Bulk Crosslinking Copolymerization: Comparison of Different Modeling Approaches

The predictions of four different models of crosslinking copolymerization,Kinetic Monte Carlo (KMC), statistic/kinetic Flory/Tobita (FT) model, and two kinetic approaches based on population balance equations (PBE) (solved with generating functions (GF) and numerical fractionation (MRNF), respectively), were compared. The approaches underlying more restrictive assumptions but asking for less computational effort, FT and MRNF, lead to very satisfactory predictions in terms of average properties (sol and gel fractions, degrees of polymerizations, crosslinking densities). On the other hand, fully detailed models (KMC) as well as more computationally demanding numerical solutions of the detailed PBE (GF) become necessary when the chain length distributions are required. The present paper compares the predictions of different modeling approaches on a bulk crosslinking copolymerization scheme. Models based on average properties match the predictions of more detailed models in terms of average predictions, but not for chain length distributions. As a result, guidelines for the most‐suitable usage of such models are provided.