共聚物
材料科学
高分子化学
高折射率聚合物
硒
折射率
单体
化学
化学工程
苯乙烯
反应性(心理学)
作者
Cheng-Jian Zhang,Lan-Fang Hu,Jia-Liang Yang,Xiao-Han Cao,Xing-Hong Zhang
标识
DOI:10.1016/j.eurpolymj.2020.109776
摘要
Abstract Polythioesters represent a promising functional polymer owing to the ubiquity and uniqueness of thioester bonds, however, to develop new examples of (functionalized) polythioesters for broadening the range of their applications is a grand challenge. Here, we report a convenient synthesis of a polythioester incorporating both thioester and selenide groups in repeating units via the alternating copolymerization of γ-selenobutyrolactone with episulfides including propylene sulfide and cyclohexene sulfide. This process mediated by a relatively mild phosphazene base of P1 exhibits very high activity with turnover of frequency (TOF) values of up to 1200 h−1, in which the nucleophilic attack of a selenol-type anion to episulfides is convinced as the rate-determining step by kinetic investigations. The prepared poly(thioester-alt-selenide)s have rigorously alternating sequences under optimized reaction conditions, molecular weights of 2.5–12.8 kg/mol, glass-transition temperatures of as low as −45.2 °C. Of unique, this copolymer exhibits remarkably high refractive indices of up to 1.74, suggesting a potential application prospect in optical materials.
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