Advertisement

Cellulose

, Volume 3, Issue 1, pp 45–61 | Cite as

Changes in substituent distribution patterns during the conversion of cellulose toO-(2-hydroxyethyl) celluloses

  • P. W. Arisz
  • H. T. T. Thai
  • J. J. Boon
  • W. G. Salomons
Article

Abstract

Monomer compositional data of a series of hydroxyethyl celluloses (HECs) with molar substitutions (MS) ranging from 0.2 to 2.4 were used to analyse the substituents in the samples. The data reveal that the reactivity of the pendant hydroxyl groups in the substituents decreases in progressed states of derivatization, and that the reactivity of the 6-O-positions is only large compared to the 2-O-positions in non-derivatized glucosyl residues. These two processes are not taken into account in any of the statistical models for the description of the substituent distribution in HECs, which shows that the assumption that the relative reaction constants of the various hydroxyl groups in HECs remain constant throughout the whole reaction is false. The occurrence of maxima in the mole fractions of the monomers was examined as a function of the MS of the samples by principal component analysis of the monomer compositional data. The results show that in the beginning phase of the derivatization mainly monosubstituted monomers are formed and that chain propagation of these substituents takes place, whereas in the progressed states of conversion mainly di- and trisubstituted moieties are formed. The changes in the reactivity of the various hydroxyl groups during the conversion of cellulose to HECs can be described by a model wherein the interactions of both NaOH and the diluents with the cellulosics are taken into account.

Keywords

cellulose hydroxyethyl cellulose methylation analysis substituent distribution 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Arisz, P. W. and Boon, J. J. (1993)Carbohydrates in the Netherlands,9, 38–42.Google Scholar
  2. Arisz, P. W., Lomax, J. A. and Boon, J. J. (1993)Carbohydr. Res.,243, 99–114.Google Scholar
  3. Dönges, R. (1990)Br. Polym. J.,23, 315–326.Google Scholar
  4. Hodges, K. L., Rester, W. E., Wiederrich, D. L. and Grover, J. A. (1979)Anal. Chem.,51, 2172–2176.Google Scholar
  5. Just, E. K. and Majewicz, T. G. (1985) InEncyclopedia of Polymer Science and Engineering, 2nd edn, vol. 3 (J. I. Kroschwitz, ed.) New York: Wiley, pp. 226–269.Google Scholar
  6. Klug, E. D. (1966) U.S. Pat. 3, 278, 521 (Oct. 11, 1966 to Hercules Inc.)Google Scholar
  7. Lindberg, B., Lindquist, U. and Stenberg, O. (1987)Carbohydr. Res.,5, 207–214.Google Scholar
  8. Lorand, E. J. and Georgi, E. A. (1937)J. Am. Chem. Soc.,59, 1166–1170.Google Scholar
  9. Ramnäs, O. and Samuelson, O. (1973)Svensk Papperstendning,15, 569–571.Google Scholar
  10. Reuben, J. (1984)Macromolecules,17, 156–161.Google Scholar
  11. Reuben, J. and Casti, T. E. (1987)Carbohydr. Res.,163, 91–98.Google Scholar
  12. Spurlin, H. M. (1939)J. Am. Soc.,61, 2222–2227.Google Scholar
  13. Spurlin, H. M. (1954) InCellulose and Cellulose Derivatives, Part II, (E. Ott, H. M. Spurlin and M. W. Graffin, eds.) New York: Interscience, p. 673–712.Google Scholar
  14. Stratta, J. J. (1963)Tappi J.,46, 717–722.Google Scholar
  15. Windig, W., Kistemaker, P. G. and Haverkamp, J. (1981/1982).J. Anal. Appl. Pyrolysis,3, 199–212.Google Scholar
  16. Yokota, H. (1985)J. Appl. Polym. Sci.,30, 263–277.Google Scholar
  17. Yokota, H. (1986a)J. Appl. Polym. Sci.,32, 3423–3433.Google Scholar
  18. Yokota, H. (1986b)Cellulose Chem. Technol.,20, 315–325.Google Scholar

Copyright information

© Blackie Academic & Professional 1996

Authors and Affiliations

  • P. W. Arisz
    • 1
  • H. T. T. Thai
    • 1
  • J. J. Boon
    • 1
  • W. G. Salomons
    • 2
  1. 1.FOM Institute for Atomic and Molecular PhysicsSJ AmsterdamThe Netherlands
  2. 2.HerculesLH ZwijndrechtThe Netherlands

Personalised recommendations