WO2018133469A1 - 一种耐久性的亲水-超疏水双极自洁复合膜及其制备方法 - Google Patents

一种耐久性的亲水-超疏水双极自洁复合膜及其制备方法 Download PDF

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WO2018133469A1
WO2018133469A1 PCT/CN2017/107461 CN2017107461W WO2018133469A1 WO 2018133469 A1 WO2018133469 A1 WO 2018133469A1 CN 2017107461 W CN2017107461 W CN 2017107461W WO 2018133469 A1 WO2018133469 A1 WO 2018133469A1
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hydrophilic
superhydrophobic
composite film
parts
hydrophobic
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PCT/CN2017/107461
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English (en)
French (fr)
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张立志
职晶慧
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华南理工大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • 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
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
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    • 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
    • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2203/00—Other substrates
    • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
    • B05D2203/35—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/10—Organic solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20—Aqueous dispersion or solution
    • B05D2401/21—Mixture of organic solvent and water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2504/00—Epoxy polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D2518/00—Other type of polymers
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    • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • B05D2601/22—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
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    • C—CHEMISTRY; METALLURGY
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention belongs to the technical field of superhydrophobic surfaces, and in particular relates to a durable hydrophilic-superhydrophobic bipolar self-cleaning composite film and a preparation method thereof.
  • the superhydrophobic surface has many unique advantages in the interface phenomenon due to the large contact angle of water droplets on its surface ( ⁇ 150°) and the small rolling angle ( ⁇ 10°), so that the superhydrophobic surface has many unique advantages in the interface phenomenon. : Self-cleaning, anti-oil, anti-corrosion, anti-condensation, anti-frosting, etc. Therefore, the study of the preparation of superhydrophobic surfaces has very important practical significance and broad application prospects.
  • CN101962514A discloses a long-durability superhydrophobic self-cleaning coating material and a preparation method thereof, which are prepared by photocatalytically active nanoparticles, a low surface free energy polymer and a crosslinking agent, but the method
  • the low surface free energy polymer needs to use fluorinated polysiloxane, and the fluoride is expensive and the use cost is high; at the same time, the bonding between the coating and the substrate is not explained; the mechanical properties of the coating are not detected.
  • CN105602412A discloses a preparation method of an abrasion-resistant superhydrophobic nano-titanium dioxide coating, which uses a silane coupling agent and an epoxy resin to fix hydrophobically modified titanium dioxide particles, but the preparation process has a long period, and only the film drying process is performed. Need 8 ⁇ 10h; the preparation of the superhydrophobic surface The tentacles are only about 150°, and the superhydrophobic effect is not particularly good; the friction test only uses the quality change to indicate the wear resistance, which is not a good illustration of the problem.
  • the surface can withstand 120 cycles of wear while remaining superhydrophobic. Although these methods all enhance the interaction between the rough structure and the low surface energy material to a certain extent, the force between the superhydrophobic film layer and the substrate is not improved, and the durability of the superhydrophobic surface is weak. The shortcomings have not been solved.
  • the primary object of the present invention is to provide a method for preparing a durable hydrophilic-superhydrophobic bipolar self-cleaning composite film.
  • Another object of the present invention is to provide a durable hydrophilic-superhydrophobic bipolar self-cleaning composite film prepared by the above method.
  • a method for preparing a durable hydrophilic-superhydrophobic bipolar self-cleaning composite film comprising the following preparation steps:
  • the epoxy silane coupling agent in the step (1) refers to an organosilane compound containing at least one of a methoxy group, an ethoxy group, a chloro group, an acetoxy group, and an epoxy group.
  • Specific examples of compounds include: ⁇ -glycidyloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, 2-(3,14-epoxy Cyclohexyl)ethyltrimethoxysilane and the like.
  • the hydrolyzable group in the epoxy silane coupling agent undergoes covalent bond reaction with the substrate after hydrolysis, and the epoxy functional group undergoes covalent crosslinking reaction with the amine curing agent to form a three-dimensional network structure, which is sticky.
