Synthesis and Characterization of UV-curable Aliphatic Epoxy Acrylate

자외선 경화형 지방족 에폭시 아크릴레이트의 합성 및 특성분석

  • Kim, Young Chul (Reliability Assessment Center, Korea Research Institute of Chemical Technology) ;
  • Lee, Byung-Hoon (Reliability Assessment Center, Korea Research Institute of Chemical Technology)
  • 김영철 (한국화학연구원 신뢰성평가센터) ;
  • 이병훈 (한국화학연구원 신뢰성평가센터)
  • Received : 2009.11.30
  • Accepted : 2009.12.18
  • Published : 2009.12.30

Abstract

UV-curable aliphatic epoxy acrylates were prepared by the reaction of glycerol diglycidyl ether (GDE) with 2-carboxyethyl acrylate (2-CEA) or 2-hydroxyethyl acrylate (2-HEA). The structures of the epoxy acrylates were characterized by FT-IR, $^1H$-NMR, and $^{13}C$-NMR and the yield was obtained by prep-LC. The UV- and the thermal-curing behaviors of the product were investigated using photo-DSC and DSC, respectively. The reactivity of 2-CEA was higher than 2-HEA and the yield of the product (GEA-C) which was prepared using 2-CEA was about 83%. The maximum UV-curing time ($T_{max}$) of the GEA-C contained non-reactive components and by-product was about 10 seconds. The GEA-C showed low color difference (${\Delta}E^*$), low viscosity, and good thermal stability - its value was 2.51, 192 cps, and $299^{\circ}C$ (at 5% weight loss), respectively. The activation energies ($E_a$) of thermal-curing reaction calculated from Kissinger and Ozawa-Flynn-Wall method were 91~92 kJ/mol.

지방족 에폭시 수지인 glycerol diglycidyl ether (GDE)에 단관능성 아크릴 수지인 2-carboxyethyl acrylate (2-CEA) 또는 2-hydroxyethyl acrylate (2-HEA)를 반응시켜 지방족 에폭시 아크릴레이트를 제조하였다. FT-IR, $^1H$-NMR, 그리고 $^{13}C$-NMR를 사용하여 생성물을 확인하였고, 수율은 prep-LC를 사용하여 얻었다. 생성물의 자외선 경화거동은 photo-DSC를 사용하였고, 열경화 반응성은 DSC를 사용하여 얻었다. 2-CEA의 반응성이 2-HEA보다 월등히 높음을 알 수 있었고, 2-CEA로부터 제조한 지방족 에폭시 아크릴레이트(GEA-C)의 수율은 약 83%이었다. 촉매를 제거한 GEA-C 생성물의 자외선 경화반응($T_{max}$)은 약 10 s로 빠르게 진행되었다. GEA-C는 투명하고, 내열성이 우수하며 저점도를 갖고 있음을 확인할 수 있었다. ${\Delta}E^*$는 2.51, 점도는 192 cps, 5% 중량감소 때의 온도는 $299^{\circ}C$이었다. Kissinger와 Ozawa-Flynn-Wall 식으로 얻은 GEA-C의 열경화 반응의 활성화에너지($E_a$)는 91~92 kJ/mol이었다.

Keywords

References

  1. "UV Curing: Science and Technology", S. P. Pappas, Ed., Technology Marketing Corp., Norwalk, CT (1985).
  2. R. Holman, "UV and EB Curing Formulation for Printing Inks, Coating and Paints," SITA Technology, London (1984).
  3. M. J. Moon, J. H. Park, G. D. Lee, C. S. Suh, and J. R. Kim, J. Korean Ind. Eng. Chem., 2, 175 (1991).
  4. J. K. Lim, D. K. Kim, and J. Y. Hwang, J. Korean Ind. Eng. Chem., 14, 818 (2003).
  5. H. G. Kim, D. H. Lee, and K. E. Min, Polymer (Korea), 31, 53 (2007).
  6. M. Ghaemy, M. Heidaripour, and M. Barghamadi, J. Appl. Polym. Sci., 106, 1917 (2007). https://doi.org/10.1002/app.26899
  7. M. Ghaemy, S. Bekhradnia, and M. Heidaripour, J. Appl. Polym. Sci., 110, 983 (2008). https://doi.org/10.1002/app.28683
  8. Ciba Specialty Chemicals, Technical Data Sheet, 1 (2001). Available from: http://www.ciba.com/irgacure 651-2.
  9. R. Seighi, E. Hewlett, and J. Kim, J. Dent. Res., 68, 1760 (1989). https://doi.org/10.1177/00220345890680120801
  10. M. Gross and J. Moser, J. Oral Rehab., 4, 311 (1977). https://doi.org/10.1111/j.1365-2842.1977.tb00997.x
  11. W. S. Ahn and S. K. Yoon, Elastomer, 42, 47 (2007).
  12. W. S. Ahn and S. H. Lee, Elastomer, 38, 326 (2003).
  13. T. Ozawa, Ball. Chem. Soc. Jpn., 38, 1881 (1965). https://doi.org/10.1246/bcsj.38.1881
  14. S. J. Park, S. J. Seok, J. G. Kang, and S. H. Kwon, Elastomer, 39, 42 (2004).