Toughening Poly(lactic acid) without Compromise – Statistical Copolymerization with a Bioderived Bicyclic Lactone

Poly(lactic acid) (PLA) offers a renewable and degradable alternative to petroleum-based plastic, but its mechanical properties are not ideal for many applications. Herein, we describe the synthesis and polymerization of 2-oxo-3,8-dioxabicyclo[3.2.1]octane (ODO), a bioderived bicyclic lactone, and show that copolymers of l-lactide (LA) with small amounts of ODO have improved mechanical properties over PLA. Homopolymerization of ODO to poly(oxo-3,8-dioxabicyclo[3.2.1]octane) (PODO) is optimized for both solution-phase, organocatalytic and melt-phase, metal-catalyzed conditions. In comparison to the monocyclic analog, ε-caprolactone (CL), ODO has a lower enthalpy of polymerization and faster rate of polymerization. PODO is an amorphous, elastomeric polyester that has a T_g 90 °C higher than poly(ε-caprolactone) (PCL). Statistical copolymerization of LA with small fractions of ODO yields tough and transparent thermoplastics that have over 12× elongation at break compared to native PLA, while maintaining T_g, Young's modulus (E), and yield strength. Together, these results describe how the incorporation of the tetrahydrofuran ring alters lactone polymerizability and the thermomechanical properties of the homopolymer and copolymer materials.