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Living polymerization and selective dimerization: Two extremes of the polymer synthesis by cationic polymerization

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Initiators — Poly-Reactions — Optical Activity

Part of the book series: Advances in Polymer Science ((POLYMER,volume 62))

Abstract

This review focuses on recent advances in selective dimerization and living polymerization of vinyl compounds by cationic mechanisms. The two reactions, which initially may appear to be completely different, are discussed on the basis of the current understanding of the nature of the propagating species in cationic polymerization. Following a classification of the cationic initiators into metal halide (MXn) and nonmetal halide (non-MXn) types and a clear definition of the differences between the growing intermediates derived from these two classes of initiators, this article emphasizes the characteristics of the nondissociated propagating species formed by non-MXn initiators, including a number of examples of selective dimerization and living polymerization.

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6 References

  1. Plesch, P. H. (Ed.): The Chemistry of Cationic Polymerization. Pergamon Press, London, 1963

    Google Scholar 

  2. Higashimura, T.: Cationic Polymerization (in Japanese). Kagaku-Dojin, Kyoto, 1971

    Google Scholar 

  3. Kennedy, J. P.: Cationic Polymerization of Olefins: Critical Inventory. Wiley-Interscience, New York, 1975

    Google Scholar 

  4. Kennedy, J. P., Maréchal, E.: Carbocationic Polymerization. Wiley-Interscience, New York, 1982

    Google Scholar 

  5. A brief review on the history of cationic polymerization, see: Ref. 3, Chapter 3

    Google Scholar 

  6. De Sorgo, M., Pepper, D. C., Szwarc, M.: Chem. Commun. 419 (1973)

    Google Scholar 

  7. Gandini, A., Plesch, P. H.: Proc. Chem. Soc. 240 (1964); J. Polym. Sci. B 3, 127 (1965); and subsequent publications

    Google Scholar 

  8. Masuda, T., Higashimura, T.: J. Polym. Sci. B 9, 783 (1971)

    Article  Google Scholar 

  9. Ref. 2, p. 89 and Ref. 4, p. 180

    Google Scholar 

  10. Ref. 4, Chapters 8 and 9

    Google Scholar 

  11. Pepper, D. C., in: Friedel-Crafts and Related Reactions. Vol. 2, Olah, G. A. (Ed.), Wiley-Interscience, New York, 1964, p. 1293

    Google Scholar 

  12. Sawamoto, M., Masuda, T., Higashimura, T.: J. Polym. Sci. Polym. Chem. Ed. 16, 2675 (1978)

    Article  Google Scholar 

  13. Hayes, M. J., Pepper, D. C.: Proc. Roy. Soc. A 263, 58, 63 (1961)

    Google Scholar 

  14. Pepper, D. C.: Makromol. Chem. 175, 1077 (1974)

    Article  Google Scholar 

  15. Pepper, D. C., Reilly, P. J.: J. Polym. Sci. 58, 639 (1962)

    Article  Google Scholar 

  16. Sawamoto, M., Masuda, T., Higashimura, T., Kobayashi, S., Saegusa, T.: Makromol. Chem. 178, 387 (1977)

    Google Scholar 

  17. Higashimura, T.: J. Polym. Sci. Polym. Symp. No. 56, 71 (1976)

    Google Scholar 

  18. Higashimura, T., Kishiro, O.: J. Polym. Sci. Polym. Chem. Ed. 12, 967 (1974)

    Article  Google Scholar 

  19. Higashimura, T., Kishiro, O., Matsuzaki, K., Uryu, T.: ibid. 13, 1393 (1975)

    Article  Google Scholar 

  20. Pepper, D. C.: J. Polym. Sci. Polym. Symp. No. 50, 51 (1975)

    Google Scholar 

  21. Gandini, A., Cheradame, H.: Adv. Polym. Sci. 34/35, 1 (1980)

    Google Scholar 

  22. Higashimura, T., Kishiro, O., Takeda, T.: J. Polym. Sci. Polym. Chem. Ed. 14, 1089 (1976)

    Article  Google Scholar 

  23. Masuda, T., Sawamoto, M., Higashimura, T.: Makromol. Chem. 177, 2981 (1976)

    Article  Google Scholar 

  24. Sawamoto, M., Masuda, T., Higashimura, T.: ibid. 177, 2995 (1976)

    Article  Google Scholar 

  25. Kennedy, J. P., Trivedi, P. D.: Adv. Polym. Sci. 28, 113 (1978)

    Google Scholar 

  26. Lenz, R. W., Westfelt, L. C.: J. Polym. Sci. Polym. Chem. Ed. 14, 2147 (1976)

    Article  Google Scholar 

  27. Review in: Ref. 4, Chapter 10

    Google Scholar 

  28. Review by: Okawara, M., Saegusa, T., Higashimura, T. (Eds.): Oligomers (in Japanese). Kodansha Scientific, Tokyo, 1976

