WO2019095961A1 - 一种柔性导电超疏水涂层及其制备方法 - Google Patents

一种柔性导电超疏水涂层及其制备方法 Download PDF

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WO2019095961A1
WO2019095961A1 PCT/CN2018/111932 CN2018111932W WO2019095961A1 WO 2019095961 A1 WO2019095961 A1 WO 2019095961A1 CN 2018111932 W CN2018111932 W CN 2018111932W WO 2019095961 A1 WO2019095961 A1 WO 2019095961A1
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flexible conductive
coating
superhydrophobic coating
silver particles
preparing
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French (fr)
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李红强
苏晓竞
曾幸荣
赖学军
陈中华
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B3/00—Spraying or sprinkling apparatus with moving outlet elements or moving deflecting elements
    • B05B3/001—Spraying or sprinkling apparatus with moving outlet elements or moving deflecting elements incorporating means for heating or cooling, e.g. the material to be sprayed
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    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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    • C09D7/60—Additives non-macromolecular
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/66—Additives characterised by particle size
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    • C08J2307/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2383/00—Characterised by the use of 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; Derivatives of such polymers
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    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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    • C08K3/02—Elements
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    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the invention relates to the field of superhydrophobic coatings, in particular to a flexible conductive superhydrophobic coating and a preparation method thereof.
  • the invention aims at the shortcomings of the super-hydrophobic coating, such as poor flexibility, resistance to stretching and bending, and the disadvantage that the conductive coating is not hydrophobic, and the conductivity is easily broken under the action of external force, thereby providing a flexible conductive superhydrophobic with simple operation.
  • the preparation method of the coating layer has the advantages of excellent hydrophobicity, electrical conductivity and acid-base stability, and the coating can maintain hydrophobicity and electrical conductivity even under tension.
  • the invention firstly uses the alkyl mercaptan to hydrophobize the silver particles, and then sprays a mixed solution of the thermoplastic elastomer, the hydrophobic silver particles and the organic solvent on the rubber substrate pre-stretched to a certain ratio by external force, to be coated. After the layer is dried, the rubber substrate is relaxed to obtain a flexible conductive superhydrophobic coating.
  • the superhydrophobic coating prepared by the invention has excellent electrical conductivity, acid and alkali stability and stretchability, and the coating can maintain hydrophobicity and electrical conductivity under the tensile state, and is resistant to ice coating and anti-adhesion. , conductive path and strain sensing have broad application prospects.
  • a flexible conductive superhydrophobic coating comprising rubber as a base and containing hydrophobic silver particles; a water contact angle of 152-162° at room temperature, a resistance of 10 1 -10 3 ⁇ ; and a strong acid and a strong alkali drop on the coating
  • the upper side is kept for 10-30 minutes or the coating is kept at 150° or more after the stretching-relaxing for 20 cycles; the coating maintains hydrophobicity and electrical conductivity under tension.
  • the preparation method of the flexible conductive superhydrophobic coating comprises the following steps:
  • thermoplastic elastomer in terms of parts by mass, first add 0.5 part of thermoplastic elastomer to 20-50 parts of organic solvent, stir at 30-60 ° C for 3-12 h, then add 1-2 parts of hydrophobic silver particles, ultrasonic dispersion 0.5- 2h, the mixed dispersion is prepared; then the rubber substrate is pre-stretched to 2-3 times of the original length by an external force, and the mixed dispersion is sprayed on the rubber substrate by a spray gun; finally, after the coating is dried, the external force is removed, so that The rubber substrate is returned to its original length to produce a flexible conductive superhydrophobic coating.
  • the alkyl mercaptan is a mixture of any one or two of dodecyl mercaptan, tetradecyl mercaptan, hexadecanethiol and octadecyl mercaptan.
  • the thermoplastic elastomer is a styrene-butadiene-styrene block copolymer, a styrene-isoprene-styrene block copolymer, a hydrogenated styrene-butadiene-styrene block A mixture of any one or both of a segment copolymer and a hydrogenated styrene-isoprene-styrene block copolymer.
  • the silver particles have a size of from 100 to 300 nm.
  • the organic solvent is any one of toluene, xylene, tetrahydrofuran and cyclohexane.
  • the rubber substrate is any one of natural rubber, silicone rubber, butyl rubber, and nitrile rubber.
  • the working pressure of the spraying is 0.4-0.7 MPa
  • the spraying distance of the spray gun from the substrate is 10-20 cm
  • the moving speed of the spray gun is 1-2 cm/s
  • the reciprocating movement is 1-3 cycles.
