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CN106167551A - 一种抗水冲刷超疏水复合膜及其制法和应用 - Google Patents

一种抗水冲刷超疏水复合膜及其制法和应用 Download PDF

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Publication number
CN106167551A
CN106167551A CN201610634412.XA CN201610634412A CN106167551A CN 106167551 A CN106167551 A CN 106167551A CN 201610634412 A CN201610634412 A CN 201610634412A CN 106167551 A CN106167551 A CN 106167551A
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solution
super
membrane
hydrophobic
composite
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王林格
吴杰
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

本发明属于高分子材料领域，公开了一种抗水冲刷超疏水复合纤维膜及其制备方法和应用。该复合纤维膜是将疏水性高分子材料溶液通过静电纺丝技术制备成高分子纤维；再将同种或异种疏水性高分子材料溶液通过静电喷涂技术涂覆在上述的纤维膜上；随后对复合膜进行物理或化学交联处理，最后得到由纤维和微球组成的、表面具有微纳结构的超疏水复合膜。所述的抗水冲刷超疏水复合膜中纤维的直径为100nm～20μm，微球尺寸在1～30μm。本发明的复合纤维膜中纤维和微球构成的微纳结构被固定，使其具有优异的超疏水和抗冲洗性能，可应用于油水分离，自清洁，防冻和抗菌等领域，经济效益潜力巨大。

Description

一种抗水冲刷超疏水复合膜及其制法和应用
技术领域
本发明属于高分子材料领域，特别涉及一种抗水冲刷超疏水复合膜及其制备方法和应用。
背景技术
超疏水材料是指水滴和材料表面静态接触角大于150°，而滚动角小于10°的材料，应用范围包括自清洁、油水分离、防冻以及降低流体阻力等。超疏水材料具备这种超疏水性能的两个关键因素是：一、表面自由能低；二、表面的粗糙度要高。因此，制备具有特殊分级结构表面的材料，如天然的荷叶表面、昆虫翅膀、鸟类羽毛等的，具有不同纳米、微米尺度的复合结构(微纳结构)表面的材料，而获得此类超疏水性能。目前，已开发出多种的相关制备方法：如无机纳米粒子表面涂覆，电化学聚合，等离子刻蚀，模板法，静电纺丝/静电喷涂法等。其中，静电纺丝法和静电喷涂法越来越受到重视。二者都是利用高压静电使高分子溶液带电，之后溶液通过注射器等容器给样，在收集装置收集。通过调控溶液浓度参数、电压条件和收集装置可以制备各种形貌和尺寸的微球或纤维。通常，低浓度的高分子溶液由于其中的分子链缠结度较低，会在电场和表面张力的共同作用下形成微球；而一种特殊的情况是，对嵌段共聚物通过采用混合溶剂配比成微相分离体系也可造成分子链的低缠结，并电喷形成微球(相关工作见文章：L.Wang等，Macromolecular Rapid Communications，36(15),1437-1443)。高浓度的高分子溶液中高分子链缠结度高，其分子链会在静电作用下形成纤维。此外，高分子量的高分子往往容易在低浓度下的溶液中就形成高的链缠结，所以其静电纺溶液浓度会较低；反之，低分子量的高分子，需配置稍高浓度值的溶液进行静电喷。在已有的报道中，通过静电纺丝和静电喷涂制备纤维-微球的复合膜生产疏水膜材料是一种可行的方法。但其也存在一个显着的缺陷，即微球和纤维的结合只是简单的物理吸附在一起，在实际应用中，在外力(如摩擦)和水的冲刷作用下，微球会从纤维表面脱落，从而造成材料超疏水性能的丧失，并失去实际的应用价值(相关工作见文章：S.T.Yoheg等，Chemical Communications,2013,49(8),804-806)。
