Kinelic Study of Thermal Dehydrochlorination of Poly (vinyl Chloride) in the Presence of Oxygen. Part II. Correlations of Derived Equations with Experimental Results

A correlation of experimental results with the equation for τ(t) derived in the first part of this study has been carried out. From the results it is evident the equation for η(t) expresses the true course of the thermal dehydrochlorination of PVC in oxygen at any temperature. It has been found that the elimination of HCl and the cleavage of C—C bonds represent a monomolecular stochastic process. The course of the kinetic curves of the first-order reaction is changed by the influence of the dissipative factors on the asymmetrical “S” curves. From the distribution function of the bonds it appears that the bonds of the same type in the polymer chain are not equivalent in respect to the energy, and they are characterized by a “predissociated state.” From the value of the frequency factor (104 sec.−1) it can be assumed that the elimination of hydrogen chloride represents a first-order reaction of nonadiabatic character. The rate of elimination of HC1 is not only caused by the interaction of oxygen with the double bonds but also by the number of cleft C—C bonds autocatalytically influenced. From the activation energy of scission the C—C bonds (57 kcal./mole it can be assumed that there is question of predominantly simple C—C bonds.