Cellulose Solubility in Ionic Liquid Mixtures: Temperature, Cosolvent, and Antisolvent Effects

J Phys Chem B. 2016 Aug 18;120(32):7906-19. doi: 10.1021/acs.jpcb.6b04309. Epub 2016 Aug 4.

Abstract

Select ionic liquids (ILs) dissolve significant quantities of cellulose through disruption and solvation of inter- and intramolecular hydrogen bonds. In this study, thermodynamic solid-liquid equilibrium was measured with microcrystalline cellulose in a model IL, 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]) and mixtures with protic antisolvents and aprotic cosolvents between 40 and 120 °C. The solubility of cellulose in pure [EMIm][DEP] exhibits an asymptotic maximum of approximately 20 mass % above 100 °C. Solubility studies conducted on antisolvent mixtures with [EMIm][DEP] and [BMIm][Cl] indicate that protic solvents, ethanol, methanol, and water, significantly reduce the cellulose capacity of IL mixtures by 38-100% even at small antisolvent loadings (<5 mass %). Alternatively, IL-aprotic cosolvent (dimethyl sulfoxide, dimethylformamide, and 1,3-dimethyl-2-imidazolidinone) mixtures at mass ratios up to 1:1 enhance cellulose dissolution by 20-60% compared to pure [EMIm][DEP] at select temperatures. Interactions between the IL and molecular solvents were investigated by Kamlet-Taft solvatochromic analysis, FTIR, and NMR spectroscopy. The results indicate that preferential solvation of the IL cation and anion by co- and antisolvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of IL-solvent mixtures.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Cellulose / chemistry*
  • Cellulose / metabolism
  • Hydrogen Bonding
  • Ionic Liquids / chemistry*
  • Molecular Structure
  • Nuclear Magnetic Resonance, Biomolecular
  • Solubility
  • Solvents / chemistry*
  • Spectroscopy, Fourier Transform Infrared
  • Thermodynamics
  • Viscosity

Substances

  • Ionic Liquids
  • Solvents
  • Cellulose