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Iron complexes as photoinitiators for radical and cationic polymerization through photoredox catalysis processes
Authors:Jing Zhang  Damien Campolo  Frederic Dumur  Pu Xiao  Jean Pierre Fouassier  Didier Gigmes  Jacques Lalevée
Affiliation:1. Institut de Science des Matériaux de Mulhouse IS2M, Mulhouse Cedex, France;2. Aix‐Marseille Université, Marseille Cedex, France
Abstract:Six iron complexes (FeCs) with various ligands have been designed and synthesized. In combination with additives (e.g., iodonium salt, N‐vinylcarbazole, amine, or chloro triazine), the FeC‐based systems are able to efficiently generate radicals, cations, and radical cations on a near UV or visible light‐emitting diode (LED) exposure. These systems are characterized by an unprecedented reactivity, that is, for very low content 0.02% FeC‐based systems is still highly efficient in photopolymerization contrary to the most famous reference systems (Bisacylphosphine oxide) illustrating the performance of the proposed catalytic approach. This work paves the way for polymerization in soft conditions (e.g., on LED irradiation). These FeC‐based systems exhibit photocatalytic properties, undergo the formation of radicals, radical cations, and cations and can operate through oxidation or/and reduction cycles. The photochemical mechanisms for the formation of the initiating species are studied using steady state photolysis, cyclic voltammetry, electron spin resonance spin trapping, and laser flash photolysis techniques. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 42–49
Keywords:cationic photopolymerization  iron complexes  LEDs  photoinitiator  photoredox catalysis  radical photopolymerization
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