    Google Scholar 

  29. Review by: Schmering, L., Ipatieff, V. N.: Advances in Catalysis and Related Subjects. Vol. 2, Academic Press, New York, 1950, p. 62

    Google Scholar 

  30. Taylor, A. R., Keen, G. W., Eisenbraun, E. J.: J. Org. Chem. 42, 3477 (1977) and References therein

    Article  Google Scholar 

  31. Sawamoto, M., Masuda, T., Nishii, H., Higashimura, T.: J. Polym. Sci. Polym. Lett. Ed. 13, 279 (1975)

    Article  Google Scholar 

  32. Higashimura, T., Nishii, H.: J. Polym. Sci. Polym. Chem. Ed. 15, 329 (1977)

    Article  Google Scholar 

  33. Higashimura, T., Hiza, M., Hasegawa, H.: Macromolecules 12, 217 (1979)

    Article  Google Scholar 

  34. Nishii, H., Higashimura, T.: J. Polym. Sci. Polym. Chem. Ed. 15, 1179 (1977)

    Article  Google Scholar 

  35. Higashimura, T., Hiza, M., Hasegawa, H.: Macromolecules 12, 1058 (1979)

    Article  Google Scholar 

  36. Hiza, M., Hasegawa, H., Higashimura, T.: Polym. J. 12, 379 (1980)

    Google Scholar 

  37. Higashimura, T., Hiza, M.: ibid. 13, 1058 (1981)

    Google Scholar 

  38. Cram, D. J., Sahyun, M. R. V.: J. Am. Chem. Soc. 85, 1257 (1963)

    Article  Google Scholar 

  39. Cocivera, M., Winstein, S.: ibid. 85, 1702 (1963)

    Article  Google Scholar 

  40. Skell, P. S., Hall, W. L.: ibid. 85, 2851 (1963)

    Article  Google Scholar 

  41. Higashimura, T., Hasegawa, H.: J. Polym. Sci. Polym. Chem. Ed. 17, 59 (1979)

    Article  Google Scholar 

  42. Butler, G. B., Angelo, R. J.: J. Am. Chem. Soc. 79, 3128 (1957)

    Article  Google Scholar 

  43. Review by: Aso, C., Kunitake, T., Tagami, S.: Prog. Polym. Sci. Japan 1, 149 (1971)

    Google Scholar 

  44. Recent review by: Butler, G. B.: Acc. Chem. Res. 15, 370 (1982)

    Article  Google Scholar 

  45. Review in: Ref. 3, p. 275

    Google Scholar 

  46. Ref. 47 and references therein

    Google Scholar 

  47. Nishimura, J., Yamashita, S.: Polym. J. 11, 619 (1979)

    Google Scholar 

  48. Furukawa, J., Nishimura, J.: J. Polym. Sci. Polym. Symp. No. 56, 437 (1976)

    Google Scholar 

  49. Hasegawa, H., Higashimura, T.: Macromolecules 13, 1350 (1980)

    Article  Google Scholar 

  50. Aoshima, S., Higashimura, T.: Polymer Preprint, Japan 31, 328 (1982); J. Polym. Sci. Polym. Chem. Ed. 22, in press (1984)

