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Thermoreversible crystallization-driven aggregation of diblock copolymer nanoparticles in mineral oil

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Abstract

A poly(behenyl methacrylate)37 (PBeMA37) macromolecular chain transfer agent is utilized for the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) directly in mineral oil at 90 °C. Polymerization-induced self-assembly (PISA) occurs under these conditions, yielding a series of sterically-stabilized PBeMA37–PBzMAx diblock copolymer spheres of tunable diameter as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies. Rheological studies indicate that a relatively transparent, free-flowing, concentrated dispersion of non-interacting 32 nm PBeMA37–PBzMA100 spheres at 50 °C forms a turbid, paste-like dispersion on cooling to 20 °C. Turbidimetry and differential scanning calorimetry (DSC) studies conducted on solutions of PBeMA37 homopolymer in mineral oil suggest that this switchable colloidal stability is linked to crystallization-induced phase separation exhibited by this stabilizer block. Indeed, variable-temperature small-angle X-ray scattering (SAXS) indicates that a loose mass fractal network of strongly interacting spheres is formed on cooling to 20 °C, which accounts for this thermoreversible sol–gel transition. Moreover, SAXS, DSC and wide-angle X-ray scattering (WAXS) analyses indicate that the behenyl (C22H45) side-chains first form crystalline domains comprising adjacent stabilizer chains within individual spherical nanoparticles, with subsequent crystallization between neighboring nanoparticles leading to the formation of the mass fractal aggregates.

Graphical abstract: Thermoreversible crystallization-driven aggregation of diblock copolymer nanoparticles in mineral oil

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Publication details

The article was received on 14 Feb 2018, accepted on 01 Apr 2018 and first published on 02 Apr 2018


Article type: Edge Article
DOI: 10.1039/C8SC00762D
Citation: Chem. Sci., 2018, Advance Article
  • Open access: Creative Commons BY license
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    Thermoreversible crystallization-driven aggregation of diblock copolymer nanoparticles in mineral oil

    M. J. Derry, O. O. Mykhaylyk, A. J. Ryan and S. P. Armes, Chem. Sci., 2018, Advance Article , DOI: 10.1039/C8SC00762D

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