  • the solid particles are encapsulated and a new functional group can be formed for covalent bond reaction with the subsequently applied hydrophobic layer solution.
  • the organic solvent solvent is at least one of methanol, ethanol, and isopropyl alcohol.
  • the amine curing agent described in the step (1) is at least one of octadecylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
  • the micron-sized solid particles in the step (1) are at least one of micron-sized silica, alumina, zinc oxide, and corundum.
  • the parts by weight of each material in the step (1) are as follows: 2 to 5 parts of the epoxy silane coupling agent, 20 to 50 parts of the organic solvent, 0.5 to 3 parts of the amine curing agent, and 0.5 to 3 parts of the distilled water.
  • the micron-sized solid particles are 0 to 0.5 parts, and the hydrophobic nano-SiO 2 particles are 0.2 to 0.6 parts.
  • the temperature is maintained in the range of 25 to 40 °C.
  • the hydrophobic modifier in the step (2) is hexamethyldisilazane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, methyltrimethoxysilane, A At least one of the group of triethoxysilanes.
  • the solvent is at least one of methanol, ethanol, propylene glycol, isopropanol, isobutanol, butanol, glycerin, and tetrahydrofuran.
  • the parts by weight of each material in the step (2) are as follows: 2 to 6 parts of the hydrophobic modifier, 10 to 50 parts of the solvent, and 0.05 to 0.3 parts of the hydrophilic nano-SiO 2 particles.
  • the substrate in the step (3) comprises a substrate of glass, iron, copper, aluminum, cement, etc.; the pretreatment comprises ultrasonic cleaning in a mixture of ethanol and acetone, followed by washing and drying with deionized water. dry.
  • a durable hydrophilic-superhydrophobic bipolar self-cleaning composite film is prepared by the above method.
  • the superhydrophobic surface prepared by the hydrophilic-superhydrophobic bipolar composite membrane can satisfy the stability of the microstructure and the durability of the low surface energy material.
  • the hydrophilic layer acts as a linking layer, and an organic material containing two functional groups having different properties is used to bond together with the substrate and the hydrophobic layer in a covalent bond, thereby enhancing the mechanical force of the film layer to the outside. Resistance.
  • the microstructure of the film layer is acted upon by micron-sized solid particles dispersed in the hydrophilic layer, and the solid particles are not loosely stacked in the hydrophilic layer, but are tightly bonded by the adhesive in the hydrophilic layer. Together, it enhances the robustness of the microstructure.
  • the hydrophobic layer and the hydrophilic layer are bonded together in a covalent bond to enhance the durability of the low surface energy material. Thereby the durability of the prepared superhydrophobic surface is greatly enhanced.
  • the membrane has both a hydrophilic group and a hydrophobic group, and is capable of being superhydrophobic and closely bonded to the underlayer by a covalent bond, which is called a bipolar membrane.
  • the substrate is glass
  • the schematic diagram of the covalent bonding reaction between the hydrophilic layer and the substrate of the present invention and the covalent bonding reaction between the hydrophilic layer and the hydrophobic layer are respectively shown in FIG. 1 and FIG. 2;
  • a schematic structural view of the obtained hydrophilic-superhydrophobic self-cleaning composite film is shown in FIG. Similar when the substrate is made of other materials.
  • the preparation process of the invention is simple, does not require expensive equipment in the preparation process, does not require expensive experimental reagents, and can be simply dried by coating film;
  • the superhydrophobic surface of the hydrophilic-superhydrophobic bipolar composite membrane obtained by the invention has good long-term stability and strong mechanical durability; the immersion in water for up to 4 days can still satisfy the self-cleaning effect; at 20g weight Under the weight, 1200 mesh sandpaper, 17cm single friction distance, can withstand more than 180 times of friction cycle, has a good industrial application prospects.
  • FIGS. 1 and 2 are schematic diagrams showing a covalent bonding reaction between a hydrophilic layer and a substrate of the present invention and a covalent bonding reaction between a hydrophilic layer and a hydrophobic layer when the substrate is glass;
  • FIG. 3 is a schematic structural view of a hydrophilic-superhydrophobic self-cleaning composite film of the present invention when the substrate is glass;
  • Example 4 is a scanning electron micrograph of a hydrophilic-superhydrophobic self-cleaning composite film obtained in Example 1 of the present invention.
