Synthesis, Characterization, and Pickering Emulsifier Performance of Anisotropic Cross-Linked Block Copolymer Worms: Effect of Aspect Ratio on Emulsion Stability in the Presence of Surfactant.

Abstract

Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization is used to prepare epoxy-functional PGMA-P(HPMA- stat-GlyMA) diblock copolymer worms, where GMA, HPMA, and GlyMA denote glycerol monomethacrylate, 2-hydroxypropyl methacrylate, and glycidyl methacrylate, respectively. The epoxy groups on the GlyMA residues were ring-opened using 3-aminopropyltriethoxysilane (APTES) in order to cross-link the worm cores via a series of hydrolysis-condensation reactions. Importantly, the worm aspect ratio can be adjusted depending on the precise conditions selected for covalent stabilization. Relatively long cross-linked worms are obtained by reaction with APTES at 20 °C, whereas much shorter worms with essentially the same copolymer composition are formed by cooling the linear worms from 20 to 4 °C prior to APTES addition. Small-angle X-ray scattering (SAXS) studies confirmed that the mean aspect ratio for the long worms is approximately eight times greater than that for the short worms. Aqueous electrophoresis studies indicated that both types of cross-linked worms acquired weak cationic surface charge at low pH as a result of protonation of APTES-derived secondary amine groups within the nanoparticle cores. These cross-linked worms were evaluated as emulsifiers for the stabilization of n-dodecane-in-water emulsions via high-shear homogenization at 20 °C and pH 8. Increasing the copolymer concentration led to a reduction in mean droplet diameter, indicating that APTES cross-linking was sufficient to allow the nanoparticles to adsorb intact at the oil/water interface and hence produce genuine Pickering emulsions, rather than undergo in situ dissociation to form surface-active diblock copolymer chains. In surfactant challenge studies, the relatively long worms required a thirty-fold higher concentration of a nonionic surfactant (Tween 80) to be displaced from the n-dodecane-water interface compared to the short worms. This suggests that the former nanoparticles are much more strongly adsorbed than the latter, indicating that significantly greater Pickering emulsion stability can be achieved by using highly anisotropic worms. In contrast, colloidosomes prepared by reacting the hydroxyl-functional adsorbed worms with an oil-soluble polymeric diisocyanate remained intact when exposed to high concentrations of Tween 80.