Advertisement

Reactions of Small Radicals with Polymers During Degradation

  • N. A. Weir
Chapter

Summary

Small free radicals are often produced in degradation reactions, and their fates have been comparatively neglected. This chapter considers radical production in degradation reactions, reactions of small free radicals with polymers, and the importance of these in initiating secondary reactions. Factors influencing radical reactivity are also discussed, and a model which represents simultaneous reaction and diffusion of small radicals is introduced. Quantitative kinetic data for photochemical reactions in the solid state, particularly those involving hydrogen abstraction, can be obtained, and rate constants obtained for reactions of radicals with styrene polymers are discussed.

Keywords

Thermal Degradation Free Volume Chain Scission Degradation Reaction Abstraction Reaction 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Rånby, B. and Rabek, J. F. Photodegradation, Photooxidation and Photostabilisation of Polymers. New York, Wiley, 1975.Google Scholar
  2. 2.
    Rånby, B. and Rabek, J. F. ESR Spectroscopy in Polymer Research. Berlin, Springer-Verlag, 1977.CrossRefGoogle Scholar
  3. 3.
    Jellinek, H. H. H. (ed.) Aspects of Degradation and Stabilization of Polymers. New York, Elsevier, 1978.Google Scholar
  4. 4.
    McKellar, J. F. and Allen, N. S. Photochemistry of Man Made Polymer. London, Applied Science Publishers, 1979.Google Scholar
  5. 5.
    Jellinek, H. H. G. (ed.) Degradation and Stabilization of Polymers—1. Amsterdam, Elsevier, 1983.Google Scholar
  6. 6.
    Partridge, R. H. J. Chem. Phys., 52 (1970), 2845, 2491.Google Scholar
  7. 7.
    Togaya, T., Amemiya, H., Shinohara, I., Hagiwara, M. and Kagiya, T., J. Polym. Sci., Polym. Chem. Ed., 13 (1975), 2843.ADSCrossRefGoogle Scholar
  8. 8.
    Helbert, J. N., Poindexter, E. H., Stahl, G. A., Chen, C. Y. and Dittman, C. U., Polym. Eng. Sci., 20 (1980), 630.CrossRefGoogle Scholar
  9. 9.
    Schnabel, W. and Rosiak, J., Europ. Polym. J., 20 (1984), 1159.CrossRefGoogle Scholar
  10. 10.
    Starns, W. H. Amer. Chem. Soc. Symp. Ser.151 (1981), 197.Google Scholar
  11. 11.
    Owen, E. D. Developments in Polymer Photochemistry, ed. N. S. Allen, p. 165. London, Applied Science Publishers, 1982.Google Scholar
  12. 12.
    Decker, C. and Balandier, M. Europ. Polym. J., 18 (1982), 1085.CrossRefGoogle Scholar
  13. 13.
    Decker, C. Europ. Polymer J., 20 (1984), 149.CrossRefGoogle Scholar
  14. 14.
    Lucas, R., Pradova, O., Michalcova, J. and Paleckova, V. J. Polym. Sci., Polym. Lett. Ed., 23 (1985), 85.ADSCrossRefGoogle Scholar
  15. 15.
    Mullik, S. U. and Norrish, R. G. W. Proc. Roy. Soc., A344 (1975), 1.ADSGoogle Scholar
  16. 16.
    Torikai, A., Takeuchi, T. and Fueki, K. Polym. Photochem., 3 (1982), 307.CrossRefGoogle Scholar
  17. 17.
    Weir, N. A. Developments in Polymer Degradation—4, p. 143, ed. N. Grassie. London, Applied Science Publishers, 1982.Google Scholar
  18. 18.
    Gupta, A., Liang, R., Tsay, F. D. and Moncanin, J. Macromolecules, 13 (1980), 1696.ADSCrossRefGoogle Scholar
  19. 19.
    Chandros, E. A., Reichmans, E., Wilkins, C. W. and Hartless, R. L. Can. J. Chem., 61 (1983), 817.CrossRefGoogle Scholar
  20. 20.
    McGill, W. J. and Ackerman, L. J. Polym. Sei., Polym. Chem. Ed., 12 (1974), 1541.CrossRefGoogle Scholar
