无添加剂的点击用于聚合物功能化和通过四-诺波伦化学的合
Claire F Hansell1, Pieter Espeel, Milan M Stamenović
1Department of Chemistry, University of Warwick, Coventry, UK.
Journal of the American Chemical Society
|August 9, 2011
概括
一种新的四素-诺伯烯点击化学可以实现高效的聚合物末端功能化和聚合物-聚合物合. 这种反应简单地在室温下混合聚合物,不需要催化剂或添加剂,从而产生双阻塞共聚合物.
科学领域:
- 聚合物化学 聚合物化学
- 有机化学 有机化学
- 材料科学 材料科学 材料科学
背景情况:
- 聚合物终端功能化和聚合物-聚合物合对于创建先进的聚合物架构至关重要.
- 现有的方法通常需要恶劣的条件,催化剂或多步骤的过程.
研究的目的:
- 开发一种温和高效的方法,用于聚合物终端功能化和聚合物-聚合物合.
- 通过使用特定的点击化学反应来证明二块化共聚物的形成.
主要方法:
- 利用了四素 - 诺伯烯反向电子需求迪尔斯 - 阿尔德反应的结合.
- 应用了反应来功能化聚合物链末,并将不同的同聚合物结合起来.
- 使用尺寸排除染色学 (SEC),扩散订序光谱核磁共振 (DOSY NMR) 和液体染色学x尺寸排除染色学 (LCxSEC) 进行了结果材料的表征.
主要成果:
- 成功实现了聚合物终端功能化和聚合物-聚合物合.
- 通过简单地混合同聚合物,证明了双块共聚物的形成.
- 在环境条件下,反应在不需要催化剂,添加剂或外部刺激的情况下有效地进行.
结论:
- 滴尔斯-阿尔德反应的四-诺波伦反向电子需求是聚合物合成的多功能和高效工具.
- 这种方法在温和,无催化剂的条件下提供了一条轻松的途径来解锁聚合物.
- 该方法简化了复杂的聚合物架构的准备,为新材料开发铺平了道路.
相关概念视频
Ziegler–Natta Chain-Growth Polymerization: Overview
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 catalyst, high molecular...
Cationic Chain-Growth Polymerization: Mechanism
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...
Radical Chain-Growth Polymerization: Overview
Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para position.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
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...


