Exploiting the Carbon and Oxa Michael Addition Reaction for the Synthesis of Yne Monomers: Towards the Conversion of Acrylates to Biocompatible Building Blocks

Abstract

Herein, we demonstrated the synthesis of multifunctional alkyne building blocks from commercially available acrylate monomers exploiting the carbon and oxa Michael addition reaction. These compounds were obtained in decent yields and show similar or even higher photoreactivity than the initial acrylates. Importantly, selected thiol‐yne formulations can be processed by stereolithography and significantly outperform the corresponding acrylate in terms of modulus and toughness. The high compatibility of such cured materials with osteosarcoma cells makes these photopolymers interesting for hard tissue engineering.

3D Printing of Thiol‐Yne Photoresins through Visible Light Photoredox Catalysis

“…Currently, most reported research of thiol‐yne 3D printing have been performed under 405 nm irradiation [9–11,15] . Very few studies have extended into the visible region of the spectrum for DLP and Stereolithography (SLA) 3D printing with thiol‐ynes [12] .…”

“…At present, the implementation of thiol‐yne photoresin for photo activated 3D printing is still in its infancy. Griesser's group reported a biocompatible thiol‐yne derived formulation, and subsequently utilized it in a DLP 3D printer ( λ max =405 nm), fabricating structures with an accuracy of 100 × 100 μm which are attractive for hard tissue engineering [9] . In another example, Chiappone's group utilized thiol‐yne formulations for fabricating 3D objects ( λ max =405 nm) with controllable surface functionality (either alkyne or thiol groups) by varying the relative stoichiometric ratio of the two components [10] .…”

Fast Hydrolytically Degradable 3D Printed Object Based on Aliphatic Polycarbonate Thiol‐Yne Photoresins

“…[ 28,36,44–46 ] All of these advantages make thiol‐yne based photoresins valuable for vat polymerization‐based 3D printing. [ 32,36,47 ] To investigate the 3D printability of the degradable AT series formulations, we employed a commercial bottom‐up DLP printer (Anycubic Photon, Shenzhen Anycubic Technology Co., Ltd., China). The printing was carried out in a layer‐by‐layer fashion set by digital slicing software with predefined parameters (the number of bottom layer, layer thickness, exposure time, and off time).…”

“…The 3D structures of square pyramid, hollow cube, hollow square pyramid, and complex C 60 molecule were all successfully fabricated with comparable resolution to the reported nondegradable thiol‐yne based DLP printing research work. [ 32,36,47 ] Lastly, all 3D printed parts were subjected to UV post curing process to ensure the complete conversion of functional groups (see Figure S8 in the Supporting Information).…”