Determination of rates of thermal decomposition of polymerization initiators with a differential scanning calorimeter

Abstract A commercial differential scanning calorimeter has been used to determine thermal and kinetic data of some typical polymerization initiators. Since the rate of heat change due to decomposition is directly related to the rate of decomposition at a given temperature, suitable analysis of the differential thermal curve can yield the Arrhenius parameters of a reaction from a single run. In order to test the method, the well‐established first‐order decomposition of azobisisobutyronitrile was determined in di‐ n ‐butyl phthalate as solvent. Reproducible results were obtained which accorded with published data by orthodox determinations. The rates of thermal decomposition in solution of benzoyl peroxide and diisopropyl peroxydicarbonate were also determined. The method provides a rapid means for the direct determination of fast rates not possible with orthodox analytical determinations.