Effects of anionic structure and lithium salts addition on the dissolution of cellulose in 1-butyl-3-methylimidazolium-based ionic liquid solvent systems
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Cellulose is the most abundant biorenewable and biodegradable resource on the earth. However, the extent of its application is limited due to its inefficient dissolution in solvents. Thus, the development of new cellulose solvents continues to be an active area of investigation. In this work, a series of ionic liquids (ILs) have been synthesized by coupling the 1-N-butyl-3-methylimidazolium cation [C4mim]+ with the Brønsted basic anions [CH3COO]−, [HSCH2COO]−, [HCOO]−, [(C6H5]COO]−, [H2NCH2COO]−, [HOCH2COO]−, [CH3CHOHCOO]− and [N(CN)2]−. The solubilities of microcrystalline cellulose (MCC) in these ionic liquids were determined as a function of temperature. The effect of the anion structure on the solubility of cellulose has been estimated, and investigated by 1H NMR and a solvatochromic UV/vis probe. It was found that the solubility of cellulose increases almost linearly with increasing hydrogen bond accepting ability of anions in the ionic liquids. At the same time, novel [C4mim][CH3COO]/lithium salt (LiCl, LiBr, LiAc, LiNO3, or LiClO4) solvent systems have been developed by adding 1.0 wt% of lithium salt into [C4mim][CH3COO]. It was shown that the addition of lithium salts significantly increased the solubility of the cellulose. This observation was studied by 13C NMR spectra, and the results suggested that the enhanced solubility of cellulose originated from the disruption of the intermolecular hydrogen bond, O(6)H⋯O(3) owing to the interaction of Li+ with the hydroxyl oxygen O(3) of cellulose. Furthermore, the cellulose materials regenerated from the ionic liquids were characterized by scanning electron micrograph, thermogravimetric analysis and Fourier transform infrared spectroscopy, and the degree of polymerization of the original and regenerated cellulose materials was also determined. Good thermal stability was found for the regenerated cellulose. It is expected that the above information is useful for the design of novel ionic liquids and ionic liquid-based solvent systems for cellulose.
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The empirical Kamlet-Taft model and the quantum mechanical COSMO-RS model have been used most frequently to predict or explain the solubility of cellulose (and other biopolymers) in ionic liquids, while few literature data exist for Hansen solubility parameters of ionic liquids.
“The empirical Kamlet-Taft model 69c,d and the quantum mechanical COSMO-RS model 88 have been used most frequently to predict or explain the solubility of cellulose (and other biopolymers) in ionic liquids, while few literature data exist for Hansen solubility parameters of ionic liquids.89”
From Deconstruction of lignocellulosic biomass with ionic liquids (2013) · cites this paper as [89]
Cites
Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2
Hallett, J. P., & Welton, T. (2011) · Chemical Reviews · doi:10.1021/cr1003248 · Cited by 12,581 · see citing works
Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis
Welton, T. (1999) · Chemical Reviews · doi:10.1021/cr980032t · Cited by 11,866 · see citing works
Cellulose: Fascinating Biopolymer and Sustainable Raw Material
Klemm, D., Heublein, B., Fink, H., & Bohn, A. (2005) · Angewandte Chemie International Edition · doi:10.1002/anie.200460587 · Cited by 7,551 · see citing works
Dissolution of Cellose with Ionic Liquids
