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Chemistry pp 1-67 | Cite as

Synthesis and modification of polymers containing a system of conjugated double bonds

  • Sebastiano Cesca
  • Aldo Priola
  • Mario Bruzzone
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 32)

Abstract

Two broad classes of hydrocarbon copolymers containing a system of conjugated double bonds randomly distributed in the chains, i. e.,
  1. (i)

    ethylene-propylene based terpolymers and

     
  2. (ii)

    triene-isobutene copolymers.

     

can be obtained by using coordinate and cationic catalysts, respectively. The diene functionality can be linear and inserted in the chains of (ii) or pendant-endocyclic, -exocyclic and -linear when it belongs to (i). The reactivity of the diene groups in typical reactions, i. e., with free radicals, chlorinating or oxidizing agents, during Diels-Alder additions, was investigated with both polymer and low molecular weight model compounds for elucidating the reaction mechanism of the reactions considered. With the results obtained one may conclude that in several cases the polymers investigated possess a reactivity which is qualitatively and quantitatively different from that shown by the corresponding polymers containing monoenic unsaturation. Furthermore, the peculiar reactivity of each dienic group permits the choice of functionality which is most suitable for the post-modification reaction which is desired.

Keywords

Double Bond Model Compound Butyl Rubber Radical Grafting Diene System 
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.

