Synthesis of Zn–Fe double metal cyanide complexes with imidazolium-based ionic liquid cocatalysts via ball milling for copolymerization of CO2 and propylene oxide

In this work, Zn–Fe double metal cyanide (DMC) catalysts were successfully synthesized via clean and efficient ball milling. Imidazolium-based ionic liquids as cocatalysts were incorporated into the structure of the DMC catalysts during the grinding process. The modified Zn–Fe DMC catalysts were effective for the alternating copolymerization of carbon dioxide and propylene oxide under controlled reaction conditions. The properties and structures of the Zn–Fe DMC catalysts and the resulting polymers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, elemental analysis, ¹H and ¹³C NMR spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The results indicate that the Zn–Fe DMC catalysts exhibit higher thermal stability compared to the DMC catalysts without imidazolium-based ionic liquids (DMC-Blank). We determined that the introduction of a small amount of imidazolium-based ionic liquids can increase the carbonate content of the poly(propylene carbonate) (PPC) copolymer in the range of 18.48–29.00%. The turnover numbers of PPC were ∼4.40. In addition, the measured number-average relative molecular mass was in the range of 2.96 × 10³–4.98 × 10³ with a narrow polydispersity index of 1.00–1.08.

Zn–Fe DMC complexes with imidazolium-based ionic liquid cocatalysts were prepared by a clean and efficient ball milling process for the copolymerization of CO₂ and propylene oxide.