Green conversion of carbon disulfide to degradable polydithiourethanes through catalyst-free multicomponent polymerizations of diamines, carbon disulfide and diacrylates

Abstract

In the pursuit of advanced functional polymer materials, sulfur-containing polymers have received tremendous attention owing to their superior chemical stability, high refractive indices, various supramolecular interactions, and robust dynamic covalent chemistry. However, their synthesis usually involves either expensive monomers or toxic byproducts and requires catalysts, thus hindering their widespread application. In this work, we present a catalyst-free multicomponent polymerization in organic solvents for the synthesis of various polydithiourethanes with excellent yields (up to 98 %) and high molecular weights (up to 112 kg/mol). This reaction involves the direct polymerization of carbon disulfide, an abundant one-carbon feedstock, with commercially available diamines and diacrylates. This polyaddition process demonstrates high atom economy and no byproduct, occurring at room temperature without the need for a catalyst, thus exhibiting excellent green chemistry metrics. By utilizing the dynamic covalent chemistry of dithiourethane groups, these polymers can be efficiently degraded via aminolysis and used to fabricate reprocessable vitrimers. This multicomponent polymerization opens up a new avenue for the efficient utilization of carbon disulfide resources and accelerates the exploration of diversified sulfur-containing functional polymer materials.