CN113308173B

CN113308173B - Composite super-hydrophobic coating and preparation method and application thereof

Info

Publication number: CN113308173B
Application number: CN202110650577.7A
Authority: CN
Inventors: 王海涛; 朱建臣; 白炳莲; 李敏
Original assignee: Suzhou Jinlan Nano Technology Co ltd
Current assignee: Suzhou Jinlan Nano Technology Co ltd
Priority date: 2021-06-10
Filing date: 2021-06-10
Publication date: 2022-10-11
Anticipated expiration: 2041-06-10
Also published as: CN113308173A

Abstract

The application provides a composite super-hydrophobic coating and a preparation method and application thereof, and belongs to the technical field of super-hydrophobic materials. The composite super-hydrophobic coating comprises a 1, 4-bis [ (3, 4-dioctyloxybenzene) -diamido ] benzene layer and a resin layer which are combined. The 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene layer is a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene xerogel layer or a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder layer. The composite super-hydrophobic coating has good wear resistance, and can still keep excellent super-hydrophobic performance after being worn for many times.

Description

Composite super-hydrophobic coating and preparation method and application thereof

Technical Field

The application relates to the technical field of super-hydrophobic materials, in particular to a composite super-hydrophobic coating and a preparation method and application thereof.

Background

The organic nano-micron structure surface is constructed by an organic molecular gel method, so that the method has the advantages of low cost, convenience in construction and the like, but the formed organic nano-micron structure film has poor mechanical property and is not wear-resistant, and the application of the organic nano-micron structure film in actual production and life is limited.

The BPH-8/EtOH xerogel coating is used as a super-hydrophobic material, but has poor friction resistance, and the BPH-8/EtOH xerogel coating is abraded by using 150-mesh, 180-mesh, 220-mesh, 240-mesh, 320-mesh and 400-mesh sandpaper, and after 5, 4, 3 and 2 cycles respectively, the surface contact angle of the BPH-8/EtOH xerogel coating is below 150 degrees, and the BPH-8/EtOH xerogel coating is not in a super-hydrophobic state.

Disclosure of Invention

The application provides a composite super-hydrophobic coating, a preparation method and application thereof, which can improve the wear resistance of the surface of the composite super-hydrophobic coating.

The embodiment of the application is realized as follows:

in a first aspect, the present application provides an example of a composite superhydrophobic coating that includes a combined 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer and resin layer.

The 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene layer is a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene xerogel layer or a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder layer.

In the technical scheme, the composite super-hydrophobic coating has better wear resistance and can still keep excellent super-hydrophobic performance after being worn for many times.

With reference to the first aspect, in a first possible example of the first aspect of the present application, a material of the resin layer includes epoxy resin, nylon, polyoxymethylene, polycarbonate, or polyetheretherketone.

In the above examples, the resin has a high glass transition temperature, and can be used as a base layer to improve the wear resistance of the composite superhydrophobic coating.

In a second possible example of the first aspect of the present application, in combination with the first aspect, the thickness of the composite superhydrophobic coating is 2-200 μm.

Optionally, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 1 to 100 μm.

Optionally, the thickness of the resin layer is 1 to 100 μm.

In a second aspect, the present application provides a preparation method of the composite superhydrophobic coating, including: coating 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel on the surface of a first substrate to form a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer, coating a composition for forming the resin layer on the surface of a second substrate to form an uncured resin layer, drying the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer to form a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer, separating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first substrate, and attaching the separated 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the uncured resin layer until the uncured resin layer is cured.

In the technical scheme, the preparation method of the composite super-hydrophobic coating is simple and convenient, and can be used for preparing large-area composite super-hydrophobic coatings.

In a first possible example of the second aspect of the present application, in combination with the second aspect, after the above-described 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer obtained by separation is applied to the surface of the uncured resin layer, a pressure is applied to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer before the uncured resin layer is cured.

In the above examples, the application of pressure to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer enables the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and the uncured resin layer to be tightly bonded.

In a second possible example of the second aspect of the present application, in combination with the second aspect, the solvent of the above-mentioned 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel includes any one or more of ethanol, chloroform, benzene, toluene, tetrahydrofuran, and dimethylsulfoxide.

In a third possible example of the second aspect of the present application in combination with the second aspect, the drying includes vacuum freeze-drying, and the vacuum freeze-drying includes drying at 1.3 to 13Pa and-50 to-10 ℃ for 8 to 48 hours.

