香豆素并咔唑基草酸酯类UV-LED可激发光引发剂的合成与研究

doi:10.7517/issn.1674-0475.190613

摘要/Abstract

摘要： 本文设计并制备了以香豆素并咔唑为共轭结构的草酸酯类光引发剂（2-OAME和4-OAME），分子中大π-共轭结构的引入实现了分子在LED光域的良好吸收。通过核磁共振谱对目标产物进行了结构验证，通过紫外-可见吸收光谱、荧光光谱和理论计算对分子的光化学及光物理性质进行了表征。研究表明，两个光引发剂在近紫外-可见光范围内均表现出优异的光吸收性质，并且在LED光源激发下具有良好的光引发聚合能力，4-OAME分子较2-OAME在同样的条件下表现出更好的光引发聚合能力，在近紫外-可见LED光聚合领域具有较大的应用潜力。

关键词: 香豆素并咔唑, 草酸酯, 光引发剂, UV-LED

Abstract: In this paper, two coumarin-carbazole based oxalate photoinitiators (2-OAME and 4-OAME) were designed and synthesized. By introducing the coumarin into carbazole group, the π-conjugated structure is enlarged, resulting to the good absorption properties in UV-visible light range. The photophysical and photochemical properties were characterized by UV-Vis absorption spectra and FT-RTIR. The two photoinitiators exhibit excellent light absorption properties in the near UV-Vis range and have good photoinitiated polymerization ability under excitation by the LED light source. The 4-OAME molecule exhibited better photoinitiated polymerization ability under the same conditions than 2-OAME. The two photoinitiators have great application potential in the field of near-ultraviolet-visible LED photopolymerization.

Key words: coumarin-carbazole, oxalate, photoinitiator, UV-LED

周茹春, 柳宜卓, 陈世雄, 王伟杰, 陈思琦, 金明. 香豆素并咔唑基草酸酯类UV-LED可激发光引发剂的合成与研究[J]. 影像科学与光化学, 2019, 37(5): 402-414.

ZHOU Ruchun, LIU Yizhuo, CHEN Shixiong, WANG Weijie, CHEN Siqi, JIN Ming. The Synthesis and Properties of UV-LED Sensitive Coumarin-carbazole-based Oxalate Photoinitiators[J]. Imaging Science and Photochemistry, 2019, 37(5): 402-414.

