CN115584189A

CN115584189A - Super-hydrophobic glass bead and preparation method thereof, and super-hydrophobic coating and preparation method thereof

Info

Publication number: CN115584189A
Application number: CN202211130260.1A
Authority: CN
Inventors: 杜庶铭; 陈寅; 张秩鸣; 王楚; 何鲲; 廖海燕; 张利平; 马俯波
Original assignee: Anhui Guodian Wanneng Wind Power Co ltd; National Energy Group New Energy Technology Research Institute Co Ltd
Current assignee: Anhui Guodian Wanneng Wind Power Co ltd; National Energy Group New Energy Technology Research Institute Co Ltd
Priority date: 2022-09-16
Filing date: 2022-09-16
Publication date: 2023-01-10

Abstract

The invention relates to the technical field of organic/inorganic composite super-hydrophobic materials, and discloses super-hydrophobic glass beads and a preparation method thereof, and a super-hydrophobic coating and a preparation method thereof. The preparation method of the super-hydrophobic glass beads comprises the following steps: dispersing glass beads in a mixed solvent, and then adding organic amine and a hydrophobic silane coupling agent for mixing and contacting; wherein the weight ratio of the glass beads to the hydrophobic silane coupling agent is 1.1-0.9; the grain diameter of the glass microballoons is 1-200 mu m. The method has simple steps, can save the cost of raw materials and can be industrially amplified, and the super-hydrophobic coating prepared by the super-hydrophobic glass beads has good hydrophobicity, wear resistance and scratch resistance.

Description

Super-hydrophobic glass bead and preparation method thereof, and super-hydrophobic coating and preparation method thereof

Technical Field

The invention relates to the technical field of organic/inorganic composite super-hydrophobic materials, in particular to super-hydrophobic glass beads and a preparation method thereof, and super-hydrophobic paint and a preparation method thereof.

Background

The super-hydrophobic material is a novel functional material, has the effects of rolling water drops and preventing water drops from being stuck on the surface of the super-hydrophobic material like a lotus leaf surface, has the remarkable excellent characteristics of hydrophobicity, easiness in cleaning, icing prevention, fog prevention and the like, can be widely applied to the fields of buildings, bridges, traffic, electrical equipment, mechanical equipment, marine pollution prevention, oil-water separation, bacteriostasis and the like, and has a good application prospect. The stable contact angle of the superhydrophobic surface and water needs to be more than 150 degrees, and generally, two conditions need to be met for preparing the superhydrophobic surface: firstly, the surface of the finished product rate is modified by low surface energy substances; the second is that the surface of the material has a micro-nano hierarchical structure. At present, the preparation of a super-hydrophobic surface is generally carried out by various technologies and methods such as a template method, a photoetching method, a plasma etching method, a layer-by-layer assembly method and the like. These methods result in high cost for preparing superhydrophobic coatings due to the high equipment requirements. Therefore, the research and development of the super-hydrophobic material with excellent performance and simple preparation process for the super-hydrophobic coating has important significance.

The raspberry-shaped particles have special properties due to the special hierarchical structure, so that the raspberry-shaped particles can be widely applied to the preparation of super-hydrophobic materials. Raspberry-like particles are particles shaped like raspberries, and are particles having a special hierarchical structure formed mainly by attaching smaller-sized particles to larger-sized particles by physical or chemical means. The raspberry-shaped particles have large specific surface area, high roughness and high light scattering property, and have very wide application prospect in the field of super-hydrophobicity.

Patent CN 107998997B discloses a preparation method of raspberry-like microspheres, which uses polymethyl methacrylate as core and silicon dioxide as shell. The raspberry-like microspheres prepared by the method have controllable sizes, and the super-hydrophobic coating obtained by utilizing the raspberry-like microspheres has good chemical stability and hydrophobicity. The surface of the silica raspberry-shaped composite particle with extremely high roughness is prepared by utilizing the covalent bond combination between amino and epoxy, and the like, and then is modified by utilizing polydimethylsiloxane, so that the finally obtained super-hydrophobic material has excellent hydrophobic property.

Although many studies show that the raspberry-shaped particles have excellent hydrophobic property, the process for preparing the big and small spheres step by step is complicated, the experiment cost is high, and the like in the process of preparing the raspberry-shaped particles.

Disclosure of Invention

The invention aims to solve the problems of high preparation cost, complicated preparation process, difficulty in industrial amplification and the like of a super-hydrophobic material in the prior art, and provides super-hydrophobic glass beads, a preparation method thereof, a super-hydrophobic coating and a preparation method thereof.

