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Alternating copolymerization of carbonyl sulfide and Cyclohexene Oxide catalyzed by zinc–cobalt double metal cyanide complex
writer:Ming Luo, Xing-Hong Zhang*, Bin-Yang Du, Qi Wang, Zhi-Qiang Fan
keywords:Carbonyl sulfide,Cyclohexene oxide,Copolymerization
source:期刊
specific source:Polymer 55 (2014) 3688-3695
Issue time:2014年

This paper describes the first example of alternating copolymerization of carbonyl sulfide (COS) with cyclohexene oxide (CHO) via heterogenous catalysis of a nano-lamellar zincecobalt(III) double metal cyanide complex (ZneCo(III) DMCC), providing an efficient method for converting COS to poly(cyclohexene monothiocarbonate) (PCHMTC) with an alternating degree up to 93%. The number-average molecular weight (Mn) of PCHMTC was 6.5e25.0 kg/mol with polydispersities (PDIs) of 1.6e2.1. The productivity of the catalyst was up to 970 g polymer/g catalyst (5.0 h). The oxygenesulfur exchange reaction (O/S ER) caused by ZneCo(III) DMCC was largely suppressed when the reaction was performed at 100e110 C in the presence of THF or CH2Cl2, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to 98%. The mechanisms of the copolymerization and O/S ER were proposed based on the ESI-MS, GCeMS and FT-IR spectra. The obtained PCHMTC is highly transparent and exhibitsgood solubility in various organic solvents, high Tg of 112 C, initial decomposition temperature of 214 C and high refractive index of 1.705.