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本文在研究二烷基磷酸、烷基膦酸单烷基酯、二烷基膦酸、单烷基磷酸与单烷基膦酸五种类型酸性磷(膦)酸酯的合成与纯化的基础上,考察了它们的缔合度和萃取稀土的机理,并计算了萃取钕、钐、镱和钇的平衡常数和分离因数。酸性磷(膦)酸酯萃取稀土的平衡常数与其反应基团解离常数密切有关,它们与取代基常数、磷(膦)酸基氧原子电荷密度间均有良好线性关系。酸性磷(膦)酸酯的结构空间位阻对萃取稀土的性能有显著影响。所研究磷(膦)酸酯萃取稀土的选择性随其平衡常数的增大而下降,符合文中提出的溶剂萃取中的反应性-选择性原理。
Based on the synthesis and purification of five types of acidic phosphorus (phosphonates), such as dialkylphosphoric acid, monoalkyl alkylphosphonic acid, dialkylphosphonic acid, monoalkylphosphoric acid and monoalkylphosphonic acid, , Their associations and mechanism of rare earth extraction were investigated. The equilibrium constants and separation factors of neodymium, samarium, ytterbium and yttrium were calculated. The equilibrium constants of rare earths extracted by acidic phosphorus (phosphine) esters are closely related to the dissociation constants of their reactive groups, which have a good linear relationship with the substituent constants and the charge density of phosphorus (phosphorus) acid oxygen atoms. The steric hindrance of acidic phosphorus (phosphine) acid esters has a significant effect on the performance of rare earth extraction. The selectivity of rare earths extracted by phosphorus (phosphonates) decreased with the increase of the equilibrium constant, which was consistent with the principle of reactivity-selectivity in the solvent extraction proposed in the paper.