  • Example 5 is a graph showing the results of contact angle test of the hydrophilic-superhydrophobic self-cleaning composite film obtained in Example 1 of the present invention.
  • Fig. 6 is a graph showing the relationship between durability and wettability of the hydrophilic-superhydrophobic self-cleaning composite film obtained in Example 1 of the present invention.
  • the solution prepared in the step (3) is also applied to the hydrophilic film layer by a drop coating method, and then the sample is placed in an oven at 140 ° C. Dry At 80 min, the hydrophilic-superhydrophobic bipolar composite membrane of this example was obtained. Under such conditions, the ethanol on the surface of the sample volatilizes, and the dehydration condensation between the hydrophilic layer and the substrate, between the hydrophilic layer and the hydrophobic layer forms a covalent bond, enhancing the ability of the superhydrophobic surface to resist external forces. .
  • FIG. 4 The scanning electron micrograph of the hydrophilic-superhydrophobic self-cleaning composite film obtained in this embodiment is shown in FIG. 4; the contact angle test result chart is shown in FIG. 5.
  • the durability and wettability of the hydrophilic-superhydrophobic self-cleaning composite film obtained in this example were tested.
  • the specific test procedure was as follows: durability was tested by sanding method: the sample was placed on 1200 mesh sandpaper at 20 g ⁇ The test was carried out under the weight of the code at a wear distance of 17 cm each time. Wettability The contact angle was measured by a contact angle meter from Dataphysics OCA 2.0, and the roll angle was measured by a laboratory-made device. The contact angle and roll angle were measured after 5 wear tests. Each contact angle and roll angle were tested at 5 different points of the sample, and the average was taken as the test result.
  • the superhydrophobic surface prepared by the present invention can withstand 180 times of friction loss while maintaining its superhydrophobicity.
  • the contact angle of the surface changed from 166° to the final 150°, while the roll angle was changed from the initial 2°, a small change in the friction test to a rapid over 90° after 180 wears. It shows that there is a strong bonding force between the coating and the substrate. After a certain abrasion, the bonding force between the coating and the substrate is broken, and the coating is detached from the surface, and the surface loses its superhydrophobicity.
  • the solution prepared in the step (3) is also applied to the hydrophilic film layer by a drop coating method, and then the sample is placed in an oven at 140 ° C. After drying for 60 minutes, the hydrophilic-superhydrophobic bipolar composite membrane of this example was obtained. Under such conditions, the ethanol on the surface of the sample volatilizes, and the dehydration condensation between the hydrophilic layer and the substrate, between the hydrophilic layer and the hydrophobic layer forms a covalent bond, enhancing the ability of the superhydrophobic surface to resist external forces. .
  • the solution prepared in the step (2) is applied onto the cleaned iron piece, and after the film is evenly coated, the iron piece is placed in an oven, and dried at a temperature of 80 ° C for 30 minutes to evaporate the ethanol to obtain a pro. Water film layer.
  • the solution prepared in the step (3) is also applied to the hydrophilic film layer by a drop coating method, and then the sample is placed in an oven at 140 ° C, After drying for 60 minutes, the hydrophilic-superhydrophobic bipolar composite membrane of this example was obtained. Under such conditions, the ethanol on the surface of the sample volatilizes, and the dehydration condensation between the hydrophilic layer and the substrate, between the hydrophilic layer and the hydrophobic layer forms a covalent bond, enhancing the ability of the superhydrophobic surface to resist external forces. .
  • the solution prepared in the step (2) is applied onto the cleaned copper sheet, and after the coating film is uniform, the copper sheet is placed in an oven, and dried at a temperature of 80 ° C for 30 minutes to evaporate the ethanol to obtain a pro. Water film layer.
