Solid-state super-smooth surface, and construction method therefor and use thereof

Abstract

The present application relates to the technical field of marine antifouling, and provides a solid-state super-smooth surface, and a construction method therefor and the use thereof. The chemical composition of the solid-state super-smooth surface constructed in the present application is a linear polyfluorosiloxane, which bonds with substrates by means of chemical covalent bonds. By means of firm bonding via chemical covalent bonds, the problem of a traditional biomimetic lubricating oil for super-smooth surfaces being easily washed away in underwater environments is solved, and longer lasting biofouling control performance can be achieved. The solid-state super-smooth surface provided by the present application is of a linear structure and has reliable underwater transparency, the underwater visible-light transmittance of the material being up to 95% or higher.

Description

A solid super-slippery surface and its construction method and application

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on January 19, 2024, with application number 202410080058.5 and invention name “A solid super-slippery surface, its construction method and application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application relates to the field of marine antifouling technology, and in particular to a solid super-slippery surface and a construction method and application thereof. Background Art

[0003] The annual global losses from marine biofouling are incalculable, severely hindering the healthy development of the marine industry. With the rapid development of my country's marine industry, demand for marine optical sensors (such as water quality monitoring instruments and underwater cameras) to monitor the marine environment is also increasing. However, biofouling on the sensor's optical window surface can cause data errors, seriously affecting the quality of the data being monitored. The development of reliable anti-fouling technology for underwater optical windows in marine instruments is of great significance for promoting the advancement of my country's marine science and technology industry.

[0004] There are currently three main methods for protecting marine instrument optical windows from biofouling. The first is the robotic arm scraping method to remove attached microorganisms, but this method requires complex equipment and tedious maintenance, which limits its further application. The second is the chemical biocide anti-fouling method, which is currently the most widely used anti-fouling method. It includes releasing organic biocides, placing copper sheets on the side, etc. The toxic substances released by this method usually have adverse effects on the surrounding environment and are not conducive to the sustainable development of marine ecology. The third is the photocatalytic method. However, the effective use range of this method can only be maintained within 1 meter below the water surface, and it cannot achieve effective protection in deeper waters. Therefore, the development of a new type of marine instrument optical window anti-fouling technology that is green, environmentally friendly, zero energy consumption, and has no scope of use restrictions is a very challenging scientific task and a topic that researchers are very concerned about.

[0005] The bionic (pitcher plant) super-slip surface has attracted widespread attention due to its good anti-fouling properties. A large number of studies have shown that this type of anti-fouling technology does not release toxic substances and can effectively prevent the attachment of microorganisms. It exhibits excellent anti-fouling performance while maintaining a high underwater transmittance. However, the lubricating oil film on this surface is prone to loss in the underwater environment, which greatly affects its anti-fouling ability. How to ensure the long-term anti-fouling ability is a technical problem that needs to be urgently solved in the practical application of bionic super-slip surfaces.

[0006] Summary of the Invention

[0007] The purpose of this application is to provide a solid super-slippery surface and its construction method and application. The solid super-slippery surface constructed in this application maintains high underwater transmittance while exhibiting excellent anti-fouling performance, and the anti-fouling ability is long-lasting.

[0008] In order to achieve the above-mentioned invention objectives, this application provides the following technical solutions:

[0009] The present application provides a method for constructing a solid super-slippery surface, comprising the following steps:

[0010] Performing surface hydroxylation modification on the substrate to obtain a hydroxyl-rich substrate;

[0011] Providing a reaction solution; the reaction solution comprises a silane monomer and an organic solvent; the silane monomer is a dichlorosilane monomer or a dimethoxysilane monomer; at least one of the dichlorosilane monomers is a fluorine-containing dichlorosilane monomer; at least one of the dimethoxysilane monomers is a fluorine-containing dimethoxysilane monomer;

[0012] The reaction solution is brought into contact with a substrate rich in hydroxyl groups, and the silane monomer is polymerized under the initiation of hydroxyl groups on the substrate to form a linear polyfluorosiloxane bonded to the substrate through a covalent bond, thereby obtaining a solid super-slippery surface.

