Mechanism-Inspired Design of Bifunctional Catalysts for the Alternating Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides

被引:127
|
作者
Abel, Brooks A. [1 ]
Lidston, Claire A. L. [1 ]
Coates, Geoffrey W. [1 ]
机构
[1] Cornell Univ, Dept Chem & Chem Biol, Baker Lab, Ithaca, NY 14853 USA
基金
美国国家科学基金会;
关键词
COMBINING HIGH-ACTIVITY; PROPYLENE-OXIDE; PHTHALIC-ANHYDRIDE; CYCLOHEXENE OXIDE; CARBON-DIOXIDE; ASYMMETRIC CATALYSIS; LEWIS PAIRS; METAL-FREE; ALIPHATIC POLYESTERS; COBALT(III) COMPLEX;
D O I
10.1021/jacs.9b05570
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Advances in catalysis have enabled the ring-opening copolymerization of epoxides and cyclic anhydrides to afford structurally and functionally diverse polyesters with controlled molecular weights and dispersities. However, the most common systems employ binary catalyst/cocatalyst pairs which suffer from slow polymerization rates at low loadings. Inspired by new mechanistic insight into the function of binary metal salen/nucleophilic cocatalyst systems at low concentrations, we report a bifunctional complex in which the salen catalyst and an aminocyclopropenium cocatalyst are covalently tethered. A modular ligand design circumvents the extended linear syntheses typical of bifunctional catalysts, enabling systematic variation to understand and enhance catalytic activity. The optimized bifunctional aluminum salen catalyst maintains excellent activity for the ring-opening copolymerization of epoxides and cyclic anhydrides at low concentrations (>= 0.025 mol %), and the aminocyclopropenium cocatalyst suppresses undesirable transesterification and epimerization side reactions, preserving the integrity of the polymer backbone.
引用
收藏
页码:12760 / 12769
页数:10
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