WO2020042415A1 - Hydrophobic composite material, preparation method and use therefor, and glass containing same - Google Patents

Hydrophobic composite material, preparation method and use therefor, and glass containing same Download PDF

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Publication number
WO2020042415A1
WO2020042415A1 PCT/CN2018/119542 CN2018119542W WO2020042415A1 WO 2020042415 A1 WO2020042415 A1 WO 2020042415A1 CN 2018119542 W CN2018119542 W CN 2018119542W WO 2020042415 A1 WO2020042415 A1 WO 2020042415A1
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acid
optionally
base layer
coating
composite material
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PCT/CN2018/119542
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French (fr)
Chinese (zh)
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孙大陟
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深圳南科新材科技有限公司
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Publication of WO2020042415A1 publication Critical patent/WO2020042415A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation

Definitions

  • the present application belongs to the field of hydrophobic materials, and in particular, relates to a hydrophobic composite material, a preparation method, a use thereof, and a glass containing the same.
  • Fluorine-containing composite materials or coatings because of their low surface free energy, have potential application values in many areas, such as the use of waterproof materials on the surface of mobile phones, automobiles, optical instruments, glasses, or LCD displays.
  • Applying a hydrophobic fluorinated composite material on the surface of the mobile phone can effectively improve the smoothness of the mobile phone.
  • the hydrophobic fluorinated coating on the surface of the eye lens can avoid scratches on the glasses and effectively extend the life of the glasses. Covering the fluorine-containing coating can prevent it from being contaminated and difficult to clean, causing scratches on the lens and avoiding damage to the optical lens.
  • Applying fluorine-containing composite materials to the performance of the building's curtain wall and window glass can keep it clean for a long time.
  • CN103068764A discloses a new method for treating a substrate by using a perfluoropolyether silane composition.
  • a perfluoropolyether silane composition can be used to treat materials such as ceramics or glass capable of having antimicrobial properties.
  • the obtained materials have antimicrobial properties and are on the surface.
  • the chemically strengthened glass coated with a low surface energy coating contains a certain concentration of silver ions.
  • CN102503164A discloses a method for preparing abrasion-resistant hydrophobic glass, including the following steps: (A) preparing a SiO 2 resin mixed sol: a hydrolysis catalyst, a solvent, and a sol precursor according to a certain volume Than mixing and stirring to get a sol, and then a resin with a specific epoxy value After curing agent was added to the sol stir to give SiO 2 / mixed sol resin; (B) front glass treatment: The cerium oxide polishing powder for polishing glass, the glass surface dirt removed, and then mixed solution of sulfuric acid and hydrogen peroxide Glass is cleaned to form active hydroxyl groups on the glass surface; (C) SiO 2 / resin composite film is plated on the glass surface: the prepared SiO 2 / resin mixed sol is coated on the glass surface before treatment
  • the purpose of this application is to provide a simple and effective method for preparing hydrophobic fluorine-containing composite materials and corresponding hydrophobic composite materials, to further improve the hydrophobic properties, friction resistance, antifouling properties, and light transmission properties of commonly used materials such as glass materials, Moreover, the preparation method needs to have the advantages of simple operation, convenient use, and suitability for large-scale promotion.
  • one object of the present application is to provide a hydrophobic composite material, which includes a hydroxyl-modified base layer whose surface is coated with an organic fluoride coating.
  • a carbon fluoride material is deposited on the surface of the hydroxyl-modified base layer.
  • the organic fluoride in the organic fluoride coating is connected to the hydroxyl-modified base layer through a chemical bond.
  • a hydroxyl group is deposited on the surface of the base layer and a fluorocarbon material is deposited, and then an organic fluoride coating is introduced through a graft reaction, so that the fluorinated carbon material deposited on the surface of the base layer is tightly covered, so that the fluorine on the surface of the base layer
  • the atom density is further increased, and the hydrophobic layer formed is denser, and a composite material with excellent hydrophobic properties can be obtained.
  • the organic fluoride coating restricts the fluorocarbon material and the fluorinated carbon material.
  • the surface of the obtained composite material has a higher density of fluorine atoms and a more uniform distribution, and the hydrophobic performance and service life can be further improved.
  • the organic fluoride in the organic fluoride coating includes any one or a mixture of at least two of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid, such as perfluorosilane and perfluorocarboxylic acid.
  • perfluorosilane perfluorocarboxylic acid
  • perfluorosulfonic acid such as perfluorosilane and perfluorocarboxylic acid.
  • the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane.
  • the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid.
  • a mixture of at least two kinds such as a mixture of perfluoro-1-butanesulfonic acid and perfluoro-1-hexanesulfonic acid, a mixture of perfluoro-1-octanesulfonic acid and perfluoro-1-decanesulfonic acid, or Perfluoro-1-butanesulfonic acid, a mixture of perfluoro-1-hexanesulfonic acid and perfluoro-1-octanesulfonic acid, and the like.
  • the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid, such as It is a mixture of perfluorohexanoic acid and perfluorodecanoic acid, a mixture of perfluoroundecanoic acid and perfluorododecanoic acid, or a mixture of perfluorohexanoic acid, perfluorononanoic acid and perfluorodecanoic acid, and the like.
  • the fluorinated carbon material includes fluorinated graphene and / or fluorinated graphite.
  • the particle size of the fluorinated carbon material is 10-100 nm, for example, 12 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 95 nm.
  • Carbonized materials can be deposited more stably on the surface of the base layer without affecting the stabilization of organic fluoride coatings by fluorinated carbon materials.
  • the hydroxyl-modified base layer is obtained by reacting a silane coupling agent with the base layer and introducing a hydroxyl-containing silane on the surface of the base layer.
  • the silane coupling agent includes hexadecyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyltrimethoxysilane. Any one or a mixture of at least two, such as a mixture of cetyltrimethoxysilane and methacryloxypropyltrimethoxysilane, isobutyltriethoxysilane and vinyltrimethoxy A mixture of silanes or a mixture of isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, and vinyltrimethoxysilane.
  • the base layer includes glass.
  • Another object of the present application is to provide a method for preparing a hydrophobic composite material.
  • the method includes the following steps:
  • Step (1) dispersing the silane coupling agent and the fluorinated carbon material in the first organic solvent to obtain a clean coating solution, and coating the solution on the surface of the base layer to obtain a hydroxyl-modified base layer;
  • Step (2) dispersing the organic fluoride and the fluorinated carbon material in a second organic solvent to obtain a post-treatment coating solution, and coating the surface on the surface of the hydroxyl-modified base layer obtained in step (1) to obtain a surface A hydroxyl-modified base layer coated with an organic fluoride coating;
  • step (3) the hydroxy-modified base layer whose surface is coated with an organic fluoride coating obtained in step (2) is heated and / or irradiated to obtain the hydrophobic composite material.
  • the content of the silane coupling agent in the cleaning coating solution described in step (1) is 0.5 to 2% by weight, for example, 0.6% by weight, 0.7% by weight, 0.8% by weight, and 0.9% by weight.
  • % 1% by weight, 1.2% by weight, 1.4% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight or 1.9% by weight, and the like.
  • the content of the fluorocarbon material in the cleaning coating solution described in step (1) is 0.05 to 0.2 wt%, for example, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1wt%, 0.12wt%, 0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.17wt%, 0.18wt% or 0.19wt%, etc.
  • the silane coupling agent described in step (1) includes cetyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyl Any one or a mixture of at least two types of trimethoxysilane, such as a mixture of cetyltrimethoxysilane and methacryloxypropyltrimethoxysilane, isobutyltriethoxysilane Mixtures with vinyltrimethoxysilane or isobutyltriethoxysilane, mixtures of methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane, and the like.
  • trimethoxysilane such as a mixture of cetyltrimethoxysilane and methacryloxypropyltrimethoxysilane, isobutyltriethoxysilane Mixtures with vinyltrimethoxysilane or isobutyltriethoxysilane, mixtures of me
  • the base layer described in step (1) includes glass.
  • the first organic solvent described in step (1) includes ethanol and / or isopropanol.
  • the fluorinated carbon material described in step (1) and step (2) includes fluorinated graphene and / or fluorinated graphite.
  • the particle size of the fluorinated carbon material described in step (1) and step (2) is 10 to 100 nm, for example, 12 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90nm or 95nm.
  • the coating described in step (1) and step (2) includes roll coating, spin coating or knife coating.
  • the dispersion described in step (1) and step (2) includes ultrasonic dispersion.
  • the content of the fluorinated carbon material in the post-treatment solution described in step (2) is 0.1 to 0.5 wt%, such as 0.15 wt%, 0.20 wt%, 0.25% wt, 0.30wt, calculated on a weight percentage basis. %, 0.35 wt%, 0.40 wt%, 0.45 wt% or 0.48 wt%, etc.
