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

Abstract

The application provides a solid super-smooth surface and a construction method and application thereof, and relates to the technical field of marine antifouling. The solid super-smooth surface constructed by the application is composed of linear polyfluorosiloxane, the linear polyfluorosiloxane is combined with a substrate through a chemical covalent bond, the chemical covalent bond is firm, the problem that traditional biomimetic super-smooth surface lubricating oil is prone to loss in an underwater environment is solved, and the solid super-smooth surface has a longer performance of preventing and treating biological fouling. The solid super-smooth surface provided by the application has a linear structure and reliable underwater transparency, and the underwater visible light transmittance of the material can reach more than 95%.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of marine antifouling technology, and particularly relates to a solid super-slippery surface and a construction method and application thereof. BACKGROUND

[0002] The loss caused by marine biofouling is difficult to estimate every year, which seriously restricts the healthy development of the marine industry. With the rapid development of China's marine industry, the application demand of marine optical sensors (such as water quality monitoring instruments, underwater cameras, etc.) for monitoring the marine environment is also increasing, however, the biofouling on the surface of the optical window of the sensor will cause data errors, which seriously affects the data quality of the monitoring. It can be predicted that the development of reliable underwater optical window antifouling technology for marine instruments is of great significance to promote the progress of China's marine science and technology industry.

[0003] At present, there are mainly three methods for protecting the optical window of marine instruments from biofouling, one is to remove the attached microorganisms by a mechanical arm, but this method requires complex equipment and tedious maintenance, which limits its further application; the second is the chemical biocide antifouling method, which is currently the most commonly used antifouling method, including releasing organic biocides, placing copper sheets, etc. The toxic substances released by this method usually have adverse effects on the surrounding environment, which is 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 water. Therefore, developing a new type of green and environmentally friendly, zero-energy-consumption and range-free antifouling technology for the optical window of marine instruments is a very challenging scientific task, and it is also a topic of great concern to researchers.

[0004] Bionic (pitcher plant) super-slippery surface has attracted extensive attention due to its good antifouling performance. A large number of studies have shown that this type of antifouling technology does not release toxic substances and can effectively prevent the attachment of microorganisms, while maintaining a high underwater light transmittance and exhibiting excellent antifouling performance. However, the lubricating oil film of this surface is prone to loss in underwater environment, which greatly affects its antifouling ability. Therefore, how to ensure the long-term effectiveness of the antifouling ability is a technical problem that needs to be solved in the practical application of bionic super-slippery surface. SUMMARY

[0005] The present application aims to provide a solid super-slippery surface and a construction method and application thereof. The solid super-slippery surface constructed by the present application exhibits excellent antifouling performance while maintaining a high underwater light transmittance, and the antifouling ability is long-lasting.

[0006] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions:

[0007] The present application provides a construction method of a solid super-slippery surface, comprising the following steps:

[0008] surface hydroxylated modification is performed on the substrate to obtain a hydroxyl-rich substrate;

[0009] a reaction solution is provided; the reaction solution comprises silane monomers and an organic solvent; the silane monomers are dichlorosilane monomers or dimethoxysilane monomers; 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;

[0010] the reaction solution is contacted with the hydroxyl-rich substrate, and the silane monomers are polymerized under the initiation of hydroxyl groups on the substrate to form linear polyfluorosiloxane covalently bonded to the substrate, thereby obtaining a solid super-slippery surface.

[0011] Preferably, the fluorine-containing dichlorosilane monomers include one or more of 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane, 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane, and dichloro(methyl)(3,3,3-trifluoropropyl)silane.

[0012] Preferably, the dichlorosilane monomers further include non-fluorine-containing dichlorosilane monomers; the non-fluorine-containing dichlorosilane monomers include one or more of diisopropyldichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, dichlorodiethylsilane, dichlorodipropylsilane, dibutyldichlorosilane, dichloro(isobutyl)(methyl)silane, dichlorodipentylsilane, dichlorodihexylsilane, dichloro(methyl)(propyl)silane, dichloroethylmethylsilane, methylvinyl dichlorosilane, 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.

