Multi-functional monomer derived hyperbranched poly(methyl methacrylate): Kinetic modelling and experimental validation

Multi-functional monomer induced hyperbranched PMMA production has been shown to be a relatively facile, one-step batch solution polymerisation reaction. Essentially, the reaction is a linear polymerisation doped with appropriate amounts of multi-functional monomer (MFM) and chain transfer agent (CTA). A theoretical model for the MFM reaction has been experimentally validated using conversion, number-average molecular weight, and branching data, by employing key reaction parameters from established linear PMMA kinetics. However, the kinetic model has been modified to account for the MFM and CTA contributions, which generate the branched architecture and inhibit the onset of gelation, respectively. An important outcome of this work is the development of a generic model for hyperbranched polymer synthesis, in which the manufacture of other free-radical hyperbranched polymers, of desired architecture or physical properties, can be guided using modelling and optimisation methods.