Preparing Well-Defined Polyacrylamide-b-polycarbonate by Integrating Photoiniferter Polymerization and TBD-Catalyzed...

The dual-initiator technique allows the polymerization of different monomers from orthogonal polymerization mechanisms to obtain block copolymers (BCPs). In this study, it is attempted to combine photoiniferter living free radical polymerization and organocatalytic ring-opening polymerization (ROP) to design a hydroxyl-functionalized carbamodithioate, i.e., 4-(hydroxymethyl)benzyl diethylcarbamodithioate (HBDC), which can integrate photoiniferter polymerization of acrylamide monomers and ROP of cyclic carbonates. As a proof of concept, the monomer applicability is further extended to acrylates and lactones. The results confirm that the two polymerization systems are experimentally compatible in a stepwise sequence as well as in a simultaneous one-pot process to synthesize BCPs. It is reasonable to assume that HBDC can allow for simple and efficient one-pot access to well-defined BCPs from a larger range of monomers, which is more advantageous from the operational, economical, and environmental points of view.