From Glassy Plastic to Ductile Elastomer: Vegetable Oil-Based UV-Curable Vitrimers and Their Potential Use in 3D Printing

Abstract

Current UV-curable resins based on acrylate or methacrylate monomers are mostly derived from nonrenewable petroleum feedstocks, and the cured resins are not easily repairable or reprocessable due to the stable cross-linked network. In this work, bio-based UV-curable dimethacrylate compounds are synthesized via reaction of the vegetable oil-derived dimer acid with glycidyl methacrylate. The length and flexibility of the chain segment between the two methacrylate groups are manipulated to tune the properties of the cross-linked polymer materials. The UV-cured materials exhibit a tensile strength of up to 9.2 MPa and an elongation at break of up to 66.4%. At elevated temperatures (>160 °C), the thermally induced dynamic transesterification reaction (DTER) between hydroxyl groups and ester bonds in the network structure provides repairability to the material. Use of the UV resin for three-dimensional (3D) printing is demonstrated. The printed objects exhibit unique welding and shape-changing properties owing to the thermally induced DTER. This work integrates the concepts of UV curing, vitrimer preparation, 3D printing, and bio-based polymers, demonstrating a feasible approach for the sustainable design of polymer materials.

Rubber Seed Oil-Based UV-Curable Polyurethane Acrylate Resins for Digital Light Processing (DLP) 3D Printing

“…As the content of HEA increased from 10 to 40%, the tensile strength and tensile modulus of the cured RSO-PUA/HEA materials dropped from the maximum values of 16.3 MPa and 330.6 MPa to 5.4 MPa and 113.3 MPa, respectively. The decreased νe (showed by the DMA above) most likely accounts for the variation in ductility and stiffness [41]. The tensile strength of the pure RSO-PUA sample was similar to that of RSO-PUA with polyfunctionality diluent (TEGDA and TMPTA), which may due to the carbon-carbon double bond functionality of the RSO-PUA oligomer (2.27 per aliphatic acid) and polyfunctional dilu-…”

“…The C gel is the insoluble fraction representing the degree of cross-linking of the UVcured RSO-PUA films, and the data was assessed with the aid of Soxhlet extraction [41]. The values of C gel are listed in Table 1.…”

Bioelastomers: current state of development

“…The interaction between the hydroxyl and ester groups in the network displayed a repairable and shape-changing character due to the presence of a thermally induced dynamic transesterification reaction (DTER). 202…”

Progress in Utilizing Dynamic Bonds to Fabricate Structurally Adaptive Self‐Healing, Shape Memory, and Liquid Crystal Polymers

“…In addition to reprogramming of the dynamic SMPs, 3D printing [139][140][141][142][143][144][145][146][147] and interface welding [148][149][150][151][152] of dynamic SMPs are also effective methods to enrich the deformation behaviors. For instance, Ji and coworkers have prepared an epoxyacid-derived vitrimer, where the transesterification can be triggered at a temperature above 160 °C in the presence of the catalyst, endowing the material with dynamic properties (Figure 11a).…”