    Google Scholar 

  51. For instance, see Bywater, S.: Ref. 1, Chapter 7

    Google Scholar 

  52. Hersberger, A. B., Heiligman, R. C.: U.S. Patent 2,429,719 (1947), as as quoted in: Ref. 4, p. 89

    Google Scholar 

  53. Kawakami, Y., Toyoshima, N., Yamashita, Y.: Chem. Lett. 13 (1980)

    Google Scholar 

  54. See for the relevant literature citations

    Article  Google Scholar 

  55. Higashimura, T., Hiza, M.: J. Polym. Sci. Polym. Chem. Ed. 19, 1957 (1981)

    Article  Google Scholar 

  56. Review in: Ref. 26, p. 29

    Article  Google Scholar 

  57. Review in: p. 87

    Google Scholar 

  58. Haag, W. O.: Chem. Eng. Prog. 63, 145 (1967)

    Google Scholar 

  59. Hasegawa, H., Higashimura, T.: J. Appl. Polym. Sci. 27, 171 (1982)

    Article  Google Scholar 

  60. Higashimura, T., Miyoshi, Y., Hasegawa, H.: ibid. 28, 241 (1983)

    Google Scholar 

  61. Sawamoto, M., Higashimura, T.: Macromolecules 14, 467 (1981)

    Article  Google Scholar 

  62. An early review by: Kennedy, J. P., Otsu, T.: Adv. Polym. Sci. 7, 369 (1970)

    Google Scholar 

  63. See also Kennedy, J. P., in: Encyclopedia of Polymer Science and Technology. Vol. 7, Mark, H. F., Gaylord, N. G., Bikales, N. M. (Eds.), Interscience, New York, 1967, p. 754

    Google Scholar 

  64. Higashimura, T., Sagane, T., Hasegawa, H.: Polym. J. 13, 487 (1981)

    Google Scholar 

  65. Hasegawa, H., Higashimura, T.: J. Polym. Sci. Polym. Chem. Ed. 17, 2439 (1979)

    Article  Google Scholar 

  66. Hasegawa, H., Higashimura, T.: Polym. J. 12, 407 (1980)

    Google Scholar 

  67. Hasegawa, H., Higashimura, T.: ibid. 13, 915 (1981)

    Google Scholar 

  68. Szwarc, M.: Nature 178, 1168 (1956); J. Am. Chem. Soc. 78, 2656 (1956)

    Google Scholar 

  69. Reviews by: Szwarc, M.: Carbanion, Living Polymers and Electron-Transfer Processes. Wiley, New York, 1968; Adv. Polym. Sci. 49, 1 (1983)

    Google Scholar 

  70. Dreyfuss, M. P., Dreyfuss, P.: Polymer 6, 93 (1965)

    Article  Google Scholar 

  71. Bawn, C. E. H., Bell, R. M., Ledwith, A.: ibid. 6, 95 (1965)

    Article  Google Scholar 

  72. Schildknecht, C. E., Zoss, A. O., Grosser, F.: Ind. Eng. Chem. 41, 2891 (1949)

    Article  Google Scholar 

  73. Asami, R., Tokura, N.: J. Polym. Sci. 42, 545 (1960)

    Article  Google Scholar 

  74. Asami, R., Tokura, N.: ibid. 42, 553 (1960)

    Article  Google Scholar 

  75. Johnson, A. F., Young, R. N.: J. Polym. Sci. Polym. Symp. No. 56, 211 (1976)

    Google Scholar 

  76. De Mola, A. H., Ledwith, A., Yanus, J. F., Limburg, W. W., Person, J. M.: J. Polym. Sci. Polym. Chem. Ed. 16, 761 (1978)

    Article  Google Scholar 

  77. Rooney, J. M., Squire, D. R., Stannett, V. T.: ibid. 14, 1877 (1976)

    Article  Google Scholar 

  78. Bossaer, P. K., Goethals, E. J., Hackett, P. J., Pepper, D. C.: Europ. Polym. J. 13, 489 (1977)

    Article  Google Scholar 

  79. Seung, S. L. N., Young, R. N.: J. Polym. Sci. Polym. Lett. Ed. 17, 233 (1979)

    Article  Google Scholar 

  80. Higashimura, T., Kishiro, O.: Polym. Prepr. Japan 24, 106 (1975); Polym. J. 9, 87 (1977)

    Google Scholar 

  81. Ohtori, T., Hirokawa, Y., Higashimura, T.: Polym. J. 11, 471 (1979)

    Google Scholar 

  82. Higashimura, T., Miyamoto, M., Sawamoto, M.: Polym. Prepr. Japan 31, 200 (1982)

    Google Scholar 

  83. Higashimura, T., Mitsuhashi, M., Sawamoto, M.: Macromolecules 12, 178 (1979)

    Article  Google Scholar 

  84. Higashimura, T., Teranishi, H., Sawamoto, M.: Polym. J. 12, 393 (1980)

    Google Scholar 

  85. Higashimura, T., Deng, Y.-X., Sawamoto, M.: ibid. 15, 385 (1983)

    Google Scholar 

  86. Higashimura, T., Tanizaki, A., Sawamoto, M.: Polym. Prepr. Japan 32, 188 (1983); J. Polym. Sci. Polym. Chem. Ed. submitted

