Inhonogeneity of Active Centers of Heterogeneous Ziegler-Natta Catalysts

  • Y. V. Kissin
Part of the Polymers book series (POLYMERS, volume 9)

Abstract

Active center inhomogeneity with respect to kinetic characteristics is a well-known attribute of any heterogeneous catalyst. In the case of usual catalytic processes, where both reagents and products are low molecular compounds, the inhomogeneity of the centers is frequently masked by overlapping adsorption and desorption phenomena: under a given set of conditions, the most active centers are blocked by adsorbed products, the least active centers weakly adsorb reagents, and only the centers of medium activity “function.” In the case of heterogeneous Ziegler-Natta catalysts these masking phenomena have no great significance. The mean olefin adsorption capacity of their active centers is low (see Section II-8) and the reaction products, polyolefin molecules, are not adsorbed on the active centers at all. For this reason, these catalysts can be regarded as good subjects for the study of active center inhomogeneity.

Keywords

Ethyl Alkene Boiling Polystyrene Macromolecule 

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References

  1. [1]
    N.G. Gaylord and H.M. Mark, “Linear and Stereoregular Addition Polymers”, Interscience, New York, 1959.Google Scholar
  2. [2]
    G. Natta, J. Polym. Sci., 34, 531 (1959).CrossRefGoogle Scholar
  3. [3]
    V.L. Folt, T.I. Shipman, and S.S. Krimm, J. Polym. Sci., 61, 517 (1962).CrossRefGoogle Scholar
  4. [4]
    G. Natta, C. Valvassori, G. Ciampelli, and G. Mazzanti, J. Polym. Sci., Part A, 3, 1 (1965).Google Scholar
  5. [5]
    G. Kennedy, G. Minkler, J. Nanles, and P. Tomas, J. Polym. Sci., Part A, 2, 2093 (1964).Google Scholar
  6. [6]
    A.A. Zharov, Y.V. Kissin, O.N. Pirogov, and N.S. Enikolopyan. Vysokomol. Soedin., 6, 962 (1964).Google Scholar
  7. [7]
    K. Gehrke, A. Bledski, and J. Ulbricht, Plaste und Kautschuk, 17, 251 (1970).Google Scholar
  8. [8]
    A. Dankovics and Y.V. Kissin, Vysokomol. Soedin., A12, 802 (1970).Google Scholar
  9. [9]
    A. Pavan, A Provassoli, G. Moraglio, and A. Zambelli, Makromol. Chem., 178, 1099 (1977).CrossRefGoogle Scholar
  10. [10]
    J.P. Sibilia and R.C. Wincklehofer, J. Appl. Polym. Sci., 6, s-56 (1962).CrossRefGoogle Scholar
  11. [11]
    A. Nakajima and H. Fujiwara, Bull. Chem. Soc. Japan, 34, 909 (1964).CrossRefGoogle Scholar
  12. [12]
    R.L. Combs, D.F. Slonaker, F.B. Joyner, and H.W. Coover, J. Polym. Sci., Part A-l, 5, 214 (1967).CrossRefGoogle Scholar
  13. [13]
    J. Natta, I. Pasquon, A. Zambelli, and A. Gatti, Makromol. Chem., 70, 191 (1964).CrossRefGoogle Scholar
  14. [14]
    C. Wolfsgruber, G. Zannoni, E. Rigamonti, and A. Zambelli, Makromol. Chem., 176, 2765 (1975).CrossRefGoogle Scholar
  15. [15]
    Y. Doi, E. Suzuki, and T. Keii, Makromol. Chem., Rapid Commun., 2, 293 (1981).CrossRefGoogle Scholar
  16. [16]
    U.V. Suter and P. Neunsehwander, Macromolecules, 14, 528 (1981).CrossRefGoogle Scholar
  17. [17]
    F.C. Stehling and J.R. Knox, Macromolecules, 8, 595 (1975).CrossRefGoogle Scholar
  18. [18]
    J.C. Woodbrey and Q.A. Trementozzi, J. Polym. Sci, Part C, 8, 113 (1964).Google Scholar
  19. [19]
    J.C. Randall, J. Polym. Sci, Part A-2, 14, 2083 (1976).Google Scholar
  20. [20]
