Excitation Dependence in Photoiniferter Polymerization
Excitation Dependence in Photoiniferter Polymerization
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DOI：
10.1021/acsmacrolett.2c00683
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发表时间：
2022-12-19
影响因子：
7.015
通讯作者：
Sumerlin, Brent S.
中科院分区：
文献类型：
--
作者：
Hughes, Rhys W.;Lott, Megan E.;Sumerlin, Brent S.
我们报道了以三硫代碳酸酯和黄原酸盐为媒介的光诱导聚合的一个基本特征。研究发现，聚合反应高度依赖于离子激活剂的电子激发。与激活pi-*pi*转变的聚合相比，当三硫代碳酸酯和黄原酸酯介导的光干扰物聚合以n-*pi*转变为靶点时，观察到聚合速度加快和对分子量更好的控制。聚合速率的差异归因于C-S光解速率的增加，这一点通过模型捕获研究得到了证实。这项研究对电子激发在光诱导聚合中的作用提供了有价值的见解，并为在光敏性很重要的应用中选择照射条件提供了指导。
We report on a fundamental feature of photo-iniferter polymerizations mediated with trithiocarbonates and xanthates. The polymerizations were found to be highly dependent on the activated electronic excitation of the iniferter. Enhanced rates of polymerization and greater control over molecular weights were observed for trithiocarbonate-and xanthate-mediated photo-iniferter polymerizations when the n-* pi* transition of the iniferter was targeted compared to the polymerizations activating the pi-* pi* transition. The disparities in rates of polymerization were attributed to the increased rate of C-S photolysis which was confirmed using model trapping studies. This study provides valuable insight into the role of electronic excitations in photoiniferter polymerization and provides guidance when selecting irradiation conditions for applications where light sensitivity is important.