Kinetic Monte Carlo Modeling Extracts Information on Chain Initiation and Termination from Complete PLP-SEC Traces

摘要: Complete pulsed laser polymerization (PLP) log-molar mass distributions (log-MMDs) are accurately simulated using kinetic Monte Carlo (kMC) modeling to gain not only knowledge on the propagation but also chain initiation and termination reactivity. The isothermal kMC model (306–325 K) accounts for diffusional limitations all relevant elementary reactions, considering n-butyl acrylate, 2,2-dimethoxy-2-phenylacetophenone (DMPA), a frequency of 500 s–1. disparate reactivities toward vinylic bonds DMPA fragments essential ensure well-defined multimodality log-MMDs necessary identify consecutive inflection points. It is illustrated that PLP log-MMD data can be used test validity models apparent rate coefficients at low monomer conversions simulations powerful tool track growth different radical types between pulses dominant reactions.