Studies on Thermal Stability and Cure Behavior of Epoxy Resins using Electron-beam Curing Technique

전자선 경화를 이용한 에폭시 수지의 열안정성과 경화동력학에 관한 연구

  • 박수진 (한국화학연구원 화학소재연구부) ;
  • 허건영 (한국화학연구원 화학소재연구부) ;
  • 이재락 (한국화학연구원 화학소재연구부)
  • Published : 2002.04.01

Abstract

The di-functional epoxy resins, i.e., diglycidylether of bisphenol A(DGEBA) and diglycidylethere of bisphenol F(DGEBF) were initiated by cationic catalyst, i.e., benzylquinoxalinium hexafluoroantimonate(BQH) using electron-beam(EB) technique. And the effect of structure of DGEBA and DGEBF on thermal stabilities and cure behaviors was investigated. According to the experimental results, the decomposed activation energy based on Horowitz-Metzger method was higher in the case of DGEBA, but intergral procedural decomposition temperature(IPDT) of DGEBA was lower than DGEBF. This could be interpreted in terms of high crosslink density resulted from hydroxyl bond of DGEBF backbone. It was confirmed in increasing the hydroxyl band at $7000\;cm^{-1}$ and $5235\;cm^{-1}$ using near-infrared spectroscopy(NIRS).

이관능성 에폭시 수지인 DGEBA와 DGEBF를 양이온 촉매인 BQH를 사용하여 전자선(electron-beam) 경화 기술에 의해 경화하였다. 그리고 수지의 구조적 차이가 열안정성과 경화동력학에 미치는 영향을 연구하였다. 실험적 결과에 의하면, Horowitz-Metzger 법에 의한 분해 활성화 에너지는 DGEBA의 경우가 높았지만 적분 열분해 온도(IPDT)는 DGEBA가 DGEBF 보다 낮았다. 이것은 DGEBF 주사슬의 수소 결합으로 인해 가교밀도가 높아졌기 때문인 것으로 사료되며, 근적외선 분광기(NIRS)를 사용하여 $5235\;cm^{-1}$$7000\;cm^{-1}$에서의 hydroxyl band의 증가로 확인하였다.

