Installing Controlled Stereo-Defects Yields Semicrystalline and Biodegradable Poly(3-Hydroxybutyrate) with High Toughness and Optical Clarity.

Stereo-defects present in stereo-regular polymers often diminish thermal and mechanical properties, and hence suppressing or eliminating them is a major aspirational goal for achieving polymers with optimal or enhanced properties. Here, we accomplish the opposite by introducing controlled stereo-defects to semicrystalline biodegradable poly(3-hydroxybutyrate) (P3HB), which offers an attractive biodegradable alternative to semicrystalline isotactic polypropylene but is brittle and opaque. We enhance the specific properties and mechanical performance of P3HB by drastically toughening it and also rendering it with the desired optical clarity while maintaining its biodegradability and crystallinity. This toughening strategy of stereo-microstructural engineering without changing the chemical compositions also departs from the conventional approach of toughening P3HB through copolymerization that increases chemical complexity, suppresses crystallization in the resulting copolymers, and is thus undesirable in the context of polymer recycling and performance. More specifically, syndio-rich P3HB ( sr -P3HB), readily synthesized from the eight-membered meso -dimethyl diolide, has a unique set of stereo-microstructures comprising enriched syndiotactic [ rr ] and no isotactic [ mm ] triads but abundant stereo-defects randomly distributed along the chain. This sr -P3HB material is characterized by high toughness ( U T = 96 MJ/m 3 ) as a result of its high elongation at break (>400%) and tensile strength (34 MPa), crystallinity ( T m = 114 °C), optical clarity (due to its submicron spherulites), and good barrier properties, while it still biodegrades in freshwater and soil.