参考文献

[1] Fouassier J P, Lalevee J. Photoinitiator for Polymer Synthesis-Scope, Reactivity, and Efficiency[M]. Wiley-VCH Berlag GmbH & Co. KGaA:Weinheim, 2012.
[2] Dietlin C, Schweizer S, Xiao P, Zhang J, Morlet-Savary F, Graff B, Fouassier J P, Lalevee J. Photopolymerization upon LEDs:new photoinitiating systems and strategies[J]. Polymer Chemistry, 2015, 6(21):3895-3912.
[3] Xia R J, Malval J P, Jin M, Spangenberg A, Wan D C, Pu H T, Vergote T, Morlet-Savary F, Chaumeil H, Baldeck P, Poizat O, Soppera O. Enhancement of acid photogeneration through a para-to-meta substitution strategy in a sulfonium-based alkoxystilbene designed for two-photon polyme-rization[J]. Chemistry of Materials, 2012, 24(2):237-244.
[4] Jin M, Xie J, Malval J P, Spangenberg A, Soppera O, Versace D-L, Leclerc T, Pan H, Wan D, Pu H, Baldeck P, Poizat O, Knopf S. Two-photon lithography in visible and NIR ranges using multibranched-based sensitizers for efficient acid generation[J]. Journal of Materials Chemistry C, 2014, 2(35):7201-7215.
[5] Wu X Y, Jin M, Xie J C, Malval J P, Wan D C. One/two-photon cationic polymerization in visible and near infrared ranges using two-branched sulfonium salts as efficient photoacid generators[J]. Dyes and Pigments, 2016, 133:363-371.
[6] Wu X, Jin M, Xie J, Malval J P, Wan D. Molecular engineering of UV/Vis light-emitting diode (LED)-sensitive donor——acceptor-type sulfonium salt photoacid generators:design, synthesis, and study of photochemical and photophysical properties[J]. Chemistry-A European Journal, 2017, 23(62):15783-15789.
[7] Pan H, Chen S, Jin M, Malval J P, Wan D, Morlet-Savary F. A substituent para-to-ortho positioning effect drives the photoreactivity of a dibenzothiophene-based oxalate series used as LED-excitable free radical photoinitiators[J]. Polymer Chemistry, 2019, 10(13):1599-1609.
[8] Cordon C, Miller C. UV-LED:Presented by RadTech-The Association for UV & EB Technology[M]. RadTech International:Bethesda, MD, 2013.
[9] Xiao P, Zhang J, Dumur F, Tehfe M A, Morlet-Savary F, Graff B, Gigmes D, Fouassier J P, Lalevee J. Visible light sensitive photoinitiating systems:recent progress in cationic and radical photopolymerization reactions under soft conditions[J]. Progress in Polymer Science, 2015, 41:32-66.
[10] Xiao P, Dumur F, Graff B, Gigmes D, Fouassier J P, Lalevee J. Variations on the benzophenone skeleton:novel nigh performance blue light sensitive photoinitiating systems[J]. Macromolecules, 2013, 46(19):7661-7667.
[11] Xiao P, Dumur F, Graff B, Morlet-Savary F, Gigmes D, Fouassier J P, Lalevee J. Design of high performance photoinitiators at 385-405 nm:search around the naphthalene scaffold[J]. Macromolecules, 2014, 47(3):973-978.
[12] Xiao P, Zhang J, Dumur F, Tehfe M A, Morlet-Savary F, Graff B, Gigmes D, Fouassier J P, Lalevée J. Visible light sensitive photoinitiating systems:recent progress in catio-nic and radical photopolymerization reactions under soft conditions[J]. Progress in Polymer Science, 2015, 41:32-66.
[13] Tian Y P, Zhang M L, Yu X Q, Xu G B, Ren Y, Yang J X, Wu J Y, Zhang X J, Tao X T, Zhang S Y, Jiang M H. Two novel two-photon polymerization initiators with extensive application prospects[J]. Chemical Physics Letters, 2004, 388(4/6):325-329.
[14] Al Mousawi A, Dumur F, Garra P, Toufaily J, Hamieh T, Graff B, Gigmes D, Fouassier J P, Lalevee J. Carba-zole scaffold based photoinitiator/photoredox catalysts:toward new high performance photoinitiating systems and application in LED projector 3D printing resins[J]. Macromolecules, 2017, 50(7):2747-2758.
[15] Yilmaz G, Tuzun A, Yagci Y. Thioxanthone-carbazole as a visible light photoinitiator for free radical polymerization[J]. Journal of Polymer Science Part a-Polymer Chemistry, 2010, 48(22):5120-5125.
[16] Nazir R, Danilevicius P, Ciuciu A I, Chatzinikolaidou M, Gray D, Flamigni L, Farsari M, Gryko D T. pi-Expanded ketocoumarins as efficient, biocompatible initiators for two-photon-induced polymerization[J]. Chemistry of Mate-rials, 2014, 26(10):3175-3184.
[17] Xu J, Ma G P, Wang K M, Gu J M, Jiang S, Nie J. Synthesis and photopolymerization kinetics of oxime ester photoinitiators[J]. Journal of Applied Polymer Science, 2012, 123(2):725-731.
[18] Liu Z Z, Liu T, Lin Q N, Bao C Y, Zhu L Y. Photoreleasable thiol chemistry for facile and efficient bioconjugation[J]. Chemical Communications, 2014, 50(10):1256-1258.
[19] Zhang X, Xi W, Wang C, Podgorski M, Bowman C N. Visible-light-initiated thiol-michael addition polymerizations with coumarin-based photobase generators:another photoclick reaction strategy[J].ACS Macro Letters, 2016, 5(2):229-233.
[20] Zhou R, Malval J P, Jin M, Spangenberg A, Pan H, Wan D, Morlet-Savary F, Knopf S. A two-photon active chevron-shaped type I photoinitiator designed for 3D stereolithography[J]. Chemical Communications, 2019, 55(44):6233-6236.
[21] Frisch M J. Gaussian 09, Revision B.01.[M]. Gaussian, Inc:Wallingford CT. Wallingford CT2009.
[22] Wu X, Jin M, Malval J P, Wan D, Pu H. Visible light-emitting diode-sensitive thioxanthone derivatives used in versatile photoinitiating systems for photopolymerizations[J]. Journal of Polymer Science Part a-Polymer Chemistry, 2017, 55(24):4037-4045.
[23] Jin M, Wu X Y, Malval J P, Wan D C, Pu H T. Dual roles for promoting monomers to polymers:a conjugated sulfonium salt photoacid generator as photoinitiator and photosensitizer in cationic photopolymerization[J]. Journal of Polymer Science Part a-Polymer Chemistry, 2016, 54(17):2722-2730.
[24] Zhang J, Xiao P, Dumur F, Guo C, Hong W, Li Y, Gigmes D, Graff B, Fouassier J-P, Lalevee J. Polymeric photoinitiators:a new search toward high performance visible light photoinitiating systems[J]. Macromolecular Chemistry and Physics, 2016, 217(19):2145-2153.
[25] Fast D E, Lauer A, Menzel J P, Kelterer A M, Gescheidt G, Barner-Kowollik C. Wavelength-dependent photoche-mistry of oxime ester photoinitiators[J]. Macromolecules, 2017, 50(5):1815-1823.
[26] Allen N S. Photochemistry and photophysics of polymer materials[M]. Wiley:New York, USA, 2010.
[27] Allonas X, Lalevee J, Fouassier J P, Tachi H, Shirai M, Tsunooka M. Triplet state of O-acyloximes studied by time-resolved absorption spectroscopy[J]. Chemistry Letters, 2000(9):1090-1091.
[28] Frick E, Schweigert C, Noble B B, Ernst H A, Lauer A, Liang Y, Voll D, Coote M L, Unterreiner A N, Barner-Kowollik C. Toward a quantitative description of radical photoinitiator structure-reactivity correlations[J]. Macromolecules, 2016, 49(1):80-89.
[29] Jin M, Yu M, Zhang Y, Wan D C, Pu H T. 2,2,2-Trif-luoroacetophenone-based D-pi-A type photoinitiators for radical and cationic photopolymerizations under near-UV and visible LEDs[J]. Journal of Polymer Science Part a-Polymer Chemistry, 2016, 54(13):1945-1954.