CN115627086A - A high-temperature-resistant broad-spectrum super-lyophobic coating and preparation method thereof - Google Patents

Abstract

A high-temperature-resistant broad-spectrum super-lyophobic coating and a preparation method thereof, the raw materials include prepared low surface energy inorganic particles and inorganic silicone resin; the raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post- Skeleton precursor, inorganic submicron particles/inorganic nanoparticles, first solvent and second solvent; the polar group fluoropolymer is 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, etc.; The preparation method is: (1) mixing and stirring the inorganic particles with the first solvent and the second solvent evenly to obtain the inorganic particle mixture; (2) adding the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture , stirring, washing, and drying to obtain low surface energy inorganic particles; (3) adding to inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry; (4) uniformly coating on a glass sheet, and standing at room temperature. The high-temperature-resistant broad-spectrum super-lyophobic coating of the present invention can be used for a long time at a high temperature of 800°C from the perspective of engineering application.

Description

A high-temperature-resistant broad-spectrum super-lyophobic coating and preparation method thereof

technical field

The invention particularly relates to a high-temperature-resistant broad-spectrum super-repellent coating and a preparation method thereof.

Background technique

Super-lyophobic coating materials, as a special new material, have gained more and more attention because of their special properties such as self-cleaning, anti-fogging, anti-icing, anti-corrosion, anti-fouling, anti-fouling, and fluid drag reduction. Superlyophobic coatings have a wide range of application scenarios, such as electronic equipment, automotive glass, marine ships, medical devices, etc. However, in engineering applications, it is difficult for super-lyophobic coatings to pass the test of high-temperature environments and low surface tension liquids, which greatly shortens the service life of super-lyophobic coatings. The main reason why the super-lyophobic coating cannot withstand high-temperature baking is that the structure of the organic polymer resin used in the super-lyophobic coating is easy to "collapse" at high temperature, that is, it is not resistant to high temperature, and the narrow-spectrum lyophobic property This is mainly due to the fact that the substances that build the surface roughness do not have low surface energy and thus cannot repel the adhesion of low surface tension liquids. Therefore, it is of great significance to develop superlyophobic coatings with high temperature resistance and broad-spectrum lyophobicity from the perspective of engineering applications.

In recent years, researchers at home and abroad have mainly improved the high temperature resistance of superlyophobic coatings or broadened the lyophobic spectrum through inorganic nanoparticles-organic polymer hybridization and multilayer assembly. The Chinese invention patent with application number 201310331586.5 discloses an in-situ preparation method for a high-temperature-resistant superhydrophobic coating. First, an organic-inorganic hybrid system is prepared by in-situ copolymerization of organosilicon monomers and nano-silica nanoparticles, and then prepared The sol nanoparticles are added to the organic-inorganic hybrid system to obtain a coating solution. Finally, the coating solution is sprayed on the surface of the substrate and baked at 140°C to 160°C to obtain a high-temperature-resistant super-hydrophobic coating. The coating is passed through 450°C It is also superhydrophobic after grilling. The Chinese invention patent with the patent number 201880081308.X discloses an object with a high-temperature-resistant super-lyophobic non-stick coating and a method of manufacturing the object. First, an adhesion promoter layer containing amorphous silica is prepared, and then the CVD plasma is used to Apply it to the inorganic substrate by body method or flame treatment method, and finally prepare a super-lyophobic and non-stick layer by means of sol-gel deposition and apply it on the tackifier layer to prepare a high-temperature-resistant super-lyophobic and non-stick coating. The coating is oleophobic, and the maximum heat-resistant temperature reaches 400°C.

In practical applications, super-lyophobic coatings are faced with the baking of higher temperature environments and the impact of complex low-surface tension liquids. Inorganic nanoparticles-organic polymer hybridization and multi-layer assembly, although effective The super-lyophobic surface can improve the ability to resist baking in high-temperature environment to a certain extent. However, these two technologies have many shortcomings, such as the super-lyophobic coating prepared by using the inorganic nanoparticle-organic polymer hybrid technology. , the surface of the rough structure constructed by the use of silicone monomer hybrid silica nanoparticles does not have low surface energy, so it cannot resist the adhesion of low surface tension liquids, and the coating uses organic polymers as the main network structure , and its high temperature resistance is relatively limited. However, the multi-layer assembly method needs to use expensive and slow special equipment in the implementation process, and has special requirements for the selection of substrates. application.

