While the conventional living cationic polymerization (LCP) provided opportunities to synthesizing well-defined polymers with predetermined molecular weights, desirable chemical structures and narrow dispersity, it is still important to continuously innovate new synthetic methods to meet the increasing requirements in advanced material engineering. Consequently, a variety of novel initiation/controlling systems have be demonstrated recently, which have enabled LCP with spatiotemporal control, broadened scopes of monomers and terminals, more user-friendly operations and reaction conditions, as well as improved thermomechanical properties for obtained polymers. In this work, recent advances in LCP is summarized with emerging initiation/controlling systems, including chemical-initiated/controlled cationic reversible addition-fragmentation chain transfer (RAFT) polymerization, photoinitiated/controlled LCP, electrochemical-controlled LCP, thionyl/selenium halide-initiated LCP, organic acid-assisted LCP, and stereoselective LCP. It is hoped that this summary will provide useful knowledge to people in related fields and stimulate new ideas to promote the development and application of LCP in both academia and industry.
Keywords: catalysis; cationic RAFT polymerization; living cationic polymerization; photocontrolled polymerization; vinyl ethers.
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