化学学报 ›› 2014, Vol. 72 ›› Issue (1): 83-88.DOI: 10.6023/A13101051 上一篇    下一篇

研究论文

苯胺四聚体-聚乙二醇-苯胺四聚体嵌段共聚物薄膜的自组装

张广萌, 杨继萍, 陈功   

  1. 北京航空航天大学材料科学与工程学院 空天先进材料与服役教育部重点实验室 北京 100191
  • 收稿日期:2013-10-12 出版日期:2014-01-14 发布日期:2013-12-17
  • 通讯作者: 杨继萍,E-mail:jyang@buaa.edu.cn;Tel.:010-82338955 E-mail:jyang@buaa.edu.cn
  • 基金资助:

    项目受国家自然科学基金(No. 21174009)资助.

Self-assembly of Tetraaniline-PEG-Tetraaniline Block Copolymer Thin Films

Zhang Guangmeng, Yang Jiping, Chen Gong   

  1. Key Laboratory of Aerospace Advanced Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191
  • Received:2013-10-12 Online:2014-01-14 Published:2013-12-17
  • Supported by:

    Project supported by National Natural Science Foundation of China (No. 21174009).

以氨基封端的苯胺四聚体为基础,以甲苯2,4-二异氰酸酯(TDI)为中间体制备了苯胺四聚体-聚乙二醇-苯胺四聚体(ANI4-PEG-ANI4,PEG600,Mn=600)嵌段共聚物,并溶于乙醇/NN-二甲基甲酰胺(DMF)混合溶剂后,涂覆于导电玻璃(ITO)表面制备成薄膜,利用原子力显微镜(AFM)、紫外-可见光谱(UV-Vis)和循环伏安(CV)等研究了薄膜的自组装及电化学行为等,讨论了诱导溶剂对嵌段共聚物薄膜形态和性能的影响. 研究发现,通过改变混合溶剂比和诱导溶剂种类,ANI4-PEG-ANI4嵌段共聚物薄膜可以实现多种形态的转变.

关键词: 苯胺四聚体, 聚乙二醇, 嵌段共聚物, 自组装, 溶剂诱导

Amphiphilic rod-coil block copolymers containing polyethylene glycol and aniline oligomers can self-assemble into specific aggregation morphologies with different electrochemical performances, which have recently attracted more attention in many fields such as optoelectronic materials, electronics and so on. In this paper, the block copolymer of tetraaniline-polyethylene glycol-tetraaniline (ANI4-PEG-ANI4, PEG600, Mn=600) was prepared using tolylene 2,4-diisocyanate (TDI) as intermediate. At first, tetraaniline was synthesised by 4-aminodiphenyamine through oxidative coupling reaction in an acidic solution. Then, TDI was used to combine tetraaniline and PEG to prepare the triblock copolymer in the presence of N,N-dimethylformamide (DMF). 1H-NMR and FT-IR were combined to confirm the chemical structure of the resulting block copolymer. The self-assembly of the block copolymer thin films was studied in detail. ANI4-PEG-ANI4 block copolymer was dissolved in a mixing solvent with ethanol and DMF. Then the solution was coated on conductive glass ITO to prepare thin films with the same thickness. And the films were dried completely before use. Atomic force microscope (AFM), UV-Vis spectroscopy and cyclic voltammetry (CV) were used to study the self-assembly behaviors of ANI4-PEG-ANI4 block copolymer thin films. The influence of mixing ratio of ethanol/DMF and different annealing solvents on the self-assembly behaviors of ANI4-PEG-ANI4 block copolymer thin films were investigated. The annealing solvents included ethanol, methanol, chloroform and tetrahydrofuran. The results showed that by changing the mixing ratio of ethanol/DMF, the morphologies of the block copolymer thin films could be changed from spheric to rod-like morphologies. And by changing the annealing solvents, the copolymer thin films could self-assemble into such as spheric, rod-like and fibrillar morphologies. The different aggregation structures of the block copolymer thin films exhibited different electrochemical performances. So the aggregation structures of ANI4-PEG-ANI4 block copolymer thin films could be tuned nicely by changing the solvents and annealing solvents.

Key words: tetraaniline, polyethylene glycol, block copolymer, self-assembly, solvent annealing