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.将四铵盐（QASS）的开发作为新的光碱发电机，对抗阴离子的影响和QASS具有1- phenenacyl-4-aza-bicyclo [2.2.2]辛烷[2.2.2]的QASS的影响和热稳定性进行了研究。在254 Nm，QAS，QAS，具有254 Nm，A Ectne ando niion eneion nion ectane and Centane octane niia octane octane octane octane niia ectane [2.2]。2 （DABCO）进一步形成硫醇酸盐 /铵络合物。在存在QA的情况下，聚（PGMA）（PGMA）膜在辐射中不溶于四氢呋喃（THF），然后加热。QASS具有硒酰胺或phthalimide阳离子的含量较低的熔融点和降解温度。含有2,4-二硝基化阴离子的QA的膜并未在具有TERT叔丁基苯甲酸酯，二苯基乙酸酯和苯并型阴离子的QASS中不溶于THF。通过1H NMR光谱和比色分析证实了DABCO的形成。我们还成功地合成了QA的合成，该QA释放了1,8-二扎比西克洛[5.4.0] -Undec-7-Ene in prifradiation.2.22.2.22.2.2.22.2.2.22.2.22.2.22.2.2.22.2。探索了交联系统，发现硫烷天线和ketobiscoumarin衍生物是366或405 nm的良好敏化剂。这些结果应用于QASS，发现具有苯甲酸酯阴离子的QA在存在异丙基thioxanthone的情况下对366 nm的辐射反应。