| Summary: | Polymers with crystallizable side chains have numerous applications, and their properties depend on their crystal morphologies and phase separation. Structural analysis on a wide spatial scale plays an important role in controlling the thermal properties and higher-order structures of these polymers. In this study, we elucidated the melting and crystallization processes of copolymers with varying crystallizable side-chain fractions over a wide spatial range. Differential scanning calorimetry revealed that the enthalpies of melting and crystallization increased linearly with increasing crystallizable side-chain fraction. The results of wide-angle X-ray scattering indicated that the crystal lattice was hexagonal. Conversely, spherulite-like higher-order architectures with linear structures and radial spreading were observed in the highly crystallizable components, but no micrometer-scale structures were observed in the less crystallizable components. In situ small-angle X-ray scattering was used to elucidate the phase separation and mixing processes. Lamellar crystallites were observed at crystallizable side-chain fractions of >55 wt.%, whereas small crystallites were observed at fractions of <45 wt.%. At temperatures above the order-disorder transition temperature, density fluctuations caused by correlation holes were observed. These properties have a strong effect on the crystallizable side-chain fraction.
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