Design of New Materials starting from Organometallics

从有机金属学出发的新材料设计

• 批准号: 04455018
• 负责人: YASUDA Hajime
• 金额: $ 4.42万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04455018/
• 关键词: Rare earth metal; Monodisperse polymer; Biodegradable polymer; Steam invigoration; Active sludge; メソポア活性炭; 高選択的吸着; 微粒子高分子錯体; ポリ(アルキルアクレリート); トヘキセンの還元; 単分散高分子量ポリマー

1)Rare earth metal complexes bearing dimethylsilylene bridged bulky cyclopentadienyl ligand have been synthesized and the polymerizations of ethylene, 1-pentene and 1-hexene were performed. As a result, high polymers of ethylene exceeding M_n of 400,000(molecular weight distribution 1.6)and of 1-pentene or 1-hexene exceeding M_n of 60,000(molecular weight distribution 1.7)were obtained. As a tytpical example of bulky rare earth metal complexes, characterization of Me_2Si[2(3), 4-(SiMe_3)_2C_5H_2]_2SmCH(SiMe_3)_2 has been made by X-ray analysis.2)Copolymerizations of an optical active lactone, MOHEL, with caprolactone and varelolactone were performed with ALEt_3-H_2O catalystsystem. In any copolymers with the ratio of 30 : 70, biodegradation with active sludge or enzymes easily occurred as compared with respective homopolymers. Biodegradation of L- and L/D lactide copolymers was also studied.3)Steam invigoration at 1000ﾟC of Cp_3Ln mixed pitch gave new carbon materials with high mesopore ratio. Absorption of high molecular weight substances such as vitamine B_<12>.dyes, maltooligosaccharides, cyclodextrin, and humic acid occurred with the resulted carbon materials has been examined.

1)合成了含二甲基硅烷桥联大体积环戊二烯配体的稀土金属络合物，并进行了乙烯、1-戊烯和1-己烯的聚合反应。结果得到了M_n超过40万(分子量分布1.6)的乙烯和超过60,000(分子量分布1.7)的1-戊烯或1-己烯的高聚合物。以Me_2Si[2(3)，4-(SiMe_3)_2C_5H_2]_2SmCH(SiMe_3)_2为典型的块状稀土金属络合物，用X-射线衍射法表征了Me_2Si[2(3)，4-(Sime_3)_2C_5H_2]_2SmCH(SiMe_3)_2。在任何比例为30：70的共聚物中，与各自的均聚物相比，活性污泥或酶更容易发生生物降解。研究了L-丙交酯和L/D丙交酯共聚物的生物降解性。3)CP_3LN混合沥青在1000ﾟC水蒸气活化可制得中孔率较高的新型炭材料。考察了合成的碳材料对维生素B、染料、低聚麦芽糖、环糊精和腐植酸等高相对分子质量物质的吸附。

项目成果

H.Yasuda: "Synthesis of monodispersed high molecular weight polymers and isolation of an organolanthanide(III) intermediate" J.Am.Chem.SOC.114. 4908-4910 (1992)

H.Yasuda：“单分散高分子量聚合物的合成和有机镧系元素 (III) 中间体的分离”J.Am.Chem.SOC.114。

H. Yasuda: "New approach to block copolymerization of ethylene with alkyl methacrylates and lactones by unique catalysis with organolanthanide complexes" Macromolecules. 25. 5115-5116 (1992)

H. Yasuda：“通过有机镧系化合物配合物的独特催化作用，实现乙烯与甲基丙烯酸烷基酯和内酯嵌段共聚的新方法”。

Hajime Yasuda: "Synthesis of high molecular weight poly(methyl methacrylate) with extremely low polydispersity" Macromolecules. 26. 7134-7143 (1993)

Hajime Yasuda：“具有极低多分散性的高分子量聚（甲基丙烯酸甲酯）的合成”大分子。

安田源: "最先端高分子" 三田出版, (1994)

安田源：“尖端聚合物”三田出版社，（1994）

H. Yasuda: "New carbon composites containing ultrafine metal particles. 2. Synthesis by pyrolysis of pitch-organometallic blends." J. Inorg. Organomet. Polym.1. 239-244 (1991)

H. Yasuda：“含有超细金属颗粒的新型碳复合材料。2.通过沥青-有机金属混合物的热解合成。”