  • the time of the ultrasonic dispersion in step 1) is 5-30 min, the time of the continuous stirring is 3-12 h; the rotation speed of the centrifugation is 6000-10000 rpm, and the time is 10-30 min;
  • the product was washed with ethanol; the vacuum drying was vacuum dried at 30-50 ° C for 5-12 h.
  • the coating of step 2) is dried by drying the coating at 30-50 ° C for 10-30 min to fully evaporate the solvent.
  • the coating prepared by the present invention has excellent resistance to acid and alkali stability and stretchability in addition to superhydrophobicity and electrical conductivity, and is a multifunctional coating.
  • the flexible conductive superhydrophobic coating prepared by the invention shrinks with the recovery of the rubber substrate, increases surface roughness and increases the number of conductive paths, and maintains excellent hydrophobicity and conductivity in a stretched state, wherein conductive
  • the behavior increases with the increase of tensile strain and has important application value on strain sensors.
  • the invention adopts the spraying method to prepare the coating, and the process is simple and can be produced in a large area.
  • Figure 1 is a graph showing the change in electrical resistance of a flexible conductive superhydrophobic coating prepared in Example 1 during stretching.
  • a hydrogenated styrene-butadiene-styrene block copolymer was added to 17.5 g of toluene, stirred at 40 ° C for 5 hours, and then 1.05 g of hydrophobic silver particles were added and ultrasonically dispersed for 1 hour to prepare a mixed dispersion.
  • the natural rubber substrate was pre-stretched to 3 times the original length by an external force, and the mixed dispersion was prepared by using a spray gun (working pressure of 0.6 MPa, spray gun 15 cm from the rubber base, moving speed of 1 cm/s, and reciprocating spray of the spray gun for 2 cycles). Spray on a rubber substrate.
  • the coating was dried at 30 ° C for 15 min to sufficiently evaporate the solvent, the external force was removed to restore the rubber substrate to its original length, and a flexible conductive superhydrophobic coating was obtained.
  • Table 1 lists the water contact angle and electrical resistance of the flexible conductive superhydrophobic coating prepared in this example. As can be seen from Table 1, the contact angle is 162.0° and the electric resistance is 15 ⁇ , which has excellent hydrophobicity and electrical conductivity. This is mainly because the silver particles will aggregate on the surface of the coating to form a certain rough structure with a large amount of solvent evaporation during the spraying process; then the pre-stretched rubber substrate will shrink the elastic coating during the recovery process, further increasing the surface roughness. Degree and form a conductive path.
  • the water contact angle of the coating becomes 160.0°, and the electric resistance becomes 21 ⁇ , which is because the thermoplastic elastomer has excellent flexibility.
  • the coating maintains a micro-nano roughness of the surface after the stretching-relaxation process, and most of the conductive paths are gradually repaired during the relaxation of the coating, and the coating still has good hydrophobicity and electrical conductivity.
  • the flexible conductive superhydrophobic coating prepared in this example In order to evaluate the hydrophobicity of the flexible conductive superhydrophobic coating prepared in this example under tension, it was stretched to 2, 3, 4, 5 and 6 times of the original length and fixed, and the surface was subjected to water contact angle test. The results obtained are shown in Table 3. As can be seen from Table 3, the flexible conductive superhydrophobic coating prepared in this example maintains superhydrophobicity when stretched to different multiples of the original length. This is mainly because the pre-stretched rubber substrate shrinks during the recovery process, and the surface roughness is greatly increased. Therefore, although the surface morphology of the coating changes during the stretching process, the micro-nano roughness structure can be maintained. It plays a key role in the maintenance of superhydrophobic properties.
  • the superhydrophobic coating prepared by using the silver particles and the thermoplastic elastomer as main raw materials on the rubber substrate not only has superhydrophobicity, but also has excellent electrical conductivity, acid and alkali stability and stretchability.
  • the coating retains hydrophobicity and electrical conductivity even under tension. Therefore, the superhydrophobic coating prepared by the present invention can maintain and use superhydrophobicity and electrical conductivity under harsh environmental conditions and external force. In the cold weather, super-hydrophobicity can prevent the ice from adhering to the surface, and the conductive ice can be used to melt a small amount of ice adhering to the surface. The combination of the two can be well applied to the anti-icing field.
  • the superhydrophobic coating prepared by the present invention can also be applied to sensors and related fields in response to tensile strain in electrical resistance during stretching.
