烷基膦酸功能型离子液体合成、 表征及对铀(Ⅵ)的萃取性能

doi:10.7503/cjcu20140991

摘要/Abstract

摘要：

以咪唑和吡啶作为阳离子基体, 设计合成了3种具有烷基膦酸功能基团的功能型离子液体, 利用傅里叶变换红外(FTIR)光谱、核磁共振氢谱(¹H NMR)和元素分析对离子液体的结构进行了确认, 测定了离子液体的相转变温度、热稳定性、密度和黏度等物理性能, 并对硝酸介质中萃取铀酰离子进行了研究. 结果表明, 所制备的功能离子液体可同时作为稀释剂和萃取剂, 在室温环境下实现对铀(Ⅵ)的萃取, 萃取率可达到90%以上.

关键词: 功能离子液体, 烷基膦酸, 铀酰离子, 萃取性能

Abstract:

Three task-specific ionic liquids with tributyl phosphates(TBP) functional group covalently tethered to the cationic part, [Phos-C₃-MIM][PF₆], [Phos-C₃-MIM][NTf₂] and [Phos-C₃-Pyr][NTf₂], were synthesized. Their structures were confirmed by FTIR, ¹H NMR and element analysis. Physical properties, such as phase transition temperatures, thermal stability, density and viscosity were also studied. The results of extraction perfermance as a single component, in the specific task of U(Ⅵ) extraction in nitric acid medium showed that they could be efficiently used to extract U(Ⅵ) in nitric acid medium at room temperature. The distribution ratio D(U) and the extraction efficience E could be achieved more than 10 and 90%, respectively, especially in high acidity environment.

Key words: Task-spcific ionic liquid, U(Ⅵ), Alkyl phosphate, Extaction

中图分类号:

O627.8

TrendMD:

李宏宇, 王博, 刘树明. 烷基膦酸功能型离子液体合成、表征及对铀(Ⅵ)的萃取性能. 高等学校化学学报, 2015, 36(4): 665.

LI Hongyu, WANG Bo, LIU Shuming. Synthesis and Characterization of Task-specific Ionic Liquids with Alkyl Phosphate Cations and for U(Ⅵ) Extraction^†. Chem. J. Chinese Universities, 2015, 36(4): 665.

图/表 11

Scheme 1 Synthetic routes of compounds 4—6

Table 1 1H NMR, 13C NMR data for compounds 2—6

Compd.	¹H NMR(300 MHz), δ	¹³C NMR(75 MHz), δ
2^a	8.63(s, 1H), 7.38(s, 1H), 7.33(s, 1H), 4.21—4.24(t, J=6.9 Hz, 2H), 3.96—3.98(m, 6H), 3.75(s, 3H), 2.13—2.16(m, 2H), 1.51—1.54(m, 4H), 1.24—1.25(m, 4H), 0.75—0.79(t, J=6.9 Hz, 6H)	12.76, 18.02, 25.65, 31.22, 36.35, 48.78, 61.34, 65.89, 121.76, 122.12, 136.23
3^a	8.82—8.83(d, J=8.5 Hz, 2H), 8.49—8.52(t, J=1H), 8.01—8.04(t, J=8.5 Hz, 2H), 4.70—4.73(t, J=6.9 Hz, 2H), 4.13—4.15(m, 2H), 3.95—4.03(m, 4H), 2.35—2.41(m, 2H), 1.52—1.59(m, 4H), 1.29—1.33(m, 4H), 0.80—0.83(t, J=6.9 Hz, 6H)	12.21, 18.60, 26.34, 31. 56, 53.13, 61,76, 65.87, 129, 11, 146.01, 147.31
4^b	8.57(s, 1H), 7.28(s, 1H), 7.22(s, 1H), 4.24—4.27(t, J=6.9 Hz, 2H), 3.96—4.00(m, 6H), 3.83(s, 3H), 2.10—2.20(m, 2H), 1.56—1.63(m, 4H), 1.29—1.38(m, 4H), 0.85—0.88(t, J=6.9 Hz, 6H)	13.23, 17.81, 27.96, 31.12, 37.21, 54.62, 62.58, 65.72, 127.15, 132.18, 147.20
5^b	8.85(s, 1H), 7.44(s, 1H), 7.21(s, 1H), 4.29—4.32(m, 2H), 3.96—4.01(m, 6H), 3.88(s, 3H), 2.18—2.19(m, 2H), 1.58—1.61(m, 4H), 1.31—1.36(m, 4H), 0.87—0.89(t, J=6.9 Hz, 6H)	13.43, 17.92, 28.20, 31.36, 37.45, 54.87, 62.94, 66.05, 127.31,132.24, 147.45, 159.47
6^b	8.89—8.90(d, J=8.5 Hz, 2H), 8.41—8.44(t, J=8.5 Hz, 1H), 7.96—8.00(t, J=8.5 Hz, 2H), 4.71—4.75(t, J=6.9 Hz, 2H), 4.01—4.03(m, 2H), 3.94—3.99(m, 4H), 2.35—2.39(m, 2H), 1.55—1.62(m, 4H), 1.28—1.37(m, 4H), 0.85—0.88(t, J=6.9 Hz, 6H)	12.68, 17,79, 26.22, 30.96, 52.66, 61.74, 65.83, 127.67, 145.68, 146.00, 152.89

