Thermally stimulated current studies of thermotropic polyesters with polymethylene spacers (I): The glass transition and relaxation behavior of anisotropic and isotropic glasses

Thermally stimulated current (TSC) and relaxation map analysis (RMA) were used to study the glass transitions and relaxation phenomena of the anisotropic and isotropic glasses for the semiflexible polyesters with various polymethylene spacers (n = 7 ˜ 10). TSC analysis indicated that the glass transition temperatures (Tg) of polymers at around 40 ˜ 50°C exhibited an apparent even‐odd behavior not only for the anisotropic glasses but also for the isotropic glasses. The Tg of the isotropic glass for the polymer with even n value was observed to be higher than those for the two neighboring polymers with odd n values. The anisotropic glass for the polymer with even n value had a lower Tg than those for the two neighboring polymers with odd n values. The lower value was attributed to the configuration and orientation effects on the behavior of polarization. RMA revealed that the relaxation modes of the investigated polymers were also influenced by the configuration and orientation effects. The dipolar relaxation of the anisotropic glass for the polymer with odd n value occurred at a higher temperature and had a lower entropy (enthalpy) of activation than that of the isotropic glass for the same polymer due to the orientation effect. However, an inverse relation was found to occur for the polymer with even n value, which came from the trans configuration of the even polymethylene spacers. Finally, the thermokinetic properties evaluated by RMA (e.g., the final state after depolarization) correlated quite well with the results obtained by TSC. © 1995 John Wiley & Sons, Inc.