  • the organic fluoride in step (2) includes any one or a mixture of at least two of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid, such as perfluorosilane and perfluorocarboxylic acid. Mixture of perfluorosulfonic acid and perfluorocarboxylic acid, or of perfluorosilane, perfluorosulfonic acid and perfluorocarboxylic acid.
  • the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane.
  • the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid.
  • a mixture of at least two kinds such as a mixture of perfluoro-1-butanesulfonic acid and perfluoro-1-hexanesulfonic acid, a mixture of perfluoro-1-octanesulfonic acid and perfluoro-1-decanesulfonic acid, or Perfluoro-1-butanesulfonic acid, a mixture of perfluoro-1-hexanesulfonic acid and perfluoro-1-octanesulfonic acid, and the like.
  • the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid, such as It is a mixture of perfluorohexanoic acid and perfluorodecanoic acid, a mixture of perfluoroundecanoic acid and perfluorododecanoic acid, or a mixture of perfluorohexanoic acid, perfluorononanoic acid and perfluorodecanoic acid, and the like.
  • the second organic solvent described in step (2) includes ethanol and / or isopropanol.
  • the heating and / or irradiation treatment time in step (3) is 1 to 10 minutes, for example, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, or 9 minutes.
  • the heating and / or irradiation treatment described in step (3) is irradiated with an infrared light source or irradiated with sunlight.
  • a third object of the present application is to provide a use of the hydrophobic composite material, which has excellent hydrophobic properties and can be used as a waterproof coating on the surface of a mobile phone, automobile, lens, display screen, or optical device.
  • the fourth object of the present application is to provide a glass, the glass surface containing the hydrophobic composite material.
  • the present application introduces hydroxyl groups on the surface of the base layer and deposits a fluorinated carbon material, and then introduces an organic fluoride coating through a graft reaction.
  • the synergy between the two is used to further increase the density of fluorine atoms on the surface of the base layer, resulting in hydrophobicity.
  • the layers are denser, and the static contact angle of the obtained hydrophobic composite material can reach above 120 °. Compared with other products, the hydrophobic capacity is increased by about 10%, and the hydrophobic performance has obvious advantages.
  • FIG. 1 is a SEM photograph of the hydrophobic composite material 6 obtained in Example 6 of the present application.
  • the hydrophobic composite material 1 is prepared by the following steps:
  • Step (1) Disperse 1 g of cetyltrimethoxysilane and 0.1 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a clean coating solution, spin-coat it on the surface of silicate glass using a spin coater, and dry to obtain a hydroxyl-modified base layer;
  • Step (2) Disperse 1 g of perfluoro-1-hexanesulfonic acid, 0.7 g of perfluorododecyltrimethoxysilane, and 0.3 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 100 g of isopropyl alcohol.
  • An ultrasonic cleaner with a power of 200 W was subjected to ultrasonic treatment for 20 minutes to make it uniformly dispersed to obtain a post-treatment coating solution, which was scraped on the surface of the hydroxyl-modified base layer obtained in step (1) to obtain a surface coated with organic A hydroxyl-modified base layer of a fluoride coating;
  • step (3) the hydroxy-modified base layer whose surface is coated with an organic fluoride coating obtained in step (2) is placed under an infrared lamp with a power of 100 W and heated and irradiated for 10 minutes to obtain the hydrophobic composite.
  • Material 1
  • Example 1 The difference from Example 1 is only that the added amount of cetyltrimethoxysilane in step (1) is 0.6 g, and the added amount of fluorinated graphene nanoparticles is 0.2 g.
  • Example 2 gave a hydrophobic composite material 2.
  • Example 1 The difference from Example 1 is only that the amount of hexadecyltrimethoxysilane added in step (1) is 2 g, and the amount of fluorinated graphene nanoparticles is 0.06 g.
  • Example 3 gives a hydrophobic composite material 3.
  • Example 1 The only difference from Example 1 is that the hexadecyltrimethoxysilane in step (1) was replaced with methacryloxypropyltrimethoxysilane.
  • Example 4 obtained a hydrophobic composite material 4.
  • Example 1 The difference from Example 1 is only that the average particle diameter of the fluorinated graphene nanoparticles in step (1) and step (2) is 45 nm.
  • Example 5 gives a hydrophobic composite material 5.
  • Example 1 The difference from Example 1 is only that the fluorinated graphene nanoparticles in step (1) and step (2) were replaced with a mixture of fluorinated graphene nanoparticles and fluorinated graphite, and the average particle diameter of the mixture was 100 nm.
  • Example 6 gives a hydrophobic composite material 6.
  • Example 1 The difference from Example 1 is only that the perfluoro-1-hexanesulfonic acid and perfluorododecyltrimethoxysilane in step (2) were replaced with 1.7 g of perfluorodecanoic acid.
  • Example 7 gives a hydrophobic composite material 7.
  • Example 1 The difference from Example 1 is only that the time of heating and irradiation treatment in step (3) is 1 min.
  • Example 8 gave a hydrophobic composite material 8.
  • Example 1 The difference from Example 1 is only that the average particle diameter of the fluorinated graphene nanoparticles in step (1) and step (2) is 5 nm.
  • Example 9 gives a hydrophobic composite material 9.
  • Example 1 The only difference from Example 1 is that the fluorinated graphene nanoparticles in step (1) and step (2) were replaced with fluorinated graphite ions, and the average particle diameter was 225 nm.
  • Example 10 gives a hydrophobic composite material 10.
  • the hydrophobic composite material 11 is prepared by the following steps:
  • Step (1) Disperse 1 g of cetyltrimethoxysilane and 0.1 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a clean coating solution, spin-coat it on the surface of silicate glass using a spin coater, and dry to obtain a hydroxyl-modified base layer;
  • step (2) the hydroxyl-modified base layer obtained in step (1) is placed under an infrared lamp with a power of 100 W, and is heated and irradiated for 10 minutes to obtain the hydrophobic composite material 11.
  • the hydrophobic composite material 12 is prepared by the following steps:
  • Step (1) Disperse 1 g of cetyltrimethoxysilane in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to uniformly disperse to obtain a clean coating solution, and use a spin coater to disperse it. Spin-coated on the surface of silicate glass and dried to obtain a hydroxyl-modified base layer;
  • Step (2) Disperse 1 g of perfluoro-1-hexanesulfonic acid and 0.7 g of perfluorododecyltrimethoxysilane in 100 g of isopropanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a post-treatment coating solution, and apply it on the surface of silicate glass to obtain a silicate glass whose surface is coated with an organic fluoride coating;
  • step (3) the silicate glass coated with the organic fluoride coating on the surface obtained in step (2) is placed under an infrared lamp with a power of 100W and heated and irradiated for 10 minutes to obtain the hydrophobic composite material. 12.
  • hydrophobic composite materials 1 to 12 obtained in the above examples and comparative examples were tested by the following test methods, and the test results are listed in Table 1.
  • test voltage 1kV-30kV The VEGA 3LMH scanning electron microscope (SEM) produced by TESCAN Company was used to conduct morphological tests on the surfaces of the hydrophobic composite materials 1-12, and the test parameters were: test voltage 1kV-30kV.
  • FIG. 1 is an SEM photograph of the hydrophobic composite material 6 obtained in Example 6 of the present application. It can be clearly seen that the fluorocarbon material is restricted by the organic fluoride coating and is uniformly and tightly deposited on the surface of the silicate glass layer.
  • Example 1 and Examples 5 to 6 and Examples 9 to 10 From the comparison between Example 1 and Examples 5 to 6 and Examples 9 to 10, it can be known that when the average particle diameter of the fluorocarbon material is in the range of 10 to 100 nm, it can be uniformly deposited on the surface of the base layer and subjected to The limiting effect of organic fluoride coatings, when the particle size is too large or too small, the corresponding limiting effect weakens, and the fluorinated carbon material is easier to leave from the surface of the base layer, resulting in the hydrophobic composite material being hydrophobic after prolonged use. Poor performance.
  • Example 1 Comparative Example 1
  • the hydrophobic effect is average, and the obtained composite material is still a hydrophilic material.
  • the fluorinated carbon material on the surface of the base layer is easy to leave when in use, which causes the hydrophobic property brought by the fluorinated carbon material to basically disappear.
  • Example 1 From the comparison between Example 1 and Comparative Example 2, it can be known that when only an organic fluoride coating is coated on the surface of the base layer, the composite material obtained has a general hydrophobic property, and is similar to other similar hydrophobic materials obtained in related technologies. (The contact angle is about 104 °).
  • the present application introduces hydroxyl groups on the surface of the base layer and deposits a fluorinated carbon material, and then introduces an organic fluoride coating through a graft reaction.
  • the synergy between the two is used to make the fluorine atom density on the surface of the base layer further Improved, the formed hydrophobic layer is denser, and the static contact angle of the obtained hydrophobic composite material can reach more than 120 °.
