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

Abstract

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.

Phosphorescent bio-based resin for digital light processing (DLP) 3D-printing

“…22 Only a few examples of publications in the recent literature with strong effort toward the implementation of biomasses in stereolithography can be found, but the biomass loading into these resins still remains very low (<15%). [23][24][25] Therefore, there is a need for the implementation of biobased compounds into the formulations for 3D printing to the final consumer. This would allow the overall reduction of the carbon footprint of 3D printing technologies as a green and sustainable approach to rapid prototyping.…”

Sustainable Photopolymers in 3D Printing: A Review on Biobased, Biodegradable, and Recyclable Alternatives

“…More recently, repairable 3D printed thermosets with a dual‐cure network have been fabricated by a two‐step strategy. [ 88 ] SLA 3D printing of photocurable resins derived from rosin and cellulose was performed to achieve a crosslinked thermoset. Next, heating triggered the reaction between hydroxyl and isocyanate groups, forming the dual‐cure network.…”

UV-Curable Bio-Based Polymers Derived from Industrial Pulp and Paper Processes

“…Lu et al [ 94 ] developed a two-step 3D-printing approach, to prepare a thermoset derived from cellulose and rosin, by means of UV-induced chain-growth polymerization and step-growth polymerization. They used the rosin to create a novel acrylate monomer named dehydroabietic acid glycidyl methacrylated (DAGMA).…”