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Substituent Effects on Photoinitiation Ability of Monoaminoanthraquinonea??Based Photoinitiating Systems for Free Radical Photopolymerization under LEDs
摘要： Three monoamino-substituted anthraquinone derivatives (AAQs), that is, 1-aminoanthraquinone (AAQ), 1-(methylamino)anthraquinone (MAAQ), and 1-(benzamido)anthraquinone (BAAQ), incorporated with various additives [e.g., triethanolamine (TEAOH) and phenacyl bromide (PhC(═O)CH2Br)] are investigated for their roles as photoinitiating systems of free radical photopolymerization of (meth)acrylate monomers upon the exposure to UV to green LEDs. The AAQs-based photoinitiating systems, AAQ/TEAOH/PhC(═O)CH2Br and BAAQ/TEAOH/PhC(═O)CH2Br photoinitiators exhibit the highest efficiency for the free radical photopolymerization of DPGDA under the irradiation of blue LED and UV LED, respectively, which is consistent with the extent of overlap between their absorption spectra and the emission spectra of the LEDs. AAQ/TEAOH/PhC(═O)CH2Br photoinitiator can also initiate the free radical photopolymerization of different (meth)acrylate monomers, with an efficiency dependent on the chemical structures of these monomers.
关键词： LEDs,free radical photopolymerization,aminoanthraquinone,photo initiators
更新于2025-09-23 15:21:01
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Carbon Dots as Promising Green Photocatalyst for Free Radical and ATRP-Based Radical?Photopolymerization with Blue LEDs
摘要： This contribution reports for the first time about the use of carbon dots (CDs) as sensitizer to initiate and activate free radical and controlled radical polymerization based on an ATRP protocol with blue LEDs, respectively. Consideration of diverse heteroatom-doped CDs indicated well-functioning of N-doped CDs as effective photocatalyst and photosensitizer in combination with LEDs emitting either at 405 nm or 470 nm. Initiation of free radical polymerization occurred by combining the CDs with an iodonium or sulfonium salt in tri(propylene glycol) diacrylate. Polymerization of methyl methacrylate (MMA) by photo-induced ATRP was achieved with CDs and ethyl a-bromophenylacetate using Cu(II) as catalyst in the ppm range. The polymers obtained showed temporal control, narrower dispersity ?1.5, and chain-end fidelity. The first order obtained from kinetic slope and ON/OFF experiments additionally approved constant concentration of polymer radicals. No remarkable cytotoxic activity was observed of the CDs underlining their biocompatibility.
关键词： blue LED,free radical photopolymerization,photo-ATRP,cytotoxicity,Carbon dot
更新于2025-09-12 10:27:22
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Carbon Dots as Promising Green Photocatalyst for Free Radical and ATRP‐Based Radical?Photopolymerization with Blue LEDs
摘要： This contribution reports for the first time about the use of carbon dots (CDs) as sensitizer to initiate and activate free radical and controlled radical polymerization based on an ATRP protocol with blue LEDs, respectively. Consideration of diverse heteroatom-doped CDs indicated well-functioning of N-doped CDs as effective photocatalyst and photosensitizer in combination with LEDs emitting either at 405 nm or 470 nm. Initiation of free radical polymerization occurred by combining the CDs with an iodonium or sulfonium salt in tri(propylene glycol) diacrylate. Polymerization of methyl methacrylate (MMA) by photo-induced ATRP was achieved with CDs and ethyl a-bromophenylacetate using Cu(II) as catalyst in the ppm range. The polymers obtained showed temporal control, narrower dispersity ?1.5, and chain-end fidelity. The first order obtained from kinetic slope and ON/OFF experiments additionally approved constant concentration of polymer radicals. No remarkable cytotoxic activity was observed of the CDs underlining their biocompatibility.
关键词： blue LED,free radical photopolymerization,photo-ATRP,cytotoxicity,Carbon dot
更新于2025-09-12 10:27:22
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Disubstituted Aminoanthraquinone-Based Photoinitiators for Free Radical Polymerization and Fast 3D Printing under Visible Light
摘要： The development of highly efficient and rapid photoinitiating systems for free radical photopolymerization under the irradiation of visible light has attracted increasing attention due to their widespread potential applications in, for example, 3D printing or dental polymers. Unfortunately, currently available visible-light-sensitive photoinitiators are not efficient enough for 3D printing applications suffering from low printing speeds. Here we describe a series of photoinitiating systems consisting of disubstituted amino-anthraquinone derivatives (i.e., 1-amino-4-hydroxy-anthraquinone, 1,4-diaminoanthraquinone, and 1,5-diamino-anthraquinone) and various additives (e.g., tertiary amine and phenacyl bromide) toward the free radical photopolymerization of various acrylate monomers (such as commercial 3D resin) under the irradiation of blue to red LEDs. It is shown that the type and position of substituents of the aminoanthraquinone derivative can significantly affect its photoinitiation properties. The most efficient disubstituted aminoanthraquinone derivative-based photoinitiating system was selected and used for the 3D printing of a commercial 3D resin in a 3D printer with polychromatic visible light as the irradiation source. It is shown that its printing speed was dramatically enhanced compared to a commercial photoinitiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO).
关键词： aminoanthraquinone derivatives,free radical photopolymerization,photoinitiating systems,visible light,3D printing
更新于2025-09-09 09:28:46