  • the solution prepared in the step (3) is also applied to the hydrophilic film layer by a drop coating method, and then the sample is placed in an oven at 140 ° C, After drying for 60 minutes, the hydrophilic-superhydrophobic bipolar composite membrane of this example was obtained. Under such conditions, the surface of the sample While evaporating, the dehydration condensation between the hydrophilic layer and the substrate and between the hydrophilic layer and the hydrophobic layer forms a covalent bond, which enhances the ability of the superhydrophobic surface to resist external forces.

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Abstract

一种耐久性的亲水-超疏水双极自洁复合膜及其制备方法，所述制备方法为：将环氧基硅烷偶联剂加入到有机溶剂中，搅拌混合均匀后加入胺类固化剂和蒸馏水，搅拌后加入微米级固体颗粒和疏水性纳米二氧化硅颗粒，继续搅拌得到亲水层溶液；将疏水改性剂和亲水性纳米二氧化硅颗粒加入到溶剂中，得到疏水层溶液；将亲水层溶液涂覆于经预处理后的基材表面，加热处理，然后涂覆疏水层溶液，加热处理，得到耐久性的亲水-超疏水双极自洁复合膜。

Description

一种耐久性的亲水-超疏水双极自洁复合膜及其制备方法 技术领域
本发明属于超疏水表面技术领域，具体涉及一种耐久性的亲水-超疏水双极自洁复合膜及其制备方法。
背景技术
随着荷叶表面的自清洁机理被发现，界面的特殊浸润现象引起了研究学者的广泛兴趣。超疏水表面由于水滴在其表面的接触角大(≧150°)，滚动角小(≦10°)，呈圆球状处于其表面，从而使超疏水表面在界面现象中具有很多独特的优势，例如：自清洁、防油污、防腐蚀、抗结露、抗结霜等。因此，研究超疏水表面的制备具有非常重要的实际意义和广阔的应用前景。
近年来，超疏水表面的制备方法急剧涌现，但是绝大多数方法制备的超疏水表面其耐久性弱。在实际生产和生活中，不可避免的，表面会受到各种外力的作用。目前，超疏水表面不能在工业生产和生活中被广泛使用的主要障碍在于，其弱的机械耐久性使其不能承受各种外力的作用。
科学工作者们通过不懈的努力来提高超疏水表面的耐久性。例如CN101962514A公开了一种长耐久性的超疏水自清洁涂层材料及其制备方法，该方法是由光催化活性的纳米粒子、低表面自由能聚合物和交联剂制备而成，但是该方法的低表面自由能聚合物需用到氟化聚硅氧烷，而氟化物价格昂贵，使用成本高；同时涂层与基材之间的结合情况没有说明；没有对涂层的机械性能进行检测。CN105602412A公开了一种耐磨超疏水纳米二氧化钛涂层的制备方法，该方法是利用硅烷偶联剂和环氧树脂固定疏水改性的二氧化钛颗粒，但是制备过程中周期长，只膜层干燥过程就需要8～10h；制备出的超疏水表面的接 触角只有150°左右，超疏水效果并不是特别好；摩擦测试只是用质量变化来表示耐磨性能，不能很好地说明问题。
