Rheological behavior and mechanism of pH-responsive wormlike micelle variations induced by isomers of phthalic acid

Abstract

Responsive wormlike micelles (WLMs) constructed by different carboxylic acids are fascinating. However, it is unknown how the position of the carboxylic groups alters the stimuli-response of wormlike micellar systems. Herein, three pH-responsive WLMs based on Gemini-like surfactants (named o-EAPA, m-EAPA, and p-EAPA) were formed and studied through the complexation of N-erucamidopropyl-N,N-dimethylamine (UC₂₂AMPM) and o-phthalic acid (o-PA), m-phthalic acid (m-PA), or p-phthalic acid (p-PA) at the molar ratio of 2 : 1. The viscoelasticity, phase behavior and aggregate microstructure were separately explored by rheological, appearance observation and cryo-TEM methods. The results show that all phthalic acids can protonate UC₂₂AMPM, thereby forming WLMs. However, with the shorter spacer distance between two carboxyl groups in phthalic acid, o-EAPA exhibits the longer length scale of aggregates and a more efficient thickening ability compared to the other two systems. Similar results in the N,N-dimethyl oleoaminde-propylamine (DOAPA) and o-PA, m-PA, and p-PA systems further verify the applicability of this mechanism. Furthermore, the phthalic acid based WLMs are found to exhibit intriguing reversible pH-responsive behaviors, which include promptly switching between a high elastic system and a low viscosity fluid by pH control. The o-EAPA system possesses a larger viscosity maximum, which produces more precipitous viscosity changes as the pH varies. This study is beneficial for the formation of pH-responsive WLMs and to determine their advantages for applications.