Polybutadiene/EPDM/용매로되는 3성분계의 열역학

이기호; 고진환; 이동주

Polymer(Korea), Vol.18, No.6, 950-956, November, 1994

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Polybutadiene/EPDM/용매로되는 3성분계의 열역학

Thermodynamics of the Polybutadiene/EPDM/Solvent Ternary System

이기호, 고진환, 이동주

초록

EPDM과 polybutadiene(PBD) 두 고분자 혼합물에 대한 상용성을 정량적으로 평가하기 위바여 고분자/고분자/용매로 되는 3성분계의 상분리 거동을 관찰하였다. 용매로는 EPDM에 빈용매로, PBD에는 양용매로 작용하는 벤젠을 사용하였고, 고분자 혼합물의 조성, 농도 및 온도 등이 3성분계 희박 용액의 cloud point curve(CPC)와 상그림(phase diagram)에 어떤 영향을 미치는가에 대하여 검토하였다. Cloud point curve에 의하면 각 고분자 시료에 대한 용매의 친화력 차이, 그리고 반발상호작용에 의한 고분자 시료간의 비상용성 때문에 온도 15℃를 전후하여 CPC에 큰 변화가 있었다. 5℃∼25℃ 영역에서 고분자 혼합물 시료의 조성비와 농도에 따라 비상용성이 나타났으며, 분리된 각 상의 고분자 혼합물 농도로부터 각 상의 조성이 상분리온도에 크게 의존되어 있음을 확인하였다. EPDM과 PBD의 상호작용 파라미타는 0.630∼1.078의 범위 내에 존재하는 것으로 확인되었으며, 따라서 이 두 고분자 물질은 상용성이 없는 것으로 결론 지었다.

The polymer-polymer interaction parameters χ₂₃^t of the polybutadiene(PBD) and EPDM system are investigated by observing the phase behaviour of the ternary system for PBD/EPDM/solvent. The solvent used in this study is benzene as a good solvent for PBD and a poor solvent for EPDM. Ternary solutions of different mixing ratios of the two component polymers and concentrations are separated into two phases by changing temperature. The cloud point curves(CPC) show that the difference of solvent affinities toward each polymer and the repulsive interaction between two polymers affect considerably the shape of CPC near 15℃. In the temperature range of 5℃∼25℃, incompatible behaviours being arised from both the difference of mixing ratios and concentration, are clearly observed. Also the phase separation temperature influences greatly the composition of each separated phase. The calculated χ₂₃^t values from Flory-Huggins theory are in the range of 0.630∼1.078, which suggest strongly the PBD-EPDM system is incompatible.

Keywords:EPDM;PBD;ternary system;cloud point curve;interaction parameter

[References]

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[1] Narasimhan V, Huang RY, Burns CM, J. Polym. Sci. B: Polym. Phys., 21, 1993 (1983)

[2] Lloyd DR, Narasimhan V, Burns CM, J. Liq. Chrom., 3, 1111 (1980)

[3] Kumaki J, Macromolecules, 19, 763 (1986)

[4] Scott RL, J. Chem. Phys., 17, 279 (1949)

[5] Schultz AR, Flory PJ, J. Am. Chem. Soc., 74, 4760 (1952)

[6] Tong Z, Einaga Y, Miyashita H, Fujita H, Macromolecules, 20, 1883 (1987)

[7] Hsu CC, Prausnitz JM, Macromolecules, 7, 320 (1974)

[8] Zeman L, Patterson D, Macromolecules, 5, 513 (1972)

[9] Patterson D, Macromolecules, 2, 672 (1969)

[10] Flory PJ, "Principles of Polymer Chemistry," Chap. XIII, Cornell Univ. Press (1971)

[11] Einaga Y, Tong Z, Macromolecules, 20, 2027 (1987)

[12] Buist JM, "Rubber Technology and Manufacture," 2nd Ed., Chap. 4, Butterworth Sci. (1981)

[13] Huggins ML, J. Am. Chem. Soc., 64, 2716 (1942)

[14] Kraemer EO, Ind. Eng. Chem., 30, 1200 (1938)

[15] Zimm BH, Lundberg JL, J. Phys. Chem., 60, 425 (1956)

[16] Billingham NC, "Molar Mass Measurements in Polymer Science," John Wiley & Sons (1977)

[17] Tong Z, Einaga Y, Miyashita H, Fujita H, Macromolecules, 17, 527 (1984)

[18] Tong Z, Einaga Y, Fujita H, Polym. J., 19, 965 (1987)

[19] Tong Z, Einaga Y, Kitagawa T, Fujita H, Macromolecules, 22, 450 (1989)

[20] Lee KH, Lee DC, Korea Polym. J., 2(1), 16 (1994)

[21] Hong JS, Lee DC, Polym.(Korea), 16(4), 470 (1992)

[22] Tong Z, Einaga Y, Miyashita H, Fujita H, Macromolecules, 20, 1888 (1987)