In a third aspect, the present application provides a preparation method of the composite superhydrophobic coating, including: coating the resin layer forming composition on the surface of a third substrate to form an uncured resin layer, and laying 1, 4-bis [ (3, 4-dioctyloxybenzene) -diamido ] benzene powder on the surface of the uncured resin layer to cure the uncured resin layer.

In a first possible example of the third aspect of the present application, in combination with the third aspect, after the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder is laid on the cured surface of the uncured resin layer, pressure is applied to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder before the uncured resin layer is cured.

In the above examples, applying pressure to 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder enables the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder and the uncured resin layer to be closely bonded.

In a fourth aspect, the present application provides a use of the composite superhydrophobic coating described above in preparation of a superhydrophobic material.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.

FIG. 1 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 4 cycles of abrasion with 150 mesh sandpaper;

FIG. 2 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 3 cycles of abrasion with 180 mesh sandpaper;

FIG. 3 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 2 cycles of abrasion with 220 mesh sandpaper;

FIG. 4 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 2 cycles of abrasion with 240 mesh sandpaper;

FIG. 5 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 2 cycles of abrasion with 320 mesh sandpaper;

FIG. 6 is a photograph of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion and after 1 cycle of abrasion with 400 mesh sandpaper;

FIG. 7 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 13 cycles of abrasion with 150 grit sandpaper;

FIG. 8 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 12 cycles of abrasion with 180 grit sandpaper;

FIG. 9 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 8 cycles of abrasion with 220 grit sandpaper;

FIG. 10 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 7 cycles of abrasion with 240 grit sandpaper;

FIG. 11 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 7 cycles of abrasion with 320 grit sandpaper;

FIG. 12 is a photograph of the composite superhydrophobic coating of example 1 of the present application before abrasion and after 4 cycles of abrasion with 400 mesh sandpaper;

FIG. 13 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 25 cycles of abrasion with 150 grit sandpaper;

FIG. 14 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 23 cycles of abrasion with 180 grit sandpaper;

FIG. 15 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 18 cycles of abrasion with 220 grit sandpaper;

FIG. 16 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 17 cycles of abrasion with 240 grit sandpaper;

FIG. 17 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 14 cycles of abrasion with 320 grit sandpaper;

FIG. 18 is a photograph of the composite superhydrophobic coating of example 2 of the present application before abrasion and after 8 cycles of abrasion with 400 mesh sandpaper;

FIG. 19 is a graph showing the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 150 mesh sandpaper;

FIG. 20 is a graph showing the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 180 mesh sandpaper;

FIG. 21 is a graph showing the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 220 mesh sandpaper;

FIG. 22 shows the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 240 grit sandpaper;

FIG. 23 is a graph showing the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 320 mesh sandpaper;

FIG. 24 is a graph showing the water static contact angle of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application during abrasion with 400 mesh sandpaper;

FIG. 25 shows the water static contact angle of the composite superhydrophobic coating of example 1 of the present application during abrasion with 150 mesh sandpaper;

FIG. 26 is the static contact angle of water during abrasion of the composite superhydrophobic coating of example 1 with 180 mesh sandpaper according to the present application;

FIG. 27 is the water static contact angle of the composite superhydrophobic coating of example 1 of the present application during abrasion with 220 grit sandpaper;

FIG. 28 is the water static contact angle of the composite superhydrophobic coating of example 1 of the present application during abrasion with 240 grit sandpaper;

FIG. 29 is the water static contact angle of the composite superhydrophobic coating of example 1 of the present application during abrasion with 320 mesh sandpaper;

FIG. 30 is the water static contact angle of the composite superhydrophobic coating of example 1 of the present application during abrasion with 400 mesh sandpaper;

FIG. 31 is the water static contact angle of the composite superhydrophobic coating of example 2 of the present application during abrasion with 150 mesh sandpaper;

FIG. 32 is the static contact angle of water during abrasion of the composite superhydrophobic coating of example 2 with 180 mesh sandpaper according to the present application;

FIG. 33 is the water static contact angle of the composite superhydrophobic coating of example 2 of the present application during abrasion with 220 grit sandpaper;

FIG. 34 is the water static contact angle of the composite superhydrophobic coating of example 2 of the present application during abrasion with 240 grit sandpaper;

FIG. 35 is the water static contact angle of the composite superhydrophobic coating of example 2 of the present application during abrasion with 320 mesh sandpaper;

FIG. 36 is the water static contact angle of the composite superhydrophobic coating of example 2 of the present application during abrasion with 400 mesh sandpaper;