  • 3 g of silver particles having a size of 250-300 nm were dispersed in 100 g of a 40% by weight solution of tetradecyl mercaptan in ethanol, sonicated for 5 min and stirred at room temperature for 3 h, and then centrifuged at 6000 rpm for 30 min to produce the product. After washing with ethanol and drying under vacuum at 30 ° C for 12 h, hydrophobic silver particles were obtained.
  • a styrene-isoprene-styrene block copolymer was added to 16 g of xylene, stirred at 30 ° C for 12 h, and then 1.2 g of hydrophobic silver particles were added and ultrasonically dispersed for 1 h to prepare a mixed dispersion.
  • the natural rubber substrate was pre-stretched to 2.5 times the original length by an external force, and the mixed dispersion was prepared by using a spray gun (working pressure: 0.7 MPa, spray gun 20 cm from the rubber substrate, moving speed 2 cm/s, and reciprocating spray of the spray gun for 2 cycles). Spray on a rubber substrate.
  • the external force was removed to return the rubber substrate to its original length, and a flexible conductive superhydrophobic coating was obtained.
  • Table 1 lists the water contact angle and electrical resistance of the flexible conductive superhydrophobic coating prepared in this example. As can be seen from Table 1, the contact angle was 159.0° and the electric resistance was 246 ⁇ , which was excellent in hydrophobicity and electrical conductivity.
  • the flexible conductive superhydrophobic coating prepared in this example has a water contact angle of 157.0° and a resistance of 269 ⁇ after 20 stretching-relaxing cycles, and the coating still maintains superhydrophobicity and excellent electrical conductivity.
  • Table 3 lists the contact angles of the flexible conductive superhydrophobic coating prepared in this example when stretched to 2, 3, 4, 5 and 6 times the original length. It can be seen from Table 3 that the prepared flexible conductive superhydrophobic coating has a surface contact angle of more than 150° when stretched to 2, 3, 4, 5 and 6 times of the original length, and has excellent resistance to stretching. The ability to deform.
  • 2g of silver particles having a size of 200-300 nm were dispersed in 100 g of a mass concentration of 2 wt% of dodecanethiol and hexadecanethiol (dodecyl mercaptan and hexadecanethiol mass ratio of 1) in an ethanol solution, and ultrasonically dispersed for 20 min. Stirring was continued for 10 h at room temperature, followed by centrifugation at 8000 rpm for 15 min. The product was washed with ethanol and dried under vacuum at 40 ° C for 8 h to obtain hydrophobic silver particles.
  • a hydrogenated styrene-isoprene-styrene block copolymer was added to 15 g of toluene, stirred at 50 ° C for 5 hours, and then 1.2 g of hydrophobic silver particles were added and ultrasonically dispersed for 2 hours to prepare a mixed dispersion.
  • the silicone rubber substrate is pre-stretched to 3 times the original length by external force, and the mixture is dispersed by a spray gun (working pressure is 0.5 MPa, the spray gun is 15 cm from the rubber base, the moving speed is 1.5 cm/s, and the spray gun is reciprocally sprayed for 1 cycle). The liquid is sprayed on a rubber substrate.
  • the coating was dried at 40 ° C for 15 min to sufficiently evaporate the solvent, the external force was removed to return the rubber substrate to its original length, and a flexible conductive superhydrophobic coating was obtained.
  • Table 1 lists the water contact angle and electrical resistance of the flexible conductive superhydrophobic coating prepared in this example. As can be seen from Table 1, the contact angle is 160.0° and the electric resistance is 592 ⁇ , which has excellent hydrophobicity and electrical conductivity.
  • the flexible conductive superhydrophobic coating prepared in this example has a water contact angle of 158.5° and a resistance of 615 ⁇ after 20 stretching-relaxing cycles, and the coating still maintains superhydrophobicity and excellent electrical conductivity.
  • Table 3 lists the contact angles of the flexible conductive superhydrophobic coating prepared in this example when stretched to 2, 3, 4, 5 and 6 times the original length. It can be seen from Table 3 that the prepared flexible conductive superhydrophobic coating has a surface contact angle of more than 150° when stretched to 2, 3, 4, 5 and 6 times of the original length, and has excellent resistance to stretching. The ability to deform.
  • 0.175 g of a styrene-butadiene-styrene block copolymer was added to 17.5 g of tetrahydrofuran, stirred at 60 ° C for 3 hours, and further 0.35 g of hydrophobic silver particles were added and ultrasonically dispersed for 0.5 h to prepare a mixed dispersion.
  • the nitrile rubber substrate was pre-stretched to 2 times the original length by external force, and the mixture was dispersed by a spray gun (working pressure: 0.4 MPa, spray gun 10 cm from the rubber base, moving speed 1 cm/s, spray gun reciprocating spray for 3 cycles). The liquid is sprayed on a rubber substrate.
