基于Am/Cm分离的芳胺基多孔树脂制备及其模型化合物的动态辐解机理研究

次锕系元素（Am，Cm）是HLLW中对环境具有潜在放射性危害的决定核素，Am与Cm的化学性质极为相似，相互分离非常困难。已商业化分离树脂因含有烷胺基，辐射稳定性差。以多孔无机材料为载体的灌装型树脂存在吸附剂易泄漏缺陷。多孔材料辐射接枝改性制备交换树脂具备灵活调控树脂组成及孔道微观结构的优势。本项目设计含芳胺基单体的辐射接枝体系，通过改变交联剂、链转移剂类型和用量制备出不同孔体积和比表面积的树脂，最终明确接枝条件-树脂微观结构-核素吸附动力学三者关系。接着,以分子结构含芳胺基或烷胺基的化合物作为树脂的模型化合物，模拟树脂吸附分离Am/Cm时所处的环境，设计合理的辐解体系，采用脉冲辐解瞬态分析技术揭示含（不含）芳胺基树脂的辐射降解过程和降解速率，从动态分子反应的角度阐明不同结构树脂辐射降解机理。本项目结合实验研究和机理分析，将对烷胺基树脂进行结构改性并应用于Am/Cm分离提供实验和理论依据。

The long-term radiotoxicity in high level liquid waste (HLLW) is governed by the existence of actinde elements (Am, Cm). The separation of americium and curium is compilcated because of their similar chemical properties in solution. The commercial anion exchange resins which contain alkylamino groups have poor stability against radiation. Furthermore, the main disadvantage of impregnated resin is their low stability due to the leakage of the extractant from the inorgnic support. Radiation induced grafting method for preparation of exchange resin has advantages of controlling the composition and micro-structure of resin. By designing grafting system which includes monomers with arylamino groups, we will prepare exchange resins with different surface area and pore volume through optimizing type and concentration of crosslinking agent and chain transfer agent. At last we will clearly indicate the relationship between grafting conditions, micro-structure of resin and adsorption kinetics. Moreover, arylamines and alkylamines will be selected as model compounds for resins. According to operating environment of resin, the pulse radiolysis technique will be used to clarify the degradation processes and degradation rate of model compounds. The results will elucidate the degradation mechanism from aspect of dynamic molecular reactions. The whole research project which combines with experimental study and mechanism analysis will provide experimental and theoretical base for modifying amino resins used for separation of Am and Cm.