中国科学院上海有机化学研究所机构知识库
Advanced  
SIOC OpenIR  > 金属有机化学国家重点实验室  > 期刊论文
学科主题: 金属有机化学
题名: 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
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: Macromolecules
发表日期: 2006
卷: 39, 期:1, 页:128-137
收录类别: SCI
部门归属: 上海有机所
英文摘要: 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.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000234500100023
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/17829
Appears in Collections:金属有机化学国家重点实验室_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2006336.pdf(260KB)----开放获取--View Download

Recommended Citation:
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.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[肖友利]'s Articles
[王正]'s Articles
[丁奎岭]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[肖友利]‘s Articles
[王正]‘s Articles
[丁奎岭]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 2006336.pdf
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace