Techniques of Block Copolymer Preparation

  • G. Allan Stahl
Part of the Polymer Science and Technology book series (POLS, volume 11)

Abstract

The unusual physical properties of block copolymers range from combination of rubbery and glassy polymers to polar and non-polar polymers. The uses of these block copolymers thus range from thermoplastic elastomers to surfactants to modifiers. It is therefore necessary that the polymer chemist stay abreast of their many preparative techniques. The purpose of this report is to classify these techniques, serve as a reservoir of literature references, and as a source of ideas to stimulate thinking on particular block copolymer preparations and their potential utility.

The block copolymer preparative techniques reviewed in this report include sequential addition to macroanions, “pseudoliving” carbenium ion systems, used of coordination catalysts, coupling of polymer termini, and various preparations employing free radical polymerization. The review covers 133 papers and patents.

Keywords

Surfactant Anhydride Diene Halide Alkoxide 

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Bibliography

  1. 1.
    M. Szwarc, M. Levy, and R. Milkovich, J. Am. Chem. Soc., 78, 2656 (1956).CrossRefGoogle Scholar
  2. 2.
    A. Noshay and J. E. McGrath, “Block Copolymers”, Academic Press, New York, 1977.Google Scholar
  3. 3.
    R. J. Geresa (ed.), “Block and Graft Copolymerization”, Vol. 1, John Wiley and Sons. New York, 1973.Google Scholar
  4. 4.
    J. J. Burke and V. Weiss, (Eds.), “Block and Graft Copolymers”, Syracuse Press, Inc., Syracuse, N.Y., 1973.Google Scholar
  5. 5.
    D. C. Allport and W. H. Janes, (Eds.), “Block Copolymers”, Applied Science Publishers, London, 1973.Google Scholar
  6. 6.
    M. Szwarc, “Carbanions, Living Polymers, and Electron Transfer Processes”, Interscience Publishers, New York, 1968.Google Scholar
  7. 7.
    R. J. Ceresa (Ed.), “Block and Graft Copolymers”, Butterworth, London, 1962.Google Scholar
  8. 8.
    W. J. Burlant and A. S. Hoffman, “Block and Graft Polymers,” Reinhold Publishing Corp., New York, 1960.Google Scholar
  9. 9.
    Shell International Research, Brit. 1, 068, 130 (1964).Google Scholar
  10. 10.
    Shell International Research, Brit. 1, 098, 570 (1965).Google Scholar
  11. 11.
    S. Bywater, Adv. Polym. Sci., 4, 66 (1965).CrossRefGoogle Scholar
  12. 12.
    M. Morton and L. J. Fetters, Macromol. Rev., 2, 71 (1967).CrossRefGoogle Scholar
  13. 13.
    L. J. Fetters, J. Polym. Sci., C26, 1 (1969).Google Scholar
  14. 14.
    S. Horiie, et al., Jap. Kokai, 74118, 689 (1974).Google Scholar
  15. 15.
    S. Horiie, et al., Ger. Offen. 2361174 (1975).Google Scholar
  16. 16.
    R. E. Cunningham, Ger. Offen. 2422724 (1974).Google Scholar
  17. 17.
    M. Morton and L. J. Fetters, Rubber Rev., 48, 359 (1975).Google Scholar
  18. 18.
    L. Bi and L. J. Fetters, Macromolecules, 9, 732 (1976).CrossRefGoogle Scholar
  19. 19.
    H. A. J. Schepers, Ger. Offen., 244, 2849 (1975).Google Scholar
  20. 20.
    A. Douy, G. Jovan, and B. Gallot, C. R. Hebd. Seances Acad. Sci., Ser. C., 281 355 (1975).Google Scholar
  21. 21.
