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Acetylation of cellulose in LiCl-N,N-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

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Abstract

The acylation of three cellulose samples by acetic anhydride, Ac2O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 °C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac2O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac2O/AGU = 3. For all celluloses, the dependence of DS on Ac2O/AGU is described by an exponential decay equation: DS = DSo − Ae−[(Ac2O/AGU)/B]; (A) and (B) are regression coefficients, and DSo is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B(M-cotton) > B(M-sisal) > B(MCC); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, Nagg, of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 Nagg. To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac2O/AGU, time, temperature.

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Acknowledgments

We thank the Fapesp (São Paulo State Research Foundation) for financial support and a research fellowship to D. L. Morgado; the CNPq (National Council of Scientific Research) for a research fellowship to V. C. da Silva, and research productivity fellowships to O. A. El Seoud and E. Frollini.

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Author notes

  1. Ludmila A. Ramos

    Present address: Bahia Specialty Cellulose, Bahia, Brazil

Authors and Affiliations

  1. Institute of Chemistry of São Carlos, University of São Paulo at São Carlos, P.O. Box 780, São Carlos, SP, 13 560 970, Brazil

    Ludmila A. Ramos, Daniella L. Morgado & Elisabete Frollini

  2. Institute of Chemistry, University of São Paulo, P.O. Box 26.077, São Paulo, SP, 05513-970, Brazil

    Omar A. El Seoud & Valdinéia C. da Silva

Authors
  1. Ludmila A. Ramos
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  2. Daniella L. Morgado
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  3. Omar A. El Seoud
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  4. Valdinéia C. da Silva
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  5. Elisabete Frollini
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Correspondence to Omar A. El Seoud or Elisabete Frollini.

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Ramos, L.A., Morgado, D.L., El Seoud, O.A. et al. Acetylation of cellulose in LiCl-N,N-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose. Cellulose 18, 385–392 (2011). https://doi.org/10.1007/s10570-011-9496-0

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