Fabrication and structural analysis of polyrotaxane fibers and films

Polyrotaxane (PR), a typical example of topological supramolecular architecture, consists of multiple cyclic molecules threaded onto a linear polymer backbone and capped with bulky end-groups. The PR system of polyethylene glycol and α-cyclodextrin (α-CD) has been extensively studied for its facile synthesis, unique molecular structure, and possible applications for various smart materials. We have previously demonstrated the fabrication of PR-based fibers without chemical cross-links by wet spinning of PR solution. In this paper, we investigate the crystal structure of α-CDs in PR fibers and the effect of drawing on it. The α-CDs in PR fiber are found to form hexagonal channel-type structure. The drawing process promotes formation of the packing arrangement of α-CDs in the c-axis because of the sliding of α-CD molecules along the polymer backbone. In addition, we demonstrate the preparation of an elastomeric PR film having similar network structure to the fibers and ethylene glycol oligomer as plasticizer.