Synthesis and Characterization of Task-specific Ionic Liquids with Alkyl Phosphate Cations and for U(Ⅵ) Extraction†

doi:10.7503/cjcu20140991

Abstract

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

CLC Number:

O627.8

TrendMD:

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

Figures/Tables 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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