CN114806232B - Multi-scale antifouling coating and preparation method and application thereof - Google Patents

Multi-scale antifouling coating and preparation method and application thereof Download PDF

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CN114806232B
CN114806232B CN202210326132.8A CN202210326132A CN114806232B CN 114806232 B CN114806232 B CN 114806232B CN 202210326132 A CN202210326132 A CN 202210326132A CN 114806232 B CN114806232 B CN 114806232B
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silicon
micro
based material
silicon dioxide
nano structure
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CN114806232A (en
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郑龙辉
沈莹
陈晓芬
王剑磊
陈颖娴
吴立新
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
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    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
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    • D06N2209/00—Properties of the materials
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  • Silicon Compounds (AREA)

Abstract

The invention discloses a multi-scale antifouling coating and a preparation method and application thereof. According to the invention, multi-scale silicon dioxide is prepared by adopting multi-step reaction, and a micro-nano structure is constructed. The coating prepared by the invention has a lotus leaf-like structure with a lotus leaf-like effect. The preparation method has the characteristics of simple process, low cost, wide applicability and the like, and is suitable for industrial production.

Description

Multi-scale antifouling coating and preparation method and application thereof
Technical Field
The invention mainly relates to the technical field related to antifouling coatings, and particularly designs a preparation method for constructing a multi-scale antifouling coating.
Background
The lotus leaves are the most typical antifouling self-cleaning material in nature. The water contact angle of the surface is more than 160 degrees, the rolling angle is less than 5 degrees, so that the adhesive force between the water drop and the lotus leaf surface is far less than the adhesive force between the water drop and the lotus leaf surface, the surface of the pipe is in a quasi-spherical shape and is easy to roll, so that surface pollutants are taken away, and the antifouling effect is achieved. The self-cleaning capability of the lotus leaf is called as the lotus leaf effect, and the special performance of the lotus leaf is derived from a waxy material with a micro-nano structure and low surface energy on the surface of the lotus leaf, wherein the micro-nano structure plays a role in reducing the contact area between water drops and the surface, and the low surface energy on the lotus leaf surface is generated by a surface waxy layer. This property of lotus leaves also results in lower surface adhesion and surface coefficient of friction.
In recent years, great attention has been paid to a strategy for constructing a superhydrophobic self-cleaning surface by inorganic nanoparticles, and an excellent superhydrophobic self-cleaning effect has been obtained. However, the materials with micro-nano structures have poor film forming property, weak adhesion with a base material and poor mechanical durability, easily lose antifouling function and severely restrict the application of the materials.
Disclosure of Invention
The technical scheme of the invention is as follows:
a preparation method of a micro-nano structure comprises the following steps:
(1) Quickly adding the solution of the first silicon-based material into an alkaline solution, and reacting to obtain a dispersion liquid containing silicon dioxide seeds;
(2) Adding halide into the dispersion liquid containing the silicon dioxide seeds obtained in the step (1), and adjusting the pH value to be alkaline; slowly adding a solution of a second silicon-based material for primary reaction, and then adding a third silicon-based material for secondary reaction to obtain a silicon dioxide dispersion liquid;
(3) Adding silane into the silicon dioxide dispersion liquid prepared in the step (2) to carry out modification reaction to obtain modified silicon dioxide dispersion liquid;
(4) And (3) mixing the organic silicon modified epoxy resin with a curing agent, coating the mixture on the surface of a base material to obtain an adhesion layer, spraying the dispersion liquid of the modified silicon dioxide obtained in the step (3) on the surface of the adhesion layer, and curing to obtain the micro-nano structure.
According to an embodiment of the present invention, in the step (1), the solution of the first silicon-based material includes a first silicon-based material and a dispersion medium.
Preferably, the concentration of the first silicon-based material in the first silicon-based material solution is 0.01 to 0.2g/mL.
According to an embodiment of the present invention, in the step (1), the alkaline solution includes an alkali, deionized water, and a dispersion medium.
