表面限制的乌尔曼聚合物的机械图像和动态分析
Marco Di Giovannantonio1, Massimo Tomellini1, Josh Lipton-Duffin2
1Istituto di Struttura della Materia, CNR , Via Fosso del Cavaliere 100, 00133 Roma, Italy.
Journal of the American Chemical Society
|December 14, 2016
概括
通过乌尔曼合的表面聚合产生 π 结合材料. 一个新的动态模型揭示了一个短暂的状态,通过核和生长实现了石墨烯纳米带的受控生长.
科学领域:
- 材料科学
- 表面化学
- 有机化学
背景情况:
- 表面受限聚合提供了新型π结合材料的途径.
- 乌尔曼合是创建这些结构的关键反应,包括石墨烯纳米带.
- 了解反应机制对于控制物质形成至关重要.
研究的目的:
- 阐明表面限制的乌尔曼聚合的机制.
- 在Cu{110}上开发1,4-dibromobenzene的表轴聚合的运动模型.
- 了解短暂状态在物质形成中的作用.
主要方法:
- 快速X射线光电子光谱 (XPS) 用于运动测量.
- 密度函数理论 (DFT) 计算用于能源景观的无弹性带 (NEB).
- 使用平均场速率方程的动力建模.
主要成果:
- 在聚合过程中发现过渡状态.
- 运动模型准确地复制了XPS实验数据.
- 聚合过程遵循一个由过渡状态先导的核和生长机制.
结论:
- 这项研究提供了表面限制的乌尔曼聚合的机制理解.
- 开发的动力模型可以合理控制材料合成.
- 这项工作推进了石墨烯纳米带和其他π合系统的自下而上的制造.
相关概念视频
Radical Chain-Growth Polymerization: Mechanism
3.7K
The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
3.7K
Anionic Chain-Growth Polymerization: Mechanism
2.6K
The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
2.6K
Cationic Chain-Growth Polymerization: Mechanism
3.0K
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...
3.0K
Ziegler–Natta Chain-Growth Polymerization: Overview
4.1K
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...
4.1K
Step-Growth Polymerization: Overview
4.6K
Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
Many natural and synthetic polymers are produced by...
4.6K
Radical Chain-Growth Polymerization: Overview
3.6K
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...
3.6K


