Two‐Step 3 D‐Printing Approach toward Sustainable, Repairable, Fluorescent Shape‐Memory Thermosets Derived from Cellulose and Rosin

Efficiently converting biomass into multifunctional polymerized materials is a challenge to effect high-valued utilization of biomass resources. A two-step 3 D-printing approach has been developed to fabricate a class of robust, fluorescent shape-memory thermosets from cellulose and rosin-based photosensitive 3 D-printing resin solution. The stereolithography 3 D printing was first performed to form the first crosslinked network by UV-induced chain-growth polymerization, which fixed the shape of thermoset. Subsequently, isocyanate was applied to react with hydroxy in the monomer to form the second crosslinked network by thermally induced step-growth polymerization. The formation of a dual-cure network, leading to phase separation and increased crosslinking density, could greatly improve the mechanical and thermal properties of 3 D-printed thermosets and endow them with thermally triggered shape-memory properties and excellent repairability. The 3 D-printed thermosets are found to have strong luminescence resulting from aggregation-induced emission originating from rosin. In addition, these 3 D-printed thermosets could degrade in the presence of NaOH aqueous solution and in situ achieved a range of flexible conductive hydrogels that have important potential application in the flexible electronic materials and smart photoelectric materials.