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

1.新型光碱生成剂季铵盐（QASs）的研制研究了反阴离子对辛烷为1-phenacyl-4-氮杂-双环[2.2.2]的季铵盐的光反应性和热稳定性的影响。在254 nm辐照下，具有硫氰酸盐阴离子的QAS生成1,4-重氮-双环[2.2.2]辛烷（DABCO），该DABCO进一步形成硫酸盐/铵配合物。在此QAS存在下，聚甲基丙烯酸缩水甘油酯（PGMA）薄膜在辐照后加热后不溶于四氢呋喃（THF）。含有硒氰酸盐或邻苯二甲酸亚胺阴离子的QASs具有较低的熔点和热降解温度。含有含有2,4-二硝基苯酚阴离子的QAS的薄膜在四氢呋喃中不溶。含有叔丁基苯甲酸酯、二苯乙酸酯和苯甲酸酯阴离子的QASs在有机溶剂中的溶解度较高，热稳定性较高。通过1H NMR和比色分析证实了DABCO的形成。我们还成功地合成了一种能在辐照下释放1,8-重氮杂环[5.4.0]-十一-7-烯的QAS。在366 nm和405 nm波长处，硫代蒽酮和酮双香豆素衍生物都是较好的增敏剂，它们能生成对交联系统有用的伯胺和邻氨基甲酰肟。将这些结果应用到QAS中，发现具有苯甲酸酯阴离子的QAS在异丙基硫代蒽酮存在下在366nm辐照下发生反应。

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.