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An Examination of the Steric and Electronic Effects in the Copolymerization of Carbonyl Sulfide and Styrene Oxide
作者:Ming Luo, Xing-Hong Zhang,* Donald J. Darensbourg*
關鍵字:Carbonyl Sulfide, Copolymerization,Styrene Oxide
論文來源:期刊
具體來源:Macromolecules 2015, 48, 6057-6062
發(fā)表時間:2015年
The completely alternating copolymerization of carbonyl sulfide (COS) and styrene oxide was found to occur under mild reaction conditions (0-30 °C and 1.5 MPa) in the presence of (salen)CrCl/onium salt catalyst systems to afford high molecular weight poly(monothiocarbonates) with narrow molecular weight distributions. Ring-opening of styrene oxide was shown to be 88% selective at the methylene carbon. That is the reaction is driven by steric hindrance, where ring-opening occurs preferentially at the less congested carbon center. Similar results were found upon utilizing the tetramethyltetraazaannulene (tmtaa)CrCl/onium salt catalyst. On the other hand, upon employing a zinc-cobalt double metal cyanide (Zn-Co DMCC) catalyst, where the ligands around the active zinc site are not sterically encumbering, ring-opening of styrene oxide occurs predominantly at the methine carbon site; i.e., the reaction is electronically driven.
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