  • the external force was removed to restore the rubber substrate to its original length, and a flexible conductive superhydrophobic coating was obtained.
  • Table 1 shows the water contact angle and electrical resistance of the flexible conductive superhydrophobic coating of the embodiment of the present invention
  • Table 1 lists the water contact angle and electrical resistance of the flexible conductive superhydrophobic coating prepared in this example.
  • the contact angle is 160.0° and the electric resistance is 135 ⁇ , which has excellent hydrophobicity and electrical conductivity.
  • the water contact angle of the coating was 156.5°
  • the electric resistance was 178 ⁇
  • the coating remained super-hydrophobic and excellent in electrical conductivity.
  • the contact angle was tested using the DSA100 tester from KRUSS, Germany, and the average of 5 points was calculated for each sample.
  • the resistance was measured using a micro-ohmmeter (TEGAM1740, USA), and an average of 3 points was calculated for each sample.
  • Table 3 shows the water contact angles of the flexible conductive superhydrophobic coatings at different draw ratios according to an embodiment of the present invention.
  • Table 3 lists the contact angles of the flexible conductive superhydrophobic coating prepared in this example at 2, 3, 4, 5 and 6 times the original length. It can be seen from Table 3 that the prepared flexible conductive superhydrophobic coating has a surface contact angle of more than 150° when stretched to 2, 3, 4, 5 and 6 times of the original length, and has excellent resistance to stretching. The ability to deform.

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Abstract

本发明公开了一种柔性导电超疏水涂层及其制备方法。首先采用烷基硫醇对银颗粒进行疏水化改性；其次，将热塑性弹性体、疏水性银颗粒在有机溶剂中混合均匀后喷涂在用外力预拉伸至一定比例的橡胶基底上；最后，待涂层干燥后将外力去除使橡胶基底松弛，赋予涂层表面明显的粗糙度并形成导电通路，制得一种基于橡胶基底的柔性导电超疏水涂层。本发明所制备的涂层室温下水接触角为152-162°，电阻为101-103Ω，具有优良的导电性、耐酸碱稳定性和可拉伸性，且涂层在拉伸状态下也能保持疏水性和导电性，具有广阔的应用前景。

Description

一种柔性导电超疏水涂层及其制备方法 技术领域
本发明涉及一种超疏水涂层领域，具体涉及一种柔性导电超疏水涂层及其制备方法。
