Development of Photobase Generators for Tertiary Amines and Its Application to Curing Systems

1.季铵盐（QAS）作为新型光产碱剂的研究在254 nm光照射下，反阴离子对1-苯甲酰甲基-4-氮杂双环[2.2.2]辛烷（QAS）的光反应活性和热稳定性的影响进行了研究，结果表明，在254 nm光照射下，具有硫氰酸根阴离子的QAS生成1，4-二氮杂双环[2.2.2]辛烷（DABCO），DABCO进一步形成硫醇盐/铵络合物。在此QAS的存在下，聚（甲基丙烯酸缩水甘油酯）（PGMA）薄膜变得不溶于四氢呋喃（THF）的照射，然后加热。QAS具有硒氰酸根或邻苯二甲酰亚胺阴离子具有较低的熔点和热降解温度。含有具有2，4-二硝基苯酚阴离子的QAS的膜在THF中不会变得不溶。具有苯甲酸叔丁酯、二苯基乙酸酯和苯甲酸酯阴离子的QAS在有机溶剂中显示出更高的溶解度和更高的热稳定性。通过1H NMR谱和比色分析证实了DABCO的形成，并成功地合成了一种在辐照下释放1，8-二氮杂双环[5.4.0]-十一碳-7-烯的QAS。2. QAS的增敏范围向更长的波长扩展探索了对O-酰基肟生成伯胺和对交联体系有用的O-氨基甲酰肟的有效增敏剂的寻找，发现噻吨酮和酮基异香豆素衍生物在366或405 nm处是很好的增敏剂。将这些结果应用于QAS，并且发现具有苯甲酸根阴离子的QAS在异丙基噻吨酮存在下在366 nm处的照射下反应。

1.Development of Quaternary ammonium salts (QASs) as novel photobase generatorsThe effect of counter anions on the photoreactivity and thermal stability of QASs having 1-phenacyl-4-aza-bicyclo[2.2.2]octane was investigated.On irradiation at 254 nm, a QAS having thiocyanate anion generated 1,4-diaza-bicyclo[2.2.2]octane (DABCO) that was further formed a thiolate / ammonium complex. In the presence of this QAS, poly(glycidyl methacrylate) (PGMA) films became insoluble in tetrahydrofuran (THF) on irradiation followed by heating.QASs having selenocyanate or phthalimide anions had lower melting points and thermal degradation temperatures. Films containing a QAS having 2,4-dinitrophenolate anion did not become insoluble in THF.QASs having tert-butylbenzoate, diphenylacetate, and benzoformate anions showed higher solubility in organic solvents and higher thermal stability. The formation of DABCO was confirmed by 1H NMR spectroscopy and colorimetric analysis.We also succeeded in the synthesis of a QAS that released 1,8-diazabicyclo[5.4.0]-undec-7-ene on irradiation.2.Extension of sensitive region of QASs to longer wavelengthThe search for effective sensitizers for O-acyloxime that generate primary amines and O-carbamoyloximes that are useful for crosslinking systems was explored, and it is found that thioxanthone and ketobiscoumarin derivatives were good sensitizers at 366 or 405 nm. These results were applied to QASs, and it is found that a QAS having a benzoformate anion reacted on irradiation at 366 nm in the presence of isopropylthioxanthone.