WO2025152302A1 - 一种固态超滑表面及其构建方法和应用 - Google Patents

一种固态超滑表面及其构建方法和应用

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Publication number
WO2025152302A1
WO2025152302A1 PCT/CN2024/092239 CN2024092239W WO2025152302A1 WO 2025152302 A1 WO2025152302 A1 WO 2025152302A1 CN 2024092239 W CN2024092239 W CN 2024092239W WO 2025152302 A1 WO2025152302 A1 WO 2025152302A1
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WO
WIPO (PCT)
Prior art keywords
monomer
silane
fluorine
methyl
dimethoxysilane
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Pending
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PCT/CN2024/092239
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English (en)
French (fr)
Inventor
张鹏
王文焕
鲍玖文
孙燕群
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Qingdao University of Technology
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Qingdao University of Technology
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Application filed by Qingdao University of Technology filed Critical Qingdao University of Technology
Publication of WO2025152302A1 publication Critical patent/WO2025152302A1/zh
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • 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.
  • the fluorine-containing dimethoxysilane monomer includes 3,3,3-trifluoropropyl(methyl)(dimethoxy)silane and/or dimethoxybis(pentafluorophenyl)silane.
  • the reaction solution further comprises an acid catalyst.
  • contacting the reaction solution with the hydroxyl-rich substrate comprises: immersing the hydroxyl-rich substrate in the reaction solution.
  • the present application provides the application of the solid super-slippery surface described in the above scheme as a marine antifouling coating.
  • 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; the reaction solution is brought into contact with a hydroxyl-rich substrate, and the silane monomer is polymerized 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.
  • the present application uses the hydroxyl groups on the substrate to initiate the polymerization reaction of silane monomers, thereby forming a linear polyfluorosilicone macromolecule and covalently bonding it to the substrate.
  • the chemical covalent bond is strong, which solves the problem that the lubricant on the traditional bionic super-slippery surface is easy to lose in the underwater environment, making it have a longer-lasting performance in preventing and controlling biological fouling.
  • the solid super-slippery surface constructed by the present application is a linear structure with reliable underwater transparency. The underwater visible light transmittance of the material can reach more than 95%.
  • the antifouling principle of the present application is: after the surface of the substrate is grafted with polyfluorosilicone, the fluorine-containing groups in the polyfluorosilicone and the highly flexible polysiloxane molecular chains work synergistically.
  • the polysiloxane molecular chains have the characteristics of high fluidity, so the surface presents "liquid-like" properties on a macro scale, and the hydrophobic properties of the lubricating oil make the interaction between it and water much smaller than that of the solid surface; at the same time, the fluorine atoms have a strong electron-withdrawing induction effect, which can form a strong shielding effect on the side chain groups, thereby limiting the sensitivity of the polyfluorosilicone macromolecular chains to van der Waals interactions, making the polyfluorosilicone-based solid super-slippery surface It has extremely low intermolecular interaction forces, and fouling substances (fouling organisms/fouling molecules) cannot have strong interaction forces with it. At the same time, it is difficult for the fouling substances to directly contact with the original solid substrate, which ultimately makes it difficult for the fouling substances to adhere to the surface.
  • the solid super-smooth surface construction method provided in the present 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.
  • FIG1 is a FTIR spectrum of a polyfluorosilicone-based solid superslippery surface prepared in Example 1 of the present application;
  • FIG2 is a dynamic wettability diagram of a droplet on a polyfluorosilicone-based solid superslippery surface (SSS) constructed in Example 3, a control group glass sample (Glass), and a control group perfluorosilane-treated sample (POTS-Glass);
  • SSS polyfluorosilicone-based solid superslippery surface
  • FIG3 is a fluorescence photograph of bacteria attachment on the polyfluorosilicone-based solid superslippery 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 culture solution of Pseudoalteromonas for 3 days and 14 days;
  • SSS polyfluorosilicone-based solid superslippery surface
  • FIG4 is a comparison diagram of underwater visible light transmittance of the polyfluorosilicone-based solid superslippery surface (SSS) constructed in Example 3 and the control group glass sample (Glass) before and after the antifouling experiment;
  • SSS polyfluorosilicone-based solid superslippery surface
  • FIG5 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 1;
  • FIG6 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 2.
  • FIG7 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 3.
  • FIG8 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 4.
  • FIG. 9 is a schematic diagram of the reaction of grafting polyfluorosilicone macromolecules in Example 5.
  • the present application provides a method for constructing a solid super-slippery surface, comprising the following steps:
  • 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;
  • 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
  • the dimethoxysilane monomer preferably also includes a fluorine-free dimethoxysilane monomer; the fluorine-free dimethoxysilane monomer preferably includes dimethoxydiphenylsilane, dimethoxy One or more of dimethylsilane, dimethoxy(methyl)silane, dimethoxy(methyl)octylsilane, dimethoxy(methyl)octylsilane, isobutyldimethoxy(methyl)silane, diisopropyldimethoxysilane, 3-mercaptopropyl(dimethoxy)methylsilane, diisobutyldimethoxysilane and methylcyclohexyldimethoxysilane.
