Structure–Reactivity Relationships of Oxime–Oxalate/Glyoxylate/Ester Derivatives: Dual Photo/Thermal Initiators for Visible Light Polymerization and Composite Preparation

作者：Tong Gao, Thybault De Monfreid, Ji Feng, Jing Zhang, Fabrice Morlet‐Savary, Céline Dietlin, Michael Schmitt, Frédéric Dumur, Jean‐Patrick Joly, Malek Nechab, Pu Xiao, Jacques Lalevée · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202521296 · 被引用次数：2 · 研究领域：Photopolymerization techniques and applications、Advanced Polymer Synthesis and Characterization、Dental materials and restorations

Abstract In this study, we reported the design, synthesis, and comprehensive evaluation of a series of nitro carbazole‐based oxime photoinitiators (OPIs, OP1: oxime oxalate, OP2: oxime glyoxylate), as a series of efficient Type I photoinitiators (PIs) for the free radical photopolymerization (FRP) of trimethylolpropane triacrylate (TMPTA) and ethoxylated trimethylolpropane triacrylate (ETPTA) under blue light‐emitting diodes and sunlight irradiation. Computational molecular modeling was employed to predict the effect of OPIs structures on the photoinitiation properties. The predictions suggest that OP1 had a higher propensity for decarboxylation and therefore a better photoinitiation behavior. Compared to OP2, OP3, and commercial benchmark photoinitiator TPO, OP1 exhibits exceptional photoinitiation performance when exposed to LED@405 nm, LED@450 nm, and sunlight. OP1 undergoes decarboxylation to efficiently produce CO 2 and free radicals, thereby initiating the photopolymerization reaction. Remarkably, OP1 is successfully applied in 3D printing, producing complete morphology with high‐resolution structure, showcasing its potential for advanced manufacturing applications. The photochemical mechanism of OPIs is comprehensively elucidated using the monitoring of the CO 2 , steady state photolysis, UV–vis absorption spectroscopy, fluorescence spectroscopy, and electron spin resonance techniques. These experimental investigations are supported by data OP1 from the molecular model...