In order to achieve the above object, one aspect of the present invention provides a method for preparing superhydrophobic glass beads, the method comprising the steps of: dispersing glass beads in a mixed solvent, and then adding organic amine and a hydrophobic silane coupling agent for mixing and contacting;

wherein the weight ratio of the glass beads to the hydrophobic silane coupling agent is 1.1-0.9;

the particle size of the glass beads is 1-200 μm.

Preferably, the glass beads are solid glass beads and/or hollow glass beads.

Preferably, the hydrophobic silane coupling agent is selected from one or more of alkyl trimethoxy silane, alkyl triethoxy silane, fluorine-containing alkyl trimethoxy silane and fluorine-containing alkyl triethoxy silane; wherein the alkyl is a C1-C20 alkyl.

Preferably, the organic amine is selected from one or more of triethanolamine, tripropanolamine, and trialkylamine.

Preferably, the weight ratio of the glass beads to the organic amine is 1.

Preferably, the conditions of the mixing contact include: the temperature of mixing and contact is 30-70 ℃, and the time of mixing and contact is 1-24h.

Preferably, the mixed solvent is obtained by mixing an organic solvent and water; wherein the organic solvent is methanol and/or ethanol.

Preferably, the proportion of the organic solvent is 10-90 parts based on 100 parts of the total volume of the mixed solvent.

In a second aspect, the invention provides a super-hydrophobic glass bead obtained by the preparation method described above.

The invention provides a super-hydrophobic coating, which is prepared from raw materials containing the super-hydrophobic glass beads, epoxy resin, a curing agent and a solvent.

Preferably, the weight ratio of the super-hydrophobic glass beads, the epoxy resin and the curing agent in the raw materials is 3 (2-6) to 0.4-1.

In a fourth aspect, the present invention provides a method for preparing the superhydrophobic coating, the method comprising the steps of:

(1) Dispersing the super-hydrophobic glass beads in a solvent, and then adding epoxy resin for mixing to obtain a mixed solution;

(2) And adding a curing agent into the mixed solution, and mixing to obtain the super-hydrophobic coating.

The invention has the beneficial effects that:

1. the super-hydrophobic glass beads adopt industrialized glass beads as raw materials, so that the formula cost can be saved, the raspberry-shaped super-hydrophobic material prepared by selecting the glass beads with the particle size of 1-200 mu m can increase the lotus effect of the finally obtained raspberry-shaped super-hydrophobic material, so that the hydrophobicity of the obtained super-hydrophobic glass beads is improved, the super-hydrophobic glass beads are applied to the preparation of the super-hydrophobic coating, the finally coated super-hydrophobic coating has excellent super-hydrophobic performance, the contact angle between the surface of the super-hydrophobic coating and water is more than 150 degrees, and the super-hydrophobic coating has a good self-cleaning function;

2. the super-hydrophobic coating obtained by finally curing the super-hydrophobic coating prepared by the method disclosed by the invention has excellent wear resistance and scratch resistance besides excellent super-hydrophobic performance, the super-hydrophobic performance of the coating before and after polishing and scratching is not influenced, and the super-hydrophobic performance of the coating is very stable;

3. the preparation method is simple and easy to implement, high temperature, high pressure and multi-step reaction are not needed, the raspberry-shaped super-hydrophobic glass beads can be directly synthesized in situ in one step, the raw materials are cheap and easy to obtain, industrial amplification can be carried out, the method has great industrial prospect, the super-hydrophobic coating obtained after industrial amplification experiments still has good super-hydrophobic performance, and the defects in the prior art are successfully overcome.

Drawings

FIG. 1 is SEM images of the super-hydrophobic glass micro beads A1 and A3 prepared in example 1 and example 3;

FIG. 2 is an SEM photograph of products D1 and D2 and hollow glass microspheres prepared in comparative examples 1 to 2;

FIG. 3 is a photograph showing the measurement of contact angle of water with a coating layer obtained by spraying the coating materials obtained in examples 4 to 6 on the surface of a substrate;

FIG. 4 is a photograph showing the measurement of contact angle of water with a coating layer obtained by spraying the coating obtained in comparative examples 3 to 5 on the surface of a substrate.

Detailed Description

The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.

In this context, dn90 refers to the particle size value of 90% of the particles in the material.

Herein, the term "superhydrophobic material" refers to a material having a stable contact angle with water of greater than 150 °.

