Eco‐friendly synthesis of non‐isocyanate polyurea using PET and CO2 upcycling: A double green approach

Abstract From the perspective of sustainability, this research explored both the recycling of polyethylene terephthalate (PET) and the conversion of carbon dioxide (CO 2 ) into polymer materials. To this end, a series of copolyurea specimens were synthesized through the polycondensation of carbon dioxide with hexamethylenediamine (HDA) and terephthalic dihydrazide (TDH), where TDH was derived from the chemical recycling of PET via the aminolysis method. FTIR spectroscopy, 1 H NMR, differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA) characterized the products of PET recycling and synthesized copolyureas. Additionally, we sought to identify the optimal parameters for both the recycling and copolymerization processes. The results of identification analyses for both the recycling and copolymerization reactions confirmed the formation of the desired structures. An increase in the hard segment (TDH) led to discrepancies between the intended and actual monomer ratios in the synthesis, possibly due to dimethyl sulfoxide (DMSO) solubility issues or unreacted TDH. Furthermore, the TGA analysis indicated that the initial degradation temperature ( T d,5% ) of the copolymer increased with the proportion of aromatic rings in the hard segment, underscoring the complex interactions within the copolymer matrix affecting its thermal and structural properties. The DSC results revealed that for copolyureas with the formula HDA x TDH 100– x (where x = 50, 60, 70, 80, 90), reducing the x fraction or increasing the TDH content lowered the melting temperature. Furthermore, at a high percentage of TDH, the melting point disappeared entirely due to the destruction of the crystalline structure, indicating a critical threshold where the copolymer transitions from a semi‐crystalline to an amorphous state.