CN109576985A - 一种制备超疏水材料的方法 - Google Patents

一种制备超疏水材料的方法 Download PDF

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CN109576985A
CN109576985A CN201710904266.2A CN201710904266A CN109576985A CN 109576985 A CN109576985 A CN 109576985A CN 201710904266 A CN201710904266 A CN 201710904266A CN 109576985 A CN109576985 A CN 109576985A
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周琪
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Abstract

本发明公开了一种制备超疏水材料的方法，该制备方法包括以下步骤：1）利用纳米材料对基底材料的整体三维结构进行修饰，构造微米‑纳米复合粗糙结构；2）用低表面能物质对已获得微米‑纳米复合粗糙结构的基底材料进行表面修饰。通过本发明制备的超疏水材料，其疏水性能优良，且制备工艺简单，反应条件温和，不需要特殊的加工设备。

Description

一种制备超疏水材料的方法
技术领域
本发明涉及高分子材料技术领域，具体涉及一种制备超疏水材料的方法。
背景技术
超疏水材料因其优异的拒水性能，在自清洁、防水防污、减阻降噪音、水处理等领域表现出了广阔的应用前景。目前，该类新型功能材料在国防、建筑、涂料等多个领域均具有巨大的市场需求。超疏水材料要求水滴在其表面的静态接触角大于150度。然而，采用传统的氟和硅材料对固体材料表面进行简单的涂覆，难以实现材料的超疏水性能，其静态接触角小于150度。近年来，超疏水材料的研究有了重大性进展，各种无机或有机的超疏水材料被相继报道。这些已有的基础研究表明，获得超疏水材料需要满足以下两个条件：一是在材料表面构造粗糙形貌；另一个是用低表面能物质对该粗糙表面进行修饰。即利用粗糙形貌作为“放大镜”来放大低表面能物质的疏水性能，使材料获得超疏水性能。
随着20世纪90年代纳米技术的出现和快速发展，在固体材料表面构造微米-纳米结构已成为获得粗糙表面形貌的最有效手段。利用激光刻蚀、静电纺丝、电腐蚀、模板法等技术可实现一系列形貌可控的具有微米-纳米结构粗糙表面的制备，在此基础上再用低表面能物质（硅或氟）进行表面修饰，即可获得形貌各异且疏水性能不同超疏水材料。然而，上述超疏水材料的制备工艺较复杂，制备材料需要特殊的加工设备，且加工设备昂贵、加工成本较高。
发明内容
本发明的目的是提供一种制备超疏水材料的方法，本发明利用纳米材料对基底材料的整体三维结构进行修饰，从而提高基底材料整体三维结构的粗糙度，并通过表面修饰技术利用低表面能物质对粗糙结构进行包裹、修饰。
本发明解决技术问题的方案是：一种制备超疏水材料的方法，该制备方法包括以下步骤：
1）利用纳米材料对基底材料的整体三维结构进行修饰，构造微米-纳米复合粗糙结构；
2）用低表面能物质对已获得微米-纳米复合粗糙结构的基底材料进行表面修饰。
所述纳米材料为粒径范围为15～150nm的TiO2纳米粒子、SiO2纳米粒子或CeO2纳米粒子。
所述基底材料包括：皮革、布料和三聚氰胺泡沫。
所述步骤1）具体为：将基底材料浸泡在TiO2纳米粒子的前驱体溶液、含纳米粒子的溶液或含纳米粒子的液溶胶中处理，然后干燥，得微米-纳米复合粗糙结构的基底材料。
所述TiO2纳米粒子的前驱体溶液为浓度为5mmol/L～1mol/L的钛酸丁酯的无水乙醇溶液；所述含纳米粒子的溶液为含纳米TiO2粒子的PU和/或PMMA溶液、或含纳米SiO2粒子的PU和/或PMMA溶液；所述含纳米粒子的液溶胶为含纳米SiO2粒子的液溶胶、或含纳米CeO2粒子的液溶胶。
所述含纳米粒子的溶液中，其纳米粒子的浓度为0.02～3g/L。
