Effects of Conjugated Systems on UV-Visible Light-sensitive D-π-A Type Sulfonium Salt Photoacid Generators

作     者：Xing-yu Wu 金明 Jian-chao Xie De-cheng Wan Jean Pierre Malval 

作者机构：School of Materials Science and EngineeringTongji UniversityShanghai 201804China Institut de Science des Mattériaux de MulhouseUMR CNRS 7361Universitéde Haute-Alsace15 rue Jean Starcky68057 MulhouseFrance 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2016年第34卷第12期

页      面：1456-1468页

核心收录：

学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：financially supported by the National Natural Science Foundation of China(Nos.51173134 and 51573139) Fundamental Research Funds for the Central Universities and the Open Measuring Fund for Large Instrument and Equipment(No.0002015033)of Tongji University 

主　　题：Sulfonium salt Photoacid generators π-conjugated structures. 

摘      要：A series of D-π-A type sulfonium salt photoacid generators with different π-conjugated structures, such as triphenyl, phenylstilbene, styryl-biphenyl, and stilbene, were designed to determine the effect of molecular structures on the photochemical and photophysical properties. The mechanisms of photochemical generation of H＋ were studied by UV-Vis spectroscopy, theoretical calculations, and fluorescence spectroscopy. It is found that the frontier orbits determine the absorption, the molar extinction coefficients, and the quantum yields of photoacid generation. Triphenyl systems connected with sulfonium are beneficial to increase the quantum yields of acid generation. The photoreactivity of four sulfonium salts was further evaluated through the polymerizations of various epoxide monomers at different irradiation wavelengths （365- 425 nm） by using the real-time infrared spectroscopy with light-emitting diodes. The high quantum yields for acid generation （ФH＋ = -0.32 to 0.58） and the high molar extinction coefficients （ε = -23500 L.mol-1.cm-1 to 31000 L.mol-1.cm-1） of the sulfonium salts lead to high conversion rates （over 50%-80%）. Hence, these photoinitiators exhibit potential for the photocuring applications.