碳基离子环开放聚合二氧化碳2基异位 δ-瓦莱洛拉克
Yuling Lin1, Kaihao Chen1, Tianwen Bai2
1MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310058, China.
ACS macro letters
|March 5, 2025
概括
我们报告了第一个α-乙烯基-δ-乙烯-δ----瓦莱洛 (EVL) 的环开放聚合,以产生循环聚PEVL. 这种方法产生了具有可调节分子量和低玻璃过渡温度的明确聚合物.
科学领域:
- 聚合物化学 聚合物化学
- 有机合成 有机合成
- 材料科学 材料科学 材料科学
背景情况:
- 乳的环开聚合 (ROP) 是聚合成的关键方法.
- α-乙烯基-δ-乙烯-δ-瓦莱洛 (EVL) 是一种具有功能化潜力的二氧化碳衍生单体.
- 通过离子环开放聚合 (CROP) 进行EVL的同聚合,带来了独特的挑战.
研究的目的:
- 为了实现EVL的第一个离子环开放聚合 (CROP),EVL.
- 为了合成明确的循环聚PEVL.
- 为了研究聚合机制和聚合物的特性.
主要方法:
- 基于碳的阴阳环开放聚合 (CROP).
- 使用NMR,MALDI-ToF MS和DFT计算进行表征.
- 可变温度聚合研究和聚合后修饰.
主要成果:
- EVL的成功CROP产生周期性聚PEVL,M_n高达12.8kg/mol,分散度为1.2.
- PEVL包含两个结构单元,由EVL衍生,通过光谱和计算方法确认.
- 可调节的M_n从6.5到12.8kg/mol通过调节温度;低Tg为-33.6°C.
- 经过多聚化后的功能化通过醇-乙烯点击反应证明,引入了42.2°C的点.
结论:
- 基于碳的CROP机制使循环PEVL的受控合成成为可能.
- 快速的分子内转移和缓慢的启动有助于循环拓的忠实性.
- 由于其低Tg和可修改结构,PEVL是功能材料的多功能平台.
相关概念视频
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
2.5K
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...
2.5K
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...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.0K
Base-Catalyzed Ring-Opening of Epoxides
8.2K
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...
8.2K
Cationic Chain-Growth Polymerization: Mechanism
2.2K
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...
2.2K
Acid-Catalyzed Ring-Opening of Epoxides
7.0K
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...
7.0K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
1.9K
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...
1.9K