所述含纳米TiO2粒子的PU溶液由以下方法制得：将1g直径为15～150nm的TiO2粒子分散在1LPU溶液中，得到含纳米TiO2粒子的PU溶液；所述含纳米SiO2粒子的液溶胶是由以下方法制得：按体积份配比计，将3份等体积的正硅酸乙酯和氨水加入到50份无水乙醇中，常温下磁力搅拌制即得含纳米SiO2粒子的液溶胶；所述氨水质量浓度为28～33%；所述含纳米SiO2粒子的PMMA溶液是由以下方法制得：将1g直径为15～150nm的SiO2粒子分散在1LPMMA溶液中，得到含纳米SiO2粒子的PMMA溶液；所述含纳米CeO2粒子的液溶胶是由以下方法制得：配制25份0.06mol/L硝酸铈的无水乙醇溶液，加入4份0.1mol/L氢氧化钠溶液，磁力搅拌下制得纳米CeO2粒子的液溶胶。
所述低表面能物质为硅烷溶液。
所述硅烷溶液包括体积浓度大于0.5%的氟硅烷溶液、物质的量浓度大于0.05mol/L硅烷偶联剂溶液。
所述步骤2）中表面修饰的方法为：将具有微米-纳米复合粗糙结构的基底材料直接浸泡在乙烯基三乙氧基硅烷的甲苯溶液或氟硅烷溶液中，然后干燥后即可制得超疏水材料；或先将具有微米-纳米复合粗糙结构的基底材料在PMMA溶液或PDMS溶液中浸泡、干燥后，再放入硅烷偶联剂溶液或氟硅烷溶液中浸泡，然后干燥后即可制得超疏水材料；所述硅烷偶联剂溶液为乙烯基三乙氧基硅烷的甲苯溶液。
本发明具有的优点是：通过本发明制备的超疏水材料，其疏水性能优良，且制备工艺简单，反应条件温和，不需要特殊的加工设备。
具体实施方式
下面结合实施例对本发明作进一步的详细说明：
实施例：
本制备超疏水材料的方法包括以下步骤：
1）利用纳米材料对基底材料的整体三维结构进行修饰，构造微米-纳米复合粗糙结构；
2）用低表面能物质对已获得微米-纳米复合粗糙结构的基底材料进行表面修饰。
所述纳米材料为粒径范围为50nm的TiO2纳米粒子、SiO2纳米粒子或CeO2纳米粒子。
所述基底材料包括：皮革、布料和三聚氰胺泡沫。
所述步骤1）具体为：将基底材料浸泡在TiO2纳米粒子的前驱体溶液、含纳米粒子的溶液或含纳米粒子的液溶胶中处理，然后干燥，得微米-纳米复合粗糙结构的基底材料。
所述TiO2纳米粒子的前驱体溶液为浓度为0.5mol/L的钛酸丁酯的无水乙醇溶液；所述含纳米粒子的溶液为含纳米TiO2粒子的PU和/或PMMA溶液、或含纳米SiO2粒子的PU和/或PMMA溶液；所述含纳米粒子的液溶胶为含纳米SiO2粒子的液溶胶、或含纳米CeO2粒子的液溶胶。
所述含纳米粒子的溶液中，其纳米粒子的浓度为2g/L。
所述含纳米TiO2粒子的PU溶液由以下方法制得：将1g直径为50nm的TiO2粒子分散在1LPU溶液中，得到含纳米TiO2粒子的PU溶液；所述含纳米SiO2粒子的液溶胶是由以下方法制得：按体积份配比计，将3份等体积的正硅酸乙酯和氨水加入到50份无水乙醇中，常温下磁力搅拌制即得含纳米SiO2粒子的液溶胶；所述氨水质量浓度为30%；所述含纳米SiO2粒子的PMMA溶液是由以下方法制得：将1g直径为15nm的SiO2粒子分散在1LPMMA溶液中，得到含纳米SiO2粒子的PMMA溶液；所述含纳米CeO2粒子的液溶胶是由以下方法制得：配制25份0.06mol/L硝酸铈的无水乙醇溶液，加入4份0.1mol/L氢氧化钠溶液，磁力搅拌下制得纳米CeO2粒子的液溶胶。
所述低表面能物质为硅烷溶液。
所述硅烷溶液包括体积浓度大于0.5%的氟硅烷溶液、物质的量浓度大于0.05mol/L硅烷偶联剂溶液。
所述步骤2）中表面修饰的方法为：将具有微米-纳米复合粗糙结构的基底材料直接浸泡在乙烯基三乙氧基硅烷的甲苯溶液或氟硅烷溶液中，然后干燥后即可制得超疏水材料；或先将具有微米-纳米复合粗糙结构的基底材料在PMMA溶液或PDMS溶液中浸泡、干燥后，再放入硅烷偶联剂溶液或氟硅烷溶液中浸泡，然后干燥后即可制得超疏水材料；所述硅烷偶联剂溶液为乙烯基三乙氧基硅烷的甲苯溶液。
本发明制备的超疏水材料，其疏水性能优良，且制备工艺简单，反应条件温和，不需要特殊的加工设备。

