Threading through Macrocycles Enhances the Performance of Carbon Nanotubes as Polymer Fillers

[Image: see text] In this work, we study the reinforcement of polymers by mechanically interlocked derivatives of single-walled carbon nanotubes (SWNTs). We compare the mechanical properties of fibers made of polymers and of composites with pristine SWNTs, mechanically interlocked derivatives of SWNTs (MINTs), and the corresponding supramolecular models. Improvements of both Young’s modulus and tensile strength of up to 200% were observed for the polystyrene–MINT samples with an optimized loading of just 0.01 wt %, while the supramolecular models with identical chemical composition and loading showed negligible or even detrimental influence. This behavior is found for three different types of SWNTs and two types of macrocycles. Molecular dynamics simulations show that the polymer adopts an elongated conformation parallel to the SWNT when interacting with MINT fillers, irrespective of the macrocycle chemical nature, whereas a more globular structure is taken upon facing with either pristine SWNTs or supramolecular models. The MINT composite architecture thus leads to a more efficient exploitation of the axial properties of the SWNTs and of the polymer chain at the interface, in agreement with experimental results. Our findings demonstrate that the mechanical bond imparts distinctive advantageous properties to SWNT derivatives as polymer fillers.