3D‐Printing of Poly(arylene ether sulfone)s: Functional High‐Performance Polymers for Vat Photopolymerization

Abstract

Vat photopolymerization (VP) is an advanced additive manufacturing (AM) platform that enables production of intricate 3D monoliths that are unattainable with conventional manufacturing methods. In this work, modification of amorphous poly(arylene ether sulfone)s (PSU) allows for VP printing. Post-polymerization telechelic functionalization with acrylate functionality yielded photocrosslinkable PSUs across a molecular weight range. 1 H NMR spectroscopy confirms chemical composition and quantitative acrylate functionalization. Addition of diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) photoinitiator to 30 wt% PSU solutions in NMP provides a photocurable composition. However, subsequent photorheological studies elucidate rapid photodegradation of the polysulfone main chain, which is especially apparent in high M n (15 kg mol −1 ) PSU formulations. UV-light intensity and wavelength range are altered to reduce degradation while allowing for efficient crosslinking. The addition of 0.5 wt% of avobenzone photoblocker produces an ill-defined structure with 6 kg mol −1 PSU. For higher molecular weights (>12 kg mol −1 ), solutions with a low molar mass reactive diluent, i.e., trimethylolpropane triacrylate, enable the printing of an organogel with a storage modulus (>10 5 Pa) sufficient for vat photopolymerization. Employing multicomponent solutions provide well-defined parts with complex geometries through vat photopolymerization.

Additive Manufacturing of High-Temperature Thermoplastic Polysulfone with Tailored Microstructure via Precipitation Printing

“…Besides material extrusion, researchers also incorporated solvent-cast three-dimensional (3D) printing for PSU and PSU-based composites, but internal pores (pore size ranges from 0.3 to 2.8 μm) existed throughout the printed samples due to the rapid evaporation of solvents . As for the powder bed fusion and vat photopolymerization methods, some preliminary works on processing free-flowing PSU powder and synthesizing photocurable PSU inks have been done, , but the mechanical properties of printed PSU samples have not been studied. Thus, additive manufacturing of PSU with high mechanical properties and low anisotropy remains an unexplored and challenging research topic.…”