Developing recyclable, reworkable, and intelligent thermosetting polymers, as a long-standing challenge, is highly desirable for modern manufacturing industries. Herein, we report a polyhexahydrotriazine thermoset (PHT) prepared by a one-pot polycondensation between 4-aminophenyl disulfide and paraformaldehyde. The PHT has a glass transition temperature of 135 °C and good solvent resistance. The incorporation of dual stimuli-responsive groups (disulfide bond and hexahydrotriazine ring) endows the PHT with re-processability, re-workability, and damage monitoring function. The PHT can be repeatedly reprocessed by hot pressing, and a near 100% recovery of flexural strength is achieved. The PHT can also degrade in inorganic acid or organic thiol solutions at room temperature. The thermally reworkable test demonstrates that, after heating the PHT at 200 °C for 1 h, the residuals can be easily wiped off. Finally, the PHT exhibits a reversible mechanochromic behavior when damaged.
Keywords: disulfide bonds; polyhexahydrotriazine; recyclability; vitrimers.