Uniaxial Stretching-Induced Alignment of Carbon Nanotubes in Cross-Linked Elastomer Enabled by Dynamic Cross-Link Reshuffling

The fascinating properties of carbon nanotubes (CNTs) make them highly promising in fabricating polymer composites. Yet, the property enhancements of polymer/CNTs composites remain far behind the theoretical predictions. A critical issue to resolve this dilemma is to align CNTs in polymer matrices. Thus far, the state of art approaches to create CNT alignment either require complicated preparation processes and specific apparatuses, or is limited to thermoplastic polymers. Here, inspired by the network rearrangement ability of vitrimer in the solid state, we bring forth a facile methodology to align CNT in covalently cross-linked polymers by uniaxially stretching dynamic. Specifically, dynamic boronic ester bond-cross-linked epoxidized natural rubber/CNTs vitrimer composites with randomly dispersed CNTs are prepared, which are able to rearrange the network topologies and release stress at elevated temperatures through boronic ester transesterifications. The alignment of CNTs is performed by the uniaxial stretching of the composites and subsequent cross-link reshuffling at elevated temperatures, which results in anisotropic composites with remarkably enhanced mechanical properties and reduced electrical conductivity along the stretching direction. Furthermore, the mechanical properties of the composites can be readily adjusted by changing the applied strain, relaxation time and temperature due to the modulated CNT alignment degree. With this example, we envisage that this work offers a conceptual and facile approach to align anisotropic fillers in covalently cross-linked polymers.