Benzylation of cellulose in the solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate

Abstract

The cellulose solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate (TBAF·3 H2O) was studied as reaction medium for the synthesis of benzyl cellulose (BC) by treating the dissolved polymer with benzyl chloride in the presence of solid NaOH or aqueous NaOH solution. BC samples with degree of substitution (DS) between 0.40 and 2.85 were accessible applying different molar ratios. The studies show that both the TBAF·3 H2O concentration and the molar ratio of the reagents to repeating unit influence the DS. The solubility of the BC synthesized in a different way, however, of comparable DS is different. Structural analyses were carried out by means of FTIR-, 1H- and 13C NMR spectroscopy. SEC measurements revealed polymer aggregation in samples of low DS synthesized in a solvent containing 9.0% TBAF·3 H2O. At higher concentration of TBAF·3 H2O in the solvent, the BC samples obtained do not form aggregates. BC of high DS is crystalline and shows thermotropic liquid crystalline behavior as analyzed by means of DSC. Melting point and degradation temperature are not related to the DS.

This is a preview of subscription content, access via your institution.

References

  1. Ass B.A.P., Frollini E. (2001). Aggregation of cellulose during dissolution and acetylation in N,N-dimethylacetamide/lithium chloride: an introductory study. Anais Assoc. Bras. Quim. 50(2):76–82

    Google Scholar 

  2. Ass B.A.P., Frollini E., Heinze Th. (2004). Studies on the homogeneous acetylation of linters cellulose in the novel solvent system tetrabutylammonium fluoride trihydrate/dimethylsulfoxide. Macromol. Biosci. 4:1008–1013

    Article  PubMed  CAS  Google Scholar 

  3. Awadel-Karim S., Nazhad M.M., Paszner L. (1999). Factors affecting crystalline structure of cellulose during solvent purification treatment. Holzforschung 53:1–8

    Article  CAS  Google Scholar 

  4. Braun D., Meuret B. (1989). Benzylcellulose als thermoplatischer Kunststoff. I. Herstellung und Charakterisierung. Papier 43(12):688–694

    CAS  Google Scholar 

  5. Browning B.L. (1967). Methods of wood chemistry. John Wiley, New York, Vol. 2, pp. 882

    Google Scholar 

  6. Buschle-Diller G., Zeronian S.H. (1992). Enhancing the reactivity and strength of cotton fibres. J. Appl. Polym. Sci. 45:967–979

    Article  CAS  Google Scholar 

  7. Ciacco G.T., Ass B.A.P., Ramos L.A., Frollini E. (2000). Acetylation of cellulose under homogeneous reaction conditions. In: Mattoso L.H.C., Leão A., Frollini E. (eds). Natural polymers and composites. EMBRAPA-USP-UNESP, Sao Paulo, Brazil, pp. 139–145

    Google Scholar 

  8. Ciacco G.T., Liebert T.F., Frollini E., Heinze Th. (2003). Application of the solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate as reaction medium for the homogeneous acylation of sisal cellulose. Cellulose 10:125–132

    Article  CAS  Google Scholar 

  9. Ciacco G.T., Ass B.A.P., Ramos L.A., Frollini E. (2004). Influence of the composition of the solvent system N,N-dimethylacetamide/lithium chloride on the solubility and acetylation of the sisal, sugarcane bagasse and Avicel celluloses. In: Mei L.H.C., Mattoso L.H.C., Curvelo A.A.S. (eds) Natural polymers and composites. EMBRAPA-USP- UNESP, Sao Paulo, Brazil, pp. 32–35

    Google Scholar 

  10. Da Roz A.L., Curvelo A.L. (2004). Thermal characterization of benzylcellulose derivatives prepared from bleached pinus Kraft pulp. J. Thermal Anal. 75:429–436

    Article  CAS  Google Scholar 

  11. Heinze Th., Dicke R., Koschella A., Kull A.H. and Koch W. (2000) Effective preparation of cellulose derivatives in a new simple cellulose solvent. Macromol. Chem. Phys. 201:627–631

    Article  CAS  Google Scholar 

  12. Ikeda I., Washino K. and Maeda Y. (2003) Graft polymerization of cyclic compounds on cellulose dissolved in tetrabutylammonium fluoride / dimethylsulfoxide. Sen’I Gakkaishi 59(3):110–114