  • the hydrophobic capacity is increased by about 10%, and the hydrophobic performance has obvious advantages.

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Abstract

Disclosed is a hydrophobic composite material, the hydrophobic composite material comprising a hydroxy-modified base layer having a surface coated in an organic fluoride coating, a carbon fluoride material being deposited on the surface of the hydroxy-modified base layer, and the organic fluoride in the organic fluoride coating being connected to the hydroxy-modified base layer by means of chemical bonds.

Description

一种疏水复合材料，其制备方法、用途和含有其的玻璃Hydrophobic composite material, preparation method and application thereof, and glass containing same 技术领域Technical field
本申请属于疏水材料领域，尤其涉及一种疏水复合材料，其制备方法、用途和含有其的玻璃。The present application belongs to the field of hydrophobic materials, and in particular, relates to a hydrophobic composite material, a preparation method, a use thereof, and a glass containing the same.
背景技术Background technique
含氟的复合材料或涂层等，因其具有较低的表面自由能，在很多领域有潜在的应用价值，例如作为手机、汽车、光学仪器、眼镜或液晶显示屏等表面的防水材料使用，在手机表面应用疏水的含氟复合材料可以有效提高手机的顺滑感，在眼睛镜片表面包覆有疏水的含氟涂层可以避免眼镜刮花，有效延长眼镜的使用寿命，在光学仪器镜头表面包覆含氟涂层可以避免其因污染且难以清理，导致镜头刮花，避免光学镜头的损坏，在建筑物的幕墙和窗玻璃等表现应用含氟复合材料，可以使其长时间保持清洁，减少玻璃清洗的次数，避免高空作业危险，在汽车后视镜和挡风玻璃等表面应用含氟复合材料，可以减少雨水在玻璃表面的停留，使水滴快速滑落，避免影响开车视线。Fluorine-containing composite materials or coatings, because of their low surface free energy, have potential application values in many areas, such as the use of waterproof materials on the surface of mobile phones, automobiles, optical instruments, glasses, or LCD displays. Applying a hydrophobic fluorinated composite material on the surface of the mobile phone can effectively improve the smoothness of the mobile phone. The hydrophobic fluorinated coating on the surface of the eye lens can avoid scratches on the glasses and effectively extend the life of the glasses. Covering the fluorine-containing coating can prevent it from being contaminated and difficult to clean, causing scratches on the lens and avoiding damage to the optical lens. Applying fluorine-containing composite materials to the performance of the building's curtain wall and window glass can keep it clean for a long time. Reduce the frequency of glass cleaning and avoid the danger of working at height. Applying fluorine-containing composite materials on the surface of the car's rearview mirror and windshield can reduce the retention of rainwater on the glass surface, make the water droplets slide quickly, and avoid affecting the sight of the car.
目前，相关技术中制备含氟复合材料或涂层的方法因其步骤复杂、操作繁琐、条件苛刻，从而限制了其在手机、汽车、眼镜、液晶显示屏或光学仪器等表面的应用，例如，CN103068764A公开了一种新的使用全氟聚醚硅烷组合物处理基底的方法，尤其是其可以用于处理诸如陶瓷或玻璃等能够具有抗微生物特性的材料，其得到的具有抗微生物特性且表面上涂覆有低表面能涂层的化学强化玻璃中含含有一定浓度的银离子，二者的协同效果使得得到的玻璃抗微生物性能和疏水性能优良，可用于抗微生物货架、桌面、医院、实验室以及其他需 要对微生物进行处理的场所；CN102503164A中公开了一种耐磨疏水玻璃的制备方法，包括如下步骤：(A)制备SiO 2树脂混合溶胶：将水解催化剂、溶剂、溶胶前驱体按照一定体积比混合并搅拌，得到溶胶，然后再将特定环氧值的树脂与固化剂搅拌均匀后加入所述溶胶中，得到SiO 2/树脂混合溶胶；(B)玻璃前处理：采用氧化铈抛光粉对玻璃抛光，去除玻璃表面污物，然后采用硫酸和双氧水的混合溶液对玻璃进行清洗，在玻璃表面形成具有活性的羟基基团；(C)在玻璃表面镀SiO 2/树脂复合膜：将配制好的SiO 2/树脂混合溶胶在经过前处理的玻璃表面镀膜；(D)固化：将镀有SiO 2/树脂复合膜的玻璃热处理进行固化；(E)修饰剂修饰：将修饰硅烷与溶剂混合得到修饰剂，然后将修饰剂在镀有复合膜层的玻璃表面形成疏水修饰剂膜层；(F)后处理：将镀有疏水修饰剂膜层的玻璃在无尘环境中常温放置数小时或者热处理10～60min，得到耐磨疏水玻璃；然而，上述制备方法较为复杂，得到的疏水材料或涂层疏水性能仍然较低，仍需进一步改进。 At present, the methods for preparing fluorine-containing composite materials or coatings in related technologies have complicated steps, cumbersome operations, and harsh conditions, which have limited their applications on surfaces such as mobile phones, automobiles, glasses, liquid crystal displays, or optical instruments. For example, CN103068764A discloses a new method for treating a substrate by using a perfluoropolyether silane composition. In particular, it can be used to treat materials such as ceramics or glass capable of having antimicrobial properties. The obtained materials have antimicrobial properties and are on the surface. The chemically strengthened glass coated with a low surface energy coating contains a certain concentration of silver ions. The synergistic effect of the two makes the resulting glass excellent in antimicrobial and hydrophobic properties, and can be used in antimicrobial shelves, tabletops, hospitals, and laboratories. And other places where microorganisms need to be treated; CN102503164A discloses a method for preparing abrasion-resistant hydrophobic glass, including the following steps: (A) preparing a SiO 2 resin mixed sol: a hydrolysis catalyst, a solvent, and a sol precursor according to a certain volume Than mixing and stirring to get a sol, and then a resin with a specific epoxy value After curing agent was added to the sol stir to give SiO 2 / mixed sol resin; (B) front glass treatment: The cerium oxide polishing powder for polishing glass, the glass surface dirt removed, and then mixed solution of sulfuric acid and hydrogen peroxide Glass is cleaned to form active hydroxyl groups on the glass surface; (C) SiO 2 / resin composite film is plated on the glass surface: the prepared SiO 2 / resin mixed sol is coated on the glass surface before treatment; (D) ) Curing: curing the glass coated with SiO 2 / resin composite film by heat treatment; (E) Modifier modification: mixing the modified silane with the solvent to obtain the modifier, and then the modifier is made hydrophobic on the glass surface coated with the composite film layer Modifier film layer; (F) Post-treatment: Place the glass coated with hydrophobic modifier film layer at room temperature in a dust-free environment for several hours or heat treatment for 10-60 minutes to obtain abrasion-resistant hydrophobic glass; however, the above preparation method is more complicated, The hydrophobic properties of the obtained hydrophobic materials or coatings are still low and need to be further improved.
因此需要提供一种简单有效的制备疏水含氟复合材料的方法以及相应的疏水复合材料，进一步改善常用材料如玻璃材料的疏水性能、耐摩擦性能防污性能和透光性性能等，而且，所述制备方法需要具有操作简单，使用方便且适合大规模推广的优点。Therefore, there is a need to provide a simple and effective method for preparing hydrophobic fluorine-containing composite materials and corresponding hydrophobic composite materials to further improve the hydrophobic properties, friction resistance, antifouling properties, and light transmission properties of commonly used materials such as glass materials. The preparation method needs to have the advantages of simple operation, convenient use, and suitability for large-scale promotion.
发明内容Summary of the Invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics detailed in this article. This summary is not intended to limit the scope of protection of the claims.
本申请的目的在于提供一种简单有效的制备疏水含氟复合材料的方法以及相应的疏水复合材料，进一步改善常用材料如玻璃材料的疏水性能、耐摩擦性 能防污性能和透光性性能等，而且，所述制备方法需要具有操作简单，使用方便且适合大规模推广的优点。The purpose of this application is to provide a simple and effective method for preparing hydrophobic fluorine-containing composite materials and corresponding hydrophobic composite materials, to further improve the hydrophobic properties, friction resistance, antifouling properties, and light transmission properties of commonly used materials such as glass materials, Moreover, the preparation method needs to have the advantages of simple operation, convenient use, and suitability for large-scale promotion.
为达此目的，本申请的目的之一在于提供一种疏水复合材料，所述疏水复合材料包括表面包覆有有机氟化物涂层的羟基修饰的基底层。To achieve this, one object of the present application is to provide a hydrophobic composite material, which includes a hydroxyl-modified base layer whose surface is coated with an organic fluoride coating.
所述羟基修饰的基底层表面沉积有氟化碳材料。A carbon fluoride material is deposited on the surface of the hydroxyl-modified base layer.
