微波辅助合成有机膦功能化离子液体及对稀土离子的萃取

用微波辐射法,合成了5个含有机膦氧基团的离子液体：1-丙基-3-(3-二苯基氧膦基)丙基咪唑双(三氟甲基磺酰基)亚胺盐([PImC3P(O)Ph2][Tf2N])、1-己基-3-(3-二苯基氧膦基)丙基咪唑双(三氟甲基磺酰基)亚胺盐([HImC3P(O)Ph2][Tf2N])、1-丙基-3-(3-苯基乙氧基氧膦基)丙基咪唑双(三氟甲基磺酰基)亚胺盐([PImC3P(O)Ph(OEt)][Tf2N])、1-己基-3-(3-苯基乙氧基氧膦基)丙基咪唑双(三氟甲基磺酰基)亚胺盐([HImC3P(O)Ph(OEt)][Tf2N])和(3-苯基乙氧基氧膦基)丙基三乙胺双(三氟甲基磺酰基)亚胺盐([TENC3P(O)Ph(OEt)][Tf2N])。 用31P NMR、1H NMR、13C NMR、MS及FT-IR对产物结构进行了表征。 研究了这类离子液体对稀土Nd(III)的萃取性能。 结果表明，这类功能化离子液体可作为单一组分萃取稀土而无需加入有机稀释剂，离子液体结构对萃取效率影响很大,相同条件下季铵盐型结构的离子液体[TENC3P(O)Ph(OEt)][Tf2N]对稀土Nd(Ⅲ)的萃取效率最高。 稀土溶液pH值对萃取效率影响显著，近中性条件下(pH=6.63),对稀土Nd(Ⅲ)的萃取率最高。 用pH=1.00的盐酸溶液可以较好的从离子液体相反萃Nd(Ⅲ),反萃率可达94%。

Microwave-assisted Synthesis of Phosphine-Functionailzed Ionic Liquids and Investigation on the Extraction of Rare Earth

Five phosphine-functionalized ionic liquids, 1-propyl-3-[3-(diphenylphosphinyl)propyl]imidazolium bis(trifluoromethylsulfonyl)amide([PImC3P(O)Ph2][Tf2N]), 1-hexyl-3-[3-(diphenylphosphinyl)propyl]imidazolium bis(trifluoromethylsulfonyl)amide([HImC3P(O)Ph2][Tf2N]), 1-propyl-3-[3-(phenylethoxyphosphinyl)propyl]imidazolium bis(trifluoromethylsulfonyl)amide([PImC3P(O)Ph(OEt)][Tf2N]), 1-hexyl-3-[3-(phenylethoxyphosphinyl)propyl]imidazolium bis(trifluoromethylsulfonyl)amide([HImC3P(O)Ph(OEt)][Tf2N]) and 3-(phenylethoxyphosphinyl)propyltriethylamonium bis(trifluoromethylsulfonyl)amide([TENC3P(O)Ph(OEt)][Tf2N]), were successfully synthesized by microwave-assisted synthesis. All compounds were characterized by 31P NMR, 1H NMR, 13C NMR, HRMS and FT-IR. These ionic liquids were studied as extraction agents for Nd(Ⅲ) ions. The results show that ionic liquids can be used as a single component agent to extract rare earth without the addition of organic diluents and the structure of ionic liquids greatly influences the extraction efficiency. [TENC3P(O)Ph(OEt)][Tf2N] ionic liquid with quaternary ammonium exhibits the best extraction efficiency. The pH value of extraction systems has a significant impact on the extraction efficiency. The highest extraction efficiency is achieved under pH=6.63, while more than 94% of Nd(Ⅲ) can be stripped from the loaded organic phase under pH=1.00.