Preferably, the concentration of base in the basic solution is 0.01-0.2g/mL, such as 0.06g/mL.
Preferably, the volume ratio of the deionized water to the dispersion medium in the alkaline solution is (0.5-2) to 1, for example 1.
According to an embodiment of the present invention, in the step (1), the mass ratio of the first silicon-based material to the base is (1-3): 1, for example 3.
According to an embodiment of the present invention, the dispersion medium is selected from at least one of methanol, ethanol, isopropanol.
According to an embodiment of the present invention, in step (1), the reaction comprises: the reaction is carried out at a constant temperature of 20-40 ℃ for 2-6 hours, for example at 35 ℃ for 5 hours.
According to an embodiment of the invention, the base is selected from at least one of ammonia, sodium hydroxide, potassium hydroxide.
According to an embodiment of the present invention, the silica seeds have a morphology substantially as shown in FIG. 1. Preferably, the silica seeds are uniform in size, e.g., 10-100nm, and, for example, 74nm.
According to an embodiment of the invention, in step (2), the halide is selected from potassium chloride, sodium chloride, calcium chloride.
According to an embodiment of the present invention, in step (2), the mass to volume ratio (mg: mL) of the halide to the dispersion containing the silica seeds is (0.1 to 10) mg:60mL, for example, 1.5mg:60ml.
According to an embodiment of the invention, the adjustment of the pH to basic in step (2) means a pH value of 8 to 10, for example 8.5. The manner of adjusting the pH in step (2) is not particularly limited in the present invention, and any manner known in the art may be used as long as the pH can be adjusted.
According to an embodiment of the present invention, in the step (2), the solution of the second silicon-based material comprises the second silicon-based material and a dispersion medium having the meaning as described above.
Preferably, the concentration of the second silicon-based material in the solution of the second silicon-based material is 0.05 to 0.3g/mL, for example, 0.094g/mL.
According to an embodiment of the present invention, in the step (2), the slow addition means that the addition rate of the solution of the second silicon-based material is 20 to 50mL/h, for example, 30mL/h.
According to an embodiment of the present invention, in the step (2), the mass ratio of the second silicon-based material to the third silicon-based material is (0.5 to 3): 1, for example 1.
According to an embodiment of the present invention, the first, second and third silicon-based materials may be the same or different and are independently selected from tetraethyl orthosilicate, silicon tetrachloride.
Preferably, the first, second and third silicon-based materials are the same, for example selected from tetraethyl orthosilicate.
According to an embodiment of the present invention, the mass ratio of the first silicon-based material and the second silicon-based material is (0.2-1): 1.
in step (2), the solution of the silica has a morphology substantially as shown in fig. 2, according to an embodiment of the present invention. Preferably, the silica has a multi-scale particle size, for example, in the range of 50-2000nm. Further, the silica includes small size microspheres (e.g., having a particle size of 50 to 250 nm) and large size microspheres (e.g., having a particle size of 250 to 2000nm, for example, 250 to 500 nm).
The inventors have found that by the above-mentioned primary and secondary reactions, two different sizes of silica can be obtained simultaneously.
According to an embodiment of the present invention, in the step (3), the silane is selected from at least one of dimethyldichlorosilane, hexamethyldisilazane, dimethylsilane, octamethylcyclotetrasiloxane.
According to an embodiment of the present invention, in step (3), a diluent may also be added. Preferably, the diluent is selected, for example, from deionized water. Further, in the step (3), silane is added first, and then a diluent is added. The rate of hydrolysis of the silane can be controlled after the diluent is added.
According to an embodiment of the present invention, in the step (3), the conditions of the modification reaction include: the reaction is carried out at 50-90 deg.C for 0.1-10h, such as at 70 deg.C for 1h.
According to an embodiment of the invention, in step (3), the morphology of the modified silica is substantially the same as the silica, which has a multi-scale particle size.
According to an embodiment of the present invention, in step (4), the epoxy equivalent of the silicone-modified epoxy resin is preferably 180 to 220, for example 185 to 205.