所述有机氟化物涂层中的有机氟化物通过化学键与羟基修饰的基底层相连。The organic fluoride in the organic fluoride coating is connected to the hydroxyl-modified base layer through a chemical bond.
本申请通过在基底层表面引入羟基并沉积氟化碳材料，再通过接枝反应引入有机氟化物涂层，使得基底层表面沉积的氟化碳材料被紧密包覆，从而使得基底层表面的氟原子密度进一步提高，形成的疏水层更密集，能够获得一种疏水性能优良的复合材料。In this application, a hydroxyl group is deposited on the surface of the base layer and a fluorocarbon material is deposited, and then an organic fluoride coating is introduced through a graft reaction, so that the fluorinated carbon material deposited on the surface of the base layer is tightly covered, so that the fluorine on the surface of the base layer The atom density is further increased, and the hydrophobic layer formed is denser, and a composite material with excellent hydrophobic properties can be obtained.
在本申请中，氟化碳材料和有机氟化物涂层之间具有协同效果，由于氟化碳材料仅通过分子间作用力吸附在基底层表面，单纯通过在基底层表面沉积氟化碳材料得到的疏水材料，随着使用次数的增多，疏水性能下降剧烈，单纯通过在基底层表面包覆有机氟化物涂层得到的疏水材料由于分子内斥力和空间位阻等因素的影响，表面氟原子密度通常较低，疏水性能通常也不高，在基底层表面同时沉积氟化碳材料并包覆有机氟化物涂层后，由于有机氟化物涂层对于氟化碳材料的限制作用和氟化碳材料对于有机氟化物中氟原子的吸引和稳定效应的存在，得到的复合材料表面氟原子密度更高、分布更均匀，疏水性能和使用寿命均能获得进一步提高。In this application, there is a synergistic effect between the fluorinated carbon material and the organic fluoride coating. Since the fluorinated carbon material is adsorbed on the surface of the base layer only by intermolecular forces, it is obtained simply by depositing the fluorinated carbon material on the surface of the base layer. With the increase of the number of uses, the hydrophobic performance decreases drastically. The hydrophobic material obtained by simply covering the surface of the base layer with an organic fluoride coating has a surface fluorine atom density due to factors such as intramolecular repulsion and steric hindrance. Usually it is low and the hydrophobic performance is usually not high. After the fluorocarbon material is deposited on the surface of the base layer and coated with the organic fluoride coating, the organic fluoride coating restricts the fluorocarbon material and the fluorinated carbon material. For the existence of the attracting and stabilizing effects of fluorine atoms in the organic fluoride, the surface of the obtained composite material has a higher density of fluorine atoms and a more uniform distribution, and the hydrophobic performance and service life can be further improved.
可选地，所述有机氟化物涂层中的有机氟化物包括全氟硅烷、全氟羧酸或全氟磺酸中的任意一种或至少两种的混合物，例如全氟硅烷与全氟羧酸的混合 物、全氟磺酸与全氟羧酸的混合物或全氟硅烷、全氟磺酸和全氟羧酸的混合物等。Optionally, the organic fluoride in the organic fluoride coating includes any one or a mixture of at least two of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid, such as perfluorosilane and perfluorocarboxylic acid. Mixtures of acids, mixtures of perfluorosulfonic acid and perfluorocarboxylic acid, or mixtures of perfluorosilane, perfluorosulfonic acid and perfluorocarboxylic acid, and the like.
可选地，所述全氟硅烷包括全氟十二烷基三氯硅烷、全氟十二烷基三甲氧基硅烷、全氟辛基三乙氧基硅烷或全氟癸基三甲氧基硅烷中的任意一种或至少两种的混合物，例如为全氟十二烷基三氯硅烷与全氟辛基三乙氧基硅烷的混合物、全氟十二烷基三氯硅烷与全氟十二烷基三甲氧基硅烷的混合物或全氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷与全氟十二烷基三氯硅烷的混合物等。Optionally, the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane. Any one or a mixture of at least two of, for example, a mixture of perfluorododecyltrichlorosilane and perfluorooctyltriethoxysilane, perfluorododecyltrichlorosilane and perfluorododecane A mixture of trimethoxysilane or perfluorooctyltriethoxysilane, a mixture of perfluorodecyltrimethoxysilane and perfluorododecyltrichlorosilane, and the like.
可选地，所述全氟磺酸包括全氟-1-丁磺酸、全氟-1-己磺酸、全氟-1-辛磺酸或全氟-1-癸磺酸中的任意一种或至少两种的混合物，例如为全氟-1-丁磺酸与全氟-1-己磺酸的混合物、全氟-1-辛磺酸与全氟-1-癸磺酸的混合物或全氟-1-丁磺酸、全氟-1-己磺酸与全氟-1-辛磺酸的混合物等。Optionally, the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid. Or a mixture of at least two kinds, such as a mixture of perfluoro-1-butanesulfonic acid and perfluoro-1-hexanesulfonic acid, a mixture of perfluoro-1-octanesulfonic acid and perfluoro-1-decanesulfonic acid, or Perfluoro-1-butanesulfonic acid, a mixture of perfluoro-1-hexanesulfonic acid and perfluoro-1-octanesulfonic acid, and the like.
可选地，所述全氟羧酸包括全氟己酸、全氟壬酸、全氟癸酸、全氟十一酸或全氟十二酸中的任意一种或至少两种的混合物，例如为全氟己酸与全氟癸酸的混合物、全氟十一酸与全氟十二酸的混合物或全氟己酸、全氟壬酸与全氟癸酸的混合物等。Optionally, the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid, such as It is a mixture of perfluorohexanoic acid and perfluorodecanoic acid, a mixture of perfluoroundecanoic acid and perfluorododecanoic acid, or a mixture of perfluorohexanoic acid, perfluorononanoic acid and perfluorodecanoic acid, and the like.
可选地，所述氟化碳材料包括氟化石墨烯和/或氟化石墨。Optionally, the fluorinated carbon material includes fluorinated graphene and / or fluorinated graphite.
可选地，所述氟化碳材料的粒径为10～100nm，例如为12nm、15nm、20nm、25nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm或95nm等，上述粒径的氟化碳材料能够更稳定地沉积在基底层表面，同时不影响氟化碳材料对于有机氟化物涂层的稳定作用。Optionally, the particle size of the fluorinated carbon material is 10-100 nm, for example, 12 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, or 95 nm. Carbonized materials can be deposited more stably on the surface of the base layer without affecting the stabilization of organic fluoride coatings by fluorinated carbon materials.
可选地，所述羟基修饰的基底层通过将硅烷偶联剂与基底层反应，在基底层表面引入含羟基的硅烷得到。Optionally, the hydroxyl-modified base layer is obtained by reacting a silane coupling agent with the base layer and introducing a hydroxyl-containing silane on the surface of the base layer.
可选地，所述硅烷偶联剂包括十六烷基三甲氧基硅烷、异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷或乙烯基三甲氧基硅烷中的任意一种或至少两种的混合物，例如为十六烷基三甲氧基硅烷与甲基丙烯酰氧基丙基三甲氧基硅烷的混合物、异丁基三乙氧基硅与乙烯基三甲氧基硅烷的混合物或异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷与乙烯基三甲氧基硅烷的混合物等。Optionally, the silane coupling agent includes hexadecyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyltrimethoxysilane. Any one or a mixture of at least two, such as a mixture of cetyltrimethoxysilane and methacryloxypropyltrimethoxysilane, isobutyltriethoxysilane and vinyltrimethoxy A mixture of silanes or a mixture of isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, and vinyltrimethoxysilane.
可选地，所述基底层包括玻璃。Optionally, the base layer includes glass.
本申请的目的之二在于提供一种疏水复合材料的制备方法，所述制备方法包括如下步骤：Another object of the present application is to provide a method for preparing a hydrophobic composite material. The method includes the following steps:
步骤(1)，将硅烷偶联剂以及氟化碳材料分散在第一有机溶剂中，得到清洁涂层溶液，将其涂覆在基底层表面，得到羟基修饰的基底层；Step (1), dispersing the silane coupling agent and the fluorinated carbon material in the first organic solvent to obtain a clean coating solution, and coating the solution on the surface of the base layer to obtain a hydroxyl-modified base layer;
步骤(2)，将有机氟化物以及氟化碳材料分散在第二有机溶剂中，得到后处理涂层溶液，将其涂覆在步骤(1)中得到的羟基修饰的基底层表面，得到表面包覆有有机氟化物涂层的羟基修饰的基底层；Step (2), dispersing the organic fluoride and the fluorinated carbon material in a second organic solvent to obtain a post-treatment coating solution, and coating the surface on the surface of the hydroxyl-modified base layer obtained in step (1) to obtain a surface A hydroxyl-modified base layer coated with an organic fluoride coating;
步骤(3)，将步骤(2)中得到的表面包覆有有机氟化物涂层的羟基修饰的基底层加热和/或辐照处理，得到所述疏水复合材料。In step (3), the hydroxy-modified base layer whose surface is coated with an organic fluoride coating obtained in step (2) is heated and / or irradiated to obtain the hydrophobic composite material.