The preparation method of the super-hydrophobic glass beads comprises the following steps: dispersing glass beads in a mixed solvent, and then mixing and contacting the obtained mixture with organic amine and a hydrophobic silane coupling agent.

In the method, the glass beads with the particle size of 1-200 mu m are used as raw materials, so that the lotus effect of the surface of the obtained super-hydrophobic material can be improved, and the hydrophobic property of the super-hydrophobic material is improved.

In a preferred embodiment, the glass beads have a particle size of 1 to 200. Mu.m, preferably 5 to 120. Mu.m, and more preferably 10 to 100. Mu.m.

In the method of the present invention, the weight ratio of the glass beads to the hydrophobic silane coupling agent is 1. Specifically, the weight ratio of the glass beads to the hydrophobic silane coupling agent may be 1.

In the method, the weight ratio of the glass beads to the hydrophobic silane coupling agent needs to be strictly controlled, and when the weight ratio of the glass beads to the hydrophobic silane coupling agent is lower than 1; when the weight ratio of the glass beads to the hydrophobic silane coupling agent is higher than 1.9, raspberry-shaped particles cannot be formed on the surfaces of the glass beads, a thick hydrophobic shell can be formed on the surfaces of the glass beads, and therefore the micro-nano hierarchical structure cannot be formed on the surfaces of the glass beads, and the hydrophobic performance is weakened.

In a specific embodiment, the glass beads are solid glass beads and/or hollow glass beads.

In the method of the present invention, the hydrophobic silane coupling agent is one or more selected from the group consisting of alkyltrimethoxysilane, alkyltriethoxysilane, fluoroalkyl-trimethoxysilane, and fluoroalkyl-triethoxysilane. Wherein the alkyl is C1-C20 alkyl, preferably C4-C12 alkyl. Specifically, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, heptyl, decyl, dodecyl, ethenyl, propenyl, butenyl, or isopropyl may be mentioned.

As used herein, fluoroalkyl refers to an alkyl group containing a fluorine substituent, preferably a C1-C20 alkyl group containing a fluorine substituent.

In a preferred embodiment, the hydrophobic silane coupling agent is selected from the group consisting of fluoroalkyl trimethoxysilane and/or fluoroalkyl triethoxysilane, wherein the alkyl group is a C1-C20 alkyl group, preferably a C1-C6 alkyl group. Specifically, for example, the hydrophobic silane coupling agent containing fluoroalkyl trimethoxysilane may be perfluorohexyltrimethoxysilane or perfluorodecyltrimethoxysilane, and the fluoroalkyl triethoxysilane may be perfluorohexyltriethoxysilane or perfluorodecyltriethoxysilane.

In a specific embodiment, the organic amine is selected from one or more of triethanolamine, tripropanolamine, and trialkylamine.

In the method of the present invention, the alkyl group in the trialkylamine is a C1-C20 alkyl group, preferably a C2-C6 alkyl group, and more preferably triethylamine or tripropylamine. The weight ratio of the glass beads to the organic amine is 1.

In the method, organic amine and hydrophobic silane coupling agent are adopted to modify the surface of the glass microsphere, so that raspberry-shaped particles with more uniform coating and micro-nano hierarchical structures on the surface are obtained, unlike the conventional method of modifying the surface of the glass microsphere by adopting inorganic amine for reaction.

In a preferred embodiment, the glass beads are dispersed in the mixed solvent, and then the organic amine is added to be heated and stirred, followed by adding the hydrophobic silane coupling agent to be reacted. Specifically, the conditions for heating and stirring include: the heating temperature is 30-70 ℃, the stirring time is 10-30min, and the stirring speed is 600-800rpm/min.

In particular embodiments, the conditions of the mixing contact include: the temperature of mixing and contacting is 30-70 ℃, and the time of mixing and contacting is 1-24h, preferably 2-6h. Specifically, the temperature of the mixing contact can be 30 ℃, 40 ℃, 50 ℃, 60 ℃ or 70 ℃; the mixing contact time can be 1h, 2h, 4h, 6h, 8h, 10h, 12h, 15h, 18h, 20h or 24h.

In the method, the mixed solvent is obtained by mixing an organic solvent and water; wherein the organic solvent is methanol and/or ethanol.

In a preferred embodiment, the organic solvent is present in a proportion of 10 to 90 parts, preferably 50 to 80 parts, based on 100 parts of the total volume of the mixed solvent. Specifically, the organic solvent may be in a proportion of 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, or 90 parts.

