含硫环开放共聚化中的单体依赖选择性:可降解聚合物的预测性设计的双金属催化
Bhargav R Manjunatha1, Mani Sengoden2, Merlin R Stühler1
1Makromolekulare Chemie, Universität Bayreuth, Universitätsstraße 30, Bayreuth, 95447, Germany.
Angewandte Chemie (International ed. in English)
|August 26, 2025
概括
研究人员开发了使用环开放共聚化制造含硫聚合物的新方法. 碳化物 (COS) 和PhNCS单体对设计可降解,高性能材料具有前景.
科学领域:
- 聚合物化学
- 材料科学
- 有机合成
背景情况:
- 含硫的聚合物具有独特的特性,如可降解性和高折射率.
- 开发精确的合成策略和理解这些聚合物的单体选择仍然是一个重大挑战.
研究的目的:
- 在统一条件下全面评估硫化环开放共聚化 (ROCOP).
- 确定控制的聚合物合成的最佳硫单体和催化剂系统.
主要方法:
- 使用单一的Cr (III) /Rb (I) 催化剂平台进行ROCOP.
- 研究了多种类型的异烯/环氧化物系统,包括碳二氧化物 (COS),PhNCS,化物和CS2.
- 分析了单体反应性,选择性和副产品的形成.
主要成果:
- 在控制活动和选择性方面展示了协同催化剂的性能.
- 在温和条件下确定碳酸 (COS) 为完美交替的共聚物中最有前途的单体.
- PhNCS成为一个可行的替代品,而化和CS2的选择性和副产品形成较低.
结论:
- 建立了首个预测框架,将硫单体身份与ROCOP的选择性和反应性联系起来.
- 能够合理设计具有量身定制的可降解,富硫的聚合物.
相关概念视频
Olefin Metathesis Polymerization: Overview
2.2K
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...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.2K
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.7K
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...
2.7K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
2.0K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
2.0K
Cationic Chain-Growth Polymerization: Mechanism
2.4K
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...
2.4K
Ziegler–Natta Chain-Growth Polymerization: Overview
3.4K
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...
3.4K
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
14.7K
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...
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...
14.7K


