Polymers containing sulfur centers with high oxidation states in the main chain, polysulfoxide and polysulfone, display desirable properties such as thermomechanical and chemical stability. To circumvent their challenging direct synthesis, methods based on the oxidation of a parent polysulfide have been developed but are plagued by uncontrolled reactions, leading either to ill-defined mixtures of polysulfoxides and polysulfones or to polysulfones with reduced degrees of polymerization due to overoxidation of the polymer. We developed an alternative method to produce well-defined polysulfoxide and polysulfone in a waterborne colloidal emulsion using different oxidants to control the oxidation state of sulfur in the final materials. The direct oxidation of water-based polysulfide latexes avoided the use of volatile organic solvents and allowed for the control of the oxidation state of the sulfur atoms. Oxidation of parent polysulfides by tert-butyl hydroperoxide led to the production of pure polysulfoxides, even after 70 days of reaction time. Additionally, hydrogen peroxide produced both species through the course of the reaction but yielded fully converted polysulfones after 24 h. By employing mild oxidants, our approach controlled the oxidation state of the sulfur atoms in the final sulfur-containing polymer and prevented any overoxidation, thus ensuring the integrity of the polymer chains and colloidal stability of the system. We also verified the selectivity, versatility, and robustness of the method by applying it to polysulfides of different chemical compositions and structures. The universality demonstrated by this method makes it a powerful yet simple platform for the design of sulfur-containing polymers and nanoparticles.
© 2021 The Authors. Published by American Chemical Society.