Abstract
AbstractPolymerization‐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.
Highlights
Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10. 1002/anie.202001436. 2020 The Authors
Lower molecular weight precursors have less propensity to form well-ordered nanostructures in the solid state. This is because microphase separation requires the product of the Flory–Huggins interaction parameter (c) and the mean degree of polymerization (N) to exceed a certain minimum value.[4]. This problem can be mitigated by designing diblock copolymers with a sufficiently high interaction parameter: this has led to the emergence of a new class of so-called “high c–low N” diblock copolymers
Reversible additionfragmentation chain transfer (RAFT) polymerization has enabled the efficient synthesis of functionally diverse block copolymers in environmentally-benign solvents using either emulsion or dispersion polymerization techniques.[10a,g] in some cases such polymerization-induced selfassembly (PISA) formulations enable one-pot syntheses via sequential monomer addition.[11]
Summary
Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10. 1002/anie.202001436. 2020 The Authors. The RAFT emulsion or dispersion polymerization of commercially-available vinyl monomers is utilized to produce a wide range of high c–low N diblock copolymers in the form of sterically-stabilized nanoparticles.
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