平面波密度函数理论研究的形成粘土聚合物纳米复合材料的自我催化 in situ 介质聚合
S Stackhouse1, P V Coveney, E Sandré
1Centre for Computational Science, Department of Chemistry, Queen Mary, University of London, Mile End Road, London E1 4NS, United Kingdom. s.stackhouse@qmul.ac.uk
Journal of the American Chemical Society
|November 22, 2001
概括
这项研究研究了粘土矿物质中的单体聚合物. 催化发生在粘土矿物边缘,而不是酸盐层,揭示了新的纳米复合材料形成途径.
科学领域:
- 材料科学 材料科学 材料科学
- 化学 化学 化学
- 纳米技术纳米技术
背景情况:
- 粘土矿物质可以容纳交的有机单体,用于新的纳米复合材料合成.
- 了解初始聚合阶段对于控制材料性质至关重要.
研究的目的:
- 在蒙莫里隆尼特中间层中研究甲和乙二的初始聚合.
- 确定控制这一过程的催化场所和反应机制.
主要方法:
- 使用了平面波密度函数理论 (DFT) 的计算.
- 模拟的重点是粘土中间层中的单体相互作用和酸位触媒.
主要成果:
- 聚合需要甲的质子化或金属协调;没有观察到水分离.
- 酸基基的布伦斯特酸度受到同态置换的影响.
- 粘土矿物质格子边缘,含有基和暴露的离子,充当主要的催化点 (布伦斯特和易斯酸).
结论:
- 这项研究阐明了在粘土中间层内现场聚合的机制.
- 确定特定的催化位点 (晶格边缘) 负责启动聚合.
- 提供了设计新型粘土基纳米复合材料的基本见解.
相关概念视频
Polymers: Molecular Weight Distribution
For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
Anionic Chain-Growth Polymerization: Overview
The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
Anionic Chain-Growth Polymerization: Mechanism
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 acceptor.
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,...
Step-Growth Polymerization: Overview
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...
Molecular Weight of Step-Growth Polymers
Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...


