An improved general kinetic analysis of non-linear irreversible polymerisations

A method to predict average molecular weights before and after gelation for general irreversible non-linear polymerisations forming tree-like molecules is described. Recently developed numerical methods for solving two point boundary value problems are essential for the success of these calculations after gelation and open the way to eventually be able to efficiently predicting chain length distributions. Anionic and free-radical polymerisation of vinyl monomers in the presence of divinyl monomers or with transfer to polymer are taken as case studies. Comparison to experimental data and with simulation results obtained through "numerical fractionation" confirms the usefulness of current approach. (C) 2004 Elsevier Ltd. All rights reserved.