형광분석기를 이용한 에폭시-산무수물계의 경화 모니터링

조동환; 김득수; 이종근; Donghwan Cho; Deuk Soo Kim; Jong Keun Lee

Polymer(Korea), Vol.25, No.2, 199-207, March, 2001

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형광분석기를 이용한 에폭시-산무수물계의 경화 모니터링

Cure Monitoring of An Epoxy-Anhydride System by Means of Fluorescence Spectroscopy

조동환^†, 김득수, 이종근

금오공과대학교 고분자공학과

Donghwan Cho^†, Deuk Soo Kim, and Jong Keun Lee

Department of Polymer Science and Engineering, Kumoh National Univerisity of Technology, Kumi, Kyungbuk 730-701, Korea

E-mail:

초록

본 연구에서는 경화촉진제로서 N,N-dimethyl benzyl amine (BDMA) 또는 1-cyanoethyl-2-ethyl-4-methyl imidazole (2E4MZ-CN)을 포함하고 있는 산무수물계 경화제에 의한 diglycidyl ether of bisphenol-A (DGEBA)의 경화거동을 형광분석기를 사용하여 광물리적 특성 변화의 관점에서 해석하였다. 이를 위해 1,3-bis-(1-pyrene)propane (BPP) probe를 에폭시수지 내에 균일하게 도입시켰다. 주위 환경 변화에 의한 분자의 공간구조 변화에 민감한 BPP probe는 분자내 여기체 형광을 잘 형성하였으며 에폭시수지의 경화반응에 따른 미세점도 변화 또는 분자의 움직임에 민감하였다. 에폭시수지의 경화거동은 경화시간, 경화온도 및 경화촉진제의 종류에 따른 단량체 형광세기(I_M), 여기체 형광세기(I_E) 그리고 I_M/I_E 값의 변화로부터 설명되었다. 그 결과는 이전의 DSC 또는 torsion pendulum을 이용하여 에폭시-산무수물계에 대하여 얻어진 경화거동 결과와 일치하였다. 또한, 형광분석 방법은 다른 분석 방법에서 해석이 어려운 저온영역에서의 열경화성 수지의 경화거동에 대한 정보를 제시하였다.

In the present study the cure behavior of diglycidyl ether of bisphenol-A (DGEBA) using an anhydride-based hardener in the presence of MN-dimethyl benzyl amine(BDMA) or 1-cyanoethyl-2-ethyl-4-methyl imidazole(2E4MZ-CN) as an accelerator has been monitored and interpreted from the viewpoint of photophysical properties by means of fluorescence spectroscopy. To do this, 1,3-bis-(1-pyrene)propane (BPP) was well incorporated in the epoxy resin system by mechanical blending. The BPP probe, which is very sensitive to conformational change of the molecule influenced by the surrounding medium, successfully formed intramolecular excimer fluorescence. It is susceptible to the micro-viscosity or local viscosity and molecular mobility according to the epoxy cure. The cure behavior was explained with monomer fluorescence intensity (I(M)), excimer fluorescence intensity (I(E)) and I(M)/I(E) ratio as a function of cure time, cure temperature and accelerator. The present work agreed with the previous report on the cure behavior of an epoxy-anhydride system studied using DSC or torsion pendulum method. This study also suggests that the use of fluorescence technique may provide information on cure behavior of a thermosetting resin in a low temperature region, which has not been well interpreted by other analytical methods.

Keywords:epoxy-anhydride system;cure behavior;fluorescence intensity;excimer formation;monomer/excimer fluorescence ratio;micro-viscosity;molecular mobility

[References]

Ulrich H, "Reaction Polymers", eds. by W.F. Gun, W. Riese, and H. Ulrich, chapter 1, Hanser Publishers, Munich (1992)
Park WH, Lee JK, Kwon KJ, Polym. J., 28, 407 (1996)
Antoon MK, Zehner BE, Koenig JL, Polym. Compos., 2, 81 (1981)
Takahama T, Geil PH, J. Polym. Sci. Polym. Lett. Ed., 20, 453 (1982)
Gillham JK, J. Macromol. Sci.-Phys., B9(2), 209 (1974)
Gillham JK, Polym. Int., 44, 262 (1997)
Bokoza L, Pham-Van-Cang C, Monnerie L, Vandendriessche J, De Schryver FD, Polymer, 30, 45 (1989)
Cho D, Poter LJ, Mattice WL, Biopolymers, 31, 537 (1991)
Hemker DJ, Char K, Oyama HT, Gast AP, Frank CW, Adv. Chem. Ser., 223, 263 (1989)
Cho D, Yang K, Drzal LT, manuscript in preparation
Sung CSP, Chin IJ, Yu WC, Macromolecules, 18, 1512 (1985)
Wachsman ED, Frank CW, Polymer, 29, 1191 (1988)
Lin KF, Wang FW, Polymer, 35(4), 687 (1994)
Lakowicz JR, "Principles of Fluorescence Spectroscopy", chapter 1, Plenum Press, New York (1983)
Guillet J, "Polymer Photophysics and Photochemistry", chapter 7, Cambridge Univ. Press, Cambridge (1985)
Morawetz H, J. Polym. Sci. A: Polym. Chem., 37(12), 1725 (1999)
Mita TF, Bauer RS, "Epoxy Resin-Chemistry and Technology", ed. by C.A. May, Marcel Dekker, Inc., New York (1988)
Ellis B, "Chemistry and Technology of Epoxy Resins", Blackie Academic and Professional, Chapman and Hall, London (1993)
Park WH, Lee JK, J. Appl. Polym. Sci., 67(6), 1101 (1998)
Kim DS, Lee JK, Choi EJ, Polym.(Korea), 23(4), 569 (1999)
Lee JK, Park WH, Korean J. Mater. Res., 6(5), 494 (1996)
Sung CSP, Sung NH, Int'l SAMPE Symp. May 8-11, 51 (1995)
Wang FW, Lowry RE, Fanconi BM, Polymer, 27, 1529 (1986)
Paik HJ, Sung NH, Polym. Eng. Sci., 34(12), 1025 (1994)
Wang FW, Lowry RE, Fanconi BM, Polym. Mater. Sci. Eng., 53, 180 (1985)
Stroeks A, Shmorhun M, Jamieson AM, Simha R, Polymer, 29, 467 (1988)
Prime RB, "Thermal Characterization of Polymeric Materials", ed. by E.A. Turi, volume 2, chapter 6, Academic Press, Inc., San Diego (1997)
Ilavsky M, "Polymer Networks: Principles of Their Formation, Structure and Properties", ed. by R.F.T. Stepto, chapter 8, Blackie Academic & Professional, London (1998)
Enns JB, Gillham JK, J. Appl. Polym. Sci., 28, 2567 (1983)
Gillham JK, Polym. Eng. Sci., 26, 1429 (1986)
Zachariasse KA, Duveneck G, Busse R, J. Am. Chem. Soc., 106, 1045 (1984)

