Photocurable Glycerol- and Vanillin-Based Resins for the Synthesis of Vitrimers

Abstract

In this study, photocurable resins based on glycerol and vanillin were designed, synthesized, and applied to digital light processing three-dimensional (3D) printing and vitrimeric abilities such as shape-memory, self-healing, and recyclability have been investigated. First, photocurable resins were prepared and synthesized by combining renewable resources and photocuring as an environmentally friendly strategy for the synthesis of vitrimers. Afterward, the most suitable resin for optical 3D printing was selected by photorheometry, and the thermal and mechanical properties of the resulting polymers were tested. Furthermore, by activating dynamic transesterification reactions at elevated temperatures, the photocured polymer exhibited self-healing, recyclability, and shape-memory properties. The vitrimer with a weight ratio of 8:2 of glycerol- and vanillin-based monomers demonstrated a welding efficiency of tensile strength up to 114.12%, 75% recyclability by alcoholysis, and shape-memory properties above and below two glass transition temperatures.

Biobased and degradable thiol–ene networks from levoglucosan for sustainable 3D printing

“…To mitigate the production and accumulation of 3D printed plastic waste, it is crucial that 3D printing resins that are both renewably sourced and degradable are developed. 19 Renewable feedstocks such as natural phenolics (eugenol, vanillin, guaiacol), 21 succinic and itaconic acid, 22 glycerol, 23 and vegetable oils, 24 have been used to create 3D printing resins via acrylation, typically resulting in nondegradable carbon–carbon bond backbones after free-radical crosslinking. Due to its many advantages, thiol–ene photopolymerization is also gradually being explored in additive manufacturing resins.…”

Renewable Photopolymers: Transformation of Biomass Resources into Value-Added Products Under Light

“…194 2-Hydroxy-2-phenoxypropyl acrylate and DGEVADM (Scheme 22B) were formulated as photocurable resins with Zn(acac) 2 as a transesterification catalyst. 195 Following UV curing, the dynamic networks were capable of swiftly experiencing a rearrangement in their network topology upon thermal activation due to the abundance of hydroxyl and ester groups.…”

“…A noteworthy antimicrobial and antifungal activity was observed in the photocured film of VD. , The activity of VDM-based films against microorganisms was comparatively lower, possibly due to the decreased concentration of carbonyl groups, which were known to have a favorable impact on the antimicrobial potency of compounds . 2-Hydroxy-2-phenoxypropyl acrylate and DGEVADM (Scheme B) were formulated as photocurable resins with Zn­(acac) 2 as a transesterification catalyst . Following UV curing, the dynamic networks were capable of swiftly experiencing a rearrangement in their network topology upon thermal activation due to the abundance of hydroxyl and ester groups.…”

Bio-based vitrimers from divanillic acid and epoxidized soybean oil

“…Among the biomass-derived monomers, vanillin and epoxidized soybean oil (ESO) have been extensively studied as building blocks for bio-based vitrimers or other dynamically crosslinked polymers. 28,[46][47][48][49][50][51][52][53][54] This is because vanillin has a relatively simple chemical structure among naturally occurring aromatics, and ESO is a low-cost, industrially produced epoxy. In many previous works, some petrochemicals or multiple reaction steps were still necessary to introduce exchangeable moieties (e.g., vinylogous urethane and imine bonds) into the monomers.…”