Beres Magdalena A, Boyer Cyrille, Hartlieb Matthias, Konkolewicz Dominik, Qiao Greg G, Sumerlin Brent S, Perrier Sébastien
Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
Cluster for Advanced Macromolecular Design, School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia.
ACS Polym Au. 2025 Mar 27;5(3):184-213. doi: 10.1021/acspolymersau.4c00101. eCollection 2025 Jun 11.
This perspective offers an in-depth guide to photopolymerizations mediated with thiocarbonylthio compounds, with a particular focus on photoiniferter and photoinduced energy/electron transfer RAFT (PET-RAFT) polymerizations, focusing on practical considerations. It is designed to provide both newcomers and experts with the practical knowledge needed to harness light-mediated polymerizations for innovative applications. The discussion begins with an overview of conventional RAFT polymerization and proceeds to highlight the distinctive advantages of the photomediated processes. The photochemical behavior of thiocarbonylthio compounds, along with the selection of appropriate light wavelengths, is critically examined for its impact on polymerization kinetics and optimization of polymer properties. Key parameters influencing polymerization successsuch as catalyst selection, solvent choice, light intensity, and temperatureare explored in detail. The importance of oxygen tolerance and end-group fidelity is also addressed, as these factors are essential for achieving well-defined polymers. Additionally, reactor configurations are reviewed, focusing on the roles of light sources, reactor geometry (batch versus flow systems), and temperature control in optimizing the reaction efficiency. The article concludes by integrating these concepts into a comprehensive framework for optimizing photoiniferter and PET-RAFT polymerizations.
这一观点为硫代羰基硫化合物介导的光聚合反应提供了深入指南，特别关注光引发转移终止剂和光诱导能量/电子转移可逆加成-断裂链转移（PET-RAFT）聚合反应，并侧重于实际考量。它旨在为新手和专家提供利用光介导聚合反应实现创新应用所需的实践知识。讨论首先概述传统的可逆加成-断裂链转移聚合反应，接着突出光介导过程的独特优势。对硫代羰基硫化合物的光化学行为以及合适光波长的选择进行了严格审视，以考察其对聚合动力学和聚合物性能优化的影响。详细探讨了影响聚合成功的关键参数，如催化剂选择、溶剂选择、光强度和温度。还讨论了耐氧性和端基保真度的重要性，因为这些因素对于获得结构明确的聚合物至关重要。此外，对反应器配置进行了综述，重点关注光源、反应器几何形状（间歇式与连续流动系统）以及温度控制在优化反应效率方面的作用。文章最后将这些概念整合到一个优化光引发转移终止剂和PET-RAFT聚合反应的综合框架中。
