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相关概念视频

Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)01:16

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...
Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Radical Chain-Growth Polymerization: Overview01:10

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...
Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
Base-Catalyzed Ring-Opening of Epoxides02:26

Base-Catalyzed Ring-Opening of Epoxides

Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH301:11

ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3

All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...

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环开放聚合催化剂的氧化控制.

Erin M Broderick1, Neng Guo, Carola S Vogel

  • 1Department of Chemistry & Biochemistry, University of California, Los Angeles, California 90095, USA.

Journal of the American Chemical Society
|May 25, 2011
PubMed
概括

和氧化物复合物的氧化控制调节了聚合率. 这种依赖于金属的活性为聚合物合成提供了新的策略,特别是L-乳和三甲烯碳酸盐.

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科学领域:

  • 有机金属化学 有机金属化学
  • 聚合物科学 聚合物科学
  • 催化剂是一种催化剂.

背景情况:

  • 环开聚合 (ROP) 对于合成可生物降解聚合物至关重要.
  • 通过外部刺激控制催化剂活动,如氧化还原变化是一个活跃的研究领域.
  • 基于铁素的配体为金属复合体提供独特的氧化还原特性.

研究的目的:

  • 为了研究在ROP中和氧化物复合物的氧化还原控制.
  • 探索金属特征对聚合行为的影响.
  • 为了合成和描述由L-乳和三甲烯碳酸盐衍生的聚合物.

主要方法:

  • 氧化物复合物的合成和表征与铁素联结体.
  • 使用化学试剂对伊复合物的氧还原操作.
  • 进行X射线晶体学,NMR,XANES和Mössbauer光谱学进行表征.
  • 环开聚合的L-乳和三甲碳酸盐.
  • 凝透色谱用于聚合物分析.

主要成果:

  • 伊复合物的聚合率是由氧化还原状态的变化调节的.
  • 复合物的氧化和还原形式表现出不同的催化活性.
  • 与伊特相比,氧化复合体表现出相反的行为.
  • 观察到一种明确的基于金属的对聚合率的依赖.

结论:

  • 可回氧切换的和氧化物复合物可以控制聚合率.
  • 观察到的金属依赖性行为凸显了金属中心在催化活动中的重要性.
  • 这项研究为设计可控聚合物合成的氧化还原反应催化剂提供了洞察力.