[0013] Preferably, the fluorine-containing dichlorosilane monomer includes one or more of 1H,1H,2H,2H-perfluorodecylmethyldichlorosilane, 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and dichloro(methyl)(3,3,3-trifluoropropyl)silane.

[0014] Preferably, the dichlorosilane monomer further comprises a fluorine-free dichlorosilane monomer; the fluorine-free dichlorosilane monomer comprises one or more of diisopropyldichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, dichlorodiethylsilane, dichlorodipropylsilane, dibutyldichlorosilane, dichloro(isobutyl)(methyl)silane, dichlorodipentylsilane, dichlorodihexylsilane, dichloro(methyl)(propyl)silane, dichloroethylmethylsilane, methylvinyldichlorosilane, hexylmethyldichlorosilane, dichlorotetramethyldisilane, dichloromethyloctylsilane, dichloro(isobutyl)(methyl)silane, 1,3-dichloro-1,1,3,3,-tetramethyldisiloxane and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane.

[0015] Preferably, the fluorine-containing dimethoxysilane monomer includes 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and / or dimethoxybis(pentafluorophenyl)silane.

[0016] Preferably, the dimethoxysilane monomer further includes a fluorine-free dimethoxysilane monomer; the fluorine-free dimethoxysilane monomer includes one or more of dimethoxydiphenylsilane, dimethoxydimethylsilane, dimethoxy(methyl)silane, dimethoxy(methyl)octylsilane, dimethoxy(methyl)octylsilane, isobutyldimethoxy(methyl)silane, diisopropyldimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, diisobutyldimethoxysilane and methylcyclohexyldimethoxysilane.

[0017] Preferably, when the silane monomer is a dimethoxysilane monomer, the reaction solution further comprises an acid catalyst.

[0018] Preferably, the acid catalyst includes one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, p-toluenesulfonic acid, hydrofluoric acid, selenic acid, hypochlorous acid, trifluoromethanesulfonic acid and chloric acid.

[0019] Preferably, contacting the reaction solution with the hydroxyl-rich substrate comprises: soaking the hydroxyl-rich substrate in the reaction solution.

[0020] The present application provides a solid super-slippery surface obtained by the construction method described in the above scheme, the chemical composition of which is linear polyfluorosilicone, and the linear polyfluorosilicone is bonded to the substrate through a chemical covalent bond.

[0021] The present application provides the application of the solid super-slip surface described in the above solution as a marine antifouling coating.

[0022] The present application provides a method for constructing a solid super-smooth surface, comprising the following steps: performing surface hydroxylation modification on a substrate to obtain a hydroxyl-rich substrate; providing a reaction solution; the reaction solution comprises a silane monomer and an organic solvent; the silane monomer is a dichlorosilane monomer or a dimethoxysilane monomer; at least one of the dichlorosilane monomers is a fluorine-containing dichlorosilane monomer; at least one of the dimethoxysilane monomers is a fluorine-containing dimethoxysilane monomer; contacting the reaction solution with a hydroxyl-rich substrate, and polymerizing the silane monomer under the initiation of hydroxyl groups on the substrate to form a linear polyfluorosiloxane bonded to the substrate by covalent bonds, thereby obtaining a solid super-smooth surface.

[0023] This application utilizes hydroxyl groups on a substrate to initiate polymerization of silane monomers, thereby forming linear polyfluorosilicone macromolecules that simultaneously form covalent bonds with the substrate. This strong chemical covalent bond overcomes the problem of lubricant loss in traditional biomimetic super-slippery surfaces in underwater environments, resulting in longer-lasting biofouling resistance. The solid-state super-slippery surface constructed in this application has a linear structure and reliable underwater transparency, with an underwater visible light transmittance of over 95%.

