Laser Single Pulse Initiated RAFT Polymerization for Assessing Chain‐Length Dependent Radical Termination Kinetics

Summary: A novel method combining RAFT polymerization with pulsed‐laser initiation for determining chain‐length dependent termination rate coefficients, k_t, is presented. Degenerative chain‐transfer in RAFT enables single‐pulse pulsed‐laser polymerization (SP‐PLP) traces to be measured on systems with a narrow radical distribution that remains essentially unchanged during the experiment. SP‐PLP‐RAFT experiments at different polymerization times allow for determining k_t as a function of chain length via classical kinetics assuming chain‐length independent k_t.

Single‐pulse pulsed‐laser polymerization trace for BMPT‐mediated RAFT polymerization of butyl acrylate.