Degradable Vinyl Random Copolymers via Photocontrolled Radical Ring‐Opening Cascade Copolymerization**
Degradable Vinyl Random Copolymers via Photocontrolled Radical Ring‐Opening Cascade Copolymerization**
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通过光控自由基环的可降解乙烯基无规共聚物——开级联聚合**
DOI：
10.1002/anie.202113302
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Niu, Jia
中科院分区：
文献类型：
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作者：
Wang, Wenqi;Zhou, Zefeng;Sathe, Devavrat;Tang, Xuanting;Moran, Stephanie;Jin, Jing;Haeffner, Fredrik;Wang, Junpeng;Niu, Jia
通过自由基开环聚合实现的可降解乙烯基聚合物是解决不可降解乙烯基塑料带来的挑战的有希望的解决方案。然而，在可降解乙烯基聚合物主链中实现不稳定官能团的均匀分布仍然具有挑战性。在此，我们报告了一种通过自由基开环级联共聚（rROCCP）制备可降解乙烯基无规共聚物的光催化方法。在环境温度下由可见光介导的大环烯丙基砜和丙烯酸酯或丙烯酰胺的rROCCP在整个进料组合物范围内实现了接近一致的共聚单体反应性比。实验和计算证据表明，原位产生的二氧化硫 (SO2) 对链增长具有异常可逆的抑制作用，通过降低 SO2 的溶解度可以成功克服这种抑制作用。这项研究为可降解乙烯基无规共聚物提供了一种强有力的方法，其材料性能与不可降解乙烯基聚合物相当。
Degradable vinyl polymers by radical ring‐opening polymerization are promising solutions to the challenges caused by non‐degradable vinyl plastics. However, achieving even distributions of labile functional groups in the backbone of degradable vinyl polymers remains challenging. Herein, we report a photocatalytic approach to degradable vinyl random copolymers via radical ring‐opening cascade copolymerization (rROCCP). The rROCCP of macrocyclic allylic sulfones and acrylates or acrylamides mediated by visible light at ambient temperature achieved near‐unity comonomer reactivity ratios over the entire range of the feed compositions. Experimental and computational evidence revealed an unusual reversible inhibition of chain propagation by in situ generated sulfur dioxide (SO2), which was successfully overcome by reducing the solubility of SO2. This study provides a powerful approach to degradable vinyl random copolymers with comparable material properties to non‐degradable vinyl polymers.