Molecular Auxetic Polymer of Intrinsic Microporosity via Conformational Switching of a Cavitand Crosslinker

Auxetics are materials characterized by a negative Poisson's ratio (NPR), an uncommon mechanical behavior corresponding to a transversal deformation tendency opposite to the traditional materials. Here, the first example of a synthetic molecular auxetic polymer obtained by embedding a conformationally expandable cavitand as a crosslinker into a rigid polymer of intrinsic microporosity (PIM) is presented. The rigidity and microporosity of the polymeric matrix are pivotal to maximizing the expansion effect of the cavitand that, under mechanical stress, can assume two different conformations: a compact vase one and an extended kite form. The auxetic behavior and the corresponding NPR of the proposed material is predicted by a specific micromechanical model that considers the cavitand volume expansion ratio, the fraction of the cavitand crosslinker in the polymer, and the mechanical characteristics of the polymer backbone. The reversible auxetic behavior of the material is experimentally verified via the digital image correlation technique performed during the mechanical tests on films obtained by blending the auxetic crosslinked polymer with pristine PIM. Two specific control experiments prove that the mechanically driven conformational expansion of the cavitand crosslinker is the sole responsible for the observed NPR of the polymer. A molecular auxetic polymer is obtained via mechanochemical switch of a conformationally expandable cavitand embedded as a crosslinker in a rigid polymer of intrinsic microporosity. The resulting material exhibits a negative Poisson's ratio upon stretching. The experimental results and the kinematic behavior of the material are supported by a micromechanical model, validating the cavitand conformational expansion as the origin of the auxeticity.image