Exploring the Upper Size Limit for Sterically Stabilized Diblock Copolymer Nanoparticles Prepared by Polymerization-Induced Self-Assembly in Non-Polar Media


Reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate is used to prepare a series of well-defined poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nanoparticles in mineral oil at 90 °C. A relatively long PSMA54 precursor acts as a steric stabilizer block and also ensures that only kinetically trapped spheres are obtained, regardless of the target degree of polymerization (DP) for the core-forming PBzMA block. This polymerization-induced self-assembly (PISA) formulation provides good control over the particle size distribution over a wide size range (24–459 nm diameter). 1H NMR spectroscopy studies confirm that high monomer conversions (≥96%) are obtained for all PISA syntheses while transmission electron microscopy and dynamic light scattering analyses show well-defined spheres with a power-law relationship between the target PBzMA DP and the mean particle diameter. Gel permeation chromatography studies indicate a gradual loss of control over the molecular weight distribution as higher DPs are targeted, but well-defined morphologies and narrow particle size distributions can be obtained for PBzMA DPs up to 3500, which corresponds to an upper particle size limit of 459 nm. Thus, these are among the largest well-defined spheres with reasonably narrow size distributions (standard deviation ≤20%) produced by any PISA formulation. Such large spheres serve as model sterically stabilized particles for analytical centrifugation studies.

Publication DOI: https://doi.org/10.1021/acs.langmuir.0c00211
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: Funding: S.P.A. thanks EPSRC for a four-year Established Career Particle Technology Fellowship (EP/J003009/1). M.J.D. and S.P.A. thank the Leverhulme Trust for a postdoctoral fellowship (RPG-2016-330) 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.
Uncontrolled Keywords: Materials Science(all),Condensed Matter Physics,Surfaces and Interfaces,Spectroscopy,Electrochemistry
Publication ISSN: 1520-5827
Last Modified: 11 Dec 2023 08:27
Date Deposited: 09 Apr 2020 08:53
Full Text Link:
Related URLs: https://pubs.ac ... angmuir.0c00211 (Publisher URL)
https://pubs.ac ... ngmuir.0c00211. (Related URL)
PURE Output Type: Article
Published Date: 2020-04-14
Published Online Date: 2020-04-02
Accepted Date: 2020-03-26
Authors: Parker, Bryony R.
Derry, Matthew J. (ORCID Profile 0000-0001-5010-6725)
Ning, Yin
Armes, Steven P.



Version: Published Version

License: Creative Commons Attribution

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