계면중합 반응 고찰 및 박막의 두께측정에 관한 연구

박종원; 진병복; 민병렬

HWAHAK KONGHAK, Vol.36, No.3, 393-398, June, 1998

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계면중합 반응 고찰 및 박막의 두께측정에 관한 연구

Reaction Mechanism and Thickness of Thin Film in Interfacial Polymerization

박종원, 진병복, 민병렬

초록

역삼투 복합막의 활성층 고분자인 aromatic polyamide 제조를 위해 수용상 MPD(m-phenylene diamine)와 유기상 TMC(trimesoyl chloride)의 계면중합 과정을 고찰하였다. 먼저, 계면중합 형성과정을 이해하는 실험방법으로서, 자외선 흡광도 분석법을 이용하여, 시간에 따른 막 중합과정을 해석하였다 그 결과 계면 반응의 조절은 초기에는 수용상 확산이 지배적이나, 유기상의 단량체가 저농도(0.125wt%)일 때는 유기상이 확산하면서 반응을 조절한다는 사실을 확인하였다. 이 때, 박막 형성은 초기에는 20s 정도의 지연시간이 있었지만, 모두 60s 이내로 비화학양론적으로 완료되었다. 또한 계면을 형성하기까지의 농도변화를 수학적으로 예측하여, 계면의 두께를 이론적으로 구한 결과 실험치와 잘 일치하였다. 한편 이론적 두께식은 다음과 같다.
δ=∫_t1^t2N₁ʝ₁dt + ∫_t1^t2N₂ʝ₂dt;

To manufacture aromatic polyamide which is active layer in reverse osmosis composite membrane, interfacial polymerization using MPD(m-phenylene diamine) in water phase and TMC(trimesoyl chloride) in HCFC(1,1-dichloro-1-fluoroethane) organic solvent was researched. By using UV absorbance analysis method, thin film formation process was studied according to time. As a result, aqueous phase diffusion was dominant in the control of interfacial polymerization of early time, but when the concentration of monomers in organic phase was low(0.125wt%), organic phase diffusion controlled the reaction. In addition, interfacial reaction which proceeded with delayed time of early 20 seconds was completed within 60 seconds unstoichiometrically. Also concentration change on the interface was mathmatically perdicted and the thickness of thin film was calculated by using this result. The calculated value of thickness of thin film provides good consistence with experimental results. Also theoretical equation of thickness in thin film is as follows.
δ=∫_t1^t2N₁ʝ₁dt + ∫_t1^t2N₂ʝ₂dt

Keywords:Reverse Osmosis;Interfacial Polymerization;Thin Film;Thin Film Thickness

[References]

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[1] Bungay PM, Londsale HH, de Pinho MN, "Synthetic Membranes: Science, Engineering and Applications," D. Reidel Publishing Company, pp. 39 (1983)

[2] Riely RL, Lonsdale HK, Lyons CR, Merten U, J. Appl. Polym. Sci., 11, 2143 (1967)

[3] Carnell PH, Cassidy HG, J. Polym. Sci., 55, 233 (1961)

[4] Cadotte JE, U.S. Patent, 4,277,344 (1981)

[5] Bartels CR, J. Membr. Sci., 32, 291 (1987)

[6] Im KB, Dept. of Chem. Eng. The Graduate School, Yonsei (1990)

[7] Pak JW, Min RB, HWAHAK KONGHAK, 29(1), 1 (1991)

[8] Baek SY, Dept. of Chem. Eng. The Graduate School, Yonsei (1991)

[9] Odian G, "Principles of Polymerization," 3rd, New York, pp. 94 (1991)

[10] Morgan PW, "Condensation Polymer by Interfacial and Solution Methods," Interscience, New York (1965)

[11] Mikos AG, Kiparissides C, J. Membr. Sci., 59, 205 (1991)

[12] Reuvers AJ, Smolders CA, J. Membr. Sci., 34, 67 (1987)

[13] Rice RG, Do DD, "Applied Mathematics and Modeling for Chemical Engineerings," John Wiley & Sons, Inc., New York, pp. 409 (1995)

[14] Danckwerts PV, "Gas-Liquid Reactions," F.R.S., MacGraw-Hill, pp. 30 (1970)

[15] Bird RB, Stewart WE, Lightfoot EN, "Transport Phenomena," John Wiley & Sons. Inc., New York, pp. 515 (1960)

[16] Chai GY, Krantz WB, J. Membr. Sci., 93(2), 175 (1994)