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

	Cyclopolymerization of Si-Containing alpha,omega-Diolefins by a Pyridylamidohafnium Catalyst with High Cyclization Selectivity and Stereoselectivity
	Wang, Bin ; Wang, Yong-Xia ; Cui, Jing ; Long,Yingyun ; Li,Yanguo ; Yuan,Xiaoyan ; Li,Yuesheng
刊名	macromolecules
	2014
卷号	47 期号:19 页码:6627-6634
关键词	OPTICALLY-ACTIVE POLY(METHYLENE-1 LIQUID-CRYSTALLINE FEATURES FOCK-SLATER CALCULATIONS OLEFIN POLYMERIZATION MAIN-CHAIN ENANTIOSELECTIVE CYCLOPOLYMERIZATION STEREOSPECIFIC CYCLOPOLYMERIZATION INTRAMOLECULAR CYCLIZATION ZIRCONOCENE CATALYSTS NONCONJUGATED DIENES 3-CYCLOPENTANE)
通讯作者	yuan,xy
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.
收录类别	SCI
语种	英语
WOS记录号	WOS:000343196200012
内容类型	期刊论文
源URL	[http://ir.ciac.jl.cn/handle/322003/52096]
专题	长春应用化学研究所_长春应用化学研究所知识产出_期刊论文
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,Yingyun.,Li,Yanguo.,...&Li,Yuesheng.(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.