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

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      Langmuir

      American Chemical Society

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          Abstract

          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 PSMA 54 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.

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          Most cited references 65

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          Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer:  The RAFT Process

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            Theory of Microphase Separation in Block Copolymers

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              Radical addition–fragmentation chemistry in polymer synthesis

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                Author and article information

                Journal
                Langmuir
                Langmuir
                la
                langd5
                Langmuir
                American Chemical Society
                0743-7463
                1520-5827
                26 March 2020
                14 April 2020
                : 36
                : 14
                : 3730-3736
                Affiliations
                Dainton Building, Department of Chemistry, University of Sheffield, Brook Hill , Sheffield, South Yorkshire S3 7HF, United Kingdom
                Author notes
                Article
                10.1021/acs.langmuir.0c00211
                7161081
                32216260
                Copyright © 2020 American Chemical Society

                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.

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                la0c00211
                la0c00211

                Physical chemistry

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