Abstract

This review describes the characterization and application of poly(hydroxyalkanoates), PHAs, a remarkable family of natural polyesters with a wide array of useful properties and potential applications. It places specific emphasis on the work of Robert H. Marchessault and his many colleagues outlining how Marchessault’s body of work both shaped the field and complemented the work of his contemporaries. Particular attention will focus on the “rediscovery” of poly(β-hydroxybutyrate), PHB, the first PHA to be discovered, from the late 1950s onward, highlighting some of the historical aspects of PHA’s path toward commercial applications. It will also cover why this class of materials is so unique, including PHA structure–properties relationships, its unique crystalline behaviour, in vivo – in vitro synthesis and degradation, and PHA-graft-copolymers.Key words: poly(hydroxyalkanoate), PHA, poly(β-hydroxybutyrate), PHB, biopolymers, bacterial polyester, random copolymers, polymer single crystals, graft copolymers.

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