    Y. Doi, Makromol. Chem., Rapid Commun., 3, 635 (1982).CrossRefGoogle Scholar
  21. [21]
    I. Pasquon, G. Natta, A. Zambelli, A. Marinangelli, and A. Surico, J. Polym. Sci., Part C, 16, 25011 (1976).Google Scholar
  22. [22]
    G. Natta, I. Pasquon, P. Corradini, M. Peraldo, M. Pegoraro, and A. Zambelli, Atti. Acad. Nazi Lincei, Rend class sci., fic. mat. e nat., [8] 28, 539 (1960).Google Scholar
  23. [23]
    H. Okamoto, K. Miyamishi, and O. Isizuka, Chem. High Polym. Japan, 21, 218 (1964).Google Scholar
  24. [24]
    K. Mitani, A. Matsuo, T. Suzuki, and J. Takagami, J. Polym. Sci., Part A-l, 12, 771 (1974).Google Scholar
  25. [25]
    Y. Doi. Makromol. Chem., 180, 2447 (1979).CrossRefGoogle Scholar
  26. [26]
    N. Kashiwa and J. Yoshitake, Makromol. Chem., Rapid Commun., 4, 41 (1983).CrossRefGoogle Scholar
  27. [27]
    G. Crespi and G. Maraglio, Chim. Ind. (Milan), 39, 275 (1957).Google Scholar
  28. [28]
    A.P. Firsov, I.V. Eremina, and N.M. Chirkov, Vysokomol. Soedin., 6, 377 (1964).Google Scholar
  29. [29]
    Y.V. Kissin, V.I. Tsvetkova, and N.M. Chirkov, Eur. Polym. J., 8, 529 (1972).CrossRefGoogle Scholar
  30. [30]
    Y.V. Kissin, V.I. Tsvetkova, and N.M. Chirkov, Vysokomol. Soedin., A9, 1104 (1967).Google Scholar
  31. [31]
    A. Zambelli, P. Locatelli, A. Pravasoli, and D.R. Ferro, Macromolecules, 13, 267 (1980).CrossRefGoogle Scholar
  32. [32]
    P. Pino, G. Guastalla, B. Rotzinger, and R. Mulhaupt, in “Transition Metal Catalyzed Polymerizations: Alkenes and Dienes” R.P. Quirk, ed., Harwood Acad. Publ., New York, 1983, p. 435.Google Scholar
  33. [33]
    J.C.W. Chien, J. Polym. Sci., Part A, 1, 425 (1963).Google Scholar
  34. [34]
    T. Keii, M. Tamura, E. Suzuki, and Y. Doi, in “Transition Metal Catalyzed Polymerizations Alkenes and Dienes” R.P. Quirk, ed., Harwood Acad. Publ., New York, 1983, p. 97.Google Scholar
  35. [35]
    A.W. Langer, T.J. Burkhardt, and J.J. Steger, in “Transition Metal Catalyzed Polymerizations: Alkenes and Dienes” R.P. Quirk, ed., Harwood Acad. Publ., New York 1983, p. 421.Google Scholar
  36. [36]
    A.J. Sivak and Y.V. Kissin, J. Polym. Sci., Polym. Chem. Ed., 22, 3729 (1984).CrossRefGoogle Scholar
  37. [37]
    N. Kashiwa, in “Transition Metal Catalyzed Polymerizations: Alkenes and Dienes”, R.P. Quirk, ed., Harwood Acad. Publ., New York, 1983, p. 379.Google Scholar
  38. [38]
    R. Spitz, J.L. Lacombe, M. Primet, and A. Guyot, in “Transition Metal Catalyzed Polymerizations: Alkenes and Dienes”, R.P. Quirk, ed., Harwood Acad. Publ., New York, 1983, p. 389.Google Scholar
  39. [39]
    E.I. Vizen, L.A. Rishina, and F.S. Dyachkowsky, Eur. Polym. J., 18, 773 (1982); 20, 1027 (1984).CrossRefGoogle Scholar
  40. [40]
    P.J. Flory, “Principles of Polymer Chemistry”, Cornell University Press, Ithaca, N.Y., 1953.Google Scholar
  41. [41]
    L.L. Bohm and H. Passing, Makromol. Chem., 177, 1097 (1976).CrossRefGoogle Scholar
  42. [42]
    H. Wesslau, Makromol. Chem., 20, 111 (1956); ibid, 26, 102 (1958).CrossRefGoogle Scholar
  43. F.I. Jacobson, 28th IUPAC Internat. Macromol. Symp., Amherst, Massachusetts, 1982, Proceedings, p. 246.Google Scholar
  44. [44]
    L.H. Tung, J. Polym. Sci., 24, 333 (1957).CrossRefGoogle Scholar
  45. [45]
    G.K. Williamson, B. Wright, and R.N. Haward, J. Appl. Chem., 14, 131 (1964).CrossRefGoogle Scholar
