, Volume 25, Issue 12, pp 6887–6900 | Cite as

Substituent effects on cellulose dissolution in imidazolium-based ionic liquids

  • Niwanthi Dissanayake
  • Vidura D. Thalangamaarachchige
  • Shelby Troxell
  • Edward L. Quitevis
  • Noureddine Abidi
Original Paper


The dissolution of cotton cellulose with ionic liquids (ILs) has been extensively studied. However, the mechanism of cellulose dissolution, especially the role of the IL cation in the dissolution process, is not well understood. This paper describes a systematic study of the effects of the substituent groups on the cation in imidazolium-based ILs on cellulose dissolution. A series of imidazolium-based ILs with acetate as the anion, 1-hepyl-3-methylimidazolium acetate ([C7C1im][OAc]), 1-(cyclohexylmethyl)-3-methylimidazolium acetate ([CyhmC1im][OAc]), 1-benzyl-3-methylimidazolium acetate ([BnzC1im][OAc]), 1,3-dibenzylimidazolium acetate ([(Bnz)2im][OAc]), and 1-(2-napthylmethyl)-3-methylimidazolium acetate ([NapmC1im][OAc]) were synthesized. In each dissolution experiment, 5% (w/w) ground cotton fiber was dissolved in the ILs at 90 °C. The progress of the dissolution was monitored periodically with a polarized light microscope. This study revealed that [BnzC1im][OAc] dissolved cotton cellulose more efficiently than the other four ILs. The results are discussed within the context of previous published theoretical and experimental studies on cellulose dissolution in ILs. For the five ILs that were investigated, we find that the effect of the cation can be rationalized on the basis of both the size and shape of the cation. In addition to the dissolution, cellulose was regenerated and characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM).

Graphical abstract


Cellulose Ionic liquids Fourier transform infrared spectroscopy Polarized light microscopy 



The authors thank Bayer Crop Science for their financial support. The authors would like to knowledge Yu Zhang for her assistance in ionic liquid synthesis.

Supplementary material

10570_2018_2055_MOESM1_ESM.docx (11.1 mb)
Supplementary material 1 (DOCX 11330 kb)


