are added into a single-mouth bottle, and stirred uniformly at room temperature to obtain a mixed solution.
And magnetically stirring the mixed solution at 50 ℃ for 1 hour to obtain the anti-icing coating mother solution.
And (3) preparing the ice-resistant coating mother solution by a tape casting method, and performing gel at room temperature for 24 hours to obtain the hydrophilic ice-resistant coating.
The anti-ice coating prepared in comparative example 2 was a colorless transparent film having an ice adhesion strength of 103.2kPa at-18 degrees celsius. The transmittance of the anti-icing layer is characterized by an ultraviolet absorption spectrometer, and the result shows that the transmittance of the prepared anti-icing layer is more than 91%, and the testing range is 400-800 nanometers. The results are shown in Table 1.
Table 1: the ice adhesion strength, transmittance and water contact angle of the coatings of examples 1-5 and comparative examples 1-2 are summarized
| Ice adhesionIntensity (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 | 24 |
| 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 subjected to an ice adhesion test, as shown in fig. 3, where a is the ice resistance of the coating after icing, and it can be seen that there is a loose ice layer between the ice layer and the coating, thereby reducing the ice adhesion strength. And b is that ice on the anti-ice coating can be easily separated from the surface of the coating after being blown by wind, which indicates that the ice adhesion strength is very small.
Claims (7)
1. The preparation method of the hydrophilic anti-icing coating is characterized by comprising the following steps:
step one: adding polyethylene glycol diglycidyl ether, diamine monomer and diluent into a solvent, and stirring to obtain a mixed solution A; the diamine monomer comprises aliphatic diamine or aromatic diamine; the first step is to add other glycidyl ether monomers and reinforcing agents; the mass ratio of the polyethylene glycol diglycidyl ether to other glycidyl ether monomers to diamine monomers to the reinforcing agent to the diluent is (1-10): (0-1 and not equal to 0): (0.1-10): (0-0.5 and not equal to 0): (5-20);
step two: stirring the mixed solution A in the step one at 0-100 ℃ for reaction for 0.5-6 hours to obtain sol B to be coated;
step three: preparing the sol B to be coated obtained in the step two into an anti-icing coating, and gelling at 0-50 ℃ for 2-48 hours to obtain a hydrophilic anti-icing coating;
in the first step, a leveling agent, a defoaming agent, an antioxidant and an anti-ultraviolet absorber are added, wherein the weight ratio of the leveling agent to the defoaming agent to the antioxidant to the anti-ultraviolet absorber is (1) (0.1-10): (0.1-10): (0.1-10), and the addition amount of the substances accounts for 0.1-10% of the total weight.
2. The method for preparing a hydrophilic anti-icing coating according to claim 1, wherein the other glycidyl ether monomers are selected from one or two of polyethylene glycol monoglycidyl ether and aromatic glycidyl ether.
3. The method of preparing a hydrophilic anti-icing coating according to claim 2, wherein the aromatic glycidyl ether has the following structure:
wherein R is 1 The structure comprises the following steps:
4. the method of preparing a hydrophilic anti-icing coating according to claim 1, wherein the aliphatic diamine comprises the following structure:
n＝2、3、4、6、8、10、12、14、16、18、20、24、30
R 2 、R 4 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 Independently selected from-CH 3 、-C 2 H 5 、- t Bu、-CH 2 OCH 3 or-CH (CH) 3 ) 2 。
5. The method of preparing a hydrophilic anti-icing coating according to claim 1, wherein the aromatic diamine comprises the following structure:
6. the method of claim 2, wherein the reinforcing agent in the first step is silica nanoparticles, light calcium carbonate, talc, titanium dioxide or a combination thereof.
7. The method for preparing a hydrophilic anti-icing coating according to claim 1, wherein the leveling agent comprises one or more of BYK-300, 301, 302, 306, 307, 310, 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;
the defoamer comprises one or more of BYK-011, 012, 014, 016, 017, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033, 034, 035, 036, 037, 038, 044, 045, 051, 052, 053, 054, 055, 057, 060N, 063, 065, 066N, 067, 070, 071, 072, 077 or 085 of Germany;
the antioxidant comprises one or more of phenol, hydroquinone, sodium hypophosphite, antioxidant 1010, antioxidant S9228, antioxidant SH120 and antioxidant B215;
the anti-ultraviolet absorbent comprises one or more of phenyl o-hydroxybenzoate, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, resorcinol monobenzoate or 2,2' -thiobis (4-tert-octylphenol oxy) nickel.
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