Claims (10)

1.一种制备超疏水材料的方法，其特征在于：该制备方法包括以下步骤：
1）利用纳米材料对基底材料的整体三维结构进行修饰，构造微米-纳米复合粗糙结构；
2）用低表面能物质对已获得微米-纳米复合粗糙结构的基底材料进行表面修饰。
2.根据权利要求1所述的一种制备超疏水材料的方法，其特征在于：所述纳米材料为粒径范围为15～150nm的TiO2纳米粒子、SiO2纳米粒子或CeO2纳米粒子。
3.根据权利要求1所述的一种制备超疏水材料的方法，其特征在于：所述基底材料包括：皮革、布料和三聚氰胺泡沫。
4.根据权利要求1或2或3所述的一种制备超疏水材料的方法，其特征在于：所述步骤1）具体为：将基底材料浸泡在TiO2纳米粒子的前驱体溶液、含纳米粒子的溶液或含纳米粒子的液溶胶中处理，然后干燥，得微米-纳米复合粗糙结构的基底材料。
5.根据权利要求4所述的一种制备超疏水材料的方法，其特征在于：所述TiO2纳米粒子的前驱体溶液为浓度为5mmol/L～1mol/L的钛酸丁酯的无水乙醇溶液；所述含纳米粒子的溶液为含纳米TiO2粒子的PU和/或PMMA溶液、或含纳米SiO2粒子的PU和/或PMMA溶液；所述含纳米粒子的液溶胶为含纳米SiO2粒子的液溶胶、或含纳米CeO2粒子的液溶胶。
6.根据权利要求4或5所述的一种制备超疏水材料的方法，其特征在于：所述含纳米粒子的溶液中，其纳米粒子的浓度为0.02～3g/L。
7.根据权利要求5所述的一种制备超疏水材料的方法，其特征在于：所述含纳米TiO2粒子的PU溶液由以下方法制得：将1g直径为15～150nm的TiO2粒子分散在1LPU溶液中，得到含纳米TiO2粒子的PU溶液；所述含纳米SiO2粒子的液溶胶是由以下方法制得：按体积份配比计，将3份等体积的正硅酸乙酯和氨水加入到50份无水乙醇中，常温下磁力搅拌制即得含纳米SiO2粒子的液溶胶；所述氨水质量浓度为28～33%；所述含纳米SiO2粒子的PMMA溶液是由以下方法制得：将1g直径为15～150nm的SiO2粒子分散在1LPMMA溶液中，得到含纳米SiO2粒子的PMMA溶液；所述含纳米CeO2粒子的液溶胶是由以下方法制得：配制25份0.06mol/L硝酸铈的无水乙醇溶液，加入4份0.1mol/L氢氧化钠溶液，磁力搅拌下制得纳米CeO2粒子的液溶胶。
8.根据权利要求1所述的一种制备超疏水材料的方法，其特征在于：所述低表面能物质为硅烷溶液。
9.根据权利要求8所述的一种制备超疏水材料的方法，其特征在于：所述硅烷溶液包括体积浓度大于0.5%的氟硅烷溶液、物质的量浓度大于0.05mol/L硅烷偶联剂溶液。
10.根据权利要求1所述的一种制备超疏水材料的方法，其特征在于：所述步骤2）中表面修饰的方法为：将具有微米-纳米复合粗糙结构的基底材料直接浸泡在乙烯基三乙氧基硅烷的甲苯溶液或氟硅烷溶液中，然后干燥后即可制得超疏水材料；或先将具有微米-纳米复合粗糙结构的基底材料在PMMA溶液或PDMS溶液中浸泡、干燥后，再放入硅烷偶联剂溶液或氟硅烷溶液中浸泡，然后干燥后即可制得超疏水材料；所述硅烷偶联剂溶液为乙烯基三乙氧基硅烷的甲苯溶液。
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