Implementation of the Pulley Effect of Polyrotaxane in Transparent Bulk Polymer for Simultaneous Strengthening and Toughening

The fascinating pulley effect from moveable α-cyclodextrin (α-CD) based polyrotaxane favors toughening of hydrogels, but the strategy is rarely applied in bulk polymers because of the severe aggregation trend of α-CDs. Herein, the authors propose a simple approach to moderately modify the α-CDs of polyrotaxane by introducing large steric side groups and reactive CC so as to minimize the unwanted hydrogen bonds-induced aggregation of α-CDs and hydrophilicity of polyrotaxane. Accordingly, the proof-of-concept material, poly(methyl acrylate) crosslinked by the modified polyrotaxane, turns out to be rather homogeneous with optical transparency. The polyrotaxane crosslinks are movable under external force as disclosed by in situ small-angle X-ray scattering and other techniques, which is correlated to the relative amount of α-CDs. A few polyrotaxane crosslinkers prove to be sufficient to simultaneously improve strength and toughness of poly(methyl acrylate) owing to the stress equalization. The present work provides an expandable toolbox for enhancing polymers.