A Study on the Thermodynamic Properties of Two Isomeric Poly(butyl methacrylates)

Cho J

Korea Polymer Journal, Vol.5, No.3, 139-144, September, 1997

The recently formulated corresponding states equation of state by Sanchez and Cho is used to compare the bulk thermodynamic data of isomeric poly(n-butyl methacrylate) (PnBMA) and poly(i-butyl methacrylate) (PiBMA). This new equation of state is based on the temperature-pressure (T-P) superposition principle of compression of polymers. The bulk data of PiBMA is measured by using the high pressure dilatometer. The T-P superpositon is shown to be supported by the volumetric data of PiBMA. The new corresponding states equation of state distinguishes polymers by characteristic mass density p^*, temperature T^*, and pressure p^*. These parameters are obtained for the two isomers by fitting the bulk data to the equation of state. The three characteristic parameters p^*, T^*, and p^* successfully describe the structural difference between the two isomeric polymethacrylates having butyl side group with different excluded volumes. The p^* shows that the packing efficiency of PiBMA is higher than that of PnBMA. PiBMA has a greater fractional free volume at the glass transition temperature (T_g), which is identical to T_g/T^*, than PnBMA does. However, the both polymers have the identical cohesive energies P^*v^* or P^*/p^*.

[References]

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[1] Parks WB, Richards RB, Trans Raraday Soc., 45, 203 (1949)

[2] Hellwege KH, Knappe W, Lehmann P, Kolloid-Z., 183, 110 (1962)

[3] Heydemann P, Guicking HD, Kolloid-Z., 193, 16 (1964)

[4] Guach A, Simha R, J. Appl. Phys., 42, 4592 (1971)

[5] Quach A, Wilson PS, Simha R, J. Macromol. Sci.-Phys., B9, 533 (1974)

[6] Olabisi O, Simha R, Macromolecules, 8, 206 (1975)

[7] Zoller P, Bolli P, Pahud V, Ackermann H, Rev. Sci. Instrum., 47, 948 (1976)

[8] Tait PG, Phys. Chem., 2, 1 (1988)

[9] Tammon G, Z. Phys. Chem., 17, 620 (1985)

[10] Murnaghan FD, Proc. Nat. Acad. Sci., 30, 244 (1944)

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

[12] Flory PJ, Orwoll RA, Vrij A, J. Am. Chem. Soc., 6, 3515 (1964)

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

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

[15] Sanchez IC, Cho J, Chen WJ, J. Phys. Chem., 97, 6120 (1993)

[16] Sanchez IC, Cho J, Chen WJ, Macromolecules, 26, 4234 (1993)

[17] Sanchez IC, Cho J, Polymer, 36(15), 2929 (1995)

[18] Owen BB, Brinkley SR, Phys. Rev., 64, 32 (1943)

[19] Bondi A, Physical Properties of Molecular Crystals, Liquids and Glasses, Wiley, New York (1968)

[20] Van Krevlan DW, Properties of Polymers, Elsevier Science Publishers B.V., Amsterdam, Netherlands (1990)

[21] Costello L, Ph.D. Dissertation, University of Texas at Austin (1994)

[22] User's Manual for Operation by Gnomix Co.

[23] Coleman MR, Ph.D. Dissertation, University of Texas at Austin (1993)