Ferulic acid-based renewable esters and amides-containing epoxy thermosets from wheat bran and beetroot pulp: Chemo-enzymatic synthesis and thermo-mechanical properties characterization

• Ferulic acid, present in rice/wheat bran, bagasse and beetroot pulp, is used as starting material.
• Aromatic epoxies are synthesized from ferulic acid using a chemo-enzymatic process.
• Epoxy networks were synthesized by reactions of the epoxies with diamines.
• Cured biobased epoxies were compared to DGEBA.
• Thermo-mechanical properties can be easily tailored by adjusting epoxies structure.

In this study, ferulic acid – a natural phenolic acid present in bagasse, wheat and rice brans, and beetroot pulp – was used as renewable starting material to prepare new biobased epoxy precursors. This biobased building block was first esterified then reduced to provide ethyl dihydroferulate which was then trans-esterified/amidified with biobased diols, triol and diamines. Immobilized Candida antarctica (aka CAL-B or Novozyme 435®) was used to perform the solvent-free-transesterification/amidation under mild conditions. The phenolic architectures synthesized were then glycidylated using a TEBAC-mediated procedure to afford four biobased epoxy precursors – with various linker structures between the ferulic units – which were then cured with conventionnal and biobased diamine curing agents. The thermal and thermomechanical properties of the thermosets prepared were assessed by TGA, DSC and DMA to highlight the influence of the linker configuration (aliphatic vs cycloaliphatic), that of the epoxy functionality (di vs tri), and that of the nature of the function used for coupling ferulic units (ester vs amide) on the thermosets properties. Analyses of these thermosets revealed glass transition temperatures ranging from 32 to 85 °C and high thermal stabilities around 300 °C. The mechanical behavior of the biobased thermosets proved equivalent to that of the DGEBA-IPDA reference sytem at low temperatures (up to 40–100 °C depending on the epoxy precursor and diamine).

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