<p>This study reports a general synthetic strategy for redox-responsive gels and porous polymers incorporating disulfide bonds. Network polymers were prepared via ring-opening addition reactions of multifunctional epoxides or a trifunctional isocyanate with dithiodicarboxylic acids or a disulfide-containing diol, affording mechanically tunable gels. The elastic modulus of the networks depended on the alkyl chain length of the disulfide crosslinkers and the extent of reaction conversion. Porous polymers were obtained through polymerization-induced phase separation in the addition reactions of a trifunctional aziridine or a trifunctional isocyanate with dithiodicarboxylic acids, yielding interconnected particle-based or co-continuous monolithic morphologies with controllable feature sizes and mechanical properties. All gels underwent efficient reductive degradation in the presence of dithiothreitol, while oxidative conditions enabled regeneration of the network structure, demonstrating reversible crosslinking. Notably, a disulfide-containing gel exhibited electrochemically triggered degradation. These results demonstrate a versatile platform for designing redox-degradable and reconfigurable polymer networks and porous materials with tunable structures and functions.</p>

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Network polymers containing disulfide bond prepared by addition reactions of multi-functional epoxies, aziridine, or isocyanates with dicarboxylic acids or diols: structure, mechanical properties, and reductive degradation

  • Naofumi Naga,
  • Kazumasa Moriyama,
  • Kazuma Hasegawa,
  • Toshiki Tajima,
  • Tamaki Nakano

摘要

This study reports a general synthetic strategy for redox-responsive gels and porous polymers incorporating disulfide bonds. Network polymers were prepared via ring-opening addition reactions of multifunctional epoxides or a trifunctional isocyanate with dithiodicarboxylic acids or a disulfide-containing diol, affording mechanically tunable gels. The elastic modulus of the networks depended on the alkyl chain length of the disulfide crosslinkers and the extent of reaction conversion. Porous polymers were obtained through polymerization-induced phase separation in the addition reactions of a trifunctional aziridine or a trifunctional isocyanate with dithiodicarboxylic acids, yielding interconnected particle-based or co-continuous monolithic morphologies with controllable feature sizes and mechanical properties. All gels underwent efficient reductive degradation in the presence of dithiothreitol, while oxidative conditions enabled regeneration of the network structure, demonstrating reversible crosslinking. Notably, a disulfide-containing gel exhibited electrochemically triggered degradation. These results demonstrate a versatile platform for designing redox-degradable and reconfigurable polymer networks and porous materials with tunable structures and functions.