CN116042059A - High-strength anti-icing paint, high-strength anti-icing coating, and preparation methods and applications thereof - Google Patents

Abstract

The invention provides a high-strength anti-icing coating, a high-strength anti-icing coating and a preparation method and application thereof, belonging to the technical field of functional materials. The high-strength anti-icing coating provided by the present invention comprises the following preparation raw materials in parts by mass: 100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 part of leveling agent, 0.2-0.8 part of defoamer, 0.2-1 part of the catalyst, 100-10000 parts of the organic solvent; the skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor. The coating prepared by adopting the high-strength anti-icing paint provided by the invention has high strength and good adhesion to the substrate, and can maintain the anti-icing performance of the interface for a long time.

Description

High-strength anti-icing paint, high-strength anti-icing coating, preparation method and application thereof

Technical Field

The present invention relates to the technical field of functional materials, and in particular to a high-strength anti-icing paint, a high-strength anti-icing coating, and a preparation method and application thereof.

Background Art

In the fields of aerospace, power grid, machinery and engineering, ice formation on the exposed surfaces of equipment or devices can cause immeasurable losses. How to prevent ice formation has attracted the attention of researchers. The key to anti-icing/de-icing research is to reduce the adhesion between ice and the surface. Existing anti-icing strategies can be divided into two methods: the first is an active strategy that mainly relies on external energy input, and the second is a passive strategy that is mainly based on liquid repellent technology. Compared with active strategies, passive strategies are free from energy and system constraints and are considered to be one of the most important components of the new generation of anti-icing systems.

Hydrophobic surfaces and lubricant-infused surfaces (SLIPS) are the most typical passive anti-icing surfaces, which rely on the solid-air interface inspired by lotus leaves and the solid/liquid interface inspired by pitcher plants, respectively. Specifically, the former mainly constructs a surface roughness structure by hydrophobic substances, and prepares super-hydrophobic surfaces by spraying, spin coating, drip coating and other methods. The latter mainly constructs a porous structure on the surface, performs hydrophobic modification, and then injects liquid lubricants (such as silicone oil, perfluoropolyether, liquid paraffin, etc.), which can effectively reduce the interfacial ice adhesion. However, the poor durability makes it difficult for these surfaces to maintain the anti-icing function in harsh external environments, such as under high speed, high pressure or high shear conditions. Among them, the use of organic gels injected with solid lubricants (such as PDMS and curing agents to form gel materials) can improve the anti-icing durability of SLIPS. The introduction of solid lubricants will enhance the interface lubricity and avoid interface function failure. However, the coating prepared in this way has weak adhesion to the substrate, low mechanical strength, and complex preparation process, which greatly limits its application in aerospace, power grid, machinery and engineering fields. In order to improve this problem, a special primer is generally constructed on the substrate surface. The preparation process is relatively complicated and the coating strength still needs to be improved.

Summary of the invention

The purpose of the present invention is to provide a high-strength anti-icing coating, a high-strength anti-icing coating and a preparation method and application thereof. The coating prepared using the high-strength anti-icing coating provided by the present invention has high strength and good adhesion to the substrate, and can maintain the anti-icing performance of the interface for a long time.

In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

The present invention provides a high-strength anti-icing coating, which comprises the following preparation raw materials in parts by mass:

100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 parts of leveling agent, 0.2-0.8 parts of defoaming agent, 0.2-1 parts of catalyst, 20-75 parts of organic solvent;

The skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor.

Preferably, the resin precursor includes one or more of polyurethane, epoxy resin, fluorosilicone resin and acrylic resin.

Preferably, the organosilicon precursor includes one or more of hydroxy silicone oil, amino silicone oil, divinyl-terminated silicone oil and polydimethylsiloxane.

Preferably, the curing agent includes a resin curing agent and a silicone curing agent.

Preferably, the resin curing agent comprises one or more of polyetheramine, polyamidoamine, hexafluorophosphate amine and isocyanate, and the mass of the resin curing agent is 5-50% of the mass of the resin precursor.

Preferably, the organosilicon curing agent includes one or more of tetraethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, ethyl titanate and polydimethylsiloxane curing agent, and the mass of the organosilicon curing agent is 5-50% of the mass of the organosilicon precursor.

Preferably, the solid lubricant includes one or more of oleamide, erucamide, stearamide, solid paraffin and octadecane.

The present invention provides a method for preparing a high-strength anti-icing coating, comprising the following steps:

The high-strength anti-icing coating described in the above technical solution is applied to the surface of a substrate, and after curing, a high-strength anti-icing coating is formed on the surface of the substrate.