Zhu et al.通过在高温高压下，将碳纳米管嵌入聚四氟乙烯模板中，由于聚四氟乙烯和碳纳米管都是疏水材料，并且碳纳米管在聚四氟乙烯中又可以起到粗糙结构的作用，由此制得的超疏水表面，其耐久性被增强。该表面可以承受20次的5.6kPa的外力磨损，其表面的接触角从159°降到152°，仍可以保持一定的超疏水性。Wong et al.利用喷涂法将疏水纳米二氧化硅喷涂固定于聚氨酯胶体中，来制备机械耐久性的超疏水表面。该表面可以承受120次的循环磨损而保持超疏水状态不变。这些方法虽然都在一定程度上增强了粗糙结构与低表面能材料之间的相互作用力，但是超疏水膜层与基材之间的作用力并没有得到提高，超疏水表面的耐久性弱的缺点并没有得到真正的解决。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的首要目的在于提供一种耐久性的亲水-超疏水双极自洁复合膜的制备方法。
本发明的另一目的在于提供一种通过上述方法制备得到的耐久性的亲水-超疏水双极自洁复合膜。
本发明目的通过以下技术方案实现：
一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，包括如下制备步骤：
(1)将环氧基硅烷偶联剂加入到有机溶剂中，搅拌混合均匀后加入胺类固化剂和蒸馏水，搅拌20～50min，然后加入微米级固体颗粒和疏水性纳米SiO2颗粒，继续搅拌1～3h，得到亲水层溶液；
(2)将疏水改性剂加入到溶剂中，同时加入亲水性纳米SiO2颗粒，搅拌混合均匀，得到疏水层溶液；
(3)将步骤(1)制备的亲水层溶液涂覆于经预处理后的基材表面，在60～80℃加热处理10～50min，然后涂覆步骤(2)所得疏水层溶液，100～140℃加 热处理50～90min，得到所述耐久性的亲水-超疏水双极自洁复合膜。
优选地，步骤(1)中所述环氧基硅烷偶联剂是指同时含有甲氧基、乙氧基、氯基、乙酰氧基中至少一种基团和环氧基团的有机硅烷化合物，作为举例的具体化合物有：γ-缩水甘油醚氧丙基三甲氧基硅烷、3-(2，3-环氧丙氧)丙基三乙氧基硅烷、2-(3，14-环氧环己基)乙基三甲氧基硅烷等。所述的环氧基硅烷偶联剂中的可水解基团在水解之后与基材发生共价键反应，同时环氧官能团与胺类固化剂发生共价交联反应生成三维网络状结构，粘结包裹固体颗粒，同时可以生成一种的新的官能团，以备与之后涂覆的疏水层溶液发生共价键反应。
所述的有机溶剂溶剂为甲醇、乙醇、异丙醇中的至少一种。
优选地，步骤(1)中所述的胺类固化剂为十八胺、乙二胺、己二胺、二乙烯三胺、三乙烯四胺中的至少一种。
优选地，步骤(1)中所述微米级固体颗粒为微米级的二氧化硅、氧化铝、氧化锌、金刚砂中的至少一种。
优选地，步骤(1)中各物料加入量的重量份如下：环氧基硅烷偶联剂2～5份，有机溶剂20～50份，胺类固化剂0.5～3份，蒸馏水0.5～3份，微米级固体颗粒0～0.5份，疏水性纳米SiO2颗粒0.2～0.6份。
优选地，步骤(1)中所述亲水层溶液的制备过程中，温度保持在25～40℃的范围。
优选地，步骤(2)中所述疏水改性剂为六甲基二硅胺烷、三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷中的至少一种。所述的溶剂为甲醇、乙醇、丙二醇、异丙醇、异丁醇、丁醇、丙三醇、四氢呋喃中的至少一种。
优选地，步骤(2)中各物料加入量的重量份如下：疏水改性剂2～6份，溶剂10～50份，亲水性纳米SiO2颗粒0.05～0.3份。
优选地，步骤(3)中所述基材包括玻璃、铁、铜、铝、水泥等基材；所述预处理包括在乙醇和丙酮的混合液中超声清洗，然后用去离子水清洗、烘干。
一种耐久性的亲水-超疏水双极自洁复合膜，通过上述方法制备得到。
本发明的原理为：
