Self-Organization and Flow of Low-Functionality Telechelic Star Polymers with Varying Attraction.

We combine state-of-the art synthesis, simulations, and physical experiments to explore the tunable, responsive character of telechelic star polymers as models for soft patchy particles. We focus on the simplest possible system: a star comprising three asymmetric block copolymer arms with solvophilic inner and solvophobic outer blocks. Our dilute solution studies reveal the onset of a second slow mode in the intermediate scattering functions as the temperature decreases below the θ-point of the outer block, as well as the size reduction of single stars upon further decreasing temperature. Clusters comprising multiple stars are formed and their average dimensions, akin to the single star size, counterintuitively decrease upon cooling. A similar phenomenology is observed in simulations upon increasing attraction between the outer blocks and is rationalized as a result of the interplay between interstar associations and steric repulsion between the star cores. Since our simulations are able to describe the experimental findings reliably, we can use them with confidence to make predictions at conditions and flow regimes that are inaccessible experimentally. Specifically, we employ simulations to investigate flow properties of the system at high shear rates, revealing shear thinning behavior caused by the breakup of interstar associations under flow. On the other hand, the zero-shear viscosity obtained experimentally exhibits a rather weak activation energy, which increases upon rising star concentration. These findings demonstrate the unusual properties of telechelic star polymers even in the dilute regime. They also offer a powerful toolbox for designing soft patchy particles and exploring their unprecedented responsive properties further on.