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New Materials Starting from Organometallic Complexes

以有机金属配合物为原料的新材料

基本信息

批准号：
01490012
负责人：
YASUDA Hajime
金额：
$ 3.52万
依托单位：
Hiroshima University (1990)Osaka University (1989)
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

项目摘要

This project has been done with the object of synthesizing new functional materials starting from organometallic compounds.1) Organolanthanide complexes of type (C_5R_5) _2LnR has first been found to catalyze the polymerization of Methyl Methacrylate (MMA) leading to high molecular weight polymers with extremely narrow polydispersity in excellent yield. Further more, preparation of highly stereoregular polymers (syndiotacticity, >95%) was also succesful by conducting the polymerization at low temperature. Block copolymerization of ethylene with MMA was also realized by introducing MMA into the samarium initiated polyethylene living end. This is the first example of copolymerization between non-polar and polar monomers. 2) Pyrolysis of organometallic polymers or polymeric metal complexes provides new carbon composites containing ultra-fine metal particles, which are dispersed homogeneously in the carbon matrices. Characteristics of these materials lie in their high stability in aerobic conditions. Carbon composites containing Pt, Pd, Rh, Ru or Fe particles serve as good catalysts for hydrogenation of olefins and decomposition of H_2O_2. Ag contained materials show good bacteriostatic activity for various bacteria.3) In order to evaluate the unique behavior of group 5 early transition metal complexes, a series of Nb-alkyne complexes was synthesized starting from a Nb-ethylene complex. As a result, the mode of reactions could be classified into 3 groups. Ethylniobiumalkyne complexes exhibits an unusual alpha-agonstic interaction between ethyl group and metal. This result indicates that formation of new Nb-carbene complexes is possible through this type of bonding.

1）首次发现（C_5R_5）_2LnR型稀土金属有机配合物催化甲基丙烯酸甲酯（MMA）的聚合，得到了高分子量的聚合物，聚合物的分子量分布窄，产率高。此外，在低温下进行聚合也成功地制备了高度立构规整的聚合物（间同立构规整度>95%）。通过在钐引发聚乙烯活性端引入甲基丙烯酸甲酯，实现了乙烯与甲基丙烯酸甲酯的嵌段共聚合。这是非极性和极性单体之间的共聚的第一个实例。2)有机金属聚合物或聚合金属络合物的热解提供了含有超细金属颗粒的新型碳复合材料，所述超细金属颗粒均匀地分散在碳基质中。这些材料的特征在于它们在有氧条件下的高稳定性。含Pt、Pd、Rh、Ru或Fe颗粒的碳复合物是烯烃加氢和H_2O_2分解的良好催化剂。含银材料对多种细菌均表现出良好的抑菌活性。3）为了评价第5族前过渡金属配合物的独特性能，以Nb-乙烯配合物为起始原料，合成了一系列Nb-炔配合物。结果表明，反应模式可分为3类。乙基鎓炔配合物表现出不寻常的乙基和金属之间的α-激动剂相互作用。这一结果表明，通过这种类型的键合，新的Nb-卡宾络合物的形成是可能的。