Micellization of pH‐sensitive poly(butadiene)‐block‐poly(2 vinylpyridine)‐block‐poly(ethylene oxide) triblock copolymers: Complex formation with anionic surfactants

The micellization of three tailor‐made triblock copolymers, such as PB₁₀₀–P2VP₁₀₀–PEO₁₀₄, PB₁₈₅–P2VP₁₀₈–PEO₁₅₄, and PB₃₇–P2VP₁₁₅–PEO₂₄₁, having similar total molecular weights and constant poly(2‐vinylpyridine) (P2VP) sequence lengths, was investigated as a function of pH and sodium dodecyl sulfate (SDS) concentration. At pH 7 the formation of intermicellar aggregates was observed, especially for copolymers of low poly(ethylene oxide) (PEO) content. A pH decrease from 7 to 3 leads to a particle size increase due to the electrostatic repulsion of the protonated P2VP chains. The influence of the PEO sequence length was also observed for zeta potential values. At pH 3, in the absence of SDS, core–shell–corona micelles are formed whereas in the presence of small amount of SDS (degree of neutralization DN = 0%–50%), a complex is formed between SDS and the protonated P2VP which leads to the shrinkage of the shell and thus to a decrease of the micellar sizes. For higher DN values, the micellar sizes increase due to the formation of large agglomerates and a transition occurs from a monomodal to a bimodal size distribution. Furthermore, it turned out that secondary aggregation, such as intermicellar aggregation, can completely be avoided if the degree of polymerization (DPn) of the water‐soluble block is significantly higher than the DPn of the water‐insoluble sequence. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45313.