Electro-Controlled Living Cationic Polymerization.

Cationic polymerizations have long been industrialized; however, stimulus-regulated cationic polymerization remains to be developed. An electrochemically controlled living cationic polymerization is presented for the first time. In the presence of external potential and organic-based electrocatalyst, a series of monomers can be polymerized under a cationic chain-transfer mechanism. The resulting polymers exhibit well-defined molecular mass, narrow dispersity, and good chain-end fidelity. By controlling the external potential to switch the electrocatalyst between its oxidized and reduced states, ON/OFF polymerization can be achieved. This method is a versatile way to a large range of monomers, including vinyl ether-type and p-substituted styrene-type monomers. Given the sustainability feature and broad interest of electrochemical synthetic techniques, we envisaged that this method would lead a new direction of external regulated living ionic polymerization.