Chain Exchange Kinetics of Asymmetric B1AB2 Linear Triblock and AB1B2 Branched Triblock Copolymers

Abstract

Equilibrium chain exchange of asymmetric B1AB2 and AB1B2 branched triblock copolymers in a B selective solvent has been studied via dissipative particle dynamics simulations. Hybridization simulations are performed using B1AB2 and AB1B2 branched triblock copolymers at varying levels of asymmetry and compared with equivalent AB diblock copolymers. It is found that B1AB2 triblocks exchange ∼1 order of magnitude faster than diblocks (persisting over various values of χNcore and total corona length), while AB1B2 triblocks exchange ∼4 times faster than diblocks. The dependence on asymmetry is weak, with very asymmetric triblocks (NB1 ≪ NB2) exchanging only 2 or 3 times faster than symmetric triblocks. Two causes are found for this: (1) increases in the density of corona beads near the micelle core for triblocks, resulting in greater stretching penalties and lower aggregation numbers, and (2) looped core blocks (B1AB2) spending more time near the surface of a micelle core than unlooped core blocks (AB1B2 and AB...