INVESTIGATION ON DEVELOPMENT AND MOLECULAR DESIGN OF HIGH-PERFORMANCE SOLVENT EXTRACTION REAGENTS FOR RARE EARTHS

高性能稀土溶剂萃取试剂的开发及分子设计研究

基本信息

批准号：
06650886
负责人：
INOUE Katsutoshi
金额：
$ 1.34万
依托单位：
SAGA UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1995
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06650886/
关键词：
SOLVENT EXTRACTION CALIXARENE DERIVATIVES RARE METALS RARE EARTHS MOLECULAR DESIGN CARBOXYLIC ACIDS HYDROXAMIC ACIDS PHOSPHONIC ACIDS 貴金属類

项目摘要

Three types of chemically modified calixarenes containing functional groupes of carboxylic acid, hydrxamic acid and phosphonic acid were synthesized to be examined on their solvent extraction behaviors for trivalent rare earths. Carboxylate and hydroxamate types of calixarenes were synthesized by introducing functional groups of carboxylic acid and hydroxamic acid into lower rim of calix [4 or 6] arenes. Monomeric and linear trimeric analogues of carboxylates were also synthesized to compare their extraction behavior with carboxylate calixarenes. It was found that the carboxylate derivatives of calixarenes have much higher extability and selectivity for mutual separation of rare earth elements compared with the monomeric and linear trimeric analogues ; but, the ring size of the calixarene derivatives does not affect the selectivity. The hydroxamate derivatives of calixarene was found to extract metal ions by cation-exchange mechanism and have high selectivity to trivalent indium and ga … More llium in particular compared with the corresponding carboxylate derivatives. At the initial stage of the synthesis of acidic phosphonate derivatives of calix [4] arene, although it was attempted to introduce the functional groups into the lower rim of the calixarene, it was found impossible owing to the bulkiness of the functional groups, which was confirmed also by the computer simulation. Consequently, they were introduced into the upper rim of the p-tert-butylcalix [4] -arene after removal of the tert-butyl groups ; alkyl groups such as propyl and octyl groups were introduced into the lower rim by substituting the hydrogen atoms of phenolyc hydroxy groups for the alkyl groups. Monomeric analogue was also synthesized to compare the extraction behavior with the calixarene derivatives. No differences of the selectivity to rare earths were found among these three kinds of compounds, which was attributed to the loss of the size recognition for ionic radii by calixarene ring caused by the introduction of the phosphonate functional groupes into upper rim, which was also confirmed by the computer simulation. It was expected that the introduction of bulky alkyl groups such as 2-ethylhexyl group into the lower rim would enhance the selectivity. Less

合成了三种类型的化学改性钙棒，其中包含羧酸，氢酸和磷酸的官能基团，以对其三价稀土的溶剂提取行为进行检查。羧酸盐和羟氨酸类型的calixarenes类型是通过将羧酸和羟基酸的官能团引入钙的下边缘[4或6]领域来合成的。羧酸盐的单体和线性三聚体类似物也被合成以将其提取行为与羧酸钙甲磷酸盐曲甲烯比进行比较。发现与单体和线性三聚体类似物相比，calixarenes的羧酸盐衍生物具有更高的稀土元素分离性和选择性。但是，calixarene衍生物的环大小不会影响选择性。发现钙甲烯的羟氨酸衍生物通过阳离子 - 交换机制提取金属离子，并且与相应的羧酸盐衍生物相比，对三价的im依和GA具有很高的选择性。在Calix [4] Arene的酸性膦酸酯衍生物合成的初始阶段，尽管它试图将官能团引入钙甲烯的下部边缘，但由于功能组的笨重，这也是不可能通过计算机模拟证实的。因此，将它们引入了丁基丁基基团后P-TERT叔丁基钙的上边缘[4] -arene。通过将苯溶羟基的氢原子取代烷基烷基，将烷基类（例如丙基和辛基）引入下边缘。还合成了单体类似物，以将提取行为与calixarene衍生物进行比较。在这三种化合物中，没有发现对稀土的选择性的差异，这归因于由于将磷酸官能团引入上部边缘引起的钙甲烯环的离子半径识别的丢失，这也通过计算机模拟证实。可以预期，将大量烷基（如2-乙基己基类）引入下边缘将提高选择性。较少的