Pd复合物促进了功能化的α,omega-dienes的循环聚合和与乙烯的共聚合,以获得具有循环重复单元的聚合物
Sehoon Park1, Daisuke Takeuchi, Kohtaro Osakada
1Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Yokohama 226-8503, Japan.
Journal of the American Chemical Society
|March 16, 2006
概括
二胺催化剂可使异基二甲基酸盐循环聚合,产生具有跨-1,2-异位循环基组的聚合物. 这一过程,特别是C2对称联体,允许高度调节的战术性和与乙烯的共聚合.
科学领域:
- 聚合物化学 聚合物化学
- 有机金属催化工艺
背景情况:
- (II) - 胺复合物是各种聚合反应的已知催化剂.
- 循环聚合为高分子提供了一条途径,其中的脊柱是循环单元.
研究的目的:
- 通过使用Pd(II) -二胺催化剂,研究异基二基酸盐的循环聚合.
- 探索连接体对称性对聚合物战术性的影响.
- 为了检查与乙烯的异利丁二利马酸盐的共聚合.
主要方法:
- 使用Palladium(II) -diimine复合物的催化环聚合.
- 通过C2-对称联结物通过受控的战术性合成聚合物.
- 乙烯大气层的聚合,用于合聚合物合并.
主要成果:
- 顺利的循环聚合物化异烯二甲基酸到具有转换-1,2-异位循环基的聚合物.
- 使用Pd复合体与C2-对称带实现高度调节的战术性.
- 通过在乙烯大气中聚合在聚乙烯中将高达42%的共体纳入.
结论:
- 二胺催化剂对于异烯二胺酸的循环聚合是有效的.
- 对于控制聚合物战术性而言,C2对称联体至关重要.
- 描述的方法允许合成具有可调节性质的新型共聚合物.
相关概念视频
Free-Radical Chain Reaction and Polymerization of Alkenes
The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
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.
Diels–Alder Reaction: Characteristics of Dienes
The Diels–Alder reaction brings together a diene and a dienophile to form a six-membered ring. Both components have unique characteristics that influence the rate of the reaction.
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
Characteristics of the diene
Conformation
The simplest example of a diene is 1,3-butadiene, an acyclic conjugated π system. At room temperature, the molecule exists as a mixture of s-cis and s-trans conformers by virtue of rotation around the carbon–carbon single bond. Although the s-trans isomer is more stable, the...
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...
Diels–Alder Reaction: Characteristics of Dienophiles
In a Diels–Alder reaction, the diene is usually an electron-rich system and acts as a nucleophile, whereas the dienophile is electron-deficient and functions as an electrophile. Much like the diene, the nature of the dienophile significantly impacts the outcome of the reaction.
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends on...
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends on...


