Polydithiocarbamates with Discontinuous <i>M</i>_ws Synthesized via Multicomponent 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(N-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(N-substituted)dithiocarbamates with high molecular weights (Mws) 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 Mws 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-Mw portion in the upper layer and a high-Mw portion in the bottom layer. These poly(N-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.