The invention also provides the superhydrophobic glass microsphere obtained by the preparation method, wherein the superhydrophobic glass microsphere comprises an inner core particle and an outer layer particle attached to the surface of the inner core particle, the size of the inner core particle is larger than that of the outer layer particle, and the contact angle of the superhydrophobic glass microsphere and water is larger than 150 degrees.

The invention further provides a super-hydrophobic coating which is prepared from the raw materials containing the super-hydrophobic glass beads, epoxy resin, a curing agent and a solvent.

In a preferred embodiment, the weight ratio of the super-hydrophobic glass beads, the epoxy resin and the curing agent in the raw materials is 3 (2-6) to (0.4-1), and is preferably 3 (2-4) to (0.4-0.7).

In addition, the present invention can provide a method for preparing the superhydrophobic coating described above, the method comprising the steps of:

In a preferred embodiment, in step (1), the solvent may be butyl acetate, xylene or propylene glycol methyl ether acetate. The process of dispersing the super-hydrophobic glass beads in the solvent comprises the step of stirring the super-hydrophobic glass beads in the solvent, wherein the stirring time is 10-30min, and the stirring speed is 500-800rpm/min. And adding epoxy resin after dispersion, and mixing, wherein the mixing process comprises the steps of adding the epoxy resin, and stirring for 10-30min at the stirring speed of 800-1000rpm/min.

In a preferred embodiment, the epoxy resin in step (1) is an E44 type epoxy resin, an amino resin, an acrylic resin, or a phenolic resin.

In a preferred embodiment, the curing agent in step (2) is diaminodiphenylmethane (DDM).

The present invention will be described in detail below by way of examples, but the scope of the present invention is not limited thereto.

In the following examples, hollow glass microspheres and E44 type epoxy resin were obtained from Kjeldahl chemical company, triethylamine, vinyltrimethoxysilane and perfluorohexyltriethoxysilane were obtained from Profenox reagent company, and curing agents DDM and butyl acetate were obtained from Profenox reagent company.

Example 1

The synthesis method of the super-hydrophobic glass beads comprises the following steps:

weighing 5g of hollow glass microspheres (the particle size is 5-60 mu m and Dn90 is less than 40 mu m) to be dispersed in a mixed solvent (the volume ratio of ethanol is 75%), then adding 5g of triethylamine, heating to 40 ℃, stirring for 15min, adding 2.5g of vinyl trimethoxy silane at the stirring speed of 700rpm/min, and reacting for 2h at the reaction temperature of 40 ℃; after the reaction is finished, filtering, washing with ethanol, and drying to obtain the super-hydrophobic glass beads A1;

wherein the weight ratio of the hollow glass beads to the hydrophobic silane coupling agent vinyl trimethoxy silane is 1.

Example 2

weighing 5g of hollow glass microspheres (the particle size is 50-110 mu m, and Dn90 is less than 75 mu m) to disperse in a mixed solvent (the volume ratio of ethanol is 30%), then adding 5g of triethylamine, heating to 30 ℃, stirring for 15min at the stirring speed of 600rpm/min, and then adding 4g of vinyltrimethoxysilane to react for 5h at the reaction temperature of 40 ℃; after the reaction is finished, filtering, washing with ethanol, and drying to obtain the super-hydrophobic glass beads A2;

Example 3

weighing 5g of hollow glass microspheres (the particle size is 5-60 mu m and Dn90 is less than 40 mu m) to be dispersed in a mixed solvent (the volume of ethanol accounts for 50 percent), then adding 5g of triethylamine, heating to 40 ℃, stirring for 15min at the stirring speed of 800rpm/min, then adding 1.5g of perfluorohexyltriethoxysilane, and reacting for 3h at the reaction temperature of 50 ℃; after the reaction is finished, filtering, washing with ethanol, and drying to obtain the super-hydrophobic glass beads A3;

wherein the weight ratio of the hollow glass beads to the hydrophobic silane coupling agent perfluorohexyltriethoxysilane is 1.

Example 4

The super-hydrophobic coating is prepared from the following raw materials: the coating comprises the following components of super-hydrophobic glass beads, E44 type epoxy resin, a curing agent DDM and a solvent butyl acetate, wherein the weight ratio of the super-hydrophobic glass beads A1 to the epoxy resin to the curing agent is 3.

