From Impossible to Possible: Atom‐Economic Polymerization of Low Strain Five‐Membered Carbonates

The direct ring-opening polymerization (ROP) of propylene carbonate (PC) only affords oligomers with substantial unidentified by-products, which hinders the efficient utilization of PC. Through detailed studies, for the first time, a careful mechanism involving the in situ release of propylene oxide (PO) from PC decarboxylation is proposed. Further, we report a novel strategy of copolymerization of PC/cyclic anhydrides via in situ capture of the formed intermediates. Results show that PC is successfully transformed into polyesters. Especially for the ring-opening alternating copolymerization (ROAC) of PC/phthalic anhydride (PA), a variety of advantages are manifold: i) slow-release of PO ensuring a perfectly alternating structure; ii) quantitative and fast transformation of PC; iii) visualization of polymerization process by a CO2 pressure gauge. Of importance, through tandem polymerizations, PC is fully transformed into polyesters and polycarbonates concurrently, thus achieving PC utilization with a high atom-economy.