Abstract
The synthesis of hyperbranched PMMA has been achieved using a facile one-step batch solution polymerization reaction. The reaction is essentially a linear polymerization doped with appropriate amounts of a multifunctional monomer (MFM) and chain transfer agent (CTA). On this basis, a theoretical model for the MFM reaction has been developed and experimentally validated for the number-aver age molecular weight and degree of branching data, by assuming isothermal batch conditions and employing key reaction parameters from established linear PMMA kinetics. A first comparison of the melt rheology of the hyperbranched polymer with that of the linear one revealed a significant reduction in melt viscosity and shear thinning. It is expected that the generic model developed here will guide the manufacture of other free-radical hyperbranched polymers, of desired architecture or physical properties, using modeling and optimization methods. © 2005 American Chemical Society.