A Novel POP-Ni Catalyst Derived from PBTP for Ambient Fixation of CO₂ into Cyclic Carbonates

The immobilization of homogeneous catalysts has always been a hot issue in the field of catalysis. In this paper, in an attempt to immobilize the homogeneous [Ni(Me₆Tren)X]X (X = I, Br, Cl)-type catalyst with porous organic polymer (POP), the heterogeneous catalyst PBTP-Me₆Tren(Ni) (POP-Ni) was designed and constructed by quaternization of the porous bromomethyl benzene polymer (PBTP) with tri[2-(dimethylamino)ethyl]amine (Me₆Tren) followed by coordination of the Ni(II) Lewis acidic center. Evaluation of the performance of the POP-Ni catalyst found it was able to catalyze the CO₂ cycloaddition with epichlorohydrin in N,N-dimethylformamide (DMF), affording 97.5% yield with 99% selectivity of chloropropylene carbonate under ambient conditions (80 °C, CO₂ balloon). The excellent catalytic performance of POP-Ni could be attributed to its porous properties, the intramolecular synergy between Lewis acid Ni(II) and nucleophilic Br anion, and the efficient adsorption of CO₂ by the multiamines Me₆Tren. In addition, POP-Ni can be conveniently recovered through simple centrifugation, and up to 91.8% yield can be obtained on the sixth run. This research provided a facile approach to multifunctional POP-supported Ni(II) catalysts and may find promising application for sustainable and green synthesis of cyclic carbonates.