通过对O-碳素化的受控环开放聚合,实现了功能化的循环多 (α-氧酸)
Ziyu Huo1, Xiaoyu Xie1, Nadim Mahmud2
1Department of Chemical Engineering, Virginia Polytechnic Institute and State University, 635 Prices Fork Road, Blacksburg, Virginia, 24061, USA.
Angewandte Chemie (International ed. in English)
|April 7, 2025
概括
研究人员开发了一种可扩展的方法,使用受控聚合来合成高分子量循环聚. 这一突破克服了以前的局限性,使得能够创建具有独特性质的高级功能循环聚合物.
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:
- 线性聚 ((α-酸) 是通过O-碳酸的环开聚合合成的至关重要的可降解聚合物.
- 以前的循环聚 (α-酸) 合成方法出现了副作用,阻碍了高分子量立体规律聚合物的生产.
研究的目的:
- 开发一种可扩展和可控制的方法来合成高分子量,立体规律的循环多 (α-基酸).
- 探索使用开发的催化系统制备循环块聚 (α-氧酸).
- 与线性对应物相比,研究合成的循环聚合物的独特物理化学特性.
主要方法:
- 采用了一种催化系统,包括一个复合物,一个硬质体积大的配体和一个烯胺,用于控制的聚合.
- 使用O-碳素化物作为单体用于环开放聚合.
- 实施了O-carboxyanhydrides的顺序添加,以合成循环块聚-α-基酸).
主要成果:
- 成功合成了高分子量 (>100 kDa) 立体规律的功能性循环多分子 (α-氧酸).
- 通过顺序的单体添加,实现了循环块聚 (α-氧酸) 的容易制备.
- 与线性类似物相比,观察到周期性聚合物的独特物理化学特性,包括相位过渡温度升高,强度提高和粘度降低.
结论:
- 已经建立了一种新的,可扩展的方法来生产高分子量立体规律循环聚合物.
- 开发的催化系统可以合成具有可调节性质的循环块共聚合物.
- 这些循环聚合物的独特特性在各种应用中比传统的线性聚合物具有潜在的优势.
相关概念视频
Anionic Chain-Growth Polymerization: Overview
2.0K
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,...
2.0K
Anionic Chain-Growth Polymerization: Mechanism
2.0K
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...
2.0K
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
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
Preparation of Acid Anhydrides
3.0K
One of the methods for preparing symmetrical or unsymmetrical acid anhydrides involves the treatment of acid chlorides with the sodium salt of carboxylic acids. The reaction proceeds via a nucleophilic acyl substitution.
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...
The carboxylate ion acts as a nucleophile that attacks the carbonyl carbon of the acid chloride to form a tetrahedral intermediate. Subsequently, the re-formation of the carbonyl group with the loss of the chloride ion as a leaving group leads to the formation of an acid...
3.0K
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


