Lettow John S, Lancaster Thomas M, Glinka Charles J, Ying Jackie Y
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Langmuir. 2005 Jun 21;21(13):5738-46. doi: 10.1021/la046918b.
The aim of this study is to determine the effects of oil solutes and alcohol cosolvents on the structure of oil-in-water microemulsions stabilized by poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers. The systems investigated involved the solubilization of 1,3,5-trimethylbenzene or 1,2-dichlorobenzene by P123 (EO(20)-PO(70)-EO(20)) pluronic surfactant micelles in water and water + ethanol solvents. The structures of these swollen micelles were determined by small-angle neutron scattering (SANS). A thermodynamic model was employed to interpret the characterization data. The results of the thermodynamic model for micellization agreed well with the SANS data from samples of micelles swollen by both oils. The model predicted the size of the micelles within 5% accuracy using only one fitting parameter, the micelle polydispersity. Ethanol had significantly different effects on the polymer micelles that contained solubilized oil compared to pure polymer micelles. For pure polymer micelles, the addition of ethanol increased the solubility of the polymer and, therefore, decreased the total volume fraction of micelles, while for polymer-oil aggregates, ethanol tended to have a positive effect on the volume fraction of micelles. SANS results showed that the greatest divergence from pure aqueous solvent results occurred at oil concentrations above the microemulsion stability limit.
本研究的目的是确定油溶质和醇类助溶剂对由聚(环氧乙烷)-聚(环氧丙烷)-聚(环氧乙烷)(PEO-PPO-PEO)三嵌段共聚物稳定的水包油微乳液结构的影响。所研究的体系涉及P123(EO(20)-PO(70)-EO(20))普朗尼克表面活性剂胶束在水和水+乙醇溶剂中对1,3,5-三甲基苯或1,2-二氯苯的增溶作用。这些溶胀胶束的结构通过小角中子散射(SANS)测定。采用热力学模型来解释表征数据。胶束化的热力学模型结果与两种油溶胀的胶束样品的SANS数据吻合良好。该模型仅使用一个拟合参数,即胶束多分散性,就能以5%的精度预测胶束大小。与纯聚合物胶束相比,乙醇对含有增溶油的聚合物胶束有显著不同的影响。对于纯聚合物胶束,添加乙醇会增加聚合物的溶解度,从而降低胶束的总体积分数,而对于聚合物-油聚集体,乙醇往往对胶束的体积分数有积极影响。SANS结果表明,在油浓度高于微乳液稳定性极限时,与纯水溶剂结果的差异最大。