Kinetics of Thermal Polymerization

Initial rates for the thermal polymerization of styrene in various 

In the search for a plausible mechanism for initiation in thermal polymerization, it is necessary to reject unimolecular processes such as the opening of the double bond to form a monomeric diradical 

The proposed mechanism leads to a second-order rate for thermal conversion of monomer in agreement with experiment. 

From measured rates of thermal polymerization, and the previously evaluated ratios k /kt, we may assign values to ki. Thus from the data given in Table XI extrapolated to 100°C, kl/kt=. bXlO for styrene 

The apparent activation energy obtained from the slope of a plot of the logarithm of the rate Rp of pol merization against /T will be related to the individual activation energies, in analogy with Eq. (19), as follows  

---