高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

利用可逆共价键pH响应性制备聚轮烷

蒋逸1, 薛洁1, 朱新远1,2, 颜德岳1   

  1. 1. 上海交通大学化学化工学院, 2. 分析测试中心, 上海 200240
  • 收稿日期:2008-09-17 修回日期:1900-01-01 出版日期:2008-12-10 发布日期:2008-12-10
  • 通讯作者: 朱新远, 颜德岳

pH Stimulated Preparation of Polyrotaxane Based on Reversible Covalent Bond in Solution

JIANG Yi1, XUE Jie1, ZHU Xin-Yuan1,2*, YAN De-Yue1*   

  1. 1. School of Chemistry and Chemical Engineering, 2. Instrumental Analysis Center, Shanghai Jiao Tong University, Shanghai 200240, China
  • Received:2008-09-17 Revised:1900-01-01 Online:2008-12-10 Published:2008-12-10
  • Contact: ZHU Xin-Yuan, YAN De-Yue

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被引次数

7

摘要： 合成了具有可逆酰腙键的2,4-二硝基苯甲醛封端的哑铃型聚乙二醇衍生物. 在60 ℃时将水溶液的pH值调节至酸性, 哑铃型聚合物上的酰腙键发生可逆的“断开”和“生成”. 在这个可逆过程中, 溶液中的α-环糊精逐步与聚乙二醇内含复合. 由于环糊精具有较强疏水作用的内部空腔, 可以与聚乙二醇形成稳定的内含结晶复合物, 在这种超分子作用力下, 哑铃型聚乙二醇衍生物的分子链上会动态地穿入更多的α-环糊精, 最终形成聚轮烷. 综合液体核磁共振、粉末X射线衍射、固体碳-13交叉极化/魔角自旋核磁共振及差示扫描量热分析结果证明, 这种利用可逆共价键pH响应性制备聚轮烷的方法是可行的. 与传统的聚轮烷制备方法不同, 这种利用动态的可逆共价键制备聚轮烷的方法并不需要预先合成准(聚)轮烷.

关键词: 环糊精, 聚乙二醇, 可逆酰腙键, pH响应性, 聚轮烷

Abstract: A novel method to prepare polyrotaxane in solution by α-cyclodextrins and dumbbell-like poly(ethylene glycol) derivative with reversible acylhydrazone bond and big end stopper (2’,4- dinitrophenyl) is described. Stimulated by the pH change to acidic in water at 60 ℃, the reversible acylhydrazone bond could undergo reversible hydrolysis. During this process, α-cyclodextrins can pass through the dynamic reversible bond and thread onto the polymer chain. Because of the relative strong supramolecular interactions between α-cyclodextrins and ethylene glycol units in water, more and more α-cyclodextrins thread onto the polymer chain, leading to the formation of polyrotaxane. Through the combination of 1H NMR, wide-angle X-ray diffraction, 13C CP/MAS NMR and differential scanning calorimetric tests, the formation of polyrotaxane prepared by dynamic method is confirmed. Differing from the traditional routes, the preparation of pseudo(poly)rotaxane is no longer a prerequisite to construct polyrotaxane in this dynamic method. The novel polyrotaxane with reversible covalent bond, which has its inherent dynamic property, has potential use in smart materials and self-healing materials.

Key words: α-Cyclodextrin, Poly(ethylene glycol), Reversible acylhydrazone bond, pH responsive, Polyrotaxane

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