背景技术
受自然界中“荷叶效应”的启发，人们发现存在超疏水表面，其静态水滴接触角大于150°，滚动角小于10°。由于这种独特的浸润性，超疏水表面在自清洁、防覆冰、防污染、阻燃、油水分离等领域具有重要的应用价值，因此引起了研究者们的广泛关注。传统方法制备的超疏水涂层存在制备工艺繁琐、反应条件苛刻、化学稳定性及机械耐久性差等缺点。为了解决以上问题，国内外研究人员进行了一系列探索研究，虽然在超疏水涂层的制备方法及耐久性上取得了一定进展，但其仍存在柔软性差、不耐拉伸和弯折等缺点。
近年来，随着科学技术的发展，人们对功能性的超疏水涂层的需求越来越大。作为一种重要的功能性超疏水涂层，导电超疏水涂层在电子电器设备中具有广泛的用途，但与其相关的研究还鲜少报道。目前用于电子电器中的导电涂层通常不具备超疏水性，主要是以高分子材料为基体并掺杂一定数量的导电物质(如银纳米线、纳米银粉、碳纳米管、石墨烯等)以及溶剂和助剂组合而成，且在外力作用下导电通路容易被破坏而失去导电性。
发明内容
本发明针对目前超疏水涂层柔软性差、不耐拉伸和弯折等缺点以及导电涂层不 具备疏水性、在外力作用下导电性易破坏等缺点，提供一种操作简单的柔性导电超疏水涂层的制备方法，所得涂层具有优良的疏水性、导电性和耐酸碱稳定性等优点，且涂层在拉伸状态下也能保持疏水性和导电性。
本发明首先采用烷基硫醇对银颗粒进行疏水化改性，再将热塑性弹性体、疏水性银颗粒和有机溶剂的混合溶液喷涂在用外力预拉伸至一定比例的橡胶基底上，待涂层干燥后松弛橡胶基底得到柔性导电超疏水涂层。本发明制备的超疏水涂层具有优良的导电性、耐酸碱稳定性和可拉伸性，且涂层在拉伸状态下也能保持疏水性和导电性，在防覆冰、抗粘附、导电通路及应变传感上具有广阔的应用前景。
本发明的目的通过如下技术方案实现：
一种柔性导电超疏水涂层，以橡胶为基底，含有疏水性银颗粒；室温下水接触角为152-162°，电阻为10 1-10 3Ω；将强酸和强碱液滴滴在涂层上保持10-30min或者涂层在拉伸-松弛20个循环后，其接触角均保持在150°以上并导电；涂层在拉伸状态下保持疏水性和导电性。
所述的柔性导电超疏水涂层的制备方法，包括以下步骤：
1)按质量份数计，将1-3份银颗粒分散在100份质量浓度为0.5-3wt％的烷基硫醇的乙醇溶液中，超声分散，并在室温下继续搅拌，离心处理，洗涤后真空干燥，即得疏水性银颗粒；
2)按质量份数计，首先将0.5份热塑性弹性体加入20-50份有机溶剂中，在30-60℃下搅拌3-12h，再加入1-2份疏水性银颗粒，超声分散0.5-2h，制得混合分散液；然后用外力将橡胶基底预拉伸至原长的2-3倍，利用喷枪将混合分散液喷涂在橡胶基底上；最后，涂层干燥后，将外力去除，使橡胶基底回复到原来的长度，制得柔性导电超疏水涂层。
为进一步实现本发明目的，优选地，所述的烷基硫醇为十二硫醇、十四硫醇、十六硫醇和十八硫醇中的任意一种或两种的混合物。
优选地，所述的热塑性弹性体为苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物和氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物中的任意一种或两种的混合物。
优选地，所述的银颗粒的尺寸为100-300nm。
优选地，所述的有机溶剂为甲苯、二甲苯、四氢呋喃和环己烷中的任意一种。
优选地，所述的橡胶基底为天然橡胶、硅橡胶、丁基橡胶和丁腈橡胶中的任意一种。
优选地，所述喷涂的工作压力为0.4-0.7MPa，喷枪与基底的喷涂距离为10-20cm，喷枪的移动速度为1-2cm/s，且往复移动1-3个循环。
优选地，步骤1)所述超声分散的时间为5-30min，所述继续搅拌的时间为3-12h；所述离心处理的转速为6000-10000rpm，时间为10-30min；所述洗涤是将产物用乙醇洗涤；所述真空干燥是30-50℃下真空干燥5-12h。
优选地，步骤2)所述涂层干燥是将涂层在30-50℃下干燥10-30min，使溶剂充分挥发。
本发明所述的柔性导电超疏水涂层的制备方法，与现有技术相比，具有如下优点：
(1)本发明制备的涂层除了具有超疏水性和导电性，还具备优良的耐酸碱稳定性和可拉伸性，属于一种多功能涂层。
(2)本发明制备的柔性导电超疏水涂层会随着橡胶基底的回复而收缩，使表面粗糙度增大和导电通路增多，在拉伸状态下能保持优良的疏水性和导电性，其中 导电性随拉伸应变的增大呈递增关系，在应变传感器上有重要应用价值。
(3)本发明采用喷涂法制备涂层，工艺简单，可大面积生产。
附图说明
图1为实施例1中制备的柔性导电超疏水涂层在拉伸过程中的电阻变化。
具体实施方法
为更好地理解本发明，下面结合实施例对本发明作进一步说明，但是本发明的实施方式不限于此。
