Abstract
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 [Et3 O]+ [B(C6 F5 )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 (Tm =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 (Tm =117.6 °C) has also been revealed.
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