Controlling polymer molecular weight distributions by light through reversible addition‐fragmentation chain transfer‐hetero‐Diels–Alder click conjugation

Abstract

AbstractLight‐regulated polymerization has emerged as a powerful tool to control the process of polymerization. However, tuning the polymer molecular weight distribution (MWD) by light is still not well developed. Here, we present a convenient approach for controlling the MWD in reversible addition‐fragmentation chain transfer (RAFT) polymerization by exploiting an ultraviolet light‐induced RAFT‐hetero‐Diels–Alder (RAFT‐HDA) reaction with a photoenol diene. The key point in this strategy is to terminate part of the propagating chains at a specific time by the RAFT‐HDA reaction. In addition, a photoenol diene with a hydroxyl group is also synthesized and successfully applied to realize this strategy, which can be further utilized for chain extension of ɛ‐caprolactone (ɛ‐CL) by ring opening polymerization to prepare diblock copolymers with different MWDs.