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V References

  1. 1.
    Natta, G., Mazzanti, G., Corradini, P.: Atti Accad. Naz. Lincei, Red. Classe, Sci. Fis. Mat. Nat. 25 (1–2) 3 (1958)Google Scholar
  2. 2.
    Chauser, M. G.: Russ. Chem. Rev. 45, 348 (1976)Google Scholar
  3. 3.
    Bell, V. L.: J. Polymer Sci. A2, 5291 (1964)Google Scholar
  4. 4.
    Baker, W. P.: J. Polymer Sci. A-1, 655 (1963)Google Scholar
  5. 5.
    Krentsel, B. A., Mushiva, E. A., Kharkova, E. M., Shishkina, M. V.: Eur. Polymer J. 11, 865 (1975)Google Scholar
  6. 6.
    Stefanovskaya, N. N., Shmonina, V. L., Gavrilenko, I. F., Tinyakova, E. I., Dolgoplosk, B. A.: Dokl. Akad. Nauk SSSR 174, 1356 (1967)Google Scholar
  7. 7.
    Baldwin, F. P., Buckley, D. J., Kuntz, I., Robinson, S. B.: Rubber Plastic Age 42, 500 (1961)Google Scholar
  8. 8.
    Baldwin, F. P., Gardner, I. J., Malatesta, A., Rae, J. A.: Paper presented at 108th A. C. S. Rubber Div. Meeting, New Orleans, October 7–10, 1975; Rubber Chem. Technol. 49, 390 (1976)Google Scholar
  9. 9.
    Cesca, S.: J. Polymer Sci., Macromol. Rev. 10, 1 (1975)Google Scholar
  10. 10.
    Priola, A., Corno, C., Cesca, S.: in preparationGoogle Scholar
  11. 11.
    1970 Book of ASTM Standards, Pt. 28, p. 607, Philadelphia, Pa.: American Society for Testing and Materials, 1970Google Scholar
  12. 12.
    Cesca, S., Arrighetti, S., Marconi, W.: Chim. Ind. (Milan) 50, 171 (1968)Google Scholar
  13. 13.
    Ghetti, G., Corradini, G., Bulla, V., Bruzzone, M.: Chim. Ind. (Milan) 51, 1361 (1969)Google Scholar
  14. 14.
    Cesca, S., Roggero, A., Salvatori, T., De Chirico, A., Santi, G.: Makromol. Chem. 133, 161 (1970)Google Scholar
  15. 15.
    Cesca, S., Bertolini, G., Santi, G., Duranti, P. V.: J. Polymer Sci. A-1, 9, 1575 (1971)Google Scholar
  16. 16.
    Cesca, S., Bertolini, G., Santi, G., Roggero, A.: J. Macromol. Sci. A-7, 475 (1973)Google Scholar
  17. 17.
    Cesca, S., Duranti, P. V., Roggero, A., Santi, G., Bruzzone, M.: J. Polymer Sci., Chem. Ed. 12, 1209 (1974)Google Scholar
  18. 18.
    Cesca, S., Arrighetti, S., Bertolini, G., Bruzzone, M.: J. Macromol. Sci., Chem. A-8, 393 (1974)Google Scholar
  19. 19.
    Cesca, S., Arrighetti, S., Priola, A., Duranti, P. V., Bruzzone, M.: Makromol. Chem. 175, 2539 (1974)Google Scholar
  20. 20.
    Cesca, S., Priola, A., Santi, G.: Polymer Letters 8, 573 (1970)Google Scholar
  21. 21.
    Arrighetti, S., Brancaccio, G., Cesca, S., Giuliani, G. P.: Chim. Ind. (Milan) 59, 483, 605, 685 (1977)Google Scholar
  22. 22.
    Musco, A., Silvani, A.: J. Organometal. Chem. 88, C41 (1975)Google Scholar
  23. 23.
    Priola, A., Ferraris, G., Di Maina, M., Giusti, P.: Makromol. Chem. 176, 2271 (1975)Google Scholar
  24. 24.
    Wassermann, A.: J. Chem. Soc. 1936, 1028 and 1939, 375Google Scholar
  25. 25.
    Atarot, H., Faucitano, A., Cesca, S.: Eur. Polymer J. 12, 169 (1976)Google Scholar
  26. 26.
    Baldwin, F. P., Borzel, P., Makowski, H. S.: Rubber Chem. Technol. 42, 1167 (1969)Google Scholar
  27. 27.
    Pearson, D. S., Böhm, G. G. A.: Rubber Chem. Technol. 45, 1, 193 (1972)Google Scholar
  28. 28.
    Sheehan, C. J., Bisio, A. L.: Rubber Chem. Technol. 39, 149 (1966)Google Scholar
  29. 29.
    Natta, G., Mazzanti, G., Valvassori, A., Sartori, G., Barbagallo, A.: J. Polymer Sci. 51, 429 (1961)Google Scholar
  30. 30.
    Kennedy, J. P.: J. Polymer Sci. A-1 6, 3139 (1968)Google Scholar
  31. 31.
    Kennedy, J. P.: J. Macromol. Sci. Chem. A-6, 329 (1972)Google Scholar
