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

doi:10.7536/PC160135

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

综述与评论

扫码查看或转发全文

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*

作者信息 +

Thiol-Epoxy Click Chemistry and Its Applications in Macromolecular Materials

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

Author information +

文章历史 +

摘要

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。

Abstract

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

Graphical abstract

关键词

巯基 / 环氧 / 点击化学 / 反应机理 / 高分子材料

Key words

thiol / epoxy / click chemistry / reaction mechanism / macromolecular materials

引用本文

引用格式 ▾

姚臻, 戴博恩, 于云飞, 曹堃. 巯基-环氧点击化学及其在高分子材料中的应用[J]. 化学进展, 2016, 28(7): 1062-1069 DOI:10.7536/PC160135

Yao Zhen, Dai Boen, Yu Yunfei, Cao Kun. Thiol-Epoxy Click Chemistry and Its Applications in Macromolecular Materials[J]. Progress in Chemistry, 2016, 28(7): 1062-1069 DOI:10.7536/PC160135

登录浏览全文

4963

注册一个新账户忘记密码

参考文献

原文顺序 | 出版日期 | 本文引用

[1] Kolb H C, Finn M G, Sharpless K B. Angew. Chem. Int. Ed., 2001, 40:2004.
[2] Hoyle C E, Lowe A B, Bowman C N. Chem. Soc. Rev., 2010, 39:1355.
[3] 杨正龙(Yang Z L),陈秋云(Chen Q Y),周丹(Zhou D),卜弋龙(Bu Y L). 化学进展(Progress in Chemistry), 2012, 24(2/3):395.
[4] Roush W R, Brown B B. J. Org. Chem., 1992, 57:3380.
[5] Kim M J, Choi Y K. J. Org. Chem., 1992, 57:1605.
[6] Meffre P, Vo-Quang L, Vo-Quang Y, Le Goffic F. Tetrahedron Lett., 1990, 31:2291.
[7] Guivisdalsky P N, Bittman R. J. Am. Chem. Soc., 1989, 111:3077.
[8] Ko S Y, Masamune H, Sharpless K B. J. Org. Chem., 1987, 52:667.
[9] Shaw K J, Luly J R, Rapoport H. J. Org. Chem., 1985, 50:4515.
[10] Maurer P J, Knudsen C G, Palkowitz A D, Rapoport H. J. Org. Chem., 1985, 50:325.
[11] Meldal M. Macromol. Rapid Commun., 2008, 29:1016.
[12] Hein J E, Fokin V V. Chem. Soc. Rev., 2010, 39:1302.
[13] Liang L, Astruc D. Coord. Chem. Rev., 2011, 255:2933.
[14] Moses J E, Moorhouse A D. Chem. Soc. Rev., 2007, 36:1249.
[15] 李娟(Li J),段明(Duan M),张烈辉(Zhang L H),蒋晓慧(Jiang X H). 化学进展(Progress in Chemistry), 2007, 19(11):1754.
[16] 邱素艳(Qiu S Y),高森(Gao S),林振宇(Lin Z Y),陈国南(Chen G N). 化学进展(Progress in Chemistry),2011, 23(4):637.
[17] Tasdelen M A. Polym. Chem., 2011, 2:2133.
[18] Liu Y, Chuo T. Polym. Chem., 2013, 4:2194.
[19] Gandini A. Prog. Polym. Sci., 2013, 38:1.
[20] 杨哲(Yang Z),魏宏亮(Wei H L),楚晖娟(Chu H J),朱靖(Zhu J),李志成(Li Z C). 高分子通报(Polymer Bulletin), 2010(1):41.
[21] 李金辉(Li J H),张国平(Zhang G P),孙蓉(Sun R),汪正平(Wang Z P). 高分子通报(Polymer Bulletin), 2014(3):8.
[22] Nair D P, Podgórski M, Chatani S, Gong T, Xi W, Fenoli C R, Bowman C N. Chem. Mater., 2014, 26:724.
[23] Hoyle C E, Lee T Y, Roper T. J. Polym. Sci., Part A:Polym. Chem., 2004, 42:5301.
[24] Hoyle C E, Bowman C N. Angew. Chem. Int. Ed., 2010, 49:1540.
