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Preparation of non-aqueous Pickering emulsions using anisotropic block copolymer nanoparticles

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Abstract

In this work, we show that amphiphilic diblock copolymer worms prepared via alcoholic RAFT dispersion polymerization can be used to stabilize non-aqueous Pickering emulsions. A previously reported synthesis protocol based on polymerization-induced self-assembly (PISA) was modified to enable the preparation of poly(2-(dimethylamino)ethyl methacrylate)-poly(benzyl methacrylate) (PDMA-PBzMA) worm-like particles directly in methanol at relatively high solids. A dilute dispersion of these highly anisotropic nanoparticles was then homogenized with sunflower oil to produce sunflower oil-in-methanol emulsions. The mean droplet diameter ranged from 9 to 104 μm, depending on the nanoparticle concentration and the stirring rate used for homogenization. The sunflower oil content was increased systematically, with stable emulsions being obtained up to a volume fraction of 0.60. In all cases, the sunflower oil droplets gradually increase in size on ageing for up to 4 days. However, stable emulsions were obtained after this time period, with no further change in the mean droplet diameter for at least 2 months on standing at ambient temperature. Turbidimetry studies of the continuous phase after sedimentation of the relatively dense emulsion droplets indicated that the initial adsorption efficiency of the PDMA-PBzMA worms is very high, but this is reduced significantly as the droplet diameter gradually increases during ageing. There is a concomitant increase in fractional surface coverage over the same time period, suggesting that the increase in droplet diameter is the result of limited coalescence, rather than an Ostwald ripening mechanism.

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Acknowledgments

We thank DSM Advanced Surfaces (Geleen, The Netherlands) and EPSRC for a CASE PhD studentship for ERJ. SPA thanks EPSRC (platform grant EP/J007846/1) for post-doctoral support of KLT and also acknowledges partial project funding from Stichting Innovatie Alliantie (Foundation Innovation Alliance).

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  1. Department of Chemistry, Dainton Building, University of Sheffield, Brook Hill, Sheffield, Yorkshire, S3 7HF, UK

    S. L. Rizzelli, E. R. Jones, K. L. Thompson & S. P. Armes

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  1. S. L. Rizzelli
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  2. E. R. Jones
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  4. S. P. Armes
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Correspondence to S. P. Armes.

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This manuscript is an invited contribution associated with the Colloid and Polymer Science Lecture 2015, awarded to Steven P. Armes jointly by the German Colloid Society and Springer at the IACIS conference in Mainz on May 28, 2015.

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Rizzelli, S.L., Jones, E.R., Thompson, K.L. et al. Preparation of non-aqueous Pickering emulsions using anisotropic block copolymer nanoparticles. Colloid Polym Sci 294, 1–12 (2016). https://doi.org/10.1007/s00396-015-3785-3

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