Ao Yinyong, Yuan Weijin, Yu Tianlin, Peng Jing, Li Jiuqiang, Zhai Maolin, Zhao Long
Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory for Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Phys Chem Chem Phys. 2015 Feb 7;17(5):3457-62. doi: 10.1039/c4cp04294h. Epub 2014 Dec 22.
The quantitative analysis and identification of the radiolytic products of dicyclohexano-18-crown-6 (DCH18C6), 4',4''(5'')-di-tert-butyldicyclohexano-18-crown-6 (DtBuCH18C6) and benzo-18-crown-6 (B18C6) in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([C4mim][NTf2]) ionic liquid after irradiation were performed for the first time. It was found that the yield for radiolytic destruction of DCH18C6 and DtBuCH18C6 was less than that for B18C6. The main radiolytic products were identified as substituted crown ethers formed between crown ether and active radicals such as methyl, trifluoromethyl, butyl, and [C4mim]˙ radicals generated during the irradiation of the crown ether-[C4mim][NTf2] system. The radiation effect on the Sr(2+) partitioning of the crown ether-[C4mim][NTf2] system shows further that DCH18C6-[C4mim][NTf2] and DtBuCH18C6-[C4mim][NTf2] still have good extractability for Sr(2+) after irradiation. The extraction ability of DCH18C6-[C4mim][NTf2] and DtBuCH18C6-[C4mim][NTf2] system for Sr(2+) decreased by 14.4% and 18.2% even at 500 kGy, respectively.
首次对二环己基-18-冠-6（DCH18C6）、4',4''(5'')-二叔丁基二环己基-18-冠-6（DtBuCH18C6）和苯并-18-冠-6（B18C6）在1-丁基-3-甲基咪唑双（三氟甲基磺酰）亚胺（[C4mim][NTf2]）离子液体辐照后的辐射分解产物进行了定量分析和鉴定。发现DCH18C6和DtBuCH18C6的辐射分解破坏产率低于B18C6。主要辐射分解产物被鉴定为冠醚与在冠醚-[C4mim][NTf2]体系辐照过程中产生的甲基、三氟甲基、丁基和[C4mim]˙等活性自由基之间形成的取代冠醚。冠醚-[C4mim][NTf2]体系对Sr(2+)分配的辐射效应进一步表明，DCH18C6-[C4mim][NTf2]和DtBuCH18C6-[C4mim][NTf2]在辐照后对Sr(2+)仍具有良好的萃取能力。即使在500 kGy时，DCH18C6-[C4mim][NTf2]和DtBuCH18C6-[C4mim][NTf2]体系对Sr(2+)的萃取能力分别下降了14.4%和18.2%。