[0024] The anti-fouling principle of the present application is: after polyfluorosilicone is grafted onto the surface of the substrate, the fluorine-containing groups in the polyfluorosilicone and the high flexibility of the polysiloxane molecular chain work synergistically. Specifically, the polysiloxane molecular chain has the characteristic of high fluidity, so the surface exhibits "liquid-like" properties on a macroscopic scale, and the hydrophobic properties of its lubricating oil make its interaction with water much smaller than that of the solid surface; at the same time, fluorine atoms have a strong electron-withdrawing inductive effect, which can form a strong shielding effect on the side chain groups, thereby limiting the sensitivity of the polyfluorosilicone macromolecular chain to van der Waals interactions, so that the polyfluorosilicone-based solid super-smooth surface has extremely low intermolecular interaction forces, and fouling substances (fouling organisms / fouling molecules) cannot exhibit strong interaction forces with it, and at the same time it is difficult for fouling substances to directly contact the original solid substrate, which ultimately makes it difficult for fouling substances to adhere to the surface.

[0025] The construction method of the solid super-smooth surface provided in this application is simple, the reaction conditions are mild and efficient, and the underwater optical window prepared with this material has long-term protection against marine biological fouling and has good application prospects in the field of marine protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] FIG1 is an FTIR spectrum of a polyfluorosilicone-based solid superslip surface prepared in Example 1 of the present application;

[0027] FIG2 is a graph showing the dynamic wettability of a droplet on the surface of a polyfluorosilicone-based solid superslippery surface (SSS) constructed in Example 3, a control glass sample (Glass), and a control perfluorosilane-treated sample (POTS-Glass);

[0028] FIG3 is a fluorescence photograph of bacteria attached to the polyfluorosilicone-based solid superslippery surface (SSS) constructed in Example 3, a control glass sample (Glass), and a control perfluorosilane-treated sample (POTS-Glass) after being immersed in a static Pseudoalteromonas culture solution for 3 days and 14 days;

[0029] FIG4 is a comparison of the underwater visible light transmittance of the polyfluorosilicone-based solid superslip surface (SSS) constructed in Example 3 and the control glass sample (Glass) before and after the antifouling experiment;

[0030] FIG5 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 1;

[0031] FIG6 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 2;

[0032] FIG7 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 3;

[0033] FIG8 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 4;

[0034] FIG9 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 5. DETAILED DESCRIPTION

[0035] The present application provides a method for constructing a solid super-slippery surface, comprising the following steps:

[0036] Performing surface hydroxylation modification on the substrate to obtain a hydroxyl-rich substrate;

[0037] Providing a reaction solution; the reaction solution comprises a silane monomer and an organic solvent; the silane monomer is a dichlorosilane monomer or a dimethoxysilane monomer; at least one of the dichlorosilane monomers is a fluorine-containing dichlorosilane monomer; at least one of the dimethoxysilane monomers is a fluorine-containing dimethoxysilane monomer;

[0038] The reaction solution is brought into contact with a substrate rich in hydroxyl groups, and the silane monomer is polymerized under the initiation of hydroxyl groups on the substrate to form a linear polyfluorosiloxane bonded to the substrate through a covalent bond, thereby obtaining a solid super-slippery surface.

[0039] In this application, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0040] The present application performs surface hydroxylation modification on a substrate to obtain a hydroxyl-rich substrate.

[0041] This application has no special requirements for the substrate, and a suitable substrate can be selected according to actual needs, such as glass, quartz, and silicon wafer. This application has no special requirements for the surface hydroxylation modification, and a surface hydroxylation modification process well known in the art is used to make the substrate carry a large number of hydroxyl groups; in the embodiment of this application, the glass slide is specifically ultrasonically cleaned in acetone, ethanol, and deionized water multiple times to remove impurities, and then immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 hour, rinsed with deionized water, and dried to obtain a glass sample with surface hydroxylation modification.

[0042] The present application provides a reaction solution; the reaction solution includes a silane monomer and an organic solvent.

[0043] In the present application, the silane monomer is a dichlorosilane monomer or a dimethoxysilane monomer; at least one of the dichlorosilane monomers is a fluorine-containing dichlorosilane monomer; and at least one of the dimethoxysilane monomers is a fluorine-containing dimethoxysilane monomer.

