阅读说明：本技术 纳米超疏水涂料添加剂及其制备方法和应用 (Nano super-hydrophobic coating additive and preparation method and application thereof ) 是由 王成 张宪楠 于 2019-01-17 设计创作，主要内容包括：本发明公开了一种纳米超疏水涂料添加剂及其制备方法和应用,纳米超疏水涂料添加剂的制备方法包括以下步骤：将纳米材料与溶剂均匀混合,得到溶液A,向所述溶液A中加入催化剂和低表面能偶联剂,得到溶液B,将所述溶液B搅拌均匀,得到产物C,对所述产物C进行固液分离,得到固体为纳米超疏水涂料添加剂。本发明与传统制备疏水涂层的显著差异在于制备纳米超疏水涂料添加剂不需要构筑微纳米结构表面这一相对复杂的过程,而是从对纳米材料表面进行化学修饰的思想入手,直接利用纳米材料表面的活性基团对其进行有机共价化学修饰,制备出纳米超疏水涂料添加剂,大大简化了超疏水表面的制备过程。(The invention discloses a nano super-hydrophobic coating additive and a preparation method and application thereof, wherein the preparation method of the nano super-hydrophobic coating additive comprises the following steps: uniformly mixing a nano material and a solvent to obtain a solution A, adding a catalyst and a low-surface-energy coupling agent into the solution A to obtain a solution B, uniformly stirring the solution B to obtain a product C, and carrying out solid-liquid separation on the product C to obtain a solid nano super-hydrophobic coating additive. The obvious difference between the method and the traditional method for preparing the hydrophobic coating is that the relatively complex process of constructing the surface of a micro-nano structure is not needed in the preparation of the nano super-hydrophobic coating additive, and the nano super-hydrophobic coating additive is prepared by directly carrying out organic covalent chemical modification on the nano material by utilizing active groups on the surface of the nano material from the thought of carrying out chemical modification on the surface of the nano material, so that the preparation process of the super-hydrophobic surface is greatly simplified.)

1. A preparation method of a nano super-hydrophobic coating additive is characterized by comprising the following steps:

step 1, uniformly mixing a nano material and a solvent to obtain a solution A, wherein the concentration of the nano material in the solution A is 0.1-5 mg/m L, and the nano material is ZnO and Al₂O₃、Cu₂O、SiO₂、TiO₂The carbon nano tube, the amorphous carbon, the graphene or the boehmite, and the solvent is more than one of ethanol, isopropanol, acetone, xylene, dimethyl sulfoxide, toluene and petroleum ether;

step 2, adding a catalyst and a low-surface-energy coupling agent into the solution A to obtain a solution B, and uniformly stirring the solution B to obtain a product C, wherein the catalyst is hydrochloric acid or acetic acid, the low-surface-energy coupling agent is more than one of methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, triethoxyvinylsilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane, and the mass fraction of the nano material, the volume fraction of the catalyst and the volume fraction of the low-surface-energy coupling agent are 500: (0.05-2): (5-12);

and 3, carrying out solid-liquid separation on the product C to obtain the nano super-hydrophobic coating additive serving as a solid.

2. The preparation method according to claim 1, wherein in the step 1, the method for uniformly mixing the nanomaterial with the solvent is as follows: mixing the nano material with a solvent, and then carrying out ultrasonic treatment or stirring for 5-15 min;

in the step 2, the solution B is uniformly stirred by magnetic stirring for 60-100 min;

in the step 3, the solid-liquid separation method is filtration or suction filtration.

3. The method according to claim 2, wherein the unit of the volume part is m L when the unit of the mass part is mg.

4. The nano super-hydrophobic coating additive obtained by the preparation method of any one of claims 1 to 3.

5. The method for preparing the nano super-hydrophobic coating by using the nano super-hydrophobic coating additive as claimed in claim 4, wherein the nano super-hydrophobic coating additive is uniformly dispersed in ethanol, coated on a substrate and dried to obtain the nano super-hydrophobic coating.

6. The method according to claim 5, wherein the ratio of the mass part of the nano super-hydrophobic coating additive to the volume part of the ethanol is 1 (0.5-2); the coating is dripping coating, spraying coating, spin coating, blade coating or roller coating; the substrate is glass, ceramic, metal, paper, cloth or sponge.

7. Use of the nano-sized superhydrophobic coating of claim 5 or 6 for enhancing hydrophobic properties upon heating.

8. The use according to claim 7, wherein the contact angle increases by at least 2 ° when the temperature is raised from 20 to 25 ℃ to 400 ℃ and then lowered to room temperature.

9. The use of the nano superhydrophobic coating additive of claim 4 in a coating.

10. The use according to claim 9, wherein the nano-sized superhydrophobic coating additive is uniformly dispersed in the coating to obtain a modified superhydrophobic coating.