  21. 21.
    McNeill, I.C. and Zulfiqar, M. Polym. Degr. Stabil., 10 (1985), 189.CrossRefGoogle Scholar
  22. 22.
    Rujimethabas, M. and Weir, N. A. Europ. Polym. J., 19 (1983), 779.CrossRefGoogle Scholar
  23. 23.
    Tanaka, H. and Otsu, T. J. Polym. Sei., Polym. Chem. Ed., 15 (1977), 2613.CrossRefGoogle Scholar
  24. 24.
    Otsu, T., Tanaka, H. and Wasaki, H. Polymer, 20 (1979), 55.CrossRefGoogle Scholar
  25. 25.
    Browning, H. L., Ackerman, H. D. and Patton, H. W. J. Polym. Sei., Al (1966), 1433.Google Scholar
  26. 26.
    Rheinöhl, V., Sedlar, J. and Navratil, M. Polym. Photochem., 1 (1981), 165.CrossRefGoogle Scholar
  27. 27.
    Jellinek, H. H. G. and Bastein, I. J. Can. J. Chem., 39 (1961), 2056.Google Scholar
  28. 28.
    Geuskens, G., Bastin, P., Lu-Vinh, Q. and Rens, M. Polym. Degr. Stabil., 3 (1981), 295.CrossRefGoogle Scholar
  29. 29.
    Roginsky, V. A. Developments in Polymer Degradation—5, p. 193, ed. N. Grassie. London, Applied Science Publishers, 1984.Google Scholar
  30. 30.
    Geuskens, G. and Kabamba, M. S. Polym. Degr. Stabil, 4 (1982), 69.CrossRefGoogle Scholar
  31. 31.
    Lola, D. and Rabek, J. F. Europ. Polym. J., 17 (1981), 7.CrossRefGoogle Scholar
  32. 32.
    Geuskens, G., Baeyens-Volant, D., Delaunois, G., Lu Vinh, Q., Piret, W. and David, C. Europ. Polym. J., 14 (1978), 299.CrossRefGoogle Scholar
  33. 33.
    Geuskens, G. and David, C. Pure Appl. Chem., 51 (1979), 233.CrossRefGoogle Scholar
  34. 34.
    Ng, H. C. and Guillet, J. E. Macromolecules, 11 (1978), 929.ADSCrossRefGoogle Scholar
  35. 35.
    Bousquet, J. A. and Fouassier, J. P. J. Polym. Sei., Polym. Chem. Ed., 22 (1984), 3865.CrossRefGoogle Scholar
  36. 36.
    Gladyshev, G. P. and Vasnetsova, O. A. Developments in Polymer Stabilization6, p. 295, ed. G. Scott, London, Applied Science Pub- Ushers, 1983.Google Scholar
  37. 37.
    Ellis, T. S. and Still, R. H. J. Appl. Polym. Sei., 23 (1979), 2855, 2871.Google Scholar
  38. 38.
    Mehdi, M. A. S. and Still, R. H. Polym. Degr. Stabil., 10 (1985), 369.CrossRefGoogle Scholar
  39. 39.
    Mehdi, M. A. S. and Still, R. H. Polym. Degr. Stabil., 11 (1985), 99.CrossRefGoogle Scholar
  40. 40.
    Braun, D. Developments in Polymer Degradation3, p. 101, ed. N. Grassie, London, Applied Science Publishers, 1981.Google Scholar
  41. 41.
    Grassie, N., Johnston, A. and Scotney, A. Polym. Degr. Stabil., 4 (1982), 173.CrossRefGoogle Scholar
  42. 42.
    Bajaj, B. and Padmanabon, M. Europ. Polym. J., 21 (1985), 93.CrossRefGoogle Scholar
  43. 43.
    Dickens, B. Polym. Degr. Stabil., 6 (1984), 211.CrossRefGoogle Scholar
  44. 44.
    Kubota, H., Kimura, M. and Ogiwara, Y. J. Polym. Sei., Polym. Lett. Ed., 23 (1985), 121.Google Scholar
  45. 45.
    Beavan, S. W. and Schnabel, W. Macromolecules, 11 (1978), 782.ADSCrossRefGoogle Scholar
  46. 46.
    Beavan, S. W. and Schnabel, W. Europ. Polym. J., 14 (1978), 385.CrossRefGoogle Scholar
  47. 47.
    Seiichi, T. and Schnabel, W. Polym. Photochem., 3 (1983), 203.CrossRefGoogle Scholar
  48. 48.
    Easton, M. J. and MacCallum, J. R. Polym. Degr. Stabil., 3 (1981), 229.CrossRefGoogle Scholar
  49. 49.
    Wolinski, L., Witkowski, K. and Turzynski, Z. Makromol. Chem., 185 (1984), 725.CrossRefGoogle Scholar
  50. 50.