Swatloski, R. P., Spear, S. K., Holbrey, J. D., & Rogers, R. D. (2002) · Journal of the American Chemical Society · doi:10.1021/ja025790m · Cited by 4,735 · see citing works
Hydrophobic, Highly Conductive Ambient-Temperature Molten Salts
Bonhôte, P., Dias, A.-P., Papageorgiou, N., Kalyanasundaram, K., & Grätzel, M. (1996) · Inorganic Chemistry · doi:10.1021/ic951325x · Cited by 4,358 · see citing works
Ionic Liquid (Molten Salt) Phase Organometallic Catalysis
Dupont, J., de Souza, R. F., & Suarez, P. A. Z. (2002) · Chemical Reviews · doi:10.1021/cr010338r · Cited by 3,753 · see citing works
Room temperature ionic liquids as novel media for ‘clean’ liquid–liquid extraction
Huddleston, J. G., Willauer, H. D., Swatloski, R. P., Visser, A. E., & Rogers, R. D. (1998) · Chemical Communications · doi:10.1039/a803999b · Cited by 2,169 · see citing works
Zhang, H., Wu, J. L., Zhang, J., & He, J. (2005) · Macromolecules · doi:10.1021/ma0505676 · Cited by 1,437 · see citing works
Room Temperature Ionic Liquids from 20 Natural Amino Acids
Fukumoto, K., Yoshizawa‐Fujita, M., & Ohno, H. (2005) · Journal of the American Chemical Society · doi:10.1021/ja043451i · Cited by 1,241 · see citing works
Ionic liquids: solvent properties and organic reactivity
Chiappe, C., & Pieraccini, D. (2005) · Journal of Physical Organic Chemistry · doi:10.1002/poc.863 · Cited by 1,169 · see citing works
Advances in cellulose ester performance and application
Edgar, K. J., Buchanan, C. M., Debenham, J. S., Rundquist, P. A., Seiler, B. D., Shelton, M. C., & Tindall, D. (2001) · Progress in Polymer Science · doi:10.1016/s0079-6700(01)00027-2 · Cited by 1,080 · see citing works
Sun, N., Rahman, M., Qin, Y., Maxim, M. L., Rodríguez, H., & Rogers, R. D. (2009) · Green Chemistry · doi:10.1039/b822702k · Cited by 988 · see citing works
Dissolution of Wood in Ionic Liquids
Kilpeläinen, I., Xie, H., King, A. W. T., Granström, M., Heikkinen, S., & Argyropoulos, D. S. (2007) · Journal of Agricultural and Food Chemistry · doi:10.1021/jf071692e · Cited by 943 · see citing works
Unconventional methods in cellulose functionalization
Heinze, T. J., & Liebert, T. F. (2001) · Progress in Polymer Science · doi:10.1016/s0079-6700(01)00022-3 · Cited by 893 · see citing works
Fort, D. A., Remsing, R. C., Swatloski, R. P., Moyna, P., Moyna, G., & Rogers, R. D. (2006) · Green Chemistry · doi:10.1039/b607614a · Cited by 815 · see citing works
Cellulose dissolution with polar ionic liquids under mild conditions: required factors for anions
Fukaya, Y., Hayashi, K., Wada, M., & Ohno, H. (2008) · Green Chem. · doi:10.1039/b713289a · Cited by 775 · see citing works
Moutos, F. T., Freed, L. E., & Guilak, F. (2007) · Nature Materials · doi:10.1038/nmat1822 · Cited by 738 · see citing works
Remsing, R. C., Swatloski, R. P., Rogers, R. D., & Moyna, G. (2006) · Chemical Communications · doi:10.1039/b600586c · Cited by 712 · see citing works
High-throughput screening for ionic liquids dissolving (ligno-)cellulose
Zavrel, M., Bross, D., Funke, M., Büchs, J., & Spieß, A. C. (2009) · Bioresource Technology · doi:10.1016/j.biortech.2008.11.052 · Cited by 696 · see citing works
Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide
McCormick, C. L., Callais, P. A., & Hutchinson, B. H. (1985) · Macromolecules · doi:10.1021/ma00154a010 · Cited by 673 · see citing works
Fukaya, Y., Sugimoto, A., & Ohno, H. (2006) · Biomacromolecules · doi:10.1021/bm060327d · Cited by 504 · see citing works
Extended dissolution studies of cellulose in imidazolium based ionic liquids
Vitz, J., Erdmenger, T., Haensch, C., & Schubert, U. S. (2009) · Green Chemistry · doi:10.1039/b818061j · Cited by 459 · see citing works
