Advertisement

Electrochemical production of initiators for polymerization processes

  • Giuseppe Silvestri
  • Salvatore Gambino
  • Giuseppe Filardo
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 38)

Abstract

The most important technological interest in initiator production lies, in the electrosynthesis of complex catalytic systems, i. e. coordination compounds and Ziegler-Natta catalysts, although the choice of olefins to be polymerized with these electrosynthesized complexes is still limited to ethylene and to very few other monomers.

Looking at “in line” continuous production of initiators for the polymerization of acrylics and vinylics, the long-life cations and anions quoted here and the “prepolymerization” effects observed in many cases make it attractive to consider these intermediates for applicative purposes as well.

Indeed, we believe that the perspectives of applicative developments of electropolymerization suffer from the same limitations one could find in other sectors of electro-organic technology: the comparison between well established “conventional” processes and processes adopting new technologies is too often favorable to the conventional ones for many and varied reasons (process experience, reliability, confidence in operation of the plants, conservative management etc.). Therefore new technologies have to prove to be much more convenient and able to solve or to overcome important and dramatic failures of the existing processes to be considered as alternatives when new industrial production is planned.

In a vast majority of cases electrochemistry just offers some moderate advantages but not revolutionary advances. Therefore a slow expansion of industrial electroorganic processes and, consequently, a problematic introduction of electropolymerization into industrial practice should be expected.

A different comment can be made on basic research: the field is very active, and combination of spectrophotometric and electroanalytical techniques for the understanding of the reaction mechanisms is usually adopted by many research groups. In fact, especially with regard to the influence of the supporting electrolyte and the evolution of the intermediate species, too often electroanalytical determinations are unadequate for the understanding of the mechanism, so the problems must be solved with still more imaginative approaches.

Keywords

Vinyl Ether Electrochemical Synthesis Anionic Polymerization Electrochemical Polymerization Cationic Polymerization 
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.

List of Abbreviations

acac

2,4-pentanedionate (acetylacetonate)

