化学学报 ›› 2013, Vol. 71 ›› Issue (08): 1141-1148.DOI: 10.6023/A13030245 上一篇    下一篇

研究论文

PI-b-P2VP两嵌段共聚物环状形貌的影响因素研究

杨慧, 彭娟, 邱枫   

  1. 聚合物分子工程国家重点实验室 复旦大学高分子科学系 上海 200433
  • 收稿日期:2013-03-06 出版日期:2013-08-14 发布日期:2013-05-02
  • 通讯作者: 彭娟, E-mail: juanpeng@fudan.edu.cn; Tel.: 021-65643498 E-mail:juanpeng@fudan.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21074026, 20990231)及国家重点基础研究发展计划(973计划)(No. 2011CB605700)的资助.

The Influencing Factors on the Ring-shaped Morphology in PI-b-P2VP Diblock Copolymer

Yang Hui, Peng Juan, Qiu Feng   

  1. State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai 200433
  • Received:2013-03-06 Online:2013-08-14 Published:2013-05-02
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21074026, 20990231) and National Basic Research Program of China (No. 2011CB605700).

基于最近Chang等在嵌段共聚物聚异戊二烯-聚2-乙烯基吡啶(PI-b-P2VP)的四氢呋喃-乙醇共混溶剂体系制备环状胶束的工作(Angew. Chem. 2009, 48, 4594), 我们在此基础上, 用原子力显微镜对该体系形成环状结构的影响因素包括嵌段共聚物浓度、混合溶剂配比、溶剂选择性、溶剂挥发速度、溶剂滴加顺序及选择性溶剂的滴加速度等进行了详细研究, 发现P2VP的选择性溶剂的引入是形成环状结构的关键因素. 利用P2VP与氯金酸的络合, 分析环状结构, 并进一步结合动、静态光散射及冷冻透射电镜对此形貌的形成机理进行探究.

关键词: 两嵌段共聚物, 环状结构, 影响因素, 共混溶剂, 形貌演化

Recently, Chang et. al. reported ring-shaped micelles of highly uniform shape and size could be formed from polyisoprene-block-poly(2-vinylpyridine) (PI-b-P2VP) diblock copolymer in THF/ethanol solvent mixture (Angew. Chem. 2009, 121, 4664). Based on their work, we prepared the ring-shaped morphology films by adding P2VP selective solvent (ethanol) dropwise into a mixture of PI-b-P2VP block copolymer in their co-solvent tetrahydrofuran with a certain volume ratio of THF/ethanol and spin-coating the solution onto the silica wafers. We systematically investigated the influencing factors on the ring-shaped morphology by tapping mode atomic force microscopy (AFM), including copolymer concentrations (0.01, 0.02, 0.2, 0.4 and 2 mg/mL), the ratios of THF to ethanol (from 100:0, to 10:200), solvent selectivity (ethanol, acetone, water selective for P2VP and toluene selective for PI), solvent evaporation rates (0.048, 0.15, 0.3 mL/h), solvent dropping sequence and the dropping rates of selective solvent (1.13 mL/h, 6.72 mL/h and injecting ethanol directly into the solution). The existence of solvent selective for P2VP and the ratio of THF to ethanol were essential for the formation of rings. In order to analyze the structure of the ring morphology, chloroauric acid (HAuCl4) was selectively loaded into P2VP phase by complexation and detected by AFM. Combining these results with dynamic light scattering (DLS), static light scattering (SLS) and cryo-transmission electron microscopy (cryo-TEM), a possible formation mechanism of rings was proposed: with the addition of ethanol which is a selective solvent for P2VP, PI-b-P2VP gradually self-assembled into ring-shaped micelles with the outer corona composed of P2VP and the inner core constituted of PI block. On the basis of a series of research, it is possible to control the ring morphology by changing experimental conditions which is promising for patterning application.

Key words: diblock copolymer, ring-shaped structure, influencing factors, mixed solvents, morphology evolution