[0013] Preferably, the fluorine-containing dimethoxysilane monomers include 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and / or dimethoxybis(pentafluorophenyl)silane.

[0014] Preferably, the dimethoxysilane monomers further include non-fluorine-containing dimethoxysilane monomers; the non-fluorine-containing dimethoxysilane monomers include one or more of dimethoxydiphenylsilane, dimethoxydimethylsilane, dimethoxy(methyl)silane, dimethoxy(methyl)octylsilane, dimethoxy(methyl)octylsilane, isobutyl dimethoxy(methyl)silane, diisopropyldimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, diisobutyl dimethoxysilane, and methylcyclohexyldimethoxysilane.

[0015] Preferably, when the silane monomers are dimethoxysilane monomers, an acid catalyst is further included in the reaction solution.

[0016] Preferably, the acid catalyst comprises one or more of permanganic acid, hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, p-toluenesulfonic acid, hydrofluoric acid, selenic acid, hypochlorous acid, triflic acid and chloric acid.

[0017] Preferably, contacting the reaction solution with the hydroxyl-rich substrate comprises soaking the hydroxyl-rich substrate in the reaction solution.

[0018] The application provides a solid super-slippery surface obtained by the construction method described in the above scheme, and the chemical composition is linear polyfluorosiloxane, which is combined with the substrate through chemical covalent bond.

[0019] The application provides an application of the solid super-slippery surface described in the above scheme as a marine antifouling coating.

[0020] The application provides a construction method of a solid super-slippery surface, comprising the following steps: surface hydroxylation modification is performed on a substrate to obtain a hydroxyl-rich substrate; a reaction solution is provided; the reaction solution comprises silane monomers and an organic solvent; the silane monomers are dichlorosilane monomers or dimethoxysilane monomers; at least one monomer in the dichlorosilane monomers is a fluorine-containing dichlorosilane monomer; at least one monomer in the dimethoxysilane monomers is a fluorine-containing dimethoxysilane monomer; the reaction solution is contacted with the hydroxyl-rich substrate, and the silane monomers are polymerized under the initiation of hydroxyl groups on the substrate to form linear polyfluorosiloxane combined with the substrate through covalent bond, thereby obtaining a solid super-slippery surface.

[0021] The application utilizes the hydroxyl groups on the substrate to initiate the polymerization of silane monomers, so that linear polyfluorosiloxane macromolecules are formed while being covalently combined with the substrate, the chemical covalent bond is firm, the problem that the lubricating oil of the traditional biomimetic super-slippery surface is easily lost in the underwater environment is solved, and the solid super-slippery surface has a longer performance of preventing and controlling biological fouling. The solid super-slippery surface constructed by the application has a linear structure and reliable underwater transparency, and the underwater visible light transmittance of the material can be up to 95% or more.

[0022] The anti-fouling principle of the present application is that when the substrate surface is grafted with polyfluorosiloxane, the fluorine-containing groups in the polyfluorosiloxane and the high flexibility of the polysiloxane molecular chain synergistically act, specifically, the polysiloxane molecular chain has the characteristics of high fluidity, so the surface presents the "liquid-like" characteristics in the macroscopic, and the hydrophobic property of the lubricating oil makes the interaction between the water and the solid surface much smaller; meanwhile, the fluorine atom has a strong electron-withdrawing inductive effect, which can form a strong shielding effect on the side chain group, thereby limiting the sensitivity of the polyfluorosiloxane macromolecular chain to van der Waals interaction, so that the polyfluorosiloxane-based solid super-smooth surface has extremely low intermolecular interaction force, and the fouling material (fouling organism / fouling molecule) cannot present strong interaction force with it, and it is also difficult to directly contact with the original solid substrate, so that the fouling material is difficult to adhere to the surface.

