Synthesis of Photodimerizable Poly(crown ether)s and Their Application

1.合成了以冠醚为阳离子结合部位，以肉桂酰基为光致二聚基团的聚合物。结果表明，光反应聚合物的阳离子结合能力高于原聚合物。研究了聚合物的光二聚程度以及在聚合物光二聚过程中用作模板的阳离子种类的影响。合成了具有不同大小冠醚和肉桂酰基的聚合物。证实了碱金属阳离子与聚合物侧链上两个不同大小的冠醚单元形成1：2的络合物。这些聚合物的碱金属阳离子结合能力和选择性与相同环尺寸冠醚单元的聚合物的预期结合能力和选择性明显不同。聚合物的光致二聚作用增强了它们的阳离子结合能力，但不改变阳离子选择性。合成了含非环聚醚(苯二甘醇)和肉桂酰基的聚合物。Glyme单元链长的增加增强了阳离子的结合能力，长的氧乙烯单元更有利于大阳离子的结合。虽然聚合物的阳离子结合能力和选择性低于含有相应环状聚醚(冠醚)的聚合物，但通过肉桂酰基单元的光二聚，它们的阳离子结合能力和选择性都得到了很大的提高。在离子色谱柱中，以包被光二聚型聚冠醚S的硅胶为固定相，水为流动相，实现了碱金属阳离子和卤化物阴离子的分离。

1. Polymers having both crown ether moieties as cation binding sites and cinnamoyl moieties as photodimerizable groups were prepared. The cation binding ability of the photoreacted polymers was found to be higher than that of original polymers. The effects of the degree of photodimerization of the polymers and of the kind of cations used as a template during photodimerization of the polymers were studied.2. Polymers which have different sized crown ethers and cinnamoyl units were prepared. A significant 1:2 complex formation of alkali metal cations with two different sized crown ether units in the side chain of the polymers was confirmed. The alkali metal cation binding ability and selectivity of the polymers were markedly different from those expected from the combination of polymers of same ring-size crown ether units. The photodimerization of the polymers enhanced their cation binding ability without change in the cation selectivity.3. Polymers with both non-cyclic polyethers (benzodiglymes) and cinnamoyl units were prepared. The increase in the chain length of glyme units enhanced the binding ability of cations and the long oxyethylene units were preferable to the binding of large cations. Although the cation binding ability and selectivity of the polymers were lower than those of polymers bearing corresponding cyclic polyethers (crown ethers), they were much improved by the photodimerization of the cinnamoyl units.4. In the ion chromatography using silica gels coated with the photodimerizable poly(crown ether)s as stationary phase and water as mobile phase, the separation of alkali metal cations and halide anions was accomplished.