Abstract
In this study, synthesis of poly (styrene)-b-poly (2-vinyl pyridine) four-arm star block copolymers ((PS-b-P2VP)4 sBCPs) possessing high interaction parameter (χ) feature was investigated. To obtain well-defined sBCPs, a challenge on ATRP of pyridine-containing monomers is foreseeable. We thus scrutinized the domino effect from PS macroinitiators (MIs) having different halogen chain ends (i.e., (PS–X)4, where X = Br/Cl) to the subsequent chain extensions. As evident from the model reactions of benzyl halides (BzX, where X = Br/Cl) and 2-methylpyridine (2 MP), the combination of BzCl and 2 MP can significantly suppress the substitution side reaction. Consequently, well-defined (PS-b-P2VP)4 sBCPs were obtained (Mn = ca. 58 k–82 k with PDI <1.5). From the analyses of small angle X-Ray scattering (SAXS), transmission electron microscopy (TEM), and atomic force microscope (AFM), self-assembly behaviors of the obtaining sBCPs were facilely observed due to the high χ feature, mainly including cylinder and lamellae morphologies, in nanoscale of approximately 30 nm.
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