Sigmatropic Rearrangements of Polymer Backbones: Vinyl Polymers from Polyesters in One Step

Abstract
Polymer modification is a fundamental scientific challenge, as a means of both upcycling plastics and extracting a stimulus response from them. To date, the overwhelming majority of polymer modifications has focused on the polymer periphery. Herein, we demonstrate nearly quantitative, scission-free modification of polymer backbones, namely, a metamorphosis of polyesters into vinyl polymers resembling commodity materials via the Ireland–Claisen sigmatropic rearrangement. The glass transition temperature (T_g) and thermal stability of the polyesters undergo dramatic changes post-transformation. Beyond polymer modification, our work advances the application of retrosynthetic analysis in polymer synthesis; the nontraditional production of vinyl polymers from lactones opens the door to a slew of previously inaccessible materials.

Citation
Sigmatropic Rearrangements of Polymer Backbones: Vinyl Polymers from Polyesters in One Step Rachael A. J. Ditzler and Aleksandr V. Zhukhovitskiy Journal of the American Chemical Society Article ASAP DOI: 10.1021/jacs.1c09657