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

叔胺光产碱剂的研制及其在固化体系中的应用

基本信息

批准号：
15550168
负责人：
SUYAMA Kanji
金额：
$ 2.5万
依托单位：
Osaka Prefecture University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

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.

1.作为新型光产碱剂的季铵盐（QAS）的开发研究了抗衡阴离子对具有1-苯甲酰基-4-氮杂-双环[2.2.2]辛烷的QAS的光反应性和热稳定性的影响。在254 nm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)，进一步形成硫醇盐/铵络合物。在该 QAS 存在下，聚甲基丙烯酸缩水甘油酯 (PGMA) 薄膜在照射和加热后变得不溶于四氢呋喃 (THF)。具有硒氰酸酯或邻苯二甲酰亚胺阴离子的 QAS 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的膜不会变得不溶于THF。具有苯甲酸叔丁酯、乙酸二苯酯和苯甲酸阴离子的QAS在有机溶剂中表现出更高的溶解度和更高的热稳定性。通过1H NMR波谱和比色分析证实了DABCO的形成。我们还成功合成了在辐照下释放1,8-二氮杂双环[5.4.0]-undec-7-ene的QAS。2.敏感区域的扩展QAS 到更长波长的探索探索了 O-酰基肟的有效敏化剂，这些敏化剂产生可用于交联系统的伯胺和 O-氨基甲酰肟，并且它研究发现，噻吨酮和酮双香豆素衍生物在 366 或 405 nm 处是良好的敏化剂。将这些结果应用于QAS，发现具有苯甲酸根阴离子的QAS在异丙基噻吨酮的存在下在366nm的照射下发生反应。