Contents of the invention

From the perspective of engineering application (environmental protection, cost, construction), the purpose of the present invention is to propose a high-temperature-resistant broad-spectrum super-lyophobic coating and a preparation method thereof, in which modified inorganic particles are incorporated into high-temperature-resistant inorganic silicon Among the resins, the prepared high-temperature-resistant broad-spectrum super-lyophobic coating not only has higher heat resistance, the heat-resistant temperature is higher than 800°C, and has a wider-spectrum lyophobic property, which has a strong rejection of oil effect, and the super-lyophobic coating uses environmentally friendly, low-toxicity solvents in the preparation process, the equipment involved is simple and easy to operate, and can be achieved by simple construction such as spraying, brushing, roller coating, etc., and the coating preparation cost Low, high construction efficiency, is expected to achieve engineering applications.

A high-temperature-resistant broad-spectrum super-lyophobic coating of the present invention, the raw materials include prepared low surface energy inorganic particles and inorganic silicone resin; the raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton Precursor, inorganic submicron particles/inorganic nanoparticles, first solvent and second solvent; the polar group fluoropolymer is 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorohexyltriethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 1H ,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluorohexyltrimethoxysilane, 3 ,3,3-Trifluoropropyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, 1H,1H,2H,2H-perfluorooctyltrichlorosilane, 1H,1H, One of 2H,2H-perfluorohexyltrichlorosilane and 3,3,3-trifluoropropyltrichlorosilane.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the post-skeleton precursor is one of tetraethyl orthosilicate, tetraethyl titanate, triethyl aluminate and tetrabutyl zirconate .

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the inorganic submicron particles are among the submicron particles of silicon dioxide, submicron particles of titanium dioxide, submicron particles of aluminum oxide and submicron particles of zirconium dioxide. The inorganic nanoparticle is one of silica nanoparticle, titanium dioxide nanoparticle, aluminum oxide nanoparticle and zirconium dioxide nanoparticle.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the size of the inorganic submicron particles is 0.1-0.8 μm.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the size of the inorganic nanoparticles is 5-90 nm.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the first solvent is one of ethanol, dimethyl carbonate, propylene glycol methyl ether and isopropanol.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the second solvent is one of ammonia water, triethylamine, formamide and pyridine.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the volume ratio of the first solvent and the second solvent in the low-surface-energy inorganic particles is 10:(1.5-10).

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the inorganic silicon resin is inorganic nano-ceramic resin SJ-1016, inorganic silicon resin SJ-482, inorganic silicon resin SJ-140M and inorganic nano-ceramic resin CeRam HD One of a kind in 1001A.

In the above-mentioned high-temperature-resistant broad-spectrum super-lyophobic coating, the mass content of the inorganic silicone resin is 5% to 20%.

A preparation method of a high-temperature-resistant broad-spectrum super-lyophobic coating, comprising the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles or inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Coat the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally.

In the above method, the mass content of the polar group fluoropolymer in the low surface energy inorganic particle precursor solution is 1-10%.

In the above method, the mass content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.1-1%.

In the above method, the mass content of the inorganic particles in the inorganic particle mixed liquid is 1-12%.

In the above method, the ultrasonic frequency of the inorganic particle mixture is 20-60 kHz.

In the above method, the mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:(4-20).

In the above method, the time for vacuuming after the low surface energy inorganic particles are mixed with the inorganic silicone resin is 1-10 minutes.

In the above method, the degree of vacuum after the low surface energy inorganic particles are mixed with the inorganic silicone resin is -0.4-0.8kPa.

In the above method, the room temperature storage time for the slurry to be uniformly coated on the glass sheet is 12-48 hours.

In the above method, the coating method is one of spray coating, spin coating, brush coating and roller coating.

Compared with the prior art, the present invention has the advantages of:

(1) The high-temperature-resistant broad-spectrum super-lyophobic coating is based on the engineering application point of view, and the low-surface-energy inorganic particles are mixed into the inorganic silicone resin, and the prepared coating has a wider-spectrum lyophobic property. It has a strong repelling effect on non-polar and low surface tension liquids; in addition, the coating has higher heat resistance and can be used at a high temperature of 800°C for a long time, and the coating still maintains a good super-lyophobic effect;

(2) In the preparation process of the high-temperature-resistant broad-spectrum super-lyophobic coating, an environmentally friendly and low-toxicity solvent is used to prepare low-surface-energy inorganic particles. Such as spraying, brushing, roller coating, etc., the coating preparation cost is low, the construction efficiency is high, and engineering application can be realized.

