Title Page
Abstract
Contents
Ⅰ. Introduction 16
References 21
Ⅱ. Part 1 - Evaluation of styrenesulfonate-based ionic liquids as draw solute for forward osmosis 27
1. Experimental 27
1.1. Materials 27
1.2. Synthesis of styrenesulfonate-based ionic liquids with tetrabutylammonium and tributylalkylphosphonium 27
1.3. Forward osmosis performance 29
1.4. Instruments 31
2. Results and discussion 31
2.1. Synthesis and structure analysis of styrenesulfonate-based ionic liquids with tributylalkylphosphonium and tetrabutylammonium 31
2.2. Conductivity 36
2.3. Osmotic pressure 39
2.4. Thermo-responsive property 41
2.5. Fo performance 44
3. Conclusions 47
References 48
Ⅲ. Part 2 - Evaluation of benzenesulfonate derivatives-based ionic liquids as draw solute for forward osmosis 51
1. Experimental 51
1.1. Materials 51
1.2. Synthesis of benzenesulfonate derivatives-based ionic liquids with tetrabutylphosphonium 51
1.3. Forward osmosis performance 52
1.4. Instruments 53
2. Results and discussion 54
2.1. Synthesis and structure analysis of benzenesulfonate derivatives-based ionic liquids with tetrabutylphosphonium 54
2.2. Conductivity 59
2.3. Osmotic pressure 61
2.4. Thermo-responsive property 64
2.5. Contact angle 67
2.6. Fo performance 69
2.7. Recyclability test 71
3. Conclusions 73
References 74
Ⅳ. Part 3 - Evaluation of 3-sulfopropylmethacrylate derivatives-based ionic liquids as draw solute for forward osmosis 78
1. Experimental 78
1.1. Materials 78
1.2. Synthesis of 3-sulfopropylmethacrylate-based ionic liquids with tributylalkylphosphonium 78
1.3. Forward osmosis performance 79
1.4. Instruments 80
2. Results and discussion 81
2.1. Synthesis and structure analysis of 3-sulfopropylmethacrylate-based ionic liquids with tributylalkylphosphonium 81
2.2. Viscosity 86
2.3. Conductivity 88
2.4. Osmotic pressure 90
2.5. Thermo-responsive property 92
2.6. Fo performance 95
3. Conclusions 98
Reference 99
Ⅳ. Part 4 - Evaluation of tributyl-4-vinylbenzylphosphonium-based ionic liquids as draw solute for forward osmosis 103
1. Experimental 103
1.1. Materials 103
1.2. Synthesis of tributyl-4-vinylbenzylphosphonium-based ionic liquids with alkanesulfonate 103
1.3. Forward osmosis performance 105
1.4. Instruments 106
2. Results and discussion 107
2.1. Synthesis and structure analysis of tributyl-4-vinylbenzylphosphonium-based ionic liquids with alkanesulfonate 107
2.2. Thermo-responsive property 113
2.3. Conductivity 119
2.4. Viscosity 121
2.5. Osmotic pressure 122
2.6. FO performance 124
2.7. Recyclability test 127
3. Conclusions 129
References 130
국문초록 134
Table 1. Comparison of forward osmosis (FO) performance of the thermo-responsive ILs-based draw solutes 20
Figure 1.1. Synthesis route for tributylalkylphosphonium styrenesulfonate ([P₄₄₄#][SS], where # indicates the number of carbons of the alkyl group in...[이미지참조] 33
Figure 1.2. Proton nuclear magnetic resonance (¹H-NMR) spectra: (a) tetrabutylphosphonium styrenesulfonate ([P₄₄₄₄][SS]), (b)... 34
Figure 1.3. Fourier-transform infrared (FT-IR) spectra of [P₄₄₄₄][SS] and [N₄₄₄₄][SS]. 35
Figure 1.4. Conductivity of [P₄₄₄₄][SS] and [N₄₄₄₄][SS] aqueous solutions according to the concentration of solution. 38
Figure 1.5. Osmotic pressure of [P₄₄₄₄][SS] and [N₄₄₄₄][SS] aqueous solutions according to the concentration of solution measured by freezing point... 40
Figure 1.6. Transmittance curve of (a) [P₄₄₄₄][SS] and (b) [N₄₄₄₄][SS] aqueous solutions according to solutions concentration measured by the temperature... 43
Figure 1.7. Water flux and reverse solute flux results using (a) [P₄₄₄₄][SS] and (b) [N₄₄₄₄][SS] as draw solution according to the concentration and distilled... 46
Figure 2.1. Synthesis route for tetrabutylphosphonium benzenesulfonate ([P₄₄₄₄][BS]), tetrabutylphosphonium p- methylbenzenesulfonate... 56