    Gunder, O. A. and Koda, V. S. Radiokhim., 11 (1969), 119.Google Scholar
  51. 51.
    Shimizu, Y. and Mitsui, H., J. Polym. Sei., Polym. Chem. Ed., 17 (1979), 2307.CrossRefGoogle Scholar
  52. 52.
    Slivinskas, J. A. and Guillet, J. E. J. Polym. Sei., Polym. Chem. Ed., 11 (1975), 3057.CrossRefGoogle Scholar
  53. 53.
    Farahani, M. and Weir, N. A. Unpublished work.Google Scholar
  54. 54.
    Weir, N. A. Europ. Polym. J., 14 (1978), 9.CrossRefGoogle Scholar
  55. 55.
    Pryor, W. A., Tong, F. Y., Tong, R. H. and Church, D. F. J. Amer. Chem. Soc., 104 (1982), 2885.CrossRefGoogle Scholar
  56. 56.
    Delman, A. D., Landy, M. and Simms, B. B. J. Polym. Sei., A17 (1969), 3375.Google Scholar
  57. 57.
    McNeill, I. C., Developments in Polymer Degradation1, p. 171, ed. N. Grassie. London, Applied Science Publishers, 1977.Google Scholar
  58. 58.
    Grassie, N. and Leeming, W. B. H. Eur. Polym. J., 11 (1975), 819.CrossRefGoogle Scholar
  59. 59.
    Dobson, B. and McNeill, I. C. J. Polym. Sei., Polym. Chem. Ed.,14 (1976), 353.Google Scholar
  60. 60.
    Camino, J., Costa, L. and Trossarelli, L. Polym. Degr. Stabil., 4 (1982), 39.CrossRefGoogle Scholar
  61. 61.
    Kiang, J. K. Y., Uden, P. C. and Chien, J. C. W. Polym. Degr. Stabil., 2 (1980), 113.CrossRefGoogle Scholar
  62. 62.
    Carabine, M. D., Cullis, C. F. and Groome, I. J. Proc. Roy. Soc., Lond. A, 324 (1971), 217.ADSCrossRefGoogle Scholar
  63. 63.
    Alsheh, P. and Maron, G. J. Appl. Polym. Sei., 22 (1978), 3177.CrossRefGoogle Scholar
  64. 64.
    Camino, J. and Costa, L., Polym. Degr. Stabil., 4 (1982), 167.CrossRefGoogle Scholar
  65. 65.
    Ranby, B. and Lucki, J. Pure Appl. Chem., 52 (1980), 295.CrossRefGoogle Scholar
  66. 66.
    Arnaud, R. and Lemaire, J. Developments in Polymer Degradation—2, p. 159, ed. N. Grassie. London, Applied Science Publishers, 1979.Google Scholar
  67. 67.
    Scott, G. and Tahon, M. Europ. Polym. J., 11 (1975), 535.CrossRefGoogle Scholar
  68. 68.
    Encinos, M. V. and Lissi, E. A. J. Photochem., 20 (1982), 151.Google Scholar
  69. 69.
    Garton, A., Carlsson, D. J. and Wiles, D. M. Makromol. Chem., 181 (1980), 1841.CrossRefGoogle Scholar
  70. 70.
    Wiles, D. M. and Carlsson, D. J. Polym. Degr. Stabil., 3 (1981), 61.CrossRefGoogle Scholar
  71. 71.
    Tang, L., Sallet, D. and Lemaire, J. Macromolecules, 15 (1982), 1432.ADSCrossRefGoogle Scholar
  72. 72.
    Behzadi, A., Borgwardt, U., Henglein, A., Schamberg, E. and Schnabel, W. Ber. Bunsenges. Phys. Chem., 74 (1970), 649.Google Scholar
  73. 73.
    Niki, E. and Kamiya, Y. J. Amer. Chem. Soc., 96 (1974), 1591.CrossRefGoogle Scholar
  74. 74.
    Tanner, D. D. and Rahim, P. M. J. Amer. Chem. Soc., 104 (1982), 225.CrossRefGoogle Scholar
  75. 75.
    Brower, K. R. J. Org. Chem., 45 (1980), 1004.CrossRefGoogle Scholar
  76. 76.
    Griva, A. P., Desinova, L. N. and Desinov, E. T. Russ. J. Phys. Chem., 58 (1984), 349.Google Scholar
  77. 77.
    Niki, E., Decker, C. and Mayo, F. R. J. Polym. Sei., Polym. Chem. Ed.,11 (1973), 2813.CrossRefGoogle Scholar
  78. 78.
    Niki, E. and Kamiya, Y. J. Amer. Chem. Soc., 96 (1974), 2129.CrossRefGoogle Scholar
  79. 79.
    Guillet, J. E. Polymer Photophysics and Photochemistry. Cambridge University Press, 1985.Google Scholar
  80. 80.
    Jellinek, H. H. G. Polym. J., 4 (1973), 489.CrossRefGoogle Scholar
