Charge Transfer Complexes (CTCs) with Pyridinium Salts: Toward Efficient Dual Photochemical/Thermal Initiators and 3D Printing Applications,Macromolecular Rapid Communications

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Charge Transfer Complexes (CTCs) with Pyridinium Salts: Toward Efficient Dual Photochemical/Thermal Initiators and 3D Printing Applications
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2022-05-08 , DOI: 10.1002/marc.202200314
Qiang Ma _{1,

2,

3} , Loïc Buchon ₁ , Valentin Magné ₄ , Bernadette Graff ₁ , Fabrice Morlet-Savary ₁ , Yangyang Xu ₅ , Mahmoud Benltifa ₆ , Sami Lakhdar ₄ , Jacques Lalevée _{1,

2}

Affiliation

In both organic and polymer synthesis, photochemistry of charge transfer complexes (CTCs) is considered as a powerful approach to expand visible-light-driven radical chemistry reaction. One reports herein on the development of a class of useful CTCs using pyridinium salts as efficient electron acceptors (combined with N, N, 3,5-tetramethylaniline, TMA) to achieve a multiwavelength (375–560 nm) metal-free LED photopolymerization process under mild conditions (open to air, without monomer purification and inhibitor removal). The UV–vis absorption spectra and molecular modeling simultaneously verify its potential blue-green absorbing wavelength range. Also, their good thermal initiation behavior at relatively low temperatures makes it easier to achieve thick samples and/or polymerization in the shadow region in practice. More importantly, with excellent photoinitiating capability, the formulation is successfully applied to direct laser write (DLW) and high-resolution 3D printing, yielding a series of objects with well-defined structures, such as letters, ring, solid squares, and chess pieces. These new pyridinium salt acceptors further extend the applicability to visible photopolymerizable resins and additive-containing formulations for efficient surface and deep curing.

中文翻译：

带有吡啶盐的电荷转移配合物 (CTC)：迈向高效的双光化学/热引发剂和 3D 打印应用

在有机和聚合物合成中，电荷转移复合物 (CTC) 的光化学被认为是扩展可见光驱动的自由基化学反应的有效方法。本文报道了使用吡啶鎓盐作为有效电子受体（与N、N结合）开发一类有用的 CTC, 3,5-四甲基苯胺, TMA) 以在温和条件下实现多波长 (375-560 nm) 无金属 LED 光聚合过程 (对空气开放, 无需单体纯化和抑制剂去除)。紫外-可见吸收光谱和分子模型同时验证了其潜在的蓝绿色吸收波长范围。此外，它们在较低温度下的良好热引发行为使得在实践中更容易在阴影区域实现厚样品和/或聚合。更重要的是，该配方具有优异的光引发能力，成功应用于激光直写（DLW）和高分辨率3D打印，产生一系列结构清晰的物体，如字母、戒指、实心方块和棋子.

更新日期：2022-05-08

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