DOI QR코드

DOI QR Code

Preparation and Properties of Polybenzoxazole Copolymers Bearing Pendants and Imide Ring in the Main Chain

  • Lee, Seul Bi (R&D Center, Korea Optics Technology Institute) ;
  • Lee, Eung Jae (Department of Bioenvironmental & Chemical Engineering, Chosun College of Science & Technology) ;
  • Choi, Jae Kon (Department of Biochemical & Polymer Engineering, Chosun University)
  • Received : 2016.07.28
  • Accepted : 2016.08.09
  • Published : 2016.09.30

Abstract

A series of aromatic poly(hydroxyamide)s (PHAs) containing varying oligo(oxyethylene) substituents and 1,3-phenylene imide ring unit in the main chain were synthesized by the direct polycondensation reaction. The inherent viscosities of the PHAs exhibited in the range of 0.89~1.12 dL/g in DMAc or DMAc/LiCl solution. The PH-2~5 copolymers were easily soluble in strong aprotic solvents: DMAc, NMP, DMSO etc. and the PH-5 copolymer was soluble in less polar solvents such as m-creasol and pyridine with LiCl salt on heating. However, all PBOs were quite insoluble in other solvents, but only partially soluble in sulfuric acid. All copolymers (PH-2~5) could afford the flexible and tough films by solution casting. We identified that the PHAs were converted to the PBOs by the thermal cyclization reaction in the range of $200{\sim}380^{\circ}C$. The 10% weight loss temperatures and char yields of the PBOs were recorded in the range of $382{\sim}647^{\circ}C$ and 38.7~73.1% values at $900^{\circ}C$. The tensile strength and initial modulus of the PH-5 in the copolmers showed the highest values of 2.46 GPa and 49.55 MPa, respectively. The LOI values of the PHAs were in the range 26.6~29.0%, and increased with increasing 1,3-phenylene imide ring unit.