AM

acrylamide

AN

acrylonitrile

bipy

bipyridine

Bu

n-butyl

Cp

cyclopentadiene

DCE

1,2-dichloroethane

DCM

dichloromethane

DEF

diethyl fumarate

DMA

9,10-dimethylanthracene

DMF

N,N-dimethylformamide

DMSO

dimethyl sulfoxide

DPA

9,10-diphenylanthracene

Et

ethyl

IBVE

isobutyl vinyl ether

MA

methyl acrylate

MeSt

α-methylstyrene

MMA

methyl methacrylate

NBVE

n-butyl vinyl ether

NVCZ

N-vinylcarbazole

OPUF

open pore urea-formaldehyde

p

perylene

9PA

9-phenylanthracene

pp

perylene perchlorate

RU

rubrene

TBAI

tetrabutylammonium iodide

TBATI

tetrabutylammonium triiodide

THF

tetrahydrofuran

TP

triphenylene

TPP

1,3,6,8-tetraphenylpyrene

TRO

1,3,5-trioxane

St

styrene

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

VI. References

  1. 1.
    Damaskin, B., Petrü, O, Batrakov, V.: Adsorption of Organic Compounds on Electrodes, Plenum Press, New York - London (1971)Google Scholar
  2. 2.
    Lund, H., Simonet, J.: J. Electroanal. Chem. Interfacial Electrochem. 65, 205 (1975)Google Scholar
  3. 3.
    Filardo, G. et al.: J. Chem. Soc. Dalton Trans. 1974, 1787Google Scholar
  4. 4.
    Dey, A. N., Rudd, E. J.: J. Electrochem. Soc. 121, 1294–1298 (1974)Google Scholar
  5. 5.
    Akbulut, U., Fernandez, J., Birke, R.: J. Polym. Sci., Polym. Chem. Ed. 13, 133 (1975)CrossRefGoogle Scholar
  6. 6.
    Parravano, G., In: Baizer, M. M.: Organic Electrochemistry, New York, Dekker: 1973Google Scholar
  7. 7.
    Funt, L., Tanner, J., In: Weinberg, N. L.: Technique of electroorganic synthesis, New York - London - Sydney - Toronto: Wiley 1975Google Scholar
  8. 8.
    Shapoval, G. S., Gorodyskii, A. V., Russ. Chem. Rev. (Engl. Transl.), 42, 370 (1973)CrossRefGoogle Scholar
  9. 9.
    Gaylord, N. G., Takahashi, A., Addition a. Condensation Polymeriz. Proc. (Platzer, N., ed.) (Adv. Chem. Ser., 91) Amer. Chem. Soc., Washington D. C. 1969, p. 94Google Scholar
  10. 10.
    Phillips, D. C., Smith, J. B., Davies, D. H.: J. Polym. Sci., Polym. Chem. Ed. 10, 3267 (1972)Google Scholar
  11. 11.
    Phillips, D. C., Smith, J. B., Davies, D. H.: ibid., 11, 1867 (1973)CrossRefGoogle Scholar
  12. 12.
    Davies, D. H., Phillips, D. C., Smith, J. B.: ibid. 10, 3253 (1972)CrossRefGoogle Scholar
  13. 13.
    Phillips, D. C., Davies, D. H., Smith, J. B.: Makromol. Chem. 154, 317 (1972)CrossRefGoogle Scholar
  14. 14.
    Phillips, D. C., Davies, D. H., Smith, J. D. B.: Macromolecules 5, 674 (1972)CrossRefGoogle Scholar
  15. 15.
    Phillips, D. C., Davies, D. H., Smith, J. D. B.: Makromol. Chem. 169, 177 (1973)CrossRefGoogle Scholar
  16. 16.
    Phillips, D. C., Davies, D. H., Jackson, J. A.: Makromol. Chem. 177, 3049 (1976)CrossRefGoogle Scholar
  17. 17.
    Davies, D. H., Phillips, D. C., Smith, J. D. B.: J. Polym. Sci., Polym. Chem. Ed. 15, 2673 (1977)CrossRefGoogle Scholar
  18. 18.
    Lehmkuhl, H., In: Baizer, M. M.: Organic Electrochemistry, New York: Dekker 1973Google Scholar
  19. 19.
    Matschiner, H., Kerrinnes, H. J., Issleit, K.: Z. Anorg. Allg. Chem. 380(I), 1, (1971)CrossRefGoogle Scholar
