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

Abstract

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 °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.