Gold-Catalyzed Post-Polymerization Modification of Commodity Aromatic Polymers.

Synthetic aromatic polymers are ubiquitous and indispensable to modern life, industry, and the global economy. The direct functionalization of these materials remains a considerable challenge on account of their unreactive aromatic C-H bonds and robust physical properties. Here, we demonstrate that homogeneous gold catalysis offers a mild, chemoselective, and practical approach to functionalize high-volume commodity aromatic polymers. Utilizing a gold-catalyzed intermolecular hydroarylation between a methyl ester functionalized alkyne, methyl propiolate, and nucleophilic arenes within polystyrene (PS) results in direct functionalization of phenyl rings with 1,2-substituted methyl acrylate functional groups. The reactivity and functionalization depend on the steric and electronic environment of the catalyst, counterion pairing, and method of activation. The reactivity is broad in scope, enabling the functionalization of arenes within commercial polysulfone (PSU) and waste polyethylene terephthalate (PET). These reactions open new opportunities to chemically transform aromatic polymers and modify their physical properties.
Competing Interests: The authors declare the following competing financial interest(s): E.R.K., S.B.H., and J.D.A. are inventors on a patent application filed by the University of Southern Mississippi for the reactions described in this Communication.
(© 2021 The Authors. Published by American Chemical Society.)