A guide to modern methods for poly(thio)ether synthesis using Earth-abundant metals

Abstract

Polyethers and polythioethers have a long and storied history dating back to the start of polymer science as a distinct field. As such, these materials have been utilized in a wide range of commercial applications and fundamental studies. The breadth of their material properties and the contexts in which they are applied is ultimately owed to their diverse monomer pre-cursors, epoxides and thiiranes, respectively. The facile polymerization of these monomers, both historically and contemporaneously, across academia and industry, has occurred through the use of Earth-abundant metals as catalysts and/or initiators. Despite this, polymerization methods for these monomers are underutilized compared to other monomer classes like cyclic olefins, vinyls, and (meth)acrylates. We feel a focused review that clearly outlines the benefits and shortcomings of extant synthetic methods for poly(thio)ethers along with their proposed mechanisms and quirks will help facilitate the utilization of these methods and by extension the unique polymer materials they create. Therefore, this Feature Article briefly describes the applications of poly(thio)ethers before discussing the feature-set of each poly(thio)ether synthetic method and qualitatively scoring them on relevant metrics (e.g., ease-of-use, molecular weight control, etc.) to help would-be poly(thio)ether-makers find an appropriate synthetic approach. The article is concluded with a look ahead at the future of poly(thio)ether synthesis with Earth-abundant metals.