因此，从应用角度出发，需要一种具有一定的微纳米结构和超疏水性能且具有抗水冲刷能力的复合膜材料。
发明内容
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种抗水冲刷超疏水复合膜。该复合膜由高分子纤维和高分子微球通过物理或化学交联组成。该复合膜表面具有大粗糙度的微纳结构，具有超疏水性能；并且抗冲洗性能优异，能在长时间保持超疏水性能。
本发明另一目的在于提供一种上述抗水冲刷超疏水复合膜的制备方法。
本发明再一目的在于提供上述抗水冲刷超疏水复合膜在油水分离、自清洁涂层、流体减阻、抗菌、防冻以及降低流体阻力等领域的应用。
本发明的目的通过以下技术方案实现：
一种抗水冲刷超疏水复合膜，是将疏水性高分子材料溶液通过静电纺丝技术制备成高分子纤维；再将同种或异种疏水性高分子材料溶液通过静电喷涂技术涂覆在在上述的纤维膜上；随后对复合膜进行物理或化学交联处理，最后得到由纤维和微球组成的、表面具有微纳结构的超疏水复合膜。
所述的抗水冲刷超疏水复合膜中纤维的直径为100nm～20μm，微球尺寸在1～30μm。
所述的疏水性高分子材料可为苯乙烯系热塑性弹性体、聚烯烃、聚苯乙烯、聚脲、聚砜、聚甲基丙烯酸、聚缩醛和聚酯中的至少一种。
优选的，所述苯乙烯系热塑性弹性体可为聚苯乙烯-聚(乙烯-丁烯)-聚苯乙烯嵌段共聚物(SEBS)、聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物(SBS)、聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物(SIS)或聚苯乙烯-聚(乙烯-丙烯)-聚苯乙烯嵌段共聚物(SEPS)。
优选的，所述聚烯烃可为聚乙烯(PE)、聚丙烯(PP)、聚乙烯-辛烯共聚物(POE)、聚氯乙烯(PVC)、聚苯乙烯(PS)或聚偏氟乙烯(PVDF)。
优选的，所述聚酯可为聚丙烯酸酯(Polyacrylate)、聚甲基丙烯酸酯(PAMA)、聚甲基丙烯酸甲酯(PMMA)、聚乙酸乙烯酯(PVAc)、聚己内酯(PCL)、聚对苯二甲酸乙二酯(PET)、聚氨酯(PU)或聚碳酸(PC)酯。
所述的物理交联包括采用温度退火交联或有机溶剂退火交联。
所述的化学交联包括采用光、热、高能辐射、机械力、超声波和交联剂交联。
一种上述抗水冲刷超疏水复合膜的制备方法，具体包括以下步骤：
(1)静电纺丝法制备超细高分子纤维：将疏水性高分子材料溶于有机溶剂中，搅拌均匀后将高分子溶液装入带有喷射头的储存容器中，通过高压静电进行静电纺丝，采用收丝装置进行收集，将所得到的纤维放置于真空烘箱或室温中干燥至无溶剂残留即可得高分子纤维；
所述高分子溶液的浓度为5～30wt％，所述高压静电的电压为10～30kV，喷射头与收丝装置的距离为10～45cm，高分子溶液从喷射头流出速度为0.5～15mL/h，静电纺丝时环境温度为15～40℃，环境湿度为30～85％；
所述收丝装置可为：①平板收丝装置，由一块平板构成，接地或与负高压相连；②滚筒收丝装置，由直径为5～20cm的金属滚筒与电机组成，滚筒转速为50～3000r/min，滚筒接地或与负高压相连；所述的负高压为-30～-0.5kV；其中滚筒收丝时，将收集得到的纤维取下，旋转1～90°重新贴附于滚筒表面继续纺丝，可实现高分子纤维在滚筒表面多层、多方向取向的三维取向结构，收丝装置表面的铺覆铝箔。
(2)静电喷涂制备高分子微球：将同种或异种疏水性高分子材料溶于有机溶剂中，搅拌均匀后将得到的高分子溶液置于带有喷射头的储存容器中，并加载高压静电场，通过高压静电喷涂，以步骤1)所得纤维为铺盖在接收装置上，将溶液喷涂在纤维上形成高分子微球，即可得到纤维-微球复合结构膜；
