The following article introduces technologies that build three dimensional (3D) objects by adding layer-upon-layer of material, also called additive manufacturing technologies. Furthermore, most important features supporting the conscious choice of 3D printing methods for applications in micro and nanomanufacturing are covered. The micromanufacturing method covers photopolymerization-based methods such as stereolithography (SLA), digital light processing (DLP), the liquid crystal display–DLP coupled method, two-photon polymerization (TPP), and inkjet-based methods. Functional photocurable materials, with magnetic, conductive, or specific optical applications in the 3D printing processes are also reviewed.

In this work, we presented a new bimolecular photoinitiating system based on 2-amino-4,6-diphenylpyridine-3-carbonitrile derivatives as visible photosensitizers of diphenyliodonium salt. Real-time FTIR and photo-DSC photopolymerization experiments with a cycloaliphatic epoxide and vinyl monomers showed surprisingly good reactivity of the bimolecular photoinitiating systems under UV-A, as well as under visible light sources. Steady-state photolysis, fluorescence experiments, theoretical calculations of molecular orbitals, and electrochemical analysis demonstrated photo-redox behavior as well as the ability to form initiating species via photo-reduction or photo-oxidation pathways, respectively. Therefore, the 2-amino-4,6-diphenylpyridine-3-carbonitrile derivatives were also investigated as a type II free-radical photoinitiator with amine. It was confirmed that the 2-amino-4,6-diphenylpyridine-3-carbonitrile derivatives, in combination with different types of additives, e.g., amine as a co-initiator or the presence of onium salt, can act as bimolecular photoinitiating systems for cationic, free-radical, and thiol-ene photopolymerization processes by hydrogen abstraction and/or electron transfer reactions stimulated by either near-UV or visible light irradiation. Finally, the 2-amino-4,6-diphenylpyridine-3-carbonitrile derivatives were selected for 3D printing rapid prototyping experiments. Test objects were successfully printed using purely cationic photosensitive resin, created on a 3D printer with a visible LED light source.

1-Amino-4-methyl-naphthalene-2-carbonitrile derivatives are proposed for the role of photosensitizers of iodonium salt during the photopolymerization processes upon near UV-A and visible ranges.

The performance of a series of 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives as fluorescent molecular sensors for monitoring photopolymerization processes of different monomers by the Fluorescence Probe Technique (FPT) was studied. It has been shown that the new derivatives are characterized by much higher sensitivity than the commercially available 7-diethylamino-4-methylcoumarin (Coumarin 1) and trans-2-(2′,5′-dimethoxyphenyl)ethenyl-2,3,4, 5,6-pentafluorobenzene (25ST) probes. It has been discovered that the 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives accelerate the cationic photopolymerization process initiated with diphenyliodonium photoinitiators at the wavelength where the photoinitiator alone does not work. They are particularly efficient for the photoinitiation of cationic photopolymerization of an epoxide and vinyl monomers. Consequently, the application of the 2-amino-4,6-diphenyl-pyridine-3-carbonitrile derivatives in a dual role: (a) as fluorescent sensors for monitoring the free-radical, thiol-ene and cationic polymerization progress, and (b) as long-wavelength co-initiators for diphenyliodonium salts initiators, is proposed.

Herein, mono-and disubstituted thioxanthones have been synthesized and introduced as photosensitizers of iodonium salt for cationic and free-radical photopolymerization of epoxy and an acrylate monomer, respectively. Photoinitiation activity of these molecules was verified during photopolymerization processes performed upon exposure to visible LEDs of 420, 455, and 470 nm. The kinetics of the photopolymerization processes was followed using FT-IR spectroscopy. Moreover, the developed compounds were proposed as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization (ATRP). Thioxanthone derivatives (with alkyl halide) efficiently activate the ATRP of methyl methacrylate using a visible LED as an irradiation source. The formed polymers in the ATRP process were characterized by SEC. Apart from studying the photopolymerization processes with the participation of obtained thioxanthones, absorption, fluorescence, as well as electrochemical properties of thioxanthone derivatives were investigated. Furthermore, the performance of studied compounds in 3D printing applications was also examined. The most important result of this study is the design and possible application of photosensitizers/photocatalysts for photopolymerization processes.