    D. J. Worsfold, Can. Pat. 973295 (1975).Google Scholar
  22. 22.
    Y. Yamashita, K. Nobutoki, Y. Nakamuna, M. Hirota, and H. Wakabayachi, Toyoda Kenkyu Hokoku, 26, 10 (1973).Google Scholar
  23. 23.
    M. Takaki, R. Asami, and M. Ichikawa, submitted for publication in Macromolecules [see ref. 2].Google Scholar
  24. 24.
    D. H. Richards, et al., Polymer, 19, 68 (1978).CrossRefGoogle Scholar
  25. 25.
    M. Takaki, R. Asami, H. Inukai, and T. Inenaga, Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem., 18 (1), 682 (1977).Google Scholar
  26. 26.
    M. Prissette, H. Magnin, M. Abadie, and F. Schue, Eur. Polym. J., 12, 713 (1976).CrossRefGoogle Scholar
  27. 27.
    J. Baca, L. Lochmann, K. Juzl, J. Coupek, and D. Lim, J. Polym. Sci., C16, 3865 (1968).Google Scholar
  28. 28.
    D. C. Evans, J. A. Barrie, and M. H. George, Polymer, 16, 151 (1975).CrossRefGoogle Scholar
  29. 29.
    J. M. Guyon-Gellin, J. Gole, and J. P. Pascault, J. Appl. Polym. Sci., 19, 3173 (1975).CrossRefGoogle Scholar
  30. 30.
    J. Rossi, and B. Gallot, Makromol. Chem., 177, 2801 (1976).CrossRefGoogle Scholar
  31. 31.
    M. Matzner, J. E. McGrath, and A. Noshay, U.S. Pat. 3,770, 849 (1973).Google Scholar
  32. 32.
    Y. Yamashita, M. Matsui, and K. Ito, J. Polym. Sci., Polymer Chem. Ed., 10, 3577 (1972).CrossRefGoogle Scholar
  33. 33.
    J. Stehlicek and J. Sebenda, Polyamidy 75, 91 (1975).Google Scholar
  34. 34.
    H. Kawamoto, Jap. Kokai 74 30 707 (1974).Google Scholar
  35. 35.
    S. A. Sundet, et al., Macromolecules, 9, 371 (1976).CrossRefGoogle Scholar
  36. 36.
    R. P. Foss, H. W. Jacobson, H. N. Cripps, and W. H. Sharkey, Macromolecules, 9, 373 (1976).CrossRefGoogle Scholar
  37. 37.
    D. R. Jackson and L. G. Lundsted, U.S. Pat. 2,677, 700 (1974).Google Scholar
  38. 38.
    D. R. Jackson and L. G. Lundsted, U.S. Pat. 3,036, 130 (1962).Google Scholar
  39. 39.
    D. H. Richards and M. Szwarc, Trans. Fara. Soc., 55, 1644 (1959).CrossRefGoogle Scholar
  40. 40.
    G. Finaz, Y. Gallot, J. Parod, and R. Rempp, J. Polym. Sci., 58, 1363 (1962).CrossRefGoogle Scholar
  41. 41.
    J. J. O’Malley and R. H. Marchessault, Macromol. Synth., 3, 35 (1972).Google Scholar
  42. 42.
    S. Marti, J. Nervo, and G. Riess, Progr. Colloid and Polymer. Sci., 58, 114 (1975).Google Scholar
  43. 43.
    G. Riess, J. Nervo, and D. Rogez, Polym. Prep., Am. Chem. Soc. Div. Polym. Chem., 18 (1), 329 (1977).Google Scholar
  44. 44.
    Y. Minoura and A. Nakano, Macromol. Synth., 4, 25 (1972).Google Scholar
  45. 45.
    M. Tomoi, Y. Shibayama, and H. Kakiuchi, Polym. J., 8, 190 (1976).CrossRefGoogle Scholar
  46. 46.
    C. W. Brown and I. F. White, J. Applied Polym. Sci., 16, 2671 (1972).CrossRefGoogle Scholar
  47. 47.
    P. T. Hale and G. A. Pope, Eur. Polym. J., 11, 677 (1975).CrossRefGoogle Scholar
  48. 48.
    A. Douy, G. Jouan, and B. Gallot, Makromol. Chem., 177, 2945 (1976).CrossRefGoogle Scholar
  49. 49.
    P. K. Wong, A. E. Zachariades, and M. Szwarc, Polymer, 17, 817 (1976).CrossRefGoogle Scholar
  50. 50.
    C. U. Pittman, Jr. and A. Hirao, J. Polym. Sci., Polym. Chem. Ed., 15, 1677 (1977).CrossRefGoogle Scholar