  • the fluorine-free dimethoxysilane monomer preferably includes dimethoxydiphenylsilane, dimethoxy One or more of dimethylsilane, dimethoxy(methyl)silane, dim
  • the dimethoxysilane monomer includes 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.
  • the reaction solution preferably also 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 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.
  • an acid catalyst is added to the reaction solution to provide the protons required for the condensation reaction of the dimethoxysilane monomer and accelerate the reaction rate.
  • the present application has no special requirements for the preparation of the reaction solution, and it is sufficient to ensure that the silane monomer is completely dissolved in the organic solvent.
  • the present application contacts the reaction solution with the hydroxyl-rich substrate, and the silane monomer polymerizes under the initiation of the hydroxyl groups on the substrate to form a linear polyfluorosiloxane covalently bonded to the substrate, thereby obtaining a solid super-slippery surface.
  • contacting the reaction solution with the hydroxyl-rich substrate preferably includes: immersing the hydroxyl-rich substrate in the reaction solution.
  • the immersion time is preferably 10s to 60min, more preferably 1 to 50min, and further preferably 10 to 40min.
  • the present application adopts the 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 monomer.
  • the immersion time is preferably short (10s to 60min), and the polymer chain growth is carried out during the process of evaporating the solvent (drying) in the air;
  • the silane monomer is dichlorosilane monomer
  • the immersion time is preferably long (30s to 60min), and the chain growth is carried out during the solution immersion stage.
  • the present application provides the application of the solid super-slippery surface described in the above scheme as a marine antifouling coating.
  • Raw materials glass slide, colorless transparent glass slide; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations with toluene as solvent;
  • 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 .
  • the molecular structure of the solid super-smooth surface prepared in Example 1 was characterized, as shown in Figure 1, where 2899 cm -1 corresponds to the stretching vibration peak of the CH bond on the polyfluorosilicone methyl group; 1355 cm -1 corresponds to the characteristic peak of the CF bond of the polyfluorosilicone.
  • the successful preparation of the polyfluorosilicone-based solid super-smooth surface was confirmed. Since the FTIR test was performed after the residual reactants were repeatedly rinsed with toluene, it was possible to confirm that the polyfluorosilicone macromolecules were grafted on the substrate.
  • Raw materials glass slide, colorless transparent glass slide; dichloro(methyl)(3,3,3-trifluoropropyl)silane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations with toluene as solvent; dimethyldichlorosilane, a colorless to pale yellow liquid, which can be used to prepare reaction solutions of different concentrations with toluene as solvent;
  • This comparative 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, and the sample was taken out after heating at 120°C for 20 minutes and the crude product on the glass surface was washed off to obtain a POTS-Glass sample.
  • POTS 1H,1H,2H,2H-perfluorodecyl-triethoxysilane
  • the sliding property of water droplets on the inclined polyfluorosilicone-based solid super-slippery surface was measured by a contact angle meter. Specifically, a water droplet (20 ⁇ L) 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 of the droplet after sliding on the surface for a period of time.
  • the droplets can slide down on the super-slippery surface (SSS) prepared in Example 3 by themselves, and the droplets can slide stably and quickly.
  • 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.
  • the droplets on the surface of the sample treated with perfluorosilane (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 surface grafted polyfluorosilicone has the best protective performance.
  • Figure 3 is a fluorescent photograph of bacteria attachment of the polyfluorosilicone-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 immersed in a static culture solution of Pseudoalteromonas for 3 days and 14 days.
  • SSS polyfluorosilicone-based solid super-smooth surface
  • 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 group glass sample (Glass) before and after the antifouling experiment. It can be seen from the figure that before the 14-day antifouling experiment, the polyfluorosilicone-based solid supersmooth surface (SSS) had an underwater transparency close to that of the control group glass (Glass), showing good underwater transparency, and after 14 days of antifouling experiments, it still had a 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.
  • SSS polyfluorosilicone-based solid supersmooth surface
  • the new polyfluorosilicone-based solid super-smooth surface achieved 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-smooth surface is easily lost in the underwater environment, and has a longer-lasting performance in preventing and controlling biological fouling, thereby making the surface lubricant have extremely reliable stability, and provides a solution to the problem of the long-term effectiveness of bionic super-smooth surfaces in protecting against marine biological fouling.

