Morphology and cation local structure in a blend of copper-neutralized carboxy-terminated polybutadiene and poly(styrene-co-4-vinylpyridine)

Carboxy-terminated polybutadiene neutralized with Cu²⁺ (CuPBD) and its blend with poly(styrene-co-4-vinylpyridine) (SVP) were examined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), small-angle x-ray scattering (SAXS), and extended x-ray absorption fine structure (EXAFS) spectroscopy. The DSC results indicate that in the blend substantial mixing occurs in the CuPBD-rich phase, although complete miscibility is not achieved, and the SVP-rich phase remains relatively pure. The TEM micrographs indicate that the morphology, while irregular, is reasonably described as bicontinuous, with a domain size of order 100 nm. The SAXS patterns show that the ionic aggregates present in CuPBD are destroyed upon blending, which is interpreted as being due to steric hindrances between ionic groups coordinated to vinylpyridine nitrogens. The EXAFS radial structure function of the blend exhibits a marked decrease in the Cu-Cu peak in comparison with CuPBD, indicating a change in local structure upon blending. The results indicate that some of the SVP is miscible with CuPBD owing to complexation between the pendant pyridine groups and the Cu²⁺ ions, which disrupts the ionic aggregates. However, the two materials are not fully miscible, leading to a rather coarse two-phase morphology.