Investigating the Effect of End-Group, Molecular Weight, and Solvents on the Catalyst-Free Depolymerization of RAFT Polymers: Possibility to Reverse the Polymerization of Heat-Sensitive Polymers.

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.