Furandicarboxylate Polyesters: A Comprehensive ADMET Study of a Novel Class of Furan‐Based α,ω‐Diene Monomers

The present research article delves into the preparation of a new class of bio-based polyesters from diene furandicarboxylate monomers. In particular, it exploits the use of acyclic diene metathesis polymerisation (ADMET) on 2,5-furandicarboxylic acid (FDCA)-derived compounds. First, a library of furan-based α,ω-diene monomers was prepared via acid- or base-catalyzed transesterification of 2,5-furandicarboxylic acid dimethyl ester (FDME) with commercially available alcohols incorporating terminal olefins, i. e., allyl alcohol, but-3-en-1-ol, hex-5-en-1-ol and dec-9-en-1-ol. Then, the novel monomers were subjected to ADMET polymerisation employing different catalysts and reaction conditions. Interestingly, first-generation Grubbs catalyst was found to be the best promoter for ADMET polymerisation. This catalyst allowed the preparation of a new family of bio-based polyesters with molecular weights up to 26.4 kDa, with good thermal stability, and adaptable cis-trans conformations. Results also revealed that the monomer structure had a direct impact on the polymerisation efficiency and the resulting thermal properties. The effect of green bio-based solvents such as Cyrene™, dimethyl isosorbide (DMI) and γ-valerolactone (GVL) on the polymerisation process was also studied. Data collected showed that the solvent concentration influenced both the yield and length of polymers formed. Furthermore, some co-polymerisation experiments were conducted; the successful integration of different monomers in the resulting copolymer was shown to affect the glass transition temperature (Tg) of the resulting materials.