Elastomers and Composites

The Rubber Society of Korea (한국고무학회)
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Preparation and Properties of Aromatic Polybenzoxazoles with high char yields

높은 char 수득률를 갖는 방향족 polybenzoxazoles의 제조 및 특성

  • Sohn, Jun-Youn (Dept. of Polymer Science & Engineering, Chosun University) ;
  • Moon, Sung-Chul (Dept. of Polymer Science & Engineering, Chosun Uninversity) ;
  • Yoon, Doo-Soo (Dept. of Polymer Science & Engineering, Chosun University) ;
  • Choi, Jae-Kon (Dept. of Polymer Science & Engineering, Chosun University)
  • 손준연 (조선대학교 응용화학소재 공학과) ;
  • 문성철 (조선대학교 응용화학소재 공학과) ;
  • 윤두수 (조선대학교 응용화학소재 공학과) ;
  • 최재곤 (조선대학교 응용화학소재 공학과)
  • Published : 2007.12.31
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Abstract

A series of polyhydroxyamides(PHAs) having ether linkages in the polymer backbone were prepared via solution polycondensation at low temperature. These polymers were studied by FT-IR, $^1H-NMR$, DSC, TGA and PCFC. The PHAs exhibited inherent viscosities in the range of $0.5{\sim}1.1dL/g\;at\;35^{\circ}C$ in DMAc solution. Most of PHAs except PHA 3 were soluble in polar organic solvents such as N,N-dimethylacetamide(DMAc), N-methyl-2-pyrrolidone(NMP), and N,N-dimethylform-amide(DMF). Subsequent thermal treatment of PHAs afforded polybenzoxazols(PBOs). However, the PBOs were insoluble in a variety of solvents. Most of the PBOs except PBO 3 showed glass-transition temperature($T_g$) in the range of $200{\sim}246^{\circ}C$ by DSC and maximum weight loss temperature in the range of $597{\sim}697^{\circ}C$ in nitrogen by TGA. PBOs showed high char yields in the range of $51{\sim}64%$. PCFC results of the PBOs showed the heat release(HR) capacity, $8{\sim}65J/gK$ and total heat release(total HR), $2.4{\sim}4.7kJ/g$.

일련의 방향족 polyhydroxyamides(PHA)를 저온 용액 중축합으로 합성하였다. 이들 중합체들은 FT-IR, $^1H-NMR$, DSC, TGA 그리고 PCFC를 이용하여 특성들을 조사하였다. PHA 중합체들의 고유점성도는 DMAc 용매 하에 $35^{\circ}C$에서 $0.5{\sim}1.1dL/g$의 값을 나타내었다. PHA 3을 제외한 중합체들은 N,N-dimethylacetamide(DMAc), N-methyl-2-pyrrolidone(NMP), N,N-dimethylformamide(DMF) 등과 같은 극성 유기 용매에 용해되었지만, 열적 고리화 반응에 의해 전환된 polybenzoxazoles(PBOs)는 용해되지 않았다. PBO 3을 제외한 PBO 중합체들에서는 DSC에서 $200{\sim}246^{\circ}C$의 유리전이온도($T_g$)를 보였고, TGA에서의 최대분해온도는 질소 분위기 하에서 $597{\sim}697^{\circ}C$의 범위를 보였다. PBO 중합체들은 $51{\sim}64%$의 높은 차 수득률을 보였다. PCFC에서 PBOs의 heat release(HR) capacity는 $8{\sim}65J/gK$의 값을 보였고, total heat release(total HR)의 값은 $2.4{\sim}4.7kJ/g$을 보였다.

