We successfully synthesized poly(l‐lactide)‐b‐poly (methyl methacrylate) diblock copolymers at ambient temperature by combining ultraviolet light‐induced copper‐catalyzed ATRP and organo‐catalyzed ring‐opening polymerization (ROP) in one‐pot. The polymerization processes were carried out by three routes: one‐pot simultaneous ATRP and ROP, one‐pot sequential ATRP followed by ROP, and one‐pot sequential ROP followed by ATRP. The structure of the block copolymers is confirmed by nuclear magnetic resonance and gel permeation chromatography, which suggests that the polymerization method is facile and attractive for preparing block copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018.
poly(l‐lactide)‐b‐poly(methyl methacrylate) diblock copolymers were synthesized by combining UV‐induced ATRP and ring‐opening polymerization (ROP) at ambient temperature in one‐pot. DBU acted not only as the ligand of copper (I) bromide in ultraviolet light‐induced ATRP but also as the catalyst of organocatalyzed ROP. It appears to be a potential method and is expected to be used for the synthesis of block copolymers with multifunctional groups and advanced properties.