Versatility of Pyrylium Salt/Vinyl Ether Initiating System for Epoxide Dual‐Cure Polymerization: Kick‐Starting Effect of the Coinitiator

Pyrylium salts combined with vinyl ethers are shown to act as new versatile dual‐cure initiating systems for both photochemical and thermal initiation of oxirane monomers. The combination of both possibilities allows the curing of thick samples through photoinduced frontal polymerization. On the basis of quantum calculations and photochemical experiments, some clues are given about the reaction mechanisms involved. Interestingly, a sequential kick‐starting effect is observed in the presence of vinyl ether enabling the curing of oxetane monomers. Thereby, this communication presents a short overview of potential of pyrylium salts in cationic polymerization of oxiranes. The reaction between pyrylium salt and vinyl ether group is a promising way to design a versatile dual‐cure initiating system for cationic polymerization of epoxide monomers. Vinyl ethers induce a kick‐starting effect, which enables tuning of the reactivity of the system.