• Syntheses, Curing Behaviors and Characterizations of Poly(amic dialkyl ester) Precursors Based on Pyromellitic Dianhydride (PMDA)/4,4'-Oxydianiline(ODA)
  • Choi SY, Kim JB
  • Pyromellitic Dianhydride(PMDA)/4,4`-Oxyaniline(ODA)계 Poly(amic dialkyl ester)전구체들의 합성과 경화 거동 및 특성
  • 최상열, 김진봉
Abstract
The three different poly(amic dialkyl ester)s of methyl (PAME), ethyl(PAEE), n-butyl ester (PABE) based on pyromellitic dianhydride (PMDA)/4,4''-oxydianiline(ODA) were synthesized. The onset temperatures of imidizatin were increased in order of PAMEPAEE>PABE which was consistent with the trend of imidization onset. In the slow last step, the reaction rates were in order of PAME>PAEE>PABE at 190-260 ℃ ranges, PAEE>PABE>PAME at 280-340 ℃ ranges, and PABE>PAEE>PAME at 380 ℃. In the high degree of imidization, the change of reaction rate is related to chain mobility of the matrix. And the remarkably reduced activation energy is considered to be attributed to the fact that the reaction mode changed Tg of the matrix. The excellent mechanical property and thermal stability were observed from the PABE based polyimide.

Pyromellitic Dianhydride(PMDA)/4,4`-Oxyaniline(ODA)계에서 methyl(PAME), ethyl(PAEE), n-butyl ester (PABE)에 따른 세 종류의 poly(amic dialkyl ester)들을 합성하였다. 이미드화 개시온도는 alcohol 탈리 에너지 cmras과 관련하여 PAMEPAEE>PABE, 그리고 280-340 ℃에서 PAEE>PABE>PAME, 380 ℃에서 PABE>PAEE>PAME 순으로 경향이 반전되어 나타났다. 고전환율에서 반응속도의 반전은 사슬 유동성과 관련되며, 활성화 에너지의 급격한 감소는 이미드화에 따른 기질의 Tg 상승으로 반응 mode가 chemical controlled treaction에서 diffusion controlled reaction으로 전환되기 때문이다. 세 전구체들 중에서 PI(PABE)의 우수한 기계적 물성과 열적 안정성이 관찰되었다.

Keywords: poly(amic dialkyl ester); curing behavior; polyimide; chemical controlled reaction; diffusion controlled reaction; poly(amic dialkyl ester); curing behavior; polyimide; chemical controlled reaction; diffusion controlled reaction

References
  • 1. Mittal KLPolyimides: Synthesis, Characterization, and Application, vol. I, Plenum Press, New York (1983)
  •  
  • 2. Tummala RR, Rymaszewski EJMicroelectronics Packaging Handbook, van Nostrand Reinhold, New York (1989)
  •  
  • 3. Mazione LTPlastic Packaging of Microelectronic Devices, van Nonstand Reinhold, New York (1990)
  •  
  • 4. Czornyj G, Chen KJ, Parada-Silva G, Arnold A, Souleotis H, Kim S, Lee M, Volksen W, Dawson D, Diepietro R, Proc. Elect. Comp. Tech. Conf., 42, 682 (1992)
  •  
  • 5. Sroog CE, Prog. Polym. Sci., 16, 561 (1991)
  •  
  • 6. Nishizaki S, Moriwaki T, Kogyo Kagaky Zasshi, 73, 1873 (1970)
  •  
  • 7. Nishizaki S, Moriwaki T, Ind. Chem. Mag., 71, 1559 (1968)
  •  
  • 8. Korshak VV, Vinogradova SV, Vygodskii YS, Gerashchenko ZV, J. Polym. Sci. USSR, 13, 1341 (1971)
  •  
  • 9. Kharkov SN, Kranov YP, Lavrova ZN, Baranova SA, Akrasnova VP, Chegolya AS, J. Polym. Sci. USSR, 13, 940 (1971)
  •  
  • 10. Volksen W, Yoon DY, Hedrick JL, Hofer D, Mater. Res. Soc. Proc., 227, 23 (1991)
  •  
  • 11. Houlihan FM, Bachman BJ, Wilkens CW, Pryde CA, Macromolecules, 22, 4477 (1989)
  •  
  • 12. Cotts PM, Volksen W, Siemens R, Polym. Mater. Sci. Eng., 59, 214 (1988)
  •  
  • 13. Chin E, Yoshikiyo M, Houlihan FM, Bertz S, Bachman BJPolyimides and Other High Temperature Polymers, eds. by M.J.M. Abadie and B. Sillion, p. 19, Elsevier Amsterdam (1991)
  •  
  • 14. Volksen W, Yoon DY, Hedrick JL, Hofer D, MRS Symp. Proc., 227, 23 (1991)
  •  
  • 15. Stoffel NC, Kramer EJ, Volksen W, Russell TP, Polymer, 34, 4524 (1993)
  •  
  • 16. Rhee SB, Park JW, Moon BS, Chang JY, Macromolecules, 26, 404 (1993)
  •  
  • 17. Flain TD, Horter Bl, Moss MGPolyimides: Materials Chemistry and Characterization, eds. by C. Feger, M.M. Khojasteh, and J.E. McGrath, Elsevier, New York (1989)
  •  
  • 18. Becker KH, Schmidt HW, Macromolecules, 25, 6784 (1992)
  •  
  • 19. Konieczny M, Xu HZ, Battaglia R, Wunder SL, Volksen W, Polymer, 38(12), 2969 (1997)
  •  
  • 20. Breker JA, Feger CJ, J. Polym. Sci. A: Polym. Chem., 25, 2479 (1987)
  •  
  • 21. Stoffel NC, Kramer EJ, Volksen W, Russell TP, Polymer, 34, 4529 (1993)
  •  
  • 22. Houlihan FM, Bachman BJ, Wilkins CW, Pryde CA, Macromolecules, 22, 4480 (1989)
  •  
  • 23. Snyder RW, Painter PC, Polym. Mat. Sci. Eng. ACS, 59, 57 (1988)
  •  
  • 24. Zubkov VAPolyamic Acids and Polyimides, Synthesis, Transformations, and Structure, ed. by M.I. Bessonov, p. 14, CRC Press (1987)
  •  
  • 25. Kreuz JA, Endrey AL, Gay FP, Sroog CE, J. Polym. Sci. A: Polym. Chem., 4, 2607 (1966)
  •  
  • 26. Snyder RW, Sheen CW, Appl. Spect., 42, 655 (1988)
  •  
  • 27. Snyder RW, Painter PC, Polym. Mat. Sci. Eng. ACS, 59, 57 (1988)
  •  
  • 28. Frayer PDPolyimides; Synthesis, Characterization, and Applications, ed. by K.L. Mittal, Vol. I, p. 273, Plenum Press, New York and London (1984)
  •  
  • 29. Kumer DJ, J. Polym. Sci. A: Polym. Chem., 18, 1375 (1980)
  •  
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This Article

  • 1999; 23(2): 220-231

    Published online Mar 25, 1999