可选地，按重量百分比计算，步骤(1)中所述的清洁涂层溶液中硅烷偶联剂的含量为0.5～2wt％，例如为0.6wt％、0.7wt％、0.8wt％、0.9wt％、1wt％、1.2wt％、1.4wt％、1.6wt％、1.7wt％、1.8wt％或1.9wt％等。Optionally, the content of the silane coupling agent in the cleaning coating solution described in step (1) is 0.5 to 2% by weight, for example, 0.6% by weight, 0.7% by weight, 0.8% by weight, and 0.9% by weight. %, 1% by weight, 1.2% by weight, 1.4% by weight, 1.6% by weight, 1.7% by weight, 1.8% by weight or 1.9% by weight, and the like.
可选地，按重量百分比计算，步骤(1)中所述的清洁涂层溶液中氟化碳材料的含量为0.05～0.2wt％，例如为0.06wt％、0.07wt％、0.08wt％、0.09wt％、0.1wt％、0.12wt％、0.13wt％、0.14wt％、0.15wt％、0.16wt％、0.17wt％、0.18 wt％或0.19wt％等Optionally, based on the weight percentage, the content of the fluorocarbon material in the cleaning coating solution described in step (1) is 0.05 to 0.2 wt%, for example, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1wt%, 0.12wt%, 0.13wt%, 0.14wt%, 0.15wt%, 0.16wt%, 0.17wt%, 0.18wt% or 0.19wt%, etc.
可选地，步骤(1)中所述的硅烷偶联剂包括十六烷基三甲氧基硅烷、异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷或乙烯基三甲氧基硅烷中的任意一种或至少两种的混合物，例如为十六烷基三甲氧基硅烷与甲基丙烯酰氧基丙基三甲氧基硅烷的混合物、异丁基三乙氧基硅与乙烯基三甲氧基硅烷的混合物或异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷与乙烯基三甲氧基硅烷的混合物等。Optionally, the silane coupling agent described in step (1) includes cetyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyl Any one or a mixture of at least two types of trimethoxysilane, such as a mixture of cetyltrimethoxysilane and methacryloxypropyltrimethoxysilane, isobutyltriethoxysilane Mixtures with vinyltrimethoxysilane or isobutyltriethoxysilane, mixtures of methacryloxypropyltrimethoxysilane and vinyltrimethoxysilane, and the like.
可选地，步骤(1)中所述的基底层包括玻璃。Optionally, the base layer described in step (1) includes glass.
可选地，步骤(1)中所述的第一有机溶剂包括乙醇和/或异丙醇。Optionally, the first organic solvent described in step (1) includes ethanol and / or isopropanol.
可选地，步骤(1)和步骤(2)中所述的氟化碳材料包括氟化石墨烯和/或氟化石墨。Optionally, the fluorinated carbon material described in step (1) and step (2) includes fluorinated graphene and / or fluorinated graphite.
可选地，步骤(1)和步骤(2)中所述的氟化碳材料的粒径为10～100nm例如为12nm、15nm、20nm、25nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm或95nm等。Optionally, the particle size of the fluorinated carbon material described in step (1) and step (2) is 10 to 100 nm, for example, 12 nm, 15 nm, 20 nm, 25 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90nm or 95nm.
可选地，步骤(1)和步骤(2)中所述的涂覆包括辊涂、旋涂或刮涂。Optionally, the coating described in step (1) and step (2) includes roll coating, spin coating or knife coating.
可选地，步骤(1)和步骤(2)中所述的分散包括超声分散。Optionally, the dispersion described in step (1) and step (2) includes ultrasonic dispersion.
可选地，按重量百分比计算，步骤(2)中所述的后处理溶液中氟化碳材料的含量为0.1～0.5wt％，例如为0.15wt％、0.20wt％、0.25wt％、0.30wt％、0.35wt％、0.40wt％、0.45wt％或0.48wt％等。Optionally, the content of the fluorinated carbon material in the post-treatment solution described in step (2) is 0.1 to 0.5 wt%, such as 0.15 wt%, 0.20 wt%, 0.25% wt, 0.30wt, calculated on a weight percentage basis. %, 0.35 wt%, 0.40 wt%, 0.45 wt% or 0.48 wt%, etc.
可选地，步骤(2)中所述的有机氟化物包括全氟硅烷、全氟羧酸或全氟磺酸中的任意一种或至少两种的混合物，例如全氟硅烷与全氟羧酸的混合物、全氟磺酸与全氟羧酸的混合物或全氟硅烷、全氟磺酸和全氟羧酸的混合物等。Optionally, the organic fluoride in step (2) includes any one or a mixture of at least two of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid, such as perfluorosilane and perfluorocarboxylic acid. Mixture of perfluorosulfonic acid and perfluorocarboxylic acid, or of perfluorosilane, perfluorosulfonic acid and perfluorocarboxylic acid.
可选地，所述全氟硅烷包括全氟十二烷基三氯硅烷、全氟十二烷基三甲氧基硅烷、全氟辛基三乙氧基硅烷或全氟癸基三甲氧基硅烷中的任意一种或至少两种的混合物，例如为全氟十二烷基三氯硅烷与全氟辛基三乙氧基硅烷的混合物、全氟十二烷基三氯硅烷与全氟十二烷基三甲氧基硅烷的混合物或全氟辛基三乙氧基硅烷、全氟癸基三甲氧基硅烷与全氟十二烷基三氯硅烷的混合物等。Optionally, the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane. Any one or a mixture of at least two of, for example, a mixture of perfluorododecyltrichlorosilane and perfluorooctyltriethoxysilane, perfluorododecyltrichlorosilane and perfluorododecane A mixture of trimethoxysilane or perfluorooctyltriethoxysilane, a mixture of perfluorodecyltrimethoxysilane and perfluorododecyltrichlorosilane, and the like.
可选地，所述全氟磺酸包括全氟-1-丁磺酸、全氟-1-己磺酸、全氟-1-辛磺酸或全氟-1-癸磺酸中的任意一种或至少两种的混合物，例如为全氟-1-丁磺酸与全氟-1-己磺酸的混合物、全氟-1-辛磺酸与全氟-1-癸磺酸的混合物或全氟-1-丁磺酸、全氟-1-己磺酸与全氟-1-辛磺酸的混合物等。Optionally, the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid. Or a mixture of at least two kinds, such as a mixture of perfluoro-1-butanesulfonic acid and perfluoro-1-hexanesulfonic acid, a mixture of perfluoro-1-octanesulfonic acid and perfluoro-1-decanesulfonic acid, or Perfluoro-1-butanesulfonic acid, a mixture of perfluoro-1-hexanesulfonic acid and perfluoro-1-octanesulfonic acid, and the like.
可选地，所述全氟羧酸包括全氟己酸、全氟壬酸、全氟癸酸、全氟十一酸或全氟十二酸中的任意一种或至少两种的混合物，例如为全氟己酸与全氟癸酸的混合物、全氟十一酸与全氟十二酸的混合物或全氟己酸、全氟壬酸与全氟癸酸的混合物等。Optionally, the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid, such as It is a mixture of perfluorohexanoic acid and perfluorodecanoic acid, a mixture of perfluoroundecanoic acid and perfluorododecanoic acid, or a mixture of perfluorohexanoic acid, perfluorononanoic acid and perfluorodecanoic acid, and the like.
可选地，步骤(2)中所述的第二有机溶剂包括乙醇和/或异丙醇。Optionally, the second organic solvent described in step (2) includes ethanol and / or isopropanol.
可选地，步骤(3)中所述的加热和/或辐照处理的时间为1～10min，例如为2min、3min、4min、5min、6min、7min、8min或9min等。Optionally, the heating and / or irradiation treatment time in step (3) is 1 to 10 minutes, for example, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, or 9 minutes.
可选地，步骤(3)中所述的加热和/或辐照处理为使用红外光源辐照或在太阳光下照射。Optionally, the heating and / or irradiation treatment described in step (3) is irradiated with an infrared light source or irradiated with sunlight.
本申请的目的之三在于提供一种所述疏水复合材料的用途，所述疏水复合材料具有优良的疏水性能，可以作为手机、汽车、镜片、显示屏或光学器件表面的防水涂层使用。A third object of the present application is to provide a use of the hydrophobic composite material, which has excellent hydrophobic properties and can be used as a waterproof coating on the surface of a mobile phone, automobile, lens, display screen, or optical device.
本申请的目的之四在于提供一种玻璃，所述玻璃表面含有所述的疏水复合 材料。The fourth object of the present application is to provide a glass, the glass surface containing the hydrophobic composite material.
