Chain‐length‐dependent termination rate coefficients of the bulk free‐radical polymerization of styrene at 80 °C are determined by combining online polymerization rate measurements (DSC) with living RAFT polymerizations. Full kt versus chain‐length plots were obtained indicating a high kt value for short chains (2 × 109 L · mol−1 · s−1) and a weak chain‐length dependence between 10 and 100 monomer units, quantified by an exponent of −0.14 in the corresponding power law 〈kti,i〉 = kt0 · P−b.
Double logarithmic plots of 〈kti,i〉 versus P, evaluated from experimental time‐resolved Rp data according to the procedure described in the text, for different CPDA and AIBN concentrations. The best linear fit for (10 < P < 100) is indicated as full line.
