Articles & Issues
- Language
- korean
- Conflict of Interest
- In relation to this article, we declare that there is no conflict of interest.
- Publication history
-
Received September 2, 2005
Accepted October 31, 2005
-
This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits
unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
Copyright © KIChE. All rights reserved.
All issues
Poly(4-vinylphenol)(PVPh)/Ethyl Acetate 및 PVPh/Butyl Acetate 용액계의 액-액 상평형
Liquid-Liquid Equilibria of Poly(4-vinylphenol)(PVPh)/Ethyl Acetate and PVPh/Butyl Acetate Solutions
강원대학교 화학공학과, 200-701 강원도 춘천시 효자2동 192-1
Department of Chemical Engineering, Kangwon National University, 192-1, Hyoja-2 dong, Chunchon 200-701, Korea
kichang@kangwon.ac.kr
Korean Chemical Engineering Research, December 2005, 43(6), 704-714(11), NONE Epub 23 January 2006
Download PDF
Abstract
본 연구에서는 Poly(4-vinylphenol)(PVPh)/Ethyl Acetate 및 PVPh/Butyl Acetate 용액계의 액-액 상분리 거동을 TOA(thermal optical analysis)법으로 측정하고, 측정된 상분리 데이터를 PC-SAFT 상태방정식을 이용한 액-액 상평형 관계로 고찰하였다. 실험을 수행한 PVPh/Ethyl Acetate 및 PVPh/Butyl Acetate 용액계의 상분리 거동은 두 용액계 모두 LCST 형태의 거동을 보였고 상분리 온도는 고분자의 분자량이 증가함에 따라 낮아지는 경향을 보였으며 또한 용매의 분자량에 의한 영향으로는 용매의 분자량이 적은 PVPh/Ethyl Acetate 용액의 상분리 온도가 PVPh/Butyl Acetate 용액의 경우보다 낮은 온도 영역에 분포하는 경향을 보였다. 한편, PVPh/Ethyl Acetate 용액에서 PVPh와 용매 분자간의 수소결합에 의한 교차회합도를 FT-IR 스펙트럼 분석법으로 측정하고, 측정된 교차회합도로부터 PC-SAFT 모델의 교차회합 파라미터를 추산하였다. 추산된 교차회합 파라미터를 이용하여 PVPh/Ethyl Acetate 및 PVPh/Butyl Acetate 용액의 binodal curve와 spinodal curve를 계산하였으며, 계산된 binodal curve는 상분리 실험에서 측정된 상분리 온도(흐림온도) curve와 어느 정도 잘 일치하는 경향을 보였다.
Phase separations of Poly(4-vinylphenol)(PVPh)/Ethyl Acetate and PVPh/Butyl Acetate solutions were measured using the thermal optical analysis (TOA) method. The experimental phase separation data were correlated with liquid-liquid equilibria relations based on PC-SAFT equation of state. The phase separations of these system showed the behaviors of LCST (lower critical solution temperature)-type. The measured cloud temperatures were lowered with increasing in molecular weights of polymer(PVPh), and cloud temperatures of PVPh/Ethyl Acetate solutions shifted to lower temperature regions, compared to the PVPh/Butyl Acetate solutions. Extents of cross-association between solvent molecule and polymer in the PVPh/Ethyl Acetate solutions were measured using the FT-IR spectrum analysis method, and cross-association parameters of PC-SAFT model were estimated from experimental extents of cross-association. By using the estimated cross-association parameters between PVPh and solvent molecule, binodal and spinodal curves of liquid-liquid equilibria in PVPh/Ethyl Acetate and PVPh/Butyl Acetate solutions were calculated from PC-SAFT equation of state. The calculated binodal curves of these system were shown to be well agreeable with the experimental cloud temperature curves.
