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Perfectly Alternating and Regioselective Copolymerization of Carbonyl Sulfide and Epoxides by Metal-Free Lewis Pairs
writer:Yang, Jia-Liang,Wu, Hai-Lin,Li, Yang,Zhang, Xing-Hong,Darensbourg, Donald J.
keywords:Carbonyl Sulfide, Epoxides, Metal-Free Lewis Pairs
source:期刊
specific source:Angew. Chem. Int. Ed. 2017, 56, 5774 –5779
Issue time:2017年

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 kgmol-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.