Effect of Monomer Solubility on the Evolution of Copolymer Morphology during Polymerization-Induced Self-Assembly in Aqueous Solution

Abstract

Polymerization-induced self-assembly (PISA) has become a widely used technique for the rational design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms, or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood, and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous PISA formulation. Using 2-hydroxybutyl methacrylate (aqueous solubility = 20 g dm–3 at 70 °C) instead of benzyl methacrylate (0.40 g dm–3 at 70 °C) for the core-forming block allows access to an unusual “monkey nut” copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new anisotropic nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI), and small-angle X-ray scattering.

Publication DOI: https://doi.org/10.1021/acs.macromol.6b02309
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
Additional Information: This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
Publication ISSN: 1520-5835
Full Text Link: http://www.scop ... tnerID=MN8TOARS
Related URLs: https://pubs.ac ... acromol.6b02309 (Publisher URL)
PURE Output Type: Article
Published Date: 2017-02-14
Published Online Date: 2017-01-26
Accepted Date: 2016-12-14
Authors: Cockram, Amy A.
Neal, Thomas J.
Derry, Matthew J. (ORCID Profile 0000-0001-5010-6725)
Mykhaylyk, Oleksandr O.
Williams, Neal S. J.
Murray, Martin W.
Emmett, Simon N.
Armes, Steven P.

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