利用亲水-超疏水双极复合膜制备的超疏水表面，既可以满足微观结构稳健，又可以实现低表面能材料的持久。在双层膜中，亲水层作为链接层，使用含有两种不同性质官能团的有机材料，分别与基材、疏水层之间以共价键的形式结合在一起，增强膜层对外界机械力的抵抗。膜层的微观结构则由分散在亲水层的微米级固体颗粒充当，并且该固体颗粒不是松散的堆放在亲水层中，而是由亲水层中的粘结胶紧实的粘结在一起，增强了微观结构的稳健性。疏水层与亲水层之间以共价键的形式结合在一起，强化了低表面能材料的持久性。从而使制备的超疏水表面的耐久性被极大的增强。该膜既有亲水基，又有憎水基，既能超疏水，又能与底层通过共价键紧密结合，称为双极膜。当基材为玻璃时，本发明所述亲水层与基材之间的共价结合反应示意图及亲水层与疏水层之间的共价结合反应示意图分别如图1和图2所示；所得亲水-超疏水自洁复合膜的结构示意图如图3所示。当基材为其他材质时类似。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明的制备过程简单，在制备过程中不需要昂贵的设备，不需要高价的实验试剂，只需简单的涂膜烘干即可；
(2)本发明所得亲水-超疏水双极复合膜的超疏水表面长期稳定性好，机械耐久性强；在水中浸泡长达4天之久依旧可以满足自清洁的效果；在20g砝码的重量下、1200目的砂纸上、17cm的单次摩擦距离，可以承受180次之多的摩擦循环，具有较好的工业应用前景。
附图说明
图1和图2为当基材为玻璃时，本发明所述亲水层与基材之间的共价结合反应示意图和亲水层与疏水层之间的共价结合反应示意图；
图3为当基材为玻璃时，本发明所述亲水-超疏水自洁复合膜的结构示意图；
图4为本发明实施例1所得亲水-超疏水自洁复合膜的扫描电镜图；
图5为本发明实施例1所得亲水-超疏水自洁复合膜的接触角测试结果图；
图6为本发明实施例1所得亲水-超疏水自洁复合膜的耐久性与润湿性的关系图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
(1)将载玻片放入烧杯中，将其放置于超声清洗机中，在70Hz的频率下，依次用乙醇、丙酮、去离子水超声清洗20min，清洗干净后，取出用干燥机吹干，备用。
(2)按重量份，取γ-缩水甘油醚氧丙基三甲氧基硅烷3份，加入到32份的乙醇溶液的烧杯中，在30℃恒温水浴下磁力搅拌1h；取出烧杯，加入1份的去离子水，再加入1份的十八胺，继续恒温水浴搅拌至固体完全溶解；取出烧杯，加入0.2份微米级二氧化硅颗粒和0.4份的疏水纳米二氧化硅颗粒(阿拉丁试剂公司)，继续恒温搅拌2h。
(3)用量筒量取4份的六甲基二硅胺烷于烧杯中，加入10份的乙醇溶液，同时称取0.05份的粒径为7～40nm的亲水纳米二氧化硅颗粒(阿拉丁试剂公司)于烧杯中，在磁力搅拌下搅拌30min。
(4)将步骤(2)制备的溶液滴涂于清洗好的载玻片上，涂膜均匀之后，将载玻片放于烘箱中，在80℃的温度下，烘干30min，使乙醇挥发，得到亲水膜层。
(5)将步骤(4)制备的载玻片取出之后，将步骤(3)制备的溶液同样利用滴涂的方法涂于亲水膜层上，之后将样品放于140℃条件下的烘箱中，烘干 80min，得到本实施例的亲水-超疏水双极复合膜。在这样的条件下，样品表面的乙醇在挥发的同时，亲水层与基材之间、亲水层与疏水层之间发生脱水缩合形成共价键，增强超疏水表面抵抗外界作用力的能力。
本实施例所得亲水-超疏水自洁复合膜的扫描电镜图如图4所示；其接触角测试结果图如图5所示。
对本实施例所得亲水-超疏水自洁复合膜的耐久性与润湿性进行测试，具体测试步骤如下：耐久性用砂纸打磨的方法进行测试：将样片放置在1200目的砂纸上，在20g砝码的重量下，每次17cm的磨损距离下，进行测试。润湿性通过Dataphysics OCA 2.0的接触角测量仪进行接触角的测量，滚动角通过实验室自制的装置进行测量。每磨损测试5次之后进行一次接触角和滚动角的测量，每次接触角和滚动角都在样片5个不同点进行测试，最后取平均值作为测试结果。
所得亲水-超疏水自洁复合膜的耐久性与润湿性的关系图如图6所示。
