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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 achiralmeso 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 purerac -8DL, subject to tuning by variation of the diastereomeric ratio and structure of the 8DL monomers. -
Abstract Bacterial polyhydroxyalkanoates (PHAs) are a unique class of biodegradable polymers because of their biodegradability in ambient environments and structural diversity enabled by side‐chain groups. However, the biosynthesis of PHAs is slow and expensive, limiting their broader applications as commodity plastics. To overcome such limitation, the catalyzed chemical synthesis of bacterial PHAs has been developed, using the metal‐catalyzed stereoselective ring‐opening (co)polymerization of racemic cyclic diolides (
rac ‐8DLR, R=alkyl group). In this combined experimental and computational study, polymerization kinetics, stereocontrol, copolymerization characteristics, and the properties of the resulting PHAs have been examined. Most notably, stereoselective copolymerizations ofrac ‐8DLMewithrac ‐8DLR(R=Et, Bu) have yielded high‐molecular‐weight, crystalline isotactic PHA copolymers that are hard, ductile, and tough plastics, and exhibit polyolefin‐like thermal and mechanical properties. -
Abstract Bacterial polyhydroxyalkanoates (PHAs) are a unique class of biodegradable polymers because of their biodegradability in ambient environments and structural diversity enabled by side‐chain groups. However, the biosynthesis of PHAs is slow and expensive, limiting their broader applications as commodity plastics. To overcome such limitation, the catalyzed chemical synthesis of bacterial PHAs has been developed, using the metal‐catalyzed stereoselective ring‐opening (co)polymerization of racemic cyclic diolides (
rac ‐8DLR, R=alkyl group). In this combined experimental and computational study, polymerization kinetics, stereocontrol, copolymerization characteristics, and the properties of the resulting PHAs have been examined. Most notably, stereoselective copolymerizations ofrac ‐8DLMewithrac ‐8DLR(R=Et, Bu) have yielded high‐molecular‐weight, crystalline isotactic PHA copolymers that are hard, ductile, and tough plastics, and exhibit polyolefin‐like thermal and mechanical properties.