Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity

doi:10.1007/s11426-014-5136-5

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	Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity
	Zhao ZhiYuan 1; Bai JianWei 2; Zhang Jie 1; Liu AnHua 3; Wan XinHua 1
刊名	SCIENCE CHINA-CHEMISTRY
	2014-07-01
卷号	57 期号:7 页码:982-994
关键词	Chiral Liquid Crystalline Polymers (Lcp) Radical Polymerization Thermal Property Helical
ISSN号	1674-7291
DOI	10.1007/s11426-014-5136-5
英文摘要	Eight chiral vinylterphenyl monomers, (+)-2,5-bis{4'-[(S)-1aEuro(3)-methylpropyloxy]phenyl}styrene (Ia), (+)-2,5-bis{4'-[(S)-2aEuro(3)-methylbutyloxy]phenyl}styrene (Ib), (+)-2,5-bis{4'-[(S)-3aEuro(3)-methylpentyloxy]phenyl}styrene (Ic), (+)-2,5-bis{4'-[(S)-4aEuro(3)-methylhexyloxy]phenyl}styrene (Id), (-)-2,5-bis{4'-[(R)-1aEuro(3)-methylpropyloxy]phenyl}styrene (Ie), (+)-2-{4'-[(S)-1aEuro(3)-methyl-propyloxy]phenyl}-5-{4'-[(R)-1aEuro(3)-methylpropyloxy]phenyl}styrene (IIa), (-)-2-{4'-[(R)-1aEuro(3)-methylpropyloxy]phenyl}-5-{4'-[(S)-1aEuro(3)-methylpropyloxy]phenyl}styrene (IIb), and (+)-2-{4'-[(S)-2''-methylbutyloxy]phenyl}-5-{4'-[(S)-1aEuro(3)-methylpropyl-oxy]phenyl}styrene (III), were synthesized and radically polymerized. These molecules were designed to further understand long-range chirality transfer in radical polymerization and to possibly tune the chiroptical properties of the polymers by varying the spatial configuration, position, and various combination of the stereogenic centers at the ends of p-terphenyl pendants. The resultant polymers adopted helical conformations with a predominant screw sense. When the stereogenic centers ran away from the terphenyl group as in Ib-d, the corresponding polymers changed the direction of optical rotation in an alternative way and showed no obvious stereomutation upon annealing in tetrahydrofuran. The two stereogenic centers of IIa, IIb, and III acted concertedly in chiral induction, whereas those of Ia and Ie played a counteractive role. The five polymers derived from Ia, Ie, IIa, IIb, and III underwent stereomutation when annealed in tetrahydrofuran. The polymers PIa-e had good thermal stability and high glass transition temperatures (T (g)s). They generated liquid crystalline phases at above T (g)s that could be kept upon cooling, with the exception of PIe. This result was consistent with the extended helical structures.
语种	英语
出版者	SCIENCE PRESS
WOS记录号	WOS:000338450800010
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/50649]
专题	中国科学院化学研究所
通讯作者	Liu AnHua
作者单位	1.Peking Univ, Beijing Natl Lab Mol Sci, Coll Chem & Mol Engn, Key Lab Polymer Chem & Phys,Minist Educ, Beijing 100871, Peoples R China 2.Harbin Engn Univ, Coll Mat Sci & Chem Engn, Polymer Mat Res Ctr, Harbin 150001, Peoples R China 3.Xiamen Univ, Coll Mat, Minist Educ, Key Lab High Performance Ceram Fibers, Xiamen 310065, Peoples R China
推荐引用方式 GB/T 7714	Zhao ZhiYuan,Bai JianWei,Zhang Jie,et al. Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity[J]. SCIENCE CHINA-CHEMISTRY,2014,57(7):982-994.
APA	Zhao ZhiYuan,Bai JianWei,Zhang Jie,Liu AnHua,&Wan XinHua.(2014).Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity.SCIENCE CHINA-CHEMISTRY,57(7),982-994.
MLA	Zhao ZhiYuan,et al."Helix-sense-selective radical polymerization of bulky styrenic monomers: chiral induction and liquid crystallinity".SCIENCE CHINA-CHEMISTRY 57.7(2014):982-994.