Monte Carlo simulation of the chain length distribution in pulsed-laser polymerization experiments in microemulsion

The Monte Carlo method has been used for numerically simulating pulsed-laser polymerization (PLP) in microemulsion, in order to establish if a shift from inflection point to peak maximum as the best measure of the propagation rate constant, k_p, will occur theoretically. Termination is assumed to be instantaneous in the simulations as droplet sizes can be very small in microemulsions. From the results of the simulations it is found that instantaneous termination indeed causes the peak maximum to become the best measure of k_p. From these results it can be deduced that in bulk it is not simply the Poisson-broadening that causes the peak maximum to yield an overestimation of k_p. This overestimation is rather caused by the fact that the termination rate is finite leading to an asymmetrical peak in the molecular weight distribution. In combination with broadening this yields the inflection point to be the best measure of k_p in the bulk.