Preferably, the epoxy resin is selected from epoxy resins having an epoxy value of 0.02 to 0.2mol/100g. The epoxy value in the present invention means the amount of the epoxy group contained in 100g of the epoxy resin.
According to an embodiment of the present invention, in the step (4), the curing agent is selected from ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diaminodicyclohexylmethane, diaminodiphenylmethane, and polyamide.
According to the embodiment of the present invention, in the step (4), the mass ratio of the silicone-modified epoxy resin to the curing agent is (5-30): 1, for example 10.
According to the embodiment of the present invention, in the step (4), the timing of spraying the dispersion of modified silica is preferably that the adhesive layer is in a semi-cured state. Preferably, the semi-cured state in the present invention means that the resin in the adhesive layer is partially cross-linked, is solid at room temperature, and is molten when heated to 60 ℃ or higher.
According to an embodiment of the present invention, in the step (4), the modified silica dispersion liquid is contained in an amount of 1 to 30% by weight, for example, 10% by weight.
According to the embodiment of the present invention, the spraying amount of the modified silica dispersion sprayed on the surface of the adhesive layer in step (4) is not particularly limited, as long as the static contact angle of the surface of the obtained coating is greater than 150 ° and the rolling angle is less than 5 °. Illustratively, the amount of the modified silica dispersion sprayed is 2mL/cm 2 。
According to an embodiment of the present invention, in step (4), the substrate may be selected from substrates known in the art, for example selected from glass, cloth, metal, plastic.
According to an embodiment of the present invention, the reactions in steps (1) to (4) may be performed under stirring. Preferably, the stirring is not particularly limited in the present invention, and may be performed by using a stirring method known in the art as long as the reaction can be achieved.
The invention also provides a micro-nano structure obtained by the preparation method, and the micro-nano structure comprises an adhesion layer and modified silicon dioxide distributed on the surface of the adhesion layer.
According to an embodiment of the invention, the particle size of the modified silica is selected from the range of 50-2000nm.
Preferably, the modified silica is prepared by performing modification reaction on the surface of silica by using silane.
Further, the silica, silane has the meaning as described above.
According to an embodiment of the present invention, the modified silica comprises silica macromicrospheres and silica minimicrospheres. Preferably, small silica microspheres are distributed around each large silica microsphere, and a nanoscale periodic concave-convex structure is preferably formed.
Further, the silica macromicrospheres have an average particle size of 250 to 2000nm, such as 250 to 500nm, and further such as 389nm. Further, the silica microspheres have a particle size of 50-250nm, for example 116nm.
According to an embodiment of the invention, the surface of the micro-nano structure has a static contact angle of water of more than 150 °, for example 158.5 °.
According to the embodiment of the invention, the surface rolling angle of the micro-nano structure is less than 5 degrees.
The invention also provides application of the micro-nano structure in the field of antifouling, such as antifouling coating.
The invention also provides a coating which comprises the micro-nano structure and a base material, wherein the micro-nano structure is positioned on at least one side of the substrate. The substrate has the meaning as described above.
Preferably, the micro-nano structure is bonded to the substrate by an adhesive layer, which has the meaning as described above.
The invention has the beneficial effects that:
(1) The invention adopts multi-step reaction to prepare multi-scale silicon dioxide and construct a micro-nano structure.
(2) The invention adopts the low surface energy organosilicon modified epoxy resin as a film forming substance and adopts the multi-scale modified silicon dioxide as a functional material to form the lotus leaf-like coating.
(3) The invention takes resin as an adhesive layer, thereby greatly improving the durability of the coating.
(4) The preparation method of the multi-scale coating provided by the invention has the characteristics of simple process, low cost, wide applicability and the like, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of the silica seed prepared in example 1.
FIG. 2 is a scanning electron micrograph of the multi-scale silica prepared in example 1.
Fig. 3 is an infrared spectrum before and after chemical modification of the multi-scale silica prepared in example 1.
Fig. 4 is a contact angle test chart of the multi-scale coating prepared in example 1.
