Development of Synthetic Methods for New Porous Materials by the Conversion of Inorganic Layred Compounds into Three-dimensional Networks

1） Reactions between a surfactant hexadecyltrimethylammonium ion （C_<16>TMA^+）and kanemite （NaHSi_2 O_5·3 H_2 O） was studied with various C_<16>TMA^+/Si rations。如果C_<16>TMA^+/Si大于0.2，则lamellar phase被捕获。固态核磁共振显示了这个阶段包含Q^4硅酸盐种类，并表明这个反应不是一个topotactic intercalation。当反应发生在环境温度下，在初始阶段包含没有Q^4硅酸盐物种的时候，建议初始产品是一个中间化合物。因此，它被假定为初始化的交互复合体在反应期间被转换成一个交叉连接的结构。2）从kanemite通过折叠板机制衍生出来的多孔材料表面被修改为使用各种硅化试剂。该表面是由RMe_2SiCl在保护性硝基大气层下的反应进行修改的。IR、固态核磁共振和DTA展示了通过硅氧基绑定成功的RMe_2Si组的非流动化。XRD分析显示，硅的结构在表面修改期间得到了维护。Pore-size分布指示，即平均Pore-size分布，如烷基链增加的长度，并建议通过表面修改对Pore-size进行成功控制。

1) Reactions between a surfactant hexadecyltrimethylammonium ion (C_<16>TMA^+)and kanemite (NaHSi_2O_5・3H_2O) was studied with various C_<16> TMA^+/Si rations. If C_<16>TMA^+/Si was larger than 0.2, lamellar phase was obtained. Solid-state NMR showed that this phase contained Q^4 silicate species, indicating that this reaction was not topotactic intercalation one. When the reaction proceeded at ambient temperature, the lamellar phase at the intial stage contained no Q^4 silicate species, suggesting that the initial product was intercalation compound. Thus, it is assumed that the initially-formed intercalation compound was converted into a cross-linked structure during the reaction.2) The surface of a porous material derived from kanemite via folded-sheet mechanism was modified by using various silylating reagents. The surface was modified by the reactions with RMe_2SiCl in toluene under protective nitrogen atmosphere. IR,solid-state NMR and DTA showed the successful immobilization of RMe_2Si-groups via siloxane bonding. XRD analysis showed that the structure of the silicate was maintained during the surface modifications. The pore-size distributions indicate that the mean pore size decreased as the length of the alkyl chain increased, suggesting successful control of pore size by surface modification.