【作者】 刘立佳； 王文帅； 王玉丹； 青木俊树； 张春红； 冈本佳男；

【Author】 Lijia Liu;Wenshuai Wang;Yudan Wang;Toshiki Aoki;Chunhong Zhang;Yoshio Okamoto;Polymer Materials Research Center, College of Materials Science and Chemical Engineering, Harbin Engineering University;

【机构】 哈尔滨工程大学材料科学与化学工程学院,高分子材料研究中心；

【摘要】 <正>聚乙炔是一类典型的动态螺旋聚合物,其共轭主链内sigma键的旋转和较低的翻转能垒赋予了其主链结构的多样性和可控性。聚乙炔可分为顺、反两种构型,由于主链中sigma键的旋转,其反式构型又可分为全反式和反顺式构象、顺式构型可分为顺反式和全顺式构象。近年来由于其在手性识别、分离材料及传感器等领域的潜在应用价值成为国际高分子领域的研究热点。尤其是由铑催化剂(如:[Rh(nbd)Cl]2)引发乙炔基单体的插入式配位聚合所制更多还原

【Abstract】 Polyacetylene prepared by rhodium catalyst, such as [Rh(nbd)Cl]2, is a typical dynamic helical polymer, and its main-chain conformation can be cis-transoidal or cis-cisoidal depending on the monomer structure and the environment.In this study, we report that a thermotropic chiral induction system consisting of a chiral amine and a polyacetylene prepared from an achiral phenylacetylene having two hydroxyl groups shows a tunable critical one-handed spiralization temperature(COST). The conformation of poly(1) in the system of poly(1)/chiral phenylethyl amine could be induced into one-handed helix along with transformation of main chain conformation from cis-transoidal to cis-cisoidal by heating the system to a temperature higher than the COST. The COST can be adjusted by changing the chiral amine concentration in the system,and the higher concentration affords the higher COST. This unique thermotropic chiral induction phenomenon may be caused by the competition of H-bonds in the system at different temperature.In addition, the induced one-handed helical clarity of the polyacetylene can be self-stabilized by intramolecular H-bonds after precipitating the polyacetylene in methanol to remove the chiral amine, i.e. the induced one-handed helical chirality of the polyacetylene can be perfectly saved in solid state.更多还原