  46. [46]
    V.V. Amerik, S.A. Bocharov, D.V. Ivanyukov, E.A. Kazaryan, F.I. Yakobson, and V.F. Petrova, Vysokomol. Soedin., B13, 902 (1971).Google Scholar
  47. [47]
    M.V. Vaughan and M.A. Francis, J. Appl. Polym. Sci., 21, 2409 (1977).CrossRefGoogle Scholar
  48. [48]
    J.M. Guenot, Z. Gallot, C. Picot, and H. Benoit, J. Appl. Polym. Sci., 21, 2181 (1977).CrossRefGoogle Scholar
  49. [49]
    A.G. Rodionov, N.M. Domareva, A.A. Baulin, E.L. Ponamareva, and S.S. Ivanchev, Vysokomol. Soedin., A23, 1560 (1981).Google Scholar
  50. [50]
    U. Zucchini and G. Cecchin, Adv. Polym. Sci., 51, 101 (1983).CrossRefGoogle Scholar
  51. [51]
    H.-G. Yuan, T.W. Taylor, K.-Y. Choi, and W.H. Ray, J. Appl. Polym. Sci., 27, 1961 (1982).CrossRefGoogle Scholar
  52. [52]
    Y. Doi and T. Keii, Makromol. Chem., 179, 2117 (1978).CrossRefGoogle Scholar
  53. [53]
    Y. Doi, M. Takeda, and T. Keii, Makromol. Chem., 180, 57 (1979).CrossRefGoogle Scholar
  54. [54]
    T. Keii, A. Morinaga, S. Echigoya, E. Suzuki, M. Tamura, G. Shinagava, and Y. Doi, 28th IUPAC Internat. Macromol. Symp., Amherst, Massachusetts, 1982, Proceedings, p. 237.Google Scholar
  55. [55]
    Y. Doi, M. Murata, and T. Keii, 28th IUPAC Internat. Macromol. Symp., Amherst, Massachusetts, 1982, Proceedings, p. 242.Google Scholar
  56. [56]
    A.B. Agasaryan, G.P. Belov, S.P. Davyan, and M.L. Erytyan, Eur. Polym. J., 11, 549 (1975).CrossRefGoogle Scholar
  57. [57]
    Y. Doi, Y. Nishimura, and T. Keii, Polymer, 22, 469 (1981).CrossRefGoogle Scholar
  58. [58]
    A. Siove, M. Fontanille, 28th IUPAC Internat. Macromol. Symp., Amherst, Massachusetts, 1982, Proceedings, p. 236.Google Scholar
  59. [59]
    V.I. Tsvetkova, A.N. Plyusnin, R.F. Bolshakova, B.A. Uvarov, and N.M. Chirkov, Vysokomol. Soedin., A11, 1817 (1969).Google Scholar
  60. [60]
    S.Y. Frenkel, “Introduction to the Statistic Theory of Polymerization Processes”, Khimia, Moscow, 1965.Google Scholar
  61. [61]
    W.L. Carrick, J. Am. Chem. Soc., 82, 3883 (1960).CrossRefGoogle Scholar
  62. [62]
    P.M. Hengry, J. Polym. Sci., 36, 3 (1959).CrossRefGoogle Scholar
  63. [63]
    L.L. Bohm, Polymer, 19, 562 (1978).CrossRefGoogle Scholar
  64. [64]
    T.E. Davis and R.L. Tobias, J. Polym. Sci., 50, 227 (1961).CrossRefGoogle Scholar
  65. [65]
    M. Pegorari, Chim. Ind. (Milan), 44, 18 (1962).Google Scholar
  66. [66]
    S. Tanaka, H. Morikawa, and A. Nakamura, Chem. High Polym. (Japan), 22, 775 (1965).Google Scholar
  67. [67]
    M. Hirooka, H. Kauda, and K. Nakaguchi, J. Polym. Sci., Part B, 1, 701 (1963).CrossRefGoogle Scholar
  68. [68]
    S. Bresler, Disc. Faraday Soc., 25, 199 (1958).CrossRefGoogle Scholar
  69. [69]
    M. Gordon and R. J. Rae, Polymer, 2, 41, 60 (1961).Google Scholar
  70. [70]
    V.W. Bulls and T.L. Higgins, J. Polym. Sci., Part A-l, 8, 1037 (1970).CrossRefGoogle Scholar
  71. [71]
    W.R. Schmeal and J.R. Street, J. Polym. Sci., Part A-2, 10, 2173 (1972).CrossRefGoogle Scholar
  72. [72]
    W.R. Schmeal and J.R. Street AICHE J., 17, 1199 (1971).CrossRefGoogle Scholar
  73. [73]
    D. Singh and R.P. Merrill, Macromolecules, 4, 599 (1971).CrossRefGoogle Scholar
  74. [74]
    A. Clark and G.C. Bailey, J. Catal., 2, 230 (1963).CrossRefGoogle Scholar
  75. [75]
    G. Natta, J. Polym. Sci., 34, 21 (1959).CrossRefGoogle Scholar