[0023] The present application provides a simple construction method of the solid super-smooth surface, and the reaction conditions are mild and efficient. The underwater optical window prepared from the material has long-term marine biofouling prevention ability, and has good application prospect in the field of marine protection. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The FTIR spectrum of the polyfluorosiloxane-based solid super-smooth surface prepared in Example 1 of the present application;

[0025] Figure 2 The dynamic wetting diagram of the droplet on the polyfluorosiloxane-based solid super-smooth surface (SSS) constructed in Example 3, the control group glass sample (Glass) and the control group perfluorosilane treated sample (POTS-Glass) surface;

[0026] Figure 3 The bacterial adhesion fluorescence photos of the polyfluorosiloxane-based solid super-smooth surface (SSS) constructed in Example 3, the control group glass sample (Glass) and the control group perfluorosilane treated sample (POTS-Glass) after being soaked in the static Pseudomonas alternanans culture solution for 3 days and 14 days;

[0027] Figure 4 The underwater visible light transmittance comparison diagram of the polyfluorosiloxane-based solid super-smooth surface (SSS) constructed in Example 3 and the control group glass sample (Glass) before and after the anti-fouling experiment;

[0028] Figure 5 The reaction schematic diagram of the polyfluorosiloxane macromolecule grafted in Example 1;

[0029] Figure 6 The reaction schematic diagram of the polyfluorosiloxane macromolecule grafted in Example 2;

[0030] Figure 7 The reaction schematic diagram of the polyfluorosiloxane macromolecule grafted in Example 3;

[0031] Figure 8 Reaction scheme for grafting polyfluorosiloxane macromolecules for Example 4;

[0032] Figure 9 Reaction scheme for grafting polyfluorosiloxane macromolecules for Example 5. DETAILED DESCRIPTION

[0033] The application provides a method for constructing a solid super-smooth surface, comprising the following steps:

[0034] The surface of the substrate is modified by hydroxylation to obtain a substrate rich in hydroxyl groups.

[0035] A reaction solution is provided; the reaction solution comprises silane monomers and an organic solvent; the silane monomers are dichlorosilane monomers or dimethoxysilane monomers; 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.

[0036] The reaction solution is contacted with the substrate rich in hydroxyl groups, and the silane monomers are polymerized under the initiation of the hydroxyl groups on the substrate to form linear polyfluorosiloxane combined with the substrate by covalent bonds, thereby obtaining a solid super-smooth surface.

[0037] In the present application, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0038] The surface of the substrate is modified by hydroxylation to obtain a substrate rich in hydroxyl groups.

[0039] The substrate in the present application has no special requirements, and a suitable substrate can be selected according to actual needs, for example, glass, quartz, silicon wafer. The surface hydroxylation modification in the present application has no special requirements, and a large number of hydroxyl groups can be brought to the substrate by using a surface hydroxylation modification process well known in the art; in the examples of the present application, the glass sample after surface hydroxylation modification is obtained by immersing the glass slide in 65% concentrated sulfuric acid after ultrasonic cleaning in acetone, ethanol and deionized water to remove impurities, heating at 85°C for 1h and then rinsing with deionized water and drying.

[0040] A reaction solution is provided; the reaction solution comprises silane monomers and an organic solvent.

[0041] In the present application, the silane monomers are dichlorosilane monomers or dimethoxysilane monomers; 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.

[0042] 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; and the fluorine-containing dimethoxysilane monomer preferably includes 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and / or dimethoxybis(pentafluorophenyl)silane.

[0043] In the present application, the dichlorosilane monomer preferably further includes a non-fluorine-containing dichlorosilane monomer; and the non-fluorine-containing 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, methylvinyl-dichlorosilane, 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 the fluorine-containing dichlorosilane monomer and the non-fluorine-containing dichlorosilane monomer, the molar ratio of the fluorine-containing dichlorosilane monomer to the non-fluorine-containing dichlorosilane monomer is preferably 1:1.

[0044] In the present application, the dimethoxysilane monomer preferably further includes a non-fluorine-containing dimethoxysilane monomer; and the non-fluorine-containing dimethoxysilane monomer preferably 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. When the dimethoxysilane monomer includes both the fluorine-containing dimethoxysilane monomer and the non-fluorine-containing dimethoxysilane monomer, the molar ratio of the fluorine-containing dimethoxysilane monomer to the non-fluorine-containing dimethoxysilane monomer is preferably 1:1.

