Biobased Bifunctional Monomers toward Functionalizable Polycarbonates and Poly(cyclic olefin)s with Tunable Properties

Biobased materials have served as an attractive alternative to replace current petroleum-based plastics because of their abundant biorenewable feedstocks and potential degradability. Here we prepared a class of seven-membered ring carbonates containing biobased Diels-Alder adduct moieties. The bifunctional monomers M1 and M2 exhibited excellent reactivity for both ring-opening polymerization and ring-opening metathesis polymerization, yielding functionalizable aliphatic polycarbonates and poly(cyclic olefin)s with a range of Tg values from 84 to 194 degrees C. The resulting polymers can be postpolymerization functionalized by click, cross-linking, hydrogenation, hydrolysis, and retro-Diels-Alder reactions, which appeared to be powerful tools to tune the thermal and mechanical properties of the resulting polymers. Ultimately, the resulting polycarbonate P(M1)ROP-SC6H13 possessed polyolefin-like mechanical performance. These polycarbonates can be completely hydrolyzed into their corresponding starting material diols, demonstrating a potential close-loop life cycle of P(M)ROP. Remarkably, this novel monomer design strategy enabled diverse functionalities to be incorporated, providing access to biobased materials with tunable properties.

Automated summary

Biobased materials are attractive alternatives to petroleum-based plastics due to their renewable nature and degradability. In this study, we synthesized a class of seven-membered ring carbonates containing biobased Diels-Alder adduct moieties. These materials exhibited excellent reactivity and could be used to produce functionalizable polymers with a range of thermal and mechanical properties. This research provides a novel design strategy for the synthesis of biobased materials with tunable properties.