DOI QR코드

DOI QR Code

Synthesis and Thermal Properties of Aromatic Polyhydroxyamides Containing Imide Ring in the Main Chain

주 사슬에 이미드 고리를 갖는 방향족 polyhydroxyamides의 합성 및 열적 특성

  • Wee, Doo-Young (Dept. of Polymer Science & Engineering, Chosun University) ;
  • Choi, Jae-Kon (Dept. of Polymer Science & Engineering, Chosun University) ;
  • Lee, Chang-Hoon (Dept. of Polymer Science & Engineering, Chosun University)
  • 위두영 (조선대학교 응용화학소재공학과) ;
  • 최재곤 (조선대학교 응용화학소재공학과) ;
  • 이창훈 (조선대학교 응용화학소재공학과)
  • Received : 2011.09.23
  • Accepted : 2011.11.25
  • Published : 2011.12.31

Abstract

A series of new aromatic polyhydroxyamides (PHAs) containing imide ring were prepared by direct polycondensation reaction of imide-diacids and two types of bis(o-aminophenol)s including 3,3'-dihydroxybenzidine and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. The polymers were characterized by FT-IR, FT-NMR, DSC and TGA. The inherent viscosities of the PHAs measured at $35^{\circ}C$ in DMAC solution were in the range of 0.49-1.13 dL/g. PHA 2 and 3, except PHA 1, were soluble in polar solvents such as DMAc, DMF and NMP. PHA 4, 5, and 6 containing 6F group showed a higher solubility in less polar solvents. But the polybenzoxazoles (PBOs,) were insoluble in a variety of solvents except partially soluble in sulfuric acid. The PBO 1, 2 and 3 showed maximum weight loss temperature in the range of $650-656^{\circ}C$ and relatively high char yields in the range of 57.4-61.9 % under a nitrogen atmosphere. These results suggested that the introduction of imide or diimide ring in the main chain was effective in improving the thermal stability of PHAs and PBOs.

3,3'-dihydroxybenzidine 과 2,2-bis (3-amino-4-hydroxyphenyl)hexafluoro-propane을 포함하는 두가지 타입의 bis(o-aminophenol)s 과 imide-diacids 를 직접 축 중합하여 imide 고리를 포함한 새로운 방향족 polyhydroxyamides(PHAs)을 합성하였다. 모든 중합체들은 FT-IR, FT-NMR, DSC 및 TGA를 이용하여 조사하였다. 중합체들의 고유점도는 $35^{\circ}C$의 DMAc 용액에서 측정하였으며, 0.49-1.13 dL/g 을 보였다. PHA 1을 제외한 PHA 2 와 3은 DMF, DMAc, NMP 등 극성 용매에 잘 용해되었으며, 6F 그룹이 포함된 PHA 4, 5, 및 6은 극성이 낮은 용매에 대해서도 좋은 용해도를 보였다. 반면에 polybenzoxazoles(PBOs)은 황산에 일부 용해되는 것 외에 다양한 용매에도 용해되지 않았다. 질소분위기 하에서 PBO 1, 2, 3의 최대 열분해온도는 $650-656^{\circ}C$ 범위의 값들을 보였고, char 수득율도 57.4-61.9 %로 비교적 높은 값을 보였다. 이로부터 고분자 주 사슬에 imide 혹은 diimide 고리의 도입은 PHA 혹은 PBO의 열안정성을 높이는데 효과적임을 알 수 있었다.

