CHAPTER 10. Organocatalytic Synthesis of CO2(COS)-based Copolymers

In this chapter, we highlight the very recent advances in organocatalytic copolymerizations of carbon dioxide (CO2) and carbonyl sulfide (COS), two typical one-carbon (C1) building blocks. The organic catalyst systems for CO2(COS)/epoxide copolymerizations are intensively discussed. Organocatalysts perform well especially in the copolymerization of COS with epoxides. Fully alternating and regioselective COS-based copolymers with precise end groups can be produced. The synthesis of various types of CO2(COS)-based copolymers including block copolymers is also presented. In correspondence, the organocatalytic mechanism involving two C1 monomers is introduced. Furthermore, by generalizing the methods for C1/epoxide copolymerization, a “supramolecular anion” strategy is proposed for controlled/living anionic polymerizations, and successfully expanded to the controlled polymerization of PO for polyethers, ROP of γ-BL for polyesters and the copolymerization of PO with cyclic anhydrides for alternating polyesters. Finally, the properties of C1-based copolymers are introduced.