与相关技术相比，本申请的有益效果包括：Compared with related technologies, the beneficial effects of this application include:
本申请通过在基底层表面引入羟基并沉积氟化碳材料，再通过接枝反应引入有机氟化物涂层，利用了二者的协同作用，使得基底层表面的氟原子密度进一步提高，形成的疏水层更密集，得到的疏水复合材料的静态接触角能够达到120°以上，相较于其他产品疏水能力提升10％左右，疏水性能具有明显优势。The present application introduces hydroxyl groups on the surface of the base layer and deposits a fluorinated carbon material, and then introduces an organic fluoride coating through a graft reaction. The synergy between the two is used to further increase the density of fluorine atoms on the surface of the base layer, resulting in hydrophobicity. The layers are denser, and the static contact angle of the obtained hydrophobic composite material can reach above 120 °. Compared with other products, the hydrophobic capacity is increased by about 10%, and the hydrophobic performance has obvious advantages.
在阅读并理解了附图和详细描述后，可以明白其他方面。After reading and understanding the drawings and detailed description, other aspects can be understood.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本申请实施例6得到的疏水复合材料6的SEM照片。FIG. 1 is a SEM photograph of the hydrophobic composite material 6 obtained in Example 6 of the present application.
具体实施方式detailed description
下面通过具体实施方式来进一步说明本申请的技术方案。The technical solutions of the present application are further described below through specific implementations.
实施例1Example 1
通过如下步骤制备疏水复合材料1：The hydrophobic composite material 1 is prepared by the following steps:
步骤(1)，将1g十六烷基三甲氧基硅烷以及0.1g平均粒径为15nm的氟化石墨烯纳米粒子分散在99g乙醇中，使用功率为200W的超声波清洗器进行超声处理20min使其分散均匀，得到清洁涂层溶液，使用旋涂机将其旋涂在硅酸盐玻璃表面，干燥，得到羟基修饰的基底层；Step (1): Disperse 1 g of cetyltrimethoxysilane and 0.1 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a clean coating solution, spin-coat it on the surface of silicate glass using a spin coater, and dry to obtain a hydroxyl-modified base layer;
步骤(2)，将1g全氟-1-己磺酸、0.7g全氟十二烷基三甲氧基硅烷以及0.3g平均粒径为15nm的氟化石墨烯纳米粒子分散在100g异丙醇中，使用功率为200W的超声波清洗器进行超声处理20min使其分散均匀，得到后处理涂层溶液，将其刮涂在步骤(1)中得到的羟基修饰的基底层表面，得到表面包覆有有 机氟化物涂层的羟基修饰的基底层；Step (2): Disperse 1 g of perfluoro-1-hexanesulfonic acid, 0.7 g of perfluorododecyltrimethoxysilane, and 0.3 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 100 g of isopropyl alcohol. An ultrasonic cleaner with a power of 200 W was subjected to ultrasonic treatment for 20 minutes to make it uniformly dispersed to obtain a post-treatment coating solution, which was scraped on the surface of the hydroxyl-modified base layer obtained in step (1) to obtain a surface coated with organic A hydroxyl-modified base layer of a fluoride coating;
步骤(3)，将步骤(2)中得到的表面包覆有有机氟化物涂层的羟基修饰的基底层放置于功率为100W的红外灯下进行加热和辐照处理10min，得到所述疏水复合材料1。In step (3), the hydroxy-modified base layer whose surface is coated with an organic fluoride coating obtained in step (2) is placed under an infrared lamp with a power of 100 W and heated and irradiated for 10 minutes to obtain the hydrophobic composite. Material 1.
实施例2Example 2
与实施例1的区别仅在于，步骤(1)中十六烷基三甲氧基硅烷的加入量为0.6g，氟化石墨烯纳米粒子的加入量为0.2g。The difference from Example 1 is only that the added amount of cetyltrimethoxysilane in step (1) is 0.6 g, and the added amount of fluorinated graphene nanoparticles is 0.2 g.
实施例2得到疏水复合材料2。Example 2 gave a hydrophobic composite material 2.
实施例3Example 3
与实施例1的区别仅在于，步骤(1)中十六烷基三甲氧基硅烷的加入量为2g，氟化石墨烯纳米粒子的加入量为0.06g。The difference from Example 1 is only that the amount of hexadecyltrimethoxysilane added in step (1) is 2 g, and the amount of fluorinated graphene nanoparticles is 0.06 g.
实施例3得到疏水复合材料3。Example 3 gives a hydrophobic composite material 3.
实施例4Example 4
与实施例1的区别仅在于，将步骤(1)中的十六烷基三甲氧基硅烷替换为甲基丙烯酰氧基丙基三甲氧基硅烷。The only difference from Example 1 is that the hexadecyltrimethoxysilane in step (1) was replaced with methacryloxypropyltrimethoxysilane.
实施例4得到疏水复合材料4。Example 4 obtained a hydrophobic composite material 4.
实施例5Example 5
与实施例1的区别仅在于，步骤(1)和步骤(2)中的氟化石墨烯纳米粒子的平均粒径为45nm。The difference from Example 1 is only that the average particle diameter of the fluorinated graphene nanoparticles in step (1) and step (2) is 45 nm.
实施例5得到疏水复合材料5。Example 5 gives a hydrophobic composite material 5.
实施例6Example 6
与实施例1的区别仅在于，步骤(1)和步骤(2)中的氟化石墨烯纳米粒 子替换为氟化石墨烯纳米粒子与氟化石墨的混合物，混合物的平均粒径为100nm。The difference from Example 1 is only that the fluorinated graphene nanoparticles in step (1) and step (2) were replaced with a mixture of fluorinated graphene nanoparticles and fluorinated graphite, and the average particle diameter of the mixture was 100 nm.
实施例6得到疏水复合材料6。Example 6 gives a hydrophobic composite material 6.
实施例7Example 7
与实施例1的区别仅在于，步骤(2)中的全氟-1-己磺酸和全氟十二烷基三甲氧基硅烷替换为1.7g全氟癸酸。The difference from Example 1 is only that the perfluoro-1-hexanesulfonic acid and perfluorododecyltrimethoxysilane in step (2) were replaced with 1.7 g of perfluorodecanoic acid.
实施例7得到疏水复合材料7。Example 7 gives a hydrophobic composite material 7.
实施例8Example 8
与实施例1的区别仅在于，步骤(3)中加热和辐照处理的时间为1min。The difference from Example 1 is only that the time of heating and irradiation treatment in step (3) is 1 min.
实施例8得到疏水复合材料8。Example 8 gave a hydrophobic composite material 8.
实施例9Example 9
与实施例1的区别仅在于，步骤(1)和步骤(2)中的氟化石墨烯纳米粒子的平均粒径为5nm。The difference from Example 1 is only that the average particle diameter of the fluorinated graphene nanoparticles in step (1) and step (2) is 5 nm.
实施例9得到疏水复合材料9。Example 9 gives a hydrophobic composite material 9.
实施例10Example 10
与实施例1的区别仅在于，步骤(1)和步骤(2)中的氟化石墨烯纳米粒子替换为氟化石墨离子，其平均粒径为225nm。The only difference from Example 1 is that the fluorinated graphene nanoparticles in step (1) and step (2) were replaced with fluorinated graphite ions, and the average particle diameter was 225 nm.
实施例10得到疏水复合材料10。Example 10 gives a hydrophobic composite material 10.
对照例1Comparative Example 1
通过如下步骤制备疏水复合材料11：The hydrophobic composite material 11 is prepared by the following steps:
步骤(1)，将1g十六烷基三甲氧基硅烷以及0.1g平均粒径为15nm的氟化石墨烯纳米粒子分散在99g乙醇中，使用功率为200W的超声波清洗器进行 超声处理20min使其分散均匀，得到清洁涂层溶液，使用旋涂机将其旋涂在硅酸盐玻璃表面，干燥，得到羟基修饰的基底层；Step (1): Disperse 1 g of cetyltrimethoxysilane and 0.1 g of fluorinated graphene nanoparticles with an average particle diameter of 15 nm in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a clean coating solution, spin-coat it on the surface of silicate glass using a spin coater, and dry to obtain a hydroxyl-modified base layer;
步骤(2)，将步骤(1)中得到的羟基修饰的基底层放置于功率为100W的红外灯下进行加热和辐照处理10min，得到所述疏水复合材料11。In step (2), the hydroxyl-modified base layer obtained in step (1) is placed under an infrared lamp with a power of 100 W, and is heated and irradiated for 10 minutes to obtain the hydrophobic composite material 11.
