Organocatalytic Synthesis of Polysulfonamides with Well-Defined Linear and Brush Architectures from a Designed/Synthesized Bis(N-sulfonyl aziridine)

We report a new synthetic methodology for polysulfonamides with well-defined linear and brush architectures by organocatalytic polymerizations. A new monomer, bis(2,3-disubstituted N-sulfonyl aziridine), has been rationally designed/synthesized and used in step-growth polymerization with various bisnucleophiles (dicarboxylic acids, diphenols, and dithiols). The branches or cross-linkages derived from the ring-opening polymerization of N-sulfonyl aziridines are suppressed using this specific bis(aziridine) monomer, resulting in a well-controlled linear polysulfonamide architecture. The synthesized polysulfonamides emit blue fluorescence in solution and exhibit excellent thermal properties with decomposition temperature at 5% weight loss (T-d,T-5%) up to 360.0 degrees C and glass-transition temperature (T-g) ranging from 62.5 to 199.2 degrees C. Furthermore, a fast one-pot cascade approach has been developed toward polysulfonamide brush copolymers with a well-controlled grafted chain length.

Automated summary

A new synthetic methodology for well-defined linear and brush polysulfonamides has been developed through organocatalytic polymerizations. The use of a specific bis(aziridine) monomer suppresses branching from N-sulfonyl aziridines, resulting in controlled linear architectures. The synthesized polysulfonamides exhibit blue fluorescence, excellent thermal properties, and a fast one-pot cascade approach has been developed for brush copolymers with controlled grafted chain length.