Engineering Segregated Structures in a Cross-Linked Elastomeric Network Enabled by Dynamic Cross-Link Reshuffling

Construction of segregated structures in polymer composites is an efficient way to improve the electrical conductivity and reduce the percolation threshold by confining conductive fillers into the interstitial areas between polymer domains. Yet, it remains a great challenge to engineer segregated structures into thermosets as the cross-linked structure prohibits the "sintering" of polymer domains into a coherent material. Thus far, the state of art approaches to create segregated network in cross-linked polymers involve tedious procedures and are limited to latex mixing technology. Here, inspired by solid state plasticity of vitrimers, we present a simple method to create segregated structures in covalently cross-linked networks by compression molding of conductive filler-coated vitrimer granules. Specifically, dynamic boronic ester-cross-linked styrene–butadiene rubber vitrimers was ground into granules and then mechanically mixed with carbon nanotubes (CNTs) to coat CNTs onto vitrimer granules, followed by hot-press molding. During the molding process, the transesterifications of boronic esters enable cross-linked granules to adhere together through molecular bonding, and the high viscosity of granules forces CNTs to selectively localize at their boundary region. As a result, coherently segregated composites with an ultralow percolation threshold, good flexibility, and healing capability are obtained. With this example, we envisage that this work provides a conceptual method to create segregated structures in cross-linked polymers.