Complex Morphology of the Intermediate Phase in Block Copolymers and Semicrystalline Polymers As Revealed by ¹H NMR Spin Diffusion Experiments

Nanostructured multiphase polymers exhibiting a mobile and a rigid phase also contain a phase of intermediate mobility that is usually assumed to be a continuous, uninterrupted interphase layer. This assumption is contrary to recent molecular-resolution micrographs and contradicts results from NMR spin diffusion experiments, all of which suggest a nontrivial interface structure. In this contribution, we reconsider our previous ¹H NMR spin diffusion data sets (Roos Colloid. Polym. Sci. 2014, 292, 1825) and perform optimized 2D and 3D numerical spin diffusion calculations to characterize the basic intermediate-phase morphological pattern, thus overcoming previous inconsistencies in data fitting. For the diblock copolymer poly­(butadiene)-poly­(styrene), PS<i>-<i>b</i>-</i>PB, we demonstrate that the interphase region comprises nanometer-size intermixed immobile, intermediate and mobile subregions. In contrast, for the semicrystalline polymer poly­(ε-caprolactone), PCL, the spin diffusion data are best reproduced by an intermediate phase that is fully embedded within the rigid phase, which is attributed to an imperfect crystalline structure. For both samples, the new findings reveal a complex discontinuous, dynamically inhomogeneous structure of the intermediate phase