  1. Abe M, Fukaya Y, Ohno H (2010) Extraction of polysaccharides from bran with phosphonate or phosphinate-derived ionic liquids under short mixing time and low temperature. Green Chem 12:1274. CrossRefGoogle Scholar
  2. Abidi N, Hequet E, Cabrales L et al (2008) Evaluating cell wall structure and composition of developing cotton fibers using fourier transform infrared spectroscopy and thermogravimetric analysis. J Appl Polym Sci 107:476–486. CrossRefGoogle Scholar
  3. Abidi N, Cabrales L, Haigler CH (2014) Changes in the cell wall and cellulose content of developing cotton fibers investigated by FTIR spectroscopy. Carbohydr Polym 100:9–16. CrossRefPubMedGoogle Scholar
  4. Andanson J-M, Bordes E, Devémy J et al (2014) Understanding the role of co-solvents in the dissolution of cellulose in ionic liquids. Green Chem 16:2528. CrossRefGoogle Scholar
  5. Andanson JM, Pádua AAH, Costa Gomes MF (2015) Thermodynamics of cellulose dissolution in an imidazolium acetate ionic liquid. Chem Commun 51:4485–4487. CrossRefGoogle Scholar
  6. Azizi Samir MAS, Alloin F, Dufresne A (2005) Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromol 6:612–626CrossRefGoogle Scholar
  7. Casas A, Palomar J, Alonso MV et al (2012) Comparison of lignin and cellulose solubilities in ionic liquids by COSMO-RS analysis and experimental validation. Ind Crops Prod 37:155–163. CrossRefGoogle Scholar
  8. Casas A, Omar S, Palomar J et al (2013) Relation between differential solubility of cellulose and lignin in ionic liquids and activity coefficients. RSC Adv 3:3453–3460. CrossRefGoogle Scholar
  9. Dassanayake RS, Gunathilake C, Jackson T et al (2016) Preparation and adsorption properties of aerocellulose-derived activated carbon monoliths. Cellulose 23:1363–1374. CrossRefGoogle Scholar
  10. Derecskei B, Derecskei-Kovacs A (2006) Molecular dynamic studies of the compatibility of some cellulose derivatives with selected ionic liquids. Mol Simul 32:109–115. CrossRefGoogle Scholar
  11. Ding ZD, Chi Z, Gu WX et al (2012) Theoretical and experimental investigation on dissolution and regeneration of cellulose in ionic liquid. Carbohydr Polym 89:7–16. CrossRefPubMedGoogle Scholar
  12. Endo T, Hosomi S, Fujii S et al (2016) Anion bridging-induced structural transformation of cellulose dissolved in ionic liquid. J Phys Chem Lett 7:5156–5161. CrossRefPubMedGoogle Scholar
  13. Endo T, Hosomi S, Fujii S et al (2017) Nano-structural investigation on cellulose highly dissolved in ionic liquid: a small angle x-ray scattering study. Molecules. CrossRefPubMedGoogle Scholar
  14. Gericke M, Fardim P, Heinze T (2012) Ionic liquids—promising but challenging solvents for homogeneous derivatization of cellulose. Molecules 17:7458–7502CrossRefGoogle Scholar
  15. Gupta KM, Jiang J (2015) Cellulose dissolution and regeneration in ionic liquids: a computational perspective. Chem Eng Sci 121:180–189. CrossRefGoogle Scholar
  16. Gupta KM, Hu Z, Jiang J (2011) Mechanistic understanding of interactions between cellulose and ionic liquids: a molecular simulation study. Polymer (Guildf) 52:5904–5911. CrossRefGoogle Scholar
  17. Haigler CH, Betancur L, Stiff MR, Tuttle JR (2012) Cotton fiber: a powerful single-cell model for cell wall and cellulose research. Front Plant Sci. CrossRefPubMedPubMedCentralGoogle Scholar
  18. Heinze T, Dorn S, Schöbitz M et al (2008) Interactions of ionic liquids with polysaccharides—2: Cellulose. In: Macromolecular Symposia, pp 8–22CrossRefGoogle Scholar
  19. Holding AJ, Parviainen A, Kilpeläinen I et al (2017) Efficiency of hydrophobic phosphonium ionic liquids and DMSO as recyclable cellulose dissolution and regeneration media. RSC Adv 7:17451–17461. CrossRefGoogle Scholar
  20. Huo F, Liu Z, Wang W (2013) Cosolvent or antisolvent? A molecular view of the interface between ionic liquids and cellulose upon addition of another molecular solvent. J Phys Chem B 117:11780–11792. CrossRefPubMedGoogle Scholar
  21. Ilharco LM, Garcia AR, Lopes da Silva J, Vieira Ferreira LF (1997) Infrared approach to the study of adsorption on cellulose: influence of cellulose crystallinity on the adsorption of benzophenone. Langmuir 13:4126–4132. CrossRefGoogle Scholar
  22. Kahlen J, Masuch K, Leonhard K (2010) Modelling cellulose solubilities in ionic liquids using COSMO-RS. Green Chem 12:2172–2181. CrossRefGoogle Scholar
  23. Kosan B, Michels C, Meister F (2008) Dissolution and forming of cellulose with ionic liquids. Cellulose 15:59–66. CrossRefGoogle Scholar
