Thioxanthone Derivatives as a New Class of Organic Photocatalysts for Photopolymerisation Processes and the 3D Printing of Photocurable Resins under Visible Light

Abstract

In the present paper, novel thioxanthone-based compounds were synthesised and evaluated as a component of photoredox catalysts/photoinitiating systems for the free-radical polymerisation (FRP) of acrylates and the ring-opening cationic polymerisation (CP) of epoxy monomers. The performance of the obtained thioxanthones in two- and three-component photoinitiating systems, in combination with amines, iodonium or sulphonium salt, as well as with alkyl halide, for photopolymerisation processes upon exposure to light emitting diodes (LEDs) with a maximum emission of 405 nm and 420 nm, was investigated. The studied compounds act also as one-component free-radical photoinitiators. Fourier transform real-time infrared spectroscopy was used to monitor the kinetics of disappearance of the functional groups of the monomers during photoinitiated polymerisation. Excellent photoinitiating efficiency and high final conversions of functional groups were observed. Moreover, the influence of thioxanthone skeleton substitution on photoinitiating efficiency was discussed. The photochemical mechanism was also investigated through cyclic voltammetry. It was discovered that thioxanthone derivatives can be used as a metal-free photoredox catalyst active for both oxidative and reductive cycles. Furthermore, a photopolymerizable system based on novel thioxanthone derivatives in a stereolithography three-dimensional (3D) printing technology under visible sources of light was used. The effects of photoinitiator type system and monomer type in photoresins during 3D printing processes were explored. The outcome of this research is the development of high-performance visible photosensitive resins with improved photosensitivity obtained thanks to the development of entirely novel photoinitiating systems specifically adapted for this application.