Influence of an ionic comonomer on polymerization-induced self-assembly of diblock copolymers in non-polar media


A series of poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) diblock copolymer nano-objects has been synthesized via reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization in n-dodecane at 20 wt%. This polymerization-induced self-assembly (PISA) formulation was modified by the incorporation of an anionic monomer, tetradodecylammonium 3-sulfopropyl methacrylate ([NDod 4] +[SPMA] -) into the oil-insoluble PBzMA block. According to the literature (M. J. Derry, et al., Chem. Sci., 2016, 7, 5078-5090), PSMA 18-PBzMA diblock copolymers only form spheres using this formulation for any core degree of polymerization. Unexpectedly, incorporating just a small fraction (<6 mol%) of [NDod 4] +[SPMA] - comonomer into the structure-directing block resulted in the formation of non-spherical diblock copolymer nano-objects, including pure worm-like and vesicular morphologies. However, only spherical micelles could be formed using a longer PSMA 34 stabilizer. These diblock copolymer nano-objects were characterized by transmission electron microscopy, small-angle X-ray scattering, and dynamic light scattering. The bulky nature of the ionic comonomer appears to make it possible to avoid the kinetically-trapped sphere morphology. This study reveals a new approach for tuning the morphology of diblock copolymer nano-objects in non-polar media.

Publication DOI:
Divisions: College of Engineering & Physical Sciences
College of Engineering & Physical Sciences > School of Infrastructure and Sustainable Engineering > Chemical Engineering & Applied Chemistry
College of Engineering & Physical Sciences > Aston Institute of Materials Research (AIMR)
College of Engineering & Physical Sciences > Aston Polymer Research Group
Additional Information: © The Royal Society of Chemistry 2020
Uncontrolled Keywords: Bioengineering,Biochemistry,Polymers and Plastics,Organic Chemistry
Publication ISSN: 1759-9962
Last Modified: 08 Dec 2023 11:28
Date Deposited: 13 Mar 2020 12:35
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Related URLs: http://pubs.rsc ... 0/PY/D0PY00101E (Publisher URL)
http://www.scop ... tnerID=8YFLogxK (Scopus URL)
PURE Output Type: Article
Published Date: 2020-04-14
Published Online Date: 2020-02-26
Accepted Date: 2020-02-22
Authors: Smith, Gregory N
Canning, Sarah
Derry, Matthew J (ORCID Profile 0000-0001-5010-6725)
Mykhaylyk, Oleksandr O
Youngs, Sarah Elizabeth
Armes, Steven P



Version: Accepted Version

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