One-component cationic photoinitiators based on coumarin scaffold iodonium salts as highly sensitive photoacid generators for 3D printing IPN photopolymers under visible LED sources,Polymer Chemistry

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One-component cationic photoinitiators based on coumarin scaffold iodonium salts as highly sensitive photoacid generators for 3D printing IPN photopolymers under visible LED sources
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-07-20 , DOI: 10.1039/d0py00677g
Monika Topa _{1,

2,

3,

4} , Emilia Hola _{1,

2,

3,

4} , Mariusz Galek _{4,

5,

6} , Filip Petko _{4,

5,

6} , Maciej Pilch _{1,

2,

3,

4} , Roman Popielarz _{1,

2,

3,

4} , Fabrice Morlet-Savary _{7,

8,

9,

10} , Bernadette Graff _{7,

8,

9,

10} , Jacques Lalevée _{7,

8,

9,

10} , Joanna Ortyl _{1,

2,

3,

4,

5}

Affiliation

This paper describes the development of four new coumarin chromophore-based iodonium salts as efficient one-component cationic photoinitiators upon light-emitting diode (LED) irradiation with maximum emission under the UV-A region at 365 nm and under visible light at 405 nm. They initiate the cationic polymerization of epoxides, oxiranes, and glycidyl and vinyl ethers upon exposure to a UV-A LED and a visible LED. Even small structural variations of iodonium cations carrying different types of aryl moieties and the same coumarin chromophore can affect their properties. The properties and reactivities of a series of iodonium salts containing various cations were compared in the context of different photopolymerization processes. The relationship between the molecular structure of the coumarin-based iodonium salts and their reaction mechanism during the different photopolymerization processes was also investigated. Based on the results from real-time FT-IR spectroscopy and photo-differential scanning calorimetric experiments, it was concluded that the structures of the cations strongly affect the photopolymerization reaction rate and the final conversion of the monomer. Photopolymerization kinetic data show that kinetic parameters are affected by the presence of substituents in the phenyl ring of coumarin scaffold based iodonium salts. Indeed, the photoinitiating process remains highly efficient during the ring opening cationic photopolymerization of epoxides, oxiranes and glycidyl monomers, as well as during the extremely fast photopolymerization of vinyl monomers. The photochemical mechanisms of these new salts are investigated for the first time through electron spin resonance, laser flash photolysis and steady-state photolysis experiments and the cyclic voltammetry technique. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. In conclusion, we have shown that new cationic iodonium photoinitiators are interesting from an industrial point of view because they can be used as efficient initiators in constructing IPN polymeric materials in the 3D printing area. These insights can encourage the utilisation of new coumarin based iodonium salts as useful photoinitiators in polymer coating synthesis, as well as for 3D printing processes.

中文翻译：

基于香豆素骨架碘鎓盐的单组分阳离子光引发剂，作为在可见LED光源下3D打印IPN光聚合物的高灵敏度光酸产生剂

本文描述了四种新的基于香豆素发色团的碘鎓盐的开发，这些盐是在发光二极管（LED）照射下在365 nm的UV-A区和405 nm的可见光下具有最大发射量的高效单组分阳离子光引发剂。当暴露于UV-A LED和可见LED时，它们会引发环氧化物，环氧乙烷和缩水甘油基和乙烯基醚的阳离子聚合。带有不同类型芳基部分和相同香豆素发色团的碘鎓阳离子即使很小的结构变化也可能影响其性能。在不同的光聚合过程中，比较了一系列含有各种阳离子的碘鎓盐的性质和反应活性。还研究了香豆素基碘鎓盐的分子结构与其在不同光聚合过程中的反应机理之间的关系。根据实时FT-IR光谱和光差扫描量热实验的结果，可以得出结论，阳离子的结构强烈影响光聚合反应速率和单体的最终转化率。光聚合动力学数据表明，动力学参数受基于香豆素支架的碘鎓盐的苯环中取代基的存在的影响。实际上，在环氧化物，环氧乙烷和缩水甘油基单体的开环阳离子光聚合过程中以及在乙烯基单体的极快光聚合过程中，光引发过程仍然非常有效。通过电子自旋共振，激光闪光光解和稳态光解实验以及循环伏安技术，首次研究了这些新盐的光化学机理。分子轨道计算也可用于阐明引发机理。总之，我们已经表明，从工业角度来看，新型阳离子碘鎓光引发剂很有趣，因为它们可以用作在3D打印领域中构建IPN聚合物材料的有效引发剂。这些见解可以鼓励在聚合物涂层合成以及3D打印过程中使用新的香豆素基碘鎓盐作为有用的光引发剂。激光闪光光解和稳态光解实验以及循环伏安技术。分子轨道计算也可用于阐明引发机理。总之，我们已经表明，从工业角度来看，新型阳离子碘鎓光引发剂很有趣，因为它们可以用作在3D打印领域中构建IPN聚合物材料的有效引发剂。这些见解可以鼓励在聚合物涂层合成以及3D打印过程中使用新的香豆素基碘鎓盐作为有用的光引发剂。激光闪光光解和稳态光解实验以及循环伏安法。分子轨道计算也可用于阐明引发机理。总之，我们已经表明，从工业角度来看，新型阳离子碘鎓光引发剂很有趣，因为它们可以用作在3D打印领域中构建IPN聚合物材料的有效引发剂。这些见解可以鼓励在聚合物涂层合成以及3D打印过程中使用新的香豆素基碘鎓盐作为有用的光引发剂。我们已经表明，从工业角度来看，新型阳离子碘鎓光引发剂很有趣，因为它们可以用作在3D打印领域中构建IPN聚合物材料的有效引发剂。这些见解可以鼓励在聚合物涂层合成以及3D打印过程中使用新的香豆素基碘鎓盐作为有用的光引发剂。我们已经表明，从工业角度来看，新型阳离子碘鎓光引发剂很有趣，因为它们可以用作在3D打印领域中构建IPN聚合物材料的有效引发剂。这些见解可以鼓励在聚合物涂层合成以及3D打印过程中使用新的香豆素基碘鎓盐作为有用的光引发剂。

更新日期：2020-08-18

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