Nearly 90% of thermosets are produced from petroleum resources, they have remarkable mechanical characteristics, are chemically durable, and dimensionally stable. However, they can contribute to global warming, depletion of petroleum reserves, and environmental contamination during manufacture, use, and disposal. Using renewable resources to form thermosetting materials is one of the most crucial aspects of addressing the aforementioned issues. Vanillin-based raw materials have been used in the industrial manufacturing of polymer materials because they are simple to modify structurally. Conversely, traditional thermosetting materials as a broad class of high-molecular-weight molecules are challenging to heal, decompose and recover owing to their permanent 3-D crosslinking network. Once the products are damaged, recycling issues could arise, causing resource loss and environmental impact. It could be solved by inserting dynamic covalent adaptable networks (DCANs) into the polymer chains, increasing product longevity, and minimizing waste. It also improves the attractiveness of these products in the prospective field. Moreover, it is essential to underline that increasing product lifespan and reducing waste is equivalent to reducing the expense of consuming resources. The detailed synthesis, reprocessing, thermal, and mechanical characteristics of partly and entirely biomass thermosetting polymers made from vanillin-modified monomers are covered in the current work. Finally, the review highlights the benefits, difficulties, and application of these emerging vanillin-modified vitrimers as a potential replacement for conventional non-recyclable thermosets.

Biobased epoxy vitrimers have reached intense interest in recent decades. The triggerable reverse bonds can be introduced into these crosslinked epoxy vitrimers through epoxy resins or hardeners. This study synthesized two imine hardeners, such as vanillin-butanediamine (V-BDA) and vanillin-hexanediamine (V-HDA), using biobased vanillin, butanediamine, and hexanediamine and their chemical structures were ensured by FTIR, ¹HNMR, ¹³CNMR, and TOF-MS. The two novel hardeners were used to cure epoxy resins, rendering vitrimers with good reprocessability, self-healing, recyclability, and solvent resistance due to the reversible imine bonds. The flexural strengths and modulus of these cured resins were consistent with those of epoxy resins that were hardened with traditional amine-based hardeners. The cured resins maintained 100% of their T_g and flexural properties after being reprocessed up to three times. It was revealed that the cured epoxy vitrimers could be degraded entirely in a particular acidic solution capable of bond-exchanging reactions within 12 h at 50 ᵒC, allowing the thermoset matrix to be chemically recycled and the monomers regenerated. This versatile recyclability, combined with the use of fully biobased feedstocks to prepare the hardeners, provides an attractive approach to help achieve a sustainable circular composite economy.

Epoxy thermosets need to be designed for simple recycling and biomass resource utilization in order to be fully sustainable building materials. The development of covalent adaptive networks (CANs) using adaptive covalent chemistry (ACC) may be helpful in this regard. Several reversible covalent bonds are incorporated into the epoxy polymer to overcome the challenge of reprocessability or recyclability, degradability and self-healability. The imine bond, also referred to as the Schiff base, is one of the reversible covalent bonds that can participate in both associative and dissociative reactions. This opens up possibilities for mechanical and chemical recycling as well as self-healing. This review summarises the progress related to the synthesis and mechanical and thermal properties of epoxy thermosets based on reversible imine bonds derived from different sustainable resources over the past few decades. The feedstocks, physical and thermal properties, recycling conditions, degradability and self-healability of the biomass epoxy thermosets are addressed along with the main obstacles, prospective improvements and potential applications.