[Referenced By]

[1] Ulrich H, "Reaction Polymers", eds. by W.F. Gun, W. Riese, and H. Ulrich, chapter 1, Hanser Publishers, Munich (1992)

[2] Park WH, Lee JK, Kwon KJ, Polym. J., 28, 407 (1996)

[3] Antoon MK, Zehner BE, Koenig JL, Polym. Compos., 2, 81 (1981)

[4] Takahama T, Geil PH, J. Polym. Sci. Polym. Lett. Ed., 20, 453 (1982)

[5] Gillham JK, J. Macromol. Sci.-Phys., B9(2), 209 (1974)

[6] Gillham JK, Polym. Int., 44, 262 (1997)

[7] Bokoza L, Pham-Van-Cang C, Monnerie L, Vandendriessche J, De Schryver FD, Polymer, 30, 45 (1989)

[8] Cho D, Poter LJ, Mattice WL, Biopolymers, 31, 537 (1991)

[9] Hemker DJ, Char K, Oyama HT, Gast AP, Frank CW, Adv. Chem. Ser., 223, 263 (1989)

[10] Cho D, Yang K, Drzal LT, manuscript in preparation

[11] Sung CSP, Chin IJ, Yu WC, Macromolecules, 18, 1512 (1985)

[12] Wachsman ED, Frank CW, Polymer, 29, 1191 (1988)

[13] Lin KF, Wang FW, Polymer, 35(4), 687 (1994)

[14] Lakowicz JR, "Principles of Fluorescence Spectroscopy", chapter 1, Plenum Press, New York (1983)

[15] Guillet J, "Polymer Photophysics and Photochemistry", chapter 7, Cambridge Univ. Press, Cambridge (1985)

[16] Morawetz H, J. Polym. Sci. A: Polym. Chem., 37(12), 1725 (1999)

[17] Mita TF, Bauer RS, "Epoxy Resin-Chemistry and Technology", ed. by C.A. May, Marcel Dekker, Inc., New York (1988)

[18] Ellis B, "Chemistry and Technology of Epoxy Resins", Blackie Academic and Professional, Chapman and Hall, London (1993)

[19] Park WH, Lee JK, J. Appl. Polym. Sci., 67(6), 1101 (1998)

[20] Kim DS, Lee JK, Choi EJ, Polym.(Korea), 23(4), 569 (1999)

[21] Lee JK, Park WH, Korean J. Mater. Res., 6(5), 494 (1996)

[22] Sung CSP, Sung NH, Int'l SAMPE Symp. May 8-11, 51 (1995)

[23] Wang FW, Lowry RE, Fanconi BM, Polymer, 27, 1529 (1986)

[24] Paik HJ, Sung NH, Polym. Eng. Sci., 34(12), 1025 (1994)

[25] Wang FW, Lowry RE, Fanconi BM, Polym. Mater. Sci. Eng., 53, 180 (1985)

[26] Stroeks A, Shmorhun M, Jamieson AM, Simha R, Polymer, 29, 467 (1988)

[27] Prime RB, "Thermal Characterization of Polymeric Materials", ed. by E.A. Turi, volume 2, chapter 6, Academic Press, Inc., San Diego (1997)

[28] Ilavsky M, "Polymer Networks: Principles of Their Formation, Structure and Properties", ed. by R.F.T. Stepto, chapter 8, Blackie Academic & Professional, London (1998)

[29] Enns JB, Gillham JK, J. Appl. Polym. Sci., 28, 2567 (1983)

[30] Gillham JK, Polym. Eng. Sci., 26, 1429 (1986)

[31] Zachariasse KA, Duveneck G, Busse R, J. Am. Chem. Soc., 106, 1045 (1984)