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的分离材料。该分离材料对有机物和金属离子具有优异的分离和提取能力，因为它们在分子中具有许多具有不同空腔大小的结合位点。在这个项目中，我们提出使用杯芳烃作为环化合物。杯芳烃是一种环酚醛低聚物，其选择性阳离子萃取能力特别吸引人。杯芳烃与某些配体（酯类、酮类和胺类）表现出对碱金属阳离子的离子亲和性。用乙酸乙酯衍生物详细测定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很少被报道。近年来，我们对杯芳烃的聚合反应进行了研究，重点研究了杯芳烃的两种聚合反应：对羟基杯芳烃和杯芳烃间苯二甲酸芳烃。它们在苯环上有反应位点，在温和的条件下容易与甲醛发生反应。由于杯芳烃单元的紧密聚集状态，聚杯芳烃有望具有新的性能和功能。聚对羟基杯[6]芳烃对碱金属阳离子的萃取能力与对羟基杯[6]芳烃本身相同，均有利于Cs+，且萃取能力随分子量的增加而增强。杯状[4]间苯二甲酸对碱金属阳离子没有亲和性。而聚杯状间苯二甲酸乙酯则表现出对Cs+的亲和力。这说明杯芳烃单元的聚集为杯芳烃的提取提供了新的途径。新位点的亲和力和选择性将取决于杯芳烃单元在聚合物链中的聚集状态。这些聚合物分子中含有溶剂，这些溶剂被笼在杯芳烃单元形成的位点上。“笼”被苯环包围，空间中充满π电子。因此，“笼子”有望成为纳米级反应堆。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