Citation: Xing-yu Wu, Jin Ming, Jian-chao Xie, De-cheng Wan, Malval Jean Pierre. Effects of Conjugated Systems on UV-Visible Light-sensitive D-π-A Type Sulfonium Salt Photoacid Generators[J]. Chinese Journal of Polymer Science, ;2016, 34(12): 1456-1468. doi: 10.1007/s10118-016-1863-8 shu

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

a.
School of Materials Science and Engineering, Tongji University, Shanghai 201804, China
b.
Institut de Science des Matériaux de Mulhouse, UMR CNRS 7361, Université de Haute-Alsace, 15 rue Jean Starcky, 68057 Mulhouse, France

Corresponding author: Jin Ming, mingjin@tongji.edu.cn
Received Date: 24 June 2016
Revised Date: 12 August 2016
Accepted Date: 12 August 2016

Fund Project: the National Natural Science Foundation of China 51173134the National Natural Science Foundation of China 51573139Fundamental Research Funds for the Central Universities and the Open Measuring Fund for Large Instrument and Equipment of Tongji University 0002015033

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 (Φ_H⁺=~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.
- Sulfonium salt,
- Photoacid generators,
- π-conjugated structures
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