[0044] In the present application, the fluorine-containing dichlorosilane monomer preferably includes one or more of 1H,1H,2H,2H-perfluorodecylmethyldichlorosilane, 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane and dichloro(methyl)(3,3,3-trifluoropropyl)silane; the fluorine-containing dimethoxysilane monomer preferably includes 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and / or dimethoxybis(pentafluorophenyl)silane.

[0045] In the present application, the dichlorosilane monomer preferably also includes a fluorine-free dichlorosilane monomer; the fluorine-free dichlorosilane monomer preferably includes one or more of diisopropyldichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, dichlorodiethylsilane, dichlorodipropylsilane, dibutyldichlorosilane, dichloro(isobutyl)(methyl)silane, dichlorodipentylsilane, dichlorodihexylsilane, dichloro(methyl)(propyl)silane, dichloroethylmethylsilane, methylvinyldichlorosilane, hexylmethyldichlorosilane, dichlorotetramethyldisilane, dichloromethyloctylsilane, dichloro(isobutyl)(methyl)silane, 1,3-dichloro-1,1,3,3,-tetramethyldisiloxane and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane. In the present application, when the dichlorosilane monomer includes both a fluorine-containing dichlorosilane monomer and a fluorine-free dichlorosilane monomer, the molar ratio of the fluorine-containing dichlorosilane monomer to the fluorine-free dichlorosilane monomer is preferably 1:1.

[0046] In the present application, the dimethoxysilane monomer preferably further comprises a fluorine-free dimethoxysilane monomer; the fluorine-free dimethoxysilane monomer preferably comprises one or more of dimethoxydiphenylsilane, dimethoxydimethylsilane, dimethoxy(methyl)silane, dimethoxy(methyl)octylsilane, dimethoxy(methyl)octylsilane, isobutyldimethoxy(methyl)silane, diisopropyldimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, diisobutyldimethoxysilane and methylcyclohexyldimethoxysilane. When the dimethoxysilane monomer comprises both a fluorine-containing dimethoxysilane monomer and a fluorine-free dimethoxysilane monomer, the molar ratio of the fluorine-containing dimethoxysilane monomer to the fluorine-free dimethoxysilane monomer is preferably 1:1.

[0047] In the present application, when the silane monomer is a dimethoxysilane monomer, the reaction solution preferably further includes an acid catalyst; the acid catalyst preferably includes one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, p-toluenesulfonic acid, hydrofluoric acid, selenic acid, hypochlorous acid, trifluoromethanesulfonic acid and chloric acid. The polymerization of dimethoxysilane monomer is relatively difficult, and the present application adds an acid catalyst to the reaction solution to provide the protons required for the condensation reaction of the dimethoxysilane monomer and accelerate the reaction rate. In the present application, the molar ratio of the dimethoxysilane monomer to the acid catalyst is preferably (0.01-100):1, more preferably (0.1-99):1, further preferably (1-95):1, and further preferably (10-80):1.

[0048] In the present application, the organic solvent preferably includes one or more of dichloromethane, chloroform, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and N,N-dimethylsulfoxide. In the present application, the molar ratio of the silane monomer to the organic solvent is preferably (0.01-100):1, more preferably (0.1-99):1, further preferably (1-95):1, and even more preferably (10-80):1.

[0049] The present application has no special requirements for the preparation of the reaction solution, as long as the silane monomer is completely dissolved in the organic solvent.

[0050] After obtaining a hydroxyl-rich substrate and a reaction solution, the present application brings the reaction solution into contact with the hydroxyl-rich substrate, and the silane monomer is polymerized under the initiation of the hydroxyl groups on the substrate to form a linear polyfluorosilicone covalently bonded to the substrate, thereby obtaining a solid super-slippery surface.

[0051] In the present application, contacting the reaction solution with a hydroxyl-rich substrate preferably includes: immersing the hydroxyl-rich substrate in the reaction solution. In the present application, the immersion time is preferably 10s to 60min, more preferably 1 to 50min, and further preferably 10 to 40min. The present application adopts an immersion method to ensure that the hydroxyl groups on the surface of the substrate are fully in contact with the reaction solution so as to initiate polymerization into a dense monolayer. In the present application, when the silane monomer is dimethoxysilane, the immersion time is preferably short (10s to 60min), and the polymer chain growth is carried out during the process of volatilizing the solvent (drying) in the air; when the silane monomer is a dichlorosilane monomer, the immersion time is preferably long (30s to 60min), and the chain growth is carried out during the solution immersion stage.