Description of drawings

Fig. 1 is the slurry appearance photo figure of the broad-spectrum super-lyophobic coating of high temperature resistance in the embodiment of the present invention 1;

Fig. 2 is a photo of the high temperature resistant broad-spectrum super-lyophobic coating in Example 1 of the present invention with 20 μL of water droplets (left) and 20 μL of n-hexadecane droplets (right) on the surface.

Detailed ways

In the implementation of the present invention, the polar group fluoropolymer, the post-skeleton precursor, the inorganic submicron particles/inorganic nanoparticles, the first solvent and the second solvent are commercially available analytical reagents.

In the embodiment of the present invention, the size of the inorganic submicron particles is 0.1-0.8 μm; the size of the inorganic nanoparticles is 5-90 nm.

In the embodiment of the present invention, the frequency of the ultrasound is 20-60 kHz.

In the embodiment of the present invention, the degree of vacuum during vacuuming is -0.4˜-0.8 kPa.

In the embodiment of the present invention, washing refers to immersing and dispersing the white precipitate with absolute ethanol, and then removing the absolute ethanol by suction filtration.

In the embodiment of the present invention, drying refers to placing the washed white precipitate at 100±5° C. for more than 12 hours.

In the embodiment of the present invention, the content of the inorganic silicone resin in the high-temperature-resistant broad-spectrum super-lyophobic coating is 5% to 20%.

Example 1

High-temperature-resistant broad-spectrum super-lyophobic coating, the raw materials include prepared low surface energy inorganic particles and inorganic silicone resin; the raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic nano Particles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane;

The precursor of the post-skeleton is tetraethyl orthosilicate;

The inorganic nanoparticles are silica nanoparticles;

The size of the inorganic nanoparticles is 5-90nm;

The first solvent is ethanol;

The second solvent is ammonia;

The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:1.5;

The inorganic silicon resin is inorganic nano-ceramic resin SJ-1016;

In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 5%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) Add low-surface-energy inorganic particles into the inorganic silicone resin, stir evenly, and then vacuumize and defoam to form a slurry; the appearance is shown in Figure 1;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, and let it dry and solidify naturally; the appearance is as shown in Figure 2;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 5.4%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.32%;

The content of inorganic particles in the inorganic particle mixture is 2.7%;

The ultrasonic frequency of the inorganic particle mixture is 20kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:10;

The vacuuming time after mixing low surface energy inorganic particles and inorganic silicone resin is 5 minutes; the vacuum degree of vacuuming after mixing low surface energy inorganic particles and inorganic silicone resin is -0.4kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 24 hours;

The way of coating is spraying.

Example 2

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 1H ,1H,2H,2H-perfluorooctyltriethoxysilane;

(2) The post-skeleton precursor is tetraethyl titanate; the size of the inorganic submicron particles is 0.1-0.8 μm;

(3) The inorganic submicron particles are silica submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is dimethyl carbonate;

(5) the second solvent is triethylamine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:2.5;

(7) The inorganic silicone resin is inorganic silicone resin SJ-482;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 6%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Coat the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally.

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution was 2.6%.

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.1%.

The content of the inorganic particles in the inorganic particle mixed liquid is 1.2%.

The ultrasonic frequency of the inorganic particle mixture is 30kHz.

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:4.

The vacuuming time after the low surface energy inorganic particles are mixed with the inorganic silicone resin is 3 minutes.

The degree of vacuum after the low surface energy inorganic particles are mixed with the inorganic silicone resin is -0.5kPa.

The time for the slurry to be uniformly coated on the glass sheet at room temperature is 12 hours.

The coating method is spin coating.

Example 3

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include a polar group fluoropolymer, a post-skeleton precursor, inorganic nanoparticles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H,2H,2H-perfluorohexyltriethoxysilane;

(2) The back skeleton precursor is triethyl aluminate;

(3) The inorganic nanoparticles are titanium dioxide nanoparticles; the size of the inorganic nanoparticles is 5-90nm;

(4) the first solvent is propylene glycol methyl ether;

(5) the second solvent is formamide;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:3.5;

(7) The inorganic silicone resin is inorganic silicone resin SJ-140M;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 7%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 6.7%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.56%;

The content of inorganic particles in the mixture of organic particles is 5.1%;

The ultrasonic frequency of the inorganic particle mixture is 40kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:14;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 8 minutes;

The vacuum degree of vacuuming after mixing low surface energy inorganic particles and inorganic silicone resin is -0.6kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 36 hours;

The method of application is brush application.

