Chain‐length dependent termination in rotating sector polymerization, 1. The evaluation of the rate constant of chain propagation kp

The chain‐length distributions (CLDs) of polymers prepared by rotating‐sector (RS) techniques under pseudostationary conditions were simulated for the case of chain‐length dependent termination and analysed for their suitability of determining the rate constant of chain propagation k_p from the positions of their points of inflection. The tendency to underestimate k_p is a little more pronounced than in pulsed‐laser polymerization (PLP) but, interestingly, the situation improves in the presence of chain‐length dependent termination. The estimates also were found to be more precise a) for smaller rates of initiation, b) for higher order points of inflection, c) if termination is by combination, d) if the role played by the shorter one of the two chains becomes less dominant. Taken in all, the determination of k_p from the points of inflection in the CLD of RS‐prepared polymers may well compete with the more famous PLP method, especially if some care is taken with respect to the choice of experimental conditions.