Article
  • Radical Copolymerization of Acrylonitrile and Methylacrylate with Phase Transfer Catalysts
  • Park SW, Moon JB, Song IT, Yang SS, Heo NH
  • 상이동촉매에 의한 Acrylonitrile과 Methylacrylate의 라디칼 공중합
  • 박상욱, 문진복, 송인태, 양삼석, 허남환
Abstract
Radical copolymerization of acrylonitrile and methylacrylate with phase transfer catalysts in aqueous-organic two phase system was studied. Conversion increased with increasing the ㏖ecular weight of phase transfer catalysts, decreased with increasing dielectric constant of organic solvents. The overall activation energy of copolymerization using HTAB was 9.6Kcal/㏖ and 32.4Kcal/㏖ smaller than those without the catalyst. The monomer reactivity ratios were 1.304 for acrylonitrile and 0.614 for methylacrylate.

수용액상과 유기상의 불균일상에서 상이동촉매를 사용하여 acrylonitrile과 methylacrylate를 라디칼 공중합하였다. 상이동촉매는 분자량이 클수록 전화율이 증가하였고, 유기용매는 극성이 클수록 전화율이 감소하였다. K2S2O8-HTAB 개시제에서의 활성화 에너지는 9.6Kcal/㏖로서 상이동촉매(HTAB)를 사용하지 않았을 경우의 42.0Kcal/㏖ 보다 32.4Kca1/㏖ 낮았다. 또한 이때의 acrylonile과 methylacrylate에 대한 반응성비는 각각 1.304와 0.614이였다.

Keywords: phase transfer catalyst; radical copolymerization; reactivity ratio; acrylonitrile

References
  • 1. Weber WP, Gokel GWPhase Transfer Catalysis in Organic Synthesis, Springer-Verlag, New York (1977)
  •  
  • 2. Starks CM, Liotta CPhase Transfer Catalysis-Principle and Techniques, Academic Press, New York (1978)
  •  
  • 3. Dehmlow EV, Dehmlow SSPhase Transfer Catalysis, 2nd ed., Verlag Chemie, Weinheim (1983)
  •  
  • 4. Starks CMPhase-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. Yamamda 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, Nakahawa K, Tabychi 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. Konbo 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. Bulascovschi 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, Ha YS, Lim GT, Polymer, 17, 100 (1993)
  •  
  • 28. Park SW, Moon JB, Ha YS, Kim JH, J. Korean Ind. Eng. Chem., 4(2), 300 (1993)
  •  
  • 29. Park SW, Kaseger CF, Baek JJ, Polym.(Korea), 19(1), 1 (1995)
  •  
  • 30. Park KY, Jang HD, Kim W, HWAHAK KONGHAK, 32(1), 79 (1994)
  •  
  • 31. Park SW, Park DW, Lee SS, Yang SS, Baek JJ, HWAHAK KONGHAK, 34(2), 215 (1996)
  •  
  • 32. Herriott AW, Picker D, J. Am. Chem. Soc., 97, 2345 (1975)
  •  
  • 33. Mihailesch C, Bulacovschi V, Simionescu C, Revue Roumaine Chimie, 34(7), 1535 (1989)
  •  
  • 34. Patra CM, Singh BC, J. Appl. Polym. Sci., 52(11), 1549 (1994)
  •  
  • 35. Simionescu C, Mihailesch C, Bulacovschi V, Acta Polym., 38, 502 (1987)
  •  
  • 36. Finemann N, Ross SD, J. Polym. Sci., 5, 259 (1950)
  •  
  • 37. Kelen T, Tudos F, J. Macromol. Sci.-Chem., A9(1), 1 (1975)
  •  
  • 38. Tamikado T, Iwakura Y, J. Polym. Sci., 36, 529 (1959)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2023 Impact Factor : 0.4
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This Article

  • 1996; 20(3): 447-454

    Published online May 25, 1996