The preparation method of the super-hydrophobic coating comprises the following steps:

(1) Taking 3g of the super-hydrophobic glass bead A1 obtained in the example 1, stirring and dispersing in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, and then adding 3g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

(2) And adding 0.7g of curing agent DDM into the mixed solution, stirring for 2min, and uniformly mixing to obtain the super-hydrophobic coating.

Example 5

The super-hydrophobic coating is prepared from the following raw materials: the paint comprises the following components, by weight, 3.

(1) Taking 3g of the super-hydrophobic glass bead A2 obtained in the example 2, stirring and dispersing in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, and then adding 2g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

(2) And adding 0.4g of curing agent DDM into the mixed solution, stirring for 2min, and uniformly mixing to obtain the super-hydrophobic coating.

Example 6

The super-hydrophobic coating is prepared from the following raw materials: the coating comprises the following components of super-hydrophobic glass beads, E44 type epoxy resin, a curing agent DDM and a solvent butyl acetate, wherein the weight ratio of the super-hydrophobic glass beads A3 to the epoxy resin to the curing agent is 3.

(1) Taking 3g of the super-hydrophobic glass bead A3 obtained in the example 3, stirring and dispersing in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, and then adding 2g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

Example 7

The super-hydrophobic coating is prepared from the following raw materials: the paint comprises the following components, by weight, 3 parts of super-hydrophobic glass beads, E44 type epoxy resin, a curing agent DDM and a solvent butyl acetate, wherein the weight ratio of the super-hydrophobic glass beads A3 to the epoxy resin to the curing agent is.

(1) Taking 15kg of the super-hydrophobic glass beads A3 obtained in the example 3, stirring and dispersing in 75L of butyl acetate, dispersing for 30min at the stirring speed of 600rpm/min, and then adding 10kg of E44 type epoxy resin, and mixing for 120min at the stirring speed of 800rpm/min to obtain a mixed solution;

(2) And adding 2kg of curing agent DDM into the mixed solution, stirring for 10min, and uniformly mixing to obtain the super-hydrophobic coating.

Comparative example 1

The procedure is as described in example 1, except that vinyltrimethoxysilane is used in an amount of 5g, giving product D1.

Comparative example 2

The procedure is as described in example 1, except that vinyltrimethoxysilane is used in an amount of 0.4g, giving product D2.

Comparative example 3

The coating is prepared from the following raw materials: the epoxy resin coating comprises modified glass beads, E44 type epoxy resin, a curing agent DDM and a solvent butyl acetate, wherein the weight ratio of a product D1 to the epoxy resin to the curing agent is 3.

The preparation method of the coating comprises the following steps:

(1) Taking 3g of the product D1 obtained in the comparative example 1, stirring and dispersing in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, and then adding 3g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

(2) And adding 0.7g of curing agent DDM into the mixed solution, stirring for 2min, and uniformly mixing to obtain the coating.

Comparative example 4

The coating is prepared from the following raw materials: the modified glass bead, the E44 type epoxy resin, the curing agent DDM and the solvent butyl acetate, wherein the weight ratio of the product D2 to the epoxy resin to the curing agent is 3.

The preparation method of the coating comprises the following steps:

(1) Taking 3g of the product D2 obtained in the comparative example 2, stirring and dispersing in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, and then adding 3g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

Comparative example 5

The coating is prepared from the following raw materials: the epoxy resin coating comprises hollow glass beads, E44 type epoxy resin, a curing agent DDM and a solvent butyl acetate, wherein the weight ratio of the hollow glass beads to the epoxy resin to the curing agent is 3.

The preparation method of the coating comprises the following steps:

(1) Taking 3g of hollow glass microspheres to stir and disperse in 15mL of butyl acetate, dispersing for 10min at the stirring speed of 600rpm/min, then adding 3g of E44 type epoxy resin, and mixing for 20min at the stirring speed of 1000rpm/min to obtain a mixed solution;

Test example

Test example 1

The shapes of the super-hydrophobic glass beads A1 and A3 obtained in the embodiments 1 and 3 are characterized by a scanning electron microscope, and the result is shown in FIG. 1; the shapes of the products D1 and D2 obtained in the comparative example 1-2 and the hollow glass beads were characterized by a scanning electron microscope, and the results are shown in FIG. 2.

