A study of polypyrrole/poly(N-isopropylacrylamide-co-acrylamide) dispersions: Electrically conducting polymer dispersions stabilised by copolymers with lower critical solution temperatures

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Brian R. Saunders, Jennifer M. Saunders, James Mrkic and Eric H. Dunlop


Abstract

Aqueous dispersions have been studied where the particles consist of an electrically conducting polymer (polypyrrole, PPy) and anchored temperature-responsive sheaths. The sheaths consist of poly(N-isopropylacrylamide-co-acrylamide) [poly(NP-xAM) (x=35, 50 and 65)] copolymer [where x represents the mol% of acrylamide (AM) used during synthesis]. The properties of PPy/PAM (PAM=polyacrylamide) and PPy/PVA [PVA=poly(vinyl alcohol)] dispersions were also investigated for comparison. Photon correlation spectroscopy (PCS) measurements show that the PPy/poly(NP-xAM) dispersions exhibit temperature induced contraction of the sheaths over the temperature range 30–70°C. The extent of contraction increases with decreasing value of x. Dispersion stability in pure water and aqueous NaCl solution was found to be due to electrosteric and steric stabilisation, respectively. Flocculation in the presence of electrolyte (NaCl) was studied using PCS and optical density measurements. PPy/poly(NP-35AM) dispersions in aqueous 0.10 and 1.90 M NaCl solution exhibited upper critical flocculation temperatures (UCFT) of 58 and 30°C, respectively. These values were indistinguishable from the lower critical solution temperature (LCST) for poly(NP-35AM) copolymer measured under identical conditions. Flocculation occurred due to segment–segment attraction of the sheaths under worse than ϑ-solvency conditions. Theoretical calculations indicate that synthesis of stable PPy dispersions requires a minimum sheath thickness (δ) to core radius (a) ratio of δ/a ∽0.30 when ferric chloride is the oxidant. Electrical conductivity measurements of pressed pellets yielded room temperature conductivities in the range 0.0035–0.14 S cm-1; increased levels of AM incorporation within the sheaths increased the conductivity.


References

  1. A. F. Diaz, K. K. Kanazawa and G. P. Gardini, J. Chem. Soc., Chem. Commun., 1979, 635 RSC.
  2. G. B. Street, in Handbook of Conducting Polymers, ed. T. A. Skotheim, Dekker, New York, 1986, vol. 1 Search PubMed.
  3. B. R. Saunders, K. S. Murray, R. J. Fleming, R. Cervini and N. S. Allen, in Handbook of Organic Conductive Molecules and Polymers, ed. H. S. Nalwa, John Wiley and Sons, Chichester, 1997, vol. 3 Search PubMed.
  4. A. O. Patil, Y. Ikenoue, F. Wudl and A. J. Heeger, J. Am. Chem. Soc., 1987, 109, 1858 CrossRef CAS.
  5. S. P. Armes and B. Vincent, J. Chem. Soc., Chem. Commun., 1987, 289 Search PubMed.
  6. S. P. Armes, J. F. Miller and B. Vincent, J. Colloid Interface Sci., 1987, 118, 411.
  7. G. Markham, T. M. Obey and B. Vincent, Colloids Surface. A, 1990, 51, 239 Search PubMed.
  8. R. B. Bjorklund and B. Liedberg, J. Chem. Soc., Chem. Commun., 1986, 1293 RSC.
  9. P. M. Beadle, S. P. Armes, S. J. Greaves and J. F. Watts, Langmuir, 1996, 12, 1784 CrossRef CAS.
  10. M. L. Digar, S. N. Battacharyya and B. M. Mandal, J. Chem. Soc., Chem. Commun., 1992, 18 RSC.
  11. P. M. Beadle and S. P. Armes, Synth. Met., 1993, 55–57, 1114 CrossRef.
  12. P. S. Mumick and C. L. McCormick, Polym. Eng. Sci., 1994, 34, 1419 Search PubMed.
  13. T. G. Park and A. S. Hoffman, Macromolecules, 1993, 26, 5045 CrossRef CAS.
  14. M. Shibayama, T. Tanaka and C. C. Han, J. Chem. Phys., 1992, 97, 6829 CrossRef CAS.
  15. B. R. Saunders and B. Vincent, J. Chem. Soc., Faraday Trans., 1996, 92, 3385 RSC.
  16. P. W. Zhu and D. H. Napper, J. Colloid Interface Sci., 1994, 164, 489 CrossRef CAS.
  17. P. G. de Gennes, C. R. Acad. Sci. Ser.2, 1991, 313, 1117 Search PubMed.
  18. L. B. Valdes, Proc. IRE, 1954, 42, 420 Search PubMed.
  19. J. Brandup, Polymer Handbook, ed. J. Brandup and E. H. Immergut, Interscience, 2nd edn., 1976, p. VII/8 Search PubMed.
  20. S. K. Chatterjee, E. Prokopova and M. Bohdanecky, Eur. Polym. J., 1978, 14, 664 CrossRef.
  21. B. R. Saunders, K. S. Murray, R. J. Fleming and Y. Korbatieh, Chem. Mater., 1993, 5, 809 CrossRef CAS.
  22. D. H. Napper, Polymeric stabilisation of colloidal dispersions, Academic Press, London, 1983 Search PubMed.
  23. D. J. Shaw, Introduction to colloid and surface chemistry, Butterworth, 1994 Search PubMed.
  24. Z. Rawi, J. Mykytiuk and S. P. Armes, Colloids Surf. A, 1992, 68, 215 CrossRef CAS.
  25. H. Eisazadeh, G. Spinks and G. G. Wallace, Polymer, 1994, 35, 3801 CrossRef CAS.
  26. S. F. Lascelles and S. P. Armes, J. Mater. Chem., 1997, 7, 1339 RSC.
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