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Abstract

本申请提供了一种固态超滑表面及其构建方法和应用，涉及海洋防污技术领域。本申请构建的固态超滑表面化学组成为线性聚氟硅氧烷，所述线性聚氟硅氧烷与基底之间通过化学共价键结合，化学共价键结合牢固，解决了传统仿生超滑表面润滑油在水下环境中容易流失的问题，使其具有更长久的防治生物污损的性能。本申请提供的固态超滑表面为线性结构，具有可靠的水下透明性，该材料水下可见光透过率最高可达95％以上。

Description

一种固态超滑表面及其构建方法和应用
本申请要求于2024年01月19日提交中国专利局、申请号为202410080058.5、发明名称为“一种固态超滑表面及其构建方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及海洋防污技术领域，尤其涉及一种固态超滑表面及其构建方法和应用。
背景技术
全球每年因海洋生物污损所产生的损失是难以估算的，严重制约着海洋产业的健康发展。随着我国海洋产业飞速发展，海洋光学传感器(如水质监测仪器、水下摄像机等)监测海洋环境的应用需求也日渐增多，然而传感器光学窗口表面产生的生物污损会造成数据误差，严重影响到其监测的数据质量。可以预见，开发可靠的海洋仪器水下光学窗口防污技术对于促进我国海洋科技产业的进步具有重要意义。
目前针对海洋仪器光学窗口生物污损的防护方法主要有三种，一是机械臂刮除法去除已附着的微生物，但该方法需要复杂的设备和繁琐的维护保养，限制了其进一步应用；二是化学杀生剂防污法，是目前应用较多的防污方法，包括释放有机杀生剂、旁置铜片等方式，该方法释放的毒性物质通常会对周边环境造成不良影响，不利于海洋生态的可持续发展；三是光催化法，然而该方法的有效使用范围仅能维持在水面下1米以内，无法在较深水域实现有效防护。因此，研发一种绿色环保、零能耗且无使用范围限制的新型海洋仪器光学窗口防污技术，是一项极具挑战的科学任务，也是研究人员十分关注的课题。
仿生(猪笼草)超滑表面因具有良好的防污性能而受到了广泛的关注，大量研究表明了该类防污技术不释放有毒物质且能够有效阻止微生物的附着，在维持较高水下透光率的同时展示出了优异的防污性能，但该表面的润滑油膜在水下环境中易发生流失，从而使其防污能力受到很大的影响，如何确保防污能力的长效性是仿生超滑表面在实用当中亟待解决的技术问题。
发明内容
本申请的目的在于提供一种固态超滑表面及其构建方法和应用。本申请构建的固态超滑表面在维持较高水下透光率的同时展示出了优异的防污性能，且防污能力具有长效性。
为了实现上述发明目的，本申请提供以下技术方案：
本申请提供了一种固态超滑表面的构建方法，包括以下步骤：
对基底进行表面羟基化修饰，得到富含羟基的基底；
提供反应溶液；所述反应溶液包括硅烷单体和有机溶剂；所述硅烷单体为二氯硅烷单体或二甲氧基硅烷单体；所述二氯硅烷单体中至少有一种单体为含氟二氯硅烷单体；所述二甲氧基硅烷单体中至少有一种单体为含氟二甲氧基硅烷单体；
使所述反应溶液与富含羟基的基底接触，在基底上羟基的引发下所述硅烷单体发生聚合，形成与基底通过共价键结合的线性聚氟硅氧烷，得到固态超滑表面。
优选的，所述含氟二氯硅烷单体包括1H,1H,2H,2H-全氟癸基甲基二氯硅烷、1H,1H,2H,2H-全氟辛基甲基二氯硅烷和二氯(甲基)(3,3,3-三氟丙基)硅烷中的一种或多种。
优选的，所述二氯硅烷单体还包括不含氟二氯硅烷单体；所述不含氟二氯硅烷单体包括二异丙基二氯硅烷、二苯二氯硅烷、二甲基二氯硅烷、二氯二乙基硅烷、二氯二丙基硅烷、二丁基二氯硅烷、二氯(异丁基)(甲基)硅、二氯二戊基硅烷、二氯二己基硅烷、二氯(甲基)(丙基)硅烷、二氯乙基甲基硅烷、甲基乙烯基二氯硅烷、己基甲基二氯硅烷、二氯四甲基二硅烷、二氯甲基辛基硅烷、二氯(异丁基)(甲基)硅、1,3-二氯-1,1,3,3,-四甲基二硅氧烷和1,3-双(氯甲基)-1,1,3,3-四甲基二硅氧烷中的一种或多种。
优选的，所述含氟二甲氧基硅烷单体包括3,3,3-三氟丙基(甲基)(二甲氧基)硅烷和/或二甲氧基双(五氟苯基)硅烷。
