Green Design of Renewable Dual-Curing Polymers with Self-Healing and Recyclable Networks for 3D Printing

Abstract

This work presents a green design approach for a novel class of dual-curing, self-healing polymers derived from vegetable oils for additive manufacturing. The polymer network is constructed from methacrylated and epoxidized monomers derived through environmentally friendly transformations, allowing for UV-curing radical polymerization followed by thermal curing via acid–epoxy reactions. The resulting materials exhibit self-healing behavior, supporting thermal reprocessing and chemical recycling via transesterification. Designed for circularity, polymers containing the vegetable oil derivatives─methacrylated and epoxidized─reached a biobased content of up to 98% and a biobased carbon content above 77%, far exceeding industry standards. The materials also display alkaline hydrolytic degradation, aligning with end-of-life strategies under a circular economy model. Dual-curing systems achieved an epoxy conversion of over 90% and gel contents above 97%, resulting in stable polymer networks suitable for reprocessing. The formulations were successfully processed using 3D printing platforms, producing well-defined structures despite viscosities exceeding the ideal printability window. The system containing the maleinized/methacrylated grapeseed oil and epoxidized castor oil showed the most favorable behavior, with lower overcuring and the lowest critical energy (37 mJ cm^– 2). Successful printing confirms the applicability of these systems.

Renewable dual-curing polymers from vegetable oils enable 3D printing, self-healing, and recyclability, offering a sustainable, circular alternative to photopolymer resins.