Azlactone-based copolymers by redox-initiated MADIX polymerization at room temperature in ethanol

Abstract

Macromolecular design via the interchange of xanthate (MADIX) polymerization of 2-vinyl-4,4-dimethylazlactone (VDM) used as comonomer is reported. Rhodixan® A1 was employed as chain transfer agent and ethanol was used as solvent. An efficient control of the MADIX polymerization with complete monomer conversion was reached after 6 h using either a thermal initiation at 70 °C or a redox initiating system at 25 °C. In contrast with thermal-initiated MADIX polymerization at 70 °C, redox-initiated MADIX polymerization allows the reaction to be carried out at 25 °C and avoids solvolysis of the azlactone ring after 6 h. The resulting azlactone-based copolymers were used as a “clickable” platform for chemical post-polymerization modification (PPM) as demonstrated using allylamine as a model of primary amine. PPM with allylamine performed in ethanol at 25 °C was quantitative and selective in 2 h.