Alkali Hydrolysis of Sulfated Cellulose Nanocrystals: Optimization of Reaction Conditions and Tailored Surface Charge
Abstract
:1. Introduction
2. Materials and Methods
2.1. Raw Materials
2.2. Nanocrystal Preparation
2.3. Surface Desulfation of H2SO4-Hydrolyzed CNCs
2.4. Conductometric Titration
2.5. Atomic Force Microscopy
2.6. ζ-Potential
2.7. Design of Experiments (DOE)
3. Results and Discussion
4. Conclusions
- Hydrolysis of sulfate half-esters on the CNC surface occurred over a broad range of different conditions: [NaOH] (<0.1 M to >2.0 M), CNC wt% (~0.5 to ≥2.0 wt%) and time (>0 to ≤6 h).
- Above 0.1–0.2 M NaOH there is only a minor observed difference in overall efficacy of –OSO3– removal.
- Based upon DOE analysis, reaction time, temperature, and NaOH concentration are significant factors for effective sulfate half-ester removal. There is a two-factor interaction between reaction time and NaOH concentration. The significance of the NaOH concentration is non-linear.
- Optimal conditions may vary depending on the initial and targeted sulfate concentration: 60–120 equivalents NaOH and a reaction time of 3–6 h gives Δ(–OSO3–) of ~60%.
- The traditional conditions (1.5 M NaOH, 60 °C, 5 h) typically remove about one-third to one-half of the available –OSO3– groups, dependent upon the selected concentration of CNCs (wt%).
- More desirable conditions still yield colloidally stable CNCs at significantly lower use of NaOH, thus improving work-up.
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Method | Conditions (Final) 1 | –OSO3– (mmol·kg−1) | Reference | |
---|---|---|---|---|
Initial | Final | |||
Acidic | 0.97 wt%, 0.024 M HCl, 80 °C, 2.5 h | 293 | 191 | [32] 1 |
×2 | 153 | |||
×3 | 103 | |||
×4 | 58 | |||
×7 | 55 | |||
4.39 wt%, 0.025 M HCl, 80 °C, 20 h | 148 ± 12 | 64 ± 8 | [36] | |
4.5 wt%, 0.025 M HCl, 80 °C, 20 h | 125 | 47 | [27] 1 | |
0.4 wt%, 2.5 N HCl, | 44 | n/a 3 | [43] 1 | |
0.5 wt%, 0.05 M HCl, 80 °C, 24 h | 280 | 120 | [38] | |
2.0 wt%, 2.5 M HCl, 100 °C, 5 h | ~430 | ~50 | [39] 4,5 | |
Alkaline | 9 wt%, 2.0 M NaOH, 65 °C, 5 h | 130 ± 95 | n/a 3 | [31,44] 2 |
2.78 wt%, 1.0 M NaOH, 60 °C, 5 h | 240 | 80 | [45] | |
2.78 wt%, 1.7 M NaOH, 85 °C, 72 h | 240 | 40 | ||
2 wt%, 0.1 M NaOH, 23 °C, 20 min | 234 | 222 | [46] 5 | |
0.56 wt%, 0.1 M NaOH, 50 °C, 20 min | 244 | 240 | ||
0.56 wt%, 0.1 M NaOH, 50 °C, 160 min | 244 | 225 | ||
0.55 wt%, 0.85 M NaOH, 50 °C, 20 min | 240 | 228 | ||
0.56 wt%, 0.85 M NaOH, 50 °C, 180 min | 240 | 229 | ||
1.33 wt%, 0.17 M NaOH, 60 °C, 1 h | 209 | 166 | [24] 1 | |
1.33 wt%, 0.33 M NaOH, 60 °C, 1.5 h | 209 | 144 | ||
1.33 wt%, 0.50 M NaOH, 60 °C, 2 h | 209 | 90.6 | ||
1.33 wt%, 0.67 M NaOH, 60 °C, 3 h | 209 | 56.3 | ||