Table 2 FTIR and elemental analysis data for compounds 2—6

Compd.	FTIR(KBr), $ν ˙$ /cm^-1	Elemental analysis(calcd., %)
Compd.	FTIR(KBr), $ν ˙$ /cm^-1	C	H	N
2	3142, 3061, 2960, 2873, 1736, 1572, 1465, 1373, 1267,	41.44(43.59)	7.34(7.32)	7.43(6.78)
	1170, 1028, 906, 862, 756, 621
3	3035, 2961, 2874, 1737, 1634, 1488, 1372, 1265, 1170,	46.12(47.07)	7.32(7.17)	3.78(3.43)
	1028, 868, 776, 684
4	3168, 3122, 2963, 2875, 1577, 1466, 1263, 1171, 1029,	37.48(37.66)	5.06(6.32)	5.80(5.86)
	840
5	3157, 3119, 2965, 2877, 1576, 1467, 1431, 1353, 1264,	33.32(33.28)	5.01(4.93)	6.69(6.85)
	1196, 1138, 1058, 1031, 803, 789, 740, 653, 617, 570
6	3138, 3071, 2964, 2877, 1637, 1491, 1468, 1353, 1266,	35.03(35.41)	4.96(4.79)	4.37(4.59)
	1194, 1137, 1058, 1030, 788, 740, 684, 617, 570

Table 2 FTIR and elemental analysis data for compounds 2—6

Compd.	FTIR(KBr), $ν ˙$ /cm^-1	Elemental analysis(calcd., %)
Compd.	FTIR(KBr), $ν ˙$ /cm^-1	C	H	N
2	3142, 3061, 2960, 2873, 1736, 1572, 1465, 1373, 1267,	41.44(43.59)	7.34(7.32)	7.43(6.78)
	1170, 1028, 906, 862, 756, 621
3	3035, 2961, 2874, 1737, 1634, 1488, 1372, 1265, 1170,	46.12(47.07)	7.32(7.17)	3.78(3.43)
	1028, 868, 776, 684
4	3168, 3122, 2963, 2875, 1577, 1466, 1263, 1171, 1029,	37.48(37.66)	5.06(6.32)	5.80(5.86)
	840
5	3157, 3119, 2965, 2877, 1576, 1467, 1431, 1353, 1264,	33.32(33.28)	5.01(4.93)	6.69(6.85)
	1196, 1138, 1058, 1031, 803, 789, 740, 653, 617, 570
6	3138, 3071, 2964, 2877, 1637, 1491, 1468, 1353, 1266,	35.03(35.41)	4.96(4.79)	4.37(4.59)
	1194, 1137, 1058, 1030, 788, 740, 684, 617, 570

Fig.1 DSC curves of TSILs compounds 4(a), 5(b)(A) and 6(B)

Fig.2 TGA curves of [Phos-C3-MIM][PF6](a), [Phos-C3-MIM][NTf2](b)(A) and [Phos-C3-Pyr][NTf2](B)

Table 3 TGA data of ionic liquids*

Compd.	T_d/℃	T_max/℃	Mass loss(%)
[Phos-C₃-MIM][PF₆](4)	260, 330	510	80
[Phos-C₃-MIM][NTf₂](5)	230, 300, 420	470	80
[Phos-C₃-Pyr][NTf₂](6)	210, 280, 310	510	80

Fig.3 Temperature dependence of density for ionic liquids compounds 4(a), 5(b)(A) and 6(B)

Fig.4 Influence of temperature on the viscosity of compounds 4(A), 5(B) and 6(C)

Fig.5 Cyclic voltammograms of compounds 4(A), 5(B) and 6(C)

Fig.6 Distribution ratio D(U) with equilibrium concentration of nitric acid for the extraction of U(Ⅵ) in different concentrations of nitric acid a. 1.1 mol/L TBP-compound 4; b. compound 4;c(U)=58 mg/L.

Fig.7 Effect of ion liquid anion structure on D(U) a. [Phos-C3-MIM][NTf2](5);b. [Phos-C3-MIM][PF6](4).c(U)=58 mg/L.

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