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Synthesis of Phenyl-Substituted Poly(3-Hydroxybutyrates) with High and Tunable Glass Transition Temperatures via
Sarah M Severson1, Alexandra A Fresh1, Luis Limon1
1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, United States.
None:
Atactic polystyrene is a commonplace transparent thermoplastic with a high glass transition temperature (Tg ∼ 100 °C), but its nondegradable backbone leads to detrimental environmental accumulation. Poly(hydroxyalkanoates) (PHAs) have emerged as biodegradable polyester alternatives to conventional olefinic plastics, but only a few PHAs possess the high Tg values (>100 °C) characteristic of polystyrene. Herein, we report the synthesis of phenyl-substituted poly(3-hydroxybutyrates) (PhPHBs) via sequential catalytic carbonylation and zinc-mediated ring-opening polymerization (ROP). Both cis and trans isomers of α-phenyl-β-butyrolactone (α-Ph-β-BL) were synthesized and polymerized to provide 13 distinct PhPHBs of varying trans incorporation and their resulting properties were systematically studied. The PhPHBs exhibit high and tunable Tg values (104-128 °C) and high thermal stability. We anticipate this work will inform the design of future high Tg PHAs as degradable alternatives to polystyrene.
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