Synthesis and Characterization of Well-Defined, Tadpole-Shaped Polystyrene with a Single Atom Junction Point
Synthesis and Characterization of Well-Defined, Tadpole-Shaped Polystyrene with a Single Atom Junction Point
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DOI：
10.1021/acs.macromol.8b01384
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发表时间：
2018-11
期刊：
影响因子：
5.5
通讯作者：
Fan Zhang;R. Quirk;Selim Gerişlioğlu;C. Wesdemiotis;Selemon Bekele;M. Tsige;Yung P. Koh;S. Simon;M. Foster
中科院分区：
文献类型：
--
作者：
Fan Zhang;R. Quirk;Selim Gerişlioğlu;C. Wesdemiotis;Selemon Bekele;M. Tsige;Yung P. Koh;S. Simon;M. Foster
一种有效的方法，用于合成定义明确，良好的特点，蝌蚪形的聚苯乙烯与一个单原子的连接点，是最佳的动力学研究已开发使用阴离子聚合，氯化硅连接化学，和复分解环闭合。以仲丁基锂为引发剂，聚苯乙烯基锂与过量的（30×）甲基三氯硅烷反应，生成双官能度的大分子交联剂ω-甲基二氯硅烷基聚苯乙烯，以消除线型二聚体和三臂星星型聚苯乙烯的生成。通过将过量的α-4-戊烯基聚苯乙烯基锂（α-PSLi）与大分子连接剂连接形成不对称的三臂星星前体，并将过量的α-PSLi用环氧乙烷官能化，然后用甲醇终止以促进色谱分离。在高稀释度的二氯甲烷中，使用Grubbs第一代催化剂双（三环），三臂，星星前体环化形成蝌蚪状聚苯乙烯。
An efficient method for synthesis of well-defined, well-characterized, tadpole-shaped polystyrene with a single atom junction point that is optimal for the study of dynamics has been developed using anionic polymerization, silicon chloride linking chemistry, and metathesis ring closure. The difunctional macromolecular linking agent, ω-methyldichlorosilylpolystyrene, was formed by reacting sec-butyllithium-initiated poly(styryl)lithium with excess (30×) methyltrichlorosilane to eliminate formation of linear dimer and three-arm star polystyrene. The asymmetric, three-arm, star precursor was formed by linking excess α-4-pentenylpoly(styryl)lithium (α-PSLi) with the macromolecular linking agent, and the excess α-PSLi functionalized with ethylene oxide before termination with methanol to facilitate chromatographic separation. Cyclization of the three-arm, star precursor to form tadpole-shaped polystyrene was effected in methylene chloride at high dilution using the Grubbs first generation catalyst, bis(tricycl...