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

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

Research output: Contribution to journalArticle

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.
Original languageEnglish
Pages (from-to)7897-7907
JournalMacromolecules
Volume49
Issue number20
Early online date5 Oct 2016
DOIs
Publication statusPublished - 25 Oct 2016

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Block copolymers
Polymerization
hydroxypropyl methacrylate
X ray scattering
Glycerol
Oils
Emulsion polymerization
Emulsions
Self assembly
Nanostructures
Ethanol
Stabilization
Nanoparticles
Transmission electron microscopy
Water
Chemical analysis
Experiments
polybenzylmethacrylate
2-hydroxypropyl methacrylate
benzyl methacrylate

Bibliographical note

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.

Cite this

Mable, C. J. ; Thompson, K. L. ; Derry, M. J. ; Mykhaylyk, O. O. ; Binks, B. P. ; Armes, S. P. / ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets. In: Macromolecules. 2016 ; Vol. 49, No. 20. pp. 7897-7907.
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ABC Triblock Copolymer Worms: Synthesis, Characterization, and Evaluation as Pickering Emulsifiers for Millimeter-Sized Droplets. / Mable, C. J.; Thompson, K. L.; Derry, M. J.; Mykhaylyk, O. O.; Binks, B. P.; Armes, S. P.

In: Macromolecules, Vol. 49, No. 20, 25.10.2016, p. 7897-7907.

Research output: Contribution to journalArticle

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