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Thermolysis of a urethane end group was observed as a first time phenomenon during activation. This unzipping mechanism revealed a new amine tethering point producing a diamine-terminated oligourea ([10]-OU), acting as a green sorbent for CO2 capturing. The oligomer backbites its end group to form propylene carbonate (PC), as proved by in situ TGA-MS, which can reflect the polymer performance by maximizing its capturing capacity. Cross polarization magic angle spinning (CP-MAS) NMR spectroscopy verified the formation of the proven ionic carbamate (1:2 mechanism) with a chemical shift at 161.7 ppm due to activation desorption at higher temperatures, viz., 100 °C (in vacuo) accompanied with bicarbonate ions (1:1 mechanism) with a peak centered at 164.9 ppm. Fortunately, the amines formed from in situ thermolysis explain the abnormal behavior (carbamates versus bicarbonates) of the prepared sample. Finally, ex situ ATR-FTIR proved the decomposition of urethanes, which can be confirmed by the disappearance of the pre-assigned peak centered at 1691 cm−1. DFT calculations supported the thermolysis of the urethane end group at elevated temperatures, and provided structural insights into the formed products. [ABSTRACT FROM AUTHOR]

Thermolysis of a urethane end group was observed as a first time phenomenon during activation. This unzipping mechanism revealed a new amine tethering point producing a diamine-terminated oligourea ([10]-OU), acting as a green sorbent for CO 2 capturing. The oligomer backbites its end group to form propylene carbonate (PC), as proved by in situ TGA-MS, which can reflect the polymer performance by maximizing its capturing capacity. Cross polarization magic angle spinning (CP-MAS) NMR spectroscopy verified the formation of the proven ionic carbamate (1:2 mechanism) with a chemical shift at 161.7 ppm due to activation desorption at higher temperatures, viz. , 100 °C ( in vacuo ) accompanied with bicarbonate ions (1:1 mechanism) with a peak centered at 164.9 ppm. Fortunately, the amines formed from in situ thermolysis explain the abnormal behavior (carbamates versus bicarbonates) of the prepared sample. Finally, ex situ ATR-FTIR proved the decomposition of urethanes, which can be confirmed by the disappearance of the pre-assigned peak centered at 1691 cm -1 . DFT calculations supported the thermolysis of the urethane end group at elevated temperatures, and provided structural insights into the formed products.