A Chemocatalytic Route to Stereoregular Poly(3-hydroxyhexanoate) and Its Statistical and Tri-Block Copolymers

Poly(3-hydroxyhexanoate) (P3HHx)-based poly(3-hydroxyalkanoate)s (PHAs) are biologically produced, commercially implemented PHAs, but little is known in the open literature about the structure and property characterizations of discrete, authentic homopolymer P3HHx, and its copolymers with poly(3-hydroxybutyrate) (P3HB). Here, we introduce a chemocatalytic route to stereoregular (both isotactic and syndiotactic) P3HHx and PHA copolymers with P3HB, including statistical copolymer P3HBHx with various levels of 3HHx incorporation and discrete hard-soft-hard triblock copolymer P3HB-<i>b</i>-P3HHx-<i>b</i>-P3HB, and present extensive characterizations of their structures, thermal properties, and mechanical performance. The synthesis is efficiently achieved by one-pot polymerization of eight-membered di(<i>n</i>-propyl) and dimethyl (for copolymerization) diolides catalyzed by chiral molecular catalysts. Notably, P3HBHx can be rapidly produced in quantitative yield and exhibits high molar mass (<i>M</i>_n up to 551 kg/mol) as well as both high modulus (up to 1.39 GPa) and ductility (up to 445%), while P3HB-<i>b</i>-P3HHx-<i>b</i>-P3HB further extends application temperature windows by possessing a unique combination of low <i>T</i>_g (-18 °C) and high <i>T</i>_m (154 °C) values. These findings highlight the stereomicrostructural and architectural versatility of chemocatalytic routes to PHAs, which, in turn, can be utilized to largely tune the PHA thermal properties and mechanical performance.