Reversing reversible deactivation radical polymerization (RDRP) to regenerate the original monomer is an attractive prospect for both fundamental research and industry. However, current depolymerization strategies are often applied to highly heat-tolerant polymers with a specific end-group and can only be performed in a specific solvent. Herein, we depolymerize a variety of poly(methyl methacrylate) materials made by reversible addition–fragmentation chain-transfer (RAFT) polymerization and terminated by various end groups (dithiobenzoate, trithiocarbonate, and pyrazole carbodithioate). The effect of the nature of the solvent on the depolymerization conversion was also investigated, and key solvents such as dioxane, xylene, toluene, and dimethylformamide were shown to facilitate efficient depolymerization reactions. Notably, our approach could selectively regenerate pure heat-sensitive monomers (e.g., tert-butyl methacrylate and glycidyl methacrylate) in the absence of previously reported side reactions. This work pushes the boundaries of reversing RAFT polymerization and considerably expands the chemical toolbox for recovering starting materials under relatively mild conditions.

中文翻译：

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研究端基、分子量和溶剂对 RAFT 聚合物无催化剂解聚的影响：逆转热敏聚合物聚合的可能性

可逆失活自由基聚合 (RDRP) 以再生原始单体对于基础研究和工业来说都是一个有吸引力的前景。然而，目前的解聚策略通常应用于具有特定端基的高耐热聚合物，并且只能在特定溶剂中进行。在此，我们解聚了多种通过可逆加成-断裂链转移 (RAFT) 聚合制备并由各种端基（二硫代苯甲酸酯、三硫代碳酸酯和吡唑碳二硫酸酯）封端的聚（甲基丙烯酸甲酯）材料。还研究了溶剂性质对解聚转化率的影响，发现关键溶剂如二恶烷、二甲苯、甲苯和二甲基甲酰胺可促进高效的解聚反应。尤其，甲基丙烯酸叔丁酯和甲基丙烯酸缩水甘油酯）在没有先前报道的副反应的情况下。这项工作突破了逆向 RAFT 聚合的界限，并大大扩展了在相对温和的条件下回收起始材料的化学工具箱。