Biobased Random Copolymers of Poly(Hexamethylene Furanoate) for Sustainable Food Packaging: Camphoric Acid as a Valuable Co-Monomer for Improved Mechanical Properties

In recent years, the unsustainable consumption of fossil resources has been causing major ecological concerns, especially for the production of polymeric materials. 2,5-furandicarboxylic acid (FDCA) is one of the most appealing biobased chemical building blocks, because of its potential to replace the industrially widespread petrochemical, terephthalic acid. Camphoric acid (CA) is also an interesting biobased chemical derived from camphor, one of the most widespread fragrances. This work had the objective of combining CA, FDCA and biobased 1,6-hexanediol to synthesize random copolymers for sustainable food packaging applications by means of a solvent-free polycondensation process, obtaining poly(hexamethylene furanoate-co-camphorate)s (PHFC). The optimization of the synthesis made it possible to obtain high molecular weight polyesters with a percentage of camphoric acid up to 17 mol%, which could be compression-molded into films. They were subjected to molecular, structural, thermal and functional characterization via NMR, GPC, WAXS, DSC, and TGA analyses, as well as mechanical and gas permeability tests. Compared to the homopolymer of reference, it was possible to obtain higher flexibility, 430% higher elongation at break, and 223% higher toughness, with comparable, excellent gas permeability properties. Calorimetric evidence suggested that camphoric acid might have enhanced the formation of a partially ordered mesomorph phase in the copolymers under study.