  76. [76]
    F.I. Yakobson, V.V. Amerik, and D.I. Ivanyukov, Vysokomol. Soedin., A15, 2795 (1973).Google Scholar
  77. [77]
    F.I. Yakobson, V.V. Amerik, D.I. Ibanyukov, V.F. Petrova, V.S. Shteinbak, and B.A. Krenstel, Vysokomol. Soedin., A13, 616 (1971).Google Scholar
  78. [78]
    E.I. Vizen and F.I. Yakobson, Vysokomol. Soedin., A20, 927 (1978).Google Scholar
  79. [79]
    K.H. Reichert, H. Franz, N. Guentherberg, 28th IUPAC Internat. Macromol. Symp., Amherst, Massachusetts, 1982, Proceedings, p. 255.Google Scholar
  80. [80]
    V. Warzelhan and T.F. Burger, Internat. Symp. Macromol., Florence, Italy, 1980, Preprints, Vol. 2, p. 13.Google Scholar
  81. [81]
    V. Warzelhan, T.F. Burger, and D.J. Stein, Makromol. Chem., 183, 489 (1982).CrossRefGoogle Scholar
  82. [82]
    P. Locatelli, A. Provasoli, and A. Zambelli, Makromol. Chem., 176, 2711 (1975).CrossRefGoogle Scholar
  83. [83]
    C. Tosi and F. Ciampelli, Adv. Polym. Sci., 12, 87 (1973).CrossRefGoogle Scholar
  84. [84]
    C. Cosewith and G. Verstrate, Macromolecules, 4, 482 (1971).CrossRefGoogle Scholar
  85. [85]
    S. Davison and G.L. Tailor, Brif. Polym. J., 4, 65 (1972).CrossRefGoogle Scholar
  86. [86]
    A. Turner-Jones, Polymer, 7, 23 (1966).CrossRefGoogle Scholar
  87. [87]
    G.E. Ham (ed.), “Copolymerization”, Interscience, New York, 1964.Google Scholar
  88. [88]
    Y.V. Kissin, Adv. Polym. Sci., 15, 91 (1974).Google Scholar
  89. [89]
    B. Baker and P.J.T. Tait, Polymer, 8, 205 (1967).CrossRefGoogle Scholar
  90. [90]
    H.W. Coover, R.L. McDonnell, F.B. Joyner, D.F. Slonaker, and R.L. Combs, J. Polym. Sci., Part A-l, 4, 2563 (1966).CrossRefGoogle Scholar
  91. [91]
    I.H. Anderson, G.M. Burnett, and P.J.T. Tait, J. Polym. Sci., 56, 391 (1962).CrossRefGoogle Scholar
  92. [92]
    E.I. Vizen and Y.V. Kissin, Vysokomol. Soedin., A11, 1774 (1969).Google Scholar
  93. [93]
    C. Tosi, Chim. Ind(Milan), 53, 459 (1971).Google Scholar
  94. [94]
    T. Simonazzi, F. Sevini, and C. Tosi, Quaderni Pic. Sci., 84, 206 (1973).Google Scholar
  95. [95]
    G. Natta, G. Mazzanti, A. Valvassori, and G. Sartori, Chim. Ind. (Milan), 40, 717, 896 (1958).Google Scholar
  96. [96]
    G. Mazzanti, A. Valvassori, and G. Pajaro, Chim. Ind. (Milan), 39, 741, 825 (1957).Google Scholar
  97. [97]
    G. Natta, G. Mazzanti, A. Valvassori, G. Sartori, and D. Fiumani, J. Polym. Sci., 51, 411 (1961).CrossRefGoogle Scholar
  98. [98]
    N.G. Bakayutov, Y.V. Kissin, I.I. Vavilova, Z.A. Arkhipova, and V.F. Erofeev, Vysokomol. Soedin., A17, 2163 (1975).Google Scholar
  99. [99]
    V.S. Shteinbak, Y.V. Kissin, V.V. Amerik, S.M. Mezhikovsky, F.I. Yakobson, and D.I. Ivanyukov, Vysokomol. Soedin., A16, 2536 (1974).Google Scholar
  100. [100]
    C.G. Overberger and S. Nozakura, J. Polym. Sci., Part A, 1, 1439 (1963).Google Scholar
  101. [101]
    J.C.W. Chien and C.-I. Kuo, J. Polym. Sci., Polym. Chem. Ed., 23, 761 (1985).CrossRefGoogle Scholar
  102. E. Chiellini, A.M. Raspolli-Galletti, and R. Solaro, Macromolecules, 17, 2212 (1984).Google Scholar

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© Springer-Verlag New York Inc. 1985

Authors and Affiliations

  • Y. V. Kissin
    • 1
  1. 1.Gulf Research and Development CompanyPittsburghUSA

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