与表面连接的反应聚合物的动力学
1Department of Physics, Sam Houston State University, Huntsville, TX, 77341-2267, USA. phy_baf@shsu.edu.
The European physical journal. E, Soft matter
|December 2, 2024
概括
缩放参数揭示了移植聚合物链的反应动态. 端到端的反应在长链中没有扩散控制,而端到壁的反应总是扩散控制.
科学领域:
- 聚合物物理 聚合物物理
- 化学动力学 化学动力学
- 软物质物理学 软物质物理学
背景情况:
- 接种的聚合物链表现出复杂的反应动态,受链相互作用和限制的影响.
- 了解端到壁和端到端反应对于设计聚合物材料和工艺至关重要.
研究的目的:
- 为了呈现移植聚合物链的端到墙和端到端反应的缩放论据.
- 研究排除体积和水力动力学相互作用对这些反应速率的影响.
- 用数值模拟来验证非自回避链的缩放预测.
主要方法:
- 开发用于移植连锁反应动力学的缩放参数.
- 对具有或没有水力动力相互作用的非自避和自避链的分析.
- 对于非自避链的Rouse动力学的数值模拟.
主要成果:
- 连锁链的端到端反应遵循质量作用定律,长链的扩散不受限制.
- 从端到壁的反应总是以扩散控制,不管排除了体积和水力动力相互作用.
- 数字结果证实了扩展预测,确定了绑定的非自我避免链中的端到端反应作为边缘情况.
结论:
- 缩放参数为理解接种聚合物反应动力学提供了一个强大的框架.
- 端到墙与端到端反应的独特扩散控制行为对聚合物系统设计有重大影响.
- 数字模拟强烈支持两个反应类型的理论缩放预测.
相关概念视频
Radical Chain-Growth Polymerization: Mechanism
2.5K
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...
2.5K
Polymers
35.0K
The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
35.0K
Anionic Chain-Growth Polymerization: Mechanism
2.0K
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...
2.0K
Cationic Chain-Growth Polymerization: Mechanism
2.3K
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...
2.3K
Radical Chain-Growth Polymerization: Overview
2.4K
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...
2.4K
Anionic Chain-Growth Polymerization: Overview
2.1K
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,...
2.1K