FIG. 37 is a graph of the surface contact angle and scanning electron microscopy of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application before abrasion;

FIG. 38 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after being abraded with 150 mesh sandpaper for 4 cycles;

FIG. 39 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after 3 cycles of abrasion with 180 mesh sandpaper;

FIG. 40 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after 2 cycles of abrasion with 220 mesh sandpaper;

FIG. 41 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after 2 cycles of abrasion with 240 mesh sandpaper;

FIG. 42 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after being abraded with 320 mesh sandpaper for 2 cycles;

FIG. 43 is a graph of the surface contact angle and scanning electron microscope of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer of comparative example 1 of the present application after 1 cycle of abrasion with 400 mesh sandpaper;

FIG. 44 is a scanning electron micrograph and a surface contact angle of the composite superhydrophobic coating of example 1 of the present application before abrasion;

FIG. 45 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 1 of the present application after wearing with 150 mesh sandpaper for 13 cycles;

FIG. 46 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 1 of the present application after 12 cycles of abrasion with 180 grit sandpaper;

FIG. 47 is a surface contact angle and scanning electron microscope image of the composite superhydrophobic coating of example 1 of the present application after being worn by 220 grit sandpaper for 8 cycles;

FIG. 48 is a surface contact angle and scanning electron microscope image of the composite superhydrophobic coating of example 1 of the present application after being abraded by 240 grit sandpaper for 7 cycles;

FIG. 49 is a surface contact angle and scanning electron microscope image of the composite superhydrophobic coating of example 1 of the application after being abraded by 320 grit sandpaper for 7 cycles;

FIG. 50 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 1 of the present application after 4 cycles of abrasion with 400 mesh sandpaper;

FIG. 51 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 2 of the present application before abrasion;

FIG. 52 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 2 of the present application after wearing with 150 mesh sandpaper for 25 cycles;

FIG. 53 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 2 of the present application after 23 cycles of abrasion with 180 mesh sandpaper;

FIG. 54 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 2 of the present application after 18 cycles of abrasion with 220 grit sandpaper;

FIG. 55 is a surface contact angle and scanning electron micrograph of the composite superhydrophobic coating of example 2 of the present application after abrasion with 240 grit sandpaper for 17 cycles;

FIG. 56 is a surface contact angle and scanning electron microscope image of the composite superhydrophobic coating of example 2 of the application after being abraded by 320 grit sandpaper for 14 cycles;

fig. 57 is a surface contact angle and a scanning electron microscope image of the composite superhydrophobic coating layer of example 2 of the present application after being abraded by 400-mesh sandpaper for 8 cycles.

Detailed Description

Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The following is a detailed description of a composite superhydrophobic coating, a preparation method and an application thereof in the embodiments of the present application:

the application provides a composite superhydrophobic coating, comprising: a combined 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene (BPH-8) layer and a resin layer.

The 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene (BPH-8) layer and the resin layer are bonded by adhesion.

Wherein the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene layer can be 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene xerogel layer or 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder layer.

The structural formula of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene is as follows:

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has good super-hydrophobicity, and the surface contact angle is more than 150 degrees.

However, the abrasion resistance of the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer alone is poor. The composite super-hydrophobic coating obtained by attaching the resin layer to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -diamido ] benzene layer has better wear resistance and can still maintain excellent super-hydrophobic performance after being worn for many times.

The resin layer is made of resin with high glass transition temperature.

Optionally, the material of the resin layer includes epoxy resin, nylon, polyoxymethylene, polycarbonate or polyetheretherketone.

Optionally, the material of the resin layer is epoxy resin.

The thickness of the composite super-hydrophobic coating is 2-200 mu m, the thickness of the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer is 1-100 mu m, and the thickness of the resin layer is 1-100 mu m.

In one embodiment of the present application, the composite superhydrophobic coating has a thickness of 100 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 50 μm, and the resin layer has a thickness of 50 μm. In other embodiments of the present application, the composite superhydrophobic coating has a thickness of 100 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 60 μm, the resin layer has a thickness of 40 μm, or the composite superhydrophobic coating has a thickness of 200 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 100 μm, and the resin layer has a thickness of 100 μm, or the composite superhydrophobic coating has a thickness of 2 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 1 μm, and the resin layer has a thickness of 1 μm, or the composite superhydrophobic coating has a thickness of 150 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 100 μm, and the resin layer has a thickness of 50 μm, or the composite superhydrophobic coating has a thickness of 50 μm, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer has a thickness of 20 μm.

