Preparation of Functional Polymers Containing Untrafine Metal Particles and Their Applications

1.本研究涉及含超细金属粒子的功能聚合物的合成及其在高选择性、高效率有机合成和高效太阳能转换方面的应用。合成功能聚合物的第一步是制备超细金属粒子分散体。在本研究中，考察了各种还原金属离子的方法，发现光还原方法是有效的，因为这种方法特别是产生小颗粒的金属和单分散胶体。在不饱和表面活性剂的存在下，通过光化学还原金属离子，然后聚合表面活性剂，成功地合成了含有超细金属粒子的功能聚合物。3.1)含有超细铂粒子的分子组件在催化烯烃加氢反应中表现出了很高的催化活性。以聚醚为亲水基团的非离子表面活性剂具有比离子型表面活性剂更高的活性。结果表明，以不饱和脂肪酸为底物的烷基链上的双键位置不同，其加氢速率也不同。这种区域选择性是由表面活性剂组件对底物的增溶作用解释的。含超细胶体铂粒子的聚合胶束在EDTA/&lt；Ru(Bpy)_3^(2+)&gt；/&lt；mv^(2+)&gt；体系中被用作光化学产氢催化剂。与普通铂催化剂相比，它具有更高的催化活性和稳定性。非离子聚合胶束负载的催化剂比离子负载的催化剂具有更高的催化活性。在目前的体系中，非离子亲水基团会带来有效的电荷分离和电子转移。

1. The present study concerns synthesis of functional polymers containing ultrafine metal particles and their application to highly selective and effective organic syntheses and effective solar energy conversion. The first step of the synthesis of the functional polymers is preparation of the dispersions of ultrafine metal particles. In this study, various methods for reduction of metal ions was examined and photo-reduction method was disclosed to be effective because this method especially produces small particles of metal and monodispersed colloid.2. Synthesis of functional polymers containing ultrafine metal particles was succeeded by photochemical reduction of metal ions in the presence of the assemblies of unsaturated surfactants followed by polymerization of the surfactants.3.1) The molecular assemblies containing ultrafine platinum particles showed high catalytic activities when they were used as the catalysts for hydrogenation of olefins. Nonionic molecular assemblies having polyether groups as hydrophilic moieties of the surfactants showed the higher activity than ionic ones. It was found that the hydrogenation rate varies with the location of double bond in alkyl chain of the unsaturated fatty acid used as a substrate. This regio-selectivity is explained by the effect of the surfactant assemblies to solubilize substrates. These polymers containing colloidal metals are expected to be developed as highly selective catalysts for hydrogenation.2) Polymerized micelle containing ultrafine colloidal platinum particles was used as a catalyst for photochemical hydrogen generation in the system of EDTA/ <Ru(bpy)_3^(2+)> / <MV^(2+)> . It showed higher catalytic activity and stability than the common platinum catalysts. The catalyst supported by nonionic polymerized micelle was more active than those supported by ionic ones. The nonionic hydrophilic group would bring effective charge separation and electron transfer in the present system.