所述高分子溶液的浓度为1～14wt％，所述高压静电场的电压为10～30kV，喷射头与接收装置的距离为10～25cm，溶液从喷射头喷出速度为1～5mL/h，静电喷涂时的环境温度为15～40℃，环境湿度为30～85％；
所述接收装置可为：①平板接收装置，由一块平板构成，接地或与负高压相连；②滚筒接收装置，由直径为5～20cm的金属滚筒与电机组成，滚筒转速为50～2000r/min，滚筒接地或与负高压相连；所述的负高压为-30～-0.5kV。
(3)交联处理：对复合纤维膜进行物理或化学交联处理，使高分子纤维和微球交联起来，最后得到抗水冲刷超疏水复合膜。
所述物理交联是把复合膜放入烘箱等可加热装置中，通过升温至高分子纤维或微球材料的熔点附近并保持一段时间，使高分子纤维和微球物理起来；交联温度范围在100～200℃，交联处理时间为30min～5h；
或者所述物理交联是把复合膜放入一个密闭容器中，放入步骤(1)或步骤(2)中所述的有机溶剂，进行交联处理一段时间，使高分子纤维和微球交联起来，之后放置于真空烘箱或室温中干燥至无溶剂残留即可得最终的复合膜；处理温度为20～70℃，处理时间为5～30min。
所述化学交联是采用光、热、高能辐射、机械力、超声波和交联剂交联。
所述交联剂为有机二元酸、多元醇等；或是分子内含有多个不饱和双键的化合物。
优选的，所述的交联剂为二乙烯基苯和二异氰酸酯，N,N-亚甲基双丙烯酰胺(MBA)或丙烯酸。
步骤(1)、(2)中所述的有机溶剂可为四氢呋喃(THF)、丙酮(Acetone)、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、醋酸甲酯(methyl acetate)、甲基异丁酮(MIBK)、二氯甲烷(DCM)、三氯甲烷(chloroform)、氯仿(CHCl3)、乙醇(Ethanol)、六氟异丙醇(HFIP)、三氟乙酸、三氟乙醇、异丙醇、N-甲基吗啉-N-氧化物(NMMO)、甲基氰(Acetonitrile)中的一种或多种混合。步骤(1)和步骤(2)中所述的有机溶剂可以相同也可以不同。
上述的超疏水复合纤维膜在油水分离、自清洁涂层、流体减阻、抗菌、防冻以及降低流体阻力等领域的应用。
本发明的机理为：
纤维和微球交叠形成一种类似荷叶表面的微米-纳米结构(微纳结构)，造成复合膜具有表面巨大的粗糙度。水滴与复合膜表面接触时的接触面由这次微纳结构和其中的空气共同构成，并使得水滴在复合膜表面具有大于150°接触角和小于10°滚动角，从而获得超疏水性能和自清洁等应用。在通过交联后，纤维和微球构成的微纳结构被固定，使得复合膜的超疏水性能能够在一定时间水流冲刷等外力作用下任被保存，从而最终得到一种抗水冲刷的超疏水复合膜。
本发明相对于现有技术，具有如下的优点及有益效果：
1、采用静电纺丝、静电喷涂、交联处理相结合的方法，构造了由纤维和微球相复合的微纳米多级结构且具有优异的抗水冲刷性能，复合纤维膜的超疏水性能相较于传统的电纺纤维膜更加优异。
2、本发明的制备方法工艺简单可行，重复性好，可适合于制备不同种类高分子材料的复合膜。
3、本发明的复合纤维膜具有优异的超疏水和抗冲洗性能，可应用于油水分离，自清洁，防冻和抗菌等领域，经济效益潜力巨大。
附图说明
图1为实施例1中温度退火交联处理后的超疏水复合膜结构示意图。
图2为实施例1中SEBS纤维和SEBS微球所构成的复合膜在温度退火交联处理之后的扫描电镜照片，其中a和b分别是不同放大倍数的扫描电镜照片。
图3为实施例2中SEBS纤维和SEBS微球所构成的复合膜的扫描电镜照片(a)，以及该复合膜接触角的测量图(b)。
图4为实施例2中SEBS纤维和SEBS微球所构成的复合膜的接触角在200小时水流冲刷过程中的变化图。
图5为实施例3中SEBS纤维和SEBS微球所构成的复合膜在温度退火交联处理之后的扫描电镜照片。
具体实施方式
以下结合实施例来进一步解释本说明，但实施例并不对本发明做任何形式的限定。
实施例中所用试剂如无特殊说明均可从市场常规购得。
