Synthesis of High <i>χ</i>–Low <i>N</i> Diblock Copolymers by Polymerization‐Induced Self‐Assembly
James Jennings, Erik Jan Cornel, Matthew J. Derry, Deborah L. Beattie, Matthew J. Rymaruk, Oliver J. Deane, Anthony J. Ryan, Steven P. Armes
Abstract
Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called "high χ-low N" diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains.