Diversified synthesis of poly(sulfonyl isourea)s by multicomponent polymerizations of isocyanides, sulfonyl azides, and alcohols/phenols

Multicomponent polymerization (MCP) has become a powerful tool for the preparation of polymers with complex or well-defined structures. The development of MCPs that can take full advantage of the great diversity of monomer combinations is attractive but still remains challenging. Herein, we report a facile MCP method using isocyanides, sulfonyl azides, and alcohol/phenols as monomers, in which the monomer combination can be readily tuned to achieve the diversity-oriented synthesis of poly(sulfonyl isourea)s in excellent atom economy. By systematically optimizing the polymerization conditions and changing the functionalities and combinations of monomers, a series of heteroatom-rich polymers with sulfonyl isourea units and high molecular weights (Mw values of up to 120 500) were successfully prepared. All the obtained polymers exhibit good thermal stability, and the variation in polymer backbone structures led to an obvious difference in their morphological stability. This diversity-oriented MCP strategy may provide inspiration and new possibilities for the development of heterochain polymers with advanced functionalities.