Keywords
References
Olabisi O, Robenson LM, Shaw MT, "Polymer-Polymer Miscibility", Academic Press, New York (1979)
Van Dijk MA, Wakker A, "Concepts of Polymer Thermodynamics", Technomic, Lancaster (1997)
Sandler SI, "Models for Thermodynamic and Phase Equilibria Calculations", Marcel Dekker, Inc., New York (1994)
Lacombe RH, Sanchez IC, J. Phys. Chem., 80(23), 2568 (1976)
Huang SH, Radosz M, Ind. Eng. Chem. Res., 29(11), 2284 (1990)
Yoo KP, Shin MS, Yoo SJ, You SS, Lee CS, Fluid Phase Equilib., 111(2), 175 (1995)
Muller EA, Gubbins KE, Ind. Eng. Chem. Res., 40(10), 2193 (2001)
Gross J, Sadowski G, Ind. Eng. Chem. Res., 40(4), 1244 (2001)
Gross J, Sadowski G, Ind. Eng. Chem. Res., 41(5), 1084 (2002)
Gross J, Spuhl O, Tumakaka F, Sadowski G, Ind. Eng. Chem. Res., 42(6), 1266 (2003)
Kouskoumvekaki IA, von Solms N, Michelsen ML, Kontogeorgis GM, Fluid Phase Equilib., 215(1), 71 (2004)
Wolbach JP, Sandler SI, AIChE J., 43(6), 1597 (1997)
Wolbach JP, Sandler SI, Ind. Eng. Chem. Res., 36(10), 4041 (1997)
Pimentel GC, McClellan AL, "The Hydrogen Bond", Freeman Co., San Francisco (1960)
Reilly JT, Walsh JM, Greenfield ML, Donohue MD, Spectrochimica Acta, 48A(10), 1459 (1992)
Kim MK, Kim KC, Korean Chem. Eng. Res., 43(5), 579 (2005)
Barker JA, Henderson D, J. Chem. Phys., 47(8), 2856 (1967)
Gross J, Sadowski G, Fluid Phase Equilib., 168(2), 183 (2000)
Walsh JM, Greenfield ML, Ikonomou GD, Donohue MD, Chem. Eng. Commun., 86, 125 (1989)
Walsh JM, Greenfield ML, Ikonomou GD, Donohue MD, International J. of Thermophysics, 11(1), 119 (1990)
Daubert TE, Danner RP, Sibul HM, Stebbins CC, "Physical and Thermodynamic Properties of Pure Chemical Data Compilation", Taylor & Francis, Washington, DC (1989)
Gupta RB, Johnston KP, Fluid Phase Equilib., 99, 135 (1994)
Kontogeorgis GM, Voutsas EC, Yakoumis IV, Tassios DP, Ind. Eng. Chem. Res., 35(11), 4310 (1996)
Moskala EJ, Howe SE, Painter PC, Coleman MM, Macromolecules, 17(9), 1671 (1984)
Widom JM, Philippe RJ, Hobbs ME, J. Am. Chem. Soc., 79(6), 1383 (1957)
Lee BC, Danner RP, AIChE J., 42(11), 3223 (1996)
Chen SJ, Economou IG, Radosz M, Macromolecules, 25(19), 4987 (1992)
Van Dijk MA, Wakker A, "Concepts of Polymer Thermodynamics", Technomic, Lancaster (1997)
Sandler SI, "Models for Thermodynamic and Phase Equilibria Calculations", Marcel Dekker, Inc., New York (1994)
Lacombe RH, Sanchez IC, J. Phys. Chem., 80(23), 2568 (1976)
Huang SH, Radosz M, Ind. Eng. Chem. Res., 29(11), 2284 (1990)
Yoo KP, Shin MS, Yoo SJ, You SS, Lee CS, Fluid Phase Equilib., 111(2), 175 (1995)
Muller EA, Gubbins KE, Ind. Eng. Chem. Res., 40(10), 2193 (2001)
Gross J, Sadowski G, Ind. Eng. Chem. Res., 40(4), 1244 (2001)
Gross J, Sadowski G, Ind. Eng. Chem. Res., 41(5), 1084 (2002)
Gross J, Spuhl O, Tumakaka F, Sadowski G, Ind. Eng. Chem. Res., 42(6), 1266 (2003)
Kouskoumvekaki IA, von Solms N, Michelsen ML, Kontogeorgis GM, Fluid Phase Equilib., 215(1), 71 (2004)
Wolbach JP, Sandler SI, AIChE J., 43(6), 1597 (1997)
Wolbach JP, Sandler SI, Ind. Eng. Chem. Res., 36(10), 4041 (1997)
Pimentel GC, McClellan AL, "The Hydrogen Bond", Freeman Co., San Francisco (1960)
Reilly JT, Walsh JM, Greenfield ML, Donohue MD, Spectrochimica Acta, 48A(10), 1459 (1992)
Kim MK, Kim KC, Korean Chem. Eng. Res., 43(5), 579 (2005)
Barker JA, Henderson D, J. Chem. Phys., 47(8), 2856 (1967)
Gross J, Sadowski G, Fluid Phase Equilib., 168(2), 183 (2000)
Walsh JM, Greenfield ML, Ikonomou GD, Donohue MD, Chem. Eng. Commun., 86, 125 (1989)
Walsh JM, Greenfield ML, Ikonomou GD, Donohue MD, International J. of Thermophysics, 11(1), 119 (1990)
Daubert TE, Danner RP, Sibul HM, Stebbins CC, "Physical and Thermodynamic Properties of Pure Chemical Data Compilation", Taylor & Francis, Washington, DC (1989)
Gupta RB, Johnston KP, Fluid Phase Equilib., 99, 135 (1994)
Kontogeorgis GM, Voutsas EC, Yakoumis IV, Tassios DP, Ind. Eng. Chem. Res., 35(11), 4310 (1996)
Moskala EJ, Howe SE, Painter PC, Coleman MM, Macromolecules, 17(9), 1671 (1984)
Widom JM, Philippe RJ, Hobbs ME, J. Am. Chem. Soc., 79(6), 1383 (1957)
Lee BC, Danner RP, AIChE J., 42(11), 3223 (1996)
Chen SJ, Economou IG, Radosz M, Macromolecules, 25(19), 4987 (1992)
