Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors

doi:10.1021/om4000709

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	Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors
	Yao, Changguang 1,2; Wu, Chunji 1; Wang, Baoli 1,2; Cui, Dongmei 1
刊名	ORGANOMETALLICS
	2013-04-08
卷号	32 期号:7 页码:2204-2209
ISSN号	0276-7333
DOI	10.1021/om4000709
英文摘要	Rare-earth metal bis(alkyl) complexes (Flu-NHC)Ln(CH2SiMe3)(2) (Ln = Dy (1), Er (2), Sc (3)) attached by fluorenyl-modified N-heterocyclic carbene ligands ((Flu H-NHC-H)Br) have been synthesized by treatment of (FluH-NHC-H)Br with (trimethylsilylmethyl)lithium (LiCH2SiMe3) and rare-earth metal tris(alkyl)s (Ln(CH2SiMe3)(3)(THF)(2)) via double-deprotonation reactions in moderate to high yields. Under mild conditions (40 degrees C and normal ethylene pressure), the scandium precursor 3, upon activation of (AlBu3)-Bu-i and [Ph3C][B(C6F5)(4)], showed high activity (4120 kg mol(Sc)(-1)h(-1) atm(-1)) for the copolymerization of ethylene and 1-hexene with moderate 1-hexene insertion ratio (20.2%), although the analogous complexes 1 and 2 were inert. In addition, this system displayed excellent catalytic performances for the copolymerization of ethylene and a higher alpha-olefin 1-octene with an activity of up to 3640 kg mol(Sc)(-1) h(-1) atm(-1). The content of 1-octene could be controlled swiftly from 2.1% to 38.7% by varying the 1-octene feed ratio. Thus the isolated P(E-co-Oct) polymers varied from opaque crystalline solids with high melting points, e.g., T-m = 103.6 degrees C, to transparent elastomers. This represents the first rare-earth metal based homogeneous catalyst that can initiate the copolymerization of ethylene and 1-octene, the catalytic performances of which are comparable with those reported for the most active group 4 metallocene systems.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000317370000022
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/46793]
专题	中国科学院化学研究所
通讯作者	Cui, Dongmei
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Chinese Acad Sci, Grad Sch, Beijing 100039, Peoples R China
推荐引用方式 GB/T 7714	Yao, Changguang,Wu, Chunji,Wang, Baoli,et al. Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors[J]. ORGANOMETALLICS,2013,32(7):2204-2209.
APA	Yao, Changguang,Wu, Chunji,Wang, Baoli,&Cui, Dongmei.(2013).Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors.ORGANOMETALLICS,32(7),2204-2209.
MLA	Yao, Changguang,et al."Copolymerization of Ethylene with 1-Hexene and 1-Octene Catalyzed by Fluorenyl N-Heterocyclic Carbene Ligated Rare-Earth Metal Precursors".ORGANOMETALLICS 32.7(2013):2204-2209.