对照例2Comparative Example 2
通过如下步骤制备疏水复合材料12：The hydrophobic composite material 12 is prepared by the following steps:
步骤(1)，将1g十六烷基三甲氧基硅烷分散在99g乙醇中，使用功率为200W的超声波清洗器进行超声处理20min使其分散均匀，得到清洁涂层溶液，使用旋涂机将其旋涂在硅酸盐玻璃表面，干燥，得到羟基修饰的基底层；Step (1): Disperse 1 g of cetyltrimethoxysilane in 99 g of ethanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to uniformly disperse to obtain a clean coating solution, and use a spin coater to disperse it. Spin-coated on the surface of silicate glass and dried to obtain a hydroxyl-modified base layer;
步骤(2)，将1g全氟-1-己磺酸和0.7g全氟十二烷基三甲氧基硅烷分散在100g异丙醇中，使用功率为200W的超声波清洗器进行超声处理20min使其分散均匀，得到后处理涂层溶液，将其刮涂在硅酸盐玻璃表面，得到表面包覆有有机氟化物涂层的硅酸盐玻璃；Step (2): Disperse 1 g of perfluoro-1-hexanesulfonic acid and 0.7 g of perfluorododecyltrimethoxysilane in 100 g of isopropanol, and use an ultrasonic cleaner with a power of 200 W to perform ultrasonic treatment for 20 min to make it Disperse uniformly to obtain a post-treatment coating solution, and apply it on the surface of silicate glass to obtain a silicate glass whose surface is coated with an organic fluoride coating;
步骤(3)，将步骤(2)中得到的表面包覆有有机氟化物涂层的硅酸盐玻璃放置于功率为100W的红外灯下进行加热和辐照处理10min，得到所述疏水复合材料12。In step (3), the silicate glass coated with the organic fluoride coating on the surface obtained in step (2) is placed under an infrared lamp with a power of 100W and heated and irradiated for 10 minutes to obtain the hydrophobic composite material. 12.
通过如下测试方法对上述实施例和对照例中得到的疏水复合材料1～12进行测试，并将测试结果列于表1。The hydrophobic composite materials 1 to 12 obtained in the above examples and comparative examples were tested by the following test methods, and the test results are listed in Table 1.
(1)形貌测试(1) Morphology test
使用TESCAN公司生产的VEGA 3 LMH型扫描电子显微镜(SEM)分别对疏水复合材料1～12的表面进行形貌测试，测试参数为：测试电压1kV～30kV。The VEGA 3LMH scanning electron microscope (SEM) produced by TESCAN Company was used to conduct morphological tests on the surfaces of the hydrophobic composite materials 1-12, and the test parameters were: test voltage 1kV-30kV.
(2)疏水性能测试(2) Hydrophobic performance test
根据国家标准GB/T 24368-2009《玻璃表面疏水污染物检测接触角测量法》中所述的方法分别测试疏水复合材料1～12对于蒸馏水的静态接触角，与实施例1中使用的硅酸盐玻璃材料的接触角(62°)进行对比，之后分别将疏水复合材料1～12浸泡在水中置于功率为200W的超声清洗器中进行超声处理1h，来模拟长时间使用时的情况，超声处理结束后使用相同的方法测试疏水复合材料1～12的疏水性能。According to the method described in the national standard GB / T 24368-2009 "Determination of Contact Angle Measurement of Hydrophobic Contaminants on Glass Surfaces", the static contact angles of hydrophobic composites 1 to 12 for distilled water were tested separately from the silicic acid used in Example 1. The contact angle (62 °) of the salt glass material is compared, and then the hydrophobic composite materials 1-12 are immersed in water and placed in a 200W ultrasonic cleaner for 1h to simulate the situation of long-term use. Ultrasound After the treatment, the same method was used to test the hydrophobic properties of the hydrophobic composites 1-12.
表1 疏水复合材料1～12的疏水性能对比表Table 1 Comparison of hydrophobic properties of hydrophobic composite materials 1-12
Figure PCTCN2018119542-appb-000001
Figure PCTCN2018119542-appb-000001
图1为本申请实施例6得到的疏水复合材料6的SEM照片，其中可以明显 看出氟化碳材料受到有机氟化物涂层的限制，均匀且紧密沉积在硅酸盐玻璃层表面。FIG. 1 is an SEM photograph of the hydrophobic composite material 6 obtained in Example 6 of the present application. It can be clearly seen that the fluorocarbon material is restricted by the organic fluoride coating and is uniformly and tightly deposited on the surface of the silicate glass layer.
从实施例1与实施例5～6和实施例9～10之间的对比可知，当氟化碳材料的平均粒径位于10～100nm的范围内时，其能够均匀沉积在基底层表面并受到有机氟化物涂层的限制作用，当其粒径过大或过小时，相应的限制作用减弱，氟化碳材料较容易从基底层表面离去，导致得到的疏水复合材料在长时间使用后疏水性能变差。From the comparison between Example 1 and Examples 5 to 6 and Examples 9 to 10, it can be known that when the average particle diameter of the fluorocarbon material is in the range of 10 to 100 nm, it can be uniformly deposited on the surface of the base layer and subjected to The limiting effect of organic fluoride coatings, when the particle size is too large or too small, the corresponding limiting effect weakens, and the fluorinated carbon material is easier to leave from the surface of the base layer, resulting in the hydrophobic composite material being hydrophobic after prolonged use. Poor performance.
从实施例1与对照例1之间的对比可知，当仅在基底层表面沉积氟化碳材料时，带来的疏水效果一般，得到的复合材料仍为亲水性材料，而且，在长时间使用时基底层表面的氟化碳材料很容易离去，导致氟化碳材料带来的疏水性能基本消失。It can be seen from the comparison between Example 1 and Comparative Example 1 that when the fluorocarbon material is deposited only on the surface of the base layer, the hydrophobic effect is average, and the obtained composite material is still a hydrophilic material. The fluorinated carbon material on the surface of the base layer is easy to leave when in use, which causes the hydrophobic property brought by the fluorinated carbon material to basically disappear.
从实施例1与对照例2之间的对比可知，当仅在基底层表面包覆一层有机氟化物涂层时，得到的复合材料疏水性能一般，与相关技术中得到的其他类似的疏水材料(接触角约104°左右)相比，性能无明显优势。From the comparison between Example 1 and Comparative Example 2, it can be known that when only an organic fluoride coating is coated on the surface of the base layer, the composite material obtained has a general hydrophobic property, and is similar to other similar hydrophobic materials obtained in related technologies. (The contact angle is about 104 °).
综上所述，本申请通过在基底层表面引入羟基并沉积氟化碳材料，再通过接枝反应引入有机氟化物涂层，利用了二者的协同作用，使得基底层表面的氟原子密度进一步提高，形成的疏水层更密集，得到的疏水复合材料的静态接触角能够达到120°以上，相较于其他产品疏水能力提升10％左右，疏水性能具有明显优势。In summary, the present application introduces hydroxyl groups on the surface of the base layer and deposits a fluorinated carbon material, and then introduces an organic fluoride coating through a graft reaction. The synergy between the two is used to make the fluorine atom density on the surface of the base layer further Improved, the formed hydrophobic layer is denser, and the static contact angle of the obtained hydrophobic composite material can reach more than 120 °. Compared with other products, the hydrophobic capacity is increased by about 10%, and the hydrophobic performance has obvious advantages.
以上所述的具体实施例，对本申请的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本申请的具体实施例而已，并不用于限制本申请。The specific embodiments described above further describe the purpose, technical solution, and beneficial effects of the present application in detail. It should be understood that the above are only specific embodiments of the present application and are not intended to limit the present application.

Claims (11)

  1. 一种疏水复合材料，其中，所述疏水复合材料包括表面包覆有有机氟化物涂层的羟基修饰的基底层；A hydrophobic composite material, wherein the hydrophobic composite material includes a hydroxyl-modified base layer whose surface is coated with an organic fluoride coating;
    所述羟基修饰的基底层表面沉积有氟化碳材料；A carbon fluoride material is deposited on the surface of the hydroxyl-modified base layer;
    所述有机氟化物涂层中的有机氟化物通过化学键与羟基修饰的基底层相连。The organic fluoride in the organic fluoride coating is connected to the hydroxyl-modified base layer through a chemical bond.
  2. 根据权利要求1所述的疏水复合材料，其中，所述氟化碳材料的粒径为10～100nm。The hydrophobic composite material according to claim 1, wherein a particle diameter of the fluorinated carbon material is 10 to 100 nm.
  3. 根据权利要求1或2所述的疏水复合材料，其中，所述羟基修饰的基底层通过将硅烷偶联剂与基底层反应，在基底层表面引入含羟基的硅烷得到。The hydrophobic composite material according to claim 1 or 2, wherein the hydroxyl-modified base layer is obtained by reacting a silane coupling agent with a base layer and introducing a hydroxyl-containing silane on the surface of the base layer.