Keywords

References

  1. C. S. Park, '난연제의 소개 및 최근동향', Rubber Technology, 1, 114 (2000)
  2. C. E. Stroog, 'Polyimides', Preg. Polym. Sci, 16, 561 (1991) https://doi.org/10.1016/0079-6700(91)90010-I
  3. M. I. Bessonov, M. M. Koton, V. V. Kundryavtsev, and L. A. Laius : Polyimides, Consultants Bureau (1987)
  4. R. E. Lyon, 'Fire-safe Aircraft Materials', PMSE, 71, 26 (1994)
  5. P. K. Kim and R. Wessling, 'Thermal and Flammability Properties of Poly (p- phenylene-benzobisoxazole)', J. Fire Science, 11, 296 (1993) https://doi.org/10.1177/073490419301100402
  6. D. H. Baik, E. K. Kim, and M. K. Kim, 'Preparation of New Heat-resistant Fiber Materials Using Polymeric Precursors to Polybenzoxazoles(I)' J. of the Korean Fiber Society, 40, 13 (2003)
  7. Y. Maruyama, Y. Oishi, M. Kakimoto, and Y. Iami, 'Synthesis and properties of fluorine-containing aromatic polybenzoxazoles from bis(o-aminophenols) and aromatic diacid chlorides by the silylation method' Macromolecules, 21, 2305 (1988) https://doi.org/10.1021/ma00186a001
  8. J. G. Hilborn, J. W. Labadie, and J. L. Hedrick, 'Poly(aryl ether-benzoxazoles)' Macromolecules, 23, 2854 (1990) https://doi.org/10.1021/ma00213a006
  9. J. L. Hedrick, J. G. Hilborn, T. D. Palmer, J. W. Labadie, and W. Volksen, 'Imidearyl ether benzoxazole block copolymers' J. Polym. Sci. Part A, Polym. Chem., 28, 2255 (1990) https://doi.org/10.1002/pola.1990.080280903
  10. S. H. Hisao, C. P. Yang, and S. H. Chen, 'Synthesis and properties of ortholinked polyamides based on a bis(ether-carboxylic acid) or a bis(ether amine) derived from 4-tertbutylcatechol' Polymer, 41, 6537 (2000) https://doi.org/10.1016/S0032-3861(99)00897-6
  11. R. N. Walters and R. E. Lyon, 'Molar group contributions to polymer flamm- ability' J. Appl. Polym. Sci. 87, 548 (2003) https://doi.org/10.1002/app.11466
  12. R. N. Walters and R. E. Lyon, 'Pyrolysis combustion flow calorimetry' J. Anal. Appl. Pyrolysis. 71, 27 (2004) https://doi.org/10.1016/S0165-2370(03)00096-2
  13. M. K. Chun, 'Synthesis and Thermal Properties of Copolymer Precursors having Aromatic Heterocyclic Group' Master's degree thesis, Chosun University (1998)
  14. S. H. Hsiao and C. F. Chang, 'Synthesis and properties of aromatic polyamides based on 4,4'-[1,4(1,3 or 1,2)-phenylenedioxy]dibenzoic acid' Macromol, Chem. Phys,. 197, 1255 (1996) https://doi.org/10.1002/macp.1996.021970407
  15. S.-H. Hsiao and W.-T. Chen, 'Syntheses and properties of new aromatic polybenzoxa-zoles bearing ether and phenylethylidene or 1-phenyl-2,2,2-trifluoroethylidene linkages' J. of Polym. Sci.: Part A: Polym. Chem., 41, 914 (2003) https://doi.org/10.1002/pola.10630
  16. S. L. C. Hsu, and W. C. Chen, 'A novel positive photosensitive polybenzoxazole pre-cursor for microelectronic applications' Polymer, 43, 6743 (2002) https://doi.org/10.1016/S0032-3861(02)00635-3
  17. G. Maglio, R. Palumbo, and M. Tortora, 'Aromatic poly(benzoxazole)s from multiring diacids containing(phenylenedioxy)diphenylene or (naphthalenedioxy) diphenylene groups: Synthesis and thermal properties' J. Polym. Sci. Part A: Polym. Chem., 38, 1172 (2000) https://doi.org/10.1002/(SICI)1099-0518(20000401)38:7<1172::AID-POLA16>3.0.CO;2-8
  18. D. S. Yoon, J. K. Choi, and B. W. Jo, 'Syntheses and Characterization of PBO Precursors Containing Dimethylphenoxy and/or MPEG Pendant Groups' Polymer (Korea), 29, 493 (2005)
  19. H. Zhang, R. J. Farris, and P. R. Westmoreland, 'Low Flammability and Thermal Decomposition Behavior of Poly(3,3'-dihydroxybiphenylisophthalamide) and Its Derivatives' Macromolecules, 36, 3944 (2003) https://doi.org/10.1021/ma021764x
  20. S. C. Moon, 'Improvement of Flame Retardancy of Polyolefin/rubber foams' Doctoral Dissertation, Chosun University (2004)
  21. 플라스틱난연화의 최근기술과동향' Plastics Science, 17(10), 21 (2003)
  22. Frost & Sullivan, 'European flame retardant market' 2006