  51. 51.
    J. P. Kennedy and E. G. Melby, J. Polym. Sci., Polym. Chem. Ed., 13, 29 (1975).CrossRefGoogle Scholar
  52. 52.
    J. P. Kennedy, E. G. Melby and A. Vidal, J. Macromol. Sci., A9, 833 (1975).Google Scholar
  53. 53.
    J. P. Kennedy and A. Vidal, J. Polym. Sci., Polym. Chem. Ed., 13, 1765 (1975).Google Scholar
  54. 54.
    J. M. Rooney, D. R. Squire, and V. T. Stannett, J. Polym. Sci., Polym. Chem. Ed., 14, 1877 (1976).CrossRefGoogle Scholar
  55. 55.
    R. J. Perry, U.S. Pat. 3859, 387 (1975).Google Scholar
  56. 56.
    M. Koga and H. Sato, Ger. Offen. 2508, 146 (1975).Google Scholar
  57. 57.
    V. S. Shteinbak, V. V. Amerik, F. I. Yakobson, Y. S. Kissin, D. V. Ivanyukov, and B. A. Krentsel, Eur. Poly. J., 11, 457 (1975).CrossRefGoogle Scholar
  58. 58.
    Y. Takeshita and Y. Shuts, Jap. Kokai 75, 141, 694 (November 14, 1975), C. A. 84, 151263y (1976).Google Scholar
  59. 59.
    G. A. Clegg, D. R. Gee, and T. P. Melia, Makromol. Chem., 132, 203 (1970).CrossRefGoogle Scholar
  60. 60.
    H. W. Coover, Jr., R. L. McConnel, F. B. Joyner, D. F. Slonaker, and R. L. Combs, J. Polym. Sci., Al, 4, 2563 (1966).Google Scholar
  61. 61.
    A. W. Langer, U.S. Pat. 3, 450, 795 (1969).Google Scholar
  62. 62.
    H. Tanzawa, T. Tanaka, and A. Soda, J. Polym. Sci., A2, 7, 929 (1969).Google Scholar
  63. 63.
    V. V. Americk, D. V. Inayvkov, F. I. Yakobson, and B. A. Krentsel, Vysokomol. Soedin., B15, 500 (1973).Google Scholar
  64. 64.
    E. Agouri, C. Parlant, P. Mornet, J. Rideau, and J. F. Teitgen, Makromol. Chem., 137, 229 (1970).CrossRefGoogle Scholar
  65. 65.
    N. S. Chu and J. L. Jezl, Fr. Pat. 1, 531, 409 (1968).Google Scholar
  66. 66.
    W. J. S. Craven, S. African Pat. 67 /06, 649 (1966).Google Scholar
  67. 67.
    P. Teyssie, et al., “Ring Opening Polymerization,” ACS Symp. Ser., 59, 165 (1977).CrossRefGoogle Scholar
  68. 68.
    J. Herman, R. Jerome, P. Teyssie, M. Gervais, B. Gallot, J. Makromol. Chem., 179, 1111 (1978).CrossRefGoogle Scholar
  69. 69.
    Y. Iwakura, K. Uno, T. Kusunoshita, and T. Nakanishi, Jap. Kokai 74 25, 439 (1974).Google Scholar
  70. 70.
    B. M. Baysal, E. H. Orhan, and I. Yilgor, Proje Kesin Rap. - Turk. Bilimsel Tek. Arastirma Kurumu. Polim. Kim. Unitesi., 11, 31 (1974).Google Scholar
  71. 71.
    L. Pohjola, O. Harva, and J. Karvinen, Finn. Chem. Lett., 1974, p 221.Google Scholar
  72. 72.
    W. L. Hergenrother and R. J. Ambrose, J. Polym. Sci., Polym. Lett. Ed., 12, 343 (1974).CrossRefGoogle Scholar
  73. 73.
    W. L. Hergenrother and R. J. Ambrose, J. Polym. Sci., Polym. Chem. Ed., 12, 2613 (1974).CrossRefGoogle Scholar
  74. 74.
    R. J. Ambrose and W. L. Hergenrother, J. Polym. Sci., Polym. Symp., 60, 15 (1977).Google Scholar
  75. 75.
    J. H. Grezlak and G. L. Wilkes, J. Appl. Polym. Sci., 19, 769 (1975).CrossRefGoogle Scholar
  76. 76.
    Y. Yamashita, N. Suzuki, and K. Nobutoki, Kobunshi Ronbunshu., 31, 623 (1974).CrossRefGoogle Scholar
  77. 77.
    D. M. White, U.S. Pat. 3, 875, 256 (1975).Google Scholar
  78. 78.
    C. Minazzi, J. Esnault, and A. Pleurdeau, Makromol. Chem., 177, 663 (1976).CrossRefGoogle Scholar
