Relaxation during polymerization on slow heating and the vibrational heat capacity of the polymers.

The real and imaginary components of the complex heat capacity, C(p) (') and C(p) ("), and C(p,app) have been measured in real time during the linear chain polymerization on 12 K/h heating of six different (partially) polymerized states of a stoichiometric mixture of cyclohexylamine and diglycidyl ether of bisphenol A. Their C(p,app) shows a sigmoid shape rise with different onset temperatures T(onset), which is followed by a deep exotherm as the viscosity decreases and further polymerization occurs at different rates. The rates of their enthalpy decrease on polymerization determined by subtracting C(p) (') from C(p,app) differ but C(p) (') and C(p,app) of their final states are the same. The relaxation time increases with polymerization and decreases with an increase in T. C(p) (') rises in a sigmoid shape manner, and C(p) (") shows a peak when the relaxation time of the polymerized state is equal to the inverse of the temperature modulation frequency, whether polymerization occurs or not. The unrelaxed or vibrational heat capacity C(p,vib) of the polymers at T>T(onset) is close to C(p) of their glassy state at T<T(onset), showing that C(p) difference between the equilibrium liquid and its glass is mostly configurational. This contradicts a calculation showing that C(p,vib) change of a polymer at T(g) is generally approximately 20% of the total C(p) change.