The present invention provides a high-strength anti-icing coating prepared by the preparation method described in the above technical solution.

The present invention provides the application of the high-strength anti-icing coating described in the above technical solution in the surface anti-icing of wind power generation, aircraft, airplanes, high-cold railways or radars.

The present invention provides a high-strength anti-icing coating, which includes the following raw materials by mass: 100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 parts of leveling agent, 0.2-0.8 parts of defoaming agent, 0.2-1 parts of catalyst, and 20-75 parts of organic solvent; the skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor. The present invention forms a coating having an interpenetrating polymer network (including a resin skeleton with hard properties and high bonding properties and an organosilicon skeleton with soft elastic properties) by using raw materials such as resin precursors and organosilicon precursors compounded with curing agents. The coating has high strength and extremely strong adhesion on the substrate surface, low interfacial ice adhesion, and can maintain the anti-icing performance of the interface for a long time, which can effectively solve the problems of wind power blades and wings anti-icing, and is suitable for various equipment surfaces with anti-icing requirements, and meets the strength requirements of the coating on the surface of devices such as aircraft.

Furthermore, by introducing solid lubricants, the coating's ability to retain liquid lubricants is improved, which helps to further improve the coating's strength and maintain extremely low ice adhesion performance in severe wear environments.

At the same time, the method provided by the present invention has simple raw materials, is easy to operate, can prepare coatings on a large area, has low production costs, and is suitable for large-scale production.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic diagram of a method for preparing a high-strength anti-icing coating according to the present invention;

FIG2 is a schematic diagram of the structure of a high-strength anti-icing coating according to the present invention;

FIG3 is a reaction flow chart of forming an organosilicon skeleton during the curing process of the present invention;

FIG4 is a reaction flow chart of forming a resin skeleton during the curing process of the present invention;

FIG5 is an optical photograph of a high-strength anti-icing coating of the present invention;

FIG6 is a graph showing the contact angle test results of the high-strength anti-icing coatings prepared in Examples 1 to 9;

FIG7 is a graph showing the test results of the slip angles of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6;

FIG8 is a graph showing the ice adhesion test results of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6;

FIG9 is a graph showing the test results of substrate adhesion of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6;

FIG10 is a schematic diagram of a wear resistance test of a medium- and high-strength anti-icing coating of the present invention;

FIG11 is a comparison chart of the thickness reduction of the high-strength anti-icing coatings prepared in Examples 4 to 9 after 200 wear cycles;

FIG12 is a graph showing the change in ice adhesion strength of the high-strength anti-icing coatings prepared in Examples 4 to 9 after 200 wear cycles;

13 is a graph showing the change in ice adhesion strength of the anti-icing coatings prepared in Example 6, Example 9, Comparative Example 3 and Comparative Example 6 after 200 wear cycles.

DETAILED DESCRIPTION

The present invention provides a high-strength anti-icing coating, which comprises the following preparation raw materials in parts by mass:

100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 parts of leveling agent, 0.2-0.8 parts of defoaming agent, 0.2-1 parts of catalyst, 20-75 parts of organic solvent;

The skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor.

In the present invention, unless otherwise specified, the raw materials used are commercially available products well known to those skilled in the art.

In terms of mass fractions, the raw materials for preparing the high-strength anti-icing coating described in the present invention include 100 parts of skeleton materials. In the present invention, the skeleton materials are coating precursors and curing agents, and the coating precursors include resin precursors and organosilicon precursors. When the coating precursors are resin precursors and organosilicon precursors, the resin precursors and organosilicon precursors can be in any ratio. Specifically, the mass ratio of the resin precursor and the organosilicon precursor is preferably (1 to 3): (1 to 3), and more preferably 1:3, 1:1 or 3:1. In the present invention, the resin precursor preferably includes one or more of polyurethane, epoxy resin, fluorosilicone resin and acrylic resin, and the epoxy resin is preferably E51 type epoxy resin; the organosilicon precursor preferably includes one or more of hydroxy silicone oil, amino silicone oil, divinyl-terminated silicone oil and polydimethylsiloxane. The present invention adopts a resin precursor and an organosilicon precursor as coating precursors, which can make the coating have higher strength and better adhesion as well as better ice-repellent performance.

