RAFT polymerization is attractive for its reliability, facile operation, and high tolerance to a wide variety of monomers, functional groups, solvents, and temperatures. Herein, we report the RAFT-based synthesis of well-defined polymers bearing hydroxyl groups at two terminals by using various monomers. We found that the molecular weight of obtained polymers was half that of a target value when a trithiocarbonate-type chain transfer agent (CTA) was used, suggesting that the polymers unexpectedly cleaved at the middle of the polymer chain as the reaction was proceeding. To address the problem, we synthesized a novel "dithiobenzoate"-type CTA, 2-[N-(2-hydroxyethyl)carbamoyl]prop-2-yl 4-hydroxydithiobenzoate (HECPHD), which bears hydroxyl groups at both terminals, and we succeeded in RAFT polymerization with various monomers without a cleavage of the polymers.
Keywords: RAFT agent; RAFT polymerization; dithiobenzoate.