[0045] In the present application, when the silane monomer is dimethoxysilane monomer, the reaction solution preferably further comprises an acid catalyst; the acid catalyst preferably comprises 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. Dimethoxysilane monomer is difficult to polymerize, and the present application adds an acid catalyst to the reaction solution to provide the required protons for the polycondensation of dimethoxysilane monomer, thereby accelerating the reaction rate. In the present application, the molar ratio of dimethoxysilane monomer to acid catalyst is preferably (0.01-100):1, more preferably (0.1-99):1, further preferably (1-95):1, and more further preferably (10-80):1.

[0046] In the present application, the organic solvent preferably comprises one or more of dichloromethane, trichloromethane, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, tetrahydrofuran, methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide and N,N-dimethyl sulfoxide. In the present application, the molar ratio of silane monomer to organic solvent is preferably (0.01-100):1, more preferably (0.1-99):1, further preferably (1-95):1, and more further preferably (10-80):1.

[0047] The present application does not have special requirements for the preparation of the reaction solution, and it is only necessary to ensure that the silane monomer is completely dissolved in the organic solvent.

[0048] After obtaining the hydroxyl-rich substrate and the reaction solution, the present application contacts the reaction solution with the hydroxyl-rich substrate, and the silane monomer is polymerized under the initiation of the hydroxyl groups on the substrate to form linear polyfluorosiloxane which is covalently bonded to the substrate, thereby obtaining a solid super-smooth surface.

[0049] In the present application, contacting the reaction solution with the hydroxyl-rich substrate preferably comprises immersing the hydroxyl-rich substrate in the reaction solution. In the present application, the immersion time is preferably 10s-60min, more preferably 1-50min, and further preferably 10-40min. The present application uses immersion to ensure that the hydroxyl groups on the surface of the substrate are in sufficient contact with the reaction solution to initiate polymerization into a dense monolayer. In the present application, when the silane monomer is dimethoxysilane, the immersion time is preferably short (10s-60min), and the polymer chain is grown during the process of volatilizing the solvent (drying) in air; when the silane monomer is dichlorosilane monomer, the immersion time is preferably long (30s-60min), and the chain growth is performed during the solution immersion stage.

[0050] When the silane monomer is dichlorosilane monomer, after being contacted, the present application preferably rinses the substrate after contacting the reaction solution with an organic solvent to form a solid super-smooth surface on the surface of the substrate;

[0051] When the silane monomer is dimethoxysilane, the substrate after being contacted is preferably dried, then washed with an organic solvent to form a solid super-slippery surface on the surface of the substrate.

[0052] In the present application, the drying is preferably air drying at room temperature, and during the drying, the dimethoxysiloxane monomer in the reaction solution further undergoes a polymerization reaction.

[0053] The present application provides a solid super-slippery surface obtained by the construction method described in the above scheme, which is linear polyfluorosiloxane, and is combined with the substrate through a chemical covalent bond.

[0054] In the present application, the solid super-slippery surface is combined with the substrate through a chemical covalent bond, which is firm, and solves the problem that the lubricating oil of the traditional biomimetic super-slippery surface is easy to lose in the underwater environment, so that it has a longer performance of preventing and controlling biofouling. The solid super-slippery surface provided by the present application has a linear structure and reliable underwater transparency, and the underwater visible light transmittance can be up to 95% or more.

[0055] The present application provides an application of the solid super-slippery surface described in the above scheme as a marine antifouling coating.

[0056] The solid super-slippery surface, the construction method and the application thereof provided by the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0057] Example 1

[0058] Raw materials: glass slides, colorless transparent glass pieces; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to light yellow liquid, which can be prepared into a reaction solution of different concentrations with toluene as a solvent;

[0059] (1) After the glass slides were cleaned by ultrasonic in acetone, ethanol and deionized water to remove impurities, they were immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 h, then washed with deionized water and dried to obtain glass samples modified by hydroxylation on the surface;

[0060] (2) Dissolve dichloro(methyl)(3,3,3-trifluoropropyl)silane in toluene solvent to prepare a reaction solution, the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane to toluene is 1:99, and then stir well and stand for use;

[0061] (5) Immerse the glass samples modified by hydroxylation in the above reaction solution, take them out after 1 h, and then wash repeatedly with toluene to obtain a polyfluorosiloxane-based solid super-slippery surface.