Fig. 5 is a contact angle test plot of the multi-scale coating prepared in example 2.
Fig. 6 is a contact angle test chart of the monodisperse silica coating prepared in comparative example 1.
Fig. 7 is a contact angle test plot of an unmodified multi-scale coating prepared in comparative example 2.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
(1) Preparing silicon dioxide seeds: mixing 25mL of absolute ethyl alcohol, 25mL of deionized water and 3mL of 28wt% ammonia water (purchased from Aladdin reagents, inc.) to obtain a mixed solution A, wherein the ammonia is used as a catalyst for hydrolyzing a silicon source; adding tetraethyl orthosilicate (purchased from national pharmaceutical group chemical reagent Co., ltd.) into 50mL of absolute ethanol to prepare 0.0841g/mL of ethanol solution of tetraethyl orthosilicate, and marking the solution as solution B; then, rapidly pouring the solution B into the solution A at one time under the magnetic stirring state, reacting in a constant-temperature oil bath kettle at 35 ℃ for 5 hours, centrifuging the reaction solution, removing the supernatant to obtain a reaction precipitate, dispersing the precipitate with a proper amount of absolute ethanol, centrifuging again to obtain a precipitate, circularly washing for more than 3 times to obtain silicon dioxide seeds, uniformly dispersing the washed silicon dioxide seeds into 60mL of ethanol by using ultrasound to obtain a silicon dioxide seed dispersion solution, and marking as a solution C.
(2) Preparing multi-scale silicon dioxide: adding 0.0015g of KCl, 6mL of deionized water and 3mL of 28wt% ammonia water (purchased from Aladdin reagent Co., ltd.) into the silicon dioxide seed dispersion liquid in the step (1) to form a mixed liquid, and recording the mixed liquid as a solution D, wherein the ammonia has the function of serving as a catalyst for hydrolysis of a silicon source, and the chlorine salt has the function of further growing the silicon dioxide seeds; adding 5.64g of tetraethyl orthosilicate into 60mL of absolute ethanol to prepare an ethanol solution of tetraethyl orthosilicate, and marking as a solution E; then, solution E was added slowly to solution D over 2h with a peristaltic pump. And then, sequentially adding the solution C and 5.64g of tetraethyl orthosilicate, continuing to react for 20 hours in a constant-temperature oil bath at 35 ℃, centrifuging the reaction solution, removing supernatant to obtain reaction precipitate, dispersing the precipitate by using a proper amount of absolute ethyl alcohol, centrifuging again to obtain the precipitate, circularly washing for more than 3 times in the way, centrifuging and washing to obtain multi-scale silicon dioxide, and dispersing the washed multi-scale silicon dioxide into 100mL of ethanol to obtain the multi-scale silicon dioxide dispersion solution.
(3) Silane-modified multi-scale silica: and (3) adding 5mL of dimethyldichlorosilane and 5g of deionized water into the multi-scale silicon dioxide dispersion liquid obtained in the step (2), and magnetically stirring and refluxing for 1h in a constant-temperature oil bath kettle at 70 ℃. And centrifuging and washing the reaction solution, and dispersing the reaction solution into ethanol to obtain the modified multi-scale silicon dioxide dispersion solution with the mass content of 10%.
(4) Uniformly mixing organosilicon modified epoxy resin (purchased from Shanghai high-tech materials (Shanghai) Co., ltd., EPSI-3201, epoxy equivalent of 185-205) and polyamide curing agent (651) (purchased from Shanghai Allandin Biotechnology Co., ltd.) by simple mechanical stirring, coating the mixture on the surface of a glass substrate to obtain an adhesive layer (the mass ratio of the organosilicon modified epoxy resin to the curing agent is 10 2 And curing to obtain the multi-scale antifouling coating.
FIG. 1 is a scanning electron micrograph of a silica seed prepared in example 1. It can be seen from FIG. 1 that the silica seeds have uniform particle size and good monodispersity, and the average particle size distribution is measured to be around 74nm.