[0052] When the silane monomer is a dichlorosilane monomer, after the contact, the present application preferably rinses the substrate after contact with the reaction solution with an organic solvent to form a solid super-slippery surface on the surface of the substrate;

[0053] When the silane monomer is dimethoxysilane, after the contact, the present application preferably dries the substrate after contact with the reaction solution, and then rinses it with an organic solvent to form a solid super-slippery surface on the surface of the substrate.

[0054] In the present application, the drying is preferably air-drying at room temperature. In the present application, during the drying process, the dimethoxysiloxane monomer in the reaction solution further undergoes polymerization reaction.

[0055] The present application provides a solid super-slippery surface obtained by the construction method described in the above scheme, the chemical composition of which is linear polyfluorosilicone, and the linear polyfluorosilicone is bonded to the substrate through a chemical covalent bond.

[0056] In this application, the solid-state superslippery surface is firmly bonded to the substrate via chemical covalent bonds. This solves the problem of lubricant loss in traditional biomimetic superslippery surfaces in underwater environments, providing longer-lasting biofouling resistance. The solid-state superslippery surface provided in this application has a linear structure and reliable underwater transparency, with an underwater visible light transmittance of over 95%.

[0057] The present application provides the application of the solid super-slip surface described in the above solution as a marine antifouling coating.

[0058] The solid super-slippery surface provided by the present application, its construction method and application are described in detail below in conjunction with the embodiments, but they should not be understood as limiting the scope of protection of the present application.

[0059] Example 1

[0060] Raw materials: glass slides, colorless transparent glass slides; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to pale yellow liquid that can be used to prepare reaction solutions of varying concentrations using toluene as a solvent;

[0061] (1) After ultrasonic cleaning of the glass slide in acetone, ethanol, and deionized water to remove impurities, the slide was immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 hour, rinsed with deionized water, and dried to obtain a glass sample with surface hydroxylation modification;

[0062] (2) dissolving dichloro(methyl)(3,3,3-trifluoropropyl)silane in toluene solvent to prepare a reaction solution, wherein the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane to toluene is 1:99, stirring thoroughly and then allowing to stand for use;

[0063] (5) The hydroxylated glass sample was immersed in the above reaction solution, taken out after 1 hour, and repeatedly rinsed with toluene to obtain a polyfluorosilicone-based solid supersmooth surface.

[0064] The polyfluorosilicone-based solid-state ultra-smooth surface glass sample prepared in Example 1 has polyfluorosilicone macromolecules grafted onto its surface. The reaction schematic diagram is shown in FIG5 .

[0065] The molecular structure of the solid super-slippery surface prepared in Example 1 was characterized, as shown in FIG1 , wherein 2899 cm -1 Corresponding to the stretching vibration peak of the CH bond on the methyl group of polyfluorosiloxane; at 1355cm -1 The characteristic peaks corresponding to the C-F bonds of polyfluorosilicone confirm the successful preparation of a polyfluorosilicone-based solid-state superslippery surface. Because FTIR analysis was performed after repeated washing of residual reactants with toluene, it was possible to confirm the grafting of polyfluorosilicone macromolecules onto the substrate.

[0066] Example 2

[0067] Raw materials: glass slides, colorless transparent glass slides; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations using toluene as a solvent; dimethyldichlorosilane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations using toluene as a solvent;

[0068] (1) After ultrasonic cleaning of the glass slide in acetone, ethanol, and deionized water to remove impurities, the slide was immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 hour, rinsed with deionized water, and dried to obtain a glass sample with surface hydroxylation modification;

[0069] (2) dissolving dichloro(methyl)(3,3,3-trifluoropropyl)silane and dimethyldichlorosilane in toluene solvent to prepare a reaction solution, wherein the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane to dimethyldichlorosilane and toluene is 1:1:98, stirring thoroughly and then allowing to stand for use;

[0070] (3) The hydroxylated glass sample was immersed in the above reaction solution, taken out after 1 hour, and rinsed with toluene to obtain a polyfluorosilicone-based solid superslippery surface.

