Poly(monothiocarbonate)s from the Alternating and Regioselective Copolymerization of Carbonyl Sulfide with Epoxides

/epoxide copolymerization. Of note, a specialty of COS/epoxide copolymerization is the occurrence of an oxygen-sulfur exchange reaction (O/S ER), which may produce carbonate and dithiocarbonate units. O/S ER, which are induced by the metal-OH bond regenerated by chain transfer reactions, can be kinetically inhibited by changing the reaction conditions. We provide a thorough mechanistic understanding of the electronic/steric effect of the catalysts on the regioselectivity of COS copolymerization. The regioselectivity of the copolymerization originates from the solely nucleophilic attack of the sulfur anion to methylene of the epoxide, and thus, the chiral configuration of the monosubstituted epoxides is retained. COS-based copolymers are highly transparent sulfur-containing polymers with excellent optical properties, such as high refractive index and Abbe number. Thanks to their good solubility and many available epoxides, COS/epoxide copolymers can potentially be a new applicable optical material. Very recently, crystalline COS-based polymers with or without chiral carbons have been synthesized, which may further expand the scope of application of these new materials.