The application also provides a preparation method of the composite super-hydrophobic coating, which comprises the following steps: coating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel on the surface of a first substrate to form a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer, coating the resin layer-forming composition on the surface of a second substrate to form an uncured resin layer, drying the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer to form a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer, separating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first substrate, applying the separated 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the uncured resin layer, and applying pressure to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer to tightly bond the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and the uncured resin layer to be cured.

Wherein, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel is prepared by the following method:

mixing 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene and a solvent to obtain a mixed solution, putting the mixed solution into a sealed container, heating to completely dissolve the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene to obtain a colorless and transparent 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene solution, and cooling to room temperature to obtain the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel.

Alternatively, the mass to volume ratio of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene to the solvent is 1.5 to 2.5mg.

Alternatively, the mass to volume ratio of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene to solvent is 2mg.

The solvent comprises one or more of ethanol, chloroform, benzene, toluene, tetrahydrofuran and dimethyl sulfoxide.

The resin layer-forming composition includes a resin and an auxiliary agent.

For example, when the resin is an epoxy resin, the auxiliary is a curing agent, and the amount of epoxy resin and curing agent used is 1.

The drying in this application is vacuum freeze drying.

Optionally, the vacuum freeze-drying comprises drying for 8-48 h at 1.3-13 Pa and-50-10 ℃.

Optionally, the vacuum freeze-drying comprises drying at 1.3 to 13Pa and-50 ℃ for 12h.

The manner of applying pressure to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer involves gentle rolling with a glass rod.

The application also provides a preparation method of the composite super-hydrophobic coating, which comprises the following steps: applying the resin layer-forming composition to the surface of a third substrate to form an uncured resin layer, spreading 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder on the surface of the uncured resin layer, applying pressure to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder to closely bond the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder and the uncured resin layer, and curing the uncured resin layer.

The particle diameter of the 1, 4-bis [ (3, 4-dioctyloxybenzene) -diamido ] benzene powder is less than or equal to 250 mu m.

The composite super-hydrophobic coating can be prepared by two preparation methods, both of which are simple and convenient, and can be used for preparing large-area composite super-hydrophobic coatings.

The application example provides an application of the composite super-hydrophobic coating in preparing a super-hydrophobic material.

The following describes a composite super-hydrophobic coating and a method for preparing the same in detail with reference to the following examples.

Example 1

The application provides a composite super-hydrophobic coating and a preparation method thereof, which comprises the following steps:

1. preparation of a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer

Mixing 2mg of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene and 1.5mL of absolute ethyl alcohol to obtain a mixed solution, adding the mixed solution into a sealed bottle, heating to completely dissolve 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene to obtain a colorless and transparent 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene solution, cooling to room temperature to obtain 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel, uniformly coating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel on the surface of a 2cm-x first glass substrate, and then placing the first glass substrate coated with the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel in a vacuum drying oven to dry gel at-50 ℃ for 12 hours to obtain a 1, 4-dioctyloxybenzene-bisamide ] benzene xerogel with a micro-nano hierarchical structure.

2. Preparation of the resin layer

And mixing 0.5mL of epoxy resin and 0.5mL of epoxy curing agent, and uniformly coating the mixture on the surface of a 2cm x 2cm second glass substrate to obtain the resin layer.

3. Preparation of composite super-hydrophobic coating

Peeling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first glass substrate by using a blade, uniformly and perfectly attaching the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the resin layer on the surface of the second glass substrate, slightly rolling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer by using a glass rod to enable the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and the resin layer to be tightly combined, and obtaining the composite super-hydrophobic coating after the epoxy resin is cured.

Example 2

1. preparation of the resin layer

And mixing 0.5mL of epoxy resin and 0.5mL of epoxy curing agent, and uniformly coating the mixture on the surface of a 2cm x 2cm glass substrate to obtain the resin layer.

2. Preparation of composite super-hydrophobic coating

Grinding 20mg1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene into fine powder by using a mortar, then uniformly spreading 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder on the surface of a resin layer on a glass substrate, slightly rolling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder by using a glass rod to tightly combine the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder and the resin layer, and preparing the composite super-hydrophobic coating after epoxy resin is cured.

Example 3

The application provides a composite super-hydrophobic coating and a preparation method thereof, wherein the preparation method comprises the following steps:

2. Preparation of the resin layer

And mixing 0.5mL of nylon resin and 0.5mL of nylon resin curing agent, and uniformly coating the mixture on the surface of a 2cm x 2cm second glass substrate to obtain the resin layer.