[0071] The polyfluorosilicone-based solid-state ultra-smooth surface glass sample prepared in Example 2 has polyfluorosilicone macromolecules grafted onto its surface. The reaction schematic diagram is shown in FIG6 .

[0072] Example 3

[0073] Raw materials: glass slides, colorless transparent glass slides; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations using toluene as a solvent; diethyldichlorosilane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations using toluene as a solvent;

[0074] (1) After ultrasonic cleaning of the glass slide in acetone, ethanol, and deionized water to remove impurities, the slide was immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 hour, rinsed with deionized water, and dried to obtain a glass sample with surface hydroxylation modification;

[0075] (2) dissolving dichloro(methyl)(3,3,3-trifluoropropyl)silane and diethyldichlorosilane in toluene solvent to prepare a reaction solution, wherein the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane to diethyldichlorosilane and toluene is 1:1:98, stirring thoroughly and then allowing to stand for use;

[0076] (3) The hydroxylated glass sample was immersed in the above reaction solution, taken out after 1 hour, and rinsed with toluene to obtain a polyfluorosilicone-based solid superslippery surface.

[0077] The polyfluorosilicone-based solid-state ultra-smooth surface glass sample prepared in Example 3 has polyfluorosilicone macromolecules grafted onto its surface. The reaction schematic diagram is shown in FIG7 .

[0078] Example 4

[0079] Materials: glass slides, colorless transparent glass slides; 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of varying concentrations using isopropanol as a solvent; dimethoxy(methyl)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of varying concentrations using isopropanol as a solvent;

[0080] (1) After ultrasonic cleaning of the glass slide in acetone, ethanol, and deionized water to remove impurities, the slide was immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 hour, rinsed with deionized water, and dried to obtain a glass sample with surface hydroxylation modification;

[0081] (2) dissolving 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, dimethoxy(methyl)silane, and concentrated sulfuric acid in isopropanol solvent to prepare a reaction solution, wherein the molar ratio of 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, dimethoxy(methyl)silane, concentrated sulfuric acid, and isopropanol is 10:10:1:79, and the mixture is stirred thoroughly and allowed to stand for standby use;

[0082] (3) The hydroxylated glass sample was immersed in the above reaction solution for 10 minutes, taken out and placed in a room temperature environment, and then dried for 1 hour and rinsed with isopropanol and toluene in sequence to obtain a polyfluorosilicone-based solid super-smooth surface.

[0083] The polyfluorosilicone-based solid-state ultra-smooth surface glass sample prepared in Example 4 has polyfluorosilicone macromolecules grafted onto its surface. The reaction schematic diagram is shown in FIG8 .

[0084] Example 5

[0085] Materials: glass slides, colorless transparent glass slides; 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of varying concentrations using isopropyl alcohol as a solvent; diisopropyldimethoxysilane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of varying concentrations using isopropyl alcohol as a solvent;

[0086] (1) After ultrasonic cleaning of the glass slide in acetone, ethanol, and deionized water to remove impurities, the slide was immersed in 65% concentrated sulfuric acid, heated for 1 hour, rinsed, and dried to obtain a glass sample with surface hydroxylation modification;

[0087] (2) dissolving 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, diisopropyldimethoxysilane, and concentrated sulfuric acid in isopropanol solvent to prepare a reaction solution, wherein the molar ratio of 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, diisopropyldimethoxysilane, concentrated sulfuric acid, and isopropanol is 10:10:1:79, and the mixture is stirred thoroughly and allowed to stand for use;

[0088] (6) The hydroxylated glass sample was immersed in the above reaction solution for 10 minutes, taken out and placed in a room temperature environment, and rinsed with isopropanol and toluene in sequence after 1 hour to obtain a polyfluorosilicone-based solid super-smooth surface.

[0089] The polyfluorosilicone-based solid-state ultra-smooth surface glass sample prepared in Example 5 has polyfluorosilicone macromolecules grafted onto its surface. The reaction schematic diagram is shown in FIG9 .

