Chemical and Mechanical Tunability of 3D-Printed Dynamic Covalent Networks Based on Boronate Esters
Lindsay L. Robinson, Jeffrey L. Self, Alexander D. Fusi, Morgan W. Bates, Javier Read de Alaniz, Craig J. Hawker, Christopher M. Bates, and Caitlin S. Sample
ACS Macro Lett. 2021, 10, 7, 857–863
Abstract: As the scope of additive manufacturing broadens, interest has developed in 3D-printed objects that are derived from recyclable resins with chemical and mechanical tunability. Dynamic covalent bonds have the potential to not only increase the sustainability of 3D-printed objects, but also serve as reactive sites for postprinting derivatization. In this study, we use boronate esters as a key building block for the development of catalyst-free, 3D-printing resins with the ability to undergo room-temperature exchange at the cross-linking sites. The orthogonality of boronate esters is exploited in fast-curing, oxygen-tolerant thiol–ene resins in which the dynamic character of 3D-printed objects can be modulated by the addition of a static, covalent cross-linker with no room-temperature bond exchange. This allows the mechanical properties of printed parts to be varied between those of a traditional thermoset and a vitrimer. Objects printed with a hybrid dynamic/static resin exhibit a balance of structural stability (residual stress = 18%) and rapid exchange (characteristic relaxation time = 7 s), allowing for interfacial welding and postprinting functionalization. Modulation of the cross-linking density postprinting is enabled by selective hydrolysis of the boronate esters to generate networks with swelling capacities tunable from 1.3 to 3.3.