Stereochemistry‐Tuned Hydrogen‐Bonding Synergistic Covalent Adaptable Networks: Towards Recycled Elastomers with Excellent Creep‐Resistant Performance

Covalent adaptable networks (CANs) offer innovative solutions for the reprocessing and recycling of thermoset polymers. However, achieving a balance between easy reprocessing and creep resistance remains a challenge. This study focuses on designing and synthesizing polyurethane (PU) materials with tailored properties by manipulating the stereochemistry of diamine chain extenders. By employing cis‐ and trans‐configurations of diamine extenders, we developed a series of PU materials with varying mechanical properties and creep resistance. The trans‐configured materials (R,R‐DAC‐PU or S,S‐DAC‐PU) exhibited superior creep resistance and mechanical strength due to dense hydrogen bonding networks. The cis‐configured materials (Cis‐DAC‐PU) exhibited enhanced processability and elasticity. Under 0.1 MPa stress, R,R‐DAC‐PU showed a mere 3.5% strain change at 170 °C over 60 minutes, highlighting its superior creep resistance. Both configurations can be recycled via urea bond exchange reactions using hot pressing or solvothermal methods. Density Functional Theory (DFT) calculations indicate that both the (R,R‐DCA‐UB‐U)₂ and (S,S‐DCA‐UB‐U)₂ segments form six hydrogen bonds with shorter bond lengths, leading to stronger hydrogen‐bonding interactions. Conversely, the (Cis‐DCA‐UB‐U)₂ segment forms four hydrogen bonds with longer bond lengths, resulting in weaker interactions. This work highlights the critical role of stereochemistry in designing high‐performance, recyclable polymer materials with tailored properties.