무정형 고분자의 압력-부피-온도 거동과 상태방정식을 이용한 분석

박성준; 차국헌; 강은아; 김창근

Polymer(Korea), Vol.20, No.2, 305-316, March, 1996

Export Citation

무정형 고분자의 압력-부피-온도 거동과 상태방정식을 이용한 분석

Pressure-Volume-Temperature Behaviors of Amorphous Polymers and Their Interpretation with Equation of State

박성준, 차국헌, 강은아, 김창근

초록

무정형 고분자들 중에서 반복단위의 구조가 서로 다른 세 종류의 폴리카보네이트들 즉 bisphenol-A polycarbonate (BPA-PC), bischloral polycarbonate (BCPC), hexafluoro-polycarbonate (HFPC)와 polymethylmethacrylate (PMMA)의 PVT 거동을 density gradient column과 딜라토미터를 이용하여 측정하고 이들의 거동을 경험적 상태방정식인 Tait equation과 이론적으로 유도된 상태방정식들을 이용하여 분석하였다. 이들 네 가지 무정형 고분자들의 압력과 온도에 따른 비용적의 변화는 무정형 고분자에서 관찰되는 전형적인 압력-부피-온도 거동을 따랐다. 경험적 상태방정식과 이론적 상태방정식 중에 본 논문에서 이용한 Sanchez-Lacombe의 lattice fluid theory와 Flory의 cell theory 모두가 고분자 가공의 이전 과정을 반영하지 않는 유체 영역에서의 고분자 압력-부피-온도 거동을 비교적 정확하게 묘사하였다. 고분자 유체의 PVT 거동과 상이동은 상압하에서 일어나는 것을 공학적으로 주로 응용하기 때문에 상압하의 고분자 흔합 물들의 PVT 거동 및 상분리 현상을 정확하게 예측하기 위해 전체 압력 범위(0-200MPa)는 물론 제한된 낮은 압력 범위(0-50 MPa)에서 characteristic properties를 구하였다. 이론적 상태방정식에 있는 characteristic properties는 항상 일정한 값을 갖고 있지 않고 이를 구한 압력의 범위에 따라 약간씩 변화를 보였다. 낮은 압력 범위에서 characteristic properties를 구하여 사용 압력 범위내의 PVT 거동을 예측하는 경우에 사용 압력 범위내의 PVT 거동을 정화하게 예측하였다. 이런 관점 에서 볼 때 낮은 압력 범위에서 구한 characteristic properties를 구하여 고분자 혼합물의 상거동을 예측하는 것이 보다 정확한 결과를 얻을 수 있다.

Pressure, temperature, and volume behaviors of three polycarbonates haying different repeat unit and a polymethylmethacylate were measured by density gradient column and dilatometer and analyzed by empirical and theoretical equations of state. Pressure-temperature-volume(PVT) behaviors of those four different polymers showed typical PVT behaviors of amorphous polymers. Among the various theoretical equations of state, the lattice fluid theory of Sanchez-Lacombe and the cell theory of Flory were used for data analysis. The empirical model of Tait and both theoretical equations of state were all found to provide good fits of polymer liquid PVT data. It Is known that characteristic properties of polymers sightly depend on the pressure and temperature at which characteristic properties are determined. Since the data and thermodynamic fucntions at low pressure are need for engineering work, the characteristic properties were calculated over a pressure range of 0 to 50 MPa, as well as over the full avaliable range of 0 to 200 MPa. The characteristic properties claculated at the different pressure ranges were not constant. The accuracy of the PVT data fits was better over a restricted data range.

Keywords:equation of state;amorphous polymer;PVT behavior

[References]