3. Preparation of composite super-hydrophobic coating

Peeling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first glass substrate by a blade, uniformly and perfectly attaching the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the resin layer on the surface of the second glass substrate, slightly rolling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer by a glass rod to enable the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and the resin layer to be tightly combined, and obtaining the composite super-hydrophobic coating after the nylon resin is cured.

Example 4

Mixing 2mg of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene and 1.5mL of absolute ethyl alcohol to obtain a mixed solution, adding the mixed solution into a sealed bottle, heating to completely dissolve the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene to obtain a colorless and transparent 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene solution, cooling to room temperature to obtain a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel, uniformly coating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel on the surface of a 2cm first glass substrate, and then drying the first glass substrate coated with the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel in a vacuum drying box at the temperature of minus 50 ℃ for 12 hours to obtain a dry gel layer of the 1, 4-dioctyloxybenzene [ (3, 4-bisamido ] benzene with a micro-nano hierarchical structure.

2. Preparation of the resin layer

And mixing 0.5mL of polycarbonate and 0.5mL of polycarbonate curing agent, and uniformly coating the mixture on the surface of a 2cm x 2cm second glass substrate to obtain the resin layer.

3. Preparation of composite super-hydrophobic coating

Peeling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first glass substrate by a blade, uniformly and perfectly attaching the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the resin layer on the surface of the second glass substrate, slightly rolling the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer by a glass rod to enable the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and the resin layer to be tightly combined, and obtaining the composite super-hydrophobic coating after polycarbonate is cured.

Comparative example 1

The comparative example of the present application provides a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer and a method for preparing the same, which comprises the following steps:

mixing 2mg of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene and 1.5mL of absolute ethyl alcohol to obtain a mixed solution, adding the mixed solution into a sealed bottle, heating to completely dissolve 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene to obtain a colorless and transparent 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene solution, cooling to room temperature to obtain 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel, uniformly coating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel on the surface of a 2cm x 2cm first glass substrate, and then drying the first glass substrate coated with the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene gel in a vacuum drying oven at-50 ℃ for 12 hours to obtain a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene xerogel layer.

Test example 1

The composite superhydrophobic coatings obtained in examples 1 and 2 and the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer obtained in comparative example 1 were taken, the composite superhydrophobic coatings obtained in examples 1 and 2 and the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer obtained in comparative example 1 were abraded with 150 mesh, 180 mesh, 220 mesh, 240 mesh, 320 mesh and 400 mesh sandpaper, respectively, as shown in fig. 1 to 18, and the surface + contact angles of the composite superhydrophobic coating or the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer after undergoing abrasion for a plurality of cycles were characterized by a scanning electron microscope and a contact angle tester, as shown in fig. 19 to 36, and the scanning electron microscope images before and after the abrasion of the surface of the composite superhydrophobic coating or the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer are shown in fig. 37 to 57.

Wherein the wear comprises: the composite superhydrophobic coating or 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer was laid upside down on sandpaper, the composite superhydrophobic coating or 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer was brought into contact with the sandpaper, and a 50g weight was placed on the composite superhydrophobic coating or 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer alone, and then a horizontal force was applied to move it laterally and longitudinally along the vertical line by 10cm, respectively, which process was defined as one abrasion cycle.

The 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 150 mesh sandpaper, and its surface contact angle was still over 150 degrees after 4 cycles, but it became 150 degrees or less after 5 cycles, and there was no super-hydrophobic state any more;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 180 mesh sandpaper, and after 3 cycles, the surface contact angle was still over 150 degrees, but after 4 cycles, the surface contact angle became under 150 degrees, and no superhydrophobic state was present;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 220 mesh sandpaper, and after 2 cycles, the surface contact angle was still over 150 degrees, but after 3 cycles, the surface contact angle became under 150 degrees, and no superhydrophobic state was present;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 240-mesh sandpaper, and its surface contact angle was still over 150 degrees after 2 cycles, but it became 150 degrees or less after 3 cycles, and there was no super-hydrophobic state any more;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 320 mesh sandpaper, and after 2 cycles, the surface contact angle was still over 150 degrees, but after 3 cycles, the surface contact angle became under 150 degrees, and no superhydrophobic state was present;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer of comparative example 1 was abraded with 400 mesh sandpaper, and its surface contact angle was still 150 degrees or more after 1 cycle, but it became 150 degrees or less after 2 cycles, and there was no super-hydrophobic state any more.

