Selective Depolymerization for Sculpting Polymethacrylate Molecular Weight Distributions

Chain-end reactivation of polymethacrylates generated by reversible-deactivation radical polymerization (RDRP) has emerged as a powerful tool for triggering depolymerization at significantly milder temperatures than those traditionally employed. In this study, we demonstrate how the facile depolymerization of poly(butyl methacrylate) (PBMA) can be leveraged to selectively skew the molecular weight distribution (MWD) and predictably alter the viscoelastic properties of blended PBMA mixtures. By mixing polymers with thermally active chain ends with polymers of different molecular weights and inactive chain ends, the MWD of the blends can be skewed to be high or low by selective depolymerization. This approach leads to the counterintuitive principle of the "destructive strengthening" of a material. Finally, we demonstrate, as a proof of concept, the encryption of information within polymer mixtures by linking Morse code with the MWDs before and after selective depolymerization, allowing for the encoding of data within blends of synthetic macromolecules.