  32. 32.
    Cesca, S., Bruzzone, M., Priola, A., Ferraris, G., Giusti, P.: Rubber Chem. Technol. 49, 937 (1976)Google Scholar
  33. 33.
    Tokita, N., Scott, R.: Rubber Chem. Technol. 46, 1019 (1973)Google Scholar
  34. 34.
    Gardner, I. J., Ver Strate, G.: Rubber Chem. Technol. 46, 1019 (1973)Google Scholar
  35. 35.
    Sonnenfeld, R. J., Kahle, G. R., Buck, O. G.: J. Appl. Polymer Sci. 13, 365 (1969)Google Scholar
  36. 36.
    Sauer, J.: Angew. Chem., int. ed. 6, 16 (1967)Google Scholar
  37. 37.
    Valvassori, A., Sartori, G., Mazzanti, G., Pajaro, G.: Makromol. Chem. 61, 46 (1963)Google Scholar
  38. 38.
    Gardner, I. J., Baldwin, F. P.: Paper presented at 108th A. C. S. Rubber Div. Meeting, New Orleans, October 7–10, 1975; Rubber Chem. Technol. 49, 391 (1976)Google Scholar
  39. 39.
    Ital. Pat. Appl. 26222, August 8, 1975, filed by Snamprogetti S. p. A.Google Scholar
  40. 40.
    Thaler, W. A., Buckley, D. J.: Rubber Chem. Technol. 49, 960 (1976)Google Scholar
  41. 41.
    Kennedy, J. P., Canter, N. H.: J. Polymer Sci. A-1, 5, 2455, 2712 (1967)Google Scholar
  42. 42.
    Ceresa, R. J.: Block and graft copolymers. London: Butterworth, 1962Google Scholar
  43. 43.
    Recent advances in polymer blends, grafts and blocks. Sperling, L. H. (ed.). New York: Plenum Press, 1974Google Scholar
  44. 44.
    Copolymers, polyblends and composites. Platzer, N. A. (ed.). Adv. Chem. Ser. 142, 141–231 (1975)Google Scholar
  45. 45.
    Placek, C.: Chemical Process Review no 46, Park Ridge, New Jersey: Noyes Data Co., 1970Google Scholar
  46. 46.
    Meredith, G. L.: Rubber Chem. Technol. 44, 1130 (1971)Google Scholar
  47. 47.
    Allen, P. W., Merrett, F. M.: J. Polymer Sci. 22, 193 (1956)Google Scholar
  48. 48.
    Locatelli, J. L., Riess, G.: Angew. Makromol. Chem. 32, 117 (1973)Google Scholar
  49. 49.
    Bevington, J. C.: J. Chem. Soc. 1954, 3707Google Scholar
  50. 50.
    Rajbenbach, A., Szwarc, M.: J. Am. Chem. Soc. 79, 6343 (1957)Google Scholar
  51. 51.
    Rajbenbach, A., Szwarc, M.: Proc. Roy. Soc. (London) A 251, 1266 (1959)Google Scholar
  52. 52.
    Gresser, J., Rajbenbach, A., Szwarc, M.: J. Am. Chem. Soc. 82, 5820 (1960)Google Scholar
  53. 53.
    Pulman, B.: J. Chem. Phys. 55, 790 (1958)Google Scholar
  54. 54.
    Hefter, H. J., Hecht, I. A., Hammond, G. S.: J. Am. Chem. Soc. 94, 2793 (1972)Google Scholar
  55. 55.
    Faucitano, A., Faucitano Martinotti, F., Buttafava, A., Cesca, S.: Eur. Polymer J. 12, 421 (1976)Google Scholar
  56. 56.
    Faucitano, A., Buttafava, A., Faucitano Martinotti, F., Cesca, S.: J. Phys. Chem. 81, 354 (1977)Google Scholar
  57. 57.
    Van Drumpt, J. D., Oosterwijk, H. H.: J. Polymer Sci., Chem. Ed. 14, 1495 (1976)Google Scholar
  58. 58.
    Loan, L. D.: J. Polymer Sci. A-2, 2127 (1964)Google Scholar
  59. 59.
    Bruzzone, M.: Hydroc. Process. 52, 153 (1973)Google Scholar
  60. 60.
    Bateman, L.: The chemistry and physics of rubber-like substances, p. 486. London: Mc Laren and Sons, 1963Google Scholar
  61. 61.
    Pryor, W. A., Fuller, D. L., Stanley, J. P.: J. Am. Chem. Soc. 94, 1632 (1972)Google Scholar
  62. 62.
    Walling, C., Thaler, W.: J. Am. Chem. Soc. 83, 3877 (1973)Google Scholar
  63. 63.
    Baldwin, F. P., Borzel, P.: Rubber Chem. Technol. 43, 552 (1970)Google Scholar
  64. 64.
    Loan, L. D.: J. Polymer Sci. A-2, 3053 (1964)Google Scholar
  65. 65.
    Baldwin, F. P., Ver Strate, G.: Rubber Chem. Technol. 45, 709 (1972)Google Scholar
  66. 66.
