Converting Non-strained γ-Valerolactone and Derivatives into Sustainable Polythioesters via Isomerization-driven Cationic Ring-Opening Polymerization of Thionolactone Intermediate.

This contribution reports the efficient conversion of γ-valerolactone and its derivatives, abundant but unexplored renewable feedstocks, into sustainable and degradable polythioesters via the establishment of the first isomerization-driven ring-opening polymerizations (IROPs) of corresponding thionolactone intermediates. The key to this success relies on the development of a new simple and robust [Et 3 O] + [B(C 6 F 5 ) 4 ] - cationic initiator which possesses high activity, exclusive selectivity, living nature, and broad scope of thionolactones. A complete inversion of configuration during IROP of enantiopure γ-thionovalerolactone is also disclosed, affording isotactic semicrystalline polythioesters (T m =87.0 °C) with mechanical property compared well to the representative commodity polyolefins. The formation of a highly crystalline supramolecular stereocomplex with enhanced thermal property (T m =117.6 °C) has also been revealed.