Chain-End Controlled Depolymerization Selectivity in α,α-Disubstituted Propionate PHAs with Dual Closed-Loop...

Within the large poly(3-hydroxyalkanoate) (PHA) family, C3 propionates are much less studied than C4 butyrates, with the exception of α,α-disubstituted propionate PHAs, particularly poly(3-hydroxy-2,2-dimethylpropionate), P3H(Me)₂P, due to its high melting temperature (T_m ∼ 230 °C) and crystallinity (∼76%). However, inefficient synthetic routes to its monomer 2,2-dimethylpropiolactone [(Me)₂PL] and extreme brittleness of P3H(Me)₂P largely hinder its broad applications. Here, we introduce simple, efficient step-growth polycondensation (SGP) of a hydroxyacid or methyl ester to afford P3H(Me)₂P with low to medium molar mass, which is then utilized to produce lactones through base-catalyzed depolymerization. The ring-opening polymerization (ROP) of the 4-membered lactone leads to high-molar-mass P3H(Me)₂P, which can be depolymerized by hydrolysis to the hydroxyacid in 99% yield or methanolysis to the hydroxyester in 91% yield, achieving closed-loop recycling via both SGP and ROP routes. Intriguingly, the chain end of the SGP-P3H(Me)₂P determines the depolymerization selectivity toward 4- or 12-membered lactone formation, while both can be repolymerized back to P3H(Me)₂P. Through the formation of copolymers P3H(Me/R)₂P (R = Et, Pr), PHAs with high tensile strength and ductility, coupled with high barriers to water vapor and oxygen, have been created. Notably, the PHA structure-property study led to P3H(Pr)₂P with a record-high T_m of 266 °C within the PHA family.