Valorisation of Chitosan Natural Building Block as a Primary Strategy for the Development of Sustainable Fully Bio-Based Epoxy Resins.

The non-toxic and biodegradable nature of chitosan makes it a valuable resource offering promising opportunities in the development of bio-based materials with enhanced mechanical and thermal properties. In this work, the combination of epoxidized linseed oil, oxalic or citric acids, and chitosan (CHI) as a curing accelerator presents an attractive strategy to create bio-based and sustainable thermosetting materials. This article aims to provide a comprehensive exploration of the systems reactivities, characteristics, and performance evaluation of the designed bio-thermosets. Both the nature of the two carboxylic acids and the presence of chitosan are shown to have a big impact on the thermomechanical properties of the developed networks. While oxalic acid favours the formation of elastic networks, with low Tg values (increasing with CHI content between 0.7 and 8.5 °C) and relatively low Young's modulus (~2.5 MPa), citric acid promotes the formation of very dense networks with lower mass of the segments between the crosslinks, having 20 times higher Tg values (from 36 to 45 °C) and ~161 times higher Young's modulus (from 94 MPa up to 404 MPa in these systems). The CHI has a strong impact on the curing reaction and on the overall properties, by increasing the materials' performance.

High content chitosan-based materials with high performance properties.

Chitosan is a valuable biopolymer with a great potential to be used in the design of sustainable materials. Its use typically requires converting the solid powder into a quite dilute solution by disrupting the hydrogen bonding between primary amine and hydroxyl groups. In this work we show that chitosan can be reacted with a tris-aromatic tris-epoxy monomer, generating thermoset materials. The design of the new structures adopted a strategy where the chitosan was mixed in its solid form, to avoid the use of solvents and additional processing steps. A combined polymerization mechanism was proposed, including growth chain polymerization and polyaddition. The obtained materials containing different epoxy/chitosan weight percentage ratios show outstanding properties: high glass transition ~230 °C, high Young's modulus ~2116 and 1716 MPa, tensile strength of ~35 MPa and T5% ~ 300 °C.