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由曙红Y催化的光加速解聚反应。

Light-accelerated depolymerization catalyzed by Eosin Y.

作者信息

Bellotti Valentina, Parkatzidis Kostas, Wang Hyun Suk, De Alwis Watuthanthrige Nethmi, Orfano Matteo, Monguzzi Angelo, Truong Nghia P, Simonutti Roberto, Anastasaki Athina

机构信息

Department of Material Science, University of Milano-Bicocca Via R. Cozzi 55 20125 Milan Italy.

Laboratory of Polymeric Materials, Department of Materials, ETH Zurich Vladimir-Prelog-Weg-5 Zurich Switzerland

出版信息

Polym Chem. 2022 Dec 20;14(3):253-258. doi: 10.1039/d2py01383e. eCollection 2023 Jan 17.

Abstract

Retrieving the starting monomers from polymers synthesized by reversible deactivation radical polymerization has recently emerged as an efficient way to increase the recyclability of such materials and potentially enable their industrial implementation. To date, most methods have primarily focused on utilizing high temperatures (typically from 120 °C to 180 °C) to trigger an efficient depolymerization reaction. In this work, we show that, in the presence of Eosin Y under light irradiation, a much faster depolymerization of polymers made by reversible addition-fragmentation chain-transfer (RAFT) polymerization can be triggered even at a lower temperature ( 100 °C). For instance, green light, in conjunction with ppm amounts of Eosin Y, resulted in the accelerated depolymerization of poly(methyl methacrylate) from 16% (thermal depolymerization at 100 °C) to 37% within 1 hour, and finally 80% depolymerization after 8 hours, as confirmed by both H-NMR and SEC analyses. The enhanced depolymerization rate was attributed to the activation of a macroCTA by Eosin Y, thus resulting in a faster macroradical generation. Notably, this method was found to be compatible with different wavelengths ( blue, red and white light irradiation), solvents, and RAFT agents, thus highlighting the potential of light to significantly improve current depolymerization approaches.

摘要

从通过可逆失活自由基聚合合成的聚合物中回收起始单体,最近已成为提高此类材料可回收性并有可能实现其工业应用的一种有效方法。迄今为止,大多数方法主要集中在利用高温(通常为120℃至180℃)来引发高效的解聚反应。在这项工作中,我们表明,在光照下曙红Y存在的情况下,即使在较低温度(100℃)下,也可以引发由可逆加成-断裂链转移(RAFT)聚合制备的聚合物更快的解聚。例如,绿光与ppm量的曙红Y结合,导致聚甲基丙烯酸甲酯在1小时内的解聚率从16%(100℃热解聚)加速至37%,8小时后最终解聚率达到80%,这通过1H-NMR和SEC分析得到证实。解聚速率的提高归因于曙红Y对大分子链转移剂(macroCTA)的活化,从而导致更快的大分子自由基生成。值得注意的是,该方法被发现与不同波长(蓝光、红光和白光照射)、溶剂和RAFT试剂兼容,从而突出了光显著改进当前解聚方法的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2565/9843692/270deedb2a3d/d2py01383e-f1.jpg

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