Influence of droplet properties on the formation of microemulsion-ABA-triblock copolymer networks

Structural equilibrium properties of transient networks formed by microemulsion droplets and ABA triblock copolymers in solution have been studied by Monte Carlo simulation. The droplets were represented by soft spheres and the polymers by junctions connected by harmonic bonds with an angular potential regulating the intrinsic chain stiffness. The interaction parameters were selected such that the end A-blocks were localized inside the droplets and the middle B-block in the continuous phase. The influence of (i) the droplet volume fraction, (ii) the droplet radius, and (iii) the contour length of the middle B-block on the formation and the structure of the microemulsion-polymer network at three-fold excess of the polymers were investigated by using polymer end-to-end separation probability distribution functions, droplet radial distribution functions, and network connectivity indicators. A universal behavior of the properties investigated was found when examining the results versus the length ratio of the polymer end-to-end separation and the surface-to-surface separation between neighboring droplets for a hypothetical homogeneous droplet distribution. At a length ratio of 0.5, few polymer bridges between droplets were established and only clusters with a small number of droplets were found. However at a length ratio of ca. 1.5 a connected network was formed and most of the polymers formed bridges between two droplets.