A Novel Approach for Investigation of Chain Transfer Events by Pulsed Laser Polymerization

Pulsed laser polymerization (PLP) with subsequent analysis of molecular mass distribution (MMD) is used to determine the rate coefficient of chain transfer to an agent A, ktrA, by varying pulse repetition rate such that the contributions of PLP‐induced and chain‐transfer‐induced peaks to the MMD change to a significant extent. It is shown by simulation that the relative heights of these peaks may be used to estimate ktrA. The method is applied to evaluation of the rate coefficient of chain transfer to dodecyl mercaptan with butyl methacrylate polymerizations at −11, 0, 20 and 40 °C. The Arrhenius parameters for this coefficient are determined to be: A(ktrA) = (2.2 ± 0.6) × 106 L · mol−1 · s−1 and Ea(ktrA) = (22.1 ± 0.7) kJ · mol−1. Frequency‐tuned pulsed laser polymerization in conjunction with analysis of molecular mass distribution of the polymeric product is used to determine the rate coefficient of chain transfer to an agent. The new method is successfully applied for deducing the rate coefficient of chain transfer to dodecyl mercaptan in butyl methacrylate polymerizations at −11, 0, 25, and 40°C.