Ferulic acid-based renewable esters and amides-containing epoxythermosets from wheat bran and beetroot pulp: Chemo-enzymaticsynthesis and thermo-mechanical properties characterization

• Published in: Industrial Crops and Products
• Main Authors: Menard, Raphaël, Caillol, Sylvain, Allais, Florent
• Other Authors: Centre des Matériaux des Mines d'Alès (C2MA), IMT - MINES ALES (IMT - MINES ALES), Institut Mines-Télécom Paris (IMT)-Institut Mines-Télécom Paris (IMT), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Génie et Microbiologie des Procédés Alimentaires (GMPA), Institut National de la Recherche Agronomique (INRA)-AgroParisTech, Region Champagne-Ardenne; Conseil General de la Marne and Reims Metropole
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2017
• Subjects: Non-feed product valorization; Ferulic acid; Biobased polyol; Chemo-enzymatic process; Fully biobased thermosets; Tunable thermo-mechanical properties; [CHIM.POLY]Chemical Sciences/Polymers; Antarc*; Antarctica
• Online Access: https://hal.science/hal-01382326; https://doi.org/10.1016/j.indcrop.2016.10.016

International audience 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 transesterified/amidified with biobased diols, triol and diamines. Immobilized Candida antarctica (aka CAL-B or Novozyme 435 (R)) 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 degrees C and high thermal stabilities around 300 degrees 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 degrees C depending on the epoxy precursor and diamine).