Mechanically interlocked polymers in dilute solution under shear and extensional flows: A Brownian dynamics study

Abstract

Mechanically interlocked polymers (MIPs) are a class of polymer structures in which the components are connected by mechanical bonds instead of covalent bonds. We measure the single-molecule rheological properties of polyrotaxanes, daisy chains, and polycatenanes under steady shear and steady uniaxial extension using coarse-grained Brownian dynamics simulations with hydrodynamic interactions. We obtain key rheological features, including tumbling dynamics, molecular extension, stress, and viscosity. By systematically varying structural features, we demonstrate how MIP topology governs flow response. Compared to linear polymers, all three MIP architectures exhibit enhanced tumbling in shear flow, weaker shear thinning, and lower normal stress differences in extensional flow. While polyrotaxanes show higher shear and extensional viscosities, polycatenanes and daisy chains have lower viscosities. In extensional and shear flows, MIPs typically extend more in the flow direction and at weaker flow strengths than linear polymers. These effects arise from the mechanically bonded rings in MIPs, which expand the polymer profile in the gradient direction and increase backbone rigidity due to ring–backbone repulsions. This study provides key insights into MIP flow properties, providing the foundation for their systematic development in engineering applications.