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Significance Statement
A powerful and facile thiol-yne click polymerization, which was carried out under very mild conditions without any normally used external catalyst, such as UV light, elevated temperature, amine and transition metal complexes, was established. Mixing the aromatic dialkynes and dithiols with equivalent molar ratio at 30 oC in THF, and then reacting for as short as 2 h readily produced soluble and regioregular poly(vinylenesulfide)s (PVSs) with (Mw up to 85200) in excellent yields (up to 97%). Furthermore, functional groups, such as tetraphenylethene, a moiety featured the aggregation-induced emission (AIE) characteristic, could be facilely incorporated via this catalyst-free thiol-yne click polymerization to make the produced PVS AIE-active.
The PVSs enjoy high thermal stability, and good film-forming ability. Thin solid films of PVSs exhibit higher refractive index values (n > 1.63) than commercially important optical plastics.
It is no doubt that such powerful catalyst-free thiol-yne click polymerization will remarkably simplify the reaction conditions and be broadly applied in various areas including in polymer, material and biologic sciences.
Journal Reference
Macromolecules, 2014, 47 (4), pp 1325–1333.
Bicheng Yao †, Ju Mei †, Jie Li §, Jian Wang †,Haiqiang Wu †, Jing Zhi Sun †, Anjun Qin *†‡, and Ben Zhong Tang *†‡§
† MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China and
‡ Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices,South China University of Technology, Guangzhou 510640, China and
§ Department of Chemistry, Institute for Advanced Study, Institute of Molecular Functional Materials, and State Key Laboratory of Molecular Neuroscience,The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong China.
Abstract
The “thio-click” polymerization is a well-expanded concept of click polymerization. Among the click polymerizations, the thiol–yne click polymerization is less developed and still in its infancy stage. In general, UV light, elevated temperature, amine, or transition metal complexes is needed to catalyze the thiol–yne click polymerization, which greatly complicates the experimental operation and limits its application. In this work, a facile and powerful thiol–yne click polymerization was developed, which could be carried out under very mild conditions without using external catalyst. Simply mixing the aromatic diynes (1a–1e) and dithiols (2–4) with equivalent molar ratio in THF at 30 °C will readily produce soluble and regioregular functional poly(vinylene sulfide)s (PIa–PIe, PII, and PIII) with high molecular weights (Mw up to 85 200) in excellent yields (up to 97%) after as short as 2 h. Furthermore, no double addition product of an ethynyl group was found. This catalyst-free thiol–yne click polymerization has remarkably simplified the reaction conditions and will facilitate the preparation of functional materials applied in diverse areas.
Copyright © 2014 American Chemical Society
