Fate of the RAFT End-Group in the Thermal Depolymerization of Polymethacrylates

Thermal RAFT depolymerization has recently emerged as a promising methodology for the chemical recycling of polymers. However, while much attention has been given to the regeneration of monomers, the fate of the RAFT end-group after depolymerization has been unexplored. Herein, we identify the dominant small molecules derived from the RAFT end-group of polymethacrylates. The major product was found to be a unimer (DP = 1) RAFT agent, which is not only challenging to synthesize using conventional single-unit monomer insertion strategies, but also a highly active RAFT agent for methyl methacrylate, exhibiting faster consumption and yielding polymers with lower dispersities compared to the original, commercially available 2-cyano-2-propyl dithiobenzoate. Solvent-derived molecules were also identified predominantly at the beginning of the depolymerization, thus suggesting a significant mechanistic contribution from the solvent. Notably, the formation of both the unimer and the solvent-derived products remained consistent regardless of the RAFT agent, monomer, or solvent employed.