Chemical and Mechanical Tunability of 3D-Printed Dynamic Covalent Networks Based on Boronate Esters

ACS Macro Lett. 2021 Jul 20;10(7):857-863. doi: 10.1021/acsmacrolett.1c00257. Epub 2021 Jun 23.

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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Esters*
  • Materials Testing
  • Printing, Three-Dimensional*
  • Resins, Plant

Substances

  • Esters
  • Resins, Plant