研究了两亲性无规共聚物聚(苯乙烯-co-甲基丙烯酸)(P(St-co-MAA))(单体摩尔比分别为6∶4和7∶3)自组装胶束的物理化学性质,及其作为假固定相( PSP)的胶束电动色谱性能。测定了聚合物胶束的临界胶束浓度( CMC),对胶束内核微环境的极性、表面电荷密度和流体力学直径等微结构参数进行了表征,对时间窗口、亚甲基选择性等电动色谱参数进行了测定,并与聚(甲基丙烯酸甲酯-co-甲基丙烯酸)(P(MMA-co-MAA))胶束、十二烷基硫酸钠( SDS)胶束体系进行了比较;利用线性溶剂化能关系( LSER)研究了聚合物PSP的选择性差异。结果表明:P( St-co-MAA)体系具有最小的CMC、最宽的时间窗口和最好的亚甲基选择性;LSER表明,疏水作用是决定聚合物PSP选择性的最主要因素,氢键酸度其次,特别是P( St-co-MAA)(单体摩尔比7∶3)体系具有最高的作用参数,显示了该PSP具有较高的分离选择性。
The amphiphilic copolymer poly ( styrene-co-methacrylic acid ) ( P ( St-co-MAA ) ) with molar ratios of 6∶4 and 7∶3 self-assembled to form micelles. The polymeric micelles were used as pseudostationary phase ( PSP ) in micellar electrokinetic chromatography ( MEKC ) . Their physicochemical properties and MEKC performance were investigated as well in the pres-ent work. The critical micelle concentration ( CMC ) , polarity, surface charge density and hydrodynamic diameter were used to characterize the solution physicochemical properties, while the methylene group selectivity was evaluated with n-alkylphenone homologous series. The time window and linear solvation energy relationship ( LSER) analysis were used to charac-terize the MEKC retention behavior and the selectivity. All of these were compared with poly ( methyl methacrylate-co-methacrylic acid ) ( P ( MMA-co-MAA ) ) with the molar ratio of 7∶3 and sodium dodecyl sulfate (SDS) micellar systems. The results showed that P(St-co-MAA) system had the minimum CMC, the widest time window and the best methylene group selectivi-ty . LSER analysis results showed that the hydrophobic effect was the most important interaction between solutes and PSPs, and the hydrogen-bonding acidity was the second significant factor on selectivity and MEKC retention behavior. P( St-co-MAA) system, especially with the molar ratio of 7∶3, had the highest effective parameter in LSER and showed a high separation selectiv-ity of PSP.