实施例1
(1)将三嵌段共聚物聚苯乙烯-聚(乙烯-丁烯)-聚苯乙烯(SEBS，Mw＝8.45×104g/mol，PS的嵌段体积比为30％)溶解在四氢呋喃(THF)中，控制SEBS的浓度为14wt％，溶液配制好以后在25℃下搅拌6～8小时至均一纺丝溶液；静电纺该溶液制备SEBS纤维，控制溶液的进给速率为2mL/h，纺丝电压为10kV，收集距离为15cm，环境温度为25℃，环境湿度为50％，采用滚筒收丝器收集，滚筒直径20cm，滚筒转速50r/min，将该溶液电纺20min制备得到SEBS纤维膜。纤维平均直径为8μm。
(2)将同种SEBS溶解在四氢呋喃(THF)和N,N-二甲基甲酰胺(DMF)中，控制SEBS的质量浓度为14wt％，THF和DMF的质量比为80:20，溶液配制好以后在25℃下搅拌6～8小时至均一溶液；静电喷涂该溶液制备SEBS微球；将步骤(1)制备的SEBS纤维附在平板收集器上，收集器接地，将SEBS溶液电喷在SEBS纤维膜上，控制溶液的进给速率为3mL/h，纺丝电压为20kV，收集距离为20cm，环境温度为25℃，环境湿度为50％，静电喷时间为10min制备得到SEBS纤维和SEBS微球的复合膜。
(3)将该复合膜放置在真空干燥箱中进行温度退火交联处理，设置温度为170℃，时间为3h。交联处理之后的复合膜的微纳复合结构示意图如图1所示，从图1中可以看出，微球与纤维通过交联结合在一起。退火交联处理之后的复合膜在不同放大倍数下的扫描电镜照片如图2所示，从图2中可以看出，微球分布在纤维上，微球平均直径为8μm；同时从图2b中可见，纤维和微球的接触位置被交联了，获得了具有稳定纤维-微球结构的复合膜。
实施例2
(1)将三嵌段共聚物聚苯乙烯-聚(乙烯-丁烯)-聚苯乙烯(SEBS，Mw＝8.45×104g/mol，PS的嵌段体积比为30％)溶解在四氢呋喃(THF)中，控制SEBS的浓度为14wt％，溶液配制好以后在25℃下搅拌6～8小时至均一纺丝溶液；静电纺该溶液制备SEBS纤维，控制溶液的进给速率为2mL/h，纺丝电压为20kV，收集距离为20cm，环境温度为25℃，环境湿度为50％，采用平板收丝器收集，将该溶液电纺20min制备得到SEBS纤维膜。纤维平均直径为8μm。
(2)将同种SEBS溶解在四氢呋喃(THF)和N,N-二甲基甲酰胺(DMF)中，控制SEBS的质量浓度为14wt％，THF和DMF的质量比为80:20，溶液配制好以后在25℃下搅拌6～8小时至均一溶液；静电喷涂该溶液制备SEBS微球；将步骤(1)制备的SEBS纤维附在滚筒收集器上，滚筒直径5cm，滚筒转速2000r/min，滚筒接负高压-30kV，将SEBS溶液电喷在SEBS纤维膜上，控制溶液的进给速率为3mL/h，静电电压为20kV，收集距离为20cm，环境温度为25℃，环境湿度为30％，静电喷时间为30min制备得到SEBS纤维和SEBS微球的复合膜。微球平均直径为8μm。
(3)将该复合膜放置在真空干燥箱中进行温度退火交联处理，设置温度为170℃，时间为3h。处理之后的复合膜的扫描电镜照片如图3a所示，从图3a中可以看出，微球分布在纤维上；同时从图3b中可见，复合膜的接触角为约158°。在经过连续水冲刷200h后(水流速度1.2米/秒)，复合膜的水接触角保持在152-155°之间，如图4所示，说明其结构和超疏水性能在长时间的水冲刷后依旧保持稳定。
实施例3
(1)将三嵌段共聚物，聚苯乙烯-乙烯-丁烯-苯乙烯(SEBS，Mw＝8.45×104g/mol，PS的嵌段体积比为30％)溶解在四氢呋喃(THF)中，控制SEBS的浓度为14wt％，溶液配制好以后在25℃下搅拌6～8小时至均一纺丝溶液；静电纺该溶液制备SEBS纤维，控制溶液的进给速率为2mL/h，纺丝电压为20kV，收集距离为20cm，环境温度为25℃，环境湿度为70％，采用滚筒收丝器收集，滚筒直径5cm，滚筒转速500r/min，滚筒接负高压-30kV，将该溶液电纺20min制备得到SEBS纤维膜。纤维平均直径为8μm。