  20. 20.
    Eisenbach, W., Lehmkuhl. H., Wilke, G.: Ger. Offen. 2,349,561, Apr. 25, 1974; Chem. Abstr. 81, 20237h (1974)Google Scholar
  21. 21.
    Lehmkuhl, H., Eisenbach, W.: Justus Liebigs Ann. Chem. 4, 672 (1975)CrossRefGoogle Scholar
  22. 22.
    Ercoli, R., Guainazzi, M., Silvestri, G.: J. Chem. Soc., Chem. Commun. 1967, 927Google Scholar
  23. 23.
    Silvestri, G. et al.: J. Chem. Soc., Dalton Trans. 1972, 2558Google Scholar
  24. 24.
    Guainazzi, M. et al.: J. Chem. Soc., Dalton Trans. 1972, 927Google Scholar
  25. 25.
    Allen, P. E. M., Patrick, C. R.: Kinetics and Mechanisms of Polymerization Reactions, p. 433, New York: Wiley 1974Google Scholar
  26. 26.
    Lehmkuhl, H., Schäfer, R.: Tetrahedron Lett. 21, 2315 (1966)CrossRefGoogle Scholar
  27. 27.
    Mottus, E. H., Ort, M. O.: J. Electrochem. Soc. 117, 885 (1970)CrossRefGoogle Scholar
  28. 28.
    Mottus, E. H., Ort, M. O.: U. S. Pat. 3,516,978, June 23 (1970)Google Scholar
  29. 29.
    Ort, M. O. et al.: U. S. Pat. 3,546,083, Dec. (1970)Google Scholar
  30. 30.
    Mottus, E. H., Ort, M. O.: Electrochem. Soc. Meeting, Vol. 73, May 1973; Abstr. 186Google Scholar
  31. 31.
    Mottus, E. H., Ort, M. O.: U. S. Pat. 3,787,383, Jan. 22 (1974) as continuation of a series of patents on the same subject, starting with the first filing in 1966Google Scholar
  32. 32.
    Ercoli, R., Guainazzi, M., Silvestri, G.: Ger. Offen. 2,116,227 Oct. 21 (1971) as extension of Ital. pat. filed on Apr. 3, (1970)Google Scholar
  33. 33.
    Ercoli, R., Guainazzi, M., Silvestri, G.: Ger. Offen. 2,233,335, Nov. 23 (1972)Google Scholar
  34. 34.
    Thomas, C. A.: Anhydrous Aluminium Chloride in Organic Chemistry, Amer. Chem. Soc. Monogr. Ser., Reinhold Publishing Corp. p. 796 (1941)Google Scholar
  35. 35.
    Guainazzi, M., Filardo, G.: Chim. Ind. (Milan) 57, 630 (1975)Google Scholar
  36. 36.
    Filardo, G., Guainazzi, M.: J. Chem. Soc., Dalton Trans. 1974, 679Google Scholar
  37. 37.
    Guainazzi, M. et al.: J. Chem. Soc., Chem. Commun. 1973, 138Google Scholar
  38. 38.
    Ercoli, R. et al.: Ger. Offen. 2,326,860, Nov. 29 (1973)Google Scholar
  39. 39.
    Koval'chuk, E. P., Tsvetkov, N. S., Fioshin, M.: Elektrokhimiya, 12, (10) 1558 (1976)Google Scholar
  40. 40.
    Koval'chuk, E. P., Tsvetkov, N. S., Fioshin, M.: Chem. Abstr. 83, 59418j (1975)Google Scholar
  41. 41.
    Koval'chuk, E. P., Komendat, L. N., Tsvetkov, N. S.: Chem. Abstr. 83, 164695v (1975)Google Scholar
  42. 42.
    Koval'chuk, E. P. et al.: Elektrokhimiya 13, (4), 614 (1977)Google Scholar
  43. 43.
    Mendis, L. P., Pemawansa, K. P. W., Hettiarachchi: Polymer 18, 100 (1977)CrossRefGoogle Scholar
  44. 44.
    Koval'chuk, E. P. et al.: Elektrokhimiya 13(1), 139 (1977)Google Scholar
  45. 45.
    Koval'chuk, E. P., Tsvetkov, N. S., Gnutenko, V. A.: Chem. Abstr. 87, 6416h (1977)Google Scholar
  46. 46.
    Levinos, S.: US Pat. 4,012,295, Mar. 15 (1977)Google Scholar
  47. 47.
    Eberson, L., Schafer, H.: Topics Curr. Chem. 21, 1 (1971)Google Scholar
  48. 48.
