分子模拟研究阴阳离子型氟表面活性剂的气液界面结构-高分子化学与物理专业论文.docx

万方数据 万方数据 浙江 浙江理工大学硕士学位论文 分子模拟研究阴阳离子型氟表面活性剂的气/液界面结构 摘要 氟表面活性剂是最重要的特种表面活性剂之一，在多个领域发挥着重要的作 用。表面活性剂的各种应用均与其在气/液界面的吸附层结构密切相关。所以探 讨氟表面活性剂分子结构以及分子间的相互作用对气/液界面层结构的影响具有 非常重要的应用价值和理论意义。 分子动力学模拟已经被广泛应用于研究表面活性剂溶液界面体系。本文采用 分子动力学方法探讨了含氟阴阳离子型表面活性剂亲水/疏水段结构以及分子间 的相互作用对单一表面活性剂体系及二元复配体系的气/液界面结构的影响。主 要结论如下： （1）全氟磺酸型表面活性剂分子的含氟段长越短则水溶性越好，含氟段越 长在气/液界面层的有序性越好；当疏水段长度相同，氟化程度越高则界面层越 有序。全氟辛基苯磺酸亲水头基之间以及与水的强相互作用使其在气/液界面层 的有序性比全氟辛基磺酸和全氟辛酸好。 （2）相比于阴离子型全氟表面活性剂，季铵盐阳离子表面活性剂的界面结 构有序性较差。该类表面活性剂亲水头基中的烷基链长度增加会使头基间的相互 作用增强，且随着相互作用增强，其在气/液界面层以及界面亚表层会形成复杂 的聚集结构。 （3）全氟辛烷磺酸与全氟辛酸复配体系的气/液界面的有序性介于两种单组 分溶液之间。全氟磺酸与六氟辛烷季铵盐混合后在气/液界面形成高度有序的单 层膜结构。两种表面活性剂之间有较强的协同作用，其复配体系的有序性高于单 组分溶液，而亲水头基间的静电吸引作用是主要原因。加入等摩尔的 NaCl 对吸 附层结构没有明显影响。 关键词：气/液界面，氟表面活性剂，复配，分子动力学，界面结构 I Abstract Fluorinated surfactants are most important special surfactants which play a key role in many fields. All the applications are closely related to the structure of fluorinated surfactants at the air/water interface. Therefore, it is necessary to investigate the relationship between the monomer structure and the interfacial structure of fluorinated surfactants. Molecular dynamics simulations has been widely employed to study the properties of different surfactant solutions. This thesis focus on exploring the influences of hydrophilic/hydrophobic segment structure on the interfacial structure of anionic and cationic fluorinated surfactants and their mixtures.The interaction between different surfactant chains and their influence on the interfcial structure was also explored through molecular dynamics simulations. The main conclusions are as follows: The aqueous solubility of sulfonated anionic fluorinated surfactant would be enhanced with the hydrophilic chain length increasing, and the adsoebed layer of surfactants monolayer would become disordered. On the contrary, the interfacial structure would be more order when the hydrophobic chain length increase. Besides, the interfcial structure of perfluorooctane sulfonic acid (SDBS) is more orded than that for