Precision copolymerization of CO2 and epoxides enabled by organoboron catalysts

Rational Optimization of Bifunctional Organoboron Catalysts for Versatile Polyethers via Ring-Opening Polymerization of Epoxides

“…CCDC deposition numbers of 8 ·(DMF) 2 , 9 ·(DMF) 2 , and 10 ·(DMF) 2 are 2012655, 1974835, and 1974836, respectively. Note: the crystals of 1 ·(DMF) 2 , 8· (DMF) 2 , and 10· (DMF) 2 have been reported in other publications. , …”

“…In recent years, our group has developed a kind of organoboron catalysts, termed a dynamic Lewis multicore system (DLMCS), which integrates the Lewis acidic boron (B) center(s) and an ammonium salt (or phosphonium salt) in one molecule. , These organoboron catalysts are efficient for epoxide-involved polymerizations and could be easily tailored through a two-step synthesis (quaternization and hydroboration reactions), enabling kilogram-scale production of catalysts. The DLMCS displayed high efficiency in producing polycarbonates via ring-opening copolymerization (ROCOP) of epoxides and CO 2 , and polyesters via ROCOP of epoxides and anhydrides (or CO). − When the dinuclear organoboron catalysts (such as catalyst 1 in Scheme ) were utilized for the ROP of epoxides, the polymerization displayed fast and controlled behavior under mild conditions (−20 to 25 °C, 1 bar). The molecular weight of the produced polyethers can reach 10 6 g/mol .…”

Recyclable, Fire-Resistant, Superstrong, and Reversible Ionic Polyurea-Based Adhesives

“…Material Characterization. 1 H NMR and 13 C NMR spectra were collected on Avance III HD 600 MHz spectrometers (Bruker, Switzerland) with d 6 -DMSO as the solvent. Fourier transform infrared (FTIR) spectra were recorded on a Nicolet iS50 (Nicolet Corporation) ranging from 525 to 4000 cm −1 .…”

“…Carbon dioxide (CO 2 ) is one of the most attractive eco-friendly C1 resources, and its conversion and utilization are receiving global consensus in terms of achieving carbon neutrality and lowering petroleum usage. − Although the inherent thermostability and chemical inertness of CO 2 encumber its upgradation to higher value-added chemicals, numerous endeavors have been devoted to converting CO 2 into hydrocarbon fuels or polymeric materials through developing exquisite catalyst systems, , cooperating with green energies (electricity, solar, or heat), − or coupling with high-energy reactants. − The reduction of CO 2 into hydrocarbon fuels is of paramount importance to alleviate energy and environmental problems, but only a few high-value products are economically viable due to low product selectivity and unsatisfied energy efficiency. − On the other hand, copolymerization of CO 2 with epoxides, diols, diamines, or amino alcohols to synthesize functional polymers [polycarbonate (PC), polyurea (PUa), and polyurethane (PU)] is a highly rewarding CO 2 -valorization approach. − …”

Borinane-based organoboron catalysts for alternating copolymerization of CO2with cyclic ethers: improved productivity and facile recovery

“…In the case of a monomer of industrial relevance such as PO, those catalysts could regulate the content of carbonate and afford a carbonate linkage content of 95.2%. 54 Based on our experience in boronmediated ROCOP of CO 2 and PO, we envision that a perfect alternating carbonate linkage and increased reactivity could be achieved by fine tuning the steric hindrance and Lewis acidity of boron centers in such bifunctional systems. Overall, it is still a challenge to bring about the organocatalytic copolymerization of CO 2 and PO to access perfectly alternating polycarbonates and effective catalyst recovery.…”