Skip to main content
Log in

Dissolution of cellulose in ethylene diamine/salt solvent systems

  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

Investigation of the dissolution of cellulose in Ethylene Diamine (EDA)/Potassium thiocyanate (KSCN) solutions by infrared spectroscopy (FTIR) and thermal analysis (DSC) indicated that changes to the solvent during freeze thaw cycling of mixtures was consistent with increased interaction between cellulose and solvent. Thermal transitions in the system, however, occurred at temperatures outside the range used in thermal cycling to promote dissolution. Further exploration of the dissolution and mixing process indicated that mixing was the limiting step in solution formation. The dissolution of two types of cellulose with different molecular weights (Degree of Polymerization (DP)=210 and >1000) was studied using EDA/KSCN solution as the solvent. The solubility and the dissolution rate of cellulose depended on both the solvent composition and cellulose molecular weight. Cellulose could dissolve faster in the solvent with lower salt concentration but the highest cellulose concentration was obtained in the solvent with 30~35% KSCN. Rheological measurements showed that cellulose solutions exhibited viscous solution behavior at low KSCN concentration but primarily elastic behavior at high salt concentration.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  • Aminuddin N. 1993. Studies on the Dissolution and Fiber Formation of Cellulose in Ammonia/Ammonium Thiocyanate. Department of Textile Engineering, Chemistry and Science, North Carolina State University, Raleigh

  • Aminuddin N. 1998. Ammonia/Ammonium Thiocyanate–Cellulose System: Dissolution, Viscoelastic Behaviour and Fiber Formation. Fiber and Polymer Science. North Carolina State University, Raleigh

  • Baeza J. and Freer J. 2001. Chemical characterization of wood and its components. In: Hon D.N.-S., Shiraishi N. (eds), Wood and Cellulosic Chemistry. Marcel Dekker, New York, pp. 295–299

    Google Scholar 

  • Brendler E., Fischer S., Leipner H. (2001) 7Li NMR as probe for solvent–cellulose interactions in cellulose dissolution. Cellulose 8: 283–288

    Article  CAS  Google Scholar 

  • Ciacco G.T., Liebert T.F., Frollini E., Heinzel T.J. (2003) Application of the solvent dimethyl sulfoxide/tetrabutyl-ammonium fluoride trihydrate as reaction medium for the homogeneous acylation of Sisal cellulose. Cellulose 10: 125–132

    Article  CAS  Google Scholar 

  • Cuculo J.A., Aminuddin N., Frey M.W. (2000) 8. Solvent spun cellulose fibers. In: Salem D. (ed.), Structure Formation in Polymeric Fibers. Hanser Publishers, Munich, pp. 296–328

    Google Scholar 

  • Cuculo J.A., Smith B., Sangwatanaroj U., Stejskal E.O., Sankar S.S. (1994a) A study on the mechanism of dissolution of the cellulose/NH3/NH4SCN system 1. J. Polym. Sci. Polym. Chem. 32: 229–240

    Article  CAS  Google Scholar 

  • Cuculo J.A., Smith B., Sangwatanaroj U., Stejskal E.O., Sankar S.S. (1994b) A study on the mechanism of dissolution of the cellulose/NH3/NH4SCN system 2. J. Polym. Sci. Polym. Chem. 32: 241–248

    Article  CAS  Google Scholar 

  • de Groot A.W., Guinnup D.E., Theil M.H., Cuculo J.A. (1991a) Light-scattering studies on solutions of cellulose in the ammonia/ammonium thiocyanate solvent system I classical light-scattering. J. Polym. Sci. B Polym. Phys. 29: 547–556

    Article  Google Scholar 

  • de Groot A.W., Guinnup D.E., Theil M.H., Cuculo J.A. (1991b) Light-scattering studies on solutions of cellulose in the ammonia/ammonium thiocyanate solvent system II quasielastic light-scattering and liquid crystal study. J. Polym. Sci. B Polym. Phys. 29: 557–564

    Article  Google Scholar 

  • Frey M.W., Khan S, Cuculo J.A. (1996a) Rheology and gelation of cellulose/ammonia/ammonium thiocyanate solutions. J. Polym. Sci. B Polym. Phy. 34: 2375–2381

    Article  CAS  Google Scholar 

  • Frey M.W., Spontak R.A., Cuculo J.A. (1996b) Morphological characteristics of the lyotropic and gel phases in the cellulose/NH3/NH4SCN system. J. Polym. Sci. B Polym. Phy. 34: 2049–2058

    Article  CAS  Google Scholar 

  • Frey M.W., Chan H., Carranko K. (2005) Rheology of cellulose/KSCN/ethylene diamine solutions and coagulation into fibers and films. J. Polym. Sci. B Polym. Phy. 43: 2013–2022

    Article  CAS  Google Scholar 

  • Frey M.W., Theil M.H. (2004) Calculated phase diagrams for cellulose/ammonia/ammonium thiocyanate solutions in comparison to experimental results. Cellulose 11:53–63

    Article  CAS  Google Scholar 

  • Hattori K., Abe E., Yoshida T., Cuculo J.A. (2004) New solvents for cellulose. II. Ethylenediamine/thiocyanate salt system. Polym. J. 36: 123–130

    Article  CAS  Google Scholar 

  • Hattori K., Cuculo J.A., Hudson S.M. (2002) New solvents for cellulose: hydrazine/thiocyanate salt system. J. Polym. Sci. A Polym. Chem. 40: 601–611

    Article  CAS  Google Scholar 

  • Miller-Chou B.A., Koenig J.L. (2003) A review of polymer dissolution. Prog. Polym. Sci. 28: 1223–1270

    Article  CAS  Google Scholar 

  • Ramos L.A., Assaf J.M., ElSeoud O.A., Frollini E. (2005a) Influence of the supramolecular structure and physicochemical properties of cellulose on its dissolution in a lithium chloride/N,N-dimethylacetamide solvent system. Biomacromolecules 6: 2638–2647

    Article  CAS  Google Scholar 

  • Ramos L.A., Frollini E. and Heinze T. 2005b. Carboxymethylation of cellulose in the new solvent dimethyl sulfoxide/tetrabutylammonium fluoride. Carbohyd. Polym. 60: 259–267

  • Swatloski R.P., Spear S.K., HolbreyJ.D. and Rogers R.D. 2002.Dissolution of cellulose with ionicliquids. J. Am. Chem. Soc. 124: 4974-4975.

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Margaret W. Frey.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Frey, M.W., Li, L., Xiao, M. et al. Dissolution of cellulose in ethylene diamine/salt solvent systems. Cellulose 13, 147–155 (2006). https://doi.org/10.1007/s10570-006-9062-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-006-9062-3

Key words

Navigation