基于多酸簇合物的星形超分子聚合物：精准制备、在基础油中的溶液行为与摩擦学应用

高性能润滑材料是各种动力系统长期高效可靠运行的重要保障，广泛应用于装备制造、交通运输、航空航天等领域。针对这些需求，本项目旨在精准制备一系列油溶性的多酸簇基星形超分子聚合物，并将该类簇基聚合物复合材料作为具有高效减摩抗磨性能的润滑油添加剂。一、利用带有阳离子端基的聚甲基丙烯酸长链烷基酯或阳离子型嵌段共聚物与多酸簇合物之间的静电组装，精准制备以多酸簇合物或多酸簇基离子微区为核，以聚甲基丙烯酸长链烷基酯为支链的星形超分子聚合物。二、研究它们在基础油中的分散性、稳定性、粘温特性、粘弹性，探讨它们在不同温度、不同浓度条件下的自组装行为和相互作用机制。三、研究它们在基础油中的减摩抗磨、抗氧化、耐腐蚀等性能，揭示其分子结构、自组装结构与减摩抗磨性能三者间的内在联系，实现对它们的摩擦学性能的有效调控，并从原子、分子、超分子三个层次探究其摩擦学本质和润滑机理，进而发展具有高润滑性能的簇基高分子复合材料。

High-performance lubricants are the important safeguard for many power systems working with long term, high efficiency, and good reliability. They are widely applied in the fields of equipment manufacturing, traffic transportation, and aerospace. These practical demands prompt us to precisely prepare oil-soluble, polyoxometalate (POM) cluster based starlike supramolecular polymers, in which the POM anions or POM-based ionic nanodomains are closely encapsulated by poly(alkyl methacrylate)s (Alkyl: Dodecyl, Stearyl, and Behenyl). The resulting POM-based polymeric composite materials can be utilized as highly effective lubricant additives for friction and wear reduction in base oils. (i) On the basis of electrostatic self-assembly, we precisely prepare a series of starlike supramolecular polymers, where the cores are POMs or POM-based ionic nanodomains, while the arms are poly(alkyl methacrylate)s. These supramolecular assemblies can be regarded as a model of starlike polymers because of their highly similar architectures. (ii) The dispersibility, stability, viscosity-temperature characteristics, and viscoelasticity of the model stars in base oils are studied in detail. Furthermore, we systematically address their self-assembled behaviors in base oils under temperature- and concentration-dependent conditions. Then, the interactions between the star and the base oil and the intra- and inter-star interactions between the segments of the poly(alkyl methacrylate) arms are clarified for the self-assembled mechanism. (iii) Meanwhile, the friction reduction, anti-wear, anti-oxidation, and anti-corrosion properties of these POM-based stars are investigated in base oil. Moreover, we will build a substantial relationship among molecular structures, self-assembled structures, and tribological performances. And also, we will clarify the tribological nature and the lubrication mechanism at atomic, molecular, and supramolecular levels. These will lead to effective regulation in the tribological nature of the POM based stars. The present concept concerning a combination of POM clusters with starlike polymers will open a new avenue to develop cluster based polymeric composites for high-performance tribological applications.