The Effects of Intramolecular Interactions of Random Copolymers on the Phase Behavior of Polymer Mixtures

M. J. Kim; J. E. Yoo; H. K. Choi; C. K. Kim

Macromolecular Research, Vol.10, No.2, 91-96, April, 2002

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The Effects of Intramolecular Interactions of Random Copolymers on the Phase Behavior of Polymer Mixtures

M. J. Kim, J. E. Yoo, H. K. Choi, and C. K. Kim^†

Department of Chemical Engineering, Chung-Ang University, 221 Huksuk-Dong, Dongjak-Gu, Seoul 156-756, Korea

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To explore the effects of intramolecular interactions within the copolymer on the phase separation behavior of polymer blends, copolymers having two different types of intramolecular interactions, i.e., intramolecular repulsion and intramolecular attraction were prepared. In this study, poly(styrene-co-methylmethacrylate) (P(S-MMA)) having intramolecular repulsion caused by positive interaction between styrene and MMA and poly(styrene-co-ethylmethacrylate) (P(S-EMA)) and poly(styrene-co-cyclohexylmethacrylate) (P(S-CHMA)) having intramolecular attraction caused by negative interaction between styrene and methacrylate were blended with tetramethyl polycarbonate (TMPC). The phase behavior of blends was examined as a function of copolymer composition and blend composition. TMPC formed miscible blends with styrenic copolymers containing less than certain amount of methacrylate. The phase separation temperature of TMPC blends with copolymer such as P(S-MMA) and P(S-EMA), first increases with methacrylate content, goes through a maximum and then decreases just prior to the limiting content of methacrylate for miscibility, while that of TMPC blends with P(S-CHMA) always decreases. The calculated interaction energy for TMPC-P(S-EMA) pair is negative and monotonically increases with EMA content of the copolymer. Such behavior contradicted the general notion that systems with more favorable energetic interactions have higher LCST. The detailed inspection of the lattice-fluid theory related to the phase behavior was performed to explain such behavior.

Keywords:intramolecular interactions;styrene-methacrylate copolymers;TMPC;LCST-type phase behavior;equation-of-state effects;interaction energy

[References]

Paul DR, Walsh DJ, Higgins JS, Polymer Blends and Mixtures, A. Maconnachie, Ed., NATO ASI Series E, Applied Science, No. 89, Martinus Nijoff Publishers, Dorrecht, Netherlands, pp 1 (1985)
Harris JE, Paul DR, Barlow JW, Polym. Eng. Sci., 23, 676 (1983)
Kwei TK, Nishi T, Rorets RF, Macromolecules, 7, 667 (1974)
Olabisi O, Macromolecules, 8, 316 (1975)
Kim CK, Paul DR, Polymer, 33, 2089 (1992)
Kim Ck, Paul DR, Polymer, 33, 4929 (1992)
Min KE, Paul DR, Macromolecules, 20, 2828 (1987)
Russell TP, Macromolecules, 26, 5819 (1993)
Callaghan TA, Paul DR, Macromolecules, 26, 2439 (1993)
Flory PJ, Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca, Chapter 12 (1953)
Sanchez IC, Encyclopedia of Physical Science and Technology, Academic Press Academic Press, New York, Vol. 11, pp 1 (1987)
Guo W, Higgins JS, Polymer, 31, 699 (1990)
Yee AF, Maxwell MA, J. Macromol. Sci.-Phys., 17, 543 (1980)
Kim MH, Kim JH, Kim CK, Kang YS, Park HC, Won JC, J. Polym. Sci. B: Polym. Phys., 37(21), 2950 (1999)
Kim JH, Park DS, Kim CK, J. Polym. Sci. B: Polym. Phys., 38(20), 2666 (2000)
Fernandes AC, Barlow JW, Paul DR, Polymer, 27, 1789 (1986)
Kim S, Liu J, Korea Polym. J., 9(3), 129 (2001)
Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2568 (1976)
Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2358 (1976)
Sanchez IC, Lacombe RH, Macromolecules, 11, 1145 (1978)
Paul DR, Barlow JW, Polymer, 25, 487 (1984)
Kambour RP, Bendler TJ, Bopp RC, Macromolecules, 16, 1827 (1983)
ten Brinke G, Karasz FE, Macknight WJ, Macromolecules, 16, 1827 (1983)
Ko MB, Korea Polym. J., 8(4), 186 (2000)
Kim H, Kim J, Kim M, Oh S, Lee J, Korea Polym. J., 9(3), 150 (2001)
Rodgers PA, J. Appl. Polym. Sci., 18, 1061 (1993)

[Referenced By]

[Related Articles]

[1] Paul DR, Walsh DJ, Higgins JS, Polymer Blends and Mixtures, A. Maconnachie, Ed., NATO ASI Series E, Applied Science, No. 89, Martinus Nijoff Publishers, Dorrecht, Netherlands, pp 1 (1985)

[2] Harris JE, Paul DR, Barlow JW, Polym. Eng. Sci., 23, 676 (1983)

[3] Kwei TK, Nishi T, Rorets RF, Macromolecules, 7, 667 (1974)

[4] Olabisi O, Macromolecules, 8, 316 (1975)

[5] Kim CK, Paul DR, Polymer, 33, 2089 (1992)

[6] Kim Ck, Paul DR, Polymer, 33, 4929 (1992)

[7] Min KE, Paul DR, Macromolecules, 20, 2828 (1987)

[8] Russell TP, Macromolecules, 26, 5819 (1993)

[9] Callaghan TA, Paul DR, Macromolecules, 26, 2439 (1993)

[10] Flory PJ, Principles of Polymer Chemistry, Cornell Univ. Press, Ithaca, Chapter 12 (1953)

[11] Sanchez IC, Encyclopedia of Physical Science and Technology, Academic Press Academic Press, New York, Vol. 11, pp 1 (1987)

[12] Guo W, Higgins JS, Polymer, 31, 699 (1990)

[13] Yee AF, Maxwell MA, J. Macromol. Sci.-Phys., 17, 543 (1980)

[14] Kim MH, Kim JH, Kim CK, Kang YS, Park HC, Won JC, J. Polym. Sci. B: Polym. Phys., 37(21), 2950 (1999)

[15] Kim JH, Park DS, Kim CK, J. Polym. Sci. B: Polym. Phys., 38(20), 2666 (2000)

[16] Fernandes AC, Barlow JW, Paul DR, Polymer, 27, 1789 (1986)

[17] Kim S, Liu J, Korea Polym. J., 9(3), 129 (2001)

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

[19] Sanchez IC, Lacombe RH, J. Phys. Chem., 80, 2358 (1976)

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

[21] Paul DR, Barlow JW, Polymer, 25, 487 (1984)

[22] Kambour RP, Bendler TJ, Bopp RC, Macromolecules, 16, 1827 (1983)

[23] ten Brinke G, Karasz FE, Macknight WJ, Macromolecules, 16, 1827 (1983)

[24] Ko MB, Korea Polym. J., 8(4), 186 (2000)

[25] Kim H, Kim J, Kim M, Oh S, Lee J, Korea Polym. J., 9(3), 150 (2001)

[26] Rodgers PA, J. Appl. Polym. Sci., 18, 1061 (1993)