碳烯化的压力捕获由聚合物骨干的变化促进
Hope M Klukovich1, Zachary S Kean, Ashley L Black Ramirez
1Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
Journal of the American Chemical Society
|June 2, 2012
概括
聚合物骨干显著影响机械活动. 在超声波下,经氧化聚乙烯表现出机械反应,与经氧化聚乙烯不同,表明依赖于脊柱的环氧化反应性.
科学领域:
- 聚合物化学 聚合物化学
- 机械化学 机械化学
- 材料科学 材料科学 材料科学
背景情况:
- 环氧化物是已知的功能组,在材料科学中具有潜在的应用.
- 机械体是对机械力做出反应而经历化学或物理变化的材料.
- 了解聚合物骨干对机械活动的影响对于设计新材料至关重要.
研究的目的:
- 为了研究嵌入在不同聚合物骨干中的环氧化物的机械活性.
- 确定超声波是否可以诱导环氧化聚合物中的反应.
- 为了表征环开放式基环氧化物的反应性.
主要方法:
- 脉冲超声波应用于环氧化聚乙烯和环氧化聚乙烯.
- 能够捕获碳烯化物的小分子被用作探针.
- 监测了聚合物的变化,例如小分子添加和环氧化物异构化 (cis 到 trans).
主要成果:
- 在超声波处理时,氧化聚乙烯没有显示可观察到的小分子添加或显著的环氧化物异构化.
- 在超声波下,经过氧化聚甲基呈现出小分子添加和 cis 到 trans 环氧化物异体化.
- 这些结果表明,聚合物骨干在环氧化物机械激活中起着关键作用.
结论:
- 环氧气体机械的活性取决于它被纳入的聚合物骨干.
- 环氧化物具有机械活性,但它们的反应是由周围的聚合物结构调节的.
- 这项研究提供了对开环的基环氧化物和含有机械孔的聚合物设计的反应性的见解.
相关概念视频
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,...
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.
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,...
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...
Polymer Classification: Stereospecificity
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...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...