实施例1
将2g尺寸为100-200nm的银颗粒分散在100g质量浓度为1wt％的十六硫醇的乙醇溶液中，超声分散15min并在室温下继续搅拌8h，然后以8000rpm的转速离心20min，将产物用乙醇洗涤后在40℃下真空干燥8h，即得疏水性银颗粒。将0.35g氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物加入17.5g甲苯中，在40℃搅拌5h，再加入1.05g疏水银颗粒，超声分散1h，制得混合分散液。其次，用外力将天然橡胶基底预拉伸至原长的3倍，利用喷枪(工作压力为0.6MPa，喷枪距离橡胶基底15cm，移动速度1cm/s，喷枪往复喷涂2个循环)将混合分散液喷涂在橡胶基底上。最后，涂层在30℃下干燥15min使溶剂充分挥发后，将外力去除使橡胶基底回复到原来的长度，制得柔性导电超疏水涂层。
表1列出了本实施例制备的柔性导电超疏水涂层的水接触角和电阻。从表1可以看出，其接触角为162.0°，电阻为15Ω，具有优良的疏水性和导电性。这主要是因为喷涂过程中随着溶剂的大量挥发，银颗粒会在涂层表面聚集形成一定的粗糙结构；随后预拉伸的橡胶基底在回复过程会使弹性涂层发生收缩，进一步增加表面粗糙度，并形成导电通路。
为了评价本实施例制备的柔性导电超疏水涂层的耐酸碱稳定性，将一滴体积10μL的pH＝0的强酸液滴和一滴体积10μL的pH＝14的强碱液滴分别滴在柔性导电超疏水涂层表面并保持20min，测试其接触角和电阻，所得结果列于表2。为了评价本实施例制备的柔性导电超疏水涂层的可拉伸性，将其拉伸至原长的3倍，再松弛回复，此过程重复20个循环，测试其接触角和电阻，所得结果列于表2。从表2可以看出，强酸(pH＝0)和强碱(pH＝14)液滴在本实施例制备的柔性导电超疏水涂层表面保持20min后，接触角均保持在150°以上，且涂层导电性基本不变。此外，本实施例制备的柔性导电超疏水涂层经20个拉伸-松弛循环后，涂层的水接触角变为160.0°，电阻变为21Ω，这是由于热塑性弹性体具有优异的柔韧性，涂层在拉伸-松弛过程后保持表面的微纳粗糙结构，且大部分导电通路在涂层松弛过程中逐渐修复，涂层仍具有良好的疏水性和导电性。
为了评价本实施例制备的柔性导电超疏水涂层在拉伸状态下的疏水性，将其拉伸至原长的2、3、4、5和6倍并固定，对表面进行水接触角测试，所得结果列于表3。从表3可以看出，本实施例制备的柔性导电超疏水涂层在拉伸至原长的不同倍数时，涂层表面保持超疏水性。这主要是因为预拉伸的橡胶基底在回复过程中，涂层发生收缩，表面粗糙度大幅度增加，因此涂层在拉伸过程中表面形貌虽然发生变化，但仍能保持微纳粗糙结构，对超疏水性能的保持起到关键作用。
为了评价本实施例制备的柔性导电超疏水涂层在拉伸状态下的导电性，采用微欧计(TEGAM1740，USA)实时记录其拉伸至原长1.5倍的形变过程中的电阻，并以涂层拉伸状态下的电阻与涂层初始电阻的比值作为纵坐标，涂层拉伸过程中的应变(涂层拉伸长度变化量与涂层原长度的比值×100％)作为横坐标，所得结果如图1所示。从图1可以看出，本实施例制备的柔性导电超疏水涂层随拉伸应变的增 大，电阻逐渐增加。这主要是因为在喷涂过程中随着溶剂的挥发，银颗粒会在涂层中形成少量导电通路；随后预拉伸的橡胶基底的回复过程使涂层发生收缩，进一步增加表面银颗粒堆积密度，形成较多的导电通路。而在拉伸过程中，部分堆积的银颗粒的导电通路发生破坏，使导电性下降。本发明制备的柔性导电超疏水涂层的电阻在拉伸过程中对拉伸应变的响应可以应用于传感器及其相关领域。
目前，大多数超疏水涂层仅具有超疏水这一特性，功能单一。而本发明采用银颗粒和热塑性弹性体为主要原料在橡胶基底上制备的超疏水涂层不仅具有超疏水性，而且还具有优良的导电性、耐酸碱稳定性和可拉伸性。涂层在拉伸状态下也能保持疏水性和导电性。因此，本发明所制备的超疏水涂层可在苛刻的环境条件和外力作用条件下保持和使用超疏水性及导电性。在严寒天气，超疏水性可以防止冰在表面粘附，而且利用导电性通电生热可以将表面粘附的少量冰融化，两者结合可以很好地应用于防覆冰领域。在拉伸过程中，利用电阻对拉伸应变的响应，本发明所制备的超疏水涂层还可应用于传感器及其相关领域。
实施例2
将3g尺寸为250-300nm的银颗粒分散在100g质量浓度为0.5wt％的十四硫醇的乙醇溶液中，超声分散5min并在室温下继续搅拌3h，然后以6000rpm的转速离心30min，将产物用乙醇洗涤后在30℃下真空干燥12h，即得疏水性银颗粒。将0.4g苯乙烯-异戊二烯-苯乙烯嵌段共聚物加入16g二甲苯中，在30℃搅拌12h，再加入1.2g疏水性银颗粒，超声分散1h，制得混合分散液。其次，用外力将天然橡胶基底预拉伸至原长的2.5倍，利用喷枪(工作压力为0.7MPa，喷枪距离橡胶基底20cm，移动速度2cm/s，喷枪往复喷涂2个循环)将混合分散液喷涂在橡胶基底上。最后，涂层在30℃下干燥30min使溶剂充分挥发后，将外力去除使橡胶基 底回复到原来的长度，制得柔性导电超疏水涂层。