[0062] The polyfluorosiloxane-based solid super-smooth surface glass sample prepared in Example 1 has polyfluorosiloxane macromolecules grafted on the surface, and the reaction schematic diagram is as shown in Figure 5 .

[0063] The molecular structure of the solid super-smooth surface prepared in Example 1 was characterized, as shown in Figure 1 -1 corresponding to the stretching vibration peak of C-H bond on the polyfluorosiloxane methyl; at 1355 cm -1 corresponding to the characteristic peak of polyfluorosiloxane C-F bond. It is proved that the polyfluorosiloxane-based solid super-smooth surface is successfully prepared. Since the FTIR test is carried out after the residual reactants are repeatedly washed with toluene, it can be proved that the polyfluorosiloxane macromolecules are grafted on the substrate.

[0064] Example 2

[0065] Raw materials: glass slides, colorless transparent glass pieces; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to light yellow liquid, which can be prepared into different concentration reaction solutions with toluene as solvent; dimethyldichlorosilane, a colorless to light yellow liquid, which can be prepared into different concentration reaction solutions with toluene as solvent;

[0066] (1) After the glass slides were ultrasonically cleaned in acetone, ethanol and deionized water to remove impurities, they were immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 h, then washed with deionized water and dried to obtain glass samples modified by surface hydroxylation;

[0067] (2) Dissolve dichloro(methyl)(3,3,3-trifluoropropyl)silane and dimethyldichlorosilane in toluene solvent to prepare reaction solution, the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane, dimethyldichlorosilane and toluene is 1:1:98, stir well and stand by;

[0068] (3) Immerse the glass sample modified by surface hydroxylation in the above reaction solution, take it out after 1 h, and wash it with toluene to obtain a polyfluorosiloxane-based solid super-smooth surface.

[0069] The polyfluorosiloxane-based solid super-smooth surface glass sample prepared in Example 2 has polyfluorosiloxane macromolecules grafted on the surface, and the reaction schematic diagram is as shown in Figure 6 .

[0070] Example 3

[0071] Raw materials: glass slides, colorless transparent glass pieces; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to light yellow liquid, which can be prepared into different concentration reaction solutions with toluene as solvent; diethyldichlorosilane, a colorless to light yellow liquid, which can be prepared into different concentration reaction solutions with toluene as solvent; ​

[0072] (1) The glass slides were cleaned by ultrasonic washing in acetone, ethanol and deionized water to remove impurities, then immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 h, rinsed with deionized water, and dried to obtain a glass sample modified by surface hydroxylation;

[0073] (2) Dichloro(methyl)(3,3,3-trifluoropropyl)silane and diethyldichlorosilane were dissolved in toluene solvent to prepare a reaction solution, and the molar ratio of dichloro(methyl)(3,3,3-trifluoropropyl)silane, diethyldichlorosilane and toluene was 1:1:98. After sufficient stirring, it was placed for standby;

[0074] (3) The glass sample modified by hydroxylation was immersed in the above reaction solution, and taken out after 1 h. It was rinsed with toluene to obtain a polyfluorosiloxane-based solid super-smooth surface.

[0075] The polyfluorosiloxane-based solid super-smooth surface glass sample prepared in Example 3 has polyfluorosiloxane macromolecules grafted on the surface, and the reaction schematic diagram is as shown in Figure 7 .

[0076] Example 4

[0077] Raw materials: glass slides, colorless transparent glass pieces; 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, a colorless to light yellow liquid, which can be prepared into a reaction solution of different concentrations with isopropanol as the solvent; dimethoxy(methyl)silane, a colorless to light yellow liquid, which can be prepared into a reaction solution of different concentrations with isopropanol as the solvent;

[0078] (1) The glass slides were cleaned by ultrasonic washing in acetone, ethanol and deionized water to remove impurities, then immersed in 65% concentrated sulfuric acid, heated at 85°C for 1 h, rinsed with deionized water, and dried to obtain a glass sample modified by surface hydroxylation;

[0079] (2) 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, dimethoxy(methyl)silane and concentrated sulfuric acid were dissolved in isopropanol solvent to prepare a reaction solution, and the molar ratio of 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, dimethoxy(methyl)silane, concentrated sulfuric acid and isopropanol was 10:10:1:79. After sufficient stirring, it was placed for standby;

[0080] (3) The glass sample modified by hydroxylation was immersed in the above reaction solution for 10 min, taken out and placed in a room temperature environment, and then rinsed with isopropanol and toluene in sequence to obtain a polyfluorosiloxane-based solid super-smooth surface.