由以上结果可以看出，本发明制备的超疏水表面可以承受180次的摩擦损耗，而保持其超疏水性。在磨擦测试过程中，表面的接触角由166°变为最终的150°，而滚动角由最初的2°，在摩擦测试中的小幅度变化，到在经受180次磨损之后迅速超过90°，说明涂层与基材之间有着很强的结合力，在经受一定的磨损之后，涂层与基材之间的结合力被破坏而使涂层从表面脱落，表面失去其超疏水性。
实施例2
(1)将表面喷砂之后的铝片放入烧杯中，将其放置于超声清洗机中，在60Hz的频率下，依次用乙醇、丙酮、去离子水超声清洗10min，清洗干净后，取出用干燥机吹干，备用。
(2)按重量份，取3-(2，3-环氧丙氧)丙基三乙氧基硅烷5份，加入到32份的乙醇溶液的烧杯中，在35℃恒温水浴下磁力搅拌1h；取出烧杯，加入 0.5份的去离子水，再加入2份的十八胺，继续恒温水浴搅拌；取出烧杯，加入0.6份疏水纳米二氧化硅颗粒，继续恒温搅拌2h。
(3)用量筒量取4份的六甲基二硅胺烷于烧杯中，加入10份的乙醇溶液，同时称取0.1份的粒径为7～40nm的亲水纳米二氧化硅颗粒于烧杯中，在磁力搅拌下搅拌30min。
(4)将步骤(2)制备的溶液滴涂于清洗好的铝片上，涂膜均匀之后，将铝片放于烘箱中，在80℃的温度下，烘干30min，使乙醇挥发，得到亲水膜层。
(5)将步骤(4)制备的铝片取出之后，将步骤(3)制备的溶液同样利用滴涂的方法涂于亲水膜层上，之后将样品放于140℃条件下的烘箱中，烘干60min，得到本实施例的亲水-超疏水双极复合膜。在这样的条件下，样品表面的乙醇在挥发的同时，亲水层与基材之间、亲水层与疏水层之间发生脱水缩合形成共价键，增强超疏水表面抵抗外界作用力的能力。
实施例3
(1)将表面喷砂之后的铁片放入烧杯中，将其放置于超声清洗机中，在60Hz的频率下，依次用乙醇、丙酮、去离子水超声清洗10min，再用pH＝12氢氧化钠和亚硝酸钠的混合溶液作为碱洗液，对铁片进行清洗，清洗干净后，取出用干燥机吹干，备用。
(2)按重量份，取γ-缩水甘油醚氧丙基三甲氧基硅烷2份，加入到32份的乙醇溶液的烧杯中，在30℃恒温水浴下磁力搅拌1h；取出烧杯，加入3份的去离子水，再加入1份的三乙烯四胺，继续恒温水浴搅拌至固体完全溶解；取出烧杯，加入0.2份疏水纳米二氧化硅颗粒，继续恒温搅拌2h。
(3)用量筒量取4份的六甲基二硅胺烷于烧杯中，加入10份的乙醇溶液，同时称取0.1份的粒径为7～40nm的亲水纳米二氧化硅颗粒于烧杯中，在磁力搅拌下搅拌30min。
(4)将步骤(2)制备的溶液滴涂于清洗好的铁片上，涂膜均匀之后，将铁片放于烘箱中，在80℃的温度下，烘干30min，使乙醇挥发，得到亲水膜层。
(5)将步骤(4)制备的铁片取出之后，将步骤(3)制备的溶液同样利用滴涂的方法涂于亲水膜层上，之后将样品放于140℃条件下的烘箱中，烘干60min，得到本实施例的亲水-超疏水双极复合膜。在这样的条件下，样品表面的乙醇在挥发的同时，亲水层与基材之间、亲水层与疏水层之间发生脱水缩合形成共价键，增强超疏水表面抵抗外界作用力的能力。
实施例4
(1)将表面喷砂之后的铜片放入烧杯中，将其放置于超声清洗机中，在60Hz的频率下，依次用乙醇、丙酮、去离子水超声清洗10min，再用pH＝12氢氧化钠和亚硝酸钠的混合溶液作为碱洗液，对铜片进行清洗，清洗干净后，取出用干燥机吹干，备用。
(2)按重量份，取2-(3，14-环氧环己基)乙基三甲氧基硅烷3.1份，加入到32份的乙醇溶液的烧杯中，在30℃恒温水浴下磁力搅拌1h；取出烧杯，加入1份的去离子水，再加入3份的己二胺，继续恒温水浴搅拌至固体完全溶解；取出烧杯，加入0.3份疏水纳米二氧化硅颗粒，继续恒温搅拌2h。
(3)用量筒量取4份的六甲基二硅胺烷于烧杯中，加入10份的乙醇溶液，同时称取0.05份的粒径为7～40nm的亲水纳米二氧化硅颗粒于烧杯中，在磁力搅拌下搅拌30min。