As can be seen from fig. 1, the super-hydrophobic glass beads A1 and A3 prepared in examples 1 and 3 have raspberry-like morphology, the core particles are large-sized glass beads, a plurality of hydrophobic siloxane small particles are attached to the surfaces of the core glass beads, and the hydrophobic siloxane small particles attached to the outer layers have uniform particle size and are uniformly attached to the surfaces of the glass beads to form a regular micro-nano hierarchical structure; as can be seen from fig. 2, the surface of the unmodified hollow glass microsphere is smooth, and it can be seen from the morphologies of the products D1 and D2 that when the hollow glass microsphere and the hydrophobic silane coupling agent are not within the range required by the present invention, the surface of the obtained glass microsphere does not have a bright micro-nano structure.

Test example 2

The coatings obtained in examples 4-7 and comparative examples 3-5 were sprayed onto the same substrate surface in the same manner, the sprayed coatings were controlled to have the same coating thickness, and the coatings were obtained after curing for 24 hours.

The contact angles of the coatings obtained by spraying the coatings obtained in examples 4 to 7 and comparative examples 3 to 5 on the surface of the substrate were measured by using a contact angle measuring instrument, wherein the contact angle measurement picture of the coating obtained by spraying the coating obtained in examples 4 to 6 on the surface of the substrate and water is shown in FIG. 3, and the contact angle measurement picture of the coating obtained by spraying the coating obtained in comparative examples 3 to 5 on the surface of the substrate and water is shown in FIG. 4;

the contact angle test results are shown in table 1.

TABLE 1

Numbering	Contact angle with water
		Example 4	155°
Example 5	151°
		Example 6	168°
Example 7	162°
		Comparative example 3	137°
Comparative example 4	108°
		Comparative example 5	63°

The results in table 1 show that the method of the present invention can obtain super-hydrophobic glass beads and super-hydrophobic coating with excellent hydrophobic property, the preparation process is simple, and the super-hydrophobic coating obtained by industrial amplification has excellent super-hydrophobic property.

Test example 3

The coatings obtained by spraying the coatings obtained in examples 4 to 7 and comparative examples 3 to 5 on the surface of a substrate were tested for abrasion resistance and scratch resistance.

Wear resistance: carrying out reciprocating friction on the surface of the coating by using 200-mesh abrasive paper under the action of 1kg of force, wherein the relative friction speed is 2m/s, after polishing for 10min, testing the contact angle between the surface of the polished coating and water by using a contact angle measuring instrument, and the test result is shown in table 2;

scratch resistance: the surface of the coating is scratched by a small blade, after the surface is scratched for 50 times, a contact angle measuring instrument is adopted to test the contact angle between the scratched surface of the coating and water, and the test result is shown in table 2.

TABLE 2

As can be seen from the data in Table 3, the super-hydrophobic coating obtained by curing the super-hydrophobic coating obtained by the method of the invention has excellent abrasion resistance and scratch resistance, and the polished and scratched coating still has excellent super-hydrophobic property and stable super-hydrophobic property.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A preparation method of super-hydrophobic glass beads is characterized by comprising the following steps: dispersing glass beads in a mixed solvent, and then adding organic amine and a hydrophobic silane coupling agent for mixing and contacting;

the particle size of the glass beads is 1-200 μm.

2. The method according to claim 1, wherein the glass beads are solid glass beads and/or hollow glass beads.

3. The method according to claim 1, wherein the hydrophobic silane coupling agent is one or more selected from the group consisting of alkyltrimethoxysilane, alkyltriethoxysilane, fluoroalkyltrimethoxysilane, and fluoroalkyltriethoxysilane;

wherein the alkyl is C1-C20 alkyl.

4. The method according to claim 1, wherein the organic amine is one or more selected from triethanolamine, tripropanolamine, and trialkylamine.

5. The method according to claim 1 or 4, wherein the weight ratio of the glass beads to the organic amine is 1.

6. The method of claim 1, wherein the conditions of the mixing contact comprise: the temperature of mixing and contact is 30-70 ℃, and the time of mixing and contact is 1-24h.

7. The method according to claim 1, wherein the mixed solvent is obtained by mixing an organic solvent and water;

wherein the organic solvent is methanol and/or ethanol;

8. Superhydrophobic glass microspheres obtained by the method of any one of claims 1-7.

9. A super-hydrophobic coating, characterized in that the super-hydrophobic coating is prepared from raw materials containing the super-hydrophobic glass beads of claim 8, epoxy resin, a curing agent and a solvent;

10. A method of preparing the superhydrophobic coating of claim 9, comprising the steps of:

(2) And adding a curing agent into the mixed solution and mixing to obtain the super-hydrophobic coating.