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DOE OSTI · 1770325

Dynamics of poly[n]catenane melts

Rauscher, Phillip M.·Schweizer, Kenneth S.·Rowan, Stuart J.·de Pablo, Juan J.
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Abstract

Inspired by advances in the chemical synthesis of interlocking polymer architectures, extensive molecular dynamics simulations have been conducted to study the dynamical properties of poly[n]catenanes-polymers composed entirely of interlocking rings-in the melt state. Both the degree of polymerization (number of links) and the number of beads per ring are systematically varied, and the results are compared to linear and ring polymers. Herein, a simple Rouse-like model is presented, and its analytical solution suggests a decomposition of the dynamics into "ring-like" and "linear-like" regimes at short and long times, respectively. In agreement with this picture, multiple sub-diffusive regimes are observed in the monomer mean-squared-displacements even though interchain entanglement is not prevalent in the system. However, the Rouse-type model does not account for the topological effects of the mechanical bonds, which significantly alter the dynamics at intermediate length scales both within the rings and at the chain segment scales. The stress relaxation in the system is extremely rapid and may be conveniently separated into ring-like and linear-like contributions, again in agreement with the Rouse picture. However, the viscosity has a non-monotonic dependence on the ring size for long chains, which disagrees strongly with theoretical predictions. This unexpected observation cannot be explained in terms of chain disentanglement and is inconsistent with other measures of polymer relaxation. Possible mechanisms for this behavior are proposed and implications for materials design are discussed.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYDiffusionEntropyFrictionMechanical stressMolecular dynamicsPolymersViscoelasticity

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Rauscher, Phillip M., Schweizer, Kenneth S., Rowan, Stuart J., de Pablo, Juan J.. 2020-06-02. Dynamics of poly[n]catenane melts. https://doi.org/10.1063/5.0007573

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