通过Butadiene的循环聚合物化进行立体选择性循环化
Stefania Pragliola1, Giuseppe Milano, Gaetano Guerra
1Dipartimento di Chimica, Università di Salerno, I-84081 Baronissi (SA), Italy.
Journal of the American Chemical Society
|April 4, 2002
概括
一种新的循环聚合反应产生了独特的以乙烯为基础的共聚合物. 这个过程产生了具有环和环环的聚合物,显示出高的转变选择性和聚烯酸应用的潜力.
科学领域:
- 聚合物化学 聚合物化学
- 有机合成 有机合成
背景情况:
- 循环聚合提供了通往新型聚合物架构的途径.
- 催化方法对于控制聚合物结构和特性至关重要.
研究的目的:
- 通过循环聚合,呈现出前所未有的循环化.
- 为了研究乙烯和丁的催化共聚合.
主要方法:
- 乙烯和丁二烯的催化共聚.
- 对反应产物的分析,以进行结构性表征.
主要成果:
- 实现了Butadiene单元的完整循环聚合,具有高的转变选择性.
- 由乙烯制成的含有环和环环的共聚物.
- 获得所需共聚合物的高产量.
结论:
- 开发的方法可以有效地合成新型多聚烯.
- 由此产生的共聚物具有与材料科学相关的独特循环结构.
- 反应机制和高立体选择性是这个过程的关键特征.
相关概念视频
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
The electrophilic addition of hydrogen halides such as HBr to alkenes and nonconjugated dienes gives a single product as per Markovnikov’s rule.
Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control
The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
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...
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.


