Nanostructured poly(l-lactic acid)-poly(ethylene glycol)-poly(l-lactic acid) triblock copolymers and their CO2/O2 permselectivity

Biodegradable poly(l-lactic acid)-poly(ethylene glycol)-poly(l-lactic acid) (PLLA-PEG-PLLA) copolymers were synthesized by ring-opening polymerization of l-lactide using dihydroxy PEG as the initiator. The effects of different PEG segments in the copolymers on the mechanical and permeative properties were investigated. It was determined that certain additions of PEG result in composition-dependent microphase separation structures with both PLLA and PEG blocks in the amorphous state. Amorphous PEGs with high CO2 affinity form gas passages that provide excellent CO2/O-2 permselectivity in such a nanostructure morphology. The gas permeability and permselectivity depend on the molecular weight and content of the PEG and are influenced by the temperature. Copolymers that have a higher molecular weight and content of PEG present better CO2 permeability at higher temperatures but provide better CO2/O-2 permselectivity at lower temperatures. In addition, the hydrophilic PEG segments improve the water vapor permeability of PLLA. Such biodegradable copolymers have great potential for use as fresh product packaging.