智能开关微乳及其清洗/回收矿物油的构效关系

According to the urgent need of ‘microemulsion is hardly possible to be fast and completely demulsified and to be widely used in industry’ and ‘the efficient treatment pollution and recovering of mineral oil’, the almost completely on-off surfactants, switching between no interfacial activity form and surfactant form under the environment-friendly stimuli of CO2/N2 (and/or H2O2/N2H4+CO2/N2, will be symmetrically designed and synthesized. Based on the relationship of structure and on-off responsiveness for surfactant-self, the oil-in-water reversible smart microemulsion of microemulsion-oil water completely phase separation-microemulsion recovering sensitively transition will be fabricated. Consequently, the relationship between the structure of surfactants and the responsiveness of oil water completely phase separation-microemulsion recovering will be revealed. And, the fabrication strategy and the control mechanism of smart microemulsion will be established. Taking advantage of the ultralow interfacial tension and the excellent solubilization of complex oil originated from the microemulsion, industrial mineral oil washing and recovering could be realized by the usage of the smart on-off surfactant-based microemulsion. It is expected that the difficulty of being hardly possible to be fast and completely demulsified for emulsion with high level of surfactants could be solved. All of these results could be powerful backup for the efficient treatment of pollution and recovering of industrial mineral oil.

针对“微乳难以快速彻底破乳制约其大规模工业应用”和“工业矿物油污染治理与油资源高效回收再利用”两大问题之亟需，采用对环境相对安全的CO2/N2(和/或H2O2/N2H4+CO2/N2双重)触发手段，系统设计并制备界面活性在非表面活性剂和表面活性剂之间可逆转换的一元和可水相循环开关表面活性剂群，研究表面活性剂本身结构与其开关响应构效关系，构筑具有灵敏“微乳-彻底分相-微乳复原”可逆转换响应的智能O/W微乳，进而研究并阐明开关表面活性剂结构与智能微乳破乳相分离-复乳可逆转换之间的构效关系，架构智能微乳的组装策略和调控机制；利用微乳的超低界面张力和对复杂油类的出色增溶能力，将基于全开关表面活性剂的智能微乳用于工业矿物油的洗除和洗后油资源的回收，以突破微乳使用后高表面活性剂含量乳液难以有效破乳的局限，为工业矿物油固体污染治理和油资源高效回收实现双赢提供有力支撑。

表面活性剂含量高、热力学稳定的微乳难以快速而彻底地破乳，成为制约微乳大规模应用的技术瓶颈之一；此外，矿物油污染是世界各国普遍遇到的问题，如何同时兼顾“环境修复”和“油资源高效回收”面临巨大挑战。本着“利用微乳的超低界面张力和对复杂油类的出色增溶能力，将基于全开关表面活性剂的智能微乳用于工业矿物油的洗除和洗后油资源的回收”学术设想，以“全开关表面活性剂为主乳化剂，构筑可以实现微乳-彻底分相可逆开关转换的智能O/W微乳，实现智能微乳用于矿物油高效洗除和洗后油资源便捷回收”为主要内容开展研究。设计并制备了一元开关和可水相循环开关表面活性剂47种，以pH、Redox、CO2/N2及其组合6种开关手段，响应性质从表面活性剂表界面吸附、自组装和乳化等成功地延伸到表面活性剂的Krafft温度，率先实现了基于Redox或CO2/N2单独和双重地可逆调控阴离子型和两性离子型表面活性剂的Krafft温度。响应体系涵盖表面活性剂胶束、自发囊泡、乳液、蠕虫状胶束和微乳(14例)等自组装体系5大类，不仅报导了第1例基于Redox开关可逆的有表面活性剂微乳，而且成功地拓展到无表面活性剂微乳，率先报导了温度调控的2例无表面活性剂开关微乳。分别从同分异构（亲水基和疏水基）、疏水链长和亲水基种类等3角度4个层面研究了表面活性剂、乳液和微乳开关响应的构效关系。对于以Se为触发开关基团的单头-单尾型表面活性剂而言，Se在疏水链中的位置是决定表面活性剂本身及其自组装体系开关响应的关键因素。率先报导了可水相循环表面活性剂，建立了一元开关、可水相开关表面活性剂分别在土壤持久性污染物、矿物油类污染治理和资源回收等方面的应用技术路线，结果表明不仅油污和持久性污染物的洗除率大于98%，而且表面活性剂、油资源和持久性污染物的定向回收比例均不低于90%。为工业矿物油固体污染治理和油资源高效回收实现双赢提供有力支撑。