Preparation of crosslinkable imide oligomers and Applications in Polyether Imides for Dual-ovenable Packaging

가교형 이미드 올리고머 제조 및 듀얼 오브너블 용기(Dual-Ovenable Packaging) 용 폴리에테르이미드에 대한 적용 연구

  • Seo, Jongchul (Department of Packaging, Yonsei University) ;
  • Park, Su-Il (Department of Packaging, Yonsei University) ;
  • Choi, Seunghyuk (Department of Chemical Engineering, Yonsei University) ;
  • Jang, Wongbong (Department of Chemical Engineering, Yonsei University) ;
  • Han, Haksoo (Department of Chemical Engineering, Yonsei University)
  • 서종철 (연세대학교 과학기술대학 패키징학과) ;
  • 박수일 (연세대학교 과학기술대학 패키징학과) ;
  • 최승혁 (연세대학교 공과대학 화학공학과) ;
  • 장원봉 (연세대학교 공과대학 화학공학과) ;
  • 한학수 (연세대학교 공과대학 화학공학과)
  • Received : 2009.07.02
  • Accepted : 2009.12.17
  • Published : 2010.02.28

Abstract

Two different imide oligomers(6FDA-ODA/APA and 6FDA-MDA/MA) having crosslinkable end groups were prepared by using a solution imidization method and their properties were investigated. Also, semi-interpenetrating polymer networks(semi-IPN) were prepared using the blends of imide oligomers with polyetherimide $Ultem^{(R)}$, which is used in dual-ovenable packaging materials. The characteristic properties of semi-IPN films were interpreted by using TGA, Thin Film Diffusion Analyzer, and WAXD. Molecular weights of imide oligomers were successfully controlled utilizing 2-aminophenylacetylene(APA) and maleic anhydride(MA) as an endcapping agent. Exotherm reactions by crosslinking appeared and the amount of exthotherm heat was linearly increased as the content of imide oligomers was increased. For semi-IPNs of $Ultem^{(R)}$ and imide oligomers, 5% and 10% weight loss temperatures increased as the contents of imide oligomers were increased. Diffusion coefficient and water uptake of semi-IPNs decreased as the content of imide oligomers was increased, which might be resulted from hydrophobic fluorine group and high packing density. It was concluded that relatively low thermal stability and hydrolytic stability of polyetherimide $Ultem^{(R)}$ were improved by incorporating new developed imide oligomers.

본 연구에서는 Dual-Ovenable Packaging 용 폴리에테르이미드의 수분흡수 특성을 개선하기 위하여 가교구조를 형성할 수 있는 말단기를 포함한 이미드 올리고머를 신규 합성하였으며, 이를 이용한 폴리에테르이미드와 가교구조 (semi-IPN, semi-interpenetrating network)를 형성을 통하여 수분흡수와 열적 특성 변화, 그리고 구조적 특성에 대하여 조사하였다. 가교 말단기와 용액 이미드화법을 이용하여 두 종류의 이미드 올리고머 6FDA-ODA/APA와 6FDA-MDA/MA를 제조하였으며, 그 특성을 고찰하였다. 또한 이미드 올리고머와 $Ultem^{(R)}$ 혼합물의 semi-IPN 구조를 제조하였으며, 열적 성질, 수분흡수 거동, 그리고 박막의 구조적 특징을 TGA, Thin Film Diffusion Analyzer, 그리고 XRD 분석을 이용하여 해석하였다. 제조한 이미드 올리고머는 말단기의 양을 이용하여 분자량 조절이 가능하였다. 그리고, 온도가 증가함에 따라 가교에 의한 발열반응이 일어나며, 가교 가능한 말단기가 증가할수록 발열량이 증가하였다. $Ultem^{(R)}$과 이미드 올리고머 혼합물에 의한 semi-IPN 구조는 이미드 올리고머의 비율이 증가할수록 5와 10% 질량감소 온도가 상승하였다. 또한, 수분에 대한 친화도가 작은 불소기를 함유하는 이미드 올리고머와 패킹정도의 증가로 인하여 semi-IPN의 확산계수와 수분흡수량이 감소하였다. 이와 같이 열적 성질과 수분에 대한 안정성이 떨어지는 단점을 semi-IPN 구조를 통하여 보완할 수 있었다.