优选的，所述二甲氧基硅烷单体还包括不含氟二甲氧基硅烷单体；所述不含氟二甲氧基硅烷单体包括二甲氧基二苯基硅烷、二甲氧基二甲基硅烷、二甲氧基(甲基)硅烷、二甲氧基(甲基)辛基硅、二甲氧基(甲基)辛基硅、异丁 基二甲氧基(甲基)硅烷、二异丙基二甲氧基硅烷、3-巯基丙基(二甲氧基)甲基硅烷、二异丁基二甲氧基硅烷和甲基环己基二甲氧基硅烷中的一种或多种。
优选的，当所述硅烷单体为二甲氧基硅烷单体，所述反应溶液中还包括酸催化剂。
优选的，所述酸催化剂包括高锰酸、盐酸、硫酸、硝酸、高氯酸、对甲苯磺酸、氢氟酸、硒酸、次氯酸、三氟甲磺酸和氯酸中的一种或多种。
优选的，使所述反应溶液与富含羟基的基底接触包括：将富含羟基的基底浸泡到反应溶液中。
本申请提供了上述方案所述构建方法得到的固态超滑表面，化学组成为线性聚氟硅氧烷，所述线性聚氟硅氧烷与基底之间通过化学共价键结合。
本申请提供了上述方案所述固态超滑表面作为海洋防污涂层的应用。
本申请提供了一种固态超滑表面的构建方法，包括以下步骤：对基底进行表面羟基化修饰，得到富含羟基的基底；提供反应溶液；所述反应溶液包括硅烷单体和有机溶剂；所述硅烷单体为二氯硅烷单体或二甲氧基硅烷单体；所述二氯硅烷单体中至少有一种单体为含氟二氯硅烷单体；所述二甲氧基硅烷单体中至少有一种单体为含氟二甲氧基硅烷单体；使所述反应溶液与富含羟基的基底接触，在基底上羟基的引发下所述硅烷单体发生聚合，形成与基底通过共价键结合的线性聚氟硅氧烷，得到固态超滑表面。
本申请利用基底上羟基引发硅烷单体发生聚合反应，从而在形成线性聚氟硅氧烷大分子的同时使其与基底产生共价键结合，化学共价键结合牢固，解决了传统仿生超滑表面润滑油在水下环境中容易流失的问题，使其具有更长久的防治生物污损的性能。本申请构建的固态超滑表面为线性结构，具有可靠的水下透明性，该材料水下可见光透过率最高可达95％以上。
本申请的防污原理为：当基底表面接枝聚氟硅氧烷后，聚氟硅氧烷中的含氟基团与聚硅氧烷分子链高度柔顺性协同作用，具体的，聚硅氧烷分子链具有高度流动性的特点，因此该表面在宏观上呈现“类液体”特性，其润滑油的疏水特性使之与水之间的相互作用远小于固体表面；同时氟原子具有较强的吸电子诱导效应，对侧链基团能够形成较强的屏蔽效应，进而限制聚氟硅氧烷大分子链对范德华相互作用的敏感性，使得聚氟硅氧烷基固态超滑表面 具有极低的分子间相互作用力，污损物质(污损生物/污损分子)无法与之呈现强相互作用力，同时又难以与原固体基底之间直接接触，最终导致污损物质难以附着到该表面上。
本申请提供的固态超滑表面的构建方法简单，反应条件温和高效，以该材料制备的水下光学窗口具备长效的海洋生物污损防护能力，在海洋防护领域具有良好的应用前景。
附图说明
图1为本申请实施例1制备的聚氟硅氧烷基固态超滑表面的FTIR谱图；
图2为液滴在实施例3构建的聚氟硅氧烷基固态超滑表面(SSS)与对照组玻璃样品(Glass)和对照组全氟硅烷处理的样品(POTS-Glass)表面的动态润湿性图；
图3为实施例3构建的聚氟硅氧烷基固态超滑表面(SSS)与对照组玻璃样品(Glass)和对照组全氟硅烷处理的样品(POTS-Glass)在静态的假交替单胞菌培养液中浸泡3天和14天后的细菌附着荧光照片；
图4为实施例3构建的聚氟硅氧烷基固态超滑表面(SSS)与对照组玻璃样品(Glass)在防污实验前后的水下可见光透光率对比图；
图5为实施例1接枝聚氟硅氧烷大分子的反应示意图；
图6为实施例2接枝聚氟硅氧烷大分子的反应示意图；
图7为实施例3接枝聚氟硅氧烷大分子的反应示意图；
图8为实施例4接枝聚氟硅氧烷大分子的反应示意图；
图9为实施例5接枝聚氟硅氧烷大分子的反应示意图。
具体实施方式
本申请提供了一种固态超滑表面的构建方法，包括以下步骤：
对基底进行表面羟基化修饰，得到富含羟基的基底；
提供反应溶液；所述反应溶液包括硅烷单体和有机溶剂；所述硅烷单体为二氯硅烷单体或二甲氧基硅烷单体；所述二氯硅烷单体中至少有一种单体为含氟二氯硅烷单体；所述二甲氧基硅烷单体中至少有一种单体为含氟二甲氧基硅烷单体；
使所述反应溶液与富含羟基的基底接触，在基底上羟基的引发下所述硅 烷单体发生聚合，形成与基底通过共价键结合的线性聚氟硅氧烷，得到固态超滑表面。
在本申请中，未经特殊说明，所用原料均为本领域熟知的市售商品。
本申请对基底进行表面羟基化修饰，得到富含羟基的基底。