In the present invention, the curing agent preferably includes a resin curing agent and an organosilicon curing agent. Specifically, the resin curing agent is compounded with the resin precursor, and the organosilicon curing agent is compounded with the organosilicon precursor. In the present invention, the resin curing agent preferably includes one or more of polyetheramine, polyamideamine, hexafluorophosphate amine and isocyanate, and the mass of the resin curing agent is preferably 5-50% of the mass of the resin precursor, and more preferably 33.3%. In the present invention, the organosilicon curing agent includes one or more of tetraethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, ethyl titanate and polydimethylsiloxane curing agent, and the polydimethylsiloxane curing agent is preferably 9400B polydimethylsiloxane curing agent; the mass of the organosilicon curing agent is preferably 5-50% of the mass of the organosilicon precursor, more preferably 6-30%, further preferably 8-20%, and further preferably 10-15%.

Based on the mass fraction of the skeleton material, the raw materials for preparing the high-strength anti-icing coating in the present invention include 0 to 40 parts of solid lubricants, preferably 5 to 30 parts, and more preferably 10 to 20 parts. In the present invention, the solid lubricant preferably includes one or more of oleamide, erucamide, stearic acid amide, solid paraffin and octadecane. In the present invention, the solid lubricant can enhance the hydrophobicity and lubricity of the coating surface, which is beneficial to enhance the wear resistance and ice-repellent properties of the surface.

Based on the mass fraction of the skeleton material, the raw materials for preparing the high-strength anti-icing coating in the present invention include 0.2 to 0.8 parts of leveling agent, preferably 0.2 to 0.5 parts. In the present invention, the leveling agent preferably includes one or more of silicone oil, terminal modified silicone, polydimethylsiloxane, polyether polyester modified silicone, alkyl modified silicone, acrylic leveling agent and fluorine leveling agent; in the embodiment of the present invention, BYK300 leveling agent is specifically used.

Based on the mass fraction of the skeleton material, the raw materials for preparing the high-strength anti-icing coating in the present invention include 0.2 to 0.8 parts of defoaming agent, preferably 0.2 to 0.5 parts. In the present invention, the defoaming agent preferably includes tributyl phosphate and/or trioctyl phosphate.

Based on the mass fraction of the skeleton material, the raw materials for preparing the high-strength anti-icing coating in the present invention include 0.2 to 1 parts of catalyst, preferably 0.3 to 0.5 parts. In the present invention, the catalyst preferably includes an organic tin catalyst, and the organic tin catalyst preferably includes one or more of dibutyltin dilaurate, stannous octoate and dibutyltin diacetate.

Based on the mass fraction of the skeleton material, the raw materials for preparing the high-strength anti-icing coating in the present invention include 100 to 10,000 parts of an organic solvent, preferably 800 to 1,000 parts. In the present invention, the organic solvent preferably includes one or more of xylene, toluene, butyl acetate, ethyl acetate, acetone and ethanol.

In the present invention, the method for preparing the high-strength anti-icing coating preferably comprises the following steps:

The coating precursor, the solid lubricant and the organic solvent are first mixed to obtain a first dispersion;

The first dispersion, curing agent, leveling agent and defoaming agent are mixed for a second time to obtain a second dispersion;

The second dispersion liquid is mixed with a catalyst for a third time to obtain a high-strength anti-icing coating.

In the present invention, the first mixing is preferably carried out under stirring and ultrasonic conditions in sequence; the stirring is preferably mechanical stirring; the stirring and ultrasonic conditions are based on ensuring that the various prepared raw materials are fully mixed and uniformly to obtain a clarified first dispersion. In the present invention, the second mixing and the third mixing are preferably carried out under stirring conditions to ensure that the various prepared raw materials are fully mixed and uniformly.

The present invention provides a method for preparing a high-strength anti-icing coating, comprising the following steps:

The high-strength anti-icing coating described in the above technical solution is applied to the surface of a substrate, and after curing, a high-strength anti-icing coating is formed on the surface of the substrate.

In the present invention, the material of the substrate preferably includes metal, glass, fabric, paper, wood, cement or carbon fiber material; the substrate can be specifically a plate. In the present invention, the substrate is preferably pretreated before use, and the pretreatment preferably includes washing and drying in sequence; the cleaning agent used for washing preferably includes ethanol, acetone or xylene; the present invention has no special restrictions on the drying conditions, as long as sufficient drying can be achieved. In the present invention, the coating method preferably includes spraying, spin coating, drip coating, dip coating or scraping; the present invention has no special restrictions on the specific coating conditions and the coating amount of the base coating, and a skeleton base layer that meets the thickness requirements can be obtained after curing. In the present invention, the curing temperature is preferably 20 to 85°C, more preferably 80 to 85°C; the time is preferably 2 to 24h, based on ensuring sufficient curing; the curing is preferably carried out under static conditions. In the present invention, the organic solvent is fully volatilized and removed during the curing process, and the coating precursor is fully cross-linked and cured under the action of the curing agent.

