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Biodegradable Polyhydroxyalkanoates by Stereoselective Copolymerization of Racemic Diolides: Stereocontrol and Polyolefin‐Like Properties
Author(s) -
Tang Xiaoyan,
Westlie Andrea H.,
Caporaso Lucia,
Cavallo Luigi,
Falivene Laura,
Chen Eugene Y.X.
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201916415
Subject(s) - polyolefin , copolymer , polyhydroxyalkanoates , polymerization , stereoselectivity , polymer chemistry , tacticity , chemistry , alkyl , polymer , organic chemistry , materials science , catalysis , bacteria , layer (electronics) , biology , genetics
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 ‐8DL R , 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 of rac ‐8DL Me with rac ‐8DL R (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.