Keywords

References

  1. M. P. Stevens, "Polymer Chemistry an Introduction", 3rd Ed. p. 106, Oxford University Press Inc., New York, 1999.
  2. J. M. Margolis, "Engineering Thermoplastics", ed. by J. M. Margolis, p. 315, Marcel Dekker Inc., New York, 1985.
  3. G. W. Ehrenstein, "Polymeric Materials", p. 4. Hanser, Cincinnati, 2001.
  4. C. E. Stroog, "Polyimides", Prog. Polym. Sci., 16, 561 (1991). https://doi.org/10.1016/0079-6700(91)90010-I
  5. M. I. Bessonov, M. M. Koton, V. V. Kudryavtsev, and L. A. Laius, "Polimides", Consultants Bureau, New York, 1988.
  6. S. H. Hsiao, G. S. Liou, Y. C. Kung, and Y. J. Lee, "Synthesis and Characterization of Electrochromic Poly(amide-imide)s Based on the Diimide-diacid from 4,4'-diamino-4''-methoxytriphenylamine and Trimellitic anhydride", Eur. Polym. J., 46, 1355 (2010). https://doi.org/10.1016/j.eurpolymj.2010.03.016
  7. N. V. Sadavarate, C. V. Avadhani, P. V. Naik, and P. P. Wadgaonkar, "Regularly Alternating Poly(amideimide)s Containing Pendent Pentadecyl Chains: Synthesis and Characterization", Eur. Polym. J., 46, 1307 (2010). https://doi.org/10.1016/j.eurpolymj.2010.03.007
  8. S. H. Hsiao and Y. H. Huang, "A New Class of Aromatic Polybenzoxazoles Containing Ortho-phenylenedioxy Groups", Eur. Polym. J., 40, 1127 (2004). https://doi.org/10.1016/j.eurpolymj.2004.01.011
  9. S. L. C. Hsu and W. C. Chen, "A Novel Positive Photosensitive Polybenzoxazole Precursor for Microelectronic", Polymer, 43, 6743 (2002). https://doi.org/10.1016/S0032-3861(02)00635-3
  10. H. Zhang, R. J. Farris, and P. R. Wesmoreland, Low Flammability and Thermal Decomposition Behavior of Poly (3,3'-dihydroxybiphenylisophthalamide) and Its Derivatives", Macromolecules, 36, 3944 (2003). https://doi.org/10.1021/ma021764x
  11. J. H. Chang, M. J. Chen, and R. J. Farris, "Effect of Heat Treatment on the Thermal and Mechanical Properties of a Precursor Polymer: Polyhydroxyamide", Polymer, 39, 5649 (1998). https://doi.org/10.1016/S0032-3861(97)10364-0
  12. S. H. Hsiao and C. P. Yang, "Preparation of Polyamide-Imide Via the Phosphorylation Reaction", J. of Polym. Sci. Part A: Polym. Chem., 28, 1149 (1990). https://doi.org/10.1002/pola.1990.080280515
  13. Y. Maruyama, Y. Oishi, M. Kakimoto, and Y. Imai, "Synthesis and Properties of Fluorine Containing Aromatic Polybenzoxazoles from Bis(o-aminophenols) and Aromatic D ArodChlorides by the Silylation Method", Macromolecules, 21, 2305 (1988). https://doi.org/10.1021/ma00186a001
  14. J. G. Hilborn, J. W. Labadie, and J. L. Hedrik, "Poly(aryl ether-benzoxazoles)", Macromolecules, 23, 2854 (1990). https://doi.org/10.1021/ma00213a006
  15. G. S. Liou and S. H. Hsiao, "Preparation and Characterization of Aromatic Polybenzoxazoles Bearing Ether and 1,4-naphthalene or 2,6-naphthalene Units in the Main Chain", Macromol. Chem. Phys., 201, 42 (2000). https://doi.org/10.1002/(SICI)1521-3935(20000101)201:1<42::AID-MACP42>3.0.CO;2-H
  16. S. H. Hsiao and Y.J. Chen, "Synthesis and Properties of Hydroxy-Containing Ortho-Linked Poly(ether-imide)s, High Perform. Polym., 12, 515 (2000).
  17. D. H. Baik, E. K. Kim, and M. K. Kim, "Preparation of New Heat-resistant Fiber Materials using Polymeric Precursors to Polybenzdxazoles(I)", J. Korean Fiber Society, 40, 13 (2003).
  18. D. S. Yoon, J. K. Choi, and B. W. Jo, "Syntheses and Characterization of PBO Precursors Containing Dimethylphenoxy and/or MPEG Pendent Groups", Polymer(Korea), 29, 493 (2005).
  19. O. C. Jeon, J. K. Choi, and B. W. Jo, "Blends of Poly(ethylene 2,6-naphthalate) and a Liquid Crystalline Polyester having Ethoxy Group in the Side Chain", J. Korean Ind. Eng., 13, 229 (2002).
  20. J. K. Choi, J. Zilberman, and R. J. Farris, "Flame Retarding Properties of Kevla and Nomex Fibers", CUMIRP Report (Univ. Mass.) Massachusetts, U.S.A., Part 1 (2006).
  21. S. Wang, Y. Hu, Z. Li, Z. Wang, Y. Zhaung, Z. Chen, and W. Fan, "Flammability and Phase-transition Studies of Nylon 6/Montmorillonite Nanocomposites", Colloid Polym. Sci., 281, 951 (2003). https://doi.org/10.1007/s00396-002-0858-x
  22. Y. Shao, Y. F. Li, X. Zhao, X. L. Wang, T. Ma, and F. C. Yang, "Synthesis and Properties of Fluorinated Polyimides from a New Unsymmetrical Diamine: 1,4-(2'-trifluoromethyl- 4,4"-diaminodiphenoxy)benzene", J. of Polym. Sci. Part A: Polym. Chem., 44, 6836 (2006). https://doi.org/10.1002/pola.21777