The composite superhydrophobic coating of example 1 was abraded with 150 mesh sandpaper, and its surface contact angle was still over 150 degrees after 13 cycles;

the composite super-hydrophobic coating of example 1 was abraded with 180 mesh sandpaper, and after 12 cycles, the surface contact angle was still over 150 degrees;

the composite superhydrophobic coating of example 1 was abraded with 220 mesh sandpaper, and its surface contact angle was still over 150 degrees after 8 cycles;

the composite superhydrophobic coating of example 1 was abraded with 240 grit sandpaper, and its surface contact angle was still over 150 degrees after 7 cycles;

the composite superhydrophobic coating of example 1 was abraded with 320 mesh sandpaper, and its surface contact angle was still over 150 degrees after 7 cycles;

the composite superhydrophobic coating of example 1 was abraded using 400 grit sandpaper and its surface contact angle was still over 150 degrees after 4 cycles.

The composite superhydrophobic coating of example 2 was abraded with 150 mesh sandpaper, and its surface contact angle was still over 150 degrees after 25 cycles;

the composite superhydrophobic coating of example 2 was abraded with 180 grit sandpaper, after 23 cycles the surface contact angle was still over 150 degrees;

the composite superhydrophobic coating of example 2 was abraded with 220 mesh sandpaper, and its surface contact angle was still over 150 degrees after 18 cycles;

the composite super-hydrophobic coating of example 2 was abraded with 240 grit sandpaper, and after 17 cycles, the surface contact angle was still over 150 degrees;

the composite superhydrophobic coating of example 2 was abraded with 320 mesh sandpaper, and its surface contact angle was still over 150 degrees after 14 cycles;

the composite superhydrophobic coating of example 2 was abraded using 400 mesh sandpaper and its surface contact angle was still above 150 degrees after 8 cycles.

In summary, the abrasion resistance of the composite superhydrophobic coating of the embodiments of the present application is significantly better than that of a single layer of 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene.

The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A preparation method of a composite super-hydrophobic coating is characterized by comprising the following steps: coating a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel on the surface of a first substrate to form a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer, coating a composition for forming a resin layer on the surface of a second substrate to form an uncured resin layer, drying the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel layer to form the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer, separating the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer from the first substrate, and attaching the separated 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer on the surface of the uncured resin layer until the uncured resin layer is cured;

the material of the resin layer comprises epoxy resin, nylon, polyformaldehyde, polycarbonate or polyether-ether-ketone;

the solvent of the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene gel is ethanol.

2. The method of claim 1, wherein after the separated 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer is attached to the surface of the uncured resin layer, pressure is applied to the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene xerogel layer before the uncured resin layer is cured.

3. The preparation method of the composite super-hydrophobic coating according to claim 1, wherein the drying comprises vacuum freeze drying, and the vacuum freeze drying comprises drying for 8 to 48h under the conditions of 1.3 to 13Pa and-50 to-10 ℃.

4. A preparation method of a composite super-hydrophobic coating is characterized by comprising the following steps: coating the resin layer forming composition on the surface of a third substrate to form an uncured resin layer, laying 1, 4-bis [ (3, 4-dioctyloxybenzene) -diamido ] benzene powder on the surface of the uncured resin layer, and curing the uncured resin layer;

the material of the resin layer comprises epoxy resin, nylon, polyformaldehyde, polycarbonate or polyether ether ketone.

5. The method of claim 4, wherein after the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder is applied to the cured surface of the uncured resin layer, the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene powder is subjected to pressure before the uncured resin layer is cured.

6. The composite super-hydrophobic coating prepared by the preparation method of the composite super-hydrophobic coating according to claim 1 or claim 4, wherein the composite super-hydrophobic coating comprises a combined 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamido ] benzene layer and a resin layer;

the 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene layer is a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene xerogel layer or a 1, 4-bis [ (3, 4-dioctyloxybenzene) -bisamide ] benzene powder layer;

the material of the resin layer comprises epoxy resin, nylon, polyformaldehyde, polycarbonate or polyether-ether-ketone.

7. The composite superhydrophobic coating of claim 6, wherein the composite superhydrophobic coating has a thickness of 2 to 200 μm.

8. The composite superhydrophobic coating of claim 7, wherein the 1, 4-bis [ (3, 4-dioctyloxybenzene) bisamido ] benzene layer has a thickness of 1 to 100 μm.

9. The composite superhydrophobic coating of claim 7, wherein the thickness of the resin layer is 1-100 μm.

10. Use of the composite superhydrophobic coating of any one of claims 6-9 in preparation of a superhydrophobic material.