Exploring the versatility of novel furan-based α,ω-diene carbonate monomers: synthesis, (co-)polymerization, and comparative study†

Abstract

In this work, a novel family of α,ω-diene carbonate monomers was synthesized via the alkoxy carbonylation reaction of bis(hydroxymethyl)furan (BHMF) with dialkyl carbonates (DACs) of varying chain lengths, containing terminal olefins, in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). These monomers were then subjected to acyclic diene metathesis (ADMET) polymerization with seven different ruthenium catalysts. The second-generation Hoveyda–Grubbs catalyst proved to be the most effective, yielding furan-based polycarbonates with molecular weights (M_n) up to 19 kDa. The resulting bio-based polymers exhibited thermal degradation temperatures (T_d5%) ranging from 156 °C to 244 °C and glass transition temperatures (T_g) from −8 °C to −36 °C. NMR studies confirmed their polymeric structures and provided insights into the polymers organization, which influenced their properties. These novel polycarbonates were then compared to previously reported polyesters and polyethers derived from similar furan-based α,ω-diene monomers. Additionally, for the first time, co-polymerization studies were conducted on three families of furan-based α,ω-diene monomers—ester, ether, and carbonate—revealing the effect of incorporating different functional groups on the properties of the resulting materials. This unprecedented comparison and co-polymerization reactions highlight the versatility of furan-based monomers, but also underscores the possibility to expand their application in creating tailored bio-based materials for diverse applications.