聚醚胺燃油清净剂的合成及构效关系

THE SYNTHESIS AND RELATIONSHIP BETWEEN STRUCTURE AND PERFOMANCE OF POLYETHER AMINE FUEL DETERGENT

采用胺基保护的方法合成了系列不同聚合单体、不同聚合度、不同端胺基结构的聚醚胺清净剂,用高分辨率质谱、核磁共振波谱、红外光谱等方法对聚醚胺的结构进行了表征;并比较了其清净性能,进而采用Material Studio软件建立了清净剂模型、汽油模型、积炭模型,研究了聚醚胺分子的构效关系。结果表明:聚醚胺的清净性能与其头部极性基团结构和聚合单元结构密切相关;分子结构相同时,数均相对分子质量为1000左右的聚醚胺清净性最好;极性基团相同时,环氧丁烷聚醚胺的清净性最好,且环氧丁烷比例较高的聚醚胺清净效果更好;聚合单元结构相同时,不同胺基封端清净剂的清净性由高到低的顺序为单伯胺聚醚胺>双伯胺聚醚胺≈N,N-二甲基-1,3-丙二胺封端的聚醚胺。分子模拟结果表明,聚醚胺的头部极性基团与积炭间的吸附能和聚环氧烷烃链与燃料油间的作用能决定了聚醚胺的清净性能。

A series of polyether amine(PEA)detergents with different polymerization monomers,different degrees of polymerization and different amino-terminated structures were synthesized by the method of amine protection,the structures of polyether amines were characterized by HRMS,NMR and IR,and their detergency were compared,furthermore,the structure-activity relationship of PEAs was studied by establishing detergent model,gasoline model and coke model with Material Studio software.The results showed that the detergency of polyetheramine was closely related to the structure of polar group in its head and the structure of polymerization unit.When the molecular structure was the same,polyether amine with average number molecular weight about 1000 had the best detergency;when polar groups were the same,the PEAs with higher proportion of epoxy butane had better detergency,and PEAs with pure epoxy butane chain had the best detergency;when the polymerization unit structures were the same,the order of detergency of the different amino-terminated detergents from high to low was mono-primary amine polyether amine>di-primary amine polyether amine≈N,N-dimethyl-1,3-propanediamine-terminated polyether amine.The results of molecular simulation showed that the adsorption energy between the head polar group and the carbon deposit,the interaction energy between the polyepoxide alkane chain and the fuel oil determined the detergency of polyether amine.