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

doi:10.3724/SP.J.1095.2014.30371

摘要/Abstract

摘要： 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%。

关键词: 微波辅助合成, 离子液体, 有机膦, 稀土, 萃取

Abstract: 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.

Key words: microwave-assisted synthesis, ionic liquid, organophosphorus, rare earth, extraction

中图分类号:

O653

朱涛峰, 郭苗, 王邃, 蒋珺, 胡可威, 赵玲玲, 梁洪泽. 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[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30371.

ZHU Taofeng, GUO Miao, WANG Sui, JIANG Jun, HU Kewei, ZHAO Lingling, LIANG Hongze*. Microwave-assisted Synthesis of Phosphine-Functionailzed Ionic Liquids and Investigation on the Extraction of Rare Earth[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30371.

参考文献

[1] Cinzia C,Daniela P. Ionic Liquids:Solvent Properties and Organic Reactivity[J]. J Phys Org Chem,2005,18:275-297.

[2] Martyn J E,Kenneth R S. Ionic Liquids. Green Solvents for the Future[J]. J Pure Appl Chem,2000,72(7):1391-1398.

[3] Welton T. Room-Temperature Ionic Liquids Solvents for Synthesis and Catalysis[J]. Chem Rev,1999,99:2071-2083.

[4] SHE Tingting,LIU Zuliang,GONG Kai. Synthesis of Amidoalkyl Naphthols:“One-pot” Reaction Catalyzed by Sulfonic Acid Ionic Liquid[J]. Chinese J Appl Chem,2010,27(7):778-782(in Chinese).

佘婷婷,刘祖亮,巩凯. 磺酸型离子液体催化“一锅法”合成酰胺烷基萘酚[J]. 应用化学,2010,27(7):778-782.

[5] Davis J H,Jr. Task-Specific Ionic Liquids[J]. Chem Lett,2004,33(9):1072-1077.

[6] Visser A E,Swatloski R P,Reichert W M,et al. Task-Specific Ionic Liquids for the Extraction of Metal Ions from Aqueous Solutions[J]. Chem Commun,2001:135-136.

[7] GUO Qingwei,LU Wenjuan,WANG Wei,et al. Extraction of Cerium(Ⅳ) by Ionic Liquid [C10min][NTf2][J]. Chinese J Appl Chem,2012,29(7):784-787(in Chinese).

郭庆伟，路文娟，王维，等. 咪唑类离子液体[C10min][NTf2]萃取铈(Ⅳ)[J]. 应用化学,2012,29(7):784-787.

[8] Luo H,Dai S,Bonnesen P V,et al. Extraction of Cesium Ions from Aqueous Solutions Using Calix[4]arene-bis-(tert-octylbenzo-crown-6) in Ionic Liquids[J]. Anal Chem,2004,76:3078-3083.

[9] Sun X Q,Ji Y,Zhang L N,et al. Separation of Cobalt and Nickel Using Inner Synergistic Extraction from Bifunctional Ionic Liquid Extractant(Bif-ILE)[J]. Hazard Mater,2010,182:447-452.

[10] Regel-Rosocka M. Extractive Removal of Zinc(Ⅱ) from Chloride Liquors with Phosphonium Ionic Liquids/Toluene Mixtures as Novel Extractants[J]. Sep Purif Technol,2009,66:19-24.

[11] Pan Z W,Lin J H,Li W J,et al. Studies on Extraction Equilibrium of Rare Earths in Ion Liquid Extraction System Using 1-Butyl-3-Methyl-Imidazolium Hexafluorophosphate and 1-Phenyl-3-Methyl-4-Benzoyl-Pyrazolone-5[J]. Adv Mater Res Vols,2013,602/604:887-891.

[12] Nakashima K,Kubota F,Maruyama T,et al. Feasibility of Ionic Liquids as Alternative Separation Media for Industrial Solvent Extraction Processes[J]. Ind Eng Chem Res,2005,44:4368-4372.

[13] Turanov A N,Karandashev V K,Evseeva N K. Extraction of Rare-Earth Elements from Nitrate Solutions by Fullerene Black Impregnated with Tetraphenylmethylenediphosphine Dioxide[J]. Russ J Phys Chem,2006,80(2):260-263.

[14] Liu Y H,Zhu L L. Toward Greener Separations of Rare Earths: Bifunctional Ionic Liquid Extractants in Biodiesel[J]. AIChE J,2010,56(9):2338-2346.

[15] Wang W,Yang H L,Cui H M,et al. Application of Bifunctional Ionic Liquid Extractants [A336][CA-12] and [A336][CA-100] to the Lanthanum Extraction and Separation from Rare Earths in the Chloride Medium[J]. Ind Eng Chem Res,2011,50:7534-7541.

[16] Sun X Q,Ji Y,Hu F C,et al. The Inner Synergistic Effect of Bifunctional Ionic Liquid Extractant for Solvent Extraction[J]. Talanta,2010,81:1877-1883.

[17] WEI Jing,GUO Miao,LIANG Hongze,et al. Synthesis of a Novel Functionalized Ionic Liquid and Studies on Liquid-Liquid Extraction to Neodymium(Ⅲ)[J]. Chinese J Anal Lab,2012,31:68-71(in Chinese).

危晶，郭苗，梁洪泽，等. 新型功能化离子液体的合成及液-液萃取钕(Ⅲ)的研究[J]. 分析试验室,2012,31:68-71.

[18] WEI Jing,WANG Sui,GUO Miao,et al. Synthesis of Novel Organophosphate Functionalized Ionic Liquid and Extraction of Samarium(Ⅲ) by In-tube Circulation-Flow Liquid-Liquid Microextraction[J]. J Chinese Rare Earths,2012,30:666-672(in Chinese).

危晶，王邃，郭苗，等. 一种新型磷酸酯类功能化离子液体的合成及管内循环流液液微萃取钐(Ⅲ)的研究[J]. 中国稀土学报,2012,30:666-672.

[19] Hewitt D G,Newland G L. Organophosphorus Compounds. P-Arylated Perhydro-1,2-azaphosphorines[J]. Aust J Chem,1977,52:579-587.

[20] ZHANG Hongqiang,HAO Dongmei,ZHANG Xuemei,et al. Determination of Cerium-Group Elements in Rare Earth Concentrate by Spectrophotometry with Tribromocarboxy Arsenaxo[J]. Chinese Rare Earths,2007,28(2):77-78(in Chinese).

张弘强，郝冬梅，张雪梅，等. 三溴偶氮胂吸光光度法测定稀土精矿中铈组稀土元素[J]. 稀土,2007,28(2):77-78.

[21] Deetlefs M,Seddon K R. Improved Preparations of Ionic Liquids Using Microwave Irradiation[J]. Green Chem,2003,5:181-186.

[22] Mu Z G,Zhou F,Zhang S X,et al. Preparation and Characterization of New Phosphonyl-Substituted Imidazolium Ionic Liquids[J]. Helv Chim Acta,2004,87(10):2549-2555.

[23] Zuo Y,Liu Y,Chen J,et al. Extraction and Recovery of Cerium(Ⅳ) Along with Fluorine(Ⅰ) from Bastnasite Leaching Liquor by DEHEHP in [C8mim]PF6[J]. J Chem Technol Biotechnol,2009,84:949-956.