表1列出了本实施例制备的柔性导电超疏水涂层的水接触角和电阻。从表1可以看出，其接触角为159.0°，电阻为246Ω，具有优良的疏水性和导电性。
表2列出了本实施例中强酸(pH＝0)和强碱(pH＝14)液滴在制备的柔性导电超疏水涂层上保持20min及涂层在拉伸-松弛20个循环后的水接触角和电阻。从表2可以看出，强酸(pH＝0)和强碱(pH＝14)液滴在本实施例制备的柔性导电超疏水涂层表面保持20min后，接触角均保持在150°以上，且电阻基本不变，具有优良的化学稳定性。此外，本实施例制备的柔性导电超疏水涂层经20个拉伸-松弛循环后，涂层的水接触角为157.0°，电阻为269Ω，涂层仍保持超疏水性和优良的导电性。
表3列出了本实施例制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时的接触角。从表3可以看出，制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时，涂层表面接触角均大于150°，具有优良的抵抗拉伸形变的能力。
实施例3
将2g尺寸为200-300nm的银颗粒分散在100g质量浓度为2wt％的十二硫醇和十六硫醇(十二硫醇和十六硫醇质量比为1)的乙醇溶液中，超声分散20min并在室温下继续搅拌10h，然后以8000rpm的转速离心15min，将产物用乙醇洗涤后在40℃下真空干燥8h，即得疏水性银颗粒。将0.3g氢化苯乙烯-异戊二烯-苯乙烯嵌段共聚物加入15g甲苯中，在50℃搅拌5h，再加入1.2g疏水性银颗粒，超声分散2h，制得混合分散液。其次，用外力将硅橡胶基底预拉伸至原长的3倍，利用喷枪(工作压力为0.5MPa，喷枪距离橡胶基底15cm，移动速度1.5cm/s，喷枪往 复喷涂1个循环)将混合分散液喷涂在橡胶基底上。最后，涂层在40℃下干燥15min使溶剂充分挥发后，将外力去除使橡胶基底回复到原来的长度，制得柔性导电超疏水涂层。
表1列出了本实施例制备的柔性导电超疏水涂层的水接触角和电阻。从表1可以看出，其接触角为160.0°，电阻为592Ω，具有优良的疏水性和导电性。
表2列出了本实施例中强酸(pH＝0)和强碱(pH＝14)液滴在制备的柔性导电超疏水涂层上保持20min及涂层在拉伸-松弛20个循环后的水接触角和电阻。从表2可以看出，强酸(pH＝0)和强碱(pH＝14)液滴在本实施例制备的柔性导电超疏水涂层表面保持20min后，接触角均保持在150°以上，且电阻基本不变，具有优良的化学稳定性。此外，本实施例制备的柔性导电超疏水涂层经20个拉伸-松弛循环后，涂层的水接触角为158.5°，电阻为615Ω，涂层仍保持超疏水性和优良的导电性。
表3列出了本实施例制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时的接触角。从表3可以看出，制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时，涂层表面接触角均大于150°，具有优良的抵抗拉伸形变的能力。
实施例4
将1g尺寸为100-150nm的银颗粒分散在100g质量浓度为3wt％的十八硫醇的乙醇溶液中，超声分散30min并在室温下继续搅拌12h，然后以10000rpm的转速离心10min，将产物用乙醇洗涤后在50℃下真空干燥5h，即得疏水性银颗粒。将0.175g苯乙烯-丁二烯-苯乙烯嵌段共聚物加入17.5g四氢呋喃中，在60℃搅拌3h，再加入0.35g疏水性银颗粒，超声分散0.5h，制得混合分散液。其次，用外力将丁 腈橡胶基底预拉伸至原长的2倍，利用喷枪(工作压力为0.4MPa，喷枪距离橡胶基底10cm，移动速度1cm/s，喷枪往复喷涂3个循环)将混合分散液喷涂在橡胶基底上。最后，涂层在50℃下干燥10min使溶剂充分挥发后，将外力去除使橡胶基底回复到原来的长度，制得柔性导电超疏水涂层。
表1为本发明实施例柔性导电超疏水涂层的水接触角和电阻；表1列出了本实施例制备的柔性导电超疏水涂层的水接触角和电阻。从表1可以看出，其接触角为160.0°，电阻为135Ω，具有优良的疏水性和导电性。
表1
Figure PCTCN2018111932-appb-000001
注：采用德国KRUSS公司的DSA100测试仪对接触角进行测试，每个样品取5个点计算平均值。
