Phase Transition Behaviors and Nanoscale Film Morphologies of Poly(δ‐valerolactone) Axles Bearing Movable and Fixed Rotaxane Wheels

Abstract

In this study, poly(δ‐valerolactone) (PVL) axles bearing movable and fixed dibenzo‐24‐crown‐8‐ether wheels (rot‐M and rot‐F) are investigated for the first time in the terms of phase transition and nanoscale film morphology: PVL‐rot‐M and PVL‐rot‐F. Interestingly, the PVL axles reveal a strong tendency to form a horizontal lamellar structure with three different rotational crystal lattice domains in nanoscale films. The morphological structural parameters are discernibly varied by the movable and fixed rotaxane wheels. In particular, the rot‐M wheel tends to be populated in both the interfacial and amorphous layers. The rot‐M wheel is found to significantly influence the phase transition characteristics of the PVL axle because of its movability along the polymer backbone chain. In contrast, the rot‐F wheel tends to be more localized in the interfacial layer rather than in the amorphous layer because of its immovability constrained at the polymer chain end. The rot‐F wheel causes severe thermal instability in the PVL axle, which can be attributed mainly to the presence of its counter anion (PF6−).

Influence of Topological Confinement on Nanoscale Film Morphologies of Tricyclic Block Copolymers

“…Synchrotron grazing-incidence small-angle and wide-angle X-ray scattering (GISAXS and GIWAXS) measurements were conducted with an X-ray beam with a wavelength (λ) of 0.12411 nm at the 3C beamline − of the Pohang Accelerator Laboratory (PAL), Pohang, Korea. The sample-to-detector distance (SDD) was set to 2951.3 and 214.7 mm for GISAXS and GIWAXS measurements, respectively.…”