Designing Nanostructured 3D Printed Materials by Controlling Macromolecular Architecture

Nanostructured polymeric materials play important roles in many advanced applications, however, controlling the morphologies of polymeric thermosets remains a challenge. This work uses multi‐arm macroCTAs to mediate polymerization‐induced microphase separation (PIMS) and prepare nanostructured materials via photoinduced 3D printing. The characteristic length scale of microphase‐separated domains is determined by the macroCTA arm length, while nanoscale morphologies are controlled by the macroCTA architecture. Specifically, using 2‐ and 4‐ arm macroCTAs provides materials with different morphologies compared to analogous monofunctional linear macroCTAs at similar compositions. The mechanical properties of these nanostructured thermosets can also be tuned while maintaining the desired morphologies. Using multi‐arm macroCTAs can thus broaden the scope of accessible nanostructures for extended applications, including the fabrication of actuators and potential drug delivery devices.