    Wawzonek, S. et al.: J. Electrochem. Soc. 103, 456 (1956)CrossRefGoogle Scholar
  49. 49.
    Umemoto, K.: Bull. Chem. Soc. Japan 40, 1058 (1967)CrossRefGoogle Scholar
  50. 50.
    Trifonov, A., Panayotov, I. M.: Makromol. Chem. 77, 237 (1964)CrossRefGoogle Scholar
  51. 51.
    Lazarov, S., Trifonov, A., Panayotov, I.: Z. Phys. Chem. (Leipzig) 233 (1–2), 49 (1966)Google Scholar
  52. 52.
    Romanin, A. M.: Chim. Ind. (Milan) 55, 432 (1973)Google Scholar
  53. 53.
    Bezuglyi, V. D., Shapovalov, V. A., Kovalev, I. P.: Vysokomol. Soedin., Ser A:18 (4), 899 (1976)Google Scholar
  54. 54.
    Bhadani, S. N., Parravano, G.: J. Polym. Sci. Part A-1, 8, 225 (1970)CrossRefGoogle Scholar
  55. 55.
    Bhadani, S. N., Prasad, S.: Makromol. Chem. 178, 187 (1977)CrossRefGoogle Scholar
  56. 56.
    Gambino, S., Silvestri, G.: Tetrahedron Lett. 32, 3025 (1973)CrossRefGoogle Scholar
  57. 57.
    Silvestri, G., Gambino, S., Filardo, G.: Electrochem. Soc. Spring Meet., Washington D. C. May 2–7 (1976), abstr. 278Google Scholar
  58. 58.
    Mengoli, G., Vidotto, G.: Makromol. Chem. 150, 277 (1971)CrossRefGoogle Scholar
  59. 59.
    Turcot, L., Glasel, A., Funt, B. L.: J. Polym. Sci., Polym. Lett. Ed. 12, 687 (1974)CrossRefGoogle Scholar
  60. 60.
    Funt, B. L., Verigin, V.: Can. J. Chem. 52, 1643 (1974)CrossRefGoogle Scholar
  61. 61.
    Glasel, A., Murray, K., Funt, B. L.: Makromol. Chem. 177, 3345 (1976)CrossRefGoogle Scholar
  62. 62.
    Mengoli, G., Vidotto, G.: J. Electroanal. Chem. Interfacial Electrochem. 75, 595 (1977)Google Scholar
  63. 63.
    Oberrauch, E., Salvatori, T., Cesca, S.: J. Polym. Sci., Polym. Lett. Ed. 16 (7), 345 (1978)CrossRefGoogle Scholar
  64. 64.
    Vallot, R., Liang, Tse Yu: C. R. Hebd. Seances Acad. Sci. Ser. C: 284, 759 (1977)Google Scholar
  65. 65.
    Pistoia, G., Ricci, A., Voso, M. A.: J. Appl. Polym. Sci. 20, 2441 (1976)CrossRefGoogle Scholar
  66. 66.
    Pistoia, G., Voso, M. A.: J. Polym. Sci., Polym. Chem. Ed. 14, 1811 (1976)CrossRefGoogle Scholar
  67. 67.
    Schouten, A. J., Challa, G.: J. Polym. Sci., Polym. Chem. Ed. 12, 2145 (1974)CrossRefGoogle Scholar
  68. 68.
    Aurizi, A., Filippeschi, V., Pistoia, G.: J. Appl. Electrochem. 7, 139 (1977)CrossRefGoogle Scholar
  69. 69.
    Pistoia, G., Scrosati, B., Voso, M. A.: Europ. Polym. J. 12, 53 (1976)CrossRefGoogle Scholar
  70. 70.
    Bhadani, S. N., Prasad, Y. K.: Makromol. Chem. 178, 1841 (1977)CrossRefGoogle Scholar
  71. 71.
    Bhadani, S. N., Prasad, Y. K.: J. Polym. Sci., Polym. Lett. Ed. 15, 721 (1977)CrossRefGoogle Scholar
  72. 72.
    Strobel, W., Schulz, R. C.: Makromol. Chem. 133, 303 (1970)CrossRefGoogle Scholar
  73. 73.
    Asahara, T., Seno, M., Tobayama, M.: Chen Fan Quei, Seisan Kenkyu 22, 167 (1970); Chem. Abstr. 73, 88194g (1970)Google Scholar
  74. 74.
    Mengoli, G., Vidotto, G.: Makromol. Chem. 165, 137 (1973)CrossRefGoogle Scholar
  75. 75.
    Mengoli, G., Vidotto, G.: Makromol. Chem. 165, 145 (1973)CrossRefGoogle Scholar
  76. 76.
    Bhadani, S. N., Ghose, A.: Trans. Soc. Adv. Electrochem. Sci. Technol. 8 (1), 13 (1973)Google Scholar