  79. 79.
    R. J. Zdrahala, E. M. Firer, and J. F. Fellers, J. Polym. Sci., Polym. Chem. Ed., 15, 689 (1977).CrossRefGoogle Scholar
  80. 80.
    H. R. Musser and W. J. Jackson, Jr., U.S. Pat. 3, 943, 189 (1976).Google Scholar
  81. 81.
    M. Sumoto, K. Tsuji, H. Furusawa, Jap. Kokai 74 48, 195 (1974).Google Scholar
  82. 82.
    T. Okano, M. Ikemi, and I. Shinohara, Polymer J., 10, 477 (1978).CrossRefGoogle Scholar
  83. 83.
    C. H. Bamford and E. F. T. White, Trans. Fara. Soc., 54, 268 (1958).CrossRefGoogle Scholar
  84. 84.
    L. J. Guilbault, J. Macromol. Sci., Chem. Ed., A7, 1581 (1973).Google Scholar
  85. 85.
    L. J. Guilbault, U.S. Pat. 3, 907, 927 (1975).Google Scholar
  86. 86.
    Y. Yamashita, Y. Iwaya, and K. Ito, Makromol. Chem., 176, 1207 (1975).CrossRefGoogle Scholar
  87. 87.
    A. Guyot, M. Ceysson, A. Michel, and A. Revillon, Inf. Chim., 116, 127 (1973).Google Scholar
  88. 88.
    C. H. Bamford and S. U. Mullik, Polymer, 17, 94 (1976).CrossRefGoogle Scholar
  89. 89.
    R. J. Ceresa, Polymer, 1, 397 (1960).CrossRefGoogle Scholar
  90. 90.
    R. J. Orr and H. L. Williams, J. Am. Chem. Soc., 79, 3137 (1957).CrossRefGoogle Scholar
  91. 91.
    E. Bigdeli, R. W. Lenz, B. Oster, and R. D. Lundberg, J. Polym. Sci., Polym. Chem. Ed., 16, 469 (1978).CrossRefGoogle Scholar
  92. 92.
    G. Smets, G. Weinand, and S. Deguchi, J. Polym. Sci., Chem. Ed., 16, 3077 (1978).CrossRefGoogle Scholar
  93. 93.
    G. Weinand and G. Smets, J. Polym. Sci., Chem. Ed., 16, 3091 (1978).CrossRefGoogle Scholar
  94. 94.
    B. M. Baysal, E. H. Orhan, and I. Yilgor, J. Polym. Sci., Polym. Symp., 46, 237 (1973).CrossRefGoogle Scholar
  95. 95.
    A. V. Tobolsky, U.S. Pat. 3, 865, 898 (1975).Google Scholar
  96. 96.
    P. Lalet, H. Fassy, and A. Miletto, Fr. Pat. 2, 213, 293, (1974).Google Scholar
  97. 97.
    E. B. Milovskaya and L. V. Zamoiskaya, Vysokomol. Soedin., Ser. B, 18, 300 (1976).Google Scholar
  98. 98.
    L. V. Zamoiskaya, E. S. Gankina, and E. B. Milovskaya, Vysokomol. Soedin., Ser A, 18, 1635 (1976).Google Scholar
  99. 99.
    J. J. Laverty and Z. G. Gardlund, Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem., 15 (2), 306 (1974).Google Scholar
  100. 100.
    S. N. Gupta and U. Nandi, Makromol. Chem., 176, 3179 (1975).CrossRefGoogle Scholar
  101. 101.
    Y. Vinchon, R. Reeb, and G. Riess, Eur. Polym. J., 12, 317 (1976).CrossRefGoogle Scholar
  102. 102.
    A. S. Dunn, B. D. Stead, and H. W. Melville, Trans. Fara. Soc., 50, 279 (1954).CrossRefGoogle Scholar
  103. 103.
    W. Kawai, J. Polym. Sci., Chem. Ed., 15, 1479 (1977).CrossRefGoogle Scholar
  104. 104.
    W. Kawai, J. Macrolmol. Sci., Chem. Ed., All, 1027 (1977).Google Scholar
  105. 105.
    A. Chapiro, F. Jaberg, and L. Perec-Spritzer, Eur. Polym. J., 11, 637 (1975).CrossRefGoogle Scholar
  106. 106.
    D. J. Angier and W. F. Watson, J. Polym. Sci., 25, 1 (1957).CrossRefGoogle Scholar
  107. 107.
    A. Casale and R. S. Porter, Adv. Polym. Sci., 17, 1 (1975).CrossRefGoogle Scholar
  108. 108.
    K. F. O’Driscoll and A. U. Sridharan, Appl. Polym. Symp., 26, 135 (1975).Google Scholar
  109. 109.