  24. Lan W, Liu CF, Yue FX et al (2011) Ultrasound-assisted dissolution of cellulose in ionic liquid. Carbohydr Polym 86:672–677. CrossRefGoogle Scholar
  25. Li Y, Liu X, Zhang S et al (2015) Dissolving process of a cellulose bunch in ionic liquids: a molecular dynamics study. Phys Chem Chem Phys 17:17894–17905. CrossRefPubMedGoogle Scholar
  26. Li Y, Liu X, Zhang Y et al (2017) Why only ionic liquids with unsaturated heterocyclic cations can dissolve cellulose: a simulation study. ACS Sustain Chem Eng 5:3417–3428. CrossRefGoogle Scholar
  27. Li Y, Wang J, Liu X, Zhang S (2018) Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects. Chem Sci 9:4027–4043CrossRefGoogle Scholar
  28. Lindman B, Karlström G, Stigsson L (2010) On the mechanism of dissolution of cellulose. J Mol Liq 156:76–81. CrossRefGoogle Scholar
  29. Liu H, Sale KL, Holmes BM et al (2010) Understanding the interactions of cellulose with ionic liquids: a molecular dynamics study. J Phys Chem B 114:4293–4301. CrossRefPubMedGoogle Scholar
  30. Liu Y-R, Thomsen K, Nie Y et al (2016) Predictive screening of ionic liquids for dissolving cellulose and experimental verification. Green Chem 18:6246–6254. CrossRefGoogle Scholar
  31. Lu B, Xu A, Wang J (2014) Cation does matter: how cationic structure affects the dissolution of cellulose in ionic liquids. Green Chem 16:1326–1335. CrossRefGoogle Scholar
  32. Madeira Lau R, Sorgedrager MJ, Carrea G et al (2004) Dissolution of Candida antarctica lipase B in ionic liquids: effects on structure and activity. Green Chem 6:483–487. CrossRefGoogle Scholar
  33. Meng X, Devemy J, Verney V et al (2017) Improving cellulose dissolution in ionic liquids by tuning the size of the ions: impact of the length of the alkyl chains in tetraalkylammonium carboxylate. Chemsuschem 10:1749–1760. CrossRefPubMedGoogle Scholar
  34. Mostofian B, Smith JC, Cheng X (2011) The solvation structures of cellulose microfibrils in ionic liquids. Interdiscip Sci Comput Life Sci 3:308–320. CrossRefGoogle Scholar
  35. Mostofian B, Cheng X, Smith JC (2014) Replica-exchange molecular dynamics simulations of cellulose solvated in water and in the ionic liquid 1-butyl-3-methylimidazolium chloride. J Phys Chem B 118:11037–11049. CrossRefPubMedGoogle Scholar
  36. Oh SY, Il Yoo D, Shin Y et al (2005a) Crystalline structure analysis of cellulose treated with sodium hydroxide and carbon dioxide by means of X-ray diffraction and FTIR spectroscopy. Carbohydr Res 340:2376–2391. CrossRefPubMedGoogle Scholar
  37. Oh SY, Il Yoo D, Shin Y, Seo G (2005b) FTIR analysis of cellulose treated with sodium hydroxide and carbon dioxide. Carbohydr Res 340:417–428. CrossRefPubMedGoogle Scholar
  38. Ohno H, Fukaya Y (2009) Task specific ionic liquids for cellulose technology. Chem Lett 38:2–7. CrossRefGoogle Scholar
  39. Olsson C, Westman G (2013) Direct dissolution of cellulose: background, means and applications. Cellul Asp. CrossRefGoogle Scholar
  40. Payal RS, Bharath R, Periyasamy G, Balasubramanian S (2012) Density functional theory investigations on the structure and dissolution mechanisms for cellobiose and xylan in an ionic liquid: gas phase and cluster calculations. J Phys Chem B 116:833–840. CrossRefPubMedGoogle Scholar
  41. Phillips DM, Drummy LF, Conrady DG et al (2004) Dissolution and regeneration of Bombyx mori silk fibroin using ionic liquids. J Am Chem Soc 126:14350–14351. CrossRefPubMedGoogle Scholar
  42. Pinkert A, Marsh KN, Pang S, Staiger MP (2009) Ionic liquids and their interaction with cellulose. Chem Rev 109:6712–6728. CrossRefPubMedGoogle Scholar
  43. Rabideau BD, Agarwal A, Ismail AE (2013) Observed mechanism for the breakup of small bundles of cellulose Iα and Iβ in ionic liquids from molecular dynamics simulations. J Phys Chem B 117:3469–3479. CrossRefPubMedGoogle Scholar
  44. Rabideau BD, Agarwal A, Ismail AE (2014) The role of the cation in the solvation of cellulose by imidazolium-based ionic liquids. J Phys Chem B 118:1621–1629. CrossRefPubMedGoogle Scholar
  45. Ragauskas AJ, Williams CK, Davison BH et al (2006) The path forward for biofuels and biomaterials. Science 311:484–489CrossRefGoogle Scholar
  46. Remsing RC, Swatloski RP, Rogers RD, Moyna G (2006) Mechanism of cellulose dissolution in the ionic liquid 1-n-butyl-3-methylimidazolium chloride: a 13C and 35/37Cl NMR relaxation study on model systems. Chem Commun. CrossRefGoogle Scholar