FIG. 2 is a scanning electron micrograph of the multi-scale silica prepared in example 1. It can be seen from fig. 2 that the multi-scale silica comprises large silica microspheres with an average particle size of 389nm, and small silica microspheres with a particle size of about 116nm are distributed around each large silica microsphere, so that a plurality of nanoscale periodic concave-convex structures are formed. The prepared multi-size silicon dioxide has different particle sizes and the particle size distribution width of 50-500nm, and two particle size distribution peaks approximately exist, wherein the proportion of 50-250nm is 50%, and the proportion of 250-500nm is 50%, so that the expected preparation of the multi-size silicon dioxide is achieved.
FIG. 3 is a Fourier infrared spectrum of the multi-scale silica prepared in example 1 before and after chemical modification. The test instrument was a Fourier transform infrared spectrometer (NICOLETIS 5, thermo Fisher Scientific, USA). From FIG. 3, it can be seen that the characteristic absorption peak corresponding to Si-OH bond in the modified silica disappeared because-OH at the end of silica reacted with-Cl of dimethyldichlorosilane to graft a low surface energy substance onto the silica surface, thereby indicating that the modified silica was successfully prepared.
FIG. 4 is a contact angle test chart of the multi-scale anti-fouling coating prepared in example 1. The testing instrument is a contact angle measuring instrument (JC 2000D, shanghai Zhongchen), and the testing method comprises the step of measuring static contact angles, rolling angles and the like of the prepared coating sample at room temperature (23 ℃), wherein the tested liquid is deionized water, the volume testing dosage of the static contact angle liquid drops is 2 mu L, the volume testing dosage of the rolling angle liquid drops is 14 mu L, the working voltage is 220V, and the power frequency is 50Hz. As can be seen from fig. 4, the static contact angle and the rolling angle of the coating prepared in example 1 are 158.49 ° and 1 °, so that it can be judged that the coating of this example has superior water repellency.
Example 2
The manufacturing method of this example is substantially the same as example 1, except that the glass substrate in step (4) is replaced with a polyester fabric.
As shown in fig. 5, the static contact angle and the rolling angle of the coating prepared in this example were 158.99 °.
Comparative example 1
(1) Preparation of monodisperse silica particles: adding 25mL of absolute ethyl alcohol, 25mL of deionized water and 3mL of ammonia water into a 250mL three-neck flask, and magnetically stirring for 5 minutes to form a mixed solution A); adding 4.5mL of tetraethyl orthosilicate into 50mL of absolute ethanol to prepare an ethanol solution of tetraethyl orthosilicate (defined as solution B); then, rapidly pouring the solution B into the solution A at one time under the magnetic stirring state, and reacting for several hours in a constant-temperature oil bath at 35 ℃; and (3) centrifugally precipitating the sol obtained by the reaction, washing precipitates with absolute ethyl alcohol, performing ultrasonic circulation for 3 times (in order to remove unreacted raw materials in the product), finally, drying in an oven at 60 ℃, and grinding into powder for later use.
(2) Monodisperse silicon dioxide, namely adding the synthesized silicon dioxide into 100mL of absolute ethyl alcohol, and stirring and ultrasonically dispersing the silicon dioxide uniformly; 5mL of dimethyldichlorosilane and 5g of deionized water were added in this order with stirring, and the mixture was stirred magnetically in a constant temperature oil bath at 70 ℃ under reflux for 1 hour. Centrifuging the reaction solution, taking filter residue, washing with anhydrous ethanol, centrifuging, performing ultrasonic circulation for 3 times, drying in an oven at 60 deg.C, and grinding into powder.
After 0.5g of the powder prepared in step (2) was dispersed in 49.5g of ethanol, a coating layer was prepared according to step (4) of example 1.
As shown in fig. 6, the coating of the present comparative example had a static contact angle of 125.63 ° and a rolling angle of greater than 10 °.
Comparative example 2
(1) Synthesis of monodisperse silica: adding 25mL of absolute ethyl alcohol, 25mL of deionized water and 3mL of ammonia water into a 250mL three-neck flask, and magnetically stirring for 5 minutes to form a mixed solution, namely a solution A; adding 4.5mL of tetraethyl orthosilicate into 50mL of absolute ethanol to prepare an ethanol solution of ethyl orthosilicate, and defining the ethanol solution as a solution B; then, rapidly pouring the solution B into the solution A at one time under the magnetic stirring state, and reacting for several hours in a constant-temperature oil bath at 35 ℃; and (3) centrifugally precipitating the sol obtained by the reaction, washing precipitates with absolute ethyl alcohol, performing ultrasonic circulation for 3 times (in order to remove unreacted raw materials in the product), finally, drying in an oven at 60 ℃, and grinding into powder for later use.
(2) Synthesis of multi-scale silica: 0.7g of the silica prepared in the step (1) is weighed and added into 30mL of absolute ethyl alcohol, and stirred and ultrasonically mixed uniformly to form a seed solution, which is defined as a solution C. Adding 0.0015g of KCl, 38mL of absolute ethyl alcohol, 6mL of deionized water and 3mL of ammonia water into a 250mL three-neck flask to form a mixed solution, namely a solution D; adding 5.64g of tetraethyl orthosilicate into 58mL of absolute ethanol to prepare an ethanol solution of the tetraethyl orthosilicate, which is defined as a solution E; then, solution E was added slowly to solution D over 2h with a peristaltic pump. Then, the solution C and 5.64g of tetraethyl orthosilicate are added in sequence, and the reaction is continued for 20 hours in a constant-temperature oil bath at 35 ℃. Centrifuging the reaction solution, taking filter residue, washing with anhydrous ethanol, performing ultrasonic circulation for 3 times, drying in an oven at 60 ℃, and grinding into powder for later use.
A coating was prepared by taking 0.5g of the powder prepared in step (2) and dispersing it in 49.5g of ethanol without chemical modification with dimethyldichlorosilane, according to step (4) of example 1.
As shown in fig. 7, the coating of the comparative example had a static contact angle of 14.39 ° and a rolling angle of greater than 10 °.
The above description is directed to exemplary embodiments of the present invention. However, the scope of protection of the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement and the like made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims (17)

1. A preparation method of a micro-nano structure is characterized by comprising the following steps:
(1) Quickly adding the solution of the first silicon-based material into an alkaline solution, and reacting to obtain a dispersion liquid containing silicon dioxide seeds; the size of the silicon dioxide seeds is uniform;
(2) Adding a halide into the dispersion liquid containing the silicon dioxide seeds obtained in the step (1), wherein the mass volume ratio of the halide to the dispersion liquid containing the silicon dioxide seeds is (0.1-10) mg:60mL, and adjusting the pH value to be alkaline; slowly adding a solution of a second silicon-based material for primary reaction, and then adding a third silicon-based material for secondary reaction to obtain a dispersion liquid of silicon dioxide, wherein the silicon dioxide comprises small-size microspheres and large-size microspheres, the particle size of the small-size microspheres is 50-250nm, and the particle size of the large-size microspheres is 250-2000nm; the mass ratio of the first silicon-based material to the second silicon-based material is (0.2-1): 1, and the mass ratio of the second silicon-based material to the third silicon-based material is (0.5-3): 1;
(3) Adding silane into the silicon dioxide dispersion liquid prepared in the step (2) to carry out modification reaction to obtain modified silicon dioxide dispersion liquid;
(4) And (3) mixing the organic silicon modified epoxy resin with a curing agent, coating the mixture on the surface of a base material to obtain an adhesion layer, spraying the dispersion liquid of the modified silicon dioxide obtained in the step (3) on the surface of the adhesion layer, and curing to obtain the micro-nano structure.
2. The production method according to claim 1, wherein in the step (1), the solution of the first silicon-based material comprises a first silicon-based material and a dispersion medium, and the concentration of the first silicon-based material is 0.01 to 0.2g/mL;
and/or, in the step (1), the alkaline solution comprises alkali, deionized water and a dispersion medium, and the concentration of the alkali is 0.01-0.2g/mL;
in the alkaline solution, the volume ratio of deionized water to a dispersion medium is (0.5-2): 1.
