Polydiacetylene (PDA) materials are appealing and gaining increasing research interest due to their outstanding chromatic transition and fluorescence enhancement effects upon exposure to various environmental stimuli. However, despite the photomask method, there are very few reports about the spatial controllable photopolymerization and subsequent 3D printing of PDA until now. Herein, for the first time, we reported the preparation of PDA photocomposite materials based on polyacrylate through the strategy of dual-wavelength polymerization and orthogonal chemistry. First, diacetylene (DA) monomers were homogeneously dispersed in acrylate resin. Then a violet light emitting diode (LED) (or laser diode) was used for the free radical polymerization of polyacrylate. Finally, UV irradiation was utilized to induce the 1,4-topopolymerization of PDA, which could show a successive blue to purple to red color transition in response to the gradient increment of temperature. Interestingly, instead of photomasks, we applied a 3D printing approach directly to this composite material and fabricated some macroscopic stereo patterns, which also illustrated thermochromic properties. This novel kind of functional photocomposite material would demonstrate a huge application prospect in many potential fields, including colorimetric sensing, information encryption, anticounterfeiting, and so on.

Herein, thirteen ketone derivatives composed of different cyclohexanone cores and peripheral moieties are designed, among which 10 ketones have never been synthesized before. These ketones are proposed as high‐performance photoinitiators for both free radical polymerizations and cationic polymerizations under soft conditions (visible LED@405 nm irradiation at room temperature). In combination with an amine and an iodonium salt (Iod), these ketones could be used in three−component photoinitiating systems to initiate the free radical polymerization of acrylates with distinct final conversions, among which the ketone−1/amine/Iod combination proved to be the most efficient one. Besides, the ketone−1/Iod two−component system also showed a remarkable photoinitiation ability for the cationic polymerization of epoxides. The photochemical sensitivity of ketone−1 in the presence of an amine and an iodonium salt was systematically investigated by steady state photolysis and excited state fluorescence quenching characterizations, respectively. Interestingly, macroscopic 3D patterns with excellent spatial resolution could be generated using the ketone−1/amine/Iod photoinitiating system for the free radical polymerization of acrylates. This high performance is also found useful to overcome the light penetration issue for the access to filled samples (silica) and the preparation of composites.

Photopolymerization of acrylates under mild conditions is promising not only for academic research, but also for industrialization applications. However, it still remains a huge challenge to develop effective photoinitiators or...

Five ketone derivatives (ketone-1~ketone-5) never synthesized in the literature and containing the same peripheral 1,3-bis(allyloxy)benzene substituting group but different central cyclohexanone cores were designed and proposed as highperformance photoinitiators for the free radical polymerization of acrylates under mild conditions. In combination with an amine and an iodonium salt (Iod), these ketones could initiate the photopolymerization of di(trimethylolpropane) tetraacrylate (TA), a tetrafunctional acrylates monomer, upon visible LED irradiation at room temperature in both thick films (1.4 mm) and thin films (25 μm) conditions. The distinct photopolymerization profiles of acrylates were studied by real time Fourier transform infrared spectroscopy, which indicated that the ketone-2/amine/Iod system could induce the highest final conversion of acrylates in thick films condition, while ketone-5/amine/Iod system could induce the highest final conversion of acrylates in thin films condition. Photoreactivity of ketone-2 and ketone-5 was systematically investigated by steady state photolysis and fluorescence quenching experiments in the presence of an amine and an iodonium salt, respectively. Moreover, eminent migration stability of ketones in photocured TA was observed. Finally, the ketone-2 and ketone-5-based three-component photoinitiating systems were applied for the laser writing experiments of TA, and macroscopically tridimensional patterns were fabricated with an excellent spatial resolution.