Crystal orientation of poly(ε-caprolactone) chains confined in lamellar nanodomains: Effects of chain-ends tethering to nanodomain interfaces

We have examined the crystal orientation of poly (ε-caprolactone) (PCL) chains covalently tethered to nanodomain interfaces at both chain-ends (T2-PCL), one chain-end (T1-PCL), and no chain-end (PCL homopolymers, T0-PCL) all confined in an identical lamellar nanodomain (nanolamella). In order to prepare these PCL chains, we synthesized two kinds of lamella-forming polystyrene-block-PCL-block-polystyrene (PS-b-PCL-b-PS) triblock copolymers with photocleavable o-nitrobenzyl groups (ONB) at either or both of block junctions. The chain-ends tethering significantly affected the tilt angle φ between the c axis of PCL crystals and the normal of nanolamella interfaces (ND). That is, the c axis of T2-PCL crystals oriented almost perpendicular to ND (φ ≥ 70°), whereas that of T0-PCL crystals took completely parallel orientation against ND (φ ∼ 0°) at high crystallization temperatures (>32 °C). The T1-PCL crystal showed an intermediate orientation between T2-PCL and T0-PCL crystals (35° < φ < 55°), which depended moderately on the crystallization temperature. The difference in crystal orientation was discussed in terms of a delicate balance between the heterogeneous nucleation rate and subsequent crystal growth rate by considering the difference in chain mobility based on the state of chain-ends tethering.