(2)将同种SEBS溶解在四氢呋喃(THF)中，控制SEBS的质量浓度为8wt％，溶液配制好以后在25℃下搅拌4小时至均一溶液；静电喷涂该溶液制备SEBS微球；将步骤(1)制备的SEBS纤维附在滚筒收集器上，滚筒直径20cm，滚筒转速100r/min，滚筒接负高压-20kV，将SEBS溶液电喷在SEBS纤维膜上，控制溶液的进给速率为1mL/h，静电电压为15kV，收集距离为25cm，环境温度为25℃，环境湿度为30％，静电喷时间为10min制备得到SEBS纤维和SEBS微球的复合膜。纤维平均直径为10μm，范围从3-30 μm。
(3)将该复合膜放置在真空干燥箱中进行温度退火交联处理，设置温度为170℃，时间为3h。处理之后的复合膜的扫描电镜照片如图5所示，从图5中可以看出，微球分布在纤维上，纤维和微球的接触位置被交联了，获得了具有稳定纤维-微球结构的复合膜。经测试，该复合膜的接触角为约150°
实施例4
(1)将聚偏氟乙烯(PVDF，Mw＝3.8×105g/mol)溶解在乙酸乙酯和N,N-二甲基甲酰胺的混合溶剂中(30/70)，其中PVDF的浓度为15wt％，溶液配制好以后在25℃下搅拌6小时至均一PVDF纺丝溶液；静电纺该溶液制备PVDF纤维，控制溶液的进给速率为0.5mL/h，纺丝电压为30kV，收集距离为20cm，环境温度为15℃，环境湿度为85％，采用平板收丝器收集，将该溶液电纺20min制备得到PVDF纤维膜。
(2)将聚苯乙烯(PS,Mw＝8.1×104g/mol)溶解在四氢呋喃(THF)中，控制PS的质量浓度为10wt％，溶液配制好以后在25℃下搅拌5小时至均一溶液；静电喷涂该溶液制备PS微球；将步骤(1)制备的PVDF纤维附在滚筒收集器上，滚筒直径20cm，滚筒转速300r/min，滚筒接负高压-1kV，将PS溶液电喷在PVDF纤维膜上，控制溶液的进给速率为5mL/h，静电电压为30kV，收集距离为40cm，环境温度为25℃，环境湿度为30％，静电喷时间为30min制备得到PVDF纤维和PS微球的复合膜。纤维平均直径为1μm，微球平均直径为8μm。
(3)将该复合膜放置在密闭玻璃箱中(10cm×10cm×10cm)，再放入装有10mL DMF的烧杯，密闭玻璃箱，溶剂退火处理30分钟即可获得具有稳定纤维-微球结构的复合膜。经测试，该复合膜的接触角为约155°。
实施例5
(1)将聚甲基丙烯酸甲酯(PMMA,Mw＝3.5×105g/mol)溶解在N,N-二甲基乙酰胺和丙酮的混合溶剂中(60/40)，其中PMMA的浓度为12wt％，溶液配制好以后在30℃下搅拌6小时至均一PMMA纺丝溶液；静电纺该溶液制备PVDF纤维，控制溶液的进给速率为2.5mL/h，纺丝电压为25kV，收集距离为25cm，环境温度为25℃，环境湿度为50％，采用平板收丝器收集，将该溶液电纺20min制备得到PMMA纤维膜。
(2)将同种PMMA溶解在N,N-二甲基乙酰胺中，控制PMMA的质量浓度为10wt％，溶液配制好以后在25℃下搅拌4小时至均一溶液；静电喷该溶液喷制备PMMA微球；将步骤(1)制备的PMMA纤维附在滚筒收集器上，滚筒直径10cm，滚筒转速1000r/min，滚筒接负高压-10kV，将PMMA溶液电喷在PMMA纤维膜上，控制溶液的进给速率为2.5mL/h，静电电压为15kV，收集距离为20cm，环境温度为25℃，环境湿度为50％，静电喷时间为30min制备得到PMMA纤维和PMMA微球的复合膜。纤维平均直径为700nm，微球平均直径为6μm。
(3)将该复合结构的纤维膜放置在真空干燥箱中进行温度退火交联处理，设置温度为130℃，时间为3h。处理之后的复合膜的接触角为154°。
实施例6
(1)将聚甲基丙烯酸甲酯(PMMA,Mw＝3.5×105g/mol)溶解在N,N-二甲基乙酰胺和丙酮的混合溶剂中(60/40)，其中PMMA的浓度为12wt％，溶液配制好以后在30℃下搅拌6小时至均一PMMA纺丝溶液；静电纺该溶液制备PVDF纤维，控制溶液的进给速率为2.5mL/h，纺丝电压为25kV，收集距离为25cm，环境温度为25℃，环境湿度为50％，采用平板收丝器收集，将该溶液电纺20min制备得到PMMA纤维膜。
