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碘鎓盐/胺复合体系,用作自由基光敏聚合的引发剂具有良好的效果,但是关于碘鎓盐和胺相互作用产生有引发活性的自由基的光化学反应机制尚不清楚。Ptitsyna曾研究了二苯基碘鎓盐和三苯基膦的光化学反应,认为首先发生鎓盐的裂解反应,接着进行芳基化作用,生成主要产物四苯基鏻和碘苯。而二芳基碘鎓盐和脂肪胺的热化学反应,则得到的主要胺类产物为原始胺的盐,芳基化产物很少。 本工作以二苯基碘鎓盐(DPIOC)/三乙胺(TEA)为例子,研究了这类化合物的光化学反应。采用高压汞灯为光源,并滤去<300nm的光,介质为CH_3CN/H_2O(14:1,V/V)混合溶剂,反应在N_2下进行,温度为30℃。关于碘鎓盐和叔胺分子间的相互作用,从
The iodonium salt / amine complex system has good effect as an initiator for radical photopolymerization. However, the mechanism of photochemical reaction of initiating active radicals with respect to iodonium salt and amine interaction is unclear. Ptitsyna studied the photochemical reaction of diphenyliodonium salt with triphenylphosphine. It is believed that the onium salt cleavage reaction first takes place, followed by the arylation, resulting in the major products tetraphenylphosphonium and iodobenzene. The thermochemical reaction of the diaryliodonium salt with the aliphatic amine then yields the main amine product as the salt of the original amine with very little arylation product. In this work, diphenyl iodonium salt (DPIOC) / triethylamine (TEA) was used as an example to study the photochemical reactions of these compounds. The high pressure mercury lamp was used as the light source, and the light with the wavelength of <300 nm was filtered out. The medium was mixed solvent of CH_3CN / H_2O (14: 1, V / V) and the reaction was carried out under N_2 temperature of 30 ℃. On the interaction between iodonium salts and tertiary amine molecules, from