Figure 2.2. ¹H-NMR spectra: (a) [P₄₄₄₄][BS], (b) [P₄₄₄₄][MBS], (c) [P₄₄₄₄][EBS], and tetrabutylphosphonium methanesulfonate ([P₄₄₄₄][MS]). 57
Figure 2.3. FT-IR spectra of (a) [P₄₄₄₄][BS], (b) [P₄₄₄₄][MBS], (c) [P₄₄₄₄][EBS], and (d) [P₄₄₄₄][MS]. 58
Figure 2.4. Conductivity of [P₄₄₄₄][MS], [P₄₄₄₄][BS], [P₄₄₄₄][MBS], and [P₄₄₄₄][EBS] aqueous solutions according to the concentration of solution. 60
Figure 2.5. Osmotic pressure of [P₄₄₄₄][MS], [P₄₄₄₄][BS], [P₄₄₄₄][MBS], and [P₄₄₄₄][EBS] aqueous solutions according to the concentration of solution... 63
Figure 2.6. Transmittance curve of (a) [P₄₄₄₄][MBS] and (b) [P₄₄₄₄][EBS] aqueous solutions according to the concentration of solution measured by... 66
Figure 2.7. Contact angle of [P₄₄₄₄][MBS] aqueous solution at concentrations of 0 (distilled water), 5, 10, 15, and 20 wt% on the FO membrane. 68
Figure 2.8. Water flux and reverse solute flux results using [P₄₄₄₄][MBS] aqueous solutions as draw solution according to the osmotic pressure and... 70
Figure 2.9. (a) Osmotic pressure and (b) LCST results using 20 wt% [P₄₄₄₄][MBS] aqueous solution as a draw solution and distilled water as a feed... 72
Figure 3.1. Synthesis route for tributylalkylphosphonium 3-sulfopropyl methacrylate ([P₄₄₄#][C3S], where # indicates the number of carbons of the...[이미지참조] 83
Figure 3.2. ¹H-NMR spectra: (a) tetrabutylphosphonium 3-sulfopropyl methacrylate ([P₄₄₄₄][C3S]), tributyl(hexyl)phosphonium 3-sulfopropyl... 84
Figure 3.3. FT-IR spectra of K[C3S], [P₄₄₄#]Br, and [P₄₄₄#][C3S].[이미지참조] 85
Figure 3.4. Viscosity of (a) [P₄₄₄₄][C3S] and (b) [P ₄₄₄₆][C3S] aqueous solutions according to the concentration of solution. 87
Figure 3.5. Conductivity of (a) [P₄₄₄₄][C3S] and (b) [P ₄₄₄₆][C3S] aqueous solutions according to the concentration of solution. 89
Figure 3.6. Osmotic pressure of (a) [P₄₄₄₄][C3S] and (b) [P ₄₄₄₆][C3S] aqueous solutions according to the concentration of solution measured by freezing... 91
Figure 3.7. Transmittance curve of [P ₄₄₄₆][C3S] aqueous solutions according to the concentration of solution measured by the temperature... 94
Figure 3.8. (a) Water flux and reverse solute flux results using [P ₄₄₄₆][C3S] aqueous solutions as draw solution according to the concentration and... 97
Figure 4.1. Synthesis route for tributyl-4-vinylbenzylphosphonium alkanesulfonate ([TVBP][CnS], n=4, 5, and 6, where n indicates the number... 109
Figure 4.2. ¹H-NMR spectra: tributyl-4-vinylbenzylphosphonium chloride ([TVBP][Cl]), tributyl-4-vinylbenzylphosphonium butanesulfonate... 110
Figure 4.3. High-resolution mass spectrometry (HRMS) spectra of (a) [TVBP]Cl, (b) [TVBP][C4S], (c) [TVBP][C5S], and (d) [TVBP][C6S]. 111
Figure 4.4. FT-IR spectra of [TVBP]Cl, Na[CnS], and [TVBP][CnS]. 112
Figure 4.5. (a) The photographic images of the phase transition behavior of [TVBP][C5S] and [TVBP][C6S] in water at concentrations of 2, 4, 6, and 8... 116
Figure 4.6. Particle size of 2 wt% of (a) [TVBP][C4S] and (b) [TVBP][C6S] solutions dynamic light scattering cumulant analysis with increasing... 117
Figure 4.7. (a) ¹H-NMR Spectrum and temperature-dependent 2D ROESY NMR spectra of 2 wt% of [TVBP][C4S] at (b) 25 and (c) 50 °C. (d) ¹H-NMR... 118
Figure 4.8. Conductivity of [TVBP][C4S], [TVBP][C5S], and [TVBP][C6S] aqueous solutions according to the concentration of solution. 120
Figure 4.9. Osmotic pressure of [TVBP][C4S], [TVBP][C5S], and [TVBP][C6S] aqueous solutions according to the concentration of solution... 123
Figure 4.10. (a) Water flux and reverse solute flux results using [TVBP][C5S] aqueous solutions as draw solution according to the concentration and... 126
Figure 4.11. (a) Osmotic pressure and (b) LCST results using 8 wt% [TVBP][C5S] aqueous solution as a draw solution and DI water as a feed... 128
Scheme 1. Schematic illustration of the FO process. 30