Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity

doi:10.1021/ma501460f

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	Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity
	Wang, Bin 1,2; Wang, Yong-Xia 1; Cui, Jing 3,4; Long, Ying-Yun 1; Li, Yan-Guo 1; Yuan, Xiao-Yan 3,4; Li, Yue-Sheng 1,3,4
刊名	MACROMOLECULES
	2014-10-14
卷号	47 期号:19 页码:6627-6634
ISSN号	0024-9297
DOI	10.1021/ma501460f
英文摘要	Cyclopolymerization of unsymmetric and symmetric Si-containing alpha,omega-diolefins by dimethylpyridylamidohafnium/organoboron catalytic system with high cyclization selectivity and stereoselectivity was first reported here. Compared with the constrained geometry catalyst [Me2Si(eta(5)-Me4C5)((NBu)-Bu-t)]TiCl2 and the typical metallocene catalyst rac-Et(Ind)(2)ZrCl2, the Hf complex has proved to be one more promising catalyst for the cyclopolymerization of unsymmetric 3,3-dimethyl-3-sila-1,5-hexadiene (DMSHD). The poly(DMSHD) with high molecular weight (up to 953 kg/mol), high cyclization selectivity (100%), high cis selectivity (>90%), and high isotactic selectivity (>90%) could be easily obtained by the catalyst under mild conditions. Moreover, the poly(DMSHD) also possessed a high glass transition temperature (up to 99.8 degrees C) and high melting temperature (T-m >200 degrees C). The insertion reaction of the vinyl group into Hf-C-Ar bond was further investigated, and a possible cyclization mechanism of DMSHD was proposed according to density functional theory calculation. Meanwhile, the Hf catalyst also showed notable catalytic activity for the cyclopolymerization of the symmetric Si-containing alpha,omega-diolefins including 4,4-dimethyl-4-sila-1,6-heptadiene, 4-methyl-4-phenyl-4-sila-1,6-heptadiene and 4,4-diphenyl-4-sila-1,6-heptadiene. Although the cyclization selectivity is somewhat low, the copolymerization by Hf catalyst still shows excellent cis/trans selectivity and isotactic selectivity.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000343196200012
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50341]
专题	中国科学院化学研究所
通讯作者	Yuan, Xiao-Yan
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Univ Chinese Acad Sci, Changchun Branch, Changchun 130022, Peoples R China 3.Tianjin Univ, Sch Mat Sci & Engn, Tianjin 300072, Peoples R China 4.Tianjin Univ, Tianjin Key Lab Composite & Funct Mat, Tianjin 300072, Peoples R China
推荐引用方式 GB/T 7714	Wang, Bin,Wang, Yong-Xia,Cui, Jing,et al. Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity[J]. MACROMOLECULES,2014,47(19):6627-6634.
APA	Wang, Bin.,Wang, Yong-Xia.,Cui, Jing.,Long, Ying-Yun.,Li, Yan-Guo.,...&Li, Yue-Sheng.(2014).Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity.MACROMOLECULES,47(19),6627-6634.
MLA	Wang, Bin,et al."Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity".MACROMOLECULES 47.19(2014):6627-6634.