Crystalization behavior of homopolymers confined in spherical nanodomains

在本研究中，我们合成了各种结晶-无定形和结晶-结晶二嵌段共聚物，以定量研究“空间限制”条件和组成聚合物（嵌段链或均聚物）的结晶行为之间的关系。此外，我们还建立了结晶均聚物被限制在各种纳米畴（球或圆柱）内的体系，以阐明“分子限制”对聚合物结晶行为和最终形态的影响，发现空间限制严重影响组成聚合物的结晶。特别是，在双结晶二嵌段的结晶laminates组成的纳米畴显示了一个非常具体的空间限制对结晶，这是不能观察到的微相分离的结晶-无定形二嵌段共聚物的结晶。分子限制被认为是不太有效的结晶比空间限制。然而，分子限制显著改变了体系的结晶行为和最终形成的形貌。特别地，我们发现它加速了栓系聚合物（或嵌段链）的初始结晶速率。从聚合物结晶的基础研究的观点来看，这些实验结果是重要的。此外，本研究结果是有用的高分子材料系统的形态控制。

In this research project, we synthesized various crystalline-amorphous and crystalline-crystalline diblock copolymers in order to quantitatively investigate the relationship between the condition of "spatial confinement" and the crystallization behavior of constituent polymers (block chains or homopolymers). Furthermore, we created the systems in which crystalline homopolymers are confined within the various nanodomains (spheres or cylinders) to clarify the effect of" molecular confinement" on the crystallization behavior and also final morphology of polymers.It was found that the spatial confinement seriously affects the crystallization of constituent polymers. In particular, the nanodomains consisting of crystallized lamellae in double crystalline diblocks showed an extremely specific spatial confinement against the crystallization, which could not be observed in the crystallization of microphase-separated crystalline-amorphous diblock copolymers. The molecular confinement was found to be less effective than the spatial confinement for the crystallization. However, the molecular confinement changed significantly the crystallization behavior and final morphology formed in the system. In particular, we found that it accelerated the initial crystallization rate of the tethered polymers (or block chains). These experimental results are important from the viewpoint of fundamental research on polymer crystallization. In addition, the present results are useful for the morphological control of polymer material systems.