Naphthoquinone derivatives: Naturally derived molecules as blue-light-sensitive photoinitiators of photopolymerization

Abstract

Two naphthoquinone derivatives, i.e. 5-hydroxy-1,4-naphthoquinone (5HNQ) and 2-hydroxy-1,4-naphthoquinone (2HNQ), combined with different additives such as diphenyliodonium hexafluorophosphate (Iod), N-vinylcarbazole (NVK), phenacyl bromide (R-Br), N-phenyl glycine (NPG) and ethyl 4-dimethylamino benzoate (EDB), are investigated as photoinitiating systems (PISs) for free radical polymerization of trimethylolpropane triacrylate (TMPTA) and cationic polymerization of triethyleneglycol divinyl ether (DVE-3). The photopolymerization of the thiol-ene system trimethylolpropane tris(3-mercaptopropionate) (Trithiol)/DVE-3 with 5HNQ or 2HNQ based PISs are also investigated. 5HNQ shows maximum absorption in visible light region (blue light) which thus has the potential to perform under the irradiation of blue LED light. For the free radical polymerization of TMPTA, 5HNQ/Iod/NPG shows the highest photoinitiating ability among all the naphthoquinone derivative-based PISs, while 2HNQ-based systems are inefficient. The addition of Trithiol to TMPTA can significantly increase the double bond conversion of TMPTA during the photopolymerization. For the cationic photopolymerization of DVE-3, 2HNQ/Iod shows the highest photoinitiating ability among all the naphthoquinone derivative-based photoinitiating systems. 5HNQ-based systems also demonstrate good photoinitiation ability for DVE-3, but with slower polymerization rate compared to 2HNQ-based systems. In thiol-ene photopolymerization, 5HNQ PISs shows better photoinitiation ability than 2HNQ PIs systems. The results illustrate that the position of hydroxyl group in 1,4-naphthoquinone molecules plays an important role on photoinitiation ability of naphthoquinone derivatives. Steady state photolysis and electron spin resonance trapping experiments are also carried out to evaluate the relevant photochemical mechanism.