Switching from Single to Simultaneous Free‐Radical and Anionic Polymerization with Enamine‐Based Organic Electron Donors

Although most monomers can polymerize through different propagation pathways, polymerization-initiating systems that switch from one mode to another are rare. In this study, we demonstrate enamine-based organic electron donors (OEDs) constitute the first able initiate either free-radical or anionic polymerization under simple, mild, and safe conditions. While direct electron-transfer reduction of by OEDs results in initiation chain-growth polymerization, introduction a competing oxidant with higher potential than monomer switches former clean radical-propagation process. The benefit dual-mode activator is highlighted synthesis an interpenetrating polymer network simultaneous radical processes.