Biodegradable Polyhydroxyalkanoates by Stereoselective Copolymerization of Racemic Diolides: Stereocontrol and Polyolefin‐Like Properties

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