    Bateman, L., Glazebrook, R. W., Moore, C. G., Porter, M., Ross, W., Saville, R. W.: J. Chem. Soc. 1958, 2838, 2846, 2866Google Scholar
  67. 67.
    Saville, D., Watson, A. A.: Rubber Chem. Technol. 40, 100 (1967)Google Scholar
  68. 68.
    Hoffmann, W.: Vulcanization and vulcanizing agents, p. 21. London: Mac Laren and Sons, 1967Google Scholar
  69. 69.
    Walker, J.: J. of IRI 8, 64 (1974)Google Scholar
  70. 70.
    Cotten, G. R.: Rubber Chem. Technol. 45, 129 (1972)Google Scholar
  71. 71.
    Block, G. A.: Organic accelereators in vulcanization of rubbers, p. 224. Jerusalem: I. P. S. I., 1968Google Scholar
  72. 72.
    Wassermann, A.: Diels-Alder reactions, p. 52. Amsterdam: Elsevier Publ. Co., 1965Google Scholar
  73. 73.
    Benford, G., Wassermann, A.: J. Chem. Soc. 1939, 362Google Scholar
  74. 74.
    Benford, G., Khambata, S., Kauffmann, H., Wassermann, A.: J. Chem. Soc. 1939, 381Google Scholar
  75. 75.
    Kaufmann, H., Wassermann, A.: J. Chem. Soc. 1939, 870Google Scholar
  76. 76.
    Bouchal, K., Toupek, J., Pokorny, S., Hzabak, F.: Makromol. Chem. 137, 95 (1970)Google Scholar
  77. 77.
    Huisgen, R., Grashey, R., Sauer, J.: The chemistry of alkenes, Patai, S., (ed.), Vol. I, p. 739. New York: Interscience, 1964Google Scholar
  78. 78.
    Wassermann, A.: Trans. Faraday Soc. 34, 128 (1938)Google Scholar
  79. 79.
    Wassermann, A.: Ber. 66, 1933 (1932)Google Scholar
  80. 80.
    Bell, V. L.: J. Polymer Sci. A-2, 5305 (1964)Google Scholar
  81. 81.
    Platé, N. A.: Pure and Appl. Chem. 46, 49 (1976)Google Scholar
  82. 82.
    Langley, R. N.: Macromolecules 1, 348 (1968)Google Scholar
  83. 83.
    Onishenko, A. S.: Diene synthesis, p. 61. Jerusalem: I. P. S. R., 1964Google Scholar
  84. 84.
    Ferry, J. D.: Viscoelastic properties of polymers, Chapt. 12. New York: Interscience, 1970Google Scholar
  85. 85.
    Tobolsky, A. V., Lyons, P. F., Hata, N.: Macromolecules 1, 515 (1968)Google Scholar
  86. 86.
    Hoffmann, W.: Vulcanization and vulcanizing agents, p. 300. London: Mac Laren and Sons, 1967Google Scholar
  87. 87.
    Bruzzone, M., Crespi, G.: Chim. Ind. (Milan) 42, 1226 (1960)Google Scholar
  88. 88.
    Flory, P. J.: Principles of polymer chemistry, p. 358. Ithaca, New York: Cornell University Press, 1953Google Scholar
  89. 89.
    Brydon, A., Burnett, G. M., Cameron, G. G.: J. Polymer Sci. Chem. Ed. 11, 3255 (1973)Google Scholar
  90. 90.
    Bodendorf, K.: Arch. Pharm. 271, 1 (1933)Google Scholar
  91. 91.
    Kern, W., Stolman, I.: Makromol. Chem. 7, 199 (1951)Google Scholar
  92. 92.
    Hock, H., Depka, F.: Ber. 84, 349 (1951)Google Scholar
  93. 93.
    British, P. 1.020.670, assigned to SNAMPROGETTI S.p.A.Google Scholar
  94. 94.
    U. S. P. 3.681.309, assigned to ESSO Co.Google Scholar
  95. 95.
    Faucitano, A., Atarot, H., Faucitano Martinotti, F., Comincioli, V., Arrighetti, S., Cesca, S.: submitted to Eur. Polymer J.Google Scholar
  96. 96.
    Gear, C. K.: Numerical initial value problems in ordinary differential equations, New York, Englewood Cliffs: Prentice Hall, 1971Google Scholar
  97. 97.
    Faucitano, A., Atarot, H., Faucitano Martinotti, F., Comincioli, V., Cesca, S.: Eur. Polymer J., in pressGoogle Scholar

Copyright information

© Springer-Verlag 1979

Authors and Affiliations

  • Sebastiano Cesca
    • 1
  • Aldo Priola
    • 1
  • Mario Bruzzone
    • 1
  1. 1.Assoreni, Polymer Research LaboratoriesSan Donato MilaneseItaly

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