化学学报 ›› 2009, Vol. 67 ›› Issue (9): 1001-1007. 上一篇    下一篇

研究论文

含氟聚合物修饰碳纳米管及其聚氨酯复合疏水膜的研究

张 超 郭述忠 汪伟志 刘天西*

  

  1. (聚合物分子工程教育部重点实验室 复旦大学高分子科学系 先进材料实验室 上海200433)

  • 投稿日期:2008-12-08 修回日期:2008-12-29 发布日期:2009-05-14
  • 通讯作者: 刘天西

Fluorinated Multi-walled Carbon Nanotubes and Fabrication of Polyurethane Composite Films with Hydrophobic Surface

Zhang, Chao Guo, Shuzhong Wang, Weizhi Liu, Tianxi*   

  1. (Key Laboratory of Molecular Engineering of Polymers of Ministry of Education, Department of Macromolecular Science, Laboratory of Advanced Materials, Fudan University, Shanghai 200433)
  • Received:2008-12-08 Revised:2008-12-29 Published:2009-05-14
  • Contact: Liu, Tianxi

利用羟基碳纳米管上的羟基与2-溴异丁基酰溴之间的简单反应, 在碳纳米管上引入了含溴ATRP引发剂, 并进一步引发含氟丙烯酸酯的ATRP聚合, 从而在碳纳米管表面接枝上了低表面能的含氟聚合物. 红外光谱(FT-IR)、热重分析(TGA)和透射电镜(TEM)的研究结果表明碳纳米管与含氟聚合物之间为化学键连接. 以此低表面能聚合物包裹的碳纳米管作为填充粒子, 采用溶液浇铸方法制备了聚氨酯/碳纳米管复合膜, 并利用溶剂四氢呋喃(THF)刻蚀表面获得了不同碳纳米管裸露程度的复合膜材料. 静态接触角测试结果表明, 无论是羟基碳纳米管还是低表面能修饰的碳纳米管均可提高其复合膜的疏水性能, 且其疏水性能随碳纳米管含量的增加而增加; 相同含量时, 含氟聚合物接枝后的碳纳米管使复合膜具有更佳的疏水性能, 膜表面经溶剂刻蚀后可显著提高其疏水性能. 采用扫描电子显微镜(SEM)研究了加入碳纳米管和溶剂刻蚀对聚合物表面微观结构以及材料表面疏水性能的影响. 上述结果表明: 利用接枝聚合物可改变碳纳米管本身的疏水性能, 并可进一步制备新型的具有表面疏水性能的聚合物纳米复合材料.

关键词: 碳纳米管, 原子转移自由基聚合, 含氟聚合物, 疏水膜

The reaction between the hydroxyl groups on the surface of acid-treated multi-walled carbon nanotubes (MWNT) and 2-bromo-2-methylpropanoyl bromide generates ATRP initiator sites on the MWNT, and then fluorinated acrylates were polymerized from MWNT via a “graft-from” method. Fourier transform infrared spectrometry (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) results indicate that the polymer was covalently attached or grafted to the surface of MWNT. Using MWNT coated with low surface energy polymer as the filler particles, a solution-casting method was employed to prepare MWNT/polyurethane composite films. The surface of composite films was exposed to tetrahydrofuran (THF) as the etchant to obtain the rough surface with microstructures. Static contact angle tests showed the hydrophobic properties of films were enhanced by adding the MWNT, and the contact angle was increased with the content of MWNT. The MWNT grafted with fluorinated polymers showed better hydrophobic performance than the pristine MWNT at the same content, and the film hydrophobicity was greatly improved after etching by solvent. Scanning electron microscopy (SEM) was used to study the microstructures of surfaces of composite films before and after etching. Effect of MWNT on the hydrophobic properties of the composite film surfaces was in-depth studied. Our experiments demonstrated that the hydrophobic properties of MWNT surfaces could be tuned via functionalization using different surface energy materials and the fabrication of polyurethane composite films with hydrophobic surfaces could be successfully achieved.

Key words: carbon nanotube, ATRP, fluorinated polymer, hydrophobic film