Calculation of Molecular Weight Distributions in Non‐Linear Free‐Radical Polymerization Using the Numerical Fractionation Technique

Mathematical Modeling of non-linear polymerization systems subject to gel formation is a challenging endeavor. At the gel point, the second and higher molecular weight moments diverge to infinity making it impossible to obtain the molecular weight distribution (MWD). The numerical fractionation (NF) technique utilizes a refinement of the method of moments to model non-linear polymerization systems that form gel. Since the method of moments yields results in terms of average quantities, some information is lost when reconstructing the MWD using NF. As a consequence, a broad shoulder appears at the high chain length end of the MWD tail. This study demonstrates that the validity of the gamma distribution deteriorates for the broader branched polymer generations and evaluates the performance of various alternative model distributions. Proper selection of the model distribution enhances the NF-reconstructed MWD. Illustration of closure approximations derived from known distribution functions, and proposed closure for the direct solution.