[25] 付长清(Fu C Q),程传杰(Cheng C J),申亮(Shen L),陈义旺(Chen Y W). 高分子通报(Polymer Bulletin), 2012(1):29.
[26] 徐源鸿(Xu Y H),熊兴泉(Xiong X Q),蔡雷(Cai Lei),唐忠科(Tang Z K),叶章基(Ye Z J). 化学进展(Progress in Chemistry), 2012, 24(2/3):385.
[27] Theato P. Multi-Component and Sequential Reactions in Polymer Synthesis. Berlin:Springer-Verlag, 2015. 87.
[28] Gadwal I, Stuparu M C, Khan A. Polym. Chem., 2015, 6:1393.
[29] Azizi N, Khajeh-Amiri A, Ghafuri H, Bolourtchian M. Phosphorus, Sulfur Silicon Relat. Elem., 2010, 185:1550.
[30] De S, Stelzer C, Khan A. Polym. Chem., 2012, 3:2342.
[31] De S, Khan A. Chem. Commun., 2012, 48:3130.
[32] Brändle A, Khan A. Polym. Chem., 2012, 3:3224.
[33] Gadwal I, Binder S, Stuparu M C, Khan A. Macromolecules, 2014, 47:5070.
[34] Gadwal I, Rao J, Baettig J, Khan A. Macromolecules, 2014, 47:35.
[35] Binder S, Gadwal I, Bielmann A, Khan A. J. Polym. Sci., Part A:Polym. Chem., 2014, 52:2040.
[36] Gadwal I, Khan A. RSC Adv., 2015, 5:43961.
[37] Fringuelli F, Pizzo F, Tortoioli S, Vaccaro L. Tetrahedron Lett., 2003, 44:6785.
[38] Albanese D, Landini D, Penso M. Synthesis, 1994:34.
[39] Fringuelli F, Pizzo F, Vittoriani C, Vaccaro L. Eur. J. Org. Chem., 2006, 2006:1231.
[40] Li S, Han J, Gao C. Polym. Chem., 2013, 4:1774.
[41] Loureiro R M, Amarelo T C, Abuin S P, Soulé E R, Williams R J. Thermochim. Acta, 2015, 616:79.
[42] Jin K, Heath W H, Torkelson J M. Polymer, 2015, 81:70.
[43] Zhang Q, Anastasaki A, Li G, Haddleton A J, Wilson P, Haddleton D M. Polym. Chem., 2014, 5:3876.
[44] Gadwal I, Khan A. Polym. Chem., 2013, 4:2440.
[45] Rahane S B, Hensarling R M, Sparks B J, Stafford C M, Patton D L. J. Mater. Chem., 2012, 22:932.
[46] Yang W J, Neoh K, Kang E, Teo S L, Rittschof D. Polym. Chem., 2013, 4:3105.
[47] Chen J, Yu C, Shi Z, Yu S, Lu Z, Jiang W, Zhang M, He W, Zhou Y, Yan D. Angew. Chem. Int. Ed., 2015, 54:3621.
[48] Cengiz N, Rao J, Sanyal A, Khan A. Chem. Commun., 2013, 49:11191.
[49] Ware T, Simon D, Hearon K, Kang T H, Maitland D J, Voit W. Macromol. Biosci., 2013, 13:1640.
[50] Katogi S, Yusa M. J. Polym. Sci., Part A:Polym. Chem., 2002, 40:4045.
[51] Sangermano M, Vitale A, Dietliker K. Polymer, 2014, 55:1628.
[52] Guzmán D, Ramis X, Fernández-Francos X, Serra A. Eur. Polym. J., 2014, 59:377.
[53] Flores M, Tomuta A M, Fernández-Francos X, Ramis X, Sangermano M, Serra A. Polymer, 2013, 54:5473.
[54] Guzmán D, Ramis X, Fernández-Francos X, Serra A. RSC Adv., 2015, 5:101623.
[55] Guzmán D, Ramis X, Fernández-Francos X, Serra A. Polymers, 2015, 7:680.
[56] Lin H, Ou J, Liu Z, Wang H, Dong J, Zou H. Anal. Chem., 2015, 87:3476.
[57] Lin H, Chen L, Ou J, Liu Z, Wang H, Dong J, Zou H. J. Chromatogr. A, 2015, 1416:74.
[58] Zhu D Y, Cao G S, Qiu W L, Rong M Z, Zhang M Q. Polymer, 2015, 69:1.