Topological Programmability of Isomerizable Polymers.

ABSTRACT

Topology isomerizable networks (TINs) can be programmed into numerous polymers exhibiting unique and spatially defined (thermo-) mechanical properties. However, capturing the dynamics in topological transformations and revealing the intrinsic mechanisms of mechanical property modulation at the microscopic level is a significant challenge. Here, we use a combination of coarse-grained molecular dynamics simulations and reaction kinetic theory to reveal the impact of dynamic bond exchange reactions on the topology of branched chains. We find that, the grafted units follow a geometric distribution with a converged uniformity, which depends solely on the average grafted units of branched chains. Furthermore, we demonstrate that the topological structure can lead to spontaneous modulation of mechanical properties. The theoretical framework provides a research paradigm for studying the topology and mechanical properties of TINs.