Example 4

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 3 ,3,3-Trifluoropropyltriethoxysilane;

(2) the back skeleton precursor is tetrabutyl zirconate;

(3) The inorganic submicron particles are titanium dioxide submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is Virahol;

(5) the second solvent is pyridine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:4.5;

(7) The inorganic silicon resin is an inorganic nano-ceramic resin CeRam HD 1001A;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 8%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 3.7%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.28%;

The content of inorganic particles in the inorganic particle mixture is 4.2%;

The ultrasonic frequency of the inorganic particle mixture is 50kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:7;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 9 minutes;

The vacuum degree of the vacuum after the mixing of low surface energy inorganic particles and inorganic silicone resin is -0.7kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 48 hours;

The way of coating is roller coating.

Example 5

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include a polar group fluoropolymer, a post-skeleton precursor, inorganic nanoparticles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H,2H,2H-perfluorodecyltrimethoxysilane;

(2) the back skeleton precursor is ethyl orthosilicate;

(3) The inorganic nanoparticles are aluminum oxide nanoparticles; the size of the inorganic nanoparticles is 5-90nm;

(4) the first solvent is ethanol;

(5) the second solvent is triethylamine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:5.5;

(7) The inorganic silicon resin is inorganic nano-ceramic resin SJ-1016;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 9%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 7.6%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.73%;

The content of inorganic particles in the inorganic particle mixture is 8.5%;

The ultrasonic frequency of the inorganic particle mixture is 60kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:18;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 6 minutes;

The vacuum degree of vacuum pumping after mixing low surface energy inorganic particles and inorganic silicone resin is -0.8kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 12 hours;

The way of coating is spraying.

Example 6

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 1H ,1H,2H,2H-perfluorooctyltrimethoxysilane;

(2) The back skeleton precursor is tetraethyl titanate;

(3) The inorganic submicron particles are aluminum oxide submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is dimethyl carbonate;

(5) the second solvent is formamide;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:6.5;

(7) The inorganic silicone resin is inorganic silicone resin SJ-482;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 10%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 8.8%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.92%;

The content of inorganic particles in the inorganic particle mixture is 10.6%;

The ultrasonic frequency of the inorganic particle mixture is 20kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:20;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 10 minutes;

The vacuum degree of vacuum pumping after mixing low surface energy inorganic particles and inorganic silicone resin is -0.5kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 30 h.

The coating method is spin coating.

Example 7

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include a polar group fluoropolymer, a post-skeleton precursor, inorganic nanoparticles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H,2H,2H-perfluorohexyltrimethoxysilane;

(2) The back skeleton precursor is triethyl aluminate;

(3) The inorganic nanoparticles are zirconia nanoparticles; the size of the inorganic nanoparticles is 5-90nm;

(4) the first solvent is propylene glycol methyl ether;

(5) the second solvent is pyridine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:7.5;

(7) The inorganic silicone resin is inorganic silicone resin SJ-140M;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 11%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 1.9%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.54%;

The content of inorganic particles in the inorganic particle mixture is 8.2%;

The ultrasonic frequency of the inorganic particle mixture is 30kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:11;

The vacuuming time after the surface energy inorganic particles are mixed with the inorganic silicone resin is 7 minutes;

The vacuum degree of vacuuming after mixing low surface energy inorganic particles and inorganic silicone resin is -0.6kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 15 hours;

The method of application is brush application.

Example 8

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 3 ,3,3-Trifluoropropyltrimethoxysilane;

(2) the back skeleton precursor is tetrabutyl zirconate;

(3) The inorganic submicron particles are zirconium dioxide submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is Virahol;

(5) the second solvent is ammoniacal liquor;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:8.5;

(7) The inorganic silicon resin is an inorganic nano-ceramic resin CeRam HD 1001A;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 13%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 5.9%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.32%;

The content of inorganic particles in the inorganic particle mixture is 7.5%;

The ultrasonic frequency of the inorganic particle mixture is 40kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:6;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 5 minutes;

The vacuum degree of the vacuum after the mixing of low surface energy inorganic particles and inorganic silicone resin is -0.7kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 40 hours;

The way of coating is roller coating.