    H. Fujiwara, H. Kakiuchi, K. Katsuhiko, and K. Goto, Kobunshi Ronbunshu, 33, 183 (1976).CrossRefGoogle Scholar
  110. 110.
    J. J. Laverty and Z. G. Gardlund, J. Polym. Sci., Polym. Chem. Ed., 15, 2001 (1977).CrossRefGoogle Scholar
  111. 111.
    I. Piirma and H. Chou, Polym. Prepr., ACS Div. Polym. Chem., 16 (2), 506 (1975).Google Scholar
  112. 112.
    N. G. Ivanova, S. S. Ivanchev, and N. M. Domareva, Vysokomol. Soedin., Ser. A., 18, 2788 (1976).Google Scholar
  113. 113.
    S. S. Ivanchev, N. G. Ivanova, Y. L. Zherebin, Plaste Kautsch, 23, 5 (1976).Google Scholar
  114. 114.
    I. Piirma and B. Gunesin, Polym. Prepr., ACS Div. Polym. Chem., 18 (1), 687 (1977).Google Scholar
  115. 115.
    A. I. Kirillov, A. D. Molinkov, and Y. A. Zvereva, Russ. 440, 378 (1974).Google Scholar
  116. 116.
    G. D. Rudkovskaya, I. N. Nikonova, I. A. Baranovskaya, V. A. Belov, and T. A. Sokolova, Vysokomol. Soedin., Ser. A, 17, 13 (1975);Google Scholar
  117. 117.
    G. D. Rudkovskaya, I. A. Baranovskyaya, I. N. Nikonova, T. A. Komogorova, and T. A. Sokolova, Vysokomol. Soedin., Ser. B, 17, 786 (1975);Google Scholar
  118. 118.
    A. J. Chapiro, Chem. Phys., 47, 747 (1950).Google Scholar
  119. 119.
    J. Hiemeleers and G. Smets, Makromol. Chem., 47, 7 (1961).CrossRefGoogle Scholar
  120. 120.
    B. Atkinson and G. R. Cotten, Trans. Fara. Soc., 54, 877 (1958).CrossRefGoogle Scholar
  121. 121.
    E. U. Tsuchida, et al., J. Chem. Soc. Japan, 70, 573 (1967).Google Scholar
  122. 122.
    R. B. Seymour, H. S. Tsang, E. E. Jones, P. D. Kincaid, and A. K. Patel, Advan. Chem. Ser., 99, 418 (1971).CrossRefGoogle Scholar
  123. 123.
    C. H. Bamford, J. Polym. Sci., 48, 37 (1960).CrossRefGoogle Scholar
  124. 124.
    Y. Minoura and Y. Ogota, J. Polym. Sci., A-1, 7, 2547 (1969).CrossRefGoogle Scholar
  125. 125.
    R. B. Seymour, D. R. Owen, G. A. Stahl, H. Wood, and W. N. Tinnerman, Appl. Polym. Symp., 25, 69 (1974).Google Scholar
  126. 126.
    R. B. Seymour, G. A. Stahl, D. R. Owen, and H. Wood, Advan. Chem. Ser., 142, 309 (1975).CrossRefGoogle Scholar
  127. 127.
    K. Horie and D. Mikulasova, Makromol. Chem., 175, 2091 (1974).CrossRefGoogle Scholar
  128. 128.
    D. Mikulasova, V. Chrastova, P. Citovicky, and K. Horie, Makromol. Chem., 178, 429 (1977).CrossRefGoogle Scholar
  129. 129.
    H. Tanaka, T. Sato, and T. Otsu, Macromol. Chem., 180, 267 (1979).CrossRefGoogle Scholar
  130. 130.
    R. B. Seymour, G. A. Stahl, and H. Wood, Appl. Polym. Symp., 26, 249 (1975).Google Scholar
  131. 131.
    G. A. Stahl, R. B. Seymour, and D. P. Garner, Coatings and Plastics Prepr., ACS Div. of Organic Coatings and Plastics Chemistry, 37 (1), 714 (1977).Google Scholar
  132. 132.
    A. V. Olevin, M. B. Lachinov, V. P. Zubov, and V. A. Kobonov, Vysokomol. Soedin., Ser. B, 18, 219 (1967);Google Scholar
  133. 133.
    A. Arfaei, R. N. Haszeldine, and S. Smith, J. Chem. Soc., Chem. Commun., 1976, 260.Google Scholar

Copyright information

© Plenum Press, New York 1980

Authors and Affiliations

  • G. Allan Stahl
    • 1
  1. 1.BF Goodrich Research and Development CenterBrecksvilleUSA

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