ABSTRACT
The efficiency of the photopolymerization technology significantly decreases when the color of materials blackens, which is contributed by the limitations of light penetration. Herein, we demonstrate rapid generation of black 3D objects up to the centimeter level in size based on melanin using near-infrared (NIR) photochemistry. Melanin, of a low absorption coefficient in the NIR range, allows thorough penetration of the 980 nm light to induce emission from upconversion nanoparticles (UCNPs) for initiating UCNP-assisted photopolymerization (UCAP). A model that describes light-attenuation gradients and dose-dependent kinetics in UCAP-guided NIR photochemistry is developed. Notably, the established model for the UCAP concept provides sufficient vertical light penetration to form scale-predictable black materials and instructs 3D printing applications. The critical control parameters were evaluated, and it was shown that complex macroscale black objects can be processed within dozens of minutes. The modeling methodologies integrated with rich functional fillers will further extend the versatility of UCAP technology in device design and manufacturing.
ABSTRACT
Efficient photopolymerization activated by nonharmful near-infrared (NIR) light is important for various biological applications. Here we propose a NIR light free-radical photoinitiator (PI) fabricated by incorporating oxime-ester coumarin functionality on the surface of upconversion nanoparticles (UCNPs). The coumarin groups of PI absorb the light emitted from the UCNP core, whereas the oxime ester groups undergo cleavage to form radicals. Upon irradiation at 980 nm, the mobile radicals, formed in a manner similar to that of dandelion seed release, initiate both free-radical and thiol-ene photopolymerizations. The superior efficiency of dandelion-like PIs assisted photopolymerizations can be attributed to the reduction of energy loss and increased local PI concentration due to Förster resonance energy transfer process and confinement effect, respectively. Moreover, the proposed PI system can initiate polymerization under low-power NIR laser and reduces the thermal side effects. The possibility of its potential use in deep curing applications was also demonstrated.
ABSTRACT
Developing efficient unimolecular visible light-emitting diode (LED) light photoinitiators (PIs) with photobleaching capability, which are essential for various biomedical applications and photopolymerization of thick materials, remains a great challenge. Herein, we demonstrate the synthesis of a series of novel PIs, containing coumarin moieties as chromophores and oxime ester groups as initiation functionalities and explore their structure-activity relationship. The investigated oxime esters can effectively induce acrylates and thiol-based click photopolymerization under 450 nm visible LED light irradiation. The initiator O-3 exhibited excellent photobleaching capability and enabled photopolymerization of thick materials (â¼4.8 mm). The efficient unimolecular photobleachable initiators show great potential in dental materials and 3D printings.
