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

光二聚聚冠醚的合成及其应用

基本信息

批准号：
61550683
负责人：
SHIRAI Masamitsu
金额：
$ 1.09万
依托单位：
University of Osaka Prefecture
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1986
资助国家：
日本
起止时间：
1986 至 1987
项目状态：
已结题

项目摘要

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.

1.制备具有作为阳离子结合位点的冠醚部分和作为可光二聚基团的肉桂酰基部分的聚合物。发现光反应聚合物的阳离子结合能力高于原始聚合物。研究了聚合物光二聚化程度和作为模板的阳离子种类对聚合物光二聚化过程的影响。 2．制备了具有不同尺寸的冠醚和肉桂酰基单元的聚合物。证实了碱金属阳离子与聚合物侧链中两个不同尺寸的冠醚单元形成显着的 1:2 络合物。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组合所预期的明显不同。聚合物的光二聚增强了其阳离子结合能力，且不改变阳离子选择性。 3．制备了具有非环状聚醚（苯并二甘醇二甲醚）和肉桂酰基单元的聚合物。甘醇二甲醚单元链长的增加增强了阳离子的结合能力，长氧乙烯单元优于大阳离子的结合。虽然聚合物的阳离子结合能力和选择性低于相应的环状聚醚（冠醚）聚合物，但通过肉桂酰基单元的光二聚作用大大提高了聚合物的阳离子结合能力和选择性。 4．在以光二聚聚冠醚包被的硅胶为固定相、水为流动相的离子色谱中，实现了碱金属阳离子和卤化物阴离子的分离。