Sagisaka Masanobu, Kudo Kotaro, Nagoya Shota, Yoshizawa Atsushi
Department of Frontier Materials Chemistry, Graduate School of Science and Technology, Hirosaki UniversityHirosaki, 036-8561, Japan.
J Oleo Sci. 2013;62(7):481-8. doi: 10.5650/jos.62.481.
To develop an efficient and fluorine-free solubilizer for a water/supercritical CO₂ microemulsion (W/CO₂ μE), in this study, a highly methyl-branched alkyl, isostearyl group was focused on as a CO₂-philic tail, and the custom-made isostearyl surfactant, sodium 2-(4,4-dimethylpentan-2-yl)-5,7,7-trimethyloctyl sulfate (SIS1) was synthesized. The surface tension (γ) of an aqueous SIS1 solution was measured at ambient pressure as a function of surfactant concentration, and it was found to be 25 mN/m at concentrations of > 1.5 mM. A low γ value can generally be reached only by a fluorocarbon surfactant, which implies that SIS1 has an excellent solubilizing power for the W/CO₂ μE, similar to some fluorocarbon surfactants reported previously. Visual observations of the SIS1/W/CO₂ mixtures revealed the formation of transparent single phases without separated water, identified as W/CO₂ μE. The μE was well-stabilized at pressures > 210 bar and temperatures > 55 °C. At 75 °C and 370 bar, SIS1 was found by spectral measurements using a water-soluble UV-light absorber to solubilize water contents up to a maximum water-to-surfactant molar ratio (W0) = 50. The achievement of W0 = 50 in a W/CO₂ μE system has not been reported previously in similar hydrocarbon surfactant/W/CO₂ systems, and this demonstrates that a highly methyl-branched alkyl group can act as a good CO₂-philic group for a W/CO₂ -type surfactant.
为开发一种用于水/超临界CO₂微乳液(W/CO₂ μE)的高效无氟增溶剂,在本研究中,高度甲基支化的烷基异硬脂基被作为亲CO₂尾基进行研究,并合成了定制的异硬脂基表面活性剂2-(4,4-二甲基戊-2-基)-5,7,7-三甲基辛基硫酸酯钠(SIS1)。在常压下测量了SIS1水溶液的表面张力(γ)随表面活性剂浓度的变化,发现在浓度>1.5 mM时其表面张力为25 mN/m。通常只有含氟表面活性剂才能达到较低的γ值,这意味着SIS1对W/CO₂ μE具有优异的增溶能力,类似于先前报道的一些含氟表面活性剂。对SIS1/W/CO₂混合物的目视观察表明形成了无水分分离的透明单相,确定为W/CO₂ μE。该微乳液在压力>210 bar和温度>55 °C时能很好地稳定。在75 °C和370 bar下,通过使用水溶性紫外光吸收剂的光谱测量发现SIS1能够增溶高达最大水与表面活性剂摩尔比(W0)=50的水含量。在类似的烃类表面活性剂/W/CO₂体系中,此前尚未报道过W/CO₂ μE体系中W0 = 50的情况,这表明高度甲基支化的烷基可作为W/CO₂型表面活性剂的良好亲CO₂基团。