  77. 77.
    Bhadani, S. N., Ghose, A.: Trans. Soc. Adv. Electrochem. Sci. Technol. 9 (4), 170 (1974)Google Scholar
  78. 78.
    Ghose, A., Bhadani, S. N.: Indian J. Technol. 12 (10), 443 (1974)Google Scholar
  79. 79.
    Mengoli, G., Valcher, S.: Europ. Polym. J. 10, 959 (1976)CrossRefGoogle Scholar
  80. 80.
    Mengoli, G., Vidotto, G.: Makromol. Chem. 175, 893 (1974)CrossRefGoogle Scholar
  81. 81.
    Mengoli, G., Vidotto, G.: J. Appl. Polym. Sci. 18, 3095 (1974)CrossRefGoogle Scholar
  82. 82.
    Yasuo, K., Kazuo, S.: Hiroshima Daigaku Kogakubu Kenkyu Hokoku 24, 1 (1975); Chem. Abstr. 84, 74660w (1975)Google Scholar
  83. 83.
    Yasuo, K., Masao, I., Kazuo, S.: ibid. 23, 13 (1975); Chem. Abstr. 83, 79725k (1975)Google Scholar
  84. 84.
    Mengoli, G., Valcher, S.: Europ. Polym. J. 11, 169 (1975)CrossRefGoogle Scholar
  85. 85.
    Fleischer, D., Schulz, R. C., Turcsanyi, B.: Makromol. Chem. 152, 305 (1972)CrossRefGoogle Scholar
  86. 86.
    Mengoli, G., Furlanetto, G.: Makromol. Chem. 176, 157 (1975)CrossRefGoogle Scholar
  87. 87.
    Nakahama, S., Hashimoto, K., Yamazaki, N.: Polym. J. 4 (4), 437 (1973)CrossRefGoogle Scholar
  88. 88.
    Pistoia, G.: J. Polym. Sci., Polym. Lett. Ed. 10, 787 (1972)CrossRefGoogle Scholar
  89. 89.
    Pistoia, G.: Europ. Polym. J. 10, 279 (1974)CrossRefGoogle Scholar
  90. 90.
    Pistoia, G.: Europ. Polym. J. 10, 285 (1974)CrossRefGoogle Scholar
  91. 91.
    Pistoia, G., Scrosati, B.: Europ. Polym. J. 10, 1115 (1974)CrossRefGoogle Scholar
  92. 92.
    Kikuchi, Y., Mitoguchi, H.: Makromol. Chem. 173, 233 (1973)CrossRefGoogle Scholar
  93. 93.
    Kikuchi, Y., Mitoguchi, H.: J. Macromol. Sci., Chem. 8 (3), 573 (1974)Google Scholar
  94. 94.
    Kikuchi, Y., Matsuno, A.: Makromol. Chem. 176, 515 (1975)CrossRefGoogle Scholar
  95. 95.
    Kikuchi, Y., Matsuno, A.: J. Appl. Polym. Sci. 20, 1711 (1976)CrossRefGoogle Scholar
  96. 96.
    Cerrai, P., Guerra, G., Tricoli, M.: Europ. Polym. J. 12, 247 (1976)CrossRefGoogle Scholar
  97. 97.
    Kikuchi, Y., Fukunda, H.: Nippon Kagaku Kaishi 1, 200 (1974); Chem. Abstr. 81, 64069j (1974)Google Scholar
  98. 98.
    Kikuchi, Y., Ueyama, T.: ibid. 5, 981 (1974); Chem. Abstr. 81, 91991k (1974)Google Scholar
  99. 99.
    Tsvetkov, N. S., Gnutenko, V. A., Koval'chuk, E. P.: Ukr. Khim. Zh. (Russ. Ed.) 41 (4), 349 (1975)Google Scholar
  100. 100.
    Bhadani, S. N., Baranwal, P.: Makromol. Chem. 178, 1049 (1977)CrossRefGoogle Scholar
  101. 101.
    Bhadani, S. N., Baranwal, P.: Makromol. Chem. 178, 2637 (1977)CrossRefGoogle Scholar
  102. 102.
    Bhadani, S. N., Baranwal, P.: Makromol. Chem. 177, 907 (1976)CrossRefGoogle Scholar
  103. 103.
    Ghose, A., Bhadani, S. N.: J. Polym. Sci., Polym. Lett. Ed. 11, 755 (1973)CrossRefGoogle Scholar
  104. 104.
    Bhadani, S. N., Baranwal, P., Prasad, Y.: Makromol. Chem. 179, 1623 (1978)CrossRefGoogle Scholar
  105. 105.
    Funt, B. L., Gray, D. C.: J. Macromol. Chem. 1 (4), 625 (1966)Google Scholar
  106. 106.
    Funt, B. L., Blain, T. J.: J. Polym. Sci. Part A-1, 9, 115 (1971)CrossRefGoogle Scholar