The present invention provides a high-strength anti-icing coating prepared by the preparation method described in the above technical solution.

The present invention forms an interpenetrating polymer network by using resin precursor and organic silicon precursor compound curing agent and other raw materials, wherein the solid lubricant is dispersed in the interpenetrating polymer network in solid form. The present invention has no special limitation on the thickness of the high-strength anti-icing coating, which can be selected according to actual needs. Specifically, the thickness of the high-strength anti-icing coating is preferably 10 to 500 μm.

The present invention provides the application of the high-strength anti-icing coating described in the above technical solution in the surface anti-icing of wind power generation, aircraft, high-cold railway or radar.

The technical solutions in the present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

Examples 1 to 9

A high-strength anti-icing coating was prepared according to the formula in Table 1, as follows:

Mixing a resin precursor (specifically E51 epoxy resin), an organosilicon precursor (specifically hydroxy silicone oil), a solid lubricant (specifically erucic acid amide) and xylene, and sequentially performing mechanical stirring and ultrasonication to uniformly mix the components to obtain a clear first dispersion;

Adding a resin curing agent (specifically polyetheramine), an organosilicon curing agent (specifically tetraethyl orthosilicate), a leveling agent (specifically BYK300 leveling agent) and a defoaming agent (specifically tributyl phosphate) to the first dispersion, stirring and mixing the mixture to obtain a second dispersion;

Adding a catalyst (specifically dibutyltin dilaurate) to the second dispersion, stirring and mixing evenly to obtain a high-strength anti-icing coating;

The substrate (specifically a glass sheet) is cleaned with a cleaning agent (specifically acetone) and then dried, and the high-strength anti-icing coating is sprayed onto the dry substrate surface using a compressed air-driven spray gun, and then cured at 80°C for 2 hours to form a high-strength anti-icing coating on the substrate surface.

Table 1 Amount of each raw material used in the high-strength anti-icing coating of Examples 1 to 9

Comparative Examples 1 to 6

The anti-icing coating was prepared according to the method of Example 1, except that the amounts of the raw materials used in preparing the anti-icing coatings in Comparative Examples 1 to 6 were as shown in Table 2.

Table 2 Amount of each raw material used in the anti-icing coating of Comparative Examples 1 to 6

FIG1 is a schematic diagram of the method for preparing a high-strength anti-icing coating according to the present invention, wherein the raw materials for preparing the high-strength anti-icing coating are mixed and then sprayed onto the surface of a substrate to form a high-strength anti-icing coating.

Figure 2 is a schematic diagram of the structure of the high-strength anti-icing coating of the present invention. The present invention forms an interpenetrating polymer network (including a resin skeleton with hard properties and high adhesion properties and a silicone skeleton with soft elastic properties) by using resin precursors and silicone precursors compounded with curing agents and other raw materials. At the same time, by introducing solid lubricants, the wear resistance of the coating is improved, the ice adhesion strength between ice and the coating surface is reduced, and it is ensured that the coating can still maintain a low ice adhesion strength after wear.

FIG3 is a reaction flow chart of forming an organosilicon skeleton during the curing process of the present invention, taking the organosilicon precursor as hydroxy silicone oil, the organosilicon curing agent as tetraethyl orthosilicate (TEOS), and the catalyst as dibutyltin dilaurate as an example, under the catalysis of dibutyltin dilaurate, a condensation reaction occurs between the hydrolysis product of TEOS and the terminal hydroxyl groups of the hydroxy silicone oil, thereby obtaining a high-strength anti-icing coating.

FIG4 is a reaction flow chart of forming a resin skeleton during the curing process of the present invention. Taking E51 epoxy resin as a resin precursor and polyetheramine as a resin curing agent as an example, the primary amine group of the polyetheramine can undergo a ring-opening reaction with the E51 epoxy resin to form a cross-linked high-strength anti-icing coating.

FIG5 is an optical photograph of the high-strength anti-icing coating of the present invention, and the result shows that the surface of the high-strength anti-icing coating is white.

Performance Testing

Figure 6 is a contact angle test result diagram of the high-strength anti-icing coating prepared in Examples 1 to 9, in which the organosilicon skeleton content is the percentage of the total mass of the organosilicon precursor and the organosilicon curing agent to the total mass of the organosilicon precursor, the organosilicon curing agent, the resin precursor and the resin curing agent. The results show that the high-strength anti-icing coating prepared in Examples 1 to 9 exhibits good hydrophobic properties, with a contact angle of 90.3° to 105°, depending on the content of the organosilicon skeleton and the content of the solid lubricant.