Example 9

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include a polar group fluoropolymer, a post-skeleton precursor, inorganic nanoparticles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H,2H,2H-perfluorodecyltrichlorosilane;

(2) the back skeleton precursor is ethyl orthosilicate;

(3) The inorganic nanoparticles are silica nanoparticles; the size of the inorganic nanoparticles is 5-90nm;

(4) the first solvent is ethanol;

(5) the second solvent is formamide;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:9.5;

(7) The inorganic silicon resin is inorganic nano-ceramic resin SJ-1016;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 15%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 6.3%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.82%;

The content of inorganic particles in the inorganic particle mixture is 9%;

The ultrasonic frequency of the inorganic particle mixture is 50kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:10;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 8 minutes;

The vacuum degree of vacuum pumping after mixing low surface energy inorganic particles and inorganic silicone resin is -0.8kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 16 hours;

The way of coating is spraying.

Example 10

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 1H ,1H,2H,2H-Perfluorooctyltrichlorosilane;

(2) The back skeleton precursor is tetraethyl titanate;

(3) The inorganic submicron particles are silica submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is dimethyl carbonate;

(5) the second solvent pyridine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:10;

(7) The inorganic silicone resin is inorganic silicone resin SJ-482;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 17%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 6.4%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.49%;

The content of inorganic particles in the inorganic particle mixture is 10.5%;

The ultrasonic frequency of the inorganic particle mixture is 60kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:13;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 5 minutes;

The vacuum degree of vacuum pumping after mixing low surface energy inorganic particles and inorganic silicone resin is -0.4kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 30 hours;

The coating method is spin coating.

Example 11

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include a polar group fluoropolymer, a post-skeleton precursor, inorganic nanoparticles, a first solvent and a second solvent; the polar group fluoropolymer is 1H, 1H,2H,2H-Perfluorohexyltrichlorosilane;

(2) The back skeleton precursor is triethyl aluminate;

(3) The inorganic nanoparticles are titanium dioxide nanoparticles; the size of the inorganic nanoparticles is 5-90nm;

(4) the first solvent is propylene glycol methyl ether;

(5) the second solvent is ammoniacal liquor;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:9;

(7) The inorganic silicone resin is inorganic silicone resin SJ-140M;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 19%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic nanoparticles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 1.6%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.7%;

The content of inorganic particles in the inorganic particle mixture is 4%;

The ultrasonic frequency of the inorganic particle mixture is 20kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:8;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 6 minutes;

The vacuum degree of vacuuming after mixing low surface energy inorganic particles and inorganic silicone resin is -0.6kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 48 hours;

The method of application is brush application.

Example 12

Raw material composition is with embodiment 1, and difference is:

(1) The raw materials of the low surface energy inorganic particles include polar group fluoropolymers, post-skeleton precursors, inorganic submicron particles, the first solvent and the second solvent; the polar group fluoropolymers are 3 ,3,3-trifluoropropyltrichlorosilane;

(2) the back skeleton precursor is tetrabutyl zirconate;

(3) The inorganic submicron particles are titanium dioxide submicron particles; the size of the inorganic submicron particles is 0.1-0.8 μm;

(4) the first solvent is Virahol;

(5) the second solvent is triethylamine;

(6) The volume ratio of the first solvent and the second solvent in the low surface energy inorganic particles is 10:7;

(7) The inorganic silicon resin is an inorganic nano-ceramic resin CeRam HD 1001A;

(8) In the high-temperature-resistant broad-spectrum super-lyophobic coating, the content of inorganic silicone resin is 20%;

The preparation method comprises the following steps:

(1) After mixing and stirring the inorganic particles evenly with the first solvent and the second solvent, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles;

(2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles;

(3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry;

(4) Apply the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally, to obtain final product;

The polar group fluoropolymer content in the low surface energy inorganic particle precursor solution is 2.9%;

The content of the post-skeleton precursor in the low surface energy inorganic particle precursor solution is 0.47%;

The content of inorganic particles in the inorganic particle mixture is 3%;

The ultrasonic frequency of the inorganic particle mixture is 30kHz;

The mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:16;

The vacuuming time after mixing low surface energy inorganic particles with inorganic silicone resin is 5 minutes;

The vacuum degree of the vacuum after the mixing of low surface energy inorganic particles and inorganic silicone resin is -0.7kPa;

The time for the slurry to be evenly coated on the glass sheet at room temperature is 22 hours;

The way of coating is roller coating.

