Theoretical Investigation on the Catalytic Activity of Bis-boron Phosphonium Salt for the Copolymerization of Propylene Oxide and Carbon Dioxide

Abstract

This study theoretically investigated the regulation mechanism of catalytic activity in the copolymerization of propylene oxide (PO) and carbon dioxide (CO₂) catalyzed by a well-designed bis-boron phosphonium salt (PBB) catalyst through density functional theory (DFT) calculations. Mechanistic analysis suggests that the alternating copolymerization of PO and CO₂ is thermodynamically and kinetically favorable. The results revealed that initiation efficiency is dependent on the counter anions of phosphonium salt, where Br. exhibited a higher ring-opening reactivity of PO than Cl.. The electronic effect of the catalyst for the initiation step is investigated by altering substituent groups in PBB catalysts and results suggest that the catalytic activity is improved by the substitution of electron-donating groups. On the other hand, the catalytic activity of such PBB catalysts is also significantly dependent on the number of methylene groups (chain length) between the phosphorus center and boron atom, suggesting a synergism and confinement characteristic of PBB catalysts. Interestingly, computational results clearly show that secondary (electrostatic) interaction induced by the tetra-coordinated boronate complex stabilizes the transition states of ring-opening of PO and accelerates the polymerization. This work provides theoretical insights for designing efficient supramolecular catalysts and optimizing CO₂ utilization strategies.

Keywords

Bis-boron catalyst / Ring-opening reaction / Catalytic activity / Copolymerization / Density functional theory

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Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH