For isotactic polypropylene, the enthalpy and entropy differences between a glass and a crystal, AH g~ and AS g~, and between a glass and a liquid, AH "g and AS as, were discussed via conformational analysis. AH g~ and AS gc are mostly attributed to the difference in bending and torsional vibration modes between a glass and a crystal. AH ag and AS ag are nearly equal to the sum of h c°nf and hint, and that of (s ?°nf- s~ °"f) and s i~t, respectively. Here h e°nf and s ~°~f are the conformational enthalpy and entropy per molar structural unit, s~ °"f (=0.38 J mol-1 K-~) is s ~°"f at 0 K, and h int and s i"t are the intermolecular interaction enthalpy and entropy per molar structural unit. The value of AH ag at 0 K, 5.6 kJ mol- x, is almost equal to the cohesive energy of a CH 3 residue, 5.7 kJ mol- 1. In a glass, the existence of localized ordered regions with enthalpy 6.78 to 9.29kJmol -~ was predicted. The conformational analysis further showed that many rod-like sequences with right- and left-handed helices may be contained in a glass.
Посилання на статтю:
Possibility of ordered regions in isotactic polypropylene glasses from heat capacity / Nobuyuki Tanaka // Polymer. – 1993. – Vol 34. – P. 4941-4944.