Figure 7 is a graph showing the slip angle test results of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6. The results show that, depending on the content of the silicone skeleton and the content of the solid lubricant, the high-strength anti-icing coatings prepared in Examples 1 to 9 exhibit excellent droplet slip characteristics, with a specific slip angle of 10° to 35°.

FIG8 is a graph showing the ice adhesion test results of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6. The results show that the high-strength anti-icing coatings prepared in Examples 1 to 9 exhibit lower ice adhesion strength (≤60 kPa).

9 is a graph showing the substrate adhesion test results of the anti-icing coatings prepared in Examples 1 to 9 and Comparative Examples 1 to 6. The results show that the high-strength anti-icing coatings prepared in Examples 1 to 9 exhibit good adhesion strength on the glass surface, specifically 3.4 to 6 MPa.

Figure 10 is a schematic diagram of the wear resistance test of the medium and high strength anti-icing coating of the present invention. Specifically, the sample is placed on a Taber wear tester, two grinding wheels are placed on the surface of the sample, and the sample is rotated at a speed of 99 rpm under a load of 250g. The grinding wheel will roll with the rotation of the sample to grind the surface, wherein one rotation of the sample is considered a wear cycle.

Figure 11 is a comparison chart of the thickness reduction of the high-strength anti-icing coatings prepared in Examples 4 to 9 after 200 wear cycles. The results show that the thickness loss range of the coating is 40 to 120 μm, and with the increase in the content of solid lubricant and resin skeleton, the coating prepared in Example 6 exhibits stronger wear resistance. After 200 wear cycles, only about 50 μm of thickness wear is produced.

Figure 12 is a graph showing the change in ice adhesion strength of the high-strength anti-icing coatings prepared in Examples 4 to 9 after 200 wear cycles. The results show that the ice adhesion of the coating is always less than 120 kPa, and with the introduction of solid lubricants, the high-strength anti-icing coatings prepared in Examples 6 and 9 always maintain a low ice adhesion of less than 60 kPa during the wear process.

Figure 13 is a graph showing the change in ice adhesion strength of the anti-icing coatings prepared in Example 6, Example 9, Comparative Example 3 and Comparative Example 6 after 200 wear cycles. The results show that the high-strength anti-icing coatings prepared in Example 6 and Example 9 exhibit stronger wear resistance and always maintain a low ice adhesion of less than 60 kPa during the wear process.

The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims (10)

1. A high-strength anti-icing coating, comprising the following raw materials by weight: 100 parts of skeleton material, 0-40 parts of solid lubricant, 0.2-0.8 parts of leveling agent, 0.2-0.8 parts of defoaming agent, 0.2-1 parts of catalyst, 100-10000 parts of organic solvent; The skeleton material is a coating precursor and a curing agent; the coating precursor includes a resin precursor and an organosilicon precursor. 2. The high-strength anti-icing coating according to claim 1 is characterized in that the resin precursor includes one or more of polyurethane, epoxy resin, fluorosilicone resin and acrylic resin. 3. The high-strength anti-icing coating according to claim 1 is characterized in that the organic silicon precursor comprises one or more of hydroxy silicone oil, amino silicone oil, divinyl-terminated silicone oil and polydimethylsiloxane. 4 . The high-strength anti-icing coating according to claim 1 , wherein the curing agent comprises a resin curing agent and a silicone curing agent. 5. The high-strength anti-icing coating according to claim 4 is characterized in that the resin curing agent includes one or more of polyetheramine, polyamideamine, hexafluorophosphate amine and isocyanate, and the mass of the resin curing agent is 5 to 50% of the mass of the resin precursor. 6. The high-strength anti-icing coating according to claim 4 is characterized in that the organosilicon curing agent includes one or more of tetraethyl orthosilicate, tetrabutyl silicate, tetrabutyl titanate, ethyl titanate and polydimethylsiloxane curing agent, and the mass of the organosilicon curing agent is 5 to 50% of the mass of the organosilicon precursor. 7. The high-strength anti-icing coating according to claim 1 is characterized in that the solid lubricant comprises one or more of oleamide, erucamide, stearamide, solid paraffin and octadecane. 8. A method for preparing a high-strength anti-icing coating, comprising the following steps: The high-strength anti-icing coating according to any one of claims 1 to 7 is applied to the surface of a substrate, and after curing, a high-strength anti-icing coating is formed on the surface of the substrate. 9. The high-strength anti-icing coating prepared by the preparation method according to claim 8. 10. Use of the high-strength anti-icing coating according to claim 9 in anti-icing of the surface of wind power generation, aircraft, airplanes, high-cold railways or radars.

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