Sliding Dynamics of Ring Chain on a Rod-Coil Block Copolymer in Rotaxane
摘要
Rotaxanes are a class of mechanically interlocked polymers characterized by the sliding motion of ring molecules along a linear backbone. The dynamic behavior of a ring plays a critical role in determining its material properties. In this study, molecular dynamics simulations were performed to investigate the sliding dynamics of a ring on a rod-coil copolymer in rotaxane. We find that both the mean square displacement g3(t) and the diffusion coefficient D of the rings are influenced by the rod-to-coil length ratio α, the stretching degree μ of the coil block, and the ring size Nring. The mean square displacement g3(t) shows sub-diffusive behavior at intermediate time scales owing to the heterogeneous backbone. The diffusion coefficient exhibits nonmonotonic dependence on α and μ. D first decreased and then increased as a increased, indicating that the ring diffused faster on more homogeneous copolymer chains. D increases with μ under a moderate stretching degree of the coil block, but decreases under near full extension, which demonstrates that the dynamics of the ring are governed by a competition between the chain flattening and the coil block’s fluctuation. Similarly, ring size Nring has a nonmonotonic influence on the diffusion coefficient D. This study provides molecular-level insights into the manipulation of sliding dynamics in rod-coil-based rotaxanes, thereby offering a theoretical basis for the design of functional slide-ring materials through topological control.