Development of New Separation Materials for Organics and Metal Ions from Cyclic Compound as a Monomer

以环状化合物为单体制备了新型分离材料。该分离材料将对有机物和金属离子具有优异的分离和萃取能力，因为它们在分子中具有许多具有各种空腔尺寸的结合位点。在本项目中，我们提出使用杯芳烃作为环状化合物。杯芳烃是环状酚类低聚物，其选择性阳离子萃取能力特别有吸引力。杯芳烃与一些配体（酯，酮和胺）显示出对碱金属阳离子的离子迁移能力。用乙酸乙酯衍生物详细研究了杯芳烃的构象和大小对碱金属阳离子选择性萃取的影响。尽管人们对杯芳烃的合成和性质进行了大量的研究，但含有杯芳烃单元的聚合物的报道却很少。近年来，我们对杯芳烃的聚合反应进行了研究，并对两种杯芳烃进行了研究 ...更多信息 ：对羟基杯[6]芳烃和杯[4]间苯二酚芳烃。它们在苯环上具有反应活性位点，在温和条件下容易与甲醛反应。聚杯芳烃具有新的性质和功能，这主要归因于杯芳烃单元的紧密聚集状态。聚对羟基杯[6]芳烃对碱金属离子的萃取能力与对羟基杯[6]芳烃相同，对Cs+的萃取能力更强，且萃取能力随分子量的增加而增强。另一方面，杯[4]间苯二酚芳烃对碱金属离子没有亲和力。然而，聚（杯[4]间苯二酚芳烃）表现出对Cs+的亲和力。这表明杯芳烃单元的聚集赋予了聚杯芳烃新的萃取能力。新位点的亲和力和选择性将取决于聚合物链中杯芳烃单元的聚集状态。这些聚合物在分子中含有溶剂，其被笼在杯芳烃单元形成的位点中。这个“笼子”被苯环包围，空间充满了π电子。因此，“笼”预计将是一个纳米尺寸的反应器。少

New separation materials were prepared from cyclic compounds as a monomer. The separation material will have an excellent separation and extraction ability for organics and also for metal ions, because they have many binding sites with various cavity sizes in the molecule. In this project, we proposed to use calixarenes as cyclic compound. Calixarenes are cyclic phenolic oligomers and their selective cation extraction ability is particularly attractive. Calixarenes with some ligands(esters, ketones and amines) showed the ionophoric abilities for alkali metal cations. The influence of conformation and size of calixarenes on the selective extraction for alkali metal cations was determined in detail by using the ethyl acetate derivatives. In spite of many studies concerning the synthesis and property of calixarens, very few of polymers containing calixarene units have been reported. Recently, we have investigated the polymerization of calixarenes and focus our interest on two calixarenes … More : p-hydroxtcalix[6]arene and calix[4]resorsinarene. These have reactive sites in benzene ring and readily react with formaldehyde under mild condition. The polycalixarenes are expected to have new properties and functions, which were attributed to closely aggregated state of calixarene units. The extraction affinity into alkali metal cations for poly(p-hydroxycalix[6]arene) was the same as p-hydroxycalix[6]arene itself, in favor to Cs+ and the ability increased with increasing the molecular weight. On the other hand, calix[4]resorcinarene showed no affinity into alkali metal cations. However, the poly(calix[4]resorcinarene) showed the affinity into Cs+. This indicated that new extraction ability was given to the poly calixarenes by aggregation of calixarene units. The affinity and selectivity of new sites will depend on the aggregated state of calixarene units in the polymer chain. These polymers contained solvent in the molecule, which was caged in the sites formed by calixarene units. The "cage" is surrounded by benzene rings and the space is full of π-electrons. Thus, the "cage" is expected to be a nano-sized reactor. Less