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Korean Chemical Engineering Research,
Vol.43, No.5, 579-587, 2005
Vol.43, No.5, 579-587, 2005
Poly(4-vinylphenol)/Ketone 용액계의 상평형
Phase Equilibria of the Poly(4-vinylphenol)/Ketone Solutions
본 연구에서는 Poly(4-vinylphenol)(PVPh)/acetone 및 PVPh/methyl ethyl ketone 용액계의 액-액 상분리 실험을 TOA(thermal optical analysis)방법으로 실행하였다. 실험을 수행한 PVPh/acetone 및 PVPh/MEK 용액계의 상분리 거동은 두 용액 계 모두 LCST 형태의 거동을 보였고 상분리 온도는 고분자의 분자량이 증가함에 따라 낮아지는 경향을 보였다. 또한, 용매의 분자량이 상분리에 미치는 영향으로는 용매의 분자량이 큰 PVPh/MEK 용액의 상분리 온도가 PVPh/acetone 용액의 경우보다 높은 온도 영역에 분포하는 경향을 보였다. 실험에서 측정된 상분리 데이터를 PVPh와 ketone 분자간의 교차회합과 PVPh의 자기회합을 고려한 PC-SAFT 상태방정식 관계를 이용하여 액-액 상평형 관점에 서 검토하여 보았다. PVPh의 PC-SAFT 상태방정식 파라미터와 교차회합 파라미터는 PVPh의 용융상태의 밀도 데이터와 PVPh/acetone 용액의 기-액 평형 데이터를 동시에 고려하여 추산하였다. 추산된 파라미터를 이용하여 각 고분자 용액계의 spinodal curve와 binodal curve를 계산하였으며, 계산된 binodal curve는 실험에서 측정된 상분리 온도와 일치하는 경향을 보였다.
Phase separations of Poly(4-vinylphenol)(PVPh)/acetone and PVPh/methyl ethyl ketone solutions were measured using the thermal optical analysis (TOA) method. The phase separations of these system showed the behaviors of LCST-type (lower critical solution temperature). The measured cloud temperatures were lowered with increasing molecular weight of PVPh, and cloud temperatures of PVPh/MEK solutions shifted to higher temperature regions, compared to the PVPh/acetone solutions. Phase equilibria of PVPh/ketone solutions were described with taking account of self-associations of PVPh and cross-associations between PVPh and solvent, by using the PC-SAFT equation of state. PC-SAFT EoS parameters of PVPh and cross-association parameters were determined by simultaneously fitting liquid density data of PVPh and VLE data of the PVPh/acetone system. The estimated parameters of PVPh and cross-association parameters were utilized to calculations of the binodal and spinodal curves, and the calculated binodal curves were in good agreements with the experimental cloud temperatures.
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