    Article  CAS  Google Scholar 

  13. Isogai A., Ishizu A. and Nakano J. (1984a). Preparation of tri-O-benzylcellulose by the use of nonaqueous cellulose solvents. J. Appl. Polym. Sci. 29: 2097–2109

    Article  CAS  Google Scholar 

  14. Isogai A., Ishizu A. and Nakano J. (1984b). Preparation of tri-O-substituted cellulose ethers by the use of nonaqueous cellulose solvents. J. Appl. Polym. Sci. 29: 3873–3882

    Article  CAS  Google Scholar 

  15. Isogai A., Ishizu A. and Nakano J. (1985). Thermal and structural properties of tri-O-substituted cellulose ethers. J. Appl. Polym. Sci. 30: 345–353

    Article  CAS  Google Scholar 

  16. Isogai A., Ishizu A. and Nakano J. (1986). Preparation of tri-O-alkylcelluloses by the use of nonaqueous cellulose solvent and their physical characteristics. J. Appl. Polym. Sci. 31: 341–352

    Article  CAS  Google Scholar 

  17. Just E.K. and Majewicz T.G. (1985). Cellulose Ethers. In: Mark H.F., Bikales N.M., Overberger C.G., Menger G. and Kroschwitz J.I. (eds) Encyclopedia of Polymer Science and Engineering. John Wiley and Sons. New York, Vol. 3, pp. 226–269

    Google Scholar 

  18. Liebert T. and Heinze Th. (1998). Synthesis path versus distribution of functional groups in cellulose ethers. Macromol. Symp. 130: 271–283

    CAS  Google Scholar 

  19. Liebert T.F. and Heinze Th. (2001). Exploitation of reactivity and selectivity in cellulose functionalization using unconventional media for the design of products showing new superstructures. Biomacromolecules 2: 1124–1132

    Article  PubMed  CAS  Google Scholar 

  20. Liebert T.F. and Heinze Th. (2005). Tailored Cellulose Esters: Synthesis and Structure Determination. Biomacromolecules 6(1): 333–340

    Article  PubMed  CAS  Google Scholar 

  21. McCormick CL, Lichatowich DK (1979) Homogeneous solution reactions of cellulose, chitin, and other polysaccharides to produce controlled-activity pesticide systems. J. Polym. Sci, Polym. Lett. Ed. 17: 479–484

    Article  CAS  Google Scholar 

  22. Marson GA, El Seoud OA (1999) A novel, efficient procedure for acylation of cellulose under homogeneous solution conditions. J. Appl. Polym. Sci. 74: 1355–1360

    Article  CAS  Google Scholar 

  23. Ramos L.A., Ciacco G.T., Assaf J.M., EL Seoud O.A. and Frollini E. (2002) Studies on dissolution and acetylation of microcrystalline, sisal, and cotton linters celluloses in DMAc/LiCl solvent system. In: Mattoso L.H.C., Frollini E. and Leão A (eds) Natural Polymers and Composites IV. EMBRAPA-USP- UNESP, Sao Paulo, Brazil, pp. 42–50

    Google Scholar 

  24. Takaragi A., Minoda M., Miyamoto T., Liu H.Q. and Zhang L.N. (1999). Reaction characteristics of cellulose in the LiCl/1,3-dimethyl-2-imidazolidinone solvent system. Cellulose 6: 93-102

    Article  CAS  Google Scholar 

  25. TAPPI Press – Viscosity of pulp (capillary viscosimeter method) (1990). In: TAPPI Test Methods 1991. Tappi Press, Atlanta, 1, Ref. T230 om–89.

Download references

Acknowledgements

E. Frollini is grateful to FAPESP (The State of São Paulo Research Foundation, Brazil) for financial support and research fellowship for L. A. Ramos and CNPq (National Council of Research, Brazil) for research fellowship.

Author information

Affiliations

Authors

Corresponding author

Correspondence to Th. Heinze.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Ramos, L.A., Frollini, E., Koschella, A. et al. Benzylation of cellulose in the solvent dimethylsulfoxide/tetrabutylammonium fluoride trihydrate. Cellulose 12, 607–619 (2005). https://doi.org/10.1007/s10570-005-9007-2

Download citation

Key words

  • Benzyl cellulose
  • Cellulose ether
  • Cellulose solvent
  • Cotton linters
  • Dimethylsulfoxide/tetrabutylammonium fluoride trihydrate
  • Sisal cellulose
  • Thermal properties