Three new photobleachable D-π-A-π-A′ type bis-chalcones-based oxime ester dyes (TAs) for radical visible photopolymerization were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR, and HR-MS. The mechanism for the radicals’ generation was proposed according to the analysis of electron paramagnetic resonance (EPR) and steady state photolysis experiments. The production of oxygen alkyl radicals from the ketone carbonyl group and as well as vinyl radicals through the homolysis of N–O bond in oxime ester demonstrates that dyes TAs are the integration of type I and type II photoinitiators. The photopolymerization experiment showed that 1, 6-hexanediol diacrylate (HDDA) as the monomer can be effectively initiated for photopolymerization by TAs under LED@455 nm exposure. In addition, the cured films initiated by TAs have low extraction rates. Particularly, TA2 with benzylidene cyclopentanone oxime ester exhibits the best double bond conversion efficiency and photobleachable characteristic. The colorless bulk acrylate materials as deep as 32 mm thickness can be obtained through the photopolymerization initiated by TA2. Investigation also shows that oxime ester dyes provides an important source for obtaining radicals which can be produced by the homolysis of N–O bond. Thus, the research consequences open up a new research direction for the structural design of dyes and widen their applications in the fields of deep photocuring.
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