Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity

Graphical The synthesis of poly(propylene monothiocarbonate)s from COS/PO copolymerization under mild conditions using the heterogeneous catalyst CoCo-PBA is reported. This study demonstrates the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate (Co 3 [Co(CN) 6 ] 2 ), a typical cobalt Prussian Blue Analogue (CoCo-PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number-average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0–3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen-sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo-PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.