Polymer Bulletin

, Volume 38, Issue 5, pp 537–543 | Cite as

Studies of moisture induced crosslinking in a novel vinyl ether-maleic anhydride copolymer

  • B. Rema
  • S. Ramakrishnan
Article

Summary

A novel vinyl ether, 2,2-dimethyl-4-vinyloxymethyl-l,3-dioxolane (DMVMD), that has a dimethyl ketal protected vicinal diol functionality, was synthesizied from readily available starting materials, such as glycerol, acetone and acetylene. Copolymerisation of DMVMD with maleic anhydride (MAH) in various molar ratios was carried out using a free radical initiator. The composition of the copolymer was established by conductometric titration, and was found to be 1:1 irrespective of the monomer feed composition thus establishing its alternating nature. The copolymer formed clear free standing films upon solvent casting which became insoluble upon prolonged exposure to ambeint atmosphere. The insolubility is ascribed to moisture induced crosslinking. A plausible mechanism for the crosslinking involves the hydrolysis of some of the anhydride groups, followed by acid catalysed deketalization, and then by the reaction of the alcoholic groups, thus generated, with the residual anhydride to give ester crosslinks. This hypothesis was confirmed both by model reactions and insitu FT-IR studies.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    M. Miyamoto, M. Sawamoto and T. Higashimura, Macromolecules 17, 265 (1984).CrossRefGoogle Scholar
  2. 2.
    T. Higashimura and M. Sawamoto in Comprehensive Polymer Science, Vol 3 (partl). G. W. Allen and J. C. Bevington Eds. Pergamon Press, Oxford, (1989) chapter 42, p. 673.Google Scholar
  3. 3.
    M. Minoda, M. Sawamoto and T. Higashimura, Macromolecules 20, 2045 (1987).CrossRefGoogle Scholar
  4. 4.
    J. M. G. Cowie in Comprehensive Polymer Science Vol 4, G. W. Allen and J. C. Bevington, Eds. Pergamon Press, Oxford, (1989) chapter 22, p. 377Google Scholar
  5. 5.
    P. Keller, Makromol Chem., Rapid Commun., 6, 707 (1985)CrossRefGoogle Scholar
  6. 6.
    Although the synthesis of this monomer and some attempts to homopolymerize it was reported in the early literature by Shoshtakovskii et al., very little details were provided. M. F. Shoshtakovskii, A. S. Atavin, N. P. Vasiliev, P. I. Dubova, L. P. Dmitrieva and A. I. Mikhaleva, Izv. Akad. Nauk. SSSR, Ser. Khim. 7, 1232 (1966)Google Scholar
  7. 7.
    B. Herald, P. Josef, W. Christian (Bayer AG) Eur. Pat. Appl. EP 307701 March (1989). CA: lll:P176301y. B. Herald, P. Josef, W. Christian (Bayer AG) Eur. Pat. Appl. EP 284,953 October (1988). CA: 110:P194759n.Google Scholar
  8. 8.
    K. Fujimori and N. A. Wickratnasinghe, J. Natn. Sei. Coun. Srilanka 7, 45, (1979)Google Scholar
  9. 9.
    J. Klein and K. Blumberg, Makromol. Chem., Rapid Commun. 7, 621 (1986)CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 1997

Authors and Affiliations

  • B. Rema
    • 1
  • S. Ramakrishnan
    • 1
  1. 1.Department of Inorganic and Physical ChemistryIndian Institute of ScienceBangaloreIndia

Personalised recommendations