1.0 wt%, 1.0 M NaOH, 60 °C, 5 h | 220 | 40 | [40,41,47]2 | |
1.0 wt%, 0.01 M NaOH, 65 °C, 30 min | ~194 | ~165 | [42] 4 | |
1.0 wt%, 0.1 M NaOH, 65 °C, 30 min | ~194 | ~152 | ||
1.0 wt%, 0.5 M NaOH, 65 °C, 30 min | ~194 | ~142 | ||
5.0 wt%, 1.5 M NaOH, 65 °C, 5 h | ~219 | ~125 | [48] 1,4 | |
2.0 wt%, 2 M NaOH, 65 °C, 5 h | ~430 | ~190 | [39] 5 | |
1.45 wt%, 1.0 M NaOH, 60 °C, 2.5 h | 150 ± 15 | 62 ± 1 | [13] |
Batch (#) | H2SO4 (wt%) | Temp (°C) | Time (min) | –OSO3– (mmol·kg−1) | ζ-Potential (mV) | Yield (%) |
---|---|---|---|---|---|---|
1 | 55 | 60 | 150 | 155 | –31.5 ± 1.5 | 43 |
2 | 65 | 55 | 60 | 197 | –40.8 ± 0.7 | 21 |
3 | 65 | 45 | 90 | 211 | –41.1 ± 1.5 | 32 |
4 | 65 | 60 | 90 | 308 | –45.3 ± 1.0 | 14 |
5 | 62 | 50 | 30 | 134 | –41.5 ± 1.1 | 39 |
Sample | CNC (wt%) | Temp (°C) | Time (h) | –OSO3– (mmol·kg−1) | Ref. or exp # | |
---|---|---|---|---|---|---|
Initial | Final | |||||
H-CNC | 3.8 | 70 | 120 | 265 2 | 90 2 | Ref. [46] |
H-CNC | 2.8 | 85 | 72 | 275 1 | 103 1 | |
H-CNC | 4.0 | 100 | 2 | 217 2 | 108 2 | |
Na-CNC | 2.8 | 85 | 72 | 275 1 | 275 1 | |
Na-CNC | 3.8 | 70 | 120 | 265 2 | 254 2 | |
H-CNC | 0.50 | 25 | 6 | 211 1 | 204 1 | #1 |
H-CNC | 0.50 | 75 | 6 | 197 1 | 87 1 | #2 |
Na-CNC | 0.50 | 25 | 0 | 211 1 | 204 1 | #3 |
Na-CNC | 0.50 | 75 | 6 | 197 1 | 193 1 | #4 |
Exp (#) | Time (min) | Temp (°C) | [NaOH] (M) | [CNC] (wt%) | Yield (%) | –OSO3– (mmol·kg−1) | Δ(–OSO3–) (%) | |
---|---|---|---|---|---|---|---|---|
Initial | Final | |||||||
#5 | 150 | 60 | 0.5 | 1.44 | 88 | 155 | 109 | 30% |
#6 | 150 | 60 | 1.0 | 1.44 | 83 | 155 | 105 | 32% |
#7 | 300 | 60 | 1.0 | 1.44 | 87 | 155 | 86 | 45% |
#8 | 300 | 30 | 1.0 | 1.44 | 83 | 155 | 121 | 21% |
#9 | 900 | 30 | 1.0 | 1.44 | 90 | 155 | 122 | 22% |
Sample | CNC (wt%) | –OSO3– (mmol·kg−1) | Δ(–OSO3–) | |
---|---|---|---|---|
Initial | Final | (%)/net | ||
#10 | 0.72 | 308 | 213 | 31|31 |
×2 | 0.58 | 213 | 162 | 24|47 |
×3 | 0.45 | 162 | 103 | 36|67 |
×4 | 0.25 | 103 | 69 | 33|78 |
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Jordan, J.H.; Easson, M.W.; Condon, B.D. Alkali Hydrolysis of Sulfated Cellulose Nanocrystals: Optimization of Reaction Conditions and Tailored Surface Charge. Nanomaterials 2019, 9, 1232. https://doi.org/10.3390/nano9091232
Jordan JH, Easson MW, Condon BD. Alkali Hydrolysis of Sulfated Cellulose Nanocrystals: Optimization of Reaction Conditions and Tailored Surface Charge. Nanomaterials. 2019; 9(9):1232. https://doi.org/10.3390/nano9091232
Chicago/Turabian StyleJordan, Jacobs H., Michael W. Easson, and Brian D. Condon. 2019. "Alkali Hydrolysis of Sulfated Cellulose Nanocrystals: Optimization of Reaction Conditions and Tailored Surface Charge" Nanomaterials 9, no. 9: 1232. https://doi.org/10.3390/nano9091232