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

Abstract

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,5% ) up to 360.0 °C and glass-transition temperature (T g ) ranging from 62.5 to 199.2 °C. Furthermore, a fast one-pot cascade approach has been developed toward polysulfonamide brush copolymers with a well-controlled grafted chain length.

Tributylphosphine-catalyzed aziridine-based cycloaddition polymerization toward thiacyclic polymers

“…((4-(4-(((R)-2-isopropylaziridin-1-yl) sulfonyl)phenoxy)phenyl)sulfonyl)aziridine were synthesized according to the previous method. 48 Instrumentation 1 H NMR spectra were recorded with a Bruker AVANCE III 400 spectrometer. 13 C NMR spectra were recorded with a Bruker AVANCE III 600 spectrometer.…”

“…7,7′-(Oxybis(4,1-phenylenesulfonyl))bis(7-azabicyclo[4.1.0]heptane), 1,1′-(oxybis(4,1-phenylenesulfonyl))bis(2-methylaziridine), ( S )-2-isopropyl-1-((4-(4-((( R )-2-isopropylaziridin-1-yl)sulfonyl)phenoxy)phenyl)sulfonyl)aziridine were synthesized according to the previous method. 48…”

“…46,47 Moreover, we recently prepared a new bis(N-sulfonal aziridine) monomer, which can undergo polyaddition reactions with dicarboxylic acids, diphenols, or dithiols toward polysulfonamides in the presence of an organocatalyst. 48 The thioether group has been introduced to the polysulfonamide chain using tributylphosphine as the catalyst (Scheme 1d). The synthesized poly (sulfonamide thioether)s exhibited excellent thermal properties.…”

“…Scheme 1 (a)-(c)Typical examples of cycloaddition polymerization,18,19,23 and (d) the synthesis of sulfur-containing polymers by Bu 3 P-catalyzed aziridine-based step-growth polymerization (our previous work,48 and this work).…”

Catalyst-free aziridine-based step-growth polymerization: a facile approach to optically active poly(sulfonamide amine)s and poly(sulfonamide dithiocarbamate)s

“…Our group recently reported the facile synthesis of linear polysulfonamides via an efficient organocatalytic step-growth polymerization of bis( N -sulfonyl aziridine) with dicarboxylic acid, diphenol, or dithiol (Scheme 1c). 37 The control of the polymer architecture has been well accomplished using a specially designed/synthesized bis(2,3-disubstituted N -sulfonyl aziridine) monomer. It should be noted that the bis(2-monosubstituted N -sulfonyl aziridine) monomer will be homopolymerized when it is employed for this organocatalytic step-growth polymerization, and a cross-linked polymer will be formed.…”