  4. 根据权利要求1～3之一所述的疏水复合材料，其中，所述有机氟化物涂层中的有机氟化物包括全氟硅烷、全氟羧酸或全氟磺酸中的任意一种或至少两种的混合物；The hydrophobic composite material according to any one of claims 1 to 3, wherein the organic fluoride in the organic fluoride coating layer comprises any one or at least one of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid. A mixture of the two
    可选地，所述全氟硅烷包括全氟十二烷基三氯硅烷、全氟十二烷基三甲氧基硅烷、全氟辛基三乙氧基硅烷或全氟癸基三甲氧基硅烷中的任意一种或至少两种的混合物；Optionally, the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane. Any one or a mixture of at least two of them;
    可选地，所述全氟磺酸包括全氟-1-丁磺酸、全氟-1-己磺酸、全氟-1-辛磺酸或全氟-1-癸磺酸中的任意一种或至少两种的混合物；Optionally, the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid. Species or a mixture of at least two species;
    可选地，所述全氟羧酸包括全氟己酸、全氟壬酸、全氟癸酸、全氟十一酸或全氟十二酸中的任意一种或至少两种的混合物。Optionally, the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid.
  5. 根据权利要求1或4所述的疏水复合材料，其中，所述氟化碳材料包括氟化石墨烯和/或氟化石墨；The hydrophobic composite material according to claim 1 or 4, wherein the fluorinated carbon material comprises fluorinated graphene and / or fluorinated graphite;
    可选地，所述硅烷偶联剂包括十六烷基三甲氧基硅烷、异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷或乙烯基三甲氧基硅烷中的任意一种或至少 两种的混合物；Optionally, the silane coupling agent includes hexadecyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyltrimethoxysilane. Any one or a mixture of at least two;
    可选地，所述基底层为玻璃。Optionally, the base layer is glass.
  6. 一种疏水复合材料的制备方法，其中，所述制备方法包括如下步骤：A method for preparing a hydrophobic composite material, wherein the method includes the following steps:
    步骤(1)，将硅烷偶联剂以及氟化碳材料分散在第一有机溶剂中，得到清洁涂层溶液，将其涂覆在基底层表面，得到羟基修饰的基底层；Step (1), dispersing the silane coupling agent and the fluorinated carbon material in the first organic solvent to obtain a clean coating solution, and coating the solution on the surface of the base layer to obtain a hydroxyl-modified base layer;
    步骤(2)，将有机氟化物以及氟化碳材料分散在第二有机溶剂中，得到后处理涂层溶液，将其涂覆在步骤(1)中得到的羟基修饰的基底层表面，得到表面包覆有有机氟化物涂层的羟基修饰的基底层；Step (2), dispersing the organic fluoride and the fluorinated carbon material in a second organic solvent to obtain a post-treatment coating solution, and coating the surface on the surface of the hydroxyl-modified base layer obtained in step (1) to obtain a surface A hydroxyl-modified base layer coated with an organic fluoride coating;
    步骤(3)，将步骤(2)中得到的表面包覆有有机氟化物涂层的羟基修饰的基底层加热和/或辐照处理，得到所述疏水复合材料。In step (3), the hydroxy-modified base layer whose surface is coated with an organic fluoride coating obtained in step (2) is heated and / or irradiated to obtain the hydrophobic composite material.
  7. 根据权利要求6所述的制备方法，其中，按重量百分比计算，步骤(1)中所述的清洁涂层溶液中硅烷偶联剂的含量为0.5～2wt％；The preparation method according to claim 6, wherein the content of the silane coupling agent in the cleaning coating solution in step (1) is 0.5 to 2 wt% based on the weight percentage;
    可选地，按重量百分比计算，步骤(1)中所述的清洁涂层溶液中氟化碳材料的含量为0.05～0.2wt％；Optionally, based on the weight percentage, the content of the fluorocarbon material in the cleaning coating solution described in step (1) is 0.05 to 0.2 wt%;
    可选地，步骤(1)中所述的硅烷偶联剂包括十六烷基三甲氧基硅烷、异丁基三乙氧基硅、甲基丙烯酰氧基丙基三甲氧基硅烷或乙烯基三甲氧基硅烷中的任意一种或至少两种的混合物；Optionally, the silane coupling agent described in step (1) includes cetyltrimethoxysilane, isobutyltriethoxysilane, methacryloxypropyltrimethoxysilane, or vinyl Any one or a mixture of at least two of trimethoxysilane;
    可选地，步骤(1)中所述的基底层为玻璃；Optionally, the base layer described in step (1) is glass;
    可选地，步骤(1)中所述的第一有机溶剂包括乙醇和/或异丙醇；Optionally, the first organic solvent described in step (1) includes ethanol and / or isopropanol;
    可选地，步骤(1)和步骤(2)中所述的氟化碳材料包括氟化石墨烯和/或氟化石墨；Optionally, the fluorinated carbon material described in step (1) and step (2) includes fluorinated graphene and / or fluorinated graphite;
    可选地，步骤(1)和步骤(2)中所述的氟化碳材料的粒径为10～100nm；Optionally, the particle diameter of the fluorinated carbon material described in step (1) and step (2) is 10-100 nm;
    可选地，步骤(1)和步骤(2)中所述的涂覆包括辊涂、旋涂或刮涂；Optionally, the coating described in step (1) and step (2) includes roll coating, spin coating, or blade coating;
    可选地，步骤(1)和步骤(2)中所述的分散包括超声分散。Optionally, the dispersion described in step (1) and step (2) includes ultrasonic dispersion.
  8. 根据权利要求6或7所述的制备方法，其中，按重量百分比计算，步骤(2)中所述的后处理溶液中氟化碳材料的含量为0.1～0.5wt％；The preparation method according to claim 6 or 7, wherein the content of the fluorinated carbon material in the post-treatment solution described in step (2) is 0.1 to 0.5% by weight;
    可选地，步骤(2)中所述的有机氟化物包括全氟硅烷、全氟羧酸或全氟磺酸中的任意一种或至少两种的混合物；Optionally, the organic fluoride in step (2) includes any one or a mixture of at least two of perfluorosilane, perfluorocarboxylic acid, or perfluorosulfonic acid;
    可选地，所述全氟硅烷包括全氟十二烷基三氯硅烷、全氟十二烷基三甲氧基硅烷、全氟辛基三乙氧基硅烷或全氟癸基三甲氧基硅烷中的任意一种或至少两种的混合物；Optionally, the perfluorosilane includes perfluorododecyltrichlorosilane, perfluorododecyltrimethoxysilane, perfluorooctyltriethoxysilane or perfluorodecyltrimethoxysilane. Any one or a mixture of at least two of them;
    可选地，所述全氟磺酸包括全氟-1-丁磺酸、全氟-1-己磺酸、全氟-1-辛磺酸或全氟-1-癸磺酸中的任意一种或至少两种的混合物；Optionally, the perfluorosulfonic acid includes any one of perfluoro-1-butanesulfonic acid, perfluoro-1-hexanesulfonic acid, perfluoro-1-octanesulfonic acid, or perfluoro-1-decanesulfonic acid. Species or a mixture of at least two species;
    可选地，所述全氟羧酸包括全氟己酸、全氟壬酸、全氟癸酸、全氟十一酸或全氟十二酸中的任意一种或至少两种的混合物；Optionally, the perfluorocarboxylic acid includes any one or a mixture of at least two of perfluorohexanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, or perfluorododecanoic acid;
    可选地，步骤(2)中所述的第二有机溶剂包括乙醇和/或异丙醇。Optionally, the second organic solvent described in step (2) includes ethanol and / or isopropanol.
  9. 根据权利要求6～8之一所述的制备方法，其中，步骤(3)中所述的加热和/或辐照处理的时间为1～10min；The preparation method according to any one of claims 6 to 8, wherein the heating and / or irradiation treatment time in step (3) is 1 to 10 minutes;
    可选地，步骤(3)中所述的加热和/或辐照处理为使用红外光源辐照或在太阳光下照射。Optionally, the heating and / or irradiation treatment described in step (3) is irradiated with an infrared light source or irradiated with sunlight.
  10. 一种如权利要求1～5之一所述的疏水复合材料的用途，其中，所述疏水复合材料作为手机、汽车、镜片、显示屏或光学器件表面的防水涂层使用。The use of the hydrophobic composite material according to any one of claims 1 to 5, wherein the hydrophobic composite material is used as a waterproof coating on a surface of a mobile phone, an automobile, a lens, a display screen, or an optical device.
  11. 一种玻璃，其中，所述玻璃表面含有如权利要求1～5之一所述的疏水复合材料。A glass, wherein the glass surface contains the hydrophobic composite material according to any one of claims 1 to 5.
PCT/CN2018/119542 2018-08-27 2018-12-06 Hydrophobic composite material, preparation method and use therefor, and glass containing same WO2020042415A1 (en)

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