Effect of Decarboxylation on the Photoinitiation Behavior of Nitrocarbazole-Based Oxime Esters

Abstract

A series of 50 oxime esters bearing various substituents were designed and synthesized as photoinitiators (48 of them were never synthesized before and only B1 and B10 were reported). Good light absorption properties in the visible range were observed for these oxime esters. Some structures exhibited better photoinitiation abilities than diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) upon exposure to a LED@405 nm. Interestingly, PIs with methyl substituent on the oxime ester group have better photoinitiation performance than the others. Substituent effects were investigated through molecular orbitals calculations, the detection of CO2, and the investigation of the generated free radicals. The results demonstrate that the substituents on the oxime ester group exert major effects on the photoinitiation ability via the decarboxylation reaction. In addition, a chemical mechanism was proposed. 3D printed objects were successfully obtained by using the most reactive oxime ester as photoinitiator, and their thermal initiation behaviors of several oxime esters were also studied (dual thermal/photochemical initiator behavior).