Synthesis of 3-arm star block copolymers by combination of core-first and coupling-onto methods using ATRP and click reactions

Three-arm star block copolymers were successfully synthesized by combination of core-first and coupling-onto strategies. First, polystyrene 3-arm star polymers (PS-Br)(3) with high bromine chain-end functionality were synthesized by atom transfer radical polymerization (ATRP) using the core-first method. After complete transformation of the bromo groups to azido groups by nucleophilic substitution with sodium azide, the product (PS-N-3)(3) was used for click reactions with alkyne-terminated poly(ethylene oxide) chains (PEO-alkyne) and produced 3-arm star block copolymers (PS-b-PEO)(3) via the coupling-onto method. The efficiency of the coupling reaction was influenced by the preservation of chain-end functionalities in both (PS-N-3)(3) and PEO-alkyne precursors. The azido functionality in the (PS-N-3)(3) star precursors was determined as high as 97% by gradient polymer elution chromatography (GPEQ analysis of the coupling product between (PS-N-3)(3) and propargyl alcohol. During the coupling reactions between (PS-N-3)(3) and PEO-alkyne, the functionality of PEO-alkyne was ca. 1.00%. In the final coupling product, the molar