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,C-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,C-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,C-app differ but C-p(') and C-p,C-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,C-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,C-vib change of a polymer