Computational Studies of Poly[n]catenanes

The rheological and dynamical behaviors of polymeric systems depend on the molecular architecture and the density of entanglements. Recently, a new polymer architecture has been realized synthetically in “poly[n]catenanes” - linear chains of mechanically interlocking ring molecules. This new architecture is dominated by topological bonds along the polymer backbone and can therefore possess entanglements not only between chains, but also between neighboring repeat units. Accordingly, these poly[n]catenanes offer an opportunity to access and exploit new dynamical and rheological regimes. Inspired by this recent advance, we present computational studies on the structure and dynamics of model poly[n]catenane systems in solution, the melt, and the solid state. In particular, we focus on the rheological properties as well as characteristic motions that are unique to interlocking molecules.