가교결합구조를 갖는 poly(vinylchloride)를 포함한 solvent(1)/solvent(2)/PVC(3)의 팽윤평형을 측정하기 위하여 PVC [poly(vinylchloride)]는 가교결합된 상태로 사용하였고, 유기용매는 acetone, trichloroethylene, ethanol 등의 3종류를 선택하여 2성분계의 acetone(1)/PVC(2), trichloroethylene(1)/PVC(2), ethanol(1)/PVC(2)계와 3성분계인 acetone(1)/trichloroethylene(2)/PVC(3), acetone(1)/ethanol(2)/PVC(3)계에 대하여 온도영역 298.15-318.15 K 범위에서 팽윤평형실험이 측정되었다. 측정된 팽윤데이터로부터 혼합용매계인 acetone(1)/trichloroethylene(2)/PVC(3)인 경우 acetone의 함량이 증가할수록 가교결합된 PVC의 팽윤비가 증가되다 감소하는 결과로 나타났고, acetone(1)/ethanol(2)/PVC(3)인 경우는 acetone의 함량이 증가함에 따라 팽윤비는 계속 증가하는 결과로 나타났다. 이로부터 acetone이 팽윤촉진제(good solvent)로 작용하고, trichloroethylene이나 ethanol은 팽윤억제제(poor solvent)로 작용하는 결과로 나타났다. 또한 acetone(1)/trichloroethylene(2)/PVC(3), acetone(1)/ethanol(2)/PVC(3)계의 팽윤평형을 계산하기 위하여 혼합에너지항과 탄성변형에너지항의 합으로 된 팽윤평형이론에 의하여 혼합에너지항에 UNIFAC모델[1]을, 탄성변형에너지항은 Flory[2], James와 Guth[3], Wall과 White[4]모델을 적용하였다. 측정된 팽윤평형데이터는 팽윤평형모델에 상호연관되어 상호작용파라미터들과 가교결합된 PVC의 주쇄를 연결하는 사슬들의 평균분자량이 추산되어 제공되었다. 또한 계산된 각 성분의 부피분율은 실험치와 비교하여 거의 오차가 없는 범위에서 일치하였다.

The crosslinked PVC[poly(vinylchloride)]s were used to measure the swelling equilibria for solbent(1)/solvent(2)/PVC(3) systems. Trichloroethylene, acetone and ethanol were chosen as the organic solvent for swelling the crosslinked PVCs. The measurement of swelling equilibria was carried out within 298.15K to 318.15K for the binary acetone(1)/PVC(2), trichloroethylene(1)/PVC(2), and ethanol(1)/PVC(2) systems, the ternary acetone(1)/trichloroethylene(2)/PVC(3), acetone(1)/ethanol(2)/PVC(3) systems. The swelling ratios of PVC were decreased after the increase of theirs for the acetone(1)/trichloroethylene(2)/PVC(3) systems and continuously increased for the acetone(1)/ethanol(2)/PVC(3) systems according to a increase of the content of acetone in their systems from the measured swelling data. Their results described that the acetone had a role of the good solvent and the trichloroethylene or the ethanol did the poor solvent. The theory of swelling equilibria was used to calculate swelling equilibria of acetone(1)/trichloroethylene(2)/PVC(3) and acetone(1)/ethanol(2)/PVC(3) systems. It consisted of a mixing energy term and an elastic deformation energy term that described the changes of the chemical potentials of each term, and the UNIFAC was chosen for a mixing energy term and each expression equation of the Flory, James and Guth, and Wall and White done for a elastic deformation term. The experimental swelling equilibria data for the acetone(1)/trichloroethylene(2)/PVC(3) systems and acetone(1)/ethanol(2)/PVC(3) systems were correlated to estimate the interaction parameters and the average molecular weights of branch chains between the main chains of cross-linked PVCs, and to calculate the volume fractions of PVCs in swelling equilibria with the swelling models. As a result, the experimental data were almost agreed with the calculated values within the experimental errors.

Swelling Equilibria Swelling Ratios Mixing Energy Elastic Deformation Energy UNIFAC

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