Perfectly Alternating and Regioselective Copolymerization of Carbonyl Sulfide and Epoxides by Metal-Free Lewis Pairs

被引:171
作者
Yang, Jia-Liang [1 ]
Wu, Hai-Lin [1 ]
Li, Yang [1 ]
Zhang, Xing-Hong [1 ]
Darensbourg, Donald J. [2 ]
机构
[1] Zhejiang Univ, Dept Polymer Sci & Engn, MOE Key Lab Macromol Synth & Functionalizat, Hangzhou 310027, Zhejiang, Peoples R China
[2] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA
基金
美国国家科学基金会;
关键词
carbonyl sulfide; epoxide; Lewis pairs; organocatalysis; poly(monothiocarbonate)s; POLYMER SYNTHESIS; SALEN COMPLEXES; PROPYLENE-OXIDE; DIOXIDE; CO2; CATALYSTS; POLYCARBONATES; SELECTIVITY; ACTIVATION; REACTIVITY;
D O I
10.1002/anie.201701780
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The preparation of perfectly alternating and regioslective copolymers derived from the copolymerization of carbonyl sulfide (COS) and epoxides by metal-free Lewis pair catalysts composed of a Lewis base (amidine, guanidine, or quaternary onium salts) and a Lewis acid (triethyl borane) is described. Colorless and highly transparent copolymers of poly(monothiocarbonate) were successfully obtained with over 99% tail-to-head content and high molecular weight (up to 92.5 kg mol(-1)). In most instances, oxygen-sulfur exchange reactions (O/S ERs), which would generate random thiocarbonate and carbonate units, were effectively suppressed. The turnover frequencies (TOF) of these Lewis pair catalyzed processes were as high as 119 h(-1) at ambient temperature.
引用
收藏
页码:5774 / 5779
页数:6
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