New families of 5-hydroxymethylfurfural derived biopolymers

Diminishing oil reserves, increasing demand, and the rising costs of petroleum-based raw materials associated with waste production has encouraged the plastic industry to seek substitute feedstocks from renewable sources [1]. As a result, the interest in polymers synthesized from natural resources - such as polysaccharides, lignin and furan-based derivatives - has been growing worldwide. One of these compounds, 5-(hydroxymethyl)furfural (HMF), which can be produced easily and in high yield from a carbohydrate source (mainly fructose) [2], has quickly emerged as the prototypical bio-based platform chemical with a broad range of applications. Having both aldehyde and alcohol functional groups and an aromatic structure HMF is considered a versatile starting material for a variety of high value chemicals that can be used as monomers for the synthesis of a selection of bio-based polymers. One very promising example are polymers based on 2,5-furandicarboxylic acid (FDCA): poly(ethylene-2,5-furandicarboxylate) (PEF) and poly(butylene-2,5-furandicarboxylate) (PBF), which have the potential to replace their petroleum-derived counterparts: polyethylene terephthalate (PET) and polybutylene terephthalate (PBT) [3], due to their enhanced thermal an mechanical properties. Although furan-based polymers have received particular attention from the scientific community in recent years, the industry is still in its infancy. With this in mind, this project developed a new furan bio-monomers starting from HMF, that can be used has building block to synthetize via addition polymerization and acyclic diene metathesis (ADMET) polymerization, several families of furanic based biopolymers. The structure and the properties of the novel furanic-based polymers were then studied to evaluate their potential industrial applications. [1] R. Bielski and G. Grynkiewicz, “Furan platform chemicals beyond fuels and plastics,” Green Chemistry, vol. 23, no. 19, pp. 7458–7487, Oct. 2021 [2] G. Trapasso, G. Mazzi, B. Chícharo, M. Annatelli, D. Dalla Torre, and F. Aricò, “Multigram Synthesis of Pure HMF and BHMF,” Organic Process Research and Development, vol. 26, no. 10. American Chemical Society, pp. 2830–2838, Oct. 21, 2022 [3] M. Jiang, Q. Liu, Q. Zhang, C. Ye, and G. Zhou, “A series of furan-aromatic polyesters synthesized via direct esterification method based on renewable resources,” J Polym Sci A Polym Chem, vol. 50, no. 5, pp. 1026–1036, Mar. 2012