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研究有机酸结构对 pH 响应蠕虫状胶束体系流变性和聚集体转变的影响。

Study on the effect of the organic acid structure on the rheological behavior and aggregate transformation of a pH-responsive wormlike micelle system.

机构信息

Shandong Key Laboratory of Oilfield Chemistry, School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, P. R. China.

出版信息

Soft Matter. 2019 Apr 10;15(15):3160-3167. doi: 10.1039/c9sm00088g.

Abstract

A worm-like micelle (WLM) system can be obtained by mixing long-chain cationic surfactants and polybasic organic acids in an aqueous solution. However, the effect of different organic acid structures on the rheological behavior of WLM systems has not been researched. Herein, a novel pH-responsive wormlike micelle system (EATA) was constructed by the complexation of N-erucamidopropyl-N,N-dimethylamine (UC22AMPM) and benzene tricarboxylic acid (TA) at a molar ratio of 3 : 1. UC22AMPM/citric acid (EACA) was also prepared to perform a comparison. The rheological behavior, aggregate transformation and thickening mechanism of EATA solutions were investigated by using rheological measurements, cryo-TEM, DLS, surface tension and 1H NMR. The results show that, at low pH, spherical micelles were formed and the EATA solution exhibited a lower viscosity than the EACA system due to the strong hydrophobicity of the phenyl groups of TA molecules, but the viscosity reaches 106 mP s at pH 4.80. Because of the lower pKa value of TA than CA, the viscosity of the EATA system drops sharply with the appearance of precipitates caused by the isoelectric point when the pH is greater than 4.80. In addition, by circularly changing the pH value several times, the wormlike micelles could maintain their original viscoelasticity without being weakened in the slightest.

摘要

在水溶液中混合长链阳离子表面活性剂和多羧酸可以得到蠕虫状胶束(WLM)体系。然而,不同有机酸结构对 WLM 体系流变行为的影响尚未得到研究。本文通过摩尔比为 3:1 的 N-鲸蜡基-N,N-二甲基丙基-1-胺(UC22AMPM)和苯三甲酸(TA)的复合,构建了一种新型 pH 响应蠕虫状胶束体系(EATA)。还制备了 UC22AMPM/柠檬酸(EACA)进行对比。通过流变测量、低温透射电镜、DLS、表面张力和 1H NMR 研究了 EATA 溶液的流变性、聚集转变和增稠机理。结果表明,在低 pH 下形成了球形胶束,由于 TA 分子苯环的强疏水性,EATA 溶液的粘度低于 EACA 体系,但在 pH 4.80 时粘度达到 106 mP s。由于 TA 的 pKa 值低于 CA,当 pH 大于 4.80 时,由于等电点的出现,EATA 体系的粘度会急剧下降,并产生沉淀。此外,通过多次循环改变 pH 值,蠕虫状胶束可以保持其原有的粘弹性,而不会有丝毫减弱。

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