Example 13

The coatings prepared in Examples 1-12 were placed in an environment with a temperature of 800°C for 200 hours, and after cooling down to room temperature, the contact angle between water (10 μL) and n-hexadecane (10 μL) was tested, as shown in Table 1;

Table 1 is the contact angle, rolling angle data of each embodiment

Its effect remains good after testing, which proves the technical effect of the present application.

Claims (10)

1. A high-temperature-resistant broad-spectrum super-lyophobic coating, characterized in that: raw materials include prepared low surface energy inorganic particles and inorganic silicone resin; the raw materials of described low surface energy inorganic particles include polar group fluoropolymers , post-skeleton precursor, inorganic submicron particles/inorganic nanoparticles, first solvent and second solvent; the polar group fluoropolymer is 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane , 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorohexyltriethoxysilane, 3,3,3-trifluoropropyltriethoxy Silane, 1H,1H,2H,2H-Perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-Perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-Perfluorohexyltrimethoxy Silane, 3,3,3-trifluoropropyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, 1H,1H,2H,2H-perfluorooctyltrichlorosilane, 1H , 1H, 2H, 2H-perfluorohexyltrichlorosilane and 3,3,3-trifluoropropyltrichlorosilane in one. 2. A kind of high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 1, characterized in that: said back-skeleton precursor is ethyl orthosilicate, tetraethyl titanate, triethyl aluminate and one of tetrabutyl zirconate; the inorganic submicron particles are one of silica submicron particles, titanium dioxide submicron particles, aluminum oxide submicron particles and zirconium dioxide submicron particles; the The inorganic nanoparticles are one of silica nanoparticles, titania nanoparticles, aluminum oxide nanoparticles and zirconium dioxide nanoparticles. 3. a kind of high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 1, is characterized in that: described first solvent is the one in ethanol, dimethyl carbonate, propylene glycol methyl ether and Virahol ; The second solvent is one of ammonia, triethylamine, formamide and pyridine. 4. a kind of high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 1 is characterized in that: the volume ratio of the first solvent and the second solvent in the described low surface energy inorganic particle is 10:(1.5～ 10). 5. A kind of high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 1, characterized in that: the inorganic silicon resin is inorganic nano-ceramic resin SJ-1016, inorganic silicon resin SJ-482, inorganic silicon resin One of SJ-140M and inorganic nano-ceramic resin CeRam HD 1001A. 6. a preparation method of the high-temperature-resistant broad-spectrum super-lyophobic coating claimed in claim 1, is characterized in that: comprises the following steps: (1) After mixing and stirring the inorganic particles with the first solvent and the second solvent evenly, ultrasonically prepare the inorganic particle mixture; the inorganic particles are inorganic submicron particles or inorganic nanoparticles; (2) Add the polar group fluoropolymer and the post-skeleton precursor to the inorganic particle mixture to prepare a low surface energy inorganic particle precursor solution. After stirring evenly, collect the white precipitate by centrifugation; and wash the white precipitate, and finally drying to prepare low surface energy inorganic particles; (3) adding low surface energy inorganic particles into the inorganic silicone resin, stirring evenly, vacuuming and defoaming to form a slurry; (4) Coat the slurry evenly on the glass sheet, place it at room temperature, let it dry and solidify naturally. 7. the preparation method of the broad-spectrum super-lyophobic coating of high temperature resistance according to claim 6, is characterized in that: the polar group fluoropolymer mass content in the described low surface energy inorganic particle precursor solution is 1 ~10%. 8. The preparation method of the high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 6, characterized in that: the mass content of the post-skeleton precursor in the low-surface-energy inorganic particle precursor solution is 0.1 to 1% . 9. The method for preparing a high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 6, characterized in that: the mass content of the inorganic particles in the inorganic particle mixture is 1-12%. 10. The method for preparing a high-temperature-resistant broad-spectrum super-lyophobic coating according to claim 6, characterized in that: the mass ratio of the low surface energy inorganic particles to the inorganic silicone resin is 1:(4-20).

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