Sustainable dynamic crosslinked networks based on thiol–ene/thiol–anhydride click chemistry

Abstract

Photo‐cured coatings are attracting a lot of attention because they offer several advantages: they use less energy, release fewer harmful volatile organic compounds, require lower initial investment, and cure quickly even at room temperature. Recently, there has been an increase in the use of vegetable oils in these coatings. This is because vegetable oils are renewable, have low toxicity, are highly versatile, and their triglyceride structure can be easily integrated into the coating's structure. In this paper, linseed oil, an eco‐friendly vegetable oil known for its high reactivity due to the presence of a high degree of linolenic moieties, is used. First, it is epoxidized and then acrylated through a ring‐opening process with acrylic acid monomer. Furthermore, a monomer containing both thiol and carboxylic acid functional groups is prepared from 1,6‐hexanedithiol and maleic anhydride. Vegetable‐oil‐based crosslinked films are obtained by photoinitiated thiol–ene click chemistry from the acrylated linseed oil and bis‐thiol terminated thioester. The resulting films are then heated at 120 °C for 1 and 24 h. The thermally, spontaneous and catalyst‐free reversibility of thioester–anhydride bonds enables the reconfiguration of the crosslinked thermoset thiol–ene network. This dynamic rearrangement contributes to enhanced thermal, mechanical and physical properties of the material. Such a dynamic chemistry approach paves the way for the development of functional materials capable of reshaping and reprocessing. © 2026 Society of Chemical Industry.