期刊
MACROMOLECULES
卷 45, 期 13, 页码 5387-5396出版社
AMER CHEMICAL SOC
DOI: 10.1021/ma301130b
关键词
-
资金
- National Science Foundation [CHE-0610183, CHE-0952054, CHE-0842654, 00006595]
- Center for Sustainable Polymers, a National Science Foundation supported Center for Chemical Innovation [CHE-1136607]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1136607, 0952054, 0842654] Funding Source: National Science Foundation
The kinetics of polymerization of epsilon-caprolactone (CL) initiated by aluminum-alkoxide complexes supported by the dianionic forms of N,N-bis[methyl-(2-hydroxy-3-tert-butyl-5-R-phenyl)]-N,N-dimethylethylenediamines, (L-R)Al(Oi-Pr) (R = OMe, Br, NO2) were studied. The ligands are sterically similar but have variable electron donating characteristics due to the differing remote (para) ligand substituents R. Saturation kinetics were observed using [CL](0) = 2-2.6 M and [complex](0) = 7 mM, enabling independent determination of the substrate coordination (K-eq) and insertion (k(2)) events in the ring-opening polymerization process. Analysis of the effects of the substituent R as a function of temperature on both K-eq and k(2) yielded thermodynamic parameters for these steps. The rate constant k(2), related to alkoxide nucleophilicity, was strongly enhanced by electron-donating R substituents, but the binding parameter K-eq is invariant as a function of ligand electronic properties. Density functional calculations provide atomic-level detail for the structures of key reaction intermediates and their associated thermochemistries.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据