Crystalization behavior of homopolymers confined in spherical nanodomains

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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.