Photoinitiation Mechanisms of Novel Phenothiazine-Based Oxime and Oxime Esters Acting as Visible Light Sensitive Type I and Multicomponent Photoinitiators

In this work, three new photoinitiators, based on the phenothiazine scaffold as a chromophore and potentially bearing the oxime ester functionality as an initiating group are designed and synthesized for the free radical polymerization of acrylates, the cationic polymerization of epoxides, and the formation of interpenetrated polymer networks upon irradiation with a light emitting diode emitting at 405 nm. These phenothiazine-based oxime and oxime esters revealed impressive photoinitiation ability manifested by excellent polymerization rates and high final reactive function conversions. Significantly, they can be used as both; one-component (Type I) and two-component photoinitiating systems. Photoinitiation mechanisms through which reactive species are produced are investigated by means of different complementary techniques including real-time Fourier transform infrared spectroscopy, UV-visible absorption spectroscopy, electron spin resonance spectroscopy, fluorescence (steady state and time resolved), cyclic voltammetry, and molecular modeling calculations. Thermal initiation behavior of the different oxime esters is also studied by using differential scanning calorimetry, highlighting their dual thermal/photochemical initiation ability. Finally, 3D printed objects are successfully fabricated by conducting both direct laser writing and 3D printing experiments.

Automated summary

In this study, three new photoinitiators based on the phenothiazine scaffold and potentially bearing the oxime ester functionality were designed and synthesized. These photoinitiators demonstrated excellent initiation ability for both radical polymerization and cationic polymerization, as well as the formation of interpenetrated polymer networks. The mechanisms of photoinitiation were investigated through various techniques, and the thermal initiation behavior of the oxime esters was also studied. In addition, successful fabrication of 3D printed objects was achieved using direct laser writing and 3D printing experiments.