Free-Radical Propagation Rate Coefficients of Diethyl Itaconate and Di-n-Propyl Itaconate Obtained via PLP–SEC

The propagation step is one of the key reactions in radical polymerization and knowledge about its kinetics is often vital for understanding and designing polymerization processes leading to new materials or optimizing technical processes. Arrhenius expressions for the propagation step in free-radical polymerization of diethyl itaconate (DEI) as well as di-n-propyl itaconate (DnPI) in bulk, for which propagation kinetics was yet unexplored, were thus determined via pulsed-laser polymerization in conjunction with size-exclusion chromatography (PLP-SEC) experiments in the temperature range of 20 to 70 °C. For DEI, the experimental data was complemented by quantum chemical calculation. The obtained Arrhenius parameters are A = 1.1 L·mol(–1)·s(–1) and E(a) = 17.5 kJ·mol(−1) for DEI and A = 1.0 L·mol(–1)·s(–1) and E(a) = 17.5 kJ·mol(−1) for DnPI.