操纵芳香度以重定向拓化学聚合途径
Qingsong Zhang1, Zhipeng Pei2, Ah-Young Song3
1The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Journal of the American Chemical Society
|April 15, 2025
概括
研究人员通过改变para-azaquinodimethane (AQM) 系统中的芳香度来控制高化学聚合 (TCP). 通过转子密度驱动的合反应,修改末端组与furyl单元使新的聚合物结构成为可能.
科学领域:
- 聚合物化学
- 有机合成
- 材料科学
背景情况:
- 拓化学聚合 (TCP) 对于通过固态反应合成区域和立体正规聚合物至关重要.
- 控制固态转化中的聚合途径仍然是聚合物科学中的一个重大挑战.
- 芳香性在有机分子的反应性和电子性质中起着关键作用.
研究的目的:
- 开发一种控制高化学聚合途径的创新策略.
- 研究终端组芳香度对聚合反应性的影响.
- 合成具有独特主链结构的新型聚合物.
主要方法:
- 在para-azaquinodimethane (AQM) 环系统中调整终端组的芳香度,通过用基替换基.
- 热激活以诱导旋转密度移位和二极管性质.
- 溶液和固态反应监测,X射线结晶学,理论建模和同位素标记实验.
主要成果:
- 在烯中进行热处理,通过烯-甲C-C合产生独特的环二聚物.
- 固态反应通过柱间基甲和柱内甲合产生聚合物.
- 芳香度调节成功控制了聚合途径,并使以前无法获得的聚合物结构得以合成.
结论:
- 在亲芳香系统中调节芳香度为控制高化学聚合提供了强大的方法.
- 旋转中心定向的机制控制了观察到的合反应.
- 这种方法提供了复杂主链架构的聚合物.
相关概念视频
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
1.9K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
1.9K
Ziegler–Natta Chain-Growth Polymerization: Overview
3.2K
Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta...
3.2K
Free-Radical Chain Reaction and Polymerization of Alkenes
7.6K
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
7.6K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
5.6K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the...
5.6K
Olefin Metathesis Polymerization: Overview
2.0K
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.0K
Polymer Classification: Stereospecificity
2.3K
Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
2.3K


