Effects of addition mode on Zn–Co double metal cyanide catalyst for synthesis of oligo(propylene‐carbonate) diols

Abstract

Zn–Co double metal cyanide (DMC) complexes are promising catalytic systems for copolymerization of epoxide and CO2. In the work reported, Zn–Co DMC catalysts were prepared by parallel‐flow dropping, forward dropping and reverse dropping methods, aiming to provide an insight into the effect of addition mode on catalyst structure and catalytic performance. Catalytic properties were evaluated using the copolymerization reaction of propylene oxide (PO) and CO2 in the presence of chain transfer agent. The results indicated that the factors that affect crystalline state are different for different modes. And excess zinc chloride is the prerequisite for organic ligands to be retained in the catalyst and affect the structure. In addition, a catalyst with flower‐like morphology was obtained with the parallel‐flow dropping method which provided larger surface area. An appropriate O/Zn value ensured abundant active PO which would suppress the backbiting process by forming consecutive PO units adjacent to CO2 units. Oligo(propylene‐carbonate) diols with average molecular weight of 1020 g mol−1, CO2 incorporation of 24.92% and WPC of 5.14 wt% were obtained at 80 °C and 2 MPa.