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Mixed solvents for cellulose derivatization under homogeneous conditions: kinetic, spectroscopic, and theoretical studies on the acetylation of the biopolymer in binary mixtures of an ionic liquid and molecular solvents

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Abstract

Rate constants for the acetylation of microcrystalline cellulose (MCC), by ethanoic anhydride in the presence of increasing concentrations of the ionic liquid (IL), 1-allyl-3-methylimidazolium chloride in dipolar aprotic solvents (DAS), N,N-dimethylacetamide (DMAC), and acetonitrile (MeCN), have been calculated from conductivity data. The third order rate constants showed a linear dependence on [IL]. We explain this result by assuming that the reacting cellulose is hydrogen-bonded to the IL. This is corroborated by kinetic data of the acetylation of cyclohexylmethanol, FTIR of the latter compound and of cellobiose in mixtures of IL/DAS, and conductivity of the binary solvent mixtures in absence, and presence of MCC. Cellulose acetylation is faster in IL/DMAC than in IL/MeCN; this difference is explained based on solvatochromic data (empirical polarity and basicity) and molecular dynamics simulations. Results of the latter indicate hydrogen-bond formation between the hydroxyl groups of the anhydroglucose unit of MCC, (Cl−) of the IL, and the dipole of the DMAC. Under identical experimental conditions, acetylation in IL/DMAC is faster than that in LiCl/DMAC (2.7–8 times), due to differences in the enthalpies and entropies of activation.

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Acknowledgments

We thank TWAS (The Academy of Sciences for the Developing World) and CNPq (National Council for Scientific and Technological Research) for a pre-doctoral fellowship to H. Nawaz, an undergraduate fellowship to T. A. Bioni, and a productivity fellowship to O. A. El Seoud, and FAPESP (São Paulo research Foundation) for financial support.

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Authors and Affiliations

  1. Institute of Chemistry, University of São Paulo, P. O. B. 26077, São Paulo, SP, 05513-970, Brazil

    Haq Nawaz, Paulo A. R. Pires, Thaís A. Bioni, Elizabeth P. G. Arêas & Omar A. El Seoud

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  1. Haq Nawaz
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  2. Paulo A. R. Pires
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  3. Thaís A. Bioni
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  4. Elizabeth P. G. Arêas
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  5. Omar A. El Seoud
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Correspondence to Omar A. El Seoud.

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Nawaz, H., Pires, P.A.R., Bioni, T.A. et al. Mixed solvents for cellulose derivatization under homogeneous conditions: kinetic, spectroscopic, and theoretical studies on the acetylation of the biopolymer in binary mixtures of an ionic liquid and molecular solvents. Cellulose 21, 1193–1204 (2014). https://doi.org/10.1007/s10570-014-0184-8

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