Thiol-ene-acrylate Ternary Photosensitive Resins for DLP 3D Printing

Abstract

Acrylate-based photosensitive resins for digital light processing (DLP) 3D printing generally suffer from large volumetric shrinkage, insufficient functionality conversion and heterogeneous networks. Based on thiol-ene click chemistry, we developed a series of thiolene-acrylate ternary formulations and systematically studied the effects of each composition on the photopolymerization kinetics and thermomechanical properties. The ternary systems exhibit very low viscosity (< 0.15 Pa•s) and sufficient thermal storage stability. The mechanical properties of the networks can be adjusted by simply altering the components ratio. With optimal parameters, the thiol-ene-acrylate ternary system can be applied to DLP 3D printing to fabricate delicate objects.

Flexible Materials for High-Resolution 3D Printing of Microfluidic Devices with Integrated Droplet Size Regulation

“…Here, we spot three significant bands potentially providing information on the structural changes upon UV polymerization. The first band at approximately 3083 cm –1 refers to CH 2 stretching of the allyl group of TATATO that is only visible in the pure TATATO spectrum . In the UV-polymerized sample, the band is overlapping with aromatic CH bands from POEA as well as vibrations of the CH 2 stretches of the vinyl group and the −CH 2 group.…”

“…The first band at approximately 3083 cm −1 refers to CH 2 stretching of the allyl group of TATATO that is only visible in the pure TATATO spectrum. 65 In the UV-polymerized sample, the band is overlapping with aromatic CH bands from POEA as well as vibrations of the CH 2 stretches of the vinyl group and the −CH 2 group. Thus, this band and changes of it cannot be easily identified in the UV-cured sample.…”

“…The first cross-linker, E8413, is a highly viscous (35 000 cP at 60 °C) cross-linker consisting of an aliphatic urethane diacrylate diluted with 33% (w/w) isobornyl acrylate (IBOA) that are both miscible with POEA. E8413 was already used as a resin component for 3D-printing elastic materials ,− The second one, TATATO is a triallyl-functionalized cross-linker, which was used in thiolene-based thin-coatings , and DLP 3D-printing. − The third one, TPGDA is a low-viscous (15 cP at 25 °C) and transparent bifunctional acrylate, which was used as a base material for material jetting and for 3D printing of microfluidic valves by our group . Formulations consisting of TPGDA usually result in stiff objects, as shown in the preliminary studies of the mechanical properties of three resins containing different fractions of TPGDA and POEA (Figure S2).…”

Straightforward Manufacturing of 3D-Printed Metallic Structures toward Customized Electrical Components

“…This observation is consistent with previously reported thiolene-acrylate ternary resins for DLP 3D printing. 33 Thiolcontaining surfaces can immobilize metal ions (e.g., Cu, Ag) through chemical covalent bonds and intermolecular interactions, where immobilized metal ions can be utilized as active seeds on the surface and subsequently facilitate further deposition of metal layers via ELP. To quantitatively investigate the metal ion adsorption behaviors promoted by thiol−metal complexation, as-printed objects with various Di-PETMP contents were immersed into an aqueous Cu 2+ solution without a reducing agent for 2 h, and their XPS spectra were analyzed.…”

Development of Microdroplet Generation Method for Organic Solvents Used in Chemical Synthesis

“…However, swelling in these devices was caused by some organic solvents, such as acetone and dichloromethane, despite the application of long-term heat treatment to increase their chemical resistance. In addition, thiol-ene-based resin shrinks during the curing process and expands during heating [32,33], which lowers the accuracy of the channel pattern. Consequently, devices fabricated from physically stable materials with high chemical resistance such as silicon and glass are essential.…”