[0081] The polyfluorosiloxane-based solid super-smooth surface glass sample prepared in Example 4 has polyfluorosiloxane macromolecules grafted on the surface, and the reaction schematic diagram is as shown in Figure 8 .

[0082] Example 5

[0083] Raw materials: glass slides, colorless transparent glass pieces; 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, a colorless to light yellow liquid, which can be prepared into a reaction solution of different concentrations with isopropanol as the solvent; diisopropyl dimethoxy silane, a colorless to light yellow liquid, which can be prepared into a reaction solution of different concentrations with isopropanol as the solvent;

[0084] (1) After the glass slides were cleaned multiple times by ultrasonic cleaning in acetone, ethanol and deionized water to remove impurities, they were immersed in 65% concentrated sulfuric acid, heated for 1 h, then rinsed and dried to obtain glass samples modified by surface hydroxylation;

[0085] (2) 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, diisopropyl dimethoxy silane and concentrated sulfuric acid were dissolved in isopropanol solvent to prepare a reaction solution, and the molar ratio of 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane, diisopropyl dimethoxy silane, concentrated sulfuric acid to isopropanol was 10:10:1:79. After sufficient stirring, it was placed for standby;

[0086] (6) The glass samples modified by hydroxylation were immersed in the above reaction solution for 10 min, taken out and placed in a room temperature environment, and then rinsed with isopropanol and toluene in sequence after 1 h to obtain a polyfluorosiloxane-based solid super-smooth surface.

[0087] The polyfluorosiloxane-based solid super-smooth surface glass sample prepared in Example 5 has polyfluorosiloxane macromolecules grafted on the surface, and the reaction schematic diagram is as shown in Figure 9 .

[0088] Comparative Example 1

[0089] This comparative sample was prepared by a gas deposition method. Specifically, after the glass slides were hydroxylated, a certain amount of 1H,1H,2H,2H-perfluorodecyl-triethoxysilane (POTS) was added to an autoclave, the sample was taken out after heating at 120°C for 20 minutes, and the crude product on the surface of the glass was washed off to prepare a POTS-Glass sample.

[0090] Performance characterization:

[0091] The sliding property of water droplets on the inclined polyfluorosiloxane-based solid super-smooth surface was measured by a contact angle measuring instrument. Specifically, a water droplet (20 μL) was dropped on the polyfluorosiloxane-based solid super-smooth surface prepared in Example 3 with an inclination of 10°, and then the distance of the liquid droplet on the surface after sliding for a period of time was recorded by the contact angle measuring instrument.

[0092] From the above results, it can be seen that the polyfluorosiloxane-based solid super-smooth surface prepared in Example 5 has a water contact angle of 0°, and the water droplet on the surface can slide on the surface without any resistance, which is a super-smooth surface. Figure 2It can be seen that the liquid drops on the super-slippery surface (SSS) prepared in Example 3 can slide by themselves, and the liquid drops can stably and quickly slide, in contrast, the liquid drops on the untreated glass surface always stay at the initial position, indicating that the solid super-slippery surface has excellent super-slippery performance. In addition, in contrast, the liquid drops on the perfluorosilane treated sample (POTS-Glass) surface always stay at the initial position, indicating that the SSS sample and water can provide lower interaction force on the intermolecular interface than the hydrophobic treated (fluorine-containing small molecule POTS) surface, because the fluorine-containing groups on the SSS surface and the high flexibility of the polysiloxane molecular chain synergistically work, and therefore the SSS with surface grafted polyfluorosiloxane has the best protection performance.

