低聚阳离子表面活性剂合成进展

Recent Progress in Synthesis of Oligomeric Cationic Surfactants

低聚表面活性剂作为一类高效低耗的新型表面活性剂,在三次采油、医药、工业缓蚀等领域展现出良好的应用前景。低聚表面活性剂由两个或更多两亲基元通过联接基团以化学键的方式联接而成,其结构介于单链表面活性剂和聚表面活性剂之间。联接基团拉近了分子中多个两亲基元的距离,使其表现出更强的聚集能力。同时,联接基团结构和分子空间拓扑结构更加多样化,使其具备了更加丰富的构象和聚集形貌转变过程。上述特性使其作为高效低耗型油田化学剂和响应性软物质材料方面独具优势,但其合成难度大,限制了该类表面活性剂的系统研究。基于此,详细归纳了线状、星状和环状3类不同空间拓扑结构的低聚阳离子表面活性剂的合成方法。着重介绍了以多元醇、多元胺、多元酚、多元环氧化合物、多元羧酸(酯)等作为原料,利用其所含的羟基、氨基、羧基、酯基等活性反应基团来制备作为联接基团骨架的星状中间体,然后将中间体末端进行季铵化反应,制得星状低聚阳离子表面活性剂。通过对3类低聚表面活性剂合成路线的总结,建议将来利用酯化反应、酰胺化反应、席夫碱反应、开环反应等的组合来设计合成具备刺激响应性及良好生物相容性的低聚阳离子季铵盐表面活性剂。

Oligomeric surfactants,as a novel class of surfactant with superior efficiency at very low concentration,have shown promising applications in the fields of enhanced oil recovery,pharmaceuticals,corrosion inhibitors,and so on.Oligomeric surfactants are composed of two or more amphiphilic moieties,which are chemically linked by a spacer group.They bridge the gap between monomeric surfactants and polymeric surfactants.With the help of the spacer group,the spatial distance of multiple amphiphilic moieties becomes closer,contributing to the stronger aggregation ability of the oligomeric surfactants.Meanwhile,the structure of the spacer group and the topological configuration are more diversified,resulting in multifarious transition processes of molecular configuration and aggregation morphology.These characteristics make them show unique advantages as highly-efficient oilfield chemicals and stimuli-responsive soft materials.But the difficult synthesis processes have been identified as the bottleneck of their systematic investigations.In this review,the synthesis methods of linear,star-like and ring-type oligomeric cationic surfactants,which were classified by the spatial topological structure,were summarized in detail.Specially,some facile reaction routes using polyols,polyamines,polyphenols,polyepoxides and polycarboxylic acids(esters)as raw materials were introduced in detail.Through these reaction routes,star-shaped intermediates,which were the backbone of spacer groups,could be well prepared based on some active groups such as hydroxyl,amino,carboxyl and ester groups.Then star-shaped oligomeric cationic surfactants could be smoothly synthesized after the quaternization of terminal groups of the intermediates.By summarizing the synthesis routes of the above three series of oligomeric surfactants,it was suggested that the combination of esterification reaction,amidation reaction,Schiff base reaction and ring-opening reaction could be used to design and prepare novel oligomeric cationic quaternary ammonium surfactant,which was stimuli-responsive and biocompatible.