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Thermal Analysis of Acrylonitrile Polymerization and Cyclization in the Presence of N,N-Dimethylformamide

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Abstract

This paper examines the polymerization of acrylonitrile to poly(acrylonitrile)(PAN), and its cyclization, in bulk form and using N,N-dimethylformamide (DMF) as solvent in which both monomer and polymer are soluble. Thermal analysis of the resultant products after polymerization has been performed by DSC and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Scanning electron microscopy has been used to study the morphology of the resultant products and after thermal treatments. The DSC thermal curve of PAN-DMF sample is quite different from the PAN bulk sample, showing a single sharp exothermic peak associated with nitrile group polymerization (cyclization) of PAN at lower temperature (240°C) than that of bulk PAN sample (314°C). Cyclization of PAN was confirmed by IR spectroscopy. It was found that the amide molecules are difficult to eliminate completely in the product obtained after the polymerization reaction, even after prolonged heating at 110°C, and remain occluded. The formation of a complex by dipolar bonding is also possible and it is discussed. It is concluded that the amount of heat evolved as well as the temperature interval over which it is released are influenced by the chemical processing of PAN when using DMF as solvent of both monomer and polymer. Pyrolysis of these PAN samples revealed the release of occluded molecules of DMF, and several compounds containing nitrogen produced from the thermal degradation processes. All these results are interesting to know the chemical processing of carbon fibres and activated carbon fibres from PAN modified precursors.

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References

  1. O. P. Bahl and L. M. Manocha, Carbon, 13 (1974) 297.

    Google Scholar 

  2. G. A. Cooper and R. M. Mayer, J. Mater. Sci., 6 (1971) 60.

    Google Scholar 

  3. R. B. Mathur, Fibre Sci. Technol., 20 (1984) 227.

    Google Scholar 

  4. O. P. Bahl, R. B. Mathur and T. L. Dhami, Mater. Sci. Eng., 73 (1985) 105.

    Google Scholar 

  5. E. Fitzer, W. Frohs and M. Heine, Carbon, 24 (1986) 387.

    Google Scholar 

  6. T. H. Ko, H. Y. Tin and C. H. Lin, J. Appl. Polymer Sci., 35 (1988) 631.

    Google Scholar 

  7. T. H. Ko, H. Y. Tin and C. H. Lin, J. Appl. Polymer Sci., 37 (1989) 553.

    Google Scholar 

  8. E. Fitzer, Acta Polymerica, 41 (1990) 381.

    Google Scholar 

  9. R. Moreton, W. Watt and W. Johnson, Nature, 213 (1967) 690.

    Google Scholar 

  10. M. Stewart, M. Feughelman and L. M. Gillin, Nature, 235 (1972) 274.

    Google Scholar 

  11. G. Henrici-Olivé and S. Olivé, in: H. J. Cantow and G. Dall.Asta (Eds), Advances in Polymer Science, Vol. 32, Springer Verlag, Berlin 1979, p. 123.

    Google Scholar 

  12. G. Henrici-Olivé and S. Olivé, Adv. Polymer. Sci., 51 (1983) 3.

    Google Scholar 

  13. M. K. Jain and A. S. Abhiraman, J. Mater. Sci., 22 (1987) 278.

    Google Scholar 

  14. M. K. Jain, M. Balasubramanian, P. Desai and A. S. Abhiraman, J. Mater. Sci., 22 (1987) 301.

    Google Scholar 

  15. T. H. Ko and S. C. Liu, J. Mater. Sci. Lett., 7 (1988) 628.

    Google Scholar 

  16. D. J. Johnson, in Carbon Fibres, Filaments and Composites, J. L. Figuereido (Ed.), NATO ASI Series, Kluwer, Dordrecht 1990, p. 128.

