Drastic Change of Mechanical Properties of Polyrotaxane Bulk: ABA-BAB Sequence Change Depending on Ring Position.

Polyrotaxane (PR), consisting of many ring molecules and an axis polymer, is a typical supramolecular structure with unique topological characteristics. In this study, we demonstrated the drastic change of the macroscopic mechanical properties depending on the ring position of PR in bulk. Poly(ethylene oxide)--poly(propylene oxide)--poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer was employed as an axis polymer to control the position of β-cyclodextrin (β-CD). To transfer the β-CD positions, hydroxypropyl groups (HPPR) and hydrophobic trimethyl silyl groups (TMS-HPPR), which have hydrophilic and hydrophobic βCD, respectively, were synthesized. β-CDs in HPPR were localized on a central PPO segment and formed crystal domains. The axis polymer of HPPR could not bridge β-CD crystal domains, resulting in a melt state at high temperature. On the other hand, β-CDs in TMS-HPPR were transferred to both PEO segments and formed crystal domains. The axis polymer in TMS-HPPR could bridge the β-CD crystal domains, resulting in an elastic state even at high temperature. We succeeded in demonstrating the potential ability of PR: the macroscopic mechanical properties of PR can be changed from a melt state to an elastic one by manipulating the ring positions.