공업화학 (Applied Chemistry for Engineering)

  • 제21권4호
  • /
  • Pages.377-384
  • /
  • 2010
  • /
  • 1225-0112(pISSN)
  • /
  • 2288-4505(eISSN)
한국공업화학회 (The Korean Society of Industrial and Engineering Chemistry)
권호 표지

3-Azidopropane-1,2-diol로 쇄연장된 GAP/PTMG 폴리우레탄의 상거동

Phase Behaviors of the GAP/PTMG Polyurethanes Chain Extended with 3-Azidopropane-1,2-Diol

  • Kim, Hyoung-Sug (Department of Chemical Engineering, Hanyang University) ;
  • You, Jong-Sung (Department of Chemical Engineering, Hanyang University) ;
  • Kweon, Jung-Ohk (Department of Chemical Engineering, Hanyang University) ;
  • Kim, Jung-Su (Department of Chemical Engineering, Hanyang University) ;
  • Lee, Tong-Sun (Department of Chemical Engineering, Hanyang University) ;
  • Noh, Si-Tae (Department of Chemical Engineering, Hanyang University) ;
  • Jang, Young-Ok (Department of Bio-Nano Technology, Hanyang University) ;
  • Kim, Dong-Kuk (Department of Applied Chemistry, Hanyang University) ;
  • Kwon, Sun-Kil (Agency for Defense Development)
  • 투고 : 2009.10.13
  • 심사 : 2010.04.13
  • 발행 : 2010.08.10
PDF 다운로드
⟨ 이전 논문 다음 논문 ⟩

초록

에너지 함유 쇄연장제인 3-azidopropane-1,2-diol (AzPD)로 쇄연장된 에너지 함유 폴리우레탄의 특성을 고찰하기 위하여 비교연구법을 수행하였다. 이를 위하여 AzPD, 1,4-BD, 또는 1,5-PD 쇄연장제를 갖는 poly(glycidyl azide)/poly(tetramethylene oxide)계 에너지 함유 세그멘티드 폴리우레탄(energetic segmented polyurethane, GAP/PTMG ESPU)을 dimethyl formamide (DMF) 용매에서 합성하여 상거동을 고찰하였다. 상거동은 fourier transform infrared.attenuated total reflection spectroscopy (ATR FT.IR), differential scanning calorimetry (DSC), 및 dynamic mechanical analysis (DMA)를 이용하여 분석하였다. ATR FT.IR spectrum 분석결과 7일 경과 시편의 GAP/PTMG AzESPU의 수소결합하지 않은 C=O 분율이 0.5로 각각 0.44 및 0.41인 GAP/PTMG BDESPU 및 GAP/PTMG PDESPU 보다 높았고, 제조 후 60일 경과 시편의 경우 0.26~0.29의 범위로 큰 차가 없었다. 제조 후 7일 경과 GAP/PTMG AzESPU 시편의 DMA curves는 무정형 고분자의 거동과 유사하였으며, GAP/PTMG BDESPU과 GAP/PTMG PDESPU는 고무평탄구간과 연성 흐름 구간을 갖는 점탄성 거동을 나타냈다. 그러나, 제조 후 60일 경과 GAP/PTMG AzESPU의 DMA curves는 GAP/PTMG PDESPU와 같이 고무평탄구간과 연성 흐름 구간을 갖는 점탄성 거동을 나타냈다. ATR FT-IR, DSC 및 DMA 분석을 이용한 상거동 고찰로부터 AzPD로 쇄연장된 GAP/PTMG ESPU는 1,4-BD 또는 1,5-PD로 쇄연장된 GAP/PTMG ESPU보다 구성성분간의 상혼합이 잘 이루어지나 적절한 조건에서 상형평에 도달되면 GAP/PTMG PDESPU와 유사한 TPE의 점탄성 거동을 나타냈다.

We perform a comparative study to investigate the properties of the new energetic chain extender (AzPD). A series of poly(glycidyl azide)/poly(tetramethylene oxide)-based energetic segmented polyurethane (GAP/PTMG ESPU) with different chain extender, which is 3-azidopropane-1,2-diol (AzPD), 1,4-butane diol (1,4-BD), or 1,5 pentane diol (1,5-PD), was synthesized by solution polymerization in dimethyl formamide (DMF) and their phase behaviors were investigated. The ESPUs were characterized with Fourier transform infrared-attenuated total reflection spectroscopy (ATR FT-IR), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The results of the ATR FT-IR analysis of the urethane carbonyl group region showed that the 'free' C=O fraction was higher in GAP/PTMG AzESPU (0.5) than GAP/PTMG BDESPU (0.44) and GAP/PTMG PDESPU (0.41) for 7 days samples after preparation and that it was similar in the range of 0.26~0.29 for three 60 days ESPU samples. DMA curves of the GAP/PTMG AzESPU for 7 days samples showed amorphous polymers, but GAP/PTMG BDESPU and GAP/PTMG PDESPU showed viscoelastic behaviors with rubbery plateau and the flow region. However, DMA curves of the GAP/PTMG AzESPU for 60 days samples showed viscoelastic behaviors with rubbery plateau and the flow region like GAP/PTMG PDESPU, but GAP/PTMG BDESPU did not show the flow region. From phase behaviors with ATR FT-IR, DSC and DMA analysis, GAP/PTMG AzESPU showed good phase-mixing between components. However, it represented viscoelastic behavior of TPE similar to GAP/PTMG PDESPM according to phase equilibrium progress with aging time.

