실리카계 메조 물질 MCM-41 지지체 위에 여러 방법으로 aminopropyltrimethoxysilane(APMS)을 표면 기능화 시킨 염기촉매를 제조하였고 표준 염기반응인 Knoevenagel 축합반응을 수행하여 촉매적 활성을 측정하였다. Methyltrimethoxysilane으로 추가 표면처리하거나, APMS를 염소함유 유기실란과 축합하여 2차 아민 형성 후 고정화시킨 MCM-41 촉매(BAPM)를 제조한 결과, MCM-41 표면의 잔류 OH를 제거하고 물과의 수소결합으로 아민 활성점의 기능이 약화되는 것을 억제하여 높은 TON을 얻을 수 있었다. 코팅에 의해 표면에 많은 양의 아민이 고정화된 MCM-41은, 세공 내부의 반응 공간이 줄어들고, 인접한 아민 간의 수소결합으로 인하여 낮은 염기도가 예상되며 촉매 활성도 상대적으로 낮았다. 제조한 촉매 중에는 BAPM이 촉매 활성이 가장 우수하였다.

A series of amine functionalized MCM-41 catalysts were prepared by aminopropyltrimethoxysilane grafting and their catalytic performance in Knoevenagel reaction of selected substrates was investigated. Water resistant and catalytically active amine grafted MCM-41 was prepared by post-synthetic silylation using methyltrimethoxysilane ; hydrogen bonding of the water molecules formed during the condensation reaction to the active N group was suppressed, which led to high TON of the reaction. Amine functionalized MCM-41 prepared by coating method produced high conversion, but the TON of the catalyst was much lower than that of the amine grafted MCM-41; pore volume of the functionalized MCM-41 decreased substantially and large portion of the immobilized amine is believed to be hydrogen bonded to each other, which can result in decrease in the basicity of the N group. A secondary amine group was prepared by room temperature condensation between aminopropylsilane and chloropropylsilane, and the MCM-41 grafted with the secondary amine group demonstrated the highest catalytic activity among the catalysts prepared.

Mesoporous Silica Aminopropyltrimethoxysilane Silylation Solid Base Catalyst Knoevenagel Condensation

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