  81. 81.
    Jellinek, H. H. G. and Lichorat, J. J. Polym. J., 12 (1980), 347.CrossRefGoogle Scholar
  82. 82.
    Grimm, H. J. and Thomas, E. L. Polymer, 26 (1985), 127.Google Scholar
  83. 83.
    Cohen, M. H. and Turnbull, D. J. Chem. Phys., 31 (1959), 1164.ADSGoogle Scholar
  84. 84.
    Kawakami, M., Iwanga, H. and Kagawa, S. Bull. Chem. Soc. Japan, 54 (1981), 869.CrossRefGoogle Scholar
  85. 85.
    Toi, K., Takeuchi, K. and Tokuda, T. J. Polym. Sci., Polym. Phys. Ed., 18 (1980), 189.ADSCrossRefGoogle Scholar
  86. 86.
    Spiess, H. W. Colloid and Polymer Science, 261 (1984), 193.CrossRefGoogle Scholar
  87. 87.
    Greenwood, R. and Weir, N. A. J. Appl. Polym. Sci., 19 (1974), 1409.CrossRefGoogle Scholar
  88. 88.
    Zantas, A. A. and Pinto, J. A. J. Amer. Chem. Soc., 94 (1972), 7590.CrossRefGoogle Scholar
  89. 89.
    Weir, N. A. and Milkie, T. H. Europ. Polym. J., 16 (1980), 141.CrossRefGoogle Scholar
  90. 90.
    Niki, E., Ohto, N., Kanauchi, T. and Kamiya, Y. Europ. Polym. J., 16 (1980), 559.CrossRefGoogle Scholar
  91. 91.
    Benson, S. W., Thermochemical Kinetics, 2nd edn. New York, Wiley, 1976.Google Scholar
  92. 92.
    Niki, E. and Kamiya, Y. J. Org. Chem., 38 (1973), 1403.CrossRefGoogle Scholar
  93. 93.
    Ohto, N., Niki, E. and Kamiya, Y. JCS Perkin, II (1977), 1416.CrossRefGoogle Scholar
  94. 94.
    Dulog, L. and David, K. H. Makromol. Chem., 177 (1976), 1717.CrossRefGoogle Scholar
  95. 95.
    Chenier, J. H. B., Tong, S. B. and Howard, J. A. Can. J. Chem., 56 (1978), 3047.CrossRefGoogle Scholar
  96. 96.
    Weir, N. A. and Milkie, T. H. Polym. Degr. Stabil, 2 (1980), 225.CrossRefGoogle Scholar
  97. 97.
    Okhatsa, Y., Tanaka, T. and Tsurata, T. Makromol. Chem., 183 (1982), 1225.CrossRefGoogle Scholar
  98. 98.
    Lissi, E. A. and Leon, A. J. Polym. Sci., Polym. Chem. Ed., 17 (1979), 3023.ADSCrossRefGoogle Scholar
  99. 99.
    Zaporozhkaya, O. A., Yasina, L. L. and Pudov, V. S. J. Phys. Chem., Russia, 53 (1979), 1394.Google Scholar
  100. 100.
    Weir, N. A. and Rujimethabas, M. Europ. Polym. J., 18 (1982), 813.CrossRefGoogle Scholar
  101. 101.
    Rujimethabas, M. and Weir, N. A. Europ. Polym. J., 19 (1983), 779.CrossRefGoogle Scholar
  102. 102.
    Weir, N. A. and Rujimethabas, M. Europ. Polym. J., 21 (1985), 493.CrossRefGoogle Scholar
  103. 103.
    Jellinek, H. H. G. and Lipovac, S. N. Macromolecules, 3 (1970), 231.ADSCrossRefGoogle Scholar
  104. 104.
    Billingham, N. C. and Walker, T. J. J. Polym. Sci., Poly. Chem. Ed., 13 (1975), 1209.CrossRefGoogle Scholar
  105. 105.
    Bondi, A. J. Phys. Chem., 68 (1964), 441.CrossRefGoogle Scholar
  106. 106.
    Huggenberger, C. and Fischer, H. Helv. Chim. Acta, 64 (1981), 338.CrossRefGoogle Scholar
  107. 107.
    Kerr, J. A. and Moss, S. J. Handbook of Bimolecular and Termolecular Gas Reactions, Vol. 1. Boca Raton, Florida, CRC Press (1981).Google Scholar
  108. 108.
    Ingold, K. U. Free Radicals, Vol. 1, ed. J. Kochi. New York, Wiley, 1973.Google Scholar
  109. 109.
    Stepanov, A. A., Tkatchenko, V. A. and Tolkatchev, V. A. Int. J. Chem. Kinet., 10 (1978), 637.CrossRefGoogle Scholar

Copyright information

© Elsevier Applied Science Publishers 1987

Authors and Affiliations

  • N. A. Weir
    • 1
  1. 1.Chemistry DepartmentLakehead UniversityCanada

Personalised recommendations