Keywords

References

  1. Macromolecular Materials and Engineering v.280;281 no.1 Toughening of electron-beam cured acrylate resins T. Glauser;A. Hult;M. Johansson;X. Kormmann;L. Berglund
  2. Radiation Physics and Chemistry v.56 no.4 Electron-bean curable epoxy resins for the manufacture of high-performance composites V. J. Lopata;C. B. Saunders;A. Singh;C. J. Janke;G. E. Wrenn;S. J. Havens https://doi.org/10.1016/S0969-806X(99)00330-8
  3. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms v.105 no.1-4 Electron beams research and technology R. Mehnert https://doi.org/10.1016/0168-583X(95)00634-6
  4. Journal of Polymer Science Part A: Polymer Chemistry v.39 no.1 Studies on epoxy resins cured by cationuc latent thermal catalysts: The effect of the catalysts on the thermal, rheological, and mechanical properties S. J. Park;M. K. Seo;J. R. Lee;D. R. Lee https://doi.org/10.1002/1099-0518(20010101)39:1<187::AID-POLA210>3.0.CO;2-H
  5. Journal of Applied Polymer Science v.80 no.1 UV curing behavior of methacrylated hyperbranched poly(amine-ester)s H. Wei;Y. Lu;W. Shi;H. Yuan;Y. Chen https://doi.org/10.1002/1097-4628(20010404)80:1<51::AID-APP1074>3.0.CO;2-W
  6. Polmyer Testing v.18 no.2 Microwave curing of epoxy-amine system ; effect of curing agent on the rate enhancement F. Y. C. Boey;B. H. Yap;L. Chia
  7. Macromolecular Materials and Engineering v.274 no.1 A comparison of radiation and thermal curing of thick composites T. Glauser;M. Johansson;A. Hult https://doi.org/10.1002/(SICI)1439-2054(20000101)274:1<25::AID-MAME25>3.0.CO;2-L
  8. Journal of Applied Polymer Science v.75 no.1 Electron beam crosslinking of fluoroalkoxy, methoxyethoxyethoxy, and substituted phenoxy polyphosphazenes: Physical and chemical characterization and comparison to a thermally induced free radical process and ionic complexation F. F. Stewart;R. E. Singler;M. K. Harrup;E. S. Peterson;R. P. Lash
  9. Ph. D. Thesis Cationic Pol Vinyl Ethers using Iodonium and Fulfonium Salts P. E. Sundell
  10. Chemistry of Materials v.9 no.5 Fabrication of Epoxy Matrix Composites by Electron Beam induced Cationic Polymerization J. V. Crivello;T. C. Walton;R. Malik https://doi.org/10.1021/cm9700312
  11. Macromolecular Materials and Engineering v.274 no.1 Electron-beam curing of thick thermoset composites: Effect of temperature and fiber T. Glauser;A. Hult;M. Johansson;X. Kornmann;L. Berglund https://doi.org/10.1002/(SICI)1439-2054(20000101)274:1<20::AID-MAME20>3.0.CO;2-E
  12. Journal of Polymer Science Part B: Polymer Physics v.38 no.16 Cure bahavior of diglycidylether of bisphenol A/trimethylolpropane tri-glycidylether epoxy blends initiated by thermal latent catalyst S. J. Park;T. J. Kim;J. R. Lee https://doi.org/10.1002/1099-0488(20000815)38:16<2114::AID-POLB50>3.0.CO;2-8
  13. Journal of Polymer Science Part A: Polymer Chemistry v.38 no.16 Isothermal cure kinetics of epoxy/phenol-novolac resin blend system initiated by cationic latent thermal catalyst S. J. Park;M. K. Seo;J. R. Lee;D. R. Lee https://doi.org/10.1002/1099-0518(20000815)38:16<2945::AID-POLA120>3.0.CO;2-6
  14. Polymers for Advanced Technologies v.12 no.3-4 A systematic study of the microwave and thermal cure kinetics of the TGDDM/DDS and TGDDM/DDM epoxy-amine resin systems D. J. T. Hill;Graeme A. George;David G. Rogers https://doi.org/10.1002/pat.139
  15. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms v.151 no.1-4 UV and electron beam-induced cationic polymerization J. V. Crivello https://doi.org/10.1016/S0168-583X(99)00109-3
  16. Polymer v.42 no.12 Cure kinetics and ultimate properties of a tetrafunctional epoxy resin toughened by a perfluoro-ether oligomer P. Musto;E. Martuscelli;G. Ragosta;L. Mascia https://doi.org/10.1016/S0032-3861(00)00884-3
  17. Journal of Polymer Science Part B: Polymer Physics v.39 no.1 Thermal stability and toughening of epoxy resin with polysulfone resin S. J. Park;H. C. Kim https://doi.org/10.1002/1099-0488(20010101)39:1<121::AID-POLB110>3.0.CO;2-N
  18. Fundamentals and Application to Polymer Science T. Hatakeyama;F. X. Quinn
  19. Journal of Polymer Science Part A: Polymer Chemistry v.37 no.21 Evaluation of the thermal oxidative stability of polyimides via TGA techniques M. J. Turk;A. S. Ansari;W. B. Alston;G. S. Gahn;A. A. Frimer;D. A. Scheiman https://doi.org/10.1002/(SICI)1099-0518(19991101)37:21<3943::AID-POLA10>3.0.CO;2-5
  20. European Polymer Journal v.33 no.6 Curing kinetics of an acrylic resin/epoxy resin system using dynamic scanning calorimetry F. Chu;T. McKenna;S. Lu https://doi.org/10.1016/S0014-3057(96)00243-1
  21. Journal of Polymer Science v.80 no.5 Activation energies for the epoxy system BADGE n= 0/m-XDA obtained using data from thermogravimetric analysis F. Fraga;E. R. Nunez
  22. Journal of Polymer Science Part B: Polymer Physics v.39 no.1 Thermal stability and toughening of epoxy resin with polysulfone resin S. J. Park;H. C. Kim https://doi.org/10.1002/1099-0488(20010101)39:1<121::AID-POLB110>3.0.CO;2-N
  23. Journal of Applied Polymer Science v.78 no.2 Thermal stability and mechanical behavior of cycloaliphatic-DGEBA epoxy blend system initiated by cationic latent catalyst G. H. Kwak;S. J. Park https://doi.org/10.1002/1097-4628(20001010)78:2<290::AID-APP80>3.0.CO;2-9
  24. Journal of Polymer Science Part B: Polymer Physics v.39 no.3 Near-infrared spectroscopic studies on the cure behaviors of the CAE/DGEBA blend system initiated by a thermal latent cataly S. J. Park;G. H. Kwak;M. K. Seo;J. R. Lee https://doi.org/10.1002/1099-0488(20010201)39:3<326::AID-POLB1004>3.0.CO;2-X
  25. Vibrational Spectroscopy v.12 no.2 Near- and mid-infrared spectroscopy studies of an epoxy reactive system N. Poisson;G. Lachenal;H. Sautereau https://doi.org/10.1016/0924-2031(96)00027-6
  26. Vibrational Spectroscopy v.9 no.1 Dispersive and fourier transform near-infrared spectroscopy of polymeric materials G. Lachenal https://doi.org/10.1016/0924-2031(94)00054-K