Cationic RAFT and DT Polymerization

ABSTRACT Since the first report of cationic reversible addition-fragmentation chain transfer (RAFT) polymerization in 2015, there have been great developments in many aspects of cationic RAFT and degenerative chain transfer (DT) polymerizations, including effective chain-transfer agents, applicable initiators or catalysts, controllable monomers, and controlled architectures of polymers. Cationic RAFT polymerizations exhibit not only many similarities to radical RAFT polymerizations in terms of thiocarbonylthio-based RAFT agents, RAFT mechanisms, and controlled polymer structures but also differences originating from the cationic polymerizations, such as novel RAFT or DT agents, initiation and propagation mechanisms, controllable monomers, and stereostructures of the resulting polymers. This review covers the progress made with cationic RAFT and DT polymerizations, focusing on the similarities and differences between cationic and radical RAFT polymerizations. In total, the characteristics and expanding potentials of cationic RAFT and DT polymerizations are discussed.