Cure Konetics and Mechanism of DGEBA-MDA-Malononitrile System

Malononitrile로 개질된 DGEBA-MDA계의 경화반응 속도론 및 반응 메카니즘

  • Im, Seong-Su (Dept. of Chemical Engineering, Seoul City University) ;
  • Jo, Seong-U (Dept. of Chemical Engineering, Seoul City University) ;
  • Yu, Hui-Yeol (Dept. of Chemical Engineering, Seoul City University) ;
  • Sim, Mi-Ja (Division of Liberal Arts, Seoul City University) ;
  • Kim, Sang-Uk (Dept.of Chemical Engineering, University of Seoul)
  • 임성수 (서울시립대학교 화학공학과) ;
  • 조성우 (서울시립대학교 화학공학과) ;
  • 유희열 (서울시립대학교 화학공학과) ;
  • 심미자 (서울시립대학교 교양과정부) ;
  • 김상욱 (서울시립대학교 화학공학과)
  • Published : 1993.06.01

Abstract

Malononitrile(MN) as a reactive additive was added to Diglycidyl ether of bisphenol A (DGEBA)/Methylene dianiline (MDA) system in order to modify a thermosetting epoxy resin. Cure ki. netics and cure mechanism of this modified system were investigated by using DSC(differential scanning calorimetry) and FT-IR(fourier transform infrared spectrometry). Cure kinetics gave an information that the DGEBA/MDA system modified with MN should cure at over $110^{\circ}C$ after curing at about $80^{\circ}C$ for the complete curing. The activation energy of the first cure was nearly constant and that of the second cure was increased as the MN content was increased. Cure mechanism for the system was investigated with the samples cured every $30^{\circ}C$, from $80^{\circ}C$ to $170^{\circ}C$, for Ihr. It was known that the cure reactions of the epoxy-diamine system were composed of PA -E, SA - E and E-OH reactions. Beside these three reactions, in the DGEBA/MDA/MN system PA-CN and CN-OH reaction was found.

에폭시 수지를 개질하기 위하여 반응성 첨가제 Malononitrild(MN)을 Diglycidy1 ether fo vispenol A (CGEBA)/Methylene dianiline(MDA)계를 첨가하여 이 계의 경화 반응속도론과 경화반응메카니즘을 시차주사 열분석(DSC)과 적외선 흡수 분광법을 통해 관찰하였다. 경화반응속도론으로부터 MN으로 개질된 DGEBA/MDA는 완전히 경화를 이루기 위하여 $80^{\circ}C$로 부터 $170^{\circ}C$까지 $30^{\circ}C$간격으로 경화시킨 시료로 반응메카니즘을 고찰한 결과 PA(primary amine)-E(epoxide)그리고 E(epoxide)-OH(hydroxy1 group)반응 이외에 PA(primary amine)-CN(nitrile)과 CN(nitrile)-OH(hydroxy1 group)반응이 일어남을 알았다.

Keywords

References

  1. Handbook of Epoxy Resins H. Lee;K. Neville
  2. J. Appl. Polym. Sci. v.26 no.889 L.T. Manzione;J.K. Gillham;C.A. McPherson
  3. J. Appl. Sci. v.29 no.3397 L.C. Chan;H.N. Nae;J.K. Gillham
  4. Polym. Eng. Sci. v.27 no.17 S.N. Lee;W.B. Yuo
  5. J. Appl. Polym. Sci. v.31 no.929 R.E. Smith;C.H. Smith
  6. J. Appl. Polym. Sci. v.33 no.1843 M. Ito;H. Hata;K. Kamagata
  7. Korean J. Mat. Res. v.2 no.191 S.W. Cho;M.J. Shim;S.W. Kim
  8. Proceedings of the second International Conference on Computer Applications to Materials and Molecular Science and Engineering S.W.Cho; M.J.Shim;S.W.Kim
  9. J. Appl. Polym. Sci. v.33 no.1173 H.N. Nae
  10. Advances in Chemistry Series v.208 no.281 Rubber Modified Thermoset Resins H.N. Nae;S. Reich;Z. Nir;C.K.Riew(ed.);J.K. Gillham(ed.)
  11. ACS Symposium Series v.221 Epoxy Resin Chemistry 2 W.A. Romanchick;J.E. Sohn;J.F. Geibel;R.S. Bauer(ed.)
  12. J. Appl. Polym. Sci. v.29 no.1391 M. Ochi;J.P. Bell
  13. J. Appl. Polym. Sci. v.32 no.5147 A. Sabra;J.P. Pascault;G. Seytre
  14. Polym. Eng. Sci. v.22 no.821 T. Donnellan;D. Roylance
  15. Polym. Eng. Sci. v.19 no.304 N.S. Schneider;J.F. Sprouse;G.L. Hagnauer;J.K. Gillhan
  16. J. Appl. Polym. Sci. v.33 no.1725 M.R. Keenan
  17. J. Appl. Polym. Sci. v.29 no.2481 C.C. Riccardi;H.E. Adabbo;R.R. J. Williams
  18. J. Polym. Sci., A-1 v.8 no.1357 K. Horie;H. Hiura;M. Sawada;I. Mita;H. Kambe
  19. Soc. Plast. Eng. Tech. Papers v.19 no.187 M.R. Kamal;S. Sourour;M. Ryan
  20. Soc. Plast. Eng. Tech. Papers v.15 no.610 O.R. Abolafia
  21. Anal. Calorim. v.2 no.201 R.B. Prime
  22. Polymer v.12 no.335 M.A. Acitelli;R.B. Prime;E. Sacher
  23. Polymer v.13 no.455 R. B. Prime;E. Sacher
  24. Polym. Eng. Sci. v.13 no.365 R.B. Prime
  25. J. Indian Chem. Soc. v.36 no.7 R.L. Dutta;R. Priyadaranjan
  26. J. Org. Chem. v.30 no.298 G.D. Diana;E.S. Zaoay;R.A. Cutler
  27. Zh. Org. Khim. v.1 no.721 Yu. I. Mushkin;A.I.Finkel'shtein
  28. J. Polym. Sci., A-1 v.5 no.1609 T.F. Saunders;M.F. Levy;J.F. Serino
  29. J. Polym. Sci. v.18 no.867 U.M. Bokare;K.S. Gandhi