ChemSusChem. 2023 Nov 8:e202301311. doi: 10.1002/cssc.202301311. Online ahead of print.
The 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 polymerization on 2,5-furandicarboxylic acid -derived monomers. 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, Then, the novel monomers were subject to ADMET polymerization employing different catalysts and reaction conditions. Interestingly, first-generation Grubbs catalyst was found to be the best promoter for ADMET polymerization. This catalyst allowed the preparation of a new family of polyesters with high molecular weights, excellent thermal stability, and adaptable cis-trans conformations. Results also revealed that the monomer structure had a direct impact on the polymerization 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 polymerization process was also studied. Data collected showed that the solvent concentration influenced both the yield and length of polymers formed. Furthermore, some copolymerization 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.