分子印迹互贯网络树脂的制备及其对稀土元素的分离特性

The properties of rare earth elements are very similar, so they are diffcult to be separated, and selectivities of the existing adsorption resins for rare earth elements are relatively low. In order to meet the requirement of separation for rare earth elements, this porject aims at the preparation of novel molecular-imprinting interpenetration network resins with spherical crosslinked polystyrene or polyacrylate as the first network and linear or crosslinked molecular-imprinting polyhydroxamic acid, polyacrylamide or polyacrylic acid polymer as the second network by molecular-imprinting technique and interpenetration polymer network technique. The effect of molecular-imprinting and network-interpenetrating processes on chemical and physical strutures and adsorption and separation properties, and the relationship of preparation, polymer structures and properties also should be illustrated. The dynamic models and thermodynamic models may be built, and the adsorption mechnism of the resins and rare earth metal ions will be analysised with molecular simlution and modern analytical instruments. It should also be studied that the separation properties of molecular-imprinting interpenetration network resins between rare earth elements and heavy metals, alkali metals or alkaline earth elements,as well as between or among various rare earth elements. Finally, the adsorption and separation models are espected to be bulid, and new materials and new technology for effctive separation of rare earth elements and for preparation of pure and single rare earth products will be invented.

针对稀土元素性质相近、难以分离和现有稀土元素吸附树脂分离选择性相对较低的难题，采用分子印迹技术和互贯聚合物网络技术，制备第一网络为球形聚苯乙烯或聚丙烯酸酯交联结构，第二网络为分子印迹聚丙烯基氧肟酸、聚丙烯酰胺或聚丙烯酸线型或交联结构的新型分子印迹互贯网络树脂。研究分子印迹过程和互贯聚合物网络对树脂化学和物理结构及吸附分离性能的影响，阐明树脂制备-结构-性能之间的关系。建立树脂的吸附动力学、热力学模型，并采用分子模拟和现代仪器分析等手段，揭示树脂与稀土金属离子的吸附机理。研究分子印迹互贯网络树脂对稀土元素与重金属、碱金属、碱土金属元素及稀土元素之间的分离特性，建立树脂对稀土元素的吸附分离模型，为稀土元素的高效分离及高纯、单一稀土的制备提供新材料与新技术。

针对稀土元素性质相近、难以分离和现有稀土元素吸附树脂分离选择性相对较低的难题，运用量子化学计算和有机合成方法，设计了丙烯基羟肟酸、2-乙基-2-己烯基羟肟酸及6-氨基己基羟肟酸等羟肟酸单体及其合成路线；采用悬浮聚合技术、互贯网络技术、分子印迹技术及聚合物接枝改性方法制备了聚苯乙烯-聚羟肟酸共聚树脂、聚苯乙烯-聚羟肟酸互贯网络树脂、聚苯乙烯-离子印迹聚羟肟酸互贯网络树脂、聚酰氨基羟肟酸螯合树脂及石墨化多孔碳材料等新型吸附材料，并对其进行了结构和性能表征。采用静态吸附实验和动态吸附实验考察了新型吸附材料对镧、铈、钇等稀土金属离子的吸附性能，研究了树脂的吸附动力学和吸附热力学，结果表明，聚苯乙烯-离子印迹聚羟肟酸互贯网络树脂对稀土金属离子具有较大的吸附容量、较快的吸附动力学速度和良好的吸附选择性。采用红外光谱分析、X-射线光电子能谱分析、扫描电镜分析等手段研究了聚苯乙烯-离子印迹聚羟肟酸互贯网络树脂与稀土金属离子的吸附作用机理。发明了一种选择性吸附稀土金属离子的新方法和新装置，实现了对稀土矿浸出液的中稀土元素的选择性分离。项目所研究的稀土元素选择性吸附分离新材料和新技术，对于促进我国稀土元素的提取技术、高纯及单一稀土的制备技术的发展具有重要意义。