Universal Scaling Behavior during Network Formation in Controlled Radical Polymerizations

Despite the ubiquity of branched and network polymers in biological, electronic, and rheological applications, it remains difficult to predict the network structure arising from polymerization of vinyl and multivinyl monomers. While controlled radical polymerization (CRP) techniques afford modularity and control in the synthesis of (hyper)branched polymers, a unifying understanding of network formation providing grounded predictive power is still lacking. A current limitation is the inability to predict the number and weight average molecular weights that arise during the synthesis of (hyper)branched polymers using CRP. This study addresses this literature gap through first building intuition via a growth boundary analysis on how certain environmental cues (concentration, monomer choice, and cross-linker choice) affect the cross-link efficiency during network formation through experimental gel point measurements. We then demonstrate, through experimental gel point normalization, universal scaling behavior of molecular weights in the synthesis of branched polymers corroborated by previous literature experiments. Moreover, the normalization employed in this analysis reveals trends in the macroscopic mechanical properties of networks synthesized using CRP techniques. Gel point normalization employed in this analysis both enables a polymer chemist to target specific number and weight average molecular weights of (hyper)branched polymers using CRP and demonstrates the utility of CRP for gel synthesis.