The
dynamics of two polyrotaxanes with different ring component
sizes were compared through viscoelastic measurements. An improved
polyrotaxane synthesis was used to develop a glass-forming polyrotaxane
composed of γ-cyclodextrin (γ-CD), which is a larger cyclic
molecule than α-cyclodextrin (α-CD)a component
of a comparative polyrotaxane. In the glass state, both polyrotaxanes
exhibited a large secondary relaxation attributed to the confined
motion of the threading polyethylene glycol as the main chain, and
their dynamics were not affected by the ring size. However, the glass-transition
dynamics were clearly steepened by the enlargement of rings. The analysis
of the glass-transition dynamics revealed that the segment motion
of polyrotaxane, which is the translation of the threading polymer
with several rings threaded cooperatively, was released near the glass-transition
temperature determined by differential scanning calorimetry, T
g(d), in the case of polyrotaxane with γ-CD,
whereas the release was relatively delayed in the case of α-CD.
This finding suggests that the enlargement of the rings weakens the
topological constraints that prolong the onset of the segment motion
of polyrotaxanes. Positron annihilation lifetime measurements showed
a negligible difference in the free volume of polyrotaxane glasses
with different ring sizes. This finding indicates that the larger
ring did not provide an additional space for the segment motion but
probably an undetectable small gap between the inner wall of the ring
and the threading polymer to facilitate the ring-chain cooperative
motion.