Room-temperature ionic liquids that dissolve carbohydrates in high concentrations
Liu, Q., Janssen, M. H. A., van Rantwijk, F., & Sheldon, R. A. (2004) · Green Chemistry · doi:10.1039/b412848f · Cited by 371 · see citing works
High-resolution 13C NMR studies of cellulose and cellulose oligomers in ionic liquid solutions
Moulthrop, J. S., Swatloski, R. P., Moyna, G., & Rogers, R. D. (2005) · Chemical Communications · doi:10.1039/b417745b · Cited by 345 · see citing works
Cao, Y., Wu, J. L., Zhang, J., Li, H., Zhang, Y., & He, J. (2008) · Chemical Engineering Journal · doi:10.1016/j.cej.2008.11.011 · Cited by 324 · see citing works
Dissolution and regeneration of cellulose in NaOH/thiourea aqueous solution
Zhang, L., Ruan, D., & Gao, S. (2002) · Journal of Polymer Science Part B Polymer Physics · doi:10.1002/polb.10215 · Cited by 320 · see citing works
A hydrogen bond accepting (HBA) scale for anions, including room temperature ionic liquids
Lungwitz, R., & Spange, S. (2008) · New Journal of Chemistry · doi:10.1039/b714629a · Cited by 282 · see citing works
New Developments in Dissolving and Processing of Cellulose in Ionic Liquids
Hermanutz, F., Gähr, F., Uerdingen, E., Meister, F., & Kosan, B. (2008) · Macromolecular Symposia · doi:10.1002/masy.200850203 · Cited by 233 · see citing works
Infrared spectra of cellulose and related polysaccharides
Higgins, H. G., Stewart, C. M., & Harrington, K. J. (1961) · Journal of Polymer Science · doi:10.1002/pol.1961.1205115505 · Cited by 229 · see citing works
Zhang, L., Ruan, D., & Zhou, J. (2001) · Industrial & Engineering Chemistry Research · doi:10.1021/ie0010417 · Cited by 227 · see citing works
KATAOKA, Y., & Kondo, T. (1998) · Macromolecules · doi:10.1021/ma970768c · Cited by 210 · see citing works
McCormick, C. L., & Dawsey, T. R. (1990) · Macromolecules · doi:10.1021/ma00217a011 · Cited by 130 · see citing works
Hydrolysis of Cotton Fiber Cellulose in Formic Acid
Sun, Y., Lin, L., Pang, C., et al. (2007) · Energy & Fuels · doi:10.1021/ef070134z · Cited by 120 · see citing works
Degradation of cellulosic materials by heating in DMAc/LiCl
Potthast, A., Rosenau, T., Sixta, H., et al. (2002) · Tetrahedron Letters · doi:10.1016/s0040-4039(02)01767-7 · Cited by 118 · see citing works
New aspects on polarity of 1-alkyl-3-methylimidazolium salts as measured by solvatochromic probes
Oehlke, A., Hofmann, K., & Spange, S. (2006) · New Journal of Chemistry · doi:10.1039/b516709d · Cited by 112 · see citing works
Use of ionic liquids for the efficient utilization of lignocellulosic materials
Zhu, S. (2008) · Journal of Chemical Technology & Biotechnology · doi:10.1002/jctb.1884 · Cited by 109 · see citing works
Dissolution of beech and spruce milled woods in LiCl/DMSO.
Wang, Z.-G., Yokoyama, T., Chang, H.-M., & Matsumoto, Y. (2009) · Journal of Agricultural and Food Chemistry · doi:10.1021/jf900441q · Cited by 106 · see citing works
Fischer, S., Voigt, W., & Fischer, K. (1999) · Cellulose · doi:10.1023/a:1009269614096 · Cited by 101 · see citing works
Effect of Solvent Exchange on the Solid Structure and Dissolution Behavior of Cellulose
Ishii, D., Tatsumi, D., & Matsumoto, T. (2003) · Biomacromolecules · doi:10.1021/bm034065g · Cited by 90 · see citing works
Zhou, Tashiro, K., Hongo, T., et al. (2001) · Macromolecules · doi:10.1021/ma001507x · Cited by 82 · see citing works
Load Distribution in Native Cellulose
Hinterstoisser, B., Åkerholm, M., & Salmén, L. (2003) · Biomacromolecules · doi:10.1021/bm030017k · Cited by 80 · see citing works
Self-Repairing DNA Based on a Reductive Electron Transfer through the Base Stack
