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.

自 2015 年首次报道阳离子可逆加成断裂链转移 (RAFT) 聚合以来，阳离子 RAFT 和退化链转移 (DT) 聚合在许多方面取得了很大进展，包括有效的链转移剂、适用的引发剂或催化剂、可控单体和聚合物的可控结构。阳离子 RAFT 聚合不仅在硫代羰基硫基 RAFT 试剂、RAFT 机制和可控聚合物结构方面与自由基 RAFT 聚合有许多相似之处，而且还表现出源自阳离子聚合的差异，例如新型 RAFT 或 DT 试剂、引发和传播机制，可控单体，以及所得聚合物的立体结构。本综述涵盖了阳离子 RAFT 和 DT 聚合的进展，重点介绍了阳离子和自由基 RAFT 聚合之间的异同。总的来说，讨论了阳离子 RAFT 和 DT 聚合的特性和扩展潜力。