Thiol‐yne 3D Printable Polymeric Resins for the Efficient Removal of a Model Pollutant from Waters

Abstract

A new 3D printable resin formulation is developed and optimized from commercially available thiol (pentaerythritol tetrakis(3-mercaptopropionate); PETMP) and alkyne (3-butyn-1-ol; BA) monomers. Printed objects are characterized by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The extraction efficiency of the printed thiol-yne device is then investigated using a model dye -malachite green (MG). The results displayed excellent dye removal efficiency with > 95% MG removed within 5 min. The 3D-printed devices are reusable and show 100% removal over six cycles after washing with deionized water and methanol. The presence of surface hydroxyl groups derived from the BA monomer is shown to enhance dye adsorption in comparison to control materials. The printing procedure and resin formulation are robust and consistent when devices from different resin batches are compared for MG dye removal. The thiol-yne 3D printed devices demonstrated excellent dye removal (> 99%) from water samples collected from a tap and a nearby river source. The successful development of this resin provides a new thiol-yne-based resin system for stereolithography (SLA) 3D printing for the removal of organic dyes from wastewater and presents a potential for broad applications in water treatment.

Biobased Transparent Thiol–Ene Polymer Networks from Levoglucosan

“…Diallyl monomer (LGA-DA) and triallyl monomer (LGA-TA) were synthesized by the reaction of LGA with allyl bromide. Targeting specific diallyl and triallyl functionalities was selected through careful stoichiometric regulation and was purified via flash chromatography prior to 1 H and 13 C NMR analyses (Supporting Information (SI) Figure S2). The selective alkylation on the hydroxyl at C2 and C4 was supported by analysis of the 2D NMR.…”

“…The crude monomers were purified via flash chromatography and their structures were supported by 1 H and 13 C NMR.…”

“…For each print, the initial three layers were provided with longer exposure times (20 s) to ensure their adherence to the printing platform. 12,13 ■ MECHANICAL ANALYSIS Tensile testing of cured polymer samples was performed in accordance with ASTM: D638−14. For tensile samples, the dog-bone tabbed ends were used.…”

“…3D printing experiments were performed on a benchtop stereolithography (SLA) printer (Elegoo, Mars 3 4K). For each print, the initial three layers were provided with longer exposure times (20 s) to ensure their adherence to the printing platform. , …”

“…This is due to their high shape stability, solvent resistance, and thermal stability. , Currently, it is standard to synthesize thermosetting materials from petroleum-derived compounds . As a result, biomass-derived materials present as a possible sustainable alternative for the production of thermoset materials. − Indeed, biomass-derived compounds are being increasingly incorporated into thermosetting systems across a wide range of applications, including coatings, adhesives, inks, electronics, and three-dimensional (3D) printing. − …”