Technical Field

The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a nano super-hydrophobic coating additive and a preparation method and application thereof.

Background

The research on the super-hydrophobic surface is derived from the self-cleaning effect of the lotus leaf surface. The super-hydrophobic surface generally refers to a surface with a contact angle with water larger than 150 degrees and a rolling angle smaller than 10 degrees, so that the surface can effectively reduce the adhesion of a solid surface to water, and has wide application prospects in the fields of self-cleaning, ice resistance, antifogging, corrosion prevention, oil-water separation, microfluidic devices, underwater drag reduction and the like.

Two approaches are generally adopted for preparing the super-hydrophobic material: one is to directly construct a micro-nano structure on a low-energy surface; and the other method is to construct a micro-nano structure on the solid surface and then carry out low surface energy modification.

Methods for preparing superhydrophobic surfaces have so far mainly been template methods, phase separation methods, electrospinning methods, crystal growth methods, chemical etching methods, plasma treatment methods, physical or chemical vapor deposition methods, sol-gel methods, electrochemical deposition methods, self-assembly methods, and the like. However, the above method has the factors of complex process, high equipment requirement, high cost and the like in the preparation technology, and is difficult to be popularized and applied in a large scale in practice.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of a nano super-hydrophobic coating additive, which is simple and convenient and can be used for large-scale production of the nano super-hydrophobic coating additive. The preparation method of the invention is to use a coupling agent with low surface energy to chemically modify the surface of the nano material, and specifically, an organic group is introduced to the surface of the nano material through a one-step synthesis method, so as to obtain the nano super-hydrophobic coating additive with a contact angle of more than 150 degrees and a rolling angle of less than 5 degrees.

The invention also aims to provide the nano super-hydrophobic coating additive obtained by the preparation method.

The invention also aims to provide the application of the nano super-hydrophobic coating additive in coating, the super-hydrophobic additive has good compatibility with commercial coating, and the obtained super-hydrophobic coating is firm, high temperature resistant, acid and alkali resistant, corrosion resistant and has good ultraviolet resistance.

The invention aims to provide a preparation method of an oil-water separation structure with super-hydrophobic/super-lipophilic performance.

The invention aims to provide the application of the oil-water separation structure in improving the oil-water separation efficiency.

The invention aims to provide a using method of the oil-water separation structure.

The invention aims to provide the oil-water separation structure obtained by the preparation method.

The purpose of the invention is realized by the following technical scheme.

A preparation method of a nano super-hydrophobic coating additive comprises the following steps:

step 1, uniformly mixing a nano material and a solvent to obtain a solution A, wherein the concentration of the nano material in the solution A is 0.1-5 mg/m L, and the nano material is ZnO and Al₂O₃、Cu₂O、SiO₂、TiO₂The carbon nano tube, the amorphous carbon, the graphene or the boehmite, and the solvent is more than one of ethanol, isopropanol, acetone, xylene, dimethyl sulfoxide, toluene and petroleum ether;

in the step 1, the method for uniformly mixing the nano material and the solvent comprises the following steps: mixing the nano material with a solvent, and then carrying out ultrasonic treatment or stirring for 5-15 min.

Step 2, adding a catalyst and a low-surface-energy coupling agent into the solution A to obtain a solution B, and uniformly stirring the solution B to obtain a product C, wherein the catalyst is hydrochloric acid or acetic acid, the low-surface-energy coupling agent is more than one of methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, triethoxyvinylsilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane and octadecyltriethoxysilane, and the mass fraction of the nano material, the volume fraction of the catalyst and the volume fraction of the low-surface-energy coupling agent are 500: (0.05-2): (5-12);

in the step 2, the method for uniformly stirring the solution B is magnetic stirring, and the uniform stirring time is 60-100 min.

And 3, carrying out solid-liquid separation on the product C to obtain the nano super-hydrophobic coating additive serving as a solid.

In the step 3, the solid-liquid separation method is filtration or suction filtration.

In the above technical solution, when the unit of the mass part is mg, the unit of the volume part is m L.

The nano super-hydrophobic coating additive obtained by the preparation method.

The method for preparing the nano super-hydrophobic coating from the nano super-hydrophobic coating additive comprises the steps of uniformly dispersing the nano super-hydrophobic coating additive in ethanol, coating the ethanol on a substrate, and drying to obtain the nano super-hydrophobic coating.

In the technical scheme, the ratio of the mass part of the nano super-hydrophobic coating additive to the volume part of the ethanol for dispersing the nano super-hydrophobic coating additive is 1 (0.5-2).

In the above technical solution, the coating is drop coating, spray coating, spin coating, blade coating or roll coating.

In the above technical scheme, the substrate is glass, ceramic, metal, paper, cloth or sponge.

The application of the nanometer super-hydrophobic coating for improving the hydrophobic property after heating.