本申请对所述基底没有特殊要求，可以根据实际需求选择合适的基底，具体如：玻璃、石英、硅片。本申请对所述表面羟基化修饰没有特殊的要求，采用本领域熟知的表面羟基化修饰过程，能够使基底带上大量羟基即可；在本申请的实施例中，具体是将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，85℃加热1h后用去离子水冲洗，烘干，获得表面羟基化修饰后的玻璃样品。
本申请提供反应溶液；所述反应溶液包括硅烷单体和有机溶剂。
在本申请中，所述硅烷单体为二氯硅烷单体或二甲氧基硅烷单体；所述二氯硅烷单体中至少有一种单体为含氟二氯硅烷单体；所述二甲氧基硅烷单体中至少有一种单体为含氟二甲氧基硅烷单体。
在本申请中，所述含氟二氯硅烷单体优选包括1H,1H,2H,2H-全氟癸基甲基二氯硅烷、1H,1H,2H,2H-全氟辛基甲基二氯硅烷和二氯(甲基)(3,3,3-三氟丙基)硅烷中的一种或多种；所述含氟二甲氧基硅烷单体优选包括3,3,3-三氟丙基(甲基)(二甲氧基)硅烷和/或二甲氧基双(五氟苯基)硅烷。
在本申请中，所述二氯硅烷单体优选还包括不含氟二氯硅烷单体；所述不含氟二氯硅烷单体优选包括二异丙基二氯硅烷、二苯二氯硅烷、二甲基二氯硅烷、二氯二乙基硅烷、二氯二丙基硅烷、二丁基二氯硅烷、二氯(异丁基)(甲基)硅、二氯二戊基硅烷、二氯二己基硅烷、二氯(甲基)(丙基)硅烷、二氯乙基甲基硅烷、甲基乙烯基二氯硅烷、己基甲基二氯硅烷、二氯四甲基二硅烷、二氯甲基辛基硅烷、二氯(异丁基)(甲基)硅、1,3-二氯-1,1,3,3,-四甲基二硅氧烷和1,3-双(氯甲基)-1,1,3,3-四甲基二硅氧烷中的一种或多种。在本申请中，当所述二氯硅烷单体同时包括含氟二氯硅烷单体和不含氟二氯硅烷单体时，所述含氟二氯硅烷单体和不含氟二氯硅烷单体的摩尔比优选为1:1。
在本申请中，所述二甲氧基硅烷单体优选还包括不含氟二甲氧基硅烷单体；所述不含氟二甲氧基硅烷单体优选包括二甲氧基二苯基硅烷、二甲氧基 二甲基硅烷、二甲氧基(甲基)硅烷、二甲氧基(甲基)辛基硅、二甲氧基(甲基)辛基硅、异丁基二甲氧基(甲基)硅烷、二异丙基二甲氧基硅烷、3-巯基丙基(二甲氧基)甲基硅烷、二异丁基二甲氧基硅烷和甲基环己基二甲氧基硅烷中的一种或多种。当所述二甲氧基硅烷单体同时包括含氟二甲氧基硅烷单体和不含氟二甲氧基硅烷单体时，所述含氟二甲氧基硅烷单体和不含氟二甲氧基硅烷单体的摩尔比优选为1:1。
在本申请中，当所述硅烷单体为二甲氧基硅烷单体时，所述反应溶液中优选还包括酸催化剂；所述酸催化剂优选包括高锰酸、盐酸、硫酸、硝酸、高氯酸、对甲苯磺酸、氢氟酸、硒酸、次氯酸、三氟甲磺酸和氯酸中的一种或多种。二甲氧基硅烷单体聚合难度较大，本申请在反应溶液中添加酸催化剂，为二甲氧基硅烷单体的缩聚提供反应所需的质子，加速反应速率。在本申请中，所述二甲氧基硅烷单体与酸催化剂的摩尔比优选为(0.01～100)：1，更优选为(0.1～99)：1，进一步优选为(1～95)：1，更进一步优选为(10～80)：1。
在本申请中，所述有机溶剂优选包括二氯甲烷、三氯甲烷、戊烷、己烷、庚烷、环己烷、苯、甲苯、二甲苯、氯苯、二氯苯、四氢呋喃、甲醇、乙醇、异丙醇、正丁醇、N,N-二甲基甲酰胺和N,N-二甲基亚砜的一种或多种。在本申请中，所述硅烷单体与有机溶剂的摩尔比优选为(0.01～100)：1，更优选为(0.1～99)：1，进一步优选为(1～95)：1，更进一步优选为(10～80)：1。
本申请对所述反应溶液的制备没有特殊要求，确保硅烷单体完全溶于有机溶剂即可。
得到富含羟基的基底和反应溶液后，本申请使所述反应溶液与富含羟基的基底接触，在基底上羟基的引发下所述硅烷单体发生聚合，形成与基底通过共价键结合的线性聚氟硅氧烷，得到固态超滑表面。
在本申请中，使所述反应溶液与富含羟基的基底接触优选包括：将富含羟基的基底浸泡到反应溶液中。在本申请中，所述浸泡的时间优选为10s～60min，更优选为1～50min，进一步优选为10～40min。本申请采用浸泡的方式，确保基底表面羟基充分与反应溶液接触，以便引发聚合成致密的单 分子层。在本申请中，当硅烷单体为二甲氧基硅烷时，优选浸泡时间短(10s～60min)，在空气中挥发溶剂(干燥)的过程中进行高分子链增长；当硅烷单体为二氯硅烷单体，优选浸泡时间长(30s～60min)，在溶液浸泡阶段进行链增长。
当硅烷单体为二氯硅烷单体时，待接触后，本申请优选将接触反应溶液后的基底用有机溶剂冲洗，在基底表面形成固态超滑表面；