Keywords

References

  1. S. H. Hsiao and J. H. Chiou, "Aromtic Polybenzoxazoles Containing Ether Sulfone Linkages", J. Polym. Sci. Part A, Polym. Chem., 39, 2262 (2001). https://doi.org/10.1002/pola.1203
  2. Y. Zhuang and Y. Gu, "Poly(benzoxazole-amide-imide) Copolymers for Interlevel Dielectrics: Interchain Hydrogen Bonding, Molecular Arrangement and Properties", J. Polym. Res., 20, 168 (2013). https://doi.org/10.1007/s10965-013-0168-7
  3. P. K. Kim, P. Pierini, and R. Wessling, "Thermal and Flammability Properties of Poly(p-phenylene-benzoxazole)", J. Fire Sci., 11, 296 (1993). https://doi.org/10.1177/073490419301100402
  4. H. Zhang, R. J. Farris, and P. R. Westmoreland, "Low Flammability and Thermal Decomposition Behavior of Poly(3,3'-dihydroxybiphenylisophthal amide) and Its Derivatives", Macromolecules, 36, 3944 (2003). https://doi.org/10.1021/ma021764x
  5. S. Y. Wu, S. M. Yuen, C. C. M. Ma, and Y. L. Huang, "Synthesis and Properties of Aromatic Polyimide, Poly(benzoxazole imide), and Poly(benzoxazole amide imide)", J. Appl. Polym. Sci., 113, 2301 (2009). https://doi.org/10.1002/app.30212
  6. J. H. Chang, M. J. Chen, and R. J. Farris, "Effect of Heat Treament on the Thermal and Mechanical Properties of a Precursor: Polyhydroxy Amide", Polymer, 39, 5649 (1998). https://doi.org/10.1016/S0032-3861(97)10364-0
  7. G. S. Liou, "New Rigid-rod and Strictly Alternating Poly(benzoxazole-imide)s Containing Methyl-Substituted p-phenylene 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
  8. D. Y. Wee, J. W. Han, and J. K. Choi, "Preparation and Characteristics of the Blends of Polyimide and Polybenzoxazole Having Imide Ring", Polymer(Korea), 37, 420 (2013).
  9. B. Y. Ryu, D. S. Yoon, S. K. Choi, J. K. Choi, and B. W. Jo, "Polybenzoxazole Precursors with Dimethylphenoxy/Alkoxy Pendant Groups for Flame Retarding Applications", J. Korean Ind. Eng. Chem., 12, 700 (2001).
  10. H. W. Jang, S. B. Lee, and J. K. Choi, "Synthesis and Thermal Properties of Poly(benzoxazole)s Based on Pendants", Elast. Compos., 50, 138 (2015). https://doi.org/10.7473/EC.2015.50.2.138
  11. E. J. Lee, D. S. Yoon, M. S. Bang, and J. K. Choi, "Synthesis and Characterization of Polybenzoxazole Precursors Having Oligo(oxyethylene) Pendant", J. Korea Academia-Industrial Cooperation Society, 14, 2550 (2013). https://doi.org/10.5762/KAIS.2013.14.5.2550
  12. Y. Maruyama, Y. Oishi, M. Kakimoto, and Y. Imai, "Synthesis and Properties of Fluorine-Containing Aromatic Poly(benzoxazole) s from Bis(o-aminophenols) and Aromatic Diacid Chlorides by the Silylation Method", Macromolecules, 21, 2305 (1998).
  13. D. S. Yoon, J. K. Choi, and B. W. Jo, "Synthesis and Characterization of PBO Precursors Containing Dimethylphenoxy and/or MPEG Pendant Groups", Polymer(Korea), 29, 493 (2005).
  14. D. Y. Wee, J. K. Choi, and C. H. Lee, "Synthesis and Thermal Properties of Aromatic Polyhydroxyamides Containing Imide Ring in the Main Chain", Elast. Compos., 46, 295 (2011).
  15. S. H. Hsiao and C. P. Yang, "Preparation of Polyamide- Imides via the Phosphorylation Reaction. II. Synthesis of Wholly Aromatic Polyamide-Imides from N-[p-(or m-)Carboxyphenyl] Trimellitimides and Various Aromatic Diamines", J. Polym. Sci. Part A: Polym. Chem., 28, 1149 (1990). https://doi.org/10.1002/pola.1990.080280515
  16. S. H. Hsiao and Y. H. Huang, "A New Class of Aromatic Polybenzoxazoles Containing Ortho-Phenylenedioxy Group", Eur. Polym. J., 40, 1127 (2004). https://doi.org/10.1016/j.eurpolymj.2004.01.011
  17. S. H. Hsiao and C. H. Yu, "Aromatic Polybenzoxazoles Bearing Ether and Isopropylidene or Hexaflouroisopropylidene Unit in the Main Chain", Macromol. Chem. Phys., 199, 1247 (1998). https://doi.org/10.1002/(SICI)1521-3935(19980701)199:7<1247::AID-MACP1247>3.0.CO;2-Y
  18. J. H. Chang and R. J. Farris, "Characterization of Two Precursor Polyblends: Polyhydroxyamide and Poly(amic acid)", Poly. Eng. & Sci., 40, 320 (2000). https://doi.org/10.1002/pen.11165
  19. M. P. Stevens, "Polymer Chemistry an Introduction", 3rd Ed. p. 375, Oxford University Press Inc, New York, 1999.
  20. T. K. Kim, K. Y. Choi, K. S. Lee, D. W. Park, and M. Y. Jin, "Thermal Conversion of t-butyloxycarbonyloxy attached Polyamides to Polybenzoxazoles", Polym. Bull., 44, 55 (2000). https://doi.org/10.1007/s002890050573
  21. S. E. Lee, Y. H. Song, and K. S. Chung, "Incombustibility of Polypropylene by Metal Addition Flame Retardant", J. KOSOS, 20, 4 (2006).
  22. 백두현, 이민호, "초고성능 PBO 섬유", Fiber Technol. Ind., 11, 261 (2007).
  23. SB Lee for MSc degree, Chosun University, Gwangju, Korea, 2016.