[0093] Figure 3 The bacterial adhesion fluorescence photos of the polyfluorosiloxane-based solid super-slippery surface (SSS) constructed in Example 3, the control group glass sample (Glass) and the control group perfluorosilane treated sample (POTS-Glass) after being soaked in the static Pseudomonas alternanans culture solution for 3 days and 14 days. It can be seen from the pictures that whether soaked for 3 days or 14 days, the control group glass sample surface has a large amount of bacterial adhesion, and the polyfluorosiloxane-based solid super-slippery surface has only a small amount of bacterial adhesion; the control group perfluorosilane treated sample (POTS-Glass) has less bacterial adhesion than the blank glass sample, indicating that the hydrophobic treated glass can inhibit bacterial adhesion to a certain extent, but is significantly more than the solid super-slippery surface (SSS), and therefore the polyfluorosiloxane-based solid super-slippery surface can effectively inhibit the adhesion of bacteria on the surface and has long-term effect, thereby preventing the decrease of the underwater optical window transmittance from the root.

[0094] Figure 4 The underwater visible light transmittance comparison chart of the polyfluorosiloxane-based solid super-slippery surface (SSS) constructed in Example 3 and the control group glass sample (Glass) before and after the antifouling experiment. It can be seen from the chart that before the 14-day antifouling experiment, the polyfluorosiloxane-based solid super-slippery surface (SSS) has close underwater transparency to the control group glass (Glass), showing good underwater transparency, and still has reliable underwater visible light transmittance after the 14-day antifouling experiment, confirming the reliability of the polyfluorosiloxane-based solid super-slippery surface as the antifouling technology of the underwater optical window of the marine instrument.

[0095] From the above examples, it can be seen that the novel polyfluorosiloxane-based solid super-slippery surface provided by the present application realizes the effect of firm combination of lubricating oil and substrate through chemical bonding, solves the problem that the lubricating oil of the traditional biomimetic super-slippery surface is easy to lose in the underwater environment, has longer performance of preventing and treating biological fouling, and therefore the surface lubricating oil has extremely reliable stability, thereby providing a solution to the long-term problem of the biomimetic super-slippery surface in the protection against marine biological fouling.

[0096] The above description is only the preferred embodiment of the present application, it should be pointed out that for those skilled in the art, without departing from the principles of the present application, can make several improvements and refinements, these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for constructing a solid super-slippery surface, characterized in that, The method comprises the following steps: surface hydroxyl modification is performed on the substrate to obtain a hydroxyl-rich substrate; a reaction solution is provided; the reaction solution comprises silane monomers and an organic solvent; the silane monomers are dichlorosilane monomers; the dichlorosilane monomers comprise fluorine-containing dichlorosilane monomers and non-fluorine-containing dichlorosilane monomers; the molar ratio of the fluorine-containing dichlorosilane monomers to the non-fluorine-containing dichlorosilane monomers is 1:1; the fluorine-containing dichlorosilane monomers comprise one or more of 1H, 1H, 2H, 2H-perfluorodecylmethyldichlorosilane, 1H, 1H, 2H, 2H-perfluorooctylmethyldichlorosilane, and dichloro(methyl)(3,3,3-trifluoropropyl)silane; the non-fluorine-containing dichlorosilane monomers comprise one or more of diisopropyldichlorosilane, diphenyldichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, dichloro(isobutyl)(methyl)silane, dipentyldichlorosilane, dihexyldichlorosilane, dichloro(methyl)(propyl)silane, dichloroethylmethylsilane, methylvinyl-dichlorosilane, 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; the reaction solution is brought into contact with the hydroxyl-rich substrate, and the silane monomers are polymerized under the initiation of the hydroxyl groups on the substrate to form linear polyfluorosiloxane that is combined with the substrate through a covalent bond, thereby obtaining a solid super-smooth surface.

2. The construction method of claim 1, wherein, The reaction solution is brought into contact with the hydroxyl-rich substrate by immersing the hydroxyl-rich substrate in the reaction solution.

3. The solid superamphiphobic surface obtained by the construction method according to any one of claims 1-2, characterized in that, The chemical composition is linear polyfluorosiloxane that is combined with the substrate through a chemical covalent bond.

4. Use of the solid super-smooth surface of claim 3 as a marine antifouling coating.

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