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

Yuxi Zhao (1) , Marion Rollet (2) , Laurence Charles (2) , Gabriel Canard (3) , Didier Gigmes (1) , Patrice Vanelle (1) , Julie Broggi Broggi (1)

1 ICR - Institut de Chimie Radicalaire
2 AMU - Aix Marseille Université
3 CINaM - Centre Interdisciplinaire de Nanoscience de Marseille

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

Mots clés: Anionic polymerization; Organic electron donors; Radical polymerization; Reduction Method; Electron transfer ET

Domaines: Chimie organique; Matériaux; Polymères

Yuxi Zhao, Marion Rollet, Laurence Charles, Gabriel Canard, Didier Gigmes, et al.. Switching from Single to Simultaneous Free-Radical and Anionic Polymerization with Enamine-Based Organic Electron Donors. Angewandte Chemie International Edition, 2021, 60 (35), pp.19389-19396. ⟨10.1002/anie.202106733⟩. ⟨hal-03402294⟩