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学科主题: 金属有机化学
题名: Polymerization of Naturally Renewable Methylene Butyrolactones by Half-Sandwich Indenyl Rare Earth Metal Dialkyls with Exceptional Activity
其他题名: 高活性的单茚基稀土金属烷基化合物催化的天然可降解的亚甲基丁内酯的聚合
作者: HU YANGJIAN ; Xu X(徐信) ; ZHANG YUETAO ; Chen YF(陈耀峰) ; CHEN EUGENE YX
通讯作者: 陈耀峰 ; CHEN EUGENE YX
刊名: Macromolecules
发表日期: 2010
卷: 43, 期:22, 页:9328-9336
收录类别: SCI
部门归属: 科罗拉多州立大学; 中国科学院上海有机化学研究所
英文摘要: Four discrete half-sandwich dialkyl rare earth metal (REM) complexes incorporating a disilylated indenyl ligand, (1,3 (SiMe3)(2)C9H5)M(CH2SiMe3)(2)(THF) (M = Sc, Y, Dy, Lu), have been investigated for the coordination addition polymerization of naturally renewable methylene butyrolactones, alpha-methylene-gamma butyrolactone (MBL) and gamma-methyl alpha-methylene gamma butyrolactone (MMBL) Initial screening for the polymerization of methyl methacrylate highlighted several differences in catalytic behavior between these half-sandwich REM catalysts and well studied sandwich REM catalysts in terms of reactivity trend, polymer tacticity and solvent dependence Most significantly all four catalysts herein exhibit exceptional activity for polymerization of MMBL in DMF, achieving quantitative monomer conversion in <1 min with a 020 mol % catalyst loading and giving a high turnover frequency of > 30 000 h(-1) Slower polymerizations occur in CH2Cl2 allowing for establishment of the activity trend within this REM series, which follows Dy (largest ion) >= Y > Lu > Sc (smallest ion) The most active and effective Dy catalyst has been examined in detail, demonstrating its ability to control the polymerization for producing PMMBL with high T-g (221 degrees C) and with molecular weight ranging from a medium M-n of 1 89 x 10(4) Da to a high M-n of 1 63 x 10(5) Da, programmed by the [MMBL]/[Dy] ratio Kinetic experiments have revealed a first order dependence on [monomer] and a second order dependence on [REM] These kinetic results, coupled to catalyst efficiencies, NMR studies, as well as with chain end group analysis by MALDI TOF mass spectrometry, have yielded a chain initiation mechanism that involves both alkyl groups on each metal center and a bimolecular chain propagation that involves two metal centers in the rate limiting C-C bond forming step The Dy catalyst response to enolizable organo acids, externally added as chain transfer agents has also been examined
语种: 英语
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WOS记录号: WOS:000284177000015
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/25331
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:
HU YANGJIAN,Xu X,ZHANG YUETAO,et al. Polymerization of Naturally Renewable Methylene Butyrolactones by Half-Sandwich Indenyl Rare Earth Metal Dialkyls with Exceptional Activity[J]. Macromolecules,2010,43(22):9328-9336.
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