[0090] Comparative Example 1

[0091] This comparative example sample was prepared by vapor deposition. Specifically, a glass slide was hydroxylated and placed in an autoclave. A certain amount of 1H,1H,2H,2H-perfluorodecyl-triethoxysilane (POTS) was added. The sample was heated at 120°C for 20 minutes, then the sample was taken out and the crude product on the glass surface was washed off to obtain a POTS-Glass sample.

[0092] Performance characterization:

[0093] The sliding properties of water droplets on the inclined polyfluorosilicone-based solid super-slippery surface were measured by a contact angle meter. Specifically, a water droplet (20 μL) was dropped on the polyfluorosilicone-based solid super-slippery surface prepared in Example 3 with an inclination of 10°, and then the contact angle meter was used to record the distance the droplet slid on the surface for a period of time.

[0094] As can be seen from Figure 2, the droplets can slide down on the super-slippery surface (SSS) prepared in Example 3. The droplets can slide stably and quickly. In contrast, the droplets on the untreated glass surface always stay at the initial position, indicating that the solid super-slippery surface has excellent super-slip properties. In addition, the droplets on the perfluorosilane-treated sample (POTS-Glass) always stay at the initial position, indicating that the SSS sample can provide a lower interaction force with water at the intermolecular interface than the hydrophobic treatment (fluorinated small molecule POTS) surface. This is due to the synergistic effect of the fluorinated groups on the SSS surface and the high flexibility of the polysiloxane molecular chain. Therefore, the SSS with polyfluorosiloxane grafted on the surface has the best protective performance.

[0095] Figure 3 is a fluorescent photograph of bacteria attached to the polyfluorosilicone-based solid super-smooth surface (SSS) constructed in Example 3, the control glass sample (Glass), and the control perfluorosilane-treated sample (POTS-Glass) after being immersed in a static Pseudoalteromonas culture solution for 3 days and 14 days. As can be seen from the pictures, whether it is immersed for 3 days or 14 days, the surface of the control glass sample has a large amount of bacteria attached, and the polyfluorosilicone-based solid super-smooth surface has only a small amount of bacteria attached; the amount of bacteria attached to the control perfluorosilane-treated sample (POTS-Glass) is less than that of the blank glass sample, indicating that the glass after hydrophobic treatment can inhibit bacterial attachment to a certain extent, but significantly more than the solid super-smooth surface (SSS). Therefore, the polyfluorosilicone-based solid super-smooth surface can effectively inhibit the attachment of bacteria on the surface, and has a long-term effect, thereby preventing the decline in the transmittance of the underwater optical window from the root.

[0096] Figure 4 is a comparison of the underwater visible light transmittance of the polyfluorosilicone-based solid supersmooth surface (SSS) constructed in Example 3 and the control glass sample (Glass) before and after the antifouling experiment. As can be seen from the figure, before the 14-day antifouling experiment, the polyfluorosilicone-based solid supersmooth surface (SSS) had an underwater transparency close to that of the control glass (Glass), demonstrating good underwater transparency. Furthermore, after the 14-day antifouling experiment, it still had reliable underwater visible light transmittance, confirming the reliability of the polyfluorosilicone-based solid supersmooth surface as an antifouling technology for underwater optical windows of marine instruments.

[0097] It can be seen from the above embodiments that the new polyfluorosilicone-based solid super-slippery surface provided by the present application achieves the effect of firm bonding between the lubricant and the substrate through chemical bonding, which solves the problem that the lubricant on the traditional bionic super-slippery surface is easily lost in the underwater environment, and has a longer-lasting performance in preventing and treating biological fouling, thereby making the surface lubricant extremely reliable and stable, and providing a solution to the long-term problem of bionic super-slippery surfaces in protecting against marine biological fouling.

[0098] The above is only a preferred embodiment of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present application. These improvements and modifications should also be regarded as the scope of protection of the present application.

Claims

1. A method for constructing a solid-state super-slippery surface, characterized in that, It includes the following steps: Perform surface hydroxylation modification on the substrate to obtain a substrate rich in hydroxyl groups; Provide a reaction solution; the reaction solution includes a silane monomer and an organic solvent; the silane monomer is a dichlorosilane monomer or a dimethoxysilane monomer; at least one of the dichlorosilane monomers is a fluorinated dichlorosilane monomer; at least one of the dimethoxysilane monomers is a fluorinated dimethoxysilane monomer; Contact the reaction solution with the substrate rich in hydroxyl groups. Under the initiation of the hydroxyl groups on the substrate, the silane monomers polymerize to form a linear polyfluorosiloxane covalently bonded to the substrate, obtaining a solid super-slippery surface.

2. The construction method according to claim 1, wherein, The fluorinated dichlorosilane monomer includes one or more of 1H,1H,2H,2H-perfluorodecylmethyldichlorosilane, 1H,1H,2H,2H-perfluorooctylmethyldichlorosilane, and dichloro(methyl)(3,3,3-trifluoropropyl)silane.

3. The construction method according to claim 1 or 2, characterized in that, The dichlorosilane monomer also includes a non-fluorinated dichlorosilane monomer; the non-fluorinated dichlorosilane monomer includes one or more of diisopropyldichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, dichlorodiethylsilane, dichlorodipropylsilane, dibutyldichlorosilane, dichloro(isobutyl)(methyl)silane, dichlorodipentylsilane, dichlorodihexylsilane, dichloro(methyl)(propyl)silane, dichloroethylmethylsilane, methylvinyldichlorosilane, hexylmethyldichlorosilane, dichlorotetramethyldisilane, dichloromethyloctylsilane, dichloro(isobutyl)(methyl)silane, 1,3-dichloro-1,1,3,3,-tetramethyldisiloxane, and 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane.

4. The construction method according to claim 3, characterized in that, The molar ratio of the fluorinated dichlorosilane monomer to the non-fluorinated dichlorosilane monomer is 1:

1.

5. The construction method according to claim 1, characterized in that, The fluorinated dimethoxysilane monomer includes 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and / or dimethoxybis(pentafluorophenyl)silane.

6. The construction method according to claim 1 or 5, characterized in that The dimethoxysilane monomer also includes a non-fluorinated dimethoxysilane monomer; the non-fluorinated dimethoxysilane monomer includes one or more of dimethoxydiphenylsilane, dimethoxydimethylsilane, dimethoxy(methyl)silane, dimethoxy(methyl)octylsilane, dimethoxy(methyl)octylsilane, isobutyldimethoxy(methyl)silane, diisopropyldimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, diisobutyldimethoxysilane, and methylcyclohexyldimethoxysilane.

7. The construction method according to claim 6, characterized in that The molar ratio of the fluorinated dimethoxysilane monomer to the non-fluorinated dimethoxysilane monomer is 1:

1.

8. The construction method according to claim 1, characterized in that, When the silane monomer is a dimethoxysilane monomer, an acid catalyst is further included in the reaction solution.

9. The construction method according to claim 8, wherein The acid catalyst includes one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, p-toluenesulfonic acid, hydrofluoric acid, selenic acid, hypochlorous acid, trifluoromethanesulfonic acid, and chloric acid.

10. The construction method according to claim 8 or 9, characterized in that, The molar ratio of the dimethoxysilane monomer to the acid catalyst is (0.01 - 100):

1.

11. The construction method according to claim 1, wherein, Contacting the reaction solution with the substrate rich in hydroxyl groups includes: immersing the substrate rich in hydroxyl groups in the reaction solution.

12. The construction method according to claim 11, wherein The immersion time is 10 s to 60 min.

13. The construction method according to claim 1, characterized in that The organic solvent includes one or more of dichloromethane, chloroform, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and N,N-dimethyl sulfoxide.

14. The solid super-slippery surface obtained by the construction method according to any one of claims 1 to 13, characterized in that, The chemical composition is linear polyfluorosiloxane, and the linear polyfluorosiloxane is bonded to the substrate through chemical covalent bonds.

15. Application of the solid super-slippery surface described in claim 14 as an anti-fouling coating for the ocean.

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