Effect of Block Length, Polydispersity, and Salt Concentration on PEO−PDEAMA Block Copolymer Structures in Dilute Solution

A series of poly(ethylene oxide)-block-poly(N,N-diethylaminoethyl methacrylate) (PEO−PDEAMA) block copolymers with relatively high polydispersity (1.36 < PDI < 1.96) have been prepared to determine the effect that polydispersity has on the self-assembly of amphiphilic block copolymers in dilute solution. Because monodisperse macroinitiators were used for the ATRP reactions, the polydispersity resides within the hydrophobic block. By adjusting the relative block lengths, spherical micelles, wormlike micelles, vesicles, or a precipitate is formed. Here, we show that relatively high polydispersity in the block copolymer does not preclude efficient self-assembly. We also discuss the effect of increasing the concentration of NaCl in the systems and show that this can result in a shift from one morphology to another. These shifts are reversible in some cases, but for PEO₁₂−PDEAMA₃₉, this method allows access to giant vesicles of between 500 nm and 1 μm in diameter.