    Google Scholar 

  17. L. Mascia and E. G. Paxton, Thermochim. Acta, 184 (1991) 251.

    Google Scholar 

  18. T. H. Ko and L. C. Huang, J. Mater. Sci., 27 (1992) 2429.

    Google Scholar 

  19. T. H. Ko, S. C. Liau and M. F. Lin, J. Mater. Sci., 27 (1992) 6071.

    Google Scholar 

  20. R. Y. Lin and J. Economy, Appl. Polym. Symp., 21 (1973) 143.

    Google Scholar 

  21. R. J. Martin and W. J. Ng, Water Res., 19 (1985) 1527.

    Google Scholar 

  22. T. H. Ko, P. Chiranairadul and C. H. Lin, J. Mater. Sci. Lett., 11 (1992) 6.

    Google Scholar 

  23. K. Kaneko, C. Ishii, M. Ruike and H. Kuwabara, Carbon, 30 (1992) 1075.

    Google Scholar 

  24. M. A. Ferro, E. Utrera, J. Rivera and C. Moreno, Carbon, 31 (1993) 857.

    Google Scholar 

  25. T. H. Ko and P. Chiranairadul, J. Mater. Res., 10 (1995) 1969.

    Google Scholar 

  26. G. Pan, N. Muto, M. Miyayama and H. Yanagida, J. Mater. Sci., 27 (1992) 3497.

    Google Scholar 

  27. C. D. E. Lakeman, G. Pan, N. Muto, M. Miyayama, H. Yanagida and D. A. Payne, Mater. Lett., 13 (1992) 330.

    Google Scholar 

  28. Y. Sugahara, K. Kuroda and C. Kato, J. Am. Ceram. Soc., 67 (1984) C247.

    Google Scholar 

  29. J. S. Tsai, J. Mater. Sci. Lett., 11 (1992) 140.

    Google Scholar 

  30. E. Volpert, J. Selb, F. Candau, N. Green, J. F. Argillier and A. Audibert, Langmuir, 14 (1998) 1870.

    Google Scholar 

  31. L. Sarvaranta, J. Appl. Polym. Sci., 56 (1995) 1085.

    Google Scholar 

  32. D. Eichenauer and H. Jung, Adv. Mater., 4 (1992) 215.

    Google Scholar 

  33. B. A. Keller, Ch. Löwe and R. Hany, Surface and Interface Analysis, 22 (1994) 284.

    Google Scholar 

  34. G. Cárdenas, C. Retamal and L. H. Tagle, Thermochim. Acta, 188 (1991) 221.

    Google Scholar 

  35. K. Frigge, A. Büchtemann and H. P. Fink, Acta Polymerica, 42 (1991) 322.

    Google Scholar 

  36. N. Grassie and R. McGuchan, Eur. Polym. J., 6 (1970) 1272.

    Google Scholar 

  37. J. N. Hay, J. Polym. Sci. A-1, 6 (1968) 2127.

    Google Scholar 

  38. J. W. Johnson, W. D. Potter, P. G. Rose and G. Scott, Br. Polym. J., 4 (1972) 527.

    Google Scholar 

  39. L. H. Peebles, Jr., in Encyclopedia of Chemical Technology, Wiley, New York 1979, p. 1.

    Google Scholar 

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Authors and Affiliations

  1. Instituto de Ciencia de Materiales de Sevilla (ICMSE), Centro Mixto Consejo Superior de Investigaciones Científicas (C.S.I.C.), Universidad de Sevilla, c/Americo Vespucio s/n, Isla de la Cartuja, 41092, Sevilla, Spain

    M. A. Avilés, J. L. Pérez-Rodríguez & P. J. Sánchez-Soto

  2. Departamento de Farmacia y Tecnología Farmaceútica, Facultad de Farmacia, Universidad de Sevilla, c/Profesor García González s/n, 41071, Sevilla, Spain

    J. M. Ginés

  3. Instituto de Recursos Naturales y Agrobiología de Sevilla, C.S.I.C., P.O. Box 1052, 41080, Sevilla, Spain

    J. C. del Rio

  4. Departamento de Ingeniería Civil, de Materiales y Fabricación, Escuela Técnica Superior de Ingenieros Industriales, Universidad de Málaga, 29013, Málaga, Spain

    J. Pascual

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  1. M. A. Avilés
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  2. J. M. Ginés
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  3. J. C. del Rio
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  4. J. Pascual
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  5. J. L. Pérez-Rodríguez
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  6. P. J. Sánchez-Soto
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Correspondence to P. J. Sánchez-Soto.

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Avilés, M.A., Ginés, J.M., del Rio, J.C. et al. Thermal Analysis of Acrylonitrile Polymerization and Cyclization in the Presence of N,N-Dimethylformamide. Journal of Thermal Analysis and Calorimetry 67, 177–188 (2002). https://doi.org/10.1023/A:1013706501882

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