4-CH_3SC_6H_4NH_2对α-磷酸锆的插层特性

A Study of the Intercalation Reactions of 4 (Methylmercapto) aniline with α Zirconium Phosphate

制备了４－ＣＨ３ＳＣ６Ｈ４ＮＨ２（ＭＭＡ）插层的α－Ｚｒ（ＨＰＯ４）２·Ｈ２Ｏ（α－ＺｒＰ），研究了不同实验条件下ＭＭＡ的插层特性．发现插层反应与ＭＭＡ和α－ＺｒＰ的摩尔比Ｒ有关：（１）当Ｒ＞２时，有插层产物相产生，但是即使在ＭＭＡ大大过量（Ｒ＝５～９）的条件下，仍然有部分α－ＺｒＰ没有发生插层反应；（２）当Ｒ＜２时，没有插层产物出现，只有α－ＺｒＰ．插层产物的产率与插层方法、α－ＺｒＰ颗粒大小等有关；插层产物的层间距约为２．３６ｎｍ，层间距的大小不随反应物浓度、温度等条件变化．ＭＭＡ在α－ＺｒＰ层板之间以双分子层的形式排列，并且有２种存在状态：一种是它的氨基被α－ＺｒＰ的酸性位质子化，另一种是未被质子化而与α－ＺｒＰ的氢原子以氢键的形式相连，这种不完全的质子化形式和不被插层的α－ＺｒＰ的存在可能与ＭＭＡ相对较弱的碱性有关．

Methylmercapto) aniline(MMA) has been intercalated into α Zr(HPO 4) 2\5H 2O( α ZrP), and the characteristics of the intercalation reactions have been studied. Under mild conditions, no intercalation was observed. Under more forcing conditions, variable amounts of intercalation compound were observed along with unreacted α ZrP. The yield of the intercalation compound is related to the ratio of MMA/ α ZrP, the reaction temperature and intercalation method. The interlayer spacing of the intercalation compound is about 2 36 nm, and does not vary significantly with different preparation conditions. The molecules of MMA which have been intercalated into α ZrP occur in two forms, one being protonated, the other being unprotonated in the ratio of 1 to 1 1 respectively. This incomplete proton transfer may be related to the relatively low base strength of MMA.