Oligomer distribution for interfacial step growth polycondensation

Abstract Low levels of oligomer molecules are generally desirable in polymeric materials. It is known that several reactor variables can affect the oligomer distribution, and therefore it is useful to have predictive models for molecular weight distribution. The normal approach of a differential equation–based model is very complex to set up if it is applied rigorously to include all the non‐Flory aspects of the step growth polycondensation and in particular the interfacial polycarbonate polymerization. In this paper, simple methods based on the Monte Carlo method and Stockmayer distribution are applied to simulate the effects of mass‐transfer, unequal reactivity, and the starting stoichiometry of the polycondensing functional groups on the oligomer distribution. It is shown that these parameters can have a significant effect on the oligomer weight distribution and polydispersity of the final polymer.