키워드

참고문헌

  1. B. D. Andrea, F. Lillo, A. Faure, and C. Perut, Acta Astronautica, 47, 2 (2000).
  2. A. Provatas, DSTO-TR-0966, (2000) ; J. P. Agrawal, Prog. Energy Combust. Sci., 24, 1 (1998). https://doi.org/10.1016/S0360-1285(97)00015-4
  3. Y. Ou, B. Chen, H. Yan, H. Jia, J. Li, and S. Dong, J. of Propulsion and power, 11, 838 (1995). https://doi.org/10.2514/3.23909
  4. A. N. Nazare, S. N. Aathana, and H. J. Singh, Energetic Materials, 10, 43 (1992). https://doi.org/10.1080/07370659208018634
  5. G. Holden, H. R. Legge, R. Quirk, and H. E. Schroeder, Thermoplastic Elastomers, Hanser/Gardner Publications, Inc., Cincinnati (1996).
  6. S. Fakirov, Handbook of Condensation Thermoplastic Elastomers, Wiley-VCH Verlag Gmbh & Co. KGaA, Weinheim.
  7. W. G. Miller and J. H. Saunders, J. Appl. Polym. Sci., 13, 1277 (1969). https://doi.org/10.1002/app.1969.070130615
  8. G. Holden, H. R. Legge, R. Quirk, and H. E. Schroeder, Thermoplastic Elastomers, 2, Hanser Gargner Publication (1996).
  9. C. Hepburn, Polyurethane Elastomers, Elsevier Science, New York (1992).
  10. J. D. Ingham, W. L. Petty, and P. L. Nichols, Jr., J. Org. Chem., 21, 373 (1956). https://doi.org/10.1021/jo01109a610
  11. Y. Li, T. Gao, J. Liu, K. Linliu, C. R. Desper, and B. Chu, Macromolecules, 25, 7365 (1992)
  12. S. Abouzahr and G. L. Wilkes, Journal of Applied Polymer Science, 29, 2695 (1984) https://doi.org/10.1002/app.1984.070290902
  13. C. E. Wilkes and C. S. Yusek, J. Macromolecular Science : Physics., B7, 157 (1973)
  14. R. Bonart and E. H. Muller, J. Macromolecular Science : Physics., B10, 177 (1974)
  15. T. R. Hesketh, J. W. C. Van Bogart, and S. L. Cooper, Polymer Engineering and Science, 20, 190 (1980) https://doi.org/10.1002/pen.760200304
  16. V. A. Vilensky and Y. S. Lipatov, Polymer, 35, 3069 (1994) https://doi.org/10.1016/0032-3861(94)90421-9
  17. J. T. Koberstein and T. P. Russell, Macromolecules, 19, 714 (1986) https://doi.org/10.1021/ma00157a039
  18. C. S. Paik Sung, C. B. Hu, and C. S. Wu, Macromolecules, 13, 111 (1980) https://doi.org/10.1021/ma60073a022
  19. R. W. Seymour and S. L. Cooper, J. Polym. Sci., Polym. Lett. Ed., 9, 689 (1971). https://doi.org/10.1002/pol.1971.110090911
  20. M. M. Coleman, K. H. Lee, D. J. Skrovanek, and P. C. Painter, Macromolecules, 19, 2149 (1986). https://doi.org/10.1021/ma00162a008
  21. C. M. Brenette, S. L. Hsu, and W. J. Macknight, Macromolecules, 15, 71 (1982) https://doi.org/10.1021/ma00229a014
  22. B. Finck and H. Graindorge, New Molecules for high Energetic Materials. In 27th int. annu. ICT Conf. (energetic materials), 23 (1996).
  23. G. Holden, H. R. Legge, R. Quirk, and H. E. Schroeder, Thermoplastic Elastomers, 15 (1996).
  24. X. R. Li, J. Zhang, and Y. Li, Macromolecules, 37, 7584 (2004). https://doi.org/10.1021/ma049232z