A Study of Inorganic Ion-exchangers. VIII. The Synthesis of the Crystalline Zr(RNH)<i><sub>x</sub></i>H<sub>2−<i>x</i></sub>(PO<sub>4</sub>)<sub>2</sub>·<i>y</i>H<sub>2</sub>O and Their Characteristics (R=(C<i><sub>n</sub></i>H<sub>2<i>n</i>+1</sub>)<sub>3</sub>and C<sub>5</sub>H<sub>5</sub>,<i>n</i>=1–6)
作者:Etsuro Kobayashi、Shigemitsu Shin
DOI:10.1246/bcsj.57.465
日期:1984.2
The synthesis of microcrystalline compounds with the formula of Zr(RNH)xH2−x(PO4)2·yH2O (R=(CnH2n+1)3, C5H5, n=1–6, x=0.1–0.6, y=1–3) and their characteristics have been investigated. The compounds were formed by means of a hydrothermal reaction between RNH·H2PO4 and ZrOCl2 in the mole ratio of 4:1 at 130–180 °C. The layer-spacings of the trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, trihexylamine, and pyridine phosphates were 9.9, 13.0, 13.6, 17.0, 16.5, 18.4, and 10.9 Å respectively. In the thermal decomposition of each phosphate, the water of crystallization was eliminated at 105–130 °C. The organic base group in the alkylamine phosphates was burned in the presence of air at 330–360 °C, but this combustion was imperfect in the case of pyridine phosphate. The phosphates condensed at 400–450 °C. Zr(RNH)xH2−x(PO4)2·yH2O was also obtained by means of an ion-exchange reaction between γ-Zr(HPO4)2·2H2O and the corresponding tertiary amine. In these products, the layer-spacings of the trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, and trihexylamine phosphates were 17.6, 16.4, 16.7, 21.0, 21.5, and 23.2 Å respectively, while those of pyridine and piperidine phosphates were 12.4 and 18.4 Å respectively. The layer-spacings of the products increased roughly with the size of the guest molecules. When Zr(RNH)xH2−x(PO4)2·yH2O was treated with HCl, the products from the hydrothermal reaction changed to α-Zr(HPO4)2·H2O, while the products from the ion-exchange reaction returned to γ-Zr(HPO4)2·2H2O the raw material.
研究了分子式为 Zr(RNH)xH2-x(PO4)2-yH2O(R=(CnH2n+1)3, C5H5, n=1-6, x=0.1-0.6, y=1-3)的微晶化合物的合成及其特性。这些化合物是通过 RNH-H2PO4 和 ZrOCl2 在 130-180 °C 下以 4:1 的摩尔比进行水热反应生成的。三甲基、三乙基、三丙基、三丁基、三戊基、三己胺和吡啶磷酸盐的层间距分别为 9.9、13.0、13.6、17.0、16.5、18.4 和 10.9 Å。在每种磷酸盐的热分解过程中,结晶水在 105-130 °C 的温度下被消除。烷基胺磷酸盐中的有机碱基在空气存在下于 330-360 ℃燃烧,但吡啶磷酸盐的燃烧并不完全。磷酸盐在 400-450 ℃ 时凝结。通过γ-Zr(HPO4)2-2H2O 和相应的叔胺之间的离子交换反应,还得到了 Zr(RNH)xH2-x(PO4)2-yH2O。在这些产物中,三甲基、三乙基、三丙基、三丁基、三戊基和三己胺磷酸盐的层间距分别为 17.6、16.4、16.7、21.0、21.5 和 23.2 Å,而吡啶和哌啶磷酸盐的层间距分别为 12.4 和 18.4 Å。产物的层间距大致随客体分子的大小而增加。当 Zr(RNH)xH2-x(PO4)2-yH2O 用盐酸处理时,水热反应的产物变成了 α-Zr(HPO4)2-H2O,而离子交换反应的产物又回到了原料 γ-Zr(HPO4)2-2H2O。