Synthesis of differentiated sulfur-containing polymers by regiodivergent polymerization of Morita–Baylis–Hillman acetates and thiols

The development of facile strategies to access differentiated functional polymers starting from identical monomers is challenging yet desirable in polymer chemistry. Herein, we report a novel regiodivergent polymerization strategy for synthesizing differentiated sulfur-containing polymers starting from Morita–Baylis–Hillman (MBH) acetates and thiols. By properly selecting the catalysts and reaction conditions, the polymerization could be performed efficiently with a range of MBH acetates and thiols under ambient conditions, allowing access to differentiated sulfur-containing polymers with excellent α- or γ-regioselectivity. Meanwhile, density functional theory calculations were used to elucidate the origin of the regioselectivity of the polymerizations. In addition, the resulting α- and γ-polymers possessed different glass transition temperatures and refractive index values, and the γ-polymers could be transformed into the corresponding α-polymers under radical conditions. This work represents a new strategy to synthesize structurally diverse functional polymers with tailored properties.