(2)将同种PMMA溶解在N,N-二甲基乙酰胺中，控制PMMA的质量浓度为10wt％，溶液配制好以后在25℃下搅拌4小时至均一溶液；静电喷涂该溶液制备PMMA微球；将步骤(1)制备的PMMA纤维附在滚筒收集器上，滚筒直径10cm，滚筒转速800r/min，滚筒接负高压-10kV，将PMMA溶液电喷在PMMA纤维膜上，控制溶液的进给速率为2.5mL/h，静电电压为15kV，收集距离为20cm，环境温度为25℃，环境湿度为50％，静电喷时间为30min制备得到PMMA纤维和PMMA微球的复合膜。纤维平均直径为700nm，微球平均直径为6μm。
(3)将该复合结构的纤维膜浸没在10wt％浓度的2,4-甲苯二异氰酸酯(TDI)/甲苯溶液中(加入相对TDI含量1wt％浓度的二丁锡二月桂酸盐作为引发剂)，环境温度为40℃，反应4小时，之后捞出放置在真空干燥箱中干燥6h。处理之后的复合膜的接触角为153°。
实施例7
(1)将聚砜(PSF,Mw＝3.5×104g/mol)溶解在N,N-二甲基甲酰胺中，其中PSF的浓度为30wt％，溶液配制好以后在25℃下搅拌6小时至均一PSF纺丝溶液；静电纺该溶液制备PSF纤维，控制溶液的进给速率为2mL/h，纺丝电压为20kV，收集距离为15cm，环境温度为25℃，环境湿度为50％，采用平板收丝器收集，将该溶液电纺20min制备得到PSF纤维膜。
(2)将同种PSF溶解在N,N-二甲基乙酰胺中，控制PSF的质量浓度为10wt％，溶液配制好以后在25℃下搅拌6小时至均一溶液；静电喷涂该溶液制备PSF微球；将步骤(1)制备的PSF纤维附在平板收集器上，平板接负高压-10kV，将PSF溶液电喷在PSF纤维膜上，控制溶液的进给速率为2mL/h，静电电压为20kV，收集距离为20cm，环境温度为25℃，环境湿度为50％，静电喷时间为30min制备得到PSF纤维和PSF微球的复合膜。纤维平均直径为2μm，微球平均直径为7μm。
(3)将该复合膜放置在密闭玻璃箱中(10cm×10cm×10cm)，再放入装有15mL N,N-二甲基乙酰胺的烧杯，密闭玻璃箱，溶剂退火处理20分钟即可获得具有稳定纤维-微球结构的复合膜。经测试，该复合膜的接触角为约158°。
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，其他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)

1.一种抗水冲刷超疏水复合膜，其特征在于：是将疏水性高分子材料溶液通过静电纺丝技术制备成高分子纤维；再将同种或异种疏水性高分子材料溶液通过静电喷涂技术涂覆在上述的纤维膜上；随后对复合膜进行物理或化学交联处理，最后得到由纤维和微球组成的、表面具有微纳结构的超疏水复合膜；所述的超疏水复合膜中纤维的直径为100nm～20μm，微球尺寸在1～30μm。
2.根据权利要求1所述的超疏水复合纤维膜，其特征在于：所述的疏水性高分子材料为苯乙烯系热塑性弹性体、聚烯烃、聚苯乙烯、聚脲、聚砜、聚甲基丙烯酸、聚缩醛和聚酯中的至少一种。
3.根据权利要求2所述的超疏水复合纤维膜，其特征在于：
所述苯乙烯系热塑性弹性体为聚苯乙烯-聚(乙烯-丁烯)-聚苯乙烯嵌段共聚物、聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-聚异戊二烯-聚苯乙烯嵌段共聚物或聚苯乙烯-聚(乙烯-丙烯)-聚苯乙烯嵌段共聚物；
所述聚烯烃为聚乙烯、聚丙烯、聚乙烯-辛烯共聚物、聚氯乙烯、聚苯乙烯或聚偏氟乙烯；
所述聚酯为聚丙烯酸酯、聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、聚乙酸乙烯酯、聚己内酯、聚对苯二甲酸乙二酯、聚氨酯或聚碳酸酯。