3. The method according to claim 2, wherein in the step (1), the mass ratio of the first silicon-based material to the base is (1-3): 1;
and/or the dispersion medium is selected from at least one of methanol, ethanol and isopropanol;
and/or the alkali is at least one of ammonia, sodium hydroxide and potassium hydroxide.
4. The method according to claim 1, wherein in the step (1), the reaction comprises: reacting for 2-6 hours at the constant temperature of 20-40 ℃.
5. The method according to claim 1, wherein in the step (2), the halide is selected from the group consisting of potassium chloride, sodium chloride, calcium chloride;
and/or, the pH value is adjusted to be alkaline in the step (2), namely the pH value is 8-10;
and/or, in the step (2), the solution of the second silicon-based material comprises the second silicon-based material and a dispersion medium, and the concentration of the second silicon-based material is 0.05-0.3g/mL;
and/or, in the step (2), the slow addition means that the addition rate of the solution of the second silicon-based material is 20-50mL/h.
6. The method according to claim 1, wherein the first, second and third silicon-based materials may be the same or different and are independently selected from the group consisting of tetraethyl orthosilicate and silicon tetrachloride.
7. The method according to claim 1, wherein the first, second and third silicon-based materials are the same.
8. The method according to claim 1, wherein in the step (3), the silane is at least one selected from the group consisting of dimethyldichlorosilane, hexamethyldisilazane, dimethylsilane, octamethylcyclotetrasiloxane;
and/or, in the step (3), a diluent is also added;
and/or, in the step (3), the conditions of the modification reaction comprise: reacting at 50-90 deg.C for 0.1-10h;
and/or in the step (3), the morphology of the modified silica is the same as that of the silica, and the modified silica has multi-scale particle sizes.
9. The production method according to claim 1, wherein in the step (4), the silicone-modified epoxy resin has an epoxy equivalent of 180 to 220;
and/or the organic silicon modified epoxy resin is selected from epoxy resin with an epoxy value of 0.02-0.2mol/100g;
and/or, in the step (4), the curing agent is selected from ethylenediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, diaminodicyclohexylmethane, diaminodiphenylmethane and polyamide;
and/or in the step (4), the mass ratio of the organosilicon modified epoxy resin to the curing agent is (5-30): 1;
and/or in the step (4), the mass content of the modified silicon dioxide dispersion liquid is 1-30wt%.
10. A micro-nano structure obtained by the preparation method of any one of claims 1 to 9, wherein the micro-nano structure comprises an adhesive layer and modified silica distributed on the surface of the adhesive layer.
11. A micro-nano structure according to claim 10, wherein the modified silica has a particle size selected from the group consisting of 50-2000nm; the modified silicon dioxide is prepared by adopting the silane to carry out modification reaction on the surface of the silicon dioxide;
and/or the static contact angle of the surface of the micro-nano structure is more than 150 degrees;
and/or the surface rolling angle of the micro-nano structure is less than 5 degrees.
12. A micro-nano structure according to claim 10, wherein the modified silica comprises large silica microspheres and small silica microspheres; and small silicon dioxide microspheres are distributed around each large silicon dioxide microsphere to form a nanoscale periodic concave-convex structure.
13. A micro-nano structure according to claim 12, wherein the average particle size of the large silica microspheres is 250-2000nm, and the particle size of the small silica microspheres is 50-250nm.
14. Use of the micro-nano structure according to any of claims 10 to 13 in the field of antifouling.
15. The use according to claim 14, wherein the micro-nano structure is used in an anti-fouling coating.
16. A coating comprising a micro-nano structure according to any one of claims 10 to 13 and a substrate, wherein the micro-nano structure is located on at least one side of the substrate.
17. A coating according to claim 16, wherein the micro-nano structure is bonded to the substrate by an adhesive layer.
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