Nanoemulsions and Nanolatexes Stabilized by Hydrophobically

Aug 11, 2017 - Department of Macromolecules Science and Engineering, Case Western Reserve University, 2100 Adelbert Rd., Cleveland, Ohio 44106, United...
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Article pubs.acs.org/Macromolecules

Nanoemulsions and Nanolatexes Stabilized by Hydrophobically Functionalized Cellulose Nanocrystals Yefei Zhang,†,§ Vahid Karimkhani,§ Brian T. Makowski,∥ Gamini Samaranayake,∥ and Stuart J. Rowan*,†,‡,§ †

Institute of Molecular Engineering and ‡Department of Chemistry, University of Chicago, 5640 S Ellis Ave., Chicago, Illinois 60637, United States § Department of Macromolecules Science and Engineering, Case Western Reserve University, 2100 Adelbert Rd., Cleveland, Ohio 44106, United States ∥ Sherwin-Williams, 601 Canal Rd., Cleveland, Ohio 44113, United States S Supporting Information *

ABSTRACT: Carboxylic acid cellulose nanocrystals (CNC-COOHs) that have been covalently functionalized (via peptide coupling chemistry) with a range of different hydrophobic groups have been investigated as nanoparticle surfactants to stabilize styrene-in-water nanoemulsions. It is shown that the size and stability of these nanoemulsions depend on both the amount of surface carboxylic acid groups as well as the amount and type of hydrophobic alkyl groups on the CNC surface. Two different biosources for the CNCs, microcrystalline cellulose (MCC) and Miscanthus x. Giganteus (MxG), were investigated to see the effect that the CNC aspect ratio has on these nanoemulsions. Stable oil-in-water (o/w) Pickering emulsions with particle diameters of only a few hundred nanometers can be accessed using these hydrophobic functionalized CNCs, and the resulting emulsions can be polymerized to access nanometer sized latexes. The hydrophobic/hydrophilic balance of the functionalized CNCs was found to be critical to lower the interfacial tension between oil and water, which allowed access to stable emulsions with droplet diameters