Mechanism‐Guided Design of Chain‐Growth Click Polymerization Based on a Thiol‐Michael Reaction

The development of chain-growth click polymerization is challenging yet desirable in modern polymer chemistry. In this work, we reported a novel chain-growth click polymerization based on the thiol-Michael reaction. This polymerization could be performed efficiently under ambient conditions and spatiotemporally regulated by ultraviolet light, allowing the synthesis of sulfur-containing polymers in excellent yields and high molecular weights. Density functional theory calculations indicated that the thiolate addition to the Michael acceptor is the rate-determining step, and introducing the phenyl group could facilitate the chain-growth process. This polymerization is a new type of chain-growth click polymerization, which will provide a unique approach to creating functional polymers.