Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene

doi:10.1021/ma500740m

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	Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene
	Liu, Siqian 1; Du, Gaixia 1; He, Jianyun 1; Long, Yingyun 2; Zhang, Shaowen 1; Li, Xiaofang 1
刊名	MACROMOLECULES
	2014-06-10
卷号	47 期号:11 页码:3567-3573
ISSN号	0024-9297
DOI	10.1021/ma500740m
英文摘要	Different nonmetallocene rare earth metal alkyl complexes such as monotropidinyl (Trop) scandium diallcyl complex (Trop)Sc(CH2SiMe3)(2)(THF) (1), ditropidinyl yttrium alkyl complex (Trop)(2)Y(CH2SiMe3)(THF) (3) as well as binuclear lutetium alkyl complex bearing one tetradentate dianionic 6-N-methyl-1,4-cycloheptadienyl (NMCH) ligand [(NMCH)Lu(CH2SiMe3)(THF)](2) (2) have been synthesized in high yields via one-pot acid-base reaction by using of the tris(trimethylsilylmethyl) rare earth metal complexes with the readily available natural product tropidine. The polymerization experiments indicate that the monotropidinyl scandium diallcyl complex 1 displays reactivity akin to that of the analogous monocyclopentadienyl scandium diallcyl complexes. In the presence of activator and a small amount of AlMe3, complex 1 exhibits similar activities (up to 1.6 x 10(6) g mol(Sc)(-1) h(-1)) but higher cis-1,4-selectivities (up to 100%) than (C5H5)Sc(CH2SiMe3)(2)(THF) (cis-1,4-selectivity as 95%) in the isoprene polymerization, yielding the pure cis-1,4-PIPs with moderate molecular weights (M-n = 0.5-11.2 x 10(4) g/mol) and bimodal molecular weight distributions (M-w/M-n = 1.48-6.07). Moreover, the complex 1/[Ph3C][B(C6F5)(4)/(AlBu3)-Bu-i ternary system also shows good comonomer incorporation ability in the copolymerization of isoprene and norbomene similar to the [C5Me4(SiMe3)]Sc(eta(3)-CH2CHCH2)(2)/activator binary system, affording the random isoprene/norbornene copolymers with a wide range of isoprene contents around 57-91 mol % containing cis-1,4 configuration up to 88%.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000337199000004
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/53063]
专题	中国科学院化学研究所
通讯作者	Zhang, Shaowen
作者单位	1.Beijing Inst Technol, Key Lab Cluster Sci, Minist Educ, Dept Chem, Beijing 100081, Peoples R China 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
推荐引用方式 GB/T 7714	Liu, Siqian,Du, Gaixia,He, Jianyun,et al. Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene[J]. MACROMOLECULES,2014,47(11):3567-3573.
APA	Liu, Siqian,Du, Gaixia,He, Jianyun,Long, Yingyun,Zhang, Shaowen,&Li, Xiaofang.(2014).Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene.MACROMOLECULES,47(11),3567-3573.
MLA	Liu, Siqian,et al."Cationic Tropidinyl Scandium Catalyst: A Perfectly Acceptable Substitute for Cationic Half-Sandwich Scandium Catalysts in cis-1,4-Polymerization of Isoprene and Copolymerization with Norbornene".MACROMOLECULES 47.11(2014):3567-3573.