Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Patxi Garra (1) , Celine Dietlin (1) , Fabrice Morlet-Savary (1) , Frederic Dumur (2, 3) , Didier Gigmes (2, 3) , Jean-Pierre Fouassier (1) , Jacques Lalevee (1)

1 IS2M - Institut de Science des Matériaux de Mulhouse
2 ICR - Institut de Chimie Radicalaire
3 AMU - Aix Marseille Université

Redox polymerizations are of huge importance throughout academic and industrial polymer science. Many authors propose the reaction of reducing (Red) and oxidizing (Ox) agents to accelerate/initiate radical or cationic polymerizations. As a result of activation energies typically below 80 kJ/mol, such reactions can occur under mild conditions, e.g., at room temperature, with reduced energy consumptions and robust in applications, such as the fabrication of composites. However, a clear definition of redox polymerization can only be found in reviews dealing with redox free radical polymerizations (FRP) published twenty years ago (or more). Therefore, a fresh and broader update is provided here for more recent work. The concepts involved when the Redand Oxagents (constituting the redox initiating system) are mixed under mild conditions are presented, followed by a discussion of the redox FRP initiating systems in bulk. Initiating systems dealing with the redox cationic polymerization (CP) are reviewed, and parallels between conventional FRP/CP and controlled polymerizations, in which redox systems are used, is provided. Many redox agents are useful in both modes. Finally, dual-cure (redox/photochemical; redox dual FRP/CP) systems is presented and selected applications are reviewed. Altogether, the state of the art for redox two-component polymerizations is provided, along with some perspectives. (C) 2019 Elsevier B.V. All rights reserved.

Domaines: Chimie

Patxi Garra, Celine Dietlin, Fabrice Morlet-Savary, Frederic Dumur, Didier Gigmes, et al.. Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications. Progress in Polymer Science, 2019, 94, pp.33--56. ⟨10.1016/j.progpolymsci.2019.04.003⟩. ⟨hal-02491502⟩