Schwögler, A., Burgdorf, L. T., & Carell, T. (2000) · Angewandte Chemie International Edition · doi:10.1002/1521-3773(20001103)39:21 · Cited by 59 · see citing works
7Li‐NMR study on cellulose/LiCl/N.N‐dimethylacetamide solutions
Morgenstern, B., Kammer, H. W., Berger, W., et al. (1992) · Acta Polymerica · doi:10.1002/actp.1992.010430612 · Cited by 53 · see citing works
7Li NMR as probe for solvent–cellulose interactions in cellulose dissolution
Brendler, E., Fischer, S., & Leipner, H. (2001) · Cellulose · doi:10.1023/a:1015120107514 · Cited by 45 · see citing works
Huddleston, J. G., Broker, G. A., Willauer, H. D., et al. (2002) · ACS symposium series · doi:10.1021/bk-2002-0818.ch022 · Cited by 29 · see citing works
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Brandt, A., Gräsvik, J., Hallett, J. P., & Welton, T. (2013) · Green Chemistry · doi:10.1039/c2gc36364j · Cited by 1,557 · see citing works
Ionic liquid processing of cellulose
Wang, H., Gurau, G., & Rogers, R. D. (2012) · Chemical Society Reviews · doi:10.1039/c2cs15311d · Cited by 1,369 · see citing works
Self-citationIonic liquid pretreatment of lignocellulosic biomass with ionic liquid–water mixtures
Brandt, A., Ray, M. J., To, T. Q., Leak, D. J., Murphy, R. J., & Welton, T. (2011) · Green Chemistry · doi:10.1039/c1gc15374a · Cited by 491 · see citing works
Dai, Y., van Spronsen, J., Witkamp, G.-J., Verpoorte, R., & Choi, Y. H. (2013) · Journal of Natural Products · doi:10.1021/np400051w · Cited by 472 · see citing works
Advances on biomass pretreatment using ionic liquids: An overview
Tadesse, H., & Luque, R. (2011) · Energy & Environmental Science · doi:10.1039/c0ee00667j · Cited by 434 · see citing works
Ionic liquids for biofuel production: Opportunities and challenges
Liu, C.-Z., Wang, F., Stiles, A. R., & Guo, C. (2012) · Applied Energy · doi:10.1016/j.apenergy.2011.11.031 · Cited by 236 · see citing works
Pretreatment of biomass using ionic liquids: Research updates
Zhang, Q., Hu, J., & Lee, D.-J. (2017) · Renewable Energy · doi:10.1016/j.renene.2017.03.093 · Cited by 163 · see citing works
Electrospun nanosized cellulose fibers using ionic liquids at room temperature
Freire, M. G., Teles, A. R. R., Ferreira, R. A. S., Carlos, L. D., Lopes-da-Silva, J. A., & Coutinho, J. A. P. (2011) · Green Chemistry · doi:10.1039/c1gc15930e · Cited by 132 · see citing works
- Authors
- Xu, A., Wang, J., & Wang, H.
- Affiliations
- Lanzhou University (CN)
- Henan Normal University (CN)
- Corresponding author
- Wang, Jianji
- Venue
- Green Chem.
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2010
- Volume
- 12
- Issue
- 2
- Pages
- 268-275
- ISSN
- 1463-9262 (ISSN-L)
- 1463-9270
- OpenAlex
- W2047505239
- Cited by
- 439
- References
- 45
- Citations by year
- 2026: 14 · 2025: 24 · 2024: 25 · 2023: 23 · 2022: 28 · 2021: 20 · 2020: 25 · 2019: 47 · 2018: 22 · 2017: 25 · 2016: 30 · 2015: 36 · 2014: 37 · 2013: 24 · 2012: 27
- FWCI
- 7.80
- Type
- journal article
- Language
- en
- Open access
- green
- 202.201.7.4:8080
- Licence
- cc-by-nc-nd
- Locations
- Green Chemistry (publishedVersion)
- Lanzhou University Institutional Repository (submittedVersion, cc-by-nc-nd)
- Topics
- Physical Sciences › Chemical Engineering › Catalysis › Ionic liquids properties and applications
- Physical Sciences › Materials Science › Biomaterials › Advanced Cellulose Research Studies
- Physical Sciences › Engineering › Biomedical Engineering › Biofuel production and bioconversion
- Keywords
- cellulose dissolution, lithium salt additives, cellulose regeneration, dicyanamide
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