Atactic, Isotactic, and Syndiotactic Methylated Polyhydroxybutyrates: An Unexpected Series of Isomorphic Polymers

Polyhydroxyalkanoates (PHAs), such as poly[(R)-3-hydroxybutyrates] [(R)-P3HB], are produced by bacteria and are promising alternatives to nondegradable polyolefin plastics, but their semicrystallinity and high melting points are only maintained at high tacticity, which are commonly seen in other semicrystalline polymers like isotactic polypropylene (iPP). We herein report a class of synthetic PHAs, cis-poly(3-hydroxy-2-methylbutyrate)s (cis-PHMBs), that exhibit tacticity-independent semicrystallinity. The syndiotactic, isotactic, and even atactic PHMBs all share high melting points (Tm > 170 °C) and nearly identical crystal structures. The isomorphism of these polymers across three different tacticities has allowed access to iPP-like, high-performance PHMB without the requirement of high tacticity.