当硅烷单体为二甲氧基硅烷时，待接触后，本申请优选将接触反应溶液后的基底进行干燥，然后用有机溶剂冲洗，在基底表面形成固态超滑表面。
在本申请中，所述干燥优选为室温晾干，本申请在所述干燥过程中，反应溶液中的二甲氧基硅氧烷单体进一步发生聚合反应。
本申请提供了上述方案所述构建方法得到的固态超滑表面，化学组成为线性聚氟硅氧烷，所述线性聚氟硅氧烷与基底之间通过化学共价键结合。
在本申请中，所述固态超滑表面通过化学共价键与基底结合，结合牢固，解决了传统仿生超滑表面润滑油在水下环境中容易流失的问题，使其具有更长久的防治生物污损的性能。本申请提供的固态超滑表面为线性结构，具有可靠的水下透明性，水下可见光透过率最高可达95％以上。
本申请提供了上述方案所述固态超滑表面作为海洋防污涂层的应用。
下面结合实施例对本申请提供的固态超滑表面及其构建方法和应用进行详细的说明，但是不能把它们理解为对本申请保护范围的限定。
实施例1
原料：载玻片，无色透明玻璃片；二氯(甲基)(3,3,3-三氟丙基)硅烷，一种无色至淡黄色液体，能够以甲苯为溶剂配制不同浓度反应溶液；
(1)将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，85℃加热1h后用去离子水冲洗，烘干，获得表面羟基化修饰后的玻璃样品；
(2)将二氯(甲基)(3,3,3-三氟丙基)硅烷溶解在甲苯溶剂中，配制反应溶液，二氯(甲基)(3,3,3-三氟丙基)硅烷与甲苯的摩尔比为1:99，充分搅拌后静置备用；
(5)将羟基化修饰后的玻璃样品浸入上述反应溶液中，1h后取出，用 甲苯反复冲洗即获得聚氟硅氧烷基固态超滑表面。
实施例1制备的聚氟硅氧烷基固态超滑表面玻璃样品，其表面接枝有聚氟硅氧烷大分子，反应示意图如图5所示。
对实施例1制备的固态超滑表面进行分子结构表征，如图1所示，其中2899cm-1对应于聚氟硅氧烷甲基上C-H键的伸缩振动峰；在1355cm-1对应于聚氟硅氧烷C-F键的特征峰。证实了聚氟硅氧烷基固态超滑表面的成功制备。由于经甲苯反复冲洗残余反应物后才进行FTIR测试，因此能够证实聚氟硅氧烷大分子接枝在基底上。
实施例2
原料：载玻片，无色透明玻璃片；二氯(甲基)(3,3,3-三氟丙基)硅烷，一种无色至淡黄色液体，能够以甲苯为溶剂配制不同浓度反应溶液；二甲基二氯硅烷，一种无色至淡黄色液体，能够以甲苯为溶剂配制不同浓度反应溶液；
(1)将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，85℃加热1h后用去离子水冲洗，烘干，获得表面羟基化修饰后的玻璃样品；
(2)将二氯(甲基)(3,3,3-三氟丙基)硅烷、二甲基二氯硅烷溶解在甲苯溶剂中，配制反应溶液，二氯(甲基)(3,3,3-三氟丙基)硅烷、二甲基二氯硅烷与甲苯的摩尔比为1:1:98，充分搅拌后静置备用；
(3)将羟基化修饰后的玻璃样品浸入上述反应溶液中，1h后取出，用甲苯冲洗即获得聚氟硅氧烷基固态超滑表面。
实施例2制备的聚氟硅氧烷基固态超滑表面玻璃样品，其表面接枝有聚氟硅氧烷大分子，反应示意图如图6所示。
实施例3
原料：载玻片，无色透明玻璃片；二氯(甲基)(3,3,3-三氟丙基)硅烷，一种无色至淡黄色液体，能够以甲苯为溶剂配制不同浓度反应溶液；二乙基二氯硅烷，一种无色至淡黄色液体，能够以甲苯为溶剂配制不同浓度反应溶液；
(1)将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，85℃加热1h后用去离子水冲洗，烘干，获得表面羟基化修饰后的玻璃样品；
(2)将二氯(甲基)(3,3,3-三氟丙基)硅烷、二乙基二氯硅烷溶解在甲苯溶剂中，配制反应溶液，二氯(甲基)(3,3,3-三氟丙基)硅烷、二乙基二氯硅烷与甲苯的摩尔比为1:1:98，充分搅拌后静置备用；
(3)将羟基化修饰后的玻璃样品浸入上述反应溶液中，1h后取出，用甲苯冲洗即获得聚氟硅氧烷基固态超滑表面。
实施例3制备的聚氟硅氧烷基固态超滑表面玻璃样品，其表面接枝有聚氟硅氧烷大分子，反应示意图如图7所示。
实施例4
原料：载玻片，无色透明玻璃片；3,3,3-三氟丙基(甲基)(二甲氧基)硅烷，一种无色至淡黄色液体，能够以异丙醇为溶剂配制不同浓度反应溶液；二甲氧基(甲基)硅烷，一种无色至淡黄色液体，能够以异丙醇为溶剂配制不同浓度反应溶液；
