Polydithiocarbamateswith Discontinuous <i>M</i>_ws Synthesized viaMulticomponent Tandem Polymerizations of CS₂, Secondary Diamines,and Dibromide

Polydithiocarbamates are a group of promising functional polymer materials with unique structures, dynamic reversible properties, and photosensitivity, but the efficient, convenient, and diversified syntheses of poly(<i>N</i>-substituted)dithiocarbamates remain challenging. In this work, room temperature transition-metal-free multicomponent tandem polymerization (MCTP) of CS₂, secondary diamines, and 1,4-di(bromomethyl)benzene was reported to construct five poly(<i>N</i>-substituted)dithiocarbamates with high molecular weights (<i>M</i>_ws) of up to 60800 g/mol and high yields of up to 91% using commercially available simple monomers under mild and convenient conditions, achieving high atom economy and about 60 g-scale synthesis. Most importantly, polymers with discontinuous <i>M</i>_ws could be obtained in one pot, depending on the amine structures and polymerization time, and the solution underwent automatic stratification during the polymerization with a low-<i>M</i>_w portion in the upper layer and a high-<i>M</i>_w portion in the bottom layer. These poly(<i>N</i>-substituted)dithiocarbamates generally possessed good solubility, high thermal stability and could be photodegraded efficiently upon UV irradiation to produce terephthalaldehyde. The MCTP has provided a simple and robust synthetic approach for polydithiocarbamates, and the self-stratification has been suggested as a facile method for molecular weight control of step-growth polymerizations, which could accelerate the development of polymerization methodology and sulfur-containing polymer materials.