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Synthesis of carbazole–chalcone bis-oxime esters (CCBOEs) as blue light photoinitiators of polymerization
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-06-05 , DOI: 10.1039/d4py00454j Zheng Liu 1 , Yijun Zhang 2 , Ji Feng 2 , Bin Song 2 , Tong Gao 2 , Céline Dietlin 2 , Fabrice Morlet-Savary 2 , Michael Schmitt 2 , Didier Gigmes 1 , Frédéric Dumur 1 , Jacques Lalevée 2
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-06-05 , DOI: 10.1039/d4py00454j Zheng Liu 1 , Yijun Zhang 2 , Ji Feng 2 , Bin Song 2 , Tong Gao 2 , Céline Dietlin 2 , Fabrice Morlet-Savary 2 , Michael Schmitt 2 , Didier Gigmes 1 , Frédéric Dumur 1 , Jacques Lalevée 2
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In this work, a series of sixteen asymmetrically substituted bis-oxime esters, CCBOEs, bearing different substituents on the oxime ester sides were designed as Type I photoinitiators for photopolymerization experiments done with blue light (405, 450 and 470 nm) under low light intensities (use of LEDs as the light sources). These natural product-inspired compounds showed a strong absorption in the visible range and exhibited a fast cleavage of the oxime ester groups upon photoexcitation, enabling complete oxime ester consumption to be achieved within 2 s. By using the above-mentioned light sources, three CCBOEs (namely CCBOE1, CCBOE4, and CCBOE5) bearing alkyl substituents on the oxime ester sides exhibited high acrylate monomer conversions but also good thermal polymerization abilities, evidencing their dual activation modes. By means of electron spin resonance (ESR) experiments, the formation of free radicals was demonstrated and led to the proposal of a plausible initiation mechanism. The hypothesis of homolytic cleavage of the N–O bond was also supported by the detection of the CO2 absorption peak by Fourier Transform Infrared spectroscopy (FT-IR). The initiating mechanism was also investigated by theoretical calculations, enabling the excited state involved in the cleavage process to be determined. Finally, high-resolution 3D patterns were successfully fabricated using the CCBOE5/TMPTA system through direct laser writing (DLW).
中文翻译：
作为蓝光聚合光引发剂的咔唑-查耳酮双肟酯（CCBOE）的合成
在这项工作中，一系列在肟酯侧带有不同取代基的十六种不对称取代的双肟酯（CCBOE）被设计为I型光引发剂，用于在低光强度下用蓝光（405、450和470 nm）进行光聚合实验（使用LED作为光源）。这些受天然产物启发的化合物在可见光范围内表现出强烈的吸收，并在光激发时表现出肟酯基团的快速裂解，使得肟酯在2秒内完全消耗。通过使用上述光源，肟酯侧带有烷基取代基的三种CCBOE（即CCBOE1、CCBOE4和CCBOE5）表现出较高的丙烯酸酯单体转化率和良好的热聚合能力，证明了它们的双重活化模式。通过电子自旋共振（ESR）实验，证明了自由基的形成，并提出了一种合理的引发机制。 N-O 键均裂的假设也得到了傅里叶变换红外光谱 (FT-IR) 检测到的 CO 2 吸收峰的支持。还通过理论计算研究了引发机制，从而确定了裂解过程中涉及的激发态。最后，使用 CCBOE5/TMPTA 系统通过直接激光写入 (DLW) 成功制造了高分辨率 3D 图案。
更新日期：2024-06-05
中文翻译：
作为蓝光聚合光引发剂的咔唑-查耳酮双肟酯（CCBOE）的合成
在这项工作中，一系列在肟酯侧带有不同取代基的十六种不对称取代的双肟酯（CCBOE）被设计为I型光引发剂，用于在低光强度下用蓝光（405、450和470 nm）进行光聚合实验（使用LED作为光源）。这些受天然产物启发的化合物在可见光范围内表现出强烈的吸收，并在光激发时表现出肟酯基团的快速裂解，使得肟酯在2秒内完全消耗。通过使用上述光源，肟酯侧带有烷基取代基的三种CCBOE（即CCBOE1、CCBOE4和CCBOE5）表现出较高的丙烯酸酯单体转化率和良好的热聚合能力，证明了它们的双重活化模式。通过电子自旋共振（ESR）实验，证明了自由基的形成，并提出了一种合理的引发机制。 N-O 键均裂的假设也得到了傅里叶变换红外光谱 (FT-IR) 检测到的 CO 2 吸收峰的支持。还通过理论计算研究了引发机制，从而确定了裂解过程中涉及的激发态。最后，使用 CCBOE5/TMPTA 系统通过直接激光写入 (DLW) 成功制造了高分辨率 3D 图案。
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