| Abstract: | The effect of thermal initiation of the radical polymerization of unsaturated monomers has been analyzed by considering a kinetic scheme that includes thermal- and catalyst-induced formation of free radicals, propagation, and termination reactions. Expressions relating the different rate constants with the instantaneous monomer concentration are derived and they indicate the great influence of thermal initiation on the kinetic results. Application to a real case suggests that evaluation of kd and kp/k from experimental results using the method of dead-end polymerization may lead to erroneous values of these constants. |