  47. Remsing RC, Hernandez G, Swatloski RP et al (2008) Solvation of carbohydrates in N, N′-dialkylimidazolium ionic liquids: a multinuclear NMR spectroscopy study. J Phys Chem B 112:11071–11078. CrossRefPubMedGoogle Scholar
  48. Rogers RD, Seddon KR (2003) Ionic liquids—solvents of the future? Science 302:792–793CrossRefGoogle Scholar
  49. Salmén L, Bergström E (2009) Cellulose structural arrangement in relation to spectral changes in tensile loading FTIR. Cellulose 16:975–982. CrossRefGoogle Scholar
  50. Schutt TC, Bharadwaj VS, Hegde GA et al (2016) In silico insights into the solvation characteristics of the ionic liquid 1-methyltriethoxy-3-ethylimidazolium acetate for cellulosic biomass. Phys Chem Chem Phys 18:23715–23726. CrossRefPubMedGoogle Scholar
  51. Schwanninger M, Rodrigues JC, Pereira H, Hinterstoisser B (2004) Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose. Vib Spectrosc 36:23–40. CrossRefGoogle Scholar
  52. Sun N, Rodríguez H, Rahman M, Rogers RD (2011) Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass? Chem Commun 47:1405–1421. CrossRefGoogle Scholar
  53. Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellose with ionic liquids. J Am Chem Soc 124:4974–4975. CrossRefPubMedGoogle Scholar
  54. Thakurathi M, Gurung E, Cetin MM et al (2018) The Stokes-Einstein equation and the diffusion of ferrocene in imidazolium-based ionic liquids studied by cyclic voltammetry: effects of cation ion symmetry and alkyl chain length. Electrochim Acta. CrossRefGoogle Scholar
  55. Velioglu S, Yao X, Devémy J et al (2014) Solvation of a cellulose microfibril in imidazolium acetate ionic liquids: effect of a cosolvent. J Phys Chem B 118:14860–14869. CrossRefPubMedGoogle Scholar
  56. Vitz J, Erdmenger T, Haensch C, Schubert US (2009) Extended dissolution studies of cellulose in imidazolium based ionic liquids. Green Chem 11:417–424. CrossRefGoogle Scholar
  57. Welton T (1999) Room-temperature ionic liquids. Solvents for synthesis and catalysis. Chem Rev 99:2071–2084. CrossRefPubMedGoogle Scholar
  58. Xu A, Wang J, Wang H (2010) Effects of anionic structure and lithium salts addition on the dissolution of cellulose in 1-butyl-3-methylimidazolium-based ionic liquid solvent systems. Green Chem 12:268–275. CrossRefGoogle Scholar
  59. Xu H, Pan W, Wang R et al (2012) Understanding the mechanism of cellulose dissolution in 1-butyl-3-methylimidazolium chloride ionic liquid via quantum chemistry calculations and molecular dynamics simulations. J Comput Aided Mol Des 26:329–337. CrossRefPubMedGoogle Scholar
  60. Yao Y, Li Y, Liu X et al (2015) Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory. Chin J Chem Eng 23:1894–1906. CrossRefGoogle Scholar
  61. Youngs TGA, Holbrey JD, Deetlefs M et al (2006) A molecular dynamics study of glucose solvation in the ionic liquid 1,3-dimethylimidazolium chloride. ChemPhysChem 7:2279–2281. CrossRefPubMedGoogle Scholar
  62. Youngs TGA, Hardacre C, Holbrey JD (2007) Glucose solvation by the ionic liquid 1,3-dimethylimidazolium chloride: a simulation study. J Phys Chem B 111:13765–13774. CrossRefPubMedGoogle Scholar
  63. Youngs TGA, Holbrey JD, Mullan CL et al (2011) Neutron diffraction, NMR and molecular dynamics study of glucose dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate. Chem Sci 2:1594. CrossRefGoogle Scholar
  64. Zavrel M, Bross D, Funke M et al (2009) High-throughput screening for ionic liquids dissolving (ligno-)cellulose. Bioresour Technol 100:2580–2587. CrossRefPubMedGoogle Scholar
  65. Zhang H, Wu J, Zhang J, He J (2005) 1-allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 38:8272–8277. CrossRefGoogle Scholar
  66. Zhang S, Sun N, He X et al (2006) Physical properties of ionic liquids: database and evaluation. J Phys Chem Ref Data 35:1475–1517CrossRefGoogle Scholar
  67. Zhao H, Baker GA, Song Z et al (2008) Designing enzyme-compatible ionic liquids that can dissolve carbohydrates. Green Chem 10:696–705. CrossRefGoogle Scholar
  68. Zhao D, Li H, Zhang J et al (2012) Dissolution of cellulose in phosphate-based ionic liquids. Carbohydr Polym 87:1490–1494. CrossRefGoogle Scholar
  69. Zhao Y, Liu X, Wang J, Zhang S (2013) Insight into the cosolvent effect of cellulose dissolution in imidazolium-based ionic liquid systems. J Phys Chem B 117:9042–9049. CrossRefPubMedGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Fiber and Biopolymer Research Institute, Department of Plant and Soil ScienceTexas Tech UniversityLubbockUSA
  2. 2.Department of Chemistry & BiochemistryTexas Tech UniversityLubbockUSA

Personalised recommendations