Well-Defined Titanium Complex for Free-Radical and Cationic Photopolymerizations under Visible Light and Photoinduction of Ti-Based Nanoparticles
Well-Defined Titanium Complex for Free-Radical and Cationic Photopolymerizations under Visible Light and Photoinduction of Ti-Based Nanoparticles
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DOI：
10.1021/acs.macromol.8b02719
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发表时间：
2019-05-28
期刊：
影响因子：
5.5
通讯作者：
Versace, Davy-Louis
中科院分区：
文献类型：
--
作者：
Breloy, Louise;Brezova, Vlasta;Versace, Davy-Louis
喹啉衍生的钛络合物（TiQ）在这里被示出为具有显著的光敏特性，当用碘鎓盐（Iod）处理以在可见光照射下引发（i）丙烯酸酯单体在充气/层压条件下的自由基光聚合，（ii）环氧单体在空气下的阳离子光聚合，以及（iii）在涂层内原位形成基于Ti的纳米颗粒（NP）时。TiQ/IOd光引发体系的光化学性质已经通过电子顺磁共振、激光闪光光解和实时傅里叶变换红外光谱来探测，这提供了对可能的自由基/阳离子途径的深入了解。通过明场常规透射电子显微镜和高角度环形暗场扫描透射电子显微镜研究了光合成的Ti基纳米颗粒的微观结构特性。所得纳米复合材料的宏观力学性能表明，在聚丙烯酸酯/聚醚共混物基体中产生的这些钛基纳米颗粒通过增韧基体导致机械阻力的增加。
A quinoline-derived titanium complex (TiQ) is shown here to possess remarkable photosensitizing properties when treated with an iodonium salt (Iod) to initiate, under visible light irradiation, (i) the free-radical photopolymerization of acrylate monomer in aerated/laminate conditions, (ii) the cationic photopolymerization of epoxy monomer under air, and (iii) the in situ formation of Ti-based nanoparticles (NPs) inside coatings. The photochemical properties of the TiQ/Iod photoinitiating system have been probed by electron paramagnetic resonance, laser flash photolysis, and real-time Fourier transform infrared spectroscopy, which provide an insight into the possible radical/cationic pathways. The microstructural properties of the photosynthesized Ti-based NPs have been investigated by bright-field conventional transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy. The macroscopic mechanical properties of the resulting nanocomposite reveal that the generation of these Ti-based NPs in a polyacrylate/polyether blend matrix leads to an increase of mechanical resistance by toughening the matrix.