Stable silanetriols that contain tert-alkoxy groups: versatile precursors of siloxane-based nanomaterials.
Stable silanetriols that contain tert-alkoxy groups: versatile precursors of siloxane-based nanomaterials.
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DOI：
10.1002/chem.200700914
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发表时间：
2008-01
期刊：
影响因子：
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通讯作者：
Jumpei Suzuki;Atsushi Shimojima;Y. Fujimoto;K. Kuroda
中科院分区：
文献类型：
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作者：
Jumpei Suzuki;Atsushi Shimojima;Y. Fujimoto;K. Kuroda
由相应的叔烷氧基三氯硅烷合成了新型叔烷氧基硅三醇(Rosi(OH)(3)，R=金刚烷基和3-乙基-3-戊基)，并成功地作为分子构块用于制备有序的硅氧烷基纳米材料。烷氧基三氯硅烷的受控水解导致生成在常温下稳定的烷氧基硅烷三醇结晶粉末。烷氧基硅烷三醇在加热时发生固相缩聚，形成层状有序的二氧化硅-有机纳米复合材料。另一方面，叔烷氧基硅三醇与氯三甲氧基硅烷的硅烷化反应使我们能够合成定义明确的低聚烷氧基硅烷(ROSI[OSI(OME)(3)](3))。这些低聚物经水解、缩聚、酸处理后，得到孔径分布较窄的微孔二氧化硅。因此，叔烷氧基不仅作为硅氧烷物种的保护基团来调节水解和缩聚，而且还作为模板来产生微孔，从而为有序二氧化硅材料的设计提供了独特的合成途径。
Novel tert-alkoxysilanetriols (ROSi(OH)(3), R=adamantyl and 3-ethyl-3-pentyl) have been prepared from the corresponding tert-alkoxytrichlorosilanes and successfully used as molecular building blocks to produce ordered siloxane-based nanomaterials. Controlled hydrolysis of the alkoxytrichlorosilanes led to the formation of crystalline powders of alkoxysilanetriols that were stable under ambient conditions. Solid-state polycondensation of the alkoxysilanetriols occurred upon heating, which led to the formation of ordered silica-organic nanocomposites with laminated morphologies. On the other hand, silylation of the tert-alkoxysilanetriols with chlorotrimethoxysilane enabled us to synthesize well-defined oligomeric alkoxysilanes (ROSi[OSi(OMe)(3)](3)). Hydrolysis and polycondensation of these oligomers followed by acid treatment gave microporous silica with narrow pore size distributions. Thus, tert-alkoxy groups serve not only as protecting groups of siloxane species to regulate hydrolysis and polycondensation, but also as templates to generate micropores thereby providing unique synthetic pathways for the design of ordered silica-based materials.