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-b-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.

中文翻译：

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¹ H NMR自旋扩散实验揭示的嵌段共聚物和半结晶聚合物中间相的复杂形态

表现出流动相和刚性相的纳米结构多相聚合物还包含中等迁移率的相，通常被认为是连续的，不间断的相间层。该假设与最近的分子分辨率显微照片相反，并且与NMR自旋扩散实验的结果相矛盾，所有这些都表明了非平凡的界面结构。在此贡献中，我们重新考虑了先前的¹ H NMR自旋扩散数据集（鲁斯 胶体。Polym。科学 2014， 292，1825），并执行优化的二维和三维数值自旋扩散计算来表征基本中间相的形态图案，因此克服在数据拟合之前的不一致。为二嵌段共聚物的聚（丁二烯） -聚（苯乙烯），PS - b -PB，我们证明了相间区域包括纳米尺寸的混合固定，中间和移动子区域。相反，对于半结晶聚合物聚（ε-己内酯）PCL，自旋扩散数据最好通过完全嵌入刚性相中的中间相来重现，这归因于不完善的晶体结构。对于这两个样品，新发现揭示了中间相的复杂不连续，动态不均匀结构。