Molecular weight distribution in living polymerization proceeding with reshuffling of polymer segments due to chain transfer to polymer with chain scission, 1. Determination ofkp/ktr ratio from DPw/DPn data. Ideal reproduction of polymer chain activities

The molecular weight distribution (MWD) curves for polymerization systems with chain transfer to polymer leading to reshuffling of polymer segments (and broadening of the MWD), but not changing chain functionalities, were simulated by the Monte Carlo method. The bimodality observed in some distributions was explained by different distribution functions of chains which did not undergo reshuffling and of those which underwent the chain transfer reaction. Using this observation, a numerical integration method for computing DPw/DPn (and the MWD curves) in the systems under consideration was devised. Plots relating DPw/DPn to monomer conversion and ktr/kp are presented and a method of determination of ktr/kp from the DPw/DPn data is proposed.