Cationic Sterically Stabilized Diblock Copolymer Nanoparticles Exhibit Exceptional Tolerance toward Added Salt.

Abstract

For certain commercial applications such as enhanced oil recovery, sterically stabilized colloidal dispersions that exhibit high tolerance toward added salt are desirable. Herein, we report a series of new cationic diblock copolymer nanoparticles that display excellent colloidal stability in concentrated aqueous salt solutions. More specifically, poly(2-(acryloyloxy)ethyltrimethylammonium chloride) (PATAC) has been chain-extended by reversible addition-fragmentation chain transfer aqueous dispersion polymerization of diacetone acrylamide (DAAM) at 70 °C to produce PATAC100-PDAAMx diblock copolymer spheres at 20% w/w solids via polymerization-induced self-assembly. Transmission electron microscopy and dynamic light scattering (DLS) analysis confirm that the mean sphere diameter can be adjusted by systematic variation of the mean degree of polymerization of the PDAAM block. Remarkably, DLS studies confirm that highly cationic PATAC100-PDAAM1500 spheres retain their colloidal stability in the presence of either 4.0 M KCl or 3.0 M ammonium sulfate for at least 115 days at 20 °C. The mole fraction of PATAC chains within the stabilizer shell was systematically varied by the chain extension of various binary mixtures of non-ionic poly(N,N-dimethylacrylamide) (PDMAC) and cationic PATAC with DAAM to produce ([n] PATAC100 + [1 - n] PDMAC67)-PDAAMz diblock copolymer spheres at 20% w/w. DLS studies confirmed that a relatively high mole fraction of cationic PATAC stabilizer chains (n ≥ 0.75) is required for the dispersions to remain colloidally stable in 4.0 M KCl. Cationic worms and vesicles could also be synthesized using a binary mixture of PATAC and PDMAC precursors, where n = 0.10. However, the vesicles only remained colloidally stable up to 1.0 M KCl, whereas the worms proved to be stable up to 2.0 M KCl. Such block copolymer nanoparticles are expected to be useful model systems for understanding the behavior of aqueous colloidal dispersions in extremely salty media. Finally, zeta potentials determined using electrophoretic light scattering are presented for such nanoparticles dispersed in highly salty media.