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Intramolecularly dinuclear magnesium complex catalyzed copolymerization of cyclohexene oxide with CO2 under ambient CO2 pressure: Kinetics and mechanism
其他题名分子内双核镁络合物催化的二氧化碳与氧化环己烯的常压共聚合反应: 动力学和机理研究
Xiao YL(肖友利); Wang Z(王正); Ding KL(丁奎岭)
2006
发表期刊Macromolecules
ISSN0024-9297
卷号39期号:1页码:128-137
摘要The intramolecularly dinuclear magnesium complexes generated in situ from the reaction of multidentate semi-azacrown ether ligands with n-Bu2Mg followed by treatment with alcohol additive were found to be efficient catalysts for the copolymerization of CO2 and cyclohexene oxide (CHO), affording the completely alternating poly(cyclohexene carbonate) (PCHC) under extremely mild conditions (1 atm pressure of CO2, temperatures ranging from 20 to 60 degrees C). Ligand substituent effects were observed to dramatically influence both the activity and the chemoselectivity of the catalysis, exemplifying the fine-tunability of this type of ligands. With regard to the mechanistic studies, end-group analysis of the copolymer by MALDI-TOF mass spectroscopy revealed the predominance of the butoxy-initiated CO2/CHO copolymerization process. The butoxy-containing catalytically active species in the present system was proposed to possess a dinuclear structure similar to an isolated model Mg complex which was characterized by X-ray crystal structural analysis. Rate studies performed on the copolymerization using the in situ prepared catalyst (molar ratio of 5a:n-Bu2Mg:n-BuOH = 1:2:0.4) at 60 degrees C demonstrate a zero-order dependence on CO2 Pressure and approximately first-order dependence on CHO and the catalyst concentration. Furthermore, the relative propensity of polycarbonate vs cyclic carbonate formation in the present system was evaluated by a comparative kinetic study of the temperature effect using the in situ IR technique. On the basis of these findings, a plausible bimetallic mechanism was tentatively proposed for the present reaction system.
学科领域金属有机化学
部门归属上海有机所
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收录类别SCI
语种英语
WOS记录号WOS:000234500100023
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被引频次:120[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/17829
专题金属有机化学国家重点实验室
通讯作者Ding KL(丁奎岭)
推荐引用方式
GB/T 7714
Xiao YL,Wang Z,Ding KL. Intramolecularly dinuclear magnesium complex catalyzed copolymerization of cyclohexene oxide with CO2 under ambient CO2 pressure: Kinetics and mechanism[J]. Macromolecules,2006,39(1):128-137.
APA 肖友利,王正,&丁奎岭.(2006).Intramolecularly dinuclear magnesium complex catalyzed copolymerization of cyclohexene oxide with CO2 under ambient CO2 pressure: Kinetics and mechanism.Macromolecules,39(1),128-137.
MLA 肖友利,et al."Intramolecularly dinuclear magnesium complex catalyzed copolymerization of cyclohexene oxide with CO2 under ambient CO2 pressure: Kinetics and mechanism".Macromolecules 39.1(2006):128-137.
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