Super-soft elastomers derived from bottlebrush polymers show promise as advanced materials for biomimetic tissue and device applications, but current processing strategies are restricted to simple molding. Here, we introduce a design concept that enables the three-dimensional (3D) printing of super-soft and solvent-free bottlebrush elastomers at room temperature. The key advance is a class of inks comprising statistical bottlebrush polymers that self-assemble into well-ordered body-centered cubic sphere phases. These soft solids undergo sharp and reversible yielding at 20°C in response to shear with a yield stress that can be tuned by manipulating the length scale of microphase separation. The addition of a soluble photocrosslinker allows complete ultraviolet curing after extrusion to form super-soft elastomers with near-perfect recoverable elasticity well beyond the yield strain. These structure-property design rules create exciting opportunities to tailor the performance of 3D-printed elastomers in ways that are not possible with current materials and processes.

Wearable electronics and biointerfacing technology require materials that are both compliant and conductive. The typical design strategy exploits polymer composites containing conductive particles, but the addition of a hard filler generally leads to a substantial increase in modulus that is not well-matched to biological tissue. Here, we report a new class of supersoft, conductive composites comprising carbon nanotubes (CNT) embedded in bottlebrush polymer networks. By virtue of the bottlebrush polymer architecture, these materials are several orders of magnitude softer than comparable composites in the literature involving linear polymer networks. For example, a CNT content of 0.25 wt % yields a shear modulus of 66 kPa while maintaining a typical conductivity for a CNT composite (ca. 10^-2 S/m). An added benefit of this bottlebrush matrix chemistry is the presence of dynamic polyester bonds that facilitate thermal (re)processing. This unique strategy of designing soft composites provides new opportunities to tailor the structure and properties of sustainable advanced materials.