表2为本发明实施例柔性导电超疏水涂层在酸碱液滴处理或拉伸-松弛循环后的水接触角和电阻；表2列出了本实施例中强酸(pH＝0)和强碱(pH＝14)液滴在制备的柔性导电超疏水涂层上保持20min及涂层在拉伸-松弛20个循环后的水接触角和电阻。从表2可以看出，强酸(pH＝0)和强碱(pH＝14)液滴在本实施例制备的柔性导电超疏水涂层表面保持20min后，接触角均保持在150°以上，且电阻基本不变，具有优良的化学稳定性。此外，本实施例制备的柔性导电超疏水涂层经20个拉伸-松弛循环后，涂层的水接触角为156.5°，电阻为178Ω，涂层仍保持超疏 水性和优良的导电性。
表2
Figure PCTCN2018111932-appb-000002
注：采用德国KRUSS公司的DSA100测试仪对接触角进行测试，每个样品取5个点计算平均值。采用微欧计(TEGAM1740，USA)对电阻进行测量，每个样品取3个点计算平均值。
表3
Figure PCTCN2018111932-appb-000003
注：采用德国KRUSS公司的DSA100测试仪对接触角进行测试，每个样品取5个点计算平均值。
表3为本发明实施例柔性导电超疏水涂层在不同拉伸倍数时的水接触角。表3列出 了本实施例制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时的接触角。从表3可以看出，制备的柔性导电超疏水涂层在拉伸至原长的2、3、4、5和6倍时，涂层表面接触角均大于150°，具有优良的抵抗拉伸形变的能力。

Claims (10)

  1. 一种柔性导电超疏水涂层，其特征在于，所述的柔性导电超疏水涂层以橡胶为基底，含有疏水性银颗粒；室温下水接触角为152-162°，电阻为10 1-10 3Ω；将强酸和强碱液滴滴在涂层上保持10-30min或者涂层在拉伸-松弛20个循环后，其接触角均保持在150°以上并导电；涂层在拉伸状态下保持疏水性和导电性。
  2. 权利要求1所述的柔性导电超疏水涂层的制备方法，其特征在于包括以下步骤：
    1)按质量份数计，将1-3份银颗粒分散在100份质量浓度为0.5-3wt％的烷基硫醇的乙醇溶液中，超声分散，并在室温下继续搅拌，离心处理，洗涤后真空干燥，即得疏水性银颗粒；
    2)按质量份数计，首先将0.5份热塑性弹性体加入20-50份有机溶剂中，在30-60℃下搅拌3-12h，再加入1-2份疏水性银颗粒，超声分散0.5-2h，制得混合分散液；然后用外力将橡胶基底预拉伸至原长的2-3倍，利用喷枪将混合分散液喷涂在橡胶基底上；最后，涂层干燥后，将外力去除，使橡胶基底回复到原来的长度，制得柔性导电超疏水涂层。
  3. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述的烷基硫醇为十二硫醇、十四硫醇、十六硫醇和十八硫醇中的任意一种或两种的混合物。
  4. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述的热塑性弹性体为苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-异戊二烯-苯乙烯嵌段共聚物、氢化苯乙烯-丁二烯-苯乙烯嵌段共聚物和氢化苯乙烯-异戊二烯-苯乙 烯嵌段共聚物中的任意一种或两种的混合物。
  5. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述的银颗粒的尺寸为100-300nm。
  6. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述的有机溶剂为甲苯、二甲苯、四氢呋喃和环己烷中的任意一种。
  7. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述的橡胶基底为天然橡胶、硅橡胶、丁基橡胶和丁腈橡胶中的任意一种。
  8. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：所述喷涂的工作压力为0.4-0.7MPa，喷枪与基底的喷涂距离为10-20cm，喷枪的移动速度为1-2cm/s，且往复移动1-3个循环。
  9. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：步骤1)所述超声分散的时间为5-30min，所述继续搅拌的时间为3-12h；所述离心处理的转速为6000-10000rpm，时间为10-30min；所述洗涤是将产物用乙醇洗涤；所述真空干燥是30-50℃下真空干燥5-12h。
  10. 根据权利要求2所述的柔性导电超疏水涂层的制备方法，其特征在于：步骤2)所述涂层干燥是将涂层在30-50℃下干燥10-30min，使溶剂充分挥发。
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