在高通量选的帮助下,发现和优化用于乙烯寡合和聚合的新催化剂
David J Jones1, Vernon C Gibson, Simon M Green
1Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom.
Journal of the American Chemical Society
|August 4, 2005
概括
新的催化剂有效地氧化和聚合乙烯. 高吞吐量选发现了新的希夫基联体,导致了高活性系统的烯酸转化.
科学领域:
- 有机金属化学 有机金属化学
- 聚合物科学 聚合物科学
- 催化剂是一种催化剂.
背景情况:
- 希夫基联体在协调化学中具有多样性.
- 基于的催化剂对于烯酸聚合是至关重要的.
- 开发高效的乙烯寡合化和聚合化催化剂仍然是一个关键的挑战.
研究的目的:
- 发现新型,高活性基催化剂,用于乙烯的寡合和聚合.
- 为了探索希夫基联体与重的整形替代剂的结构-活性关系.
主要方法:
- 一个205个成员的Schiff基salicylaldimine连接物库的高吞吐量选 (HTS).
- 配体与 (p-tolyl) CrCl2 ((thf) 3.3) 的现场反应.
- 使用X射线晶体学对催化剂前体的表征.
主要成果:
- 确定了两种新类型的高活性基系统.
- 聚合系统:双酸甲基希夫基,产量高达3000gxmmol{-1) h{-1) bar{-1).
- 寡合化催化剂:三酸三乙烯基希夫基,产量高达10 000g×mmol{-1) h{-1) bar{-1) }.
结论:
- 庞大的正确替代的希夫基联体使乙烯转化具有高度活性的催化剂.
- 连接体结构决定了氧化或聚合的催化活性.
- 射线晶体学证实了关键催化剂前体的结构.
相关概念视频
Catalysis
The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
Cationic Chain-Growth Polymerization: Mechanism
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 generated carbocation,...
Ziegler–Natta Chain-Growth Polymerization: Overview
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 catalyst, high molecular...
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...
Catalysis
Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...
Heterogeneous Catalysis
Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...


