양이온 촉매/에폭시 경화계에서 에폭시 수지의 당량 및 촉매 함량이 경화반응에 미치는 영향

김연철; 박수진; 이재락

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.6, 960-966, December, 1997

Effects of Equivalent Weight of Epoxy Resins and Content of Catalyst on the Curing Reaction in Cationic Catalyst/Epoxy Cure System

김연철, 박수진, 이재락

초록

양이온 촉매(N-Benzylpyrazinium hexafluoroantimonate, BPH)/에폭시 경화계에서 에폭시 수지(DGEBA/DGEBF)의 에폭시 당량 및 촉매함량이 경화 거동, 열적특성 및 유변학적 특성에 미치는 영향을 FT-IR, DSC 및 Dynamic Viscometer를 이용하여 연구하였다. 0.5wt% BPH를 함유하는 DGEBA의 경우 DGEBF/BPH에 비하여 반응 속도가 빠르고 반응 초기에서의 반응 진행(전환율)이 크게 나타나는 것을 등온 DSC 및 FT-IR 결과에서 확인할 수 있었다. 반면 BPH의 함량이 증가함에 따라 반응속도와 전환율이 거의 같은 값을 보여줌을 알 수 있었다. 겔화점(Gel point)으로 정의되는 저장 탄성율(G')과 손실 탄성율(G")의 교차점(G'/G"=1)의 경우 하이드록시기를 포함할 때 도달시간이 빠르게 나타나는데 이는 반응 초기에 하이드록시기의 반응 참여에 의해 반응 초기에 3차원 가교 구조를 형성하는 것으로 생각되었고 또한 DSC 및 FT-IR 결과와 일치하는 결과를 보여주었다. 겔화점에 도달하는 시간을 이용하여 구한 활성화에너지 값은 31-39 kJ.mol^-1의 값을 나타내었다.

The effects of epoxy resins and content of catalyst on the cure characteristics were studied by FT-IR, DSC and dynamic viscometer for the thermal properties and rheological properties of the catalytic (N-Benzylpyrazinium hexafluoroantimonate, BPH) epoxy thermosetting system. Compared with DSC results of DEGBF containing 0.5wt% BPH, the DSC thermograms of DGEBA containing 0.5wt% BPH indicated that the reaction was faster than that of DGEBF/BPH and the conversion rate of DGEBA/BPH was high in the initial stage of the reaction. As the concentration of BPH increases, the reaction and conversion rates show similar value in both the cases. The influence of hydroxyl group of epoxy resin on gel point defined from the crossover point of storage modulus (G') and loss modulus (G") could be explained by the formation of 3-dimensional network in the initial stage owing to the curing reaction between epoxides and hydroxyl groups of epoxy resin. This was consistent with the gel point obtained from DSC, FT-IR and moduli crossover. The activation energy (E_t) obtained from the crossover point (G'/G"=1) are 31-39 kJ.mol^-1 for various BPH compositions in case of two epoxy systems.

[References]

Crivello JV, Lee JL, Macromolecules, 14, 1141 (1981)
Abu-Abdoun II, Ali A, Eur. Polym. J., 29, 1439 (1993)
Pappas SP, Hill LH, J. Coat. Technol., 53, 43 (1981)
Endo T, Kikkawa A, Uno H, Sato H, J. Polym. Sci. C: Polym. Lett., 27, 73 (1989)
Morio K, Murase H, Tsuchiya H, J. Appl. Polym. Sci., 32, 5727 (1986)
Gu J, Narang SC, Pearce EM, J. Appl. Polym. Sci., 30, 2997 (1985)
Skourlis TP, Mccullough RL, J. Appl. Polym. Sci., 62(3), 481 (1996)
Lee SB, Park YS, Lee KW, Endo T, Chem. Lett., 17, 287 (1995)
Kim YC, Park SJ, Lee JR, Polym. J., 29, 759 (1997)
Mark HF, Bikales RM, Overberger CG, Menges G, Kroschwitz JI, Encyclopedia Polym. Sci. Eng. 2nd Ed., 6, 340 (1986)
Lin YG, Sautereau H, Pascault JP, J. Polym. Sci. A: Polym. Chem., 24, 2171 (1986)
Wang X, Gillham JK, J. Appl. Polym. Sci., 43, 2267 (1991)
Skourlis TP, Mccullough RL, J. Appl. Polym. Sci., 62(3), 481 (1996)
Tung CM, Dynes PJ, J. Appl. Polym. Sci., 27, 569 (1982)
Adolf D, Martin JE, Wilcoxon JP, Macromolecules, 23, 527 (1990)
Imaz JJ, Markaide N, Jurado MJ, Corcuera MA, Mondragon I, Eur. Polym. J., 28, 299 (1992)
Halley PJ, Mackay ME, Polym. Eng. Sci., 36(5), 593 (1996)
Kenny JM, Maffezzoli A, Nicolais L, Compos. Sci. Technol., 38, 339 (1990)
Kenny JM, Opalicki M, Compos. Part A, 27A, 229 (1996)

[Referenced By]

[1] Crivello JV, Lee JL, Macromolecules, 14, 1141 (1981)

[2] Abu-Abdoun II, Ali A, Eur. Polym. J., 29, 1439 (1993)

[3] Pappas SP, Hill LH, J. Coat. Technol., 53, 43 (1981)

[4] Endo T, Kikkawa A, Uno H, Sato H, J. Polym. Sci. C: Polym. Lett., 27, 73 (1989)

[5] Morio K, Murase H, Tsuchiya H, J. Appl. Polym. Sci., 32, 5727 (1986)

[6] Gu J, Narang SC, Pearce EM, J. Appl. Polym. Sci., 30, 2997 (1985)

[7] Skourlis TP, Mccullough RL, J. Appl. Polym. Sci., 62(3), 481 (1996)

[8] Lee SB, Park YS, Lee KW, Endo T, Chem. Lett., 17, 287 (1995)

[9] Kim YC, Park SJ, Lee JR, Polym. J., 29, 759 (1997)

[10] Mark HF, Bikales RM, Overberger CG, Menges G, Kroschwitz JI, Encyclopedia Polym. Sci. Eng. 2nd Ed., 6, 340 (1986)

[11] Lin YG, Sautereau H, Pascault JP, J. Polym. Sci. A: Polym. Chem., 24, 2171 (1986)

[12] Wang X, Gillham JK, J. Appl. Polym. Sci., 43, 2267 (1991)

[13] Skourlis TP, Mccullough RL, J. Appl. Polym. Sci., 62(3), 481 (1996)

[14] Tung CM, Dynes PJ, J. Appl. Polym. Sci., 27, 569 (1982)

[15] Adolf D, Martin JE, Wilcoxon JP, Macromolecules, 23, 527 (1990)

[16] Imaz JJ, Markaide N, Jurado MJ, Corcuera MA, Mondragon I, Eur. Polym. J., 28, 299 (1992)

[17] Halley PJ, Mackay ME, Polym. Eng. Sci., 36(5), 593 (1996)

[18] Kenny JM, Maffezzoli A, Nicolais L, Compos. Sci. Technol., 38, 339 (1990)

[19] Kenny JM, Opalicki M, Compos. Part A, 27A, 229 (1996)