Ketone derivatives as photoinitiators for both radical and cationic photopolymerizations under visible LED and application in 3D printing

Abstract

Six ketones (abbreviated as ketones 1–6) varying by the substitution pattern of the central cyclohexanones and the choice of the peripheral groups (thiophene or furane) were synthesized and proposed as unprecedented visible light sensitive photoinitiators, in combination with an amine and an iodonium salt, for the free radical polymerization of acrylates upon LED irradiation at 405 nm. For the photopolymerization of acrylates carried out as thin samples in laminate, all these ketones showed high photoinitiating abilities. Conversely, when tested as photoinitiators for thick samples, compared to the other 4 ketones, ketone 3 and ketone 5 both based onpiperidin-4-one as the central core and comprising furanes as peripheral groups proved to be the most efficient photoinitiators. Notably, the highest final polymerization conversion of Ebecryl 40, a tetrafunctional polyether acrylate, could be obtained using these two photoinitiators. The high photoreactivity of ketone 3 was highlighted by the steady state photolysis experiments. Meanwhile, ketone 3 could also promote the cationic polymerization of epoxides upon LED irradiation at 405 nm, in the presence of an iodonium salt. Interestingly, some 3D patterns could also be fabricated by free radical polymerization of Ebecryl 40 while using the ketone 3-based photoinitiating system.