Molecular Weight Distribution Shape as a Versatile Approach to Tailoring Block Copolymer Phase Behavior

The molecular weight distributions (MWDs) of block copolymers significantly impact their morphological phase behavior, but exploiting these features as a means to tune material properties has been limited to the MWD breadth, or dispersity (Đ). Manipulation of the entire MWD has promising potential to address this challenge by providing a convenient and versatile route toward tailoring polymer nanostructure. Herein, we describe the self-assembly of poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) where the PS blocks have systematically deviating compositions of molecular weights. We find that controlling the MWD shape, breadth and skew, afforded access to different morphologies in samples with the same molecular characteristics, including Đ. As such, we illustrate the generality and effectiveness of this strategy and anticipate that it will facilitate the increased deployment of disperse polymer compositions in advanced materials applications.