4.根据权利要求1所述的超疏水复合纤维膜，其特征在于：
所述的物理交联包括采用温度退火交联或有机溶剂退火交联；
所述的化学交联包括采用光、热、高能辐射、机械力、超声波和交联剂交联。
5.一种根据权利要求1～4任一项所述的抗水冲刷超疏水复合纤维膜的制备方法，其特征在于：具体步骤为：
(1)静电纺丝法制备超细高分子纤维：将疏水性高分子材料溶于有机溶剂中，搅拌均匀后将高分子溶液装入带有喷射头的储存容器中，通过高压静电进行静电纺丝，采用收丝装置进行收集，将所得到的纤维放置于真空烘箱或室温中干燥至无溶剂残留即得高分子纤维；
(2)静电喷涂制备高分子微球：将同种或异种疏水性高分子材料溶于有机溶剂中，搅拌均匀后将得到的高分子溶液置于带有喷射头的储存容器中，并加载高压静电场，通过高压静电喷涂，以步骤(1)所得纤维为铺盖在接收装置上，将溶液喷涂在纤维上形成高分子微球，即得到纤维-微球复合结构膜；
(3)交联处理：对复合纤维膜进行物理或化学交联处理，使高分子纤维和微球交联起来，最后得到抗水冲刷超疏水复合膜。
6.根据权利要求5所述的抗水冲刷超疏水复合纤维膜的制备方法，其特征在于：
步骤(1)中所述高分子溶液的浓度为5～30wt％，所述高压静电的电压为10～30kV，喷射头与接丝装置的距离为10～45cm，高分子溶液从喷射头流出速度为0.5～15mL/h，环境温度为15～40℃，环境湿度为30～85％；
步骤(1)所述收丝装置为：平板收丝装置，由一块平板构成，接地或与负高压相连；或者，滚筒收丝装置，由直径为5～20cm的金属滚筒与电机组成，滚筒转速为50～3000r/min，滚筒接地或与负高压相连，所述的负高压为-30～-0.5kV。
7.根据权利要求5所述的抗水冲刷超疏水复合纤维膜的制备方法，其特征在于：
步骤(2)中所述高分子溶液的浓度为1～14wt％，所述高压静电场的电压为10～30kV，喷射头与接收装置的距离为10～25cm，混合溶液从喷头喷出速度为1～5mL/h，环境温度为15～40℃，环境湿度为30～85％；
步骤(2)所述接收装置为：平板接收装置，由一块平板构成，接地或与负高压相连；或者滚筒接收装置，由直径为5～20cm的金属滚筒与电机组成，滚筒转速为50～2000r/min，滚筒接地或与负高压相连，所述的负高压为-30～-0.5kV。
8.根据权利要求5所述的抗水冲刷超疏水复合纤维膜的制备方法，其特征在于：
步骤(3)所述物理交联是把复合膜放入可加热装置中，通过升温至高分子纤维或微球材料的熔点附近并保持一段时间，使高分子纤维和微球物理起来；交联温度范围在100～200℃，交联处理时间为30min～5h；
或者，所述物理交联是把复合膜放入一个密闭容器中，放入步骤(1)或步骤(2)中所述的有机溶剂，进行交联处理一段时间，使高分子纤维和微球物理起来，之后放置于真空烘箱或室温中干燥至无溶剂残留即得最终的复合膜；处理温度为20～70℃，处理时间为5～30min；
步骤(3)所述化学交联是采用光、热、高能辐射、机械力、超声波和交联剂交联，其中所述的交联剂为有机二元酸、多元醇或分子内含有多个不饱和双键的化合物。
9.根据权利要求5所述的一种抗水冲刷超疏水复合纤维膜的制备方法，其特征在于：
步骤(1)、(2)中所述的有机溶剂为四氢呋喃、丙酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、醋酸甲酯、甲基异丁酮、二氯甲烷、三氯甲烷、氯仿、乙醇、六氟异丙醇、三氟乙酸、三氟乙醇、异丙醇、N-甲基吗啉-N-氧化物、甲基氰中的一种或多种混合；步骤(1)和步骤(2)中的溶剂可以相同也可以不同。
10.根据权利要求1～4任一项所述的抗水冲刷超疏水复合纤维膜在油水分离、自清洁涂层、流体减阻、抗菌、防冻以及降低流体阻力方面的应用。
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CN113774517A (zh) * 2021-08-06 2021-12-10 华南理工大学 一种用于纸质文物预防性保护复合纤维膜及其制备方法
