Switchable Radical Polymerization of α-Olefins via Remote Hydrogen Atom or Group Transfer

Introducing polar groups into non-polar polyolefins can significantly enhance the important properties of materials. However, producing polyolefin backbones consisting of polar blocks remains elusive, due to the substantial difference of reactivity ratios between polar and non-polar olefin monomers in radical polymerization or the poisoning of transition-metal catalysts by polar groups in coordination polymerization. Herein we present a practical way for the preparation of polyethylene-based polymers with distinct polar groups by radical polymerization of α-olefins. A strategy of switchable remote hydrogen atom or group transfer is devised, leading to a diverse range of AAB or ABC sequence-defined carbon-chain polyolefins. The utility of these polymers is demonstrated by using poly(ethyl 2-cyanohept-6-enoate) (P2) as an interphase layer material in anode-free Li metal battery, which effectively improves the cycling stability of the battery and indicates its potential in energy storage applications.