Keywords

References

  1. Sidwell, J. A., Food Contact Polymeric Materials, iSmithers Rapra Publishing, Shropshire(England), (1992).
  2. Kentrick, A. J., "Heat Retaining Food Container," U.S. Patent No. 5,052,369(1991).
  3. Kim, C., Basis and Application of Plastic Packaging, Packaging Industry Publishing, Seoul(2003).
  4. Domininghaus, H., Plastics for Engineers; Materials, Properties, Applications, Hanser Publishers, New York(1988).
  5. http://www.stouffers.com.
  6. Ghosh, M. K. and Mittal, K. L., Polyimides: Fundamentals and Applications, Marcel Dekker: New York(1996).
  7. Wilson, D., Stenzenberger, H. D. and Hergenrother, P. M., Polyimides, Chapman and Hall, New York(1990).
  8. Sperling, L. H., Interpenetrating Polymer Networks and Related Materials, Plenum Press, New York(1981).
  9. Srinivas, S., Caputo, F. E. and Wilkes, G. L., "Semicrystalline Polyimides Based on Controlled Molecular-Weight Phthalimide End- Capped 1,3-bis(4-Aminophenoxy)Benzene and 3,3',4,4'-Biphenyltetracarboxylic Dianhydride - Synthesis, Crystallization, Melting, and Thermal-Stability," Macromolecules, 30, 1012-1022(1997). https://doi.org/10.1021/ma9604597
  10. Seo, J., Jang, W., Lee, S. and Han, H., "The stability of Semiinterpenetrating Polymer Networks Based on Sulfonated Polyimide and Poly(ethylene glycol) Diacrylate for Fuel Cell Applications," Polym. Degrad. Stabil., 93, 298-304(2008). https://doi.org/10.1016/j.polymdegradstab.2007.08.011
  11. Seo, J., Lee, C., Jang, W., Sundar, S. and Han, H., "Water Sorption and Diffusion Behaviors in Composite Films of Poly(ether imide) and Bismaleimide," J. Appl. Polym. Sci., 99, 1692-1697(2006). https://doi.org/10.1002/app.22665
  12. Seo, J., Jang, W. and Han, H., "Thermal, Optical, and Water Sorption Properties in Composite Films of Poly(ether imide) and Bismaleimides: Effect of Chemical Structure," J. Appl. Polym. Sci., 113, 777-783(2009). https://doi.org/10.1002/app.29694
  13. Douglas, W. E. and Overend, A. S., "Curing Reactions in Acetylene-terminated Resins. Part 5. Cyclotrimerization versus Linear Polyene Formation in the Catalysed Cure of Ethynylaryl-terminated Monomers," J. Mater. Chem., 4, 1167-1172(1994). https://doi.org/10.1039/jm9940401167
  14. Crank, J. and Park, G. S., Diffusion in Polymers, Academic Press, London(1968).
  15. Biemann, K., Spectral Data for Structure Determination of Organic Compounds, Springer-Verlag: Berlin(1989).
  16. Torrecilla, R., Regnier, N. and Mortaigne, B., "Thermal Degradation of Bismaleimide and Bisnadimide Networks - Products of Thermal Degradation and Type of Crosslinking Points," Polym. Degrad. Stabil., 51, 307-318(1996). https://doi.org/10.1016/0141-3910(95)00197-2
  17. Kurdi, J. and Kumar, A., "Performance of PEI/BMI Semi-IPN Membranes for Separations of Various Binary Gaseous Mixtures," Polymer, 53, 301-311(2007).
  18. Van Krevelen, D. W., Properties of Polymers, Elsevier, Amsterdam (1990).
  19. Van Alsten, J. G. and Coburn, J. C., "Structural Effects on the Transport of Water in Polyimides," Macromolecules, 27, 3746-3752(1994). https://doi.org/10.1021/ma00092a011