Heat capacity of poly(trimethylene terephthalate)

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Abstract

Thermal analysis of poly(trimethylene terephthalate) (PTT) has been carried out using standard differential scanning calorimetry and temperature-modulated differential scanning calorimetry. Heat capacities of the solid and liquid states of semicrystalline PTT are reported from 190 K to 570 K. The semicrystalline PTT has a glass transition temperature of about 331 K. Between 460 K and 480 K, PTT shows an exothermic ordering. The melting endotherm occurs between 480 K and 505 K with an onset temperature of 489.15 K (216 C). The heat of fusion of typical semicrystalline samples is 13.8 kJ/mol. For 100% crystalline PTT the heat of fusion is estimated to be 28--30 kJ/mol. The heat capacity of solid PTT is linked to an approximate group vibrational spectrum, and the Tarasov equation is used to estimate the skeletal vibrational heat capacity ({Theta}{sub 1} = 542 K and {Theta}{sub 3} = 42 K). A comparison of calculation and experimental heat capacities show agreement of better than {+-}2% between 190--300 K. The experimental heat capacity of liquid PTT can be expressed as a linear function of temperature: C{sub p} {sup L}(exp) = 211.6 + 0.434 T J/(K mol) and compares well with estimations from the ATHAS data bank using group contributions of other polymers with the same constituent groups ({+-} 0.5%). The change of heat capacity at T{sub g} of amorphous PTT has been estimated from the heat capacities of liquid and solid to be 86.4 J/(K mol). Knowing C{sub p} of the solid, liquid, and the transition parameters, the thermodynamic functions: enthalpy, entropy and Gibbs function were obtained.

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