Toughening Glassy Poly(lactide) with Block Copolymer Micelles

Poly­(lactide) (PLA), a compostable bioderived polyester, can be produced at a cost and scale that makes it an attractive replacement for nondegradable petroleum-derived thermoplastics. However, pristine PLA is brittle and unsuitable for use in applications where high impact strength and ductility are required. In this work we demonstrate that poly­(l-lactide) (PLLA) in the glassy state can be toughened significantly via addition of an amphiphilic diblock polymer. Notably, a PLLA blend containing only 5 wt% poly­(ethylene oxide)-b-poly­(butylene oxide) (PEO–PBO) exhibited tensile toughness and notched Izod impact strength over an order of magnitude higher than neat amorphous PLLA without a significant reduction in transparency or elastic modulus. For a series of PLLA blends containing PEO–PBO of fixed composition (∼70% volume fraction PBO), the toughness was inversely related to the molar mass of the added modifier with the highest toughness observed for the blend containing the smallest diblock (∼7 kg/mol). Interestingly, at fixed composition and molar mass poly­(l-lactide)-b-poly­(butylene oxide) (PLLA–PBO) exhibited a substantial but reduced toughening efficiency compared to PEO–PBO. We attribute this difference to a change in the solubility parameter of the amphiphilc block. Using TEM, we show that the greatest toughening is observed when the diblock modifier forms small cylindrical micelles that are well dispersed in the PLLA matrix. This morphology is facilitated by a negative Flory–Huggins interaction parameter (χ) between PEO and PLLA. These insights suggest a new and versatile strategy for the facile and efficient toughening of brittle thermoplastics.