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学科主题: 金属有机化学
题名: Copolymerization of cyclohexene oxide with CO2 by using intramolecular dinuclear zinc catalysts
其他题名: 分子内双核锌络合物用于环己烯环氧与二氧化碳的共聚合反应
作者: Xiao YL(肖友利) ; Wang Z(王正) ; Ding KL(丁奎岭)
通讯作者: 丁奎岭
刊名: Chem.-Eur. J.
发表日期: 2005-01-01
卷: 11, 期:12, 页:3668-3678
收录类别: SCI
部门归属: 中科院上海有机化学研究所金属有机
英文摘要: The intramolecular dinuclear zinc complexes generated in situ from the reaction of multidentate semi-azacrown ether ligands with Et2Zn, followed by treatment with an alcohol additive, were found to promote the copolymerization of CO2 and cyclohexene oxide (CHO) with completely alternating polycarbonate selectivity and high efficiency. With this type of novel initiator, the copolymerization could be accomplished under mild conditions at 1 atm pressure of CO2, which represents a significant advantage over most catalytic systems developed for this reaction so tar. The copolymerization reaction was demonstrated to be a living process as a result of the narrow polydispersities and the linear increase in the molecular weight with conversion of CHO. In addition, the solid-state structure of the dinuclear zinc complex was characterized by X-ray crystal structural analysis and can be considered as a model of the active catalyst. On the basis of the various efforts made to understand the mechanisms of the catalytic reaction, including MALDI-TOF mass analysis of the copolymers' end-groups. the effect of alcohol additives on the catalysis and CO2 pressure on the conversion of CHO, as well as the kinetic data gained from in situ IR spectroscopy. a plausible catalytic cycle for the present reaction system is outlined. The copolymerization is initiated by the insertion of CO2 into the Zn OEt bond to afford a carbonate ester-bridged complex. The dinuclear zinc structure of the catalyst remains intact throughout the copolymerization. The bridged zinc centers may have a synergistic effect on the copolymerization reaction: one zinc center could activate the epoxide through its coordination and the second zinc atom may be responsible for carbonate propagation by nucleophilic attack by the carbonate ester on the back side of the cis-epoxide ring to afford the carbonate. The mechanistic implication of this is particularly important for future research into the design of efficient and practical catalysts for the copolymerization of epoxides with CO2.
语种: 英语
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WOS记录号: WOS:000229729300020
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/17801
Appears in Collections:金属有机化学国家重点实验室_期刊论文

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Recommended Citation:
Xiao YL,Wang Z,Ding KL. Copolymerization of cyclohexene oxide with CO2 by using intramolecular dinuclear zinc catalysts[J]. Chem.-Eur. J.,2005,11(12):3668-3678.
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