  107. 107.
    Tidswell, B. M., Doughty, A. G.: Polymer 12, 431 (1971)CrossRefGoogle Scholar
  108. 108.
    Phillips, D. C., Meier, J. F., Jackson, J. A.: J. Polym. Sci. Polym. Chem. Ed. 12, 1193 (1974)CrossRefGoogle Scholar
  109. 109.
    Salyer, I. O., Usmani, A. M.: J. Appl. Polym. Sci. 22, 3469 (1978)CrossRefGoogle Scholar
  110. 110.
    Tidswell, B. M., Train, A. W.: Brit. Polym. J. 7, 409 (1975)CrossRefGoogle Scholar
  111. 111.
    Tidswell, B. M., Train, A. W.: Brit. Polym. J. 7, 417 (1975)CrossRefGoogle Scholar
  112. 112.
    Tidswell, B. M., Train, A. W.: Brit. Polym. J. 7, 429 (1975)CrossRefGoogle Scholar
  113. 113.
    Smith, J. D., Phillips, D. C., Davies, D. H.: J. Polym. Sci., Polym. Chem. Ed. 15, 1555 (1977)CrossRefGoogle Scholar
  114. 114.
    Collins, G. L., Thomas, N. W.: J. Polym. Sci., Polym. Lett. Ed. 13, 73 (1975)CrossRefGoogle Scholar
  115. 115.
    Sato, K., Ogasawara, M., Kayashi, K.: J. Polym. Sci., Polym. Lett. Ed. 11, 5 (1973)CrossRefGoogle Scholar
  116. 116.
    Giusti, P. et al.: Makromol. Chem. 133, 299 (1970)CrossRefGoogle Scholar
  117. 117.
    Cerrai, P. et al.: Europ. Polym. J. 10, 1195 (1974)CrossRefGoogle Scholar
  118. 118.
    Cerrai, P. et al.: Europ. Polym. J. 11, 101 (1975)CrossRefGoogle Scholar
  119. 119.
    Cerrai, P. et al.: Europ. Polym. J. 10, 1141 (1974)CrossRefGoogle Scholar
  120. 120.
    Albeck, M., Königsbuch, M., Relis, J.: J. Polym. Sci., Part A-1, 9, 1375 (1971)Google Scholar
  121. 121.
    Albeck, M., Relis, J.: J. Polym. Sci., Part A-1, 9, 1789 (1971)Google Scholar
  122. 122.
    Albeck, M., Relis, J.: J. Polym. Sci., Part A-1, 9, 2963 (1971)Google Scholar
  123. 123.
    Kikuchi, Y., Mitoguchi, H.: Makromol. Chem. 175, 687 (1974)CrossRefGoogle Scholar
  124. 124.
    Mengoli, G., Daolio, S.: J. Polym. Sci., Polym. Lett. Ed. 13, 743 (1975)CrossRefGoogle Scholar
  125. 125.
    Haas, H. C., Moreau, R.: J. Polym. Sci., Polym. Chem. Ed. 16, 699 (1978)CrossRefGoogle Scholar
  126. 126.
    Eberson, L., In: Baizer, M. M. (ed.) Organic Electrochemistry, p. 470, New York: Dekker 1973Google Scholar
  127. 127.
    Albeck, M., Karoly, A.: J. Polym. Sci., Polym. Chem. Ed. 13, 2699 (1975)CrossRefGoogle Scholar
  128. 128.
    Tsvetkov, N. S., Gnutenko, V. A., Koval'chuk, E. P.: Sint. Fiz. Khim. Polim. 11, 16 (1973)Google Scholar
  129. 129.
    Zempachi, O. et al.: Bull. Chem. Soc. Japan, 47, 1843 (1974)CrossRefGoogle Scholar
  130. 130.
    Zempachi, O. et al.: Bull. Chem. Soc. Japan, 49, 2883 (1976)CrossRefGoogle Scholar
  131. 131.
    Shiro, Y. et al.: Denki Kagaku 40, 724 (1972)Google Scholar
  132. 132.
    Yoshizawa, S. et al.: J. Appl. Electrochem. 6 (2), 147 (1976)CrossRefGoogle Scholar
  133. 133.
    Karapetyan, K. et al.: Elektrokhimiya 13 (4), 544 (1977)Google Scholar

Copyright information

© Springer-Verlag 1981

Authors and Affiliations

  • Giuseppe Silvestri
    • 1
  • Salvatore Gambino
    • 1
  • Giuseppe Filardo
    • 1
  1. 1.Istituto di Ingegneria ChimicaUniversita di PalermoPalermoItaly

Personalised recommendations