(1)将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，85℃加热1h后用去离子水冲洗，烘干，获得表面羟基化修饰后的玻璃样品；
(2)将3,3,3-三氟丙基(甲基)(二甲氧基)硅烷、二甲氧基(甲基)硅烷、浓硫酸溶解在异丙醇溶剂中，配制反应溶液，3,3,3-三氟丙基(甲基)(二甲氧基)硅烷、二甲氧基(甲基)硅烷、浓硫酸与异丙醇的摩尔比为10:10:1:79，充分搅拌后静置备用；
(3)将羟基化修饰后的玻璃样品浸入上述反应溶液中10min，取出静置于室温环境中，晾干1h后依次用异丙醇、甲苯冲洗干净即获得聚氟硅氧烷基固态超滑表面。
实施例4制备的聚氟硅氧烷基固态超滑表面玻璃样品，其表面接枝有聚氟硅氧烷大分子，反应示意图如图8所示。
实施例5
原料：载玻片，无色透明玻璃片；3,3,3-三氟丙基(甲基)(二甲氧基)硅烷，一种无色至淡黄色液体，能够以异丙醇为溶剂配制不同浓度反应溶液；二异丙基二甲氧基硅烷，一种无色至淡黄色液体，能够以异丙醇为溶剂配制不同浓度反应溶液；
(1)将载玻片在丙酮、乙醇和去离子水中多次超声清洗去除杂质后，浸泡在65％的浓硫酸中，加热1h后冲洗、烘干，获得表面羟基化修饰后的玻璃样品；
(2)将3,3,3-三氟丙基(甲基)(二甲氧基)硅烷、二异丙基二甲氧基硅烷、浓硫酸溶解在异丙醇溶剂中，配制反应溶液，3,3,3-三氟丙基(甲基)(二甲氧基)硅烷、二异丙基二甲氧基硅烷、浓硫酸与异丙醇的摩尔比为10:10:1:79，充分搅拌后静置备用；
(6)将羟基化修饰后的玻璃样品浸入上述反应溶液中10min，取出静置于室温环境中，1h后依次用异丙醇、甲苯冲洗干净即获得聚氟硅氧烷基固态超滑表面。
实施例5制备的聚氟硅氧烷基固态超滑表面玻璃样品，其表面接枝有聚氟硅氧烷大分子，反应示意图如图9所示。
对比例1
此对比例样品经气相沉积法制备，具体的，将载玻片经羟基化后置于高压釜中，加入一定量的1H,1H,2H,2H-全氟癸基-三乙氧基硅烷(POTS)，保持120℃加热20分钟后取出样品并洗去玻璃表面的粗产物，制得POTS-Glass样品。
性能表征：
通过接触角测量仪测定水滴在倾斜的聚氟硅氧烷基固态超滑表面的滑动性，具体为：将水滴(20μL)滴在倾斜度为10°的实施例3中制备的聚氟硅氧烷基固态超滑表面上，然后用接触角测量仪记录液滴在表面滑动一段时间后的距离。
由图2可以看出液滴在实施例3中制备的超滑表面(SSS)上可以自行滑落，液滴能够稳定较快地滑动，与之相对照的液滴在未经处理的玻璃表面则始终停留在初始位置，表明该固态超滑表面具有优异的超滑性能。此外，与之相对照的液滴在全氟硅烷处理的样品(POTS-Glass)表面则始终停留在初始位置，表明SSS样品与水在分子间界面上能够提供比疏水处理(含氟小分子POTS)表面更低的相互作用力，这是由于SSS表面含氟基团与聚硅氧烷分子链高度柔顺性的协同作用，因此表面接枝聚氟硅氧烷的SSS具有最优 的防护性能。
图3为实施例3构建的聚氟硅氧烷基固态超滑表面(SSS)与对照组玻璃样品(Glass)和对照组全氟硅烷处理的样品(POTS-Glass)在静态的假交替单胞菌培养液中浸泡3天和14天后的细菌附着荧光照片。由图片可以看出，无论浸泡3天还是14天，对照组玻璃样品表面具有大量的细菌附着，聚氟硅氧烷基固态超滑表面只有很少量的细菌附着；对照组全氟硅烷处理的样品(POTS-Glass)细菌附着量少于空白玻璃样品，表明经疏水处理后的玻璃能够在一定程度上抑制细菌附着，却显著多于固态超滑表面(SSS)，因此聚氟硅氧烷基固态超滑表面可以有效抑制细菌在表面的附着，且具有长效性，从而从根源上阻止水下光学窗口透光率的下降。
图4为实施例3构建的聚氟硅氧烷基固态超滑表面(SSS)与对照组玻璃样品(Glass)在防污实验前后的水下可见光透光率对比图。由图中可以看出，在14天的防污实验前，聚氟硅氧烷基固态超滑表面(SSS)具有与对照组玻璃(Glass)接近的水下透明性，展现出了良好的水下透明性，并且在经过14天的防污实验之后仍具有可靠的水下可见光透过率，证实了聚氟硅氧烷基固态超滑表面作为海洋仪器水下光学窗口防污技术的可靠性。
由以上实施例可知，本申请提供的新型聚氟硅氧烷基固态超滑表面，通过化学键合实现润滑油与基底牢固结合的效果，解决了传统仿生超滑表面润滑油在水下环境中容易流失的问题，具有更长久的防治生物污损的性能，从而使表面润滑油具有极为可靠的稳定性，为仿生超滑表面在海洋生物污损防护中的长效性问题提供了一种解决方法。
