Interfacial Dilatational Rheology as a Bridge to Connect Amphiphilic Heterografted Bottlebrush Copolymer Architecture to Emulsifying Efficiency

Abstract Hypothesis: Molecular architecture and composition of amphiphilic bottlebrush copolymers will dictate the dominant interfacial relaxation modes and the corresponding dilatational rheology for adsorbed layers at oil/water interfaces in a way that will correlate with the emulsifying efficiency of different bottlebrush copolymers. Experiments: Amphiphilic, xylene-soluble poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PBA) heterografted bottlebrush copolymers with controlled differences in backbone length, hydrophilicity and arm length were synthesized by atom transfer radical polymerization. Dilatational rheology of adsorbed layers at the xylene/water interface was probed via pendant drop tensiometry by measuring the interfacial stress response to either large-amplitude strain cycling or small-amplitude strain oscillation. The rheological response was recorded as a function of interfacial pressure for adsorbed layers under different compression states. Emulsifying efficiency was determined as the lowest copolymer concentration that yielded water-in-xylene emulsions with at least one-month stability against coalescence. Findings: The more hydrophilic copolymers with longer PEO arms exhibited non-hysteretic stress-strain response curves in large-amplitude strain cycling and a tendency for the modulus to increase with increasing interfacial pressure. These were more efficient emulsifiers than less hydrophilic copolymers that exhibited hysteretic interfacial rheology. Mere existence of significant moduli did not correlate with high emulsifying efficiency, while an increase in modulus with increasing interfacial pressure did so.