ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets.

C J Mable,K L Thompson,O O Mykhaylyk,S P Armes,B P Binks,M J Derry

doi:10.1021/acs.macromol.6b01729

C J Mable, K L Thompson + Show 4 more

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https://doi.org/10.1021/acs.macromol.6b01729

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Journal: Macromolecules	Publication Date: Oct 5, 2016
Citations: 80	License type: cc-by

Affiliation: University of Sheffield, University of Hull

Abstract

Polymerization-induced self-assembly (PISA) is used to prepare linear poly(glycerol monomethacrylate)–poly(2-hydroxypropyl methacrylate)–poly(benzyl methacrylate) [PGMA–PHPMA–PBzMA] triblock copolymer nano-objects in the form of a concentrated aqueous dispersion via a three-step synthesis based on reversible addition–fragmentation chain transfer (RAFT) polymerization. First, GMA is polymerized via RAFT solution polymerization in ethanol, then HPMA is polymerized via RAFT aqueous solution polymerization, and finally BzMA is polymerized via “seeded” RAFT aqueous emulsion polymerization. For certain block compositions, highly anisotropic worm-like particles are obtained, which are characterized by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The design rules for accessing higher order morphologies (i.e., worms or vesicles) are briefly explored. Surprisingly, vesicular morphologies cannot be accessed by targeting longer PBzMA blocks—instead, only spherical nanoparticles are formed. SAXS is used to rationalize these counterintuitive observations, which are best explained by considering subtle changes in the relative enthalpic incompatibilities between the three blocks during the growth of the PBzMA block. Finally, the PGMA–PHPMA–PBzMA worms are evaluated as Pickering emulsifiers for the stabilization of oil-in-water emulsions. Millimeter-sized oil droplets can be obtained using low-shear homogenization (hand-shaking) in the presence of 20 vol % n-dodecane. In contrast, control experiments performed using PGMA–PHPMA diblock copolymer worms indicate that these more delicate nanostructures do not survive even these mild conditions.

Highlights

Particle-stabilized emulsions, otherwise known as Pickering emulsions, have been recognized for more than a century.[1]
The initial reversible addition−fragmentation chain transfer (RAFT) solution polymerization of glycerol monomethacrylate (GMA) was conducted in ethanol at 70 °C to generate a near-monodisperse
Aqueous solution polymerization of hydroxypropyl methacrylate (HPMA) at 15% w/w solids, yielding a 100 g batch of G37H60 diblock copolymer precursor. 1H NMR studies indicated that more than 99% HPMA conversion was achieved within 2 h at 70 °C

Summary

Introduction

Particle-stabilized emulsions, otherwise known as Pickering emulsions, have been recognized for more than a century.[1] Many classes of particles including silica,[2−6] polymer latexes,[6−10] and clays[11−14] can be used to stabilize such emulsions, with surface wettability usually dictating the emulsion type. Noble et al reported the use of polymeric microrods to prepare water-in-oil emulsions and colloidosomes.[18] More recently, Kalashnikova et al evaluated various types of cellulose-based Pickering emulsifiers of ribbon-like shape.[19−21] Wege et al.[22] utilized hydrophobic anisotropic cellulose microparticles to stabilize water-in-oil emulsions. Vermant and co-workers[23] employed a multiple backscattering technique to demonstrate that more stable Pickering emulsions are obtained when employing ellipsoidal polystyrene latexes (mean aspect ratio ∼9)

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