Stereosequenced crystalline polyhydroxyalkanoates from diastereomeric monomer mixtures

Stereoselective polymerization of chiral or prochiral monomers is a powerful method to produce high-performance stereoregular crystalline polymeric materials. However, for monomers with two stereogenic centers, it is generally necessary to separate diastereomers before polymerization, resulting in substantial material loss and added energy cost associated with the separation and purification process. Here we report a diastereoselective polymerization methodology enabled by catalysts that directly polymerize mixtures of eight-membered diolide (8DL) monomers with varying starting ratios of chiral racemic (rac) and achiral meso diastereomers into stereosequenced crystalline polyhydroxyalkanoates with isotactic and syndiotactic stereodiblock or stereotapered block microstructures. These polymers show enhanced ductility and toughness relative to polymers of pure rac-8DL, subject to tuning by variation of the diastereomeric ratio and structure of the 8DL monomers.