Search / Korean Journal of Chemical Engineering
HWAHAK KONGHAK,
Vol.33, No.1, 79-88, 1995
Hexadecyltrimethylammonium Bromide상이동촉매에 의한 Acrylonitrile의 라디칼 중합
Radical Polymerization of Acrylonitrile with Phase Transfer Catalyst Hexadecyltrimethylammonium Bromide
(NH4)2S2O8수용액과 toluene 용액의 2상에서 유기상에 용해하는 Hexadecyltrimethylammonium bromide 상이동촉매를 사용하여 단량체인 acrylonitrile(AN)의 라디칼 중합반응에서 초기중합속도와 상이동촉매의 분배계수 및 평형상수를 측정하여, 액-액 불균일계 접촉계면을 통한 중합반응기구를 해석하였다. AN의 중합속도는 수용액상에 존재하는 4급암모니움 이온의 농도와 S2O8-2 이온의 농도가 결합된 항에 정비례하고, AN의 농도에 정비례하였다. 재래적인 개시제를 사용한 라디칼 중합반응기구에 상이동촉매에 의한 반응기구를 적용하여 액-액 불균일 2상계에서 AN의 중합반응속도식을 해석하였다.
The phase-transfer polymerization of acrylonitrile system was investigated in a (NH4)2S2O8 aqueous-organic two-phase system with hexadecyltrimethylammonium bromide. The observed initial rates of polymerization were compared with those obtained from the polymerization mechanism proposed with a cyclic phase-transfer initiation step. The rate of polymerization was found to be proportional to the combined terms of concentrations of quaternary ammonium ion and S2O8-2 in the aqueous solution, and concentration of monomer. The rate of polymerization of acrylonitrile in the liquid-liquid heterogeneous system was interpreted with the polymerization mechanism by phase transfer catalyst applied to that by conventional initiators.
[References]
  1. Weber WP, Gokel GW, "Phase Transfer Catalysis in Organic Synthesis," Springer-Verlag, New York, 1977
  2. Starks CM, Liotta C, "Phase Transfer Catalysis-Principles and Techniques," Academic Press, New York, 1978
  3. Dehmlow EV, Dehmlow SS, "Phase Transfer Catalysis," 2nd ed., Verlag Chemie, Weinheim, 1983
  4. Starks CM, "Phase-Transfer Catalysis, New Chemistry, Catalysis, and Applications," Am. Chem. Soc., Washington, D.C., 1987
  5. Imai Y, Abe S, Ueda M, J. Polym. Sci. A: Polym. Chem., 19, 3285, 1981
  6. Podkoscielny W, kultys A, J. Appl. Polym. Sci., 26, 1143, 1981
  7. Yamazaki N, Imai Y, Polym. J., 15, 603, 1983
  8. Tsai H, Lee Y, J. Polym. Sci. A: Polym. Chem., 25, 1505, 1987
  9. Kellman R, Williams RF, Dimotsis G, Gerbi DJ, Williams JC, J. Am. Chem. Soc., 109, 128, 1987
  10. Yamada B, Yasuda Y, Matsudita T, Otsu T, J. Polym. Sci. C: Polym. Lett., 14, 277, 1976
  11. Reetz MT, Ostarek R, J. Chem. Soc.-Chem. Commun., 213, 1988
  12. Rasmussen JK, Smith HK, J. Am. Chem. Soc., 103, 730, 1981
  13. Jayakrishnan A, Shah DO, J. Polym. Sci. A: Polym. Chem., 21, 3201, 1983
  14. Jayakrishnan A, Shah DO, J. Appl. Polym. Sci., 29, 2937, 1984
  15. Rasmussen JK, Heilmann SM, Krepski LR, Smith HK, J. Am. Chem. Soc., 109, 116, 1987
  16. Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305, 1991
  17. Tabuchi K, Sakota N, Polym. J., 15, 713, 1983
  18. Shimada S, Nakagawa K, Tabuchi K, Polym. J., 21, 275, 1989
  19. Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 22, 777, 1990
  20. Nishikubo N, Iizawa T, Kobayasi K, Masuda Y, Macromolecules, 16, 722, 1983
  21. Kondo S, Yasui H, Ohta K, Tsuda K, J. Chem. Soc.-Chem. Commun., 400, 1985
  22. Nicholas PP, J. Am. Chem. Soc., 109, 155, 1987
  23. Martinez G, Mijangos C, Terroba P, Millan J, J. Polym. Sci. A: Polym. Chem., 26, 1629, 1988
  24. Percec S, J. Appl. Polym. Sci., 36, 415, 1988
  25. Bulacovschi V, Mihailescu C, Ioan S, Simionescu BC, J. Macromol. Sci.-Chem., A28, 613, 1991
  26. Shimada S, Obata Y, Nakagawa K, Tabuchi K, Polym. J., 23, 305, 1991
  27. Park SW, Moon JB, Park DW, Shin JH, HWAHAK KONGHAK, 30(5), 612, 1992
  28. Park SW, Moon JB, Ha YS, Lim GT, Polym.(Korea), 17(1), 100, 1993
  29. Park SW, Moon JB, Ha YS, Kim JH, J. Korean Ind. Eng. Chem., 4(2), 300, 1993
  30. Park SW, Christiawaty FK, Baek JJ, Polymer, to be submitted, 18, 1994
  31. Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, London, 106, 1953
  32. JIS Commun., J.I.S., K0101, 107, 1986