    Google Scholar 

  87. Higashimura, T., Ogawa, Y., Sawamoto, M.: ibid. 31, 1137 (1982); Polym. J. 16, in press (1984)

    Google Scholar 

  88. Teranishi, H., Sawamoto, M., Higashimura, T.: ibid. 29, 104 (1980)

    Google Scholar 

  89. Miyamoto, M., Sawamoto, M., Higashimura, T.: Macromolecules 17, March issue (1984)

    Google Scholar 

  90. For instance, see: Eley, D. D., Richard, A. W.: Trans. Faraday Soc. 45, 425 (1949)

    Article  Google Scholar 

  91. Okamura, S., Kanoh, N., Higashimura, T.: Makromol. Chem. 47, 19 (1961) and subsequent publications

    Article  Google Scholar 

  92. Giusti, P., Puce, G., Andruzzi, F.: Makromol. Chem. 98, 170 (1966)

    Article  Google Scholar 

  93. Giusti, P., Andruzzi, F.: J. Polym. Sci. C 16, 3797 (1968)

    Google Scholar 

  94. Ledwith, A., Sherrington, D. C.: Polymer 12, 344 (1971)

    Article  Google Scholar 

  95. Review by: Olah, G. A.: Angew. Chem. 85, 183 (1973)

    Google Scholar 

  96. Kennedy, J. P., Melby, E., Johnston, J.: J. Macromol. Sci.-Chem. A 8, 463 (1974)

    Google Scholar 

  97. Kennedy, J. P., Kelen, T.: ibid. A 18, 1189 (1982–83)

    Google Scholar 

  98. Faust, R., Fehérvári, A., Kennedy, J. P.: ibid. A 18, 1209 (1982–83)

    Google Scholar 

  99. Sawamoto, M., Kennedy, J. P., in: Elastmers and Rubber Elasticity, ACS Symp. Ser. 193, 213 (1982), Mark, J. E., Lal, J. (Eds.)

    Google Scholar 

  100. Sawamoto, M., Kennedy, J. P.: J. Macromol. Sci.-Chem. A 18, 1275 (1982–83)

    Google Scholar 

  101. Sawamoto, M., Kennedy, J. P.: ibid. A 18, 1293 (1982–83)

    Google Scholar 

  102. Sawamoto, M., Kennedy, J. P.: ibid. A 18, 1301 (1982–83)

    Google Scholar 

  103. Puskás, J., Kaszás, G., Kennedy, J. P., Kelen, T.: ibid. A 18, 1229 (1982–83)

    Google Scholar 

  104. Puskás, J., Kaszás, G., Kennedy, J. P., Kelen, T., Tüdős, F.: ibid. A 18, 1245 (1982–83)

    Google Scholar 

  105. Puskás, J., Kaszás, G., Kennedy, J. P., Kelen, T., Tüdős, F.: ibid. A 18, 1263 (1982–83)

    Google Scholar 

  106. Puskás, J., Kaszás, G., Kennedy, J. P., Kelen, T., Tüdős, F.: ibid. A 18, 1315 (1982–83)

    Google Scholar 

  107. Kelen, T.: ibid. A 18, 1339 (1982–83)

    Google Scholar 

  108. Puskás, J., Kaszás, G., Kennedy, J. P., Kelen, T., Tüdős, F.: ibid. A 18, 1353 (1982–83)

    Google Scholar 

  109. Kaszás, G., Győr, M., Kennedy, J. P., Tüdős, F.: ibid. A 18, 1367 (1982–83)

    Google Scholar 

  110. Review by: Ledwith, A., Sherrington, D. C.: Adv. Polym. Sci. 19, 1 (1975)

    Article  Google Scholar 

  111. Miyamoto, M., Sawamoto, M., Higashimura, T.: Polym. Prepr., Japan 32, 1439 (1983); to be published

    Google Scholar 

  112. Szwarc, M., Zimm, B. H.: Macromolecules 16, 1918 (1983)

    Article  Google Scholar 

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  1. Department of Polymer Chemistry, Faculty of Engineering, Kyoto University, 606, Kyoto, Japan

    Toshinobu Higashimura & Mitsuo Sawamoto

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  1. Toshinobu Higashimura
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  2. Mitsuo Sawamoto
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© 1984 Springer-Verlag

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Higashimura, T., Sawamoto, M. (1984). Living polymerization and selective dimerization: Two extremes of the polymer synthesis by cationic polymerization. In: Initiators — Poly-Reactions — Optical Activity. Advances in Polymer Science, vol 62. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0024035

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  • DOI: https://doi.org/10.1007/BFb0024035

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