Synthesis of Linear and Branched Polycarbonate Polyols via Double Metal Cyanide-Catalyzed Ring-Opening (Co)polymerization of Epoxides.

A series of polyether and poly(ether carbonate) polyols have been synthesized via Zn(II)-Co(III) double metal cyanide (DMC)-catalyzed ring-opening (co)polymerization of various epoxides, such as propylene oxide, 1,2-epoxybutane, epichlorohydrin, styrene oxide, and glycidol, with and without CO2. The resulting polyether polyols exhibit linear and branched architectures (degrees of branching, DB = 0.27), high catalytic activities with turnover frequencies up to 461 min-1, narrow dispersities (1.15-1.25), and low levels of unsaturation (0.004 meq g-1). The DMC catalysts also enable the efficient synthesis of poly(propylene carbonate) polyol with carbonate contents up to 40% and yields reaching 63%. Additionally, branched poly(ether carbonate) polyols with tunable DB values (0.14-0.21), yields up to 70%, and carbonate contents up to 33% are synthesized via CO2 fixation to glycidol. The synthesized polyols hold strong potential for industrial applications in polyurethanes and other advanced materials, offering versatile performance for use in coatings, adhesives, sealants, and elastomers. Overall, this study highlights the effectiveness of DMC catalysts in producing high-performance polyols, contributing to the development of sustainable materials with precise architectural control.