Graft polymer synthesis by RAFT transfer‐to

ABSTRACT The synthesis of graft polymers via controlled polymerization techniques has enabled the facile modification of the surface properties of a variety of substrates. Three grafting methods are typically highlighted in the literature: grafting‐to, grafting‐from, and grafting‐through. However, a fourth method exists when grafting is conducted using reversible addition‐fragmentation chain transfer (RAFT) polymerization, which we refer to as transfer‐to. Transfer‐to differs from the other grafting strategies in the types of structural defects and impurities that arise during polymerization. This review addresses important considerations when conducting RAFT transfer‐to, including RAFT chain transfer agent selection, monomer structure, and reaction conditions. In addition, we highlight key mechanistic differences between grafting‐from and transfer‐to and their effects on the structure and sample composition of the resulting graft polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2865–2876 Three grafting methods are typically utilized: grafting‐to, grafting‐from, and grafting‐through. A fourth method exists when conducting RAFT polymerization: transfer‐to. Transfer‐to differs from the other grafting strategies in the types of structural defects and impurities that arise during polymerization. This review addresses important considerations when conducting RAFT transfer‐to graft polymerization. In addition, we highlight key mechanistic differences between grafting‐from and transfer‐to and their effects on the structure and sample composition of the resulting graft polymers.