In the technical scheme, the temperature is raised from room temperature of 20-25 ℃ to 400 ℃ and then is reduced to the room temperature, and the contact angle is increased by at least 2 degrees.

The contact angle of the surface of the nano super-hydrophobic coating is 173-177 degrees, and the rolling angle is 3.0-5.0 degrees.

The application of the nano super-hydrophobic coating additive in coating.

And uniformly dispersing the nano super-hydrophobic coating additive in the coating to obtain the modified super-hydrophobic coating.

In the technical scheme, the method for uniformly dispersing the nano super-hydrophobic coating additive in the coating comprises the following steps: and adding the nano super-hydrophobic coating additive into the coating, and stirring for 5-20 min to uniformly disperse the nano super-hydrophobic coating additive.

In the technical scheme, the nano super-hydrophobic coating additive in the modified super-hydrophobic coating is 0.5-5.0 wt%.

A preparation method of an oil-water separation structure with super-hydrophobic/super-lipophilic performance comprises the following steps:

1) uniformly dispersing the nano super-hydrophobic coating additive in a coating to obtain a modified super-hydrophobic coating, wherein the mass fraction of the nano super-hydrophobic coating additive in the modified super-hydrophobic coating is 0.5-5.0 wt%;

2) covering the modified super-hydrophobic coating on a separation substrate to form a modified super-hydrophobic coating with the thickness of 10-50 mu m, and drying to obtain the oil-water separation structure, wherein the separation substrate is a metal net, sponge or cloth.

In the technical scheme, the method for covering the modified super-hydrophobic coating on the separation substrate comprises the following steps: spraying with a spray gun at a spraying speed of 0.3-0.5 m/s and a spraying pressure of at least 0.3MPa, wherein the distance between the nozzle and the separated substrate is 5-30 cm.

In the technical scheme, the spraying pressure is 0.3-0.7 MPa.

In the technical scheme, when the separation substrate is a sponge, the thickness of the sponge is 2-20 mm;

when the separation substrate is a metal mesh, the metal mesh is 80-400 meshes.

In the technical scheme, the caliber of the spray gun is 0.4-4.0 mm.

The oil-water separation structure obtained by the preparation method.

The oil-water separation structure is applied to improving the oil-water separation efficiency.

The oil-water separation structure is fixed into a container, and the container is placed on the liquid level of the oil-water mixture, so that oil in the oil-water mixture enters the container and water is blocked outside the container.

In the above technical solution, the container is a cuboid box without a cover.

The obvious difference between the method and the traditional method for preparing the hydrophobic coating is that the relatively complex process of constructing the surface of a micro-nano structure is not needed in the preparation of the nano super-hydrophobic coating additive, and the nano super-hydrophobic coating additive is prepared by directly carrying out organic covalent chemical modification on the nano material by utilizing active groups on the surface of the nano material from the thought of carrying out chemical modification on the surface of the nano material, so that the preparation process of the super-hydrophobic surface is greatly simplified. In addition, the nano super-hydrophobic coating additive prepared by the invention has high chemical stability and heat resistance exceeding that of common commercial coatings, does not influence the use of the coatings, and can remarkably improve the hydrophobic property of the coatings.

The oil-water separation structure can be used for quickly separating oil from water. The oil-water separation structure has good super-hydrophobicity/super-lipophilicity, can continuously work and can be recycled. The preparation method is simple, and the spraying mode is adopted to directly spray metal nets (such as copper nets, iron nets, stainless steel nets and other metal fiber fabrics), sponges, cloth (cotton/linen) and the like without pretreatment. The invention has no special requirements on the size and the shape of a spraying object, and can design the appearance and the scale at will according to actual needs.

Drawings

FIG. 1(a) is the contact angle of the surface of the nano-sized superhydrophobic coating obtained in example 1;

FIG. 1(b) is the rolling angle of the surface of the nano-sized superhydrophobic coating obtained in example 1;

FIG. 2(a) is the contact angle (after UV irradiation) of the surface of the nano-sized super-hydrophobic coating obtained in example 1;

FIG. 2(b) is the rolling angle (after UV irradiation) of the surface of the nano-sized superhydrophobic coating obtained in example 1.

FIG. 3(a) is the contact angle of the metal mesh with water;

FIG. 3(b) is a contact angle of the oil-water separating structure with water;

FIG. 3(c) is the contact angle of the oil-water separation structure with the volatile oil;

FIG. 4(a) is the contact angle of the metal mesh with water;

FIG. 4(b) is a contact angle of the oil-water separating structure with water;

FIG. 4(c) is the contact angle of the oil-water separation structure with the volatile oil.

Detailed Description

The raw material purchase sources in the following examples are as follows:

the equipment and its manufacturer referred to in the following examples are as follows:

the technical scheme of the invention is further explained by combining specific examples.

In the examples described below, parts by mass are in mg and parts by volume are in m L.