CN113832610A (zh) * 2021-09-27 2021-12-24 武汉大学 一种柔性超拉伸超疏水电子器件基底及其制备方法和应用
CN114642970A (zh) * 2020-12-18 2022-06-21 中国石油化工股份有限公司 一种POSS-PMMA-b-PDMS超疏水化合物附着的纳米纤维膜和制备方法
CN114687074A (zh) * 2022-04-01 2022-07-01 苏州大学 超疏水性聚氨酯薄膜的制备方法
CN115748246A (zh) * 2022-10-14 2023-03-07 四川大学 具有力电双异质特性结构可拉伸电子材料及其制备和应用

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CN107460733A (zh) * 2017-07-21 2017-12-12 东华大学 一种持久疏水织物的制备方法
CN107574497B (zh) * 2017-07-26 2021-02-19 华南理工大学 一种静电纺纤维改性复合膜及其制备方法
CN107574497A (zh) * 2017-07-26 2018-01-12 华南理工大学 一种静电纺纤维改性复合膜及其制备方法
CN107475902A (zh) * 2017-08-28 2017-12-15 天津工业大学 一种超疏水纤维膜的制备方法
CN107475902B (zh) * 2017-08-28 2020-01-07 天津工业大学 一种超疏水纤维膜的制备方法
CN107789675A (zh) * 2017-10-31 2018-03-13 无锡中科光远生物材料有限公司 一种用于减轻植入材料异物反应的多重药物纤维膜的制备方法
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CN110548417A (zh) * 2018-05-30 2019-12-10 中国科学院苏州纳米技术与纳米仿生研究所 一种高分子材料、超疏水多孔膜、涂层、制备方法与应用
CN110760994B (zh) * 2018-07-25 2022-02-01 中国科学院宁波材料技术与工程研究所 一种三维交联的超浸润纳米纤维膜及其制备方法
CN110760994A (zh) * 2018-07-25 2020-02-07 中国科学院宁波材料技术与工程研究所 一种三维交联的超浸润纳米纤维膜及其制备方法
CN109248570A (zh) * 2018-09-28 2019-01-22 成都其其小数科技有限公司 一种PAN/PAMS/ZnO油水分离膜的制备方法
CN109553902B (zh) * 2018-10-17 2021-03-23 江汉大学 透明阻燃聚乙烯醇薄膜及其制备方法
CN109553902A (zh) * 2018-10-17 2019-04-02 江汉大学 透明阻燃聚乙烯醇薄膜及其制备方法
CN111136980A (zh) * 2020-01-02 2020-05-12 北京石油化工学院 一种复合疏水膜及其制备方法
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CN111926463A (zh) * 2020-07-09 2020-11-13 浙江理工大学 一种苯乙烯-丁二烯-苯乙烯嵌段共聚物和聚偏氟乙烯混纺纳米纤维膜的制备方法
CN114642970A (zh) * 2020-12-18 2022-06-21 中国石油化工股份有限公司 一种POSS-PMMA-b-PDMS超疏水化合物附着的纳米纤维膜和制备方法
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Application publication date: 20161130