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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)

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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...
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Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule02:17

Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule

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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
13.9K
Olefin Metathesis Polymerization: Overview01:13

Olefin Metathesis Polymerization: Overview

2.0K
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...
2.0K
Base-Catalyzed Ring-Opening of Epoxides02:26

Base-Catalyzed Ring-Opening of Epoxides

8.3K
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...
8.3K
Acid-Catalyzed Ring-Opening of Epoxides02:24

Acid-Catalyzed Ring-Opening of Epoxides

7.1K
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...
7.1K
Preparation and Reactions of Sulfides02:26

Preparation and Reactions of Sulfides

4.7K
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
4.7K

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相关实验视频

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Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene
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对于硫化环开环共聚合物的单体中心选择性指南.

Merlin R Stühler1,2, Marie Kreische2, Christoph Fornacon-Wood1

  • 1Makromolekulare Chemie, Universität Bayreuth Universitätsstraße 30 95447 Bayreuth Germany alex.plajer@uni-bayreuth.de.

Chemical science
|October 31, 2024
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概括

现在可以通过催化环开放共聚合 (ROCOP) 来实现含硫聚合物的受控合成. 本研究确定了选择性的关键因素,使得创建先进的,可持续的硫化聚合物成为可能.

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科学领域:

  • 聚合物化学 聚合物化学
  • 可持续材料科学科学 可持续材料科学
  • 有机合成 有机合成

背景情况:

  • 含硫聚合物提供可持续性好处,如可降解性和可回收性.
  • 目前的合成方法,特别是催化环开放共聚合 (ROCOP),缺乏对微观结构和性质的控制.
  • 为了推进这些材料,需要在硫化ROCOP中进行选择性的预测模型.

研究的目的:

  • 调查硫化ROCOP反应中控制选择性的因素.
  • 开发用于控制聚合物微观结构和特性的策略.
  • 为了使精确定义的含硫聚合物的合成.

主要方法:

  • 使用多种单体进行ROCOP的勘探:硫化硫酸/二硫化碳和环氧化物,硫酸,氧化.
  • 对反应机制的分析,重点关注催化剂结合的链末和反反应.
  • 实施单体选择,环应变优化和受控终止策略.

主要成果:

  • 鉴定了与催化剂结合的氧化物链末端的反作为副产品的主要来源.
  • 通过特定的单体选择,最大限度地减轻副作用,最大限度地减轻环应变和及时终止.
  • 通过使用乙烯氧化物和各种氧乙,成功合成了完美交替的聚 (?? Ester-Alt-Thioester).

结论:

  • 硫化ROCOP的选择性可以通过战略性单体选择来控制,而不仅仅是催化剂设计.
  • 机械学的洞察力为开发未来选择性聚合方法提供了基础.
  • 这项工作将硫化聚合物推进为传统材料的可行,可持续的替代品.