Synthesis and Properties of Poly(alkylene vanillate) Polyesters, A New Class of Bio-Based Polymers

Nowadays, modern societies are striving to adopt a more environmental-friendly lifestyle. In this context, the conversion of biomass to value-added products has attracted a lot of interest both from academia and industry, and replacing monomers based on fossil resources by bio-based monomers is one of the key issues in polymer science. Lignin, among others, is a renewable feedstock, that can be used for the production of monomers for the preparation of bio-based polymers [1]. An interesting alternative bio-based building block which can be produced from lignin is vanillic acid or 4-hydroxy-3-methoxybenzoic acid [2]. In the present communication, our recent work on the synthesis of vanillic polyesters and their copolymers with poly(ethylene furanoate) will be presented [3]. Vanillic acid has been derivatized via a Williamson reaction to afford ω-hydroxyalkylene vanillic acids which were further polymerized. The thermal properties and crystallization behavior of the obtained polymers has been studied with differential scanning calorimetry, polarizing light microscopy and X-ray diffractometry. New insights, such as the enthalpy and entropy of fusion of 100% crystalline polyesters and the equilibrium melting temperature, will be presented. Additionally, the thermal stability of these polyesters has been measured by thermogravimetric analysis and the thermal decomposition mechanism has been studied by pyrolysis-gas chromatography/mass spectroscopy. Finally, the synthesis and characterization of novel poly(ethylene vanillate)-poly(ethylene furanoate) copolymers will be presented.

[1] Hillmyer, M.A. The promise of plastics from plants. Science 2017, 358, 868

[2] Fache, M.; Darroman, E.; Besse, V.; Auvergne, R.; Caillol, S.; Boutevin, B. Vanillin, a promising biobased building-block for monomer synthesis. Green Chem. 2014, 16, 1987

[3] Zamboulis, A.; Papadopoulos, L.; Terzopoulou, Z.; Bikiaris, D.N.; Patsiaoura, D.; Chrissafis, K.; Gazzano, M.; Lotti, N.; Papageorgiou, G.Z. Synthesis, Thermal Properties and Decomposition Mechanism of Poly(Ethylene Vanillate) Polyester, Polymers 2019, 11, 1672