| Project/Area Number |
15350093
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Environmental chemistry
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| Research Institution | Yokohama National University (2004-2005)
Gifu University (2003) |
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Principal Investigator |
KUBOTA Yoshihiro Yokohama National University, Graduate School of Engineering, Associate Professor, 大学院・工学研究院, 助教授 (30283279)
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| Co-Investigator(Kenkyū-buntansha) |
FUNABIKI Kazumasa Gifu University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (50273123)
SUGI Yoshihiro Gifu University, Faculty of Engineering, Professor, 工学部, 教授 (90281047)
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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 |
¥11,200,000 (Direct Cost: ¥11,200,000)
Fiscal Year 2005: ¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2004: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2003: ¥3,900,000 (Direct Cost: ¥3,900,000)
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| Keywords | mesoporous silica / synergistic effect / solid base catalyst / C-C bond formation / fluorine-containing material / OFMS-type catalyst / SOCM-type catalyst / composite material / 有機基固定化 / 塩基触媒 / アニオン性界面活性剤 / Michael反応 / Knoevenagel縮合反応 / ナノ構造制御多孔体 / メソポーラス / シリカゲル / 有機基 / 直接的アルドール反応 / ヘミアセタール / ジアステレオ選択性 / ナノ構造制御多孔質 / マイクロポーラス / シリケート / 固定化 |
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| Research Abstract |
Basic organic group-immobilized silicate materials have been utilized as the heterogeneous catalysts for C-C bond formation reactions such as Knoevenagel condensation, aldol condensation, and Michael addition. When using the amine-immobilized mesoporous silicas as base catalysts, the real effects of amine site and silica support have not been well investigated. Here we examined the effect of amine itself on the reaction as well as the conjugate effect of silicate additives such as SBA-15, and other ordered porous silicates. As a result, the combination of some secondary amine (as a base) and periodical mesoporous silicate (as an additive) drastically enhanced the reactivity in the reaction of aromatic aldehydes with acetone leading to the selective formation of β-hydroxyketones. The yield was low in the absence of the mesoporous silicate and the mesoposous silica itself was totally inert. It was suggested that the prominent effect of the silicate is not only due to the increase in the reactant concentration on the silicate surface but also to synergistic effect of base with acid. Activity of amine-immobilized silicate (organic-functionalized molecular sieves ; OFMSs) is higher than that of the simple mixture of amine and silicate. Very often, the OFMSs were effective when the supports were ordered mesoporous material and the reaction was carried out in polar solvents ; however, the yield was low in a non-polar solvent. In contrast, silicate-organic composite materials (SOCMs) were remarkably active in a non-polar solvent. The mesoporous silicate was more active than the microporous silicate. The active sites of the SOCM catalysts were considered to be SiO^-(^+NR_4) moieties located inside the pore near the pore-entrance. Although the high activity was not due to the leached species, a gradual loss of activity was observed after repeated use.
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