Generic Method to Create Segregated Structures toward Robust, Flexible, Highly Conductive Elastomer Composites

Electrically and thermally conductive polymer composites are extensively used in our daily life. It is of great significance to fulfill the conductivity requirement while maintaining desirable mechanical performance. An efficient solution to achieve this goal is to construct segregated structures in polymer composites by confining fillers into the interstitial areas among polymer domains. Thus far, it still remains a challenge to create segregated structures in cross-linked polymeric networks. Herein, we report a facile methodology to construct segregated structures in sulfur-cured rubbers using an industrially accessible process toward robust, flexible, highly conductive elastomer composites. Specifically, natural rubber granules (NR-RGs) with reactive di- and polysulfides on the surface are fabricated and then mixed with NR gum, carbon nanotubes (CNTs), and curing additives, followed by compression molding to yield two-phase separate composites. In the composites, CNTs are selectively dispersed in the continuous NR phase due to the volume exclusion effect caused by the separate NR-RG phase, leading to overwhelming electrical conductivity compared to the counterparts with randomly dispersed CNTs. In addition, NR-RGs can serve as novel reinforcement for NR, imparting the composites with remarkably improved modulus and retained stretchability. The simultaneously improved electrical conductivity and mechanical properties are due to the strong interfacial adhesion between the NR matrix and NR-RGs, as the di- and polysulfides on the surface of NR-RGs can participate in the cross-linking reactions of NR gum and enable the establishment of covalent bonding across the interfaces. The universality of this approach in preparing segregated composites with a combination of high conductivities and robust mechanical properties is demonstrated using other diene rubbers as the matrix and boron nitride as the filler.