Liese David, Wenk Hans Henning, Lu Xin, Kleinen Jochen, Haberhauer Gebhard
Institut für Organische Chemie, Universität Duisburg-Essen, Universitätsstraße 7, D-45117 Essen, Germany.
Evonik Operations GmbH, Evonik Industries AG, Goldschmidtstraße 100, D-45139 Essen, Germany.
Beilstein J Org Chem. 2020 Nov 19;16:2820-2830. doi: 10.3762/bjoc.16.232. eCollection 2020.
We report new dirhamnolipid ester forming reverse wormlike micelles in nonpolar solvents without the addition of any primer. Therefore, these compounds represent a rare case of a binary system showing this gel-like behavior. In this study, the influence of the concentration of the rhamnolipid ester and the ester alkyl chain length on the rheological properties of the reverse wormlike micelles in toluene was investigated in detail. Highly viscoelastic solutions were obtained even at a relatively low concentration of less than 1 wt %. The phase transition temperatures indicate that the formation of reverse wormlike micelles is favored for dirhamnolipid esters with shorter alkyl chain lengths. Oscillatory shear measurements for the viscoelastic samples reveal that the storage modulus () and the loss modulus () cross each other and fit the Maxwell model very well in the low-ω region. As is typical for wormlike micelle systems, the normalized Cole-Cole plot of / against / was obtained as a semicircle centered at / = 1. The formation of network structures was also verified by polarized light microscopy. The sample was birefringent at ambient temperature and anisotropic at an elevated temperature. Differential scanning calorimetry analysis yielded a transition enthalpy of about Δ = ±7.2 kJ/mol. This value corresponds to a strong dispersion energy and explains the formation of the highly viscous gels by the entanglement of wormlike micelles through the interaction of the alkyl chains.
我们报道了一种新型鼠李糖脂酯,它在不添加任何引发剂的情况下于非极性溶剂中形成反向蠕虫状胶束。因此,这些化合物代表了二元体系中呈现这种凝胶状行为的罕见案例。在本研究中,详细研究了鼠李糖脂酯浓度和酯烷基链长度对甲苯中反向蠕虫状胶束流变性质的影响。即使在相对较低的浓度(小于1 wt%)下也能获得高粘弹性溶液。相变温度表明,对于烷基链长度较短的鼠李糖脂酯,更有利于形成反向蠕虫状胶束。对粘弹性样品进行的振荡剪切测量表明,储能模量(G')和损耗模量(G'')相互交叉,并且在低ω区域与麦克斯韦模型拟合得非常好。正如蠕虫状胶束体系的典型情况那样,G'/G'' 相对于 ω/ω0 的归一化科尔 - 科尔图呈以 ω/ω0 = 1为中心的半圆。通过偏光显微镜也证实了网络结构的形成。该样品在环境温度下具有双折射性,在升高温度下具有各向异性。差示扫描量热法分析得出约ΔH = ±7.2 kJ/mol的转变焓。该值对应于强分散能,并解释了通过烷基链相互作用使蠕虫状胶束缠结而形成高粘性凝胶的原因。