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Carboxylated poly(styrene-b-ethylene-co-butylene-b-styrene) (CSEBS) with different car- boxylation extents (-COOH) were prepared. The (-COOH) dependence of the self-assembly of CSEBS in water was investigated by a combination of static and dynamic laser light scattering. The addition of a dilute CSEBS tetrahydrofuran solution dropwise into water leads to a microphase inversion, resulting in surfactant-free polymeric nanoparticles stable in water. As (-COOH) increases, the particle size first decreases and then slightly increases; namely, there exists a minimum in particle size when (-COOH) 21 mol %. On the other hand, the decrease of the average particle density 〈F〉 and the increase of the ratio of the average radius of gyration to the average hydrodynamic radius (〈Rg〉/〈Rh〉 )a s (-COOH) increases reveal that the CSEBS nanoparticle gradually changes from a uniform and compact globule to a hyperbranched and loose cluster. The cluster can be broken by a simple dilution of the dispersion, indicating that there exists a delicate balance between hydrophobic and hydrophilic interactions in the self-assembly.

macromolecules

Self-Assembly of Carboxylated Poly(styrene-b-ethylene-co-butylene-b-styrene) Triblock Copolymer Chains in Water via a Microphase Inversion