Linking microscopic structural changes and macroscopic mechanical responses in a near-ideal bottlebrush elastomer...

Bottlebrush (BB) elastomers, in which load-bearing network strands are densely grafted with side chains, are gaining much attention due to their unique mechanical properties. Herein, we used in situ small-angle X-ray scattering coupled with tensile tests to investigate the microscopic structural changes induced in a model BB elastomer with a controlled network structure under uniaxial deformation. The model BB elastomer was synthesized by end-linking a monodisperse star-shaped BB polymer, which ensured a controlled network structure. The BB elastomer exhibited both significant strain stiffening and backbone chain alignment under uniaxial loading, and these properties were not observed in an analogous side chain-free elastomer and gel. It was also found that the side chains in the BB elastomer did not show any sign of chain orientation even when the attached backbone chain was aligned in the stretching direction. These observations highlighted the roles of side chains: they were structurally disordered at the segment level but their steric repulsion made the backbone chain aligned and overstretched.