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Silyl Glyoxylates as a New Class of High Performance Photoinitiators: Blue LED Induced Polymerization of Methacrylates in Thin and Thick Films
Macromolecules ( IF 5.1 ) Pub Date : 2017-08-31 00:00:00 , DOI: 10.1021/acs.macromol.7b01370 Mariem Bouzrati-Zerelli 1 , Julie Kirschner 1 , Christoph P. Fik 2 , Maximilian Maier 2 , Celine Dietlin 1 , Fabrice Morlet-Savary 1 , Jean Pierre Fouassier 1 , Jean-Michel Becht 1 , Joachim E. Klee 2 , Jacques Lalevée 1
Macromolecules ( IF 5.1 ) Pub Date : 2017-08-31 00:00:00 , DOI: 10.1021/acs.macromol.7b01370 Mariem Bouzrati-Zerelli 1 , Julie Kirschner 1 , Christoph P. Fik 2 , Maximilian Maier 2 , Celine Dietlin 1 , Fabrice Morlet-Savary 1 , Jean Pierre Fouassier 1 , Jean-Michel Becht 1 , Joachim E. Klee 2 , Jacques Lalevée 1
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Silyl glyoxylates are proposed here as a new class of high performance type I photoinitiators for free radical polymerization under air or in laminate (e.g., (meth)acrylates) upon exposure to different near-UV (at 395 nm; at 405 nm) and blue (at 477 nm) LEDs. The new proposed photoinitiators can also be used in the presence of additives that can enhance their initiating ability: an iodonium salt and an amine or a phosphine. The silyl glyoxylate-based photoinitiating systems exhibit excellent polymerization performances upon blue LED light (at 477 nm) with exceptional bleaching properties compared to camphorquinone (CQ)-based systems. This can be highly worthwhile for the preparation of colorless polymers upon visible light. Real-time Fourier transform infrared spectroscopy (RT-FTIR) experiments are used to monitor the polymerization profiles. The involved chemical mechanisms are investigated by fluorescence, laser flash photolysis, electron spin resonance (ESR), and steady state photolysis experiments. Molecular orbital calculations are also carried out. The overall excited state processes and the chemical mechanisms involved in the initiation step are detailed.
中文翻译：
乙醛酸甲硅烷酯作为一类新型的高性能光引发剂：蓝光LED诱导甲基丙烯酸酯在薄膜和厚膜中的聚合
在此，乙醛酸甲硅烷基酯是一类新型的高性能I型光引发剂，用于在空气中或在层压板（例如（甲基）丙烯酸酯）中暴露于不同的近紫外光（在395 nm；在405 nm时）和蓝光下进行自由基聚合。 （在477 nm处）LED。新提出的光引发剂还可以在能增强其引发能力的添加剂的存在下使用：碘鎓盐和胺或膦。与基于樟脑醌（CQ）的系统相比，基于甲硅烷基乙二酸酯的光引发体系在蓝色LED光（在477 nm）下表现出出色的聚合性能，具有出色的漂白性能。这对于在可见光下制备无色聚合物非常有价值。实时傅立叶变换红外光谱（RT-FTIR）实验用于监控聚合曲线。通过荧光，激光闪光光解，电子自旋共振（ESR）和稳态光解实验研究了涉及的化学机理。还进行了分子轨道计算。详细介绍了整个激发态过程和引发步骤涉及的化学机理。
更新日期：2017-08-31
中文翻译：
乙醛酸甲硅烷酯作为一类新型的高性能光引发剂：蓝光LED诱导甲基丙烯酸酯在薄膜和厚膜中的聚合
在此，乙醛酸甲硅烷基酯是一类新型的高性能I型光引发剂，用于在空气中或在层压板（例如（甲基）丙烯酸酯）中暴露于不同的近紫外光（在395 nm；在405 nm时）和蓝光下进行自由基聚合。 （在477 nm处）LED。新提出的光引发剂还可以在能增强其引发能力的添加剂的存在下使用：碘鎓盐和胺或膦。与基于樟脑醌（CQ）的系统相比，基于甲硅烷基乙二酸酯的光引发体系在蓝色LED光（在477 nm）下表现出出色的聚合性能，具有出色的漂白性能。这对于在可见光下制备无色聚合物非常有价值。实时傅立叶变换红外光谱（RT-FTIR）实验用于监控聚合曲线。通过荧光，激光闪光光解，电子自旋共振（ESR）和稳态光解实验研究了涉及的化学机理。还进行了分子轨道计算。详细介绍了整个激发态过程和引发步骤涉及的化学机理。
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