Prigogine I, Trappeniers N, Mathot V, Discuss. Faraday Soc., 15, 93 (1953)
Prigogine I, Trappeniers N, Mathot V, J. Chem. Phys., 26, 751 (1957)
Prigogine I, "The Molecular Theory of Solutions," North-Holland, Amsterdam (1957)
Flory PJ, Orwell KA, Vrij A, J. Am. Chem. Soc., 86, 3503 (1964)
Flory PJ, J. Am. Chem. Soc., 87, 1833 (1965)
Eichineger BE, Flory PJ, Trans. Faraday Soc., 64, 2035 (1968)
Flory PJ, Discuss. Faraday Soc., 49, 7 (1970)
Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2352 (1976)
Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2568 (1976)
Sanchez IC, Lacombe RH, Macromolecules, 11, 1145 (1978)
Sanchez IC, Balazs AC, Macromolecules, 22, 2325 (1989)
Simha R, Somcynsky T, Macromolecules, 2, 342 (1969)
Simha R, Macromolecules, 10, 1025 (1977)
Dee GT, Walsh DJ, Macromolecules, 21, 811 (1988)
Dee GT, Walsh DJ, Macromolecules, 21, 815 (1988)
Sanchez IC, "Polymer Blends," Vol. 1, Chapter 3, D.R. Paul and S. Newman Eds., Academic Press, New York (1978)
Sanchez IC, Lacombe RH, J. Polym. Sci. C: Polym. Lett., 15, 71 (1977)
Zoller PJ, J. Polym. Sci. B: Polym. Phys., 18, 157 (1980)
Zoller PJ, J. Polym. Sci. B: Polym. Phys., 20, 1453 (1982)
Tait PG, J. Phys. Chem., 2, 1 (1888)
Nanda VS, Simha R, J. Chem. Phys., 41, 1884 (1964)
Nanda VS, Simha R, J. Chem. Phys., 41, 3870 (1964)
Quach A, Simha R, J. Appl. Phys., 42, 4592 (1971)
Technical Information Bulletin No. AL-176, Aldrich Chemical Company, Inc.
Eckert H, Forster B, Angew. Chem.-Int. Edit., 99, 922 (1987)
Daly WH, Poche D, Tetrahedron Lett., 29(10), 5859 (1988)
Vernaleken H, "Interfacial Synthesis," F. Millich and C.E. Carraher Jr. Eds., Vol. 11, p. 65, Marcel Dekker Inc., New York (1977)
Starks CM, Liotta C, "Phase Transfer Catalysis, Priciples and Techniques," Academic Press, New York (1978)
Quach A, Simha R, J. Phys. Chem., 78, 416 (1972)
Zoller P, J. Polym. Sci. B: Polym. Phys., 16, 1261 (1978)
Kim CK, Paul DR, Polymer, 33, 1630 (1992)
Sanchez IC, "Encyclopedia of Physical Science and Technology," vol. XL, p. 1, Academic Press, New York (1987)
Rodgers PA, Ph.D. Dissertation, University of Texas at Austin (1989)

[Referenced By]

[1] Prigogine I, Trappeniers N, Mathot V, Discuss. Faraday Soc., 15, 93 (1953)

[2] Prigogine I, Trappeniers N, Mathot V, J. Chem. Phys., 26, 751 (1957)

[3] Prigogine I, "The Molecular Theory of Solutions," North-Holland, Amsterdam (1957)

[4] Flory PJ, Orwell KA, Vrij A, J. Am. Chem. Soc., 86, 3503 (1964)

[5] Flory PJ, J. Am. Chem. Soc., 87, 1833 (1965)

[6] Eichineger BE, Flory PJ, Trans. Faraday Soc., 64, 2035 (1968)

[7] Flory PJ, Discuss. Faraday Soc., 49, 7 (1970)

[8] Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2352 (1976)

[9] Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2568 (1976)

[10] Sanchez IC, Lacombe RH, Macromolecules, 11, 1145 (1978)

[11] Sanchez IC, Balazs AC, Macromolecules, 22, 2325 (1989)

[12] Simha R, Somcynsky T, Macromolecules, 2, 342 (1969)

[13] Simha R, Macromolecules, 10, 1025 (1977)

[14] Dee GT, Walsh DJ, Macromolecules, 21, 811 (1988)

[15] Dee GT, Walsh DJ, Macromolecules, 21, 815 (1988)

[16] Sanchez IC, "Polymer Blends," Vol. 1, Chapter 3, D.R. Paul and S. Newman Eds., Academic Press, New York (1978)

[17] Sanchez IC, Lacombe RH, J. Polym. Sci. C: Polym. Lett., 15, 71 (1977)

[18] Zoller PJ, J. Polym. Sci. B: Polym. Phys., 18, 157 (1980)

[19] Zoller PJ, J. Polym. Sci. B: Polym. Phys., 20, 1453 (1982)

[20] Tait PG, J. Phys. Chem., 2, 1 (1888)

[21] Nanda VS, Simha R, J. Chem. Phys., 41, 1884 (1964)

[22] Nanda VS, Simha R, J. Chem. Phys., 41, 3870 (1964)

[23] Quach A, Simha R, J. Appl. Phys., 42, 4592 (1971)

[24] Technical Information Bulletin No. AL-176, Aldrich Chemical Company, Inc.

[25] Eckert H, Forster B, Angew. Chem.-Int. Edit., 99, 922 (1987)

[26] Daly WH, Poche D, Tetrahedron Lett., 29(10), 5859 (1988)

[27] Vernaleken H, "Interfacial Synthesis," F. Millich and C.E. Carraher Jr. Eds., Vol. 11, p. 65, Marcel Dekker Inc., New York (1977)

[28] Starks CM, Liotta C, "Phase Transfer Catalysis, Priciples and Techniques," Academic Press, New York (1978)

[29] Quach A, Simha R, J. Phys. Chem., 78, 416 (1972)

[30] Zoller P, J. Polym. Sci. B: Polym. Phys., 16, 1261 (1978)

[31] Kim CK, Paul DR, Polymer, 33, 1630 (1992)

[32] Sanchez IC, "Encyclopedia of Physical Science and Technology," vol. XL, p. 1, Academic Press, New York (1987)

[33] Rodgers PA, Ph.D. Dissertation, University of Texas at Austin (1989)