(4)将步骤(2)制备的溶液滴涂于清洗好的铜片上，涂膜均匀之后，将铜片放于烘箱中，在80℃的温度下，烘干30min，使乙醇挥发，得到亲水膜层。
(5)将步骤(4)制备的铜片取出之后，将步骤(3)制备的溶液同样利用滴涂的方法涂于亲水膜层上，之后将样品放于140℃条件下的烘箱中，烘干60min，得到本实施例的亲水-超疏水双极复合膜。在这样的条件下，样品表面的 乙醇在挥发的同时，亲水层与基材之间、亲水层与疏水层之间发生脱水缩合形成共价键，增强超疏水表面抵抗外界作用力的能力。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于包括如下制备步骤：
    (1)将环氧基硅烷偶联剂加入到有机溶剂中，搅拌混合均匀后加入胺类固化剂和蒸馏水，搅拌20～50min，然后加入微米级固体颗粒和疏水性纳米SiO2颗粒，继续搅拌1～3h，得到亲水层溶液；
    (2)将疏水改性剂加入到溶剂中，同时加入亲水性纳米SiO2颗粒，搅拌混合均匀，得到疏水层溶液；
    (3)将步骤(1)制备的亲水层溶液涂覆于经预处理后的基材表面，在60～80℃加热处理10～50min，然后涂覆步骤(2)所得疏水层溶液，100～140℃加热处理50～90min，得到所述耐久性的亲水-超疏水双极自洁复合膜。
  2. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(1)中所述环氧基硅烷偶联剂是指同时含有甲氧基、乙氧基、氯基、乙酰氧基中至少一种基团和环氧基团的有机硅烷化合物；所述的有机溶剂为甲醇、乙醇、异丙醇中的至少一种。
  3. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(1)中所述的胺类固化剂为十八胺、乙二胺、己二胺、二乙烯三胺、三乙烯四胺中的至少一种。
  4. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(1)中所述微米级固体颗粒为微米级的二氧化硅、氧化铝、氧化锌、金刚砂中的至少一种。
  5. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(1)中各物料加入量的重量份如下：环氧基硅烷偶联剂2～5份，有机溶剂20～50份，胺类固化剂0.5～3份，蒸馏水0.5～3份，微米级固体颗粒0～0.5份，疏水性纳米SiO2颗粒0.2～0.6份。
  6. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(1)中所述亲水层溶液的制备过程中，温度保持在25～40℃的范围。
  7. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(2)中所述疏水改性剂为六甲基二硅胺烷、三甲基氯硅烷、二甲基二氯硅烷、甲基三氯硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷中的至少一种；所述的溶剂为甲醇、乙醇、丙二醇、异丙醇、异丁醇、丁醇、丙三醇、四氢呋喃中的至少一种。
  8. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(2)中各物料加入量的重量份如下：疏水改性剂2～6份，溶剂10～50份，亲水性纳米SiO2颗粒0.05～0.3份。
  9. 根据权利要求1所述的一种耐久性的亲水-超疏水双极自洁复合膜的制备方法，其特征在于：步骤(3)中所述基材包括玻璃、铁、铜、铝或水泥基材；所述预处理包括在乙醇和丙酮的混合液中超声清洗，然后用去离子水清洗、烘干。
  10. 一种耐久性的亲水-超疏水双极自洁复合膜，其特征在于：通过权利要求1～9任一项所述的方法制备得到。
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