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化学进展 2016, Vol. 28 Issue (7): 1062-1069 DOI: 10.7536/PC160135 前一篇   后一篇

• 综述与评论 •

巯基-环氧点击化学及其在高分子材料中的应用

姚臻, 戴博恩, 于云飞, 曹堃*   

  1. 浙江大学化学工程与生物工程学院 化学工程联合国家重点实验室 杭州 310027
  • 收稿日期:2016-01-01 修回日期:2016-03-01 出版日期:2016-07-15 发布日期:2016-05-17
  • 通讯作者: 曹堃 E-mail:kcao@che.zju.edu.cn
  • 基金资助:
    国家自然科学基金项目（No.51473146）资助
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Thiol-Epoxy Click Chemistry and Its Applications in Macromolecular Materials

Yao Zhen, Dai Boen, Yu Yunfei, Cao Kun*   

  1. State Key Laboratory of Chemical Engineering, College of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2016-01-01 Revised:2016-03-01 Online:2016-07-15 Published:2016-05-17
  • Supported by:
    The work was supported by the National Natural Science Foundation of China (No.51473146).
巯基-环氧反应作为一类典型的“点击化学”具有反应速度快、选择性高且反应条件温和等优点，近年来备受关注。本文首先阐述了巯基-环氧反应的碱催化机理，并评述了碱性催化剂、取代基团以及溶剂等因素对于巯基-环氧反应速率的影响。归纳认为，无机碱如氢氧化锂以及有机碱如四丁基氟化铵具有较高催化活性，并比较了无机碱和有机碱催化剂的优缺点；与供电子基团连接的巯基化合物以及与吸电子基团连接的环氧化合物具有较高的反应活性，位阻效应也对其有影响；在无溶剂的本体条件下反应活性较高。同时，重点介绍了巯基-环氧反应在高分子材料领域中应用的最新进展，并将其分为在溶剂中合成结构可控的高分子（包括线型或复杂结构高分子的合成和高分子或表面的修饰改性）以及本体条件下制备性能优良且具有应用价值的高分子网络两大类进行讨论。最后，简要展望了其发展前景。
关键词： 巯基, 环氧, 点击化学, 反应机理, 高分子材料
As one kind of "click chemistry", thiol-epoxy reaction has drawn intensive attention in recent years due to its outstanding advantages, such as fast reaction rate, high selectivity, and mild reaction conditions. This review illustrates the base-catalyzed mechanism of thiol-epoxy reaction in details. The influences of base catalysts, substituent groups and solvents on the thiol-epoxy reaction rate are summarized. The inorganic base such as lithium hydrate and organic base such as tetrabutylammonium fluoride are excellent catalytic activity. The advantages and disadvantages of inorganic and organic base catalysts are compared as well. Thiols with electron-donating groups and epoxy with electron-withdrawing groups are more active, which are also influenced by steric effect. The reactions in bulk system usually have higher yield than the reactions in solution. Moreover, the applications of thiol-epoxy reaction in macromolecular materials are also demonstrated and classified into two types according to their different focuses: one is synthesis of structure-controllable macromolecules in the solvents, including the synthesis of macromolecules with linear or complicated structures and the modifications of macromolecules or surfaces; and the other one is preparation of crosslinking polymeric networks with excellent properties and practical potential in the bulk condition. Furthermore, the trends of thiol-epoxy reaction are prospected in brief.

Contents
1 Introduction
2 Mechanism of thiol-epoxy reaction
2.1 Base-catalyzed mechanism
2.2 Influence of base catalysts
2.3 Influence of substituent groups
2.4 Influence of solvent
3 Application of thiol-epoxy reaction in polymer science
3.1 Polymer with special structures in solvent
3.2 Crosslinking networks with high performances in bulk condition
4 Conclusion

Key words: thiol, epoxy, click chemistry, reaction mechanism, macromolecular materials

中图分类号: 

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