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Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation
High-performance photoinitiators (PIs) are essential for ultraviolet–visible (UV-Vis) light emitting diode (LED) photopolymerization. In this study, a series of coumarin ketoxime esters (COXEs) with electron-donating substituents (tert-butyl, methoxy, dimethylamino and methylthio) were synthesized t...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9655686/ https://www.ncbi.nlm.nih.gov/pubmed/36365582 http://dx.doi.org/10.3390/polym14214588 |
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author | Fan, Shuheng Sun, Xun He, Xianglong Pang, Yulian Xin, Yangyang Ding, Yanhua Zou, Yingquan |
author_facet | Fan, Shuheng Sun, Xun He, Xianglong Pang, Yulian Xin, Yangyang Ding, Yanhua Zou, Yingquan |
author_sort | Fan, Shuheng |
collection | PubMed |
description | High-performance photoinitiators (PIs) are essential for ultraviolet–visible (UV-Vis) light emitting diode (LED) photopolymerization. In this study, a series of coumarin ketoxime esters (COXEs) with electron-donating substituents (tert-butyl, methoxy, dimethylamino and methylthio) were synthesized to study the structure/reactivity/efficiency relationships for substituents for the photoinitiation performance of PIs. The introduction of heteroatom electron-donating substituents leads to a redshift in the COXE absorption of more than 60 nm, which matches the UV-Vis LED emission spectra. The PIs also show acceptable thermal stability via differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The results from real-time Fourier transform infrared (RT-FTIR) measurements indicate that COXEs show an excellent photoinitiation efficiency for free radical polymerization under UV-Vis LED irradiation (365–450 nm); in particular, the conversion efficiency for tri-(propylene glycol) diacrylate (TPGDA) polymerization initiated by COXE-O and COXE-S (4.8 × 10(−5) mol·g(−1)) in 3 s can reach more than 85% under UV-LED irradiation (365, 385 nm). Moreover, the photosensitization of COXEs in the iodonium hexafluorophosphate (Iod-PF(6)) and hexaarylbiimidazole/N-phenylglycine (BCIM/NPG) systems was investigated via RT-FTIR. As a coinitiator, COXEs show excellent performance in dry film photoresist (DFR) photolithography. This excellent performance of COXEs demonstrates great potential for UV-curing and photoresist applications, providing a new idea for the design of PIs. |
format | Online Article Text |
id | pubmed-9655686 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-96556862022-11-15 Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation Fan, Shuheng Sun, Xun He, Xianglong Pang, Yulian Xin, Yangyang Ding, Yanhua Zou, Yingquan Polymers (Basel) Article High-performance photoinitiators (PIs) are essential for ultraviolet–visible (UV-Vis) light emitting diode (LED) photopolymerization. In this study, a series of coumarin ketoxime esters (COXEs) with electron-donating substituents (tert-butyl, methoxy, dimethylamino and methylthio) were synthesized to study the structure/reactivity/efficiency relationships for substituents for the photoinitiation performance of PIs. The introduction of heteroatom electron-donating substituents leads to a redshift in the COXE absorption of more than 60 nm, which matches the UV-Vis LED emission spectra. The PIs also show acceptable thermal stability via differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The results from real-time Fourier transform infrared (RT-FTIR) measurements indicate that COXEs show an excellent photoinitiation efficiency for free radical polymerization under UV-Vis LED irradiation (365–450 nm); in particular, the conversion efficiency for tri-(propylene glycol) diacrylate (TPGDA) polymerization initiated by COXE-O and COXE-S (4.8 × 10(−5) mol·g(−1)) in 3 s can reach more than 85% under UV-LED irradiation (365, 385 nm). Moreover, the photosensitization of COXEs in the iodonium hexafluorophosphate (Iod-PF(6)) and hexaarylbiimidazole/N-phenylglycine (BCIM/NPG) systems was investigated via RT-FTIR. As a coinitiator, COXEs show excellent performance in dry film photoresist (DFR) photolithography. This excellent performance of COXEs demonstrates great potential for UV-curing and photoresist applications, providing a new idea for the design of PIs. MDPI 2022-10-28 /pmc/articles/PMC9655686/ /pubmed/36365582 http://dx.doi.org/10.3390/polym14214588 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Fan, Shuheng Sun, Xun He, Xianglong Pang, Yulian Xin, Yangyang Ding, Yanhua Zou, Yingquan Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title | Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title_full | Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title_fullStr | Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title_full_unstemmed | Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title_short | Coumarin Ketoxime Ester with Electron-Donating Substituents as Photoinitiators and Photosensitizers for Photopolymerization upon UV-Vis LED Irradiation |
title_sort | coumarin ketoxime ester with electron-donating substituents as photoinitiators and photosensitizers for photopolymerization upon uv-vis led irradiation |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9655686/ https://www.ncbi.nlm.nih.gov/pubmed/36365582 http://dx.doi.org/10.3390/polym14214588 |
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