dl-Methionine-Mediated Reversible Deactivation Radical Polymerization of Styrene and Methyl Methacrylate.

Reversible deactivation radical polymerization (RDRP) is a facile and highly efficient technique for the synthesis of well-defined polymer with precise structure. dl-Methionine (Met) as a RDRP control agent is described and assessed for RDRP of styrene (St) and methyl methacrylate (MMA) with AIBN as radical initiator at 75 °C, which enables excellent control of this polymerization. The addition of dl-Methionine significantly decreased the dispersity (Đ) of the polymers for both monomers and first-order linear kinetic plots of polymethyl methacrylate (PMMA) are observed in DMSO. Considering the heat resistance of dl-Methionine, kinetic studies indicate that polymerization develops at a faster rate at higher reaction temperature (100 °C) with the same dl-Methionine content. Well-defined polymethyl methacrylate-block-polystyrene (PMMA-block-PSt) is successfully achieved by the chain extension reaction that demonstrates the high end fidelities of this polymerization approach. The system allows the use of dl-Methionine, a rich source and easily synthesized agent, to mediate RDRP strategy.