以上所述仅是本申请的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。

Claims (15)

  1. 一种固态超滑表面的构建方法，其特征在于，包括以下步骤：
    对基底进行表面羟基化修饰，得到富含羟基的基底；
    提供反应溶液；所述反应溶液包括硅烷单体和有机溶剂；所述硅烷单体为二氯硅烷单体或二甲氧基硅烷单体；所述二氯硅烷单体中至少有一种单体为含氟二氯硅烷单体；所述二甲氧基硅烷单体中至少有一种单体为含氟二甲氧基硅烷单体；
    使所述反应溶液与富含羟基的基底接触，在基底上羟基的引发下所述硅烷单体发生聚合，形成与基底通过共价键结合的线性聚氟硅氧烷，得到固态超滑表面。
  2. 根据权利要求1所述的构建方法，其特征在于，所述含氟二氯硅烷单体包括1H,1H,2H,2H-全氟癸基甲基二氯硅烷、1H,1H,2H,2H-全氟辛基甲基二氯硅烷和二氯(甲基)(3,3,3-三氟丙基)硅烷中的一种或多种。
  3. 根据权利要求1或2所述的构建方法，其特征在于，所述二氯硅烷单体还包括不含氟二氯硅烷单体；所述不含氟二氯硅烷单体包括二异丙基二氯硅烷、二苯二氯硅烷、二甲基二氯硅烷、二氯二乙基硅烷、二氯二丙基硅烷、二丁基二氯硅烷、二氯(异丁基)(甲基)硅、二氯二戊基硅烷、二氯二己基硅烷、二氯(甲基)(丙基)硅烷、二氯乙基甲基硅烷、甲基乙烯基二氯硅烷、己基甲基二氯硅烷、二氯四甲基二硅烷、二氯甲基辛基硅烷、二氯(异丁基)(甲基)硅、1,3-二氯-1,1,3,3,-四甲基二硅氧烷和1,3-双(氯甲基)-1,1,3,3-四甲基二硅氧烷中的一种或多种。
  4. 根据权利要求3所述的构建方法，其特征在于，所述含氟二氯硅烷单体和不含氟二氯硅烷单体的摩尔比为1:1。
  5. 根据权利要求1所述的构建方法，其特征在于，所述含氟二甲氧基硅烷单体包括3,3,3-三氟丙基(甲基)(二甲氧基)硅烷和/或二甲氧基双(五氟苯基)硅烷。
  6. 根据权利要求1或5所述的构建方法，其特征在于，所述二甲氧基硅烷单体还包括不含氟二甲氧基硅烷单体；所述不含氟二甲氧基硅烷单体包括二甲氧基二苯基硅烷、二甲氧基二甲基硅烷、二甲氧基(甲基)硅烷、二甲氧基(甲基)辛基硅、二甲氧基(甲基)辛基硅、异丁基二甲氧基(甲基)硅烷、二 异丙基二甲氧基硅烷、3-巯基丙基(二甲氧基)甲基硅烷、二异丁基二甲氧基硅烷和甲基环己基二甲氧基硅烷中的一种或多种。
  7. 根据权利要求6所述的构建方法，其特征在于，所述含氟二甲氧基硅烷单体和不含氟二甲氧基硅烷单体的摩尔比为1:1。
  8. 根据权利要求1所述的构建方法，其特征在于，当所述硅烷单体为二甲氧基硅烷单体，所述反应溶液中还包括酸催化剂。
  9. 根据权利要求8所述的构建方法，其特征在于，所述酸催化剂包括高锰酸、盐酸、硫酸、硝酸、高氯酸、对甲苯磺酸、氢氟酸、硒酸、次氯酸、三氟甲磺酸和氯酸中的一种或多种。
  10. 根据权利要求8或9所述的构建方法，其特征在于，所述二甲氧基硅烷单体与酸催化剂的摩尔比为(0.01～100)：1。
  11. 根据权利要求1所述的构建方法，其特征在于，使所述反应溶液与富含羟基的基底接触包括：将富含羟基的基底浸泡到反应溶液中。
  12. 根据权利要求11所述的构建方法，其特征在于，所述浸泡的时间为10s～60min。
  13. 根据权利要求1所述的构建方法，其特征在于，所述有机溶剂包括二氯甲烷、三氯甲烷、戊烷、己烷、庚烷、环己烷、苯、甲苯、二甲苯、氯苯、二氯苯、四氢呋喃、甲醇、乙醇、异丙醇、正丁醇、N,N-二甲基甲酰胺和N,N-二甲基亚砜的一种或多种。
  14. 权利要求1～13任一项所述构建方法得到的固态超滑表面，其特征在于，化学组成为线性聚氟硅氧烷，所述线性聚氟硅氧烷与基底之间通过化学共价键结合。
  15. 权利要求14所述固态超滑表面作为海洋防污涂层的应用。
PCT/CN2024/092239 2024-01-19 2024-05-10 一种固态超滑表面及其构建方法和应用 Pending WO2025152302A1 (zh)

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