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

Abstract

AbstractThe present research article delves into the preparation of a new class of bio‐based polyesters from α,ω‐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.