Development of Photobase Generators for Tertiary Amines and Its Application to Curing Systems
| Project/Area Number |
15550168
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic industrial materials
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| Research Institution | Osaka Prefecture University |
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Principal Investigator |
SUYAMA Kanji Osaka Prefecture University, Department of Applied Chemistry, Lecturer, 工学研究科, 講師 (90305649)
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| Co-Investigator(Kenkyū-buntansha) |
SHIRAI Masamitsu Osaka Prefecture University, Department of Applied Chemistry, Professor, 工学研究科, 教授 (00081331)
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| Project Period (FY) |
2003 – 2005
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| Project Status |
Completed (Fiscal Year 2005)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,900,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2003: ¥2,500,000 (Direct Cost: ¥2,500,000)
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| Keywords | photobase generator / quaternary ammonium salt / carboxylate / photo-reaction / tertiary amine / sensitization / UV curing / crosslinking / ベンゾエート / 熱安定性 / エポキシ樹脂 / 硬化剤 / チオシアナート |
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| Research Abstract |
1.Development of Quaternary ammonium salts (QASs) as novel photobase generators
The 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 wavelength
The 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.
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Report
(4 results)
Research Products
(23 results)
