化学学报 ›› 2014, Vol. 72 ›› Issue (9): 1023-1028.DOI: 10.6023/A14070510 上一篇    下一篇

研究论文

尼龙表面的超疏水及高度疏油改性

郝威, 邵正中   

  1. 聚合物分子工程国家重点实验室 复旦大学先进材料实验室 高分子科学系 上海 200433
  • 收稿日期:2014-07-05 出版日期:2014-09-14 发布日期:2014-08-27
  • 通讯作者: 邵正中 E-mail:zzshao@fudan.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No. 21034003)和上海市优秀学术带头人计划(No. 12XD1401000)资助.

Superhydrophobic and Highly Oleophobic Nylon Surface

Hao Wei, Shao Zhengzhong   

  1. State Key Laboratory of Molecular Engineering of Polymers, Advanced Materials Laboratory and Department of Macromolecular Science, Fudan University, Shanghai 200433
  • Received:2014-07-05 Online:2014-09-14 Published:2014-08-27
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21034003) and Program of Shanghai Subject Chief Scientist (No. 12XD1401000).

在聚合物表面引入多级粗糙结构并降低表面能可以提高其表面的疏水疏油性. 采用三种不同方法在尼龙6(聚酰胺)表面引入活性基团, 即或将尼龙6材料表面的酰胺键还原成仲胺, 或硅羟基化, 或使用低温等离子体处理得到羟基, 并通过X-射线光电子能谱(XPS)进行验证. 实验结果表明, 表面含有仲胺基团的尼龙6可静电吸附硅球; 而表面含有硅羟基及羟基的尼龙6可原位生长纳米硅层, 再经过3-氨基丙基三甲氧基硅烷(APS)处理可达到硅球吸附的目的. 经比较了不同改性方法对在尼龙6表面构建粗糙结构的影响, 我们认为等离子体处理更利于方便快捷地制备稳定均匀的粗糙结构. 当被全氟十二烷基三氯硅烷(Rf-Si)氟化修饰后, 具有粗糙结构的尼龙6表面均具有超疏水性, 但其疏油性则与表面引入的硅球尺寸密切相关, 如在500~900 nm硅球构建的粗糙表面上, 十六烷烃(3 μL)的静态接触角为140°左右, 滚动角为20°; 而在20~200 nm硅球构建的粗糙表面上, 其静态接触角和滚动角则分别为125°和40°左右. 实验结果还显示, 这类具有一定双疏性的尼龙表面也有较好的抗细菌粘附性.

关键词: 尼龙, 表面改性, 超疏水, 高度疏油, 抗细菌粘附

Superhydrophobic and superoleophobic surfaces are desirable for many practical applications. Creating a rough structure on polymer surface then modified by materials with low surface free energy can broaden the potential applications of polymers. In this research, we used three different methods to modify nylon 6 surface, then compared their effect on preparing nylon 6 surface roughness. Activation of amides by chemical reduction with borane-THF complex resulted in secondary amine groups, which could absorb silica spheres with different sizes driven by electrostatic attraction. On the other side, alkylation with (3-glycidoxypropyl) triethoxysilane (GPTES) was utilized to introduce silica-like reactivity to the surface, while plasma-treatment could import hydroxyl groups on nylon 6 surface. Then silica layer was generated and covalently bonded to the nylon 6 in situ. After treated with 3-aminopropyl-triethoxysiloxane (APS), silica spheres could be introduced to the sample more evenly than the first method, and then reacted with silicon tetrachloride to enhance mechanical robustness. Plasma-treatment was more fast and clean in preparing the stable roughness, which made this modification a favorable method. Different size silica spheres were used to construct roughness on nylon textile. After being modified with a perfluoroalkyl silane, the surface with all roughness had superhydrophobic property, while the wettability of low-energy liquid on the surface was depending on the micro structure size. Silica spheres with size between 500 nm and 900 nm were propitious to achieve stable Cassie state, which could cause high contact angles (about 140°) and low roll-off angles (about 20°) for 3 μL hexadecane droplets. On the other hand, for the samples adsorbed silica spheres with size between 20 nm and 200 nm, the contact angles and roll-off angles for 3 μL hexadecane were about 125° and 40°, respectively. Because of the air trapped between the roughnesses, the obtained superhydrophobic and highly oleophobic nylon textile also show high resistance to bacterial contamination. This may broaden the application of nylon.

Key words: nylon, surface modification, superhydrophobicity, highly oleophobicity, anti-bacterial adhesion